Post on 06-Feb-2018
Research ArticleEvaluation of Heavy Metals Contamination from Environmentto Food Matrix by TXRF The Case of Rice and Rice Husk
Fabjola Bilo Marco Lodolo Laura Borgese Alberto Bosio Laura BenassiLaura Eleonora Depero and Elza Bontempi
Chemistry for Technologies Laboratory Department of Mechanical and Industrial Engineering University of BresciaVia Branze 38 25123 Brescia Italy
Correspondence should be addressed to Elza Bontempi elzabontempiunibsit
Received 4 December 2014 Revised 2 March 2015 Accepted 3 March 2015
Academic Editor Javier Hernandez-Borges
Copyright copy 2015 Fabjola Bilo et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited
This paper is devoted to the chemical analysis of contaminated soils of India and the rice grown in the same area Total reflectionX-ray fluorescence spectroscopy is a well-established technique for elemental chemical analysis of environmental samples and itcan be a useful tool to assess food safety Metals uptake in rice crop grown in soils from different areas was studied In this worksoil rice husk and rice samples were analyzed after complete solubilization of samples by microwave acid digestion Heavy metalsconcentration detected in rice samples decreases in the following order Mn gt Zn gt Cu gt Ni gt Pb gt Cr The metal content in ricehusk was higher than in rice This study suggests for the first time a possible role of heavy metals filter played by rice husk Theknowledge of metals sequestration capability of rice husk may promote some new management practices for rice cultivation topreserve it from pollution
1 Introduction
Heavy-metal pollution of soil affects the quality of the enviro-nment leading to serious consequences Heavy metals groupincludes Ag Ba Cd Co Cr Mn Hg Mo Ni Pb Cu SnTl V Zn and some metalloids such as As Sb Bi and SeArsenic for example is often considered as a heavy metaldue to the similarity of its chemical properties and behaviorwith the other heavy metals Heavy metals accumulation insoil and in the environment in general may be related to thephenomenon of bioaccumulation ability of living organismsthat is increasing the concentration at human organism dueto industrial activities and the food chain The main sourcesof heavy-metal pollution in soil are irrigation especiallywith sewage solid-waste disposal for example sludge andcompost refuse the use of pesticides and fertilizers andatmospheric deposition [1]
Plants acquire the necessary nutrients such asN P andKfrom the environment However they may also accumulateunnecessary and toxic metals such as Pb and Cd Severalplants have the ability to accumulate high metal concentra-tions [2] Many studies have reported data for the transfer of
heavymetals from soil to plants and vegetables through rootsand shoot [3] Therefore toxic metals such as As Cd and Pbcan be taken up from cereal crops and transferred to theirgrains [4] Toxic metals may be classified according to theircapability of being transferred from soil to plants in mobilemetals such as Cd and poorlymobilemetals such as PbThisproperty may affect their bioaccumulation in plants [5]
Rice is one of the most important and widespread cerealsin the world It is the staff of life for 3 billion people mainly inAsia [6] contributing over 70 of the energy and 50 of theprotein provided by their daily food intake In the last reportof EU Commission India was presented as the first countryfor rice production with 19 of export India is followed byCambodia and Thailand United States and Vietnam are thecountries with less amount of imported rice [7] About 80ofthe rice production of Europe takes place in Italy and Spainwith a further 12 in Greece and Portugal
On this basis the presence of toxic heavy metals in ricewhich may raise the metal daily intake should be stronglyavoided in order to prevent negative effects on human healthThe following elements are consideredmacronutrients in riceand their content is usually in some P S K Ca and Mg
Hindawi Publishing CorporationJournal of ChemistryVolume 2015 Article ID 274340 12 pageshttpdxdoiorg1011552015274340
2 Journal of Chemistry
Other elements like Mn Fe Cu Zn Se and Ni are classifiedasmicronutrients and they are present in lower amount whileAs Cr Pb and Cd are undesirable elements because of theirtoxic effects even in very low quantity As a consequence itis crucially necessary to reduce possible accumulation effectsin rice grains from the environment for safe food productionGreat efforts are necessary to remediate polluted sites Otherapproaches could be developed to reduce metals accumula-tion in edible parts of plants For instance favorable agro-nomic practices and chemical regulators may decrease plantheavymetals uptake In this context it is important to identifywhich parts of the plant accumulate more toxic substances
Rice husk (RH) is the external protecting covering of eachrice grainThe chemical composition of RH varies from sam-ple to sample depending on rice variety climate and originOrganic compounds and water are the main components ofRH (about 74) followed by amorphous silica (between 15and 22) and other inorganic compounds (about 4) suchas Al2O3 Fe2O3 CaO and MgO [8] Omatola and Onojah
[9] reported the following list of elements detected by X-ray fluorescence (XRF) in RH K Ca Cr Mn Fe Ni CuZn Sr Br I As and Cl These elements owing to theirlow concentrations are considered as impurities Sun andGong reported that the main application of RH [10] is theproduction of thermal energy due to its high calorific valueabout 13607 kJkg Several other destinations of RH werereported such as livestock for the cattle agricultural fertilizeringredient for substrates in floriculture and horticultureand simple fertilizer for plants RH was also used for theproduction of biodegradable pots instead of using oil
It is also known that the produced byproduct of rice huskis called rice husk ash (RHA) RHA is widely used by the steelindustry in the production of high quality flat steel for auto-motive body panels [11] Owing to its insulating propertiesRHA has been used in the manufacture of refractory brickswhich are exposed to extreme temperatures in furnacessuch as the blast furnaces employed for producing molteniron and in the production of cement clinker The IndianSpace Research Organization has successfully developed thetechnology for producing high purity precipitated silica fromRHA which has a potential use in the computer industry[12 13] American and Brazilian scientists also developed newways to extract and purify silicon from RHA to use it insemiconductor manufacture Other uses have been exploredIn the frame of theCOSMOS-RICEproject RHA is employedas metals stabilizer for municipal solid waste incineration flyash treatment [14 15]
It is very interesting to verify the higher capability ofheavy accumulation by RH with respect to riceThis can playa fundamental role in the management of rice cultivation
Elemental chemical analysis of rice is usually performedby normative techniques such as FAAS [16] In this study weused total reflectionX-ray fluorescence (TXRF) to analyze thechemical composition of rice RH and soils of two differentareas of India The aim was the evaluation of metal uptakefrom soil to rice and the investigation of possible sources ofenvironmental pollution in the studied areas Moreover thiswork aims to highlight the possible role of RH in preservingrice from bioaccumulation of heavy metals
Table 1 Type of samples and their corresponding numbers sampledfrom the studied areas
City Samples Number of samplesRaipur SoilRaipur A 5Raipur B 5Raipur Rice husk (RH) 5Raipur Rice 5Korba Soil 5Korba Rice husk (RH) 5Korba Rice 5
2 Materials and Methods
21 Study Areas Elemental chemical analysis of soils comingfrom the central-east area of India where soil contains highconcentration of heavy metals was performed The state ofChhattisgarh (India) is rich in minerals such as iron lime-stone dolomite coal bauxite garnet quartz marble alexan-drite and diamonds Because of the huge production of riceChhattisgarh district nickname is ldquorice bowl of Central IndiardquoIndustrial activities in this area increased a lot in the last yearsIn fact the construction of new coal-fired power plants hasincreased up to 50 the production of ashes which exposesthe human and the environment to high pollution risksTherefore Raipur and Korba were chosen as the target citiesof this study Raipur is located at 21∘ 131015840 60 N and 81∘ 371015840 60E and hundreds varieties of rice grow Different studies havealready confirmed the presence of heavy metals in soils fromthis area demonstrating a degradation of the environmentalquality [17ndash19]Meanwhile Korba is located at 22∘ 211015840 0N and82∘ 401015840 60 E and as well as Raipur it is also a ldquovictimrdquo of theindustrial growth especially of cement industry Soil and ricesamples from each city region were collected in 5 differentareas Samples in Raipur were collected in duplicate to checkthe homogeneity of its compositionThe two samples namedas A and B in Table 1 were collected in the same area at a dis-tance less than 1 km from each other
22 Samples Preparation Procedure Soil samples were homo-genized through a mortar and dried for 90min at 90∘CSamples were weighed before and after this process in orderto determine their humidity Rice samples were transportedfrom India as they were collected Rice grains were insidetheir husk The separation of each rice grain from its outershell (husk) was carried out manually in the first step ofsample preparation Some differences were noticed at a gla-nce Rice samples had different husk colors from green toyellow and crop dimensions
23 Digestion of Samples About 05 g soil sample was addedto 9mL of nitric acid 65 (Fluka) 3mL of hydrofluoric acid(Fluka) and 2mL of hydrochloric acid 37 (Fluka) in Teflonvessels HF was necessary to perform total solubilization ofsoil probably due to the high content of silicates This proce-dure was performed according to US-EPA 3050B method
Journal of Chemistry 3
Cr Mn Fe Ni Cu Zn GaBi
AsPb Br Rb SrCaAr
BiPbMo
Cl
AlBrRbSrSi VKP S
BaTiPu
lses (
cps)
106
105
104
103
102
E (keV)2 4 6 8 10 12 14
Figure 1 TXRF spectra of soil samples from Korba (black) and Raipur (grey)
[20] Smaller quantities of RH and rice samples were usedfor digestion About 030 g of rice and rice husk was weighedtransferred inside the vessel and mixed with 10mL of nitricacid 65 (Fluka) A magnetic shaker was inserted in eachvessel and then the vessel was closed with a cap providedwith a hole to allow the leakage of gases formed during thedigestion A CEM microwave digestion device was used todigest the samples at 200∘C and 400 Psi After complete sam-ple solubilization the solutions were transferred to 25 and10mL volumetric flasks respectively for soil and riceRH andfilled with MilliQ water to the exact volume
24 TXRF Analysis of Soils Rice Husk and Rice SamplesChemical analysis of the solutions obtained by digestionwas performed bymeans of TXRF spectroscopy Quantitativeanalysis was performed by the internal standard addition pro-cedure [21] using Ga as internal standard element becauseit was not present in all the original samples 10 120583L of Ga(1 gL) was added to 990 120583L of soil samples in order to obtaina final Ga concentration of 10mgL Ga concentration inrice and RH solutions was 1mgL 10 120583L of each samplesolution was deposited on a three-quartz glass sample carriercleaned and siliconized and then dried on a hot plate at 50∘CTXRF measurements were performed by Bruker S2 Picofoxequipped with Mo tube operating at 50 kV and 750120583A andSilicon-Drift Detector Live time for each measurement was600 seconds
3 Results and Discussion
31 TXRF Analysis of Soils Humidity in Raipur soils washigher than in Korba samples It ranges from 14 to 67while in Korba soils humidity was in the interval from 17 to29
TXRF spectra of soil samples from Korba and Raipur areshown in Figure 1 Signals of Al K Ca Ti V Cr Mn FeNi Cu Zn As Rb Ba Pb and Sr are clearly identified in allthe samples of both cities region Bi was present only in thesoils from Raipur suggesting possible anthropogenic causes
Regarding the nonmetals signals of S Cl and Br were alwaysidentified
TXRFmeasurement was performed in air for this reasonit is not possible to give an accurate estimation of the contentof lighter elements such as Al P and S Their concentrationmay be underestimated and higher standard deviations mayoccur (about 20 in the case of Al) The content of Feis higher compared to the other elements For this reasonfitting of TXRF spectra was performed considering the pileup peak of Fe K120572 However as it was demonstrated in arecent publication TXRF is a successful technique to performquantitative analysis of soils [22] Background levels werekept to a minimum with the use of quartz sample carriersreducing at minimum their contact time with HF
Results of quantitative analysis of soil samples are repor-ted in Table 2 Heavy metals content is higher in Raipursoil samples compared with Korba samples Almost all theelements concentrations are 4-5 times higher in Raipur thanin Korba Relative standard deviation (RSD) is used to evalu-ate the precision of the measurements RSD for most of theelements (Mn Fe Ni Cu and Zn) is in the range from 1 to64 Slightly higher RSDvalues are observed forV 94 andfor Ba from65 to 246 due to the reasons already discussed[22] The highest RSD values are observed for Bi probablydue to its low concentration which is near the lowest limitof detection (LLD)
Descriptive statistics of elemental content in soil samplesis reported in Table 3 Concentration of Bi is significantlylower compared to other elements in soils Mn is the elementwith the widest range of concentrations and the largest differ-ences in the two studies areas Zn concentration is almost thesame in both cities while Cr and Pb are significantly higherin all the Raipur samples highlighting the possible adverseeffects of the metallurgy industry in Raipur The data of soilscollected in the same area of Raipur in two different pointsdo not show any significant difference This result figures outa homogeneous distribution of metals in the studied regions
A comparison of our results with the guidelines and limitsproposed for the determination of heavy metals pollution
4 Journal of Chemistry
Table2Elem
entalcon
centratio
n(m
gkg)insoilsamples
from
Korbaa
ndRa
ipurR
esultsaree
xpressed
asthea
verageplusmnstandard
deviation
Sample
Elem
entsconcentration(m
gKg
)K
CaTi
VCr
Mn
FeNi
CuZn
As
BaSr
PbBi
Korba
S1K
4524plusmn203
2560plusmn297
1550plusmn85
14plusmn1
22plusmn1
254plusmn12
7071plusmn309
9plusmn1
11plusmn1
52plusmn3
4plusmn1
152plusmn18
28plusmn2
11plusmn1
nd
S2K
3829plusmn175
1448plusmn463
1562plusmn68
17plusmn2
25plusmn1
230plusmn10
8409plusmn379
10plusmn1
10plusmn1
58plusmn3
3plusmn1
76plusmn9
14plusmn2
12plusmn1
nd
S3K
5705plusmn44
7110
1plusmn417
1572plusmn72
15plusmn2
19plusmn1
83plusmn4
5676plusmn246
10plusmn1
6plusmn1
14plusmn1
4plusmn1
57plusmn8
3plusmn01
10plusmn1
nd
S4K
5031plusmn239
421plusmn
251350plusmn59
15plusmn1
24plusmn1
102plusmn4
7257plusmn316
12plusmn1
7plusmn1
15plusmn1
5plusmn1
117plusmn13
11plusmn1
11plusmn1
nd
S5K
6217plusmn511
441plusmn
341293plusmn63
11plusmn1
15plusmn1
143plusmn7
5781plusmn254
7plusmn1
6plusmn1
22plusmn1
5plusmn1
136plusmn10
15plusmn1
13plusmn1
nd
Raipur
S1A
R7617plusmn391
2660plusmn1637
4337plusmn197
61plusmn6
112plusmn6
1455plusmn66
38863plusmn1737
39plusmn2
34plusmn2
60plusmn4
15plusmn1
166plusmn28
23plusmn6
64plusmn5
4plusmn1
S1B
R8117plusmn356
786plusmn57
4893plusmn213
55plusmn4
120plusmn5
1055plusmn46
39578plusmn1716
45plusmn2
37plusmn2
60plusmn2
12plusmn2
162plusmn12
16plusmn1
55plusmn5
5plusmn1
S2A
R6172plusmn318
1088plusmn228
4610plusmn222
65plusmn5
111plusmn
5973plusmn46
38183plusmn1671
45plusmn3
34plusmn2
60plusmn5
13plusmn2
160plusmn22
20plusmn3
46plusmn5
5plusmn1
S2B
R4895plusmn226
1199plusmn66
4716plusmn207
60plusmn4
127plusmn6
463plusmn20
37942plusmn1647
49plusmn2
34plusmn1
51plusmn2
15plusmn2
158plusmn18
21plusmn1
46plusmn5
5plusmn1
S3A
R9251plusmn477
837plusmn151
5246plusmn248
107plusmn10
145plusmn7
1855plusmn81
32937plusmn1437
80plusmn4
43plusmn2
60plusmn3
21plusmn3
170plusmn42
16plusmn2
55plusmn8
5plusmn2
S3B
R9149plusmn40
0786plusmn42
5959plusmn258
116plusmn7
121plusmn
51389plusmn61
27203plusmn1331
75plusmn3
46plusmn2
50plusmn2
26plusmn1
147plusmn22
11plusmn2
44plusmn2
4plusmn1
S4A
R5318plusmn233
1078plusmn115
4993plusmn218
74plusmn4
131plusmn
61304plusmn58
42808plusmn1863
55plusmn2
36plusmn2
54plusmn7
18plusmn2
191plusmn
1317plusmn1
54plusmn5
5plusmn2
S4B
R5497plusmn270
824plusmn137
5270plusmn254
116plusmn11
122plusmn6
1984plusmn90
31119plusmn1360
80plusmn5
49plusmn14
56plusmn3
30plusmn3
129plusmn30
11plusmn4
55plusmn6
4plusmn1
S5A
R7477plusmn510
1275plusmn594
4672plusmn205
127plusmn8
174plusmn8
2597plusmn113
43853plusmn2203
79plusmn4
44plusmn2
54plusmn6
36plusmn3
261plusmn
11617plusmn6
69plusmn3
5plusmn1
S5B
58599plusmn422
2557plusmn237
5285plusmn232
111plusmn
6155plusmn7
1701plusmn75
40033plusmn1767
71plusmn3
43plusmn2
55plusmn2
24plusmn3
427plusmn54
31plusmn3
67plusmn6
8plusmn1
Journal of Chemistry 5
Table 3 Descriptive statistics results of elemental chemical analysis for Korba and Raipur soils
K Ca Ti V Cr Mn Fe Ni Cu Zn As Ba Rb Sr Pb BiKorba
Mean 506110 119582 146522 1438 2078 16239 683882 954 796 3220 420 10751 2362 1424 1135 ndSD 94297 88066 13332 229 410 7601 113639 190 229 2111 064 3998 720 898 120 ndMin 382912 42076 129266 1108 1456 8290 567619 654 595 1415 338 5699 1381 316 985 ndMax 621660 255993 157193 1732 2468 25370 840931 1162 1084 5818 486 17160 3073 2782 1280 nd
RaipurMean 720917 130909 498811 8934 13188 147754 3720198 6184 3959 5586 2096 19705 2624 1845 5545 511SD 162834 70736 47133 2831 2011 59658 518952 1660 591 386 805 8800 1664 632 894 118Min 489548 78577 433685 5544 11148 46253 2720251 3934 3109 5003 1190 12943 1023 1076 4355 383Max 925130 365998 595869 12684 17361 257907 4335400 7993 4851 6011 3568 42757 7132 3275 6921 815
[23] indicates that all the soil samples of Korba are notcontaminated while soils from Raipur are contaminated byNi Cu Cr As and Ba
A more detailed comparison of our data with thoseobtained in other studies of soil contamination in the samearea reveals a good agreement The comparison with datareported by Kabata Pendias for uncontaminated soils (Cr04ndash29mgkg Mn 25ndash8000mgkg Ni 3ndash150mgkg Cu 05ndash135mgkg Zn 1ndash750mgkg and Pb 06ndash63mgkg) [24] sug-gests that Cr and Pb contamination is present in RaipurMorerecent studies by Srinivasa Gowd et al [25] and Patel et al[26] reported higher content of Pb Zn and Cr Thus onlycontamination by Cr would be present However it should beconsidered that Pb Zn andCr concentration increased easilyduring the industrial activity particularly in themining areasSo the increasing inmetal concentration in these soils may bea consequence of anthropogenic influence
Statistical analysis was used to evaluate the correlationof the elements present in soil Cluster analysis was usedto highlight the differences between soils from Korba andRaipur Hierarchical division was performed using the Wardmethod which is based on the analysis of variances insteadof distances The varimax rotation with Kaiser normalizationmethod was used for factor analysis By extracting the eigen-values the number of significant factors was determinedData treatment was performed using the JMP 10 softwareResults of cluster analysis are reported in Figure 2The dend-rogram clearly points out the division of the samples intwo clusters corresponding to the different sampled areas ofKorba and Raipur Considering that the two studied citiesbelong to the same region of India and supposing the samecrustal composition this result suggests a different degree ofpollution
Results of factor analysis show that the three eigenvaluesexplain 9018 of the variance Therefore they were selectedfor further factor analysis The loadings of elements withrespect to each one of the three identified factors are reportedin Table 4 All the elements with high loadings for the samefactor may have a common origin in soils The first factor isresponsible for 563 of the total variance and it includes KTi V Cr Mn Fe Ni Cu Zn As Pb and Bi Consideringthe nature of these elements and their simultaneous presencethis suggests their anthropogenic origin The second factor
1 2 3 4 5 6 7 8 9 12 10 11 13 14 15
Figure 2 Dendrogram of cluster analysis for Korba (red) andRaipur (green) samples
accounts for 1709 of the total variance and it includes Caand Sr Ca and Sr are included in the list of the eight mostabundant rock forming elements of biosphere which may beadded to the soil from wind dispersion of dust from minetailing and wastes tips [27 28] The third principal compo-nent represented 1679 of the total variance and it includesAl Rb and Ba The presence of Al would suggest a crustalorigin Indeed Al acts as a natural marker element while itsanthropogenic origin is still unknown Al is a conservativeelement and is contained in aluminosilicates as is reported byVodyanitskii [29] However the crustal origin of Rb and Ba isnot assessed
32 TXRF Analysis of Rice and Rice Husk TXRF spectra ofrice and rice husk are shown in Figure 3 Signals of Mg AlP S Cl K Ca Ti Cr Mn Fe Ni Cu Zn Ba Rb Pb Br andSr are identified in both rice and RH samples After spectradeconvolution concentration of each was determined except
6 Journal of Chemistry
Pulse
s (cp
s)
E (keV)
SrRbBrPbGaZnCuNiFeMnCrBaTiCaKArCl
Mo
SPSiGa
Mg Sr
E RbAl
Zn
Pb
2 4 6 8 10 12 14
times1E3
30
20
10
00
Figure 3 Spectra of rice husk (black) and rice (gray) sample 2 from Korba measured by S2 Picofox
Table 4 Rotated component matrix for soil samples
(a)
Variables Rotated factor1 2 3
Al 04877 03792 07279K 05859 minus00676 05477Ca 00419 09249 01358Ti 09527 01259 00972V 09167 00068 03339Cr 09421 01997 0203Mn 08834 00792 02768Fe 08929 03231 00015Ni 09423 minus00077 02811Cu 09715 01256 01389Zn 06599 05904 minus01872As 08862 minus004 029Rb 00402 0147 09675Sr 00761 09325 02809Ba 04065 05243 06689Pb 09163 0287 01481Bi 08439 03457 02535
(b)
Variance explained by each factorFactor Variance Percent Cum percentFactor 1 95731 56313 56313Factor 2 29045 17085 73398Factor 3 28535 16785 90183
for elements lighter thanKQuantification of the detected lowZ elements is not reported because our measurements wereperformed in air and vacuum conditions are recommendedin this case [30] Results of quantitative analysis of rice andrice husk samples are reported in Table 5
Elemental composition of rice husk and rice is similarfor all the studied samples even if Ca Ti Mn Fe and Pbare higher in RH with respect to rice The concentrationof metals in the two matrices is usually correlated In thesamples from Korba the highest concentrations of Ti Fe andZn were detected in sample 3 for both the analyzed matrices(3R K and 3RH K) and the highest concentration of Ca andMn in sample 1 (1R K and 1RH K) In the samples fromRaipur the highest concentrations of Fe and Zn are foundin sample 3 (3R R and 3RH R) while the highest content ofMn was in sample 4 (4R R and 4RH R) Rice husk samplesof Korba contain Cr that is not detected in rice while Cris present in both the matrices collected in Raipur with theusual correlationThis can be due to the higher concentrationof Cr in Raipur than Korba soilsThe correlation observed forthe other elements is not present in the case of Pb Indeed thehighest value of Pb for rice husk samples is present in sample5RH K while the highest value of Pb for rice is present insample 2R K A similar behavior is observed for Ca and Ti inthe samples from Raipur
Descriptive statistics of elemental content in rice and ricehusk samples is reported in Table 6The comparison of heavymetals concentration in rice grain from the two studied areasshows no significant differences among K Ca Ti Ni Cuand Zn Other elements such as Cr Fe and Pb are higherin Raipur samples while Mn and Rb are higher in Korbasamples Concentration of heavymetals detected in rice sam-ples decreases in the following order Mn gt Zn gt Cu gt Ni gtPb gt Cr
Metal uptake is higher for plants germinated in soilsenriched with metals from anthropogenic factors Thereforebioaccumulation ability of plants is one of the most criticalproblems faced in agriculture and environmental studiesTransfer factor (TF) is an indicator of the plant species abilityor tendency to uptake a certain element from the soil [31]TF is obtained by dividing the element concentration in theplant by its concentration in soil according to (1) where119862p is the metal concentration in plant and 119862s is the metal
Journal of Chemistry 7
Table5Elem
entalcon
centratio
nin
rice(R)
andric
ehusk(RH)sam
ples
from
Korbaa
ndRa
ipur
Sample
Elem
entalcon
centratio
n(m
gKg
)K
CaTi
CrMn
FeNi
CuZn
RbSr
BaPb
Korba
1RK
2179plusmn122
267plusmn67
19plusmn04
00plusmn00
44plusmn2
18plusmn3
04plusmn01
22plusmn02
29plusmn1
186plusmn10
067plusmn014
nd
027plusmn001
2RK
2911plusmn160
225plusmn19
05plusmn03
00plusmn00
29plusmn1
19plusmn2
09plusmn01
24plusmn01
30plusmn1
352plusmn17
033plusmn005
nd
051plusmn003
3RK
2603plusmn184
227plusmn17
40plusmn03
00plusmn00
32plusmn1
21plusmn1
05plusmn01
30plusmn02
39plusmn2
42plusmn03
052plusmn003
nd
025plusmn002
4RK
1604plusmn111
223plusmn20
14plusmn04
00plusmn00
27plusmn1
13plusmn1
20plusmn06
30plusmn02
22plusmn1
57plusmn03
029plusmn002
nd
008plusmn002
5RK
2162plusmn113
175plusmn11
07plusmn02
00plusmn00
24plusmn1
15plusmn1
04plusmn01
25plusmn01
24plusmn1
225plusmn10
033plusmn001
nd
013plusmn001
1RH
K4152plusmn303
1500plusmn68
28plusmn09
04plusmn01
325plusmn15
93plusmn4
06plusmn01
20plusmn01
32plusmn1
223plusmn12
476plusmn022
32plusmn2
041plusmn004
2RH
K3894plusmn311
1277plusmn61
73plusmn24
00plusmn00
174plusmn8
161plusmn
1133plusmn02
18plusmn04
26plusmn1
287plusmn20
268plusmn013
15plusmn1
047plusmn003
3RH
K2277plusmn152
1485plusmn106
599plusmn456
09plusmn02
210plusmn9
409plusmn26
10plusmn01
21plusmn
02
33plusmn3
37plusmn03
449plusmn023
26plusmn2
070plusmn007
4RH
K44
41plusmn196
1072plusmn47
60plusmn24
02plusmn01
213plusmn9
184plusmn9
26plusmn01
22plusmn01
28plusmn1
111plusmn05
224plusmn010
25plusmn1
043plusmn002
5RH
K3782plusmn167
948plusmn61
23plusmn03
00plusmn00
206plusmn9
93plusmn4
06plusmn01
19plusmn01
27plusmn2
234plusmn11
289plusmn015
30plusmn1
102plusmn005
Raipur
1RR
3021plusmn221
395plusmn54
24plusmn11
03plusmn01
21plusmn1
33plusmn22
06plusmn01
34plusmn04
30plusmn2
06plusmn003
031plusmn003
nd
038plusmn002
2RR
2201plusmn101
232plusmn12
08plusmn02
00plusmn00
20plusmn1
13plusmn1
02plusmn01
17plusmn01
19plusmn1
32plusmn02
038plusmn002
nd
045plusmn004
3RR
2621plusmn120
347plusmn98
32plusmn04
03plusmn01
33plusmn1
24plusmn1
04plusmn01
23plusmn02
31plusmn2
11plusmn01
055plusmn004
nd
040plusmn003
4RR
2441plusmn134
345plusmn40
22plusmn05
02plusmn01
35plusmn2
22plusmn1
14plusmn01
31plusmn
02
30plusmn5
67plusmn03
049plusmn002
nd
026plusmn002
5RR
2295plusmn119
453plusmn182
17plusmn07
16plusmn07
26plusmn1
32plusmn2
18plusmn01
23plusmn01
25plusmn4
49plusmn03
059plusmn012
nd
024plusmn004
1RH
R6134plusmn284
1407plusmn237
248plusmn77
17plusmn09
159plusmn7
747plusmn43
09plusmn03
31plusmn
03
32plusmn3
13plusmn01
289plusmn015
5plusmn1
404plusmn018
2RH
R5088plusmn320
1727plusmn284
116plusmn28
10plusmn02
155plusmn8
601plusmn
3208plusmn04
22plusmn01
38plusmn8
48plusmn03
424plusmn056
5plusmn1
104plusmn012
3RH
R5474plusmn273
2165plusmn284
68plusmn07
08plusmn01
263plusmn12
589plusmn26
05plusmn01
24plusmn01
34plusmn2
18plusmn04
563plusmn026
8plusmn2
076plusmn005
4RH
R4866plusmn214
1367plusmn113
114plusmn07
433plusmn23
398plusmn18
957plusmn50
380plusmn19
29plusmn02
33plusmn3
92plusmn04
313plusmn019
14plusmn1
105plusmn007
5RH
R5930plusmn341
1441plusmn220
427plusmn115
84plusmn05
232plusmn10
918plusmn167
130plusmn06
27plusmn08
33plusmn4
71plusmn03
362plusmn023
6plusmn1
087plusmn034
8 Journal of Chemistry
Table 6 Descriptive statistics results of elemental chemical analysis for rice and rice husk from Korba and Raipur
K Ca Ti Cr Mn Fe Ni Cu Zn Rb Sr Ba PbKorba
RiceMean 229161 22352 171 000 3119 1725 085 261 2892 1724 043 nd 025SD 49562 3267 141 000 763 314 067 036 664 1279 016 nd 017Min 160361 17506 047 000 2397 1320 039 222 2218 418 029 nd 008Max 291056 26713 402 000 4367 2086 201 300 3909 3519 067 nd 051
RHMean 370919 125624 1567 032 22562 18803 162 201 2949 1785 341 2562 061SD 83990 24548 2483 009 5767 13003 122 013 322 1018 114 645 026Min 227706 94776 230 000 17433 9274 062 185 2587 369 224 1540 041Max 444080 149997 5992 090 32500 40897 325 217 3331 2869 476 3196 102
RaipurRiceMean 251578 35445 209 047 2685 2473 088 256 2707 329 046 nd 034SD 32375 8134 088 011 691 824 066 071 509 256 012 nd 009Min 220082 23192 084 000 1966 1267 022 166 1909 058 031 nd 024Max 302055 45290 324 160 3450 3261 177 344 3136 669 059 nd 045
RHMean 549853 162125 1948 1102 24133 76237 1064 266 3412 484 390 767 155SD 53845 33542 1463 1830 9908 17201 621 035 213 339 109 386 139Min 486602 136679 683 080 15514 58874 052 219 3218 131 289 467 076Max 613438 216507 4273 4326 39779 95678 3805 308 3765 921 563 1417 404
concentration in soil The variation observed in TFs for thesame species may be due to several factors such as the age ofthe plant the tissue and the environment in which the plantis grown It was demonstrated that the absorption ofmineralsand their distribution in the plant hang on the bioavailabilityof the minerals in soil root structure and shoot system[32] Moreover the bioavailability of elements from soil toplants is determined by other factors including pH redoxconditions speciation soil texture and mineralogy organicmatter content and the presence of competing ions
TFs calculated for rice and RH using the average valuesof elemental concentration in rice RH and soils of Korbaand Raipur are shown in Figure 4 In our study TFs for RHwere always higher than rice samples for both the studiedareas TFs of K Mn Cu Zn Rb and Ba are higher in Korbasamples compared to those of Raipur Elements such as Caand Cr show TFs higher in Raipur samples while Ti Fe Niand Pb were in the same range Our results clearly show thatthe bioaccumulation is higher in RH than in rice
TF =119862p
119862s (1)
A comparison with the literature data [33] for the content ofAs Ba Cu Pb Ni Mn and Cr in rice is reported in Table 7The average values calculated as the arithmetic mean forKorba and Raipur are reported separately The literaturereports that geometric means (GM) illustrate more exactdistribution of the element concentrations in rice samplesbut comparison withmany other studies is difficult due to thelack of information on GM [33] As and Ba are not present
0000
0001
0010
0100
1000
10000K
Ca
Ti
Cr
Mn
Fe
NiCu
Zn
Rb
Sr
Ba
Pb
Rice RaipurRH Raipur
Rice KorbaRH Korba
Figure 4 Transfer factors calculated for rice and rice husk sampleswith respect to soil samples from Korba and Raipur
in our samples Our values of Cu and Ni are aligned mainlywith those from Vietnam The concentrations of Pb and Mnare aligned respectively with commercial rice from China
Journal of Chemistry 9
Table 7 Concentration of hazardous elements in rice samples reported in different literature studies (a) arithmetic means (b) arithmeticstandard deviations (c) [34] (d) [35] and (e) [36]
Element Area 119873 AM (a) ASD (b) MIN MAX
Cu
Taizhou 13 4260 826 3037 5184Commercial rice China 5 3326 774 2812 4478
Vietnam (c) 31 2600 1100 5800Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2560 710 1662 3438Korba 5 2610 360 2222 2995
Pb
Taizhou 13 2042 2070 256 2602Commercial rice China 4 356 267 167 745
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 23700 19800 20100 24000Hangzhou (e) 5 131 103 45 308
Raipur 5 340 90 235 452Korba 5 250 170 78 514
Ni
Taizhou 13 761 391 339 1134Commercial rice China 4 476 276 201 818
Vietnam (c) 31 869 lt100 2022Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 880 660 216 1770Korba 5 850 670 387 2009
Mn
Taizhou 13 28640 5570 21977 37490Commercial rice China 4 9363 3288 5804 12708
Vietnam (c) 31 9900 5900 16300Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2685 6910 19700 34500Korba 5 31200 7600 24000 43700
Cr
Taizhou 13 107 83 6 279Commercial rice China 4 199 157 62 424
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 740 340 650 830Hangzhou (e) mdash mdash mdash mdash
Raipur 5 470 110 0 1600Korba 5 nd nd nd nd
and Taizhou The content of Cr in the samples of Raipur isexceptionally high
Despite all the reported data of metal content in riceaccording to the national standard for safety milled rice cri-teria [37] (NY5115-2002) themaximum allowable concentra-tions (MAC) ofAs and Pb are 050 and 020120583gg respectivelyMoreover the World Health Organization (WHO) provides020mgKg as the safe limit for Pb in rice [38] but it doesnot report any limit for other analyzed metals In the presentstudy Pb concentration is much higher than the reportedlimit in many samples both from Raipur and Korba evenif the average value is aligned with that of WHO Even it isknown as a toxic element Cr safe limit from WHOFAO is
not determined Since rice is the common food for the Asiancontinent and especially in China the MAC criteria deter-mine the same limit for some metals such as Cu 10mgKgZn 50mgKg Cr 1mgKg and Pb as that decided by WHO[39]
Statistical analysis does not show any significant differ-ence between rice and rice husk samples of the two areas ofinterest
Figure 5 shows the concentration of selected elements inall samples classified by species soil rice husk and riceThisfigure highlights the possible transfer andor accumulation ofelements from soil into the other twomatrices In some casesrice husk seems to act as a barrier for some heavymetals such
10 Journal of Chemistry
0
1
10
100
1000Cr
conc
entr
atio
n (m
gkg
)
Samples
Cr
1
10
100
As c
once
ntra
tion
(mg
kg)
As
0
1
10
100
Pb co
ncen
trat
ion
(mg
kg) Pb
0
2000
4000
6000
8000
10000
12000
K co
ncen
trat
ion
(mg
kg) K
010203040506070
Cu co
ncen
trat
ion
(mg
kg) Cu
010203040506070
Zn co
ncen
trat
ion
(mg
kg) Zn
0
1
10
100
Ni c
once
ntra
tion
(mg
kg) Ni
1
10
100
1000
10000
100000
Fe co
ncen
trat
ion
(mg
kg) Fe
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2 RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Figure 5 Concentration of elements in soil rice husk and rice samples from Korba and Raipur
as Cr K Fe and Pb The possible barrier role of rice husk isinteresting and it can be hypothesized also for Mn Ba andSr Unfortunately it is not clear in the case of Cu Ni Zn RbBi Ti and V
4 Conclusions
This work reports the chemical composition study of soilsrice and rice husk from Korba and Raipur (India) by means
Journal of Chemistry 11
of TXRF Results show some metals uptake from soil to ricein particular Pb and Cr from the Raipur region The noveltyof this study is the chemical characterization of rice made inparallel with the analysis of soils and corresponding rice huskA detailed analysis of all the data shows that rice husk accu-mulates more heavy metals than rice suggesting a possiblebarrier effect of the husk Despite that dedicated studiesshould be done to verify the clear role of husk and other para-meters such as rice species soils characteristics (pH claycontent and organic matter) and other variables Based onthe extremely interesting results obtained in this study someapproaches may be developed to promote low metals accu-mulation in rice
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study was supported by LIFE+ the financial instrumentof the European Community to support environmentalprojects (LIFE+ 2011 Project ENVIT000256) The authorsare grateful to Directorate-General Environment EuropeanCommission for inclusion of COSMOS-RICE Project inScience for Environment Policy Information Service (seehttpeceuropaeuenvironmentintegrationresearchnew-salertpdf383na2 enpdf) The authors acknowledge Profe-ssor Patel School of Studies in Chemistry Pt RavishankarShukla University Raipur India for the support in samplescollection
References
[1] C Huamain Z Chunrong T Cong and Z Yongguan ldquoHeavymetal pollution in soils in China status and countermeasuresrdquoAmbio vol 28 no 2 pp 130ndash134 1999
[2] M E Watanabe ldquoPhytoremediation on the brink of commer-cializationrdquo Environmental Science amp Technology vol 31 pp82Andash187A 1997
[3] S Uchida K Tagami and N Ishikawa ldquoConcentration soil-to-plant transfer factor and soil-soil solution distribution coeffi-cient of selenium in the surface environment -9106rdquo in Proceed-ings of the Symposium onWasteManagement (WM rsquo09 ) pp 1ndash5Phoenix Ariz USA March 2009
[4] X F Hu Y Jiang Y Shu X Hu L Liu and F Luo ldquoEffectsof mining wastewater discharges on heavy metal pollution andsoil enzyme activity of the paddy fieldsrdquo Journal of GeochemicalExploration vol 147 part B pp 139ndash150 2014
[5] A Sekara M Poniedziałek J Ciura and E Jedrszczyk ldquoCad-mium and lead accumulation and distribution in the organs ofnine crops implications for phytoremediationrdquo Polish Journalof Environmental Studies vol 14 no 4 pp 509ndash516 2005
[6] R Stone ldquoFood safetymdasharsenic and paddy rice a neglectedcancer riskrdquo Science vol 321 no 5886 pp 184ndash185 2008
[7] Committee for the Common Organisation of Agricultural Mar-kets 11 2014 httpeceuropaeuagriculturecerealspresenta-tionsricemarket-situation enpdf
[8] K R Dikshit and J E Schwartzberg ldquoIndia iI paeserdquo in Enci-clopedia Britannica pp 9ndash10 2007
[9] K M Omatola and A D Onojah ldquoElemental analysis of ricehusk ash using X-ray fluorescence techniquerdquo InternationalJournal of Physical Sciences vol 4 no 4 pp 189ndash193 2009
[10] L Sun and K Gong ldquoSilicon-based materials from rice husksand their applicationsrdquo Industrial and Engineering ChemistryResearch vol 40 no 25 pp 5861ndash5877 2001
[11] S Sugita ldquoOn the economical production of large quantities ofhighly reactive rice husk ashrdquo in Proceedings of the InternationalSymposium on Innovative World of Concrete (ICI-IWC rsquo93) pp2 3ndash71 1993
[12] I R Shaikh and A A Shaikh ldquoUtilization of wheat husk ashas silica source for the synthesis of MCM-41 type mesoporoussilicates a sustainable approach towards valorization of the agri-cultural waste streamrdquo Research Journal of Chemical Sciencesvol 3 pp 66ndash72 2013
[13] K M Omatola and A D Onojah ldquoRice husk as a potentialsource of high technological raw materials a reviewrdquo Journalof Polymer Science Innovation vol 4 pp 30ndash35 2012
[14] A Bosio N Rodella A Gianoncelli et al ldquoA new method toinertize incinerator toxic fly ash with silica from rice husk ashrdquoEnvironmental Chemistry Letters vol 11 no 4 pp 329ndash3332013
[15] A Bosio A Zacco L Borgese et al ldquoA sustainable technologyfor Pb and Zn stabilization based on the use of only wastematerials a green chemistry approach to avoid chemicals andpromote CO
2sequestrationrdquoChemical Engineering Journal vol
253 pp 377ndash384 2014[16] A Taylor S Branch M P Day M Patriarca and M White
ldquoAtomic spectrometry update Clinical and biological materialsfoods and beveragesrdquo Journal of Analytical Atomic Spectrometryvol 24 no 4 pp 535ndash579 2009
[17] K S Patel K Shrivas P Hoffmann and N Jakubowski ldquoAsurvey of lead pollution in Chhattisgarh State central IndiardquoEnvironmental Geochemistry and Health vol 28 no 1-2 pp 11ndash17 2006
[18] K S Patel K Shrivas R Brandt N Jakubowski W Corns andP Hoffmann ldquoArsenic contamination in water soil sedimentand rice of central Indiardquo Environmental Geochemistry andHealth vol 27 no 2 pp 131ndash145 2005
[19] B Giri K S Patel N K Jaiswal et al ldquoComposition and sourcesof organic tracers in aerosol particles of industrial central IndiardquoAtmospheric Research vol 120-121 pp 312ndash324 2013
[20] httpwwwepagovoswhazardtestmethodssw846pdfs3050bpdf
[21] L Borgese A Zacco E Bontempi et al ldquoTotal reflection of x-ray fluorescence (TXRF) amature technique for environmentalchemical nanoscale metrologyrdquoMeasurement Science and Tech-nology vol 20 no 8 Article ID 084027 2009
[22] F Bilo L Borgese D Cazzago et al ldquoTXRF analysis ofsoils and sediments to assess environmental contaminationrdquoEnvironmental Science and Pollution Research vol 21 no 23 pp13208ndash13214 2014
[23] Esdat 2000 Dutch Target and Intervention Values The newDutch list 2000 httpwwwesdatnet
[24] A Kabata-Pendias ldquoEnvironmental biogeochemistrymdashoutlineof the developmentrdquo Przeglad Geologiczny vol 49 no 10 pp957ndash959 2001
[25] S Srinivasa Gowd M Ramakrishna Reddy and P K GovilldquoAssessment of heavy metal contamination in soils at Jajmau
12 Journal of Chemistry
(Kanpur) and Unnao industrial areas of the Ganga Plain UttarPradesh Indiardquo Journal ofHazardousMaterials vol 174 no 1ndash3pp 113ndash121 2010
[26] K S Patel A Verma N K Jaiswal et al ldquoArsenic concentrationin soil rice and straw in central Indiardquo in Proceedings of the 4thInternational Congress on Arsenic in the Environment pp 508ndash509 July 2012
[27] A Kabata-Pendias Trace Elements in Soils and Plants Technol-ogy amp Engineering CRC Press 3rd edition 2000
[28] A D Jacobson and J D Blum ldquoCaSr and 87Sr86Sr geochem-istry of disseminated calcite in Himalayan silicate rocks fromNanga Parbat influence on river-water chemistryrdquoGeology vol28 no 5 pp 463ndash466 2000
[29] Y N Vodyanitskii ldquoCriteria of the technogenic nature ofheavy metals and metalloids in soils a review of publicationsrdquoEurasian Soil Science vol 42 no 9 pp 1053ndash1061 2009
[30] H Hoefler C Streli P Wobrauschek M Ovari and G ZarayldquoAnalysis of low Z elements in various environmental sampleswith total reflection X-ray fluorescence (TXRF) spectrometryrdquoSpectrochimica Acta Part B Atomic Spectroscopy vol 61 no 10-11 pp 1135ndash1140 2006
[31] K K Taha I M Shmou H M Osman and M H ShayoubldquoSoil-plant transfer and accumulation factors for trace elementsat the Blue and White Nilesrdquo Journal of Applied and IndustrialSciences vol 1 pp 97ndash102 2013
[32] H Papaefthymiou G Papatheodorou A Moustakli DChristodoulou and M Geraga ldquoNatural radionuclides and137Cs distributions and their relationship with sedimentologicalprocesses in Patras Harbour Greecerdquo Journal of EnvironmentalRadioactivity vol 94 no 2 pp 55ndash74 2007
[33] J Fu Q Zhou J Liu et al ldquoHigh levels of heavy metals inrice (Oryza sativa L) from a typical E-waste recycling areain southeast China and its potential risk to human healthrdquoChemosphere vol 71 no 7 pp 1269ndash1275 2008
[34] T D Phuong P Van Chuong D T Khiem and S Kokot ldquoEle-mental content of Vietnamese rice Part 1 Sampling analysisand comparison with previous studiesrdquo Analyst vol 124 no 4pp 553ndash560 1999
[35] S W Al Rmalli P I Haris C F Harrington and M AyubldquoA survey of arsenic in foodstuffs on sale in the UnitedKingdom and imported from Bangladeshrdquo Science of the TotalEnvironment vol 337 no 1ndash3 pp 23ndash30 2005
[36] C Fangmin Z Ningchun X Haiming et al ldquoCadmium andlead contamination in japonica rice grains and its variationamong the different locations in southeast Chinardquo Science of theTotal Environment vol 359 no 1ndash3 pp 156ndash166 2006
[37] National Programme on Safety Food SafetyMilled Rice Criteriaof PR China (NY5115-2002) China Ministry of AgricultureBeijing China 2002
[38] FAOWHOCodexAlimentariusGeneral Standards for Contam-inants and Toxins in Food Schedule1 Maximum and GuidelineLevels for Contaminants and Toxins in Food Joint FAOWHOFood Standards Programme Reference CXFAC 0216 CodexCommittee Rotterdam The Netherlands 2002
[39] The Ministry of Health of China GB 2762-2012 Standards forChinese Food Sanitation TheMinistry of Health of China 2012
Submit your manuscripts athttpwwwhindawicom
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Inorganic ChemistryInternational Journal of
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CatalystsJournal of
2 Journal of Chemistry
Other elements like Mn Fe Cu Zn Se and Ni are classifiedasmicronutrients and they are present in lower amount whileAs Cr Pb and Cd are undesirable elements because of theirtoxic effects even in very low quantity As a consequence itis crucially necessary to reduce possible accumulation effectsin rice grains from the environment for safe food productionGreat efforts are necessary to remediate polluted sites Otherapproaches could be developed to reduce metals accumula-tion in edible parts of plants For instance favorable agro-nomic practices and chemical regulators may decrease plantheavymetals uptake In this context it is important to identifywhich parts of the plant accumulate more toxic substances
Rice husk (RH) is the external protecting covering of eachrice grainThe chemical composition of RH varies from sam-ple to sample depending on rice variety climate and originOrganic compounds and water are the main components ofRH (about 74) followed by amorphous silica (between 15and 22) and other inorganic compounds (about 4) suchas Al2O3 Fe2O3 CaO and MgO [8] Omatola and Onojah
[9] reported the following list of elements detected by X-ray fluorescence (XRF) in RH K Ca Cr Mn Fe Ni CuZn Sr Br I As and Cl These elements owing to theirlow concentrations are considered as impurities Sun andGong reported that the main application of RH [10] is theproduction of thermal energy due to its high calorific valueabout 13607 kJkg Several other destinations of RH werereported such as livestock for the cattle agricultural fertilizeringredient for substrates in floriculture and horticultureand simple fertilizer for plants RH was also used for theproduction of biodegradable pots instead of using oil
It is also known that the produced byproduct of rice huskis called rice husk ash (RHA) RHA is widely used by the steelindustry in the production of high quality flat steel for auto-motive body panels [11] Owing to its insulating propertiesRHA has been used in the manufacture of refractory brickswhich are exposed to extreme temperatures in furnacessuch as the blast furnaces employed for producing molteniron and in the production of cement clinker The IndianSpace Research Organization has successfully developed thetechnology for producing high purity precipitated silica fromRHA which has a potential use in the computer industry[12 13] American and Brazilian scientists also developed newways to extract and purify silicon from RHA to use it insemiconductor manufacture Other uses have been exploredIn the frame of theCOSMOS-RICEproject RHA is employedas metals stabilizer for municipal solid waste incineration flyash treatment [14 15]
It is very interesting to verify the higher capability ofheavy accumulation by RH with respect to riceThis can playa fundamental role in the management of rice cultivation
Elemental chemical analysis of rice is usually performedby normative techniques such as FAAS [16] In this study weused total reflectionX-ray fluorescence (TXRF) to analyze thechemical composition of rice RH and soils of two differentareas of India The aim was the evaluation of metal uptakefrom soil to rice and the investigation of possible sources ofenvironmental pollution in the studied areas Moreover thiswork aims to highlight the possible role of RH in preservingrice from bioaccumulation of heavy metals
Table 1 Type of samples and their corresponding numbers sampledfrom the studied areas
City Samples Number of samplesRaipur SoilRaipur A 5Raipur B 5Raipur Rice husk (RH) 5Raipur Rice 5Korba Soil 5Korba Rice husk (RH) 5Korba Rice 5
2 Materials and Methods
21 Study Areas Elemental chemical analysis of soils comingfrom the central-east area of India where soil contains highconcentration of heavy metals was performed The state ofChhattisgarh (India) is rich in minerals such as iron lime-stone dolomite coal bauxite garnet quartz marble alexan-drite and diamonds Because of the huge production of riceChhattisgarh district nickname is ldquorice bowl of Central IndiardquoIndustrial activities in this area increased a lot in the last yearsIn fact the construction of new coal-fired power plants hasincreased up to 50 the production of ashes which exposesthe human and the environment to high pollution risksTherefore Raipur and Korba were chosen as the target citiesof this study Raipur is located at 21∘ 131015840 60 N and 81∘ 371015840 60E and hundreds varieties of rice grow Different studies havealready confirmed the presence of heavy metals in soils fromthis area demonstrating a degradation of the environmentalquality [17ndash19]Meanwhile Korba is located at 22∘ 211015840 0N and82∘ 401015840 60 E and as well as Raipur it is also a ldquovictimrdquo of theindustrial growth especially of cement industry Soil and ricesamples from each city region were collected in 5 differentareas Samples in Raipur were collected in duplicate to checkthe homogeneity of its compositionThe two samples namedas A and B in Table 1 were collected in the same area at a dis-tance less than 1 km from each other
22 Samples Preparation Procedure Soil samples were homo-genized through a mortar and dried for 90min at 90∘CSamples were weighed before and after this process in orderto determine their humidity Rice samples were transportedfrom India as they were collected Rice grains were insidetheir husk The separation of each rice grain from its outershell (husk) was carried out manually in the first step ofsample preparation Some differences were noticed at a gla-nce Rice samples had different husk colors from green toyellow and crop dimensions
23 Digestion of Samples About 05 g soil sample was addedto 9mL of nitric acid 65 (Fluka) 3mL of hydrofluoric acid(Fluka) and 2mL of hydrochloric acid 37 (Fluka) in Teflonvessels HF was necessary to perform total solubilization ofsoil probably due to the high content of silicates This proce-dure was performed according to US-EPA 3050B method
Journal of Chemistry 3
Cr Mn Fe Ni Cu Zn GaBi
AsPb Br Rb SrCaAr
BiPbMo
Cl
AlBrRbSrSi VKP S
BaTiPu
lses (
cps)
106
105
104
103
102
E (keV)2 4 6 8 10 12 14
Figure 1 TXRF spectra of soil samples from Korba (black) and Raipur (grey)
[20] Smaller quantities of RH and rice samples were usedfor digestion About 030 g of rice and rice husk was weighedtransferred inside the vessel and mixed with 10mL of nitricacid 65 (Fluka) A magnetic shaker was inserted in eachvessel and then the vessel was closed with a cap providedwith a hole to allow the leakage of gases formed during thedigestion A CEM microwave digestion device was used todigest the samples at 200∘C and 400 Psi After complete sam-ple solubilization the solutions were transferred to 25 and10mL volumetric flasks respectively for soil and riceRH andfilled with MilliQ water to the exact volume
24 TXRF Analysis of Soils Rice Husk and Rice SamplesChemical analysis of the solutions obtained by digestionwas performed bymeans of TXRF spectroscopy Quantitativeanalysis was performed by the internal standard addition pro-cedure [21] using Ga as internal standard element becauseit was not present in all the original samples 10 120583L of Ga(1 gL) was added to 990 120583L of soil samples in order to obtaina final Ga concentration of 10mgL Ga concentration inrice and RH solutions was 1mgL 10 120583L of each samplesolution was deposited on a three-quartz glass sample carriercleaned and siliconized and then dried on a hot plate at 50∘CTXRF measurements were performed by Bruker S2 Picofoxequipped with Mo tube operating at 50 kV and 750120583A andSilicon-Drift Detector Live time for each measurement was600 seconds
3 Results and Discussion
31 TXRF Analysis of Soils Humidity in Raipur soils washigher than in Korba samples It ranges from 14 to 67while in Korba soils humidity was in the interval from 17 to29
TXRF spectra of soil samples from Korba and Raipur areshown in Figure 1 Signals of Al K Ca Ti V Cr Mn FeNi Cu Zn As Rb Ba Pb and Sr are clearly identified in allthe samples of both cities region Bi was present only in thesoils from Raipur suggesting possible anthropogenic causes
Regarding the nonmetals signals of S Cl and Br were alwaysidentified
TXRFmeasurement was performed in air for this reasonit is not possible to give an accurate estimation of the contentof lighter elements such as Al P and S Their concentrationmay be underestimated and higher standard deviations mayoccur (about 20 in the case of Al) The content of Feis higher compared to the other elements For this reasonfitting of TXRF spectra was performed considering the pileup peak of Fe K120572 However as it was demonstrated in arecent publication TXRF is a successful technique to performquantitative analysis of soils [22] Background levels werekept to a minimum with the use of quartz sample carriersreducing at minimum their contact time with HF
Results of quantitative analysis of soil samples are repor-ted in Table 2 Heavy metals content is higher in Raipursoil samples compared with Korba samples Almost all theelements concentrations are 4-5 times higher in Raipur thanin Korba Relative standard deviation (RSD) is used to evalu-ate the precision of the measurements RSD for most of theelements (Mn Fe Ni Cu and Zn) is in the range from 1 to64 Slightly higher RSDvalues are observed forV 94 andfor Ba from65 to 246 due to the reasons already discussed[22] The highest RSD values are observed for Bi probablydue to its low concentration which is near the lowest limitof detection (LLD)
Descriptive statistics of elemental content in soil samplesis reported in Table 3 Concentration of Bi is significantlylower compared to other elements in soils Mn is the elementwith the widest range of concentrations and the largest differ-ences in the two studies areas Zn concentration is almost thesame in both cities while Cr and Pb are significantly higherin all the Raipur samples highlighting the possible adverseeffects of the metallurgy industry in Raipur The data of soilscollected in the same area of Raipur in two different pointsdo not show any significant difference This result figures outa homogeneous distribution of metals in the studied regions
A comparison of our results with the guidelines and limitsproposed for the determination of heavy metals pollution
4 Journal of Chemistry
Table2Elem
entalcon
centratio
n(m
gkg)insoilsamples
from
Korbaa
ndRa
ipurR
esultsaree
xpressed
asthea
verageplusmnstandard
deviation
Sample
Elem
entsconcentration(m
gKg
)K
CaTi
VCr
Mn
FeNi
CuZn
As
BaSr
PbBi
Korba
S1K
4524plusmn203
2560plusmn297
1550plusmn85
14plusmn1
22plusmn1
254plusmn12
7071plusmn309
9plusmn1
11plusmn1
52plusmn3
4plusmn1
152plusmn18
28plusmn2
11plusmn1
nd
S2K
3829plusmn175
1448plusmn463
1562plusmn68
17plusmn2
25plusmn1
230plusmn10
8409plusmn379
10plusmn1
10plusmn1
58plusmn3
3plusmn1
76plusmn9
14plusmn2
12plusmn1
nd
S3K
5705plusmn44
7110
1plusmn417
1572plusmn72
15plusmn2
19plusmn1
83plusmn4
5676plusmn246
10plusmn1
6plusmn1
14plusmn1
4plusmn1
57plusmn8
3plusmn01
10plusmn1
nd
S4K
5031plusmn239
421plusmn
251350plusmn59
15plusmn1
24plusmn1
102plusmn4
7257plusmn316
12plusmn1
7plusmn1
15plusmn1
5plusmn1
117plusmn13
11plusmn1
11plusmn1
nd
S5K
6217plusmn511
441plusmn
341293plusmn63
11plusmn1
15plusmn1
143plusmn7
5781plusmn254
7plusmn1
6plusmn1
22plusmn1
5plusmn1
136plusmn10
15plusmn1
13plusmn1
nd
Raipur
S1A
R7617plusmn391
2660plusmn1637
4337plusmn197
61plusmn6
112plusmn6
1455plusmn66
38863plusmn1737
39plusmn2
34plusmn2
60plusmn4
15plusmn1
166plusmn28
23plusmn6
64plusmn5
4plusmn1
S1B
R8117plusmn356
786plusmn57
4893plusmn213
55plusmn4
120plusmn5
1055plusmn46
39578plusmn1716
45plusmn2
37plusmn2
60plusmn2
12plusmn2
162plusmn12
16plusmn1
55plusmn5
5plusmn1
S2A
R6172plusmn318
1088plusmn228
4610plusmn222
65plusmn5
111plusmn
5973plusmn46
38183plusmn1671
45plusmn3
34plusmn2
60plusmn5
13plusmn2
160plusmn22
20plusmn3
46plusmn5
5plusmn1
S2B
R4895plusmn226
1199plusmn66
4716plusmn207
60plusmn4
127plusmn6
463plusmn20
37942plusmn1647
49plusmn2
34plusmn1
51plusmn2
15plusmn2
158plusmn18
21plusmn1
46plusmn5
5plusmn1
S3A
R9251plusmn477
837plusmn151
5246plusmn248
107plusmn10
145plusmn7
1855plusmn81
32937plusmn1437
80plusmn4
43plusmn2
60plusmn3
21plusmn3
170plusmn42
16plusmn2
55plusmn8
5plusmn2
S3B
R9149plusmn40
0786plusmn42
5959plusmn258
116plusmn7
121plusmn
51389plusmn61
27203plusmn1331
75plusmn3
46plusmn2
50plusmn2
26plusmn1
147plusmn22
11plusmn2
44plusmn2
4plusmn1
S4A
R5318plusmn233
1078plusmn115
4993plusmn218
74plusmn4
131plusmn
61304plusmn58
42808plusmn1863
55plusmn2
36plusmn2
54plusmn7
18plusmn2
191plusmn
1317plusmn1
54plusmn5
5plusmn2
S4B
R5497plusmn270
824plusmn137
5270plusmn254
116plusmn11
122plusmn6
1984plusmn90
31119plusmn1360
80plusmn5
49plusmn14
56plusmn3
30plusmn3
129plusmn30
11plusmn4
55plusmn6
4plusmn1
S5A
R7477plusmn510
1275plusmn594
4672plusmn205
127plusmn8
174plusmn8
2597plusmn113
43853plusmn2203
79plusmn4
44plusmn2
54plusmn6
36plusmn3
261plusmn
11617plusmn6
69plusmn3
5plusmn1
S5B
58599plusmn422
2557plusmn237
5285plusmn232
111plusmn
6155plusmn7
1701plusmn75
40033plusmn1767
71plusmn3
43plusmn2
55plusmn2
24plusmn3
427plusmn54
31plusmn3
67plusmn6
8plusmn1
Journal of Chemistry 5
Table 3 Descriptive statistics results of elemental chemical analysis for Korba and Raipur soils
K Ca Ti V Cr Mn Fe Ni Cu Zn As Ba Rb Sr Pb BiKorba
Mean 506110 119582 146522 1438 2078 16239 683882 954 796 3220 420 10751 2362 1424 1135 ndSD 94297 88066 13332 229 410 7601 113639 190 229 2111 064 3998 720 898 120 ndMin 382912 42076 129266 1108 1456 8290 567619 654 595 1415 338 5699 1381 316 985 ndMax 621660 255993 157193 1732 2468 25370 840931 1162 1084 5818 486 17160 3073 2782 1280 nd
RaipurMean 720917 130909 498811 8934 13188 147754 3720198 6184 3959 5586 2096 19705 2624 1845 5545 511SD 162834 70736 47133 2831 2011 59658 518952 1660 591 386 805 8800 1664 632 894 118Min 489548 78577 433685 5544 11148 46253 2720251 3934 3109 5003 1190 12943 1023 1076 4355 383Max 925130 365998 595869 12684 17361 257907 4335400 7993 4851 6011 3568 42757 7132 3275 6921 815
[23] indicates that all the soil samples of Korba are notcontaminated while soils from Raipur are contaminated byNi Cu Cr As and Ba
A more detailed comparison of our data with thoseobtained in other studies of soil contamination in the samearea reveals a good agreement The comparison with datareported by Kabata Pendias for uncontaminated soils (Cr04ndash29mgkg Mn 25ndash8000mgkg Ni 3ndash150mgkg Cu 05ndash135mgkg Zn 1ndash750mgkg and Pb 06ndash63mgkg) [24] sug-gests that Cr and Pb contamination is present in RaipurMorerecent studies by Srinivasa Gowd et al [25] and Patel et al[26] reported higher content of Pb Zn and Cr Thus onlycontamination by Cr would be present However it should beconsidered that Pb Zn andCr concentration increased easilyduring the industrial activity particularly in themining areasSo the increasing inmetal concentration in these soils may bea consequence of anthropogenic influence
Statistical analysis was used to evaluate the correlationof the elements present in soil Cluster analysis was usedto highlight the differences between soils from Korba andRaipur Hierarchical division was performed using the Wardmethod which is based on the analysis of variances insteadof distances The varimax rotation with Kaiser normalizationmethod was used for factor analysis By extracting the eigen-values the number of significant factors was determinedData treatment was performed using the JMP 10 softwareResults of cluster analysis are reported in Figure 2The dend-rogram clearly points out the division of the samples intwo clusters corresponding to the different sampled areas ofKorba and Raipur Considering that the two studied citiesbelong to the same region of India and supposing the samecrustal composition this result suggests a different degree ofpollution
Results of factor analysis show that the three eigenvaluesexplain 9018 of the variance Therefore they were selectedfor further factor analysis The loadings of elements withrespect to each one of the three identified factors are reportedin Table 4 All the elements with high loadings for the samefactor may have a common origin in soils The first factor isresponsible for 563 of the total variance and it includes KTi V Cr Mn Fe Ni Cu Zn As Pb and Bi Consideringthe nature of these elements and their simultaneous presencethis suggests their anthropogenic origin The second factor
1 2 3 4 5 6 7 8 9 12 10 11 13 14 15
Figure 2 Dendrogram of cluster analysis for Korba (red) andRaipur (green) samples
accounts for 1709 of the total variance and it includes Caand Sr Ca and Sr are included in the list of the eight mostabundant rock forming elements of biosphere which may beadded to the soil from wind dispersion of dust from minetailing and wastes tips [27 28] The third principal compo-nent represented 1679 of the total variance and it includesAl Rb and Ba The presence of Al would suggest a crustalorigin Indeed Al acts as a natural marker element while itsanthropogenic origin is still unknown Al is a conservativeelement and is contained in aluminosilicates as is reported byVodyanitskii [29] However the crustal origin of Rb and Ba isnot assessed
32 TXRF Analysis of Rice and Rice Husk TXRF spectra ofrice and rice husk are shown in Figure 3 Signals of Mg AlP S Cl K Ca Ti Cr Mn Fe Ni Cu Zn Ba Rb Pb Br andSr are identified in both rice and RH samples After spectradeconvolution concentration of each was determined except
6 Journal of Chemistry
Pulse
s (cp
s)
E (keV)
SrRbBrPbGaZnCuNiFeMnCrBaTiCaKArCl
Mo
SPSiGa
Mg Sr
E RbAl
Zn
Pb
2 4 6 8 10 12 14
times1E3
30
20
10
00
Figure 3 Spectra of rice husk (black) and rice (gray) sample 2 from Korba measured by S2 Picofox
Table 4 Rotated component matrix for soil samples
(a)
Variables Rotated factor1 2 3
Al 04877 03792 07279K 05859 minus00676 05477Ca 00419 09249 01358Ti 09527 01259 00972V 09167 00068 03339Cr 09421 01997 0203Mn 08834 00792 02768Fe 08929 03231 00015Ni 09423 minus00077 02811Cu 09715 01256 01389Zn 06599 05904 minus01872As 08862 minus004 029Rb 00402 0147 09675Sr 00761 09325 02809Ba 04065 05243 06689Pb 09163 0287 01481Bi 08439 03457 02535
(b)
Variance explained by each factorFactor Variance Percent Cum percentFactor 1 95731 56313 56313Factor 2 29045 17085 73398Factor 3 28535 16785 90183
for elements lighter thanKQuantification of the detected lowZ elements is not reported because our measurements wereperformed in air and vacuum conditions are recommendedin this case [30] Results of quantitative analysis of rice andrice husk samples are reported in Table 5
Elemental composition of rice husk and rice is similarfor all the studied samples even if Ca Ti Mn Fe and Pbare higher in RH with respect to rice The concentrationof metals in the two matrices is usually correlated In thesamples from Korba the highest concentrations of Ti Fe andZn were detected in sample 3 for both the analyzed matrices(3R K and 3RH K) and the highest concentration of Ca andMn in sample 1 (1R K and 1RH K) In the samples fromRaipur the highest concentrations of Fe and Zn are foundin sample 3 (3R R and 3RH R) while the highest content ofMn was in sample 4 (4R R and 4RH R) Rice husk samplesof Korba contain Cr that is not detected in rice while Cris present in both the matrices collected in Raipur with theusual correlationThis can be due to the higher concentrationof Cr in Raipur than Korba soilsThe correlation observed forthe other elements is not present in the case of Pb Indeed thehighest value of Pb for rice husk samples is present in sample5RH K while the highest value of Pb for rice is present insample 2R K A similar behavior is observed for Ca and Ti inthe samples from Raipur
Descriptive statistics of elemental content in rice and ricehusk samples is reported in Table 6The comparison of heavymetals concentration in rice grain from the two studied areasshows no significant differences among K Ca Ti Ni Cuand Zn Other elements such as Cr Fe and Pb are higherin Raipur samples while Mn and Rb are higher in Korbasamples Concentration of heavymetals detected in rice sam-ples decreases in the following order Mn gt Zn gt Cu gt Ni gtPb gt Cr
Metal uptake is higher for plants germinated in soilsenriched with metals from anthropogenic factors Thereforebioaccumulation ability of plants is one of the most criticalproblems faced in agriculture and environmental studiesTransfer factor (TF) is an indicator of the plant species abilityor tendency to uptake a certain element from the soil [31]TF is obtained by dividing the element concentration in theplant by its concentration in soil according to (1) where119862p is the metal concentration in plant and 119862s is the metal
Journal of Chemistry 7
Table5Elem
entalcon
centratio
nin
rice(R)
andric
ehusk(RH)sam
ples
from
Korbaa
ndRa
ipur
Sample
Elem
entalcon
centratio
n(m
gKg
)K
CaTi
CrMn
FeNi
CuZn
RbSr
BaPb
Korba
1RK
2179plusmn122
267plusmn67
19plusmn04
00plusmn00
44plusmn2
18plusmn3
04plusmn01
22plusmn02
29plusmn1
186plusmn10
067plusmn014
nd
027plusmn001
2RK
2911plusmn160
225plusmn19
05plusmn03
00plusmn00
29plusmn1
19plusmn2
09plusmn01
24plusmn01
30plusmn1
352plusmn17
033plusmn005
nd
051plusmn003
3RK
2603plusmn184
227plusmn17
40plusmn03
00plusmn00
32plusmn1
21plusmn1
05plusmn01
30plusmn02
39plusmn2
42plusmn03
052plusmn003
nd
025plusmn002
4RK
1604plusmn111
223plusmn20
14plusmn04
00plusmn00
27plusmn1
13plusmn1
20plusmn06
30plusmn02
22plusmn1
57plusmn03
029plusmn002
nd
008plusmn002
5RK
2162plusmn113
175plusmn11
07plusmn02
00plusmn00
24plusmn1
15plusmn1
04plusmn01
25plusmn01
24plusmn1
225plusmn10
033plusmn001
nd
013plusmn001
1RH
K4152plusmn303
1500plusmn68
28plusmn09
04plusmn01
325plusmn15
93plusmn4
06plusmn01
20plusmn01
32plusmn1
223plusmn12
476plusmn022
32plusmn2
041plusmn004
2RH
K3894plusmn311
1277plusmn61
73plusmn24
00plusmn00
174plusmn8
161plusmn
1133plusmn02
18plusmn04
26plusmn1
287plusmn20
268plusmn013
15plusmn1
047plusmn003
3RH
K2277plusmn152
1485plusmn106
599plusmn456
09plusmn02
210plusmn9
409plusmn26
10plusmn01
21plusmn
02
33plusmn3
37plusmn03
449plusmn023
26plusmn2
070plusmn007
4RH
K44
41plusmn196
1072plusmn47
60plusmn24
02plusmn01
213plusmn9
184plusmn9
26plusmn01
22plusmn01
28plusmn1
111plusmn05
224plusmn010
25plusmn1
043plusmn002
5RH
K3782plusmn167
948plusmn61
23plusmn03
00plusmn00
206plusmn9
93plusmn4
06plusmn01
19plusmn01
27plusmn2
234plusmn11
289plusmn015
30plusmn1
102plusmn005
Raipur
1RR
3021plusmn221
395plusmn54
24plusmn11
03plusmn01
21plusmn1
33plusmn22
06plusmn01
34plusmn04
30plusmn2
06plusmn003
031plusmn003
nd
038plusmn002
2RR
2201plusmn101
232plusmn12
08plusmn02
00plusmn00
20plusmn1
13plusmn1
02plusmn01
17plusmn01
19plusmn1
32plusmn02
038plusmn002
nd
045plusmn004
3RR
2621plusmn120
347plusmn98
32plusmn04
03plusmn01
33plusmn1
24plusmn1
04plusmn01
23plusmn02
31plusmn2
11plusmn01
055plusmn004
nd
040plusmn003
4RR
2441plusmn134
345plusmn40
22plusmn05
02plusmn01
35plusmn2
22plusmn1
14plusmn01
31plusmn
02
30plusmn5
67plusmn03
049plusmn002
nd
026plusmn002
5RR
2295plusmn119
453plusmn182
17plusmn07
16plusmn07
26plusmn1
32plusmn2
18plusmn01
23plusmn01
25plusmn4
49plusmn03
059plusmn012
nd
024plusmn004
1RH
R6134plusmn284
1407plusmn237
248plusmn77
17plusmn09
159plusmn7
747plusmn43
09plusmn03
31plusmn
03
32plusmn3
13plusmn01
289plusmn015
5plusmn1
404plusmn018
2RH
R5088plusmn320
1727plusmn284
116plusmn28
10plusmn02
155plusmn8
601plusmn
3208plusmn04
22plusmn01
38plusmn8
48plusmn03
424plusmn056
5plusmn1
104plusmn012
3RH
R5474plusmn273
2165plusmn284
68plusmn07
08plusmn01
263plusmn12
589plusmn26
05plusmn01
24plusmn01
34plusmn2
18plusmn04
563plusmn026
8plusmn2
076plusmn005
4RH
R4866plusmn214
1367plusmn113
114plusmn07
433plusmn23
398plusmn18
957plusmn50
380plusmn19
29plusmn02
33plusmn3
92plusmn04
313plusmn019
14plusmn1
105plusmn007
5RH
R5930plusmn341
1441plusmn220
427plusmn115
84plusmn05
232plusmn10
918plusmn167
130plusmn06
27plusmn08
33plusmn4
71plusmn03
362plusmn023
6plusmn1
087plusmn034
8 Journal of Chemistry
Table 6 Descriptive statistics results of elemental chemical analysis for rice and rice husk from Korba and Raipur
K Ca Ti Cr Mn Fe Ni Cu Zn Rb Sr Ba PbKorba
RiceMean 229161 22352 171 000 3119 1725 085 261 2892 1724 043 nd 025SD 49562 3267 141 000 763 314 067 036 664 1279 016 nd 017Min 160361 17506 047 000 2397 1320 039 222 2218 418 029 nd 008Max 291056 26713 402 000 4367 2086 201 300 3909 3519 067 nd 051
RHMean 370919 125624 1567 032 22562 18803 162 201 2949 1785 341 2562 061SD 83990 24548 2483 009 5767 13003 122 013 322 1018 114 645 026Min 227706 94776 230 000 17433 9274 062 185 2587 369 224 1540 041Max 444080 149997 5992 090 32500 40897 325 217 3331 2869 476 3196 102
RaipurRiceMean 251578 35445 209 047 2685 2473 088 256 2707 329 046 nd 034SD 32375 8134 088 011 691 824 066 071 509 256 012 nd 009Min 220082 23192 084 000 1966 1267 022 166 1909 058 031 nd 024Max 302055 45290 324 160 3450 3261 177 344 3136 669 059 nd 045
RHMean 549853 162125 1948 1102 24133 76237 1064 266 3412 484 390 767 155SD 53845 33542 1463 1830 9908 17201 621 035 213 339 109 386 139Min 486602 136679 683 080 15514 58874 052 219 3218 131 289 467 076Max 613438 216507 4273 4326 39779 95678 3805 308 3765 921 563 1417 404
concentration in soil The variation observed in TFs for thesame species may be due to several factors such as the age ofthe plant the tissue and the environment in which the plantis grown It was demonstrated that the absorption ofmineralsand their distribution in the plant hang on the bioavailabilityof the minerals in soil root structure and shoot system[32] Moreover the bioavailability of elements from soil toplants is determined by other factors including pH redoxconditions speciation soil texture and mineralogy organicmatter content and the presence of competing ions
TFs calculated for rice and RH using the average valuesof elemental concentration in rice RH and soils of Korbaand Raipur are shown in Figure 4 In our study TFs for RHwere always higher than rice samples for both the studiedareas TFs of K Mn Cu Zn Rb and Ba are higher in Korbasamples compared to those of Raipur Elements such as Caand Cr show TFs higher in Raipur samples while Ti Fe Niand Pb were in the same range Our results clearly show thatthe bioaccumulation is higher in RH than in rice
TF =119862p
119862s (1)
A comparison with the literature data [33] for the content ofAs Ba Cu Pb Ni Mn and Cr in rice is reported in Table 7The average values calculated as the arithmetic mean forKorba and Raipur are reported separately The literaturereports that geometric means (GM) illustrate more exactdistribution of the element concentrations in rice samplesbut comparison withmany other studies is difficult due to thelack of information on GM [33] As and Ba are not present
0000
0001
0010
0100
1000
10000K
Ca
Ti
Cr
Mn
Fe
NiCu
Zn
Rb
Sr
Ba
Pb
Rice RaipurRH Raipur
Rice KorbaRH Korba
Figure 4 Transfer factors calculated for rice and rice husk sampleswith respect to soil samples from Korba and Raipur
in our samples Our values of Cu and Ni are aligned mainlywith those from Vietnam The concentrations of Pb and Mnare aligned respectively with commercial rice from China
Journal of Chemistry 9
Table 7 Concentration of hazardous elements in rice samples reported in different literature studies (a) arithmetic means (b) arithmeticstandard deviations (c) [34] (d) [35] and (e) [36]
Element Area 119873 AM (a) ASD (b) MIN MAX
Cu
Taizhou 13 4260 826 3037 5184Commercial rice China 5 3326 774 2812 4478
Vietnam (c) 31 2600 1100 5800Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2560 710 1662 3438Korba 5 2610 360 2222 2995
Pb
Taizhou 13 2042 2070 256 2602Commercial rice China 4 356 267 167 745
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 23700 19800 20100 24000Hangzhou (e) 5 131 103 45 308
Raipur 5 340 90 235 452Korba 5 250 170 78 514
Ni
Taizhou 13 761 391 339 1134Commercial rice China 4 476 276 201 818
Vietnam (c) 31 869 lt100 2022Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 880 660 216 1770Korba 5 850 670 387 2009
Mn
Taizhou 13 28640 5570 21977 37490Commercial rice China 4 9363 3288 5804 12708
Vietnam (c) 31 9900 5900 16300Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2685 6910 19700 34500Korba 5 31200 7600 24000 43700
Cr
Taizhou 13 107 83 6 279Commercial rice China 4 199 157 62 424
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 740 340 650 830Hangzhou (e) mdash mdash mdash mdash
Raipur 5 470 110 0 1600Korba 5 nd nd nd nd
and Taizhou The content of Cr in the samples of Raipur isexceptionally high
Despite all the reported data of metal content in riceaccording to the national standard for safety milled rice cri-teria [37] (NY5115-2002) themaximum allowable concentra-tions (MAC) ofAs and Pb are 050 and 020120583gg respectivelyMoreover the World Health Organization (WHO) provides020mgKg as the safe limit for Pb in rice [38] but it doesnot report any limit for other analyzed metals In the presentstudy Pb concentration is much higher than the reportedlimit in many samples both from Raipur and Korba evenif the average value is aligned with that of WHO Even it isknown as a toxic element Cr safe limit from WHOFAO is
not determined Since rice is the common food for the Asiancontinent and especially in China the MAC criteria deter-mine the same limit for some metals such as Cu 10mgKgZn 50mgKg Cr 1mgKg and Pb as that decided by WHO[39]
Statistical analysis does not show any significant differ-ence between rice and rice husk samples of the two areas ofinterest
Figure 5 shows the concentration of selected elements inall samples classified by species soil rice husk and riceThisfigure highlights the possible transfer andor accumulation ofelements from soil into the other twomatrices In some casesrice husk seems to act as a barrier for some heavymetals such
10 Journal of Chemistry
0
1
10
100
1000Cr
conc
entr
atio
n (m
gkg
)
Samples
Cr
1
10
100
As c
once
ntra
tion
(mg
kg)
As
0
1
10
100
Pb co
ncen
trat
ion
(mg
kg) Pb
0
2000
4000
6000
8000
10000
12000
K co
ncen
trat
ion
(mg
kg) K
010203040506070
Cu co
ncen
trat
ion
(mg
kg) Cu
010203040506070
Zn co
ncen
trat
ion
(mg
kg) Zn
0
1
10
100
Ni c
once
ntra
tion
(mg
kg) Ni
1
10
100
1000
10000
100000
Fe co
ncen
trat
ion
(mg
kg) Fe
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2 RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Figure 5 Concentration of elements in soil rice husk and rice samples from Korba and Raipur
as Cr K Fe and Pb The possible barrier role of rice husk isinteresting and it can be hypothesized also for Mn Ba andSr Unfortunately it is not clear in the case of Cu Ni Zn RbBi Ti and V
4 Conclusions
This work reports the chemical composition study of soilsrice and rice husk from Korba and Raipur (India) by means
Journal of Chemistry 11
of TXRF Results show some metals uptake from soil to ricein particular Pb and Cr from the Raipur region The noveltyof this study is the chemical characterization of rice made inparallel with the analysis of soils and corresponding rice huskA detailed analysis of all the data shows that rice husk accu-mulates more heavy metals than rice suggesting a possiblebarrier effect of the husk Despite that dedicated studiesshould be done to verify the clear role of husk and other para-meters such as rice species soils characteristics (pH claycontent and organic matter) and other variables Based onthe extremely interesting results obtained in this study someapproaches may be developed to promote low metals accu-mulation in rice
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study was supported by LIFE+ the financial instrumentof the European Community to support environmentalprojects (LIFE+ 2011 Project ENVIT000256) The authorsare grateful to Directorate-General Environment EuropeanCommission for inclusion of COSMOS-RICE Project inScience for Environment Policy Information Service (seehttpeceuropaeuenvironmentintegrationresearchnew-salertpdf383na2 enpdf) The authors acknowledge Profe-ssor Patel School of Studies in Chemistry Pt RavishankarShukla University Raipur India for the support in samplescollection
References
[1] C Huamain Z Chunrong T Cong and Z Yongguan ldquoHeavymetal pollution in soils in China status and countermeasuresrdquoAmbio vol 28 no 2 pp 130ndash134 1999
[2] M E Watanabe ldquoPhytoremediation on the brink of commer-cializationrdquo Environmental Science amp Technology vol 31 pp82Andash187A 1997
[3] S Uchida K Tagami and N Ishikawa ldquoConcentration soil-to-plant transfer factor and soil-soil solution distribution coeffi-cient of selenium in the surface environment -9106rdquo in Proceed-ings of the Symposium onWasteManagement (WM rsquo09 ) pp 1ndash5Phoenix Ariz USA March 2009
[4] X F Hu Y Jiang Y Shu X Hu L Liu and F Luo ldquoEffectsof mining wastewater discharges on heavy metal pollution andsoil enzyme activity of the paddy fieldsrdquo Journal of GeochemicalExploration vol 147 part B pp 139ndash150 2014
[5] A Sekara M Poniedziałek J Ciura and E Jedrszczyk ldquoCad-mium and lead accumulation and distribution in the organs ofnine crops implications for phytoremediationrdquo Polish Journalof Environmental Studies vol 14 no 4 pp 509ndash516 2005
[6] R Stone ldquoFood safetymdasharsenic and paddy rice a neglectedcancer riskrdquo Science vol 321 no 5886 pp 184ndash185 2008
[7] Committee for the Common Organisation of Agricultural Mar-kets 11 2014 httpeceuropaeuagriculturecerealspresenta-tionsricemarket-situation enpdf
[8] K R Dikshit and J E Schwartzberg ldquoIndia iI paeserdquo in Enci-clopedia Britannica pp 9ndash10 2007
[9] K M Omatola and A D Onojah ldquoElemental analysis of ricehusk ash using X-ray fluorescence techniquerdquo InternationalJournal of Physical Sciences vol 4 no 4 pp 189ndash193 2009
[10] L Sun and K Gong ldquoSilicon-based materials from rice husksand their applicationsrdquo Industrial and Engineering ChemistryResearch vol 40 no 25 pp 5861ndash5877 2001
[11] S Sugita ldquoOn the economical production of large quantities ofhighly reactive rice husk ashrdquo in Proceedings of the InternationalSymposium on Innovative World of Concrete (ICI-IWC rsquo93) pp2 3ndash71 1993
[12] I R Shaikh and A A Shaikh ldquoUtilization of wheat husk ashas silica source for the synthesis of MCM-41 type mesoporoussilicates a sustainable approach towards valorization of the agri-cultural waste streamrdquo Research Journal of Chemical Sciencesvol 3 pp 66ndash72 2013
[13] K M Omatola and A D Onojah ldquoRice husk as a potentialsource of high technological raw materials a reviewrdquo Journalof Polymer Science Innovation vol 4 pp 30ndash35 2012
[14] A Bosio N Rodella A Gianoncelli et al ldquoA new method toinertize incinerator toxic fly ash with silica from rice husk ashrdquoEnvironmental Chemistry Letters vol 11 no 4 pp 329ndash3332013
[15] A Bosio A Zacco L Borgese et al ldquoA sustainable technologyfor Pb and Zn stabilization based on the use of only wastematerials a green chemistry approach to avoid chemicals andpromote CO
2sequestrationrdquoChemical Engineering Journal vol
253 pp 377ndash384 2014[16] A Taylor S Branch M P Day M Patriarca and M White
ldquoAtomic spectrometry update Clinical and biological materialsfoods and beveragesrdquo Journal of Analytical Atomic Spectrometryvol 24 no 4 pp 535ndash579 2009
[17] K S Patel K Shrivas P Hoffmann and N Jakubowski ldquoAsurvey of lead pollution in Chhattisgarh State central IndiardquoEnvironmental Geochemistry and Health vol 28 no 1-2 pp 11ndash17 2006
[18] K S Patel K Shrivas R Brandt N Jakubowski W Corns andP Hoffmann ldquoArsenic contamination in water soil sedimentand rice of central Indiardquo Environmental Geochemistry andHealth vol 27 no 2 pp 131ndash145 2005
[19] B Giri K S Patel N K Jaiswal et al ldquoComposition and sourcesof organic tracers in aerosol particles of industrial central IndiardquoAtmospheric Research vol 120-121 pp 312ndash324 2013
[20] httpwwwepagovoswhazardtestmethodssw846pdfs3050bpdf
[21] L Borgese A Zacco E Bontempi et al ldquoTotal reflection of x-ray fluorescence (TXRF) amature technique for environmentalchemical nanoscale metrologyrdquoMeasurement Science and Tech-nology vol 20 no 8 Article ID 084027 2009
[22] F Bilo L Borgese D Cazzago et al ldquoTXRF analysis ofsoils and sediments to assess environmental contaminationrdquoEnvironmental Science and Pollution Research vol 21 no 23 pp13208ndash13214 2014
[23] Esdat 2000 Dutch Target and Intervention Values The newDutch list 2000 httpwwwesdatnet
[24] A Kabata-Pendias ldquoEnvironmental biogeochemistrymdashoutlineof the developmentrdquo Przeglad Geologiczny vol 49 no 10 pp957ndash959 2001
[25] S Srinivasa Gowd M Ramakrishna Reddy and P K GovilldquoAssessment of heavy metal contamination in soils at Jajmau
12 Journal of Chemistry
(Kanpur) and Unnao industrial areas of the Ganga Plain UttarPradesh Indiardquo Journal ofHazardousMaterials vol 174 no 1ndash3pp 113ndash121 2010
[26] K S Patel A Verma N K Jaiswal et al ldquoArsenic concentrationin soil rice and straw in central Indiardquo in Proceedings of the 4thInternational Congress on Arsenic in the Environment pp 508ndash509 July 2012
[27] A Kabata-Pendias Trace Elements in Soils and Plants Technol-ogy amp Engineering CRC Press 3rd edition 2000
[28] A D Jacobson and J D Blum ldquoCaSr and 87Sr86Sr geochem-istry of disseminated calcite in Himalayan silicate rocks fromNanga Parbat influence on river-water chemistryrdquoGeology vol28 no 5 pp 463ndash466 2000
[29] Y N Vodyanitskii ldquoCriteria of the technogenic nature ofheavy metals and metalloids in soils a review of publicationsrdquoEurasian Soil Science vol 42 no 9 pp 1053ndash1061 2009
[30] H Hoefler C Streli P Wobrauschek M Ovari and G ZarayldquoAnalysis of low Z elements in various environmental sampleswith total reflection X-ray fluorescence (TXRF) spectrometryrdquoSpectrochimica Acta Part B Atomic Spectroscopy vol 61 no 10-11 pp 1135ndash1140 2006
[31] K K Taha I M Shmou H M Osman and M H ShayoubldquoSoil-plant transfer and accumulation factors for trace elementsat the Blue and White Nilesrdquo Journal of Applied and IndustrialSciences vol 1 pp 97ndash102 2013
[32] H Papaefthymiou G Papatheodorou A Moustakli DChristodoulou and M Geraga ldquoNatural radionuclides and137Cs distributions and their relationship with sedimentologicalprocesses in Patras Harbour Greecerdquo Journal of EnvironmentalRadioactivity vol 94 no 2 pp 55ndash74 2007
[33] J Fu Q Zhou J Liu et al ldquoHigh levels of heavy metals inrice (Oryza sativa L) from a typical E-waste recycling areain southeast China and its potential risk to human healthrdquoChemosphere vol 71 no 7 pp 1269ndash1275 2008
[34] T D Phuong P Van Chuong D T Khiem and S Kokot ldquoEle-mental content of Vietnamese rice Part 1 Sampling analysisand comparison with previous studiesrdquo Analyst vol 124 no 4pp 553ndash560 1999
[35] S W Al Rmalli P I Haris C F Harrington and M AyubldquoA survey of arsenic in foodstuffs on sale in the UnitedKingdom and imported from Bangladeshrdquo Science of the TotalEnvironment vol 337 no 1ndash3 pp 23ndash30 2005
[36] C Fangmin Z Ningchun X Haiming et al ldquoCadmium andlead contamination in japonica rice grains and its variationamong the different locations in southeast Chinardquo Science of theTotal Environment vol 359 no 1ndash3 pp 156ndash166 2006
[37] National Programme on Safety Food SafetyMilled Rice Criteriaof PR China (NY5115-2002) China Ministry of AgricultureBeijing China 2002
[38] FAOWHOCodexAlimentariusGeneral Standards for Contam-inants and Toxins in Food Schedule1 Maximum and GuidelineLevels for Contaminants and Toxins in Food Joint FAOWHOFood Standards Programme Reference CXFAC 0216 CodexCommittee Rotterdam The Netherlands 2002
[39] The Ministry of Health of China GB 2762-2012 Standards forChinese Food Sanitation TheMinistry of Health of China 2012
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
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Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 3
Cr Mn Fe Ni Cu Zn GaBi
AsPb Br Rb SrCaAr
BiPbMo
Cl
AlBrRbSrSi VKP S
BaTiPu
lses (
cps)
106
105
104
103
102
E (keV)2 4 6 8 10 12 14
Figure 1 TXRF spectra of soil samples from Korba (black) and Raipur (grey)
[20] Smaller quantities of RH and rice samples were usedfor digestion About 030 g of rice and rice husk was weighedtransferred inside the vessel and mixed with 10mL of nitricacid 65 (Fluka) A magnetic shaker was inserted in eachvessel and then the vessel was closed with a cap providedwith a hole to allow the leakage of gases formed during thedigestion A CEM microwave digestion device was used todigest the samples at 200∘C and 400 Psi After complete sam-ple solubilization the solutions were transferred to 25 and10mL volumetric flasks respectively for soil and riceRH andfilled with MilliQ water to the exact volume
24 TXRF Analysis of Soils Rice Husk and Rice SamplesChemical analysis of the solutions obtained by digestionwas performed bymeans of TXRF spectroscopy Quantitativeanalysis was performed by the internal standard addition pro-cedure [21] using Ga as internal standard element becauseit was not present in all the original samples 10 120583L of Ga(1 gL) was added to 990 120583L of soil samples in order to obtaina final Ga concentration of 10mgL Ga concentration inrice and RH solutions was 1mgL 10 120583L of each samplesolution was deposited on a three-quartz glass sample carriercleaned and siliconized and then dried on a hot plate at 50∘CTXRF measurements were performed by Bruker S2 Picofoxequipped with Mo tube operating at 50 kV and 750120583A andSilicon-Drift Detector Live time for each measurement was600 seconds
3 Results and Discussion
31 TXRF Analysis of Soils Humidity in Raipur soils washigher than in Korba samples It ranges from 14 to 67while in Korba soils humidity was in the interval from 17 to29
TXRF spectra of soil samples from Korba and Raipur areshown in Figure 1 Signals of Al K Ca Ti V Cr Mn FeNi Cu Zn As Rb Ba Pb and Sr are clearly identified in allthe samples of both cities region Bi was present only in thesoils from Raipur suggesting possible anthropogenic causes
Regarding the nonmetals signals of S Cl and Br were alwaysidentified
TXRFmeasurement was performed in air for this reasonit is not possible to give an accurate estimation of the contentof lighter elements such as Al P and S Their concentrationmay be underestimated and higher standard deviations mayoccur (about 20 in the case of Al) The content of Feis higher compared to the other elements For this reasonfitting of TXRF spectra was performed considering the pileup peak of Fe K120572 However as it was demonstrated in arecent publication TXRF is a successful technique to performquantitative analysis of soils [22] Background levels werekept to a minimum with the use of quartz sample carriersreducing at minimum their contact time with HF
Results of quantitative analysis of soil samples are repor-ted in Table 2 Heavy metals content is higher in Raipursoil samples compared with Korba samples Almost all theelements concentrations are 4-5 times higher in Raipur thanin Korba Relative standard deviation (RSD) is used to evalu-ate the precision of the measurements RSD for most of theelements (Mn Fe Ni Cu and Zn) is in the range from 1 to64 Slightly higher RSDvalues are observed forV 94 andfor Ba from65 to 246 due to the reasons already discussed[22] The highest RSD values are observed for Bi probablydue to its low concentration which is near the lowest limitof detection (LLD)
Descriptive statistics of elemental content in soil samplesis reported in Table 3 Concentration of Bi is significantlylower compared to other elements in soils Mn is the elementwith the widest range of concentrations and the largest differ-ences in the two studies areas Zn concentration is almost thesame in both cities while Cr and Pb are significantly higherin all the Raipur samples highlighting the possible adverseeffects of the metallurgy industry in Raipur The data of soilscollected in the same area of Raipur in two different pointsdo not show any significant difference This result figures outa homogeneous distribution of metals in the studied regions
A comparison of our results with the guidelines and limitsproposed for the determination of heavy metals pollution
4 Journal of Chemistry
Table2Elem
entalcon
centratio
n(m
gkg)insoilsamples
from
Korbaa
ndRa
ipurR
esultsaree
xpressed
asthea
verageplusmnstandard
deviation
Sample
Elem
entsconcentration(m
gKg
)K
CaTi
VCr
Mn
FeNi
CuZn
As
BaSr
PbBi
Korba
S1K
4524plusmn203
2560plusmn297
1550plusmn85
14plusmn1
22plusmn1
254plusmn12
7071plusmn309
9plusmn1
11plusmn1
52plusmn3
4plusmn1
152plusmn18
28plusmn2
11plusmn1
nd
S2K
3829plusmn175
1448plusmn463
1562plusmn68
17plusmn2
25plusmn1
230plusmn10
8409plusmn379
10plusmn1
10plusmn1
58plusmn3
3plusmn1
76plusmn9
14plusmn2
12plusmn1
nd
S3K
5705plusmn44
7110
1plusmn417
1572plusmn72
15plusmn2
19plusmn1
83plusmn4
5676plusmn246
10plusmn1
6plusmn1
14plusmn1
4plusmn1
57plusmn8
3plusmn01
10plusmn1
nd
S4K
5031plusmn239
421plusmn
251350plusmn59
15plusmn1
24plusmn1
102plusmn4
7257plusmn316
12plusmn1
7plusmn1
15plusmn1
5plusmn1
117plusmn13
11plusmn1
11plusmn1
nd
S5K
6217plusmn511
441plusmn
341293plusmn63
11plusmn1
15plusmn1
143plusmn7
5781plusmn254
7plusmn1
6plusmn1
22plusmn1
5plusmn1
136plusmn10
15plusmn1
13plusmn1
nd
Raipur
S1A
R7617plusmn391
2660plusmn1637
4337plusmn197
61plusmn6
112plusmn6
1455plusmn66
38863plusmn1737
39plusmn2
34plusmn2
60plusmn4
15plusmn1
166plusmn28
23plusmn6
64plusmn5
4plusmn1
S1B
R8117plusmn356
786plusmn57
4893plusmn213
55plusmn4
120plusmn5
1055plusmn46
39578plusmn1716
45plusmn2
37plusmn2
60plusmn2
12plusmn2
162plusmn12
16plusmn1
55plusmn5
5plusmn1
S2A
R6172plusmn318
1088plusmn228
4610plusmn222
65plusmn5
111plusmn
5973plusmn46
38183plusmn1671
45plusmn3
34plusmn2
60plusmn5
13plusmn2
160plusmn22
20plusmn3
46plusmn5
5plusmn1
S2B
R4895plusmn226
1199plusmn66
4716plusmn207
60plusmn4
127plusmn6
463plusmn20
37942plusmn1647
49plusmn2
34plusmn1
51plusmn2
15plusmn2
158plusmn18
21plusmn1
46plusmn5
5plusmn1
S3A
R9251plusmn477
837plusmn151
5246plusmn248
107plusmn10
145plusmn7
1855plusmn81
32937plusmn1437
80plusmn4
43plusmn2
60plusmn3
21plusmn3
170plusmn42
16plusmn2
55plusmn8
5plusmn2
S3B
R9149plusmn40
0786plusmn42
5959plusmn258
116plusmn7
121plusmn
51389plusmn61
27203plusmn1331
75plusmn3
46plusmn2
50plusmn2
26plusmn1
147plusmn22
11plusmn2
44plusmn2
4plusmn1
S4A
R5318plusmn233
1078plusmn115
4993plusmn218
74plusmn4
131plusmn
61304plusmn58
42808plusmn1863
55plusmn2
36plusmn2
54plusmn7
18plusmn2
191plusmn
1317plusmn1
54plusmn5
5plusmn2
S4B
R5497plusmn270
824plusmn137
5270plusmn254
116plusmn11
122plusmn6
1984plusmn90
31119plusmn1360
80plusmn5
49plusmn14
56plusmn3
30plusmn3
129plusmn30
11plusmn4
55plusmn6
4plusmn1
S5A
R7477plusmn510
1275plusmn594
4672plusmn205
127plusmn8
174plusmn8
2597plusmn113
43853plusmn2203
79plusmn4
44plusmn2
54plusmn6
36plusmn3
261plusmn
11617plusmn6
69plusmn3
5plusmn1
S5B
58599plusmn422
2557plusmn237
5285plusmn232
111plusmn
6155plusmn7
1701plusmn75
40033plusmn1767
71plusmn3
43plusmn2
55plusmn2
24plusmn3
427plusmn54
31plusmn3
67plusmn6
8plusmn1
Journal of Chemistry 5
Table 3 Descriptive statistics results of elemental chemical analysis for Korba and Raipur soils
K Ca Ti V Cr Mn Fe Ni Cu Zn As Ba Rb Sr Pb BiKorba
Mean 506110 119582 146522 1438 2078 16239 683882 954 796 3220 420 10751 2362 1424 1135 ndSD 94297 88066 13332 229 410 7601 113639 190 229 2111 064 3998 720 898 120 ndMin 382912 42076 129266 1108 1456 8290 567619 654 595 1415 338 5699 1381 316 985 ndMax 621660 255993 157193 1732 2468 25370 840931 1162 1084 5818 486 17160 3073 2782 1280 nd
RaipurMean 720917 130909 498811 8934 13188 147754 3720198 6184 3959 5586 2096 19705 2624 1845 5545 511SD 162834 70736 47133 2831 2011 59658 518952 1660 591 386 805 8800 1664 632 894 118Min 489548 78577 433685 5544 11148 46253 2720251 3934 3109 5003 1190 12943 1023 1076 4355 383Max 925130 365998 595869 12684 17361 257907 4335400 7993 4851 6011 3568 42757 7132 3275 6921 815
[23] indicates that all the soil samples of Korba are notcontaminated while soils from Raipur are contaminated byNi Cu Cr As and Ba
A more detailed comparison of our data with thoseobtained in other studies of soil contamination in the samearea reveals a good agreement The comparison with datareported by Kabata Pendias for uncontaminated soils (Cr04ndash29mgkg Mn 25ndash8000mgkg Ni 3ndash150mgkg Cu 05ndash135mgkg Zn 1ndash750mgkg and Pb 06ndash63mgkg) [24] sug-gests that Cr and Pb contamination is present in RaipurMorerecent studies by Srinivasa Gowd et al [25] and Patel et al[26] reported higher content of Pb Zn and Cr Thus onlycontamination by Cr would be present However it should beconsidered that Pb Zn andCr concentration increased easilyduring the industrial activity particularly in themining areasSo the increasing inmetal concentration in these soils may bea consequence of anthropogenic influence
Statistical analysis was used to evaluate the correlationof the elements present in soil Cluster analysis was usedto highlight the differences between soils from Korba andRaipur Hierarchical division was performed using the Wardmethod which is based on the analysis of variances insteadof distances The varimax rotation with Kaiser normalizationmethod was used for factor analysis By extracting the eigen-values the number of significant factors was determinedData treatment was performed using the JMP 10 softwareResults of cluster analysis are reported in Figure 2The dend-rogram clearly points out the division of the samples intwo clusters corresponding to the different sampled areas ofKorba and Raipur Considering that the two studied citiesbelong to the same region of India and supposing the samecrustal composition this result suggests a different degree ofpollution
Results of factor analysis show that the three eigenvaluesexplain 9018 of the variance Therefore they were selectedfor further factor analysis The loadings of elements withrespect to each one of the three identified factors are reportedin Table 4 All the elements with high loadings for the samefactor may have a common origin in soils The first factor isresponsible for 563 of the total variance and it includes KTi V Cr Mn Fe Ni Cu Zn As Pb and Bi Consideringthe nature of these elements and their simultaneous presencethis suggests their anthropogenic origin The second factor
1 2 3 4 5 6 7 8 9 12 10 11 13 14 15
Figure 2 Dendrogram of cluster analysis for Korba (red) andRaipur (green) samples
accounts for 1709 of the total variance and it includes Caand Sr Ca and Sr are included in the list of the eight mostabundant rock forming elements of biosphere which may beadded to the soil from wind dispersion of dust from minetailing and wastes tips [27 28] The third principal compo-nent represented 1679 of the total variance and it includesAl Rb and Ba The presence of Al would suggest a crustalorigin Indeed Al acts as a natural marker element while itsanthropogenic origin is still unknown Al is a conservativeelement and is contained in aluminosilicates as is reported byVodyanitskii [29] However the crustal origin of Rb and Ba isnot assessed
32 TXRF Analysis of Rice and Rice Husk TXRF spectra ofrice and rice husk are shown in Figure 3 Signals of Mg AlP S Cl K Ca Ti Cr Mn Fe Ni Cu Zn Ba Rb Pb Br andSr are identified in both rice and RH samples After spectradeconvolution concentration of each was determined except
6 Journal of Chemistry
Pulse
s (cp
s)
E (keV)
SrRbBrPbGaZnCuNiFeMnCrBaTiCaKArCl
Mo
SPSiGa
Mg Sr
E RbAl
Zn
Pb
2 4 6 8 10 12 14
times1E3
30
20
10
00
Figure 3 Spectra of rice husk (black) and rice (gray) sample 2 from Korba measured by S2 Picofox
Table 4 Rotated component matrix for soil samples
(a)
Variables Rotated factor1 2 3
Al 04877 03792 07279K 05859 minus00676 05477Ca 00419 09249 01358Ti 09527 01259 00972V 09167 00068 03339Cr 09421 01997 0203Mn 08834 00792 02768Fe 08929 03231 00015Ni 09423 minus00077 02811Cu 09715 01256 01389Zn 06599 05904 minus01872As 08862 minus004 029Rb 00402 0147 09675Sr 00761 09325 02809Ba 04065 05243 06689Pb 09163 0287 01481Bi 08439 03457 02535
(b)
Variance explained by each factorFactor Variance Percent Cum percentFactor 1 95731 56313 56313Factor 2 29045 17085 73398Factor 3 28535 16785 90183
for elements lighter thanKQuantification of the detected lowZ elements is not reported because our measurements wereperformed in air and vacuum conditions are recommendedin this case [30] Results of quantitative analysis of rice andrice husk samples are reported in Table 5
Elemental composition of rice husk and rice is similarfor all the studied samples even if Ca Ti Mn Fe and Pbare higher in RH with respect to rice The concentrationof metals in the two matrices is usually correlated In thesamples from Korba the highest concentrations of Ti Fe andZn were detected in sample 3 for both the analyzed matrices(3R K and 3RH K) and the highest concentration of Ca andMn in sample 1 (1R K and 1RH K) In the samples fromRaipur the highest concentrations of Fe and Zn are foundin sample 3 (3R R and 3RH R) while the highest content ofMn was in sample 4 (4R R and 4RH R) Rice husk samplesof Korba contain Cr that is not detected in rice while Cris present in both the matrices collected in Raipur with theusual correlationThis can be due to the higher concentrationof Cr in Raipur than Korba soilsThe correlation observed forthe other elements is not present in the case of Pb Indeed thehighest value of Pb for rice husk samples is present in sample5RH K while the highest value of Pb for rice is present insample 2R K A similar behavior is observed for Ca and Ti inthe samples from Raipur
Descriptive statistics of elemental content in rice and ricehusk samples is reported in Table 6The comparison of heavymetals concentration in rice grain from the two studied areasshows no significant differences among K Ca Ti Ni Cuand Zn Other elements such as Cr Fe and Pb are higherin Raipur samples while Mn and Rb are higher in Korbasamples Concentration of heavymetals detected in rice sam-ples decreases in the following order Mn gt Zn gt Cu gt Ni gtPb gt Cr
Metal uptake is higher for plants germinated in soilsenriched with metals from anthropogenic factors Thereforebioaccumulation ability of plants is one of the most criticalproblems faced in agriculture and environmental studiesTransfer factor (TF) is an indicator of the plant species abilityor tendency to uptake a certain element from the soil [31]TF is obtained by dividing the element concentration in theplant by its concentration in soil according to (1) where119862p is the metal concentration in plant and 119862s is the metal
Journal of Chemistry 7
Table5Elem
entalcon
centratio
nin
rice(R)
andric
ehusk(RH)sam
ples
from
Korbaa
ndRa
ipur
Sample
Elem
entalcon
centratio
n(m
gKg
)K
CaTi
CrMn
FeNi
CuZn
RbSr
BaPb
Korba
1RK
2179plusmn122
267plusmn67
19plusmn04
00plusmn00
44plusmn2
18plusmn3
04plusmn01
22plusmn02
29plusmn1
186plusmn10
067plusmn014
nd
027plusmn001
2RK
2911plusmn160
225plusmn19
05plusmn03
00plusmn00
29plusmn1
19plusmn2
09plusmn01
24plusmn01
30plusmn1
352plusmn17
033plusmn005
nd
051plusmn003
3RK
2603plusmn184
227plusmn17
40plusmn03
00plusmn00
32plusmn1
21plusmn1
05plusmn01
30plusmn02
39plusmn2
42plusmn03
052plusmn003
nd
025plusmn002
4RK
1604plusmn111
223plusmn20
14plusmn04
00plusmn00
27plusmn1
13plusmn1
20plusmn06
30plusmn02
22plusmn1
57plusmn03
029plusmn002
nd
008plusmn002
5RK
2162plusmn113
175plusmn11
07plusmn02
00plusmn00
24plusmn1
15plusmn1
04plusmn01
25plusmn01
24plusmn1
225plusmn10
033plusmn001
nd
013plusmn001
1RH
K4152plusmn303
1500plusmn68
28plusmn09
04plusmn01
325plusmn15
93plusmn4
06plusmn01
20plusmn01
32plusmn1
223plusmn12
476plusmn022
32plusmn2
041plusmn004
2RH
K3894plusmn311
1277plusmn61
73plusmn24
00plusmn00
174plusmn8
161plusmn
1133plusmn02
18plusmn04
26plusmn1
287plusmn20
268plusmn013
15plusmn1
047plusmn003
3RH
K2277plusmn152
1485plusmn106
599plusmn456
09plusmn02
210plusmn9
409plusmn26
10plusmn01
21plusmn
02
33plusmn3
37plusmn03
449plusmn023
26plusmn2
070plusmn007
4RH
K44
41plusmn196
1072plusmn47
60plusmn24
02plusmn01
213plusmn9
184plusmn9
26plusmn01
22plusmn01
28plusmn1
111plusmn05
224plusmn010
25plusmn1
043plusmn002
5RH
K3782plusmn167
948plusmn61
23plusmn03
00plusmn00
206plusmn9
93plusmn4
06plusmn01
19plusmn01
27plusmn2
234plusmn11
289plusmn015
30plusmn1
102plusmn005
Raipur
1RR
3021plusmn221
395plusmn54
24plusmn11
03plusmn01
21plusmn1
33plusmn22
06plusmn01
34plusmn04
30plusmn2
06plusmn003
031plusmn003
nd
038plusmn002
2RR
2201plusmn101
232plusmn12
08plusmn02
00plusmn00
20plusmn1
13plusmn1
02plusmn01
17plusmn01
19plusmn1
32plusmn02
038plusmn002
nd
045plusmn004
3RR
2621plusmn120
347plusmn98
32plusmn04
03plusmn01
33plusmn1
24plusmn1
04plusmn01
23plusmn02
31plusmn2
11plusmn01
055plusmn004
nd
040plusmn003
4RR
2441plusmn134
345plusmn40
22plusmn05
02plusmn01
35plusmn2
22plusmn1
14plusmn01
31plusmn
02
30plusmn5
67plusmn03
049plusmn002
nd
026plusmn002
5RR
2295plusmn119
453plusmn182
17plusmn07
16plusmn07
26plusmn1
32plusmn2
18plusmn01
23plusmn01
25plusmn4
49plusmn03
059plusmn012
nd
024plusmn004
1RH
R6134plusmn284
1407plusmn237
248plusmn77
17plusmn09
159plusmn7
747plusmn43
09plusmn03
31plusmn
03
32plusmn3
13plusmn01
289plusmn015
5plusmn1
404plusmn018
2RH
R5088plusmn320
1727plusmn284
116plusmn28
10plusmn02
155plusmn8
601plusmn
3208plusmn04
22plusmn01
38plusmn8
48plusmn03
424plusmn056
5plusmn1
104plusmn012
3RH
R5474plusmn273
2165plusmn284
68plusmn07
08plusmn01
263plusmn12
589plusmn26
05plusmn01
24plusmn01
34plusmn2
18plusmn04
563plusmn026
8plusmn2
076plusmn005
4RH
R4866plusmn214
1367plusmn113
114plusmn07
433plusmn23
398plusmn18
957plusmn50
380plusmn19
29plusmn02
33plusmn3
92plusmn04
313plusmn019
14plusmn1
105plusmn007
5RH
R5930plusmn341
1441plusmn220
427plusmn115
84plusmn05
232plusmn10
918plusmn167
130plusmn06
27plusmn08
33plusmn4
71plusmn03
362plusmn023
6plusmn1
087plusmn034
8 Journal of Chemistry
Table 6 Descriptive statistics results of elemental chemical analysis for rice and rice husk from Korba and Raipur
K Ca Ti Cr Mn Fe Ni Cu Zn Rb Sr Ba PbKorba
RiceMean 229161 22352 171 000 3119 1725 085 261 2892 1724 043 nd 025SD 49562 3267 141 000 763 314 067 036 664 1279 016 nd 017Min 160361 17506 047 000 2397 1320 039 222 2218 418 029 nd 008Max 291056 26713 402 000 4367 2086 201 300 3909 3519 067 nd 051
RHMean 370919 125624 1567 032 22562 18803 162 201 2949 1785 341 2562 061SD 83990 24548 2483 009 5767 13003 122 013 322 1018 114 645 026Min 227706 94776 230 000 17433 9274 062 185 2587 369 224 1540 041Max 444080 149997 5992 090 32500 40897 325 217 3331 2869 476 3196 102
RaipurRiceMean 251578 35445 209 047 2685 2473 088 256 2707 329 046 nd 034SD 32375 8134 088 011 691 824 066 071 509 256 012 nd 009Min 220082 23192 084 000 1966 1267 022 166 1909 058 031 nd 024Max 302055 45290 324 160 3450 3261 177 344 3136 669 059 nd 045
RHMean 549853 162125 1948 1102 24133 76237 1064 266 3412 484 390 767 155SD 53845 33542 1463 1830 9908 17201 621 035 213 339 109 386 139Min 486602 136679 683 080 15514 58874 052 219 3218 131 289 467 076Max 613438 216507 4273 4326 39779 95678 3805 308 3765 921 563 1417 404
concentration in soil The variation observed in TFs for thesame species may be due to several factors such as the age ofthe plant the tissue and the environment in which the plantis grown It was demonstrated that the absorption ofmineralsand their distribution in the plant hang on the bioavailabilityof the minerals in soil root structure and shoot system[32] Moreover the bioavailability of elements from soil toplants is determined by other factors including pH redoxconditions speciation soil texture and mineralogy organicmatter content and the presence of competing ions
TFs calculated for rice and RH using the average valuesof elemental concentration in rice RH and soils of Korbaand Raipur are shown in Figure 4 In our study TFs for RHwere always higher than rice samples for both the studiedareas TFs of K Mn Cu Zn Rb and Ba are higher in Korbasamples compared to those of Raipur Elements such as Caand Cr show TFs higher in Raipur samples while Ti Fe Niand Pb were in the same range Our results clearly show thatthe bioaccumulation is higher in RH than in rice
TF =119862p
119862s (1)
A comparison with the literature data [33] for the content ofAs Ba Cu Pb Ni Mn and Cr in rice is reported in Table 7The average values calculated as the arithmetic mean forKorba and Raipur are reported separately The literaturereports that geometric means (GM) illustrate more exactdistribution of the element concentrations in rice samplesbut comparison withmany other studies is difficult due to thelack of information on GM [33] As and Ba are not present
0000
0001
0010
0100
1000
10000K
Ca
Ti
Cr
Mn
Fe
NiCu
Zn
Rb
Sr
Ba
Pb
Rice RaipurRH Raipur
Rice KorbaRH Korba
Figure 4 Transfer factors calculated for rice and rice husk sampleswith respect to soil samples from Korba and Raipur
in our samples Our values of Cu and Ni are aligned mainlywith those from Vietnam The concentrations of Pb and Mnare aligned respectively with commercial rice from China
Journal of Chemistry 9
Table 7 Concentration of hazardous elements in rice samples reported in different literature studies (a) arithmetic means (b) arithmeticstandard deviations (c) [34] (d) [35] and (e) [36]
Element Area 119873 AM (a) ASD (b) MIN MAX
Cu
Taizhou 13 4260 826 3037 5184Commercial rice China 5 3326 774 2812 4478
Vietnam (c) 31 2600 1100 5800Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2560 710 1662 3438Korba 5 2610 360 2222 2995
Pb
Taizhou 13 2042 2070 256 2602Commercial rice China 4 356 267 167 745
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 23700 19800 20100 24000Hangzhou (e) 5 131 103 45 308
Raipur 5 340 90 235 452Korba 5 250 170 78 514
Ni
Taizhou 13 761 391 339 1134Commercial rice China 4 476 276 201 818
Vietnam (c) 31 869 lt100 2022Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 880 660 216 1770Korba 5 850 670 387 2009
Mn
Taizhou 13 28640 5570 21977 37490Commercial rice China 4 9363 3288 5804 12708
Vietnam (c) 31 9900 5900 16300Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2685 6910 19700 34500Korba 5 31200 7600 24000 43700
Cr
Taizhou 13 107 83 6 279Commercial rice China 4 199 157 62 424
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 740 340 650 830Hangzhou (e) mdash mdash mdash mdash
Raipur 5 470 110 0 1600Korba 5 nd nd nd nd
and Taizhou The content of Cr in the samples of Raipur isexceptionally high
Despite all the reported data of metal content in riceaccording to the national standard for safety milled rice cri-teria [37] (NY5115-2002) themaximum allowable concentra-tions (MAC) ofAs and Pb are 050 and 020120583gg respectivelyMoreover the World Health Organization (WHO) provides020mgKg as the safe limit for Pb in rice [38] but it doesnot report any limit for other analyzed metals In the presentstudy Pb concentration is much higher than the reportedlimit in many samples both from Raipur and Korba evenif the average value is aligned with that of WHO Even it isknown as a toxic element Cr safe limit from WHOFAO is
not determined Since rice is the common food for the Asiancontinent and especially in China the MAC criteria deter-mine the same limit for some metals such as Cu 10mgKgZn 50mgKg Cr 1mgKg and Pb as that decided by WHO[39]
Statistical analysis does not show any significant differ-ence between rice and rice husk samples of the two areas ofinterest
Figure 5 shows the concentration of selected elements inall samples classified by species soil rice husk and riceThisfigure highlights the possible transfer andor accumulation ofelements from soil into the other twomatrices In some casesrice husk seems to act as a barrier for some heavymetals such
10 Journal of Chemistry
0
1
10
100
1000Cr
conc
entr
atio
n (m
gkg
)
Samples
Cr
1
10
100
As c
once
ntra
tion
(mg
kg)
As
0
1
10
100
Pb co
ncen
trat
ion
(mg
kg) Pb
0
2000
4000
6000
8000
10000
12000
K co
ncen
trat
ion
(mg
kg) K
010203040506070
Cu co
ncen
trat
ion
(mg
kg) Cu
010203040506070
Zn co
ncen
trat
ion
(mg
kg) Zn
0
1
10
100
Ni c
once
ntra
tion
(mg
kg) Ni
1
10
100
1000
10000
100000
Fe co
ncen
trat
ion
(mg
kg) Fe
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2 RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Figure 5 Concentration of elements in soil rice husk and rice samples from Korba and Raipur
as Cr K Fe and Pb The possible barrier role of rice husk isinteresting and it can be hypothesized also for Mn Ba andSr Unfortunately it is not clear in the case of Cu Ni Zn RbBi Ti and V
4 Conclusions
This work reports the chemical composition study of soilsrice and rice husk from Korba and Raipur (India) by means
Journal of Chemistry 11
of TXRF Results show some metals uptake from soil to ricein particular Pb and Cr from the Raipur region The noveltyof this study is the chemical characterization of rice made inparallel with the analysis of soils and corresponding rice huskA detailed analysis of all the data shows that rice husk accu-mulates more heavy metals than rice suggesting a possiblebarrier effect of the husk Despite that dedicated studiesshould be done to verify the clear role of husk and other para-meters such as rice species soils characteristics (pH claycontent and organic matter) and other variables Based onthe extremely interesting results obtained in this study someapproaches may be developed to promote low metals accu-mulation in rice
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study was supported by LIFE+ the financial instrumentof the European Community to support environmentalprojects (LIFE+ 2011 Project ENVIT000256) The authorsare grateful to Directorate-General Environment EuropeanCommission for inclusion of COSMOS-RICE Project inScience for Environment Policy Information Service (seehttpeceuropaeuenvironmentintegrationresearchnew-salertpdf383na2 enpdf) The authors acknowledge Profe-ssor Patel School of Studies in Chemistry Pt RavishankarShukla University Raipur India for the support in samplescollection
References
[1] C Huamain Z Chunrong T Cong and Z Yongguan ldquoHeavymetal pollution in soils in China status and countermeasuresrdquoAmbio vol 28 no 2 pp 130ndash134 1999
[2] M E Watanabe ldquoPhytoremediation on the brink of commer-cializationrdquo Environmental Science amp Technology vol 31 pp82Andash187A 1997
[3] S Uchida K Tagami and N Ishikawa ldquoConcentration soil-to-plant transfer factor and soil-soil solution distribution coeffi-cient of selenium in the surface environment -9106rdquo in Proceed-ings of the Symposium onWasteManagement (WM rsquo09 ) pp 1ndash5Phoenix Ariz USA March 2009
[4] X F Hu Y Jiang Y Shu X Hu L Liu and F Luo ldquoEffectsof mining wastewater discharges on heavy metal pollution andsoil enzyme activity of the paddy fieldsrdquo Journal of GeochemicalExploration vol 147 part B pp 139ndash150 2014
[5] A Sekara M Poniedziałek J Ciura and E Jedrszczyk ldquoCad-mium and lead accumulation and distribution in the organs ofnine crops implications for phytoremediationrdquo Polish Journalof Environmental Studies vol 14 no 4 pp 509ndash516 2005
[6] R Stone ldquoFood safetymdasharsenic and paddy rice a neglectedcancer riskrdquo Science vol 321 no 5886 pp 184ndash185 2008
[7] Committee for the Common Organisation of Agricultural Mar-kets 11 2014 httpeceuropaeuagriculturecerealspresenta-tionsricemarket-situation enpdf
[8] K R Dikshit and J E Schwartzberg ldquoIndia iI paeserdquo in Enci-clopedia Britannica pp 9ndash10 2007
[9] K M Omatola and A D Onojah ldquoElemental analysis of ricehusk ash using X-ray fluorescence techniquerdquo InternationalJournal of Physical Sciences vol 4 no 4 pp 189ndash193 2009
[10] L Sun and K Gong ldquoSilicon-based materials from rice husksand their applicationsrdquo Industrial and Engineering ChemistryResearch vol 40 no 25 pp 5861ndash5877 2001
[11] S Sugita ldquoOn the economical production of large quantities ofhighly reactive rice husk ashrdquo in Proceedings of the InternationalSymposium on Innovative World of Concrete (ICI-IWC rsquo93) pp2 3ndash71 1993
[12] I R Shaikh and A A Shaikh ldquoUtilization of wheat husk ashas silica source for the synthesis of MCM-41 type mesoporoussilicates a sustainable approach towards valorization of the agri-cultural waste streamrdquo Research Journal of Chemical Sciencesvol 3 pp 66ndash72 2013
[13] K M Omatola and A D Onojah ldquoRice husk as a potentialsource of high technological raw materials a reviewrdquo Journalof Polymer Science Innovation vol 4 pp 30ndash35 2012
[14] A Bosio N Rodella A Gianoncelli et al ldquoA new method toinertize incinerator toxic fly ash with silica from rice husk ashrdquoEnvironmental Chemistry Letters vol 11 no 4 pp 329ndash3332013
[15] A Bosio A Zacco L Borgese et al ldquoA sustainable technologyfor Pb and Zn stabilization based on the use of only wastematerials a green chemistry approach to avoid chemicals andpromote CO
2sequestrationrdquoChemical Engineering Journal vol
253 pp 377ndash384 2014[16] A Taylor S Branch M P Day M Patriarca and M White
ldquoAtomic spectrometry update Clinical and biological materialsfoods and beveragesrdquo Journal of Analytical Atomic Spectrometryvol 24 no 4 pp 535ndash579 2009
[17] K S Patel K Shrivas P Hoffmann and N Jakubowski ldquoAsurvey of lead pollution in Chhattisgarh State central IndiardquoEnvironmental Geochemistry and Health vol 28 no 1-2 pp 11ndash17 2006
[18] K S Patel K Shrivas R Brandt N Jakubowski W Corns andP Hoffmann ldquoArsenic contamination in water soil sedimentand rice of central Indiardquo Environmental Geochemistry andHealth vol 27 no 2 pp 131ndash145 2005
[19] B Giri K S Patel N K Jaiswal et al ldquoComposition and sourcesof organic tracers in aerosol particles of industrial central IndiardquoAtmospheric Research vol 120-121 pp 312ndash324 2013
[20] httpwwwepagovoswhazardtestmethodssw846pdfs3050bpdf
[21] L Borgese A Zacco E Bontempi et al ldquoTotal reflection of x-ray fluorescence (TXRF) amature technique for environmentalchemical nanoscale metrologyrdquoMeasurement Science and Tech-nology vol 20 no 8 Article ID 084027 2009
[22] F Bilo L Borgese D Cazzago et al ldquoTXRF analysis ofsoils and sediments to assess environmental contaminationrdquoEnvironmental Science and Pollution Research vol 21 no 23 pp13208ndash13214 2014
[23] Esdat 2000 Dutch Target and Intervention Values The newDutch list 2000 httpwwwesdatnet
[24] A Kabata-Pendias ldquoEnvironmental biogeochemistrymdashoutlineof the developmentrdquo Przeglad Geologiczny vol 49 no 10 pp957ndash959 2001
[25] S Srinivasa Gowd M Ramakrishna Reddy and P K GovilldquoAssessment of heavy metal contamination in soils at Jajmau
12 Journal of Chemistry
(Kanpur) and Unnao industrial areas of the Ganga Plain UttarPradesh Indiardquo Journal ofHazardousMaterials vol 174 no 1ndash3pp 113ndash121 2010
[26] K S Patel A Verma N K Jaiswal et al ldquoArsenic concentrationin soil rice and straw in central Indiardquo in Proceedings of the 4thInternational Congress on Arsenic in the Environment pp 508ndash509 July 2012
[27] A Kabata-Pendias Trace Elements in Soils and Plants Technol-ogy amp Engineering CRC Press 3rd edition 2000
[28] A D Jacobson and J D Blum ldquoCaSr and 87Sr86Sr geochem-istry of disseminated calcite in Himalayan silicate rocks fromNanga Parbat influence on river-water chemistryrdquoGeology vol28 no 5 pp 463ndash466 2000
[29] Y N Vodyanitskii ldquoCriteria of the technogenic nature ofheavy metals and metalloids in soils a review of publicationsrdquoEurasian Soil Science vol 42 no 9 pp 1053ndash1061 2009
[30] H Hoefler C Streli P Wobrauschek M Ovari and G ZarayldquoAnalysis of low Z elements in various environmental sampleswith total reflection X-ray fluorescence (TXRF) spectrometryrdquoSpectrochimica Acta Part B Atomic Spectroscopy vol 61 no 10-11 pp 1135ndash1140 2006
[31] K K Taha I M Shmou H M Osman and M H ShayoubldquoSoil-plant transfer and accumulation factors for trace elementsat the Blue and White Nilesrdquo Journal of Applied and IndustrialSciences vol 1 pp 97ndash102 2013
[32] H Papaefthymiou G Papatheodorou A Moustakli DChristodoulou and M Geraga ldquoNatural radionuclides and137Cs distributions and their relationship with sedimentologicalprocesses in Patras Harbour Greecerdquo Journal of EnvironmentalRadioactivity vol 94 no 2 pp 55ndash74 2007
[33] J Fu Q Zhou J Liu et al ldquoHigh levels of heavy metals inrice (Oryza sativa L) from a typical E-waste recycling areain southeast China and its potential risk to human healthrdquoChemosphere vol 71 no 7 pp 1269ndash1275 2008
[34] T D Phuong P Van Chuong D T Khiem and S Kokot ldquoEle-mental content of Vietnamese rice Part 1 Sampling analysisand comparison with previous studiesrdquo Analyst vol 124 no 4pp 553ndash560 1999
[35] S W Al Rmalli P I Haris C F Harrington and M AyubldquoA survey of arsenic in foodstuffs on sale in the UnitedKingdom and imported from Bangladeshrdquo Science of the TotalEnvironment vol 337 no 1ndash3 pp 23ndash30 2005
[36] C Fangmin Z Ningchun X Haiming et al ldquoCadmium andlead contamination in japonica rice grains and its variationamong the different locations in southeast Chinardquo Science of theTotal Environment vol 359 no 1ndash3 pp 156ndash166 2006
[37] National Programme on Safety Food SafetyMilled Rice Criteriaof PR China (NY5115-2002) China Ministry of AgricultureBeijing China 2002
[38] FAOWHOCodexAlimentariusGeneral Standards for Contam-inants and Toxins in Food Schedule1 Maximum and GuidelineLevels for Contaminants and Toxins in Food Joint FAOWHOFood Standards Programme Reference CXFAC 0216 CodexCommittee Rotterdam The Netherlands 2002
[39] The Ministry of Health of China GB 2762-2012 Standards forChinese Food Sanitation TheMinistry of Health of China 2012
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4 Journal of Chemistry
Table2Elem
entalcon
centratio
n(m
gkg)insoilsamples
from
Korbaa
ndRa
ipurR
esultsaree
xpressed
asthea
verageplusmnstandard
deviation
Sample
Elem
entsconcentration(m
gKg
)K
CaTi
VCr
Mn
FeNi
CuZn
As
BaSr
PbBi
Korba
S1K
4524plusmn203
2560plusmn297
1550plusmn85
14plusmn1
22plusmn1
254plusmn12
7071plusmn309
9plusmn1
11plusmn1
52plusmn3
4plusmn1
152plusmn18
28plusmn2
11plusmn1
nd
S2K
3829plusmn175
1448plusmn463
1562plusmn68
17plusmn2
25plusmn1
230plusmn10
8409plusmn379
10plusmn1
10plusmn1
58plusmn3
3plusmn1
76plusmn9
14plusmn2
12plusmn1
nd
S3K
5705plusmn44
7110
1plusmn417
1572plusmn72
15plusmn2
19plusmn1
83plusmn4
5676plusmn246
10plusmn1
6plusmn1
14plusmn1
4plusmn1
57plusmn8
3plusmn01
10plusmn1
nd
S4K
5031plusmn239
421plusmn
251350plusmn59
15plusmn1
24plusmn1
102plusmn4
7257plusmn316
12plusmn1
7plusmn1
15plusmn1
5plusmn1
117plusmn13
11plusmn1
11plusmn1
nd
S5K
6217plusmn511
441plusmn
341293plusmn63
11plusmn1
15plusmn1
143plusmn7
5781plusmn254
7plusmn1
6plusmn1
22plusmn1
5plusmn1
136plusmn10
15plusmn1
13plusmn1
nd
Raipur
S1A
R7617plusmn391
2660plusmn1637
4337plusmn197
61plusmn6
112plusmn6
1455plusmn66
38863plusmn1737
39plusmn2
34plusmn2
60plusmn4
15plusmn1
166plusmn28
23plusmn6
64plusmn5
4plusmn1
S1B
R8117plusmn356
786plusmn57
4893plusmn213
55plusmn4
120plusmn5
1055plusmn46
39578plusmn1716
45plusmn2
37plusmn2
60plusmn2
12plusmn2
162plusmn12
16plusmn1
55plusmn5
5plusmn1
S2A
R6172plusmn318
1088plusmn228
4610plusmn222
65plusmn5
111plusmn
5973plusmn46
38183plusmn1671
45plusmn3
34plusmn2
60plusmn5
13plusmn2
160plusmn22
20plusmn3
46plusmn5
5plusmn1
S2B
R4895plusmn226
1199plusmn66
4716plusmn207
60plusmn4
127plusmn6
463plusmn20
37942plusmn1647
49plusmn2
34plusmn1
51plusmn2
15plusmn2
158plusmn18
21plusmn1
46plusmn5
5plusmn1
S3A
R9251plusmn477
837plusmn151
5246plusmn248
107plusmn10
145plusmn7
1855plusmn81
32937plusmn1437
80plusmn4
43plusmn2
60plusmn3
21plusmn3
170plusmn42
16plusmn2
55plusmn8
5plusmn2
S3B
R9149plusmn40
0786plusmn42
5959plusmn258
116plusmn7
121plusmn
51389plusmn61
27203plusmn1331
75plusmn3
46plusmn2
50plusmn2
26plusmn1
147plusmn22
11plusmn2
44plusmn2
4plusmn1
S4A
R5318plusmn233
1078plusmn115
4993plusmn218
74plusmn4
131plusmn
61304plusmn58
42808plusmn1863
55plusmn2
36plusmn2
54plusmn7
18plusmn2
191plusmn
1317plusmn1
54plusmn5
5plusmn2
S4B
R5497plusmn270
824plusmn137
5270plusmn254
116plusmn11
122plusmn6
1984plusmn90
31119plusmn1360
80plusmn5
49plusmn14
56plusmn3
30plusmn3
129plusmn30
11plusmn4
55plusmn6
4plusmn1
S5A
R7477plusmn510
1275plusmn594
4672plusmn205
127plusmn8
174plusmn8
2597plusmn113
43853plusmn2203
79plusmn4
44plusmn2
54plusmn6
36plusmn3
261plusmn
11617plusmn6
69plusmn3
5plusmn1
S5B
58599plusmn422
2557plusmn237
5285plusmn232
111plusmn
6155plusmn7
1701plusmn75
40033plusmn1767
71plusmn3
43plusmn2
55plusmn2
24plusmn3
427plusmn54
31plusmn3
67plusmn6
8plusmn1
Journal of Chemistry 5
Table 3 Descriptive statistics results of elemental chemical analysis for Korba and Raipur soils
K Ca Ti V Cr Mn Fe Ni Cu Zn As Ba Rb Sr Pb BiKorba
Mean 506110 119582 146522 1438 2078 16239 683882 954 796 3220 420 10751 2362 1424 1135 ndSD 94297 88066 13332 229 410 7601 113639 190 229 2111 064 3998 720 898 120 ndMin 382912 42076 129266 1108 1456 8290 567619 654 595 1415 338 5699 1381 316 985 ndMax 621660 255993 157193 1732 2468 25370 840931 1162 1084 5818 486 17160 3073 2782 1280 nd
RaipurMean 720917 130909 498811 8934 13188 147754 3720198 6184 3959 5586 2096 19705 2624 1845 5545 511SD 162834 70736 47133 2831 2011 59658 518952 1660 591 386 805 8800 1664 632 894 118Min 489548 78577 433685 5544 11148 46253 2720251 3934 3109 5003 1190 12943 1023 1076 4355 383Max 925130 365998 595869 12684 17361 257907 4335400 7993 4851 6011 3568 42757 7132 3275 6921 815
[23] indicates that all the soil samples of Korba are notcontaminated while soils from Raipur are contaminated byNi Cu Cr As and Ba
A more detailed comparison of our data with thoseobtained in other studies of soil contamination in the samearea reveals a good agreement The comparison with datareported by Kabata Pendias for uncontaminated soils (Cr04ndash29mgkg Mn 25ndash8000mgkg Ni 3ndash150mgkg Cu 05ndash135mgkg Zn 1ndash750mgkg and Pb 06ndash63mgkg) [24] sug-gests that Cr and Pb contamination is present in RaipurMorerecent studies by Srinivasa Gowd et al [25] and Patel et al[26] reported higher content of Pb Zn and Cr Thus onlycontamination by Cr would be present However it should beconsidered that Pb Zn andCr concentration increased easilyduring the industrial activity particularly in themining areasSo the increasing inmetal concentration in these soils may bea consequence of anthropogenic influence
Statistical analysis was used to evaluate the correlationof the elements present in soil Cluster analysis was usedto highlight the differences between soils from Korba andRaipur Hierarchical division was performed using the Wardmethod which is based on the analysis of variances insteadof distances The varimax rotation with Kaiser normalizationmethod was used for factor analysis By extracting the eigen-values the number of significant factors was determinedData treatment was performed using the JMP 10 softwareResults of cluster analysis are reported in Figure 2The dend-rogram clearly points out the division of the samples intwo clusters corresponding to the different sampled areas ofKorba and Raipur Considering that the two studied citiesbelong to the same region of India and supposing the samecrustal composition this result suggests a different degree ofpollution
Results of factor analysis show that the three eigenvaluesexplain 9018 of the variance Therefore they were selectedfor further factor analysis The loadings of elements withrespect to each one of the three identified factors are reportedin Table 4 All the elements with high loadings for the samefactor may have a common origin in soils The first factor isresponsible for 563 of the total variance and it includes KTi V Cr Mn Fe Ni Cu Zn As Pb and Bi Consideringthe nature of these elements and their simultaneous presencethis suggests their anthropogenic origin The second factor
1 2 3 4 5 6 7 8 9 12 10 11 13 14 15
Figure 2 Dendrogram of cluster analysis for Korba (red) andRaipur (green) samples
accounts for 1709 of the total variance and it includes Caand Sr Ca and Sr are included in the list of the eight mostabundant rock forming elements of biosphere which may beadded to the soil from wind dispersion of dust from minetailing and wastes tips [27 28] The third principal compo-nent represented 1679 of the total variance and it includesAl Rb and Ba The presence of Al would suggest a crustalorigin Indeed Al acts as a natural marker element while itsanthropogenic origin is still unknown Al is a conservativeelement and is contained in aluminosilicates as is reported byVodyanitskii [29] However the crustal origin of Rb and Ba isnot assessed
32 TXRF Analysis of Rice and Rice Husk TXRF spectra ofrice and rice husk are shown in Figure 3 Signals of Mg AlP S Cl K Ca Ti Cr Mn Fe Ni Cu Zn Ba Rb Pb Br andSr are identified in both rice and RH samples After spectradeconvolution concentration of each was determined except
6 Journal of Chemistry
Pulse
s (cp
s)
E (keV)
SrRbBrPbGaZnCuNiFeMnCrBaTiCaKArCl
Mo
SPSiGa
Mg Sr
E RbAl
Zn
Pb
2 4 6 8 10 12 14
times1E3
30
20
10
00
Figure 3 Spectra of rice husk (black) and rice (gray) sample 2 from Korba measured by S2 Picofox
Table 4 Rotated component matrix for soil samples
(a)
Variables Rotated factor1 2 3
Al 04877 03792 07279K 05859 minus00676 05477Ca 00419 09249 01358Ti 09527 01259 00972V 09167 00068 03339Cr 09421 01997 0203Mn 08834 00792 02768Fe 08929 03231 00015Ni 09423 minus00077 02811Cu 09715 01256 01389Zn 06599 05904 minus01872As 08862 minus004 029Rb 00402 0147 09675Sr 00761 09325 02809Ba 04065 05243 06689Pb 09163 0287 01481Bi 08439 03457 02535
(b)
Variance explained by each factorFactor Variance Percent Cum percentFactor 1 95731 56313 56313Factor 2 29045 17085 73398Factor 3 28535 16785 90183
for elements lighter thanKQuantification of the detected lowZ elements is not reported because our measurements wereperformed in air and vacuum conditions are recommendedin this case [30] Results of quantitative analysis of rice andrice husk samples are reported in Table 5
Elemental composition of rice husk and rice is similarfor all the studied samples even if Ca Ti Mn Fe and Pbare higher in RH with respect to rice The concentrationof metals in the two matrices is usually correlated In thesamples from Korba the highest concentrations of Ti Fe andZn were detected in sample 3 for both the analyzed matrices(3R K and 3RH K) and the highest concentration of Ca andMn in sample 1 (1R K and 1RH K) In the samples fromRaipur the highest concentrations of Fe and Zn are foundin sample 3 (3R R and 3RH R) while the highest content ofMn was in sample 4 (4R R and 4RH R) Rice husk samplesof Korba contain Cr that is not detected in rice while Cris present in both the matrices collected in Raipur with theusual correlationThis can be due to the higher concentrationof Cr in Raipur than Korba soilsThe correlation observed forthe other elements is not present in the case of Pb Indeed thehighest value of Pb for rice husk samples is present in sample5RH K while the highest value of Pb for rice is present insample 2R K A similar behavior is observed for Ca and Ti inthe samples from Raipur
Descriptive statistics of elemental content in rice and ricehusk samples is reported in Table 6The comparison of heavymetals concentration in rice grain from the two studied areasshows no significant differences among K Ca Ti Ni Cuand Zn Other elements such as Cr Fe and Pb are higherin Raipur samples while Mn and Rb are higher in Korbasamples Concentration of heavymetals detected in rice sam-ples decreases in the following order Mn gt Zn gt Cu gt Ni gtPb gt Cr
Metal uptake is higher for plants germinated in soilsenriched with metals from anthropogenic factors Thereforebioaccumulation ability of plants is one of the most criticalproblems faced in agriculture and environmental studiesTransfer factor (TF) is an indicator of the plant species abilityor tendency to uptake a certain element from the soil [31]TF is obtained by dividing the element concentration in theplant by its concentration in soil according to (1) where119862p is the metal concentration in plant and 119862s is the metal
Journal of Chemistry 7
Table5Elem
entalcon
centratio
nin
rice(R)
andric
ehusk(RH)sam
ples
from
Korbaa
ndRa
ipur
Sample
Elem
entalcon
centratio
n(m
gKg
)K
CaTi
CrMn
FeNi
CuZn
RbSr
BaPb
Korba
1RK
2179plusmn122
267plusmn67
19plusmn04
00plusmn00
44plusmn2
18plusmn3
04plusmn01
22plusmn02
29plusmn1
186plusmn10
067plusmn014
nd
027plusmn001
2RK
2911plusmn160
225plusmn19
05plusmn03
00plusmn00
29plusmn1
19plusmn2
09plusmn01
24plusmn01
30plusmn1
352plusmn17
033plusmn005
nd
051plusmn003
3RK
2603plusmn184
227plusmn17
40plusmn03
00plusmn00
32plusmn1
21plusmn1
05plusmn01
30plusmn02
39plusmn2
42plusmn03
052plusmn003
nd
025plusmn002
4RK
1604plusmn111
223plusmn20
14plusmn04
00plusmn00
27plusmn1
13plusmn1
20plusmn06
30plusmn02
22plusmn1
57plusmn03
029plusmn002
nd
008plusmn002
5RK
2162plusmn113
175plusmn11
07plusmn02
00plusmn00
24plusmn1
15plusmn1
04plusmn01
25plusmn01
24plusmn1
225plusmn10
033plusmn001
nd
013plusmn001
1RH
K4152plusmn303
1500plusmn68
28plusmn09
04plusmn01
325plusmn15
93plusmn4
06plusmn01
20plusmn01
32plusmn1
223plusmn12
476plusmn022
32plusmn2
041plusmn004
2RH
K3894plusmn311
1277plusmn61
73plusmn24
00plusmn00
174plusmn8
161plusmn
1133plusmn02
18plusmn04
26plusmn1
287plusmn20
268plusmn013
15plusmn1
047plusmn003
3RH
K2277plusmn152
1485plusmn106
599plusmn456
09plusmn02
210plusmn9
409plusmn26
10plusmn01
21plusmn
02
33plusmn3
37plusmn03
449plusmn023
26plusmn2
070plusmn007
4RH
K44
41plusmn196
1072plusmn47
60plusmn24
02plusmn01
213plusmn9
184plusmn9
26plusmn01
22plusmn01
28plusmn1
111plusmn05
224plusmn010
25plusmn1
043plusmn002
5RH
K3782plusmn167
948plusmn61
23plusmn03
00plusmn00
206plusmn9
93plusmn4
06plusmn01
19plusmn01
27plusmn2
234plusmn11
289plusmn015
30plusmn1
102plusmn005
Raipur
1RR
3021plusmn221
395plusmn54
24plusmn11
03plusmn01
21plusmn1
33plusmn22
06plusmn01
34plusmn04
30plusmn2
06plusmn003
031plusmn003
nd
038plusmn002
2RR
2201plusmn101
232plusmn12
08plusmn02
00plusmn00
20plusmn1
13plusmn1
02plusmn01
17plusmn01
19plusmn1
32plusmn02
038plusmn002
nd
045plusmn004
3RR
2621plusmn120
347plusmn98
32plusmn04
03plusmn01
33plusmn1
24plusmn1
04plusmn01
23plusmn02
31plusmn2
11plusmn01
055plusmn004
nd
040plusmn003
4RR
2441plusmn134
345plusmn40
22plusmn05
02plusmn01
35plusmn2
22plusmn1
14plusmn01
31plusmn
02
30plusmn5
67plusmn03
049plusmn002
nd
026plusmn002
5RR
2295plusmn119
453plusmn182
17plusmn07
16plusmn07
26plusmn1
32plusmn2
18plusmn01
23plusmn01
25plusmn4
49plusmn03
059plusmn012
nd
024plusmn004
1RH
R6134plusmn284
1407plusmn237
248plusmn77
17plusmn09
159plusmn7
747plusmn43
09plusmn03
31plusmn
03
32plusmn3
13plusmn01
289plusmn015
5plusmn1
404plusmn018
2RH
R5088plusmn320
1727plusmn284
116plusmn28
10plusmn02
155plusmn8
601plusmn
3208plusmn04
22plusmn01
38plusmn8
48plusmn03
424plusmn056
5plusmn1
104plusmn012
3RH
R5474plusmn273
2165plusmn284
68plusmn07
08plusmn01
263plusmn12
589plusmn26
05plusmn01
24plusmn01
34plusmn2
18plusmn04
563plusmn026
8plusmn2
076plusmn005
4RH
R4866plusmn214
1367plusmn113
114plusmn07
433plusmn23
398plusmn18
957plusmn50
380plusmn19
29plusmn02
33plusmn3
92plusmn04
313plusmn019
14plusmn1
105plusmn007
5RH
R5930plusmn341
1441plusmn220
427plusmn115
84plusmn05
232plusmn10
918plusmn167
130plusmn06
27plusmn08
33plusmn4
71plusmn03
362plusmn023
6plusmn1
087plusmn034
8 Journal of Chemistry
Table 6 Descriptive statistics results of elemental chemical analysis for rice and rice husk from Korba and Raipur
K Ca Ti Cr Mn Fe Ni Cu Zn Rb Sr Ba PbKorba
RiceMean 229161 22352 171 000 3119 1725 085 261 2892 1724 043 nd 025SD 49562 3267 141 000 763 314 067 036 664 1279 016 nd 017Min 160361 17506 047 000 2397 1320 039 222 2218 418 029 nd 008Max 291056 26713 402 000 4367 2086 201 300 3909 3519 067 nd 051
RHMean 370919 125624 1567 032 22562 18803 162 201 2949 1785 341 2562 061SD 83990 24548 2483 009 5767 13003 122 013 322 1018 114 645 026Min 227706 94776 230 000 17433 9274 062 185 2587 369 224 1540 041Max 444080 149997 5992 090 32500 40897 325 217 3331 2869 476 3196 102
RaipurRiceMean 251578 35445 209 047 2685 2473 088 256 2707 329 046 nd 034SD 32375 8134 088 011 691 824 066 071 509 256 012 nd 009Min 220082 23192 084 000 1966 1267 022 166 1909 058 031 nd 024Max 302055 45290 324 160 3450 3261 177 344 3136 669 059 nd 045
RHMean 549853 162125 1948 1102 24133 76237 1064 266 3412 484 390 767 155SD 53845 33542 1463 1830 9908 17201 621 035 213 339 109 386 139Min 486602 136679 683 080 15514 58874 052 219 3218 131 289 467 076Max 613438 216507 4273 4326 39779 95678 3805 308 3765 921 563 1417 404
concentration in soil The variation observed in TFs for thesame species may be due to several factors such as the age ofthe plant the tissue and the environment in which the plantis grown It was demonstrated that the absorption ofmineralsand their distribution in the plant hang on the bioavailabilityof the minerals in soil root structure and shoot system[32] Moreover the bioavailability of elements from soil toplants is determined by other factors including pH redoxconditions speciation soil texture and mineralogy organicmatter content and the presence of competing ions
TFs calculated for rice and RH using the average valuesof elemental concentration in rice RH and soils of Korbaand Raipur are shown in Figure 4 In our study TFs for RHwere always higher than rice samples for both the studiedareas TFs of K Mn Cu Zn Rb and Ba are higher in Korbasamples compared to those of Raipur Elements such as Caand Cr show TFs higher in Raipur samples while Ti Fe Niand Pb were in the same range Our results clearly show thatthe bioaccumulation is higher in RH than in rice
TF =119862p
119862s (1)
A comparison with the literature data [33] for the content ofAs Ba Cu Pb Ni Mn and Cr in rice is reported in Table 7The average values calculated as the arithmetic mean forKorba and Raipur are reported separately The literaturereports that geometric means (GM) illustrate more exactdistribution of the element concentrations in rice samplesbut comparison withmany other studies is difficult due to thelack of information on GM [33] As and Ba are not present
0000
0001
0010
0100
1000
10000K
Ca
Ti
Cr
Mn
Fe
NiCu
Zn
Rb
Sr
Ba
Pb
Rice RaipurRH Raipur
Rice KorbaRH Korba
Figure 4 Transfer factors calculated for rice and rice husk sampleswith respect to soil samples from Korba and Raipur
in our samples Our values of Cu and Ni are aligned mainlywith those from Vietnam The concentrations of Pb and Mnare aligned respectively with commercial rice from China
Journal of Chemistry 9
Table 7 Concentration of hazardous elements in rice samples reported in different literature studies (a) arithmetic means (b) arithmeticstandard deviations (c) [34] (d) [35] and (e) [36]
Element Area 119873 AM (a) ASD (b) MIN MAX
Cu
Taizhou 13 4260 826 3037 5184Commercial rice China 5 3326 774 2812 4478
Vietnam (c) 31 2600 1100 5800Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2560 710 1662 3438Korba 5 2610 360 2222 2995
Pb
Taizhou 13 2042 2070 256 2602Commercial rice China 4 356 267 167 745
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 23700 19800 20100 24000Hangzhou (e) 5 131 103 45 308
Raipur 5 340 90 235 452Korba 5 250 170 78 514
Ni
Taizhou 13 761 391 339 1134Commercial rice China 4 476 276 201 818
Vietnam (c) 31 869 lt100 2022Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 880 660 216 1770Korba 5 850 670 387 2009
Mn
Taizhou 13 28640 5570 21977 37490Commercial rice China 4 9363 3288 5804 12708
Vietnam (c) 31 9900 5900 16300Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2685 6910 19700 34500Korba 5 31200 7600 24000 43700
Cr
Taizhou 13 107 83 6 279Commercial rice China 4 199 157 62 424
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 740 340 650 830Hangzhou (e) mdash mdash mdash mdash
Raipur 5 470 110 0 1600Korba 5 nd nd nd nd
and Taizhou The content of Cr in the samples of Raipur isexceptionally high
Despite all the reported data of metal content in riceaccording to the national standard for safety milled rice cri-teria [37] (NY5115-2002) themaximum allowable concentra-tions (MAC) ofAs and Pb are 050 and 020120583gg respectivelyMoreover the World Health Organization (WHO) provides020mgKg as the safe limit for Pb in rice [38] but it doesnot report any limit for other analyzed metals In the presentstudy Pb concentration is much higher than the reportedlimit in many samples both from Raipur and Korba evenif the average value is aligned with that of WHO Even it isknown as a toxic element Cr safe limit from WHOFAO is
not determined Since rice is the common food for the Asiancontinent and especially in China the MAC criteria deter-mine the same limit for some metals such as Cu 10mgKgZn 50mgKg Cr 1mgKg and Pb as that decided by WHO[39]
Statistical analysis does not show any significant differ-ence between rice and rice husk samples of the two areas ofinterest
Figure 5 shows the concentration of selected elements inall samples classified by species soil rice husk and riceThisfigure highlights the possible transfer andor accumulation ofelements from soil into the other twomatrices In some casesrice husk seems to act as a barrier for some heavymetals such
10 Journal of Chemistry
0
1
10
100
1000Cr
conc
entr
atio
n (m
gkg
)
Samples
Cr
1
10
100
As c
once
ntra
tion
(mg
kg)
As
0
1
10
100
Pb co
ncen
trat
ion
(mg
kg) Pb
0
2000
4000
6000
8000
10000
12000
K co
ncen
trat
ion
(mg
kg) K
010203040506070
Cu co
ncen
trat
ion
(mg
kg) Cu
010203040506070
Zn co
ncen
trat
ion
(mg
kg) Zn
0
1
10
100
Ni c
once
ntra
tion
(mg
kg) Ni
1
10
100
1000
10000
100000
Fe co
ncen
trat
ion
(mg
kg) Fe
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2 RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Figure 5 Concentration of elements in soil rice husk and rice samples from Korba and Raipur
as Cr K Fe and Pb The possible barrier role of rice husk isinteresting and it can be hypothesized also for Mn Ba andSr Unfortunately it is not clear in the case of Cu Ni Zn RbBi Ti and V
4 Conclusions
This work reports the chemical composition study of soilsrice and rice husk from Korba and Raipur (India) by means
Journal of Chemistry 11
of TXRF Results show some metals uptake from soil to ricein particular Pb and Cr from the Raipur region The noveltyof this study is the chemical characterization of rice made inparallel with the analysis of soils and corresponding rice huskA detailed analysis of all the data shows that rice husk accu-mulates more heavy metals than rice suggesting a possiblebarrier effect of the husk Despite that dedicated studiesshould be done to verify the clear role of husk and other para-meters such as rice species soils characteristics (pH claycontent and organic matter) and other variables Based onthe extremely interesting results obtained in this study someapproaches may be developed to promote low metals accu-mulation in rice
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study was supported by LIFE+ the financial instrumentof the European Community to support environmentalprojects (LIFE+ 2011 Project ENVIT000256) The authorsare grateful to Directorate-General Environment EuropeanCommission for inclusion of COSMOS-RICE Project inScience for Environment Policy Information Service (seehttpeceuropaeuenvironmentintegrationresearchnew-salertpdf383na2 enpdf) The authors acknowledge Profe-ssor Patel School of Studies in Chemistry Pt RavishankarShukla University Raipur India for the support in samplescollection
References
[1] C Huamain Z Chunrong T Cong and Z Yongguan ldquoHeavymetal pollution in soils in China status and countermeasuresrdquoAmbio vol 28 no 2 pp 130ndash134 1999
[2] M E Watanabe ldquoPhytoremediation on the brink of commer-cializationrdquo Environmental Science amp Technology vol 31 pp82Andash187A 1997
[3] S Uchida K Tagami and N Ishikawa ldquoConcentration soil-to-plant transfer factor and soil-soil solution distribution coeffi-cient of selenium in the surface environment -9106rdquo in Proceed-ings of the Symposium onWasteManagement (WM rsquo09 ) pp 1ndash5Phoenix Ariz USA March 2009
[4] X F Hu Y Jiang Y Shu X Hu L Liu and F Luo ldquoEffectsof mining wastewater discharges on heavy metal pollution andsoil enzyme activity of the paddy fieldsrdquo Journal of GeochemicalExploration vol 147 part B pp 139ndash150 2014
[5] A Sekara M Poniedziałek J Ciura and E Jedrszczyk ldquoCad-mium and lead accumulation and distribution in the organs ofnine crops implications for phytoremediationrdquo Polish Journalof Environmental Studies vol 14 no 4 pp 509ndash516 2005
[6] R Stone ldquoFood safetymdasharsenic and paddy rice a neglectedcancer riskrdquo Science vol 321 no 5886 pp 184ndash185 2008
[7] Committee for the Common Organisation of Agricultural Mar-kets 11 2014 httpeceuropaeuagriculturecerealspresenta-tionsricemarket-situation enpdf
[8] K R Dikshit and J E Schwartzberg ldquoIndia iI paeserdquo in Enci-clopedia Britannica pp 9ndash10 2007
[9] K M Omatola and A D Onojah ldquoElemental analysis of ricehusk ash using X-ray fluorescence techniquerdquo InternationalJournal of Physical Sciences vol 4 no 4 pp 189ndash193 2009
[10] L Sun and K Gong ldquoSilicon-based materials from rice husksand their applicationsrdquo Industrial and Engineering ChemistryResearch vol 40 no 25 pp 5861ndash5877 2001
[11] S Sugita ldquoOn the economical production of large quantities ofhighly reactive rice husk ashrdquo in Proceedings of the InternationalSymposium on Innovative World of Concrete (ICI-IWC rsquo93) pp2 3ndash71 1993
[12] I R Shaikh and A A Shaikh ldquoUtilization of wheat husk ashas silica source for the synthesis of MCM-41 type mesoporoussilicates a sustainable approach towards valorization of the agri-cultural waste streamrdquo Research Journal of Chemical Sciencesvol 3 pp 66ndash72 2013
[13] K M Omatola and A D Onojah ldquoRice husk as a potentialsource of high technological raw materials a reviewrdquo Journalof Polymer Science Innovation vol 4 pp 30ndash35 2012
[14] A Bosio N Rodella A Gianoncelli et al ldquoA new method toinertize incinerator toxic fly ash with silica from rice husk ashrdquoEnvironmental Chemistry Letters vol 11 no 4 pp 329ndash3332013
[15] A Bosio A Zacco L Borgese et al ldquoA sustainable technologyfor Pb and Zn stabilization based on the use of only wastematerials a green chemistry approach to avoid chemicals andpromote CO
2sequestrationrdquoChemical Engineering Journal vol
253 pp 377ndash384 2014[16] A Taylor S Branch M P Day M Patriarca and M White
ldquoAtomic spectrometry update Clinical and biological materialsfoods and beveragesrdquo Journal of Analytical Atomic Spectrometryvol 24 no 4 pp 535ndash579 2009
[17] K S Patel K Shrivas P Hoffmann and N Jakubowski ldquoAsurvey of lead pollution in Chhattisgarh State central IndiardquoEnvironmental Geochemistry and Health vol 28 no 1-2 pp 11ndash17 2006
[18] K S Patel K Shrivas R Brandt N Jakubowski W Corns andP Hoffmann ldquoArsenic contamination in water soil sedimentand rice of central Indiardquo Environmental Geochemistry andHealth vol 27 no 2 pp 131ndash145 2005
[19] B Giri K S Patel N K Jaiswal et al ldquoComposition and sourcesof organic tracers in aerosol particles of industrial central IndiardquoAtmospheric Research vol 120-121 pp 312ndash324 2013
[20] httpwwwepagovoswhazardtestmethodssw846pdfs3050bpdf
[21] L Borgese A Zacco E Bontempi et al ldquoTotal reflection of x-ray fluorescence (TXRF) amature technique for environmentalchemical nanoscale metrologyrdquoMeasurement Science and Tech-nology vol 20 no 8 Article ID 084027 2009
[22] F Bilo L Borgese D Cazzago et al ldquoTXRF analysis ofsoils and sediments to assess environmental contaminationrdquoEnvironmental Science and Pollution Research vol 21 no 23 pp13208ndash13214 2014
[23] Esdat 2000 Dutch Target and Intervention Values The newDutch list 2000 httpwwwesdatnet
[24] A Kabata-Pendias ldquoEnvironmental biogeochemistrymdashoutlineof the developmentrdquo Przeglad Geologiczny vol 49 no 10 pp957ndash959 2001
[25] S Srinivasa Gowd M Ramakrishna Reddy and P K GovilldquoAssessment of heavy metal contamination in soils at Jajmau
12 Journal of Chemistry
(Kanpur) and Unnao industrial areas of the Ganga Plain UttarPradesh Indiardquo Journal ofHazardousMaterials vol 174 no 1ndash3pp 113ndash121 2010
[26] K S Patel A Verma N K Jaiswal et al ldquoArsenic concentrationin soil rice and straw in central Indiardquo in Proceedings of the 4thInternational Congress on Arsenic in the Environment pp 508ndash509 July 2012
[27] A Kabata-Pendias Trace Elements in Soils and Plants Technol-ogy amp Engineering CRC Press 3rd edition 2000
[28] A D Jacobson and J D Blum ldquoCaSr and 87Sr86Sr geochem-istry of disseminated calcite in Himalayan silicate rocks fromNanga Parbat influence on river-water chemistryrdquoGeology vol28 no 5 pp 463ndash466 2000
[29] Y N Vodyanitskii ldquoCriteria of the technogenic nature ofheavy metals and metalloids in soils a review of publicationsrdquoEurasian Soil Science vol 42 no 9 pp 1053ndash1061 2009
[30] H Hoefler C Streli P Wobrauschek M Ovari and G ZarayldquoAnalysis of low Z elements in various environmental sampleswith total reflection X-ray fluorescence (TXRF) spectrometryrdquoSpectrochimica Acta Part B Atomic Spectroscopy vol 61 no 10-11 pp 1135ndash1140 2006
[31] K K Taha I M Shmou H M Osman and M H ShayoubldquoSoil-plant transfer and accumulation factors for trace elementsat the Blue and White Nilesrdquo Journal of Applied and IndustrialSciences vol 1 pp 97ndash102 2013
[32] H Papaefthymiou G Papatheodorou A Moustakli DChristodoulou and M Geraga ldquoNatural radionuclides and137Cs distributions and their relationship with sedimentologicalprocesses in Patras Harbour Greecerdquo Journal of EnvironmentalRadioactivity vol 94 no 2 pp 55ndash74 2007
[33] J Fu Q Zhou J Liu et al ldquoHigh levels of heavy metals inrice (Oryza sativa L) from a typical E-waste recycling areain southeast China and its potential risk to human healthrdquoChemosphere vol 71 no 7 pp 1269ndash1275 2008
[34] T D Phuong P Van Chuong D T Khiem and S Kokot ldquoEle-mental content of Vietnamese rice Part 1 Sampling analysisand comparison with previous studiesrdquo Analyst vol 124 no 4pp 553ndash560 1999
[35] S W Al Rmalli P I Haris C F Harrington and M AyubldquoA survey of arsenic in foodstuffs on sale in the UnitedKingdom and imported from Bangladeshrdquo Science of the TotalEnvironment vol 337 no 1ndash3 pp 23ndash30 2005
[36] C Fangmin Z Ningchun X Haiming et al ldquoCadmium andlead contamination in japonica rice grains and its variationamong the different locations in southeast Chinardquo Science of theTotal Environment vol 359 no 1ndash3 pp 156ndash166 2006
[37] National Programme on Safety Food SafetyMilled Rice Criteriaof PR China (NY5115-2002) China Ministry of AgricultureBeijing China 2002
[38] FAOWHOCodexAlimentariusGeneral Standards for Contam-inants and Toxins in Food Schedule1 Maximum and GuidelineLevels for Contaminants and Toxins in Food Joint FAOWHOFood Standards Programme Reference CXFAC 0216 CodexCommittee Rotterdam The Netherlands 2002
[39] The Ministry of Health of China GB 2762-2012 Standards forChinese Food Sanitation TheMinistry of Health of China 2012
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
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Carbohydrate Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Chromatography Research International
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
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Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 5
Table 3 Descriptive statistics results of elemental chemical analysis for Korba and Raipur soils
K Ca Ti V Cr Mn Fe Ni Cu Zn As Ba Rb Sr Pb BiKorba
Mean 506110 119582 146522 1438 2078 16239 683882 954 796 3220 420 10751 2362 1424 1135 ndSD 94297 88066 13332 229 410 7601 113639 190 229 2111 064 3998 720 898 120 ndMin 382912 42076 129266 1108 1456 8290 567619 654 595 1415 338 5699 1381 316 985 ndMax 621660 255993 157193 1732 2468 25370 840931 1162 1084 5818 486 17160 3073 2782 1280 nd
RaipurMean 720917 130909 498811 8934 13188 147754 3720198 6184 3959 5586 2096 19705 2624 1845 5545 511SD 162834 70736 47133 2831 2011 59658 518952 1660 591 386 805 8800 1664 632 894 118Min 489548 78577 433685 5544 11148 46253 2720251 3934 3109 5003 1190 12943 1023 1076 4355 383Max 925130 365998 595869 12684 17361 257907 4335400 7993 4851 6011 3568 42757 7132 3275 6921 815
[23] indicates that all the soil samples of Korba are notcontaminated while soils from Raipur are contaminated byNi Cu Cr As and Ba
A more detailed comparison of our data with thoseobtained in other studies of soil contamination in the samearea reveals a good agreement The comparison with datareported by Kabata Pendias for uncontaminated soils (Cr04ndash29mgkg Mn 25ndash8000mgkg Ni 3ndash150mgkg Cu 05ndash135mgkg Zn 1ndash750mgkg and Pb 06ndash63mgkg) [24] sug-gests that Cr and Pb contamination is present in RaipurMorerecent studies by Srinivasa Gowd et al [25] and Patel et al[26] reported higher content of Pb Zn and Cr Thus onlycontamination by Cr would be present However it should beconsidered that Pb Zn andCr concentration increased easilyduring the industrial activity particularly in themining areasSo the increasing inmetal concentration in these soils may bea consequence of anthropogenic influence
Statistical analysis was used to evaluate the correlationof the elements present in soil Cluster analysis was usedto highlight the differences between soils from Korba andRaipur Hierarchical division was performed using the Wardmethod which is based on the analysis of variances insteadof distances The varimax rotation with Kaiser normalizationmethod was used for factor analysis By extracting the eigen-values the number of significant factors was determinedData treatment was performed using the JMP 10 softwareResults of cluster analysis are reported in Figure 2The dend-rogram clearly points out the division of the samples intwo clusters corresponding to the different sampled areas ofKorba and Raipur Considering that the two studied citiesbelong to the same region of India and supposing the samecrustal composition this result suggests a different degree ofpollution
Results of factor analysis show that the three eigenvaluesexplain 9018 of the variance Therefore they were selectedfor further factor analysis The loadings of elements withrespect to each one of the three identified factors are reportedin Table 4 All the elements with high loadings for the samefactor may have a common origin in soils The first factor isresponsible for 563 of the total variance and it includes KTi V Cr Mn Fe Ni Cu Zn As Pb and Bi Consideringthe nature of these elements and their simultaneous presencethis suggests their anthropogenic origin The second factor
1 2 3 4 5 6 7 8 9 12 10 11 13 14 15
Figure 2 Dendrogram of cluster analysis for Korba (red) andRaipur (green) samples
accounts for 1709 of the total variance and it includes Caand Sr Ca and Sr are included in the list of the eight mostabundant rock forming elements of biosphere which may beadded to the soil from wind dispersion of dust from minetailing and wastes tips [27 28] The third principal compo-nent represented 1679 of the total variance and it includesAl Rb and Ba The presence of Al would suggest a crustalorigin Indeed Al acts as a natural marker element while itsanthropogenic origin is still unknown Al is a conservativeelement and is contained in aluminosilicates as is reported byVodyanitskii [29] However the crustal origin of Rb and Ba isnot assessed
32 TXRF Analysis of Rice and Rice Husk TXRF spectra ofrice and rice husk are shown in Figure 3 Signals of Mg AlP S Cl K Ca Ti Cr Mn Fe Ni Cu Zn Ba Rb Pb Br andSr are identified in both rice and RH samples After spectradeconvolution concentration of each was determined except
6 Journal of Chemistry
Pulse
s (cp
s)
E (keV)
SrRbBrPbGaZnCuNiFeMnCrBaTiCaKArCl
Mo
SPSiGa
Mg Sr
E RbAl
Zn
Pb
2 4 6 8 10 12 14
times1E3
30
20
10
00
Figure 3 Spectra of rice husk (black) and rice (gray) sample 2 from Korba measured by S2 Picofox
Table 4 Rotated component matrix for soil samples
(a)
Variables Rotated factor1 2 3
Al 04877 03792 07279K 05859 minus00676 05477Ca 00419 09249 01358Ti 09527 01259 00972V 09167 00068 03339Cr 09421 01997 0203Mn 08834 00792 02768Fe 08929 03231 00015Ni 09423 minus00077 02811Cu 09715 01256 01389Zn 06599 05904 minus01872As 08862 minus004 029Rb 00402 0147 09675Sr 00761 09325 02809Ba 04065 05243 06689Pb 09163 0287 01481Bi 08439 03457 02535
(b)
Variance explained by each factorFactor Variance Percent Cum percentFactor 1 95731 56313 56313Factor 2 29045 17085 73398Factor 3 28535 16785 90183
for elements lighter thanKQuantification of the detected lowZ elements is not reported because our measurements wereperformed in air and vacuum conditions are recommendedin this case [30] Results of quantitative analysis of rice andrice husk samples are reported in Table 5
Elemental composition of rice husk and rice is similarfor all the studied samples even if Ca Ti Mn Fe and Pbare higher in RH with respect to rice The concentrationof metals in the two matrices is usually correlated In thesamples from Korba the highest concentrations of Ti Fe andZn were detected in sample 3 for both the analyzed matrices(3R K and 3RH K) and the highest concentration of Ca andMn in sample 1 (1R K and 1RH K) In the samples fromRaipur the highest concentrations of Fe and Zn are foundin sample 3 (3R R and 3RH R) while the highest content ofMn was in sample 4 (4R R and 4RH R) Rice husk samplesof Korba contain Cr that is not detected in rice while Cris present in both the matrices collected in Raipur with theusual correlationThis can be due to the higher concentrationof Cr in Raipur than Korba soilsThe correlation observed forthe other elements is not present in the case of Pb Indeed thehighest value of Pb for rice husk samples is present in sample5RH K while the highest value of Pb for rice is present insample 2R K A similar behavior is observed for Ca and Ti inthe samples from Raipur
Descriptive statistics of elemental content in rice and ricehusk samples is reported in Table 6The comparison of heavymetals concentration in rice grain from the two studied areasshows no significant differences among K Ca Ti Ni Cuand Zn Other elements such as Cr Fe and Pb are higherin Raipur samples while Mn and Rb are higher in Korbasamples Concentration of heavymetals detected in rice sam-ples decreases in the following order Mn gt Zn gt Cu gt Ni gtPb gt Cr
Metal uptake is higher for plants germinated in soilsenriched with metals from anthropogenic factors Thereforebioaccumulation ability of plants is one of the most criticalproblems faced in agriculture and environmental studiesTransfer factor (TF) is an indicator of the plant species abilityor tendency to uptake a certain element from the soil [31]TF is obtained by dividing the element concentration in theplant by its concentration in soil according to (1) where119862p is the metal concentration in plant and 119862s is the metal
Journal of Chemistry 7
Table5Elem
entalcon
centratio
nin
rice(R)
andric
ehusk(RH)sam
ples
from
Korbaa
ndRa
ipur
Sample
Elem
entalcon
centratio
n(m
gKg
)K
CaTi
CrMn
FeNi
CuZn
RbSr
BaPb
Korba
1RK
2179plusmn122
267plusmn67
19plusmn04
00plusmn00
44plusmn2
18plusmn3
04plusmn01
22plusmn02
29plusmn1
186plusmn10
067plusmn014
nd
027plusmn001
2RK
2911plusmn160
225plusmn19
05plusmn03
00plusmn00
29plusmn1
19plusmn2
09plusmn01
24plusmn01
30plusmn1
352plusmn17
033plusmn005
nd
051plusmn003
3RK
2603plusmn184
227plusmn17
40plusmn03
00plusmn00
32plusmn1
21plusmn1
05plusmn01
30plusmn02
39plusmn2
42plusmn03
052plusmn003
nd
025plusmn002
4RK
1604plusmn111
223plusmn20
14plusmn04
00plusmn00
27plusmn1
13plusmn1
20plusmn06
30plusmn02
22plusmn1
57plusmn03
029plusmn002
nd
008plusmn002
5RK
2162plusmn113
175plusmn11
07plusmn02
00plusmn00
24plusmn1
15plusmn1
04plusmn01
25plusmn01
24plusmn1
225plusmn10
033plusmn001
nd
013plusmn001
1RH
K4152plusmn303
1500plusmn68
28plusmn09
04plusmn01
325plusmn15
93plusmn4
06plusmn01
20plusmn01
32plusmn1
223plusmn12
476plusmn022
32plusmn2
041plusmn004
2RH
K3894plusmn311
1277plusmn61
73plusmn24
00plusmn00
174plusmn8
161plusmn
1133plusmn02
18plusmn04
26plusmn1
287plusmn20
268plusmn013
15plusmn1
047plusmn003
3RH
K2277plusmn152
1485plusmn106
599plusmn456
09plusmn02
210plusmn9
409plusmn26
10plusmn01
21plusmn
02
33plusmn3
37plusmn03
449plusmn023
26plusmn2
070plusmn007
4RH
K44
41plusmn196
1072plusmn47
60plusmn24
02plusmn01
213plusmn9
184plusmn9
26plusmn01
22plusmn01
28plusmn1
111plusmn05
224plusmn010
25plusmn1
043plusmn002
5RH
K3782plusmn167
948plusmn61
23plusmn03
00plusmn00
206plusmn9
93plusmn4
06plusmn01
19plusmn01
27plusmn2
234plusmn11
289plusmn015
30plusmn1
102plusmn005
Raipur
1RR
3021plusmn221
395plusmn54
24plusmn11
03plusmn01
21plusmn1
33plusmn22
06plusmn01
34plusmn04
30plusmn2
06plusmn003
031plusmn003
nd
038plusmn002
2RR
2201plusmn101
232plusmn12
08plusmn02
00plusmn00
20plusmn1
13plusmn1
02plusmn01
17plusmn01
19plusmn1
32plusmn02
038plusmn002
nd
045plusmn004
3RR
2621plusmn120
347plusmn98
32plusmn04
03plusmn01
33plusmn1
24plusmn1
04plusmn01
23plusmn02
31plusmn2
11plusmn01
055plusmn004
nd
040plusmn003
4RR
2441plusmn134
345plusmn40
22plusmn05
02plusmn01
35plusmn2
22plusmn1
14plusmn01
31plusmn
02
30plusmn5
67plusmn03
049plusmn002
nd
026plusmn002
5RR
2295plusmn119
453plusmn182
17plusmn07
16plusmn07
26plusmn1
32plusmn2
18plusmn01
23plusmn01
25plusmn4
49plusmn03
059plusmn012
nd
024plusmn004
1RH
R6134plusmn284
1407plusmn237
248plusmn77
17plusmn09
159plusmn7
747plusmn43
09plusmn03
31plusmn
03
32plusmn3
13plusmn01
289plusmn015
5plusmn1
404plusmn018
2RH
R5088plusmn320
1727plusmn284
116plusmn28
10plusmn02
155plusmn8
601plusmn
3208plusmn04
22plusmn01
38plusmn8
48plusmn03
424plusmn056
5plusmn1
104plusmn012
3RH
R5474plusmn273
2165plusmn284
68plusmn07
08plusmn01
263plusmn12
589plusmn26
05plusmn01
24plusmn01
34plusmn2
18plusmn04
563plusmn026
8plusmn2
076plusmn005
4RH
R4866plusmn214
1367plusmn113
114plusmn07
433plusmn23
398plusmn18
957plusmn50
380plusmn19
29plusmn02
33plusmn3
92plusmn04
313plusmn019
14plusmn1
105plusmn007
5RH
R5930plusmn341
1441plusmn220
427plusmn115
84plusmn05
232plusmn10
918plusmn167
130plusmn06
27plusmn08
33plusmn4
71plusmn03
362plusmn023
6plusmn1
087plusmn034
8 Journal of Chemistry
Table 6 Descriptive statistics results of elemental chemical analysis for rice and rice husk from Korba and Raipur
K Ca Ti Cr Mn Fe Ni Cu Zn Rb Sr Ba PbKorba
RiceMean 229161 22352 171 000 3119 1725 085 261 2892 1724 043 nd 025SD 49562 3267 141 000 763 314 067 036 664 1279 016 nd 017Min 160361 17506 047 000 2397 1320 039 222 2218 418 029 nd 008Max 291056 26713 402 000 4367 2086 201 300 3909 3519 067 nd 051
RHMean 370919 125624 1567 032 22562 18803 162 201 2949 1785 341 2562 061SD 83990 24548 2483 009 5767 13003 122 013 322 1018 114 645 026Min 227706 94776 230 000 17433 9274 062 185 2587 369 224 1540 041Max 444080 149997 5992 090 32500 40897 325 217 3331 2869 476 3196 102
RaipurRiceMean 251578 35445 209 047 2685 2473 088 256 2707 329 046 nd 034SD 32375 8134 088 011 691 824 066 071 509 256 012 nd 009Min 220082 23192 084 000 1966 1267 022 166 1909 058 031 nd 024Max 302055 45290 324 160 3450 3261 177 344 3136 669 059 nd 045
RHMean 549853 162125 1948 1102 24133 76237 1064 266 3412 484 390 767 155SD 53845 33542 1463 1830 9908 17201 621 035 213 339 109 386 139Min 486602 136679 683 080 15514 58874 052 219 3218 131 289 467 076Max 613438 216507 4273 4326 39779 95678 3805 308 3765 921 563 1417 404
concentration in soil The variation observed in TFs for thesame species may be due to several factors such as the age ofthe plant the tissue and the environment in which the plantis grown It was demonstrated that the absorption ofmineralsand their distribution in the plant hang on the bioavailabilityof the minerals in soil root structure and shoot system[32] Moreover the bioavailability of elements from soil toplants is determined by other factors including pH redoxconditions speciation soil texture and mineralogy organicmatter content and the presence of competing ions
TFs calculated for rice and RH using the average valuesof elemental concentration in rice RH and soils of Korbaand Raipur are shown in Figure 4 In our study TFs for RHwere always higher than rice samples for both the studiedareas TFs of K Mn Cu Zn Rb and Ba are higher in Korbasamples compared to those of Raipur Elements such as Caand Cr show TFs higher in Raipur samples while Ti Fe Niand Pb were in the same range Our results clearly show thatthe bioaccumulation is higher in RH than in rice
TF =119862p
119862s (1)
A comparison with the literature data [33] for the content ofAs Ba Cu Pb Ni Mn and Cr in rice is reported in Table 7The average values calculated as the arithmetic mean forKorba and Raipur are reported separately The literaturereports that geometric means (GM) illustrate more exactdistribution of the element concentrations in rice samplesbut comparison withmany other studies is difficult due to thelack of information on GM [33] As and Ba are not present
0000
0001
0010
0100
1000
10000K
Ca
Ti
Cr
Mn
Fe
NiCu
Zn
Rb
Sr
Ba
Pb
Rice RaipurRH Raipur
Rice KorbaRH Korba
Figure 4 Transfer factors calculated for rice and rice husk sampleswith respect to soil samples from Korba and Raipur
in our samples Our values of Cu and Ni are aligned mainlywith those from Vietnam The concentrations of Pb and Mnare aligned respectively with commercial rice from China
Journal of Chemistry 9
Table 7 Concentration of hazardous elements in rice samples reported in different literature studies (a) arithmetic means (b) arithmeticstandard deviations (c) [34] (d) [35] and (e) [36]
Element Area 119873 AM (a) ASD (b) MIN MAX
Cu
Taizhou 13 4260 826 3037 5184Commercial rice China 5 3326 774 2812 4478
Vietnam (c) 31 2600 1100 5800Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2560 710 1662 3438Korba 5 2610 360 2222 2995
Pb
Taizhou 13 2042 2070 256 2602Commercial rice China 4 356 267 167 745
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 23700 19800 20100 24000Hangzhou (e) 5 131 103 45 308
Raipur 5 340 90 235 452Korba 5 250 170 78 514
Ni
Taizhou 13 761 391 339 1134Commercial rice China 4 476 276 201 818
Vietnam (c) 31 869 lt100 2022Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 880 660 216 1770Korba 5 850 670 387 2009
Mn
Taizhou 13 28640 5570 21977 37490Commercial rice China 4 9363 3288 5804 12708
Vietnam (c) 31 9900 5900 16300Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2685 6910 19700 34500Korba 5 31200 7600 24000 43700
Cr
Taizhou 13 107 83 6 279Commercial rice China 4 199 157 62 424
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 740 340 650 830Hangzhou (e) mdash mdash mdash mdash
Raipur 5 470 110 0 1600Korba 5 nd nd nd nd
and Taizhou The content of Cr in the samples of Raipur isexceptionally high
Despite all the reported data of metal content in riceaccording to the national standard for safety milled rice cri-teria [37] (NY5115-2002) themaximum allowable concentra-tions (MAC) ofAs and Pb are 050 and 020120583gg respectivelyMoreover the World Health Organization (WHO) provides020mgKg as the safe limit for Pb in rice [38] but it doesnot report any limit for other analyzed metals In the presentstudy Pb concentration is much higher than the reportedlimit in many samples both from Raipur and Korba evenif the average value is aligned with that of WHO Even it isknown as a toxic element Cr safe limit from WHOFAO is
not determined Since rice is the common food for the Asiancontinent and especially in China the MAC criteria deter-mine the same limit for some metals such as Cu 10mgKgZn 50mgKg Cr 1mgKg and Pb as that decided by WHO[39]
Statistical analysis does not show any significant differ-ence between rice and rice husk samples of the two areas ofinterest
Figure 5 shows the concentration of selected elements inall samples classified by species soil rice husk and riceThisfigure highlights the possible transfer andor accumulation ofelements from soil into the other twomatrices In some casesrice husk seems to act as a barrier for some heavymetals such
10 Journal of Chemistry
0
1
10
100
1000Cr
conc
entr
atio
n (m
gkg
)
Samples
Cr
1
10
100
As c
once
ntra
tion
(mg
kg)
As
0
1
10
100
Pb co
ncen
trat
ion
(mg
kg) Pb
0
2000
4000
6000
8000
10000
12000
K co
ncen
trat
ion
(mg
kg) K
010203040506070
Cu co
ncen
trat
ion
(mg
kg) Cu
010203040506070
Zn co
ncen
trat
ion
(mg
kg) Zn
0
1
10
100
Ni c
once
ntra
tion
(mg
kg) Ni
1
10
100
1000
10000
100000
Fe co
ncen
trat
ion
(mg
kg) Fe
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2 RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Figure 5 Concentration of elements in soil rice husk and rice samples from Korba and Raipur
as Cr K Fe and Pb The possible barrier role of rice husk isinteresting and it can be hypothesized also for Mn Ba andSr Unfortunately it is not clear in the case of Cu Ni Zn RbBi Ti and V
4 Conclusions
This work reports the chemical composition study of soilsrice and rice husk from Korba and Raipur (India) by means
Journal of Chemistry 11
of TXRF Results show some metals uptake from soil to ricein particular Pb and Cr from the Raipur region The noveltyof this study is the chemical characterization of rice made inparallel with the analysis of soils and corresponding rice huskA detailed analysis of all the data shows that rice husk accu-mulates more heavy metals than rice suggesting a possiblebarrier effect of the husk Despite that dedicated studiesshould be done to verify the clear role of husk and other para-meters such as rice species soils characteristics (pH claycontent and organic matter) and other variables Based onthe extremely interesting results obtained in this study someapproaches may be developed to promote low metals accu-mulation in rice
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study was supported by LIFE+ the financial instrumentof the European Community to support environmentalprojects (LIFE+ 2011 Project ENVIT000256) The authorsare grateful to Directorate-General Environment EuropeanCommission for inclusion of COSMOS-RICE Project inScience for Environment Policy Information Service (seehttpeceuropaeuenvironmentintegrationresearchnew-salertpdf383na2 enpdf) The authors acknowledge Profe-ssor Patel School of Studies in Chemistry Pt RavishankarShukla University Raipur India for the support in samplescollection
References
[1] C Huamain Z Chunrong T Cong and Z Yongguan ldquoHeavymetal pollution in soils in China status and countermeasuresrdquoAmbio vol 28 no 2 pp 130ndash134 1999
[2] M E Watanabe ldquoPhytoremediation on the brink of commer-cializationrdquo Environmental Science amp Technology vol 31 pp82Andash187A 1997
[3] S Uchida K Tagami and N Ishikawa ldquoConcentration soil-to-plant transfer factor and soil-soil solution distribution coeffi-cient of selenium in the surface environment -9106rdquo in Proceed-ings of the Symposium onWasteManagement (WM rsquo09 ) pp 1ndash5Phoenix Ariz USA March 2009
[4] X F Hu Y Jiang Y Shu X Hu L Liu and F Luo ldquoEffectsof mining wastewater discharges on heavy metal pollution andsoil enzyme activity of the paddy fieldsrdquo Journal of GeochemicalExploration vol 147 part B pp 139ndash150 2014
[5] A Sekara M Poniedziałek J Ciura and E Jedrszczyk ldquoCad-mium and lead accumulation and distribution in the organs ofnine crops implications for phytoremediationrdquo Polish Journalof Environmental Studies vol 14 no 4 pp 509ndash516 2005
[6] R Stone ldquoFood safetymdasharsenic and paddy rice a neglectedcancer riskrdquo Science vol 321 no 5886 pp 184ndash185 2008
[7] Committee for the Common Organisation of Agricultural Mar-kets 11 2014 httpeceuropaeuagriculturecerealspresenta-tionsricemarket-situation enpdf
[8] K R Dikshit and J E Schwartzberg ldquoIndia iI paeserdquo in Enci-clopedia Britannica pp 9ndash10 2007
[9] K M Omatola and A D Onojah ldquoElemental analysis of ricehusk ash using X-ray fluorescence techniquerdquo InternationalJournal of Physical Sciences vol 4 no 4 pp 189ndash193 2009
[10] L Sun and K Gong ldquoSilicon-based materials from rice husksand their applicationsrdquo Industrial and Engineering ChemistryResearch vol 40 no 25 pp 5861ndash5877 2001
[11] S Sugita ldquoOn the economical production of large quantities ofhighly reactive rice husk ashrdquo in Proceedings of the InternationalSymposium on Innovative World of Concrete (ICI-IWC rsquo93) pp2 3ndash71 1993
[12] I R Shaikh and A A Shaikh ldquoUtilization of wheat husk ashas silica source for the synthesis of MCM-41 type mesoporoussilicates a sustainable approach towards valorization of the agri-cultural waste streamrdquo Research Journal of Chemical Sciencesvol 3 pp 66ndash72 2013
[13] K M Omatola and A D Onojah ldquoRice husk as a potentialsource of high technological raw materials a reviewrdquo Journalof Polymer Science Innovation vol 4 pp 30ndash35 2012
[14] A Bosio N Rodella A Gianoncelli et al ldquoA new method toinertize incinerator toxic fly ash with silica from rice husk ashrdquoEnvironmental Chemistry Letters vol 11 no 4 pp 329ndash3332013
[15] A Bosio A Zacco L Borgese et al ldquoA sustainable technologyfor Pb and Zn stabilization based on the use of only wastematerials a green chemistry approach to avoid chemicals andpromote CO
2sequestrationrdquoChemical Engineering Journal vol
253 pp 377ndash384 2014[16] A Taylor S Branch M P Day M Patriarca and M White
ldquoAtomic spectrometry update Clinical and biological materialsfoods and beveragesrdquo Journal of Analytical Atomic Spectrometryvol 24 no 4 pp 535ndash579 2009
[17] K S Patel K Shrivas P Hoffmann and N Jakubowski ldquoAsurvey of lead pollution in Chhattisgarh State central IndiardquoEnvironmental Geochemistry and Health vol 28 no 1-2 pp 11ndash17 2006
[18] K S Patel K Shrivas R Brandt N Jakubowski W Corns andP Hoffmann ldquoArsenic contamination in water soil sedimentand rice of central Indiardquo Environmental Geochemistry andHealth vol 27 no 2 pp 131ndash145 2005
[19] B Giri K S Patel N K Jaiswal et al ldquoComposition and sourcesof organic tracers in aerosol particles of industrial central IndiardquoAtmospheric Research vol 120-121 pp 312ndash324 2013
[20] httpwwwepagovoswhazardtestmethodssw846pdfs3050bpdf
[21] L Borgese A Zacco E Bontempi et al ldquoTotal reflection of x-ray fluorescence (TXRF) amature technique for environmentalchemical nanoscale metrologyrdquoMeasurement Science and Tech-nology vol 20 no 8 Article ID 084027 2009
[22] F Bilo L Borgese D Cazzago et al ldquoTXRF analysis ofsoils and sediments to assess environmental contaminationrdquoEnvironmental Science and Pollution Research vol 21 no 23 pp13208ndash13214 2014
[23] Esdat 2000 Dutch Target and Intervention Values The newDutch list 2000 httpwwwesdatnet
[24] A Kabata-Pendias ldquoEnvironmental biogeochemistrymdashoutlineof the developmentrdquo Przeglad Geologiczny vol 49 no 10 pp957ndash959 2001
[25] S Srinivasa Gowd M Ramakrishna Reddy and P K GovilldquoAssessment of heavy metal contamination in soils at Jajmau
12 Journal of Chemistry
(Kanpur) and Unnao industrial areas of the Ganga Plain UttarPradesh Indiardquo Journal ofHazardousMaterials vol 174 no 1ndash3pp 113ndash121 2010
[26] K S Patel A Verma N K Jaiswal et al ldquoArsenic concentrationin soil rice and straw in central Indiardquo in Proceedings of the 4thInternational Congress on Arsenic in the Environment pp 508ndash509 July 2012
[27] A Kabata-Pendias Trace Elements in Soils and Plants Technol-ogy amp Engineering CRC Press 3rd edition 2000
[28] A D Jacobson and J D Blum ldquoCaSr and 87Sr86Sr geochem-istry of disseminated calcite in Himalayan silicate rocks fromNanga Parbat influence on river-water chemistryrdquoGeology vol28 no 5 pp 463ndash466 2000
[29] Y N Vodyanitskii ldquoCriteria of the technogenic nature ofheavy metals and metalloids in soils a review of publicationsrdquoEurasian Soil Science vol 42 no 9 pp 1053ndash1061 2009
[30] H Hoefler C Streli P Wobrauschek M Ovari and G ZarayldquoAnalysis of low Z elements in various environmental sampleswith total reflection X-ray fluorescence (TXRF) spectrometryrdquoSpectrochimica Acta Part B Atomic Spectroscopy vol 61 no 10-11 pp 1135ndash1140 2006
[31] K K Taha I M Shmou H M Osman and M H ShayoubldquoSoil-plant transfer and accumulation factors for trace elementsat the Blue and White Nilesrdquo Journal of Applied and IndustrialSciences vol 1 pp 97ndash102 2013
[32] H Papaefthymiou G Papatheodorou A Moustakli DChristodoulou and M Geraga ldquoNatural radionuclides and137Cs distributions and their relationship with sedimentologicalprocesses in Patras Harbour Greecerdquo Journal of EnvironmentalRadioactivity vol 94 no 2 pp 55ndash74 2007
[33] J Fu Q Zhou J Liu et al ldquoHigh levels of heavy metals inrice (Oryza sativa L) from a typical E-waste recycling areain southeast China and its potential risk to human healthrdquoChemosphere vol 71 no 7 pp 1269ndash1275 2008
[34] T D Phuong P Van Chuong D T Khiem and S Kokot ldquoEle-mental content of Vietnamese rice Part 1 Sampling analysisand comparison with previous studiesrdquo Analyst vol 124 no 4pp 553ndash560 1999
[35] S W Al Rmalli P I Haris C F Harrington and M AyubldquoA survey of arsenic in foodstuffs on sale in the UnitedKingdom and imported from Bangladeshrdquo Science of the TotalEnvironment vol 337 no 1ndash3 pp 23ndash30 2005
[36] C Fangmin Z Ningchun X Haiming et al ldquoCadmium andlead contamination in japonica rice grains and its variationamong the different locations in southeast Chinardquo Science of theTotal Environment vol 359 no 1ndash3 pp 156ndash166 2006
[37] National Programme on Safety Food SafetyMilled Rice Criteriaof PR China (NY5115-2002) China Ministry of AgricultureBeijing China 2002
[38] FAOWHOCodexAlimentariusGeneral Standards for Contam-inants and Toxins in Food Schedule1 Maximum and GuidelineLevels for Contaminants and Toxins in Food Joint FAOWHOFood Standards Programme Reference CXFAC 0216 CodexCommittee Rotterdam The Netherlands 2002
[39] The Ministry of Health of China GB 2762-2012 Standards forChinese Food Sanitation TheMinistry of Health of China 2012
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
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Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
6 Journal of Chemistry
Pulse
s (cp
s)
E (keV)
SrRbBrPbGaZnCuNiFeMnCrBaTiCaKArCl
Mo
SPSiGa
Mg Sr
E RbAl
Zn
Pb
2 4 6 8 10 12 14
times1E3
30
20
10
00
Figure 3 Spectra of rice husk (black) and rice (gray) sample 2 from Korba measured by S2 Picofox
Table 4 Rotated component matrix for soil samples
(a)
Variables Rotated factor1 2 3
Al 04877 03792 07279K 05859 minus00676 05477Ca 00419 09249 01358Ti 09527 01259 00972V 09167 00068 03339Cr 09421 01997 0203Mn 08834 00792 02768Fe 08929 03231 00015Ni 09423 minus00077 02811Cu 09715 01256 01389Zn 06599 05904 minus01872As 08862 minus004 029Rb 00402 0147 09675Sr 00761 09325 02809Ba 04065 05243 06689Pb 09163 0287 01481Bi 08439 03457 02535
(b)
Variance explained by each factorFactor Variance Percent Cum percentFactor 1 95731 56313 56313Factor 2 29045 17085 73398Factor 3 28535 16785 90183
for elements lighter thanKQuantification of the detected lowZ elements is not reported because our measurements wereperformed in air and vacuum conditions are recommendedin this case [30] Results of quantitative analysis of rice andrice husk samples are reported in Table 5
Elemental composition of rice husk and rice is similarfor all the studied samples even if Ca Ti Mn Fe and Pbare higher in RH with respect to rice The concentrationof metals in the two matrices is usually correlated In thesamples from Korba the highest concentrations of Ti Fe andZn were detected in sample 3 for both the analyzed matrices(3R K and 3RH K) and the highest concentration of Ca andMn in sample 1 (1R K and 1RH K) In the samples fromRaipur the highest concentrations of Fe and Zn are foundin sample 3 (3R R and 3RH R) while the highest content ofMn was in sample 4 (4R R and 4RH R) Rice husk samplesof Korba contain Cr that is not detected in rice while Cris present in both the matrices collected in Raipur with theusual correlationThis can be due to the higher concentrationof Cr in Raipur than Korba soilsThe correlation observed forthe other elements is not present in the case of Pb Indeed thehighest value of Pb for rice husk samples is present in sample5RH K while the highest value of Pb for rice is present insample 2R K A similar behavior is observed for Ca and Ti inthe samples from Raipur
Descriptive statistics of elemental content in rice and ricehusk samples is reported in Table 6The comparison of heavymetals concentration in rice grain from the two studied areasshows no significant differences among K Ca Ti Ni Cuand Zn Other elements such as Cr Fe and Pb are higherin Raipur samples while Mn and Rb are higher in Korbasamples Concentration of heavymetals detected in rice sam-ples decreases in the following order Mn gt Zn gt Cu gt Ni gtPb gt Cr
Metal uptake is higher for plants germinated in soilsenriched with metals from anthropogenic factors Thereforebioaccumulation ability of plants is one of the most criticalproblems faced in agriculture and environmental studiesTransfer factor (TF) is an indicator of the plant species abilityor tendency to uptake a certain element from the soil [31]TF is obtained by dividing the element concentration in theplant by its concentration in soil according to (1) where119862p is the metal concentration in plant and 119862s is the metal
Journal of Chemistry 7
Table5Elem
entalcon
centratio
nin
rice(R)
andric
ehusk(RH)sam
ples
from
Korbaa
ndRa
ipur
Sample
Elem
entalcon
centratio
n(m
gKg
)K
CaTi
CrMn
FeNi
CuZn
RbSr
BaPb
Korba
1RK
2179plusmn122
267plusmn67
19plusmn04
00plusmn00
44plusmn2
18plusmn3
04plusmn01
22plusmn02
29plusmn1
186plusmn10
067plusmn014
nd
027plusmn001
2RK
2911plusmn160
225plusmn19
05plusmn03
00plusmn00
29plusmn1
19plusmn2
09plusmn01
24plusmn01
30plusmn1
352plusmn17
033plusmn005
nd
051plusmn003
3RK
2603plusmn184
227plusmn17
40plusmn03
00plusmn00
32plusmn1
21plusmn1
05plusmn01
30plusmn02
39plusmn2
42plusmn03
052plusmn003
nd
025plusmn002
4RK
1604plusmn111
223plusmn20
14plusmn04
00plusmn00
27plusmn1
13plusmn1
20plusmn06
30plusmn02
22plusmn1
57plusmn03
029plusmn002
nd
008plusmn002
5RK
2162plusmn113
175plusmn11
07plusmn02
00plusmn00
24plusmn1
15plusmn1
04plusmn01
25plusmn01
24plusmn1
225plusmn10
033plusmn001
nd
013plusmn001
1RH
K4152plusmn303
1500plusmn68
28plusmn09
04plusmn01
325plusmn15
93plusmn4
06plusmn01
20plusmn01
32plusmn1
223plusmn12
476plusmn022
32plusmn2
041plusmn004
2RH
K3894plusmn311
1277plusmn61
73plusmn24
00plusmn00
174plusmn8
161plusmn
1133plusmn02
18plusmn04
26plusmn1
287plusmn20
268plusmn013
15plusmn1
047plusmn003
3RH
K2277plusmn152
1485plusmn106
599plusmn456
09plusmn02
210plusmn9
409plusmn26
10plusmn01
21plusmn
02
33plusmn3
37plusmn03
449plusmn023
26plusmn2
070plusmn007
4RH
K44
41plusmn196
1072plusmn47
60plusmn24
02plusmn01
213plusmn9
184plusmn9
26plusmn01
22plusmn01
28plusmn1
111plusmn05
224plusmn010
25plusmn1
043plusmn002
5RH
K3782plusmn167
948plusmn61
23plusmn03
00plusmn00
206plusmn9
93plusmn4
06plusmn01
19plusmn01
27plusmn2
234plusmn11
289plusmn015
30plusmn1
102plusmn005
Raipur
1RR
3021plusmn221
395plusmn54
24plusmn11
03plusmn01
21plusmn1
33plusmn22
06plusmn01
34plusmn04
30plusmn2
06plusmn003
031plusmn003
nd
038plusmn002
2RR
2201plusmn101
232plusmn12
08plusmn02
00plusmn00
20plusmn1
13plusmn1
02plusmn01
17plusmn01
19plusmn1
32plusmn02
038plusmn002
nd
045plusmn004
3RR
2621plusmn120
347plusmn98
32plusmn04
03plusmn01
33plusmn1
24plusmn1
04plusmn01
23plusmn02
31plusmn2
11plusmn01
055plusmn004
nd
040plusmn003
4RR
2441plusmn134
345plusmn40
22plusmn05
02plusmn01
35plusmn2
22plusmn1
14plusmn01
31plusmn
02
30plusmn5
67plusmn03
049plusmn002
nd
026plusmn002
5RR
2295plusmn119
453plusmn182
17plusmn07
16plusmn07
26plusmn1
32plusmn2
18plusmn01
23plusmn01
25plusmn4
49plusmn03
059plusmn012
nd
024plusmn004
1RH
R6134plusmn284
1407plusmn237
248plusmn77
17plusmn09
159plusmn7
747plusmn43
09plusmn03
31plusmn
03
32plusmn3
13plusmn01
289plusmn015
5plusmn1
404plusmn018
2RH
R5088plusmn320
1727plusmn284
116plusmn28
10plusmn02
155plusmn8
601plusmn
3208plusmn04
22plusmn01
38plusmn8
48plusmn03
424plusmn056
5plusmn1
104plusmn012
3RH
R5474plusmn273
2165plusmn284
68plusmn07
08plusmn01
263plusmn12
589plusmn26
05plusmn01
24plusmn01
34plusmn2
18plusmn04
563plusmn026
8plusmn2
076plusmn005
4RH
R4866plusmn214
1367plusmn113
114plusmn07
433plusmn23
398plusmn18
957plusmn50
380plusmn19
29plusmn02
33plusmn3
92plusmn04
313plusmn019
14plusmn1
105plusmn007
5RH
R5930plusmn341
1441plusmn220
427plusmn115
84plusmn05
232plusmn10
918plusmn167
130plusmn06
27plusmn08
33plusmn4
71plusmn03
362plusmn023
6plusmn1
087plusmn034
8 Journal of Chemistry
Table 6 Descriptive statistics results of elemental chemical analysis for rice and rice husk from Korba and Raipur
K Ca Ti Cr Mn Fe Ni Cu Zn Rb Sr Ba PbKorba
RiceMean 229161 22352 171 000 3119 1725 085 261 2892 1724 043 nd 025SD 49562 3267 141 000 763 314 067 036 664 1279 016 nd 017Min 160361 17506 047 000 2397 1320 039 222 2218 418 029 nd 008Max 291056 26713 402 000 4367 2086 201 300 3909 3519 067 nd 051
RHMean 370919 125624 1567 032 22562 18803 162 201 2949 1785 341 2562 061SD 83990 24548 2483 009 5767 13003 122 013 322 1018 114 645 026Min 227706 94776 230 000 17433 9274 062 185 2587 369 224 1540 041Max 444080 149997 5992 090 32500 40897 325 217 3331 2869 476 3196 102
RaipurRiceMean 251578 35445 209 047 2685 2473 088 256 2707 329 046 nd 034SD 32375 8134 088 011 691 824 066 071 509 256 012 nd 009Min 220082 23192 084 000 1966 1267 022 166 1909 058 031 nd 024Max 302055 45290 324 160 3450 3261 177 344 3136 669 059 nd 045
RHMean 549853 162125 1948 1102 24133 76237 1064 266 3412 484 390 767 155SD 53845 33542 1463 1830 9908 17201 621 035 213 339 109 386 139Min 486602 136679 683 080 15514 58874 052 219 3218 131 289 467 076Max 613438 216507 4273 4326 39779 95678 3805 308 3765 921 563 1417 404
concentration in soil The variation observed in TFs for thesame species may be due to several factors such as the age ofthe plant the tissue and the environment in which the plantis grown It was demonstrated that the absorption ofmineralsand their distribution in the plant hang on the bioavailabilityof the minerals in soil root structure and shoot system[32] Moreover the bioavailability of elements from soil toplants is determined by other factors including pH redoxconditions speciation soil texture and mineralogy organicmatter content and the presence of competing ions
TFs calculated for rice and RH using the average valuesof elemental concentration in rice RH and soils of Korbaand Raipur are shown in Figure 4 In our study TFs for RHwere always higher than rice samples for both the studiedareas TFs of K Mn Cu Zn Rb and Ba are higher in Korbasamples compared to those of Raipur Elements such as Caand Cr show TFs higher in Raipur samples while Ti Fe Niand Pb were in the same range Our results clearly show thatthe bioaccumulation is higher in RH than in rice
TF =119862p
119862s (1)
A comparison with the literature data [33] for the content ofAs Ba Cu Pb Ni Mn and Cr in rice is reported in Table 7The average values calculated as the arithmetic mean forKorba and Raipur are reported separately The literaturereports that geometric means (GM) illustrate more exactdistribution of the element concentrations in rice samplesbut comparison withmany other studies is difficult due to thelack of information on GM [33] As and Ba are not present
0000
0001
0010
0100
1000
10000K
Ca
Ti
Cr
Mn
Fe
NiCu
Zn
Rb
Sr
Ba
Pb
Rice RaipurRH Raipur
Rice KorbaRH Korba
Figure 4 Transfer factors calculated for rice and rice husk sampleswith respect to soil samples from Korba and Raipur
in our samples Our values of Cu and Ni are aligned mainlywith those from Vietnam The concentrations of Pb and Mnare aligned respectively with commercial rice from China
Journal of Chemistry 9
Table 7 Concentration of hazardous elements in rice samples reported in different literature studies (a) arithmetic means (b) arithmeticstandard deviations (c) [34] (d) [35] and (e) [36]
Element Area 119873 AM (a) ASD (b) MIN MAX
Cu
Taizhou 13 4260 826 3037 5184Commercial rice China 5 3326 774 2812 4478
Vietnam (c) 31 2600 1100 5800Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2560 710 1662 3438Korba 5 2610 360 2222 2995
Pb
Taizhou 13 2042 2070 256 2602Commercial rice China 4 356 267 167 745
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 23700 19800 20100 24000Hangzhou (e) 5 131 103 45 308
Raipur 5 340 90 235 452Korba 5 250 170 78 514
Ni
Taizhou 13 761 391 339 1134Commercial rice China 4 476 276 201 818
Vietnam (c) 31 869 lt100 2022Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 880 660 216 1770Korba 5 850 670 387 2009
Mn
Taizhou 13 28640 5570 21977 37490Commercial rice China 4 9363 3288 5804 12708
Vietnam (c) 31 9900 5900 16300Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2685 6910 19700 34500Korba 5 31200 7600 24000 43700
Cr
Taizhou 13 107 83 6 279Commercial rice China 4 199 157 62 424
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 740 340 650 830Hangzhou (e) mdash mdash mdash mdash
Raipur 5 470 110 0 1600Korba 5 nd nd nd nd
and Taizhou The content of Cr in the samples of Raipur isexceptionally high
Despite all the reported data of metal content in riceaccording to the national standard for safety milled rice cri-teria [37] (NY5115-2002) themaximum allowable concentra-tions (MAC) ofAs and Pb are 050 and 020120583gg respectivelyMoreover the World Health Organization (WHO) provides020mgKg as the safe limit for Pb in rice [38] but it doesnot report any limit for other analyzed metals In the presentstudy Pb concentration is much higher than the reportedlimit in many samples both from Raipur and Korba evenif the average value is aligned with that of WHO Even it isknown as a toxic element Cr safe limit from WHOFAO is
not determined Since rice is the common food for the Asiancontinent and especially in China the MAC criteria deter-mine the same limit for some metals such as Cu 10mgKgZn 50mgKg Cr 1mgKg and Pb as that decided by WHO[39]
Statistical analysis does not show any significant differ-ence between rice and rice husk samples of the two areas ofinterest
Figure 5 shows the concentration of selected elements inall samples classified by species soil rice husk and riceThisfigure highlights the possible transfer andor accumulation ofelements from soil into the other twomatrices In some casesrice husk seems to act as a barrier for some heavymetals such
10 Journal of Chemistry
0
1
10
100
1000Cr
conc
entr
atio
n (m
gkg
)
Samples
Cr
1
10
100
As c
once
ntra
tion
(mg
kg)
As
0
1
10
100
Pb co
ncen
trat
ion
(mg
kg) Pb
0
2000
4000
6000
8000
10000
12000
K co
ncen
trat
ion
(mg
kg) K
010203040506070
Cu co
ncen
trat
ion
(mg
kg) Cu
010203040506070
Zn co
ncen
trat
ion
(mg
kg) Zn
0
1
10
100
Ni c
once
ntra
tion
(mg
kg) Ni
1
10
100
1000
10000
100000
Fe co
ncen
trat
ion
(mg
kg) Fe
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2 RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Figure 5 Concentration of elements in soil rice husk and rice samples from Korba and Raipur
as Cr K Fe and Pb The possible barrier role of rice husk isinteresting and it can be hypothesized also for Mn Ba andSr Unfortunately it is not clear in the case of Cu Ni Zn RbBi Ti and V
4 Conclusions
This work reports the chemical composition study of soilsrice and rice husk from Korba and Raipur (India) by means
Journal of Chemistry 11
of TXRF Results show some metals uptake from soil to ricein particular Pb and Cr from the Raipur region The noveltyof this study is the chemical characterization of rice made inparallel with the analysis of soils and corresponding rice huskA detailed analysis of all the data shows that rice husk accu-mulates more heavy metals than rice suggesting a possiblebarrier effect of the husk Despite that dedicated studiesshould be done to verify the clear role of husk and other para-meters such as rice species soils characteristics (pH claycontent and organic matter) and other variables Based onthe extremely interesting results obtained in this study someapproaches may be developed to promote low metals accu-mulation in rice
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study was supported by LIFE+ the financial instrumentof the European Community to support environmentalprojects (LIFE+ 2011 Project ENVIT000256) The authorsare grateful to Directorate-General Environment EuropeanCommission for inclusion of COSMOS-RICE Project inScience for Environment Policy Information Service (seehttpeceuropaeuenvironmentintegrationresearchnew-salertpdf383na2 enpdf) The authors acknowledge Profe-ssor Patel School of Studies in Chemistry Pt RavishankarShukla University Raipur India for the support in samplescollection
References
[1] C Huamain Z Chunrong T Cong and Z Yongguan ldquoHeavymetal pollution in soils in China status and countermeasuresrdquoAmbio vol 28 no 2 pp 130ndash134 1999
[2] M E Watanabe ldquoPhytoremediation on the brink of commer-cializationrdquo Environmental Science amp Technology vol 31 pp82Andash187A 1997
[3] S Uchida K Tagami and N Ishikawa ldquoConcentration soil-to-plant transfer factor and soil-soil solution distribution coeffi-cient of selenium in the surface environment -9106rdquo in Proceed-ings of the Symposium onWasteManagement (WM rsquo09 ) pp 1ndash5Phoenix Ariz USA March 2009
[4] X F Hu Y Jiang Y Shu X Hu L Liu and F Luo ldquoEffectsof mining wastewater discharges on heavy metal pollution andsoil enzyme activity of the paddy fieldsrdquo Journal of GeochemicalExploration vol 147 part B pp 139ndash150 2014
[5] A Sekara M Poniedziałek J Ciura and E Jedrszczyk ldquoCad-mium and lead accumulation and distribution in the organs ofnine crops implications for phytoremediationrdquo Polish Journalof Environmental Studies vol 14 no 4 pp 509ndash516 2005
[6] R Stone ldquoFood safetymdasharsenic and paddy rice a neglectedcancer riskrdquo Science vol 321 no 5886 pp 184ndash185 2008
[7] Committee for the Common Organisation of Agricultural Mar-kets 11 2014 httpeceuropaeuagriculturecerealspresenta-tionsricemarket-situation enpdf
[8] K R Dikshit and J E Schwartzberg ldquoIndia iI paeserdquo in Enci-clopedia Britannica pp 9ndash10 2007
[9] K M Omatola and A D Onojah ldquoElemental analysis of ricehusk ash using X-ray fluorescence techniquerdquo InternationalJournal of Physical Sciences vol 4 no 4 pp 189ndash193 2009
[10] L Sun and K Gong ldquoSilicon-based materials from rice husksand their applicationsrdquo Industrial and Engineering ChemistryResearch vol 40 no 25 pp 5861ndash5877 2001
[11] S Sugita ldquoOn the economical production of large quantities ofhighly reactive rice husk ashrdquo in Proceedings of the InternationalSymposium on Innovative World of Concrete (ICI-IWC rsquo93) pp2 3ndash71 1993
[12] I R Shaikh and A A Shaikh ldquoUtilization of wheat husk ashas silica source for the synthesis of MCM-41 type mesoporoussilicates a sustainable approach towards valorization of the agri-cultural waste streamrdquo Research Journal of Chemical Sciencesvol 3 pp 66ndash72 2013
[13] K M Omatola and A D Onojah ldquoRice husk as a potentialsource of high technological raw materials a reviewrdquo Journalof Polymer Science Innovation vol 4 pp 30ndash35 2012
[14] A Bosio N Rodella A Gianoncelli et al ldquoA new method toinertize incinerator toxic fly ash with silica from rice husk ashrdquoEnvironmental Chemistry Letters vol 11 no 4 pp 329ndash3332013
[15] A Bosio A Zacco L Borgese et al ldquoA sustainable technologyfor Pb and Zn stabilization based on the use of only wastematerials a green chemistry approach to avoid chemicals andpromote CO
2sequestrationrdquoChemical Engineering Journal vol
253 pp 377ndash384 2014[16] A Taylor S Branch M P Day M Patriarca and M White
ldquoAtomic spectrometry update Clinical and biological materialsfoods and beveragesrdquo Journal of Analytical Atomic Spectrometryvol 24 no 4 pp 535ndash579 2009
[17] K S Patel K Shrivas P Hoffmann and N Jakubowski ldquoAsurvey of lead pollution in Chhattisgarh State central IndiardquoEnvironmental Geochemistry and Health vol 28 no 1-2 pp 11ndash17 2006
[18] K S Patel K Shrivas R Brandt N Jakubowski W Corns andP Hoffmann ldquoArsenic contamination in water soil sedimentand rice of central Indiardquo Environmental Geochemistry andHealth vol 27 no 2 pp 131ndash145 2005
[19] B Giri K S Patel N K Jaiswal et al ldquoComposition and sourcesof organic tracers in aerosol particles of industrial central IndiardquoAtmospheric Research vol 120-121 pp 312ndash324 2013
[20] httpwwwepagovoswhazardtestmethodssw846pdfs3050bpdf
[21] L Borgese A Zacco E Bontempi et al ldquoTotal reflection of x-ray fluorescence (TXRF) amature technique for environmentalchemical nanoscale metrologyrdquoMeasurement Science and Tech-nology vol 20 no 8 Article ID 084027 2009
[22] F Bilo L Borgese D Cazzago et al ldquoTXRF analysis ofsoils and sediments to assess environmental contaminationrdquoEnvironmental Science and Pollution Research vol 21 no 23 pp13208ndash13214 2014
[23] Esdat 2000 Dutch Target and Intervention Values The newDutch list 2000 httpwwwesdatnet
[24] A Kabata-Pendias ldquoEnvironmental biogeochemistrymdashoutlineof the developmentrdquo Przeglad Geologiczny vol 49 no 10 pp957ndash959 2001
[25] S Srinivasa Gowd M Ramakrishna Reddy and P K GovilldquoAssessment of heavy metal contamination in soils at Jajmau
12 Journal of Chemistry
(Kanpur) and Unnao industrial areas of the Ganga Plain UttarPradesh Indiardquo Journal ofHazardousMaterials vol 174 no 1ndash3pp 113ndash121 2010
[26] K S Patel A Verma N K Jaiswal et al ldquoArsenic concentrationin soil rice and straw in central Indiardquo in Proceedings of the 4thInternational Congress on Arsenic in the Environment pp 508ndash509 July 2012
[27] A Kabata-Pendias Trace Elements in Soils and Plants Technol-ogy amp Engineering CRC Press 3rd edition 2000
[28] A D Jacobson and J D Blum ldquoCaSr and 87Sr86Sr geochem-istry of disseminated calcite in Himalayan silicate rocks fromNanga Parbat influence on river-water chemistryrdquoGeology vol28 no 5 pp 463ndash466 2000
[29] Y N Vodyanitskii ldquoCriteria of the technogenic nature ofheavy metals and metalloids in soils a review of publicationsrdquoEurasian Soil Science vol 42 no 9 pp 1053ndash1061 2009
[30] H Hoefler C Streli P Wobrauschek M Ovari and G ZarayldquoAnalysis of low Z elements in various environmental sampleswith total reflection X-ray fluorescence (TXRF) spectrometryrdquoSpectrochimica Acta Part B Atomic Spectroscopy vol 61 no 10-11 pp 1135ndash1140 2006
[31] K K Taha I M Shmou H M Osman and M H ShayoubldquoSoil-plant transfer and accumulation factors for trace elementsat the Blue and White Nilesrdquo Journal of Applied and IndustrialSciences vol 1 pp 97ndash102 2013
[32] H Papaefthymiou G Papatheodorou A Moustakli DChristodoulou and M Geraga ldquoNatural radionuclides and137Cs distributions and their relationship with sedimentologicalprocesses in Patras Harbour Greecerdquo Journal of EnvironmentalRadioactivity vol 94 no 2 pp 55ndash74 2007
[33] J Fu Q Zhou J Liu et al ldquoHigh levels of heavy metals inrice (Oryza sativa L) from a typical E-waste recycling areain southeast China and its potential risk to human healthrdquoChemosphere vol 71 no 7 pp 1269ndash1275 2008
[34] T D Phuong P Van Chuong D T Khiem and S Kokot ldquoEle-mental content of Vietnamese rice Part 1 Sampling analysisand comparison with previous studiesrdquo Analyst vol 124 no 4pp 553ndash560 1999
[35] S W Al Rmalli P I Haris C F Harrington and M AyubldquoA survey of arsenic in foodstuffs on sale in the UnitedKingdom and imported from Bangladeshrdquo Science of the TotalEnvironment vol 337 no 1ndash3 pp 23ndash30 2005
[36] C Fangmin Z Ningchun X Haiming et al ldquoCadmium andlead contamination in japonica rice grains and its variationamong the different locations in southeast Chinardquo Science of theTotal Environment vol 359 no 1ndash3 pp 156ndash166 2006
[37] National Programme on Safety Food SafetyMilled Rice Criteriaof PR China (NY5115-2002) China Ministry of AgricultureBeijing China 2002
[38] FAOWHOCodexAlimentariusGeneral Standards for Contam-inants and Toxins in Food Schedule1 Maximum and GuidelineLevels for Contaminants and Toxins in Food Joint FAOWHOFood Standards Programme Reference CXFAC 0216 CodexCommittee Rotterdam The Netherlands 2002
[39] The Ministry of Health of China GB 2762-2012 Standards forChinese Food Sanitation TheMinistry of Health of China 2012
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
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CatalystsJournal of
Journal of Chemistry 7
Table5Elem
entalcon
centratio
nin
rice(R)
andric
ehusk(RH)sam
ples
from
Korbaa
ndRa
ipur
Sample
Elem
entalcon
centratio
n(m
gKg
)K
CaTi
CrMn
FeNi
CuZn
RbSr
BaPb
Korba
1RK
2179plusmn122
267plusmn67
19plusmn04
00plusmn00
44plusmn2
18plusmn3
04plusmn01
22plusmn02
29plusmn1
186plusmn10
067plusmn014
nd
027plusmn001
2RK
2911plusmn160
225plusmn19
05plusmn03
00plusmn00
29plusmn1
19plusmn2
09plusmn01
24plusmn01
30plusmn1
352plusmn17
033plusmn005
nd
051plusmn003
3RK
2603plusmn184
227plusmn17
40plusmn03
00plusmn00
32plusmn1
21plusmn1
05plusmn01
30plusmn02
39plusmn2
42plusmn03
052plusmn003
nd
025plusmn002
4RK
1604plusmn111
223plusmn20
14plusmn04
00plusmn00
27plusmn1
13plusmn1
20plusmn06
30plusmn02
22plusmn1
57plusmn03
029plusmn002
nd
008plusmn002
5RK
2162plusmn113
175plusmn11
07plusmn02
00plusmn00
24plusmn1
15plusmn1
04plusmn01
25plusmn01
24plusmn1
225plusmn10
033plusmn001
nd
013plusmn001
1RH
K4152plusmn303
1500plusmn68
28plusmn09
04plusmn01
325plusmn15
93plusmn4
06plusmn01
20plusmn01
32plusmn1
223plusmn12
476plusmn022
32plusmn2
041plusmn004
2RH
K3894plusmn311
1277plusmn61
73plusmn24
00plusmn00
174plusmn8
161plusmn
1133plusmn02
18plusmn04
26plusmn1
287plusmn20
268plusmn013
15plusmn1
047plusmn003
3RH
K2277plusmn152
1485plusmn106
599plusmn456
09plusmn02
210plusmn9
409plusmn26
10plusmn01
21plusmn
02
33plusmn3
37plusmn03
449plusmn023
26plusmn2
070plusmn007
4RH
K44
41plusmn196
1072plusmn47
60plusmn24
02plusmn01
213plusmn9
184plusmn9
26plusmn01
22plusmn01
28plusmn1
111plusmn05
224plusmn010
25plusmn1
043plusmn002
5RH
K3782plusmn167
948plusmn61
23plusmn03
00plusmn00
206plusmn9
93plusmn4
06plusmn01
19plusmn01
27plusmn2
234plusmn11
289plusmn015
30plusmn1
102plusmn005
Raipur
1RR
3021plusmn221
395plusmn54
24plusmn11
03plusmn01
21plusmn1
33plusmn22
06plusmn01
34plusmn04
30plusmn2
06plusmn003
031plusmn003
nd
038plusmn002
2RR
2201plusmn101
232plusmn12
08plusmn02
00plusmn00
20plusmn1
13plusmn1
02plusmn01
17plusmn01
19plusmn1
32plusmn02
038plusmn002
nd
045plusmn004
3RR
2621plusmn120
347plusmn98
32plusmn04
03plusmn01
33plusmn1
24plusmn1
04plusmn01
23plusmn02
31plusmn2
11plusmn01
055plusmn004
nd
040plusmn003
4RR
2441plusmn134
345plusmn40
22plusmn05
02plusmn01
35plusmn2
22plusmn1
14plusmn01
31plusmn
02
30plusmn5
67plusmn03
049plusmn002
nd
026plusmn002
5RR
2295plusmn119
453plusmn182
17plusmn07
16plusmn07
26plusmn1
32plusmn2
18plusmn01
23plusmn01
25plusmn4
49plusmn03
059plusmn012
nd
024plusmn004
1RH
R6134plusmn284
1407plusmn237
248plusmn77
17plusmn09
159plusmn7
747plusmn43
09plusmn03
31plusmn
03
32plusmn3
13plusmn01
289plusmn015
5plusmn1
404plusmn018
2RH
R5088plusmn320
1727plusmn284
116plusmn28
10plusmn02
155plusmn8
601plusmn
3208plusmn04
22plusmn01
38plusmn8
48plusmn03
424plusmn056
5plusmn1
104plusmn012
3RH
R5474plusmn273
2165plusmn284
68plusmn07
08plusmn01
263plusmn12
589plusmn26
05plusmn01
24plusmn01
34plusmn2
18plusmn04
563plusmn026
8plusmn2
076plusmn005
4RH
R4866plusmn214
1367plusmn113
114plusmn07
433plusmn23
398plusmn18
957plusmn50
380plusmn19
29plusmn02
33plusmn3
92plusmn04
313plusmn019
14plusmn1
105plusmn007
5RH
R5930plusmn341
1441plusmn220
427plusmn115
84plusmn05
232plusmn10
918plusmn167
130plusmn06
27plusmn08
33plusmn4
71plusmn03
362plusmn023
6plusmn1
087plusmn034
8 Journal of Chemistry
Table 6 Descriptive statistics results of elemental chemical analysis for rice and rice husk from Korba and Raipur
K Ca Ti Cr Mn Fe Ni Cu Zn Rb Sr Ba PbKorba
RiceMean 229161 22352 171 000 3119 1725 085 261 2892 1724 043 nd 025SD 49562 3267 141 000 763 314 067 036 664 1279 016 nd 017Min 160361 17506 047 000 2397 1320 039 222 2218 418 029 nd 008Max 291056 26713 402 000 4367 2086 201 300 3909 3519 067 nd 051
RHMean 370919 125624 1567 032 22562 18803 162 201 2949 1785 341 2562 061SD 83990 24548 2483 009 5767 13003 122 013 322 1018 114 645 026Min 227706 94776 230 000 17433 9274 062 185 2587 369 224 1540 041Max 444080 149997 5992 090 32500 40897 325 217 3331 2869 476 3196 102
RaipurRiceMean 251578 35445 209 047 2685 2473 088 256 2707 329 046 nd 034SD 32375 8134 088 011 691 824 066 071 509 256 012 nd 009Min 220082 23192 084 000 1966 1267 022 166 1909 058 031 nd 024Max 302055 45290 324 160 3450 3261 177 344 3136 669 059 nd 045
RHMean 549853 162125 1948 1102 24133 76237 1064 266 3412 484 390 767 155SD 53845 33542 1463 1830 9908 17201 621 035 213 339 109 386 139Min 486602 136679 683 080 15514 58874 052 219 3218 131 289 467 076Max 613438 216507 4273 4326 39779 95678 3805 308 3765 921 563 1417 404
concentration in soil The variation observed in TFs for thesame species may be due to several factors such as the age ofthe plant the tissue and the environment in which the plantis grown It was demonstrated that the absorption ofmineralsand their distribution in the plant hang on the bioavailabilityof the minerals in soil root structure and shoot system[32] Moreover the bioavailability of elements from soil toplants is determined by other factors including pH redoxconditions speciation soil texture and mineralogy organicmatter content and the presence of competing ions
TFs calculated for rice and RH using the average valuesof elemental concentration in rice RH and soils of Korbaand Raipur are shown in Figure 4 In our study TFs for RHwere always higher than rice samples for both the studiedareas TFs of K Mn Cu Zn Rb and Ba are higher in Korbasamples compared to those of Raipur Elements such as Caand Cr show TFs higher in Raipur samples while Ti Fe Niand Pb were in the same range Our results clearly show thatthe bioaccumulation is higher in RH than in rice
TF =119862p
119862s (1)
A comparison with the literature data [33] for the content ofAs Ba Cu Pb Ni Mn and Cr in rice is reported in Table 7The average values calculated as the arithmetic mean forKorba and Raipur are reported separately The literaturereports that geometric means (GM) illustrate more exactdistribution of the element concentrations in rice samplesbut comparison withmany other studies is difficult due to thelack of information on GM [33] As and Ba are not present
0000
0001
0010
0100
1000
10000K
Ca
Ti
Cr
Mn
Fe
NiCu
Zn
Rb
Sr
Ba
Pb
Rice RaipurRH Raipur
Rice KorbaRH Korba
Figure 4 Transfer factors calculated for rice and rice husk sampleswith respect to soil samples from Korba and Raipur
in our samples Our values of Cu and Ni are aligned mainlywith those from Vietnam The concentrations of Pb and Mnare aligned respectively with commercial rice from China
Journal of Chemistry 9
Table 7 Concentration of hazardous elements in rice samples reported in different literature studies (a) arithmetic means (b) arithmeticstandard deviations (c) [34] (d) [35] and (e) [36]
Element Area 119873 AM (a) ASD (b) MIN MAX
Cu
Taizhou 13 4260 826 3037 5184Commercial rice China 5 3326 774 2812 4478
Vietnam (c) 31 2600 1100 5800Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2560 710 1662 3438Korba 5 2610 360 2222 2995
Pb
Taizhou 13 2042 2070 256 2602Commercial rice China 4 356 267 167 745
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 23700 19800 20100 24000Hangzhou (e) 5 131 103 45 308
Raipur 5 340 90 235 452Korba 5 250 170 78 514
Ni
Taizhou 13 761 391 339 1134Commercial rice China 4 476 276 201 818
Vietnam (c) 31 869 lt100 2022Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 880 660 216 1770Korba 5 850 670 387 2009
Mn
Taizhou 13 28640 5570 21977 37490Commercial rice China 4 9363 3288 5804 12708
Vietnam (c) 31 9900 5900 16300Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2685 6910 19700 34500Korba 5 31200 7600 24000 43700
Cr
Taizhou 13 107 83 6 279Commercial rice China 4 199 157 62 424
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 740 340 650 830Hangzhou (e) mdash mdash mdash mdash
Raipur 5 470 110 0 1600Korba 5 nd nd nd nd
and Taizhou The content of Cr in the samples of Raipur isexceptionally high
Despite all the reported data of metal content in riceaccording to the national standard for safety milled rice cri-teria [37] (NY5115-2002) themaximum allowable concentra-tions (MAC) ofAs and Pb are 050 and 020120583gg respectivelyMoreover the World Health Organization (WHO) provides020mgKg as the safe limit for Pb in rice [38] but it doesnot report any limit for other analyzed metals In the presentstudy Pb concentration is much higher than the reportedlimit in many samples both from Raipur and Korba evenif the average value is aligned with that of WHO Even it isknown as a toxic element Cr safe limit from WHOFAO is
not determined Since rice is the common food for the Asiancontinent and especially in China the MAC criteria deter-mine the same limit for some metals such as Cu 10mgKgZn 50mgKg Cr 1mgKg and Pb as that decided by WHO[39]
Statistical analysis does not show any significant differ-ence between rice and rice husk samples of the two areas ofinterest
Figure 5 shows the concentration of selected elements inall samples classified by species soil rice husk and riceThisfigure highlights the possible transfer andor accumulation ofelements from soil into the other twomatrices In some casesrice husk seems to act as a barrier for some heavymetals such
10 Journal of Chemistry
0
1
10
100
1000Cr
conc
entr
atio
n (m
gkg
)
Samples
Cr
1
10
100
As c
once
ntra
tion
(mg
kg)
As
0
1
10
100
Pb co
ncen
trat
ion
(mg
kg) Pb
0
2000
4000
6000
8000
10000
12000
K co
ncen
trat
ion
(mg
kg) K
010203040506070
Cu co
ncen
trat
ion
(mg
kg) Cu
010203040506070
Zn co
ncen
trat
ion
(mg
kg) Zn
0
1
10
100
Ni c
once
ntra
tion
(mg
kg) Ni
1
10
100
1000
10000
100000
Fe co
ncen
trat
ion
(mg
kg) Fe
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2 RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Figure 5 Concentration of elements in soil rice husk and rice samples from Korba and Raipur
as Cr K Fe and Pb The possible barrier role of rice husk isinteresting and it can be hypothesized also for Mn Ba andSr Unfortunately it is not clear in the case of Cu Ni Zn RbBi Ti and V
4 Conclusions
This work reports the chemical composition study of soilsrice and rice husk from Korba and Raipur (India) by means
Journal of Chemistry 11
of TXRF Results show some metals uptake from soil to ricein particular Pb and Cr from the Raipur region The noveltyof this study is the chemical characterization of rice made inparallel with the analysis of soils and corresponding rice huskA detailed analysis of all the data shows that rice husk accu-mulates more heavy metals than rice suggesting a possiblebarrier effect of the husk Despite that dedicated studiesshould be done to verify the clear role of husk and other para-meters such as rice species soils characteristics (pH claycontent and organic matter) and other variables Based onthe extremely interesting results obtained in this study someapproaches may be developed to promote low metals accu-mulation in rice
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study was supported by LIFE+ the financial instrumentof the European Community to support environmentalprojects (LIFE+ 2011 Project ENVIT000256) The authorsare grateful to Directorate-General Environment EuropeanCommission for inclusion of COSMOS-RICE Project inScience for Environment Policy Information Service (seehttpeceuropaeuenvironmentintegrationresearchnew-salertpdf383na2 enpdf) The authors acknowledge Profe-ssor Patel School of Studies in Chemistry Pt RavishankarShukla University Raipur India for the support in samplescollection
References
[1] C Huamain Z Chunrong T Cong and Z Yongguan ldquoHeavymetal pollution in soils in China status and countermeasuresrdquoAmbio vol 28 no 2 pp 130ndash134 1999
[2] M E Watanabe ldquoPhytoremediation on the brink of commer-cializationrdquo Environmental Science amp Technology vol 31 pp82Andash187A 1997
[3] S Uchida K Tagami and N Ishikawa ldquoConcentration soil-to-plant transfer factor and soil-soil solution distribution coeffi-cient of selenium in the surface environment -9106rdquo in Proceed-ings of the Symposium onWasteManagement (WM rsquo09 ) pp 1ndash5Phoenix Ariz USA March 2009
[4] X F Hu Y Jiang Y Shu X Hu L Liu and F Luo ldquoEffectsof mining wastewater discharges on heavy metal pollution andsoil enzyme activity of the paddy fieldsrdquo Journal of GeochemicalExploration vol 147 part B pp 139ndash150 2014
[5] A Sekara M Poniedziałek J Ciura and E Jedrszczyk ldquoCad-mium and lead accumulation and distribution in the organs ofnine crops implications for phytoremediationrdquo Polish Journalof Environmental Studies vol 14 no 4 pp 509ndash516 2005
[6] R Stone ldquoFood safetymdasharsenic and paddy rice a neglectedcancer riskrdquo Science vol 321 no 5886 pp 184ndash185 2008
[7] Committee for the Common Organisation of Agricultural Mar-kets 11 2014 httpeceuropaeuagriculturecerealspresenta-tionsricemarket-situation enpdf
[8] K R Dikshit and J E Schwartzberg ldquoIndia iI paeserdquo in Enci-clopedia Britannica pp 9ndash10 2007
[9] K M Omatola and A D Onojah ldquoElemental analysis of ricehusk ash using X-ray fluorescence techniquerdquo InternationalJournal of Physical Sciences vol 4 no 4 pp 189ndash193 2009
[10] L Sun and K Gong ldquoSilicon-based materials from rice husksand their applicationsrdquo Industrial and Engineering ChemistryResearch vol 40 no 25 pp 5861ndash5877 2001
[11] S Sugita ldquoOn the economical production of large quantities ofhighly reactive rice husk ashrdquo in Proceedings of the InternationalSymposium on Innovative World of Concrete (ICI-IWC rsquo93) pp2 3ndash71 1993
[12] I R Shaikh and A A Shaikh ldquoUtilization of wheat husk ashas silica source for the synthesis of MCM-41 type mesoporoussilicates a sustainable approach towards valorization of the agri-cultural waste streamrdquo Research Journal of Chemical Sciencesvol 3 pp 66ndash72 2013
[13] K M Omatola and A D Onojah ldquoRice husk as a potentialsource of high technological raw materials a reviewrdquo Journalof Polymer Science Innovation vol 4 pp 30ndash35 2012
[14] A Bosio N Rodella A Gianoncelli et al ldquoA new method toinertize incinerator toxic fly ash with silica from rice husk ashrdquoEnvironmental Chemistry Letters vol 11 no 4 pp 329ndash3332013
[15] A Bosio A Zacco L Borgese et al ldquoA sustainable technologyfor Pb and Zn stabilization based on the use of only wastematerials a green chemistry approach to avoid chemicals andpromote CO
2sequestrationrdquoChemical Engineering Journal vol
253 pp 377ndash384 2014[16] A Taylor S Branch M P Day M Patriarca and M White
ldquoAtomic spectrometry update Clinical and biological materialsfoods and beveragesrdquo Journal of Analytical Atomic Spectrometryvol 24 no 4 pp 535ndash579 2009
[17] K S Patel K Shrivas P Hoffmann and N Jakubowski ldquoAsurvey of lead pollution in Chhattisgarh State central IndiardquoEnvironmental Geochemistry and Health vol 28 no 1-2 pp 11ndash17 2006
[18] K S Patel K Shrivas R Brandt N Jakubowski W Corns andP Hoffmann ldquoArsenic contamination in water soil sedimentand rice of central Indiardquo Environmental Geochemistry andHealth vol 27 no 2 pp 131ndash145 2005
[19] B Giri K S Patel N K Jaiswal et al ldquoComposition and sourcesof organic tracers in aerosol particles of industrial central IndiardquoAtmospheric Research vol 120-121 pp 312ndash324 2013
[20] httpwwwepagovoswhazardtestmethodssw846pdfs3050bpdf
[21] L Borgese A Zacco E Bontempi et al ldquoTotal reflection of x-ray fluorescence (TXRF) amature technique for environmentalchemical nanoscale metrologyrdquoMeasurement Science and Tech-nology vol 20 no 8 Article ID 084027 2009
[22] F Bilo L Borgese D Cazzago et al ldquoTXRF analysis ofsoils and sediments to assess environmental contaminationrdquoEnvironmental Science and Pollution Research vol 21 no 23 pp13208ndash13214 2014
[23] Esdat 2000 Dutch Target and Intervention Values The newDutch list 2000 httpwwwesdatnet
[24] A Kabata-Pendias ldquoEnvironmental biogeochemistrymdashoutlineof the developmentrdquo Przeglad Geologiczny vol 49 no 10 pp957ndash959 2001
[25] S Srinivasa Gowd M Ramakrishna Reddy and P K GovilldquoAssessment of heavy metal contamination in soils at Jajmau
12 Journal of Chemistry
(Kanpur) and Unnao industrial areas of the Ganga Plain UttarPradesh Indiardquo Journal ofHazardousMaterials vol 174 no 1ndash3pp 113ndash121 2010
[26] K S Patel A Verma N K Jaiswal et al ldquoArsenic concentrationin soil rice and straw in central Indiardquo in Proceedings of the 4thInternational Congress on Arsenic in the Environment pp 508ndash509 July 2012
[27] A Kabata-Pendias Trace Elements in Soils and Plants Technol-ogy amp Engineering CRC Press 3rd edition 2000
[28] A D Jacobson and J D Blum ldquoCaSr and 87Sr86Sr geochem-istry of disseminated calcite in Himalayan silicate rocks fromNanga Parbat influence on river-water chemistryrdquoGeology vol28 no 5 pp 463ndash466 2000
[29] Y N Vodyanitskii ldquoCriteria of the technogenic nature ofheavy metals and metalloids in soils a review of publicationsrdquoEurasian Soil Science vol 42 no 9 pp 1053ndash1061 2009
[30] H Hoefler C Streli P Wobrauschek M Ovari and G ZarayldquoAnalysis of low Z elements in various environmental sampleswith total reflection X-ray fluorescence (TXRF) spectrometryrdquoSpectrochimica Acta Part B Atomic Spectroscopy vol 61 no 10-11 pp 1135ndash1140 2006
[31] K K Taha I M Shmou H M Osman and M H ShayoubldquoSoil-plant transfer and accumulation factors for trace elementsat the Blue and White Nilesrdquo Journal of Applied and IndustrialSciences vol 1 pp 97ndash102 2013
[32] H Papaefthymiou G Papatheodorou A Moustakli DChristodoulou and M Geraga ldquoNatural radionuclides and137Cs distributions and their relationship with sedimentologicalprocesses in Patras Harbour Greecerdquo Journal of EnvironmentalRadioactivity vol 94 no 2 pp 55ndash74 2007
[33] J Fu Q Zhou J Liu et al ldquoHigh levels of heavy metals inrice (Oryza sativa L) from a typical E-waste recycling areain southeast China and its potential risk to human healthrdquoChemosphere vol 71 no 7 pp 1269ndash1275 2008
[34] T D Phuong P Van Chuong D T Khiem and S Kokot ldquoEle-mental content of Vietnamese rice Part 1 Sampling analysisand comparison with previous studiesrdquo Analyst vol 124 no 4pp 553ndash560 1999
[35] S W Al Rmalli P I Haris C F Harrington and M AyubldquoA survey of arsenic in foodstuffs on sale in the UnitedKingdom and imported from Bangladeshrdquo Science of the TotalEnvironment vol 337 no 1ndash3 pp 23ndash30 2005
[36] C Fangmin Z Ningchun X Haiming et al ldquoCadmium andlead contamination in japonica rice grains and its variationamong the different locations in southeast Chinardquo Science of theTotal Environment vol 359 no 1ndash3 pp 156ndash166 2006
[37] National Programme on Safety Food SafetyMilled Rice Criteriaof PR China (NY5115-2002) China Ministry of AgricultureBeijing China 2002
[38] FAOWHOCodexAlimentariusGeneral Standards for Contam-inants and Toxins in Food Schedule1 Maximum and GuidelineLevels for Contaminants and Toxins in Food Joint FAOWHOFood Standards Programme Reference CXFAC 0216 CodexCommittee Rotterdam The Netherlands 2002
[39] The Ministry of Health of China GB 2762-2012 Standards forChinese Food Sanitation TheMinistry of Health of China 2012
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
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Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
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Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
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Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
8 Journal of Chemistry
Table 6 Descriptive statistics results of elemental chemical analysis for rice and rice husk from Korba and Raipur
K Ca Ti Cr Mn Fe Ni Cu Zn Rb Sr Ba PbKorba
RiceMean 229161 22352 171 000 3119 1725 085 261 2892 1724 043 nd 025SD 49562 3267 141 000 763 314 067 036 664 1279 016 nd 017Min 160361 17506 047 000 2397 1320 039 222 2218 418 029 nd 008Max 291056 26713 402 000 4367 2086 201 300 3909 3519 067 nd 051
RHMean 370919 125624 1567 032 22562 18803 162 201 2949 1785 341 2562 061SD 83990 24548 2483 009 5767 13003 122 013 322 1018 114 645 026Min 227706 94776 230 000 17433 9274 062 185 2587 369 224 1540 041Max 444080 149997 5992 090 32500 40897 325 217 3331 2869 476 3196 102
RaipurRiceMean 251578 35445 209 047 2685 2473 088 256 2707 329 046 nd 034SD 32375 8134 088 011 691 824 066 071 509 256 012 nd 009Min 220082 23192 084 000 1966 1267 022 166 1909 058 031 nd 024Max 302055 45290 324 160 3450 3261 177 344 3136 669 059 nd 045
RHMean 549853 162125 1948 1102 24133 76237 1064 266 3412 484 390 767 155SD 53845 33542 1463 1830 9908 17201 621 035 213 339 109 386 139Min 486602 136679 683 080 15514 58874 052 219 3218 131 289 467 076Max 613438 216507 4273 4326 39779 95678 3805 308 3765 921 563 1417 404
concentration in soil The variation observed in TFs for thesame species may be due to several factors such as the age ofthe plant the tissue and the environment in which the plantis grown It was demonstrated that the absorption ofmineralsand their distribution in the plant hang on the bioavailabilityof the minerals in soil root structure and shoot system[32] Moreover the bioavailability of elements from soil toplants is determined by other factors including pH redoxconditions speciation soil texture and mineralogy organicmatter content and the presence of competing ions
TFs calculated for rice and RH using the average valuesof elemental concentration in rice RH and soils of Korbaand Raipur are shown in Figure 4 In our study TFs for RHwere always higher than rice samples for both the studiedareas TFs of K Mn Cu Zn Rb and Ba are higher in Korbasamples compared to those of Raipur Elements such as Caand Cr show TFs higher in Raipur samples while Ti Fe Niand Pb were in the same range Our results clearly show thatthe bioaccumulation is higher in RH than in rice
TF =119862p
119862s (1)
A comparison with the literature data [33] for the content ofAs Ba Cu Pb Ni Mn and Cr in rice is reported in Table 7The average values calculated as the arithmetic mean forKorba and Raipur are reported separately The literaturereports that geometric means (GM) illustrate more exactdistribution of the element concentrations in rice samplesbut comparison withmany other studies is difficult due to thelack of information on GM [33] As and Ba are not present
0000
0001
0010
0100
1000
10000K
Ca
Ti
Cr
Mn
Fe
NiCu
Zn
Rb
Sr
Ba
Pb
Rice RaipurRH Raipur
Rice KorbaRH Korba
Figure 4 Transfer factors calculated for rice and rice husk sampleswith respect to soil samples from Korba and Raipur
in our samples Our values of Cu and Ni are aligned mainlywith those from Vietnam The concentrations of Pb and Mnare aligned respectively with commercial rice from China
Journal of Chemistry 9
Table 7 Concentration of hazardous elements in rice samples reported in different literature studies (a) arithmetic means (b) arithmeticstandard deviations (c) [34] (d) [35] and (e) [36]
Element Area 119873 AM (a) ASD (b) MIN MAX
Cu
Taizhou 13 4260 826 3037 5184Commercial rice China 5 3326 774 2812 4478
Vietnam (c) 31 2600 1100 5800Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2560 710 1662 3438Korba 5 2610 360 2222 2995
Pb
Taizhou 13 2042 2070 256 2602Commercial rice China 4 356 267 167 745
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 23700 19800 20100 24000Hangzhou (e) 5 131 103 45 308
Raipur 5 340 90 235 452Korba 5 250 170 78 514
Ni
Taizhou 13 761 391 339 1134Commercial rice China 4 476 276 201 818
Vietnam (c) 31 869 lt100 2022Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 880 660 216 1770Korba 5 850 670 387 2009
Mn
Taizhou 13 28640 5570 21977 37490Commercial rice China 4 9363 3288 5804 12708
Vietnam (c) 31 9900 5900 16300Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2685 6910 19700 34500Korba 5 31200 7600 24000 43700
Cr
Taizhou 13 107 83 6 279Commercial rice China 4 199 157 62 424
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 740 340 650 830Hangzhou (e) mdash mdash mdash mdash
Raipur 5 470 110 0 1600Korba 5 nd nd nd nd
and Taizhou The content of Cr in the samples of Raipur isexceptionally high
Despite all the reported data of metal content in riceaccording to the national standard for safety milled rice cri-teria [37] (NY5115-2002) themaximum allowable concentra-tions (MAC) ofAs and Pb are 050 and 020120583gg respectivelyMoreover the World Health Organization (WHO) provides020mgKg as the safe limit for Pb in rice [38] but it doesnot report any limit for other analyzed metals In the presentstudy Pb concentration is much higher than the reportedlimit in many samples both from Raipur and Korba evenif the average value is aligned with that of WHO Even it isknown as a toxic element Cr safe limit from WHOFAO is
not determined Since rice is the common food for the Asiancontinent and especially in China the MAC criteria deter-mine the same limit for some metals such as Cu 10mgKgZn 50mgKg Cr 1mgKg and Pb as that decided by WHO[39]
Statistical analysis does not show any significant differ-ence between rice and rice husk samples of the two areas ofinterest
Figure 5 shows the concentration of selected elements inall samples classified by species soil rice husk and riceThisfigure highlights the possible transfer andor accumulation ofelements from soil into the other twomatrices In some casesrice husk seems to act as a barrier for some heavymetals such
10 Journal of Chemistry
0
1
10
100
1000Cr
conc
entr
atio
n (m
gkg
)
Samples
Cr
1
10
100
As c
once
ntra
tion
(mg
kg)
As
0
1
10
100
Pb co
ncen
trat
ion
(mg
kg) Pb
0
2000
4000
6000
8000
10000
12000
K co
ncen
trat
ion
(mg
kg) K
010203040506070
Cu co
ncen
trat
ion
(mg
kg) Cu
010203040506070
Zn co
ncen
trat
ion
(mg
kg) Zn
0
1
10
100
Ni c
once
ntra
tion
(mg
kg) Ni
1
10
100
1000
10000
100000
Fe co
ncen
trat
ion
(mg
kg) Fe
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2 RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Figure 5 Concentration of elements in soil rice husk and rice samples from Korba and Raipur
as Cr K Fe and Pb The possible barrier role of rice husk isinteresting and it can be hypothesized also for Mn Ba andSr Unfortunately it is not clear in the case of Cu Ni Zn RbBi Ti and V
4 Conclusions
This work reports the chemical composition study of soilsrice and rice husk from Korba and Raipur (India) by means
Journal of Chemistry 11
of TXRF Results show some metals uptake from soil to ricein particular Pb and Cr from the Raipur region The noveltyof this study is the chemical characterization of rice made inparallel with the analysis of soils and corresponding rice huskA detailed analysis of all the data shows that rice husk accu-mulates more heavy metals than rice suggesting a possiblebarrier effect of the husk Despite that dedicated studiesshould be done to verify the clear role of husk and other para-meters such as rice species soils characteristics (pH claycontent and organic matter) and other variables Based onthe extremely interesting results obtained in this study someapproaches may be developed to promote low metals accu-mulation in rice
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study was supported by LIFE+ the financial instrumentof the European Community to support environmentalprojects (LIFE+ 2011 Project ENVIT000256) The authorsare grateful to Directorate-General Environment EuropeanCommission for inclusion of COSMOS-RICE Project inScience for Environment Policy Information Service (seehttpeceuropaeuenvironmentintegrationresearchnew-salertpdf383na2 enpdf) The authors acknowledge Profe-ssor Patel School of Studies in Chemistry Pt RavishankarShukla University Raipur India for the support in samplescollection
References
[1] C Huamain Z Chunrong T Cong and Z Yongguan ldquoHeavymetal pollution in soils in China status and countermeasuresrdquoAmbio vol 28 no 2 pp 130ndash134 1999
[2] M E Watanabe ldquoPhytoremediation on the brink of commer-cializationrdquo Environmental Science amp Technology vol 31 pp82Andash187A 1997
[3] S Uchida K Tagami and N Ishikawa ldquoConcentration soil-to-plant transfer factor and soil-soil solution distribution coeffi-cient of selenium in the surface environment -9106rdquo in Proceed-ings of the Symposium onWasteManagement (WM rsquo09 ) pp 1ndash5Phoenix Ariz USA March 2009
[4] X F Hu Y Jiang Y Shu X Hu L Liu and F Luo ldquoEffectsof mining wastewater discharges on heavy metal pollution andsoil enzyme activity of the paddy fieldsrdquo Journal of GeochemicalExploration vol 147 part B pp 139ndash150 2014
[5] A Sekara M Poniedziałek J Ciura and E Jedrszczyk ldquoCad-mium and lead accumulation and distribution in the organs ofnine crops implications for phytoremediationrdquo Polish Journalof Environmental Studies vol 14 no 4 pp 509ndash516 2005
[6] R Stone ldquoFood safetymdasharsenic and paddy rice a neglectedcancer riskrdquo Science vol 321 no 5886 pp 184ndash185 2008
[7] Committee for the Common Organisation of Agricultural Mar-kets 11 2014 httpeceuropaeuagriculturecerealspresenta-tionsricemarket-situation enpdf
[8] K R Dikshit and J E Schwartzberg ldquoIndia iI paeserdquo in Enci-clopedia Britannica pp 9ndash10 2007
[9] K M Omatola and A D Onojah ldquoElemental analysis of ricehusk ash using X-ray fluorescence techniquerdquo InternationalJournal of Physical Sciences vol 4 no 4 pp 189ndash193 2009
[10] L Sun and K Gong ldquoSilicon-based materials from rice husksand their applicationsrdquo Industrial and Engineering ChemistryResearch vol 40 no 25 pp 5861ndash5877 2001
[11] S Sugita ldquoOn the economical production of large quantities ofhighly reactive rice husk ashrdquo in Proceedings of the InternationalSymposium on Innovative World of Concrete (ICI-IWC rsquo93) pp2 3ndash71 1993
[12] I R Shaikh and A A Shaikh ldquoUtilization of wheat husk ashas silica source for the synthesis of MCM-41 type mesoporoussilicates a sustainable approach towards valorization of the agri-cultural waste streamrdquo Research Journal of Chemical Sciencesvol 3 pp 66ndash72 2013
[13] K M Omatola and A D Onojah ldquoRice husk as a potentialsource of high technological raw materials a reviewrdquo Journalof Polymer Science Innovation vol 4 pp 30ndash35 2012
[14] A Bosio N Rodella A Gianoncelli et al ldquoA new method toinertize incinerator toxic fly ash with silica from rice husk ashrdquoEnvironmental Chemistry Letters vol 11 no 4 pp 329ndash3332013
[15] A Bosio A Zacco L Borgese et al ldquoA sustainable technologyfor Pb and Zn stabilization based on the use of only wastematerials a green chemistry approach to avoid chemicals andpromote CO
2sequestrationrdquoChemical Engineering Journal vol
253 pp 377ndash384 2014[16] A Taylor S Branch M P Day M Patriarca and M White
ldquoAtomic spectrometry update Clinical and biological materialsfoods and beveragesrdquo Journal of Analytical Atomic Spectrometryvol 24 no 4 pp 535ndash579 2009
[17] K S Patel K Shrivas P Hoffmann and N Jakubowski ldquoAsurvey of lead pollution in Chhattisgarh State central IndiardquoEnvironmental Geochemistry and Health vol 28 no 1-2 pp 11ndash17 2006
[18] K S Patel K Shrivas R Brandt N Jakubowski W Corns andP Hoffmann ldquoArsenic contamination in water soil sedimentand rice of central Indiardquo Environmental Geochemistry andHealth vol 27 no 2 pp 131ndash145 2005
[19] B Giri K S Patel N K Jaiswal et al ldquoComposition and sourcesof organic tracers in aerosol particles of industrial central IndiardquoAtmospheric Research vol 120-121 pp 312ndash324 2013
[20] httpwwwepagovoswhazardtestmethodssw846pdfs3050bpdf
[21] L Borgese A Zacco E Bontempi et al ldquoTotal reflection of x-ray fluorescence (TXRF) amature technique for environmentalchemical nanoscale metrologyrdquoMeasurement Science and Tech-nology vol 20 no 8 Article ID 084027 2009
[22] F Bilo L Borgese D Cazzago et al ldquoTXRF analysis ofsoils and sediments to assess environmental contaminationrdquoEnvironmental Science and Pollution Research vol 21 no 23 pp13208ndash13214 2014
[23] Esdat 2000 Dutch Target and Intervention Values The newDutch list 2000 httpwwwesdatnet
[24] A Kabata-Pendias ldquoEnvironmental biogeochemistrymdashoutlineof the developmentrdquo Przeglad Geologiczny vol 49 no 10 pp957ndash959 2001
[25] S Srinivasa Gowd M Ramakrishna Reddy and P K GovilldquoAssessment of heavy metal contamination in soils at Jajmau
12 Journal of Chemistry
(Kanpur) and Unnao industrial areas of the Ganga Plain UttarPradesh Indiardquo Journal ofHazardousMaterials vol 174 no 1ndash3pp 113ndash121 2010
[26] K S Patel A Verma N K Jaiswal et al ldquoArsenic concentrationin soil rice and straw in central Indiardquo in Proceedings of the 4thInternational Congress on Arsenic in the Environment pp 508ndash509 July 2012
[27] A Kabata-Pendias Trace Elements in Soils and Plants Technol-ogy amp Engineering CRC Press 3rd edition 2000
[28] A D Jacobson and J D Blum ldquoCaSr and 87Sr86Sr geochem-istry of disseminated calcite in Himalayan silicate rocks fromNanga Parbat influence on river-water chemistryrdquoGeology vol28 no 5 pp 463ndash466 2000
[29] Y N Vodyanitskii ldquoCriteria of the technogenic nature ofheavy metals and metalloids in soils a review of publicationsrdquoEurasian Soil Science vol 42 no 9 pp 1053ndash1061 2009
[30] H Hoefler C Streli P Wobrauschek M Ovari and G ZarayldquoAnalysis of low Z elements in various environmental sampleswith total reflection X-ray fluorescence (TXRF) spectrometryrdquoSpectrochimica Acta Part B Atomic Spectroscopy vol 61 no 10-11 pp 1135ndash1140 2006
[31] K K Taha I M Shmou H M Osman and M H ShayoubldquoSoil-plant transfer and accumulation factors for trace elementsat the Blue and White Nilesrdquo Journal of Applied and IndustrialSciences vol 1 pp 97ndash102 2013
[32] H Papaefthymiou G Papatheodorou A Moustakli DChristodoulou and M Geraga ldquoNatural radionuclides and137Cs distributions and their relationship with sedimentologicalprocesses in Patras Harbour Greecerdquo Journal of EnvironmentalRadioactivity vol 94 no 2 pp 55ndash74 2007
[33] J Fu Q Zhou J Liu et al ldquoHigh levels of heavy metals inrice (Oryza sativa L) from a typical E-waste recycling areain southeast China and its potential risk to human healthrdquoChemosphere vol 71 no 7 pp 1269ndash1275 2008
[34] T D Phuong P Van Chuong D T Khiem and S Kokot ldquoEle-mental content of Vietnamese rice Part 1 Sampling analysisand comparison with previous studiesrdquo Analyst vol 124 no 4pp 553ndash560 1999
[35] S W Al Rmalli P I Haris C F Harrington and M AyubldquoA survey of arsenic in foodstuffs on sale in the UnitedKingdom and imported from Bangladeshrdquo Science of the TotalEnvironment vol 337 no 1ndash3 pp 23ndash30 2005
[36] C Fangmin Z Ningchun X Haiming et al ldquoCadmium andlead contamination in japonica rice grains and its variationamong the different locations in southeast Chinardquo Science of theTotal Environment vol 359 no 1ndash3 pp 156ndash166 2006
[37] National Programme on Safety Food SafetyMilled Rice Criteriaof PR China (NY5115-2002) China Ministry of AgricultureBeijing China 2002
[38] FAOWHOCodexAlimentariusGeneral Standards for Contam-inants and Toxins in Food Schedule1 Maximum and GuidelineLevels for Contaminants and Toxins in Food Joint FAOWHOFood Standards Programme Reference CXFAC 0216 CodexCommittee Rotterdam The Netherlands 2002
[39] The Ministry of Health of China GB 2762-2012 Standards forChinese Food Sanitation TheMinistry of Health of China 2012
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 9
Table 7 Concentration of hazardous elements in rice samples reported in different literature studies (a) arithmetic means (b) arithmeticstandard deviations (c) [34] (d) [35] and (e) [36]
Element Area 119873 AM (a) ASD (b) MIN MAX
Cu
Taizhou 13 4260 826 3037 5184Commercial rice China 5 3326 774 2812 4478
Vietnam (c) 31 2600 1100 5800Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2560 710 1662 3438Korba 5 2610 360 2222 2995
Pb
Taizhou 13 2042 2070 256 2602Commercial rice China 4 356 267 167 745
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 23700 19800 20100 24000Hangzhou (e) 5 131 103 45 308
Raipur 5 340 90 235 452Korba 5 250 170 78 514
Ni
Taizhou 13 761 391 339 1134Commercial rice China 4 476 276 201 818
Vietnam (c) 31 869 lt100 2022Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 880 660 216 1770Korba 5 850 670 387 2009
Mn
Taizhou 13 28640 5570 21977 37490Commercial rice China 4 9363 3288 5804 12708
Vietnam (c) 31 9900 5900 16300Bangladesh (d) mdash mdash mdash mdashHangzhou (e) mdash mdash mdash mdash
Raipur 5 2685 6910 19700 34500Korba 5 31200 7600 24000 43700
Cr
Taizhou 13 107 83 6 279Commercial rice China 4 199 157 62 424
Vietnam (c) mdash mdash mdash mdashBangladesh (d) 3 740 340 650 830Hangzhou (e) mdash mdash mdash mdash
Raipur 5 470 110 0 1600Korba 5 nd nd nd nd
and Taizhou The content of Cr in the samples of Raipur isexceptionally high
Despite all the reported data of metal content in riceaccording to the national standard for safety milled rice cri-teria [37] (NY5115-2002) themaximum allowable concentra-tions (MAC) ofAs and Pb are 050 and 020120583gg respectivelyMoreover the World Health Organization (WHO) provides020mgKg as the safe limit for Pb in rice [38] but it doesnot report any limit for other analyzed metals In the presentstudy Pb concentration is much higher than the reportedlimit in many samples both from Raipur and Korba evenif the average value is aligned with that of WHO Even it isknown as a toxic element Cr safe limit from WHOFAO is
not determined Since rice is the common food for the Asiancontinent and especially in China the MAC criteria deter-mine the same limit for some metals such as Cu 10mgKgZn 50mgKg Cr 1mgKg and Pb as that decided by WHO[39]
Statistical analysis does not show any significant differ-ence between rice and rice husk samples of the two areas ofinterest
Figure 5 shows the concentration of selected elements inall samples classified by species soil rice husk and riceThisfigure highlights the possible transfer andor accumulation ofelements from soil into the other twomatrices In some casesrice husk seems to act as a barrier for some heavymetals such
10 Journal of Chemistry
0
1
10
100
1000Cr
conc
entr
atio
n (m
gkg
)
Samples
Cr
1
10
100
As c
once
ntra
tion
(mg
kg)
As
0
1
10
100
Pb co
ncen
trat
ion
(mg
kg) Pb
0
2000
4000
6000
8000
10000
12000
K co
ncen
trat
ion
(mg
kg) K
010203040506070
Cu co
ncen
trat
ion
(mg
kg) Cu
010203040506070
Zn co
ncen
trat
ion
(mg
kg) Zn
0
1
10
100
Ni c
once
ntra
tion
(mg
kg) Ni
1
10
100
1000
10000
100000
Fe co
ncen
trat
ion
(mg
kg) Fe
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2 RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Figure 5 Concentration of elements in soil rice husk and rice samples from Korba and Raipur
as Cr K Fe and Pb The possible barrier role of rice husk isinteresting and it can be hypothesized also for Mn Ba andSr Unfortunately it is not clear in the case of Cu Ni Zn RbBi Ti and V
4 Conclusions
This work reports the chemical composition study of soilsrice and rice husk from Korba and Raipur (India) by means
Journal of Chemistry 11
of TXRF Results show some metals uptake from soil to ricein particular Pb and Cr from the Raipur region The noveltyof this study is the chemical characterization of rice made inparallel with the analysis of soils and corresponding rice huskA detailed analysis of all the data shows that rice husk accu-mulates more heavy metals than rice suggesting a possiblebarrier effect of the husk Despite that dedicated studiesshould be done to verify the clear role of husk and other para-meters such as rice species soils characteristics (pH claycontent and organic matter) and other variables Based onthe extremely interesting results obtained in this study someapproaches may be developed to promote low metals accu-mulation in rice
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study was supported by LIFE+ the financial instrumentof the European Community to support environmentalprojects (LIFE+ 2011 Project ENVIT000256) The authorsare grateful to Directorate-General Environment EuropeanCommission for inclusion of COSMOS-RICE Project inScience for Environment Policy Information Service (seehttpeceuropaeuenvironmentintegrationresearchnew-salertpdf383na2 enpdf) The authors acknowledge Profe-ssor Patel School of Studies in Chemistry Pt RavishankarShukla University Raipur India for the support in samplescollection
References
[1] C Huamain Z Chunrong T Cong and Z Yongguan ldquoHeavymetal pollution in soils in China status and countermeasuresrdquoAmbio vol 28 no 2 pp 130ndash134 1999
[2] M E Watanabe ldquoPhytoremediation on the brink of commer-cializationrdquo Environmental Science amp Technology vol 31 pp82Andash187A 1997
[3] S Uchida K Tagami and N Ishikawa ldquoConcentration soil-to-plant transfer factor and soil-soil solution distribution coeffi-cient of selenium in the surface environment -9106rdquo in Proceed-ings of the Symposium onWasteManagement (WM rsquo09 ) pp 1ndash5Phoenix Ariz USA March 2009
[4] X F Hu Y Jiang Y Shu X Hu L Liu and F Luo ldquoEffectsof mining wastewater discharges on heavy metal pollution andsoil enzyme activity of the paddy fieldsrdquo Journal of GeochemicalExploration vol 147 part B pp 139ndash150 2014
[5] A Sekara M Poniedziałek J Ciura and E Jedrszczyk ldquoCad-mium and lead accumulation and distribution in the organs ofnine crops implications for phytoremediationrdquo Polish Journalof Environmental Studies vol 14 no 4 pp 509ndash516 2005
[6] R Stone ldquoFood safetymdasharsenic and paddy rice a neglectedcancer riskrdquo Science vol 321 no 5886 pp 184ndash185 2008
[7] Committee for the Common Organisation of Agricultural Mar-kets 11 2014 httpeceuropaeuagriculturecerealspresenta-tionsricemarket-situation enpdf
[8] K R Dikshit and J E Schwartzberg ldquoIndia iI paeserdquo in Enci-clopedia Britannica pp 9ndash10 2007
[9] K M Omatola and A D Onojah ldquoElemental analysis of ricehusk ash using X-ray fluorescence techniquerdquo InternationalJournal of Physical Sciences vol 4 no 4 pp 189ndash193 2009
[10] L Sun and K Gong ldquoSilicon-based materials from rice husksand their applicationsrdquo Industrial and Engineering ChemistryResearch vol 40 no 25 pp 5861ndash5877 2001
[11] S Sugita ldquoOn the economical production of large quantities ofhighly reactive rice husk ashrdquo in Proceedings of the InternationalSymposium on Innovative World of Concrete (ICI-IWC rsquo93) pp2 3ndash71 1993
[12] I R Shaikh and A A Shaikh ldquoUtilization of wheat husk ashas silica source for the synthesis of MCM-41 type mesoporoussilicates a sustainable approach towards valorization of the agri-cultural waste streamrdquo Research Journal of Chemical Sciencesvol 3 pp 66ndash72 2013
[13] K M Omatola and A D Onojah ldquoRice husk as a potentialsource of high technological raw materials a reviewrdquo Journalof Polymer Science Innovation vol 4 pp 30ndash35 2012
[14] A Bosio N Rodella A Gianoncelli et al ldquoA new method toinertize incinerator toxic fly ash with silica from rice husk ashrdquoEnvironmental Chemistry Letters vol 11 no 4 pp 329ndash3332013
[15] A Bosio A Zacco L Borgese et al ldquoA sustainable technologyfor Pb and Zn stabilization based on the use of only wastematerials a green chemistry approach to avoid chemicals andpromote CO
2sequestrationrdquoChemical Engineering Journal vol
253 pp 377ndash384 2014[16] A Taylor S Branch M P Day M Patriarca and M White
ldquoAtomic spectrometry update Clinical and biological materialsfoods and beveragesrdquo Journal of Analytical Atomic Spectrometryvol 24 no 4 pp 535ndash579 2009
[17] K S Patel K Shrivas P Hoffmann and N Jakubowski ldquoAsurvey of lead pollution in Chhattisgarh State central IndiardquoEnvironmental Geochemistry and Health vol 28 no 1-2 pp 11ndash17 2006
[18] K S Patel K Shrivas R Brandt N Jakubowski W Corns andP Hoffmann ldquoArsenic contamination in water soil sedimentand rice of central Indiardquo Environmental Geochemistry andHealth vol 27 no 2 pp 131ndash145 2005
[19] B Giri K S Patel N K Jaiswal et al ldquoComposition and sourcesof organic tracers in aerosol particles of industrial central IndiardquoAtmospheric Research vol 120-121 pp 312ndash324 2013
[20] httpwwwepagovoswhazardtestmethodssw846pdfs3050bpdf
[21] L Borgese A Zacco E Bontempi et al ldquoTotal reflection of x-ray fluorescence (TXRF) amature technique for environmentalchemical nanoscale metrologyrdquoMeasurement Science and Tech-nology vol 20 no 8 Article ID 084027 2009
[22] F Bilo L Borgese D Cazzago et al ldquoTXRF analysis ofsoils and sediments to assess environmental contaminationrdquoEnvironmental Science and Pollution Research vol 21 no 23 pp13208ndash13214 2014
[23] Esdat 2000 Dutch Target and Intervention Values The newDutch list 2000 httpwwwesdatnet
[24] A Kabata-Pendias ldquoEnvironmental biogeochemistrymdashoutlineof the developmentrdquo Przeglad Geologiczny vol 49 no 10 pp957ndash959 2001
[25] S Srinivasa Gowd M Ramakrishna Reddy and P K GovilldquoAssessment of heavy metal contamination in soils at Jajmau
12 Journal of Chemistry
(Kanpur) and Unnao industrial areas of the Ganga Plain UttarPradesh Indiardquo Journal ofHazardousMaterials vol 174 no 1ndash3pp 113ndash121 2010
[26] K S Patel A Verma N K Jaiswal et al ldquoArsenic concentrationin soil rice and straw in central Indiardquo in Proceedings of the 4thInternational Congress on Arsenic in the Environment pp 508ndash509 July 2012
[27] A Kabata-Pendias Trace Elements in Soils and Plants Technol-ogy amp Engineering CRC Press 3rd edition 2000
[28] A D Jacobson and J D Blum ldquoCaSr and 87Sr86Sr geochem-istry of disseminated calcite in Himalayan silicate rocks fromNanga Parbat influence on river-water chemistryrdquoGeology vol28 no 5 pp 463ndash466 2000
[29] Y N Vodyanitskii ldquoCriteria of the technogenic nature ofheavy metals and metalloids in soils a review of publicationsrdquoEurasian Soil Science vol 42 no 9 pp 1053ndash1061 2009
[30] H Hoefler C Streli P Wobrauschek M Ovari and G ZarayldquoAnalysis of low Z elements in various environmental sampleswith total reflection X-ray fluorescence (TXRF) spectrometryrdquoSpectrochimica Acta Part B Atomic Spectroscopy vol 61 no 10-11 pp 1135ndash1140 2006
[31] K K Taha I M Shmou H M Osman and M H ShayoubldquoSoil-plant transfer and accumulation factors for trace elementsat the Blue and White Nilesrdquo Journal of Applied and IndustrialSciences vol 1 pp 97ndash102 2013
[32] H Papaefthymiou G Papatheodorou A Moustakli DChristodoulou and M Geraga ldquoNatural radionuclides and137Cs distributions and their relationship with sedimentologicalprocesses in Patras Harbour Greecerdquo Journal of EnvironmentalRadioactivity vol 94 no 2 pp 55ndash74 2007
[33] J Fu Q Zhou J Liu et al ldquoHigh levels of heavy metals inrice (Oryza sativa L) from a typical E-waste recycling areain southeast China and its potential risk to human healthrdquoChemosphere vol 71 no 7 pp 1269ndash1275 2008
[34] T D Phuong P Van Chuong D T Khiem and S Kokot ldquoEle-mental content of Vietnamese rice Part 1 Sampling analysisand comparison with previous studiesrdquo Analyst vol 124 no 4pp 553ndash560 1999
[35] S W Al Rmalli P I Haris C F Harrington and M AyubldquoA survey of arsenic in foodstuffs on sale in the UnitedKingdom and imported from Bangladeshrdquo Science of the TotalEnvironment vol 337 no 1ndash3 pp 23ndash30 2005
[36] C Fangmin Z Ningchun X Haiming et al ldquoCadmium andlead contamination in japonica rice grains and its variationamong the different locations in southeast Chinardquo Science of theTotal Environment vol 359 no 1ndash3 pp 156ndash166 2006
[37] National Programme on Safety Food SafetyMilled Rice Criteriaof PR China (NY5115-2002) China Ministry of AgricultureBeijing China 2002
[38] FAOWHOCodexAlimentariusGeneral Standards for Contam-inants and Toxins in Food Schedule1 Maximum and GuidelineLevels for Contaminants and Toxins in Food Joint FAOWHOFood Standards Programme Reference CXFAC 0216 CodexCommittee Rotterdam The Netherlands 2002
[39] The Ministry of Health of China GB 2762-2012 Standards forChinese Food Sanitation TheMinistry of Health of China 2012
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
10 Journal of Chemistry
0
1
10
100
1000Cr
conc
entr
atio
n (m
gkg
)
Samples
Cr
1
10
100
As c
once
ntra
tion
(mg
kg)
As
0
1
10
100
Pb co
ncen
trat
ion
(mg
kg) Pb
0
2000
4000
6000
8000
10000
12000
K co
ncen
trat
ion
(mg
kg) K
010203040506070
Cu co
ncen
trat
ion
(mg
kg) Cu
010203040506070
Zn co
ncen
trat
ion
(mg
kg) Zn
0
1
10
100
Ni c
once
ntra
tion
(mg
kg) Ni
1
10
100
1000
10000
100000
Fe co
ncen
trat
ion
(mg
kg) Fe
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1_K
S3_K
S5_K
S1B_
RS2
B_R
S3B_
RS4
B_R
S5B_
R2
RH_K
4RH
_K1
RH_R
3RH
_R5
RH_R
2R_
K4
R_K
1R_
R3
R_R
5R_
R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2 RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Samples
S1
_KS3
_KS5
_KS1
B_R
S2
B_R
S3
B_R
S4
B_R
S5
B_R
2RH
_K4
RH_K
1RH
_R3
RH_R
5RH
_R2
R_K
4R_
K1
R_R
3R_
R5
R_R
Figure 5 Concentration of elements in soil rice husk and rice samples from Korba and Raipur
as Cr K Fe and Pb The possible barrier role of rice husk isinteresting and it can be hypothesized also for Mn Ba andSr Unfortunately it is not clear in the case of Cu Ni Zn RbBi Ti and V
4 Conclusions
This work reports the chemical composition study of soilsrice and rice husk from Korba and Raipur (India) by means
Journal of Chemistry 11
of TXRF Results show some metals uptake from soil to ricein particular Pb and Cr from the Raipur region The noveltyof this study is the chemical characterization of rice made inparallel with the analysis of soils and corresponding rice huskA detailed analysis of all the data shows that rice husk accu-mulates more heavy metals than rice suggesting a possiblebarrier effect of the husk Despite that dedicated studiesshould be done to verify the clear role of husk and other para-meters such as rice species soils characteristics (pH claycontent and organic matter) and other variables Based onthe extremely interesting results obtained in this study someapproaches may be developed to promote low metals accu-mulation in rice
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study was supported by LIFE+ the financial instrumentof the European Community to support environmentalprojects (LIFE+ 2011 Project ENVIT000256) The authorsare grateful to Directorate-General Environment EuropeanCommission for inclusion of COSMOS-RICE Project inScience for Environment Policy Information Service (seehttpeceuropaeuenvironmentintegrationresearchnew-salertpdf383na2 enpdf) The authors acknowledge Profe-ssor Patel School of Studies in Chemistry Pt RavishankarShukla University Raipur India for the support in samplescollection
References
[1] C Huamain Z Chunrong T Cong and Z Yongguan ldquoHeavymetal pollution in soils in China status and countermeasuresrdquoAmbio vol 28 no 2 pp 130ndash134 1999
[2] M E Watanabe ldquoPhytoremediation on the brink of commer-cializationrdquo Environmental Science amp Technology vol 31 pp82Andash187A 1997
[3] S Uchida K Tagami and N Ishikawa ldquoConcentration soil-to-plant transfer factor and soil-soil solution distribution coeffi-cient of selenium in the surface environment -9106rdquo in Proceed-ings of the Symposium onWasteManagement (WM rsquo09 ) pp 1ndash5Phoenix Ariz USA March 2009
[4] X F Hu Y Jiang Y Shu X Hu L Liu and F Luo ldquoEffectsof mining wastewater discharges on heavy metal pollution andsoil enzyme activity of the paddy fieldsrdquo Journal of GeochemicalExploration vol 147 part B pp 139ndash150 2014
[5] A Sekara M Poniedziałek J Ciura and E Jedrszczyk ldquoCad-mium and lead accumulation and distribution in the organs ofnine crops implications for phytoremediationrdquo Polish Journalof Environmental Studies vol 14 no 4 pp 509ndash516 2005
[6] R Stone ldquoFood safetymdasharsenic and paddy rice a neglectedcancer riskrdquo Science vol 321 no 5886 pp 184ndash185 2008
[7] Committee for the Common Organisation of Agricultural Mar-kets 11 2014 httpeceuropaeuagriculturecerealspresenta-tionsricemarket-situation enpdf
[8] K R Dikshit and J E Schwartzberg ldquoIndia iI paeserdquo in Enci-clopedia Britannica pp 9ndash10 2007
[9] K M Omatola and A D Onojah ldquoElemental analysis of ricehusk ash using X-ray fluorescence techniquerdquo InternationalJournal of Physical Sciences vol 4 no 4 pp 189ndash193 2009
[10] L Sun and K Gong ldquoSilicon-based materials from rice husksand their applicationsrdquo Industrial and Engineering ChemistryResearch vol 40 no 25 pp 5861ndash5877 2001
[11] S Sugita ldquoOn the economical production of large quantities ofhighly reactive rice husk ashrdquo in Proceedings of the InternationalSymposium on Innovative World of Concrete (ICI-IWC rsquo93) pp2 3ndash71 1993
[12] I R Shaikh and A A Shaikh ldquoUtilization of wheat husk ashas silica source for the synthesis of MCM-41 type mesoporoussilicates a sustainable approach towards valorization of the agri-cultural waste streamrdquo Research Journal of Chemical Sciencesvol 3 pp 66ndash72 2013
[13] K M Omatola and A D Onojah ldquoRice husk as a potentialsource of high technological raw materials a reviewrdquo Journalof Polymer Science Innovation vol 4 pp 30ndash35 2012
[14] A Bosio N Rodella A Gianoncelli et al ldquoA new method toinertize incinerator toxic fly ash with silica from rice husk ashrdquoEnvironmental Chemistry Letters vol 11 no 4 pp 329ndash3332013
[15] A Bosio A Zacco L Borgese et al ldquoA sustainable technologyfor Pb and Zn stabilization based on the use of only wastematerials a green chemistry approach to avoid chemicals andpromote CO
2sequestrationrdquoChemical Engineering Journal vol
253 pp 377ndash384 2014[16] A Taylor S Branch M P Day M Patriarca and M White
ldquoAtomic spectrometry update Clinical and biological materialsfoods and beveragesrdquo Journal of Analytical Atomic Spectrometryvol 24 no 4 pp 535ndash579 2009
[17] K S Patel K Shrivas P Hoffmann and N Jakubowski ldquoAsurvey of lead pollution in Chhattisgarh State central IndiardquoEnvironmental Geochemistry and Health vol 28 no 1-2 pp 11ndash17 2006
[18] K S Patel K Shrivas R Brandt N Jakubowski W Corns andP Hoffmann ldquoArsenic contamination in water soil sedimentand rice of central Indiardquo Environmental Geochemistry andHealth vol 27 no 2 pp 131ndash145 2005
[19] B Giri K S Patel N K Jaiswal et al ldquoComposition and sourcesof organic tracers in aerosol particles of industrial central IndiardquoAtmospheric Research vol 120-121 pp 312ndash324 2013
[20] httpwwwepagovoswhazardtestmethodssw846pdfs3050bpdf
[21] L Borgese A Zacco E Bontempi et al ldquoTotal reflection of x-ray fluorescence (TXRF) amature technique for environmentalchemical nanoscale metrologyrdquoMeasurement Science and Tech-nology vol 20 no 8 Article ID 084027 2009
[22] F Bilo L Borgese D Cazzago et al ldquoTXRF analysis ofsoils and sediments to assess environmental contaminationrdquoEnvironmental Science and Pollution Research vol 21 no 23 pp13208ndash13214 2014
[23] Esdat 2000 Dutch Target and Intervention Values The newDutch list 2000 httpwwwesdatnet
[24] A Kabata-Pendias ldquoEnvironmental biogeochemistrymdashoutlineof the developmentrdquo Przeglad Geologiczny vol 49 no 10 pp957ndash959 2001
[25] S Srinivasa Gowd M Ramakrishna Reddy and P K GovilldquoAssessment of heavy metal contamination in soils at Jajmau
12 Journal of Chemistry
(Kanpur) and Unnao industrial areas of the Ganga Plain UttarPradesh Indiardquo Journal ofHazardousMaterials vol 174 no 1ndash3pp 113ndash121 2010
[26] K S Patel A Verma N K Jaiswal et al ldquoArsenic concentrationin soil rice and straw in central Indiardquo in Proceedings of the 4thInternational Congress on Arsenic in the Environment pp 508ndash509 July 2012
[27] A Kabata-Pendias Trace Elements in Soils and Plants Technol-ogy amp Engineering CRC Press 3rd edition 2000
[28] A D Jacobson and J D Blum ldquoCaSr and 87Sr86Sr geochem-istry of disseminated calcite in Himalayan silicate rocks fromNanga Parbat influence on river-water chemistryrdquoGeology vol28 no 5 pp 463ndash466 2000
[29] Y N Vodyanitskii ldquoCriteria of the technogenic nature ofheavy metals and metalloids in soils a review of publicationsrdquoEurasian Soil Science vol 42 no 9 pp 1053ndash1061 2009
[30] H Hoefler C Streli P Wobrauschek M Ovari and G ZarayldquoAnalysis of low Z elements in various environmental sampleswith total reflection X-ray fluorescence (TXRF) spectrometryrdquoSpectrochimica Acta Part B Atomic Spectroscopy vol 61 no 10-11 pp 1135ndash1140 2006
[31] K K Taha I M Shmou H M Osman and M H ShayoubldquoSoil-plant transfer and accumulation factors for trace elementsat the Blue and White Nilesrdquo Journal of Applied and IndustrialSciences vol 1 pp 97ndash102 2013
[32] H Papaefthymiou G Papatheodorou A Moustakli DChristodoulou and M Geraga ldquoNatural radionuclides and137Cs distributions and their relationship with sedimentologicalprocesses in Patras Harbour Greecerdquo Journal of EnvironmentalRadioactivity vol 94 no 2 pp 55ndash74 2007
[33] J Fu Q Zhou J Liu et al ldquoHigh levels of heavy metals inrice (Oryza sativa L) from a typical E-waste recycling areain southeast China and its potential risk to human healthrdquoChemosphere vol 71 no 7 pp 1269ndash1275 2008
[34] T D Phuong P Van Chuong D T Khiem and S Kokot ldquoEle-mental content of Vietnamese rice Part 1 Sampling analysisand comparison with previous studiesrdquo Analyst vol 124 no 4pp 553ndash560 1999
[35] S W Al Rmalli P I Haris C F Harrington and M AyubldquoA survey of arsenic in foodstuffs on sale in the UnitedKingdom and imported from Bangladeshrdquo Science of the TotalEnvironment vol 337 no 1ndash3 pp 23ndash30 2005
[36] C Fangmin Z Ningchun X Haiming et al ldquoCadmium andlead contamination in japonica rice grains and its variationamong the different locations in southeast Chinardquo Science of theTotal Environment vol 359 no 1ndash3 pp 156ndash166 2006
[37] National Programme on Safety Food SafetyMilled Rice Criteriaof PR China (NY5115-2002) China Ministry of AgricultureBeijing China 2002
[38] FAOWHOCodexAlimentariusGeneral Standards for Contam-inants and Toxins in Food Schedule1 Maximum and GuidelineLevels for Contaminants and Toxins in Food Joint FAOWHOFood Standards Programme Reference CXFAC 0216 CodexCommittee Rotterdam The Netherlands 2002
[39] The Ministry of Health of China GB 2762-2012 Standards forChinese Food Sanitation TheMinistry of Health of China 2012
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 11
of TXRF Results show some metals uptake from soil to ricein particular Pb and Cr from the Raipur region The noveltyof this study is the chemical characterization of rice made inparallel with the analysis of soils and corresponding rice huskA detailed analysis of all the data shows that rice husk accu-mulates more heavy metals than rice suggesting a possiblebarrier effect of the husk Despite that dedicated studiesshould be done to verify the clear role of husk and other para-meters such as rice species soils characteristics (pH claycontent and organic matter) and other variables Based onthe extremely interesting results obtained in this study someapproaches may be developed to promote low metals accu-mulation in rice
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study was supported by LIFE+ the financial instrumentof the European Community to support environmentalprojects (LIFE+ 2011 Project ENVIT000256) The authorsare grateful to Directorate-General Environment EuropeanCommission for inclusion of COSMOS-RICE Project inScience for Environment Policy Information Service (seehttpeceuropaeuenvironmentintegrationresearchnew-salertpdf383na2 enpdf) The authors acknowledge Profe-ssor Patel School of Studies in Chemistry Pt RavishankarShukla University Raipur India for the support in samplescollection
References
[1] C Huamain Z Chunrong T Cong and Z Yongguan ldquoHeavymetal pollution in soils in China status and countermeasuresrdquoAmbio vol 28 no 2 pp 130ndash134 1999
[2] M E Watanabe ldquoPhytoremediation on the brink of commer-cializationrdquo Environmental Science amp Technology vol 31 pp82Andash187A 1997
[3] S Uchida K Tagami and N Ishikawa ldquoConcentration soil-to-plant transfer factor and soil-soil solution distribution coeffi-cient of selenium in the surface environment -9106rdquo in Proceed-ings of the Symposium onWasteManagement (WM rsquo09 ) pp 1ndash5Phoenix Ariz USA March 2009
[4] X F Hu Y Jiang Y Shu X Hu L Liu and F Luo ldquoEffectsof mining wastewater discharges on heavy metal pollution andsoil enzyme activity of the paddy fieldsrdquo Journal of GeochemicalExploration vol 147 part B pp 139ndash150 2014
[5] A Sekara M Poniedziałek J Ciura and E Jedrszczyk ldquoCad-mium and lead accumulation and distribution in the organs ofnine crops implications for phytoremediationrdquo Polish Journalof Environmental Studies vol 14 no 4 pp 509ndash516 2005
[6] R Stone ldquoFood safetymdasharsenic and paddy rice a neglectedcancer riskrdquo Science vol 321 no 5886 pp 184ndash185 2008
[7] Committee for the Common Organisation of Agricultural Mar-kets 11 2014 httpeceuropaeuagriculturecerealspresenta-tionsricemarket-situation enpdf
[8] K R Dikshit and J E Schwartzberg ldquoIndia iI paeserdquo in Enci-clopedia Britannica pp 9ndash10 2007
[9] K M Omatola and A D Onojah ldquoElemental analysis of ricehusk ash using X-ray fluorescence techniquerdquo InternationalJournal of Physical Sciences vol 4 no 4 pp 189ndash193 2009
[10] L Sun and K Gong ldquoSilicon-based materials from rice husksand their applicationsrdquo Industrial and Engineering ChemistryResearch vol 40 no 25 pp 5861ndash5877 2001
[11] S Sugita ldquoOn the economical production of large quantities ofhighly reactive rice husk ashrdquo in Proceedings of the InternationalSymposium on Innovative World of Concrete (ICI-IWC rsquo93) pp2 3ndash71 1993
[12] I R Shaikh and A A Shaikh ldquoUtilization of wheat husk ashas silica source for the synthesis of MCM-41 type mesoporoussilicates a sustainable approach towards valorization of the agri-cultural waste streamrdquo Research Journal of Chemical Sciencesvol 3 pp 66ndash72 2013
[13] K M Omatola and A D Onojah ldquoRice husk as a potentialsource of high technological raw materials a reviewrdquo Journalof Polymer Science Innovation vol 4 pp 30ndash35 2012
[14] A Bosio N Rodella A Gianoncelli et al ldquoA new method toinertize incinerator toxic fly ash with silica from rice husk ashrdquoEnvironmental Chemistry Letters vol 11 no 4 pp 329ndash3332013
[15] A Bosio A Zacco L Borgese et al ldquoA sustainable technologyfor Pb and Zn stabilization based on the use of only wastematerials a green chemistry approach to avoid chemicals andpromote CO
2sequestrationrdquoChemical Engineering Journal vol
253 pp 377ndash384 2014[16] A Taylor S Branch M P Day M Patriarca and M White
ldquoAtomic spectrometry update Clinical and biological materialsfoods and beveragesrdquo Journal of Analytical Atomic Spectrometryvol 24 no 4 pp 535ndash579 2009
[17] K S Patel K Shrivas P Hoffmann and N Jakubowski ldquoAsurvey of lead pollution in Chhattisgarh State central IndiardquoEnvironmental Geochemistry and Health vol 28 no 1-2 pp 11ndash17 2006
[18] K S Patel K Shrivas R Brandt N Jakubowski W Corns andP Hoffmann ldquoArsenic contamination in water soil sedimentand rice of central Indiardquo Environmental Geochemistry andHealth vol 27 no 2 pp 131ndash145 2005
[19] B Giri K S Patel N K Jaiswal et al ldquoComposition and sourcesof organic tracers in aerosol particles of industrial central IndiardquoAtmospheric Research vol 120-121 pp 312ndash324 2013
[20] httpwwwepagovoswhazardtestmethodssw846pdfs3050bpdf
[21] L Borgese A Zacco E Bontempi et al ldquoTotal reflection of x-ray fluorescence (TXRF) amature technique for environmentalchemical nanoscale metrologyrdquoMeasurement Science and Tech-nology vol 20 no 8 Article ID 084027 2009
[22] F Bilo L Borgese D Cazzago et al ldquoTXRF analysis ofsoils and sediments to assess environmental contaminationrdquoEnvironmental Science and Pollution Research vol 21 no 23 pp13208ndash13214 2014
[23] Esdat 2000 Dutch Target and Intervention Values The newDutch list 2000 httpwwwesdatnet
[24] A Kabata-Pendias ldquoEnvironmental biogeochemistrymdashoutlineof the developmentrdquo Przeglad Geologiczny vol 49 no 10 pp957ndash959 2001
[25] S Srinivasa Gowd M Ramakrishna Reddy and P K GovilldquoAssessment of heavy metal contamination in soils at Jajmau
12 Journal of Chemistry
(Kanpur) and Unnao industrial areas of the Ganga Plain UttarPradesh Indiardquo Journal ofHazardousMaterials vol 174 no 1ndash3pp 113ndash121 2010
[26] K S Patel A Verma N K Jaiswal et al ldquoArsenic concentrationin soil rice and straw in central Indiardquo in Proceedings of the 4thInternational Congress on Arsenic in the Environment pp 508ndash509 July 2012
[27] A Kabata-Pendias Trace Elements in Soils and Plants Technol-ogy amp Engineering CRC Press 3rd edition 2000
[28] A D Jacobson and J D Blum ldquoCaSr and 87Sr86Sr geochem-istry of disseminated calcite in Himalayan silicate rocks fromNanga Parbat influence on river-water chemistryrdquoGeology vol28 no 5 pp 463ndash466 2000
[29] Y N Vodyanitskii ldquoCriteria of the technogenic nature ofheavy metals and metalloids in soils a review of publicationsrdquoEurasian Soil Science vol 42 no 9 pp 1053ndash1061 2009
[30] H Hoefler C Streli P Wobrauschek M Ovari and G ZarayldquoAnalysis of low Z elements in various environmental sampleswith total reflection X-ray fluorescence (TXRF) spectrometryrdquoSpectrochimica Acta Part B Atomic Spectroscopy vol 61 no 10-11 pp 1135ndash1140 2006
[31] K K Taha I M Shmou H M Osman and M H ShayoubldquoSoil-plant transfer and accumulation factors for trace elementsat the Blue and White Nilesrdquo Journal of Applied and IndustrialSciences vol 1 pp 97ndash102 2013
[32] H Papaefthymiou G Papatheodorou A Moustakli DChristodoulou and M Geraga ldquoNatural radionuclides and137Cs distributions and their relationship with sedimentologicalprocesses in Patras Harbour Greecerdquo Journal of EnvironmentalRadioactivity vol 94 no 2 pp 55ndash74 2007
[33] J Fu Q Zhou J Liu et al ldquoHigh levels of heavy metals inrice (Oryza sativa L) from a typical E-waste recycling areain southeast China and its potential risk to human healthrdquoChemosphere vol 71 no 7 pp 1269ndash1275 2008
[34] T D Phuong P Van Chuong D T Khiem and S Kokot ldquoEle-mental content of Vietnamese rice Part 1 Sampling analysisand comparison with previous studiesrdquo Analyst vol 124 no 4pp 553ndash560 1999
[35] S W Al Rmalli P I Haris C F Harrington and M AyubldquoA survey of arsenic in foodstuffs on sale in the UnitedKingdom and imported from Bangladeshrdquo Science of the TotalEnvironment vol 337 no 1ndash3 pp 23ndash30 2005
[36] C Fangmin Z Ningchun X Haiming et al ldquoCadmium andlead contamination in japonica rice grains and its variationamong the different locations in southeast Chinardquo Science of theTotal Environment vol 359 no 1ndash3 pp 156ndash166 2006
[37] National Programme on Safety Food SafetyMilled Rice Criteriaof PR China (NY5115-2002) China Ministry of AgricultureBeijing China 2002
[38] FAOWHOCodexAlimentariusGeneral Standards for Contam-inants and Toxins in Food Schedule1 Maximum and GuidelineLevels for Contaminants and Toxins in Food Joint FAOWHOFood Standards Programme Reference CXFAC 0216 CodexCommittee Rotterdam The Netherlands 2002
[39] The Ministry of Health of China GB 2762-2012 Standards forChinese Food Sanitation TheMinistry of Health of China 2012
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
12 Journal of Chemistry
(Kanpur) and Unnao industrial areas of the Ganga Plain UttarPradesh Indiardquo Journal ofHazardousMaterials vol 174 no 1ndash3pp 113ndash121 2010
[26] K S Patel A Verma N K Jaiswal et al ldquoArsenic concentrationin soil rice and straw in central Indiardquo in Proceedings of the 4thInternational Congress on Arsenic in the Environment pp 508ndash509 July 2012
[27] A Kabata-Pendias Trace Elements in Soils and Plants Technol-ogy amp Engineering CRC Press 3rd edition 2000
[28] A D Jacobson and J D Blum ldquoCaSr and 87Sr86Sr geochem-istry of disseminated calcite in Himalayan silicate rocks fromNanga Parbat influence on river-water chemistryrdquoGeology vol28 no 5 pp 463ndash466 2000
[29] Y N Vodyanitskii ldquoCriteria of the technogenic nature ofheavy metals and metalloids in soils a review of publicationsrdquoEurasian Soil Science vol 42 no 9 pp 1053ndash1061 2009
[30] H Hoefler C Streli P Wobrauschek M Ovari and G ZarayldquoAnalysis of low Z elements in various environmental sampleswith total reflection X-ray fluorescence (TXRF) spectrometryrdquoSpectrochimica Acta Part B Atomic Spectroscopy vol 61 no 10-11 pp 1135ndash1140 2006
[31] K K Taha I M Shmou H M Osman and M H ShayoubldquoSoil-plant transfer and accumulation factors for trace elementsat the Blue and White Nilesrdquo Journal of Applied and IndustrialSciences vol 1 pp 97ndash102 2013
[32] H Papaefthymiou G Papatheodorou A Moustakli DChristodoulou and M Geraga ldquoNatural radionuclides and137Cs distributions and their relationship with sedimentologicalprocesses in Patras Harbour Greecerdquo Journal of EnvironmentalRadioactivity vol 94 no 2 pp 55ndash74 2007
[33] J Fu Q Zhou J Liu et al ldquoHigh levels of heavy metals inrice (Oryza sativa L) from a typical E-waste recycling areain southeast China and its potential risk to human healthrdquoChemosphere vol 71 no 7 pp 1269ndash1275 2008
[34] T D Phuong P Van Chuong D T Khiem and S Kokot ldquoEle-mental content of Vietnamese rice Part 1 Sampling analysisand comparison with previous studiesrdquo Analyst vol 124 no 4pp 553ndash560 1999
[35] S W Al Rmalli P I Haris C F Harrington and M AyubldquoA survey of arsenic in foodstuffs on sale in the UnitedKingdom and imported from Bangladeshrdquo Science of the TotalEnvironment vol 337 no 1ndash3 pp 23ndash30 2005
[36] C Fangmin Z Ningchun X Haiming et al ldquoCadmium andlead contamination in japonica rice grains and its variationamong the different locations in southeast Chinardquo Science of theTotal Environment vol 359 no 1ndash3 pp 156ndash166 2006
[37] National Programme on Safety Food SafetyMilled Rice Criteriaof PR China (NY5115-2002) China Ministry of AgricultureBeijing China 2002
[38] FAOWHOCodexAlimentariusGeneral Standards for Contam-inants and Toxins in Food Schedule1 Maximum and GuidelineLevels for Contaminants and Toxins in Food Joint FAOWHOFood Standards Programme Reference CXFAC 0216 CodexCommittee Rotterdam The Netherlands 2002
[39] The Ministry of Health of China GB 2762-2012 Standards forChinese Food Sanitation TheMinistry of Health of China 2012
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of