Research Article Manganese Fractionation in Soils after...

Research ArticleManganese Fractionation in Soils after Application of MunicipalSolid Wastes Compost in Two Consecutive Years

Molod Samiei and Abdolamir Bostani

Department of Soil Science Shahed University Tehran Iran

Correspondence should be addressed to Abdolamir Bostani bostanishahedacir

Received 15 May 2016 Revised 5 August 2016 Accepted 23 August 2016

Academic Editor Marco Trevisan

Copyright copy 2016 M Samiei and A Bostani This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

In order to study the effect of Tehran municipal solid wastes compost on manganese accumulation in soil and to determine itsconcentration in any readily available plant forms (exchangeable and carbonates-bonded) Mn-oxides bonded fraction organicmatter bonded fraction and residual fraction in a calcareous soil a factorial experiment based on completely randomized blockdesign (RCBD) was conducted in research field of Shahed university at different levels of municipal solid wastes compost (0 15 30and 60 tonha) as first factor and application times (one- or two-year compost application) as second factor in three replicationsResults showed that by increasing compost level totalMn concentrationDTPA-extractable concentration and amounts existing inall five fractions were increased so lowest and highest amounts of Mn were observed in control and 60 tonha compost applicationBased on results from Mn fractionation using Tessier consecutive extraction method Mn fractions in all samples were in thefollowing order residual gt Fe-Mn oxides gt carbonates-bonded gt organic matter-bonded ≫ exchangeable fractions in whichresidual fraction (RE) at first and second year was dominant rather than other fractions by 3428ndash4304 and 3428ndash4948 percentrespectively Mn concentration in Fe-Mn oxides-bonded fraction at both years was considerable Mn amounts in Fe-Mn oxides-bonded application times were decreased

1 Introduction

The importance of microelements for plants has already beenwell documented in the literature Manganese is an essentialmicronutrient for all organisms playing an important rolein tissue and bone formation in reproductive functions andin carbohydrate and lipid metabolisms and is an importantcofactor in numerous enzymes [1] but at higher levels it canbe toxic In man chronic manganese poisoning affects thecentral nervous system with symptoms resembling those ofParkinsonrsquos diseaseManganese toxicity is a serious constraintto crop cultivation sincemanganese is taken-up by plants andcan easily be passed into the food chain [2 3] Thereforethe determination of manganese in several matrices samplesis very important for some areas such as environmentalchemistry and food control [4] High manganese contenthinders the uptake of calcium and magnesium In turn adeficiency of manganese is most often found in soils that aresaline and alkaline calcareous or peaty [5]

Physiochemical forms of nutrients among soil compo-nents determine nutrients mobility and transferring andconsequently their availability By considering the differentforms of heavy metals in soil and their changes we couldbecome aware of nutrients status and eventually we can planfor decrease of their absorption by plant and consequentlypreventing their contaminant effects by reducing transferof these nutrients to food chain and water resources [6]According to recent definition of international union of pureand applied chemistry (IUPAC) a practice which is widelyused for recognizing nutrients distribution in solid phase isknown as fractionation which is a sequential application ofa chemical extractor collection for consecutive and selectivesolubility of chemical forms of a nutrient which was thoughtto be holder of major part of interested nutrients [7]

In order to determine plantrsquos available form of nutrientsdifferent extractors were used It should be noted that initialpurpose of each chemical extraction method is to evaluatethe available amount of a nutrient for plants [8] Consecutive

Hindawi Publishing CorporationApplied and Environmental Soil ScienceVolume 2016 Article ID 5202789 8 pageshttpdxdoiorg10115520165202789

2 Applied and Environmental Soil Science

extraction method was developed as common and essentialfor fractionation of trace and necessary elements such ascadmium cobalt nickel lead cupper iron and manganesein soil and deposits and divided them into five fractionsincluding exchangeable carbonate- iron-manganese oxides-organic matter-bonded and residual fractions Althoughusing of this method is time consuming it gives comprehen-sive information about trace elements origin occurring waybioavailability mobility and transferring to users [7]

Nadaska et al [9] studied environmental aspects of man-ganese using consecutive extraction and believed that thismethod gave accurate information about origin occurrenceway bioavailability potential mobility and metals transfer innatural environments Mescouto et al [10] showed that thehighest concentration of iron and manganese is associatedwith residual fraction Also this study showed that in frac-tions related to iron-manganese oxides iron and manganeseavailability was in the range of 1265139 to 181812mgkg and4851 to 830mgkg respectively

The aim of the present research was to determine thefractionation of manganese in the soil in the conditionsof two-year application of Tehran municipal solid wastecompost in a calcareous soil Our study can contribute tobetter understanding of the multidirectional transformationof those elements and to an evaluation of the amount ofbioavailable forms

2 Methods and Materials

In order to evaluate the different levels of Tehran municipalsolid waste compost on manganese (Mn) concentration anddistribution in different soil fractions an experiment wasconducted in research station of agriculture faculty of ShahedUniversity (35∘341015840N latitude and 51∘341015840E longitude) Withregard to slow releasing of metals frommunicipal solid waste(MSW) compost in addition to different compost applica-tion levels compost application times are tested Thereforeexperiment was conducted as split plot (compost amounts inmain plots and application times in secondary plots) in threereplications on 2011-2012 and 2012-2013 cropping years Butconsidering homogenous conditions in experimental blocksand nonsignificant errors in main plots traits were analyzedas factorial based on completely randomized block design(RCBD) Experimental factors including four levels of MSWapplication (0 15 30 and 60 tonha) were considered as firstfactor and compost application times (annual and biannualapplication) as second factor So main plot characterized infirst year and different treatment levels were added to plots onApril 2012 On April 2012 plots were divided into two partsand in one part compost was added to soil in equal amountof previous year

After few months and reaching balance in soil 24 soilsamples were collected from surface soil of plots and after air-drying and sieving from 2mmsieve some of soil physical andchemical properties were determined including saturationpercent saturated extract preparing EC and pH [11] soiltexture by hydrometer method [12] organic matter by wetoxidation [13] CEC by Bower et al [14] and CaCO

3by

pressured calcimetric method [13] For determination of the

total and available Fe andMn respectively DTPA [15]HNO3

H2O2and HCl [16] methods were used Mn fractionation

was conducted in five fractions exchangeable carbonates-bonded Fe and Mn oxides organic matter-bonded andresidual using consecutive extraction method [17] Finallyelements concentrations were determined by atomic absorp-tion Analytic Jena Contra AA300 Statistical analyses wasconducted by SAS statistical software and graphs were byExcel software

3 Results and Discussion

Results from determination of soil physical and chemi-cal properties before applying treatments are presented inTable 1 After applying compost treatments it is identified thataddition of compost caused the decrease in pH and increasein organic carbon in all levels compared to control Studiedcompost by 25 organic carbon and pH by 27 is classified instandard range defined by soil and water research organiza-tion Also according to definition of recycling organization(2004) for compost classification in Iran this compost dueto high EC amount fell into second degree type Total Mn inmentioned compost was determined as 42664mgkg

31 Effect ofMSWCompost onConcentration andDistributionofMn in Soil Table 2 shows the results on analysis of variance(ANOVA) of the effect of MSW compost on total and DTPA-extractable concentration ofMn in soil Also this table showsthe results for ANOVA of distribution of elements among fivedifferent fractions including exchangeable (EX) carbonate-bonded (CA) or acid-soluble reductive Fe and Mn oxides-bonded (FM) organic matter-bonded (OM) and residualfraction (RE)

Table 3 shows mean comparisons of total and DTPA-extractable concentrations and existing amounts in five dif-ferent soil fractions for Mn at different levels of municipalsolid waste compost Results showed that by increasingcompost application percent total and DTPA-extractableconcentrations and existing amounts in five different soilfractions of Mn increased which the lowest and highestconcentration in all studied forms observed in control and60 tonha compost treatments respectively Osakwe [18]stated that Mn strongly attached to soil matrix So it isnot readily available to appear in food chain It should benoted that since total Fe and Mn concentrations in soils weremeasured by digestion of separate samples in related acidstotalmeasured forms essentiallywere not equal to total Fe andMn Reyhani Tabar et al [19] found similar results in studyingthe distribution of different forms of Zn in calcareous soilsof Tehran Mohammad and Athamneh [20] reported theincrease in DTPA-extractable Fe and Mn concentration dueto addition of sewage sludge compared to control Theyalso stated that Fe and Mn concentrations increased from382 and 719mgkg in control to 1383 and 3163mgkg inthe highest level of sewage sludge treatment (160 tonha)respectively

Formation of stable metal complexes could decreasesolubility of metal ions in soils [21] Great amount of organic

Applied and Environmental Soil Science 3

Table 1 Results of soil physical and chemical properties

Texture OC () EC (dSm) pH CCE () CEC (cmolkg) Fe (mgkg) Mn (mgkg)Total Available Total Available

Loam 117 10 828 115 1213 257125 278 124792 1189

Table 2 Analysis of variance and mean square values of total manganese DTPA and various components of municipal solid waste compostin two years

Sources of variation Degree of freedom MnEX CA FM OM RE DTPA Total

Repeat 2 00047ns 23752ns 20839ns 0063ns 715367ns 1845ns 158327lowast

MSW 3 6224lowastlowast 5114509lowastlowast 1239928lowastlowast 7563lowastlowast 83627076lowastlowast 18613lowastlowast 34566166lowastlowast

Application time 1 0484lowastlowast 338701lowast 606417lowastlowast 12499lowastlowast 5410251lowastlowast 37697lowastlowast 4686376lowastlowast

Time timesMSW 3 0077lowastlowast 144723lowast 85137lowast 1769lowastlowast 6955364lowast 4308ns 1130339lowastlowast

Error 14 000465 41417 17148 0065 360789 1609 389Coefficient of variation 1575 2805 1105 4258 8757 877 047lowast lowastlowast and ns respectively mean significant at 5 significant at 1 and nonsignificant

Table 3 Mean comparison of total and DTPA-extractable concentrations and existing amounts in 5 different soil fractions for Mnrespectively at different levels of MSW

MSW Mn

Thaminus1 EX CA FM OM RE DTPA Total(mg kgminus1)

Control 3156d 19264d 356347d 4466d 29042c 11889b 1247917d

15 3871c 220827c 37206c 5945c 38883b 14802a 1288458c

30 4825b 246453b 378833b 6493b 43104b 15269a 1324375b

60 5461a 258413a 3908a 7088a 57471a 15847a 1425272a

Similar letters in each column show nonsignificant difference at 5 probability level according to Duncanrsquos multiple range test

matter its oxidation and destruction and neutral pH incompost results in increasingmicronutrients availability suchas Fe Mn Zn and Cu The highest metal concentration wasobserved in the greatest compost treatments [22]The highestconcentrations of carbonates-bonded Mn were observed inplots in which 60 tonha compost was applied This possiblyis due to reaction of micronutrients with CO

2resulting from

increasing in microbial activity due to higher amounts ofcompost application [21]

Table 4 shows the results of mean comparison of theeffect of municipal solid wastes compost application timeson Mn concentration Based on these results it is rec-ognized that addition of 2 times municipal solid wastescompost over 2 years to soil significantly increased totaland DTPA-extractable concentrations in all fractions exceptfor carbonates-bonded fraction compared to one-time appli-cation Total DTPA-extractable exchangeable reductiveoxidative and residual concentrations of Mn in second yearcompared to first year by 213 1899 678 273 2736 and254 percent respectively It should be noted that carbonates-bonded fraction concentration in Mn at two-year compostapplication decreased about 321 percent compared to one-year application Sorrenti et al [23] in the study of comparing

the soil application of iron chelate and municipal solidwastes compost on nutrition status management of pear treesgrown on calcareous soil showed that annual application ofmunicipal solid wastes compost is effective in improving ironnutrition status of pear andhas negative impact on availabilityof cations such as Mn K and Cu for plant absorption Socompost could serve as an inexpensive and valuable strategyfor improving productivity of fruit trees or orchards whichhas environmental and cropping advantages

32 Soil Mn Fractionation In the present study consecutiveextractionmethod as described byTessier et al [17] was usedforMn fractionation Asmentioned earlier in Tessiermethodtotal metal concentration could be divided into five fractionsincluding exchangeable (EX) carbonate-bonded (CA) ironandmanganese oxides-bonded (FM) organic matter bonded(OM) and residual fractions (RE) Consecutive extractionmethod is useful for indirect evaluation of potential mobilityand availability of metals for plants in soil Assuming thatavailability is related to solubility it can be concluded thatmetal availability decreased in following order dissolved +exchangeable gt carbonate gt Fe- and Mn- oxides gt residual


Table 4 Mean comparison of total and DTPA-extractable concentrations and existing amounts in 5 different soil fractions for Mnrespectively at application times

Application times Mn


One time 4186b 23334a 369483b 5276b 37377b 13198b 1307532b

2 times 447a 225827b 379537a 672a 46873a 15705a 1335479a


The above order just provides qualitative information aboutnutrients availability for plants [24]

Table 2 shows the significant effect of different com-post levels and their application times on total and DTPA-extractable Mn concentrations (119875 lt 001) In spite of signif-icant differences of interactions of compost and applicationtimes on total Mn concentration (119875 lt 001) the effectof this factor on DTPA-extractable Mn concentration wasnot significant The effect of compost levels for all fractions(119875 lt 001) and the effect of application times on allfractions except for carbonates-bonded fraction (119875 lt 005)and also the interaction of compost level and applicationtimes on exchangeable and organic matter bonded fraction(119875 lt 001) and in carbonates-bonded Fe- and Mn-oxidesand residual fraction (119875 lt 005) were significant (Table 2)Mean comparison of total Mn exchangeable Mn carbonate-bonded Fe and Mn oxides and organic matter bonded wassignificant in all treatments (Table 3) Mn concentrations invarious soil fractions in all samples have similar trends andcould be presented as follows

RE gt FM gt CA≫ OM gt EX

Residual fraction (RE) in first and second year wasdominant rather than other fractions in 3428ndash4304 and3428ndash4948 percent respectively

Fe and Mn oxides fraction (FM) at both years wasconsiderable so after one year compost application changedfrom 4207 percent in control treatment to 3346 percentin 60 tonha compost These amounts for second year ofcompost application reached 2998 percent in 60 tonha treat-ment As realized Mn amounts in reductive fraction afterincreasing compost levels and compost application timeswere decreased Exchangeable fractionrsquos (EX) proportion atfirst year for control 15 30 and 60 tonha was 037 038 045and 046 percent of total extracted fractions and for secondyear in all treatments was very low because of higher increasein proportion of other fractions

Proportion of carbonates-bonded fraction (CA) was con-siderable for Mn Its proportion from total Mn for composttreatments by 0 15 30 and 60 tonha at first year were 22742453 2499 and 2247 percent and at second year were 22742021 2140 and 1952 percent Mn proportion organic matterbonded fraction (OM) at one-year application was 049 to055 and at two-year compost application was 052 to 069percent

Ghaffari Nejad and Karimian [25] by determination ofchemical forms of Mn and their relation with plant response

at calcareous soils of Fars province Iran stated that greatestplant available Mn had the following order carbonate-bonded organic matter-bonded and dissolved + exchange-able forms Wang and Liu [26] reported that Mn concentra-tion in Fe and Mn oxides fraction was more than carbonate-bonded and then exchangeable fraction In a calcareoussoil concentration of metals in carbonate-bonded fractionfollowed the following order cadmium ≪ copper-lead ltzinc lt manganese [27] So with regard to great affinity ofMn to binding with carbonates higher concentration of Mncompared to Fe in the same fraction and also compared toMnpresented in organic matter bonded fraction is expectableAlso Fe and Mn oxides-bonded concentration of Mn com-pared to other fractions except for residual fraction washigher which is consistent with Ajayi et alrsquos [27] findingsshowing the compatibility of studied metals in Fe and Mnoxides fraction with the following order Cd ≪ Cu lt Pb ltMn Therefore this fraction by stable and strong behaviorwas accounted as most effective phase for binding to heavymetals in soil and important absorbent for them Based onAdriano reportrsquos [28] with regard to attitude of heavy metalsto formation of insoluble organic complexes in the order ofZn2+ ltMn2+ lt Co2+ lt Ni2+ lt Pb2+ lt Fe2+ lt Cd2+ lt Cu2+we could explain considerably lower concentration of organicmatter-bonded Mn compared to other fractions

Results from interactions of different levels of municipalsolid wastes compost and application times on Mn concen-tration at different fractions are shown in Figure 1

Mn concentration in exchangeable phase (instable posi-tion) increased from 3156mgkg soil at control treatment to5563mgkg in two-year application of 60 tonha compostOxidation and reduction of soil Mn could occur simultane-ously (but independently) at close positions [29] which couldbe determinative in increase or decrease of Mn availabilityOxidative-reductive status of Fe rather than Mn usually isreversible So different reactions ofMn to oxidative-reductivechanges are slower [30] Also results showed that exchange-able Mn content significantly increased after addition ofcompost as well as two-year application (119875 lt 001)

Higher amounts ofMn in other soil fractions (stable posi-tions) are related to residual fraction and the lowest amountis related to organic matter-bonded fraction Mn existedin reductive oxidative and residual fractions significantlyincreased by increasing compost application at one-year aswell as increasing application times from one-year to two-year Mn content increasing could be due to the effect of timeon conversion of soil Mn to more stable form Also results


g

f

d

b

g

e

c

a

3

4

5

e

c

ab

a

e

d

b

a

190

200

210

220

230

240

250

260

15 30 60

d

d

c

b

d

bb

a

350

360

370

380

390

400

ee

d

c

e

bab

a

6

7

8

d

cdc

b

d

b

b

a

420

510

600

Control 15 30 60Control

6

5

4

660630

570540

480450

390360330300270

15 30 60Control15 30 60Control

15 30 60Control

Resid

ual f

ract

ion(m

gkgminus

1)

Org

anic

mat

ter b

onde

d fr

actio

n(m

gkgminus

1)

Fe- a

nd M

n-ox

ides

bon

ded

frac

tion(m

gkgminus

1)

Carb

onat

e bon

ded

frac

tion(m

gkgminus

1)

Exch

ange

able

frac

tion(m

gkgminus

1)

First yearSecond year

Compost application levels (ton haminus1)

Figure 1 Effect of interactions between compost application levels and compost application times over two consecutive years on variouscomponents of manganese concentration in soil Letters andashg indicate significant difference between means according to Duncan multiplerange test at 5 probability level


20

25

30

35

40

45

CA Fe-Mn Re0

01

02

03

04

05

06

07

EX OM

Perc

enta

ge o

f tot

al m

anga

nese

Control15

3060

Control15

3060

(a)

03

04

05

06

EX OM

Perc

enta

ge o

f tot

al m

anga

nese

15

20

25

30

35

40

45

50

CA Fe-Mn Re

Control15

3060

Control15

3060

(b)

Figure 2 Fractionation of manganese after one-year (a) and two-year (b) application of municipal solid waste compost

showed that almost in all studied samples carbonate-bondedfraction after residual and Fe and Mn oxides has the highestMn amounts Mn amount in this fraction after addition ofcompost levels separately in each year significantly increased(119875 lt 001) whileMn amount in all treatments fromone-timeapplication to two-time significantly decreased (119875 lt 005)So carbonates-bonded Mn in 15 30 and 60 tonha at secondyear compared to first year significantly decreased by 1033285 and 055 percent respectively

Organic matter-bonded fraction was followed by resid-ual Fe- and Mn-oxides and carbonates-bonded fractionsChanges of this fraction are in the range between 446mgkgin control and 774mgkg in two-year 60 tonha compost

application which is lower than carbonate-bonded Fe andMn oxides and residual fractions but higher than that forexchangeable fraction Mn in the form of organic matterbonded form increased by addition of compost from 0 to 1530 and 60 tonha at first and second years by 47 2376 4417and 6165 6726 and 7354 percent (Figure 2) Mescouto etal [10] studied the distribution and availability of nutrientslike Cu Fe Mn and Zn according to Tessier consecutiveextraction method and found that highest concentrations ofnutrients are associated with residual fraction ZheljazkovandWarman [31] studied the fractionation of CuMn and Znin soils after application of two compost types one resultingfrom municipal solid waste for sugar beet and basil and the


Table 5 Correlation coefficient between soil physical and chemical properties and total and available forms of Mn

Mn Forms EC pH OC CCE CECdsmminus1 mdash cmolc kg

minus1

EX 098lowastlowast minus088lowastlowast 093lowastlowast minus036ns 098lowastlowast

CA 090lowastlowast minus083lowastlowast 078lowastlowast minus050lowast 086lowastlowast

FM 091lowastlowast minus089lowastlowast 095lowastlowast minus040lowast 093lowastlowast

OM 081lowastlowast minus084lowastlowast 092lowastlowast minus033ns 082lowastlowast

RE 089lowastlowast minus083lowastlowast 094lowastlowast minus039ns 090lowastlowast

DTPA 091lowastlowast minus099lowastlowast 093lowastlowast minus060lowast 088lowastlowast

Total 094lowastlowast minus080lowastlowast 094lowastlowast minus038ns 095lowastlowast

lowast lowastlowast and ns respectively mean significant at 5 significant at 1 and nonsignificant

other one a compost fertilizer containing great amounts ofCu for tomato and mint and found that using of municipalsolid wastes compost increased Cu and Zn concentrationin all fractions and Mn concentration in carbonates- Fe-Mn oxides- and organic matter-bonded fractions whileresulting in decrease in exchangeable fraction Achiba et al[32] studied the heavy metals distribution among differentfractions of treated and untreated soils and showed thatafter residual fraction Fe-Mn oxides fractions are domi-nant Organic matter bonded fraction of Cu increased byincreasing compost application possibly due to formationof organic complexes Based on results of Osakwe [18] forchemical and mobile species of Fe Co Ni and Mn usingTessier consecutive extraction method [17] in soils aroundautomobile wastes landfill in Nigeria it was determined thatgreat parts of Fe andMn are associated with residual fraction

33 Correlation between Different Forms of Mn and SoilPhysical and Chemical Properties Results from correlationbetween soil physical and chemical properties and total andavailable forms as well as exchangeable carbonates-bondedFe-Mn oxides-bonded organic matter bonded and residualfractions of Mn are shown in Table 5 There was significantand negative correlation between calcium carbonate equal(CCE) content and carbonate-bonded Mn fraction (minus050)There was significant and strong correlation between soilorganic matter and organic matter bonded fraction of Mn(092) Soil pH has significant and negative correlation withall forms of Mn In these soils pH is in the neutral andalkaline range which caused more absorption of Mn and lesssolubility of these nutrients hence exchangeableMn in thesesoils was very low Results from linear correlation coefficientshowed that by increasing soil cation exchange capacity andorganic matter concentration of various fractions of Mnwould increase and by decreasing soil pH and carbonatesMnabsorption by different soil phases was lower and its solubilitywill increase

Ghaffari Nejad and Karimian [25] studied the relationsbetween soil physical and chemical properties and chemicalforms ofMn and found the correlation between soil CCE andcarbonate-bonded Mn Moharrami and Jalali [6] studied thecompetitive absorption of heavy metals and showed that soil

pH clay and silt content were effective on CEC and CCE waseffective on Cd and Mn and only CCE influenced Mn

4 Conclusion

Results showed that by increasing compost level total con-centration of Mn and DTPA-extractable concentrations inall fractions increased so that lowest and highest amountsof Mn were observed in control and 60 tonha compostapplication

Mn fractionation showed that the highest amount wasassociated with residual fraction and the lowest amount wasfor organic matter bonded fraction Mn existed in Fe-Mnoxides and organic matter-bonded and residual fractionsincreased by increasing compost application amount at first-year and two-year compost application further increasedMncontent in all fractions This represents the effect of time onconversion of more amounts of soil Mn to more stable formsAlso results showed that almost in all studied samplescarbonates-bonded fraction after residual and Fe-Mn oxidesfraction had the highest Mn amounts Exchangeable fraction(EX) contribution at first year for 0 15 30 and 60 toncompostha was 037 038 045 and 046 percent from thesum of all extracted fractions and in second year very lowamounts were obtained but exchangeable Mn amount afteraddition of compost and increase in application time to twoyears significantly increased

Competing Interests

The authors declare that they have no competing interests

Acknowledgments

The authors gratefully acknowledge the support of IranNational Science Foundation (INSF) for conducting thepresent study

References

[1] A P dos Anjos L Cornejo-Ponce S Cadore and N BaccanldquoDetermination of manganese by flame atomic absorptionspectrometry after its adsorption onto naphthalene modified


with 1-(2-pyridylazo)-2-naphthol (PAN)rdquo Talanta vol 71 no3 pp 1252ndash1256 2007

[2] C E Banks J Kruusma R R Moore et al ldquoManganese detec-tion inmarine sediments anodic vs cathodic stripping voltam-metryrdquo Talanta vol 65 no 2 pp 423ndash429 2005

[3] G F Pearson and G M Greenway ldquoRecent developments inmanganese speciationrdquo TrACndashTrends in Analytical Chemistryvol 24 no 9 pp 803ndash809 2005

[4] V A Lemos P X Baliza A L de Carvalho R V OliveiraL S G Teixeira and M A Bezerra ldquoDevelopment of anew sequential injection in-line cloud point extraction systemfor flame atomic absorption spectrometric determination ofmanganese in food samplesrdquo Talanta vol 77 no 1 pp 388ndash3932008

[5] M B McBride Environmental Chemistry of Soils OxfordUniversity Press 1994

[6] SMoharrami andM Jalali ldquoEffect of cationsCaNH4Na K ondistribution of species heavy metals in contaminated soilsrdquo inProceedings of the Soil Conference Environment and SustainableDevelopment 2006

[7] Ch Gleyzes S Tellier and M Astruc ldquoFractionation studies oftrace elements in contaminated soils and sediments a reviewof sequential extraction proceduresrdquoTrACndashTrends in AnalyticalChemistry vol 21 no 6-7 pp 451ndash467 2002

[8] M Zarrabi and M Jalali ldquoComparison of several extractorto extract available Potassium for wheat in some soils ofHamedanrdquo Iranian Journal of Soil and Water Research vol 2no 40 pp 155ndash149 2009

[9] G Nadaska J Lesny and I Michalik ldquoEnvironmental aspect ofmanganese chemistryrdquo Chemistry HEJ ENV-100702-A 2010

[10] C S T Mescouto V P Lemos H A Dantas Filho M Lda Costa D C Kern and K G Fernandes ldquoDistributionand availability of copper iron manganese and zinc in thearchaeological black earth profile from the amazon regionrdquoJournal of the Brazilian Chemical Society vol 22 pp 1484ndash14922011

[11] J D Rhoades ldquoSoluble saltsrdquo in Method of Soil Analysis Part2 Chemical and Microbiological Properties A L Page EdAgronomy Monograph No 9 pp 167ndash179 SSSA and ASAMadison Wis USA 2nd edition 1982

[12] G W Gee and J W Bauder ldquoParticle-size analysisrdquo inMethodsof Soil Analysis Part 1 A Klute Ed pp 383ndash412 ASA SSSAMadison Wis USA 2nd edition 1986

[13] DWNelson and L E Sommers ldquoTotal carbon organic carbonand organic matterrdquo in Methods of Soil Analysis Part II A LPage et al Ed pp 539ndash579 ASA SSSA Madison Wis USA2nd edition 1982

[14] C A Bower R F Reitemeier and M Fireman ldquoExchangeablecation analysis of saline and alkali soilsrdquo Soil Science vol 73 no4 pp 251ndash262 1952

[15] W L Lindsay andW A Norvell ldquoDevelopment of a DTPA soiltest for zinc iron manganese and copperrdquo Soil Science SocietyAmerican Journal vol 42 no 3 pp 421ndash428 1978

[16] P K Gupta Soil Plant Water and Fertilizer Analysis AgrobiosNew Delhi India 2000

[17] A Tessier P G C Campbell and M Blsson ldquoSequentialextraction procedure for the speciation of particulate tracemetalsrdquo Analytical Chemistry vol 51 no 7 pp 844ndash851 1979

[18] S A Osakwe ldquoChemical speciation andmobility of some heavymetals in soils around automobile waste dumpsites in northernpart of Niger Delta South Central Nigeriardquo Journal of Applied

Sciences and Environmental Management vol 14 no 4 pp 123ndash130 2010

[19] A Reyhani Tabar N Karimiyan M Mezardelan and MGhannadha ldquoDistribution of various forms of Zinc and com-municate themwith Soil characteristics of some calcareous soilsof Tehranrdquo Science and Technology of Agriculture and NaturalResources vol 3 pp 125ndash135 2006

[20] M JMohammad andBMAthamneh ldquoChanges in soil fertilityand plant uptake of nutrients and heavy metals in responseto sewage sludge application to calcareous soilsrdquo Journal ofAgronomy vol 3 no 3 pp 229ndash236 2004

[21] M Hamidpour M Afyuni E Khadivi A Zorpas and VInglezakis ldquoCompostedmunicipal waste effect on chosen prop-erties of calcareous soilrdquo International Agrophysics vol 26 no4 pp 365ndash374 2012

[22] S Roghanian HMirsyedhosseini G H Savaghebi L HalajianM Jamei and H Etesami ldquoEffects of Composted MunicipalWaste and its leachate on some soile chemical properties andCorn plant responsesrdquo International Journal of Agriculture vol2 no 6 pp 801ndash814 2012

[23] G Sorrenti M Toselli and B Marangoni ldquoUse of compost tomanage Fe nutrition of pear trees grown in calcareous soilrdquoScientia Horticulturae vol 136 pp 87ndash94 2012

[24] F X Han and A Banin ldquoSelective sequential dissolutiontechniques for trace metals in arid-zone soils the carbonatedissolution steprdquo Communications in Soil Science and PlantAnalysis vol 26 no 3-4 pp 553ndash576 1995

[25] S A Ghaffari Nejad and N Karimian ldquoDetermination ofchemical forms of manganese and their relations with soybeanresponses in some calcareous soils of fars provincerdquo Journal ofWater and Soil Sciences vol 11 no 1 pp 125ndash134 2007

[26] J F Wang and Z Liu ldquoEffect of nitrogen and manganesefertilizer on chemical form of manganese influvo-aquie soilrdquoJiangsu Journal of Agricultural Sciences vol 15 no 4 pp 223ndash236 1999

[27] S O Ajayi B O Odesanya A O Avwioroko G S Adebamboand B Okafor ldquoEffects of long term fertilizer use on trace metallevels of soils in a farm settlementrdquo Agricultural Research andDevelopment vol 2 no 2 pp 44ndash51 2012

[28] D C Adriano Trace Elements in Terrestrial EnvironmentsBiogeochemistry Bioavailability and Risks of Metals SpringerNew York NY USA 2001

[29] L A Sparrow and N C Uren ldquoOxidation and reduction of Mnin acidic soils effect of temperature and soil pHrdquo Soil Biologyand Biochemistry vol 19 no 2 pp 143ndash148 1987

[30] H L Bohn B L McNeal and G A Oconner Oconner SoilChemistry John Wiley amp Sons New York NY USA 2ndedition 1985

[31] V D Zheljazkov and P R Warman ldquoPhytoavailability andfractionation of copper manganese and zinc in soil followingapplication of two composts to four cropsrdquo EnvironmentalPollution vol 131 no 2 pp 187ndash195 2004

[32] W B Achiba N Gabteni A Lakhdar et al ldquoEffects of 5-yearapplication of municipal solid waste compost on the distribu-tion andmobility of heavy metals in a Tunisian calcareous soilrdquoAgriculture Ecosystems and Environment vol 130 no 3-4 pp156ndash163 2009

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extraction method was developed as common and essentialfor fractionation of trace and necessary elements such ascadmium cobalt nickel lead cupper iron and manganesein soil and deposits and divided them into five fractionsincluding exchangeable carbonate- iron-manganese oxides-organic matter-bonded and residual fractions Althoughusing of this method is time consuming it gives comprehen-sive information about trace elements origin occurring waybioavailability mobility and transferring to users [7]

Nadaska et al [9] studied environmental aspects of man-ganese using consecutive extraction and believed that thismethod gave accurate information about origin occurrenceway bioavailability potential mobility and metals transfer innatural environments Mescouto et al [10] showed that thehighest concentration of iron and manganese is associatedwith residual fraction Also this study showed that in frac-tions related to iron-manganese oxides iron and manganeseavailability was in the range of 1265139 to 181812mgkg and4851 to 830mgkg respectively

The aim of the present research was to determine thefractionation of manganese in the soil in the conditionsof two-year application of Tehran municipal solid wastecompost in a calcareous soil Our study can contribute tobetter understanding of the multidirectional transformationof those elements and to an evaluation of the amount ofbioavailable forms

2 Methods and Materials

In order to evaluate the different levels of Tehran municipalsolid waste compost on manganese (Mn) concentration anddistribution in different soil fractions an experiment wasconducted in research station of agriculture faculty of ShahedUniversity (35∘341015840N latitude and 51∘341015840E longitude) Withregard to slow releasing of metals frommunicipal solid waste(MSW) compost in addition to different compost applica-tion levels compost application times are tested Thereforeexperiment was conducted as split plot (compost amounts inmain plots and application times in secondary plots) in threereplications on 2011-2012 and 2012-2013 cropping years Butconsidering homogenous conditions in experimental blocksand nonsignificant errors in main plots traits were analyzedas factorial based on completely randomized block design(RCBD) Experimental factors including four levels of MSWapplication (0 15 30 and 60 tonha) were considered as firstfactor and compost application times (annual and biannualapplication) as second factor So main plot characterized infirst year and different treatment levels were added to plots onApril 2012 On April 2012 plots were divided into two partsand in one part compost was added to soil in equal amountof previous year

After few months and reaching balance in soil 24 soilsamples were collected from surface soil of plots and after air-drying and sieving from 2mmsieve some of soil physical andchemical properties were determined including saturationpercent saturated extract preparing EC and pH [11] soiltexture by hydrometer method [12] organic matter by wetoxidation [13] CEC by Bower et al [14] and CaCO

3by

pressured calcimetric method [13] For determination of the

total and available Fe andMn respectively DTPA [15]HNO3

H2O2and HCl [16] methods were used Mn fractionation

was conducted in five fractions exchangeable carbonates-bonded Fe and Mn oxides organic matter-bonded andresidual using consecutive extraction method [17] Finallyelements concentrations were determined by atomic absorp-tion Analytic Jena Contra AA300 Statistical analyses wasconducted by SAS statistical software and graphs were byExcel software

3 Results and Discussion

Results from determination of soil physical and chemi-cal properties before applying treatments are presented inTable 1 After applying compost treatments it is identified thataddition of compost caused the decrease in pH and increasein organic carbon in all levels compared to control Studiedcompost by 25 organic carbon and pH by 27 is classified instandard range defined by soil and water research organiza-tion Also according to definition of recycling organization(2004) for compost classification in Iran this compost dueto high EC amount fell into second degree type Total Mn inmentioned compost was determined as 42664mgkg

31 Effect ofMSWCompost onConcentration andDistributionofMn in Soil Table 2 shows the results on analysis of variance(ANOVA) of the effect of MSW compost on total and DTPA-extractable concentration ofMn in soil Also this table showsthe results for ANOVA of distribution of elements among fivedifferent fractions including exchangeable (EX) carbonate-bonded (CA) or acid-soluble reductive Fe and Mn oxides-bonded (FM) organic matter-bonded (OM) and residualfraction (RE)

Table 3 shows mean comparisons of total and DTPA-extractable concentrations and existing amounts in five dif-ferent soil fractions for Mn at different levels of municipalsolid waste compost Results showed that by increasingcompost application percent total and DTPA-extractableconcentrations and existing amounts in five different soilfractions of Mn increased which the lowest and highestconcentration in all studied forms observed in control and60 tonha compost treatments respectively Osakwe [18]stated that Mn strongly attached to soil matrix So it isnot readily available to appear in food chain It should benoted that since total Fe and Mn concentrations in soils weremeasured by digestion of separate samples in related acidstotalmeasured forms essentiallywere not equal to total Fe andMn Reyhani Tabar et al [19] found similar results in studyingthe distribution of different forms of Zn in calcareous soilsof Tehran Mohammad and Athamneh [20] reported theincrease in DTPA-extractable Fe and Mn concentration dueto addition of sewage sludge compared to control Theyalso stated that Fe and Mn concentrations increased from382 and 719mgkg in control to 1383 and 3163mgkg inthe highest level of sewage sludge treatment (160 tonha)respectively

Formation of stable metal complexes could decreasesolubility of metal ions in soils [21] Great amount of organic




Loam 117 10 828 115 1213 257125 278 124792 1189









MSW Mn


Control 3156d 19264d 356347d 4466d 29042c 11889b 1247917d

15 3871c 220827c 37206c 5945c 38883b 14802a 1288458c

30 4825b 246453b 378833b 6493b 43104b 15269a 1324375b

60 5461a 258413a 3908a 7088a 57471a 15847a 1425272a



2resulting from









One time 4186b 23334a 369483b 5276b 37377b 13198b 1307532b

2 times 447a 225827b 379537a 672a 46873a 15705a 1335479a














g

f

d

b

g

e

c

a

3

4

5

e

c

ab

a

e

d

b

a

190

200

210

220

230

240

250

260

15 30 60

d

d

c

b

d

bb

a

350

360

370

380

390

400

ee

d

c

e

bab

a

6

7

8

d

cdc

b

d

b

b

a

420

510

600


6

5

4

660630

570540

480450

390360330300270


15 30 60Control

Resid

ual f

ract

ion(m

gkgminus

1)

Org

anic

mat

ter b

onde

d fr

actio

n(m

gkgminus

1)

Fe- a

nd M

n-ox

ides

bon

ded

frac

tion(m

gkgminus

1)

Carb

onat

e bon

ded

frac

tion(m

gkgminus

1)

Exch

ange

able

frac

tion(m

gkgminus

1)





20

25

30

35

40

45

CA Fe-Mn Re0

01

02

03

04

05

06

07

EX OM

Perc

enta

ge o

f tot

al m

anga

nese

Control15

3060

Control15

3060

(a)

03

04

05

06

EX OM

Perc

enta

ge o

f tot

al m

anga

nese

15

20

25

30

35

40

45

50

CA Fe-Mn Re

Control15

3060

Control15

3060

(b)








minus1













4 Conclusion



Competing Interests


Acknowledgments


References








































Journal of












Volume 2014

Advances in









Geophysics

















Loam 117 10 828 115 1213 257125 278 124792 1189









MSW Mn


Control 3156d 19264d 356347d 4466d 29042c 11889b 1247917d

15 3871c 220827c 37206c 5945c 38883b 14802a 1288458c

30 4825b 246453b 378833b 6493b 43104b 15269a 1324375b

60 5461a 258413a 3908a 7088a 57471a 15847a 1425272a



2resulting from









One time 4186b 23334a 369483b 5276b 37377b 13198b 1307532b

2 times 447a 225827b 379537a 672a 46873a 15705a 1335479a














g

f

d

b

g

e

c

a

3

4

5

e

c

ab

a

e

d

b

a

190

200

210

220

230

240

250

260

15 30 60

d

d

c

b

d

bb

a

350

360

370

380

390

400

ee

d

c

e

bab

a

6

7

8

d

cdc

b

d

b

b

a

420

510

600


6

5

4

660630

570540

480450

390360330300270


15 30 60Control

Resid

ual f

ract

ion(m

gkgminus

1)

Org

anic

mat

ter b

onde

d fr

actio

n(m

gkgminus

1)

Fe- a

nd M

n-ox

ides

bon

ded

frac

tion(m

gkgminus

1)

Carb

onat

e bon

ded

frac

tion(m

gkgminus

1)

Exch

ange

able

frac

tion(m

gkgminus

1)





20

25

30

35

40

45

CA Fe-Mn Re0

01

02

03

04

05

06

07

EX OM

Perc

enta

ge o

f tot

al m

anga

nese

Control15

3060

Control15

3060

(a)

03

04

05

06

EX OM

Perc

enta

ge o

f tot

al m

anga

nese

15

20

25

30

35

40

45

50

CA Fe-Mn Re

Control15

3060

Control15

3060

(b)








minus1













4 Conclusion



Competing Interests


Acknowledgments


References








































Journal of












Volume 2014

Advances in









Geophysics


















One time 4186b 23334a 369483b 5276b 37377b 13198b 1307532b

2 times 447a 225827b 379537a 672a 46873a 15705a 1335479a














g

f

d

b

g

e

c

a

3

4

5

e

c

ab

a

e

d

b

a

190

200

210

220

230

240

250

260

15 30 60

d

d

c

b

d

bb

a

350

360

370

380

390

400

ee

d

c

e

bab

a

6

7

8

d

cdc

b

d

b

b

a

420

510

600


6

5

4

660630

570540

480450

390360330300270


15 30 60Control

Resid

ual f

ract

ion(m

gkgminus

1)

Org

anic

mat

ter b

onde

d fr

actio

n(m

gkgminus

1)

Fe- a

nd M

n-ox

ides

bon

ded

frac

tion(m

gkgminus

1)

Carb

onat

e bon

ded

frac

tion(m

gkgminus

1)

Exch

ange

able

frac

tion(m

gkgminus

1)





20

25

30

35

40

45

CA Fe-Mn Re0

01

02

03

04

05

06

07

EX OM

Perc

enta

ge o

f tot

al m

anga

nese

Control15

3060

Control15

3060

(a)

03

04

05

06

EX OM

Perc

enta

ge o

f tot

al m

anga

nese

15

20

25

30

35

40

45

50

CA Fe-Mn Re

Control15

3060

Control15

3060

(b)








minus1













4 Conclusion



Competing Interests


Acknowledgments


References








































Journal of












Volume 2014

Advances in









Geophysics















g

f

d

b

g

e

c

a

3

4

5

e

c

ab

a

e

d

b

a

190

200

210

220

230

240

250

260

15 30 60

d

d

c

b

d

bb

a

350

360

370

380

390

400

ee

d

c

e

bab

a

6

7

8

d

cdc

b

d

b

b

a

420

510

600


6

5

4

660630

570540

480450

390360330300270


15 30 60Control

Resid

ual f

ract

ion(m

gkgminus

1)

Org

anic

mat

ter b

onde

d fr

actio

n(m

gkgminus

1)

Fe- a

nd M

n-ox

ides

bon

ded

frac

tion(m

gkgminus

1)

Carb

onat

e bon

ded

frac

tion(m

gkgminus

1)

Exch

ange

able

frac

tion(m

gkgminus

1)





20

25

30

35

40

45

CA Fe-Mn Re0

01

02

03

04

05

06

07

EX OM

Perc

enta

ge o

f tot

al m

anga

nese

Control15

3060

Control15

3060

(a)

03

04

05

06

EX OM

Perc

enta

ge o

f tot

al m

anga

nese

15

20

25

30

35

40

45

50

CA Fe-Mn Re

Control15

3060

Control15

3060

(b)








minus1













4 Conclusion



Competing Interests


Acknowledgments


References








































Journal of












Volume 2014

Advances in









Geophysics















20

25

30

35

40

45

CA Fe-Mn Re0

01

02

03

04

05

06

07

EX OM

Perc

enta

ge o

f tot

al m

anga

nese

Control15

3060

Control15

3060

(a)

03

04

05

06

EX OM

Perc

enta

ge o

f tot

al m

anga

nese

15

20

25

30

35

40

45

50

CA Fe-Mn Re

Control15

3060

Control15

3060

(b)








minus1













4 Conclusion



Competing Interests


Acknowledgments


References








































Journal of












Volume 2014

Advances in









Geophysics

















minus1













4 Conclusion



Competing Interests


Acknowledgments


References








































Journal of












Volume 2014

Advances in









Geophysics




















































Journal of












Volume 2014

Advances in









Geophysics














Research Article Manganese Fractionation in Soils after...

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