UNIVERSITY OF AGRICULTURAL SCIENCES AND VETERINARY MEDICINE CLUJ-NAPOCA

AGRICULTURE FACULTY

Doctoral student Vaum (Ivasuc) Melinda Maria

STUDY OF THE DEGREE OF CONTAMINATION WITH HEAVY METALS OF CERTAIN VEGETABLES GROWN IN

THE BAIA MARE AREA

(SUMMARY OF PhD THESIS)

PhD COORDINATOR: Prof. PhD MIHAI RUSU

CLUJ-NAPOCA

2011

23

INTRODUCTION

We live in a world facing major global issues, including continuing

environmental degradation with its unwanted component, pollution, which, through its

omnipresence, has negative, dramatic influence on living organisms, especially on

human health.

The problem of approach related to heavy metals is contemporary, so the

proposed thesis thematic has objectives aimed towards the complex phenomenon of

heavy metal contamination in Baia Mare area, frequently mentioned on the heavily

polluted urban centers list.

OBJECTIVES OF PRESENT RESEARCH

The main purpose of the research conducted in this doctoral thesis is to identify

the main sources of pollution with heavy metals, measurement of heavy metal contents

for certain types of vegetables grown in at varying distances from the pollution sources

in Baia Mare depression.

To achieve its purpose, the research activity was conducted with the following

objectives:

• determination of specific climate conditions in the area of research and their

effects in the amount of pollution / contamination;

• determination of the main physical and chemical parameters for the investigated

soil samples and their characterization as involved factors;

• determination of heavy metal quantities in total and mobile forms in soil and

interpretation of values in connection with the phenomenon of soil pollution /

contamination by comparing with reference values;

• determination of heavy metal quantities in plant samples from lettuce and

spinach crops and interpretation of the results from the level of contamination

and food safety hazard points of view by comparing values with the maximum

permitted levels;

• assessing capacity to absorb studied heavy metals (Cu, Pb, Zn, Cd) by

vegetables (lettuce, spinach), through the concentration factor (CF);

24

• highlighting the behavior of heavy metals (Cu, Pb, Zn, Cd) absorbed by

vegetables (lettuce, spinach) through translocation factor (TF), that indicates the

transition intensity of heavy metals from inedible to edible parts of vegetables;

• research options for control / monitoring of heavy metals in the soil-plant

system to disseminate results in producing analytical organization charts or

analytical guide model, approachable in environmental impact studies specific

to heavy metals.

SOIL SAMPLES AND PLANT MATERIAL

The species chosen for gathering plant samples are very common vegetables

used in human nourishment for their leaves rich in nutrients – lettuce (Lactuca sativa

L. var. capitata) and spinach (Spinacia oleracea L. var. matador). These plant species

were chosen specifically because, among vegetables, they have the greatest capacity to

accumulate heavy metals, especially Cd, without showing visible phytotoxicity

symptoms, a fact that enhances the risk to human health.

Lettuce and spinach crops were planted in March 2011 and sampling was done

in May 2011. To show the heavy metal translocation phenomenon, measurements

were made for the contents of Pb, Cd, Cu and Zn, in both roots and leaves of these

plants separately. Together with plant sampling, agrochemical and pedological soil

sampling was performed.

STUDY AREA AND SAMPLING LOCATIONS

The four sampling areas were chosen at various distances from existing

pollution sources in Baia Mare depression. The plots where the soil samples and plant

samples were collected are located in Ferneziu, Tăuţii de Sus, Baia Mare (Valea

Borcutului), Cicârlău, with Sighetu-Marmaţiei as the reference area, because is not

directly affected by pollution sources. All of them are classified as sensitive type of

land.

25

ANALYTICAL METHODS USED IN DETERMINATION OF HEAVY

METAL LEVELS

To achieve the proposed objectives, a number of physical and chemical

determinations for soil and plant samples (lettuce and spinach) were performed.

Analytical methods used for soil characterization and determination of heavy metal

levels in soil and vegetables are shown in the following figure (fig.1).

Fig.1 Analytical method performed with plant and soil samples

SOIL SAMPLES

1. From sensitive type of land under direct impact of pollution sources: Ferneziu, Tăuţii de Sus, Valea Borcutului (Baia Mare), Cicârlău.

2. From unpolluted sensitive type of land: Sighetu-Marmaţiei

SR ISO 11464 :1994

1. Particle size composition-texture 2. Humus content 3. Clay content 4. pH; ICPA, 1981 5. Heavy metal content (total and mobile

forms) :Cu, Pb, Zn, Cd - Drying at room temperature and grinding soil samples; SR ISO 11464 :1994 - Determination of water content; SR ISO 11465 :1998 - Extraction of trace elements in aqua regia for total forms determination; SR ISO 11466 :1999 - Selective extraction with 0.05M EDTA for mobile forms determination Wear and Evans, 1968 -Heavy metal determination with AAS

PLANT SAMPLES

LEAVES: lettuce and spinach ROOTS: lettuce and spinach Plants were sampled at the same time with soil

1. Dry matter 2. Heavy metal content: Cu, Pb, Zn, Cd - Oven drying of plant samples - Mineralization of plant samples with HNO3 (65%) and H2O2 (20%) Marinussen and Van der Zee, 1997 - Heavy metal determination with AAS

26

DATA ANALYSIS

The measured concentrations of Cu, Pb, Zn and Cd in total and mobile forms,

in soil, roots and leaves of lettuce and spinach were processed using the statistical

package SPSS 17, descriptive statistics include minimum values, maximum values,

arithmetic mean and standard deviation.

To measure the influence of soil physical and chemical factors (pH, humus

content, clay content) on the content of Cu, Pb, Zn, Cd (total and mobile forms) in soil

and roots of lettuce and spinach, simple correlations were performed using the

statistical package SPSS 17 with the Pearson correlation coefficient values as results,

that were compared with the limit values, with probabilities of transgression 5% and

1% for n = 5 studied cases.

To determine whether the relationship between the content of Cu, Pb, Zn, Cd in

mobile forms in soil and the content in vegetable roots is influenced by physical and

chemical soil factors (pH, humus content, clay content) partial correlations were

performed using the statistical package SPSS 17.

In order to assess the mobility and translocation of heavy metals (Cu, Pb, Zn,

Cd) in the soil-plant system, values for concentration factor (CF) and translocation

factor (TF) were computed.

To assess the degree of pollution / contamination of the soil-plant system,

values for soil were compared with normal reference values, alert threshold values and

intervention threshold values for sensitive type of land, provided by Order no.

756/1997 of the Ministry of Waters, Forests and Environmental Protection. The values

for vegetables were compared with the maximum permitted levels provided by

FAO/WHO- Codex alimentarius commission, 2001, (table 1).

To assess the degree of pollution of studied areas, methods for calculating the

index of pollution ”Z” by calculating the geochemical abundance index for each

element were employed, (Fiedler and Rösler, 1988).

27

Table 1

Reference values for sensitive type of land and for leafy vegetables

Metal Standards for sensitive type of land a

(mg/kg dry mass)

Standards for leafy vegetables b

Normal

values Warning threshold

Intervention

threshold Maximum permitted levels

Cd 1 3 5 0.2

Cu 20 100 200 73.3

Pb 20 50 100 0.3

Zn 100 300 600 99.4 a Order no.756/1997 of the Ministry of Waters, Forests and Environmental Protection; b FAO/WHO – Codex Alimentarius Commission, 2001.

Values for heavy metal content in polluted areas were compared with values

from the reference area using the Paired Samples T-Test from the SPSS 19 statistical

package, verifying if there are significant differences between the mean values (the

difference between the two variables was calculated for each case and it was tested

whether the differences between their averages differ from zero within 95%

confidence hypothesis).

28

ACCUMULATION OF HEAVY METALS IN SOIL

Table 2

Range of variation for Cu, Pb, Zn, Cd total forms content in soil

Range of variation Metal

(total forms) Minimum

mg·kg-1

Maximum

mg·kg-1

Cu 27.463

(Cicârlău)

216.042

(Ferneziu)

Pb 38.671

(Sighet)

2036.362

(Ferneziu)

Zn 122.635

(Cicârlău)

1992.322

(Ferneziu)

Cd 0.789

(Cicârlău)

7.854

(Ferneziu)

Table 3

Range of variation for Cu, Pb, Zn, Cd mobile forms content in soil

Range of variation Metal

(mobile forms) Minimum

mg·kg-1

Maximum

mg·kg-1

Cu 7.277

(Sighet)

33.028

(Ferneziu)

Pb 10.621

(Sighet)

331.202

(Ferneziu)

Zn 29.635

(Sighet)

315.288

(Ferneziu)

Cd 0.217

(Sighet)

2.430

(Ferneziu)

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ACCUMULATION OF HEAVY METALS IN PLANTS

Accumulation of heavy metals in lettuce

Table 4

Range of variation for Cu, Pb, Zn, Cd content in lettuce roots

Range of variation in roots

Metal Minimum

mg·kg-1

Maximum

mg·kg-1

Cu 4.611

(Sighet)

14.651

(Ferneziu)

Pb 2.653

(Sighet)

138.721

(Ferneziu)

Zn 10.700

(Sighet)

99.562

(Ferneziu)

Cd 0.109

(Cicârlău)

1.017

(Ferneziu)

Table 5

Range of variation for Cu, Pb, Zn, Cd content in lettuce leaves

Range of variation in leaves

Metal Minimum

mg·kg-1

Maximum

mg·kg-1

Cu 3.662

(Sighet)

12.077

(Ferneziu)

Pb 1.662

(Sighet)

100.432

(Ferneziu)

Zn 9.963

(Sighet)

97.621

(Ferneziu)

Cd 0.051

(Sighet)

1.132

(Ferneziu)

30

Accumulation of heavy metals in spinach

Table 6

Range of variation for Cu, Pb, Zn, Cd content in spinach roots

Range of variation in roots

Metal Minimum

mg·kg-1

Maximum

mg·kg-1

Cu 4.621

(Cicârlău)

15.672

(Ferneziu)

Pb 6.938

(Sighet)

181.672

(Ferneziu)

Zn 15.672

(Sighet)

100.653

(Ferneziu)

Cd 0.065

(Sighet)

1.121

(Ferneziu)

Table 7

Range of variation for Cu, Pb, Zn, Cd content in spinach leaves

Range of variation in leaves

Metal Minimum

mg·kg-1

Maximum

mg·kg-1

Cu 5.733

(Cicârlău)

16.355

(Tăuţii de Sus)

Pb 2.881

(Sighet)

102.412

(Ferneziu)

Zn 12.726

(Sighet)

89.643

(Ferneziu)

Cd 0.052

(Sighet)

1.113

(Ferneziu)

31

INTERACTIONS AND DEPENDENCIES OF HEAVY METALS IN THE

SOIL-PLANT SYSTEM

Correlation between results and pH values

Analyzing the values of correlation coefficients between heavy metal content in

soil (total and mobile forms) and pH, it is observed that for all four metals it has

negative values, fact that explains that the decrease of pH increases the total

concentration of heavy metals in soil, but also favors the occurrence of their mobile-

accessible-soluble forms, (table 8).

Table 8

Correlation coefficients between heavy metal contents in soil (total and mobile forms)

and pH and between heavy metal contents in vegetable roots and pH

Simple correlations

Heavy metal contents

(mg·kg-1) - pH

Correlation coefficient

values

Total forms in soil -0.943*

Mobile forms in soil -0.986**

Lettuce root -0.926* Cu (mg·kg-1)

Spinach root -0.873

Total forms in soil -0.933*

Mobile forms in soil -0.907*

Lettuce root -0.940* Pb (mg·kg-1)

Spinach root -0942*

Total forms in soil -0.944*

Mobile forms in soil -0.930*

Lettuce root -0.874 Zn (mg·kg-1)

Spinach root -0.861

Total forms in soil -0.877

Mobile forms in soil -0.915*

Lettuce root -0.869 Cd (mg·kg-1)

Spinach root -0.917*

∗ correlation is significant at 0.05 level;** correlation is significant at 0.01 level

32

Correlation between results and humus contents

Table 9

Correlation coefficients between heavy metal contents in soil (total and mobile forms) and

humus content and between heavy metal contents in vegetable roots and humus content

Simple correlations

Heavy metal contents

(mg·kg-1) - humus content

Correlation coefficients

values

Total forms in soil 0.887* Mobile forms in soil 0.776 In lettuce roots 0.921*

Cu (mg·kg-1)

In spinach roots 0.949* Total forms in soil 0.850 Mobile forms in soil 0.921* In lettuce roots 0.881*

Pb (mg·kg-1)

In spinach roots 0.868 Total forms in soil 0.614 Mobile forms in soil 0.799 In lettuce roots 0.919*

Zn (mg·kg-1)

In spinach roots 0.903* Total forms in soil 0.950* Mobile forms in soil 0.885* In lettuce roots 0.901*

Cd (mg·kg-1)

In spinach roots 0.906*

∗ correlation is significant at 0.05 level;** correlation is significant at 0.01 level;

33

Correlation between results and clay contents

Table 10

Correlation coefficients between heavy metal contents in soil (total and mobile forms)

and clay content and between heavy metal contents in vegetables roots and clay

content

Simple correlations

Heavy metal contents (mg·kg-1) - clay content

Correlation coefficients

values

Total forms in soil 0.903* Mobile forms in soil 0.825 In lettuce roots 0.936*

Cu (mg·kg-1)

In spinach roots 0.939* Total forms in soil 0.853 Mobile forms in soil 0.917* In lettuce roots 0.892*

Pb (mg·kg-1)

In spinach roots 0.877 Total forms in soil 0.665 Mobile forms in soil 0.801 In lettuce roots 0.904*

Zn (mg·kg-1)

In spinach roots 0.878 Total forms in soil 0.941* Mobile forms in soil 0.883* In lettuce roots 0.871

Cd (mg·kg-1)

In spinach roots 0.905*

∗correlation is significant at 0.05 level;** correlation is significant at 0.01 level

34

PARTIAL CORRELATIONS

Table 11

Partial correlation coefficients

Partial correlation pH Humus content Clay content

Cu mobile forms soil-Cu root lettuce 0.643 0.972** 0.912*

Cu mobile forms soil-Cu root spinach 0.673 0.904* 0.726

Pb mobile forms soil-Pb root lettuce 0.990** 0.994** 0.981**

Pb mobile forms soil-Pb root spinach 0.961** 0.987** 0.971**

Zn mobile forms soil-Zn root lettuce 0.782 0.920* 0.893*

Zn mobile forms soil-Zn root spinach 0.847 0.920* 0.893*

Cd mobile forms soil-Cd root lettuce 0.952** 0.929* 0.936*

Cd mobile forms soil-Cd root spinach 0.975** 0.986** 0.986**

∗ correlation is significant at 0.05 level;** correlation is significant at 0.01 level

CONCENTRATION FACTOR (CF)

The order of average values of the concentration factor (CF) in lettuce roots

was: Cd> Cu> Zn> Pb. For lettuce leaves the order was similar to that for spinach

leaves and was: Cu> Cd> Zn> Pb. The order of average values for the concentration

factor in spinach roots was: Pb> Zn> Cu> Cd.

The average values for the concentration factor being smaller than 1 for all

metals indicated low translocation from soil to plant, fact that shows that both species

manifest the behavior to exclude these metals, (table 12).

TRANSLOCATION FACTOR (TF)

The translocation factor (TF) of heavy metals from roots to leaves is an

essential indicator that allows the assessment of mobility of heavy metals in plants and

the danger of metal translocation to their edible parts, (table 13).

The order for average values of the translocation factor from roots to leaves for

lettuce was: Zn> Cu> Cd> Pb. The order for average values of the translocation factor

from roots to leaves for spinach was: Cu> Cd> Zn> Pb.

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Table 12

Average values for the concentration factor (CF)

Range of variation for CF (average values) Metal

Minimum Maximum

Cu 0.06 – lettuce leaves

(Ferneziu)

0.20 – spinach leaves

(Cicârlău)

Pb 0.03 – lettuce leaves

(Sighet)

0.21 – spinach roots

(Valea Borcutului)

Zn

0.04 – spinach leaves

(Ferneziu)

0.16 – spinach roots

(Tăuţii de Sus; Cicârlău)

0.16 – lettuce roots

(Tăuţii de Sus)

Cd 0.05 – spinach leaves

(Sighet)

0.18 – lettuce roots and

spinach leaves (Ferneziu)

Table 13

Average values for the translocation factor from roots to leaves

Range of variation for TF (average values) Metal

Minimum Maximum

Lettuce Cu

Spinach

0.78

1.08

0.85

1.13

Lettuce Pb

Spinach

0.62

0.45

0.76

0.80

Lettuce Zn

Spinach

0.66

0.66

0.97

0.91

Lettuce Cd

Spinach

0.29

0.78

0.96

1.12

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ASSESSMENT OF THE DEGREE OF SOIL POLLUTION

Assessment the degree of soil pollution through comparing the measured

values with reference values

Measurements indicate the highest degree of soil pollution with Cu, Zn, Cd in

Tăuţii de Sus and Ferneziu areas and with Pb in Tăuţii de Sus, Ferneziu and Valea

Borcutului areas, in these areas the recorded values frequently exceeded the

intervention threshold for all four studied metals. Measurements allow classification of

areas according to their degree of pollution in the following order: Ferneziu> Tăuţii de

Sus> Valea Borcutului. (fig.2).

a)

b)

Exceedings of the intervention threshold for Pb

39%

38%

23%

Tăuţii de Sus Ferneziu Valea Borcutului

Exceedings of the intervention threshold for Cu

33%

67%

Tăuţii de SusFerneziu

37

c)

d)

Fig. 2 The ratio of exceedings of the intervention threshold

a) for Cu; b) for Pb; c) for Zn; d) for Cd

Exceedings of the intervention threshold for Zn

29%

71%

Tăuţii de SusFerneziu

Exceedings of the intervention threshold for Cd

67%

33%

Tăuţii de SusFerneziu

38

ASSESSMENT OF THE DEGREE OF SOIL POLLUTION

BY POLLUTION INDEX

Table 14

The calculated values of geochemical abundance (“Z” index)

and the pollution levels for the studied areas

Sampling area Distance from

sources of pollution (km)

Metal Geochemical abundance

(AG)

The calculated value of Z

Significance of Z

Cu 2.91 Pb 63.15 Zn 6.64 Tăuţii de Sus

C4.28

R5.86 Cd

40.35

110.05 Very strong

pollution

Cu 0.65 Pb 3.85 Zn 2.07 Cicârlău

C17.92

R20.49 Cd

8.03

11.63 Slight

pollution

Cu 1.24 Pb 6.65 Zn 2.12 Valea Borcutului

C7.9

R10.48 Cd

14.04

21.05 Moderate pollution

Cu 3.94 Pb 96.80 Zn 21.16 Ferneziu

C3.05

R2.35 Cd

42.02

160.92 Excessive pollution

Cu 0.95 Pb 3.54 Zn 1.90 Sighet

C62.81

R64.39 Cd 7.73

11.12 Slight

pollution

C distance from Cuprom S.A. Baia Mare R distance from Romplumb S.A. Baia Mare

It can be observed that the areas have different degrees of pollution depending

on the distance from the two sources of industrial pollution. The “Z” index calculated

for Ferneziu area indicates excessive pollution, being the closest area to the pollution

39

sources. Tăuţii de Sus area has a “Z” index which indicates very strong pollution. The

“Z” index for Valea Borcutului area indicates moderate pollution. Cicârlău and Sighet

areas have “Z” indexes corresponding to slight pollution.

ASSESSMENT OF THE DEGREE OF POLLUTION IN VEGETABLES

Table 15

Reporting obtained average values for Cu, Pb, Zn, Cd in vegetables at the maximum

permitted levels (mg·kg-1)

Metal Maximum levels in vegetables

FAO/WHO- Commission Codex Alimentarius (mg·kg-1)

Recorded exceedings for

lettuce Recorded exceedings

for spinach

Cu 73.3 - -

Pb 0.3 In all areas

5.5 (Sighet)-334.6 times higher (Ferneziu)

9.6 (Sighet)-341.3

(Ferneziu) times higher

Zn 99.4 - -

Cd 0.2

3.2-4.89 times higher (Tăuţii de Sus)

3.3-5.6 times higher (Ferneziu)

1.34 times higher (Valea

Borcutului) 3.5-4.7 times higher

(Tăuţii de Sus) 3.8-5.5 times higher

(Ferneziu)

40

COMPARISON BETWEEN MEASURED VALUES FOR SOIL IN

POLLUTED AREAS AND MEASURED VALUES FROM THE

REFRENCE AREA

Table 16

Paired Samples Test results for Cu, Pb, Zn, Cd total form contents in soil

Pairs t significance in the

“Paired Samples Test” Cu total soil Tăuţii de Sus - Cu total soil Sighet ,016* Cu total soil Cicârlău - Cu total soil Sighet ,012 * Cu total soil Valea Borcutului - Cu total soil Sighet ,038 * Cu total soil Ferneziu - Cu total soil Sighet ,001 * Pb total soil Tăuţii de Sus - Pb total soil Sighet ,000 * Pb total soil Cicârlău - Pb total soil Sighet ,495 Pb total soil Valea Borcutului - Pb total soil Sighet ,008 * Pb total soil Ferneziu - Pb total soil Sighet ,000 * Zn total soil Tăuţii de Sus - Zn total soil Sighet ,005 * Zn total soil Cicârlău - Zn total soil Sighet ,561 Zn total soil Valea Borcutului - Zn total soil Sighet ,166 Zn total soil Ferneziu - Zn total soil Sighet ,000 * Cd total soil Tăuţii de Sus - Cd total soil Sighet ,000 * Cd total soil Cicârlău - Cd total soil Sighet ,567 Cd total soil Valea Borcutului - Cd total soil Sighet ,007 * Cd total soil Ferneziu - Cd total soil Sighet ,005 *

∗ differences is significant at 0.05 level

41

COMPARISON BETWEEN MEASURED VALUES FOR LETTUCE IN

POLLUTED AREAS AND MEASURED VALUES FROM THE

REFRENCE AREA

Table 17

Paired Samples Test results for Cu, Pb, Zn, Cd total form contents in lettuce

Pairs t significance in the

“Paired Samples Test” Cu leaves lettuce Tăuţii de Sus - Cu leaves lettuce Sighet ,001* Cu leaves lettuce Cicârlău - Cu leaves lettuce Sighet ,000* Cu leaves lettuce Valea Borcutului - Cu leaves lettuce Sighet ,005* Cu leaves lettuce Ferneziu - Cu leaves lettuce Sighet ,000* Pb leaves lettuce Tăuţii de Sus - Pb leaves lettuce Sighet ,000* Pb leaves lettuce Cicârlău - Pb leaves lettuce Sighet ,000* Pb leaves lettuce Valea Borcutului - Pb leaves lettuce Sighet ,000* Pb leaves lettuce Ferneziu - Pb leaves lettuce Sighet ,000* Zn leaves lettuce Tăuţii de Sus - Zn leaves lettuce Sighet ,000* Zn leaves lettuce Cicârlău - Zn leaves lettuce Sighet ,000* Zn leaves lettuce Valea Borcutului - Zn leaves lettuce Sighet ,000* Zn leaves lettuce Ferneziu - Zn leaves lettuce Sighet ,000* Cd leaves lettuce Tăuţii de Sus - Cd leaves lettuce Sighet ,001* Cd leaves lettuce Cicârlău - Cd leaves lettuce Sighet ,122* Cd leaves lettuce Valea borcutului - Cd leaves lettuce Sighet ,039* Cd leaves lettuce Ferneziu - Cd leaves lettuce Sighet ,001*

∗ differences is significant at 0.05 level

42

COMPARISON BETWEEN MEASURED VALUES FOR SPINACH IN

POLLUTED AREAS AND MEASURED VALUES FROM THE

REFRENCE AREA

Table 18

Paired Samples Test results for Cu, Pb, Zn, Cd total form contents in spinach

Pairs t significance in the

“Paired Samples Test” Cu leaves spinach Tăuţii de Sus - Cu leaves spinach Sighet ,000* Cu leaves spinach Cicârlău - Cu leaves spinach Sighet ,425 Cu leaves spinach Valea Borcutului - Cu leaves spinach Sighet ,000* Cu leaves spinach Ferneziu - Cu leaves spinach Sighet ,000* Pb leaves spinach Tăuţii de Sus - Pb leaves spinach Sighet ,000* Pb leaves spinach Cicârlău - Pb leaves spinach Sighet ,006* Pb leaves spinach Valea Borcutului - Pb leaves spinach Sighet ,000* Pb leaves spinach Ferneziu - Pb leaves spinach Sighet ,000* Zn leaves spinach Tăuţii de Sus - Zn leaves spinach Sighet ,000* Zn leaves spinach Cicârlău - Zn leaves spinach Sighet ,000* Zn leaves spinach Valea Borcutului - Zn leaves spinach Sighet ,000* Zn leaves spinach Ferneziu - Zn leaves spinach Sighet ,000* Cd leaves spinach Tăuţii de Sus - Cd leaves spinach Sighet ,000* Cd root spinach Cicârlău - Cd root spinach Sighet ,147 Cd leaves spinach Valea Borcutului - Cd leaves spinach Sighet ,005* Cd leaves spinach Ferneziu - Cd leaves spinach Sighet ,000*

∗ differences is significant at 0.05 level

43

BUILDING THE ANALYTICAL ORGANIZATIONAL CHARTS

Based on the methodology for elaborating studies in the field of agro-chemistry

in our country, methodological approaches necessary to control the agrochemical soil-

plant system for vegetables can be defined, to build analytical organizational charts,

(fig. 3, 4).

Fig. 3 Analytical organizational chart for plant samples

Plant samples

Plant sampling: roots, leaves

Heavy metal content Marinussen and Van der Zee, 1997

Drying of plant samples Mineralizing plant samples with HNO3 (65%) and H2O2 (20%)

44

Soil samples

Soil physical properties

ICPA, 1981

Soil chemical properties

ICPA, 1981

Heavy metal content, through

AAS method

Soil sampling SR ISO 11464:

1994

Granulometric

analysis – texture

Clay content

pH

humus content

Drying at room temperature and grinding of soil

samples SRISO 11464:

1994

Measuring of water content

SR ISO 11465: 1998

Extraction of microelements soluble in aqua

regia – total forms SR ISO 11466:

1999

Selective extraction with EDTA 0.05M – mobile forms,

Wear and Evans, 1968

Fig. 4 Analytical organizational charts for soil samples

45

CONCLUSIONS

• Regarding the first objective we can conclude that in areas Tăuţii de Sus,

Cicârlău, Valea Borcutului, Ferneziu specific weather conditions exist (high

number of days with fog, atmospheric calm, thermal inversion) that favor the

persistence of pollutants in the atmosphere and support the existence of high

concentrations of pollutants in the lower troposphere, influencing negatively the

state of pollution in the concerned areas.

• Regarding the second objective we conclude that physical and chemical soil

parameters (pH, humus content, clay content) are key factors in mobility and

accessibility of heavy metals (Cu, Pb, Zn, Cd) in the soil-plant system. Low pH

values, especially in Tăuţii de Sus and Ferneziu areas, increase the total heavy metal

content in soil, but also favor the occurrence of mobile-accessible-soluble forms.

Higher levels of humus content in areas with low pH are a result of work to increase

soil fertility. Although colloidal components of the adsorption complex (humus and

clay minerals) should have a decisive effect in soil pH adjustment, under excessive

pollution (Tăuţii de Sus, Ferneziu) degradation of colloidal state of soil components

and destruction of adsorption complex occurs.

• Regarding the third objective we conclude that the variation of heavy metal

(Cu, Pb, Zn, Cd) content (total and mobile forms) is very dependant on the distance

from the sources of pollution to the sampling site. In the areas adjacent to sources

of pollution most values exceeded the warning threshold for sensitive type of land.

Also the intervention threshold for sensitive type of land for Cu, Pb, Zn, Cd was

frequently exceeded in Tăuţii de Sus and Ferneziu areas and for Pb it was exceeded

even in Valea Borcutului area. Following the assessment of pollution of studied

areas by calculating the “Z” pollution index we conclude that the areas are affected

by different degrees of pollution depending on the distance from the two sources of

industrial pollution. The “Z” index for Ferneziu area indicated excessive pollution,

being the closest area to the pollution sources. Tăuţii de Sus area has a “Z” index

which indicated very strong pollution. The pollution index for Valea Borcutului

46

area indicated moderate pollution. Cicârlău and Sighet areas have a “Z” index

corresponding to slight pollution.

• Regarding the fourth objective we conclude that the Pb content in vegetable leaves

exceeded the maximum permitted level by the FAO / WHO Codex Alimentarius

Commission, 2001, in all studied areas. Values for Cd content in lettuce leaves

exceeded the maximum permitted level in Tăuţii de Sus and Ferneziu areas and

values for Cd content in spinach leaves exceeded the maximum permitted level in

Tăuţii de Sus and Ferneziu areas and sporadically in Valea Borcutului area. For Cu

and Zn the maximum permitted content levels in vegetables were not exceeded.

• Regarding the fifth objective we conclude that the roots of the two vegetables

have antagonistic behavior in terms of concentration of these metals. While lettuce

roots mainly accumulate Cd, the roots of spinach accumulate more Pb, in both

cases mechanisms of blocking and sequestration of these metals at root level

intervene. Edible parts of vegetables concentrate Cd more intensely than Pb.

Considering the toxicity of Cd it is very important to monitor this metal more

closely. The average values for the concentration factor less than 1 for all metals

indicated a low translocation form soil to plant, which shows that both species

manifest exclusion behavior towards these metals.

• Regarding the sixth objective we conclude that Pb is more retained at root level

both by lettuce and spinach while Cd is more easily translocated to the spinach

leaves, which indicates a higher penetration risk in the food chain.

47

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