Research Collection

Master Thesis

Extraction of heavy metals from soil with selected biodegradablecomplexing agentsdiploma thesis

Author(s): Ritschel, Jens

Publication Date: 2003

Permanent Link: https://doi.org/10.3929/ethz-a-004596586

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ETH Library

F A C HH O C HSCHULEJ E N A

UNIVERSITY OF APPLIED SCIENCES

Extraction of heavy metals from soil with

selected biodegradable complexing agents

Diploma thesis

by

Jens Ritschel

Study course Environmental Engineering, FH Jena

Jena, May 2003

Table of contents

1 Introduction ...................................................................................................................... 1

1.1 Importance of metals.................................................................................................. 1

1.2 Treatment of contaminated soils ................................................................................ 1

1.3 Results of other researches......................................................................................... 3

1.4 Objective of thesis...................................................................................................... 3

2 Material and methods ...................................................................................................... 4

2.1 Characterisation of soils ............................................................................................. 4

2.2 Used complexing agents............................................................................................. 7 2.2.1 EDTA ................................................................................................................. 7 2.2.2 EDDS ................................................................................................................. 7 2.2.3 NTA.................................................................................................................... 7

2.3 Other chemicals used ................................................................................................. 8

2.4 Analytical methods..................................................................................................... 9 2.4.1 Atomic absorption spectrometry (AAS) ............................................................ 9 2.4.2 X-ray fluorescence analysis (XRF) .................................................................. 10

2.5 Experimental methods.............................................................................................. 11 2.5.1 Kinetic experiment ........................................................................................... 11 2.5.2 pH variation...................................................................................................... 11 2.5.3 Methods of sequential extraction ..................................................................... 12

2.6 Consideration of complex stability .......................................................................... 13

3 Results ............................................................................................................................. 16

3.1 Kinetics of extraction (Rafz soil) ............................................................................. 16 3.1.1 Calcium ............................................................................................................ 17 3.1.2 Magnesium....................................................................................................... 18 3.1.3 Iron ................................................................................................................... 19 3.1.4 Zinc................................................................................................................... 20 3.1.5 Lead.................................................................................................................. 21 3.1.6 Influence of detergents ..................................................................................... 22

3.2 Variation of pH value............................................................................................... 23 3.2.1 Calcium ............................................................................................................ 23 3.2.2 Magnesium....................................................................................................... 25 3.2.3 Manganese........................................................................................................ 27 3.2.4 Iron ................................................................................................................... 29 3.2.5 Copper .............................................................................................................. 31 3.2.6 Zinc................................................................................................................... 32 3.2.7 Lead.................................................................................................................. 34 3.2.8 Humic acid ....................................................................................................... 34

3.3 Sequential extraction ................................................................................................ 36 3.3.1 Fe and Mn......................................................................................................... 36 3.3.2 Copper .............................................................................................................. 38 3.3.3 Zinc................................................................................................................... 40 3.3.4 Lead.................................................................................................................. 42

4 Discussion........................................................................................................................ 43

4.1 Extraction with EDDS compared to EDTA ............................................................. 43 4.1.1 Conditional formation constants of Me-EDTA and Me-EDDS....................... 43 4.1.2 Effectiveness of extraction with EDDS compared to EDTA........................... 44

4.2 Extraction with NTA................................................................................................ 46 4.2.1 Conditional formation constants and speciation of Me-NTA .......................... 46 4.2.2 Effectiveness of extraction with NTA.............................................................. 51

4.3 Error discussion........................................................................................................ 51

5 Summary......................................................................................................................... 53

6 Acknowledgments........................................................................................................... 54

7 References ....................................................................................................................... 55

Table of figures Figure 2-1: Structural formula EDTA........................................................................................ 7 Figure 2-2: Structural formula EDDS ........................................................................................ 7 Figure 2-3: Structural formula NTA .......................................................................................... 8 Figure 2-4: Dilution of reference soil with glucose ................................................................. 10 Figure 3-1: Kinetics of the Ca extraction with different complexing agents at pH 4 and 7 .... 17 Figure 3-2: Kinetics of the Mg extraction with different complexing agents at pH 4 and 7 ... 18 Figure 3-3: Kinetics of the Fe extraction with different complexing agents at pH 4 and 7..... 19 Figure 3-4: Kinetics of the Zn extraction with different complexing agents at pH 4 and 7 .... 20 Figure 3-5: Kinetics of the Pb extraction with different complexing agents at pH 4 and 7..... 21 Figure 3-6: Extracted Ca from Kirschgarten soil as a function of pH ..................................... 24 Figure 3-7: Extracted Ca from Rafz soil as a function of pH .................................................. 24 Figure 3-8: Extracted Mg from Kirschgarten soil as a function of pH .................................... 25 Figure 3-9: Extracted Mg from Rafz soil as a function of pH ................................................. 26 Figure 3-10: Extracted Mn from Kirschgarten soil as a function of pH .................................. 27 Figure 3-11: Extracted Mn from Rafz soil as a function of pH ............................................... 28 Figure 3-12: Extracted Fe from Kirschgarten soil as a function pH ........................................ 29 Figure 3-13: Extracted Fe from Rafz soil as a function of pH................................................. 30 Figure 3-14: Extracted Cu from Kirschgarten soil as a function of pH ................................... 31 Figure 3-15: Extracted Zn from Kirschgarten soil as a function of pH ................................... 32 Figure 3-16: Extracted Zn from Rafz soil as a function of pH ................................................ 33 Figure 3-17: Extracted Pb from Rafz soil as a function of pH................................................. 34 Figure 3-18: UV/Vis extinction as function of humic acid concentration ............................... 35 Figure 3-19: Extracted humic acid as function of pH .............................................................. 35 Figure 3-20: Binding forms of Fe in Kirschgarten soil ............................................................ 37 Figure 3-21: Binding forms of Mn in Rafz soil ....................................................................... 37 Figure 3-22: Binding forms of Cu in Kirschgarten soil ........................................................... 38 Figure 3-23: Binding forms of Cu in Mattenweg soil .............................................................. 39 Figure 3-24: Binding forms of Zn in Kirschgarten soil ........................................................... 40 Figure 3-25: Binding forms of Zn in Mattenweg soil .............................................................. 41 Figure 3-26: Binding forms of Zn in Rafz soil......................................................................... 41 Figure 3-27: Binding forms of Pb in Rafz soil......................................................................... 42 Figure 4-1: Conditional formation constant lg Keff of Me-EDTA as function of pH............... 43 Figure 4-2: Conditional formation constant lg Keff of Me-EDDS as function of pH............... 44 Figure 4-3: Conditional formation constant lgKeff of Me-NTA as function of pH.................. 46 Figure 4-4: Molar concentrations in extraction solution at pH 4 ............................................. 47 Figure 4-5: Molar concentrations in extraction solution at pH 6 ............................................. 47 Figure 4-6: Molar concentrations in extraction solution at pH 8 ............................................. 48 Figure 4-7: Calculated speciation of NTA concentration 1 (ChemEQL) ................................ 49 Figure 4-8: Calculated speciation of NTA concentration 2 (ChemEQL) ................................ 50

Table of abbreviations

Complexing agents

EDTA Ethylenediamine tetra acetic acid

EDDS N,N’-Ethylenediamine disuccinic acid

NTA Nitriliotriacetic acid

IDSA Iminodisuccinic acid

MGDA Methylglycinediacetic acid

Analytical methods

AAS Atomic absorption spectrometry

UV/Vis Ultraviolet / visible absorption spectrometry

XRF X-ray fluorescence analysis

1

1 Introduction

1.1 Importance of metals

Metals can be found in all parts of the lithosphere. Most of them are dispersely distributed,

only small portions are concentrated in ores. Beside these geogenic concentrations, human use

of metals has led to significant changes in the circulation of metals.

Many metals are of great importance for biological processes. These metals needed as

nutrients by organisms are called essential metals. Some of them are needed in higher

amounts (macro-elements), others in smaller amounts (trace-elements). Shortage, but also

surplus of essential metals have negative influence on biomass growth. Non-essential metals

however can cause toxic effects at low concentrations.

This thesis is focused on the metals Cu, Pb and Zn as examples for relevant anthropogenic

contaminants of soil. While Pb is a non-essential metal, Cu and Zn are trace-elements. High

concentrations of these metals, typical for anthropogenic contamination, can have serious

effects on growth of organisms especially plants. Another danger is the accumulation in upper

parts of the food chain.

Additionally the essential metals Ca, Fe, Mg and Mn are observed with respect to negative

side effects of extraction.

1.2 Treatment of contaminated soils

Anthropogenic heavy metal contamination cannot be degraded chemically or biologically

because metals are elements. This limits the possibilities for treatment:

• Securing the contaminated area:

These are actions taken to lower the risk caused by the contamination, including

immobilisation and local binding, without actually removing the heavy metals from soil.

Introduction

2

• Removing the contaminated soil:

Removing all of the contaminated soil is probably the safest method, but only suited for

locally concentrated contamination. Otherwise the expenses of removing and disposing

the soil are too high. Additionally this method has a big impact on the ecosystem around

the contamination site and moves the problem to another site rather than solves it.

• Soil washing / chemical extraction

With suitable extraction agents most metals can be brought into solution and so washed

out from soil. Problems are caused by non-specific solving of essential material, such as

essential elements and organic matter and possible side effects of extraction solution

itself.

In this thesis chemical extractions with bio-degradable complexing agents are to be

investigated.

• Phytoextraction

Phytoextraction is a very soft method which causes the least negative changes to soil. The

principle is the absorption of bio-available metals by selected plants followed by their

harvest and removal. The main disadvantage is the long treatment time.

Introduction

3

1.3 Results of other researches

The basis of this work is the thesis by Bossart/Müller (4). They compared different

complexing agents like EDTA, EDDS, IDSA and MGDA with regard to their properties for

extraction of Zn and Cu from Dornach soils. Pb and Cd were not examined due to low

contaminations with these metals. The result showed EDDS as most promising biodegradable

alternative to EDTA. With concentrations equal to the molar sum of heavy metals in soil up to

72 % of Cu and 36 % of Zn could be extracted from a non-calcareous soil. Higher

concentrations of complexing agent led to better extraction results, but also to an increase in

the extraction of Ca, Fe and humic matter. Additionally better results were achieved by the

use of detergents together with EDDS.

1.4 Objective of thesis

The suitability of EDDS and NTA as biodegradable substitutes for EDTA in extraction of

heavy metal contaminated soils shall be investigated. This thesis is part of a research project

at the ETH Zurich. The experiments done here complement the results of former experiments

within this project.

In this thesis EDDS shall be investigated further. One experiment examines the kinetics of

EDTA and EDDS extractions for a soil with significant Pb contamination at two different pH

values. Extraction of Pb with EDDS has not been examined in the previous experiments by

Bossart/Müller (4). Additionally sequential extractions are done for original soil and already

extracted soil. This helps to understand how the binding forms of metals and the extraction

affect each other.

Finally, NTA shall be used in two concentrations for the extraction of Cu, Zn and Pb at

different pH values. NTA was not considered in the previous experiments, but is known as

strong and biodegradable chelating agent.

In all experiments negative side effects of the extraction have to be observed. These effects

include extraction of essential metals and organic material.

Material and methods

4

2 Material and methods

2.1 Characterisation of soils

For the experiments soils from three different Swiss locations were used. Two of them,

Kirschgarten and Mattenweg, are situated in Dornach (south of Basel), which is one of the

largest areas of high contamination with heavy metals in Switzerland. This pollution is caused

by air emissions from the non-ferrous metal industry. The third sample is from an

agriculturally used soil near Rafz (15 km north of Zurich) which was contaminated with

heavy metals by sludge fertilizer.

Samples from all soils were already dried at 40°C, ground and sieved to a particle size of 2

mm. General characteristics of the soils, except dry residue, were determined according to

VBBo. (16). Dry residue was measured according to DIN EN 13040 (7). The results are shown

in Table 2-1.

Mattenweg soil is a calcareous soil which results in a high pH value, it also has a the highest

organic matter content of all the soils. Kirschgarten is a silty soil which is non-calcareous.

Sandy Rafz soil has the lowest pH value and organic matter. Dry residue was determined for

testing purposes.

Table 2-1: Characteristics of soils used

pH value in

0.01 M

CaCl2

Organic

matter

Dry

residue

Carbonate

content

Particle-size distribution

(Pipett method)

Sand

(50 µm –

2 mm)

Silt

(2 µm –

50 µm)

Clay

(< 2 µm)

[%] [%] [% CaCO3] [%] [%] [%]

Kirschgarten 6.3

8.8 98.3 0.76 13 59 28

Mattenweg 7.1

12.7 98.0 12.22 25 40 35

Rafz 5.5

3.4 99.3 0.88 54 30 17

Material and methods

5

Table 2-2: Total metal concentrations [µg/g] measured with XRF

Na

Mg Al Ca Mn Fe Ni Cu Zn Cd Pb

Kirschgarten 4283 6220 51513 11636 894 27150 46.4 448 656 1.8 73.5

Mattenweg 2083 6806 52493 60276 840 30986 56.4 522 660 1.6 56.7

Rafz 7283 6416 46973 10620 845 19000 23.1 75.9 983 1.3 723

Reference soil

measured 3336

10326 53986 42246 1181 33413 46.7

95.7

507 2.7 171

Reference soil

Median 1 5548

11200 56900 42700 1205 32000 43.0

94.0

523 2.5 166

Difference in % -66.3

-8.5 -5.4 -1.1 -2.0 4.2 7.9

1.7

-3.0 7.4 3.3

Total metal concentrations were analysed using XRF. Table 2-2 shows the results. For

validation a reference soil (inter-laboratory test 2001.3/921) was also measured. The largest

difference between measured concentration and Median 1 was determined for Na and metals

with small concentrations. However, analyses for Ca, Fe, Mg, Mn, Pb and Zn are reliable with

XRF.

Obviously anthropogenic heavy metal contamination is found in all soils. The most

significant contamination is Cu in Kirschgarten and Mattenweg soils, Pb in Rafz soil and Zn

in all three soils.

The XRF analysis is not yet a standardised method. Therefore in addition an open digestion

with 2 M HNO3 was done. Extracts were analysed using AAS. Although not all metals can be

brought into solution with HNO3, the results represent ‘total metals’ according to VBBo. (16).

The soluble metals were determined by extraction with 0.1 M NaNO3. The extraction

solutions were analysed using AAS. The results of both extractions are shown in Table 2-3.

Material and methods

6

Table 2-3: ‘Soluble’ portion (NaNO3 extractable) and ‘total’ (HNO3 extractable) metals [µg/g] measured with AAS

Cu

Pb

Zn

Extractable

with

NaNO3

(‘soluble’)

HNO3

(‘total’)

NaNO3

(‘soluble’)

HNO3

(‘total’)

NaNO3

(‘soluble’)

HNO3

(‘total’)

Kirschgarten

0.91 445

< 0.25 70.7

1.20 794

Mattenweg

0.94 470

< 0.25 54.9

0.10 726

Rafz

0.24 66.0

< 0.25 747

11.1 1072

Results for total metals analysed with AAS are slightly different to the XRF results mainly for

Zn. Tests with reference soil showed that results for Zn were generally too high (cp.

appendix). After a maintenance of the AAS this problem was solved.

As expected Pb is immobile in all soils. A strikingly high amount of mobile Zn is found in

Rafz soil.

Beside all differences the molar sum of heavy metal contamination is similar in all three soils

(Table 2-4). Therefore the same concentrations of extraction agents could be used.

Table 2-4: Molar concentrations of heavy metals

Cu

[µmol/g]

Zn

[µmol/g]

Cd

[µmol/g]

Pb

[µmol/g]

Ni

[µmol/g]

∑

[µmol/g]

Kirschgarten 7.1 10.0 0.0 0.4 0.8 18.3

Mattenweg 8.2 10.1 0.0 0.3 1.0 19.6

Rafz 1.2 15.0 0.0 3.5 0.4 20.1

Material and methods

7

2.2 Used complexing agents

2.2.1 EDTA

EDTA (Ethylenediamine tetra acetic acid) is the most

widely used complexing agent. It forms strong

complexes with many metals. Disadvantages are its

unselective nature and the poor biodegradability (5).

For the experiments Na2-EDTA was used (company

Merck, M = 336.2 g/mol).

Figure 2-1: Structural formula EDTA

2.2.2 EDDS EDDS (N,N’-Ethylenediamine disuccinic acid) is a structural isomer of EDTA. Its ability to

form stable complexes is similar to EDTA.

It has been reported that both EDDS and its metal complexes are readily biodegradable (14).

This only relates to the stereoisomer SS-EDDS.

In the last years many investigations have tried to

test its suitability as a substitute for EDTA for many

purposes, e.g. in laundry detergents.

EDDS was used as Na3-N,N’-EDDS (company

Procter & Gamble, M = 358.2 g/mol).

Figure 2-2: Structural formula EDDS

2.2.3 NTA NTA (Nitrilotriacetic acid) is also a strong complexing agent. It is widely used in many

countries, but restricted or banned in others because NTA is rated as a possible carcinogen.

Newer examinations query a risk for humans at usual concentrations (17).

Material and methods

8

NTA is reported to be readily biodegradable in some

sources, but this seems to depend on adaptation of

micro-organisms (5) (13).

The chemical form used was Na3-NTA salt (company

Fluka, purity purum, M = 257.1 g/mol).

Figure 2-3: Structural formula NTA

2.3 Other chemicals used

NaNO3

Sodium nitrate (company Fluka, purity pa) was used to simulate the ionic strength of tap

water which would be used in a big scale operation, without introducing metal ions present in

tap water. It was basis for all extraction solutions.

HNO3

Nitric acid (company Merck, purity pa) of different concentrations was used to set pH value

and to acidify samples for AAS.

NaOH

Sodium hydroxide (company Fluka, purity pa) of different concentrations was also used to set

the pH value.

Glucopon 650 EC

Glucopon (company Henkel) is an aqueous, non-ionic solution of alkyl polyclycosides based

on natural fatty alcohols.

Schinkel solution

Schinkel solution contains 10 g/L CsCl (caesium chloride) and 100 g/L LaCl (lanthanum

chloride). It is used to eliminate chemical interferences which depress absorbance of Ca and

Mg during measurement with AAS.

Material and methods

9

2.4 Analytical methods

2.4.1 Atomic absorption spectrometry (AAS)

AAS is the standard method for determination of metals in solutions. Per analysis only one

element can be determined.

Samples are centrifuged for 15 minutes at 2500 rpm and then vacuum filtrated with pore size

0,45 µm. The used Flame-AAS (type Varian) has got a slot burner, an auto sampler and

computer based evaluation. All measurements were done with an oxidising air-acetylene

flame (T ≈ 2200 °C). Table 2-5 shows the other working conditions.

Table 2-5: Working conditions for AAS measurements (based on Recommended instrument parameters (15))

Element Wavelength

[nm]

Slit width

[nm]

Optimum working range

[µg/mL]

Remarks

Ca 422.7 0.5 0.01 - 3 Schinkel solution added as releasing agent (cp. 2.3)

Cu 324.7 0.5 0.03 - 10

Fe 248.3 0.2 0.06 - 15

Mg 285.2 0.5 0.003 - 1 Schinkel solution added as releasing agent (cp. 2.3)

Mn 279.5 0.2 0.02 - 5

Pb 217.0 1.0 0.1 - 30

Zn 213.9 1.0 0.01 - 2

Material and methods

10

2.4.2 X-ray fluorescence analysis (XRF)

XRF is a physical measuring method which allows non-destructive analysis of solid samples.

With one analysis all elements measurable with the used detector can be captured.

4 g of ground soil are mixed with 0.9 g wax C micro powder and then shaken for 8 minutes at

17 Hz. The mixed powder will be pressed to a pellet at 150 kN. After that the pellet is

analysed with XRF. The used energy-dispersive XRF with a Si (Li) solid-state detector allows

analysis for elements from atomic number 11 (Na) to 92 (U).

Samples of sequential extraction residue were not sufficient for XRF. Therefore these samples

were diluted with glucose. A test with reference soil in different relations soil / glucose was

done to confirm that glucose does not affect the results significantly. Figure 2-4 shows the

measured results compared to the reference values. Due to this results a dilution of

approximately 1:1 was chosen for the residue.

0

100

200

300

400

500

600

1 2 3weight of soil in 3 g sample [g]

met

al c

once

ntra

tion

[ug/

g]

Pb measured Zn measured Cu measuredReference Pb Reference Zn Reference Cu

Figure 2-4: Dilution of reference soil with glucose

Material and methods

11

2.5 Experimental methods

2.5.1 Kinetic experiment

8 g of fine ground Rafz soil were extracted for 48 hours with constant shaking. The extraction

solution was 400 mL 0.01 M NaNO3 containing 400 µmol/L complexing agent. This

concentration equals the molar sum of Cd, Cu, Ni, Pb, Zn (about 20 µmol/g soil, cp. Table

2-4).

EDDS and EDTA (reference) were used as complexing agents, additionally one sample was

extracted without complexing agent. The soil was extracted at pH 4 and pH 7 by both

chelating agents. The pH value was set and kept constant during extraction by addition of

HNO3 or NaOH. Correction of pH was done before every sample taking with a tolerance of

± 0.1. An additional sample containing EDDS and the detergent Glucopon (20 g/L) was

extracted at pH 7.

After 1, 2, 4, 8, 24, 32, 48 hours samples of 30 mL were taken. Here an attempt was made to

keep the soil / solution ratio constant by taking the sample from the shaken solution. These

samples were analysed for Ca, Cu, Fe, Mg, Pb and Zn by Flame-AAS (cp. 2.4.1).

It has to be noted that the solution containing soil and NaNO3 was made 2.5 days before the

beginning of the extraction. This was necessary to set a stable pH value. Therefore the

solutions could already contain dissolved metals at the beginning of extraction, mainly at

pH 4.

2.5.2 pH variation

Always 0.8 g of fine ground soil from Kirschgarten, Mattenweg and Rafz were used for

extraction. Extraction time was 24 hours with constant shaking.

The extraction solution was 40 mL 0.01 M NaNO3 to get the same soil / solution ratio as in

the kinetics experiment. Two different concentrations of NTA were added as complexing

agent: concentration 1 (400 µmol/L) which equals the molar sum of Cd, Cu, Ni, Pb, Zn and

concentration 2 (4000 µmol/L) which is ten times this concentration (cp. Table 2-4).

Additionally one extraction was done without complexing agent.

Material and methods

12

For each concentration of NTA with each combination soil / extraction solution, pH values

were set between 3 and 8 in steps of 0.5 by adding HNO3 or NaOH. Twice a day the pH value

was controlled and set with a tolerance of ± 0.1. After the extraction all samples were

analysed with Flame-AAS for Ca, Cu, Fe, Mg, Mn, Pb and Zn (cp. 2.4.1).

During experiments it could be observed that the colours of the extraction solutions differed.

With increasing pH value it changed from clear over yellow to brown. Generally the colour

was stronger for higher concentrations of NTA. To find a quantification for this effect

exemplary all solutions from Kirschgarten soil were analysed with UV/Vis at a wavelength of

432 nm. It could be expected that solved humic acids are the main cause for the colour

change. Therefore the UV/Vis was calibrated with humic-acid-Na-salt.

2.5.3 Methods of sequential extraction

The sequential extraction was accomplished according to the process developed by Zeien

(18). The principle is a sequence of different extraction steps with increasing strength of

extraction agent and decreasing pH value of extraction solution. Metals found in each

extracted fraction can be assigned to specific binding forms in soil.

All 7 extraction steps are shown in Table 2-6. However, the residual fraction was not

determined by digestion but with XRF. The samples from all other extraction steps were

analysed with Flame-AAS for Cu, Fe, Mn, Pb and Zn.

Before the start of sequential extraction 5 g from Kirschgarten, Mattenweg and Rafz soil were

extracted with 400 µmol/L EDDS in 250 mL 0.01 M NaNO3. From each soil and a blank

extractions were done for 24 hours and for 48 hours in duplicate analysis. The pH value was

observed but not changed. Extraction solution was then analysed with Flame-AAS. Residue

was rinsed with 50 mL of 0.01 M NaNO3 twice, each time including centrifugation and

filtration. After that 2 g of each dried residue and 2 g from each fresh soil were taken for

sequential extraction. This was done also including a blank and in duplicate analysis.

Material and methods

13

Table 2-6: Sequential extraction (18)

Scheme of sequential extraction

Fraction

1. Mobile

2. Easy available

3. Occluded in Mn-Oxides

4. Organic bound

5. Occluded in amorphous

Fe-oxides

6. Occluded in crystalline

Fe-oxides

7. Residue (bound in

silicates)

Extraction agent used

• 1 M NH4NO3

• 1 M NH4OAc. (pH 6.0)

• 0.1 M NH2OH-HCl + 1 M NH4OAc. (pH 5.5)

• 0.025 M NH4EDTA (pH 4.6)

• 0.2 M NH4Oxalate (pH 3.25)

• 0.1 M Ascorbic acid in 0.2 M NH4Oxalate (pH

3.25)

• HNO3 + H2O2 + HF conc.

2.6 Consideration of complex stability

To understand the reactions during extraction with complexing agents it is important to know

the metal ion – ligand interactions. The complexation can be regarded as equilibrium reaction

between the ligand and the competing metal ions:

M i+ + L j- ⇔ ML (i-j) (1)

with M Metal ion (e- pair acceptor)

i charge of M

L Ligand (e- pair donor)

j charge of L

Material and methods

14

According to the principle of mass action the activities of M, L and ML relate as follows:

]][[][ )(

−+

+−

= ji

ji

ML LMMLK (2)

with [..] activity

KML equilibrium constant

For complexations KML is also called formation constant or stability constant KSt. This

constant describes the strength of a complex with this specific metal. However, it does not

take into account the effects of pH value. For this reason a conditional stability constant Kcond

can be defined:

lg Kcond (pH) = lg KSt – lg αHL – lg αM (3)

with Kcond conditional stability constant

KSt stability constant, equals KML from equation (2)

αHL coefficient of ligand protonation

αM coefficient of side reactions competing with the ligand for the metal ions

Note: lg always means logarithm to the base 10

Ligand protonation

L j- is a reasonable strong base. Therefore the amount of free L j- increases with increasing

pH value. The single steps of protonation are described by the equilibrium constants

K1, K2,.. , Km.

αHL is defined as:

αHL = 1 + [H+] K1 + [H+]2 K1 K2 + … + [H+]m Km! (4)

Note: Km! means factorial of Km

Material and methods

15

Competing reactions

Side reactions include formation of metal hydroxides, effects of buffers and forming of MLH

(metal ion – ligand – proton) or MLOH (metal ion – ligand – hydroxide) species. For

simplification this calculation considers only formation of metal hydroxides as most

important effect.

Formation of insoluble metal hydroxides prevents these metal ions from being complexed.

The concentration of metal hydroxides increases with increasing pH value. The steps of OH-

acceptance by the metal ion are described by the equilibrium constants KI, KII,.. , Kn.

However, only the species which are formed in the system may be considered.

αM is defined as:

αM = 1 + sI [OH-] KI + sII [OH-]2 KI KII + … + sn [OH-]n Kn! (5)

with s factor which determines if species n exists (s = 1) or not (s = 0)

The calculation and the definitions are based on Davidge et al (6). Selected results calculated

with these equations will be used in chapter 4.

Results

16

3 Results

3.1 Kinetics of extraction (Rafz soil)

The values from the AAS were used to calculate concentrations of metals extracted from soil

in µg metal per g dry soil. These results can be found in the appendix.

With these values and the total concentrations measured with XRF it was possible to calculate

the extracted metal in % of the total concentration in soil. These results were chosen for

graphical presentation except for the extraction of Fe. Here the concentration in µg/g soil was

used because the percentage portion is very small but the total concentration is relevant as

Fe complexes.

The diagrams show the development of the concentration of the specific metal in the

extraction solution during extraction time.

The results for the different extraction solutions (EDTA, EDDS and without complexing

agent) at pH values 4 and 7 are shown in one diagram.

Results

17

3.1.1 Calcium

The extraction of Ca occurs very fast. The maximum for most of the extraction solutions is

reached within the first hour. Then the curves stay nearly constant.

45 to 50 % was extracted at pH 4 and about 15 % at pH 7. There is no significant influence of

the extracting agent on the amount of Ca in the extraction solution.

0

10

20

30

40

50

60

0 10 20 30 40 50

extraction time [h]

extr

acte

d m

etal

in %

of t

otal

EDTA pH4

EDTA pH7

EDDS pH4

EDDS pH7

w/o complexingagent pH4

w/o complexingagent pH7

Figure 3-1: Kinetics of the Ca extraction with different complexing agents at pH 4 and 7

Results

18

3.1.2 Magnesium

The kinetic of the Mg extraction is very similar to that of Ca, but at a lower level. At pH 4

about 10 % was extracted and at pH 7 about 2 %. Again the only significant increase in

extraction is during the first hour and the presence of a complexing agent had no effect on the

Mg concentration measured with AAS.

0

5

10

15

0 10 20 30 40 50

extraction time [h]

extr

acte

d m

etal

in %

of t

otal

EDTA pH4

EDTA pH7

EDDS pH4

EDDS pH7

w/o complexingagent pH4

w/o complexingagent pH7

Figure 3-2: Kinetics of the Mg extraction with different complexing agents at pH 4 and 7

Results

19

3.1.3 Iron

The kinetics of the Fe extraction show a different trend to Ca and Mg. There are no significant

amounts of Fe extracted without a complexing agent or with EDTA at pH 7, but with EDDS

at pH 7 there is a steadily increasing amount of Fe extracted over time. After 48 hours about

180 µg/g soil was extracted and the extraction has not reached a steady state. At pH 4 the

value is even higher with a maximum of 450 µg/g soil. Also EDTA was able to extract up to

300 µg/g soil at this pH value during the 48 hours. EDDS at pH 4 seems to reach a maximum

extraction at 32 hours, but to ensure this is correct it would be necessary to study a longer

extraction time.

The observed amounts of extracted iron have no influence on plant growth. However, the

importance of Fe lies in its properties as competitive ion of complexation.

0

100

200

300

400

500

0 10 20 30 40 50extraction time [h]

extr

acte

d m

etal

in u

g/g

EDTA pH4

EDTA pH7

EDDS pH4

EDDS pH7

w/o complexing agentpH4

w/o complexing agentpH7

Figure 3-3: Kinetics of the Fe extraction with different complexing agents at pH 4 and 7

Results

20

3.1.4 Zinc

Zn is not mobile at pH 7 due to forming of insoluble Zn-hydoxides, so practically nothing

could be extracted without a complexing agent at this pH value. With EDTA and EDDS it

was possible to extract about 50 % of the Zn from soil. There is no significant difference

between the two complexing agents at this pH value. The extraction shows an exponential rise

within the first hour and then the increase slows considerably.

At pH 4 Zn in Rafz soil is very mobile, about 60 % is extracted without adding any

complexing agent. With EDTA this can be increased up to 90 %. EDDS performs worse than

EDTA extracting up to 80 % of total Zn. Again the largest increase is within the first hour.

EDTA extraction then stays constant around 80 % and EDDS drops down to the level reached

without complexing agent by 32 hours.

0

20

40

60

80

100

0 10 20 30 40 50

extraction time [h]

extr

acte

d m

etal

in %

of t

otal

EDTA pH4

EDTA pH7

EDDS pH4

EDDS pH7

w/o complexingagent pH4

w/o complexingagent pH7

Figure 3-4: Kinetics of the Zn extraction with different complexing agents at pH 4 and 7

Results

21

3.1.5 Lead

Pb is mobile neither at pH 4 nor at pH 7. Without complexing agent the extracted amount was

below 2 %.

At pH 7 the addition of EDTA or EDDS leads to an extraction of about 25 %. In the first 24

hours both performed identically, then the extraction with EDTA rose further but EDDS

dropped slightly.

At pH 4 EDTA was able to extract nearly 60 % of the Pb from soil. The extraction reaches its

maximum after 8 hours which is slower than most of the kinetics examined. EDDS showed at

this pH value no significant effect compared to the extraction solution without complexing

agent.

0

10

20

30

40

50

60

70

0 10 20 30 40 50extraction time [h]

extr

acte

d m

etal

in %

of t

otal

EDTA pH4

EDTA pH7

EDDS pH4

EDDS pH7

w/o complexing agent pH4

w/o complexing agent pH7

Figure 3-5: Kinetics of the Pb extraction with different complexing agents at pH 4 and 7

Results

22

3.1.6 Influence of detergents

Contrary to the expectation the use of Glucopon as detergent did not change the kinetics and

total extracted amounts of metals. The results can be found in the appendix. Obviously the

increased dispersion of soil particles does not increase the metal extraction.

It has to be considered that for all experiments the soil was fine ground. If the grain size is

much bigger, e.g. in big-scale extractions, detergents could have influence on the kinetics.

Additionally the results of Bossart/Müller (4) show a significant increase in extracted Zn and

Cu for different soils. Compared to the soils examined there, Rafz soil is very sandy. This

suggests that the soil character is also of importance for the effect of detergents.

Results

23

3.2 Variation of pH value

The results from the AAS were used to calculate metal concentrations in µg/g soil taking into

account dilutions made for analysis. These results can be found in the appendix.

With these results and the total concentrations measured with XRF it was possible to calculate

the extracted metal in % of the total concentration in soil. These results were chosen for

graphical presentation except for the extraction of Fe. Here the concentration in µg/g soil was

used because the percentage portion is very small but the total concentration is relevant as Fe

complexes. As for all experiments Pb for Kirschgarten and Cu for Rafz were not evaluated

because little contamination was found there.

The diagrams show the development of the concentration of the specific metal in the

extraction solution as a function of pH. The results for the different extraction solutions (NTA

1, NTA 2 and without complexing agent) are shown in one diagram. NTA 1 concentration

(400 µmol/L) equals the molar sum of Cd, Cu, Ni, Pb, Zn in soil used. NTA 2 concentration

(4000 µmol/L) equals ten times this concentration (cp. Table 2-4).

3.2.1 Calcium

The curves of the extraction of Ca as a function of pH are not smooth for both soils.

Additionally some results do not seem to be logical (higher amounts of extracted metal

without complexing agent than with the use of NTA).

The general trend is the decrease of extracted Ca with increasing pH value. For Rafz there is a

abrupt drop from pH 7 with NTA 1 and without complexing agent, while the decrease for

Kirschgarten is more gradual.

For pH values from 6.5 to 8 there is an increasing effect of NTA 2 on extraction leading to a

difference of about 30 % compared to NTA 1 at pH 8.

Results

24

0

10

20

30

40

50

60

70

3 4 5 6 7 8

pH

extr

acte

d m

etal

in %

of t

otal

.

NTA concentration 1

NTA concentration 2

w/o complexing agent

Figure 3-6: Extracted Ca from Kirschgarten soil as a function of pH

0

10

20

30

40

50

60

70

3 4 5 6 7 8

pH

extr

acte

d m

etal

in %

of t

otal

NTA concentration 1

NTA concentration 2

w/o complexing agent

Figure 3-7: Extracted Ca from Rafz soil as a function of pH

Results

25

3.2.2 Magnesium

Only small percentages of Mg were extracted. The amounts range from about 4 %

(Kirschgarten) to 10 % (Rafz) at pH 3 to about 1 % at pH 8.

There was no significant difference in the extraction between NTA 1 and without complexing

agent (the value for Rafz at pH 3 can be considered as outlier).

NTA 2 increased the extracted amount of Mg slightly at pH values higher than 7 for

Kirschgarten compared to NTA 1 and without NTA.

0

1

2

3

4

3 4 5 6 7 8

pH

extr

acte

d m

etal

in %

of t

otal

NTA concentration 1

NTA concentration 2

w/o com plexing agent

Figure 3-8: Extracted Mg from Kirschgarten soil as a function of pH

Results

26

0

10

20

3 4 5 6 7 8

pH

extr

acte

d m

etal

in %

of t

otal

NTA concentration 1

NTA concentration 2

w/o complexing agent

Figure 3-9: Extracted Mg from Rafz soil as a function of pH

Results

27

3.2.3 Manganese

As for most metals the amount of extracted Mn increases with lowering pH values. Without

complexing agent it ranges from about 40 % (Kirschgarten) - 20 % (Rafz) at pH 3 to 1 % at

pH 8.

A significant increase in extraction due to NTA 1 can only be observed for Rafz at pH 3 to 4.

The use of NTA 2 led to a higher extraction rate of Mn. The highest increase compared to the

extraction with NTA 1 can be observed at pH values from 5 to 6 for Kirschgarten and 4 to 6

for Rafz. At higher pH values the difference decreases abruptly for Kirschgarten at pH 7.5 and

more slowly for Rafz.

0

10

20

30

40

50

60

70

3 4 5 6 7 8

pH

extr

acte

d m

etal

in %

of t

otal NTA concentration 1

NTA concentration 2

w/o complexing agent

Figure 3-10: Extracted Mn from Kirschgarten soil as a function of pH

Results

28

0

10

20

30

40

50

60

3 4 5 6 7 8

pH

extr

acte

d m

etal

in %

of t

otal

.

NTA concentration 1

NTA concentration 2

w/o complexing agent

Figure 3-11: Extracted Mn from Rafz soil as a function of pH

Results

29

3.2.4 Iron

The results are similar for both soils. Without complexing agent there is no significant

extraction of Fe. With NTA 1 the amount of extracted Fe decreases with increasing pH value

steadily from about 300 µg/g to about 30 µg/g.

The use of NTA 2 led to a greatly increasing extraction of Fe, about 1000 µg/g more at pH 3

compared to NTA 1. In the discussion it will be shown how this amount of extracted Fe

influences the formation of complexes.

0

200

400

600

800

1000

1200

1400

3 4 5 6 7 8

pH

extr

acte

d m

etal

in u

g/g NTA concentration 1

NTA concentration 2

w/o complexing agent

Figure 3-12: Extracted Fe from Kirschgarten soil as a function pH

Results

30

0

200

400

600

800

1000

1200

1400

3 4 5 6 7 8

pH

extr

acte

d m

etal

in u

g/g

.

NTA concentration 1

NTA concentration 2

w/o com plexing agent

Figure 3-13: Extracted Fe from Rafz soil as a function of pH

Results

31

3.2.5 Copper

With NTA 1 up to 58 % could be extracted at pH 4.5. For lower pH values this percentage

decreases slightly to 50 % at pH 3. Also higher pH values lead to a decreasing extracted

amount of Cu. The decrease is slight to 46 % at pH 7 and then steeper down to 25 % at pH 8.

With NTA 2 the extraction curve has a different shape. The maximum lies here at pH 3 with

82 %. With higher pH values the extracted percentage decreases steadily to 56 % at pH 8.

Without complexing agent Cu goes into solution only at low pH values.

0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8

pH

extr

acte

d m

etal

in %

of t

otal NTA concentration 1

NTA concentration 2

w/o complexing agent

Figure 3-14: Extracted Cu from Kirschgarten soil as a function of pH

Results

32

3.2.6 Zinc

The shape of the extraction curves are similar for both soils but for Rafz generally more

extraction occurs. Compared to Cu, Zn is more mobile, leading to higher extraction without

the use of complexing agents especially at low pH values.

With NTA 1 the amount of extracted Zn can be held nearly constant at 40 % for Kirschgarten.

For Rafz it decreases slowly from 80 % to about 60 % by pH 7. After pH 7 there is a drop in

extraction by about 20 %.

The effect of NTA 2 is not as big as for Cu. The extracted amounts are in average 10 %

higher than with concentration 1. At pH values below 4.5 and for Rafz at 7.5 and 8 the higher

concentration has a bigger influence than in the intermediate pH ranges.

0

10

20

30

40

50

60

70

3 4 5 6 7 8

pH

extr

acte

d m

etal

in %

of t

otal NTA concentration 1

NTA concentration 2

w/o complexing agent

Figure 3-15: Extracted Zn from Kirschgarten soil as a function of pH

Results

33

0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8

pH

extr

acte

d m

etal

in %

of t

otal

NTA concentration 1

NTA concentration 2

w/o complexing agent

Figure 3-16: Extracted Zn from Rafz soil as a function of pH

Results

34

3.2.7 Lead

Pb is nearly immobile at pH values higher than 4. So only at very low pH values there is a

significant extraction without complexing agents.

With NTA 1 the extracted amount of Pb is generally higher. Surprisingly the maximum is not

reached at very low pH values but at pH 5.5 with 31 %.

The use of NTA 2 causes the largest increase in amount of extracted metal compared to NTA

1. At pH values below 5 over 90 % of Pb was extracted. And at pH 8 still over 50 % was

found in the extraction solution.

0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8

pH

extr

acte

d m

etal

in %

of t

otal

NTA concentration 1

NTA concentration 2

w/o complexing agent

Figure 3-17: Extracted Pb from Rafz soil as a function of pH

3.2.8 Humic acid

The calibration shows a linear correlation of extinction and humic acid concentration between

0 and 100 mg/L (Figure 3-18). Therefore it could be used for the determination of humic acid

concentration in the extraction solutions. The results from the UV/Vis analyses were

calculated as % of organic matter and are shown in Figure 3-19.

Results

35

Calibration of UV/Vis

R2 = 0,9993

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0 20 40 60 80 100 120

c [mg/L] of humic acid

Extin

ctio

n

Figure 3-18: UV/Vis extinction as function of humic acid concentration

0

1

2

3

4

5

6

7

3 4 5 6 7 8

pH

extr

acte

d hu

mic

aci

d in

%

of o

rgan

ic m

atte

r

NTA concentration 1

NTA concentration 2

w/o complexingagent

Figure 3-19: Extracted humic acid as function of pH

The results confirm the observations made with the naked eye. With increasing pH value the

amount of extracted organic matter increases steadily, but for NTA 2 at pH > 7 the increase is

exponential. However, it has to be considered that probably not only humic acids have been

Results

36

measured. Despite that, the results can be seen as an indication for the extracted organic

material dependent on pH value and NTA concentration.

3.3 Sequential extraction

The results of all fractions measured with the AAS were calculated as µg per g soil. Then all

fractions were added up to get the total metal concentration in the soil. With this value it was

possible to calculate the percentage of metal in the single fractions in relation to the total

concentration. The total concentrations from the characterisation with XRF (Table 2-2) were

not used because of the large differences between the two results. These were caused by the

sum up of errors during the single extraction steps (cp. 4.3).

Beam diagrams were used for the graphical presentation of the results. Each beam equals

100% of the specific metal in the soil. The different shades represent the 7 fractions.

Additionally the part which was extracted with EDDS is shown. So it is possible to see from

which fractions the metal could be extracted.

3.3.1 Fe and Mn

Fe and Mn were only measured to show the reliability of the extraction used. The results

show that the distribution is similar for all soils. Fe and Mn are found in the expected

fractions, Mn in Mn-oxides fraction, Fe in Fe-oxides fractions. Suspicious is the large amount

of Fe in the residual fraction.

As examples Figure 3-20 shows the distribution of Fe in Kirschgarten soil and Figure 3-21

shows the distribution of Mn in Rafz soil. The other results are given in the appendix.

Results

37

Figure 3-20: Binding forms of Fe in Kirschgarten soil

Figure 3-21: Binding forms of Mn in Rafz soil

Results

38

3.3.2 Copper

As in the other experiments Cu was only evaluated for Kirschgarten and Mattenweg. In both

evaluated soils most of the copper (69 % for Kirschgarten and 60 % for Mattenweg) can be

found in the organic fraction. This corresponds to data in literature (3). About 20 % in total

are found in the Fe-oxides and the residue fractions. The remaining 10 % (Kirschgarten)

respectively 19 % (Mattenweg) of Cu are in the first three fractions.

From Kirschgarten 59 % of Cu could be extracted after 24 hours and 64 % after 48 hours with

EDDS. The extraction results for Mattenweg are 42 % after 24 hours and 48 % after 48 hours.

For both soils there is no significant change in Fe-oxides and residue fractions during

extraction. Mobile, easily available and Mn-oxides fractions nearly disappear and the organic

fraction decreases greatly.

Figure 3-22: Binding forms of Cu in Kirschgarten soil

Results

39

Figure 3-23: Binding forms of Cu in Mattenweg soil

Results

40

3.3.3 Zinc

The distribution of Zn was evaluated for all three soils. All soils have in common that a big

portion of Zn is bound in Fe-oxides and residue fractions. These are 60 % for Kirschgarten,

69 % for Mattenweg and 44 % for Rafz soil.

16 % of Zn can be found in the organic fraction of all soils. 26 % of Zn in Rafz is mobile or

easily available, 14 % of Kirschgarten’s Zn and only 9 % of Zn in Mattenweg soil. The

remaining Zn (8 to 14 %) is bound in the Mn-oxide fraction.

The extraction results are disappointing. Only 12 % of Mattenwegs Zn could be extracted

after 24 hours, 28 % of Kirschgarten and 33 % of Rafz with EDDS. After 48 hours the results

are only slightly better. Again it is obviously that the Fe-oxides and residue fractions are

nearly unchanged during extraction.

Figure 3-24: Binding forms of Zn in Kirschgarten soil

Results

41

Figure 3-25: Binding forms of Zn in Mattenweg soil

Figure 3-26: Binding forms of Zn in Rafz soil

Results

42

3.3.4 Lead

The only significant contamination with Pb was found in Rafz soil, therefore only these

results were evaluated.

In the unextracted soil 4 % of Pb were bound in the Fe-oxides and residue fractions, 51 % in

the organic fraction, 31 % occluded in Mn-oxides and 15 % were mobile or easy available.

Only 22 % of Pb was extracted after 24 hours and this did not change after 48 hours. This

result seems strange, because the extraction result for the other metals have indicated that the

fractions up to the organic fraction can be well extracted with EDDS. The reasons for the poor

extraction of Pb will be discussed later.

The changes in Fe-oxides and residue fractions are within the error range (± 5%, cp. 4.3), all

other fractions have decreased slightly.

Figure 3-27: Binding forms of Pb in Rafz soil

43

4 Discussion

4.1 Extraction with EDDS compared to EDTA

4.1.1 Conditional formation constants of Me-EDTA and Me-EDDS

For an interpretation of the results it is helpful to know the complex stabilities. These are

described by the formation constants. In Figure 4-1 and Figure 4-2 lg Keff as function of pH

value is shown. Keff was calculated according to the equations in chapter 2.6. The used

constants can be found in the appendix.

Suspicious is the decrease of complex strength below pH 6 due to ligand protonation. The

effect of Fe hydroxilation at high pH values leads to a change in the order of complex

formation ( pH 4: Fe > Cu > Pb > Zn > Mn > Ca; pH 7: Cu > Pb > Fe > Zn > Mn > Ca ).

-10,00

-5,00

0,00

5,00

10,00

15,00

20,00

25,00

0 1 2 3 4 5 6 7 8 9 10 11

pH

log

(Kef

f) CuEDTA

FeEDTA

PbEDTA

ZnEDTA

CaEDTA

MnEDTA

Figure 4-1: Conditional formation constant lg Keff of Me-EDTA as function of pH

Discussion

44

-20,00

-15,00

-10,00

-5,00

0,00

5,00

10,00

15,00

20,00

25,00

0 1 2 3 4 5 6 7 8 9 10 11

pH

log

(Kef

f) CuEDDS

FeEDDS

PbEDDS

ZnEDDS

CaEDDS

MnEDDS

Figure 4-2: Conditional formation constant lg Keff of Me-EDDS as function of pH

4.1.2 Effectiveness of extraction with EDDS compared to EDTA

At neutral pH values EDDS performed similarly to EDTA in the extraction of Pb and Zn.

However, there are still significant concentrations of these two metals in soil after extraction.

For example, the best extraction results for Rafz leave about 500 µg/g Pb and about 540 µg/g

Zn in soil. This is far above the limits of AbfKlärV (1) for agricultural soils (pH 5-6) which

are allowed to be fertilised with sludge: 100 µg/g Pb and 160 µg/g Zn. The sequential

extraction results indicated that while Zn extraction is limited mainly by the binding forms,

Pb may benefit from a higher concentration of EDDS. This assumption is supported by results

of experiments with different concentrations of NTA. Generally it has been shown that strong

Fe complexes compete with weaker Pb and Zn complexes. This effect is even more severe at

low pH values. Here EDDS is nearly of no use for Pb and Zn extraction at the concentration

used. Fe ions are stronger competitors in EDDS complexation than in EDTA complexation.

This effect would have to be compensated with higher concentrations of EDDS.

Discussion

45

Other potentially competitive ions are Ca and Mn. Although the total amount of these metals

is not changed by the complexing agent, they form complexes if ligands are available. The

smaller stability of these complexes is compensated by the higher concentration of the metal

ions. The largest effect can be expected by Ca at high pH values. However, due to a very

weak Ca-EDDS species compared to Ca-EDTA this problem is substantially greater for

EDTA.

Chapter 4.1.1 shows that Cu forms very strong complexes over a wide pH range. Although no

evaluation of Cu kinetics was done, sequential extraction results show that Cu can be well

extracted by EDDS. Best extraction results are 65 % of Cu from Kirschgarten soil, leaving

about 160 µg/g in soil. However this concentration still fails to comply to AbfKlärV (1) which

gives a limit of 60 µg/g. Although Kirschgarten soil is not an agriculturally used soil, this

value can be seen as a guideline.

The kinetics show that most metals are extracted within the first 8 hours. The only exception

is Fe which shows slow kinetics due to binding in amorphous and crystalline form. The

increasing amount of Fe being dissolved means that a shorter extraction time may benefit the

extraction of other metals due to less competition from Fe.

Negative side effects with regard to the extraction of essential metals are not increased

significantly by the use of EDTA or EDDS at the concentration used. However, chemical

extraction is no soft process for decontamination of soils and does always change the soil

characteristics considerably. If higher concentrations of complexing agent are used, these

effects can be expected to increase similarly to the ones examined with NTA concentration 2.

The results of the sequential extraction showed that EDDS is able to extract metals from Mn-

oxides and organic complexes, together with the mobile and easily available metals these

fractions are the potential extractable portion of heavy metals in soil. On the other hand it is

not possible to extract significant amounts of metals from the Fe oxides and the silicates. This

must be considered when the suitability of a contaminated soil for chemical extraction has to

be determined.

Discussion

46

4.2 Extraction with NTA

4.2.1 Conditional formation constants and speciation of Me-NTA

As for EDTA and EDDS a calculation of the conditional formation constants was done using

equations from chapter 2.6. Resulting lg Keff as a function of pH value is shown in Figure 4-3:

-10,00

-5,00

0,00

5,00

10,00

15,00

20,00

0 2 4 6 8 10

pH

log

(Kef

f)

CuNTA

FeNTA

PbNTA

ZnNTA

CaNTA

MnNTA

Figure 4-3: Conditional formation constant lgKeff of Me-NTA as function of pH

The amount of formed complexes depends not only on the stability constants, but also on the

concentration of free ions in solution. Figures 4-4 to 4-6 show the molar concentrations of

metals at selected pH values for Rafz soil. Ca is the major fraction, however it has the lowest

complex stability. A strange effect is the fact that the Ca and Mg concentrations at lower pH

values are smaller with NTA 1 than they are without complexing agent. This was also

observed for Kirschgarten soil, but cannot be explained.

Discussion

47

0

500

1000

1500

2000

2500

3000

3500

4000

4500

w/o NTA NTA1 NTA2

c in

um

ol/L

Pb

Mn

Cu

Fe

Zn

Mg

Ca

Figure 4-4: Molar concentrations in extraction solution at pH 4

0

500

1000

1500

2000

2500

3000

w/o NTA NTA1 NTA2

c in

um

ol/L

Pb

Mn

Cu

Fe

Zn

Mg

Ca

Figure 4-5: Molar concentrations in extraction solution at pH 6

Discussion

48

0

500

1000

1500

2000

2500

3000

w/o NTA NTA1 NTA2

c in

um

ol/L

Pb

Mn

Cu

Fe

Zn

Mg

Ca

Figure 4-6: Molar concentrations in extraction solution at pH 8

A calculation concerning all metals and side reactions would be very complicated. Therefore

a software model was used.

The availability of measured metal concentrations at different pH values allowed a software

speciation. For this the program ChemEQL V2.0 (11) was used. It contains a database with all

relevant constants and species. For given concentrations of metal ions the program calculates

the concentration of specific complexes at equilibrium. Different complexes with the same

central ion were combined. Mg and Mn complexes are not shown due to the concentrations of

these complexes not being relevant in the speciation. An example calculation was done for

Rafz soil only. The results, calculated in molar % of present complexing agent, are shown in

Figure 4-7 and Figure 4-8 as function of pH value.

It has to be considered that this model delivers data for a solution in equilibrium. Therefore

the results can only give an approximate idea of what complexes exist in the extraction

solution at measuring time. Nevertheless, in speciation it is possible to include more species

than in conditional formation calculations and to consider the competition between the ions. A

comparison between both ways to describe complex stability has been made by Davidge et at

(6), showing that speciation is more effective and accurate.

Discussion

49

Complexes with NTA concentration 1

0

10

20

30

40

50

3 4 5 6 7 8

pH value

com

plex

es in

mol

ar %

of p

rese

nt N

TA

Ca-NTAFe-NTAPb-NTAZn-NTA

Figure 4-7: Calculated speciation of NTA concentration 1 (ChemEQL)

With NTA concentration 1 up to 50 % of available NTA forms Zn complexes. At low pH

values competing Fe and at high pH values competing Ca decrease this value. Pb forms less

complexes than Zn because of the smaller molar concentration of Pb in solution.

Discussion

50

Complexes with NTA concentration 2

0

10

20

30

40

50

3 3,5 4 4,5 5 5,5 6 6,5 7 7,5 8

pH value

com

plex

es in

mol

ar %

of p

rese

nt N

TA

Ca-NTAFe-NTAPb-NTAZn-NTA

Figure 4-8: Calculated speciation of NTA concentration 2 (ChemEQL)

With NTA concentration 2 the complex formation of Zn-NTA and Pb-NTA is nearly constant

across the whole pH range. Despite competing Fe and Ca there is still NTA available in

excess for the weaker complexes to form.

Suspicious is the fact, that the percentage of complexing agent bound by Ca does not depend

on the NTA concentration. However, only at pH values > 6.5 the amount of extracted Ca

increases with higher NTA concentrations (cp. Figure 3-6 and Figure 3-7).

Discussion

51

4.2.2 Effectiveness of extraction with NTA NTA is able to remove about 50 % of Cu and Zn from soil when a concentration equal to the

molar sum of heavy metal concentration in soil is used. The results can be compared to EDTA

and EDDS. The pH value for the extraction has to be chosen so that the effect of competing

Ca and Fe ions is minimal. The experiments show an optimum pH of 6.5. Higher

concentrations of NTA improve the results for Zn and Cu slightly, but it has to be carefully

considered whether better extraction results compensate for the negative side effects on the

soil and the higher expenses.

The effect of NTA concentration 2 compared to NTA concentration 1 is enormous for Pb

extraction. When NTA is limited, the weaker Pb-NTA has difficulties to compete with the

other ions. Only when the complexing agent is in excess, good Pb extraction results are

obtained even at pH values where Pb is considered immobile (above pH 4). So if Pb

contamination has to be removed, the concentration of complexing agent chosen should be

higher than the molar sum of metals to be extracted (cp. Figure 3-17).

However, a higher concentration of complexing agent also increases the negative side effects

on soil. More organic material is extracted mainly at high pH values. Also Mn extraction

increases at low and medium pH values up to 7 and Ca extraction increases for pH values

above 6.5. Additionally these metals have to be considered as competing ions despite their

weak complex stabilities due to high concentrations in solution.

4.3 Error discussion

For an estimation of errors made in the AAS analyses the results from the EDDS extractions

before the sequential extraction (cp. 2.5.3) were used, because the conditions during these

extractions are comparable to the other experiments. Table 4-1 shows the results for σ of

samples extracted with EDDS (24 hours or 48 hours). The complete results can be found in

the appendix.

Apart from two outliers all results are within acceptable range for a duplicate analysis. The

highest error of 30 % for Pb in Kirschgarten is due to the small absolute concentration.

However, the kinetics and the pH variation experiments were done only in single analyses due

to the large amount of necessary measurements and shortage of time. Therefore the single

Discussion

52

results have to be examined critically. Despite that the accuracy is sufficient for the

interpretation of the data as it has been made in the discussion.

Table 4-1: Relative standard deviation σ for EDDS extractions

σ [%] Soil Extraction time [h] Cu Fe Mn Pb Zn 24 2.5 3.8 0.5 1.2 0.8 Kirschgarten

48 2.1 1.8 9.0 30 2.5

24 1.9 1.6 3.4 5.2 1.8 Mattenweg

48 0.7 0.8 0.4 0.1 0.3

24 0.6 1.0 0.2 0.3 1.3 Rafz

48 0.0 0.1 1.5 0.2 6.3

For the sequential extraction two additional facts effect the error of the results: the different

extraction solutions in the single extraction steps and sum up of errors. To find a

quantification for the error of concentration sum, the sum of absolute standard deviations was

determined exemplary for Rafz soil (samples not extracted with EDDS). In order to get the

total relative standard deviation, this sum was set in relation to the sum of concentrations. The

results are shown in Table 4-2, together with the concentrations sum of the single extraction

steps compared to the XRF total concentrations.

Table 4-2: Sum of concentrations compared to total concentration by XRF (Rafz soil)

Cu Fe Mn Pb Zn

σ of sum[%] 5.7 3.8 8.8 4.8 3.3

Sum of concentrations [µg/g]

90 15000 760 770 1200

Total concentration by XRF [µg/g]

76 19000 850 720 980

While the standard deviations are acceptable for a seven step extraction, the differences

between the sum up and the XRF results are significant. This indicates that methodical errors

are caused by the use of different solutions during sequential extraction. Therefore the results

of sequential extraction were rounded to full percents.

Summary

53

5 Summary

In principle, both EDDS and NTA can be used as biodegradable substitutes for EDTA in

extraction of heavy metal contaminated soils. However, problems of EDDS are its weak Pb

complexes giving rise to low Pb extraction and the high amounts of extracted Fe even at high

pH values, mainly with longer extraction times. Additionally the expenses for EDDS are

higher than for EDTA. For 1000 kg of contaminated soil about 9 kg of EDDS (industrial

product) would be needed costing 63 – 72 Euro compared to 18 – 27 Euro for EDTA (EDTA

and EDDS prices according to private correspondence with Procter & Gamble European

Center). With an approximate price of 150 Euro per 1000 kg soil for an off-site extraction

process this is a relevant difference (8). The amount of needed complexing agent is assumed

for a soil comparable with the soils used in the experiments. Doing this the concentration of

complexing agent equals the molar concentrations of the contaminating heavy metals (20

µmol/g soil, cp. Table 2-4). As the experiments have shown this concentration may not be

sufficient for the extraction of some heavy metals, mainly Pb.

Generally, costs for the extraction of typical contamination sites are enormous. An area of

1 hectare with a contamination depth of 0.25 m would bring a factor of 6000 to the costs for

1000 kg soil.

The price of NTA is nearly the same as for EDTA, but because of the smaller molar mass the

costs should be a bit lower than for EDTA. Extraction results for NTA are satisfying for Cu

and Zn. As for EDDS, for the removal of Pb higher concentrations of complexing agent are

needed, resulting in more negative side effects on soil and higher expenses. The main

disadvantage of NTA is its unclear health rating (possible carcinogen, cp. 2.2.3). In many

countries the use of NTA is restricted or banned.

An improvement in economy of extractions could be achieved by repeated use of the

complexing agent. Studies by Lee/Marshall (10) indicate that a cyclic extraction with

complexing agents can reduce the costs for treatment of contaminated soils.

Further researches are necessary to find the optimum concentrations. These concentrations

have to be a compromise between high extraction rates of heavy metals, low extraction rates

of essential substances and possibly small expenses. Other interesting aspects are the

influence of the extraction on soil structure and soil biology. Additionally the validation of the

found relations for a big scale use have to be examined.

A general problem even with EDTA is the fact, that heavy metal concentrations of several

hundred microgram per gram cannot be extracted to a level complying to legal requirements.

Acknowledgments

54

However, despite this and the high costs there are not many alternatives for rehabilitation of

heavy metal contamination. Therefore, until other processes are developed EDDS and NTA as

biodegradable complexing agents are a promising substitute for EDTA and should be

examined further.

6 Acknowledgments

The author wishes to thank Prof. R. Schulin for the possibility to do the experiments at ITÖ in

Schlieren; Prof. B. Rudolph and Dr. B. Nowack for supervising; Sue for all the help with

language and content; Anna and Werner for indispensable support in the laboratory; anyone

who did proof-reading and last but not least Yvonne for solving all bureaucratic problems

before and during the stay in Switzerland.

References

55

7 References

(1) AbfKlärV, Klärschlammverordnung, 15.04.1992; Bundesgesetzblatt Teil I, Germany,

1992

(2) Barona, A.; Aranguiz, I.; Elías, A.; Metal associations in soils before and after EDTA

extractive decontamination: implications for the effectiveness of further clean-up

procedures; Environmental Pollution 113, pp. 79-85, 2001

(3) Blume, H.-P.; Handbuch des Bodenschutzes; 2nd edition; ecomed Verlag Landsberg,

Germany, 1992

(4) Bossart, K.; Müller, R.; Schwermetallextraktion aus kontaminierten Böden mittels

biologisch abbaubarer Chelatbildner; Diploma thesis, ETH Zürich, 2002

(5) Bucheli-Witschel, M.; Egli, T.; Environmental fate and microbial degradation of

aminopolycarboxylic acids; FEMS Microbiol. Rew. 25, pp. 69-106, 2001

(6) Davidge, J.; Thomas, C. P.; Williams, D. R.; Conditional formation constants or

chemical speciation data?; Chemical Speciation and Bioavailibility 13(4), pp. 129-134,

2001

(7) DIN EN 13040; Soil improvers and growing media – Sample preparation for chemical

and physical tests, determination of dry matter content, moisture content and laboratory

compacted bulk density; German version EN 13040:1999, Deutsches Institut für

Normung e. V., Germany, 2000

(8) Görner, K.; Hübner, K.; Hütte Umweltschutztechnik; Springer Verlag Berlin Heidelberg,

Germany, 1999

References

56

(9) Keller, R.; Mermet, J.-M.; Otto, M.; Widmer, H.M.; Analytical Chemistry; Wiley-VCH

Weinheim, Germany, 1998

(10) Lee, C. C.; Marshall, W. D.; Recycling of complexometric extractants to remediate of

soil contaminated with heavy metals; J. Environ. Monitor 4, pp. 325-329, 2002

(11) Müller, B.; ChemEQL V2.0; Eidgenössische Anstalt für Wasserversorgung,

Abwasserreinigung und Gewässerschutz, Kastanienbaum, Switzerland, 1996

(12) Smith, A. E.; Martell, R. M.; Critical stability constants, Vol. 1; Amino Acids Plenum

press, 1974

(13) Swedish Society for Nature Conservation; Complexing Agents 2000, Draft for public

hearing; 2000

(14) Vandevivere, P.C.; Saveyn, H.; Verstraete, W.; Feijtel, T.C.J.; Schowanek, D. R.;

Biodegration of Metal-[S,S]-EDDS Complexes; Environmental Science & Technology,

Vol. 35, No. 9, pp. 1765-1770, 2001

(15) Varian; Analytical Methods, Flame Absorption Spectrometry; Varian Australia Pty Ltd,

Mulgrave, Victoria, Australia, 1989

(16) VBBo. 1998; Verordnung über Belastungen des Bodens; SR 814.12; Eidgenössische

Drucksachen- und Materialzentrale, Bern, Switzerland, 1998

(17) WHO; Guidelines for drinking-water quality, Vol. 2: Health criteria and other

supporting information; pp. 565-573; World Health Organization, Geneva, Switzerland,

1996

(18) Zeien, H.; Chemische Extraktion zur Bestimmung der Bindungsformen von

Schwermetallen in Böden; Bonner Bodenkundliche Abhandlungen Bd. 17, pp. 87-98,

1995

Appendix

A1

A Appendix Table A-1: pH value of soil in CaCl2 solution

Sample No. pH value Kirschgarten A 5.5 B 5.5 ∅ 5.5 Mattenweg A 6.3 B 6.3 ∅ 6.3 Rafz A 7.1 B 7.1 ∅ 7.1 Table A-2: Determination of organic matter

Sample No. Tare [g]

Input weight [g] net

Output weight [g] gross

Output weight [g] net

org. matter [g]

org. matter [g/kg]

org. matter [%]

Kirschgarten A 118.58 50.11 164.24 45.66 4.45 89 8.9 B 120.96 50.09 166.63 45.67 4.42 88 8.8 C 83.29 50.14 129.06 45.77 4.37 87 8.7 ∅ 88 8.8 σ [%] 0.95 Mattenweg A 83.45 50.18 131.93 48.48 1.70 34 3.4 B 83.47 50.28 132.09 48.62 1.66 33 3.3 C 83.34 50.02 131.64 48.30 1.72 34 3.4 ∅ 34 3.4 σ [%] 2.1 Rafz A 120.41 50.06 164.05 43.64 6.42 128 13 B 97.23 50.08 140.90 43.67 6.41 128 13 C 97.05 50.11 140.94 43.89 6.22 124 12 ∅ 127 13 σ [%] 1.8

Appendix

A2

Table A-3: Determination of dry residue

Sample No. Tare [g] Input weight [g] net

Dry weight [g] gross

Dry weight [g] net

Dry weight [%]

Kirschgarten A 37.478 5.147 42.531 5.052 98.2 B 36.391 5.280 41.589 5.198 98.5 ∅ 98.3 σ [%] 0.22 Mattenweg A 35.884 5.068 40.854 4.971 98.1 B 36.828 5.000 41.726 4.897 97.9 ∅ 98.0 σ [%] 0.10 Rafz A 35.897 5.380 41.238 5.341 99.3 B 35.778 5.134 40.874 5.096 99.3 ∅ 99.3 σ [%] 0.02 Table A-4: Determination of carbonate content

Sample No.

Input weight [g]

Formed gas [ml]

Formed gas [mol]

Formed CO3 [g]

Formed CO3 [%]

Formed CaCO3 [%]

Kirschgarten A 5.12 10 0.00039 0.02365 0.46 0.77 B 4.94 9 0.00035 0.02128 0.43 0.72 C 5.06 10 0.00039 0.02365 0.47 0.78 ∅ 0.45 0.76 Mattenweg A 5.05 154 0.00607 0.36414 7.2 12 B 5.01 148 0.00583 0.34995 7.0 12 C 5.05 166 0.00654 0.39251 7.8 13 ∅ 7.3 12 Rafz A 5.17 12 0.00047 0.02837 0.55 0.92 B 5.08 10 0.00039 0.02365 0.47 0.78 C 4.99 12 0.00047 0.02837 0.57 0.95 ∅ 0.53 0.88 Reference (CaCO3) 1 246 0.00969 0.58167 58 97

Appendix

A3

Table A-5: Determination of particle size distribution

84" sedimentation 120`09" sedimentation

Sample No. Tare weight [g] gross

weight [g] net Tare

weight [g] gross

weight [g] net

Sand [%]

Silt [%]

Clay [%]

Kirschgarten A 1 23.3805 23.4885 0.0880 23.5128 23.5611 0.0283 2 25.8056 25.9125 0.0869 23.7046 23.7527 0.0281 B 1 24.0628 24.1682 0.0854 22.9164 22.9644 0.0280 2 23.2965 23.4036 0.0871 25.1329 25.1812 0.0283 C 1 22.7436 22.8505 0.0869 23.6242 23.6721 0.0279 2 21.7527 21.8589 0.0862 25.2864 25.3346 0.0282 ∅ 0.0867 0.0281 13 59 28 σ[%] 1.0122 0.5804 Mattenweg A 1 25.2649 25.3558 0.0709 25.8090 25.8629 0.0339 2 23.6179 23.7118 0.0739 24.1888 24.2437 0.0349 B 1 24.0338 24.1292 0.0754 23.4374 23.4924 0.0350 2 26.1624 26.2584 0.0760 24.6606 24.7159 0.0353 C 1 24.7015 24.7994 0.0779 23.7439 23.8001 0.0362 2 23.7415 23.8392 0.0777 23.9164 23.9722 0.0358 ∅ 0.0753 0.0352 25 40 35 σ[%] 3.4803 2.2697 Rafz A 1 28.5938 28.6598 0.0460 20.5534 20.5900 0.0166 2 23.8149 23.8821 0.0472 23.7877 23.8248 0.0171 B 1 22.4407 22.5065 0.0458 26.3520 26.3880 0.0160 2 28.0773 28.1437 0.0464 26.6137 26.6504 0.0167 C 1 27.1777 27.2435 0.0458 28.8356 28.8719 0.0163 2 24.0154 24.0813 0.0459 28.5909 28.6275 0.0166 ∅ 0.0462 0.0166 54 30 17 σ[%] 1.1814 2.2527

Table A-6 Total metals determined with XRF

Sample No. Na

[µg/g] Mg

[µg/g] Al

[µg/g]Ca

[µg/g]Mn

[µg/g]Fe

[µg/g]Ni

[µg/g]Cu

[µg/g] Zn

[µg/g]Cd

[µg/g]Pb

[µg/g] Kirschgarten A 4750 6140 51710 11670 903.7 27300 45.8 451.0 656.8 1.8 73.2 B 3450 6360 51670 11660 890.4 26990 45.6 448.6 657.0 1.8 73.8 C 4650 6160 51160 11580 888.7 27160 47.7 445.4 656.3 1.9 73.5 ∅ 4300 6220 51500 11600 894 27200 46.4 448 656.7 1.8 73.5 σ [%] 16.9 2.0 0.6 0.4 0.9 0.6 2.5 0.6 0.1 3.1 0.4 Mattenweg A 1820 6820 53240 60590 840.8 30720 56.0 523.8 660.1 1.5 57.3 B 2130 6810 52760 60290 821.3 30650 55.6 528.1 661.6 1.8 55.4 C 2300 6790 51480 59950 860.0 31590 57.6 516.5 660.4 1.6 57.4 ∅ 2100 6806 52500 60300 841 31000 56.4 523 660.7 1.6 56.7 σ [%] 11.7 0.2 1.7 0.5 2.3 1.7 1.9 1.1 0.1 9.4 2.0 Rafz A 7500 6750 48200 10800 796.7 17470 23.3 75.5 998.3 1.3 730.9 B 6760 6730 47270 10520 856.1 19470 23.4 77.9 979.6 1.4 719.5 C 7590 5770 45450 10540 883.8 20060 22.5 74.4 972.1 1.2 719.0 ∅ 7300 6500 47000 10600 846 19000 23.1 75.9 983 1.3 723 σ [%] 6.3 8.7 3.0 1.5 5.3 7.1 2.1 2.4 1.4 7.7 0.9 Reference A 3510 10300 53780 42480 1184 33410 46.1 96.3 506.0 2.6 172.62001.3/921 B 3220 10240 53900 42070 1186 33360 47.4 95.8 509.9 2.6 171.7 C 3280 10440 54280 42190 1174 33470 46.5 94.9 507.1 2.9 170.5 ∅ 3300 10300 54000 42200 1180 33400 46.7 95.7 508 2.7 172 σ [%] 4.6 1.0 0.5 0.5 0.5 0.2 1.4 0.7 0.4 6.4 0.6 Median1 5548 11200 56900 42700 1205 32000 43.0 94.0 523.0 2.5 166.0

Diff. [%] -66 -8.5 -5.4 -1.1 -2.0 4.2 7.9 1.7 -3.0 7.4 3.3

Table A-7: NaNO3 extractable metals

Sample No. Input weight

Ref. V AAS results Resolved of blank

[g]

[mL] Pb [mg/L]

Zn [mg/L]

Cu [mg/L]

Pb [mg/L]

Zn [mg/L]

Cu [mg/L] Pb [µg/g]

Zn [µg/g]

Cu [µg/g]

Kirschgarten A 20.63 50 0.00 0.51 0.37 0.00 0.49 0.36 <0.25 1.19 0.88 B 20.25 50 0.00 0.49 0.37 0.00 0.48 0.37 <0.25 1.18 0.91 C 20.33 50 0.00 0.51 0.39 0.00 0.50 0.38 <0.25 1.22 0.95

∅ <0.25

1.20 0.91 σ [%] 1.9 3.4 Mattenweg A 20.18 50 0.00 0.05 0.38 0.00 0.04 0.37 <0.25 0.10 0.92 B 20.03 50 0.00 0.05 0.39 0.00 0.03 0.38 <0.25 0.08 0.96 C 20.17 50 0.00 0.05 0.38 0.00 0.03 0.38 <0.25 0.09 0.93 ∅ <0.25 0.09 0.94 σ [%] 11 2.1 Rafz A 20.25 50 0.00 4.51 0.10 0.00 4.50 0.10 <0.25 11.11 0.24 B 20.10 50 0.00 4.47 0.11 0.00 4.46 0.10 <0.25 11.09 0.24 C 20.09 50 0.00 4.47 0.10 0.00 4.46 0.10 <0.25 11.09 0.24 ∅ <0.25 11.10 0.24 σ [%] 0.1 1.2 Reference A 20.46 50 0.00 0.06 0.23 0.00 0.05 0.22 <0.25 0.11 0.542001.3/921 B 20.21 50 0.00 0.06 0.23 0.00 0.04 0.22 <0.25 0.11 0.55 ∅ <0.25 0.11 0.55 σ [%] 5.0 0.3 Median1 0.0014 0.08 0.5Blank value ∅ 50 0.00 0.01 0.01 0 0 0 σ [%] 31.9 1.2 0.3 Det. limit 0.10 0.001 0.0001 0.25 0.0024 0.0003

Table A-8: HNO3 extractable metals

Sample No. Input weight Ref. V AAS results Resolved of blank

[g] V [mL]

Pb [mg/L]

Zn [mg/L]

Cu [mg/L]

Pb [mg/L]

Zn [mg/L]

Cu [mg/L]

Pb [µg/g] Zn [µg/g]

Cu [µg/g]

Kirschgarten A 5.00 50 7.17 79.27 44.21 7.14 79.26 44.20 71.40 792.56 441.95 B 5.01 50 7.10 79.49 44.48 7.07 79.48 44.46 70.58 793.19 443.69 C 5.01 50 7.06 80.03 44.92 7.03 80.01 44.90 70.13 798.52 448.11 ∅ 70.7 795 445 σ [%] 0.91 0.41 0.71 Mattenweg A 5.00 50 5.52 76.03 46.80 5.48 76.01 46.78 54.83 760.14 467.84 B 5.07 50 5.74 78.08 48.12 5.71 78.07 48.11 769.92 474.42 C 5.00 50 5.53 65.04 46.88 5.49 65.03 46.87 54.94 650.30 468.66 ∅ 54.9 730 470 σ [%] 0.13 9.1 0.76 Rafz A 5.04 50 71.73 81.27 6.42 71.70 81.25 6.40 711.29 806.08 63.49 B 5.02 50 76.31 122.31 6.49 76.27 122.30 6.47 759.70 1218.09 64.47 C 5.07 50 78.19 121.07 7.12 78.15 121.05 7.11 770.75 1193.81 70.08 ∅ 750 1100 66 σ [%] 4.2 22 5.4 Reference A 5.45 50 20.48 70.14 9.93 20.45 70.13 9.91 187.60 643.40 90.902001.3/921 B 5.05 50 18.50 63.64 8.90 18.47 63.63 8.88 182.84 629.99 87.96 ∅ 185 637 89 σ [%] 1.8 1.5 2.3 Median1 165.0 504.0 89.2Blank value ∅ 50 0.032 0.013 0.018 0 0 0 σ [%] 12.4 1.2 16 Det. limit 0.024 0.001 0.017 0.06 0.0024 0.043

Appendix

A7

Table A-9: Kinetics of Rafz extracted with EDTA at pH 4

extraction time metal mg/L µg/g

dissolved % theor. mg/L µmol/L remarks

0 Ca 0.0 0 0 0 0 1 1.8 4500 43 90 2300 2 1.9 4700 44 94 2300 4 2.0 4900 47 99 2500 8 2.0 5000 48 100 2500

24 1.9 4800 45 96 2400 32 2.0 4800 46 98 2400 48 2.0 4900 46 98 2400

dilution1:50

0 Cu 0.0 0 0 0.0 0.0 1 0.6 27 36 0.6 8.7 2 0.5 27 36 0.5 8.5 4 0.6 31 40 0.6 9.7 8 0.7 37 48 0.7 12

24 0.6 31 41 0.6 9.8 32 0.4 22 29 0.4 7.0 48 0.4 20 27 0.4 6.3

0 Mg 0.0 0 0.0 0.0 0 1 13.2 654 10.3 13.2 542 2 13.1 648 10.2 13.1 537 4 13.2 653 10.2 13.1 541 8 14.2 700 11.0 14.1 580

24 13.8 683 10.7 13.8 566 32 13.6 673 10.6 13.6 557 48 14.4 711 11.2 14.3 589

0 Fe 0.0 0 0.00 0.0 0 1 1.7 85 0.45 1.7 31 2 1.9 92 0.49 1.9 33 4 2.2 110 0.58 2.2 40 8 2.7 130 0.70 2.7 48

24 4.0 200 1.1 4.0 72 32 5.8 290 1.5 5.8 100 48 6.1 300 1.6 6.1 110

0 Pb 0.0 0 0 0.0 0 1 6.4 330 44 6.4 31 2 7.0 350 48 7.0 34 4 8.0 400 55 8.0 39 8 8.5 420 58 8.4 41

24 7.9 390 54 7.8 38 32 8.1 400 56 8.1 39 48 8.4 410 58 8.3 40

0 Zn 0.0 0 0.0 0.0 0 1 16.0 788 80.7 15.9 243 2 16.7 823 84.2 16.6 254 4 15.3 754 77.2 15.2 232 8 17.6 867 88.8 17.5 267

24 15.5 764 78.2 15.4 235 32 15.4 761 77.9 15.3 234 48 16.3 802 82.2 16.2 247

Appendix

A8

Table A-10: Kinetics of Rafz extracted with EDDS at pH 4

extraction time metal mg/L µg/g

dissolved %

theor. mg/L µmol/L remarks

0 Ca 0.0 0 0 0 0 1 2.0 4900 46 98 2400 2 2.0 5000 47 100 2500 4 2.0 4900 47 99 2500 8 2.0 4900 46 98 2400

24 2.0 4900 46 98 2400 32 1.9 4700 45 95 2400 48 2.0 4900 46 98 2500

dilution 1:50

0 Cu 0.0 0 0 0.0 0.0 1 0.6 28 37 0.6 8.8 2 0.6 29 38 0.6 9.1 4 0.7 34 45 0.7 10 8 0.8 42 55 0.8 13

24 0.7 36 47 0.7 11 32 0.6 29 38 0.6 9.1 48 0.5 27 36 0.5 8.5

0 Mg 0.0 0 0.0 0.0 0 1 15.3 756 11.9 15.2 626 2 13.7 676 10.6 13.6 560 4 14.3 705 11.1 14.2 584 8 13.6 670 10.5 13.5 555

24 14.5 717 11.3 14.4 594 32 14.8 734 11.5 14.8 608 48 14.8 730 11.5 14.7 605

0 Fe 0.0 0 0.0 0.0 0 1 1.7 85 0.5 1.7 31 2 2.4 120 0.6 2.4 43 4 3.0 150 0.8 3.0 54 8 4.2 210 1.1 4.2 75

24 6.2 310 1.6 6.2 110 32 9.0 450 2.4 9.0 160 48 8.2 410 2.2 8.2 150

0 Pb 0.0 0 0.0 0.0 0.0 1 0.3 14 2.0 0.3 1.4 2 0.2 10 1.4 0.2 1.0 4 0.2 12 1.7 0.2 1.2 8 0.3 13 1.8 0.3 1.3

24 0.2 8 1.2 0.2 0.8 32 0.3 15 2.0 0.3 1.4 48 0.3 13 1.8 0.3 1.3

0 Zn 0.0 0 0.0 0.0 0 1 15.7 774 79.2 15.6 238 2 14.3 707 72.4 14.3 218 4 14.7 726 74.3 14.6 224 8 13.6 670 68.6 13.5 206

24 12.2 600 61.7 12.1 185 32 11.0 545 55.8 11.0 168 48 12.8 634 64.9 12.8 195

Appendix

A9

Table A-11: Kinetics of Rafz extracted without complexing agent at pH 4

extraction time metal mg/L µg/g

dissolved %

theor. mg/L µmol/L

remarks

0 Ca 0.0 0.0 0 0 0 1 2.0 5000 47 100 2500 2 2.1 5200 49 100 2600 4 2.2 5300 50 110 2700 8 2.0 5000 47 99 2500

24 2.1 5200 49 100 2600 32 2.0 4900 47 99 2500

48 2.0 4900 47 99 2500

dilution 1:50

0 Cu 0.0 0 0 0.0 0.0 1 0.0 2 3 0.0 0.7 2 0.0 2 3 0.0 0.7 4 0.1 3 4 0.1 0.9 8 0.0 2 3 0.1 0.7

24 0.0 2 2 0.0 0.6 32 0.0 2 3 0.0 0.7 48 0.0 2 3 0.0 0.8

0 Mg 0.0 0 0.0 0.00 0.00 1 14.4 716 11.2 14.4 593 2 14.0 694 10.9 14.0 575 4 14.4 714 11.2 14.4 591 8 11.9 588 9.2 12.0 487

24 13.8 685 10.8 13.8 567 32 14.4 712 11.2 14.3 590 48 14.1 699 11.0 14.1 579

0 Fe 0.0 0.0 0.0 0.0 0.0 1 0.0 0.9 0.0 0.0 0.3 2 0.0 0.4 0.0 0.0 0.1 4 0.0 0.0 0.0 0.0 0.0 8 0.0 0.0 0.0 0.0 0.0

24 0.0 0.0 0.0 0.0 0.0 32 0.1 6.0 0.0 0.1 2.2 48 0.0 1.2 0.0 0.0 0.4

0 Pb 0.0 0.0 0.0 0.0 0.0 1 0.2 12 1.6 0.2 1.1 2 0.2 7.8 1.1 0.2 0.8 4 0.2 11 1.5 0.2 1.1 8 0.2 10 1.4 0.2 1.0

24 0.2 7.5 1.1 0.2 0.7 32 0.3 14 1.9 0.3 1.3 48 0.2 9 1.3 0.2 0.9

0 Zn 0.0 0 0.0 0.0 0 1 12.4 615 63.0 12.4 190 2 12.1 599 61.3 12.1 184 4 12.8 633 64.8 12.8 195 8 10.6 524 53.6 10.6 161

24 11.2 554 56.7 11.2 171 32 11.5 572 58.5 11.5 176 48 11.7 583 59.7 11.7 179

Appendix

A10

Table A-12: Kinetics of Rafz extracted with EDTA at pH 7

extraction time metal mg/L µg/g

dissolved % theor. mg/L µmol/L remarks

0 Ca 0.0 0 0 0 0 1 0.6 1500 14 30 750 2 0.6 1500 14 29 730 4 0.6 1400 14 29 720 8 0.6 1400 14 29 730

24 0.7 1600 15 32 800 32 0.6 1600 15 32 800 48 0.7 1600 15 33 810

dilution 1:50

0 Cu 0.0 0 0 0.0 0.0 1 0.2 12 16 0.3 3.9 2 0.3 12 17 0.3 3.9 4 0.3 14 18 0.3 4.4 8 0.3 17 23 0.3 5.4

24 0.3 17 23 0.3 5.4 32 0.3 14 18 0.3 4.3 48 0.3 13 18 0.3 4.2

0 Mg 0.0 0 0.0 0.0 0 1 1.5 76 1.2 1.5 63 2 1.8 90 1.4 1.8 74 4 1.7 86 1.4 1.7 71 8 1.7 86 1.4 1.7 72

24 1.9 95 1.5 1.9 79 32 2.0 100 1.6 2.0 83 48 2.1 100 1.6 2.1 86

0 Fe 0.0 0.0 0.00 0.0 0.0 1 0.2 8.4 0.04 0.2 3.0 2 0.3 17 0.09 0.4 6.2 4 0.1 7.2 0.04 0.2 2.6 8 0.1 7.0 0.04 0.1 2.5

24 0.2 9.0 0.05 0.2 3.2 32 0.3 13 0.07 0.3 4.5 48 0.3 16 0.08 0.3 5.7

0 Pb 0.0 0.0 0 0.0 0 1 3.1 150 21 3.1 15 2 2.9 140 20 2.9 14 4 3.5 170 24 3.5 17 8 3.9 190 27 3.8 19

24 4.0 200 27 4.0 19 32 4.5 220 31 4.5 22 48 5.0 250 34 5.0 24

0 Zn 0.0 0 0 0.0 0 1 8.0 400 41 8.0 120 2 7.9 390 40 7.9 120 4 8.5 420 43 8.5 130 8 8.9 440 45 8.9 140

24 9.0 450 46 9.0 140 32 8.7 430 44 8.7 130 48 10.1 500 51 10.1 150

Appendix

A11

Table A-13: Kinetics of Rafz extracted with EDDS at pH 7

extraction time metal mg/L µg/g

dissolved %

theor. mg/L µmol/L remarks

0 Ca 0.0 0.0 0 0 0 1 0.6 1400 13 28 710 2 0.6 1400 13 28 710 4 0.6 1400 14 29 720 8 0.6 1600 15 32 790

24 0.7 1600 15 32 800 32 0.6 1600 15 32 790 48 0.6 1600 15 31 780

dilution 1:50

0 Cu 0.0 0 0 0.0 0.0 1 0.3 17 22 0.3 5.3 2 0.4 19 25 0.4 5.9 4 0.5 23 30 0.5 7.3 8 0.6 28 37 0.6 8.8

24 0.5 24 32 0.5 7.7 32 0.4 21 28 0.4 6.7 48 0.4 22 28 0.4 6.8

0 Mg 0.0 0 0.0 0.0 0 1 2.7 130 2.1 2.6 110 2 2.3 110 1.8 2.3 94 4 2.3 110 1.8 2.3 94 8 2.2 110 1.7 2.2 91

24 2.4 120 1.9 2.4 99 32 2.3 120 1.8 2.3 96 48 2.5 120 1.9 2.5 100

0 Fe 0.0 0 0.0 0.0 0 1 0.6 28 0.2 0.6 10 2 0.8 38 0.2 0.8 14 4 1.1 54 0.3 1.1 19 8 1.5 72 0.4 1.5 26

24 2.2 111 0.6 2.2 40 32 3.3 170 0.9 3.3 60 48 3.7 180 1.0 3.7 66

0 Pb 0.0 0 0 0.0 0 1 3.2 160 22 3.1 15 2 3.0 150 20 3.0 14 4 3.8 190 26 3.8 18 8 4.0 200 27 3.9 19

24 4.0 200 27 3.9 19 32 4.1 200 28 4.0 19 48 3.8 190 26 3.8 18

0 Zn 0.0 0 0 0.0 0 1 8.6 420 43 8.5 130 2 7.8 390 40 7.8 120 4 8.6 430 44 8.6 130 8 8.9 440 45 8.9 140

24 9.5 470 48 9.5 150 32 9.8 490 50 9.8 150 48 10.6 530 54 10.6 160

Appendix

A12

Table A-14: Kinetics of Rafz extracted with EDDS and Glucopon at pH 7

extraction time metal mg/L µg/g

dissolved %

theor. mg/L µmol/L remarks

0 Ca 0.0 0 0 0 0 1 0.6 1500 14 29 730 2 0.6 1400 13 28 690 4 0.6 1400 13 29 710 6 0.6 1400 13 28 700 8 0.6 1500 14 30 740

24 0.6 1400 14 29 730 32 0.6 1400 13 28 700 48 0.6 1400 14 29 720

dilution 1:50

0 Cu 0.0 0 0 0.0 0.0 1 0.3 17 22 0.3 5.4 2 0.4 19 25 0.4 5.9 4 0.5 23 31 0.5 7.4 6 0.6 30 40 0.6 9.5 8 0.6 27 36 0.6 8.7

24 0.5 24 32 0.5 7.5 32 0.4 20 26 0.4 6.2 48 0.4 20 26 0.4 6.3

0 Mg 0.0 0 0.0 0.0 0 1 2.6 130 2.0 2.6 110 2 2.2 110 1.7 2.2 92 4 2.3 110 1.8 2.3 93 6 2.1 100 1.6 2.1 86 8 1.9 95 1.5 1.9 79

24 2.2 110 1.7 2.2 92 32 2.0 99 1.6 2.0 82 48 2.3 110 1.8 2.3 93

0 Fe 0.0 0 0.0 0.0 0.0 1 0.5 27 0.1 0.6 9.8 2 0.7 36 0.2 0.7 13 4 1.0 51 0.3 1.0 18 6 1.6 77 0.4 1.5 28 8 1.5 73 0.4 1.5 26

24 2.2 110 0.6 2.2 39 32 3.3 160 0.9 3.3 59 48 3.6 180 0.9 3.6 64

0 Pb 0.0 0 0 0.0 0 1 2.9 140 20 2.9 14 2 3.1 150 21 3.1 15 4 3.8 190 26 3.7 18 6 4.0 200 27 4.0 19 8 3.9 190 27 3.8 19

24 3.4 170 23 3.4 16 32 3.5 170 24 3.5 17 48 3.1 150 21 3.1 15

0 Zn 0.0 0 0 0.0 0 1 7.8 390 40 7.8 120 2 7.8 380 39 7.7 120 4 8.4 410 42 8.3 130 6 9.0 440 46 9.0 140 8 8.6 420 43 8.5 130

24 9.5 470 48 9.4 140 32 9.7 480 49 9.6 150 48 10.3 510 52 10.2 160

Appendix

A13

Table A-15: Kinetics of Rafz extracted without complexing agent at pH 7

extraction time metal mg/L µg/g

dissolved %

theor. mg/L µmol/L

remarks

0 Ca 0.0 0.0 0 0 0 1 0.6 1500 14 30 750 2 0.6 1400 14 29 720 4 0.6 1400 14 29 730 8 0.6 1500 14 29 730

24 0.6 1400 13 28 710 32 0.6 1400 13 28 700 48 0.6 1400 13 28 700

dilution 1:50

0 Cu 0.0 0.0 0.0 0.0 0.0 1 0.0 0.9 1.1 0.0 0.3 2 0.0 0.8 1.0 0.0 0.3 4 0.0 0.7 1.0 0.0 0.2 8 0.0 0.8 1.0 0.0 0.2

24 0.0 1.3 1.8 0.0 0.4 32 0.0 0.7 0.9 0.0 0.2 48 0.0 0.2 0.3 0.0 0.1

0 Mg 0.0 0 0.0 0.0 0 1 2.2 110 1.7 2.2 89 2 2.3 110 1.8 2.3 93 4 2.3 120 1.8 2.3 96 8 2.0 100 1.5 2.0 80

24 2.3 120 1.8 2.3 96 32 2.2 110 1.7 2.2 90 48 2.2 110 1.7 2.2 89

0 Fe 0.0 0 0.0 0.0 0.0 1 0.0 0 0.0 0.0 0.0 2 0.0 0 0.0 0.0 0.0 4 0.0 0 0.0 0.0 0.0 8 0.0 0 0.0 0.0 0.0

24 0.3 14 0.1 0.3 4.9 32 0.0 1.2 0.0 0.0 0.4 48 0.4 20 0.1 0.4 7.1

0 Pb 0.0 0.0 0.0 0.0 0.0 1 0.1 4.2 0.6 0.1 0.4 2 0.1 7.3 1.0 0.2 0.7 4 0.1 5.1 0.7 0.1 0.5 8 0.1 3.8 0.5 0.1 0.4

24 0.1 7.1 1.0 0.1 0.7 32 0.1 6.6 0.9 0.1 0.6 48 0.2 7.8 1.1 0.2 0.8

0 Zn 0.0 0 0.0 0.0 0.0 1 0.2 12 1.2 0.2 3.7 2 0.3 16 1.6 0.3 4.9 4 0.4 18 1.9 0.4 5.6 8 0.2 12 1.2 0.2 3.7

24 0.3 17 1.7 0.3 5.2 32 0.3 13 1.3 0.3 4.0 48 0.3 17 1.8 0.4 5.3

Appendix

A14

Table A-16: pH variation of Kirschgarten soil with NTA 1

pH value mg/L µg/g dissolved % theor. mg/L µmol/L remarks

3 5.1 6300 55 130 3200

3.5 4.3 5300 46 110 2700 4 3.8 4700 41 95 2400

4.5 3.3 4100 35 83 2100 5 2.4 3000 26 60 1500

5.5 2.3 2900 25 58 1500 6 1.7 2100 18 42 1000

6.5 2.1 2500 22 52 1300 7 1.6 2000 17 40 990

7.5 0.9 1200 10 24 590 8

Ca 0.9 1100 9.7 23 560

dilution 1:25

3 4.5 220 51 4.5 71

3.5 4.8 240 54 4.8 76 4 5.1 250 57 5.1 80

4.5 5.2 260 58 5.2 82 5 5.1 250 57 5.1 81

5.5 4.7 230 52 4.7 74 6 4.5 220 50 4.5 71

6.5 4.4 220 49 4.4 69 7 4.1 200 46 4.1 65

7.5 2.7 130 30 2.7 42 8

Cu 2.2 110 25 2.2 35

3 0.17 210 3.5 4.3 180

3.5 0.16 190 3.1 3.9 160 4 0.14 180 2.9 3.6 150

4.5 0.13 160 2.6 3.3 130 5 0.11 140 2.3 2.9 120

5.5 0.10 130 2.1 2.6 110 6 0.09 110 1.8 2.3 93

6.5 0.10 120 2.0 2.5 100 7 0.08 100 1.7 2.1 85

7.5 0.05 67 1.1 1.4 56 8

Mg 0.05 63 1.0 1.3 53

dilution 1:25

3 7.4 370 42 7.5 140

3.5 5.3 260 30 5.4 97 4 4.2 210 24 4.2 77

4.5 3.0 150 17 3.0 54 5 2.2 110 12 2.2 41

5.5 1.5 75 8.5 1.5 28 6 1.1 56 6.3 1.1 21

6.5 1.4 71 8.1 1.5 26 7 1.2 58 6.6 1.2 21

7.5 0.1 4 0.4 0.1 1.4 8

Mn 0.1 5 0.6 0.1 1.9

Appendix

A15

Table A-16 continued

pH value mg/L µg/g dissolved % theor. mg/L µmol/L remarks

3 6.5 320 1.2 6.5 120

3.5 4.1 200 0.8 4.2 74 4 3.6 180 0.7 3.6 65

4.5 2.7 130 0.5 2.7 48 5 2.4 120 0.4 2.4 43

5.5 1.8 87 0.3 1.8 32 6 1.5 76 0.3 1.5 28

6.5 1.5 72 0.3 1.5 26 7 1.4 69 0.3 1.4 25

7.5 0.5 24 0.1 0.5 8.9 8

Fe 1.1 54 0.2 1.1 20

3 0.1 4 6 0.1 0.4

3.5 0.1 6 8 0.1 0.6 4 0.1 7 10 0.1 0.7

4.5 0.2 10 10 0.2 1 5 0.2 10 20 0.3 1

5.5 0.2 10 20 0.2 1 6 0.2 10 10 0.2 1

6.5 0.2 8 10 0.2 0.8 7 0.1 7 10 0.1 0.7

7.5 0.1 3 5 0.1 0.3 8

Pb 0.1 3 5 0.1 0.3

3 5.9 290 45 5.9 91

3.5 4.7 230 36 4.7 72 4 5.1 250 39 5.2 79

4.5 5.7 280 44 5.8 88 5 5.8 290 44 5.8 89

5.5 5.1 250 39 5.2 79 6 5.1 250 39 5.2 79

6.5 5.5 270 42 5.6 85 7 5.1 250 39 5.2 79

7.5 2.9 140 22 3.0 45 8

Zn 2.6 130 20 2.6 40

3 4.7 230 0.27 4.7

3.5 6.1 300 0.35 6.1 4 6.5 320 0.37 6.5

4.5 7.7 380 0.44 7.7 5 8.4 410 0.48 8.4

5.5 7.1 350 0.40 7.1 6 8.0 400 0.46 8.0

6.5 9.2 460 0.53 9.3 7 11.9 590 0.68 12.0

7.5 17.1 840 0.97 17.2 8

Huminic acids 27.2 1340 1.55 27.3

Appendix

A16

Table A-17: pH variation of Kirschgarten soil with NTA 2

pH value mg/L µg/g dissolved % theor. mg/L µmol/L remarks

3 5.2 6700 59 140 3400

3.5 3.4 4300 38 88 2200 4 3.9 5000 44 100 2600

4.5 3.1 3900 34 80 2000 5 3.4 4300 38 88 2200

5.5 2.2 2900 25 58 1500 6 2.3 3000 26 61 1500

6.5 2.6 3400 29 68 1700 7 3.0 3800 33 78 1900

7.5 3.5 4500 39 91 2300 8

Ca 3.8 4900 43 100 2500

dilution 1:25

3 7.0 360 82 7.4 120

3.5 6.7 350 78 7.0 110 4 6.5 330 75 6.8 110

4.5 6.3 320 73 6.6 100 5 6.0 310 70 6.3 99

5.5 5.9 300 69 6.2 97 6 5.9 300 68 6.1 96

6.5 5.8 300 67 6.0 95 7 5.7 290 66 5.9 93

7.5 5.0 250 58 5.2 82 8

Cu 4.8 250 56 5.0 79

3 0.17 220 3.6 4.4 180

3.5 0.14 180 3.0 3.7 150 4 0.14 180 3.0 3.7 150

4.5 0.12 160 2.6 3.2 130 5 0.12 150 2.5 3.1 130

5.5 0.10 120 2.0 2.5 100 6 0.09 110 1.8 2.3 94

6.5 0.10 130 2.1 2.6 110 7 0.08 110 1.8 2.2 90

7.5 0.15 190 3.1 3.9 160 8

Mg 0.17 220 3.5 4.4 180

dilution 1:25

3 9.9 510 58 10 190

3.5 7.9 400 46 8.2 150 4 7.4 380 43 7.7 140

4.5 7.4 380 43 7.7 140 5 6.9 350 40 7.2 130

5.5 6.7 340 39 7 130 6 5.7 290 33 5.9 110

6.5 5.6 290 33 5.9 110 7 4.9 250 29 5.2 94

7.5 0.2 11 1.3 0.2 4 8

Mn 0.3 13 1.5 0.3 5

Appendix

A17

Table A-17 continued

pH value mg/L µg/g dissolved % theor. mg/L µmol/L remarks

3 25.2 1300 4.9 26 470

3.5 17.9 920 3.4 19 330 4 12.3 630 2.4 13 230

4.5 8.4 430 1.6 8.8 160 5 7.0 360 1.3 7.3 130

5.5 6.4 330 1.2 6.7 120 6 5.2 270 1.0 5.5 98

6.5 5.6 290 1.1 5.8 100 7 5.2 270 1.0 5.4 97

7.5 3.2 160 0.6 3.3 59 8

Fe 3.3 170 0.6 3.5 62

3 1.7 88 100 1.8 8.7

3.5 1.1 56 77 1.1 5.5 4 0.9 48 67 1.0 4.7

4.5 0.9 45 63 0.9 4.5 5 0.9 44 61 0.9 4.3

5.5 0.8 39 54 0.8 3.8 6 0.7 35 48 0.7 3.4

6.5 0.7 35 48 0.7 3.4 7 0.6 31 42 0.6 3.0

7.5 0.3 17 24 0.4 1.7 8

Pb 0.4 20 27 0.4 1.9

3 8.0 410 64 8.4 130

3.5 7.5 390 60 7.9 120 4 7.3 370 58 7.6 120

4.5 6.8 350 54 7.1 110 5 6.5 330 52 6.8 100

5.5 6.4 330 50 6.6 100 6 6.1 310 48 6.3 97

6.5 6.3 320 50 6.6 100 7 6.3 320 50 6.6 100

7.5 4.4 220 35 4.6 70 8

Zn 4.2 210 33 4.4 67

3 11.1 571 0.66 11.6

3.5 12.7 650 0.80 13.2 4 12.0 614 0.70 12.5

4.5 12.7 651 0.80 13.2 5 15.3 785 0.90 16

5.5 19.4 994 1.20 20.2 6 22.6 1160 1.30 23.6

6.5 29.2 1490 1.70 30.4 7 34.7 1780 2.10 36.1

7.5 77.2 3960 4.60 80.5 8

Huminic acids 101.1 5180 6.00 105

Appendix

A18

Table A-18: pH variation of Kirschgarten soil without complexing agent

pH value mg/L µg/g dissolved % theor. mg/L µmol/L remarks

3 4.8 6000 52 120 3000

3.5 4.7 5700 50 120 2900 4 4.9 6100 53 120 3100

4.5 4.4 5400 47 110 2700 5 2.8 3500 31 71 1800

5.5 2.0 2500 22 51 1300 6 3.1 3900 34 79 2000

6.5 1.9 2400 21 49 1200 7 1.5 1800 16 37 930

7.5 0.9 1100 9.2 21 540 8

Ca 0.7 900 7.9 18 460

dilution 1:25

3 1.5 73 17 1.5 23

3.5 0.7 33 7.4 0.7 10 4 0.4 19 4.3 0.4 6.1

4.5 0.4 18 4.1 0.4 5.8 5 0.3 13 3.0 0.3 4.3

5.5 0.2 10 2.3 0.2 3.3 6 0.2 10 2.3 0.2 3.3

6.5 0.2 9.5 2.2 0.2 3.0 7 0.2 9.3 2.1 0.2 3.0

7.5 0.2 8.7 2.0 0.2 2.8 8

Cu 0.2 8.4 1.9 0.2 2.7

3 0.18 220 3.6 4.4 180

3.5 0.16 190 3.2 3.9 160 4 0.15 180 3.0 3.7 150

4.5 0.15 180 3.0 3.7 150 5 0.12 150 2.5 3.0 130

5.5 0.10 130 2.1 2.6 110 6 0.12 150 2.4 3.0 120

6.5 0.10 120 2.0 2.5 100 7 0.09 110 1.7 2.2 89

7.5 0.06 71 1.2 1.5 60 8

Mg 0.05 64 1.1 1.3 54

dilution 1:25

3 6.8 330 38 6.8 120

3.5 4.4 220 25 4.4 80 4 3.0 150 17 3.0 55

4.5 4.0 200 22 4.0 73 5 2.1 100 12 2.1 38

5.5 0.9 46 5 0.9 17 6 2.1 100 12 2.1 38

6.5 0.8 41 5 0.8 15 7 0.5 26 3 0.5 10

7.5 0.1 4 0.4 0.1 1 8

Mn 0.1 4 0.5 0.1 2

Appendix

A19

Table A-18 continued

pH value mg/L µg/g dissolved % theor. mg/L µmol/L remarks

3 0.3 16 0.06 0.3 6

3.5 0.1 7 0.03 0.1 3 4 0.1 5 0.02 0.1 2

4.5 0.1 4 0.02 0.1 2 5 0.1 3 0.01 0.1 1

5.5 0.0 2 0.01 0.0 1 6 0.1 3 0.01 0.1 1

6.5 0.1 3 0.01 0.1 1 7 0.1 3 0.01 0.1 1

7.5 0.1 5 0.02 0.1 2 8

Fe 0.1 5 0.02 0.1 2

3 0.1 3 4 0.1 0.3

3.5 0.0 2 3 0.0 0.2 4 0.0 2 3 0.1 0.2

4.5 0.1 3 4 0.1 0.3 5 0.0 2 3 0.0 0.2

5.5 0.1 3 4 0.1 0.3 6 0.1 3 4 0.1 0.3

6.5 0.0 2 3 0.0 0.2 7 0.0 2 2 0.0 0.2

7.5 0.0 2 3 0.0 0.2 8

Pb 0.0 2 2 0.0 0.2

3 6.3 310 48 6.3 96

3.5 4.5 220 34 4.5 69 4 3.1 150 24 3.1 47

4.5 3.1 160 24 3.2 48 5 1.6 79 12 1.6 24

5.5 0.6 30 5 0.6 9 6 0.8 39 6 0.8 12

6.5 0.3 13 2 0.3 4 7 0.1 6 1 0.1 2

7.5 0.1 5 1 0.1 1 8

Zn 0.1 4 1 0.1 1

3 4.5 220 0.26 4.5

3.5 4.5 220 0.26 4.5 4 5.9 290 0.34 5.9

4.5 4.7 230 0.27 4.7 5 5.2 260 0.30 5.2

5.5 5.5 270 0.31 5.5 6 5.3 260 0.30 5.3

6.5 6.4 320 0.37 6.4 7 8.0 400 0.46 8.0

7.5 13.6 670 0.77 13.6 8

Huminic acids 13.1 640 0.74 13.1

Appendix

A20

Table A-19: pH variation of Rafz soil with NTA 1

pH value mg/L µg/g dissolved % theor. mg/L µmol/L remarks

3 4.5 5800 55 116 2900

3.5 4.1 5200 50 106 2600 4 3.7 4700 45 95 2400

4.5 3.9 5000 47 101 2500 5 3.1 4000 38 81 2000

5.5 2.4 3100 29 62 1600 6 2.3 3000 28 60 1500

6.5 2.7 3400 32 69 1700 7 2.7 3500 33 70 1800

7.5 0.7 900 9 18 500 8

Ca 0.7 900 8 17 400

dilution 1:25

3 0.5 27 36 0.5 9

3.5 0.6 28 37 0.6 9 4 0.6 29 38 0.6 9

4.5 0.6 28 37 0.6 9 5 0.5 26 35 0.5 8

5.5 0.5 25 33 0.5 8 6 0.5 24 32 0.5 8

6.5 0.5 24 32 0.5 8 7 0.4 21 28 0.4 7

7.5 0.3 14 19 0.3 4 8

Cu 0.2 12 16 0.2 4

3 0.80 1020 16.1 20.6 850

3.5 0.54 700 11.0 14.2 580 4 0.48 620 9.7 12.4 510

4.5 0.56 720 11.3 14.4 590 5 0.43 550 8.6 11.0 450

5.5 0.27 350 5.5 7.1 290 6 0.23 290 4.6 5.9 240

6.5 0.36 470 7.3 9.4 390 7 0.28 370 5.7 7.4 300

7.5 0.05 70 1.0 1.3 50 8

Mg 0.05 60 0.9 1.2 50

dilution 1:25

3 4.6 230 27 4.6 84

3.5 3.8 190 23 3.8 70 4 2.3 110 14 2.3 42

4.5 1.4 70 8 1.4 26 5 1.0 50 6 1.0 19

5.5 0.5 30 3 0.5 9 6 0.4 20 2 0.4 8

6.5 0.6 30 3 0.6 10 7 0.4 20 2 0.4 8

7.5 0.1 10 1 0.1 2 8

Mn 0.1 10 1 0.1 2

Appendix

A21

Table A-19 continued

pH value mg/L µg/g dissolved % theor. mg/L µmol/L remarks

3 8.8 440 2.3 8.9 160

3.5 6.9 350 1.8 7.0 125 4 4.6 230 1.2 4.7 83

4.5 3.1 160 0.8 3.2 56 5 2.8 140 0.7 2.8 50

5.5 2.3 110 0.6 2.3 41 6 2.1 100 0.5 2.1 37

6.5 1.4 70 0.4 1.4 25 7 1.5 70 0.4 1.5 27

7.5 0.8 40 0.2 0.8 14 8

Fe 0.6 30 0.2 0.6 11

3 3.1 160 22 3.1 15

3.5 2.6 130 18 2.7 13 4 3.0 150 21 3.0 15

4.5 3.7 180 26 3.7 18 5 3.8 190 27 3.9 19

5.5 4.5 230 31 4.5 22 6 4.3 210 30 4.3 21

6.5 4.2 210 29 4.2 20 7 3.3 160 23 3.3 16

7.5 1.6 80 11 1.6 8 8

Pb 1.1 50 8 1.1 5

3 15.4 773 79.2 15.6 238

3.5 14.0 704 72.1 14.2 217 4 13.0 647 66.3 13.0 199

4.5 13.0 651 66.6 13.1 200 5 12.7 635 65 12.8 196

5.5 11.2 560 57.3 11.3 172 6 10.7 535 54.7 10.8 165

6.5 11.9 598 61.2 12.0 184 7 11.2 563 57.7 11.4 174

7.5 6.8 340 34.8 6.8 105 8

Zn 6.7 335 34.3 6.7 103

Appendix

A22

Table A-20: pH variation of Rafz soil with NTA 2

pH value mg/L µg/g dissolved % theor. mg/L µmol/L remarks

3 3.9 5100 49 104 2600

3.5 4.1 5500 52 111 2800 4 4.4 5900 56 118 3000

4.5 3.6 4800 45 96 2400 5 2.7 3600 34 73 1800

5.5 3.4 4500 43 91 2300 6 2.9 3800 36 77 1900

6.5 3.3 4400 42 89 2200 7 3.3 4400 42 88 2200

7.5 2.7 3600 34 72 1800 8

Ca 3.0 4000 38 80 2000

dilution 1:25

3 0.8 44 58 0.9 14

3.5 0.8 43 57 0.9 14 4 0.8 41 54 0.8 13

4.5 0.8 40 52 0.8 13 5 0.7 38 50 0.8 12

5.5 0.7 37 49 0.7 12 6 0.7 34 45 0.7 11

6.5 0.6 33 44 0.7 11 7 0.6 33 43 0.7 10

7.5 0.7 34 46 0.7 11 8

Cu 0.6 31 41 0.6 10

3 0.49 650 10.3 13.2 540

3.5 0.56 740 11.7 15.0 610 4 0.45 600 9.4 12.1 500

4.5 0.45 600 9.4 12.0 490 5 0.38 510 8.0 10.3 420

5.5 0.35 460 7.2 9.3 380 6 0.22 300 4.6 6.0 250

6.5 0.26 350 5.5 7.1 290 7 0.23 310 4.9 6.3 260

7.5 0.10 130 2.1 2.6 110 8

Mg 0.10 140 2.2 2.8 110

dilution 1:25

3 8.5 440 53 8.9 163

3.5 8.1 420 50 8.4 154 4 7.7 400 47 8.0 146

4.5 6.7 350 41 7.0 127 5 5.9 300 36 6.1 111

5.5 5.1 260 31 5.3 96 6 4.0 210 25 4.2 76

6.5 2.6 130 16 2.7 49 7 1.5 80 9 1.6 29

7.5 1.4 70 9 1.5 27 8

Mn 0.9 50 6 0.9 17

Appendix

A23

Table A-20 continued

pH value mg/L µg/g dissolved % theor. mg/L µmol/L remarks

3 26.0 1350 7.2 27.2 487

3.5 20.7 1070 5.7 21.6 387 4 15.2 790 4.2 15.9 285

4.5 12.9 670 3.6 13.5 242 5 11.6 600 3.2 12.1 217

5.5 9.1 470 2.5 9.5 170 6 8.3 430 2.3 8.6 154

6.5 7.5 390 2.1 7.9 141 7 6.5 340 1.8 6.8 122

7.5 7.1 370 2.0 7.4 133 8

Fe 6.2 320 1.7 6.5 116

3 12.6 650 91 13.2 64

3.5 13.1 680 95 13.7 66 4 13.1 680 94 13.6 66

4.5 12.6 650 91 13.1 63 5 12.1 620 87 12.6 61

5.5 11.5 590 83 12.0 58 6 10.4 540 75 10.8 52

6.5 10.1 520 73 10.6 51 7 9.0 470 65 9.4 45

7.5 8.5 440 62 8.9 43 8

Pb 7.1 370 52 7.5 36

3 16.0 835 85.5 16.8 257

3.5 16.6 860 88 17.3 265 4 16.0 827 84.7 16.7 255

4.5 14.8 769 78.8 15.5 237 5 14.0 726 74.3 14.6 224

5.5 13.0 675 69.2 13.6 208 6 11.6 599 61.4 12.1 185

6.5 13.1 680 69.7 13.7 210 7 11.9 619 63.4 12.5 191

7.5 10.7 556 57 11.2 171 8

Zn 10.1 522 53.4 10.5 161

Appendix

A24

Table A-21: pH variation of Rafz soil without complexing agent

pH value mg/L µg/g dissolved % theor. mg/L µmol/L remarks

3 4.8 6100 58 123 3100

3.5 4.4 5700 54 115 2900 4 3.8 4900 46 98 2400

4.5 3.9 5000 48 102 2500 5 3.0 3900 37 78 1900

5.5 2.9 3700 35 75 1900 6 2.9 3700 35 74 1800

6.5 2.7 3400 33 69 1700 7 2.9 3800 36 76 1900

7.5 0.5 600 6 12 300 8

Ca 0.4 500 5 10 200

dilution 1:25

3 0.3 13 17 0.3 4

3.5 0.1 7 9 0.1 2 4 0.1 6 8 0.1 2

4.5 0.1 5 7 0.1 2 5 0.1 5 6 0.1 2

5.5 0.1 5 6 0.1 1 6 0.1 5 6 0.1 2

6.5 0.1 4 6 0.1 1 7 0.1 4 5 0.1 1

7.5 0.1 4 5 0.1 1 8

Cu 0.1 4 5 0.1 1

3 0.52 670 10.6 13.5 560

3.5 0.57 730 11.5 14.7 610 4 0.50 640 10.0 12.8 530

4.5 0.50 630 10.0 12.8 530 5 0.38 490 7.7 9.8 400

5.5 0.25 320 5.0 6.4 260 6 0.32 410 6.4 8.2 340

6.5 0.33 420 6.6 8.5 350 7 0.28 360 5.6 7.2 300

7.5 0.06 70 1.1 1.4 60 8

Mg 0.05 60 1.0 1.3 50

dilution 1:25

3 3.0 150 18 3.0 54

3.5 2.0 100 12 2.0 36 4 1.7 80 10 1.7 30

4.5 1.3 70 8 1.4 25 5 0.9 40 5 0.9 16

5.5 0.5 30 3 0.5 10 6 0.7 30 4 0.7 12

6.5 0.5 30 3 0.5 10 7 0.3 20 2 0.3 6

7.5 0.1 0 0 0.1 1 8

Mn 0.1 0 0 0.1 1

Appendix

A25

Table A-21 continued

pH value mg/L µg/g dissolved % theor. mg/L µmol/L remarks

3 0.2 8 0.0 0.2 2.9

3.5 0.1 5 0.0 0.1 1.9 4 0.1 4 0.0 0.1 1.5

4.5 0.1 3 0.0 0.1 1.1 5 0.0 2 0.0 0.1 0.9

5.5 0.1 3 0.0 0.1 0.9 6 0.0 2 0.0 0.1 0.8

6.5 0.0 2 0.0 0.0 0.7 7 0.0 2 0.0 0.0 0.6

7.5 0.1 4 0.0 0.1 1.4 8

Fe 0.1 3 0.0 0.1 1.2

3 1.9 95 13.3 1.9 9.3

3.5 0.6 28 3.9 0.6 2.7 4 0.3 14 2 0.3 1.4

4.5 0.2 9 1.3 0.2 0.9 5 0.1 6 0.8 0.1 0.6

5.5 0.1 6 0.8 0.1 0.6 6 0.1 6 0.8 0.1 0.6

6.5 0.1 6 0.8 0.1 0.6 7 0.1 6 0.8 0.1 0.6

7.5 0.1 7 0.9 0.1 0.6 8

Pb 0.1 6 0.9 0.1 0.6

3 15.6 780 79.9 15.7 240

3.5 13.3 663 67.9 13.3 204 4 11.8 588 60.2 11.8 181

4.5 9.6 479 49.0 9.6 147 5 6.7 334 34.2 6.7 103

5.5 3.7 182 18.6 3.7 56 6 4.1 204 20.9 4.1 63

6.5 1.9 97 10.0 2.0 30 7 0.7 34 3.5 0.7 11

7.5 0.2 9 1.0 0.2 3 8

Zn 0.2 8 0.8 0.2 2

Table A-22: Sequential extraction Fe

Fraction EDDS 1 2 3 4 5 6 7 ∑ V [mL] 250.00 50.50 75.50 100.50 75.00 300.00 300.00 m [g] 5.00 2.00 2.00 2.00 2.00 2.00 2.00 Blank value A [mg/L] 0.45 0.00 0.01 0.02 0.01 0.09 -0.00 (24h) B [mg/L] 0.03 -0.01 0.01 0.05 0.01 0.09 0.00 ∅ [mg/L] 0.24 -0.01 0.01 0.04 0.01 0.09 0.00 Blank value A [mg/L] 0.12 (48h) B [mg/L] 0.01 ∅ [mg/L] 0.06 Kirschgarten A [mg/L] 0.05 0.12 0.50 18.45 20.75 58.63 B [mg/L] 0.06 0.13 0.54 18.23 22.08 56.13 ∅ [mg/L] 0.05 0.12 0.52 18.34 21.41 57.38 σ [%] 8.63 8.40 5.07 0.85 4.40 3.08 ∅-BV [mg/L] 0.06 0.11 0.48 18.33 21.33 57.38 [µg/g] 1.53 4.15 24.31 687.53 3198.86 8607.21 8085.94 20609.53 % of total 0.01 0.02 0.12 3.34 15.52 41.76 39.23 100.00 Mattenweg A [mg/L] 0.03 0.14 0.83 27.02 15.92 49.79 B [mg/L] 0.03 0.13 0.83 27.45 18.31 54.69 ∅ [mg/L] 0.03 0.14 0.83 27.24 17.11 52.24 σ [%] 6.41 4.61 0.11 1.10 9.86 6.63 ∅-BV [mg/L] 0.04 0.12 0.80 27.23 17.02 52.24 [µg/g] 0.94 4.66 40.04 1021.04 2553.55 7836.29 6503.38 17959.91 % of total 0.01 0.03 0.22 5.69 14.22 43.63 36.21 100.00 Rafz A [mg/L] 0.03 0.09 0.80 18.71 11.85 30.42 B [mg/L] 0.03 0.08 0.81 18.11 11.33 32.61 ∅ [mg/L] 0.03 0.09 0.81 18.41 11.59 31.52 σ [%] 13.10 2.71 1.34 2.31 3.17 4.91 ∅-BV [mg/L] 0.04 0.07 0.77 18.40 11.50 31.52 [µg/g] 0.95 2.71 38.73 689.96 1724.57 4727.57 8197.75 15382.24 % of total 0.01 0.02 0.25 4.49 11.21 30.73 53.29 100.00

Table A-22 continued

Fraction EDDS 1 2 3 4 5 6 7 ∑ Kirschgarten A [mg/L] 2.82 0.08 0.12 0.25 16.95 22.26 74.10 24 B [mg/L] 2.67 0.16 0.11 0.31 16.40 21.15 66.44 ∅ [mg/L] 2.74 0.12 0.11 0.28 16.67 21.70 70.27 σ [%] 3.78 49.95 6.71 14.51 2.34 3.62 7.70 ∅-BV [mg/L] 2.51 0.12 0.10 0.25 16.67 21.62 70.27 [µg/g] 125.30 3.13 3.71 12.38 624.96 3242.38 10540.23 10098.93 24651.02 % of total 0.51 0.01 0.02 0.05 2.54 13.15 42.76 40.97 100.00 Mattenweg A [mg/L] 1.72 0.06 0.11 0.29 28.74 19.22 75.57 24 B [mg/L] 1.68 0.05 0.12 0.33 28.88 21.00 84.24 ∅ [mg/L] 1.70 0.06 0.11 0.31 28.81 20.11 79.90 σ [%] 1.56 5.58 5.50 8.36 0.36 6.27 7.68 ∅-BV [mg/L] 1.46 0.06 0.10 0.27 28.80 20.02 79.90 [µg/g] 72.96 1.57 3.73 13.65 1080.05 3003.64 11985.28 9626.25 25787.13 % of total 0.28 0.01 0.01 0.05 4.19 11.65 46.48 37.33 100.00 Rafz A [mg/L] 2.81 0.04 0.07 0.58 20.80 15.59 45.17 24 B [mg/L] 2.78 0.05 0.07 0.54 20.94 14.90 48.34 ∅ [mg/L] 2.80 0.05 0.07 0.56 20.87 15.25 46.75 σ [%] 0.94 12.86 6.30 5.07 0.46 3.22 4.80 ∅-BV [mg/L] 2.56 0.05 0.05 0.52 20.86 15.16 46.75 [µg/g] 127.84 1.36 2.03 26.22 782.27 2273.66 7012.73 9605.89 19832.00 % of total 0.64 0.01 0.01 0.13 3.94 11.46 35.36 48.44 100.00

Table A-22 continued

Fraction EDDS 1 2 3 4 5 6 7 ∑ Kirschgarten A [mg/L] 3.44 0.07 0.09 0.27 17.18 21.25 75.74 48 B [mg/L] 3.36 0.07 0.10 0.26 17.40 22.65 67.80 ∅ [mg/L] 3.40 0.07 0.10 0.26 17.29 21.95 71.77 σ [%] 1.77 0.22 3.11 2.28 0.91 4.49 7.83 ∅-BV [mg/L] 3.34 0.07 0.08 0.23 17.28 21.86 71.77 [µg/g] 166.92 1.81 3.06 11.45 647.96 3279.13 10764.93 10099.65 24974.91 % of total 0.67 0.01 0.01 0.05 2.59 13.13 43.10 40.44 100.00 Mattenweg A [mg/L] 2.16 0.03 0.11 0.31 29.62 19.73 62.99 48 B [mg/L] 2.19 0.03 0.14 0.33 28.23 20.29 68.75 ∅ [mg/L] 2.17 0.03 0.13 0.32 28.93 20.01 65.87 σ [%] 0.76 18.89 11.70 4.86 3.40 1.99 6.18 ∅-BV [mg/L] 2.11 0.04 0.11 0.29 28.92 19.92 65.87 [µg/g] 105.55 0.90 4.18 14.41 1084.43 2987.79 9880.62 10363.99 24441.87 % of total 0.43 0.00 0.02 0.06 4.44 12.22 40.42 42.40 100.00 Rafz A [mg/L] 3.53 0.04 0.06 0.58 19.01 15.12 32.91 48 B [mg/L] 3.54 0.02 0.07 0.60 18.91 15.26 38.40 ∅ [mg/L] 3.54 0.03 0.07 0.59 18.96 15.19 35.66 σ [%] 0.13 43.19 8.71 2.03 0.38 0.67 10.89 ∅-BV [mg/L] 3.47 0.04 0.05 0.55 18.95 15.10 35.66 [µg/g] 173.57 0.92 1.99 27.69 710.58 2264.92 5348.52 10487.16 19015.35 % of total 0.91 0.00 0.01 0.15 3.74 11.91 28.13 55.15 100.00

Table A-23: Sequential extraction Mn

Fraction EDDS 1 2 3 4 5 6 7 ∑ V [mL] 250.00 50.50 75.50 100.50 75.00 300.00 300.00 m [g] 5.00 2.00 2.00 2.00 2.00 2.00 2.00 Blank value A [mg/L] 0.00 0.01 -0.01 0.01 0.00 0.01 0.00 (24h) B [mg/L] -0.01 0.00 -0.01 0.01 0.01 0.01 0.00 ∅ [mg/L] -0.01 0.00 -0.01 0.01 0.01 0.01 0.00 Blank value A [mg/L] 0.00 (48h) B [mg/L] -0.01 ∅ [mg/L] 0.00 Kirschgarten A [mg/L] 1.35 2.38 7.58 1.64 0.67 0.44 B [mg/L] 1.41 2.29 7.88 1.49 0.71 0.42 ∅ [mg/L] 1.38 2.34 7.73 1.56 0.69 0.43 σ [%] 2.99 2.88 2.67 6.77 3.93 3.60 ∅-BV [mg/L] 1.37 2.35 7.72 1.56 0.68 0.42 [µg/g] 34.67 88.57 387.92 58.37 101.84 63.62 77.06 812.06 % of total 4.27 10.91 47.77 7.19 12.54 7.83 9.49 100.00 Mattenweg A [mg/L] 0.31 2.15 7.90 1.20 0.25 0.31 B [mg/L] 0.32 2.17 8.02 1.31 0.40 0.31 ∅ [mg/L] 0.32 2.16 7.96 1.25 0.33 0.31 σ [%] 2.14 0.88 1.04 5.98 32.79 1.02 ∅-BV [mg/L] 0.31 2.17 7.95 1.25 0.32 0.31 [µg/g] 7.89 82.06 399.41 46.80 47.78 46.31 51.60 681.85 % of total 1.16 12.04 58.58 6.86 7.01 6.79 7.57 100.00 Rafz A [mg/L] 0.31 0.84 9.82 1.48 0.62 0.22 B [mg/L] 0.32 0.82 8.80 1.08 0.52 0.24 ∅ [mg/L] 0.32 0.83 9.31 1.28 0.57 0.23 σ [%] 1.86 1.26 7.72 22.02 12.15 5.50 ∅-BV [mg/L] 0.31 0.84 9.30 1.28 0.56 0.23 [µg/g] 7.84 31.69 467.25 47.97 84.41 33.95 82.26 755.36 % of total 1.04 4.20 61.86 6.35 11.17 4.49 10.89 100.00

Table A-23 continued

Fraction EDDS 1 2 3 4 5 6 7 ∑ Kirschgarten A [mg/L] 1.23 2.50 4.01 5.66 1.86 0.72 0.37 24 B [mg/L] 1.22 2.10 4.14 5.93 2.17 0.92 0.35 ∅ [mg/L] 1.22 2.30 4.07 5.80 2.02 0.82 0.35 σ [%] 0.47 12.37 2.27 3.34 10.87 17.45 3.32 ∅-BV [mg/L] 1.23 2.29 4.08 5.79 2.01 0.81 0.35 [µg/g] 61.50 57.85 154.10 290.85 75.47 121.44 52.64 80.81 894.65 % of total 6.88 6.47 17.22 32.51 8.44 13.57 5.88 9.03 100.00 Mattenweg A [mg/L] 0.23 1.09 4.96 5.78 1.85 0.32 0.32 24 B [mg/L] 0.22 1.16 5.05 6.05 2.00 0.32 0.39 ∅ [mg/L] 0.22 1.12 5.00 5.91 1.92 0.32 0.36 σ [%] 3.35 4.66 1.23 3.24 5.32 1.67 13.44 ∅-BV [mg/L] 0.23 1.12 5.01 5.90 1.92 0.31 0.35 [µg/g] 11.42 28.22 189.52 296.66 71.98 46.88 53.24 62.92 760.84 % of total 1.50 3.71 24.91 38.99 9.46 6.16 7.00 8.27 100.00 Rafz A [mg/L] 0.44 1.32 2.67 8.03 1.65 0.60 0.30 24 B [mg/L] 0.43 1.10 2.64 8.32 1.68 0.57 0.32 ∅ [mg/L] 0.44 1.21 2.65 8.18 1.66 0.58 0.31 σ [%] 0.21 12.64 0.87 2.45 1.39 3.58 3.70 ∅-BV [mg/L] 0.44 1.21 2.67 8.17 1.66 0.57 0.31 [µg/g] 22.10 30.51 100.61 410.40 62.19 85.94 45.85 97.07 854.67 % of total 2.59 3.57 11.77 48.02 7.28 10.06 5.36 11.36 100.00

Table A-23 continued

Fraction EDDS 1 2 3 4 5 6 7 ∑ Kirschgarten A [mg/L] 0.43 3.31 4.27 5.67 2.17 0.88 0.42 48 B [mg/L] 0.38 3.18 4.43 5.80 2.04 0.70 0.34 ∅ [mg/L] 0.40 3.25 4.35 5.74 2.11 0.79 0.38 σ [%] 9.04 2.78 2.64 1.57 4.30 15.72 14.48 ∅-BV [mg/L] 0.41 3.24 4.36 5.73 2.10 0.78 0.38 [µg/g] 20.45 81.84 164.65 287.76 78.87 117.33 56.84 81.09 888.84 % of total 2.30 9.21 18.52 32.37 8.87 13.20 6.40 9.12 100.00 Mattenweg A [mg/L] 0.29 1.00 4.91 6.02 1.96 0.33 0.36 48 B [mg/L] 0.29 1.11 4.92 5.85 1.90 0.34 0.40 ∅ [mg/L] 0.29 1.05 4.91 5.94 1.93 0.33 0.38 σ [%] 0.42 7.42 0.26 2.02 2.21 2.44 7.67 ∅-BV [mg/L] 0.29 1.05 4.92 5.93 1.92 0.32 0.38 [µg/g] 14.71 26.43 186.15 297.84 72.08 48.35 56.91 66.62 769.08 % of total 1.91 3.44 24.20 38.73 9.37 6.29 7.40 8.66 100.00 Rafz A [mg/L] 0.69 1.17 2.66 8.02 1.85 0.69 0.29 48 B [mg/L] 0.67 1.10 2.51 7.97 1.61 0.63 0.33 ∅ [mg/L] 0.68 1.13 2.58 7.99 1.73 0.66 0.31 σ [%] 1.46 4.56 4.18 0.36 9.70 6.20 8.01 ∅-BV [mg/L] 0.68 1.13 2.59 7.99 1.72 0.65 0.31 [µg/g] 34.21 28.50 97.93 401.29 64.57 97.86 45.99 109.58 879.92 % of total 3.89 3.24 11.13 45.60 7.34 11.12 5.23 12.45 100.00

Table A-24: Sequential extraction Cu

Fraction EDDS 1 2 3 4 5 6 7 ∑ V [mL] 250.00 50.50 75.50 100.50 75.00 300.00 300.00 m [g] 5.00 2.00 2.00 2.00 2.00 2.00 2.00 Blank value A [mg/L] 0.10 0.00 0.01 0.00 0.01 -0.00 0.00 (24h) B [mg/L] 0.02 0.00 0.01 0.01 0.01 -0.01 0.00 ∅ [mg/L] 0.06 0.00 0.01 0.01 0.01 -0.01 0.00 Blank value A [mg/L] 0.01 (48h) B [mg/L] 0.01 ∅ [mg/L] 0.01 Kirschgarten A [mg/L] 0.48 0.51 0.32 8.58 0.37 0.20 B [mg/L] 0.38 0.56 0.38 8.60 0.37 0.19 ∅ [mg/L] 0.43 0.54 0.35 8.59 0.37 0.19 σ [%] 15.27 5.89 11.27 0.17 1.30 3.76 ∅-BV [mg/L] 0.43 0.53 0.34 8.58 0.37 0.19 [µg/g] 10.88 20.04 17.30 321.68 56.18 28.61 14.73 469.42 % of total 2.32 4.27 3.68 68.53 11.97 6.10 3.14 100.00 Mattenweg A [mg/L] 0.93 0.96 0.72 8.10 0.39 0.22 B [mg/L] 0.94 1.10 0.75 8.27 0.44 0.23 ∅ [mg/L] 0.93 1.03 0.73 8.18 0.41 0.23 σ [%] 0.98 9.26 2.39 1.54 8.70 1.48 ∅-BV [mg/L] 0.94 1.03 0.73 8.18 0.42 0.22 [µg/g] 23.65 38.81 36.59 306.57 62.93 33.63 13.84 516.03 % of total 4.58 7.52 7.09 59.41 12.20 6.52 2.68 100.00 Rafz A [mg/L] 0.07 0.13 0.11 1.15 0.10 0.03 B [mg/L] 0.06 0.09 0.07 1.12 0.10 0.03 ∅ [mg/L] 0.07 0.11 0.09 1.14 0.10 0.03 σ [%] 9.37 27.29 32.32 1.92 1.69 1.27 ∅-BV [mg/L] 0.07 0.10 0.08 1.13 0.11 0.03 [µg/g] 1.78 3.87 4.10 42.37 15.82 4.90 17.28 90.11 % of total 1.98 4.29 4.54 47.02 17.55 5.44 19.17 100.00

Table A-24 continued

Fraction EDDS 1 2 3 4 5 6 7 ∑ Kirschgarten A [mg/L] 5.96 0.25 0.09 0.04 2.83 0.25 0.18 24 B [mg/L] 5.75 0.28 0.08 0.04 2.80 0.27 0.16 ∅ [mg/L] 5.86 0.27 0.08 0.04 2.81 0.26 0.17 σ [%] 2.51 7.53 2.78 4.39 0.71 4.24 6.36 ∅-BV [mg/L] 5.80 0.27 0.08 0.03 2.81 0.26 0.17 [µg/g] 289.96 6.81 2.95 1.59 105.22 39.53 25.21 20.85 492.12 % of total 58.92 1.38 0.60 0.32 21.38 8.03 5.12 4.24 100.00 Mattenweg A [mg/L] 5.14 0.37 0.19 0.11 4.98 0.42 0.27 24 B [mg/L] 5.01 0.41 0.20 0.12 5.19 0.42 0.32 ∅ [mg/L] 5.08 0.39 0.20 0.12 5.08 0.42 0.30 σ [%] 1.91 6.59 2.19 7.18 2.92 0.88 10.33 ∅-BV [mg/L] 5.02 0.39 0.19 0.11 5.07 0.42 0.29 [µg/g] 250.91 9.96 7.24 5.67 190.18 63.74 44.21 21.05 592.96 % of total 42.31 1.68 1.22 0.96 32.07 10.75 7.46 3.55 100.00 Rafz A [mg/L] 0.75 0.16 0.04 0.03 0.71 0.08 0.05 24 B [mg/L] 0.75 0.18 0.03 0.02 0.76 0.08 0.05 ∅ [mg/L] 0.75 0.17 0.03 0.03 0.73 0.08 0.05 σ [%] 0.56 8.40 18.28 3.94 4.12 0.61 6.41 ∅-BV [mg/L] 0.69 0.18 0.03 0.02 0.73 0.09 0.05 [µg/g] 34.73 4.43 1.06 0.99 27.20 12.92 7.15 12.53 101.00 % of total 34.38 4.38 1.05 0.98 26.93 12.79 7.08 12.41 100.00

Table A-24 continued

Fraction EDDS 1 2 3 4 5 6 7 ∑ Kirschgarten A [mg/L] 6.68 0.23 0.06 0.03 2.32 0.24 0.18 48 B [mg/L] 6.49 0.24 0.06 0.04 2.37 0.25 0.17 ∅ [mg/L] 6.59 0.24 0.06 0.03 2.35 0.24 0.17 σ [%] 2.05 1.90 2.37 5.97 1.36 1.65 3.76 ∅-BV [mg/L] 6.58 0.24 0.06 0.03 2.34 0.25 0.17 [µg/g] 328.77 6.06 2.15 1.46 87.67 37.52 25.52 21.85 510.98 % of total 64.34 1.19 0.42 0.29 17.16 7.34 4.99 4.28 100.00 Mattenweg A [mg/L] 5.67 0.41 0.15 0.09 4.39 0.39 0.28 48 B [mg/L] 5.72 0.39 0.15 0.10 4.29 0.42 0.29 ∅ [mg/L] 5.69 0.40 0.15 0.09 4.34 0.40 0.29 σ [%] 0.65 5.04 2.49 5.23 1.72 5.36 2.50 ∅-BV [mg/L] 5.68 0.40 0.14 0.09 4.33 0.41 0.29 [µg/g] 284.06 10.14 5.37 4.48 162.46 61.50 43.07 24.31 595.39 % of total 47.71 1.70 0.90 0.75 27.29 10.33 7.23 4.08 100.00 Rafz A [mg/L] 0.84 0.13 0.03 0.03 0.60 0.06 0.05 48 B [mg/L] 0.84 0.13 0.02 0.02 0.59 0.06 0.05 ∅ [mg/L] 0.84 0.13 0.02 0.02 0.60 0.06 0.05 σ [%] 0.03 2.85 13.37 13.32 1.64 3.25 3.81 ∅-BV [mg/L] 0.83 0.13 0.02 0.02 0.59 0.07 0.05 [µg/g] 41.39 3.31 0.73 0.98 22.08 9.92 7.66 14.49 100.55 % of total 41.16 3.29 0.72 0.98 21.95 9.87 7.62 14.41 100.00

Table A-25: Sequential extraction Pb

Fraction EDDS 1 2 3 4 5 6 7 ∑ V [mL] 250.00 50.50 75.50 100.50 75.00 300.00 300.00 m [g] 5.00 2.00 2.00 2.00 2.00 2.00 2.00 Blank value A [mg/L] 0.10 -0.16 -0.01 0.02 -0.01 0.07 -0.03 (24h) B [mg/L] -0.07 -0.17 0.00 0.02 -0.01 0.02 -0.03 ∅ [mg/L] 0.01 -0.17 -0.01 0.02 -0.01 0.04 -0.03 Blank value A [mg/L] -0.02 (48h) B [mg/L] -0.09 ∅ [mg/L] -0.05 Kirschgarten A [mg/L] -0.04 0.08 0.17 1.20 0.13 -0.02 B [mg/L] -0.09 0.07 0.19 1.20 0.12 -0.03 ∅ [mg/L] -0.06 0.07 0.18 1.20 0.13 -0.03 σ [%] -60.70 9.12 5.53 0.02 4.90 -28.82 ∅-BV [mg/L] 0.10 0.08 0.16 1.21 0.08 0.00 [µg/g] 2.58 3.06 8.18 45.51 12.47 0.47 6.78 79.05 % of total 3.26 3.88 10.35 57.57 15.77 0.60 8.58 100.00 Mattenweg A [mg/L] -0.02 0.16 0.20 0.97 0.17 -0.03 B [mg/L] -0.11 0.15 0.19 0.98 0.07 -0.05 ∅ [mg/L] -0.07 0.15 0.19 0.97 0.12 -0.04 σ [%] -91.05 4.12 2.66 0.91 57.93 -33.72 ∅-BV [mg/L] 0.10 0.16 0.18 0.98 0.08 -0.01 [µg/g] 2.44 6.21 8.83 36.82 11.63 3.97 69.89 % of total 3.50 8.88 12.63 52.67 16.64 5.68 100.00 Rafz A [mg/L] 0.06 2.75 4.88 10.70 0.17 -0.00 B [mg/L] 0.01 2.89 4.71 9.95 0.09 0.02 ∅ [mg/L] 0.04 2.82 4.79 10.33 0.13 0.01 σ [%] 108.34 3.69 2.54 5.14 41.89 161.62 ∅-BV [mg/L] 0.20 2.83 4.77 10.34 0.09 0.04 [µg/g] 5.06 106.80 239.92 387.68 13.09 5.67 9.08 767.29 % of total 0.66 13.92 31.27 50.53 1.71 0.74 1.18 100.00

Table A-25 continued

Fraction EDDS 1 2 3 4 5 6 7 ∑ Kirschgarten A [mg/L] 0.16 -0.02 0.05 0.14 1.17 0.13 0.01 24 B [mg/L] 0.16 -0.06 0.06 0.19 1.14 0.06 -0.01 ∅ [mg/L] 0.16 -0.04 0.05 0.16 1.15 0.10 0.00 σ [%] 1.24 -71.04 13.88 22.51 2.19 45.65 -1478.50 ∅-BV [mg/L] 0.15 0.12 0.06 0.15 1.16 0.05 0.03 [µg/g] 7.31 3.09 2.41 7.33 43.65 7.68 4.33 5.49 81.29 % of total 8.99 3.80 2.97 9.02 53.69 9.45 5.32 6.75 100.00 Mattenweg A [mg/L] 0.18 -0.12 0.14 0.11 0.94 0.13 -0.01 24 B [mg/L] 0.16 -0.04 0.13 0.11 0.98 0.13 -0.01 ∅ [mg/L] 0.17 -0.08 0.13 0.11 0.96 0.13 -0.01 σ [%] 5.18 -63.56 4.14 4.05 2.98 0.00 -47.69 ∅-BV [mg/L] 0.16 0.08 0.14 0.09 0.97 0.09 0.02 [µg/g] 7.83 2.11 5.41 4.50 36.22 13.23 2.31 71.61 % of total 10.93 2.95 7.56 6.29 50.57 18.48 3.22 100.00 Rafz A [mg/L] 4.21 0.07 2.15 3.87 10.39 0.35 0.02 24 B [mg/L] 4.23 0.02 2.23 3.66 10.60 0.31 0.02 ∅ [mg/L] 4.22 0.04 2.19 3.77 10.49 0.33 0.02 σ [%] 0.26 83.47 2.39 3.98 1.44 9.08 8.50 ∅-BV [mg/L] 4.21 0.21 2.20 3.75 10.50 0.28 0.05 [µg/g] 210.31 5.21 82.99 188.28 393.86 42.59 7.16 12.40 942.79 % of total 22.31 0.55 8.80 19.97 41.78 4.52 0.76 1.32 100.00

Table A-25 continued

Fraction EDDS 1 2 3 4 5 6 7 ∑ Kirschgarten A [mg/L] 0.03 -0.02 0.05 0.15 1.28 0.38 -0.02 48 B [mg/L] 0.04 -0.08 0.05 0.15 1.29 0.21 -0.03 ∅ [mg/L] 0.04 -0.05 0.05 0.15 1.28 0.30 -0.02 σ [%] 29.38 -89.51 9.22 3.83 0.41 40.51 -14.63 ∅-BV [mg/L] 0.09 0.12 0.06 0.13 1.29 0.25 0.01 [µg/g] 4.36 2.96 2.28 6.58 48.46 37.90 0.93 4.45 107.91 % of total 4.04 2.74 2.11 6.09 44.91 35.12 0.86 4.12 100.00 Mattenweg A [mg/L] 0.20 -0.06 0.14 0.08 0.98 0.24 -0.04 48 B [mg/L] 0.20 -0.10 0.13 0.11 0.94 0.22 -0.03 ∅ [mg/L] 0.20 -0.08 0.14 0.09 0.96 0.23 -0.03 σ [%] 0.07 -34.35 6.41 25.05 3.17 6.83 -13.98 ∅-BV [mg/L] 0.25 0.09 0.15 0.07 0.97 0.19 -0.01 [µg/g] 12.48 2.17 5.58 3.76 36.46 27.89 3.36 91.70 % of total 13.61 2.37 6.09 4.10 39.76 30.41 3.67 100.00 Rafz A [mg/L] 4.04 0.03 2.41 3.75 10.05 0.30 0.00 48 B [mg/L] 4.05 0.02 2.48 3.92 10.30 0.36 -0.01 ∅ [mg/L] 4.04 0.02 2.45 3.84 10.17 0.33 0.00 σ [%] 0.19 6.98 2.00 3.12 1.79 12.75 -413.79 ∅-BV [mg/L] 4.09 0.19 2.46 3.82 10.18 0.29 0.03 [µg/g] 204.63 4.79 92.74 191.83 381.87 42.81 4.21 13.48 936.34 % of total 21.85 0.51 9.90 20.49 40.78 4.57 0.45 1.44 100.00

Table A-26: Sequential extraction Zn

Fraction EDDS 1 2 3 4 5 6 7 ∑ V [mL] 250.00 50.50 75.50 100.50 75.00 300.00 300.00 m [g] 5.00 2.00 2.00 2.00 2.00 2.00 2.00 Blank value A [mg/L] 0.00 -0.01 0.00 0.02 0.02 -0.01 0.01 (24h) B [mg/L] 0.02 -0.01 0.00 0.01 0.00 -0.02 0.01 ∅ [mg/L] 0.01 -0.01 0.00 0.01 0.01 -0.01 0.01 Blank value A [mg/L] 0.00 (48h) B [mg/L] 0.00 ∅ [mg/L] 0.00 Kirschgarten A [mg/L] 0.23 2.39 1.56 3.10 1.18 1.19 B [mg/L] 0.30 2.37 1.61 2.99 1.19 1.05 ∅ [mg/L] 0.27 2.38 1.58 3.05 1.19 1.12 σ [%] 19.88 0.55 2.15 2.73 0.13 9.18 ∅-BV [mg/L] 0.28 2.38 1.57 3.04 1.20 1.12 [µg/g] 6.98 89.90 78.77 113.86 179.61 167.42 76.20 712.73 % of total 0.98 12.61 11.05 15.97 25.20 23.49 10.69 100.00 Mattenweg A [mg/L] 0.09 1.57 1.12 2.87 1.93 0.91 B [mg/L] 0.08 1.58 1.12 2.99 2.10 0.91 ∅ [mg/L] 0.08 1.57 1.12 2.93 2.02 0.91 σ [%] 6.73 0.77 0.08 2.98 5.69 0.02 ∅-BV [mg/L] 0.09 1.57 1.10 2.92 2.03 0.90 [µg/g] 2.33 59.41 55.39 109.47 304.23 134.90 60.24 725.97 % of total 0.32 8.18 7.63 15.08 41.91 18.58 8.30 100.00 Rafz A [mg/L] 1.23 7.40 3.33 5.22 1.8 1.02 B [mg/L] 1.18 7.53 3.20 4.85 1.71 1.15 ∅ [mg/L] 1.20 7.46 3.27 5.04 1.77 1.09 σ [%] 3.21 1.20 2.83 5.25 4.65 8.45 ∅-BV [mg/L] 1.21 7.46 3.25 5.03 1.78 1.08 [µg/g] 30.60 281.68 163.34 188.48 267.30 162.33 86.93 1180.65 % of total 2.59 23.86 13.83 15.96 22.64 13.75 7.36 100.00

Table A-26 continued

Fraction EDDS 1 2 3 4 5 6 7 ∑ Kirschgarten A [mg/L] 4.25 0.04 0.42 0.47 1.81 1.04 1.26 24 B [mg/L] 4.20 0.03 0.46 0.65 1.83 0.97 1.12 ∅ [mg/L] 4.23 0.03 0.44 0.56 1.82 1.01 1.19 σ [%] 0.78 28.73 5.62 22.71 0.96 4.77 8.12 ∅-BV [mg/L] 4.21 0.04 0.44 0.54 1.81 1.02 1.18 [µg/g] 210.73 1.03 16.58 27.24 67.88 153.15 177.71 108.48 762.80 % of total 27.63 0.13 2.17 3.57 8.90 20.08 23.30 14.22 100.00 Mattenweg A [mg/L] 2.20 0.02 0.61 0.49 2.65 2.35 1.13 24 B [mg/L] 2.15 0.03 0.61 0.51 2.76 2.53 1.23 ∅ [mg/L] 2.18 0.02 0.61 0.50 2.70 2.44 1.18 σ [%] 1.75 36.33 0.19 2.65 2.67 5.32 5.88 ∅-BV [mg/L] 2.17 0.03 0.61 0.48 2.69 2.45 1.17 [µg/g] 108.37 0.78 22.94 24.19 101.05 367.74 176.09 98.62 899.79 % of total 12.04 0.09 2.55 2.69 11.23 40.87 19.57 10.96 100.00 Rafz A [mg/L] 9.18 0.10 1.76 1.48 3.50 1.92 1.53 24 B [mg/L] 9.35 0.10 1.79 1.30 3.58 1.91 1.61 ∅ [mg/L] 9.27 0.10 1.77 1.39 3.54 1.91 1.57 σ [%] 1.34 0.90 1.40 9.48 1.71 0.36 3.62 ∅-BV [mg/L] 9.26 0.11 1.77 1.38 3.53 1.92 1.56 [µg/g] 462.75 2.80 66.86 69.16 132.31 288.47 234.51 127.53 1384.39 % of total 33.43 0.20 4.83 5.00 9.56 20.84 16.94 9.21 100.00

Table A-26 continued

Fraction EDDS 1 2 3 4 5 6 7 ∑ Kirschgarten A [mg/L] 4.47 0.04 0.36 0.40 1.85 1.15 1.30 48 B [mg/L] 4.63 0.03 0.36 0.41 1.86 0.99 1.15 ∅ [mg/L] 4.55 0.04 0.36 0.41 1.85 1.07 1.22 σ [%] 2.48 10.05 1.00 1.59 0.51 10.59 8.35 ∅-BV [mg/L] 4.55 0.05 0.36 0.39 1.84 1.08 1.22 [µg/g] 227.63 1.16 13.50 19.84 69.09 161.72 182.74 109.28 784.95 % of total 29.00 0.15 1.72 2.53 8.80 20.60 23.28 13.92 100.00 Mattenweg A [mg/L] 2.45 0.02 0.52 0.45 2.62 2.25 1.15 48 B [mg/L] 2.47 0.02 0.50 0.47 2.58 2.25 1.26 ∅ [mg/L] 2.46 0.02 0.51 0.46 2.60 2.25 1.20 σ [%] 0.33 0.37 2.07 3.07 1.19 0.21 6.49 ∅-BV [mg/L] 2.46 0.03 0.51 0.44 2.59 2.26 1.19 [µg/g] 122.93 0.72 19.26 22.33 97.04 339.20 179.22 100.30 880.99 % of total 13.95 0.08 2.19 2.53 11.01 38.50 20.34 11.38 100.00 Rafz A [mg/L] 9.89 0.09 1.50 1.24 3.68 1.85 1.34 48 B [mg/L] 9.04 0.08 1.54 1.27 3.60 1.71 1.43 ∅ [mg/L] 9.47 0.08 1.52 1.26 3.64 1.78 1.39 σ [%] 6.34 7.21 1.75 1.81 1.45 5.67 4.90 ∅-BV [mg/L] 9.46 0.09 1.51 1.24 3.63 1.79 1.38 [µg/g] 473.18 2.36 57.17 62.43 136.10 268.92 207.06 128.49 1335.72 % of total 35.43 0.18 4.28 4.67 10.19 20.13 15.50 9.62 100.00

Table A-27: Results of dilution with Cellulose (Kirschgarten soil)

Extraction time (EDDS): 0 24h 48h Weight: Soil Cellulose Sample Soil Cellulose Sample Soil Cellulose Sample A [g] 1.678 1.322 3 1.748 1.252 3 1.72 1.28 3 B [g] 1.775 1.225 3 1.738 1.262 3 1.774 1.226 3 Pb A [µg/g] 1.9 2.4 4.2 5.3 2.9 3.7 B [µg/g] 7.7 11.2 3.9 5.7 3.6 5.2 ∅ [µg/g] 6.8 5.5 4.4 σ [%] 91.2 4.1 24.4 Zn A [µg/g] 59.1 75.0 78.0 99.0 73.1 92.8 B [µg/g] 53.4 77.4 81.4 117.9 86.8 125.8 ∅ [µg/g] 76.2 108.5 109.3 σ [%] 2.2 12.3 21.3 Cu A [µg/g] 14.3 18.2 14.7 18.7 15.7 19.9 B [µg/g] 7.8 11.3 15.9 23.0 16.4 23.8 ∅ [µg/g] 14.7 20.8 21.8 σ [%] 32.9 14.9 12.4 Fe A [µg/g] 6573.0 8343.0 7327.0 9300.1 7069.0 8972.6 B [µg/g] 5403.0 7828.8 7521.0 10897.8 7748.0 11226.7 ∅ [µg/g] 8085.9 10098.9 10099.6 σ [%] 4.5 11.2 15.8 Mn A [µg/g] 57.5 73.0 59.4 75.4 57.0 72.3 B [µg/g] 56.0 81.1 59.5 86.2 62.0 89.8 ∅ [µg/g] 77.1 80.8 81.1 σ [%] 7.5 9.5 15.2

Table A-28: Results of dilution with Cellulose (Mattenweg soil)

Extraction time (EDDS): 0 24h 48h Weight: Soil Cellulose Sample Soil Cellulose Sample Soil Cellulose Sample A [g] 1.478 1.522 3 1.575 1.425 3 1.557 1.443 3 B [g] 1.511 1.489 3 1.585 1.415 3 1.544 1.456 3 Pb A [µg/g] 6.5 6.3 3.5 3.4 4.0 3.9 B [µg/g] 1.6 1.6 1.2 1.2 2.8 2.8 ∅ [µg/g] 4.0 2.3 3.4 σ [%] 83.6 66.8 21.9 Zn A [µg/g] 55.3 53.7 98.3 95.5 109.8 106.6 B [µg/g] 65.8 66.8 100.3 101.8 92.6 94.0 ∅ [µg/g] 60.2 98.6 100.3 σ [%] 15.3 4.5 8.9 Cu A [µg/g] 12.2 11.8 19.0 18.5 25.5 24.8 B [µg/g] 15.6 15.8 23.3 23.6 23.5 23.8 ∅ [µg/g] 13.8 21.0 24.3 σ [%] 20.4 17.4 2.7 Fe A [µg/g] 5845.0 5676.0 9334.0 9064.2 11030.0 10711.1 B [µg/g] 7224.0 7330.7 10040.0 10188.3 9871.0 10016.8 ∅ [µg/g] 6503.4 9626.3 10364.0 σ [%] 18.0 8.3 4.7 Mn A [µg/g] 46.7 45.3 62.5 60.7 69.9 67.9 B [µg/g] 57.0 57.8 64.2 65.1 64.4 65.4 ∅ [µg/g] 51.6 62.9 66.6 σ [%] 17.1 5.0 2.7

Table A-29: Results of dilution with Cellulose (Rafz soil)

Extraction time (EDDS): 0 24h 48h Weight: Soil Cellulose Sample Soil Cellulose Sample Soil Cellulose Sample A [g] 1.725 1.275 3 1.841 1.159 3 1.825 1.175 3 B [g] 1.719 1.281 3 1.835 1.165 3 1.809 1.191 3 Pb A [µg/g] 3.9 5.3 9.5 12.9 10.5 14.2 B [µg/g] 9.6 12.9 8.9 11.9 9.5 12.7 ∅ [µg/g] 9.1 12.4 13.5 σ [%] 59.2 5.2 7.6 Zn A [µg/g] 67.9 91.9 93.6 126.6 97.9 132.5 B [µg/g] 61.1 82.0 95.7 128.4 92.8 124.5 ∅ [µg/g] 86.9 127.5 128.5 σ [%] 8.0 1.0 4.4 Cu A [µg/g] 18.2 24.6 9.6 13.0 11.3 15.3 B [µg/g] 7.4 9.9 9.0 12.1 10.2 13.7 ∅ [µg/g] 17.3 12.5 14.5 σ [%] 60.1 5.1 7.8 Fe A [µg/g] 6812.0 9216.2 6895.0 9328.5 8290.0 11215.9 B [µg/g] 5350.0 7179.3 7365.0 9883.2 7272.0 9758.4 ∅ [µg/g] 8197.8 9605.9 10487.2 σ [%] 17.6 4.1 9.8 Mn A [µg/g] 61.1 82.7 69.4 93.9 87.3 118.1 B [µg/g] 61.0 81.9 74.7 100.2 75.3 101.0 ∅ [µg/g] 82.3 97.1 109.6 σ [%] 0.7 4.6 11.0

Appendix

A44

Table A-30: lg K values for protonation of EDTA,EDDS, NTA (10)

reaction EDTA EDDS NTAlg K1 L+H=LH 2 2.4 0.8lg K2 LH+H=LH2 2.7 3.9 1.8lg K3 LH2+H=LH3 6.2 6.8 2.48lg K4 LH3+H=LH4 10.3 9.8 9.65 Table A-31: lg K values for hydroxylation of selected metals (10)

reaction Cu Fe Mn Pb Zn Ca lg K1 / sI M+OH=MOH 5.97 / 0 11.26 / 1 3.07 / 1 5.97 / 1 4.67 / 1 - / 0 lg K2 / sII MOH+OH=M(OH)2 6.389 / 1 10.19 / 1 2.289 / 1 4.489 / 1 5.989 / 1 - / 0 lg K3 / sIII M(OH)2+OH=M(OH)3 1.811 / 0 7 / 0 1.511 / 0 3.111 / 0 2.611 / 0 - / 0 lg K4 / sIV M(OH)3+OH=M(OH)4 2.23 / 0 5.07 / 0 0.83 / 0 36.14 / 0 1.53 / 0 - / 0 Table A-32: lg KSt for selected species of EDTA, EDDS, NTA at 25°C (* at 20°C) and 0.01M ionic strength (10)

EDTA EDDS NTA Ca 10.61 4.2 6.39Cu 18.70 18.4 12.94Fe(III) 25.10 22 15.9Mg 8.83 5.8 5.5Mn 13.81 8.95* 7.4Pb 17.80 12.7 11.34Zn 16.44 13.5 10.7 Table A-33: Calculated lg αHL for EDTA, EDDS, NTA

pH EDTA EDDS NTA 1 1.72E+01 1.89E+01 1.07E+012 1.32E+01 1.49E+01 6.73E+003 9.20E+00 1.09E+01 2.73E+004 5.20E+00 6.90E+00 2.30E-025 1.23E+00 2.90E+00 2.98E-056 7.31E-04 3.33E-02 2.74E-067 4.41E-06 1.44E-05 2.74E-078 4.34E-07 1.09E-06 2.74E-089 4.34E-08 1.09E-07 2.74E-09

10 4.34E-09 1.09E-08 2.74E-10 Table A-34: Calculated lg αM(OH) for selected metal hydroxides

pOH Cu2++OH- Fe3++OH- Mn2++OH- Pb2++OH- Zn2++OH- Ca2++OH-

4 4.36E+00 1.34E+01 4.91E-02 2.58E+00 2.66E+00 0.00E+005 2.36E+00 1.14E+01 5.08E-03 1.12E+00 7.80E-01 0.00E+006 5.17E-01 9.45E+00 5.10E-04 2.93E-01 3.84E-02 0.00E+007 9.81E-03 7.45E+00 5.10E-05 3.89E-02 2.22E-03 0.00E+008 9.93E-05 5.45E+00 5.10E-06 4.04E-03 2.05E-04 0.00E+009 9.93E-07 3.48E+00 5.10E-07 4.05E-04 2.03E-05 0.00E+00

10 9.93E-09 1.67E+00 5.10E-08 4.05E-05 2.03E-06 0.00E+0011 9.93E-11 4.91E-01 5.10E-09 4.05E-06 2.03E-07 0.00E+0012 9.93E-13 7.35E-02 5.10E-10 4.05E-07 2.03E-08 0.00E+0013 9.93E-15 7.83E-03 5.10E-11 4.05E-08 2.03E-09 0.00E+00

Appendix

A45

Table A-35: Calculated Keff for selected EDTA species

pH CuEDTA FeEDTA MnEDTA PbEDTA ZnEDTA CaEDTA 1 1.50 7.89 -3.39 0.60 -0.76 -6.592 5.50 11.83 0.61 4.60 3.24 -2.593 9.50 15.41 4.61 8.60 7.24 1.414 13.50 18.23 8.61 12.60 11.24 5.415 17.47 20.40 12.58 16.57 15.21 9.386 18.70 19.65 13.81 17.80 16.44 10.617 18.69 17.65 13.81 17.76 16.44 10.618 18.18 15.65 13.81 17.51 16.40 10.619 16.34 13.65 13.80 16.68 15.66 10.61

10 14.34 11.65 13.76 15.22 13.78 10.61

Table A-36: Calculated Keff for selected EDDS species

pH CuEDDS FeEDDS MnEDDS PbEDDS ZnEDDS CaEDDS 1 -0.50 3.09 -9.95 -6.20 -5.40 -14.702 3.50 7.03 -5.95 -2.20 -1.40 -10.703 7.50 10.61 -1.95 1.80 2.60 -6.704 11.50 13.43 2.05 5.80 6.60 -2.705 15.50 15.62 6.05 9.80 10.60 1.306 18.37 16.51 8.92 12.66 13.47 4.177 18.39 14.55 8.95 12.66 13.50 4.208 17.88 12.55 8.95 12.41 13.46 4.209 16.04 10.55 8.94 11.58 12.72 4.20

10 14.04 8.55 8.90 10.12 10.84 4.20

Table A-37: Calculated Keff for selected NTA species

pH CuNTA FeNTA MnNTA PbNTA ZnNTA CaNTA 1 2.21 5.16 -3.33 0.61 -0.03 -4.342 6.21 9.10 0.67 4.61 3.97 -0.343 10.21 12.68 4.67 8.61 7.97 3.664 12.92 14.20 7.38 11.32 10.68 6.375 12.94 12.42 7.40 11.34 10.70 6.396 12.94 10.45 7.40 11.34 10.70 6.397 12.93 8.45 7.40 11.30 10.70 6.398 12.42 6.45 7.40 11.05 10.66 6.399 10.58 4.45 7.39 10.22 9.92 6.39

10 8.58 2.45 7.35 8.76 8.04 6.39