Table 1: Sources of transfer functions, number of citations on 29.07.2021, measured variables, extraction procedure and n° of equation (for correspondence with tables 2 and 3) collected from the selected papers.Cu-ISE = copper ion-selective electrode, DPASV = differential pulse anodic stripping voltammetry
DOI
|
Authors
|
Year of publication
|
Times cited
|
Yearly citation rate
|
"Total" Cu measurement
|
Solution extraction
|
free Cu estimation
|
response variable
|
N° equation in the next tables
|
10.18174/njas.v28i3.17030
|
Lexmond et al.
|
1980
|
114
|
2.8
|
HNO3, HClO4 and H2SO4 in a ratio of 40:4:1
|
0.01M CaCl2
|
resine extraction
|
pCu
|
11
|
10.1111/j.1365-2389.1997.tb00554.x
|
McBride et al.
|
1997
|
882
|
36.8
|
Nitric acid microwave digestion and H2SO4-HNO3 (1:1 by volume), completing digestion with a few drops of HCIO
|
Water extract and 0.01M CaCl2
|
Cu-ISE
|
pCu; Cu solution
|
3a-e
|
10.1023/A:1018312109677
|
Sauvé et al.
|
1997
|
383
|
16
|
HNO3 microwave
|
0.01M CaCl2
|
Cu-ISE
|
pCu
|
5a,5b
|
10.1021/es9907764
|
Sauvé et al.
|
2000
|
1279
|
60.9
|
review of "total"
|
Water displacement, lysimeter, and water or neutral salt extractions
|
|
Cu solution
|
6
|
10.1021/es0000910
|
Vulkan et al.
|
2000
|
180
|
8.6
|
aqua regia
|
soil pore water
|
Cu-ISE
|
pCu
|
13
|
10.1016/S0269-7491(03)00058-7
|
Tipping et al.
|
2003
|
405
|
22.5
|
nitric and perchloric acids, followed by leaching of the residues with 5 mol l1 HCl, and analysis by ICP–AES.
|
2%HNO3
|
WHAM
|
pCu
|
14a-b
|
10.1021/es030155h
|
Lofts et al.
|
2004
|
219
|
12.8
|
EDTA
|
0.02MCaCl2, +data from Tipping 2003 , Sauvé 1997
|
CU-ISE and WHAM
|
pCu
|
15
|
Alterra Report 305, May 2004
http://edepot.wur.nl/16988.
|
Römkens et al.
|
2004
|
66
|
3.8
|
0.43 HNO3
|
0.05 mol.L Ca-EDTA
|
CHARON model
|
Cu solution ; pCu
|
|
10.1016/S1001-0742(06)60016-8
|
Luo et al.
|
2006
|
18
|
1.2
|
HF, HClO4 and HNO3 with a ratio of 3:1:1
|
0.01 Kcl
|
electrode (DPASV)
|
Cu solution; pCu
|
7a-b
|
10.1016/j.jhazmat.2005.09.033
|
Luo et al.
|
2006
|
84
|
5.6
|
HF, HClO4 and HNO3 with a ratio of 3:1:1
|
0.01 Kcl
|
electrode (DPASV)
|
Cu solution; pCu
|
8
|
10.1097/SS.0b013e3181bf2f52
|
Unanumo et al.
|
2009
|
12
|
0.8
|
aqua regia
|
0.01M CaCl2
|
WHAM
|
pCu
|
12
|
10.1111/j.1365-2389.2009.01201.x
|
Groenenberg et al.
|
2010
|
102
|
9.3
|
0.43 HNO3
|
0.01 ou 0.02 CaCl2
|
WHAM-and Cu-ISE for partial data
|
pCu
|
16
|
10.1080/09064710.2013.785586
|
Ivezic et al.
|
2012
|
6
|
0.7
|
1:15 HNO3
|
water 1:10
|
WHAM
|
Cu solution
|
4a
|
10.1002/jpln.201400349
|
Mondaca et al.
|
2015
|
15
|
2.5
|
were digested in boiling nitric acid followed by perchloric acid addition
|
0.1 MKNO3
|
Cu-ISE
|
Cu solution; pCu
|
9a-c
|
10.1080/09542299.2017.1404437
|
Li et al.
|
2017
|
3
|
1
|
aqua regia
|
filtred pore water
|
Cu-ISE
|
Cu solution; pCu
|
10a-c
|
Table 2: Transfer functions for Cu available reviewed from literature under the form log10Cu solution = a log10Cutot + b log10OM + c log10clay + d log10pH +e..Cu is expressed in mg.kg soil-1, OM is expressed in g.kg soil-1 or in % of OM ( specified in the row), DOC is expressed in mgC.L-1 and clay in %. hen parameters incertitude’s were provided, they have been reported in the table.
a.
Source
|
N°
|
R.V
|
e
|
Log (Cu tot)
|
pH
|
Log (OM)
|
Log (DOC)
|
Log (clay)
|
R2
|
number of data
|
Range Cu tot (mg.kg-1)
|
Range OM (g.kg-1)
|
Range pH
|
(McBride et al., 1997)
|
3a
|
Log (Cusolution ) (µg.L-1)
|
0.699
|
0.86
|
-0.11
|
|
|
|
0.87
|
67
|
14-2600
|
|
3.3-6.6
|
3b
|
Log (Cusolution) (µg.L-1
|
1.42
|
0.94
|
-0.1
|
-0.68 (g.kg-1)
|
|
|
0.85
|
70
|
14-2600
|
|
3.3-6.6
|
3c
|
Log (Cusolution) (µg.L-1)
|
0.05
|
0.76
|
|
|
|
|
0.86
|
31
|
7-1010
|
2.4-27.4
|
4.2-7.8
|
(Ivezić et al., 2012)
|
4a
|
Log (Cusolution)
|
-0.24
|
0.80
|
-0.02
|
-0.53 (%)
|
0.54
|
|
0.42
|
74
|
5.7-141
|
1.8-20.4
|
4.3-8.1
|
4b
|
Log (Cusolution) (µg.L-1)
|
-0.45
|
0.77
|
|
-0.62 (%)
|
0.65
|
|
0.42
|
74
|
5.7-141
|
1.8-20.4
|
4.3-8.1
|
(Sauvé et al., 1997)
|
5a
|
Log (Cu solution) (µg.L-1)
|
13.2 (±7.9)
|
0.32 (±0.01)
|
|
|
|
|
0.89
|
66
|
14-3083
|
4.1-554.6
|
3.3-7.6
|
|
(Sauvé et al., 2000)
|
6a
|
Log (Cu solution)
|
1.37 (±0.14)
|
0.931 (±0.05)
|
-0.21 (±0.02)
|
-0.211 (±0.02)
|
|
|
0.611
|
353
|
|
|
2-9
|
|
(Luo et al., 2006b)
|
7a
|
Log (Cu solution) (µg.L-1)
|
1.21 (±0.45)
|
0.32 (±0.16)
|
|
1.08 (±0.33) (%)
|
|
|
0.32
|
39
|
280-1752
|
|
5.3-7.61
|
|
|
7b
|
Log (Cu solution) (µg.L-1)
|
2.08 (±0.11)
|
|
|
1.33 (±0.32) (%)
|
|
|
0.38
|
39
|
280-1752
|
|
5.3-7.61
|
|
(Luo et al., 2006a)
|
8a
|
Log (Cu solution) (µg.L-1)
|
2.20 (±0.11)
|
|
|
0.88 (±0.28) (%)
|
|
|
0.205
|
40
|
280-1930
|
26-62
|
5.5-7.8
|
|
(Mondaca et al., 2015)
|
9a
|
Log (Cu solution) (µg.L-1)
|
0.69
|
0.5
|
|
0.73
|
|
|
0.36
|
86
|
56-4441
|
12.0-62
|
6.2-7.8
|
|
9b
|
Log (Cu solution) (µg.L-1)
|
-1.01
|
0.75
|
|
0.95
|
|
1.23
|
0.70
|
86
|
56-4441
|
12.0-62
|
6.2-7.8
|
|
(Li et al., 2017)
|
10a
|
Log (Cu solution) (µmol.L-1)
|
-2.976
|
0.515
|
|
|
|
1.23
|
0.63
|
34
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
1.Data expressed in percentage of C 2 Data expressed in mg Cu .kg soil
Table 3. Transfer functions for (bio-)available Cu reviewed from literature for estimation of pCu (units in brackets). pCu = a log10Cutot + b log10OM + c log10clay + d log10pH +e. R.V is for response variable and e. for intercept. Total Cu is expressed in mg.kg-1, OM in g.kg-1 or percentage (precision in the row), clay in percentage.
Source
|
Eq .
|
R.V
|
e
|
Log (Cu tot)
|
pH
|
Log (OM)
|
Log (CEC)
|
other
|
Log (clay)
|
R2
|
number of data
|
Range CuTot
|
Range OM g.kg
|
Range pH
|
(Lexmond, 1980)
|
11
|
pCu (mol L-1)
|
5.08
|
-2.38
|
1.07
|
|
|
|
|
0.989
|
16
|
10-400
|
16.8
|
3.9-6.2b
|
(McBride et al., 1997)
|
3d
|
pCu (µg L-1)
|
1.28
|
-1.95
|
1.37
|
1.95(g.kg-1)
|
|
|
|
0.897
|
70
|
17-2600
|
|
3.3-6.6
|
(McBride et al., 1997)
|
3e
|
pCu (µg L-1)
|
1.8
|
-1.1
|
1.6
|
1.8 (g kg-1)
|
|
|
|
0.91
|
10
|
6-1440
|
15-395
|
4.5-7.2
|
(Sauvé et al., 1997)
|
5b
|
pCu (µg L-1)
|
3.42 (±0.5)
|
-1.7 (±0.12)
|
1.4 (±0.08)
|
|
|
|
|
0.848
|
66
|
14-3083
|
4.1-554.6
|
3.3-7.6
|
(Unamuno et al., 2009)
|
12a
|
Log (Cu2+) (mg.kg-1)
|
-2.1
|
|
0.085
|
|
|
|
0.005
|
29
|
18-10389
|
|
|
|
(Unamuno et al., 2009)
|
12b
|
Log (Cu2+) (mg.kg-1)
|
-2.079
|
0.593
|
-0.053
|
|
|
|
0.73
|
|
|
|
|
|
(Unamuno et al., 2009)
|
12c
|
Log (Cu 2+) (mg.kg-1)
|
-2.259
|
0.594
|
-0.058
|
0.09 (g.kg-1)
|
|
|
0.732
|
29
|
18-10389
|
|
|
|
(Vulkan et al., 2000)
|
13a
|
pCu (µg.L-1)
|
-0.53
|
-1.47
|
1.79
|
|
|
|
|
0.89
|
22
|
19.4-8645
|
98-698
|
5.5-8
|
(Tipping et al., 2003)
|
14a
|
pCu (µg.kg-1)
|
-1.34
|
-0.54 (µmol.g-1)
|
1.15
|
0.40 (%)
|
|
|
|
0.94
|
98
|
|
100-1000
|
|
(Tipping et al., 2003)
|
14b
|
pCu (µg.kg-1)
|
-5.35
|
-1.09 (µmol.g-1)
|
1.17
|
0.52 (%)
|
|
|
|
0.87
|
165
|
|
|
|
(Lofts et al., 2004)
|
15
|
pCu(nM)
|
-4.99
|
-0.93
|
1.26
|
0.63(%)
|
|
|
|
0.9
|
151
|
0.96-637
|
0.41-97.8
|
3.35-8.27
|
(Luo et al., 2006b)
|
7b
|
pCu (µg.L-1)
|
-2.24 (±0.96)
|
|
1.47 (±0.14)
|
|
|
|
|
0.76
|
39
|
280-1752
|
|
5.3-7.61
|
(Groenenberg et al., 2010)
|
16
|
pCu (mol.L-1)
|
0.48
|
0.81
|
-1
|
-0.89 (%)
|
|
|
0.83
|
216
|
0.6-326
|
2-97.8
|
|
3.3-8.3
|
(Mondaca et al., 2015)
|
9c
|
pCu (µg L-1)
|
5.54
|
-0.74
|
0.67
|
0.75(%)
|
|
|
|
0.58
|
86
|
56-4441
|
12.0-62
|
|
(Li et al., 2017)
|
10b
|
pCu (mol.L-1)
|
-4.303
|
-1.639
|
1.171
|
|
|
|
|
0.65
|
34
|
|
|
|
(Li et al., 2017)
|
10c
|
pCu (mol.L-1)
|
-0.783
|
-1.6 (Cu solution, µg L-1)
|
1.3 log
|
|
|
|
|
0.65
|
34
|
|
|
|
- pH in the resin extraction ; b. pH in soil solution determined by CaCl2 ; c. Alox and Feox are respectively aluminum and iron oxydes
0.85 with [Cu] in mol respectively per kg en per liters.
Table 4: Deciles of concentration for total soil Cu contents (mg.kg-1), Cu in solution (µg L-1) and free Cu (mg kg-1), also expressed as pCu (-log(freeCu))
decile
|
0.00
|
0.01
|
0.05
|
0.10
|
0.15
|
0.20
|
0.25
|
0.40
|
0.50
|
total Cu
|
0.81
|
3.44
|
5.03
|
6.25
|
7.23
|
8.08
|
8.89
|
11.36
|
13.21
|
Cu solution
|
0.20
|
0.68
|
1.01
|
1.26
|
1.45
|
1.63
|
1.83
|
2.63
|
3.36
|
pCu
|
-2.01
|
-0.78
|
-0.45
|
-0.28
|
-0.15
|
-0.04
|
0.07
|
0.49
|
0.78
|
free Cu
|
9.48 E-05
|
0.001
|
0.003
|
0.006
|
0.010
|
0.017
|
0.028
|
0.085
|
0.165
|
decile
|
0.60
|
0.70
|
0.75
|
0.8
|
0.90
|
0.95
|
0.99
|
1.00
|
total Cu
|
15.35
|
17.94
|
19.56
|
21.65
|
28.38
|
36.8
|
28.38
|
129.95
|
Cu solution
|
4.17
|
5.08
|
5.64
|
6.33
|
8.49
|
10.71
|
15.60
|
45.05
|
pCu
|
1.07
|
1.38
|
1.56
|
1.77
|
2.25
|
2.58
|
3.14
|
4.02
|
free Cu
|
0.324
|
0.636
|
0.845
|
1.095
|
1.892
|
2.823
|
5.965
|
101.771
|
References for the table 1 to 3 of empirical equations from the literature
Groenenberg, J. E., Römkens, P. F. A. M., Comans, R. N. J., Luster, J., Pampura, T., Shotbolt, L., et al. (2010). Transfer functions for solid-solution partitioning of cadmium, copper, nickel, lead and zinc in soils: Derivation of relationships for free metal ion activities and validation with independent data. Eur. J. Soil Sci. 61, 58–73. doi:10.1111/j.1365-2389.2009.01201.x.
Ivezić, V., Almås, Å. R., and Singh, B. R. (2012). Predicting the solubility of Cd, Cu, Pb and Zn in uncontaminated Croatian soils under different land uses by applying established regression models. Geoderma 170, 89–95. doi:10.1016/j.geoderma.2011.11.024.
Lexmond, T. M. (1980). The effect of soil pH on copper toxicity to forage maize grown under field conditions. Netherlands J. Agric. Sci. 28, 164–184. doi:10.18174/njas.v28i3.17030.
Li, B., Ma, Y., and Yang, J. (2017). Is the computed speciation of copper in a wide range of Chinese soils reliable? Chem. Speciat. Bioavailab. 29, 205–215. doi:10.1080/09542299.2017.1404437.
Lofts, S., Spurgeon, D. J., Svendsen, C., and Tipping, E. (2004). Deriving soil critical limits for Cu, Zn, Cd, and Ph: A method based on free ion concentrations. Environ. Sci. Technol. 38, 3623–3631. doi:10.1021/es030155h.
Luo, X. S., Zhou, D. M., Liu, X. H., and Wang, Y. J. (2006a). Solid/solution partitioning and speciation of heavy metals in the contaminated agricultural soils around a copper mine in eastern Nanjing city, China. J. Hazard. Mater. 131, 19–27. doi:10.1016/j.jhazmat.2005.09.033.
Luo, X. S., Zhou, D. M., and Wang, Y. J. (2006b). Free cupric ions in contaminated agricultural soils around a copper mine in eastern Nanjing City, China. J. Environ. Sci. (China) 18, 927–931. doi:10.1016/S1001-0742(06)60016-8.
McBride, M., Sauvé, S., and Hendershot, W. (1997). Solubility control of Cu, Zn, Cd and Pb in contaminated soils. Eur. J. Soil Sci. 48, 337–346. doi:10.1111/j.1365-2389.1997.tb00554.x.
Mondaca, P., Neaman, A., Sauvé, S., Salgado, E., and Bravo, M. (2015). Solubility, partitioning, and activity of copper-contaminated soils in a semiarid region. J. Plant Nutr. Soil Sci. 178, 452–459. doi:10.1002/jpln.201400349.
Römkens, P. F. A. M., Groenenberg, J. E., Bonten, L. T. C., de Vries, W., and Bril, J. (2004). Derivation of partition relationships to calculate Cd, Cu, Ni, Pb, Zn solubility and activity in soil solutions. Alterra 305, 75. Available at: http://edepot.wur.nl/16988.
Sauvé, S., Hendershot, W., and Allen, H. E. (2000). Solid-solution partitioning of metals in contaminated soils: Dependence on pH, total metal burden, and organic matter. Environ. Sci. Technol. 34, 1125–1131. doi:10.1021/es9907764.
Sébastien Sauvé, Murray B., M., Wendell A., N., and William H., H. (1997). Copper Solubility and Speciation of In Situ Contaminated Soils: Effects of Copper Level, pH and Organic Matter. Water. Air. Soil Pollut. 100, 133–149.
Tipping, E., Rieuwerts, J., Pan, G., Ashmore, M. R., Lofts, S., Hill, M. T. R., et al. (2003). The solid-solution partitioning of heavy metals (Cu, Zn, Cd, Pb) in upland soils of England and Wales. Environ. Pollut. 125, 213–225. doi:10.1016/S0269-7491(03)00058-7.
Unamuno, V. I. R., Meers, E., Du Laing, G., and Tack, F. M. G. (2009). Effect of physicochemical soil characteristics on copper and lead solubility in polluted and unpolluted soils. Soil Sci. 174, 601–610. doi:10.1097/SS.0b013e3181bf2f52.
Vulkan, R., Zhao, F. J., Barbosa-Jefferson, V., Preston, S., Paton, G. I., Tipping, E., et al. (2000). Copper speciation and impacts on bacterial biosensors in the pore water of copper-contaminated soils. Environ. Sci. Technol. 34, 5115–5121. doi:10.1021/es0000910.