Prediction of metal and metalloid partitioning

coefficients (Kd) in soil using mid-infrared diffuse

reflectance spectroscopy

Les J. Janik, Sean Forrester, Jason K. Kirby, Michael J. McLaughlin, Jos M.

Soriano-Disla,
Clemens Reimann
Sustainable Agriculture Flagship

05 December 2013

EGS Geochemistry Expert Group, FAO

Background
Solid-solution partitioning coefficients (Kd values)

Msolid phase
Kd
Msolution phase
Assessment of potential risks posed by metals (mobile and
bioavalable fraction)
Mobile fraction might affect organisms, biological processes
and be leached
Laborious determination. A reliable, cheap and quick method
is needed

2 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Background
MIR-PLSR as an alternative for Kd assessment

Mid-infrared light absorbed by molecules in soil containing

C-H, N-H, O-H, C-O, C-N, C-C, N-O, Al-O, Fe-O and Si-O
bonds
Spectrum determined by the chemical nature of the soil:
absorbance peaks at specific wave numbers related to soil
compounds

MIR-active compounds influence Kd

3 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Objectives
MIR diffuse reflectance infrared Fourier transform
(DRIFT)-PLSR method to develop predictive models
for Kd values using 500 GEMAS soil samples for:
Metallic cations Ag+, Co2+, Cu2+, Mn2+, Ni2+, Pb2+,
Sn4+, and Zn2+
Metal and metalloid oxoanions MoO42-, Sb(OH)6-,
SeO42-, TeO42-, VO3-, and uncharged boron H3BO30
Use these models to predict Kd values for the
complete GEMAS data set of 4313 soil samples
4 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Material and methods

Soil samples and MIR scanning

GEMAS agricultural and grazing land soil samples (n

= 4813)
Soil sieved at <2 mm and oven dried at 40C
Perkin-Elmer Spectrum
One
Fourier Transform infrared
spectrometer
Diffuse reflectance spectra
Range: 4000-500/cm
Resolution 8 /cm

5 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Material and methods

Selection of samples and determination K d experimental values

N = 500 by APSpectroscopy
StdSelect application
Single
point soluble
(Unscrambler
9.8) metal or
radioactive isotope spike. Rates
chosen to be in linear region of
sorption curve and closer to
ecotoxicity thresholds (PNECs)
and predicted exposure
concentrations (PECs)
(OECD, 2000)

6 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Material and methods

Infrared models

Model development: Partial Least Squares

(Unscrambler V 9.8)
Calibration models trained by leave-one-out crossvalidation
Models used to predict samples in the 4313 unknown
samples

7 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Material and methods

Statistical assessment of model and predictions

PLSR models reported in terms of:

Coefficient of determination: R2
Root mean square error of the CV (RMSECV).
Residual predictive deviation (RPD)=standard
deviation/RMSECV
<1.5: poor; 1.5-2.0: indicator quality; 2.0-3.0: good quality;
>3.0 analytical quality (Chang et al., 2001; Janik et al.,
The
uncertainty of Kd value prediction of unknown
2009)

soil samples expressed as empirical deviation

values (Unscrambler)

<0.2 Excellent spectral fit of the unknowns with the model

0.2-0.4 Good spectral fit of the unknowns with the model
0.4-0.6 Marginal spectral fit of the unknowns with the model
>0.6 Poor spectral fit of the unknowns with the model
8 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Results and discussion:

Metal

Zn
Mn
Co
Ni
Pb
Cu
Sn
Ag

Range
Median
(L/kg)
2-20,276
1737
1-14,288
1195
3-15,739
2285
4-3925
549
10-339,624
10,939
23-8589
1643
60-22,079
2500
159-4655
2623

Cations

log-Kd (DRIFT)

log-Kd (DRIFT+pH)

Class

pH
R2

R2

RMSE

RPD

R2

RMSE

RPD

0.84

0.78

0.47

2.1

0.93

0.27

3.7

0.84

0.70

0.79

1.8

0.88

0.50

2.9

0.71

0.71

0.62

1.9

0.83

0.48

2.4

0.59

0.72

0.35

1.9

0.87

0.24

2.8

0.57

0.70

0.48

1.9

0.84

0.35

2.6

0.26

0.40

0.30

1.3

0.46

0.28

1.4

0.15

0.32

0.47

1.2

0.32

0.47

1.2

0.05

0.33

0.24

1.2

0.35

0.23

1.2

9 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Results and discussion

Prediction maps cations: example of Ni

Grassland

Arable

(From Janik et al.,2014, Fig. 11.1, p.186)

(From Janik et al., 2014, Fig. 11.1, p.186)

Lower strength in northern Europe, rest more variable with

highest in southern and eastern Europe. Patterns
associated to pH induced by climate (mainly rainfall) and
parent material.
10 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Results and discussion:

Cations

Figure. Histograms of the

distribution of log-transformed
Kd (L/kg) deviation values for
the Class 1 metals for
calibration (dark) and
predicted Unknown (light)
using PLSR (DRIFT+pH).
Janik et al., 2014 (submitted)

Few unknowns with deviation values >0.6:

unknowns predicted with similar accuracy to
calibration samples
11 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Results and discussion

Anions

Element

Te
Mo
Sb
V
B
Se

Range
Median
(L/kg)
0.32-2443
193
0.70-7078
41.7
0.51-5494
67.9
0.35-11507
596
0.38-51.88
2.15
0.58-6339
2.20

log-Kd (DRIFT)

log-Kd (DRIFT+pH)

Class

pH
R2

R2

RMSE

RPD

R2

RMSE

RPD

0.62

0.72

0.52

1.9

0.79

0.45

2.2

0.43

0.63

0.48

1.7

0.75

0.38

2.1

0.26

0.64

0.31

1.7

0.74

0.27

2.0

0.09

0.61

0.39

1.6

0.62

0.39

1.6

0.13

0.66

0.19

1.7

0.68

0.18

1.8

0.30

0.43

0.56

1.3

0.43

0.56

1.3

12 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Results and discussion

Prediction maps oxoanions: example of Mo

Arable

(From Janik et al.,2014, Fig. 11.2, p.187)

Grassland

(From Janik et al., 2014, Fig. 11.2, p.187)

Opposite patterns to Ni, negatively related to pH

More variability, especially southern and eastern Europe
Lowest for eastern Spain. Highest in western Iberian
peninsula, Dinarides
13 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Results and discussion

Figure: Histograms
of the distribution of
log-transformed Kd
(L/kg) deviation
values for the anionic
metals for calibration
(dark) and predicted
Unknown (light)
using PLSR
(DRIFT+pH).
Janik et al., 2014
(submitted)

Few unknowns with deviation values >0.6:

unknowns predicted with similar accuracy to
calibration samples
14 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Conclusions
The MIR-PLSR (plus pH) technique is suitable for K d prediction
with models dependent on the metal under study:
Good for cationic metals (Co2+, Mn2+, Ni2+ , Pb2+ and Zn2+) and oxoanions
(MoO42-, Sb(OH)6-, TeO42-):

RPD > 2.0 and R2 > 0.74

Indicator quality for H3BO30 and VO3-:

RPD > 1.5 and R2 > 0.62

Unsuccessful for Ag+, Cu2+, Sn4+ and SeO42-:

RPD < 1.5 and R2 < 0.46

Capability further expanded by the possibility of predicting K d

values in the field using DRIFT hand-held spectrometers.

15 | Prediction of metal and metalloid partitioning coefficients (Kd) in soil using mid-infrared diffuse reflectance
spectroscopy| Janik et al.

Acknowledgements
Cathy Fiebiger (CSIRO L&W)
Government of Valencia (Conselleria de Educacin)
for a Post-Doctoral Fellowship

16 | Prediction of PBI by mid-infrared reflectance spectroscopy | Soriano-Disla et al.

GEMAS The Project Team

Thank you
CSIRO Land and Water
Jose Martin Soriano Disla (PhD)
Tel.: +61883038425
E-mail:

jose.sorianodisla@csiro.au

Website: www.clw.csiro.au
Sustainable Agriculture Flagship

Referen
ces

References
SLIDE 8:
Chang, C.W., Laird, D.A., Mausbach, M.J. and Hurburgh C.R., J., 2001. Near-infrared reflectance spectroscopy - Principal
components regression analyses of soil properties. Soil Sci. Soc. Am. J., 65:480-490.
Janik, L.J., Forrester, S.T. & Rawson, A., 2009. The prediction of soil chemical and physical properties from mid-infrared
spectroscopy and combined partial least-squares regression and neural networks (PLS-NN) analysis. Chemometrics and
Intelligent Laboratory Systems, 97, 179-188.
SLIDES 10, 13:
Janik, L.J., Forrester, S., Kirby, J.K., McLaughlin, M.J., Soriano-Disla, J.M. & Reimann, C., 2014. Prediction of metal and
metalloid partioning coefficients (Kd) in soil using Mid-Infrared diffuse reflectance spectroscopy. Chapter 11 In: C. Reimann, M.
Birke, A. Demetriades, P. Filzmoser & P. OConnor (Editors), Chemistry of Europe's agricultural soils Part B: General
background information and further analysis of the GEMAS data set. Geologisches Jahrbuch (Reihe B 103), Schweizerbarth,
183-188.
SLIDES 6:
OECD, 2000. OECD guideline for the testing of chemicals. Section 1. Physical-chemical properties. Test No. 106.
Adsorption-desorption using a batch equilibrium method. Organisation for Economic Cooperation and Development Publishing,
44 pp.
SLIDES 11, 14:
Janik, L., Forrester, S., Kirby, J.K., McLaughlin, M.J., Soriano-Disla, J.M., Reimann, C. & The GEMAS Project Team, 2014a.
GEMAS: Prediction of solid-solution partitioning coefficients (K d) for cationic metals in soils using mid-infrared diffuse
reflectance spectroscopy. Science of the Total Environment (submitted).
Janik, L., Forrester, S., Soriano-Disla, J.M., Kirby, J.K., McLaughlin, M.J., Reimann, C. & The GEMAS Project Team, 2014b.
GEMAS: Prediction of solid-solution phase partitioning coefficients (K d) for boric acid and oxyanions in soils using mid-infrared
diffuse reflectance spectroscopy. Science of the Total Environment (submitted).

19 | Prediction of PBI by mid-infrared reflectance spectroscopy | Soriano-Disla et al.