Published online May 16, 2007

A Mechanism Study of Reflectance Spectroscopy

for Investigating Heavy Metals in Soils
SOIL CHEMISTRY

Conventional methods for investigating heavy metal contamination in soil are time consuming
Yunzhao Wu* and expensive. In this study, we (i) explored reflectance spectroscopy as an alternative method for
State Key Lab. of Remote Sensing Science assessing heavy metals, and (ii) further explored the physicochemical mechanism that allows estima-
jointly sponsored by the Inst. of Remote tion of heavy metals with the reflectance spectroscopy method. We first investigated the spectral
Sensing Applications of Chinese Academy of
response of changing concentrations of heavy metals in soils. The results indicated that only at very
Sciences and Beijing Normal Univ.
high concentration can transition elements exhibit their inherent absorption features. In spite of this
State Key Lab. of Mineral Deposit Research observation, we successfully predicted low levels of heavy metals in agricultural soils. The best predic-
Inst. of Surficial Geochemistry tion accuracies were obtained for the siderophile elements Ni, Cr, and Co. The poorest prediction
Dep. of Earth Sciences was for Cd. The order of prediction accuracy for metals was approximately the same as the order of
Nanjing Univ. their correlation coefficients with Fe. Complementary to some previous studies that found that the
Nanjing 210093 intercorrelation between heavy metals and active soil components (such as Fe oxides, organic matter,
China and clay) is the major predictive mechanism, in the present study we concluded that the correlation
with total Fe (including active and residual Fe) is the major mechanism. This conclusion was fur-
Jun Chen ther supported by both correlation analysis and chemical sequential extraction. Correlation analysis
Junfeng Ji showed that all metals are negatively correlated with reflectance while positively correlated with the
State Key Lab. of Mineral Deposit Research absorption depth at about 500 nm, a feature resulting from goethite. The chemical forms of heavy
Inst. of Surficial Geochemistry metals, which showed that besides the crystalline Fe oxide and organic matter fractions, heavy metals
Dep. of Earth Sciences have significant amounts in the residual fraction, also strengthened the conclusion.
Nanjing Univ.
Nanjing 210093 Abbreviations: CSE, chemical sequential extraction; ICP–AES, inductively coupled plasma–atomic
China emission spectroscopy; ICP–MS, inductively coupled plasma–mass spectroscopy; PI, pollution index;
PLSR, partial least-squares regression; RMSEP, root-mean-square error of prediction; RPD, ratio of the
Peng Gong standard deviation of the population to the root-mean-square error of prediction; VNIRS, visible and
State Key Lab. of Remote Sensing Science near-infrared reflectance spectroscopy.
jointly sponsored by the Inst. of Remote
Sensing Applications of Chinese Academy of
Sciences and Beijing Normal Univ.

Qilin Liao
H eavy metals, trace elements in natural media at concen-
trations of <0.1%, are prevalent in soils. It is well known
that excessive levels of heavy metals can be detrimental to organ-
Geological Survey of Jiangsu Province isms and human health. Conventional methods for investigating
Nanjing 210093
soil heavy metal contamination are based mostly on field sam-
China
pling and wet digestion in concentrated acids and either atomic
Qingjiu Tian absorption spectrometry or inductively coupled plasma spectros-
International Inst. for Earth System Science copy measurements, which are time consuming and relatively
Nanjing Univ. expensive. The expense is a serious problem because heavy metal
Nanjing 210093 contamination in soils is particularly prevalent in developing
China
countries, where money is invested in economic development
Hongrui Ma while environmental protection is relatively ignored. Therefore,
State Key Lab. of Mineral Deposit Research the development of rapid and inexpensive techniques for investi-
Inst. of Surficial Geochemistry gating heavy metal soil contamination could be of great value.
Dep. of Earth Sciences Reflectance spectroscopy within the visible and near-infrared
Nanjing Univ.
reflectance spectroscopy (VNIRS) region (380–2500 nm) has been
Nanjing 210093
China widely used as an inexpensive tool for rapid analysis of a wide range
of soil properties (Deaton and Balsam, 1991; Ben-Dor and Banin,
1995; Malley and Williams, 1997; Chang et al., 2001). In addi-
Soil Sci. Soc. Am. J. 71:918–926
tion to rapidity and relatively low cost, it has another advantage in
doi:10.2136/sssaj2006.0285
Received 17 Aug. 2006. that reflectance spectra can be measured in the field using portable
*Corresponding author (njuessi@yahoo.com.cn). spectroradiometers. A successful prediction of various soil charac-
© Soil Science Society of America teristics based on reflectance spectra can open the possibilities for
677 S. Segoe Rd. Madison WI 53711 USA a rapid and dynamic mapping using remote sensing technology.
All rights reserved. No part of this periodical may be reproduced or
Recently there has been growing interest in the use of reflectance
transmitted in any form or by any means, electronic or mechanical,
including photocopying, recording, or any information storage and spectroscopy for soil characterization (Ji et al., 2002; Siebielec et
retrieval system, without permission in writing from the publisher. al., 2004; Wu et al., 2005a, 2005b; Brown et al., 2006).
Permission for printing and for reprinting the material contained Early work on the spectral reflectance signatures of soil con-
herein has been obtained by the publisher. centrated on qualitative identification of soil components (Condit,

918 SSSAJ: Volume 71: Number 3 • May–June 2007

1970; Stoner and Baumgardner, 1981). Since about the 1990s, prediction mechanism by combining statistical methods and chemi-
with the advent of various mathematic methods such as partial cal sequential extraction procedures.
least-squares regression, artificial neural networks, and multivariate
adaptive regression splines, research has concentrated more on the MATERIALS AND METHODS
quantitative prediction with reflectance spectroscopy of various soil This study was performed in two phases. First, we investigated
constituents, most of which have absorptions within the VNIRS the spectral response of heavy metals at various concentrations by
region, such as water (Liu et al., 2002; Whiting et al., 2004), Fe artificially modeling contamination in the laboratory. Second, heavy
oxides (Scheinost et al., 1998; Ji et al., 2002; Grygar et al., 2003), car- metal concentrations in natural soil samples were predicted.
bonates (Ben-Dor and Banin, 1990), and organic matter (Dalal and
Henry, 1986; Fidencio et al., 2002; Reeves et al., 2002). In addition, Study Area and Soil Samples
because of the intercorrelations to these spectral constituents, even The study area, Baguazhou Island, is located at the northeast outskirts
spectrally featureless soil properties such as cation exchange capacity, of Nanjing City, the capital of Jiangsu Province (Fig. 1). The climate of the
base saturation, pH, exchangeable bases, and extractable P can been Nanjing area is northern subtropical, with an average annual temperature
estimated, but only indirectly (Ben-Dor and Banin, 1995; Dunn et of 16.7°C and mean annual precipitation 1239 mm. The topography of
al., 2002; Shepherd and Walsh, 2002; Brown et al., 2006). Baguazhou Island is flat with a maximum elevation of 5 m, which is below
Some heavy metals, such as Ni, Cr, and Co, are transition ele- the water level of the Changjiang (Yangtze) River during the flood season.
ments. These elements have an unfilled d shell. The energy levels of As a result, a dike was built around the entire island to prevent flooding.
d orbits will split when the atom of a transition element is located Baguazhou Island is the third largest island in the Changjiang River. It has
in a crystal field. Electromagnetic energy is absorbed when an elec- a long history of cultivation. This alluvial island is dominated by paddy
tron moves from a lower level into a higher one (Burns, 1993; soil (USDA taxonomic classification of Agrudalf), with a small quantity of
Clark, 1999). Malley and Williams (1997) first predicted heavy fluvo-aquic soil in the northwest. The industrial area of Nanjing is located
metals in sediments using reflectance spectroscopy. After several off the north bank of Baguazhou Island and contains large industrial plants,
years, the quantitative prediction of heavy metals was made again such as iron and steel, chemical, and petrochemical works.
for sediments (Kooistra et al., 2001), soils polluted by a mining A total of 61 topsoil samples (0–20 cm) were collected across
accident (Kemper and Sommer, 2002), soils from a metal mining the entire island, with a sampling density of one sample/km2. At each
region (Siebielec et al., 2004), and agricultural soils (Malley et al., sampling point, three subsamples were taken and mixed to obtain a
2000; Wu et al., 2005a, 2005b). representative bulk sample that was used to estimate the heavy metal
These studies made significant improvements in the applica- concentration at that sample locality. The soil samples were air dried
tion of reflectance spectroscopy from soil composition to the soil at 20°C for 4 d and sieved through a 2-mm polyethylene sieve to
microelements. There are some deficiencies, however. First, to our remove large debris, stones, and pebbles. The samples were then
knowledge, there are no publications that report how great a con- ground and passed through a standard 0.15-mm (100-mesh) poly-
centration of a heavy metal is needed for it to directly express its ethylene screen. Each sample was divided into two subsamples. One
intrinsic absorption features on the soil spectral curves. Second, was used for spectral measurements and the other analyzed for heavy
most of the predictions have been based largely on mathematical metal concentrations.
relationships between spectra and chemical data, but did not show
the physical relationship between them; i.e., the prediction mecha- Reflectance Measurements and
nism by which trace metals, whose spectra are featureless, can be pre- Spectral Pretreatments
dicted, was seldom investigated. Even though, in some studies, the Reflectance spectra of the soil samples were recorded with a
prediction mechanism was investigated, it was concluded indirectly PerkinElmer Lambda 900 spectrophotometer (PerkinElmer, Waltham,
using statistical methods such as regression coef-
ficients or correlation analysis, and the conclusion
was that heavy metal bonded to active soil compo-
nents such as organic matter, Fe oxides, or clay is
the predictive mechanism (Malley and Williams,
1997; Kooistra et al., 2001; Kemper and Sommer,
2002). Besides these fractions, heavy metals in soils
can also exist in other chemical fractions, such as in
the residue. In this study we used chemical sequen-
tial extraction (CSE) procedures to investigate the
chemical forms of heavy metals (Shuman, 1985;
Hall et al., 1996; Sahuquillo et al., 1999), and
thereby hope to contribute to the revelation of the
predictive mechanism.
Based on previous research, the objectives of
this study were (i) to investigate the concentration
at which heavy metals can exhibit their intrinsic
absorption features, (ii) to assess the predictability
of heavy metals in agricultural soils using reflec-
tance spectroscopy, and (iii) to further explore the Fig. 1. The map of Baguazhou Island with sample locations.

SSSAJ: Volume 71: Number 3 • May–June 2007 919

 MA). For the current measurements, we used a slit width of 2 nm in
the 380- to 860-nm region and 20 nm in the 862- to 2500-nm region,
at 2-nm increments, which produced 1061 spectral points between
380 and 2500 nm. Ground samples were made into a slurry on a glass
microslide with distilled water, smoothed, and dried slowly at low tem-
perature (<40°C). Data, reflectance intensity relative to a white spectralon
standard, were written directly to a computer disk. Artifacts at detector
changes, due to insensitivity at the limits of the detectors, were eliminated
in the range of 842 to 898 nm. Because of low signal-to-noise levels near
2500 nm, only the 380- to 2300-nm wavelength range was used.
To diminish noise, the spectra were smoothed using a Savitzky–
Golay smoothing algorithm. Because the finely ground soil sample was
used for the spectral measurements, multiplicative spectral effects are
very low. Therefore, in this study, multiplicative scatter correction was
not used. To establish a robust prediction model, the first and second
derivative spectra were calculated using Savitzky–Golay smoothing with
a second-order polynomial fit on the smoothed reflectance data. The
absorption features of metals are shallow and hence difficult to describe.
One more transformation method—continuum removal—was used to
enhance the weak absorption features. Continuum removal was accom-
plished using a program that ratios the spectrum with the lowest convex
curve lying above the spectrum (Clark and Roush, 1984). In that case,
the absorption band depth, D, was defined as follows:
D = 1 - R b/R c [1]
where Rb is the reflectance at the band center and Rc is the reflectance
of the continuum at the same wavelength as Rb.
Modeling Contamination Experiments
One sample selected from the 61 soil samples was used for the mod-
eling contamination experiments. In accordance with crystal field theory,
three spectrally active heavy metals, Ni, Cr, and Cu were chosen to investi-
gate the level at which they can exhibit their inherent absorption features.
To provide a comparison, Hg was also modeled, although its spectra are
featureless. Table 1 shows the sequential concentrations of heavy metals
added artificially and the chemical reagents used in the modeling process.
The electron configuration and the crustal abundance of the metal cation
are also shown in Table 1. All the solutions used in this study were made
with deionized water (Milli-Q, 18.2 MΩ/cm).
For the samples in which the metal concentration was ≤1000 mg kg-1,
2-g soil samples were placed in 40-mL glass beakers and wetted with deion-
ized water. The volumes of solution calculated according to the concentra-
tion shown in Table 1 were added to the slurries to obtain the desired con-
centrations, and then immediately placed in an ultrasonic bath for 15 min.
For the samples in which the metal concentration was >1000 mg kg–1, the
solid reagents instead of solution were added to 2-g soil samples and ground
Table 1. The sequential concentrations of metals and reagents for modeling contamination.
Crustal Electron
Reagents
abundance†‡ configuration‡ 1 2
———————— mg kg−1 ———————
HgCl2 0.05 [Xe]4f145d10 0.5
Ni(NO3)2 ⋅ 6H2O 80 [Ar]3d8 50 100
CrCl3 ⋅ 6H2O 100 [Ar]3d3 50 500
CuCl2 ⋅ 2H2O 50 [Ar]3d9 100 500
† For the metal ion.
‡ Bowen (1979).
§ Values refer to the elements.
920
in an agate grinder to homogenize the samples. The above distinction in
sample preparation was made to avoid overadsorption at the interface due
to high concentration while pouring the solution into the soils. Finally,
additional water was added so that all the samples were 40 mL. The beakers
were covered with a watch glass in a forced-air oven at 40°C. When there
was no visible water, another 40 mL of deionized water was added to the
sample. The above process was repeated four times (22 d) before reflectance
spectra were measured on these artificially contaminated samples.
Prediction Experiments
Chemical Analysis
The 61 soil samples were analyzed for Ni, Cr, Co, Cu, As, Zn,
and Pb using an acid digestion method (Li and Thornton, 1993)
and with inductively coupled plasma–atomic emission spectroscopy
(ICP–AES, PerkinElmer 3300DV). Cadmium was analyzed by atomic
absorption spectrometry. Although Fe is not a toxic metal, it was also
analyzed with ICP–AES because it strongly affects soil spectra and Fe
oxides can adsorb heavy metals. Soil organic carbon (SOC) has many
of the same effects described for Fe. The SOC content was determined
by wet digestion with an acid solution of potassium dichromate with
external heat and reflux condensers. This was followed by a titration
of the excess potassium dichromate using a solution of ferrous ammo-
nium sulfate following modifications of Cambardella and Elliott
(1992). The pH of the soils in water (1:2) was measured using an
Orion Model 810 pH meter (Orion Research, Boston, MA).
Model Construction and Validation
The regression method used to establish relations between the spec-
tral responses (reflectance and their derivatives) and soil heavy metal con-
centration was partial least squares regression (PLSR) performed using the
Unscrambler software package version 8.0.5 (CAMO ASA, Trondheim,
Norway). Unscrambler has two types of regression, PLS1 for calibrating
one variable at a time and PLS2, which includes all the variables in the cali-
bration. In our research, the PLS1 regression was used to build the model. A
leave-one-out cross-validation procedure was used to estimate the optimum
number of terms to avoid overfitting. With leave-one-out cross-validation,
one sample was left out of the global data set and the model was calculated
on the remaining data points. The value for the left-out sample was then
predicted, and the prediction residual computed. The process was repeated
with another sample of the data set, and so on, until every sample had been
left out once; then all prediction residuals were combined to compute the
root-mean-square error of prediction (RMSEP). The optimum number of
terms was taken as the number resulting in the minimum RMSEP. For
validation, only the cross-validation was performed while not using test set
validation due to a limited number of samples. Moreover, the ratio of the
standard deviation of the population to RMSEP, also know as RPD, was
also calculated. The RPD demon-
strates how well the calibration models
Concentrations§ could predict chemical data (Fearn,
3 4 5 6 2002; Moron and Cozzolino, 2004).
1 10 100 400 1 000 Chemical Sequential
200 400 800 1 000
Extraction
Eight samples, the Fe concentra-
1000 4000 8000 10 000
tions of which exhibited significant
1000 4000 8000 10 000 variation, were selected from the 61
samples for the analysis of chemi-
cal fractions of soil metals. Selected
properties of the eight soil samples are
SSSAJ: Volume 71: Number 3 • May–June 2007
Table 2. Selected characteristics of the eight samples used for the
chemical sequential extraction.
Specific
Mean
Samples surface Fe2O3 pH SOC†
reflectance
area
m2 g−1 g kg−1 g kg−1
062c 39.17 8.29 51.3 7.66 10.8
026b 40.08 10.69 55.1 7.85 14.4
048a 38.93 12.4 59.9 7.80 8.2
041a 37.74 15.26 64.4 7.87 10.6
063a 39.11 17.66 65.0 7.70 13.2
040a 34.14 16.99 69.0 7.54 14.1
025d 37.05 19.78 72.4 7.94 14.4
052a 33.76 22.78 78.0 7.79 13.8
Fecorrel‡ −0.82 0.98 1.00 0.14 0.45
SOCcorrel§ −0.38 0.49 0.45 −0.02 1.00
† Soil organic C.
‡ Correlation coefficients with Fe.
§ Correlation coefficients with soil organic C.

given in Table 2. The measurement of the specific surface area for the eight
samples was obtained from gas-adsorption isotherms. Nitrogen adsorp-
tion isotherm measurements were performed on an ASAP2010 volumet-
ric adsorption analyzer from Micromeritics (Norcross, GA) at liquid N2
temperature (77K) in a relative pressure (p/p0) range from about 0.01 to
0.995 using about 1.0000 g of soil samples. Before isotherm measurements,
each sample was outgassed to the pressure of <0.02 Pa at 423K for about
10 h. The specific surface area (SBET) was calculated using the standard
Brunauer–Emmett–Teller (BET) method (Brunauer et al., 1938) with a p/
p0 range between 0.05 and 0.20. The primary aim of the CSE in this study
was to explore the mechanism that allows reflectance spectroscopy to pre-
dict heavy metal concentration. Iron oxides and organic matter in soils are
important because they are spectrally active and both of them can adsorb
heavy metals. Therefore, with emphasis on the species bound to the two soil
components and based on examining and comparing numerous published
results (Shuman, 1985; Hall et al., 1996; Sahuquillo et al., 1999; Ahnstrom
and Parker, 1999), the CSE used in our study is shown in Table 3.
An aliquot of the supernatant was filtered into clean glass test tubes.
To ensure one uniform matrix for inductively coupled plasma–mass spec-
troscopy (ICP–MS) analysis, the various extraction matrices were digested
with concentrated HNO3. To the 5-mL aliquots of extractant solutions, 5
mL of HNO3 (concentrated, 70% v/v) was added, and then the solutions
were heated to dryness at 90°C. The residue in the tubes was then leached
and 2% HNO3 added to produce a final volume of 10 mL. The concen-
tration of trace elements in the extracts was determined by ICP–MS, and
Fig. 2. The mean reflectance spectra of (a) the eight soil samples
after each sequential extraction step and (b) the continuum-
removed spectra (original = original soil; F1 = carbonates
removed; F2 = carbonates and Mn oxides removed; F3 =
carbonates, Mn oxides, and organic matter removed; F4 =
carbonates, Mn oxides, organic matter, and amorphous Fe
oxides removed; F5 = carbonates, Mn oxides, organic matter,
amorphous Fe oxides, and crystalline Fe oxides removed).
by ICP–AES for Fe. Two independent replicates were performed for each
sample and blanks were measured in parallel for each set of analyses using
the extraction reagents described above. For each step, reflectance spectra
were measured for the residue.
RESULTS
Spectral Response of Heavy Metals in Soils
Figure 2 shows the mean reflectance spectra of the eight soil
samples after each sequential extraction step and the continuum-
removed spectra. In the near-infrared region, the absorption features
are narrow and sharp, while in the visible region the features tend

Table 3. Sequential extraction procedure.

Step Fraction Chemical reagents and conditions
To a 2.5-g soil sample, add 90 mL of 0.11 M HOAc (pH 2); shake for 16 h at 22 ± 5°C;
F1 exchangeable and weak acid soluble
separate extract from the solid residue by centrifugation at 3000 × g for 20 min.
To Step 1 residue, add 20 mL of 0.1 M NH4OH·HCl (pH 2); shake for 16 h at 22 ± 5°C;
F2 Mn oxides
centrifuge at 3000 × g for 20 min.
To Step 2 residue, add 15 mL of H2O2 (pH 2), let stand 1 h at room temperature; heat to 85
F3 organic matter ± 2°C for 1 h; add a further 15 mL of H2O2 and heat to 85 ± 2°C for 1 h; add 60 mL of 1 M
NH4OAc (pH 2) and shake for 16 h at 22 ± 5°C; centrifuge at 3000 × g for 20 min.
To Step 3 residue, add 60 mL of 0.2 M (NH4)2C2O4·H2O–0.2 M H2C2O4 (pH 3); shake for 4 h
F4 amorphous Fe oxides
at room temperature in the dark; centrifuge at 3000 × g for 20 min.
To Step 4 residue, add 50 mL of solution as for Step 4 plus 0.1 M ascorbic acid; boiling water
F5 crystalline Fe oxides
bath for 30 min; stir occasionally.
F6 residual Subtract the sum of the five metal binding fractions from the total content of the metal.

SSSAJ: Volume 71: Number 3 • May–June 2007 921


Fig. 3. Continuum-removed reflectance spectra of soils with varying concentrations of Cr centrations and, indirectly, the activity of the ele-
and Cu. The “continuum-removed” spectrum was calculated as the ratio of the re-
flectance of the artificially contaminated samples to that of the untreated samples.
to be wider and weaker. The three most distinct absorption bands
at 1400 and 1900 nm are attributable to vibrational frequencies
of OH groups in the adsorbed water, and the absorption feature
at 2200 nm is related to OH groups in the crystal lattice water of
illite (x-ray diffraction not shown data). The presence of Fe results
in absorption at wavelengths in the 380- to 1300-nm region and
rapid fall-off of reflectance toward the blue wavelengths, while the
absorption features are weak (Hunt et al., 1971; Burns, 1993). After
removing carbonates, Mn oxides, and organic matter, the absorp-
tion features in the visible region became obvious (Fig. 2a). Through
continuum removal, a doublet absorption feature near 500 nm,
which is caused by goethite, can be exhibited (Fig. 2b). Although
the absorption bands of goethite at 950 nm are also strong, it can-
not be exhibited on either the original or the continuum-removed
curve, even with the soil organic matter removed. Therefore, the
diagnostic spectral feature for identifying goethite in soils is 500 nm
but not 950 nm, and this has been validated by previous research
(Balsam and Deaton, 1991; Wu et al., 2005a).
Similar to Fe, the absorption bands of the studied transition
metals are shorter than 1300 nm (Fig. 3). Soil spectral features
within this region are weak, and thus it is difficult to identify the
922
spectral difference of the soils with different heavy
metal concentrations from the original reflectance
curve. Making a ratio of the spectra against that
of the untreated sample can enhance the spectral
difference, thereby contributing to the identifica-
tion of spectral features. Moreover, continuum
removal was used on the ratio spectra to further
enhance the weak absorption features of transi-
tion elements. From Fig. 3 it can be seen that,
regardless of the absorption features, heavy metal
elements cannot be detected with reflectance
spectroscopy at concentrations ≤1000 mg kg–1
When the concentration for Cr and Cu is as high
as 4000 mg kg–1, their absorption features around
610 and 830 nm can be distinguished and the
depth increases as concentration increases.
The modeling contamination experiment
answered the question about the concentration
at which heavy metals can exhibit their inherent
absorption features. For agricultural soils, how-
ever, few are contaminated to such high levels.
Therefore, under real-world conditions, heavy
metals cannot be identified directly by their
absorption features with reflectance spectros-
copy. New questions then emerge: (i) can heavy
metals in agricultural soils be predicted with
reflectance spectroscopy; and (ii) if the answer
is positive, what is the predictive mechanism?
Prediction for Agricultural Soils
Descriptive data statistics for the 61 soil
samples, including mean, SD, minimum and
maximum concentrations, CV, etc., are shown
in Table 4. The CV, which is SD/mean, indicates
the degree of discrete distribution of metal con-
ment. To approximate the intensity of soil con-
tamination, a pollution index (PI) was defined.
The PI was calculated as the ratio between the
mean concentration and the background value specifically for
this element. The background value comes from the research
results of the Geological Survey of China (Wang, 2003).
Principal component analysis (PCA) can be used to clarify
the relationships between the heavy metals (Li et al., 2004;
Han et al., 2006). A component loading plot of Factors 1 and
2 obtained from the results of PCA for all analyzed elements of
the 61 soil samples shows that the four siderophile elements Fe,
Co, Ni, and Cr cluster together (Fig. 4). Correlation analysis
also indicates that the correlation coefficients between Fe and
the other three siderophile elements is very high (R > 0.97).
The two chalcophile elements Cd and Pb are separated from
the other elements. Their correlation coefficients with Fe are
lower than those of other heavy metals (Table 4). From Table
4 it can be seen that Cd has the highest PI and CV values.
The three siderophile elements, Ni, Cr, and Co, have PI values
near 1.0, suggesting that they are closely related, which is not
surprising considering their affinity during geochemical cycles.
Cadmium, however, behaves differently than the other metals.
SSSAJ: Volume 71: Number 3 • May–June 2007
Table 4. Statistical information for the 61 soil samples.
Ni Cr Co Cu As Zn Pb Cd SOC† Fe2O3 pH
————————————————— mg kg−1 —————————————————— — g kg−1 —
Min. 27.3 60.8 11.5 26.5 6.13 68.8 21.4 0.22 4.3 48.5 7.27
Max. 50.6 104.0 19.7 55.3 13.30 120.0 42.8 0.54 57 79.4 8.02
Mean 39.53 83.03 16.0 43.75 10.42 99.08 33.48 0.33 12.7 66.3 7.75
SD 5.46 10.49 2.03 6.53 1.63 11.92 5.35 0.061 0.65 0.77 0.16
CV, % 14 13 13 15 16 12 16 18 51 12 2
BV‡ 36.11 76.95 15.28 31.69 9.24 80.71 31.28 0.2
PI§ 1.09 1.08 1.05 1.38 1.13 1.23 1.07 1.65
Fecorrel¶ 0.98 0.97 0.98 0.91 0.88 0.81 0.61 0.52
SOCcorrel# 0.17 0.10 0.13 0.23 0.14 0.26 0.14 0.15
† Soil organic C.
‡ Background value of the study area.
§ Pollution index: the ratio between the mean concentration and the background value.
¶ Correlation coefficients between Fe and heavy metals.
# Correlation coefficients between soil organic C and heavy metals.

The RMSEP is known as a good criterion to judge the pre-
diction performance of PLSR models (Shenk and Westerhaus,
1993). Here, the smallest RMSEP value was used to determine
the optimal calibration model. Table 5 shows the optimal vali-
dation results of the PLSR models for the heavy metals of the
61 agricultural soil samples. The best prediction results for Cr
and As were acquired with the first derivative spectra. For other
metals, the best predictions were acquired with the reflectance
percentage data. The results of the second derivative spectral
data were all unsatisfactory.
From Table 5 it can be seen that the highest prediction
accuracies were acquired for the three siderophile elements—
the R2 for these elements was about 0.8, and RPDs > 2.0. The
validation results for Cu and As, the two chalcophile elements,
gave R2 near 0.7, and RPDs > 1.7. The poorest prediction was
for Cd. Figure 5 shows the scatterplots of predicted vs. mea-
sured concentrations in the validation stage for the 61 samples.
The points for all the metals except Cd fall in the vicinity of the
1:1 line. For Cd, the points at the higher end of the measured
range show an underestimation of the predicted value. In this
study, the prediction accuracies for the siderophile elements
Ni, Cr, and Co are the highest, Cu, As, Zn, and Pb are moder-
ate, while Cd is the worst.
DISCUSSION
To further understand the mechanism that allows estima-
tion of heavy metals with reflectance spectroscopy, some sta-
tistical analysis was first made. Figure 6 shows the correlation
coefficients between reflectance and heavy metals as well as Fe
across the spectral range. For all eight trace elements, the gen-
eral trend of the curves of their correlation coefficients as a
function of wavelength was virtually similar, and similar to the
coefficients of Fe. In general, metals are all negatively correlated
with reflectance. Regions around 480 to 510 nm, the feature
resulting from goethite, had particularly high correlation coef-
ficients. Conversely, metals are positively correlated with the
absorption depth at 500 nm (Fig. 7). The highest correlation
coefficients were acquired for the three siderophile elements
Ni, Cr, and Co, while the correlation coefficient for Cd was the
lowest among the eight elements.
The results shown for the relationships between spectral
parameters (absorption depth and reflectance values) and heavy
metal concentration indicate that Fe oxides play an important
role in the prediction of soil heavy metals using reflectance spec-
tra. The crystalline Fe oxides in soils of the research area are
almost entirely goethite (Y. Wu, unpublished data, 2005). The
yellowish color of soil is attributable to the Fe3+ absorption near
the 500 nm of goethite. Specimens of goethite have large surface
areas and can adsorb heavy metals. As goethite content in soils
increases, the heavy metal concentrations increase accordingly.
On the other hand, the absorption depth at 500 nm becomes
deeper with increased goethite content (Wu et al., 2005a).
Therefore, heavy metals are positively correlated with the absorp-
tion depth at 500 nm. In contrast, the reflectance values of soils
decrease because of the absorption of goethite. Therefore, soil
reflectance is negatively correlated with heavy metals.
Besides being bonded to Fe oxides, heavy metals in soils can
also exist in several other chemical fractions as well as Fe. The results
from sequential extraction show that Fe was primarily in the crystal-
line Fe oxide, residue, and amorphous Fe oxide fractions (Fig. 8).
Other forms of Fe were almost negligible. The distributions of Ni
and Co among different fractions were visually almost identical,
with the highest in the crystalline Fe oxide fraction and lower in
residual fraction. Chromium was highest in the residue and low in
the crystalline Fe oxide fraction, showing abnormity with Ni and
Fig. 4. Loading plot of heavy metals and Fe by principal compo-
nent analysis of 61 samples.

SSSAJ: Volume 71: Number 3 • May–June 2007 923

 Table 5. Cross validation statistics for heavy metals of the 61 soil samples. other forms of Fe such as residual and
Statistic Ni Cr Co Cu As Zn Pb Cd amorphous Fe oxide can also contribute
Math treatment† R D R R D R R R to soil reflectance. For example, they may
R2 0.81 0.85 0.80 0.67 0.72 0.56 0.55 0.20 reduce the values of reflectance within the
RMSEP‡ 2.32 4.20 0.93 3.74 0.86 8.2 3.58 0.05 whole spectral region. Note that in this
RPD§ 2.35 2.50 2.18 1.74 1.90 1.45 1.49 1.23 study, the prediction of heavy metals also
† R = reflectance; D = first derivative. uses whole wavebands instead of 500-nm
‡ Root-mean-square error of prediction. absorption peaks. Therefore, complemen-
§ Ratio of the standard deviation of the population to the root-mean-square error of prediction. tary to the previous study in which the
correlation with active soil components
Co despite being a siderophile element. Although the fractionation (such as Fe oxides, organic matter, and
scheme is diverse for all the metals, the results of chemical sequen- clay) allowed estimation of heavy metals with reflectance spectros-
tial extraction indicate that, besides the crystalline Fe oxide fraction, copy (Malley and Williams, 1997; Kooistra et al., 2001; Kemper
heavy metals also have significant amounts in the residual fraction. and Sommer, 2002), in this study it was concluded that the inter-
Although only crystalline Fe oxides have distinct absorption peaks, correlation between heavy metals and total Fe (including active and
residual Fe) is the major mechanism.
This conclusion is further supported
by the relationships between heavy met-
als, Fe and reflectance. Comparing the
prediction results and the correlation
coefficients between Fe and heavy met-
als (Tables 4 and 5), it is interesting to
note that all the heavy metals that have
a high correlation with Fe also have high
cross-validation statistics. The three sider-
ophile elements Ni, Cr, and Co have the
highest correlation coefficients with Fe.
Their predictive accuracy is also the high-
est among the eight elements. The most
poorly predicted element, Cd, shows the
lowest correlation with Fe.
In addition to Fe content, there are
many other properties affecting soil reflec-
tance, such as moisture, particle size, organic
matter, and roughness. In this study, mois-
ture, particle size, and roughness were simi-
lar for all the samples because the samples
had been dried and ground before the
spectral measurements. Another important
property of soil, organic matter, can absorb
electromagnetic waves and adsorb heavy
metals; however, the correlation between
organic matter and heavy metals is very
poor in the study area (Table 4). The crys-
talline Fe oxide content (i.e., goethite) was
also positively correlated with the crystalline
Fe oxide fractions for all the metals (Fig. 7),
while the correlation coefficients between
organically bound heavy metals and organic
matter content were not significant (Y. Wu,
unpublished data, 2005). Moreover, as seen
from Fig. 8, the sum of the fractions related
to Fe, such as that bonded to amorphous
Fe oxide, crystalline Fe oxide, and residue
(i.e., F4 + F5 + F6) is significantly larger
than the fraction bonded to organic matter.
Therefore, it is thought that Fe plays a more
Fig. 5. Plots of measured vs. predicted concentrations of eight heavy metals. The 1:1 line important role in predicting heavy metals
is indicated on each figure. than organic matter. The reason is perhaps

924 SSSAJ: Volume 71: Number 3 • May–June 2007

because the content of inorganic component frac-
tions in dry soils is much larger than the organic
component. Here, it should be clarified that it does
not mean that organic matter does not have any
effect on the relationship between soil spectra and
heavy metals. Soil organic matter also contributes
to the relationship, although its contribution is not
so much as that of total Fe. This is different from
food and forage crop research by reflectance spec-
troscopy. In that case, the content of inorganic ele-
ments is low relative to the organic matrix. Thus,
successful prediction for inorganic components
in forage crops could be based on the correlations
between the inorganic components and the organic
constituents (Siebielec et al., 2004).
The poorer predictive results for Cd suggest that
it behaves differently than the other metals. Figure
8 shows that Cd is the element with the highest
exchangeable fraction, whereas the residual fraction
is low in comparison with other elements. It is not
like the siderophile elements, which are closely cor-
related with each other. Cadmium is separated from
the other chalcophile elements Zn and Cu (Fig. 4).
Moreover, it has the highest PI value (PI = 1.65) and
CV (0.18) among the eight elements.

CONCLUSIONS
Reflectance spectroscopy is a simple and non-
destructive analytical method that can be used to
predict not only spectral active constituents but also
trace elements, which are spectrally featureless. This
study shows that only transition elements, which
have an unfilled d shell and are present at very high Fig. 6. Correlation coefficients between reflectance and metals.
concentration, can exhibit their inherent absorp-
tion features. The results of modeling experiments accuracy for metals is approximately the same as the order of their
indicate that when the concentration of Cr or Cu is increased to correlation coefficients with Fe. Complementary to the previous
4000 mg kg–1, their absorption features can be exhibited, and the study in which the intercorrelation between heavy metals and active
intensity increases with increasing concentration. Although few soil components (such as Fe oxides, organic matter, and clay) was
agricultural soils have heavy metal contaminants that can be identi- elucidated as the major mechanism by which trace metals can be
fied directly by reflectance spectroscopy, it still can be used to esti- predicted, in the present study it was concluded that the correlation
mate heavy metal concentrations. For the research area, the highest with total Fe is the major mechanism. This conclusion was further
prediction accuracies were for the siderophile elements Ni, Cr, and supported by both statistical analysis and the chemical sequential
Co, and the poorest prediction was for Cd. The order of prediction extraction procedures. Correlation analysis showed that all metals

Fig. 8. Average percentage distribution of heavy metals and Fe

between various fractions determined by the chemical se-
Fig. 7. Correlation coefficients between absorption depth around 500 quential extraction procedure (F1 = exchangeable; F2 = Mn
nm and metal concentrations (D_500), and crystalline Fe oxide oxides; F3 = organic matter; F4 = amorphous Fe oxides; F5
content and crystalline Fe oxide fractions for all the metals. = crystalline Fe oxides; F6 = residual).

SSSAJ: Volume 71: Number 3 • May–June 2007 925

 are negatively correlated with reflectance while positively correlated
with the absorption depth at about 500 nm, a feature resulting from
goethite in soils. The chemical forms of heavy metals, which showed
that besides the crystalline Fe oxide and organic matter fractions,
heavy metals have significant amounts in the residual fraction, also
strengthened the relationship.
ACKNOWLEDGMENTS
This research was supported by the Geological Survey of Jiangsu Province
and the Hundred Talent Project of the Chinese Academy of Sciences. We
are grateful to Emeritus Professor Joseph Giles of North Dakota State
University, Professor Arthur P. Cracknell of the University of Dundee, and
Professor William L. Balsam of University of Texas at Arlington for technical
assistance and English language support. We thank professor Xiancai Lu of
Nanjing University for specific surface area measurements.
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