Catena 139 (2016) 220–231

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Utilizing portable X-ray fluorescence spectrometry for in-field

investigation of pedogenesis
U. Stockmann ⁎, S.R. Cattle, B. Minasny, Alex B. McBratney
Soil Security Laboratory, Department of Environmental Sciences, Faculty of Agriculture and Environment, The University of Sydney, Suite 401, Biomedical Building C81, 1 Central Avenue, ATP,
Eveleigh, NSW, Australia

a r t i c l e i n f o a b s t r a c t

Article history: In recent years portable X-ray fluorescence (pXRF) spectrometers have been recognised as an in-field tool for soil
Received 13 August 2015 analyses as they offer rapid, real-time, simultaneous multi-element analysis of soil samples with no or minimal
Received in revised form 7 January 2016 sample preparation. Portable XRF has been used quite extensively to estimate the degree of soil contamination
Accepted 7 January 2016
with heavy metals and to measure the concentration of elements in soils that are important for the soil's fertility,
Available online xxxx
but more recently it has also been used to calibrate for a range of soil chemical and physical properties to perform
Keywords:
digital soil morphometrics. However, this still relatively new technology also offers an opportunity for soil scien-
Portable X-ray fluorescence spectrometer tists to investigate processes of pedogenesis in the field, which in turn will complement the in-field descriptions
Pedogenesis of soils profoundly. Here, we employed a handheld pXRF spectrometer to investigate the pedogenesis pathways
Weathering indices and likely parent materials of three different soil types, utilizing elemental concentration data and geochemical
Geochemical indices indices. Our study site, a property called ‘Nowley’, is situated on the Liverpool Plains in the Spring Ridge district
Elemental ratios on the North West Slopes of New South Wales, Australia, in one of the most versatile dryland cropping regions of
Lithologic discontinuity the continent. The variation in soil types and parent materials across the property offers an unique opportunity to
study the impact of parent materials and topography on soil formation. A total of three soil pits were excavated to
a depth of 1.0 m to expose the lower B horizons. Soil pit faces were then scanned at 0.1 m depth increments
starting from the top of the soil profile to the lowest B horizon exposed. Our results show that elemental data ac-
quired in field condition, which are affected by sample heterogeneities and soil moisture content, are comparable
to elemental data acquired in air-dried, ground condition, as geochemical index values show similar trends down
the soil profile. We found that the use of pXRF is a very effective in-field tool to assess pedogenic pathways and
parent material origin, because of the instant computation of weathering indices and elemental ratios. We
conclude that pXRF can be applied successfully and readily to study the soil's weathering history and identify
processes of soil formation in the field.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction readings are inexpensive to obtain when compared to traditional

Lately, portable X-ray fluorescence spectrometers (pXRF) have been
recognised as a laboratory and in-field tool to enhance soil profile de-
scriptions as they offer rapid (within minutes), simultaneous multi-
element analysis of soil samples with no or minimal sample prepara-
tion. The use of handheld pXRF devices has been well established for
geological prospecting applications (Fisher et al., 2014; Hall et al.,
2014), but with recent advances in pXRF technology their in-field use
through scanning the soil in its natural condition has become very at-
tractive for soil scientists (Horta et al., 2015; Hou et al., 2004; West
et al., 2013). More explicitly, this new technology offers the opportunity
to investigate processes of pedogenesis in the field as it reports elemen-
tal data directly and non-destructively which in turn complements the
in-field descriptions of soil profiles. Furthermore, pXRF total elemental
⁎ Corresponding author.
E-mail address: uta.stockmann@sydney.edu.au (U. Stockmann).
laboratory-based analytical techniques, which are also considerably
more time-consuming.
The operation of handheld pXRF spectrometers relies on the fact that
excess energy in the form of an X-ray photon (fluorescence) is emitted
when an excited inner shell electron is replaced by an outer shell elec-
tron. This fluorescence energy is characteristic of the elements present
in a sample of interest, and so, theoretically, the XRF spectrum of any el-
ement may be determined by the pXRF detector. However, because of
low energy responses, not all elements of the periodic table can be effec-
tively measured and there is also a limit of detection depending on the
amount of the element of interest in the sample (Hou et al., 2004; Potts,
2008).
Portable XRF has been used quite extensively to estimate the degree
of contamination of soils with heavy metals and other elements of inter-
est such as As, Ba, Cr, Cu, Hg, Mo, Ni, Pb, Sn, V and Zn (e.g. Bernick et al.,
1995; Kalnicky and Singhvi, 2001; Laiho and Perämäki, 2005; Radu and
Diamond, 2009; Ramsey, 2008; Weindorf et al., 2008, 2012a). Overall,

http://dx.doi.org/10.1016/j.catena.2016.01.007
0341-8162/© 2016 Elsevier B.V. All rights reserved.
 U. Stockmann et al. / Catena 139 (2016) 220–231
results showed that pXRF devices provide good analytical precision
when compared to laboratory-based, conventional methods of analysis
such as inductively coupled plasma atomic emission spectrometry (ICP-
AES) (Horta et al., 2015). Furthermore, pXRF has been used to measure
the concentration of elements in soils that are important for the soil's
fertility and thus plant production. For example, Zhu and Weindorf
(2009) used pXRF spectroscopy to determine the total concentration
of calcium (Ca) in soils, concluding that this element can be measured
rapidly and accurately employing this technology. McLaren et al.
(2012) used pXRF for rapid total elemental analysis of agriculturally im-
portant elements in Vertisols of northern NSW, Australia, and found
that non-destructive pXRF analysis compared well to laboratory based
measurements such as ICP-OES analysis, particularly for Ca, Fe, Mn
and P. More recently, pXRF results have also been used to calibrate for
a range of soil chemical and physical properties. These studies use the
total elemental concentrations to infer a range of soil properties using
multiple linear regression models. For example, Weindorf et al. (2009)
and Weindorf et al. (2013) used pXRF to quantify the amount of gypsum
(CaSO4·2H2O) in soils. Zhu et al. (2011) related pXRF elemental esti-
mates to soil texture, and found that Fe and Rb were of particular signif-
icance for predicting clay content. More recently, Wang et al. (2013)
proposed the complementary use of pXRF elemental measurements
and Fourier transform NIR spectral data to infer soil texture, while
Weindorf et al. (2012c) attempted to differentiate spodic and andic fea-
tures of soil horizons employing pXRF based on the assumption that
spodic/andic horizons are often characterized by particular metallic
complexes. Sharma et al. (2014) employed elemental data acquired
through pXRF as a proxy for soil pH, however predictions were of rea-
sonable accuracy only. Adding additional auxiliary information such as
texture and organic matter slightly improved predictions.
Pedogenetic aspects, however, have not been specifically addressed
in most of these studies. Weindorf et al. (2012b) used pXRF to investigate
soil profile development by characterizing the degree of horizonation for
a range of soil profiles. The authors characterized the changes in elemen-
tal concentrations throughout a soil profile in relation to topsoil and sub-
soil horizons and found that elemental data aligned with morphological
horizon descriptions, and concluded that pXRF could be used as an addi-
tional tool to distinguish characteristic soil horizons (such as multiple
spodic, gypsic horizons). More recently, Weindorf et al. (2015) assessed
lithologic discontinuities in soils via abrupt changes in standardized
pXRF-measured differences in element concentrations and differences
in vis–NIR reflectance spectra.
There is the opportunity, however, to also use pXRF data to investi-
gate soil development by estimating the degree of soil weathering;
which previously could only be conducted employing laboratory instru-
ments such as ICP-AES, XRD or XRF (e.g. Che et al., 2012; Chittleborough,
1991; Chittleborough et al., 1984; Sauer et al., 2007). This new and read-
ily available technology now needs to be embraced and taken to the
field to perform ‘digital soil morphometrics’ (Hartemink and Minasny,
2014) as well as investigations into the degree of soil weathering ‘on
the spot’. In this work, we employed a handheld pXRF spectrometer to
investigate the likely parent materials and degree of weathering under-
gone by a variety of soil types, utilizing geochemical indices.
2. Materials and methods
2.1. Study site
This study was conducted at the E.J. Holtsbaum Agricultural Re-
search Station, ‘Nowley’, which is operated and managed by the Faculty
of Agriculture and Environment at The University of Sydney. The
Nowley property covers a total of 2083 ha and is currently run as a com-
mercial mixed farming enterprise. Nowley is located on the Liverpool
Plains in the Spring Ridge district of the North West Slopes of New
South Wales, Australia, near the town of Gunnedah in one of the most
versatile dryland cropping regions of Australia (Fig. 1).
221
The property Nowley is entirely contained within the Curlewis
1:250,000 Soil Landscape Mapsheet area (Banks, 1995). The two most
prominent soil landscape units mapped across Nowley are ‘Noojee’
and ‘Trinkey Forest’, with very small areas of ‘Mount Milbulla’ and
‘Quirindi Creek’ at the eastern and western margins of the property,
respectively (Fig. 2) (Banks, 1995). The dominant lithological units of
the Noojee soil landscape are Jurassic basalts, dolerites and tuffs of the
Garrawilla Volcanics while for the Trinkey Forest soil landscape the
main lithological units are horizontally-bedded sandstones and mud-
stones of the Jurassic Purlewaugh Beds and Pilliga Sandstones, with
some areas of conglomerates (Banks, 1995). The Mount Milbulla soil
landscape lithology is also characterized by Jurassic basalts and dolerites
of the Garrawilla Volcanics, while the Quirindi Creek soil landscape is
dominated by alluvium. Topographically, Nowley is comprised mainly
of Quaternary alluvial plains and outwash fans derived from the
Garrawilla Volcanics, Purlewaugh Beds and Pilliga Sandstones that un-
derlie and flank the steeply sloping eastern edge of the property. The
north–south running range of hills to the immediate east of Nowley,
which includes the Mount Coolanbilla and Mount Colly Blue ‘peaks’
(Fig. 3), attains an average height of approximately 625 m a.s.l., while
the lower-lying western half of the property has an elevation of approx-
imately 320 m a.s.l. The Liverpool Plains area, which includes Nowley,
experiences a dry sub-humid climate with a summer dominant rainfall
system and has an average annual rainfall of about 650 mm.
The varying topography and soil parent materials of Nowley have
given rise to a variety of soil types across the property. On the upper
slopes at the eastern end of the property, shallow and stony soils weath-
ered from basalt are present, grading to deeper and dark-coloured
Vertosols (World Reference Base equivalent Vertisols, Soil Taxonomy
equivalent Udic Haplusterts) in the upper mid-slope and mid-slope
positions. Also prominent in these mid-slope positions are texture-
contrast Chromosols (World Reference Base equivalent Luvisols, Soil
Taxonomy equivalent Udic Rhodustalfs), while in the lower slope
positions poorly drained, grey-brown Vertosols (World Reference Base
equivalent Vertisols, Soil Taxonomy equivalent Sodic Gypsiusterts), and
texture-contrast Sodosols (World Reference Base equivalent Solonetz,
Soil Taxonomy equivalent Aquic-Arenic Natrustalfs) are present.
This general pattern of soil type distribution is well reflected in Fig. 4,
which shows the total gamma radiometric emissions from the topsoil.
The area of conspicuously low gamma radiometric counts in the south-
west of Nowley corresponds to the extent of Sodosols, which exhibit
very low topsoil clay contents. The area of higher counts in the centre
of the property corresponds to the more clayey topsoils of the dark-
coloured Vertosols and Chromosols, while the poorly drained grey-
brown Vertosols in the northwest of the farm emit an intermediate
gamma radiometric count.
2.2. Study soils — and presumed pedogenesis pathways
As indicated on Fig. 2, three soil types present at Nowley were
selected for this work; a Black Vertosol, a Red Chromosol and a Brown
Sodosol. The Black Vertosol soil profile is situated on the upper
footslopes of Mt. Coolanbilla and is situated within the Noojee soil land-
scape unit as defined by Banks (1995). The presumed pedogenesis of
this soil is the weathering of Jurassic basalt, along with short-range col-
luvial transport of this weathered material, to yield black, smectitic soil
showing characteristic vertic features, viz. high clay content throughout,
the presence of pronounced shrinkage cracks through the profile, and
lenticular peds and slickensides in the Bw and Bk1 horizons. Some sec-
ondary calcium carbonate (calcite) accumulation is also apparent in
the lower B horizons (N0.6 m depth). The pH (1:5, soil:water) of the
topsoil is 6.9 and gradually increases down the profile to 8.9 at the
depth of 0.9 m. Also at this depth of approximately 0.9 m, an abrupt
lithologic discontinuity occurs, with a seam of water-worn gravels over-
lying a distinctly reddish-brown buried soil.
222 U. Stockmann et al. / Catena 139 (2016) 220–231
Fig. 1. Study site in respect to New South Wales, Australia.
The Chromosol profile is situated in a mid-slope position on the long,
gentle footslope of the range of hills to the east of Nowley. Its location
falls within the area mapped as the Noojee soil landscape unit in
Fig. 3, but the particular stretch of unit boundary near this profile is
marked as being ‘approximate’. This soil type does not appear in the typ-
ical catenary sequence of soils for the Noojee soil landscape, but is sim-
ilar to an upper footslope soil type described in the adjoining Trinkey
Forest soil landscape. It is therefore presumed that this soil evolved
from the weathering and partial colluvial transport of soil material
from the mudstones of the Purlewaugh Beds of this soil landscape
unit. The Red Chromosol is a texture-contrast soil, with a shallow
(0.1 m thick), brown, clay loam A horizon overlying a series of strongly
prismatic, red, light medium clay B horizons. A hypercalcic horizon con-
taining soft, pedogenic carbonates occurs in the lower part of the profile.
The pH (1:5, soil:water) of the topsoil is 7.1 and ranges between 7.7 and
8.5 in the subsoil horizons. This profile shows features consistent with
argilluviation (lessivage), including the presence of smooth ped fabric
for the angular blocky peds of the B horizons, and clay coatings
(argillans) evident in thin section (Fig. 5a). The profile also shows evi-
dence of some vertic character, with occasional lenticular peds present
in the Bt3 horizon; the clay mineral smectite was also identified through
X-ray diffraction analysis of this horizon (Quilty, 2007). At a depth of
1.2 m, a lithologic discontinuity is observed, with a thin stone line giving
way to a horizon of red, fine sand.
The Sodosol profile is located on the flat, lower footslopes at the
western margin of Nowley and is located within the ‘Trinkey Forest’
soil landscape unit. This Sodosol exhibits classic solonetzic features,
and matches precisely the floodplain soil of the Trinkey forest soil land-
scape catena (Banks, 1995). The profile exhibits a strong texture-
contrast, with a pinkish, apedal, sandy topsoil abruptly overlying a
strongly columnar, mottled, orange-brown, light to medium clay subsoil
at a depth of 0.4 m. A further feature of this profile indicating the past
processes of solodization is the presence of a 0.05 m thick silicified
(silica-rich) and cemented layer at the interface of the top- and subsoil,
effectively capping the domes of the large columnar peds of the B hori-
zon. The pH (1:5, soil:water) of the sandy topsoil is 6.0 and increases to
around 6.5 in the clayey subsoil horizons. The pedogenesis of this soil is
assumed to follow the model set-out by Hallsworth and Waring (1964)
for solodized-solonetz soils of northern New South Wales; the long-
term weathering and organisation of a coarse-textured parent material
in a semi-arid environment, with abundant argilluviation, a dearth of
calcium-bearing minerals, a source of sodium, and the cycling of silica
through the rhizosphere via plant roots and leaf fall. Fig. 5b shows the
prominence of clay coatings and plugs in the upper B horizon of this
Sodosol. An alternative pedogenic pathway for this profile is that
sandy colluvium sourced from the Jurassic sandstone of the district
has been deposited over a pre-existing sodic, clayey alluvium to yield
a texture-contrast, solonetzic profile.
2.3. In-field soil profile scanning utilizing pXRF
For each of the three soil types, a pit was excavated to a depth of
more than 1.0 m in order to expose the lower B horizons (refer
to Fig. 1 for locations). An Olympus Delta Premium handheld portable
 U. Stockmann et al. / Catena 139 (2016) 220–231 223

Fig. 2. Soil landscape units of the Curlewis 1: 100,000 sheet map (Banks, 1995) encompassing Nowley Farm.

Fig. 3. Soil pit locations on Nowley Farm.

224 U. Stockmann et al. / Catena 139 (2016) 220–231

Fig. 4. Spatial variation in soil total gamma radiometric emissions on Nowley Farm.

X-ray fluorescence analyser was used to scan the soil pit faces in field
condition at 0.1 m depth increments starting from the top of the soil
profile, with a total of 9 samples for the Vertosol, 13 samples for the
Chromosol and 10 samples for the Sodosol (Olympus InnovX-Systems,
US, 2010). The Olympus Delta Premium pXRF features an Au anode
X-ray tube of 10–50 kVp at 10–200 μA and operates based on an internal
factory installed calibration procedure which uses the Compton
Normalization method to estimate the elemental concentration of the
soil directly in mg kg−1 or %. In-field measurements were first taken
in the soil mode, followed by the geochem operational mode. The soil
mode operates in a three-beam configuration at 50, 40 and 15 kV, re-
spectively, whereas the geochem mode operates in a two-beam config-
uration at 50 and 10 kV. Samples were scanned for a duration of 30 s
per beam. The geochem mode uses longer count rates, which makes it
possible to use this configuration for the measurement of low atomic
number elements, such as Al and Si (LOD of 1%), that are of importance
for calculating geochemical weathering indices. The soil mode was used
to measure the concentration of K, Ca, Mn, Ti and Zr whereas the
geochem mode was employed to measure the concentration of Al, Si
and Fe.
Prior to pXRF measurements in the field, the instrument was
calibrated using an Alloy 316 Stainless Steel Cal Check Standardization
Coupon, containing 16.13% Cr, 1.78% Mn, 68.76% Fe, 10.42% Ni, 0.20%
Cu and 2.10% Mo, and the scanning of the SiO2 blank to detect potential
contamination on the pXRF measurement window. The performance of
the pXRF instrument was verified using a range of NIST soil standards
with varying elemental concentrations (SRM 2709, SRM 2710, and
SRM 2711a). Performance results of NIST SRM 2709, San Joaquin soil,
for the elements of interest in this study were (pXRF reported/NIST cer-
tified [recovery]): K, 20,300/18,854 mg kg−1 [1.08]; Ca, 18,900/
19,581 mg kg− 1 [0.97], Mn 538/527 mg kg− 1 [1.02]; Ti, 3420/
3341 mg kg−1 [1.02]; Zr, 160/123 mg kg− 1 [1.30]; Si, 29.66/27.84%
[1.07]; Al, 7.5/6.56% [1.14]; Fe, 3.5/3.84% [0.91]. Following the scanning
of each pit face at 0.1 m increments (Fig. 6), sub-samples of soil were

Fig. 5. Micrographs of (a) the Bt2 horizon of the Red Chromosol profile, with A indicating a clay coating, and (b) the Btn2 horizon of the Brown Sodosol profile, with B indicating a zone of
prodigious clay coatings and clay plugs.
 U. Stockmann et al. / Catena 139 (2016) 220–231
Fig. 6. pXRF pit scanning of the Red Chromosol profile.
taken from each scanning site for air-drying, grinding to less than 2 mm
and pXRF scanning in a laboratory setting. Also, samples of basalt, doler-
ite, mudstone and sandstone rock collected from the eastern margin of
Nowley were scanned in field condition in both the soil and geochem
modes, and were pulverized and scanned in a laboratory setting in
both the soil and geochem modes.
2.4. Weathering indices and elemental trends calculated using pXRF
measurements
Portable, handheld XRF technology offers the opportunity of esti-
mating pedological features, and inferring pedological processes, in
the field through the virtually instant computation of weathering indi-
ces and elemental ratios that have been developed to assess the
weathering history of soil profiles (Sauer et al., 2007). Until now, this
was only possible after analysing soil samples in the laboratory,
employing time-consuming, destructive and cost-intensive sample
pre-treatments. Bringing laboratory-based weathering indices to the
field is therefore a significant advantage for objectively investigating
and understanding the evolution of soil in the field.
We used the pXRF measurements of total amounts of Al, Si, Fe, Zr
and Ti estimated through an internal factory installed calibration proce-
dure to calculate geochemical indices and elemental ratios, from soil
scanned down the pit wall in field condition as well as in laboratory con-
dition (air-dried and ground to less than 2 mm), and from parent mate-
rial rocks in field and laboratory condition (air-dried and pulverized).
All elemental data used to calculate the geochemical indices are pre-
sented as oxides because the main balancing anion is usually oxygen
and weathering indices have therefore been generated using elements
in their oxide form (Birkeland, 1999).
There is a range of molar ratios that have been used to investigate the
degree of chemical weathering within rocks and soil profiles. Most com-
pensate for different molecular weights of the oxides used in the calcu-
lations by determining the relative number of atoms. This is achieved by
dividing the percentage of the oxide of interest in a sample by its molec-
ular weight (Birkeland, 1999). At the moment, because of the limit of
detection for various elements of current handheld pXRF spectrometers,
there is only a handful of molar ratios or weathering indices that can be
employed in conjunction with pXRF measurements. In particular, the
operational setup of contemporary pXRF devices is not sufficient to
225
detect the element sodium (Na), which is used in numerous weathering
indices. However, as technology evolves, this might become possible in
the future.
The general principle behind geochemical indices is the assumption
that the content of a weatherable (mobile) mineral in the soil decreases
whereas the content of a resistant (immobile) mineral increases propor-
tionally throughout the weathering process (Taylor and Eggleton,
2001). For example, major oxides such as Al2O3, Fe2O3 or TiO2 are con-
sidered immobile, whereas SiO2, K2O, Na2O, MgO and CaO are consid-
ered mobile. The concentration of these oxides in the soil therefore
varies in relation to pedogenic processes, and relative to the parent
rock. More specifically, most of the major elements such as Mg, Ca, K
and Na are depleted during soil formation in a leaching environment.
The amount of SiO2 in the soil also generally decreases with weathering
intensity relative to the parent material. Al2O3 on the other hand has a
low solubility under normal weathering pH and as it is an essential
part of most clay minerals, its content generally increases in weathered
materials. Most fresh rock contains Fe in its ferrous state (Fe2+) where it
is quite soluble and can be leached through percolating waters, but most
weathering occurs in oxidizing conditions where Fe is present in its fer-
ric (Fe3+), insoluble form, and becomes part of Fe-bearing minerals and
clay minerals (Fe2O3). Therefore, Fe also has the tendency to remain
in weathered materials. In general, Ti is also immobile as it forms
part of various minerals such as rutile, ilmenite, micas and pyroxenes
(Birkeland, 1999; Maynard, 1992; Schaetzel and Anderson, 2005).
Geochemical index values are assumed to decrease with weathering
intensity in a leaching environment, so in well-developed (in-situ) soils
these index values should increase with depth (Schaetzel and Anderson,
2005). In this study, we employed the following weathering indices to
show how they can be applied to investigate pedogenesis in the field:
• Ruxton weathering index — SiO2 / Al2O3
The Ruxton weathering index developed originally to assess the ex-
tent of chemical weathering in rocks (Ruxton, 1968) relates the loss of
silica to total elemental loss during weathering. Silica is assumed to be
the mobile oxide whereas the sesquioxidic aluminium is assumed to
be the immobile element during weathering. A decreasing Ruxton
weathering index value is indicative of an increase in weathering inten-
sity. This ratio is usually related to a scale between 0 and 10 where 0 is
considered the optimum weathered value whereas 10 is considered to
be the optimum fresh value. In general, the Ruxton index is best suited
to investigating the weathering history of soils evolved from uniform
acid to intermediate bedrock (Fiantis et al., 2009).
• Desilication index — SiO2 / (Al2O3 + Fe2O3 + TiO2)
The desilication index after Singh et al. (1998) is a molar ratio of sil-
ica to resistant oxides. Substituting Zr for Ti may be useful as Ti has the
potential of being mobile during the weathering process. This index can
be calculated by horizon, weighted by horizon or summed for the entire
profile.
In addition, we also used the elemental ratio of Ti and Zr, elements
that are considered resistant to weathering, to investigate pedogenesis:
• Elemental ratio of elements resistant to weathering — Ti / Zr
Both of these elements are considered to be relatively resistant to
weathering, and so their amounts generally increase proportionally
during weathering. It is therefore assumed that the Ti/Zr ratio remains
constant throughout a soil profile under in-situ soil formation. As both
elements are generally considered immobile this ratio is also a good in-
dicator of the origin and homogeneity of parent material(s) (Maynard,
1992).
2.5. Portable XRF in-field performance
The in-field performance of the pXRF is affected by a range of factors
that can lead to an over- or under-estimation of elemental contents. The
226 U. Stockmann et al. / Catena 139 (2016) 220–231

Fig. 7. a. Concentrations of major elements with increasing depth in the Vertosol profile, assessed in both field condition and air-dried and ground condition. b. Concentration of major
elements with increasing depth in the Chromosol profile, assessed in both field condition and air-dried and ground condition. c. Concentrations of major elements with increasing
depth in the Sodosol profile, assessed in both field condition and air-dried and ground condition.

Table 1
Major element concentrations for the expected Nowley Farm soil parent materials.

Parent material Soil type Al Si Fe K Ca Mn Ti Zr

(%) (%) (%) (mg kg−1) (mg kg−1) (mg kg−1) (mg kg−1) (mg kg−1)

Sample condition: rocks in field condition

Jurassic basalt Black Vertosol 5.8 16.6 7.2 11,000 72,300 1016 10,200 113
Jurassic dolerite Black Vertosol 4.5 14.7 8.9 5227 21,700 3652 12,600 96
Jurassic Purlewaugh Beds mudstone Red Chromosol 5.7 15.0 17.6 21,200 b50 314 18,850 306
Jurassic Purlewaugh Beds and Pilliga sandstone Brown Sodosol 4.6 30.8 0.5 2975 349 b10 1983 65

Sample condition: air-dry, pulverized

Jurassic basalt Black Vertosol 9.9 21.0 7.6 13,069 79,040 1236 10,889 194
Jurassic dolerite Black Vertosol 8.9 20.0 7.3 8881 57,687 1275 7365 146
Jurassic Purlewaugh Beds mudstone Red Chromosol 11.5 20.1 28.2 2915 b50 1979 4365 260
Jurassic Purlewaugh Beds and Pilliga sandstone Brown Sodosol b1.0 45.2 0.1 64 1810 31 1417 192
 U. Stockmann et al. / Catena 139 (2016) 220–231
most significant effect is related to the nature of the sample matrix, i.e.
the less homogeneous the sample, the less precise is the estimate
(Hou et al., 2004; Laiho and Perämäki, 2005; Markowicz, 2008). Fur-
thermore, soil moisture can also affect the estimation of the elemental
concentrations through pXRF (Ge et al., 2005). Low atomic number ele-
ments such as Al, Si and Ti which are important for weathering studies
are especially affected. In addition, a recent study by Brand and Brand
(2014) found that the performance of handheld pXRF spectrometers is
also related to the manufacturer's internal calibrations, which need to
be updated regularly. Deterioration of the instrument's performance
can occur within several months after calibrations through the manu-
facturer. The instruments battery-packs can also have a measureable in-
fluence on the instrument's performance. It is therefore important to
keep track of these changes by testing the pXRF's performance using
NIST standards prior to every sampling round. Because of these various
influences on the pXRF's performance, in this work we compared the el-
emental and geochemical index estimates acquired from the field mea-
surements of soil and rock with those acquired in the laboratory using
the air-dried and ground (b 2 mm) soil samples, and the air-dried and
pulverized rock samples.
3. Results and discussion
3.1. Concentrations of major elements down the soil profile
Fig. 7a, b and c shows the depth functions of K, Ca, Fe, Mn and Ti,
measured by pXRF in field condition as well as air-dry, ground condi-
tion. It is immediately evident that for certain elements and profiles,
the estimates of element concentration vary markedly between the
field and laboratory measurements, but for both scanning conditions
the changes in elemental concentrations down the profile follow gener-
ally similar trends. Similarly, in some cases, the major elemental con-
centrations of the rock samples (Table 1) vary quite considerably
between the field and laboratory scanning conditions, but the order of
magnitude for the various elements in the four rock types is generally
consistent.
For the Vertosol profile, most element concentrations are relatively
constant down the profile (Fig. 7a), which relates well to the uniformly
high clay content of this soil. A slight enrichment of elements such as Fe
and Mn occurs, however, where the texture grade reaches a heavy clay
at around 0.6 m depth. A prominent spike in Ca content below 0.6 m
depth is related to the presence of secondary carbonates (calcite) at
depth. Comparing the Vertosol elemental data with that of the four
Nowley rock types sampled (Table 1), the Fe, Mn and Ti data in particu-
lar show a strong match to the basalt and dolerite.
The variation of most elements down the profile is also relatively
minor for the Chromosol but this profile development also shows
some loss and enrichment of elements in the topsoil and subsoil. The
Fe content is relatively high at about 4% throughout the profile, but
based on either the field or laboratory scanning, there is enrichment
in Fe content noticeable in the Bt2 horizon between the depths of 0.2
and 0.4 m, which presumably reflects the accumulation of clay by
argilluviation evident in Fig. 4a. The Mn concentration varies somewhat
with depth, showing depletion in the Bt2 horizon and enrichment in the
adjacent horizons. The prominent spikes in Ca content below 0.7 m
depth are also related to the formation of secondary carbonates (calcite)
through processes of calcification. The comparison of the Chromosol el-
emental data to that of the potential parent rocks does not give a clear
match, the Chromosol Ca concentrations suggest a contribution from
basalt or dolerite, while K, Mn and Ti concentrations are more consistent
with an input from the mudstone. The large discrepancies in elemental
values between the field and laboratory-scanned mudstone samples
makes this comparison difficult, but it seems likely that the Chromosol
has a combination of generally fine-grained parent rocks.
In contrast to the Vertosol and Chromosol, for the Sodosol, most el-
ement concentrations show a very distinct increase in the B horizons
227
below the occurrence of the silicified layer at a depth of 0.45 m. Concen-
trations of the major elements K, Fe and Ti increase sharply in alignment
with the abrupt change in texture from a sand in the topsoil to a light to
medium clay in the subsoil. This indicates that there is a change in ma-
terials and an enrichment in clay minerals caused by the processes of
argilluviation (Fig. 5b). The Ca and Mn concentrations do not show
this trend and are uniformly low throughout the profile. Elemental
concentrations of the Sodosol topsoil match very well with those of
the sandstone, while those of the subsoil match quite well those of the
mudstone.
3.2. Investigating pedogenesis employing geochemical indices and elemen-
tal ratios sourced from pXRF measurements
3.2.1. Changes in geochemical indices and elemental ratios with soil depth
As in the case of the elemental concentration data, although there
are some substantial differences in geochemical index and elemental
ratio values obtained under field and laboratory scanning conditions,
the depth trends are generally similar. The Ruxton and Desilication
index values for the Vertosol (Fig. 8a) and Chromosol (Fig. 8b) soil pro-
file change only marginally down the profile, especially those calculated
from laboratory scanned elemental data. There is no clear tendency,
for these index values to increase with soil depth, suggesting that
weathering intensity or duration has varied little in these profiles. The
Ruxton index values for the Chromosol profile range between 1 and 4
whereas the values for the Vertosol profile are slightly lower, ranging
between 1 and 2, with soil depth. Similarly, for the Desilication index,
the Chromosol values range between 0.4 and 1.2, whereas the Vertosol
values range between 0.3 and 0.9. These different ranges of values
presumably reflect the different parent rocks of the two soils. The
Ti/Zr elemental ratio depth functions for the Vertosol and Chromosol
are conspicuously more variable, particularly in the B horizons and par-
ticularly for the field-based measurements, but again there is no consis-
tent trend with depth. The Ti/Zr ratio of the Vertosol is approximately
twice that of the Chromosol, again reflecting the different parent mate-
rials of the two soils.
From a pedogenetic point of view we can conclude that the Vertosol
and Chromosol profiles have both been derived from long-term
weathering of colluvium, but that the sources of the colluvial materials
differ somewhat for the two soils. To strengthen this argument we com-
pared the index and elemental ratio values of the soil profiles with those
of the four Nowley rock types (Table 2). The geochemical index values
of the basalt, dolerite and mudstone are all similar to each other, and
so are not good discriminators of likely soil parent material in this con-
text, but the Ti/Zr ratios, of the basalt and dolerite were distinctly higher
than those of the mudstone. This difference is mirrored in the compari-
son of the Vertosol and Chromosol Ti/Zr ratios, strengthening the notion
that the Vertosol is derived from colluvium sourced from the basalt and
possibly dolerite, while the Chromosol is derived from colluvium
sourced primarily from mudstone, but also some basalt and/or dolerite.
In contrast to the generally uniform geochemical trends in the
Vertosol and Chromosol, the Ruxton and Desilication indices and Ti/Zr
ratio of the Sodosol profile do show a conspicuous change with soil
depth (Fig. 8c). Prominent spikes in all three geochemical measures
occur at the boundary between the A and E horizons and above the
Btqn horizon (Fig. 8c). The Ruxton index value changes significantly
throughout the soil profile, with the A horizon having a value close to
10, the E horizon reaching a maximum value of 55 between 0.3 and
0.5 m depth, and the B horizons showing values of less than 4 from a
depth of 0.6 m. These Ruxton index values suggest that the clayey B
horizons have experienced the longest weathering history and/or
that they evolved from different parent material. Both, the Ruxton and
Desilication index values from the E horizon are very similar to the
values calculated for the Purlewaugh Beds and Pilliga sandstone
(Table 2), which suggests to us that the upper part of the Sodosol profile
is evolved from alluvial and colluvial deposits sourced from these
228 U. Stockmann et al. / Catena 139 (2016) 220–231
 U. Stockmann et al. / Catena 139 (2016) 220–231 229

Table 2
Geochemical indices and elemental ratio readings for the expected Nowley Farm soil parent materials.

Parent material Soil type Ruxton index Desilication index Stable element ratio

Sample condition: rocks in field condition

Jurassic basalt Black Vertosol 1.6 0.8 90.3
Jurassic dolerite Black Vertosol 1.9 0.7 131.3
Jurassic Purlewaugh Beds mudstone Red Chromosol 1.5 0.4 61.7
Jurassic Purlewaugh Beds and Pilliga sandstone Brown Sodosol 3.8 3.5 30.4

Sample condition: air-dry, pulverized

Jurassic basalt Black Vertosol 1.2 0.7 56.2
Jurassic dolerite Black Vertosol 1.3 0.8 50.4
Jurassic Purlewaugh Beds mudstone Red Chromosol 1.0 0.3 16.8
Jurassic Purlewaugh Beds and Pilliga sandstone Brown Sodosol 51.1 29.1 7.4

Fig. 9. Comparison of geochemical indices values and the elemental ratio of Ti/Zr, calculated from soil samples in field condition and air-dried and ground condition.

sandstones. The subsoil, however, with its very low Ruxton and
Desilication index values, and Ti/Zr ratios similar to those of the
Chromosol, looks to have formed through the long-term weathering
of alluvium and colluvium sourced from the Purlewaugh Beds mud-
stone. In conclusion, the geochemical changes throughout the Sodosol
profile indicate that the topsoil did not evolve from the same parent ma-
terial as the subsoil, and the Sodosol profile can thus be regarded as con-
taining a lithological discontinuity. Considerable changes in weathering
indices values down the Sodosol profile confirm that the pedogenesis
model set-out by Hallsworth and Waring (1964) for solodized-
solonetz soils of northern New South Wales discussed in Section 2.2,
cannot be applied here. The results strengthen our proposal of an alter-
native pedogenic pathway, i.e. that sandy colluvium sourced from Juras-
sic sandstone has been deposited over a pre-existing sodic, clayey
alluvium to produce a texture-contrast, solonetzic profile.
For all three profiles examined, the Ti/Zr ratio values showed consid-
erably more variability with depth than the other two indices. Maynard
(1992) discussed that this variability is generally related to soil mineralo-
gy. During weathering zirconium will most likely reside in zircon which is
considered to be one of the most weathering resistant minerals. In con-
trast, titanium will most likely reside in minerals that are comparatively
more easily weathered such as mica or ilmenite. In addition, clay mobility
throughout the profile which becomes more pronounced after alkalis are
leached out can also influence the vertical distribution of these elements.
If one element (most likely Ti) is redistributed through dissolution or clay
eluviation, the Ti/Zr ratio tends to increase with depth, a tendency that is
noticeable for the Sodosol profile in particular.
3.2.2. Comparison of in-field and laboratory-based pXRF performance
As discussed in Section 2.4, scanning the soil in field condition is
affected by several factors such as soil matrix heterogeneity, sample
density, surface roughness and soil moisture. Geochemical indices and
elemental ratio values calculated from soil samples scanned in field con-
dition were therefore related to those scanned in air-dry, ground condi-
tion. This relationship was evaluated using x–y plots and the values of
goodness of fit, i.e. the R2 (R squared coefficient of determination) and
the RMSE (root mean squared error) (Horta et al., 2015). Here, it is as-
sumed that weathering indices values calculated from the air-dry,
ground data are more precise as they are in the same condition as the
standards used to calibrate the pXRF.
Fig. 9 and Table 3 show the goodness of fit for all soil profiles and it is
evident that indices/ratio values acceptably compare. The relationship
between weathering index values calculated from air-dried and ground
samples as compared to field-moist samples shows good agreement,
with R2 values of 0.79, 0.81 and 0.61 for the Ruxton index, Desilication
index and Ti/Zr elemental ratio, respectively. The Desilication index
values exhibit the best fit with the highest R2 and the lowest RMSE.
This is most likely due to the fact that the limit of detection varies for
the pXRF elemental concentrations used to populate the weathering in-
dices; with b 1% (Al, Si), b 10 mg kg−1 (Fe, Ti) and b5 mg kg−1 (Zr); and
the abundance of these elements naturally in the soil. The detection of
lighter elements in respect to the periodic table such as Al, Si and Ti, is
also affected by the fact that these cannot be measured as sufficiently
with current operational pXRF setups. This is due to their (reduced)
fluorescence signal after X-ray excitation and thus the presence of less

Fig. 8. a. Pattern of geochemical indices and the elemental ratio of Ti/Zr with increasing depth in the Vertosol profile, assessed in both field condition and air-dried and ground condition. b.
Pattern of geochemical indices and the elemental ratio of Ti/Zr with increasing depth in the Chromosol profile, assessed in both field condition and air-dried and ground condition. c.
Pattern of geochemical indices and the elemental ratio of Ti/Zr with increasing depth in the Sodosol profile, assessed in both field condition and air-dried and ground condition.
230 U. Stockmann et al. / Catena 139 (2016) 220–231
Table 3
Goodness of fit of comparisons of geochemical indices and elemental ratio of Ti/Zr values,
calculated from soil samples in field condition and air-dry, ground condition.
Geochemical index/elemental ratio R2 RMSE
Ruxton index 0.79 8.58
Desilication index 0.81 3.97
Ti/Zr elemental ratio 0.61 29.54
distinct fundamental peak(s). All of these factors affect the measure-
ment of these elements under field conditions.
For example, Fe (Fe2O3) is used as part of the immobile elements in
the calculation of the Desilication index and previous research has
shown that Fe concentrations measured from samples in field-moist
condition compared very well to air-dried and ground conditions
(Stockmann et al., in press). In addition, Fe is usually found in high con-
centrations in the soil, considerably above its pXRF detection limit. For
lighter elements such as Al, Si and Ti, and/or elements whose concentra-
tions in the soil are closer to their pXRF detection limit (e.g. Al and Ti),
measured quantities show much more variability between field-moist
and air-dried and ground conditions.
There is the possibility, however, to fit a linear relationship, and cor-
rect for measurements taken in field conditions by applying a correction
factor which was proposed and successfully applied in Stockmann et al.
(in press):
Ruxton index (air-dry) = 0.0257381 + 1.4367172 × Ruxton index
(field-moist)
Desilication index (air-dry) = 0.3931542 + 1.4465694 × Desilication
Desilication index (field-moist)
Ti/Zr ratio (air-dry) = 4.5874652 + 0.3908987 × Ti/Zr ratio (field-
moist).
4. Conclusions
In this study, pXRF elemental data measured in field condition were
employed to investigate the pedogenetic pathways of three distinct soil
profiles, a Black Vertosol, a Red Chromosol and a Brown Sodosol.
Although these three soil profiles are found within relatively close prox-
imity to each other, they have originated from a variety of parent mate-
rials. When coupled with measurements of elemental concentrations
from assumed parent rocks, we found that in-field pXRF elemental mea-
surements were very effective for verifying soil parent materials, and for
objectively identifying the main pedological processes that have been
operating on these soils. Portable XRF spectroscopy offers a rapid, inex-
pensive, non-destructive alternative to laboratory-based geochemical
techniques for generating soil elemental concentration data, and can
add considerable value to in-field soil description for the objective
assessment of soil formation pathways. We found that the use of
pXRF is a very effective in-field tool to assess pedogenic pathways and
parent material origin, because of the virtually instant computation of
weathering indices and elemental ratios. Our results show that elemen-
tal data acquired in field condition which are affected by sample hetero-
geneities and soil moisture are comparable to elemental data acquired
in air-dried and ground condition, as geochemical index values show
similar trends down the soil profile.
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