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Journal of Geochemical Exploration: Krishangi D. Groover, John A. Izbicki

This document summarizes a study that analyzed the concentrations of 27 elements, including arsenic, chromium, and uranium, in 217 samples of alluvium and rock from the western Mojave Desert in southern California using portable and laboratory X-ray fluorescence. Principal component analysis showed that different source terrains were associated with distinct elemental assemblages in the alluvium. Changes in the geologic source terrain along the Mojave River over the past 1-5 million years reduced the mafic fraction and increased the felsic fraction of alluvium, lowering chromium concentrations. Comparison of portable X-ray fluorescence and sequential extraction data suggested arsenic and uranium were more readily mobilized than chromium or vanadium.

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0% found this document useful (0 votes)
149 views15 pages

Journal of Geochemical Exploration: Krishangi D. Groover, John A. Izbicki

This document summarizes a study that analyzed the concentrations of 27 elements, including arsenic, chromium, and uranium, in 217 samples of alluvium and rock from the western Mojave Desert in southern California using portable and laboratory X-ray fluorescence. Principal component analysis showed that different source terrains were associated with distinct elemental assemblages in the alluvium. Changes in the geologic source terrain along the Mojave River over the past 1-5 million years reduced the mafic fraction and increased the felsic fraction of alluvium, lowering chromium concentrations. Comparison of portable X-ray fluorescence and sequential extraction data suggested arsenic and uranium were more readily mobilized than chromium or vanadium.

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Ruliansyah L
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

Contents lists available at ScienceDirect

Journal of Geochemical Exploration


journal homepage: www.elsevier.com/locate/gexplo

Selected trace-elements in alluvium and rocks, western Mojave Desert,


southern California
Krishangi D. Groover , John A. Izbicki

U.S. Geological Survey, California Water Science Center, 4165 Spruance Road, Suite 200, San Diego, CA 92101, United States of America

ARTICLE INFO ABSTRACT

Keywords: Concentrations of twenty-seven elements, including naturally-occurring water-quality contaminants arsenic,


Arsenic chromium, and uranium, were measured in 217 samples of alluvium and rock from the western Mojave Desert,
Chromium southern California, using portable (pXRF) and laboratory (LXRF) X-ray fluorescence. Comparison of measure-
Regional geochemistry ments with NIST-traceable standards was good, although pXRF overestimated iron compared to LXRF. Results
Sequential extractions
suggest pXRF survey data are sufficiently accurate to assess regional geochemical differences in geologic-source
Uranium
X-ray fluorescence
terrains. Principal component analysis showed rubidium and potassium were associated with alluvium eroded
from felsic terrain, while iron, copper, chromium, and to a lesser extent titanium, manganese, and nickel were
associated with alluvium eroded from mafic terrain. Zinc, vanadium, and arsenic were associated with alluvium
eroded from hydrothermal terrain. Elemental assemblages associated with different source terrains were traced
spatially to identify the source and composition of alluvium composing aquifers pumped for water supply.
Changes in geologic source terrain to the Mojave River, associated with movement along the San Andreas Fault
over the past one to five million years, reduced the mafic fraction and increased the felsic fraction of alluvium
deposited to the regionally important floodplain aquifer along the Mojave River—lowering chromium con-
centrations in alluvium through geologic time. Comparison of pXRF and sequential extraction data from 40
samples showed arsenic and uranium were more abundant on the surfaces of mineral grains, while chromium
and vanadium remained mostly within unweathered mineral grains—suggesting arsenic and uranium may be
more readily mobilized into groundwater with changes in pH, redox, or ionic strength than chromium or va-
nadium.

1. Introduction similar patterns in elemental distributions. However, alluvium from


stream channels often provides a better approximation of average
Large-scale geochemical surveys are an efficient method of evalu- concentrations within the larger area of the stream drainage than other
ating the distribution of elements in the near-surface environment matrices (Webb et al., 1964), and provides data on the trace element
(Graham et al., 2015). Data from these surveys are important for mi- composition of bedrock upstream of the sample point (Chaffee, 1975;
neral exploration, risk-based assessment of contaminated land, en- Painter et al., 1994; Webb et al., 1964). With the exception of areas
vironmental regulation, human and animal health, agriculture, land-use near large fault systems, alluvium in stream channels also may be
planning, and water quality. Over the years numerous regional, na- considered a proxy for the composition of nearby alluvial aquifers,
tional, and international-scale surveys describing the elemental and which typically contain alluvium eroded from surrounding areas.
mineral composition of the near-surface environment have been com- In the United States, large-scale geochemical surveys were first at-
pleted (Gough et al., 1988, 2005; Graham et al., 2015; Shacklette and tempted in 1947 (Hawkes, 1976), but systematic, national-scale geo-
Boerngen, 1984; Shacklette et al., 1971; Smith et al., 2014; U.S. chemical surveys of soils and plants were not done until 1961
Geological Survey, 2004; Webb et al., 1978). These surveys commonly (Shacklette et al., 1971). These surveys were periodically updated
use rock, soil, plants, or alluvium from stream channels as the sample (Shacklette and Boerngen, 1984; Gough et al., 1988, 2005) with the
medium and commonly display elemental abundances and spatial most recent national-scale survey published by Smith et al. (2014). In
variation in map format (Reimann, 2005). these continental-scale surveys, sample density is necessarily low, and
Geochemical surveys of rock, soil, and stream sediments reveal the most recent continental-scale survey by Smith et al. (2014) had a


Corresponding author.
E-mail address: kgroover@usgs.gov (K.D. Groover).

https://doi.org/10.1016/j.gexplo.2018.09.005
Received 4 February 2017; Received in revised form 25 August 2018; Accepted 3 September 2018
0375-6742/ Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/BY-NC-ND/4.0/).

Please cite this article as: Groover, K.D., Journal of Geochemical Exploration, https://doi.org/10.1016/j.gexplo.2018.09.005
K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

sample density of one sample per 1600 square kilometers (km2). Grid- 2016).
based sampling approaches used in continental-scale surveys are ef- The most productive aquifer within the Mojave River Groundwater
fective at determining the chemical composition of a large area, but Basin is the floodplain aquifer, which extends along the length of the
may neglect local-scale variations in chemistry that could be captured Mojave River (California Department of Water Resources, 2003; Stamos
by other, more detailed sampling approaches. et al., 2001). The floodplain aquifer is commonly < 1 to 2 km wide and
The study area in the western part of the Mojave Desert, California, typically < 70 m thick (Stamos et al., 2001), and is surrounded and
between 100 and 200 kilometers (km) northeast of Los Angeles (Fig. 1), underlain by a regional aquifer composed of older Mojave River de-
is composed of multiple closed basins containing alluvium eroded from posits (Pliocene to Pleistocene age) and alluvium eroded from local
surrounding mountains. Weathering of minerals within alluvium and mountains. Older Mojave River alluvium covers a large area within the
rock from these areas may release a range of elements into groundwater Mojave River Groundwater Basin, ranging from Deep Creek in the
under the proper geochemical conditions (Hem, 1992). Except for some southwest and extending nearly to Barstow in the central part of the
streams at high elevations on the edge of the study area, there are no study area (Fig. 1B; Stamos et al., 2001). For the purposes of this report,
perennial streams, and groundwater is the only dependable source of the older Mojave River deposits also include the Victorville fan (Fig. 1B;
water supply. Meisling and Weldon, 1989), which was deposited by streams that were
Groundwater quality in alluvial aquifers underlying the western tributary to the Mojave River before the fan was beheaded by erosion
Mojave Desert has been most recently described by Dawson and Belitz along the San Andreas Fault. The Morongo Groundwater Basin, and
(2012) and Metzger et al. (2015), and some recent work has linked parts of the study area not included in the Mojave River Groundwater
naturally occurring trace elements in groundwater, such as chromium Basin, are composed of numerous small alluvial basins separated by
and vanadium, to weathering of minerals eroded and transported from faults and bedrock outcrops (California Department of Water Resources,
rocks in upland drainages (Izbicki et al., 2008; Wright and Belitz, 2003).
2010). Some high concentrations of trace elements dissolved in Bedrock is dominated by felsic plutonic and volcanic rocks, with
groundwater in exceedance of California maximum contaminant levels lesser amounts of mafic plutonic and volcanic, metamorphic, and se-
(MCL) may be naturally occurring and attributable to local geologic dimentary rocks that are commonly overlain by alluvial and playa de-
sources (Dawson and Belitz, 2012; Izbicki et al., 2008; Metzger et al., posits (Fig. 1B; Dibblee, 1967; Jennings et al., 2010). Rocks have been
2015). Given the widespread occurrence of trace elements in ground- locally altered and mineralized by hydrothermal activity, and a number
water from alluvial aquifers in the area, geochemical-survey data tar- of active and historic mining operations have targeted gold, silver, and
geting alluvium within stream channels eroded from specific geologic boron resources (U.S. Geological Survey, 2005a, 2005b). Hydro-
source terrains may help identify natural geologic sources of selected thermally altered rocks have not been formally mapped at the regional
trace elements. scale, and are not shown on Fig. 1B.
The purpose of this paper is to evaluate concentrations of selected The San Bernardino Mountains, composed largely of granitic rock,
trace elements from natural geologic sources in alluvium and rocks in form the southern boundary of the study area and contain high con-
the western Mojave Desert, and assess the potential mobility of selected centrations of uranium (U.S. Geological Survey, 2004). The San Gabriel
trace elements such as arsenic, chromium, and uranium to ground- Mountains southwest of Victorville are composed of a wider variety of
water. The scope of this study included field collection and elemental rock types including the Pelona Schist (Ehlig, 1958, 1968), which is a
analyses of samples from alluvium in stream channels and from rock in gray mica-schist (Ehlig, 1958; Evans, 1982) containing a minor (5% of
upland source areas that compose specific geologic source terrains. The the total mapped formation) mafic greenschist facies (Evans, 1982).
study also included comparison of elemental analyses from various The greenschist facies contain actinolite and mica with high con-
sample matrixes, made using different techniques, to determine how centrations of chromium, iron, and nickel (Izbicki et al., 2008). Sedi-
available these elements may be to groundwater under changing pH, ment eroded from the Pelona Schist composes the Sheep Creek alluvial
redox, and ionic strength. fan that extends northward from the mountains towards El Mirage (dry)
This paper is part of a larger study of trace element concentrations Lake (Fig. 1) (Izbicki et al., 2008; Meisling and Weldon, 1989; Miller
in rock, alluvium, and groundwater in the western Mojave Desert. and Bedford, 2000; Stamos et al., 2001).
Ongoing work addresses the aqueous geochemistry of selected naturally Movement along the right-lateral San Andreas Fault, near the
occurring trace elements dissolved in groundwater in the area. southwestern margin of the study area (Fig. 1B), has transported the
mafic Pelona Schist to the northwest over the last one to five million
2. Description of study area years to its present position in the San Gabriel Mountains near the
headwaters of Sheep Creek (Cox et al., 2003; Meisling and Weldon,
The study area includes the Mojave River and Morongo 1989). This movement has changed geologic source areas contributing
Groundwater Basins (California Department of Water Resources, 2003), alluvium to the Mojave River and the Victorville fan over time (Cox
and smaller groundwater basins within Fort Irwin National Training et al., 2003; Izbicki et al., 2008). Consequently, older Mojave River
Center to the northeast (Fig. 1A). Elevations within the study area range deposits contain a greater fraction of material eroded from the Pelona
between 450 and 2600 m, and precipitation ranges from 110 milli- Schist than present-day Mojave River alluvium (Cox et al., 2003;
meters per year (mm/yr) near Barstow in the central part of the study Meisling and Weldon, 1989). Multiple smaller northwest striking faults
area, up to 1000 mm/yr, in the higher altitudes of the San Bernardino also are active within the study area (Dibblee, 1967; Glazner et al.,
and San Gabriel Mountains to the southwest (Fig. 1A; Izbicki et al., 2002; Miller and Yount, 2002), and movement along these faults may
2008). have resulted in similar, smaller-scale changes in local alluvial source
The area is internally drained, with several large ephemeral streams terrains.
that flow from south to north. The Mojave River, the largest of these Groundwater in alluvial aquifers within the study area is generally
streams, extends nearly 200 km from the San Bernardino and San oxic, with neutral to alkaline pH (Dawson and Belitz, 2012; Metzger
Gabriel mountains south of Victorville to its terminus east of Afton et al., 2015). Except for groundwater in the floodplain aquifer re-
Canyon (Fig. 1A; Thompson, 1929). The Mojave River is typically dry charged by occasional large flows along the Mojave River, most
along most of its reach, except where groundwater discharge maintains groundwater in the study area was recharged many thousands of years
perennial streamflow near the Upper and Lower Narrows at Victorville, ago (Izbicki and Michel, 2004). Groundwater ages in the regional
and near Afton Canyon. Large flows, extending the entire length of the aquifer increase to > 20,000 years away from the mountain front and
Mojave River from the mountain front to Afton Canyon, occur on away from the Mojave River (Ball and Izbicki, 2004; Izbicki and Michel,
average every 5 to 7 years (Lines, 1996; Stamos et al., 2001; Seymour, 2004). The chemistry and age of groundwater combine to create

2
K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

Fig. 1. Sample locations (A), and generalized surficial geology (B) within the western Mojave Desert, southern California.
3
K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

conditions that may allow certain naturally occurring trace elements analyzer (Olympus, Waltham, MA), equipped with a 4-watt Ta/Au X-
such as arsenic, chromium, uranium, and vanadium in alluvium to ray tube operated between 15 and 40 keV in “Soil” mode. Each mea-
enter groundwater at concentrations that may be a public health con- surement was done for 2 min across an oval area approximately 5 mm
cern (Ball and Izbicki, 2004; Dawson and Belitz, 2012; Hem, 1992; across its larger diameter, and was generally repeated 3 times per
Izbicki and Michel, 2004; Metzger et al., 2015). sample to assess variability in composition. Measurements were opti-
mized for high concentrations of chromium (based on instrument per-
formance with standard reference materials) by adjusting instrument
3. Methods settings when samples with high chromium concentrations were en-
countered.
A total of 161 samples of alluvium, 36 samples of rock, and 20 Two NIST (National Institute of Standards and Technology) soil
subsamples of alluvium from 8 wells (drilled between 2011 and 2013) standards (2710a and 2711a), a USGS rock standard (BHVO-2), and a
were collected between January 2014 and June 2016 (Supplementary silicon dioxide blank (99.99% purity) were measured daily using por-
Data A). Most alluvial samples were collected from small stream table X-ray fluorescence (pXRF) before data collection to monitor the
channels draining distinct geologic source terrains. Detailed, closely- accuracy of the measurements (Supplementary Data B). Data quality
spaced sampling along the length of the Mojave River and other large associated with measurements, chromium-optimized measurements,
streams was done to evaluate changes in alluvium chemistry with and non-optimized measurements are presented in Table 1. Most
changes in bedrock along the stream length. Most alluvium samples measurements were within ± 10% of the NIST- and USGS-certified
consisted of silt, sand, and granules to small pebbles, and generally did standard values. Blank data showed contamination at low levels for
not contain material that had been extensively altered by soil-forming titanium (12–20 mg/kg) and iron (9–10 mg/kg), representing 0.74 and
processes (dissolution and precipitation, hydrolysis, etc.). Rock samples 0.05% of the average concentrations for these elements, respectively.
from selected locations provide compositional end members for dif- Laboratory XRF (LXRF) measurements for major and trace elements
ferent geologic source terrains. Samples were taken to the U.S. were completed on splits from 33 samples of alluvium and core sam-
Geological Survey (USGS) San Diego office to allow for consistent ples. For major elements, samples were powdered, homogenized, and
sample preparation and handling prior to measurement. The average fused into a glass disk at 1000 °C. For trace elements, samples were
sample density in this study is one sample per 80 km2, which is much powdered, mixed with elvacite (a plastic binder), and compressed into
denser sampling than the one sample per approximately 1600 km2 disks using 23 tons of pressure (Supplementary Data C). Samples were
within the study area available from the most recent continental-scale analyzed using a wavelength dispersive LXRF (Philips MagiX PRO) at
survey by Smith et al. (2014). San Diego State University. The LXRF is equipped with a 4000-watt X-
A total of 831 measurements were completed on alluvium and core ray tube, approximately 1000 time more powerful than the X-ray tube
material, and 112 measurements were done on samples of rocks. in the pXRF. LXRF data were compared to pXRF data to determine
Sample preparation for alluvial material consisted of manually re- accuracy of pXRF data.
moving cobbles and twigs from the sample and either air drying or oven Sequential extractions were done on splits from 40 samples of al-
drying samples at 80 °C for 4 h prior to measurement. Sample pre- luvium and core material to determine the concentrations of selected
paration for rocks consisted of rinsing a freshly exposed surface with trace elements on operationally-defined sorption sites on the surfaces of
tap water, and allowing the sample to air dry prior to measurement. mineral grains. Extractions, done using progressively stronger extrac-
Samples were analyzed for 27 elements (Supplementary Data A) using a tion solutions, were prepared at the USGS San Diego Office using a
portable energy-dispersive DP-4000 Delta Premium X-ray fluorescence

Table 1
Portable X-ray fluorescence (pXRF) measurements compared to National Institute of Standards and Technology (NIST) 2710a, NIST 2711a, and U.S. Geological
Survey (USGS) BHVO-2 standard reference materials.
All measurements Chromium-optimized measurements Non-optimized measurements
(n = 239) (n = 78) (n = 161)

Element Average percent of reference Intercept Average percent of reference Intercept Average percent of reference Intercept
concentration concentration concentration

Arsenic (As) 93 −16 98 N.D. 90 −16


Calcium (Ca)a 104 −4150 N.D. N.D. 104 −4150
Chromium (Cr) 118 16 100 −2 130 25
Copper (Cu) 100 2 116 37 90 −14
Iron (Fe) 100 −2461 105 5568 97 −3513
Lead (Pb)b 97 −2 98 N.D. 97 2
Manganese (Mn) 95 −130 98 −178 92 −120
Mercury (Hg)b 437 −125 580 N.D. 366 −123
Nickel (Ni) 95 5 90 2 98 6
Potassium (K)a 92 −1148 N.D. N.D. 92 −1148
Rubidium (Rb) 91 −2 92 −2 91 −2
Selenium (Se)b 588 14 837 N.D. 464 14
Strontium (Sr) 100 −7 102 7 99 −6
Titanium (Ti) 108 −479 117 −225 103 −352
Uranium (U)b 94 3 83 10 100 3
Vanadium (V) 338 240 322 260 348 229
Zinc (Zn) 94 −32 103 0 88 −41
Zirconium (Zr)b 143 −368 145 −375 141 −370

“N.D.” = no data available; “Optimized” = measurements were optimized by adjusting instrument beam settings to measure chromium accurately.
a
Data not available from chromium-optimized measurements.
b
Standard reference concentrations not available for all standards. Bold font indicates accuracy of ± 10% of standard reference value or better; italics indicate
statistically significant differences between optimized and non-optimized measurements on the basis of a Wilcoxon ranked sum test with a confidence criterion of
α = 0.05.

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K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

Table 2 vanadium because the least-squares regression intercept between pXRF


Summary of sequential extraction procedure (modified from Chao and and LXRF data (11,600 mg/kg; Table 3) did not agree with the mea-
Sanzolone, 1989, and Wenzel et al., 2001). sured differences with the standard reference materials (Table 1).
Extraction solution Operationally defined Reaction Comparison of LXRF and pXRF data for copper, nickel, and zinc
surface-sorption sites time yielded R2 values of 0.89 to 0.95, although the slopes of least-squares
regression lines through the data were significantly < 1 (on the basis of
0.05 M KCl Weakly sorbed 4h
the t-test, with a confidence criterion of α = 0.05). These results in-
0.05 M (NH4)H2PO4 Specifically sorbed 16 h
dicate systematic lower concentration measurements for these elements
Sample material split into two equal portions
for the pXRF relative to the LXRF method, especially at higher en-
0.2 M (NH4)2C2O4·H2O Amorphous Al, Fe, and 4 h in the
Mn hydroxidesa dark vironmental concentrations (Fig. 2).
0.2 M (NH4)2C2O4·H2O + 0.1 M Well-crystallized Al, Fe, 30 min In contrast, least-squares regression comparison of LXRF and pXRF
C6H8O6 and Mn hydroxidesa data for iron and calcium showed slopes significantly > 1, but a high R2
4 N HNO3 Acid extractable (strong- 16 h value of 0.90 for both elements. The pXRF has a smaller power source
acid)b
compared to the LXRF, and X-rays generated by the pXRF penetrate less
a
Extraction done on split 1. deeply into sample material than those generated by the LXRF. As a
b
Extraction done on split 2. consequence, the pXRF may be more sensitive to iron oxide coatings on
the surfaces of mineral grains than the LXRF data collected on homo-
procedure adapted from Chao and Sanzolone (1989) and Wenzel et al. genized, fused-glass disks. Furthermore, high temperature fusion of
(2001) (Table 2). Sample extracts were preserved (if needed) and LXRF samples prior to analysis is sufficient to vaporize calcium-com-
shipped to the USGS National Water Quality Laboratory (NWQL) in plexes such as calcium carbonate, as supported by loss on ignition
Denver Colo. for analyses of selected elements (including aluminum, during LXRF sample preparation. Consequently, pXRF data for calcium
arsenic, chromium, iron, manganese, uranium, and vanadium) by In- are believed to be more accurate than LXRF data.
ductively Coupled Plasma Mass Spectrometry (ICP-MS) (Garbarino Arsenic was not measured by the LXRF and it was not possible to
et al., 2005). Sample extract solutions were diluted prior to analyses by compare LXRF and pXRF data, although arsenic data from the pXRF
ICP-MS to ensure instruments would not be damaged by chemicals in compared well with concentrations expected for powdered standard
the solutions. This resulted in laboratory reporting levels for chromium reference materials (Table 1).
in the various sample extract solutions that ranged from 9 to 150 μg/L
(0.045 to 0.75 mg/kg in mass per mass units used in this paper), and 4.2. Portable X-ray fluorescence
chromium concentrations were not quantifiable in most sample ex-
tracts. Sample extracts were reanalyzed for chromium by graphite 4.2.1. Distribution of selected trace elements in alluvium and rock
furnace using US EPA Method 7010 (U.S. Environmental Protection Median and maximum concentrations of arsenic, chromium, and
Agency, 2007), without dilution prior to analyses, at the USGS trace uranium in alluvium and rock samples from different geologic terrains
element laboratory in Boulder Colo. to obtain a lower reporting level of in the western Mojave Desert are presented in Table 4. Arsenic con-
0.02 μg/L (0.001 mg/kg in mass per mass units) for sequential extrac- centrations in alluvium ranged from < 1.4 mg/kg to 125 mg/kg. The
tion data. Extraction data were compared with pXRF data to determine median concentration of 4.3 mg/kg (Fig. 3; Table 4) was greater than
if trace elements were associated with surface coatings on mineral the average concentration in bulk continental crust of 1 mg/kg (Taylor
grains or unweathered mineral grains to assess the potential availability and McLennan, 1995), with 96% of data exceeding the pXRF reporting
of these elements to groundwater under changing geochemical condi- level (Fig. 3). Arsenic concentrations in 35% of data exceeded the
tions. median concentration of arsenic in continental U.S. soils of 5.7 mg/kg
(Smith et al., 2014). The highest concentrations in alluvium were
measured in material eroded from hydrothermally altered felsic vol-
4. Results and discussion canic rock east of Barstow. The median concentration of arsenic in re-
cent Mojave River alluvium, 2.2 mg/kg, is low compared to regional
4.1. Comparison of laboratory and portable X-ray fluorescence data concentrations of arsenic in the Mojave Desert. Arsenic concentrations
were generally higher in source rocks than alluvium. The highest con-
LXRF data were compared to pXRF data to determine the accuracy centration of arsenic in rocks (1400 mg/kg) was measured in a hydro-
of pXRF data. This was done to determine if pXRF survey data were thermally altered malachite-bearing sample northwest of Barstow. This
sufficiently accurate to assess regional geochemical differences in geo- sample also contained elevated antimony, copper, lead, manganese,
logic source terrains prior to interpretation of the larger and aerially silver, sulfur, uranium, and vanadium concentrations.
extensive pXRF data set. Chromium concentrations in alluvium collected in the western
Comparison of LXRF (Supplementary Data C) and pXRF data for Mojave Desert ranged from < 3.3 mg/kg to 490 mg/kg. The median
chromium, manganese, rubidium, strontium, titanium, and uranium concentration of 26 mg/kg (Fig. 4; Table 4) was less than the average
returned least-squares regression slopes statistically similar to 1 (on the concentration in bulk continental crust of 185 mg/kg (Taylor and
basis of the t-test with a confidence criterion of α = 0.05) (Neter and McLennan, 1995). Chromium concentrations in 41% of the data ex-
Wasserman, 1974), intercepts near 0, and R-squared (R2) values ran- ceeded the median concentration of chromium in continental U.S. soils
ging from 0.73 to 0.95 (Fig. 2; Table 3). Potassium and vanadium also of 30 mg/kg (Smith et al., 2014). Concentrations of chromium in mafic
had least-squares regression slopes statistically similar to 1, but lower alluvium eroded from Pelona Schist near Sheep Creek and El Mirage
R2 values of 0.52 and 0.66, respectively. The regression intercepts for (dry) Lake are as high as 300 mg/kg and 490 mg/kg, respectively. Older
vanadium (300 mg/kg) and potassium (11,600 mg/kg) were large re- Mojave River alluvium, which contains some alluvium eroded from the
lative to the magnitude of the sample concentrations. Vanadium pXRF Pelona Schist, had slightly lower chromium concentrations, with a
data were consistently 300 ± 50 mg/kg greater than the reported median value of 27 mg/kg (Table 4). In contrast, concentrations of
standard reference material concentrations (Supplementary Data B); as chromium in recent alluvium from the Mojave River and alluvium
a consequence, vanadium concentrations reported in this study were eroded from felsic terrain were even lower, with median values of
corrected by subtracting 300 from the pXRF measurement. Measured 7.6 mg/kg and 18 mg/kg, respectively. Chromium concentrations were
potassium pXRF data were 1000–2000 mg/kg less than the standard generally higher in rocks than in alluvium, with values as high as
reference materials. Potassium was not corrected in the same manner as 8600 mg/kg in mafic rocks from the Pelona Schist, and 420 and

5
K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

Fig. 2. Comparison between elemental concentrations in alluvium measured using portable (pXRF) and laboratory (LXRF) X-ray fluorescence, western Mojave
Desert, southern California.

350 mg/kg in rocks from Joshua Tree and Iron Mountain, respectively. average concentration in bulk continental crust.
Nickel, typically associated with chromium-bearing minerals in Uranium concentrations in alluvium ranged from < 2.8 mg/kg to
mafic rocks (Garver et al., 1996; Izbicki et al., 2008; Morrison et al., 13 mg/kg (Table 4), with only 12% of samples containing detectable
2015; Reimann and Caritat, 1998), had a similar distribution to chro- uranium (Fig. 5). The 2.8 mg/kg detection limit for uranium is greater
mium in alluvium and rock samples. The highest nickel concentrations than the average concentration in bulk continental crust of 0.91 mg/kg
(in exceedance of the average concentration in bulk continental crust of (Taylor and McLennan, 1995) and U.S. soils of 2.1 mg/kg (Smith et al.,
105 mg/kg; Taylor and McLennan, 1995) were in playa/lake deposits, 2014). The highest concentration of uranium in alluvium was measured
and in alluvium and rock eroded from mafic terrains and Pelona Schist in a fine-grained, clay-rich sample collected from older Mojave River
(Supplementary Data A). Only 4% of alluvium measurements and 23% deposits west of Iron Mountain (13 mg/kg), with other high con-
of rock measurements had concentrations of nickel in exceedance of the centrations measured in alluvium eroded from unaltered and

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K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

Table 3 Barstow. High uranium concentrations were also measured in mafic


Comparison between laboratory (LXRF) and portable (pXRF) X-ray fluorescence rock near the headwaters of Sheep Creek with a maximum concentra-
data, western Mojave Desert, southern California. tion of 18 mg/kg.
Element Slope R2 value Standard error Intercept

Arsenic (As) N.D. N.D. N.D. N.D. 4.2.2. Principal component analyses
Calcium (Ca) 1.41 0.90 1.05 −7950 Principal component analysis (PCA) (Hotelling, 1933; Wold et al.,
Chromium (Cr) 1.04 0.84 5.10 1.4 1987) was used to understand the spatial variability and differences in
Copper (Cu) 0.79 0.94 0.85 2.4 elemental concentration data of alluvium eroded from different geo-
Iron (Fe) 1.71 0.90 1.43 380
logic source terrains. PCA is a multivariate statistical technique used to
Lead (Pb) 0.66 0.31 3.50 2.8
Manganese (Mn) 0.91 0.91 0.01 1.9 transform potentially correlated, and potentially non-linear data (in this
Molybdenum (Mo) 0.73 0.88 0.83 1.7 case, elemental concentrations of alluvium measured using pXRF) into
Nickel (Ni) 0.78 0.89 1.77 20 new variables called principal components that are uncorrelated, linear
Potassium (K) 0.94 0.52 0.56 11,600
combinations of the original data. The values of the principal compo-
Rubidium (Rb) 0.94 0.92 4.28 10
Strontium (Sr) 0.98 0.95 18.41 51
nents are known as scores. Eigenvectors calculated from the PCA that
Tin (Sn) N.D. N.D. N.D. N.D. describe the direction and magnitude of elemental contributions to the
Titanium (Ti) 0.95 0.73 0.14 −23 PCA scores were used to evaluate elemental co-occurrence in alluvium
Uranium (U) 1.00 0.95 0.52 2.1 eroded from different geologic terrains. PCA results are sensitive to the
Vanadium (V) 1.05 0.66 13.36 300
scaling and magnitude of the data. As a consequence, data from rocks,
Zinc (Zn) 0.79 0.98 2.02 0.85
Zirconium (Zr) 1.32 0.91 12.53 11 which commonly have higher elemental concentrations than alluvium,
were not used to calculate PCA scores. Instead, PCA scores for rocks
N.D. = no data, element not measured using laboratory X-ray fluorescence (Srn) were calculated from eigenvectors estimated from alluvial con-
(LXRF) or no detections were made during measurements; number of sam- centration data according to the following equation:
ples = 33; LXRF data were the independent variable and portable X-ray fluor-
escence (pXRF) data were the dependent variable in the calculations. Bold font ¯

indicates elements with slopes within ± 10% of 1 between the two methods.
Xr Xa
Srn = E n
a
(1)
hydrothermally altered felsic volcanic rocks east of Barstow (7 mg/kg)
and northwest of Barstow (6 mg/kg), respectively. Uranium was com- where a = alluvium, r = rock; γ = is the individual element As, Ca,
monly detected in alluvium within Pipes Wash that drains the uranium- Cr…; Xrγ = concentration of element γ for a given rock measurement,
rich granitic rock in the San Bernardino Mountains (U.S. Geological ¯
Xa = mean concentration of element γ in alluvium measurements, and
Survey, 2004), but was less commonly detected in recent Mojave River
σ = standard deviation from the mean for element γ in alluvium;
deposits despite the abundance of granitic fragments eroded from ur-
E = nth eigenvector for element γ where n = 1, 2, 3, …
anium-rich rocks in the San Bernardino Mountains (U.S. Geological
The first and second principal components captured 45% of the total
Survey, 2004). Uranium was detected more frequently and at higher
variability in the pXRF data; the addition of the third principal com-
concentrations in rocks. Concentrations in rocks were as high as
ponent explained 57% of the total variability (Table 5).
180 mg/kg in hydrothermally altered felsic volcanic rock northwest of
PCA results, grouped by geologic terrain, were plotted with the first

Table 4
Arsenic, chromium, and uranium concentrations measured using portable X-ray fluorescence (pXRF) in generalized geologic materials, western Mojave Desert,
southern California.
Geologic material Arsenic (mg/kg) Chromium (mg/kg) Uranium (mg/kg) Number of samples

Median Max Median Max Median Max Detection frequency

Alluvium
Felsic 3.0 11 18 54 < 2.8 6.2 10% 22
Felsic (volcanic) 11 24 32 68 < 2.8 7.0 28% 8
Hydrothermally altered volcanics 30 125 22 43 < 2.8 6.0 24% 6
Mojave River alluvium 2.2 36 7.6 52 < 2.8 3.4 4% 16
Older Mojave River alluvium 3.2 49 27 87 < 2.8 13 14% 13
Mafic 4.6 31 54 300 < 2.8 3.5 1% 15
Mafic (volcanic) 6.4 13 60 135 < 2.8 3.8 7% 7
Mafic (Pelona Schist) 3.8 5.8 150 300 < 2.8 5.0 30% 6
Sedimentary 4.3 15 24 78 < 2.8 4.3 9% 50
Playa/lake deposits 8.9 16 58 490 < 2.8 < 2.8 0% 8
Carbonate 5.8 10 25 133 < 2.8 6.7 10% 5

Rock
Felsic 5.6 13 20 150 < 2.8 12 37% 7
Felsic (volcanic) 8.6 30 34 45 < 2.8 7.5 31% 4
Hydrothermally altered volcanics 45 1400 27 350 < 2.8 180 14% 3
Mafic 4.5 11 64 420 < 2.8 < 2.8 0% 6
Mafic (volcanic) 7.6 20 154 400 < 2.8 8.8 18% 10
Mafic (Pelona Schist) 5.1 55 5000 8600 < 2.8 18 12% 3
Carbonate 2.5 4.5 8.1 16 < 2.8 3.1 11% 3
Reporting level 1.4 3.3 2.8 Total: 192a
Median measured concentration of alluvium 4.3 26 < 2.8
Average bulk continental crust 1.0 185 0.91

Concentrations in milligrams per kilogram (mg/kg). Bulk continental crust concentrations cited from Taylor and McLennan, 1995.
a
Total sample count does not include 25 samples that were measured after being sieved or powdered. Raw data are available in Supplementary Data A.

7
K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

Fig. 3. Arsenic concentrations in alluvium and rocks, western Mojave Desert,


southern California.

principal component scores on the x-axis and the second principal


component scores on the y-axis (Fig. 6A, B, and C). The first principal
component was dominated by three large-magnitude, positive eigen-
vectors for iron, copper, and chromium, whereas the second principal
component was dominated by two large-magnitude, positive eigen-
vectors for potassium and rubidium (Table 5). As the first principal
component scores in alluvium eroded from mafic terrains increased
(Fig. 6A), concentrations of iron, copper, and chromium in alluvium
increased; similarly, as the second principal component scores in allu-
vium eroded from felsic terrains increased (Fig. 6A), concentrations of
potassium and rubidium in alluvium increased. Calculated scores for
rocks (Eq (1)) collected from both mafic and felsic terrains were greater
in magnitude than scores for alluvium, while data from alluvium
showed some mixing between the felsic and mafic end members. Al-
luvium eroded from hydrothermally altered terrains (Fig. 6A) had po-
sitive first and second principal component scores consistent with
higher concentrations of trace and major elements in hydrothermally
altered rocks.
The elemental compositions of alluvium eroded from carbonate and
sedimentary terrains (Fig. 6B) were less variable within the first and
second principal components than alluvium eroded from either mafic or
felsic terrain. Large-magnitude, negative third principal component
eigenvectors for calcium and strontium (Table 5) are consistent with co-
occurrence of these elements in alluvium eroded from carbonate terrain
(not shown on Fig. 6).
Samples from playas represent materials at the terminus of surface
drainage systems, and some playas are in regional groundwater dis-
charge areas. Playas act as areas of accumulation for fine-grained se-
diment and trace elements sorbed to the sediments. Playas sampled as
part of this study had high first principal component scores consistent
with higher concentrations of chromium and iron—in addition to other
elements that occupy sorption sites on fine-grained sediment such as
arsenic, copper, nickel, uranium, and zinc. The 3 data points in the
lower right corner of Fig. 6B are from El Mirage (dry) Lake at the ter-
minus of Sheep Creek. The magnitude of the first and second principal
component scores for these data is similar to scores for the source rocks
eroded from the Pelona Schist.
The first and second principal component scores for recent alluvium
from the Mojave River (Fig. 6C) are consistent with scores from felsic
terrain, and erosion and transport of material from granitic rock in the
San Bernardino Mountains. In contrast, older Mojave River deposits had
more positive first principal component scores—consistent with a more
mafic source and increased contribution of alluvium eroded from mafic
rocks in the San Gabriel Mountains (Meisling and Weldon, 1989; Izbicki
et al., 2008) (Fig. 6C).

4.2.3. Distribution of selected trace elements along selected stream channels


In order to evaluate the role of changes in bedrock geology along the
length of stream channels as well as hydrologic sorting, physical dis-
integration, and chemical weathering of less resistant minerals on al-
luvium chemistry, detailed sampling was done along the length of ac-
tive channels of several large streams. Samples included: 1) 15 samples
along an almost 170 km reach of the Mojave River (the longest stream
having the largest drainage, 5500 km2, in the study area), 2) four to five
samples each along about 30 km reaches of Sheep Creek, Fremont
Wash, and Oro Grande Wash, 3) nine samples along a nearly 40 km
reach of Pipes Wash, and 4) nine samples from smaller reaches along
three washes in the Joshua Tree area.
Recent alluvium within the active channel of the Mojave River,
composing the highly productive floodplain aquifer along the river, had
low median concentrations of arsenic (2.2 mg/kg) and chromium
(7.6 mg/kg) (Table 4). Arsenic concentrations increased along the

8
K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

Fig. 4. Chromium concentrations in alluvium and rocks, western Mojave


Desert, southern California.

downstream reaches of the river east of Barstow, apparently due to


contributions of alluvium eroded from unaltered and hydrothermally
altered felsic volcanic terrain in this area (Figs. 1B and 7A). In contrast,
chromium concentrations did not increase downstream from chro-
mium-bearing bedrock in Iron Mountain, or downstream from Oro
Grande Wash or Fremont Wash—which deliver reworked alluvium,
high in chromium, originally sourced from the Pelona Schist to the river
(discussed below; Figs. 1 and 7). Uranium concentrations in the Mojave
River were uniformly low along the length of the river (not shown on
Fig. 7) despite high concentrations in source rock in the San Bernardino
Mountains (U.S. Geological Survey, 2004). Hydrologic sorting of dense
uranium-bearing minerals (Brady and Jobson, 1973; Deer et al., 1992;
Hughes et al., 2000; Pettijohn, 1941; Pettijohn et al., 1987; Morton and
Hallsworth, 1999) within Mojave River alluvium may have resulted in
selective removal of uranium-rich minerals and explains the apparent
low concentrations of uranium in our samples.
Prior to about 8000 years ago, Sheep Creek and Fremont Wash
formed a continuous stream that extended from the San Gabriel
Mountains to the Mojave River (Fig. 1). However, as the Sheep Creek
fan encroached into the Mojave Desert, the fan blocked surface drai-
nage from the area, creating the topographically closed El Mirage (dry)
Lake (Miller and Bedford, 2000; Miller et al., 2010). Chromium and
nickel concentrations as high as 300 and 140 mg/kg, respectively, in
mafic alluvium from the upstream reach of the combined Sheep Creek/
Fremont Wash channel decreased downstream to concentrations similar
to those of alluvium along the Mojave River (Fig. 7B). Under present-
day conditions, the Sheep Creek/Fremont Wash drainage does not
contribute large amounts of chromium or nickel to the Mojave River
(Fig. 7A and B). Concentrations of other elements, such as arsenic and
uranium, also decreased along Sheep Creek and Fremont Wash (not
shown on Fig. 7).
Oro Grande Wash crosses the Victorville fan, which has been se-
parated (beheaded) from its original headwaters in the San Gabriel
Mountains by right lateral movement along the San Andreas Fault and
subsequent erosion by westward draining streams near Cajon Pass.
Thus, the mafic Pelona Schist in the present-day headwaters of Sheep
Creek would have been near the headwaters of Oro Grande Wash one to
five million years ago (Cox et al., 2003; Meisling and Weldon, 1989).
Chromium concentrations in alluvium in Oro Grande Wash were higher
along the upstream reaches and decreased downstream, similar to
Sheep Creek and Fremont Wash. Urban development in the final 5 km
reach of Oro Grande Wash may have resulted in the slight increase in
nickel (but not chromium) concentrations near Victorville (Fig. 7C).
Although chromium and nickel concentrations in alluvium from Oro
Grande Wash are higher than those in recent Mojave River alluvium,
Oro Grande Wash does not appear to contribute to an increase in the
concentrations of these elements in present-day Mojave River alluvium
(Fig. 7A). Uranium was detected in 4 of the 5 samples from Oro Grande
Wash. The canyon walls of Oro Grande Wash are rich in clay, which
may contain uranium released from weathering of uranium-bearing
minerals (Guthrie and Kleeman, 1986; Tieh et al., 1980; Sato et al.,
1997).
Pipes Wash drains the San Bernardino Mountains northwest of
Joshua Tree (Fig. 1), which are locally composed of felsic quartz
monzonite and mafic basalt. Chromium concentrations in alluvium
within Pipes Wash increase as the wash passes basalt outcrops down-
stream from the mountain front, while nickel concentrations remain
relatively constant (Fig. 7D). Chromium concentrations in Pipes Wash
are higher at the terminus of the wash near a dry playa/lake, in part due
to finer-grained material near its terminus. Arsenic concentrations
(generally below study median; not shown in Fig. 7D) increased over
the final 10 km reach of Pipes Wash. Uranium was detected in 5 of the 9

9
K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

Fig. 5. Uranium concentrations in alluvium and rocks, western Mojave Desert,


southern California.

Table 5
Mean concentration, standard deviation, and the first, second, and third ei-
genvectors from principal component analysis (PCA) of selected portable X-ray
fluorescence (pXRF) measurements of alluvium, western Mojave Desert,
southern California.
Element Mean Standard First Second Third
deviation eigenvector eigenvector eigenvector

Arsenic (As) 6.9 11.3 0.1885 0.2917 −0.3146


Calcium (Ca) 26,800 30,500 0.1629 0.0698 −0.3203
Chromium 38 52 0.3412 −0.1661 0.1302
(Cr)
Copper (Cu) 16 14 0.3518 −0.1245 −0.0220
Iron (Fe) 20,800 17,000 0.4000 −0.1366 0.0409
Lead (Pb) 18 23 0.0820 0.3136 0.1930
Manganese 412 312 0.3236 −0.0262 0.0493
(Mn)
Molybdenum 1.6 2.8 0.1424 0.3241 −0.4401
(Mo)
Nickel (Ni) 39 28 0.2878 −0.1630 0.1724
Potassium (K) 25,400 7470 −0.0211 0.4450 0.3237
Rubidium 107 39 −0.0046 0.4222 0.3450
(Rb)
Strontium (Sr) 512 844 0.0700 0.3139 −0.4147
Tin (Sn) 14 6.6 0.1595 −0.0003 0.1356
Titanium (Ti) 2720 1760 0.3293 −0.1556 −0.0319
Uranium (U) 1.7 1.0 0.0369 0.1031 0.1770
Vanadium (V) 116 67 0.2324 0.2108 0.2537
Zinc (Zn) 42 40 0.3321 0.2263 0.0288
Zirconium (Zr) 200 100 0.1351 −0.1111 −0.0671
Total variance explained 28% 45% 57%

Bold type indicates magnitude (either positive or negative) of eigenvector is


within the upper 10% of all eigenvectors calculated by the principal component
analysis. Vanadium concentration corrected on the basis of laboratory X-ray
fluorescence (LXRF) and standard reference data.

samples collected from Pipes Wash (Fig. 5; not shown in Fig. 7). The
frequent detection of uranium in Pipes Wash alluvium was likely due to
higher concentrations of uranium in source rocks from the San Ber-
nardino Mountains (U.S. Geological Survey, 2004).
Samples also were collected from several small stream channels that
drain felsic quartz monzonite bedrock with small outcrops of mafic rock
near Joshua Tree. Chromium concentrations within the channels in-
creased locally near mafic outcrops and then decreased farther down-
stream (not shown on Fig. 7).
Changes in the elemental composition of alluvium in Pipes Wash
and smaller washes near Joshua Tree is likely a consequence of the
relatively low volume of alluvium transported by these smaller systems,
and the greater sensitivity of those small systems to changes in bedrock
geology. This contrasts with the large volume of alluvium transported
by the Mojave River that dilutes additions of locally-derived alluvium
from mafic rock in Iron Mountain (Fig. 7A). However, regional changes
in geologic source terrain east of Barstow were large enough to affect
the elemental composition of alluvium in downstream reaches of the
Mojave River.

4.2.4. Distribution of selected trace elements in older and recent Mojave


River alluvium
Ages of samples collected from older Mojave River deposits were
estimated based on mapped outcrops and the timing of the encroach-
ment of the Mojave River into the Mojave Desert (Cox et al., 2003;
Stamos et al., 2001). Systematic shifts in alluvium chemistry over the
past one million years correspond to these estimated ages of the allu-
vium (Fig. 8). Chromium and nickel concentrations systematically in-
crease and potassium and rubidium decrease with increasing age. These
geochemical trends, identified with PCA in Fig. 6C, are consistent with

10
K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

Fig. 6. First and second principal component scores from elemental concentrations in rock (calculated) and alluvium grouped by rock and alluvium eroded from
felsic, mafic and hydrothermal terrains (A); rock and alluvium eroded from carbonate, sedimentary, and alluvium in playa/lake terrains (B); and for alluvium from
the Mojave River, older Mojave River, and Pelona Schist (C), western Mojave Desert, southern California.

decreasing contributions of alluvium eroded from mafic rocks in the they were associated with crystalline aluminum, iron, and manganese
San Gabriel Mountains and increasing contributions of alluvium from oxide coatings and other minor phases including secondary sulfides.
felsic rocks in the San Bernardino Mountains. This occurred over the Concentrations of extracted elements were lower in the 0.2 M ammo-
past one million years as a result of movement of geologic-source ter- nium oxalate and 0.2 M ammonium oxalate plus 0.1 M ascorbic acid
rains contributing alluvium to the Mojave River, including the mafic extractions modified from Wenzel et al. (2001). Comparison of data
Pelona Schist, along the San Andreas Fault. from the two extractions suggests that the extractions proposed by
A Wilcoxon ranked sum test (with a confidence criterion of Wenzel et al. (2001) were not sufficiently rigorous to extract all the
α ≤ 0.05) was used to test differences between the chemical composi- trace elements sorbed to aluminum, iron, and manganese oxides on the
tion of recent versus older Mojave River deposits to confirm the shift in surfaces of mineral grains.
source rock type as a consequence of the movement along the San Of the trace elements measured, only arsenic was present at sig-
Andreas fault. Median concentrations of elements in the two deposits nificant concentrations in the specifically sorbed fraction (Fig. 9; Ap-
were statistically different for all elements measured using pXRF, ex- pendix Table S3). This differs from the distribution of sorbed arsenic on
cept for nickel and uranium. The lack of a statistically significant dif- soils, where most arsenic is in the amorphous phase (Wenzel et al.,
ference in uranium concentrations in alluvium may result because ur- 2001). In general, results from this study are similar to results obtained
anium is high in both the San Bernardino and San Gabriel Mountains. for alluvium elsewhere in the Mojave Desert (Izbicki et al., 2008, 2015),
Nickel concentrations in both recent and older Mojave River deposits except that previous data showed uranium concentrations nearly an
were generally low, with median concentrations of 23 and 34 mg/kg, order of magnitude greater, with about half of the uranium contained
respectively. The decrease in the ratio of chromium to nickel from 0.79 within the non-specifically sorbed, 0.05 M KCl fraction and likely as-
in older Mojave River deposits to 0.31 in recent Mojave River deposits sociated with carbonate minerals. Uranium concentrations may be
is consistent with removal of the mafic Pelona Schist–which has a high higher in those data because many of the previous samples were allu-
chromium to nickel ratio of 4.3–from the geologic source areas con- vium eroded from the uranium-rich Pipes Wash drainage.
tributing to the river. Extracted elements were present at higher concentrations in fine-
grained deposits (on the basis of Wilcoxon ranked sum tests with a
4.3. Sequential extractions confidence criterion of α ≤ 0.05) (Fig. 9). This is consistent with
greater surface area and a greater abundance of iron, manganese, and
Elements sorbed onto coatings on mineral grains are potentially aluminum oxide surface sites available for exchange on clay and silt
soluble and may enter groundwater under the proper geochemical sized material. Kim et al. (2011) observed a similar correlation between
conditions (Morrison et al., 2015). In contrast, elements contained increasing trace-element concentrations, including arsenic and chro-
within primary mineral grains must weather from the mineral before mium, and decreasing grain size. Izbicki et al. (2008) reported higher
they can enter groundwater, and may be of lesser concern to ground- chromium concentrations in extractions from samples distal from the
water consumers. Selected elements sorbed on the surfaces of mineral San Gabriel Mountains in the Sheep Creek fan. This coincided with an
grains were extracted from samples of alluvium and core material increase in iron and manganese sorption sites that they attributed to
(Appendix Table S1) using progressively stronger extraction solutions finer grain-size.
to evaluate elements associated with operationally defined surface- Comparison of extraction data to total elemental abundance mea-
sorption sites (Table 2). Sequential extraction results (Appendix Tables sured by pXRF indicates that arsenic, uranium, and manganese are
S2–S6) were compared to total elemental concentrations measured by present at higher concentrations in the extracts from material on the
pXRF to evaluate the potential availability of selected trace elements to surfaces of mineral grains than within the grains (Fig. 9). In contrast,
groundwater. Uranium concentration data measured using LXRF chromium and vanadium were present in lower concentrations in the
(Supplementary Data C) were used in place of pXRF data that were less extracts than within mineral grains. This pattern is consistent across the
than the detection limit of 2.8 mg/kg. range of size fractions from clay to coarse sand.
Arsenic, chromium, uranium, and vanadium in extraction solutions Surface coatings in finer-grained, clayey deposits contained ur-
were present at the highest concentrations in the strong-acid (4 N anium at concentrations as high as 70% of the total concentration
HNO3) extraction modified from Chao and Sanzolone (1989), indicating measured by pXRF, with almost all the uranium present in the strong-

11
K.D. Groover, J.A. Izbicki

Fig. 7. Selected trace-element concentrations in alluvium along the Mojave River (A), Sheep Creek and Fremont Wash (B), Oro Grande Wash (C), and Pipes Wash (D),
western Mojave Desert, southern California. Drainage locations shown on Fig. 1.

acid extraction fraction and associated with crystalline oxides. Some the strong acid and the specifically sorbed phases, where sorption is pH
coarse-grained samples of alluvium immediately west of Barstow con- dependent. Arsenic sorption on the specifically sorbed phase increased
tained uranium at concentrations as high as 50% of the total pXRF or with decreasing particle size.
LXRF concentration in the strong-acid extraction (Figs. 5, 9). Arsenic in Sequential extraction and pXRF data suggest that some elements
fine-grained, clayey deposits was almost equally distributed between such as manganese, uranium, and especially arsenic in fine-grained
K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

Fig. 8. Chromium, nickel, potassium, and rubidium concentrations in older Mojave River deposits plotted against approximate age, western Mojave Desert, southern
California.

sediments may be more available for release to groundwater than continental crust of 1 mg/kg. Arsenic concentrations as high as 125 and
chromium or vanadium if redox conditions change. This is attributed to 1400 mg/kg were associated with alluvium and rock, respectively,
chromium and vanadium residing largely in primary minerals. Arsenic collected from hydrothermally altered felsic volcanic terrain.
mobilization in particular may be sensitive to changes in pH of Chromium concentrations in the Mojave Desert were generally low, and
groundwater (Wenzel et al., 2001), or increases in ionic strength that only 4% of alluvium samples had chromium concentrations greater
are accompanied by increasing concentrations of ions, such as phos- than average concentrations in bulk continental crust of 185 mg/kg.
phate, which compete with arsenic for sorption sites (Welch et al., However, chromium concentrations were as high as 490 and 8600 mg/
2000). kg in playa lake deposits eroded from the Pelona Schist and rocks
Manganese sorbed to the surfaces of mineral grains in clayey de- collected from the Pelona Schist, respectively. Median chromium con-
posits, and to a lesser extent coarse-grained felsic volcanic terrain (not centrations were as low as 7.6 mg/kg in recent Mojave River alluvium.
shown in Fig. 9), could potentially oxidize insoluble trivalent chro- Uranium concentrations were generally less than the pXRF reporting
mium, Cr(III), on surface exchange sites, to highly soluble hexavalent level of 2.8 mg/kg, which was greater than the average bulk continental
chromium, Cr(VI) (Morrison et al., 2015). Once oxidized, Cr(VI) may crust abundance of 0.91 mg/kg. However, uranium concentrations as
subsequently enter groundwater under redox and pH conditions present high as 13 and 180 mg/kg were measured in clayey older Mojave River
within the study area (Dawson and Belitz, 2012; Metzger et al., 2015). alluvium and hydrothermally altered volcanic rocks, respectively. In
However, sequential extraction and pXRF data show that oxidation of general, erosion of hydrothermally altered and mineralized felsic vol-
Cr(III) to Cr(VI) under natural conditions may be limited because canic rocks yields alluvium with high arsenic concentrations, erosion of
weathering of chromium from mineral grains prior to its release to chromium-rich mafic rocks (specifically the Pelona Schist) yields allu-
groundwater is a comparatively slow process. vium with high chromium concentrations, and erosion from felsic
volcanic and plutonic source rocks yield generally uranium-rich sedi-
ments.
5. Conclusions Principal component analysis (PCA) quantified the relation between
geologic source terrain and alluvium eroded from those terrains. PCA of
Systematic comparison between pXRF and LXRF data, and with pXRF data demonstrate higher concentrations of iron, copper, chro-
NIST-traceable standard reference material, showed pXRF data were mium, and to a lesser extent titanium, manganese, and nickel (in
suitable for evaluating the occurrence and spatial distribution of trace principal component one) characterize alluvium eroded from mafic
elements of potential public-health concern in groundwater including terrain, while higher concentrations of rubidium and potassium (in
arsenic, chromium, and uranium. principal component two) characterize alluvium eroded from felsic
Arsenic concentrations were generally high in the Mojave Desert, terrain. In contrast, alluvium eroded from hydrothermally altered vol-
and 96% of samples had measurable arsenic greater than the pXRF canics was characterized by high concentrations of mafic and felsic
reporting level of 1.4 mg/kg compared to the average concentration in

13
K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

contributed from local sources. However, regional changes in bedrock


source terrain east of Barstow were sufficiently large to alter the
chemistry of alluvium within the downstream reaches of the Mojave
River.
The alluvial chemistry of the Mojave River has changed over the
past one to five million years as the river's source area changed from
more mafic rock within the San Gabriel Mountains to more felsic rock
within the San Bernardino Mountains. This change resulted from right-
lateral movement of mafic rock along the San Andreas Fault. The
change in source area influences not only the alluvium composition, but
also the potential availability and mobility of certain elements, such as
chromium, into groundwater.
Comparison of pXRF and sequential-extraction data for selected
elements (including arsenic, chromium, uranium, and vanadium) sug-
gests that arsenic and uranium may be potentially mobile to ground-
water under redox and pH conditions found within alluvial aquifers in
the study area. Arsenic, which is abundant in the specifically sorbed
fraction on the surfaces of mineral grains, may be mobilized into
groundwater by changes in pH, redox, increases in ionic strength, and
increases in the concentrations of ions such as phosphate that compete
with arsenic for exchange sites. In contrast, chromium and vanadium
are potentially less mobile to groundwater because they are largely
present within unweathered primary minerals and must chemically
weather from those minerals. In addition, once weathered from mineral
grains, chromium must then be oxidized from trivalent chromium, Cr
(III), to hexavalent chromium, Cr(VI), before it can be mobilized into
groundwater. Manganese present at high concentrations on oxide
coatings on mineral grains may be sufficiently available and reactive to
oxidize Cr(III) to Cr(VI). Concentrations in extractions increased with
decreased grain size for arsenic, chromium, uranium, and vanadium,
and for aluminum, iron, and manganese oxides which form sorption
sites on those grains.
Additional work relating the geologic abundance of naturally oc-
curring trace elements and their potential mobility to groundwater with
groundwater geochemistry may help identify how naturally occurring
sources in alluvium and rock interact with geochemical processes to
control trace element concentrations in water from wells.
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.gexplo.2018.09.005.

Acknowledgments

This study was funded by the Mojave Water Agency, with additional
funding from Joshua Basin Water District, the Lahontan Regional Water
Quality Control Board, and the Fort Irwin National Training Center. The
authors thank Amanda Lopez and Tony Winkel (Mojave Water Agency),
Jill Judy-Densmore, Joseph Nawikas, and Andy Morita (U.S. Geological
Survey) for their assistance in the field collecting samples; Joan
Fig. 9. Concentrations of arsenic, chromium, and other selected trace and Kimbrough and Heather Webb of the Department of Geological
major elements in sequential extractions normalized to concentrations of ele-
Sciences at San Diego State University for assistance with preparation
ments in alluvium measured using X-ray fluorescence (XRF), western Mojave
and analysis of samples using the laboratory XRF; and Russell Johnson
Desert, southern California.
(U.S. Geological Survey, retired) for his assistance in preparing the
sequential extractions. The authors also thank Kathy Thorbjarnarson
elements, and also had high concentrations of zinc, vanadium, and (San Diego State University) and David Miller (U.S. Geological Survey)
arsenic. for their advice, thoughtful comments, and assistance during this study.
Changes in alluvium chemistry occur along stream channels because
of factors such as dilution, mineral grain size, and the accretion of al- References
luvium from different bedrock source terrains along the stream length.
If a geochemically distinctive rock outcrop (e.g., a mafic-rich outcrop Ball, J.W., Izbicki, J.A., 2004. Occurrence of hexavalent chromium in ground water in the
versus a felsic outcrop) is sufficiently large relative to the volume of western Mojave Desert, California. Appl. Geochem. 19, 1123–1135.
sediment in the stream derived from upstream sources, the elemental Brady, L.L., Jobson, H.E., 1973. An experimental study of heavy-mineral segregation
under alluvial - flow conditions. U.S. Geological Survey Professional Paper 562-K.
signature of alluvium eroded from this outcrop may be distinguishable. (38 pp.).
If the outcrop is small relative to the volume of sediment in the stream California Department of Water Resources, 2003. California's groundwater. In: California
derived from upstream sources, the elemental signature of alluvium Department of Water Resources Bulletin 118, . http://www.water.ca.gov/
groundwater/bulletin118/update_2003.cfm (August 2015, 246 pp.).
may be diluted. The volume of alluvium transported by the Mojave Chaffee, M.A., 1975. Geochemical exploration techniques applicable in the search for
River is large enough to dilute elemental signatures of alluvium copper deposits. In: U.S. Geological Survey Professional Paper 907-B, (26 pp.).

14
K.D. Groover, J.A. Izbicki Journal of Geochemical Exploration xxx (xxxx) xxx–xxx

Chao, T.T., Sanzolone, R.F., 1989. Fractionation of soil selenium by sequential partial Report 00-222, . http://wrgis.wr.usgs.gov/open-file/of00-222 (March 2016).
dissolution. Soil Sci. Soc. Am. J. 53, 385–392. Miller, D.M., Yount, J.C., 2002. Late Cenozoic tectonic evolution of the north-central
Cox, B.F., Hillhouse, J.W., Owen, L.A., Enzel, Y., Wells, S.G., Lancaster, N., 2003. Pliocene Mojave Desert inferred from fault history and physiographic evolution of the Fort
and Pleistocene evolution of the Mojave River, and associated tectonic development Irwin area, California. Geol. Soc. Am. Mem. 195, 173–197. https://doi.org/10.1130/
of the Transverse Ranges and Mojave Desert, based on borehole stratigraphy studies 0-8137-1195-9.173.
and mapping of landforms and sediments near Victorville, California. In: Miller, D.M., Schmidt, K.M., Mahan, S.A., McGeehin, J.P., Owen, L.A., Baron, J.A.,
Paleoenvironments and Paleohydrology of the Mojave and Southern Great Basin Lehmkuhl, F., Löhrer, R., 2010. Holocene landscape response to seasonality of storms
Deserts: Boulder, Colorado, Geological Society of America Special Paper 368, pp. in the Mojave Desert. Quat. Int. 215 (1–2), 45–61. https://doi.org/10.1016/j.quaint.
1–42. 2009.10.001.
Dawson, B.J., Belitz, K., 2012. Status of groundwater quality in the California Desert Morrison, J.M., Goldhaber, M.B., Mills, C.T., Breit, G.N., Hooper, R.L., Holloway, J.M.,
Region, 2006–2008: California GAMA Priority Basin Project. In: U.S. Geological Diehl, S.F., Ranville, J.F., 2015. Weathering and transport of chromium and nickel
Survey Scientific Investigations Report 2012–5040, (110 pp.). from serpentinite in the Coast Range ophiolite to the Sacramento Valley, California,
Deer, W.A., Howie, R.A., Zussman, J., 1992. An introduction to the rock-forming mi- USA. Appl. Geochem. 61, 72–86. https://doi.org/10.1016/j.apgeochem.2015.05.
nerals, 2nd ed. Pearson Education Limited, Essex, England (696 pp.). 018.
Dibblee, T.W., 1967. Areal geology of the western Mojave Desert, California. In: U.S. Morton, A.C., Hallsworth, C.R., 1999. Processes controlling the composition of heavy
Geological Survey Professional Paper 522, (153 pp.). mineral assemblages in sandstones. Sediment. Geol. 124, 3–29.
Ehlig, P.L., 1958. The Geology of the Mount Baldy Region of the San Gabriel Mountains, Neter, J., Wasserman, W., 1974. Applied Linear Statistical Models. Richard D. Irwin, Inc.,
California. University of California, Los Angeles (Ph.D. thesis: 195 pp.). Homewood, Illinois (842 pp.).
Ehlig, P.L., 1968. Causes of distribution of Pelona, Rand, and Orocopia Schist along the Painter, S., Cameron, E.M., Allan, R., Rouse, J., 1994. Reconnaissance geochemistry and
San Andreas and Garlock faults. In: Dickinson, W.K., Grants, A. (Eds.), Proceedings of its environmental relevance. J. Geochem. Explor. 51 (3), 213–246. https://doi.org/
Conference on Geologic Problems of San Andreas Fault System. 11. Stanford 10.1016/0375-6742(94)90008-6.
University Publications, Geological Sciences, pp. 294–306. Pettijohn, F.J., 1941. Persistence of heavy minerals and geologic age. J. Geol. 49 (6),
Evans, J.G., 1982. The Vincent Thrust, eastern San Gabriel Mountains, California. In: U.S. 610–625.
Geological Survey Bulletin 1507, (15 pp.). Pettijohn, F.J., Potter, P.E., Siever, R., 1987. Sand and Sandstone, 2nd ed. Springer-
Garbarino, J.R., Kanagy, L.K., Cree, M.E., 2005. Determination of elements in natural- Verlag, New York (553 pp.).
water, biota, sediment and soil samples using collision/reaction cell inductively Reimann, C., 2005. Sub-continental scale geochemical mapping: sampling, quality control
coupled plasma-mass spectrometry. In: U.S. Geological Survey Techniques and and data analysis issues. Geochem.: Explor., Environ., Anal. 5 (4), 311–323.
Methods, (book 5, sec. B, chap.1, 88 p. Method ID: I-2020-05 https://nwql.usgs.gov/ Reimann, C., Caritat, P., 1998. Chemical Elements in the Environment. Springer-Verlag,
Public/rpt.shtml?TM-5-B1, accessed March 21, 2018). Berlin, Germany (398 pp.).
Garver, J.I., Royce, P.R., Smick, T.A., 1996. Chromium and nickel in shale of the Taconic Sato, T., Murakami, T., Yanase, N., Isobe, H., Payne, T.E., Airey, P.L., 1997. Iron nodules
foreland: a case study for the provenance of fine-grained sediments with an ultra- scavenging uranium from groundwater. Environ. Sci. Technol. 31, 2854–2858.
mafic source. J. Sediment. Res. 66 (1), 100–106. Seymour, W.A., 2016. Hydrologic and Geologic Controls on Groundwater Recharge Along
Glazner, A.F., Walker, D.J., Bartley, J.M., Fletcher, J.M., 2002. Cenozoic evolution of the the Mojave River Floodplain Aquifer. San Diego State University, San Diego,
Mojave block of southern California. Geol. Soc. Am. Mem. 195, 19–41. California (M.S. thesis, 59 pp. http://sdsu-dspace.calstate.edu/bitstream/handle/
Gough, L.P., Severson, R.C., Shacklette, H.T., 1988. Element concentrations in soils and 10211.3/175391/Seymour_sdsu_0220N_11429.pdf?sequence=1 (December 2017)).
other surficial materials of Alaska. In: U.S. Geological Survey Professional Paper Shacklette, H.T., Boerngen, J.G., 1984. Element concentrations in soils and other surficial
1458, (53 pp.). materials of the conterminous United States. In: U.S. Geological Survey Professional
Gough, L.P., Wang, B., Smith, D.B., Gustavsson, N., 2005. Geochemical landscapes of Paper 1270, (63 pp.).
Alaska – new map presentations and interpretations for 23 elements in surficial Shacklette, H.T., Hamilton, J.C., Boerngen, J.G., Bowles, J.M., 1971. Element composi-
materials. In: U.S. Geological Survey Professional Paper 1716, (36 pp.). tion of surficial materials of the conterminous United States. In: U.S. Geological
Graham, G.E., Taylor, R.D., Lee, G., Tripp, R.B., 2015. Targeting Cu-Au and Mo resources Survey Professional Paper, 574-D.
using multi-media exploration geochemistry: an example from Tyonek Quadrangle, Smith, D.B., Cannon, W.F., Woodruff, L.G., Solano, F., Ellefson, K.J., 2014. Geochemical
Alaska Range, Alaska. J. Geochem. Explor. 52–65. https://doi.org/10.1016/j.gexplo. and mineralogical maps for soils of the conterminous United States. In: U.S.
2015.014. Geological Survey Open-File Report 2014-1082, https://doi.org/10.3133/
Guthrie, V.A., Kleeman, J.D., 1986. Changing uranium distributions during weathering of ofr20141082. (386 pp.).
granite. Chem. Geol. 54 (1–2), 113–126. https://doi.org/10.1016/0009-2541(86) Stamos, C.L., Martin, P., Nishikawa, T., Cox, B.F., 2001. Simulation of ground-water flow
90075-6. in the Mojave River Basin, California. In: U.S. Geological Survey Water-resources
Hawkes, H.E., 1976. The early days of exploration geochemistry. J. Geochem. Explor. 6 Investigations Report 01-4002, (113 pp.).
(1–2), 1–11. Taylor, S.R., McLennan, S.M., 1995. The geochemical evolution of the continental crust.
Hem, J.D., 1992. Study and interpretation of the chemical characteristics of natural Rev. Geophys. 33, 241–265.
water. In: U.S. Geological Survey Water-supply Paper 2254, (263 pp.). Thompson, D.G., 1929. The Mojave Desert region, California: a geographic, geologic, and
Hotelling, H., 1933. Analysis of a complex of statistical variables into principal compo- hydrologic reconnaissance. In: U.S. Geological Survey Water-supply Paper 578,
nents. J. Educ. Psychol. 24 (6), 417–441. (759 pp.).
Hughes, M.G., Keene, J.B., Joseph, R.G., 2000. Hydraulic sorting of heavy-mineral grains Tieh, T.T., Ledger, E.B., Rowe, M.W., 1980. Release of uranium from granitic rocks during
by swash on a medium-sand beach. J. Sediment. Res. 70 (5), 994–1004. in situ weathering and initial erosion (central Texas). Chem. Geol. 29 (1–4), 227–248.
Izbicki, J.A., Michel, R.L., 2004. Movement and age of ground water in the western part of https://doi.org/10.1016/0009-2541(80)90022-4.
the Mojave Desert, Southern California, USA. In: U.S. Geological Survey Water-re- U.S. Environmental Protection Agency, 2007. Method 7010: graphite furnace atomic
sources Investigations Report 03-4314, (35 pp.). absorption spectrometry, Revision 0. https://www.epa.gov/sites/production/files/
Izbicki, J.A., Ball, J.W., Bullen, T.D., Sutley, S.J., 2008. Chromium, chromium isotopes 2015-12/documents/7010.pdf, Accessed date: 21 March 2018.
and selected trace elements, western Mojave Desert, USA. Appl. Geochem. 23, U.S. Geological Survey, 2004. The National Geochemical Survey - database and doc-
1325–1352. https://doi.org/10.1016/j.apgeochem.2007.11.015. umentation. In: U.S. Geological Survey Open-file Report 04-1001, . http://mrdta.
Izbicki, J.A., Kulp, T., Suarez, D., Barnes, T., Ajwani, C., Kim, T.J., Tseng, I., 2015. In-situ usgs.gov/geochem/ (February 2016).
Arsenic Removal During Groundwater Recharge Through Unsaturated Alluvium. U.S. Geological Survey, 2005a. Active Mines and Mineral Processing Plants in the United
Water Research Foundation (Web Report #4299, 59 pp. http://www.waterrf.org/ States in 2003. U.S. Geological Survey, Reston, Virginia. http://mrdata.usgs.gov/
PublicReportLibrary/4299.pdf (March 2016)). mineplant/ (February 2016).
Jennings, C.W., with modifications by Gutierrez, C., Bryant, W., Saucedo, G., and Wills, U.S. Geological Survey, 2005b. Mineral Resources Data System. U.S. Geological Survey,
C., 2010, Geologic map of California: California Geological Survey, Geologic Data Reston, Virginia. http://mrdata.usgs.gov/mrds/ (February 2016).
Map No. 2, scale 1:750,000. Webb, J.S., Fortescue, J., Nichol, I., Tooms, J.S., 1964. Regional Geochemical
Kim, C.S., Wilson, K.M., Rytuba, J.J., 2011. Particle-size dependence on metal(loid) Reconnaissance in the Namwala Concession Area, Zambia: Technical Communication
distributions in mine wastes: implications for water contamination and human ex- 47. Geochemical Prospecting Research Centre.
posure. Appl. Geochem. 26, 484–495. https://doi.org/10.1016/j.apgeochem.2011. Webb, J.S., Thornton, I., Thompson, M., Howarth, R.J., Lowenstein, P.L., 1978. The
01.007. Wolfson Geochemical Atlas of England and Wales. Oxford University Press, Oxford
Lines, Gregory C., 1996. Ground-Water and Surface-Water relations along the Mojave (70 pp.).
River, southern California. In: U.S. Geological Survey Water-resources Investigations Welch, A.H., Westjohn, D.B., Helsel, D.R., Wanty, R.B., 2000. Arsenic in ground water of
Report 95-4189, (42 pp.). the United States: occurrence and geochemistry. Ground Water 38 (4), 589–604.
Meisling, K.E., Weldon, R.J., 1989. Late Cenozoic tectonics of the northwestern San Wenzel, W.W., Kirchbaumer, N., Prohaska, T., Stingeder, G., Enzo, L., Adriano, D.C.,
Bernardino Mountains, southern California. Geol. Soc. Am. Bull. 101, 106–128. 2001. Arsenic fractionation in soils using an improved sequential extraction proce-
Metzger, L.F., Landon, M.K., House, S.F., Olsen, L.D., 2015. Mapping selected trace ele- dure. Anal. Chim. Acta 436, 309–323.
ments and major ions, 2000–2012. In: Mojave River and Morongo Groundwater Wold, S., Esbensen, K., Geladi, P., 1987. Principal component analysis. Chemom. Intell.
Basins, Southwestern Mojave Desert, San Bernardino County, California: U.S. Lab. Syst. 2, 37–52.
Geological Survey Data Release, https://doi.org/10.5066/F7Q23X95. (http://ca. Wright, M.T., Belitz, K., 2010. Factors controlling the regional distribution of vanadium in
water.usgs.gov/mojave/water-quality.html). groundwater. Ground Water 48 (4), 515–525. https://doi.org/10.1111/j.1745-6584.
Miller, D.M., Bedford, D.F., 2000. Geologic map database of the El Mirage Lake area, San 2009.00666.x.
Bernardino and Los Angeles counties, California. In: U.S. Geological Survey Open-file

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