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USGS2008

Anthropogenic influences on the input and biogeochemical cycling of nutrients and mercury in Great Salt Lake, Utah, USA

Despite the ecological and economic importance of Great Salt Lake (GSL), little is known about the input and biogeochemical cycling of nutrients and trace elements in the lake. In response to increasing public concern regarding anthropogenic inputs to the GSL ecosystem, the US Geological Survey (USGS) and US Fish and Wildlife Service (USFWS) initiated coordinated studies to quantify and evaluate the significance of nutrient and Hg inputs into GSL. A 6??? decrease in ??15N observed in brine shrimp (Artemia franciscana) samples collected from GSL during summer time periods is likely due to the consumption of cyanobacteria produced in freshwater bays entering the lake. Supporting data collected from the outflow of Farmington Bay indicates decreasing trends in ??15N in particulate organic matter (POM) during the mid-summer time period, reflective of increasing proportions of cyanobacteria in algae exported to GSL on a seasonal basis. The C:N molar ratio of POM in outflow from Farmington Bay decreases during the summer period, supportive of the increased activity of N fixation indicated by decreasing ??15N in brine shrimp and POM. Although N fixation is only taking place in the relatively freshwater inflows to GSL, data indicate that influx of fresh water influences large areas of the lake. Separation of GSL into two distinct hydrologic and geochemical systems from the construction of a railroad causeway in the late 1950s has created a persistent and widespread anoxic layer in the southern part of GSL. This anoxic layer, referred to as the deep brine layer (DBL), has high rates of SO42 - reduction, likely increasing the Hg methylation capacity. High concentrations of methyl mercury (CH3Hg) (median concentration = 24 ng/L) were observed in the DBL with a significant proportion (31-60%) of total Hg in the CH3Hg form. Hydroacoustic and sediment-trap evidence indicate that turbulence introduced by internal waves generated during sustained wind events can temporarily mix the elevated CH3Hg concentrations in the DBL with the more biologically active upper brine layer (UBL). Brine shrimp collected during the summer/fall time periods contained elevated Hg concentrations (median concentration = 0.34 mg/kg, dry weight (dw)) relative to samples collected during the spring (median concentration < 0.2 mg/kg, dw). Higher Hg in brine shrimp during the summer and fall may reflect the higher proportion of adult brine shrimp during this time period, resulting in an increased time for bioaccumulation of Hg. Eared grebes (Podiceps nigricollis) consume brine shrimp from GSL during the fall molting period. Median Hg concentrations in eared grebe livers increased by almost three times during the 3-5 month fall molting period. Selected duck species utilizing GSL have consistently exceeded the US Environmental Protection Agency (USEPA) screening level for Hg (0.3 mg/kg Hg wet weight), resulting in the issuance of warnings against unlimited human consumption of breast muscle tissue.

Applied Geochemistry↗
USGS2008

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d'Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models.

Idaho↗
USGS2008

Growing up green on serpentine soils: Biogeochemistry of serpentine vegetation in the Central Coast Range of California

Serpentine soils derived from the weathering of ultramafic rocks and their metamorphic derivatives (serpentinites) are chemically prohibitive for vegetative growth. Evaluating how serpentine vegetation is able to persist under these chemical conditions is difficult to ascertain due to the numerous factors (climate, relief, time, water availability, etc.) controlling and affecting plant growth. Here, the uptake, incorporation, and distribution of a wide variety of elements into the biomass of serpentine vegetation has been investigated relative to vegetation growing on an adjacent chert-derived soil. Soil pH, electrical conductivity, organic C, total N, soil extractable elements, total soil elemental compositions and plant digestions in conjunction with spider diagrams are utilized to determine the chemical relationships of these soil and plant systems. Plant available Mg and Ca in serpentine soils exceed values assessed in chert soils. Magnesium is nearly 3 times more abundant than Ca in the serpentine soils; however, the serpentine soils are not Ca deficient with Ca concentrations as high as 2235 mg kg-1. Calcium to Mg ratios (Ca:Mg) in both serpentine and chert vegetation are greater than one in both below and above ground tissues. Soil and plant chemistry analyses support that Ca is not a limiting factor for plant growth and that serpentine vegetation is actively moderating Mg uptake as well as tolerating elevated concentrations of bioavailable Mg. Additionally, results demonstrate that serpentine vegetation suppresses the uptake of Fe, Cr, Ni, Mn and Co into its biomass. The suppressed uptake of these metals mainly occurs in the plants' roots as evident by the comparatively lower metal concentrations present in above ground tissues (twigs, leaves and shoots). This research supports earlier studies that have suggested that ion uptake discrimination and ion suppression in the roots are major mechanisms for serpentine vegetation to tolerate the chemistry of serpentine soils. ?? 2008 Elsevier Ltd.

Applied Geochemistry↗
USGS2008

Laboratory and field evaluation of a flushable oxic limestone drain for treatment of net-acidic drainage from a flooded anthracite mine, Pennsylvania, USA

This paper demonstrates the use of dissolution-rate data obtained in the laboratory to indicate the potential quality of effluent from a field-scale oxic limestone drain (OLD) treatment system for neutralization of dilute acidic mine drainage (AMD). Effluent from the Reevesdale Mine South Dip Tunnel, a large source of AMD and base flow to the Wabash Creek and Little Schuylkill River in the Southern Anthracite Coalfield of east-central Pennsylvania, is representative of AMD with low concentrations but high loadings of dissolved Fe, Al and other metals because of a high flow rate. In January 2003, rapid neutralization of the AMD from the Reevesdale Mine was achieved in laboratory tests of its reaction rate with crushed limestone in closed, collapsible containers (Cubitainers). The tests showed that net-alkaline effluent could be achieved with retention times greater than 3 h and that effluent alkalinities and associated dissolution rates were equivalent for Fe(OH)3-coated and uncoated limestone. On the basis of the laboratory results, a flushable OLD containing 1450 metric tons of high-purity calcitic limestone followed by two 0.7-m deep wetlands were constructed at the Reevesdale Mine. During the first year of operation, monthly data at the inflow, outflow and intermediate points within the treatment system were collected (April 2006-2007). The inflow to the treatment system ranged from 6.8 to 27.4 L/s, with median pH of 4.7, net acidity of 9.1 mg/L CaCO3, and concentrations of dissolved Al, Fe and Mn of 1.0, 1.9 and 0.89 mg/L, respectively. The corresponding effluent from the OLD had computed void-volume retention times of 4.5-18 h, with median pH of 6.6, net acidity of -93.2 mg/L CaCO3, and concentrations of dissolved Al, Fe and Mn of <0.1, 0.08 and 0.52 mg/L, respectively. The wetlands below the OLD were effective for retaining metal-rich solids flushed at monthly or more frequent intervals from the OLD, but otherwise had little effect on the effluent quality. During the first year of operation, approximately 43 metric tons of limestone were dissolved and 2 metric tons of Al, Fe and Mn were precipitated within the OLD. However, because of the accumulation of these metals within the OLD and possibly other debris from the mine, the effectiveness of the treatment system declined. Despite the installation of a flush-pipe network at the base of the OLD to remove precipitated solids, the limestone bed clogged near the inflow. Consequently, a large fraction of the AMD bypassed the treatment system. To promote flow through the OLD, the flush pipes were open continuously during the last 4 months of the study; however, this effluent was only partially treated because short-circuiting through the pipes decreased contact between the effluent and limestone. A reconfiguration of the flow path through the limestone bed from horizontal to vertical upward could increase the limestone surface area exposed to the metal-laden influent, increase the cross-sectional area perpendicular to flow, decrease the flow path for solids removal, and, consequently, decrease potential for clogging.

Applied Geochemistry↗
USGS2009

An empirical method for estimating instream pre-mining pH and dissolved Cu concentration in catchments with acidic drainage and ferricrete

Methods for assessing natural background water quality of streams affected by historical mining are vigorously debated. An empirical method is proposed in which stream-specific estimation equations are generated from relationships between either pH or dissolved Cu concentration in stream water and the Fe/Cu concentration ratio in Fe-precipitates presently forming in the stream. The equations and Fe/Cu ratios for pre-mining deposits of alluvial ferricrete then were used to reconstruct estimated pre-mining longitudinal profiles for pH and dissolved Cu in three acidic streams in Montana, USA. Primary assumptions underlying the proposed method are that alluvial ferricretes and modern Fe-precipitates share a common origin, that the Cu content of Fe-precipitates remains constant during and after conversion to ferricrete, and that geochemical factors other than pH and dissolved Cu concentration play a lesser role in determining Fe/Cu ratios in Fe-precipitates. The method was evaluated by applying it in a fourth, naturally acidic stream unaffected by mining, where estimated pre-mining pH and Cu concentrations were similar to present-day values, and by demonstrating that inflows, particularly from unmined areas, had consistent effects on both the pre-mining and measured profiles of pH and Cu concentration. Using this method, it was estimated that mining has affected about 480 m of Daisy Creek, 1.8 km of Fisher Creek, and at least 1 km of Swift Gulch. Mean values of pH decreased by about 0.6 pH units to about 3.2 in Daisy Creek and by 1-1.5 pH units to about 3.5 in Fisher Creek. In Swift Gulch, mining appears to have decreased pH from about 5.5 to as low as 3.6. Dissolved Cu concentrations increased due to mining almost 40% in Daisy Creek to a mean of 11.7 mg/L and as much as 230% in Fisher Creek to 0.690 mg/L. Uncertainty in the fate of Cu during the conversion of Fe-precipitates to ferricrete translates to potential errors in pre-mining estimates of as much as 0.25 units for pH and 22% for dissolved Cu concentration. The method warrants further testing in other mined and unmined watersheds. Comparison of pre-mining water-quality estimates derived from the ferricrete and other methods in single watersheds would be particularly valuable. The method has potential for use in monitoring remedial efforts at mine sites with ferricrete deposits. A reasonable remediation objective might be realized when the downstream pattern of Fe/Cu ratios in modern streambed Fe-precipitates corresponds to the pattern in pre-mining alluvial ferricrete deposits along a stream valley.

Applied Geochemistry↗
USGS2009

Naturally acidic surface and ground waters draining porphyry-related mineralized areas of the Southern Rocky Mountains, Colorado and New Mexico

Acidic, metal-rich waters produced by the oxidative weathering and resulting leaching of major and trace elements from pyritic rocks can adversely affect water quality in receiving streams and riparian ecosystems. Five study areas in the southern Rocky Mountains with naturally acidic waters associated with porphyry mineralization were studied to document variations in water chemistry and processes that control the chemical variations. Study areas include the Upper Animas River watershed, East Alpine Gulch, Mount Emmons, and Handcart Gulch in Colorado and the Red River in New Mexico. Although host-rock lithologies in all these areas range from Precambrian gneisses to Cretaceous sedimentary units to Tertiary volcanic complexes, the mineralization is Tertiary in age and associated with intermediate to felsic composition, porphyritic plutons. Pyrite is ubiquitous, ranging from ???1 to >5 vol.%. Springs and headwater streams have pH values as low as 2.6, SO4 up to 3700 mg/L and high dissolved metal concentrations (for example: Fe up to 400 mg/L; Cu up to 3.5 mg/L; and Zn up to 14.4 mg/L). Intensity of hydrothermal alteration and presence of sulfides are the primary controls of water chemistry of these naturally acidic waters. Subbasins underlain by intensely hydrothermally altered lithologies are poorly vegetated and quite susceptible to storm-induced surface runoff. Within the Red River study area, results from a storm runoff study documented downstream changes in river chemistry: pH decreased from 7.80 to 4.83, alkalinity decreased from 49.4 to <1 mg/L, SO4 increased from 162 to 314 mg/L, dissolved Fe increased from to 0.011 to 0.596 mg/L, and dissolved Zn increased from 0.056 to 0.607 mg/L. Compared to mine drainage in the same study areas, the chemistry of naturally acidic waters tends to overlap but not reach the extreme concentrations of metals and acidity as some mine waters. The chemistry of waters draining these mineralized but unmined areas can be used to estimate premining conditions at sites with similar geologic and hydrologic conditions. For example, the US Geological Survey was asked to estimate premining ground-water chemistry at the Questa Mo mine, and the proximal analog approach was used because a mineralized but unmined area was located adjacent to the mine property. By comparing and contrasting water chemistry from different porphyry mineralized areas, this study not only documents the range in concentrations of constituents of interest but also provides insight into the primary controls of water chemistry.

Applied Geochemistry↗
USGS2009

The Drenchwater deposit, Alaska: An example of a natural low pH environment resulting from weathering of an undisturbed shale-hosted Zn-Pb-Ag deposit

The Drenchwater shale-hosted Zn-Pb-Ag deposit and the immediate vicinity, on the northern flank of the Brooks Range in north-central Alaska, is an ideal example of a naturally low pH system. The two drainages, Drenchwater and False Wager Creeks, which bound the deposit, differ in their acidity and metal contents. Moderately acidic waters with elevated concentrations of metals (pH ??? 4.3, Zn ??? 1400 ??g/L) in the Drenchwater Creek drainage basin are attributed to weathering of an exposed base-metal-rich massive sulfide occurrence. Stream sediment and water chemistry data collected from False Wager Creek suggest that an unexposed base-metal sulfide occurrence may account for the lower pH (2.7-3.1) and very metal-rich waters (up to 2600 ??g/L Zn, ??? 260 ??g/L Cu and ???89 ??g/L Tl) collected at least 2 km upstream of known mineralized exposures. These more acidic conditions produce jarosite, schwertmannite and Fe-hydroxides commonly associated with acid-mine drainage. The high metal concentrations in some water samples from both streams naturally exceed Alaska state regulatory limits for freshwater aquatic life, affirming the importance of establishing base-line conditions in the event of human land development. The studies at the Drenchwater deposit demonstrate that poor water quality can be generated through entirely natural weathering of base-metal occurrences, and, possibly unmineralized black shale.

Applied Geochemistry↗
USGS2009

Geochemical gradients in soil O-horizon samples from southern Norway: Natural or anthropogenic?

Forty soil O- and C-horizon samples were collected along a south-to-north transect extending inland for approximately 200 km from the southern tip of Norway. The elements As, Au, Bi, Cd, Cu, Ga, Ge, Hf, Hg, In, Mg, Mn, Mo, Na, Ni, Pb, Sb, Se, V, W, Zn and Zr all show a distinct decrease in concentration in soil O-horizons with increasing distance from the coast. The elements showing the strongest coastal enrichment, some by more than an order of magnitude compared to inland samples, are Au, Bi, As, Pb, Sb and Sn. Furthermore, the elements Cd (median O-/median C-horizon = 31), C, Sb, Ag, K, S, Ge (10), Hg, Pb, As, Bi, Sr (5), Se, Au, Ba, Na, Zn, P, Cu and Sn (2) are all strongly enriched in the O-horizon when compared to the underlying C-horizon. Lead isotope ratios, however, do not show any gradient with distance from the coast (declining Pb concentration). Along a 50 km topographically steep east-west transect in the centre of the survey area, far from the coast but crossing several vegetation zones, similar element enrichment patterns and concentration gradients can be observed in the O-horizon. Lead isotope ratios in the O-horizon correlate along both transects with pH and the C/N-ratio, both proxies for the quality of the organic material. Natural conditions in southern Norway, related to climate and vegetation, rather than long range atmospheric transport of air pollutants (LRT), cause the observed features. ?? 2008 Elsevier Ltd.

Applied Geochemistry↗
USGS2009

Diffuse gas emissions at the Ukinrek Maars, Alaska: Implications for magmatic degassing and volcanic monitoring

Diffuse CO2 efflux near the Ukinrek Maars, two small volcanic craters that formed in 1977 in a remote part of the Alaska Peninsula, was investigated using accumulation chamber measurements. High CO2 efflux, in many places exceeding 1000 g m−2 d−1, was found in conspicuous zones of plant damage or kill that cover 30,000–50,000 m2 in area. Total diffuse CO2 emission was estimated at 21–44 t d−1. Gas vents 3-km away at The Gas Rocks produce 0.5 t d−1 of CO2 that probably derives from the Ukinrek Maars basalt based on similar δ13C values (∼−6‰), 3He/4He ratios (5.9–7.2 RA), and CO2/3He ratios (1–2 × 109) in the two areas. A lower 3He/4He ratio (2.7 RA) and much higher CO2/3He ratio (9 × 1010) in gas from the nearest arc-front volcanic center (Mount Peulik/Ugashik) provide a useful comparison. The large diffuse CO2 emission at Ukinrek has important implications for magmatic degassing, subsurface gas transport, and local toxicity hazards. Gas–water–rock interactions play a major role in the location, magnitude and chemistry of the emissions.

Alaska↗
USGS2009

Potential environmental issues of CO 2 storage in deep saline aquifers: Geochemical results from the Frio-I Brine Pilot test, Texas, USA

Sedimentary basins in general, and deep saline aquifers in particular, are being investigated as possible repositories for large volumes of anthropogenic CO 2 that must be sequestered to mitigate global warming and related climate changes. To investigate the potential for the long-term storage of CO 2 in such aquifers, 1600 t of CO 2 were injected at 1500 m depth into a 24-m-thick "C" sandstone unit of the Frio Formation, a regional aquifer in the US Gulf Coast. Fluid samples obtained before CO 2 injection from the injection well and an observation well 30 m updip showed a Na–Ca–Cl type brine with ∼93,000 mg/L TDS at saturation with CH 4 at reservoir conditions; gas analyses showed that CH 4 comprised ∼95% of dissolved gas, but CO 2 was low at 0.3%. Following CO 2 breakthrough, 51 h after injection, samples showed sharp drops in pH (6.5–5.7), pronounced increases in alkalinity (100–3000 mg/L as HCO 3 ) and in Fe (30–1100 mg/L), a slug of very high DOC values, and significant shifts in the isotopic compositions of H 2 O, DIC, and CH 4 . These data, coupled with geochemical modeling, indicate corrosion of pipe and well casing as well as rapid dissolution of minerals, especially calcite and iron oxyhydroxides, both caused by lowered pH (initially ∼3.0 at subsurface conditions) of the brine in contact with supercritical CO 2 . These geochemical parameters, together with perfluorocarbon tracer gases (PFTs), were used to monitor migration of the injected CO 2 into the overlying Frio “B”, composed of a 4-m-thick sandstone and separated from the “C” by ∼15 m of shale and siltstone beds. Results obtained from the Frio “B” 6 months after injection gave chemical and isotopic markers that show significant CO 2 (2.9% compared with 0.3% CO 2 in dissolved gas) migration into the “B” sandstone. Results of samples collected 15 months after injection, however, are ambiguous, and can be interpreted to show no additional injected CO 2 in the “B” sandstone. The presence of injected CO 2 may indicate migration from “C” to “B” through the intervening beds or, more likely, a short-term leakage through the remedial cement around the casing of a 50-year old well. Results obtained to date from four shallow monitoring groundwater wells show no brine or CO 2 leakage through the Anahuac Formation, the regional cap rock.

Texas↗
USGS2009

Estimating selenium removal by sedimentation from the Great Salt Lake, Utah

The mass of Se deposited annually to sediment in the Great Salt Lake (GSL) was estimated to determine the significance of sedimentation as a permanent Se removal mechanism. Lake sediment cores were used to qualitatively delineate sedimentation regions (very high to very low), estimate mass accumulation rates (MARs) and determine sediment Se concentrations. Sedimentation regions were defined by comparison of isopach contours of Holocene sediment thicknesses to linear sedimentation rates determined via analysis of 210 Pb, 226 Ra, 7 Be and 137 Cs activity in 20 short cores (<5 cm), yielding quantifiable results in 13 cores. MARs were developed via analysis of the same radioisotopes in eight long cores (>10 cm). These MARs in the upper 1-2 cm of each long core ranged from 0.019 to 0.105 g sed /cm 2 /a. Surface sediment Se concentrations in the upper 1 or 2 cm of each long core ranged from 0.79 to 2.47 mg/kg. Representative MARs and Se concentrations were used to develop mean annual Se removal by sedimentation in the corresponding sedimentation region. The spatially integrated Se sedimentation rate was estimated to be 624 kg/a within a range of uncertainty between 285 and 960 kg/a. Comparison to annual Se loading and other potential removal processes suggests burial by sedimentation is not the primary removal process for Se from the GSL. ?? 2009 Elsevier Ltd.

Applied Geochemistry↗
USGS2009

Pilot studies for the North American Soil Geochemical Landscapes Project - Site selection, sampling protocols, analytical methods, and quality control protocols

In 2004, the US Geological Survey (USGS) and the Geological Survey of Canada sampled and chemically analyzed soils along two transects across Canada and the USA in preparation for a planned soil geochemical survey of North America. This effort was a pilot study to test and refine sampling protocols, analytical methods, quality control protocols, and field logistics for the continental survey. A total of 220 sample sites were selected at approximately 40-km intervals along the two transects. The ideal sampling protocol at each site called for a sample from a depth of 0-5 cm and a composite of each of the O, A, and C horizons. The <2-mm fraction of each sample was analyzed for Al, Ca, Fe, K, Mg, Na, S, Ti, Ag, As, Ba, Be, Bi, Cd, Ce, Co, Cr, Cs, Cu, Ga, In, La, Li, Mn, Mo, Nb, Ni, P, Pb, Rb, Sb, Sc, Sn, Sr, Te, Th, Tl, U, V, W, Y, and Zn by inductively coupled plasma-mass spectrometry and inductively coupled plasma-atomic emission spectrometry following a near-total digestion in a mixture of HCl, HNO 3 , HClO 4 , and HF. Separate methods were used for Hg, Se, total C, and carbonate-C on this same size fraction. Only Ag, In, and Te had a large percentage of concentrations below the detection limit. Quality control (QC) of the analyses was monitored at three levels: the laboratory performing the analysis, the USGS QC officer, and the principal investigator for the study. This level of review resulted in an average of one QC sample for every 20 field samples, which proved to be minimally adequate for such a large-scale survey. Additional QC samples should be added to monitor within-batch quality to the extent that no more than 10 samples are analyzed between a QC sample. Only Cr (77%), Y (82%), and Sb (80%) fell outside the acceptable limits of accuracy (% recovery between 85 and 115%) because of likely residence in mineral phases resistant to the acid digestion. A separate sample of 0-5-cm material was collected at each site for determination of organic compounds. A subset of 73 of these samples was analyzed for a suite of 19 organochlorine pesticides by gas chromatography. Only three of these samples had detectable pesticide concentrations. A separate sample of A-horizon soil was collected for microbial characterization by phospholipid fatty acid analysis (PLFA), soil enzyme assays, and determination of selected human and agricultural pathogens. Collection, preservation and analysis of samples for both organic compounds and microbial characterization add a great degree of complication to the sampling and preservation protocols and a significant increase to the cost for a continental-scale survey. Both these issues must be considered carefully prior to adopting these parameters as part of the soil geochemical survey of North America.

Applied Geochemistry↗
USGS2009

A water-leach procedure for estimating bioaccessibility of elements in soils from transects across the United States and Canada

An objective of the North American Soil Geochemical Landscapes Project is to provide relevant data concerning bioaccessible concentrations of elements in soil to government and other institutions undertaking environmental studies. A protocol was developed that employs a 1-g soil sample agitated overnight with 40 mL of reverse-osmosis de-ionized water for 20 h, and determination of 63 elements following three steps of centrifugation by inductively coupled plasma&ndash;atomic emission spectrometry and inductively coupled plasma&ndash;mass spectrometry the following day. Statistical summaries are presented for those 48 elements (Ag, Al, As, B, Ba, Be, Br, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Ho, I, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, P, Pb, Pr, Rb, Re, S, Sb, Si, Sm, Sn, Sr, Tb, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr, and pH) for which <20% of their data were reported as below the detection limit. The resulting data set contains analyses for 161 A-horizon soils collected along two transects, one along the 38th parallel across the USA and the other from northern Manitoba to the USA&ndash;Mexico border. The spatial distribution of three selected elements (Ca, Cu, and Pb) along the two transects is discussed in this paper both as absolute amounts liberated by the leach and expressed as a percentage of the total, or near-total, amounts determined for the elements. The Ca data reflect broad trends in soil parent materials, their weathering, and subsequent soil development. Calcium concentrations are generally found to be lower in the older soils of the eastern USA. The Cu data are higher in the eastern half of the USA, correlating with soil organic C, with which it is sequestered. The Pb data exhibit little regional variability due to natural sources, but are influenced by anthropogenic sources. Based on the Pb results, the percentage water-extractable data demonstrate promise as a tool for identifying anthropogenic components. The soil&ndash;water partition (distribution) coefficients, K d s (L/kg), were determined and their relevance to estimating bioaccessible amounts of elements to soil fauna and flora is discussed. Finally, a possible link between W concentrations in human urine and water-extractable W levels in Nevada soils is discussed.

Applied Geochemistry↗
USGS2009

Application of in vitro extraction studies to evaluate element bioaccessibility in soils from a transect across the United States and Canada

In vitro bioaccessibility tests (IVBA) are inexpensive, physiologically-based extraction tests designed to estimate the bioaccessibility of elements along ingestion exposure pathways. Published IVBA protocols call for the testing to be done on the <250-??m fraction of soil, as these particles are most likely to adhere to the hands of children and be ingested. Most IVBA in the literature to date have been applied to soil samples from highly contaminated sites or to spiked samples, and relatively little work has been done to evaluate bioaccessibility of elements in a wide variety of uncontaminated 'background' soils. In 2004, the US Geological Survey and the Geological Survey of Canada sampled soils along north-south and east-west transects across the two countries to test and refine sampling and analytical protocols recommended for the planned soil geochemical survey of North America. Samples were collected at 220 sites selected randomly at approximately 40-km intervals. The focus of the investigation presented in this paper was twofold: (1) to begin to examine variations in bioaccessibility of As, Cd, Cr, Ni and Pb in a number of 'background' (i.e., unpolluted) soils from around North America and (2) to determine if there are significant differences that would preclude using the standard size fraction of <2 mm for extraction with a simulated gastric fluid as an expeditious and inexpensive bioaccessibility screening tool for the large numbers of future samples to be collected by this continental-scale project. A subset of 20 soil samples collected along the north-south transect at a depth of 0-5 cm was used for this study. Two separate size fractions (<2 mm and <250 ??m) were extracted using a simulated human gastric fluid consisting of a solution of HCl and glycine adjusted to a pH of 1.5. In general, the leachate results for the <2-mm size fraction were not substantially different than those for the <250-??m size fraction for concentrations of As, Cd, Cr, Ni and Pb. Leachate concentrations for Cd, Ni and Pb appear to be controlled to some extent by the total concentration of the element in soil. Bioaccessibility of the elements in this study decreased in the order, Cd > Pb > Ni > As > Cr.

Applied Geochemistry↗