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At least 217 records · Page 12Linked to original sources

A survey of the occurrence of Bacillus anthracis in North American soils over two long-range transects and within post-Katrina New Orleans

Soil samples were collected along a north-south transect extending from Manitoba, Canada, to the US-Mexico border near El Paso, Texas in 2004 (104 samples), a group of sites within New Orleans, Louisiana following Hurricane Katrina in 2005 (19 samples), and a Gulf Coast transect extending from Sulphur, Louisiana, to DeFuniak Springs, Florida, in 2007 (38 samples). Samples were collected from the top 40 cm of soil and were screened for the presence of total Bacillus species and Bacillus anthracis (anthrax), specifically using multiplex-polymerase chain reaction (PCR). Using an assay with a sensitivity of ???170 equivalent colony-forming units (CFU) g -1 field moist soil, the prevalence rate of Bacillus sp./B. anthracis in the north-south transect and the 2005 New Orleans post-Katrina sample set were 20/5% and 26/26%, respectively. Prevalence in the 2007 Gulf Coast sample set using an assay with a sensitivity of ???4 CFU g -1 of soil was 63/0%. Individual transect-set data indicate a positive relation between occurrences of species and soil moisture or soil constituents (i.e., Zn and Cu content). The 2005 New Orleans post-Katrina data indicated that B. anthracis is readily detectable in Gulf Coast soils following flood events. The data also indicated that occurrence, as it relates to soil chemistry, may be confounded by flood-induced dissemination of germinated cells and the mixing of soil constituents for short temporal periods following an event.

Applied Geochemistry↗

The potential of mid- and near-infrared diffuse reflectance spectroscopy for determining major- and trace-element concentrations in soils from a geochemical survey of North America

In 2004, soils were collected at 220 sites along two transects across the USA and Canada as a pilot study for a planned soil geochemical survey of North America (North American Soil Geochemical Landscapes Project). The objective of the current study was to examine the potential of diffuse reflectance (DR) Fourier Transform (FT) mid-infrared (mid-IR) and near-infrared (NIRS) spectroscopy to reduce the need for conventional analysis for the determination of major and trace elements in such continental-scale surveys. Soil samples (n = 720) were collected from two transects (east-west across the USA, and north-south from Manitoba, Canada to El Paso, Texas (USA), n = 453 and 267, respectively). The samples came from 19 USA states and the province of Manitoba in Canada. They represented 31 types of land use (e.g., national forest, rangeland, etc.), and 123 different land covers (e.g., soybeans, oak forest, etc.). The samples represented a combination of depth-based sampling (0-5 cm) and horizon-based sampling (O, A and C horizons) with 123 different depths identified. The set was very diverse with few samples similar in land use, land cover, etc. All samples were analyzed by conventional means for the near-total concentration of 49 analytes (C total , C carbonate and C organic , and 46 major and trace elements). Spectra were obtained using dried, ground samples using a Digilab FTS-7000 FT spectrometer in the mid- (4000-400 cm -1 ) and near-infrared (10,000-4000 cm -1 ) at 4 cm -1 resolution (64 co-added scans per spectrum) using a Pike AutoDIFF DR autosampler. Partial least squares calibrations were develop using: (1) all samples as a calibration set; (2) samples evenly divided into calibration and validation sets based on spectral diversity; and (3) samples divided to have matching analyte concentrations in calibration and validation sets. In general, results supported the conclusion that neither mid-IR nor NIRS would be particularly useful in reducing the need for conventional analysis of soils from this continental-scale geochemical survey. The extreme sample diversity, likely caused by the widely varied parent material, land use at the site of collection (e.g., grazing, recreation, agriculture, etc.), and climate resulted in poor calibrations even for C total , C organic and C carbonate . The results indicated potential for mid-IR and NIRS to differentiate soils containing high concentrations (>100 mg/kg) of some metals (e.g., Co, Cr, Ni) from low-level samples (<50 mg/kg). However, because of the small number of high-level samples, it is possible that differentiation was based on factors other than metal concentration. Results for Mg and Sr were good, but results for other metals examined were fair to poor, at best. In essence, it appears that the great variation in chemical and physical properties seen in soils from this continental-scale survey resulted in each sample being virtually unique. Thus, suitable spectroscopic calibrations were generally not possible.

Applied Geochemistry↗

Regional variations in water quality and relationships to soil and bedrock weathering in the southern Sacramento Valley, California, USA

Regional patterns in ground- and surface-water chemistry of the southern Sacramento Valley in California were evaluated using publicly available geochemical data from the US Geological Survey's National Water Information System (NWIS). Within the boundaries of the study area, more than 2300 ground-water analyses and more than 20,000 surface-water analyses were available. Ground-waters from the west side of the Sacramento Valley contain greater concentrations of Na, Ca, Mg, B, Cl and SO 4 , while the east-side ground-waters contain greater concentrations of silica and K. These differences result from variations in surface-water chemistry as well as from chemical reactions between water and aquifer materials. Sediments that fill the Sacramento Valley were derived from highlands to the west (the Coast Ranges) and east (the Sierra Nevada Mountains), the former having an oceanic provenance and the latter continental. These geologic differences are at least in part responsible for the observed patterns in ground-water chemistry. Thermal springs that are common along the west side of the Sacramento Valley appear to have an effect on surface-water chemistry, which in turn may affect the ground-water chemistry.

Applied Geochemistry↗

Geomorphic controls on mercury accumulation in soils from a historically mined watershed, Central California Coast Range, USA

Historic Hg mining in the Cache Creek watershed in the Central California Coast Range has contributed to the downstream transport of Hg to the San Francisco Bay-Delta. Different aspects of Hg mobilization in soils, including pedogenesis, fluvial redistribution of sediment, volatilization and eolian transport were considered. The greatest soil concentrations (>30 mg Hg kg -1 ) in Cache Creek are associated with mineralized serpentinite, the host rock for Hg deposits. Upland soils with non-mineralized serpentine and sedimentary parent material also had elevated concentrations (0.9-3.7 mg Hg kg -1 ) relative to the average concentration in the region and throughout the conterminous United States (0.06 mg kg -1 ). Erosion of soil and destabilized rock and mobilization of tailings and calcines into surrounding streams have contributed to Hg-rich alluvial soil forming in wetlands and floodplains. The concentration of Hg in floodplain sediment shows sediment dispersion from low-order catchments (5.6-9.6 mg Hg kg -1 in Sulphur Creek; 0.5-61 mg Hg kg -1 in Davis Creek) to Cache Creek (0.1-0.4 mg Hg kg -1 ). These sediments, deposited onto the floodplain during high-flow storm events, yield elevated Hg concentrations (0.2-55 mg Hg kg -1 ) in alluvial soils in upland watersheds. Alluvial soils within the Cache Creek watershed accumulate Hg from upstream mining areas, with concentrations between 0.06 and 0.22 mg Hg kg -1 measured in soils ~90 km downstream from Hg mining areas. Alluvial soils have accumulated Hg released through historic mining activities, remobilizing this Hg to streams as the soils erode.

Applied Geochemistry↗

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop-Zones A-C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite-smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.

Applied Geochemistry↗

Soil geochemical signature of urbanization and industrialization – Chicago, Illinois, USA

The concentrations of 45 elements in ambient (not obviously disturbed) surface soils were determined for 57 sites distributed throughout the city of Chicago, Illinois in the upper Midwestern United States. These concentrations were compared to soils from 105 sites from a largely agricultural region within a 500-km radius surrounding the city and to soils collected from 90 sites across the state of Illinois. Although the bulk composition of the Chicago urban soils reflects largely natural sources, the soils are significantly enriched in many trace elements, apparently from anthropogenic sources. The median concentration of Pb in Chicago soils is 198 mg/kg, a 13-fold enrichment compared to regional concentrations. Zinc (median 235 mg/kg), Cu (59 mg/kg), and Ni (31 mg/kg) are also enriched from 2- to 4-fold in Chicago soils and all four elements show strong mutual correlations. These elevated concentrations are most likely related to vehicular and roadway sources and represent uneven distribution across the city as airborne material. Other airborne particulate material from a combination of fossil fuel combustion, waste incineration, and steel production may contribute to apparent elevated concentrations in Chicago soil of Fe (median 2.9%), Mo (5 mg/kg), V (82 mg/kg) and S (0.09%). Chicago soils are enriched from about 1.6- to 3-fold in these elements. Enrichments in P and Se may be caused by direct addition of phosphate fertilizer to parklands, lawns and gardens. The density of the sampling (1 site per 10 km 2 ) is inadequate to define the distribution of the observed enrichments within the city or to predict soil compositions for most of the areas between sample sites, but does provide a statistically significant signature of the history of urban and industrial activity within the city in contrast to the surrounding agricultural lands.

Illinois↗

Size and elemental distributions of nano- to micro-particulates in the geochemically-stratified Great Salt Lake

The characterization of trace elements in terms of their apportionment among dissolved, macromolecular, nano- and micro-particulate phases in the water column of the Great Salt Lake carries implications for the potential entry of toxins into the food web of the lake. Samples from the anoxic deep and oxic shallow brine layers of the lake were fractionated using asymmetric flow field-flow fractionation (AF4). The associated trace elements were measured via online collision cell inductively-coupled plasma mass spectrometry (CC-ICP-MS). Results showed that of the total (dissolved + particulate) trace element mass, the percent associated with particulates varied from negligible (e.g. Sb), to greater than 50% (e.g. Al, Fe, Pb). Elements such as Cu, Zn, Mn, Co, Au, Hg, and U were associated with nanoparticles, as well as being present as dissolved species. Particulate-associated trace elements were predominantly associated with particulates larger than 450 nm in size. Among the smaller nanoparticulates (<450 nm), some trace elements (Ni, Zn, Au and Pb) showed higher percent mass (associated with nanoparticles) in the 0.9-7.5 nm size range relative to the 10-250 nm size range. The apparent nanoparticle size distributions were similar between the two brine layers; whereas, important differences in elemental associations to nanoparticles were discerned between the two layers. Elements such as Zn, Cu, Pb and Mo showed increasing signal intensities from oxic shallow to anoxic deep brine, suggesting the formation of sulfide nanoparticles, although this may also reflect association with dissolved organic matter. Aluminum and Fe showed greatly increased concentration with depth and equivalent size distributions that differed from those of Zn, Cu, Pb and Mo. Other elements (e.g. Mn, Ni, and Co) showed no significant change in signal intensity with depth. Arsenic was associated with <2 nm nanoparticles, and showed no increase in concentration with depth, possibly indicating dissolved arsenite. Mercury was associated with <2 nm nanoparticles, and showed greatly increased concentration with depth, possibly indicating association with dissolved organic matter. ?? 2009 Elsevier Ltd.

Applied Geochemistry↗

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies. Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.

Applied Geochemistry↗

Elevated naturally occurring arsenic in a semiarid oxidizing system, Southern High Plains aquifer, Texas, USA

High groundwater As concentrations in oxidizing systems are generally associated with As adsorption onto hydrous metal (Al, Fe or Mn) oxides and mobilization with increased pH. The objective of this study was to evaluate the distribution, sources and mobilization mechanisms of As in the Southern High Plains (SHP) aquifer, Texas, relative to those in other semiarid, oxidizing systems. Elevated groundwater As levels are widespread in the southern part of the SHP (SHP-S) aquifer, with 47% of wells exceeding the current EPA maximum contaminant level (MCL) of 10 μg/L (range 0.3–164 μg/L), whereas As levels are much lower in the north (SHP-N: 9% ⩾ As MCL of 10 μg/L; range 0.2–43 μg/L). The sharp contrast in As levels between the north and south coincides with a change in total dissolved solids (TDS) from 395 mg/L (median north) to 885 mg/L (median south). Arsenic is present as arsenate (As V) in this oxidizing system and is correlated with groundwater TDS (Spearman’s ρ = 0.57). The most likely current source of As is sorbed As onto hydrous metal oxides based on correlations between As and other oxyanion-forming elements (V, ρ = 0.88; Se, ρ = 0.54; B, ρ = 0.51 and Mo, ρ = 0.46). This source is similar to that in other oxidizing systems and constitutes a secondary source; the most likely primary source being volcanic ashes in the SHP aquifer or original source rocks in the Rockies, based on co-occurrence of As and F ( ρ = 0.56), oxyanion-forming elements and SiO 2 ( ρ = 0.41), which are found in volcanic ashes. High groundwater As concentrations in some semiarid oxidizing systems are related to high evaporation. Although correlation of As with TDS in the SHP aquifer may suggest evaporative concentration, unenriched stable isotopes (δ 2 H: −65 to −27; δ 18 O: −9.1 to −4.2) in the SHP aquifer do not support evaporation. High TDS in the SHP aquifer is most likely related to upward movement of saline water from the underlying Triassic Dockum aquifer. Mobilization of As in other semiarid oxidizing systems is caused by increased pH; however, pH in the SHP aquifer is near neutral (10–90 percentiles, 7.0–7.6). Although many processes, such as competitive desorption with SiO 2 , VO 4 , or PO 4 , could be responsible for local mobilization of As in the SHP aquifer, the most plausible explanation for the regional As distribution and correlation with TDS is the counterion effect caused by a change from Ca- to Na-rich, water as shown by the high correlation between As and Na/(Ca) 0.5 ratios ( ρ = 0.57). This change in chemistry is related to mixing with saline water that moves upward from the underlying Dockum aquifer. This counterion effect may mobilize other anions and oxyanion-forming elements that are correlated with As (F, V, Se, B, Mo and SiO 2 ). Competition among the oxyanions for sorption sites may enhance As mobilization. The SHP case study has similar As sources to those of other semiarid, oxidizing systems (original volcanic ash source followed by sorption onto hydrous metal oxides) but contrasts with these systems by showing lack of evaporative concentration and pH mobilization of As but counterion mobilization of As instead in the SHP-S aquifer.

Texas↗

Feldspar dissolution rates in the Topopah Spring Tuff, Yucca Mountain, Nevada

Two different field-based methods are used here to calculate feldspar dissolution rates in the Topopah Spring Tuff, the host rock for the proposed nuclear waste repository at Yucca Mountain, Nevada. The center of the tuff is a high silica rhyolite, consisting largely of alkali feldspar (∼60 wt%) and quartz polymorphs (∼35 wt%) that formed by devitrification of rhyolitic glass as the tuff cooled. First, the abundance of secondary aluminosilicates is used to estimate the cumulative amount of feldspar dissolution over the history of the tuff, and an ambient dissolution rate is calculated by using the estimated thermal history. Second, the feldspar dissolution rate is calculated by using measured Sr isotope compositions for the pore water and rock. Pore waters display systematic changes in Sr isotopic composition with depth that are caused by feldspar dissolution. The range in dissolution rates determined from secondary mineral abundances varies from 10 −16 to 10 −17 mol s −1 kg tuff −1 with the largest uncertainty being the effect of the early thermal history of the tuff. Dissolution rates based on pore water Sr isotopic data were calculated by treating percolation flux parametrically, and vary from 10 −15 to 10 −16 mol s −1 kg tuff −1 for percolation fluxes of 15 mm a −1 and 1 mm a −1 , respectively. Reconciling the rates from the two methods requires that percolation fluxes at the sampled locations be a few mm a −1 or less. The calculated feldspar dissolution rates are low relative to other measured field-based feldspar dissolution rates, possibly due to the age (12.8 Ma) of the unsaturated system at Yucca Mountain; because oxidizing and organic-poor conditions limit biological activity; and/or because elevated silica concentrations in the pore waters (∼50 mg L −1 ) may inhibit feldspar dissolution.

Nevada↗

Investigating hydraulic connections and the origin of water in a mine tunnel using stable isotopes and hydrographs

Turquoise Lake is a water-supply reservoir located north of the historic Sugarloaf Mining district near Leadville, Colorado, USA. Elevated water levels in the reservoir may increase flow of low-quality water from abandoned mine tunnels in the Sugarloaf District and degrade water quality downstream. The objective of this study was to understand the sources of water to Dinero mine drainage tunnel and evaluate whether or not there was a direct hydrologic connection between Dinero mine tunnel and Turquoise Lake from late 2002 to early 2008. This study utilized hydrograph data from nearby draining mine tunnels and the lake, and stable isotope (&delta; 18 O and &delta; 2 H) data from the lake, nearby draining mine tunnels, imported water, and springs to characterize water sources in the study area. Hydrograph results indicate that flow from the Dinero mine tunnel decreased 26% (2006) and 10% (2007) when lake elevation (above mean sea level) decreased below approximately 3004 m (approximately 9855 feet). Results of isotope analysis delineated two meteoric water lines in the study area. One line characterizes surface water and water imported to the study area from the western side of the Continental Divide. The other line characterizes groundwater including draining mine tunnels, springs, and seeps. Isotope mixing calculations indicate that water from Turquoise Lake or seasonal groundwater recharge from snowmelt represents approximately 10% or less of the water in Dinero mine tunnel. However, most of the water in Dinero mine tunnel is from deep groundwater having minimal isotopic variation. The asymmetric shape of the Dinero mine tunnel hydrograph may indicate that a limited mine pool exists behind a collapse in the tunnel and attenutates seasonal recharge. Alternatively, a conceptual model is presented (and supported with MODFLOW simulations) that is consistent with current and previous data collected in the study area, and illustrates how fluctuating lake levels change the local water-table elevation which can affect discharge from the Dinero mine tunnel without physical transfer of water between the two locations.

Colorado↗

Mineralogy and the release of trace elements from slag from the Hegeler Zinc smelter, Illinois (USA)

Slag from the former Hegeler Zn-smelting facility in Illinois (USA) is mainly composed of spinifex Ca-rich plagioclase, fine-grained dendritic or coarse-grained subhedral to anhedral clinopyroxenes, euhedral to subhedral spinels, spherical blebs of Fe sulfides, silicate glass, and less commonly fayalitic olivine. Mullite and quartz were also identified in one sample as representing remnants of the furnace lining. Secondary phases such as goethite, hematite and gypsum are significant in some samples and reflect surficial weathering of the dump piles or represent byproducts of roasting. A relatively rare Zn-rich material contains anhedral willemite, subhedral gahnite, massive zincite, hardystonite and a Zn sulfate (brianyoungite), among other phases, and likely represents the molten content of the smelting furnace before Zn extraction. The bulk major-element chemistry of most slag samples is dominated by SiO 2 , Al 2 O 3 , Fe 2 O 3 and CaO. The bulk composition of the slag suggests a high viscosity of the melt and the mineralogy suggests a high silica content of the melt. Bulk slag trace-element chemistry shows that the dominant metal is Zn with >28.4 wt.% in the Zn-rich material and between 212 and 14,900 mg/kg in the other slags. The concentrations of other trace elements reach the following: 45 mg/kg As, 1170 mg/kg Ba, 191 mg/kg Cd, 242 mg/kg Co, 103 mg/kg Cr, 6360 mg/kg Cu, 107 mg/kg Ni, and 711 mg/kg Pb. Zinc, as the dominant metal in the slags, is likely the most environmentally significant metal in these samples; Cd, Cu, and Pb are also of concern and their concentrations exceed US Environmental Protection Agency preliminary remediation goals for residential soils. Spinel was found to be the dominant concentrator of Zn for samples containing significant Zn (>1 wt.%); the silicate glass also contained relatively high concentrations of Zn compared to other phases. Zinc partitioned into the silicates and oxides in these samples is generally more resistant to weathering and therefore less leached when compared to the slag samples with lower bulk Zn concentrations where Zn is likely partitioned into volumetrically minor sulfides. This is confirmed by leachate tests that resulted in low leachate Zn concentrations for samples with Zn partitioned into spinel. In contrast, the concentrations of Zn and SO 4 are close to those expected from the dissolution of stoichiometric ZnS in leachates from samples in which the dominant host of Zn is suspected to be sulfides. The fact that Zn and other metals occur commonly as sulfides, which are more reactive than the silicates and oxides into which they dominantly partition according to other slag studies, indicates the Hegeler slag pile may be more of an environmental concern than other slag piles.

Illinois↗

Using chloride and other ions to trace sewage and road salt in the Illinois Waterway

Chloride concentrations in waterways of northern USA are increasing at alarming rates and road salt is commonly assumed to be the cause. However, there are additional sources of Cl - in metropolitan areas, such as treated wastewater (TWW) and water conditioning salts, which may be contributing to Cl - loads entering surface waters. In this study, the potential sources of Cl - and Cl - loads in the Illinois River Basin from the Chicago area to the Illinois River's confluence with the Mississippi River were investigated using halide data in stream samples and published Cl - and river discharge data. The investigation showed that road salt runoff and TWW from the Chicago region dominate Cl - loads in the Illinois Waterway, defined as the navigable sections of the Illinois River and two major tributaries in the Chicago region. Treated wastewater discharges at a relatively constant rate throughout the year and is the primary source of Cl - and other elements such as F - and B. Chloride loads are highest in the winter and early spring as a result of road salt runoff which can increase Cl - concentrations by up to several hundred mg/L. Chloride concentrations decrease downstream in the Illinois Waterway due to dilution, but are always elevated relative to tributaries downriver from Chicago. The TWW component is especially noticeable downstream under low discharge conditions during summer and early autumn when surface drainage is at a minimum and agricultural drain tiles are not flowing. Increases in population, urban and residential areas, and roadways in the Chicago area have caused an increase in the flux of Cl - from both road salt and TWW. Chloride concentrations have been increasing in the Illinois Waterway since around 1960 at a rate of about 1 mg/L/a. The increase is largest in the winter months due to road salt runoff. Shallow groundwater Cl - concentrations are also increasing, potentially producing higher base flow concentrations. Projected increases in population and urbanization over the next several decades suggest that the trend of increasing Cl - concentrations and loads will continue. Given the susceptibility of aquatic ecosystems to increasing Cl - concentrations, especially short-term spikes following snow melts, deleterious effects on riverine ecosystems would be expected. ?? 2010 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

An approach to quantify sources, seasonal change, and biogeochemical processes affecting metal loading in streams: Facilitating decisions for remediation of mine drainage

Historical mining has left complex problems in catchments throughout the world. Land managers are faced with making cost-effective plans to remediate mine influences. Remediation plans are facilitated by spatial mass-loading profiles that indicate the locations of metal mass-loading, seasonal changes, and the extent of biogeochemical processes. Field-scale experiments during both low- and high-flow conditions and time-series data over diel cycles illustrate how this can be accomplished. A low-flow experiment provided spatially detailed loading profiles to indicate where loading occurred. For example, SO 4 2 - was principally derived from sources upstream from the study reach, but three principal locations also were important for SO 4 2 - loading within the reach. During high-flow conditions, Lagrangian sampling provided data to interpret seasonal changes and indicated locations where snowmelt runoff flushed metals to the stream. Comparison of metal concentrations between the low- and high-flow experiments indicated substantial increases in metal loading at high flow, but little change in metal concentrations, showing that toxicity at the most downstream sampling site was not substantially greater during snowmelt runoff. During high-flow conditions, a detailed temporal sampling at fixed sites indicated that Zn concentration more than doubled during the diel cycle. Monitoring programs must account for diel variation to provide meaningful results. Mass-loading studies during different flow conditions and detailed time-series over diel cycles provide useful scientific support for stream management decisions.

Applied Geochemistry↗

Identifying sources of stream water sulfate after a summer drought in the Sleepers River watershed (Vermont, USA) using hydrological, chemical, and isotopic techniques

In many forested headwater catchments, peak SO 4 2 - concentrations in stream water occur in the late summer or fall following drought potentially resulting in episodic stream acidification. The sources of highly elevated stream water SO 4 2 - concentrations were investigated in a first order stream at the Sleepers River watershed (Vermont, USA) after the particularly dry summer of 2001 using a combination of hydrological, chemical and isotopic approaches. Throughout the summer of 2001 SO 4 2 - concentrations in stream water doubled from ???130 to 270 ??eq/L while flows decreased. Simultaneously increasing Na + and Ca 2+ concentrations and ?? 34 S values increasing from +7??? towards those of bedrock S (???+10.5???) indicated that chemical weathering involving hydrolysis of silicates and oxidation of sulfide minerals in schists and phyllites was the cause for the initial increase in SO 4 2 - concentrations. During re-wetting of the watershed in late September and early October of 2001, increasing stream flows were accompanied by decreasing Na + and Ca 2+ concentrations, but SO 4 2 - concentrations continued to increase up to 568 ??eq/L, indicating that a major source of SO 4 2 - in addition to bedrock weathering contributed to peak SO 4 2 - concentrations. The further increase in SO 4 2 - concentrations coincided with an abrupt decrease of ?? 34 S values in stream water SO 4 2 - from maximum values near +10??? to minimum values near -3???. Soil investigations revealed that some C-horizons in the Spodsols of the watershed contained secondary sulfide minerals with ?? 34 S values near -22???. The shift to negative ?? 34 S values of stream water SO 4 2 - indicates that secondary sulfides in C-horizons were oxidized to SO 4 2 - during the particularly dry summer of 2001. The newly formed SO 4 2 - was transported to the streams during re-wetting of the watershed contributing ???60% of the SO 4 2 - during peak concentrations in the stream water. Thereafter, the contribution of SO 4 2 - from oxidation of secondary sulfides in C-horizons decreased rapidly and pedogenic SO 4 2 - reemerged as a dominant SO 4 2 - source in concert with decreasing SO 4 2 - concentrations in spring of 2002. The study provides evidence that a quantitative assessment of the sources of stream water SO 4 2 - in forested watersheds is possible by combining hydrological, chemical and isotopic techniques, provided that the isotopic compositions of all potential SO 4 2 - sources are distinctly different. ?? 2010 Elsevier Ltd.

Applied Geochemistry↗

Aquifer Storage Recovery (ASR) of chlorinated municipal drinking water in a confined aquifer

About 1.02 × 10 6 m 3 of chlorinated municipal drinking water was injected into a confined aquifer, 94–137 m below Roseville, California, between December 2005 and April 2006. The water was stored in the aquifer for 438 days, and 2.64 × 10 6 m 3 of water were extracted between July 2007 and February 2008. On the basis of Cl − data, 35% of the injected water was recovered and 65% of the injected water and associated disinfection by-products (DBPs) remained in the aquifer at the end of extraction. About 46.3 kg of total trihalomethanes (TTHM) entered the aquifer with the injected water and 37.6 kg of TTHM were extracted. As much as 44 kg of TTHMs remained in the aquifer at the end of extraction because of incomplete recovery of injected water and formation of THMs within the aquifer by reactions with free-chlorine in the injected water. Well-bore velocity log data collected from the Aquifer Storage Recovery (ASR) well show as much as 60% of the injected water entered the aquifer through a 9 m thick, high-permeability layer within the confined aquifer near the top of the screened interval. Model simulations of ground-water flow near the ASR well indicate that (1) aquifer heterogeneity allowed injected water to move rapidly through the aquifer to nearby monitoring wells, (2) aquifer heterogeneity caused injected water to move further than expected assuming uniform aquifer properties, and (3) physical clogging of high-permeability layers is the probable cause for the observed change in the distribution of borehole flow. Aquifer heterogeneity also enhanced mixing of native anoxic ground water with oxic injected water, promoting removal of THMs primarily through sorption. A 3 to 4-fold reduction in TTHM concentrations was observed in the furthest monitoring well 427 m downgradient from the ASR well, and similar magnitude reductions were observed in depth-dependent water samples collected from the upper part of the screened interval in the ASR well near the end of the extraction phase. Haloacetic acids (HAAs) were completely sorbed or degraded within 10 months of injection.

California↗

Distribution, behavior, and transport of inorganic and methylmercury in a high gradient stream

Concentrations of Hg remain elevated in physical and biological media of the South River (Virginia, USA), despite the cessation of the industrial use of Hg in its watershed nearly six decades ago, and physical characteristics that would not seem to favor Hg(II)-methylation. A 3-a study of inorganic Hg (IHg) and methylmercury (MeHg) was conducted in physical media (soil, sediment, surface water, porewater and soil/sediment extracts) to identify non-point sources, transport mechanisms, and potential controls on Hg(II)-methylation. Data collected from surface water and sediment indicate that the majority of the non-point sources of IHg to the South River are within the first 14. km downstream from the historic point source. Partitioning data indicate that particle bound IHg is introduced in this reach, releasing dissolved and colloidal bound IHg, which is transported downstream. Extraction experiments revealed that floodplain soils released a higher fraction of their IHg content in aqueous extractions than fine-grained sediment (FGS). Based on ultrafiltration [<5000 nominal molecular weight cutoff (NMWC)] the majority of soil IHg released was colloidal in nature, providing evidence for the continued evolution of IHg for Hg(II)-methylation from soil. Strong seasonal patterns in MeHg concentrations were observed in surface water and sediment. The highest concentrations of MeHg in surface water were observed at moderate temperatures, suggesting that other factors limit net Hg(II)-methylation. Seasonal changes in sediment organic content and the fraction of 1. N KOH-extractable THg were also observed and may be important factors in controlling net Hg(II)-methylation rates. Sulfate concentrations in surface water are low and the evidence suggests that Fe reduction may be an important Hg(II)-methylation process. The highest sediment MeHg concentrations were observed in habitats with large amounts of FGS, which are more prevalent in the upper half of the study area due to the lower hydrologic gradient and agricultural impacts. Past and present land use practices and other geomorphologic controls contribute to the erosion of banks and accumulation of fine-grained sediment in this section of the river, acting as sources of IHg. ?? 2010 Elsevier Ltd.

Applied Geochemistry↗