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Lead exposure of waterfowl ingesting Coeur d'Alene River Basin sediments

Feces from tundra swans [ Cygnus columbianus (Ord)], Canada geese [ Branta canadensis (L.)], and mallards [ Arias platyrhynchos (L.)] were collected from the Coeur d'Alene River Basin and two reference areas in Idaho to estimate exposure to lead from mining activities and relate that exposure to the ingestion of contaminated sediments. The average acid-insoluble ash content of the feces, a measure of sediment ingestion, was 18% for Canada geese and tundra swans, and 12% for ducks. The 18% value corresponded to an estimated 9% sediment ingestion rate (dry weight). The 90th percentile for acid-insoluble ash in feces of tundra swans corresponded to an estimated 22% sediment in the diet. The average lead concentration (dry weight) of tundra swan feces from all Coeur d'Alene River Basin wetlands sampled was 880 mg/kg, compared to 2.1 mg kg −1 from reference areas. The 90th percentile of lead in tundra swan feces from the Coeur d'Alene River Basin sites was 2700 mg kg −1 . Fecal lead concentrations of tundra swans were correlated (Spearman's rho = 0.74, P < 0.05) with the acid-insoluble ash content of the feces. The very low lead concentrations in feces having low acid-insoluble ash contents established that the sediment was the primary source of the lead ingested by waterfowl. Sediment lead concentrations at 11 wetland sites were closely correlated ( r = 0.91, P < 0.05) with average fecal lead concentrations for all waterfowl, corrected for the average percent acid-insoluble ash in the feces.

Idaho↗

Tributary stream infiltration as a source of herbicides in an alluvial aquifer

Where Walnut Creek flows across the South Skunk River alluvial aquifer, it provides a potential source of herbicides and herbicide metabolites. This straightened reach of the creek loses water and dissolved contaminants to the alluvial aquifer through a layer of fine-grained flood plain deposits. Estimates of potential flux of chemicals were based on measurements taken during baseflow in April 1994 before herbicides were applied to the watershed and in June 1994 after chemical application and when stream discharge included runoff and tile-drainage water. Hydraulic head measurements between the creek and flood plain deposits and between the creek and aquifer confirmed the potential for downward groundwater flow during both sampling periods. Hydraulic conductivity estimates from slug tests were used to calculate an average linear groundwater velocity of 0.5 m d −1 in the fine-grained flood plain deposits. At this velocity, contaminants could be advectively transported to the aquifer within 6 d. The potential for atrazine (2-chloro-4-ethylamino-6-isopropylamino- s -triazine) flux to the aquifer from the creek was estimated to be between 60 and 3000 µg d −1 m −2 . This rate is one to three orders of magnitude greater than the estimated flux via leaching beneath a typical field. If the process of vertical stream leakage occurs in many hydrologic settings, it may constitute a substantial source of herbicides to shallow alluvial aquifers in many areas of the Midwest.

Iowa↗

Oxidation and mobilization of selenium by nitrate in irrigation drainage

Selenium (Se) can be oxidized by nitrate (NO − 3 ) from irrigation on Cretaceous marine shale in western Colorado. Dissolved Se concentrations are positively correlated with dissolved NO − 3 concentrations in surface water and ground water samples from irrigated areas. Redox conditions dominate in the mobilization of Se in marine shale hydrogeologic settings; dissolved Se concentrations increase with increasing platinum-electrode potentials. Theoretical calculations for the oxidation of Se by NO − 3 and oxygen show favorable Gibbs free energies for the oxidation of Se by NO − 3 , indicating NO − 3 can act as an electron acceptor for the oxidation of Se. Laboratory batch experiments were performed by adding Mancos Shale samples to zero-dissolved-oxygen water containing 0, 5, 50, and 100 mg/L NO − 3 as N (mg N/L). Samples were incubated in airtight bottles at 25°C for 188 d; samples collected from the batch experiment bottles show increased Se concentrations over time with increased NO − 3 concentrations. Pseudo first-order rate constants for NO − 3 oxidation of Se ranged from 0.0007 to 0.0048/d for 0 to 100 mg N/L NO − 3 concentrations, respectively. Management of N fertilizer applications in Cretaceous shale settings might help to control the oxidation and mobilization of Se and other trace constituents into the environment.

Journal of Environmental Quality↗

Determining travel time and stream mixing using tracers and empirical equations

Water-supply managers need adequate warning to protect water supplies if a contaminant is spilled in an upgradient tributary. The city of Lincoln draws water from alluvium associated with the Platte River near Ashland, eastern Nebraska. Using constant-rate injection methods and a conservative tracer, travel time and degree of mixing of contaminants in the Elkhorn and Platte Rivers were evaluated in 1995 and 1996. The results indicate that, for flows of 584 to 162 m 3 /s in the Platte River at Ashland with 13 to 28% of its flow contributed by the Elkhorn River, 8.2 to 13.2 h are required for the leading edge of a chemical plume to travel from the Elkhorn River at Waterloo to the Platte River at Ashland. The peak concentration of a chemical spilled as a slug in the Elkhorn River near Waterloo would pass the well field after 11.3 to 16.1 h. Existing empirical equations for calculation of travel time were shown to apply to reaches of streams studied, but underestimated the leading edge up to 14% and overestimated the plateau concentration up to 11% at Site 5. However, time of travel may be influenced by the relative contribution of a tributary. The plateau concentration of the chemical in the Platte River at Ashland was 45 to 60% of its concentration in the Elkhorn River. The degree of mixing of the tracer in the Platte River at Ashland increased from 53 to 65% as the relative contribution of the Elkhorn River increased.

Journal of Environmental Quality↗

Observations on preferential flow and horizontal transport of nitrogen fertilizer in the unsaturated zone

A study site underlain by a claypan soil was instrumented to examine the transport of fertilizer nitrogen (N) under corn ( Zea mays L.) cultivation. The study was designed to examine N transport within the unsaturated zone and in intedlow (the saturated flow of water on top of the claypan). A 15 N-labeled fertilizer (labeled N), bromide (Br), and chloride (Cl) were used as field tracers. Rapid or prolonged infiltration events allowed water and dissolved solutes to perch on the claypan for brief periods. However, a well-developed network of preferential flow paths quickly diverted water and solutes through the claypan and into the underlying glacial till aquifer. Excess fertilizer N in the unsaturated zone supplied a continuous, but declining input of N to ground water for a period of 15 mo after a single fertilizer application. Calculated solute velocities through the claypan matrix (6.4 × 10 −6 cm s −1 ) were similar to horizontal transport rates along the claypan (3.5 to 7.3 × 10 −6 cm s −1 ) but much slower than infiltration rates determined for preferential flow paths (1.67 × 10 −3 cm s −1 ). These flow paths accounted for 35% of the transport. A seasonally variable, dual mode of transport (matrix and preferential flow) prevented the daypan from being an effective barrier to vertical transport. Simulations of selected field observations, conducted using the variably saturated two-dimensional flow and transport model, VS2DT, confirmed the presence of a dual flow regime in the claypan.

Journal of Environmental Quality↗

Occurrence and transport of acetochlor in streams of the Mississippi River Basin

The herbicide acetochlor [2-chloro- N -(ethoxymethyl)- N -(2-ethyl-6-methylphenyl) acetamide] was first used on corn ( Zea mays L.) in the USA during the growing season of 1994. By 1996, it was the third most heavily used corn herbicide in the midwestern USA. During the growing season of 1997, 78% of 375 samples collected at 32 stream sites in the Mississippi River Basin contained detectable concentrations of acetochlor. However, concentrations in only 2% of the samples exceeded 2/µg/L, the maximum annual average concentration allowable in public water supplies derived primarily from surface water. The largest acetochlor concentrations were detected in streams draining basins in parts of Illinois, Indiana, and Iowa. The median concentration of acetochlor in streams was about 10% that of atrazine (6-chloro- N -ethyl- N -isopropyl-1,3,5-triazine-2,4-diamine), about 25% that of metolachlor [2-chloro- N -(2-ethyl-6-methylphenyl)- N -(2-methoxy-1-methylethyl) acetamide], about 50% that of cyanazine [2-[[4-chloro-6-(ethylamino)-l,3,5-triazin-2-yl]amino]-2-methylpropionitrile], and about threefold that of alachlor [2-chloro-2′,6′-diethyl- N -(methoxymethyl) acetanilide]. Load estimates indicate that, during the growing season of 1997, agricultural subbasins draining areas of Illinois, Indiana, and Iowa contributed about 37 000 kg, or 74%, of the 50 000 kg of acetochlor measured in streams of the Mississippi River Basin.

Journal of Environmental Quality↗

Agrichemicals in ground water of the midwestern USA: Relations to soil characteristics

A comprehensive set of soil characteristics were examined to determine the effect of soil on the transport of agrichemicals to ground water. This paper examines the relation of local soil characteristics to concentrations and occurrence of nitrate, atrazine (2-chloro-4 ethylamino-6-isopropylamino- s -trazine), and atrazine residue [atrazine + deethylatrazine (2-amino-4-chloro-6-isopropylamino- s -triazine) + deisopropylatrazine (2-amino-4-chloro-6-ethylamino- s -triazine)] from 99 wells completed in unconsolidated aquifers across the midwestern USA. The occurrence and concentrations of nitrate and atrazine in ground water were directly related to soil characteristics that determine the rate of water movement. The substantial differences in the relations found among soil characteristics and nitrate and atrazine in ground water suggest that different processes affect the transformation, adsorption, and transport of these contaminants. A multivariate analysis determined that the soil characteristics examined explained the amount of variability in concentrations for nitrate (19.0%), atrazine (33.4%), and atrazine residue (28.6%). These results document that, although soils do affect the transport of agrichemicals to ground water, other factors such as hydrology, land use, and climate must also be considered to understand the occurrence of agrichemicals in ground water.

Journal of Environmental Quality↗

Estimation of nitrate contamination of an agro-ecosystem outwash aquifer using a nitrogen mass-balance budget

A mass-balance budget of N cycling was developed for an intensive agricultural area in west-central Minnesota to better understand NO3/- contamination of ground water in the Otter Tail outwash aquifer. Fertilizer, biological fixation, atmospheric deposition, and animal feed were the N sources, and crop harvests, animal product exports, volatilization from fertilizer and manure, and denitrification were the N sinks in the model. Excess N, calculated as the difference between the sources and sinks, was assumed to leach to ground water as NO3/-. The budget was developed using ground water data collected throughout the 212-km2 study area. Denitrification was estimated by adjusting its value so the predicted and measured concentrations of NO3/- in ground water agreed. Although biological fixation was the largest single N source, most was removed when crops were harvested, indicating that inorganic fertilizer was the primary source of N reaching the water table. It was estimated that denitrification removed almost half of the excess NO3/- that leached below the root zone. Even after accounting for denitrification losses, however, it was concluded that the ground water system was receiving approximately three times as much N as would be expected under background conditions.

Journal of Environmental Quality↗

Water selenium speciation and sediment fractionation in a California flow-through wetland system

A flow-through wetland system was established in the Tulare Lake Drainage District (TLDD) in California to determine if selenium (Se) from saline irrigation drainage can be removed prior to impoundment in evaporation basins to reduce potential toxicity to waterbirds. The objective of this research was to evaluate Se speciation, accumulation, and fractionation in the waters and sediments of the newly developed wetland system. The inlet water was dominated by selenate [Se(VI), 92%], with smaller percentages of selenite [Se(IV), 5%] and organic Se [org-Se(-II), 3%]. For the outflow water, the average percentage of Se(VI) was 72% in November 1997 and 59% in February 1999. This change may be due to an increase in either residence time and/or accumulation of organic detrital matter, which may enhance Se(VI) reduction processes. Selenium accumulation, transformation, and incorporation with the solid phase were all intensified in the surface sediment (<20 cm). The highest total Se concentrations in the sediments were found in the top 5 cm and concentrations dramatically decreased with depth. Elemental Se [Se(0)], as extracted by Na2SO3, was the largest fraction (average of 46%) of the total sediment Se, followed by organic matter-associated Se (OM-Se) extracted by NaOH (average of 34%). Soluble, adsorbed, and carbonate-associated Se, as extracted by KCl, K2HPO4 (pH 8.0), and NaOAc (pH 5.0), were about 3, 10, and 3% of the total sediment Se, respectively. After establishing the wetland for 2 yr, significant Se removal from the flowing water was observed. The major sink mechanisms in the sediment are reduction to Se(0) and immobilization into the organic phase.A flow-through wetland system was established in the Tulare Lake Drainage District (TLDD) in California to determine if selenium (Se) from saline irrigation drainage can be removed prior to impoundment in evaporation basins to reduce potential toxicity to waterbirds. The objective of this research was to evaluate Se speciation, accumulation, and fractionation in the waters and sediments of the newly developed wetland system. The inlet water was dominated by selenate [Se(VI), 92%], with smaller percentages of selenite [Se(IV), 5%] and organic Se [org-Se(-II), 3%]. For the outflow water, the average percentage of Se(VI) was 72% in November 1997 and 59% in February 1999. This change may be due to an increase in either residence time and/or accumulation of organic detrital matter, which may enhance Se(VI) reduction processes. Selenium accumulation, transformation, and incorporation with the solid phase were all intensified in the surface sediment (<20 cm). The highest total Se concentrations in the sediments were found in the top 5 cm and concentrations dramatically decreased with depth. Elemental Se [Se(0)], as extracted by Na2SO3, was the largest fraction (average of 46%) of the total sediment Se, followed by organic matter-associated Se (OM-Se) extracted by NaOH (average of 34%). Soluble, adsorbed, and carbonate-associated Se, as extracted by KCl, K2HPO4 (pH 8.0), and NaOAc (pH 5.0), were about 3, 10, and 3% of the total sediment Se, respectively. After establishing the wetland for 2 yr, significant Se removal from the flowing water was observed. The major sink mechanisms in the sediment are reduction to Se(0) and immobilization into the organic phase.

California↗

Hazards to wildlife from soil-borne cadmium reconsidered

Cadmium is a toxic element that should be included in environmental risk assessments of contaminated soils. This paper argues, however, that hazards to wildlife from cadmium have often been overstated. The literature contains only meager evidence that wild animals have been seriously harmed by cadmium, even at severely contaminated sites. Although some researchers have reported that wildlife have accumulated concentrations of cadmium in their kidneys that were above suggested injury thresholds, the thresholds may be disputed, since they were well below the World Health Organization criterion of 200 mg/kg (wet weight) of cadmium in the renal cortex for protecting human health. Recent risk assessments have concluded that soil cadmium concentrations less than 1 mg/kg are toxic to soil organisms and wildlife, which implies that background concentrations of cadmium naturally found in soils are hazardous. An examination of the databases used to support these assessments suggested that the toxicity of cadmium has been exaggerated.

Journal of Environmental Quality↗

Atrazine adsorption and colloid-facilitated transport through the unsaturated zone

One explanation for unexpectedly widespread ground water contamination from atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) may be the occurrence of colloid-facilitated transport, whereby the dissolved herbicide becomes adsorbed to mobile colloids that migrate through preferential flow-paths in the soil zone and into the ground water. The objectives of this study were to determine the extent of adsorpton of atrazine to bulk soil and to soil colloids and to determine the extent of colloid-facilitated transport of atrazine at a field site in Virginia during simulated rainfall events. Equilibrium batch adsorption experiments were performed over a concentration range of 0.05 to 10.0 mg atrazine L-1 on bulk soil samples and on colloidal suspensions of 75 mg L-1, a concentration comparable with those observed at the field site. Linear partition coefficients ranged from 0.496 to 2.48 L kg-1 for the bulk soil and from 70.8 to 832 L kg-1 for the soil colloids. In the field, gravity lysimeters were insured at a depth of 25 cm below the surface of six 0.25-m2 undisturbed plots. Mass recovery of surface-applied atrazine in the lysimeters was not significantly affected by rainfall rate and was, on average, 2.7% for plots receiving 25 mm h-1 simulated rainfall and 3.6% for plots receiving 50 mm h-1 simulated rainfall. Of the total atrazine collected in the lysimeters, the fraction that was colloid-associated ranged from 4.9 to 30% (mean of 15%), indicating that a measurable portion of mobile atrazine is transported via association with colloids.One explanation for unexpectedly widespread ground water contamination from atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) may be the occurrence of colloid-facilitated transport, whereby the dissolved herbicide becomes adsorbed to mobile colloids that migrate through preferential flow-paths in the soil zone and into the ground water. The objectives of this study were to determine the extent of adsorption of atrazine to bulk soil and to soil colloids and to determine the extent of colloid-facilitated transport of atrazine at a field site in Virginia during simulated rainfall events. Equilibrium batch adsorption experiments were performed over a concentration range of 0.05 to 10.0 mg atrazine L-1 on bulk soil samples and on colloidal suspensions of 75 mg L-1, a concentration comparable with those observed at the field site. Linear partition coefficients ranged from 0.496 to 2.48 L kg-1 for the bulk soil and from 70.8 to 832 L kg-1 for the soil colloids. In the field, gravity lysimeters were installed at a depth of 25 cm below the surface of six 0.25-m2 undisturbed plots. Mass recovery of surface-applied atrazine in the lysimeters was not significantly affected by rainfall rate and was, on average, 2.7% for plots receiving 25 mm h-1 simulated rainfall and 3.6% for plots receiving 50 mm h-1 simulated rainfall. Of the total atrazine collected in the lysimeters, the fraction that was colloid-associated ranged from 4.9 to 30% (mean of 15%), indicating that a measurable portion of mobile atrazine is transported via association with colloids.In the Muddy Creek watershed, VA, the extent of atrazine adsorption to the immobile soil matrix and mobile soil colloids was examined in an agricultural silt loam soil, and atrazine transport during simulated rainfall events of different intensities was assessed. Results from batch equilibration experiments revealed that atrazine adsorption was significantly greater on the colloids than on the bulk soil, which was attributed to the higher specific surface area and organic content of the colloids. Despite the mobilization of colloids, however, the mass recovery of colloid-associated atrazine was low for all plots. Precipitation rate did not significantly affect atrazine mass recovery.

Journal of Environmental Quality↗

The relationship of nitrate concentrations in streams to row crop land use in Iowa

The relationship between row crop land use and nitrate N concentrations in surface water was evaluated for 15 Iowa watersheds ranging from 1002 to 2774 km 2 and 10 smaller watersheds ranging from 47 to 775 km 2 for the period 1996 to 1998. The percentage of land in row crop varied from 24 to >87% in the 15 large watersheds, and mean annual NO 3 -N concentrations ranged from 0.5 to 10.8 mg/L. In the small watersheds, row crop percentage varied from 28 to 87% and mean annual NO 3 -N concentrations ranged from 3.0 to 10.5 mg/L. In both cases, nitrate N concentrations were directly related to the percentage of row crop in the watershed ( p < 0.0003). Linear regression showed similar slope for both sets of watersheds (0.11) suggesting that average annual sudace water nitrate concentrations in Iowa, and possibly similar agricultural areas in the midwestern USA, can be approximated by multiplying a watershed's row crop percentage by 0.1. Comparing the Iowa watershed data with similar data collected at a subwatershed scale in Iowa (0.1 to 8.1 km 2 ) and a larger midcontinent scale (7300 to 237 100 km 2 ) suggests that watershed scale affects the relationship of nitrate concentration and land use. The slope of nitrate concentration versus row crop percentage decreases with increasing watershed size.

Iowa↗

Biogeochemistry of a treeline watershed, northwestern Alaska

Since 1950, mean annual temperatures in northwestern Alaska have increased. Change in forest floor and soil temperature or moisture could alter N mineralization rates, production of dissolved organic carbon (DOC) and organic nitrogen (DON), and their export to the aquatic ecosystem. In 1990, we began study of nutrient cycles in the 800-ha Asik watershed, located at treeline in the Noatak National Preserve, northwestern Alaska. This paper summarizes relationships between topographic aspect, soil temperature and moisture, inorganic and organic N pools, C pools, CO 2 efflux, growing season net N mineralization rates, and stream water chemistry. Forest floor (O2) C/N ratios, C pools, temperature, and moisture were greater on south aspects. More rapid melt of the soil active layer (zone of annual freeze–thaw) and permafrost accounted for the higher moisture. The O2 C and N content were correlated with moisture, inorganic N pools, CO 2 efflux, and inversely with temperature. Inorganic N pools were correlated with temperature and CO 2 efflux. Net N mineralization rates were positive in early summer, and correlated with O2 moisture, temperature, and C and N pools. Net nitrification rates were inversely correlated with moisture, total C and N. The CO 2 efflux increased with temperature and moisture, and was greater on south aspects. Stream ion concentrations declined and DOC increased with discharge. Stream inorganic nitrogen (DIN) output exceeded input by 70%. Alpine stream water nitrate (NO − 3 ) and DOC concentrations indicated substantial contributions to the watershed DIN and DOC budgets.

Alaska↗

Sources of salinity near a coal mine spoil pile, north-central Colorado

A small (1 km 2 ) salt-affected stream drainage on the High Plains north of Denver, Colorado was sampled to determine the near-surface dispersion of soluble salts and metals from low-sulfur coal mining waste (spoil). Surface waters collected along the 0.8-km stream reach, and aqueous leachates of spoil and naturally saline local soil, were analyzed for chemical constituents and sulfur isotopes. In this semiarid setting with abundant carbonate-bearing surficial sediments, the limited, mildly acidic drainage from the spoil pile is quickly neutralized, restricting the mobility of many elements. However, some spoil-derived constituents were clearly traceable within the upper 0.4 km of the stream reach. Spoil leachates and surface water near the spoil pile have distinctive compositions of major anions and cations, and elevated levels of dissolved nitrate compared with downstream waters. Spoil-derived sulfate was traceable because it has generally positive values of δ 34 S that contrasted with generally negative values of δ 34 S in soil leachates and evaporite salts from the surrounding area. Spatial–chemical sampling of surface water showed an abrupt increase in dissolved U, Se, B, Li, and Mn in the lower 0.4 km of the stream reach where shallow ground water from surrounding irrigated fields contributed to surface flow. The downstream evolution of surface water chemistry and sulfur isotopic composition is consistent with mixing between spoil-affected upstream water and irrigation-return water. The methods described should be applicable at other sites in similar settings where the environmental effect of low-sulfur coal mining waste must be assessed and where access to samples of shallow ground water is limited.

Colorado↗

Differentiating nonpoint sources of deisopropylatrazine in surface water using discrimination diagrams

Pesticide degradates account for a significant portion of the pesticide load in surface water. Because pesticides with similar structures may degrade to the same degradate, it is important to distinguish between different sources of parent compounds that have different regulatory and environmental implications. A discrimination diagram, which is a sample plot of chemical data that differentiates between different parent compounds, was used for the first time to distinguish whether sources other than atrazine (6-chloro- N 2 -ethyl- N 4 -isopropyl-1,3,5-triazine-2,4-diamine) contributed the chlorinated degradate, deisopropylatrazine (DIA; 6-chloro- N -ethyl-1,3,5-triazine-2,4-diamine) to the Iroquois and Delaware Rivers. The concentration ratio of deisopropylatrazine to deethylatrazine [6-chloro- N -(1-methylethyl)-1,3,5-triazine-2,4-diamine], called the D 2 R, was used to discriminate atrazine as a source of DIA from other parent sources, such as cyanazine (2-[[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino]-2-methylpropionitrile) and simazine (6-chloro- N , N ′-diethyl-1,3,5-triazine-2,4-diamine). The ratio of atrazine to cyanazine (ACR) used in conjunction with the D 2 R showed that after atrazine, cyanazine was the main contributor of DIA in surface water. The D 2 R also showed that cyanazine, and to a much lesser extent simazine, contributed a considerable amount (∼40%) of the DIA that was transported during the flood of the Mississippi River in 1993. The D 2 R may continue to be a useful discriminator in determining changes in the nonpoint sources of DIA in surface water as cyanazine is currently being removed from the market.

Kansas↗

Selenium stable isotope ratios in California agricultural drainage water management systems

Selenium stable isotope ratios are known to shift in predictable ways during various microbial, chemical, and biological processes, and can be used to better understand Se cycling in contaminated environments. In this study we used Se stable isotopes to discern the mechanisms controlling the transformation of oxidized, aqueous forms of Se to reduced, insoluble forms in sediments of Se-affected environments. We measured 80Se/76Se in surface waters, shallow ground waters, evaporites, digested plants and sediments, and sequential extracts from several sites where agricultural drainage water is processed in the San Joaquin Valley of California. Selenium isotope analyses of samples obtained from the Tulare Lake Drainage District flow-through wetland reveal small isotopic contrasts (mean difference 0.7%o) between surface water and reduced Se species in the underlying sediments. Selenium in aquatic macrophytes was very similar isotopically to the NaOH and Na2SO3 sediment extracts designed to recover soluble organic Se and Se(O), respectively. For the integrated on-farm drainage management sites, evaporite salts were slightly (approximately 0.6%o) enriched in the heavier isotope relative to the inferred parent waters, whereas surface soils were slightly (approximately 1.4%o) depleted. Bacterial or chemical reduction of Se(VI) or Se(IV) may be occurring at these sites, but the small isotopic contrasts suggest that other, less isotopically fractionating mechanisms are responsible for accumulation of reduced forms in the sediments. These findings provide evidence that Se assimilation by plants and algae followed by deposition and mineralization is the dominant transformation pathway responsible for accumulation of reduced forms of Se in the wetland sediments.

California↗

Tracing sources of sulfur in the Florida Everglades

We examined concentrations and sulfur isotopic ratios ( 34 S/ 32 S, expressed as δ 34 S in parts per thousand [‰] units) of sulfate in surface water, ground water, and rain water from sites throughout the northern Everglades to establish the sources of sulfur to the ecosystem. The geochemistry of sulfur is of particular interest in the Everglades because of its link, through processes mediated by sulfate-reducing bacteria, to the production of toxic methylmercury in this wetland ecosystem. Methylmercury, a neurotoxin that is bioaccumulated, has been found in high concentrations in freshwater fish from the Everglades, and poses a potential threat to fish-eating wildlife and to human health through fish consumption. Results show that surface water in large portions of the Everglades is heavily contaminated with sulfate, with the highest concentrations observed in canals and marsh areas receiving canal discharge. Spatial patterns in the range of concentrations and δ 34 S values of sulfate in surface water indicate that the major source of sulfate in sulfur-contaminated marshes is water from canals draining the Everglades Agricultural Area. Shallow ground water underlying the Everglades and rain water samples had much lower sulfate concentrations and δ 34 S values distinct from those found in surface water. The δ 34 S results implicate agricultural fertilizer as a major contributor to the sulfate contaminating the Everglades, but ground water under the Everglades Agricultural Area (EAA) may also be a contributing source. The contamination of the northern Everglades with sulfate from canal discharge may be a key factor in controlling the distribution and extent of methylmercury production in the Everglades.

Florida↗

Transport and fate of nitrate in a glacial outwash aquifer in relation to ground water age, land use practices, and redox processes

A combination of ground water modeling, chemical and dissolved gas analyses, and chlorofluorocarbon age dating of water was used to determine the relation between changes in agricultural practices, and NO − 3 concentrations in ground water of a glacial outwash aquifer in west-central Minnesota. The results revealed a redox zonation throughout the saturated zone with oxygen reduction occurring near the water table, NO − 3 reduction immediately below it, and then a large zone of ferric iron reduction, with a small area of sulfate (SO 2− 4 ) reduction and methanogenesis (CH 4 ) near the end of the transect. Analytical and NETPATH modeling results supported the hypothesis that organic carbon served as the electron donor for the redox reactions. Denitrification rates were quite small, 0.005 to 0.047 mmol NO − 3 yr −1 , and were limited by the small amounts of organic carbon, 0.01 to 1.45%. In spite of the organic carbon limitation, denitrification was virtually complete because residence time is sufficient to allow even slow processes to reach completion. Ground water sample ages showed that maximum residence times were on the order of 50 to 70 yr. Reconstructed NO − 3 concentrations, estimated from measured NO − 3 and dissolved N gas showed that NO − 3 concentrations have been increasing in the aquifer since the 1940s, and have been above the 714 μmol L −1 maximum contaminant level at most sites since the mid- to late-1960s. This increase in NO − 3 has been accompanied by a corresponding increase in agricultural use of fertilizer, identified as the major source of NO − 3 to the aquifer.

Minnesota↗