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Model predictions of realgar precipitation by reaction of As(III) with synthetic mackinawite under anoxic conditions

This study investigates the removal of As(III) from solution using mackinawite, a nanoparticulate reduced iron sulfide. Mackinawite suspensions (0.1−40 g/L) effectively lower initial concentrations of 1.3×10 −5 M As(III) from pH 5−10, with maximum removal occurring under acidic conditions. Based on E h measurements, it was found that the redox state of the system depended on the mackinawite solids concentration and pH. Higher initial mackinawite concentrations and alkaline pH resulted in a more reducing redox condition. Given this, the pH edge data were modeled thermodynamically using pe (−log[e − ]) as a fitting parameter and linear pe−pH relationships within the range of measured E h values as a function of pH and mackinawite concentration. The model predicts removal of As(III) from solution by precipitation of realgar with the formation of secondary oxidation products, greigite or a mixed-valence iron oxide phase, depending on pH. This study demonstrates that mackinawite is an effective sequestration agent for As(III) and highlights the importance of incorporating redox into models describing the As−Fe−S−H 2 O system.

Environmental Science & Technology↗

Aquatic toxicity of airfield-pavement deicer materials and implications for airport runoff

Concentrations of airfield-pavement deicer materials (PDM) in a study of airport runoff often exceeded levels of concern regarding aquatic toxicity. Toxicity tests on Vibrio fischeri, Pimephales promelas, Ceriodaphnia dubia, and Pseudokirchneriella subcapitata (commonly known as Selenastrum capricornutum) were performed with potassium acetate (K-Ac) PDM, sodium formate (Na-For) PDM, and with freezing- point depressants (K-Ac and Na-For). Results indicate that toxicity in PDM is driven by the freezing-point depressants in all tests except the Vibrio fisheri test for Na-For PDM which is influenced by an additive. Acute toxicity end points for different organisms ranged from 298 to 6560 mg/L (as acetate) for K-Ac PDM and from 1780 to 4130 mg/L (as formate) for Na- For PDM. Chronic toxicity end points ranged from 19.9 to 336 mg/L (as acetate) for K-Ac PDM and from 584 to 1670 mg/L (as formate) for Na-For PDM. Sample results from outfalls at General Mitchell International Airport in Milwaukee, Wl (GMIA) indicated that 40% of samples had concentrations greater than the aquatic-life benchmark for K-Ac PDM. K-Ac has replaced urea during the 1990s as the most widely used PDM at GMIA and in the United States. Results of ammonia samples from airport outfalls during periods when urea-based PDM was used at GMIA indicated that41% of samples had concentrations exceeding the U.S. Environmental Protection Agency (USEPA) 1 -h water-quality criterion. The USEPA 1-h water-quality criterion for chloride was exceeded in 68% of samples collected in the receiving stream, a result of road-salt runoff from urban influence near the airport. Results demonstrate that PDM must be considered to comprehensively evaluate the impact of chemical deicers on aquatic toxicity in water containing airport runoff. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

Summer E. coli patterns and responses along 23 Chicago beaches

Concentrations of E. coli in recreational beach water are highly variable both locally and temporally, but a broader understanding of these fluctuations may be explained through coastal observations. Currently, beach contamination study approaches tend to be site-specific underthe belief that politically delineated beaches are unique and management of beaches cannot be regionally oriented. E. coli data collected over five years from 23 Chicago beaches clearly identified ambient linked patterns at the regional scale. Temporal fluctuations were similar, with all beaches having simultaneous peaks and troughs of E. coli concentrations. Spatially, E. coli concentrations for beaches more closely situated were more closely correlated, indicating spatial autocorrelation. Julian day, wave height, and barometric pressure explained up to 40% of the variation, a value comparable to individual, less parsimonious site-specific models. Day of sampling could explain the majority of the variation in E. coli concentrations, more so than beach, depth, or time of day. Comparing beaches along a targeted coastline allows a better understanding of inherent background regional fluctuations and, ultimately, better predictions of E. coli concentrations in coastal recreational water.

Environmental Science & Technology↗

Geochemistry of inorganic nitrogen in waters released from coal-bed natural gas production wells in the Powder River Basin, Wyoming

Water originating from coal-bed natural gas (CBNG) production wells typically contains ammonium and is often disposed via discharge to ephemeral channels. A study conducted in the Powder River Basin, Wyoming, documented downstream changes in CBNG water composition, emphasizing nitrogen-cycling processes and the fate of ammonium. Dissolved ammonium concentrations from 19 CBNG discharge points ranged from 95 to 527 μM. Within specific channels, ammonium concentrations decreased with transport distance, with subsequent increases in nitrite and nitrate concentrations. Removal efficiency, or uptake, of total dissolved inorganic nitrogen (DIN) varied between channel types. DIN uptake was greater in the gentle-sloped, vegetated channel as compared to the incised, steep, and sparsely vegetated channel and was highly correlated with diel patterns of incident light and dissolved oxygen concentration. In a larger main channel with multiple discharge inputs ( n = 13), DIN concentrations were >300 μM, with pH > 8.5, after 5 km of transport. Ammonium represented 25−30% of the large-channel DIN, and ammonium concentrations remained relatively constant with time, with only a weak diel pattern evident. In July 2003, the average daily large-channel DIN load was 23 kg N day −1 entering the Powder River, an amount which substantially increased the total Powder River DIN load after the channel confluence. These results suggest that CBNG discharge may be an important source of DIN to western watersheds, at least at certain times of the year, and that net oxidation and/or removal is dependent upon the extent of contact with sediment and biomass, type of drainage channel, and time of day.

Wyoming↗

Mercury cycling in stream ecosystems. 1. Water column chemistry and transport

We studied total mercury (THg) and methylmercury (MeHg) in eight streams, located in Oregon, Wisconsin, and Florida, that span large ranges in climate, landscape characteristics, atmospheric Hg deposition, and water chemistry. While atmospheric deposition was the source of Hg at each site, basin characteristics appeared to mediate this source by providing controls on methylation and fluvial THg and MeHg transport. Instantaneous concentrations of filtered total mercury (FTHg) and filtered methylmercury (FMeHg) exhibited strong positive correlations with both dissolved organic carbon (DOC) concentrations and streamflow for most streams, whereas mean FTHg and FMeHg concentrations were correlated with wetland density of the basins. For all streams combined, whole water concentrations (sum of filtered and particulate forms) of THg and MeHg correlated strongly with DOC and suspended sediment concentrations in the water column.

Environmental Science & Technology↗

Mercury cycling in stream ecosystems. 2. Benthic methylmercury production and bed sediment - Pore water partitioning

Mercury speciation, controls on methylmercury (MeHg) production, and bed sediment−pore water partitioning of total Hg (THg) and MeHg were examined in bed sediment from eight geochemically diverse streams where atmospheric deposition was the predominant Hg input. Across all streams, sediment THg concentrations were best described as a combined function of sediment percent fines (%fines; particles < 63 μm) and organic content. MeHg concentrations were best described as a combined function of organic content and the activity of the Hg(II)-methylating microbial community and were comparable to MeHg concentrations in streams with Hg inputs from industrial and mining sources. Whole sediment tin-reducible inorganic reactive Hg (Hg(II) R ) was used as a proxy measure for the Hg(II) pool available for microbial methylation. In conjunction with radiotracer-derived rate constants of 203 Hg(II) methylation, Hg(II) R was used to calculate MeHg production potential rates and to explain the spatial variability in MeHg concentration. The %Hg(II) R (of THg) was low (2.1 ± 5.7%) and was inversely related to both microbial sulfate reduction rates and sediment total reduced sulfur concentration. While sediment THg concentrations were higher in urban streams, %MeHg and %Hg(II) R were higher in nonurban streams. Sediment pore water distribution coefficients (log K d ’s) for both THg and MeHg were inversely related to the log-transformed ratio of pore water dissolved organic carbon (DOC) to bed sediment %fines. The stream with the highest drainage basin wetland density also had the highest pore water DOC concentration and the lowest log K d ’s for both THg and MeHg. No significant relationship existed between overlying water MeHg concentrations and those in bed sediment or pore water, suggesting upstream sources of MeHg production may be more important than local streambed production as a driver of water column MeHg concentration in drainage basins that receive Hg inputs primarily from atmospheric sources.

Environmental Science & Technology↗

Mercury cycling in stream ecosystems. 3. Trophic dynamics and methylmercury bioaccumulation

Trophic dynamics (community composition and feeding relationships) have been identified as important drivers of methylmercury (MeHg) bioaccumulation in lakes, reservoirs, and marine ecosystems. The relative importance of trophic dynamics and geochemical controls on MeHg bioaccumulation in streams, however, remains poorly characterized. MeHg bioaccumulation was evaluated in eight stream ecosystems across the United States (Oregon, Wisconsin, and Florida) spanning large ranges in climate, landscape characteristics, atmospheric Hg deposition, and stream chemistry. Across all geographic regions and all streams, concentrations of total Hg (THg) in top predator fish and forage fish, and MeHg in invertebrates, were strongly positively correlated to concentrations of filtered THg (FTHg), filtered MeHg (FMeHg), and dissolved organic carbon (DOC); to DOC complexity (as measured by specific ultraviolet absorbance); and to percent wetland in the stream basins. Correlations were strongest for nonurban streams. Although regressions of log[Hg] versus δ 15 N indicate that Hg in biota increased significantly with increasing trophic position within seven of eight individual streams, Hg concentrations in top predator fish (including cutthroat, rainbow, and brown trout; green sunfish; and largemouth bass) were not strongly influenced by differences in relative trophic position. Slopes of log[Hg] versus δ 15 N, an indicator of the efficiency of trophic enrichment, ranged from 0.14 to 0.27 for all streams. These data suggest that, across the large ranges in FTHg (0.14−14.2 ng L −1 ), FMeHg (0.023−1.03 ng L −1 ), and DOC (0.50−61.0 mg L −1 ) found in this study, Hg contamination in top predator fish in streams likely is dominated by the amount of MeHg available for uptake at the base of the food web rather than by differences in the trophic position of top predator fish.

Environmental Science & Technology↗

Biodegradation of 17β-estradiol, estrone and testosterone in stream sediments

Biodegradation of 17&beta;-estradiol (E2), estrone (E1), and testosterone (T) was investigated in three wastewater treatment plant (WWTP) affected streams in the United States. Relative differences in the mineralization of [4- 14 C] substrates were assessed in oxic microcosms containing saturated sediment or water-only from locations upstream and downstream of the WWTP outfall in each system. Upstream sediment demonstrated significant mineralization of the &ldquo;A&rdquo; ring of E2, E1, and T, with biodegradation of T consistently greater than that of E2 and no systematic difference in E2 and E1 biodegradation. &ldquo;A&rdquo; ring mineralization also was observed in downstream sediment, with E1 and T mineralization being substantially depressed relative to upstream samples. In marked contrast, E2 mineralization in sediment immediately downstream from the WWTP outfalls was more than double that in upstream sediment. E2 mineralization was observed in water, albeit at insufficient rate to prevent substantial downstream transport. The results indicate that, in combination with sediment sorption processes which effectively scavenge hydrophobic contaminants from the water column and immobilize them in the vicinity of the WWTP outfall, aerobic biodegradation of reproductive hormones can be an environmentally important mechanism for nonconservative (destructive) attenuation of hormonal endocrine disruptors in effluent-affected streams.

Colorado, Iowa↗

Spatial pattern of groundwater arsenic occurrence and association with bedrock geology in greater augusta, maine

In New England, groundwater arsenic occurrence has been linked to bedrock geology on regional scales. To ascertain and quantify this linkage at intermediate (10 0 -10 1 km) scales, 790 groundwater samples from fractured bedrock aquifers in the greater Augusta, Maine area are analyzed, and 31% of the sampled wells have arsenic concentrations >10 ??g/L. The probability of [As] exceeding 10 ??g/L mapped by indicator kriging is highest in Silurian pelite-sandstone and pelite-limestone units (???40%). This probability differs significantly (p < 0.001) from those in the Silurian - Ordovician sandstone (24%), the Devonian granite (15%), and the Ordovician - Cambrian volcanic rocks (9%). The spatial pattern of groundwater arsenic distribution resembles the bedrock map. Thus, bedrock geology is associated with arsenic occurrence in fractured bedrock aquifers of the study area at intermediate scales relevant to water resources planning. The arsenic exceedance rate for each rock unit is considered robust because low, medium, and high arsenic occurrences in four cluster areas (3-20 km 2 ) with a low sampling density of 1-6 wells per km 2 are comparable to those with a greater density of 5-42 wells per km 2 . About 12,000 people (21% of the population) in the greater Augusta area (???1135 km 2 ) are at risk of exposure to >10 ??g/L arsenic in groundwater. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

Fate of sulfamethoxazole, 4-nonylphenol, and 17β-estradiol in groundwater contaminated by wastewater treatment plant effluent

Organic wastewater contaminants (OWCs) were measured in samples collected from monitoring wells located along a 4.5-km transect of a plume of groundwater contaminated by 60 years of continuous rapid infiltration disposal of wastewater treatment plant effluent. Fifteen percent of the 212 OWCs analyzed were detected, including the antibiotic sulfamethoxazole (SX), the nonionic surfactant degradation product 4-nonylphenol (NP), the solvent tetrachloroethene (PCE), and the disinfectant 1,4-dichlorobenzene (DCB). Comparison of the 2005 sampling results to data collected from the same wells in 1985 indicates that PCE and DCB are transported more rapidly in the aquifer than NP, consistent with predictions based on compound hydrophobicity. Natural gradient in situ tracer experiments were conducted to evaluate the subsurface behavior of SX, NP, and the female sex hormone 17&beta;-estradiol (E2) in two oxic zones in the aquifer: (1) a downgradient transition zone at the interface between the contamination plume and the overlying uncontaminated groundwater and (2) a contaminated zone located beneath the infiltration beds, which have not been loaded for 10 years. In both zones, breakthrough curves for the conservative tracer bromide (Br &minus; ) and SX were nearly coincident, whereas NP and E2 were retarded relative to Br &minus; and showed mass loss. Retardation was greater in the contaminated zone than in the transition zone. Attenuation of NP and E2 in the aquifer was attributed to biotransformation, and oxic laboratory microcosm experiments using sediments from the transition and contaminated zones show that uniform-ring-labeled 14 C 4-normal-NP was biodegraded more rapidly (30&minus;60% recovered as 14 CO 2 in 13 days) than 4- 14 C E2 (20&minus;90% recovered as 14 CO 2 in 54 days). There was little difference in mineralization potential between sites.

Massachusetts↗

Using oxygen isotopes of phosphate to trace phosphorus sources and cycling in lake Erie

Water samples collected during three sampling trips to Lake Erie displayed oxygen isotopic values of dissolved phosphate (δ 18 O p ) that were largely out of equilibrium with ambient conditions, indicating that source signatures may be discerned. δ 18 O p values in the Lake ranged from +10‰ to +17‰, whereas the equilibrium value was expected to be around +14‰. The riverine weighted average δ 18 O p value was +11‰ and may represent one source of phosphate to the Lake. The lake δ 18 O p values indicated that there must be one or more as yet uncharacterized source(s) of phosphate with a high δ 18 O p value. Potential sources other than rivers are not yet well-characterized with respect to δ 18 O of phosphate, but we speculate that a likely source may be the release of phosphate from sediments under reducing conditions created during anoxic events in the hypolimnion of the central basin of Lake Erie. Identifying potential phosphorus sources to the Lake is vital for designing effective management plans for reducing nutrient inputs and associated eutrophication.

Environmental Science & Technology↗

Semivolatile organic compounds in residential air along the Arizona - Mexico border

Concerns about indoor air quality and the potential effects on people living in these environments are increasing as more reports about the toxicities and the potential indoor air exposure levels of household-use chemicals and chemicals fromhousingandfurnishingmanufactureinairarebeingassessed. Gas chromatography/mass spectrometry was used to confirm numerous airborne contaminants obtained from the analysis of semipermeable membrane devices deployed inside of 52 homes situated along the border between Arizona and Mexico. We also describe nontarget analytes in the organochlorine pesticide fractions of 12 of these homes; this fraction is also the most likelytocontainthebroadestscopeofbioconcentratablechemicals accumulated from the indoor air. Approximately 400 individual components were identified, ranging from pesticides to a wide array of hydrocarbons, fragrances such as the musk xylenes, flavors relating to spices, aldehydes, alcohols, esters and phthalate esters, and other miscellaneous types of chemicals. The results presented in this study demonstrate unequivocally that the mixture of airborne chemicals present indoors is far more complex than previously demonstrated. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

Regional nutrient trends in streams and rivers of the United States, 1993-2003

Trends in flow-adjusted concentrations (indicators of anthropogenic changes) and observed concentrations (indicators of natural and anthropogenic changes) of total phosphorus and total nitrogen from 1993 to 2003 were evaluated in the eastern, central, and western United States by adapting the Regional Kendall trend test to account for seasonality and spatial correlation. The only significant regional trend was an increase in flow-adjusted concentrations of total phosphorus in the central United States, which corresponded to increases in phosphorus inputs from fertilizer in the region, particularly west of the Mississippi River. A similar upward regional trend in observed total phosphorus concentrations in the central United States was not found, likely because precipitation and runoff decreased during drought conditions in the region, offsetting the increased source loading on the land surface. A greater number of regional trends would have been significant if spatial correlation had been disregarded, indicating the importance of spatial correlation modifications in regional trend assessments when sites are not spatially independent.

Environmental Science & Technology↗

Application of a rule-based model to estimate mercury exchange for three background biomes in the continental United States

Ecosystems that have low mercury (Hg) concentrations (i.e., not enriched or impactedbygeologic or anthropogenic processes) cover most of the terrestrial surface area of the earth yet their role as a net source or sink for atmospheric Hg is uncertain. Here we use empirical data to develop a rule-based model implemented within a geographic information system framework to estimate the spatial and temporal patterns of Hg flux for semiarid deserts, grasslands, and deciduous forests representing 45% of the continental United States. This exercise provides an indication of whether these ecosystems are a net source or sink for atmospheric Hg as well as a basis for recommendation of data to collect in future field sampling campaigns. Results indicated that soil alone was a small net source of atmospheric Hg and that emitted Hg could be accounted for based on Hg input by wet deposition. When foliar assimilation and wet deposition are added to the area estimate of soil Hg flux these biomes are a sink for atmospheric Hg. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

PCBs and DDE in tree swallow ( Tachycineta bicolor ) eggs and nestlings from an estuarine PCB superfund site, New Bedford Harbor, MA, U.S.A.

While breeding tree swallows ( Tachycineta bicolor ) have been used as biomonitors for freshwater sites, we report the first use of this species to assess contaminant bioaccumulation from estuarine breeding grounds into these aerial insectivores. Eggs and nestlings were collected from nest boxes in a polychlorinated biphenyl (PCB) contaminated estuary, the New Bedford Harbor Superfund site (NBH, Massachusetts, USA), and a reference salt marsh, Fox Hill (FH, Jamestown, Rhode Island, USA). Sediments, eggs, and nestlings were compared on a ng g −1 wet weight basis for total PCBs and DDE (1,1- bis -(4-chlorophenyl)-2,2-dichloroethene), metabolite of DDT (1,1,1-trichloro-2,2- bis -(p-chlorophenyl)ethane). NBH samples contained high concentrations of PCBs compared to FH for sediment (36,500 and 0.2), eggs (11,200 and 323), and nestlings (16,800 and 26). PCB homologue patterns linked tree swallow contamination to NBH sediment. NBH samples were also contaminated with DDE compared to FH for sediment (207 and 0.9) and nestlings (235 and 30) but not for eggs (526 and 488), suggesting both NBH and nonbreeding ground sources for DDE. The relationships between sediment and tree swallow egg and nestling PCBs were similar to those reported for freshwater sites. Like some highly contaminated freshwater sites, NBH PCB bioaccumulation had little apparent effect on reproductive success.

Massachusetts↗

Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems

The oxygen isotopic composition of dissolved inorganic phosphate (δ 18 O p ) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source δ 18 O p . Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for δ 18 O p to be a useful tool for source tracking, the δ 18 O p of phosphate sources must be distinguishable from one another; however, the δ 18 O p of potential sources has not been well characterized. We measured the δ 18 O p of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of δ 18 O p values (from +8.4 to +24.9‰) for the various sources, and statistically significant differences were found between several of the source types. δ 18 O p measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in δ 18 O p values among the groups of samples, our results indicate that some sources are isotopically distinct and δ 18 O p can be used for identifying phosphate sources to aquatic systems.

Environmental Science & Technology↗

Inputs of fossil carbon from wastewater treatment plants to U.S. Rivers and oceans

Every day more than 500 million cubic meters of treated wastewater are discharged into rivers, estuaries, and oceans, an amount slightly less than the average flow of the Danube River. Typically, wastewaters have high organic carbon (OC) concentrations and represent a large fraction of total river flow and a higher fraction of river OC in densely populated watersheds. Here, we report the first direct measurements of radiocarbon ( 14 C) in municipal wastewater treatment plant (WWTP) effluent. The radiocarbon ages of particulate and dissolved organic carbon (POC and DOC) in effluent are old and relatively uniform across a range of WWTPs in New York and Connecticut. Wastewater DOC has a mean radiocarbon age of 1630 ?? 500 years B.P. and a mean ?? 13 C of -26.0 ?? 1???. Mass balance calculations indicate that 25% of wastewater DOC is fossil carbon, which is likely derived from petroleumbased household products such as detergents and pharmaceuticals. Thesefindings warrant reevaluation of the "apparent age" of riverine DOC, the total flux of petroleum carbon to U.S. oceans, and OC source assignments in waters impacted by sewage. ?? 2009 American Chemical Society.

Environmental Science & Technology↗