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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↗

U.S. Geological Survey external quality-assurance project report to the National Atmospheric Deposition Program / National Trends Network and Mercury Deposition Network, 2007-08

The U.S. Geological Survey (USGS) used six distinct programs to provide external quality-assurance monitoring for the National Atmospheric Deposition Program / National Trends Network (NTN) and Mercury Deposition Network (MDN) during 2007-08. The field-audit program assessed the effects of onsite exposure, sample handling, and shipping on the chemistry of NTN samples, and a system-blank program assessed the same effects for MDN. Two interlaboratory-comparison programs assessed the bias and variability of the chemical analysis data from the Central Analytical Laboratory (CAL), Mercury (Hg) Analytical Laboratory (HAL), and 12 other participating laboratories. A blind-audit program was also implemented for the MDN to evaluate analytical bias in HAL total Hg concentration data. A co-located-sampler program was used to identify and quantify potential shifts in NADP data resulting from replacement of original network instrumentation with new electronic recording rain gages (E-gages) and prototype precipitation collectors. The results indicate that NADP data continue to be of sufficient quality for the analysis of spatial distributions and time trends of chemical constituents in wet deposition across the U.S. NADP data-quality objectives continued to be achieved during 2007-08. Results also indicate that retrofit of the NADP networks with the new E-gages is not likely to create step-function type shifts in NADP precipitation-depth records, except for sites where annual precipitation depth is dominated by snow because the E-gages tend to catch more snow than the original NADP rain gages. Evaluation of prototype precipitation collectors revealed no difference in sample volumes and analyte concentrations between the original NADP collectors and modified, deep-bucket collectors, but the Yankee Environmental Systems, Inc. (YES) collector obtained samples of significantly higher volumes and analyte concentrations than the standard NADP collector.

Report↗

Critical shifts in trace metal transport and remediation performance under future low river flows

Exceptionally low river flows are predicted to become more frequent and more severe across many global regions as a consequence of climate change. Investigations of trace metal transport dynamics across streamflows reveal stark changes in water chemistry, metal transformation processes, and remediation effectiveness under exceptionally low-flow conditions. High spatial resolution hydrological and water quality datasets indicate that metal-rich groundwater will exert a greater control on stream water chemistry and metal concentrations because of climate change. This is because the proportion of stream water sourced from mined areas and mineralized strata will increase under predicted future low-flow scenarios (from 25% under Q45 flow to 66% under Q99 flow in this study). However, mineral speciation modelling indicates that changes in stream pH and hydraulic conditions at low flow will decrease aqueous metal transport and increase sediment metal concentrations by enhancing metal sorption directly to streambed sediments. Solute transport modelling further demonstrates how increases in the importance of metal-rich diffuse groundwater sources at low flow could minimize the benefits of point source metal contamination treatment. Understanding metal transport dynamics under exceptionally low flows, as well as under high flows, is crucial to evaluate ecosystem service provision and remediation effectiveness in watersheds under future climate change scenarios.

Environmental Science & Technology↗

Water-quality and bottom-material characteristics of Cross Lake, Caddo Parish, Louisiana, 1997-99

Cross Lake is a shallow, monomictic lake that was formed in 1926 by the impoundment of Cross Bayou. The lake is the primary drinking-water supply for the City of Shreveport, Louisiana. In recent years, the lakeshore has become increasinginly urbanized. In addition, the land use of the watershed contributing runoff to Cross Lake has changed. Changes in land use and urbanization could affect the water chemistry and biology of the Lake. Water-quality data were collected at 10 sites on Cross Lake from February 1997 to February 1999. Water-column and bottom-material samples were collected. The water-column samples were collected at least four times per year. These samples included physical and chemical-related properties such as water temperature, dissolved oxygen, pH, and specific conductance; selected major inorganic ions; nutrients; minor elements; organic chemical constituents; and bacteria. Suspended-sediment samples were collected seven times during the sampling period. The bottom-material samples, which were collected once during the sampling period, were analyzed for selected minor elements and inorganic carbon. Aside from the nutrient-enriched condition of Cross Lake, the overall water-quality of Cross Lake is good. No primary Federal or State water-quality criteria were exceeded by any of the water-quality constituents analyzed for this report. Concentrations of major inorganic constituents, except iron and manganese, were low. Water from the lake is a sodium-bicarbonate type and is soft. Minor elements and organic compounds were present in low concentrations, many below detection limits. Nitrogen and phosphorus were the nutrients occurring in the highest concentrations. Nutrients were evenly distributed across the lake with no particular water-quality site indicating consistently higher or lower nutrient concentrations. No water samples analyzed for nitrate exceeded the U.S. Environmental Protection Agency's Maximum Contaminant Level of 10 milligrams per liter. Based on nitrogen to phosphorus ratios calculated for Cross Lake, median values for all water-quality sites were within the nitrogen-limited range (less than or equal to 5). Historical Trophic State Indexes for Cross Lake classified the lake as eutrophic. Recent (1998-99) Trophic State Indexes classify Cross Lake as mesotrophic-eutrophic, which might indicate a recution in eutrophication. Sedimentation traps indicate that Cross Lake is filling at an average rate of 0.41 inches per year. Concentrations of fecal-coliform and streptococci bacteria generally were low. Fecal coliform was detected in higher concentrations than fecal streptococci. High bacterial concentrations were measured shortly after rainfall-runoff events, possibly washing bacteria from surrounding areas into the lake.

Louisiana↗

Major-ion and selected trace-metal chemistry of the Biscayne Aquifer, Southeast Florida

The major-ion and selected trace-metal chemistry of the Biscayne aquifer was characterized as part of the Florida Ground-Water Quality Monitoring Network Program, a multiagency cooperative effort concerned with delineating baseline water quality for major aquifer systems in the State. The Biscayne aquifer is unconfined and serves as the sole source of drinking water for more than 3 million people in southeast Florida. The Biscayne aquifer consists of highly permeable interbedded limestone and sandstone of Pleistocene and Pliocene age underlying most of Dade and Broward Counties and parts of Palm Beach and Monroe Counties. The high permeability is largely caused by extensive carbonate dissolution. Water sampled from 189 wells tapping the Biscayne aquifer was predominantly a calcium bicarbonate type with some mixed types occurring in coastal areas and near major canals. Major - ion is areally uniform throughout the aquifer. According to nonparametric statistical tests of major ions and dissolved solids, the concentrations of calcium, sodium, bicarbonate, and dissolved solids increased significantly with well depth ( 0.05 significance level ), probably a result of less circulation at depth. Potassium and nitrate concentrations decreased significantly with depth. Although the source of recharge to the aquifer varies seasonally, there was no statistical difference in the concentration of major ions in pared water samples from 27 shallow wells collected during wet and dry seasons. Median concentrations for barium, chromium, copper, lead, and manganese were below maximum or secondary maximum contaminant levels set by the US Environmental Protection Agency. The median iron concentration only slightly exceeded the secondary maximum contaminant level. The concentration of barium was significantly related (0.05 significance level) to calcium and bicarbonate concentration. No distinct areal pattern or vertical distribution of the selected trace metals was evident in water from the Biscayne aquifer. Sources for trace metals found in water from the Biscayne aquifer may include local contamination, well-construction techniques, canal - aquifer interactions, and natural occurrence in area soils and rock.

Florida↗

Baseline Characteristics of Jordan Creek, Juneau, Alaska

Anadromous fish populations historically have found healthy habitat in Jordan Creek, Juneau, Alaska. Concern regarding potential degradation to the habitat by urban development within the Mendenhall Valley led to a cooperative study among the City and Borough of Juneau, Alaska Department of Environmental Conservation, and the U.S. Geological Survey, that assessed current hydrologic, water-quality, and physical-habitat conditions of the stream corridor. Periods of no streamflow were not uncommon at the Jordan Creek below Egan Drive near Auke Bay stream gaging station. Additional flow measurements indicate that periods of no flow are more frequent downstream of the gaging station. Although periods of no flow typically were in March and April, streamflow measurements collected prior to 1999 indicate similar periods in January, suggesting that no flow conditions may occur at any time during the winter months. This dewatering in the lower reaches likely limits fish rearing and spawning habitat as well as limiting the migration of juvenile salmon out to the ocean during some years. Dissolved-oxygen concentrations may not be suitable for fish survival during some winter periods in the Jordan Creek watershed. Dissolved-oxygen concentrations were measured as low as 2.8 mg/L at the gaging station and were measured as low as 0.85 mg/L in a tributary to Jordan Creek. Intermittent measurements of pH and dissolved-oxygen concentrations in the mid-reaches of Jordan Creek were all within acceptable limits for fish survival, however, few measurements of these parameters were made during winter-low-flow conditions. One set of water quality samples was collected at six different sites in the Jordan Creek watershed and analyzed for major ions and dissolved nutrients. Major-ion chemistry showed Jordan Creek is calcium bicarbonate type water with little variation between sampling sites.

Open-File Report↗

Forensic applications of nitrogen and oxygen isotopes in tracing nitrate sources in urban environments

Ground and surface waters in urban areas are susceptible to nitrate contamination from septic systems, leaking sewer lines, and fertilizer applications. Source identification is a primary step toward a successful remediation plan in affected areas. In this respect, nitrogen and oxygen isotope ratios of nitrate, in conjunction with hydrologic data and water chemistry, have proven valuable in urban studies from Austin, Texas, and Tacoma, Washington. In Austin, stream water was sampled during stremflow and baseflow conditions to assess surface and subsurface sources of nitrate, respectively. In Tacoma, well waters were sampled in adjacent sewered and un-sewered areas to determine if locally high nitrate concentrations were caused by septic systems in the un-sewered areas. In both studies, sewage was identified as a nitrate source and mixing between sewage and other sources of nitrate was apparent. In addition to source identification, combined nitrogen and oxygen isotopes were important in determining the significance of denitrification, which can complicate source assessment by reducing nitrate concentrations and increasing ??15N values. The two studies illustrate the value of nitrogen and oxygen isotopes of nitrate for forensic applications in urban areas. ?? Published by Elsevier Science Ltd. on behalf of AEHS.

Environmental Forensics↗

Assessment of ecosystem response to a temporary water level drawdown and subsequent refilling at Topock Marsh, Arizona—July 2011–October 2014

Topock Marsh is a 1,637-hectare (4,045-acre) wetland adjacent to the Colorado River near Needles, California, and a main feature of Havasu National Wildlife Refuge (NWR). The U.S. Fish and Wildlife Service, in cooperation with the Bureau of Reclamation, began construction of an infrastructure improvement project in 2010 to increase the efficiency of water use and to help protect the habitats and species found within the Havasu NWR. During construction, normal water delivery from the Colorado River into Topock Marsh through the Inlet Canal was restricted, which resulted in unusually low water elevations in 2011. The U.S. Geological Survey, commissioned by the U.S. Fish and Wildlife Service, undertook the investigation of the water quality and aquatic flora and fauna during the low water conditions. Subsequently, water elevations in the marsh returned to more normal elevations after the new concrete-lined Fire Break Canal became fully operational in January 2012. The U.S. Geological Survey made 11 field trips to the Havasu NWR between July 2011 and October 2014 to assess the effects of the temporary low water conditions and the change of inflow location (from the Inlet Canal to the Fire Break Canal) on water quality and aquatic habitat. The following conditions were monitored: water quality, sediment and plant chemistry, phytoplankton, zooplankton, aquatic macro-invertebrates, and emergent and submerged aquatic vegetation (SAV). Water-quality and biota data collected during 2013–14 were then compared with data collected during the 2011–12 low water period. Once the new Fire Break Canal became operational and Colorado River water flowed regularly into the marsh, concentrations of several water quality parameters decreased (for example, specific conductance, total dissolved solids, turbidity, chlorophyll a , and total and organic nitrogen), and phytoplankton abundance was reduced at the upstream sampling stations (TP-3, TP-2, and TP-6); the water flow pushed water with higher concentrations of these components downstream (measured at TP-8). The upstream sampling locations in 2013–14 had decreased turbidity, therefore more SAV biomass accumulated, especially in shallow areas with water depths of ≤1.0 meter (≤3.3 feet). However, the furthest downstream station had higher turbidity caused by both the suspension of autochthonous sediment and high phytoplankton density and biovolume. This higher turbidity resulted in minimal SAV growth, especially in the deeper water (>1.0 meter [>3.3 feet]). Emergent vegetation not only survived the low water conditions of 2011, but expanded its areal coverage and subsequently thrived in the higher water elevations. Overall, no immediate critically negative consequences were detected for aquatic fauna or flora that could be attributd unequivocally to the effect of low water levels. Concentrations of nutrient and trace elements in all water samples were below wildlife toxicity thresholds as established by Arizona Department of Environmental Quality. Three nonnative species were discovered shortly after the Fire Break Canal went into operation. Of the three, gizzard shad ( Dorosoma cepedianum ) and Eurasian watermilfoil ( Myriophyllum spicatum ) increased substantially in numbers from 2011–14, but quagga mussels ( Dreissena bugensis ) did not increase. Future monitoring will determine the long-term impact of the new flow regime

Arizona↗

Influence of flow-through and renewal exposures on the toxicity of copper to rainbow trout

We examined changes in water chemistry and copper (Cu) toxicity in three paired renewal and flow-through acute bioassays with rainbow trout (Oncorhynchus mykiss). Test exposure methodology influenced both exposure water chemistry and measured Cu toxicity. Ammonia and organic carbon concentrations were higher and the fraction of dissolved Cu lower in renewal tests than in paired flow-through tests. Cu toxicity was also lower in renewal tests; 96 h dissolved Cu LC50 values were 7-60% higher than LC50s from matching flow-through tests. LC50 values in both types of tests were related to dissolved organic carbon (DOC) concentrations in exposure tanks. Increases in organic carbon concentrations in renewal tests were associated with reduced Cu toxicity, likely as a result of the lower bioavailability of Cu-organic carbon complexes. The biotic ligand model of acute Cu toxicity tended to underpredict toxicity in the presence of DOC. Model fits between predicted and observed toxicity were improved by assuming that only 50% of the measured DOC was reactive, and that this reactive fraction was present as fulvic acid. ?? 2007 Elsevier Inc. All rights reserved.

Ecotoxicology and Environmental Safety↗

What makes a natural clay antibacterial?

Natural clays have been used in ancient and modern medicine, but the mechanism(s) that make certain clays lethal against bacterial pathogens has not been identified. We have compared the depositional environments, mineralogies, and chemistries of clays that exhibit antibacterial effects on a broad spectrum of human pathogens including antibiotic resistant strains. Natural antibacterial clays contain nanoscale (<200 nm), illite-smectite and reduced iron phases. The role of clay minerals in the bactericidal process is to buffer the aqueous pH and oxidation state to conditions that promote Fe 2+ solubility. Chemical analyses of E. coli killed by aqueous leachates of an antibacterial clay show that intracellular concentrations of Fe and P are elevated relative to controls. Phosphorus uptake by the cells supports a regulatory role of polyphosphate or phospholipids in controlling Fe 2+ . Fenton reaction products can degrade critical cell components, but we deduce that extracellular processes do not cause cell death. Rather, Fe 2+ overwhelms outer membrane regulatory proteins and is oxidized when it enters the cell, precipitating Fe 3+ and producing lethal hydroxyl radicals.

Environmental Science & Technology↗

Geochemical relations and distribution of selected trace elements in ground water of the northern part of the western San Joaquin Valley, California

Water samples were collected from 44 wells in the northern part of the western San Joaquin Valley, California, between March and July 1985 to assess the geochemical relations and distribution of major ions and selected trace-element concentrations in ground water of the area. The ground-waterflow system consists of a semiconfined zone and a confined zone separated by a regionally extensive clay bed. The data show that the areal and vertical distribution of ground-water chemistry in the ground-water-flow system has been affected by different agricultural and natural sources of recharge and the source and redox status of the sediments. Tritium and stable-isotope data indicate extensive infiltration of the semiconfined zone by post-1952 irrigation water originating as runoff from the Sierra Nevada. Tritium concentrations greater than 2 tritium units in most samples from the confined zone indicate that the post-1952 water also has infiltrated to wells completed in this zone. Stable-isotope data indicate that ground water from the semiconfined zone, characterized by the enriched oxygen-18 that is indicative of a Coast Ranges source, occurs in many wells in the confined zone. Movement of water from the semiconfined zone to the confined zone likely is taking place by downward flow through the many wells that perforate the confining clay bed. Trace-element concentrations in the semiconfined and confined zones generally are similar. In contrast, concentrations were significantly different between ground water from Coast Ranges sediments and ground water from Sierra Nevada sediments in both zones. Ground water from Coast Ranges sediments contains significantly higher concentrations of nitrate, boron, and selenium than water from Sierra Nevada sediments. Ground water from Sierra Nevada sediments was significantly higher in arsenic, molybdenum, and manganese than ground water from Coast Ranges sediments. These differences result from a combination of variable availability of the constituents and redox controls on mobility. Selenium, the only priority pollutant to exceed the U.S. Environmental Protection Agency's drinking-water standard, equaled or exceeded the standard of 10 micrograms per liter in water from two wells completed in the semiconfined zone and one well in the confined zone. The conservative nature of selenium behavior in the oxidized Coast Ranges deposits is shown by the high correlation (r=0.88) between selenium concentrations and specific conductance in water from these deposits in the semiconfined zone. High selenium concentrations in both zones are spatially related to the location of Coast Ranges streams that have high selenium concentrations and that were historical sources of recharge to the zones. Principal-component analysis confirmed the association of boron, chromium, lithium, and selenium, and the association of arsenic, iron, manganese, and molybdenum to sediments in the study area. The analysis indicated that the first group is associated with Coast Ranges sediments and the second with Sierra Nevada sediments.

Water Supply Paper↗

Occurrence, transport, and fate of trace elements, Blue River Basin, Summit County, Colorado: an integrated approach

Mining activities in the Blue River Basin, Summit County, Colorado, have affected the trace-element chemistry and biota along French Gulch and the Blue River. Elevated concentrations of As, Cd, Cu, Pb, and Zn were present in the bed and suspended sediments. Bed sediment trace-element concentrations were high in the streams in and near mining activities in the basin and remained high as water flowed into Dillon Reservoir about 3.5 km downstream. Bed-sediment (< 63 μm) data were useful in assessing the distribution of trace elements in the basin. Suspended-sediment measurements provided information as to the transport of the trace elements. Filtered (< 0.45 μm) water-column trace-element concentrations were orders of magnitude less than the sediment concentrations. Concentrations of Cd and Zn in the water column at some sites exceeded stream water-quality standards. Elevated trace-element concentrations in the sediment and water column are a source of contamination and must be considered in water-quality management of the Blue River Basin.

Environmental Geology↗

De facto water reuse: Bioassay suite approach delivers depth and breadth in endocrine active compound detection

Although endocrine disrupting compounds (EDCs) have been detected in wastewater and surface waters worldwide using a variety of in vitro effects-based screening tools, e.g. bioassays, few have examined potential attenuation of environmental contaminants by both natural (sorption, degradation, etc) and anthropogenic (water treatment practices) processes. This study used several bioassays and quantitative chemical analyses to assess residence-time weighted samples at six sites along a river in the northeastern United States beginning upstream of a waste water treatment plant (WWTP) outfall and proceeding downstream along the stream reach to a drinking water treatment plant (DWTP). Known steroidal estrogens were quantified and changes in signaling pathway molecular initiating events (activation of estrogen, androgen, glucocorticoid, peroxisome proliferator-activated, pregnane X receptor, and aryl hydrocarbon receptor signaling networks) were identified in water extracts. In initial multi-endpoint assays geographic and receptor-specific endocrine activity patterns in transcription factor signatures and nuclear receptor activation were discovered. In subsequent single endpoint receptor-specific bioassays, estrogen (16 of 18 samples; 0.01 to 28 ng estradiol equivalents [E2Eqs]/L) glucocorticoid (3 of 18 samples; 1.8 to 21 ng dexamethasone equivalents [DexEqs]/L), and androgen (2 of 18 samples; 0.95 to 2.1 ng dihydrotestosterone equivalents [DHTEqs]/L) receptor transcriptional activation occurred above respective assay method detection limits (0.04 ng E2Eqs/L, 1.2 ng DexEqs/L, and 0.77 ng DHTEqs/L) in multiple sampling events. Estrogen activity, the most often detected, correlated well with measured concentrations of known steroidal estrogens (R2 = 0.890). Overall, activity indicative of multiple types of endocrine active compounds was highest in wastewater effluent samples, while activity downstream was progressively lower, and negligible in (unfinished) treated water. This multiple bioassay approach, in conjunction with targeted analytical chemistry methods, has gained acceptance among water quality screening programs. Not only was estrogenic and glucocorticoid activity confirmed in the effluent by utilizing multiple methods concurrently, but other activated signaling networks that historically received less attention (i.e. peroxisome proliferator-activated receptor) were also detected.

Science of the Total Environment↗

Ground-water quality data in the Kern County Subbasin study unit, 2006— Results from the California GAMA Program

Ground-water quality in the approximately 3,000 square-mile Kern County Subbasin study unit (KERN) was investigated from January to March, 2006, as part of the Priority Basin Assessment Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin Assessment project was developed in response to the Groundwater Quality Monitoring Act of 2001, and is being conducted by the California State Water Resources Control Board (SWRCB) in collaboration with the U.S. Geological Survey (USGS) and the Lawrence Livermore National Laboratory (LLNL). The Kern County Subbasin study was designed to provide a spatially unbiased assessment of raw (untreated) ground-water quality within KERN, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 50 wells within the San Joaquin Valley portion of Kern County. Forty-seven of the wells were selected using a randomized grid-based method to provide a statistical representation of the ground-water resources within the study unit. Three additional wells were sampled to aid in the evaluation of changes in water chemistry along regional ground-water flow paths. The ground-water samples were analyzed for a large number of man-made organic constituents (volatile organic compounds [VOCs], pesticides, and pesticide degradates), constituents of special interest (perchlorate, N-nitrosodimethylamine [NDMA], and 1,2,3-trichloropropane [1,2,3-TCP]), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial indicators. Naturally occurring isotopes (tritium, carbon-14, and stable isotopes of hydrogen, oxygen, nitrogen, and carbon) and dissolved noble gases also were measured to help identify the source and age of the sampled ground water. Quality-control samples (blanks, replicates, and laboratory matrix spikes) were collected and analyzed at approximately 10 percent of the wells, and the results for these samples were used to evaluate the quality of the data from the ground-water samples. Assessment of the quality-control information resulted in censoring of less than 0.4 percent of the data collected for ground-water samples. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, raw ground water typically is treated, disinfected, or blended with other waters to maintain acceptable water quality. Regulatory thresholds apply, not to the raw ground water, but to treated water that is served to the consumer. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and the California Department of Public Health (CDPH), and as well as with thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CDPH. VOCs and pesticides each were detected in approximately 60 percent of the grid wells, and detections of all compounds but one were below health-based thresholds. The fumigant, 1,2-dibromo-3-chloropropane (DBCP), was detected above the USEPA maximum contaminant level (MCL-US) in one sample. Detections of most inorganic constituents were also below health-based thresholds. Constituents detected above health-based thresholds include: nitrate, (MCL-US, 2 samples), arsenic (MCL-US, 2 samples), and vanadium (California notification level, NL-CA, 1 sample). All detections of radioactive constituents were below health-based thresholds, although nine samples had activities of radon-222 above the lower proposed MCL-US. Most of the samples from KERN wells had concentrations of major elements, total dissolved solids, and trace elements below the non-enforceable thresholds set for aesthetic concerns.

California↗

Competition between dissolved organic matter and freshwater plankton control methylmercury isotope fractionation during uptake and photochemical demethylation

Isotope fractionation related to photochemical reactions and planktonic uptake at the base of the food web is a major uncertainty in the biological application of mercury (Hg) stable isotopes. In freshwater systems, it is unclear how competitive interactions among methylmercury (MeHg), dissolved organic matter (DOM), and phytoplankton govern the magnitude of mass-dependent and mass-independent fractionation. This study investigated how DOM alters rates of planktonic MeHg uptake and photodegradation and corresponding Hg isotope fractionation in the presence of freshwater phytoplankton species, Raphidocelis subcapitata . Outdoor sunlight exposure experiments utilizing R. subcapitata were performed in the presence of different DOM samples using environmentally relevant ratios of MeHg-DOM thiol groups. The extent of Δ 199 Hg in phytoplankton incubations (2.99‰ St. Louis River HPOA, 1.88‰ Lake Erie HPOA) was lower compared to paired abiotic control experiments (4.29 and 2.86‰, respectively) after ∼30 h of irradiation, resulting from cell shading or other limiting factors reducing the extent of photodemethylation. Although the Δ 199 Hg/Δ 201 Hg ratio was uniform across experiments (∼1.4), Δ 199 Hg/δ 202 Hg slopes varied dramatically (from −0.96 to 15.4) across incubations with R. subcapitata and DOM. In addition, no evidence of Hg isotope fractionation was observed within R. subcapitata cells. This study provides a refined examination of Hg isotope fractionation markers for key processes occurring in the lower food web prior to bioaccumulation, critical for accurately accounting for the photochemical processing of Hg isotopes across a wide spectrum of freshwater systems.

ACS Earth and Space Chemistry↗

Ground-water quality data in the Southern Sierra study unit, 2006— Results from the California GAMA program

Ground-water quality in the approximately 1,800 square-mile Southern Sierra study unit (SOSA) was investigated in June 2006 as part of the Statewide Basin Assessment Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Statewide Basin Assessment Project was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). The Southern Sierra study was designed to provide a spatially unbiased assessment of raw ground-water quality within SOSA, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from fifty wells in Kern and Tulare Counties. Thirty-five of the wells were selected using a randomized grid-based method to provide statistical representation of the study area, and fifteen were selected to evaluate changes in water chemistry along ground-water flow paths. The ground-water samples were analyzed for a large number of synthetic organic constituents [volatile organic compounds (VOCs), pesticides and pesticide degradates, pharmaceutical compounds, and wastewater-indicator compounds], constituents of special interest [perchlorate, N-nitrosodimethylamine (NDMA), and 1,2,3-trichloropropane (1,2,3-TCP)], naturally occurring inorganic constituents [nutrients, major and minor ions, and trace elements], radioactive constituents, and microbial indicators. Naturally occurring isotopes [tritium, and carbon-14, and stable isotopes of hydrogen and oxygen in water], and dissolved noble gases also were measured to help identify the source and age of the sampled ground water. Quality-control samples (blanks, replicates, and samples for matrix spikes) were collected for approximately one-eighth of the wells, and the results for these samples were used to evaluate the quality of the data for the ground-water samples. Assessment of the quality-control information resulted in censoring of less than 0.2 percent of the data collected for ground-water samples. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, or blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to treated water that is served to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and California Department of Public Health (CDPH) and thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CDPH. VOCs and pesticides were detected in less than one-third of the grid wells, and all detections in samples from SOSA wells were below health-based thresholds. All detections of trace elements and nutrients in samples from SOSA wells were below health-based thresholds, with the exception of four detections of arsenic that were above the USEPA maximum contaminant level (MCL-US) and one detection of boron that was above the CDPH notification level (NL-CA). All detections of radioactive constituents were below health-based thresholds, although four samples had activities of radon-222 above the proposed MCL-US. Most of the samples from SOSA wells had concentrations of major elements, total dissolved solids, and trace elements below the non-enforceable thresholds set for aesthetic concerns. A few samples contained iron, manganese, or total dissolved solids at concentrations above the SMCL-CA thresholds.

California↗

Environmental aspects of produced-water salt releases in onshore and coastal petroleum-producing areas of the conterminous U.S. - a bibliography

Environmental effects associated with the production of oil and gas have been reported since the first oil wells were drilled in the Appalachian Basin in Pennsylvania and Kentucky in the early to mid-1800s. The most significant of these effects are the degradation of soils, ground water, surface water, and ecosystems they support by releases of suspended and dissolved hydrocarbons and co-produced saline water. Produced water salts are less likely than hydrocarbons to be adsorbed by mineral phases in the soil and sediment and are not subject to degradation by biologic processes. Sodium is a major dissolved constituent in most produced waters and it causes substantial degradation of soils through altering of clays and soil textures and subsequent erosion. Produced water salts seem to have the most wide-ranging effects on soils, water quality, and ecosystems. Trace elements, including boron, lithium, bromine, fluorine, and radium, also occur in elevated concentrations in some produced waters. Many trace elements are phytotoxic and are adsorbed and may remain in soils after the saline water has been flushed away. Radium-bearing scale and sludge found in oilfield equipment and discarded on soils pose additional hazards to human health and ecosystems. This bibliography includes studies from across the oil- and natural-gas-producing areas of the conterminous United States that were published in the last 80 yrs. The studies describe the effects of produced water salts on soils, water quality, and ecosystems. Also included are reports that describe (1) the inorganic chemistry of produced waters included in studies of formation waters for various purposes, (2) other sources of salt affecting water quality that may be mistaken for produced water effects, (3) geochemical and geophysical techniques that allow discrimination of salt sources, (4) remediation technologies designed to repair damage caused to soils and ground water by produced water salts, and (5) contamination by naturally occurring radioactive materials (NORM)at oilfield sites.

Open-File Report↗

Isolation of methylmercury using distillation and anion-exchange chromatography for isotopic analyses in natural matrices

The development of mercury (Hg) stable isotope measurements has enhanced the study of Hg sources and transformations in the environment. As a result of the mixing of inorganic Hg (iHg) and methylmercury (MeHg) species within organisms of the aquatic food web, understanding species-specific Hg stable isotopic compositions is of significant importance. The lack of MeHg isotope measurements is due to the analytical difficulty in the separation of the MeHg from the total Hg pool, with only a few methods having been tested over the past decade with varying degrees of success, and only a handful of environmentally relevant measurements. Here, we present a novel anion-exchange resin separation method using AG 1-X4 that further isolates MeHg from the sample matrix, following a distillation pretreatment, in order to obtain ambient MeHg stable isotopic compositions. This method avoids the use of organic reagents, does not require complex instrumentation, and is applicable across matrices. Separation tests across sediment, water, and biotic matrices showed acceptable recoveries (98 ± 5%, n = 54) and reproducible δ 202 Hg isotope results (2 SDs ≤ 0.15‰) down to 5 ng of MeHg. The measured MeHg pools in natural matrices, such as plankton and sediments, showed large deviations from the non-speciated total Hg measurement, indicating that there is an important isotopic shift during methylation that is not recorded by typical measurements, but is vital in order to assess sources of Hg during bioaccumulation.

Analytical and Bioanalytical Chemistry↗