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USGS2010

The plight of the bees

The loss of biodiversity is a trend that is garnering much concern. As organisms have evolved mutualistic and synergistic relationships, the loss of one or a few species can have a much wider environmental impact. Since much pollination is facilitated by bees, the reported colony collapse disorder has many worried of widespread agricultural fallout and thus deleterious impact on human foodstocks. In this Feature, Spivak et al. review what is known of the present state of bee populations and provide information on how to mitigate and reverse the trend.

Environmental Science & Technology↗
USGS2010

A role for analytical chemistry in advancing our understanding of the occurrence, fate, and effects of Corexit Oil Dispersants

On April 24, 2010, the sinking of the Deepwater Horizon oil rig resulted in the release of oil into the Gulf of Mexico. As of July 19, 2010, the federal government's Deepwater Horizon Incident Joint Information Center estimates the cumulative range of oil released is 3,067,000 to 5,258,000 barrels, with a relief well to be completed in early August. By comparison, the Exxon Valdez oil spill released a total of 260,000 barrels of crude oil into the environment. As of June 9, BP has used over 1 million gallons of Corexit oil dispersants to solubilize oil and help prevent the development of a surface oil slick. Oil dispersants are mixtures containing solvents and surfactants that can exhibit toxicity toward aquatic life and may enhance the toxicity of components of weathered crude oil. Detailed knowledge of the composition of both Corexit formulations and other dispersants applied in the Gulf will facilitate comprehensive monitoring programs for determining the occurrence, fate, and biological effects of the dispersant chemicals. The lack of information on the potential impacts of oil dispersants has caught industry, federal, and state officials off guard. Until compositions of Corexit 9500 and 9527 were released by the U.S. Environmental Protection Agency online, the only information available consisted of Material Safety Data Sheets (MSDS), patent documentation, and a National Research Council report on oil dispersants. Several trade and common names are used for the components of the Corexits. For example, Tween 80 and Tween 85 are oligomeric mixtures.

Environmental Science & Technology↗
USGS2010

New technique for quantification of elemental hg in mine wastes and its implications for mercury evasion into the atmosphere

Mercury in the environment is of prime concern to both ecosystem and human health. Determination of the molecular-level speciation of Hg in soils and mine wastes is important for understanding its sequestration, mobility, and availability for methylation. Extended X-ray absorption fine structure (EXAFS) spectroscopy carried out under ambient P-T conditions has been used in a number of past studies to determine Hg speciation in complex mine wastes and associated soils. However, this approach cannot detect elemental (liquid) mercury in Hg-polluted soils and sediments due to the significant structural disorder of liquid Hg at ambient-temperature. A new sample preparation protocol involving slow cooling through the crystallization temperature of Hg(0) (234 K) results in its transformation to crystalline α-Hg(0). The presence and proportion of Hg(0), relative to other crystalline Hg-bearing phases, in samples prepared in this way can be quantified by low-temperature (77 K) EXAFS spectroscopy. Using this approach, we have determined the relative concentrations of liquid Hg(0) in Hg mine wastes from several sites in the California Coast Range and have found that they correlate well with measured fluxes of gaseous Hg released during light and dark exposure of the same samples, with higher evasion ratios from samples containing higher concentrations of liquid Hg(0). Two different linear relationships are observed in plots of the ratio of Hg emission under light and dark conditions vs % Hg(0), corresponding to silica−carbonate- and hot springs-type Hg deposits, with the hot springs-type samples exhibiting higher evasion fluxes than silica−carbonate type samples at similar Hg(0) concentrations. Our findings help explain significant differences in Hg evasion data for different mine sites in the California Coast Range.

Environmental Science & Technology↗
USGS2010

Measurement of dissolved organic matter fluorescense in aquatic environments: An interlaboratory comparison

The fluorescent properties of dissolved organic matter (DOM) are often studied in order to infer DOM characteristics in aquatic environments, including source, quantity, composition, and behavior. While a potentially powerful technique, a single widely implemented standard method for correcting and presenting fluorescence measurements is lacking, leading to difficulties when comparing data collected by different research groups. This paper reports on a large-scale interlaboratory comparison in which natural samples and well-characterized fluorophores were analyzed in 20 laboratories in the U.S., Europe, and Australia. Shortcomings were evident in several areas, including data quality-assurance, the accuracy of spectral correction factors used to correct EEMs, and the treatment of optically dense samples. Data corrected by participants according to individual laboratory procedures were more variable than when corrected under a standard protocol. Wavelength dependency in measurement precision and accuracy were observed within and between instruments, even in corrected data. In an effort to reduce future occurrences of similar problems, algorithms for correcting and calibrating EEMs are described in detail, and MATLAB scripts for implementing the study's protocol are provided. Combined with the recent expansion of spectral fluorescence standards, this approach will serve to increase the intercomparability of DOM fluorescence studies.

Environmental Science & Technology↗
USGS2010

Natural chlorate in the environment: Application of a new IC-ESI/MS/MS method with a Cl18O3- internal standard

A new ion chromatography electrospray tandem mass spectrometry (IC-ESI/MS/MS) method has been developed for quantification and confirmation of chlorate (ClO 3 − ) in environmental samples. The method involves the electro-chemical generation of isotopically labeled chlorate internal standard (Cl 18 O 3 − ) using 18 O water (H 2 18 O). The standard was added to all samples prior to analysis thereby minimizing the matrix effects that are associated with common ions without the need for expensive sample pretreatments. The method detection limit (MDL) for ClO 3 − was 2 ng L −1 for a 1 mL volume sample injection. The proposed method was successfully applied to analyze ClO 3 − in difficult environmental samples including soil and plant leachates. The IC-ESI/MS/MS method described here was also compared to established EPA method 317.0 for ClO 3 − analysis. Samples collected from a variety of environments previously shown to contain natural perchlorate (ClO 4 − ) occurrence were analyzed using the proposed method and ClO 3 − was found to co-occur with ClO 4 − at concentrations ranging from <2 ng L −1 in precipitation from Texas and Puerto Rico to >500 mg kg −1 in caliche salt deposits from the Atacama Desert in Chile. Relatively low concentrations of ClO 3 − in some natural groundwater samples (<0.1 μg L −1 ) analyzed in this work may indicate lower stability when compared to ClO 4 − in the subsurface. The high concentrations of ClO 3 − in caliches and soils (3−6 orders of magnitude greater) as compared to precipitation samples indicate that ClO 3 − , like ClO 4 − , may be atmospherically produced and deposited, then concentrated in dry soils, and is possibly a minor component in the biogeochemical cycle of chlorine.

Environmental Science & Technology↗
USGS2010

Zinc isotopic composition of particulate matter generated during the combustion of coal and coal + tire-derived fuels

Atmospheric Zn emissions from the burning of coal and tire-derived fuel (TDF) for power generation can be considerable. In an effort to lay the foundation for tracking these contributions, we evaluated the Zn isotopes of coal, a mixture of 95 wt % coal + 5 wt % TDF, and the particulate matter (PM) derived from their combustion in a power-generating plant. The average Zn concentrations and δ(66)Zn were 36 mg/kg and 183 mg/kg and +0.24‰ and +0.13‰ for the coal and coal + TDF, respectively. The δ(66)Zn of the PM sequestered in the cyclone-type mechanical separator was the lightest measured, -0.48‰ for coal and -0.81‰ for coal+TDF. The δ(66)Zn of the PM from the electrostatic precipitator showed a slight enrichment in the heavier Zn isotopes relative to the starting material. PM collected from the stack had the heaviest δ(66)Zn in the system, +0.63‰ and +0.50‰ for the coal and coal + TDF, respectively. Initial fractionation during the generation of a Zn-rich vapor is followed by temperature-dependent fractionation as Zn condenses onto the PM. The isotopic changes of the two fuel types are similar, suggesting that their inherent chemical differences have only a secondary impact on the isotopic fractionation process.

Environmental Science & Technology↗
USGS2010

Tapping environmental history to recreate America's colonial hydrology

Throughout American history water resources have played integral roles in shaping patterns of human settlement and networks of biological and economic exchange. In turn, humans have altered hydrologic systems to meet their needs. A paucity of climate and water discharge data for the seventeenth and eighteenth centuries, however, has left America's preindustrial hydrology largely unstudied. As a result, there have been few detailed, quantifiable, regional assessments of hydrologic change between the time of first European settlement and the dawn of industrial expansion. As scientists labor to understand present-day hydrologic systems and make predictions about the future, the value of expanding the geographic (1, 2) and temporal scopes (3, 4) of their studies has become increasingly evident. Pollen and tree-ring analyses have helped shed light on past climate and land-use patterns. But other nonscientific sources and methods can be equally revealing and in some cases complement empirical studies (5). This paper argues that environmental science, particularly that concerned with the human dimensions of water resources, stands to profit from using historical literature and archival sources. By considering work in environmental history, forging closer working relationships between the geophysical and social sciences, and seriously entertaining narratives as a form of evidence, environmental scientists can not only look farther into the past and across broader geographic areas, but they can also more accurately describe the nuances and complexities that define the ways humans have changed the world around them. In this paper, we present the recommendations of a multidisciplinary summer institute that developed 1) a conceptual and methodological framework for conducting historical hydrology, and 2) suggestions for ways that historical information can be used to inform the hydrologic sciences. Our intent here is to encourage further work along these or similar lines. We believe that future efforts that build on our famework and draw and expand upon the sources referenced below will produce scholarship of great utility to both environmental and social sciences.

Environmental Science & Technology↗
USGS2010

The need for simultaneous evaluation of ecosystem services and land use change

We are living in a period of massive global change. This rate of change may be almost without precedent in geologic history ( 1 ). Even the most remote areas of the planet are influenced by human activities. Modern landscapes have been highly modified to accommodate a growing human population that the United Nations has forecast to peak at 9.1 billion by 2050. Over this past century, reliance on services from ecosystems has increased significantly and, over past decades, sustainability of our modern, intensively managed ecosystems has been a topic of serious international concern ( 1 ). Numerous papers addressing a particular land-use change effect on specific ecosystem services have recently been published. For example, there is currently great interest in increasing biofuel production to achieve energy inde- pendence goals and recent papers have independently focused attention on impacts of land-use change on single ecosystem services such as carbon sequestration ( 2 ) and many others (e.g., water availability, biodiversity, pollination). However, land-use change clearly affects myriad ecosystem services simultaneously. Hence, a broader perspective and context is needed to evaluate and understand interrelated affects on multiple ecosystem services, especially as we strive for the goal of sustainably managing global ecosystems. Similarly, land uses affect ecosystem services synergistically; single land-use evaluations may be misleading because the overall impact on an ecosystem is not evaluated. A more holistic approach would provide a means and framework to characterize how land-use change affects provisioning of goods and services of complete ecosystems.

Environmental Science & Technology↗
USGS2010

Regional contamination versus regional dietary differences: Understanding geographic variation in brominated and chlorinated contaminant levels in polar bears

The relative contribution of regional contamination versus dietary differences to geographic variation in polar bear ( Ursus maritimus ) contaminant levels is unknown. Dietary variation between Alaska, Canada, East Greenland, and Svalbard subpopulations was assessed by muscle nitrogen and carbon stable isotope (δ 15 N, δ 13 C) and adipose fatty acid (FA) signatures relative to their main prey (ringed seals). Western and southern Hudson Bay signatures were characterized by depleted δ 15 N and δ 13 C, lower proportions of C 20 and C 22 monounsaturated FAs and higher proportions of C 18 and longer chain polyunsaturated FAs. East Greenland and Svalbard signatures were reversed relative to Hudson Bay. Alaskan and Canadian Arctic signatures were intermediate. Between-subpopulation dietary differences predominated over interannual, seasonal, sex, or age variation. Among various brominated and chlorinated contaminants, diet signatures significantly explained variation in adipose levels of polybrominated diphenyl ether (PBDE) flame retardants (14−15%) and legacy PCBs (18−21%). However, dietary influence was contaminant class-specific, since only low or nonsignificant proportions of variation in organochlorine pesticide (e.g., chlordane) levels were explained by diet. Hudson Bay diet signatures were associated with lower PCB and PBDE levels, whereas East Greenland and Svalbard signatures were associated with higher levels. Understanding diet/food web factors is important to accurately interpret contaminant trends, particularly in a changing Arctic.

Environmental Science & Technology↗
USGS2010

Flood hydrology and methylmercury availability in Coastal Plain rivers

Mercury (Hg) burdens in top-predator fish differ substantially between adjacent South Carolina Coastal Plain river basins with similar wetlands coverage. In the Congaree River, floodwaters frequently originate in the Blue Ridge and Piedmont regions, where wetlands coverage and surface water dissolved methylmercury (MeHg) concentrations are low. Piedmont-driven flood events can lead to downward hydraulic gradients in the Coastal Plain riparian wetland margins, inhibiting MeHg transport from wetland sediments, and decreasing MeHg availability in the Congaree River habitat. In the adjacent Edisto River basin, floodwaters originate only within Coastal Plain sediments, maintaining upward hydraulic gradients even during flood events, promoting MeHg transport to the water column, and enhancing MeHg availability in the Edisto River habitat. These results indicate that flood hydrodynamics contribute to the variability in Hg vulnerability between Coastal Plain rivers and that comprehensive regional assessment of the relationship between flood hydrodynamics and Hg risk in Coastal Plain streams is warranted.

South Carolina↗
USGS2011

Effects of humic substances on precipitation and aggregation of zinc sulfide nanoparticles

Nanoparticulate metal sulfides such as ZnS can influence the transport and bioavailability of pollutant metals in anaerobic environments. The aim of this work was to investigate how the composition of dissolved natural organic matter (NOM) influences the stability of zinc sulfide nanoparticles as they nucleate and aggregate in water with dissolved NOM. We compared NOM fractions that were isolated from several surface waters and represented a range of characteristics including molecular weight, type of carbon, and ligand density. Dynamic light scattering was employed to monitor the growth and aggregation of Zn−S−NOM nanoparticles in supersaturated solutions containing dissolved aquatic humic substances. The NOM was observed to reduce particle growth rates, depending on solution variables such as type and concentration of NOM, monovalent electrolyte concentration, and pH. The rates of growth increased with increasing ionic strength, indicating that observed growth rates primarily represented aggregation of charged Zn−S−NOM particles. Furthermore, the observed rates decreased with increasing molecular weight and aromatic content of the NOM fractions, while carboxylate and reduced sulfur content had little effect. Differences between NOM were likely due to properties that increased electrosteric hindrances for aggregation. Overall, results of this study suggest that the composition and source of NOM are key factors that contribute to the stabilization and persistence of zinc sulfide nanoparticles in the aquatic environment.

Environmental Science & Technology↗
USGS2011

Differential effects of dissolved organic carbon upon re-entrainment and surface properties of groundwater bacteria and bacteria-sized microspheres during transport through a contaminated, sandy aquifer

Injection-and-recovery studies involving a contaminated, sandy aquifer (Cape Cod, Massachusetts) were conducted to assess the relative susceptibility for in situ re-entrainment of attached groundwater bacteria ( Pseudomonas stuzeri ML2, and uncultured, native bacteria) and carboxylate-modified microspheres (0.2 and 1.0 μm diameters). Different patterns of re-entrainment were evident for the two colloids in response to subsequent injections of groundwater (hydrodynamic perturbation), deionized water (ionic strength alteration), 77 μM linear alkylbenzene sulfonates (LAS, anionic surfactant), and 76 μM Tween 80 (polyoxyethylene sorbitan monooleate, a very hydrophobic nonionic surfactant). An injection of deionized water was more effective in causing detachment of micrsopheres than were either of the surfactants, consistent with the more electrostatic nature of microsphere’s attachment, their extreme hydrophilicity (hydrophilicity index, HI, of 0.99), and negative charge (zeta potentials, ζ, of −44 to −49 mv). In contrast, Tween 80 was considerably more effective in re-entraining the more-hydrophobic native bacteria. Both the hydrophilicities and zeta potentials of the native bacteria were highly sensitive to and linearly correlated with levels of groundwater dissolved organic carbon (DOC), which varied modestly from 0.6 to 1.3 mg L −1 . The most hydrophilic (0.52 HI) and negatively charged (ζ −38.1 mv) indigenous bacteria were associated with the lowest DOC. FTIR spectra indicated the latter community had the highest average density of surface carboxyl groups. In contrast, differences in groundwater (DOC) had no measurable effect on hydrophilicity of the bacteria-sized microspheres and only a minor effect on their ζ. These findings suggest that microspheres may not be very good surrogates for bacteria in field-scale transport studies and that adaptive (biological) changes in bacterial surface characteristics may need to be considered where there is longer-term exposure to contaminant DOC.

Environmental Science & Technology↗
USGS2011

Probability of detecting perchlorate under natural conditions in deep groundwater in California and the Southwestern United States

We use data from 1626 groundwater samples collected in California, primarily from public drinking water supply wells, to investigate the distribution of perchlorate in deep groundwater under natural conditions. The wells were sampled for the California Groundwater Ambient Monitoring and Assessment Priority Basin Project. We develop a logistic regression model for predicting probabilities of detecting perchlorate at concentrations greater than multiple threshold concentrations as a function of climate (represented by an aridity index) and potential anthropogenic contributions of perchlorate (quantified as an anthropogenic score, AS). AS is a composite categorical variable including terms for nitrate, pesticides, and volatile organic compounds. Incorporating water-quality parameters in AS permits identification of perturbation of natural occurrence patterns by flushing of natural perchlorate salts from unsaturated zones by irrigation recharge as well as addition of perchlorate from industrial and agricultural sources. The data and model results indicate low concentrations (0.1-0.5 &mu;g/L) of perchlorate occur under natural conditions in groundwater across a wide range of climates, beyond the arid to semiarid climates in which they mostly have been previously reported. The probability of detecting perchlorate at concentrations greater than 0.1 &mu;g/L under natural conditions ranges from 50-70% in semiarid to arid regions of California and the Southwestern United States to 5-15% in the wettest regions sampled (the Northern California coast). The probability of concentrations above 1 &mu;g/L under natural conditions is low (generally <3%).

California↗
USGS2011

Trophic magnification of PCBs and its relationship to the octanol-water partition coefficient

We investigated polychlorinated biphenyl (PCB) bioaccumulation relative to octanol-water partition coefficient (KOW) and organism trophic position (TP) at the Lake Hartwell Superfund site (South Carolina). We measured PCBs (127 congeners) and stable isotopes (??15N) in sediment, organic matter, phytoplankton, zooplankton, macroinvertebrates, and fish. TP, as calculated from ??15N, was significantly, positively related to PCB concentrations, and food web trophic magnification factors (TMFs) ranged from 1.5-6.6 among congeners. TMFs of individual congeners increased strongly with log KOW, as did the predictive power (r2) of individual TP-PCB regression models used to calculate TMFs. We developed log KOW-TMF models for eight food webs with vastly different environments (freshwater, marine, arctic, temperate) and species composition (cold- vs warmblooded consumers). The effect of KOW on congener TMFs varied strongly across food webs (model slopes 0.0-15.0) because the range of TMFs among studies was also highly variable. We standardized TMFs within studies to mean = 0, standard deviation (SD) = 1 to normalize for scale differences and found a remarkably consistent KOW effect on TMFs (no difference in model slopes among food webs). Our findings underscore the importance of hydrophobicity (as characterized by KOW) in regulating bioaccumulation of recalcitrant compounds in aquatic systems, and demonstrate that relationships between chemical KOW and bioaccumulation from field studies are more generalized than previously recognized. ?? This article not subject to U.S. Copyright. Published 2011 by the American Chemical Society.

Environmental Science & Technology↗
USGS2011

Effects of the antimicrobial sulfamethoxazole on groundwater bacterial enrichment

The effects of “trace” (environmentally relevant) concentrations of the antimicrobial agent sulfamethoxazole (SMX) on the growth, nitrate reduction activity, and bacterial composition of an enrichment culture prepared with groundwater from a pristine zone of a sandy drinking-water aquifer on Cape Cod, MA, were assessed by laboratory incubations. When the enrichments were grown under heterotrophic denitrifying conditions and exposed to SMX, noticeable differences from the control (no SMX) were observed. Exposure to SMX in concentrations as low as 0.005 μM delayed the initiation of cell growth by up to 1 day and decreased nitrate reduction potential (total amount of nitrate reduced after 19 days) by 47% ( p = 0.02). Exposure to 1 μM SMX, a concentration below those prescribed for clinical applications but higher than concentrations typically detected in aqueous environments, resulted in additional inhibitions: reduced growth rates ( p = 5 × 10 −6 ), lower nitrate reduction rate potentials ( p = 0.01), and decreased overall representation of 16S rRNA gene sequences belonging to the genus Pseudomonas . The reduced abundance of Pseudomonas sequences in the libraries was replaced by sequences representing the genus Variovorax . Results of these growth and nitrate reduction experiments collectively suggest that subtherapeutic concentrations of SMX altered the composition of the enriched nitrate-reducing microcosms and inhibited nitrate reduction capabilities.

Environmental Science & Technology↗
USGS2011

Spatial and seasonal variability of dissolved methylmercury in two stream basins in the Eastern United States

We assessed methylmercury (MeHg) concentrations across multiple ecological scales in the Edisto (South Carolina) and Upper Hudson (New York) River basins. Out-of-channel wetland/floodplain environments were primary sources of filtered MeHg (F-MeHg) to the stream habitat in both systems. Shallow, open-water areas in both basins exhibited low F-MeHg concentrations and decreasing F-MeHg mass flux. Downstream increases in out-of-channel wetlands/floodplains and the absence of impoundments result in high MeHg throughout the Edisto. Despite substantial wetlands coverage and elevated F-MeHg concentrations at the headwater margins, numerous impoundments on primary stream channels favor spatial variability and lower F-MeHg concentrations in the Upper Hudson. The results indicated that, even in geographically, climatically, and ecologically diverse streams, production in wetland/floodplain areas, hydrologic transport to the stream aquatic environment, and conservative/nonconservative attenuation processes in open water areas are fundamental controls on dissolved MeHg concentrations and, by extension, MeHg availability for potential biotic uptake.

New York, South Carolina↗
USGS2011

Influence of dissolved organic matter on the environmental fate of metals, nanoparticles, and colloids

We have known for decades that dissolved organic matter (DOM) plays a critical role in the biogeochemical cycling of trace metals and the mobility of colloidal particles in aquatic environments. In recent years, concerns about the ecological and human health effects of metal-based engineered nanoparticles released into natural waters have increased efforts to better define the nature of DOM interactions with metals and surfaces. Nanomaterials exhibit unique properties and enhanced reactivities that are not apparent in larger materials of the same composition 1,2 or dissolved ions of metals that comprise the nanoparticles. These nanoparticle-specific properties generally result from the relatively large proportion of the atoms located at the surface, which leads to very high specific surface areas and a high proportion of crystal lattice imperfections relative to exposed surface area. Nanoscale colloids are ubiquitous in nature,2 and many engineered nanomaterials have analogs in the natural world. The properties of these materials, whether natural or manmade, are poorly understood, and new challenges have been presented in assessing their environmental fate. These challenges are particularly relevant in aquatic environments where interactions with DOM are key, albeit often overlooked, moderators of reactivity at the molecular and nanocolloidal scales.

Environmental Science & Technology↗