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Application of mixed-mode, solid-phase extraction in environmental and clinical chemistry. Combining hydrogen-bonding, cation-exchange and Van der Waals interactions

Silica- and styrene-divinylbenzene-based mixed-mode resins that contain C8, C18 and sulphonated cation-exchange groups were compared for their efficiency in isolation of neutral triazine compounds from water and of the basic drug, benzoylecgonine, from urine. The triazine compounds were isolated by a combination of Van der Waals and hydrogen-bonding interactions, and benzoylecgonine was isolated by Van der Waals interactions and cation exchange. All analytes were eluted with a polar organic solvent contaning 2% ammonium hydroxide. Larger recoveries (95%) were achieved on copolymerized mixed-mode resins where C18 and sulfonic acid are in closer proximity than on 'blended' mixed-mode resins (60-70% recovery).

Journal of Chromatography A↗

Recovery and validation of historical sediment quality data from coastal and estuarine areas: An integrated approach

A comprehensive database of sediment chemistry and environmental parameters has been compiled for Boston Harbor and Massachusetts Bay. This work illustrates methodologies for rescuing and validating sediment data from heterogeneous historical sources. It greatly expands spatial and temporal data coverage of estuarine and coastal sediments. The database contains about 3500 samples containing inorganic chemical, organic, texture and other environmental data dating from 1955 to 1994. Cooperation with local and federal agencies as well as universities was essential in locating and screening documents for the database. More than 80% of references utilized came from sources with limited distribution (gray literature). Task sharing was facilitated by a comprehensive and clearly defined data dictionary for sediments. It also served as a data entry template and flat file format for data processing and as a basis for interpretation and graphical illustration. Standard QA/QC protocols are usually inapplicable to historical sediment data. In this work outliers and data quality problems were identified by batch screening techniques that also provide visualizations of data relationships and geochemical affinities. No data were excluded, but qualifying comments warn users of problem data. For Boston Harbor, the proportion of irreparable or seriously questioned data was remarkably small (<5%), although concentration values for metals and organic contaminants spanned 3 orders of magnitude for many elements or compounds. Data from the historical database provide alternatives to dated cores for measuring changes in surficial sediment contamination level with time. The data indicate that spatial inhomogeneity in harbor environments can be large with respect to sediment-hosted contaminants. Boston Inner Harbor surficial sediments showed decreases in concentrations of Cu, Hg, and Zn of 40 to 60% over a 17-year period.A comprehensive database of sediment chemistry and environmental parameters has been compiled for Boston Harbor and Massachusetts Bay. This work illustrates methodologies for rescuing and validating sediment data from heterogeneous historical sources. It greatly expands spatial and temporal data coverage of estuarine and coastal sediments. The database contains about 3500 samples containing inorganic chemical, organic, texture and other environmental data dating from 1995 to 1994. Cooperation with local and federal agencies as well as universities was essential in locating and screening documents for the database. More than 80% of references utilized came from sources with limited distribution (gray Task sharing was facilitated by a comprehensive and clearly defined data dictionary for sediments. It also served as a data entry template and flat file format for data processing and as a basis for interpretation and graphical illustration. Standard QA/QC protocols are usually inapplicable to historical sediment data. In this work outliers and data quality problems were identified by batch screening techniques that also provide visualizations of data relationships and geochemical affinities. No data were excluded, but qualifying comments warn users of problem data. For Boston Harbor, the proportion of irreparable or seriously questioned data was remarkably small (<5%), although concentration values for metals and organic contaminants spanned 3 orders of magnitude for many elements or compounds. Data from the historical database provide alternatives to dated cores for measuring changes in surficial sediment contamination level with time. The data indicate that spatial inhomogeneity in harbor environments can be large with respect to sediment-hosted contaminants. Boston Inner Harbor surficial sediments showed decreases in concentrations Cu, Hg, and Zn of 40 to 60% over a 17-year period.

Massachusetts↗

National Water Quality Laboratory - A profile

The U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL) is a full-service laboratory that specializes in environmental analytical chemistry. The NWQL's primary mission is to support USGS programs requiring environmental analyses that provide consistent methodology for national assessment and trends analysis. The NWQL provides the following: high-quality chemical data; consistent, published, state-of-the-art methodology; extremely low-detection levels; high-volume capability; biological unit for identifying benthic invertebrates; quality assurance for determining long-term water-quality trends; and a professional staff.

Fact Sheet↗

Moving beyond p<0.05 in ecotoxicology: A guide for practitioners

Statistical inferences play a critical role in ecotoxicology. Historically, Null Hypothesis Significance Testing (NHST) has been the dominant method for inference in ecotoxicology. As a brief and informal definition of the NHST approach, researchers compare (or test) an experimental treatment or observation against a hypothesis of no relationship or effect (the null hypothesis) using the collected data to see if the observed values are statistically significant given predefined error rates. The resulting probability of observing a value equal to or greater than the observed value assuming the null hypothesis is true is the p-value. Historically, criticisms of NHST have existed for almost a century and more recently these have grown to the point where statisticians, including the American Statistical Association, have felt the need to clarify the role of NHST and p-values in science beyond their current, common use. These limitations also exist in ecotoxicology. For example, a review of the 2010 Environmental Toxicology & Chemistry (ET&C) volume found many authors did not correctly report p-values. We repeated this review looking at the 2019 volume of ET&C and the incorrect reporting of p-values still occurred almost a decade later. Problems with NHST and p-values highlight the need for statistical inferences besides NHST, something that has long been known in ecotoxicology and the broader scientific and statistical communities. Furthermore, concerns such as these led the Executive Director of the American Statistical Association to recommend against use of statistical significance in 2019. In light of these criticisms, however, ecotoxicologists require alternative methods. In this paper, we describe some alternative methods including confidence intervals, regression analysis, dose-response curves, Bayes factors, survival analysis, and model selection. Lastly, we provide insights for what ecotoxicology might look like in a post-p-value world.

Environmental Toxicology and Chemistry↗

Vegetation community recovery on restored bottomland hardwood forests in northeast Indiana, USA

Vegetation communities in restored bottomland hardwood forests in northeast Indiana were studied 6–21 years after restoration to assess progress toward restoration objectives. The study focused on four sites that were restored to compensate for resource injuries after contaminant releases. The restored sites were compared with four reference-site conditions, including crops (prerestoration condition), old field communities representing a no-management alternative, locally sampled second-growth mature forests, and forest community types described by the US National Vegetation Classification (USNVC), which represent ideal or defining conditions of recognized vegetation communities. Fixed-area plots provided data on field-sampled environmental variables, vegetation, soil, and hydrological conditions for crops, old fields, restored areas, and mature forests. The USNVC database provided quantitative data for three historically and geographically relevant reference forest community types for comparison with the sampled communities. Results of nonmetric multidimensional scaling based on species cover revealed clear gradients relating to site age and canopy development. Along those gradients, restored areas demonstrated increasing similarity to mature forest reference communities in terms of floristic composition. Specifically, the floristic quality of restored areas was significantly greater than that of crops and old fields. Furthermore, soil health measurements of physical, chemical, and hydrological conditions indicated significant improvements in restored site soils compared with prerestoration conditions represented by cropland soils. Descriptions and data from the USNVC provided ecological context for restoration target conditions and facilitated the assessment of restoration recovery along a trajectory from starting conditions to those target conditions. Descriptions by USNVC also helped identify deviations from the intended restoration objectives (e.g., invasive species recruitment) and potential adaptive management actions to return sites to their intended trajectories. Integr Environ Assess Manag 2024;00:1–22. Published 2024. This article is a U.S. Government work and is in the public domain in the USA. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Indiana↗

Multiple lines of evidence for identifying potential hazards to fish from contaminants of emerging concern in Great Lakes tributaries

Contaminants of emerging concern (CECs; e.g., pharmaceuticals, flame retardants, pesticides, and industrial chemicals) are omnipresent throughout tributaries to the Great Lakes. Furthermore, CECs are often present at concentrations that are potentially hazardous to aquatic species. Since 2010, we characterized the presence of CECs at 309 sites within 47 Great Lakes tributaries and characterized responses of fathead minnow ( Pimephales promelas ) exposed to river water at a subset of 26 sites within four tributaries. Our work resulted in three independent lines of evidence related to the potential hazards of CEC exposure to fish. First, vulnerability (where vulnerability refers to likelihood) of surface waters to CEC presence was predicted using select watershed characteristics. Second, hazard to fish (where hazard means the potential for adverse biological responses) was predicted using screening values for a subset of CECs. Third, biological responses of fathead minnow exposed to river water in streamside exposures were measured. We assessed the congruence of these three lines of evidence for identifying sites with elevated hazards to CEC exposure. Predicted vulnerability and hazards agreed at 66% of all sites. Where the two indices did not agree, vulnerability often underestimated predicted hazard. When compared with measured biological responses from streamside exposures, predicted hazards agreed for 42% of samples. Furthermore, when predicted hazards for specific effect categories were compared with similar measured biomarkers, 26% and 46% of samples agreed for reproductive and physiological effect categories, respectively. Overall, vulnerability and hazard predictions tended to overestimate the measured biological responses, providing a protective estimate of the potential hazards of CEC exposure to fish. When used together, these three approaches can help resource managers prioritize management activities in minimizing hazards of CEC exposure and can be used by researchers to prioritize studies focused on understanding the hazards of CEC exposure to fish. Integr Environ Assess Manag 2022;18:1246–1259. © 2021 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC). This article has been contributed to by US Government employees and their work is in the public domain in the USA.

Great Lakes↗

Sampling dragonflies for mercury analysis in Grand Canyon National Park, 2018–2024: A contribution of the Dragonfly Mercury Project

The Dragonfly Mercury Project is a collaborative initiative that utilizes dragonfly larvae as biosentinels to monitor mercury concentrations across 180 national parks and other protected lands, including Grand Canyon National Park (GRCA). These indicators serve as surrogates for environmental risk and can indicate where fish consumption could pose health risks through exposure to mercury. From 2018–2024, citizen scientists and staff from the National Park Service and U.S. Geological Survey helped collect close to 400 larvae from 25 GRCA sites across nearly 300 river miles, revealing mercury concentrations ranging 3.0–1337 ng/g (parts per billion) dry weight. Results were available for 20 sites. Upon comparing mercury concentrations to an impairment index, most sites were classified as low or no risk for ecological impairment, though 10% (2 sites) exceeded moderate or severe risk benchmarks (Pete’s Pocket and Buck Farm Canyon, respectively). Sources of mercury to GRCA likely stem from a combination of atmospheric deposition, upstream discharge from Lake Powell, and other watershed contributions. In addition, food web dynamics, underlying water chemistry, and environmental disturbances (e.g., floods) contribute to mercury mobilization, production, and bioaccumulation. Report findings provide a baseline for connecting ongoing science in the Colorado River watershed, informing management actions, and enhancing public engagement through citizen science.

Arizona↗

The role of sample preparation in interpretation of trace element concentration variability in moss bioindication studies

Trace element concentrations in plant bioindicators are often determined to assess the quality of the environment. Instrumental methods used for trace element determination require digestion of samples. There are different methods of sample preparation for trace element analysis, and the selection of the best method should be fitted for the purpose of a study. Our hypothesis is that the method of sample preparation is important for interpretation of the results. Here we compare the results of 36 element determinations performed by ICP-MS on ashed and on acid-digested (HNO 3 , H 2 O 2 ) samples of two moss species ( Hylocomium splendens and Pleurozium schreberi ) collected in Alaska and in south-central Poland. We found that dry ashing of the moss samples prior to analysis resulted in considerably lower detection limits of all the elements examined. We also show that this sample preparation technique facilitated the determination of interregional and interspecies differences in the chemistry of trace elements. Compared to the Polish mosses, the Alaskan mosses displayed more positive correlations of the major rock-forming elements with ash content, reflecting those elements’ geogenic origin. Of the two moss species, P. schreberi from both Alaska and Poland was also highlighted by a larger number of positive element pair correlations. The cluster analysis suggests that the more uniform element distribution pattern of the Polish mosses primarily reflects regional air pollution sources. Our study has shown that the method of sample preparation is an important factor in statistical interpretation of the results of trace element determinations.

Environmental Chemistry Letters↗

Evaluating the reliability of environmental concentration data to characterize exposure in environmental risk assessments

Environmental risk assessments often rely on measured concentrations in environmental matrices to characterize exposure of the population of interest—typically, humans, aquatic biota, or other wildlife. Yet, there is limited guidance available on how to report and evaluate exposure datasets for reliability and relevance, despite their importance to regulatory decision-making. This paper is the second of a four-paper series detailing the outcomes of a Society of Environmental Toxicology and Chemistry Technical Workshop that has developed Criteria for Reporting and Evaluating Exposure Datasets (CREED). It presents specific criteria to systematically evaluate the reliability of environmental exposure datasets. These criteria can help risk assessors understand and characterize uncertainties when existing data are used in various types of assessments and can serve as guidance on best practice for the reporting of data for data generators (to maximize utility of their datasets). Although most reliability criteria are universal, some practices may need to be evaluated considering the purpose of the assessment. Reliability refers to the inherent quality of the dataset and evaluation criteria address the identification of analytes, study sites, environmental matrices, sampling dates, sample collection methods, analytical method performance, data handling or aggregation, treatment of censored data, and generation of summary statistics. Each criterion is evaluated as “fully met,” “partly met,” “not met or inappropriate,” “not reported,” or “not applicable” for the dataset being reviewed. The evaluation concludes with a scheme for scoring the dataset as reliable with or without restrictions, not reliable, or not assignable, and is demonstrated with three case studies representing both organic and inorganic constituents, and different study designs and assessment purposes. Reliability evaluation can be used in conjunction with relevance evaluation (assessed separately) to determine the extent to which environmental monitoring datasets are “fit for purpose,” that is, suitable for use in various types of assessments. Integr Environ Assess Manag 2024;00:1–23. © 2024 Society of Environmental Toxicology & Chemistry (SETAC). This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Integrated Environmental Assessment and Management↗

Aerobic biodegradation potential of endocrine disrupting chemicals in surface-water sediment at Rocky Mountains National Park, USA

Endocrine disrupting chemicals (EDC) in surface water and bed sediment threaten the structure and function of aquatic ecosystems. In natural, remote, and protected surface-water environments where contaminant releases are sporadic, contaminant biodegradation is a fundamental driver of exposure concentration, timing, duration, and, thus, EDC ecological risk. Anthropogenic contaminants, including known and suspected EDC, were detected in surface water and sediment collected from 2 streams and 2 lakes in Rocky Mountains National Park (ROMO). The potential for aerobic EDC biodegradation was assessed in collected sediments using 6 14 C-radiolabeled model compounds. Aerobic microbial mineralization of natural (estrone and 17&beta;-estradiol) and synthetic (17&alpha;-ethinylestradiol) estrogen was significant at all sites. ROMO bed sediment microbial communities also effectively degraded the xenoestrogens, bisphenol-A and 4-nonylphenol. The same sediment samples exhibited little potential for aerobic biodegradation of triclocarban, however, illustrating the need to assess a wider range of contaminant compounds. The current results support recent concerns over the widespread environmental occurrence of carbanalide antibacterials, like triclocarban and triclosan, and suggest that backcountry use of products containing these compounds should be discouraged.

Rocky Mountain National Park↗

Characterization of ecological risks at the Milltown Reservoir-Clark Fork River Sediments Superfund Site, Montana

A comprehensive field and laboratory approach to the ecological risk assessment for the Milltown Reservoir-Clark Fork River Sediments Site, a Superfund site in the Rocky Mountains of Montana, has been described in the preceding reports of this series. The risk assessment addresses concerns over the ecological impacts of upstream releases of mining wastes to fisheries of the upper Clark Fork River (CFR) and the benthic and terrestrial habitats further downstream in Milltown Reservoir. The risk characterization component of the process integrated results from a triad of information sources: (a) chemistry studies of environmental media to identify and quantify exposures of terrestrial and aquatic organisms to site-related contaminants; (b) ecological or population studies of terrestrial vegetation, birds, benthic communities, and fish; and (c) in situ and laboratory toxicity studies with terrestrial and aquatic invertebrates and plants, small mammals, amphibians, and fish exposed to contaminated surface water, sediments, wetland soils, and food sources. Trophic transfer studies were performed on waterfowl, mammals, and predatory birds using field measurement data on metals concentrations in environmental media and lower trophic food sources. Studies with sediment exposures were incorporated into the Sediment Quality Triad approach to evaluate risks to benthic ecology. Overall results of the wetland and terrestrial studies suggested that acute adverse biological effects were largely absent from the wetland; however, adverse effects to reproductive, growth, and physiological end points of various terrestrial and aquatic species were related to metals exposures in more highly contaminated depositional areas. Feeding studies with contaminated diet collected from the upper CFR indicated that trout are at high risk from elevated metals concentrations in surface water, sediment, and aquatic invertebrates. Integration of chemical analyses with toxicological and ecological evaluations of metal effects on the wetland and fishery has provided an important foundation for environmental decisions at this site.

Montana↗

Occurrence of transformation products in the environment

Historically, most environmental occurrence research has focused on the parent compounds of organic contaminants. Research, however, has documented that the environmental transport of chemicals, such as pesticides and emerging contaminants, are substantially underestimated if transformation products are not considered. Although most examples described herein were drawn from research conducted by the U.S. Geological Survey, such results are generally reflective of those found in other parts of the world. Results from a study of 51 streams in the Midwestern United States found that transformation products were seven of the ten most frequently detected pesticide compounds in late spring runoff (after application of pre-emergent herbicides), and nine of the ten most frequently detected compounds in fall season runoff (during and after harvest). In fact, 70% of the total herbicide concentration in water from the Mississippi River Basin was from transformation products. Results from a study of 86 municipal wells in Iowa found the frequency of detection increased from 17%, when pesticide parent compounds were considered, to 53%, when both parents and transformation products were considered. Transformation products were 12 of the 15 most frequently detected compounds for this groundwater study. Although studies on transformation products of synthetic organic compounds other than pesticides are not as common, wastewater treatment plant discharges have repeatedly been shown to contribute such transformation products to streams. In addition, select detergent transformation products have been commonly found in solid waste in the 1000's mg/kg. These findings and many others document that transformation products must be considered to fully assess the potential environmental occurrence of chemical contaminants and their transport and fate in various compartments of the hydrologic system. ?? 2008 Springer-Verlag Berlin Heidelberg.

The Handbook of Environmental Chemistry series↗

Concentration, UV-spectroscopic characteristics and fractionation of DOC in stormflow from an urban stream, Southern California, USA

The composition of dissolved organic carbon (DOC) in stormflow from urban areas has been greatly altered, both directly and indirectly, by human activities and there is concern that there may be public health issues associated with DOC, which has unknown composition from different sources within urban watersheds. This study evaluated changes in the concentration and composition of DOC in stormflow in the Santa Ana River and its tributaries between 1995 and 2004 using a simplified approach based on the differences in the optical properties of DOC and using operationally defined differences in molecular weight and solubility. The data show changes in the composition of DOC in stormflow during the rainy season and differences associated with runoff from different parts of the basin, including extensive upland areas burned prior to the 2004 rainy season. Samples were collected from the Santa Ana River, which drains ~6950 km 2 of the densely populated coastal area of southern California, during 23 stormflows between 1995 and 2004. Dissolved organic carbon (DOC) concentrations during the first stormflows of the ‘winter’ (November to March) rainy season increased rapidly with streamflow and were positively correlated with increased faecal indicator bacteria concentrations. DOC concentrations were not correlated with streamflow or with other constituents during stormflows later in the rainy season and DOC had increasing UV absorbance per unit carbon as the rainy season progressed. DOC concentrations in stormflow from an urban drain tributary to the river also increased during stormflow and were greater than concentrations in the river. DOC concentrations in stormflow from a tributary stream, draining urban and agricultural land that contained more than 320 000 animals, mostly dairy cows, were higher than concentrations in stormflow from the river and from the urban drain. Fires that burned large areas of the basin before the 2004 rainy season did not increase DOC concentrations in the river during stormflow after the fires – possibly because the large watershed of the river damped the effect of the fires. However, the fires increased the hydrophobic neutral organic carbon fraction of DOC in stormflow from the urban drain and the tributary stream.

California↗

Fractionation of stable isotopes in perchlorate and nitrate during in situ biodegradation in a sandy aquifer

An in situ experiment was performed in a shallow alluvial aquifer in Maryland to quantify the fractionation of stable isotopes in perchlorate (Cl and O) and nitrate (N and O) during biodegradation. An emulsified soybean oil substrate that was previously injected into this aquifer provided the electron donor necessary for biological perchlorate reduction and denitrification. During the field experiment, groundwater extracted from an upgradient well was pumped into an injection well located within the in situ oil barrier, and then groundwater samples were withdrawn for the next 30 h. After correction for dilution (using Br– as a conservative tracer of the injectate), perchlorate concentrations decreased by 78% and nitrate concentrations decreased by 82% during the initial 8.6 h after the injection. The observed ratio of fractionation effects of O and Cl isotopes in perchlorate (e18O/e37Cl) was 2.6, which is similar to that observed in the laboratory using pure cultures (2.5). Denitrification by indigenous bacteria fractionated O and N isotopes in nitrate at a ratio of ~0.8 (e18O/e15N), which is within the range of values reported previously for denitrification. However, the magnitudes of the individual apparent in situ isotope fractionation effects for perchlorate and nitrate were appreciably smaller than those reported in homogeneous closed systems (0.2 to 0.6 times), even after adjustment for dilution. These results indicate that (1) isotope fractionation factor ratios (e18O/e37Cl, e18O/e15N) derived from homogeneous laboratory systems (e.g. pure culture studies) can be used qualitatively to confirm the occurrence of in situ biodegradation of both perchlorate and nitrate, but (2) the magnitudes of the individual apparent e values cannot be used quantitatively to estimate the in situ extent of biodegradation of either anion.

Environmental Chemistry↗

Arsenic speciation in food chains from mid-Atlantic hydrothermal vents

Arsenic concentration and speciation were determined in benthic fauna collected from the Mid-Atlantic Ridge hydrothermal vents. The shrimp species, Rimicaris exoculata, the vent chimney-dwelling mussel, Bathymodiolus azoricus, Branchipolynoe seepensis, a commensal worm of B. azoricus and the gastropod Peltospira smaragdina showed variations in As concentration and in stable isotope (δ 13 C and δ 15 N) signature between species, suggesting different sources of As uptake. Arsenic speciation showed arsenobetaine to be the dominant species in R. exoculata, whereas in B. azoricus and B. seepensis arsenosugars were most abundant, although arsenobetaine, dimethylarsinate and inorganic arsenic were also observed, along with several unidentified species. Scrape samples from outside the vent chimneys covered with microbial mat, which is a presumed food source for many vent organisms, contained high levels of total As, but organic species were not detectable. The formation of arsenosugars in pelagic environments is typically attributed to marine algae, and the pathway to arsenobetaine is still unknown. The occurrence of arsenosugars and arsenobetaine in these deep sea organisms, where primary production is chemolithoautotrophic and stable isotope analyses indicate food sources are of vent origin, suggests that organic arsenicals can occur in a foodweb without algae or other photosynthetic life.

Environmental Chemistry↗

Isotopically modified silver nanoparticles to assess nanosilver bioavailability and toxicity at environmentally relevant exposures

A major challenge in understanding the environmental implications of nanotechnology lies in studying nanoparticle uptake in organisms at environmentally realistic exposure concentrations. Typically, high exposure concentrations are needed to trigger measurable effects and to detect accumulation above background. But application of tracer techniques can overcome these limitations. Here we synthesised, for the first time, citrate-coated Ag nanoparticles using Ag that was 99.7 % 109 Ag. In addition to conducting reactivity and dissolution studies, we assessed the bioavailability and toxicity of these isotopically modified Ag nanoparticles ( 109 Ag NPs) to a freshwater snail under conditions typical of nature. We showed that accumulation of 109 Ag from 109 Ag NPs is detectable in the tissues of Lymnaea stagnalis after 24-h exposure to aqueous concentrations as low as 6 ng L –1 as well as after 3 h of dietary exposure to concentrations as low as 0.07 μg g –1 . Silver uptake from unlabelled Ag NPs would not have been detected under similar exposure conditions. Uptake rates of 109 Ag from 109 Ag NPs mixed with food or dispersed in water were largely linear over a wide range of concentrations. Particle dissolution was most important at low waterborne concentrations. We estimated that 70 % of the bioaccumulated 109 Ag concentration in L. stagnalis at exposures <0.1 µg L –1 originated from the newly solubilised Ag. Above this concentration, we predicted that 80 % of the bioaccumulated 109 Ag concentration originated from the 109 Ag NPs. It was not clear if agglomeration had a major influence on uptake rates.

Environmental Chemistry↗

Bioaccumulation trends of arsenic and antimony in a freshwater ecosystem affected by mine drainage

We compared As and Sb bioaccumulation and biomagnification when these metalloids co-occurred at varying environmental concentrations in a stream and wetlands near a contaminated mine site in Idaho (USA). We measured As and Sb concentrations in water and substrate samples, and in tissues of organisms representing several trophic levels. Bioaccumulation of both As and Sb was observed in stream organisms with the following trend of bio-diminution with increasing trophic level: primary producers > tadpoles > macroinvertebrates > trout. We also note reductions in metalloid concentrations in one of two stream remediation reaches engineered within the past 17 years to ameliorate metalloid contamination in the stream. Several wetlands contained thick microbial mats and were highly populated with boreal toad tadpoles that fed on them. The mats were extremely contaminated (up to 76 564 mg kg –1 As and 675 mg kg –1 Sb) with amorphous As- and Sb-bearing minerals that we interpret as biogenic precipitates from geomicrobiological As- and Sb-cycling. Ingested mat material provided a direct source of metalloids to tadpoles, and concentrations of 3867 mg kg –1 (As) and 375 mg kg –1 (Sb) reported here represent the highest whole body As and Sb levels ever reported in living tadpoles. The bulk of tadpole metalloid burden remained in the gut despite attempts to purge the tadpoles prior to analysis. This study adds to a number of recent investigations reporting bioaccumulation, but not biomagnification, of As and Sb in food webs. Moreover, our results suggest that tadpoles, in particular, may be more resistant to metalloid contamination than previously assumed.

Environmental Chemistry↗

First national-scale reconnaissance of neonicotinoid insecticides in streams across the USA

To better understand the fate and transport of neonicotinoid insecticides, water samples were collected from streams across the United States. In a nationwide study, at least one neonicotinoid was detected in 53 % of the samples collected, with imidacloprid detected most frequently (37 %), followed by clothianidin (24 %), thiamethoxam (21 %), dinotefuran (13 %), acetamiprid (3 %) and thiacloprid (0 %). Clothianidin and thiamethoxam concentrations were positively related to the percentage of the land use in cultivated crop production and imidacloprid concentrations were positively related to the percentage of urban area within the basin. Additional sampling was also conducted in targeted research areas to complement these national-scale results, including determining: (1) neonicotinoid concentrations during elevated flow conditions in an intensely agricultural region; (2) temporal patterns of neonicotinoids in heavily urbanised basins; (3) neonicotinoid concentrations in agricultural basins in a nationally important ecosystem; and (4) in-stream transport of neonicotinoids near a wastewater treatment plant. Across all study areas, at least one neonicotinoid was detected in 63 % of the 48 streams sampled.

Environmental Chemistry↗