Variation in metal concentrations across a large contamination gradient is reflected in stream but not linked riparian food webs.

Aquatic insects link food web dynamics across freshwater-terrestrial boundaries and subsidize terrestrial consumer populations. Contaminants that accumulate in larval aquatic insects and are retained across metamorphosis can increase dietary exposure for riparian insectivores. To better understand potential exposure of terrestrial insectivores to aquatically-derived trace metals, metal concentrations in water and tissues were analyzed from different components of streams and riparian food webs across a large (2-3 orders of magnitude) metal gradient (e.g., Zn, Cu, Cd, Pb) in the Rocky Mountains (USA). Our research indicates that the trace metal concentration gradient present among streams was lost during metamorphosis of aquatic larval insects into terrestrially flying adults, decoupling terrestrial exposures from aquatic concentrations. This pattern was caused by declines in 1) among-stream variation in trace metal concentrations, 2) relationships between metal concentrations in paired water and food web components, and 3) mean metal concentrations within aquatic food webs and across the aquatic-terrestrial boundary. Specifically, among-stream variation in trace metal concentrations was highest for water and aquatic vegetation, intermediate for aquatic insect larvae (~30% lower than water) and lowest for adult aquatic insects and riparian spiders (~65% lower). Metal concentrations in paired water and food web components ranged from highly related across the stream-metal gradient (slopes ~1) for water and aquatic vegetation, to less related (slopes closer to 0) for aquatic vegetation and aquatic insect larvae, to unrelated (slopes ~0) for aquatic larval and adult insects. Finally, mean metal concentrations were highest in aquatic vegetation and lowest in adult aquatic insects emerging from streams (~50% lower than aquatic vegetation). Our results indicate less efficient trophic transfer and higher metamorphic loss of trace metals from high metal streams (i.e., exposure-dependent transfer). For many trace metals, aquatic-terrestrial dietary transfer is unlikely to be an important source of exposure for terrestrial insectivores of adult aquatic insects.

Modifications to EPA Method 3060A to Improve Extraction of Cr(VI) from Chromium Ore Processing Residue-Contaminated Soils.

It has been shown that EPA Method 3060A does not adequately extract Cr(VI) from chromium ore processing residue (COPR). We modified various parameters of EPA 3060A toward understanding the transformation of COPR minerals in the alkaline extraction and improving extraction of Cr(VI) from NIST SRM 2701, a standard COPR-contaminated soil. Aluminum and Si were the major elements dissolved from NIST 2701, and their concentrations in solution were correlated with Cr(VI). The extraction fluid leached additional Al and Si from the method-prescribed borosilicate glass vessels which appeared to suppress the release of Cr(VI). Use of polytetrafluoroethylene vessels and intensive grinding of NIST 2701 increased the amount of Cr(VI) extracted. These modifications, combined with an increased extraction fluid to sample ratio of ≥900 mL g-1 and 48-h extraction time resulted in a maximum release of 1274 ± 7 mg kg-1 Cr(VI). This is greater than the NIST 2701 certified value of 551 ± 35 mg kg-1 but less than 3050 mg kg-1 Cr(VI) previously estimated by X-ray absorption near edge structure spectroscopy. Some of the increased Cr(VI) may have resulted from oxidation of Cr(III) released from brownmillerite which rapidly transformed during the extractions. Layered-double hydroxides remained stable during extractions and represent a potential residence for unextracted Cr(VI).

In vivo isotopic fractionation of zinc and biodynamic modeling yield insights into detoxification mechanisms in the mayfly Neocloeon triangulifer.

Diversity and biomass of aquatic insects decline in metal-rich aquatic environments, but the mechanisms by which insects from such environments cope with potentially toxic metal concentrations to survive through adulthood are less well understood. In this study, we measured Zn concentrations and isotopes in laboratory-reared diatoms and mayflies (Neocloeon triangulifer) from larval through adult stages. The larvae were fed Zn-enriched diatoms, and bio-concentrated Zn by a factor of 2.5-5 relative to the diatoms but maintained the same Zn-isotopic ratio. These results reflect the importance of dietary uptake and the greater rate of uptake relative to excretion or growth. Upon metamorphosis to subimago, Zn concentrations declined by >70%, but isotopically heavy Zn remained in the subimago bodies. We surmised that the loss of isotopically light Zn during metamorphosis was due to the loss of detoxified Zn and retention of metabolically useful Zn. Through the transition from subimago to imago, Zn concentrations and isotope ratios were virtually unchanged. Because the decrease in Zn body concentration and increase in heavier Zn are seen in the subimagos relative to the larvae, the compartmentalization of Zn must be occurring within the larvae. A biodynamic model was constructed, allowing for isotopic fractionation and partitioning of Zn between metabolically essential and detoxified Zn reservoirs within larvae. The model provides a consistent set of rate and fractionation constants that successfully describe the experimental observations. Specifically, metabolically essential Zn is isotopically heavier and is tightly held once assimilated, and excess, isotopically light Zn is sequestered, detoxified, and ultimately lost during the metamorphosis of larvae to subimagos. To our knowledge, this is the first documentation of in vivo isotopic fractionation in insects, offering an improved understanding of the mechanisms and rates by which the N. triangulifer larvae regulate excess Zn in their bodies.

Metamorphosis Affects Metal Concentrations and Isotopic Signatures in a Mayfly (Baetis tricaudatus): Implications for the Aquatic-Terrestrial Transfer of Metals.

Insect metamorphosis often results in substantial chemical changes that can alter contaminant concentrations and fractionate isotopes. We exposed larval mayflies (Baetis tricaudatus) and their food (periphyton) to an aqueous zinc gradient (3-340 µg Zn/l) and measured zinc concentrations at different stages of metamorphosis: larval, subimago, and imago. We also measured changes in stable isotopes (δ15N and δ13C) in unexposed mayflies. Larval zinc concentrations were positively related to aqueous zinc, increasing 9-fold across the exposure gradient. Adult zinc concentrations were also positively related to aqueous zinc, but were 7-fold lower than larvae. This relationship varied according to adult substage and sex. Tissue concentrations in female imagoes were not related to exposure concentrations, but the converse was true for all other stage-by-sex combinations. Metamorphosis also increased δ15N by ∼0.8‰, but not δ13C. Thus, the main effects of metamorphosis on insect chemistry were large declines in zinc concentrations coupled with increased δ15N signatures. For zinc, this change was largely consistent across the aqueous exposure gradient. However, differences among sexes and stages suggest that caution is warranted when using nitrogen isotopes or metal concentrations measured in one insect stage (e.g., larvae) to assess risk to wildlife that feed on subsequent life stages (e.g., adults).

Improving the ecological relevance of toxicity tests on scleractinian corals: Influence of season, life stage, and seawater temperature.

Metal pollutants in marine systems are broadly acknowledged as deleterious: however, very little data exist for tropical scleractinian corals. We address this gap by investigating how life-history stage, season and thermal stress influence the toxicity of copper (Cu) and lead (Pb) in the coral Pocillopora damicornis. Our results show that under ambient temperature, adults and larvae appear to tolerate exposure to unusually high levels of copper (96 h-LC50 ranging from 167 to 251 µg Cu L(-1)) and lead (from 477 to 742 µg Pb L(-1)). Our work also highlights that warmer conditions (seasonal and experimentally manipulated) reduce the tolerance of adults and larvae to Cu toxicity. Despite a similar trend observed for the response of larvae to Pb toxicity to experimentally induced increase in temperature, surprisingly adults were more resistant in warmer condition to Pb toxicity. In the summer adults were less resistant to Cu toxicity (96 h-LC50 = 175 µg L(-1)) than in the winter (251 µg L(-1)). An opposite trend was observed for the Pb toxicity on adults between summer and winter (96 h-LC50 of 742 vs 471 µg L(-1), respectively). Larvae displayed a slightly higher sensitivity to Cu and Pb than adults. An experimentally induced 3 °C increase in temperature above ambient decreased larval resistance to Cu and Pb toxicity by 23-30% (96 h-LC50 of 167 vs 129 µg Cu L(-1) and 681 vs 462 µg Pb L(-1)). Our data support the paradigm that upward excursions in temperature influence physiological processes in corals that play key roles in regulating metal toxicity. These influences are more pronounced in larva versus adult corals. These findings are important when contextualized climate change-driven warming in the oceans and highlight that predictions of ecological outcomes to metal pollutants will be improved by considering environmental context and the life stages of organism under study.

Cross-ecosystem impacts of stream pollution reduce resource and contaminant flux to riparian food webs.

The effects of aquatic contaminants are propagated across ecosystem boundaries by aquatic insects that export resources and contaminants to terrestrial food webs; however, the mechanisms driving these effects are poorly understood. We examined how emergence, contaminant concentration, and total contaminant flux by adult aquatic insects changed over a gradient of bioavailable metals in streams and how these changes affected riparian web-building spiders. Insect emergence decreased 97% over the metal gradient, whereas metal concentrations in adult insects changed relatively little. As a result, total metal exported by insects (flux) was lowest at the most contaminated streams, declining 96% among sites. Spiders were affected by the decrease in prey biomass, but not by metal exposure or metal flux to land in aquatic prey. Aquatic insects are increasingly thought to increase exposure of terrestrial consumers to aquatic contaminants, but stream metals reduce contaminant flux to riparian consumers by strongly impacting the resource linkage. Our results demonstrate the importance of understanding the contaminant-specific effects of aquatic pollutants on adult insect emergence and contaminant accumulation in adults to predict impacts on terrestrial food webs.

Linking geological and health sciences to assess childhood lead poisoning from artisanal gold mining in Nigeria.

BACKGROUND: In 2010, Médecins Sans Frontières discovered a lead poisoning outbreak linked to artisanal gold processing in northwestern Nigeria. The outbreak has killed approximately 400 young children and affected thousands more. OBJECTIVES: Our aim was to undertake an interdisciplinary geological- and health-science assessment to clarify lead sources and exposure pathways, identify additional toxicants of concern and populations at risk, and examine potential for similar lead poisoning globally. METHODS: We applied diverse analytical methods to ore samples, soil and sweep samples from villages and family compounds, and plant foodstuff samples. RESULTS: Natural weathering of lead-rich gold ores before mining formed abundant, highly gastric-bioaccessible lead carbonates. The same fingerprint of lead minerals found in all sample types confirms that ore processing caused extreme contamination, with up to 185,000 ppm lead in soils/sweep samples and up to 145 ppm lead in plant foodstuffs. Incidental ingestion of soils via hand-to-mouth transmission and of dusts cleared from the respiratory tract is the dominant exposure pathway. Consumption of water and foodstuffs contaminated by the processing is likely lesser, but these are still significant exposure pathways. Although young children suffered the most immediate and severe consequences, results indicate that older children, adult workers, pregnant women, and breastfed infants are also at risk for lead poisoning. Mercury, arsenic, manganese, antimony, and crystalline silica exposures pose additional health threats. CONCLUSIONS: Results inform ongoing efforts in Nigeria to assess lead contamination and poisoning, treat victims, mitigate exposures, and remediate contamination. Ore deposit geology, pre-mining weathering, and burgeoning artisanal mining may combine to cause similar lead poisoning disasters elsewhere globally.

Simultaneous speciation of arsenic, selenium, and chromium: species stability, sample preservation, and analysis of ash and soil leachates.

An analytical method using high-performance liquid chromatography separation with inductively coupled plasma mass spectrometry (ICP-MS) detection previously developed for the determination of Cr(III) and Cr(VI) has been adapted to allow the determination of As(III), As(V), Se(IV), Se(VI), Cr(III), and Cr(VI) under the same chromatographic conditions. Using this method, all six inorganic species can be determined in less than 3 min. A dynamic reaction cell (DRC)-ICP-MS system was used to detect the species eluted from the chromatographic column in order to reduce interferences. A variety of reaction cell gases and conditions may be utilized with the DRC-ICP-MS, and final selection of conditions is determined by data quality objectives. Results indicated all starting standards, reagents, and sample vials should be thoroughly tested for contamination. Tests on species stability indicated that refrigeration at 10 °C was preferential to freezing for most species, particularly when all species were present, and that sample solutions and extracts should be analyzed as soon as possible to eliminate species instability and interconversion effects. A variety of environmental and geological samples, including waters and deionized water [leachates] and simulated biological leachates from soils and wildfire ashes have been analyzed using this method. Analytical spikes performed on each sample were used to evaluate data quality. Speciation analyses were conducted on deionized water leachates and simulated lung fluid leachates of ash and soils impacted by wildfires. These results show that, for leachates containing high levels of total Cr, the majority of the chromium was present in the hexavalent Cr(VI) form. In general, total and hexavalent chromium levels for samples taken from burned residential areas were higher than those obtained from non-residential forested areas. Arsenic, when found, was generally in the more oxidized As(V) form. Selenium (IV) and (VI) were present, but typically at low levels.

Evaluating the behavior of gadolinium and other rare earth elements through large metropolitan sewage treatment plants.

A primary pathway for emerging contaminants (pharmaceuticals, personal care products, steroids, and hormones) to enter aquatic ecosystems is effluent from sewage treatment plants (STP), and identifying technologies to minimize the amount of these contaminants released is important. Quantifying the flux of these contaminants through STPs is difficult. This study evaluates the behavior of gadolinium, a rare earth element (REE) utilized as a contrasting agent in magnetic resonance imaging (MRI), through four full-scale metropolitan STPs that utilize several biosolids thickening, conditioning, stabilization, and dewatering processing technologies. The organically complexed Gd from MRIs has been shown to be stable in aquatic systems and has the potential to be utilized as a conservative tracer in STP operations to compare to an emerging contaminant of interest. Influent and effluent waters display large enrichments in Gd compared to other REEs. In contrast, most sludge samples from the STPs do not display Gd enrichments, including primary sludges and end-product sludges. The excess Gd appears to remain in the liquid phase throughout the STP operations, but detailed quantification of the input Gd load and residence times of various STP operations is needed to utilize Gd as a conservative tracer.

Measurement of total Zn and Zn isotope ratios by quadrupole ICP-MS for evaluation of Zn uptake in gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss).

This study evaluates the potential use of stable zinc isotopes in toxicity studies measuring zinc uptake by the gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss). The use of stable isotopes in such studies has several advantages over the use of radioisotopes, including cost, ease of handling, elimination of permit requirements, and waste disposal. A pilot study using brown trout was performed to evaluate sample preparation methods and the ability of a quadrupole inductively coupled plasma mass spectrometer (ICP-MS) system to successfully measure changes in the (67)Zn/(66)Zn ratios for planned exposure levels and duration. After completion of the pilot study, a full-scale zinc exposure study using rainbow trout was performed. The results of these studies indicate that there are several factors that affect the precision of the measured (67)Zn/(66)Zn ratios in the sample digests, including variations in sample size, endogenous zinc levels, and zinc uptake rates by individual fish. However, since these factors were incorporated in the calculation of the total zinc accumulated by the gills during the exposures, the data obtained were adequate for their intended use in calculating zinc binding and evaluating the influences of differences in water quality parameters.

An enriched stable-isotope approach to determine the gill-zinc binding properties of juvenile rainbow trout (Oncorhynchus mykiss) during acute zinc exposures in hard and soft waters.

The objective of the present study was to employ an enriched stable-isotope approach to characterize Zn uptake in the gills of rainbow trout (Oncorhynchus mykiss) during acute Zn exposures in hard water (approximately 140 mg/L as CaCO3) and soft water (approximately 30 mg/L as CaCO3). Juvenile rainbow trout were acclimated to the test hardnesses and then exposed for up to 72 h in static exposures to a range of Zn concentrations in hard water (0-1000 microg/L) and soft water (0-250 microg/L). To facilitate detection of new gill Zn from endogenous gill Zn, the exposure media was significantly enriched with 67Zn stable isotope (89.60% vs. 4.1% natural abundance). Additionally, acute Zn toxicity thresholds (96-h median lethal concentration [LC50]) were determined experimentally through traditional, flow-through toxicity tests in hard water (580 microg/L) and soft water (110 microg/L). Following short-term (< or =3 h) exposures, significant differences in gill accumulation of Zn between hard and soft water treatments were observed at the three common concentrations (75, 150, and 250 microg/L), with soft water gills accumulating more Zn than hard water gills. Short-term gill Zn accumulation at hard and soft water LCS0s (45-min median lethal accumulation) was similar (0.27 and 0.20 microg/g wet wt, respectively). Finally, comparison of experimental gill Zn accumulation, with accumulation predicted by the biotic ligand model, demonstrated that model output reflected short-term (<1 h) experimental gill Zn accumulation and predicted observed differences in accumulation between hard and soft water rainbow trout gills. Our results indicate that measurable differences exist in short-term gill Zn accumulation following acclimation and exposure in different water hardnesses and that short-term Zn accumulation appears to be predictive of Zn acute toxicity thresholds (96-h LC50s).