The precipitation of indium at elevated pH in a stream influenced by acid mine drainage.

Indium is an increasingly important metal in semiconductors and electronics and has uses in important energy technologies such as photovoltaic cells and light-emitting diodes (LEDs). One significant flux of indium to the environment is from lead, zinc, copper, and tin mining and smelting, but little is known about its aqueous behavior after it is mobilized. In this study, we use Mineral Creek, a headwater stream in southwestern Colorado severely affected by heavy metal contamination as a result of acid mine drainage, as a natural laboratory to study the aqueous behavior of indium. At the existing pH of ~3, indium concentrations are 6-29µg/L (10,000× those found in natural rivers), and are completely filterable through a 0.45µm filter. During a pH modification experiment, the pH of the system was raised to >8, and >99% of the indium became associated with the suspended solid phase (i.e. does not pass through a 0.45µm filter). To determine the mechanism of removal of indium from the filterable and likely primarily dissolved phase, we conducted laboratory experiments to determine an upper bound for a sorption constant to iron oxides, and used this, along with other published thermodynamic constants, to model the partitioning of indium in Mineral Creek. Modeling results suggest that the removal of indium from the filterable phase is consistent with precipitation of indium hydroxide from a dissolved phase. This work demonstrates that nonferrous mining processes can be a significant source of indium to the environment, and provides critical information about the aqueous behavior of indium.

Exposure Potential and Health Impacts of Indium and Gallium, Metals Critical to Emerging Electronics and Energy Technologies.

The rapid growth of new electronics and energy technologies requires the use of rare elements of the periodic table. For many of these elements, little is known about their environmental behavior or human health impacts. This is true for indium and gallium, two technology critical elements. Increased environmental concentrations of both indium and gallium create the potential for increased environmental exposure, though little is known about the extent of this exposure. Evidence is mounting that indium and gallium can have substantial toxicity, including in occupational settings where indium lung disease has been recognized as a potentially fatal disease caused by the inhalation of indium particles. This paper aims to review the basic chemistry, changing environmental concentrations, potential for human exposure, and known health effects of indium and gallium.

Statistical evaluation of biogeochemical variables affecting spatiotemporal distributions of multiple free metal ion concentrations in an urban estuary.

Free metal ion concentrations have been recognized as a better indicator of metal bioavailability in aquatic environments than total dissolved metal concentrations. However, our understanding of the determinants of free ion concentrations, especially in a metal mixture, is limited, due to underexplored techniques for measuring multiple free metal ions simultaneously. In this work, we performed statistical analyses on a large dataset containing repeated measurements of free ion concentrations of Cu, Zn, Pb, Ni, and Cd, the most commonly measured metals in seawater, at five inshore locations in Boston Harbor, previously collected using an in-situ equilibrium-based multi-metal free ion sampler, the 'Gellyfish'. We examined correlations among these five metals by season, and evaluated effects of 10 biogeochemical variables on free ion concentrations over time and location through multivariate regressions. We also explored potential clustering among the five metals through a principal component analysis. We found significant correlations among metals, with varying patterns over season. Our regression results suggest that instead of dissolved metals, pH, salinity, temperature and rainfall were the most significant determinants of free metal ion concentrations. For example, a one-unit decrease in pH was associated with a 2.2 (Cd) to 99 (Cu) times increase in free ion concentrations. This work is among the first to reveal key contributors to spatiotemporal variations in free ion concentrations, and demonstrated the usefulness of the Gellyfish sampler in routine sampling of free ions within metal mixtures and in generating data for statistical analyses.

Associations between metals in residential environmental media and exposure biomarkers over time in infants living near a mining-impacted site.

Infant exposures to metals are a concern for mining-impacted communities, although limited information is available to assess residential exposures over the first year of life. We measured lead (Pb), manganese, arsenic, and cadmium in indoor air, house dust, yard soil, and tap water from 53 infants' homes near the Tar Creek Superfund Site (Oklahoma, USA) at two time points representing developmental stages before and during initial ambulation (age 0-6 and 6-12 months). We measured infant metal biomarkers in: umbilical cord blood (n=53); 12- (n=43) and 24- (n=22) month blood; and hair at age 12 months (n=39). We evaluated cross-sectional and longitudinal associations between infant residential and biomarker concentrations. A doubling of mean dust Pb concentration was consistently associated with 36-49% higher 12-month blood Pb adjusting for cord blood Pb (P⩽0.05). Adjusted dust concentration explained 29-35% of blood Pb variance, and consistent associations with other media were not observed. Although concentrations in dust and blood were generally low, strong and consistent associations between dust and body burden suggest that house dust in mining-impacted communities may impact children's health. These relationships were observed at a young age, typically before blood Pb levels peak and when children's development may be particularly vulnerable to toxic insult.

The Gellyfish: An in situ equilibrium-based sampler for determining multiple free metal ion concentrations in marine ecosystems.

Free metal ions are usually the most bioavailable and toxic metal species to aquatic organisms, but they are difficult to measure because of their extremely low concentrations in the marine environment. Many of the current methods for determining free metal ions are complicated and time-consuming, and they can only measure 1 metal at a time. The authors developed a new version of the "Gellyfish," an in situ equilibrium-based sampler, with significantly reduced equilibration time and the capability of measuring multiple free metal ions simultaneously. By calibrating the Gellyfish to account for its uptake of cationic metal complexes and validating them in multi-metal competition experiments, the authors were able to determine free metal ion concentrations previously collected over 10 mo at 5 locations in Boston Harbor for Cu, Zn, Pb, Ni, and Cd. This generated 1 of the largest free metal ion datasets and demonstrated the applicability of the Gellyfish as an easy-to-use and inexpensive tool for monitoring free ion concentrations of metal mixtures in marine ecosystems.

A longitudinal study of mercury exposure associated with consumption of freshwater fish from a reservoir in rural south central USA.

Methylmercury (MeHg) exposure through fish consumption is a worldwide health concern. Saltwater fish account for most dietary MeHg exposure in the general U.S. population, but less is known about seasonal variations in MeHg exposure and fish consumption among millions of freshwater anglers. This longitudinal study examined associations between MeHg exposure and fish consumption in a rural, low-income population relying on a freshwater reservoir (Oklahoma, USA) for recreational and subsistence fishing. We interviewed 151 participants, primarily anglers and their families, seasonally for one year using 90-day recall food frequency questionnaires to assess general and species-specific fish consumption, and tested hair biomarker samples for total mercury (THg hair). Mean THg hair was 0.27 µg/g (n=595, range: 0.0044-3.1 µg/g), with 4% of participants above U.S. EPA's guideline for women of childbearing age and children. Mean fish consumption was 58 g/d (95% CI: 49-67 g/d), within the range previously reported for recreational freshwater anglers and above the national average. Unlike the general U.S. population, freshwater species contributed the majority of fish consumption (69%) and dietary Hg exposure (60%) among participants, despite relatively low THg in local fish. THg hair increased with fish consumption, age, and education, and was higher among male participants and the lowest in winter. Our results suggest that future studies of anglers should consider seasonality in fish consumption and MeHg exposure and include household members who share their catch. Efforts to evaluate benefits of reducing Hg emissions should consider dietary patterns among consumers of fish from local freshwater bodies.

Contaminated turmeric is a potential source of lead exposure for children in rural Bangladesh.

BACKGROUND: During the conduct of a cohort study intended to study the associations between mixed metal exposures and child health outcomes, we found that 78% of 309 children aged 20-40 months evaluated in the Munshiganj District of Bangladesh had blood lead concentrations ≥5 µg/dL and 27% had concentrations ≥10 µg/dL. HYPOTHESIS: Environmental sources such as spices (e.g., turmeric, which has already faced recalls in Bangladesh due to high lead levels) may be a potential route of lead exposure. METHODS: We conducted visits to the homes of 28 children randomly selected from among high and low blood lead concentration groups. During the visits, we administered a structured questionnaire and obtained soil, dust, rice, and spice samples. We obtained water samples from community water sources, as well as environmental samples from neighborhood businesses. RESULTS: Lead concentrations in many turmeric samples were elevated, with lead concentrations as high as 483 ppm. Analyses showed high bioaccessibility of lead. CONCLUSIONS: Contamination of turmeric powder is a potentially important source of lead exposure in this population.

Assessing sources of human methylmercury exposure using stable mercury isotopes.

Seafood consumption is the primary route of methylmercury (MeHg) exposure for most populations. Inherent uncertainties in dietary survey data point to the need for an empirical tool to confirm exposure sources. We therefore explore the utility of Hg stable isotope ratios in human hair as a new method for discerning MeHg exposure sources. We characterized Hg isotope fractionation between humans and their diets using hair samples from Faroese whalers exposed to MeHg predominantly from pilot whales. We observed an increase of 1.75‰ in δ(202)Hg values between pilot whale muscle tissue and Faroese whalers' hair but no mass-independent fractionation. We found a similar offset in δ(202)Hg between consumed seafood and hair samples from Gulf of Mexico recreational anglers who are exposed to lower levels of MeHg from a variety of seafood sources. An isotope mixing model was used to estimate individual MeHg exposure sources and confirmed that both Δ(199)Hg and δ(202)Hg values in human hair can help identify dietary MeHg sources. Variability in isotopic signatures among coastal fish consumers in the Gulf of Mexico likely reflects both differences in environmental sources of MeHg to coastal fish and uncertainty in dietary recall data. Additional data are needed to fully refine this approach for individuals with complex seafood consumption patterns.

Sources and fates of heavy metals in a mining-impacted stream: temporal variability and the role of iron oxides.

Heavy metal contamination of surface waters at mining sites often involves complex interactions of multiple sources and varying biogeochemical conditions. We compared surface and subsurface metal loading from mine waste pile runoff and mine drainage discharge and characterized the influence of iron oxides on metal fate along a 0.9-km stretch of Tar Creek (Oklahoma, USA), which drains an abandoned Zn/Pb mining area. The importance of each source varied by metal; mine waste pile runoff contributed 70% of Cd, while mine drainage contributed 90% of Pb, and both sources contributed similarly to Zn loading. Subsurface inputs accounted for 40% of flow and 40-70% of metal loading along this stretch. Streambed iron oxide aggregate material contained highly elevated Zn (up to 27,000 µg g(-1)), Pb (up to 550 µg g(-1)) and Cd (up to 200 µg g(-1)) and was characterized as a heterogeneous mixture of iron oxides, fine-grain mine waste, and organic material. Sequential extractions confirmed preferential sequestration of Pb by iron oxides, as well as substantial concentrations of Zn and Cd in iron oxide fractions, with additional accumulation of Zn, Pb, and Cd during downstream transport. Comparisons with historical data show that while metal concentrations in mine drainage have decreased by more than an order of magnitude in recent decades, the chemical composition of mine waste pile runoff has remained relatively constant, indicating less attenuation and increased relative importance of pile runoff. These results highlight the importance of monitoring temporal changes at contaminated sites associated with evolving speciation and simultaneously addressing surface and subsurface contamination from both mine waste piles and mine drainage.

Benchscale Assessment of the Efficacy of a Reactive Core Mat to Isolate PAH-spiked Aquatic Sediments.

This paper describes the results of a benchscale testing program to assess the efficacy of a reactive core mat (RCM) for short term isolation and partial remediation of contaminated, subaqueous sediments. The 1.25 cm thick RCM (with a core reactive material such as organoclay with filtering layers on top and bottom) is placed on the sediment, and approximately 7.5 - 10 cm of overlying soil is placed on the RCM for stability and protection. A set of experiments were conducted to measure the sorption characteristics of the mat core (organoclay) and sediment used in the experiments, and to determine the fate of semi-volatile organic contaminants and non-reactive tracers through the sediment and reactive mat. The experimental study was conducted on naphthalene-spiked Neponset River (Milton, MA) sediment. The results show nonlinear sorption behavior for organoclay, with sorption capacity increasing with increasing naphthalene concentration. Neponset River sediment showed a notably high sorption capacity, likely due to the relatively high organic carbon fraction (14%). The fate and transport experiments demonstrated the short term efficiency of the reactive mat to capture the contamination that is associated with the post-capping period during which the highest consolidation-induced advective flux occurs, driving solid particles, pore fluid and soluble contaminants toward the reactive mat. The goal of the mat placement is to provide a physical filtering and chemically reactive layer to isolate contamination from the overlying water column. An important finding is that because of the high sorption capacity of the Neponset River sediment, the physical filtering capability of the mat is as critical as its chemical reactive capacity.

Bioavailability of hydrophobic organic compounds in thin-layered capped sediments.

The effect of a thin sand capping layer (7.5 cm) on the bioavailability of hydrophobic organic compounds (HOCs, i.e., PCBs and naphthalene) was studied using oligochaete worms, and the results compared to previously obtained bioavailability tests with a reactive core mat (RCM) cap. The study investigated the difference in HOC concentration in worms exposed to: (a) a grab sample of sediment used as sampled for PCBs and spiked for PAHs; (b) an initially clean mixture of sand and organic matter (biouptake layer) directly overlying the sediment; and (c) the biouptake layer placed on top of the RCM-capped sediment. Benchscale experiments were performed to induce pore fluid flux through the sediment and into the overlying layer(s). Principal component analysis (PCA) was used to assess PCB homolog group concentrations. Results indicate that the thin sand cap alone reduced the average bioavailability of PCBs by a factor of 100 compared to direct exposure, but had no effect on the bioavailability of naphthalene. However, worms exposed to the RCM-protected biouptake layer show virtually the same HOC concentrations as those in the background worm samples, indicating effective isolation by the RCM.

Passive sampling methods for contaminated sediments: risk assessment and management.

This paper details how activity-based passive sampling methods (PSMs), which provide information on bioavailability in terms of freely dissolved contaminant concentrations (Cfree ), can be used to better inform risk management decision making at multiple points in the process of assessing and managing contaminated sediment sites. PSMs can increase certainty in site investigation and management, because Cfree is a better predictor of bioavailability than total bulk sediment concentration (Ctotal ) for 4 key endpoints included in conceptual site models (benthic organism toxicity, bioaccumulation, sediment flux, and water column exposures). The use of passive sampling devices (PSDs) presents challenges with respect to representative sampling for estimating average concentrations and other metrics relevant for exposure and risk assessment. These challenges can be addressed by designing studies that account for sources of variation associated with PSMs and considering appropriate spatial scales to meet study objectives. Possible applications of PSMs include: quantifying spatial and temporal trends in bioavailable contaminants, identifying and evaluating contaminant source contributions, calibrating site-specific models, and, improving weight-of-evidence based decision frameworks. PSM data can be used to assist in delineating sediment management zones based on likelihood of exposure effects, monitor remedy effectiveness, and, evaluate risk reduction after sediment treatment, disposal, or beneficial reuse after management actions. Examples are provided illustrating why PSMs and freely dissolved contaminant concentrations (Cfree ) should be incorporated into contaminated sediment investigations and study designs to better focus on and understand contaminant bioavailability, more accurately estimate exposure to sediment-associated contaminants, and better inform risk management decisions. Research and communication needs for encouraging broader use are discussed.

Mineralogy affects geoavailability, bioaccessibility and bioavailability of zinc.

We correlated mineralogical and particle characteristics of Zn-containing particles with Zn geoavailability, bioaccessibility, and bioavailability following gavage and intranasal (IN) administration in rats. We compared samples of Zn/Pb mine waste and five pulverized pure-phase Zn minerals (<38 µm). Particles were neutron-activated to produce radioactive (65)Zn. We assessed geoavailability using sequential extractions and bioaccessibility using in vitro extraction tests simulating various pH and biological conditions. Zn in vivo bioavailability and in vitro bioaccessibility decreased as follows: mine waste > hydrozincite > hemimorphite > zincite ≈ smithsonite >> sphalerite. We found significant correlations among geoavailability, bioaccessibility and bioavailability. In particular, Zn bioavailability post-gavage and post-IN was significantly correlated with bioaccessibility in simulated phagolysosomal fluid and gastric fluid. These data indicate that solid phase speciation influences biological uptake of Zn and that in vitro tests can be used to predict Zn bioavailability in exposure assessment and effective remediation design.

Prioritizing environmental risk of prescription pharmaceuticals.

Low levels of pharmaceutical compounds have been detected in aquatic environments worldwide, but their human and ecological health risks associated with low dose environmental exposure is largely unknown due to the large number of these compounds and a lack of information. Therefore prioritization and ranking methods are needed for screening target compounds for research and risk assessment. Previous efforts to rank pharmaceutical compounds have often focused on occurrence data and have paid less attention to removal mechanisms such as human metabolism. This study proposes a simple prioritization approach based on number of prescriptions and toxicity information, accounting for metabolism and wastewater treatment removal, and can be applied to unmeasured compounds. The approach was performed on the 200 most-prescribed drugs in the US in 2009. Our results showed that under-studied compounds such as levothyroxine and montelukast sodium received the highest scores, suggesting the importance of removal mechanisms in influencing the ranking, and the need for future environmental research to include other less-studied but potentially harmful pharmaceutical compounds.

Effect of reactive core mat application on bioavailability of hydrophobic organic compounds.

Sediment remediation techniques to limit the bioavailability of contaminants are of special interest due to related acute or chronic toxicities associated with sediment contaminants. Bioavailability in aquatic sediments can be particularly problematic due to their accessibility to food chain biota, and interactions with surface and ground water. The effect of a reactive core mat (RCM) containing organoclay on the bioavailability of hydrophobic organic compounds (HOCs) (i.e., PCBs and naphthalene) was studied using oligochaete worms (Lumbriculus variegatus). Sediment sampled from the Neponset River (Milton, MA) with 10 ppm background PCB contamination was used in the experimental study. The objective of this study is to investigate the difference in HOC concentration of worms exposed to: a) a grab sample of contaminated sediment (10.4% total organic carbon); and b) an initially clean mixture of sand and organic matter (the so-called biouptake layer), placed on top of the RCM-capped sediment during consolidation coupled solute transport experiments. In addition to the experimental data, the U.S. Army Corps of Engineers (USACE) biota-sediment accumulation factor (BSAF) database was validated and used to model biouptake of contaminants for certain cases. Results indicate that RCM capping reduced the average bioavailability of both PCBs and naphthalene by a factor of about 50. In fact, worms exposed to the RCM-protected biouptake layer show virtually the same HOC concentrations as those measured in the control worm samples.

Co-leaching of brominated compounds and antimony from bottled water.

A fast-growing bottled water market is occasionally challenged by reports calling for contaminant leaching from water-contact materials (plastics). Our focus was on leaching of antimony (Sb) and brominated compounds expressed by total soluble bromine (Br) measurements, including those of polybrominated diphenyl ethers (PBDE). Studies are lacking on concomitant leaching of two or more inorganic plastic constituents from the same bottle. A market-representative basket survey of bottled water was initiated in Boston, USA supermarkets. Bottled water classes sampled were: i) non-carbonated (NCR), ii) carbonated (CR), and iii) non-carbonated and enriched (NCRE). Plastic bottle materials sampled were: polyethylene terephthalate (PET), high-density polyethylene (HDPE), polystyrene (PS), and polycarbonate (PC). Storage conditions for the 31 bottled water samples were: 23°C temperature, no-shaking and 12h/12h light/dark for 60days of equilibration. Average Br and Sb concentrations after 60-days of storage followed the order of NCR

Incorporating contaminant bioavailability into sediment quality assessment frameworks.

The recently adopted sediment quality assessment framework for evaluating bay and estuarine sediments in the state of California incorporates bulk sediment chemistry as a key line of evidence (LOE) but does not address the bioavailability of measured contaminants. Thus, the chemistry-based LOE likely does not provide an accurate depiction of organism exposure in all cases, nor is it particularly well suited for assessment of causality. In recent years, several methods for evaluating the bioavailability of sediment-associated contaminants have emerged, which, if optimized and validated, could be applied to improve the applicability and broaden the scope of sediment quality assessment. Such methods include equilibrium-based biomimetic extractions using either passive sampling devices (PSDs) or measures of rapidly desorbing contaminant pools, which provide information compatible with existing mechanistic approaches. Currently, these methods show promise in relating bioaccessible chemicals to effects endpoints, including bioaccumulation of hydrophobic organic compounds and/or toxicity due to metals. Using these methods, a bioavailability LOE for organics is proposed based on PSD and equilibrium partitioning theory that can be employed as an independent LOE or in assessing causality in tiered toxicity identification evaluations. Current and future research should be aimed at comparing the performance of PSDs and their relationships with effects concentrations, field validation of the most promising methods, addressing contaminant mixtures, further developing the parameterization of the proposed bioavailability LOE, and providing a better understanding of the underlying diagenetic cycling of metal contaminants that lead to exposure, affect bioavailability, and drive adverse outcomes.

Frequency of use controls chemical leaching from drinking-water containers subject to disinfection.

Microbial-, and chemical-based burden of disease associated with lack of access to safe water continues to primarily impact developing countries. Cost-effective health risk-mitigating measures, such as of solar disinfection applied to microbial-contaminated water stored in plastic bottles have been increasingly tested in developing countries adversely impacted by epidemic water-borne diseases. Public health concerns associated with chemical leaching from water packaging materials led us to investigate the magnitude and variability of antimony (Sb) and bromine (Br) leaching from reused plastic containers (polyethylene terephthalate, PET; and polycarbonate, PC) subject to UV and/or temperature-driven disinfection. The overall objective of this study was to determine the main and interactive effects of temperature, UV exposure duration, and frequency of bottle reuse on the extent of leaching of Sb and Br from plastic bottles into water. Regardless of UV exposure duration, frequency of reuse (up to 27 times) was the major factor that linearly increased Sb leaching from PET bottles at all temperatures tested (13-47 °C). Leached Sb concentrations (∼360 ng L(-1)) from the highly reused (27 times) PET bottles (minimal Sb leaching from PC bottles, <15 ng L(-1)) did not pose a serious risk to human health according to current daily Sb acceptable intake estimates. Leached Br concentrations from both PET and PC containers (up to ∼15 µg L(-1)) did not pose a consumer health risk either, however, no acceptable daily dose estimates exist for oral ingestion of organo-brominated, or other plasticizers/additives compounds if they were to be found in bottled water at much lower concentrations. Additional research on potential leaching of organic chemicals from water packaging materials is deemed necessary under relevant environmental conditions.

Metal sources and exposures in the homes of young children living near a mining-impacted Superfund site.

Children living near hazardous waste sites may be exposed to environmental contaminants, yet few studies have conducted multi-media exposure assessments, including residential environments where children spend most of their time. We sampled yard soil, house dust, and particulate matter with aerodynamic diameter <2.5 in 59 homes of young children near an abandoned mining area and analyzed samples for lead (Pb), zinc (Zn), cadmium (Cd), arsenic (As), and manganese (Mn). In over half of the homes, dust concentrations of Pb, Zn, Cd, and As were higher than those in soil. Proximity to mine waste (chat) piles and the presence of chat in the driveway significantly predicted dust metals levels. Homes with both chat sources had Pb, Zn, Cd, and As dust levels two to three times higher than homes with no known chat sources after controlling for other sources. In contrast, Mn concentrations in dust were consistently lower than in soil and were not associated with chat sources. Mn dust concentrations were predicted by soil concentrations and occupant density. These findings suggest that nearby outdoor sources of metal contaminants from mine waste may migrate indoors. Populations farther away from the mining site may also be exposed if secondary uses of chat are in close proximity to the home.

Temporal increase in organic mercury in an endangered pelagic seabird assessed by century-old museum specimens.

Methylmercury cycling in the Pacific Ocean has garnered significant attention in recent years, especially with regard to rising mercury emissions from Asia. Uncertainty exists concerning whether increases in anthropogenic emissions over time may have caused increased mercury bioaccumulation in the biota. To address this, we measured total mercury and, for a subset of samples, methylmercury (the bioaccumulated form of mercury) in museum feathers from an endangered seabird, the black-footed albatross (Phoebastria nigripes), spanning a 120-y period. We analyzed stable isotopes of nitrogen (δ(15)N) and carbon (δ(13)C) to control for temporal changes in trophic structure and diet. In post-1940 and -1990 feathers, we detected significantly higher mean methylmercury concentrations and higher proportions of samples exhibiting above deleterious threshold levels (∼ 40,000 ng · g(-1)) of methylmercury relative to prior time points, suggesting that mercury toxicity may undermine reproductive effort in the species. We also found higher levels of (presumably curator-mediated) inorganic mercury in older specimens of albatross as well as two nonpelagic species lacking historical exposure to bioavailable mercury, patterns suggesting that studies on bioaccumulation should measure methylmercury rather than total mercury when using museum collections. δ(15)N contributed substantially to models explaining the observed methylmercury variation. After simultaneously controlling for significant trends in δ(13)C over time and δ(15)N with methylmercury exposure, year remained a significant independent covariate with feather methylmercury levels among the albatrosses. These data show that remote seabird colonies in the Pacific basin exhibit temporal changes in methylmercury levels consistent with historical global and recent regional increases in anthropogenic emissions.