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Stability of inorganic and methylated arsenic species in laboratory standards, surface water and groundwater under three different preservation regimes

Geogenic arsenic (As) adversely affects drinking water quality in geologically diverse aquifers across the globe. Although the species of As significantly affects its fate, transport, toxicity, and As treatment technology efficacy, reported effectiveness of As species preservation methods varies widely with preservation methods and natural water geochemistry. Our study 1) evaluates the shelf life of As(III), As(V), dimethylarsinate (DMA), and monomethylarsonate (MMA) in standards prepared with ultrapure water; 2) establishes a hold time for these As species in low-iron (Fe) groundwater and surface water samples preserved with a concentration of EDTA that exceeded the sum of the molar concentrations of Al, Fe, Mn, Ca, Mg, and Sr (molar excess of EDTA); and 3) evaluates As(III) species stability in groundwater samples with detectable SO 4 and up to 6.5 mg/L Fe concentrations preserved in 3 ways: less than molar excess EDTA, molar excess EDTA, and Vacuette® tubes with an unknown (proprietary) amount of EDTA. Arsenic species standards prepared with 2.5 mM EDTA in ultrapure water and stored at 4 °C had a shelf life of at least 180 days. As(III) was stable for at least 15 days and DMA and MMA were stable for at least 90 days in environmental samples with Fe less than 1 mg/L that were preserved with a molar excess of EDTA and stored in opaque containers at 4 °C. As(III) species were not stable for any holding time in samples with Fe greater than 1 mg/L and detectable SO 4 when preserved with a molar excess of EDTA and stored in white high density polyethylene bottles at room temperature, or when preserved by storage in EDTA containing Vacuette® tubes at 4 °C. For geochemical or water quality studies where the distribution of As(III) and As(V) is a critical factor, an understanding of the sample chemistry, rapid As speciation analysis after sample collection, and collecting a field spike with the sample can be helpful for collecting accurate inorganic As species data.

Applied Geochemistry↗

The feasibility of well-logging measurements of arsenic levels using neutron-activation analysis

Arsenic is an extremely toxic metal, which poses a significant problem in many mining environments. Arsenic contamination is also a major problem in ground and surface waters. A feasibility study was conducted to determine if neutron-activation analysis is a practical method of measuring in situ arsenic levels. The response of hypothetical well-logging tools to arsenic was simulated using a readily available Monte Carlo simulation code (MCNP). Simulations were made for probes with both hyperpure germanium (HPGe) and bismuth germanate (BGO) detectors using accelerator and isotopic neutron sources. Both sources produce similar results; however, the BGO detector is much more susceptible to spectral interference than the HPGe detector. Spectral interference from copper can preclude low-level arsenic measurements when using the BGO detector. Results show that a borehole probe could be built that would measure arsenic concentrations of 100 ppm by weight to an uncertainty of 50 ppm in about 15 min. ?? 2006 Elsevier Ltd. All rights reserved.

Applied Radiation and Isotopes↗

Contaminants as viral cofactors: assessing indirect population effects

Current toxicological methods often miss contaminant effects, particularly when immune suppression is involved. The failure to recognize and evaluate indirect and sublethal effects severely limits the applicability of those methods at the population level. In this study, the Vitality model is used to evaluate the population level effects of a contaminant exerting only indirect, sublethal effects at the individual level. Juvenile rainbow trout ( Oncorhynchus mykiss ) were injected with 2.5 or 10.0 mg/kg doses of the model CYP1A inducer, β-naphthoflavone (BNF) as a pre-stressor, then exposed to a challenge dose of 10 2 or 10 4 pfu/fish of infectious hematopoietic necrosis virus (IHNV), an important viral pathogen of salmonids in North America. At the end of the 28-d challenge, the mortality data were processed according to the Vitality model which indicated that the correlation between the average rate of vitality loss and the pre-stressor dose was strong: R 2 = 0.9944. Average time to death and cumulative mortality were dependent on the BNF dose, while no significant difference between the two viral dosages was shown, implying that the history of the organism at the time of stressor exposure is an important factor in determining the virulence or toxicity of the stressor. The conceptual framework of this model permits a smoother transfer of results to a more complex stratum, namely the population level, which allows the immunosuppressive results generated by doses of a CYP1A inducer that more accurately represent the effects elicited by environmentally-relevant contaminant concentrations to be extrapolated to target populations. The indirect effects of other environmental contaminants with similar biotransformation pathways, such as polycyclic aromatic hydrocarbons (PAH), could be assessed and quantified with this model and the results applied to a more complex biological hierarchy.

Aquatic Toxicology↗

The effect of chronic chromium exposure on the health of Chinook salmon (Oncorhynchus tshawytscha)

This study was designed to determine fish health impairment of Chinook salmon ( Oncorhynchus tshawytscha ) exposed to chromium. Juvenile Chinook salmon were exposed to aqueous chromium concentrations (0–266 μg l −1 ) that have been documented in porewater from bottom sediments and in well waters near salmon spawning areas in the Columbia River in the northwestern United States. After Chinook salmon parr were exposed to 24 and 54 μg Cr l −1 for 105 days, neither growth nor survival of parr was affected. On day 105, concentrations were increased from 24 to 120 μg Cr l −1 and from 54 to 266 μg Cr l −1 until the end of the experiment on day 134. Weight of parr was decreased in the 24/120 μg Cr l −1 treatment, and survival was decreased in the 54/266 μg Cr l −1 treatment. Fish health was significantly impaired in both the 24/120 and 54/266 μg Cr l −1 treatments. The kidney is the target organ during chromium exposures through the water column. The kidneys of fish exposed to the greatest concentrations of chromium had gross and microscopic lesions (e.g. necrosis of cells lining kidney tububules) and products of lipid peroxidation were elevated. These changes were associated with elevated concentrations of chromium in the kidney, and reduced growth and survival. Also, variations in DNA in the blood were associated with pathological changes in the kidney and spleen. These changes suggest that chromium accumulates and enters the lipid peroxidation pathway where fatty acid damage and DNA damage (expressed as chromosome changes) occur to cause cell death and tissue damage. While most of the physiological malfunctions occurred following parr exposures to concentrations ≥120 μg Cr l −1 , nuclear DNA damage followed exposures to 24 μg Cr l −1 , which was the smallest concentration tested. The abnormalities measured during this study are particularly important because they are associated with impaired growth and reduced survival at concentrations ≥120 μg Cr l −1 . Therefore, these changes can be used to investigate the health of resident fish in natural waters with high chromium concentrations as well as provide insight into the mechanisms of chromium toxicity.

Aquatic Toxicology↗

Determining metal assimilation efficiency in aquatic invertebrates using enriched stable metal isotope tracers

We employ a novel approach that combines pulse-chase feeding and multi-labelled stable isotopes to determine gut passage time (GPT), gut retention time (GRT), food ingestion rate (IR) and assimilation efficiency (AE) of three trace elements for a freshwater gastropod. Lettuce isotopically enriched in 53 Cr, 65 Cu and 106 Cd was fed for 2 h to Lymnaea stagnalis . The release of tracers in feces and water was monitored for 48 h, during which unlabelled lettuce was provided ad libidum . The first defecation of 53 Cr occurred after 5 h of depuration (GPT), whereas 90% of the ingested 53 Cr was recovered in the feces after 22.5 h of depuration (GRT). 53 Chromium was not significantly accumulated in the soft tissues upon exposure. In contrast, 65 Cu and 106 Cd assimilation was detectable for most experimental snails, i.e., 65/63 Cu and 106/114 Cd ratios in exposed snails were higher than those for controls. Food IR during the labelled feeding phase was 0.16 ± 0.07 g g −1 d −1 . IR was inferred from the amount of 53 Cr egested in the feces during depuration and the concentration of 53 Cr in the labelled lettuce. Assimilation efficiencies (±95% CI) determined using mass balance calculations were 84 ± 4% for Cu and 85 ± 3% for Cd. The ratio method yields similar AE estimates. Expanding the application of this novel stable isotope tracer technique to other metals in a wide variety of species will provide unique opportunities to evaluate the interplay between digestive processes and dietary influx of metals. Understanding the biological processes that modulate dietborne metal uptake is crucial to assess the toxicity of dietborne metals.

Aquatic Toxicology↗

Impairment of the reproductive potential of male fathead minnows by environmentally relevant exposures to 4-nonylphenolf

The synthetic organic compound 4-nonylphenol (NP) has been detected in many human-impacted surface waters in North America. In this study, we examined the ability of NP to alter reproductive competence in male fathead minnows after a 28 day flow-through exposure in a range of environmentally relevant concentrations bracketing the U.S. Environmental Protection Agency toxicity-based NP chronic exposure criterion of 6.1 μg NP/L. Exposure to NP at and above the EPA chronic exposure criterion resulted in an induction of plasma vitellogenin (VTG) within 14 days. However, 7 days after the cessation of exposure, VTG concentrations had dropped more than 50% and few males expressed VTG above the detection threshold. All of the morphological endpoints, including gonadosomatic index, hepatosomatic index, secondary sexual characters, and histopathology, were unaltered by all NP treatments. However, when NP-exposed male fish were allowed to compete with control males for access to nest sites and females, most treatments altered the reproductive competence of exposed males. At lower NP concentrations, exposed males out-competed control males, possibly by being primed through the estrogenic NP exposure in a fashion similar to priming by pheromones released from female fathead minnows. At higher NP exposure concentrations, this priming effect was negated by the adverse effects of the exposure and control males out-competed treated males. Results of this study indicate the complexity of endocrine disrupting effects and the need for multiple analysis levels to assess the effects of these compounds on aquatic organisms.

Aquatic Toxicology↗

Sublethal red tide toxin exposure in free-ranging manatees (Trichechus manatus) affects the immune system through reduced lymphocyte proliferation responses, inflammation, and oxidative stress

The health of many Florida manatees (Trichechus manatus latirostris) is adversely affected by exposure to blooms of the toxic dinoflagellate, Karenia brevis. K. brevis blooms are common in manatee habitats of Florida's southwestern coast and produce a group of cyclic polyether toxins collectively referred to as red tide toxins, or brevetoxins. Although a large number of manatees exposed to significant levels of red tide toxins die, several manatees are rescued from sublethal exposure and are successfully treated and returned to the wild. Sublethal brevetoxin exposure may potentially impact the manatee immune system. Lymphocyte proliferative responses and a suite of immune function parameters in the plasma were used to evaluate effects of brevetoxin exposure on health of manatees rescued from natural exposure to red tide toxins in their habitat. Blood samples were collected from rescued manatees at Lowry Park Zoo in Tampa, FL and from healthy, unexposed manatees in Crystal River, FL. Peripheral blood leukocytes (PBL) isolated from whole blood were stimulated with T-cell mitogens, ConA and PHA. A suite of plasma parameters, including plasma protein electrophoresis profiles, lysozyme activity, superoxide dismutase (SOD) activity, and reactive oxygen/nitrogen (ROS/RNS) species, was also used to assess manatee health. Significant decreases (p<0.05) in lymphocyte proliferation were observed in ConA and PHA stimulated lymphocytes from rescued animals compared to non-exposed animals. Significant correlations were observed between oxidative stress markers (SOD, ROS/RNS) and plasma brevetoxin concentrations. Sublethal exposure to brevetoxins in the wild impacts some immune function components, and thus, overall health, in the Florida manatee.

Florida↗

Biodynamics of copper oxide nanoparticles and copper ions in an oligochaete - Part II: Subcellular distribution following sediment exposure

The use and likely incidental release of metal nanoparticles (NPs) is steadily increasing. Despite the increasing amount of published literature on metal NP toxicity in the aquatic environment, very little is known about the biological fate of NPs after sediment exposures. Here, we compare the bioavailability and subcellular distribution of copper oxide (CuO) NPs and aqueous Cu (Cu-Aq) in the sediment-dwelling worm Lumbriculus variegatus. Ten days (d) sediment exposure resulted in marginal Cu bioaccumulation in L. variegatus for both forms of Cu. Bioaccumulation was detected because isotopically enriched 65 Cu was used as a tracer. Neither burrowing behavior or survival was affected by the exposure. Once incorporated into tissue, Cu loss was negligible over 10 d of elimination in clean sediment (Cu elimination rate constants were not different from zero). With the exception of day 10, differences in bioaccumulation and subcellular distribution between Cu forms were either not detectable or marginal. After 10 d of exposure to Cu-Aq, the accumulated Cu was primarily partitioned in the subcellular fraction containing metallothionein-like proteins (MTLP, ≈40%) and cellular debris (CD, ≈30%). Cu concentrations in these fractions were significantly higher than in controls. For worms exposed to CuO NPs for 10 d, most of the accumulated Cu was partitioned in the CD fraction (≈40%), which was the only subcellular fraction where the Cu concentration was significantly higher than for the control group. Our results indicate that L. variegatus handle the two Cu forms differently. However, longer-term exposures are suggested in order to clearly highlight differences in the subcellular distribution of these two Cu forms.

Aquatic Toxicology↗

Exposure to Deepwater Horizon crude oil increases free cholesterol in larval red drum (Sciaenops ocellatus)

The 2010 Deepwater Horizon oil spill impacted over 2100 km of shoreline along the northern Gulf of Mexico, which coincided with the spawning season of many coastal species, including red drum ( Sciaenops ocellatus ). Red drum develop rapidly and are sensitive to crude oil exposure during the embryonic and larval periods. This study investigates the predictions from recent transcriptomic studies that cholesterol biosynthetic processes are impacted by oil exposure in fish early life stages. We found that red drum larvae exposed for 72-hours to ΣPAH 50 3.55 - 15.45 µg L −1 exhibited significantly increased pericardial area, a cardiotoxicity metric, but the expression of several genes targeted in the cholesterol synthesis pathway was not affected. However, whole-mount staining revealed significant increases in free cholesterol throughout the larval body (ΣPAH 50 4.71 – 16.15 µg L −1 ), and total cholesterol followed an increasing trend (ΣPAH 50 3.55 - 15.45 µg L −1 ). Cholesterol plays a critical role in fish embryo development and ion channel function. Therefore, the disruption of cholesterol homeostasis, as observed here, could play a role in the oil toxicity phenotype observed across many fish species.

Aquatic Toxicology↗

Influence of cardiotoxicity on visual function in developing zebrafish ( Danio rerio ) exposed to Deepwater Horizon crude oil

Polycyclic aromatic hydrocarbons (PAHs) are toxic constituents of crude oil that can induce cardiac dysfunction and vision impairment in early life stage (ELS) fishes. However, it is currently unknown whether visual impairments are independent effects or if they result from underlying PAH cardiotoxicity. To better understand this mechanism, microinjection of microRNA 133b (miR133b) was used to impair cardiac development in ELS zebrafish (injected at <1.25 hpf). Vision and cardiac endpoints were compared between miR133b-injected and oil-exposed zebrafish (4–72 hpf, 54.68–60.41 µg/L tPAH 50 ) to determine the influence of cardiac dysfunction and oil exposure on visual function. At 7 dpf, pericardial area and eye area were measured, and visual function was assessed by optokinetic response (OKR). Over 94 % of miR133b larvae and 45 % of oil-exposed larvae exhibited pericardial edema. Across treatments, there was a strong negative linear correlation between pericardial area and eye area ( r =-0.839, p < 0.0001). All miR133b larvae that exhibited pericardial edema and 18 % of the oil-exposed larvae that exhibited pericardial edema also exhibited reduced eye area (microphthalmia). In both the miR133b and oil groups, OKR was significantly reduced in larvae exhibiting pericardial edema ( p < 0.0001) and in larvae exhibiting reduced eye area ( p < 0.0001). A negative binomial generalized linear model (GLM) indicated that reduced eye area ( p < 0.0001), rather than pericardial edema ( p = 0.76), was a significant predictor of OKR. However, pericardial edema was strongly correlated with reduced eye area across treatments. These results suggest that visual effects may result from an interaction of cardiotoxicity as well as direct impacts to the visual system.

Aquatic Toxicology↗

PFAS exposure suppresses leaf litter decomposition in a stream ecosystem

Decomposition of organic matter is critical to the biogeochemical cycling of carbon and nutrients in all ecosystems. In streams, decomposition can be influenced by anthropogenic impacts, including contaminants. Per- and polyfluoroalkyl substances (PFAS) are resistant to degradation and widespread in freshwater ecosystems, yet little is known about their influence on organic matter processing in streams. We paired an observational field study of a PFAS-impacted stream via food processing wastewater with a 28-day laboratory experiment to investigate PFAS effects on leaf litter processing using multiple lines of evidence. Leaf litter decomposition rates and microbial respiration were significantly lower downstream of the PFAS point-source compared to the paired upstream site. We hypothesized that PFAS suppressed microbial activity thereby resulting in slower decomposition rates. To investigate further and better isolate PFAS, we dosed aquatic mesocosms containing leaf packs with differing concentrations of perfluorooctane sulfonate (PFOS). Over the 28-day incubation, decomposition rates did not differ, but we observed lower respiration rates on day 28 and higher dissolved organic carbon (DOC) in PFOS-dosed mesocosms, suggesting that PFAS may suppress microbial activity and inhibit carbon processing. These results underscore that concerns regarding PFAS contamination extend beyond organismal toxicity to ecosystem-level effects. Further research is needed to understand the scale, implications, and mechanisms responsible for these changes.

Upper Mississippi River Basin↗

Acid rain and its environmental effects: Recent scientific advances

The term ‘acid rain’ refers to atmospheric deposition of acidic constituents that impact the earth as rain, snow, particulates, gases, and vapor. Acid rain was first recognized by Ducros (1845) and subsequently described by the English chemist Robert Angus Smith (Smith, 1852) whose pioneering studies linked the sources to industrial emissions and included early observations of deleterious environmental effects (Smith, 1872). Smith's work was largely forgotten until the mid-20th century when observations began to link air pollution to the deposition of atmospheric sulfate (SO 4 2− ) and other chemical constituents, first near the metal smelter at Sudbury, Ontario, Canada, and later at locations in Europe, North America, and Australia (Gorham, 1961). Our modern understanding of acid rain as an environmental problem caused largely by regional emissions of sulfur dioxide (SO 2 ) and nitrogen oxides (NO x ) stems from observations in the 1960s and early 1970s in Sweden by Svante Odén (Odén, 1976), and in North America by Gene Likens and colleagues (Likens and Bormann, 1974). These scientists and many who followed showed the link to emissions from coal-fired power plants and other industrial sources, and documented the environmental effects of acid rain such as the acidification of surface waters and toxic effects on vegetation, fish, and other biota.

Atmospheric Environment↗

Metformin prevents endoplasmic reticulum stress-induced apoptosis through AMPK-PI3K-c-Jun NH2 pathway

Type 2 diabetes mellitus is thought to be partially associated with endoplasmic reticulum (ER) stress toxicity on pancreatic beta cells and the result of decreased insulin synthesis and secretion. In this study, we showed that a well-known insulin sensitizer, metformin, directly protects against dysfunction and death of ER stress-induced NIT-1 cells (a mouse pancreatic beta cell line) via AMP-activated protein kinase (AMPK) and phosphatidylinositol-3 (PI3) kinase activation. We also showed that exposure of NIT-1 cells to metformin (5mM) increases cellular resistance against ER stress-induced NIT-1 cell dysfunction and death. AMPK and PI3 kinase inhibitors abolished the effect of metformin on cell function and death. Metformin-mediated protective effects on ER stress-induced apoptosis were not a result of an unfolded protein response or the induced inhibitors of apoptotic proteins. In addition, we showed that exposure of ER stressed-induced NIT-1 cells to metformin decreases the phosphorylation of c-Jun NH(2) terminal kinase (JNK). These data suggest that metformin is an important determinant of ER stress-induced apoptosis in NIT-1 cells and may have implications for ER stress-mediated pancreatic beta cell destruction via regulation of the AMPK-PI3 kinase-JNK pathway.

Biochemical and Biophysical Research Communication↗

Anticoagulant rodenticides in Strix owls indicate widespread exposure in west coast forests

Exposure of nontarget wildlife to anticoagulant rodenticides (AR) is a global conservation concern typically centered around urban or agricultural areas. Recently, however, the illegal use of ARs in remote forests of California, USA, has exposed sensitive predators, including the federally threatened northern spotted owl ( Strix occidentalis caurina ). We used congeneric barred owls ( S. varia ) as a sentinel species to investigate whether ARs pose a threat to spotted owls and other old-forest wildlife in northern regions of the Pacific Northwest. We analyzed the liver tissue from 40 barred owls collected in Oregon and Washington and confirmed exposure to ≥1 AR compounds in 48% of the owls examined. Brodifacoum, an extremely toxic second-generation AR, was the most common compound detected (89% of positive cases), followed by bromadiolone (11%), difethialone (11%), and warfarin (5%). Brodifacoum was also detected in one barred owl and one spotted owl opportunistically found dead (liver concentrations were 0.091 and 0.049 µg/g, respectively). We found no evidence that exposure varied with proximity to developed and agricultural areas, or among different study areas, age-classes, and sexes. Rather, exposure was ubiquitous, and the rates we observed in our study (38 – 64%) were similar to or greater than that reported previously for barred owls in California (40%). Together these studies indicate widespread contamination in forested landscapes used by spotted owls and other wildlife of conservation concern. Owls collected in older forests may have been exposed via illegal use of ARs, highlighting a mounting challenge for land managers and policy makers.

California↗

Ammonia causes decreased brain monoamines in fathead minnows (Pimephales promelas)

Hyperammonemia, arising from variety of disorders, leads to severe neurological dysfunction. The mechanisms of ammonia toxicity in brain are not completely understood. This study investigated the effects of ammonia on monoaminergic systems in brains of fathead minnows (Pimephales promelas). Fish serve as a good model system to investigate hyperammonemic effects on brain function since no liver manipulations are necessary to increase endogenous ammonia concentrations. Using high performance liquid chromatography with electrochemical detection, monoamines and some associated metabolites were measured from whole brain homogenate. Adult males were exposed for 48 h to six different concentrations of ammonia (0.01–2.36 mg/l unionized) which bracketed the 96-h LC50 for this species. Ammonia concentration-dependent decreases were found for the catecholamines (norepinephrine and dopamine) and the indoleamine serotonin (5-HT). After an initial increase in the 5-HT precursor 5-hydroxytryptophan it too decreased with increasing ammonia concentrations. There were also significant increases in the 5-HIAA/5-HT and DOPAC/DA ratios, often used as measures of turnover. There were no changes in epinephrine (Epi) or monoamine catabolites (DOPAC, 5-HIAA) at any ammonia concentrations tested. Results suggest that ammonia causes decreased synthesis while also causing increased release and degradation. Increased release may underlie behavioral reactions to ammonia exposure in fish. This study adds weight to a growing body of evidence demonstrating that ammonia leads to dysfunctional monoaminergic systems in brain which may underlie neurological symptoms associated with human disorders such as hepatic encephalopathy.

Brain Research↗

Responses of hybrid striped bass to waterborne and dietary copper in freshwater and saltwater

Mechanisms of copper toxicity and consequences of exposure vary due to uptake route and ionoregulatory status. The goal of this research was to develop a model fish system to assess the influence of different Cu exposure routes (waterborne or dietary) on bioavailability, uptake, and effects in hybrid striped bass ( Morone chrysops × Morone saxatilis ) acclimated to fresh- or saltwater. Initially, hybrid striped bass were exposed to dietary Cu concentrations of 571, 785, and 1013 μg Cu/g, along with a control (∼ 5 μg Cu/g), for 14 days in saltwater. Intestinal and liver Cu accumulated in a dose-dependent manner in fish exposed to increasing levels of dietary Cu. Chronic (42 days) experiments were then conducted to determine sub-lethal effects of aqueous, dietary, and combined aqueous and dietary Cu exposures to both freshwater- and saltwater-acclimated hybrid striped bass. Growth and Cu accumulation in the gill, intestine, and liver were measured. Although no significant effects were observed in fish exposed to waterborne Cu, those exposed through the diet accumulated significant liver and intestinal Cu but showed no significant change in growth. Overall, these results suggest that at the levels tested, exposure to elevated waterborne Cu did not cause significant long-term tissue Cu accumulation, whereas dietary Cu exposure caused significant liver and intestinal Cu accumulation in hybrid striped bass which was comparable in both freshwater and saltwater (15 g/L).

Comparative Biochemistry and Physiology, Part C: T↗

Spatial and seasonal variations in mercury methylation and microbial community structure in a historic mercury mining area, Yolo County, California

The relationships between soil parent lithology, nutrient concentrations, microbial biomass and community structure were evaluated in soils from a small watershed impacted by historic Hg mining. Upland and wetland soils, stream sediments and tailings were collected and analyzed for nutrients (DOC, SO 4 = , NO 3 - ), Hg, MeHg, and phospholipid fatty acids (PLFA). Stream sediment was derived from serpentinite, siltstone, volcanic rocks and mineralized serpentine with cinnabar, metacinnabar and other Hg phases. Soils from different parent materials had distinct PLFA biomass and community structures that are related to nutrient concentrations and toxicity effects of trace metals including Hg. The formation of MeHg appears to be most strongly linked to soil moisture, which in turn has a correlative relationship with PLFA biomass in wetland soils. The greatest concentrations of MeHg (> 0.5??ng g - 1 MeHg) were measured in wetland soils and soil with a volcanic parent (9.5-37????g g - 1 Hg). Mercury methylation was associated with sulfate-reducing bacteria, including Desulfobacter sp. and Desulfovibrio sp., although these organisms are not exclusively responsible for Hg methylation. Statistical models of the data demonstrated that soil microbial communities varied more with soil type than with season.

Chemical Geology↗

Quantifying biomineralization of zinc in the Rio Naracauli (Sardinia, Italy), using a tracer injection and synoptic sampling

Streams draining mined areas throughout the world commonly have high concentrations of Zn. Because Zn is not easily removed from stream water and because it can be toxic to aquatic organisms, its presence is a persistent problem. The discovery of biomineralization of Zn-bearing solids in the mine drainage of Rio Naracauli, in Sardinia, Italy, provides insights into strategies for removing Zn and improving water quality in streams affected by mine drainage. Until now, the transport and attenuation of Zn has not been quantified in this stream setting. A continuous tracer injection experiment was conducted to quantify the biomineralization process and to identify the loading of constituents that causes a change from precipitation of hydrozincite [Zn 5 (CO 3 ) 2 (OH) 6 ] in the upstream reach to precipitation of a Zn-silicate phase downstream. Based on the mass-load calculations derived from the tracer experiment, about 1.2 kg/day of Zn is sequestered in hydrozincite. This biomineralization represents nearly 90% removal of Zn. Other elements such as Pb and Cd also are sequestered, either in the hydrozincite, or in a separate phase that forms simultaneously. In the lower 600 m of the stream, where the Zn-silicate forms, as much as 0.7 kg/day Zn are sequestered in this solid, but additions of Zn to the stream from groundwater discharge lead to an overall increase in load in that portion of the Rio Naracauli.

Sardinia↗