Toxicity of cobalt-complexed cyanide to <Emphasis Type="Italic">Oncorhynchus mykiss,Daphnia magna</Emphasis>, and <Emphasis Type="Italic">Ceriodaphnia dubia</Emphasis>

Background Cobalt cyanide complexes often result when ore is treated with cyanide solutions to extract gold and other metals. These have recently been discovered in low but significant concentrations in effluents from gold leach operations. This study was conducted to determine the potential toxicity of cobalt-cyanide complexes to freshwater organisms and the extent to which ultraviolet radiation (UV) potentiates this toxicity. Tests were also conducted to determine if humic acids or if adaptation to UV influenced sensitivity to the cyanide complexes. Methods Rainbow trout (Oncorhynchus mykiss), Daphnia magna, and Ceriodaphnia dubia were exposed to potassium hexacyanocobaltate in the presence and absence of UV radiation, in the presence and absence of humic acids. Cyano-cobalt exposures were also conducted with C. dubia from cultures adapted to elevated UV. Results With an LC50 concentration of 0.38 mg/L, cyanocobalt was over a 1000 times more toxic to rainbow trout in the presence of UV at a low, environmentally relevant irradiance level (4 μW/cm² as UVB) than exposure to this compound in the absence of UV with an LC50 of 112.9 mg/L. Toxicity was immediately apparent, with mortality occurring within an hour of the onset of exposure at the highest concentration. Fish were unaffected by exposure to UV alone. Weak-acid dissociable cyanide concentrations were observed in irradiated aqueous solutions of cyanocobaltate within hours of UV exposure and persisted in the presence of UV for at least 96 hours, whereas negligible concentrations were observed in the absence of UV. The presence of humic acids significantly diminished cyanocobalt toxicity to D. magna and reduced mortality from UV exposure. Humic acids did not significantly influence survival among C. dubia. C. dubia from UV-adapted populations were less sensitive to metallocyanide compounds than organisms from unadapted populations. Conclusions The results indicate that metallocyanide complexes may pose a hazard to aquatic life through photochemically induced processes. Factors that decrease UV exposure such as dissolved organic carbon or increased pigmentation would diminish toxicity.     

Evaluations of combined zebrafish (Danio rerio) embryo and marine phytoplankton (Diacronema lutheri) toxicity of dissolved organic contaminants in the Ythan catchment,Scotland, UK

A wide variety of organic contaminants including pesticides, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) have previously been detected in surface waters in the river Ythan catchment, North East Scotland UK. While the concentrations detected were below Water Framework Directive Environmental Quality Standards (WFD-EQSs) environmental exposures to the diverse mixtures of contaminants, known and unknown, may pose chronic and/or sublethal effects to non target organisms. The present study assessed the embryo and algal toxicity potential of freely dissolved organic contaminants from the Ythan catchment using silicone rubber passive sampling devices (SR-PSDs) and miniaturised bioassay techniques. Zebrafish (Danio rerio) embryos and marine phytoplankton species (Diacronema lutheri) were exposed to extracts from SR-PSDs deployed at different locations along the river Ythan and an undeployed procedural blank. Statistically significant developmental and algal toxicities were measured in all tests of extracts from deployed samples compared with the procedural blanks. This indicates environmental exposure to, and the combined toxicity potential of, freely dissolved organic contaminants in the catchment. The present and previous studies in the Ythan catchment, coupling SR-PSDs and bioassay techniques, have both helped to understand the interactions and combined effects of dissolved organic contaminants in the catchment. They have further revealed the need for improvement in the techniques currently used to assess environmental impact.     

Measurement of transferable chemical residue from nylon carpet using the California roller and a new mega-California roller

Human chemical exposures resulting from transfer of surface deposition on indoor nylon carpets may be estimated by measuring transferable residues (μ g chemical/cm² carpet). A weighted roller developed at California Department of Food and Agriculture (CDFA) has been extensively used to sample transferable residue for estimates of human exposure in risk characterization. A modified roller has been developed to evaluate the influence of pressure on transferable chemical residue since weight and force (or pressure, kg/m²) may vary person-to-person and activity-to-activity. A 30.5 cm diameter roller was used to apply 60 to 2100 kg/m² to bracket pressures exerted by humans on a flat nylon-carpeted surface. Measurements of transferable cyfluthrin residues were made after 1, 7, and 21 days. Total Soxhlet extractable cyfluthrin residues were relatively constant during the test period. Residue transferability decreased during the study period. Modest increases in the transferability of surface residues were observed over the broad range of pressures applied by the modified roller.     

Kinetics and Mechanism of the Reaction of Azide with Ozone in Aqueous Solution

ABSTRACT

The stoichiometry of the reaction of aqueous ozone with sodium azide was studied at pH 12 (mainly) where a yellow metastable intermediate is observed. We propose that this is hypoazidite (N₃O^- ), analogous to hypobromite, and that it plays a central role in the azide catalyzed decompostion of ozone. The yellow intermediate is unstable in acid, in which it rapidly decomposes, generating N₂ and NO₂ ^-.

The rate of reaction was studied at pH 2.0–3.5, with the ionic strength at 0.6 M and temperature at 3–15 ° C. The intrinsic second-order rate constants were found to be k _HN3 ≤ ≈ 400 M^-1sec^-1 and k _N3- = (8.7 ± 0.5) × 10⁵ M^-1sec^-1 (3 °C, 0.6 M), both in agreement with the only other previous study. The rate constant at 25 °C was estimated using the following experimentally determined parameters: ln k_N3- (M^-1sec^-1) = (5.73 ± 0.36) × 10³/T (K) + (28.34 ± 1.27). The value of k_N3- estimated in this way is (2.5 ± 0.1) × 10⁶ M^-1sec^-1 at 25 °C and 0.6 M. The enthalpy of reaction (A H) is -48 ± 3 kJ mol^-1.     

The Effect of Reformulated Gasoline on Ambient Carbon Monoxide Concentrations in Southeastern Wisconsin

Abstract

Reformulated gasoline (RFG) contains oxygen additives such as methyl tertiary butyl ether or ethanol. The additives enable vehicles to burn fuel with a higher air/fuel ratio, thereby lowering the emission of carbon monoxide (CO) and volatile organic compounds (VOCs). Because VOCs react with sunlight to form ozone (O₃), the Clean Air Act requires severe O₃ nonattainment areas such as southeastern Wisconsin to use RFG. On July 17, 2001, the U.S. Environmental Protection Agency (EPA) granted Milwaukee, WI, and Chicago, IL, a waiver from the VOC reduction requirement of Phase II RFG. The VOC reduction requirement was lowered from 27.4% of the 1990 baseline fuel to 25.4%. The assumption was that ethanol-blended RFG would lower summertime CO concentrations sufficiently to offset the increased VOC emissions. The waiver is estimated to increase VOC emissions by ～0.8%, or 0.4 t of VOC on a hot summer weekday. This study evaluates whether RFG has been effective in lowering southeastern Wisconsin ambient CO concentrations. Three years of ambient CO data before RFG was introduced were compared with the first three years of ambient CO data after RFG was introduced. This paper also evaluates how the meteorology, vehicle inspection/maintenance program, vehicle miles traveled, and stationary source emissions influence CO concentrations. The winter decrease in ambient CO concentrations was found to be statistically significant, while the summer data showed no statistically significant change, indicating that RFG is most effective lowering ambient CO concentrations in cold weather.     

Is shrimp farming a successful adaptation to salinity intrusion? A geospatial associative analysis of poverty in the populous Ganges–Brahmaputra–Meghna Delta of Bangladesh

The Ganges–Brahmaputra–Meghna delta of Bangladesh is one of the most populous deltas in the world, supporting as many as 140 million people. The delta is threatened by diverse environmental stressors including salinity intrusion, with adverse consequences for livelihood and health. Shrimp farming is recognised as one of the few economic adaptations to the impacts of the rapidly salinizing delta. Although salinity intrusion and shrimp farming are geographically co-located in the delta, there has been no systematic study to examine their geospatial associations with poverty. In this study, we use multiple data sources including Census, Landsat Satellite Imagery and soil salinity survey data to examine the extent of geospatial clustering of poverty within the delta and their associative relationships with salinity intensity and shrimp farming. The analysis was conducted at the union level, which is the lowest local government administrative unit in Bangladesh. The findings show a strong clustering of poverty in the delta, and whilst different intensities of salinization are significantly associated with increasing poverty, neither saline nor freshwater shrimp farming has a significant association with poverty. These findings suggest that whilst shrimp farming may produce economic growth, in its present form it has not been an effective adaptation for the poor and marginalised areas of the delta. The study demonstrates that there are a series of drivers of poverty in the delta, including salinization, water logging, wetland/mudflats, employment, education and access to roads, amongst others that are discernible spatially, indicating that poverty alleviation programmes in the delta require strengthening with area-specific targeted interventions.     

Mobilization of arsenic in aquifers from the Datong Basin,China: Evidence from geochemical and iron isotopic data

Iron isotope compositions of various Fe pools in aquifer sediments were measured at a known As-contaminated site in the Datong Basin, China. The δ⁵⁶Fe values of HCl-extracted poor-crystalline Fe(III) range widely from ?0.41‰ to 0.36‰. We interpret the low Fe(II)/Fe_Extractable ratios (<50%) and the negative correlation between Fe(II)/Fe_Extractable and δ⁵⁶Fe values in HCl-extracted poor-crystalline Fe to be best explained by redox cycling of Fe induced by microbial Fe(III) reduction. However, the high Fe(II)/Fe_Extractable ratios (?70%) and positive correlation between Fe(II)/Fe_Extractable and δ⁵⁶Fe values for HCl-extracted poor-crystalline Fe indicates production of sulfides (FeSs). The δ⁵⁶Fe values of crystalline Fe(III) extracted by reductant appears to be comparatively small varying from ?0.01‰ to 0.24‰, which is consistent with the δ⁵⁶Fe values for ferric oxides/hydroxides having undergone microbial Fe(III) reduction. The Fe isotope composition of various Fe pools shows the transformation between crystalline Fe(III) and poor-crystalline crystalline Fe(III) and the secondary Fe(II) phases has already occurred or is occurring in aquifer sediments. More importantly, there is a significant difference in the As concentrations in crystalline Fe(III) oxides/hydroxides and HCl-extracted Fe phases. The concentrations of As range from 1.6 to 29.9 mg kg^?1 and from 0.6 to 3.0 mg kg^?1, for crystalline Fe(III) and HCl-extracted Fe phases respectively. Accordingly, the transformation of Fe minerals induced by microbial Fe(III) reduction can contribute to the mobilization of As. This study is the first to examine the Fe isotope compositions in high As aquifer sediments; the results show that the Fe isotope would be an important tool in demonstrating the enrichment of As in groundwater.     

Rapid and Sensitive LC/MS/MS Direct Injection Method for the Determination of Trace Level Corexit EC9500A Oil Dispersant in Seawater

A rapid and sensitive liquid chromatography tandem mass spectrometry (LC/MS/MS) method for the determination of trace dioctyl sulfosuccinate (DOSS) concentrations in seawater samples has been established. The method is well suited to aquatic environment impact monitoring following application of the dispersant Corexit EC9500A. Linearity of the method was demonstrated down to 0.05 ng/mL^?1 (0.05 µgL^?1) DOSS in seawater, with a 2.4% relative standard deviation precision for preparation replicates. A US EPA method limit of detection of <0.02 ng/mL^?1 (<0.02 µgL^?1) was calculated and specificity was confirmed by monitoring of two qualifier ions at 291.1 m/z and 227.1 m/z. These transitions were confirmed by QToF analysis to be associated with the DOSS precursor ion at 421.2 m/z. For application to seawater samples and samples containing oil particulates, a practical and repeatable calibration range of 0.5 ng/mL^?1 (0.5 µgL^?1) to 25.0 ng/mL^?1 (25.0 µgL^?1) DOSS is reported. The method was shown to have excellent precision and accuracy, with a consistent ≤1.6% relative standard deviation for system suitability standards at 0.5 ng/mL^?1 (0.5 µgL^?1) and linear weighted (1/x) regression coefficients of determination ≥0.995. The surfactant nature of the analyte is discussed in relation to detection limit and loss of analyte. Speculation of a relationship between DOSS in association or aggregation with divalent cations, such as Ca²⁺ present in salt water and hard water, is suggested. The consequent effects on cell ionic balance and membrane function are discussed.     

Intensive fishing of marine consumers causes a dramatic shift in the benthic habitat on temperate rocky reefs

Intensive fishing can cause dramatic, long-lasting shifts in benthic habitat. This study used three approaches to test whether overharvesting of blacklip abalone (Haliotis rubra) can cause a shift in benthic habitat to a configuration that is unsuitable for abalone, on the east coast of Tasmania, Australia. After 18 months of removing abalone from rocks, encrusting red algae (ERA) became overgrown by filamentous and foliose algae, sessile invertebrates and accumulated sediment. The differences in the community composition between locations, sites nested within locations and rocks were minor. Throughout the study, abalone were largely associated with areas of rock covered in ERA but avoided other habitats. A transplant experiment demonstrated that abalone preferred areas of rock covered in ERA but move away from overgrown rocks. These results suggest overharvesting of abalone results in a shift to benthic habitat poorly preferred by abalone. This could form a positive feedback loop that limits recovery of abalone populations and ERA.     

Unified methodology for site-characterization and sampling of highway runoff

Hydrology, roadway traffic conditions, and atmospheric deposition are three essential data categories for the planning and implementation of highway-runoff monitoring and characterization programs. Causal variables pertaining to each data category could be site specific but have been shown to correlate with runoff pollutant loads. These data categories were combined to derive statistical relationships for characterization and prioritization of the respective pollutant loads at highway runoff sites. Storm runoff data of total suspended solids (TSS), total dissolved solid (TDS), chemical oxygen demand (COD), total Kjeldahl nitrogen (TKN) and total phosphorus (TP) collected from three highway sites in Charlotte, North Carolina, USA, were used to illustrate the development of site-specific highway-runoff pollutant loading models. This unified methodology provides a basis for initial assessment of the pollutant-constituent loads from highway runoff using hydrologic component variables. Improved reliability is achievable when additional traffic and/or atmospheric component variables are incorporated into the basic hydrologic regression model. In addition, operational guidance is suggested for implementing highway-runoff monitoring programs that are subject to sampling and resources constraints.