Speciation and transport of arsenic in an acid sulfate soil-dominated catchment, eastern Australia

Factors controlling the transport of geogenically-derived arsenic from a coastal acid sulfate soil into downstream sediments are identified in this study with both solid-phase associations and aqueous speciation clearly critical to the mobility and toxicity of arsenic. The data from both sequential extractions and X-ray adsorption spectroscopy indicate that arsenic in the unoxidised Holocene acid sulfate soils is essentially non-labile in the absence of prolonged oxidation, existing primarily as arsenopyrite or as an arsenopyrite-like species, likely arsenian pyrite. Anthropogenically-accelerated pedogenic processes, which have oxidised this material over time, have greatly enhanced the potential bioavailability of arsenic, with solid-phase arsenic almost solely present as As(V) associated with secondary Fe(III) minerals present. Analyses of downstream sediments reveal that a portion of the arsenic is retained as a mixed As(III)/As(V) solid-phase, though not at levels considered to be environmentally deleterious. Determination of arsenic speciation in pore waters using high performance liquid chromatography/Inductively Coupled Plasma-Mass Spectrometry shows a dominance of As(III) in upstream pore waters whilst an unidentified As species reaches comparative levels within the downstream, estuarine locations. Pore water As(V) was detected at trace concentrations only. The results demonstrate the importance of landscape processes to arsenic transport and availability within acid sulfate soil environments.     

The dynamics of arsenic in four paddy fields in the Bengal delta

Irrigation with arsenic contaminated groundwater in the Bengal Delta may lead to As accumulation in the soil and rice grain. The dynamics of As concentration and speciation in paddy fields during dry season (boro) rice cultivation were investigated at 4 sites in Bangladesh and West Bengal, India. Three sites which were irrigated with high As groundwater had elevated As concentrations in the soils, showing a significant gradient from the irrigation inlet across the field. Arsenic concentration and speciation in soil pore water varied temporally and spatially; higher As concentrations were associated with an increasing percentage of arsenite, indicating a reductive mobilization. Concentrations of As in rice grain varied by 2-7 fold within individual fields and were poorly related with the soil As concentration. A field site employing alternating flooded-dry irrigation produced the lowest range of grain As concentration, suggesting a lower soil As availability caused by periodic aerobic conditions.     

Growth of soybean at future tropospheric ozone concentrations decreases canopy evapotranspiration and soil water depletion

Tropospheric ozone is increasing in many agricultural regions resulting in decreased stomatal conductance and overall biomass of sensitive crop species. These physiological effects of ozone forecast changes in evapotranspiration and thus in the terrestrial hydrological cycle, particularly in intercontinental interiors. Soybean plots were fumigated with ozone to achieve concentrations above ambient levels over five growing seasons in open-air field conditions. Mean season increases in ozone concentrations ([O₃]) varied between growing seasons from 22 to 37% above background concentrations. The objective of this experiment was to examine the effects of future [O₃] on crop ecosystem energy fluxes and water use. Elevated [O₃] caused decreases in canopy evapotranspiration resulting in decreased water use by as much as 15% in high ozone years and decreased soil water removal. In addition, ozone treatment resulted in increased sensible heat flux in all years indicative of day-time increase in canopy temperature of up to 0.7 °C.     

Impact of soil quality on elemental uptake by, and distribution in, Colocasia esculenta (Amadumbe), an edible root

In this study the elemental distribution of selected essential (Ca, Mg, Al, Mn, Cu, Fe, Co, Cr, Zn, Ni and Se) and the non-essential (Pb, Hg and As) elements were determined in the bulb and peel of Amadumbe (Colocasia esculenta) samples from eight different sites in KwaZulu-Natal, South Africa. The concentration of Se and As in the soil and in the Amadumbe bulbs were below the detection limit of 0.09 μg g?1. The total and bioavailable concentrations of the elements in conjunction with pH, soil organic matter (SOM) and cation exchange capacity (CEC) were determined in the soil samples from the eight sites. Statistical analysis was done to evaluate the impact of soil quality parameters on the chemical composition of the Amadumbe root. The results show accumulation or exclusion of certain elements by the bulb as evidenced by the noticeable increase or decrease of the concentrations of elements, respectively. Ca and Mg were found to be major elements in the range (2000-12000 μg g?1), whilst Mn, Zn, Fe and Al were found to be minor elements in the range (20-400 μg g?1). A general trend observed was that the plant favours the absorption of Zn over Cu. A positive correlation between Mg & Ca, Cu & Fe and Co & Ni was also observed. Statistical analysis revealed that the plant tended to accumulate Mg, Ca, Co, Cr and Pb whilst it excluded Hg and Fe, to a lesser extent.     

Probability of intellectual disability is associated with soil concentrations of arsenic and lead

Background

The association between metals in water and soil and adverse child neurologic outcomes has focused on the singular effect of lead (Pb), mercury (Hg), and arsenic (As). This study describes the complex association between soil concentrations of As combined with Pb and the probability of intellectual disability (ID) in children.

Methods

We used a retrospective cohort design with 3988 mother child pairs who were insured by Medicaid and lived during pregnancy and early childhood in South Carolina between 1/1/97 and 12/31/02. The children were followed until 6/1/08, using computerized service files, to identify the diagnosis of ID in medical records and verified by either school placement or disability service records. The soil was sampled using a uniform grid and analyzed for eight metals. The metal concentrations were interpolated using Bayesian Kriging to estimate concentration at individual residences.

Results

The probability of ID increased for increasing concentrations of As and Pb in the soil. The Odds Ratio for ID, for one unit change in As was 1.130 (95% confidence interval 1.048-1.218) for Pb was 1.002 (95% confidence interval 1.000-1.004). We identified effect modification for the infants based on their birth weight for gestational age status and only infants who were normal size for their gestational age had increased probability of ID based on the As and Pb soil concentrations (OR for As at normal weight for gestational age = 1.151 (95% CI: 1.061-1.249) and OR for Pb at normal for gestational age = 1.002 (95% CI: 1.002-1.004)). For normal weight for gestational age children when As = 22 mg kg⁻¹ and Pb = 200 mg kg⁻¹ the risk for ID was 11% and when As = 22 mg kg⁻¹and Pb = 400 mg kg⁻¹ the probability of ID was 65%.

Conclusion

The probability of ID is significantly associated with the interaction between Pb and As for normal weight for gestational age infants.     

Innovative applications of subgrade biogeochemical reactors: Three case studies

Subgrade biogeochemical reactors (SBGRs) are an in situ remediation technology shown to be effective in treating contaminant source areas and groundwater hot spots, while being sustainable and economical. This technology has been applied for over a decade to treat chlorinated volatile organic compound source areas where groundwater is shallow (e.g., less than approximately 30 feet below ground surface [ft bgs]). However, this article provides three case studies describing innovative SBGR configurations recently developed and tested that are outside of this norm, which enable use of this technology under more challenging site conditions or for treatment of alternative contaminant classes. The first SBGR case study addresses a site with groundwater deeper than 30 ft bgs and limited space for construction, where an SBGR column configuration reduced the maximum trichloroethene (TCE) groundwater concentration from 9,900 micrograms per liter (μg/L) to <1 μg/L (nondetect) within approximately 15 months. The second SBGR is a recirculating trench configuration that is supporting remediation of a 5.7‐acre TCE plume, which has significant surface footprint constraints due to the presence of endangered species habitat. The third SBGR was constructed with a new amendment mixture and reduced groundwater contaminant concentrations in a petroleum hydrocarbon source area by over 97% within approximately 1 year. Additionally, a summary is provided for new SBGR configurations that are planned for treatment of additional classes of contaminants (e.g., hexavalent chromium, 1,4‐dioxane, dissolved explosives constituents, etc.). A discussion is also provided describing research being conducted to further understand and optimize treatment mechanisms within SBGRs, including a recently developed sampling approach called the aquifer matrix probe.     

A case study of an isolated wind powered electricity system meeting 100% of local demand

Using meteorological and electricity demand data for a 4-year period, electricity demand in Shetland was modeled to provide an estimate of the demand over a 30-year period from 1 January 1981. That modeled demand was then compared to estimated wind power output over the same period using the WAsP model. The wind farm output was estimated for a range of sizes of wind farm up to the consented 370 MW Viking Wind Farm in Shetland. Some wind power was available for 94% of the time and the 370 MW wind farm would meet 100% of demand for nearly 80% of the time. The statistics of single and accumulated deficits were calculated for a range of wind farms and estimates of the amount of additional generation capacity and additional power requirements were assessed. The study suggests that with storage, wind power in Shetland could meet all electricity demand in Shetland at around £130 to £150/MWh (excluding subsidy) and with a grid connection allowing the sale of excess power, those costs could be reduced.     

Contaminant mass flux and forensic assessment of polycyclic aromatic hydrocarbons: Tools to inform remediation decision making at a contaminated site in Canada

Polycyclic aromatic hydrocarbons (PAHs) and metal(loid) mass flux estimates and forensic assessment using PAH diagnostic ratios were used to inform remediation decision making at the Sydney Tar Ponds (STPs) and Coke Ovens cleanup project in eastern Canada. Environmental effects monitoring of surface marine sediments in Sydney Harbor indicated significantly higher PAH concentrations during the first year of remediation monitoring compared to baseline. This was equivalent to PAH loadings of ～2,000 kg over a 15‐month period. Increases in sediment PAH concentrations raised serious concerns for regulators, who requested cessation of remediation activities early in the $400 M (CAD) project. Historically, the STPs were reported as the primary source of PAH contamination in Sydney Harbor with estimated discharges of 300 to 800 kg/year between 1989 and 2001. Mass flux estimates of PAHs and metal(loid)s and PAH diagnostic ratios were used to evaluate if increases in PAH concentrations in marine sediments were the result of the STPs remediation activities. PAH mass flux estimates approximated that 17 to 97 kg/year were discharged from the STPs during three years of remediation and were corroborated by an independent PAH flux estimate of 119 kg in year 1. PAH fluxes to the Sydney Harbor were mostly surface water derived, with groundwater contributing negligible quantities (0.002–0.005 kg/year). Fluxes of metal(loid)s to harbor sediments were stable or declining across all years and were mirrored in sediment metal(loid) concentrations, which lacked temporal variation, unlike total PAH concentrations. Flux results were also corroborated using PAH diagnostic ratios, which found a common source of PAHs. Coal combustion was likely the principal source of PAHs and not migration from the STPs during remediation. Although short‐term residual sediment PAH increases during onset of remediation raised concerns for regulators, calls for premature cessation of remediation early in the project were unwarranted based on only one year of monitoring data. Mass flux estimates and forensic assessments using PAH diagnostic ratios proved useful tools to inform remediation decision making that helped environmental protection and reduced costs associated with lost cleanup time.     

Identifying natural and anthropogenic sources of metals in urban and rural soils using GIS-based data,PCA, and spatial interpolation

Determining sources of neurotoxic metals in rural and urban soils is important for mitigating human exposure. Surface soil from four areas with significant clusters of mental retardation and developmental delay (MR/DD) in children, and one control site were analyzed for nine metals and characterized by soil type, climate, ecological region, land use and industrial facilities using readily available GIS-based data. Kriging, principal component analysis (PCA) and cluster analysis (CA) were used to identify commonalities of metal distribution. Three MR/DD areas (one rural and two urban) had similar soil types and significantly higher soil metal concentrations. PCA and CA results suggested that Ba, Be and Mn were consistently from natural sources; Pb and Hg from anthropogenic sources; and As, Cr, Cu, and Ni from both sources. Arsenic had low commonality estimates, was highly associated with a third PCA factor, and had a complex distribution, complicating mitigation strategies to minimize concentrations and exposures.     

TBT contamination of remote marine environments: ship groundings and ice-breakers as sources of organotins in the Great Barrier Reef and Antarctica

Remote marine environments such as many parts of the Great Barrier Reef (GBR) and the Antarctic are often assumed to be among the most pristine natural habitats. While distance protects them from many sources of pollution, recent studies have revealed extremely high concentrations of organotins in areas associated with shipping activities. Sediments at sites of ship groundings on the GBR have been found to contain up to 340,000 microg Sn kg(-1). Very high concentrations (up to 2290 microg Sn kg(-1)) have been detected in nearshore Antarctic sediments adjacent to channels cut through sea ice by ice-breaking vessels. In both cases, the bulk of the contamination is associated with flakes of antifouling paint abraded from vessel hulls, resulting in patchy but locally intense contamination of sediments. These particulates are likely to continue releasing organotins, rendering grounding sites and ice-breaking routes point-sources of contamination of surrounding environments. While the areas exposed to biologically-harmful concentrations of leached chemicals are likely to be limited in extent (1000-10,000 m(2)), deposition of antifouling paints constitutes a persistent ecological risk in otherwise pristine marine environments of high conservation value. The risk of contamination of GBR and Antarctic sediments by organotins needs to be considered against an important alternative risk: that less effective antifouling of ships hulls may increase the frequency of successful invasions by non-indigenous species. Additional options to minimise ecological risk include accident prevention and reducing organotin contamination from grounding sites through removal or treatment of contaminated sediments, as has been done at some sites in the GBR.