Chemical extraction methods to assess bioavailable arsenic in soil and solid media

Soil ingestion by children is an important pathway in assessing public health risks associated with exposure to arsenic-contaminated soils. Soil chemical methods are available to extract various pools of soil arsenic, but their ability to measure bioavailable arsenic from soil ingestion is unknown. Arsenic extracted by five commonly used soil extractants was compared with bioavailable arsenic measured in vivo by immature swine (Sus scrofa) dosing trials. Fifteen contaminated soils that contained 233 to 17 500 mg kg(-1) arsenic were studied. Soil extractants were selected to dissolve surficially adsorbed and/or readily soluble arsenic (water, 1 M sodium acetate, 0.1 M Na2HPO4/0.1 M NaH2PO4) and arsenic in Fe and Mn oxide minerals (hydroxylamine hydrochloride, ammonium oxalate). The mean percent of total arsenic extracted was: ammonium oxalate (53.6%) > or = hydroxylamine hydrochloride (51.7%) > phosphate (10.5%), acetate (7.16%) > water (0.15%). The strongest relationship between arsenic determined by soil chemical extraction and in vivo bioavailable arsenic was found for hydroxylamine hydrochloride extractant (r = 0.88, significant at the 0.01 probability level). Comparison of the amount of arsenic extracted by soil methods with bioavailable arsenic showed the following trend: ammonium oxalate, hydroxylamine hydrochloride > in vivo > phosphate, acetate > water. The amount of arsenic dissolved in the stomach (potentially bioavailable) is between surficially adsorbed (extracted by phosphate or acetate) and surficially adsorbed + nonsurficial forms in Fe and Mn oxides (extracted by hydroxylamine hydrochloride or ammonium oxalate). Soil extraction methods that dissolve some of the amorphous Fe, such as hydroxylamine hydrochloride, can be designed to provide closer estimates of bioavailable arsenic.     

Metal bioavailability and speciation in a wetland tailings repository amended with biosolids compost,wood ash,and sulfate

Lead poisoning of waterfowl from direct ingestion of wetland mine tailings has been reported at the Coeur d'Alene River basin in Idaho. A greenhouse study was conducted to evaluate the effects of surface applications of amendments on lead bioavailability in the tailings. Treatments included sediment only, and sediment with three different surface amendments: (i) biosolids compost plus wood ash, (ii) compost + wood ash + a low SO4(2-) addition as K2SO4, and (iii) compost + wood ash + a high SO4(2-) addition. Measured variables included growth and tissue Pb, Zn, and Cd concentration of arrowhead (Sagittaria latifolia Willd.) and cattail (Typha latifolia L.) and soil pH, redox potential (Eh), pore water Pb, Pb speciation by X-ray absorption spectroscopy, and in vitro Pb bioavailability. The compost + ash amendment alleviated phytotoxicity for both plant species. Bioavailability of Pb as measured by a rapid in vitro extract decreased by 24 to 34% (over control) in the tailings directly below the amendment layer in the compost + SO4 treatments. The ratio of acid volatile sulfide (AVS) to simultaneously extracted metals (SEM) also indicated a reduction in Pb bioavailability (1:40 control, 1:20 compost, 1:8 compost + low SO4, and 1:3 compost + high SO4). Extended X-ray adsorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy data indicated that lead sulfide was greater after 99 d in the treatments that included additions of sulfate. These results indicated that, under reducing conditions, surface amendments of compost + wood ash (with or without sulfate) decreased the bioavailability of Pb in metal-contaminated mine tailings.     

Prioritizing Wetland Restoration for Sediment Yield Reduction: A Conceptual Model

In a climate of limited resources, it is often necessary to prioritize restoration efforts geographically. The synoptic approach is an ecologically based tool for geographic prioritization of wetland protection and restoration efforts. The approach was specifically designed to incorporate best professional judgment in cases where information and resources are otherwise limited. Synoptic assessments calculate indices for functional criteria in subunits (watersheds, counties, etc.) of a region and then rank the subunits. Ranks can be visualized in region-scale maps which enable managers to identify areas where efforts optimize functional performance on a regional scale. In this paper, we develop a conceptual model for prioritizing watersheds whose wetlands can be restored to reduce total sediment yield at the watershed outlet. The conceptual model is designed to rank watersheds but not individual wetlands within a watershed. The synoptic approach is valid for applying the sediment yield reduction model because there is high demand for prioritizing disturbed wetlands for restoration, but there is limited, quantitative, accurate information available with which to make decisions. Furthermore, the cost of creating a comprehensive database is prohibitively high. Finally, because the model will be used for planning purposes, and, specifically, for prioritizing based on multiple decisions rather than optimizing a single decision, the consequence of prioritization errors is low. Model results cannot be treated as scientific findings. The conclusions of an assessment are based on judgement, but this judgement is guided by scientific principles and a general understanding of relevant ecological processes. The conceptual model was developed as the first step towards prioritizing of wetland restoration for sediment yield reduction in US EPA Region 4.     

Environmental Water-Quality Zones for Streams: A Regional Classification Scheme

Various approaches have been used to classify large geographical areas into smaller regions of similar water quality or extrapolate water-quality data from a few streams to other unmonitored streams. A combination of some of the strengths of existing techniques is used to develop a new approach for these purposes. In this new approach, referred to here as SPARTA (SPAtial Regression-Tree Analysis), environmental characteristics for each monitored stream are first quantified using a Geographic Information System (GIS) and then regression-tree analysis is used to determine which characteristics are most statistically important in describing the distribution of a specific water-quality constituent. GIS coverages of only the most statistically significant environmental characteristics are then used to subdivide the area of interest into relatively homogeneous environmental water-quality zones. Results from the regression-tree analysis not only define the most important environmental characteristics, but also describe how to subdivide the coverage of the specific characteristic (for example, areas with <26% or ≥26% soil clay content). The resulting regionalization scheme is customized for each water-quality constituent based on the environmental characteristics most statistically related to that constituent. SPARTA was used to delineate areas of similar phosphorus, nitrogen, and sediment concentrations (by including land-use characteristics) and areas of similar potential water quality (by excluding land-use characteristics). The SPARTA approach reduced the variability in water-quality concentrations (phosphorus, total nitrogen, Kjeldahl nitrogen, and suspended sediment) within similarly classified zones from that obtained using the US Environmental Protection Agency's nutrient ecoregions.     

EMMC process for combined removal of organics, nitrogen and an odor producing substance

In order to improve the process performance regarding the removal of organics, nitrogen, and an odor-causing compound (sulfide) contained in domestic wastewater, an entrapped-mixed-microbial cell (EMMC) with and without humic substances for both fixed and moving carrier reactors and conventional suspended growth culture (i.e. conventional activated sludge process) were investigated simultaneously. Both synthetic (simulated to the organics concentration of general domestic sewage) and actual domestic wastewater were investigated under operational conditions of 12 h of hydraulic retention time (HRT) with 1 h of aeration and 1 h of non-aeration, and 6 h of HRT with continuous aeration, at a room temperature of 25 +/- 2 degrees C. It was found that entrapping humic substances in the EMMC carriers had no impact on the removal of organics, nitrogen, and the odor-producing compound. Additionally, the performance of the EMMC moving carrier system for the removal of these pollutants is similar to that of the EMMC fixed carrier system. In general, the EMMC associated systems which provide high solids retention time achieve a better removal of chemical oxygen demand (COD), nitrogen, and the odor-producing substance than the suspended growth system for both HRTs of 6 h (continuous aeration) and 12 h (1 h of aeration and 1 h of non-aeration). Both the fixed and moving carrier EMMC processes, therefore, have the potential for improvement or replacement of the existing conventional activated sludge process with regard to improving the effluent qualities (such as COD, nitrogen and odor-producing compound) for reuse/disposal.     

Evaluating factors influencing groundwater vulnerability to nitrate pollution: developing the potential of GIS

The 1991 EU Nitrate Directive was designed to reduce water pollution from agriculturally derived nitrates. England and Wales implemented this Directive by controlling agricultural activities within their most vulnerable areas termed Nitrate Vulnerable Zones. These were designated by identifying drinking water catchments (surface and groundwater), at risk from nitrate pollution. However, this method contravened the Nitrate Directive because it only protected drinking water and not all waters. In this paper, a GIS was used to identify all areas of groundwater vulnerable to nitrate pollution. This was achieved by constructing a model containing data on four characteristics: the quality of the water leaving the root zone of a piece of land; soil information; presence of low permeability superficial (drift) material; and aquifer properties. These were combined in a GIS and the various combinations converted into a measure of vulnerability using expert knowledge. Several model variants were produced using different estimates of the quality of the water leaving the root zone and contrasting methods of weighting the input data. When the final models were assessed all produced similar spatial patterns and, when verified by comparison with trend data derived from monitored nitrate concentrations, all the models were statistically significant predictors of groundwater nitrate concentrations. The best predictive model contained a model of nitrate leaching but no land use information, implying that changes in land use will not affect designations based upon this model. The relationship between nitrate levels and borehole intake depths was investigated since there was concern that the observed contrasts in nitrate levels between vulnerability categories might be reflecting differences in borehole intake depths and not actual vulnerability. However, this was not found to be statistically important. Our preferred model provides the basis for developing a new set of groundwater Nitrate Vulnerable Zones that should help England and Wales to comply with the EU Nitrate Directive.     

Importance of Sediment–Water Interactions in Coeur d’Alene Lake,Idaho, USA: Management Implications

A field study at Coeur dAlene Lake, Idaho, USA, was conducted between October 1998 and August 2001 to examine the potential importance of sediment–water interactions on contaminant transport and to provide the first direct measurements of the benthic flux of dissolved solutes of environmental concern in this lake. Because of potential ecological effects, dissolved zinc and orthophosphate were the solutes of primary interest. Results from deployments of an in situ flux chamber indicated that benthic fluxes of dissolved Zn and orthophosphate were comparable in magnitude to riverine inputs. Tracer analyses and benthic-community metrics provided evidence that solute benthic flux were diffusion-controlled at the flux-chamber deployment sites. That is, effects of biomixing (or bioturbation) and ground-water interactions did not strongly influence benthic flux. Remediation efforts in the river might not produce desired water-quality effects in the lake because imposed shifts in concentration gradients near the sediment–water interface would generate a benthic feedback response. Therefore, development of water-quality models to justify remediation strategies requires consideration of contaminant flux between the water column and underlying sediment in basins that have been affected by long-term (decadal) anthropogenic activities.     

Comparison of Four <Emphasis Type="Italic">Sesbania</Emphasis> Species to Remediate Pb/Zn and Cu Mine Tailings

A 6-month greenhouse pot trial was performed, aimed at screening appropriate Sesbania species for remediation of Pb/Zn and Cu mine tailings. Performances of young seedlings of four Sesbania species (S. cannabina, S. grandiflora, S. rostrata, and S. sesban) were compared with and without inoculation of rhizobia. Seedlings were planted in two types of tailings amended with garden soil or garden soil mixed with river sediment. The results indicated that inoculated plants generally produced a higher biomass than samples without inoculation. Pb/Zn mine tailings containing rather high concentrations of total and water-soluble Cu, Pb, and Zn were toxic to plant growth compared with Cu mine tailings, according to the growth performance of the four species. Sesbania sesban and S. rostrata showed superior growth performance, compared to the other two species. Thus, they can serve as pioneer species to modify the barren environment, by providing organic matter and essential nutrients such as nitrogen, upon decomposition, in a relatively short period of time. This is especially true for S. rostrata, which is an annual plant that forms both stem and root nodules. However, a longer-term field trial should be conducted to investigate if superior species can beneficially modify the habitat for the growth of subsequent plant communities.     

Agricultural Land Use Effects on Sediment Loading and Fish Assemblages in Two Minnesota (USA) Watersheds

We examined the relationship between water quality and fish communities within two agricultural areas using a computer simulation model. Our analyses focused on a coolwater stream, Wells Creek in southeastern Minnesota, and a warmwater stream, the Chippewa River in western Minnesota. We used the Agricultural Drainage and Pesticide Transport (ADAPT) model in relation to land use to calculate instream suspended sediment concentrations using estimates of sediment delivery, runoff, baseflow and streambank erosion, and quantified the effects of suspended sediment exposure on fish communities. We predicted the effects of agricultural practices on stream fish communities under several possible land use scenarios, with reference to current conditions. Land use changes led to reductions in sediment loading of up to 84% in Wells Creek and 49% in the Chippewa River. The reduction in sediment loading across scenarios may be directly related to a reduction in runoff by about 35% in both study areas. We found a 98% decrease in lethal concentrations of suspended sediment on fish in Wells Creek with an increase in conservation tillage, riparian buffers, and permanent vegetative cover. However, the effects of suspended sediment did not significantly decrease in the Chippewa River. This difference between study areas was likely due to differences in tolerance to suspended sediment between coolwater and warmwater fish communities and differences in topography, runoff and bank erosion between the two streams. The Minnesota Cooperative Fish and Wildlife Research Unit is jointly sponsored by the US Geological Survey, the University of Minnesota, the Minnesota Department of Natural Resources, and the Wildlife Management Institute.     

Measuring Plant Diversity in the Tall Threetip Sagebrush Steppe: Influence of Previous Grazing Management Practices

In July 2000, a 490-ha wildfire burned a portion of a long-term grazing study that had been established in 1924 at the US Sheep Experiment Station north of Dubois, Idaho, USA. Earlier vegetation measurements in this tall threetip sagebrush (Artemisia tripartita spp. tripartita) bunchgrass plant community documented significant changes in vegetation due to grazing and the timing of grazing by sheep. A study was initiated in May 2001 using 12 multiscale modified Whittaker plots to determine the consequences of previous grazing practices on postfire vegetation composition. Because there was only one wildfire and it did not burn all of the original plots, the treatments are not replicated in time or space. We reduce the potential effects of psuedoreplication by confining our discussion to the sample area only. There were a total of 84 species in the sampled areas with 69 in the spring-grazed area and 70 each in the fall- and ungrazed areas. Vegetation within plots was equally rich and even with similar numbers of abundant species. The spring-grazed plots, however, had half as much plant cover as the fall- and ungrazed plots and the spring-grazed plots had the largest proportion of plant cover composed of introduced (27%) and annual (34%) plants. The fall-grazed plots had the highest proportion of native perennial grasses (43%) and the lowest proportion of native annual forbs (1%). The ungrazed plots had the lowest proportion of introduced plants (4%) and the highest proportion of native perennial forbs (66%). The vegetation of spring-grazed plots is in a degraded condition for the environment and further degradation may continue, with or without continued grazing or some other disturbance. If ecosystem condition was based solely on plant diversity and only a count of species numbers was used to determine plant diversity, this research would have falsely concluded that grazing and timing of grazing did not impact the condition of the ecosystem.