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.     

Roles of land use resolution and unit-area load rates in assessment of diffuse nutrient emissions

In contrast to its counterparts in Europe and North America, the Australian National Pollutant Inventory (NPI) includes estimates of aggregated emissions of nutrients (total nitrogen and total phosphorus) from catchments and facilities. Sparse or inadequate data limit the extent to which nutrient exports may be estimated from direct observations. The paucity of data for calibration and simulation limits the use of sophisticated models in most Australian catchments. Therefore, a simple unit-area load model-Catchment Management Support System (CMSS)-was selected to estimate aggregated catchment emissions for the NPI. Estimates from models like CMSS are sensitive to spatial and categorical resolution of land uses identified within the catchment and to nutrient generation rates selected for each land use category. Using three Hawkesbury-Nepean subcatchments, we show that while high spatial resolution of land use mapping is useful, only four or five major land use categories with carefully selected generation rates were required to estimate potential nutrient exports sufficiently well and to determine subcatchments contributing most. Nutrient emission estimates proved to be highly dependent on selection of generation rates so a bootstrap technique was adopted to reduce subjectivity and to improve estimates of confidence limits. This led to a specification of new generation rates for Natural, Unimproved pasture, Rural and Urban land uses and to establishment of uncertainty limits.     

Geographic Analysis of Forest Health Indicators Using Spatial Scan Statistics

Geographically explicit analysis tools are needed to assess forest health indicators that are measured over large regions. Spatial scan statistics can be used to detect spatial or spatiotemporal clusters of forests representing hotspots of extreme indicator values. This paper demonstrates the approach through analyses of forest fragmentation indicators in the southeastern United States and insect and pathogen indicators in the Pacific Northwest United States. The scan statistic detected four spatial clusters of fragmented forest including a hotspot in the Piedmont and Coastal Plain region. Three recurring clusters of insect and pathogen occurrence were found in the Pacific Northwest. Spatial scan statistics are a powerful new tool that can be used to identify potential forest health problems.     

Field testing of particulate matter continuous emission monitors at the DOE Oak Ridge TSCA incinerator. Toxic Substances Control Act

A field study to evaluate the performance of three commercially available particulate matter (PM) continuous emission monitors (CEMs) was conducted in 1999-2000 at the US Department of Energy (DOE) Toxic Substances Control Act (TSCA) Incinerator. This study offers unique features that are believed to enhance the collective US experience with PM CEMs. The TSCA Incinerator is permitted to treat PCB-contaminated RCRA hazardous low-level radioactive wastes. The air pollution control system utilizes MACT control technology and is comprised of a rapid quench, venturi scrubber, packed bed scrubber, and two ionizing wet scrubbers in series, which create a saturated flue gas that must be conditioned by the CEMs prior to measurement. The incinerator routinely treats a wide variety of wastes including high and low BTU organic liquids, aqueous, and solid wastes. The various possible combinations for treating liquid and solid wastes may present a challenge in establishing a single, acceptable correlation relationship for individual CEMs. The effect of low-level radioactive material present in the waste is a unique site-specific factor not evaluated in previous tests. The three systems chosen for evaluation were two beta gauge devices and a light scattering device. The performance of the CEMs was evaluated using the requirements in draft Environmental Protection Agency (EPA) Performance Specification 11 (PS11) and Procedure 2. The results of Reference Method 5i stack tests for establishing statistical correlations between the reference method data and the CEMs responses are discussed.     

Chemistry of Selected High-Elevation Lakes in Seven National Parks in the Western United States

A chemical survey of 69 high-altitude lakes in seven national parks in the western United States was conducted during the fallof 1999; the lakes were previously sampled during the fall of 1985, as part of the Western Lake Survey. Lakes in parks in the Sierra/southern Cascades (Lassen Volcanic, Yosemite, Sequoia/Kings Canyon National Parks) and in the southern RockyMountains (Rocky Mountain National Park) were very dilute; medianspecific conductance ranged from 4.4 to 12.2 S cm^-1 andmedian alkalinity concentrations ranged from 32.2 to 72.9 eqL^-1. Specific conductances and alkalinity concentrations were substantially higher in lakes in the central and northernRocky Mountains parks (Grand Teton, Yellowstone, and GlacierNational Parks), probably due to the prevalence of more reactivebedrock types. Regional patterns in lake concentrations of NO₃ and SO₄ were similar to regional patterns in NO₃ and SO₄ concentrations in precipitation, suggestingthat the lakes are showing a response to atmospheric deposition.Concentrations of NO₃ were particularly high in Rocky Mountain National Park, where some ecosystems appear to be undergoing nitrogen saturation.     

A statistical approach to estimate O3 uptake of ponderosa pine in a mediterranean climate

In highly polluted sites, stomatal behavior is sluggish with respect to light, vapor pressure deficit, and internal CO2 concentration (Ci) and poorly described by existing models. Statistical models were developed to estimate stomatal conductance (gs) of 40-year-old ponderosa pine at three sites differing in pollutant exposure for the purpose of calculating O3 uptake. Gs was estimated using julian day, hour of day, pre-dawn xylem potential and photosynthetic photon flux density (PPFD). The median difference between estimated and observed field gs did not exceed 10 mmol H2O m(-2) s(-1), and estimated gs within 95% confidence intervals. 03 uptake was calculated from hourly estimated gs, hourly O3 concentration, and a constant to correct for the difference in diffusivity between water vapor and 03. The simulation model TREGRO was also used to calculate the cumulative 03 uptake at all three sites. 03 uptake estimated by the statistical model was higher than that simulated by TREGRO because gas exchange rates were proportionally higher. O3 exposure and uptake were significantly correlated (r2>0.92), because O3 exposure and gs were highly correlated in both statistical and simulation models.     

Response of Ceriodaphnia dubia to ionic silver: discrepancies among model predictions, measured concentrations and mortality

Silver thiosulfate, often a waste product of photoprocessing, is less bioavailable or toxic to aquatic organisms than is ionic silver. We conducted duplicate 48-h Ceriodaphnia dubia tests in reconstituted laboratory water using treatments of 92.7 nM Ag+ with various concentrations of thiosulfate. Expected Ag+ concentrations were generated for thiosulfate treatment levels using MINEQL + chemical equilibrium modeling. Ag+ concentrations in treatments were determined using a novel silicon-based sensor. Based on predicted Ag+ and published 48-h LC50 values for C. dubia, we did not expect to observe adverse effects. Yet, 100% mortality was observed at low thiosulfate treatments, whereas > 85% and > 95% survival was observed at higher thiosulfate treatment levels, respectively. Our results indicate that biotic responses match the sensor-based Ag+ concentrations. However, there is a discrepancy between these empirical results and responses expected to occur with Ag+ concentrations as predicted by MINEQL + chemical modeling. By correlating silicon sensor data with toxicity results obtained from our laboratory, our work clearly relates a specific chemical form (Ag+) to toxicity results.     

A GIS/Simulation Framework for Assessing Change in Water Yield over Large Spatial Scales

Recent legislation to initiate vegetation management in the Central Sierra hydrologic region of California includes a focus on corresponding changes in water yield. This served as the impetus for developing a combined geographic information system (GIS) and simulation assessment framework. Using the existing vegetation density condition, together with proposed rules for thinning to reduce fire risk, a set of simulation model inputs were generated for examining the impact of the thinning scenario on water yield. The approach allows results to be expressed as the mean and standard deviation of change in water yield for each 1-km² map cell that is thinned. Values for groups of cells are aggregated for typical watershed units using area-weighted averaging. Wet, dry, and average precipitation years were simulated over a large region. Where snow plays an important role in hydrologic processes, the simulated change in water yield was less than 0.5% of expected annual runoff for a typical watershed. Such small changes would be undetectable in the field using conventional stream flow analysis. These results suggest that use of water yield increases to help justify forest-thinning activities or offset their cost will be difficult.     

Stray field nuclear magnetic resonance of soil water: development of a new, large probe and preliminary results

Development, characterization, and preliminary results of a recent technique capable of local measurements of pore-size distribution by a spatially resolved low resolution nuclear magnetic resonance (NMR) technique are described. Potential environmental uses include studying the change in pore-size distribution caused by surface compaction, which influences surface runoff, and obtaining information on the physical state of non-aqueous compounds in porous materials, which should aid the selection of appropriate soil remediation methods. Stray field (STRAFI) imaging is an NMR technique that allows distortion-free imaging of materials with short NMR relaxation times. The sample is placed in the strong axial fringe field gradient of a superconducting NMR magnet. We report on a new, unique, large 5-cm-diameter STRAFI probe, and its use for three preliminary test cases: water in ceramics of known pore size, paraffin wax and oil in sandstone rock, and water in soil at different matric potentials. The imaging is confined to one dimension with a spatial resolution of the order of 100 microm for protons. The optimum position for imaging occurs at 2.62 T and a gradient of 12.1 T/m. Water relaxation decay curves can be measured at any position in the 8-cm-long sample. These curves are decomposed into a series of terms each corresponding to a different pore size. Preliminary results show continuum fits to decay curves for a soil drained to three different matric potentials. Such information will be useful for interpreting water retention curves and will lead to understanding of the behavior of fluids in the vadose zone.