Sequential Extraction Versus Comprehensive Characterization of Heavy Metal Species in Brownfield Soils

The applicability of sequential extraction as a means to determine species of heavy-metals was examined by a study on soil samples from two Superfund sites: the National Lead Company site in Pedricktown, NJ, and the Roebling Steel, Inc., site in Florence, NJ. Data from a standard sequential extraction procedure were compared to those from a comprehensive study that combined optical- and scanning-electron microscopy, X-ray diffraction, and chemical analyses. The study shows that larger particles of contaminants, encapsulated contaminants, and/or man-made materials such as slags, coke, metals, and plastics are subject to incasement, non-selectivity, and redistribution in the sequential extraction process. The results indicate that standard sequential extraction procedures that were developed for characterizing species of contaminants in river sediments may be unsuitable for stand-alone determinative evaluations of contaminant species in industrial-site materials. However, if employed as part of a comprehensive, site-specific characterization study, sequential extraction could be a very useful tool.     

Prediction of Streamflow Regime and Annual Runoff for Ungauged Basins Using a Distributed Monthly Water Balance Model1

Moore, R.D. (Dan), J.W. Trubilowicz, and J.M. Buttle, 2011. Prediction of Streamflow Regime and Annual Runoff for Ungauged Basins Using a Distributed Monthly Water Balance Model. Journal of the American Water Resources Association (JAWRA) 48(1): 32‐42. DOI: 10.1111/j.1752‐1688.2011.00595.x Abstract: Prediction of streamflow in ungauged basins is a global challenge, but is particularly an issue in physiographically complex regions like British Columbia (BC), Canada. The objective of this study was to assess the accuracy of a simple water balance model that can be run using existing spatial datasets. The model was developed by modifying an existing monthly water balance model to account for interception loss from forest canopy, glacier melt, and evaporation from lakes. The model was run using monthly climate normals from the ClimateBC application, which have a horizontal resolution of 400 m. Each ClimateBC grid cell was classified as forest, open land, glacier or water surface based on provincial scale digital maps of biogeoclimatic zones, glaciers, and water. The output was monthly mean runoff from each grid cell. These values were integrated within the catchment boundaries for streams gauged by the Water Survey of Canada. Annual runoff was predicted with modest accuracy: after updating the predicted runoff by interpolating errors from neighboring gauged streams, the mean absolute error was 25.4% of the gauged value, and 52% of the streams had errors less than 20%. However, the model appears to be quite robust in distinguishing between pluvial, hybrid, and melt‐dominated hydroclimatic regimes, and therefore has promise as a tool for catchment classification.     

Watershed Regressions for Pesticides (warp) Models for Predicting Atrazine Concentrations in Corn Belt Streams1

Stone, Wesley W. and Robert J. Gilliom, 2012. Watershed Regressions for Pesticides (WARP) Models for Predicting Atrazine Concentrations in Corn Belt Streams. Journal of the American Water Resources Association (JAWRA) 48(5): 970‐986. DOI: 10.1111/j.1752‐1688.2012.00661.x Abstract: Watershed Regressions for Pesticides (WARP) models, previously developed for atrazine at the national scale, are improved for application to the United States (U.S.) Corn Belt region by developing region‐specific models that include watershed characteristics that are influential in predicting atrazine concentration statistics within the Corn Belt. WARP models for the Corn Belt (WARP‐CB) were developed for annual maximum moving‐average (14‐, 21‐, 30‐, 60‐, and 90‐day durations) and annual 95th‐percentile atrazine concentrations in streams of the Corn Belt region. The WARP‐CB models accounted for 53 to 62% of the variability in the various concentration statistics among the model‐development sites. Model predictions were within a factor of 5 of the observed concentration statistic for over 90% of the model‐development sites. The WARP‐CB residuals and uncertainty are lower than those of the National WARP model for the same sites. Although atrazine‐use intensity is the most important explanatory variable in the National WARP models, it is not a significant variable in the WARP‐CB models. The WARP‐CB models provide improved predictions for Corn Belt streams draining watersheds with atrazine‐use intensities of 17 kg/km² of watershed area or greater.     

Modeled Summer Background Concentration of Nutrients and Suspended Sediment in the Mid‐Continent (USA) Great Rivers1

Angradi, Ted R., David W. Bolgrien, Matt A. Starry, and Brian H. Hill, 2012. Modeled Summer Background Concentration of Nutrients and Suspended Sediment in the Mid‐Continent (USA) Great Rivers. Journal of the American Water Resources Association (JAWRA) 48(5): 1054‐1070. DOI: 10.1111/j.1752‐1688.2012.00669.x Abstract: We used regression models to predict summer background concentration of total nitrogen (N), total phosphorus (P), and total suspended solids (TSS), in the mid‐continent great rivers: the Upper Mississippi, the Lower Missouri, and the Ohio. From multiple linear regressions of water quality indicators with land use and other stressor variables, we determined the concentration of the indicators when the predictor variables were all set to zero — the y‐intercept. Except for total P on the Upper Mississippi River, we could predict background concentration using regression models. Predicted background concentration of total N was about the same on the Upper Mississippi and Lower Missouri Rivers (430 μg l^?1), which was lower than percentile‐based values, but was similar to concentrations derived from the response of sestonic chlorophyll a to great river total N concentration. Background concentration of total P on the Lower Missouri (65 μg l^?1) was also lower than published and percentile‐based concentrations. Background TSS concentration was higher on the Lower Missouri (40 mg l^?1) than the other rivers. Background TSS concentration on the Upper Mississippi (16 mg l^?1) was below a threshold (30 mg l^?1) designed to protect aquatic vegetation. Our model‐predicted concentrations for the great rivers are an attempt to estimate background concentrations for water quality indicators independent from thresholds based on percentiles or derived from stressor‐response relationships.     

Photocatalytic oxidation of monuron in the suspension of WO3 under the irradiation of UV-visible light

A comprehensive study of the degradation of monuron, one of the phenylurea herbicides, was conducted by UV-Vis/WO₃ process. It was found that hydroxyl radicals played a major role in the decay of monuron while other radicals (e.g. superoxide) and hole might also contribute to the decomposition of monuron. The oxidation path likely plays a major role in the generation of hydroxyl radicals. The effects of initial pH level, initial concentration of monuron, and inorganic oxidants on the performance of UV-Vis/WO₃ process were also investigated and optimized. Comparison between monuron decay pathways by UV-Vis/WO₃ and UV/TiO₂ was conducted. The decay mechanisms, including N-terminus demethylation, dechlorination and direct hydroxylation on benzene ring, were observed to be involved in the oxidation of monuron in these two processes. Sixteen intermediates were identified during the photodegradation of monuron and degradation pathways were proposed accordingly.     

Evaluation of effects of exposure time on aquatic toxicity with zooplanktons using a reduced life expectancy model

Traditionally in toxicological studies time is not studied as quantifiable variable but as a fixed endpoint. The Reduced Life Expectancy (RLE) model which relates exposure time and exposure concentration with lethal toxic effects was tested previously using fish data. In this current paper the effects of exposure time on aquatic toxicity with zooplanktons and various toxicants were evaluated using the RLE model based on ambient exposure concentration. The model was evaluated by plotting ln LT₅₀ against LC₅₀ using toxicity data with zooplanktons from the literature for metal, metalloid and organic compounds. Most of the experimental data sets can be satisfactorily correlated by use of the RLE model, but deviations occurred for some data sets. Those data sets were satisfactorily fitted by a two stage RLE model. This model was based on two phases: one in the peripheral system and other in the central system. Both the single and two stage RLE model support the hypothesis that toxicity is time dependent and decreases in a systematic way with increasing exposure time. A calculated normal life expectancy (NLT) can be obtained from the single stage model and is in accord with reported NLT but those obtained from the two stage RLE model are in excellent agreement.     

Changes in the pore network structure of Hanford sediment after reaction with caustic tank wastes

At the former nuclear weapon production site in Hanford, WA, caustic radioactive tank waste leaks into subsurface sediments and causes dissolution of quartz and aluminosilicate minerals, and precipitation of sodalite and cancrinite. This work examines changes in pore structure due to these reactions in a previously-conducted column experiment. The column was sectioned and 2D images of the pore space were generated using backscattered electron microscopy and energy dispersive X-ray spectroscopy. A pre-precipitation scenario was created by digitally removing mineral matter identified as secondary precipitates. Porosity, determined by segmenting the images to distinguish pore space from mineral matter, was up to 0.11 less after reaction. Erosion-dilation analysis was used to compute pore and throat size distributions. Images with precipitation had more small and fewer large pores. Precipitation decreased throat sizes and the abundance of large throats. These findings agree with previous findings based on 3D X-ray CMT imaging, observing decreased porosity, clogging of small throats, and little change in large throats. However, 2D imaging found an increase in small pores, mainly in intragranular regions or below the resolution of the 3D images. Also, an increase in large pores observed via 3D imaging was not observed in the 2D analysis. Changes in flow conducting throats that are the key permeability-controlling features were observed in both methods.     

Microwave enhanced advanced oxidation process for treating dairy manure at low pH

This study investigated the treatment of dairy manure using the microwave enhanced advanced oxidation process (MW-AOP) at pH 2. An experimental design was developed based on a statistical program using response surface methodology to explore the effects of temperature, hydrogen peroxide dosage and heating time on sugar production, nutrient release and solids destruction. Temperature, hydrogen peroxide dosage and acid concentration were key factors affecting reducing sugar production. The highest reducing sugar yield of 7.4% was obtained at 160°C, 0 mL, 15 min heating time, and no H(2)O(2) addition. Temperature was a dominant factor for an increase of soluble chemical oxygen demand (SCOD) in the treated dairy manure. The important factors for volatile fatty acids (VFA) production were microwave temperature and hydrogen peroxide dosage. Temperature was the most important parameter, and heating time, to a lesser extent affecting orthophosphate release. Heating time, hydrogen peroxide dosage and temperature were significant factors for ammonia release. There was a maximum of 96% and 196% increase in orthophosphate and ammonia concentration, respectively at 160°C, 0.5 mL H(2)O(2) and 15 min heating time. The MW-AOP is an effective method in dairy manure treatment for sugar production, nutrient solubilisation, and solids disintegration.     

Persistence of repeated triadimefon application and its impact on soil microbial functional diversity

The effects of repeated applications of the fungicide triadimefon in agricultural soil on the microbial functional diversity of the soil and on the persistence of the fungicide in the soil were investigated under laboratory conditions. The degradation half-lives of triadimefon at the recommended dosage, simulated by a first-order kinetic model, were 23.90, 22.95, and 21.52 days for the first, second, and third applications, respectively. Throughout this study, no significant inhibition of the Shannon-Wiener index (H') was observed. However, the Simpson index (1/D) and the McIntosh index (U) were obviously reduced (p ≤ 0.05) during the initial 3 days after the first triadimefon application and thereafter, gradually recovered to or exceeded the level of the control soil. A similar trend in variation but with a faster recovery in the 1/D and U was observed after the second and third triadimefon applications, respectively. Taken together, the above results indicate that the repeated application of triadimefon enhanced the degradation rate of the fungicide and the recovery rate of the soil microbial functional diversity. It is concluded that repeated triadimefon applications in soil have a transient or temporary inhibitory effect on soil microbial communities.