Assessing watershed transport of atrazine and nitrate to evaluate conservation practice effects and advise future monitoring strategies

Continued public support for U.S. taxpayer funded programs aimed at reducing agricultural pollutants depends on clear demonstrations of water quality improvements. The objective of this research was to determine if implementation of agricultural best management practices (BMPs) in the Goodwater Creek Experimental Watershed (GCEW) resulted in changes to atrazine and nitrate (NO₃–N) loads during storm events. An additional objective was to estimate future monitoring periods necessary to detect a 5, 10, 20, and 25% reduction in atrazine and NO₃–N event load. The GCEW is a 73 km² watershed located in northcentral Missouri, USA. Linear regressions and Akaike Information Criteria were used to determine if reductions in atrazine and NO₃–N event loads occurred as BMPs were implemented. No effects due to any BMP type were indicated for the period of record. Further investigation of event sampling from the long-term GCEW monitoring program indicated errors in atrazine load calculations may be possible due to pre-existing minimum threshold levels used to trigger autosampling and sample compositing. Variation of event loads was better explained by linear regressions for NO₃–N than for atrazine. Decommissioning of upstream monitoring stations during the study period represented a missed opportunity to further explain variation of event loads at the watershed outlet. Atrazine requires approximately twice the monitoring period relative to NO₃–N to detect future reductions in event load. Appropriate matching of pollutant transport mechanisms with autosampling protocols remains a critical information need when setting up or adapting watershed monitoring networks aimed at detecting watershed-scale BMP effects.     

In vitro methane removal by volcanic pumice soil biofilter columns over one year

Soil methane (CH(4)) biofilters, containing CH(4)-oxidizing bacteria (methanotrophs), are a promising technology for mitigating greenhouse gas emissions. However, little is known about long-term biofilter performance. In this study, volcanic pumice topsoils (0-10 cm) and subsoils (10-50 cm) were tested for their ability to oxidize a range of CH(4) fluxes over 1 yr. The soils were sampled from an 8-yr-old and a 2-yr-old grassed landfill cover and from a nearby undisturbed pasture away from the influence of CH(4) generated by the decomposing refuse. Methane was passed through the soils in laboratory chambers with fluxes ranging from 0.5 g to 24 g CH(4) m(-3) h(-1). All topsoils efficiently oxidized CH(4). The undisturbed pasture topsoil exhibited the highest removal efficiency (24 g CH(4) m(-3) h(-1)), indicating rapid activation of the methanotroph population to the high CH(4) fluxes. The subsoils were less efficient at oxidizing CH(4) than the topsoils, achieving a maximum rate oxidation rate of 7 g CH(4) m(-3) h(-1). The topsoils exhibited higher porosities; moisture contents; surface areas; and total C, N, and available-P concentrations than the subsoils, suggesting that these characteristics strongly influence growth and activity of the CH(4)-oxidizing bacteria. Soil pH values and available-P levels gradually declined during the trial, indicating a need to monitor chemical parameters closely so that adjustments can be made when necessary. However, other key soil physicochemical parameters (moisture, total C, total N) increased over the course of the trial. This study showed that the selected topsoils were capable of continually sustaining high CH(4) removal rates over 1 yr, which is encouraging for the development of biofilters as a low-maintenance greenhouse gas mitigation technology.     

Interference with xenobiotic metabolic activity by the commonly used vehicle solvents dimethylsulfoxide and methanol in zebrafish (Danio rerio) larvae but not Daphnia magna

Organic solvents, such as dimethylsulfoxide (DMSO) and methanol are widely used as vehicles to solubilise lipophilic test compounds in toxicity testing. However, the effects of such solvents upon innate detoxification processes in aquatic organisms are poorly understood. This study assessed the effect of solvent exposure upon cytochrome P450 (CYP)-mediated xenobiotic metabolism in Daphnia magna and zebrafish larvae (4 d post fertilisation). Adult D. magna were demonstrated to have a low, but detectable, metabolism of ethoxyresorufin in vivo and this activity was not modulated by pre-exposure to DMSO or methanol (24 h, up to 0.1% and 0.05% v/v, respectively). In contrast, the metabolism of ethoxyresorufin in zebrafish larvae was significantly reduced by both solvents (0.1% and 0.05% v/v, respectively) after 24 h of exposure. In zebrafish, these observed decreases in activity towards ethoxyresorufin were accompanied by decreased expression of a variety of genes coding for drug metabolising enzymes (corresponding to CYP1, CYP2, CYP3 and UDP-glucuronyl transferase [UGT] family enzymes), measured by quantitative PCR. Reduction of gene expression and CYP1 enzyme activities by methanol (0.05% v/v) in zebrafish larvae was partially reversed by co-exposure with Aroclor 1254 (100 μg L⁻¹). Overall this study suggests that relatively low concentrations of organic solvents can impact upon the biotransformation of certain xenobiotics in zebrafish larvae, and that this warrants consideration when assessing compounds for metabolism and toxicity in this species.     

Influence of Suwannee River humic acid on particle properties and toxicity of silver nanoparticles

Adsorption of natural organic matter (NOM) on nanoparticles can have dramatic impacts on particle dispersion resulting in altered fate and transport as well as bioavailability and toxicity. In this study, the adsorption of Suwannee River humic acid (SRHA) on silver nanoparticles (nano-Ag) was determined and showed a Langmuir adsorption at pH 7 with an adsorption maximum of 28.6 mg g⁻¹ nano-Ag. It was also revealed that addition of <10 mg L⁻¹ total organic carbon (TOC) increased the total Ag content suspended in the aquatic system, likely due to increased dispersion. Total silver content decreased with concentrations of NOM greater than 10 mg TOC L⁻¹ indicating an increase in nanoparticle agglomeration and settling above this concentration. However, SRHA did not have any significant effect on the equilibrium concentration of ionic Ag dissolved in solution. Exposure of Daphnia to nano-Ag particles (50 μg L⁻¹ and pH 7) produced a linear decrease in toxicity with increasing NOM. These results clearly indicate the importance of water chemistry on the fate and toxicity of nanoparticulates.     

A retrospective comparison of model-based forecasted PM2.5 concentrations with measurements

This study presents an assessment of the performance of the Community Multiscale Air Quality (CMAQ) photochemical model in forecasting daily PM2.5 (particulate matter < or = 2.5 microm in aerodynamic diameter) mass concentrations over most of the eastern United States for a 2-yr period from June 14, 2006 to June 13, 2008. Model predictions were compared with filter-based and continuous measurements of PM2.5 mass and species on a seasonal and regional basis. Results indicate an underprediction of PM2.5 mass in spring and summer, resulting from under-predictions in sulfate and total carbon concentrations. During winter, the model overpredicted mass concentrations, mostly at the urban sites in the northeastern United States because of overpredictions in unspeciated PM2.5 (suggesting possible overestimation of primary emissions) and sulfate. A comparison of observed and predicted diurnal profiles of PM2.5 mass at five sites in the domain showed significant discrepancies. Sulfate diurnal profiles agreed in shape across three sites in the southern portion of the domain but differed at two sites in the northern portion of the domain. Predicted organic carbon (OC) profiles were similar in shape to mass, suggesting that discrepancies in mass profiles probably resulted from the underprediction in OC. The diurnal profiles at a highly urbanized site in New York City suggested that the overpredictions at that site might be resulting from overpredictions during the morning and evening hours, displayed as sharp peaks in predicted profiles. An examination of the predicted planetary boundary layer (PBL) heights also showed possible issues in the modeling of PBL.     

Analytical Solutions to the Linearized Boussinesq Equation for Assessing the Effects of Recharge on Aquifer Discharge1

Boggs, Kevin G., Robert W. Van Kirk, Gary S. Johnson, Jerry P. Fairley, and P. Steve Porter, 2010. Analytical Solutions to the Linearized Boussinesq Equation for Assessing the Effects of Recharge on Aquifer Discharge. Journal of the American Water Resources Association (JAWRA) 46(6):1116–1132. DOI: 10.1111/j.1752-1688.2010.00479.x Abstract: There is a need to develop a general understanding of how variations in aquifer recharge are reflected in discharge. Analytical solutions to the linearized Boussinesq equation governing flow in an unconfined aquifer provide a unified mathematical framework to quantify relationships among lag time, attenuation and distance between aquifer recharge and discharge and the effect of an up-gradient no-flow boundary. We applied this framework to three types of recharge: (1) instantaneous, (2) periodic, and (3) constant rate for a finite duration. When the temporal scale of recharge exceeds the diffusive aquifer time scale, recharge will be reflected in discharge quickly and with little attenuation. When aquifer time scale is large, most recharge events are shorter in scale than that of the aquifer, resulting in large attenuation. Attenuation is more sensitive to boundary effects than lag time, and boundary effects increase as recharge time scale increases. Boundary effects can often be ignored when the recharge source is farther than 1/3 of the domain length away from the no-flow boundary. We illustrate analytical results with application to the economically critical Eastern Snake River Plain Aquifer in Idaho. In this aquifer, detectable annual and decadal cycles in discharge can result from recharge no farther than 20 and 60 km away from the discharge point, respectively. The effects of more distant, long-term recharge can be detected only after a time lag of several decades.     

Development of competitive immunoassays to hydroxyl containing fungicide metabolites

This paper describes the isolation of monoclonal antibodies and the development of competitive immunoassays to pesticide metabolites of the fungicides imazalil, carbendazim and thiabendazole. The metabolite specific hydroxyl residues were used as the reactive group with which to link the metabolite to the carrier proteins Keyhole Limpet Haemocyanin (KLH) and Bovine Serum Albumin (BSA). In each case immune responses in mice were raised and monoclonal antibodies were produced. Antibodies were developed into competitive ELISAs to the appropriate metabolite. The antibody raised to a metabolite of imazalil was optimised into a competitive ELISA format which had an assay IC50 of 7.5 μg/L and a limit of detection (LOD) of 1.1 μg/L. A single antibody isolated against the metabolite of carbendazim had assay IC50s of 3.2 and 2.7 μg/L for the metabolites of carbendazim and thiabendazole respectively with an LOD of 0.38 μg/L for both. These sensitive immunoassays may have application in the monitoring of human exposure to these fungicide residues either by occupational or non-occupational routes.     

The formation of bound residues of diazinon in four UK soils: implications for risk assessment

The behaviour of diazinon in the soil determines the likelihood of further pollution incidents, particularly leaching to water. The most significant processes in the control of the fate of diazinon in the soil are microbial degradation and the formation of bound residues. Soils from four sites in the UK were amended with diazinon and its ¹⁴C labelled analogue and incubated for 100 days. After 0, 10, 21, 50 and 100 days, the formation of bound residues was assessed by solvent extraction, and the microbial degradation of diazinon by mineralisation assay. In microbially active soils, diazinon is degraded rapidly, reducing the risk of future pollution incidents. However, where there was limited mineralisation there was also significantly lower formation of bound residues, which may lead to water pollution via leaching. The formation of bound residues was dependent on extraction type. Acetonitrile extraction identified bound residues in all soils, with the bound residue fraction increasing with increasing incubation time.     

Preventing corruption in humanitarian assistance: perceptions, gaps and challenges

Corruption is a threat to the purpose of humanitarian assistance. Until fairly recently, humanitarian assistance has not been considered an important arena in broader efforts aimed at curbing corruption, and corruption has not always been considered a particularly important concern for humanitarian assistance despite the obviously challenging nature of the context of humanitarian emergencies. Corruption, though, is a threat to humanitarian action because it can prevent assistance from getting to the people who most need it, and because it can potentially undermine public support for such assistance. This paper examines perceptions of corruption and its affects, documents best practices, and outlines gaps in understanding. It suggests recommendations for improving the capacity of humanitarian agencies to prevent and manage the risk of corruption. Agencies have taken steps to combat corruption and improve accountability--downwards and upwards--but scope remains for improvement and for greater sharing of learning and good practice.