Geospatial approaches to characterizing agriculture in the Chincoteague Bay Subbasin

Most agricultural information is reported by government sources on a state or county basis. The purpose of this study was to demonstrate use of geospatial data, the 2002 Agricultural Cropland Data Layer (CDL) for the mid-Atlantic region, to characterize agricultural, environmental, and other scientific parameters for the Chincoteague Bay subbasin using geographic information systems. This study demonstrated that agriculture can be characterized accurately on subbasin and subwatershed bases, thus complimenting various assessment technologies. Approximately 28% of the dry land of the subbasin was cropland. Field corn was the largest crop. Soybeans, either singly or double-cropped with wheat, were the second most predominant crop. Although the subbasin is relatively small, cropping practices in the northern part were different from those in the southern portion. Other crops, such as fresh vegetables and vegetables grown for processing, were less than 10% of the total cropland. A conservative approximation of the total pesticide usage in the subbasin in 2002 was over 277,000 lbs of active ingredients. Herbicides represented the most frequently used pesticides in the subbasin, both in number (17) and in total active ingredients (over 261,000 lbs). Ten insecticides predominated in the watershed, while only small quantities of three fungicides were used. Total pesticide usage and intensity were estimated using the CDL. Nutrient inputs to cropland from animal manure, chemical fertilizer, and atmospheric deposition were modeled at over 30 million pounds of nitrogen and over 7 million pounds of phosphorous. Crops under conservation tillage had the largest input of both nutrients.     

Validation of reliable and selective methods for direct determination of glyphosate and aminomethylphosphonic acid in milk and urine using LC-MS/MS

Simple high-throughput procedures were developed for the direct analysis of glyphosate [N-(phosphonomethyl)glycine] and aminomethylphosphonic acid (AMPA) in human and bovine milk and human urine matrices. Samples were extracted with an acidified aqueous solution on a high-speed shaker. Stable isotope labeled internal standards were added with the extraction solvent to ensure accurate tracking and quantitation. An additional cleanup procedure using partitioning with methylene chloride was required for milk matrices to minimize the presence of matrix components that can impact the longevity of the analytical column. Both analytes were analyzed directly, without derivatization, by liquid chromatography tandem mass spectrometry using two separate precursor-to-product transitions that ensure and confirm the accuracy of the measured results. Method performance was evaluated during validation through a series of assessments that included linearity, accuracy, precision, selectivity, ionization effects and carryover. Limits of quantitation (LOQ) were determined to be 0.1 and 10 µg/L (ppb) for urine and milk, respectively, for both glyphosate and AMPA. Mean recoveries for all matrices were within 89–107% at three separate fortification levels including the LOQ. Precision for replicates was ≤7.4% relative standard deviation (RSD) for milk and ≤11.4% RSD for urine across all fortification levels. All human and bovine milk samples used for selectivity and ionization effects assessments were free of any detectable levels of glyphosate and AMPA. Some of the human urine samples contained trace levels of glyphosate and AMPA, which were background subtracted for accuracy assessments. Ionization effects testing showed no significant biases from the matrix. A successful independent external validation was conducted using the more complicated milk matrices to demonstrate method transferability.     

Trapping phosphorus in runoff with a phosphorus removal structure

Reduction of phosphorus (P) inputs to surface waters may decrease eutrophication. Some researchers have proposed filtering dissolved P in runoff with P-sorptive byproducts in structures placed in hydrologically active areas with high soil P concentrations. The objectives of this study were to construct and monitor a P removal structure in a suburban watershed and test the ability of empirically developed flow-through equations to predict structure performance. Steel slag was used as the P sorption material in the P removal structure. Water samples were collected before and after the structure using automatic samples and analyzed for total dissolved P. During the first 5 mo of structure operation, 25% of all dissolved P was removed from rainfall and irrigation events. Phosphorus was removed more efficiently during low flow rate irrigation events with a high retention time than during high flow rate rainfall events with a low retention time. The six largest flow events occurred during storm flow and accounted for 75% of the P entering the structure and 54% of the P removed by the structure. Flow-through equations developed for predicting structure performance produced reasonable estimates of structure "lifetime" (16.8 mo). However, the equations overpredicted cumulative P removal. This was likely due to differences in pH, total Ca and Fe, and alkalinity between the slag used in the structure and the slag used for model development. This suggests the need for an overall model that can predict structure performance based on individual material properties.     

Long-term copper partitioning of metal-spiked sediments used in outdoor mesocosms

Understanding the effects of sediment contaminants is pivotal to reducing their impact in aquatic environments. Outdoor mesocosms enable us to decipher the effects of these contaminants in environmentally realistic scenarios, providing a valuable link between laboratory and field experiments. However, because of their scale, mesocosm experiments are often complex to set up and manage. The creation of environmentally realistic conditions, particularly when using artificially contaminated sediment, is one issue. Here, we describe changes in geochemistry over 1.5 years of a sediment spiked with four different concentrations of copper, within a large freshwater mesocosm facility. The spiking procedure included proportional amendments with garden lime to counteract the decreases in pH caused by the copper additions. The majority of copper within the spiked mesocosm sediments partitioned to the particulate phase with low microgram per liter concentrations measured in the pore waters and overlying waters. The minimum partition coefficient following equilibration between pore waters and sediments was 1.5?×?10⁴ L/kg, which is well within the range observed for field-contaminated sediments (1?×?10⁴ to 1?×?10⁶ L/kg). Recommendations are made for the in situ spiking of sediments with metals in large outdoor mesocosms. These include selecting an appropriate sediment type, adjusting the pH, allowing sufficient equilibration time, and regular mixing and monitoring of metal partitioning throughout the experimental period.     

Managing for Desired Experiences and Site Preferences: The Case of Fee-Fishing Anglers

Fee-fishing involves paying a fee for the privilege of fishing a body of water where fish populations are enhanced by stocking fish. Past literature on this activity has focused more on the operation of the enterprise and management of the fish than the people and site characteristics. The objectives of the study were to profile anglers and describe their site/management preferences. This study utilized an on-site interview and mail-back questionnaire at fee-fishing establishments in West Virginia (n = 212). Factor analysis of desired recreation experiences yielded five factors: Experience nature & adventure, Stress release & relaxation, Trophy fishing, Escape, and Family time. Cluster analysis showed that these anglers can be segmented into two distinct clusters, differing by sociodemographic characteristics, fishing behavior, and site/management preferences. The findings from this study provide baseline data to aid public resource managers and fee-fishing business owners in determining how to provide satisfying outdoor experiences and deliver desired services on-site. Future research will be needed from additional fee-fishing sites to obtain more detail about this outdoor recreation cohort and be able to generalize to a larger population of participants.     

Partitioning of mono- and polycyclic aromatic hydrocarbons in a river sediment adjacent to a former manufactured gas plant site

The equilibrium distributions, between water and coal-tar contaminated sediment, of 16 monocyclic and polycyclic aromatic hydrocarbons were measured and evaluated for consistency with a Raoult's Law-based quantitative relationship. The quantitative relationship calculates the pore water concentration as the product of the aqueous solubility (or for compounds that are solid at room temperature, the aqueous super-cooled liquid solubility) and the mole fraction concentration of the compound within the liquid coal tar. Sediment was collected at five locations at two depths within a 120 m stretch of a river adjacent to a former manufactured gas plant, and all samples contained non-aqueous phase liquid (NAPL) coal tar. Although the amount of coal tar varied between samples by over an order of magnitude, the Raoult's Law-based NAPL-water partition coefficients for each monocyclic or 2- or 3-ring polycyclic aromatic hydrocarbon measured in this study generally varied within a factor of 2 over all sediments.     

Laboratory studies to characterize the efficacy of sand capping a coal tar-contaminated sediment

Placement of a microbial active sand cap on a coal tar-contaminated river sediment has been suggested as a cost effective remediation strategy. This approach assumes that the flux of contaminants from the sediment is sufficiently balanced by oxygen and nutrient fluxes into the sand layer such that microbial activity will reduce contaminant concentrations within the new benthic zone and reduce the contaminant flux to the water column. The dynamics of such a system were evaluated using batch and column studies with microbial communities from tar-contaminated sediment under different aeration and nutrient inputs. In a 30-d batch degradation study on aqueous extracts of coal tar sediment, oxygen and nutrient concentrations were found to be key parameters controlling the degradation rates of polycyclic aromatic hydrocarbons (PAHs). For the five PAHs monitored (naphthalene, fluorene, phenanthrene, anthracene, and pyrene), degradation rates were inversely proportional to molecular size. For the column studies, where three columns were packed with a 20-cm sand layer on the top of a 5 cm of sediment layer, flow was established to sand layers with (1) aerated water, (2) N(2) sparged water, or (3) HgCl(2)-sterilized N(2) sparged water. After steady-state conditions, PAH concentrations in effluents were the lowest in the aerated column, except for pyrene, whose concentration was invariant with all effluents. These laboratory scale studies support that if sufficient aeration can be achieved in the field through either active and passive means, the resulting microbially active sand layer can improve the water quality of the benthic zone and reduce the flux of many, but not all, PAHs to the water column.