Development,validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water,soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L^?1, and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L^?1), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L^?1 and 20.4, 9.0, 21.6, and 13.0 ng L^?1, respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L^?1 and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg^?1), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg^?1), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg^?1). The relative standard deviation for the recovery of pesticides was under 15%.     

Structural changes in soil communities after triclopyr application in soils invaded by Acacia dealbata Link

Triclopyr is a commonly used herbicide in the control of woody plants and can exhibit toxic effects to soil microorganisms. However, the impact on soils invaded by plant exotics has not yet been addressed. Here, we present the results of an 18-month field study conducted to evaluate the impact of triclopyr on the structure of fungal and bacterial communities in soils invaded by Acacia dealbata Link, through the use of denature gradient gel electrophoresis. After triclopyr application, analyses of bacterial fingerprints suggested a change in the structure of the soil bacterial community, whereas the structure of the soil fungal community remained unaltered. Bacterial density and F:B ratio values changed across the year but were not altered due to herbicide spraying. On the contrary, fungal diversity was increased in plots sprayed with triclopyr 5 months after the first application. Richness and diversity (H´) of both bacteria and fungi were not modified after triclopyr application.     

Guidance for the Field Demonstration of Remediation Technologies

This paper will focus on the demonstration of hazardous waste cleanup technologies in the field. The technologies will be at the pilot- or full-scale, and further referred to as field-scale. The main objectives of demonstration at the field-scale are development of reliable performance and cost data. Technology demonstrations provide performance, cost effectiveness, and reliability data so that potential technology users have sufficient information to make effective decisions as to the applicability of the technology to a specific situation. The demonstration and evaluation of a technology should be conducted with the purpose of characterizing performance, need for pre- and post-processing of the waste feed, identification of waste type and constituents applicable to the technology, system throughput, problems and limitations of the technology, and operating and maintenance costs. Table I provides a summary of remediation activities for demonstration projects.     

Modeling Emissions from Elevated Cylindrical Bins

Abstract

This paper demonstrates how wind tunnel modeling data that accurately describe plume characteristics near an unconventional emission source can be used to improve the near-field downwind plume profiles predicted by conventional air pollution dispersion models. The study considers a vertical, cylindrical-shaped, elevated bin similar to large product storage bins that can be found at many industrial plant sites. Two dispersion models are considered: the U.S. Environmental Protection Agency's ISC2(ST) model and the Ontario Ministry of the Environment and Energy's GAS model. The wind tunnel study showed that plume behavior was contrary to what was predicted using conventional dispersion models such as ISC2(ST) and GAS and default values of input parameters. The wind tunnel data were used to develop a protocol for correcting the dispersion models inputs, resulting in a substantial improvement in the accuracy of the dispersion estimates.     

An Air Quality Modeling Study Comparing Two Possible Sites for the New International Airport for Mexico City

Abstract

Using an air quality model, two future urban scenarios induced by the construction of the new international airport for Mexico City are compared at a regional level. The air quality model couples the meteorology model MM5 and state-of-the-art photochemistry. The air quality comparison is made using metrics for the criterion gases selected for the study. From the two urban scenarios compared, the option for Tizayuca is moderately better than the option for Texcoco, because relative reductions in O₃ and other photochemical pollutants are achieved over highly populated areas. Regardless of the site, the air quality for the central region of Mexico in the future will deteriorate. In the region of central Mexico, SO₂ and NO₂ will become important pollutants.     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): Overview and Statistical Considerations

Abstract

Average concentrations of particulate matter with an aerodynamic diameter less than or equal to 2.5 μm (PM_2.5) in Steubenville, OH, have decreased by more than 10 μg/m³ since the landmark Harvard Six Cities Study¹ associated the city’s elevated PM_2.5 concentrations with adverse health effects in the 1980s. Given the promulgation of a new National Ambient Air Quality Standard (NAAQS) for PM_2.5 in 1997, a current assessment of PM_2.5 in the Steubenville region is warranted. The Steubenville Comprehensive Air Monitoring Program (SCAMP) was conducted from 2000 through 2002 to provide such an assessment. The program included both an outdoor ambient air monitoring component and an indoor and personal air sampling component. This paper, which is the first in a series of four that will present results from the outdoor portion of SCAMP, provides an overview of the outdoor ambient air monitoring program and addresses statistical issues, most notably autocorrelation, that have been overlooked by many PM_2.5 data analyses. The average PM_2.5 concentration measured in Steubenville during SCAMP (18.4 μg/m³) was 3.4g/m³ above the annual PM_2.5 NAAQS. On average, sulfate and organic material accounted for ～31% and 25%, respectively, of the total PM_2.5 mass. Local sources contributed an estimated 4.6 μg/m³ to Steubenville’s mean PM_2.5 concentration. PM_2.5 and each of its major ionic components were significantly correlated in space across all pairs of monitoring sites in the region, suggesting the influence of meteorology and long-range transport on regional PM_2.5 concentrations. Statistically significant autocorrelation was observed among time series of PM_2.5 and component data collected at daily and 1-in-4-day frequencies during SCAMP. Results of spatial analyses that accounted for autocorrelation were generally consistent with findings from previous studies that did not consider autocorrelation; however, these analyses also indicated that failure to account for autocorrelation can lead to incorrect conclusions about statistical significance.     

Identifying Differences Between Off-Highway Vehicle (OHV) and Non-OHV User Groups for Recreation Resource Planning

Off-highway vehicle (OHV) riding is among the fastest growing recreational activities in the United States. However, little research exists about the central components of outcomes-focused management (OFM) as it relates to motorized recreation. Utilizing a two-activity dichotomy, OHV and non-OHV centric user groups were compared on several key concepts associated with OFM, including desired experiences, perceived and desired recreation opportunity spectrum-type settings, and intentional behaviors (i.e., place-protective behavior, spending-time intentions) toward potential changes in settings. Results indicated that the two groups were different in terms of intensity and relative rankings of their perceived experiences and settings. Although both groups preferred social bonding, stress relief, nostalgia and learning experiences, the OHV user group ranked using equipment and achieving physical fitness experiences as more important than the non-OHV group. The non-OHV user group preferred enjoying nature and solitude/tranquility experiences more strongly than the OHV user group. Further analysis found that both groups perceived settings that they recreated in to be pristine and preferred such conditions, and both groups preferred moderate levels of rules and regulations. Finally, the OHV user group was more reactive to rules and regulations, while the non-OHV user group expressed stronger intentions to protect the environmental quality of recreation areas. The results suggest that planners and managers who understand OHV user's perceptions and behaviors could provide enhanced recreation opportunities potentially providing additional beneficial outcomes for motorized and non-motorized groups in spatially different zones. Additional implications for planners and managers and future studies are discussed.     

River Restoration in Spain: Theoretical and Practical Approach in the Context of the European Water Framework Directive

River restoration is becoming a priority in many countries because of increasing the awareness of environmental degradation. In Europe, the EU Water Framework Directive (WFD) has significantly reinforced river restoration, encouraging the improvement of ecological status for water bodies. To fulfill the WFD requirements, the Spanish Ministry of the Environment developed in 2006 a National Strategy for River Restoration whose design and implementation are described in this paper. At the same time many restoration projects have been conducted, and sixty of them have been evaluated in terms of stated objectives and pressures and implemented restoration measures. Riparian vegetation enhancement, weir removal and fish passes were the most frequently implemented restoration measures, although the greatest pressures came from hydrologic alteration caused by flow regulation for irrigation purposes. Water deficits in quantity and quality associated with uncontrolled water demands seriously affect Mediterranean rivers and represent the main constraint to achieving good ecological status of Spanish rivers, most of them intensively regulated. Proper environmental allocation of in-stream flows would need deep restrictions in agricultural water use which seem to be of very difficult social acceptance. This situation highlights the need to integrate land-use and rural development policies with water resources and river management, and identifies additional difficulties in achieving the WFD objectives and good ecological status of rivers in Mediterranean countries.     

Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System1

Stoeckel, James A., Jade Morris, Elizabeth Ames, David C. Glover, Michael J. Vanni, William Renwick, and María J. González, 2012. Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System. Journal of the American Water Resources Association (JAWRA) 48(3): 616-634. DOI: 10.1111/j.1752-1688.2011.00633.x Abstract: We used enzyme-linked immunosorbent assay to examine reservoir-mediated shifts in spring to fall exposure of aquatic organisms to the spring atrazine pulse over four years in a Midwestern stream-reservoir system. Peak atrazine concentrations in the major inflowing stream exceeded 10 μg/l in all four years. The reservoir had a beneficial effect in two of four years by diluting atrazine below the 10 μg/l threshold. However, during the other two years, exposure times above 10 μg/l were approximately doubled in the reservoir compared to the major inflowing stream. Thresholds of 3 and 5 μg/l were exceeded during all four years in the reservoir. The uplake and downlake reservoir sites were four to five times more likely to exceed these thresholds and aquatic organisms were subjected to longer exposure times above these thresholds compared to the inflowing stream. Release of elevated atrazine concentrations from the reservoir extended exposure times in the outflowing stream. This effect was most pronounced just below the dam. Aquatic organisms upstream of the reservoir were most likely to experience acute exposures whereas organisms within and immediately downstream of the reservoir were more likely to experience chronic exposures. The ubiquity of reservoirs and the annual spring herbicide flush highlight the importance of considering the presence and relative location of reservoirs when assessing risk to aquatic communities as well as locations of drinking water intakes.