Occurrence of boscalid and other selected fungicides in surface water and groundwater in three targeted use areas in the United States

Although the use of the insecticide γ-hexachlorocyclohexane (HCH) is now prohibited in many countries because of its hazardousness, stockpiles of γ-HCH still exist. In this study, we subjected γ-HCH to mechanochemical (MC) treatment with a planetary ball mill in the presence of CaO to investigate the feasibility of using this method for the treatment of γ-HCH stockpiles. We confirmed the degradation of γ-HCH and investigated the degradation mechanism. The major intermediates were identified to be 1,3,4,5,6-pentachlorocyclohexene (γ-PCCH) and chlorobenzenes (CBzs). Analysis of the steric structure of γ-HCH and identification of the degradation intermediates suggested that successive dehydrochlorination led to the formation of trichlorobenzenes. Products of further degradation (dichlorobenzenes, monochlorobenzene, and benzene) were also detected. Surprisingly, methane and ethane were also detected, which suggests cleavage of the C-C bonds of the cyclohexane ring and hydrogenation. All of the chlorine atoms in the γ-HCH could be transformed into inorganic chloride compounds by the MC treatment with CaO. Our results indicate that γ-HCH can be completely dechlorinated by MC treatment.     

Post-fire surface water quality: comparison of fire retardant versus wildfire-related effects

An understanding of the environmental effects of the use of wildland fire retardant is needed to provide informed decision-making regarding forest management. We compiled data from all post-fire surface water monitoring programs where the fire retardant constituents ammonia, phosphorus, and cyanide were measured, and data were available in the public domain. For streams near four major wildfires, we evaluated whether these chemicals originated primarily from fire or from retardant use. We compared measured concentrations in streams where chemical wildland fire retardant was applied with concentrations in streams draining areas where retardant was not used. Correlations with calcium provided an additional line of evidence, because calcium concentrations in ash are much higher than in retardant. Ammonia, phosphorus, and total cyanide were found in streams in burned areas where retardant was not used, at concentrations similar to those found in areas where retardant was applied. Concentrations of weak acid dissociable cyanide were generally non-detected or very low, whether or not wildland fire retardant was used in the watershed. These results indicate that the application of wildland fire retardant had minimal effects on proximate surface water quality. Cyanide concentrations in post-fire stormwater runoff were not affected by the presence of ferrocyanide in the retardant formulas and were due to pyrogenic sources.     

Copper desorption in flooded agricultural soils and toxicity to the Florida apple snail (Pomacea paludosa): implications in Everglades restoration

Copper (Cu) desorption and toxicity to the Florida apple snail were investigated from soils obtained from agricultural sites acquired under the Comprehensive Everglades Restoration Plan. Copper concentrations in 11 flooded soils ranged from 5 to 234 mg/kg on day 0 and from 6.2 to 204 mg/kg on day 28 (steady-state). The steady-state Cu concentration in overlying water ranged from 9.1 to 308.2 microg/L. In a 28-d growth study, high mortality in snails occurred within 9 to 16 d in two of three soil treatments tested. Growth of apple snails over 28 d was affected by Cu in these two treatments. Tissue Cu concentrations by day 14 were 12-23-fold higher in snails exposed to the three soil treatments compared to controls. The endangered Florida snail kite and its main food source, the Florida apple snail, may be at risk from Cu exposure in these managed agricultural soil-water ecosystems.     

Transport and dispersion during wintertime particulate matter episodes in the San Joaquin Valley, California

Data analysis and modeling were performed to characterize the spatial and temporal variability of wintertime transport and dispersion processes and the impact of these processes on particulate matter (PM) concentrations in the California San Joaquin Valley (SJV). Radar wind profiler (RWP) and radio acoustic sounding system (RASS) data collected from 18 sites throughout Central California were used to estimate hourly mixing heights for a 3-month period and to create case studies of high-resolution diagnostic wind fields, which were used for trajectory and dispersion analyses. Data analyses show that PM episodes were characterized by an upper-level ridge of high pressure that generally produced light winds through the entire depth of the atmospheric boundary layer and low mixing heights compared with nonepisode days. Peak daytime mixing heights during episodes were -400 m above ground level (agl) compared with -800 m agl during nonepisodes. These episode/nonepisode differences were observed throughout the SJV. Dispersion modeling indicates that the range of influence of primary PM emitted in major population centers within the SJV ranged from -15 to 50 km. Trajectory analyses revealed that little intrabasin pollutant transport occurred among major population centers in the SJV; however, interbasin transport from the northern SJV and Sacramento regions into the San Francisco Bay Area (SFBA) was often observed. In addition, this analysis demonstrates the usefulness of integrating RWP/RASS measurements into data analyses and modeling to improve the understanding of meteorological processes that impact pollution, such as aloft transport and boundary layer evolution.     

The mobile source effect on curbside 1,3-butadiene,benzene, and particle-bound polycyclic aromatic hydrocarbons assessed at a tollbooth

On-road mobile sources contribute substantially to ambient air concentrations of the carcinogens 1,3-butadiene, benzene, and polycyclic aromatic hydrocarbons (PAHs). The current study measured benzene and 1,3-butadiene at the Baltimore Harbor Tunnel tollbooth over 3-hr intervals on seven weekdays (n = 56). Particle-bound PAH was measured on a subset of three days. The 3-hr outdoor 1,3-butadiene levels varied according to time of day and traffic volume. The minimum occurred at night (12 a.m.-3 a.m.) with a mean of 2 microg/m3 (SD = 1.3, n = 7), while the maximum occurred during the morning rush hour (6 a.m.-9 a.m.) with a mean of 11.9 microg/m3 (SD = 4.6, n = 7). The corresponding traffic counts were 1413 (SD = 144) and 16,893 (SD = 692), respectively. During the same intervals, mean benzene concentration varied from 3 microg/m3 (SD = 3.1, n = 7) to 22.3 microg/m3 (SD = 7.6, n = 7). Median PAH concentrations ranged from 9 to 199 ng/m3. Using multivariate regression, a significant association (p < 0.001) between traffic and curbside concentration was observed. Much of the pollutant variability (1,3-butadiene 62%, benzene 77%, and PAH 85%) was explained by traffic volume, class, and meteorology. Results suggest > 2-axle vehicles emit 60, 32, and 9 times more PAH, 1,3-butadiene, and benzene, respectively, than do 2-axle vehicles. This study provides a model for estimating curbside pollution levels associated with traffic that may be relevant to exposures in the urban environment.     

A river is reborn--Use Attainability Analysis for the Lower Des Plaines River, Illinois.

The goal of the Use Attainability Analysis (UAA) of the Lower Des Plaines River was to upgrade the designated "Secondary Contact Recreation and Indigenous Aquatic Life Use" to a higher use that would be commensurate with the goals of the Clean Water Act (CWA). In Illinois, the water body use in compliance with the goals of the CWA is named "General Use". The river has been extensively modified and receives most point-source and urban runoff discharges from the Chicago metropolitan area (9.5 million inhabitants). The study included an extensive assessment of the physical, chemical, biological, and bacteriological integrity status of the water body and sediments. The UAA found that the water quality situation of the river has improved significantly since the 1970s, when the Illinois Pollution Control Board defined and assigned the Secondary Contact Recreation and Indigenous Aquatic Life Use designation to the Lower Des Plaines River. The study defined and suggested a "Modified Impounded Use" for one highly modified reach, with adjusted standards for dissolved oxygen and recreation. The study also recommended adoption of the General Use standards, some of them in a modified form, for other water quality parameters. Standards for limited recreation were also developed. The UAA also outlines a suggested action plan that will bring UAA segments of the Lower Des Plaines River in compliance with UAA goals.     

Residences with anomalous soil concentrations of dioxin-like compounds in two communities in Michigan, USA: a case study

Most contamination of residential property soil with dioxin-like compounds occurs as a result of proximity to industrial activity that produces such compounds and, outside the industrially impacted zone, the soil concentrations are at background levels. However, as part of the University of Michigan Dioxin Exposure Study, residential properties in the lower peninsula of Michigan, USA, were identified that were located far enough from known sources of these compounds that the soil concentrations should have been at background levels and yet the toxic equivalent (TEQ) of some properties' soil was greater than 2.5 standard deviations above the mean background level. In the three cases presented here from Midland/Saginaw Counties, the anomalously high-TEQ values were primarily due to the presence of polychlorinated dibenzofurans. Based on interviews with the residents and a comparison of soil congener profiles, it was deduced that these values resulted from anthropogenic soil movement from historically contaminated areas. In the cases from Jackson/Calhoun Counties, the unusually high-TEQ values were primarily due to polychlorinated biphenyls. In the case profiled here, it appears that the soil became contaminated through sandblasting to remove paint from the swimming pool. This study identified two mechanisms for soil contamination outside zones of industrial impact; thus, an assumption of background levels of soil contamination outside industrial zones may not be valid.     

Consistency of Ozone and Nitrogen Oxides Standards at Tropospherically Relevant Mixing Ratios

Abstract

The absolute accuracy and long‐term precision of atmospheric measurements hinge on the quality of the instrumentation and calibration standards. To assess the consistency of the ozone (O₃) and nitrogen oxides (NO_x) standards maintained at the National Institute of Standards and Technology (NIST), these standards were compared through the gas‐phase titration of O3 with nitric oxide (NO). NO and O₃ were monitored using chemiluminescence and UV absorption, respectively. Nitrogen dioxide (NO₂) was monitored directly by laser‐induced fluorescence and indirectly by catalytic conversion to NO, followed by chemiluminescence. The observed equivalent loss of both NO and O₃ and the formation of NO₂ in these experiments was within 1% on average over the range of 40–200 nmol mol^?1 of NO in excess O3, indicating that these instruments, when calibrated with the NIST O₃ and NO standards and the NO₂ permeation calibration system, are consistent to within 1% at tropospherically relevant mixing ratios of O₃. Experiments conducted at higher initial NO mixing ratios or in excess NO are not in as good agreement. The largest discrepancies are associated with the chemiluminescence measurements. These results indicate the presence of systematic biases under these specific conditions. Prospects for improving these experiments are discussed.