Assessment of Arsenic Losses during Ashing: A Comparison of Two Methods Applied to Atmospheric Participates

A comparison was made of over 300 pairs of arsenic results from instrumental neutron activation and flameless atomic absorption analyses of atmospheric particulates collected on glass fiber filters. Atomic absorption analyses involved low temperature ashing of filters at high power levels. No matrix modification chemicals were added to the acid extract which was analyzed. Neutron activation results are on the average 9% higher than those obtained by atomic absorption and the difference is statistically significant. This small difference is probably due to the analytical techniques or acid extraction and not in any important way to losses during low temperature ashing. This conclusion is in sharp contrast to other recently reported situations where low temperature ashing losses in analyzing atmospheric particulate were sizable. Although the atmospheres sampled differed somewhat between these situations the most obvious difference was in the combustibility of the filters used in sampling.     

Uncertainty requirements of the European Union’s Industrial Emissions Directive for monitoring sulfur dioxide emissions: Implications from a blind comparison of sulfate measurements by accredited laboratories

When annual average PM_2.5 (fine particulate matter sized 2.5 microns and less) data for 2005 became available in April 2006 and the 3-yr average PM_2.5 concentration in an area just north of the Houston Ship Channel reached 15.0 µg/m³, the Texas Commission on Environmental Quality (TCEQ) initiated daily collection of quartz fiber as well as Teflon PM_2.5 filter samples for chemical speciation analysis. The purpose of the chemical speciation analysis was to use the speciation data, together with meteorological data and hourly TEOM (tapered element oscillating microbalance) PM_2.5 mass data, to identify the causes of the high PM_2.5 concentrations affecting the monitoring site and the neighborhood. The ultimate purpose was to target emission reduction efforts to sources contributing to the high measured PM_2.5 concentrations. After a year of data collection, it was recognized that a specific source, unpaved driveways and loading areas along the Ship Channel and dirt tracked onto Clinton Drive, the main artery running east-west north of the Ship Channel, were the primary cause for the Clinton Drive site's measuring PM_2.5 concentrations significantly higher than other sites in Houston. The source characterization and remediation steps that have led to sustained reduced concentrations are described in this paper.

Implications: With PM_2.5 exceedances it can be essential to have or develop chemical speciation data as part of the process of identifying the source types causing exceedances of an annual standard. Positive matrix factorization (PMF) analysis proved to be a powerful tool that identified the two locally emitted species contributing to exceedances, which did not occur at other sites in the region. They were calcium sulfate (gypsum), an industrial by-product, and soil minerals. Other data analysis approaches were necessary to distinguish North African dust events, which PMF failed to identify.     

Statistical Assumptions Matter in Data Analysis for Texas Ozone Nonattainment Sites

Strategies for control of ozone aim at regulation of its chemical precursors, non-methane organic compounds (NMOC) and nitrogen oxides (NOx). It is therefore important to analyze how these precursors vary temporally and geographically. This study finds significant and important differences among four Texas ozone nonattainment sites, Dallas, Ft. Worth, El Paso, and Houston, for 1984, 1985, and 1986 for NMOC, NOx, and their ratio NNR. These differences were detected through nonparametric analysis of variance and Student-New-man-Keuls’s test for multiple comparisons on rank-transformed data. A noteworthy feature of the data analysis is its attention to the assumptions underlying the statistical methods. Classical models based on normal or lognormal theory had to be abandoned for lack of realism. It is demonstrated how alternative models may be applied to yield appropriate, rather than inappropriate, conclusions.     

The Impact of Increased Recycle Rates on Markets in Florida

The State of Florida passed The Florida Solid Waste Management Act of 1988 mandating that county recycling programs be initiated by July 1, 1989. The legislation further expressed the goal that, at a minimum, recycling efforts reduce the amount of solid waste requiring final disposal or resource recovery by 30 percent by the end of 1994. This study was performed to determine the impact on recycle markets when the amounts of materials recycled from the municipal solid waste stream are increased by 30 percent in Florida.

The composition of the municipal waste stream was quantified in terms of the amounts of paper, plastic, metals, glass, and rubber. The effect of a 30 percent increase in the recycle rate of each class of material was calculated and compared to existing recycle rates in the State of Florida. It was determined that there are few capacity constraints on the increase in recycle rates for aluminum, steel (i.e., tin cans), and color separated glass. There are, however, serious constraints on increasing recycle rates for paper, plastics and rubber tires.     

Air Quality Modeling and Decisions for Ozone Reduction Strategies

Abstract

Despite the widespread application of photochemical air quality models (AQMs) in U.S. state implementation planning (SIP) for attainment of the ambient ozone standard, documentation for the reliability of projections has remained highly subjective. An “idealized” evaluation framework is proposed that provides a means for assessing reliability. Applied to 18 cases of regulatory modeling in the early 1990s in North America, a comparative review of these applications is reported. The intercomparisons suggest that more than two thirds of these AQM applications suffered from having inadequate air quality and meteorological databases. Emissions representations often were unreliable; uncertainties were too high. More than two thirds of the performance evaluation efforts were judged to be substandard compared with idealized goals. Meteorological conditions chosen according regulatory guidelines were limited to one or two cases and tended to be similar, thus limiting the extent to which public policy makers could be confident that the emission controls adopted would yield attainment for a broad range of adverse atmospheric conditions. More than half of the studies reviewed did not give sufficient attention to addressing the potential for compensating errors. Corroborative analyses were conducted in only one of the 18 studies reviewed. Insufficient attention was given to the estimation of model and/or input database errors, uncertainties, or variability in all of the cases examined. However, recent SIP and policy‐related regional modeling provides evidence of substantial improvements in the underlying science and available modeling systems used for regulatory decision making. Nevertheless, the availability of suitable databases to support increasingly sophisticated modeling continues to be a concern for many locations. Thus, AQM results may still be subject to significant uncertainties. The evaluative process used here provides a framework for modelers and public policy makers to assess the adequacy of contemporary and future modeling work.     

HPLC determination of chlorate metabolism in bovine ruminal fluid

Salmonella and Escherichia coli are two bacteria that are important causes of human and animal disease worldwide. Chlorate is converted in the cell to chlorite, which is lethal to these bacteria. An HPLC procedure was developed for the rapid analysis of chlorate (ClO₃ ^?), nitrate (NO₃ ^?), and nitrite (NO₂ ^?) ions in bovine ruminal fluid samples. Standard curves for chlorite, nitrite, nitrate, and chlorate were well defined linear curves with R² values of 0.99846, 0.99106, 0.99854, and 0.99138, respectively. Concentrations of chlorite could not be accurately determined in bovine ruminal fluid because chlorite reacts with or binds a component(s) or is reduced to chloride in bovine ruminal fluid resulting in low chlorite measurements. A standard curve ranging from 25 to 150 ppm ClO₃ ^? ion was used to measure chlorate fortified into ruminal fluid. The concentration of chlorate was more rapidly lowered (P < 0.01) under anaerobic compared to aerobic incubation conditions. Chlorate alone or chlorate supplemented with the reductants sodium lactate or glycerol were bactericidal in anaerobic incubations. In anaerobic culture, the addition of sodium formate to chlorate-fortified ruminal fluid appeared to decrease chlorate concentrations; however, formate also appeared to moderate the bactericidal effect of chlorate against E. coli. Addition of the reductants, glycerol or lactate, to chlorate-fortified ruminal fluid did not increase the killing of E. coli at 24 h, but may be useful when the reducing equivalents are limiting as in waste holding reservoirs or composting systems required for intense animal production.     

Temperature and salinity effects on the toxicity of common pesticides to the grass shrimp,Palaemonetes pugio

This study investigated the effects of increased temperature and salinity, two potential impacts of global climate change, on the toxicity of two common pesticides to the estuarine grass shrimp, Palaemonetes pugio. Larval and adult grass shrimp were exposed to the fungicide chlorothalonil and the insecticide Scourge® under standard toxicity test conditions, a 10°C increase in temperature, a 10 ppt increase in salinity, and a combined increased temperature and salinity exposure. Toxicity of the fungicide chlorothalonil increased with temperature and salinity. Toxicity of the insecticide Scourge® also increased with temperature; while increased salinity reduced Scourge® toxicity, but only in adult shrimp. These findings suggest that changes in temperature and salinity may alter the toxicity of certain pesticides, and that the nature of the effect will depend on both the organism's life stage and the chemical contaminant. Standard toxicity bioassays may not be predictive of actual pesticide toxicity under variable environmental conditions, and testing under a wider range of exposure conditions could improve the accuracy of chemical risk assessments.     

Comparison of surface emissions and subsurface distribution of cis- and trans-1,3-dichloropropne and chloropicrin in sandy field beds covered with four different plastic films

The purpose of this study was to conduct a field study at a Florida field site on surface emissions and subsurface distribution of cis-and trans-1,3-dichloropropene (1,3-D) and chloropicrin (CP) in raised beds injected with Telone C35 with four replications. A total of 16 beds were applied with Telone C35 by chisel injection and covered with four different plastic films, 4 beds for each film. Each bed was installed with five 20-cm long soil pore air probes and a surface air collection pan at arbitrarily locations along the length of each bed for sampling soil pore air and surface air, respectively, for analysis of the three biologically active compounds, cis- and trans-1,3-D and CP. We found that average concentrations of the three compounds at 20-cm depth among the beds covered with four different plastic films generally were not statistically different. Among the four beds covered with the same plastic film, average concentrations of the three compounds were statistically different only in the four metallic PE covered beds at 5 and 24 hours after injection. Volatilization rates of the three compounds among the beds covered with four different plastic films, with the exception of CP at 48 hours after injection, were not statistically different. It appeared that initial upward diffusion and volatilization flux were influenced by solar radiation. Initial subsurface concentrations of the three compounds and volatilization flux, especially cis-1,3-D, were greater in the beds on the east side of the field than that in the beds on the west side of the field. Whether or not difference in initial subsurface concentrations of the compounds between east side beds and west side beds may influence fumigant efficacy remains to be determined.