Metolachlor and chlorothalonil dissipation in gypsum-amended soil

This work focused on the interactive effects of the fungicide chlorothalonil (2,3,4,6-tetrachloro-1,3-benzendicarbonitrile) and gypsum on the persistence of the soil-residual herbicide metolachlor (2-chloro-N-(6-ethyl-o-tolyl)-N-[(1RS)-2-methoxy-1-methylethyl]acetamide). Gypsum application was included due to its widespread use on peanut (Arachis hypogaea). Both agricultural grade gypsum and reagent CaSO₄-2H₂O were tested. A laboratory soil incubation was conducted to evaluate interactive effects. Results indicated 1.5X greater metolachlor half-life (DT₅₀) in soil amended with chlorothalonil (37 d) as compared to control soil (25 d). The two gypsum sources alone increased metolachlor DT₅₀ to about 32 d and with the combination of chlorothalonil and gypsum, DT50 was 50 d, 2-fold greater than the control. Chlorothalonil dissipation was rapid (DT₅₀ < 4d). A possible explanation for metolachlor dissipation kinetics is a build-up of the chlorothalonil intermediate (4-hydroxychlorothalonil) which limited soil microbial activity and depleted glutathione S-transferase (GST) from chlorothalonil detoxification. Further information related to gypsum impacts is needed. Results confirm previous reports of chlorothalonil impeding metolachlor dissipation and showed the gypsum application extended persistence even longer. Farming practices, such as reducing metolachlor application rates, may need to be adjusted for peanut cropping systems where chlorothalonil and gypsum are used.     

Evidence of degradation of polybrominated biphenyls in soil samples from michigan

Abstract

Soil samples obtained from the former polybrominated biphenyls (PBB) manufacturing site in Michigan were analyzed by gas chromatography and gas chromatography with mass spectrometric detection. The results indicate significant degradation of the PBB residue in the soil sample. The soil sample with the highest concentration of PBB has the greatest degree of degradation. Principal degradation products include 2,3’,4,4’,5‐pentabromo‐biphenyl, 2,2’,4,4’,5‐pencabromobiphenyl and two unidentified tetrabromobiphenyls.

The degradation pattern observed supports a photochemical decomposition mechanism. These degraded residues may be more toxic than the original Firemaster residues. The implications of the results are discussed.     

Comparison of the Annular Denuder System and the Transition Flow Reactor for Measurements of Selected Dry Deposition Species

An intensive field study was conducted in Research Triangle Park, North Carolina in the fall of 1986. Ambient concentrations of the following constituents were obtained: nitric acid, nitrous acid, nitrogen dioxide, sulfur dioxide, ammonia, hydrogen ion, and particulate nitrate, sulfate, and ammonium. Results collected using the annular denuder system (ADS) and the transition flow reactor (TFR) are presented and compared.

Both types of samplers had operational detection limits on daily (22-hour) samples that were generally below 1 μg m_-3 suggesting that both samplers can provide sensitive measurements for most of the constituents of interest. Both the ADS and TFR show reasonable (>25 percent) within-sampler precision for most of the measured species concentrations, except TFR fine particulate nitrate measurements where results were frequently negative (The TFR fine particulate nitrate measurement is calculated using subtraction of positive numbers).

Comparison of ADS and TFR daily results showed good agreement for total particulate sulfate, the sum of total (coarse plus fine) particulate and gaseous nitrate, and ammonia. As a result of different inlet particle collection efficiencies, the ADS fine particulate sulfate exceeded the TFR (5 percent). In the absence of a filter to collect volatilized particulate ammonium in the ADS, the sum of total particulate and gaseous ammonium in the TFR exceeded that in the ADS. Of potentially more importance, ADS measurements of SO₂ and H⁺ exceeded those of the TFR, while TFR measurements of HNO₃ exceeded those of the ADS. Results of this study suggest that the TFR may provide biased measurements of SO₂, H⁺, HNO₃, and Fine NO₃ ^- that cannot be corrected without modifications to the fundamental design of the sampling system.     

Assessment of Needs for Technical Information in EPA’s Hazardous and Solid Waste Programs

Headquarters managers and Regional staff in the U.S. Environmental Protection Agency’s hazardous and solid waste programs were surveyed to determine priorities for technical information and guidance among EPA Regional staff, state hazardous waste management staff, EPA contractors, and the regulated community. The survey also examined delivery systems effective for EPA Regional staff. The fifteen highest ranked technical needs for RCRA, Superfund, and UST reflect a pervasive interest in hazardous waste remediation. Top priority technical needs focus on establishing cleanup levels, subsurface fate and transport, field monitoring and quality assurance, remedy selection, and most importantly, which remedies work and which do not in specific situations. Technical needs of non- EPA audiences are quite similar to those for EPA field staff. Preferences for technology transfer delivery systems are generally for conventional distribution methods (such as print materials and workshops) rather than electronic or video media. Regional staff report serious problems in utilizing technology transfer because of time constraints, insufficient knowledge of available products, insufficient travel funds, and limited access to and training on computers.     

Estimation of Trends in Atmospheric Concentrations of Sulfate in the Northeastern United States

Abstract

Daily atmospheric concentrations of sulfate collected at six locations in the northeastern United States are regressed against meteorological factors, ozone, seasonal cycles, and time in order to determine if a significant trend in sulfate can be detected. The data used in this analysis were collected during the Sulfate Regional Experiment (SURE, 1977-1978) and the Eulerian Model Evaluation Field Study (EMEFS, 1988-1989). Ozone, specific humidity, and seasonal terms (reflecting the potential of the atmosphere for oxidation of sulfur dioxide) emerged as important explanatory variables. After accounting for the variability explained by environmental factors, the median estimated change in sulfate concentration from the six locations over the 11-year period is -22% (or -28% if ozone is not used as an explanatory variable). Although there are wide variations among locations, these changes are commensurate with an estimated 25% decline in sulfur emissions in the northeastern U.S. during the same period. These analyses provide insight into methods for detecting reductions in sulfate that may be expected to occur as a result of the Clean Air Act Amendments of 1990. Uncertainties in the estimates, with consideration of serial correlation in the data, imply a minimum detectable reduction of 10% using this modeling procedure with similar data availability.     

Aerosol Research and Inhalation Epidemiological Study (ARIES): Air Quality and Daily Mortality Statistical Modeling— Interim Results

ABSTRACT

The Aerosol Research and Inhalation Epidemiological Study (ARIES) is an EPRI-sponsored project to collect air quality and meteorological data at a single site in northwestern Atlanta, GA. Seventy high-resolution air quality indicators (AQIs) are used to examine statistical relationships between air quality and health outcome end points. Contemporaneous mortality data are collected for Fulton and DeKalb counties in Georgia. Currently, 12 months of air quality and weather data are available for analysis, from August 1998 through July 1999.

The interim mortality analysis used Poisson regression in generalized additive models (GAMs). The estimated log-linear association of mortality with various AQIs was adjusted for smoothed functions of time and meteorological data. The analysis considered daily deaths due to all nonaccidental causes, deaths to persons 65 years or older, and deaths in each of the two constituent counties. The fine particle effect associated with the four mortality subgroups, using only today (lag 0), yesterday (lag 1), 2-day average (average of today and yesterday), and first difference (today minus yesterday) measurements of the air quality relative to today's number of deaths was positive for lag 0, lag 1, and 2-day average and positive only for decedents at least 65 years of age using first difference. The t values ranged from 0.81 to 1.15 for lag 0, 1.04 to 1.53 for lag 1, 1.10 to 1.66 for 2-day average, and -0.32 to 0.33 for first difference with 346 or 347 days of data. No statistically significant estimate of the linear coefficient was found for the other 14 air quality variables in our interim analysis for the four mortality subgroups. We discuss diagnostics to support these models.

These interim analyses did not include an evaluation of sensitivity to a larger set of lag structures, nonlinear model specifications, multipollutant analyses, alternative weather model and smoothing model specifications, air pollution imputation schemes, or cause-specific mortality indicators, nor did they include a full reporting of model selection or goodness-of-fit indicators. No conclusion can be drawn at this time about whether the findings from subsequent studies have sufficiently greater power to detect effects comparable to those found in other U.S. cities including at least 2 or 3 years of data.     

Particulate Emissions from Construction Activities

Abstract

Although it has long been recognized that road and building construction activity constitutes an important source of particulate matter (PM) emissions throughout the United States, until recently only limited research has been directed to its characterization. This paper presents the results of PM₁₀ and PM_2.5 (particles ≤10 μm and ≤2.5 μm in aerodynamic diameter, respectively) emission factor development from the onsite testing of component operations at actual construction sites during the period 1998 –2001. Much of the testing effort was directed at earthmoving operations with scrapers, because earthmoving is the most important contributor of PM emissions across the construction industry. Other sources tested were truck loading and dumping of crushed rock and mud and dirt carryout from construction site access points onto adjacent public paved roads. Also tested were the effects of watering for control of scraper travel routes and the use of paved and graveled aprons at construction site access points for reducing mud and dirt carryout. The PM₁₀ emissions from earthmoving were found to be up to an order of magnitude greater than predicted by AP-42 emission factors drawn from other industries. As expected, the observed PM_2.5:PM₁₀ emission factor ratios reflected the relative importance of the vehicle exhaust and the resuspended dust components of each type of construction activity. An unexpected finding was that PM_2.5 emissions from mud and dirt carryout were much less than anticipated. Finally, the control efficiency of watering of scraper travel routes was found to closely follow a bilinear moisture model.     

A Method of Predicting Point and Path- Averaged Ambient Air VOC Concentrations,Using Meteorological Data

A method of predicting point and path-averaged ambient air VOC concentrations is described. This method was developed for the case of a plume generated from a single point source, and is based on the relationship between wind directional frequency and concentration. One-minute means of wind direction and wind speed were used as inputs to a Gaussian dispersion model to develop this relationship.

Both FTIR spectrometry and a whole-air sampling method were used to monitor VOC plumes during simulated field tests. One test set was also conducted using only whole-air samplers deployed in a closely-spaced network, thus providing an evaluation of the prediction technique free of any bias that might exist between the two analytical methods.

Correlations between observed point concentrations and wind directional frequencies were significant at the 0.05 level in most cases. Predicted path-integrated concentrations, based on observed point concentrations and meteorological data, were strongly correlated with observed values. Predicted point concentrations, based on observed path-integrated concentrations and meteorological data, accurately reflected the location and magnitude of the highest concentrations from each test, as well as the shape of the concentration-versus-crosswind distance curve.     

Aerosol species concentrations and source apportionment of ammonia at Rocky Mountain National Park

Changes in ecosystem function at Rocky Mountain National Park (RMNP) are occurring because of emissions of nitrogen and sulfate species along the Front Range of the Colorado Rocky Mountains, as well as sources farther east and west. The nitrogen compounds include both oxidized and reduced nitrogen. A year-long monitoring program of various oxidized and reduced nitrogen species was initiated to better understand their origins as well as the complex chemistry occurring during transport from source to receptor. Specifically, the goals of the study were to characterize the atmospheric concentrations of nitrogen species in gaseous, particulate, and aqueous phases (precipitation and clouds) along the east and west sides of the Continental Divide; identify the relative contributions to atmospheric nitrogen species in RMNP from within and outside of the state of Colorado; identify the relative contributions to atmospheric nitrogen species in RMNP from emission sources along the Colorado Front Range versus other areas within Colorado; and identify the relative contributions to atmospheric nitrogen species from mobile sources, agricultural activities, and large and small point sources within the state of Colorado. Measured ammonia concentrations are combined with modeled releases of conservative tracers from ammonia source regions around the United States to apportion ammonia to its respective sources, using receptor modeling tools.

Implications: Increased deposition of nitrogen in RMNP has been demonstrated to contribute to a number of important ecosystem changes. The rate of deposition of nitrogen compounds in RMNP has crossed a crucial threshold called the “critical load.” This means that changes are occurring to park ecosystems and that these changes may soon reach a point where they are difficult or impossible to reverse. Several key issues need attention to develop an effective strategy for protecting park resources from adverse impacts of elevated nitrogen deposition. These include determining the importance of previously unquantified nitrogen inputs within the park and identification of important nitrogen sources and transport pathways.