Predicting pesticide emissions and downwind concentrations using correlations with estimated vapor pressures.

Pesticide emissions to air have been shown to correlate with compound vapor pressure values taken from the published literature. In the present study, emissions correlations based on vapor pressures derived from chemical property estimation methods are formulated and compared with correlations based on the literature data. Comparison was made by using the two types of correlations to estimate emission rates for five herbicides, a fungicide, and an insecticide, for which field-measured emission rates from treated soil, foliage, and water were available. In addition, downwind concentrations were estimated for two herbicides, three fungicides, four insecticides, and two fumigants, for which concentration measurements had been made near treated sources. The comparison results demonstrated that correlations based on vapor pressures derived from chemical property estimation methods were essentially equivalent to correlations based on literature data. The estimation approach for vapor pressures is a viable alternative to the inherently more subjective process of selecting literature values.

Quantitative integration of the Salmonella microsuspension assay with supercritical fluid extraction of model airborne vapor-phase mutagens.

Vapor-phase mutagens are potentially a major class of toxic contaminants in ambient and indoor air. These compounds are not routinely analyzed due to a lack of an established integrated methodology to quantitatively trap, extract and test the compounds in a bioassay. In a previous report, we emphasized the trapping of volatile and semi-volatile mutagens and the extraction of these compounds using supercritical carbon dioxide (CO2). In the present study, we discuss the use of a bioassay for the quantitation of the model mutagens, ethylene dibromide(EDB) and 4-nitrobiphenyl (4-NB), trapped from an airstream. The compounds EDB and 4-NB were released into a controlled airstream, trapped on XAD-4 adsorbent, and were extracted using supercritical CO2. The extract was tested in a microsuspension modification of the Ames Salmonella/microsome test adapted for volatile compounds. Linear dose-response relationships were obtained for supercritical CO2-extracted EDB using tester strain TA100 (+/- S9) and for 4-NB using tester strains TA98 and TA100 (-S9). Standard dose-response curves with known amounts of the compounds were also determined for comparison with measured amounts of the model compounds collected in an airstream. The gas chromatographic (GC)- and bioassay-determined quantities of EDB and 4-NB were highly correlated, accurate and precise. For example, bioassay-determined EDB concentrations were within 10% of the GC-determined concentrations. Our results demonstrate that the integrated methodology for vapor-phase mutagens developed in this study would be useful for quantitative analysis of these and related airborne vapor-phase mutagenic compounds.

Determination of volatile and semivolatile mutagens in air using solid absorbents and supercritical fluid extraction.

Volatile toxicants may be present in emissions from mobile and stationary sources as well as in ambient air. Methods for collecting and concentrating volatiles from air samples have been developed. Solid-phase adsorbents were compared in their trapping efficiencies for dichloromethane (DCM), ethylene dibromide (EDB), 4-nitroblphenyl (4-NB), 2-nitrofluorene (2-NF), and fluoranthene (FI). Charcoal and Carbosieve were the most efficient media for retaining DCM, while XAD-4 was the best adsorbent for EDB and the aromatic compounds. Extraction of direct spikes of compounds from adsorbents using supercritical carbon dioxide resulted in greater than 90% recovery of EDB and 60-92% recovery of the aromatics. Integration of trapping and desorption methods with the Salmonella microsuspension bioassay was demonstrated with EDB and 4-NB recoveries from air; chemical analysis and bioassay gave comparable results (within 10%).

Sampling and analysis of airborne residues of paraquat in treated cotton field environments.

A method was developed for the analysis of paraquat residues in airborne particulate matter collected by filtration or impaction. The method is based on extraction of paraquat with 6N hydrochloric acid, transfer of residue to saturated ammonium bicarbonate solution, and reduction of the resulting residue with alkaline sodium borohydride to a mixture of two tertiary amines with subsequent determination by nitrogen-selective gas chromatography (GLC). Recoveries ranged from 74 to 96% for filters spiked at 0.05 microgram and above; the limit of detection is approximately 0.5 ng/m3 for high volume air samples. Paraquat concentrations measured in the air downwind from two commercial applications to cotton during spraying fell regularly from extrapolated interval-average values of 4.31 and 10.7 microgram/m3 at the 1 m downwind edge of the two fields to less than 50 ng/m3 at approximately 400 m downwind. Downwind samples taken 2 to 4 hr after spraying contained 1 to 10% as much paraquat as those during spraying, and by 5 to 7 hr no paraquat was detectable in the downwind air. Paraquat was also found in the airborne particulate matter during mechanical harvesting of one of the fields, the maximum interval-average values being 1,245 and 516 ng/m3 just outside and inside an open cab, respectively. The analytical findings for paraquat are compared with those for S,S,S-tributylphosphorotrithioate (DEF), a component of the harvest aid mixture employed, and discussed in terms of occupational exposure, potential hazard, and recommended occupational practices.

Airborne and surface residues of parathion and its conversion products in a treated plum orchard environment.

Airborne pesticide residues were collected both within and downwind from a parathion-treated plum orchard by high volume sampling through XAD-4 macroreticular resin. Levels of paraoxon in excess of 100 ng/m3 were found in orchard air, along with parathion, during the early days of two 21-day sampling studies. Paraoxon:parathion ratios in the orchard air were relatively constant, averaging ca. 0.5 for days 1 to 21 following treatment. Likely sources of airborne paraoxon include vaporization and dislodgement from soil and leaf surfaces, and chemical conversion of parathion in the air. Support for the latter came from observation of an increased paraoxon:parathion ration in air samples collected downwind from the orchard. Atmospheric conversion of parathion to paraoxon, accelerated by sunlight, was indicated by both field and laboratory studies. Overall dissipation of parathion from the orchard air, soil, and leaf tissue proceeded to a considerable extent through breakdown to paraozon under the dry climatic conditions of these studies. Eventual conversion to the relatively stable breakdown product, p-nitrophenol, was indicated from analysis of air in the orchard vicinity.