Pesticides and Related Toxicants in the Atmosphere.

Pesticides and other toxicants released into the environment can contaminate air, water, soil, and biota. This review focuses on sources, exposures, fate, analysis, and trends. The potential for exposures due to atmospheric transport and deposition of pesticides and related contaminants may pose risks to humans and wildlife. Emissions of chemicals to air are related to physicochemical properties (e.g., vapor pressure and chemical stability). Experimental design and computer-based modeling, as related to emissions and dispersion of pesticides along transects downwind from release sources, will be discussed using the example of pesticide volatilization and drift in California agriculture that results in the transport and deposition downwind to the Sierra Nevada mountains, where much work has been done to refine exposure data for use in risk assessment and management. Predictably, those chemicals found frequently in air are those used most extensively, have multiple emission sources, and resist degradation. Yet to be determined are definitive connections with adverse impacts to humans and wildlife, although the accumulating evidence suggests that endocrine disrupting chemicals, ChE inhibitors, and others warrant further attention. Steps that are being taken to limit emissions, such as in pest control and fuel combustion, offer promising opportunities for improving the quality of air and of the overall environment. Chemical degradation rates and products from trace organics in the air merit more attention, as do the potential for activation by photooxidation and bioaccumulation in food chains. The potential effect of climate change, on atmospheric processes affecting contaminant behavior, is an area ripe for further study.

Acrylamide release resulting from sunlight irradiation of aqueous polyacrylamide/iron mixtures.

Linear anionic polyacrylamide (PAM) has been used in irrigation practices as a flocculating agent to minimize water losses through seepage in earthen canals. The stability of PAM is of concern because of the possibility of acrylamide (AMD) monomer release during environmental weathering. Aqueous solutions of commercial PAM mixed with ferric sulfate, subjected to simulated and natural sunlight irradiation, showed polymer chain scission and release of the AMD monomer. At acid/neutral pH, the amount of AMD released was directly related to the concentration of ferric ion and the irradiation time. At alkaline pH (approximately 8), PAM/Fe(3+) mixtures were stable under irradiation. PAM chain scission involved the hydroxyl radical, but specific AMD release appeared to require PAM-bound iron. Low iron concentrations and alkaline pH of irrigation water would limit AMD release. Residual monomer in PAM can contribute AMD to irrigation water, but concentrations would remain below the U.S. EPA drinking water standard of 0.5 ppb.

Differences in DNA-damage in non-smoking men and women exposed to environmental tobacco smoke (ETS).

There is much data implicating environmental tobacco smoke (ETS) in the development and progression of disease, notably cancer, yet the mechanisms for this remain unclear. As ETS is both a pro-oxidant stressor and carcinogen, we investigated the relationship of ETS exposure to intracellular and serum levels of DNA-damage, both oxidative 8-hydroxy-2-deoxyguanosine (8OHdG) and general, in non-smokers from non-smoking households, occupationally exposed to ETS. General DNA-damage consisting of single and double strand breaks, alkali-labile sites and incomplete base-excision repair, increased significantly in a dose-dependent manner with ETS exposure in men (P=0.015, n=32, Pearson) but not women (P=0.736, n=17). Intracellular 8OHdG-DNA-damage and general DNA-damage were both greater in men than women (P=0.0005 and 0.016, respectively) but 8OHdG serum levels did not differ between the genders. Neither 8OHdG-DNA-damage nor serum levels correlated with increasing ETS exposure. This is the first study to demonstrate dose-dependent increases in DNA-damage from workplace ETS exposure. Perhaps most interesting was that despite equivalent ETS exposure, significantly greater DNA-damage occurred in men than women. These data may begin to provide a mechanistic rationale for the generally higher incidence of some diseases in males due to tobacco smoke and/or other genotoxic stressors.

Environmental behavior and analysis of agricultural sulfur.

Sulfur has been widely used for centuries as a staple for pest and disease management in agriculture. Presently, it is the largest-volume pesticide in use worldwide. This review describes the sources and recovery methods for sulfur, its allotropic forms and properties and its agricultural uses, including development and potential advantages of nanosulfur as a fungicide. Chemical and microbial reactivity, interactions in soil and water and analytical methods for determination in environmental samples and foodstuffs, including inexpensive analytical methods for sulfur residues in wine, beer and other food/beverage substrates, will be reviewed. The toxicology of sulfur towards humans and agriculturally important fungi is included, with some restrictions on use to promote safety. The review concludes with areas for which more research is warranted.

Determination of methyl isocyanate in outdoor residential air near metam-sodium soil fumigations.

The soil fumigant metam-sodium (CH3NHCS2Na) produces the bioactive respiratory irritant methyl isothiocyanate (MITC). Recent laboratory gas-phase oxidative studies indicate that MITC rapidly transforms to the more toxic methyl isocyanate (MIC) in the lower atmosphere. Inhalation exposure risks from MITC plus MIC may therefore be an occupational worker and/or bystander health concern. To address this concern, MIC was monitored, along with MITC, in outdoor residential air in Washington state during the peak fall metam fumigation season. XAD-7 cartridges, coated with 1-(2-pyridyl)piperazine, were developed to retain MIC as its stable substituted urea derivative. Of the 68 residential air measurements of MIC, 15 (22%) were observed to be above the California Environmental Protection Agency's chronic inhalation reference level of 1 µg/m(3), with an observed maximum MIC air concentration of 4.4 µg/m(3). This study indicates MIC air concentrations can be anticipated along with MITC in residential air where seasonal metam soil fumigant applications occur.

Correlation to estimate emission rates for soil-applied fumigants.

The emission rates [ER (µg m⁻² s⁻¹)] for subsurface injections and surface chemigations for 15 fumigant applications were combined with the physicochemical properties of the fumigants [vapor pressure, VP (Pa); water solubility, S(w) (mg L⁻¹); soil adsorption coefficient, K(oc) (mL g⁻¹)] and with application conditions [application rate, AR (kg ha⁻¹); depth of application, d (cm)]. This resulted in the regression Ln ER = 3.598 + 0.9400 Ln R [R = (VP × AR)/(S(w) × K(oc) × d)], which can be used to estimate emissions for new applications. Emission rates derived from the linear correlation were used as input to an atmospheric dispersion model to estimate concentrations of fumigants in air at various downwind distances, and the results were compared with concentration values measured in the field near sources. The fumigant correlation along with an atmospheric dispersion model can be used as a rapid screening method by regulatory and enforcement agencies for exposure and risk assessment.

Determination of methyl isothiocyanate in air downwind of fields treated with metam-sodium by subsurface drip irrigation.

Air concentrations of methyl isothiocyanate (MITC) were determined near two fields treated with metam-sodium (MS) by subsurface drip irrigation. The two study fields showed measurable airborne MITC residues during application of MS and for periods up to 48 h postapplication. Using a Gaussian plume dispersion model, flux values were estimated for all of the sampling periods. On the basis of the flux estimates, the amount of MITC that volatilized within the 48 h period was about 1.4% of the applied material. Compared to other studies, MITC residues in air measured during application by subsurface drip irrigation were up to four orders-of-magnitude lower than those previously published for applications involving delivery through surface irrigation water. Our measured concentrations of MITC in field air were at levels below current regulatory guidance and thresholds for adverse human health effects.