Photodegradation and volatility of pesticides

BACKGROUND AND OBJECTIVES: Among the factors affecting the environmental fate of surface-applied pesticides several biological as well as abiotic factors, such as volatilization and photochemical transformations are of particular interest. Whereas reliable measurement methods and models for estimating direct photodegradation are already available for the compartments of water and atmosphere and individual subprocesses have already been described in detail, there is still a need for further elucidation concerning the key processes of heterogeneous photodegradation of environmental chemicals on surfaces. METHODS: In order to systematically examine the direct and indirect photodegradation of 14C-labeled pesticides on various surfaces and their volatilization behavior, a new laboratory device ('photovolatility chamber') was designed according to US EPA Guideline 161-3. Model experiments under controlled conditions were conducted investigating the impact of different surfaces, i.e. glass, soil dust and radish plants, and environmental factors, i.e. irradiation and atmospheric ozone (O3), on the photodegradation and volatilization of surface-deposited [phenyl-UL-14C]parathion-methyl (PM). RESULTS AND DISCUSSION: Depending on the experimental conditions, parathion-methyl was converted to paraoxon-methyl, 4-nitrophenol, unknown polar products and 14CO2. With respect to the direct photodegradation of PM (experiments without O3), the major products were polar compounds and 14CO2, due to the rapid photochemical mineralization of 4-nitrophenol to 14CO2. Paraoxon-methyl and 4-nitrophenol formation was mainly mediated by the combination of light, O3, and *OH radicals. In radish experiments PM photodegradation was presumably located in the cuticle compartment, which exhibited a sensitized photodegradation, as more unknown products were yielded compared to the glass and soil dust experiments. This could be explained by intensifying the inherent PM degradation in the dark with the same product spectrum. Due to photochemical product formation, which is an antagonistic process to the volatilization of parent compound, the volatilization of unaltered parathion-methyl from each surface generally decreased in the presence of light, particularly in combination with increasing O3 concentrations and *OH radical production rates. CONCLUSION: First results demonstrated that the photovolatility chamber provides a special tool for the systematic evaluation of (a) photodegradation of surface-located pesticide residues, i.e. measuring qualitative aspects of direct and indirect photodegradation together with relative photodegradation rates, and (b) volatilization of pesticides on surfaces by including and optionally varying relevant parameters such as light, atmospheric O3 concentration, surface temperature, air temperature, air flow rate. OUTLOOK: The experimental facility represents an important complement to lysimeter and field studies, in particular for experiments on the volatilization of pesticides using the wind tunnel system. With the photovolatility chamber special experiments on photodegradation, volatilization and plant uptake can be conducted to study key processes in more detail and this will lead to a better understanding of the effects of certain environmental processes on the fate of released agrochemicals contributing to an improved risk assessment.     

Use and validation of novel snow samplers for hydrophobic, semi-volatile organic compounds (SVOCs)

Two novel gas-tight snow samplers (snow-can and snow-tube) are presented and the performance of the snow-can in a field trial was assessed. The methodology for the sampling, extraction and analysis of persistent organic pollutants (POPs) are detailed. These samplers allow the various components of a snow sample to be analysed separately; these included the meltwater (MW), particulate matter (GFF) and vapour in the headspace (HS). Snow samples collected on the Punta Indren glacier in the Italian Alps revealed the occurrence of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OC). Replicate samples of the same snow type were undertaken as a test of sampling precision. Relative standard deviations (RSDs) for SigmaPCBs and SigmaPAHs were approximately 30% and approximately 35% respectively. The lowest precision was found for the particle-laden snow, notably for the heavier PCB homologues. For the chlorinated compounds, the pesticides lindane and endosulfan-I had the highest levels in snow, with mean concentrations of 402 and 103 pgl(-1) (snow meltwater) respectively. The vapour present in the headspace (HS) comprised a minor component of a collected sample for all compounds, but HS concentrations for three lighter PAHs gave good agreement with those calculated based on their dimensionless Henry's law constants. This suggests that volatilisation during melting of aged snow-can be reasonably predicted with knowledge of the temperature-dependent Henry's law constant.     

Complex interactions between autotrophs in shallow marine and freshwater ecosystems: implications for community responses to nutrient stress

The relative biomass of autotrophs (vascular plants, macroalgae, microphytobenthos, phytoplankton) in shallow aquatic ecosystems is thought to be controlled by nutrient inputs and underwater irradiance. Widely accepted conceptual models indicate that this is the case both in marine and freshwater systems. In this paper we examine four case studies and test whether these models generally apply. We also identify other complex interactions among the autotrophs that may influence ecosystem response to cultural eutrophication. The marine case studies focus on macroalgae and its interactions with sediments and vascular plants. The freshwater case studies focus on interactions between phytoplankton, epiphyton, and benthic microalgae. In Waquoit Bay, MA (estuary), controlled experiments documented that blooms of macroalgae were responsible for the loss of eelgrass beds at nutrient-enriched locations. Macroalgae covered eelgrass and reduced irradiance to the extent that the plants could not maintain net growth. In Hog Island Bay, VA (estuary), a dense lawn of macroalgae covered the bottom sediments. There was reduced sediment-water nitrogen exchange when the algae were actively growing and high nitrogen release during algal senescence. In Lakes Brobo (West Africa) and Okeechobee (FL), there were dramatic seasonal changes in the biomass and phosphorus content of planktonic versus attached algae, and these changes were coupled with changes in water level and abiotic turbidity. Deeper water and/or greater turbidity favored dominance by phytoplankton. In Lake Brobo there also was evidence that phytoplankton growth was stimulated following a die-off of vascular plants. The case studies from Waquoit Bay and Lake Okeechobee support conceptual models of succession from vascular plants to benthic algae to phytoplankton along gradients of increasing nutrients and decreasing under-water irradiance. The case studies from Hog Island Bay and Lake Brobo illustrate additional effects (modified sediment-water nutrient fluxes, allelopathy or nutrient release during plant senescence) that could play a role in ecosystem response to nutrient stress.     

Effect of gasoline formulation on the formation of photosmog: a box model study

Based on exhaust gas analyses from the combustion of five different types of gasoline in a passenger car operated on a chassis dynamometer, box model simulations of the irradiation of exhaust/NOx/air mixtures using an established chemical mechanism for a standardized photosmog scenario were performed. The fuel matrix used covered wide fractional ranges for paraffinic, olefinic, and aromatic hydrocarbons. Two fuels also contained methyl tertiary butyl ether (MTBE). The different O3 profiles calculated for each run were compared and interpreted. The O3 levels obtained were strongly influenced by the exhaust gas concentrations of aromatic and olefinic hydrocarbons. The higher exhaust content of these compounds caused higher O3 production in the smog system investigated. The conclusion of the present study is that the composition of gasoline cannot be taken directly for the estimation of the emissions' O3 creation potential from its combustion. Variation of the dilution in the different calculations showed evidence for an additional influence of transport effects. Accordingly, further detailed exhaust gas analyses followed by more complex modeling studies are necessary for a proper characterization of the relationship between fuel blend and gasoline combustion products.     

Polybrominated diphenyl ethers (PBDEs) in grey seals during their first year of life--are they thyroid hormone endocrine disrupters?

Blubber biopsy and blood samples were collected from weaned grey seal pups and juveniles in 1998 and 1999. The relationship between the concentration of total PDBEs in the blubber and the circulating concentrations of serum proteins, minerals and thyroid hormones was investigated. Fifty-four post-weaned pups were sampled and 55 first year juveniles, of which 13 were recaptured post-weaned pups. The median concentration of total PBDEs in the pups' blubber was 170 and 460 ng g(-1) in the first-year animals. Total blubber PBDEs contributed significantly to the prediction of circulating thyroid hormone concentrations, after controlling for age and condition. Cholesterol and albumin concentrations were also positively related to blubber PBDEs. The results of this study suggest a link between thyroid hormones and exposure to PBDEs in grey seals during their first year of life. Such an association is not alone sufficient evidence for a cause and effect relationship, however it is in accordance with the hypothesis that these compounds are endocrine disrupters in grey seal pups.     

Photolytic degradation of hexacyanoferrate (II) in aqueous media: the determination of the degradation kinetics

Upon exposure to ultraviolet (UV) radiation, non-toxic hexacyanoferrate (II) (Fe(CN)6(-4)) undergoes direct photolysis, resulting in the liberation of toxic free cyanide (HCN,CN-). This experimental study employed manipulation of several environmental parameters with the objective of characterizing their effects on the photolysis rate of hexacyanoferrate (II). The photolysis rate was not affected significantly by varying (1) the initial hexacyanoferrate (II) concentration (from 10 to 400 microg/l as total CN), (2) the solution turbidity (kaolin clay concentration from 0 to 5 mg/l), and (3) pH (from pH 4 to 12). Parameters that exhibited a significant effect (significance level, alpha < 0.05) on the photolysis rate included the intensity of incident ultraviolet radiation (from 30 to 110 micromol/m2s photons) and the concentration of dissolved organic matter (color) from added humic acid (from 0 to 10 mg/l). In addition, observations made by spiking both deionized and natural waters demonstrated that the rate of hexacyanoferrate (II) photolysis (1) significantly exceeded the rate of free cyanide formation from photolysis and (2) exhibited significant retardation that directly depended on the free cyanide concentration in solution. The hexacyanoferrate (II) photolysis data were consistent with a simple, semi-empirical kinetic model that included the reversible formation of at least one cyanoferrate intermediate. The reverse reaction, in turn, behaved in a manner that was consistent with a second order rate law with respect to free cyanide concentration.     

Evaluation of membrane bioreactor process capabilities to meet stringent effluent nutrient discharge requirements.

A six-stage membrane bioreactor (MBR) pilot plant was operated to determine and demonstrate the capability of this process to produce a low-nutrient effluent, consistent with the nutrient reduction goals for the Chesapeake Bay. Biological nitrogen removal was accomplished using a multistage configuration with an initial anoxic zone (using the carbon in the influent wastewater), an aerobic zone (where nitrification occurred), a downstream anoxic zone (where methanol was added as a carbon source), and the aerated submerged membrane zone. The capability to reliably reduce effluent total nitrogen to less than 3 mg/L as nitrogen (N) was demonstrated. A combination of biological (using an initial anaerobic zone) and chemical (using alum) phosphorus removal was used to achieve effluent total phosphate concentrations reliably less than 0.1 mg/L as phosphorus (P) and as low as 0.03 mg/L as P. Alum addition also appeared to enhance the filtration characteristics of the MBR sludge and to reduce membrane fouling. Aeration of the submerged membranes results in thickened sludge with a high dissolved oxygen concentration (approaching saturation), which can be recycled to the main aeration zone rather than to an anoxic or anaerobic zone to optimize biological nutrient removal. Biological nutrient removal was characterized using the International Water Association Activated Sludge Model No. 2d. The stoichiometry of chemical phosphorus removal was also consistent with conventional theory and experience. The characteristics of the solids produced in the MBR were compared with those of a parallel full-scale conventional biological nitrogen removal process and were generally found to be similar. These results provide valuable insight to the design and operating characteristics of MBRs intended to produce effluents with very low nutrient concentrations.     

Heterogeneity of chlorinated hydrocarbon sorption properties in a sandy aquifer

Hydraulic conductivity and sorption coefficients for chlorinated hydrocarbons (chloroform, carbon tetrachloride and tetrachloroethylene) were evaluated for 216 sediment samples collected across a 15 m transect and a 21 m depth interval in a contaminated aquifer near Schoolcraft, Michigan. Relationships between hydraulic conductivity, linear sorption partition coefficients, grain size classes, and spatial location were investigated using linear regression analysis and geostatistical techniques. Clear evidence of layering was found in sorption properties, hydraulic conductivity and grain sizes. Conductivity correlated well with grain size, as expected, but sorption varied inversely with grain size, contrary to some previous reports. No significant correlation was found between sorption properties and hydraulic conductivity. This is likely due to the unexpected presence of small amounts of highly sorptive coal-like solids, which dominate the sorption behavior but have little effect on conductivity. The results demonstrate that recent findings regarding the high sorption capacity of coal materials found in soils can exert a controlling influence on contaminant transport. Designers of in situ remediation systems should be cautioned that 1) it is not reasonable to assume that sorption capacity and hydraulic conductivity are related, 2) sorption capacity and hydraulic conductivity are critical measurements for contaminant site characterization and subsequent transport modeling, 3) estimating sorption capacity from organic carbon measurement may lead to greater errors than performing sorption isotherms, and 4) it is more important to characterize vertical heterogeneity rather than horizontal heterogeneity because both sorption and hydraulic conductivity are correlated across longer distances in the horizontal plane.     

Organic mercury levels among the Yanomama of the Brazilian Amazon Basin

The Catrimani River basin in northern Brazil is the home of the Yanomama and has been the site of renegade gold mining since 1980. Gold-mining operations release inorganic mercury (Hg) into the environment where it is organified and biomagnified in aquatic ecosystems. Ingestion of mercury-contaminated fish poses a potential hazard to fish-eating populations such as the Yanomama. We surveyed Hg levels in Yanomama villagers living near mined and unmined rivers in 1994 and 1995, and analyzed Hg levels in piranha caught by villagers. In 1994, 90 Yanomama Indians from 5 villages and in 1995, 62 Yanomama Indians from 3 villages participated in the studies. Four villages surveyed in 1994 were located directly on the Catrimani River, approximately 140-160 km downstream from past gold-mining activities. The other village surveyed in 1994 was situated on the unmined Ajaraní River. In 1995, 2 of the Catrimani River villages were revisited, and a third Yanomama village, on the unmined Pacu River, was surveyed. Blood organic mercury levels among all villagers surveyed ranged from 0 to 62.6 microg L(-1) (mean levels in each village between 21.2 microg L(-1) and 43.1 microg L(-1)). Mercury levels in piranha from the mined Catrimani River ranged from 235 to 1084 parts per billion (ppb). Nine of 13 piranhas, measuring 30 cm or longer had total mercury levels which exceeded mercury consumption limits (500 ppb) set by both the World Health Organization and the Brazilian Ministry of Health. Unexpectedly, high mercury levels were also observed in fish and villagers along the unmined Ajaraní and Pacu Rivers suggesting that indirect sources may contribute to environmental mercury contamination in the Amazon basin.