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.     

Organochlorine pesticides and polychlorinated biphenyls (PCBs) in eggs of red-legged frogs (Rana aurora) and northwestern salamanders (Ambystoma gracile) in an agricultural landscape

Organochlorine pesticides were widely used in the past in Sumas Prairie, British Columbia, Canada. In the 1990s, the hatching success of amphibians from agricultural sites was significantly depressed in the Sumas Prairie compared to reference sites. Therefore, in this study, organochlorine pesticides and polychlorinated biphenyls (PCBs) were measured in eggs of red-legged frogs (Rana aurora) and northwestern salamanders (Ambystoma gracile) from the Sumas Prairie. Egg masses were sampled from three agricultural sites that were exposed to agricultural runoff, and three reference sites that had lower agricultural runoff exposures. Not only was there little difference in contamination between agricultural and reference sites, but the levels of pesticides and PCBs found were lower than the concentrations reported to cause developmental or behavioural problems in amphibians.     

Agricultural soil as a potential source of input of organochlorine pesticides into a nearby pond

A study was conducted in the southeastern region of Buenos Aires province, Argentina, to assess an agricultural soil as a potential source of organochlorine (OC) pesticides for the aquatic biota of a nearby pond. We analyzed gamma-HCH (lindane), still in use, and the following banned compounds: DDT, DDE, DDD heptachlor, heptachlor epoxide, aldrin, dieldrin and endrin in soil, bulrush, grass shrimp and fish using gas chromatography with electron capture detection (GC-ECD). Among the OC pesticides, lindane was most dominant in the soil (32.6 ng/g dry wt in the upper and 173.9 ng/g dry wt in the lower horizon) and bulrush (1.9 pg/g lipid). Macrophyte also accumulated high levels of heptachlor epoxide (1.5 pg/g lipid). Heptachlor, although present in the soil, was below the detection limit in all aquatic biota studied. Its primary degradation product, heptachlor epoxide, was found in both soil and biota samples. DDT was found at low levels in the surface soil (6.8 ng/g dry wt), but at higher concentrations in fish (3.6 pg/g lipid), although levels were still below permissible levels for human consumption. Since most of the compounds were found in both soil and aquatic biota, our study suggests that agricultural soil could be an important source for OC pesticides in the nearby pond.     

Short-term responses of Oryzias latipes (Pisces: Adrianichthyidae) and Macrobrachium nipponense (Crustacea: Palaemonidae) to municipal and pharmaceutical waste water in Beijing, China: survival, behaviour, biochemical biomarkers

Whole effluent toxicity was assessed for the fish Oryzias latipes and the prawn Macrobrachium nipponense for 18 h in a dilution series (0-66%) of the inflow and effluent of a municipal waste water treatment plant as well as waste water from a teramycin producing pharmaceutical industry, before, during and after a pilot laboratory purification process. The waste waters caused acute toxicity as measured by inhibition of light emission in the luminiscent bacterium Vibrio qingaiensis sp. nov. (Q67). EROD and aryl hydrocarbon hydroxylase activity in in vitro carp liver-cells showed a dose-dependent toxic response to the municipal waste water. Behavioural responses and time-to-death of fish and prawn, recorded online with the "Multispecies Freshwater Biomonitor" proved to be concentration- and time-dependent sensitive toxicity indicators in both types of waste water. Behaviour changed stepwise from normal activity to (increased or decreased) activity to more time spent on ventilation and finally to increased morbidity at higher concentration and time of exposure. The municipal waste water treatment plant managed to reduce toxicity to bacteria (Q67), prawn and fish. The pharmaceutical waste water treatment process still has to be improved, in order to reduce toxicity for fish and prawn.     

An analytical method to determine Henry's law constant for selected volatile organic compounds at concentrations and temperatures corresponding to tap water use

Henry's law constants (H) are needed to model human exposure to Volatile Organic Compounds (VOCs) in indoor air resulting from the use of tap water. This paper presents an experimental method to determine Hs for several common tap water pollutants at concentrations and temperatures used in household water. For 5 VOCs Henry's law constants were obtained simultaneously over the 25 degrees C to 45 degrees C temperature range, providing data on H beyond the currently available data (up to 35 degrees C). Henry's law constants were obtained as the ratio of equilibrium concentrations of VOCs in air and water, using simultaneous sampling from sealed bottles kept at constant temperatures. Air and water samples were concentrated by a purge-and-trap method, thermally desorbed from a Tenax trap, and analyzed with a gas chromatograph with an electron capture detector (GC-ECD). Experimental results agreed well with available literature data.     

The effects of land use change on mercury distribution in soils of Alta Floresta, Southern Amazon

This study presents the spatial distribution, degree of contamination and storage capacity of Hg in surface forest and pasture soils from Alta Floresta, Southern Amazon, a significant gold mining site from 1980 to 1996. During that period, average annual gold production was about 6.5 tons, with an estimated Hg annual emission to the environment of about 8.8 tons, 60-80% of it being emitted to the atmosphere. Mercury sources to the region are mining sites and gold-dealer shops at the city of Alta Floresta, where gold is smelted and commercialized. Mercury concentrations in forest soils (15-248 ng g(-1), average=61.9 ng g(-1)) were 1.5-3.0 times higher than in pasture soils (10-74 ng g(-1), average=33.8 ng g(-1)), suggesting strong re-mobilization after deforestation. Highest Hg concentrations were found within a distance of 20-30 km from mining sites in both soil types. The influence of the refining operations within the city of Alta Floresta, however, was less clear. Somewhat higher concentrations were observed only within a 5 km radius from the city center where gold-dealer shops are located. Wind direction controls the spatial distribution of Hg. Background concentrations (15-50 ng g(-1)) were generally found at the outer perimeter of the sampling grid, about 40 km from sources. This suggests that Hg released from mining and refining activities undergoes rapid deposition. Estimated cumulative Hg burdens for the first 10 cm of soil averaged 8.3 mg m(-2) and 4.9 mg m(-2), for forest and pasture soils respectively and compare well with ultisols and hydromorphic oxisols, but were lower than those found in yellow-red and yellow latosols and podsols from other Amazonian areas. Our results show that changing land use in the Amazon is a strong re-mobilizing agent of Hg deposited on soils from the atmosphere.     

Water technology for specific water usage

BACKGROUND: Water is the basis for life and culture. In addition to the availability of water its quality has become a major issue in industrialized areas and in developing countries as well. Water usage has to be seen as part of the hydrological cycle. As a consequence water management has to be sustainable. The aim of the contribution is to give water usage oriented quality criteria and to focus on the technical means to achieve them. MAIN FEATURES: Water is used for many purposes, ranging from drinking and irrigation to a broad variety of technical processes. Most applications need specific hygienic, chemical and/or physical properties. RESULTS: To meet these demands separation and reaction principles are applied. The reuse of water and the application of water treatment with little or no waste and by-product formation is the way to go. Membrane separation and advanced oxidation including catalytic reactions are promising methods that apply natural processes in sustainable technical performance. Thus elimination of specific water constituents (e.g. salts and metals, microorganisms) and waste water cleaning (e.g. pollutants, nutrients and organic water) can be done efficiently. OUTLOOK: Learning from nature and helping nature with appropriate technology is a convincing strategy for sustainable water management.     

Hormetic effect of glyphosate on Urochloa decumbens plants

Abstract

Urochloa decumbens plants may be reached by herbicide drift from applications of glyphosate from neighboring areas or by variations during applications. Considering the different phenological stages and size of plants in these areas, the amount of active ingredient that reaches the plants probably varies. The objective of this study was to evaluate the effects of the application of different doses of glyphosate on U. decumbens plants. Two greenhouse experiments were conducted with two replications at different times. The first experiment evaluated the biological response of U. decumbens plants to glyphosate doses (0, 2.81, 5.63, 11.25, 22.5, 45, 90, 180, 360, 720, and 1,440?g a.e. ha^?1), with six replications. The second experiment evaluated the response of U. decumbens plants to the application of a selected low dose of 11.25?g a.e. ha^?1. Evaluations of injury were performed at 0, 7, 14, and 21?days after application, and dry weight of plants was determined for each evaluation period. U. decumbens plants increased in dry weight when using the glyphosate dose of 11.25?g a.e. ha^?1. However, plants had different responses to the application of this low dose. It can promote both stimulation and inhibition of plant growth.     

Formation of Nitrate and Sulfate in the Plume of Berlin (8 pp)

Background, Aims and Scope Secondary inorganic aerosol (SIA), i.e. particulate sulphate (S(VI)), ammonium and nitrate (N(V)) is formed from gaseous precursors i.e., sulfur dioxide (S(IV)), ammonia and nitrogen oxides, in polluted air on the time-scale of hours to days. Besides particulate ammonium and nitrate, the respective gaseous species ammonia and nitric acid can be formed, too. SIA contributes significantly to elevated levels of respirable particulate matter in urban areas and in strongly anthropogenically influenced air in general. Methods The near-ground aerosol chemical composition was studied at two stationary sites in the vicinity of Berlin during a field campaign in summer 1998. By means of analysis of the wind field, two episodes were identified which allow to study changes within individual air masses during transport i.e., a Lagrangian type of experiment, with one station being upwind and the other downwind of the city. By reference to a passive tracer (Na+) and estimates on dry depositional losses, the influences of dispersion and mixing on concentration changes can be eliminated from the data analysis. Results and Discussion Chemical changes in N(-III), N(V) and S(VI) species were observed. SIA i.e., N(V) and S(VI), was formed from emissions in the city within a few hours. The significance of emissions in the city was furthermore confirmed by missing SIA formation in the case of transport around the city. For the two episodes, SIA formation rates could be derived, albeit not more precise than by an order of magnitude. N(V) formation rates were between 1.4 and 20 and between 1.9 and 59 % h-1 on the two days, respectively, and S(VI) formation rates were > 17 and > 10 % h-1. The area south of the city was identified as a source of ammonia. Conclusion The probability of occurrence of situations during which the downwind site (50 km downwind of Berlin) would be hit by an urban plume is > 7.4%. Furthermore, for the general case of rural areas in Germany it is estimated that for more than half of these there is a significant probability to be hit by an urban plume (> 8%). The S(VI) formation rates are higher than explainable by homogeneous gas-phase chemistry and suggest the involvement of heterogeneous reactions of aerosol particles. Recommendation and Outlook The possible contribution of heterogeneous processes to S(VI) formation should be addressed in laboratory studies. Measurements at more than two sites could improve the potential of Lagrangian field experiments for the quantification of atmospheric chemical transformations, if a second downwind site is chosen in such a way that, at least under particular stability conditions, measurements there are representative for the source area.     

Impact of sublethal doses of 2,4-D, simulating drift, on tomato yield

Tomato is considered one of the most sensitive crops regarding 2,4-D drift. In many cases, such susceptibility has led to important restrictions in the use of 2,4-D based products. Field experiments were carried out for two consecutive years in tomato, by applying sublethal doses of 2,4-D (ranging from 0.42 to 13.44 g a.i. ha(-1)) directly to plants, at different stages of growth, as a simulation of eventual drifts to the crop. The range of rates was based on the assumption of a 0.0625-2.0% drift level of a 1 L ha(-1) of the most common formulated herbicides. For this crop, the range of rates between 0.42 and 13.44 g a.i ha(-1) applied at the beginning of flowering caused a linear crop reduction. On the other hand, rates < or = 13.44 g a.i. ha(-1) applied after full development of fourth truss stage or latter had no effect on crop yield or development. For tomato, tolerance to 2,4-D strongly increases with plant age.