Atmospheric Transport and Air-Surface Exchange of Pesticides

Atmospheric transport and exchange of pesticides with soil, vegetation, water and atmospheric particles are discussed, with an emphasis on applying physicochemical properties of the compound to describe environmental partitioning. The octanol-air partition coefficient is promoted as a unifying property for describing volatilization of pesticides from soil and sorption to aerosols. Present-day sources of organochlorine (OC) pesticides to the atmosphere are continued usage in certain countries and volatilization from contaminated soils where they were used in the past. Models are available to predict volatilization from soil; however, their implementation is hampered by lack of soil residue data on a regional scale. The need to differentiate "new" and "old" sources is increasing, as countries negotiate international controls on persistent organic pollutants (POPs). A new technique, based on the analysis of individual pesticide enantiomers, is proposed to follow emission of chiral OC pesticides from soil and water. Air monitoring programs in the Arctic show the ubiquitous presence of OC pesticides, PCBs and other POPs, and recently a few "modern" pesticides have been identified in fog and surface seawater. Atmospheric loadings of POPs to oceans and large lakes take place mainly by air-water gas exchange. In the case of OC pesticides and PCBs, aquatic systems are often near air-water equilibrium or even oversaturated. Measurement of water/air fugacity ratios suggests revolatilization of PCBs and several OC pesticides in the Great Lakes and, for α-hexachloroacyclohexane (α-HCH), in the Arctic Ocean. Outgassing of α-HCH in large lakes and arctic waters has been confirmed by enantiomeric tracer studies. The potential for pesticides to be atmospherically transported depends on their ability to be mobilized into air and the removal processes that take place enroute: wet and dry deposition of gases and particles and chemical reactions in the atmosphere. Measurement of reaction rate constants for pesticides in the gas and particle phase at a range of environmental temperatures is a critical research need. The transport distance of a chemical is related to its overall environmental persistence, determined by the partitioning among different compartments (water, sediment, soil, air), degradation rates in each compartment and mode of emission (into water, soil, air). Several pesticides found in the arctic environment have predicted lifetimes in the gas phase of only a few days in temperate climates, pointing out the need for monitoring and evaluation of persistence in cold regions.     

SBSE-GC-ECD/FPD in the analysis of pesticide residues in Passiflora alata Dryander herbal teas

Stir bar sorptive extraction (SBSE) in combination with GC-ECD/FPD analysis is here applied to the determination of the residues of 11 pesticides (hexachlorobenzene, lindane, chlorothalonil, parathion methyl, parathion ethyl, fenitrothion, malathion, dieldrin, alpha- and beta-endosulfan, and tetradifon) in herbal teas prepared with Passiflora alata Dryander spiked leaves. The method was optimized using spiked herbal teas in a range from 0.05 to 1 pg/microL for organochlorine pesticides and from 0.15 to 3 pg/microL for organophosphorus pesticides. The method is reproducible and repeatable with recoveries calculated from herbal teas prepared with spiked plant material versus spiked herbal teas, varying from about 30% for tetradifon to about 90% for parathion methyl and malathion. The limits of quantitation (LOQs) ranged from 0.017 pg/microL for lindane to 0.117 pg/microL for malathion.     

Survey of Underutilized Grain Legume Production Systems in the Southwest Agricultural Zone of Nigeria

ABSTRACT

A socio-economic survey of production systems was carried out in four out of the eight states that make up the southwest agricultural zone of Nigeria. A total of 157 minor grain legume farmers selected by multi-stage sampling were interviewed using structured questionnaires. The study shows that lima bean, pigeon pea, African yam bean, and bambara groundnut are the prominent minor grain legumes grown on less than 10% of the total cultivated land area. The minor grain legumes are grown on an average land size ranging from 0.2 to 0.4ha and predominantly in mixture with crops like cassava, maize, yam, sorghum, cocoyam, etc. The use of modern inputs like herbicides, pesticides, fertilizers, and improved varieties is uncommon in minor legume production systems. The cultivation of these legumes is more popular among the older members of the farming communities, about 78% of which are above 40 years of age. The average yield of the legumes on farms is considerably low, estimated at 271kg/ha, 265kg/ha, 174kg/ha, and 275kg/ha for lima bean, pigeon pea, African yambean, and bambara groundnut, respectively. Major constraints identified by the farmers include low market demand, inadequate seed supply, high cost of labour, and low yield. Research work is therefore needed in agronomy and breeding for improved yield and utilization for expanded market and, consequently, increased production.     

新疆典型农业地区土壤中有机氯农药（OCPs）分布特征及风险评价

为加强有机氯农药(organic chlorinated pesticides,OCPs)的污染预防与控制,该研究分析了新疆典型农业地区有机氯农药的污染状况并对其进行了风险评价。采集表层土壤样品36个,分析其中15种OCPs的残留状况。六六六(Hexachlorocyclohexanes,HCHs)、滴滴涕(dichlorodiphenyltrichloroethanes,DDTs)、氯丹类化合物、硫丹和硫丹盐的质量分数范围分别是0.37～22.82、0.91～858.47、0.15～47.08ng/g、N.D(未检出)～16.27和N.D～73.83ng/g。对OCPs的来源进行分析,发现HCHs来源于历史上工业HCHs的使用或近期林丹的输入,DDT来源于工业品的违法使用和三氯杀螨醇的使用,研究区域氯丹存在新的来源,而硫丹新来源较少。通过主成分分析,从15种OCPs中提取了5个主成分,总方差解释量达到了79.93%。5个主成分分别归因于DDT和工业HCH s的使用、OCPs原料的差异以及研究区域内病虫害的发病特征等。利用灰色关联分析研究区域内OCPs污染状况,结果表明石河子污染水平最高,各研究区域土壤均需要采取进一步的污染控制措施。     

Atmospheric pollution and fallout by PCBS and organochlorine pesticides (Ile-De-France)

Air pollution and atmospheric deposition by PCBs and organochlorine pesticides (isomers of HCH and p,p′-DDE) were studied at Paris from January 1986 to June 1987. The deposition measured as total (wet plus dry) was also followed during 1986 on two suburban and two rural sites. The distribution of the pollutants between the vapor phase and aerosols was evaluated by sampling air through a glass microfiber filter connected to a Tenax resin cartridge. The study shows that in the atmosphere as in waters of the catchment area of the Seine river, PCBs are the main organochlorine pollutants. Pollution by OCL is of the same order as the one described in literature (mean γ-HCH concentration 1.4 ng m^?3) while PCB concentrations in the atmosphere are equal to or higher than those observed in USA and Europe (range 5 to 44 ng m^?3). On the average, 93% of the PCBs are in the vapor phase with a composition approximating Aroclor 1242. In aerosols and precipitations the composition is closely related to Aroclor 1254. The total fallout for 1986 was 40 μg m^?2 for PCBs and 20 μg m^?2 for γ-HCH, rainfall being 611 mm.     

Occurrence and distribution of organochlorine pesticides (OCPs) in tomato (Lycopersicon esculentum) crops from organic production

Organochlorine pesticides (OCPs) were quantified by GC-ECD in tomato (Lycopersicon esculentum) during a vegetation period. Plants were harvested at 15, 60, and 151 days after seed germination. Leaves, stem, roots, and fruit (peel and flesh) were analyzed separately. The results showed that tomato plants were able to accumulate OCPs from soils, and a trend to reach the equilibrium among tissues at mature stages was also observed. Endosulfans comprised the main OCP group, probably due to its spray during summer months in the surrounding areas. Banned pesticides such as DDTs, heptachlor, and dieldrin were found. OCPs levels in the fruit were below the maximum residues limits (MRL) considered by the Codex Alimentarius. DDE/DDT and alpha-/gamma-HCH ratios of <1 would indicate recent inputs of DDT and lindane in the environment. The occurrence of OCPs in the study farm, where agrochemicals have never been used, is a result of atmospheric deposition of those pesticides.     

Occurrence and distribution of chemical pollutants in Lake Mariut,Egypt

Occurrence and distribution of organochlorine pesticides in the water of Lake Mariut, a brackish coastal Egyptian lake suffering from pollution, and their accumulation in the common fish Tilapia were studied. The major pesticides detected in the lake water were lindane, p,p′-DDE, o,p′-DDT, and p,p′-DDT. These compounds, except o,p′-DDT, were detected in the fish samples in exceedingly higher concentrations compared with those found in the lake water.     

Literature Review: Occurrence,Degradation and Fate of Pesticides During Composting: Part II: Occurrence and Fate of Pesticides in Compost and Composting Systems

This paper reviews the findings of research reported in the currently available literature regarding the occurrence and transformations of pesticides through the composting process and the use of compost. Part I summarizes the composting process, pesticides and mechanisms of pesticide degradation. Part II reviews research studies concerning the occurrence and fate of pesticides during composting. Investigations of pesticide residues in composting feedstocks and finished compost detected few of the target pesticides. The compounds that were found occurred at low concentrations. The majority of the compounds detected were insecticides in the organochlorine category, including chemicals that have been banned from use in the U.S. for many years. Generally, organophosphate and carbamate insecticides and most herbicides were rarely detected. Comparisons of pesticide concentrations before and after composting also showed organochlorine compounds to be most resistant to biodegradation during composting. With some exceptions, pesticides in other categories decomposed moderately well to very well. Studies that followed the mechanisms of degradation indicate that mineralization accounts for only a small portion of pesticide disappearance. Other prominent fates include partial degradation to secondary compounds, adsorption, humification, and volatilization. In general the research results suggest that the pattern of pesticide degradation during composting is similar to the degradatiion observed in soils. With a few important distinctions, composting can be considered a biologically active soil environment in which degradation is accelerated. However, as some studies noted, composting does not always speed the degradation of all pesticides. The nature of the pesticide, specific composting conditions and procedures, the microbial communities present, and the duration of composting affect the extent and the mechanisms of degradation.     

Sulfuric acid cleanup and KOH-ethanol treatment for confirmation of organochlorine pesticides and polychlorinated biphenyls: application to wastewater samples

The efficacy of sulfuric acid cleanup and KOH-ethanol hydrolysis confirmation was studied for 22 organochlorine pesticides and 2 polychlorinated biphenyls (PCBs). Mean recoveries for different treatment times are given. The method was applied to analysis of several wastewater samples by gas chromatography with electron capture detection. Organochlorine compounds were extracted by using separatory funnels and 15% diethyl ether in hexane as extractant. All the compounds studied could be analyzed except trifluralin, dichloran, dieldrin, and endrin, which were destroyed after treatment with concentrated H2SO4. The pesticides found most commonly in the samples analyzed were fenson, tetradifon, lindane, methoxychlor, and dicofol.     

Occurrence,Degradation and Fate of Pesticides During Composting

This paper reviews the findings of research reported in the currently available literature regarding the occurrence and transformations of pesticides through the composting process and the use of compost. Part I summarizes the composting process, pesticides and mechanisms of pesticide degradation. Part II reviews research studies concerning the occurrence and fate of pesticides during composting. Investigations of pesticide residues in composting feedstocks and finished compost detected few of the target pesticides. The compounds that were found occurred at low concentrations. The majority of the compounds detected were insecticides in the organochlorine category, including chemicals that have been banned from use in the U.S. for many years. Generally, organophosphate and carbamate insecticides and most herbicides were rarely detected. Comparisons of pesticide concentrations before and after composting also showed organochlorine compounds to be most resistant to biodegradation during composting. With some exceptions, pesticides in other categories decomposed moderately well to very well. Studies that followed the mechanisms of degradation indicate that mineralization accounts for only a small portion of pesticide disappearance. Other prominent fates include partial degradation to secondary compounds, adsorption, humification, and volatilization. In general the research results suggest that the pattern of pesticide degradation during composting is similar to the degradation observed in soils. With a few important distinctions, composting can be considered a biologically active soil environment in which degradation is accelerated. However, as some studies noted, composting does not always speed the degradation of all pesticides. The nature of the pesticide, specific composting conditions and procedures, the microbial communities present, and the duration of composting affect the extent and the mechanisms of degradation.     

A field evaluation of the Hasl wet-dry deposition collector

Samples of precipitation, dry deposition and total deposition have been obtained from Tutuila Island, American Samoa, since April 1976. These collections are part of a study of global levels of pollutants. The volume of rain water collected by a HASL wet/dry collector has averaged within 4% of the volume expected based on data obtained using a standard rain gauge. The deposition of Cl^?, SO ₄ ^?2 , NA⁺. Mg^?2 and K⁺ in the total collector, which is exposed continuously to the atmosphere, is about 10% greater than the deposition in the wet plus dry sides of the HASL collector.     

On processes controlling the distribution and fluxes of boron in natural waters and air along transects across the South Island of New Zealand

The concentrations of boron were measured in rain, air and soil water along transects across the Southern Alps, New Zealand, during southern autumn and early winter 1999. Estimates of wet deposition, dry deposition, and flux of boron leaving the soil in soil water are presented. At the Main Divide of the Southern Alps, strong and constant orographic effects on rain-bearing fronts resulted in low concentrations and little variation of boron in rain. Areas with less orographic influence received varying boron concentrations in the rain depending on the origin and character of the fronts. Concentrations of boron in air were greater near the sea than in the intramontane basin. High mean concentrations in air go together with large variations caused by changes of wind direction and speed during frontal passages. Air reaching the intramontane basin was depleted of boron because of washout over the eastern and western ranges and by dry deposition. After a long dry summer spell, the first autumn flush of soil water contained high concentrations of boron at low soil water flow. Later, as the soil wetted up, the soil water concentration approached that of rain water at all sites. Wet deposition was least at sites away from the coast where there was little rain and less boron in it. High rainfall with low boron concentrations or mean rainfall with high boron concentrations occurred near the eastern and western divides. Dry deposition varied over shorter time intervals and distances than wet deposition. It was high near the coastlines during onshore winds and low in the intramontane basin, especially with weak convective turbulence. The concentrations of boron in springs resembled those in rain and soil water, increasing from the western coastal plain eastwards across the Southern Alps.     

Organochlorine pesticides in gamebirds of Eastern Tennessee

Muscular tissue specimens of adult grouse, quail and woodcock from the rural counties of upper East Tennessee have been analyzed by gas chromatography for the organochlorine pesticides lindane, heptachlor, endrin, aldrin, dieldrin, DDT (total) and methoxychlor. Procedures for the analyses are described. The pesticidal levels in the muscle of all gamebirds exceeded the acceptable levels shown in governmental sources and professional journals. The observed concentrations constitute a serious threat to the wildlife of the region and permit accumulation and magnification even in man, who eats gamebirds as a part of his diet.     

PCBs and Organochlorine Pesticides in Lake Orta (Northern Italy) Sediments

PCB congeners and organochlorine pesticides (DDT, lindane and HCB) distribution were studied in Lake Orta sediments. The results indicated a contaminated area in the nor-them part of the sub-basin. The observed high levels of organochlorine compounds (OCs) may he explained by the focusing phenomenon, ie. the preferential transport of lighter and smaller particles from the emission sources to this area. The PCBs and DDT values were correlated with the organic carbon content and the heavy metal contamination. The toxicity of the sediment samples was related also to PCB content. PCBs and OCs pollution of Lake Orta was of the same order of magnitude as in Lake Como, which is the most contamined lake in Northern Italy.     

Wet and Dry Deposition Fluxes of Polychlorinated Biphenyls (PCBs) in an Urban Area of Turkey

Atmospheric polychlorinated bihenyls (PCBs) deposit by dry and wet deposition mechanisms, and therefore they constitute a significant polluting source for lands and surface waters. Various samplers have been used to determine the PCB pollution level resulting from deposition. In the presented study, a modified wet deposition sampler (WDS) was used for sampling both wet and dry deposition samples with the same instrument by which wet deposition reservoir of the WDS is opened and dry deposition reservoir is closed when rain starts. Wet and dry deposition samples were collected between June 2008 and June 2009. In the samples taken from BUTAL which is known as an urban area with heavy traffic, ??PCB dry deposition fluxes were determined as 18?±?10 ng/m²??day, and wet deposition fluxes for dissolved and particle phase were measured as 480?±?1,185 and 475?±?1,000 ng/m²??day, respectively. The dissolved and particle-phase PCB concentrations in rain were 10?±?13 and 13?±?14 ng/l, respectively. The contribution of wet deposition to total PCB deposition was determined as 52%. PCB concentrations in the ambient air were measured to be 370?±?200 and 20?±?20 pg/m³ for gas and particle phases, respectively. Washout ratio was determined by proportioning rain concentration to concentration in air. The washout ratios of the samples were between 1,675?C311,800 and 12,775?C2,511,120 for dissolved and particulate phases, respectively.     

Organochlorine pesticide residues in leek (Allium porrum) crops grown on untreated soils from an agricultural environment

Leek (Allium porrum) plants from organic farming were harvested at 15, 59, and 210 days after seed germination. Organochlorine pesticide (OCP) levels were quantified by GC-ECD in vegetative tissues (roots and aerial), bulk soil and rhizosphere. Leek plant bioaccumulate OCPs efficiently in their aerial and root tissues and alter the concentration of the soil where they are grown. OCPs distribution pattern of bulk soil was endosulfans > DDTs > dieldrin, while it was endosulfans > HCHs > DDTs in leek tissues. There were statistically significant declines in DDTs, chlordane, dieldrin, and heptachlor in the rhizosphere, indicating that recalcitrant residues of OCPs may be removed from contaminated soil using leek crops under normal growing conditions. The DDE/DDT and alpha-/gamma-HCH ratios of < 1 would indicate recent inputs of DDT and lindane in the environment. The occurrence of OCPs in this farm could be the result of atmospheric deposition and/or surface runoff of these pesticides.     

Atmospheric bulk deposition of trace metals to the Seine river Basin, France: concentrations, sources and evolution from 1988 to 2001 in Paris

Concentrations of Cd, Cu, Ni, Pb and Zn were determined in bulk atmospheric deposition collected at five stations in the Seine River basin (France), to evaluate sources and fluxes of atmospheric trace metals. Bulk deposition (wet + dry) was sampled weekly from March 2001 to February 2002 for 4 sites and from March to December 2001 for the last one. The concentrations of the elements in bulk deposition (dissolved + particulate form) followed the order: Zn > Pb > Cu > Ni > Cd. Concentrations of Zn, Pb and Ni were highly correlated with one another, suggesting a common source, related to the combustion of coal and heavy fuel. Metal concentrations in bulk deposition did not exhibit a high degree of temporal variability over the annual cycle and were not obviously related to meteorological parameters (rainfall, wind). Estimates of the total annual direct atmospheric deposition of metals to the Seine Estuary ranged from 16 kg yr^{? 1} for Cd to 5600 kg yr^{? 1} for Zn. Loadings of Cd, Cu and Ni from direct atmospheric inputs were less than 1% of those contributed by the Seine River and loadings of Pb and Zn represented 1.27% and 1.56% of the Seine contribution. Direct atmospheric inputs are negligible compared to fluvial inputs, but the indirect atmospheric deposition to the estuary was not estimated. Based on these results, trace metal concentrations in Paris have decreased by a factor of 4.6 for Zn and by a factor of 50 for Ni from 1988 to 2001. Of particular interest is the continued decrease in bulk deposition of Pb during this period, underlining the impact of policy initiatives concerning the reduction of lead on emissions in France.     

Wet deposition of current use pesticides at a rural location on the Delmarva Peninsula: impact of rainfall patterns and agricultural activity

Event-based precipitation samples were collected during the main agricultural season (April-September) over 4 years (2000-2003) at one site in the Choptank River Watershed on the Delmarva Peninsula. The samples were analyzed for 19 agricultural pesticides to determine the contribution of wet deposition as a source of these compounds to the Chesapeake Bay and the factors affecting the temporal trends in deposition. Chlorothalonil was detected most frequently (92% samples) followed by metolachlor (66%) and endosulfans (49%). Although chlorothalonil is the single biggest contributor to pesticide flux (33-46%), pesticide wet deposition is dominated by herbicides (46-61%), with the greatest fluxes occurring during the time of herbicide application on corn and soybeans. The analysis suggests that the extent of wet deposition of herbicides depends on the timing of precipitation relative to herbicide application. The insecticide and fungicide flux was greater in years with above-average rainfall (2001 and 2003), suggesting that for these pesticides deposition flux is dependent on the total amount of rainfall in the agricultural season. The data indicate that the use of chlorpyrifos, an organophosphate insecticide which is on the Toxics of Concern list for the Bay, is on the increase. Total pesticide flux ranged from 90 microg/m2 (2001) to 180 microg/m2 (2000). Wet deposition can account for up to 10-20% of the annual loadings of pesticides to the Bay.     

Composition, Distribution, and Characterization of Organochlorine Pesticides in Sandstorm Depositions in Beijing, China

Sandstorms which distribute a great number of particles are a special atmospheric occurrence and are uncommon in northern China. This study was conducted to determine, for the first time, the concentration of organochlorine pesticides (OCPs) in sandstorm depositions. Samples were collected from urban areas of Beijing and a total of eight OCPs were measured. All samples contained OCP residues. The total hexachlorocyclohexane (HCHs) concentration ranged from 20.6 to 59.8ng g^?1 and the total dichlorodiphenyltrichloroethane (DDTs) concentration ranged from 12.0 to 14.3ng g^?1. Furthermore, increasing HCH contamination was observed from the northwest to the southeast and a uniform distribution of DDT contamination was discovered in Beijing. Analysis of the sources of contamination showed that HCHs in the sandstorm depositions were derived from a relatively old source of lindane, and DDTs mainly originated from an old source of dicofol in Beijing. The preliminary pollution assessment of the samples indicated that HCH levels might be categorized as low pollution and DDT levels might be categorized as no pollution. The present study suggests that sandstorm depositions may not produce the special risk of adverse health effect from OCPs for the residents of Beijing, China.