The significance of entry routes as point and non-point sources of pesticides in small streams

In an agricultural catchment area in Germany we analyzed water samples from five entry routes for 2 insecticides. 5 fungicides and 13 herbicides. The sewage plant outlet and the emergency overflow of a sewage sewer contained only herbicides. In each farmyard runoff we found on average 24 g pesticides during application period, presumably caused by cleaning the spraying equipment. In comparison, the field runoff and the rainwater sewer contained less load, but also insecticides, fungicides and herbicides. The sewage plant caused 65.9% of the total herbicide load, the sewage sewer 19.8% and the farmyard runoff 12.8%. The farmyards also caused 83.7% of total insecticide and 83.8% of fungicide load. The total load of all entry routes is correlated with the amount of pesticides applied in the catchment area and the Ko/w value for each pesticide (mult. regress. r2: 0.82; p<0.0001; n = 14). In stream A the sewage plant caused a slight but continuous contamination by herbicides with 82% of the total load found during low-water phases. In comparison, stream B had only farmyard runoff and non-point sources, which caused high peaks of herbicide and a contamination by insecticides. Consequently, high-water phases generated 70% of the total pesticide load.     

Comparison of different sampling techniques for the evaluation of pesticide spray drift in apple orchards

An analytical method using gas chromatography-mass spectrometry has been developed for the evaluation of different sampling techniques to characterise spray drift in a commercial apple orchard. Eleven pesticides were studied (fungicides, insecticides and herbicides). A collection of airborne spray-drift pesticides released from a low-profile air-blast orchard sprayer was investigated using six types of samplers: (1) a Perkin-Elmer low volume automatic air sampler using with glass tube packed with Supelpak-2; (2) a high volume air sampler: (3, 4) an impinger containing cyclohexane that could be preceded by a glass fibre filter; and (5, 6) glass cartridges packed with Supelpak-2 that could be preceded by a glass fibre filter. Retention efficiencies of the different sampling techniques are compared, and physical forms of the retained pesticides are discussed. These techniques have allowed us to evaluate pesticide spray-drift in the orchard. Results have shown that the molecules' properties (k(H) and vapour pressure) and weather conditions (temperature and relative humidity) strongly influence pesticide gas and particles distribution. However, in the studied orchard, it is difficult to differentiate pesticide spray-drift and post-application transfers since treatment duration was > 2 days.     

Pesticides in Portuguese surface and ground waters

Pesticides used in Portuguese agricultural areas have been found in surface and ground waters. In the surface water collected in three river basins from 1983 to 1999, insecticides and herbicides were detected from the monitored pesticides, particularly atrazine, chlorfenvinphos (Z+E), alpha- and beta-endosulfan, lindane, molinate and simazine, reaching the maximum values, respectively, of 0.63, 31.6, 0.18 microg/L (alpha-endosulfan), 0.18 microg/L (beta-endosulfan), 0.24, 48 and 0.3 microg/L. In the ground water collected from the wells of seven agricultural areas from 1991 to 1998, several monitored herbicides were detected: alachlor, atrazine, metolachlor, metribuzine and simazine, reaching the maximum concentration values of 13, 30, 56, 1.4 and 0.4 microg/L, respectively. The herbicides more frequently detected were atrazine (64%), simazine (45%) and alachlor (25%). Other than these, the monitored pesticides can be present in Portuguese surface and ground waters. Therefore, to improve the analytical conditions, the use of multiresidue methods and automated techniques are desirable in future work.     

Fire and Pesticides, A Review and Analysis of Recent Work

There are a number of circumstances that involve the burning of toxic materials, including pesticides, herbicides, insecticides, and poisonous plant or plant products. Toxicity issues of smoke from the Anacardiaceae family and the Oleander are discussed and contrasted with that from pesticides, herbicides, insecticides, and other organic materials. Work in two major European programs is reviewed. Survival fractions in smoke of 1 to 10% can be expected for some toxic compounds in fires. Survival fractions are dependent not only upon the specific toxic compound but on the fire scenario and other fuels present. Of importance, flaming combustion mat not ensure destruction of such compounds in real fire incidents.     

Concentrations and loads of suspended sediment-associated pesticides in the San Joaquin River, California and tributaries during storm events

Current-use pesticides associated with suspended sediments were measured in the San Joaquin River, California and its tributaries during two storm events in 2008. Nineteen pesticides were detected: eight herbicides, nine insecticides, one fungicide and one insecticide synergist. Concentrations for the herbicides (0.1 to 3000 ng/g; median of 6.1 ng/g) were generally greater than those for the insecticides (0.2 to 51 ng/g; median of 1.5 ng/g). Concentrations in the tributaries were usually greater than in the mainstem San Joaquin River and the west side tributaries were higher than the east side tributaries. Estimated instantaneous loads ranged from 1.3 to 320 g/day for herbicides and 0.03 to 53 g/day for insecticides. The greatest instantaneous loads came from the Merced River on the east side. Instantaneous loads were greater for the first storm of 2008 than the second storm in the tributaries while the instantaneous loads within the San Joaquin River were greater during the second storm. Pesticide detections generally reflected pesticide application, but other factors such as physical-chemical properties and timing of application were also important to pesticide loads.     

Assessment of photo-Fenton and biological treatment coupling for Diuron and Linuron removal from water

The coupling of photo-Fenton (chemical) and biological treatments has been used for the removal of Diuron and Linuron herbicides from water. The chemical reaction was employed as a pre-treatment step for the conversion of the toxic and non-biodegradable herbicides into biodegradable intermediates that were subsequently removed by means of a biological sequencing batch reactor (SBR). Multivariate experimental design was used to select four photo-Fenton reagent dose combinations for the coupling experiments. Concentrations of hydrogen peroxide between 10 and 250 mg L(-1), and iron (II) concentrations between 2 and 20 mg L(-1) have been tested. 15.9 mg L(-1) of Fe(II) and 202 mg L(-1) of H(2)O(2) were needed to convert initial toxic and non-biodegradable herbicides into suitable intermediates for a subsequent biological treatment. Detrimental effects due to the excess of reactants were detected. Chemical oxygen demand (COD), average oxidation state (AOS), total organic carbon (TOC) and hydrogen peroxide concentration are the parameters used to trace the experiments course. Also, toxicity (EC(50)(15)) and biodegradability (BOD(5)/COD) tests were carried out at the end of each chemical oxidation. Complete disappearance of the herbicides from water was observed after the chemical treatment, while 3,4-dichloroaniline and 3,4-dichlorophenyl isocyanate were identified as the main by-products of the degradation process. Complete TOC removal was achieved after biological treatment in a SBR using a hydraulic retention time (HRT) of 2 days.     

Occurrence of cotton herbicides and insecticides in playa lakes of the High Plains of West Texas

During the summer of 1997, water samples were collected and analyzed for pesticides from 32 playa lakes of the High Plains that receive drainage from both cotton and corn agriculture in West Texas. The major cotton herbicides detected in the water samples were diuron, fluometuron, metolachlor, norflurazon, and prometryn. Atrazine and propazine, corn and sorghum herbicides, were also routinely detected in samples from the playa lakes. Furthermore, the metabolites of all the herbicides studied were found in the playa lake samples. In some cases, the concentration of metabolites was equal to or exceeded the concentration of the parent compound. The types of metabolites detected suggested that the parent compounds had been transported to and had undergone degradation in the playa lakes. The types of metabolites and the ratio of metabolites to parent compounds may be useful in indicating the time that the herbicides were transported to the playa lakes. The median concentration of total herbicides was 7.2 microg/l, with the largest total concentrations exceeding 30 microg/l. Organophosphate insecticides were detected in only one water sample. Further work will improve the understanding of the fate of these compounds in the playa lake area.     

Detection of the marine toxin okadaic acid in mussels during a diarrhetic shellfish poisoning (DSP) episode in Thermaikos Gulf, Greece, using biological, chemical and immunological methods

An approach involving chemical and biological techniques was taken for the detection and quantification of the marine toxin okadaic acid (OA) in mussels from Thermaikos Gulf, Greece, during a 4-month DSP episode that occurred in 2002. Samples were analyzed using the mouse bioassay, high performance liquid chromatography (HPLC) with fluorimetric detection and an enzyme-linked immunosorbent assay (ELISA). Okadaic acid was quantifiable at three different sites of Thermaikos Gulf reaching a maximum concentration of 36 microg/g hepatopancreas. High correlation was revealed between results derived from HPLC and ELISA (R2=0.998), while 91% consistency between HPLC and the mouse bioassay results was observed.     

Pesticides in the atmosphere of the Mississippi River Valley, part II--air

Weekly composite air samples were collected from early April through to mid-September 1995 at three paired urban and agricultural sites along the Mississippi River region of the Midwestern United States. The paired sampling sites were located in Mississippi, Iowa, and Minnesota. A background site, removed from dense urban and agricultural areas, was located on the shore of Lake Superior in Michigan. Each sample was analyzed for 49 compounds; of these, 21 of 26 herbicides, 13 of 19 insecticides, and 4 of 4 related transformation products were detected during the study, with most pesticides detected in more than one sample. The maximum number of pesticides detected in an air sample was 18. Herbicides were the predominant type of pesticide detected at every site. Detection frequencies of most herbicides were similar at the urban and agricultural sites in Iowa and Minnesota. In Mississippi, herbicides generally were detected more frequently at the agricultural site. The insecticides chlorpyrifos, diazinon, and carbaryl, which are used in agricultural and non-agricultural settings, were detected more frequently in urban sites than agricultural sites in Mississippi and Iowa. Methyl parathion was detected in 70% of the samples from the Mississippi agricultural site and at the highest concentration (62 ng/m3 air) of any insecticide measured in the study. At the background site, dacthal (100%), atrazine (35%), cyanazine (22%), and the (primarily atrazine) triazine transformation products CIAT (35%) and CEAT (17%) were detected most frequently, suggesting their potential for long-range atmospheric transport.     

A comparison of microbial bioassays for the detection of aquatic toxicants

The toxicity of 35 test chemicals was analyzed using two microbial bioassay systems. The commercially available Microtox Toxicity Analyzer System™ and the two-organism procedure of Tchan were used to determine the concentration of test chemicals resulting in a 50% reduction in response (EC₅₀). Both of the tests employed a luminescent bacterium while the procedure of Tchan also utilized an alga. Results from the two microbial tests were compared with available data obtained with fish toxicity bioassays and with each other. The Microtox™ procedure was somewhat more sensitive than the Tchan bioassay in detecting most of the test chemicals and fish bioassays were generally more sensitive than either of the microbial tests. As a notable exception, photosynthesis-inhibiting herbicides were detected at remarkably lower concentrations with the procedure of Tchan than any of the other bioassays. Potential applications for these tests are discussed.     

Concentrations of urinary pesticide metabolites in small-scale farmers in Chiang Mai Province, Thailand

Our research goal was to assess exposure to currently used pesticides among small-scale male farmers residing in two topographically different areas in Chiang Mai Province, Thailand. Farmers (N = 136) were recruited from Pong Yaeng subdistrict (N = 67) and Inthakhin subdistrict (N = 69). Each farmer provided a morning urine void for the analysis of 30 urinary metabolites of insecticides, herbicides, and fungicides. Farmers in Pong Yaeng had significantly higher urinary concentrations of metabolites of organophosphorus insecticides and ethylene bisdithiocarbamates, while farmers from Inthakhin had significantly higher concentrations of malathion, 2,4-D, alachlor, and parathion or EPN metabolites. Based upon the metabolites measured in the urine of the farmers, chlorpyrifos and pyrethroid insecticides seemed to be commonly used across both communities; no significant differences in metabolite concentrations of these insecticides were observed between the two farmer groups. The presence of methamidaphos in the urine of farmers suggests that, despite a ban on its use, methamidaphos continues to be used in the communities. A similar finding with metabolites of methyl parathion must be further investigated. Overall, our results suggest that while each community may use different pesticides, Thai farmers are exposed to a wide variety of pesticides with a broad range in exposure magnitude. Furthermore, age, field size, crop production type, and the use of protective equipment were found to be potential factors influencing the degree of exposure.     

Detection of persistent organic pollutants in the Mississippi Delta using semipermeable membrane devices

From semipermeable membrane devices (SPMDs) placed in five Mississippi Delta streams in 1996 and 1997, the persistent organic pollutants (POPs) aldrin, chlordane, DCPA, DDT, dieldrin, endrin, heptachlor, mirex, nonachlor, and toxaphene were detected. In addition, the insecticides chlorpyriphos, endosulfan, and hexachlorocyclohexanes were detected. Two low-solubility herbicides not detected commonly in surface water, pendimethalin and trifluralin, were also detected.     

Comparison of algal assay systems for detecting waterborne herbicides and metals

The EPA Bottle Test was compared to a short-term algal bioassay method (Oxygen Evolution Assay) for detecting waterborne herbicides and metals. Although the Bottle Test proved to be a more sensitive assay system, the responses of the two bioassays correlated well. The Oxygen Evolution Assay may be useful as a rapid preliminary screening method for determining which chemicals should undergo further testing. In both bioassays, differences were observed in the results of experiments conducted in the standard algal growth medium and in nutrient-enriched water samples, suggesting that water chemistry plays an important role in the determination of specific toxicity thresholds for algae.     

A bacterial bioassay for assessment of wastewater toxicity

A bioassay using freeze-dried Nitrobacter as the test organism has been shown to successfully detect various toxicants in municipal and industrial wastewaters. The test is simple, sensitive, rapid and inexpensive; as a result, this test shows potential as a quantitative measurement technique for wastewater toxicity.The bioassay technique was applied in the analysis of a wastewater treatment system at a fiberboard plant near Portland, Oregon. The fiberboard is manufactured from a slurry of chipped wood, shavings and sawdust.Wastewater from the process is treated at an on-site facility consisting of settling ponds, activated sludge basin, clarifier and holding ponds. Treated water is recycled to the mill for reuse. Recently the removal of BOD by the activated sludge system dropped significantly and soluble and particulate organics began to accumulate. The influent and effluent flows for the treatment facility were tested with the Nitrobacter bioassay and both were determined to have significant toxicity. Further tests at points in the process showed that the toxicity was not associated with a single waste stream and was prevalent throughout the entire wastewater treatment system. In an effort to identify the toxicant, toxicity tests were conducted for known chemicals used in the process. The wastewater was treated with various physical and chemical unit processes to determine the most effective method for toxicity removal.Due to the complexity of the wastewater composition, no specific agents have been identified as solely responsible for the observed toxic response, however, several possible explanations for the apparent toxicity are discussed.     

Transgenic plants – prospects and problems

Genetic engineering leading to the development of transgenic organisms is emerging as the latest thrust area of biotechnology related research. New methods of gene transfer have made it possible to transfer genes to unrelated species, thus eliminating some of the difficulties of conventional methods of crop improvement. Conventional genetic management practices, such as hybridization are possible only with sexually compatible species thus limiting its scope, whereas the genetic manipulation has unlimited scope. Today, the DNA of plants can be directly modified by recombinant DNA (R‐DNA) techniques. New varieties of agronomical plants possessing any possible combination of desired characteristics can be theoretically developed by this technology. The principal objective of plant biotechnology is to increase the biological productivity by creating new varieties of cultivated plants. The basis for change in traits by transgenesis is identification, characterization, isolation, purification and cloning of genes followed by the transfer to the target plant. Plant varieties with tolerance to several diseases, pathogens, pests, extreme climatic conditions, herbicides, environmental stress, senescence etc. have been produced by genetic engineering. These plants will undoubtedly play a significant role in feeding the world's population in the future.     

An algal biosensor for the monitoring of water toxicity in estuarine environments

An algal biosensor for toxicity assessment of estuarine waters is proposed. The sensor was obtained by coupling a suited algal bioreceptor (the cyanobacterium Spirulina subsalsa) to an amperometric gas diffusion electrode. The analytical device allows the monitoring of the evolution of photosynthetic O2 and the detection of alterations due to toxic effects caused by environmental pollutants present in the medium. Four chemical species representative of three main different classes of pollutants (heavy metals, triazinic herbicides, carbamate insecticides) were tested at different concentrations using a standardized natural water as experimental medium. In all the cases a toxic response was detected (i.e. a dose-related inhibition of photosynthetic activity was recorded) with good reproducibility.     

Pesticides in the Rhône river delta (France): Basic data for a field-based exposure assessment

The pesticide concentration levels flowing into paddy fields and surrounding lagoons of the Rhône river delta were investigated over a period of 6 months in 2004. Water samples were collected at the outlets of the major ditches and in the lagoons in order to study the seasonal variation in pesticide concentrations and the spatial contamination profile. Twenty four pesticides were monitored, mainly herbicides and insecticides. Rice pesticides accounted for 90% of the detection rates while the pesticides transported by the Rhône river water dissolved phase only accounted for 10%. Pretilachlor, oxadiazon, MCPA and bentazone herbicides were found at the highest frequencies into the effluent waters of ditches with maximum concentration levels of 1.2, 0.8, 2.5 and 1.6 μg/L, respectively. Only one insecticide, tebufenozide, was sporadically detected at a maximum concentration level of 0.12 μg/L. There were two main peaks of contamination. The first one in April corresponded to the use of pre-emergence herbicides (oxadiazon and pretilachlor) and the second one in June was related to the post-emergence herbicides (MCPA and bentazone). These concentration peaks were well correlated with the pesticide application period time and rapid pesticide transfer (1–2 weeks) from fields to lagoons were observed. Increased loads of the pre-emergence herbicides were induced by the specific management of paddy fields which includes water emptying of fields before and after rice seeding. Pesticide dissipation into the lagoons occurred very quickly and the duration of the exposure of non-target aquatic organisms to high pesticide concentrations (in total a few μg/L level) was no longer than 2 weeks. According to the physico-chemical properties of the chemicals, contrasting results were observed when studying the spatial variation in pesticide concentrations through the lagoons. The concentrations of bentazone and MCPA, two substances with high phototransformation abilities, quickly decreased between the ditches and the lagoons while the oxadiazon and pretilachlor concentrations were more homogeneous.     

Pesticides in the Rhône river delta (France): basic data for a field-based exposure assessment

The pesticide concentration levels flowing into paddy fields and surrounding lagoons of the Rh?ne river delta were investigated over a period of 6 months in 2004. Water samples were collected at the outlets of the major ditches and in the lagoons in order to study the seasonal variation in pesticide concentrations and the spatial contamination profile. Twenty four pesticides were monitored, mainly herbicides and insecticides. Rice pesticides accounted for 90% of the detection rates while the pesticides transported by the Rh?ne river water dissolved phase only accounted for 10%. Pretilachlor, oxadiazon, MCPA and bentazone herbicides were found at the highest frequencies into the effluent waters of ditches with maximum concentration levels of 1.2, 0.8, 2.5 and 1.6 microg/L, respectively. Only one insecticide, tebufenozide, was sporadically detected at a maximum concentration level of 0.12 microg/L. There were two main peaks of contamination. The first one in April corresponded to the use of pre-emergence herbicides (oxadiazon and pretilachlor) and the second one in June was related to the post-emergence herbicides (MCPA and bentazone). These concentration peaks were well correlated with the pesticide application period time and rapid pesticide transfer (1-2 weeks) from fields to lagoons were observed. Increased loads of the pre-emergence herbicides were induced by the specific management of paddy fields which includes water emptying of fields before and after rice seeding. Pesticide dissipation into the lagoons occurred very quickly and the duration of the exposure of non-target aquatic organisms to high pesticide concentrations (in total a few microg/L level) was no longer than 2 weeks. According to the physico-chemical properties of the chemicals, contrasting results were observed when studying the spatial variation in pesticide concentrations through the lagoons. The concentrations of bentazone and MCPA, two substances with high phototransformation abilities, quickly decreased between the ditches and the lagoons while the oxadiazon and pretilachlor concentrations were more homogeneous.     

Rapid exposure assessment of PSII herbicides in surface water using a novel chlorophyll a fluorescence imaging assay

Recently a new Maxi-Imaging-PAM (Max-I-PAM) instrument for phytotoxicity assessment via chlorophyll fluorescence imaging was introduced. This new instrument allows rapid detection of the effects of PS II inhibiting herbicides which are high use agricultural chemicals frequently detected in surface waters in Australia and elsewhere. Several studies have applied the new instrument for detection of phytotoxicants in water using microalgae suspensions; however, these use preliminary protocols and to date no validated method is available for high throughput testing of environmental samples in 96-well plates. Here we developed and applied a new protocol allowing dose-response assessment of four samples within 2 h (8 dilutions in duplicate). The technique was found to be sensitive, with a detection limit of 2.3 ng l(-1) for the herbicide diuron when testing solid phase extracts (SPE) of 1000 ml water samples, and reproducible both between experiments (coefficient of variation (CV)=0.30) and within the 96-well plate (CV=0.06). Relative potencies were determined for four reference PS II impacting herbicides (diuron>hexazinone>atrazine>simazine). Extracts from 1000 ml environmental samples and diuron spiked ultrapure water as well as passive sampler extracts were evaluated and good agreement was found between diuron equivalent concentrations calculated from bioassay results (DEQ(IPAM)) and DEQ(CHEM) values calculated from LCMS chemical analysis of the four reference compounds in the same samples. Overall, the technique provides a valuable bioanalytical tool for rapid and inexpensive effects-based assessment of PS II impacting herbicides in environmental mixtures.     

DRE-CALUX bioassay in comparison with HRGC/MS for measurement of toxic equivalence in environmental samples

CALUX, Chemically Activated LUciferase gene eXpression bioassay, has proven valuable for screening for and assessing toxic equivalents of dioxin-like compounds, because it detects all AhR (arylhydrocarbon receptor) ligands in a variety of sample matrices. In this study, we tried to validate DRE (dioxin-response elements)-CALUX bioassay, which has been developed by cloning mouse cyp1a1 gene in front of luciferase reporter gene. We compared DRE-CALUX bioassay with high resolution gas chromatography/mass spectrometry (HRGC/MS) for assessing environmental samples from Korea. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) dose response study showed high correlation (r2=0.89) between DRE-CALUX bioassay and EROD (ethoxyresorufin O-deethylase) bioassay, a commonly used bioassay method. The mean TEQ value of water samples was 0.57 pg-TEQ(HRGC/MS)/L and 4.97 pg-TEQ(CALUX)/L. For soil samples, HRGC/MS-TEQ values ranged from 0 to 47.18 pg-TEQ/g (dry) and correlated well (r2=0.98) with values obtained by CALUX-TEQ which ranged from 0.92 to 649.97 pg-TEQ/g (dry). The difference between the absolute TEQ values might be due to the presence of dioxin-like compounds without WHO-TEQ values rather than the difference between CALUX-REP and WHO-TEQ. Based on this study, we suggest that DRE-CALUX bioassay can serve as an alternative bioassay method for high-throughput analysis of large number of environmental samples.