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Duplicate sampling reproducibility of atmospheric residues of herbicides for paired pan and high-volume air samplers.

The reproducibility of collection of atmospheric residues of the herbicides 2,4-D and triallate as bulk (wet plus dry) deposition samples by paired pan samplers and as particulate (filter) and vapour (PUF/XAD-2 resin cartridge) samples by paired high-volume air samplers was determined. Variability of herbicide concentrations in paired bulk deposition samples was within 25% for 65 and 80% of the samples for 2,4-D and triallate, respectively, with approximately 90% of the paired samples being within a factor of 2 for both herbicides. The vapour samples of 2,4-D and triallate showed similar reproducibilities. The highest reproducibility was observed for the filter samples with 92% of the paired data sets for 2,4-D being within 25% variability. No triallate was detected in the filter samples.

2,4-Dichlorophenoxyacetic Acid↗

Evaluation of polyurethane foam as a trapping medium for herbicide vapor in air monitoring and worker inhalation studies.

Polyurethane foam was an efficient adsorbent for trapping vapors of butyl esters of 2,4-D (2,4-dichlorophenoxyacetic acid) and triallate (S-(2,3,3-trichloroallyl)diisopropylthiocarbamate) in high volume air monitoring studies and of butyl esters of 2,4-D, iso-octyl ester of 2,4-D, n-butyl ester of 2,4,5-T (2,4,5-trichlorophenoxyacetic acid), bromoxynil octanoate (2,5-dibromo-4-hydroxybenzonitrile), triallate, and trifluralin (alpha, alpha, alpha-trifluoro-2,6-dinitro-N-N-dipropyl-p-toluidine) in short-term, low volume, worker inhalation exposure studies. The collected herbicide vapor was readily desorbed under soxhlet extraction with n-hexane and subsequently analyzed with electron-capture GLC. The overall efficiencies, for both trapping and extraction, were over 90%, using a single plug, for all herbicides, except triallate. In the case of triallate, two plugs in series were required for efficient trapping under the high volume air monitoring situation.

2,4-Dichlorophenoxyacetic Acid↗

Determination of the immunotoxic potential of pesticides on functional activity of sheep leukocytes in vitro.

The effect of eight pesticides with different chemical structure (atrazine, bentazone, chloridazone, dichlofluanid, endosulfan, MCPA, simazine, triallate) on sheep peripheral blood phagocytes and lymphocytes was examined under in vitro conditions by iodo-nitro-tetrazolium reductase test and leukocyte migration-inhibition assay. The pesticides, dissolved in DMSO, were tested at the concentrations of 10(-1)-10(-6) M. The significant suppression of metabolic activity of phagocytic cells was registered after exposure to dichlofluanid (10(-1)-10(-3) M), endosulfan, simazine and triallate (10(-1) M). The significant cytotoxic effect (the decrease of spontaneous migration of leukocytes) was registered for bentazone, dichlofluanid, endosulfan and MCPA (10(-1) M); chloridazone (10(-1) M-10(-2) M) and triallate (10(-1)-10(-5) M). The significant immunotoxic effect (the decrease of lymphocyte activation with PHA) was observed for atrazine (10(-1)-10(-2) M); bentazone (10(-2)-10(-4) M); dichlofluanid, endosulfan (10(-2)-10(-3) M); MCPA (10(-2)-10(-6) M) and simazine (10(-1)-10(-4) M). Three of the pesticides tested suppressed both, the metabolic activity of phagocytes and mitogenic activation of lymphocytes (dichlofluanid, endosulfan and simazine). Triallate suppressed the metabolic activity of phagocytes and showed a strong cytotoxic effect. Pesticides atrazine, bentazone and MCPA influenced the mitogenic activation of lymphocytes and chloridazone showed a significant cytotoxic effect. The different chemical structure of pesticides influenced the metabolic activity of phagocytic cells as well as mitogenic activation of lymphocytes to various intensity.

Animals↗

Mutagenicity of dichlorvos and other structurally related pesticides in Salmonella and Streptomyces.

The following pesticides: azinphosmethyl, diallate, dichlorvos, EPTC, fenchlorphos, mevinphos, monocrotophos, noruron, parathionmethyl, triallate, trichlorphon and vegadex were tested for the ability to induce his+ revertants in four histidines requiring strains of Salmonella typhimurium--TAI 535(missense), TAI 536, TAI 537 and TAI 538 (frame-shift)- and resistance to low levels of streptomycin in Streptomyces coelicolor. Dichlorvos, which is a phosphoric ester with a dichlorovinyl group as side chain, and trichlorphon, which is known for its spontaneous conversion in dichlorvos, are both mutagenic in Salmonella (strain TAI535) and Streptomyces. Five organophosphorus pesticides similar to dichlorvos but devoid of the vinyl group are not mutagenic. Three carbamates, diallate, triallate and vegadex, which contain a chloroallyl group similar to the vinyl group of dichlorvos are mutagenic in Streptomyes; triallate and vegadex are powerful mutagens also in Salmonella (strain TAI535); two other carbamates devoid of the chlorinated group are not mutagenic. The results suggest that the presence of a vinyl chloride or allyl chloride group in the molecule of these pesticides is responsible for the ability to induce point mutations in Salmonella and Streptomyces.

Animals↗

Microbiological mutagenicity studies of pesticides in vitro.

14 pesticides were tested as pure compounds for the induction of point mutations in four strains of Salmonella typhimurium--TA1535, TA1536, TA1537 and TA1538--in the presence and in the absence of rat-liver microsomal fractions and for the induction of resistance to low concentrations of streptomycin in the filamentous bacterium, Streptomyces coelicolor. The technique used was essentially the so-called "spot test". The pesticides investigated were: aminotriazole, Benomyl, Captafol, Captan, Dichlorvos, Dalapon-Na, Dinobuton, Dodine, Ioxynil, Mecoprop, Neburon, Picloram, Triallate and Trichlorphon. In Salmonella, Captan and Triallate were mutagenic on the TA1535 strain; Dichlorvos and Trichlorphon were negative in the spot test but mutagenic after incubation in liquid cultures of strain TA1535. By using the S. coelicolor forward-mutation test, aminotriazole, Dichlorvos, Picloram, Trichlorphon and Triallate were mutagenic with the "spot test" technique; Captan showed a weak mutagenic activity with a "plate-incorporated" technique.

Drug Resistance, Microbial↗

Dissipation of s-triazines and thiocarbamates from soil as related to soil moisture content.

Half-lives (t1/2) of two soil incorporated s-triazines (atrazine and prometon) and two thiocarbamate (EPTC and triallate) herbicides were determined in relation to soil moisture content in two California soils. Treated soils were incubated at three moisture levels in aerated glass vials at 25 +/- 1 degree C and were analyzed at 0, 7, 16, 28, 56 and 112 day intervals. Loss of herbicides in all treatments followed first-order kinetics. The t1/2-values of all herbicides decreased with increasing soil moisture and followed an empirical equation, t1/2 = aM(-b) (where t1/2 is half-life; M the moisture content; and a and b are constants). Soil moisture had a greater effect on carbamates than on s-triazines . Prometon exhibited the longest half-life in both soils, whereas EPTC was least persistent in one soil and atrazine in another. The t1/2-values for atrazine, prometon, EPTC, and triallate with medium moisture levels and 10 microg/g concentration were 34.6, 43.2, 25.4 and 38.1 days in sandy loam and 26.5, 44.4, 44.1 and 25.9 days in loamy sand, respectively. Disappearance of 50% of the applied concentrations of most of the herbicide-soil combinations (except EPTC and triallate in one soil) took longer for lower initial concentrations (1 microg/g) than for higher concentrations (10 microg/g).

Journal Article↗

Atmospheric concentrations and dry and wet deposits of some herbicides currently used on the Canadian Prairies.

High volume air sampling in the Canadian Prairies was used to characterize atmospheric concentrations for 10 herbicides (alachlor, atrazine, ethalfluralin, metolachlor, 2,4-D, dicamba, bromoxynil, MCPA, trifluralin, and triallate) along a 500-km north-south transect. Atmospheric concentration measurements at various altitudes identified that of the six herbicides present in the highest concentrations, triallate was strongly influenced by local sources, while 2,4-D, dicamba, bromoxynil, MCPA and trifluralin were dominated by regional atmospheric transport. Concentrations of the herbicides measured at various altitudes were compared with dry deposition rates measured using a dry/wet deposition sampler and used to calculate deposition velocities V(d). The primary atmospheric transport mechanism for MCPA and bromoxynil was shown to be adsorption to particles dispersed in the atmosphere, with the same mechanism also confirmed for 2,4-D and dicamba, while trifluralin was shown to be transported mainly in the gas phase. This method of calculation indicated that transportation of triallate was influenced by particle adsorption. Weekly maximum atmospheric loadings of the major herbicides present in the Prairies were estimated to range from 73 kg for trifluralin to 541 kg for 2,4-D.

Air Pollutants↗

Comparative sensitivity of Selenastrum capricornutum and Lemna minor to sixteen herbicides.

Aquatic plant toxicity tests are frequently conducted in environmental risk assessments to determine the potential impacts of contaminants on primary producers. An examination of published plant toxicity data demonstrates that wide differences in sensitivity can occur across phylogenetic groups of plants. Yet relatively few studies have been conducted with the specific intent to compare the relative sensitivity of various aquatic plant species to contaminants. We compared the relative sensitivity of the algae Selenastrum capricornutum and the floating vascular plant Lemna minor to 16 herbicides (atrazine, metribuzin, simazine, cyanazine, alachlor, metolachlor, chlorsulfuron, metsulfuron, triallate, EPTC, trifluralin, diquat, paraquat, dicamba, bromoxynil, and 2,4-D). The herbicides studied represented nine chemical classes and several modes of action and were chosen to represent major current uses in the United States. Both plant species were generally sensitive to the triazines (atrazine, metribuzin, simazine, and cyanazine), sulfonureas (metsulfuron and chlorsulfuron), pyridines (diquat and paraquat), dinitroaniline (trifluralin), and acetanilide (alachlor and metolachlor) herbicides. Neither plant species was uniformly more sensitive than the other across the broad range of herbicides tested. Lemna was more sensitive to the sulfonureas (metsulfuron and chlorsulfuron) and the pyridines (diquat and paraquat) than Selenastrum. However Selenastrum was more sensitive than Lemna to one of two thiocarbamates (triallate) and one of the triazines (cyanazine). Neither species was sensitive to selective broadleaf herbicides including bromoxynil, EPTC, dicamba, or 2,4-D. Results were not always predictable in spite of obvious differences in herbicide modes of action and plant phylogeny. Major departures in sensitivity ofSelenastrum occurred between chemicals within individual classes of the triazine, acetanilide, and thiocarbamate herbicides. Results indicate that neither species is predictively most sensitive, and that a number of species including a dicot species such as Myriophyllum are needed to perform accurate risk assessments of herbicides.

Chlorophyta↗

Effects of metyrapone on microsomal-dependent Salmonella mutagenesis. Studies with chloroallyl ethers and model compounds.

Metyrapone (2-methyl-1,2-di-3-pyridyl-1-propanone, MTP) is used as an inhibitor of cytochrome P-450 enzymes, particularly those induced by phenobarbital (PB). We examined the effects of MTP on the microsomal dependent mutagenesis of a newly isolated promutagen, 3-(2-chloroethoxy)-1,2-dichloropropene (CP), three S-chloroallyl thiocarbamate herbicides, and four model promutagens aflatoxin B1 (AFB), 2-acetylaminofluorene (2AAF), 2-aminoanthracene (2AA) and benzo[a]pyrene (BP). Salmonella tester strains TA98, TA100 and TA1535 and liver microsomal preparations (S9) from rats induced with PB or Aroclor 1254 (PCB) were employed. For statistical analysis, mutagenesis data were transformed and subjected to two-way analysis of variance. Metyrapone alone was not mutagenic in the absence or presence of S9. In a dose-dependent manner, MTP inhibited mutagenesis of AFB for strains TA98 and TA100 and enhanced mutagenesis of 2AAF, 2AA and BP for these strains. 3-(2-Chloroethoxy)-1, 2-dichloropropene and the herbicides diallate, triallate and sulfallate are all chloroallyl ethers. They are similar in their mutagenesis for Salmonella with respect to strain specificity, mutagenic potency, and requirement for activation by specifically-induced microsomes. Metyrapone inhibited the mutagenesis of CP, triallate and sulfallate for strain TA100 in the presence of either PB- or PCB-induced S9, and had no apparent effect on diallate mutagenesis; the same results were obtained for TA1535 with PCB-induced S9. On this basis, the mutagenic activation of diallate appears to be different from that of the other chloroallyl ethers tested. Our results indicate that MTP can inhibit as well as enhance microsomal dependent mutagenesis for Salmonella. We conclude that MTP may be a useful tool in characterizing pathways for promutagen activation.

Allyl Compounds↗

Herbicide levels in rivers draining two prairie agricultural watersheds (1984).

A monitoring survey was conducted during 1984 on the Ochre and Turtle Rivers, which flow into Dauphin Lake in western Manitoba, Canada, to determine levels of the herbicides MCPA, diclofop-methyl, dicamba, bromoxynil, 2,4-D, triallate and trifluralin which were widely used in each watershed. Triallate concentrations exceeded 4 ng/L in 50% and 10% of the 21 samples taken from each of the Turtle and Ochre River, respectively, during the period March to October 1984. Trifluralin concentrations exceeded 3 ng/L in 14% and 10% of the samples from the respective rivers. Maximum concentrations did not exceed 25 ng/L and were unrelated to changes in river flow. Bromoxynil and diclofop were detected in the Turtle River, at concentrations of 113 and 476 ng/L, respectively, following a major high water event in late June, but were undetectable (less than 2 and 12 ng/L, respectively) at other sampling times. Dicamba and 2,4-D were detectable throughout most of the sampling period in both rivers at low levels (less than 100 ng/L). High levels of dicamba and 2,4-D (5476 and 2568 ng/L respectively) were found in water from the Turtle River prior to the high water event event possibly caused by spraying of ditches or rights-of-way near the river. Discharges (grams/year) of all seven herbicides monitored in the study represented less than 0.1% of the amounts estimated to be used in each watershed. Unit loadings (mg/ha/year) of 2,4-D and dicamba were similar to those reported for Southern Ontario streams in the mid-1970's. The results indicate that herbicide contamination of Manitoba streams draining agricultural areas is generally low except when major runoff occurs during the application period in May and June.

Chromatography, Gas↗

[Genetic activity of carbamate herbicides in Escherichia coli and Saccharomyces cerevisiae].

DNA-damaging activity and herbicide-induction of gene point mutations, and intragenic mitotic recombination were studied in bacteria and the yeast tester strains. Herbicide (eptam, triallate, tillam, surpass) were not effective in DNA-damaging and mitotic recombination tests. Of the 4 chemicals, only eptam was strongly mutagenic. Dose response curves for eptam differed in bacteria and yeast; maximum mutagenic activity was registered in bacteria at 5 mg/l. Maximum yield of prototrophs was observed after 2 h incubation time. Triallate was moderate, tillam and surpass being weak mutagens for the strains used.

Carbamates↗

Tandem mass spectrometry of herbicide residues in lipid-rich tissue.

A tandem mass spectrometry procedure, originally developed for bacterial biofilms was adapted for the identification of herbicide residues in lipid-rich tissue of amphipods collected from microcosms in a prairie wetland. For this application, the amounts of tissue employed (less than 1 mg wet weight), and detection of target analytes at picogram levels, were similar to the values reported for bacterial biofilms. Described is an application of the technique for the identification of residues of the herbicide S-2,3,3-trichloroallyl diisopropyl thiocarbamate (triallate; trade name Avadex-BW). For amphipods collected from microcosms exposed to the herbicide 2-[4-(2,4-dichlorophenoxy)phenoxy]propionic acid methyl ester (diclofop-methyl, trade name Hoe Grass), there were detectable levels of only the hydrolysis product, diclofop acid, in the lipid-rich tissue. Other transformation products reported for bacterial biofilms were not observed in the amphipods.

Halogenated Diphenyl Ethers↗

Body mass index and bromoxynil exposure in a sample of rural residents during spring herbicide application.

Bromoxynil (3,5-dibromo-4-hydroxybenzonitrile), a phenolic herbicide, is widely used in production of cereals and other crops. Little is known, however, about bromoxynil exposure in humans. Results of previous research suggest a longer residence time in the body for bromoxynil compared to phenoxy herbicides [e.g., (2,4-dichlorophenoxy)acetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA)] and that bromoxynil would tend to partition into fatty tissue more so than 2,4-D. In previous research, body mass index (BMI) was found to be an independent predictor of plasma concentrations of 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE), the persistent lipophilic metabolite of the chlorinated pesticide bis(4-chlorophenyl)-1,1,1-trichloroethane (DDT). As part of the Prairie Ecosystem Study, gas chromatography/mass spectrometry analysis was used to measure concentrations of bromoxynil and seven other herbicides (2,4-D, dicamba, fenoxaprop, MCPA, ethalfluralin, triallate, and trifluralin) in plasma from residents (104 men, 88 women, 24 youths age 12-17 yr) of a cereal-producing region in Saskatchewan, Canada, during spring herbicide application, 1996. Multiple logistic regression analysis was used to explore whether BMI predicted detection of bromoxynil in plasma from the adults. The prevalence of detection (detection limits: 2-50 microg/L) was markedly higher for bromoxynil (men, 44.2%; women, 14.8%; youths, 20.8%) compared to each of the other herbicides including 2,4-D (men, 16.5%; women, 3.4%; youths, 12.5%) and MCPA (men, 6.8%; women, 1.1%; youths, 4.2%), although bromoxynil is commonly formulated or tank mixed with these herbicides. In the multiple logistic regression analysis, the variables BMI, exposure group [bromoxynil applicators, non-applicator family members of bromoxynil applicators, all others (reference group)], and days elapsed since the last use of bromoxynil were found to be independent predictors of detection of bromoxynil, while age, gender, and farm residency were not statistically significant. With adjustment for exposure group [bromoxynil applicators: odds ratio (OR = 24.30, 95% confidence interval (CI) = 9.59-61.58; nonapplicator family members of bromoxynil applicators: OR = 3.53, 95% CI = 1.19-10.44; all others (reference group)], the OR for detection of bromoxynil was 2.35 (95% CI = 0.87-6.33) for participants in the middle (25.53-29.00 kg/m2) tertile (men: OR = 2.85, 95% CI = 0.75-10.82; women: OR = 1.63, 95% CI = 0.36-7.40) of BMI and 4.01 (95% CI = 1.46-11.03) for participants in the highest (> 29.00 kg/m2) tertile (men: OR = 4.67, 95% CI = 1.17-18.58; women: OR = 2.20, 95% CI = 0.44-10.99) with participants in the lowest (< 25.53 kg/m2) tertile as the reference group. Similar ORs were observed for BMI with adjustment for days elapsed since the last use of bromoxynil. In conclusion, further research is needed to investigate whether adiposity is an important modifying factor for persistence of bromoxynil in the body.

2,4-Dichlorophenoxyacetic Acid↗

Aldehyde dehydrogenase of mice inhibited by thiocarbamate herbicides.

The herbicide S-ethyl N,N-dipropylthiocarbamate (EPTC) and three of its candidate metabolites (the sulfoxide, N-depropyl and S-methyl derivatives) inhibit mitochondrial low-Km aldehyde dehydrogenase (ALDH) in liver by 56 to 82% 2 hr after these thiocarbamates are administered intraperitoneally (ip) to mice at 8 mg/kg. They also greatly elevate the acetaldehyde level (determined as the O-benzyloxime ether) in blood (up to 500 microM) and brain (up to 3 ppm) 30 min after two ip treatments, the first with the thiocarbamate at 40 mg/kg and 2 hr later with ethanol at 1000 mg/kg. EPTC at 4 mg/kg inhibits liver ALDH activity by 50% and at 8 and 18 mg/kg gives half of the maximum ethanol-dependent elevation of acetaldehyde levels in blood and brain, respectively. The in vivo effects of other thiocarbamate herbicides at 8 mg/kg on ALDH activity and 40 mg/kg on acetaldehyde levels decrease in the order of thiobencarb, pebulate, vernolate and molinate > butylate and triallate >> cycloate. The percentage inhibition of liver ALDH activity generally correlates with the elevation in blood and brain acetaldehyde under these treatment protocols. B.W. Hart and M.D. Faiman (Biochem. Pharmacol. 43 403-406, 1992) have shown that the alcohol-aversion drug disulfiram is metabolized to S-methyl N,N-diethylthiocarbamate and its sulfoxide as the penultimate and ultimate metabolites inhibiting ALDH. Thus, the thiocarbamate herbicides and their metabolites are similar to the disulfiram metabolites not only in homologous structure but also in their potency range as ALDH inhibitors in vivo. On this basis some of the thiocarbamate herbicides may sensitize agricultural workers to ethanol intoxication.

Acetaldehyde↗

Evaluation of the genetic activity profiles of 65 pesticides.

We have previously reported the qualitative results of a major study on 65 pesticides (Waters et al., 1982). Dose information from this investigation (either lowest effective or highest ineffective dose tested) has now been incorporated into a computerized data management system. This report focuses on the qualitative profiles of genetic activity produced by these pesticides and our efforts to classify them according to their genotoxic effects and chemical structures. Three main categories may be distinguished based on the qualitative results: Category 1 pesticides were active in most of the in vitro and in vivo assays employed. These 9 compounds include the structurally similar organophosphate insecticides, acephate, demeton, monocrotophos and trichlorfon; the phthalimide fungicide analogues, captan and folpet; and the thiocarbamate herbicide analogues, diallate, sulfallate and triallate. The 26 Category 2 compounds demonstrated fewer positive results and may be subdivided into two parts, one of which contains 12 halogenated aromatic or heterocyclic ring compounds, including the phenoxy herbicides, 2,4-D, 2,4-DB and 2,4,5-T. The remaining part of Category 2 (14 compounds) consists of structurally similar organophosphate insecticides, azinphos-methyl, crotoxyphos, disulfoton, methyl parathion; three similar ethylenebisdithiocarbamate fungicides, maneb, mancozeb, and zineb; three similar pyrethroid insecticides, allethrin, chrysanthemic acid, and ethyl chrysanthemate; and four structurally diverse compounds, cacodylic acid, dinoseb, sec.-butylamine and benomyl. The third category of 30 pesticides gave negative results in all tests and represents structurally diverse compounds. Using the computerized profile matching methodology, from 2080 possible pairwise chemical combinations of the 65 pesticides, 20 statistically significant pairs were selected, 6 groups of pesticides were identified which were substantially similar to groups of pesticides we had formed previously (Waters et al., 1982) based on genetic activity and chemical structure. The matches showed excellent qualitative and, in most cases, excellent quantitative agreement. Hence it appears that specific patterns of test results present in the genetic activity profiles are related directly to chemical structure. Conversely, the data suggests that certain groups of compounds may be recognized by a well defined series of concordant tests results. As additional data is added, comparison of test results for new chemicals with existing data for known genotoxicants should aid in the evaluation of potential genetic health hazards.

Animals↗

Aliphatic halogenated hydrocarbons produce volatile Salmonella mutagens.

Production of volatile mutagenic metabolites from 5 halogenated promutagens was examined by a simple modification of the conventional Salmonella/microsome mutagenicity assay. This method incorporates the taping together of 2 agar plates face to face during the initial portion of their incubation at 37 degrees C. By varying the contents of the soft agar in each of the two plates with respect to promutagen, S9 and tester strain cells, mutagenesis due to volatile promutagens and their metabolites could be quantitated separately. Using the taped plate assay, volatile mutagenic metabolites were detected from the promutagens 3-(2-chloroethoxy)-1,2-dichloropropene, the herbicides diallate, triallate and sulfallate, and the flame-retardant tris-(2,3-dibromopropyl) phosphate (Tris-BP). All compounds except Tris-BP were also found to be volatile promutagens. The mutagenic metabolites accounted for 50-80% of the activity of these compounds observed in the standard assay. Morever, our studies suggest that a small, but appreciable percentage of the mutagenic metabolites from all 5 compounds escaped detection in the conventional, untaped assay. Mutagenic activity of the volatile mutagenic metabolites from diallate was quenched by various Salmonella tester strains independent of their responsiveness to diallate mutagenesis. Detection of volatile mutagen formation from diallate was also prevented by cysteine and glutathione, but not by DNA or metyrapone. This taped plate method for the Salmonella assay should facilitate future investigations of the detection, isolation and identification of volatile mutagenic metabolites from other promutagenic compounds or mixtures.

Allyl Compounds↗

Agricultural pesticides threaten the ecological integrity of northern prairie wetlands.

The northern Great Plains of North America has millions of small wetlands, and these are often dispersed through cultivated fields. We investigated relationship between pesticide occurrence and precipitation in selected wetlands in a 30.4 x 10(4) km2 area of the Great Plains with relatively uniform farming practices and 1,777,600 wetlands (southern Saskatchewan, Canada). By early July after pesticides have been applied to crops, the mean number of pesticides detected in wetlands ranged from 1.8 in regions with little precipitation (< 21 mm rain during the previous 15 days) to 3.2 in regions under higher rainfall (> 90 mm). The proportion of wetlands in which at least one pesticide exceeded Canadian guidelines for the protection of aquatic life increased from 0% to 60% over this same precipitation range. The maximum number of pesticides detected in a single wetland was six. Concentration of lindane in wetlands increased with increasing precipitation. Using geographic information on rainfall, wetland densities, area seeded to crops, and region specific relationships between pesticides and precipitation, we estimated the number of wetlands in Saskatchewan with elevated levels of pesticides. In early July, during 3 of the 6 years, the number of wetlands subjected to pesticide levels that exceeded guidelines for the protection of aquatic life was significant, ranging from 152,000 to 424,000 wetlands or 9-24%, respectively, of the total. Lindane and triallate exceeded the guidelines most frequently.

Agriculture↗

Analysis of pesticides in honey by solid-phase extraction and gas chromatography-mass spectrometry.

An analytical method for the simultaneous determination of 51 pesticides in commercial honeys was developed. Honey (10 g) was dissolved in water/methanol (70:30; 10 mL) and transferred to a C(18) column (1 g) preconditioned with acetonitrile and water. Pesticides were subsequently eluted with a hexane/ethyl acetate mixture (50:50) and determined by gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode (GC-MS-SIM). Spiked blank samples were used as standards to counteract the matrix effect observed in the chromatographic determination. Pesticides were confirmed by their retention times, their qualifier and target ions, and their qualifier/target abundance ratios. Recovery studies were performed at 0.1, 0.05, and 0.025 microg/g fortification levels for each pesticide, and the recoveries obtained were >86% with relative standard deviations of <10%. Good resolution of the pesticide mixture was achieved in approximately 41 min. The detection limits of the method ranged from 0.1 to 6.1 microg/kg for the different pesticides studied. The developed method is linear over the range assayed, 25-200 microg/L, with determination coefficients of >0.996. The proposed method was applied to the analysis of pesticides in honey samples, and low levels of a few pesticides (dichlofluanid, ethalfluralin, and triallate) were detected in some samples.

Food Contamination↗