Preservation of organophosphorous pesticides in water samples.

Four techniques were studied for capacity to preserve sixteen organophosphorous pesticides in distilled water and in creek water. A technique using chloroform effectively preserved all sixteen pesticides for the three weeks of the study and refrigeration was effective for fourteen of the pesticides, but buffers of pH 4 and pH 7 appeared undependable as preservatives.     

Removal technology for pesticide contaminants in potable water

Abstract

Granular activated carbon adsorption is one of the reliable and effective means of removing organochlorine pesticides from water. Continuous stirred tank and fix bed reactor systems were used for the screening of indigenous granular activated carbons in the removal of organochlorine pesticides from water at low microgram levels in simulated samples. The carbon dose reguired to treat raw water at initial concentrations of 5–10 ug/1 of Y‐HCH, p,p'‐DDT and p,p'‐DDE to <2 ug/1 potable level was computed. Data leads to the development of a tap attachable water treatment unit for pesticides removal for applications on domestic scale.     

Determining the role of humic substances in the fate of pesticides in the environment

Abstract

The data presented in this paper emphasize that the behavior and fate of pesticides in the environment is influenced by humic substances. Various methods most frequently used for the characterization of humic substances are discussed. Both humic acid and fulvic acid can solubilize in water certain organic compounds and are important carriers of some pesticides in soil. Humic substances have the potential for promoting the nonbiological degradation of many pesticides. Several methods of bleaching humus color from drinking water, including chlorination, ozonation, and UV‐radiation, are described. Finally, the photochemical stability to UV‐radiation of certain pesticides in aqueous fulvic acid solution is discussed.     

Paper electrophoretic separations of some common pesticides : Determination of monocrotophos,rogor and malathion in soil samples

Abstract

Paper electrophoretic movements of a number of pesticides belonging to organophosphorus, organochlorine and pyethroid groups in various acid background electrolytes have been studied. The effect of pH and pKa of the acids on the movement of these pesticides have also been studied. It has been observed that the movement of most of the pesticides is enhanced with increase in the degree of ionisation of the acids (pKa) studied as background electrolytes. The movement also increases with increase in the pH of acids. On the basis of differential movement of pesticides towards cathode and anode, a number of separations have been achieved from binary mixtures. Monocrotophos, rogor and malathion have been determined quantitatively (28.6 ‐ 29.2 μg) in alcoholic extracts of soil samples.     

Solid‐phase extraction and GC analyses of select agricultural pesticides and metabolites in stream water

Abstract

The occurrence of agricultural pesticides in surface waters around the USA has created a concern over the status of safe drinking water. Solid‐phase extraction (SPE) or liquid‐liquid extraction (LLE) is usually employed to concentrate trace levels of pesticides in water samples to concentrations that are measurable with advanced chromatographic instruments. We describe here a SPE and capillary gas chromatographic (GC) procedure to extract and concentrate trace levels of select agricultural pesticides and metabolites from stream water. Our SPE and GC method provides high sensitivity, with recoveries between 85% to 95%, and high reproducibility for 9 of the pesticides studied. The described method provided marginal recoveries of 19 and 60% for the atrazine metabolites.     

Pesticides in ground water in the united states: Monitoring,modeling, and risks from the U.S. perspective

Abstract

Scientific and regulatory interest in ground water contamination by pesticides increased significantly in 1979. This was prompted by findings of the nematicide 1,2‐dibromo‐3‐chloropropane (DBCP) and the nematicide/insecticide aldicarb (Temik®) in ground water in several states. Since that time, at least 130 pesticides and pesticide metabolites have been detected in ground water in over 150 studies, but detection frequencies are 4–10% nationally. Detection frequencies of pesticides over Health Advisory Levels are generally lower. Screening‐level models and detailed computer simulation models are useful for risk assessments and regulatory decisions. Attenuation Factor, CMLS, PRZM2, GLEAMS, and LEACHM are all useful models.     

Residues of organochlorine pesticides in fishes in Sudan

Abstract

Cotton‐producing areas of the Centrol Sudan, bordered by the Blue and the White Nile, have been subjected to repeated applications of pesticides. This region is irrigated by a series of canals, the Gezira canals, which hold large amounts of fresh water. Lake Nubia at the Sudan‐Egypt border is another important fresh water reservoir and fisheries ground. Fish from both the Gezira and Lake Nubia showed elevated concentrations of pesticides, suggesting that continued pesticides application would endanger the equatic fauna of this region and the proposed fresh water fishery.     

Analytical approaches for determining human exposure to pesticides

Abstract

The presence of pesticides, both persistent and biodegradable, in the environment is a problem which is both significant and potentially dangerous to humans. An index of biodegradability is presented which is based on the correlation between environmental stability and fat solubility. Halogenated pesticides are, therefore, both more fat soluable and more resistant to biodegradation, while methylated pesticides are more water soluable and, therefore, more biodegradable. Three methods for detecting low‐levels of halogenated pesticides are presented: the Macro, the Micro “Florisil,”; and the Micro “Silica.”; A method is also presented to detect these chemicals in blood. Two methods for the detection of nonpersistent, organophosphorus and carbamate insecticides, Cholinesterase inhibition and urinary metabolites, are described. Finally, methods of monitoring human exposure through the detection of phenols, phenoxy acids, alkyl phophates, and anilines are presented.     

Application of Automated Mass Spectrometry Deconvolution and Identification Software for Pesticide Analysis in Surface Waters

A new approach to surface water analysis has been investigated in order to enhance the detection of different organic contaminants in Nathan Creek, British Columbia. Water samples from Nathan Creek were prepared by liquid/liquid extraction using dichloromethane (DCM) as an extraction solvent and analyzed by gas chromatography mass spectrometry method in scan mode (GC-MS scan). To increase sensitivity for pesticides detection, acquired scan data were further analyzed by Automated Mass Spectrometry Deconvolution and Identification Software (AMDIS) incorporated into the Agilent Deconvolution Reporting Software (DRS), which also includes mass spectral libraries for 567 pesticides. Extracts were reanalyzed by gas chromatography mass spectrometry single ion monitoring (GC-MS-SIM) to confirm and quantitate detected pesticides. Pesticides: atrazine, dimethoate, diazinone, metalaxyl, myclobutanil, napropamide, oxadiazon, propazine and simazine were detected at three sampling sites on the mainstream of the Nathan Creek. Results of the study are further discussed in terms of detectivity and identification level for each pesticide found. The proposed approach of monitoring pesticides in surface waters enables their detection and identification at trace levels.     

Multiresidue method for high-performance liquid chromatography determination of carbamate pesticides residues in tea samples

A multiresidue method was developed to determine 19 carbamate pesticides in tea samples. Optimizations of different parameters, such as the type of extraction solvents, clean-up cartridges, and elution solvents were carried out. The developed method used acetonitrile as extraction solvent, amino cartridge for adsorbents and acetone-n-hexane as the eluting solution. Nineteen carbamate residues were then analyzed by high-pressure liquid chromatography (HPLC) with fluorescence detector. The present results showed good linearity by correlation coefficients of more than 0.9999 for all analyses. Limits of detection and quantification varied from 0.0005–0.023 mg L^{? 1}, 0.008–0.077 mg L^{? 1}, respectively. Recoveries of sixteen carbamate pesticides ranged from 65% to 135% at the spiked level of 0.5, 1.0 and 2.0 mg L^{? 1}. The relative standard deviations were lower than 20% and coefficient of variations were lower than 15%. The results indicate that the proposed method provides an effective multi and trace level screening determination of carbamate pesticides residues for tea samples.     

Pesticides in the surface waters of the Camanducaia River watershed,Brazil

Abstract

Camanducaia River is part of the Piracicaba watershed responsible for pumping water into the Cantareira System, which is one of the main water sources for the metropolis of São Paulo and Campinas, Brazil. Intensive use of pesticides and hilly topography represents a situation of high risk for river water contamination. Therefore, water samples from 12 locations were collected along the Camanducaia River and its tributaries, over a period of 4?mo during the rainy season, and analyzed by GC-MS/MS or UPLC- MS/MS for the presence of 46 pesticides. Seven pesticides (fipronil, methyl parathion, metolachlor, atrazine, carbofuran, diuron, and simazine) were positively detected. Only atrazine (the most frequently detected) and diuron were present at concentrations above the limit of quantification of the analytical method (0.32 and 0.57?μg L^?1 for atrazine and diuron, respectively). Pesticides detection frequency was higher than expected for a river system where only 11.8% of the land area is under agriculture. The vulnerability of the Camanducaia basin to pesticide contamination is attributed to the high annual precipitation (> 1.5?m y^?1 in the headwaters), associated with topographical features (steep terrain) and soil types that favor surface runoff, which has been exacerbated by poor soil management practices.     

Effects of synthetic pyrethroids and methidation on activities of some digestive enzymes in carp (Cyprinus carpio L.)

Abstract

The effects of pyrethroid pesticides (deltamethrin, permethrin and cypermethrin) and an organophosphate ester (methidation) on the activities of carp trypsin, α‐chymotrypsin, carboxypeptidase A and lipase were studied. The enzymes were isolated from the gastrointestinal tract and the effects of the pesticides were investigated during incubation for 5 min. The activity of trypsin was influenced only slightly by the presence of deltamethrin and methidation, whereas permethrin and cypermethrin caused significant inhibition. The pyrethroid pesticides at lower concentrations resulted in a slight activation of α‐chymotrypsin. Methidation inhibited the α‐chymotrypsin activity by about 20%. These pesticides modified the lipase activity to a lesser extent; the highest inhibition was measured with cypermethrin. The carboxypeptidase A activity was inhibited by both pyrethroid pesticides and methidation. The results suggest that these pesticides might interact with the active conformation of the studied hydrolytic enzymes, resulting in changes in their activities.     

Ecological Risk Assessment of Neem-Based Pesticides

Abstract

A tiered process was used to evaluate the risks of pure azadirachtin (AZA) and two neem-based insecticides (Neemix? and Bioneem?) on six aquatic animals [crayfish (Procambarus clarkii), white shrimp (Penaeus setiferus), grass shrimp (Palaemonetes pugio), blue crabs (Callinectes sapidus), water fleas (Daphnia pulex), and mosquito larvae (Culex quinquefasciatus)] through short term acute toxicity tests. The risk was calculated using the level of concern endpoints (Q values) and relative hazard index (RHI) for acute and chronic exposure scenarios. The Q values of Neemix?, Bioneem?, and pure AZA derived from acute exposure tests indicated that D. pulex is the only sensitive species to the test pesticides. Furthermore, the RHI values of Neemix? and Bioneem? for D. pulex were above the critical limit of 10 indicating that these pesticides may pose a moderate hazard to this species and related crustaceans in acute exposure scenarios. The RHI values of the two pesticides and pure AZA were all below the critical limit of 10 for P. clarkii, P. setiferus, P. pugio, C. sapidus, and C. quinquefasciatus. The aquatic risk assessment process showed that the risk values of tested pesticides did not exceed the criteria, and therefore, no ecological hazard is likely to result from their use.     

Investigation of pesticide residues in water,sediments and fish samples from Tapi River,India as a case study and its forensic significance

Abstract

This research is a case study on detection of pesticides in river water, sediment as well as fish samples from Tapi River, among the major rivers of Gujarat, India. To investigate the misuse, concentration level and occurrence patterns of persistent pesticides, samples were collected from the river. Chlorpyrifos, methyl parathion, hexachlorocyclohexane (HCH), dichloro diphenyl trichloroethane (DDT) and endosulfan were analyzed by gas chromatography technique with flame ionization detector (FID). Scanty reports are available, but after 1999, no such data are reported as some of these pesticides have been banned. Although these pesticides are still in use which we observed from the obtained results. In this river, the amount of endosulfan, chlorpyrifos, and methyl parathion was observed in surface water with concentrations of 37.56?µg/L, 0.86?µg/L and 0.43?µg/L, respectively. Endosulfan, DDT and methyl parathion detected in sediment were 38.38?ng/g, 0.65?ng/g and 0.77?ng/g, respectively. In fish samples, levels of endosulfan, chlorpyrifos, and methyl parathion detected were 101.28, 0.392, and 3.49?ng/g correspondingly. Results showed that highly toxic pesticides are still being used in the surrounding area, and there is an urgent need for enforcement of rules to control the production and application of such pesticides.     

Effects of cyclodextrin on the stereoselectivity inhibition of acetylcholinesterase by isomalathion

ABSTRACT

In attempt to evaluate the effects of cyclodextrins (CDs) on enantioselectivity of chiral pesticides toxicity, this study investigated effects of three kinds of cyclodextrins including α-CD, β-CD and randomly methylated β-CD (RAMEB) on toxicity of four enantiomers of isomalathion including (1R, 3R)-isomalathion, (1S, 3S)-isomalathion, (1S, 3R)-isomalathion and (1R, 3S)-isomalathion. Generally, the addition of α-CD and RAMEB (1.5 g/L to 3.5 g/L concentration) could lead to reduction of isomalathion toxicity in most cases, while the presence of β-CD (0.3 g/L to 1.5 g/L concentration) enhanced the toxicity of isomalathion. It was speculated that higher electronic cloud density and lower water solubility of β-CD than α-CD and RAMEB might favor to combination between acetylcholinesterase (AChE) and isomalathion included by β-CD. With respect for α-CD and RAMEB, isomalathion included by them could be easily dissolved in water because of high water solubility of the two CDs. Therefore, α-CD and RAMEB can be used as remediation regent for the pollution of isomalathion, and β-CD can act as an additive in improving bioactivity of such pesticides. In addition, the presence of CDs can alter enantioselectivity of chiral pesticides. The differences on the extent of enantioselectivity variation of isomalathion induced by α-CD, RAMEB and β-CD might be ascribe to the different cavity, electron cloud density and solubility among the three CDs. In conclusion, the above results gave researchers a possibility to change enantioselectivity of chiral pesticides from undesirable outcomes to desirable ones.     

Agricultural Pesticide Residues in Farm Ditches of the Lower Fraser Valley,British Columbia,Canada

Transient and permanent farm ditches flowing to the Lower Fraser River tributary fish streams of British Columbia, Canada, were sampled at several locations in 2003–2004 to determine the occurrence and concentration of residues of selected pesticides, their transformation products, and soluble/extractable Cu⁺⁺ ions. Of the 43 compounds analyzed, 28 and 22 pesticides were detected in transient farm ditch water and sediments, respectively. About 34% fewer pesticides, however, were found in both matrices of permanent farm ditches. Average concentrations (μ g L^?1) of those most frequently detected in permanent farm ditch water were atrazine (0.20), α -chlordane (0.06), desethylatrazine (0.13), diazinon (0.55), dieldrin (0.28), endosulfan sulfate (0.16), glyphosate (6), metalaxyl (0.27); and soluble Cu⁺⁺ ions (25). Those most often found in ditch sediments (μ g kg^?1) were aminomethylphosphonic acid (AMPA) (2,300), 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane (DDT) (250), endosulfan sulfate (500), glyphosate (1,225); and extractable Cu⁺⁺ ions (58,000). The risk potential of these pesticide residues to non-target aquatic organisms inhabiting Fraser River tributary fish streams contiguous to permanent farm ditches is evaluated and discussed.     

Evaluation of an activated carbon filter for the retention of selected pesticide vapours

Abstract

An activated charcoal bed unit (ACBU) was constructed using teflon stock. The unit duplicated the flow and bed design of a commercially available tractor mounted filter for removing pesticides from the air.

Eight pesticides (4 herbicides and 4 insecticides) were used to test the retention efficiency of ACBU over a 12–48 h period with the ACBU in place. Polyurethane foam (PUF) plugs in series trapped any residual pesticide that came through the ACBU.

The ACBU retained 93–100% of the pesticides tested. The unit thus provides an efficient mechanism for removing airborne pesticides.     

Determination of organochlorine and organophosphate pesticide residues in fruits,vegetables and sediments

Abstract

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean‐up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean‐up for sediment extract was carried out on a10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL.

The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'‐DDT and endosulfan sulphate, which was 0.01 mg/kg.

The detection limit for oganochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 μg/kg and for organophosphate pesticides less than 10 μg/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

Evaluation of C18 solid‐phase extraction cartridges for the isolation of select pesticides and metabolites

Abstract

Nine different C₁₈ solid‐phase extraction (SPE) cartridges were evaluated for their efficiency at extracting nine pesticides and two s‐triazine metabolites from spiked deionized water samples. The SPE cartridges were found to contain nitrogen (N) and/or phosphorus (P) contaminants and varied in their extraction efficiency for certain pesticides and metabolites. Four of the nine SPE cartridges gave acceptable (70 to 120%) pesticide and metabolite recovery percentages, while five cartridges had marginal (50 to 70%) to poor (< 50%) recoveries. Statistical analyses showed that the poor to marginal recoveries found for three compounds could not be explained by considering several indigenous chemical and physical traits of the cartridge. It is suggested that proper SPE cartridge selection for pesticide recovery should be evaluated using several different cartridges.     

Evaluation of the genotoxic and cytochrome P450 monooxygenase‐inhibitory potential of dicuran on procaryotic and eucaryotic test systems

Abstract

The effect of the herbicide Dicuran 500 FL (formulated product) on the phenotypical and genotypical changes in procaryotic and eucaryotic organisms was investigated using short‐term tests for detecting genotoxins. Since pesticides discharged in the water environment can modulate the mixed‐function monooxygenases (MFO) detoxification system of water organisms, the in vivo and in vitro effects of Dicuran on hepatic cytochrome P450 (cyt P450) monooxygenase activities were also examined in juvenile carp (Cyprinus carpio L.). By measuring the activities of MFO in experimental carp exposed to Dicuran an attempt was made to establish whether Dicuran could be bioactivated by MFO into ultimate mutagens. Our results on the bacterial strains Salmonella typhimurium TA100 and TA98 show that Dicuran does not possess either mutagenic or premutagenic characteristics. The micronucleus test on the erythrocytes of experimental carp did not establish any clastogenic effect either. However, Dicuran significantly inhibited the MFO activity of 7‐ethoxyresorufin‐O‐deethylase (EROD) and benzo[a]pyrene monooxygenase (BaPMO) in the liver of experimental carp in vitro, as well as in in vivo conditions. These findings demonstrate the potentially damaging effect of Dicuran on the xenobiotic metabolizing enzyme systems of fish, and suggest the applicability of described methods for the prediction of the ecotoxicological significance of the presence of pesticides in the water environment.