Preservation of organophosphorous pesticides in water samples

Abstract

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 A and pH 7 appeared undependable as preservatives.     

LogD: lipophilicity for ionisable compounds

The octanol/water partition coefficient (Kow) for organic compounds is widely used in predictive environmental studies. A significant proportion of contaminants of surface and ground water are ionisable (e.g. many pesticides, pharmaceuticals, metabolites). Such compounds may be partially ionised dependent on the pH. Since the neutral and ionic species exhibit different polarities, the Kow value of ionisable pesticides is pH dependent. It is therefore essential to determine Kow values over the full range of pH that occurs in the environment in order to get appropriate predictors. Numerous methods are available to measure lipophilicity but only a few are appropriate for ionisable pesticides (e.g. pH metric and filter probe methods). Parameters such as pH and ionic strength need to be carefully controlled when working with ionisable compounds. Variation of these factors probably explains why literature can yield Kow values that differ by more than one order of magnitude for some compounds. In this article, Kow values obtained for six acidic pesticides with three different methods are compared as well (data from the literature, measured by pH metric method and calculated with five computer programs). The values used in predictive regression equations needs to be either measured with a suitable method or selected from the literature with great care.     

Influence of suspended clay minerals and humic matter on the solid phase extraction efficiency of selected pesticides from water

The purpose of this investigation was to determine the influence of humic acids (HA) and Ca-montmorillonite (CaM) on the solid-phase extraction (SPE) efficiency of atrazine, alachlor and alpha-cypermethrin from water samples at various pH-values. The nature and intensity of binding of the studied pesticides to CaM were determined by X-ray diffraction analysis and termogravimetric analysis (TGA) test. The studied pesticides eluted from discs were analysed by thin-layer chromatography (TLC). The effects of CaM and humic acid were generally pH-dependent and acted independently in extraction efficiency influence. Lower recovery of pesticides was observed at higher pH values when CaM was > or =0.1 g and was attributed to greater dispersion of clay, increased surface area and subsequent adsorption. Concentrations of dissolved organic carbon (DOC) in humic acid had less effect on the extraction efficiency when water was at pH 8 compared to water at pH 2, which was probably due to greater nonpolar interactions of the pesticides to the charge-neutralized humic acid molecule.     

Adsorption of pesticides on resins

The objective of this work was to assess the capability of organic hydrophobic polymeric resins Amberlite XAD-4 and XAD-7 to remove the pesticides alachlor and amitrole from water. The pesticides adsorption on the two different adsorbents was measured by batch equilibrium technique and isotherm types and parameters were estimated. Two theoretical models were applied based on a Freundlich and a Langmuir isotherms. The effect of pesticides chemical composition and structure as well as the nature of solid surface on the efficiency of adsorption was evaluated. The influence of pH also was studied. In low pH solutions adsorption of amitrole was higher upon the nonionic aliphatic acrylic ester copolymer XAD-7 in comparison to the nonionic, crosslinked macroreticular copolymer of styrene divinylbenzene XAD-4. In neutral and intermediate pH solutions the polar acrylic ester copolymer XAD-7 was more effective to the retention of alachlor. The acrylic ester copolymer showed at pH 3 the lower effectiveness in alachlor removal from water. The data of the adsorption isotherms of pesticides upon the examined polymeric resins seemed to conform to both the Freundlich and the Langmuir isotherm models.     

Influence of Suspended Clay Minerals and Humic Matter on the Solid Phase Extraction Efficiency of Selected Pesticides from Water

The purpose of this investigation was to determine the influence of humic acids (HA) and Ca-montmorillonite (CaM) on the solid-phase extraction (SPE) efficiency of atrazine, alachlor and α-cypermethrin from water samples at various pH-values. The nature and intensity of binding of the studied pesticides to CaM were determined by X-ray diffraction analysis and termogravimetric analysis (TGA) test. The studied pesticides eluted from discs were analysed by thin-layer chromatography (TLC). The effects of CaM and humic acid were generally pH-dependent and acted independently in extraction efficiency influence. Lower recovery of pesticides was observed at higher pH values when CaM was ≥0.1 g and was attributed to greater dispersion of clay, increased surface area and subsequent adsorption. Concentrations of dissolved organic carbon (DOC) in humic acid had less effect on the extraction efficiency when water was at pH 8 compared to water at pH 2, which was probably due to greater nonpolar interactions of the pesticides to the charge-neutralized humic acid molecule.     

Pesticide contamination of ground water in the United States--a review

Over 70 pesticides have been detected in ground water. Aldicarb and atrazine along with the soil fumigants EDB and DCP and DBCP have been the pesticides most frequently detected in ground water. Atrazine concentrations have been correlated with high nitrate concentrations. The triazine herbicides, simazine and cyanazine, have also been detected in ground water. The annual amount of recharge, soil type, depth of aquifer from the surface, nitrate contamination and soil pH are important field parameters in determining ground-water contamination potential by pesticides. Pesticide leaching is reduced by proper choice of crop rotation, increasing pesticide application efficiency, and integrated pest management.     

Rapid treatment of water contamined with atrazine and parathion with zero-valent iron.

The utility of fine-grained iron metal in the remediation of water contamined with Atrazine and Parathion was investigated. Batch procedures under water treatment conditions (ambient temperature and pH of approximately 7) indicated that these pesticides degrade rapidly in the presence of iron powder (40-60 mesh, 40 g/l). The decline in the concentration of pesticide was monitored by HPLC. Experiments with unbuffered solutions showed a steady increase in pH values during the reactions. Therefore, experiments were run in buffered solutions. Different buffered solutions resulted in different degradation rates indicating that the buffer plays an important role in enhancing the degradation process. Tests were also performed on an industrial effluent solution containing a variety of pesticides. Although the products of degradation were not characterized, our HPLC results indicated the disappearance of all the parent pollutants.     

Sources of phenolic compounds in two catchments of southern Portugal - effect of season, land use and soil type

Water quality monitoring in reservoirs used for human water consumption, carried out by the Alentejo Regional Authorities of the Environment (south Portugal), revealed seasonal peaks of phenolic compounds above the water-quality legislation. The main objectives of this work were to identify the main phenolic compounds present in water and soil leachates, and to determine the sources of the seasonal concentrations of phenolic compounds in two catchments with different land use patterns: Roxo and Santa Clara catchments. The main phenolic compound detected was 2,4-dinitrophenol (2,4-DNP), both in stream water and soil leachates, with concentrations higher in Roxo catchment. Roxo catchment represents a larger agricultural area than Santa Clara, and it is likely that the origin of the 2,4-DNP is associated with the use of pesticides. A peak of 2,4-DNP concentrations was observed in stream water of both catchments during February, when farmers plough their fields and apply pesticides. The 2,4-DNP peak was probably caused by a precipitation event shortly after the application of pesticides, increasing their transfer from land surfaces to adjacent streams. The leaching behaviour of 2,4-DNP was strongly dependent on the type of soil and pH. In soils with high clay content and low pH, 2,4-DNP was easily adsorbed, and its runoff from the soil to adjacent streams was reduced. Ribeira de Santa Vitória, from Roxo catchment, was the only stream showing a high abundance of vegetation, and the lowest concentrations of 2,4-DNP in water. Plants may play a role in removing contaminants from stream water.     

Application of chemometric analysis based on physicochemical and chromatographic data for the differentiation origin of plant protection products containing chlorpyrifos

The aim of this study was to investigate the similarities and dissimilarities between the pesticide samples in form of emulsifiable concentrates (EC) formulation containing chlorpyrifos as active ingredient coming from different sources (i.e., shops and wholesales) and also belonging to various series. The results obtained by the Headspace Gas Chromatography–Mass Spectrometry method and also some selected physicochemical properties of examined pesticides including pH, density, stability, active ingredient and water content in pesticides tested were compared using two chemometric methods. Applicability of simple cluster analysis and also principal component analysis of obtained data in differentiation of examined plant protection products coming from different sources was confirmed. It would be advantageous in the routine control of originality and also in the detection of counterfeit pesticides, respectively, among commercially available pesticides containing chlorpyrifos as an active ingredient.     

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.     

Sample preparation for GC analysis of selected pesticides in surface water.

A new isolation procedure for the determination of nitrogen/phosphorous containing pesticides and organochlorine pesticides in water was tested, and statistical evaluation of the recoveries was performed. The procedure, designed specifically for the analysis of semi-volatile compounds in water containing Suspended Particulate Matter (SPM), utilizes a specially designed filtration vessel coupled directly to an SPE cartridge. The studies were based on surface water samples (from the Vistula River) spiked with pesticides. SPM separation and analyte isolation/concentration were carried out in a special filtration vessel. Pesticides were sorbed both on the SPE cartridge and on the suspended matter. The cartridge and the filter with the suspended matter were extracted separately with a solvent, which enabled the determination of analyte distribution between the two. For organochlorine pesticides, between 3 and 60% of the initial amount was found on the filter, while the recoveries in the filtrate ranged from 30 to 98%. Total recoveries of organochlorine pesticides from surface water samples spiked with pesticides using the method described were high, ranging from 90 to 101%. The amounts of nitrogen/phosphorus containing pesticides recovered from the filter were lower than 2%, while those from the filtrate ranged from 69 to 92%. Total recoveries of nitrogen/phosphorus containing pesticides from surface water samples were high, ranging from 71 to 92%.     

北京城市雨水、树冠水和地表径流中有机氯农药的污染特征

对北京降雨过程中雨水、树冠水、地表径流等介质中有机氯农药(OCPs)的污染特征进行了研究,研究的污染物包括六氯苯(HCB)、六六六(HCH)和滴滴涕(DDT)。结果显示,在雨水、树冠水和地表径流中,HCH含量最高(几何平均浓度分别为11.1、21.6和25.1 ng/L),其次是HCB(几何平均浓度分别为3.71、3.54和5.91 ng/L)和DDT(几何平均浓度分别为2.64、4.66和10.6 ng/L)。对地表径流样品中所测的OCPs组分浓度与径流水质参数和气象参数的相关分析显示,所测各OCPs组分浓度与pH呈显著负相关,与径流的溶解性有机碳含量呈显著正相关,降雨量和雨前晴天数对不同组分OCPs的影响并不完全相同。平均贡献率的计算表明,雨水是城市地表径流中OCPs的一个重要来源,树冠水的贡献也不可忽视。     

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

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.     

Pesticide residues in rivers of a Brazilian Rain Forest Reserve: assessing potential concern for effects on aquatic life and human health

Pesticide residues in water, sediment, and fish samples from rivers of a Brazilian Rain Forest Reserve were measured in November 1998, March 1999, and January 2000. Concentrations of the individual pesticides were compared to ecotoxicological benchmarks based on acute toxicity tests, and to regulatory guidelines to determine the potential concern for effects on aquatic life and human health. Pesticides and metabolites were detected at all 7 sites surveyed. Residues of a total of 27 pesticides or metabolites were found in water and/or sediment samples and fish have accumulated some of the most persistent of these residues. Measured concentrations in water and sediment indicated concern for preservation of aquatic fauna. Several pesticides in water were above levels for drinking water recommended by Brazilian and/or European Union authorities, indicating also a concern for human health.     

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.     

Controlled release and retarded leaching of pesticides by encapsulating in carboxymethyl chitosan /bentonite composite gel

A novel composite gel composed of carboxymethyl-chitosan (CM-chit) and bentonite (H-bent) was used as the carrier for encapsulating atrazine and imidacloprid to control their release in water and retard their leaching in soil. Strong interactions between CM-chit and H-bent in the composite were confirmed by FT-IR, and good dispersion of pesticides in the carrier was observed by SEM. According to the results of release experiments in water, the CM-chit/H-bent composite carrier showed double advantages of both encapsulation by the polymer and sorption by the bentonite. The time taken for 50 % of active ingredients to be released, t??, was prolonged to 572 h for atrazine and 24 h for imidacloprid, respectively. The difference between the two pesticides on release behavior was related to their hydrophobicity and water solubility. Leaching experiments through a soil layer showed that this novel carrier reduced the amount of pesticides available for leaching, and would be useful for diminishing the environmental pollution of pesticides.     

Organochlorine pesticide distribution in an organic production system for cow's milk in Chiapas,Mexico

The objective of this study was to evaluate the presence of organochlorine pesticides in samples of forage, soil, water, and milk in four units of an organic production system for cow´s milk (samples of forage, milk, soil, and water) in Tecpatan, Chiapas, Mexico. The organochlorine pesticides were extracted from forage, soil and water based on the USEPA (2005) guideline and from milk based on the IDF 1991 guideline. The pesticides were identified and quantified by gas chromatography with electron capture detector (CG-ECD). In general, the highest average concentration of total pesticides was found in the samples of milk and forage (311 ± 328 and 116.5 ±77 ng g^?1 respectively). Although, the production systems analyzed are organic, organochlorine pesticides were detected in all environmental samples (forage, soil, water, and organic milk). Although no values surpassed the defined limits of Mexican and International regulation it is advisable that a monitoring program of contaminants in these production systems is continued.     

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.     

Effects of cyclodextrins on photodegradation of organophosphorus pesticides in humic water

Cyclodextrin (CyD) effects on photodegradations of organophosphorus pesticides in humic water were monitored on the basis of the increase percentage of the photodegradation rate constant for CyD-containing humic water. Remarkable promotion effects of CyDs were observed in humic water for photo-induced radical generation. The promotion effects could be mainly assigned to the inclusion effects of CyDs to catalyze interactions of pesticides with reactive radicals generated by the humin photosensitizer and inclusion-trapped in CyDs.