Pesticides in water

U.S. EPA, Metliod SIS.1-Determination of Chlorinated Pesticide in Water hyGCjECD, draft, Apr. 15, 1988 available from U.S. EPA Environmental Monitoring and Support Laboratory, Cincinnati, Ohio, 1988. 

High performance Hquid chromatography with electrochemical detection has been used to determine 2—7 ppb of carbamate pesticides in water (40). The investigated pesticides were aminocarb, asulam, j -butylphenyknethylcarbamate (BPMC), carbaryl, carbenda2im, chlorpropham, desmedipham, and phenmedipham. 

In 1980 the Drinking Water Directive was introduced, which specified a maximum limit of 0.1 /rgU for any pesticide in drinking water and 0.5 /rgU for total pesticides. Monitoring was needed for a wide range of pesticides in water and this became the impetus for developing new analytical techniques capable of detecting pesticides at very low levels. Consequently, analytical techniques improved and more pesticides were detected in watercourses and water supplies. 

E. A. Hogendoom, U. A. Th Brinkman and P. van Zoonen, Coupled-column reversed-phase liquid cliromatography-UV analyser for the determination of polar pesticides in water , 7. Chromatogr. 644 307-314 (1993). 

Figure 13.7 Selectivity effected by employing different step gradients in the coupled-column RPLC analysis of a surface water containing 0.40 p-g 1 bentazone, by using direct sample injection (2.00 ml). Clean-up volumes, (a), (c) and (d) 4.65 ml of M-1, and (b) 3.75 ml of M-1 transfer volumes, (a), (c) and (d), 0.50 ml of M-1, and (b), 0.40 ml of M-1. The displayed cliromatograms start after clean-up on the first column. Reprinted from Journal of Chromatography, A 644, E. A. Hogendoom et al, Coupled-column reversed-phase liquid chromatography-UV analyser for the determination of polar pesticides in water , pp. 307-314, copyright 1993, with permission from Elsevier Science.

Figure 13.19 Chromatograms obtained by on-line SPE-GC-MS(SIM) of (a) 10 ml of tap water spiked with pesticides at levels of 0.1 ng 1 (b) 10 ml of a sample of unspiked tap water. Peak identification foi (a) is as follows 1, molinate 2, a-HCH 3, dimethoate 4, simazine 5, ati azine 6, y-HCH 7, S-HCH 8, heptachloi 9, ametiyn 10, prometiyn 11, fen-itrothion 12, aldrin 13, malatliion 14, endo-heptachlor 15, a-endosulfan 16, teti achlor-vinphos 17, dieldrin. Reprinted from Journal of Chromatography, A 818, E. Pocumll et al., On-line coupling of solid-phase exti action to gas cliromatography with mass specti ometiic detection to determine pesticides in water , pp. 85-93, copyright 1998, with permission from Elsevier Science.

E. Pocurull, C. Aguilar, E. Borrull and R. M. Marce, On-line coupling of solid-phase extraction to gas cliromatography with mass spectrometric detection to determine pesticides in water , 7. Chromatogr. 818 85-93 (1998). 

T. H. M. Noij, M. E. Margo and M. E. van der Kooi, Automated analysis of polar pesticides in water by on-line solid phase extr action and gas cliromatography using the cosolvent effect , 7. High Resolut. Chromatogr. 18 535-539 (1995). 

Marutoiu C, Vlassa M, Sarbu C, et al. 1987. Separation and identification of organophosphorus pesticides in water by HPTE. J High Resolution Chromatog Chromatog Comm 19 465-466. 

EPA. 1997d. Methods and guidance for analysis of water. Method 508 Determination of chlorinated pesticides in water by gas chromatography with an electron capture detector. U.S. Environmental Protection Agency, Washington, DC. EPA 821-C-97-001. 

Rekolainen S. 1988. Occurrence and leaching of pesticides in waters draining from agricultural land. 

Because of the great importance of drinking water for human health, quality standards for pesticides in water were developed at Community level based on the precautionary principle. Toxicological considerations were not taken into account to derive the general limit for pesticides. 

An SPE method has been developed to replace the classical LLP method. Water sample is extracted with an SPE column such as Cig and styrene-divinylbenzene copolymer (PS-2) cartridges, which consist of a reversed bonded-phase silica sorbent, provided as an extraction tool. This is a simple and rapid method, and applied to the determination of residual amounts of naproanilide, propanil, mefenacet, etc. This system determines the residual amounts of most of the pesticides and has been successfully applied to determination of pesticides in water. 

Although SPME was applied initially for the analysis of relatively volatile environmental pollutants in waters, rapid developments have enabled SPME to be successfully applied for the analysis of pesticides in water, wine and more complex food samples such as honey, fruit juice and pears, vegetables and strawberries. With food samples, most analysts recognize the need for some sample pretreatment in order to minimize matrix effects. The matrix can affect the SPME efficiency, resulting in a reduced recovery of pesticides. The most common method is simply to dilute the sample or sample extract with water. Simpltcio and Boas comminuted pears in water prior to the determination of pesticides. Volante et al. extracted over 100 pesticides... 

E.B. Tribaldo, Residue analysis of carbamate pesticides in water, in Food Science Technology, Marcel Dekker, New York, pp. 537-570 (2000). 

Marvin, C. H., Brindle, I. D., Singh, R. P., Hall, C. D., and Chiba, M., Simultaneous determination of trace concentrations of benomyl, carbendazim (MBC) and nine other pesticides in water using an automated on-line pre-concentration high-performance liquid chromatographic method, /. Chromatogr., 518, 242, 1990. 

Monitoring and controlling pesticides in water (the way it was done in Russia and all other countries) does not give a true picture of the danger of pesticides in bodies of water, since it does not take into account the distribution of pesticides within the water mass layers [1,3]. The concentration of pesticides in the thin layer of water near the surface can be hundreds ( ) of times higher than in the rest of the water mass. The role of the surface layer is exceptionally important, not only for substance exchange between the atmosphere and the water, but also for the lives of many hydro organisms. 

Walsh J.E., MacCraith B.D., Meany M., Vos J.G., Regan F., Lancia A., Artjushenko S., Sensing of chlorinated hydrocarbons and pesticides in water using polymer coated mid-infrared optical fibres, Analyst, 1996 121 789-792. 

T. Montensinos, S.P. Munguia, F. Valdez, and J.L. Marty, Disposable cholinesterase biosensor for the detection of pesticides in water-miscible organic solvents. Anal. Chim. Acta 431, 231-237 (2001). 

Wilson and co-workers [332, 333] have discussed the determination of aldrin, chlordane, dieldrin, endrin, lindane, o,p and p,p isomers of DDT and its metabolites, mirex, and toxaphene in seawater and molluscs. The US environmental Protection Agency has also published methods for organochlo-rine pesticides in water and wastewater. The Food and Drug Administration (USA) [334] has conducted a collaborative study of a method for multiple organochlorine insecticides in fish. Earlier work by Wilson et al. [333, 335] in 1968 indicated that organochlorine pesticides were not stable in seawater. 

D. Following signal detection, select the optimal set of column wells (this will be dependent on the goal of the assay if, for instance, a screening assay is required with a certain cutoff concentration, e.g., 0.1 ng/mL for pesticides in water, then the labeled antigen concentration that yields a B/BO of 50% at 0.1 ng/mL will be ideal). 

In response to the concern expressed by the shellfish farmers operating in the Ebro River delta about the potential positive role of pesticides on the oyster and mussel mortalities observed in the area, our group, commissioned by and with the collaboration of the Catalan Water Agency (ACA), carried out a comprehensive study in which chemical and toxicity data were combined to assess potential toxic presures present in the delta. To this end, a combined approach scheme integrating the measurement of various general physicochemical parameters in water, quantitative chemical analysis of pesticides in water and biota, and ecotoxicity assays in water was applied to a series of samples collected at springtime (between mid-April and mid-June 2008) from six selected sites of the delta the two (northern and southern)... 

Analysis of pesticides in water was performed by fully automated online solid-phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/ MS) [25, 31]. These pesticides (a total of 22 belonging to the classes of triazines, OP, chloroacetanilides, phenylureas, thiocarbamates, acid herbicides, and anilides) were selected on the basis of previously published studies [20, 25], information gathered from the water authorities, and known use in rice crops. 

Feo ML, Eljarrat E, Ginebreda A et al (2010) Presence of pyrethroid pesticides in water and sediments of Ebro River Delta. J Hydrol doi 10.1016/j.jhydrol.2010.08.012... 

Freed, V.H., C.T. Chiou, and D.W. Schmedding. 1979. Degradation of selected organophosphate pesticides in water and soil. Jour. Agric. Food Chem. 27 706. 

Alford-Stevens, A.L., J.W. Eichelberger, and W.L. Budde. 1988. Multilaboratory study of automated determinations of polychlorinated biphenyls and chlorinated pesticides in water, soil, and sediment by gas chromatography/mass spectrometry. Environ. Sci. Technol. 22 304/312. 

TFC was used to measure 11 pesticides in water (Asperger et al. 2002). Five TFC columns (50 x 1 mm inner diameter) were tested. The columns were the silica-based Turbo C18 and Turbo... 

Asperger A. et al., 2002. Trace determination of priority pesticide in water by means of high-speed online solid-phase extraction-liquid chromatography-tandem mass spectrometry using turbulent-flow chromatography columns for enrichment and a short monolithic column for fast liquid chromatographic separation. J Chromatogr A 960 109. 

Katagi T (2006) Behavior of pesticides in water-sediment systems. Rev Environ Contam Toxicol 187 133-251... 

Table 6. Concentrations and ratio of persistent organochlorinated pesticides in water currents of the Mugano-Salyansk region (Azerbaijan) entering the Caspian Sea (Galiulin 1995).

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