{ 9140006086 _ United States Environmental Protection Agency Office of Water Regulations and Standards | REFERENCE Industrial Technology Division y od Office of Water July 1989 Method 1618: Organo-halide Pesticides, Organo-phosphorus Pesticides, and Phenoxy-acid Herbicides by Wide Bore Capillary Column Gas Chromatography with Selective Detectors CTMethod 1618 Revision A July 1989 Organo-halide Pesticides, Organo-phosphorus Pesticides, and Phenoxy-acid Herbicides by Wide Bore Capillary Column Gas Chromatography with Selective Detectors 1 16 SCOPE AND APPLICATION This method is designed to meet the survey Fequirenents of the USEPA ITD. The method is used to determine the organo-hal ide Pesticides and polychlorinated biphenyls (PcB's), the organo-phosphorus pesticides, and the phenoxy-acid herbicides and herbicide esters, associated with the Clean Water Act Cas amended 1987); the Resouree Conservaticn and Recovery Act (as amended 1986); the Conprehensive Environmental Response, Compensation and Liability Act (as amended 1986); and other compounds amenable to extraction and analysis by autonated, wide bore capillary colum gas chromatography (GC) with halogen specific end organo-phosphorus detectors. The chenicat compounds Listed in Tables 1 3 may be determined in waters, soils, sediments, and sludges by this’ method, The method is a consolidation of EPA Methods 608, 608.1, 614, 615, 617, 622, and 701. "For waters, the ‘sample extraction and concentration steps are essentially the sane as in these method: Nowever, the extraction and concentration steps have been extended to other sample matrices. The method should be applicable to other pesticides and herbicides. The quality assurence/qual ity control require Rents in Section 8.6 of this method give the steps necessary to determine its applicsbil ity. When this wethod is applied to analysis of unfamiliar samples, compound identity shall be supported by at lesst one additional qualitative technique. This method describes analytical conditions for 8 second gas chromatographic column that can be used to confirm measurements made with the primary column. as chrometography-mass spectrometry (6CNS) on be used to confirm compounds in extracts produced by this method when analyte levels are sufficient. The detection Limits of this method are usually dependent on the Level of 1s at at are 243 22 interferences rather than _instrunental Limitations. The Limite in Tebles 4 = 6 typify the minimum quantities that can be detected with no interferences present. This method is for use by or under the supervision of analysts experienced in the use of @ gas chromatograph and in. the interpretation of gas chromatographic data. Each Laboratory that uses this nethod must dencnstrate the ability to Generate acceptable results using the procedure in Section 8.2, sueNaRY OF METHOD extraction The percent solids content of a sample is determined. Aqueous samples containing 1 - 30 percent Solids -- the sample is diluted ‘to one Percent solids, if necessery. The Pesticides and PCB's are extracted from a one Liter sample with methylene chloride using continuous extraction techniques. For the herbicides, the pH of the sample is raised to 12 - 13 to hydrolyze esters, the sample is back-extracted to ronove basic and neutral species, the pH is then reduced to less than 2, and the senple is extracted with diethylether using separatory funnel techniques. Somples containing greater than 30 percent solids -- the sample is extracted with ecetonitrile and then methylene chloride Using ultrasonic techniques. the extract fs back extracted with tho percent (w/v) sodium sulfate in reagent water to renove water soluble interferences and residual acetonitrile. Samples in which phenoxy- ‘acid herbicides are to be determined are acidified prior to extraction. Concentration and cleanup -- For sem in sinich pesticides are to be deternined, ‘each extract 1s dried over sodium sulfate, concentrated using a Kuderna-Danish evaporator, cleaned up Cif necessary) Using get permeation chromatography (GPC),Ae i 42 43 44 45 SAFETY The toxicity or carcinogenicity of each compound or reagent used in this method has not been precisely dotermined; however, each chemical compound should be treated as potential health. hazard. Exposure to these compounds should be reduced to the lovest possible level. The laboratory is responsible for maintaining 2 current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material handling sheets should also be made available to all personnel involved in these analyses. Additional information on Laboratory safety can be found in References 1 - 3. The following compounds covered by this Inethod have been tentatively classified as noun of suspected furan or marmalian carcinogens: 4,4/-D00, 4,4/-00T, the SHCS and the PCBs. Primary standards of these compounds shall be prepared ina hood, and 8 NIOSH/HESA approved toxie gas respirator should be worn when high concentrations are handled. Diszonethane is 2 toxle carcinogen which can decospose or explode under certain conditions. Solutions decompose rapidly in the presence of solid materials such as copper powder, calcium chloride, and boiling chips. The following operations may cause explosion: heating above 90 *¢; Use of grinding surfaces such as ground Glass joints, sleeve bearings, ond glass stirvers; and storage near alkali wetals. Diazomethane shall be used only behind @ safety scroon in a well ventilated hood and should be pipetted with mechanical devices onty. Mercury vapor is highly toric. If mercury fs used for sulfur renoval, all operations involving mercury shall be performed in a hod. Unknown samples may contain high concentrations of volatile toxie compounds. Saeple containers “should be ‘opened in @ hood and handled with gloves that wilt prevent exposure. The even used for sample drying to determine percent moisture should be located in @ hood 20 ‘that vapors fron samples do not create a heatth hazard in the laboratory. 5.1 Baa Batt 5.4.2 5.14.3 5.1 5.1.0.5 5.1.5.4 5.2 5.2.4 5.2.2 5.2.3 APPARATUS AMD MATERIALS Sempling equipment for composite sampling. diserete or Semple bottles and caps Liquid semples (waters, sludges and similar materials that contain tess than five percent solids) -- Sample bottle, aber gloss, 1 liter or 1 quart, with serew cap. Solid samples (soils, sediments, sludges, filter cake, compost, and similar materials that contain more than five Percent solids) -- Sample bottle, wide mouth, ssber glass, 500 al minimum. If anber bottles are not available, Samples shall be protected from light. Bottle caps -- Threaded to fit somle bottles. Caps shall be Lined with Teflon, Cleaning Bottles are detergent water washed, then solvent rinsed or baked at 450 °C for one hour minimum before use. Liners are detergent water washed, then reagent water and solvent rinsed, and baked at approx 200 °C for one” hour ‘sininum prior to use. Compositing equipment -- Automatic or manual compositing systea incorporating Glass éontsiners cleaned per bottle cleaning procedure above. Sample containers are kept at 0 - 4 °C during sompling. Glass or Teflon tubing only shall be used. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be Used in the pump only. Before use, the tubing shall be thoroushly rinsed with methanol, followed by repeated rinsings with reagent water to minimize sanple contanination. An integrating flow meter is used to collect proportional composite samples. Equipnent for determining pereent moisture oven, capable of. being controlled at 110 25 ¢c, temperature Dessicetor crucibles, porcelain