ASTM_D_5659_-_14.pdf

Designation:D565914Standard Test Method forChlorophenoxy Acid Herbicides in Waste Using HPLC1This standard is issued under the fixed designation D5659;the number immediately following the designation indicates the year oforiginal adoption or,in the case of revision,the year of last revision.A number in parentheses indicates the year of last reapproval.Asuperscript epsilon()indicates an editorial change since the last revision or reapproval.1.Scope1.1 Thistestmethodcoverstheanalysisof2,4-dichlorophenoxyaceticacid(2,4-D),2,4,5-trichlorophenoxyaceticacid(2,4,5-T),and2,4,5-trichlorophenoxypropionic acid(silvex)in liquids and solids,using high performance liquid chromatography with an ultra-violet detector(HPLC/UV).This test method is applicable fora concentration range from approximately 50 to 1000 ppm.This range takes into consideration the sample preparation anddilutions outlined in Section 10.Lower detection levels can beobtained by using larger sample sizes,smaller total finalvolumes,or with the use of in-line or solid phase extraction,concentration,or cleanup,or combinations thereof.1.2 The chlorophenoxy herbicides may be present as avariety of salts or esters,which are converted to,analyzed,andreported as their respective acids.1.3 This test method is applicable to liquid and solid wasteand waste extract matrices including aqueous,oil,spentsolvent,soil,ash,leachates,etc.1.4 This test method may be applicable to other phenoxyacid herbicides.1.5 This standard does not purport to address all of thesafety concerns,if any,associated with its use.It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.See Section 7 and10.3.1 for specific precautionary statements.2.Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent Water2.2 EPA Documents:Method 8150Chlorinated Herbicides,Test Methods forEvaluating Solid Waste Physical/Chemical Methods SW-846 Third Edition3Method 8000AGas Chromatography,Test Methods forEvaluating Solid Waste Physical/Chemical Methods,SW-846,3rd Edition,Final Update 13Method 555 Determination of ChlorinatedAcids in Water byHigh Performance Liquid Chromatography with a Photo-diode Array Ultraviolet Detector EPA/600/R-92/129,Methods for the Determination of Organic Compounds inDrinking Water,Supplement No.233.Summary of Test Method3.1 The chlorophenoxy acids and esters are hydrolyzed totheir respective salts by heating and stirring the sample withaqueous alkali.The salts are then converted to their respectiveacids by the addition of HCl.The aqueous solutions of the freeacids are then analyzed using High Performance Liquid Chro-matography(HPLC)using ultraviolet detection.4.Significance of Use4.1 Phenoxy acid herbicides are used extensively for weedcontrol.Esters and salts of 2,4-D,2,4,5-T,and Silvex havebeen used for agricultural crop and lawn care.5.Interferences5.1 Organic liquids that have high percent levels of chlori-nated organics and are denser than water may interfere with theextraction of Silvex.It is necessary to mix these samples withhexadecane,typically in a 1:1 ratio,before hydrolysis.5.2 Phenols,especially chlorophenols interfere with theprocedure,by coeluting with the analytes of interest.5.3 Interferences may be encountered from other organiccompounds that absorb UV at the specified wavelengths.Also,closely eluting compounds may complicate identificationbased solely on retention time.When these types of interfer-ences are encountered,the analyst must rely on other sourcesof information for positive identification,such as the follow-ing:1This test method is under the jurisdiction of ASTM Committee D34 on WasteManagement and is the direct responsibility of Subcommittee D34.02 on Dischargeof Organic Wastes into Sanitary Sewers.Current edition approved Nov.1,2014.Published December 2014.Originallyapproved in 1995.Last previous edition approved in 2006 as D5659 95(2006).DOI:10.1520/D5659-14.2For referenced ASTM standards,visit the ASTM website,www.astm.org,orcontact ASTM Customer Service at serviceastm.org.For Annual Book of ASTMStandards volume information,refer to the standards Document Summary page onthe ASTM website.3Available from the Superintendent of Documents,U.S.Government PrintingOffice,Washington,DC 20402.Copyright ASTM International,100 Barr Harbor Drive,PO Box C700,West Conshohocken,PA 19428-2959.United States1 5.3.1 Secondary confirmation wavelengths such as 227 nmor 235 nm.5.3.2 Use of a confirmation column.5.3.3 Use of a confirmatory chromatography program suchas changing the mobile phase composition or gradient.6.Apparatus6.1 Analytical High-Pressure Liquid Chromatograph,ca-pable of achieving pressures of 4000 psi and flow rates of 3mL/min.6.2 Variable Wavelength Ultraviolet Detector,capable ofmonitoring at 207,227,and 235 nm,either simultaneously orindividually.6.3 Chromatographic Column,C18 radial compression 8 by100 mm,4-m parti