Document MoBGLR38EEoqjwgnrkaYr5p3M

Designation: D 3304 - 74 AMERICAN SOCIETY FOR TESTING ANO MATERIALS 1916 Rie** Si , Pliiltdtiphit, Pa.. 19103 Horn the Annua* Book o* ASTM Slenderdv Copv'iqM ASTM II not Hstad in tha currant combined Indax, will apoaar m tha naat edition Standard Method for ANALYSIS OF ENVIRONMENTAL MATERIALS POLYCHLORINATED BIPHENYLS' This Standard i issued under the fixed designation D ,1104; the number immediately following ihe de'iyojuun indicates the year of original adoption or, in the cate or revision, the year of last revision A number m pjrcnthi.-ve>. indicates the year of last reapprovat. 1. Scope 1.1 This method covers the determination of the amount and type of polychlorinated biphenyls (PCB's) in environmental mate rials, specifically air. water, soils, and sedi ments. Absolute confirmation of PCB struc tures is not obtained with this method. Structure proof can be obtained using addi tional techniques such as mass spectrometry. 2. Applicable Documents 2.1 ASTM Standards: D5I0 Sampling Industrial Water1 DIS87 Thin-Walled Tube Sampling of Soils1. D 1605 Recommended Practices for Sam pling Atmospheres for Analysis of Gases and Vapors' D 2928 Sampling Stacks for Particulate Matter' 4.1.2 The sample collected should he at least 250 ml. 4.2 Stdimtnt and Soil Sampling--A sedi ment or soil sample of at least 1000 g should be taken according to Method I) Ior :my other acceptable procedure, taking due pre cautions to minimize contamination 4.3 Air Sampling: 4.3 I Environmental sampling of ambient air or source sampling is under the jurisdic tion of ASTM Committee D-22 on Methods of Sampling and Analysis of Atmospheres There are various methods of sampling from stacks or ambient air available. See Method D 1605 or Method D2928, or both. 4.3.2 For the measurements of airborne PCB's the air sample is drawn through one or more fritted bubbler absorbers ('tiled with nanograde toluene. The PCB's are absorbed in the toluene. 3. Significance 3.1 Since it is possible for minute quan tities of PCB's to find their way into the environment, it is desirable to have a method to identify and measure the quantity of such trace amounts. 5. Principle 5.1 The PCB's present in envirttnmem.il samples are isolated from the bulk of ihc sample matrix by solvent extraction. Inter fering matrix components and endogenous residues are then removed from the sample 4. Sampling 4.1 Wottr 5flm/y//ng~Environmental sampling of natural bodies of water and effluents are covered in many methods under the jurisdiction of Committee D-19 on water. Method D5I0 is recommended with the following stipulations: 4.1.1 Linder 26.1 a final rinse with Nanograde* hexane should be udded. `This method it under the jurivdiciKin l ASTM Committee D-J7 on Electric*! Iniuluimg Liquid' end Osset Current edition approved Feb. It, 1974 Published April 1974. 1 1973 Annual Book of ASIM Standards. Pad 2 1 * 1974 Annual Book of ASIM Standards. Purl ll `"Rengenl Chemicals. American Chemical Society Specifications,"' Am. Chemical Soc. Wuthmgion. I> ( For suggestions on the testing of reagents noi lined by the American Chemical Society, sec "Kcaacni ChcrmceU end Standards. " by Joseph Rosin. I) Van Nutirand C'n Inc . New York, N. Y , and the "Unned States Pharmaconeu ` 1 MONS 077968 D 9304 extract! by a suitable combination of of the Committee on Analytical Reagents of clean-up procedures and the amount and the American Chemical Society, where such type of PCB's present determined by elec specifications are available.* Other grades tron capture gas chromatography (EC/GC). 6. Apparatus may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accu 6.1 Separatory Funnels, equipped with racy of the determination. ground-glass stoppers and TFE-fluorocarbon 7.2 Acetonitrile, Nanogradc.1 stopcocks: 12$, 250, 500, 1000, and 2000-ml Note --Ntnograde designates impurities of no capacities. more thin 10 pane per trillion. 6.2 Kunderna-Danish Evaporative Concen trators, 500-ml capacity equipped with 3-ball Snyder columns and graduated 5-ml capacity vials. 7.3 Alcoholic Potassium Hydroxide Solu tion (2.3 % weight per volume)--Dissolve 12.5 g of potassium hydroxide in 500 ml of ethanol. 6.3 Chromatographic Columns, glass, 10 7.4 Alumina (for chromatographic adsorp in. (254 mm) long by 20 mm in outside tion), 80/200 mesh. Heat at 400*C for a diameter with a reservoir 5 in. (127 him) long minimum period of 4 h and deactivate with S by 50-mm in outside diameter at the lop, % (w/w) distilled water. equipped with TFE-Auorocarbon stopcocks. 7.4.1 Alumina Column Preparation--Fill 6.4 Buchner Filter Funnels, borosilicate a chromatographic column (6.3) with hexane glass, fritted, 90 mm in inside diameter, 600-ml up to the point where the reservoir joins the capacity, medium porosity. column and push a glass wool plug to the 6.5 Bolling Flasks, flat-bottomed, 125-ml bottom with a glass rod. In a 50-ml beaker capacity. 6.6 Liebig Condensers, 200 mm in length. 6.7 Hot Flates. measure 35 ml of deactivated alumina (30 g), and pour this slowly into the column. Tap or vibrate the column to settle the alumina and 6.8 Water Bath. 6.9 Reciprocating Variable-SpeedShaker. top the alumina with 2 to 3 cm of anhydrous sodium sulfate. Wash the column with 50 to 6.10 Syringes, 10-pl. 100 ml of hexane prior to the addition of the 6.11 Mortar end Festle, all glass. 32-oz (or sample. 1-litre). 7.5 Distilled Water, extracted with hex 6.12 Baking Dishes, borosilicate, 2V*-qt ane to remove hexane-soluble electron-cap (2.4-litre). 8 by 12 by 2-in. (203 by 305 by turing impurities. 50-mm). 7.6 Ertowo/--Formula 2B. 6.13 S/eve--U.S. Standard sieve No. 30 7.7 Hexane, Nanograde.* (600-um). 7.8 FCB Standards, production grade. PCB 6.14 Gas Scrubbing Bottles, high-form, Standards Aroclor 1221,' Aroclor 1242. and ground-glass joint, fritted-coarse disks, Aroclor 1254. 250-ml capacity. 7.9 Potassium Hydroxide (KOH). 6.15 Dry Test Meter, 0.1 ft* per revolu 7.10 Sodium Sulfate, anydrous. granular. tion. Heat the sodium sulfate (NaiSO) at 400*C 6.16 Laboratory Vacuum Fump. for l h prior to use. 6.17 Rotary Vacuum Evaporator. 7.11 Sulfuric Acid {sp gr 1.84)--Concen 6.18 For the apparatus used in the Elec trated sulfuric acid (HiSOt). tron Capture Gas Chromatographic Proce 7.12 Toluene, Nanograde.* dure, see Section 10. I. Sample Preparation and Extraction 7. Reagents 8.1 Water: 7.1 Furity of Reagents--Reagent grade 8.1.1 Where possible, the entire water chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all reagents shall conform to the specifications ` aa|,.tr*e trademark of Matlinckrotft fhamteal Worki. ' Xajiitafod trndtmark of Monsanto Co 2 HONS 077969 sample is extracted with hexane. With larger samples, where this is not physically possi ble. the containers are simply agitated and a 250-ml portion used for analysis. 8.1.2 Extraction of Water Samples--After agitating, transfer the entire aqueous sample or a 250-ml aliquot into a graduated glass cylinder. Record the volume of the sample and quantitatively transfer it to a separatory funnel with distilled water. 8.1.3 Rinse the sample container and graduate cylinder with two 50-ml portions of hexane, adding each to the separatory fun nel. If the entire sample is not consumed, rinse only the graduate cylinder. 8.1.4 Stopper the separatory funnel and hand shake vigorously for at least I min. Allow the layers to separate and transfer the lower aqueous phase to a second separatory funnel. 8.1.5 Extract the water sample a second time with a 50-ml portion of hexane. After the layers have separated, add the first hexane extract to the second separatory funnel and transfer the aqueous layer to the original separatory funnel. 8.1.6 Repeal the extraction with a third 50-ml portion of hexane. Discard the aqueous layer and combine the hexane extracts. 8.1.7 Filter the combined extracts through a 4-in. (100-mm) funnel plugged with glass wool that is covered with sodium sulfate. Collect the filtrate in a Kunderna-Danish evaporative concentrator; add a small boil ing chip. Put the Snyder column in place, and reduce the hexane volume to less than 5 ml by healing the apparatus in an 80 to 90*C water beth. CAUTION--So/vr/tf vapors must be vented into a hood. Remove the evaporative concentrator from the waier bath and after cooling to room temperature adjust the volume to 3.0 ml. 8.1.8 Inject a fraction of a microlitre of the concentrate into the gas chromatograph to chack for interferences and determine the approximate level of PC 0's present. If no interferences are present, dilute or concen trate the sample to a known volume, as determined by the electron capture chromat ogram, and proceed with the gas chromato graphic anatysii. 8.1.9 If interferences are present, proceed with the chemical treatment and column chromatographic cleanup procedures. 8.2 Sediment and Soil. 8.2.1 Any excess water is decanted and the entire sediment or soil sample transferred to a glass baking dish to air dry at room temperature. The dried materia) is trans ferred from the dish into a mortar and pestle and ground. The ground sediment is sieved, remixed, and a 250 g portion taken for analysis. 8.2.2 Weigh 250 g (to the nearest 0 01 |>) into a I6-02 (or 500-ml) narrow-neck screwcap glass bottle (with an aluminum foil liner). 8.2.3 Moisten the soli with water (10 ml) and add 150 ml of acetonitrile. Cap the bottle tightly, and mechanically shake for a minimum period of 1 h. 8.2.4 Quantitatively transfer the acetoni trile extract into a siniered-glass filter funnel containing a /-. (6.4-rnm) layer of anhy drous NaSO. Collect the filtrate in a 600-ml beaker (vacuum filtration may be necessary). 8.2.5 After the acetonitrile has completely drained into the beaker, wash the bottle twice with 50-ml portions of acetonitrile, adding each wash to the funnel after the previous has completely percolated through the sediment. 8.2.6 Quantitatively transfer the extract to a Kunderna-Danish evaporative concen trator; add a small boiling chip. Put the Snyder column in place, and reduce the solvent volume to less than 5 ml by heatmg the apparatus in a 80 to 90*C water bath. CAUTION--Solvent vapors must be vented into a hood. 8.2.7 Carefully evaporate the acetonitrile extracts to dryness with the aid of a gentle stream of dry nitrogen. Redissolve (he resi due in maximum of 5 ml of hexane. 8.2.8 Inject a fraction of a microlitre of (he concentrate into (he gas chromatograph to check for interferences and determine the approximate level of PCB's present If no interferences are present, dilule or concen trate the sample to a known volume, as determined by the electron capture chromat ogram, and proceed with (he gns chromato graphic analysis. 3 MGNS 077970 # 0 3304 8.2.9 If interferences are present, proceed with the chemical treatment and column chromaiotraphic cleanup procedures. 8.3 Airborne PCB's: 8.3.1 After scrubbing the desired amount of air, record the metered volume, pressure, and temperature. 8.3.2 Quantitatively transfer the scrub* bing solvent to a round-bottom flask and reduce the volume to approximately 2 ml by rotary vacuum evaporation. 8.3.3 Quantitatively transfer the concen trate to a 30-ml beaker with the aid of several small portions of toluene. 8.3.4 Inject a fraction of a microlitre of the concentrate into the gas chromatograph to check for interferences and determine the approximate level of PCB's present. If no interferences are present dilute or concen trate the sample to a known volume, as determined by the electron capture chromat ogram. and proceed with the gas chromato graphic analysis. 8.3.5 If interferences are present, proceed with the chemical treatment and column chromatographic cleanup procedures. 9. Supporting Procedures--Sample Clean UP 9.1 Saponification with Alcoholic Potas sium Hydroxide and Extraction with Sulfu ric Acid: 9.1.1 Quantitatively transfer the concen trated extracts to a 125-ml extraction flask with the aid of several small portions of solvent. 9.1.2 Evaporate the extract just to dryness with a gentle steam of dry filtered air (5A mo lecular sieve of equivalent to remove oil, water, and particles above 12 urn) and add 25 ml of 2.5% alcoholic KOH. 9.1.3 Add a boiling chip, put a water condenser in place, and allow the solution to reflux on a hot plate for 45 min. 9.1.4 After cooling, transfer the solution to a 250-ml separatory funnel with the aid of 25 ml of distilled water. 9.1.5 Rinse the extraction flask with 25 ml of hexane and add it to the separatory funnel. 9.1.6 Stopper the separatory funnel and shake vigorously for at least I min. Allow the layers to separate and transfer the lower aqueous phase to a second separatory funnel. 9.1.7 Extract the saponification solution with a second 25-ml portion of hexane. After the layers have separated, add the first hexane extract to the second separatory funnel and transfer the aqueous alcohol layer to the original separatory funnel. 9.1.8 Repeat the extraction with a third 25-ml portion of hexane. Discard the saponi fication solution and combine the hexane extracts. 9.1.9 Carefully add 25 ml of concentrated H|S0, in small portions, to the hexane extracts. 9.1.10 Stopper the separatory funnel and shake vigorously for at least I min, venting the funnel as necessary. Allow the layers to separate and discard the lower aqueous-acid layer. Repeat this until the acid layer is colorless. 9.1.11 Wash the hexane with a 25-ml por tion of water. Discard the water wash. 9.1.12 Filter the hexane extract through a 4- in. (100-mm) funnel plugged with glass wool that is covered with a layer of anhy drous NaSO. Collect the filtrate in a Kundema-Danish evaporative concentrator, add a small boiling chip, put the Snyder column in place, and reduce the hexane volume to leas than 5 ml by heating the apparatus in an 80 to 90*C water bath. CAUTION--Solvent vapors must be vented into a hood. Remove the evaporative concentrator from the water bath and after cooling to room temperature adjust the volume to 5.0 ml. 9.2 Liquid-Solid Chromatographic Clean up With Alumina: 9.2.1 After preparation of the alumina column, as described in Section 7, quantita tively transfer the hexane extracts (5 ml or less) on to the column with the aid of several 5- ml portions of hexane (lowering the solvent level to the adsorbam level afler each addi tion of solvent. Do not allow the top of the column to become dry). 9.2.2 Carefully add 125 ml of hexane to the column reservoir and collect the total eluent in a Kunderna-Danish evaporative concentrator. 9.2.3 Add a small boiling chip to the Kunderna-Danish evaporative concentrator. 4 MGNS 077*71 D 3304 put the Snyder column in place, and reduce the hexane volume to less than 5 mi by heating the apparatus in an 80 to 90*C water bath. CAUTION--Solvent vapors must be vented into a hood. Remove the evaporative concentrator From the water bath and after cooling to room temperature adjust the vol ume to S.O mi. 10. Electron Capture Gas Chromatographic Procedure . 10.1 Instruments--A gas chromatograph equipped with isothermal oven temperature control. 10.2 Detector--High-temperiture *'Ni Electron Capture Cell 10.3 Column--A 6-mm by 6-ft (1.8-m) glass column, 4% XE-60 on 80/100 mesh Chromosorb W. high-performance 10.4 Column Temperature--The column temperature shall be as follows for the vari ous Arodors: Aroclor 1221, I70*C; Arodor 1242, |90*C; Aroclor 1254, 205C. 10.5 Detector Temperature--The detector temperature shall be 2SO to 300*C. 10.6 Injection Fort Temperature--The in jection port temperature shall be 220*C. 10.7 Pulse--The pulse rate shall be SO us. 10.8 Flow Rates--The flow rates shall be as follows: 10.8.1 Helium Carrier--60 ml/min. 10.8.2 90% Argon-10% Methane Purge-- 20 ml/min. 10.9 Using EC/GC as the determinative step, inject in duplicate 2 to 8 of each sample solution into the chromatograph. By comparison with standard solutions injected, under the same operating conditions, deter mine the amount and type of Aroclor using the total area method. 11. Quantitative Deter ruination I l.l Quantitative determinations employing the electron capture detector are non-stoichiometric measurements made by comparing the total areas for known concentrations with those for unknown concentrations. Four vari ations of the area quantification procedure have been employed, as follows: II.1.1 Case /--EC gas chromatogram of PCB unknown unchanged with respect to standard PCB with no evidence of interfer ences. 11.1.2 Case II-- EC gas chromatogram of PCB unknown altered with respect to stan dard PCB with no evidence ot interference. 11.1.3 Case III--EC gas chromatogram of PCB unknown unchanged with respect to standard PCB with evidence of interference 11.1.4 Case IV--EC gas chromatogram of PCB unknown altered with respect to stan dard PCB with evidence of interference. 11.2 Determine the PCB level in Case I and II samples by comparison of the total area of (he peaks in the unknown with a calibration curve prepared by plotting the total area of the peaks in the electron capture chromatogram of the corresponding standard versus the number of nanograms of the standard injected. Initially subject Case III and IV samples to the chemical cleanup procedure and follow by chromatography on alumina. If the interferences are removed by this treatment, calculate the PCB levels for Cases lit and IV in the same manner as Cases I and H. If dominant interferencc(s) is (are) still present, estimate the maximum PCB level in accordance with Cases I and II after correcting the total area for that of the interfering peak(s). In all cases, the response of the electron capture must be linear for quantitative analysis. 12. Calculations 12.1 Assuming that the calibration curve is prepared by plotting the electron capture response (total peak area) versus nanogrums of the PCB standard injected, calculate the PCB level present in the air, water, or sediment-soil sample as follows: 12.1.1 Water and Sediment-Soil Sample* C - \(A!B){D x I0'*l)/ml(l0 ' mg/ng)|/6' 12.1.2 Air Samples: F U^/)(Px tOVD/ml (10~* mg/ng)j "c (28 32 liue/ft'Xm*/10* litre) </\ - P,/P,)|T./273 4 T,) where: A - PCB in unknown from calibration curve, ng, B - final concentrate injected into ihe in strument, ul, C - concentration of PCB's in water, and sediment-soil sample, mg/kg (or ppm). 5 HONS C77972 0 - volume of final concentrate, ml, - sample weight, kg, F - concentration of PCB's in air sample, mg/m', at one atmosphere and 25C, G - air sampled from meter, ft*. Pt - standard pressure. 760 mm Hg, P, - differential pressure of gas stream, mm Hg. Tt standard temperature, 298 K. and 7\ - temperature of sampled gas, C. 12.2 The corrections for the pressure drop through the scrubbers and for the gas tern* perature are necessary to get an accurate measurement of the gas volume sampled. 13. Precision and Accuracy 13.1 In order to establish the precision and accuracy of the method used for estimating PCB content in the environment, a roundrobin testing experiment was set up. Sam ples were prepared by spiking water with PCB's at the level of about $00 ppb. Individ ual preparations included blanks (no PCB), Aroclor 1242 only, Aroclor 1254 only. Arodor 1260 only, all 50-50 two-component mix tures, and a '/), 'A, `4 preparation containing all three Arodors. Six samples of each mix ture were prepared, and tested by two ana lytical laboratories. Each result, expressed in ppb of the individual components was con verted to percent of the total PCB added. Analysis of variance was run on all the data taken together and on each laboratory inde pendently. Two obviously defective samples were deleted from the data. 13.2 The precision and accuracy of this method on standard air and soil-sediment sam ples have not been established. 13.3 Conclusions: 13.3.1 The 95% confidence limns for indi vidual results were as follows: Either laboratory 17.5 IJ R Laboratory A Laboratory a II J* 46.4% 43.7*16 2% 13.3.2 The repeatability for the individual laboratories, based on repeat test* of sample* having identical prepared compositions is as follows: Laboralory A Laboratory B *42 0% *114% 13.3.3 In general. Laboratory B comes closer to properly identifying the individual Aroclors with one exception, Arodor 1234 found in a mixture of Aroclor 1242 and Aroclor 1260. as follows: Mixturn Present Laboratory A Laboratory B 1 1242 1242.(1234) 1242 2 <242.1234 1242.1234. (1260) 1242.1234 ) 1242.1254. 1242. ( ). 1242. >234, 1260 4 1234 1260 1260 1234.(1260) 1234.(1260) 3 1242, 1260 1242. 1260 1242.0234), 1260 6 1260 (1241), 1260 1260 7 1234. 1260 (1241), 1234 1234. 1260 1260 Number* in parentheses indicate misideniifications. 14. Contamination 14.1 In determining PCB's by electron capture gas chromatography, laboratory sources of contamination can be a major problem. The samples and extracts should never be allowed to come in contact with materials other than glass, TFE-fluorocarbon. or metal. Laboratory glassware and sampling gear should be thoroughly washed with hot, soapy water, rinsed with distilled water, acetone, and then hexane. All equip ment should also he rinsed again with hex ane just prior to use and blanks should be frequently carried through all steps of the procedure to insure against the possibility of contamination. APPENDIX ELECTRON CAPTURE CHROMATOCRAMS OF COMMERICAL PCB MIXTURES 6 MOMS 077973 0 3304 AKOCtOK 1221 B4P 402 Wl-63 1C 1/4"I* 4X XI-40 on 10/100 Chroaooork H nr Col. Toap. - 170*C InJ. Toap. - 220*C One. Toap. - 250*C CarrLor Coo - Ho 40 ol/aln. 2ro On* - 101 CMA/Argon 120 al/aln Pulao Interval - 50 po Aat. InJoetaA - 5 yl ltd. Cone. - 1.41 X 10"* |/al Kongo - 10 Attn. - 4 % - - 3c FIG. Al Aradar Oil Elwtrao Captor* Chraaioia|rnm. 7 HONS 077974 # D1304 8 MONS 077873  D 3304 By pMkailoa of Iklt iiaadafa so potlllos It lahta with rnpttl to tht voMUy of any paitm m ronwiiw thtrtwkh, and tkt Amtrltas Sockty for Twist asd Malthah lot* not mdtnah* to iwurr nnyont unhung tht nandard ofainti ttaMUy far lufristtmtsi of any Ltutrt Fatoai nor atiumt any intA Uahlliy 9 MOMS C77976