Document 2jJzmG7nv4y8prRRx50E2BLmg

MV --r (||) Designation'. D 3304. - 74 - " 'r AMERICAN SOCIETY FOR TESTING AND MATERIALS 1916 ncft St.. FM.ildnph.. P**. 19103 Rtptirttoti tioiTi rhe krmu*l Ooo* ot AS1 M S'-.'VJu'Or, Cof>v,r igM ASTM l< not I'ttod in Ui* u"*nt eemhinoa Irtdea, v,ll appear in tn naar ed> non Standard Method for ANALYSIS OF ENVIRONMENTAL MATERIALS POLYCHLORINATED BIPHENYLS1 7Kit Sli'<tmd it iitpcd under () Toed dfsip nation 0 3304; the number immediately following the destenation indtcaitt the tear of criminal jdcption or. in the e**e of <vmon, the year of last revision. A number m parenilieset indicates the >ea> of tail te*|*pro*al. 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 PCft struclittes is not obtained with this method. Structuic proof can be obtained using addi tion:1.] techniques such as mass spectrometry. 2. Applicnblc Documents 2.1 ASTM Standards: D 510 Sampling Industrial Water1 D1587 Thin-Walled Tube Sampling of Soils'. D 1605 Recommended Practices for Sum- pling Atmospheres for Analysis of Gases and Vapors* D 2928 Sampling Stacks for Paniculate Mailer* . 4.1.2 The sample collected should be at least 250 ml. -> 4.2 Sediment and Soil Sampling--A sedi- . ment or soil sample of at. least 1000 g should be taken according to Method D 1587 or any other acceptable procedure, taking due pre cautions to minimize contamination. 4.3 Air Sampling: 4.3.1 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. Sec Method D 160S or Method D 2928, or both. 4.3.2 for the measurements of airborne PCB's the air sample is drawn through one or more fritted bubbler absorbers filled with nanogradc toluene. The PCB's arc absorbed in the toluene. 3. Significance 3.1 Since it is possible for minute quan tities of PCB's to fmd their way into the environment, it is desirable lo have a method lo identify .aid measure the quantity of such truce amounts. 5. Principle 5.1 The PCB's present in environmental samples arc isolated from the bulk of the sample matrix hy solvent extraction. Inter fering matrix components and endogenous residues arc then removed from the sample 4. Sampling 4.1 Water Sampling -- Environmental sampling of natural bodies of water and effluents arc covered in many methods under (he jurisdiction of Committee D-19 on it.ner. Method D510 is recommended with the following stipulations: 4.1.1 Under. 76,1 a final rinse with Nanogt.idc* hexane should l>c added. 1 Ttiit m cl hod i* under the junsihetiun or ASTM Coniitnucc I>-27 on hlrtiocul tmuljiihr Luiuujt .mil (i.i*ei. Cuiicm edition approved leb. 27. 1974. I'uhtnhed April 1074. 1 /V7J Auninif f'onk <<f ASTM Sior.ltinh. I'.irl 2). * IV?4 Aruud Win>4 i>( ,4.V / 4/ Shi'ui.ifilt, I'.tri I S '"Kc.irvnl CWum.ih. Anirrn.in Oiemi, it Sncieij Sl'Ciifu.ini'i**." Am (1irina.il Nm... W.i'li.nrinn, i) C. tror iriyfrMiont on die letiinr uf nvij'rm* noi nsinj l>v (lie Ament.m L'heinieat Si-nvly, .ee "Kc.)-m (.'litontjU .mil Standnidt." Nv Joseph Kovin, 1> V.in Nmiuml l <* . Inc , New Toil., N. V.. 411J lilt "Untied .Sure* rii.iiniJtimeu.'' i :i HONS 002708 r r' # D 3304 extracts by * suitable combination of dttn*up ptoctduiu and the amount and type of PCB'i present determined by elec, iron capture gas chromatography (EC/GC). 6. Apparatus ' ' 6.1 Separatory Funnels, equipped with ground-glass stoppers and TFE-fluorocarbon stopcocks: 125, 250. 500. 1000. and 2000-ml capacities. 6.2 Kunderna-DanLsh Evaporative Concen trators, 500-ml capacity equipped with 3-ball Snyder columns and graduated 5-ml capacity vials. "* 6.3 Chromatographic Columns, glass, 10 in. (254 mm) long by 20 mm in outside diameter with a reservoir 5 in. (127 mm) long by 50-mm in outside diameter at the top, equipped with TFE-Doorocarbon stopcocks. 6.4 Buchner Filler Funnels, borosilicate glass, fritted, 90 mm in inside diameter, 600-ml capacity, medium porosity. 6.5 Boiling Flasks, Hat-bottomed, 125-ml capacity. 6.6 Liebig Condensers. 200 mm in length. 6.7 Hot Plates. 6.8 Water Bath. 6.9 Reciprocating Variable-Speed Shaker. 6.10 Syringes, 10-jrl. 6.11 Mortar and Pestle, all glass, 32-oa (or Mitre). 6.12 Baking Dishes, borosilicate, 2*A-qi (2.4-litre), 8 by 12 by 2-in. (203 by 305 by 50-mm). 6.13 5i>vr--U-S. Standard sieve No. 30 (600-pm). i 6.14 Gas Scrubbing Bottles, high-form, ground-glass joint, fritted-coarse . disks, 250-ml capacity. 6.15 Dry Test Meter, 0.1 ft1 per revolu tion. 6.16 Laboratory Vacuum Pump. 6.17 Rotary Vacuum Evaporator. 6.18 For the apparatus used in the Elec tron Capture Gas Chromatographic Proce dure, see Section 10. 7. Reagents 7.1 Purity of Reagents--Reagent grade chemicals shall be used in ait tests. Unless otherwise indicated, it is intended that all reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where such specifications are available.* Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accu racy of the determination. 7.2 Acetonitrile. Nanograde.* NotB -- Nanograde designates impurities of no more than 10 parts per trillion. 7.3 Alcoholic Potassium Hydroxide Solu tion (2.5 % weight per volumny--Dissolve 12.5 g of potassium hydroxide in 500 ml of ethanol. 7.4 Alumina (for chromatographic adsorp tion), 80/200 mesh. Heal at 400*C for a minimum period of 4 h and deactivate with 5 % (w/w) distilled water. 7.4.1 Alumina Column Preparation--Fill a chromatographic column (6.3) with hexane up to the point where the reservoir joins the column and push a glass wool plug to the bottom with a glass rod. In a 50-ml beaker 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 top the alumina with 2 to 3 cm of anhydrous sodium sulfate. Wash the column with 50 to 100 ml of hexane prior to the addition of the sample. '" 1 7.5 Distilled Water, extracted with hex ane to remove hexane-soluble electron-cap turing impurities. 7.6 Ethanol--Formula 2B. 7.7 Hexane, Nanograde.* 7.8 PCB Standards, production grade. PCB Standards Aroclor 1221,* Aroelor 1242, and Aroclor 1254. 7.9 Potassium Hydroxide (KOH). 7.10 Sodium Sulfate, anydrous. granular. Heat the sodium sulfate (NaiSO,) at 400VC for I h prior to use. 7.11 Sulfuric Acid (sp gr /.5y>--Concen trated sulfuric acid (H,SO<). 7.12 Toluene, Nanograde.* 8. Sample Preparation and Extraction 8.1 Water: 8.1.1 Where possible, the entire water ` Krfttitrtd trademark t( Mallinckrodt Chrmicai Werki. * Rtsiitctcd Uadcmatk ef Murnamo Co 2 HONS 002709 ................. D 3304 r sample is extracted with hexane. With larger samples, where tins is not physically possi ble, the containers are simply agitated and a 250-ml potlion used for analysis. 8.1.2 Extraction of Water Samples--After agitating. transfer the entire aqueous sample or a 250-mi aliquot into a graduated Hass cylinder. Record the volume of the sample and quantitatively tiansfci it to a separatory funnel with distilled water. 8.1.3 Rinse (he 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 ! 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-ntl portion of hexane. After the luyers have separated, add the first hexane extract to the second separatory funnel and transfer the aqueous layer to the original seperatoty 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 I 4-in. (100-mm) funnel plugged with glass wool that is covered with sodium sulfate. Collect the filtrate in a Kunderna-Danish evaporative conccntiator; add a small boil ing chip. Pul the Snyder column in place, and reduce the hexane volume to levs than 5 ml by heating the apparatus in an 80 to 90C water bath. CAUTION--SoJvenl vapor.% must be vented into a hood. Remove the evaporative concentrator from the witter hath and after cooling to room temperature adjust the volume to 5 0 ml. 8.1.8 Inject a fraction of a microlitrr. of (he couceniraie into the gas chromatograph to check for interferences and determine the approximate level ol I'CU's present, if no inlcrfctenccs 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. 8.1.9 If interferences ate present, proceed with the chemical ticatmcnt and column chromatographic cleanup procedures. 8.2 Sediment and SotI: 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. `Ihe dried material 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 g) into a 16-oz (or 500>ml) narrow-neck scrcw- cap glass bottle (with an aluminum foil liner). 8.2.3 Moisten the soil with water (10 ml) and add 150 ml of acetonitrile. Cap the bottle tightly, and mechanically shake for a minimum period of l h. - -- 8.2.4 Quantitatively transfer the acetoni trile extract into a sintcied-plass filter funnel containing a 'A-in. (6.4-ntm) 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 Ktmdcrna-Dnnish evaporative concen trator; add a small boiling chip. Put the Snyder column in place, and reduce the solvent volume to less than S ml by healme the apparatus in a SO to 90C water hath. CAUTION--Soivent 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. Kcdissolvc the icsi- due m maximum of 5 ml of hexane. 8.2.8 Inject a fraction oT a microlitrc of the concentrate into the gas chromatograph to check for interferences and determine the approximate level of FCH's present. If no mterfeicnc.es arc present, dilute or concen trate the sample to a knoun volume, as determined by the electron capture chromat ogram, and proceed with the gas chromato graphic anal) sis. HONS 002710 (r 0 3304 8.2.9 If interferences are present, proceed with the chemical treatment and column chromatographic 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. 1.3.3 Quantitatively transfer the concen trate to a 30-ml beaker with the aid of several tmiil portions of toluene. 1.3.4 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 Gcan 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 pm) 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 hfixane. 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 1 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 Filler the hexane extract through a 4- in. (100-mm) funnel plugged with glass wool that is covered with a layer of anhy drous NaiSO*. Collect the filtrate in a Kundcrna-Danisb evaporative concentrator, add a small boiling chip, put the Snyder column in plnce, and reduce the hexane volume to less than 5 ml by hcatinc 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 adsorhant level after each addi tion of solvent. Do not allow the top of the column to become dry). 9.2.2 Carefully add 125 ml uf hexane to the column reservoir and collect the total eluent in a Kondcrtia-Daimh evaporative concentrator. 9.2.3 Add a small boding chip to the Kundenta-Danish evaporative concentrator; ' HONS 002711 D 3304 .r put the Snyder column In place, and reduce the hexane volume to less .than 5 ml by beating the apparatus in an 80 to 90C 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 5.0 ml. 10. Electron Capture Cat Chromatographic Procedure 10.1 Instruments--A gas chromatograph equipped with isothermal oven temperature eontrol. 10.2 Detector-- High-temperature '*Ni Electron Capture Cell 10.3 Column--A 6-rmn by 6-ft (1.8-m) glass column, 4% XE-60 on 80/100 mesh Chromotorb W, high-performance. 10.4 Column Temperature--The column temperature shall be as follows for the vari ous Aroclors: Arocior 1221. !70"C; Aroclor 1242, 190*0: Aroclor 1254. 205*C. 10.5 Detector Temperature--The detector temperature shall be 250 to 300aC. 10.6 Injection Tort Temperature--The in jection port temperature shall be 22Q*C. 10.7 Pulse--The pulse rate shall be 50 /is. 10.8 Flow Rates--The flow rates shall be as follows: 10.8.1 Helium Carrier--(i0 ml/min. 10.8.2 90% Argon~l0% Methane Purge-- 20 ml/min. 10.9 Using EC/GC as the determinative step, inject in duplicate 2 to 8 j<l 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 aica method. ences. ' 11.1.2 Case II-- EC gas chromatogram of PCD unknown altered with respect to stan dard PCH with no evidence of interference. 11.1.3 Case ///--tC gas chromatogram of PCD unknown unchanged wiih respect to Standard PCD with evidence of interference. 11.1.4 Case IV-- EC gas chromatogram of PCB unknown altered with respect to stan dard PCD with evidence of interference. 11.2 Determine the PCB level in Case I and II samples by comparison of the total area of tiic 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 ill and IV samples to the chemical cleanup procedure and follow by chromatography on alumina. If the interferences are removed by this treatment, calculate the PCD levels for Cases III and IV in the same manner as Cases I and II. if dominant inierfcrencc(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 nanograins of the PCD standard injected, calculate the PCB level present in the air, water, or sediment-soil sample as follows: 12.1.1 Water and Sediment-Soil Samples: C - [{AtO){D x 10* *il)/ml (10"* mg/ng)\/F. 11. Quantitatiic Determination 11.1 Quantitative determinations employing the electron captmr detector are non-stoichiometric measurements marie 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: 11.1.1 Coif /--hC gas chromatogram of PCD unknown unchanged with respect to standard PCD with no evidence of interfer- 12.1.2 Air Samples: F IWW x IO%l)/ml(tQ-*niff/nc)| G (28.32 htre/ft'HmVlO1 litre) (P.- l,,/P.KT./273 +T,> where: A m PCD in unknown from calibration curve, tig, B - final concentrate injected into the in strument, Alt, C concentration of I'CD's in water, and sediment-soil sample, mg/kg (or ppm). HONS 002712 .... 0 3304 f Z> - volume of final concentrate, mi, m sample weight, kg. F concentration of PCB's in air sample, ing/m', nt one atmosphere and 25"C. C air sampled from meter, ft*, Ft standard pressure, 760 mm Hg, Ft m differential pressure of gas stream, mm Kg, s TV - standard temperature, 298 K. and T% - temperature of sampled gas. *C. 12.2 The corrections for the pressure drop through the scrubbers and for the gas tem perature arc 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 (he method used for estimating PCB content in the environment, a roundrobin testing experiment was set up. Sam ple! were prepared by spiking water with PCB'i at the level of about 500 ppb. Individ ual preparations included blanks (no PCB), Aroclor 1242 only, Arodor 1254 only, Arodor 1260 only, all 50-50 two-component mix tures, and a 'A, 'A, 'A preparation containing all three Arodors. Six samples of each mix ture were prepared, and tested by two ana lytical laboiatories. 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 Coc/nsi#i.t; 1J.3.1 The 95?# confidence limits for indi vidual results were as follows: CitbcrlabMMory 17.5*35.2% . Laboratory A Laboratory-B II.) *46.4% fJ.7 * 19.2% 13.3.2 The repeatability for the individual laboratories, based on repeat tests of samples having identical prepared compositions is as follows: LabaratoryA Laboiaiory *42.0% *11.6% 13.3.3 In general. Laboratory B comes closer to properly identifying the individual ArocJors with one exception, Arodor 1254 found in a mixture of Arodor 1242 and Arodor 1260, as follows: Mix* lure Prtuni 1 1247 2 1242,1254 ) 1242. 1254, 1260 4 1254 J 1242, 1260 6 1260 7 >254. 1260 Laboratory A 1742.(1254) 1242. 1254. (1260) 1242. ( ). 1260 1254,(1760) 1242. 1260 (I24S). 1260 (1241). 1254 1260 Liboraiory 8 1242 1242. 1254 1242. 1254. ' 1260 1254,(1260) 1242.(1254), 1260 1260 1254,1260 Numbett in parentht*** indicate miiidaniificationt. 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 mcla). 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 be 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 J 6 MOWS OOZ713 r/ D 3304 7 HONS 002714  O 3304 HONS 002715  0 3304 pukhtation af tkll ttondartl no pmlHon u mien tk resprft la ike vehjite of any patent ngkn in ronneetmn ikerenilk, and the Ameneon Svutty for Truing end Hairnuti does not umleimke to tnuor anyone unhung ike Standard againji liaMty for In/nngtmtm of any Letters Talent nor auamt anv Sueh hatntiiy. HONS 002716