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PlI: S0045-6535(96)00214-7

Chemosphere, Vol. 33, No. 4, pp. 603-623, 1996

Copyright 1996 Elsevier Science Ltd Printed in Great Britain. All fights reserved 0045-6535/96 $15.00+0.00

COMPREHENSIVE, QUANTITATIVE, CONGENER-SPECIFIC ANALYSES OF EIGHT AROCLORS AND COMPLETE PCB CONGENER ASSIGNMENTS ON DB-I CAPILLARY GC COLUMNS

George M. Frame*, Robert E. Wagner*l , James C. Carnahan, John F. Brown, Jr., Ralph J. May, Lynn A. Smullen, and Donna L. Bedard

General Electric Corporate Research and Development, P.O. Box 8 Schenectady,/flY, 12301-0008, USA
(Received in Germany 15 April 1996; accepted 14 May 1996)

ABSTRACT We have determined complete polycldorinated biphenyl (PCB) congener assignments end weight percent distributions for all major ( > 0.5 wt % ) FCB components of Aroclors 1221, 1232, 1242, 1016, 1248, 1254, 1260, 1262 that are resolved by DB-1 (polydimethylsiloxane) capillary C,-Ccolumns. Aroclor components present between 0.05 and 0.5 wt % were also identified but not quantified. Quantitadon was done using a combination of GC-ELCD (Hall electrolytic conductivity detector) and GC-MS measurements. All 209 PCB congeners have been assigned to the 124 peaks that can be resolved on DB-I columns. The data support use of these eight Aroclors individually or in customized standards for calibrating the comprehensive, quantitative, congenerspecific PCB analyses that are necessary for accurate quantitation of the complex and often radically altered mixtures of PCBs typically found in the environment. Copyright 1996 Elsevier Science Ltd INTRODUCTION From 1929 to 1979, polycldorinated biphenyls (PCBs) were widely used as dielectric fluids in capacitors and transformers, and also as hydraulic fluids, solvents, and plastieizers. FCBs are considered potentially toxic, hence the PCBs that still persist in soils, sediments, and biota are a major environmental concern. Commercial PCBs were manufactured by catalytic chlorination of biphenyl to produce complex mixtures, each containing 60 to 90 different molecular species (congeners) and a specified weight percent of chlorine.

Current address: Northeast Analytical, Inc., 301 Nott Street, Schenectady, NY, 12305

603

604 Congener distributions in environmental samples resemble those of the parent commercial mixtures (Aroclors in the USA and Great Britain, Clophens in Germany, or Kanechlors in Japan), but are often modified due to evaporation, water extraction, microbial oxidation or dechlorination (1,2,3), or photochemical dechlorination (4). There are 209 distinct congener structures possible, of which about 140 to 150 have been detected at significant levels in commercial PCBs (5). Thus a comprehensive analysis of the congener distributions in an environmental or research sample presents a daunting analytical problem. Regulatory agencies in Europe have simplified the problem somewhat by specifying a list of seven "indicator" congeners (6) or 36 "priority" congeners (7) targeted for individual quantitation. The US EPA specifies that PCB quantitation must be done by comparison of total area or total height of sample peaks to those of one or more reference Arociors, depending on the chromatographic pattern of the sample (8). However, many research studies require complete, quantitative measurements of all the PCBs that can be resolved and detected. Analytical methods that attempt to achieve complete, quantitative, congener-specific measurement of PCBs will be referred to as comprehensive, quanatative, congener-_specific (COCS) PCB analyses. The use of well-characterized individual Aroclor standards for calibrating CQCS PCB analyses has several advantages. (1) Aroclor standards are easier to use and are far less expensive than standards based on complete sets of individual congeners. (2) Their congener distributions are similar to those found in the environment, hence they are well-suited to calibrations based on diluting or concentrating the sample extract to match a single concentration of the standard (9). (3) Individual Aroclor standards can be combined in various proportions to match the chromatographic pattern in a sample, and can be supplemented with individual congeners to make customized standards. This permits accurate quantitation of the complex mixtures of PCBs typically found in the environment, including those altered by degradation, dechlorination, evaporation, and water extraction (10). To employ Aroclors as standards for CQCS analyses, the analyst requires the individual weight percent values of total PCBs in each peak on the particular HP,GC column, and for GC-MS methods the proportions of different homologs (congeners of a particular chlorine number) within a peak. Accurate quantitation generally requires assignment of all likely congeners to each resolvable peak of each Aroclor on a particular HR.GC column because the chlorine substitution pattern affects the molar response of the detectors most often used for PCB analysis, i.e. the electron capture detector (ECD), and mass spectrometer (MS) (11, 12). Bush et al. (13,14) and Eganhouse et al. (15) have described CQCS PCB analyses calibrated against single specific mixtures of three or four Arociors employed as secondary standards. Such methods employ tables of the amounts of PCB in each peak of the mixed Aroclor standard on a particular HRGC column, as determined by a primary analysis of the mixed Aroclor standard, together with an assignment of congeners to the peaks of the system. Unfortunately, many of the 209 PCB congeners were not available as reference standards when these studies were done, and consequently there were errors in the congener assignments made by these investigators. There is also some concern about the quantitation because both groups relied on detectors that may be sensitive to the chlorine substitution patterns of individual congeners. Bush et al. (13, 14) used MS homolog responses, and Eganhouse et al. (15) used a combination of FID and MS homolog responses to calibrate their secondary standard mixture of Aroclors. There is general agreement that MS detectors are sensitive to chlorine substitution patterns (12), but there is some disagreement about whether this is also true for FID de~eetors. Albro and Fishbein (11, 16) reported that the relative molar response of the FrD detector to PCB

605 congeners can vary significantlywith the chlorine substitution pattern. However, in more recent work Krupcik el al. (17) reported that the molar response factors of the FID detector to all PCB congeners are constant to within about .4- 10%. Krupcik et al. (17) recommended a procedure for combining GC-FID and GC-MS measurements of Aroclors or Clophens to support their use as secondary standards for CQCS PCB analyses o n specific capillary GC columns. These authors subsequently proposed the use of GC-FID data to calibrate peak responses of more selective detectors for particular Aroclors or Clophens on any capillary column (18). As an illustration, they showed how this procedure could be used to produce relative response factors (RRFs) for GC-ECD, GC-MS-SIM and GC-MS-TIC (total ion current from scanned acquisition) for individual peaks of Aroclors 1242 and 1260 on a polydimethylsiloxane capillary column very similar to the DB-1 phase and reported weight percentages for major peaks of their samples of Aroclors 1242 and 1260 (17). However, there are major discrepancies between the congeners they reported as major constituents of Aroclor 1242 and 1260 peaks and those we report in this paper. Another Aroclor-calibrated CQCS PCB analysis employs Mullin's "Green Bay Calibration Mixture" (19) which is composed of Aroclors 1232:1248:1262 in the ratios 28:18; 18. These Aroclors were obtained from a US EPA repository. Mullin assigned 126 Aroclor congeners to 103 peaks on a DB-5 column after analyzing the mixture on several different columns against individual congener standards and using mass spectral detection in some cases. Although the method has not been formally published, Mullin makes available a new mixture using a new source of EPA Aroclors, together with updated elution order and peak quantitation tables. The calibration has been employed in several studies, (e.g. 20, 21), particularly in the Great Lakes (USA) regional surveys. Despite its usefulness, the Green Bay Calibration Method has several significant shortcomings. First, the standard skips from Aroclor 1248 to Aroclor 1262 and thereby excludes many pentachlorobiphenyls that reach significant proportions only in Aroclor 1254. Thus the method may not be well-suited for quantitation of samples that contain significant proportions of Aroclor 1254 or of pentachlorobiphenyls formed by dechlorination of more chlorinated congeners. Second, since this method is based on a fixed standard, it does not afford the flexibility that can be achieved from methods based on well-characterized inc~vidual Aroclor standards. Previously, only two groups (22, 23) have attempted complete CQCS analyses calibrated against primary standards of all 209 congeners, most of which were specifically synthesized by the researchers for that purpose. Mullin et al. (22) used a 100m SE-54 column with a 2 hour run time and reported resolution of 187 of the 209 congeners. Schulz et al. (23) employed heart-cutting 2-dimensional HRGC to determine complete congener distributions of four Aroclor and four Clophen mixtures. Both of these procedures are too slow and difficult for routine CQCS analyses of large numbers of samples, and shorter columns and run times do not achieve the same resolution (6). Unfortunately, there is still no single HRGC system that will resolve all 209 PCB congeners or even all those that occur in Aroclors. To calibrate CQCS PCB analyses in our labs, we measured the total PCB content of each peak in samples of eight different Aroclors by combining data on the chlorine content measured by an electrolytic conductivity detector (ELCD, also known as a Hall detector) with data on the homolog composition determined by GC-MS. The ELCD afforded a distinct advantage over other methods of quantitation because the response of this detector is directly proportional to the number of chlorines irrespective of the position of the chlorines (12).

606 Webb and McCall (24) used a combination of ELCD and MS data for quantifying the PCB composition of Arodors by packed column GC because this approach permits accurate quantitation of the PCBs in each Aroclor peak even when the PCB congener composition is not known. Using DB-I (polydimethyisiloxane) capillary columns we were able to resolve 118 PCB peaks to which we assigned 184 of the 209 congeners. Over the past 9 years, our congener assignments and weight percent distributions for these Aroclors provided the foundation for analytical methods implemented by a number of industrial research, contract and academic laboratories to support environmental and in vitro microbial PCB degradation and dechlorination studies (25-34). As more pure congener reference standards became available, and the chromatographic conditions of the analytical method were altered and optimized, we revised and extended some of the initial congener assignments and made several additions and deletions in the peak numbering system. The purpose of this paper is to report the DB-1 peak assignments for all 209 congeners, to indicate which of the congeners are significant components of Aroclors, and to present tables of congener assignments and weight percent distributions for all peaks resolved on DB-1 columns for each of the eight Aroclors used as secondary caiibration standards for our CQCS PCB analyses. MATERIALS AND METHODS Reagents. Aroclors and PCB congeners were dissolved in high purity hexane or isooetane. The eight Aroclors characterized in this study were obtained from the manufacturer (Monsanto Corp., St. Louis, MO, USA) during the time when Aroclors were still widely used. These specific Aroclor samples have subsequently been used as secondary standards in all of our studies. Initial calibration standard PCB congeners, chloronaphthalene internal standards, and individual PCB congener standards were obtained either from Ultra Scientific (North Kingston R/, USA), or AccuStandard Inc., (New Haven CT, USA). A complete set of 209 PCB congeners used for the final comprehensive DB-1 column peak assignments was obtained from AccuStandard Inc. Standard Solutions. A calibration standard of congeners representing each homolog class was prepared by weighing out - 5 mg each of PCBs 3, 5, 18, 49, 101, 153, 185, 202, 206 and 209 and dissolving them in hexane at a final volume of 25 ml. This stock was diluted to produce three calibration levels of each congener at ~ 10, ~ 50, and - 1 0 0 pg/ml. A calibration check standard representing all homolog classes except nonachlorobiphenyis was prepared in the same way using PCBs 1, 12, 30, 52, 101, 156, 185, 201 and 209 and was diluted to ~50 pg/ml. Each calibration solution contained 1,2-dichloronaphthalene, 1,2,3,4-tetrachloronaphthalene, and octachloronaphthalene as internal standards (I. S.) at individual concentrations of 50 I~g/ml. Concentrated solutions ( ~ 1000 pg/ml) of Aroclors 1221, 1232, 1016, 1242, 1248, 1254, 1260 and 1262 were prepared in hexane. 1,2-Dichloronaphthaiene was added to each Aroclor solution at a final concentration of 50 pg/mL Either one or both of the other two chloronaphthalenes were also added at the same concentration whenever they did not coelute with a PCB peak in the Asoclor. GC-ELCD Analyses. Capillary GC with detection by the ELCD was carried out on a Varian 4600 gas chromatograph equipped with a Tracor Model 700A ELCD Splitless injections (1.0 pl) were made using a Varian Model 8000 autosampler and a 1070 split/splitless injector with a splitless time of 0.9 min at 300C. The column was a DB-1 (bonded, cross-linked, 100% polydimethylsiloxane) capillary column (J&W, 30m x 0.25ram i.d. x l.0 pm film thickness). The thick film was necessary to provide adequate sample capacity for the high

607 concentration (1000 p.g/mi) Aroclor injections. The column temperature was held at 40C for 2 rain., programmed to 80C at 10C/rain and then to 225C at 6C/rain and held for 10 min. The carder gas was helium at a flow rate of 1.8 ml/min. The ELCD detector base was maintained at 300C and the reactor was provided with hydrogen gas (serving also as column makeup gas) at a flow rate of 50.0 ml/min and n-propanol solvent flow of approximately 1.0 ml/min (corresponding to a setting of 6.8 on the detector). The ELCD reactor was operated at 920C, and the column efiluent was diverted for the first 0.35 rain atter injection to avoid contamination from the injection solvent. Peak areas were measured using a Vadan 402 workstation. 1,2-Dichloronaphthalene was chosen as the I.S. for the Aroclor quantitation because it did not coelute with any Aroclor peaks. The remaining I.S. compounds were introduced into Aroclor solutions when they did not coelute with Aroclor peaks and served as a check on the stability of the ELCD detector response, but they were not used in the quantitative calculations. GC-MS Analyses. The same DB-I column was transferred to a GC-MS system in order to determine the PCB homolog composition of each resolvable peak on the GC-ELCD system described above. Aroclor solutions (5000 I~g/ml) were analyzed on a Varian 1440 GC directly interfaced to a VG ZAB 2F mass spectrometer operated in the low resolution mode. Depending on the particular Aroclor, a variety of different column flow and temperature programs were employed with the G-C-MS system to produce peak distributions and resolutions matching those recorded during the GC-ELCD analyses. Electron impact (70eV) mass spectra were acquired by continuouslyscanning the range of 154 to 500 atomic mass units. The PCB homolog composition of each resolvable peak in each Aroclor was determined from the mass spectra. Chromatographic peak areas from the mass chromatograms of each chlorine isotope mass peak in the homolog molecular ion clusters were summed to yield total cluster signal values for that homolog. The weight fraction of each homolog in the peak was assumed to be the ratio of its molecular ion cluster area to the sum of the areas of the pair. In most instances the relative proportions of coeluting homologs in any GC peak could be accurately determined when they differed by a single chlorine, which was generally the case. However, there were two instances, peaks 60 and 96, where coeluting homologs differed by two chlorines. chlorines precluded measurement of the less chlorinated homolog. GC-ECD Analyses. Routine CQCS PCB analyses were performed using thinner film DB-1 columns with more sensitive detectors, especially the ECD. We determined how closely the distribution and resolution of peaks on the DB-1 thick film column systems described above matched such a G-C-ECD system. We used a J&W DB-I column (30 m x 0.25 mm i.d. x 0.25 ~m film) and a Varian ECD installed in the GC system previously used for GC-ELCD determinations. The temperature and flow parameters were the same except that the column linear flow rate for the helium carder gas was 30 cm/sec. Nitrogen at 25 ml/min was employed as the makeup gas. The resolution of congeners was identical to that on the GC-ELCD and GC-MS systems in all but 4 cases. These exceptions were taken into account during the calculation of the final Aroclor weight percent distributions, which are presented for the thin film column/ECD peak distribution. The biphenyl content of our samples of Aroclors 1221 and 1232 was determined by analyzing hexane solutions of these Arociors (~100 ~g/ml) in triplicate (RSD = 5% and 3% respectively) against a 5 point standard curve using a DB-I capillary column with flame ionization detection. The more chlorinated homolog was predominant in each of these peaks, hence the fragment produced by the loss of two

Biphenyl Analysis.

608 Elemental (C, H, CI) Analysis. The eight Aroclor samples were sent to Galbraith Laboratories (Knoxville, TN, USA) for analysis of carbon and hydrogen content by automated elemental analyzer and of chlorine content by Sch6niger flask oxygen combustion followed by potentiometric titration. RESULTS

Confirmation of ELCD Linear Response to Chlorines. The calibration standard and calibration check
standard were each analyzed several times on the GC-ELCD system to verify that the ELCD response was directly proportional to the number of chlorines and not sensitive to chlorine position. The results confirmed this and verified that congeners of a given chlorination level yielded the same responses relative to an individual I.S. The ratios of all three internal standards relative to each other were monitored both in the calibration standards and in the Arociors to ensure that the response of the ELCD did not change during analysis. These ratios remained constant, demonstrating that the ELCD response was stable. Determination of Homolng Composition of Aroclors. The homolog composition (i.e. chlorination level) of each peak in our samples of each of the eight Aroclors was determined from GC-MS data. In cases where the GC-MS analysis revealed coelution of more than one homolog in a peak, the approximate weight fraction of each was calculated as described above. Calculation of PCB Concentrations in Aroclors. Each of the three concentrations of the calibration mix was analyzed six times on the GC-ELCD system using 1,2-dichloronaphthalene as an internal standard to normalize the data and compensate for any shit, s in the ELCD response. The mean ratios (PCB peak area/I.S. peak area) were calculated for each calibration level and used to generate 3-point linear calibration curves for each of the ten chlorination levels. The slopes and intercepts were calculated for each chlorination level. Each of the Aroclors was then analyzed six times. Because the ELCD response for each chlorination level is constant, the concentration of the PCB was calculated directly using the formula: PCB Cone. (~g/ml) = S x (Peak Area/I.S. Area) + I where S is the slope (for the chlorination level) and I is the intercept. For peaks with mixed chlorination levels, GC-MS analysis was used to determine approximate weight fractions of pairs of coeluting homologs, and these were introduced into the formulas: PCB Cone.L (p.g/ml)= SL x (Peak Area x FL/I.S" Area)+ IL and PCB Cone.H (~g/ml) = SH (Peak Area FH/I.S. Area) + IH where F is the approximate weight fraction determined by GC-MS, and L and H designate the lower and higher homologs, respectively. The combined sum of the PCB concentrations for the higher and lower homologs constitute the "total" Izg/mlconcentration for each mixed peak. Calculation of Weight Percent PCB Distributions for Peaks Quantifiable by ELCD. The PCB concentrations for each peak were summed to give the total PCB concentration for each replicate run. The weight percentages for each homolog in each peak were calculated for each replicate run using the formula: Weight A PCB = [ Cone. PCB (~g/ml)/Total Cone. (~g/mi) ] x 100

609 The final weight percent values for each peak (including different homolog chlorination levels within peaks) were generated by taking the mean of the six replicate values. The percent relative standard deviations of these means for individual peaks in the eight Aroclors averaged - 3% with a maximum range of 0.42% to 7.2%. Identification of Minor Aroclor Peaks. We were able to detect a number of minor Aroclor peaks with GC-ECD or GS-MS-SIM that were not quantifiable by the GC-ELCD used in this study. We used semiquantitative analyses of each Aroclor on several different systems to identify congeners in DB-1 column peaks that were present within the concentration range of 0.05 to 0.50 weight percent. Peaks in this range detected on a DB-1 column by GC-ECD were quantified using tables of response factors adapted from Mullin et al. (22) and corrected for our ECD. The homolog composition of these peaks was determined by GC-MS-SIM on the same column. Each Aroclor was also analyzed against individual standards of all 209 congeners on both a 30 m DB-XLB column (J&W Scientific) using MS-SIM detection and a 30 m SPB-Octyl column (Supelco, Inc. Bellefonte, PA, USA) using ECD detection (G. Frame, unpublished data). Ratios of peak heights to the individual standards provided a semi-quantitative estimate of the amounts present. These additional systems also enabled resolution and quantitation of congeners that coelute on DB-1 columns. Total PCB Concentration and Weight Percentage of Chlorine for Eight Aroclors. Table 1 gives the actual concentrations of each of the Aroclor solutions and compares them to the range of values calculated from the six replicate GC-ELCD analyses. Aroclors 1221 and 1232 contain substantial amounts ofbiphenyl that were not detected by the ELCD detector. We determined by DB-1 capillary GC-FID that biphenyl constitutes 11.7 weight percent of Aroclor 1221 and 6.2 weight percent of Aroclor 1232 and included these values in the totals reported in Table 1. The actual PCB concentration of several Aroclors fell outside the range calculated based on our data. However, in those instances the actual concentrations differed from the calculated range by only 2 to 8% except that of Aroclor 1242 which differed by 12%. The chlorine percentages calculated from the ELCD analysis were close to the values obtained by elemental analysis, and to the nominal percentages specified for each Aroclor. Table 1. Total PCB Concentration and Weight Percentages of Chlorine for Eight Aroclors: Direct Measurements Vs Calculations Based on GC-ELCD / GC-MS Data Aroclor Actual Cone. (~g/ml) I018 1036 1024 1041 1033 1048 1097 994 Calcul~ed Cone. Range (~g/ml) 928- I000 1010- 1050 l l 6 0 - 1220 1020-1060 980- 1070 1130 - 1180 1140 -1290 1080 - 1100 Elemental Analvsis Weight Percents C H C1 73.59 64.76 54.42 55.95 49.67 43.88 38.36 37.26 4.50 3.59 2.55 2.72 2.08 1.50 0.94 0.82 21.96 31.82 43.22 41.31 48.12 54.77 60.52 62.01 ELCD Data Cl Wt % 23.8 34.0 43.7 41.I 48.1 54.6 60.5 61.8

1221 1232 1242 1016 1248 1254 1260 1262

Congener Peak Elution Assignments for DB-1 Columns. We initially determined the peak elution positions for 70 PCB congeners by Co-injecting pure congener standards with Aroclors. Estimates of probable DB-1 relative retention times were made for congeners without reference standards based on published relative

610 retention times of 209 congeners on a slightly different column phase (SE-54) (22). Thus, assignments were made for 184 of the 209 congeners to 118 distinct, potentially resolvable DB-1 peaks (26). These assignments included some congeners which are not observed in any of the commercial Aroclor mixtures Our peak assignments were revised and extended in 1992 (10) and finally completed and reconfirmed in 1994 using the complete set of 209 congeners. The complete congener peak assignments for DB-1 columns are listed in Table 2. DB-I Chromatograms for Individual Aroclors, Figures IA and B show the ECD chromatograms for each of the eight Aroclors characterized in this study and identifies all major peaks and most minor peaks. Aroclors 1221, 1232, 1016, and 1242 are all plotted on the same time scale to permit direct comparisons of the peak distributions. Aroclors 1248 and 1254 are plotted on a second time scale and Aroclors 1260 and 1262 on a third time scale. Each chromatogram is plotted to show the highest peak on scale. Congener Assignments for Individual Aroclors. Potential congeners contributing to individual Aroclor peaks were identified by elution position on DB-I columns. The presence or absence of coeluting congeners that differ in chlorine number was determined by GC-MS. In instances where individual isomers coelute on the DB-1 column, those congeners that significantly contribute to a given peak in each Arocior were initially identified on the basis of observed single phenyl ring substitution probabilities. For example, in peak 48, congener 95 (236-25-CB) was listed as the major pentachiorobiphenyl component because the 236- and 25chlorophenyl substitutions are very common in the Aroclors. Congener 102 (245-26-CB) was thought to be present, but less abundant because the 26- substitution is rare in Aroclors, congener 98 (246-23-CB) was not thought to be present because the 246- substitution is extremely uncommon in Aroclors, and congeners 88 and 93 (2346-2-CB and 2356-2-CB) were not thought to be present because of the highly unbalanced chlorine distribution on the rings of these congeners. The individual congeners assigned as significant constituents of each individual Aroclor were recently verified by chromatographing the individual Aroclors against individual standards of all 209 congeners on two additional GC column phases (DB-XLB and SPB-Octyl) (G. Frame, unpublished data). Table 2 gives the congener and weight percent distributions for each of the eight Aroclors we analyzed. The first column gives the peak numbers on the DB-I GC column in order of increasing elution time. The peak numbers are based on the initial 118 peak assignments. Changes in the GC column flow and temperature programs that we now use have improved the resolution of certain closely eluting pairs. Interpolations of additional peak numbers are indicated by multiple decimal values of the original numbers so that peaks can be sorted numerically by computer programs. Peaks 18 (congener 23), 86 (congener 166) and 97 (congener 157) of the original system are no longer found to be resolvable, and are therefore omitted. We have listed the IUPAC number of each congener. Six of the IUPAC numbers differ from the original Ballschmiter and Zell numbers, (BZ#), (35): IUPAC #s 107, 108, 109, 199, 200, 201 correspond to BZ#s 108, 109, 107, 201, 199, and 200, respectively (36). Congeners determined to be present in any of the Aroclors at >0.05 wt % (see below) are indicated in a larger boldface font whereas those not present in the Aroclors are indicated by a smaller italicized font. We have identified each congener by its individual phenyl ring chlorine substitution patterns according to the convention: 234-245 = 2,2',3,4,4',5'-hexachlorobiphenyl. This permits easy visualization of the chlorination pattern on each ring and assists interpretation of how the overall chlorine substitution pattern on each ring affects elution position.

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dissolved in isooctane at a concentration of 2 pg/ml and analyzed on a Hewlett Packard 5890 GC using chromatography conditions similar to those described in the text. Aroclor peaks have been indicated by DB-1 peaknumber (see Table 2) or by tick marks. Some of the minor peaks were not visible under these conditions.

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613

Table 2.

Congener and Weight Percent Distributions in DB-1 Peaks for Eight Aroclors (a)

Wt % of Quantifiable Peaks in Aroclors ( Total in Peak; Total for each Homolc } A1232 A1016 A1242 A1248 A1254 A1280 A1262 DB1 CI IUPAC Congener A1221 Peak # # I.D. Tot. Horn. Tot. Horn. Tot. Horn. Tot. Horn. Tot. Horn. Tot. Horn. 2 1 1 2 42.24 20.48 # # 3 1 2 3 2.62 1.73 4 1 3 4 20.66 9.13 # # 5 2 4 2-2 6.34 5.23 3.70 2.74 5 2 I0 26 C C C C 6 2 7 24 C C C C 6 2 9 25 2.49 1.82 1.05 1.02 7 2 6 2-3 2.99 2.34 1.55 1.34 8 2 5 23 C C C C 8 2 8 2-4 12.88 10.67 8.94 6.~ # 9 2 14 35 10 3 19 26-2 # .79 .97 .96 # 11 3 30 246 12 2 11 3-3 # 13 2 12 34 C C C C # # 13 2 13 3-4 1.34 1.09 14 2 15 4-4 4.00 3.66 4.95 2.59 C 5.93 C 3.19 # ND # 14 3 18 25-2 C .34 C 2.36 12.84 6.91 10.17 6.98 2.95 2.95 # 3.70 5.93 4.57 1.22 15 3 17 24-2 # 16 3 24 236 C C C C .75 .78 .83 # 16 3 27 26-3 # 2.30 6.20 5.14 1.62 17 3 16 23-2 .89 17 3 32 26-4 C C C C C 19 3 23 235 # # 19 3 34 35-2 19 4 54 26-26
., ., .,

.68
24 24 25 25 25 25 26 26 27 28 29 30 I31.1 31.1 31.2 32 32 !33 33 34 34 35 35 3 4 3 3 3 4 3 4 4 3 4 3 4 4 4 4 4 3 4 4 4 4 4
28
50

20 21 33 53 22 51 45
36

46
39

52
68 73

43 49
38

47 48 75 62 s5

24-4 246-2 23-3 2 34 34-2 25-26 23-4 24-26 236-2 35-3 23-26 35-4 25-25 246-3 26-35 235-2 24-25 345 24-24 245-2 246-4 2346 2356

~
C

.~ ND

3.80
C

3.80 ND

9.79
C

9.79 ND

8.01
C

8.01 ND

6.09
C

6.09 ND

.69

.69 ND

89 .79 #

.89 ND .79 ND

2.74 1.41 .83 #

2.74 ND 1.41 ND

7.63 C 3.38 # 1.20 .75

6.83 .80 3.38 ND

6.28 C 2.88 C 1.10 .80

5.95 .33 2.79 .09

2.78 C 1.60 C. 1.17 .84

2.11 .76 1.34 .26

.69 C

.47 .22

C # # #

C 1.36

C 3.35

C 2.63 ND I.I0

C 4.59
2.55 2.19 ND 2.55

1.28 # #

.83 .98

ND .83

ND 1.17 1.17 I.I0 1.79 1.48

614

Table 2. continued DB1 CI IUPAC Congener Peak # # I.D. 36 3 35 34-3 37.1 5 1o4 246-26 37.2 4 44 23-25 38 3 37 34-4 38 4 42 23-24 38 4 59 236-3 39 4 41 234-2 39 4 64 236-4 39 4 71 26-34 39 4 72 25-35 40 4 o8 24-35 41 5 96 236-26 42 4 40 23-23 43 4 57 235-3 43 5 1o3 246-25 44 4 58 23-35 44 4 67 245-3 44 5 log 246-24 45 4 63 235-4 46.1 4 74 245-4 46.1 5 94 235-26 46.2 4 e; 2345 47 4 70 25-34 48.1 4 66 24-34 48.1 4 76 345-2 48.1 5 9a 246-23 48.2 4 ao 35-35 48.2 5 93 2356-2 48.2 5 95 236-25 48.2 5 102 245-26 48.3 5 aa 2346-2 49 4 55 234-3 49 5 91 236-24 49 5 121 246-35 50 4 56 23-34 150 4 60 234-4 I i51 5 84 236-23 51 5 92 235-25 51 6 155 246-246 52 5 89 234-26 53 5 90 235-24 53 5 1 0 I 245-25 54 4 79 34-35 54 5 99 245-24 54 5 113 236-35 55 5 119 246-34 55 6 15o 236-246 56.1 4 7s 345-3 56.1 5 83 235-23 56.1 5 112 2356-3 56.2 5 Ioa 2346-3 57.1 5 97 245-23 57.1 6 152 2356-26

Wt % of Quantifiable Peaks in Aroclors ( Total in Peak; Total for A1221 A1232 A1016 A1242 A1248 A1254 A1260
rot. Horn. Tot. Horn, Tot. Horn. Tot. Horn. Tot. Horn. Tot. Horn. Tot.

A1262
Horn

Horn, Tot.

#
# # C C # C 1.55 1.58 C C C 1.47 C

4.17 3.26 5.00 2.12 .91 C NQ 3.32 1.94 C NQI .67 2.88 NQ C 1.38 2.91 NQ C C C C C C 3.78 3.11 6.10 .93 C C C C

#
.90 1.01 1.18

#
#

#
C # # # .68 #

#
C #

#
C

#
1.00 1.00 ND

# .78 .68 1.60 1.60 4.50 4.5C ND ND ND

# .87

.87 ND

#
#

1.63 1.72 1.72

.75 .81

3.41 7.55 3.17 .81 3.62 3.47 9.63 8.65 @95 2,61

# @66 C

# @66 C

.15 @66 C ND .70

.98 7.59 4.98 2.35 C ND ND .83 1.08 1.08

1.15 1.15

#
C

.70 c 2.51 .76 c

.83

1.27
.70 C

c c 5.34 .81 .76 1.o6 1.o6 3.58 3.58 c c ND ND ND

.63 c

#
C .75 ND .70 .70 C .88 .74

#
C 2.07

#
C 8.38 C 3.09 c 1.32

ND ND ND .74 1.76 1.76 2.96 2.96 # #

.77

.69

.69 ND

.72

.721 1.05 1.05 2.19 2.19 ND ND ND

615
Table 2. continued Wt % of Quantifiable Peaks in Aroclors ( Total in Peak; Total for each Homolo~l ) DB1 CI IUPAC Congener A1221 A1232 A1016 A1242 A1248 A1254 A1260 A1262 Peak # # I.D. Tot. Horn. Tot. Horn. Tot. Horn. i Tot. Horn. Tot. Horn. T o t . Horn. 57.2 5 56 2345-2 ND ND ND ND ND 58.1 4 81 345-4 .70 .70 .78 .78 1.35 1.351 4.00 4.00 .66 .66 # 58.1 5 87 234-25 58.1 5 I;7 2356-4 58.1 5 125 345-26 58.2 5 111 235-35 58.2 5 115 2346-4 @87 @87 087 @87 58.2 5 118 23456 58.2 6 145 2346-26 59 5 85 234-24 .71 1.25 1.33 60 4 77 34-34 @110 # ~110 #i @110 ND 60 5 12o 245-35 60 6 136 236-236 OII0 # O110 ~ 0110 NDI 1.53 .90 .9C 1.00 1.00 2.73 2.73 9.00 9.00 1.47 1.47 1.04 1.04 61 5 110 236-34 38 .78 ND ND 61 6 t4a 235-246 ND 62 6 154 245-246 .69 .85 1.01 63 5 82 234-23 # 64 6 151 2356-25 # .89 3.10 3.01 # C .38 ND ND 65 5 124 345-25 65 6 135 235-236 1.13 .75 1 . 1 8 1.18 .92 .92 66 6 144 2346-25 ~67 .14 1.18 .92 67 5 Io7 234-35 67 5 109 235-34 # .85 .721 67 6 147 2356-24 68 5 ;23 345-24 69 5 toe 2345-3 69 5 118 245-34 .74 .74 .80 .80 2.35 2.35 10.45 7.12 C .95 C .71 69 6 13~ 2346-24 69 6 149 236-245 ND ND # ND C 3.33 10.30 9.35 7.70 6.99 70 6 14o 234-246 71 5 114 2345-4 # .30 ND bid 71 6 134 2356-23 .78 .48 .64 .64 .63 .63 71 6 143 2345-26 72 5 122 345-23 C # # 72 6 131 2346-23 72 6 133 235-235 C C 72 6 ;42 23456-2 # 73 6 146 235-245 .80 .8C 1 . 1 6 1.16 .80 .8C 73 6 165 2356-35 73 7 ;55 2356-246 ND ND ND 74 5 105 234-34 .72 .72 .74 .74 1.82 1.82 C 1.51 # ND 74 6 132 234-236 ND ND # biD 3.98 2.47 2.73 2.73 @153 74 6 ;6; 2346-35 75 6 153 245-245 76 5 f27 345-35 76 6 ;65 246-345 76 7 I5 4 2346-246 77 6 141 2345-25 1.01 2.49 1.60 78 7 179 2356-236 # 2.08 3.03 79 6 137 2345-24 .74 80 6 130 234-235 .74 # 81 7 176 2346-236 # # .85

616 Table 2. continued DB1 CI IUPAC Congener Peak # # I.D. 82 6 138 234-245 82 6 163 2356-34 82 6 ] 6 4 236-345 83 6 ]58 2346-34 83 6 16o 23456-3 83 7 766 23456-26 84 5 126 345-34 84 6 | 2 9 2345-23 85 6 t 6 6 23456-4 85 7 178 2356-235 87.1 7 175 2346-235 87.2 6 16s 2345-35 88 7 1a2 2345-246 88 7 187 2356-245 89 6 128 234-234 89 6 162 235-345 90 7 183 2346-245 91 6 167 245-345 92 7 185 23456-25 93 7 174 2345-236 93 7 181 23456-24 94 7 177 2356-234 95 6 156 2345-34 95 7 171 2346-234 96 6 157 234-345 96 8 202 2356-2356 98 7 173 23456-23 99 8 201 2346-2356 100 7 172 2345-235 100 8 2o4 23456-246 101 7 t 9 2 23456-35 101 8 197 2346-2346 102 7 180 2345-245 103 7 193 2356-345 104 7 191 2346-345 105.1 8 200 23456-236 105.2 6 t 6 s 345-345 106 7 170 2345-234 107 7 190 23456-34 108 109 110 110 111 112 113 114 115 116 117 118
I I *, !,

Wt % of Quantifiable Peaks in Aroclors ( Total in Peak; Total for each Homolo ) A1221 A1232 AIO1E A1242 A1248 A1254 A1260 A1262
Tot. Horn. Tot. Hem. Tot. Horn. Tot. Hem. Tot. Hem.

.78
C

6.20
C C 1.00

10.70
C C #

5.01
C C #

1,00
ND ND .71

.71 #

# .90 1.11

# #

.61 1.39 # .65 .63 .59 .94 C

#

5.22 # 3.10

8.85 # 3.10 .88 6.02 2.61 # 1.04

#
.72 4.63 2.51 C 1.72 C #

.89 .05

.68 1.04

NE 1.0z N(: 1.07 1.0~

# #
.59 .59 ND .93 .93 ND

#
.85 .82
.82 NE

#
.74 11.10

#
14.01

# # #
.65

# #
.83
2.65 .87

3.76 .94

8 8 8 8 7 8 9 9 8 8 9 10

23456-235 2345-2356 2345-2346 23456-245 2345-345 23456-234 23456-2356 207 23456-2346 194 2345-2345 205 23456-345 266 23456-2345 2o9 23456-23456
~ - I d ~ ~] * I i . | [i'll[ill ~'T~ I ! 1[ [i'il[i| I [i'ilt ,]'11 [It'll

198 199 196 203 189 195 208

#
1.66 C 2.09

#
4.97 C 5.17

#
.88

1.25

1.65

3.60

#
31

#
1.30

I llliI/-1T*l ~

i [l'l|

| |l~il

617 (a) - Key to Conventions, Symbols and Abbreviations in Table 2: Peak 1 in the 118 peak numbering system is biphenyi (not listed in the table). See text for determination of the amount of biphenyl in Aroclors 1221 and 1232. Congener IUPAC numbers in the larger boldface font were present in at least one of the Aroclors at or above 0.05 wt %. Those in small italic print were absent or present at < 0.05 wt % Congener designations denote the positions of the chlorine atoms on each ring of biphenyl and the hyphen represents separation of the rings. Tot. column for each Aroclor lists the total wt % of all congeners in each peak. as determined by GC/ELCD Hem. column for each Aroclor lists wt % values of different homologs in each peak as determined by GC-MS in scan mode. # indicates that more sensitive GC-MS-SIM or GC-ECD analyses have determined that the peak or congener is present between 0.05 and 0.5 wt %. C indicates that the congener contributes to the total wt % displayed for the major congener in a peak, and is above 0.05 wt %. Wlam C is combined with # and no wt % is given, # is the major component, and the total wt % of the peak is _>0.05 % but < 0.5 wt %. @ IUPAC# indicates that the congener duted in a different peak in this particular Aroclor. Its observed elation position is indicated by the IUPAC# of the congener with with it elated. See text for more details. ND indicates that the coelating homolng (congener of differeat CI number) was not detected by full-scan GC-MS. NQ indicates that the coeluting homolog was present, but was not quantifiable due to interference from CF loss fragments from higher coehiting homoings. Comprehensive Quantitative Congener-Specific Weight Percent Data for Eight Aroclors. Table 2 give two columns of weight percent information for each of the eight Aroclors. The first gives the total weight percent of the PCB congeners in each peak as determined by GC-ELCD and is printed on the line of the congener thought to be present at the highest concentration in the peak. Peaks present at < 0.5 wt % could not be quantified by GC-ELCD because of sensitivity limitations. However, we used semi-quantitative data from GC-ECD and/or GC-MS to identify peaks that are present at > 0.05 wt % but < 0.5 wt % and have indicated these by the symbol # on the line of the most abundant congener in the peak. In cases where several congeners coelute in a particular peak, we have indicated those that are present in each Aroclor by a wt % value, a C, or the symbol # or @. "C" indicates that a congener significantly contributes to the total weight percent for that peak. "@" indicates that the congener is present but coelutes with a major component in a peak different from the one to which it would be assigned by its retention time if eluting by itself. Such instances result from disparate proportions of closely eluting congeners and are indicated by the convention "@ IUPAC#" where the IUPAC# is that of the congener with which it actually elutes and with which its weight percentage was calculated. Examples of this type of variation in elution assignment and quantitation may be observed in the peak pairs 48.1/48.2, 60/61, and 74/75. Congeners assigned to a peak without any further notation were not found to be present at significant levels in that particular Aroclor. For peaks where the CJC-MS scan data provided relative amounts for different homolog sets within a peak, the weight percentages of the homologs of each chlorinatidn level are listed in the second column for each Aroclor. The symbol ND indicates that the homolog was not detected by GC-MS in the scan mode. There are several instances where analysis on a different column phase by GC-SIM determined that a particular homolog not detected in scan mode was actually present at levels between 0.05 and 0.5 wt %. These are indicated by the symbol # in the first column and ND in the second column for the particular Aroclor (see pks 14, 69, and 74 in Aroclor 1248 and pk 26 in Aroclor 1016). Finally, in several cases the individual proportions of coeluting

618 homologs could not be accurately determined by GC-MS because of interference from the chlorine loss fragments of the higher coeluting ho~olog(s). These instances are indicated by the symbol NQ (e.g. see pk 38). The listed weight percent values were calculated as percentages of the total GC-ELCD-measured PCB content, not as percentages of the actual weight of Aroclor. Therefore, for use as calibration standards, the tabulated PCB congener distributions of the Aroclor 1221 or 1232 standards should be multiplied by 0.883 and 0.938, respectively, to compensate for the amounts of biphenyl found in these two Arociors. In addition, we estimate that the sum of peaks > 0.05% but not quantifiable by GC-ELCD in any one Aroclor ranges from - 3.5 to 8.7 weight percent. Hence the values for major components listed in Table 2 may differ from a more complete determination by this amount PCB Homolog Distributions of Eight Aroclors. Homolog distributions provide another useful way of analyzing PCB mixtures. Individual Aroclors were manufactured to contain specified weight percents of chlorine, except for Aroclor 1232, which was a blend of 1221 and 1242 (roughly 50:50), and Aroclor 1016, which was made by distillation from Aroclor 1242 to remove the more highly chlorinated congeners Table 3 shows the homolog weight percent distributions for each of the eight Aroclor samples that we analyzed Table 3. Comparison of Homolog Distributions in Different Aroclors and Different Lots of Aroclors Weiaht % in Aroclors Determined in This Study 1221 1232 1016 1242 1248 1254 1260 1262
65.5 31.3 29.7 23.7 21.2 14.7 4.8 23.4 51.5 46.0 20.9 5.8 1.8 9.2 4.2 15.7 27.3 30.6 60.3 17.1 8.7 18.1 49.3 21.5 15.0 49.8 35.3 1.2 0.I 1.0 27.8 32.6 16.6

CI No.
I 2 3 4 5

Weiaht % in Aroclors ( Ref. 22) 1016 1242 1254 1260

1.0 13.2 51.0 13.5

6 7
8

9 10

0.8 27.8 46.9 30.9 3.9 36.9 45.8 6.3 17.7 0.7 1.3

0.2

2.4 23.9 47.0 0.2 4.4 33.8 0.7 7.5 0.7 0.1

DISCUSSION We have prepared calibration tables that assign 135 congeners and 104 peaks to the Aroclors. The remaining 74 congeners have been assigned to either these 104 peaks or to 20 additional peaks that are resolved on a DB-I column. Our tables include weight percent distributions for all major ( > 0.5 wt %) PCB components of Aroclors 1221, 1232, 1242, 1016, 1248, 1254, 1260, and 1262. Aroclor components present between 0.05 and 0.5 wt % were also identified, but not quantified. Our data for samples of the eight Aroclors indicate that there are significant errors in congener assignments and in quanfitation in several recently published studies. In 1993 the World Health Organization published a comprehensive table of the distributions of congeners in Aroclors 1016, 1242, 1248, 1254 and 1260 (37).

619 Unfortunately, these values were compiled from early data (38,39) that relied on different sets of packed or capillary GC columns to help resolve ~oeluting congener pairs. With fewer than 50 individual congener standards available at that time, most assignments of congeners to peaks were made from estimated retention times based on single ring half-retention indices. A comparison of the Aroclor congener distributions in the W.H.O. table with those of SchuLz et al. (23) and those reported here indicates many likely misassignments and quantitative inaccuracies in the W.H.O. table. Therefore, it should not be used as a basis for calibrating CQCS analyses. We found similar discrepancies in tables of major constituents of Aroclors 1242 and 1260 that were recently published by Krupcik et al. (17). Their table of Aroclor 1242 constituents present above 0.2 wt % omits six congeners that we report at ~ 0.7 wt %, namely congeners 82, 85, 87, 91, 97, and 105. Conversely, the table includes congeners 69, 72, 76, and 113 (albeit with no values listed), but we found these to he below 0.05 wt %. The table is also misleading in that it does not clearly identify which congeners coelute and does not assign values to different coeluting homologs. Hence, congeners 53 and 51 are listed on a par with coeluting congeners 33 and 22, whereas our data show that congeners 53 and 51 constitute < 5% of tbeir respective peaks (see DB-1 peaks 25 and 26 in Table 1). Serious omissions in the table of Aroclor 1260 constituents > 0.4% published by Krupcik et al. (17) raise even more concern. The table omits congener 153 which we report at 12.2 wt % and which is generally recognized as the most significant single component in Arociors and the one most frequently reported. The table also omits congeners 172, 177, 195, 199, and 206 which we found to be present between 0.7 and 2.5 wt % and gives no values for congeners 149 and 187 which we report as 3.3 and 5.2 wt %, respectively. Conversely, congeners 66, 123, 148, 159, and 182 are all listed as major constituents, hut we found them to be well below
0.05 wt %.

The discrepancies between the Aroclor 1242 and 1260 constitutents reported by Krupcik et al. (17) and those reported here and by Schulz et al. (23) are too large to he explained by variations in Aroclor lots and are more likely due to congener misassignments, reporting omissions, and quantitative inaccuracies in the tables published in ref. 16. Consequently, the procedure recommended by Krupcik et al. (17) for combining GC-FID and GC-MS measurements of Aroclors to support their use as secondary standards is only as good as the accuracy of the congener assignments allows and should be used with caution. The only other CQCS data for individual Aroclors are those determined by 2-D GC for Arodors 1016, 1242, 1254, and 1260 (23). However, Larsen (6) cautioned in a recent review that the 2D-GC method can miss all or parts of some congeners in peaks if the secondary column lacks sufficient discrimination, or iftbe heart cuts are not made exactly right. He also pointed out that congeners proven to be present in significant amounts in Aroclors, such as 71, 163, 43 and 102 are not listed in the 2D-GC tables of Schulz et al. We concur, and we further note that we detected substantial amounts of congeners 114, 124 and 144 that were not reported by Schuiz et al. Therefore, although the Schulz tables are extremely valuable for an overview of Aroclor congener distributions, they must be approached with caution as the basis e r a CQCS PCB analysis calibration. It is important to recognize that there may be significant variations in different lots of the same Aroclors. Table 3 illustrates differences between the homolog distributions that we report for the Aroclors and those that can be calculated for Aroclors 1016, 1242, 1254, and 1260 from the 2-D GC tables of Schulz et al. (23). Undoubtedly some of these differences are due to the different methods of analysis, hut others are most likely due to differences in the particular Aroclor lots analyzed. Thus it is important that the Aroclor lots used for a

620 secondary calibration standard be well-matched to those from which the published weight percent distributions were determined. Our eight Aroclor standards, together with the congener distributions in Table 2, provide much greater flexibility than the single fixed mixtures used by most other methods (13, 14, 15, 19). Site-specific customized standards can easily be created by mixing the individual Aroclors in various proportions to match the chromatographic patterns observed at individual sites. In instances where a particular Aroclor distribution has undergone major alteration, including the production of unusual dechlorination products, the standard can be further customized by the addition of the congeners observed as dechlorination products (10). CQCS PCB analysis methods using our Aroclor standards and the values in Table 2 have been employed in a number of published studies (25-34). Our complete peak assignment table makes it possible to measure minor Arocior peaks and non-Aroclor peaks (such as dechlorination products) by calibrating against pure congener standards run separately or by using tables of response factors corrected for the actual instrument being used. Two recent PCB dechiorination studies that relied on our weight percent tables with such supplementation attest to their accuracy by demonstrating that the calibrations based on these tables permitted stoichiometric mass balances for parent congeners and their dechlorination products (33, 34). There is still a need for readily available Aroclor calibration standards for CQCS PCB analyses. Ideally, these would consist of a set of individual Aroclor solutions covering the full range of congener distributions; namely, Aroclors 1221, 1242, 1248, 1254, 1260, and 1262, for which the weight percent distributions of all congeners present at or above 0.05% have been carefully determined by state-of-the-art multicolumn/multidetector methods against primary standards of all congeners found in the Aroclors. These Aroclor solutions should remain available over a long duration together with their weight percent distributions. LITERATURE CITED 1. Abramowicz, D.A.; Brown, J.F. Jr., Harkness, M.R. and O~)onnell, M.K.; In situ Anaerobic PCB Dechlorination and Aerobic PCB Biodegradation in Hudson River Sediments. In: Hickey, R.F. (Ed) The Imple-

mentation of Biotechnology in Industrial Waste Treatment and Bioremediation.

Lewis Publishers, p57 - 92 (1995) 2. Bedard, D.L.; Wagner, R.E.; Brennan, M.J.; Haberl, M.L. and Brown, J.F. Jr.; Extensive Degradation of Arolors and Environmentally Transformed Polychlorinated Biphenyls by Alcaligenes eutrophus H850.

Appl. Environ. Microbiol., 53, 1094 (1987)

3. Bedard, D.L. and Quensen, J.F.; Microbial Reductive Dechlorination of Polychlorinated Biphenyls. In: Young, L.Y., Cerniglia, C. CEds.) Microbial Transformation and Degradation of Toxic Organic

Chemicals, Wiley-Liss Division, John Wiley & Sons, Inc., New York, p. 127 - 217 (1995)
4. LApine, F; Milot, S.; and Vincent, N.; Formation of Toxic PCB Congeners and PCB-Soivent Adducts in a Sunlight Irradiated Cyciohexane Solution of Aroclor 1254. Bull. Environ. Contain. Toxicol., 48, 152 (1992)

621 5. Frame, G.M.; Cochran, J.W.; Bzwadt, S.S.; Capillary GC Systems Optimized for Determination of Complete Congener Distributions in Aroclor Mixtures. Abstract in: National American Chemical Society

Meeting, New Orleans, LA. (1996)

6. 7. Larsen, B.; [Critical Review] HRGC Separation of PCB Congeners. J. High Resoi. Chromatogr., 18, 1 (1995) McFarland, V.A. and Clarke, J.U.; Environmental Occurrence, Abundance, and Potential Toxicity of Polychlorinated Biphenyl Congeners: Considerations for a Congener-Specific Analysis. Environmental

Health Perspectives, 81, 225 (1989)

8. 9. 10. Organochlorine Pesticides and PCBs as Aroclors by Gas Chromatography: Capillary Column Technique US EPA Method 8081, Sept 1994 Kimbrough, D. E.; Chin, R. and Wakakuwa, J.; Widespread and Systematic Errors in the Analysis of Soils for Polychlorinated Biphenyls: Part 3. Gas Chromatography. Analyst, 119, 1293 (1994) Smullen, L.A., DeWeerd, K.A.; Bedard, D.L.; Fessler, W.A., Carnahan, J.C. and Wagner, R.E.; Development of a Customized Congener-Specific PCB Standard for Quantification of Woods Pond Sediment PCBs. In: G.E. Corporate R&D Programfor Destruction of PCBs, 12th Progress Report GE Corporate Research and Development 1993, Schenectady, NY pp 45-65 11. 12. 13. 14. 15. Hutzinger, O., Safe, S., Zitko, V., The ChemistryofPCBs. CRC Press, Cleveland, OH., p. 211-218 (1974) Erickson, M.D.; Analytical Chemistry ofPCBs. Butterworth Publishers. Stoneham, MA., p. 210-211. (1985) Bush, B.; Cannot, S. and Snow, J.; Glass Capillary Gas Chromatography for Sensitive, Accurate Polychlorinated Biphenyl Analysis. J. Assoc. Off. Anal. Chem., 65, 555 (1982) Bush, B.; Murphy, M.J., Cannot, S., Snow, J. and Barnard, E.; Improvements In Glass Capillary Gas Chromatographic Polychlorobiphenyl Analysis. J. Chromatogr. Sci., 23, 509 (1985) Eganhouse, R.P.; Gould, B.R.; Olaguer, D.M.; Phlnney, C.S. and Sherblom, P.M., Congener-Specific Determination of Chlorobiphenyls in Biological Tissues using an Aroclor-Based Secondary Calibration Standard. Intern. J. Environ. Anal. Chem., 35, 175 (1988) 16. 17. Albro, P.W. and Fishbein, L.; Quantitative and Qualitative Analysis ofPolychlorinated Biphenyls by GasLiquid Chromatography and Flame Ionization Detection. J. Chromatogr., 69, 273 (1972) Krupcik, J.: Kocan, A.; Petrik, J.: Leclercq, P.A., and Ballschmiter, K.; On the Use of Reference Standards for Quantitative Trace Analysis of PCBs by HRGC. Analysis of Technical PCB Formulations by

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