Polychlorobiphenyls (5503)
POLYCHLOROBIPHENYLS
mixture:
C12H10-x Clx [where x = 1 to 10]
MW: ca. 258 (42% Cl ; C12H7Cl3); ca. 326 (54% Cl ; C12H5Cl5)
METHOD: 5503, Issue 2
CAS: Table 1
EVALUATION: PARTIAL
OSHA : 1 mg/m3 (42% Cl); 0.5 mg/m3 (54% Cl) NIOSH: 0.001 mg/m3/10 h (carcinogen) ACGIH: 1 mg/m3 (42% Cl) (skin) 0.5 mg/m3 (54% Cl) (skin)
5503
RTECS: Table 1
Issue 1: 15 February 1984 Revision #1: 15 August 1987 Issue 2: 15 August 1994
PROPERTIES: 42% Cl: BP 325 to 366 °C; MP -19 °C; d 1.38 g/mL @ 25 °C; VP 0.01 Pa (8 x 10-5 mm Hg; 1 mg/m3) @ 20 °C 54% Cl: BP 365 to 390 °C; MP 10 °C; d 1.54 g/mL @ 25 °C; VP 0.0004 Pa (3 x 10-6 mm Hg; 0.05 mg/m3) @ 20 °C
SYNONYMS: PCB; 1,1'-biphenyl chloro; chlorodiphenyl, 42% Cl (Aroclor 1242); and 54% Cl (Aroclor 1254)
SAMPLING SAMPLER:
FILTER + SOLID SORBENT (13-mm glass fiber + Florisil, 100 mg/50 mg)
FLOW RATE: 0.05 to 0.2 L/min or less VOL-MIN: -MAX:
1 L @ 0.5 mg/m3 50 L
SHIPMENT:
transfer filters to glass vials after sampling
SAMPLE STABILITY:
MEASUREMENT TECHNIQUE:
GAS CHROMATOGRAPHY, ECD (6 3Ni)
ANALYTE:
polychlorobiphenyls
DESORPTION:
filter + front section, 5 mL hexane; back section, 2 mL hexane
INJECTION VOLUME:
unknown for filters; 2 months for Florisil tubes [1]
4-µL with 1-µL backflush
TEMPERATURE-INJECTION: -DETECTOR: -COLUMN: CARRIER GAS:
BLANKS:
250 to 300 °C 300 to 325 °C 180 °C
N2, 40 mL/min
2 to 10 field blanks per set COLUMN:
glass, 1.8 m x 2-mm ID, 1.5% OV-17/1.95% QF-1 on 80/100 mesh Chromosorb WHP
ACCURACY RANGE STUDIED:
not studied
BIAS:
none identified
ˆ ): not evaluated OVERALL PRECISION (S rT ACCURACY:
not determined
CALIBRATION:
standard PCB mixture in hexane
RANGE:
0.4 to 4 µg per sample [2]
ESTIMATED LOD: 0.03 µg per sample [2] PRECISION (Sr):
0.044 [1]
APPLICABILITY: The working range is 0.01 to 10 mg/m3 for a 40-L air sample [1]. With modifications, surface wipe samples may be analyzed [3,4].
INTERFERENCES: Chlorinated pesticides, such as DDT and DDE, may interfere with quantification of PCB. Sulfur-containing compounds in petroleum products also interfere [5].
OTHER METHODS: This method revises methods S120 [6] and P&CAM 244 [1]. Methods S121 [7] and P&CAM 253 [8] for PCB have not been revised.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94 POLYCHLOROBIPHENYLS: METHOD 5503, Issue 2, dated 15 August 1994 - Page 2 of 5 REAGENTS:
EQUIPMENT:
1. Hexane, pesticide quality. 2. Florisil, 30/48 mesh sieved from 30/60 mesh. After sieving, dry at 105 °C for 45 min. Mix the cooled Florisil with 3% (w/w) distilled water. 3. Nitrogen, purified. 4. Stock standard solution of the PCB in methanol or isooctane (commercially available).*
See SPECIAL PRECAUTIONS.
1. Sampler: 13-mm glass fiber filter without binders in a Swinnex cassette (Cat. No. SX 0001300, Millipore Corp.) followed by a glass tube, 7 cm long, 6-mm OD, 4-mm ID containing two sections of 30/48 mesh deactivated Florisil. The front section is preceded by glass wool and contains 100 mg and the backup section contains 50 mg; urethane foam between sections and behind the backup section. (SKC 226-39, Supelco ORBO-60, or equivalent) Join the cassette and Florisil tube with PVC tubing, 3/8" L x 9/32" OD x 5/32" ID, on the outlet of the cassette and with another piece of PVC tubing, 3/4" L x 5/16" OD x 3/16" ID, complete the union. 2. Personal sampling pump, 0.05 to 0.2 L/min, with flexible connecting tubing. 3. Tweezers. 4. Vials, glass, 4- and 7-mL, with aluminum or PTFE-lined caps 5. Gas chromatograph, electron capture detection ( 63Ni), integrator and column (page 5503-1). 6. Volumetric flasks, 10-mL and other convenient sizes for preparing standards. 7. Syringe, 10-µL.
SPECIAL PRECAUTIONS: Avoid prolonged or repeated contact of skin with PCB and prolonged or repeated breathing of the vapor [9-11].
SAMPLING: 1. 2. 3.
4.
Calibrate each personal sampling pump with a representative sampler in line. Break the ends of the Florisil tube immediately before sampling. Connect Florisil tube to Swinnex cassette and attach sampler to personal sampling pump with flexible tubing. Sample at an accurately known flow rate between 0.05 and 0.2 L/min for a total sample size of 1 to 50 L. NOTE: At low PCB concentrations, the sampler was found to be efficient when operated at flow rates up to 1 L/min, for 24 hours [4]. Under these conditions, the limit of detection was 0.02 µg/m 3. Transfer the glass fiber filters to 7-mL vials. Cap the Florisil tubes with plastic (not rubber) caps and pack securely for shipment.
SAMPLE PREPARATION: 5. 6. 7.
Place the glass wool and 100-mg Florisil bed in the same 7-mL vial in which the filter was stored. Add 5.0 mL hexane. In a 4-mL vial, place the 50-mg Florisil bed including the two urethane plugs. Add 2.0 mL hexane. Allow to stand 20 min with occasional agitation. NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94 POLYCHLOROBIPHENYLS: METHOD 5503, Issue 2, dated 15 August 1994 - Page 3 of 5 CALIBRATION AND QUALITY CONTROL: 8.
9.
10.
Calibrate daily with at least six working standards over the range 10 to 500 ng/mL PCB. a. Add known amounts of stock standard solution to hexane in 10-mL volumetric flasks and dilute to the mark. b. Analyze together with samples and blanks (steps 11 and 12). c. Prepare calibration graph (sum of areas of selected peaks vs. ng PCB per sample). Determine desorption efficiency (DE) at least once for each lot of glass fiber filters and Florisil used for sampling in the calibration range (step 8). Prepare three tubes at each of five levels plus three media blanks. a. Remove and discard back sorbent section of a media blank Florisil tube. b. Inject known amounts of stock standard solution directly onto front sorbent section and onto a media blank filter with a microliter syringe. c. Cap the tube. Allow to stand overnight. d. Desorb (steps 5 through 7) and analyze together with working standards (steps 11 and 12). e. Prepare a graph of DE vs. µg PCB recovered. Analyze three quality control blind spikes and three analyst spikes to ensure that the calibration graph and DE graph are in control.
MEASUREMENT: 11.
12.
Set gas chromatograph according to manufacturer's recommendations and to conditions given on page 5503-1. Inject sample aliquot manually using solvent flush technique or with autosampler. NOTE 1: Where individual identification of PCB is needed, a procedure using a capillary column may be used [12]. NOTE 2: If peak area is above the linear range of the working standards, dilute with hexane, reanalyze and apply the appropriate dilution factor in calculations. Sum the areas for five or more selected peaks.
CALCULATIONS: 13.
14.
Determine the mass, µg (corrected for DE) of PCB found on the glass fiber filter (W) and in the Florisil front (W f) and back (W b) sorbent sections, and in the average media blank filter (B) and front (B f) and back (B b) sorbent sections. NOTE: If W b > W f/10, report breakthrough and possible sample loss. Calculate concentration, C, of PCB in the air volume sampled, V (L):
EVALUATION OF METHOD: This method uses 13-mm glass fiber filters which have not been evaluated for collecting PCB. In Method S120, however, Aroclor 1242 was completely recovered from 37-mm glass fiber filters using 15 mL isooctane [8,13,14]. With 5 mL of hexane, Aroclor 1016 was also completely recovered from 100mg Florisil beds after one-day storage [1]. Thus, with no adsorption effect likely on glass fiber filters for PCB, 5 mL hexane should be adequate to completely extract PCB from combined filters and front sorbent sections. Sample stability on glass fiber filters has not been investigated. Breakthrough volume was >48 L for the Florisil tube at 75% RH in an atmosphere containing 10 mg/m 3 Aroclor 1016 [1].
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94 POLYCHLOROBIPHENYLS: METHOD 5503, Issue 2, dated 15 August 1994 - Page 4 of 5 REFERENCES: [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12]
[13] [14]
[15]
NIOSH Manual of Analytical Methods, 2nd ed., V. 1, P&CAM 244, U.S. Department of health, Education, and Welfare, Publ. (NIOSH) 77-157-A (1977). User check, Southern Research Institute, NIOSH Sequence #4121-U (unpublished, January 25, 1984). Kominsky, J. Applied Ind. Hyg. 1 (4), R-6 (1986). NIOSH Health Hazard Evaluation Report, HETA 85-289-1738 (unpublished, 1986). Hofstader, R. A., C. A. Bache, and D. J. Lisk. Bull, Environ. Contam. Toxicol., 11, 136 (1974). NIOSH Manual of Analytical Methods, 2nd ed., V. 4, S120, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 78-175 (1978). Ibid, V. 2, S121, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-157-B (1977). Ibid, Vol. 1, P&CAM 253 Criteria for a Recommended Standard . . . Occupational Exposure to Polychlorinated Biphenyls, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-225 (1977). Current Intelligence Bulletin 7, Polychlorinated Biphenyls (PCBs), U.S. Department of Health and Human Services, Publ. (NIOSH) 78-127 (1975). Occupational Diseases, A Guide to Their Recognition, revised ed., 255-256, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-181 (1978). Dunker, J. C. and M. T. J. Hillebrand. Characterization of PCB Components in Clophen Formulations by Capillary GC-MS and GC-ECD Techniques, Environ. Sci. Technol., 17 (8), 449456 (1983). Backup Data Report for S120, prepared under NIOSH Contract 210-76-0123, available as "Ten NIOSH Analytical Methods, Set 2," Order No. Pb 271-464 from NTIS, Springfield, VA 22161. NIOSH Research Report-Development and Validation of Methods for Sampling and Analysis of Workplace Toxic Substances, U.S. Department of Health and Human Services, Publ. (NIOSH) 80-133 (1980). Hutzinger, O., S. Safe, and V. Zitko. The Chemistry of PCBs, CRC Press, Inc., Cleveland, OH (1974).
METHOD REVISED BY: James E. Arnold, NIOSH/DPSE; S120 originally validated under NIOSH Contract 210-76-0123.
Table 1. General Information. Compound
CAS
RTECS
Polychlorinated Biphenyls Chlorobiphenyl Aroclor 1016 (41% Cl) Aroclor 1242 (42% Cl) Aroclor 1254 (54% Cl)
1336-36-3 27323-18-8 12674-11-2 53469-21-9 11097-69-1
TQ1350000 DV2063000 TQ1351000 TQ1356000 TQ1360000
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94 POLYCHLOROBIPHENYLS: METHOD 5503, Issue 2, dated 15 August 1994 - Page 5 of 5 Table 2. Composition of some Aroclors [15]. Major Components Biphenyl Monochlorobiphenyls Dichlorobiphenyls Trichlorobiphenyls Tetrachlorobiphenyls Pentachlorobiphenyls Hexachlorobiphenyls Heptachlorobiphenyls Octachlorobiphenyls
Aroclor 1016 0.1% 1 20 57 21 1 <0.1 none detected none detected
Aroclor 1242 <0.1% 1 16 49 25 8 1 <0.1 none detected
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94
Aroclor 1254 <0.1% <0.1 0.5 1 21 48 23 6 none detected