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ASSESSMENT CF HUMAN EXPOSURE TO POLYCHLORINATED DIBENZOFURANS AND DIOXINS \ Christoffer Rappe, Martin Nygren, Stellan Marklund, Lars-Owe Kjeller, Per-Anders Bergqvist and Marianne Hansson Presented at the International Workshop on Occupational Hazards Caused by Polychlorinated Biphenyls (PCBs) and Chlorobenzenes in Capacitors and Transformers Espoo, Finland. September 1983. 2 ABSTRACT Fires explosions and other accidents in PCB filled equipment can result in possible exposure of firemen, cleaning personel and the normal workers.' j Inhalation, dermal exposure and ingestion are the possible routes of ex posure. An indirect assessment of the exposure can be made by analyses of wipes, air and water samples and clothes. A direct assessment of exposure can be made by analyses of blood samples, adipose and other tissue samples, feces and bile. Key words: PCB PCB Fires Capaci tors Transformers Polychlorinated dibenzofurans Polychlorinated dioxins Exposure 783463 GENP 010652 INTRODUCTION The PC8 accidents discussed in Ref. 1 resulted in a possible exposure of firemen, cleaning personel and partly also the normal workers. The pos sible routes of exposure are Inhalation Ingestion Dermal The assessment of exposure can be made from the analyses of a variety of samples like wipes, air, water samples and clothes. These assessments are indirect as the amount absorbed through the skin is 1-102, via inha lation S0-70S and via ingestion 50-90* is taken up. A direct assessment of the exposure can be made by analyses of samples taken from the exposed persons like blood, adipose and other tissues, feces and bile. INDIRECT ASSESSMENTS OF EXPOSURE The most important samples for the indirect assessment of exposure are wipe tests. The results from the recent Scandinavian PCB accidents discussed in Reference 1 indicate a large variation in the levels of PCDOs and PCBPs. The isomeric pattern are almost identical in these samples consequently the risk of exposure is parallel to the levels found for PCDFs and PCBPs, see Table 1. Water is used to extinguish the fire and for washing. Water samples from the Surahanvnar fire were analyzed, see Table 2. A series of PCDFs could be identified in a water sample from the high pressure washing also containing suspended soot particles. However, when the soot particles had sedimented, the supernatant water phase contained less than 0.1 pg/ml of each PCOF isomer including 2,3,7,8-tetra-CDF. No solubility studies GENP 010653 783464 V' 4 of PCDFs can be found 1n the literature, but in laboratory experiments the solubility of 2,3,7,8-tetra-CDD has been found to be 200 pg/ml (2). It can be assumed that the solubility of PCODs and PCDFs is quite simi lar, consequently the solubility in the washing water is highly reduced possibly due to the adsorption of PCDFs on soot particles. Air samples have been collected and analyzed in order to estimate the amount of exposure via Inhalation. The cartridges used in this study consisted of a filter and a XAD-2 layer, both were analyzed together. Samples were taken during and after the cleaning operations at the Surahammar steel mill and during the cleaning operations of the railway locomotive (1), see Table 3. In Surahammar the levels were below the detection level, 2 pg/m3 for each isomer. In a sample collected close to the exploded capaci tor of the railway locomotive, the level of 2,3,7,8-tetra-CDF was 50 pg/m^. No soot was found in this accident. From the Surahammar fire we have analyzed overalls and underwear. The overalls were washed after use every day. After being used for 14 days 2 an overall was found to have 28 ng 2,3,7,8-tetra-CDF/m and about 100 ng 2 of all tetra-CDFs/m,. Another overall used and washed for one month fol lowed by dry cleaning had almost the same levels. A set of underwear also 2 used for one month had less than 5 ng 2,3,7,8-tetra-CDF/m . In order to avoid dermal exposure the workers should be protected by double layers of protective clothings. DIRECT ASSESSMENT OF EXPOSURE Blood samples have been collected from more than forty firemen and ana lyzed by a method earlier described in Reference 3. No PCDFs were de tected in these samples at a detection level of 0.1 pg/ml blood serum for the toxic 2,3,7,8-tetra-CDF and 1,2,3,7,8- and 2,3,4,7,8-penta-CDFs. GENP 010654 5 We have analyzed a sample of adipose tissue from a man engaged in the clean-up operations in the Binghamton State Office Building. The levels found were 8 ppt of 2,3,7,8-tetra-CDF and 9 ppt for 2,3,4,7,8-penta-CDF, which is close to background levels found in the general population (4). CHECKING LIST AFTER PCB ACCIDENTS Information: Workers Industrial hygienists Authorities: Occupational Environmental Local medical Press, TV Coordination: Local coordinator for sampling and cleaning Sampling: Areas (indoor and outdoor) Exposed personel (blood) Air Water Analyses: PCBs; Levels and isomeric pattern PCOFs, PC8Ps, PCDDs; Isomer specific Contact: Cleaning firm Cleaning firm: Experienced Good protection of workers Good equipment Vacuum cleaning - high pressure washing GENP 010655 . .* -L i 783466 Resampling: Maste: Contaminated areas - Analyses Controlled degradation 6 1*> ' ' GBt* o l06S6 783467 ? 4 Table 1. Comparison of PCDF levels 1n wipe samples GENP 010657 iu. * "v l 00 CO 05 00 $ Sample Sktivde Surahammar Stockholm Hallstahammar Imatra Railway locomotive Kisa Halmstad Type PCB f oil fire _II ^ PCB Explosion _II -- _11^ M- Levels 1 pg/mZ i - 10 _u_ 1.5 _*1 _ 1 - 10 1- 3 1 - 100 -- 1 - 1000 _ll^ 0.1 - 500 _II_ Other Constituents + PCBPs (rajor) + PCBPs (minor + PCBPs (minor) + PCBPs (minor) 9 `If-A t- Table 2. Analyses of PCDFs In water samples, Surahammar (pg/ml) Sample t C14 High pressure washing (incl. soot) 4500 High pressure washing (after sedimentation) < 2.5* 23781500 < 0.1 Cl 5 2000 < 2.5* E Cl6 500 z ci7 15 < 1.5* < 2.5 C,B 15 < 2.5 .i N < 0.1 pg each Isomer CO a Q Table 3 Analyses of PCDFs in air samples (pg/mJ) Sample Surahammar During cleaning Surahammar After cleaning Railway locomotive During cleaning i ci4 < 20 2378<2 C15 < 10 < 10 < 2.5 < 10 500 50 50 EC16 < 10 < 10 30 Cl? < 10 < 10 20 C,8 < 10 < 10 20 IO I  l-' , * REFERENCES 10 (1) Rappe, C., Marklund, S ., Kjeller, l.-O., Bergqvist, P.-A. and Hansson, M. Strategies and techniques for sample collection and analyses. Experience from the Swedish PCS accidents. Environm. Health Perspect. In press (1984). (2) Crunmett, U.B. and Stehl, R.H. Determination of chlorinated dibenzo--dioxin$ and dibenzofurans in various materials. Health Perspect. 15-25 (1973). (3) Rappe, C., Nygren, M. and Gustafsson, G. Human exposure to polychlorinated dioxins and dibenzofurans in Chlorinated Dioxins and Dibenzofurans in the Total Environment. Vol. 1. Eds. Choudhary, C., Keith, L. and Rappe, C. In press. (4) Rappe, C., Nygren, M. and Hansson, M. Unpublished results.