Document 7RxdVzd5jOnxz8zmZ37aMpb38

LOUISIANA DIVISION INDUSTRIAL HYGIENE REPORT AN OPERATING UNIT OF THE DOW CHEMICAL COMPANY Department LAD-MD-92.01 File Number J 2/3/92. Date Title: Evaluation of employees' exposure to benzene, 1,3-butadiene, C5LA Blend (benzene), chloroform, ethylene dichloride, methylene chloride, propylene oxide, pyrolysis gasoline (benzene), toluene, vinyl chloride, xylene, and associated Industrial Hygiene Activities at the Louisiana Division Marine Operations, Plaquemine, Louisiana during 1991. During 1991, personal time-weighted average (TWA) exposures to benzene, 1,3-butadiene, C5-LA Blend (benzene), chloroform, ethylene dichloride, methylene chloride, propylene oxide, Pyrolysis gasoline(benzene), toluene, vinyl chloride, and xylene were evaluated. Excursion or short term exposures to benzene, 1,3-butadiene, chloroform, ethylene dichloride, methylene chloride, propylene oxide, toluene, vinyl chloride, xylene were also performed. Employee exposures to the chemicals listed above were monitored during 12-hour shift operations, and task specific excursion jobs such as connection, disconnection, sampling, and gauging. Continued periodic monitoring for potential exposures to these chemicals is planned. (continued on next page) DISTRIBUTION; EiaquemijQ^L K. Hasenback* G. Kusch R. Fitzgerald G. Meier* C. Holmes* 2306 2303 4101 3502W 3302P P. Usie* D. Wesson* 4701 3801 Midland: S. Dombrowski * Cover Sheets Only 1803 RESTRICTED FOR USE WITHIN DOW Do 0?4703 CONf Tn&NTTA! SUMMARY: (continued) Potential exposures to benzene for full shift time-weighted average (TWA) exposures ranged from <0.01 to 28 ppm. Short term exposures ranged from none detected (ND) to 374 ppm. The peak benzene sample result of 374 ppm was taken during the disconnection of a benzene barge by the marine specialist. Respiratory protection is worn during this job procedure. The OSHA PEL for benzene is 1 ppm for an 8-hr. TWA and 5 ppm for the short term exposure limit (STEL). A personal 8-hr. TWA sample for 1,3 butadiene was 0.1 ppm. STEL samples for the sampling and disconnect tasks were 0.06 and 2.1 ppm respectively. All job tasks were below the ACGIH threshold limit value (TLV) of 10 ppm. Potential benzene exposures from C5-LA Blend and Pyrolysis Gas were measured. C5-LA Blend benzene results were all below the analytical limit of quantitation (0.01 ppm). PYGAS benzene results ranged from 1.3 to 18 ppm. Respiratory protection was worn during all job tasks. Personal 8-hr. TWA samples for chloroform ranged from 0.04 to 11 ppm. These represent potential exposures because respiratory protection was worn while performing all job tasks. Short term exposures while performing connection, sampling, and disconnection tasks ranged from 0.22 to 71 ppm. The OSHA PEL 8-hr. TWA is 2 ppm and no STEL has been given. Personal 8-hr. TWA samples were collected for potential exposure to ethylene dichloride (EDC) at Marine Dock 1. The analytical results ranged from 5.7 to 34 ppm for the 8-hr. samples. The OSHA PEL for EDC is 1 ppm with a STEL of 2 ppm. Respiratory protection was worn during the loading and disconnect job tasks. Personal 8-hr. TWA and STEL samples for potential exposure to methylene chloride were collected at Marine Dock 1. The full shift samples ranged from 3.9 to 16 ppm which were below the ACGIH TLV of 50 ppm. The short term samples ranged from 0.04 to 395 ppm. Respiratory protection was worn during the loading, sampling, and disconnect procedures. The peak value of 395 ppm occurred on a ship with a leaking header valve. All short term exposures were below the OSHA Ceiling of 1000 ppm. OO 074704 OONFTDFNTT RESTRICTED FOR USE WITHIN DOW PAGE 2 SUMMARY; (continued) Potential Propylene Oxide exposures were measured at Dock 1. Three 8-hr. samples ranged from 0.02 to 0.05 ppm and four STEL samples ranged from 3.5 to 283 ppm. Respirators were worn during the connect and disconnect job tasks. The Dow IHG for propylene oxide is 3 ppm. Monitoring during loading and unloading operations of Benzene, Toluene, Xylene Mixture(BTX) was performed and the samples were analyzed for Toluene and Xylene. Five 8-hr. TWA samples ranged from ND to 0.29 for toluene and ND to 0.02 ppm for xylene. The STEL samples ranged from ND to 15 for toluene and ND to 0.1 ppm for xylene. The OSHA PEL is 100 ppm for toluene and xylene. The OSHA STEL for both is 150 ppm. Vinyl chloride is loaded onto ships at Marine Dock 2. Six 8-hr. TWA samples ranged from 0.02 to 0.88 ppm. One sample was above the action level of 0.5 ppm. This sample was taken during the inhibiting procedure. However, this was a potential exposure because respiratory protection is required for disconnecting and adding inhibiter. Twenty-one STEL samples were collected for various job tasks. The results ranged from 0.1 to 186 ppm. The 186 ppm peak was caused by a ship's leaking header system. Hazard communication, hearing conservation, and respiratory protection training was given to all employees during the year. Analysis of the monitoring data included in this report were provided by LAD Environmental Services Laboratory and analytical report numbers are found in the discussion section of this report. RESTRICTED FOR USE WITHIN DOW Dn 07470S CONFTDFNTTAi PAGE 3 RESULTS AND DISCUSSION Personal time-weighted average (TWA) and excursion or short term exposures (STEL) to benzene, benzene from pyrolysis gasoline(PYGAS), benzene from C5-LA Blend, 1,3-butadiene, chloroform, ethylene dichloride, methylene chloride, propylene oxide, toluene, vinyl chloride, and xylene were evaluated. Employee exposures to the chemicals listed above were monitored during 12-hour shift operations, and task specific excursion jobs such as connection, disconnection, sampling, and gauging. Personnel are monitored for potential exposures to benzene on a semiannual basis in accordance with CFR 29 Part 1910.1028. Continued periodic monitoring is planned to determine levels and predict monitoring requirements. Vinyl chloride monitoring is performed according to the Vinyl Chloride Standard 1910.1017 on a periodic basis dictated by the sampling results. Potential exposures to benzene for full shift (TWA) exposures ranged from <0.01 to 28 ppm and are found in Table 1. Short term (STEL) exposures ranged from none detected (ND) to 374 ppm and are found in Table 2. The peak benzene sample result of 374 ppm was taken during the disconnection of a benzene barge by the marine specialist. Respiratory protection is worn during this job procedure. The OSHA PEL for benzene is 1 ppm and 5 ppm for the STEL. Potential benzene exposures from handling C5-LA Blend and Pyrolysis Gas were determined and summarized in Tables 1 and 2. C5-LA Blend benzene results were all below the analytical limit of quantitation (0.01 ppm). PYGAS benzene results ranged from 1.3 to 18 ppm. Respiratory protection was worn during all job tasks associated with handling these materials. Monitoring during loading and unloading operations of Benzene, Toluene, Xylene Mixture(BTX) was performed and samples were analyzed for Toluene and Xylene. Five 8-hr. TWA samples ranged from none detected to 0.29 for toluene and none detected to 0.02 ppm for xylene. The STEL samples ranged from none detected to 15 for toluene and none detected to 0.1 ppm for xylene. Short and long term results are foundin Table 8. The OSHA PEL is 100 ppm for toluene and xylene. The OSHA STEL is 150 ppm. DO 074706 CONFIDENT TAt RESTRICTED FOR USE WITHIN DOW PAGE 8 A personal 8-hr. TWA sample for 1,3 butadiene was 0.11 ppm. STEL monitoring of the sampling and disconnect tasks were 0.06 and 2.1 ppm respectively. These results are found in Table 3. All job tasks were below the ACGIH TLV of 10 ppm. One area sample was taken on a barge being loaded with carbon tetrachloride. This sample was 1.0 ppm for the 8-hr. TWA and is found on Table 4. The OSHA PEL is 2 ppm. Personal 8-hr. TWA results for chloroform ranged from 0.04 to 11 ppm and are found in Table 4. These represent potential exposures because respiratory protection was worn while performing all job tasks. Short term exposures while performing connection, sampling, and disconnection ranged from 0.22 to 71 ppm. The OSHA PEL is 2 ppm. Personal 8-hr. TWA samples were collected for potential exposure to ethylene dichloride (EDO) at Marine Dock 1. These results are given in Table 5. The analytical results ranged from 5.7 to 34 ppm for the 8-hr. samples The OSHA PEL for EDO is 1 ppm with a STEL of 2 ppm. Personal 8-hr. TWA and STEL samples for potential exposure to methylene chloride were collected at Marine Dock 1. The full shift samples ranged from 3.9 to 16 ppm which were below the ACGIH TLV of 50 ppm. The short term monitoring results ranged from 0.04 to 395 ppm. The results are found in Table 6. The peak value of 395 ppm occurred on a ship with a leaking header valve. All short term exposures were below the OSHA Ceiling of 1000 ppm. Potential propylene oxide exposures were measured at Dock 1. Three 8-hr samples ranged from 0.02 to 0.05 ppm and four STEL samples ranged from 3.5 to 283 ppm. Respirators were worn during the connect and disconnect job tasks. The results are located in Table 7. The Dow IHG for propylene oxide is 3 ppm. Vinyl chloride is loaded onto ships at Marine Dock 2. Six 8 hour TWA samples ranged from 0.02 to 0.88 ppm and the results are found in Table 9. One sample was above the action level of 0.5 ppm and respresented the potential exposure from the job task of adding inhibitor. Respiratory protection is required for the job tasks of disconnecting and inhibiting. Twenty one STEL samples were collected for various job tasks. The results ranging from 0.1 to 186 ppm are found in Table 10. The 186 ppm peak came from a ship's leaking header system. DO 074707 CONFIDENT! RESTRICTED FOR USE WITHIN DOW PAGE 9 Tabl 1: R suits f Employees' Tlme-W Ight d Av rag (TWA) Exposur to B nz ne at Marin D ck 1, Plaqu min , Louisiana during 1991. Sample # 10923 11031 11032 11040 12876 12879 12880 12888 13145 13152 13204 13206 13209 13212 13215 13314 jo^a Assignment SMS PSC MS PSC PSC PSC MS PSC PSC PSC PSC PSC MS PSC PSC PSC Date Feb-13 Apr-09 Apr-09 Apr-14 Aug-21 Aug-23 Aug-29 Aug-15 Dec-07 Dec-01 Dec-10 Dec-10 Dec-10 Dec-12 Dec-13 Dec-20 Benzene Concentration Duration ppm(V/V) Comm ntsb 350 0.56 Benzene load only 310 0.57 Benzene load no disconnect or sampling 300 0.06 Benzene load no disconnect or sampling 345 28 Benzene load and disconnect 180 5.3 Benzene load no disconnect or samples 275 0.93 Loading benzene barge 300 0.38 Loading benzene barge 190 1.0 Benzene load no disconnect or samples 265 1.2 Loading benzene barge 175 0.01 Loading benzene barge 300 ND(0.04)C Discharging BTX 255 4.8 Discharging Pygas DC-325 320 0.13 Loading BTX 322 0.32 Loading benzene barge 240 0.06 Loading benzene barge 165 <0.08d Loading NM-1001 with C-5 LA Blend Industrial Hvaiene^ Exposure Benzene OSHA PEL 8-hr. TWA OSHA STEL Guideline 1 ppm 5 ppm 8 MS st Marine Specialist SMS = Senior Marine Specialist PSC = Petroleum Service Corporation Tankerman b Respiratory protection was worn during all job tasks. c None detected with the analytical limit of quantitation noted in parenthesis. d Detectable amount but below the limit of quantitation for the survey sampling conditions. HO 074708 CONFIDENTIAL RESTRICTED FOR USE WITHIN DOW PAGE 10 Table 2: Results of Employ es' Short Term Excursion (STEL) Exposure to Benzene at Marine Dock 1, Plaquemine, Louisiana during 1991. Sample # 12874 12875 12878 12881 12889 12891 13144 13154 13192 13194 13195 13196 13197 13205 13207 13208 13210 13211 13213 13214 13316 jo^a Assignment MS PSC PSC MS PSC MS PSC PSC PSC PSC MS MS MS MS PSC PSC MS PSC MS PSC PSC Date Aug-18 Aug-21 Aug-23 Aug-29 Aug-15 Aug-19 Dec-17 Dec-02 Dec-06 Dec-06 Dec-06 Dec-07 Dec-07 Dec-10 Dec-10 Dec-10 Dec-12 Dec-12 Dec-13 Dec-13 Dec-20 Concentration Duration ppm( V/V) Comments^ 15 68 Benzene disconnect only 40 13 Benzene disconnect only 30 374 Disconnect DC - 309 60 2.8 RIO-2400 Disconnect 30 5.4 Benzene disconnect only 20 168 Benzene disconnect only 9 17 Disconnect WEB- 103 Pygas 35 30 Benzene disconnect RIO - 2400 30 <0.02c Disconnecting lb-925 65 41 Rio-2400 Hemetric sampler used 45 26 Disconnect Benzene 15 70 Benzene barge disconnect 15 287 Sampling benzene barge 20 <0.04 Disconnect DC - 309 34 0.07 Disconnect Pygas DC-325 30 0.16 Disconnect DC-351 BTX 25 0.33 R10-2400 Disconnect 10 9.9 Disconnect Web-103 Pygas 1 1 17 Sampling RIO - 2400 35 2.4 Discharge DC-325 Pygas 75 <0.01 Disconnect NM 1001 c-5 Industrial __Hygiene_ Exposure. --Guideline Benzene OSHA PEL 8-hr. TWA OSHA STEL 1 ppm 5 ppm 8 MS = Marine Specialist SMS = Senior Marine Specialist PSC = Petroleum Service Corporation Tankerman b Respiratory protection was worn during all job tasks. c Detectable amount but below the limit of quantitation for the survey sampling conditions. DO 074709 CONFIDENTIAL RESTRICTED FOR USE WITHIN DOW PAGE 11 Tabl 3: R suits of Employe s' Tlme-W ighted Average (TWA) and Short Term Excursion (STEL) Exposure to 1,3-Butadiene at Marine Dock 1, Plaquemine, Louisiana during 1991. Sample # 13159 13191 13160 j0pa Assignment MS PSC PSC Date 12/5/91 12/5/91 12/5/91 Concentration Duration ppm( V/V) Comm ntsb 20 0.06 Sampling DC-540 30 2.1 Disconnect DC-540 210 0.11 Inhibiting & Load ing DC-540 Industrial __Hygjene... Exposure Guideline: 1,3-Butadiene ACGIH TLV 8-hr. TWA 10 ppm a MS = Marine Specialist PSC = Petroleum Service Corporation Tankerman b Respiratory protection was worn during all job tasks. 074710 CONFTOEHTTAl- RESTRICTED FOR USE WITHIN DOW PAGE 12