Document x1q1jdmJBBGynd6D23ok7dXqb
INDUSTRIAL HYGIENE REPORT TEXAS OPERATIONS
DOW CHEMICAL U.SA
FILE NUMBER: OC-3138-89C DATE ISSUED: JULY 31, 1990 PLANTCODE: 58274
TITLE :
EVALUATION OF EMPLOYEE EXPOSURES TO CHLORINATED HYDROCARBONS AT THE UNIT I/VINYL CHLORIDE PLANT, OYSTER CREEK , 1989
AUTHOR(S) :
REVIEWER(S): SUMMARY
/[} A &CLM. A. BLUE
.
T. W. PARSONS
Personnel monitoring was conducted in 1989 to evaluate employee exposures to vinyl chloride, ethylene dichloride, ethyl chloride, 1,1,1-trichIoroethane, 1,1,2-trichloroethane, and carbon tetrachloride. Both 8hour time-weighted average (TWA) and short-term exposures were evaluated.
Eight-hour TWA exposures were measured for Process Technicians and Contractors. The average exposures for each job classification were significantly less than the acceptable guidelines for each respective chemical with two exceptions. The Technicians in the loading area exceeded the OSHA Action Level for vinyl chloride and the Contractors exceeded the OSHA Permissable Exposure Limit (PEL) for ethylene dichloride (EDC). Quarterly monitoring is required for the Loading Technicians.
Short-term personal exposures were monitored during specific job activities including process sampling and analysis, tank car unloading activities, and during various maintenance activities. Exposures were within acceptable guidelines with a few exceptions. Process Technicians in the direct chlorination and repair areas exceeded the Short-Term Exposure Limit (STEL) for EDC and Process Technicians in the loading area and vinyl distillation area exceeded the STEL for vinyl chloride. New sampling systems have been implemented in the loading and direct chlorination areas to reduce exposures. Employees wear full face airline respirators whenever there is a significant potential for exposure.
Recommendations include follow-up monitoring to verify the effectiveness of the new sampling systems.
All personnel of Unit I have been informed of the results of this survey. DISTRIBUTION:
L. J. Burmeier, OC-101 W. L. Myles, OC-lOl C. A. Armstrong, OC-101 J. H. Lippman, OC-1120 R. A. Jones, OC-1120 H. Robles, Jr, OC-101
D. E, Cragar, B-101 C. K. Browdy, B-101 G. W. Engdahl, 1803, Midland *L. W. Rampy, 1803. Midland *J. E. LeBeau, 1803, Midland
'Cover Sheet Only
RESTRICTED FOR USE WITHIN THE DOW CHEMICAL COMPANY ONLY
DO "128386 CONFTDFNTTAl
IHS File #OC-3138-89C
Page 2
EVALUATION OF EMPLOYEE EXPOSURES TO CHLORINATED HYDROCARBONS AT THE UNIT I/VINYL CHLORIDE PLANT, OYSTER CREEK, 1989
INTRODUCTION
Personnel monitoring was conducted at the Unit I/Vinyl Chloride plant to evaluate employee exposures to
vinyl chloride, ethylene dichloride, ethyl chloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, and carbon tetrachloride. Both short-term and 8-hour time-weighted average (TWA) exposures Were evaluated
as outlined in the 1988-89 protocol for Unit I (IHS File #00-3138-89).
I
RESULTS AND CONCLUSIONS
,
1. Results of 8-hour TWA personnel monitoring are summarized in Table I. Process Technicians from seven areas of the plant and Contractors were monitored for exposures to vinyl chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, carbon tetrachloride, and ethylene dichloride. The average exposures from all monitored job classifications were less than the acceptable guidelines with the two exceptions. The Loading Technicians exceeded the OSHA Action Level for vinyl chloride of 0.5 ppm and the Contractors exceeded the OSHA Permissable Exposure Limit (PEL) of 1 ppm for ethylene dichloride (EDO).
2. Individual 8-hour TWA exposures are summarized in Table II. Individual exposures were less than the acceptable guidelines with a few exceptions. One vinyl distillation technican and four leading technicians had exposures exceeding the OSHA PEL for vinyl chloride. The reason for the Vinyl Distillation technician exposure that exceeded the guideline was not identified. Short-term monitoring identified tank car sampling/analysis and Shimech meter test as a possible reason for the Loading Technician exposures.
3. One contractor sample exceeded the OSHA PEL for EDC. On the day in which this exposure occurred the contractor was breaking up cement with chlorinated hydrocarbons below it. The contractor exposure was potential as full face airline respirators were used while breaking up the cement.
4. Short-term personal exposures were monitored for Process Technicians during specific job activities including process sampling and analysis, tank car unloading activities, quench pump removal, E-35 head removal, and during the repair of a compressor (C-203). Results are summarized in Table III.
5. Short-term exposures were below acceptable guidelines with a few exceptions. The Process Technicians in the direct chlorination area had exposures that exceeded the short-term exposure limit (STEL) for EDC during sampling and analysis. Since the completion of this survey, a new sampling system with quick connect fittings has been installed in this area. Analysis procedures were also changed that included filling the sample vials in a laboratory hood as opposed to on an open lab bench.
6. Repair Technicians exceeded the STEL for EDC during the quench pump removal and E-35 (exchanger) head removal. These exposures were potential as full face airline respirators were used during both tasks.
7. One Process Technician in the vinyl distillation area had an exposure that exceeded the STEL for vinyl chloride. On the day in which this exposure occurred, the sample bomb O ring failed, causing a very brief elevated exposure.
8. One Process Technican in the loading area had an exposure above the STEL for vinyl chloride. A new sampling system remote from the tank cars has been installed in the loading area to reduce exposures.
DO 1 2-838? PjFHT T Al
f,ONF
IHS File #OC-3138-89C
Page 3
EVALUATION OF EMPLOYEE EXPOSURES TO CHLORINATED HYDROCARBONS AT THE UNIT I/VINYL CHLORIDE PLANT, OYSTER CREEK, 1989
RECOMMENDATIONS
1. Follow-up excursion monitoring needs to be conducted for Process Technicians in the direct chlorination area to evaluate the effectiveness of the new sampling system in reducing exposures to EDO.
2. The average exposure for Loading Technicians exceeded the Action Level for Vinyl Chloride of 0.5 ppm, therefore quarterly monitoring is required. However, monthly monitoring is recommended as a significant number of the individual 8-hour TWA exposures exceeded the PEL of 1 ppm.
3. Follow-up 8-hour TWA and excursion monitoring needs to be conducted for Loading Technicians to verify the effectiveness of the new sampling system in the tank car unloading area in reducing exposures to vinyl chloride.
4. Full face airline respirators should continue to be used for line openings and manway removals.
5. An improved maintenance system for the sample bombs needs to be developed to reduce the chance of leaks.
EXPOSURE EVALUATION CRITERIA
The evaluation of the chemical exposure levels in this survey was based on the following criteria:
AGENX Vinyl Chloride
Ethylene Dichloride
1,1,1-Triehioroethane
Ethyl Chloride 1,1,2-Trichloroethane Carbon Tetrachloride
EXPOSURE GUIDELINE
1 ppm - 8-hour TWA 5 ppm - STEL 1 ppm- 8-hour TWA 2 ppm - STEL 350 ppm - 8-hour TWA 450 ppm - STEL 1000 ppm - 8-hour TWA 10 ppm - 8-hour TWA, Skin 2 ppm - 8-hour TWA
SOURCE
OSHA - PEL OSHA - PEL OSHA - PEL OSHA - PEL OSHA - PEL OSHA - PEL OSHA - PEL OSHA - PEL OSHA - PEL
Eight-hour TWA exposures represent time-weighted average airborne concentrations for an 8 hour workday, 40 hour work week. Limited exposures greater than the 8-hour TWA are acceptable for most materials as long as the 8-hour TWA exposure does not exceed the acceptable guideline. Short-term exposure limits (STEL) are 15 minute TWA's and are established for materials which could cause adverse effects from brief exposures to elevated concentrations For chemicals in which a short term acceptable guideline does not exist, excursion concentrations should not exceed three times the 8-hour TWA for more than a total of 30 minutes and under no circumstances should they exceed five times the 8-hour TWA. A "skin" ranking indicates the material may be absorbed through the skin and may cause effects other than at the point of contact with the skin.
DO 1P8888 OONFTDFNTTAl
IHS File #OC-3138-89C
Page 4
EVALUATION OF EMPLOYEE EXPOSURES TO CHLORINATED HYDROCARBONS AT THE UNIT I/VINYL CHLORIDE PLANT, OYSTER CREEK, 1989
SAMPLING AND ANALYSIS METHODOLOGY
Both 8-hour TWA and excursion samples were collected on 1 gram charcoal tubes using an air sampling pump. Pumps were calibrated before and after use at 50 cc/min for the 8-hour TWA samples and 200 cc/min for the excursion samples ( as outlined in DLI-IHM-83-25A). Samples were collected by lab personnel from Unit I. Analysis was performed by Analytical Services.
Samples were also analyzed for vinylidene chloride and benzene however the data was inconclusive and the monitoring will be repeated.
on
-1 TDFM-n
CONF
IHS FILE #OC-3138-89C
TABLE I SUMMARY OF AVERAGE 8-HOUR TWA EXPOSURES
UNIT I/VINYL CHLORIDE, 1989
JOB CLASS/
NUMBER OF
JOB CODE________________ SAMPLES
Process Technician
Oxychlorination/ 127005800X
Direct Chlorination/ 12700580DC
Vinyl Distillation/ 12700580VD
Vinyl Furnace/ 12700580VIF
By-Product Recovery/ 12700580BPR
Loading/ 12700580LO
Repair/ 12700580R
Contractor/ Utility Man
4 7 7 4 4 10 4 2
8-HOUR TWA CONCENTRATION (PPM)1-2
VINYL CHLORIDE
ETHYLENE DICHLORIDE
ND (0.07) 0.10 0.40 0.09 0.09 0.94 0.17 0.09
0.06 0.25 0.11 0.18 0.14 ND (0.04) 0.36 1.7
IHG (8-HR TWA)
1
1
* Ethyl Chloride, 1.1.1-Trichloroethane, 1,1,2-Trichloroethane, and Carbon Tetrachloride were also monitored however all samples were less than 5% of their respective IHG's
ry
ND = non-detectable; The detection limit is in parenthesis.
CoOnNFTDFNTTAl,
IIIS RLE #OC-3l38 89C
TABLE II SUMMARY OF INDIVIDUAL *-HR TWA PERSONNEL EXPOSURES
UNIT I/VINYL. CHLORIDE, 1989
JOB MASTER
CLASSIFICATION------------------ NUMJlE-BDate
SAMPLE
time imini
8-HOUR TWA CONCENTRATION fEEMl1-2 vinyl chloride fthylent:dichi.pride
Process Tech.. Oaychlorination Direct Chlorination
Vinyl Distillation
Vinyl Furnace
202732 202732 202070 141893
202468 206683 206685 206870 206870 206142 206683
202182 202182 144694 202432 202182 144694 202432
202462 202407 2063 3 B 206338
07-19-89 07-20*89 07-28-89 08-08-89
06-16-89 06-20-89 06-22-89 06-23-89 07-13-89 07-14-89 08-11-89
07-19-89 07-20-89 07-28-89 08-08-89 09-02-90 09-15-89 10-17-89
10-05-89 10-06-89 10-11-89 10-18-89
480 480 480 425
480 472 480 480 480 480 480
480 480 480 480 480 520 500
480 480 47 5 480
S3 to to to
to to to to
0.19 0.13 ND
0.12 0.89 0.16 1.1 0.11 0.38
to
0.16 ND ND ND
0.07 0.06 0.06 ND
0.11 0.34 0.23 0.44 0.35 ND 0.26
0.05 0.07 0.17 0.09 0.08 0.24 0.07
0.31 ND 0.20 0.16
By-product Recovery Loading
206801 202221 206312 202221
202337 202101 202337
202101 202101 202337 141102 202337 202337 141102
10-05-89 10-06-89 10-11-89 10-18-89
03-21-89 03-21-89 05-1 1-893
03-1 1-893 08-11-89 08-11-89 10-19-89 11-01-89 11-03-89 11-09-89
480 495 490 480
420 420
420
420 425 423 480 495 500 465
0.14 ND ND ND
0.91 0.70
1.2
1.6 0.47 0.77 0.49 1.0 1.4 0.88
0.30 0.07 0.13 0.04
ND ND
ND
ND ND ND ND ND ND ND
Repair Conlractor/Utiility Man
206813 202433 281545 202800
11-28-89 11-28-89
11-30-89 10-19-89
606-10-2084 10-27-89 461-89-1577 11-01-89
500 500 465 450
410 410
0.16 0.19 ND 0.24
0.10 0.07
0.35 0.54 0.49 ND
3.2 0.26
IHG (8-HR TWA)
1
* Ethyl Chloride, 1,1,1-Trichloroethane, 1,1,2-Trichloroethane, and Carbon Tetrachloride were alio monitored however all samples were less than 3% of their respective IHG's
ND non-deiectablc; Detection limits are as follows; Vinyl Chloride - 0.07 ppm. Ethylene Dichloridc 0.04. ^ Shintech meter test was performed during the sampling period; full face airline respirators were used during the meter test.
DO 178391 OONFTDFNT TAl
IHS FILE OOC-3138-89C
table hi
SUMMARY OF PROCESS TECHNICIAN SHORT-TERM EXPOSURES UNIT 1, 198*
JB
MASTER
SAMPLE
CLASS----------------------------NUMB KB---------QAXE------------TIME fMINl
Oxychlorination
202732 202732 202070
07-19-89 07-20-89 07-28-89
I7 30 15
Direct chlorination
202468 206685 206685 206870 206870 206142 206685
06-16-89 06-20-89 06-22-89 06-23-89 07-13-89
07-14-89 08-11-89
AVE. a
24 17 20 24 17 22 35
Vinyl distillation
202182 202736 1 446V4
202432 202182 144694 202432
07-19-89 07-20-89 07-28-89 08-07-89 09-02-89 09-15-89 10-17-89
AVE. =
15 20 60 60 21 45 30
l furnace
202462 206558 2065 5 8
10-05-89 10-11-89 10-18-89
AVE. =
15 20 15
By-product recovery
206801 2063 1 2 202221
10-05-89 10-11-89 10-18-89
AVE. s
30 40 30
Loading area
141102 202337 202337
141102
10-19-89 11-01-89 1 1-03-89 11-09-89
AVE. =
45 20 20 40
AVE. =
141102 202337 202337
141102
10-19-89 11-01-89
11-03-89 11-09-89
20 20 25 20
AVE- =
141102 202337 202337 141102
10-19-89 1 1-01-89 11-03-89 11-09-89
25 20 25 25
AVE. =
SHORT-TERM CONCENTR ATION fPPMlM
VINYL
ETHYLENE
CHLORIDE
niCHLORFDEIOB TASK
ND (0.39) ND (0.22) ND (0.44)
0.02 0.35 0.84
Sampling/analytit
Sampling/anilyiii Sampling/analyiii
0.35
ND (0.67) ND (0.97) ND (0.33) 0.02 1.3 ND (0.31) ND (0.30)
0.40
1.2 6.6 3.8 4.1 4.6 ND (0.19) 2.7
Sampling/analysii
Sampling/analytit Sampling/analytit Sampling/analysii Sampling/analytit Sampling/analysii Sampling/analysis
0.54
3.3
3.3 16 0.61 ND (0.09) ND (0.34) 0.44 ND (0.22)
ND (0..12) 0.18 0.71 0.15 0.71 0.55 0.19
Sampling/analytit Sampling/analytit Sampling/analytit Sampling/analytit Sampling/analytit Sampling/analytit Sampling/analytit
3.0 0.37
ND (0.44) ND (0.33) ND (0.43)
0.40
ND (0.28) 1.9 ND (0.28)
0.82
Sampling/analytit Sampling/analytit Sampling/analytit
0.38 ND (0.17) ND (0.17)
0.24
0.75 0.89 0.73
0.79
Sampling/analytit Sampling/analytit Sampling/analytit
0.22 0.51 1.1 0.17
0.50
ND (0.10) ND (0.21) ND (0.21) ND (0.11)
ND (0.16)
T/C Hook-up T/C Hook-up T/C Hook-up T/C Hook-up
1.5
11 3.0 0.43
ND (0.21) ND (0.21) ND (0.21) ND (0.21)
T/C Sampling T/C Sampling
T/C Sampling T/C Sampling
4.0
0.4 0.96 0.78 0.28
ND (0.21)
ND (0.17) ND (0.21) ND (0.17) ND (0.17)
T/C Ditcooneci T/C Ditconnect T/C Ditcooneci T/C Ditconnect
0.63
ND (0.18)
00 C-ONF
IHS FILE #OC-3138-89C
JOB CLASS
Repair
TABLE ID (CONTINUED)
MASTER
SAMPLE
flUMJBEB--------- DATE-------------- time fMiNi
206813 202435
11-28-89 11-28-89
17 16
AVE. =
202468
11-30-89
45
202800
10-19-89
15
SHORT-TERM CONCENTRATION IPPMI1*2
VINYL
chloride
ETHYLENE
bichloride
JOB
task
ND (0.39) 3.7
0.61 7.5
kjucneh Pump iQuench Pump
2.1 0.31 ND (0.43)
4.1 13.9 ND (0.27)
i E-35 Head Removal | C-203 Repair
IHG (8-HR TWA) = IHG (STEL) =
11 52
* Ethyl Chloride, 1,1,1-Triehloroethine, 1,1,2-Trichlorocthane, and Carbon Tetrachloride were alio monitored however all samples were less than 5% of their respective IHC's
O non-detectablc; Detection limits arc in parenthesis
DO 138393 CONFTDFNTTAI