Document VG2yrkLe4Y1a7kzGv04rgapEo
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BUSINESS CONFIDENTIAL
PROJECT REPORT
"TEXAS CIT^ PLANT
TOXIC POLLUTAOTANAETsIS OF EPA SPLIT-SAMPLES TAKEN JUNE 12-15, 1978
DEC - 7AS78
RECD.
RVM
AUTHORSt HORK BY: SUPERVISOR:
S. A. Siegrist (20 B( E. Wilkes (2)
LJ.
C. J.
Boggs Priestley
W. C. Kuryla (3)
date: December 1, 1978 PROJECT HO: 510A16 FILE HO: 25749
SUMMARY
Toxic pollutant analyses were completed for these EPA split-samples taken at Texas City June 12-15, 1978.
Concentration, mg/1
Volatile Organics Benzene
1,2 Dichloroethane Ethylbenzene
Toluene
Dilute
Effluent
Marine
No. 3
Waste to
From
Terminal Olefins Gulf Coast O.P.D
140.0(a) 250.0
54.0 380.0(a)
160.0
(-) 34.0 58.0
0.69 0.72
(-) 0.006
0.27
(-) (-) (-)
Semi-Volatile Organics
Acenaphthene
0.16(a) 3.9
Acenaphthylene Anthracene
(-) 18.0 0.009(a) 29.0
Bis-2-chloroethyl ether (-)
(-)
Dioctyl phthalate 2.2 2.8
Fluoranthene Fluorene Isophorone
(-) (-) 23.0
6.6 13.0
(-)
Naphthalene
0.26
57.0
Phenol
57.0(a)
1.4
Polynuclear Aromatic
Hydrocarbons Pyrene
(-) 17.0 (-) 12.0
0.05 0.12 0.12 0.71 0.10 0.01 0.058 (-) 0.92 0.047
(-) 0.028
(+) (+) 0.14(1 (+) (-) (-) (-) (-) 0.011 2.6
(-) (-)
Con * t.
RESEARCH AMO DEVELOPMENT DEPARTMENT CHEMICALS AND PLASTICS
UNION CARBIDE CORPORATION SOUTH CHARLESTON, WEST VIRGINIA
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Metals
'Chromium
Copper Silver
Thallium Zinc
i
Dilute
Effluent
Marine
No. 3
Waste to
From
Terminal Olefins Gulf Coast O.P.D.A.
0,20 0.48 0.20 <0,35 2,0
0.52 0.15 0.15 <0.35 0.32
4.2
0.20 0,12 <0.35 0,89
0.66 0.15 0.15 <0.35 0.31
(+) Detected by GC-MS analysis only. (-) Not detected by GC-MS analysis.
(a) The compound was detected as a multi-component peak, and the concentration may be high,
INTRODUCTION
EPA sampled the Texas City plant June 5-15,
1978 for the verification phase of the BAT
program. This sampling and analysis was to quantify those
toxic pollutants detected by the screening analysis August 9-12,
1977, Carolyn Harvey, from the Texas City Plant, had requested
that R/D take split-samples at four locations - Dilute Waste to
Gulf Coast, Effluent from 0,P,D.A,, No, 3 Olefins Unit, and
Marine Terminal - to provide a comparative analysis with EPA's
results,
DISCUSSION
Toxic pollutants were analyzed using the EPA
protocol methods for screening wastewaters (1).
The toxic organic pollutants were identified by GC-MS analysis,
then quantified by a separate GC-FID analysis (Table I), The
toxic metal pollutants were identified by flame or flameless
atomic absorption analysis (Table II),
Four isomers of polynuclear aromatic hydro carbons (PNAs) were detected by GC-MS, but not specifically identified, in the No, 3 Olefins sample. The total PNA con
centration contributed by the Isomers was estimated at 17 mg/1. These PNA isomers were not detected in the other samples.
The EPA screening analysis in August 1977 had
detected metals at concentrations as high as 27 mg/1,. Five of the EPA toxic metals - chromium, copper, silver, thallium, and zinc - were analyzed by flame or flameless atomic absorption. Chromium was detected in the Dilute Waste to Gulf Coast at a concentration of 4,2 mg/1. Zinc was detected in the Marine Terminal at a concentration of 2,0 mg/1. All other metals were detected at concentrations less than 1,0 mg/1.
EPA. planned to analyze for the toxic.pollutants using specific methods submitted for the verification phase. The methods include analysis of phthalate esters, polynuclear aromatic hydrocarbons, volatile organics, and metals.
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PROJECT NO, 510A16
Flame Ionization, electron capture and ultra-violet detectors would be used to detect or `'Identify*' the toxic pollutants.
No identifications would be made by GC-MS analysis. These methods have not been validated, and their precision and
accuracy are not known. EPA asked the Texas City plant and R/D to use these methods for the split analysis, so that the data could be used as a partial validation of the methods. R/D chose not to use these specific methods. The GC-MS analytical scheme used by the Environmental Analytical Group unequivically identifies the toxic pollutants to a detection limit of 10 ppb, A separate GC-FID analysis provides an accurate and precise quantitative analysis of the identified toxics, A comparison of R/D and EPA'A results should agree within the same order of magnitude,
EXPERIMENTAL
EPA sampled at Texas City June 5-15, 1978,
sampling procedures were documented in an
earlier memorandum (2). Grab samples were taken for volatile
organics analysis (VOA). Composite samples were taken manually
and with automatic samplers for semi-volatile organics analysis.
Four split-samples were taken June 12-15 and the composites
varied with each one: (1) The Marine Terminal was taken as a
grab sample each of the three days; (2,3^ TheNo. 3 Olefins
Unit and the Dilute Waste to Gulf Coast samples were composited
with an ISCOS automatic sampler; threq 24 hour composites were taken; (4) the Effluent from O.P.D.A. was taken as a grab
sample each day and combined for a 72-hour composite.
!H
Volatile Organics
All grab samples collected for a particular wastewater were combined in the lab prior to analysis. Thus, VOA concentrations represent a three-day average value. A 5.0 ml volume was purged with nitrogen, adsorbing the volatile organics on Tenax/silica gel columns. The organics were ther mally desorbed atf 250C and chromatographed using these con ditions:
Column: 0.2% Carbowax 1500 on 60/80 , Carbopack C; glass; 6 ft. x 2mm I.D.
Detector: Mass spectrometry, then flame ionization.
A direct aqueous injection technique was used to confirm concentrations detected greater than 5 mg/1.
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BUSINESS CONFIDENTIAL 4 PROJECT NO. 510A16
^ Semi-Volatile Organics
Equal portions of the three 24-hour composite samples taken for a particular wastewater were combined for a final volume of 2.0 liters. The semi-volatile organics con
centrations represent a three-day average value. The organics were separated by liquid - liquid extraction at pH 11 and 2 with methylene chloride. These gas chromatographic conditions were used:
Columns:
3% OV-17 on 100/200 Supelcoport, glass, 6 ft. x 2 mm I.D.
Superpak 20 M, glass, 6 ft. x 2mm I.D.
Detectors: Mass spectrometry, then flame ionization.
Metals
An aliquot of each sample was digested with acid, then analyzed by flame or flameless atomic absorption.
REFERENCES
1. "Sampling and Analysis Procedures for Screening of Industrial Effluents for Priority Pollutants" EPA Publication, April, 1977,
2. Siegrist, S. A., "EPA Sampling at the Texas City Plant, June 5-16, 1978" B/D Memorandum, July 21, 1978, File No. 25313.
ACKNOWLEDGEMENTS The laboratory assistance of L. J. Priestly for GC-MS analysis and J. C. Boggs for
quantitative analysis is greatly appreciated. The authors also thank R. A. Singer and D. E. Nixon for_the metals
analysis.
B. E. Wilkes Manuscript Date: November 14, 1978 Date Typed: December 1, 1978
Attachments: 2 Tables
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TABLE I
TOXIC ORGANIC POLLUTANTS DETECTED IN TEXAS CITY/EPA SPLIT-SAMPLES FROM JUNE 12-15, 1978
Concentration, mg/1
Dilute
Effluent
Marine
No. 3
Waste to
From
Terminal Olefins Gulf Coast O.P.D.A.
Volatile Organics
Benzene 1, 2 Dichloroethane Ethylbenzene Toluene
140.0(a) 250.0
54.0 380.0(a)
160.0
(-) 34.0 58.0
Seml-Volatile Organics
Acenaphthene
0.16(a) 3.9
Acenaphthylene
(-) 18.0
Anthracene
0.009(a) 29.0
Bis-2-chloroethyl ether (-)
(-)
Dioctyl phthalate 2.2 2.8
Fluoranthene Fluorene
<-) 6.6 (-) 13.0
Isophorone
23.0
(-)
Naphthalene
0.26
57.0
Phenol
57.0(a)
1.4
Polynuclear Aromatic
Hydrocarbons
(-) 17.0
Pryene
_ <t)
12.0
0.69 0.72 (-) 0.006
0.05 0.12 0.12 0.71 0.10 0.01 0.058 (-) 0.92 0.047
(-) 0.028
0.27 (-) (-) (-)
(+) (+) 0.14(a) (+) (-) (-) (-) (-) 0.011 2.6
(-) (-)
(+) Detected by GC-MS analysis only.
(-) Not detected by GC-MS analysis. (a) The compound was detected as a multi-component peak, and
the concentration may be high
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TABLE I
TOXIC METALS DETECTED IN TEXAS CITY/EPA SPLIT-SAMPLES FROM JUNE 12-15, 1978
Concentration^ m^/l
Dilute
Effluent
Marine
No. 3
Waste to
From
Terminal Olefins Gulf Coast O.P.D
Chromium Copper Silver Thallium Zinc
0.20 0.48 0.20 ND(a) 2.0
0.52 0.15 0.15
ND 0.32
4.2 0.20 0.12
ND 0.89
0.66 0.15 0.15
ND 0.31
(a) Thallium was not detected (ND) at concentration greater than 0.35 mg/1, the thallium detection limit by flame atomic absorption.
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DISTRIBUTION: Mr. F. D. Bess, 3005 Ms. Carolyn Harvey, 515 Mr. J. C. Hovlous, 3002 Mr. J. B. Johnson, 511 Mr. R. T. Kramer, 3005 Mr. J. B. Leverton, 515 Mr. E. R. Lashley, 511 Mr. D. C. Macauley, 511 Ms. M. G. Manettl, NYO-46 Mr. R. Van Mynen, NYO-21 Ms. Marilyn Pineda, 515 Mr. R. R. Rankin, 515 Mr. J. C. Ronnander, 515
* Mr. J. J. Smith, 511 Mr. W. F. Tully, 511 Mr. B. E. Wilkes, 511 Mr. B. A. Young, 511
Summary Only
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