PB88-125901
Case Studies of Hazardous Waste
Treatment to Remove Volatile Organics
Volume 2
Research Triangle Inst.
Research Triangle Park, NC
Prepared for
Environmental Protection Agency, Cincinnati, OH
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
NTIS
-------
PB8b-125901
EPA/600/2-87/094b
November 1987
CASE STUDIES OF HAZARDOUS WASTE TREATMENT
TO REMOVE VOLATILE ORGANICS: VOLUME II
Prepared by
C. Allen, M. Branscome, C. Northelm, K. Leese, and S. Harkins
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, NC 27709
Contract No. 68-02-3992
Task 50
Prepared for
Benjamin L. Blaney
Proiect Officer
Thermal Destruction Branch
Alternative Technologies Division
HAZARDOUS WASTE ENGINEERING RESEARCH LABORATORY
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OH 45268
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1 PCrORT NO 2
EPA/600/2-87/094b
3 RECIPIENT'S ACCESSIOheNO.
1 i ; ; ' - . '\ij
t title anc subtitle
Case Studies of Hazardous Waste Treatment to Remove
Volatile Organics: Volume II
5 REPORT DATE -
November 1987
6 PERFORMING ORGANIZATION CODE
7 AUTHOR(S)
C. Allen, M. Branscome, C. Northeim, K. Leese, and
S. Harkins
8. PERFORMING ORGANIZATION REPORT NO.
3 performing organization name and aooress
Research Triangle Institute
P.Q. Box 12194
Research Triangle Park, NC 27709
10 PROGRAM ELEMENT NO.
11 CONTRACT/GRANT NO
68-02-3992, Task 50 -
12. SPONSORING agency name and aooress
Hazardous Waste Engineering Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA-600/12
is. supplementary notes
16 abstract
Case studies are presented for treatment of refinery wastes in a pilot-scale thin-
film evaporator, the removal of volatiles from industrial wastewater for two steam
strippers, and the removal of semi vol atiles from water by steam stripping followed by
liquid-phase carbon adsorption. This report provides data on removal efficiency, air
emissions, process residuals, treatment costs, and process limitations. Details on
sampling and analytical procedures, quality assurance, and process data are contained
in the Appendixes (Volume II).
17 KEY WORDS AND DOCUMENT ANALYSIS
i DESCRIPTORS
b IDENTIFIERS/OPEN* ENDED TERMS
c COSATi Field'Crouc
Hazardous waste
Volatile organic compounds
Treatment or pretreatment
Thin-film evaporation
Steam stripping
15 DISTRIBUTION ST AT6MENT
RELEASE TO PUBLIC
19 SECURITY CLASS (This Report)
UNCLASSIFIED
21 NO OF PAGES
116
JO SECURITY CLASS (Thu page/
UNCLASSIFIED
22 PRICE
EPA Form 22JO-1 (»-71)
1
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NOTICE
The information 1n this document has been funded wholly or in part by the
United States Environmental Protection Agency under Contract 68-02-3992, Task
No. 50, to Research Triangle Institute. It has been subject to the Agency's
peer and administrative review, and has been approved for publication as an
EPA document. The use or mention of trade names or commercial products does
not constitute an endorsement or recommendation for use.
ii
-------
Today's rapidly developing and changing technologies and Industrial
products and practices frequently carry with them Increased generation of
solid and hazardous wastes. These materials, 1f Improperly dealt with, can
threaten both public health and the environment. Abandoned waste sites and
accidental releases of toxic and hazardous substances to the environment also
have Important environmental and public health Implications. The Hazardous
Waste Engineering Research Laboratory assists 1n providing an authoritative
and defensible engineering basis for assessing and solving these problems.
Its products support the policies, programs, and regulations of the Environ-
mental Protection Agency, the permitting and other responsibilities of State
and local governments and the needs of both large and small and businesses in
handling their wastes responsibly and economically.
This report presents the results of field assessments of three waste
treatment techniques that have the potential for use In control of emissions
of volatile organic compounds from hazardous waste facilities by removing
those compounds from the waste streams. Those treatment techniques are thin-
film evaporation, steam stripping, and steam stripping with carbon adsorption.
The report 1s Intended for use by government agencies which are considering
ways to reduce emissions from hazardous waste facilities and by facility
operators and managers who wish to do the same. For additional Information,
please contact the Alternative Technologies Division of the Hazardous Waste
Engineering Research Laboratory.
Thomas R. Hauser. Director
Hazardous Waste Engineering Research Laboratory
-------
ABSTRACT
Three treatment processes were Investigated for the removal of volatile
organic (VO) compounds from -hazardous waste: th1n-f11m evaporation, steam
stripping, and steam stripping with carbon adsorption. The data collected
Included the VO removal effectiveness, air emissions from the process, cost,
and process limitations.
The th1n-f11m evaporator (TFE) study was a pilot-scale evaluation of the
TFE for removal of VO from petroleum refinery wastes. The study was performed
under different controlled conditions at three temperatures, three flow rates,
and under both vacuum and atmospheric pressure. The removal of volatile com-
pounds was greater than 99 percent, and the removal of semivolatiles ranged
from 10 to 75 percent depending upon the processing conditions. When the
system was operated under vacuum, some carryover of the feed resulted in a
condensate that was a milky-white emulsion, which would require additional
treatment to separate the oils and water. Vent rates from the condenser were
found to depend on the type of waste and the quantity of light hydrocarbons,
which are difficult to condense. The cost estimates for the TFE plus land
treatment of the residuals yielded costs that were comparable to or less than
the cost of land treating the original waste without pretreatment to remove
VO.
Two full-scale steam strippers used to treat Industrial wastewater
containing about 6,000 ppm of purgeable VO were tested. The tray column
stripper processed about 850 L/min of water that contained primarily ethylene
dichloride and chloroform. Total V0 removal averaged about 99.8 percent with
an average concentration of 9.7 ppm in the bottoms. The condenser removed
about 99 percent of the V0 from the vapor and yielded a vent rate of about 20
Mg/yr. The packed column steam stripper proce-ssed about 42 L/min of water
that contained primarily methylene chloride and chloroform. Total V0 removal
averaged 99.999 percent with an average concentration of less than 37 ppb in
the bottoms. The condenser removed about 91 percent of the organic vapors and
yielded a condenser vent rate of 11 Mg/yr. Emissions from the solids decanter
and storage tank were estimated as 46 Mg/yr. The tray column stripper proc-
essed water containing 1.4 g/L of filterable solids compared to 0.01 g/L for
the packed column. Costs for the small unit were confidential; the costs for
the larger steam stripper were about $0.89/1,000 L treated.
The steam stripping/carbon adsorption unit was used to remove semivola-
tiles from water, which contained nitrobenzene, 2-nitrotoluene, and 4-
nitrotoluene. Steam stripping reduced the concentration from 634 ppm to 48
ppm, a reduction of 92 percent. Liquid-phase carbon adsorption decreased the
concentration in the bottoms to below detection limits (0.8 ppm) and yielded
an overall removal efficiency of greater than 99.6 percent. Maximum air emis-
sions were estimated as 35 kg/yr. The total cost of treatment was estimated
as $8.90/1,000 L treated.
This report 1s submitted 1n partial fulfillment of EPA Contract Number
68-02-3992, Task 50, by Research Triangle Institute under the sponsorship of
the U.S. Environmental Protection Agency. This report covers a period from
April 1986 to May 1987, and work was completed as of June 1987.
i v
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TABLE OF CONTENTS VOLUME I
Notice ii
Foreword i i i
Abstract iv
LIST OF FIGURES vii
LIST OF TABLES viii
SECTION
1 INTRODUCTION 1-1
Background 1-1
Purpose of the Program 1-1
Procedures 1-2
Scope of the Report 1-2
2 CONCLUSIONS 2-1
General Conclusions 2-1
Thin-film evaporator (TFE) Conclusions . 2-1
Plant I Steam Stripping Conclusions 2-4
Plant H Steam Stripping Conclusions 2-5
Plant G Steam Stripping/Carbon Adsorption
Conclusions 2-6
3 RESULTS OF THE THIN-FILM EVAPORATOR TESTS 3-1
Description of Pilot Facility 3-1
Tests Performed with Thin-film Evaporators 3-4
Process Residuals 3-33
Bottoms Sludge 3-33
Organic Condensate 3-33
Aqueous Condensate 3-34
Cost of Thin-film Evaporation 3-34
4 FIELD TEST RESULTS: STEAM STRIPPING 4-1
Results for Plant I 4-1
Process Description for Plant I 4-1
VO Removal From Water 4-3
Air Emissions 4-7
Results for Plant H 4-21
Process Description for Plant H 4-21
Removal of VO From Water 4-23
Condenser Efficiency 4-31
Process Costs and Limitations 4-31
v
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TABLE OF CONTENTS VOLUME I (Continued)
5 FIELD TEST RESULTS: STEAM STRIPPING/CARBON
ADSORPTION 5-1
Site and Process Description for Plant 6 5-1
Results for Plant G 5-5
Process Stream Composition 5-5
Removal Efficiencies of the Steam Stripper-Carbon
Adsorber 5-5
Process Limitations 5-5
Process Residuals 5-11
Air Emissions 5-11
Liquid and Solid Residuals 5-14
Process Cost 5-14
6 PROCESS LIMITATIONS AND COMPARISONS 6-1
Process Limitations for Thin-f11m Evaporation 6-1
Process Limitations for Steam Stripping 6-1
Comparisons 6-2
7 REFERENCES 7-1
TABLE OF CONTENTS VOLUME II
APPENDIX A SAMPLING AND DATA COLLECTION PROCEDURES A-l
APPENDIX B SUMMARY OF ADDITIONAL MEASUREMENT B-l
APPENDIX C PROCESS DATA C-l
APPENDIX D ANALTYICAL PROCEDURES D-l
APPENDIX E QUALITY ASSURANCE E-l
vi
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LIST OF FIGURES
NUMBER PAGE
3-1 Configuration of test equipment 3-2
3-2 Condensate flow rates as a function of feed rate at
150 *C 3-9
3-3 Bottoms flow rate as a function of feed rate at 150 *C 3-10
3-4 Condensate flow rates as a function of feed rate at
320 'C 3-11
3-5 Bottoms flow rate as a function of feed rate at 320 *C 3-13
3-6 Condensate flow rates as a function of feed rate at
230 *C 3-14
3-7 Bottoms flow rate as a function of feed rate at 230 *C 3-15
4-1 Simplified schematic of sampling points 4-2
4-2 Schematic of steam stripper and sampling locations 4-22
5-1 Plant layout (not to scale) 5-2
5-2 Flow diagram of continuous steam stripping and carbon
absorption unit 5-3
vii
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LIST OF TABLES
NUMBER PAGE
2-1 Summary of Steam Stripper Performance Purgeable Volatile
Organics 2-2
2-2 Summary of Steam Stripper and Carbon Adsorber Performance
for Semi volatlles 2-3
2-3 Summary of Thin-Film Evaporator Results for Two
Temperatures 2-3
3-1 Process Equipment Specifications 3-3
3-2 Test Matrix for Th1n-F1lm Evaporator Tests 3-5
3-3 Run Process Conditions and Flow Rates 3-7
3-4 Condensate Organic/Aqueous Splits 3-8
3-5 Reduction in Headspace Volatile Organic Concentrations,
From Onsite GC Analysis of Headspace 3-18
3-6 Reduction 1n Headspace Volatile Organic Concentrations,
Bacharach TLV Sniffer Results 3-19
3-7 Volatile Analysis of Liquid and Sludge Process Samples
(CompuChem Data) 3-20
3-8 Semivolatile Analysis of Liquid and Sludge Process
Samples (CompuChem Data) 3-22
3-9 Metals Analysis of Liquid and Sludge Process Samples
(CompuChem Data) 3-23
3-10 Performance of Th1n-Fi1m Evaporator, Volatile and
Semivolatile Compounds, Run #5 3-24
3-11 Performance of Thin-Film Evaporator, Volatile and
Semivolatile Compounds, Run §7 3-25
3-12 Performance of Thin-Film Evaporator, Volatile and
Semivolatile Compounds, Run §Z 3-26
3-13 Performance of Thin-Film Evaporator, Volatile and
Semivolatile Compounds, Run i? 10 3-27
vi i i
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LIST OF TABLES (Continued)
SECTION PAGE
3-14 Measurements of Vent Gas Flow Rate and Bacharach TLV
Sniffer Measurements 3-28
3-15 Vent Gas Concentrations 3-30
3-16 GC/MS Analysis of Gas Samples, Vent Gas, and Headspace
(IEA) 3-31
3-17 Oil, Water, and Solids Analysis of Process Streams for
Runs 5, 7, 8, and 10 3-32
3-18 TFE Cost Estimation 3-35
4-1 Stripper Feed (In) and Bottoms (Out) Concentrations for
First Test Day (ppm) 4-4
4-2 Stripper Feed (In) and Bottoms (Out) Concentrations for
Second Test Day (ppm) 4-5
4-3 Summary of Feed and Bottoms Concentrations (ppm) 4-6
4-4 Removal Efficiency from Water for First Test Day
(Percent) 4-8
4-5 Removal Efficiency from Water for Second Test Day
(Percent) 4-9
4-6 Results of Vapor Analyses 4-10
4-7 Comparison of Vapor Concentrations at Primary (S8) and
Secondary (S9) Condenser Vents (Volume Percent) 4-11
4-8 Vapor Flow Rate from Primary Condenser (S8) 4-13
4-9 Flow Rate Measurements from Secondary Condenser Vent 4-14
4-10 Mass Flow Rates into and from the Primary Condenser (S8)
and Condenser Efficiency 4-15
4-11 Comparison of Measured and Predicted Efficiencies for
Primary Consenser (S8) 4-16
4-12 Estimates of Emissions from Storage Tank (S10) 4-18
4-13 Estimates of Emissions from Solids Decanters (S12) 4-19
4-14 Summary of Vapor Emissions 4-20
ix
-------
LIST OF TABLES (Continued)
SECTION PAGE
4-15 Stripper Feed (In) and Bottoms (Out) Concentrations for
First Test Day (ppm) 4-24
4-16 Stripper Feed (In) and Bottoms (Out) Concentrations for
Second Test Day (ppm) 4-25
4-17 Removal Efficiencies from Water for First Test Day
(Percent) 4-27
4-18 Removal Efficiencies from Water for Second Test Day
(Percent) 4-28
4-19 Results for Chloroform 4-29
4-20 Headspace Results for Feed and Bottoms (mg/L at 25 *C) .... 4-30
4-21 Organic Loading on the Condenser (g/s) 4-32
4-22 Condenser Vent Rates (g/s) and Condenser Removal
Efficiency (Percent) 4-33
4-23 Process Instrumentation 4-34
4-24 Cost Estimate for the Steam Stripper 4-35
5-1 Process Stream Characterization 5-4
5-2 Measured Concentration of Organics 1n Process Streams 5-7
5-3 Process Stream Characterization 5-8
5-4 Component Mass Balance Around Steam Stripper and
Condensate Tank (Streams F, B, C, 0, S) 5-9
5-5 Characteristics of Measured Organics 5-10
5-6 Removal Efficiencies (Percent) 5-10
5-7 Vent Gas Measurements, Sample Location 6-VOC 5-12
5-8 Estimation of Maximum Condensate Tank Vent Emissions 5-13
6-1 Comparison of Steam Usage Rates 6-3
6-2 Comparison of Performance 6-4
6-3 Cost Comparison 6-7
6-4 Summary of Average Condenser Vent Rates and Efficiencies .. 6-8
x
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APPENDIX A
SAMPLING AND DATA COLLECTION PROCEDURES
ft-l
-------
APPENDIX A
SAMPLING AND DATA COLLECTION PROCEDURES
PROCEDURES FOR THIN-FILM EVAPORATOR PILOT STUDY
The TFE process consisted of the feed tank, feed pump, feed preheater,
TFE, and condenser. Instrumentation for the process included thermocouples
(Type K) for temperature measurements, oil heater control, and adjustable
gear-driven Moyno positive displacement pump for flow control. The TFE rotor
speed was constant during testing (1,300 r/min), and the preheater temperature
was varied by adjusting the steam pressure to the preheater heat exchanger.
The temperatures were measured by a multipoint temperature logger, with
process temperatures read directly from the chart when the process was operat-
ing at a steady state. The bottoms and distillate flows were measured by
collecting the material in collection buckets (bottoms) or flasks (distillate)
over a timed interval. The amount of material collected was weighed and the
flow rates calculated. The feed rate to the TFE was determined by summing the
bottoms and distillate flow rates.
The TFE operating pressure was measured using a U-tube manometer adjacent
to the apparatus, and the rotor current was measured by an ammeter attached to
the TFE rotor's drive motor.
Figure A-l shows the sampling points and process measurements for the TFE
process.
Samples were taken 1n accordance with the Site Specific Test and Quality
Assurance Plan (Contract 68-02-3992, W.A. No. 1-6, August 1986) to character-
ize the wastes treated during the pilot studies and to determine the effi-
ciency and cost-effectiveness of the TFE process. Four process streams were
sampled: feed (SI), bottoms (S2), condensate (S3), and condenser vent gas
(S4). Table A-l summarizes the number of samples taken during the testing,
and Table A-2 lists the samples collected from these locations and the type of
sample collected.
The feed (SI) was sampled from a sample port just after the Moyno feed
pump. The valve for the sample port was opened, the sample line purged with a
small amount of feed sludge, and the feed sludge samples were collected
directly into clean amber bottles with Teflon-lined caps. Samples were sealed
immediately after collection and refrigerated.
The process bottoms (S2) were collected in a bucket contained in a sealed
pot directly under the TFE. The pot was sealed with the base of the TFE,
preventing volatile loss and allowing the system to be under vacuum for the
low-pressure runs. Bottoms were collected over a timed interval, and the
collected bottoms were poured directly into clean amber sample jars after the
A-2
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Steam
CO
I
JL
100 Gallon
Feed Tank
^ ©0
®6
Belt Drive (1300 rpm)
Condenser
(Water)
I
G*3
BPV
K&5
Of
LUWA
LN/LB-0028
TFE
fi"
Recirculation
Pump
Preheater
5
Entrainment
Separator
(no demister pads)
Heated
Oil
~©
Moyno
Feed
Pump
Atm.
Steam
&
Wet
Testmeter
Vent
^-To Vacuum
Evacuated Pot
with 5 gallon bucket
S Sampling point
T Temperature
P Pressure
A Motor current
Figure A-1. Sampling and measurement points.
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TABLE A-l. THIN-FILM EVAPORATOR SAMPLING
Location Type Number taken
51-Feed sludge 1-L amber bottle 5
500-cm3 bottles (full) 9
500-cm3 bottles (1/2 ful1)a 5
52-Bottoms 1-L amber bottle 24
500-cm3 bottles (full) 10
500-cm3 bottles (1/2 full)3 30
53-Condensate 1-L amber bottles 26
54-Vent gas Evacuated S.S. canisters 7
aUsed for onslte headspace analysis.
A-4
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TABLE A-2. COLLECTED LIQUID AND GAS SAMPLES,
LUWA THIN-FILM EVAPORATOR TESTS
Sample
Test number Date - Time number Description Comments
9/9/86
9:30 am
LUWA-24
SI,
Feed
1 L
full
Used material left
Feed
9/9/86
-
9:30 am
LUWA-25
si,
Feed
500
1/2
from first day of
Batch
A
9/9/86
-
9:30 am
LUWA-26
si,
Feed
500
1/2
preliminary tests,
9/9/86
-
9:30 am
LUWA-28
Si,
Feed
500
full
drums #1 and §2.
1
9/9/86
_
9:30 am
LUWA-29
S3,
Cond
1 L
full
1
9/9/86
-
9:30 am
LUWA-30
S2,
Bott
1 L
full
1
9/9/86
-
9:30 am
LUWA-31
S2,
Bott
500
1/2
1
9/9/86
-
9:30 am
LUWA-32
S2,
Bott
500
1/2
2
9/9/86
_
10:05 am
LUWA-33
S3,
Cond
1 L
full
2
9/9/86
-
10:05 am
LUWA-34
S2,
Bott
500
1/2
2
9/9/86
-
10:05 am
LUWA-27
S2,
Bott
1 L
full
3
9/9/86
10:40 am
LUWA-35
S3,
Cond
1 L
full
3
9/9/86
-
10:40 am
LUWA-36
S2,
Bott
500
1/2
3
9/9/86
-
10:40 am
LUWA-37
S2,
Bott
500
1/2
3
9/9/86
-
10:40 am
LUWA-38
S2,
Bott
1 L
full
4
9/9/86
_
11:20 am
LUWA-39
S3,
Cond
1 L
full
4
9/9/86
-
11:20 am
LUWA-40
S2,
Bott
500
1/2
4
9/9/86
-
11:20 am
LUWA-41
S2,
Bott
1 L
full
9/9/86
_
1:10 pm
LUWA-42
SI,
Feed
1 L
full
Drum #3 added to
Feed
9/9/86
-
1:10 pm
LUWA-43
Si,
Feed
500
1/2
empty feed tank
Batch
B
9/9/86
-
1:10 pm
LUWA-44
si,
Feed
500
1/2
9/9/86
-
1:10 pm
LUWA-45
si,
Feed
500
full
5
9/9/86
_
1:10 pm
LUWA-46
S3,
Cond
1 L
full
5
9/9/86
-
1:10 pm
LUWA-47
S2,
Bott
500
1/2
5
9/9/86
-
1:10 pm
LUWA-48
S2,
Bott
1 L
full
5
9/9/86
-
2:40 pm
LUWA-63
S2,
Bott
1 L
full
5
9/9/86
-
2:40 pm
LUWA-64
S3,
Cond
1 L
full
5
9/9/86
-
2:40 pm
LUWA-65
S2,
Bott
500
1/2
5
9/9/86
-
2:40 pm
LUWA-66
52,
Bott
500
1/2
5
9/9/86
-
2:40 pm
LUWA-67
S2,
Bott
500
full
5
9/9/86
-
2:40 pm
LUWA-68
S2,
Bott
500
full
5
9/9/86
-
2:50 pm
LUWA-69
S2,
Bott
500
full
5
9/9/86
-
2:50 pm
LUWA-70
S4,
Vent
Gas
SS§
A-60
6
9/9/86
_
1:40 pm
LJWA-49
S3,
Cond
1 L
full
6
9/9/86
-
1:40 pm
LUWA-50
S2,
Bott
500
1/2
6
9/9/86
—
1:40 pm
LUWA-51
S2,
Bott
1 L
full
(continued)
A-5
-------
Fi
B
8
8
8
8
8
8
8
8
8
8
9
9
9
TABLE A-2 (continued)
Date - Time
Sample
number
Description
Comments
9/9/86 - 2:05
pm
LUWA-52
S3,
Cond
1 "L
full
9/9/86 - 2:05
pm
LUWA-53
S3,
Cond
1 L
full
9/9/86 - 2:05
pm
LUWA-54
S2,
Bott
1 L
full
9/9/86 - 2:05
pm
LUWA-55
S2,
Bott
1 L
full
9/9/86 - 2:05
pm
LUWA-56
S2,
Bott
500
1/2
9/9/86 - 2:05
pm
LUWA-57
S2,
Bott
500
1/2
9/9/86 - 2:05
pm
LUWA-58
S2,
Bott
500
full
9/9/86 - 2:05
pm
LUWA-59
S2,
Bott
500
full
9/9/86 - 2:05
pm
LUWA-60
S2,
Bott
500
full
9/9/86 - 2:23
pm
LUWA-61
S4,
Vent
gas,
I
SS# A-160
9/9/86 - 2:23
pm
LUWA-62
S4,
Vent
gas,
F
9/10/86
-
O
CO
00
am
LUWA-80
SI, Feed
8:30 am
1 L full
9/10/86
-
8:30
am
LUWA-81
SI, Feed
8:30 am
500 1/2
9/10/86
-
8:30
am
LUWA-82
SI, Feed
8:30 am
500 1/2
9/10/86
-
8:30
am
LUWA-83
SI, Feed
8:30 am
500 full
9/10/86
_
9:10
am
LUWA-71
S3, Cond
1 L full
9/10/86
-
9:10
am
LUWA-72
S3, Cond
1 L full
9/10/86
-
9:10
am
LUWA-74
S2, Bott
1 L full
9/10/86
-
9:10
am
LUWA-75
S2, Bott
500 1/2
9/10/86
-
9:10
am
LUWA-76
S2, Bott
500 1/2
9/10/86
-
9:10
am
LUWA-77
S2, Bott
500 full
9/10/86
-
9:10
am
LUWA-78
S2, Bott
500 full
9/10/86
-
9:10
am
LUWA-79
S2, Bott
500 full
9/10/86
-
9:16
am
LUWA-84
S4, Vent
gas SS#
A-100
9/10/86
-
9:18
am
LUWA-85
S4, Vent
gas SS#
Drum #4 added to
feed tank
A-104
9/10/86 - 11:25 am LUWA-86 S3, Cond 1 L full
9/10/86 - 11:25 am LUWA-87 S2, Bott 500 1/2
9/10/86 - 11:25 am LUWA-88 S2, Bott full
9/10/86 - 11:55 am LUWA-89 S3, Cond 1 L full
9/10/86 - 11:55 am LUWA-90 S3, Cond 1 L full
A-6
(continued)
-------
10
10
10
10
10
10
10
10
10
11
11
Fe
Ba
12
12
12
13
13
13
14
14
15
15
15
15
15
16
TABLE A-2 (continued)
Sample
Date - Time number Description Comments
9/10/86 -
11:55
am
LUWA-91
S2,
Bott
1 L
full
9/10/86 -
11:55
am
LUWA-92
S2,
Bott
1 L
full
9/10/86 -
11:55
am
LUWA-93
S2,
Bott
500
1/2
9/10/86 -
11:55
am
LUWA-94
S2,
Bott
500
1/2
9/10/86 -
11:55
am
LUWA-95
S2,
Bott
500
full
9/10/86 -
11:55
am
LUWA-96
S2,
Bott
500
full
9/10/86 -
11:55
am
LUWA-97
S2,
Bott
500
full
9/10/86 -
12:01
pm
LUWA-98
S4,
Vent
gas
ss#
A-
115
9/10/86 -
12:04
pm
LUWA-99
S4,
Vent
gas
ss#
A-
178
9/10/86 -
12:04
pm
LUWA-100
Blank canister
SS# A-188
9/10/86
_
2:35
pm
LUWA-101
S3, Cond
1 L
full
Only limited
9/10/86
-
2:35
pm
LUWA-103
S2, Bott
500
1/2
amounts of bottoms
produced on this
vacuum run
9/10/86
3:30
pm
LUWA-105
SI, Feed
1 L
full
Drum #5 added to
9/10/86
-
3:30
pm
LUWA-106
SI, Feed
500
1/2
feed tank
9/10/86
-
3:30
pm
LUWA-107
SI, Feed
500
1/2
9/10/86
-
3:30
pm
LUWA-108
SI, Feed
500
full
9/10/86
_
4:00
pm
LUWA-109
Cond 1 L
ful
Preheater was off
9/10/86
-
4:00
pm
LUWA-110
Bott 500
1/2
for runs #13 and 14
9/10/86
-
4:00
pm
LUWA-111
Bott 1 L
ful
9/10/86
_
4:40
pm
LUWA-112
Cond 1 L
ful
9/10/86
-
4:40
pm
LUWA-113
Bott 500
1/2
9/10/86
-
4:40
pm
LUWA-114
Bott 1 L
ful
9/10/86
_
5:30
pm
LUWA-115
Cond 1 L
ful
LUWA-117 not
9/10/86
-
5:30
pm
LUWA-116
Bott 500
1/2
collected
9/10/86
5:50
pm
LUWA-118
Cond 1 L
ful
9/10/86
-
5:50
pm
LUWA-119
Bott 500
1/2
9/10/86
-
5:50
pm
LUWA-120
Bott 1 L
ful
9/10/86
_
6:20
pm
LUWA-121
Cond 1 L
ful
9/10/86
-
6:20
pm
LUWA-122
Bott 500
1/2
9/10/86
-
6:20
pm
LUWA-123
Bott 1 L
ful
(continued)
A-7
-------
17
17
17
18
18
18
Fe
Ba
19
19
19
20
20
20
21
21
21
22
22
22
TABLE A-2 (continued)
Date - Time
Sample
number
Description
Comments
9/10/86 - 7:30 pm LUWA-124 Cond 1 L full
9/10/86 - 7:30 pm LUWA-125 Bott 500 1/2
9/10/86 - 7:30 pm LUWA-126 Bott 1 L full
9/10/86 - 8:20 pm LUWA-127 Cond 1 L full
9/10/86 - 8:20 pm LUWA-128 Bott 500 1/2
9/10/86 - 8:20 pm LUWA-129 Bott 1 L full
9/11/86 - 9:15 am LUWA-130
9/11/86
9/11/86
9/11/86
9/11/86
9/11/86
9/11/86
9/11/86
9/11/86
9/11/86
9/11/86
9/11/86
9/11/86
9/11/86
9/11/86
SI, 1 L full
Waste §2
-
9:15 am
LUWA-131
SI,
500
1/2
-
9:15 am
LUWA-132
SI,
500 full
_
9:35 am
LUWA-133
S3,
Cond
1 L
full
-
9:35 am
LUWA-134
S2,
Bott
500
1/2
-
9:35 am
LUWA-135
S2,
Bott
1 L
full
_
10:30 am
LUWA-136
S3,
Cond
1 L
full
-
10:30 am
LUWA-137
S2,
Bott
500
1/2
-
10:30 am
LUWA-138
S2,
Bott
500
full
_
12:15 pm
LUWA-139
S3,
Cond
1 L
full
-
12:15 pm
LUWA-140
S2,
Bott
500
1/2
-
12:15 pm
LUWA-141
S2,
Bott
full
1 L
_
1:00 pm
LUWA-142
S3,
Cond
1 L
full
-
1:00 pm
LUWA-143
S2,
Bott
500
1/2
-
1:00 pm
LUWA-144
S2,
Bott
full
1 L
Two barrels of the
second waste were
added to the empty
feed tank
A-8
-------
bottoms were weighed. The bottoms were relatively hot as collected, and some
very minor amount of VO compounds was lost during this transfer. The concen-
tration of VO in the pot was measured frequently during the testing with a
Bacharach hydrocarbon analyzer and was typically near 200 ppm. The low con-
centration of hydrocarbons directly above the bottoms samples after exposure
to the air, the relatively high viscosity of the samples, and rapid transfer
of collected samples to the sample containers ensured that the loss of vola-
tlles was insignificant during collection. Samples were rapidly covered with
Teflon-lined caps and refrigerated.
Collection of condensate samples during testing required special precau-
tions to ensure that representative condensate samples were collected. Vapors
condensing to liquids formed both an organic layer and an aqueous layer. Any
holdup of liquid between the condenser and collection flasks split condensate
Into two fractions, with sample flowing from the system being nonrepresenta-
tive of the actual condensate. Condensing liquid flowed directly into sample
collection bottles with no holdup of condensate, allowing samples to be col-
lected as two layers that were representative of the condensate. Samples were
collected by placing clean 1-L amber bottles directly under the sample port as
the condensate flowed out of the condenser. Sampling continued until the
collection bottle was full, then it was sealed with a Teflon-Hned cap and
refrigerated. These condensate samples were later split into the organic and
aqueous fractions. Samples that were prepared from collected samples prior to
analysis are listed in Table A-3. Volumes and weights of aqueous and organic
fractions were measured during the sample splitting. The density of each
fraction and the relative amounts of each fraction were determined from these
data.
Gas canister samples were taken directly from the condenser vent directly
after the condenser. The gas canisters were evacuated stainless steel canis-
ters that were cleaned and evacuated as described in the QA plan. The vacuum
was first checked on the canisters prior to sample collection, then a sampling
port valve to the condenser vent was opened to permit vent gas to flow into
the gas canister. The valve on the sample canister was then closed and the
canister sealed with a Swagelok plug prior to shipment of the samples to the
analytical laboratory.
PROCEDURES FOR PLANT I
Details on sampling procedures can be found in Section 3 of the site-
specific test and QA plan dated September 12, 1986. A summary is provided in
this section. The test was conducted September 23-25, 1986.
The field test included the collection of process data throughout the test
and the collection of liquid and vapor samples for analysis. Process data
included the feed flow rate and temperature, steam flow rate and temperature,
cooling water temperature, column pressure drop, heat exchanger temperatures,
and outage measurements for the holding tanks.
Samples of the stripper feed, bottoms, and condensate were taken five
times at approximately 2-hour intervals during the day shift for each day of
the 2-day test for VO analysis. These sample points are identified as S5, S6,
A-9
-------
TABLE A-3. SAMPLES SPLIT FROM COLLECTED SAMPLES
(Runs 5, 7, 8, 10)
Sample number Test number Description Split from sample
LUWA-145
5
Cond
Aq
500
mL
LUWA-64
and
46
LUWA-146
5
Cond
Aq
500
mL
LUWA-64
and
46
LUWA-147
5
Cond
Aq
VOA
40
mL
LUWA-64
and
46
LUWA-148
5
Cond
Aq
V0A
40
mL
LUWA-64
and
46
LUWA-149
5
Cond
Org
VOA
40
mL
LUWA-64
and
46
LUWA-150
5
Cond
Org
VOA
40
mL
LUWA-64
and
46
LUWA-151
5
Cond
Org
500
mL
LUWA-64
and
46
LUWA-152
7
Cond
Aq
500
mL
LUWA-52
and
53
LUWA-153
7
Cond
Aq
500
mL
LUWA-52
and
53
LUWA-154
7
Cond
Aq
VOA
LUWA-52
and
53
LUWA-155
7
Cond
Aq
V OA
LUWA-52
and
53
LUWA-156
7
Cond
Org
VOA
LUWA-52
and
53
LUWA-157
7
Cond
Org
VOA
LUWA-52
and
53
LUWA-159
7
Cond
Org
500
mL
LUWA-52
and
53
LUWA-160
8
Cond
Aq
500
mL
LUWA-71
and
72
LUWA-161
8
Cond
Aq
500
mL
LUWA-71
and
72
LUWA-162
8
Cond
Aq
VOA
LUWA-71
and
72
LUWA-163
8
Cond
Aq
VOA
LUWA-71
and
72
LUWA-164
8
Cond
Org
VOA
LUWA-71
and
72
LUWA-165
8
Cond
Org
VOA
LUWA-71
and
72
LUWA-166
8
Cond
Org
V OA
LUWA-71
and
72
LUWA-169
10
Cond
Aq
500
mL
LUWA-89
and
90
LUWA-168
10
Cond
Aq
500
mL
LUWA-89
and
90
LUWA-170
10
Cond
Aq
VOA
LUWA-89
and
90
LUWA-171
10
Cond
Aq
VOA
LUWA-89
and
90
LUWA-172
10
Cond
Org
VOA
LUWA-89
and
90
LUWA-173
10
Cond
Org
VOA
LUWA-89
and
90
LUWA-174
10
Cond
Org
500
mL
LUWA-89
and
90
LUWA-175
5
Bott
VOA
LUWA-67
LUWA-176
5
Bott
VOA
LUWA-67
LUWA-177
7
Bott
VOA
LUWA-58
LUWA-178
7
Bott
VOA
LUWA-58
LUWA-179
8
Bott
VOA
LUWA-77
LUWA-180
8
Bott
VOA
LUWA-77
LUWA-181
10
Bott
VOA
LUWA-95
LUWA-182
10
Bott
VOA
LUWA-95
(continued)
A-10
-------
TABLE A-3 (continued)
Sample number Test number Description Split from sample
LUWA-183
Feed 4th
Drum
VOA
LUWA-80
LUWA-184
Feed 4th
Drum
VOA
LUWA-80
LUWA-185
Feed 4th
Drum
500
mL
LUWA-80
LUWA-186
Feed 3rd
Drum
VOA
LUWA-42
LUWA-187
Feed 3rd
Drum
VOA
LUWA-42
LUWA-188
Feed 3rd
Drum
500
mL
LUWA-42
A-ll
-------
and S7 1n Figure 4-1. In addition, samples for headspace analysis were taken
at each point. Composite samples were taken from S5 and S6 for filterable
solids and dissolved solids. Composite samples from S5 also were analyzed for
metals. Preliminary samples from S5 were taken to determine if any
extractable organlcs were present in the wastewater. The pH and temperature
of the liquid samples were measured several times during each test day.
Samples for V0 also were taken around the Initial solids decanters. The
wastewater feed to the decanter (SI) was sampled throughout the first test day
when wastewater was being pumped Into the decanter. This wastewater also was
analyzed for filterable and dissolved solids, metals, and VO 1n the headspace.
Samples of the organic layer (S2) were taken for VO analysis, VO 1n the head-
space, and filterable and dissolved solids. Samples of the sludge (S3) were
taken for VO analysis, VO 1n the headspace, total solids, and for analysis by
EPA's toxicity characteristic leaching procedures (TCLP). The wastewater
decanted from the tank was sampled for VO, VO in the headspace, filterable
solids, and dissolved solids.
The liquid samples for VO were taken 1n 40-mi11111ter (mL) glass VOA vials
with septa and no headspace. Samples for extractable organlcs were taken in
1-1 Iter (L) amber glass bottles with no headspace. The samples for solids and
metals were taken In 0.5-L plastic bottles, and the metals samples were acidi-
fied to a pH < 2 with redistilled HNO3. All samples were shipped packed 1n
ice.
Vapor samples were taken three times each test day from the primary con-
denser vent (S8), secondary or tank condenser vent (S9), and the vent of the
stripper's feed (storage) tank (S10). Vapor samples also were collected over
the open organic collection tank (SI1) and from the decanter vent prior to the
vent condenser (S12). The vapor samples from the condensers were taken in
evacuated electropollshed stainless steel canisters. Before each vapor sample
was taken, the presence of a vacuum was confirmed by connecting a vacuum gauge
and recording the vacuum reading. When the vapor flowrates were sampled, the
overflow pipes on the decanter were taped closed and the conservation vents
were monitored to be certain that they remained closed.
PROCEDURES FOR PLANT H
Details on sampling procedures can be found 1n Section 3 of the site-
specific test and quality assurance plan dated July 7, 1986. A summary is
provided in this section. The test was conducted July 21-23, 1986.
General Samples
The field test included the collection of process data throughout the test
period and the collection of samples for analysis. Process data were recorded
by plant personnel and Included the flow rate and temperature of the feed
stream to the stripper, the flow rate and temperature of the bottoms stream
from the stripper, the flow rate and pressure of the steam, and the supply
temperatures of the cooling water and refrigerated glycol. In addition, the
A-12
-------
plant Installed an orifice flow meter to measure the rate of condensate col-
lection. These data were recorded at one-half hour intervals throughout each
test day.
Samples of the stripper feed, bottoms, and condensate were taken 5 times
at 2-hour intervals (time = 0, 2, 4, 6, and 8 hours) during the day shift for
each day of the 2-day test for VO analysis. These sample points are identi-
fied as SI, S2, and S3 in Figure 4-2. The condensate separated into an aque-
ous phase and a heavier organic phase (primarily EDC). The volumes of each
phase were recorded, and samples of both the aqueous layer and the organic
layer were submitted for analysis. Samples for extractable organics, solids,
and metals were taken each hour during the test. The extractable organic
samples were composited over a 4-hour period to yield 2 samples per day at
each point, and the samples for solids and metals were composited over an 8-
hour period to yield one sample per day. The pH and temperature of the liquid
samples were also measured several times during each test day.
Samples of vapor from each of the two condensers were taken at S4 and S5
in Figure 4-2. Three samples from each point were taken each day at time = 0,
4.5, and 8 hours 1n evacuated stainless steel canisters.
The samples for VO were taken 1n 40-mL glass VOA vials with septa and no
headspace. Samples for extractable organics were taken in 1-L amber glass
bottles with no headspace. The samples for solids and metals were taken in
0.5-L plastic bottles, and the metals samples were acidified to a pH < 2 with
redistilled HNO3. All samples were shipped packed in ice and were analyzed
within 14 days of the sample collection time.
The vapor samples from the condensers were taken 1n evacuated electro-
polished stainless steel canisters. Before each vapor sample was taken, the
presence of a vacuum was confirmed by connecting a vacuum gage and recording
the vacuum reading. The vapor sample line was purged briefly before sample
collection.
Tracer Gas Samples
A tracer gas dilution technique was used to measure the vapor flow rate
after the refrigerated glycol condenser because this was a closed system under
pressure that was vented to an incinerator. Pure propane gas was metered into
sample point S5 with a tracer injection system consisting of a propane gas
cylinder, pressure regulator, check valve, flow controller, and Teflon trans-
fer line. The flow controller was calibrated in the laboratory at RTI by
measuring the flow of propane at specific flow controller set points with a
soap film flowmeter. The flow controller is capable of delivering constant
flow with a constant upstream pressure and varying downstream pressure as long
as a minimum of 10 psig pressure differential is maintained. The upstream
pressure was held at 40 psig with the pressure regulator and downstream pres-
sure (i.e. duct pressure) was approximately 4 psig.
Samples of overhead vapor were collected from sample point S4 and analyzed
for propane by gas chromatography with flame ionization detection. Two tech-
niques were used for sampling on the first test day. The first involved
A-13
-------
purging a 500 cc glass flask with vapor by connecting one end of the flask to
the sample port, opening both stopcocks (one at each end), opening the sample
port shut-off valve, and observing the flask outlet until vapor flow was evi-
dent. The flask was then sealed and transported to the mobile lab for analy-
sis. The second sampling technique involved purging the sample port transfer
line until vapor flow was observed, attachment of a silicone rubber septum to
a 1/4 inch union on the port with a Swagelok nut and back ferrule, and with-
drawal of vapor samples via a one cubic centimeter gas sampling syringe. The
syringe was equipped with a shut-off valve to allow transport of sample to the
lab for analysis without loss of syringe contents. All samples collected on
the second test day were collected in the gas-tight syringe with a minimum
flow rate used to purge the sample port prior to sample collection.
PROCEDURES FOR PLANT G
The objective of this sampling program is to determine how effectively the
Whitewater at Plant 6 is treated. Determinations are made using steam strip-
ping of the water, followed by carbon adsorption. Samples of the feed water,
organic condensate, aqueous condensate, steam stripper liquid effluent, and
carbon adsorber effluent were collected during the steady-state operation of
the steam stripper-carbon adsorber. Gas samples of the condenser vent were
also collected.
Liquid Samples
Liquid samples from the steam stripper were collected from the sample
lines into 40-mL volatile organic analyzer (VOA) bottles. The samples of the
column feed and discharge and the carbon adsorption unit discharge were taken
from appropriate process lines by filling a sample collection bottle. The
liquid was then transferred to a VOA bottle. An additional sample was col-
lected from the waste feed stream in a 1-L glass bottle for determination of
pH and sol Ids content.
Liquid samples were collected from the condensate collection vessel by
draining the material received from the separator into a 1-L collection bottle
equipped with a funnel. A 40-mL VOA bottle was then filled for volatiles
determination.
Vent Gas Samples
Air samples from the condenser vent were collected in evacuated steel
canisters. The evacuated sampling containers were connected to a vacuum gauge
in the field, and the presence of a vacuum was confirmed. The pressure read-
ing on the vacuum gauge was recorded. The sampling container was connected to
a flexible tube that terminated in the vent. The valve was opened on the
sampling container, and the container was filled with gas from the sampling
location. The sample valve was then closed, the 1/4-inch Swagelok fitting was
capped with a brass plug, and the sample description written on the sample
container label.
A-14
-------
APPENDIX B
SUMMARY OF ADDITIONAL MEASUREMENTS
b-i
-------
APPENDIX B
SUMMARY OF ADDITIONAL MEASUREMENTS
ADDITIONAL MEASUREMENTS AT PLANT I
The additional measurements made at Plant I included evaluation of the
removal of solids and metals in the decanter, mass and energy balances for the
process, and estimate of Henry's law constants for the untreated wastewater.
The vapor-liquid equilibrium constant was estimated from the vapor
canister analyses for the storage tank (S10) and the average liquid-phase
concentration measured in the feed from the storage tank. The wastewater had
been in the storage tank for several days; consequently, the vapor samples
taken from the tank's headspace should represent equilibrium with the tank's
liquid contents. The vapor samples from S10 contained percent levels of the
chlorinated compounds with average vapor-phase concentrations of 382 mg/L for
methylene chloride, 140 mg/L for chloroform, 48 mg/L for carbon tetrachloride,
and 3.9 mg/L for chloromethane. The equilibrium constant calculated from the
measured vapor and liquid concentrations 1n the storage tank are given in
Table B-l. The comparison of the measured values with theoretical values of
Henry's law constant shows reasonable agreement, although the measured values
are less than the predicted values for all compounds.
The feed to the solids decanter (SI) was sampled for VO during the first
test day when water was pumped from collection sumps into the decanter. On
the second test day, no samples were taken because no water was pumped into
the decanters. The results are given in Table B-2 and show that the major
components are methylene chloride and chloroform. The average methylene
chloride concentration at SI was 2,970 ppm, the average concentration of
chloroform was 1,770 ppm, and the average total VO 1n the wastewater at SI was
4,820 ppm.
The results of samples taken from the water in the sol Ids decanter (S4)
before and after the settling period are given in Table B-3. The settling
appears to decrease the VO concentration slightly. The concentration of meth-
ylene chloride in the decanter (3,800 to 5,420 ppm) is comparable to the con-
centration measured in the storage tank (3,419 to 6,788 ppm). Similar results
are found for chloroform with levels of 1,630 to 2,283 ppm In the solids
decanter and 864 to 2,829 ppm in the storage tank.
The sludge samples (S3) were analyzed by two different laboratories with
the results shown in Table B-4. The measured levels of methylene chloride
ranged from 4 to 20 percent (by weight), and the levels of chloroform ranged
from 4.6 to 9.8 percent. Carbon tetrachloride was the other major V0 compo-
nent of the sludge with levels of 4 to 11 percent. The sludge was a viscous
B-2
-------
TABLE B-1 VAPOR-LIQUID EQUILIBRIUM DATA
Vapor-liquid equilibrium
constant at 25 "C
Compound
Measured3
(atm*m3/g*mol)
Theoretical'3
(atm*m3/g*mol)
Chloromethane
2.9 x 10"3
8.1 x 10"3
Methylene chloride
2.1 x 10"3
3.2 x 10"3
Chloroform
2.7 x 10"3
3.4 x 10"3
Carbon tetrachloride
CSJ
1
o
X
1—H
CSJ
3.0 x 10"2
aMeasured from vapor space analysis of the storage tank and
analyses of the feed stream from the storage tank.
lvalue for Henry's law constant in aqueous solution from
OAQPS data base.
B-3
-------
TABLE B-2. RESULTS FOR VOLATILE ORGANICS IN FEED
TO SOLIDS DECANTER (Sl)a
Time
Methylene
Chloride
Chloroform
Carbon
tetrachloride
1,1,2-Trichloroethane
Total
9:30
3,990
2,630
94.5
6.3
6,720
9:30&
1,250
967
73.9
3.4
2,290
11:00
1,520
1,220
23.9
6.0
2,770
13:00
5,110
2,280
81.8
10.3
7,480
Average
2,970
1,770
68.5
6.5
4,820
aAl1 results in parts per million.
^Sample taken immediately after collection of first sample.
B-4
-------
TABLE B-3 VOLATILE ORGANICS IN WATER FROM SOLIDS DECANTER (ppm)a
Locati on
Ch1oromethane
Methylene
chloride
Ch1oroform
Carbon
tetrachloride
1,1,2-Tri ch1oroethane
Total VO
North decanter fS4)
Before treatment
39
4,670
1,640
144
8.0
6,500
After treatment
20
3,800
1,630
28
5.9
5,480
South decanter (S4)
Before treatment
17
5,420
2,283
136
6.0
7,860
After treatment
12
4,780
2,150
114
5.2
7,060
aSamples were takon before and after treatment. Treatment included addition of flocculant, mixing, and
settling for solids and organic phase separation.
-------
TABLE B-4. RESULTS OF SLUDGE ANALYSIS FOR VOLATILE ORGANICS
(percent unless otherwise noted)
1. IEA Results
Sludge from
Sludge from
Compound
Day 1
Day 2
Methylene chloride
19.6
8.0
Chloroform
9.8
4.7
Carbon tetrachloride
a
7.2
2. E and E Results
Sludge from
Sludge from
Compound
Day 1
Day 2
Methylene chloride
17.0
4.4
Chloroform
9.2
4.6
Carbon tetrachloride
4.1
11
Chloromethane'3
99.7
170
Trichloroethyleneb
--
380
1,1,2-Trichloroethyleneb
413
407
aNot detected and detection limit not determined. However, a
spike of 3.2 percent carbon tetrachloride resulted in 60-percent
recovery.
^These results are in parts per million.
B-6
-------
material with pockets of an organic phase dispersed in the solids. Conse-
quently, obtaining representative samples during sampling and analysis 1s
difficult and may contribute to imprecision in the sludge analyses.
The organic layer from the sol Ids decanter (S2) and from the steam strip-
per decanter (S7) also were analyzed for VO. The results listed in Tables B-5
and B-6 show that methylene chloride and chloroform are the major components.
Other VO constituents that may have been present at much smaller levels could
not be identified and quantified because of the loss of sensitivity to
quantify the two major components and because of the large tailing peaks of
methylene chloride and chloroform.
Several samples were analyzed for metals content, with the results given
in Table B-7. The feed to the solids decanter (SI) was sampled throughout the
first test day when rainwater was being collected in the sumps. This sample
1s untreated and yielded the highest concentration of metals. Samples also
were taken from the sol Ids decanter before and after a treatment step that
Includes flocculation and settling. The treatment appeared to decrease the
levels of cadmium, chromium, copper, nickel, lead, and zinc in the wastewater
that was transferred eventually to the storage tank for steam stripping.
The results for solids content given 1n Table B-8 are Inconclusive. The
results for the South decanter show a significant decrease in filterable
solids (1,079 to 50 ppm). However, the results for a batch of wastewater in
the North decanter appear to show an increase 1n filterable sol Ids. The batch
1n the North decanter during the test was very troublesome because of diffi-
culty 1n adjusting the pH and in obtaining a clear separation. The anomalous
results for the North decanter may have arisen from these difficulties and the
Inability to collect samples that were known to be representative.
The solids results for the stripper feed and bottoms show that the levels
of dissolved and filterable solids are much lower than the levels measured in
the solids decanter, which may result from variations among different batches.
The small decrease in solids concentration between the feed and bottoms sug-
gests that there may be a small net accumulation of solids in the steam strip-
ping process.
The sludge (S3) also was analyzed for solids. The results given in
Table B-9 reveal levels of 11 to 24 percent solids. EPA's TCLP also was
performed on the sludge. The results in Table B-10 show that very high levels
of the three major compounds were found in the extract from the TCLP. These
concentrations were essentially determined by the compound's solubility in the
extracting fluid. This was confirmed in the laboratory when attempts to spike
the extracting fluid with additional VO resulted in a phase separation. The
TCLP results for metals are given in Table B-ll. The major metals found from
the TCLP were nickel (59 to 83 ppm), zinc (36 to 57 ppm), and iron (10 to
28 ppm).
The primary purpose of the initial decanters is to remove any separate
organic phase and solids from the wastewater prior to steam stripping. During
the test, the filterable solids in the stripper feed ranged from 10.7 to
12 mg/L. The processing of two batches of wastewater in the decanters
B-7
-------
TABLE B-5. ANALYSIS OF DECANTED ORGANIC LAYER FROM S2 (g/L)
Test da)/
Time
Methylene chloride
Chloroform
1
9:30
1,200
495
1
14:30
920
362
2
12:10
890
449
12:10
892
387
12:10
917
405
Average
964
420
B-8
-------
TABLE B-& ANALYSIS OF ORGANIC CONDENSATE FROM S7 (g/L)
Run number
Methylene chloride
Chloroform
1-1
1,180
309
1-2
1,290
306
1-3
1,100
269
1-4
1,160
313
1-5
1,250
322
2-1
970
269
2-2
1,130
308
2-3
1,110
321
2-4
1,250
318
2-5
1,260
400
2-6
1,320
378
Average
1,180
319
B-9
-------
TABLE B-7 RESULTS OF ANALYSES FOR METALS (ppb unless otherwise noted)
Meta 1
Stripper
Day 1
feed (S5)
Day 2
Solids decanter (SI)
feed for Day 1
Solids decanter (S4)
(mi xed)
Solids decanter (S4)
(after treatment)
Arson ic
<1.0
8.7
179
8.3
8.1
Bery11i um
0.62
0.99
4.6
1.6
1.5
Cadmi um
8.0
<0.1
151
29
<0.1
Chromi um
2.5
5.0
19,400
1,800
53
Copper
73
53
3,611
572
122
Mercury
a
a
a
a
a
Ni eke 1k
1.7
0.07
88.2
12.7
0.39
Lead
2.2
<1.0
429
72.6
6.0
Se1 en i um
<2.0
<2.0
<2.0
<2.0
<2.0
Z i nc*3
0.26
0.36
53.8
6.6
1.1
aNot detected at a level of 4 ng.
^Results for nickel and zinc are in parts per million.
-------
TABLE B-8 RESULTS FOR TOTAL AND FILTERABLE SOLIDS (ppm)
Location Dissolved solids Filterable solids
South decanter (S4)
Before treatment3 11,600 1,079
After treatment 17,600 50
North decanter (S4)
Before treatment 45,000 51
After treatment 40,400 208
Stripper feed (S5)
Day 1 4,600 10.7
Day 2 6,200 12.0
Stripper bottoms (S6)
Day 1 4,160 9.5
Day 2 5,930 8.0
treatment includes addition of flocculant, mixing, and settling in
decanter.
B-ll
-------
TABLE B-9. RESULTS FOR ANALYSIS OF TOTAL
SOLIDS IN SLUDGE (S3)
Test day Percent solids
1 11.1
1 13.1
1 11.9
2 24.4
B-12
-------
TABLE B-10. RESULTS OF TOXICITY CHARACTERISTIC LEACHING PROCEDURE
ON SLUDGE FOR VOLATILE ORGANICS (ppm)a
Compound^
Sludge from
Day lc
Sludge from
Day 2
B1 ank
Carbon tetrachloride
213
380
0.22
Methylene chloride
7,070
3,700
0.043
Chloroform
2,600
1,700
0.008
aAnalysis of extract (simulated leachate) from decanter sludge.
^No other volatile compounds were detected at a limit of approximately
250 ppm.
cAverage of 3 replicates.
B-13
-------
TABLE B-11. RESULTS OF TOXICITY CHARACTERISTIC
LEACHING PROCEDURE ON SLUDGE
FOR METALS (ppm)a
Sludge from Sludge from
Metal Day 1& Day 2
Arsenic <0.04 <0.04
Barium 0.59 0.015
Beryllium 0.003 0.007
Cadmium 0.18 0.188
Chromium 0.107 0.248
Copper 0.345 0.103
Iron 10.4 28.1
Lead <0.02 0.03
Mercury 0.0005 0.0012
Nickel 59.4 83.4
Selenium <0.04 <0.04
Silver <0.01 <0.01
Zinc 36.2 57
aAnalysis of extract from decanter sludge.
^Average of 3 replicates.
B-14
-------
revealed solids levels of 50 to 208 mg/L after treatment. Because of the many
sources of wastewater, including runoff from rain, solids levels are likely to
vary from batch to batch. The process appeared to be effective in reducing
the solids content because fouling of the packed column was not a problem
during the test and has not been a significant problem for the plant, accord-
ing to company personnel. The solids removal step also decreased the levels
of cadmium, chromium, copper, nickel, lead, and zinc in the wastewater. Con-
sequently, solids removal prior to steam stripping resulted in lower concen-
trations of metals In the effluent as well as improved consistency in the
steam stripper's performance and fewer problems from fouling of the packing
material.
The decanter 1s also designed to remove any separate organic phase. This
step should also improve the consistency of operation and performance of the
steam stripper. A slug of a separate organic phase 1n the feed could cause
flooding, high concentrations in the bottoms, and other operational problems.
Data supplied by the company indicated that roughly 50 Mg/yr of a separate
organic phase 1s removed from the initial decanters. The generation of sludge
was estimated as 220 Mg/yr with a water treatment rate of 16,500 Mg/yr (based
on 11 gal/min for 75 percent of the year).
A summary of the process data collected during the 2-day test is given 1n
Table B-12. The feed rate to the stripper and the steam rate shows very
little variation «5 percent) throughout each test day. For the first test
day, the feed rate averaged 41 L/min (10.8 gal/min) and the steam rate
averaged 252 kilograms per hour (kg/h) or 555 pounds per hour (lb/h). On the
second test day, the feed rate averaged 40.5 L/min (10.7 gal/min) with a steam
rate of 254 kg/h (559 lb/h). The rate of steam usage was about 0.1 kg/kg
water. The pH of the feed and bottoms was consistently at 5.0 during the first
test day. No water was added to the feed (storage) tank during the first
test. Prior to the second test, a batch of wastewater was transferred from
the solids decanter with a very high pH after caustic addition. Throughout
the second test, the pH of the feed and bottoms was 11.3 to 11.5.
The process data were used to estimate the distribution of mass and energy
around the steam stripper. The results are summarized in Table B-13. The
mass flowrates of the feed, steam, and vapor were measured directly. Attempts
to measure the condensate rate directly were hampered by an inability to empty
the decanter completely, inaccuracies because of separate phases and a
partially suspended organic phase, and the continuous generation of
condensate.
Because only a pure organic phase is removed from the system as conden-
sate, the condensate rate was estimated from the amount of organics entering
with the feed minus the amount of organics leaving with the vapors from the
condenser vent. (Organics 1n the bottoms from the stripper were negligible.)
An attempt was made to measure the bottoms rate by measuring the change in
volume of the holding tanks as a function of time. This approach was not very
accurate and resulted in highly variable rates. The bottoms rate presented in
Table B-13 was estimated from the total in (feed and steam) minus the quantity
leaving with the condensate and vapors.
B-15
-------
TABLE B-12. SUMMARY OF PROCESS DATA
Parameter 9-24-86 9-25-86
Steam rate (kg/h) 252 254
Feed rate (kg/h) 2,450 2,430
Bottoms rate (kg/h) 2,690 2,670
Pressure drop (mm H2O) 267 292
Feed pH 5.0 11.5-11.6
Bottoms pH 5.0 11.3-11.5
Cooling water temperature (°C) 17-20 18-21
Condensate temperature (#C) 18-22 18-22
Heat exchanger temperatures (*C)
Feed in 24 26
Feed out 82 79
Bottoms in 98 99
Bottoms out 41 46
Bottoms temperature (*C)a 108 105
aBottoms temperature recorded by plant.
B-16
-------
TABLE B-13. DISTRIBUTION OF MASS AND ENERGY
9-24-86
9-25-95
Stream
kg/h
106 Btu/h
kg/h
106 Btu/h
Feed
Steam
2,450
252
0.799
0.641
2,430
254
0.760
0.650
Total in
2,700
1.44
2,680
1.41
Bottoms
Condensate3
Vapors
Cooling water0
2,690
12
1.2
1.15
b
b
0.290
2,670
12
1.2
1.11
b
b
0.300
Total out
2,700
1.44
2,680
1.41
Recycled condensate
waterd
Heat exchanger
dutye
114
0.567
118
0.509
aCondensate rate estimated from organics in with feed minus organics out with
uncondensed vapor and bottoms (negligible).
^Negligible contribution to overall balance.
cHeat removed by the condenser was estimated by difference (total in minus out
with bottoms, vapor, and condensate).
^The rate of recycle for the condensed water was estimated from energy removed
by the condenser divided by the latent heat of vaporization of water.
eEnergy exchanged in heat exchanger based on feed flowrate and temperature
increase.
B-17
-------
The energy balance data show that the heat exchanger recovers and provides
about 36 to 40 percent of the total energy entering the stripper. Heat 1s
exchanged at a rate of 0.5 to 0.6 million Btu/h. The primary condenser
removes about 0.3 million Btu/h from the overhead vapors.
All of the condensed water from this process 1s returned to the steam
stripper. The rate of recycle was estimated from the energy balance as 114 to
118 kilograms per hour (kg/h) or about 5 percent of the feed rate.
ADDITIONAL MEASUREMENTS AT PLANT H
Additional measurements made by the sampling team are summarized in Table
B-14 to correspond with the run numbers for the samples of wastewater entering
and leaving the steam stripper. During the start of the test during the first
day, the heat exchanger started to foul and the feed temperature was measured
at 67 and 63 *C (for Runs 1-1 and 1-2). The heat exchanger and column were
backflushed. After backflushlng, the feed temperature increased to a range of
80 to 88 °C for the balance of the test. The data in Table B-14 also show an
Increase in pH 1n the wastewater after steam stripping.
The results for priority pollutant metals and solids are summarized in
Table B-15. Copper was found at levels higher than any of the other metals
and probably originates from the catalyst used in the production of 1,2-
dlchloroethane (see Section 3.0). The results for solids reveal levels 1n
excess of 1 percent for dissolved solids and about 0.1 percent for suspended
solids. The differences in concentrations between the feed and bottoms
suggest that there may be a net accumulation of solids in the steam stripper
and/or heat exchanger.
Overall mass and energy balances were performed on the steam stripper.
During the morning of the first test day, some operating problems with the
steam stripper were experienced because of fouling 1n the heat exchanger and
column. The flow rates were quite variable during this period; consequently,
this time period (7:30 to 10:30) was treated separately for the first test
day. Flow rates were relatively consistent for the balance of the first test
day (11:00 - 16:30) and throughout the second test day. Mass and energy
balances were performed for these three time periods and are summarized in
Table B-16.
The energy balances are based on the measured flow rates of each stream
entering and leaving the stripper, the temperatures of the liquid streams, and
steam at 50 psig (64.7 psla). Heat removal with the overhead vapors is based
on saturated steam at 4 psig (the overhead pressure) being cooled to approxi-
mately 33 'C (the typical condensate temperature).
The mass balance results in Table B-16 for the time period 7:00 to 10:30
do not represent 100 percent closure because of wide ranging flow rates
recorded at one-half hour intervals and the difficulty in obtaining a
reasonably accurate average for the period. Flow rates were consistent for
the balance of the test period and reasonably accurate averages could be
obtained. The result is a percent closure approaching 100 percent and a high
B-18
-------
1
2
3
'1
5
1
2
3
1
T
TABLE B-14. TEMPERATURE, pH, AND CONDENSATE SEPARATION MEASUREMENTS
1 Hmppratui'es (°C)
PH
Inf liient Rffluent Coiicieus.t le
(S7
63
85
84
84
4 2
39
40
38
40
32
3 1
33
3C>
33
TnfLuenl Effluent Condensate
6 7
7 3
5 2
7 0
8 7
Volume I'erciMil
Organics in Condensates
8 7
9 0
9 2
9 0
8 9
6 3
0 2
6 2
C. .3
6 0
18 3
18 8
17 0
15 0
14 .0
81
80
8 I
87
84
4 3
4 3
I I
48
4 I
33
34
35
39
3f>
6 0
7 0
7 I
5 0
4 9
8 8
9 3
5 6
6 r>
8 (>
6 0
6 2
6 2
6 2
6 4
I 1 4
20 6
12 1
10 0
12 1
-------
TABLE B-15 RESULTS OF METALS AND SOLIDS ANALYSES
(All Results in ppms or mg/L)
Parameter
Test Day 1
Test
Day 2
Feed
8ottoms
Feed
Bottoms
Arsenic
031
015
044
028
Cadmium
< 01
< .01
< .01
01
Chromium
18
. 14
.11
12
Copper
33
34
31
38
Lead
<.005
< 005
< 005
005
Mercury
007
010
007
008
Nicke L
.73
54
53
52
Selenium
< 005
< 005
< 005
< 005
Zinc
1 2
.35
30
. 17
Antimony
< 2
< .2
< 2
2
Beryl 1 mm
<.01
< 01
< 01
< 01
Dissolved
Sol 1dsa
13,000
1 I ,000
14.000
J , 000
Suspended
So I ids*1
1 ,400
910
L .400
950
dThese results represent
only 2
s i^ri l f 11 ant f i t;ur<»s
B-20
-------
TABLE B-16. MASS AND ENERGY BALANCES
<7
7/22/86
00-10 30)b
(11
7/22/86
00-16-30)
C-
7/23/86
00-16 30)
Stream*5
Mass
(Mg/h)
Energy
(106 BTU/h)
Mass
(Me/h)
Energy
(106 BTU/h)
Mass
(Mg/h)
Energy
(106 BTU/h)
Feed
45 7
12 5
51 0
15 9
49 5
16 1
Steam
3 9
10 2
1 6
4.2
1 8
4 6
Total In
49 6
22 7
52 6
20 1
51 3
20 7
Bottoms
41 4
17 9
51 .9
22.0
50 7
20 7
Condensate
4 0
5.0
0 7
1 7
1 1
2 3
Total Out
45 4
22.9
52 6
23 7
51 8
23 0
Percent Closure0
109
!
1 99
I
100
i
j 85
99
1
| 90
aMass and energy in the vented gas is negligible in comparison to major
streams
Whis time interval was treated separately because of large fluctuations in
flow because of column and heat exchanger fouling problems Other time
intervals represent steady operation
cDefined as In -f Out x 100
B-21
-------
level of confidence in the distribution of mass for 7/22 (11:00 - 16:30) and
7/23.
The energy balances show reasonable percent closure values for an Indus-
trial process and the Instrumentation Involved. However, the differences 1n
percent closure between the mass and energy balances for each period suggests
a consistent bias 1n the energy balance, I.e., either the energy 1n is under-
estimated by about 10 percent or the energy out is overestimated by about 10
percent. The data were examined to assess probable causes of the bias in the
energy balance. The column pressure was approximately 4 ps1g and corresponds
to a vapor pressure of water of 18.7 psia. Water 1n equilibrium with Its
vapor at 18.7 psia has a temperature of 106.8 *C. This suggests that the
measured temperature of the stripper bottoms (effluent) at 107-108 *C was
accurate because it corresponds to the water temperature predicted at 4 ps1g
or 18.7 psia (106.8 °C). Consequently, the feed temperature (entering the
column after preheating in the heat exchanger) is suspected as the likely
source of the bias. A sensitivity analysis was performed to assess the
effects of small changes in mass flow rates and temperatures on the percent
closure of the material and energy balances and the results are listed below.
The first row ("overall") shows the percent closure based on the actual
experimental results. The other rows show how the percent closure changes if
the value of one of the parameters is altered.
Reported Altered Percent Closure
Parameter Adjusted Value Value Mass Energy
Overal1
—
—
100
85
Feed temperature
80 •C
90 #C
100
94
Bottoms temperature
107 *C
100 *C
100
91
Steam rate
1.6 Mg/h
2.0 Mg/h
99.3
90
Condensate
0.6 Mg/h
0.3 Mg/h
99.4
89
Bottoms
51.9 Mg/h
50 Mg/h
96.4
89
Overhead temperature
102.5 'C
80 #C
100
86
The results given above suggest that an actual feed temperature slightly high-
er than the reported value yields a much better percent closure on the energy
balance without affecting the percent closure on the mass balance.
The condensers for the overhead vapors remove energy from the system at a
rate of roughly 1.7 to 2.3 million BTU's per hour. The condensers include a
primary condenser that uses cooling tower water at approximately 29 *C follow-
ed by a refrigerated glycol condenser at approximately 2 *C. The second con-
denser probably represents the maximum cooling that can be supplied by con-
densers of this type because operation at temperatures below 2 °C could lead
to freezing and fouling or plugging problems.
The heat duty of the plate and frame heat exchanger used to preheat the
feed was estimated from the effluent flow rate and the temperature difference
in the effluent entering and leaving the heat exchanger. The average flow
B-22
-------
rate of effluent over the test period was approximately 51.3 Mg/h and the
average temperature drop was from 108 'C to 43 *C. The heat exchanged under
these conditions is approximately 13.2 million BTU's/h. The total energy
entering the steam stripper from Table B-16 was about 20.4 million Btu's/h;
consequently, the preheat heat exchanger recovers and supplies about 65
percent of the total energy needed for the operation. Because steam stripping
is energy intensive and total operating costs are strongly affected by the
cost of steam, the use of this heat exchanger represents significant energy
and operating cost savings.
Mass balances were performed for two constituents that represent the two
extremes in the pathway of removal from the process. Vinyl chloride 1s very
volatile and condenser vent measurements showed that essentially all of the
vinyl chloride left through the condenser vent and was routed to the inciner-
ator. On the other extreme, essentially all (99+ percent) of the 1,2-
dlchloroethane entering with the wastewater is recovered with the condensate.
Because the condensate rate was highly variable, averages from each test day
were determined from Table B-17 and the quantity of l,2-d1chloroethane removed
was estimated from a composition of about 90 percent In the organic phase and
roughly 1.8 to 2.1 percent in the water phase. The most reliable and complete
vent rate measurements were made on the second test day; therefore, the vinyl
chloride rate through the condenser vent is probably most reliable for this
time period. The mass balance results for vinyl chloride and 1,2-
dichloroethane are given in Table B-18.
B-23
-------
TABLE B-17. RATE OF CONDENSATE COLLECTION
Kun No
TotaJ
Condensate
(gdl/nuri)
% Organic
by Voitiim;3
Water
Condensate
Rate (g/s)
Orgum
Condensate
Rale (g/s)'3
1-1V
1-2V
1-3V
9 14
4.0
3 22
18 8
16 6
14 0
468
211
175
137
52.8
35 H
2 -IV
2-2V
2-3V
4 69
11 .85
4 10
11 4
10 0
12 1
262
673
227
42 5
94 2
39 4
aThese values were averaged over time intervals that overlap or Liielude the
tame at which the vapor samples were taken
^Specific gravity - 1 26
B-24
-------
TABLE B-18. RATE OF VINYL CHLORIDE AND 1,2-DICHLOROETHANE
(All rates in g/s)
Day 1
Day 2
Average (95% linuts)a Average (95% limits )a
Vinyl chloride
In with feed
Out condenser vent
.092b ( 03 - 29)
078c ( 05 - 12)
070 ( 05 - 11)
074 ( 04 - lf>)
1,2-Dichlorocthaned
In with feed
Out with organic condensate
Out with water condensate
Out condenser vent
Total Out
77 (45 - 130)
68 (12 - 388)
5 (7-34)
0 2 ( 07 - 6)
69 (49 - 97)
58 (23 - 145)
8 (2 2 - 29)
0 4(2- 8)
73
66
a(Jorif idence limits determined from propagat lori-of-error analysis Assumes
no bias in measurements of flow rates and concentrations and a log normal
distribution for repeat measurements throughout the test day The greatest
uncertainty is in the mass rate of the compound in the condensate, which is
estimated from three measurements (condensate (low rate, percent organjc.s
by volume, and concentration in the organic layer)
^Vinyl chloride concentrations in the feed were highly variable for the
first test day and were fairly constant for the second test day \o vinyl
chloride detected m the stripper bottoms
cBased on only one measurement of the mass llow rate out ol the condenser
vent for the first test day An average of 3 measurements were used for
the second test day
dThe mass flow rate ot 1.2- dich1oroethane in the stripper bottoms was
negligible ( 10~3 to 10~4 g/s)
B-25
-------
APPENDIX C
PROCESS DATA
-------
TABLE C-1. PROCESS DATA STEAM STRIPPER, PLANT Ga
Steam (S)
Feed (F)
T ime
Flow rate
kg/h
Temperature
°C
Pressure
kPa
Flow rate
kg/h
11:45
1,926
128.9
262
29,900
12:00
2,027
128.9
262
29,900
12:15
1,928
129.3
248
29,900
12:30
2,010
128.9
269
29,900
13:15
2,111
128.7
262
29,900
13:30
2,101
128.4
276
29,900
14:27
2,129
128.5
262
29,$00
Average
2,033
128.8
263
29,900
Std. dev.
84
0.3
8.5
-
aThese data were
gal/min.
originally
collected in units
of lb/h, °F,
psig, and
C-2
-------
TABLE C-2. PROCESS DATA: STEAM STRIPPER, PLANT Ga
Time
Bottom level
of liquid in
column, %
Pressure at
bottom of
column, kPa
Heat exchanger
temperature, ®C
F1 F
B1
11:00
60
103
27
85
58
11:57
55
103
27
84
57
12:33
55
103
27
84
57
1:06
55
103
27
83
58
1:35
60
103
27
83
58
2:13
60
103
27
82
58
2:35
55
103
27
82
58
Average
57
103
27
83
58
aThese data were originally collected in units of %, psig, and °F.
-------
TABLE C-a PROCESS DATA FOR PLANT H (FIRST TEST DAY)
Date
7-22-86
Str
i ppor
Feed
St.r ipper
Bottoms
Steam to
Str ipper
Condensate
Cooling
Sys tem
Temperature ("C)
T line
Cooling
Towei
!•' 1 ow
Ttl in | >
!•' 1 ow
IVmp
K 1 ow
Pressure
!•' 1 ow
Rate
_W,il_er
Glycol
(g.tl/min)
(°C)
(gal/mm)
( °C)
(lbs/hour)
(psig)
(gal/min)
Supply
Return
Supply Return
0700
227
6
7 .<
210
108
8,590
50
9
42
29
2
0730
225
(>
fi f>
240
108
8,710
50
9
40
29
2
080O
228
I
67
244
108
7 .070
50
9
27
29
2
0830
233
6
01
170
1 11
9 ,910
50
9
40
29
2
0000
230
6
60
240
112
8,750
51
9
14
29
2
0930
1 I'J
0
7tt
80
1 19
10.600
50
40
47
29
2
1000
172
6
81
ICO
102
9 ,320
50
32
33
29
2
1030
172
5
77
80
106
6 ,020
50
23
21
29
2
1 10()
209
56
200
108
3,790
48
8
17
29
2
1130
24 L
65
210
107
4 ,460
51
4
15
29
2
1200
218
82
220
107
3,210
51
4
24
29
2
1 230
217
91
220
108
3 ,190
50
4
60
29
2
1300
217
88
220
107
3,220
50
3
29
29
2
1 330
232
84
232
108
4 .690
50
2
76
28
2
1400
221
82
232
108
3,220
50
2
37
29
2
14 30
22 4
7
a i
220
107
3,270
50
3 .
35
29
2
1 500
219
75
220
107
3,220
50
3
85
29
2
1530
225
70
240
107
3 . 220
50
1
67
29
2
1000
228
71
24 8
107
3.320
49
2
90
29
2
J (->30
• >pr
i. v *
8
73
24 O
108
3 . 670
4 9
3
22
29
2
-------
TABLE C-4. PROCESS DATA FOR PLANT H (SECOND TEST DAY)
Date •
7-23-80
Stripper Feed Stripper Bottoms Steam to Stripper Condensate Cooling System Temperature (°C)
Time Cooling Tower
Flow Temp. Flow Temp Flow Pressure Flow Kate Wat er Glycol
(gal/inin) (°C) (gal/nun) (°C) (lbs/hour) (psig) (gal/min) Supply Return Supply Return
0700
231 a
240
107
4 ,600
50
4
34
29
36
2 2
0730
23 J
240
J Of!
4 , 240
50
4.
,69
30
36
2 0
0800
228
232
108
4 . 210
50
4
69
30
36
2.0
230
236
108
4,020
50
3
63
30
36
2.0
090(1
229
232
109
4,550
50
4
10
29
36
2 2
0930
234
232
110
3,900
50
4
34
29
35
2 2
1000
227
226
111
4 , 300
50
3
.74
29
35
2 0
1030
232
220
108
4 , 510
50
3,
.46
29
35
2.0
1100
225
232
108
3, 690
50
3
85
29
35
2 0
1 I'U)
227
224
108
4.250
50
3
35
29
35
2 2
1200
227
232
108
4 , 150
50
4
52
28
33
2 0
1230
231
230
109
4,450
50
4 .
. 15
28
33
2 2
1300
209
230
112
3,990
50
12
54
28
34
2 0
1330
1 35
220
107
3. 240
50
1 1
85
28
34
2 0
1400
197
200
108
3,210
50
4
43
28
34
2 2
1430
195
240
108
3, 220
50
3
79
28
34
2 0
1500
191
130
107
3.260
50
4
52
28
35
2 0
1 530
187
](->()
108
3.210
50
4
30
29
35
2 2
ril> lant
ranged
instrument in.i 1 1
from 8t-38 "C
tllK.I 1 (lIHMl
throughout
Feed toinpei
the test
rtil urc was
Dicnsui (;d
by the sampling
team wi tti
a
tliermomete
-------
TABLE C-5. PROCESS DATA FOR PLANT I (9/24/86)
Pressure
Bottoms
Hold
i ng
Decanter tanks
Storage
Steam
Flow
Feed
drop
temp .
tanks (
inches)
(K ful1)
tank
T i me
(Ib/h)
Totalizer
(ga1/mi n)
(in. H20)
( C)
East
West
North
South
(X full)
7:45
556
60596
10.8
10 . 6
104
139
32
76.5
32
30
8 : 30
555
50981
11.0
10.6
104
128
49
78
33
30
9: 16
556
61431
10. 8
10.6
104
20
70
85
35
30
9 : 45
556
61738
10.8
10 . 6
104
0
83
86.6
42
30
10:15
566
51961
10.8
10.6
104
0
94
86
44 .
6
30
11 :00
556
62383
10. 9
10.6
104
0
113
86
47
30
11:46
665
52734
10. 8
10.5
104
0
128
88
47
30
12 : 30
556
63169
10. 8
10.6
104
0
140
89
66
29
13:15
566
53359
10.9
10.6
104
0
139
94
83
29
14 : 00
660
53942
10. 9
10.5
104
30
139
96
87 .
6
28.6
16:00
660
55111
10. 8
10.6
104
87
100
96
82.
6
28.6
-------
TABLE C-6 PROCESS DATA FOR PLANT I (9/25/86)
Pressure
Bottoms
Holding
Decanter tanks
Storage
Steam
F 1 ON
Food
drop
temp .
tanks
(i nches)
(X
full)
tank
T i mo
(lb/h)
Tots 1 i zer
(ga1/mi n)
(in. H20)
( C)
East
West
North
South
(X ful1)
7:45
665
3550
10 . 9
11.6
105
0
68
94
88
26
8:46
666
4113
10.7
11.6
105
0
92
94
88
26
9:30
680
4482
10.6
11 .6
105
0
108
94
88
26
10:30
660
4985
10.7
11.5
105
0
116
94
88
26
11:45
666
6717
10.2
11.0
105
22
138
94
88
24
0
1
-"-j
-------
APPENDIX D "
ANALYTICAL PROCEDURES
o-J-
-------
APPENDIX D
ANALYTICAL PROCEDURES
ANALYTICAL PROCEDURES FOR THIN-FILM EVAPORATOR TEST
The analytical procedures for both the field analyses and the contracted
analyses are discussed in this section. Analyses were performed by RTI per-
sonnel at the test facility and by two contract analytical laboratories, IEA
and CompuChem.
The onsite measurements performed by RTI were: (1) the analysis of head-
space concentrations of VO from feed sludge samples and bottoms samples and
(2) the measurement of vent gas flow rates and overall VO concentrations in
the vent gas and bottoms collection pot. Two types of analyses for headspace
concentrations of VO were employed. The first used syringes to transfer gas
samples from half-filled 500-cm^ sample bottles and a portable GC to measure
the concentrations of VO in air above the samples.
The samples for headspace analysis of VO compounds were half-filled 500-mL
amber bottles with modified caps to allow gas sample removal through a septum
on the bottle's cap. Samples were withdrawn from the bottle and injected into
a GC with a flame ionization detector. The GC system is listed in Table 6-1.
It was calibrated with both a CI to C7 gas hydrocarbon standard (methane,
ethane, propane, butane, pentane, and hexane 100 ppm in N2) and a liquid
benzene standard (200 /tg/mL). Samples of toluene were injected to determine
the retention time of the compound. The field analysis was conducted without
knowing the specific organic compounds that would be present in the samples.
The compound peaks were identified by the retention times of eluting com-
pounds, and the identification was confirmed by GC/MS analysis of headspace
samples by IEA. The headspace samples were found to contain propane, butane,
pentane, hexane, benzene, and toluene. Also detected were 2-butene, cyclopen-
tane, 2-methyl pentane, and 2-methyl butane in substantial concentrations.
The operating manual for the GC can be found in the project Quality Assurance
Plan.
The second method of measuring the headspace concentrations of VO used a
calibrated total hydrocarbon analyzer. This instrument was a Bacharach TLV
Sniffer that pulls a continuous sample that is continuously oxidized by a
catalyst-coated resistance element. The resistance of this element varies
with temperature, which is in turn proportional to the hydrocarbon concentra-
tion of the analyzed gas. For headspace concentration measurement, the sample
probe of the sniffer was inserted into the half-filled sample jars, headspace
sample was pulled into the analyzer, and the resulting maximum measured con-
centration recorded as the headspace concentration of VO for the sample.
These readings gave the total hydrocarbon concentration of the headspace
gases, expressed as parts per million hexane. These measurement were intended
D-2
-------
to be a rough measurement of headspace concentrations and to confirm the re-
sults from GC analysis of headspace concentrations. The Bacharach TLV Sniffer
had a maximum measurable concentration of 10,000 ppm and this range was
exceeded by all of the headspace samples of the feed samples. Although unable
to measure the actual headspace concentration of these samples, the sniffer
did give a qualitative measurement of the concentrations (greater than 10,000
ppm).
The Bacharach TLV was also used to measure concentrations of organics in
the vent gas, feed tank headspace, and vapors above the bottoms when the sam-
ple pot was removed from the TFE. Measured organic concentration of the vent
gas and feed tank headspace also exceeded the range of the instrument.
A wet test meter was used to measure the vent gas flow rate from the
primary condenser. This Instrument (Precision Scientific catalog No. G3115)
1s considered a primary standard for the measurement of relatively small flow
rates and was attached directly to the vent gas outlet. Measurements of the
vent gas flow rate were taken only when no diversion of the vent gas (i.e.,
through the condenser condensate sample line) was occurring.
Volatile Analyses by CompuChem
The volatile samples were prepared for analysis according to the EPA
Contract Laboratory Program (CLP) protocols for volatile analyses. Sample
Luwa 168 was analyzed by purging 175 fit. The liquid oil samples, LUWA 149,
156, 164, and 172, were diluted 1:1,000 with methanol prior to the Injection
of 1.0 pi into a megabore capillary column. The six sludge samples were
analyzed as medium-level methanol extracts. Approximately 4 grams of each
sample was extracted with 10 mL of methanol. From 1 to 100 /
-------
• Bromofluorobenzene—150 ng
• d8-Tolaene~150 ng.
The Internal standard compounds used are:
• Bromochloromethane--150 ng
• 1,4-Dichlorobenzene—150 ng
• d5-chlorobenzene--150 ng.
The Internal standard areas are required to be within -50 and +100 percent
of the corresponding area in the shift standard. Failure to meet this
criterion requires the repreparation and reanalysis of the sample.
A Finnigan OWA GC/MS equipped with a Tekmar purge and trap device and a
6 ft x 1/4 in. glass column packed with 1 percent SP-1000 on Carbopack B was
used for the volatile analysis of the sludge extracts and aqueous condensate.
The following temperature program was used:
• Initial temperature—50°
• Initial hoid--3 min
• Ramp rate«8Vmin
• Final temperature—215*.
The four liquid oil samples required analysis using a Finnigan OWA
equipped with a 30-m megabore DB624 column. The following temperature program
was used for those analyses:
• Initial temperature—30°
• Ramp rate—8*/min
• Final temperature—260*.
Semi volatile Analyses by CompuChem
The semi volatile samples were prepared for analysis according to the EPA
CLP protocols for semi volatile analyses. The water sample was analyzed by
extracting 100 mL of liquid with methylene chloride after pH adjustment to
greater than 11 and to less than 2 and concentrating the resulting extract to
1.0 mL. The 1.0 g of each oil sample was diluted to 25.0 mL with methylene
chloride. The sludge samples were extracted using approximately 30 g of sam-
ples. Final extract volumes for the sludge samples ranged from 8.0 to 20 mL.
All semi volatile analyses have been analyzed within the CLP-specified
12-hour tune timeframe. Quantitations are based on a five-point calibration
or verifying shift standard. At the beginning of each 12-hour period, the
D-4
-------
instrument met all decafluorotrlphenyl phosphlne (DFTPP) tuning criteria
specified by the CLP protocols. Method blanks were prepared and analyzed with
each batch of samples. These blanks met the following criteria:
• Phthalate levels must be below two times the reported detection limit.
• All compounds other than the phthalates must be below the reported
detection limits.
Surrogate standards were added to each sample (except the oil samples)
immediately prior to extraction. The surrogate compounds used are:
• 2-Fluorophenol--100 /
-------
• Initial temperature—30s
• Initial hoid--3 m1n
• Ramp rate--l9Vm1n
• Final temperature--310°.
Sample Notes and Observations
The purpose of this section 1s to summarize observations made during the
processing and analysis of the volatile and semivolatHe samples analyzed by
Compuchem.
The oil samples were not completely soluble in methanol. The diluted
samples were allowed to sit for 48 hours before analysis. At the time of
analysis, a small bead of oil was still visible in the dilutions of samples
Luwa 164 and 172. These two samples were the oil condensates from the high-
temperature runs. They contained substantial amounts of higher boiling hydro-
carbons that would not be expected to dissolve 1n methanol. The volatile
hydrocarbons would be dissolved, however, so that the presence of a small
amount of Insoluble oil would not substantially affect the analysis.
The high background present in the volatile analysis of Luwa 188 has
obscured the xylenes. Although xylenes may be present 1n this sample, a posi-
tive identification was not possible. This was a feed sample and had substan-
tially different results than the other feed samples analyzed. The material
analyzed was probably an aqueous fraction of the feed that had much lower
concentrations of volatlles than the actual feed.
The high toluene and benzene content of sample Luwa 185 (feed sample)
required additional analysis for quantitation. A composite report has been
issued for this sample. Benzene and toluene values have been reported from
purging 1.0 /iL of the methanol extract. All other values, detection limits,
and tentatively identified compounds have been reported from purging 25 jil of
the methanol extract.
Some of the samples contained volatile compounds that were present at low
levels in the associated volatile blanks. In each case, the affected analyte
has been reported with a "B" footnote beside the affected value. The concen-
trations found in the corresponding blanks are presented below.
Blank Associated samples Compound/concentration
104199 Luwa 59, 68, 78, 168, Methylene chloride, 500 /
-------
Blank
Associated samples
Compound/concentrati on
104735 Luwa 96
Methylene chloride, 450 /ig/kg
Acetone, 1,900 /ig/kg
2-Butanone, 11,000 /ig/kg
Toluene, 275 /ig/kg
Chlorobenzene, 440 /ig/kg
None of these compounds (except toluene) was found 1n significant quanti-
ties 1n the analyzed sludges and condensates. Only toluene was listed in the
analytical data compilations, and 1t was generally present at much greater
concentrations than the level found in the blanks.
Inorganic Analyses
Four samples were analyzed for metals following the EPA CLP by Compuchem.
The three solid samples were digested and brought to a 100-mL final volume.
This then was analyzed by inductively coupled plasma (aluminum, antimony,
arsenic, beryllium, cadmium, calcium, chromium, cobalt, copper, Iron, lead,
magnesium, manganese, nickel, silver, sodium, vanadium, and zinc), furnace
atomic absorption (barium, selenium, and thallium), flame atomic absorption
(potassium), and cold vapor atomic absorption (mercury). All analytical
equipment was initially calibrated and verified with continuing calibration
samples. Both soil and water matrix blanks were run prior to analysis, an
ICAP interference check sample was analyzed, and spiked samples using one
sludge sample (Luwa-96) and the aqueous condensate (Luwa-172) were prepared
and analyzed. Duplicates and spiked samples for both a sludge sample
(Luwa-185) and the aqueous condensate were prepared and analyzed. Serial
dilutions (1:4) were performed on the Luwa-188 sample to verify measured
values.
GC and 6C/MS Analysis of Volatiles at IEA
IEA analyzed the VO concentrations of six gas canisters by GC with a
flame-ionization detector, two canisters by GC/MS, and the vapor headspace of
two feed sludge samples by GC/MS. This was done to identify the major com-
pounds in the condenser vent gas, their approximate concentrations, and the VO
in the feed headspace. The conditions for the GC/FID analysis are:
• Column—3 ft x 1/8 in. SS column packed with 0.19 percent picric acid
on Carbopack B
• Initial temperature—50°
• Initial hold—6 min
• Ramp rate--6*/min
• Final temperature—110®
• Standard—Supelco CI to C6 hydrocarbon standard.
D-7
-------
The data obtained by this procedure are quantitative and Indicate the
relative amounts of VOs found in the condenser vent gas. Because of the rela-
tively large number of peaks found in this GC analysis, it was not possible to
identify Individual compounds in the vent gas. These samples were not ana-
lyzed by GC/MS because of the very low vent gas flow rates observed during the
TFE tests; 1t 1s not possible to estimate vent gas emissions accurately from
the process.
The 6C/MS analysis of vent gas canisters and feed headspace was intended
both to identify the specific compounds 1n these samples and to measure their
concentrations. The GC/MS analysis of the feed headspace samples was very
Important 1n that these analyses confirmed the compound identification of VOs
identified by retention times during the onsite GC/FID analysis of the sam-
ples. The analytical conditions for the GC/MS analysis of feed headspace and
vent gas canisters are:
• Instrument—Flnnigan OWA GC/MS/DS
• Column—3 ft x 1/8 1n. SS column packed with 0.19 percent picric acid
on Carbopack B
• Initial temperature—45*
• Initial hold—3 min
• Ramp rate—8Vm1n
• Final temperature—220"
• Final time—15 min
• Standard—Purge and trap of 10 mL of 100-ng/mL benzene standard.
Duplicate GC/MS analysis of the one vent gas sample (Luwa-98) was per-
formed. The analysis of two feed headspaces also constituted a duplicate
sample analysis.
V/ater and Solids Analysis
IEA performed oil, water, and solids analysis on 15 samples from the Luwa
testing. The oil analysis was performed by standard method No. 413.2 (Freon
extraction followed by spectrophotometry measurement of the oil content),
water analysis by ASTM D1744 (Karl Fisher titration), and solids analysis by a
slightly modified Method 224G for solid and semisolid samples.
ANALYTICAL PROCEDURES FOR PLANT I
Samples for volatile and extractable organics initially screened for
volatiles and semlvolatlles by gas chromatography/mass spectroscopy (GC/MS).
After the Individual compounds were identified by GC/MS, the compounds were
quantified by EPA Method 601. Method 601 is a purge-and-trap procedure that
is used for analysis of purgeable halocarbons by gas chromatography (GC). The
D-8
-------
VO data for water in this report are reported for the Method 601 results. The
level of VO 1n the organic phase was determined by direct-injection GC. All
of the vapor samples were analyzed by GC with calibration standards for the
components of interest. The level of VO 1n the sludge sample was quantified
by EPA Method 5030 (methanol and water extraction followed by purge and trap).
EPA's TCLP also was performed on the sludge. Additional details on the
analytical procedures can be found in Section 4 of the site-specific test and
QA plan dated September 12, 1986.
Several laboratories participated in the analyses because they offered
different areas of experience and expertise. Industrial and Environmental
Analysts, Inc. (IEA) performed the VO analysis of the sludge. Alliance Tech-
nologies Corporation (formerly GCA) performed the TCLP analysis of the sludge.
Vapor samples were analyzed at Research Triangle Institute (RTI). Liquid
samples of the wastewater and organic phases comprised the vast majority of
the analyses conducted. This major analytical effort was provided by EPA's
contract laboratory, Engineering and Economics Research, Inc. (EER). EER also
performed the analysis of headspace, metals, and sol Ids contents.
ANALYTICAL PROCEDURES FOR PLANT H
The samples for volatile organics in water were analyzed by modified EPA
Method 624 (40 CFR Part 136, October 26, 1984). Method 624 is a purge and
trap procedure with separation and quantification provided by gas chroma-
tography/mass spectroscopy (GC/MS). This method is particularly well-suited
for analysis of ppb levels of the volatile organic compounds and provides a
nominal detection limit of 10 ppb. The concentrations of the VO compounds in
the stripper feed, aqueous condensate, and effluent spanned several orders of
magnitude. Multiple GC/MS runs were required for each sample at various
levels of dilution to quantify both the high level and low level constituents.
The organic phase of the condensate was analyzed by direct injection gas
chromatography and calibration standards of the components of interest.
Additional details on analytical procedures can be found in Section 4 of the
site-specific test and quality assurance plan dated July 7, 1986.
Tracer gas samples were analyzed by injection of 0.5 cc into a gas chroma-
tograph equipped with a 6 foot by 1/8 inch 0D stainless steel column packed
with 3 percent SP-1500 on 80/120 mesh Carbopack B and a flame ionization
detector. The column temperature was held at 28 "C until propane eluted and
then increased to 150 *C to elute the remaining components of the vapor.
The FID response was calibrated by injection of 0.5 cc of 98.5 ppm propane
in nitrogen mixed with 0.5 cc of overhead vapor sample (no tracer gas pres-
ent). Such a mixture was used to provide consistent measurement of the pro-
pane peak area since there was some overlap between the propane peak and one
of the vapor component peaks. The FID response was recorded on strip chart
and the propane peak area was determined by electronic integration. Selected
samples were analyzed by Plant H's laboratory to corroborate our analyses.
D-9
-------
ANALYSIS PROCEDURES FOR PLANT G
The analyses that were carried out on the process samples are outlined
below. Details of the analytical procedures are presented in the Site Specif-
ic Test and QA Plan Addendum (RTI, 1984).
Onsite Analysis and Measurements
The onsite analyses were limited to (1) determination of hydrocarbon con-
tent of the vent gas stream with a Bacharach TLC meter, and (2) measurement of
the vent gas flow with a pltot tube flowmeter attached to an Inclined manome-
ter.
Offsite Analysis
Analysis of Vent Gas Samples—
The contents of the evacuated stainless steel canister used to sample the
vents were analyzed for volatile organics using the headspace GC method.
Analysis of Liquid Samples—
Semi volatile Organics—The semivolatile organics were measured by extract-
ing the collected liquid samples with methylene chloride, and then analyzing
the methylene chloride by GC. Confirmation of peak identification was per-
formed by GC/MS.
Determination of Liquid pH—The pH of liquid samples was measured using pH
indicator paper.
Determination of Sol ids Content—The total sol ids content of the feed
11 quid was determined using Method 209C.
D-10
-------
APPENDIX E
QUALITY ASSURANCE
-------
APPENDIX E
QUALITY ASSURANCE
The quality assurance (QA) program for these tests included a generic QA
plan that was submitted to and approved by EPA. In addition, a site-specific
test and QA plan for each site tested was submitted to and approved by the EPA
Project Officer and Quality Assurance Officer. The QA program included sys-
tems and performance audits of the analytical laboratories. In general, the
quality assurance objectives for the most critical measurements associated
with the treatment system's perfomance were met. The following sections pro-
vide additional details on the QA results for each test.
THIN-FILM EVAPORATOR PILOT STUDY
This section documents the specific quality assurance (QA) procedures used
1n the analytical measurements of samples. The analyses were: (1) 6C/MS
analysis of volatiles and semivolatlles by CompuChem, (2) metals analysis by
CompuChem, (3) onsite analysis of sludge headspace concentrations by GC/FID
and using a total hydrocarbon analyzer, (4) vent gas analysis by GC/MS per-
formed by IEA, and (5) oil, water, and solids analysis performed by IEA. The
specific QA procedures used for each set of analyses and any results from QA
procedures are described below.
GC/MS Analysis of Volatiles by CompuChem
The sludge samples (feed and bottoms) were extracted with methanol, the
011 condensate samples were diluted 1:1000 with methanol, and the aqueous
condensate was used as a dilute aqueous sample. All analyses were performed
within a 12-hour timeframe of instrument tuning. At the beginning of this
12 hours, the instrument met all bromofluorobenzene (BFB) tuning criteria.
The quantitations are based on a five-point calibration and/or verifying shift
standard. Acceptable instrument blanks were run prior to processing samples.
Three sample surrogates were added to each sample prior to sample prep-
aration and subsequent analysis. Three internal standards were added to the
extracted samples just prior to analysis. (The internal standards and surro-
gates were added directly to the aqueous condensate just prior to analysis.)
Internal standard areas were required to be within -50 to +100 percent of the
corresponding area of the shift standard (sample surrogate). Deviations from
this range would require the repreparatlon and analysis of the samples.
Recoveries of surrogate sample spikes are listed in Table E-l. The average
deviation of surrogate recovery was between 13.7 and 17 percent. Because the
surrogate was added to samples prior to sample extraction, this deviation
should be a measure of the variation associated with the analysis (analytical
precision). The extraction of surrogates from the samples into the methanol
was fairly high for most of the samples but noticeably lower (between 70 and
E-2
-------
TABLE E-1 SURROGATE RECOVERY FROM VOLATILE ANALYSES (COMPUCHEM DATA)
LUWA run #
Sample number
Sample type
LUWA-185
feed,
%
LUWA-188
feed,
X
6
LUWA-68
bottoms,
X
7
LUWA-59
bottoms,
X
8
LUWA-78
bottoms,
X
10
LUWA-98
bottoms,
X
10
LUWA-168
aq cond,
X
Average
deviation
of analysis,
X
Control range
for surrogate
analysis,
X
Sample prep/analytical
B
a
a
a
a
a
b
Surrogate recovery
d4-l,2-Di ch1oroethane
68
100
86
99
77
77
97
13.7
70-121
Bromof1uorobenzene
102
96
79
78
69
69
97
16.4
74-121
d8-To1uene
86
86
81
96
68
68
104
17.0
81-117
^Extraction of 4 g of sample (nominal weight) with 10 mL methanol, GC/MS.
bPurge and trap of 176 fJL sample, GC/MS.
m
i
CO
-------
80 percent) for the two bottoms samples from the high-temperature runs
(Luwa-96 and Luwa-78). Measuring surrogates added to the oil samples was not
possible because of the large dilutions applied to the prepared samples prior
to analysis. This was unfortunate but not catastrophic, as the volatile
removal from the sludge was based on analyses of the feed and bottoms samples
only.
GC/MS Analysis of Semivolatiles
Samples were prepared for analysis as described in the analytical section
of this report. All samples were prepared as extracts (or dilutions with the
oil samples) in methylene chloride. Seven surrogate semivolatile compounds
were added to the extracted samples prior to extraction of the samples with
methylene chloride. No surrogates were added to the diluted oil samples. Six
internal standards were added to the extracts just prior to analysis. The
Instrument met all DFTPP tuning criteria at the beginning of the 12-hour
period when the samples were analyzed. Sample quantitation was based on a
f1ve-po1nt calibration and/or verifying shift standard. A method blank was
prepared and analyzed with the batch of samples.
Of the samples analyzed for semivolatiles, the surrogates were only meas-
ured in a single sample, the aqueous condensate extract. The other extracted
samples were diluted below the detection limits of the surrogates after '
extraction. This permitted the major components to be analyzed, but does not
allow any assessment to be made of the extractions and sample preparation.
The surrogate recovery for the aqueous condensate sample is listed in Table
E-2. This sample showed recoveries of between 47 and 93 percent. It is
unfortunate that surrogates were not measured in the feed and bottoms samples.
If they were, there might be a trend showing less extraction of the surrogate
compounds from the bottoms samples than in the feed samples, which would
explain the bias observed in the process mass balances using these results.
If time and budget had permitted, the samples could have been reanalyzed using
both spiked samples (spikes of the actual compounds of Interest) and surrogate
spikes. As this project was primarily directed to documenting the removal of
VOs from the tested sludge, and the concentrations of the semivolatiles would
be expected to change drastically with whatever sludge is treated, these
results are probably adequate for the project.
Analysis of Metals
Four samples were analyzed for metals following the EPA CLP (Contract Lab
Protocol) by COMPUCHEM. The three solid samples were digested and brought to
a 100-mL final volume. This was then analyzed by inductively coupled plasma
(aluminum, antimony, arsenic, beryllium, cadmium, calcium, chromium, cobalt,
copper, iron, lead, manganese, nickel, silver, sodium, vanadium, and zinc),
furnace atomic absorption (barium, selenium, and thallium), flame atomic
absorption (potassium), and cold vapor atomic absorption (mercury). All
analytical equipment was initially calibrated and verified with continuing
calibrations samples. Both soil and water matrix blanks were run prior to
analysis, an ICAP Interference check sample was analyzed, and spiked samples
using one sludge sample (Luwa-96) and the organic condensate (Luwa-172) were
prepared and analyzed. Duplicates and spiked samples for both a sludge sample
E-4
-------
TABLE E-2 SURROGATE RECOVERY DURING SEMIVOLATILE ANALYSIS (COMPUCHEM DATA)
LUWA run # E 6 7 7 8 8 10 10 10
Sample number LUWA-185 LUWA-188 LUWA-68 LUWA-149 LUWA-59 LUWA-166 LUWA-78 LUWA-164 LUWA-96 LUWA-172 LUWA-168
Sample type feed feed bottoms org cond bottoms org cond bottoms org cond bottoms org cond aq cond
mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg
Sample prep/analytical aaababababc
Surrogate recovery
2-FI uoropheno I dddedededeS9
d6-Phenol 47
d5-Nitrobenzene 87
2-FIuorobenzene 84
2,4,6-TribromophenoI 88
dl4-TerphenyI 93
dl0-Pyrene 92
®30-g (nominal) samples extracted with methylene chloride, final extract volume 8-10 mL, GC/MS.
m b1.0 g oil diluted to 26 mL with methylene chloride, GC/MS.
^ mL of sample extracted with methylene chloride at pH >11 and pH <2, extract concentrated to 1.0 mL, GC/MS.
"Sample was diluted for analysis, surrogates below detection limits.
^Surrogates were not added to diluted oil samples.
-------
(Luwa-185) and the organic condensate were prepared and analyzed. Serial
dilutions (1:4) were performed on the Luwa-188 sample to verify measured
values.
RTI: Analysis of Feed and Bottoms Headspace Concentrations
The analysis of feed and bottoms sludge headspace by GC with a flame-
1on1zat1on detector at the test site required a fairly general approach with
respect to both the compounds analyzed and the concentration ranges examined.
The composition of the feed sludge for testing was not well known prior to the
tests. It was a sample of emulsion tank sludge, and its specific composition
would vary widely with whatever emulsions were generated and stored 1n the
tank prior to the removal of the sludge from the tank. The onsite analysis
was therefore directed toward the analysis of VOs 1n the vapor headspace,
without having to know precisely which compounds were being measured onsite.
The specific compounds were determined initially by compound retention times
and confirmed later by GC/MS analysis of of the feed headspace.
The samples for headspace analysis of VO compounds were half-filled 500-mL
amber bottles, with modified caps to allow gas sample removal through a septum
on the bottle's cap. Samples (25 /iL) were withdrawn from the bottle and
injected Into a GC with a flame-ionization detector. It was calibrated with
both a CI to C6 gas hydrocarbon standard (methane, ethane, propane, butane,
pentane, and hexane 100 ppm in N2) and a liquid benzene standard (200 /ig/mL).
A hexane standard (500 ppm, also used the Bacharach TLV calibration) was
Injected to verify quantitation of hydrocarbons. Table E-3 shows the results
of this standard analysis. Samples of toluene were injected to determine the
retention time of the compound. The field analysis was conducted without
knowing the specific organic compounds that would be present in the samples.
The compound peaks were Identified by the retention times of eluting com-
pounds, and the identification was confirmed by GC/MS analysis of headspace
samples by IEA. The headspace samples were found to contain propane, butane,
pentane, hexane, benzene, and toluene. 2-Butene, cyclopentane, 2-methyl pen-
tane, and 2-methyl butane were also detected in substantial concentrations.
The headspaces of two sets of triplicate feed samples were measured by
this procedure. Table E-4 shows the average concentrations measured, the
standard deviation of the measurements, and the percent relative standard
deviation (RSD) of the six measurements. The percent RSD was below 10 percent
for all components except for the most volatile (propane) and toluene. The
toluene peaks eluted relatively late and had some peak broadening that would
increase the errors associated with area measurement. The percent RSDs in
this table are a measure of the precision of the procedure while the hexane
standard was a measure of its accuracy. Table E-5 shows the results of a
duplicate sample injection of feed sludge headspace. The percent differences
between the two injections are generally smaller than the percent RSDs In
Table E-4, but display the same trends with respect to propane and toluene
concentrations.
The second method of measuring the headspace concentrations of VOs uses a
calibrated total hydrocarbon analyzer. This instrument was a Bacharach TLV
Sniffer, which pulls a continuous sample that is continuously oxidized by a
E-6
-------
TABLE E-3. HEXANE STANDARD ANALYSIS3
Concentrations
Actual, Measured,
Compound
/ig/mL /ig/mL % Difference
Hexane
1.92 1.79 7.4
aUsed 500 p/m hexane standard in nitrogen (*5%).
E-7
-------
TABLE E-4 RELATIVE STANDARD DEVIATION OF ONSITE GC/FID ANALYSES3
Average
% Relative
concentration,
Standard
standard
Compound
/*g/L
deviation
deviation
Propane
121
20
16
Butane
1,065
55
5
2-Methylbutane
1,138
66
6
Pentane
1,029
79
8
2-Methylpentane
421
36
9
Benzene
1,516
105
7
Hexane
432
36
8
Toluene
1,143
277
24
aResults from six analyses of feed headspace concentrations, from
triplicate samples of feed sludge from runs 5, 6, and 7 (feed
drum #3) and runs 8, 9, and 10 (feed drum #4).
E-8
-------
TABLE E-5. DUPLICATE SAMPLE INJECTION, FEED DRUM NO. 3
Concentrations
Compound
/ig/mL
fi g/mL
% Difference
Propane
102
136
28.5
Butane
1,019
1,076
5.4
2-Methylbutane
1,158
1,202
3.8
Pentane
1,000
1,019
1.9
2-Methylpentane
423
392
7.6
Benzene
1,519
1,434
5.8
Hexane
435
413
5.2
Toluene
1,588
1,033
42.3
E-9
-------
catalyst-coated resistance element. The resistance of this element varies
with temperature, which is in turn proportional to the hydrocarbon concentra-
tion of the analyzed gas. The instrument was calibrated with a 500-ppm hexane
standard immediately prior to the analysis of samples. For headspace concen-
tration measurement, the sample probe of the sniffer was inserted into the
half-filled sample jars, the headspace sample was pulled into the analyzer,
and the resulting maximum measured concentration was recorded as the headspace
concentration of VOs for the sample. These readings gave the total hydrocar-
bon concentration of the headspace gases, expressed as parts per million
hexane. These measurements were intended to be a rough measurement of head-
space concentrations and to confirm the results from GC analysis of headspace
concentrations. All of the samples for concentration measurement were mixed
randomly, and the analysis of all the samples took on>y about 15 minutes. The
results of a triplicate sample (run 5) and three duplicate samples are pre-
sented 1n Table E-6. This shows that the technique was fairly reproducible,
although no specific measurements of the unit's accuracy were made during the
testing. The Bacharach TLV Sniffer had a maximum measurable concentration of
10,000 ppm and its range was exceeded by all of the headspace samples of the
feed samples. Although unable to measure the actual headspace concentration
of these samples, the sniffer did give a qualitative measurement of the con-
centrations (greater than 10,000 ppm). The calibration of the Bacharach TLV
was checked using the 500 ppm hexane standard immediately after the analyses
were completed to verify that the instrument did not drift significantly.
This showed a drift of less than 5 percent during the course of the measure-
ments.
The Bacharach TLV was also used to measure concentrations of organics in
the vent gas, feed tank headspace, and vapors above the bottoms when the
sample pot was removed from the TFE. Measured organic concentration of the
vent gas and feed tank headspace also exceeded the range of the instrument.
IEA: 011, Water. Sol Ids, GC, and GC/MS Analysis of Vent Gas
Concentrations
An attempt was made to perform oil, water, and sol Ids analysis of selected
feed sludge, bottoms, organic condensate, and aqueous condensate samples. The
oil analysis was performed by Standard Method No. 413.2 (Freon extraction
followed by spectrophotometry measurement of the oil content), water analysis
by ASTM D1744 (Karl Fisher titration), and solids analysis by a slightly modi-
fied method 224G for solid and semisolid samples. For both the oil analysis
(by Freon extraction) and the sol Ids (by Method 244G), the amount of residue
or oil measured is actually defined by the procedure itself (e.g., the amount
of Freon-extractable oil is the amount of oil extracted by this procedure).
The procedures were applied in a qualitative manner to the samples, and the
results should be viewed as relative applications of the procedures. There
were no specific procedures to assess the data quality of these procedures,
with the exception of duplicate sample analyses. The results of the duplicate
oil, water, and solids analyses are presented in Table E-7.
IEA analyzed the V0 concentrations of six gas canisters by GC with a
flame-ionization detector, two canisters by GC/MS, and the vapor headspace of
two feed sludge samples by GC/MS. This was to identify the major compounds in
E-10
-------
TABLE E-6 BACHARACH TLV DUPLICATE
MEASUREMENTS OF TOTAL HYDROCARBON
IN SAMPLE HEADSPACE
Sample
No.
Headspace
Run concentration
No. (p/m hexane)3
LUWA-47 5
LUWA-65 5
LUWA-66 5
Run #5 Average
Run #5 Standard Dev
Run #5 %RSD
82
78
81
80
1.7
2.1%
LUWA-56
LUWA-57
Run #7 Average
Run #7 ^Difference
120
120
120
0.0%
LUWA-75
LUWA-76
Run #8 Average
Run #8 ^Difference
8
8
83
72
77.5
14.2%
LUWA-93
LUWA-94
Run #8 Average
Run i8 %Difference
10
10
32
23
27.5
32.7%
Measurements taken at 25 "C.
E-ll
-------
TABLE E-7. OIL, WATER, AND SOLIDS ANALYSIS,
PERCENT DIFFERENCE OF DUPLICATE SAMPLE
Feed Feed
drum #4 drum #4
LUWA-83 LUWA-83D Average % Difference
Residue 105 °C
36.6%
Residue 300 *C
3.4%
Residue 550 *C
1.8%
Oil (g/L)
850
Water (weight %)
59.00%
34.4%
35.5%
6.2
5.7%
4.6%
50.5
1.8%
1.8%
0.0
840
845
1.2
59.00%
59.00%
0.0
E-12
-------
the condenser vent gas, their approximate concentrations, and the VOs in the
feed headspace.
The GC data on the vent gas concentration used only a CI to C6 hydrocarbon
standard for calibration and then grouped the eluting compounds into CI, C2,
C3, C4, C5, C6, and C7 ranges to which the appropriate response factor was
applied for the entire range. The data obtained by this procedure are quanti-
tative and indicate the relative amounts of VOs found in the condenser vent
gas. Because of the relatively large number of peaks found in this GC analy-
sis, it was not possible to identify individual compounds in the vent gas.
These samples were not analyzed by GC/MS because of the wide variation of
results expected and the very low vent gas flow rates observed during the TFE
tests. It would not have been possible to estimate accurately vent gas emis-
sions from the process even if there were an excellent analysis of the sam-
ples, so this less expensive and qualitative approach was used Instead. This
procedure was not audited, and the two duplicate samples analyzed (run 8,
Luwa-84, and Luwa-85) show exceptionally poor reproducibility.
The GC/MS analysis of vent gas canisters and feed headspace was intended
both to identify the specific compounds in these samples and to measure their
concentrations. The GC/MS analysis of the feed headspace samples was very
Important in that these analyses confirmed the compound identification of VOs
identified by retention times during the onsite GC/FID analysis of the sam-
ples. The analytical conditions for this analysis are contained 1n Section 5
of this report. A single 100-ng/mL benzene standard was used to calibrate the
analytical method. Although the quality of these data is substantially below
that produced by CompuChem, the Identification of specific compounds is
probably very accurate.
Duplicate GC/MS analysis of the one vent gas sample (Luwa-98) was per-
formed. The analysis of two feed headspaces also constituted a duplicate
sample analysis. These results, and the calculated percent differences, are
shown 1n Table E-8.
QUALITY ASSURANCE FOR PLANT I
The QA program for this test is described in the site-specific test and QA
plan dated September 12, 1986. In addition, an audit of the field sampling
activities was conducted for EPA by an independent contractor (S-Cubed). No
significant problems were found in the audit.
The QA goals for this test are summarized in Table E-9. The results of
the number of samples planned and those successfully analyzed are given in
Table E-10.
Accuracy results for VO in water are presented in Table E-ll and show a
percent recovery of 90 to 117 percent or a percent bias of -10 to 17 percent.
A total of nine samples were spiked with the target to evaluate the effects of
the sample matrix on percent recovery. Precision results for the stripper
feed and bottoms are presented in Tables E-12 and E-13, respectively. The
various replicate samples were taken sequentially in the field and submitted
blind to the laboratory; consequently, the precision results represent the
E-13
-------
TABLE E-8 % DIFFERENCE, GC/MS ANALYSIS OF GAS SAMPLES, VENT GAS AND HEADSPACE (IEA)
Feed
Feed
Vent gas
Vent gas
headspace
headspace
run §10
run #10
X Difference
drum #3
drum §4
X Difference
LUWA-98,
LUWA-98,
vent gas
LUWA-44,
LUWA-81,
feed
Compound
/fc/L
/tt/L
run #10
/fc/L
/i3/L
headspace
2-Methy1 propane
1,800
Butane
2,800
2,800
7
2,200
3,800
63
2-Butene
890
1,400
46
Cyc1opentane
870
1,000
14
2-Methy1 butane
6,000
4,800
22
4,600
6,300
33
Pentane
8,800
6,800
26
6,300
8,300
27
2-Methy1-1-pentene
1,200
Methyl cyc1opentane
2,300
1,700
30
1,600
1,900
17
3-Methyl pentane
2,500
1,800
33
2-Methy1 pentane
6,300
4,400
36
4,300
6,000
16
Benzene
3,000
2,000
40
1,800
2,000
11
Hexane
3,900
2,600
44
2,300
2,600
12
Methyl cyclohexane
1,600
1,000
40
1,000
3-Mothy 1 hexane
1,400
To 1uene
10,000
7,200
33
7,600
8,000
6
-------
TABLE E-9. PRECISION, ACCURACY, AND COMPLETENESS OBJECTIVES
Parameter
Precision
(X RSD)
Accuracy
(% Bias)
Completeness
(*)
Volatile organics
25
25
90
Extractable organics
25
25
90
Metals
15
20
95
Dissolved solids
20
b
100
Filterable solids
20
b
100
aRSD = relative standard deviation.
^The method states that there is no satisfactory procedure to
obtain a measure of accuracy.
E-15
-------
TABLE E-10. PERCENT COMPLETENESS RESULTS
Location
Type
Number of samples
Planned Analyzed
Percent
completed
SI
Water to decanter
Volatile organics
13
5
38*
Sol ids
4
2
50a
Metals
4
3
75a
Headspace
2
1
50
S2
Organic phase
Volatile organics
6
5
83
Headspace
2
2
100
Sol ids
2
1
50
S3
Sludge
Volatile organics
7
7
100
Sol ids
4
4
100
Headspace
2
1
50
TCLP
4
4
100
S4
Water from decanter
Volatile organics
6
8
133u
Sol ids
4
5
125b
Headspace
2
3
150
Metals
0
2
—
S5
Stripper feed
Volatile organics
13
15
115
Headspace
4
2
50c
Sol ids
4
2
50
Metals
5
5
100
S6
Stripper bottoms
Volatile organics
13
15
115
Solids
2
3
150
Headspace
2
2
100
S7
Organic condensate
Volatile organics
12
12
100
Headspace
2
2
100
S8
Primary condenser
Volatile organics
8
8
100
S9
Secondary condenser
Volatile organics
8
8
100
S10
Storage tank
Volatile organics
6
6
100
Sll
Condensate tank
Volatile organics
4
2
50d
S12
Decanter
Volatile organics
4
3
75d
The number of samples taken at SI were decreased because flow occurred at SI
into the decanter on only one test day. Because of no flow on the second
test day, the number of samples at S5 and S6 was increased.
^The number of samples taken at S4 was increased to assess concentrations
before and after treatment in the decanter.
cThe replicate analysis for soids was performed on S6 instead of S5.
dThe number of vapor canister samples was reduced because of inadequate vacuum
on several vapor canisters before sampling.
E-16
-------
TABLE E-11. ACCURACY RESULTS FROM MATRIX SPIKES OF VOLATILE
ORGAN ICS IN WATER3
Number of
Average recovery
Standard
Compound
samples
(percent)
devi ation
Chloromethane
9
96.1
13.6
Methylene chloride
9
117
9.4
1,1-Dichloroethene
9
90.4
10.2
Chloroform
9
94.5
0.25
1,2-Dichloroethane
9
103
12.6
Carbon tetrachloride
9
97.0
8.6
Trichloroethene
9
91.5
7.0
1,1,2-Trichloroethane
9
96.7
9.3
aSpike levels ranged from 7 to 125 ppb.
E-17
-------
TABLE E-12. PRECISION RESULTS FOR VOLATILE ORGANICS IN STRIPPER FEED (S5)
Replicates (ppm) Relative standard
Compound 12 3 4 deviation (percent)
ChIoromethane 31.1 19.2 26.3 24.6 19
Methylene chloride 3,680 3,505 4,072 2,899 14
Chloroform 1,227 1,164 784 2,090 42
Carbon tetrachloride 67.7 54.8 45.4 65.3 18
TrichIoroethyIene 6.4 6.2 10.2 0 77
-------
TABLE E-13. PRECISION RESULTS FOR VOLATILE ORGANICS IN STRIPPER BOTTOMS (S6)
Replicates (ppm) Relative standard
Compound 12 3 4 deviation (percent)
Ch1oromethane
<0.005
<0.005
<0.005
<0.005
0
Methylene chloride
33.3
16.8
8.4
9.4
68
Ch 1 oroform
<0.005
<0.005
<0.005
<0.005
0
Carbon tetrachloride
<0.005
<0.005
<0.005
<0.005
0
Trichloroethylene
<0.005
<0.005
<0.005
<0.005
0
-------
overall precision and include variations in the process over the sampling
time, sampling, and analysis. The precision for two of the three major com-
pounds 1n the feed, methylene chloride and carbon tetrachloride, are within
the target goals of 25 percent. The results for chloroform and trichloro-
ethylene are more variable with percent relative standard deviations of 42 and
77 percent, respectively. Precision results for VO components in the waste-
water from the solids decanter (S4) are given in Table E-14. These results
show reasonable precision for all compounds except carbon tetrachloride. The
precision results for the pure organic phase are given in Table E-15. These
precision results meet the target goals except for one set of replicates for
chloroform (S7).
The percent recovery of VO from the sludge is shown in Table E-16. The
target compounds were spiked into the sludge matrix, and the results show a
low recovery of the spike for all compounds. Precision results for VO in the
sludge are given in Table E-17 and show that the precision goals were met
except for carbon tetrachloride. One of these samples had a high reported
concentration of carbon tetrachloride (14 percent) compared with two values at
3.7 and 3.8 percent.
The accuracy results for vapor analyses are given 1n Table E-18. The
recoveries were all high; however, each analysis was within the target goals
for accuracy. The precision results for the vapor canisters are given 1n
Tables E-19 and E-20. All of these samples also were submitted blind to the
laboratory, I.e., the analyst did not know that the samples were replicates.
The precision goals were met except for carbon tetrachloride 1n one set of
replicates.
The precision results for metals in the wastewater are summarized in
Table E-21 and show reasonable precision except for one low value for chromium
and one low value for lead that significantly increased the relative standard
deviation. Table E-22 presents the analytical precision for the solids
measurements. These samples were split in the laboratory and analyzed as
replicates. The overall precision results for solids are given in Table E-23
and include the variations in both sampling and analysis.
The accuracy results for VO in the TCLP extract are given in Table E-24
with reported recoveries of 66 to 84 percent (-16 to -34 percent bias). The
precision results in Table E-25 show acceptable agreement among the three
replicates. The accuracy results for metals in the TCLP extract are given in
Table E-26 and reveal a range of 92 to 106 percent recovery. The precision
results for metals in Table E-27 also show a good agreement among the three
replicates.
Although some of the data failed to meet the target goals for precision,
the data provide a reasonable assessment of the system's performance for
removal of VO compounds from the waste. For example, the variations in meas-
ured feed and bottoms concentrations do not affect the calculated percent
removal for the various compounds. The greatest variability was noted in
analyses for carbon tetrachloride, which contributed about 1 percent of the
total VO in the feed. The system's performance for total VO removal should be
reasonably accurate because of acceptable accuracy and precision data for
E-20
-------
TABLE E-14 PRECISION RESULTS FOR VOLATILE ORGANICS FROM SOLIDS DECANTER (S4)a
Rep 1i cates
(before
treatment)
Relative standard
deviation (percent)
Compound
1
2
3
ChIoromethane
43.5
29.8
44.7
21
Methylene chloride
4,869
6,576
3,571
22
ChIoroform
1,170
1,821
1,920
25
Carbon tetrachloride
310
60.5
62.4
99
1,1,2-Tr i chIoroethane
6.4
8.0
9.7
21
Rep 1i cates
(after
treatment)
Relative standard
deviation (percent)
Compound
1
2
3
Ch1oromethane
—
17.5
21.4
—
Methylene chloride
3,970
3,071
4,358
17
Ch1oroform
1,464
1,967
1,467
18
Carbon tetrachloride
16.8
21.1
45.1
55
1,1,2-Tr i ch1oroethane
4.6
6.2
6.9
20
aAII results in parts per million.
-------
TABLE E-15. PRECISION RESULTS FOR ORGANIC SAMPLES (g/L)
Location
Methylene chloride
Chloroform
Solid decanter (S2)
890
449
892
387
917
405
Percent relative
1.7
7.7
standard deviation
Condenser decanter (S7)
905
254
1,040
284
Relative percent difference
14
11
Condenser decanter (S7)
1,300
325
1,220
469
Relative percent difference
6.3
36
E-22
-------
TABLE E-16. ACCURACY RESULTS FOR VOLATILE ORGANICS IN SLUDGE (PERCENT)3
Measured Measured Spike Percent recovery
Compound after spiking before spiking recovery of spike
Methylene
chloride
9.44
7.58
1.86
58
Chloroform
6.68
4.28
2.40
75
Carbon
tetrachloride
5.63
3.72
1.91
60
aSpiked into the sludge sample.
^Based on a spiked concentration of 3.2 percent.
E-23
-------
TABLE E-17 PRECISION RESULTS FOR VOLATILE ORGANICS IN SLUDGE (S3)
Compound
Replicates (percent)
1 2 3
Relative standard
deviation
Methylene chloride 7.66 7.49 8.93
Chloroform 4.32 4.23 5.50
Carbon tetrachloride 3.66 3.81 14.1
9.8
15
83
Compound
Replicates (percent)
1 2
Relative percent
difference
Methylene chloride
Chloroform
18.5
9.56
20.6
10.0
11
4.5
E-24
-------
TABLE E-18. ACCURACY RESULTS FOR VAPOR ANALYSES (ppm)
Compound
True
concentration
Measured
1
values
2
Percent
1
recovery
2
Methylene
chloride
6.0
6.0
6.9
100
115
Chloroform
342
348
349
102
102
Carbon
tetrachloride
20.8
23.3
21.0
112
101
E-25
-------
TABLE E-19. PRECISION RESULTS FOR VAPOR ANALYSES AT S8
Replicates (percent) Relative standard
Compound 12 3 deviation (percent)
Chloromethane
0.63
0.62
0.63
0.9
Methylene chloride
39.16
38.71
38.79
0.6
Chloroform
3.99
3.88
3.91
1.4
Carbon tetrachloride
0.192
0.168
0.179
6.7
E-26
-------
TABLE E-20 PRECISION RESULTS FOR VAPOR ANALYSES AT S9
Replicates (percent) Re]at,ve standard
Compound 12 3 deviation (percent)
Chloromethane
0.59
0.58
0.45
14
Methylene chloride
38.16
38.52
31.55
11
Chloroform
4.41
4.13
3.21
16
Carbon tetrachloride
0.575
0.324
0.209
51
E-27
-------
TABLE E-21 PRECISION RESULTS FOR METALS IN STRIPPER FEED (S5)
(ppb unless otherwise noted)
Replicates
Relative standard
deviation (percent)
Metal
1
2
3
Arsenic
<1.0
<1.0
<1.0
0
Beryl 1i um
0.57
0.52
0.46
10.7
Cadmium
8.76
8.49
6.89
12.6
Chromium
0.80
3.46
3.10
59
Copper
70.6
69.6
78.2
6.5
Mercury
a
a
a
a
Nickel'5
1.55
1.89
1.74
9.8
Lead
2.62
0.26
3.80
81
Seleni um
<2.0
<2.0
<2.0
0
Zi nc&
0.25
0.26
0.26
2.2
aNot detected at an absolute detection limit of 4 ng.
^Results for nickel and zinc are in parts per million.
E-28
-------
TABLE E-22. ANALYTICAL PRECISION FOR SOLIDS
Analysi s
Location
Replicates
1 2
Relative percent
di fference
Dissolved
(percent)
S6
0.42
0.41
2.4
S4
2.27
1.76
25
S4
1.18
1.14
3.4
Filterable
(ppm)
S6
11
8.0
32
S4
51
40
24
S4
1,126
1,032
8.7
Total
(percent)
SI
2.38
2.33
2.1
E-29
-------
TABLE E-2a OVERALL PRECISION RESULTS FOR SOLIDS ANALYSES
Replicates
Relative standard
Analysis
Location
1
2
3
deviation (percent)
Dissolved
S4
5.05
4.32
4.15
11
(percent)
S4
2.01
1.66
1.61
12
S5
0.47
0.46
0.46
1.2
Filterable
S4
48
56
48
9.1
(ppm)
S4
8.0
8.0
16
43
S5
51
40
64
23
Total
S3
11.1
13.1
11.9
8.4
(percent)
SI
2.38
2.33
2.53
4.3
E-30
-------
TABLE E-24 ACCURACY RESULTS FOR TCLP VOLATILE ORGANICS
ANALYSIS OF SLUDGE
Expected3
Measured
Percent
Compound
(ppm)
(ppm)
recovery
Carbon tetrachloride
10
6.6
66
Chloroform
10
7.8
78
Methylene chloride
10
8.4
84
aSpiked into the extraction blank.
E-31
-------
TABLE E-25 PRECISION RESULTS FOR TCLP VOLATILE ORGANICS
ANALYSIS OF SLUDGE (S3)
Replicates (ppm)
Relative standard
deviation (percent)
Compound
1
2
3
Carbon
tetrachloride
220
210
210
2.7
Chloroform
2,500
2,600
2,600
2.2
Methylene
chloride
7,100
6,600
7,500
9.0
E-32
-------
TABLE E-26. ACCURACY RESULTS FOR TCLP METALS ANALYSIS OF SLUDGE (S3)
Metal
Expected3
(ppm)
Measured
(ppm)
Percent
recovery
Arsenic
0.50
0.52
104
Barium
1.12
1.03
92
Cadmi um
0.681
0.661
97
Chromium
0.603
0.597
99
Lead
0.50
0.52
104
Mercury
0.0055
0.0053
96
Selenium
0.50
0.53
106
Silver
0.50
0.46
92
aBased on
sample.
original analysis plus
known amount spiked into
E-33
-------
TABLE E-27 PRECISION RESULTS FOR TCLP METALS ANALYSIS OF SLUDGE (S3)
Replicates (ppm)
Relative standard
Metal
1 2
3
deviation (percent)
Arsenic
<0.04
<0.04
<0.04
0
Bari um
0.57
0.63
0.57
5.6
Beryl 1i um
0.003
0.003
0.003
0
Cadmium
0.180
0.180
0.174
1.9
Chromi um
0.113
0.106
0.102
5.2
Copper
0.368
0.334
0.334
5.7
Iron
11.1
11.0
9.1
11
Lead
<0.02
<0.02
<0.02
0
Mercury
0.0006
0.0005
0.0005
11
Nickel
58.4
59.5
60.4
1.7
Zinc
36.5
37.9
34.2
5.2
E-34
-------
methylene chloride, which was the major component in the feed (77 percent of
the total VO).
QUALITY ASSURANCE FOR PLANT H
The quality assurance program for this test 1s described in the site-
specific test and quality assurance plan dated July 7, 1986. A complete tech-
nical systems audit of the analytical laboratory (IEA, Inc.) was conducted on
July 10, 1986, by RTI and a final audit report was Issued on August 12, 1986.
The laboratory was rated "acceptable" in this audit report.
The quality assurance goals for this test are summarized in Table E-28.
The results of the number of samples planned and those successfully analyzed
(percent completeness) are given in Table E-29.
Two types of performance samples were used to assess the accuracy of ana-
lysis of volatile organlcs 1n water. One sample was spiked with a high level
of 1,2-dichloroethane to simulate levels expected in the stripper Influent,
and another sample was spiked at lower levels to assess the accuracy of chlor-
inated organic compounds found at levels lower than 1,2-dichloroethane. Both
types of samples were submitted as unknowns (constituents and concentrations
were not given to the analyst) to the analytical laboratory for analysis and
the results are given 1n Table E-30. Recovery of methylene chloride was high
(+39 percent bias) and exceeded the goal of * 20 percent. Precision was
assessed for volatile organics 1n water by the analysis of triplicate samples
taken sequentially from the Influent (high levels) and effluent (low levels).
The precision results are summarized in Table E-31.
The accuracy of analysis of volatile organic compounds in the vapor phase
was assessed by the analysis of the constituents of interest in audit gas
cylinders (Table E-32). These results show low percent recoveries for 1,2-
dichloroethane and 1,1-dichloroethene. The actual results for 1,2-dichloro-
ethane from the vapor canisters are not expected to be low by a factor of ten.
The vapor pressure of pure 1,2-dichloroethane at 2 to 10 *C 1s 23 to 62 mm Hg.
The vapor phase concentration for the pure compound based on this vapor pres-
sure is 130 to 205 mg/L. Most of the vapor canisters were reported to contain
around 160 mg/L of 1,2-dichloroethane; consequently, the reported results
could not be low by an order of magnitude. Calibration or calculation errors
on the analysis of audit cylinders were suspected, but no problems were found.
The data from the vapor-phase analyses are considered suspect and affect the
estimates of condenser vent rate and efficiency. Precision was assessed by
the analysis of triplicate vapor canister samples taken sequentially from the
condenser vent (Table E-33). The goal of 25 percent was exceeded for all
compounds except the major constituent (1,2-dichloroethane).
Accuracy for metals analysis was evaluated by matrix spiking of the major
metals found in the analysis with the results given in Table E-34. Precision
was assessed by the analysis of triplicate samples with results shown in Table
E-35. Precision results for filterable and dissolved solids are given in
Table E-36.
E-35
-------
TABLE E-28 QUALITY ASSURANCE GOALS
Parameter
Precisi on
(as RSD)a
Accuracy
(% Bias)
Completeness
r«)
Volatile organic compounds
(in liquid phase)
25
20
90
Volatile organic compounds
(111 vapor phase)
25
20
90
Metals
15
20
95
Dissolved solids
20b
b
100
Filterable solids
20b
b
100
aRSD = Relative standard deviation.
hThe method states that there is no satisfactory procedure to oht.iin Rccur;t
-------
TABLE E-29 COMPLETENESS RESULTS
Sample Type
Number
Planned
Number Collected
and Analyzed
Percent
Completeness
Volatile organics
(influent)
14
14
100
Volatile organics
(effluent)
14
14
100
Volatile organics
(condensate)
12
20a
167a
Headspace
8
4b
50
Volatile organics
(vapor canisters)
14
14
100
Filterable solids
6
6
100
Dissolved solids
6
6
100
Metals
6
6
100
dumber of samples increased during
organlc and aqueous phases
the test to provide separate
samples for
^One sample broken
in shipment and
triplicates were missed.
E-37
-------
TABLE E-30. ACCURACY RESULTS FOR VOLATILE ORGANICS
Compound
Spiked
Concentrat ion
(mg/L)
Measured
Concentration
(mg/L)
Percent
Bi as
1, 2-Dichloroethane
102,000
110,000
*7 8
Benzene
442
470
+-6.3
Chloroform
5,380
5,000
-7 1
Methylene chloride
1,008
1 ,400
-39
E-38
-------
TABLE E-31 PRECISION RESULTS FOR VOLATILE ORGANICS (mg/L)
Influent Effluent
Compound % RSD % RSD
No 1 No 2 No 3 No 1 No 2 No 3
1 , 2-L) i c hloroet hdiie 4.700 4.500 4,700
Chloroform 240 230 260
llen/oiif <2 <2 <2
Carbon tetrachloride 2 4 12 17
Chlorohen/ene 28 24 22
Chloroethane 6 8 5 7 3 3
1 , 1-D j c.li 1 oroe thane 8 4 7 1 7 8
1,1-Diohloroethene 2 7 2 3 12
1 , 2-Di cliloi oet hern- 5 4 4 9 5 2
Methylene chloride 16 11 11
Ti'lrachloroethene 0 80 74 0 70
1,1,2-Trichloroethane 6 7 5 0 5 4
Tr ichloroel ht-nt' 3 2 2 8 2 7
Vinyl chloride 7 9 6 3 6 9
2 5
6 3
0 0
34
12
34
8 4
38
4 9
23
6 7
11
9 1
11
22
56
< 01
< .01
< 01
< 01
< 01
< 01
< 01
< 01
< 01
< 01
< 01
< 01
20
61
< 01
< 01
< 03
< 01
< 01
< 01
< 01
< 01
< 01
< 01
< 01
< 01
18
62
< 01
< 01
< 01
< 01
< 01
< .01
< 01
< 01
< 01
< 01
< 01
< 01
10
5 4
0
0
0
0
0
0
0
0
0
0
0
0
-------
TABLE E-32 ACCURACY RESULTS FOR AUDIT GAS CYLINDERS
Cylinder A Cylinder B Cylinder C
Compound Reported True Percent Reported True Percent Reported True Percent
(ppm) (ppm) Ujhs (ppni) (ppm) Bias (ppm) (ppm)
I , 2-Uicliloroet lirinf 9 5 97 -90 --- -
I , 1 -D ichloroethene 8 47 15 2 -44
Vinyl chloride - - - - - 5 78 6 1 -5 2
-------
TABLE E-33 PRECISION RESULTS FOR VAPOR CANISTERS (mg/L)a
Compound
No. 1
CM
O
z
No 3
% RSDb
RPDC
(No 2 and 3)
Vinyl chloride
26
61
64
42
4 8
Chloroethane
14
28
31
37
10
1,1-Djchloroethene
7 9
23
25)
54
23
1,1-Dichloroethane
4 2-
9.0
11 0
43
20
1,2-Dichloroethene
3.2
6 9
8.0
42
15
Chloroform
40
76
89
37
16
1,2-Dichloroethane
160
230
250
22
8 3
aThe precision results include both sampling and analytical precision because
the samples are not exact replicates The canisters were filled sequentially
from the vapor line
^RSD = relative standard deviation.
CRPD = relative percent difference between No 2 and No 3
E-41
-------
TABLE E-34 ACCURACY RESULTS FOR METALS
Metal
Units
Measured
Conoentrat l ori
(unspiked sample)
Spike
Concentration
Total
Measured
in
Spiked Sample
Spike
Recovery
(Percent)
-t.
ro
Coppei
N1nke I
Z 1 IK.
Chromium
mg/L
mg./L
nig/ r.
0 42
<0 03
0 01
<0.03
0.40
0 10
0.10
0 20
.82
10
.11
.20
.53
08
08
22
65
80
70
110
-------
30
0
5 1
1 9
0
17
8 2
0
8 8
29
0
TABLE E-35 PRECISION RESULTS FOR METALS (ppm)
No 1 No 2 No 3
.041 .032 .058
<01 <01 <.01
12 11 .11
30 31 31
< 005 <.005 < 005
006 008 006
51 50 58
< 005 < 005 < 005
28 33 29
<2 .32 <2
<01 <01 <01
E-43
-------
TABLE E-36. PRECISION RESULTS FOR SOLIDS (g/L)
Dissolved Solicls
Filterable Solids
No. 1
14
1 .3
No. 2
14
1 4
No. 3
14
1 4
% RSD
0 0
4 2
E-44
-------
QUALITY ASSURANCE FOR PLANT G
The general QA/QC project plan Is presented In Quality Assurance Plan:
Hazardous Waste Pretreatment for Emissions Control, RTI, 1984, and the site-
specific plan is described in Site Specific Test and QA Project Plan Addendum
Hazardous Waste Pretreatment for Emissions Control: Field Evaluation Plant~G,
RTI, 1985. The analytical work was performed by Industrial Environmental
Analysts, Inc. (IEA). The program's data quality objectives are given in
Table E-37.
GC and GC/MS Analyses
A standard mixture of VOC in nitrogen is prepared in a large glass con-
tainer. A sample of the standard gaseous mixture is withdrawn periodically to
serve as the control for the GC headspace analyses. The gas sample from the
standard is analyzed in an identical manner to the gas sample withdrawn from
the headspace.
Liquid samples are analyzed by gas chromatography using flame ionization
detectors. The liquid samples were extracted with methylene chloride, and the
methylene chloride Injected Into the chromatograph.
GC/MC was used 1n a qualitative mode to verify the components identified
by retention time by the gas chromatography. All reported compounds were
verified by GC/MS.
Data Assessment
For each major measurement parameter, the completeness, precision, and
accuracy of the measured data were evaluated. Completeness is a measure of
the number of acceptable samples or data points actually obtained, divided by
the number that were planned. Ways in which a sample can become "incomplete"
or voided Include not collecting the sample, sampling incorrectly, losing or
breaking the sample In shipment, Improper sample preservation, consuming the
whole sample in a voided analysis, or outlier data point rejection. The com-
pleteness of the field tests was 93 percent.
After the field sampling at Plant G, an audit sample was provided to IEA
by the RTI QA officer. The sample consisted of several organics and was anal-
yzed neat by GC/FID. The results were an average of 30 percent higher than
the known concentrations (Table E-38). This exceeds the bias objective for
the project (25 percent) and indicates the reported concentrations of the
analyzed samples are probably higher than the actual concentrations.
Duplicate Analyses
Duplicate analyses were not performed on the collected samples because of
sample size limitations. Because multiple samples were taken from sampled
process streams, with the process operating at steady state, the variations
within these multiple samples are composed of both the analytical variations
E-45
-------
TABLE E-37 PRECISION, ACCURACY, AND COMPLETENESS OBJECTIVES
Parameter
Uni ts
Method
Prec i s i on
(X RSD)
Accuracy
(X bias)8
Completeness^
(*)
Waste material flow rate
g/s
Mass flowmeter
or calibrated
conta i ner
10
10
100
Source dimensions
cm
Ru 1 er
6
3
100
Gas temperature
°C
Thermometer
6
1
100
Liquid temperature
°C
Thermometer
6
1
100
Waste volume
m3
Dip stick
E
2
100
Gas flow rate
m3/s
Calculated
10
10
100
pH of 1i qu i d
pH
EPA 160.1
1.1 units
1.1 units
100
Liquid density
g/m3
Grav imetr i c
1
1
100
Solids content of liquids
percent
209 C, D, E,c
H as applicab le
10
10
100
Water content of liquids
percent
ASTM, D-1744
20
10
100
Volatile organic compounds
in vent gas
g/m3
Evacuated canister/
GC-FID
26
26
100
Volatile organic compounds
in liquid samples
mg/L
GC-FID headspace
GC-TCD direct analysis
GC-MS
26
26
Qua 1 .
26
26
Qua 1 .
100
100
100
observed - expected
"Percent bias = expected * 10051
''The number of valid data points divided by the number of planned data points expressed as a percentage.
cStandard Methods for the Examination of Water and Wastewater. ISth. ed.
-------
TABLE E-38. OA SAMPLE ANALYSIS
Compound
Actual
volume (ppm)
Concentration
(/ig/mL)
Measured
concentration
(/ig/mL)
% Error
Nitrobenzene3
30.0
36.1
48.7
34.9
2-Nitrotoluenea
1.0
1.16
1.56
34.5
4-Nitrotolueneb
5.59
6.73
20.4
Average % error
29.9
aSample prepared
^Sample prepared
by
by
volume ppm.
weight.
E-47
-------
and any concentration changes occurring within the sampled streams. Table E-
39 shows the high value, low value, mean, standard deviation, and percent RSD
for each of the concentrations measured.
Each of these RSDs exceeds the accuracy objectives (25 percent), but
because the calculated RSD also includes actual concentration differences of
the streams, the collected data are probably acceptable. It is impossible to
determine how much of the observed deviation was due to actual concentration
changes or to analytical variation because no duplicate analyses were per-
formed on an individual sample.
The very high RSDs for the toluene and 1,5-hexadiyne result primarily from
concentration variations in the vent gas, which was confirmed by total hydro-
carbon analysis onsite.
Spiked Samples
Liquid sample FCC-1-V0C-3A was spiked with known concentrations of nitro-
benzene, 2-nitrotoluene, and 4-nitrotoluene, then analyzed in the same manner
as the samples. The recovery of the spikes was 142 percent for nitrobenzene,
99 percent for 2-nitrotoluene, and 124 percent for 4-nitrotoluene. These data
indicate that the analytical data produced by this field trip can be consid-
ered only marginally acceptable.
E-48
-------
TABLE E-39. CONCENTRATION VARIATION WITHIN SAMPLED STREAMS
Nitrobenzene (^g/mL)
Sample stream
High
Low
Mean
SD
%RSD
Feed F1
620
380
505
133
26
Aqueous effluent B1
66
28
41
19
46
Carbon effluent B2
4.3
<0.8
<0.8
—
--
Organic condensate 0
890,000
760,000
787,000
93,000
12
Aqueous condensate C
2,700
1,430
1,900
696
37
Vent gas V
<0.015
<0.015
<0.015
—
--
Average % RSD
30
2-Nitrotoluene
(tfg/mL)
High
Low
Mean
SD
ZRSD
Feed F1
110
54
78
28
36
Aqueous effluent B1
4.6
0.9
2.4
1.6
67
Carbon effluent B2
<0.8
<0.8
<0.8
—
—
Organic condensate 0
220,000
170,000
193,000
25,000
13
Aqueous condensate C
110
42
87
39
45
Vent gas V
<0.015
<0.015
<0.015
—
--
Average % RSD
40
4-Nitrotoluene
Ug/mL)
High
Low
Mean
SD
%RSD
Feed F1
68
42
51
12
24
Aqueous affluent B1
5.6
4.0
4.4
0.9
21
Carbon effluent B2
<0.8
<0.8
<0.8
—
—
Organic condensate 0
110,000
70,000
97,000
23,000
24
Aqueous condensate C
57
23
45
19
42
Vent gas V
<0.015
<0.015
<0.015
--
—
Average X RSD
28
Toluene (tfg/mL)
High
Low
Mean
SD
%RSD
Feed F1
_ _
_ _
_ _
_ _
Aqueous effluent B1
--
--
—
--
Carbon effluent B2
--
--
--
--
--
Organic condensate 0
--
Aqueous condensate C
--
--
Vent gas V
1.4
0.077
0.413
0,559
135
1,5
Hexadiyne
(tfs/mL)
High
Low
Mean
SD
%RSD
Feed F1
Aqueous effluent B1
Carbon effluent B2
Organic condensate 0
Aqueous condensate C
Vent gas V 5.5 0.12 1.4 2.3 164
__
------- |