am a. of Ak Ou tty EMB R.po’t .$-W .O6
ErMfonmsn Pv .ceon Planning and 8lar 8ZPTD ER 1991
RIP, NC 27711
EPA INDUSTRIAL WASTEWATER
METHOD 25D
DEVELOPMENT
EMISSION TEST REPORT
SHELL MANUFACTURING COMPLEX
DEER PARK, TEXAS
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8501 Mo-Pac Blvd.
P.O. Box 201088
Austin, TX 78720-1088
(512)454-4797
INDUSTRIAL WASTEWATER
METHOD 25D
DEVELOPMENT
Final Test Report
Prepared for:
T. Harrison
Emission Measurement Branch
U.S. Environmental Protection Agency
TSD (MD-14), TSD/OAQPS
Research Triangle Park, NC 27711
Prepared by:
Radian Corporation
8501 Mo-Pac Boulevard
P. 0. Box 201088
Austin, Texas 78720-1088
September, 1991
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TABLE OF CONTENTS
Page
1.0 INTRODUCTION 1-1
1.1 Project Description 1-1
1.2 Project Objectives 1-2
1.3 Project Organization and Responsibilities 1-3
1.4 Report Organization 1-4
2.0 SUMMARY AND DISCUSSION OF RESULTS 2-1
2.1 Variability of Method 25D Results 2-4
2.2 Comparison of Method 25D and Methods 8240/8270 2-4
2.3 Comparison of 8240 and 25D Purge Species Analyses 2-9
2.4 Sewer Collection System Liquid to Vapor Comparison.... 2-15
3.0 PROCESS DESCRIPTION AND OPERATION 3-1
3.1 Description of Sample Streams 3-1
3.1.1 M-Plant C-38 Dehydrating Column Bottoms 3-1
3.1.2 IPA C-53 Column Bottoms 3-1
3.1.3 IPA Vacuum Hotwell 3-3
3.1.4 Butanol-Waste Stream Collection Vessel 3-3
3.1.5 Phenol-Acetone Oily Water Sewer Effluent 3-3
3.1.6 Phenol-Acetone Extractor Bottoms 3-3
3.1.7 Olefins-CPI Influent 3-4
3.1.8 T-2800 3-4
3.1.9 Sewer Junction Boxes 3-5
4.0 SAMPLING LOCATIONS 4-1
4.1 M-Plant C-38 Dehydrating Column Bottoms 4-1
4.2 IPA C-53 Column Bottoms 4-1
4.3 IPA Vacuum Hotwell 4-2
11 .
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TABLE OF CONTENTS (Continued)
Page
4.4 Butanol-Waste Stream Collection Vessel 4-2
4.5 Phenol-Acetone Oily Water Sewer Effluent 4-2
4.6 Phenol-Acetone Extractor Bottoms 4-3
4.7 Olefins-CPI Influent 4-3
4.8 T-2800 4-3
4.9 Sewer Junction Boxes 4-4
5.0 SAMPLING AND ANALYTICAL PROCEDURES 5-1
5.1 Sampling Procedures 5-1
5.1.1 Tap Sampling 5-1
5.1.2 Grab Sampling 5-3
5.1.3 Sample Preparation and Handling 5-3
5.1.4 Sampling Matrix and Schedule 5-6
5.2 Analytical Procedures 5-6
5.2.1 Method 25D Analytical Techniques 5-10
5.2.2 Calibration 5-10
5.2.3 Quantitation 5-12
5.3 Departures from Analytical Plan 5-13
6.0 INTERNAL QUALITY CONTROL 6-1
6.1 QA/QC For Methods 8240 and 8270 6-8
6.1.1 Matrix Spike/Matrix Spike Duplicates 6-11
6.1.2 Surrogate Spikes 6-11
6.1.3 Field Blanks 6-21
6.2 Method 25D Quality Control 6-21
6.3 QA/QC For Gas Canisters 6-22
6.4 QA/QC Total Suspended Solids (TSS) and pH 6-22
7.0
REFERENCES
7-1
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LIST OF TABLES
Page
2-1 Analysis of Total Method 25D VOC Variance for Selected
Streams, Variances of Discrete Components of the
Measurement Program 2-2
2-2 Comparison of TNMHC Results for Methods 25D, 8240 (P&T and
DI) and 8270 Recovery of Method 25D Related to Methods
8240/8270 Results, Converted to mg C/g of Sample 2-3
2-3 Method 25D Sampling Matrix and Analysis 2-6
2-4 M-Plant, Liquid Analyses Compared to Method 25D, Qualitative
Analysis Only, Gas Purge Stream Analysis 2-13
2-5 Butanol Waste Stream, Liquid Analyses Compared to Method
25D, Qualitative Analysis Only, Gas Purge Stream Analysis . . 2-16
2-6 Phenol Acetone Oily Water Sever Effluent, Liquid Analyses
Compared to Method 25D, Qualitative Analysis Only, Gas
Purge Stream Analysis 2-19
2-7 Dephenolation Bottoms, Liquid Analyses Compared to Method
25D, Qualitative Analysis Only, Gas Purge Stream Analysis - . 2-21
2-8 Olefins Heavy CPI, Liquid Analyses Compared to Method 25D
Qualitative Analysis Only, Gas Purge Stream Analysis 2-25
3-1 Estimated Sample Stream Composition 3-2
5-1 Sampling Matrix and Schedule 5-7
5-2 Standard Methods and Procedures 5-9
5-3 Analytical Instrumentation and Parameters for Method 25D . . . 5-il
5-4 Analytes Detected in Sample Streams Using Method 8270
With and Without Acid Extraction 5-15
6-1 Summary of Internal Quality Control Procedures 6-2
6-2 Method 8270 CCC and SPCC Results for 2-19-90 6-6
6-3 Method 8270 CCC and SPCC Results for 2-20-90
6-4 Method 8240 Calibration Check Results (100 ppb stcL)
Concentration (ppb)a 6-9
iv
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LIST OF TABLES (Continued)
6-10
Method 8240, Duplicate Matrix Spike Recoveries
Method 8240 D.I., Duplicate Matrix Spike Recoveries
Method 8270 Recovery Check/Recovery Check Duplicates
Surrogate Spiking Specifications for EPA Methods 8240
and 8270
Method 8240, Surrogate Recoveries (%)
Method 8240 D.I., Surrogate Recoveries (%)
Method 8270, Surrogate Recoveries (%)
Method 25D Multipoint Calibration Data
Method 25D Daily Quality Control Data
6-5 8240 System Performance Check Compound (SPCCs) Response
Factor (RF) Results
Page
6-12
6-13
6-14
6-6
6-7
6-8
6-9
6-15
6-10 . . 6-16
6-11 . . 6-19
6-12 6-20
6-13 6-23
6-14 6-25
6-15 Method 25D Audit Samples 6-27
6-16 Summary of Laboratory Quality Control Check Sample Results
for Total Suspended Solids and pH
5-1
Sample Apparatus
LIST OF FIGURES
6-28
5-2
V
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1.0 INTRODUCTION
The Environmental Protection Agency (EPA), Emission Measurement
Branch (EMB), is currently developing and testing Method 25D, a new sampling
and analytical technique to measure the Volatile Organic Content (VOC) of
wastewater. Among other components of the testing program, actual industrial
wastewater streams are being tested to evaluate the method. The testing
program described in this report performs several tests on Method 25D. Method
25D analyses of some selected wastewater streams are compared to other
established testing methods, and the variation of Method 25D results is
evaluated separately for sampling, analysis, and process stream variation.
Additionally, the sewer collection system vapor headspace and corresponding
liquid waste was sampled and analyzed for use in emission estimates by the
Emission Standards Division of EPA.
1.1 Prolect Descrivtion
This work assignment involves support of the technical functions
carried out by the U.S. Environmental Protection Agency, Emission Measurement
Branch, Research Triangle Park, NC. In support of the development of Method
25D, the EPA coordinated a field sampling and analytical program on the
process sewer system at the Shell, Deer Park, Texas petrochemical facility.
Radian was contracted to assist in the planning, sampling, and analysis for
this program.
A pretest survey was carried out by Radian and RTI scientists
together with EPA staff to examine the facilities and to perform some
screening measurements. A set of sampling and analysis objectives were
subsequently developed jointly by the EPA and Radian. The sampling program
was described in the test plan (Radian, 1989).
The pre-test survey was performed on August 8, 1989, at which time
objectives were discussed and sample points were tentatively identified. The
sampling points and their probable constituents were then reviewed by Radian
staff to determine the feasibility of meeting the objectives by analyzing the
1-1
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identified process streams. The objectives were revised after a review by
EPA, EMB and a final matrix of sample points versus objectives was developed
on November 9, 1989. Based on the revised sample stream matrix a sample plan
was developed and sent to the EPA for review November 22, 1989. A sample
preparation trip was made December 14, 1989, to determine exact sample
locations and preparations necessary to perform the sampling task. A sample
site preparation plan was distributed to EPA and Shell, Deer Park on January
5, 1990. Sample preparation began in December, 1989 for a scheduled January
15-19, 1990 sampling trip. The sampling trip was delayed until February 5-9,
1990 due to partial plant shutdowns resulting from freezing temperatures in
December.
1.2 Prolect Oblectives
This test report is a portion of a program undertaken by the EPA,
EMB to assess the following:
• The validity of major assumptions inherent in the methods for
estimating sewer emissions;
• The applicability of Method 25D to actual waste streams; and
• The variability of VOC emission rates from process waste
streams.
The test program described in this report provides analytical results to aid
in the assessments listed above.
The specific objectives of the field test program described in this
report evolved from an initial set of objectives listed in Technical Directive
No. 2, which is provided in Appendix E of this report. After an evaluation by
EPA and Radian Engineers and Scientists, the following set of feasible
objectives for the Shell sampling program were developed:
1-2
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1. Determine whether the samples mess up the glassware (make the
cleanup of analytical equipment difficult).
2. Determine the analytical variability of the method for actual
samples.
3. Determine the variability of the sampling and analysis
components combined.
4. Determine what compounds are in the waste.
5. Comparison of the relative quantities of specific compounds
removed by the 25D purging procedure with the compounds in the
waste stream.
6. Compare the concentrations of compounds found in the sewer
collection system waste streams to the concentrations of the
same compounds in the corresponding vapor headspaces.
1.3 Project Orp anization and Responsibilities
This work assignment (No. 9) is being performed under EPA contract
No. 68D90054. The sampling and analysis portion of the project was performed
by Radian Corporation, Austin, Texas. The sampling site selection was
performed by EPA-EMB, Radian Corporation, and Research Triangle Institute
(RTI). Some other on-site physical measurements such as emission velocity of
the sewer system manholes were performed by RTI. Valuable assistance
throughout the whole testing program was provided by the staff at the Shell,
Deer Park petrochemical facility.
The following sampling streams at the Shell Deer Park facility were
chosen for performance of the tests:
• M-Plant C-38 Recovery Column bottoms;
• IPA Unit C-53 Distillation bottoms;
1-3
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• IPA Vacuum Hotwell;
• Butanol Waste Streams Collection Vessel V-5305;
• Phenol-Acetone Plant Oily Water Sewer effluent;
• Phenol-Acetone Extractor EX-70 bottoms;
• Olefins Plant (heavy side) CPI Influent;
• Olefins Plant (light side) CPI Influent; and
• Anaerobic Treatment Tank T-2800 recycle.
The Sampling Plan was followed except for minor changes in sampling
schedule. All originally planned sample sites were sampled. Changes in the
number of duplicates at some sites were made just prior to the sampling
period, and changes were made to the sampling schedule during the sampling
program to optimize the sampling efficiency.
1.4 Report Organization
Section 2 of this report presents tabulated results of the Method
25D analyses, the measured variabilities, and the comparisons between Method
25D and SW-846 Methods 8240 and 8270. The raw analytical data reports are
presented in the Appendices. Section 3 of this report provides a description
of the processes that were sampled. The sampling locations are identified in
Section 4. The sampling procedures and apparatus are described in Section 5.
The analytical methods also are described in Section 5. Quality Assurance
procedures and results are provided in Section 6 and in the Appendices.
1-4
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2.0 SUMMARY AND DISCUSSION OF RESULTS
The Method 25D field testing program performed at the Shell
Petrochemical complex was performed to evaluate the method using actual
industrial wastewater samples. This evaluation included an assessment the
variability of the various components of the measurement system and also a
comparison of Method 25D to other established methods.
The sampling and analytical program met most of the objectives
of the program as stated in Section 1.2. In this section the results are
discussed and tabulated: In summary, the major findings of the measurement
program related to the specific objectives are as follows:
1. In all cases the deposits on the glassware could be
cleaned well enough to reuse.
2. The analytical variability, presented in Table 2-1, was at
or below the estimated detection limit of 0.03 nig.C/g
sample. Four of the scheduled five streams were tested
for this component. The analytical variability in three
cases out of the four was lower than the sampling and
stream variabilities.
3. The variability of the sampling and analysis combined was
lower in all cases than the temporal variability.
4. Compounds found in the waste were determined by
established SW846 Methods 8240, 8240 DI, and 8270. The
total organic content of the streams as determined by
Method 25D is compared to the established methods (Table
2-2), as well as species comparisons of each stream. As
expected, the results varied greatly from stream to
stream.
2-1
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TABLE 2-1. ANALYSIS OF TOTAL METHOD 25D VOC VARIANCE FOR SELECTED STREAMS
Variances of Discrete Components of the Measurement Program
Sample
Point
(as
/g
Meanb
mg C
methane)
sample
Overall
Standard
Deviationc
Temporal
Variabilityd
Sampling & Analysis
Variabilitye
Analytical
Variability
Std. No. Of
Dev. Samples
Std. No. Of
Dev. Samples
Std. No. Of
Dev. Samples
M-Plant C-38 Dehydration
Column Bottoms 0.204 0.560 2.956 9 0.021 6 N.A.a 0
IPA C-53 Column Bottoms 0.197 0.338 0.396 9 0.153 6 0.003 3
Butanol-Waste Stream
Collection Vessel 20.397 6.888 4.570 9 0.993 7 0.028 2
Phenol-Acetone Oily
Water Sewer Effluent 1.544 0.289 0.577 9 0.306 6 0.412 2
Phenol-Acetone Extractor
Bottoms 2.186 0.494 0.553 8 0.310 4 0.127 3
NOTES: Std. Dev. denotes standard deviation.
No analytical replicates performed for this stream.
bMean of all samples analyzed (25D results reported as mg C (as methane)/g sample).
cvariance of all samples analyzed.
dVariance over 3 sampling days, 3 sampling events per day.
evariance between samples collected during one sampling event.
VarIance of results of replicate analyses made from one sample.
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Table 2-2.
Comparison of TNMHC Results for Methods 25D, 8240 (P&T and DI) and 8270
Recovery of Method 25D Related to Methods 8240/8270 Results, Converted to mg C/g of Sample
Date
-Sampled
25D Sample Code
# of 2$D
Samples
25D Result
Average (mg C
(t)lg)
8240 P&T plus
TICS 5 Results
(mg C (l)fg)
Recovery
- (25DI8240
PIT) (Z) (6)
8240 D I plus
TICSC Results
(eg C (1)lg)
8270 plus
TICS* Results
(mg C (l) g)
Sum of Results
8240 P&T + 8240 DI
+ 8270
(mg C (l)lg) (7)
Recovery
(25D!Sum) (I)
(6)
02106190
MP-l—1-25D
4
0.004
0.038
11
2.45
MS
2.49
0.1
02106190
C53—1-3-25D
4
0.103
0.022
468
2.58
0.0005
2.60
4
02107190
BW-2—l-25D
4
11.9
3.88
307
28.14
MS
32.02
37
02107190
0W-2—3-25D
4
1.38
3.36
41
0.143
0.158
3.66
38
02101190
OL-2—2-25D
1
0.004
0.024
17
1 15
0.018
0.042
10
02107190
0H-2—3-25D
1
0.006
0.351
2
11$
0.042
0.393
2
02I08I90
T28—3-3-25D
4
0.003
MS
—--
3.96
0.03
3.99
0.1
02108190
EB-3—1-25D
4
1.99
1.64
121.34
0.325
0.134
2.10
94.81
(1) Carbon expressed as methane. Results given per gram of sample.
* TICS Tentatively Identified Compound,.
MS No Sample Collected
NOTES:
L 3
1. TNMHC values for 8240 (PIT and DI) and 8270 reported as mg C (as methane)Ig sample. This is based on an assumption that the aqueous samples
analyzed have a density - lgl lml.
2. 824018270 results originally reported in units of &glL. Results converted to mg C (as methane)Ig sample for direct comparison to Method 25D
results.
3. TNHHC for 824018270 samples calculated by:
* 1L * 1mg * . . !!!i * % carbon * 1 mrnole C * 16 mg CH4 = tug C (as methane )
L 1,000ml 1,000 pg ig 12 tug C 3. rnmole C g of sample
4. Average results for 250 TNMHC calculated by randoming “not detected” results between zero and 0.0075 (the LOD).
5. Because of concern for temporal variability in the concentrations, results on this page compare to results of samples collected at
approximately the same time.
6. See discussion in report; comparisons are expected to be dependent on compounds present.
7. In some cases, the same compound is reported in 8240, and 8240 DI, leading to an overestimate of this sum.
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5. The purged stream from the Method 25D analytical apparatus
was sampled by canister and analyzed using the Radian
abstracted TO-14 Method. The top 25 species, benzene,
methane, and TNMRC were compared to 8240 analyses of the
same streams. The results of the canisters are compared
to the SW846 analytical results.
6. The sewer headspace top 25 species analyses are compared
to the 8240 analyses of the corresponding waste streams.
Only in several cases were the profiles of species similar
in the corresponding samples.
2.1 Variability of Method 25D Results
In order to assess the variability of the method, the sampling
program was designed to test the analysis and the sampling portions
separately. For some of sampling points, nine sampling events were set up so
that the variability of the streams, over a period of three days could be
evaluated. For some of the streams multiple Method 25D samples were taken at
the same time to evaluate the sampling technique. In addition, laboratory
replicates (produced by splitting sample vials in the laboratory) of some of
the samples were analyzed to assess the analytical variability. The standard
deviations of the 25D samples were calculated for the laboratory replicates,
for the multiple samples taken during the same sampling event, and for all of
the samples taken. The number of samples available for each type of analysis
is listed in Table 2-3. The results of the standard deviation calculations
are presented in Table 2-1. The analytical results are provided in Appendix
A- 1.
The detection limit for the combined FID and HECD responses was
approximately 0.03 mg/g. Detection limits are calculated from calibration
data using MDL methodology found in the Federal Register, Volume 49, No. 289,
Friday, October 26, 1984, page 43430. Standard diviations of area counts were
calculated for 18 analyses of 2.52 mg C (as CH4) and 0.143 mg Cl standards.
2-4
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These standards were analyzed non-consecutively over a period of six weeks.
The standard deviations were multiplied by 2.602, ‘the student +‘ value at the
99 percent confidence level for 16 replicates, to obtain a detection limit in
mg C and mg Cl. A sample size of lOg was assumed to determine detection
limits of 0.026 mgC (as CH4)/gram sample and 0.004 mgCl/gram sample for a
combined detection limit of 0.03 ingC (as CH4)/gram sample.
2.2 Comparison of Method 25D and Methods 8240/8270
Comparisons between the Method 25D results and the 8240/8270
analyses performed on the same sample streams at the same time are made in
this section. Method 25D results are reported in mgC as CH4/gram sample. The
8240, 8240 DI and 8270 results were reported in units of ug/L. These also
have been converted to unit of mgC (CH4)/gram sample assuming a density of
lg/InL of sample and the percent of carbon in each analyte. Unknown analytes
are assumed to contain 75 percent carbon. The formula for conversion is as
follows.
mgC (CH4) - ig analyte 1L 1 mg analyte 1 mL sample
g sample L sample 1000 mL 1000 .ig analyte 1 g sample
x c
mg analyte 12 rngC 1 mmole C mmole CH4
The comparisons of the SW-846 methods to 25D for each sample stream are shown
in Table 2-2. Under the rigorous purge conditions associated with 25D, it may
be possible to purge some of the water soluble analytes detected by Method
8240 DI or some of the semi-volatile analytes detected by Method 8270, which
is the purpose of the Method 25D purging conditions. A percentage of the mass
recovered by 25D as compared to the SW-846 methods has been included to give a
qualitative indication of the mass detected by 25D in relationship to the
total organic loading of the stream as determined by these methods. The total
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TABLE 2-3. METHOD 25D SAMPLING MATRIX AND ANALYSIS
Sample Point Day Event Number of
Bottles
Number of
Replicates
M-Plant C-38 Dehydration 1 1 4
Column Bottoms 2 1
3 1
2 1 1
2 1
3 1
3 1 2
2 1
3 1
IPA C-53 Column Bottoms 1 1 1
2 1
3 4 3
2 1 1
2 1
3 1
3 1 1
2 1
3 1
Butanol-Waste Stream
Collection Vessel 1 1 1
2 1
3 1
2 1 4 2
2 1
3 1
3 1 1
2 1
3 3
2-6
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TABLE 2-3. (Continued)
Sample Point Day Event Number of
Bottles
Number of
Replicates
Phenol-Acetone Oily
Water Sewer Effluent 1 1 1
2 1
3 2
2 1 1
2 1
3 4 2
3 1 1
2 1
3 1
Phenol-Acetone Extractor Bottoms 1 1 0
2 1
3 1
2 1 1
2 1
3 1
3 1 4 3
2 1
3 1
T-2800 3 3 4 2
2-7
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mass obtained by summing 8240, 8240 DI and 8270 is most likely an over
estimation since some components show up in more than one method. Because of
assumptions notes above and the limited SW-846 method analysis results, the
reader is cautioned that these comparisons are not considered to be
quantitative. A more detailed statistical analyses was not attempted for this
report; the reader may obtain the individual results from Appendix A of this
report.
Very little material was observed in the average results from
the Method 25D analysis of M-plant C-38 Dehydrating Column Bottoms. Method
8240 also detected small amounts of carbon which was primarily two very water
soluble compounds, acetone and methyl isobutyl ketone. Most of the organic
content in this sample was contained in one compound, a C5 alcohol, which was
only detected in the direct injection at a concentration of 2700 mg/L. In
this case, Method 25D is detecting little of the organic mass in the sample,
which may be a result of the water solubility of the organics.
Method 25D detected, on the average, 100 ppm of carbon in the
IPA C-53 Column Bottoms stream. This amount was approximately 470 percent of
the total amount detected by the purgables Method 8240. However, it accounted
for only 4% of the total organic mass in the stream as measured by 8240, 8240
DI and 8270. As with the M-Plant stream, most of the mass was in one compound
identified as a C-5 alcohol, which was detected by the 8240 DI method.
The Butanol-Waste Stream Collection Vessel sample contained a
large amount of carbon as detected by Method 25D. Method 25D accounted for
over 300 percent of the 8240 total. The major components detected by Method
8240 were C 4 -aldehydes (butanals). These compounds were also detected at
higher concentrations in the 8240 DI methods. Therefore, addition of the
Method 8240 mass to the 8240 DI mass would overestimate volatile carbon.
Removal of the mass from the C 4 aldehydes from the 8240 totals leaves 36 ug/g
carbon in 8240. The total of 8240 and 8240 DI would then be 21140 ug/g; and
Method 25D would therefore account for 56 percent of the total mass. Method
25D had compounds purging from the water at the end of the 30 minute purge
2-8
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period, indicating water soluble compounds with low purge efficiencies were
being removed. The compounds and concentrations detected by Method 8240 and
8240 DI appear to confirm this observation. The 8270 sample for this location
was not taken.
Method 25D accounted for 41 percent of the total volatile
carbon detected by Method 8240 in the phenol-acetone oily water sewer effluent
(OW). Most of the carbon detected in Method 8240 was in two compounds,
acetone and toluene, with the majority being acetone which is water soluble
and more difficult to purge. The interaction between acetone and polyethylene
glycol (PEG) is unknown and may cause a lower purging efficiency in the Method
25D samples.
Concentrations of organics in the Olefins Light Combined
Influent (OL) stream were likely too low for Method 25D to detect easily.
Most of the compounds present were light aromatics which purge easily, but
were not present in sufficient concentration to detect on a consistent basis.
Method 25D also detected purgeable components in the Olef ins
Heavy Combined Influent (OH) stream. A considerable amount of organic mass,
351 ug/gC (CH 4 ) was detected in the 8240 analysis of this sample stream.
However, almost all of this carbon was in C 4 -aldehydes which may not purge
efficiently from the PEG solution.
Volatile components were not expected in the T-2800 stream
(T28) and were not readily observed by Method 25D. Two compounds were
observed in the 8240 DI analysis, propanol and an unknown compound. Both are
likely to be very polar and not purge efficiently.
For the Phenol-Acetone Extractor Bottoms (ER) sample, Method
25D shows shows very good recovery when compared to the sum of the other three
analyses. Since many of the compounds detected by 8240 and 8270 are aromatic
hydrocarbons and ketones, it is suspected that this sample had a non-miscible
oil layer on the water. The 8240 sample was diluted by a factor of 10 due to
2-9
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the high levels of acetone present. If a non-miscible layer was present,
dilution of the 8240 sample could result in underestimation of the organics.
An underestimation could occur if the water sample for dilution was taken from
below the surface of the liquid, as is normally done. In Method 25D, all of
the sample is purged which would result in measurement of all of the organics.
The 8240 and 8270 laboratory reports are provided in Appendix A-Il.
2.3 Comparison of 8240 and 25D Purge Species Analyses
The analytical purge stream analysis was compared to the liquid
analysis for five sample streams. An integrated sample was drawn from the
purge stream of the Method 25D analysis apparatus in the laboratory. The
speciation of the VOC analysis for this stream is compared to the species
found by the 8240 analyses of the same sample points. The sample points
compared are the following:
fl-Plant C-38 Dehydrating Column (Table 2-4)
Butanol-Waste Stream Collection Vessel (Table 2-5)
Phenol-Acetone Oily Water Sever Effluent (Table 2-6)
Phenol-Acetone Extractor (EX-70) Bottoms (Table 2-7)
Olefins Combined Heavy CPI Influent (Table 2-8)
Method 25D purges the sample at a flow rate of 6L per minute.
It is not feasible to collect all of this stream, so a slip stream of around
15 mi/mm was integrated into a 2.8L canister over the 30 minute purge time.
Since an integrated sample is collected, the concentration of the organic
compound in the canister is dependent on the rate of purge from the sample
(purge efficiency) and the concentration of the analyte in the sample. A
percent recovery of Method 25D as compared to the other methods has been
included in the tables however, this should not be considered quantitative.
This value has been estimated by converting the Method 25 results and SW-846
method results into total ug of analyte for direct comparison. The following
assumptions and calculations are being made:
2-10
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• A sample size of 10 niL is assumed;
• Assume a linear purge rate and a linear collection rate
for the canister over 30 minutes;
• The amount of sample collected in the canister is
corrected for the percentage of total purge;
• The canister gas phase concentration is converted to total
mass; and
• ug of analyte is calculated from both techniques for
comparison.
The calculations are made as follows:
pg analyte x 0.O1L total pg in 10 niL
L sample
Canister ppbv x L sample x 22.45nL X 2.1
total purge flow 1 pg = total g
amount split to cani8ter 1000 rig
The canister samples were not generally taken from samples
collected at the same time as the 8240 samples. From the Method 25D results
it is clear that the stream concentration will vary from day to day and within
each day. Insufficient data exists to determine if the same compounds are
present from day to day. In addition, the canister samples were used to
collect a water vapor laden slip stream; this might have resulted in loss of
organics in the canister. Finally, the multiple detector analysis system used
to analyze the canister sample may lose some of the water soluble organics
during analyses. Hence the comparisons shown in Tables 2-4 through 2-8 at
best should be considered qualitatively; no quantitative analyses is
inferred.
2-11
-------
As a general observation the compounds detected at the highest
levels in Method 8240 are also those detected at the highest levels in the
canister. The butanol waste stream (Table 2-4) is a good example. Acetone
was the highest concentration in both the 8240 and canister analysis.
Benzene, toluene, and propene recoveries by 25D were approximately 2.5 times
those determined by 8240. It is interesting to note that comparison of Method
25D to 8240 for C4 aldehydes (butyraldehyde) gives high recoveries by 25D.
However, comparison to the higher value determined by 8240 DI results in 66
percent recovery by 25D. This may indicate the purge conditions by 25D are
more rigorous than 8240, but not rigorous enough to completely remove a water
soluble compound such as butyraldehyde.
The Dephenolation Extractor Bottoms has propionaldehyde as the
dominant species in the canister sample and acetone predominant in the 8240
sample. The reason for this anomoly is not known.
2.4 Sewer Collection System Liquid to Vapor Comparison
The liquid and vapor analyses of fifteen sewer collection
system samples are compared in this section. Speciated analyses of grab
samples of the industrial sewer liquid and corresponding vapor headspace are
provided separately in Tables 2-9 to 2-21. The target compounds in the tables
are listed in order of the canister ‘hits’. The TNMHC concentration is
provided as a sum of the tentatively identified compounds (TICs) and hits.
The following sewer samples had no corresponding 8240 sample analyses: The
dephendation Extractor bottoms (CS-EB), the Olefins Plant Manhole East of the
control room (OP-3A), and the repeat of Sewer spot #5 (CSSR).
A report on the sewer study has been produced by Clark Allen.
Mr. Allen’s report is included in the appendices to this report.
2-12
-------
7/19/91
Table 2-4.
N-PLANT
LIQUID ANALYSES C PARED TO METH(I) 25D
Qualit.ativ. Analyst. Only
GAS PURGE STREAM ANALYSIS
Species 8240 P&T Flag 8240 P&T Flag 8240 DI FLag 8240 DI Flag 25D Gas Purge FLag Recovery
(ppb) TICS (pç b) (ppb) TICS (ppb) (ppbv) (Z) a,b Flag
Acetone 18000.0 114000.0 295000
Propionaldehyde 51900.0
Unidentified VOC 10200.0 ac
Methyl isobutylketone 8500.0 4910.0 m 46000
C8 Alkane 2030.0
Ethanol 1800.0
Methanol 324.0
n-Hexane 78.5
F 2-Pentanone 52.2
Methylcyclopentane 13.3
Totuene 12.1
3-Octanone 5.4
Benzaldehyde 4.9
ClOf Alkane 4.5
3-Nethylpentane 4.1
Methylene chloride 1.4
Benzene 1.1
1 1 1- Dichloroethane .8
dO. Alkane .8
C10+ ALkane .6
DichLorodiftouromethane .6
1,4-Dioxane 0.0 (1)
Alcohol CS 2700000.0
Alcohol C6 1600.0
AlkyL pentene CS 7800.0
-------
7/19/91
Table 2-4.
N-PLANT
LICIJID ANALYSES COMPARED TO METHOD 250
Qualitative Analysia Only
GAS PURGE STREAII ANALYSIS
species 8240 PH Flag 8240 P&T Flag 8240 DI Flag 8240 Dl Flag 25D Gas Purge Flag Recovery
(ppb) TICS (ppb) (pub) TICS (ppb) (ppbv) CX) a b Flag
Isobutanol 0.0 (1)
Ketone C6 46.0
Ketone C6 4800.0
Ketone C9 7.0
Methacrylonitrile 0.0 (1)
Unknown 16.0 (2)
Unknown 54.0 (2)
-------
7/19/91
Table 2-4.
N-PLANT
LIQUID ANALYSES COMPARED TO METHOD 25D
Qualitative Analycis Only
GAS PURGE STREAM ANALYSIS
PIT - Purge and trap.
DI - Direct inject.
TICS- TenativeLy identified ccn ounds.
• - Estimated result less than S times detection limit.
(1) - San Le did not contain detectable levels of conçounds
(2) - Unknowns contain 75 Carbon by assuipt ion -
a - Percent Recovery = Total mass (ug) analyte from canister divided by total mass Cug) analyte from Method 8240 multiplied by 100.
ac - Value based on the sun of identified VOCs.
b - All values are converted to ug. Method 8240 results are converted by multiplying the ug/L resuLts by 0.010 1 (assuned
volune of saiiçLe). Canister results are converted by muLtiplying the analyte votune by the density of the analyte:
nL 1 ninole MW 6000 m I/mm purged 1 ug
----xLSa,ple x x -- x x
1 22.45 nI 1 ninole ant, collected in can, mI/mm 1000 ug
g - Ouantitation biased due to interference peak.
m - Detector response outside linear range of integrator. Concentration biased low.
q - Coelutes with broinodichloromethane.
r - Butyraldehyde and 2-Butanone coetute.
-------
6/26/91
Table 2-5.
BUTAJIOL %UISTE STREAM
LIQUID ANALYSES C PARED TO METHOD 250
Qualitative Mlalyaia Only
GAS PURGE STREAM AMALYSIS
Species 8240 P&T Flag 8240 P&T Flag 8240 Dl FLag 8240 DI Flag 25D Gas Purge FLag Recovery FLag
(ppb) TICS (ppb) (ppb) TICS (ppb) (ppbv) (%) a b
Butyraldehyde 256800.0 r c
Unidentified VOC 50900.0 ac
Acetone 10000.0 5040.0 g 2350.0
Ethanol 1660.0 47.0 d
CT Atkene 1520.0
1-Butanol 1490.0
Methanol 1260.0
OletheyL ether 574.0
dO. Atkene 368.0
Propionaldehyde 323.0
C6 Alkene 317.0
C6 Atkene 282.0
Propylene 224.0 280.0 e
C6 Alkene 180.0
C? Atkene 99.3
n-Hexane 61.6
C6 Atkene 42.7
Benzatdehyde 41.2
ToLuene 900.0 • 35.6 290.0
C9 ALkene 31.7
CT Alkene 30.7
Benzene 570.0 * 21.5 240.0
3-Methylheptane 12.5
C, Atkane 12.3
dO. Alkane 11.5
-------
6/26/91
TabLe 2-5.
BUTANOL WASTE STREAM
LIQUID ANALYSES COMPARED TO METHOD 25D
Qualitative Analysis Only
GAS PURGE STREAM ANALYSIS
Species 8240 P&T FLag 8240 P&T Flag 8240 DI Flag 8240 DI FLag 250 Gas Purge Flag Recovery FLag
Cppb) TICS (ppb) (ppb) TICS (ppb) Cppbv) CX) a,b
dO. Alkane 11.0
Trichloroethylene 9.4 q
n-Heptane 8.5
Alkene C l 1100.0 7.8
dO. ALkene 5.3
C9 Alkane 34
Nethylene chloride 720.0 • 1.1 10.0
1,2-Dichloroethane .6
DichtorodifLuorcmethane 1000.0 * .6 5.8
Carbon tetrach(oride .2
1,4-Dioxane 0.0 (1)
Alcohol C2 130000.0
Aldehyde C4 21000000.0 66.0 c
ALdehyde C4 1300000.0
Aldehyde C4 3000000.0 325.0 c
Alkene Cli 25000.0
Carboxylic acid C5 3600.0
Carboxylic acid C7 16000.0
D imethox)methytpropane 170000.0
0 imethoxymethylpropane 930000.0
Isobutanol 0.0 (1)
Ketone Cl 1000.0
Methacrylonitrile 0.0 (1)
Propane 2700.0
Unknown 8500000.0 (2)
-------
6/26191
TabLe 2-5.
BUTANOL WASTE STREAM
LIQUID ANALYSES COMPARED TO METHOD 25D
Qualitative Analyai. Only
GAS PURGE STREAM ANALYSIS
P&T - Purge and trap.
DI - Direct inject.
TICS- Tenatively identified conpounds.
* - Estiumted result less than 5 tImes detection limit.
(I) - S p(e did not contain detectable levels of con ,ounds.
(2) Unknowns contain 75X Carbon by essuiption.
a - Percent Recovery Total mess (ug) anatyte from canister divided by total mess (ug) analyte from Method 8240 uu LtIplled by 100.
ac - Value based on the sue of Identified VOCs.
b - All values are converted to ug. Method 8240 results are converted by aLiltipLying the ug/L results by O.OIOL
(assuned voL,..ie of sneple). Canister results are converted by imaltiptying the analyte volune by the density of the analyte:
nL 1 mole MW 6000 mt/mm purged 1 ug
---x LsanpLe x x x
1 22.45 ml 1 rinole Amt. collected in cane mI/mm 1000 ug
c - Butyratdehyde coepared to C4 atdehydes identified as TICs for 8240 and 8240 DI.
d - Conpared to value from 8240 DI TICS for C2 alcohol.
e - Cuepared to value from Method 8240 TICS.
g - Quantitation biased .ie to Interference peak.
q - Coelutes with bronodichLoromethane.
r - Butyraldehyde and 2-Butanone coelute.
-------
TI 191 91
Table 2-6:
PHENOL ACETONE OILY WATER SEWER EFFLUENT
LIQUID ANALYSES COMPARED TO METHOD 25D
Qualitative Aa alyai. Only
GAS PURGE STREAM ANALYSIS
Species 8240 P&T Flag 8240 P&T Flag 8240 DI Flag 8240 DI Flag 8270 FLag 8270 TICS Flag 250 Gas Purge Flag
(ppb) TICS (ppb) (ppb) TICS Cppb) (ppb) (ppb) (pç bv) X Recovery a,b
Methanol 2800.0
Acetone 3600000.0 1460.0 g 2
Toluene 230000.0 551.0 18
Proplona ldehyde 314.0
W 1dent1fled VOC 104.0 ac
Ienzene 32000.0 59.9 12
n-Hexane 45.6
Nethylene chloride 38.6
1 1,1-Trlchloroethane .5
1,4-Dioxane 0.0 (1)
Acetophenone 7200.0
Alcohol C5 150.0
Alkyt benzene C3 27000.0
Alkyl benzene C3 55000.0
Alkyl benzene C4 9200.0
ALkyl bcnzene Cs 5000.0
Alkyl methoiiy benzene C 27000.0
Alkyl thiophene C2 5400.0
Carboxylic acid C5 3300.0
Ethyl benzene S7.0 •
Nydroxybutanone 65000.0
Isobutanol 0.0 (1)
Methacrylonitrile 0.0 (1)
Methyl ethyl ketone 1100.0 *
Phenol 38000.0
-------
7/19/91
TabLe 2-6.
PHENOL ACETONE OILY WATER SEWER EFFLUENT
LIQUID AMALYSES COMPARED TO METHOD 25D
Qualitative A alyaia Only
GAS PURGE STREAM ANALYSIS
Species 8240 P&T Flag 8240 P&T Flag 8240 DI Flag 8240 DI Flag 8270 Flag 8270 TICS Flag 25D Gas Purge Flag
( ) TICS (pç b) (ppb) TICS (ppb) Cppb) (ppb) (ppbv) % Recovery a,b
Phenol 96000.0
Unknown 2100.0 (2)
Unknown 2900.0 (2)
Unknown 3800.0 (2)
unknown 3800.0 (2)
Unknown 6200.0 (2)
Unknown 7500.0 (2)
PH - Purge and trap.
DI - Direct inject.
TICS- Tenatively identified ccapouads.
* - Estimeted result less than 5 times detection limit.
(1) - Sample did not contain detectable Levels of compotrds.
(2) - Unknowns contain 75% Carbon by aasLmption.
a - Percent recovery — Total mess Cug) analyte from canister divided by total mess (ug) anelyte from Method 8240 siltipI led by 100.
- Value based on the c i a of Identified VOCs.
b - All values are converted to ug. Method 8240 results are converted by ittlplying the ug/L results by 0.O1OL (asataed
voluee of sple). Canister results are converted by um lt1plyIng the analyte volimie by the density of the analyte:
nL 1 ,simile NW 6000 mllmln purged 1 ug
----xLSanplex x x x
L 22.45 ml I resole Aint. collected In can 1 mI/mm 1000 ug
g - Quantitalon biased dee to interference peek.
q - Coelutes with bromodichlorcmethane.
r - Butyraldehyde and 2-Butanone coelute.
-------
6/26/91
Table 2-7.
DEPHENOLAT ION BOTTOMS
LIQUID ANALYSES COMPARED TO METHOD 250
Qualitative Analysis Only
GAS PURGE STREAM ANALYSIS
Species 8240 P&T Flag 8240 P&T Flag 8240 DI Flag 8240 DI Flag 8270 Flag 8270 TICS Flag 25D Gas Purge Flag Recovery Flag
(ppb) TICS (ppb) (pç b) TICS (ppb) (ppb) (ppb) (ppbv) (%) a b
PropionaldeIi de 2710.0
Toluene 400000.0 2540.0 47.0
MethanoL 2270.0
Acetone 1200000.0 1680.0 6.5
Unidentified VOC 167.0 ac
Isopropytbenzene 99.0 23.0
Butyratdehyde 26.3 r 49.0 c
Propane 16.4
Ethyl benzene 130.0 * 8.8 576.0
p-Xylene + m-Xylene 7.5
n-Decane 6.5
Nethytene chLoride 78.0 * 6.2 536.0
C, Alkane 5.9
n-Hexane 4.6
C10+ Alkene 4.3
C10+ Atkene 3.4
Benzene 3.1
C1O+ Atkene 2.6
3-Nethytpentane 2.2
ClO. Atkene 2.0
C9 Alkane 1.5
C1O+ Alkene 1.3
C10+ Atkane .8
1,1-Dich toroethane .2
1,1-Dichloroethylene .1
-------
6/26/91
Table 2-7.
DEPHENOLAT I 0* 1 BOTTOMS
LIQUID ANALYSES COMPARED TO METHOD 25D
Qualitative Analyci. Only
GAS PURGE STREAM ANALYSIS
Species 8240 P&T Flag 8240 P&T Flag 8240 DI Flag 8240 DI Flag 8270 Flag 8270 TICS Flag 250 Gas Purge Flag Recovery Flag
(ppb) TICS (ppb) (ppb) TICS (ppb) (ppb) (ppb) (ppbv) CX) a b
Dichlorodifluoromethane 130.0 * .1 12.3
1 1 4-D loiiane 0.0 (1)
Alcohol C3 89000.0
Alcohol C5 50.0
Alcohol C6 60.0
Aldehyde C6 790.0
ALdehyde C6 2300.0
Alkenyl benzene C3 8600.0
Alkyl benzene C3 260.0
‘ ‘ Alkyl benzene C3 41000.0
Alkyl furanone C3 4100.0
Alkyl thiophene Cl 15000.0
Diethylphthalate 23.0 *
Hexanedione 17000.0
Hydroxyb tanone 110000.0
Isobutanol 0.0 (1)
Ketone C5 80.0
Ketone C5 160.0
Ketone C6 160.0
Methacrylonitrile 0.0 Cl)
Pentenone CI 3700.0
Phenol 170000.0 72000.0
Unknown 1600.0 (2)
Unknown 1600.0 (2)
Unknown 1600.0 (2)
Unknown 2500.0 (2)
-------
6/26/91
TabLe 2-7.
DEPHENOLAT lOW DOT TOWS
LIQUID ANALYSES COMPARED TO METHOD 25D
Qualitative Analyai. Only
GAS PURGE STREAM ANALYSIS
Species 8240 P&T Flag 8240 P&T Flag 8240 DI Flag 8240 DI Flag 8270 Flag 8270 TICS FLag 25D Gas Purge Flag Recovery Flag
(ppb) TICS (ppb) (ppb) TICS (ppb) (ppb) (ppb) (ppbv) (%) a,b
Unknoi,i 2500.0 (2)
Unknoi 2900.0 (2)
Unknown 4100.0 (2)
Unknown 4500.0 (2)
Unknown 5300.0 (2)
-------
6/26/91
TabLe 2-7.
DEPHENOLAT I ON BOTTOMS
LIQUID ANALYSES COMPARED TO METHOD 250
Qualitative AnaLyala Only
GAS PURGE STREAM ANALYSIS
P&T - Purge and trap.
DI - Direct inject.
TICS- Tenativety identified coqc..iids.
* - Estimated result tess than 5 times detection Limit.
(1) - Sai Le did not contain detectable levels of ccapoueds.
(2) - Unknowns contain 75Z Carbon by asstmption.
a - Percent recovery • Total mass (ug) anatyte from canister divided by totaL mass (ug) anatyte from Method 8240 uuLt lpl led by 100.
ac - Value based on the sue of identified VOCs.
b - Alt values are converted to ug. Method 8240 results are converted by siltiplying the ug/L results by O.O1OL (assuned
votune of smupte). Canister resuLts are converted by nuttiplying the analyte value, by the density of the analyte:
nL 1 rinole M W 6000 mt/mm purged 1 ug
----xLSmiplex x X X
L 22.45 ml I raiiote Amt. collected in cane mL/min 1000 ug
c - Canister butyraldehyde results conpared to C4-aLdehydes identified as 8240 TICs.
g - Quantitation biased due to interference peak.
q - Coetutes with brmnodichlorc,nethene.
r - Butyraldehyde and 2-Butanone coelute.
-------
6/26/91
Table 2-8.
OLEFINS HEAVY CPI
Ll JID ANALYSES COMPARED TO METHOD 25D
Qualitative Analya a Only
GAS PURGE STREAM ANALYSIS
Species 8240 P&T Flag 8240 P&T Flag 8270 FLag 8270 TICS Flag 250 Gas Purge Flag Recovery Flag
(pçth) TICS (ppb) (ppb) pçb .ppbv C a,b
AcetaLdehyde 236.0 g
Methanol 181.0 g
n-Hexane 104.0
Butyreldehyde 76.5 r 1.1 c
Nethytcyclopentane 22.1
Acetone 19.3
Unidentified VOC 17.5 ac
3-Methylpentane 10.3
Propane 9.7
J1 To tuene 5.4
Thiophene 3.2
Benzene 3.1
Ethane 2.9
Cyctohexane 1.1
C1O+ Atkene .9
C7 ALkane .9
1,1-Dichtoroethytene .8
Isohexane .8
Dichtorodiftuoromethane 1100.0 * .6 5.2
1 1-Dichtoroethane .4
2-MethytnaphthaLene 7100.0
Acenaphthene 1800.0
AcenaphthyLene 58.0 a
Aldehyde C4 35000.0
Atdehyde C4 37000.0
-------
6/26/91
Table 2-8.
OLEFINS HEAVY CPI
LIQUID ANALYSES COMPARED TO METHOD 250
Qualitative Analysis Only
GAS PURGE STREAI ANALYSIS
Species 8240 P&T Flag 8240 P&T Flag 8270 Flag 8270 TICS FLag 25D Gas Purge Flag Recovery Flag
(ppb) TICS (ppb) (ppb) (ppb) Cppbv) CX) a,b
Atdehyde C4 320000.0
Atkane C4 770.0
ALkene CII 1800.0
ALkyL biphenyL Cl 890.0
AlkyL biphenyt C2 450.0
AlkyL biphenyl C2 850.0
Alkyl biphenyl C2 1000.0
Alkyl dihydronaphthalen 450.0
Alkyt naphthatene C2 1000.0
Alkyl naphthatene C2 1400.0
AlkyL naphthatene C2 2900.0
AlkyL naphthaterte C3 450.0
Alkyl naphthalene C3 620.0
AIkyl naphthalene C3 670.0
Anthracene 290.0
Butoxyethanol 850.0
Dihydroacenaphthytene 1400.0
Dihydrobiphenyl 1800.0
D iphenytmethane 1300.0
Ftuoranthene 89.0 *
Ftuorene 700.0
Indene 740.0
Methytene chloride 770.0 *
Naphthatene 620.0
Phenanthrene 1200.0
PhenoL 110.0 *
-------
6/26/91
Table 2-8.
OLEFINS HEAVY CPI
LIQUID ANALYSES COMPARED TO METHOD 25D
Qualitativs inalyets Only
GAS PURGE STREAM ANALYSIS
Species 8240 P&T Flag 8240 P&T Flag 8270 Flag 8270 TICS Flag 25D Gas Purge Flag Recovery Flag
(ppb) TICS (ppb) (ppb) (ppb) (ppbv) CX) a,b
Pyrene 220.0 *
QuinoLine 170.0
Unknown 540.0 (2)
Unknown 540.0 (2)
Unknown 890.0 (2)
Unknown 1100.0 (2)
Unknown 3000.0 (2)
PAT - Purge and trap.
DI - Direct inject.
TICS- Tenatively Identified co rpouids.
* - Estimated result less than 5 times detection limit.
(1) - Sasple did not contain detectable Levels of conpoulds.
(2) - Unknowns contain 75% Carbon by asstmption.
a - Percent Recovery = Total mass (ug) analyte from canister divided by total mass (ug) anatyte from Method 8240 nu Ltiplied by 100.
ac - Value based on the s ri of identified VOCs.
b - ALL values are converted to ug. Method 8240 results are converted by suLtiplying the ug/L results by O.O1OL (assuned
volune of smiple). Canister results are converted by uultiplying the anaLyte volune by the density of the analyte:
nL I rmiole NW 6000 mI/mm purged 1 ug
x LSanplex x x
L 22.45 ml 1 nsole amt. collected in can, mL/min 1000 ug
c - Conpared to total C4 - aldhydes from 8240 TICs.
g Quantitation biased due to interference peak.
r Butyraldellyde and 2-Butanone coelute.
-------
2.5 Total Suspended Solids and DH Results
The Total Suspended Solids (TSS) and pH analysis results for
each of the streams is presented in Table 2-22. The samples were taken
during the same sampling event as the 8240, 8240 DI, and the 8270 samples were
taken.
2—28
-------
3.0 PROCESS DESCRIPTION AND OPERATION
Nine process streams were sampled. These streams are described
below. In addition, fifteen sewer junction boxes as identified by RTI and EPA
resulting from OVA and velocity measurements were sampled by Radian. Two sam-
pling procedures, grab and tap, were used to sample these process waters.
These methods are described in Section 4. The sampling matrix and schedule
followed are described in Section 5.
3.1 Description of Sample Streams
The sample streams are described below. The actual sampling points
and the physical connections are described in section 4 of this report.
3.1.1 M-Plant C-38 Dehydrating Column Bottoms
The M-Plant, C-38 Bottoms sample was collected just downstream of
the pressure flow controller in the bottoms line. This stream has an average
flow rate of approximately 10 gallons per minute (gpm) at a pressure of about
3 pounds per square inch (psi). This stream was expected to contain acetone,
dialkyl acetone, hexylene glycol, mesityl oxide, methyl isobutyl carbinol and
methyl isobutyl ketone (see Table 3-1).
3.1.2 IPA C-53 Column Bottoms
The IPA C-53 Column Bottoms was sampled from the discharge of pump
CP 31037. This stream was temperature about 200°F and the pressure was about
25 psi. The sample was expected to contain about 400 parts per million (ppm)
isopropyl alcohol (IPA).
3-1
-------
TABLE 3-1. ESTIMATED SAMPLE STREAM COMPOSITION
Sample Point
Butanol
Phenol-Acetone
Phenol -Acetone
N-Plant C-38
IPA C-53
IPA
Waste Stream
Oily Water
Extractor
Dehydrating
Column
Vacuum
Collection
Saver Effluent
Bottoms
Compound
Column Bottoms
Bottoms
Eotvel.l
Vessel
(ppm)
CX Vt)
Acetone
P
1300
0.27
Benzene
9
(0.01
Isobutyl aldehyde
P
n-Butyl aldehyde
P
Cumene
265
(0.01
Dialkyl acetone
P
Diacetene alcohol
sa
<0.01
DIPB
20
Ethylbensene
3
<0.01
Bexylene glycol
P
Bydroxyaceton.
860
0.08
Isebutyl alcohol
p
n-Butyl alcohol
p
Isopropyl alcohol
P
P
Isopropyl ether
Mesityl oxide
P
6
Methanol.
875
0.O4MethyL ethyl ketone
8
Methyl isobutyl carbinol
P
Methyl isobutyl ketone
P
Phenol
113
0.02
Toluene
570
0.05
P — Present
-------
3.1.3 IPA Vacuum }Iotwell
The IPA Vacuum Hotwell sample point was located just after the steam
stripping column of the IPA Unit Acid Concentrator Vacuum Hotwell. This
sample was the effluent from the steam stripper which has an average flow rate
of 100 gpm at a temperature of 150°F. This sample was collected with the grab
method using a bailer. This sample stream contains IPA.
3.1.4 Butanol-Waste Stream Collection Vessel
The Butanol Unit sample point was located at a pump which is on the
discharge side of the Waste Streams Collection Vessel V-5305. The stream is
by product wastevater and condensate from feed gas knock-out pots, and is at
about 100°F. The flow rate of this stream is intermittent but was adjusted
for constant flow during each sampling event. The process stream was expected
to contain 5.3% organics including, iso-butylaldehyde, n-butylaldehyde, and
isobutyl alcohol (see Table 3-1).
3.1.5 Phenol-Acetone Oily Water Sewer Effluent
The Phenol-Acetone Oily Water Sewer Effluent sample point was
located as near to the discharge as possible, at one of the two pumps P 8194
and P 8199. These pumps transfer the oily water from the sewer junction box
to the chemical plant biotreater. The feed to this sewer comes from the
Cumene Unit, the Oxidation Unit, and the Dephenolation Unit. The stream has
an average flow rate of 120 gpm and generally contains about 4500 ppm organics
including: acetone, benzene, cumene, diacetone alcohol, DIPB, ethylbenzene,
hydroxyacetone, mesityl oxide, methanol, methyl ethyl ketone, phenol, and
toluene (see Table 3-1).
3.1.6 Phenol-Acetone Extractor Bottoms
The Phenol-Acetone Extractor Bottoms sampling point was located on
the line between the Dephenolation Extractor and the Oily Water Sewer Drum
Hub. The feed to the Dephenolation Extractor consisted of neutralization
3-3
-------
water from the Phenol-Acetone Unit and water from the PADS Sump. The flow
rate of this stream was about 80 gpm. This stream was expected to contain
concentrations of acetone, phenol, and toluene (see Table 3-1).
3.1.7 Olefins-CPI Influent
Radian sampled the Olefins-CPI Influent at two points:
Olefins-Light Combined Influent - This sample point was located
at the Plate Separator sump of the sewage collection system.
These sources are from washing drains, storm drainage, steamed
pumps, and condensate. Wastewater for this stream are from the
light side of the Olefins Unit.
• Olefins-Heavy Combined Influent - This sample point is located
at the Plate Separator sump of the sewer collection system.
Sources of this sample are from washing equipment, blowdown,
and tank drainage. Wastewater in this area is from the heavy
side of the Olefins Unit and will usually contain C 5 fractions
or heavier.
These sample pits are located about 12 feet below the grate level and were
sampled with bailors. These sample streams were expected to contain high
levels of hydrocarbons, paraff ins, alkyls, and aromatic compounds.
3.1.8 T-2800
This sample stream is located on the Anaerobic treatment Tank
recycle line. The stream was sampled near to the discharge of the recycle
pump. No information was received on the expected composition of this stream.
3-4
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3.1.9 Sewer Junction Boxes
RTI was on site to perform velocity measurements at the sewer
junction boxes. RTI, in conjunction with the EPA Project Officer, identified
15 sewer junction boxes which were sampled for volatile compounds by Radian.
Liquid samples were drawn at the junction boxes immediately after a grab
sample of the vapor headspace in the junction box was taken by VOC canister.
The three separate sewer subsystems sampled were the Main Chemical Sewer, the
Alkene Plant Sewer, and the Phenol Acetone Sewer. Appendix F (provided by
Clarke Allen of RTI) shows the sewer system layout for the three separate
systems tested, including screening of air flows with a velocimeter and
screening of vapor headspace with portable VOC analysis.
3-5
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4.0 SAMPLING LOCATIONS
The sampling location for each of the sample streams was determined
on the basis of site visit information and process stream characteristics.
The objectives of the program, as described in Section 1.2, were the main
determinant in deciding which streams to sample and analyze. The locations of
the sample points were chosen based on the ability to obtain a representative,
well mixed sample of each sample stream. In general, the sample points were
chosen as near to the discharge of a pump so that a well-mixed stream could be
obtained. The requirements of the Method 25D samples call for a cooled
sample, so a sample cooler was installed at each possible sample point.
Bypass purge lines were installed by Shell personnel prior to the
sampling on some of the sample streams which contained particulates to avoid
clogging the sampling apparatus.
A description of each of the sample point locations is provided in
the following subsections.
4.1 M-Plant C-38 Dehydrating Column Bottoms
The M-Plant, C-38 Bottoms was collected from an existing sample line
that is located approximately two feet to the right of the sample collection
bottle and drain (used by plant personnel for sample collection). and a
pressure flow control valve. This sample line has an existing valve, from
which an open ended pipe extends. The end of this pipe was modified with a
by-pass purge line, a 3-way valve, to end with a 1/4” female NPT fitting.
According to Shell personnel, the typical temperature and pressure ranges are
l75-22O F and 2-5 psig, respectively.
4.2 IPA C-53 Column Bottoms
The IPA C-53 Column Bottoms was sampled from the drain line on the
discharge side of the automatic sampler that samples from the discharge of
pump CP-31037. This automatic sampler is located approximately seven feet
4-1
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from the pump, and has discharge pressure of 25 psig, and a temperature of
approximately 200°F. Piping which ends in a female 1/4” female fitting was
installed prior to sampling.
4.3 IPA Vacuum Hotwell
The IPA Vacuum Hotwell sample point is located just after the steam
stripping column of the IPA Unit Acid Concentrator Vacuum Hotwell. The sample
was collected from the open effluent weir using a bailer. The temperature of
this discharge water is only moderately warm.
4.4 Butanol-Waste Stream Collection Vessel
The Butanol Unit sample point was at valve downstream of pump P-
5322, which is located on the discharge side of the Waste Streams Collection
Vessel V-5305. This valve is labeled “FEP E BA300A 0383L”. is approximately
three inches above the pad, and is located 15 feet from a sewer drain. The
temperature was ambient, and the pressure was 2-3 psig. A 3-way valve, by-
pass purge line, and a female 1/4” fitting for the sample cooler connection
was installed at the discharge end of the valve.
4.5 Phenol-Acetone Oily Water Sewer Effluent
The Phenol-Acetone Oily Water Sewer Effluent sample point was
located on the discharge side of pump P-8l94. This pump transfers the oily
water from the sewer junction box to the chemical plant biotreater (the feed
comes from the Cumene Unit, the Oxidation Unit, and the Dephenolation Unit).
From side of the discharge pipe, approximately four feet from the pump, there
is an existing sample valve and pressure gage. At the time of the site visit,
the pressure and temperature was 55 psig and 100°F, respectively. At the
discharge of the last valve on the sample line, a female 1/4” fitting was
installed for the sample cooler connection.
4-2
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4.6 Phenol-Acetone Extractor Bottoms
The Phenol-Acetone Extractor Bottoms sampling point was located on
the line between the Dephenolation Extractor and the Oily Water Sewer Drain
Hub. A 3-way valve, and by-pass purge line, and piping which ends in a female
1/4” fitting was installed be extended from a small side tap located on the
small diameter sampling line that extends from the piping between the two
process units.
4.7 Olefins-CPI Influent
The Olefins-CPI Influent, Heavy and Light, was sampled from the
sewage collection system pit (the water surface is located approximately 15-17
feet below grade). Samples were obtained by lowering a stainless steel bucket
through an inspection opening in the grate down to the water. The grating
opening to use for obtaining the Heavy side sample is located in the top right
corner (as facing from the road) of the pit, which is near the tank labeled
“Turbo-68-Oil”. For the Light sample of the Olefins Unit, the grating
opening located on the left corner (as facing from the road) of the middle
section of the pit was used. This opening Is located over a large influent
pipe, just to the left of the two large diameter steam pipes, and is the third
grating opening from the top left corner.
4.8 T-2800
The sampling location for the Anaerobic Treatment Tank was located
on the sample tap off of the influent line into the automatic pH sampler
located in the left corner of the tank pad (as facing the rail spur). This
sampling line was connected to discharge of the recycle pump. Temperature and
pressure of this sample line are ambient and 80 psig, respectively. No
additional piping, fittings, or modifications were required at this point. The
sample tap ends in 3/8” tubing, to which the sample cooler was connected.
4-3
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4.9 Sewer Junction boxes
The sampling locations for the sewer junction boxes are described in
Appendix F. The sample identifiers for the results of the Method 8240 and
canister analyses are different from the location identifiers found in
Appendix F. The results Tables (2-8 - 2-20) provide the sample I.D.’s
corresponding to the locations identified in Appendix F.
4-4
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5.0 SAMPLING AND ANALYTICAL PROCEDURES
This section summarizes the sampling and analytical procedures
followed on this program. The procedures described in the Test Plan were
followed except for the deviations described below in the relevant
subsections.
5.1 Sanmilna Procedures
Three different sampling procedures were used to sample the various
process streams. A grab sample was used on pit and sewer liquid samples. All
piped streams were sampled through a sample tap and cooler with minimum
exposure to air. Vapor grab samples of the sewer headspace were taken with
evacuated canisters. Laboratory integrated samples of some of the method 25D
samples were also taken with evacuated canisters. A description of each
procedure is included in this section.
The sample custody procedures identified in the sampling plan were
followed explicitly. The samples were shipped daily to Austin, Texas for
analysis.
5.1.1 Tao Samoling
Waste samples in enclosed pipes were sampled with the apparatus
shown in Figure 5-1. Before collecting the sample, all sample lines were
purged with 3 to 4 volumes of the wastewater. The purge wastewater was
diverted to sewer via a separate flexible line prior to sampling. When
sampling, the sample flow was directed into the appropriate sample containers.
The sample flow was shut off after filling each sample container and the
containers were immediately capped. A separate sampling apparatus
(connection, cooling coil, and collection vessel) was set up at each sampling
point to prevent cross contamination of the samples.
5-1
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FROM
SOURCE
STAINLESS STEEL
COIL
(1/4” REDUCER)
THREE—WAY
VALVE
TO SEWER UNE
M
Figure 5-1.
Sample Apparatus
-------
5.1.2 Grab Sam 1ing
A 1000 mL stainless steel container was used to sample the Olefin-
Light Influent, Olefin-Heavy Influent, and the IPA Vacuum Hotwell. The Sever
Junction Box samples were drawn with a sample thief borrowed from the Shell
staff. The containers were lowered beneath the surface of the sampled medium,
allowed to fill, and brought to the surface. The sample was then allowed to
cool to at least 60°F. EPA Method 8240, TSS and pH samples were then poured
into the appropriate sample containers. EPA Method 8270 samples were
collected directly into the one-liter glass bottles. One bailer was used at
each site except for the sewer junction boxes. One bailer was used for all
sewer junction box sample points. The bailers were cleaned with deionized
water between sampling events. A field blank was taken after one of these
cleaning procedures to help assess the possibility of cross-contamination of
the samples.
5.1.3 Sample Preparation and Handlina
Samples collection, preservation, and holding time requirements are
discussed below.
EPA Method 25D
These sample were collected into polyethylene glycol (PEG) to reduce
the loss of volatile organics (VO) during sampling. Thesample container was
prepared by adding approximately 40-50 mL PEG to a 50-60 mL glass sample
container (approximately 10 mL less than the container volume). The container
was weighed with the screw cap, PEG, and any labels to the nearest 0.01 g and
the weight (met) was recorded. Before sampling, the prepared sample
containers were stored in an ice bath until the temperature of the PEG
(measured in a separate aliquot) was less than 40°F. After purging the
sample lines the cooled sample flow (about 50° F) was directed into the con-
tainer. The temperature of each sample stream was checked with a fast-
response digital thermometer inserted into the purge stream prior to each
sampling event. The sample container was filled by immersing the flexible
5-3
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teflon tube end of the sample cooler underneath the surface of the PEG to
avoid contact with the air. As the liquid level was approaching the container
top, the sample container was lowered slightly so chat the tube end was just
above the surface of the collected sample. This allowed the sample container
to be completely filled while avoiding a headspace, and minimizing the loss of
PEG due to overfilling. The container was then capped immediately so that no
headspace existed in the container. The number of drops lost, if any, was
logged for each container filled.
Crab samples were poured from the sample cooling vessel into the
prepared (PEG added and weighed) sample containers. The sample container was
filled and capped immediately so that no headspace existed in the container.
Immediately after sampling, the samples were stored on ice (35-40°F)
to prevent VO loss. The samples were also stored inverted to prevent gas
permeation across the Teflon Septa. Just prior to analyses the sample bottle
was wiped to remove excess moisture and reweighed (ma) to determine the
amount of sample collected.
EPA Method 8240
The EPA Method 8240 samples were collected using two different
methods. The samples to be collected for process water ‘purge and trap’
analyses were collected in VOA vials. The sample plan specified collection of
these samples in PEG, just as the 25d samples were collected. A decision to
change the method of collection was agreed upon between the EPA project
manager and Radian’s Analytical task leader for analytical reasons. Therefore
the 8240 ‘purge and trap’ samples were not collected in PEG, they were
collected in VOA vials without any preservative. The direct injection samples
and the Sewer Junction Boxes purge and trap samples were collected as
described above, also into sample containers which did not contain PEG. These
samples were also stored inverted at 35-40°F.
5-4
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EPA Method 8270
EPA Method 8270 samples were collected into one-liter glass bottles.
Tap samples are collected after purging the sample lines. The cooled sample
flow (about 50°F) was directed into a one-liter glass bottle. The bottle was
filled and capped immediately. Grab samples were poured directly from the
bailer into the sample containers. Immediately after sampling, the samples
were stored on ice (35-40°F).
EPA Methods 150.1 (OH) and 160.2 (TSS )
EPA Methods 150.1 (pH) and 160.2 (TSS) samples were collected into
250 mL plastic bottles using the technique described in Section 2.2.3.
Radian Gas Canister Samples
Two types of Radian gas canister samples were collected. Fifteen
grab samples were collected at Sewer Junction Boxes. After ensuring that the
valve on the evacuated canister was closed, the cap from the filter inlet was
removed. The initial canister pressure was taken and the pressure guage was
left on the canister. The sample inlet tubing (an assembly of one-quarter
inch stainless steel and teflon tubing) was purged by drawing air through it
with a portable gas analyzer pump for approximately one minute. One end of a
length of Teflon tubing was extended into the sewer headspace and the other
end was connected to the canister filter inlet. The canister inlet valve was
opened until the canister pressure dropped below 10 psi. The sample inlet
tubing was removed, the cap was replaced on the filter inlet, and sampling
information was recorded on the canister sample tag. The sample custody
sheets were completed and the canister was shipped to the laboratory within
two days for analysis.
Time integrated canister samples were drawn from five EPA Method 25D
sample purges during their analyses. These samples were collected at the
flowmeter vent over the 30 minute purging and analyses period. The samples
that were drawn in the laboratory did not correspond to the sampling plan In
5-5
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all cases. The plan called for analysis of the canister samples to coincide
with the 8240 analyses of the same sample point. For three of the five tests
the canister samples were taken from a different sampling event than the 8240
sampling.
5.1.4 Sampling Matrix and Schedule
The sampling matrix and schedule are given in Table 5-1. This
schedule varies slightly from the sampling schedule in the sampling plan. The
Olefins separator samples were taken on the second event of the second day
instead of the third day, and then they were repeated again on the second day
because the 8240 samples were forgotten in the second event. The integrated
canister samples differed from those identified in the plan.
5.2 AnalytIcal Procedures
The method and procedures used to prepare and analyze samples are
discussed in this section. Analyses was performed according to EPA SW-846
(U.S. EPA, 1986), EPA 600 (U.S. EPA, 1979), Radian (Radian, 1989), and an
Abstracted Method T0-l4, (Radian, 1987). The standard methods and procedures
used on this project are summarized In Table 5-2, showing the parameter,
method, and method references for each sample type.
The procedures listed in Table 5-2 were followed without significant
modification. In accordance with EPA’s Prevaration Aid for HWERL’s Category
II Quality Assurance Prolect Plans , procedures which are generally recognized
as approved, standard methods are described by reference in this document.
These include SW-846 and EPA-600 methods.
5-6
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TABLE 5-1. SAXPLING MATRIX AND SCHEDULE
IPA C-33 Coluizri Bottoms
(C53)
Method 25D
PEG (a)
4 Cd)
1 (d)
1 (d)
2 1 1 Cd)
2 1(d)
3 1 Cd)
3 1 1 Cd)
2 1(d)
3 1 Cd)
Tap 1 1 lCd)
2 1(d)
3 4(d)
2 1 1 (d)
2 1 Cd)
3 1 Cd)
3 1 1 Cd)
2 1 Cd)
3 1 Cd)
Grab 1 1 1(d)
Tap 1 1 1(d)
2 1 Cd)
3 4 Cd)
2 1 4 Cd)
2 lCd)
3 1 Cd)
3 1 1 Cd)
2 lCd)
3 1 Cd)
EPA
Methods
EPA 130.1 and
Method 160.2
8270 (TSS and pH)
1 (g)
Sample Point
N-Plant C-38 Dehydrating Column Bottoms
CMI ’)
Sample
Type
Tap
Sampling
Day Event
1 1
2
3
EPA Method 8240
P & T D.I. (b)
1 Ce) 1 (1)
Radian Canister
Grab Integrated Cc)
IPA Vacuum Hotwell
CVH)
Butanol-Waste Stream Collection Vessel
(EU)
1 (e) 1 Cf) 3 (h)Ci) 2 (1 dup)
1 (g)
1
1 Ce) 1 CE)
1 Ce) 1 CE)
1 Cs)
1 (g)
(Continued)
-------
TABLE 5-1. (Continued)
Phenol-Acetone Oily Water Sever Effluent
(OW)
Tap 1 1 lCd)
2 lCd)
3 1 Cd)
Phenol—Acetone Extractor Bottoms
(EB)
2 1 1 (d)
2 1(d)
3 4 Cd)
3 1 1 Cd)
2 1(d)
3 1 Cd)
Tap 1 1
2
3
1 Cd)
1 Cd)
2 1 1 (d)
2 1(d)
3 1(d)
3 1 4 (d)
2 1(d)
3 1(d)
2 2 1 (d)
2 2 1 Cd)
2 3 1 Cd)
3 3 4 Cd)
1 (h) 1 Cs)
1 (h) 1 (a)
1 (h) 1 Cs)
1 CE) 1 (h) 1 (g)
15 Sewer Junction Boxes (CS)
Csamples listed to be collected per box)
(a) Sample collected in polyethylene glycol.
(b) Sample collected In vial with no additives.
(c) Gas sample collected from liquid sample purge vent during Method 250 analysis in the laboratory.
Cd) Collect a set of five vials for each sample.
Ce) Collect a set of 3 vials for each sample. Samples for EPA Method 8240 Purge and Trap.
Cf) Collect a set of 3 vials for each sample. Samples for EPA Method 8240 Direct Injection.
Cs) Collect sample in a 250 aL plastic bottle.
Ch) Sample collected in a one-liter glass bottle.
Ci) Collect a set of 3 vials for each sample. (Do NOT collect in PEG). Samples for EPA Method 8240 Purge and Trap.
NS - Not specified, sample as schedule permits. Must coordinate sampling with RTI.
17 (2 dupa)
EPA
Methods
Sample
Sampling
Method 250
EPA Method 8240
EPA
Method
150.1 and
160.2
Radian Canister
Sample Point Type Day Event
PEG Ca)
P 1 T
D.I.
(b)
8270
CTSS and
pH)
Grab Integrated Cc)
;I1
1 Ce) 1 (f) 1 (h) 1 (g)
1 Ce) 1 CE) 1 (h) 1 (g)
Olef ins-C?! In.fluent
a) Olefina-Light Combined (OL.)
b) Olef ins-Heavy Combined (OH)
T-2800 CT28)
Crab
Grab
Grab
Tap
1
1
1
1 Ce)
1 Ce)
Crab MS MS 15 (1)
-------
TABLE 5-2. STANDARD METHODS AND PROCEDURES
Parameter
Sample
Type
Method
Title
Method Type
References
Volatile Organics Purge
and Trap
A
EPA Method 8240
GCIMS for Volatile Organic.
CCIMS
SW-846
Volatile Organic. - Direct
Injection
A
EPA Method 8240
GCIMS for Volatile Organic.
CCIMS
SW-816
Volatile Organic. -
Content
A
EPA Method 25D
Determination of the Volatile
Organic Content of Waite
Samples
GC-FIDIEECD
Radian
Volatile Organic.
C
Radian Gas Canister
Method (Abstracted
Method TO-14)
Determination of VOCs in
Ambient Air Using 5 13 1 1 1*
Passivated Canister Sampling
and CC Analysis
GC-FIDIPIDIHECD
Cox
Semivolatile Organic
Compounds
A
EPA Method 3320
Continuous Liquid-Liquid
Extract ion
SW-846
A
EPA Method 8270
CC(NS for Semivolatile
Organics: Capillary Column
Technique
CCIMS
SU-846
TSS
A
EPA Method 160.2
Residue, Non-Filterable
Gravimstric
EPA 600
pH
A
EPA Method 150.1
pH
Electrometric
EPA 600
A — Aqueous sample.
C — Gas canister sample.
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5.2 Method 25D Analytical Techniciues
The analytical techniques used during sample analysis and data
reporting are described in this section. Instrumentation, calibration and
quantitation procedures used in conjunction with Method 25D analyses are
discussed in this section.
5.2 .1 Instrumentation
The purge unit used for the proposed Method 25D analyses was
constructed by the Research Triangle Institute (RTI) for the EPA. The
apparatus was loaned to Radian by the EPA for use in the interlaboratory study
of Method 25D and was also used in this study.
Per RTI instructions, the purge unit was constructed in a fume hood.
The purge apparatus was connected to the Flame Ionization Detector (FID) and
the Hall Electrolytic Conductivity Detector (E1CD or HECD) via two 4 meter
sections of heat traced 1/8” stainless steel tubing. Table 5-3 outlines the
instrumentation and parameters for the proposed Method 25D. Data acquisition
on to a magnetic format was accomplished by Model 3357 Laboratory Automation
System, a Hewlett-Packard software package. Manual integration of the total
area of each sample (over the 30 minute purge time) was performed by the
peripheral program CPLOT.
5.2.2 Calibration
A single calibration gas, containing 503.9 mg carbon (C) as methane
and 26.68 mg chlorine (Cl) per liter in the form of propane and 1,l-dichloreo-
thane (balance air), was used to obtain calibration for both detectors.
Different load volumes of the calibration gas provided four point calibration
curves for each detector to determine detector response and linearity. High
mass loading of the detectors was used during calibration to simulate possible
high concentrations is waste samples. Calibration at these high levels
produced a nonlinear HECD calibration curve. This nonlinearity is suspected
to be a result of detector saturation and/or reaction tube carbonization. As
5-10
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TABLE 5-3. ANALYTICAL INSTRUMENTATION AND PARAMETERS FOR METHOD 25D
Analytical Ins trumentation
Instrument: Tracor 560 Gas Chromatograph
Detectors: Flame Ionization Detector (FID)
Hall Electrolytic Conductivity Detector (HECD)
Carrier Flows: U}IP Nitrogen at 17 mL/min for the HECD
UHP Nitrogen at 30 mL/min for the FID
Detector Flows: FID — H 2 at 80 mL/min; Air at 350 inL/min
HECD — H 2 at 35 mL/min; 1-propanol at 400 uL/min
Detector Temp: FID — 125°C
HECD — 250°C base and 850°C furnace
CC Oven Temp: Isothermal at 100°C
Purge Parameters
Temperature: 75°C
Purge: UIIP Nitrogen at 6 L/min
Pressure: 3.5 plus or minus 0.75 psig
Rotameter: 3.2
Data Acquisition
Hardware: Hewlett-Packard 18652A Analog/Digital Converter
Hewlett-Packard 1000 Series E Mainframe CPU
Hewlett-Packard 150 Terminal
Hewlett-Packard 2932A Printer
Software: Hewlett-Packard Laboratory Automation System
5-11
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a result, the acceptance criteria for the HECD calibration curve was a
correlation coefficient (r) equal to on greater than 0.980. For FID calibra-
tion criteria, r is greater than 0.995 as stated in the method.
Detector calibration was monitored on a daily basis through the
analysis of quality control checks prior to analysis of samples. The daily
quality control check involved the analysis of a middle concentration standard
from the standards used in the multipoint calibration. The response factor
obtained was then compared to the response factors from the original multi-
point. For the FID daily QC, the acceptance criteria was a relative percent
difference (RPD) of less than 10% from the average multipoint calibration
response factor. The daily QC HECD acceptance criteria was a RPD of less than
30% between the daily QC response factor and the average response factor from
the multipoint calibration responses.
Upon completion of sample analysis each day, calibration checks were
performed at concentrations that bracketed the responses observed in the
samples. Typically, one low and one high level standard were analyzed at the
end of the day. The results of these calibration checks were then compared to
the multipoint calibration curve and used during quantitation.
5.2.3 Ouantitation
Quantitation of samples was achieved via the use of average response
factors from the multipoint calibration curve. If required, according to the
method, the end of the day calibration checks would also be used. The
concentration of total carbon in each sample was obtained by the following
calculation if the end FID calibration check was within 20% of the average
multipoint RP:
Conc. Total C (as CH 4 ) Total FID x Avg. Multipoint RF
Area Count (mg C (as CH 4 )/area count)
5-12
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If the end of the day FID calibration check was different from the
average multipoint RF by 20-50%, the end calibration check’s RF would be
averaged with the multipoint’s RF before calculating carbon concentrations in
samples. A difference of greater than 50% between the end of the day FID
calibration check and the RF from the same concentration in the calibration
curve mean the average multipoint RF was used for quantitation and the data
were flagged.
Units of mg.C (as methane)/g sample were used when reporting
volatile organic concentrations. All calculations and the calibration curves
were reported in units of mg.C (as methane)/L. The results are reported as
methane in order to represent the contribution due to both the carbon and
hydrogen molecules, in the final concentration. The measured concentration
(mg C (as methane)/L) was divided by the sample weight (final weight minus
bottle weight minus PEG weight) to obtain the units of mg C as methane per g
of sample.
Total mg Cl from the HECD response was quantitated in a similar
manner to that of the mg C calculations. Since a 0.995 or better correlation
coefficient is generally required to use a RF based on a linear regression
slope, the average RF from the concentration level in the calibration point
closest to the sample’s concentration was used for quantitation. No data
flags were used in this quantitation method as no components were observed on
the HECD detector.
5.3 Departures from Analytical Plan
An error was made in the sample preparation laboratory and the
samples collected for Method 8270 analyses were not extracted under acidic
conditions. Unfortunately, when the mistake was discovered, the samples had
been discarded and the acidic extraction could not be performed on these
samples.
In order to obtain semi-volatile information on these sample
streams, unused VOA samples from Methods 8240 and 8240 P1 were combined and
5-13
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extracted under base/neutral and acid conditions. Generally, 100 to 150 mL of
sample were available for extraction. These extracts were then concentrated
and analyzed by Method 8270. As a general rule, analyte concentrations were
such that little or no sensitivity was lost due to the smaller sample size.
Table 5-3 presents concentrations for the Method 8270 analytes in
the selected sample streams. A comparison is made between the samples
extracted under base/neutral conditions and those extracted under base/neutral
and acidic conditions. The agreement is very good with the major differences
being in acidic compounds such as phenol, as would be expected. Some minor
discrepancies are observed near the detection limits. Some differences are
observed in the Heavy Combined Influent Olefins stream. However, this stream
contained an oil layer on the water which could account for some of the
differences.
The matrix spike and matrix spike duplicate samples were not
extracted under acidic conditions. Relative Percent Differences (RPDs) for
the neutral compounds were very good with the exception of N-nitrosodipropyla-
mine for the Phenol-Acitone Oily water stream. RPDs for neutral compounds
from the IPA C-53 column bottoms stream were good. Analytical reports for the
8270 analyses, including the samples having only the base/neutral extraction
performed are in Appendix E.
5-14
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TABLE 5-4. ANALYTES DETECTED IN SAMPLE STREAMS USING METHOD 8270
WITH AND WITHOUT ACID EXTRACTION
Concentration
Sample Stream Compound 8270 w/o Acids
(ug/L)
8270 w/Acid
IPA C-53 Column Bottoms Pyridine 46 31
Olefins-Light Combined Acenaphthene 120 100
Influent Fluorene <97 45
2-Methylnaphthalene 740 520
Naphthalene 890 240
Benzyl Alcohol <97 190
Phenanthrene <97 48
U’
Olefins-Heavy Combined Acenaphthene 380 1800
Influent Acenaphthylene 13 58
Anthracene 63 290
Fluoranthene 19 89
Fluorene 140 700
2-Methylnaphtha lene 1100 7100
Naphthalene 250 620
Phenanthrene 300 1200
Pyrene 47 220
Phenol-Acetone Oily Water Acetophenone 7200 7200
Server Effluent Phenol 4800 38000
Phenol-Acetone Extractor Acetophenone 30 <20
Bottoms Phenol 5500 72000
Diethylphtha late <29 23
T-2800 ND ND ND
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6.0 INTERNAL QUALITY CONTROL
An internal quality control system is a set of routine internal
procedures for assuring that the data output of a measurement system meets
prescribed criteria for data quality. Inherent and implied in this control
function is a parallel function of measuring and defining the quality of the
data output.
Generally, internal quality control procedures may be divided into
two overlapping categories. One category includes those procedures which are
used to control data quality within prescribed limits of acceptability. These
acceptability limits are usually related to data precision, accuracy, and
completeness. The other category includes those procedures designed to
provide a quantitative assessment of data quality, again in terms of
precision, accuracy, and completeness. Some internal QC procedures, by their
nature, serve both control and assessment functions.
This section addresses QC procedures associated with the various
sampling and analytical efforts. Included are general quality control
considerations related to each procedure, as well as specific quality control
checks which provide ongoing control and assessment of data quality, in terms
of precision and accuracy. Quality control checks which provide the basis for
quantitative control and assessment of data quality, along with required
frequency, acceptance criteria, and corrective action, are summarized in Table
6-1.
Data collected for the project met quality control criteria
described in Table 6-1 with few exceptions. Surrogate spike recoveries for
Methods 8240 and 8240 Direct Injection indicate more variability than expected
in approximately 25% of the analyses. In one of four matrix spiked samples
analyzed by Method 8270, spike recoveries for l,4-Dichlorobenzene and 1,2,4-
Trichlorobenzene were slightly outside the project accuracy objectives. In
one of four matrix spiked samples analyzed by Method 8240, spike recoveries
for toluene were outside the project accuracy objective.
6-1
-------
TABLE 6-1. SUMMARY OF INTERNAL QUALITY CONTROL PROCEDURES
EPA Method 8240
(GC/HS)
Daily prior to
sanpte
analyses
Daily prior to
sairpLe
anaLyses
Every 12
hours
Every sanpte
Daily prior to
sanple
analyses
Retune instrunent
1) EvaLuate system
2) Repeat
CaLibration
FLag data
1) CLean system
2) Repeat blank
analysis
Volatile Organic EPA Method 250
Content
Matrix spike
Matrix spike dupLicate
CaLibration standard
check - FID
5% or 1 per
batch
5%
Daily
Refer to method
Refer to method
±10% of nn Ltipoint curve
1) Run check
standard
2) Correct
probLem
3) FLag data
1) Run check
standard
2) Correct
probLem
3) FLag data
1) Rerun
2) Recalculate
(Contirued)
Parameter
Chemical Tests
Volatile Organic
Conipo i.mds
Duality
AnalyticaL Method Control Check Frequency Criteria Corrective Action
Mass scale calibration
using PFTBA
Check of mass spectral
ion intensities using
BFB
System performance
check conpounds
Surrogate spikes
System blank anaLysis
Repeat calibration
See text
Refer to method
RF 0.300 (0.250 for
bromoform)
Refer to method
See Method
-------
TABLE 6-1. (Continued)
Quality
Parameter Analytical Method Control Check Frequency Criteria Corrective Action
Calibration standard Daily ±25% of source 1) Rerui
check - HECD concentration in niiltipoint 2) Recalculate
curve
Duplicate analysis All WA Report average
with RPD
Volatile Radian Gas Canister Fieldlcleaning blank 10% of total TNMHC 20 ppbv-C 1) Repeat
Organics Method (Abstracted sanples analysis
Method T0-14) 2) Reclean all
canisters in
that set and
analyze one as
a cleaning
blank
Method blank analysis Daily prior to TNMHC 25 pçibv-C 1) Repeat bLank
sasple analysis
analyses, then 2) Clean system
after sa pLe and check for
with >lO area leaks
cotrits
Linearity check MonthLy or Correlation coeffIcient 1) Repeat
(itultipoint after >0.995 (see text, Section calibration
calibration) using maintenance 6) 2) Repeat
propane/hexane linearity
standard check
Single point response Weekly or when Response factor agreement 1) Repeat RF
factor (RF) check detectors are within ±30% of most recent check
using hexane stanard altered average RFs for nuttipoint 2) Repeat
(FID/PID) calibrations for FID calibration
Veriflowa regulator At (east once Specified rate ±5% 1) Reset flow
sanpling flow rate during each 2) RepLace
period - regulator
(Continued)
-------
TABLE 6-1. (Continued)
Quality
Parameter Analytical Method Control Check Frequency Criteria Corrective Action
Semi-VotatiLee SW 8270 Mass scale calibration Daily prior to Refer to method Repeat calibration
with PPTBA sauple
analyses
DPTPP relative Ion Daily prior to Refer to method Repeat calibration
abundance check sasple
analyses
InternaL standard Daily prior to Refer to method Rettaie Instrusent,
check sasple repeat
analyses
Semi-VolatiLes System performance Every 12 hours Refer to method 1) Evaluate system
(Continued) check cospounds 2) Take corrective
action
3) Repeat test
4) See Lab manager
Surrogate spike AlL sasples Based on accetabiLity tests Flag results as
(refer to method) outside data
control Limits
Extraction blank Daily prior to Refer to method 1) CLean system
sasple 2) Repeat bLank
analysis analysis
(Continued)
-------
TABLE 6-1. (Continued)
Quality
Parameter Analytical Method Control Check Frequency Criteria Corrective Action
Matrix spike duplicate 5% or per Refer to method 1) Run check
sanples batch <20 standard
2) Correct problmn
3) flag data
Surrogate spikes Every sairple Refer to method 1) Check
calculations
2) Reanalyze
extract
3) Reextract and
reanalyze
4) FLag data
pH EPA Method 150.1 Two-point calibration Daily prior to Reading within 0.05 pH unit 1) Repeat
saspte of buffer solution values calibration
anaLyses 2) See instrusent
marsial
Duplicate analyses 10% ±0.05 pH units 1) Repeat sasple
analyses
2) Use to
determine
analytical
variability
TotaL Suspended EPA Method 160.2 DupLicate analyses 10% RPD 20% 1) Repeat sanple
Solids analyses
2) Use to
determine
analyticaL
variability
Control sanple 10% RPD 20% Flag data
-------
TABLE 6-2. METHOD 8270 CCC AND SPCC RESULTS FOR 2-19-90
QL)ANT REPORT
Operator ID. MCK
Output File. C83353:.QT
Data File: >83353: :A1
Name: AP9 80 PPM STD
Moat:
Quant Rev 6 Quent Tome:
Injected at:
Dilution Factor:
900219 09 33
900219 08:59
I .00000
8TLQ 1
1) C 130
2) C370
3) C 150
4) C510
5) C560
6) C555
1 ,4-DICHLOROBENZENE-d4 RI:
N_NITROSODI-n-PROPTLAMINERT:
ACENAPHTHENE-d lO RI:
HExACHLOROCTCLOPENTADIENERT:
4-NITROPMENOL RI:
2 .4 -DINITROPHENOL RI:
ID File: IDCC I::DB
Title: CALIBRATION CHECK COMPOUNDS FOR MSD #1
Last Calibration: 900215 10:08
R.T
Scant
Area
Conc Unite
q
7.24
562
87267
40 00 PPM
95
6 87
522
330454
78.27 PPM
b5
7.27
565
295237
80 60 PPM
97
ID 10
868
320778
40 00 PPM
99
9.30
782
134584
76 44 PPM
89
9.91
848
198239
79.58 PPM
94
£0 65
927
103268
70.77 PPM
93
I l 77
1047
211042
17.59 PPM
70
14.42
1330
153418
40.00 PPM
90
12.67
1143
147364
77.98 PPM
87
14 50
1339
382196
76.86 PPM
96
16.18
1518
236928
71.35 PPM
90
18.08
1721
184104
60.00 PPM
99
17.85
1697
56654
83.84 PPM
97
21.11
2046
379721
75.27 PPM
91
24.71
2432
64459
40.00 PPM
95
26 59
2633
394317
84.69 PPM
90
2m.o2
27.90
2786
2773
34419
96633
40 00 PPM
78.28 PPM
100
90
Compound
1) *CI3O I,4-DICHLOROBENZENE-d4
2) C315 PHENOL
3) C340 I.4-DICKLORO BENZENE
4) oCt40 NAPHTHALENE-dR
5) C420 2-NITROPHENOL
6) C440 2.4-DICKLOROPHENOL
7) C460 HEXACHLOROBUTADIENE
8) C465 4-CHLORO-3-METHYLPHENO/.
9) oCt50 ACENAPHTHENE-d lO
10) CSIS 2,4,6-TRICHLOROPHENOL
11) C550 ACENAPHTHENE
12) C615 N-NITROSODI-N-PHENTLAMINE
13) oCt60 PHENANTHRENE-d IO
14) C635 PENTACHLOROPHENOL
IS) C655 FLUORANTHENE
16) oCt70 CHRYSENE-d12
17) C760 DI-n-OCTTLPHTHALATE
18) oCt75 PERYLENE—d12
19) C775 BENZ(e)PTRENE
Compound is ISTD
FMCR : qcal.e83353
Quant Output File. 583353: g D
From ID File: IDSPI::DB
Quant Time: 900219 09:35
Quant ID File: IDSPI::DB
Title: system performance
Recalibrating
check compoude for med #1
Done
7.24
Scan:
562
(1510)
8 33
Scan:
678
(New RI :1.165484)
14 42
Scan:
1330
(ISTO)
12.43
Scan:
1117
(New R I : . 190828)
15.14
Scan:
1407
(New RI = .116606)
14 67
Scan:
1357
(New RI : 097583)
6—6
-------
TABLE 6-3. METHOD 8270 CCC AND SPCC RESULTS FOR 2-20-90
QUANT REPORT
Operator ID: lICK
Output File: C83371: :QT
Data File: >83371: :A1
Name: AP9 80 PPM STD
Misc:
Quint Rev. 6 Quint Time:
Injected at:
Dilution Factor:
900220 10:05
900220 09 13
1 .00000
BTLU I
1) C 130
2) C370
3) CISO
4) CS1O
5) C560
6) C555
1 .4-DICHLORO8ENZENE-d4 RT
N-NITROS0Dt-n-PR0PYLAMINERT
ACENAPHT IIENE-d IO RT:
IIEXACHLOROCYCLOPENTADIENERT.
4-NITROPHENOL RT.
2 ,4-DIN ITROPHENOL RT:
R T.
6 89
7 28
10.12
Q 31
9.92
10.67
Il 79
14 43
12.69
14 53
16.20
18.09
17.81
21. 14
24.73
26.62
28.04
27 92
Zcan t
S S 7
520
562
065
779
844
924
1044
1326
1140
1336
1514
1716
1693
2042
2426
2627
2779
2766
Area
137 494
505302
446123
488845
216160
312078
171656
316427
226811
241012
565867
376711
292402
114553
642327
130567
636313
63628
184901
Core
.0.00
75 17
79.98
40 00
78.00
77.95
76 83
74.41
40.00
86.48
76.84
74 54
40.00
75 11
79.61
40.00
11 .75
40.00
83.23
ID File: IDXCI::SC
Title: CALIBRATION CHECK COMPOUNDS FOR MSD #1
Lace Calibration: 900220 10:05
Compound
1. •C 130 1,4-DICNLOROBENZENE-d4
2) C315 PHENOL
3) C340 1,4-DICNLOROBENZENE
4) *C140 NAPHTHALENE-dB
5) C420 2-NITROPHENOL
b) C440 2 .4-DICHLOROPHENOL
7) C460 HEXACHLOROBUTADIENE
8 C465 4-CHLDRO-3-METHTLPHENOL
9 ) iCISO ACENAPHTHENE-d lO
10) C5l5 2,4,6-TRICHLOROPHENOL
11) C550 ACENAPHTHENE
12) C615 N-NITROSODI-N-PHEN’fLAM INE
13) .C160 PKENANTNRENE—dIO
14) C635 PENTACHLOROPHENOL
IS) C655 FLUORANTNENE
16) eCI7O CHRYSENE-d12
I ?) C760 DI-n-OCTTLPHTNALATE
18) CI75 PERTLENE-d12
19) C775 BENZ(a)PTRENE
Compound Ia ISTD
ffMGR . qcal.s83371
Quint Output File: 58337): :QT
From ED File: EDSPI::DB
Quint Time: 900220 09:56
Quint ID File: IDSP I. :08
Title. ayetem performance check compouda for mad QI
Recalibrating
Units q
PPM
PPM 45
PPM 98
PPM 99
PPM 85
PPM 94
PPM f l
PPM 72
PPM 94
PPM 96
PPM 98
PPM 86
PPM 97
PPM 93
PPM 92
PPM 91
PPM 97
PPM 100
PPM 80
Done
7 25
Scan:
559
(ISTD)
8.34
Scan:
675
(New RI :1.047413)
14.43
Scan:
1326
(ISTD)
12.44
Scan:
1)13
(New RI : .197134)
15.16
Scan:
1404
(New RI .133616)
14.70
Scan:
1354
(New RI : .103707)
6 —7
-------
6.1 OA/OC For Methods 8240 and 8270
Tables 6-2 and 6-3 are the calibration check sample results for
CC/MS Method 8270 for 2-19-90 and 2-20-90. All samples were analyzed on these
two days. The top of the page has recovery data for the calibration check
compounds (CCC’S) which were present at 80 ppm. The internal standards were
spiked 40 ppm. Acceptance criteria for this method are ±30 percent,
recoveries between 56 and 104 ppm are acceptable for 80 ppm spikes. All
concentrations are well within this range.
The lower part of each table presents the response factors for the
system performance check compounds (SPCCs). The acceptance criteria for all
SPCCs are response factors (RF) of greater than 0.050 for each compound. All
compounds passed the acceptance criteria.
The tuning criteria for the semi-volatile analysis on the days
samples were analyzed are in Appendix C. Tuning criteria for
decafluorotriphenyiphosphine (DflPP) were met both days. System blank data
for the 8270 analysis are also presented in Appendix C. The data reveals only
two target analytes, pyridine and isophorone of which both were misidentified.
The compound identified as pyridine is cyclohexene which used as a
preservative in the extraction solvent, methylene chloride. The component
matching the retention time for Isophorone is the internal standard,
naphthalene-d8. Therefore, no target analytes were observed in the system
blanks.
Table 6-4 presents the results of the Method 8240 calibration check
compounds (CCCs) for the days on which the samples were analyzed. All
compounds met the ±25% acceptance criteria. Table 6-5 shows the results for
the system performance check compounds (SPCCs) for the days of analysis. All
SPCCs met the acceptance criteria for these days. The raw data for these
check samples is contained in Appendix C. Broinofluorobenzene (BFB) tuning
checks also may be found in Appendix C. The tuning criteria was passed each
day of analysis.
6-8
-------
TABLE 6-4. METHOD 8240 CALIBRATION CHECK RESULTS (100 ppb std.) CONCENTRATION (ppb)a
r
‘.O
Compound
2/10/90
2111190 b
2/12/90
2/13/90
2/14/90
Vinyl Chloride
102
45
102
81
82
1,1-Dichiorethylene
92
45
99
89
78
Chloroform
91
48
98
85
83
1,2-dichioropropane
87
45
100
83
80
Toluene
100
47
10
101
102
Ethyl Benzene
93
38
97
91
91
aAcceptance Criteria ±25%
bspiked at 50 ppb
-------
TABLE 6-5. 8240 SYSTEM PERFORMANCE CHECK COMPOUND (SPCCs) RESPONSE FACTOR (RF) RESULTSa
‘ -I
0
Compound
2/10/90
21111 90 b
2/12/90
2/13/90
2/14/90
Chioromethane
1.19
0.991
1.17
0.873
0.863
11-Dichioroethane
2.72
2.80
2.87
2.40
2.45
Bromoforin
0.257
0.259
0.259
0.272
0.256
1,1,2 ,2-
Tetrachioroethane
0.515
0.485
0.518
0.511
0.507
Ch lorobenzene
1.04
1.05
1.05
1.09
1.09
aAcceptance Criteria — RF 0.3 for all compounds except bromoform;
RF 0.250 for bromoform
-------
All 8240 DI analyses were performed on 2-15-90. There are no
performance measures established for this method, so a five point calibration
was performed. The multipoint calibration data may be found in Appendix C.
No target analytes were observed in the system blanks.
6.1.1 Matrix Spike/Matrix Spike Duplicates
Matrix spike and matrix spike duplicate analyses were performed on
two samples for Method 8240. Due to the departure from the analytical plan
described in Section 5.3, matrix spike recoveries for the Method 8270 analyses
are not presented. Recovery checks and recovery check duplicates of spiked
reagent water were performed instead. The two samples were for the IPA Column
Bottoms (C53-l-3-8240P/8270), and for the Phenol-Acetone Oily Water Sewer
Effluent (OW-2-3-8240P/8270). The results are provided in Table 6-6 for the
Method 8240 analyses, in Table 6-7 for the Method 8240 Direct Inject analyses,
and in Table 6-8 for the Method 8270 analyses.
All matrix spike compounds were recovered within the recovery limits
established for the USEPA CIP SOW with three exceptions. Toluene OW-2-3-8240P
MSD (37%). In the 8270 analysis of C53-l-3-8270MSD, l,4-Dichlorobenzene (29%)
and l,2,4-Trichlorobenzene (34%) were recovered below the acceptance limits
(36-97, 39-98 respectively). Acceptance criteria have not been established
for 8240 Direct Injection.
6.1.2 Surrop ate Spikes
Method 8240 and 8270 samples were spiked with surrogate compounds to
estimate the effectiveness of the extraction and analysis. The specification
for the surrogate spiking program are listed in Table 6-9. The surrogate
recoveries are presented in Tables 6-10, 6-11, and 6-12.
All Method 8270 surrogate spike recoveries calculated were within
the acceptance limits. Matrix interferences precluded quantitation of five of
the six 8270 surrogates spiked in sample OW-2-3-8240P and two of the six 8270
surrogates spiked in sample EB-3-l-8240P. All Method 8240 surrogate spike
6-fl
-------
7/03/90
TABLE 6—6.
METHOD 8240
DUPLICATE MATRIX SPIKE RECOVERIES
Matrix Matrix Spike
Compound Sample ID Spike (%) Duplicate (%) RPD (%)
Benzene C53—1-3—8240P 90 91 1.10
O -2-3-824OP 89 86 3.42
Chlorobenzene C53—1-3—8240P 95 93 2.12
0W-2-3-8240P 95 98 3.10
1.1-Dichioroethene C53-1-3—8240P 137 142 3.58
0W-2-3-8240P 63 64 1.57
Toluene C53—1-3-8240P 99 96 3.07
OW-2-3-8240P 104 37 Q 95.0
Trichioroethene C53—1-3-8240P 87 86 1.15
0W-2-3-8240P 84 85 1.18
Q — Outside control limits.
6—12
-------
7/03/90
TABLE 6—7.
METHOD 8240 D.I.
DUPLICATE MATRIX SPIKE RECOVERIES
Matrix Matrix Spike
Compound Sample ID Spike CX) Duplicate (%) RPD (%)
1,4-Dioxane C53-1—3-8240 190 X 190 X 0.00
Isobutanol C53-1—3-8240 21D X 218 X 3.73
Methacrylonitrile C53-1—3-824D 120 X 132 X 9.52
X - Outside Control Limits
6—13
-------
TABLE 6-8. METHOD 8270 RECOVERY CHECK/RECOVERY CHECK DUPLICATES
Reagent Reagent Spike
Compound Sample ID Spike (%) Duplicate (%) RPD (%)
Acenaphthene C53-1-3-8270 55 53 3.70
0W-2-3-8270 58 54 7.14
4-Chloro-3—methylphenol C53-1—3-8270 51 76 39.3
OW-2-3-8270 74 70 5.55
2—Chiorophenol C53-1—3-8270 34 68 66.6
0W-2-3-8270 66 65 1.52
1.4-Dichlorobenzene C53-1-3-8270 36 29 Q 21.5
OW-2-3-8270 67 44 41.4
2.4-Dinitrotoluene C53-1-3-8270 66 66 0.00
OW-2-3-827 0 69 69 0.00
t4—Nltrosodipropylamine C53-1—3-8270 66 59 11.2
OW-2—3-8270 61 53 14.0
4-Nitrophenol C53-1-3-8270 26 74 96.0
OW-2—3-8270 68 64 6.06
Pentachiorophenol C53-1—3-8270 22 77 111.
OW-2-3-8270 55 43 24.4
Phenol C53-1—3-8270 36 65 57.4
0l I-2—3-8270 54 52 3.77
Pyrene C53-1-3-8270 83 73 12.8
OW-2-3-8270 74 76 2.66
1.2.4—Trichlorobenzene C53-1-3-8270 39 34 0 13.6
0W-2—3-8270 70 49 35.2
Q - Outside control limits.
6—14
-------
TABLE 6-9. SURROGATE SPIKING SPECIFICATIONS FOR
EPA METHODS 8240 AND 8270
EPA
Method
Surrogate Compound
Spiking Level
in Extract
(sg/mL)
Acceptable
Recovery Range. %
Aqueous•
Solids
8240
] .,2-Dichloroethane-44
To luene-d8
p-Bromofluorobenzene
50
50
50
76 - 114
88 - 110
86 - 115
90 - 121
81 - 117
74 - 121
8270
2-Fluorophenol
Phenol-d6
Nitrobenzene-d5
2-Fluorobiphenyl
2,4,6-Tribromophenol
Terpheny l-d14
200
200
100
100
200
100
21 - 100
10 - 94
35 - 114
43 - 116
10 - 123
33 - 141
25 - 121
24 - 113
23 - 120
30 - 115
19 - 122
18 - 137
6-15
-------
6/28/90
TABLE 6—10.
METHOD 8240
SURROGATE RECOVERIES (%)
Acceptance BLK
Conipound Limits C53-l-3-8240P MP-1-1—8240P C5—1B C5-5 C5-5C C5-6 C5-1O C5-OWS BW-2—1-8240P OH—2-3-8240P OH-2—3—8240P
1.4-Bromofluorobenzene 86—115 97 90 95 93 100 98 98 106 100 99 105
BLK
OL-2-2-8240P 0P3-BW 0P3-CV 0P3-DW 0P3-EW 0P3-FV 0W-2-3-8240P CS1BRW CS6R CS6RV WI
105 101 102 73 Q 98 67 Q 87 77 Q 79 Q 80 Q 83 Q
c
I -I
0’ System System System
Blank Blank Blank
F8-2-1-8240-P OL-2-2-8240P EB-3- 1-8240P wo#9002072 wo#9002098 wo#9002106
79 Q 79 Q 87 99 101 85 Q
-------
6/28/90
TABLE 6—10. (Continued)
METHOD 8240
SURROGATE RECOVERIES (%)
Acceptance BLK
Canpound Limits C53—1-3—8240P HP-1—1-8240P C5-1B C5-5 C5-5C C5-6 C5-1O C5—OVS BW—2—1—8240P OH-2-3—8240P OH-2-3-8240P
1.2-Dichloroethane d4 76-114 89 86 NC 86 NC 90 MC 94 99 99 100
BLK
OL-2-2-8240P 0P3-BW 0P3-CW 0P3-DW 0P3-EW 0P3—FV OW—2—3-8240P CSIBRW CS6R CS6RW Swi
97 104 103 79 78 76 75 Q 98 75 Q 74 Q 74 Q
cr
Syst n Syst n System
Blank Blank Blank
FB—2- 1—8240-P OL-2-2-8240P EB—3- 1—8240P wo#9002072 wo#9002098 wo#9002 106
77 77 75Q 88 90 79
-------
6/28/90
TABLE 6—10. (Continued)
METHOD 8240
SURROGATE RECOVERIES (%)
Acceptance BLK
Compound Limits C53—1-3—8240P MP-1—1-8240P C5-1B C5-5 C5-5C C5-6 C5-10 C5—OWS BW—2-1—8240P OH-2-3—8240P OH-2—3—8240P
Toluene d8 88-110 116 Q NC NC 156 Q 124 Q 159 0 144 Q 18 Q 115 Q 112 0 105
61K
0L-2—2-8240P 0P3-BW 0P3-CW 0P3—DW 0P3-EW 0P3—FV OW—2—3-8240P CS IBRW CS6R CS6RW Swi
105 115 Q 111 Q 81 Q 78 Q 86 Q 95 100 102 109 94
a’
System System System
Blank Blank Blank
FB—2-1 -8240—P OL-2—2-824OP EB-3—1-8240P wo9002072 wo#9002098 wo#9002106
95 109 87 Q 105 100 96
Q - Outside control limits.
NC - Not calculated.
-------
TABLE 6—11. 7/03/90
METHOD 8240 D.I.
SURROGATE RECOVERIES ( )
System System System
Acceptance Blank Blank Blank
Compound Limits MP—1-1-8240 C53-1-3-8240 BW-2-1-8240 OW-2-3-8240 EB-3-1-8240 128-3-3—8240 wo#9002072 wo#9002098 wo#9002106
1,4-Bromofluorobenzene 86-115 108 103 102 109 108 106 98 98 98
1.2-Dichloroethane d4 76-114 95 105 104 110 105 100 105 105 105
Toluene d8 88-110 84 Q 88 85 82 87 Q 75 0 95 95 95
Q - Outside control limits
-------
6/28/90
TABLE 6-12.
METHOD 8270
SURROGATE RECOVERIES (%)
Reagent Reagent
Acceptance Blank Blank
Coilipound Limits OI1-2—3-8240P C53-1—3-8240 OL-2—2-8240P OV—2—3-8240P T28—3-3-8240 EB-3-1—824OP wo#9002072 wo#9002106
2-Fluorobiphenyl 43-116 64 60 69 NC * 57 75 54 61
2-Fluorophenol 21-100 27 72 45 NC * 78 NC * 50 75
Nitrobenzene 35-114 51 86 74 NC * 40 88 61 82
a ..
Phenol d5 10-94 38 46 63 NC * 60 NC * 54 64
Terphenyl d14 33-141 67 82 82 106 98 127 82 89
2.4.6—Tribromophenol 10-123 51 82 43 NC * 69 93 65 36
* - Matrix interferences preclude quatitation of these surrogates.
o - Outside control limits.
NC - Not calculated.
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compounds were recovered within the acceptance limits with the exception of
22.6% which were recovered below the limits, 10.7% which were recovered above
the limits and 6% which could not be calculated. All Method 8240 Direct
Injection surrogate spike compouns were recovered within the acceptance
limits, with the exception of 19% which were recovered below the limits.
6.1.3 Field Blanks
Field blanks were taken during the first event of the second
sampling day (Sample ID. FB-2-l-8240P and FB-2-l-8270). These blanks were
taken by pouring distilled water into the sample containers directly, without
passing them through the cooler. The results (Appendix A) show no detectable
levels of the target compounds. Sampling apparatus blanks (OH-2-3, OH-2-2)
were taken for the dip sampling containers by following a sampling event with
the prescribed cleaning procedure and then filling the container with
distilled water and transfering it to the sample bottles. This procedure was
performed after the Olefins Light and Heavy Combined sewer samples were taken.
The results, as shown in the laboratory reports in Appendix A, show some of
the same compounds that were detected in the Olefins sewer, but at a much
reduced level.
6.2 Method 25D Quality Control
The calibration results for the Flame Ionization Detector (FID) and
the Hall Electrolytic Conductivity Detector (HECD or EICD), and some audit
sample results are given in this section. The multipoint calibration data
for the time period during which the Shell samples were analyzed are presented
in Table 6-13. The single point daily and end of day checks are presented in
Table 6-14. The EPA prepared audit samples which were analyzed close to the
time period of the actual samples are presented in Table 6-15. Radian was not
given the actual concentrations of the audit samples, therefore there are no
comparisons are made in this table. Field blanks were taken on the second day
of the sampling period. The blanks were identified as FB-2-l-25D-A,-B,-C. No
VOCs were detected in the field blank samples.
6-21
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6.3 QA/OC For Gas Canisters
Two sets of duplicates were taken of actual sewer vapor samples.
One field blank and one system blank were also taken. The canisters which
were used on this project are generally used with high expected
concentrations. One duplicate sample set, taken at sample point CS6,
identified as samples CS6-R and CS6-RD (provided in Appendix A), agreed within
ten percent for Benzene, TNMHC, and the top three identified compounds. The
concentrations of VOCs at this location (457OppmV-483OppmV) were near the
middle of the range of concentrations measured in this program. The
agreement between the second duplicate sample set (samples 0P3-Cl and 0P3-C2)
was not as good. The levels of VOCs measured at this location were much lower
(l9ppmV-56ppmV). Earlier measurement of much higher levels, insufficient
purging of the sample tubing, and retention of previous sample in the pressure
guage could have affected the quality of agreement between the second
duplicate set. Sample 0P3-D, taken a few minutes earlier, measured many of
the same compounds as one of the duplicate samples. The trip blank,
identified as B-i, measured 6ppmV of THC, the lowest of all the samples, and
3ppmV of Toluene.
6.4 pA/aC Total Suspended Solids(TSS) and H
Quality control check sample results for the TSS and pH ressults are
summarized in table 6-16. All checks were within acceptance limits.
6-22
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TABLE 6-13.
METHOD 250 MULTIPOINT CALIBRATION DATA
Cal. Concentration Area Count Avg. RF Avg. RF Std. Rel. Std. Rel. Corr. Corr.
Date mgCuiig Cia FID ( lCD FIDRFb (lCD RFb F1Dc EICDC Dev.FID Dev.EICD Coeff. rID Coeff. (lCD
1 2/06/90 2.52 .14 9268 13807 .000272 .000010 .999 .999
1 2/06/90 2.52 .14 8872 16853 .000284 .000009 .999 .999
2/06/90 2.52 .14 9145 17049 .000275 .000008 .000277 .000009 1.83 9.99 .999 .999
1 2/06/90 10 08 .57 38622 109687 .000261 .000005 .999 .999
1 2/06/90 10.08 .57 39322 117944 .000256 .000005 .000259 .000005 .90 3.63 .999 .999
1 2/06/90 50.38 2.87 207779 756173 .000242 .000004 .999 .999
1 2/06/90 50.38 2.87 211080 786495 .000239 .000004 .000241 .000004 .79 1.97 .999 .999
2 2/08/90 2.52 .14 10453 21483 .000241 .000007 .999 .995
2 2/08/90 2.52 .14 10411 26798 .000242 .000005 .000241 .000006 11.01 11.01 .999 .995
2 2/08/90 10.08 .57 41876 162362 .000241 .000004 .999 .995
2 2/08/90 10.08 .57 45974 159013 .000219 .000004 .000230 .000004 1.04 1.04 .999 .995
2 2/08/90 50.38 2.87 218545 890961 .000231 .000003 .999 .995
2 2/08/90 50.38 2.87 219554 917848 .000229 .000003 .000230 .000003 1.49 1.49 .999 .995
3 2/13/90 2.52 .14 7792 28160 .000323 .000005 .999 .999
3 2/13/90 2.52 .14 8477 26404 .000297 .000005 .000310 .000005 3.22 3.22 .999 .999
3 2/13/90 10.08 .57 36155 154564 .000279 .000004 .999 .999
3 2/13/90 10.08 .57 36552 177024 .000276 .000003 .000277 .000003 6.77 6.77 .999 .999
3 2/13/90 50.38 2.87 182025 934522 .000277 .000003 .999 .999
3 2/13/90 50.38 2.87 183191 976959 .000275 .000003 .000276 .000003 2.22 2.22 .999 .999
4 2/19/90 2.52 .14 8350 13955 .000302 .000010 .999 .999
4 2/19/90 2.52 .14 9260 17571 .000272 .000008 .000287 .000009 11.47 11.47 .999 .999
4 2/19/90 10.08 .57 40611 80982 .000248 .000007 .999 .999
4 2/19/90 10.08 .57 41081 77364 .000245 .000007 .000247 .000007 2.28 .58 .999 .999
4 2119/90 50.38 2.87 215287 540888 .000234 .000005 .999 .999
4 2/19/90 50.38 2.87 211539 526581 .000238 .000005 .000236 .000005 1.34 .88 .999 .999
5 2/20/90 2 52 .14 14967 28321 .000168 .000005 .999 .999
5 2/20/90 2.52 .14 15636 30724 .000161 .000005 .000165 .000005 4.07 4.07 .999 .999
5 2/20/90 10.08 .57 66531 156533 .000152 .000004 .999 .999
5 2/20/90 10.08 .57 67535 151498 .000149 .000004 .000150 .000004 1.63 .75 .999 .999
5 2/20/90 50.38 2.87 324505 847741 .000155 .000003 .999 .999
5 2/20/90 50.38 2.87 318174 844471 .000158 .000003 .000157 .000003 .19 .99 .999 .999
6 2/26/90 2.52 .14 9444 23682 .000267 .000006 .999 .999
6 2/26/90 2.52 .14 9368 22444 .000269 .000006 .000268 .000006 2.68 2.68 .999 .999
6 2/26/90 10.08 .57 423E4 114489 .000238 .000005 .999 .999
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TABLE 6—13. (Continued)
METHOD 25D MULTIPOINT CALIBRATION DATA
Cal. Concentration Area Count Avg. RF Avg. RF Std. Rel. Std. Rel. Corr. Corr.
No. Date mg C mg Cl FID [ lCD FID RF [ lCD RF FID [ lCD 0ev. FID 0ev. [ lCD Coeff. FID Coeff. [ lCD
6 2126/90 10.08 .57 42971 119822 .000235 .000005 .000236 .000005 2.28 .71 .999 .999
6 2/26/90 50.38 2.87 208950 628818 .000241 .000005 .999 .999
6 2/26/90 50.38 2.87 196779 591126 .000256 .000005 .000249 .000005 3.09 3.00 .999 .999
7 2/28/90 2.52 .14 8194 16887 .00030? .000008 .999 .998
7 2/28/90 2.52 .14 8150 18326 .000309 .000008 .000308 .000008 4.09 4.09 .999 .998
7 2128/90 10.08 .57 35770 68756 .000282 .000008 .999 .998
7 2/28/90 10.08 .57 38814 98173 .000260 .000006 .000271 .000007 17.62 4.08 .999 .998
7 2128/90 50.38 2.87 194096 498489 .000260 .000006 .999 .998
7 2/28/90 50.38 2.87 188849 483818 .000267 .000006 .000263 .000006 1.49 1.3? .999 .998
8 3/12/90 2.52 .14 6469 21590 .000389 .000007 .999 .998
8 3/12/90 2.52 .14 6600 20569 .000382 .000007 .000386 .000007 2.42 2.42 .999 .998
8 3/12/90 10.08 .57 29053 103557 .000347 .000006 .999 .998
8 3/12/90 10.08 .57 28936 102371 .000348 .000006 .000348 .000006 .58 .20 .999 .998
8 3/12/90 50.38 2.87 151780 648178 .000332 .000004 .999 .998
8 3/12/90 50.38 2.87 154669 600877 .000326 .000005 .000329 .000005 3.79 .94 .999 .998
9 3/15/90 2.52 .14 6952 20943 .000362 .000007 .999 •ggg
9 3/15/90 2.52 .14 7123 26012 .000354 .000006 .000358 .000006 10.80 10.80 .999 .999
9 3115/90 10.08 .57 30441 115616 .000331 .000005 .999
9 3/15/90 10.08 .57 30178 98309 .000334 .000006 .000333 .000005 8.09 .43 .999 .999
9 3/15/90 50.38 2.87 155613 610241 .000324 .000005 .999 .999
9 3/15/90 50.38 2.87 158209 643535 .000318 .000004 .000321 .000005 2.66 .63 .999 .999
10 3/19/90 2.52 .14 6050 31537 .000416 .000005 .999 .999
10 3/19/90 2.52 .14 6482 32150 .000389 .000004 .000402 .000005 .96 .96 .999 .999
10 3/19/90 10.08 .57 25032 145706 .000403 .000004 .999 .999
10 3/19/90 10.08 .57 24535 148652 .000411 .000004 .000407 .000004 1.00 1.00 .999 .999
10 3/19/90 50.38 2.87 118949 706310 .000424 .000004 .999 .999
10 3119/90 50.38 2.87 121292 694292 .000415 .000004 .000419 .000004 .86 .98 .999 .999
Notes:
a — lug C is expressed as Methane
b — Response Factor=Concentration (maC or maC f l
Response (A ! Counts)
C — Average Response Factor = Ex
d — Correlation Coefficient of linear regression.
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TABLE 6—14. 7/03/90
METHOD 25D DAILY QUALITY CONTROL DATA
Concentration Response Factor a R.F. Used for
Date QC Check mg C mg Cl FID (lCD Rel. % FID b,c 01ff. (lCD Quantitation Cocnnents
2/06/90 End day 10.08 0.5736 0.0002435194 0.0000050284 -5.98 -15.63 0.000259
2/08/90 End day 10.08 0.2868 0.0002310602 0.0000023982 -1.26 -43.57 0.000234
2/09/90 Daily check 10.08 0.2868 0.0002290545 0.0000020301 -2.11 -52.23 0.000234
2/14/90 Daily check 10.08 0.5736 0.0002298169 0.0000028423 -20.20 -27.12 0.000288
2/14/90 End day 10.08 0.5736 0.0002444762 0.0000033711 -15.11 -13.56 0.000288
2/15/90 Daily check 10.08 0.5736 0.0002348282 0.0000032311 -18.46 -17.15 0.000288
2/15/90 Daily check 10.08 0.5736 0.0002351733 0.0000031925 -18.34 -18.14 0.000288
2/19/90 End day 10.08 0.5736 0.0000000000 0.0000130168 0.00 78.80 0.000245 Data flagged
2/20/90 End day 10.08 0.5736 0.0001715715 0.0000039368 9.28 -1.33 0.000157
2/21/90 DaIly check 10.08 0.5736 0.0001636257 0.0000036175 4.22 -9.34 0.000157
2/21/90 End day 10.08 0.5736 0.0001586627 0.0000116889 1.06 192.96 0.000157
2/22/90 DaIly check 10.08 0.5736 0.0001807326 0.0000040464 15.12 1.41 0.000157
9 r 2/22/90 End day 10.08 0.5736 0.0002393447 0.0000066785 52.45 67.38 0.000157 Data flagged
2/26/90 End day 10.08 0.5736 0.000254873? 0.0000065800 1.54 24.62 0.000251
2/27/90 DaIly check 10.08 0.5736 0.0002439910 0.0000055548 -2.79 5.20 0.000251
2/27/90 End day 10.08 0.5736 0.0002713543 0.0000099974 8.11 89.34 0.000251
2/27/90 End day 151.14 8.6040 0.0002534719 0.0000267047 0.98 405.17 0.000251
2/28/90 End day 10.08 0.5736 0.0002671472 0.0000066630 -4.93 -5.22 0.000281
3/01/90 DaIly check 10.08 0.5736 0.0002770372 0.0000065955 -1.41 -6.18 0.000281
3/01/90 End day 10.08 0.5736 0.0002989945 0.0000089222 6.40 26.92 0.000281
3/01/90 End day 261.95 14.910 0.0002667021 0.0000060682 -5.09 -13.68 0.000281
3/02/90 DaIly check 10.08 0.5736 0.0002783685 0.0000062535 -0.94 -11.05 0.000281
3/02/90 End day 10.08 0.5736 0.0003179610 0.0000099681 13.15 41.80 0.000281
3/02/90 End day 292.30 16.640 0.0002800632 0.0000060969 -0.33 -13.27 0.000281
3/08/90 DaIly check 10.08 0.5736 0.0003229838 0.0000062883 14.94 -10.55 0.000281
3/08/90 End day 10.08 0.5736 0.0003043754 0.0000081102 8.32 15.37 0.000281
3/09/90 DaIly check 10.08 0.5736 0.0002750491 0.0000061130 -2.12 -13.04 0.000281
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TABLE 6—14. (Continued) 7/03/90
METHOD 250 DAILY QUALITY CONTROL DATA
Concentration Response Factor R.F. Used for
Date QC Check ing C mg Cl FID EICD Rel. % FID Diff. EICD Quantitation Coimients
3/09/90 End day 10.08 0.5736 0.0004479005 0.0000084876 59.39 20.73 0.000281 Data flagged
3/12/90 End day 10.08 0.5736 0.0003818326 0.0000071124 7.86 25.66 0.000354
3/13/90 DaIly check 10.08 0.5736 0.0003387211 0.0000055821 -4.32 —1.38 0.000354
3/13/90 End day 10.08 0.5736 0.0003895502 0.0000077899 10.04 37.63 0.000354
3/14/90 DaIly check 10.08 0.5736 0.0003732227 0.0000057107 5.43 0.89 0.000354
3/14/90 End day 10.08 0.5736 0.0003981357 0.0000138644 12.47 144.95 0.000354
3/14/90 End day 100.80 5.7360 0.0003954306 0.0000547992 11.70 868.18 0.000354
3/19/90 End day 10.08 0.5736 0.0004041214 0.0000052853 -1.43 26.75 0.000410
3/20/90 Daily check 10.08 0.5736 0 0004036359 0.0000043445 —1.55 4.19 0.000410
3/20/90 End day 10.08 0.5736 0 0004394838 0.0000042130 7.19 1.03 0.000410
3/21/90 Daily check 10.08 0.5736 0.0004497390 0.0000051397 9.69 23.25 0.000410
3/21/90 End day 10.08 0.5736 0.0004624065 0.0000046557 12.78 11.65 0.000410
0 ’ 3/21/90 End day 100.80 5.7360 0.0004760983 0.0000041141 16.12 -1.34 0.000410
3/22/90 DaIly check 10.08 0.5736 0.0004771598 0.0000042619 16.38 2.20 0.000410
3/22/90 DaIly check 10.08 0.5736 0.0004504021 0.0000040963 9.85 -1.77 0.000410
3/22/90 End day 10.08 0.5736 0.0004636401 0.0000049280 13.08 18.18 0.000410
3/23/90 Daily check 10.08 0.5736 0.0004436229 0.0000045198 8.20 8.39 0.000410
3/23/90 End day 10.08 0.5736 0.0004600009 0.0000048829 12.19 17.09 0.000410
3/26/90 DaIly check 10.08 0.5736 0.0004510471 0.0000056318 10.01 35.06 0.000410
3/26/90 DaIly check 10.08 0.5736 0.0004534413 0.0000041036 10.59 -1.59 0.000410
3/26/90 End day 10.08 0.5736 0.0005019170 0.0000050456 22.42 20.99 0.000410
3/28/90 DaIly check 10.08 0.5736 0.0003932584 0.0000035754 -4.08 -14.26 0.000410
3/28/90 End day 10.08 0.5736 0.0004451904 0.0000040697 8.58 -2.41 0.000410
3/28/90 End day 100.80 5.7360 0.0004488838 0.0000037386 9.48 -10.35 0.000410
a — Response Factor=Concentration (maC or maCi )
Response (Area Counts)
b-RPC=DailyRF xlOO
Multipoint RF
c - Acceptanc Limits = 10% for FID and 30% for HECD for daily
check, Acceptance limits = 30% for FIC and HECD for end of day
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7/03/90
TABLE 6—15.
METHOD 250 AUDIT SAMPLES
Sample No. Date Analyzed ng C (as CH4) mg Cl Comiients
100-1-A 2/14/90 12.42 1.61
100-1-B 2/14/90 17.75 1.84
100-2-A 2/15/90 8.71 1.08
100-2-B 2/19/90 10.89 * 1.60 * ing Cl Is 1.18 if closest mp rf used
100-3-A 2/15/90 ND 1.35
100-3-B 2/19/90 ND * ND *
* End of day calibration check was .50% different from the multipoint RF.
6—27
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7/03/90
TABLE 6—16.
SUMMARY OF LABORATORY QUALITY CONTROL
CHECK SAMPLE RESULTS FOR
TOTAL SUSPENDED SOLIDS AND pH
Standard deviation
Parameter Number of QCCS Mean % Recovery CX Recovery) Acceptance Limits
pH 8 100.99 1.213 80% - 120%
TSS 4 94.950 5.275 80% — 120%
6—28
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7.0 REFERENCES
Radian Corporation, 1989, “Test Plan FOR Method 25D Development and
Testing at the Shell, Deer Park Industrial Wastewater Facilities.”
U.S. EPA, “Proposed EPA Method 25D: Determination of the Volatile
Organic Content of Water Samples,” EPA 25D Interlaboratory Study,
Radian, 1989.
Cox, R.D. and R.F. Earp, “Determination of Trace Level Organics in
Ambient Air by High Resolution Gas Chromatography with Simultaneous
Photo Ionization and Flame Ionization Detection,” Anal. Chem .
54:2265, 1982.
U.S. EPA, 1979. Methods for the Chemical Analysis of Water and
Wastes. U.S. EPA, 4-79-020, March 1979.
U.S. EPA, 1986. Test Methods for Evaluating Solid Waste (SW-846).
U.S. EPA Volumes 1A, lB. 1C, and II, Third Edition, U.S. EPA
Document Control Number 955-001-00000-1, November 1986.
Federal Register, October 1984. Volume 49, No. 209, pp. 198 and
199, Friday, October 28, 1984.
7-1
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