vvEPA
United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EMB Report 83-WWS-4
March 1984
Air
Petroleum Refineries
Waste Water
Treatment System
Emission Test Report
Golden West
Refining Company
Sante Fe Springs,
California
-------
Contract No. 68-02-3545
Work Assignment 14
EMB Report No. 83 WWS 4
EPA Task Manager
W. E. Kelly
EMISSION TEST REPORT
PETROLEUM REFINERY WASTEWATER
TREATMENT SYSTEM
GOLDEN WEST REFINING COMPANY
SANTA FE SPRINGS, CALIFORNIA
Contractor
TRW Environmental Operations
Post Office Box 13000
Research Triangle Park, North Carolina 27709
TRW Project Manager
J. B. Homolya
Prepared By
C. Stackhouse and M. Hartman
Prepared For
Emission Measurement Branch
Emission Standards and Engineering Division
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
March 1984
-------
GLOSSARY OF TERMS
EMB - Emission Measurement Branch
EPA - Environmental Protection Agency
NSPS - New Source Performance Standard
Golden West - Golden West Refinery Company
IAF - Induced Air Flotation
VOC - Volatile Organic Carbon
COD - Chemical Oxygen Demand
TOC - Total Organic Carbon
TCO - Total Chromatographic Organics
FID - Flame lonization Detector
GC - Gas Chromatograph
MS - Mass Spectrometer
THC - Total Hydrocarbon
OVA - Organic Vapor Analyzer
TCD - Thermal Conductivity Detection
VOA - Void of Air
QA - Quality Assurance
QC - Quality Control
As C3H8 - Based on Propane Standard
ppm - Parts per million
scfm - Standard cubic feet per minute
ii
-------
TABLE OF CONTENTS
Section Page
1 INTRODUCTION 1-1
2 SUMMARY AND DISCUSSION OF RESULTS 2-1
2.1 Ventilation Air Sampling Results 2-1
2.2 Process Water Analyses 2-15
3 PROCESS DESCRIPTION 3-1
3.1 Refinery Wastewater System 3-1
3.2 Emission Control Techniques 3-5
3.3 Monitoring of Wastewater Treatment System .... 3-6
4 LOCATION OF SAMPLE POINTS 4-1
5 SAMPLING AND ANALYTICAL METHODS 5-1
5.1 Gaseous VOC Methods 5-1
5.2 Permanent Gas Analysis 5-12
5.3 Gaseous Volumetric Flow Measurement 5-15
5.4 Liquid Sample Methods 5-15
5.5 Liquid Sample Analysis Methods 5-16
-------
LIST OF FIGURES
Figure Page
2-1 Wastewater treatment facilities with sample
locations at Santa Fe Springs, California 2-2
3-1 Wastewater treatment facility, Golden West
Refining Co 3-2
3-2 Sour water treating system 3-3
4-1 Sample locations at the wastewater treatment
facility: Golden West - Santa Fe Springs, California . 4-2
4-2 IAF tank system before off-gas line modification:
Golden West, Santa Fe Springs, California 4-3
4-3 IAF measurement system modifications:
Golden West, Santa Fe Springs, California 4-4
5-1 Gas bag sampling system 5-2
5-2 Example of GC/FID calibration for C!-C5 speciation . . . 5-4
5-3 Example of GC/FID analysis on IAF ventilation
air - gas bag sample for Cx-Cs speciation 5-5
5-4 Example of GC/FID calibration for C6~C9 speciation . . . 5-7
5-5 Example of GC/FID analysis on IAF ventilation
air - gas bag sample for C6-C9 speciation 5-8
5-6 Example of a calibration check with a
recalibration required 5-11
5-7 Example of GC/TCD calibration for stationary
gas analysis 5-13
5-8 Example of GC/TCD analysis on equalization tank #2
gas bag sample for stationary gases 5-14
(continued)
IV
-------
LIST OF FIGURES (Concluded)
Figure Page
5-9 Mass spectrometer qualitative analysis by purge
and trap, sample no. IAF-INLET-VOA-0740 5-22
5-10 Mass spectrometer qualitative analysis by purge
and trap, sample no. IAF-OUT-VOA-0740 5-23
5-12 GC/FID quantitative analysis by purge and trap,
sample no. IAF-INLET-VOA-0740 5-24
5-13 GC/FID quantitative analysis by purge and trap,
sample no. IAF-OUT-VOA-0740 5-25
-------
LIST OF TABLES
Table
2-1 Daily Time Table of Sampling Activities at Golden
West - Santa Fe Springs, California 2-3
2-2 Daily Emission Rate Averages at the IAF Outlet Sample
Location on Test Days 8/15/83 to 8/19/83 - Golden
West Refinery - Santa Fe Springs, California 2-5
2-3 Continuous Emission Results: Hydrocarbon Monitoring
at the IAF Outlet Sample Location - Golden West,
Santa Fe Springs, California - Test Day 8/15/83 .... 2-6
2-4 Continuous Emission Results: Hydrocarbon Monitoring
at the IAF Outlet Sample Location - Golden West,
Santa Fe Springs, California - Test Day 8/16/83 .... 2-7
2-5 Continuous Emission Results: Hydrocarbon Monitoring
at the IAF Outlet Sample Location - Golden West,
Santa Fe Springs, California - Test Day 8/17/83 .... 2-8
2-6 Continuous Emission Results: Hydrocarbon Monitoring
at the IAF Outlet Sample Location - Golden West,
Santa Fe Springs, California - Test Day 8/18/83 .... 2-9
2-7 Continuous Emission Results: Hydrocarbon Monitoring
at the IAF Outlet Sample Location - Golden West,
Santa Fe Springs, California - Test Day 8/19/83 .... 2-10
2-8 Flow Measurements with Anemometer: Golden West -
Santa Fe Springs, California 2-12
2-9 Gas Chromatograph Results From the IAF Test Days -
8/16/83 and 8/17/83, Golden West, Santa Fe Springs,
California : 2-13
2-10 Gas Chromatograph Results From the IAF Test Days -
8/18/83 and 8/19/83, Golden West, Santa Fe Springs,
California 2-14
(continued)
VI
-------
LIST OF TABLES (Concluded)
Table Page
2-11 Golden West Samples Taken on 8/16/83 2-16
2-12 Golden West Samples Taken on 8/17/83 2-18
2-13 Golden West Samples Taken on 8/18/83 2-23
2-14 Golden West Samples Taken on 8/19/83 2-25
2-15 Cj to C7 Speciation by GC/FID Purge and Trap,
Golden West, Santa Fe Springs, California 2-26
3-1 Crude Throughputs During the Test Period 3-4
3-2 Wastewater Flows to IAF During Test Period 3-7
5-1 Replicated COD and Oil and Grease Measurements 5-19
5-2 GC/FID Readings for Accuracy/Precision Estimates .... 5-26
5-3 Precision/Accuracy Estimates for IAF/DAF Samples .... 5-28
-------
1. INTRODUCTION
Under Section 111 of the Clean Air Act, the Environmental Protection
Agency is required to develop standards of performance for stationary
sources that have been determined to contribute significantly to air
pollution. EPA is conducting a study to develop standards that would
limit volatile organic compound emissions from new waste water treatment
systems in petroleum refineries. Under contract to the Emission
Measurement Branch, EPA, TRW Environmental Operations personnel conducted
a testing program at the waste water treatment system at Golden West
Refinery Company, Santa Fe Springs, California during August 15 to 19,
1983.
The purpose of the test program was to provide estimates of the
organic compound release rate from the induced air flotation (IAF) unit.
This information is necessary to estimate uncontrolled emission rates
from uncovered flotation devices for potential emission reduction and
cost effectiveness calculations.
The IAF at Golden West is equipped with a cover with access doors
that can be tightly sealed. Plant air is introduced at the influent end
of the unit to purge organic vapors from the unit. The ventilation air
stream exit the IAF through a vent at the effluent end of the IAF. This
vent stream is assisted by a blower which drives the organic laden
stream to low pressure nozzles in a nearby fired heater. The ventilation
air stream was measured to estimate the organic release rate that would
have occurred if the flotation device had been uncovered. This approach
was used to estimate uncovered unit emission because of the difficulty
in measuring a dispersed fugitive emission. It is assumed that the
dominant factors affecting organic emission rates are the water charac-
teristics and the physical turbulence caused by bubbling air through the
water, and that meterological factors such as air temperature and wind
speed are secondary parameters.
-------
Tests were conducted to determine the mass flow rate and the organic
species composition of the ventilation air from the IAF. During these
measurements, samples of waste water were collected to characterize the
streams from the IAF influent and effluent, and the API separation
influent. These samples were analyzed for chemical oxygen demand (COD),
total organic carbon (TOC), total chromatographical organics (TCO), and
oil and grease content using standard methods for water analysis.
The results of these tests are presented in Section 2. A description
of the process and the operation during the test period is given in
Section 3. The sampling locations and the sampling and analytical
procedures are discussed in Sections 4 and 5 respectively. The appendices
to this report contain example calculations, field data, test logs and a
list of project participants.
1-2
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2. SUMMARY AND DISCUSSION OF RESULTS
This section details the results of the testing and analysis at
Golden West Refinery Company waste water treatment unit. The refinery
waste water treatment system is illustrated in Figure 3-1, and the
sampling locations are indicated in Figure 2-1. Table 2-1 presents a
summary of the periods during which continuous hydrocarbon monitoring
was performed, and the periods during which integrated gas samples were
collected, flow rate measurements were performed, and when liquid samples
were collected. The results are presented in separate sections for air
and water samples.
2.1 VENTILATION AIR SAMPLING RESULTS
A summary of the daily average total hydrocarbon mass flow rates in
the IAF ventilation air stream is presented in Table 2-2. The total
hydrocarbon measurement does not exclude methane. The hydrocarbon mass
flow in the IAF ventilation air ranged from 1.17 to 1.40 Ibs/hr (24 hr.
basis) and averaged 1.31 Ibs/hr over the five days of testing. The test
results on a one-hour average basis are presented in Tables 2-3 to 2-7.
The average total hydrocarbon concentration based on equivalents of
propane is presented for each one-hour period. Propane was chosen as
the calibration species because it is a stable compound and calibration
mixtures are easily acquired and stored. For the organic species expected
at refineries, the response of the analysis is directly proportional to
the carbon content. While the concentration results are on a propane
basis and are not equal to the time hydrocarbon concentration, the
calculated mass flow rates are equivalent to true hydrocarbon mass flow
rates.
The average gaseous flow rate result that was used for calculation
of the hydrocarbon mass flow is also given for each day of monitoring.
This value represents the average flow over a two to six hour test
-------
r\>
ro
Air I 1" H20
IAF-INLET
Water
Samp.lt
Floated
Oil
Water
Water
API-INLET
Water
Sample
IAF-OUTLET
J (GAS SAMPLE)
Covered and Sealed IAF
Covered
API Separator
Covered
API Separator
IAF-OUTLET
Water Sample
Platform
Boiler
Blower
Equalization
Tanks
*»» Water
Discharge/
Figure 2-1. Wastewater treatment facilities with sample locations at Santa Fe Springs, California.
-------
Table 2-1. DAILY TIME TABLE OF SAMPLING ACTIVITIES AT GOLDEN WEST - SANTA FE SPRINGS, CALIFORNIA
0700
0800 0900 1000 1100 1200 1300 1400 1500
1600 1700
1800
ro
CO
L9C«t
-------
Lpc«t1on/0*U
IAF OUTLET 8/18
Table 2-1. Concluded
0700 0800 0900 1000 1100 1200 1300 1400 1500 1600 1700 1800
- (0000-2400)
£> A
a a
a
ro
4*
IAF INLET 8/18
API INLET 8/18
IAF OUTLET 8/19
IAF INLET 8/19
API INLET 8/19
^^-MM^V
a . a
o
o
o
o
A A
a a
0
o
a
o
0
a
LEGEND
A (Mtthod 18-G« Big)
O (Vcloclty-inMomttr)
O (Liquid Composite)
O (Liquid VOA)
C 3 (Method Z5-A THC)
-------
Table 2-2. DAILY EMISSION RATE AVERAGES AT THE IAF OUTLET
SAMPLE LOCATION ON TEST DAYS 8/15/83 to 8/19/83
GOLDEN WEST REFINERY - SANTA FE SPRINGS, CALIFORNIA
Average daily emission rate
Test day (Ib/hr as C3H8)
8/15/83 1.40
8/16/83 1.39
8/17/83 1.17
8/18/83 1.25
8/19/83 1.39
2-5
-------
Table 2-3. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF OUTLET SAMPLE LOCATION - GOLDEN WEST,
SANTA FE SPRINGS, CALIFORNIA - TEST DAY 8/15/83
Time
1600°
1700
1800
1900
2000
2100
2200
2300
2400
Average
Concentration3
(ppm as C3H8)
7092
7042
6925
6792
6400
6258
6170
6083
6050
Flowb
(SCFM)
30.4
30.4
30.4
30.4
30.4
30.4
30.4
30.4
30.4
Emission rate
(Ibs/hr as C3H8)
1.38
1.53
1.50
1.47
1.39
1.36
1.34
1.32
1.31
1.40
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
No flow measurement on 8/15/83; therefore, used average of IAF daily
flows. See Table 2-8.
Continuous Hydrocarbon Analyzer (Beckman 402) on-line at IAF outlet
starting the test period.
2-6
-------
Table 2-4. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF OUTLET SAMPLE LOCATION - GOLDEN WEST,
SANTA FE SPRINGS, CALIFORNIA - TEST DAY 8/16/83
Time
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Average
Concentration3
(ppra as C3HS)
6250
6125
6100
6300
6750
6675
6844
6700
6458
6725
7483
7267
6908
6289
5850
5850
6058
5725
5650
6100
6233
6300
6708
6883
Flowb
(SCFM)
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
33.9
Emission rate
(Ibs/hr as C3H8)
1.36
1.33
1.32
1.37
1.47
1.45
1.49
1.45
1.40
1.46
1.62
1.58
1.50
1.37
1.27
1.27
1.31
1.24
1.23
1.32
1.35
1.37
1.46
1.49
1.39
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-rainute readings.
Two flow measurements taken on 8/16/83; therefore, average used for daily
flow. See Table 2-8.
2-7
-------
Table 2-5. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF OUTLET SAMPLE LOCATION - GOLDEN WEST,
SANTA FE SPRINGS, CALIFORNIA - TEST DAY 8/17/83
Time
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Average
Concentration3
(ppm as C3H8)
6925
6783
6075
6608
6950
7033
7150
6867
7992
8675
8592
8811
7500
6508
6558
6175
6367
6667
6958
7308
7392
7017
6825
6917
Flow5
(SCFM)
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
Emission rate
(Ibs/hr as C3H8)
1.14
1.12
1.01
1.09
1.14
1.16
1.17
1.13
1.32
1.43
1.41
1.45
1.23
1.07
1.08
1.02
1.04
1.10
1.14
1.20
1.21
1.15
1.12
1.14
1.17
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
One flow measurement taken across day period (7:40-14:19) on 8/17/83 and
used as average daily flow. See Table 2-8.
2-8
-------
Table 2-6. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF OUTLET SAMPLE LOCATION - GOLDEN WEST,
SANTA FE SPRINGS, CALIFORNIA - TEST DAY 8/18/83
Time
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Average
Concentration
(ppm as C3H8)
7192
7300
7483
7500
7473
6942
6800
c
c
6010 :-..
5940
6475
6650
6800
7150
7050
6750
6700
6440
6710
6650
6630
6750
6660
Flowb
(SCFM) <
28.7
28.7
28.7
28.7
28.7
28.7
28.7
. -
28:7
28.7
28.7
28.7
28.7
28.7
28.7
28.7
28.7
28.7
28.7
28.7
28.7
28.7
28.7
Emission rate
[Ibs/hr as C3H8)
1.32
1.34
1.37
1.37
1.32
1.27
1.25
1.11
1.09
1.19
1.22
1.25
1.31
1.29
1.24
1.25
1.18
1.23
1.22
1.22
1.24
1.22
1.25
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
u \
One flow measurement taken across day period (10:25-15:03) on 8/18/83 and
used as average daily flow. See Table 2-8.
°Process interrupt!on/With instruments off-line.
2-9
-------
Table 2-7. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF OUTLET SAMPLE LOCATION - GOLDEN WEST,
SANTA FE SPRINGS, CALIFORNIA - TEST DAY 8/19/83
Time
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300C
Average
Concentration3
(ppm as C3H8)
6440
6210
5920
5900
6090
6150
6360
6200
6210
6325
6630
6760
6640
Flowb
(SCFM)
34.5
34.5
34.5
34.5
34.5
34.5
34.5
34.5
34.5
34.5
34.5
34.5
34.5
Emission rate
(Ibs/hr as C3H8)
1.42
1.37
1.31
1.30
1.35
1.36
1.41
1.37
1.37
1.40
1.46
1.49
1.47
1.39
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
One flow measurement taken across day period (8:34-14:03) on 8/19/83 and
used as average daily flow. See Table 2-8.
eEnd of test at the IAF Outlet/Golden West Refinery.
2-10
-------
period each day of testing. The results of the flow measurement are
presented in Table 2-8. A single average value can be used because the
flow rate was determined to be constant based on intermediate readings
during the test. The field data sheets containing intermediate measure-
ments are contained in Appendix A.
The results of the analysis of the integrated gas samples of the
IAF ventilation air are presented in Tables 2-9 and 2-10. The species
analyses were obtained using two field gas chromatographic systems and
were intended to generally identify the major components and their
approximate concentrations. Calibration standards were available
for Cl to C5, benzene and m-xylene, so the results for these compounds
can be calculated directly. Hexane, heptane, and p-xylene are calculated
as equivalents of the nearest carbon number calibration species. Other
peaks were also grouped with the closest eluting calibration species for
computation. Since a benzene standard was used to establish a specific
retention time for that compound, it can be concluded that the peak
occurring at that time was benzene. However, these are some compounds
found at refineries that tend to elute near benzene (such as
methylcyclopentane and cyclohexane) and would be indistinguishable with
this analytical system. However, since clear identification of toluene
and xylene were present, it is probable that at least part of the
concentrations attributed to benzene was actually benzenes. Additional
descriptions of the chromatographic techniques are given in Section 5.
The general results of the species analysis are consistent in the
relative amounts of the compounds found. The major peaks were distributed
in the C4 to C7 range. The results of these analyses can be used to
calculate a non-methane hydrocarbon emission rate, but this calculation
was not performed for this report.
The results of chromatographic analysis to determine the balance
gas composition are generally as expected, with the analysis being
approximately air. However, several of the analysis results show oxygen
concentrations greater than found in ambient air. These higher results
are probably due to a variation in the operation conditions of the
analyzer between calibrations and do not represent real values. This
has no affect on any of the other calculated results.
2-11
-------
Table 2-8. FLOW MEASUREMENTS WITH ANEMOMETER:
GOLDEN WEST - SANTA FE SPRINGS, CALIFORNIA
ro
»-
ro
Date
8/16/83
8/16/83
8/17/83
8/18/83
8/19/83
Time
0800-1200
1200-1400
0740-1419
1026-1503
0834-1403
Temperature
(°F) Feet
123
128
117
116
115
110300
46900
125500
98000
142000
Time
period
in min
265
104
399
277
329
Anemometer
average rate
(ft/min)
Indicated
416
450
314
354
432
True
416
450
324
360
432
Actual
volumetric
flowrate
(ACFM)
36.3
39.3
28.3
31.4
37.7
Standard
vblumetric
flowrate
(SCFM)
32.7
35.1
25.7
28.7
34.5
-------
Table 2-9. GAS CHROMATOGRAPH RESULTS FROM THE IAF
TEST DAYS - 8/16/83 AND 8/17/83
GOLDEN WEST, SANTA FE SPRINGS, CALIFORNIA
DATE
TIME
RUN NO.
ANALYTICAL RESULTS
(ppmv as compound)
C-l
C-2
C-3
C-4
C-.5
Hexane
Benzene
Toluene
m-Xylene
o-Xylene
TOTAL HYDROCARBONb
(ppmv as compound)
CONTINUOUS MONITOR
DATA
Hydrocarbon Level
(ppmv as C3H8)
Emission Rate
(Ib/hr)
PROCESS CONDITIONS
% N2
% 02
% C02
8/16
735-835
1
74.0
6.8
14.2
38.6
52.0
115
1357
1346
933
326
4262
6772
1.47
76.17
18.60
8/16
1020-
1120
2
110
9.4
22.1
269
250
370
2851
2486
1458
467
8292
7104
1.54
75.69
19.50
8/16
1235-
1335
3
90.8
9.6
14.4
108
130
1068
2424
2321
1578
510
8253
7087
1.54
73.46
18.52
0.94
8/17
0745-
0845
1
138
7.8
19.0
140
183
180
1758
1629
905
305
5265
7008
1.15
75.92
21.66
8/17a
1000-
1100
2
135
20.9
78.5
315
685
577
3638
2376
813
283
8921
8675
1.42
73.75
20.04
8/17a
1153-
1253
3
262
122
365
341
524
3530
2476
885
308
8813
8811
1.45
73.09
21.12
0.40
See explanation in Section 2.2.2.
5Total includes unidentified hydrocarbon responsive to GC/FID.
2-13
-------
Table 2-10. GAS CHROHATOGRAPH RESULTS FROM THE IAF
TEST DAYS - 8/18/83 AND 8/19/83
GOLDEN WEST, SANTA FE SPRINGS, CALIFORNIA
DATE
TIME
RUN NO.
ANALYTICAL RESULTS
(ppmv as compound)
C-l
C-2
C-3
C-4
C-5
Hexane
Benzene
Toluene
m-Xylene
o-Xyl ene
TOTAL HYDROCARBON3
(ppmv as compound)
CONTINUOUS MONITOR DATA
Hydrocarbon Level
(ppmv as C3H8)
Emission Rate
(Ib/hr)
PROCESS CONDITIONS
% N2
% 02
% C02
8/18
1030-
1146
1
44.5
3.0
4.2
10.5
14.9
49.7
547
889
647
236
2446
5975
1.08
75.75
21.57
0.76
8/18
1310-
1410
2
94.7
4.1
8.0
96.5
71.0
81.4
1106
1661
1164
407
4695
6725
1.21
72.69
. 21.21
1.18
8/19
850-
950
1
66.0
5.3
8.1
28.4
90.3
93.5
865
1110
640
228
3135
6205
1.37
73.61
23.43
0.43
8/19
1030-
1130
2
72.8
6.8
10.0
50.7
78.9
116
1236
1785
890
297
4544
6327
1.43
70.92
27.74
0.33
aTotal includes unidentified hydrocarbon responsive to GC/FID.
2-14
-------
2.2 PROCESS WATER ANALYSES
Tables 2-11 through 2-15 provide the process water analysis for the
composite and grab samples taken during the hydrocarbon (air) monitoring.
Designated samples (item, location) were analyzed for the following
parameters:
TOC (total organic carbon);
COD (chemical oxygen demand);
oil and grease; and
TCO (total chromatographable organics/hydrocarbon speciation
(Cr-C30) and VGA by purge and trap GC/FID.
All analytical parameters are reported in milligrams per liter (ppmw),
except purge and trap values which are given in parts per billion (ppbw).
The most critical factors in the measurement of the process water
parameters were the collection of representative samples at the site
location and obtaining a representative aliquot for analysis in the
laboratory. In most cases the samples involved two-phase oil/water
mixtures which contributed to the non-homogeneity of the samples and to
the variation in the sample values.
The sampling points at the Golden West treatment plant were dictated
by the physical layout and available sample locations. The samples were
collected from streams at elevated temperatures, stored on ice, and
shipped to the TRW laboratory. Sample preservatives were not utilized
in preference to immediate analysis (24-48 hours) and to the elevated
levels of hydrocarbons in the streams. Upon arrival at the laboratory
all samples were homogenized prior to analysis; however, the two-phased
system and the cooling of the sampling affected the homogeneity of the
samples. All samples were brought to room temperature and shaken
vigorously before samples were removed. In addition, due to the high
levels of the parameters being measured, the size of the sample aliquots
were small which also contributed to the variability from sample to
sample.
2-15
-------
Table 2-11. GOLDEN WEST SAMPLES TAKEN ON 8/16/83
COD Oil/grease TOC TCO
TRW No. mg/L rag/L mg/L mg/L
Liquid Composite Samples
lAF-in
lAF-out
API-in
Volatile Organic Samples
IAF-in VOA (0805)
lAF-in VOA (1400)
lAF-out VOA (0805)
lAF-out VOA (1400)
5,047 2,323
5,051 909
5,043 2,020
5,055
5,056
5,063
5,064
11.31 104.46
21.89 40.78
23.37 25.64
344
411
237
304
(continued)
2-16
-------
Table 2-11. 'Concluded
TRW No.
mg/L
Liquid Composite Samples
lAF-in
lAF-out
API- in
5,047 Toluene
C8
C10
C10
Cjo
C12
Cj3
Cjs
Cl4
C15
Cl6
C17
C19
C21
5,051 Toluene
C8
C9
C9
Cjo
C10
C12
5,043 Toluene
C8
C9
C10
C12
Cis
C14
ClS
C16
Cl7
7.611
5.581
28.782
8.904
6.967
11. 572
12.999
3.990
6.041
11.920
5.032
229.816
60.938
65.569
34.653
34.247
24. 253
3.721
1.841
0.899
21. 115
6.998
13.501
1.888
2.546
1.632
5.749
3.522
4.173
2.765
2.646
1.699
2.621
1.395
65.244
2-17
-------
Table 2-12. GOLDEN WEST SAMPLES TAKEN ON 8/17/83
COD Oil/grease TOC TCO
TRW No. mg/L mg/L mg/L mg/L
Liquid Composite Samples
lAF-in
lAF-out
API- in
Volatile Organic Samples
lAF-in VGA (0740)
lAF-in VOA (1300)
lAF-out VOA (1300)
lAF-out VOA (0740)
5,048 4,089 14.09
5,052 2,328 4.59
5,044 5,628 17.62
5,057
5,058
5,065
5,066
158.5
109.32
244.30
554
426
323
137
(continued)
2-18
-------
Table 2-12. Continued
TRW No. rag/L
Liquid Composite Samples
lAF-in 5,048 Toluene
C7
C8
C8
C8
C8
C8
C8
C9
C9
-C9
C9
C9
' Cg
" C9
C9
C9
CIQ
CIQ
CIQ
Cii
Cn
Cn
Cn
Cn
Cn
C12
C12
dl
C12
C13
C13
Cl4
ds
ClS
Cl6
C16
Cl7
\ °17
76. 223
1.835
3.602
2.422
2.066
5.420
17.959
6.712
3.833
1.632
2.160
2.644
3.057
4.577
2.640
5.201
5.709
3.968
8.078
11.172
4.848
2.108
3.772
1.906
1.556
2.039
7.783
2.979
2.162
2.496
13.111
14.532
7.058
3.105
4.510
3.376
10.791
4.026
5.481
2.347
91.409
224.621
(continued)
2-19
-------
Table 2-12. Continued
TRW No.
5,048 C18
Cis
Cj9
C20
C21
C22
C23
C24
C25
lAF-out - 5,052 Toluene
C7
C7
C7
C8
C8
C8
C8
C8
C8
C9
C9
C9
C9
C9
C9
C9
CIQ
CIQ
C10
c"
CIQ
CIQ
CIQ
Cn
Cn
Cj.
Cn
Cn
Cn
Cn
Cn
*' f*
c"
(continued)
2-20
mg/L
87.140
84.054
110.444
73.046
90.032
73.718
46.656
55.906
30.594
50.025
0.482
0.516
0.957
0.688
0.563
2.543
10.277
3.919
1.296
0.628
0.618
1.126
1.611
2.743
1.290
30.117
2.226
2.117
0.971
0.588
0.889
9.658
20.001
2.108
0.666
1.663
2.282
0.674
2.144
0.726
0.916
0.681
1.092
2.921
-------
Table 2-12. Continued
TRW No.
5,052 C12
C12
C12
C12
Cj3
C13
c"
C14
C15
C15
CIB
C17
Cj9
C2o
: . c2i
C22
C24
API- in 5,044 Toluene
C7
C7
C8
C8
C8
C8
C8
C9
C9
C9
C9
C9
C9
C9
Cj,o
C10
C10
' CIQ
CIQ
C10
' (continued)
/ 2-21
mg/L
1.337
1.231
1.445
7.804
8.226
1.390
1.850
2.598
1.808
5.846
2.174
84.094
105.381
39.690
50.973
36.077
29.241
20.598
23.798
14. 621
23.873
1.593
2.085
2.157
5.764
24.131
9.263
2.470
3.303
4.726
6.821
3.696
1.205
4.956
9.215
5.188
2.297
2.867
1.772
8.807
4.265
2.081
-------
Table 2-12. -Concluded
TRW No.
5,044 Cia
Cn
Cn
Cn
Cn
Cn
Cn
c«
Cn
Cj2
C12
£12
C12
Ci2
Ci2
Cl3
Cl4
Cl4
Cl5
Cie
Ci7
C18
mg/L
3.670
1.726
3.837
4.716
1.931
1.812
5.883
2.842
6.898
2.667
3.212
3.528
2.250
15.183
15.331
7.276
15.577
7.765
3.512
63.229
180.452
86.216
-------
Table 2-13. GOLDEN WEST SAMPLES TAKEN ON 8/18/83
COD Oil/grease TOC TCO
TRW No. mg/L mg/L mg/L mg/L
Liquid Composite Samples
lAF-in
lAF-out
API-4 (1130)
Volatile Organic Samples
IAF-in VOA (1050)
lAF-in VOA (1500)
lAF-out VOA (1050)
lAF-out VOA (1500)
5,049 1,162 31.83
5,053 1,111 16.71
5,045 1,364 15.16
5,059
5,060
5,062a
5,067
46.48
34.34
36.04
204
283
315
aSample broken in laboratory.
(continued)
2-23
-------
Table 2-13. Concluded
TRW No.
mg/L
Liquid Composite Samples
lAF-in
5,049
lAF-out
5,053
API-4 (1130)
5,045
Toluene
C8
C10
C12
Toluene
C8
C9
C9
Cjo
C12
Toluene
C8
<£
9.752
4.435
.832
,299
1.
1.
22.145
7.012
14.987
2.081
1.203
29.697
5.949
2.174
1.071
16,975
5.575
10.822
0.853
5.477
2.531
0.971
1.052
17.101
5.889
12.505
1.399
0.976
25.959
2-24
-------
Table 2-14. GOLDEN WEST SAMPLES TAKEN ON 8/19/83
COD Oil/grease TOC TOO
TRW No. mg/L mg/L mg/L mg/L
Liquid Composite Samples
lAF-in
lAF-out
API- in
Volatile Organic Samples
lAF-in VOA (0830)
lAF-in VOA (1400)
lAF-out VOA (0830)
lAF-out VOA (140)
5,050 1,194 348
5,054 830 332
960 201
5,046 3,482 1,321
5,061 289
5,070 509
5,068 293
5,069 607
2-25
-------
Table 2-15.
GOLDEN WEST, SANTA FE SPRINGS, CALIFORNIA
TO C? SPECIATION BY GC/FID PURGE AND TRAP
TRW No. Sample Number Compound
5056 IAF- INLET- VOA- 1400 C3H60
CsHia
C6H140
Benzene
Hexane
C7H14
C7H16
Toluene
5064 IAF-OUT-VOA-1400 C3H60
C5H12
C6H140
Benzene
Hexane
C7H14
C?H16
Toluene
5057 IAF- INLET- VOA-0740 C3H60
C5H12
C6H140
Benzene
Hexane
C7H14
C7H16
Toluene
Concentration
Date Taken (in ppb)
8/16/83 342
87.0
12.6
136
36.8
18.4
14.4
243
8/16/83 310
108
71.2
5710
8.21
48.8
166
7620
8/17/83 379
103
91.0
6450
13.7
74.0
11.9
8640
(continued)
2-26
-------
Table 2-15. .Concluded
TRW No. Sample Number Compound
5066 IAF-OUT-VOA-0740 C3H60
C5H12
C6H140
Benzene
Hexane
C7H14
C7H16
Toluene
5059 IAF- INLET- VOA-1050 C3H60
C5H12
C6H140
Benzene
Hexane
C7H14
C7H16
Toluene
5067 IAF-OUT-VOA-1050 C3H60
CSH12
Benzene
Toluene
Concentration
Date Taken (in ppb)
8/17/83 359
106
73.8
5990
22.5
80.6
4.32
8350
8/18/83 260
104
147
6230
25.2
136
15.0
11000
8/18/83 234
102
487
646
2-27
-------
3. PROCESS DESCRIPTION
The Golden West Refining Company's Santa Fe Springs facility is a
small refinery located in a semi-industrial area of Santa Fe Springs,
California. The refinery has a crude throughput capacity of 51,000 barrels
per calendar day (b/cd) and was operating at approximately 65 percent
capacity during the time of the test. Crude throughputs recorded during
the test period are listed in Table 3-1.
The Effluent Guidelines Division of the Environmental Protection
Agency places Golden West in refinery subcategory B which includes
refineries producing petroleum products by the use of topping and cracking
operations. Wastewater produced by the refinery undergoes primary and
secondary oil removal before being sent to a Publicly Owned Treatment
Works (POTW).
3.1 REFINERY WASTEWATER SYSTEM
The refinery wastewater system at Golden West is shown schematically
in Figure 3-1. Oily wastewaters are collected in the process units and
directed to the distribution box of the API separators through
two trunk!ines. Stormwaters are segregated from the oily wastewaters as
much as possible and are collected in three trunk!ines which converge on
a diversion box located near the API separators. During periods of
heavy rainfall, stormwater will be diverted to storage facilities located
away from the treatment system. Otherwise, the small quantities of
wastewater collected by three storm mains will enter the API distribution
box. Sour wastewaters undergo inplant treatment before reaching the API
separators. The sour water treatment system is shown in Figure 3-2.
The distribution box divides wastewater flow equally between the
two API separators. Each separator is approximately 15 feet wide,
60 feet long, 10 feet deep, and is provided with a wooden cover. Chain
-------
outfall to PCTV
sludge tank
(out of Mrrica
slop oil tank
slucfyt drswoff by
truck
to rilnwatar storage facilities
Oivtrslon Box
PH «
-------
offjii to Ml fur
* »» » « * «l
CO
CO
lour tttt«p
FrM mlti
10
ti
T
..-i ~
^M
«r Mt
itk
bmt
i i r
trl
4n
*
»
(C
(71
1
Sw
a
'
iklmd
Tnflm KM
(JSiiB
(1 lit SU
VLibitU
i
3
4
NT MUr .
trlpiMr .
1
i
« , ..
I
,.,.., .
r »
I
r "
ii ! !*
t
brocut ImfU
fttpirtttr |
, 1
^C
! *
fc
T ' -.
1 sour rnttr 1
M U
fejAltt
xUlitr
lew MUr
HkltMiUr
fr*cii* wilt
tlljr
.^ To County
S«Mr SystM
Figure 3-2. Sour water treating system.
-------
Table 3-1. CRUDE THROUGHPUTS DURING THE TEST PERIOD
Date Barrels per calendar day
8-15-83 34,288
8-16-83 33,939
8-17-83 33,323
8-18-83 33,062
8-19-83 33,233
3-4
-------
driven wooden skimming bars continually push floating oil to slop oil
pits and scrape settled sludge into sludge hoppers. Oil collected in
the slop oil pits flows to a channel located between the separators.
Settled sludge is removed from the sludge hoppers by vacuum trucks
two to three times per week.
Effluent from the API separators is pumped to the IAF for secondary
oil removal. The induced air flotation unit (IAF) was installed by
WEMCO and is designed to treat a wastewater flow of 750 gallons per
minute (gpm). Small quantities of chemical coagulant are added to the
wastewater prior to the IAF. The coagulant aids in breaking oily emulsions
and improves the performance of the system. Floated oil removed from
the IAF is recirculated to the API separators. Wastewater effluent is
pumped to dual open bays which are adjacent to the API separators. The
open bays are similar in configuration to the API separators. The bays
are uncovered and do not have mechanical skimmers.
The open bays are the final treatment step at Golden West. Each
tank is divided into two sections by a curtain wall which acts to retain
any floating oil. Slop oil pits located in each section collect the
floating oil which then flows into the collection channel between the
two bays. All the oil collected in the channel is pumped to a slop oil
holding tank located next to the wastewater treatment facilities.
3.2 EMISSION CONTROL TECHNIQUES
Volatile organic compound (VOC) emissions are controlled from the
API separators and the IAF system. The separators are equipped with
wooden covers and are sealed as tightly as possible. Access doors are
used to inspect the operation of the separators. The covers can be
easily removed to allow maintenance procedures to be carried out.
During the test period, one API separator was emptied and uncovered in
order to repair the mechanical skimmer.
The IAF is designed with a cover and eight access doors allow
visual inspection of the unit. These doors are gasketed and can be
tightly sealed. Plant air is introduced at the influent end of the IAF
to purge VOC from the vapor space. The purged vapors leave the IAF
through a vent at the effluent end of the unit. This vent leads to a
3-5
-------
blower which drives the VOC emissions to the fuel gas input of a fired
heater located near the wastewater treatment system. The vent from the
IAF and blower are also shown in Figure 3-1.
3.3 MONITORING OF WASTEWATER TREATMENT SYSTEM
The effluent from the wastewater treatment system at Golden West is
sent to a Los Angeles County Treatment Works before final disposal. The
refinery wastewater system must meet pretreatment requirements specified
by the county. Golden West routinely monitors refinery effluent for pH,
thiosulfate sulfur, BOD, suspended solids, fluorides, and ammonia. An
outside contractor conducts further wastewater analysis on a quarterly
basis to insure compliance with the county requirements.
A circular chart records wastewater flow to the IAF. Table 3-2 is
a summary of flow readings taken during the test period. Average
wastewater flow to the IAF was 450 to 500 gallons'pef minute. Golden
West reported an average flow of 400 to 450 gpm as being the normal
range. The slightly higher average flow recorded during the test may be
a result of rainfall during the week. The wastewater system in general
is capable of handling peak flows of 1000 gpm. This would represent
extreme conditions, however, since the IAF is designed to handle only
750 gpm.
Oily wastewater from all process units is directed to the API
separators. However, it is impossible to monitor flow from specific
units and it is therefore difficult to anticipate upset conditions which
would influence the wastewater system. The operators responsible for
the system must regularly observe the operation at the API separators,
IAF, and open bays to detect upsets. During the test period, one instance
of upset condition was observed.
On Wednesday morning, August 17, large amounts of floating oil were
observed in the open bays. Normally, very little, if any, floating oil
would be seen at this stage of treatment. Investigations by plant
operators revealed that an excessive quantity of oil had accidently
entered the sour water stripping system. The oil which entered the
system during the upset had apparently come from the crude slop tank.
Unusually high quantities of oil were being drawn from the tank with the
sour waters. Normal procedures at Golden West call for the sour water
3-6
-------
Table 3-2. WASTEWATER FLOWS TO IAF DURING TEST PERIOD
Date Time
8-16-83 0830
1040
1400
8-17-83 0200
0400
0715
0930
1200
1400
8-18-83 0300
0530
0600
0730
0900
1000
1100
1130
1200
0300
8-19-83 0000
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
Gallons per minute (gpm)
495
510
250
525
600
525
675
375
375
488
675
450
525
450
375
413
420
375
413
>700
525
563
600
525
450
450
488
525
563
600
>675
525
3-7
-------
system to be drained regularly so that accumulated sludge can be removed.
It was during this maintenance procedure that the upset occurred. The
sour water treating system is shown in Figure 3-2.
As a result of the upset, abnormal operating procedures were also
observed on Thursday, August 18. Plant operators determined a need to
increase coagulant addition to the IAF. In order to accomplish this,
one access door on the IAF was opened and coagulant fed manually to the
unit. During this time, the plant air used to purge vapors from the IAF
was turned off. This procedure was followed from approximately 07:30
to 10:10 on Thursday.
The amount of floating oil in the open basins gradually subsided as
a result of remedial measures taken by the plant. Along with an increase
of coagulant to the IAF, coagulant had also been directly added to the
open bays on Wednesday in an effort to remove the floating oil.
3-8
-------
4. LOCATION OF SAMPLE POINTS
The gaseous and water sampling locations used for the testing of
the effluent treatment system serving the process waste waters are shown
in Figures 4-1 through 4-3. The treatment system consisted of dual API
separators feeding to an induced air flotation (IAF) tank. The inlet
and outlet process water samples were taken from both the API and IAF
systems. The gaseous sampling was performed on the ventilation air of
the IAF tank.
The sample location for the ventilation air from the IAF unit was
located in an adaptation configured in the ventilation air line. The
pipe was disconnected prior to the off-gas blower feeding the IAF
ventilation air to the process boiler. The locations of the gaseous
sampling point and velocity measurement system are provided in Figure 4-3.
The IAF ventilation line adapted with the measurement system was a
three-inch steel pipe. The steel pipe was fitted with a four-foot
section of four-inch aluminum pipe, a volumetric totalizing flow meter,
and four-inch plastic flexible ducting. The total flow in this line was
routed through the flow volume measurement meter. Samples for determi-
nation of gaseous components were extracted through a %-inch hole in the
aluminum piping prior to the meter.
The water sampling sites during these tests were the influent and
effluent of the IAF system and the influent to the API separator system.
The IAF influent was obtained from a sampling tap installed in the feed
line from the API separator to the IAF tank. The API influent sample
was obtained from a sampling tap in the oil water influent piping. The
IAF outlet sample was obtained from a sampling tap after the IAF discharge
pump.
-------
ro
A1r t 1" H20
IAF-INLET
Water
Sample <
Floated
Oil
Mater
Mater
API-INLET
Mater
Sample
IAF-OUTLET
I (GAS SAMPLE)
Covertd and Sealed IAF
Covered
API Separator
Covered
API Separator
IAF-OUTLET
Mater Sample
Platform
Boiler
Blower
Equalization
Tanks
-»» Mater
Discharge.?
Figure 4-1.
Sample locations at the wastewater treatment facility:
Golden West - Santa Fe Springs, .California.
-------
IAF Outlet-Water
Sampling Location
-
I
*»
£
Walkway
1
1
1
1
1
1
1
1
1
Depurator
O
Depurator
O
Depurator
Depurator
O
o=Q=
4" Breather
1
1
1
1
1
1
1
1
1
1
Off-Gas to Fired Heater
(See Fig. 4-3 Modification)
Ffgure 4-2. IAF tank system before off-gas line modification:
Golden West, Santa Fe Springs, California
4-3
-------
4" Breather
Valve
Q
Pressure
Relief Valve
4*
Sample Line
Vane Anemometer
IAF Outlet
Composite and VGA
Sampling Location
Figure 4-3.
IAF measurement system modifications:
Golden West, Santa Fe Springs, California.
-------
5. SAMPLING AND ANALYTICAL PROCEDURES
The sampling and analytical procedures used to evaluate the gaseous
and liquid streams are presented in this section. The methodologies are
discussed separately as gaseous VOC methods (5.1), fixed gas analysis (5.2),
gas flow measurement (5.3), liquid sampling (5.4), and liquid sample
analysis (5.5).
5.1 -GASEOUS VOC METHODS
Two procedures were used to measure the VOC content of the gaseous
streams. EPA Method 18 was used to determine the general VOC species in
the samples, and a procedure similiar to EPA Method 25A was used to
measure the equivalent total hydrocarbon content of the streams.
5.1.1 EPA Method 18
"EPA Method 18. Measurement of Gaseous Organic Compound Emissions
by Gas Chromotography", (promulgated October 18, 1983, Federal Register
48 FR 48328) was used to characterize the organic components in the
streams tested. Samples were collected using the integrated bag technique
of Method 18. Figure 5-1 illustrates the apparatus.
fit
A clean 2.5 cubic foot TEDLAR flexible bag was used for each run.
The bags were cleaned by filling with dry nitrogen and venting the bag
contents to the atmosphere until no background organics were detected by
the analysis system. Prior to sampling the sampling apparatus and
flexible bag were leak checked by evacuating each to 29" Hg vacuum and
monitoring the pressure for 10 minutes. If a change of less than 1" Hg
is observed, the components are judged leak-free. The sample probe,
sample connecting tubing, and the sample bag were operated at ambient
temperature. To prepare for sampling the vacuum source can was evacuated
to -29" Hg. The system was then assembled and the sample probe was
placed near the centroid of the duct to be sampled. Sampling was
-------
PVC Tubing
Probe
5' Teflon Tubing
Pinch Clamp
in
ro
Gromnet
Air Tight Steel Drum
Sample Bag
Directional
Needle Valve
Quick Disconnectors
Evacuated Steel
Drum
Figure 5-1. Gas Bag Sampling System.
-------
started by opening the flow control valve and was maintained at a constant
rate using the rotameter for about one hour. At the end of the sampling
period, the flow valve was closed, the probe was disconnected, and the
bag inlet was sealed. The sample bag was transported to the on-site
mobile laboratory for analysis.
Two gas chromatograph systems with flame ionization detectors were
used to analyze each sample. One system was used to separate and quantify
low molecular weight parafins and olefins while the other system was
used to measure aromatics and higher molecular weight components.
The system used to measure low molecular weight compounds (termed
Cj-Cs components) was a Shimadzu GC Mini 1 with a Shimadzu Chromatopac
CRI-A digital integrator/recorder. The operating parameters were:
Column: 6 ft x 1/8 in. I.D. stainless steel.
Column support: Poracil C.
Column temperature/program: 35°C/constant.
Sample loop size/temperature: 1 ml/ambient.
Carrier gas/flow: He/50 ml/min.
A calibration gas mixture containing known concentrations of methane,
(15.1 ppm) ethane (14.6 ppm), propane (15.6 ppm), butane (15.2 ppm), and
pentane (15.6 ppm) in nitrogen was used to obtain a area factor and
retention time for each of these compounds. Figure 5-2 presents an
example of a GC/FID calibration run for Cj-Cs speciation. During sample
analysis, the peaks near these retention times were grouped as the
nearest carbon number, and the concentration was calculated using the
corresponding calibration factor for that carbon number. Figure 5-3
presents an example of GC/FID analysis runs for Cj-C5 speciation at the
IAF sample location.
The GC/FID analysis run for Cj-Cg speciation (Figure 5-3) provides
an illustrative example of problems in the analytical procedures.
Standards were not available to provide elution time reference for all
peaks identified by the GC/FID with areas. Therefore, the total organic
concentration from the analysis was a sum of all the peaks and not just
the identified peaks. Another problem was the slight variance of the
elution time during the test day. The GC/FID operator noted an increase
5-3
-------
CflL
STflRT 08.16.87.27
^fes
3.18
7.05
8.31
9.35
9.95
STOP
C-R1R
SMPL f 66
FILE * 7
REPT # 118
METHOD 44
# NftME TIME
6.17
6.29
1 HETH 6.39
2 ETHfl 6.63
1.31
2.78
3.18
7.65
8.31
9.35
9.95
TOTftL
.
CONC . MK
V
6 V
6 V
V
V
V
- T
T
e
RRER
43
1167
1362
1955
. 2652
27
3443
232
4556
25
94
15566
Figure 5-2. Example of GC/FID calibration for Cj-C5 speciation.
5-4
-------
IftF-3
.START M. 14.13.53.
13.75
'STOP
C-R1B
SHPL
FILE
*EPT
METHOD
8
7
127
44
1
2
3
4
5
5
6 '
MMfE
HETH
ETHA
PROP
BUTft
PEHT
PENT
^
MEXM
TIK
8.13
.19
8.2
8.22
8.3
8.39
8.6
8.77
1.
1.15
1.67
2.3
2.65
3.
3.98
4.33
5.51
5.98
6.51
8.85
18.61
12.81
'13.75
16.41
COHC
8
8
8
8
8
8
TOTAL
me
v
v
v
v
v
v
v
v
v
T
V
V
V
V
V
V
V
T
V
V
V
V
MEft
187
16
16
931
913
7851
366
52614
29131 C>
8899
1117
2987
95587
>1529 .
68486 =*
183
26986
68118
227161
88746
797575
Figure 5-3.
Example of GC/FID analysis on IAF ventilation air
gas bag sample for C^-CS speciation.
5-5
-------
in elution time with the increase in field lab temperature. The operator
noted the temperature differential in the field laboratory across a test
day on the Chromatopac. The analysis peak times were adjusted accordingly.
The system used to measure aromatic and higher molecular weight
compounds (termed semi-volatile) was a Shimadzu GC Mini II equipped with
a Shimadzu Chromatopac integrator. The operating parameters were:
Column: 6 ft x 1/8 in. I.D. stainless steel.
Column support: OV-1 on 80/100 Supelco.
Column temperature/program: 25°C/constant.
Sample loop size/temperature: 1 ml/225°C.
~ Carrier gas/flow: He/20 ml/min.
A calibration mixture of 49.8 ppm benzene and 49.9 ppm m-xylene in
nitrogen was used to determine calibration factors and retention times
for these two compounds. Qualitative gaseous standards were prepared
from liquid hexane, heptane and toluene were used to determine the
retention time for these compounds. Figure 5-4 presents an example of a
GC/FID calibration run for C6-C9 speciation. During sample analysis,
hexane, heptane, benzene and toluene were expressed as equivalent benzene
concentrations and C8 and higher components were expressed as m-xylene
equivalent concentrations. Figure 5-5 presents an example of GC/FID
analysis runs for C6-C9 speciation at the IAF sample location.
5.1.2 EPA Method 25A
Procedures similiar to those described in EPA Method 25A (Federal
Register 48 FR 37595) were used to continuously measure the total
hydrocarbon concentration in the gaseous streams tested. A Beckraan
Model 402 flame ionization analyzer was used at the IAF sample locations.
The sample probes were placed near the centroid of the duct to be sampled.
£k
A continuous sample flow was maintained through heated Teflon sampling
lines. The instrument operating parameters were:
5-6
-------
CRL
ftTTEN 8
STflRT 88.16.14.23.
8.01t 8.
8.76
1.21
2.9
STOP
C-R1R
SHPL f
PILE f
KEPT t
METHOD
08
2
246
44
* NRME TIME
1 C1-C3 8.76
1.21
2.9
TOTRL
COHC
8
8
MK
V
V
RRER
5792
8198
8288
22263
Figure 5-4. Example of GC/FID calibration for C6-C9 speciation.
5-7
-------
CA
IHF-3
STBKT 68.16.13.31
8*81
C-R1R
FTLE »
KEPT »
HETHO&
9.49
11.32
13.11
STOM-65
88
2
243
NW1C
3
4
5
6
7
BENZ
HEPT
TOLD
-« XVL
ODXVL
8.87
1.82
1.23
1.37
1.8
2.13
2.62
3.81
3.4
3.83
4.18
3.23
6.39
7.43
9.49
11.32
13.11
14.65
TOTM.
COHC
0
e
8
8
e
HK
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
flREfi
88338
156277
356181
73398
341358
66129
47881
246554
79863
26431
13648
156822
63788
48313
42367
23872
2488
1879
1819139
Figure 5-5.
Example of GC/FID analysis on IAF ventilation air
gas bag sample for C6-C9 speciation.
5-8
-------
Site: IAF ventilation air and carbon drum
Analyzer: Beckman Model 402.
Serial #: 1001303.
Fuel Pressure: 25 PSI.
Sample Pressure: 3.0 PSI.
Air Pressure: 16 PSI.
Sample line length/approximate temperature: 25 feet/ambient.
The analyzers were operated continuously 24-hours per day. The
analyzers were equipped with strip chart recorders for data reduction.
The instruments were calibrated with compressed gas standards of propane
in a balance of air.
The calibration gas standards were supplied by Scott Specialty
Gases and certified to within ±2 percent of the labeled calibration gas
values. The calibration gas standards used at Golden West are, listed
in ppm as propane: 49.9, 100.1, 500.5, 1002.5, and 4010.1.
The initial calibration prior to commencing a test series at a test
location, or follow-up calibration prior to re-commencing a test series
after an instrument shut-down, included the following calibration sequence.
First a trial sampling of the source stream would indicate the appropriate
concentration range for which the instrument would be operated. Second,
the initial calibration of the instrument on this pre-determined scale
included introducing zero gas and the high-level calibration gas separately
to the sample manifold. The output was then adjusted to the appropriate
levels. No instrument adjustments were made after this time. Third, a
periodic response, check was performed by introducing the zero and high
level calibration gas with no adjustments. A response within ±1 percent
of span value was required or recalibration would have been performed.
Fourth, a linearity check was performed on the instrument span range by
introducing mid-level and low-level calibration gases. The difference
between the measurement system responses and the predicted response were
recorded. The differences were assured to be less than five percent of
the respective calibration gas values before the measurement system was
placed on-line for monitoring.
5-9
-------
The operational parameters and calibration gas standards used at
the IAF sample location were as follows:
Instrument: Beckman 402.
Scale: 0-10,000 ppm.
Low-level calibration gas standard: 500.5 ppmv as C3H8.
Mid-level calibration gas standard: 1002.1 ppmv as C3H8.
High-level calibration gas standard: 4010.0 ppmv as C3H8.
A monitor system response time check was performed at the IAF
sample location. The check was performed by introducing the high-level
calibration gas at the inlet to the sample line feeding the measurement
system. The time interval was measured for the analyzer to respond by
95 percent of the calibration gas value. The short sample lines gave
response time of 17 seconds and is within the allowed limit of 30 seconds.
Zero and span drift determinations were made during and after each
test period. The frequency of drift checks were determined by the
operational status of the analyzer and total length of the test. During
the initial operation of the analyzer, after the measurement system had
been powered down, the FIA required frequent drift checks (one to
two hours) for maintaining the drift values below the specified
three percent limit. A complete calibration sequence was completed if a
drift check demonstrated the necessity. After the frequent drift checks
verified the calibration stability of the measurement system, the drift
checks were performed three times during the 12-hour test day period
(0600, 1200, 1700). Test periods of before a 12-hour instrument operation
period required the two-hour drift check frequency.
Figure 5-6 presents an example of a calibration check at the IAF
sampling location with a recalibration required. The sequence was
initiated by introducing zero, high, and mid-calibration gases separately.
The upward drift at the three levels was approximately one percent.
Therefore, the zero and high standards were re-introduced and analyzer
adjustments made. Next, a linearity check is performed with the mid
standard (no adjustment) and the sample reconnected for monitoring.
The calibration gas level reintroduced for the drift check was
determined by the sample measurement levels. The IAF sample locations
5-10
-------
Figure 5-6. Example of a calibration check with
a recalioration required.
5-11
-------
ranged from 6000-7500 ppm and the 4010.0 ppmv as C3H8 was used for the
span drift check.
The continuous monitor data were reduced by determining the average
organic concentration measured into ppmv as propane. Direct computation
of the recorded stripchart outputs was applicable because the high-level
standard was calibrated on the same span value as the recorder. The IAF
measurement system was calibrated on the 0-10,000 ppm scale. Therefore,
the IAF calibration was performed with 40 percent of scale being equivalent
to the 4010 ppmv as propane.
The measured concentrations are presented on a ppmv as propane
equivalent. The one-hour concentration averages were calculated from
direct output readings at five-minute intervals. The average results
were calculated on the hour. Hour periods with drift checks and
calibration were normalized to the hour from the partial segments of the
hour.
5.2 PERMANENT GAS ANALYSIS
A gas chromatograph equipped with a thermal conductivity detector
was used to analyze each bag sample collected for VOC analysis to determine
the nitrogen, oxygen, and carbon dioxide content. This procedure was
intended to characterize the balance gas constituents and is allowed in
Section 1.2 of EPA Method 3 (42 FR 41768) for this purpose.
The chromatograph used was a Shimadzu GC-3BT with a Shimadzu
Chromotopac integrator. The operating parameters were:
Column: 6 ft x 1/8 in. I.D. stainless steel.
Column support: 60/80 molecular sieve.
Column temperature/program: 105°C/constant.
Sample loop size/temperature: 2 ml/35°C.
Carrier gas/pressure: He/3 PSI.
The chromatograph was calibrated with a cylinder standard of Scotty II-Mix
containing (by volume) 14.8 percent C02, 7.07 percent 02, 78.13 percent
N2 with a ±2 percent certification. Figure 5-7 provides an example of
GC/TCD calibration and Figure 5-8 provides an example of a GC/TCD analysis
run for the balance gas constituents in the IAF unit #1 sample.
5-12
-------
CRL
STRRT 98.16.14.93.
1
9.53
2.21
STOP
C-Rlfi
SMPL #
FILE #
KEPT ft
METHOD
*
1
2
3
4
99
4
1597
44
NRHE
RIR
CP-2
0-2
N-2
TIME
9.53
1.1
1.8
2.21
TOTflL
COHC
98.97
14.726
6.9846
75.4922
194.373
MK
RRER
47427
8973
3338
37134
96865
Figure 5-7. Example of GC/TCD calibration for stationary gas analysis.
5-13
-------
IflF-3
STRRT 98.16.13.43.
1
*.*»
STOP
9.53
2.22
SMPL *
FILE #
REPT #
METHOD
1
2
3
4
88
4
1593
44
NRHE
RIR
CP-2
0-2
H-2
TIME
e.53
1.18
1.78
2.22
TOTRL
COHC MK
119.0737
9.9662
IS.3754
72.5523 V
291.9699
RRER
53233
588
18858
35688
99569
Figure 5-8.
Example of GC/TCD analysis on equalization tank #2
gas bag sample for stationary gases.
5-14
-------
5.3 GASEOUS VOLUMETRIC FLOW MEASUREMENT
At the induced air flotation unit vent a modification of EPA Method 2A
(Federal Register.Vol. 48, No. 247, December 22, 1983) was used. The
flow rate at this site was small and the pressure insufficient for
driving a meter recommended by Method 2A. Unsuccessful attempts were
made using a turbine-type meter with a 9000 cubic foot per hour rating.
The system that proved useable was a fabricated meter based on a four-inch
diameter anemometer housed in a section of duct with the same nominal
diameter as the aneometer:
A jewelled anemometer was used at the IAF sample location for
measuring the velocity through a four-inch adaption between the IAF
ventilation air and a pseudo-exhaust (not an ambient exhaust in original
configuration). Figure 4-3 provides a schematic representation of the
velocity measurement system.
The anemometer was calibrated by the manufacturer (Davis Instrument
Mfg.) and the calibration/correction data is provided in Appendix A. No
in-house calibration was performed since this was the first use of the
anemometer.
The operation of the IAF unit was constant in flow rate and direction.
Initial measurements at short time intervals during the test period
exemplified the constant flowrate. Therefore, four to six-hour time
intervals were sufficient in cumulating a total volumetric measurement
over a known time period.
5.4 LIQUID SAMPLE METHODS
Liquid process samples were collected from sample taps used by the
refinery for process quality control. Two types of samples were collected
and were termed "void of air" (VOA) and "composite".
The void of air samples were collected by completely filling a
40 mL bottle with a grab sample. These bottles are fitted with a special
cap to eliminate air bubbles from the sample. The composite samples
were collected by combining three to four equal volume grab samples into
a one gallon amber bottle.
Both sample types were taken from a process stream flowing in a
pipe, through a sample line which was purged prior to sample collection.
The samples were stored on ice in insulated containers after collecting,
5-15
-------
and during shipment to the TRW facility at the Research Triangle Park,
North Carolina for analysis. The bottles were prepared by the following
cleaning procedures:
a) strong soap solution;
b) liberal tap water rinse;
c) nitric acid, 15 percent v/v;
d) distilled water rinse;
e) methanol rinse;
f) methylene chloride rinse; and
g) drying a clean, hot air stream or placing in an oven at 40°C
(140°F).
After the containers have been cleaned, dried and capped, they are
stored in boxes to prevent spurious contamination.
5.5 LIQUID SAMPLE ANALYSIS METHODS
5.5.1 Total Organic Carbon (TOC)
This method is applicable to the measurement of organic carbon in
drinking and surface waters as well as domestic and industrial wastes.
5.5.1.1 Summary of Method. Organic carbon in a sample is converted
to carbon dioxide (C02) by photochemical oxidation. The C02 is measured
to determine the total organic carbon. The sample is initially purged
by vacuum to remove inorganic carbon. Sample inorganic carbon is
eliminated or must be compensated for because it is usually a large part
of the total carbon. The instrument is calibrated versus a standard
solution of potassium hydrogen phthalate (KHP).
5.5.1.2 Interferences/Quality Control. Removal of carbonate and
bicarbonate by acidification and purging with nitrogen or other inert
gas can result in the loss of volatile organic substances. Volatiles
also can be lost if the samples are allowed to heat up.
Repeatability of replicate injections can be effected by non-
homogeneity of samples. This can occur if large carbon containing
particulate matter is not representatively collected in the sample
injection syringe. It is also necessary to collect and maintain the
samples in bottles with no head space so as to minimize the volatilization
5-16
-------
of organic components. This phenomenon is apparent after the TOC analysis
of theoretically identical samples in which one was collected in a VGA
bottle (no head space) and another collected in a larger sample bottle
only half to three-quarters full. Repeatability and representativeness
can be improved by homogenizing (by mixing) the samples prior to analysis.
The precision measurement based upon repeated injection of three
randomly selected samples appears to be a function of the concentration
when measured on the basis of the standard deviation. The standard
deviations in one case for two of the samples cannot be considered to be
equal (at the 95% level of significance), but there appears to be no
difference between the standard deviations when comparing one of the
first two with the third. When compared on the basis of the relative
standard deviation, RSD, (or % RSD), the precision for all three measure-
ments appears to be the same.
The accuracy of the technique is best represented here by injecting
a known volume of the calibration standard and comparing the results to
the theoretical value. In this case, the highest standard used to
calibrate was a 100 mg/L (100 ppm) solution of KHP.
The accuracy measurement is based on an in-house standard and
indicates about a 9% positive bias (or accuracy), based on the mean of
the measurements. However, a statistical hypothesis test that the bias
is zero would be accepted at the 95% level of confidence. Stated
differently there is a 95% probability of being correct if the data does
not show a significant difference from zero.
All samples were diluted as necessary to fall within the limits of
the calibration.
5.5.2 Chemical Oxygen Demand (COD)
This test method is considered an independent measurement of the
organic matter in a sample. The Chemical Oxygen Demand (COD) method
determines the quantity of oxygen required to oxidize the organic matter
in a waste sample, under specific conditions of oxidizing agent,
temperature, and time.
5.5.2.1 Summary of Method. Organic and oxidizable inorganic
substances in the sample are oxidized by potassium dichromate in 50%
sulfuric acid solution at reflux temperature. Silver sulfate is used as
a catalyst and mercuric sulfate is added to remove chloride interference.
5-17
-------
The excess dichromate is titrated with standard ferrous ammonium sulfate,
using orthophenanthroline ferrous complex as an indicator.
5.5.2.2 Interferences/Quality Control. Volatile straight-chain
aliphatic compounds are not oxidized to any appreciable extent. This
limitation occurs partly because volatile organics are present in the
vapor space and do not come in contact with the oxidizing liquid.
Straight-chain aliphatic compounds are oxidized more effectively when
silver sulfate is added as a catalyst. However, silver sulfate reacts
with the halides to produce precipitates that are only oxidized partially.
This can be partially overcome by adding mercuric sulfate to complex the
halides prior to the reflux step.
The replicated chemical oxygen demand readings are given in Table 5-1.
Seven samples were replicated and the means, standard deviations, and
coefficients of variation for the COD readings are given in Columns 4,
6, and 8, respectively in the table. Assuming that the coefficient of
variation of the chemical oxygen demand (COD) readings should remain
constant, the pooled estimate of the coefficient of variation is 0.0435,
or 4.4% and is a good measure of the precision.
5.5.3 Oil and Grease
This method includes the measurement of fluorocarbon-113 extractable
matter from industrial and domestic wastes. It is applicable to the
determination of relatively nonvolatile hydrocarbons, vegetable oils,
animal fats, waxes, soaps, greases and related matter.
5.5.3.1 Summary of Method. The sample is acidified to a low pH
(<2) and serially extracted with fluorocarbon-113 in a separatory funnel.
The solvent is evaporated from the extract and the residue weighed on an
analytical balance.
5.5.3.2 Interferences/Quali ty Control. Fluorocarbon-113 has the
ability to dissolve not only oil and grease but also other organic
substances. No known solvent will selectively dissolve only oil and
grease. Solvent removal results in the loss of short-chain hydrocarbons
and simple aromatics by volatization. Significant portions of petroleum
distillates from gasoline through No. 2 fuel oil are lost in the process.
In addition, heavier residuals of crude oils and heavy fuel oils contain
a significant percentage of residue-type materials that are not soluble
in fluorocarbon-113.
5-18
-------
Table 5-1. REPLICATED COD AND OIL AND GREASE MEASUREMENTS
en
i
COD
TRW Sample # mg/L
4957 2968
3508
4958 4106
4024
4228
4960 2155
2114
4961 1748
1748
4962 1545
1585
1565
4971 1240
1301
4973 1911
1870
0 & G
mg/L
491
535
453
440
441
382
376
133
144
125
94
126
110
109
123
120
Standard
Means Deviation
COD 0 & G COD 0 & G
mg/L mg/L mg/L mg/L
3238 513.0 381.8 31.1
4119 444.7 102.6 7.23
2135 379.0 29.0 4.24
1748 133.5 0.0 0.71
1565 115.0 20.0 18.2
1271 109.5 43.1 0.71
1891 121.5 29.0 2.12
Coefficient
of
Variation
COD 0
0.1179 0.
0.0249 0.
0.0136 0.
0.0000 0.
0.0218 0.
0.0340 0.
0.0153 0.
& G
0606
0163
0112
0053
1582
0065
0175
-------
Replicated oil and grease (0 & G) readings for seven samples are
shown in Table 5-1. Sample means, standard deviations, and coefficients
of variation are shown in Columns 5, 7, and 9, respectively. Pooling
the coefficients of variation for oil and grease gives a precision of
7.9, or almost double the precision of the COD readings.
5.5.4 Total Chromatographable Orgam'cs (TCO)/Hydrocarbon Speciation
This method is applicable for the measurement of hydrocarbons in
surfaces waters, domestic and industrial wastes.
5.5.4.1 Summary of Method. The analysis for TCO was performed by
gas chromatography with flame ionization detection. Component speciation
was done by separation with a fused silica capillary (0.25 mm), GC
column (SPB-1 boiling point column). The reported values are in milli-
grams per liter of sample, and is a total integrated value representing
hydrocarbons ranging between C5 and C30.
For additional breakdown, i.e., hydrocarbon speciation, the resulting
chromotography was broken down into C (toluene) through C30 hydrocarbons.
The values in milligrams per liter were calculated using average response
factors of C7-C1:l, C^-C^ and C17 to C2S hydrocarbons. Due to the
reduced response on a FID of C17 to C2s hydrocarbons as compared to
C7-Cu high values of some C17-C2s compounds were found.
Each sample was prepared by extracting a 500 ml aliquot with methylene
chloride both at an acidic and basic pH, combining the methylene chloride
extracts, and then reducing the solvent to a final volume of 25 ml.
Each sample was spiked with an internal spike to check recovery.
5.5.4.2 Interferences/Quality Control. The sample is serially
extracted with methylene chloride and concentrated to provide sufficient
hydrocarbons for analysis. The concentration step results in the loss
of short-chain hydrocarbons and simple aromatics (BP < 100°C) by
volatilization. In addition, the extraction partition coefficient for
certain compounds does vary. For a measure of extraction efficiency,
each sample and control samples (distilled organic free water) were
spiked with Napthalene-d8 which resulted in recoveries between 75 and
85 percent.
5.5.5 Purge and Trap (Volatile Organic Analysis)
The volatile organics in water were qualitatively identified by
utilizing EPA Method 624 with mass spectral identification. After
5-20
-------
examination of several representative samples, each water sample was
quantitated by purge and trap with GC/FID.
5.5.5.1 Summary of Method. The GC/MS analysis was performed on a
Finnigan 4000 with an INCOS data system. A Tekmar purge and trap apparatus
was used according to EPA Method 624. The GC column used was a 6 ft x 1/8
in stainless steel packed with 0.2% CW 1500 on 60/80 Carbopack C. Oven
conditions were 15°C programmed to 190°C at 10°C/min and held for
25 minutes. A 5 ml aliquot of each sample was taken for analysis and
spiked with 750 ng Bromofluorobenzene (BFB) for an internal standard.
Comparison by identification by GC/MS was done by spectral library
searches and comparison with known standards (Figures 5-9 and 5-10).
Quantitative analysis was obtained by GC/FID (Figures 5-11 and 5-12)
using the same identical chromatography conditions as employed with
GC/MS qualitative analysis runs.
5.5.5.2 Interferences/Quality Control. Contamination can occur
whenever high-level and low-level samples are analyzed sequentially.
When utilizing GC/FID detection only, co-eluting peaks can give a positive
bias to values obtained for the components of interest.
Data quality techniques utilized for these analyses included the
following:
1. A complete page of the system following a high level VOA
sample.
2. Bromoflurobenzene (BFB) was used as an internal standard in
all samples and control standards. In addition, benzene and
toluene were quantitatively based on their respective response
values to BFB.
3. When evidence of co-eluting was detected, values were not
reported for selected compounds.
Table 5-2 gives concentration and quality parameters for an in-house
standard and replicated results for TRW Sample No. 4973. BFB is bromo-
fluorobenzene and was spiked into the in-house standard sample and the
three replicated samples at the same concentration. The accuracy is
estimated as the percent bias the mean of the three BFB readings is from
the in-house standard, and is calculated to be about 52 percent. Precision
is estimated as the pooled coefficient of variation for all the compounds
(including BFB) and is calculated to be 9.6 percent. The sample here
was not filtered before the replicated samples were drawn.
5-21
-------
100.0-1
01
ro
ro
RIC DATA! 83096 II
09/26/83 17i57100 CALIl 6923 14
SAMPLEi TRHI5057UAF-IHH758MG BFB
RAHGEi G 1,1609 LABELS H 8, 4.8 QUANi A 8. 1.8 BASEi U 29, 3
6i3
i TO ieea
200
6(48
Figure 5-9. Mass spectrometer qualitative analysis by purge and trap,
sample no. IAF-INLET-VOA-0740.
23392*
1000 SCAN
33«28 TINE
-------
190.8-1
en
N
CO
RIC
RIC
09/26^83 16I49100
SAMPLEi TRM* 5e66UAF-OUTH730HG BFB
RAHGEt G 1,1000 LABELi H 6. 4.8 OUAHl A 6* 1.8
DATAl 83093 II
CM.Il 0923 14
SCANS i TO ieee
I U 28, 3
93 138
164869
260
6:49
400
13l 28
608
20 tee
888
26i49
1808 SCW
33120 TI«
Figure 5-10. Mass spectrometer qualitative analysis by purge and trap»
sample no. IAF-OUT-VOA-0740.
-------
ro
c
u
w
M
Ct .
VI PI
Mil"
-------
en
r\j
in
\
E
o
K
ui
a
IV III
T t-
IWXU6JOO
I. .3.
Figure 5-12. GC/FID quantitative analysis by purge and trap, sample no. IAF-OUT-VOA-0740.
-------
Table 5-2. GC/FID READINGS FOR ACCURACY/PRECISION ESTIMATES
TRW Sample No. 4973
Compound
C2H6S2
C6H6
C6H5CH3
BFB
In-house
Standard
ppb
-
352
348
596
Replication No.
1
ppb
240
187
502
863
2
ppb
227
174
519
927
3
ppb
198
142
441
927
Means
ppb
221.7
167.7
487.3
905.7
Std. dev.
ppb
21.5
23.1
41.0
37.0
CV
0.0970
0.1381
0.0842
0. 0408
% Precision = pooled CV for compounds in Sample No. 4973 = 9.6%.
5-26
-------
Table 5-3 gives GC/FID data for an induced air flotation (IAF)
sample and a dissolved air flotation sample. These samples were filtered
before analysis. Accuracy estimates for IAF and OAF, respectively are
9.8 and 19.3 percent. The precision is 29.3 and 3.7 percent, respectively.
In view of the fact that only duplicate analyses were performed, the
precision figures for the filtered samples appears not to be significantly
different (29.3 and 3.7 percent) from those for the unfiltered sample
(9.6 percent). The accuracy for the filtered samples (9.8 and
19.3 percent) appear to be significantly better than the accuracy of the
unfiltered sample (52 percent). It appears that the solid material in
the unfiltered matrix decreased the accuracy possible in the analysis.
5-27
-------
Table 5-3. PRECISION/ACCURACY ESTIMATES FOR IAF/DAF SAMPLES
IAF, TRW #4987 DAF, TRW #4994
Compound
C6H2S2, ppb
C6H6, ppb
C4H10S2, ppb
C6H6CH3, ppb
BFB, counts
For IAF:
Standard 1
939
1970
411
5710
170417 143078
170417 - ((143078 +
2
943
1770
410
5020
164324
164324)72)
CV 1
0.0030
0.3860 2120
0.0017
0.0909 2110
0.5370 135529
v inn - Q a*
2 CV
1980 0.0483
2000 0.0379
139579 0.0208
170417
For DAF:
Accuracy = 170417 - ((135529+ 139579)72)
Precision:
Pooled CV for IAF = + 29.8%.
Pooled CV for DAF = + 3.7%.
= ig 3%
5-28
-------
APPENDIX A
SAMPLE CALCULATIONS AND RESULTS
t Flow and Emission Rate Calculation
Examples
Summary Gas Analysis Sheets
t Continuous Monitor Results
-------
SUMMARY GAS ANALYSIS SHEETS
-------
APPENDIX A
EXAMPLE CALCULATIONS
Example #1 IAF - Flow Measurement with Vane Anemometers
Ftan 9
Van (CFM) = -4H X Area Fr
an mi n an
V__ X 17.64 X PL
(SCFH) .
(Example of flow measurement calculation during IAF run on 8/17/83)
Van Run 8-17 (CFM) = X .0873 ft2
= 27.5 CFMan
Krnvn - r27-5 x 17-64 x
(SCFM) - ( U7 + 46Q
= 25.0 SCFM
SCFM = standard cubic feet per minute
V = volume measured through vane anemometer
an
V = vqlume standardized to standard temperature and pressure
P. = barometric pressure
T = temperature of stack gas
-------
Example #2 Mass Emission Rate for VOC as
(A) Sample calculation to provide the conversion factor
of CH from ppm to mg/m3
C3H8~
(^M) (
x mole ' '
3
106ppm
1 mole \
' 25.71 L ;
, 28.32 L * , 35.31 ft0 >
* 3 ' * 3 '
ftJ fn"3
/ 1000 mg
1 -ig
= 1.71 mg/m3
(B) Emission rate = Ib/hr
~nr~ \ f 1.71 mq \/ m \/s \/60min
.ppm ) ( 3^ ) ( ^ ) ( . ) ( -j
mj 35.31 ftj mln nr
1000"
... Ib
Example - of Emission Rate calculation on IAF 8/17/83 run at 0900
3
r - / -TOO? ««m \ f 1.71 mg \ / m % / 25.0 ft \ / 60 min
EVOC ( 7992 ppm ' ( 3~~^ ' ( 3 ' ( min ) ( hr
VUL mJ 35.31 ftj mn nr
v 1000 mg ; x 453.6 g
= 1.28 Ibs/hr
-------
Davis Anemometer Correction Chart
C»VH iHTnuum mn. eo, «c.
CAUtHATIOH CQHfilCTIOH CHAUT
EftUt. NO
June If, 1?83
TY« lALLKAMWO
TRUE
MJ».
so
so
70
«0
100
too
100
400
KO
MO
TOO
00
00
1000
1200
1*00
1*00
IIDfCATfD
tut.
II
M
S3
- n
IS
1*0
3*0
400
SOS
*IO
TIS
120
«7S
1030
ins
1*41
I»SS
TRUE
ft*.
1*00
zooo
2200
2400
2*00
2*00
1000
3200
3400
3*00
3100
4000
4200
4400
4*00
4*00
MOO
mOICATEO
ftM.
IMO
20*5 '-
227S
24*0
2700
2*10
3120
SS3S
SJSO
37*1
W73
41M
43*0
4S*S
4*00
W2S
12*0
-------
WORK SHEET
-------
WORK SHEET
/ .
UL
JtdL
73
^773
36/1
fe//?
-Asa.
-------
WORK SHEET
I "feU'lpy"MST*
J
-7137
2.
.of
A3
//>?
100 /?
0-X
R//-T
//SI,
-------
"VWIRONMENTAL ENGINEERING DIVISION
SUMMARY GAS ANALYSIS
COMPONENT RUN
C-l
IM.-X
C-2
32,7
C-3
u/i
C 4
B
ZENE
IS"/
TC.UENE
!?».
LENE
d/d
to
AL
HC
% C02
% CO
N?
% 0?
% CH4
TOTAL %
-------
TRW
tWmONt.lENJAt ENGINEERING DIVISION
SUMMARY GAS ANALYSIS
COMPONENT RUN
C-l
UoS"
6- A
C-2
UK
C-3
3 if
or?
S S
BE^ENE
TOLUENE
UK
Sv-J
m(,
2
XyiENE UK'
,5-V
1%fcc
TOTAL
HC
tj/
%M
% C02
% CO
2 N?
% 02
% CHfl
TOTAL %
-------
ENVIRONMENTAL ENGINEERING DIVISION
SUMMARY GAS ANALYSIS _
COMPONENT RUN
.Li.
C-2
C-3
JZaL
H-X
^4
CM
5-6^
BENZENE
TOLUENE l/X
3y
U/i
XLENE
7
WAL
iibi A. -
%M
% C02
% CO
_N2_
% 02
% CH4
TOTAL %
-------
TRS&
£NVIRONM£NTAL ENGINEERING DIVISION
SUMMARY GAS ANALYSIS
. COMPONENT RUN
C-l
C-2
Uli.
C-3
UK.
rot-
1*1
$
'«. /
BEZENE
TOlUENE
XY1ENE
/2-b
T(TAL
S5M
* C02
CO
N?
% 0?
% CHa
TOTAL %
2-1
-------
WVIRONMENTAL ENGINEERING DIVISION
SUMMARY GAS ANALYSIS
. COMPONENT RUN
C-l
C-2
BE
ZENE
TOLUENE
X^LENE C-T
f
TOTAL
HC
XM
% C02
% CO
% N2
% 02
% CH4
TOTAL %
34.1
o
40,7
n<>t>
2.5
it *-
M/i
2.S55
/1 3
Oil
-------
COMPONENT RUN
C-l
ENVIRONMENTAL ENGINEERING DIVISION
SUMMARY GAS ANALYSIS
f Z
CJ3
s
l/kl
C-6
BET
JZENE
22 sy-
-------
'mats?
iNVlRONMZNTAL ENGINEERING DIVISION
SUMMARY GAS ANALYSIS
COMPONENT RUN
C-l
C-2
*/./
W/.7
C-3
37/7
2,3
BENZENE
i
TOlUENE
U/i.
, 7
5
U>L
XYZENE C
-------
fNVIRONMENTAL ENGINEERING DIVISION
SUMMARY GAS ANALYSIS
-- J
COMPONENT RUN
C-1
C-2
Act
3.0
CG too/ -
C-3
C/5
~C/6
«/' -
4-3*'
BENZENE «iu:
230
ToluENE
n-b'
X^
ENE
-S/S
(ilL
TOTAL
% C02
o.-z'i
CO
#-
N?
% 0?
% CH4
TOTAL %
-------
ENVIRONMENTAL ENGINEERING DIVISION
SUMMARY GAS ANALYSIS
COMPONENT RUN
C-l
67,8
zn
C-2
^LL
', 3
C-3
8, <
C-A
-7-21
mi.
bU-
»o3
T0LUENE «»<
/ if
TOTAL
5SC02
% CO
% N?
02
% CHa
TOTAL %
-------
fNVIRONfMNTAL tNCINEERINC DIVISION
SUMMARY GAS ANALYSIS
8
. COMPONENT RUN
C-l
.2£j
C-2
-},(,
/-3..0
C-3
11, ?
C/6
BENZENE
UENE
/'Si
57, «
/
7?.")
XYLENE
'' 3?
2,3V' 3S3
S.r -
TOTAL
HC
55M
CO?
. 3 «./
* CO
% N?
% 02
% cm
TOTAL %
-------
CONTINUOUS MONITOR RESULTS
-------
TRW
LOCATION
POLLUTANT
INSTRUMENT RANGE (PPM)/?
Record Data Every 3-5 Minutes
Time
/ooo
t Scale
Readi ng
^6,75
6/oQ
]/Q
DATE
CALIBRATED BY
Time
/ItoO
^000
Scale
Reading
A-o
ppm-
NOTES
-------
TRW
LOCATION &wvw fA/ei>7
POLLUTANT
DATE
INSTRUMENT RANGE (PPM) £> -
Record Data Every 3-5 Minutes
CALIBRATED BY
Time
o
}oo&
Time
I f
Scale
Reading
tb I
TO-/ 7
s
ppm-
NOTES:
-------
TRW
LOCATION £0*^ ^Lr TAF D^^ POLLUTANT ]/oc
DATE
INSTRUMENT RANGE (PPM) p ^
Record Data Every 3-5 Minutes
JO
Time
C?
Scale
Reading
_EEH_
^SO?
CALIBRATED BY
Time
Scale
Readi ng
ppm-
NOTES:
-------
TRW
LOCATION
POLLUTANT 1/0 o
ppm-
~>\, 50
O
£630
Time
^60
0
as oo
1 ooo
/toO
I1OO
Scale
Reading
60. 9o
60
PPttT
636O
62OO
/O
NOTES:
-------
APPENDIX B
FIELD DATA SHEETS
-------
IAF Anemometer Measurements
-------
TRW
LOCATION
POLLUTANT
DATE
INSTRUMENT RANGE (PPM)
Record Data Every 3-5 Minutes
CALIBRATED BY
Time
Reading
/ ^
DOG
/( I
<<
Time
Scale
Reading
ppm-
NOTES:
-------
PIANT (j>Mt»lJ l*\C
DATE ?//*K?
LOCATION ' T^H*-"
STACK I.D.
BAROMETRIC PRESSURE, in Hj
STACK GAUGE PRE
OPERATORS _DJ
SSURE. in. H20
S'^/\v/'j/»
ftfcij...- "nl^_
TRAVhriSt
POINT
NUMBER
a$eo =
Go oo
IgOoQ
9^000
S 3>sxo a
7 |H6 0
^s^o
^6,66)0
I'goo o
AVERAGE
VELOCITY
HEAD
Ups), in-HjO
~~~?v 't57vT' '
F ('^''"^ / * O ^3
(I'/O'-HS
/l-3
K?
[9&
IQ&
in
;,^
EPA (Dun 233
472
SCHEMATIC OF TRAVERSE POINT LAYOUT
TRAVERSE
POINT
NUMBER
.
i
AVERAGE
VELOCITY
HEAD
(Aps),in.H20
-
STACK
TEMPERATURE
-------
HATF fr//?/^
| prflTION .-t*Vp
STACK I.D.
BAROMETRIC PRESSURE, in Hf>
STACK GAUGEPRE
OPERATORS!!^
5SURE. in H70
> f z
i/li///7
-fW/X ~fi~>~
POINT
NUMBER
QOna
WOO
/ C 00 o
3 O"\0 0
n v
IPd
190
I9.fi
"1
//?
7/5^
I/ <^
//*?
/n
1!^
UH
^\
^
-* 4
3v-\- J'
v
EPA (Out) 233 >.
472
SCHEMATIC OF TRAVERSE POINT LAYOUT
TRAVERSE
POINT
NUMBER
AVERAGE
VELOCITY
HEAD
(Aps), in.H20
STACK
TEMPERATURE
(Ts). °F
-------
PRELIMINARY VELOCITY
?IANT
LOCATION
STACK I.D. 1
BAROMETRIC PRESSURE, in. Hj_
STACK GAUGE PRESSURE, in. H,0
D,T) p l
flueJ6 J/)
lAlp -£>^-f
f*
TRAVER
POINT
NUMBER
~Y7oo
?/ (+00
67 O
AVERAGE
EPA (Durl 233
472
HEAU
tip.*.
rn-A?.^
7
7
T^k
7 53
06
SCHEMATIC OF TRAVERSE POINT LAYOUT
STACK
TEMPERATURE
(Ts), -F
33
Or
TRAVERSE
POINT
NUMBER
DOO o
AVERAGE
VELOCITY
HEAD
(Aps), in.H20
: oo
STACK
TEMPERATURE
(Ts). CF
-------
Liquid Sampling Log
-------
WORK SHEET
A*
^ ' r
7:35-
/n't,
\f-2f\
y
70
S77VCT
10
OOt*
S' Shu /)&
STOf?
-------
WORK SHEET
Y
V//V
Ml
/*>'/ u
/ .>/
fe-
7 /I C ".
/C V 0
j-£/)/L
-------
APPENDIX C
ANALYTICAL DATA
Gas Chromatograph Worksheet
Continuous Monitor Example
t GC/FID Examples of IAF #3
Analysis on 8/16/83
-------
GC WORKSHEETS
-------
COLUMN:
. 6C WORKSHEET
RUN* NUMBER! T/VrT*- -/
COMPOUND
RETENTION TIME
IN CM.
COUNTS
SEAN
ATTENTION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTRATION AS
BENZENE
7-0
o. t.
/C.I
Cu
r.//
c.f
G .6cO C.
C>.o
6 00"? ^
LUENi
J.-jfc>
*,<}>$!
o . oo JT
XYL
1X79
if
TOTAL
HYDRO-
CARBONS
(iTHC)
ENVIRONMENTAL ENGINEERING DIVISION
-------
GC WORKSHEET
COLUMN:
RUN NUMBER:
DATE;
COMPOUND
RETENTION TIME
IN CM.
COUNTS
SPAN
ATTENUATION
DILUTION FACTOR
(Diluted w/N)
CONCENTRATION AS
COMPOUND
CONCENTEATfON AS
3)3
O ,
i.t
3 ^ 3 3*7
1"4"
ULlL-
X-HS
3-
^ ?, s-
«) S^
321
3x5
TO
.UEND
XYllENE
ir-1-7
7.7?
/ * 7/7
I0-*tf
."3
TOTAL
HYDRO-
CARBONS
ClTHC)
CNVIRONMENTAL
-------
11
COLUMN:
. GC WORKSHEET
RUN NUMBER: 14-F --«-
DATE:
RETENTION TIME
IN CM.
COUNTS
ATTENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTRATION AS
0-0/65
c , o Q^>
no-SS"
'0
!,,/<
95-
/o
. -*'//
O . CO
a c ?
ENVIRONMENTAL ENGINEERING DIVISION
-------
COLUMN;
GC WORKSHEET
RUN NUMBER:_jT,*-e~
DATE:
COMPOUND
RETENTION TIME
IN CM.
COUNTS
SPAN
ATTENUATION
DILUTION FACTOR
(Diluted w/N)
CONCENTRATION AS
COMPOUND
CONCENTR
a
A.
AS
M
r
37
ENZENE
LUENE
LENE
I3SS9
/V5
V/
TAL
DRO-
\RBONS
HC)
ENVIRONMENTAL ENGINEERING DIVISION
-------
GC WORKSHEET
COLUMN:
-I
RUN NUMBER:
COMPOUND
RETENTION TIME
IN CM.
COUNTS
SPAN
ATTENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTR^HON AS
673'f
O.0074
7' 3
7o 5V
BlNZENi-
/.-fee
130-
i,
HI"?
CC.
o 003-?
6 /«*
r
TOTAL
HYDRO-
CARBONS
(iTHC)
837/6-
ENVIRONMENTAL £NGlN££fVNG DIVISION
-------
COLUMN:
r .
-
GC WORKSHEET
'J
RUN NUMBER;
DATE:
COMPOUND
RETENTION TIME
IN CM.
COUNTS
ATTENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTRATION AS
_^-^N?ENr
!
"
-r// 3-0* .
O.crt
o , c-t
3.8*
i ».'/
10 >7
6.S3&
TOl
HYDRO-
CARBONS
CiTHd)
ENVIRONMENTAL ENGINEERING DIVISION
-------
GC WORKSHEET
COLUMN;
RUN NUMBER:
DATE:
COMPOUND
RETENTION TIME
IN CM.
COUNTS
SPAN
ATTENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTRAWON AS
7S-/
9. «
8945
'<-//
0.0 6
0.0^3
TOUENE?
1011-i,
Cfe
f 3-
3/4,
TOT
HYDRO-
CARfeONS
ClTHl)
X C?(* -
ENVIRONMENTAL ENGINEERING DIVISION
-------
U>5
. -At i
GC WORKSHEET
COLUMN:
NUMBER:
DATE:
COMPOUND
RETENTION TIME
IN CM.
COUNTS
SPAN
ATTENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTRATION AS
BENZENE
-<**.
i.oY
a
ISO
i i
Wt
I.V-
N
as?
1 1
BENZEN£Z
3V
TLUENE
.m
9 oo
XY^ENE
US
itn 4m, LLII t o.oc'/te
130
TOL
HYDRb-
CAREONS
(|THC)
SVS'J
./of
.90
TRW
ENVIRONMENTAL ENGINEERING DIVISION
-------
GC WORKSHEET
COLUMN:
RUN NUMBER:
DATE:
COMPOUND
RETENTION TIME
IN CM.
COUNTS
SPAN
ATTENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTRAHON AS
&*
rz.
{it,
'7.7
o, otcx
o. oe>
c/%
( 1
0.661**}
0.3
3H.,?
i i
it
JO
. o o
71.3
VS.
Lf-
TOUENE
7(o
o.ooll
i.OJ
3s", l ?S/t
C-Hl
/s*
TOTAl
HYDRO-
CARBONS
(iTHC)
VJ1X77
7 /
^ -j ?
6*<
23
CNV/RONMENTAL ENGINEERING DIVISION
-------
-fit/jut **-
GC WORKSHEET
COLUMN:
V-
RUN NUMBER:
DATE:
COMPOUND
RETENTION TIME
IN CM.
COUNTS
SPAN
ATTENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTRATION AS
BENZENE
'.i
US'/
Ci
ill 9S61
l5
II
A.Ur
'3*?-?
ll
4
BNZENE
o. c. o «yc
o.oo^/d
TOUENE
M.MS
CM "5
4 ."
3J7
TOTAL
HYDRO-
CARBONS
(|THC)
lo
tl
f
CNVIRONMENTAL ENGINEERING DIVISION
-------
GC WORKSHEET
COLUMN:
RUN NUMBER:
DATE;
v.y
c<.
COMPOUND
C1
Jf C^
6 u^
d CK
^ ^
c]^u"
_/ "t
V^ Ll^i
ToluEf^
XYLENE'**
TOTAL
HYDRO-
CARBONS
ClTHC)
* .
RETENTION TIME
IN CM.
oV .
0,H
o.-fi
M1
I /?<»
A -V
** noast
^l . -^k/ r> ^ ^.j
^x/t* (JtoS: ^ j->**-
COUNTS
1^*5 oo
lZv«5S
-70 yt,
-,/wt
S?5\?V
^fe^-
^
^63PVJ
V^ ^ ^^?
8'^(t tJ/
'J'O iklt)
3)1-Z'O
SPAN
ATTENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
1<-^
/AX
^*'?/79
3^-T
f C& 'v
/ O ^*y jb*
14/y
3 *v y
O "i 4
/$ 3
f^t^
t°5/
*a*fr
CONCENTRATION AS
BeNZENE
^ ^ C*/ "^
O / C* 0 4? 7
ci-* f))re>1v$
V
0,ooS/
^A^^
"
o, i?c»>-v3
< i
< i
o.'oo-bt
(>3 f3siff>tf-*S
I,
il
-
ENVIRONMENTAL ENGINEERING DIVISION
-------
o;
GC WORKSHEET
COLUMN:
RUN NUMBER:
DATE:
COMPOUND
RETENTION TIME
IN CM.
COUNTS
SPAN
AHENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTRAHON AS
U'l
tf.oo.sr5~
UK-
roi
I.S7
I-'SI
-------
GC WORKSHEET
COLUMN:
RUN NUMBER:
DATE:
COMPOUND
RETENTION TIME
IN CM.
COUNTS
SPAN
ATTENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTRAJWN AS
306,
6,00
/ u
TOUENE
XYI1ENE
/e>/7
TOTAL
HYDRO-
CARBONS
(|THC)
ENVIRONMENTAL ENGINEERING DIVISION
-------
-"2-
GC WORKSHEET
COLUMN:
RUN NUMBER:
DATE:
COMPOUND
RETENTION TIME
IN CM.
COUNTS
ATTENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTRATION AS
BENZENE
7o A7
23.7
1.*
/33
. to?
^.5-7 6 3 j>
c.tfimyy o.oony
3 3
/90>5
TOTAL
HYDRO-
CARBONS
ClTHC)
c.// fa .%t>
£NVWONM£NTAL ENGINEERING DIVISION
-------
GC WORKSHEET
cr
*
COLUMN: <* !*<<"' 'll *< RUN NUMBER: IH-F-7- DATE: S-I8-W
COMPOUND
C1
C2
C3
% UK
L. UK
c6 ) o/
BSdzEfff
TOLjbENf
vv/C r»if ^^
AiuhNh
) U/^-
C u/C
k^
TOTAL
HYDRO-
CARBONS
(ITHC)
RETENTION TIME
IN CM.
t,v\
6.V
6-^<
«.«»/
liH
/3*
/. 8 A
^S(J"
1^
*^ * y J
0 A S" 7*7
Jo^
SPAN
*
ATTENUATION
';
DILUTION FACTOR
(Diluted w/N2)
*
*
CONCENTRATION AS
COMPOUND
^.-7
V-/
.*,£>
^0
3^0
%. r
// y
77. 0
^* V
/ 5| "^
^. t
CONCENTMWeiTAS
&BT2ENE
0 , 012-7
o, oo
-------
GC WORKSHEET
COLUMN:
RUN NUMBER;
DATE: *-»*-*>
COMPOUND
<51 W6
f
4 WT.
ft w«- '
% ro>
IT u/^
7 *l
BENZENE
TOLUENE
XVlENE
XYA.ENE
1
TOTAL
HYDRO-
CARBONS
ClTHC)
RETENTION TIME
IN CM.
l.oC .
Mb
\ ,VI
.7-7
a*t
I.'!?
LSI
1;«
l^iv
I'.Vfc
/^sl
COUNTS
CJ^SS?
. tt (L (L^
y* o "^> (* ^5
H,n>
ioS~9 !>^
t/Xt)<^o
3 ^C'^f
7?Ji*
'Jf*r
io <><;?
s^ieS'
7U-S ^
SPAN
AHENUATION
'; '
DILUTION FACTOR
(Diluted w/Ng)
;
CONCENTRATION AS
COMPOUND
7.3$
81-V
.1,1^
xa V
/*6<
/jt
/'^
^
112
t&Z.
2.ci>
«y/»7
//6
CONCENTRAHON AS
BCNZENE
1-^iaAu. utv-t
-------
GC WORKSHEET
COLUMN:
RUN NUMBER:
DATE:
COMPOUND
RETENTION TIME
IN CM.
COUNTS
JSWtfl
ATTENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTRA
a
/a.
AS
7,3
6 . 00*76-
SrV
3r\y> 'iiPtur /uj
o.oo-t
-irr*/
/ //
BEZENE
00,3
TOLENE
XYLE^E
7J.J
>H>
il
TOTAL
HYDRO-
CARBONS
C.THC)
ENVIRONMENTAL ENGINEERING DIVISION
-------
GC WORKSHEET
COLUMN:
RUN NUMBER:
DATE:
COMPOUND
RETENTION TIME
IN CM.
COUNTS
SPAN
ATTENUATION
DILUTION FACTOR
(Diluted w/N)
CONCENTRATION AS
COMPOUND
n.
AS
H+o /Co
ho''
am
f7'3
46375"
in
u
3-U'ir
Mil
ll
3.57
Or
J.tot
57.3
TOTAL
HYDRO-
CARBONS
(iTHC)
**-**
ENVIRONMENTAL ENGINC£RING DIVISION
-------
GC WORKSHEET
COLUMN:
NUMBER;
DATE:
COMPOUND
Cl
C2
C3
r, <«< '
T4 o<^
Si f
/ *'<-
fyj u»i
BENZENE
TOLUENE
XJIENE
c<,,
TOTAL
HYDRO-
CARBONS
(iTHC)
RETENTION TIME
IN CM.
6,T-°I .
6-^'
6,(e^
0.^7
i.T-b
| 4/7
i-v;
^v
%->>
5"*»3
.V/s S"
^. ^
9.i»-
/o-a^ ,6^-»
;^.is
A*^ '3-y7
HAIL, "*''***
ILT^:
COUNTS
-Siaib
fcZ^
t
w-
±i>
c,?~>1
rtb~>t>i
*<**>&
S7t>9
&$&'
s^v
SPAN
trsd'
ISO
/S?*-
rr?s
q^r«v
//<-T?
«»?
^»X«f
/S9u7
C'/C?
;S$.5T
Ib^W
5H11?-
5W)
^(^L-
'^0^
ATTENUATION
'_
DILUTION FACTOR
(Diluted w/N2)
*
CONCENTRATION AS
COMPOUND
*7/«7 7f/t>
^.o 7.6,
f / f //<- 9
0. 1 *A. t-
/a.-S Z-j-V"
V^ r^,b
^' r 3- M-
/6S /T^
"?"7'"> S-o.^
v/./ 3 1
y.y~
/. >,
V3.5 />c
7b^ <£-t7
/9j,->. li^
it- sT z-/, ^
*vx
37-^ 7C.V-
CONCENTRAHON AS
BENZENE
/^
6,0/^~>
0,0 o9^
o-t>°t>3
CJLJ (2x«)r7£^cg_
'< ^
o4j>,^ej)>^*1t'
«*
o.ooV"1-
Ca* />l-c/)<**~r
tt
**?i}rqfio*st
i
(
0 00 J
i
-.
CNVIRONMENTAL ENGINEERING DIVISION
-------
COLUMN;
GC WORKSHEET
NUMBER; T *-r-~
DATE;
COMPOUND
RETENTION TIME
IN CM.
COUNTS
SPAN
ATTENUATION
DILUTION FACTOR
(Diluted w/N2)
CONCENTRATION AS
COMPOUND
CONCENTRAJMN AS
BEWZtNE
t 005-1,
.11
//7
1.85
M
m-MI
*c - *H
Of 2.13
BENZENE
O,
T(LUENE
5-.M
// V // f
XYLENE
97-2.
CARBONS
CiTHC)
ENVIRONMENTAL ENGINEERING DIVISION
-------
CftL
STflR-T 88.16.07.2?.
3.18
7.05
8.31
9.35
9.95
STOP
C-R1R
SMPL ft
FILE ft
REPT ft
METHOD
1
2
88
7
118
44
NfiME
METH
ETHfl
TIME
0.17
8.29
0.39
0.63
1.31
2.
3.
7.
78
18
65
31
8
9.35
9.95
TOTflL
CONC
8
6
MK
V
V
V
V
V
V
T
T
8
flREft
43
11 &7
1362
1955
2652
27
3443
232
4556
25
94
15560
Example of GC/FID Calibration for C.-Cg Speciation
-------
Example of Continuous Monitor Stripchart With a Calibration Sequence:
IAF - Outlet on Test Day 8/15/83
-------
IAf-3
START tB.lt.13.33.
13.75
STOP
C-R1A
SMPL t
FILE
REPT
HETHOD
ee
7
127
44
NAME
HETH
ETHfl
PROP
BUTA
PEHT
PENT
HCXfl
TIME
e.i3
9.19
9.2
8.22
8.3
8.39
6.6
8.77
1.
1.15
1.67
2.3
2.65
3.
3.98
4.33
5.51
5.98
6.51
8.65
10.61
12.91
13.75
16.41
CONC
TOTW.
e
e
HK
V
V
V
V
V
V
V
V
V
T
V
V
V
V
V
V
V
T
V
V
V
V
AREA
167
16
16
17
6734
931
913
7851
19822- CM
366
52614
29131 C$
8899
1117
2987
95587
91529 ,
68486 '~-c->
183
26986
68118
227161
88746
797575
Example of GC/FID Analysis on IAF #3
Gas Bag Sample for C-C Speciation
-------
CRL
flTTEH 0
STRRT 08.16.14.23.
0.01 s 0.1
0.76
1.21
2.9
STOP
C-R1R
5«PL f 00
FILE f 2
PERT t 246
METHOD 44
* NRNE TIME COHC MX flREfl
1 C1-C3 0.76 0 V 5792
1.21 V 8198
2.9 8280
TOTRL 0 22263
Example of 6C/FID Calibration for Cg-Cg Speciation
-------
CR
TRF-3
STRRT 88.16.13.31.
C-Rlfl
"MPL t
FILE »
REPT t
J1ETHOD
9.49
11.32
13.11
STOM-65
89
2
243
44
«
3
4
5
6
7
NRttC
BENZ
HEPT
TOLU
-M XVL
ODXVL
TIME
8.87
1.82
1.25
1.57
1.8
2.15
2.62
3.81
3.4
3.83
4.18
5.23
6.39
7.43
9.49
11.32
13.11
14.65
TOTBL
3.81
CONC
8
8
8
8
UK
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
RREfl
88538
156277 K<*
356181
73398
341358 -in
66129
47881
246554 »-
79865 -
2643)
13648
156822
63788
48513
42567
23872
2488
1879
1819139
Example of GC/FID Analysis on IAF #3
Gas Bag Sample for Cg-Cg Speciation
-------
CBL
STflRT 98.16.14.03.
0.53
2.21
STOP
C-Rlfl
SMPL #
FILE #
KEPT «
HETHOD
*
1
2
3
4
00
4
1597
44
NfiHE
RIR
CP-2
0-2
N-2
TIKE
8.53
1.
1,
2.
1
8
21
TOTftL
CONC
98.97
14.726
6.0846
75.4922
194.373
MK
RREfl
47427
8973
3330
37134
96865
Example of GC/TCD Calibration for Stationary Gas Analysis
-------
IflF-3
STftRT 98.16.13.43.
STOP
9.53
2.22
C-Rlfl
SMPL *
FILE t»
REPT *
METHOD
*
1
2
3
4
08
4
1595
44
HflHE
RIR
CP-2
0-2
N-2
TIME
6.53
,18
,78
1.
1.
2.
22
TOTRL
CONC MK
119.8757
8.9662
18.3754
72.5525 V
281.9699
RREft
53233
588
1B858
35688
99569
Example of GC/TCD Analysis on IAF #3
Gas Bag Sample for Stationary Gases
-------
APPENDIX D
SAMPLING METHODS AND ANALYTICAL TECHNIQUE
-------
503 OIL AND GREASE
In the determination of oil and grease.
an absolute quantity of a specific sub-
stance is not measured. Rather, groups of
substance* with similar physical charac-
teristics are determined quantitatively on
the basis of their common solubility in tri-
chlorotrifluoroethane. "Oil and grease" is
an> material recovered as a substance sol-
uble in trichlorotrifluoroethane. It in-
cludes other material extracted by the
solvent from an acidified sample (such as
sulfur compounds, certain organic dyes.
and chlorophyll) and not volatilized during
the test. It is important that this limitation
be understood clearly. Unlike some con-
stituents that represent distinct chemical
elements, ions, compounds, or groups of
compounds, oils and greases are defined
by the method used for their determina-
tion.
The methods presented here are suit-
able for biological lipids and mineral hy-
drocarbons. They also may be suitable for
most industrial wastewaters or treated ef-
Huents containing these materials, al-
though sample complexity may result in
cither low or high results because of lack
of analytical specificity. The method is not
applicable to measurement of low-boiling
fractions that volatilize at temperatures
below 70 C.
1. Significance
Certain constituents measured by the oil
and grease analysis may influence waste-
water treatment systems. If present in ex-
cessive amounts, they may interfere with
aerobic and anaerobic biological process
es and lead to decreased wastewater treat-
ment efficiency. When discharged in
W'astewater or treated effluents, they ma\
cause surface films and shoreline deport-
leading to environmental degradation.
A knowledge of the quantity of oil and
grease present is helpful in proper desigr.
and operation of wastewater treatmen;
systems and also may call attention to cer
tain treatment difficulties.
2. Selection of Method
For liquid samples, three methods arc
presented: the partition-gravimetric meth
od (A), the partition-infrared methoJ
(B), and the Soxhlet method (C). Meth
od B is designed for samples that migh:
contain volatile hydrocarbons that other
wise would be lost-in the solvent remo\j
operations of the gravimetric procedure
Method C is the method of choice wher
relatively polar, heavy petroleum fra,
tions are present, or when the Ievel> ^'
nonvolatile greases may challenge the MV
ubility limit of the solvent. For low level-
of oil and grease (<10 mg'L). Method BI-
the method of choice because gravimetr-
methods do not provide the needed preci-
sion.
Method D is a modification of the Sox
hlet Method and is suitable for sludge* an.:
similar materials. Method E can be used i'
-------
OH ft GREASE/Partition-Gravimetric Method
461
conjunction with Methods A. B. C, or D to
obtain a hydrocarbon measurement in ad-
dition to. or instead of. the oil and grease
measurement. This method separates hy-
drocarbons from the total oil and grease
on the basis of polarity.
3. Sampling and Storage
Collect a representative sample in a
wide-mouth glass bottle that has been
rinsed with the solvent to remove any de-
tergent film, and acidify in the sample
bottle. Collect a separate sample for an oiL
and grease determination and do not
divide in the laboratory. When informa-
fiorTis rcquTrebTabout average grease con-
centration over an extended period, exam-
ine individual portions collected at
prescribed time intervals to eliminate loss-
es of grease on sampling equipment during
collection of a composite sample.
In sampling sludges, take every possible
precaution to obtain a representative
sample. When analysis cannot be made
immediately, preserve samples withlmL
cone HCI/80 g sample. Never preserve
samples wiin cHl_l3 or sodium benzoate.
503 A. Partition-Gravimetric Method
1. General Discussion
a. Principle: Dissolved or emulsified oil
and grease is extracted from water by in-
timate contact with trichlorotrifluoro-
ethane. Some extractables, especially
unsaturated fats and fatty acids, oxidize
readily; hence, special precautions regard-
ing temperature and solvent vapor dis-
placement are included to minimize this
effect.
b. Interference: Trichlorotrifluoroethane
has the ability to dissolve not only oil
and grease but also other organic sub-
stances. No known solvent will selectively
dissolve only oil and grease. Solvent re-
moval results in the loss of short-chain hy-
drocarbons and simple aromatics by vol-
atilization. Significant portions of petro-
leum distillates from gasoline through No.
2 fuel oil are lost in this process. In addi-
tion, heavier residuals of petroleum may
contain a significant portion of materials
that are not extractable with the solvent.
2. Apparatus
a. Separator? funnel, I L, with TFE*
Hopcock.
Ttfco or equivalent.
h. Distilling flask. 125 mL.
f. Water bath.
d. Filter paper, 11 cm diam.t
3. Reagents
a. Hydrochloric acid. HCI. 1 + 1.
h. Trichlorotrifluoroethane^ (1,1,2-tri-
chloro-1.2,2-trifluoroethane). boiling point
47 C. The solvent should leave no measur-\
able residue on evaporation: distill if nee-/
essary. Do not use any plastic tubing to
transfer solvent between containers.
c. Sodium sulfate, Na..SO.,, anhydrous
crystal.
4. Procedure
Collect about 1 L of sample and mark
sample level in bottle for later determina-
tion of sample volume. Acidify to pH 2 or
lower; generally. 5 mL HCI is sufficient.
Transfer to a separatory funnel. Carefully
rinse sample bottle with 30 mL tri-
chlorotrifluoroethane and add solvent
washings to separatory funnel. Preferably
shake vigorously for 2 min. However, if it
* Whatman No. 40 or equivalent.
JFreon or equivalent.
-------
462
ORGANIC CONSTITUENTS (500)
is suspected that a stable emulsion will
form, shake gently for 5 to 10 min. Let lay-
ers separate. Drain solvent layer through a
funnel containing solvent-moistened filter
paper into a clean, tared distilling flask. If
a clear solvent layer cannot be obtained.
add I g Na;SO, to the filter paper cone and
slowly drain emulsified solvent onto the'
crystals. Add more Na;SO4 if necessary.
Extract twice more with 30 mL solvent
each but first rinse sample container with
each solvent portion. Combine extracts in
lured distilling flask and wash filter paper
with an additional 10 to 20 mL solvent.
Distill solvent from distilling flask in a wa-
ter bath at 70 C. Place flask on a water
bath at 70 C for 15 min and draw air
through it w ith an applied vacuum for the
final I min. Cool in a desiccator for 30 min
and weigh.
5. Calculation
If the organic solvent is free of residue.
the gain in weight of the tared distilling
flask is mainly due to oil and grease. Total
gain in weight. A. of tared flask less calcu-
lated residue. B. from solvent blank is the
amount of oil and grease in the sample:
(A - fll x I.QOO
mL
mg oil and grease/L
6. Precision and Accuracy
Methods A. B. and C were tested b> a
single laboratory on a sewage sample. B>
this method the oil and grease concentra-
tion was 12.6 mg/L. When 1-L portions of
the sewage were dosed with 14.0 mg of a
mixture of No. 2 fuel oil and Wesson oil.
recovery of added oils was 93^ with a
standard deviation of 0.9 mg.
503 B. Partition-Infrared Method (TENTATIVE)
1. General Discussion
ii. Principle: Although the extraction
procedure for this method is identical to
that of Method A. infrared detection per-
mits the measurement of many relatively
volatile hvdrocarbons. Thus, the lighter
petroleum distillates, with the exception
of gasoline, may be measured accurately.
Adequate instrumentation allows for the
measurement of as little as 0.2 mg oil and
grease L.
h. Interference: Some degree of selec-
tivity is offered by this method to over-
come some, of the coextracted inter-
ferences discussed in Method A. Heavier
residuals of petroleum may contain a sig-
nificant portion of materials insoluble in
trichlorotrifluoroethane.
c. Definitions: A "known oil" is de-
fined as a sample of oil and/or grease that
represents the only material of that type
used or manufactured in the processes
represented by a wastewater. An "un-
known oil" is defined as one for which a
representative sample of the oil or grease
is not available for preparation of a stan-
dard.
2. Apparatus
a. Separatiiry fiinneI. 1 L. with TFE
stopcock.
h. Infrared xpectrophotonicter, double
beam, recording.
r. Cells, near-infrared silica.
d. Filter paper, II cm diam.^
3. Reagents
u. Hydrochloric mill. HCI. I + I.
h. Trichhrntrifliioritethiinc. See 503A.3/1
c. Sodium xiilfute. NaoSO4. anhydrous.
crystal.
"Teflon or equivalent.
^Whatman No. 40 or equivalent.
-------
OIL ft GREASBSoxhlet Extraction Method
463
d. Reference oil: Prepare a mixture, by
volume, of 37.5*£ iso-octane. 37.5"^ hex-
adecane. and 25<# benzene. Store in
sealed container to prevent evaporation.
4. Procedure
Refer to Method A for sample collec-
tion, acidification, and extraction. Collect
combined extracts in a 100-mL volumetric
flask and adjust final volume to 100 mL
with solvent.
Prepare a stock solution of known oil by
rapidly transferring about I mL (0.5 to 1.0
gi of the oil or grease to a tared 100-mL
volumetric flask. Stopper flask and weigh
to nearest milligram. Add solvent to dis-
solve and dilute to mark. If the oil identity
is unknown If Ic) use the reference oil
ir i/l as the standard. Using volumetric
technics, prepare a series of standards
over the range of interest. Select a pair of
matched near-infrared silica cells. A 1-cm-
path-length cell is appropriate for a work-
ing range of about 4 to 40 mg. Scan stan-
dards and samples from 3.200 cm"1 to
2.700 cm"1 with solvent in the reference
beam and record results on absorbance
paper. Measure absorbances of samples
and standards by constructing a straight
baseline over the scan range and measur-
ing absorbance of the peak maximum at
2.930 cm~' and subtracting baseline ab-
sorbance at that point. If the absorbance
exceeds 0.8 for a sample, select a shorter
pathlength or dilute as required. Use scans
of standards to prepare a calibration
curve.
5. Calculation
mg oil and grease/L
A x 1.000
mL sample
where:
A = mg of oil or grease in extract as deter-
mined from calibration curve.
6. Precision and Accuracy
See 503A.6. By this method the oil and
grease concentration was 17.5 mg'L.
When 1-L portions of the sewage were
dosed with 14.0 mg of a mixture of No. 2
fuel oil and Wesson oil. the recovery of
added oils was 999£ with a standard devia-
tion of 1.4 mg.
503 C. Soxhlet Extraction Method
1. General Discussion
a. Principle: Soluble metallic soaps are
fndrolyzed by acidification. Any oils and
-olid or viscous grease present are sepa-
rated from the liquid samples by filtration.
After extraction in a Soxhlet apparatus
»«h trichlorotrifluoroethane. the residue
remaining after solvent evaporation is
»eighed to determine the oil and grease
content. Compounds volatilized at or be-
low 103 C will be lost when the filter is
dried.
*. Interference: The method is entirely
empirical and duplicate results can be ob-
tained only by strict adherence to all de-
tails. By definition, any material recov-
ered is oil and grease and any filtrable tri-
chlorotrifluoroethane-soluble substances.
such as elemental sulfur and certain organ-
ic dyes, will be extracted as oil and grease.
The rate and time of extraction in the
Soxhlet apparatus must be exactly as di-
rected because of varying solubilities of
different greases. In addition, the length of
time required for drying and cooling ex-
tracted material cannot be varied. There
may be a gradual increase in weight, pre-
sumably due to the absorption of oxygen.
and/or a gradual loss of weight due to vol-
atilization.
-------
464
ORGANIC CONSTITUENTS (500)
2. Apparatus
iin nppnnitn\. Soxhlet.
/>. Viiciiiini /'limp or other source of
vacuum.
c . RiH-lini r funnel. \2 cm.
i/. /./!< 7nV liciiiiiii; nuinile.
i . E\triietion tliimhle. puper.
f. l-'ilter paper. llcmdiam.*
.v- Minlin (/<>//; i//.vA.v. II cm diam.
3. Reagents
n. Hvilrnfliliiric ucitl. HCI. 1+1.
h. TrieliliirittriHiinntethane: See 503A.3/>.
e. Diti1»»iiui'«ns-siiicii filter nid sns-
pen\i<>n.^ 10 g L distilled water.
4. Procedure
Collect about 1 L of sample in a wide-
mouth glass bottle and mark sample level
in bottle for later determination of sample
v olume. Acidify to pH 2 or lower: general-
ly . 5 mL HCI is sufficient. Prepare a filter
consisting of a muslin cloth disk overlaid
with filter paper. Wet paper and muslin
and press down edges of paper. Using a
vacuum, pass 100 mL filter aid suspension
through prepared filler and wash with I L
distilled water. Apply vacuum until no
more water passes tiller. Filter acidified
sample. Apply vacuum until no more wa-
ter passes through filter. Using forceps.
Whatman No. 40 or equivalent.
'Hvlli' Super-C'el. Johns-Manxille Corp.. or eqima-
lent.
transfer filter paper to a watch glass. Add
material adhering to edges of muslin cloth
disk. Wipe sides and bottom of collecting
vessel and Buchner funnel with pieces of
filter paper soaked in solvent, taking care
to remove all films caused by grease and to
collect all solid material. Add pieces of fil-
ter paper to filter paper on watch glass.
Roll all filter paper containing sample and
fit into a paper extraction thimble. Add
any pieces of material remaining on watch
glass. Wipe watch glass with a filter paper
soaked in solvent and place in paper ex-
traction thimble. Dry filled thimble in a
hot-air oven at 103 C for 30 min. Fill
thimble with glass wool or small glass
beads. Weigh extraction flask. Extract oil
and grease in a Soxhlet apparatus, using
trichlorotrifluoroethane at a rate of 20 cy-
cles hr for 4 hr. Time from first cycle. Dis-
till solvent from extraction flask in a water
bath at 70 C. Place flask on a water bath at
70 C for 15 min and draw air through it us-
ing an applied vacuum for the final I min.
Cool in a desiccator for 30 min and weigh.
5. Calculation
See Section 503A.5.
6. Precision and Accuracy
See Section 503.A.6. By this method the
oil and grease concentration was 14.8 mg
L. When 1-L portions of the sewage were
dosed with 14.0 mg of a mixture of No. 2
fuel oil and Wesson oil. the recovery of
added oils was 88rr with a standard devia-
tion of 1.1 mg.
503 D. Extraction Method for Sludge Samples
1. General Discussion
u. Principle: Drying acidified sludge by
heating leads to low results. Magnesium
sulfate monohydrate is capable of com-
bining with 75rf of its own weight in water
in forming MgSO,-7H;O and is used to dr>
sludge. After drying, the oil and grease
can be extracted with trichlorotrifluoro-
ethane.
b. Inierfereme: See503C.l/>.
-------
OB. & GREASE/Hydrocarbons
465
2. Apparatus
a. Extraction uppimniix. Soxhlet.
b. Vacuum pump or other source of
vacuum.
c. Extraction thimble, paper.
d. Crease-free cotton: Extract non-
absorbent cotton with solvent.
3. Reagents
a. HytlrtH-hltiric acid. HCI. cone.
h. Magnesium siilftite monoltyiinite:
Prepare MgSOj-HjO by overnight drying
of a thin layer in an oven at 150 C.
r. Triclili>n>rriJiniiriH'tluine: See 503A.3/».
4. Procedure
In a 150-mL beaker weigh a sample of
wet sludge. 20 ± 0.5 g. of which the dry-
solids content is known. Acidify to pH 2.0
(generally. 0.3 mL cone HCI is sufficient).
Add 25 g MgSO4 H,O. Stir to a smooth
paste and spread on sides of beaker to fa-
cilitate subsequent removal. Let stand un-
til solidified. 15 to 30 min. Remove solids
and grind in a porcelain mortar. Add the
powder to a paper extraction thimble.
Wipe beaker and mortar with small pieces
of filter paper moistened with solvent and
add to thimble. Fill thimble with glass
wool or small glass beads. Extract in a
Soxhlet apparatus, using trichlorotri-
fluorocthane. at a rate of 20 cycles/hr for 4
hr. If any turbidity or suspended matter is
present in the extraction flask, remove by
filtering through grease-free cotton into
another weighed flask. Rinse flask and cot-
ton with solvent. Distill solvent from ex-
traction flask in water at 70 C. Place flask
on a water bath at 70 C for 15 min and
draw air through it using an applied vacu-
um for the final 1 min. Cool in a desiccator
for 30 min and weigh.
5. Calculation
Oil and grease as % of dry solids
gain in weight of Bask, g x 100
weight of wet solids, g x dry solids fraction
6. Precision
The examination of six replicate sam-
ples of sludge yielded a standard deviation
of 4.69?.
503 E. Hydrocarbons
1. Significance
In the absence of specially modified in-
dustrial products, oil and grease is com-
posed primarily of fatty matter from ani-
mal and vegetable sources and hydro-
carbons of petroleum origin. A knowledge
of the percentage of each of these constit-
uents in the total oil and grease minimizes
the difficulty in determining the major
source of the material and simplifies the
correction of oil and grease problems in
»astewater treatment plant operation and
stream pollution abatement.
2. General Discussion
ti. Principle: Silica gel has the ability to
absorb polar materials. If a solution of hy-
drocarbons and fatty materials in tri-
chlorotrifluoroethane is mixed with silica
gel. the fatty acids are selectively removed
from solution. The materials not eliminat-
ed by silica gel adsorption are designated
hydrocarbons by this test.
b. Interference: The more polar hydro-
carbons, such as complex aromatic com-
pounds and hydrocarbon derivatives of
chlorine, sulfur, and nitrogen, may be ad-
-------
OXYGEN DEMAND (CHEMICAL)
489
rection is unnecessary if dilution water
meets the blank criteria stipulated above.
If the dilution water does not meet these
criteria, proper corrections are difficult
and results become questionable.
7 Precision and Accuracy
In a series of interlaboratory studies.
each involving 86 to 102 laboratories (and
as man) riser water and wastewater
seedsi. ?-dav BOD measurements were
nude on svnthetic water samples contain-
ing a 1:1 mixture of glucose and glutamic
a;id in the total concentration range of 5 to
340 mg L. The regression equations for
mean value. T. and standard deviation. 5.
from these studies were:
7= 0.665 ladded level, mg L) - 0.149
5 = 0.120 (added level, mg L) - 1.04
For the 300-mg L mixed primary standard.
the average 5-dav BOD uas 199.4 mg L
with a standard de\ iation of 37.0 mg L.
8 References
I YIIING. JX 19*9. Chemical methods for
mtnficaiiori control. J. \\iin-r Pollm. Cnntml
t\J. 4<:6".
2. L.S. HS.VIRII\VK si AI PROIKTIOX Ao»s-
rv. Or net ot RESEARCH & DEVELOP-
MENT. ENVIRONMENTAL MONITORING &
Si PPORT LABORATORY. CIM INNATI. OHIO.
1978. Personal communication. D.W. Bal-
linger to G.N. McDcrmolt.
9. Bibliography
i r. H.J.. P D Me N A VIM & C T.
1931. Selection of dilution
water for use in oxygen demand tests, fith.
Hftilrli K,-n 48:1084.
Ln.W.L.A M.S.NICHOLS 1937. Influence of
phosphorus and nitrogen on biochemical
oxygen demand. Sen-tin*' WurAi J. 9:34.
RUHHOFT. C.C. 1941. Report on the coopera-
tive study of dilution waters made for the
Standard Methods Committee of the Fed-
eration of Sewage Works Associations.
Si'H-am- WurAj J. 13:669.
SAVV^R. C.N. & L BRAONM . 1946 Modern-
ization of the BOD test for determining the
efficiency of the sewage treatment process.
Srin/vi- U<>rX.
-------
490
ORGANIC CONSTITUENTS (500)
di/ed if they have sufficient contact with
the oxidants.- While the carbonaceous
portion of nitrogen-containing organic
matter is oxidized, no oxidation of am-
monia, either present in a waste or liber-
ated from the nitrogen-containing organic
matter. takes place in the absence of sig-
nificant chloride concentrations.
2. Sampling and Storage
Ic»t unstable samples without delay.
Homogenize samples containing settleable
solids in a blender to permit representative
sampling. IftherejsJU>Jbe_a_.delay before
analysis, preserve ffte.sample.by acid-
ification to pH 2 or lower with cone sulfu-
ric-acid THjTjOj'C'Make preliminary dilu-
tion? Tor wastes containing a high COD to
reduce the error inherent in measuring
small volumes of sample.
508 A. Dichromate Reflux Method
1 General Discussion
,i. /'»//, (/>/i-.- Most types of organic mat-
ter are oxidised bv a Killing mixture of
chromic and sulfuric acids. A sample is re-
lluxed in stronglv acid solution with a
known excess ofjotassium dichrqmate
50 mg L using
0.250.V K5Cr,O:. With 0.025.% K;Cr,0-.
COD values from 5 to 50 mg. L can be de-
termined but with lesser accuracy.'
2. Apparatus
tx apparatus, consisting of 500-mL
-------
OXYGEN DEMAND (CHEMICAU/Dichromate Rtflux Method
or 250-mL erlenmeyer flasks with ground-
glass 24 40 neck" and 300-mm jacket Lie-
big. West, or equivalent condensers.*
with 24.40 ground-glass joint, and a hot
plate having sufficient power to produce at
least 1.4 Wonr of heating surface, or
equivalent.
3. Reagents
a. StiiiiiltirJ p,>iti\. standard grade, previously dried
at 10? C for 2 hr. in distilled water and
dilute to 1 .000m L.
h. Silver Miltiite. Ag..SO4. reagent or
technical grade, crystals or powder.
i . Siiltiiric in-itl reagent: Add Ag;SO4 to
cone H.SO, at the rate of 22 g Ag..SO*4 kg
bottle. Let stand I to 2 days to dissolve
Ag.SO,.
J. Sultiirii ncitl. HjSd. cone.
e. berroin imlii-ator .\iilntiiiii: Dissolve
1.485 g 1.10-phenanthroline monohydrate
and 695 mg FeSO,-7H..O in distilled water
and dilute to 100 mL. This indicator solu-
tion ma> be purchased already prepared. ±
/. SliiiuliirJ terrou.i itniinotiiuni siilftiie
liirtim. approximately 0.25V: Dissolve 98
fFeiNH.MSO.l.-eH.O (FAS) in distilled
water. Add 20 mL cone H..SO,. cool, and
dilute to 1.000 mL. Standardize this solu-
tion daily against standard K.Cr..O: solu-
tion. as follows:
Dilute 10.0 mL standard K:Cr;O: solu-
tion to about 100 mL. Add 30 mL cone
H:SO, and cool. Titrate with FAS titrant.
using 0. 10 to 0. 1 5 mL (2 to 3 drops) ferroin
indicator.
Normality of FAS solution
x 0.25
Volume 0.25V
solution titrated. mL
Volume FAS used in tiiration. mL
"Coming 5000 or equivalent.
^Corning JJM. 91548. or equivalent.
JO F. Smuh Chemical Co.. Columhuv Ohio.
V- Men-uric itnlfiite: HgSO4. crystals or
powder.
h. Siilfainic iwiil: Required only if the
interference of nitrites is to be eliminated
(see f \h above).
/. Potassium hydrogen phthnlitte Man-
ilnnl: Lightly crush and then dry potas-
sium acid phthalate (HOOCC*Ht Minipla with ^511 /HV
COD L: Place 50.0 mL sample (for sam-
ples with COD >900 mg COD'L. use a
smaller sample portion diluted to 50.0 mL)
in the 500-mL refluxing flask. Add I g
HgSOj. several glass beads, and very
slowly add 5.0 mL sulfuric acid reagent.
with mixing to dissolve HgSO4. Cool while
mixing to avoid possible loss of volatile
materials. Add 25.0 mL 0.250V K,Cr,O7
solution and mix. Attach flask to condens-
er and turn on cooling water. Add remain-
ing sulfuric acid reagent (70 mL) through
open end of condenser. Continue swirling
and mixing while adding sulfuric acid re-
agent. CALIION: Afi'.v reflux mixture tlior-
-------
492
ORGANIC CONSTITUENTS (500)
(Ami .Mm I. Rt *(.is,i
AND NORM Mints Km VARIOIS S*»w t Strts
Sample
Si/e
ml.
100
200
lulii»i:
Evaluate the technic and qualiu of re-
agents by testing a standard potassium hy-
drogen phthalate solution.
5 Calculation
mg COD L
(A - fll » .V x K.OOO
mL sample
where:
A " volume FAS used for blank. mL.
B m volume FAS used for sample. mL. and
.V normality of FAS.
-------
PESTICIDES (OAGANlQ/Organochlohrw PMtiodts
493
6 Precision and Accuracy
A set of synthetic samples containing
potassium hydrogen phthalate and NaCI
was tested by 74 laboratories.5 At 200 mg
COD L in the absence of chloride, the
standard deviation was ± 13 mg'L (coeffi-
cient of variation. 6.5%). At 160 mgCOOL
and 100 mg chloride/1, the standard de-
viation was - 14 mg/L (coefficient of vari-
ation. 10.8^).
508 B. References
MUORL. W.A.. R. C. KROMR & C.f.
RUHHOII. 1949. Dichrotnate reflux meth-
od for determination of oxygen consumed.
\na\. Chrm. : 1:953.
MOORE. W.A.. F. J. l.ir>/\«K A
C-C. RICHHOFT. 1951. Determination of
oxygen-consumed values of organic wastes.
Anul. Chem. 23:1297.
MEDALIA. A.I. 1951. Test for traces of or-
ganic matter in water. Anul. (.'ln-m. 23:13IK.
DOHHS. R A. & R.T. W ii i UMV l%3. Hlimi
nation of chloride interference in the chem-
ical oxygen demanJ_teM. Anul. <"/irm
35: IOM.
ANALYTIC*!. REFERENCE SERVICF. USHHW-
PHS. 1965. Oxygen Demand No. :. Study
No. 21. Environmental Health Scr. Water.
PHS Publ. No. 999-WP-26.
-------
ORGANIC CARBON, TOTAL
Method 415.1 (Combustion or Oxidation)
i
STORET NO. Total 00680
Dissolved 00681
1. Scope and Application
1.1 This method includes the measurement of organic carbon in drinking, surface and saline
waters, domestic and industrial wastes. Exclusions are noted under Definitions and
Interferences.
1.2 The method is most applicable to measurement of organic carbon above 1 mg/1.
2. Summary of Method
2.1 Organic carbon in a sample is converted to carbon dioxide (CO2) by catalytic combustion
or wet chemical oxidation. The CO2 formed can be measured directly by an infrared
detector or converted to methane (CH4) and measured by a flame ionization detector.
The amount of CO2 or CH4 is directly proportional to the concentration of carbonaceous
material in the sample.
3. Definitions
3.1 The carbonaceous analyzer measures all of the carbon in a sample. Because of various
properties of carbon-containing compounds in liquid samples, preliminary treatment of
the sample prior to analysis dictates the definition of the carbon as it is measured. Forms
of carbon that are measured by the method are:
A) soluble, nonvolatile organic carbon; for instance, natural sugars.
B) soluble, volatile organic carbon; for instance, mercaptans.
C) insoluble, partially volatile carbon; for instance, oils.
D) insoluble, paniculate carbonaceous materials, for instance; cellulose fibers.
E) soluble or insoluble carbonaceous materials adsorbed or entrapped on insoluble
inorganic suspended matter, for instance, oily matter adsorbed on silt particles.
3.2 The final usefulness of the carbon measurement is in assessing the potential oxygen-
demanding load of organic material on a receiving stream. This statement applies
whether the carbon measurement is made on a sewage plant effluent, industrial waste, or
on water taken directly from the stream. In this light, carbonate and bicarbonate carbon
are not a part of the oxygen demand in the stream and therefore should be discounted in
the final calculation or removed prior to analysis. The manner of preliminary treatment
of the sample and instrument settings defines the types of carbon which are measured.
Instrument manufacturer's instructions should be followed.
Approved for NPDES
Issued 1971
Editorial revision 1974
415.1-1
-------
4. Sample Handling and Preservation
4.1 Sampling and storage of samples in glass bottles is preferable. Sampling and storage in
plastic bottles such as conventional polyethylene and cubitainers is permissible if it is
established that the containers do not contribute contaminating organics to the samples.
NOTE 1: A brief study performed in the EPA Laboratory indicated that distilled water
stored in new, one quart cubitainers did not show any increase in organic carbon after
two weeks exposure.
4.2 Because of the possibility of oxidation or bacterial decomposition of some components of
aqueous samples, the lapse of time between collection of samples and start of analysis
should be kept to a minimum. Also, samples should be kept cool (4"C) and protected
from sunlight and atmospheric oxygen.
4.3 In instances where analysis cannot be performed within two hours (2 hours) from time of
sampling, the sample is acidified (pH < 2) with HC1 or H2SO4.
5. Interferences
5.1 Carbonate and bicarbonate carbon represent an interference under the terms of this test
and must be removed or accounted for in the final calculation.
5.2 This procedure is applicable only to homogeneous samples which can be injected into the
apparatus reproducibly by means of a microliter type syringe or pipette. The openings of
the syringe or pipette limit the maximum size of particles which may be included in the
sample.
6. Apparatus
6.1 Apparatus for blending or homogenizing samples: Generally, a Waring-type blender is
satisfactory.
6.2 Apparatus for total and dissolved organic carbon:
6.2.1 A number of companies manufacture systems for measuring carbonaceous
material in liquid samples. Considerations should be made as to the types of
samples to be analyzed, the expected concentration range, and forms of carbon to
be measured.
6.2.2 No specific analyzer is recommended as superior.
7. Reagents
7.1 Distilled water used in preparation of standards and for dilution of samples should be
ultra pure to reduce the carbon concentration of the blank. Carbon dioxide-free, double
distilled water is recommended. Ion exchanged waters are not recommended because of
the possibilities of contamination with organic materials from the resins.
7.2 Potassium hydrogen phthalate, stock solution, 1000 mg carbon/liter: Dissolve 0.2128 g
of potassium hydrogen phthalate (Primary Standard Grade) in distilled water and dilute
to 100.0 ml.
NOTE 2: Sodium oxalate and acetic acid are not recommended as stock solutions.
7.3 Potassium hydrogen phthalate, standard solutions: Prepare standard solutions from the
stock solution by dilution with distilled water.
7.4 Carbonate-bicarbonate, stock solution, 1000 mg carbon/liter: Weigh 0.3500 g of sodium
bicarbonate and 0.4418 g of sodium carbonate and transfer both to the same 100 ml
volumetric flask. Dissolve with distilled water.
415.1-2
-------
7.5 Carbonate-bicarbonate, standard solution: Prepare a series of standards similar to step
7.3.
NOTE 3: This standard is not required by some instruments.
7.6 Blank solution: Use the same distilled water (or similar quality water) used for the
preparation of the standard solutions.
8. Procedure
8.1 Follow instrument manufacturer's instructions for calibration, procedure, and
calculations.
8.2 For calibration of the instrument, it is recommended that a series of standards
encompassing the expected concentration range of the samples be used.
9. Precision and Accuracy
9.1 Twenty-eight analysts in twenty-one laboratories analyzed distilled water solutions
containing exact increments of oxidizable organic compounds, with the following results:
Increment as Precision as Accuracy as
TOC Standard Deviation Bias, Bias,
nig/liter TOC. mg/liter % ing/liter
4.9 3.93 +15.27 +0.75
107 8.32 + 1.01 +1.08
(FWPCA Method Study 3, Demand Analyses)
Bibliography
1. Annual Book of ASTM Standards, Part 31, "Water", Standard D 2574-79, p 469 (1976).
2. Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 532,
Method 505, (1975).
415.1-3
-------
APPENDIX E
TEST LOG
-------
APPENDIX E
TEST LOG
Date
8/15/83
8/16/83
8/17/83
Time
0900
0930
1300
1400
1600
1730
0700
0735
0805
0810
0830
1020
1235
1400
1600
0700
0740
0745
0830
Task Performed
TRW test crew and EPA representative arrive
at the Golden West Refinery facility in
Santa Fe Springs, California.
Crew begins set-up at test sites. Some
problem with electricity supply.
Continuous hydrocarbon monitor (Beckman 402)
placed on-line for testing at the lAF-outlet
sample location.
Problem with electricity supply.
Beckman 402 back on-line at lAF-outlet.
Crew departs test facility.
TRW test crew and EPA representative arrive
at the Golden West facility.
IAF gas bag sample #1.
Liquid VOA sample taken and composite
sample began at lAF-inlet.
Liquid VOA sample taken and composite began
at lAF-outlet.
Liquid composite sample at API-inlet.
IAF gas bag sample #2.
IAF gas bag sample #3.
Liquid VOA samples at lAF-inlet and lAF-outlet.
Crew departs test facility.
TRW test crew and EPA representative arrive
at the Golden West facility.
Liquid VOA and composite samples at lAF-
inlet, lAF-outlet, and API-inlet (composite
only).
IAF gas bag sample #1.
Perform monitoring check of drain system
with EPA and NSPS representatives.
-------
APPENDIX E (Concluded)
Date
8/17/83
8/18/83
8/19/83
Time
1000
1153
1300
1600
0700
0800
1000
1030
1040
1130
1310
1500
0730
0800
0830
0850
1030
1400
1530
Task Performed
IAF gas bag sample #2.
IAF gas bag sample #3.
Liquid VOA samples at lAF-inlet and
lAF-outlet.
Crew departs test facility.
TRW test crew and EPA representative arrive
at the Golden West facility.
Process interruption - instruments off-line.
Process stable - instrument back on-line.
IAF gas bag sample #1.
Liquid VOA and composite samples at lAF-
inlet and lAF-outlet.
Liquid composite sample at API-inlet.
IAF gas bag sample #2.
Crew departs test facility.
TRW test crew and EPA representative arrive
at the Golden West facility.
Perform monitoring check of drain system
with EPA and NSPS representative.
Liquid VOA and composite samples at the
lAF-inlet, lAF-outlet and API-inlet
(composite only).
IAF gas bag sample #1.
IAF gas bag sample #2.
Liquid VOA samples at the lAF-inlet and
lAF-outlet.
Instruments off-line and flame-out.
End of test period.
Crew departs test facility.
-------
APPENDIX F
PROJECT PARTICIPANTS
-------
APPENDIX F
PROJECT PARTICIPANTS
U.S. Environmental Protection Agency (Representatives)
Winton Kelly
Randy McDonald
Radian Corporation (NSPS Representatives)
Barry Mitsch
Golden West Refinery Company (Plant Contacts)
Doug Ayre
Mike Murray
TRN Inc. (Field Test Team)
Cecil Stackhouse
Don Ackerman
Gary Henry
Dave Savia
------- |