&EPA
United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EMB Report 83-WWS-3
March 1984
Air
Petroleum
Waste Water
Treatment Systems
Emission Test Report
Phillips Petroleum
Company
Sweeny Refinery
Sweeny, Texas
-------
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
PHILLIPS PETROLEUM COMPANY
SWEENY, TEXAS
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
Phillips - Phillips Petroleum 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
-------
TABLE OF CONTENTS
Section Page
1 INTRODUCTION 1-1
2 SUMMARY AND DISCUSSION OF RESULTS 2-1
2.1 IAF System 2-1
2.2 Process Water Analyses 2-23
3 PROCESS DESCRIPTION 3-1
3.1 Plant Description 3-1
3.2 Refinery Wastewater System 3-1
3.3 Monitoring of Wastewater Treatment Facilities . . 3-8
3.4 Process Upsets and Irregularities During Test . . 3-10
3.5 Additional Notes Regarding Wastewater
Treatment System 3-10
4 LOCATION OF SAMPLE POINTS 4-1
4.1 Gaseous Sample Locations 4-1
4.2 Water Sample Locations 4-1
5 SAMPLING AND ANALYTICAL PROCEDURES 5-1
5.1 Gaseous VOC Methods 5-1
5.2 Permanent Gas Analysis 5-13
5.3 Gaseous Volumetric Flow Measurement 5-13
5.4 Liquid Sample Methods 5-15
5.5 Liquid Sample Analysis Methods 5-16
m
-------
LIST OF FIGURES
Figure Page
3-1 Wastewater treatment system for new process units . . . 3-4
3-2 Induced air flotation system, "Hydrocell" designed
by U.S. Filter 3-6
3-3 Flow pattern of gas and water in IAF system cell .... 3-7
4-1 Schematic representation of the IAF process with
sample points and induced air system:
Phillips Petroleum - Sweeny, Texas 4-2
4-2 lAF-outlet sample locations fabricated:
Phillips Petroleum - Sweeny, Texas 4-3
4-3 CPI separator processes with process sample
locations: Phillips Petroleum - Sweeny, Texas 4-4
5-1 Gas bag sampling system 5-2
5-2 Example of GC/FID calibration for Ci-Cs speciation . . . 5-4
5-3 Example of GC/FID analysis on IAF unit #1 exhaust
air - gas bag sample for Cj-Cs speciation 5-5
5-4 Example of GC/FID analysis on IAF unit #2 exhaust
air - gas bag sample for C^-C5 speciation 5-6
5-5 Example of GC/FID calibration for C6-C9 speciation . . . 5-8
5-6 Example of GC/FID analysis on IAF unit #1 exhaust
air - gas bag sample for C6-C9 speciation 5-9
5-7 Example of GC/FID analysis on IAF unit #2 exhaust
air - gas bag sample for C6-C9 speciation 5-10
5-8 Example of a calibration check with a
recalibration required 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
5-11 GC/FID quantitative analysis by purge and trap,
sample no. IAF-INLET-VOA-0740 5-24
5-12 GC/FID quantitative analysis by purge and trap,
sample no. IAF-OUT-VOA-0740 5-25
-------
LIST OF TABLES
Table Page
2-1 Sampling Log of Continuous Hydrocarbon Mnitoring:
Sampling Locations at the Phillips Petroleum
Refinery - Sweeny, Texas 2-2
2-2 Daily Time Table of Sampling Activities at Phillips
Petroleum Refinery - Sweeny, Texas 2-3
2-3 Daily Emission Rate Averages at the IAF Outlet Sample
Location on Test Days 9/19/83 to 9/23/83, Phillips
Petroleum Facility - Sweeny, Texas 2-7
2-4 Continuous Emissions Results: Hydrocarbon Monitoring
at the IAF #1 Outlet Sample Location - Phillips
Petroleum, Sweeny, Texas - Test Day 9/19/83 2-8
2-5 Continuous Emissions Results: Hydrocarbon Monitoring
at the IAF #1 Outlet Sample Location - Phillips
Petroleum, Sweeny, Texas - Test Day 9/20/83 2-9
2-6 Continuous Emissions Results: Hydrocarbon Monitoring
at the IAF #1 Outlet Sample Location - Phillips
Petroleum, Sweeny, Texas - Test Day 9/21/83 2-10
2-7 Continuous Emissions Results: Hydrocarbon Monitoring
at the IAF #1 Outlet Sample Location - Phillips
Petroleum, Sweeny, Texas - Test Day 9/22/83 2-11
2-8 Continuous Emissions Results: Hydrocarbon Monitoring
at the IAF #1 Outlet Sample Location - Phillips
Petroleum, Sweeny, Texas - Test Day 9/23/83 2-12
2-9 Flow Monitoring Results: IAF #1 Flow Measurements at
the Inlet and Outlet Gaseous Sample Locations -
Phillips Petroleum, Sweeny, Texas 2-13
2-10 Continuous Emissions Results: Hydrocarbon Monitoring
at the IAF #2 Outlet Sample Location - Phillips
Petroleum, Sweeny, Texas - Test Day 9/20/83 2-14
(continued)
VI
-------
LIST OF TABLES (Continued)
Table Page
2-11 Continuous Emissions Results: Hydrocarbon Monitoring
at the IAF #2 Outlet Sample Location - Phillips
Petroleum, Sweeny, Texas - Test Day 9/21/83 2-15
2-12 Continuous Emissions Results: Hydrocarbon Monitoring
at the IAF #2 Outlet Sample Location - Phillips
Petroleum, Sweeny, Texas - Test Day 9/22/83 2-16
2-13 Continuous Emissions Results: Hydrocarbon Monitoring
at the IAF #2 Outlet Sample Location - Phillips
Petroleum, Sweeny, Texas - Test Day 9/23/83 2-17
2-14 Flow Monitoring Results: IAF #2 Flow Measurements at
the Inlet and Outlet Gaseous Sample Locations -
Phillips Petroleum, Sweeny, Texas 2-19
2-15 Gas Chromatograph Results From the Sample Location
at IAF #1 (Phillips South Unit) Phillips Petroleum,
Sweeny, Texas 2-20
2-16 Gas Chromatograph Results From the Sample Location
at IAF #2 (Phillips North Unit) Phillips Petroleum,
Sweeny, Texas 2-22
2-17 Liquid Analyses for Process Samples on Test Day
9/20/83, Phillips Petroleum - Sweeny, Texas 2-24
2-18 Liquid Analyses for Process Samples on Test Day
9/21/83, Phillips Petroleum - Sweeny, Texas 2-25
2-19 Liquid Analyses for Process Samples on Test Day
9/22/83, Phillips Petroleum - Sweeny, Texas 2-26
2-20 Liquid Analyses for Process Samples on Test Day
9/23/83, Phillips Petroleum - Sweeny, Texas 2-27
2-21 Cj to C7 Speciation by GC/FID Purge and Trap,
Phillips Petroleum, Sweeny, Texas 2-28
2-22 Gas Chromatograph Results from Liquid VOA and
Composite Samples at IAF Sample Locations - 9/22/83,
Phillips Petroleum - Sweeny, Texas 2-32
2-23 Gas Chromatograph Results from Liquid VGA and
Composite Samples at CPI Sample Locations - 9/22/83,
Phillips Petroleum - Sweeny, Texas 2-33
(continued)
-------
LIST OF TABLES (Concluded)
Table Page
3-1 Unit Charge Rates During Test Period 3-2
3-2 Estimated Wastewater Flow Rates to CPI Separators
During Test Period 3-9
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 .... 5-27
vm
-------
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 wastewater treatment
systems in petroleum refineries. Under contract to the Emission
Measurement Branch, EPA, TRW Environmental Operations personnel conducted
a testing program at the wastewater treatment system at Phillips Petroleum
Company's Sweeny Refinery in Sweeny, Texas, during September 19-23,
1983.
The purpose of this test program was to provide estimates of the
organic release rates from the induced air flotation (IAF) units. This
information is necessary to estimate uncontrolled emission rates from
uncovered flotation devices for potential emission reduction and cost
effectiveness calculations.
The IAF system at the Sweeny Refinery consists of two parallel
units. Each IAF is covered and is equipped with inspection doors. An
air or inert purge is not used to ventilate the IAF head space. For
test purposes, a ventilation air stream was purged through the head
space of each unit, with the inspection doors being sealed as tightly as
possible. 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
emissions because of the difficulty in measuring a dispersed-source
fugitive emission. It is assumed that the dominant factors affecting
organic emission rates are the water characteristics 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.
-------
However, the results of these tests do not necessarily represent
the emissions from the IAF units under normal operation when an air
purge stream is not used and the inspection doors are closed.
Tests were conducted to determine the mass flow rate and the organic
species composition of the added ventilation air from the two IAF units.
During these measurements, samples of wastewater were collected from the
IAF influents and effluents and from the CPI separator influents and
effluents to characterize the liquid stream.
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
-------
2. SUMMARY AND DISCUSSION OF RESULTS
This section details the results of the testing and analysis at the
Sweeny Refinery wastewater treatment units. The overall refinery waste
water treatment system is illustrated in Figure 3-1 and the sampling
locations are indicated in Figures 4-1 to 4-3. Table 2-1 presents a
summary of the periods during which continuous hydrocarbon monitoring
was performed at the indicated sample locations. Table 2-2 presents a
summary of the periods during which integrated gas samples were collected,
velocity or flow rate measurements were measured and when liquid samples
were collected from each location. The results are discussed separately
for the dual tank IAF water systems and the process water analyses.
2.1 IAF SYSTEM
A summary of the daily average total hydrocarbon mass flow rates in
the dual IAF exhaust air is presented in Table 2-3. The total hydrocarbon
measurement does not exclude methane. The hydrocarbon mass flow in the
IAF ventilation air ranged from 0.36 Ib/hr to 0.93 Ib/hr for unit #1 and
0.34 Ib/hr to 0.80 Ibs/hr for unit #2 (24-hour average basis) over the
five days of testing. The average mass flow was 0.56 Ib/hr (24-hour
basis) for the complete IAF system. The average mass flow for each IAF
unit was 0.60 Ib/hr and 0.52 Ib/hr (24-hour basis) for unit #1 and #2,
respectively. The test results on a one-hour average basis for each day
of testing are presented in Tables 2-4 to 2-8 for unit #1 and in
Tables 2-10 to 2-13 for unit #2. 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
-------
Table 2-1. SAMPLING LOG OF CONTINUOUS HYDROCARBON MONITORING:
SAMPLING LOCATIONS AT THE PHILLIPS PETROLEUM REFINERY - SWEENY, TEXAS
Test day
9/19/83
9/20/83
9/20/83
9/21/83
9/21/83
9/21/83
9/22/83
9/22/83
9/23/83
Sample
location
lAF-Outlet #1
lAF-Outlet #1
lAF-Outlet #2
lAF-Outlet #1
lAF-Outlet #2
lAF-Outlet #2
lAF-Outlet #1
lAF-Outlet #2
lAF-Outlet #1
Time
sampled
1700-2400
0001-2400
1700-2400
0000-2400
0000-1100
1200-2400
0000-2400
0900-2400
0000-1330
Duration
sampled (hr)
7
24
7
24
11
12
24
15
13
2-2
-------
Table 2-2. DAILY TIME TABLE OF SAMPLING ACTIVITIES AT
PHILLIPS PETROLEUM REFINERY - SWEENY, TEXAS
no
i
GO
(TIM) 0700 0800 0900
ygttjog/jhyt
IAF-OUTLET fl 9/19
IAF-OUTLET fl 9/20
IAF- INLET fl 9/20
IAF-OUTLET 12 9/20
A' 9/20
CPI(I) 9/20
1000 1100 1200 1300 1400 1500 1600 1700 1800
(1700 • 2400)
a a
o o o o
o o
A A A A
o
o
a
o o o o
o
o o o o
o o
o
(1)CTI iMludM CPI Inlet 1,2,31 CPI outltt 2.3.
legend
(0000-0000) (Hethod 2SA-TCH)
O (Velocity)
O (Liquid Composite)
O (Liquid VOA)
A (Method 18-G«j Big)
0 (Grab Sanple)
-------
Table 2-2. Continued
(TlM) 0700 0800 0900 1000 1100 1200 1300 1400 1500 1600 1700 IBOQ
Locition/paU
IAF-OUTLET II 9/21
IAF-INLET fl 9/21
O
O
(0001 - 2400)
a
o
o
o
IAF-OUTLET K 9/21
ro
A' 9/21
n a a
00 00
0 °
• A A
00 0 °
O 0
0(D (D
0 O
"*CPI Includes CPI Inlet 1,2,3; CPI outlet 1,2,3.
Legend
(0000-0000) (Method 2SA-TCH)
O (Velocity)
O (Liquid Composite)
O (Liquid VOA)
A (Method IB-Gas Bag)
0 (Grab Sample)
-------
Table 2-2. Continued
(TIM)
0700 0800 0900 1000 HOP IMP 1300 1400 1500 1600 1700 1800
IAF-OUTLET tl 9/22
(0001 - 2400)
IAF-INLET f1 9/22
o
o
A A
O
A
IAF-OUTIET 12 • 9/22
(0900 - 2400)
r\>
t
01
IAF-INLET 12 9/22
O
O
'CM includes CPI inlet 1,2,3; CM outlet 2,3.
0 0
o
<«(l) 0<»
o
o o
o
V"
o
Legend
(0000-0000) (Method 25A-TCH)
D (Velocity)
O (Liquid Coqwslte)
O (Liquid VOA)
A (Netted IB-Gat Big)
0 (Grab Simple)
-------
Table 2-2. Concluded
(TIM
loc«t1on/PiU
0700 0800 0900 1000 1100 1200 1300 1400 1500 IMP 1700 1SOO
IAF-OUTLET fl 9/23
(0001 - 1330)
IAF-IM.ET 12
9/23
O
O
IAF-INLET fl
9/23
D
INS
I
IAF-OUTIET 12 9/23
O
O
a
o
CPI
(1)
0
Includes CPI Inlet 1,2,3: CPI outlet 2.3.
(0000-0000)
O
O
O
legend
(Method 2SA-TCH)
(Velocity)
(Liquid Composite)
(Liquid VOA)
(Method 18-fes Bag)
(Grab Sample)
-------
Table 2-3. DAILY EMISSION RATE AVERAGES AT THE IAF OUTLET
SAMPLE LOCATION ON TEST DAYS 9/19/83 to 9/23/83
PHILLIPS PETROLEUM FACILITY - SWEENY, TEXAS
Average daily emission rate
(Ib/hr as CSH8)
Test day
9/19/83
9/20/83
9/21/83
9/22/83
9/23/83
IAF #1
0.51
0.47
0.71
0.93
0.36
IAF #2
a
0.34
0.54
0.80
0.42
aIAF #2 not on-line for monitoring on 9/19/83.
2-7
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Table 2-4. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF #1 OUTLET SAMPLE LOCATION - PHILLIPS PETROLEUM, SWEENY, TEXAS
TEST DAY 9/19/83
Time
1700b
1800
1900
2000
2100
2200
2300
2400
Average
Concentration3
(ppm as C3H8)
1492
1537
1320
1291
1250
1061
1054
1091
Flow
(SCFM)
62.5
62.5
62.5
62.5
62.5
62.5
62.5
62.5
Emission rate
(Ibs/hr as C3H8)
0.60
0.61
0.53
0.52
0.50
0.42
0.42
0.44
0.51
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
Begin test period with Beckman 402 analyzer on-line at the IAF #1 (South)
sample location.
2-8
-------
Table 2-5. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF #1 OUTLET SAMPLE LOCATION - PHILLIPS PETROLEUM, SWEENY, TEXAS
TEST DAY 9/20/83
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)
1075
1057
1021
1028
1078
1161
1236
1081
905
1040
1199
1262
1138
1313
1834
1577
1201
1182
1142
1142
1176
1299
1178
1297
Flow
(SCFM)
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
61.3
Emission rate
(Ibs/hr as C3H8)
0.42
0.41
0.40
0.40
0.42
0.46
0.48
0.42
0.35
0.41
0.47
0.50
0.45
0.52
0.72
0.62
0.47
0.46
0.45
0.45
0.46
0.51
0.46
0.51
0.47
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
2-9
-------
Table 2-6. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF #1 OUTLET SAMPLE LOCATION - PHILLIPS PETROLEUM, SWEENY, TEXAS
TEST DAY 9/21/83
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)
1845
1969
2035
2052
1974
1952
1918
1877
1637
1695
1625
1521
1387
1508
1458
1990
2022
1928
1681
1434
1244
1249
1322
1772
Flow
(SCFM)
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
64.6
Emission rate
(Ibs/hr as C3H8)
0.76
0.81
0.84
0.85
0.82
0.81
0.79
0.78
0.68
0.70
0.67
0.63
0.57
0.62
0.60
0.82
0.84
0.80
0.70
0.59
0.51
0.52
0.55
0.73
0.71
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
2-10
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Table 2-7. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF #1 OUTLET SAMPLE LOCATIONS - PHILLIPS PETROLEUM, SWEENY, TEXAS
TEST DAY 9/22/83
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)
1754
2224
2533
2619
2834
3111
3002
2924
3358
2485
2067
2271
2378
2087
2190
2124
1979
1618
1648
1478
1159
1791
2073
1560
Flow
(SCFM)
65.4
65.4
65.4
65.4
64.5
65.4
65.4
65.4
65.4
65.4
65.4
65.4
65.4
65.4
65.4
65.4
65.4
65.4
65.4
65.4
65.4
65.4
65.4
65.4
Emission rate
(Ibs/hr as C3H8)
0.74
0.93
1.06
1.10
1.19
1.30
1.26
1.22
1.41
1.04
0.87
0.95
1.00
0.87
0.92
0.89
0.83
0.68
0.69
0.62
0.49
0.75
0.87
0.65
0.93
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
2-11
-------
Table 2-8. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF #1 OUTLET SAMPLE LOCATION - PHILLIPS PETROLEUM, SWEENY, TEXAS
TEST DAY 9/23/83
Time
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100b
1200C
1300d
e
Average
Concentration3
(ppm as C3H8)
1468
1158
1139
913
865
677
996
1025
1199
1053
2118
2613
3090
(Reduced
(No Flow
Flow
(SCFM)
53.6
53.6
53.6
53.6
53.6
53.6
53.6
53.6
53.6
53.6
26.9
26.9
2.4
Rate)
Induced)
Emission rate
(Ibs/hr as C3H8)
0.50
0.40
0.39
0.31
0.30
0.23
0.34
0.35
0.41
0.36
0.36
0.45
0.05
0.36
0.40
0.05
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
Air flow through IAF reduced 50%.
cSampling with 30 min. 50% and 30 min. no flow through IAF system.
No induced air flow through IAF system.
6End of test period at IAF #1 (South) sample location.
2-12
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Table 2-9. FLOW MONITORING RESULTS: IAF #1 FLOW MEASUREMENTS AT THE
INLET AND OUTLET GASEOUS SAMPLE LOCATIONS - PHILLIPS PETROLEUM, SWEENY, TEXAS
ro
i
Sample location
Inlet
Inlet
Outlet
Outlet0
Date
9/19/83
9/20/83
9/21/83
9/21/83
9/22/83
9/22/83
9/23/83
9/23/83
9/20/83
9/20/83
9/21/83
9/21/83
9/22/83
9/22/83
9/23/82
9/23/83
Time
1540-1613
1003-1033
1425-1455
858- 938
1637-1657
854- 916
1056-1236b
1136-1236
1436-1451
1127-1142
1550-1610
1100-1115
1521-1536
1000-1015
1242-1328
Temperature
(°F)
94
60
70
65
75
68
76
99
101
85
92
102
110
103
120
Actual
volumetric
flowrate
(ACFM)
—
64.5
58.2
67.9
77.4
51.1
52.5
26.8
18.4
16.1
28.5
27.8
31.0
29.4
33.5
2.6
Standard
volumetric
flowrate
(SCFM)
62. 5a
61.3
60.3
69.0
79.4
51.4
53.6
26.9
17.4
15.1
28.2
27.1
29.7
27.8
32.1
2.4
Flow not measured on initial test day (9/19/83), therefore, used average of remaining test days.
Monitoring reduced flow (50%) through IAF; not included in 9/19/83 flow average.
cMonitoring no flow condition through IAF.
-------
Table 2-10. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF #2 OUTLET SAMPLE LOCATION - PHILLIPS PETROLEUM, SWEENY, TEXAS
TEST DAY 9/20/83
Time
1700b
1800
1900
2000
2100
2200
2300
2400
Average
Concentration3
(ppm as C3H8)
1154
1025
1074
1118
1135
1197
1042
1152
Flow
(SCFM)
48.4
48.4
48.4
48.4
48.4
48.4
48.4
48.4
Emission rate
(Ibs/hr as C3H8)
0.36
0.32
0.33
0.35
0.35
0.37
0.32
0.36
0.34
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
Begin test period with Beckman 400 analyzer on-line at the IAF #2 (North)
sample location.
2-14
-------
Table 2-11. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF #2 OUTLET SAMPLE LOCATION - PHILLIPS PETROLEUM, SWEENY, TEXAS
TEST DAY 9/21/83
Time
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100b
1200
1300
1400b
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
Average
Concentration9
(ppm as C3H8)
1448
1356
1525
1525
1571
1546
1634
1559
1739
1834
1420
1610
2319
2692
2642
1917
1696
1643
1449
1387
1359
1794
Flow
(SCFM)
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
49.6
Emission rate
(Ibs/hr as C3H8)
0.46
0.43
0.48
0.48
0.50
0.49
0.52
0.49
0.55
0.58
0.45
0.51
0.74
0.85
0.84
0.61
0.54
0.52
0.46
0.44
0.43
0.57
0.54
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
Continuous analyzer (Beckman 400) flamed out and recalibration required;
therefore, sample off-line.
2-15
-------
Table 2-12. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF #2 OUTLET SAMPLE LOCATION - PHILLIPS PETROLEUM, SWEENY, TEXAS
TEST DAY 9/22/83
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)
2015
2348
2744
3121
3549
3760
3805
3595
3240
3428
2960
2716
2981
2694
2892
2777
1937
1373
1173
993
1011
1483
1443
1300
Flow
(SCFM)
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
50.8
Emission rate
(Ibs/hr as C3H8)
0.66
0.76
0.89
1.02
1.15
1.22
1.24
1.17
1.05
1.11
0.96
0.88
0.97
0.88
0.94
0.90
0.63
0.45
0.38
0.32
0.33
0.48
0.47
0.42
0.80
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
2-16
-------
Table 2-13. CONTINUOUS EMISSION RESULTS: HYDROCARBON MONITORING AT
THE IAF #2 OUTLET SAMPLE LOCATION - PHILLIPS PETROLEUM, SWEENY, TEXAS
TEST DAY 9/23/83
Time
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100b
1200C
1300d
Average
Concentration3
(ppm as C3H8)
1274
1106
1055
957
1054
674
837
948
1250
1278
2576
2651
2934
Flow
(SCFM)
63.0
63.0
63.0
63.0
63.0
63.0
63.0
63.0
63.0
63.0
26.9
26.9
2.4e
(Reduced Rate)
(No Induced Flow)
Emission rate
(Ibs/hr as C3H8)
0.51
0.45
0.43
0.42
0.42
0.27
0.34
0.38
0.50
0.52
0.44
0.46
0.04
0.42
0.45
0.04
Concentration is average value for continuous readings across the hour
(0-55 minutes) based on 5-minute readings.
Air flow through IAF system reduced 50%.
GSampling with 30 min. 50% and 30 min. no flow through IAF system.
No air flow through IAF system.
eEnd of test period at IAF #2 (North) sample location.
2-17
-------
the carbon content. While the concentration results are on a propane
basis and are not equal to the true hydrocarbon concentration, the
calculated mass flow rates are equivalent to true hydrocarbon mass flow
rates. The average volumetric flow rate result that was used for
calculation of the mass flow is also given for each day of monitoring.
A single value is used for each day because the ventilation blowers
operated at constant speed and no changes were made to the ventilation
configuration. The average volumetric flow rate results are presented
in Table 2-9 for unit #1 and Table 2-14 for unit #2.
The integrity of the closed system across the IAF units was checked
by measuring inlet and outlet flow rates. Problems with sealing the
units were evident and the difference in the flow rate measurement was
filtration lost in the system. Monitored rates across the test day
determined that 65-85 percent of the inlet flow exited the system via
the fabricated outlet duct.
The results of the analysis of integrated gas samples of the IAF
unit #1 and unit #2 exhaust air are presented in Tables 2-15 and 2-16.
The species analyses were obtained using two field gas chromatographic
systems and were intended to generally identify the major components and
their approximate concentrations. Calibrations 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 methyl-
cyclopentane and cyclohexane) and would be indistinguishable with the
analytical systems employed. However, since clear identification of
toluene and xylene was present, it is probable that at least part of the
concentrations attributed to benzene was actually benzene. Additional
descriptions of the chromatographic techniques are given in Section 5.
On 8/19/83, a test was performed to observe the off-gasing effect
caused by the purge air across the system. The first check was decreasing
the flow rate by one-half. The result was essentially as expected, the
2-18
-------
Table 2-14.
ro
H-*
vo
FLOW MONITORING RESULTS: IAF #2 FLOW MEASUREMENTS AT THE INLET AND OUTLET
GASEOUS SAMPLE LOCATIONS - PHILLIPS PETROLEUM, SWEENY, TEXAS
Sample location
Inlet
Outlet
Date
9/20/83
9/21/83
9/21/83
9/22/83
9/22/83
9/23/83
9/21/83
9/21/83
9/22/83
9/22/83
9/23/83
Time
1813-1843
830- 905
1507-1537
948-1028
1611-1631
934- 954
1355-1410
1620-1635
1122-1137
1543-1558
1020-1035
Temperature
(°F)
78
58
71
68
77
72
88
89
98
102
102
Actual
volumetric
flowrate
(ACFM)
49.5
47.5
49.3
54.1
46.4
62.2
21.0
21.7
21.0
22.9
24.2
Standard
volumetric
flowrate
(SCFM)
48.4
49.3
49.9
55.2
46.5
63.0
20.7
21.3
20.2
21.9
23.2
-------
Table 2-15. ,GAS CHROMATQGRAPH RESULTS FROM THE SAMPLE LOCATION
AT IAF #1 (PHILLIPS SOUTH UNIT) PHILLIPS PETROLEUM, SWEENY, TEXAS
DATE
TIME
RUN NO.
ANALYTICAL RESULTS
(ppmv as compound)
C-l
C-2
C-3
C-4
C-5
Hexane
Benzene
Heptane
Toluene
m-Xylene
o-Xylene
TOTAL HYDROCARBON3
(ppmv as compound)
CONTINUOUS MONITOR DATA
Hydrocarbon Level
(ppmv as C3H8)
Emission Rate
(Ib/hr)
9/20/83
1500
1
87.2
4.9
6.7
18.4
20.4
145.3
161.1
25.9
139.4
45.4
20.7
675.4
1834
0.72
9/20/83
1645
2
57.7
—
4.2
11.7
17.6
85.9
99.0
16.8
95.2
34.2
12.4
434.7
1577
0.62
9/21/83
1100
3
65.1
4.3
3.9
15.2
20.3
110.0
135.2
37.0
94.1
33.3
10.3
528.7
1625
0.67
9/21/83
1430
4
57.5
6.0
4.7
1.1
3.9
63.6
95.1
21.1
67.0
21.1
8.5
349.6
1508
0.62
(continued)
2-20
-------
Table 2-15. Concluded
DATE 9/22/83 9/22/83 9/23/83
TIME 0930 1430 0915
RUN NO. 567
ANALYTICAL RESULTS
(ppmv as compound)
C-l
C-2
C-3
C-4
C-5
Hexane
Benzene
Heptane
Toluene
m-Xylene
o-Xylene
TOTAL HYDROCARBON
(ppmv as compound) 1388.2 955.7 349.8
CONTINUOUS MONITOR DATA
Hydrocarbon Level
(ppmv as C3H8) 3358 2087 1199
Emission Rate
(Ib/hr) 1.41 0.87 0.41
aTotal includes unidentified hydrocarbon responsive to GC/FID.
218.2
6.2
5.6
21.2
52.4
352.2
353.4
—
217.4
118.4
43.2
197.5
5.7
6.0
15.5
16.2
213.5
201.1
78.7
140.2
62.4
18.9
115.7
4.0
2.7
4.6
10.5
41.3
60.9
20.2
53.7
26.2
10.0
2-21
-------
Table 2-16. GAS CHROMATOGRAPH RESULTS FROM THE SAMPLE LOCATION
AT IAF #2 (PHILLIPS NORTH UNIT) PHILLIPS PETROLEUM, SWEENY, TEXAS
DATE
TIME
RUN NO.
ANALYTICAL RESULTS
(ppmv as compound)
C-l
C-2
C-3
C-4
C-5
Hexane
Benzene
Heptane
Toluene
m-Xylene
o-Xylene
TOTAL HYDROCARBON5
(ppmv as compound)
CONTINUOUS MONITOR
Hydrocarbon Level
(ppmv as C3H8)
Emission Rate
(Ib/hr)
9/21/83
0930
3a
58.7
4.2
4.4
17.5
21.5
128.5
134.3
35.9
84.0
26.1
8.1
523.2
DATA
1739
0.55
9/21/83
1545
4
78.6
7.5
5.9
22.6
10.5
133.7
171.8
46.6
116.5
43.9
13.6
651.2
2319
0.74
9/22/83
1050
5
226.2
7.3
5.6
21.5
59.5
292.5
287.0
113.1
178.2
73.9
20.0
1284.8
3428
1.11
9/22/83
1550
6
167.2
3.8
3.6
8.6
7.7
109.7
122.4
50.2
96.5
46.9
14.5
631.1
2892
0.94
9/23/83
1015
7
93.0
3.4
2.2
3.5
8.9
33.1
53.4
20.3
52.2
26.1
8.5
251.2
1278
0.52
IAF #2 not monitored on 9/20/83 during Run No. 1 and Run No. 2.
3Total includes unidentified hydrocarbon responsive to GC/FID.
2-22
-------
concentrations in the exhaust air doubled. Unit #1 concentration changed
from 1,000 ppm to 2,100 ppm and unit #2 concentration changed from
1,200 ppm to 2,500 ppm. The second check was a no flow situation with
the inlet blower system off. The no flow situation was monitored for
one hour. The results were identical in both units. The concentration
dropped to 1,000 ppm; but increased to 3,000 ppm as the headspace
concentration in the IAF units forced the mass concentration through the
outlet exhaust vent.
The general results of the species analysis are relatively consistent.
The major components were methane and C6 to C8 components. The results
of these analyses can be used to calculate a non-methane hydrocarbon
emission rate, but these calculations were not performed for this report.
2.2 PROCESS WATER ANALYSES
Tables 2-17 through 2-21 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
(C7-C30) and VOA 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 Phillips 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
2-23
-------
TABLE 2-17. LIQUID ANALYSES FOR PROCESS SAMPLES ON TEST DAY 9/20/83
PHILLIPS PETROLEUM - SWEENY, TEXAS
Liquid Composite and Grab
IAF #2-out-D
IAF #l-out-C
lAF-inlet-A1
CPI-3-in (1700)
CPI-2-out (1700)
CPI-2-out (1700)
CPI-3-in (1700)
Void of Air Samples
CPI-2-out (1813)
IAF #2-out-C (1830)
CPI-3-in (1700)
lAF-in-A (1830)
IAF #2-out-C (1030)
CPI-2-in (1700)
lAF-in-A (1030)
CPI-l-in (1700)
CPI-3-out (1700)
IAF #2-out-D (1830)
IAF #l-out-C (1030)
COD Oil /grease
TRW No. mg/1 mg/1
Samples
5404 539.3 40.6
5405 628.4 150.1
5406-A' 4221.8 3059.5
5407 2061.4 1065.1
5408 681.2 69.6
5410 2267. 1 121. 0
5412 2810.7 339.9
5366
5367
5368
5369
5370
5371
5372
5373
5374
5375
5376
TOC
mg/1
502.5
308.5
205
478.5
107
664.5
358
478.5
204
138
229.5
2-24
-------
TABLE 2-18. LIQUID ANALYSES FOR PROCESS SAMPLES ON TEST DAY 9/21/83
PHILLIPS PETROLEUM - SWEENY, TEXAS
Liquid Composite and Grab
CPI-3-out (0930)
CPI-2-in (0945)
CPI-l-in (0945)
lAF-in-A1
IAF #2-out-D
IAF #l-out-C
CPI-2-inlet (0945)
CPI-1-out (0930)
CPI-3-out (0930)
Void of Air Samples
CPI-l-in (1600)
CPI-3-in (1600)
CPI-2-in (1600)
CPI-2-out (1600)
CPI-3-out (1600)
CPI-1-out (1600)
CPI-2-inlet (0945)
IAF #2-out-D (1445)
IAF #l-out-C (0855)
CPI-1-inlet (0945)
lAF-in-A (0855)
IAF #2-out-D (0855)
CPI-2-outlet (0930)
CPI-3-outlet (0930)
CPI-3-inlet (0945)
IAF #l-out-C (1445)
IAF- in- A1 (1445)
CPI-1-outlet (0930)
COD Oil/grease
TRW No. mg/1 mg/1
Samples
5409 1991.0 269.6
5411 2149.1 267.4
5413 2697.8 687.7
5414 1476.6 126.0
5415 2300.7 34.2
5416 1369. 5 58. 0
5417 1042.7 40.5
5418 2114.8 168.3
5419 2395.0 209.4
5353
5354
5355
5357
5358
5359
5361
5365
5377
5378
5379
5380
5381
5382
5383
5384
5385
5386
TOC
mg/1
310
259
250
157.5
198
549
36
218.5
129.5
155.5
237
226.5
223.5
194.5
451.5
242
278
262.5
2-25
-------
TABLE 2-19. LIQUID ANALYSES FOR PROCESS SAMPLES ON TEST DAY 9/22/83
PHILLIPS PETROLEUM - SWEENY, TEXAS
Liquid Composite and Grab
CPI #3-outlet (0930)
IAF-in-Al
IAF-#l-out-C
CPI-#l-inlet (0940)
CPI-#l-outlet (0930)
CPI-#3-inlet (0940)
CPI-#2-inlet (0940)
CPI-#2-outlet (0940)
IAF-#2-out-D
Void of Air Samples
CPI-#3-outlet (0920)
IAF-#2-out-D (0920)
CPI-#2-outlet (1600)
CPI-#2-inlet (1600)
CPI-#2-inlet (0930)
IAF-#l-out-C (0920)
IAF-#l-out-C (1600)
lAF-in-A1 (0920)
CPI-#l-outlet (0920)
CPI-#2-outlet (0920)
CPI-#l-inlet (1600)
lAF-in-A1 (1600)
CPI-#3-outlet (1600)
IAF-#2-out-D (1600)
CPI-#l-outlet (1600)
CPI-#3-inlet (1600)
CPI-#1- inlet (0930)
CPI-#3- inlet (0930)
COD Oil /grease
TRW No. mg/1 mg/1
Samples
5420 3000.5 232.5
5421 2941.7 262.8
5422 1312.9 152.3
5423 1811.2 32.1
5424 3400.2 705.3
5425 2290.5 31.7
5426 2065.1 34.8
5427 5045.2 4293.6
5428 1140.3 74.4
5348
5349
5350
5351
5352
5356
5360
5362
5363
5364
5387
5388
5389
5390
5391
5392
5393
5394
TOC
mg/1
192.5
410
80
199.5
302.5
366
688.5
531.5
146.5
194.5
166
274
242.5
335
396
210.5
297
208
2-26
-------
TABLE 2-20. LIQUID ANALYSES FOR PROCESS SAMPLES ON TEST DAY 9/23/83
PHILLIPS PETROLEUM - SWEENY, TEXAS
Liquid Composite and Grab
CPI-#3-outlet (1000)
lAF-in-A1
CPI-#l-inlet (0930)
CPI-#2-inlet (0930)
CPI-#3-outlet (1000)
CPI-#3-inlet (0930)
CPI-#l-outlet (1000)
CPI-#2-out1et (0930)
IAF-#2-out-D
IAF-#l-out-C
Void of Air Samples
CPI-#3-in (1000)
CPI-#l-outlet (1000)
lAF-in-A1 (0900)
CPI-#2-outlet (1000)
IAF-#2-out-D (0900)
IAF-#l-out-C (0900)
CPI-#3-outlet (1000)
CPI-#l-in (1000)
CPI-#2-in (1000)
TRW No.
Samples
5429
5430
5431
5432
5433
5434
5435
5436
5437
5438
5395
5396
5397
5398
5399
5400
5401
5402
5403
COD
mg/1
1503.3
160.9
1604.4
29194
1352.2
1135.2
2230.3
2354.4
1927. 6
1910.7
Oil/grease
mg/1
469.4
250.0
107.4
10617
90.0
48.3
405.6
336.2
21.2
26.6
TOC
mg/1
204.5
105
224.5
444.5
248
225.5
251
107
153.5
2-27
-------
Table 2-21. C,. TO C7 SPECIATION BY GC/FID PURGE AND TRAP
PHILLIPS PETROLEUM, SWEENY, TEXAS
TRW Date
no. Sample no. taken Run
5372 Phi llips-A'-VOA- 1030 9/20/83 1
2
5369 Phi llips-A'-VOA- 1830 9/20/83 1
? 2
ro
00
5370 Phillips-C-VOA-1030 9/20/83 1
2
5367 Phi llips-C-VOA- 1830 9/20/83 1
2
5375 Phi llips-D-VOA- 1830 9/20/83 1
2
5368 Phillips-CPI 03-IN-VOA-1700 9/20/83 1
2
Concentration
Compound (in ppb)
C6H6 2100
C6H5CH3 2160
C6H6 2040
C6H5CH3 2010
C6H6 2470
C6H5CH3 2700
P~H~ 99M\
v>gng ££.OVJ
r u PU Odin
LgnsLnjj tHJLU
P H 'i'm
o 6 wwxj
/* M r»ij CA C
Lgngun3 OHO
r» M C*>O
Lgng O^lc
p^u^ru,, 401;
w A 1 IQV| 1 Q • J W
CgH6 1940
/* M r»i| OOTA
1*6115^113 £.£-/\J
P^H^ 17QO
L*gng x/ «/u
C6H5CH3 2110
C6Hg 1850
C6H5CH3 2190
C6H6 1740
C6H5CH3 2020
C6H6 1080
Cu ru 1Q7n
gn5wr13 J.3/U
C6H6 1130
C6H5CH3 2480
(continued)
-------
Table 2-21. Continued
TRW Date
no. Sample no. taken Run
5379 Phi llips-VOA-IAFA1 -0855 9/21/83 1
2
3
5377 Phillips-VOA-IAF-C-0855 9/21/83 1
2
ro
i
ro
^ 5384 Phillips-VOA-IAF-C-1445 9/21/83 1
2
5381 Phillips-VOA-CPI #2-OUTLET 9/21/83 1
2
3
4
5382 Phillips-VOA-CPI 03-OUTLET 9/21/83 1
2
Concentration
Compound (in ppb)
C6H6 2270
r u ru "3(\oi\
I>gn5l*n3 OUcU
C6H6 2080
C6H5CH3 2600
C6H6 1770
CM fuj oocn
gnitUno £*3DU
C6H6 1910
CgHsCHj} 2500
CgHg 1890
p u PU oyi£n
LgncUtlg £*tDU
*j
C6H6 2090
C6H5CH3 2500
C6H6 1870
Cu /»M oocn
ensLns coOU
C6H6 7060
c u f*u "7ocn
Lgri5Ln3 / jDU
C6H6 5442
C6H5CH3 6240
C6H6 5060
P U P14 £QQA
Ugn5On3 uo^U
C6H6 4390
C6H5CH3 4890
P H 7Q4
L»gng / y^
Cu PU T ton
61)50113 J.DJU
C6H6 697
/» u pu 1 O7fl
Lgn5l/n3 J.O/U
(continued)
-------
Table 2-21. Concluded
TRW Date Concentration
no. Sample no. taken Run Compound (in ppb)
5360 Phillips-C-VOA-1600 9/22/83 1 C6H6 1450
C6H5CH3 2090
2 C6H6 1380
C6H5CH3 2030
5363 Phillips-CPI #1-VOA-OUT-0920 9/22/83 1 C6H6 1760
/* u PU TQOft
Ugn5L>n3 ±;)L.\J
2 C6H6 1390
Cu ru i^7n
gnsLtlg J.J/U
K> 5392 Phillips-CPI 03-INLET-VOA-1600 9/22/83 1 C6H6 447
i p u pu n7n
co LgM5l>n3 1J./U
2 Cgng jo4
CU PU "IC/I
cncUna /Dt
5389 Phillips-CPI 03-OUTLET-VOA-1600 9/22/83 1 C6H6 537
CM CU flflA
grlsLns oo't
2 CgHg 488
CfiHcCHo 840
5399 Phillips-D-VOA-0900 9/23/83 1 C6H6 636
C U PU QA7
v^gngwng ,?*TO
2 C6H6 601
:H, 942
5396 Phillips-CPI #1-OUT-VOA-1000 9/23/83 1 C6H6 2170
C6H5CH3 2340
2 C6H6 2120
2290
-------
immediate analysis (24-48 hours) due to the expected 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.
Process water samples for test day 9/22/83 were used for an analysis
on the integrity check on sampling methods. Table 2-22 provides the
results comparing liquid VGA and composite sample. Table 2-23 provides
the results comparing liquid VGA and grab samples.
2-31
-------
Table 2-22. GAS CHROMATOGRAPH RESULTS FROM LIQUID VGA AND
COMPOSITE SAMPLES AT IAF SAMPLE LOCATIONS - 9/22/83
PHILLIPS PETROLEUM - SWEENY, TEXAS
SAMPLE
LOCATION:
TYPE SAMPLE:
TIME:
IAF
IN-A1
Composite
IAF
IN-A'
VOA
0920
IAF#1
oirr-c
Composite
IAFI1
OUT-C
VOA
0920
IAFI2
OUT-D
Composite
IAF#2
OUT-D
VOA
0920
Purge & Trap
Analysis (mg/1)
Benzene!* 0.80
Toluene 1.44
Extraction
Analysis (mg/1)
Benzene 0.85
Toluene 0.72
C-9 22.27
C-10 5.38
C-10 10.30
C-ll 1.24
C-12 0.98
C-13 <0.50
C-14 <0.50
C-15 <0.50
C-16 <0.50
C-17 1.48
C-18 4.02
C-19 6.10
TOCC
1.81
2.62
1.22
1.70
1.58
2.53
1.19
1.91
<0.50
0.77
40.96
8.54
18.07
1.66
0.86
<0.50
<0.50
<0.50
<0.50
1.22
3.20
4.71
<0.50
0.66
44.14
9.02
19.16
1.72
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
1.64
2.25
1.52
2.21
1017
954
678
737
427
419
-
Purge and trap results for benzene and toluene are prefered over the extraction
results, because of the potential for losing benzene and toluene during the
extraction and concentration steps associated with the extraction method.
Extraction analysis performed on composite and grab samples only.
c Duplicate analysis performed.
2-32
-------
ro
is
Table 2-23. GAS CHROMATOGRAPH RESULTS FROM LIQUID VOA AND GRAB SAMPLES
AT CPI SAMPLE LOCATIONS - 9/22/83, PHILLIPS PETROLEUM - SWEENY, TEXAS
SAMPLE
LOCATION:
CPIil
OUT,
TYPE SAMPLE: GRAB
TIME:
0930
CPIil CPII2
OUT OUT
VOA GRAB
0920 0930
CPIi2
OUT
VOA
0920
CPU 3
OUT
GRAB
0930
CPII3
OUT
VOA
0920
CPIil
IN
GRAB
0940
CPIil
IN
VOA
0930
CPII2
IN
GRAB
0940
CP1I2
IN
VOA
0930
CPII3
IN
GRAB
0940
Purge & Trap
Analysis
Benzene"
Toluene
Extraction
Analysis'
Benzene
Toluene
C-8
C-9
C-10
C-ll
C-12
C-13
C-14
C-15
C-16
C-17
C-18
C-19
TOCC
(mg/1)
2.480
2.920
(mg/1)
0.75
1.68
<0.50
-
-
-
<0.50
<0.50
<0.50
<0.50
<0.50
1.44
4.12
5.60
871
961
1.580 0.008
1.650 0.070
t
-b 0.75
1.20
<0.50
-
<0.50
.
-
<0.50
<0.50
<0.50
<0.50
1.11
3.20
4.40
179
195
8.920
8.350
_b
-
.
.
-
-
-
-
-
•R
.
_
-
-
_
-
1.270
0.114
0.56
0.70
0.46
-
<0.50
<0.50
0.65
2.26
0.67
0.59
<0.50
2.13
4.00
5.51
1116
1007
0.863
1.170
_b
.
-
.
.
_
-
-
.
.
.
_
-
-
.
-
0.284
1.850
<0.50
<0.40
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
773
788
0.891
1.470
.b
.
_
.
-
_
_
_
.
.
.
-
_
-
.
-
0.423
0.091
1.62
<0.40
<0.50
<0.50
<0.50
<0.60
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
912
802
0.199
0.044
_b
-
-
-
-
.
.
.
.
-
.
-
-
-
_
-
0.522
0.146
2.77
<0.40
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
<0.50
1005
902
Purge and trap results for benzene and toluene are prefered over the extraction results, because of the potential for
losing benzene and toluene during the extraction and concentration steps associated with the extraction method.
Extraction analysis performed on composite and grab samples only.
Duplicate analysis performed.
-------
3. PROCESS DESCRIPTION
3.1 PLANT DESCRIPTION
The Phillips refinery in Sweeny has a crude throughput capacity of
175,000 barrels per calendar day (b/cd). The Effluent Guidelines Division
of the Environmental Protection Agency (EPA) places Phillips in refinery
subcategory C which includes refineries producing petroleum products by
the use of topping, cracking, and petrochemical operation. Phillips has
recently added new process units which enable the refinery to process
sour, heavier crudes. These new process units include an atmospheric
crude distillation unit, a distillate hydrodesulfurization unit, an
atmospheric residuum desulfurization (ARDS) unit, a heavy oil cracking
unit, and sulfur recovery facilities. Additional wastewater treatment
facilities were added to handle wastewater produced by these new units.
The induced air flotation systems tested at Sweeny were part of the new
wastewater treatment facilities.
The charge rates for the units listed above are given in Table 3-1.
These charge rates are for the days on which emissions testing was
conducted. Design charge rates for each unit are also provided in the
table.
3.2 REFINERY WASTEWATER SYSTEM
The refinery wastewater system at Phillips consists of two separate
oil separation facilities. Wastewater generated in the older sections
of the refinery is first treated by dual API separators which are followed
by air flotation systems. The air flotation systems are converted API
separators which have been equipped with air diffusers. Wastewater
generated by the new process units is treated in three corrugated plate
interceptor (CPI) type separators which are followed by two IAF systems.
Effluent from the old and new wastewater systems is then combined before
-------
Table 3-1. UNIT CHARGE RATES DURING TEST PERIOD
Process unit
(unit #1)
Crude (25.1)
Hydrodesul f uri zat i on
(25.2)
Atmos. residuum
desulfurization
(26.1)
CO
rJj H2 purification
(26.2)
Heavy oil cracking
(27.1)
Wet gas (27.2)
Sulfur (28.2)
9-19
105,600
28,800
Down
a
105 MMCFD3
43,200
22,200
201 LT/Db
Unit charge
9-20
105,600 105
28,000 28
'
Down
104.6 MMCFD
43,200 43
22,000 22
63 LT/D
(barrels/day
9-21
,600
,000
Down
110 MMCFD
,200
,320
71 LT/D
unless noted)
9-22
116,700
31,495
50,610
122 MMCFD
47,688
23,592
190 LT/D
9-23 Design rate
130,000
50,000
72,000 75,000
192 MMCFD
50,000
27,500
35 LT/D
aMMCFD - million cubic feet per day.
LT/D - long ton per day.
-------
being further treated by biological processes. The wastewater treatment
system serving the new process units will be described in further detail
below.
3.2.1 New Wastewater Treatment Facilities
Wastewater in each of the new process units is collected in a
process drain system. Water from the unit drains flows to a separate
junction box associated with individual process units. Wastewater is
pumped from the junction boxes to the CPI separators.
As shown in Figure 3-1, wastewater from each unit is designated to
one CPI. However, the CPI's are interconnected allowing the flow to
equalize between the three units. The CPI's were manufactured by
Pielkenroad of Houston, Texas and are completely closed tanks. Each CPI
has an observation port which allows for visual inspection of the unit.
Wastewater flow to the CPI's is intermittent and dependent on water
flow to the junction boxes. The junction boxes are equipped with level
control devices which trigger the pumps when the boxes become full.
Therefore, surges in wastewater flow to the CPI separator occur regularly.
In addition to process unit wastewater, wastewater from other
sources is treated by the CPI separators. Wastewater from the contaminated
water ponds, catalyst disposal area, alkyl sludge ponds, and oily solids
area is also pumped to the CPI's.
Wastewater from the three CPI separators converges into a flash mix
tank. The flash mix tank is a concrete structure that is completely
covered. An uncovered overflow tank is located next to the flash mix
tank and can be used to handle extreme surges in wastewater flow. The
purpose of the flash mix tank is to control the pH level of the wastewater
and to serve as a mixing tank for chemical coagulant addition. The
addition of coagulant enhances oil and suspended solids removal in the
IAF systems.
From the flash mix tank, wastewater splits into two parallel IAF
systems. The lAF's were installed by U.S. Filter and are designed to
treat 1100 gallons per minute of wastewater. Each IAF is 32 feet long
and 8 feet, one inch wide. By design, wastewater retention time would
be 4 minutes in the IAF.
3-3
-------
CO
•£»
Atmospheric Distillation (2S.I) .
Distillate llydrodesulfurliatlon (2S.2)
— 1
Atmospheric Residual Desulfurliatlon (26.1]
Heavy Oil Cracking (27.1)
Sulfur Recovery (28.2)
—— J
1 Additional Uastewater Sources to
II) contaminated water ponds
2) refinery disposal area (
I- catalyst disposal
- alky sludga .1
i - oily solids
1
|
._»~- - - .
'
'
~~ v r i
•fc r t I
t
CM Separators
(enow* MX (RUN) ,
350 gpm)
•
I
-^^ I A r ^ .
Fl.th
*" Hlx ""^" >* llologlcal TreaUujnt
! i
1 f* t n t f"] '
DAF Makeup Treated Wastewater fro*
water as needed Dissolved Air Flotation
(ISOflgpMMx) Syste*
1
1
1
1
1
1
|
Figure 3-1. Wastewater treatment system for new process units.
-------
Figure 3-2 shows a U.S. Filter "Hydrocell" IAF similar to that used
at Phillips. Figure 3-3 shows the flow pattern of water in each cell of
the unit and also the mechanism by which air is introduced into the
system. The Hydrbcell has four flotation cells, plus inlet and outlet
compartments. In the Hydrocell IAF, a portion of the treated wastewater
is recycled through the distribution header to each air induction assembly.
The recycled water draws air or gas into the liquid by means of the
venturi effect. The Hydrocell does not use external blowers or pressurized
gas to produce aeration.
Skimmer mechanisms located in each cell remove floating oil and
suspended solids. Water level is controlled in the outlet compartment
by a pneumatic level controller. Five inspection doors are located on
each side of the unit to allow for observation of IAF operation. The
inspection doors remain closed during normal IAF operation.
The two IAF systems at Phillips were designated as the North and
South units. Observations made during the test period found that the
operation of the two systems varied. The water level in the South unit
remained consistently higher than the North unit. The South unit appeared
to be more effective in skimming floating oil and solids from the surface
of the cells. The water level in the North unit was too low to allow
for proper skimming. Therefore, a substantial sludge layer developed on
the surface of the water. Periodically, this sludge layer would rise to
a level where skimming was possible.
The North unit was also experiencing problems draining the sludge
collected in the side launders. For this reason, a steam line was
placed in one side launder to prevent clogging by the sludge. This
caused the temperature inside the North unit to be slightly higher than
the South unit.
3.2.2 Additional Wastewater Treatment Facilities
Effluent from the IAF systems combines with effluent from the DAF
system of the older wastewater treatment facilities. This wastewater
then enters a series of aerated ponds. Following the aerated ponds,
biological treatment is accomplished by rotating biological contactors
(RBC). The RBC units are followed by a clarifier, two stabilization
ponds, and filters. Effluent from the filters is discharged to the
Linville Bayou.
3-5
-------
co
en
Inlet
1 reclrculatlon of wastewatcr
to flotation colls"
skinning,mechanism
and side launder
access door
level control
outlet
Figure 3-2. Induced Air Flotation System, "Hydrocell" designed by U.S. Filter.
(Source: U.S. Filter Fluid System Corporation - Flotation General Catalog)
-------
side . .
launder
gas drawn down
standpipe from vapor space
recirculated wastewater
skfnmer
Figure 3-3. Flow pattern of gas and water in IAF system cell.
(Source: U.S. Filter Fluid Systems Corp., Flotation General Catalog)
3-7
-------
Auxiliary wastewater facilities have been mentioned above. These
include the contaminated water ponds, catalyst disposal area, alkyl
sludge ponds, and oily solids ponds. These facilities store waste from
specialized areas of the refinery and produce small quantities of
wastewater. For example, spent catalyst fines are sent to the catalyst
disposal area. The catalyst fines settle out, leaving the surface water
to be drawn off and treated by the newer wastewater facilities.
3.3 MONITORING OF WASTEWATER TREATMENT FACILITIES
Phillips monitors a number of pollutant parameters to insure
compliance with the refinery NPDES (National Pollution Discharge
Elimination System) permit. Among the parameters monitored are: total
organic carbon (TOC), pH, ammonia, sulfides, oil and grease, fluorides,
and chromium. Data regarding these parameters were not acquired from
Phillips during the test. However, the test plan required that samples
be drawn to measure TOC and oil and grease concentrations to and from
the IAF systems.
During the test period, monitoring of wastewater flow to the IAF
systems was accomplished by observing instrument readings in the control
room of the wastewater treatment facility. Flow meters in the control
room provided estimates of flow to each of the CPI separators. Because
flow to the separators was intermittent, the meters often were reading
"0." Table 3-2 summarizes the flow readings observed during the test
period. The flow rates were calculated by recording the meter reading
at an instantaneous time and correcting by a factor given by Phillips
for each meter. Applying the correction factor to the instantaneous
reading gave measurements in gallon per minute (gpm). Readings were
taken as often as possible, usually every one to two hours during each
day of testing.
The data shown in Table 3-2 do not provide an accurate estimation
of wastewater flow to the IAF systems. A stripchart in the control room
recorded flow from the flash mix tank to the IAF. Again, instantaneous
readings were recorded on the chart and these readings often indicated
zero flow. The stripchart reading generally coincided with the flow
reading for the CPI separators.
3-8
-------
Table 3-2. ESTIMATED WASTEWATER FLOW RATES TO
CPI SEPARATORS DURING TEST PERIOD
Wastewater
flow in
gallons
per minute (GPM)
Estimated flow to separators
Date
9-20-83
9-21-83
9-22-83
9-23-83
Time
0900
1025
1035
1045
1100
1125
1140
1205
1450
1513
1530
1715
0900
0901
0925
0930
0935
1030
1105
1145
1325
1705
0900
0925
0930
0935
0945
1015
1215
1450
1455
1604
1610
1655
0925
0945
1130
1240
1205
1325
1330
CPI-1
345
331
331
0
0
331
0
0
552
0
0
345
276
621
276
538
593
276
331
552
290
1035
207
621
276
207
179
621
759
152
621
442
731
179
0
0
0
552
552
538
593
CPI-2
304
274
262
0
0
274
0
0
0
0
0
274
192
411
0
425
438
178
205
643
192
247
0
480
192
0
0
480
589
0
493
219
589
0
0
0
0
356
370
562
562
CPI-3
291
260
281
0
0
281
0
0
114
0
0
459
177
364
187
406
416
177
135
364
0
20
0
21
21
0
0
135
239
0
125
0
291
0
0
0
0
125
52
270
270
Total flow
940
865
874
-
-
886
-
-
666
-
-
1078
645
1396
463
1369
1447
631
671
1519
482
1302
207
1122
489
207
179
1236
1587
152
1239
661
1611
179
-
-
-
1033
974
1370
1425
3-9
-------
As mentioned above, the water level in the IAF systems was monitored
throughout the test. Visual inspection of the water level in each IAF
was made periodically on each day of testing. The submersion depth of
the skimmer bars was used as a reference point to determine changes in
water level. In general, these water levels remained consistent in each
IAF during the test period. Operators at Phillips adjusted the water
levels on the initial day of testing to insure proper operation of the
units during the test. Only slight fluctuations were observed.
3.4 PROCESS UPSETS AND IRREGULARITIES DURING TEST
Consistent fluctuations in the concentration of VOC recorded by the
continuous monitoring equipment were noted throughout the test period.
One possible explanation for these fluctuations is the intermittent flow
of oily wastewater to the CPI separators. As noted above, oil wastewater
is pumped to the CPI separators from junction boxes located in each
process unit. Pumping is dependent on the amount of wastewater generated
in the process units. According to plant personnel, when the pumps are
engaged, normal pumping times are roughly 17 to 20 minutes in duration.
This time interval agrees with peak wastewater flows recorded on
stripcharts in the control room. Further, peak VOC concentrations also
appeared to coincide with these time intervals.
Water levels remained constant in the IAF systems despite fluctuation
in the flow to the CPI separators. Flow to the IAF systems could be
supplemented by effluent from the IAF system located in the older treatment
system. Therefore, fluctuations in quantity of wastewater in the lAF's
were not observed. However, the quality of oily wastewater could fluctuate
dur to the intermittent flow from the CPI separators.
During the first three days of testing (9-19 to 9-21), the atmospheric
residuum desulfurization (ARDS) units was not being charged. Preparation
activities to bring this unit back on line began at approximately midnight
on September 22. Plant records indicate that full operations of this
unit began at 04:20 of that day.
3.5 ADDITIONAL NOTES REGARDING WASTEWATER TREATMENT SYSTEM
• Wastewater generated by desalter in Unit 25.1 is treated by
the older wastewater treatment system. This was due to an
effort to hasten startup of the new crude unit. The new
wastewater treatment system was not complete when the unit was
first charged.
3-10
-------
• According to Phillips personnel, Units 25, 27, and 28 would
have the highest potential for producing wastewater high in
VOC content. Unit 26 (ARDS) would have lowest VOC potential
of the new units.
• Major maintenance procedures in process units are carried out
during mid-evening shifts. Large quantities of wastewater may
be produced during this time period (3:00 p.m. to 11:00 p.m.)
due to routine maintenance practices.
• Total wastewater flow from the refinery is approximately
3850 gpm. This flow is measured as the flow rate to the
rotating biological contactors.
3-11
-------
4. LOCATION OF SAMPLE POINTS
This section presents a description of the sampling locations
within the process at Phillips Petroleum in Sweeny, Texas. An explanation
is provided of the sample point maintained at the gaseous sampling
location for continuous monitoring, gas bag sampling, and flow measurement.
Figure 3-1 presents a diagram of the petroleum wastewater system with
the IAF treatment process units and sample locations.
4.1 GASEOUS SAMPLE LOCATIONS
The gaseous sample locations -t the IAF #1 and IAF #2 outlets were
fabricated to provide a measurable gaseous flow through the IAF units.
Figure 4-1 provides a schematic of the IAF system and shows the
configuration of the blower system to introduce a ventilation air to the
IAF unit's headspace. Figure 4-2 illustrates the fabricated ductwork
and the sampling location at the outlet of IAF #1 and IAF #2.
In attempt to create a closed system so that only the outlet
ventilation air would have to be measured, weatherstripping and tape was
used to seal the inspection doors. However, since some doors had to be
accessible for maintenance and adjustment of the unit, a closed system
could not be continually attained.
4.2 WATER SAMPLE LOCATIONS
The process water sample locations were the same as those used by
Phillips to collect plant process water samples. Figure 4-3 provides a
diagram of the sample locations within the process.
Figure 4-1 provides a schematic of the sample locations at the IAF
units. The sample location IAF-A1 was the common process line feeding
both IAF #1 and IAF #2 (see Figure 4-3). IAF-C and IAF-D sample locations
were maintained at the recirculation pump to the two separate units.
-------
TOP VIEW
I
INJ
FMNMMD
NIX TANK
H.O/AIR INJEaiOHS
'
INTEGRATED BAG * THC MONITOR
TEST POINT
PURGE AIR BLOWER
P
IAF- C
EXHAUST
AIR
H20/AIR INJEaiONS
fi • n n n
i 11 i
INTEGRATED BAG & THC MONITOR TEST POINT
NMILE UBORATORY
EXHAUST
PUMP
IAF - 0
HEATED SAMPLE LINES FOR
CONTINUOUS THC ANALYZERS
IAF II . SOUTH
I IIOLDGICAL TREATMENT
II- NORTH
SIDE VIEW
r4
END VIEW
T
r \
K-,
1
Figure 4-1. Schematic representation of the IAF process with sample points
and induced air system: Phillips Petroleum - Sweeny, Texas.
-------
END VIEW
CO
4" FLEXDUCT TO ANEMOMETER,
THEN TO EXHAUST
TEaON LINE TO INTEGRATED
BAG SAMPLING UNIT
FABRICATED METAL REDUCING
COLLAR INSERTED IN PLACE
OF REMOVED IAF DOOR
DOOR REMOVED
HEATED SAMPLE LINE TO
THC ANALYZERS
IAF UNIT
Figure 4-2. lAF-outlet sample locations fabricated:
Phillips Petroleum - Sweeny, Texas.
-------
INLET H,0 SAMPLE
I
FROM CRUDE
CPI f 1
•£
t
OUTLET H20 SAMPLE
INLET H20 SAMPLE
1
FROM STORM DRAINS ^ ^
CPI 1 2
.
t
OUTLET H20 SAMPLE
INLI
1
1
FROM FCC ^
* ^
rr H2o SAMPLE
CPI 1 3
•»
^-
t
OUTLET H20 SAMPLE
PH ADJUSTMENT
•5
•^
| PURGE AIR IN
1
\l/
IAF I 1 - SOUTH
I
OUTLET AIR SAMPLE)
1
^
C • OUTLET HjO S
V
-5j
A'- INLET H20 SAMPLE
'
**
1 PURGE AIR IN
M/
IAF f 2 - NORTH
1
<
'
•
TO AERATED PONDS
^
0 • OUTLET HjO S
y
f OUTLET AIR SAMPLE
SAMPLE
I
Figure 4-3. CPI separator processes with process sample locations: »
Phillips Petroleum - Sweeny, Texas.
-------
Figure 4-3 provides the locations of the sample points around the
CPI separators. The CPI-inlet sample points were sample valves from the
process line feeding the CPI separators. The CPI-outlet sample points
were sample valves from the process sample piping to a Phillips sampling
facility.
4-5
-------
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.
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
-------
Probe
5' Teflon Tubing
Pinch Clamp
en
i
ro
Grommet
A1r Tight Steel Drum
Sample Bag
PVC Tubing
Directional
Needle Valve
Quick Disconnectors
TCMIP8"
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-Cg components) was a Shimadzu GC Mini 1 with a Shimadzu Chromatopac
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 C^-C5 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. Figures 5-3
and 5-4 present an example of GC/FID analysis runs for C!-C5 speciation
at the IAF sample locations.
The GC/FID analysis example run for Cj-Cs speciation (Figure 5-3)
provides an illustration of problems in the analytical procedures.
Standards were not available to provide elution time standards for all
peaks identified by the GC/FID. Therefore, the total organic concen-
tration 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 operator noted the temperature difference
5-3
-------
STflRT 89.21.17.22.
16.26
STOP
-Ki.l
i^PL »
RI-PT »
METHOD
n
1
2
3
5
88
6
1688
44
NftME TIME
C-l 8.57
C-2 8.82
C-3 1.3
2.63
6.3
f-5 7.13
£rC 16.26
TOTflL
^ —..
CC
13.3842
18.4426
11.2547
18.7832
45.7849
MIC
V
flP-.fl
1888
251
399
568
749*
778
722
5261
Figure 5-2. Example of GC/FID calibration for
speciation.
5-4
-------
SBUTH-4-1438
STftRT 89.21.15.32.
5.67
6.63
7.5
1 STOP
C-Rlft
SMPL ft
FILE #
REPT ft
METHOD
89
6
1678
44
#
1
2
3
5
NAME
C-l
C-2
C-3
C-5
TIME
9.24
9.6
9.83
1.32
2.32
2.73
5.67
6.63
7.5
TOTflL
CONC
55.7426
5.2292
3.9738
5.8931
78.8389
V
V
V
V
V
V
V
RREfl
163
7542
126
141
178
551
1975
1995
367
11242
Figure 5-3.
Example of GC/FID analysis on IAF unit #1 exhaust air
gas bag sample for C:-C5 speciation.
5-5
-------
N0PTH-5-1050
STPRT 99.22.12.11.
~l
C-R1R
SMPL *
PILE *
pCpT £
METHOD
t
3
4
5
00
A
1701
44
WftMF TIME
C-1 0,6
C-2 0.84
C-3 1 . 39
2.54
3O4 3.91
6.48
C-5 7.64
8.68
TnTflL
CONC
^6.' 2414
5.4103
46.5562
391.5484
V
V
V
V
64R
5750
6943
1 53R
99838
Figure 5-4.
Example of GC/FID analysis on IAF unit #2 exhaust air
gas bag sample for Cj-C5 speciation.
5-6
-------
in the field laboratory across a test day and adjusted the peak labels
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.
t 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 prepared from
liquid mixture of hexane, heptane, and toluene, were used to determine
the retention time for these compounds. Figure 5-5 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. Figures 5-6 and 5-7 present an example of
GC/FID analysis runs for C6-C9 speciation at the IAF sample locations.
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 Beckman
Model 402 and a Beckman 400 flame ionization analyzer were used at the
IAF sample locations. The sample probes were placed near the centroid
of the fabricated outlet duct of the unit to be sampled. A continuous
tSt
sample flow was maintained through heated Teflon sampling lines. The
instrument operating parameters was:
5-7
-------
CRL-PBX-45PPH
STflRT 99.21.17.98.
0.9
3.46
3.63
STOP
C-Rlfi
SHPL *
FILE #
REPT *
METHOD
09
4
1686
44
# NRHE TIME
1 PR0PRN 8.9
2 BENZEN 1.46
3 XVLENE 3.63
TOTftL
CONC MK flREfl
46.3155 1849
50.5438-^-1 3294
52.2691 -V«i 5594
149.1195 19558
Figure 5-5. Example of GC/FID calibration for C6-C9 speciation.
5-8
-------
S8UTH-3-1180
STflRT 99.21.11.24.
7.41
8.34
9.21
STOP
C-Rlfl
SMPL #
FILE #
REPT *
METHOD
88
5
1664
41
HOME
8
8
8
8
8
8
8
8
8
8
8
8
8
8
TIME
8.89
,02
,25
,56
,99
2.33
2,
3,
4.
4,
,88
,48
,11
,68
5.34
7.41
8.34
9.21
TOTflL
CONC
10.3662
10.4288
16.184
19.6886
5.3847
13.8817
3.1757
2.867
8.5664
2.8875
1.6188
3.89
0.4509
1.4251
99.9999
HK
V
V
V
V
V
V
V
V
V
V
V
V
V
flREfl
4578
4594
7135
8688
2374
6128
1488
1264
. 3776
1273
718
1362
198
628
44089
Figure 5-6.
Example of GC/FID analysis on IAF unit #1 exhaust air
gas bag sample for C6-C9 speciation.
5-9
-------
STftPT 99.22.11.47.
i •>•?
19.97
12.87
STQ!»4.27
C-Rlfi
SMPL *
FILE »
P.EPT »
METHOD
44
1 PPRpflN
2 8EHZEN
3 XVLENE
3 XVLENE
TIME
1.02
1.22
1.52
1.8ft
2.22
2.64
3.17
4J24
4.77
6.47
7.17
8.PI
9.27
12ip7
14.27
CONC
124.1267
288.1822
74.6997
19.168
V
V
V
V
V
V
V
V
V
V
V
v
V
V
V
V
flppfl
4714
6373
18815
11577
551B
6*63
*99p
597
Qfl4
•5B6.176R
Figure 5-7. Example of GC/FID analysis on IAF unit #2 exhaust air
gas bag sample for C6-C9 speciation.
-------
Site: IAF unit #1 exhaust air
• 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.
Site: IAF unit #2 exhaust air
• Analyzer: Beckman Model 400.
• Serial #: 100216
• Fuel Pressure: 22 PSI.
• Sample Pressure: 3.0 PSI.
• Air Pressure: 15 PSI.
• Sample line length/approximate temperature: 25 feet/ambient.
The analyzer 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 Speciality
Gases and certified to within ±2 percent of the labeled calibration gas
values. The calibration gas standards used at Phillips 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
5-11
-------
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. The operational parameters and calibration
gas standards used at the IAF sample location were as follows:
• Instrument: Beckman 402 and Beckman 400.
• Scale: 0-5,000 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 15-20 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.
Test periods before a 12-hour instrument operation period, required the
two-hour drift check frequency.
5-12
-------
Figure 5-8 presents an example of a calibration check at the IAF
unit #1 sampling location with a recalibration required. The sequence
was initiated at 0850 on 9/22/83 by introducing zero, high, and mid-
calibration gases separately. The upward drift at the three levels was
approximately two 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
ranged from 900-2000 ppm. Therefore, the 1002.5 ppmv as C3H8 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 0-5,000 ppm scale. Therefore,
the IAF calibration was performed with 80 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 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
The assumption was maintained that the process gas permanent
constituents are at ambient levels because the induced ambient air was a
major portion of the process gas. This permitted a modification of
permanent gas analyses instead of EPA Reference Method 3. The permanent
oxygen level was assumed to be 21.8 percent with the remaining portion a
balance of the monitored THC level and nitrogen.
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 across the IAF units was created by a dual blower
5-13
-------
T
Figure 5-8. Example of a calibration check with
a recalioration required.
5-14
-------
fabricated into an inspection door. A small, constant flow was forced
across the IAF unit with the inlet pump and the sealed doors. An exhaust
outlet was fabricated for measuring the exhaust air. The system used
was based on a four-inch diameter anemometer housed in a section of
exhaust 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
exhaust air and the fabricated outlet duct. Figure 4-2 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 on the anemometer.
The blower generated flow rate across the IAF unit was constant and
total volumetric measurements were not required. Monitoring of the flow
rate was maintained at the inlet and outlet ducts. The differences in
the inlet and outlet flow rate was used for determining the integrity of
the sealed IAF unit.
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" (VGA) 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 five to six 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,
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;
5-15
-------
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
of organic components. This phenomenon is apparent after the TOC analysis
of theoretically identical samples in which one was collected in a VOA
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.
5-16
-------
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.
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
5-17
-------
vapor space and does 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/Qua!ity 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.
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 0 & G gives a precision of 7.9, or
almost double the precision of the COD readings.
5-18
-------
Table 5-1. REPLICATED COD AND OIL AND GREASE MEASUREMENTS
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
Means
0 & G COD 0 & G
mg/L mg/L mg/L
491 3238 513.0
535
453 4119 444. 7
440 '
441
382 2135 379.0
376
133 1748 133.5
144
125 1565 115.0
94
126
110 1271 109.5
109
123 1891 121. 5
120
Standard
Deviation
COD 0 & G
mg/L mg/L
381.8 31.1
102.6 7.23
29.0 4.24
0.0 0.71
20.0 18.2
43.1 0.71
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
-------
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-Cllf C^-C^ and C17 to C25 hydrocarbons. Due to the
reduced response on a FID of C17 to C2s hydrocarbons as compared to
C7-Cu high values of some C17-C25 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
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
5-20
-------
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 sample was drawn.
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 DAF, respectively are
5-21
-------
ro
ro
109.9-
RIC
UHIH1 ftttUb II
CM.Il 8923 14
K1C
09/26/83 17i57i88
SAMPLE: TRHI5057+758NG BFB
RANGE* c 1,1 eee uwa« N e, 4.e OUAHI A e, i.e BASEI u 20. 3
613
iu 1MW
260
6i4fl
886
26140
2339291
1080 SB»
33129 TIME
Figure 5-9. Mass spectrometer qualitative analysis by purge and trap, sample no. IAF-INLET-VOA-0740.
-------
RIC
ro
co
16:49100
SANPLEi TRWI 5e66
-------
en
i
ro
• u
— M
a
U!»
IU
a
45
t*rlM luimyvftto. caltt p ;i 03 9063ft? (Ml
Figure 5-11. GC/FID quantitative analysis by purge and trap, sample no. IAF-INLET-VOA-0740.
-------
*
"I
en
i
po
01
— M
O
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
Compound
C2H6S2
C6H6
C6H5CH3
BFB
In-house
Standard
ppb
—
352
348
596
Replication
I
ppb
240
187
502
863
2
ppb
227
174
519
927
TRW
No.
3
ppb
198
142
441
927
Sample No. 4973
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
* Ar-r-im.-i™ - 905.7~596 v inn - C1 QV
596
% Precision = pooled CV for compounds in Sample No. 4973 = 9.6%.
5-26
-------
Table 5-3. PRECISION/ACCURACY ESTIMATES FOR IAF/DAF SAMPLES
In-house
Compound Standard
C6H2S2, ppb —
C6H6, ppb —
C4H10S2, ppb —
C6H6CH3, ppb —
BFB, counts 170417
IAF, TRW #4987 DAF, TRW #4994
1
939
1970
411
5710
143078
2
943
1770
410
5020
164324
CV 1
0.0030 —
0.3860 2120
0.0017 —
0.0909 2110
0.5370 135529
2 CV
— —
1980 0.0483
— —
2000 0.0379
139579 0.0208
For IAF:
For DAF:
- 170417 - ((143078 + 164324)72)
170417
170417 - ((135529 139579)/2)
x 100 =
Accuracy «
Precision:
Pooled CV for IAF = + 29.8%.
Pooled CV for DAF = + 3.7%.
, „
5-27
-------
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 arid 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.
5-28
-------
APPENDIX A
SAMPLE CALCULATIONS AND RESULTS
• Flow and Emission Rate Calculation
Examples
t Summary Gas Analysis Sheets
t Continuous Monitor Results
-------
APPENDIX A
EXAMPLE CALCULATIONS
Example #1 IAF - Flow Measurement with Vane Anemometers
Ftan 9
Va« (CFM) = -r^"- X Area Ft*
an mm an
Van X 17.64 X P.
V (SCFM) -(-SJU-- b->
(Example of flow measurement calculation during IAF #2-Inlet run on
9/22/83 at 943.
Van Run 9-22 (CFM) = X .0873 ft2
54.1 CFMan
- i 54.1 X 17.64 X 30.54
- ( 68
=55.2 SCFM
SCFM = standard cubic feet per minute
V _ = volume measured through vane anemometer
an
V = volume standardized to standard temperature and pressure
P. = barometric pressure
T = temperature of stack gas
-------
Example # 2 Mass Emission Rate for VOC as C.HD
J O
(A) Sample calculation to3provide the conversion factor of
C,H from ppm to mg/m
44.g \ ( * "K^e \ i 28.32 L * , 35.31 ft3 x , 1000 mg
~ - - - -
.
o 25.71 L 3 - - 3 - ' - g
, mg/m >
10 ppm
1.71 mg/m
(B) Emission rate » Ib/hr
= ( VOC ppm ) ( ^lJ!!i , ( f3 , ( ^_ } ( 60jnin
mj 35.31 ftj min hr
1000 453. 6g
Example - of Emission Rate calculation on IAF #2 9/22/83 run at 0948
c = f ioAn nrm \ f 1-71 mg > / m , / 50.85 ft > / 60 min
Evnr ' ( 3240 ppm ) ( —3—=- ) ( j } ( ——r- ) ( hr
voc mj 35.31 ftj min nr
v 1000 mg ' v 453.6 g
1.05 Ibs/hr
-------
Davis Anemometer Correction Chart
BAVB usTHMim •?•. w, MR.
BUM. NO.
June If i
TTK • •AU.UAJUWO
TRUE
9t».
30
M
TO
«0
100
200
100
400
MO
MM
TOO
MO
«00
1000
1300
1400
IMO
wnurtg
rtM.
it
M
S3
- T5
ts
1M
2W
400
MS
•10
TIS
120
m
1030
I23S
1441
«*>»
nut
rut.
IMO
2000
2300
2400
3MO
2»00
3000
3100
3400
3400
3*00
4000
4200
4400
4400
4*00
MOO
HMCATID
ffM.
IMO
204S '-
22TS
34*0
IWM
3*10
1130
333S
S3M
STU
S*T»
4IM
43*0
4S*S
4MO
M»
1340
-------
SUMMARY GAS ANALYSIS SHEETS
-------
OWMONMSMTAt INGINEEHING DTVtSlON
SUMMARY GAS ANALYSI
COMPONENT RUN
'*
C-l
5" 7. S
C-2
C-3
C-4
J±+
/AT-
75,2
AZ
C-5
12^.
$ s. ?
BENZENE
/MS. 2
7s./
31. I
j£L
ILL
(,!-,ۥ
. r
TOTAL
HC
XH
C02
X CO
% N?
0?
% CH4
TOTAL X
-------
TRW
SUMMARY GAS ANALYSIS
COMPONENT RUN
C-l
C-2
C-3
C-4
C-5
¥•/.?>
BENZENE
/, /
d *.!«».•
d *.!«».•»/ C
/Ye.
5?. 7-
/o.O
TOTAL
XM
C02
CO
N?
2 0?
X CH4
TOTAL %
I Wo
-------
TRW
tWmONM£NTAt tNGMEERING DIVISION
SUMMARY 6AS ANALYSIS
COMPONENT RUN
C-l
/67.3k
C-2
JZ^L
C-3
C-4
C-5
BENZENE
122.^-
lanu
//$./
UL
XYLENE^r.^
TOTAL
_%M
% C02
% CO
% N?
g 0?
g CHa
TOTAL
HC
-------
•mw
BMHQNMWTAL fWQWfMJNG O/VWCW
StWMARY GAS ANALYSIS
COMPONENT RUN
C-l
C-2
C-3
C-4
3-S
C-5
BENZENE
-7"
» a ».ii«?. vfc.*
TOTAL
g C02
I CO
8 N?
2 0?
X CH4
TOTAL
-------
CONTINUOUS MONITOR RESULTS
-------
TRW
\
LOCATION
* I -
POLLUTANT TMC
DATE
INSTRUMENT RANGE (PPM) Q-SOQO
Record Data Every 3-5 Minutes
Time
noo
18oo
HOD
Z000
7.1 oo
^^oo
1300
Scale
Reading
30.3
31.2.
2?.o
2&,Z
2S.^
Zl. 5
21. q
•
ppm
1MSI.9
1536,?
1320.0
12.^1.0
12.S0.3
10^0. "3
10SM.1
CALIBRATED BYP*u<-ft J
Time
cale
Reading
NOTES:
-------
TRW
LOCATION ±4P » >>5euHk POLLUTANT Y \\ C- DATE_^
INSTRUMENT RANGE (PPM) O>SOOO CALIBRATED BY 0*««jftj /)A/
Record Data Every 3-5 Minutes^
-------
TRW
LOCATION 14 P * \-
POLLUTANT Tl)e_
DATE Q-7J-83
INSTRUMENT RANGE (PPM)_
Record Data Every 3-5 Minutes*
40U.
Scale
Time I Reading
n
'
O
^/*
Mo.Q
I «L i fa * VP .
mo.2
CALIBRATED
T* kt.rfy
Time
C*oo
(fcoo
(100
1000
"L\oo
tloo
T300
Scale
Reading
40.7
3S,?
33.9
2^.9
25.1
25.2
2C.7-
ppn
"20Z2.5
192S.O
/6^/.S
HJ3V. I
IZH3.S
I2^?.S
I3Z/.^
NOTES:
-------
TRW
LOCATION *3l4f
POLLUTANT
DATE
INSTRUHENT
Record Oat
Time
Onon
Of On
O-LOo
£&OQ
O^Oo
OS oo
0600
0^-00
o%rcr>
O*no
fOoo
Uoo
17,00
1 ^0 O
ft/00
I £OO
* feoo
RANGE (PPM) O-S000 CALIBRATED W Om~.fi, J {).„***
B Every 3-5 Mi
Scale*
Reading
35.T
35.3
t/L/.?
S0.9
Sl.j^
56.9
te.s
60.3 •
58.?
65.9
H?.?
Mo.fe
MQ.6
^.T
m.o
43J
93.Z
nutes i>Co«»
pprn
!7?2.3
t-J 5W W
2223.lt
2S33.5
26 JS.S
2^34. 1
-3U0.4
3002.*^
2923.^
335?.?
^S5.3
1&&M
2Zfo.6
23??.q
zos^.o
•ZI90.5
2I23.S
*K>t*y
« . / i
rC KOUM /y
Time
(^fiO
* 8 r7 O
( 4 tf C?
1 000
1100
2100
Z3o0
Scale
Reading
t/O.T.
33.0
33.6
30.1
23.7
*36.$
42,2
— i
ppr
j»jm
\t>\*.o
It,
-------
TRW
\
its
LOCATION ± A F lfc 1 -Se..«/L POLLUTANT >U^_ DATE c^7.3-&3
INSTRUMENT
Record Dat<
Time
OOflO
0(0o
OlOn
OV00
OSoo
Q6oo
0?c?o
O^rto
(?9(5O
lOOrj
1/00
ILOO
1^00
RANGE (PPM) D-9000
i Every 3-5 Mi
Scale
Reading
31. S
2^.9
-23.7
23.3
18,?
17.7
13.9
20. V'
21.0
2V.O
21.1
42.V
S2.Z
61,3
nutes
-------
TRW
LOCATION XAF
POLLUTANTTHC
INSTRUMENT RANGE (PPM) Q «» SOOO
____ DATE q
CALIBRATED BY Ofttf*.P«ul
Record Data Every 3-5 Minutes^ c.*igeicW T«
Time
1^00
JBOO
1100
2.OOO
2.1 00
Z200
Z300
AOV.
Scale
Reading
23.0
20.4
ZI.H
22.3
22. G
23.9
2c,8
•
pprn
115M.2
IOZM.8
I0?3.9
IH8.S
U35.3
m^.H
1042.0
Time
Scale
Reading
ppr
NOTES:
-------
TRW
\
LOCATION TAP ttZ - Afon-t-k POLLUTANT T WC,
DATE Q-2I-S3
INSTRUMENT RANGE (PPM). O-BOOO
CALIBRATED
Record Data Every 3-5 Minutes + CMUUA.W 1*0 Uunly
Time
oooo
01 00
02.00
03oo
OSoo
0600
0*700
IOOO
• ^Jfi^e
1^00
ifco o
Scale
Reading
23.0
28.8
30.8
32.5
3S.3
3G.I
32.3
* e? uT •*• (
HM.9
ppm
II5I.6
IHHS.2
1356.2
I526.H
152.5.^
15H6.0
I63H.2
155^.3
IGio.S
Time
(Soo
"iooo
"ZZOO
I'boo
Scale
Reading
3^.9
33.9
30.0
ppr
^W •^ 9 ^ » "
27^0.^
NOTES:
-------
TRW
LOCATION £ A F fr 2. -
POLLUTANT T H C
DATE
INSTRUMENT RANGE (PPM) O
Record Data Every 3-5 Minutes
CALIBRATED BY flwe-A J Cky/w
c»Mo««.t*«/ >o kouit/y
Time
0000
0(00
0100
030O
oc/oo
0500
0600
07-00
OSOO
O^OO
(0 CO
lIC? 0
\T-0 0
1300
Wrto
1500
Ifcoo
Scale
Reading
-5C. 9
Ml. 3
H8.0
56.0
£3.5
72.1
76.3
?7.a
73.0
G5.9
6S.7
60.3
£5.^
60.7-
55.0
59.9
55.?
ppm
J?
-------
TRW
\
LOCATION !TAF *Z -/¥. a
POLLUTANT T U C
INSTRUMENT RANGE (PPM) Q-(
Record Data Every 3-5 Minutes + c
Time
Oooo
0100
03OO
OMOO
OSon
OCoo
070O
OSoo
0*500
1 Ooo
UDo
12,00
40V.
Scale
Reading
2S.9
21. S
11.6
21.5
^5.3
2S.9
53.1
ppm
1055.0
1053.8
673.1
25^.0
DATE q-23-33
CALIBRATED BY
Time
Scale
Reading
pp
NOTES:
CUT
; UoA
-------
APPENDIX B
FIELD DATA SHEETS
-------
IAF Anemometer Measurements
-------
TRW
Vs\ \*^£
^° ^^^ FLOW MONITORING
LOCATION lAf1 Nltfl 6.-^™) INSTRUMENT A^^^trt* DATE' 9 (zo
a^c^^
os&f
FAr*.
^trO
wz
pctft
\j*
RUN NUMBER BY
RECORD DATA EVERY (Jho MINUTES
'Time
c o
^-OC7
/0*o
7^0
a AI
2.4-^
1- U.,^0!
Oc^O
WO
9-:o>
|4oo
'*«»
•53*^° <
Anemometer
Reading
c<=
^30, ~,0
77»
^ 5**T/^
fC 2AP
i*
C^'o
"BAc«Lt^CC
^& C^
^^ "•'^^'7 £3 "N
\ ^ . •»• ^
/o3eo
nno
&VO
*
Temperature
9/V
91^
9^
y,v
^
-------
TRW
LOCATION 1 ft Ffslo/
RUN NUMBER
FLOW MONITORING
INSTRUMENT
BY T
DATE
-------
TRW
LOCATION 3ft F- I -
FLOW MONITORING
INSTRUMENT
DATE i(
RUN NUMBER p^U Xl»/t iuto_T4P BY T- Su^~*
to-cO
/s-x?,->
_.T
2^-00
30-.^
NOTES:
?RJLV»^
Anemometer
Reading pr
9otfov ^
/134^^
/ S-4ff of J
/ yK W^TTl
' ^' 1 -*'•« f f*CJ
2/uro
2 ST£4C
'2_ 8 9^
• 30.^3 •
Temperature
S-eV
fcoV
60*P
^•p •
toV
W
€tf'^ :
L
•»$ ,4-25-
Time
^:c,o
5-,*^
/c ;oc^
/^-«o
-c:^o
i^'Oo
z.,.Cc,
Anemometer
Reading fT
ftlOG
//43C7
J
/ V *2o
2.3285-
273fcO
5 /4Z5-
Temoerature
•70°p
7ccF
70 V
70 V
72^.
74ZTP
70^
70 °P
•*-\
-------
TRW
FLOW MONITORING
LOCATION "TAP-I.-oT
DATE
6-rwrTi*
t*&4
D O: C&
*•:<*
io ca
If.W
2»»
^^^
Anemometer
Reading PT
75flo
^/SJ ^
/ ««* ^
/ Z4oc'
^^
Temoerature
€,^P
es'F
•S5°^
04-1*
12£>
^Hff
O&r v^
t'-OO
/*..«
ir:oo
Z <3 •-*>
-------
TRW
LOCATION
RUN NUMBER
FLOW MONITORING
INSTRUMENT
BY
DATE
RECORD DATA EVERY 5-10 MINUTES
fe<4«.i»>
Time
0^
0
20 •• O o
V>--c-
4 £>:£>£>
NOTES:
/?M^fc»
Anemometer
Reading fT
*-/(>
1360 .t.,.
/en*"
X
27025-
ir?7o
.rn*c
&£<->&£ -3t»-
Temperature
^-f
*4*
^p ^T
^0c9 r^
t,1°F
a^
,»
TJ'me*'^
CVJ
r.'.*4-
/e-ot»
^>0
,'^D]OO
( „-,
Anemometer
Readi no ^T
55#"
74S-0
IPZ70
/^5 •'i "? O
' (r. \ a •* 3
_••
**
Temperature
7«_"F
7:T>
•7s>
75*?
7s'*F
-------
TRW
LOCATION
RUN NUMBER
FLOW MONITORING
INSTRUMENT
BY
DATE
RECORD DATA EVERY
nob
(MINUTES
•+•** Vfc*-
**mf
e>o
^'00
IO:oD
/3T--50
Anemometer
Reading P
9/66...,,
/«&«>,^.
/ 2^50^^
TrZV
/ 46 f £7
B
*F
Temperature
10?*J=
f*Z~f
to*°e
UZ°F
i*i«» •»!«.
*H» «*»*-"»
Time
oo'oo
5 *Z
f«» c-i
I^'O
Anemometer
Readinq Pf
C.|^d
7*7^0
fs-sr>
11,122
I
°F
Temoerature
\\\*F
»x«°F
il\°r
(c^?cr
NOTES:
76 *
-------
TRW
LOCATION
FLOW MONITORING
*^1N5TRUMENT
DATE _£
RUN NUMBER
BY -3-
RECORD DATA EVERY 5-10 MINUTES
Z,: -
Time
'00
2.0 : 33
Anemometer
Reading
Temperature
72
Time
// -
Sff-'CZ-
Anemometer
Reading
Temperature
76
76°**
ZOO
NOTES:
67"?
-------
TRW
LOCATION
No^ 5oor«
RUN NUMBER
oon-27"
FLOW MONITORING
INSTRUMENT
BY ^
DATE
RECORD DATA EVERY 5-INUTES
&*
©0
j"^rf'C)"i~r^7 fl-rnr/i^
^j
Anemometer
Reading PT
Temperature
Time
3^
Anemometer
Readinq
Temperature
NOTES:
-------
TRW
FLOW MONITORING
J^\.«f LOCATION X^Fuo/ SO-TW INSTRUMENT A*s*~~>~ DATE 7/23/£3
1 . /J IS ,f
f*\^s • *i
!/*^
^own^e
i <'^
T . ~
i ^**^
^ vl^
RUN NUMBER Fr.o«^ ^ BY
RECORD DATA EVERY 5-10 MINUTES
Time
DO
2*: 2^
srs-/
/7-- /<
46 «s-
Anemometer
Reading
X'ilfc
^Soo
^r^,
7
^r^o
.-
Temperature
n%*F
n^
-------
TRW
^o
LOCATION
RUN NUMBER
MONITORING
INSTRUMENT
BY 4".
DATE:
RECORD DATA EVERY /5>10 MINUTES
*n*: *>tc.
Time
GO
fT.-/r
/DiO^
i$'0o
tO\ 00
25'vo*?
SOiOC
Anemometer
Reading ^"f
1000, . -
.*• y^J>
4005*^
* 0ASnt(J
^TT»W
^ 55"*
«3«j-'(>r
v*.ij^
\2,335-
'^'^.^
**?<»
*•
»F
Temperature
73°^
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APPENDIX C
ANALYTICAL DATA
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Example of Continuous Monitor Stripchart With
Calibration Check - IAF #2 (North) Outlet
Sample Location on 9/22/83
-------
NWRTH-5-l8.se
5TPPT 89.22.12.11.
1
C-Rlfl
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PILE *
R'EPT *
METHOD
2
3
4
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8, Aft
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4A.5562 V
V
381.5404
Example of GC/FID Analysis on IAF #2 (North)
Gas Bag Sample for C-C Speciation
-------
99.22.11.47.
18.87
12.97
SNPL «
ritE »
PEPT »
METHOD
4
9
44
« HRHE
1 PRBPRN
2 8EMZEN
3
XVLEME
TTME
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1.22
1.52
1.88
2.22
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9.27
14.27
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288.1822
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v
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V
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4714
11577
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Example of GC/FID Analysis on IAF #2 (North)
Gas Bag Sample for C-C Speciation
-------
APPENDIX D
SAMPLING METHODS AND ANALYTICAL TECHNIQUE
-------
503 OIL AND GREASE
In (he determination of oil and grease.
an absolute quantity of a specific sub-
stance is not measured. Rather, groups of
substances with similar physical charac-
teristics are determined quantitatively on
the basis of their common solubility in tri-
chlorutrifluoroethane. "Oil and grease" is
an> material recovered as a substance sol-
uble in trichlorotriftuoroethane. 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
mo»t industrial wastewaters or treated ef-
fluents containing these materials, al-
though sample complexity may result in
either 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
wastewater or treated effluents, they mat
cause surface films and shoreline deposit-
leading to environmental degradation.
A knowledge of the quantity of oil and
grease present is helpful in proper desigr
and operation of wastewater treatment
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 remou
operations of the gravimetric procedure
Method C is the method of choice *hr
relatively polar, heavy petroleum fra.
lions are present, or when the leveN »''
nonvolatile greases may challenge the v
ubility limit of the solvent. For low le^e'-
of oil and grease (< 10 mg'L). Method 6 ••-
the method of choice because gravimetr..
methods do not provide the needed pre-
sion.
Method D is a modification of the Sox
hlet Method and is suitable for sludgo-"^
similar materials. Method E can be useJ "'
-------
OL & GREAS&P«««oiv6nMRwMeMt«wd
461
conjunction with Methods A. B. C. or D to
attain 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
OB the basis of polarity.
3. Sampling and Storage
Collect a representative sample in a
•ide-mouth glass bottle that has been
nosed with the solvent to remove any de-
terrent film, and acidify hi the sample
bottle. Collect a separate sample for an oil.
and grease determination and do not sub-
divide in the laboratory. When informa-
tion is required" about 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 with 1 mL
cone HO/80 g sample. Never preserve
samples witn
or sodium benzoate.
503 A. Partition-Gravimetric Method
1. General Discussion
a. Prim-iplr: Dissolved or emulsified oil
nd grease is extracted from water by in-
tonate contact with trichlorotrifluoro-
ethane. Some extractables, especially
Htsaturated 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: TrichJorotrifluoroethane
bat the ability to dissolve not only oil
aid grease but also other organic sub-
stances. No known solvent will selectively
dissolve only oil and grease. Solvent re-
•oval 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 extractabie with the solvent.
i Apparatus
«, Separator) funnel. \ L. with TFE*
stopcock.
A. Distilling flask. 125 mL.
r. Water bath.
d. Fitter paper. 11 cm diam.t
3. Reagents
a. Hydrochloric acid. HO. 1*1.
A. Trichlomtrifluuroethanet (1,1.2-tri-
chloro-I^.2-trifluoroethune). boiling point
47 C. The solvent should leave no measur-v
able residue on evaporation: distill if nee-/
essary. Do not use any plastic tubing to
transfer solvent between containers.
r. Sodium sulfute. Na,SO4. 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
tFma or tqutvtleitt.
-------
462
ORGANIC CONSTITUENTS (500)
is suspected thai a stable emulsion will
form, shake gently for 5 to 10 min. Let lay-
er* 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'/V^iJrr
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:
cr>Mals. Add more Na.SO4 if necessary.
Extract twice more with 30 mL solvent
each hut first rinse sample container with
each solvent portion. Combine extracts in
tared 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 with an applied vacuum for the
final I min. Cool in a desiccator for 30 min
and weigh.
mg oil and grease/L -
(A - B} x i.OOO
mL sample
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 I-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
a. 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 tudrocarbons. 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.
t. 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. Separatory funnel. I L. with TFE
stopcock.
b. Infrared spectntplwlimieier. double
beam, recording.
c. Cells, near-infrared silica.
J. Filler paper. 11 cm diam.*
3. Reagents
a. HyJriK-hlnrir aciil. HCI. I * I.
h. Trii-hkmarifimmteihune. See 503A.V1
r. SiHlium xulftite. Na«SO4. anhydrous.
crystal.
•Teflon or equivalent.
twtutman No. 40 or equivalent.
-------
Oft. ft GREASESosMM Extraction MMhod
463
4. Referrnre nil: Prepare a mixture, by
volume, of 37.5Q iso-octane. 37.5SF hex-
•dccane. and 25*7 benzene. Store in
tcaled container to prevent evaporation.
4. Procadure
Refer to Method A for sample collec-
tion, acidification, and extraction. Collect
combined extracts in a 100-mL volumetric
fhsfc and adjust final volume to 100 mL
»ith solvent.
Prepare a stock solution of known oil by
rapidly Transferring about 1 mL (0.5 to 1.0
fi 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
K unknown if If) use the reference oil
i' Ul as the standard. Using volumetric
technics, prepare a series of standards
over the range of interest. Select a pair of
mulched near-infrared silica cells. A 1-cm-
ptth-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~' 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 cor* 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.
Calculation
Big ofl and grease/L
A x I.QOO
mL sample
where:
A » ing of OB or grease in extract as deter-
mined from calibration curve.
6. Precision and Accuracy
See S03A.6. By this method the oil and
grease concentration was 17.5 mg L.
When I-L portions of the sewage *ere
dosed with 14.0 mg of a mixture of No. 2
"fuel oil and Wesson oil. the recovery of
added oils was 99£c with * standard devia-
tion of 1.4 mg.
503 C. Soxhlet Extraction Method
1. Genera) Discussion
•. Principle: Soluble metallic soaps are
kxtfrolyzed by acidification. Any oils and
MjJid or viscous grease present are sepa-
rated from the liquid samples by filtration.
*fter extraction in a Soxhlet apparatus
•rth trichlorotrifluoroethane. the residue
remaining after solvent evaporation is
•eifhed to determine the oil and grease
awtem. Compounds volatilized at or be-
** 103 C will be lost when the filter is
feed.
*• hterference: The method is entirely
«pirical 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 tiltrable 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
a. Kxtrurtinn iippiirutiia. Soxhlet.
/>. \iniitini i>ninp or other source of
vacuum.
c . flin Inn r funnel. \2 cm.
J. Klcfirif liciitinf! mantle.
i. K\tnntii>n thiinhlf. paper.
1. I'ilter paper. llcmdiam/
y. \tn\lin tintli ilixlks. II cm diam.
3. Reagents
il. H\dr,ti liltirit- tifiil. HG. 1 + I.
/>. Tritlili>nitritiiuinn-tlninr: See503A.3/>.
«•. ftititiHiitireiimt-xilicti .filler uid xiis-
/>«•«.%/«»«.* 10 g. L distilled Muter.
4. Procedure
Collect about I L of sample in a wide-
mouth glass bottle and murk sample level
in KM tie for luter determination of sample
volume. Acidify to pH 2 or lower: general-
ly . 5 mL HCI is sufficient. Prepare u filter
consisting of u muslin cloth disk overlaid
with filter paper. Wet paper and muslin
and press down edges of paper. Using u
vacuum, pass 100 mL filter uid suspension
through prepared filter and wash with I L
distilled water. Appl> vacuum until no
more water passes filter. Filter acidified
sample. Apply vacuum until no more wa-
ter passes through filter. Using forceps.
•Whatman No 40 or equivalent.
Super-C'd. Johni-Manullf 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 und w eigh.
5. Calculation
See Section 503A.5.
6. Precision and Accuracy
See Section 503A.fr. By this method the
oil and grease concentration was 14.8 me
L. When I-L portions of the sewage were
dosed with 14.0 mg of a mixture of No 2
fuel oil and Wesson oil. the recover) of
added oils was 88r? with a standard devia-
tion of I. I mg.
503 D. Extraction Method for Sludge Samples
General Discussion
a. Principle: Drying acidified sludge by
healing leads to low results. Magnesium
bining with 75r/ of its own weight in water
in forming MgSO, 7H:O and is used to dr>
sludge. After drying, the oil and grea>e
can be extracted with trichlorotrifluoro-
ethane.
sulfate monohydrate is capable of com- h. Interference: See 503C. l/».
-------
gift GREASE/HyOocvtoons
465
I Apparatus
i. Extraction apparatus, Soxhlet.
k. Vacuum pump or other source of
vacuum.
r. Extraction thimble, paper.
d. Grease-free cotton: Extract non-
^sorbent cotton with solvent.
1 Reagents
g. HydriH-Moric acid. HO. cone.
4. Magnesium sulfate monoliyjrute:
Prepare MgSO4-H.O by overnight drying
of a thin layer in an oven at 150 C.
r. TmUifnvrijiminteiluine: See 5Q3A.36.
4. Procedure
In a 150-mL beaker weigh a sample of
vet sludge. 20 a 0.5 g. of which the dry-
•atids content is known. Acidify to pH 2.0
neutrally. 0.3 mL cone HG is sufficient).
Add 25 g MgSO< HzO. 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
po»der 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-
fluoroethane. 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. Race flask
on a water bath at 70 C for 15 min and
draw sir through it using an applied vacu-
um for the final I min. Cool in a desiccator
for 30 min and weigh.
5. Calculation
Oil and crease as C? of dry solids
pin in weight of flash, g x 100
weight of »et solids, g x dry solids fraction
6. Precision
The examination of six replicate sam-
ples of sludge yielded a standard deviation
of4.6Cf.
503 E. Hydrocarbons
1. Significance
In the absence of specially modified in-
dustrial products, oil and grease is com-
peted 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
lite difficulty in determining the major
source of the material and simplifies the
correction of oil and grease problems in
•astewater treatment plant operation and
Mnam pollution abatement.
2. General Discussion
u. 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.
h. 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)
499
itction 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 end Accuracy
In a series of interiaboratory studies.
each involving «i to 102 laboratories (and
as man) river water and wastewater
seedsi. 5-dav BOD measurements were
nuJeon synthetic water samples contain-
ing a 1:1 mixture of glucose and glutamic
*.-ui in the total concentration range of 5 to
.VtO mg L. The regression equations for
mean value. T. and standard deviation. 5.
from these studies were:
T • O.M>5 liidded level, mg D - 0.149
5 - O.i:0 (added level, mg L) - 1.04
For the 300-mg L mixed primary standard.
the average 5-dav BUD was 199 4 mg L
»nh a standard deviation of 37.0 mg L.
8 References
I Y.HNG. J C. IT9. Chemical methods for
•dnfication control. J. \\iiu-r P,tUni. Control
hJ 4.V63T
I I.S.
rv. OFFICE or RESEARCH A
MINT. EsVIROSMtNTAL M«)SITO«INf, &
Si'PTORi LABORATORY. CIM ISSATI. OHIO.
1978. Personal communication. D.W. Bal-
linger to G.N. McDermoil.
9. Bibliography
r. h.J.. P.D Me NAVIM & C'.T
Bi IURIIH i>. 1931. Selection of dilution
water for use in oxygen demand tests. Puh.
Ht-iilih K,-r 4* IOW.
Li A. W.L. & M.S. Nu HOLS 1937. Influence of
phosphorus and nitrogen on biochemical
oxygen demand. Sr»nnf H,;ri< J. 9:34.
RUHHOH. C.C. 1941. Repon on the coopera-
tive study of dilution waters nude for the
Standard Methods Committee of the Fed-
eration of Sewage Works Associations.
St-HUgr Ui'rli J. 13:669.
SAW\»R. t'.V & L BHAPMV l»4ft Modem-
ization of the BOD test for determining the
efficiency of the se»age treatment process.
Sfoagr H,>rl*J. 18:1113.
RUHHOIT. C C".. O.K. HLAI AK. J. KAI HM»H
& C.K. C AI •( Hi. 1948. Variations in BOD
velocity constant of sewage dilutions. Intl.
Lny. Cllem. 40:1290.
ABBIHI. W.K. I94t(. The bacteriostatic eflects
Of methylene blue on the BOD test. ».*/• r
5<-»«i'i- W. "it 95:424
MOHIMAS. F.W.. R. Hi«v\iT7. C R. BAK-
%m & H.R. RAVI*. 1950 Experience
with moditied methods for BOD Si-uauf
ln,l M«.»;i-« 22:31.
C.N.. P. t'M I »JAS. M. M«H»«I i
A 0 V. TOM. 1950. Pnmarv standards for
BOD work. Si-»iu'< In
508 OXYGEN DEMAND (CHEMICAL)
The chemical oxygen demand (COD) is
a measure of the oxygen equivalent of the
orpnic matter content of a sample that is
M»weptible to oxidation by a strong chem-
wJ oxidant. For samples from a specific
">urce. COD can be related empirically to
BOO. organic carbon, or organic matter
1 Selection of Method
The dichromate reflux method is pre-
ferred over other methods using oxidants
because of superior oxidizability. appli-
cability to a wide variety of samples, and
ease of manipulation. The test is most use-
ful for monitoring and control, especially
after correlations with constituents'- such
as BOD and organic carbon have been de-
veloped. For most organic compounds
oxidation is 95 to IWi of the theoretical
value.1-' Pyridine is not oxidized.*' Ben-
zene and other volatile organics are oxi-
-------
490
ORGANIC CONSTITUENTS (500)
di/ed if they have sufficient contact with
the oxidants.- While the carbonaceous
portion of nitrogen-containing organic
nutter » oxidized, no oxidation of am-
monia, either present in a waste or liber*
ated from the nitrogen-containing organic
nutter, takes place in the absence of sig-
niticant chloride concentration*.
2. Sampling and Storage
unstable samples without delay.
Homogenize samples containing settleabk
•old* hi * blender to permit representative
sampling. If there jjjp JbCLA delay before
analysis, preserve lrje sample.by acid-
ification to pH 2 or lower with cone sulfu-
TJC -acflj THjSOj.. Make preliminary dilu-
tions lor wastes containing a high COD to
reduce the error inherent in measuring
small volumes of sample.
508 A. Dichromate Reflux Method
i Genera) Discussion
K. 1'ii'h /;>/<•: MOM types of organic mat-
ter are oxidi/ed h\ a boiling mixture of
chromic and sulluric acids. A sample is re-
lluxcd in strong! > acid solution with a
kmmn excess of potassium dJchromate
tK.Cr.Ori. After digestion the remaining
unreduced K.X-'r.O- is titrated withjerrous
umrno.oium luUatc t£AS*. the amount of
K.-C'r.-Or consumed is determined, and the
amount of oxidizable organic matter is cal-
culated in terms of oxvgen equivalent.
n. litti-rtrr<.-me\ titiii liiniluium\: Vola-
tile straight-chain aliphatic compounds are
not oxidi/ed to any appreciable extent.
I his failure occurs partly because volatile
oryanics are present in the vapor space
and do not come in contact with the oxi-
dixmp liquid. Straight-chain aliphatic com-
pounds are oxidized more effectively
»hen silver sulfate t Ag;SOi) is added as a
catalyst. However. Ag^SO, reacts with
chlt«ride. hromide. and iodide to produce
precipitates that are oxidized only partial-
ly. The difficulties caused by the presence
of haihJes can be largely, though not com-
pletely, overcome by completing *ith
mercuric swlfate iHg>jO«} before the re-
fluxing procedure.' Do not use the test for
samples containing more than 2.000 my
chloride L.
Nitme (NO- I exerts a COO of I.I my
O.-mg NO.- -N. Because concentrations
of NO;" in polluted waters rarely exceed
I or 2 mg NO; -N L the interference i>
considered insignificant and usually is ig-
nored. To eliminate a significant inter-
ference due to NO..", add 10 mg sulfamn:
acid mg NO.- -N present in the refluxmg
flask. Also add the same amount of sul-
famic acid to the reflux flask containing
the distilled water blank.
Reduced inorganic species such as fer-
rous iron, sultide. manganous manganese.
etc.. are oxidized quantitatively under the
test conditions. For samples containing
significant levels of these species, sioi-
chiometric oxidation can be assumed
from known initial concentration of the in-
terfering species and corrections can be
made to the COO value obtained.
r. Minimum Jrtt-ituhle vttnrvntrutitw
Determine COO values of "--50 mg L using
0.1SXV KjCrjOr. With 0.025\ K;Cr.O-.
COO values from 3 to 50 mg. L can be de-
termined but with lesser accuracy.'
2. Apparatus
Reflux upptiratus. consisting of 500-mL
-------
OXYGEN DEMAND (CHEMlCAU/Dcfromat* tote*
491
or 250-mL erlenmeyer flasks with ground*
glass 2440 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 Wcnv of healing surface, or
equivalent.
3. Reagents
a. Shiiithmlpt>tti**iiim Jifhntmate nnlu~
ti,m. 0.250V: Dissolve 12.259 g KjCrjOj.
prinur) standard grade, previously dried
at 10? C for 2 hr. in distilled water and
dilute to I.OOOmL.
h. Sihrr \iiltiite. Ag;S04. reagent or
technical grade, crystals or powder.
i. Sulfiirir tniil rrsiui-nt: Add Ag.SOi 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. SiiltiirH ,niJ. H-SO,. cone.
r. ferrnin inili\-ut»r \iiliiiiiiii: Dissolve
1.485 g I.IO-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.?
/. SliiHtliirtl ferr,in\ iiiniiiiiniiini xnlfiite
titrunt. approximately 0.25V: Dissolve 98
g Fe(NH,i:iSO,);-6H;O (FASl in distilled
»ater. 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 follow >:
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 titrunt.
using 0.10 to 0.15 mL (2 to 3 drops) ferroin
indicator.
Normality of FAS solution
x 0.25
Volume 0.23.V
solution titrated. mL
Volume FAS u»ed in litretion. mL
•Canuaj JOOO or tqinviltM.
'Cenwj JW). »!54I or c^w
* F. SiMk Chmtcal Co.. CoJum«w. Ohio.
V. .Vrrrnrit Mil fine: HjSO4. crystals or
powder.
/t. SMlfiiinic mill: Required only if the
interference of nitrites is to be eliminated
(see 1 \h above).
i. Potassium hvilrogen phthaliile stan-
dard: Lightly crush and then dry potas-
sium acid phthalate (HOOCC.H,COOKi
to constant weight at 120 C. dissolve 425
mg in distilled water, and dilute to 1.000
mL. Potassium hydrogen phthalate has a
theoretical COO of 1.176 g Oyg and this
solution has a theoretical COD of 500 mg
O,L. Prepare fresh for each use.
4. Procedure
a. Treatment nf Mnnplen with 5.VJ MI.C
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 reflating flask. Add I g
HgSO«. several glass beads, and ver>
slowly add 5.0 mL sulfuric acid reagent.
with mixing to dissolve HgSO*. Cool while
mixing to avoid possible loss of volatile
materials. Add 25.0 mL 0.250V K.Cr,Or
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. C'Atl'lov -W/.V reflux mixture tlinr-
imglily hefiire apphing heat tii prevent In-
<•«»/ heating i»J'tfu\t hnttntn ami a p»t\\ihle
MowiHit of flu\L. t-untentx. If sample vol-
umes other than 50 mL are used, keep ra-
tios of reagent weights, volumes, and
strengths constant. See Table 508:1 for ex-
amples of applicable ratios. Maintain
these ratios and follow the procedure as
outlined above.
Use I g HgSO. with a 50.0-mL sample
to complex up to a maximum of 100 mg
chloride (2.000 mg'L) For smaller samples
use less HgSO,. according to the chloride
concentration: maintain a 10:1 ratio of
HgSO,:CI. A slight precipitate does not
affect the determination adversely. Cener-
-------
492
ORGANIC CONSTITUENTS (500)
Sample
S./*
m/.
100
5t*:l. R| Mil SI
0.25V
Standard
Dwhronuie
ml
V reappear.
Reflux and titrate in the same manner a
blank containing the reagents and a vol-
ume of distilled water equal to thai of
sample.
h. Alli-riitilc prineJurr fttr Im-COD
\t, \. Follow the above procedure.
• JK. with two exceptions: ti) L'se stan-
dard 0.025\ K.Cr^Or. and (//) titrate with
0.025V FAS. Exercise extreme care with
this procedure because even a trace of or-
ganic matter on glassware or from the at-
mosphere may cause gros» errors.
If a further increase in sensitivity is re-
quired. concentrate a larger volume of
sample before digesting under reflux as
follows: Add all reagents to a sample
larger than 50 mL and reduce total volume
to 150 mL by boiling in the refluxing flask
open to the atmosphere without the con-
denser attached. Compute amount of
HgSO, to be added (before concentration)
on the basi* of a weight ratio of 10:1.
HgSO«:Cl. using the amount of chloride
present in the original volume of sample.
Carry a blank reagent through the same
procedure.
This technic has the advantage of con-
centrating the sample without significant
losses of easily digested volatile materials.
Hard-to-digest volatile materials such a*
volatile acids are lost, but an improvement
n gained over ordinary evaporative con-
centration methods.
nj' \tiimliirJ Wnr«i»i
Evaluate the technic and quality of re-
agents by testing a standard potassium h>-
drogen phthalate solution.
5. Calculation
mgCODL
M - g' » .V * *.0"0
mL sample
where:
A • volume FAS ineJ Tor hbnk. mL.
B • volume FAS uteJ for sample. mL.
.V » normality of FAS.
-------
KSTtOOES (OAGANICVOrgvwcNarirM P
493
6 Pnc&on and Accuracy
A set of synthetic samples containing
potassium hydrogen phthaiale and NaCI
mas tested by 74 laboratories.* At 200 mg
COD L in the absence of chloride, the
standard deviation was s 13 mg'L (coeffi-
cient of variation. 6.5%). At 160 mg fODL
and 100 mg chloride/1, the standard de-
viation was ± 14 mg/L (coefficient of vari-
ation. 10.8?,).
508 B. References
I Moo*i. U \.. R. C. KnoNtii & C C.
RUMHOI i. tfen demand lest. Anal. ( it,m
3.VIOM
5. ANAIVTITM. REFEHNCE Stuvirr. USHKW-
PHS. I96.V Oxygen Demand No. :. Sludy
No. 21. Environmental Health Ser. Water.
PHS Publ. No. VW-WP-26.
-------
ORGANIC CARBON, TOTAL
Method 415.1 (Combustion or Oxidation)
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 (COj) 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 Cm 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.
Q insoluble, partially volatile carbon; for instance, oils.
D) insoluble, paniculate carbonaceous materials, for instance; cellulose fibers.
£) 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
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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 Emit 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 100.0ml.
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
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7.5 Carbonate-bicarbonate, standard solution: Prepare a series of standards similar to step
7J.
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:
Precision as Accuracy as
TOC Standard Deviation Bias, Bias,
ing/liter TOC mg/liter % mg/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
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APPENDIX E
TEST LOG
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FIELD LOG
Date
Time
Task Performed
9/19/83
0800
0900
1000
9/20/83
1700
1800
0830
1030
1045
1300
1435
1530
TRW Test Crew and EPA Representatives arrive
at the Phillips Petroleum Facility in Sweeny,
Texas.
Phillips Petroleum Personnel provide intro-
duction and safety meeting.
Crew begins set-up at test location. Con-
tinuous monitor and GC systems fabricated
and lite for warm-up period. IAF #1 (Phillips'
South Process) is prepared for testing by
cleaning, sealing, and installing inlet blower.
The IAF Outlet sample point was fabricated
and installed.
Continuous analyzer (Beckman 402) on-line at
IAF #1 sample location.
Test Crew departs test facility.
TRW Test Crew and EPA Representatives arrive
at the Phillips Petroleum Facility in Sweeny,
Texas.
Liquid VOA and composite samples at sample
locations A1 (lAF-Inlet), C (IAF #1 Outlet)
and D (IAF #2 Outlet).
Preparing IAF #2 for testing.
Leak check with OVA-128 on sealed doors on
IAF #1. Marked leaks and attempted to reseal.
Measured flow at IAF #1 Outlet.
IAF #1 gas bag sample #1.
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Date
Time
Task Performed
9/20/83
Continued
1600
1615
1710
9/21/83
1813
1830
1900
0800
0830
0855
0930
0945
1000
1003
1100
1115
1220
1330
1415
1430
Check air flow from blower to IAF #1. With-
out a backpressure for pump flow and with the
backpressure in-line between the IAF unit and
the blower.
IAF #1 gas bag sample #2.
Continuous analyzer (Beckman 400) on-line at
IAF #2 sample location. Liquid VGA and com-
posite samples at CPI-Inlet #1, #2, #3 and CPI-
Outlet #2, #3. (CPI-Outlet #1 not flowing).
Air flow measurement at IAF #2.
Liquid VOA samples at A1, C, D.
Test Crew departs test facility.
TRW Test Crew and EPA Representative arrive
at the Phillips Petroleum Facility in Sweeny,
Texas.
IAF #2 gas bag sample #1. Air flow measure-
ment at IAF #2.
Liquid VOA and composite samples at A1, C, D.
Liquid VOA and grab sample at CPI-Outlet 1,2,3.
Liquid VOA and grab sample at CPI-Inlet 1,2,3.
IAF #1 gas bag sample #1.
Air flow measurement at IAF #1 Inlet.
Air flow measurement at IAF #1 Outlet.
IAF #2 overflows into sludge trough. Beckman
400 taken offline.
IAF #2 back on-line with Beckman 400 monitoring.
IAF #1 gas bag sample #2.
Air flow measurement at IAF #2.
Air flow measurement at IAF #1 Inlet.
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Date
Time
Task Performed
9/21/83
Continued
9/22/83
1500
1505
1600
1630
1700
0845
9/23/83
0858
0900
0915
0920
0930
0940
0948'
1005
1400
1515
1600
1700
0830
Liquid VOA samples at A1, C, D, CPI-Inlet
1,2,3 and CPI-Outlet 1,2,3.
IAF #2 gas bag sample #2.
Air flow measurement at IAF #1 Outlet.
Air flow measurement at IAF #2 Outlet.
Test Crew departs test facility.
TRW Test Crew and EPA Representative arrive
at the Phillips Petroleum Facility in Sweeny,
Texas. Beckman 400 on IAF #2 had flame-out
1 hour before; relight and calibration performed.
Air flow measurement at IAF #1 Inlet.
IAF #1 gas bag sample #1.
Liquid Composite started at A1, C, D.
Liquid VOA sample at A1, C, D.
Liquid VOA and grab samples at CPI-Outlet
1,2,3.
Liquid VOA and grab samples at CPI-Inlet
1,2,3.
Air flow measurement at IAF #2 Inlet.
IAF #2 gas bag sample #1.
IAF #2 gas bag sample #2.
IAF #1 gas bag sample #2.
Liquid VOA samples at A1, C, D, CPI-Outlet
1,2,3 and CPI-Inlet 1,2,3.
Test Crew departs test facility.
TRW Test Crew and EPA Representative arrive
at the Phillips Petroleum Facility in Sweeny,
Texas.
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Date Time Task Performed
9/23/83 0845 IAF #1 gas bag sample #1. Liquid composite
Continued started at A1, C, D.
0854 Air flow measurement at IAF #1 Inlet.
0900 Liquid VOA samples at A1, C, D.
0930 Liquid VOA and grab samples at CPI-Outlet
1,2,3.
0934 Air flow measurement at IAF #2 Inlet.
0945 IAF #2 gas bag sample #1.
1000 Liquid VOA and grab samples at CPI-Inlet
1,2,3. Air flow measurement at IAF #1 Outlet.
1020 Air flow measurement at IAF #2 Outlet.
1053 Reduced flow 50% at IAF #1 and #2 Inlets.
1056 Reduce flow, THC monitoring and flow
measurements.
1230 Stopped induced flow at IAF #1 and #2 Inlet
for "No Flow" test. THC monitoring and flow
measurements at the IAF Outlets.
1330 End of test period.
1600 TRW test facility disassembled and Crew
departs test facility.
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APPENDIX F
PROJECT PARTICIPANTS
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APPENDIX F
PROJECT PARTICIPANTS
U.S. Environmental Protection Agency (Representatives)
Winton Kelly
Randy McDonald
Radian Corporation (NSPS Representatives)
Anwar Shareef
Barry Mitsch
Phillips Petroleum Company (Plant Contacts)
Larry Chi Ides
Lynn Stern
TRW Inc. (Field Test Team)
Mike Hartman
Cecil Stackhouse
Jeff Shumaker
Dave Dayton
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