&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

-------
    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

-------
    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

-------
                        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°^
7fiT^
7&"P
78 *F
7fi'^
7fi*/::
76'/= =







.




















Time

















Anemometer
Readlno

















Temoerature

















   NOTES:

-------
TRW
                               FLOW MONITORING
LOCATION

RUN NUMBER
                               INSTRUMENT A

                               BY
                                                            DATE
    RECORD DATA EVERY$-10 MINUTES    /
         .
       Time
      /O : C J
     So oo
            Anemometer
             Reading F-
                1000.  _
                 ;/7ir;
                  7  /-2.T5
                         op
                       Temperature
                         sr&'r
NOTES:
                    It*?'-
Time
                                          10 <.
                                          7^'
Anemometer
 Reading
                                                 6/co
                                                      ****-
                                                     I 74Z0
Temperature
                                                                              7'"*

-------
TRW
                        ROW MONITORING
                        >ft>T'
r LOCATION j./tr-^O*t*v INSTRUMENT rt^-o^r-**- DATE etftil&_
RUN NUMBER FLC.^ BY
RECORD DATA EVERY(J)lO MINUTES
|3s-£"
Time
60
f'cyj
lO'oO
l£:to













Anemometer
Readinq
£eeo . ...^

73?5-
66*5-











•

Temoerature
S90^
A1V
^g^
&~r










•






















J~£^f» SMor*w*<-€^ .
\(c>1&
Time
00.^^
5-100
10:^
15: 00













Anemometer
Readina
s3£ZV'
guc
#
/072S-
' /












Temoerature
v^? C? *^i^
«y ^ /^

-------
TRW
LOCATION -£& P 2
   RUN NUMBER
FLOW MONITORING




   INSTRUMENT



   BY      T-
                                                        DATE
   RECORD DATA EVERY 5-10 MINUTES
                                         i
Time
00
/O-&3
£.t>d













Anemometer
Reading
lio
L-3S°
I <*>-!££>













Temperature

Time
£?u . CL>
^,^46
(L> Cc'
;/• .v
.1 o <• rt












Anemometer
Readinq
^oo
t 'z^'-r
/&?±~
\ <£->=>•>
'2 -'' i"%-'












Temperature
7c-<:P
7^'T
7?"r
7f- f~
7,-fV












   NOTES:
                                                 c
                                           76"

-------
TRW
               FLOW MONITORING
                >T*4r-
   LOCATION XAP 1- i^carri ***   INSTRUMENT Afj-~~~t-nx. DATT  1-/2.2/63
                                                               . ^M—^   t

   RUN NUMBER   RgcJ C^r&eT"   BY
   RECORD DATA EVERY 5-10 MINUTES
       Time
        6-30
       10:00
Anemometer
 Readino
Temperature
Anemometer
 Readinq r*
Temperature
                                                           *£•£++
   NOTES
                             /
                           ib

-------
TRW
r . FLOW MONITORING
s%
ckTt£f • - / /,
LOCATION TAP MO 2 H**T» . INSTRUMENT /k^^to-vera DATE- 9A?>/&-
RUN NUMBER f^c^cJ oorz-tr. BY

&
RECORD DATA EVERY^plO MINUTES
**•«• -^**
lime
^0
C-.oo
10^
1&C&













Anemometer
Readingff
OTcsT
2.)^7
5^0 ^
4&^













Temperature
toi^p
lot 8F
/3eiF
rcsr^ '


-,




























Time

















Anemometer
Readinq

















Temperature

















  NOTES:
                                        \o

-------
TRW
   LOCATION
 FLOW MONITORING

r    INSTRUMENT
   RUN NUMBER
    BY    -T
   RECORD DATA EVERY 5-10 MINUTES
    CRB4-
   NOTES:
                                                               IS'

-------
Liquid Sampling Log

-------
  C
7
'
                                                                                                               A-  r---o    A1-
                                                                                                                 *.*
                                                                                  1

-------
WORK SHEET
                     •3B
                                /
     7J
                   1 •
                   fv
      'T>- /A/
                                     /Too
                   • 1
                             n
                             M
                  WO
     17
       13
                             n
for-
              c
'1

-------
                                                SAMPU PACKING  SHffT
  Seirple Sltet,
                                                                            CCS  ID  Not	  Test  Not.
Siirple No
                                                        I
                                                        •'
ICo I lectcd ! Date  R««av-! Time   {Weight!  Vofuire   '.
                                     L-.J...1I.L1—i.
                                                                      pH
                                                                            Field  Ad justments/Dbservat Ions
                                       .4..
                                                I.
                                               .A.
                                                        «
                                                                 J
                                                                .1.
                          .A,
                           !
                                        I
                                       .A.
                                             .i.
                                                                .A.

                                                                 i.
                          .A.
                           <
                                    .A.
                                     •
                                                                       :
                                                                      .1.
                I
                t
                t
               .A.
                        I
                        t

                        .1.
                                    I
                                   > A.
                                I
                                I

                               .A.
 I

 I
»•*«
                                                                  .A.

                                                                   I

                                                                  .1.

                                                                       .1.
           •>  i,
           *
                                     I


                                    .A.
                                     I
                                               .A.
                                                               J

                                                              .1.
3
               .A.
                I
                        .A.
                        I
                                    I
                                   .A.
                                    I
                                        •
                                       .A.
                                        I
                                                                  .A.

                                                                   J
                I
               .A.
                <
                        .A.
                                    I
                                   . A.
                                    •
               , A.
                           •
                          .A.
                                     •
                                     I
                                    .A.
                                                                       .A.



                                                                       .A.
                                                        1
                                                                   i
i tec* for a-  re?
                                                                                                          of

-------
SAMPir PACKING SHCET
Sites
                             CCS ID Not _______  Test Not,
       i
San-pie No {Co 1 lectcdIOate Recov-1 Time iHe
........... .i.lxti/pOli-tttU^EtftD-i 	 	 l_i

H »' ^i M - 'I
if TL ^ /i
'• i. I iflar- "
•• '« 3 l «t •«
	 ...Ai™ 	 1
i, H 3 ! »i «,
	 . 	 i 	
§ »
* j . . A 1* *l /^* /I <7 / ) J[
H «^ _ M
" j^ "
J
« 1
/7 -T-./I i- // c-
'.A. *.„,/' - .jL/7/r - /T ~ /
t. ! £
1 .„-!
	 . 	 l_i_> 	
1
1
1
I
\JJ»{
•

•
§

j i,
j
— t /y*
»
i "
j ..
j
•

•
i • •
•
i
•
•
•
t
•
i
i
KS. 	 i 	
i i
'. 	 L_.
•
i
•
	 i 	
t
	 t 	
' J
	 1 	
^.-.-..L-.
J
•
•
i
•
,. i
s' i
.. J
	 i 	



!
i
i
	 i._


j
	 i..
t
t
i
«
j

i

i

IgKt Volure
1
	 i 	
t
*
t
	 1 	 ....

1
1
J
i
	 i 	
•
*
»
	 1 	




• '
I pH i field Adjustments/Observations I
* *
I
\
\
...J 	
S
*

|
t
J
1





. i - .


1
•
	 J 	

I
J
1
	 i 	 . 	 . 	 ....
• s

*
]
,'
{


t

-------
                                                                    Tn.
                                             SAMPLf  PACKING SHCPT
Seirplr Sltei,
CCS 10 Noi	   Test  Not.
t
1
J Sin-pie No
1 	
• /V ' ) '•


^(•j-i^ S
•
1
t/"f'Tl^J( i
i
'tPli* 3 ''
• "^^ *^^
• , (
1r i J*^ /
f~~ '** /
t
*£&'•}
\
%• ' J ''J
,
^%'V A-^e-r
v/i
j* /7w-s
•
^/^ •*• * ft ' '
. •' O
;
SCol
; (Y

^Ot
\ ,

\ '
1
1

'""1*2^
I .,

1
1

1



1 *

1
if ^ ft
•
,



I



f
1 1 '

1
lectcdJOate
Ci/OQli_JE££l

L4P...I 	


» *
:


^ ~%/1^ i ^ '-J^
•
« * '•


.. i ;

•

t
II I **

'1 ' •/
i '

*
i * /
(, • i,


' ' O* ' *> >
1

1
IJ f
I
1
1
Reco v- !
}£££.&£_ J.
J



	 i.



> 	 i.

j^
• .
i
	 i.

*


\


i



a
	 i.
i

i
i
•
i
i
i
i
Time J
...... .....I
J

I

J


•




	 i
:
i


,*


i









i

^ i
•.
Weight: Voluire
_ifll 	 a— lull 	
1




5


	 	 i 	
J







J




i



•


t
9
• ,
J
•
!
i
J
I


i






i



!

J


*



J





•


t 5
PH ! Field Adjustments/Observations
•
^ .



t
	 1 	


t •
^
J

t



^ '
, m ••••••
I
i
•
1
•
i
1
:
_j
i
i
!

•
I

for IT TC?
                                                                                          Page
                          of

-------
eirplr Sltet
                                              SAMPU PACKING SHCET
                                                                CCS 10  Nol	   Tut Hoi.
 Si
-------
                                SAMPLf PACKING  SHfET
                                                                        7/Jj/i?
Seirple SI
                                                              CCS  ID  Noi _______  Test No:.
  Siirple No   tCol lectcdSOate Recov-J  Time  !Weight!   Voluire
                                                      pH
                                       Field  Adjustments/Observations
                                             J
                                        J
                                                  .1.
                            J
                           ..i.
.A.
 I
                                J
                               .i.
 •
...
                               .A..
                                •
                                •
                                                     I
                                                    .1.
           :-.
          .JL__
                                       .J.

                                        I

                                       ...
                                                               .A.

                                                                I
 s
.1.
           .A.
           t
                                             .A.

                                             J
                                             I
                                       .A.
                                                  .1.
 "I
 <
.4.
                                                                        i
                                                                        i

                                                                       .A.
                       .A.
                        t
                                                                       I
                                                                       t

                                                                       ...
                                                                       I
           .A.
           I
                                                                       t
                                                                       .A.
                                                                       I
                                                                       I

                                                                       .A.
.A.
                                I
                               .A.
       rorr
                                                                                         of

-------
                                           SAMPtr PACKING snrn




Sivplf Sltti	JJiiiif&./--^*i&*£	  CCS  10  Not	   Test Noi
1
Sirpte No

/*/- / .
l-j -^ c&/nf

^rt. '*




















•
*
I

*
•
•
t 	

t
i
ICol
.i.ia

: ,

J i,
.1 	
I
f


j
5



i
i

J
..i 	


1




•

i
i
i

•
lectedtOate

1....L-.

	 i 	
•
	 1 	

•

i
^
•

j


' •

•
_•
;

i
	 1 	





•


i
i
Recov-J Time
HftfiC.l.. 	 ..
I
j

J
	 i 	
I



	 i 	


' I
	 1 	
•
i

I
	 i 	
*

J




	 	 i 	


«
•
i -i
J
iWel
..i-lfl
1
I
..i 	
1
|
•
i


..i 	
J
..i 	
:
..l 	
j
i

J
1
:





t


•

j
i
j
gl-tt Vofure
J..J 	 ifil..
t
	 i 	
J
	 i 	
I
	 i 	 . 	
t
f

I
...I 	
1
_•
J
	 1 	
«
i

•
	 i 	
J

J
	 1. 	


I


•
	 J

i '
1
J
}
1
1
S

J
j
t
«

i
I
j

t
[
t
i

I
!
t

*
j[
•

t



;

1
T i
PH I field Adjustments/Observations I


I
_•
J
j[
•
•

* «
j
J
	 i 	
1
*
• m
• g
A '


s

J
j
1
1
{
_J
I .
J


„ • 	 . 	 ,„.„„.„.„.. 	 	 	 .. — ... 	 ....

-------
     APPENDIX C
   ANALYTICAL DATA

t  Gas Ch-romatograph Worksheet
•  Continuous Monitor Example
0  GC/FID Examples

-------
GC WORKSHEETS

-------
     WORK-SHEET
                                                                                     X
                                        x
              •'•A
     ,
                                                            3/Vf
t <: i if
^iMf-flr.
                                                                               C'. C.T -^
                                                                         *?.«.'/? 2T
                                                                                           }, C I/O
                     }.*','
                                                             TH
                                                                             \
                                                                                           t>
               J~J-
                      US.
                                  ^h
                             >j£L
/L

                                                                                            /. Vt

-------
WORK SHEET
                                                        **_/&>,  I
                  -^pL
                                                       2.JL,
                                                               m
                                                  9/2 /
                                           $
                                                  9x,
1/jt*
                *
       Ik
      •
                         6/3

-------
                                                      GC WORKSHEET
COLUMN:
:  '  9.
RUN" NUMBER:'
DATE:
COMPOUND
C1
C2
C3
nuTAnT,irMrl

C5
C6&-J>
BENZENE
TOLUENE
XYlffNE
c=S3i:!?c
•Trrrf t*
:Jt^J7w^s
STYR):NE
TOTAL
HYDRO-
CARBONS
(iTKC)
RETENTION TIME
IN CM.
./•a
,*
U«
OJK i-'"
2.; 7
UK V-J7-
v-.^/
^ ?<57- •
J/< v.^7- •
UK ^/
ik ^:71/

*
•
COUNTS
'7^/3
/^3
>/3>
a.3
77^
/*/
/Ul
5?V
3|1?
y^/
^^/


•.
SPAN










*
•
ATTENUATION
. •

•







,

DILUTION FACTOR
(Diluted w/N2)

*
•








•
CONCENTRATION AS
COMPOUND
W-^ '
• v-.r
.t.T
ii+
a^Mj-
Z&.+



-
* *
•
•
CONCENTRATION AS
t§^E

,


.




•
•
••
                                               ENVIRONMENTAL ENGINEERING DIVISION

-------
                                              6C WORKSHEET
COLUMN
MM;'   D\l~l°l
RUN7 NUMBER: '
DATS:  ?
COMPOUND
%
h
»
4
C3
RI'TAHTCWf

C5
C6liktfj)
BENZENE
TOLUENE
XYLENE
eft'fr-c
S. 1 H" -r™
ftct/ygiig
UU.tl.k.Mu
STYRENE
TOTAL
HYDRO-
CARBONS
(iTHC)
RETENTION TIME
IN CM.
•

t

i* £>«
/«!>:* •
it /«(./ l^w)
* MT2.
uk J.S/
i,ys
«k1-*
^•7JL
-^Hr^
Ux s.^6
UK £.'/•
• •
COUNTS
•

•

v*7^
s^ys
*f/3a«/.
6C.S-/
1S772-
3
M-l
25,9
&> i&<{
ts.^/
Ztf^f-
•
"

-------
COLUMN:
           GC WORKSHEET.
RUN"' NUMBER; "3J\ £*!)(*>..,»
DATE:
COMPOUND
Cl
C2
C3
•fll'-TAnT-FMFl
<•*
C5
Ce4^
BENZENE
TOLUENE
XYLENE
ff.-5*jtf['?«-

;Jt^ilF^
STYRENE
TOTAL
HYDRO-
CARBONS
CiTKC)
RETENTION TIME
IN CM.
,

•

L»4 o, 1
& io(o
I ^
J* 1,1,* Wr^)
V**- », >«.
•j/t; 3- <.
^•^b
*5,^
u< ^.73
Ok. 56^
0/< ?-$
•
COUNTS


•

5^2.
53io
^/^
^A
b/t.
?/4^
//S3
/^T
VJV
SV

SPAN










•
•
ATTENUATION
•

.







f

DILUTION FACTOR
(Diluted w/N2)

•









•
CONCENTRATION AS
COMPOUND
•
•
.


?s. 7
n*
//..•§
•'/3. I-
5f. 2.
/•^t
•
•
CONCENTRATION AS
BENZENE

.
•

.




• .


                                                         a I it/is
                                              ENVIRONMENTAL ENGINCCRING DIVISION

-------
COLUMN:
GC WORKSHEET
RUN NUMBER:
                           DATE:
COMPOUND
Cl
C2
C3
fll'TAHTFMr

C5
Vllt*^
BENZENE
TOLUENE
XYLENE
r-ffrtec-
G C VIC 11*
ytt\i*n£
STYRENE
TOTAL
HYDRO-
CARBONS
(iTKC)
RETENTION TIME
IN CM.
/),k/
b^Tii-fr-
/.ll.
UK I.V3
UK l,o V"
^'^>
UK 5./1T
iJC^^-'rf/
5.W
UK (*>,&$
•



, *
* -
COUNTS
•
tey^
j&+
iw
/ai
/7f
t I
'%<,
&<•





t ,
SPAN






•


•
*
•
ATTENUATION
• «
•
»




•


.
•
DILUTION FACTOR
(Diluted w/N2)

•
•
•



^


•

•
CONCENTRATION AS
COMPOUND
5*7- '
•
*3hu
•zrf
•*rt -
/'•jiT i
we; 5.
i^.*f
/T./U
JMJ


•
• * .
•
•
CONCENTRATION AS
BENZENE

t
. •
•
»



•
»
•
••
    TRW

-------
                                                  GC WORKSHEET
COLUMN:
_  RUN NUMBER:'
.'/grv J 73 <.
DATE:
                                                              fat #3'
COMPOUND
C1
C2
C3
nuTAnurMfl
<-*
°5 ~A
c6&t*Ji
BENZENE:
TOLUENE
XYLENE
fiAft'?8-

DtriitrtS
STYRENE
TOTAL
HYDRO-
CARBONS
(iTKC)
RETENTION TIME
IN CM.
0.4
o.i+
A59
P/" 2-Sf-
3.ol
U< S.JJ
uk ^,S^
"^ 7.77 •
b^ %>$ '



*
• <
COUNTS
K
7?%
/^/
/S3
»>?•
757
/I?/
nw
&<{




••
5 PAN
//»"V
58-^
^3
y.j&
*a
/SL7






•

ATTENUATION
' / y^












7W5
'••>o
/^5
^(•yuwaMe;
fr?
^<. i
X/^3
/y3x
3V3



,

DILUTION FACTOR
(Diluted w/N2)
j^^
Sfc7
'^.2.
Vi^,
Itf


'




•
CONCENTRATION AS
COMPOUND—^
7^t5
^A
/5^
•JSo
*₯*.
/«>
/^^
^4-

•
• •
•
•
CONCENTRATION AS
^ BiHteWfl
^ ^>»pp>
Slr.T-
»;>.
4-^f
/?.*»
.
i/'S
•


•
•
"
                                            £NVIRONMMTAL CNGINCCRING DIVISION

-------
GC WORKSHEET
COLUMN:
NUMBER; '
f30
                            DATE:
COMPOUND
/i
^
4>
-flHTAnUTHf
G<£
^
Ce4e^
BENZENE
Ultff/*i-jt—
TOLUENE
XYLENE
fiffi?^-c
Zrl fTT IT™
4CI>!3CMC
otMztNS
STYRENE
TOTAL
HYDRO-
CARBONS
(iTKC)
RETENTION TIME
IN CM.
•

*
IX 6. ')
UK l,a 3
flfe /.^^ •
/.&-7"
— «fc z
4* J iV
^/^ ^.Jf5
U*. i.S
*/
^ v-?/
u/< Siy;
i>/\ Xy1/
UA £-ttf
U/
-
SPAN






•


•
•
4
•
AT


•




ENUATION
acfcd
• •

•
•
V^S7
SJf/
S/tf-
fajo
i *2i)
SJtfS .
llit-

u;
2Va5
Wl
j JfJ>
! s'jy
y/.T-
t •
»
,
DILUTION 1
(Diluted

•
%
•



•


•

•
"ACTOR
w/N2)
/vo£

•

•f5^X
Si7*>
nv;
$t*to
w*L
SiJSl
nfS
'<}b
APS,
bH.
3V>
w
4W
zz>
Vf6

CONCENTRATION AS
COMPOUND
•
•
•

,
W±
M,*>
'S5-T
J^t-o
#//
^.1
* •
•
•
CONCENTRATION AS
BENZENE

•
. • .
•
«



•
•
•
••

-------
                                                      GC WORKSHEET.
COLUMN:
RUN* NUMBER;
DATE:
COMPOUND
{
4
^
•AVTAilTCMI"
cu
c^
C6&e*Ji
BENZENE
jWW/vrt 	
lOLUENE
XYLENE
sffifo™*-

i3C.?V££rlu
STYRENE
TOTAL
HYDRO-
CARBONS
(iTKC)
RETENTION TIME
IN CM.
(

•
u/< ^ip
ok Aoz
tft/,^^
1,56, •
-w /• ?1
*» r M
q.X 2. H f
0,c j.yy
₯•//
ia» ^.i-V
«J^ S". JV
w/t 7^/
u/<^ r^v
W ?•*-(
•
COUNTS
/^
'

• •
V^To
Hit
7/3-S
•gt^o
7>Vf
<;/*<>
,ll/OC>
mi
*>n<,
/MJ
7/0
/J^2-
/7Jf
^/
..
SPAN






•



* .
«
ATTENUATION
^«Su
/ ' '
1
•
1i,U
vsn
^f?3
)C6
^rn
I mf •
/o^
r>v>
y«
^o
7fc"3
. //6
*/7/v

DILUTION FACTOR
(Diluted w/NJ
\ Ao't^

•




'• :


•

•

•

Hlb
KH
7°54
J(.>2
MT>
vfli
isv
i-'j'lJ^
|IC'/
S'/b
/t>fc,l_
*s?-
5'5I
•
CONCENTRATION AS
COMPOUND
•
•
«


//«?,£>
JJS.2,
S?,o
'/V-. (
^J.^
/o. 3
•
•
CONCENTRATION AS
BENZENE


• •
•
.




•
•
••
                                               £NViRONM£N7AL ENGINEERING DIVISION

-------
COLUMN:
      6C WORKSHEET
RUN NUMBER:'
                                     DATE;
COMPOUND
Cl
r»
C3
RI'TAni.PNF

Cc 	 	
5 	
CC/H \
O\HWV»J
BENZENE
TOLUENE
XYLENE
&.>:$j«NcT
ftPt'IpMB
SCKZJtt.
STYRENE
TOTAL
HYDRO-
CARBONS
(iTKC)
RETENTION TIME
IN CM.
t/e
M
•
t\k£ 1 ^*
OK^-V
u Ic w • bS
—^ 1 <
7 t . j>
^^T-




• •
COUNTS
_ *T
^^A"
?M
1 *^_
'•I5|
'^i
l$if
1*)
H^




..
SPAN
np^
ffr^y"
ftnt
ty
to •


•



'

ATTENUATION
*^f ^ij£
* 0 /
loS
IS'/
^3
sVat
i^7
JS^
•


.
*
DILUTI
(Dili

•
•



"

ON FACTOR
ted w/H2)
Jatf
)D(,'
is/
•^.O.-!
ujolj
/Vb
Jo/.?-
'



; ' '
CONCENTRATION AS
COMPOUND
£5,1 '
' t>
• _j» •
^^^^*^1*"

^o. ?


.
• •
•
•
CONCENTRATION AS
BENZENE

,,
. . .
•
.



•
•
•
"
           TRW   '
£fJVJRONM£AiTAL ENGIKtCttlNG DMSfOff

-------
                                                  GC  WORKSHEET
COLUMN:
           RUN7 NUMBER;
                                                                   DATE;
                                                                                       '  .   ,
 COMPOUND
RETENTION TIME
    IN CM.
COUNTS
SPAN
ATTENUATIOJ^
DILUTION FACTOR
 (Diluted w/fU
CONCENTRATION AS
   COMPOUND
CONCENTRATION AS
    BENZENE
                                                                               (**>.(»
  BENZENE
   l.sl
                              77-7-
 TOLUENE
                                                                               •xr,|
 XYLEME
            OIC
                                                  /ofS
                                                          >,0
            tifc
 STYRENE
             uk.
 TOTAL
 HYDRO-
 CARBONS
  (iTKC)
                                           {NVIRONMSN7AL ENGINttfUNG DIVISION

-------
                       I   *t
          GC WORKSHEET
COLUMN:
RUNJNUMBER:
DATE:
3 .
                        &**₯
               ftJcliMrf/ttNO DIVISION

-------
COLUMN
MN:'   ji
                                                    GC WORKSHEET
v
 }
DATE;
3>

COMPOUND
Cl
C2
C3
]

C5"^\
"Art|f /!!• ^T
BENZENE
TOLUENE
XYLENE
rJf,^*NC,
*% r* \**1 f*| 1 **
Jt,.\
u< II. o



*
•
COUNTS
/<£$/
11*1-
>|0
CP
5w
•^88
-i —




•.
SPAN
74.7-
?.o
t c>
tf

yo,ry




•

/^tf1/- • ' • ' • •
A
1







(
TTENUATION
*i\v.
*
/ 5 /
iu

\ib
ffil-i
m
9s;



.
*
DILUT
(Dili
V.b
•7,X
(i.O


/6-/


ION FACTOR
Jted w/N«)
l.o^l
' 1^'
->H
i^Si
m3
?s«
/15




•
CONCENTRATION AS
COMPOUND
^-5,V
7.5,
5.9
2 ?»^/>

|^ Vy / ^«-5


•

•
•
CONCENTRATION AS
BENZENE




.




•
•
••
                                              ENVIRONMENTAL £NGINCEMNG DIVISION

-------

                                                   GC WORKSHEET
COLUMN:
lt \
DAT£t
COMPOUND
C1
C2
C3
•-RIT-AnTFMF

C5
ce6e*Ji
BENZENE
TOLUENE
XYLENE
E.-f.tfl*'^
fcrr-irijn
BtNZJiu
STYRENE
TOTAL
HYDRO-
CARBONS
dTKC)
RETENTION TIME
IN CM.
,

*

ufc /,&/
«a |.2 /
!. 5 I • .
^ i$pMf'f/w)
"i 6 

•

ATTENUATION
*

*
i
w7u r
C?(i 1
/-«(.
F?l
££
£r
• *$£
*
DILUTK
(Dllu


•

)N FACTOR
;cd w/N2)

•



/ «s?7
*>•? I /*WV
1 > 'IS/
1 P
Vj.^ / ^6.4^
1 1^3
/ '/^7-
10 \
•
CONCENTRATION AS
COMPOUND
•
•
.

t
M.I
nu
i%.l
45^ ,
.1.6
•
t
CONCENTRATION AS
BENZENE

*
• •
•
.



•
•
•
"
                                                             KMftS QMS/ON

-------
COLUMN:
- )*('
                                GC WORKSHEET
NUMBER: 'dtyr*
frs.
DATE:

COMPOUND
Cl
C2
C3
m'TAnicMO

C5
c64^
BENZENE
TOLUENE
XYLENE
,.->;&**«-
^r-fll^.lr-
BLKZJiu
STOTO
TOTAL
HYDRO-
CARBONS
(iTHC)
RETENTION TIME
IN CM.
t

•


U'C )•» 1.
1.52. •
1 ft ^ 1 L ~* * * V- \
we z. ?
Uk J.JJ
5.77-
'C* v ^
u< ^ 7-
"" •'5f-^
COUNTS


.


slil
Jif^l
^ •
"yU
/*^to 2
J rt 'i
1 ^'/^
67
SPAN






i^^,o

^,

•
t
i
/&u /^ •?•
AHENUATION
•

. .


\
\

%i+
'w
' ?£
' 73
DILUTION FACTOR
(Diluted w/N2)

*
•



y i o

•\/ o


•
CONCENTRATION AS
COMPOUND
•
•
t





.

•
•
CONCENTRATION AS

.
• • •
•
^pT
^ ^
^-7
^•J:
•-26. Z.
)O.U
•
"
                                  'TRW   •
                          £NViaONM£NTAL fNGINCSNNQ DIVISION

-------
                                      GC WORKSHEET
COLUMN;
NUMBER? '
oft*
DATE:
                                                                    i   t
COMPOUND
Cl
C2
C3
ftMTAniFMF

C5
Ce6e^
BENZENE
TOLUENE
XYLENE
HWi*?*-
sTinTCT"
4CU3CM8
atftitNu
STYRENE
TOTAL
HYDRO-
CARBONS
CTKC)
RETENTION TIME
IN CM.
£,^
t>$5
\,y*
•ai»
p^- »
/*7^
m?





-
SPAN
I/VT* i
I^.S
l-.t
iA
s.jr '
;^,6>

•


•
.
•
ATTENUATION
;^
SWJT
y^v
• • '/>>
^'
«i
i*<&
/•**>
/M"

•


t
*
t
DILUTION FACTOR
(Diluted w/N2)
no
•
5.^f
ZZ
y.s
y,^




*

•
•
CONCENTRATION AS
COMPOUND
•
•
•





*
• •
•
•
CONCENTRATION AS
amatt
N5.1-

|^^S»



•
•
*
"
                                          way

-------
COLUMN
'MM:'   ySftoci^
                                                 GC WORKSHEET
NUMBER;
DATEt
                                                                    ' 7
COMPOUND
C1
C2
C3
fH'TAnTCMFl

C5
Ce4f^
BENZENE
TOLUENE
XYLENE
*rfcft*?**
fl(Tt '7 CMC
stfvttiHu
STYRENE
TOTAL
HYDRO-
CARBONS
(iTKC)
RETENTION TIME
IN CM.
6,k
D.W
' A3?
|u«: '.93
£.f*
u* v f
jjk. 
/'7T-
/^^
^ s
I'VV
31£
W^JVo
li^Cir/
fail
V





••
SPAN
fft^
%/
/.₯
^.z
?.5 /
^ !
i
•



*
•
ATTENUATION
/ (+.^
1 ' W
/
)9V
' ' 1^
(a>
'H
i'l1/
. ' • '
2.i
},S
*•*>

'




•
CONCENTRATION AS
COMPOUND
•
•
,





.

•
•
CONCENTRATION AS
BENZENE
?3,£>
•**
1.-L
3.5
W




•
•

                                           ENVIRONMENTAL ENGINCWNQ DIVISION

-------
                                              GC WORKSHEET
COLUMN:
                                       7
RUN NUMBER:
DATE:
S\ - . If f
a/K/ti- ...
COMPOUND
C1
C2
C3
flUTAnic»|d

RETENTION TIME
IN CM.
#

'

C5 1 We Aoi
C66**i
BENZENE
TOLUENE
XYLENE
€#$£**
sENZJJi.
STYRENE
TOTAL
HYDRO-
CARBONS
dTHC)
;,i-*- •
m •
<* *!&<*<«*,:>
PJtr ?•<*.
u/t '•'a-
J.62.
ufc fct>
OK $. s J
L>K 7- F
uK. >?«>^-
COUNTS


• *

fin
*>•*/
3u/
/*.* '

,,/yt
7>/ .
/
\
1 7»I7

1 W
/ gj'^
;' /D 5 3
i*J>Jo
<>o f-
*
DILUTION FACTOR
(Diluted w/N2)

*
t
•



fit-

*.1

.
\
CONCENTRATION AS
COMPOUND
•
•
.

.



.

•
•
CONCENTRATION AS
mmt

..
. . .
•
» •
33 J
55- f
1.0. >
2t./
>iS
•
"
                                                   TRW  '

-------
                                                  GC WORKSHEET
COLUMN;'   £>\l~- 1° V
                                          7
           RUN NUMBER: '3*?*
                                                                   DATE:
 COMPOUND
RETENTION TIME
    IN CM.
COUNTS
SPAN
ATTENUATION
DILUTION FACTOR
 (Diluted w/N)
CONCENTRATION AS
   COMPOUND
CONCENTRATION AS
  BENZENE
                                                                 1s?,1/
 TOLUENE
  Ml
  ?..*>
                 -#
                       /VMS
                        i* >i
                                /3//31
                                Li(t*+-
 XYLENE
                              114
                                    Jlfc-3
 Sfftffft
                                                                            ti , z
 STYRENE
           014
 TOTAL
 HYDRO-
 CARBONS
  (iTHC)
                                           ENVIRONMENTAL ENGINEERING DIVISION

-------
                                                GC WORKSHEET
COLUMN:
NUMBER:'
DATE:
COMPOUND
»
h
i»
U2
RETENTION TIME
IN CM.
*

'a f
ni'TAnT.ciirl

-
C5 1 UK. U^
Ce6c^
BENZENE
TOLUENE
XYLENS
i=ftjfli*?«-
DClIICMS
StflZuNg
STYRENE
TOTAL
HYDRO-
CARBONS
CiTKC)
** \.*\
}.&> ' .
*&• J.^1 VHiVI-4M\
*• 7.11 ' /
\>* Z.^5
»*- V1 1
'i,^
»fA>
uk f,^
,JK j.-T-
(>K 6.9
ak ->.z.
UK fr,o>
bK^.jH-
uK I)
u|02,l^ •
COUNTS
f V
»

*
* *

(M*
m»+
Hm-
Wi
nail-
*? *^^
«>tf}i
s^n
A^i4
3s n
»i>l
*fl5^
;t-^5
iii^
^^^-L
*H
)ctf
SPAN



• .


^«%f

fi,|
3o/)
ATTENUATION
1 2"l>.
I • t

1 ' '•'


?^>
il^l
. JM/
1 »*4*
1 yfTo
1 . Hi, i.
1 m
•



^yiU

7^.1-
^,2,
.
•
•
CONCENTRATION AS
COMPOUND
•
•
•


*72,<;
3*7. <=>
/f*« /
l.l₯,l»
•^3,7 •
2.«?fo
• •
•
i
CONCENTRATION AS
BENZENE

, ,
. •
•
.



•
•
•
"

-------
COLUMN:
                                              6C WORKSHEET

NUMBER;
                                                              DATE:

COXPOUND
C1
C2
C3
RHTAniiCNF

C5
W£/|| \
Oxrff*'^* J
BENZENE
TOLUENE
XYLENE
^.Jfj^tNC.
ar-iU^n-
SE.NZJu
STYRENE
TOTAL
HYDRO-
CARBONS
(STKC)
RETENTION TIME
IN CM.
o.t*
o,ri
«

"7-1.4
UK £,fe}j
•



'
'•
COUNTS
j^c,
3^7
Vw
v^O yO
/ (jt \i "2
•?«





•.
SPAN
.^5,d»
^A
5,»/
^,3>
^,6,





•

fat/«i ' ' . . '
AHENUATION
ik^
1 w
f's"5>
avol"
,?w'
l»7So..




t

DILUTION FACTOR
,( Diluted w/N-)
^

•^.S ' '
5/7-
^.?
9b.+






•
CONCENTRATION AS
COMPOUND
^_
•
.





.

•
•
CONCENTRATION AS
2*6, 1-
7v>
s..^
2LS
S7.-S




•
•
••
t
                                       ^^
                                        ENVIRONMENTAL ENGINEERING DIVISION

-------
                                                              .   •
                                                                 *
                                                GC WORKSHEET
COLUMN:
NUMBER; •
DAT£!
COMPOUND
*
Cl
r«
02
C3
fli'TAniFMrt
C*
C5
c6&n*Ji
BENZENE
TffifiBK
XYLENE
^tec
tri'ftTC*
•ft CM 7 CMC
"trtcEH*
STYRENE
TOTAL
HYDRO-
CARBONS
(ITHC)
RETENTION TIME
IN CM.
,

*

•
y.z
}»3
y,
ys,-//
72iP
2/^u
2#,r
i-j>y
/ Vt?/
i»tf
SPAN






^o//i


/?.o
AHENUATION
~««
x' /?*-.»•
. •

•


/m*
/?765
5//^
to
•/Ai'j
•<•*>>
'V*- Jto)T-.
2tV-fr
[ ^5f
I . &*•'/
n /2
-------
                                                     6C WORKSHEET
COLUMN
     7
!    ./?y?oCl.L

NUMBER;
COMPOUND
Cl
C2
C3
fll'TAnTlTMl*
<-«*•
'5^-
Ce4^
BENZENE
TOLUENE
XYLENE
-^W^

!Jt!\£!in*
STYRENE
TOTAL
HYDRO-
CARBONS
(iTKC)
RETENTION TIME
IN CM.
0,(s
f).ty-
/.3S
we /.Uu
U* at/.
2,Vf
u« lf.'/'
UK ("01
t{/< 7.of
" — afc f.'/y-
Ukl |l,1«/
•



'
• •
COUNTS
r^1'1^
l*$ft
33o
'Wf
'T-/
75 K
;W
"^
4,11*4
4T-»7
/l>$0
£92.





-.
SPAN
rt|)r»s
W4.?
5.T
^./
ys,s






*

ATTENUATION
2^
• •
hu*-
in
lib
i:)i
~H*t
f~Ho
!•')
6 We
tl\ '
|3W
x-V^
^r
.


\ -
/
DILUTION FACTOR
(Diluted w/N2)
/f^
^.V1
•£? '
^,6
;i.6

'





•
CONCENTRATION AS
COMPOUND
•
•
,





•

•
•
CONCENTRATION AS
&*$PE
C/n/V
/n.5
5,7-
L>,o
/s.S
.
/6. -a-



•
•
"
                                                         TRW   •

                                              ENVIRONMENTAL ENGINEWING DIVISION

-------
          GC WORKSHEET
COLUMN:
        '.




RUN7NUMBER:
COMPOUND
C1
C2
C3
--WTAniCMfl

C5
ce6wJi
BENZENE
TOLlSfflT
XYLENE
j-J^i'NC.
«riUrMff
3l\i.JT
vs&v
nt
••
SPAN






Hi. 7"


/S.G
'

•
AHENUATION
• •

*
•

?V97
To/,
7W5
i ^
lilt
ji
* *y/.
•
DILUTION FACTOR
(Diluted w/N2)

•
t
• '



0X2.


*'

*
•
CONCENTRATION AS
COMPOUND
•
•
•


/
-------
COLUMN
           t




MN;    foAoc
                                                  GC WORKSHEET
RUN' NUMBER: '
DATEt
COMPOUND
Cl
C2
C3
WTAHTCMri

Cg 	
Cs6t*^
BENZENE
TOLUENE
XYLENE
effete^
fttrvicMS
3t?\£Er(C
STYRENE
TOTAL
HYDRO-
CARBONS
(iTHC)
RETENTION TIME
IN CM.
O.t
0,?3
l-!>3>
u^ )••»'•>
u^^vf
u« 4--V
ui* y.%
> i>'< /j.^
^7.^3
•




•
COUNTS
;^M
?ot?
^^
>?s
A
^^
Jifif
«/*»!
7fl>Y
/tyo





-.
SPAN
/a?
3-7
3.6
*••/•

/J.o




'

ATTENUATION
2 "A.
W
7.7-
ife
3?f
•/is
s/ .
a-wa
1HX1.

-------
ii
 I
                                    i!   S
                                     ii: is
T
                 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
5MP)  *
PILE *
R'EPT *
METHOD
2
3

4

5
                                                                 .
             8.68
        STOP
     6
     t
    44
          C-2
3C-4
                TIME
                1. . ^9
                2.54
                3.R!
                A. 4ft
                7.A4
                8, Aft
                     A.2414
                     5.4107.
                                          A4R
            TOTRL
                    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
i!e2
1.22
1.52
1.88
2.22
3^17
                 4.77

                 7!'7
                 8.«1
                 9.27
   14.27
TfJTflL
                            CONC
                           124.1267
                           288.1822
                              .1*8
                         v
                         V
                         V
                         V
                         V
                         V
                         V
                         V
                         V
                         V
                         V
                         V
                         V
                         V
                         V
                         V
                                  4714
                                              11577
                                                11?
                              .. \7fit*
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

-------
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

-------
      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

-------
APPENDIX E



 TEST LOG

-------
                               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.

-------
  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.

-------
  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.

-------
  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.

-------
     APPENDIX F
PROJECT PARTICIPANTS

-------
                              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

-------