&EPA
United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
RTF, NC 27711
EMB Report 86-HWS-5
DECEMBER 1988
Air
HAZARDOUS WASTE TREATMENT,
STORAGE, AND DISPOSAL FACILITIES
HOLDING LAGOON
FIELD STUDY
TEST REPORT
FIRST CHEMICAL CORPORATION
PASCAGOULA, MISSISSIPPI
SUMMARY REPORT
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86-HWS-05
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air Quality Planning and Standards
Emissions Measurement Branch
Research Triangle Park, NC 27711
EPA Contract No. 68-02-3851
Work Assignment No. 10
FIRST CHEMICAL CORPORATION
WASTEWATER HOLDING
LAGOON FIELD STUDY
Final Report
August 1986
Prepared by
Douglas E. Seely
Richard Roat
GCA CORPORATION
GCA TECHNOLOGY DIVISION, INC.
Bedford, Massachusetts 01730
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DISCLAIMER
This Final Report was furnished to the Environmental Protection Agency by
Alliance Technologies, Inc. formerly GCA Corporation, GCA Technology Division,
Inc., Bedford, Massachusetts 01730, in fulfillment of Contract No. 68-02-3851,
Work Assignment No. 10. The opinions, findings, and conclusions expressed are
those of the authors and not necessarily those of the Environmental Protection
Agency or the cooperating agencies. Mention of company or product names is
not to be considered as an endorsement by the Environmental Protection Agency.
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TABLE OF CONTENTS
SECTION
1.0 INTRODUCTION
1.1 Program Objectives
1.2 Site Description
1.3 Measurement Program
1.4 Test Parameters
1.5 Description of Report Sections
2.0 SUMMARY OF RESULTS AND CONCLUSIONS
2.1 Stratification Study
2.2 Surrogate Analytical Parameter Study
2.3 Syringe Sampler Field Trial
2.4 Flux Chamber Direct Emission Measurement Program
t
3.0 PROCESS DESCRIPTION AND OPERATION
3.1 Process Description
3.2 Process Operating Conditions
4.0 SAMPLING LOCATIONS
4.1 Stratification Study
4.2 Surrogate Analytical Parameter Study
4.3 Composite VOC Syringe Sample Study
4.4 Steam Stripper Process Study
4.5 Direct Emissions Measurement Program
5.0 Sampling and Analytical Methods
5.1 Sampling Equipment/Procedures
5.1.1 Liquid and Sediment Sampling
5.1.2 Air Monitoring
5.2 Onsite Sample Analysis
5.3 Laboratory Analytical Procedures
5.4 References
6.0 DETAILED RESULTS
6.1 Stratification Study
6.2 Surrogate Analytical Parameter Study
6.3 Syringe Composite VOC Sampler
6.4 Flux Chamber Direct Emission Measurement Program
7.0 QUALITY ASSURANCE/QUALITY CONTROL
7.1 Method Precision, Accuracy, and Completeness . .
7.2 Laboratory Analyses
7.3 On-Site Analyses
7.4 Calibration Procedures and Frequency
7.5 ' Sample Custody
7.6 Data Reduction
7.7 Deviations from the QA Plan ...
PAGE
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86
139
139
139
141
145
APPENDICES
A
B
Raw Data
Radian Report
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LIST OF FIGURES
FIGURE
3-1
4-1
4-2
4-3
4-4
5-1
5-2
5-3
5-4
5-5
5-6
6-1
6-2
6-3
6-4
7-1
Steam Stripper Process Diagram
FCC Wastewater Holding Lagoon Schematic and Sampling
Locations
Approximate Condition of Surface Sludge Layer at FCC
Lagoon
Steam Stripper Process Sampling Locations
Floating Flux Chamber and Support Equipment
Bacon Bomb Sampler
Liquid Core Sampler
Telescoping Pole Sampler
Time Integrated Liquid Volatile Organic Seimpler ....
Cutaway Diagram of Flux Chamber and Support Equipment .
Liquid Core B
Liquid Core E
Liquid Core F
PAGE
11
18
22
25
26
28
30
32
33
35
37
50
51
52
53
85
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LIST OF TABLES
TABLE PAGE
2-1 Summary of Results Stratification Study 7
3-1 Lagoon Depths in Meters 13
3-2 Wastewater Holding Lagoon General Characteristics ... 14
3-3 Process Operating Parameters Effluent Control System . 15
4-1 Sampling Summary 19
4-2 Steam Stripper Sampling 24
5-1 Instrument Conditions for Volatile Organics Analysis . 41
5-2 Volatile and Semi-Volatile Components for GC/FID
Analysis 42
5-3 GC/MS and GC/FID Operating Conditions for Extractables
Analysis 43
6-1 Results of Onsite Analysis 47
6-2 Lagoon Concentrations as Measured by GC/FID Analyses
Grid Point: A 55
6-3 Lagoon Concentrations as Measured by GC/FID Analyses
Grid Point: B . 56
6-4 Lagoon Concentrations as Measured by GC/FID Analyses
Grid Point: E 57
6-5 Lagoon Concentrations as Measured by GC/FID Analyses
Grid Point: F 58
6-6 Liquid:Sludge Organic Content Comparison 60
6-7 Lagoon Concentrations as Measured by GC/MS Analyses
Surface Liquid Location 61
6-8 Lagoon Concentrations as Measured by GC/MS Analyses
Bottom Sludge Locations 62
6-9 Surrogate Study Results, POC VS. GC/MS VOC 64
6-10 Surrogate Study Results, TOC VS. GC/MS VOC and SVOC
Liquid Samples 65
6-11 Surrogate Study Results, TOC VS. GC/MS VOC and SVOC
Sludge Samples 66
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LIST OF TABLES
(Continued)
TABLE PAGE
6-12 Syringe Sampler Field Trial Results 68
6-13 Emission Rates Measured Using the Flux Chamber -
Syringe Sample 71
6-14 Average Surface Liquid Concentrations 72
6-15 Emission Rates Measured Using the Flux Chaimber -
Canister Samples 74
6-16 Summary of Mass Transfer Rates Calculated from Measured
Emission Rates 75
6-17 Syringe, Canister, and Liquid Concentration Data for
Grid Point A -76
6-18 Syringe, Canister, and Liquid Concentration Data for
Grid Point B 77
6-19 Syringe, Canister, and Liquid Concentration Data for
Grid Point E 78
6-20 Syringe, Canister, and Liquid Concentration Data for
Grid Point F 79
6-21 Canister and Liquid Concentration Data for Southwest
Corner 80
6-22 Summary of Flux Chamber Sampling and Analyses 81
7-1 Sample QA Objectives for Precision, Accuracy, and
Completeness - Offsite Laboratory Analysis 83
7-2 GC/FID Volatile Organic Analyses, Liquid Samples Blank
Results 87
7-3 GC/FID Volatile Organics, Liquid Samples Replicate
Analyses 88
7-4 GC/FID Volatile Organic Analyses, Liquid Samples Matrix
Spike Recoveries 89
7-5 GC/FID Volatile Organic Analyses, Sludge Samples Blank
Results 92
7-6 GC/FID Volatile Organics, Sludge Samples Replicate
Analyses 93
7-7 GC/FID Volatile Organics, Sludge Samples Replicate
Analyses 94
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LIST OF TABLES
(Continued)
TABLE PAGE
7-8 GC/FID Volatile Organic Analyses, Sludge Samples Matrix
Spike Recoveries 96
7-9 Semi-Volatile Organic Analyses, Liquid Samples Blank
Results 97
7-10 GC/FID Volatile Organics, Liquid Samples Fteplicate
Analyses 98
7-11 GC/FID Semi-Volatile Organic Analyses, Liquid Samples
Matrix Spike Recoveries, Sample B-l, 46396 100
7-12 GC/FID Semi-Volatile Organic Analyses, Liquid Samples
Surrogate Recoveries 101
7-13 GC/FID Semi-Volatile Organic Analyses, Sludge Samples
Blank Results 103
7-14 GC/FID Semi-Volatile Organic Analyses, Sludge Sample
Replicates 104
7-15 GC/FID Semi-Volatile Organic Analyses, Sludge Samples
Matrix Spike Recoveries, Sample E-5, 46435 105
7-16 GC/FID Semi-Volatile Organic Analyses, Sludge Samples
Surrogate Recoveries 106
7-17 GC/MS Volatile Organic Analyses, Liquid Samples Blank
Results 108
7-18 GC/MS Volatile Organic Analyses, Liquid Samples Matrix
Spike Recoveries 109
7-19 GC/MS Volatile Organic Analyses, Liquid Samples
Surrogate Recoveries 110
7-20 GC/MS Volatile Organic Analyses, Sludge Samples Blank
Results 112
7-21 GC/MS Volatile Organic Analyses, Sludge Samples Matrix
Spike Recoveries 113
7-22 GC/MS Volatile Organic Analyses, Sludge Samples
Surrogate Recoveries 114
7-23 GC/MS Semi-Volatile Organic Analyses, Liquid Sample
Matrix Spike Recoveries, Sample B-l, 46396 116
7-24 GC/MS Semi-Volatile Organic Analyses, Liquid Samples
Surrogate Recoveries 117
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LIST OF TABLES
(Continued)
TABLE PAGE
7-25 GC/MS Semi-Volatile Organic Analyses, Sludge Samples
Blank Results 118
7-26 GC/MS Semi-Volatile Organic Analyses, Sludge Sample
Matrix Spike Recoveries (Sample 46435) 119
7-27 GC/MS Semi-Volatile Organic Analyses, Sludge Samples
Surrogate Recoveries 121
7-28 TOC Analyses Method Blank Results 122
7-29 TOC Analyses, Liquid Samples Replicate Results .... 123
7-30 TOC Analyses, Sludge Samples Duplicate Results .... 125
7-31 TOC Analyses Matrix Spike Results 126
7-32 TOC Analyses, Liquid Samples EMSL QC Sample Results . . 127
7-33 TOC Analyses, Sludge Samples EMSL QC Sample Results . . 128
7-34 POC Analyses Blank Results 129
7-35 POC Analyses, Liquid Samples Replicate Analyses .... 130
7-36 POC Analyses Matrix Spike Results 131
7-37 POC Analyses EMSL QC Sample Results 132
7-38 GC/PID Volatile Organic Analyses Blank Results .... 134
7-39 Duplicate Analyses, GC/PID Volatile Organic Analyses . 135
7-40 Duplicate Analyses, GC/PID Volatile Organic Analyses . 136
7-41 Duplicate Analyses, GC/PID Volatile Organic Analyses . 137
7-42 GC/PID Volatile Organic Analyses Matrix Spike
Recoveries 138
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1.0 INTRODUCTION
The U.S. Environmental Protection Agency is currently developing emission
standards for hazardous waste treatment, storage and disposal facilities
(TSDF). To assist with the development of these standards, EPA's Office of
Air Quality Planning and Standards (OAQPS) is developing an air emissions data
base designed to assess TSDF emission characteristics. Non-point sources such
as ponds, land treatment areas and waste water treatment systems are the focus
of some of these research activities. To date, many of the air emission
estimation techniques in use assume a homogeneous composition in liquid waste
impoundments, although this assumption is unverified. The principal purpose
of this sampling and analytical program was to evaluate this assumption at an
operating site.
1.1 Program Objectives
The primary objective of this field study was to investigate the
variability of the organic chemical composition of a liquid surface
impoundment at the First Chemical Corporation (FCC) in Pascagoula,
Mississippi. Samples were collected from varying horizontal and vertical
points within the impoundment to investigate the stratification of material in
the lagoon. Below are listed some of the sampling objectives of this program:
evaluate the three-dimensional variation of organic chemical
concentrations in the FCC wastewater holding lagoon;
collect samples for use in surrogate analytical parameter study to
evaluate total organic carbon (TOG) and purgeable organic carbon
(POC) as surrogate analyses;
complete field trials of time-integrated volatile organic
compounds (VOC) sampling method using a composite syringe sampler;
measure lagoon air emissions using emissions isolation flux
chambers; and
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characterize the FCC steam stripper treatment process (results are
presented in "Field Evaluations of Hazardous Waste Pretreatment as
an Air Pollution Technique", Draft, U.S. Environmental Protection
Agency, Office of Research and Development, March 31, 1987).
To achieve these objectives a mobile office trailer was set up at FCC and
an extended reach boom unit was used to access the desired sampling areas of
the lagoon. Technical activities included on and offsite analyses,
qualitative and quantitative measurements, visual recordings and
meteorological monitoring.
1.2 Site Description
The First Chemical Corporation facility is a chemical manufacturing plant
which produces primarily nitrated aromatics and aromatic amines. The raw
materials for this process include benzene, toluene, nitric and sulfuric
acid. The lagoon which was studied during the testing program was the
wastewater holding pond for the wastewater treatment system at the plant. The
wastewater treatment system includes two decant tanks, a steam stripper,
carbon adsorption system, and final pH adjustment tank prior to the discharge
of the wastewater stream into the Mississippi Sound.
1.3 Measurement Program
This Field Study Program was conducted at First Chemical Corporation in
Pascagoula, Mississippi during a three day period from November 18 to
November 20, 1985.
To investigate the stratification of organic compounds in lagoons, EPA
conducted the following sampling and analysis tasks:
collection of liquid samples from the surface and at various
depths at four locations.
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bottom sludge sampling at four locations,
onsite analysis for pH, turbidity, specific conductance, dissolved
oxygen,
liquid core sampling using a clear PVC core sampler at each sample
point,
meteorological monitoring onsite, and
a brief study of surface wind effects using a video camera and
cassette recorder.
The collection of liquid samples from the surface and at various depths,
bottom sludge sampling, and the liquid core sampling wore performed to detect
any phase separation or stratification within the lagoon. All of the onsite
analyses performed are typical indicators of contamination. The
meteorological monitoring and the study on surface wind effects were performed
in order to quantify evaporation rates and therefore emissions.
Direct measurement of air emission rates were made at four (4) locations
concurrently with the liquid stratification sampling program. In addition,
two smaller method development tasks were conducted at the FCC lagoon. As a
continuing phase of a surrogate analytical parameter study, field samples were
collected to further evaluate the ability of TOC and/or POC analyses to serve
as surrogates for more expensive compound-specific analyses. In addition,
eight (8) hour field trials of a time-integrated VOC sampling method using a
composite syringe sampler were performed to further evaluate the utility of
this method which may prove useful for the investigation of long-term
compositional variations in liquid processes or impoundments.
1.4 Test Parameters
The parameters collected during the technical activities of this field
study are itemized below:
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Stratification Study,
1. Sample locations and depths,
2. Sample temperatures,
3. Liquid core pictures and descriptions,
4. Onsite analyses: pH, turbidity, conductivity,, dissolved oxygen,
5. Laboratory analyses: GC/FID for a limited number of compounds
expected to be present; for selected samples by GC/MS for all
identifiable compounds which are listed below::
Volatiles
Benzene
Toluene
Acetone
Semi-Volatiles
Phenol
4-Methylphenol
2-Nitrophenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
Nitrobenzene
2,6-Dinitrotoluene
2,4-Dinitrotoluene
Nitroaniline isomers
6. Meteorological data: ambient wind speed, direction,
temperature, and pressure,
7. Surface wind effects video recording, and
8. Process data and information monitored by the plant.
Surrogate Analytical Parameter Study
1. Collection of additional samples for TOG and POC analyses to
compare to GC/MS results from stratification study.
Syringe Composite VOC Sampler Field Trials
1. GC/PID analysis of 8 hour composite syringe samples, and
2. GC/PID analysis of grab samples collected at 2 hour intervals
for comparison to composite syringe samples.
Direct Emissions Measurement
1. Sample location
2. Surface liquid concentration
3. Flux chamber concentrations of specific compounds
4. Flux chamber purge rate
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1.5 Description of Report Sections
The remaining sections of this report present the summary of results and
conclusions in Section 2, process description and operation in Section 3,
sampling locations in Section 4, sampling and analytical methods in Section 5,
detailed results in Section 6, and quality assurance results in Section 7.
Also, included as Appendix A is raw data and Appendix B, the report on the
flux chamber air emission study.
More detailed description of procedures and methods can be found in the
Quality Assurance Project Plan (QAPP) for this program.
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2.0 SUMMARY OF RESULTS AND CONCLUSIONS
2.1 Stratification Study
The stratification study results are based upon samples collected at four
locations in the wastewater holding lagoon. Samples of: liquid and sludge were
collected at up to five vertical points at each of these locations. Table 2-1
summarizes the organic analysis results from these samples. The results are
presented separately for the liquid and sludge samples. Based on the results
of sample analyses, no clear pattern of stratification,, either horizontally or
vertically, exists in either the liquid or sludge phases in the lagoon.
However, the sludge layer is much more concentrated with both volatile and
semivolatile organic compounds. Comparison of the calculated relative
standard deviations (RSD) included in Table 2-1 with the sampling and
analytical method precision estimates reported in the Section 7, Quality
Assurance, reveals that the variations in the reported concentrations in both
phases are similar in magnitude to the precision estimates reported for the
methodology utilized to generate the data.
The data show that approximately 100 times more organic material is
present in the bottom sludge than in the liquid phase^ in the lagoon. This
observation is based only on the target compounds analyzed by GC/FID and is,
therefore, an underestimate since the GC/MS analyses confirmed the presence of
additional compounds in both phases. (Detailed results documenting this
conclusion appear in Table 6-6.)
Further review of the onsite analytical results
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TABLE 2-1
SUMMARY OF RESULTS1 STRATIFICATION STUDY
SAMPLE3
DATE LOCATION
A-l
B-l
E-l
F-l
A-2
B-2
E-2
F-2
A-3
E-3
F-3
A-4
A-5
B-5
E-5
F-5
SAMPLE SAMPLE
TYPE DEPTH
LIQUID 0-.3m
LIQUID 0- . 3m
LIQUID 0-.3m
LIQUID 0-.3m
LIQUID 0.9m
LIQUID 0.9m
LIQUID 0.9m
LIQUID 0.9m
LIQUID 1.2m
LIQUID 1.2m
LIQUID 1.2m
LIQUID 1 . 5m
AVERAGE
SUM(Xi2)
(SUM Xi)2
STD. DEV.
REL.STD.DEV.
SLUDGE 1 . Sin
SLUDGE 1 . 2m
SLUDGE 1.5m
SLUDGE 1 . 5m
AVERAGE
SUM(Xi2)
(SUM Xi)2
STD. DEV.
REL.STD.DEV.
Nitro-
benzene
440
630
390
670
560
880
420
460
480
380
350
1,100
563
4,374,800
45,697,600
227
40
87,000
130,000
14,000
120,000
87,750
3.91E+10
1.23E+11
52,487
60
2,4-Dinitro-
phenol
1,400
160
130
470
250
320
<20
2,000
210
260
110
210
460
6,556,200
30,470,400
604
131
4,600
18,000
9,300
5,200
9,275
4.59E-I-08
1.38E+10
6,180
67
4,6-Dinitro-
6-cresol
32
38
25
63
28
45
15
82
45
<10
30
56
38
22,881
210,681
22
58
2,300
7,700
3,300
2,600
3,975
8.22E+07
2.53E+08
2,518
63
Benzene
12
15
17
16
13
23
21
30
9.4
32
59
23,0002
22
7,546.36
61,206.76
14
63
1,000
1,000
372
2,400
1,193
7.90E+05
2.28E+07
857
72
Toluene
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2.2 Surrogate Analytical Parameter Study
The surrogate parameter study compared the GC/MS organic results to those
generated by TOG and POC analyses for both liquid and sludge samples.
Correlation factors were calculated based on the surrogate parameter result
(POC or TOG) divided by the carbon-weighted cumulative GC/MS analysis
results. The correlation factors developed from these comparisons are:
POC, liquid 4.26 + 1.09, 26% RSD*
(volatile
organics only)
TOC liquid 3.76 + 1.30, 35% RSD
(volatile and
semivolatile
organics)
TOC sludge 1.73 + 1.01, 58% RSD
(volatile and
semivolatile
organics)
* RSD = Relative Standard Deviation
The small size of the data set from which these comparisons were made, is
insufficient to determine if the shift from a 1:1 correlation and/or the
26 percent to 58 percent relative standard deviation (RSD) are truly
characteristic of the performance of these proposed surrogate parameters.
More data are required to further evaluate the performance and adequacy of
these analyses.
2.3 Syringe Sampler Field Trial
Two successful field trials were completed during this program. Utilizing
the ability of the syringe pump to collect multiple samples, a total of three
syringes were collected using the peristaltic pump sample delivery system and
two syringes using a capillary tubing delivery system. The analytical results
(GC/PID for benzene and toluene) for each composite syringe sample were
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compared to the average of five grab samples collected at regular intervals
during the sampling run.
In summary, losses of volatile organics were reported for both composite
syringe systems. The syringe with the peristaltic pump delivery system was
the better of the two syringe systems in terms of the relative amount of VOC
loss. On the average the losses, represented by percent differences between
the syringe composite sample and the average of five grab samples, were:
Syringe with pump - 19 percent
Syringe with capillary - 42 percent
2.4 Flux Chamber Direct Emission Measurement Program
The results of the flux chamber testing are provided in Appendix B.
Calculated air emission rates from the First Chemical Corporation Wastewater
Holding Lagoon ranged from 1.36 x 10~3 to 2.76 x 1CI~2 kg/m2/day of total
nonmethane hydrocarbons, and averaged 1.10 x 10~2 kg/m^/day.
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3.0 PROCESS DESCRIPTION AND OPERATION
3.1 Process Description
The wastewater treatment system at First Chemical Corporation is comprised
primarily of a wastewater holding pond and a steam stripper treatment
process. The process described in this section reflects revisions to that
presented previously in the QAPP. The revisions are based on the collection
of additional data while onsite. The process is outlined in Figure 3-1.
There are four wastewater streams handled by this system, two of which pass
through the entire treatment process, with two entering the system immediately
prior to the discharge of the treated wastewater stream into the Mississippi
Sound.
A wastewater stream which enters the process at the beginning is the
nitrobenzene production wastewater (K104). This wastewater stream flows into
a holding tank, called the "red" tank, due to the color of the wastewater
streams. As the tank is filled, the overflow passes through a submerged
outlet into the wastewater holding lagoon. The second process stream which
enters the lagoon is the plant sump wastewater. This stream is intermittent
and occurs primarily during periods of heavy rain. Two sump pumps are
activated when needed, both of which pump into the lagoon.
The lagoon is 105m x 36m x 3m (the depth is measured from the plant
roadway elevation rather than the top of the berm). It is surrounded by a
cement wall and a plant roadway on the east or plant aide. The wall extends
.3m above the road surface. The berm on the other three sides is 1.7m wide
and consists of ground seashells and extends to approximately the same height
above the lagoon contents as the cement wall. The liquid level in the lagoon
ranged from 4' to 7' in depth, with about 16" of freeboard (measured down from
the level of the plant roadway) above the liquid surface. The remaining depth
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pH-12
Vastevater
Holding
Lagoon No. 1
nitration process vastevater
"Red" tank
Plant tump wastewater
Decant tank
(backwash from carbon change)
(Backflush HO)
STEAM
Boiler
Blowdovn
Non-Contact
Cooling Water
Discharge to
Mississippi Sound
FIGURE 3-1
STEAM STRIPPER PROCESS DIAGRAM
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was comprised of a bottom sludge layer the thickness of which was never
measured directly. By subtraction this layer varied from about 2' to 5' deep.
From the lagoon the wastewater is pumped to the first of two decant
tanks. The bottom organic layer is drawn off and pumped to a holding tank
known as the organic recovery or slop tank. At the time of this study, the
slop tank was a tanker truck. The tanker truck is changed when it becomes
full. The tanker truck and contents are removed from the plant and sold to
another chemical plant where this organic waste is used as an alternate fuel
source. The aqueous top layer from the initial decant tank flows to the steam
stripper feed tank where the pH is adjusted to approximately 3.5.
After pH adjustment, the wastewater stream is fed to the steam stripper.
The average feed rate is reported to be 90-100 gal/min to the stripper. Steam
is fed directly into the bottom of the stripper, stripping the organics from
the wastewater as it passes up through the stripper. The overhead from the
stripper passes through a condenser to the second decant tank. The bottom
organic layer in the decant tank is pumped off to the slop tank, while the top
aqueous layer overflows to return to the steam stripper feed tank. The
bottoms from the steam stripper which are mainly water, are then pumped
through a carbon adsorption system consisting of two columns in parallel. One
column is in use at any particular time while the second column is being
recharged. A carbon column recharge occurs twice daily (once per day per
column) and involves backflushing the column with water and pumping of this
backflush water to the wastewater holding lagoon. The carbon recharge water
is splash filled into the lagoon through a pipe approximately 2 feet above the
lagoon liquid surface. This recharge process removes carbon fines from the
columns and possibly contributes to a surface sludge layer in the lagoon which
appears as a floating black foam. Fresh carbon is added to the column after
the backwash cycle. Calgon Activated Carbon Division has a service contract
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with First Chemical to provide fresh carbon and for the removal and disposal
of the spent carbon.
After passing through the activated carbon system, the wastewater is
pumped to a pH adjustment tank where the pH is adjusted to 7.5 to 8. After pH
adjustment the wastewater stream passes to a fire water holding pond.
Overflow from the fire water holding pond passes to a surge tank where two
additional wastewater streams are added, a boiler blowdown stream and a
non-contact cooling water stream. The combined streams are then discharged to
the Mississippi Sound.
Table 3-1 presents the liquid sludge and total depth measurements taken
during this testing program. The depths were used to calculate total waste
volumes and amounts. A summary of the physical characteristics of the Lagoon
is provided as Table 3-2. This table includes dimensions, volumes, estimates
of retention time and other descriptive information regarding the wastewater
holding lagoon.
TABLE 3-1
LAGOON DEPTHS IN METERS
Sample^
Location
A
B
E
F
Avg.
Liquid
1.29
0.93
0.95
1.15
1.08
Sludge
1.00
1.36
1.34
1.14
1.21
Freeboard
0.76
0.76
0.76
0.76
0.76
Total
3.05
3.05
3.05
3.05
3.05
1 See Figure 4-1 for a diagram of the sampling locations.
3.2 Process Operating Conditions
Based on the information obtained in the pretest survey conducted in
September 1985, a list of process operational variables was developed for
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TABLE 3-2
WASTEWATER HOLDING LAGOON GENERAL CHARACTERISTICS
Variable
Value
Dimension
Type of Sides
Total Capacity
Berm Type
Liner Type
Soil Type
down to -1m depth
-1m depth
Average Depth
Freeboard
Liquid
Sludge
Estimated Waste Volume
Liquid
Sludge
Retention Time
Influent Wastestreams
Wastestream Data
K083
K104
105m x 36m x 3m
1:1 slope
12,000 cubic meters
Crushed Seashells
1m high x 1.5m wide
Packed Clay
Firm to loose fine silty sands
Soft clays
0.8 meters
1.1 meters
1.1 meters
4,400 cubic meters
4,100 cubic meters
20.8 days
K104 - wastewater from production
of nitrobenzene
0.1% sulfur
0.1% chloride
10.5% total water
pH = 7.4
10,600 Btu/lb
Flashpoint = 117 (F)
Viscosity = 4.3 (cs)
4.5 ppm phenol
27 ppm 2-nitrophonol
360 ppm 2,4-dinitrophenol
77 ppm 2,6-dinitrophenol
2,000 ppm nitrobenzene
pH = 2.6
-14-
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TABLE 3-3
PROCESS OPERATING PARAMETERS EFFLUENT CONTROL SYSTEM*
Date
11/18/85
11/19/85
11/20/85
Time
0500
0700
0900
1100
1300
1500
1700
1900
2100
2300
0100
0300
0500
0700
0900
1100
1300
1500
1700
1900
2100
2300
0100
0300
0500
Feed Rate
to Steam
Stripper
(gpm)
116
114
114
116
120
126
126
120
122
112
120
110
183
187
195
196
190
191
194
Inlet to
Steam
Stripper
(pH)
1.93
2.63
1.57
4
1.57
1.46
1.67
1.77
1.4
1.58
1.5
1.61
2.01
1.85
1.85
1.7
1.77
1.75
1.81
1.84
Steam Rate
to Stripper
(Ib/hr)
4100
3700
3800
3558
3558
3640
3580
3765
3547
2901
3000
3572
3740
3740
3790
3859
3944
3925
* All data included in this table is from the Effluent Control
System Data Log provided by First Chemical Corporation.
-15-
-------
collection during testing. Data for many variables on this list were
unavailable because the plant does not monitor flowrates for many of the
selected locations. Copies of the First Chemical Effluent Control System Data
Log are included in Appendix A of this report. Selected parameters from this
data log are presented in Table 3-3, Process Variables.
Because of an approaching hurricane, an abnormal process condition
occurred on 11/20/85, the last or second day of lagoon sampling. The
hurricane watch safety practices used by First Chemical included an increase
in the process rate for the steam stripper to reduce the liquid level in the
lagoon to prevent on overflow in the event of heavy rciinfall. The increased
rate is noticeable in the stripper feed rate data. During an actual hurricane
the production processes are stopped which would further serve to reduce
wastewater flow into the lagoon. Weather predictions of the storm track
forced evacuation of all testing program personnel from the site by the end of
the day on 11/20/85, therefore, the testing program was terminated at this
time.
The following flowrates, which were proposed for data collection during
the program, were not available:
decant water return flowrate to the feed tank;
plant sump wastewater flowrate (this flow was estimated by plant
personnel using a flow integrator at about 1,400 gallons for
11/19/85);
primary plant effluent flowrate;
boiler blowdown flowrate;
non-contact cooling water flowrate and
flowrate through the carbon beds (this flow is reported to be
essentially the same as the feedrate to the steam stripper since
the only difference is the organic material which is sent to the
slop tank).
-16-
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4.0 SAMPLING LOCATIONS
4.1 Stratification Study
Sampling locations at the FCC wastewater holding lagoon were selected
using a systematic approach. The lagoon was divided into fifteen grids of
equal area. Figure 4-1 illustrates the lagoon grids and identifies the four
grids that were sampled, labeled as A, B, E and F. The grids each represented
an area of about 40' x 70' (12m x 21m), or 2800 ft2 (252 m2) of the total
117' x 345' (36m x 105m) or 40,365 ft2 (3780 m2) for the entire lagoon.
Figure 4-1 has been revised since its inclusion in the QAPP utilizing
information obtained from the plant engineering personnel during the field
study. The revision entails a correction to the labelling of the influents to
the lagoon. Details of these corrections are included in the process
description discussion in Section 3 of this report. Originally, it was
proposed that eight (8) of the fifteen (15) total grids would be sampled
during the field study. These eight grids were labeled A through H in the
QAPP. The grids were selected to include in the sampling plan all pertinent
areas of the lagoon including active areas near the inflows and outflows,
potential stagnant areas in the corners and offshore points near the center
line of the lagoon.
During the planning of the sampling program collection of QC samples were
determined by assigning method specific QC set collection to specific sampling
points: (these designations are detailed in the Table 4-1 of the QAPP and
revised in Table 4-1 of this report).
Location QC Set Designation
A none
B-l GC/FID VOC & SVOC
C-3 GC/FID VOC & SVOC
D-4 GC/FID VOC & SVOC
E-5 GC/FID VOC & SVOC
F-l POC
G-l TOC
H-5 TOC
-17-
-------
1
34
5'
V
/
E
-f-
1~
r
| j
1
I
.J_4
*
i
li1
1
1
r
r F~
in
i_
~
__B
fl 1
35-40'
/
V
N
-«-
9
i
§
£
^
1
70'
T
N
__ PT AUT *!TTMP 1'KKI TTFTTT
STEAM STRIPPER
^ INFLUENT/LAI300N
EFFLUENT (SUBMERGED)
CARBON ABSOIU'TION SYSTEM
* '" BACK>LUSH WATER (INT'ERMITTENT
SPLASH FILLING)
PARTIALLY SUBMERGED
BOOM
"
^ PRIMARY PLANT EFFLUENT
(SUBMERGED)
SAMPLING LOCATIONS
FIGURE 4-1
FCC WASTEWATER HOLDING LAGOON SCHEMATIC AND SAMPLING LOCATIONS
-18-
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TABLE 4-1
SAMPLING SUMMARY
Location
A-lb
A-2
A-3
A-4
A-5
B-lb
B-2
B-5
E-lb
E-2
E-3
E-5
F-l»>
F-2
F-3
F-5
Depth
(meters)
0.3
0.9
1.2
1.5
1.8
0.3
0.9
1.2
0.3
0.9
1.2
1.5
0.3
0.9
1.2
1.5
Matrix
Liquid
Liquid
Liquid'
Liquid
Sediment
Liquid
Liquid
Sediment
Liquid
Liquid
Liquid
Sediment
Liquid
Liquid
Liquid
Sediment
GC/FID GC/MS
VOA VOA
Sampl i ng 40 ml 40 ml
method septum vial septum vial
Bacon Bomb
Bacon Bomb
Bacon Bomb
Bacon Bomb
Ponar Grab
Bacon Bomb
Bacon Bomb
Ponar Grab
Bacon Bomb
Bacon Bomb
Bacon Bomb
Ponar Grab
Bacon Bomb
Bacon Bomb
Bacon Bomb
Ponar Grab
X X
X
X
X
X X
X* X
X
X X
X X
X
X
X* X
X X
X
X
X X
GC/FID
SVOC
250 or 500 ml
Amber glass
X
X
X
X
X
X
X
X
X
X
X
X*
X
X
X
X
GC/MS Onsite3 TOC POC
SVOC analysis 40 ml 40 ml
250 or 500 ml 250 ml septum septum
Amber glass Amber glass vial vial
X XXX
X
X
X
X c X
X XXX
X
X c X
X d X X
d
d
X d X
X XXX*
X
X
c X
a Onsite analyses included temperature, pH, conductivity, turbidity and dissolved oxygen.
b Liquid core sample collected for full depth of lagoon at this location.
c Sediment pH was measured using pH paper, and was the only onsite analytical parameter measured for sediment samples.
d Onsite laboratory inoperative, therefore, onsite analysis data not available.
Indicates QC sample set collected at this location for the designated analysis.
-------
The sample locations were not actually assigned to physical points in the
lagoon until the field sampling was initiated, since an arbitrary assignment
might not provide for optimal returns on the placement of QC set collection
within the lagoon.
On November 19 and 20 two grids were sampled each day for a total of four
sample locations. Locations A and B were selected for November 19 for several
reasons discussed below. The movement of a hurricane weather system into the
Pascagoula, MS area on November 20, 1985, made it necessary to select the best
two of the remaining six locations for collection on November 20. Locations E
and F were selected for the reasons also listed below.
11/19/85 Locations A & B
These two grids, A and B, were closest to the primary plant
effluent along the south side of the lagoon and would possibly
provide data most representative of the worst case concentrations
in the lagoon.
Grid location A was designated for no QC sampling and was,
therefore, the best choice as the first sampling point for the
team to accomplish.
Grid location B was designated for a GC/FID QC sample set for the
surface liquid layer. GC/FID analyses are the primary analyses
for the stratification study, therefore, this grid location was
selected as the second point.
On the first day of sampling, it was unclear as to how much time
sampling would require, therefore, the two sampled locations were
selected side by side to minimize change-over time.
11/20/85 Location E
Grid E was chosen to collect samples along the north side of the
lagoon. The north side location provides a sampling site near the
plant sump waste inflow.
Location E was also selected as a possible "stagnant" area site.
The major inflows and outflows are in the south half of the lagoon
which might contribute to more static conditions in the north half.
-20-
-------
Originally, site E was chosen to provide one set of samples
collected at a site where the surface sludge layer was present.
Figure 4-2 illustrates the condition of this layer for the two
sampling days. A wind direction change on 11/20/85 prevented this
goal from being attained as the sludge layer was blown back to the
already sampled south end of the lagoon.
11/20/85 Location F
Grid location F was selected as the third sampling point due to
its proximity to the lagoon effluent. This point was thought to
be fairly representative of the steam stripper inlet material.
Grid F was close to the carbon absorption system backflush water
effluent stream which is the major secondary lagoon influent waste
water stream.
The central location selected for F was also intended to obtain
samples from the middle of the lagoon.
Grid F was designated as the point for a QC sample set for POC and
as was therefore an important part of the surrogate analytical
parameter study.
Location F was designated for a QC set for the sediment layer by
GD/FID.
Table 4-1 summarizes the sampling methods utilized at the various sample
locations and lists the designated analyses.
4.2 Surrogate Analytical Parameter Study
Samples collected for analysis by the surrogate techniques, TOO and POC,
were collected simultaneously with the stratification study sampling.
Table 4-1 outlines the surrogate sampling. In summary, TOG and POC samples
were collected from the surface liquid layer at all four locations plus TOC
samples from the bottom sludge layer at all four locations.
4.3 Composite VOC Syringe Sample Study
Composite syringe samples and grab samples were collected from the surface
liquid layer at the southeast (SE) corner of the lagoon. This corner was
-21-
-------
PARTIALLY
SUBMERGED
BOOM
E
«
11/19/85
AVERAGE METEOROLOGICAL CONDITIONS (8AM-7PM)
8.3mph (3.7mps)
N
11/20/85
AVERAGE METEOROLOGICAL CONDITIONS (SAM-3PM)
N
13.9mph (6.2mps)
FIGURE 4-2
APPROXIMATE CONDITION OF SURFACE SLUDGE LAYER, AT FCC LAGOON
-22-
-------
nearest to the main lagoon influent and it was thought that it would yield the
highest volatile organics (benzene, toluene) concentrations for this study.
The samples were collected through sample lines which extended approximately
two feet into the lagoon from the SE corner. 'Che sampling location,
designated S, is identified in Figure 4-1.
4.4 Steam Stripper Process Study
The steam stripper process was sampled for one day in conjunction with
other work being done by EPA-ORD. The results of this study will be presented
in a separate report by EPA-ORD. The sampling performed is outlined in
Table 4-2 and Figure 4-3. Table 4-2 summarizes the sampling information and
Figure 4-3 illustrates the sampling locations.
4.5 Direct Emissions Measurement Program
Direct emissions measurements were conducted using isolation flux chambers
at the four grid points A, B, E, and F. Figure 4-4 presents a diagram of the
floating flux chamber sampling system. Sampling involved the collection of
teflon air syringes for onsite analysis, and evacuated electropolished
stainless steel canister samples for laboratory analysis. Further details can
be found in the report included as Appendix B. It should be noted that the
lagoon schematic and sampling locations. Figure 3-1 of the report in
Appendix B do not reflect the revised influent/effluent designation or the
location and extent of the surface sludge layer on the sampling days.
Figures 4-1 and 4-2 are more accurate representations of these features.
-23-
-------
TABLE 4-2
STEAM STRIPPER SAMPLING
1.
2.
Location
Influent to
Stripper
Stripper Eff./
Sample Type/
Analytical
Parameter
Liquid/VOC
Liguid/pHb
Liguid/Diss. Solids
Liquid/VOC
Number
4
4
1
4
Sample
Volume
40 ml
50 ml
200 ml
40 ml
Number
Duplicates
1
1
1
1
CA Influent
3. Carbon
Absorption (CA)
Unit Effluent
Liquid/VOC
40 ml
4.
5.
6.
Aqueous
Condensate
Organic
Condensate
Tank Vent
Liquid/VOC
Liquid/VOC
Gas/VOCc
Tank Vent Gas Flow6
Rate
4
2
4
4
40 ml
40 ml
N/A
800 mle
0
0
1
1
a All liguid samples were grab samples as per Section 4.3.3 of the QAPP except
where sampling was conducted from a process line equipped with a valve or
tap. In this case, the valve was purged prior to sample collection. The
dissolved solids sample was collected in a 200 ml nalgene bottle. Also, one
liguid field biased blank (FBB) for VOCs was collected on the day of
sampling.
b pH was measured in the field.
c Tank vent was grab sampled at sample location designated on Figure 4-3.
d Gas samples were collected in 800 ml stainless steel sampling canisters.
Onsite VOC readings using a portable analyzer were also conducted.
e Gas velocity was measured in the field using a "pitot" type system. The
sampling location was an 1" ID. vent pipe which was riot amenable to velocity
monitoring using a conventional EPA Reference Method pitot tube system.
Figure 5-6 illustrates the system utilized in an attempt to get an estimate
of the gas velocity. Data generated using this system is highly suspect and
only useful as an estimate.
-24-
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pK 12
Uasteuater
Holding
Lagoon No. 1
Kltration process vastewater
"Red" tank
Plant rump vactcvater
I Vent Pipe
Decant tank aqueous
. (backwash froc carbon change)
ush H,0) ^.
t
ojc ©
Carbon
Absorption
System
_J
/
X
ft^l Bottoms (mo*
pH
Adjustment
Tank
STEA.V
STRIPPER
STEAM
pH-7.5-8
Tire Hater
Pond
Boiler
Blovdovn
_ Non-Contact
Cooling Water
Discharge to
Mississippi Sound
FIGURE 4-3
STEAM STRIPPER PROCESS SAMPLING LOCATIONS
-25-
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FIGURE 4-4
FLOATING FLUX CHAMBER AND SUPPORT EQUIPMENT
-26-
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5.0 SAMPLING AND ANALYTICAL METHODS
All sampling and analysis procedures utilized to conduct this field study
are fully described in the Quality Assurance Project Plan (QA-064, submitted
under EPA Contract 68-02-3892, WA Number 13). Brief overviews and discussions
are included in this section of the report along with diagrams illustrating
the equipment utilized. All sample containers and sampling equipment were
precleaned and prepared as required in the QAPP. Sample coding and
preservation procedures for collected samples were also adhered to during this
field program. Any deviations or modifications to the procedures and methods
described in the QAPP are summarized in Section 7, Quality Assurance.
5.1 Sampling Equipment/Procedures
5.1.1 Liquid and Sediment Sampling
Bacon Bomb Sampler
This sampler was used to obtain liquid grab samples from a specified depth
in the lagoon. Made completely of brass, and heavily nickel plated, the bomb
is designed to open automatically when the protruding plunger strikes the
bottom of a storage tank (see Figure 5-1). The plunger seals automatically
when the bomb is raised. For collecting samples at specified depths as
intended during this program, a cord was attached to the upper end of the
plunger (Figure 5-1, Chain B). A slight pull on the cord opens the bomb;
closing is automatic when the tension on the cord is released. Samples were
aliquotted from the 500 or 1000 ml sampling capacity of. the Bacon Bomb.
The samplers were cleaned with Alconox and water, with a distilled water
rinse prior to sampling at each of the four sample locations. Alternatively,
if the sampler required additional cleaning between points, an Alconox and
water cleaning solution was added. To prevent contamination of samples, no
organic solvents were used onsite.
-27-
-------
CLOSED
CHAIN
A
OPEN
LOCK
m LOCK
BOnOM OF TANK
FIGURE 5-1
BACON BOMB SAMPLER
-28-
-------
Ponar Grab Sediment Sampler
The Ponar grab sampler is a clamshell type scoop activated by a counter
lever system. The shell is opened and latched in place and slowly lowered to
the bottom. When tension is released on the lowering cable the latch releases
and the lifting action of the cable on the lever system closes the clamshell
(see Figure 5-2).
The Ponar sampler was used to sample sediment and sludge from the bottom
of the lagoon. The "petite" version was used so it could be operated without
a winch or crane.
Penetration depths did not usually exceed several centimeters. Grab
samplers are not capable of collecting undisturbed samples. As a result,
material in the first centimeter of sludge cannot be separated from that at
lower depths. The sampling action of these devices causes agitation currents
which may temporarily resuspend some settled solids. This disturbance was
minimized by slowly lowering the sampler the last half meter and allowing a
soft contact with the bottom. Sediment samples were collected after all
overlying water samples were obtained. The sediment sample from the sampler
was emptied into a large stainless steel bowl from which the sample bottles
were then filled.
Liquid Core Sampler
The liquid core sampler is a modification of the COLIWASA, a much cited
sampler designed to permit representative sampling of multiphase wastes. The
sampler is fabricated from a variety of materials including PVC and Teflon.
In this configuration it consisted of a section of 1 in. ID clear PVC tubing
with a Teflon stopper at one end attached by a wire running the length of the
tube to a locking mechanism at the other end. Manipulation of the wire
locking mechanism opens and closes the sampler by raising and lowering the
-29-
-------
FIGURE 5-2
PONAR GRAB SAMPLER
-30-
-------
Teflon stopper. A schematic of the Liquid Core Sampler is shown in
Figure 5-3. The Liquid Core Sampler was used at each sample location.
Flanges were cemented to one end of the sampler so that it could be
extended for greater depths by adding additional 5 ft lengths of PVC tubing.
After photo documentation (see photos, Figures 6-1 through 6-4), the liquid
core sample was dumped back into the lagoon.
Liquid Grab Sampling With a Telescoping Pole Sampler
Impoundment grab samples were collected using telescoping aluminum poles
modified to hold a sample collection vial, illustrated in Figure 5-4. The
collection containers were glass septum vials with a capacity of 40 ml. The
screw caps have a center hole and a Teflon-faced silicone septum which is used
to seal the vial. Vials and septa were detergent-washed, tap and distilled
water rinsed and oven dried at 105°C prior to use.
The general procedure used for the collection of samples is to secure the
sample vial to the pole with a screw clamp, extend the pole to the required
length and gently submerge and fill the vial. The sample is then carefully
retrieved and sealed using the septum cap, such that no air bubbles are
entrapped in it (i.e., head space free).
Syringe Composite VOC Sampler
A previous EPA task performed involved the research, development, and
testing of a composite VOC sampler for collection of liquid wastewaters. This
system underwent a field trial as a part of the field program. The field
trial involved the collection of duplicate syringe composites and grab samples
from a readily accessible surface location at the lagoon. The average
concentrations of the four grab samples collected every 2 hours were compared
-31-
-------
SET SCREW
LOCKING WIRE
1" ID PVC CLEAR TUBING
TEFLON PLUG
EYE BOLT, FOR PLUG REMOVAL
FIGURE 5-3
LIQUID CORE SAMPLER
-32-
-------
Vrrlgrlp clasp
Bolt hole
Beaker, stainless
steel or disposable
L
Pole, telescoping, aluminum, heavy
duty, 250-650 co (96.160")
FIGURE 5-4
TELESCOPING POLE SAMPLER
-33-
-------
to the result of the syringe composite analysis. One eight (8) hour run was
conducted for each sampling day.
The syringe sampler is illustrated in Figure 5-5. The primary sample
collection method utilized a peristaltic pump as illustrated in this figure.
In the field, three syringes were fitted to the sampler. Two were inserted
into separate septum fittings in the sample line as illustrated. The third
syringe was connected to a passive collection system consisting of a length of
teflon capillary tubing inserted directly onto the syringe needle. The
capillary tubing was prefilled with distilled deionissed water and extended
into the lagoon liquid at the designated sample location. The prefilling was
necessary to eliminate any air bubbles from the sample collection system prior
to the syringe. At the conclusion of sampling, the inlet end of the capillary
tube was inserted into a container of distilled deionized water and the
syringe manually withdrawn to flush all sample from the tubing into the
syringe. The volume of all diluent water used in this technique was recorded
to calculate a dilution correction factor to apply during analytical data
reduction.
5.1.2 Air Monitoring
Meteorological Monitoring
A meteorological monitoring station was set up at a down wind location
near the lagoon. The station was equipped to measure wind speed and
direction. Barometric pressure and temperature was also recorded on days of
sampling using data provided through the National Weather Service from Keesler
Air Force Base in Pensacola, Florida.
Meteorological equipment for the measurement of wind speed and direction
was the Weather Measure Mark III Wind Measuring System. Wind speed is
measured by a stainless steel three-cup anemometer, and converted to an
-34-
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WASTE STREAM
PERISTALTIC PUMP
01
I
SVRMOE PUMP
\
FIGURE 5-5
TIME INTEGRATED LIQUID VOLATILE ORGANIC SAMPLER
-------
electrical signal by a photochopper, which uses a solid state light source for
maximum reliability. Wind direction is obtained with a counterbalanced wind
vane, coupled to a precision potentiometer. Wind speed and direction was
recorded continuously on a dual channel recorder. The meteorological system
was calibrated prior to installation on the site using a synchronous motor
calibrator for wind speed and a compass for direction (as specified in
Section 6.3 of the QAPP). Each instrument and recorder was checked daily to
ensure proper operation. The strip chart was labeled for parameter, time and
date.
Procedure for Surface Wind Effects Recording
Wind effects on the surface of a liquid impoundment are known to affect
the mixing of dissolved and suspended materials within an impoundment. As
documentation of surface wind effects, a short test of the micrometeorological
conditions was conducted as close as possible to the surface of the Wastewater
Holding Lagoon. In general, the test involved the generation of smoke plumes
at the upwind edge of the lagoon and videocassette recording of the plumes as
they pass over the lagoon surface. The plumes were generated by a carbon
dioxide fire extinguisher at the edge of the wastewater lagoon. Plant
personnel were consulted prior to conducting this task. The videocassette
camera was mounted on a tripod at two different locations during the test, one
at 90° to the plume direction and one at 0° to the plume (looking down the
plume from upwind).
Flux Chamber Methodology
The stainless steel components of the flux chamber were cleaned with
acetone, rinsed with water, and dried before each use. A diagram of the flux
chamber is shown in Figure 5-6. The flux chamber was then placed over the
-36-
-------
INCLINED
MICROMANOMETER
(0 to 1" HO)
STATIC
PRESSURE TUBE
(1/8" SS TUBING).
POSITIVE
PRESSURE TUBE
(1/4" ID TEFLON)
SAMPLE
LINE
ft" ID TEFLON)
VENT STACK
(2" ID)
GAS FLOW
DIRECTION
FIGURE 5-6
CUTAWAY DIAGRAM OF FLUX CHAMBER AND SUPPORT EQUIPMENT
-37-
-------
surface area to be sampled. The sweep air was turned on, set at 0.005 m^/min
(5 2./min) flow rate, and the time noted. The outlet gas concentration was
monitored until steady state conditions were reached (typically 3 to 4
residence times). At this time, sample collection was initiated. Samples
collected included liquid samples from the outlet of the flux chamber in both
electropolished stainless steel canisters and glass syringes. The glass
syringe samples were analyzed on site; the remainder of the samples were
returned to the laboratory for analysis. A more detailed description is
provided in Appendix B and includes a description of the ancillary
measurements taken such as flow rates and temperatures.
5.2 Onsite Sample Analysis
Specified parameters were determined onsite with, the use of portable
analytical instruments. Listed below are the parameters which were measured
and the methodology involved. These methods for pH, temperature, turbidity,
conductance and dissolved oxygen are all from EPA-600/4-84-017 "Methods for
Chemical Analysis of Water and Wastes".
pH
The pH of each sample was determined electrometrically using a glass
combination electrode. Samples were analyzed as soon as possible on the same
day as sample collection. Calibration and analytical procedures followed EPA
Method 150.1.
Water Temperature
The lagoon water temperatures were measured with a thermocouple and
digital readout. This thermocouple system measured at-depth liquid
temperatures using a 10-foot thermocouple probe graduated at the selected
-38-
-------
sampling depths. The general procedure used for this determination is EPA
Method 170-1. Calibration prior to sampling was conducted against an NBS
traceable mercury in glass thermometer, for 0°C and 100°C. Calibration data
sheets are included in Appendix A.
Turbidity
The turbidity of the samples were measured using a HACK DR-EL/2 portable
test kit. The turbidimeter consists of a nephelometeir with a Tungsten Lamp
light source and a photo-electric detector. All samples were analyzed on the
same day as collection following procedures specified in EPA Method 180.1.
Specific Conductance
Specific conductance was measured by a Horizon Conductivity meter with a
tungsten reference electrode. All samples were analyzed on the same day as
collection following procedures specified in EPA Method 120.1.
Dissolved Oxygen
Onsite analysis for dissolved oxygen was accomplished using a YSI Model 54
Dissolved Oxygen meter with a membrane electrode. Samples were analyzed as
soon as possible on the same day as sample collection following the procedures
of EPA Method 360.1.
During this program no corrections or modifications were employed to
eliminate bias from dissolved organic materials or inorganic salts.
Calibration against aerated distilled water was the only readily available
procedure employed to minimize the expected interferences.
-39-
-------
5.3 Laboratory Analytical Procedures
GC/FID Analysis - Volatile Organics
Liquid samples submitted for volatile organics analysis were introduced
into the gas chromatograph via direct injection and following the procedures
described in Method 8015 (Reference 1). Instrumental operating conditions for
this analysis are shown in Table 5-1.
Solid samples were dispersed in methanol as described in Method 8240
(Reference 1). Instrumental analysis was conducted according to Method 8015
(Reference 1) and using the instrumental operating conditions as shown in
Table 5-1. Compounds for analysis via this method are s;hown in Table 5-2.
GC/FID Analysis - Extractable Organics
Liquid samples were prepared for analysis by filtration prior to the
methylene chloride extraction as described in Method 62:5 (Reference 2). Solid
samples were soxhlet-extracted in acetone-hexane according to procedures in
Method 3540 (Reference 1). Instrumental analysis for phenols determination
were conducted according to the procedures in Method 8040 (Reference 1).
Quantitation of nitrobenzene and dinitrotoluene followed the protocol in
Method 8090 (Reference 1). Instrumental operating conditions are listed in
Table 5-3. Compounds for analysis via this method are listed in Table 5-2.
GC/MS Analysis - Volatile Organics
Liquid samples were analyzed by the purge and trap technique described in
Method 624 (Reference 2). Instrumental operating conditions are listed in
Table 5-1.
Solid samples were dispersed in methanol and analyzed for volatile
organics as described in Method 8240 (Reference 1). Instrumental operating
conditions are shown in Table 5-1.
-40-
-------
TABLE 5-1
INSTRUMENT CONDITIONS FOR VOLATILE ORGANICS ANALYSIS
GC Conditions
Column
Temperature program
Injector temperature
Carrier flow
GC/FID Instrument Hewlett Packard 5890
GC/MS Instrument Finnegan MAT OWA
Purge and Trap Conditions
Purge gas
Desorption temperature
Desorption time
Oven temperature
MS Conditions
Emission
Electron energy
Scan rate
Mass interval
1% SP-1000 on Carbopack B,
6 ft. x 2 rnm ID column
60°C held for 4 min, then 10/min
to 220°C and held
220°C
UHP helium., 30 ml/min
UHP helium, 40 ml/min
180°C
4 min
200°C
300 a
70 eV
133.3 amu/sec
45-350 amu
-41-
-------
TABLE 5-2
VOLATILE AND SEMI-VOLATILE COMPONENTS
FOR GC/FID ANALYSIS
Volatile Organic Species
Benzene
Toluene
Acetone
Semi-Volatile Organic Species
Phenol
4-Methylphenol
2-Nitrophenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
Nitrobenzene
2,6-Dinitrotoluene
2,4-Dinitrotoluene
Nitroaniline isomers
-42-
-------
TABLE 5-3
GC/MS AND GC/FID OPERATING CONDITIONS FOR EXTRACTABLES ANALYSIS
GC/MS Instrument
GC/FID Instrument
GC Conditions
Column
Temperature program
Injector temperature
Injection volume
Column flow
MS Conditions
Emission
Electron energy
Scan time
Mass interval
Source temperature
Hewlett-Packard 5985, quadrupole
mass spectrometer
Hewlett-Packard 5890
DB-5 30M fused silica capillary
50°C held for 4 min then lOVmin
to 300 °C and held
250°C
1 1, splitless
UHP helium, 0.5 ml/min
300 A
70 eV
1.0 s/scan
45 to 450 amu
200°C
-43-
-------
GC/MS Analysis - Extractable Organics
Liquid samples were subjected to filtration prior to the methylene
chloride extraction described in Method 625 (Reference 2). Instrumental
analysis was conducted according to Method 625. Operating conditions are
shown in Table 5-3.
Solid samples were soxhlet-extracted in acetone-hexane according to
procedures in Method 3540 (Reference 1). Instrumental analysis followed the
procedures described in Method 8270 (Reference 1), with instrumental operating
conditions listed in Table 5-3.
GC/PID Analysis
Samples submitted from the syringe composite sampler study were analyzed
for volatile organics according to the procedures described in Method 8020
(Reference 1), using a GC/PID system.
Total Organic Carbon (TOG)
Total organic carbon analysis was conducted according to the procedures
described in EPA Method 415.2 (Reference 2) utilizing a Dohrmann Model DC-80
Total Organic Carbon Analyzer. The injected sample was transferred to a
quartz ultraviolet reaction coil where it was subjected to intense ultraviolet
illumination in the presence of acidified persulfate reagent. The organic
carbon is converted to carbon dioxide which was then measured by a
non-dispersive infra-red detector (NDIR).
Solid samples were prepared for analysis by slurryirig a weighed aliquot of
sediment with a measured volume of deionized water. The resulting extract was
then analyzed for TOC as described above.
-44-
-------
Purgeable Organic Carbon (POC)
Determination of purgeable organic carbon in the submitted samples was
performed utilizing a Dohrmann Model DC-80 Total Organic Carbon Analyzer
equipped with a PRG-1 Purgeable Organics accessory (Reference 4). Carbon
dioxide from inorganics and the purgeable organics were removed from the
sample by the carrier gas. This carrier gas mixture flowed through a lithium
hydroxide scrubber that removed the carbon dioxide and allowed the purgeable
organics to pass to the hot cupric oxide furnace. The organic matter was then
converted to carbon dioxide which was measured by non-dispersive infra-red
detector (NDIR).
5.4 References
1. Test Methods for Evaluating Solid Waste: Physical/Chemical
Methods, 2nd Edition, SW 846, U.S. Environmental Protection
Agency, Washington, D.C., July 1982.
2. Methods for Chemical Analysis of Water and Wastes,
EPA-600/14-79-020, U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio,
March 1983.
3. Total Organic Carbon - Systems Manual, Dohrmann Division, Xertex
Corporation, Santa Clara, CA, Edition 6, January 1984.
-45-
-------
6.0 DETAILED RESULTS
The detailed results for the investigations conducted during this study
are presented in this section. Results are included for the lagoon
stratification study based on the organic analytical data from samples
collected at varying vertical and horizontal locations in the lagoon, a
surrogate analytical parameter study based on the comparison of TOC and POC
analyses to GC/MS analytical data, the results of field trials of a composite
syringe sampler for volatile organic compounds, and the results of flux
chamber direct emission measurements conducted by Radian Corporation. Raw
data generated from this study, except the flux chamber emissions data, are
presented in Appendix A. Flux chamber data are reported separately in
Appendix B.
6.1 Stratification Study
The investigation of the stratification of the wastewater holding lagoon
at FCC, was the primary goal of this program. The investigation was based on
the collection of onsite information as well as the analytical results of
samples collected and returned to the laboratory.
Onsite Measurements
The results of the onsite analytical work are included in Table 6-1. The
parameters monitored include sample depth, conductivity, temperature, pH,
dissolved oxygen, and turbidity. Sampling points ranged from the top liquid
layer at the surface of the lagoon to the bottom sludge layer. The liquid
depth ranged from 1.4 to 1.7 meters, and the bottom sludge layer varied in
depth from 0.8 to 1.4 meters. (Table 3-1 in Section 3 provides more detail on
the depths and estimated volumes of materials in the lagoon.) Conductivity
readings taken onsite were compromised by the limited range of the field
-46-
-------
TABLE 6-1
RESULTS OF ONSITE ANALYSIS
-J
I
SAMPLE
LOCATION
Al
A2
A3
A4
A5
Bl
B2
B5
El
E2
E3
E5
Fl
F2
F3
F5
DEPTH
(meters)
0-0.3
0.9
1.2
1.5
1.8
0-0.3
0.9
1.7
0-0.3
0.9
1.2
1.5
0-0.3
0.9
1.2
1.5
ONSITE
CONDUCTIVITY
(umhos/cm)
15,500
>20,000
>20,000
>20,000
b
16,500
20,000
b
c
c
c
c
>20,000
>20,000
>20,000
b
CONDUCTIVITY3
(umhos/cm)
14,000
20,000
58,000
b
b
16,000
14,500
15,000
b
15,900
58,000
58,000
b
16,300
15,400
15,700
56,000
62,000
b
AT-DEPTH
SAMPLE
TEMPERATURE
(Celsius) pH
21.5 4.2
21.5 2.0
21.5 0.7
21.5 0.9
21.5 <1
23.0 2.6
21.0 1.6
21.0 <1
c c
c c
c c
c c
19.0 2.3
19.0 1.4
18.0 1.2
19.0 <1
DISSOLVED 02
(ppm)
4.2
2.8
5.2
6.0
b
4.0
4.0
b
c
c
c
c
6.0
3.2
4.6
b
TURBIDITY
(ntu)
971.4
708.1
23.5
971.4
b
971.4
339.5
b
c
c
c
c
708.1
971.4
971.4
b
a Conductivity analysis performed using a YSI model 31 conductivity bridge which has an extended operating range up
to 250,000 umhos/cm versus 20,000 for the field unit.
b Analysis not performed due to potential for damage to analyzer probe.
c Analysis not performed due to demobilization forced by hurricane evacuation.
-------
analyzer. The 20,000 mhos/cm upper limit was exceeded for most samples
necessitating reanalysis following the return of samples to the laboratory.
The resulting data indicate an increase in conductivity with depth, with the
general trend being from 16,000 mhos/cm at the surface to 60,000 mhos/cm above
the bottom sludge layer. No readings were taken of the sludge material itself
due to the potential for damage to the analyzer probe.
With the exception of depth and temperature measurements, these laboratory
conductivity readings were the only onsite analytical measurements taken for
sample location E, due to the hasty evacuation from the site required by an
approaching hurricane storm system. In order to complete the evacuation on
schedule, the field laboratory was broken down and packed for transport off
the site, making it impossible to measure the samples collected from this last
sample point.
Temperature readings indicated no significant temperature gradient in the
lagoon. The data ranged from 18 to 23 degrees Celsius. Since each horizontal
sample location was monitored at a different time over the 2-day sampling
period, the temperature fluctuations are more likely due to overall changes in
the lagoon temperature from day to day or morning versus afternoon, rather
than localized variations within the lagoon.
The sample measurements taken for pH indicated a range of 4.2 to 1. The
data clearly indicate that the lagoon becomes more acidic with depth, with pH
levels decreasing in a steady progression from the top surface layer to the
bottom sludge. The surface layer samples ranged from 2.3 to 4.2, while the
bottom sludge samples all measured 1. This data would indicate that waste
acids tend to accumulate in the bottom sludge in the lagoon.
No significant variation in the dissolved oxygen content of the lagoon
were detected. The collected data ranged from 2.8 to 6.0 ppm, all low values.
-48-
-------
The turbidity results present some indication of stratification within the
lagoon, however, these results are not conclusive. One reading of 24 ntu at
the middle depth of location A indicates a clearer layer at this location, but
all the other readings are between 340 and 970 nephelometry turbidity unit
(ntu). The sample is compared against a standard which is a suspension of
silica of a specified particle size selected such that a 1.0 mg/1 suspension
is one unit of turbidity. The common method of measurement uses a
photoelectric detector that makes use of nephelometry to measure the intensity
of the scattered light.
For additional clarification of the appearance of the various liquid
layers at the four samples locations, pictures of liquid cores collected at
each location are provided in the following Figures 6-1 through 6-4. The low
turbidity value for location A-3 coincides with a light yellow layer in the
photo. The color ranges from a black bottom sludge and surface sludge layer,
to red, orange and yellow zones within the liquid layers.
In addition to these chemical measurements conducted on the samples of the
lagoon contents, meteorological monitoring was conducted. The onsite
meteorological monitoring station provided ambient wind speed and direction
data during the sampling period from sensors mounted on a 10-meter tower at
the downwind northwest corner of the lagoon. The results are provided in
Tables A-l and A-2 in Appendix A of this report. Ambient temperature and
barometric pressure data were obtained from a National Weather Service
monitoring station at nearby Keesler Air Force Base in Pensacola, Florida.
These data are also included in Appendix A, Tables A-3 and A-4. Average
results for the 2 sampling days (11/19/85 and 11/20/85) are:
Wind speed, 3.7 meters/second (from 0000 11/19/85 to 1500 11/20/85).
Wind direction, 175° (from 0000 11/19/85 to 1900 11/19/85) and 75°
(from 1900 11/19/85 to 1500 11/20/85). (Two readings are provided
here to indicate the two distinct wind conditions during sampling.)
-49-
-------
LIQUID CORE SAMPLE; A
DATE COLLECTED
TOTAL DEPTH
NUMBER OF LAYERS
FILM ROLL NO.
FRAME NO.
11/19/85
1.58 meters
4
1
0
Core A shows four distinct zones through the 5 feet of lagoon material
collected. The top zone is a very thin layer, 1 cm, of a floating black oily
sludge. The second reddish-orange liquid layer is opaque and extends to a
depth of 0.6 meters below the surface and blends gradually into the third
layer. The third layer is a clearer greenish-yellow liquid with very little
visible suspended solids and occupies the depths between 0.6 and 1.29 meters,
below the surface. The bottom sludge layer forms a fairly distinct boundary
with the bottom liquid layer and occupies the bottom 0.29 meters of the liquid
core sample, at a depth from 1.29 to 1.58 meters below the liquid surface.
When sampling was conducted no attempt was made to penetrate to the bottom of
this sludge layer, therefore, the total depth of sludge is greater than the
0.29 meters observed in the core.
FIGURE 6-1
LIQUID CORE A
-50-
-------
LIQUID CORE SAMPLE: B
DATE COLLECTED
TOTAL DEPTH
NUMBER OF LAYERS
FILM ROLL NO.
FRAME NO.
11/19/85
1.21 meters
4
1
6
Liquid core sample B, collected from the southeast corner of the lagoon, shows
four distinct layers. The top layer is a thin layer of floating black oil or
sludge, of 1 cm in depth. The second liquid layer is a dull red ranging from
reddish-brown to reddish-orange extending to a depth of 0.5 meters, becoming
less opaque with depth. The third layer is a yellowish-green liquid which
extends between 0.5 and 0.93 meters. The color changes gradually from
yellow-orange at the top of this layer to yellow-green at the bottom. This
layer is less opaque than the upper red layer. The bottom layer is a black
sludge material comprised of fairly fine grained material which extends
between 0.93 and 1.21 meters below the surface. No attempt was made to
penetrate to the bottom of this sludge layer when sampling, therefore the
total depth of sludge is greater than the 0.28 meters observed in the core.
FIGURE 6-2
LIQUID CORE B
-51-
-------
LIQUID CORE SAMPLE: E
DATE COLLECTED
TOTAL DEPTH
NUMBER OF LAYERS
FILM ROLL NO.
FRAME NO.
11/20/85
1.22 meters
5
1
12
Liquid core E was collected from the northwest corner of the lagoon. This
core revealed the presence of five layers in the lagoon. The top-most layer
is an oily film of about 2 cm in depth. This layer is black, contains visible
solid material and forms a distinct boundary with the liquid layer below it.
The second layer is a reddish-orange liquid layer which extends to a depth of
0.52 meters below the surface, becoming less opaque with depth. The third
layer is also liquid and occupies the depth between 0.52 and 0.97 meters.
This third layer is yellow-green and appears less opaque than the reddish
layer above it. Between this lower liquid layer and the bottom sludge or
fifth layer is a fourth layer not noticed in the other three cores. This
layer is a greyish cloudy mixture which hangs above the bottom sludge. This
layer is fairly thin extending only 5 cm in depth. The bottom sludge layer is
comprised of a black sludge and was measured to be the bottom 0.2 meters of
the core. No attempt was made to penetrate to the bottom of the sludge layer
during sampling so the total depth of sludge is greater than that observed in
the core sampler.
FIGURE 6-3 LIQUID CORE E
-52-
-------
LIQUID CORE SAMPLE; F
DATE COLLECTED
TOTAL DEPTH
NUMBER OF LAYERS
FILM ROLL NO.
FRAME NO.
11/20/85
1.76 meters
4
1
10
Liquid core sample F was collected from a point near the center of the
lagoon. Four layers are present in this core. A thin oily layer is visible
as the upper-most layer in the core. This black oily layer is 1 cm in depth.
The second layer is the upper liquid layer which is an opaque brownish-yellow
color. This brownish-yellow layer extends to a depth of 0.23 meters. The
liquid color gradually blends to yellow-orange in the third layer which
extends between 0.23 and 1.15 meters. The color in this layer ranges from an
opaque yellow-brown at the top to a yellow-green at the bottom. The bottom
sludge layer is black in color and extends between 1.15 and 1.76 meters. The
bottom sludge layer depth is greater than that observed in the core sampler
since no attempt to penetrate this layer was made during sampling.
FIGURE 6-4
LIQUID CORE F
-53-
-------
Ambient air temperature, 22°C (from 0000 11/19/85 to 2400 11/20/85).
Barometric pressure, 30.1 inches of Hg (from 0000 11/19/85 to
240011/20/85).
GC/FID Organic Analyses
Samples collected at all liquid depths and from the bottom sludge were
subjected to GC/FID analysis for volatile organics and extractable (or semi-
volatile) organics. The results for these analyses are presented in the
following Tables 6-2 through 6-5, for grid points A, B, E, and F. Summary
tables are provided in Appendix A which summarize the results of all GC/FID
analyses for volatile organics. Table A-5 and for extractable organics,
Table A-6. Review of these results for each grid point provides fairly
conclusive evidence of stratification between the liquid and sludge layers in
the lagoon but not in the liquid layer itself, with the sludge layer ranging
up to several hundred-fold more concentrated than the liquid layer.
With a few exceptions the seven volatile and extractable organics
identified in the liquid layer samples indicate a close agreement in
concentrations for the various layers sampled at each location as well as
between locations. The major components of the liquid samples as measured by
the GC/FID method in order of decreasing concentration are: nitrobenzene,
2,4-dinitrophenol, 4,6-dinitro-o-cresol and benzene.
The major components of the sludge layer are the same as measured in the
liquid samples: nitrobenzene, 2,4-dinitrophenol, 4,6-dinitro-o-cresol and
benzene. The concentration of organic materials in the sludge is much higher
for every compound reported, ranging up to several hundred times more
concentrated for some locations. If it is assumed that the sludge results are
representative of the entire depth of the sludge layer, it is clear that the
organic material found in the liquid layer is only a small fraction of the
-54-
-------
TABLE 6-2
LAGOON CONCENTRATIONS AS MEASURED BY GC/FID ANALYSES3'b
Grid Point: A
Date Sampled: 11/19/1985
Compound
depth =
Benzene
Toluene
Nitrobenzene
2,4 Dinitrotoluene
2-Nitrophenol
2 , 4-Dinitrophenol
4,6-Dinitro-o-cresol
A-l
Liquid
(0-0. 3m)
(mg/1)
12
<1
440
<11
3.5
1,400
32
A-2
Liquid
(0.9 m)
(mg/1)
13
<5
560
<10
<16
250
28
A-3
Liquid
(1.2 m)
(mg/1)
9.4
<5
580
<10
<16
210
45
A-4C
Liquid
(1.5 m)
(mg/1)
23,000
(12,000)
9,900
(4,700)
1,100
11
<16
210
56
A-5
Bottom Sludge
(1.8 m)
(mg/kg)
(1,000)
(520)
(87,000)
(340)
(260)
(4,600)
(2,300)
a Concentrations in parentheses are for sludges; all others represent liquid
concentrations.
b Results are averages where multiple analyses were conducted.
c The volatile fraction of A-4 contained a large amount of sludge material,
such that the liquid and the sludge fractions were analyzed separately.
-55-
-------
TABLE 6-3
LAGOON CONCENTRATIONS AS MEASURED BY GC/FID ANALYSES3'15
Grid Point: B
Date Sampled: 11/19/1985
Compound
depth =
Benzene
Toluene
Nitrobenzene
2,4 Dinitrotoluene
2-Nitrophenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
B-l
Liquid
(0-0. 3m)
(mg/1)
15
<5
630
<20
<43
160
38
B-2
Liquid
(0.9 m)
(mg/1)
23
-------
TABLE 6-4
LAGOON CONCENTRATIONS AS MEASURED BY GC/FID ANALYSES3'b
Grid Point: E
Date Sampled: 11/20/1985
Compound
depth =
Benzene
Toluene
Nitrobenzene
2,4 Dinitrotoluene
2-Nitrophenol
2,4-Dinitrophenol
4 , 6-Dinitro-o-cresol
E-l
Liquid
(0-0. 3m)
(mg/1)
17
<5
390
<11
3.5
130
25
E-2
Liquid
(0.9 m)
(mg/1)
21
<5
420
<10
<16
<20
15
E-3
Liquid
(1.2 m)
(mg/1)
32
<5
380
<10
<16
260
<10
E-5
Bottom Sludge
(1.5 m)
(mg/kg)
(372)
(73)
(14,000)
(315)
(1,000)
(9,300)
(3,300)
a Concentrations in parentheses are for sludges; all others represent liquid
concentrations.
b Results are averages where multiple analyses were conducted.
-57-
-------
TABLE 6-5
LAGOON CONCENTRATIONS AS MEASURED BY GC/FID ANALYSES3'b
Grid Point: F
Date Sampled: 11/20/1985
Compound
depth =
Benzene
Toluene
Nitrobenzene
2,4 Dinitrotoluene
2-Nitrophenol
2,4-Dinitrophenol
4 , 6-Dinitro-o-cresol
F-l
Liquid
(0-0. 3m)
(mg/1)
16
<5
670
<10
<16
470
63
F-2
Liquid
(0.9 m)
(mg/1)
30
<5
460
<20
<43
2,000
82
F-3
Liquid
(1.2 m)
(mg/1)
59
<20
350
<20
C43
110
30
F-5
Bottom Sludge
(1.5 m)
(mg/kg)
(2,400)
(580)
(120,000)
(380)
(320)
(5,200)
(2,600)
a Concentrations in parentheses are for sludges; all others represent liquid
concentrations.
b Results are averages where multiple analyses were conducted.
-58-
-------
total organics in the lagoon. When these concentration results are combined
with the liquid and sludge volume estimates (provided in the preceding
Table 3-1) a rough idea of the ratio between the weight of organics present in
the liquid and sludge layers can be determined. Table 6-6 provides the
results of such a comparison using an average concentration for each of the
four primary lagoon organic components reported in the liquid and sludge
layers.
The results indicate clearly that the majority of the organic material in
the lagoon is in the sludge layer. The ratio of organic weight between the
sludge and liquid layer in this comparison ranged from 19 to 144, with an
average of 77.
GC/MS Organic Analyses
The analytical procedure followed for the previously reported GC/FID
analyses called only for the reporting of the targeted compounds listed in the
project QAPP. In order to document these results and to determine if any
other organic compounds were present at detectable levels, GC/MS
confirmational analyses were conducted on the surface liquid layer samples,
A-l, B-l, E-l, F-l, and on the bottom sludge samples, A-5, B-5, E-5, F-5.
These samples were analyzed for any compound present above the method
detection limit, identifiably using the mass-spectral computer-matching
library of the GC/MS instrument. Using the integration capabilities of the
instruments data reduction software, an integrated total organic estimate was
also calculated. Tables 6-7 and 6-8 provide the results for the liquid and
sludge samples, respectively.
6.2 Surrogate Analytical Parameter Study
The stratification study results provide compound-specific analytical data
required for the investigation of surrogate analytical parameters on samples
-59-
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TABLE 6-6
LIQUID:SLUDGE ORGANIC CONTENT COMPARISON
LIQUID DATA
SLUDGE DATA
WEIGHT RATIO
SLUDGE:LIQUID
ESTIMATED WASTE VOLUME:
AVERAGE WASTE CONCENTRATIONS:1
Nitrobenzene
2,4 Dinitrophenol
4,6-Dinitro-o-cresol
Benzene
4400 cubic meters 4100 cubic meters
560 mg/1
460 mg/1
38 mg/1
22 mg/1
88,000 mg/kg
9,300 mg/kg
4,000 mg/kg
1,200 mg/kg
ESTIMATED WEIGHT OF WASTE COMPOUND:2
Nitrobenzene
2,4 Dinitrophenol
4 , 6-Dinitro-o-cresol
Benzene
2,500 kg
2,000 kg
170 kg
100 kg
360,000 kg
38,000 kg
16,000 kg
4,900 kg
AVERAGE
144
19
94
49
= 77
1 Average concentrations calculated using all liquid values greater than detection
limits from Tables 6-2 through 6-5^
2 Weights for liquid calculated as per the following equation:
weight = (mg/l)(m3 of liquid)(l.OE+03 l/m3)/(1.0E+06 mg/kg)
Weights for sludge calculated as per the following equation:
weight = (mg/kg)(m3 of sludge)(g sludge/ml)(1.0E+Q6 ml/m3)/
(l.OE+03 g/kg)(1.0E+06 mg/kg)
(density of 1 g/ml used for sludge for calculation purposes, the higher
actual density will increase for these waste estimates)
-60-
-------
TABLE 6-7
LAGOON CONCENTRATIONS AS MEASURED BY GC/MS ANALYSES
SURFACE LIQUID LOCATION
Date Sampled: 11/20/1985
Compound
depth
Benzene
Toluene
Nitrobenzene*
Unknown VOC (1)
Unknown VOC (2)
2-Nitrophenol
2,4 Dinitrophenol
4 , 6-Dinitro-o-cresol
4-Nitrophenol
Benzole acid
SUM of reported VOCs
Calculated SUMb-all VOCs
SUM of reported SVOCs
Calculated SUMb-all SVOCs
TOTAL of reported HCs
Calculated TOTAL-all HCs
A-l
(0-0.3 m)
(tng/1)
17
2.0
23/320
<10
<10
9.7
1,100
83
<3.0
42
32
1,510
101,730
1552
101,762
B-l
(0-0.3 m)
(mg/1)
17
2.3
36/270
<10
<10
7.0
190
34
3.5
3.0
55
30
508
199,840
563
199,870
E-l
(0-0.3 m)
(mg/1)
14
2.3
39/240
<10
<10
6.7
180
33
3.4
2.6
55
27
466
37,445
521
37,472
F-l
(0-0.3 m)
(mg/1)
14
2.1
52/340
<10
<10
7.9
300
47
6.1
68
32
736
208,600
804
208,632
a calculated relative to internal standard
b calculated SUMs determined by integrating entire chromatograph and
quantifying against the nearest internal standard
-61-
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TABLE 6-8
LAGOON CONCENTRATIONS AS MEASURED BY GC/MS ANALYSES
BOTTOM SLUDGE LOCATIONS
Date Sampled: 11/20/1985
Compound
depth
Benzene
Toluene
Nitrobenzene*
Unknown VOC (1)
Unknown VOC (2)
2-Nitrophenol
2,4 Dinitrophenol
4 , 6-Dinitro-o-cresol
4-Nitrophenol
Benzole Acid
I some r of Nitrobenzene
I some r of Nitrobenzene
I some r of Nitrobenzene
Isomer of Nitrobenzene
SUM of reported VOCs
Calculated SUMb-all VOCs
SUM of reported SVOCs
Calculated SUMb-all SVOCs
TOTAL of reported HCs
Calculated TOTAL-all HCs
A-5
(1.8 m)
(mg/kg)
1,100
620
450/61,000
<100
500
<2,000
6,400
4,300
<2,000
<1,000
4,800
2,700
2,100
76,500
101,730
79,200
103,830
B-5
(1.2 m)
(mg/kg)
1,100
300
740/135,000
<100
300
760
11,700
5,100
<550
<550
6,800
2,300
14,200
2,100
2,400
1,700
177,200
199,840
179,600
201,540
E-5
(1.5 m)
(mg/kg)
1,500
430
1,000/8,100
<100
450
120
5,500
3,300
200
<1,000
1,380
175
960
670
340
2,800
20,405
37,445
20,745
40,245
F-5
(1.5 m)
(mg/kg)
2,100
590
1,500/121,000
800
440
125
16,800
12,600
<500
<500
41,150
14,650
27,000
2,350
5,400
3,400
, 235,675
208,600
241,075
212,000
a calculated relative to internal standard
b calculated SUMs determined by integrating entire chromatograph and
quantifying against the nearest internal standard
-62-
-------
collected at the First Chemical wastewater holding lagoon. The selected
surrogate parameters to which these compound-specific results are compared are
purgeable organic carbon (POC) and total organic carbon (TOC). The goal of
this investigation is to compare the sum of carbon-weighted compound specific
results to POC and TOC analyses of the same samples. POC analyses are
compared to the results of GC/MS volatile organic results and TOC analyses are
compared to the results of GC/MS volatile organic and semi-volatile organic
results.
Samples were collected from the surface liquid layer and the bottom sludge
layer to evaluate the correlation factors for the two sample matrices. The
liquid samples were evaluated for both the POC and IOC surrogates and the
sludge samples were evaluated only for TOC. The correlation factors were
calculated by dividing the surrogate result by the sum of the carbon-weighted
compound-specific results provided by the GC/MS analysis. The data generated
by this comparison are presented in the following Tables 6-9, 6-10 and 6-11.
(QC results for the TOC and POC analyses including EMSL spikes, matrix spikes,
duplicates, and blanks are included in Section 7). Table 6-9 presents the
data generated for the POC comparison of the liquid samples. Table 6-10 the
results of the TOC comparison for the liquid samples, and Table 6-11 the
results of the TOC comparison for the sludge samples. The populations for
these three comparisons are very small, with four (4) data pairs for each
category. The abbreviated sampling program was a critical factor in this
outcome, as the original goal was to have eight (8) data pairs for each
comparison.
The following results were obtained for correlation factors:
POC Liquid 4.26 +/- 1.09
TOC Liquid 3.76 +/- 1.30
TOC Sludge 1.73 +/- 1.01
-63-
-------
TABLE 6-9
SURROGATE STUDY RESULTS, POC VS. GC/MS VOC
i
en
SAMPLE
LOCATION
A-l
B-l
E-l
F-l
Cs
POC
(ppm)
178
166
144
145
Ct Ri
GC/MS Cs/Ct GC/MS
VDA** PARAMETER
30.97 5.75 Benzene
Toluene
Nitrobenzene
38.85 4.26 Benzene
Toluene
Nitrobenzene
37 . 84 3 . 82 Benzene
Toluene
Nitrobenzene
45.27 3.20 Benzene
Toluene
Nitrobenzene
MW
MOLECULAR
WEIGHT
78.12
92.15
123.11
78.12
92.15
123.11
78.12
92.15
123.11
78.12
92.15
123.11
NUMBER
OF CARBONS
6
7
6
6
7
6
6
7
6
6
7
6
Wcx
WEIGHT of
CARBONS
72.06
84.07
72.06
72.06
84.07
72.06
72.06
84.07
72.06
72.06
84.07
72.06
Cx
SAMPLE
CONCENTRATION
(ppm)
17.0
2.0
23.0
17.0
2.3
36.0
14.0
2.3
39.0
14.0
2.1
52.0
Cti
WEIGHTED
CONCENTRATION
15.68
1.82
13.46
15.68
2.10
21.07
12.91
2.10
22.83
12.91
1.92
30.44
AVG of Ri = 4.26
SUM of {Ri)- = 76.05
(SUM of Ri)2 = 290.05
S = 1.09
-------
TABLE 6-10
SURROGATE STUDY RESULTS, TOC VS. GC/MS VOC AND SVOC LIQUID SAMPLES
CM
cn
Cs Ct Ri MW
SAMPLE TOC GC/MS Cs/Ct GC/MS MOLECULAR
LOCATION (ppm) (ppm) PARAMETER WEIGHT
A-l 1454 675.59 2.15 Benzene
Toluene
Nitrobenzene
2-Nitrophenol
2 , 4-Dimtrophenol
4 , 6-Dinitro-o-cresol
4-Ni t rophenol
Benzole Acid
B-l 1250 272.11 4.59 Benzene
Toluene
Nitrobenzene
2-Nitrophenol
2 ,4-Dinit rophenol
4 , 6-Dinitro-o-cresol
4-Nit rophenol
Benzoic Acid
E-l 1240 246.97 5.02 Benzene
Toluene
Nitrobenzene
2 -Ni t rophenol
2 ,4-Dinit rophenol
4 , 6-Dinitro-o-cresol
4-Nit rophenol
Benzoic Acid
F-l 1183 359.49 3.29 Benzene
Toluene
Nitrobenzene
2-Nitrophenol
2 ,4-Dinitrophenol
4 , 6-Dinitro-o-cresol
4-Nit rophenol
Benzoic Acid
AVG of Ri _ = 3.76
SUM of {Ri)2, = 61.77
(SUM of Ri)2 = 226.73
S = 1.30
78.12
92.15
123.11
139.11
184.11
198.14
139.11
122.13
78.12
92.15
123.11
139.11
184.11
198.14
139.11
122.13
78.12
92.15
123.11
139.11
184.11
198.14
139.11
122.13
78.12
92.15
123.11
139.11
184.11
198.14
139.11
122.13
Wcx
NUMBER WEIGHT of
OF CARBONS CARBONS
6
7
6
6
6
7
6
7
6
7
6
6
6
7
6
7
6
7
6
6
6
7
6
7
6
7
- 6
6
6
7
6
7
72.06
84.07
72.06
72.06
72.06
84.07
72.06
84.07
72.06
84.07
72.06
72.06
72.06
84.07
72.06
84.07
72.06
84.07
72.06
72.06
72.06
84.07
72.06
84.07
72.06
84.07
72.06
72.06
72.06
84.07
72.06
84.07
Cx
SAMPLE
CONCENTRATION
(ppm)
17.0
2.0
320.0
9.7
1,100.0
83.0
<3
ND
17.0
2.3
270.0
7.0
190.0
34.0
3.5
3.0
14.0
2.3
240.0
6.7
180.0
33.0
3.4
2.6
14.0
2.1
340.0
7.9
300.0
47.0
8.1
ND
Cti
WEIGHTED
CONCENTRATION
15.68
1.82
187.31
5.02
430.54
35.22
0.00
0.00
15.68
2.10
158.04
3.63
74.37
14.43
1.81
2.07
12.91
2.10
140.48
3.47
70.45
14.00
1.76
1.79
12.91
1.92
199.01
4.09
117.42
19.94
4.20
0.00
-------
TABLE 6-11
SURROGATE STUDY RESULTS, TOC VS. GC/MS VOC AND SVOC SLUDGE SAMPLES
i
CTi
CTi
I
Cs Ct Ri MW Wcx Cx Cti
SAMPLE
SAMPLE TOC GC/MS Cs/Ct GC/MS MOLECULAR NUMBER WEIGHT of CONCENTRATION WEIGHTED
LOCATION (ppm) (ppm) PARAMETER WEIGHT OF CARBONS CARBONS (ppm) CONCENTRATION
A-5 86,946 4,4424.44 1.96 Benzene
Toluene
Nitrobenzene
2-Nitrophenol
2 ,4-Dimt rophenol
4 , 6-Dinitro-o-cresol
4-Bit rophenol
Benzoic Acid
I some r of Nitrobenzene
B-5 120,862 102,312.26 1.18 Benzene
Toluene
Nitrobenzene
2-Nitrophenol
2 ,4-Dim.t rophenol
4 , 6-Dinitro-o-cresol
4-Nit rophenol
Benzoic Acid
I some r of Nitrobenzene
E-5 36,854 12,100.01 3.05 Benzene
Toluene
Nitrobenzene
2-Nitrophenol
2 , 4-Dimtrophenol
4 , 6-Dinitro-o-cresol
4-Nitrophenol
Eenscic Acid
I some r of Nitrobenzene
F-5 99,620 135,127.52 0.74 Benzene
Toluene
Nitrobenzene
2-Nitrophenol
2 ,4-Dinit rophenol
4 , 6-Dinitro-o-cresol
4-Nitrophenol
Benzoic Acid
Isomer of Nitrobenzene
AVG of Ri _ = 1.73
SUM of (Ri)2, = 15.05
(SUM of Ri)2 = 47.91
S = 1.01
78.12
92.15
123.11
139.11
184.11
198.14
139.11
122.13
123.11
78.12
92.15
123.11
139.11
184.11
198.14
139.11
122.13
123.11
78.12
92.15
123.11
139.11
184.11
198.14
139.11
122.13
123.11
78.12
92.15
123.11
139.11
184.11
198.14
139.11
122.13
123.11
6
7
6
6
6
7
6
7
6
6
7
6
6
6
7
6
7
6
6
7
6
6
6
7
6
7
6
6
7
6
6
6
7
6
7
6
72.06
84.07
72.06
72.06
72.06
84.07
72.06
84.07
72.06
72.06
84.07
72.06
72.06
72.06
84.07
72.06
84.07
72.06
72.06
84.07
72.06
72.06
72.06
84.07
72.06
84 = 07
72.06
72.06
84.07
72.06
72.06
72.06
84.07
72.06
84.07
72.06
1,100.0
620.0
61,000.0
<2,000
6,400.0
4,300.0
<2,000
<1,000
4,800.00
1,100.0
300.00
135,000.0
760.0
11,700.0
5,100.0
<550
<550
25,400.00
1,500.0
430.0
8,100.0
120.0
5,500.0
3,300.0
200.0
<1.-000
3,185.00
2,100.0
590.0
121,000.0
125.0
16,800.0
12,600.0
<500
<500
85,150.00
1,014.67
565.64
35,705.14
0.00
2,504.94
1,824.47
0.00
0.00
2,809.58
1,014.67
273.70
79,019.58
393.69
4,579.34
2,163.91
0.00
0.00
14,867.39
1,383.64
392.30
4,741.17
62.16
2,152.68
1,400.18
103.60
0.00
1,864.28
1,937.10
538.27
70,824.95
64.75
6,575.46
5,346.13
0.00
0.00
49,841
-------
Theoretically, one would expect that the correlation factors would range
much closer to one, however, with the complex sample matrix found at this
lagoon, the shift away from a one to one correlation is not unexpected. Also,
one variable involved in the POC comparison is the difference in the purge
time utilized by the two different methods. The GC/MS method has a
characteristically different purge cycle than the less flexible POC analyzer.
A definitive conclusion as to the adequacy of the surrogate nature of the POC
and TOG analyses is not possible based on the small data set presented in this
report, however, the statistical distribution of the four results within each
category are fairly close as evidenced by the standard deviation for the
correlation factors being between 26 percent and 35 percent of the average for
both liquid surrogates. The correlation factor for sludges is much closer to
1 at 1.73, but demonstrated a higher standard deviation of about 60 percent of
this average. More extensive application of this surrogate analysis program
is necessary before any further conclusions can be drawn. Ideally, a larger
numbers of samples and a greater variety of waste types should be evaluated.
6.3 Syringe Composite VOC Sampler
During this testing program field trials of a time-integrating volatile
organic compounds sampler were conducted. The sampler is illustrated in the
sampling methods discussion of Section 5. Again due to the abbreviated
duration of the field testing program, only a small data set was obtained. In
order to maximize the results obtained from this study triplicate analyses
were performed on all syringe samples collected. The results of the syringe
to grab sample comparisons are presented in Table 6-12. In all cases the
syringe composite sample analysis was compared to the average of the results
of five (5) grab samples collected at two (2) hour intervals during the runs.
-67-
-------
TABLE 6-12
SYRINGE SAMPLER FIELD TRIAL RESULTS
i
CTi
OD
CONTROL
NUMBER
46477
46479
46481
46483
46485
46488
46490
46478
46480
46482
464S4
46486
46489A
46489A
46490
GC/PID
RESULTS
SAMPLE BENZENE
TYPE (mg/1)
GRAB #1
GRAB #2
GRAB #3
GRAB #4
GRAB #5
SYRINGE PUMP
SYRINGE PUMP
SYRINGE PUMP
SYRINGE CAPILLARY
SYRINGE CAPILLARY
SYRINGE CAPILLARY
(dilution factor = 1.32)
GRAB #1
GRAB #2
GRAB #3
GRAB #4
GRAB #5
SYRINGE PUMP
SYRINGE PUMP
SYRINGE PUMP
SYRINGE PUMP - DUP
SYRINGE PUMP - DUP
SYRINGE PUMP - DUP
SYRINGE CAPILLARY
SYRINGE CAPILLARY
SYRINGE CAPILLARY
27
28
28
26
31
23
23
22
17
17
17
34
36
33
O A
o-±
27
26
27
27
24
25
24
25
24
24
GC/PID
RESULTS AVERAGE
BENZENE
TOLUENE CONCENTRATION PERCENT
(mg/1) (mg/1) DIFFERENCE
2.7
3.2
2.8
2.8
2.7 26.0
2.9
2.8
2.8 22.7 -19.05
1.3
1.2
1.3 17.1 -38.91
5.1
4.3
3.8
c n
J W
4.4 32.8
3.8
3.7
3.8 26.7 -18.70
3.2
3.1
3.0 24.3 -25.81
2.6
2.5
2.5 24.1 -26.60
TOLUENE
CONCENTRATION PERCENT
(mg/1) DIFFERENCE
2.84
2.83 -0.23
1.25 -55.99
4.52
3.77 -16.67
3.10 -31.42
2.55 -43.67
(dilution factor = 1.39)
-------
All analyses were done via GC/PID for two principle volatile organic
components of the lagoon wastewater, benzene and toluene.
A total of three runs were conducted, one each on 11/18/85, 11/19/85 and
11/20/85. Run 1 collected on 11/18/85 was discarded in the field due to a jam
in the syringe withdrawal mechanism, therefore no analyses were performed for
this run. The jam was discovered too late to prevent a significant loss of
sample in the syringe. Run 2, collected on 11/19/85, was uneventful and
involved the collection of duplicate syringe samples. One syringe was used to
sample from the peristaltic sample delivery system for the full run. The
second syringe sampled the lagoon through a passive capillary tubing delivery
system which used no pumping device but drew sample simply from the withdrawal
of the syringe barrel. (The particulars of the two methods themselves are
described in Section 5). Run 3 involved the collection of three syringe
samples. Two syringes were used to collect duplicate samples using the
peristaltic pump sampling system. The third syringe was used with the
capillary tubing sampling system.
This study resulted in the collection of three (3) syringe composite
samples with the peristaltic pump system and two (2) syringe composite samples
using a capillary tubing sampling system. Review of the results provided in
Table 6-12 indicates that both syringe sampling methods resulted in
significant volatile organic losses. The limited amount of data precludes the
application of more elaborate statistical evaluations of this data, however,
the percent differences are indicative of the composite sampler performance.
The following percent differences were reported:
Syringe with Pump
benzene -19, -19 and -26 %
toluene -0.2, -17 and -31 %
Syringe with Capillary Tubing
benzene -39, and -21 %
toluene -56, and -44 %
-69-
-------
Earlier bench studies conducted using this sampler indicated that the
syringe was capable of accurately sampling a test tank under varying dilute
concentrations of volatile organics. The major differences in the field
application of this methodology versus the bench study are likely to
contribute to the observed sample loss. These differences are listed below:
1. Both of the sampling systems employed to deliver lagoon wastewater
to the syringe used five (5) foot lengths of 1/8 inch diameter
teflon tubing extending from the lagoon surface to the syringe
sampler. It is possible sample losses occurred through adsorption
or absorption of sample components to the tubing walls. The bench
study involved collection of samples through a much shorter length
of tubing, about one (1) foot.
2. The concentrations of the volatile organic components of the
wastewater were much higher than the test stream generated during
the bench study. The lagoon had concentrations of 1 to 36 mg/1
levels versus the 100 g/1 levels used during the bench study.
These higher concentrations could have contributed to the poorer
performance of the syringe sampler.
3. Beyond the elevated volatile organics concentrations cited
previously, the complex sample matrix of the lagoon wastewater
could also have impacted syringe sampler performance. The bench
study utilized a dilute water stream which is enormously different
from the concentrated mixture of volatile and semivolatile
components of the lagoon wastewater.
6.4 Flux Chamber Direct Emission Measurement Program
The specific objective for this program was to conduct volatile organic
compound emission rate measurements using an isolation flux chamber and
associated sampling techniques and analyses. In support of this objective,
gas and liquid samples were collected at each of the four grid locations at
the wastewater holding lagoon for analysis.
The emission rate data obtained from this program are tabulated in the
following tables:
6-13 - Emission Rates as Measured by On-Site Syringe Sample Analyses
6-14 - Average Surface Liquid Concentrations
-70-
-------
TABLE 6-13
EMISSION RATES MEASURED USING THE
FLUX CHAMBER - SYRINGE SAMPLE
Emission Rate
Grid A Grid B Grid E Grid F Mean
Total NMHC 167 316 237 195 226
a Average emission rate based upon analysis of duplicate samples, TNMHC.
-71-
-------
TABLE 6-14
Average Surface Liquid Concentrations
to
Compound
N-Butane
1-Nonene
Chloromethane
Cyc lohexane
Chloroethane
Tetrachloroethylene
Toluene
Benzene
N-Undecane
Methylchloride
Hethylcyc lopentene
2,3-Dimethylpentane +
Isoheptane
C9 Alkane
CIO * Alkane
Isobutene + 1-Butene
2-Methyl-2-Butene
C-2-Butene
A-Piriene
Styrene
C8 Alkene
CIO * Arcaatic
Trichlorof loromethane
1 ,1-Dichloroethylene
Paraffins
Olef ins
Total Aromatic s
Total Halogenated RC
Unidentified VOC
Total NMHC
Henry's
Constant
(atmnH/mol)
2.15E+01b
1.57E+OOb
1.01E+OOb
9.57E-01b
3.08E-01b
2.80E-02
6.64E-03
5.50E-03v
4.59E-03b
3.19E-03
8.67E-04b
Grid A
(ppm)
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
2.45E+00
2.02E+01
1.80E-01
<.007
4.42E-01
6.23E-02
O.OOE+00
O.OOE+00
2.09E-02
3.79E-02
O.OOE+00
O.OOE+00
1.36E-01
O.OOE+00
2.38E-02
5.55E-02
8.85E-02
O.OOE+00
2.82E-01
6.39E-01
2.27E+01
6.33E-01
7.64E+01
1.01E+02
Grid Ba
(ppm)
4.87E-02
O.OOE+00
O.OOE+00
6.41E-02
O.OOE+00
2.89E-02
1.88E+00
1.42E+01
1.20E-01
2.68E-02
1.64E-01
O.OOE+00
O.OOE+00
1.15E-01
O.OOE+00
3.18E-02
O.OOE+00
5.50E-02
8.86E-02
8.94E-02
2.27E-02
U.39E Oi
4.39E-01
1.43E-02
2.57E-01
2.42E-01
1.65E+01
3.17E-01
4.46E+01
6.18E+01
Grid Ea
(ppm)
O.OOE+00
O.OOE+00
6.14E-03
O.OOE+00
1.28E-01
O.OOE+00
2.29E+00
1.41E+01
1.46E-01
3.82E-02
2.92E-01
4.99E-02
O.OOE+00
O.OOE+00
O.OOE+00
2.52E-02
O.OOE+00
O.OOE+00
1.12E-01
O.OOE+00
O.OOE+00
H. / 4.C. \lf.
8.92E-01
O.OOE+00
1.96E-01
4.16E-01
1.64E+01
1.15E+00
5.34E+01
7.16E+01
Grid Pa
(ppm)
O.OOE+00
6.94E-02
O.OOE+00
5.58E-02
O.OOE+00
O.OOE+00
2.05E+00
1.33E+01
1.11E-01
7.27E-02
1.77E-01
4.72E-02
O.OOE+00
O.OOE+00
O.OOE+00
9.27E-02
3.50E-03
O.OOE+00
7.12E-02
O.OOE+00
1.89E-02
6.22E-02
5.20E-01
O.OOE+00
1.31E-01
3.87E-01
1.54E+01
5.35E-01
3.62E+01
5.26E+01
SW Corner8
(ppm)
O.OOE+00
O.OOE+00
O.OOE+00
6.97E-02
1.91E-02
2.63E-01
4.49E+00
2.54E+01
1.67E-01
7.15E-03
1.73E-01
5.18E-02
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
1.20E-01
O.OOE+00
O.OOE+00
G.GOE+00
6.89E-01
5.46E-02
2.62E-01
2.93E-01
2.99E+01
1.25E+00
5.85E+01
8.99E+01
Mean
Cone .
(ppm)
1.35E-02
1.39E-02
1.23E-03
3.79E-02
2.94E-02
5.84E-02
2.63E+00
1.74E+01
1.45E-01
2.89E-02
2.50E-01
4.22E-02
O.OOE+00
2.30E-02
4.18E-03
3.75E-02
7.00E-04
1 . 10E-02
1.05E-01
1.79E-02
1.31E-02
1 .61E-G1
5.26E-01
1.38E-02
2.25E-01
3.95E-01
2.01E+01
7.76E-01
5.38E+01
7.54E+01
aAverage concentration based upon duplicate gas canister samples.
bEstimated value,(Equation A-6).
-------
6-15 - Emission Rates as Measured by Canister Sample Analysis
6-16 - Summary of Mass Transfer Rates
6-17 - Summary of Concentration Data for Grid Point A
6-18 - Summary of Concentration Data for Grid Point B
6-19 - Summary of Concentration Data for Grid Point E
6-20 - Summary of Concentration Data for Grid Point F
6-21 - Summary of Concentration Data for Southwest Corner
6-22 - Summary of Flux Chamber Sampling and Analyses:
The emission factors isolation flux chamber (or flux chamber) is an enclosure
device used to make direct emission rate measurements. The flux chamber
isolates a defined surface area and encloses gaseous emissions. Clean, dry
sweep air is added to the chamber at a fixed, controlled rate. The sweep air
flow rate through the chamber is recorded and the concentration of the species
of interest is measured at the exit of the chamber. The emission rate is
calculated as:
Where:
ERi = emission rate of species, i,
Yi = measured concentration of species i, (ug/1)
Q = sweep air flow rate (1/min)
A = exposed surface area, m2
Normally three to five residence times (volume divided by flow rate) is needed
to establish steady-state conditions in the chamber for sampling. The
analytical results of a sample of the floating foam material on the lagoon
surface are presented in Appendix B, along with the full report of the flux
chamber monitoring activities.
-73-
-------
TABLE 6-15
Emission Rates Measured Using the Flux Chamber - Canister Samples
Henry ' 8
Compound Constant
(atm m-Vmol)
N-Pentane
N-Rexane
Cyc lohexane
N-Heptane
Tetrachloroethylene
N-Decane
Toluene
Ethylbenzene
Benzene
1 ,1 ,1-Trichloroethane
N-Undecane
Chloroform
Methylchloride
Trichloroethylene +
Bromodichloromethane
C3 VOC
Paraffins
Olefins
Total Aroma tic 8
Total Halcgenated KG
Unidentified VOC
Total NHHC
6.05E+OOb
1 . 78E+OOb
9.57E-01b
5.40E-01b
2.80E-02
1.52E-02b
6.64E-03
5.88E-03b
5.50E-03
4.92E-03
4.59E-03b
3.93E-03
3.19E-03
Emission Rates (kg/m^-day)a
Grid A
(ppm)
O.OOE+00
O.OOE+00
6.41E-06
O.OOE+00
O.OOE+00
O.OOE+00
5.14E-03
O.OOE+00
9.42E-03
O.OOE+00
1.33E-05
3.53E-06
3.38E-04
O.OOE+00
3.43E-05
4.14E-05
4.53E-03
1 .45E-02
5 /.ni?_n/.
-^ TV/4J Vt
8.12E-03
2.76E-02
Grid B
(ppm)
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
2.76E-05
2.87E-03
O.OOE+00
6.69E-03
O.OOE+00
O.OOE+00
O.OOE+00
4.80E-06
O.OOE+00
O.OOE+00
2.76E-05
O.OOE+00
6.52E-03
4.80E-06
5.01E-03
1.16E-02
Grid E
(ppm)
2.78E-04
3.60E-04
O.OOE+00
1.09E-04
O.OOE+00
O.OOE+00
8.51E-04
O.OOE+00
3.86E-03
O.OOE+00
O.OOE+00
O.OOE+00
2.71E-05
O.OOE+00
O.OOE+00
7.48E-04
O.OOE+00
4.71E-03
2.71E-05
2.29E-04
5.35E-03
Grid P
(ppm)
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
1.12E-03
3.75E-05
6.92E-03
O.OOE+00
O.OOE+00
O.OOE+00
2.90E-05
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
8.07E-03
i f\f\vr f\e
*- m 7VKt\/J
1.14E-03
9.25E-03
SH Corner
(ppm)
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
2.61E-06
O.OOE+00
2.69E-04
O.OOE+00
7.58E-04
4.13E-05
O.OOE+00
O.OOE+00
3.69E-05
2.14E-06
O.OOE+00
O.OOE+00
O.OOE+00
1.03E-03
4.15E-05
2.99E-04
1.36E-03
Mean
(ppm)
5.56E-05
7.20E-05
1.28E-C6
2.18E-05
5.22E-07
5.52E-06
2.05E-03
7.50E-06
5.53E-03
8.26E-06
2.66E-06
7.06E-07
8.72E-05
4.28E-07
6.86E-06
1.63E-04
9.06E-04
6.97E-03
8.85E-05
2.96E-03
1.10E-02
aAverage emission rate based upon duplicate gas canister samples.
''Estimated value,(Equation A-6).
-------
TABLE 6-16
Summary of Mass Transfer Rates
Calculated from Measured Emission Rates
Compound
N-Butane
N-Pentane
N-Hexane
1-Nonene
Chlorome thane
Cyclohezane
N-Heptane
Chi o roe thane
Tetrachloroethylene
N-Decane
Toluene
Ethylbenzene
Benzene
1,1. 1-Trichloroethane
N-Undecane
Chloroform
Methylchloride
Methylcyclopentene
Trichloroethylene +
Bromodichlorome thane
C3 VOC
2.3-Dimethylpentane +
Isoheptane
C9 Alkane
CIO + Alkane
Isobutene + 1-Butene
2-Methyl-2-Butene
C-2-Butene
A-Pinene
Styrene
C8 Alkene
CIO + Aromatic
Trichlorofloromethane
1 , 1-Dichloroethylene
Paraffins
Olefins
Total Aroma tics
Total Halogenated HC
Unidentified VOC
Total NMHC
Henry ' s
Constant
(atm m^/mol)
2.15E+01C
6.05E+00C
1.78E+00C
1.57E+00C
1.01E+00C
9.57E-01C
5.40E-01C
3.08E-01C
2.80E-02d
1.52E-02C
6.6AE-03d
5.88E-03C
5.50E-03d
4.92E-03d
4.59E-03C
3.93E-03d
3.19E-03d
8.67E-04C
Liquid
Cone . a
(mg/m3)
1.35E+01
1.39E+1
1.23
3.79E+1
2.94E+1
5.84E+1
2.63E+3
1.74E+4
1.45E+2
2.89E+1
2.50E+2
4.22E+1
2.30E-H
4.18
3.75E+1
7.00E-1
1.10E+1
1.05E+2
1.79E+1
1.31E+1
1.61E+2
5.26E+2
1.38E+1
2.25E+2
3.95E+2
2.01E+4
7.76E+2
5.38E+4
7.54E+4
Em is e ion
Rateb
(mg/sec m2)
6.43E-04
8.33E-04
1.48E-05
2.52E-04
6.04E-06
6.39E-05
2.37E-02
8.68E-05
6.40E-02
9.56E-05
3.08E-05
8.17E-06
1.01E-03
4.95E-06
7.94E-05
1.8SIE-03
1.05E-02
8.06E-02
1.02E-03
3.42E-02
1.27E-01
Mass Transfer
Rate
(m/s)
3.91E-07
1.03E-07
9.02E-06
3 . 68E-06
2.13E-07
3.49E-05
8.37E-06
2.65E-05
4.00E-06
1.32E-06
6.37E-07
1.69E-06
aAvcrage of concentrations measured at Grid Points A.B.E.F and the SW
Corner, VOA vials
"Average of concentrations measured at Grid Points A,B,E,F and the SW
Corner, gas canister.
cEstimated value (Eauation A-6).
-75-
-------
TABLE 6-17
Syringe, Canister, and Liquid Concentration Data
for Grid Point A
Compound
R-Butane
Cyc lohexane
Toluene
Benzene
N-Undecane
Chloroform
Methylchloride
Methylcyclopentene
2,3-Dimethylpentane +
Isoheptane
C-3 VOC
C8 Alkane
C9 Alkane
CIO + Alkane
C8 Alkene
Isobutene + 1-Butene
A-Pinene
CIO + Aromatic
Trichlorof loromethane
Paraffins
Olef ins
Total Aroma tic s
Total Halogenated HC
Unidentified VOC
Total NMHC
Henry ' s
Constant
(atm m^/mol)
2.15E+01
9.57E-01c
6.64E-03
5.50E-03
4.59E-03c
3.93E-03
3.19E-03
8.67E-04c
Syringe Canister
Sample8 Conc.b
(g/m3) (g/m3)
1.14E-04
9.14E-02
1.68E-01
2.39E-04
6.28E-05
6.02E-03
6.10E-04
9.88E-05
1.81E-04
1.05E-04
7.39E-04
8.06E-02
2.59E-01
6.05E-03
1.45E-01
8.59E-02 4.90E-01
Liquid
Cone.
(ppm)
0.0189
2.45
20.2
0.18
<.007
0.442
0.0623
0.0209
0.0238
0.0379
0.136
0.0555
0.0885
0.282
0.639
22.7
0.633
76.4
101
Calculated as toluene.
bAverage concentrations based upon duplicate samples.
cEstimated value (Equation A-6).
-76-
-------
TABLE 6-18
Syringe, Canister, and Liquid Concentration Data
for Grid Point B
Compound
N-Butane
Cyc lohexane
Tetrachloroethylene
N-Decane
Toluene
Benzene
N-Undecane
Methylchloride
Methylcyclopentene
C9 Alkane
C8 Alkene
Isobutene + 1-Butene
C-2-Butene
A-Pinene
Styrene
CIO + Aromatic
Trichlorof lorome thane
1 ,1-Dichloroethylene
Paraffins
Olef ins
Total Aroma tics
Total Halogenated HC
Unidentified VOC
Total NMHC
Henry ' s
Constant
(atm m^/mol)
2.15E-K)lc
9.57E-01c
2.80E-02
1.52E-02C
6.64E-03
5.50E-03
4.59E-03c
3.19E-03
8.67E-04c
Syringe Canister
Samplea»b Conc.b
(g/m3) (g/m3)
4.91E-04
1.36E-02
1.02E-01
8.54E-05
4.91E-04
1.16E-01
8.54E-05
8.91E-02
1.62E-01 2.05E-01
Liquid
Conc.b
(ppm)
0.0487
0.0641
0.0289
1.875
14.2
0.1195
0.02675
0.164
0.115
0.0227
0.0318
0.055
0.08855
0.0894
0.639
0.439
0.0143
0.2565
0.2415
16.45
0.317
44.55
61.8
Calculated as toluene.
bAverage concentrations based upon duplicate samples.
cEstimated value (Equation A-6).
-77-
-------
TABLE 6-19
Syringe, Canister, and Liquid Concentration Data
for Grid Point E
Compound
N-Pentane
N-Hexane
1-Honene
Cblorome thane
Cyc lobexane
N-Heptane
Chloroe thane
Toluene
Benzene
N-Undecane
Methylcbloride
Methy Icyc lopentene
2 ,3-Dimethylpentane +
Isoheptane
Isobutene + 1-Butene
A-Pinene
CIO + Aromatic
Tr ichlor of loorme thane
Paraffins
Olef ins
Total Aromatic s
Total Halogenated HC
Unidentified VOC
Total NMHC
Henry's Syringe
Constant Sample8
(atm m^/mol) (g/m^)
6.05E+OOC
1.78E+OOC
1.57E+OOc
l.OlE+OOc
9.57E-01c
5.40E-01c
3.08E-01c
6.64E-03
5.50E-03
4.59E-03C
3.19E-03
8.67E-04c
1.22E-01
Canister
Conc.b
(g/m3)
4.95E-03
6.41E-03
1.94E-03
1.51E-02
6.87E-02
4.82E-04
1.33E-02
8.38E-02
4.82E-04
4.08E-03
9.51E-02
Liquid
Cone .b
(ppm)
0.00614
0.128
2.29
14.05
0.1455
0.03815
0.2915
0.0499
0.0252
0.112
0.0472
0.8915
0.1955
0.416
16.35
1.1515
53.35
71.55
aCalculated as toluene.
bAverage concentrations based on duplicate samples!
cEstimated value (Equation A-6).
-78-
-------
TABLE 6-20
Syringe, Canister, and Liquid Concentration Data
for Grid Point F
Compound
1-Nonene
Cyclohexane
Toluene
Ethylbenzene
Benzene
N-Ondecane
Methylcbloride
Methylcyclopentene
2 ,3-Dimethylpentane *
Isoheptane
C8 Alkene
Isobutene + 1-Butene
2-Methyl-2-Butene
A-Pinene
CIO + Aromatic
Trichlorof lorome thane
Paraffins
Olefins
Total Aroma tic s
Total Halogens ted HC
Unidentified VOC
Total NMHC
Henry's Syringe
Constant Sample8
(atm m^/mol) (g/m^)
1.57E-K)Oc
9.57E-01c
6.64E-03
5.88E-03c
5.50E-03
4.59E-03c
3.19E-03
8.67E-04C
l.OOE-01
Canister
Cone .b
(g/m3)
1.99E-02
6.67E-04
1.23E-01
5.15E-04
1.44E-01
5.15E-04
2.04E-02
1.65E-01
Liquid
Conc.b
(ppm)
0.0694
0.0558
2.045
13.25
0.111
0.07265
0.177
0.0472
0.0189
0.09265
0.0035
0.0712
0.0622
0.52
0.13085
0.3865
15.35
0.5345
36.15
52.55
Calculated as toluene.
"Average concentrations are based on duplicate samples.
cEstimated value (Equation A-6).
-79-
-------
TABLE 6-21
Canister and Liquid Concentration Data
for Southwest Corner
Compound
Henry ' B
Constant
(a tin m^/mol)
Syringe
Sam
(g/m
pie
3)
Canister
Cone . a
(g/m3)
Liquid
Conc.a
(ppm)
Cyclobezane
Chloroethane
Tetrachloroethylene
Toluene
Benzene
1,1,1-Trichloroethane
N-Undecane
Methylchloride
Metbylcyclopentene
2,3-Dimethylpentane +
Isobeptane
A-Pinene
Trichlorofloromethane
1,1-Dichloroetbylene
Trichloroethylene +
Bromodichloromethane
Paraffins
Olefins
Total Aromatics
Total Halogenated HC
Unidentified VOC
Total NMHC
9.57E-01b
3.08E-01b
2.80E-02
6.64E-03
5.50E-03
.92E-03
,59E-03b
.19E-03
4.
4.
3,
8.67E-04b
4.65E-05
4.78E-03
1.35E-02
7.35E-04
6.57E-04
3.81E-05
N/A
1.83E-02
7.39E-04
5.31E-03
2.43E-02
0.0697
0.019145
0.263
4.49
23.35
0.1665
0.00715
0.173
0.0518
0.1195
0.6885
0.0546
0.2615
0.2925
29.85
1.245
58.45
89.9
aAverage concentrations are based on duplicate sampleu.
^Estimated value (Equation A-6).
-80-
-------
TABLE 6-22
Summary of Flux Chamber Sampling and Analyses
Sample
Number
1
2
3
4
7
8
9
10
11
12
13
14
15
16
17
20
21
22
23
24
25
26
27
28
29
Samp 1 ing
Point
A
A
A
A
B
B
B
B
B
B
F
F
F
F
F
E
E
E
E
E
SV Corner
SV Corner
SW Corner
SW Corner
SV Corner
Sample
Type
Syringe
Canister
Canister
Liquid
Syringe
Canister
Canister
Liquid
Liquid
Syringe
Syringe
Canister
Canister
Liquid
Liquid
Syringe
Canister
Canister
Liquid
Liquid
Canister
Canister
Sludge
Liquid
Liquid
Analysis
Type
END GC
Varian 401 GC
Varian 401 GC
Varian 401 GC
HNU GC
Varian 401 GC
Varian 401 GC
Varian 401 GC
Varian 401 GC
HNU GC
HNU GC
Varian 401 GC
Varian 401 GC
Varian 401 GC
Varian 401 GC
HNU GC
Varian 401 GC
Varian 401 GC
Varian 401 GC
Varian 401 GC
Varian 401 GC
Varian 401 GC
Varian 401 GC
Varian 401 GC
Varian 401 GC
8HNU GC analyses performed on site. Varian 3700 GC analyses performed at
Radian's Gas Cbromatography Lab in Austin, Texas
-81-
-------
7.0 QUALITY ASSURANCE/QUALITY CONTROL
7.1 Method Precision, Accuracy, and Completeness
As part of a rigorous Quality Assurance Program, quality control
procedures were routinely implemented during the performance of this field
monitoring program. The QAPP submitted to EPA for this project describes in
detail the technical approach for the three major tasks conducted; the
stratification study, the surrogate analytical parameter study, and the
composite VOC syringe sampler field trial. Quality control results are
presented in this section for the assessment of method precision, accuracy,
and completeness. Goals for each of the methods utilized are provided in
Table 7-1 and discussed in the method specific discussions which follow.
Assessment of sampling and analytical methods for precision and accuracy was
accomplished in the following manner.
It must be emphasized that the precision and accuracy estimates reported
for each of the methods utilized in this program are just that; estimates.
The data set sizes upon which these estimates are made are often very small,
ranging from a single data point to larger data sets. Thus, true method
precision and accuracy determinations are not possible. These estimations are
made, however, for all methods, due to the importance of understanding the
influence of measurement errors on the reported lagoon characteristics and air
emission estimates. Also, these estimations will hopefully assist in the
ultimate selection of sampling and analytical methodology for use in
monitoring compliance with future regulations.
Precision
Sampling and analytical precision is assessed through replicate sampling
and analysis. To maximize the amount of precision information available for
review, a detailed QC Sample Set was designed. This QC sample set was
-82-
-------
TABLE 7-1
SAMPLE QA OBJECTIVES FOR PRECISION, ACCURACY, AND COMPLETENESS
- OFFSITE LABORATORY ANALYSIS
Matrix Parameter
Liquid Volatiles
Extractables
TOG
POC
GC/PID
Sediment Volatiles
Extractables
TOC
Method3
GC/FID
GC/MS
GC/FID
GC/MS
EPA 415.2
b
EPA 8020
GC/FID
GC/MS
GC/FID
GC/MS
EPA 415.2
Precision
(Relative
Standard
Deviation)
50
_50
50
_50
_15
c
_75
75
_75
75
_75
_25
Accuracy
(% Recovery)
60-145
60-145
10-130
10-130
85-115
c
60-145
50-160
50-160
10-150
10-150
75-125
Completeness
(%)
95
95
95
95
95
95
95
95
95
95
95
95
a Complete descriptions of these methods and their references are available in
Section 7.0 Analytical Procedures.
b Refer to TOC instrument manual.
c Precision and accuracy goals were not available at the time of QA Plan
preparation.
-83-
-------
collected for those lagoon samples requiring POC, IOC, and volatile and
extractable organics analysis by GC/FID at locations shown in Table 4-1. Each
QC sample set included three Bacon bomb samples which were collected from the
same sampling point (see Figure 7-1). The first sampling bomb was aliguoted
into seven replicate samples; the standard deviation of the analytical results
of these seven samples indicating the homogeneity of the bomb sample. The
remaining two bombs were each aliguoted into triplicate samples resulting in a
total number of 13 samples from one sampling point.
Overall measurement precision is estimated by the standard deviation of
the analytical results for all 13 samples. Analytical precision is estimated
by the standard deviation of a triplicate analyses performed on one sample
from each one of the QC sampling sets described above (usually aliquot
number 4). Since no QC sample sets were collected for GC/MS and GC/PID
analysis, the laboratory performed a triplicate analysis on a randomly
selected sample for each parameter to assess analytical precision. Ideally
sampling precision could be determined by subtracting the analytical precision
achieved from the overall measurement precision. Realistically, however, this
is not the case and sampling precision is estimated as the standard deviation
of the analytical results of samples 1 through 7 of the QA samples set.
Accuracy
Measurement accuracy cannot readily be estimated since the true content of
the wastewater holding lagoon samples is not known. The accuracy of the
analytical procedures alone is assessed through the use of spiked field
samples (matrix spike and matrix spike duplicates) and laboratory control
samples whose true values are known to the Laboratory QC Coordinator.
Analytical accuracy is estimated as the percent recovery of the known value.
-84-
-------
500ml
SAMPLING
BOMBS
oo
01
I
I
STANDARD DEVIATIONS OF THE
ANALYTICAL RESULTS WILL
ASSESS BOMB HOMOGENITY
(SAMPLE COLLECTION)
STANDARD DEVIATIONS OF THE ANALYTICAL
RESULTS WILL ASSESS SAMPLING AND
ANALYTICAL PRECISION (MEASUREMENT)
14 15
STANDARD DEVIATIONS OF TRIPLICATE
ANALYSIS OF ONE ALIQUOT WILL ASSESS
ANALYTICAL PRECISION ALONE (ANALYTICAL)
FIGURE 7-1
QUALITY CONTROL SAMPLING SET
-------
Completeness
Completeness is defined as the percentage of measurements made judged to
be valid measurements. Every attempt was made to have all data generated be
valid data. The objective was to have 95 percent of the data valid. Results
are presented with each method.
7.2 Laboratory Analyses
GC/FID Volatile Organic Analyses - Liquids
Quality control analyses conducted for the GC/FID volatile organic liquid
sample analytical activities included analysis of field-biased blanks (FBB)
and method blanks (MB), replicate sample analyses, matrix spikes (MS), and
matrix spike duplicates (MSD). The results of these analyses are summarized
in this section. Table 7-2 provides the results of blank sample analyses.
Table 7-3 presents the results of replicate analyses, and Table 7-4 presents
the results of matrix spike and matrix spike duplicates,,
Overall, the GC/FID volatile organic analysis of liquid samples generated
the following precision, accuracy, and completeness results; based on the
benzene results only, since no toluene was found above the method detection
limits,
Actual (%) Goals (%)
Precision (% RSD)
Overall measurement 34 50
Sample collection 33
Analytical NA
Accuracy (% REG) 118 60 - 145
Completeness (%) 100 95
-86-
-------
TABLE 7-2
GC/FID VOLATILE ORGANIC ANALYSES, LIQUID SAMPLES
BLANK RESULTS
SAMPLE Benzene Toluene
LOCATION (mg/1) (mg/1)
FBB-19 <5 <5
FBB-20 <5 <5
BLANK <5 <5
-87-
-------
TABLE 7-3
GC/FID VOLATILE ORGANICS, LIQUID SAMPLES
.REPLICATE ANALYSES
SAMPLE
LOCATION
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
SAMPLE
TYPE
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
MEASUREMENT
(1-13)
SAMPLE
COLLECTION
(1-7)
ANALYTICAL3
(4,14,15)
CONTROL NO.
46380
46381
46382
46383
46384
46385
46386
46387
46388
46375
46376
46377
46378
AVERAGE
SUM (xi2)
(SUM Xi)2
STD.DEV.
REL.STD.DEV.
AVERAGE
SUM (Xi2)
(SUM Xi)2
STD.DEV.
REL.STD.DEV.
AVERAGE
SUM (Xi2)
(SUM xi)2
STD.DEV.
REL.STD.DEV.
QC SET
ALIQUOT
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
Benzene
(mg/1)
9
12
12
12
22
20
19
19
18
11
6
17
11
14
3,010
35,344
5
34%
15
1,758
11,236
5
33%
NA
NA
NA
NA
NA
Toluene
(mg/1)
-------
TABLE 7-4
GC/FID VOLATILE ORGANIC ANALYSES, LIQUID SAMPLES
MATRIX SPIKE RECOVERIES
SAMPLE
LOCATION
B-l
A-l
SAMPLE
CONTROL NO. TYPE PARAMETER
46375 Liguid-MS Benzene
Liguid-MSD
Liquid-MS Toluene
Liquid-MSD
46368 Liquid-MS Benzene
Liquid-MSD
Liquid-MS Toluene
Liquid-MSD
AMOUNT
REPORTED3
(mg/1)
310
300
540
470
193
178
188
173
TRUE
VALUE
(mg/1)
250
250
250
250
250
250
250
250
AVERAGE
PERCENT
RECOVERY
124%
120%
216%b
186%b
77%
71%
75%
69%
118%
a Value corrected for native concentration.
" Response increased by occurrence of chromatographic interference.
-89-
-------
All blank results in Table 7-2 were below the method detection limit of
5 mg/L for both target compounds, benzene and toluene. These results indicate
that no contamination of samples occurred between the field and the laboratory
based on the results of the two field-biased blanks. The three method blank
analyses indicate the lack of sample contamination due to analytical reagents
of glassware. In this case, all blanks were samples of distilled deionized
water which were carried through the same sample preparation and analytical
procedures as the samples.
Precision data is provided in Table 7-3. Table 7-3 presents the replicate
analyses for a surface liquid sample collected at Location B-l in the lagoon.
This sample was designated for a full QC set analysis. Due to an oversight,
the triplicate split proposed in the QC set outline for assessment of the
analytical precision was not performed. The available analytical data
indicate a sampling precision for benzene of 33 percent relative standard
deviation (RSD), and an overall measurement precision of 34 percent RSD. The
close agreement between the sampling and overall measurement values would
indicate good analytical precision (in the absence of the proposed triplicate
analysis).
In addition to the results of these replicate analyses, matrix spike (MS)
and matrix spike duplicate (MSD) analyses were conducted, the results of which
are reported in Table 7-4. The 118 percent average recovery is an indication
of acceptable method accuracy.
GC/FID Volatile Organic Analyses - Sludges
Precision, accuracy and completeness estimates were also made for the
GC/FID volatile organic analysis of sludge samples. The QC samples used to
make this assessment included blanks, replicates, and spikes. Overall, the
results were:
-90-
-------
Actual (%) Goals (%)
Precision (% RSD)
Overall measurement 67 75
Sample collection 107
Analytical 45, 16
Accuracy (% REG) 99 50 - 160
Completeness (%) 100 95
Table 7-5 provides the results of a blank analysis showing no levels above
the method detection limit. Tables 7-6 and 7-7 contain the results of
replicate analyses for sludge samples analyzed by GC/FIEi for volatile organics.
Review of these results indicates the greater variability involved in the
sampling and analysis of sludge material versus liquid samples. The sample
collection precision result is over the anticipated goal of 75 percent RSD.
The main reason for this lesser precision is thought to be the more complex
nature of the sludge material itself and how the sample matrix is affected by
the sample collection procedure. The sludge was found to be much more
concentrated than the liquid samples. Variation in the production process at
FCC would contribute to wide variations in the settleable organics in the
lagoon over time. By nature, the sludge is a non-homogeneous material due to
its accumulation over time via deposition. Thus, it is likely that the sludge
material is composed of layers of varying concentration which are disturbed by
the sampling process itself. This unavoidable disturbance contributes
increased variability to the sludge sample concentrations. When these
dynamics are considered, the low precision appears reasonable.
The analytical precision is reported for two samples, one as part of a
full QC set 45 percent RSD, and one additional random sample analyzed in
triplicate, 16 percent RSD. Both of these values are within the stated goals.
-91-
-------
TABLE 7-5
GC/FID VOLATILE ORGANIC ANALYSES, SLUDGE SAMPLES
BLANK RESULTS
SAMPLE Benzene: Toluene
LOCATION CONTROL NO. (mg/1) (mg/1)
BLANK V5448 <130 <55
-92-
-------
TABLE 7-6
GC/FID VOLATILE ORGANICS, SLUDGE SAMPLES
REPLICATE ANALYSES
SAMPLE
LOCATION
E-5
E-5
E-5
E-5
E-5
E-5
E-5
E-5
E-5
E-5
E-5
E-5
E-5
SAMPLE
TYPE
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
MEASUREMENT
(1-13)
SAMPLE
COLLECTION
(1-7)
ANALYTICAL
(4,14,15,16)
CONTROL NO.
46415
46416
46417
46418
46419
46420
46421
46422
46423
46423
46424
46425
46426
AVERAGE
SUM (Xi2)
(SUM Xi)2
STD.DEV.
REL.STD.DEV.
AVERAGE
SUM (xi2)
(SUM Xi)2
STD.DEV.
REL.STD.DEV.
AVERAGE
SUM (xi2)
(SUM Xi)2
STD.DEV.
REL.STD.DEV.
QC SET
ALIQUOT
NUMBER
1
2
3
4
14
15
16
5
6
7
8
9
10
11
12
13
Benzene
(mg/kg)
1300
760
380
300
190
130
120
220
76
320
270
650
450
<210
300
480
459
3,676,876
30,316,036
323
70%
479
2,658,576
11,262,736
418
87%
185
157,400
547,600
83
45%
Toluene
(mg/kg)
350
180
98
<85
<85
<85
<85
<65
<65
<85
<60
200
110
85
<50
<65
171
223,829
1,046,529
109
64%
171
171,729
508,369
129
126%
NA
NA
NA
NA
NA
-93-
-------
TABLE 7-7
GC/FID VOLATILE ORGANICS, SLUDGE SAMPLES
REPLICATE ANALYSES
SAMPLE
LOCATION
SAMPLE
TYPE
CONTROL NO.
Benzene
(mg/kg)
Toluene
(mg/kg)
F-5
Sludge
46455
2,000
2,800
2,300
510
670
560
ANALYTICAL
AVERAGE
SUM (Xi2;
(SUM Xi)2
STD.DEV.
REL.STD.DEV.
2367
17,130,000
50,410,000
404
17%
580
1,022,600
3,027,600
82
14%
-94-
-------
The magnitude of the percent recovery for the MS and MSD results reported
in Table 7-8, is useful as an indicator of the method accuracy. The
91 percent to 108 percent recoveries for the two samples indicate acceptable
method accuracy.
GC/FID Semivolatile Organics - Liquid Samples
Extractable organics determinations were performed on liquid samples
collected from the lagoon. Quality control samples analyzed included blanks,
surrogate spikes on every sample, replicates, and a matrix spike and matrix
spike duplicate. The overall precision, accuracy, and completeness results
are listed below:
Actual (%) Goals (%)
Precision (% RSD)
Overall measurement 35 <50
Sample collection 36
Analytical 36
Surrogates 48
Accuracy (% REC) 107 1C) - 130
Surrogates 50
Completeness (%) 100 95
The results of the analysis of blank samples are provided in Table 7-9.
No results above the detection limit are reported for either the field-biased
blanks (FBB) or the laboratory method blanks.
Table 7-10 provides the results of a full QC set of analyses conducted on
samples collected at location B-l. A total of five compounds are reported, of
which only three were identified at levels above the detection limits. The
-95-
-------
TABLE 7-8
GC/FID VOLATILE ORGANIC ANALYSES, SLUDGE SAMPLES
MATRIX SPIKE RECOVERIES
SAMPLE
LOCATION
F-5
SAMPLE
CONTROL NO. TYPE PARAMETER
46455 Liquid-MS Benzene
Liquid-MSD
Liquid-MS Toluene
Liquid-MSD
AMOUNT
REPORTED
(mg/kg)
10,100
10,800
9,100
9,700
TRUE
VALUE
(mg/kg)
10,000
10,000
10,000
10,000
PERCENT
RECOVERY
101%
100%
91%
97%
AVERAGE 99%
-96-
-------
TABLE 7-9
SEMI-VOLATILE ORGANIC ANALYSES,
LIQUID SAMPLES BLANK RESULTS
SAMPLE 2,4-Dinitrotoluene Nitrobenzene 2-Nitrophenol 2,4-Dinotrophenol 4,6-Dinitro-o-cresol
LOCATION CONTROL NO. (mg/1) (mg/1) (mg/1) (mg/1) (mg/1)
FBB1-20
FBB1-20
BLANK
BLANK
BLANK
46449 <10
46450 <10
QC 1566 <10
QC 1567 <10
QC 1568 <10
<10 <3
<10 <3
<10 <3
<10 <3
<10 <3
<50 <10
<50 <10
<50 <10
<50 <10
<50 <10
-------
TABLE 7-10
GC/FID VOLATILE ORGANICS, LIQUID SAMPLES
REPLICATE ANALYSES
oo
SAMPLE
LOCATION
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
B-l
SAMPLE
TYPE
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
MEASUREMENT
(1-13)
SAMPLE
COLLECTION
(1-7)
ANALYTICAL*
(4,14,15)
CONTROL NO.
46396
46397
46398
46399
46400
46401
46402
46403
46404
46405
46406
46407
46408
AVERAGE
SUM (Xi2
(SUM Xi)
STD.DEV.
REL.STD.
AVERAGE
SUM (Xj2
(SUM Xi)
STD.DEV.
REL.STD.
AVERAGE
SUM (Xi2
(SUM Xi)
STD.DEV.
REL.STD.
QC SET
ALIQUOT
NUMBER
1
2
3
4
14
15
5
6
7
8
9
10
11
12
13
)
2
DEV.
)
2
DEV.
)
2
DEV.
2,4-Dinitro- Nitro-
toluene benzene
(mg/1) (mg/l)
<11 320
<10 510
<10 580
<10 530
<10 580
<10 500
<10 650
<10 530
<10 820
<10 630
<10 560
<10 780
<10 830
<20 830
<20 750
640
5,614,800
69,222,400
155
24%
563
2,355,600
15,523,600
152
27%
537
867,300
2,592,100
40
8%
2-Nitro- 2,4-Dinitro-
phenol phenol
(mg/1) (mg/1)
8.2 100
<16 330
<16 210
<16 250
<16 89
<16 120
<16 82
<16 190
<16 89
<16 160
<16 180
<16 84
<16 62
<43 190
<43 280
179
459,645
4,870,849
84
50%
179
276,245
1,565,001
94
52%
153
84,821
210,681
85
56%
4,6-Dinitro-
o-cresol
(mg/1)
24
45
23
33
56
24
46
27
33
42
27
25
39
53
59
37
19,082
226,576
12
32%
33
8,153
53,361
9
28%
38
4,801
12,769
17
44%
-------
precision estimation results for these three compounds average out to the
reported 35 percent RSD, 36 percent RSD, and 37 percent RSD for the overall
measurement, sample collection and analytical procedures, respectively. The
overall measurement precision is better than that proposed in the QA plan
goals.
Table 7-11 provides the results of the recovery percentages for the MS and
MSD samples. Based on these results, an estimate of the method accuracy is
determined to be 107 percent. This result can be further interpreted when
considered with the average surrogate recovery percentage of 50 percent,
derived from data included in Table 7-12. Both of these results are within
the goals originally proposed for this analytical technique. Also, a relative
standard deviation calculation based on the surrogate recovery data indicates
an overall 51 percent RSD for the analytical technique.
GC/FID Semivolatile Organics - Sludge Samples
The results of quality control analyses conducted on lagoon sludge samples
for semivolatile organics are summarized below:
Actual (%) Goals (%)
Precision (% RSD)
Overall measurement 70 < 75
Sample collection 88
Analytical 4
Surrogates 25
Accuracy (% REC) 69 10 - 150
Surrogates 70
Completeness (%) 100 95
-99-
-------
TABLE 7-11
GC/FID SEMI-VOLATILE ORGANIC ANALYSES, LIQUID SAMPLES
MATRIX SPIKE RECOVERIES, SAMPLE B-l, 46396
o
o
. PARAMETER
1,2, 4-Trichlorobenzene
Acenaphthene
2 ,4-Dinitrotoluene
Pyrene
n-Nitroso-di-n-propylamine
1,4 Dichlorobenzene
Pentachlorophenol
Phenol
Chlorophenol
4-Chloro-e-methylphenol
4-Nitrophenol
QC
AMOUNT
REPORTED
(mg/1)
8.3
14.0
12.2
14.2
<1.0*
<1.0*
30.0
11.0
20.0
21.4
22.4
MS
1577
AMOUNT
SPIKED
(mg/1)
10
10
10
10
10
10
20
20
20
20
20
PERCENT
RECOVERY
83
140
122
142
NA
NA
150
55
100
107
112
AMOUNT
REPORTED
(mg/1)
13.0
12.8
11.0
14.2
<1.0*
7.2
27.6
12.0
21.2
24.4
24.2
MSD
QC 1578
AMOUNT
SPIKED
(mg/1)
10
10
10
10
10
10
20
20
20
20
20
PERCENT
RECOVERY
130
128
110
142
NA
72
138
60
106
122
121
TOTAL
AVERAGE
PERCENT
RECOVERY
107
134
116
142
NA
36
144
58
103
115
117
107
* chromatographic interference
-------
TABLE 7-12
GC/FID SEMI-VOLATILE ORGANIC ANALYSES,
LIQUID SAMPLES SURROGATE RECOVERIES
SAMPLE
LOCATION
A-l
A-2
A-3
A-4
B-l(l)
B-l(2)
B-K3)
B-l(4)
B-l(5)
B-l(6)
B-l(8)
B-l(9)
B-l(lO)
B-l(ll)
B-I(12)
B-l(13)
B-K14)
B-2
E-l
E-2
E-3
F-l
F-2
F-3
FBB1-20
FBB2-20
BLANK
BLANK
BLANK
SPIKE
SPIKE
CONTROL NO.
46373
46370
46371
46372
46396
46397
46398
46399
46400
46401
46402
46403
46404
46405
46406
46407
46408
46409
46447
46433
46434
46476
46473
46474
46449
46450
QC 1566
QC 1567
QC 1568
QC 1577
QC 1578
AVERAGE RECOVERY in %
SUM(x^2)
(SUMx^)2
STD.DEV.
-
of RECOVERY %
REL.STD.DEV. in %
2 -F 1 uo r ob i pheny 1
%
80
77
82
58
76
62
64
59
72
103
96
97
38
68
112
75
30
14
21
65
68
50
64
14
52
89
95
49
29
29
73
114
65
157,505
4,305,625
32
49%
Terphenyl-dl4
%
48
106
98
65
41
60
72
50
80
20
30
30
91
10
30
20
14
30
50
35
77
44
59
50
56
101
57
62
63
66
36
38
53
108,777
2,852,721
28
54%
2-Fluorophenol
%
27
27
27
60
48
27
20
10
20
50
50
25
20
25
25
50
0
17
33
47
18
27
40
27
33
25
25
28
40
50
42
39
31
36,972
1,004,004
16
50%
-101-
-------
Table 7-13 contains the results of blank analyses conducted on distilled
water carried through the extraction procedure. No results above the
detection limit were reported.
Replicate analyses were conducted on a full QC set of samples from
location E-5, documented in Table 7-14. Review of the results again indicates
that the sludge sample collection technique is an imiprecise operation. The
high relative standard deviations (RSD) calculated for the overall measurement
and sample collection in conjunction with the low RSD calculated for the
analytical technique support this conclusion.
Accuracy, estimated as the percent recovery of the matrix spike and matrix
spike duplicate, and surrogate spiked compounds are presented in Tables 7-15
and 7-16. Overall values of 69 percent and 70 percent were reported. The
relative standard deviation of the surrogate recoveries, averages 25 percent.
This result can be compared with the analytical precision estimated from the
replicate sample analyses.
GO/MS Volatile Orqanics - Liquid Samples
Quality control samples analyzed via this method included blanks, a matrix
spike and matrix spike duplicate, and spiked surrogate: compounds. No QC set
replicate analyses were conducted on samples via GC/MS to keep the sample load
manageable. Therefore, only overall method precision estimates can be made.
The precision and accuracy indicators and completeness; results are summarized
below. All results indicate acceptable method performance.
Actual (%) Goals (%)
Precision (% RSD)
Surrogates 4 < 50
-102-
-------
TABLE 7-13
SEMI-VOLATILE ORGANIC ANALYSES,
SLUDGE SAMPLES BLANK RESULTS
SAMPLE
LOCATION CONTROL NO.
2,4 Dinitrotoluene Nitrobenzene 2-Nitrophenol 2,4-Dinitrophenol 4,6-Dinitro-o-cresol
(mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg)
BLANK
BLANK
QC 1591
QC 1598
<50
<50
<50 <1
<50 <1
5 <250
5 <250
<50
<50
I
M
O
-------
TABLE 7-14
GC/FID SEMI-VOLATILE ORGANIC ANALYSES,
SLUDGE SAMPLE REPLICATES
I
M
o
I
SAMPLE
LOCATION
E-5
E-5
E-5
E-5
E-5
E-5
E-5
E-5
E-5
E-5
E-5
E-5
E-5
SAMPLE
TYPE CONTROL NO.
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
MEASUREMENT
(1-13)
SAMPLE
COLLECTION
(1-7)
ANALYTICAL
(4,14,15)
46435
46436
46437
46438
46439
46440
46441
46445
46446
46432
46442
46443
46444
AVERAGE
SUM (Xi2
(SUM Xi)
STD.DEV.
REL.STD.
AVERAGE
SUM (Xi2
(SUM XA)
STD.DEV.
REL.STD.
AVERAGE
SUM (Xi2
(SUM Xi)
STD.DEV.
REL.STD.
QC SET
ALIQUOT
NUMBER
1
2
3
4
14
15
5
6
7
8
9
10
11
12
13
)
2
DEV.
)
2
DEV.
)
2
DEV.
2,4-Dinitro- Nitro-
toluene
(mg/1)
230
410
380
<200
<200
<200
<400
<200
240
<400
<400
<400
<400
<400
<400
315
423,000
1,587,600 32
158
50%
315
423,000 1
1,587,600 11
181
57%
__
1
benzene
(mg/1)
7,000
13,000
12,000
14,000
15,000
15,000
8,400
20,000
31,000
6,800
10,000
6,800
15,000
15,000
20,000
13,769
303,204,000 55
,041,000,000 189
6,876
50%
15,057
,989,560,000 42
,109,160,000 75
8,191
54%
14,667
646,000,000
,936,000,000 1
577
4%
2-Nitro-
phenol
(mg/1)
110
6,400
200
410
440
440
220
560
800
<1,000
290
3,500
390
390
490
1,147
,060,600 1
,337,600 14
1,837
160%
1,243
,182,200
,690,000 4
2,287
184%
430
555,300
,664,100
17
4%
2,4-Dinitro- 4,6-Dinitro-
phenol
(mg/1)
4,400
7,800
7,700
9,200
8,800
9,100
5,700
12,000
22,000
4,200
6,400
4,000
11,000
11,000
16,000
9,338
,457,220,000
,737,960,000
5,192
56%
9,829
884,520,000
,733,440,000
5,894
60%
9,033
344,890,000
734,410,000
208
2%
o-cresol
(mg/1)
2,000
3,000
2,800
3,800
3,400
3,500
2,200
4,400
6,000
1,700
2,900
2,300
3,400
3,200
4,200
3,223 AVERAGE
151,510,000
1,755,610,000
1,171
36%
3,457
95,480,000
585,640,000
1,403
41%
3,567
3,825,000
114,490,000
208
6%
70%
88%
4%
-------
TABLE 7-15
GC/FID SEMI-VOLATILE ORGANIC ANALYSES, SLUDGE SAMPLES
MATRIX SPIKE RECOVERIES, SAMPLE E-5, 46435
MS
QC 1589
PARAMETER
Phenol
2-4-Dinitrotoluene
i
o
Ul
AMOUNT
REPORTED
(mg/kg)
715.0
440.0
AMOUNT PERCENT
SPIKED RECOVERY
(mg/kg) %
1,100 65
550 80
MS
QC 1590
AMOUNT
REPORTED
(mg/kg)
605.0
401.5
AMOUNT PERCENT
SPIKED RECOVERY
(mg/kg) %
1,100 55
550 73
AVERAGE
AVERAGE
PERCENT
RECOVERY
%
60
77
69
-------
TABLE 7-16
GC/FID SEMI-VOLATILE ORGANIC ANALYSES,
SLUDGE SAMPLES SURROGATE RECOVERIES
SAMPLE
LOCATION
A-5
B-5
E-5(l)
E-5(2)
E-5(3)
E-5(4)
E-5(5)
E-5{6)
E-5{7)
E-5(ll)
E-5(12)
E-5(13)
E-5(8)
E-5(9)
E-5(10)
F-5
BLANK
BLANK
SPIKE
SPIKE
CONTROL NO.
46374
46410
46435
46436
46437
46438
46438B
46438C
46439
46440
46441
46442
46443
46444
46445
46446
46432
46475
QC 1591
QC 1598
QC 1589
QC 1590
AVERAGE RECOVERY in %
SUM(Xj2)
(SUMxi)2
STD.DEV.
of RECOVERY %
REL.STD.DEV. in %
2-Fluorobiphenyl
%
47
95
68
73
72
72
79
78
75
77
79
79
78
87
76
83
112
55
36
76
68
63
74
125,468
2,650,384
15
21%
Terphenyl-dl4
%
37
73
59
58
54
57
47
50
50
43
46
55
49
55
88
63
109
65
41
88
59
54
59
82,974
1,690,000
17
29%
2-Fluorophenol
*
61
82
77
85
84
88
98
83
87
87
94
88
84
97
25
79
103
29
50
80
80
75
78
142,316
2,944,656
20
26%
-106-
-------
Actual (%) Goals (%)
Accuracy (% REG)
MS and MSB 86 60 - 145
Surrogates 98
Completeness (%) 100 95
The blank results are provided in Table 7-17, and indicate that
field-biased blanks and laboratory method blanks contained no data above the
detection limits. Tables 7-18 and 7-19 contain the matrix spike and matrix
spike duplicate recoveries and surrogate compound recoveries. The averaged
recoveries presented on these two tables estimate accuracy as 86 percent and
98 percent, respectively.
A rough indication of the method precision is provided by determining the
relative standard deviation of the surrogate recovery percentage. The
4 percent value reported on Table 7-19 indicates good precision. The lack of
replicate sample aliguots precludes a better estimate of this parameter.
GC/MS Volatile Organics Analyses - Sludges
QC sample analyses for sludges were conducted on blanks, a matrix spike
and a matrix spike duplicate, and spiked surrogate compounds. Results of
these analyses are useful as indicators of precision and accuracy, as well as
the completeness result are presented below:
Actual (%) Coals (%)
Precision (% RSD)
Surrogates 2 < 75
Accuracy (% REG)
MS and MSD 110 S»0 - 160
Surrogates 100
Completeness (%) 100 95
-107-
-------
TABLE 7-17
VOLATILE ORGANIC ANALYSES,
LIQUID SAMPLES BLANK RESULTS
Nitro- Unknown Unknown Sum of the
SAMPLE Benzene Toluene Benzene* (1) (2) Sum of Cpds. Integrated
LOCATION CONTROL NO. (mg/1) (mg/1) (mg/1) (mg/1) (mg/1) Reported Chromatograph
FBB-19 46395 <5 <1 <10 <10 <10 <10 <100
FBB-19 46431 <5 <1 <10 <10 <10 <10 <100
BLANK V5480 <5 <1 <10 <10 <10 <10 <100
BLANK V5478 <5 <1 <10 <10 <10 <10 <100
* Calculated relative to internal standard
o
oo
i
-------
TABLE 7-18
GC/FID VOLATILE ORGANIC ANALYSES, LIQUID SAMPLES
MATRIX SPIKE RECOVERIES
SAMPLE
LOCATION
F-5
SAMPLE
CONTROL NO. TYPE PARAMETER
46368 Liguid-MS Benzene
Liguid-MSD
Liquid-MS Toluene
Liguid-MSD
AMOUNT
REPORTED
(mg/1)
235
185
220
220
TRUE
VALUE
(mg/1)
250
250
250
250
AVERAGE
PERCENT
RECOVERY
-%-t
94%
74%
88%
88%
86%
-109-
-------
TABLE 7-19
GC/FID VOLATILE ORGANIC ANALYSES,
LIQUID SAMPLES SURROGATE RECOVERIES
1,2-Dichloro-
SAMPLE
LOCATION
A-l
B-l
E-l
F-l
FBB-19
FBB-20
BLANK
BLANK
AVERAGE
SUM(x i2)
(SUMxi)2
STD.DEV.
REL.STD.
CONTROL NO.
46368
MS 46368
MSD 46368
46379
46412
46452
46395
46431
V5480
V5478
RECOVERY in %
of RECOVERY %
DEV. in %
Toluene-dB
%
100
98
97
95
95
91
102
101
101
99
98
95,951
958,441
3
4%
BFB
%
97
97
99
99
98
100
96
97
99
85
98
95,475
954,529
2
2%
ethane-dB
%
98
96
100
101
101
104
102
95
97
88
98
96,620
964,324
5
5%
AVERAGE
98%
4%
-110-
-------
Table 7-20 provides the results for the sludge blank sample analysis.
This sample was distilled water which was carried through the sludge
extraction procedure. No compounds were present at levels above the stated
detection limits.
Table 7-21 lists the matrix spike and matrix spike duplicate results. The
results indicate the method accuracy, as an average of 110 percent recovery.
Recoveries of surrogate compounds are reported in Table 7-22 for seven
sludge sample analyses. The average percent recovery of 100 percent is a
further indicator of method accuracy. The relative standard deviation,
2 percent, of the recovery percentages serves as an indicator of analytical
precision.
GC/MS Semivolatile Organics - Liquids
QC sample analyses included matrix spike, matrix spike duplicate, and
spiked surrogate compounds analyses. No sample blanks or duplicate samples
were analyzed by this method. This procedure was used as confirmation of the
GC/FID results, rather than as a primary analysis for the stratification
study. Since the GC/FID blank samples were below detection limits, no GC/MS
analysis for blanks were performed. The precision and accuracy indicators and
calculation of completeness are listed below:
Actual (%) Goals (%)
Precision (% RSD)
Surrogates 17 <50
Accuracy (% REG)
MS and MSD 92 10 - 130
Surrogates 109
Completeness (%) 100 95
-111-
-------
TABLE 7-20
GC/MS VOLATILE ORGANIC ANALYSES,
SLUDGE SAMPLES BLANK RESULTS
SAMPLE
LOCATION CONTROL NO.
BLANK V5448
Benzene
(rag/kg)
<30
Toluene
(rag/kg)
<30
Nitro-
Benzene*
(mg/kg)
<100
Unknown
(1)
(rag/kg)
<100
Unknown
(2)
(mg/kg)
<100
Sum of Cpds.
Reported
<100
Sum of the
Integrated
Chromatograph
<1000
* Calculated relative to internal standard
to
I
-------
TABLE 7-21
GC/MS VOLATILE ORGANIC ANALYSES, SLUDGE SAMPLES
MATRIX SPIKE RECOVERIES
SAMPLE
LOCATION
F-5
GCA SAMPLE
CONTROL NO. TYPE PARAMETER
46455 Sludge-MS Benzene
Sludge-MSD
Sludge-MS Toluene
Sludge-MSD
AMOUNT
REPORTED
(mg/kg)
12,200
8,800
13,000
10,000
TRUE
VALUE
(mg/kg)
10,000
10,000
10,000
10,000
PERCENT
RECOVERY
122%
88%
130%
100%
AVERAGE 110%
-113-
-------
TABLE 7-22
GC/MS VOLATILE ORGANIC ANALYSES,
SLUDGE SAMPLES SURROGATE RECOVERIES
1,2-Dichloro-
SAMPLE
LOCATION
A-5
B-5
E-5
F-5
BLANK
AVERAGE
SUM(Xi2)
STD.DEV.
REL.STD.
CONTROL NO.
46362
46392
46415
46455
MS 46455
MSD 46455
V5448
RECOVERY in %
of RECOVERY %
DEV. in %
Toluene-dB
%
102
100
99
97
95
98
103
99
68,852
481,636
3
3%
BFB
%
99
99
100
101
100
101
100
100
70,004
490,000
1
1%
ethane-dB
%
103
99
102
102
106
101
101
102
72,856
509,796
2
2%
AVERAGE
100%
2%
-114-
-------
Table 7-23 provides the results of the matrix spike and matrix spike
duplicate results for the GC/MS semivolatile organic analysis of liquid
samples. The average percent recovery of 92 percent provides an indication of
the method accuracy.
The surrogate spike recovery results, presented in Table 7-24, provide
indicators of both precision and accuracy. The average surrogate recovery of
109 percent serves as an accuracy indicator and the 17 percent relative
standard deviation of the surrogate recovery percentages provides an
estimation of the method precision.
GC/MS Semivolatile Organics - Sludge Samples
Blank samples, matrix spike and matrix spike duplicates, and surrogate
spiked compounds were used to assess method precision and accuracy. The QC
results are summarized below:
Actual (%) Goals
Precision (% RSD)
Surrogates 40 <75
Accuracy (% REG)
MS and MSD 68 10 - 150
Surrogates 77
Completeness (%) 100 95
Table 7-25 provides the results of the blank sample analysis, revealing no
levels above the stated detection limits. Results of the analysis of matrix
spike and matrix spike recoveries appear in Table 7-26. The average percent
recovery of 68 percent serves as an indicator of method accuracy. The results
of three compounds were invalidated by high matrix interference and were not
included in the average percent recovery calculation.
-115-
-------
TABLE 7-23
GC/MS SEMI-VOLATILE ORGANIC ANALYSES, LIQUID SAMPLES
MATRIX SPIKE RECOVERIES, SAMPLE B-l, 46396
CTl
I
PARAMETER
1,2, 4-Trichlorobenzene
Acenaphthene
2 ,4-Dinitrotoluene
Pyrene
n-Nitroso-di-n-propylamine
1,4 Dichlorobenzene
Pentachlorophenol
Phenol
Chlorophenol
4-Chloro-e-methylphenol
4-Nitrophenol
AMOUNT
REPORTED
(mg/1)
8.3
7.9
7.3
6.4
7.4
7.9
27.2
8.4
17.2
20.4
18.0
QC 1577
AMOUNT
SPIKED
(mg/1)
10
10
10
10
10
10
20
20
20
20
20
PERCENT
RECOVERY
83
79
73
64
74
79
136
42
86
102
90
AMOUNT
REPORTED
(mg/1)
8.8
9.2
8.4
7.0
8.1
9.2
25.8
7.6
15.6
18.6
17.2
QC 1578
AMOUNT
SPIKED
(mg/1)
10
10
10
10
10
10
20
20
20
20
20
PERCENT
RECOVERY
88
92
84
70
81
92
129
38
78
93
86
AVERAGE
AVERAGE
PERCENT
RECOVERY
85.5
85.5
78.5
67.0
77.5
85.5
132.5
40.0
82.0
97.5
88.0
92.0
-------
TABLE 7-24
GC/MS SEMI-VOLATILE ORGANIC ANALYSES,
LIQUID SAMPLES SURROGATE RECOVERIES
SAMPLE
LOCATION
A-l
B-l
E-l
F-l
FBB1-20
FBB2-20
BLANK
BLANK
BLANK
BLANK
SPIKE
SPIKE
SPIKE
SPIKE
CONTROL NO.
46373
46396
46447
46476
46449
46450
QC 1566
QC 1567
QC 1568
QC 1588
QC 1577
QC 1578
QC 1589
QC 1590
AVERAGE RECOVERY in %
SUM(xi2)
(SUMxi)2
STD. DEV.
REL.STD.DEV. in %
2-Fluorobiphenyl
%
112
94
100
130
108
104
104
102
106
100
94
104
81
42
126
141,193
1,907,161
20
16%
Terphenyl-dl4
%
70
60
64
128
72
66
78
80
74
100
60
60
42
54
92
78,360
1,016,064
21
23%
2-Fluorophenol
%
48
90
92
90
84
80
94
86
86
100
96
88
88
80
109
105,156 .
1,444,804
17
11%
AVERAGES
109%
17%
-117-
-------
TABLE 7-25
GC/MS SEMI-VOLATILE ORGANIC ANALYSES,
SLUDGE SAMPLES BLANK RESULTS
Nitro- 2-Nitro-
SAMPLE benzene phenol
LOCATION CONTROL NO. (mg/kg) (mg/kg)
2,4-Dinitro-
phenol
(mg/kg)
4,6-Dinitro-
o-cresol
(mg/kg)
4-Nitro-
phenol
(mg/kg)
Benzole
Acid
(mg/kg)
BLANK QC 1586
<330
<330
<1650
<1650
<1650
<1650
i
M
M
00
-------
TABLE 7-26
GC/MS SEMI-VOLATILE ORGANIC ANALYSES, SLUDGE SAMPLES
MATRIX SPIKE RECOVERIES (SAMPLE 46435)
PARAMETER
Nitrobenzene (1)
1,2, 4-t richlorobenzene
Acenaphthene
2 , 4-Dinitrotoluene
Pyrene
4-Chloro-m-cresol
1,4 Dichlorobenzene
Pentachlorophenol
Phenol
Chlorophenol
2-Nitrophenol
4-Nitrophenol
2,4-Dinitrophenol (1)
4,6-Dinitro-o-cresol (1)
AMOUNT
REPORTED
(mg/kg)
7,900
270
330
500
220
770
300
810
560
520
110
2,000
25,000
3,800
MS
QC 1589
AMOUNT
SPIKED
(mg/kg)
1,100
550
550
1,100
550
1,100
550
1,100
1,100
1,100
1,100
1,100
1,100
1,100
AVERAGE
PERCENT
RECOVERY
718%
49%
60%
45%
40%
70%
55%
74%
51%
47%
10%
182%
2273%
345%
62%
AMOUNT
REPORTED
(mg/kg)
8,300
310
320
1,200
580
1,200
310
1,600
810
990
170
1,600
10,600
2,800
MSD
QC 1590
AMOUNT
SPIKED
(mg/kg)
1,300
630
630
1,300
630
1,300
630
1,300
1,300
1,300
1,300
1,300
1,300
1,300
PERCENT
RECOVERY
638%
49%
51%
92%
92%
92%
49%
123%
62%
76%
13%
123%
815%
215%
75%
AVERAGE
PERCENT
RECOVERY
678%
49%
55%
69%
66%
81%
52%
98%
57%
62%
12%
152%
1544%
280%
68%
(1) High matrix interference invalidated these compounds.
-------
The surrogate compounds recovery data are presented in Table 7-27. The
average percent recovery result of 77 percent provides a further measure of
method accuracy. The 40 percent relative standard deviation of the surrogate
recovery percentages provides an estimate of the method precision.
Total Organic Carbon (TOC) Analyses
The total organic carbon analysis included typical' QC sample analyses for
the estimation of method precision and accuracy. Th«s following values were
determined for this method:
Actual (%) Goals (%)
TOC - LIQUIDS
Precision (% RSD)
Duplicates 2 <15
Accuracy (% REC)
MS
EMSL spike
Completeness (%)
96
99
100
85 - 115
95
TOC - SLUDGES
Precision (% RSD)
Duplicates 7 <25
Accuracy (% REC)
EMSL spike 96 75 - 125
Completeness (%) 100 95
The data from which these estimates were calculated are provided in
Table 7-28, blank results; Table 7-29, duplicate results for liquid samples;
-120-
-------
TABLE 7-27
GC/MS SEMI-VOLATILE ORGANIC ANALYSES,
SLUDGE SAMPLES SURROGATE RECOVERIES
SAMPLE
LOCATION
A-5
B-5
E-5
F-5
SPIKE
SPIKE
BLANK
CONTROL NO.
46374
46410
46435
46475
QC 1589
QC 1590
QC 1588
AVERAGE
STD.DEV.
REL.STD.DEV
2-Fluorobiphenyl
68
123
41
160
81
42
100
68
65,359
378,225
43
49%
Terphenyl-dl4
45
115
27
68
42
54
100
64
35,283
203,401
32
50%
2-Fluorophenol
69
90
83
46
88
80
100
AVERAGES
79
46,010
309,136
18
22%
77%
40%
-121-
-------
TABLE 7-28
TOG ANALYSES METHOD BLANK RESULTS
SAMPLE mg/m3 of
CONTROL NO. TYPE PARAMETER carbon
DI H20 BLANK TOC 0.477
DI H20 BLANK TOC 0.302
-122-
-------
TABLE 7-29
TOG ANALYSES, LIQUID SAMPLES REPLICATE RESULTS
SAMPLE
LOCATION
A-l
B-l
E-l
F-l
SAMPLE
CONTROL ANALYSES
NUMBER (mg/m3 of carbon)
46360 1,471
1,415
1,426
46394 1,327
1,280
1,318
46430 1,202
1,157
1,166
46460 1,167
1,168
1,189
A\rERAGE
CONCIJNTRATION
(mg/m3 of carbon)
1,436
1,304
1,180
1,173
RELATIVE
STANDARD
DEVIATION
2%
2%
2%
1%
AVERAGE
-123-
-------
Table 7-30, duplicate results for sludge samples; Teible 7-31, matrix spike
results; and the results of EMSL - QC sample analyses in Tables 7-32 and 7-33.
Purgeable Organic Carbon (POC) Analyses
Performance standards for the analysis of purgeable organic carbon, POC,
in liquid samples were not available at the time this method was proposed for
use in this project. Because this procedure has not reached EPA standard
method status or acceptance and lacks EPA standard method development results,
standards for precision and accuracy are not obtainable. The research into
the use of POC as a surrogate analytical parameter for liquid samples provided
the following results:
Actual (%) Gtoals (%)
Precision (% RSD)
Measurement 3 NA
Sample collection 3 NA
Analytical 4 NA
Accuracy (% REG)
MS 90 NA
EMSL spike 89 NA
Completeness (%) 100 95
The actual QC sample results from which these precision and accuracy
determinations were made are provided in the following tables. Table 7-34
provides blank results. Table 7-35 provides the results of the QC set of
replicate analyses. Table 7-36 provides matrix spike results, and Table 7-37
provides the EMSL spike results.
-124-
-------
TABLE 7-30
TOC ANALYSES, SLUDGE SAMPLES DUPLICATE RESULTS
SAMPLE
SAMPLE CONTROL ANALYSES
LOCATION NUMBER (mg/m3 of carbon)
A\rERAGE
CONCENTRATION
(mg/m3 of carbon)
RELATIVE
STANDARD
DEVIATION
E-5
46448
39,938
34,829
35,794
36,854
-125-
-------
TABLE 7-31
TOC ANALYSES MATRIX SPIKE RESULTS
AMOUNT TRUE
REPORTED VALUE PERCENT
SAMPLE GCA SAMPLE (mg/m3 (mg/m3 RECOVERY
LOCATION CONTROL NO. TYPE PARAMETER of carbon) of carbon)
F-l 46460 Liquid TOC 87.9 91.5 96.1
-126-
-------
TABLE 7-32
TOC ANALYSES, LIQUID SAMPLES
EMSL QC SAMPLE RESULTS
SAMPLE
NUMBER
WP782-4
WP782-4
WP782-4
WP782-4
WP782-4
PARAMETER
TOC
TOC
TOC
TOC
TOC
AMOUNT
REPORTED
(mg/m^
of carbon)
92.44
91.37
85.86
91.75
89.18
TRUE
VALUE
(mg/m^
of carbon)
91.5
91.5
91.5
91.5
91.5
AVERAGE
PERCENT
RECOVERY
101.0
99.9
93.8
100.3
97.5
98.5%
-127-
-------
TABLE 7-33
TOC ANALYSES, SLUDGE SAMPLES
EMSL QC SAMPLE RESULTS
AMOUNT TROT
REPORTED VALUE PERCENT
SAMPLE (mg/m3 (mg/m3 RECOVERY
NUMBER PARAMETER of carbon) of carbon)
EPA QC TOC 216.4 225.7 95.9
-128-
-------
TABLE 7-34
POC ANALYSES BLANK RESULTS
GCA SAMPLE tng/m3 of
CONTROL NO. TYPE PARAMETER carbon
DI H20 BLANK POC 0.009
DI H20 BLANK POC 0.008
-129-
-------
TABLE 7-35
POC ANALYSES, LIQUID SAMPLES
REPLICATE ANALYSES
SAMPLE
LOCATION
F-l
F-l
F-l
F-l
F-l
F-l
F-l
F-l
F-l
F-l
F-l
F-l
F-l
MEASUREMENT
(1-13)
SAMPLE
COLLECTION
(1-7)
ANALYTICAL
(3,14,15)
SAMPLE
TYPE
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
CONTROL NO.
46460
46461
46462
46463
46464
46465
46466
46467
46468
46469
46470
46471
46472
AVERAGE
SUM (Xi2)
(SUM Xi)2
STD.DEV.
REL.STD.DEV.
AVERAGE
SUM (Xi2)
(SUM Xi)2
STD.DEV.
REL.STD.DEV.
AVERAGE
SUM (Xi2)
(SUM Xi)2
STD.DEV.
REL.STD.DEV.
QC SET POC
ALIQUOT (mg/m3
NUMBER of carbon
1 150
146
2 154
143
3 146
140
136
4 139
140
5 147
145
6 149
145
7 149
147
8 147
146
9 151
151
142
10 143
145
11 144
12 141
13 142
145
526,930
13,162,384
4
3%
145
315,984
4,734,976
5
3%
141
59,412
178,084
5
4%
-130-
-------
TABLE 7-36
POC ANALYSES MATRIX SPIKE RESULTS
AMOUNT TRUE
REPORTED VALUE PERCENT
SAMPLE SAMPLE (mg/m3 (mg/m3 RECOVERY
LOCATION CONTROL NO. TYPE PARAMETER of carbon) of carbon)
F-l 46470 Liquid POC 8.23 10 82.3
F-l 46471 Liquid POC 10.11 10 101.1
F-l 46472 Liquid POC 8.73 10 87.3
AVERAGE 90.2%
-131-
-------
TABLE 7-37
POC ANALYSES EMSL QC SAMPLE RESULTS
AMOUNT TRUE
REPORTED VALUE PERCENT
SAMPLE SAMPLE (mg/m3 (itng/m3 RECOVERY
NUMBER TYPE PARAMETER of carbon) of carbon) ~%-^-
WP782-4 SPIKE POC 81.16 91.5 88.7
-132-
-------
GC/PID Volatile Organics Analysis
Quality control samples for the GC/PID analysis of samples collected
during the composite syringe field trials included blanks, duplicates, matrix
spikes and EMSL spikes. The results presented in this section indicate that
the analytical methodology performed well for this study. Table 7-38 shows no
detectable level of benzene or toluene in the field-biased syringe blank.
Since these compounds were the only analytical parameters selected for this
field study, no sample contamination is indicated to have occurred.
All syringe samples were analyzed in triplicate. The results of these
analyses and the calculated relative standard deviations are presented in
Tables 7-39 and 7-40. Also, summarized in Table 7-41 are the results of two
grab samples which were analyzed in duplicate. Table 7-42 provides the
results of spiked sample analyses. In summary, the precision and accuracy
estimates for these procedures are indicated by the following results:
Actual (%) Goals (%)
Precision (% RSD)
Syringe with pump 2 <75
Syringe with capillary 2
Accuracy (% REG) 96 60 - 145
Completeness (%) 100 95
In order to assess the accuracy of the GC/PID methodology, a matrix spike
and an EMSL QC sample were analyzed. The results ranged from 85 percent to
112 percent recovery. These results are well within the goal stated in the
QAPP of 60 to 145 percent.
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TABLE 7-38
GC/PID VOLATILE ORGANIC ANALYSES BLANK 1ZESULTS
SAMPLE Benzene Toluene
LOCATION CONTROL NO. (mg/1) (mg/1)
SYRINGE FBB 46487 0.5 <0.5
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TABLE 7-39
DUPLICATE ANALYSES, GC/PID VOLATILE ORGANIC ANALYSES
CONCENTRATION ( mg/ 1 )
CONTROL SAMPLE SAMPLE
NUMBER LOCATION TYPE PARAMETER ABC
46408 S-l Syringe Benzene 23 23 23
Pump
Toluene 2.9 2.8 2.8
46489A S-l Syringe Benzene 26 27 27
Pump
£ Toluene 3.8 3.7 3.8
i
46489B S-l Syringe Benzene 24 25 . 24
Pump
Toluene 3.2 3.1 3.0
RELATIVE
STANDARD
AVERAGE DEVIATION
23.0 0.0%
2.8 2.0%
26.7 2.9%
3.8 1.5%
24.3 2.4%
3.1 3.2%
AVERAGE
REL. STD. DEV.
1.9%
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TABLE 7-40
DUPLICATE ANALYSES, GC/PID VOLATILE ORGANIC ANALYSES
1
M
U)
CTl
CONCENTRATION ( mg/ 1 )
CONTROL SAMPLE SAMPLE
NUMBER LOCATION TYPE PARAMETER ABC
46491 S-l Syringe Benzene 25 24 24
Capillary
Toluene 2.6 2.5 2.5
46490 S-l Syringe Benzene 17 17 17
Capillary
Toluene 1.3 1.2 1.3
RELATIVE
STANDARD
AVERAGE DEVIATION
24.1 3.4%
2.5 3.2%
17.1 0.0%
1.3 1.1%
AVERAGE
REL. STD. DEV.
1.9%
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TABLE 7-41
DUPLICATE ANALYSES, GC/PID VOLATILE ORGANIC ANALYSES
CONCENTRATION in mq/1
CONTROL SAMPLE SAMPLE
NUMBER LOCATION TYPE PARAMETER A B
46481 S-3 Grab Benzene 28 29
Toluene 2.8 2.8
46480 S-2 Grab Benzene 36 36
Toluene 4.3 4.3
AVERAGE
28.5
2.8
36.0
4.3
RELATIVE
STANDARD
DEVIATION
2.5%
0.0%
0.0%
0.0%
AVERAGE
REL. STD. DEV. 0.2%
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TABLE 7-42
GC/PID VOLATILE ORGANIC ANALYSES MATRIX SPIKE RECOVERIES
SAMPLE
LOCATION
CONTROL NO.
AMOUNT
REPORTED
PARAMETER (mg/1)
TRUE
VALUE PERCENT
(mg/1) RECOVERY
EPA-EMBL-QC
S-2
WP879
46479
Benzene
Toluene
Benzene
Toluene
26
4.6
9.1
9.5
30.6
4.1
10
10
85%
112%
91%
95%
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7.3 On-Site Analyses
The precision and accuracy of the onsite analyticetl methods were assured
by adhering to the procedures and guidelines of the methods discussed in
Section 5. No actual QC sample analyses were conducted in the field.
7.4 Calibration Procedures and Frequency
Laboratory Instruments
All analytical instruments, including the GC/FID, GC/MS, GC/PID, TOC and
PCX! systems, were calibrated in accordance with the procedures listed in the
QAPP, and following the guidelines of the referenced EPA, methodology.
Onsite Instrumentation
Field instruments were used at First Chemical Corporation following
procedures outlined in U.S. EPA Methodology EPA-600/4-84-017 "Methods for
Chemical Analysis of Water and Wastes." The field instruments were tested and
calibrated following manufacturers specifications and the frequency table
listed in the program QAPP.
7.5 Sample Custody
The purpose of chain-of-custody procedures is to document the identity of
the sample and its handling from its first existence as a sample until
analysis and data reduction are completed. Sample custody procedures and the
forms used at First Chemical Corporation are discussed in this section.
Sample bank custody procedures will also be discussed.
Field Chain-of-Custody Record Sheets
A two-part carbonless copy custody record was used following the NEIC
format. Samples obtained from First Chemical Corporation were recorded daily
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on the custody forms, signed by the sampler, and relinquished by the field
team leader. Copies of the forms are included in Appendix A.
Sample Identification
Each sample, including replicates and field-biased blanks have a field
sample tag completely filled in with analysis requested, sampler and sample
location. The tag is printed on a waterproof, tear-resistant paper which
insures legibility.
Custody Seals and Shipped Samples
Samples collected at First Chemical Corporation were shipped on a daily
basis back to the contractor laboratory by a Air Carrier (e.g.. Federal
Express). Shipments were made following DOT protocols in steel-lined
coolers. Each cooler contained a chain-of-custody record of the samples
within. The package was then closed with strapping tape and custody seals, so
that the carrier is transporting a sealed container.
Sample Bank Custody
A Division Sample Bank was maintained to implement chain-of-custody
procedures and to provide proper storage for all samples submitted to the
Division.
Upon receipt at the Sample Bank, each shipment was inspected to assess the
condition of the shipping container and the samples within. The enclosed
chain-of-custody forms were cross-referenced with all the samples in the
shipment. The records were signed by the Sample Bank Assistant and recorded
in the bound master Sample Log under a Control Number.
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7.6 Data Reduction
Precision
Precision was determined by the analysis of replicate samples and is
expressed as the standard deviation, S, which is determined according to the
following equation:
N 2 1
Z X
S = / i=l i N \i=l (1)
N - 1
where: S = standard deviation
xi = individual measurement result
N = number of measurements
Relative standard deviation is also reported. It is calculated as follows:
(*\
RSD = 100 I (2)
\X /
where: RSD = relative standard deviation, expressed in percent
S = standard deviation
X = arithmetic mean of replicate measurements
Precision of duplicate samples is expressed as the relative percent
difference, which is determined according to the following equation:
Value 1 - Value 2
Relative % Difference = x 100 (3)
arithmetic mean of
value 1 and 2
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Accuracy
Accuracy was estimated from the analysis of spiked samples, or Laboratory
Control samples whose true values are known to the Laboratory QC Coordinator.
Accuracy is expressed as percent recovery or as relative error. The formulas
to calculate these values are:
/Measured Value\
Percent Recovery = 100 I I (4)
\ True Value /
(Measured Value - True Value \
) (5)
Trace Value /
Completeness
Completeness is reported as the percentage of all measurements made whose
results are judged to be valid. The procedures used for validating data and
determination of outliers are contained in Section 8.0 of this QA plan. The
following formula was used to estimate completeness:
(V \
] (6)
I
where: C = percent completeness
V = number of measurements judged valid
T = total number of measurements
Surrogate Study
Presentation of the surrogate study results included comparisons of the
GC/MS compound specific results to those generated by the surrogate analytical
parameters, POC and TOC. The volatile surrogate parameter comparison were
made according to the following equations using POC and GC/MS VOC data.
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N
C = I Cx
T x = 1
(7)
(8)
where:
Wc =
MWX =
N =
N
S
S =
y
z
u = i
y
z
a = 1
(9)
y - 1
weight of carbon per compound
molecular weight of compound
number of compounds identified in GC/MS VOC analysis
total carbon-weighted GC/MS VOC concentration, ppm as
carbon
specific volatile organic compound result from GC/MS scan,
ppm
POC concentration, ppm of carbon
correlation factor between POC surrogate and GC/MS VOC
total
number of analytical comparisons
standard deviation of correlation factors
The total organic surrogate parameter comparison were made according to
the following equations using the TOC and GC/MS VOC and SVOC results:
N
Z
x = 1
MW,
CB
(ii)
1
/ y 2\
f T p V.
1 ,
/
( y
y
. 2
\
D 1
(12)
y -
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where: CA = total carbon weighted GC/MS concentration including both
vex:
and SVOC results
N = number of compounds identified in GC/MS VOC and SVOC
analysis
Ri = correlation factor between TOC surrogate and GC/MS VOC
and SVOC
CB = TOC concentration, ppm carbon
Time-Integrated Syringe VOC Sampler Field Trial
Each of the four field trial sampling runs compared the analytical results
from the duplicate composite syringe samples to the average of the four grab
samples collected per run. The comparisons were made for each of the selected
compounds analyzed. The analytical results were tabulated for each run, and
percent differences calculated using the following equation.
% Difference = - x 100 (13)
Xi
Steam Stripper Vent Flow Measurement
An approximate stack velocity was calculated from the basic pitot tube
velocity formula:
/ 2 A P
V = J (14)
V P
where: V = velocity [ft/sec]
P = pressure [LBF/ft2]
p = density [slugs/ft^]
The smallest readable increment on the manometer was .005 inches H20, or
0.026 pounds force per square foot. The density of the stack gas was assumed
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to be that of 80°C air at 1 ATM, or .0021 slugs/ft^. The minimum detection
limit of the device is then:
2 (.026)
V=/ ~ 5.0 feet/sec (15)
.0021
Given an inside pipe diameter of 2.0 inches, the minimum detectable flow
is 6.5 CFM.
7.7 Deviations from the QA Plan
This section of the quality assurance discussion iss meant to identify the
deviations which occurred during the program from that which was proposed in
the quality assurance project plan. Several issues of this type did occur
during the implementation of the lagoon study. One primary deviation was the
reduction in the scope of the sampling and analytical activities. This
reduction was the result of curtailed sampling necessitated by the hurricane
warning conditions imposed by the facility. Four sampling locations were
selected instead of the eight which were originally proposed.
Technically, the analytical methodology proposed for the collected samples
was implemented consistent with the QAPP. The TOC and POC analyses for the
surrogate study and the GC/PID analyses for the syringe composite sampler
field trials were completed on schedule. The nature of the samples collected
as well as severe instrumental impacts resulted in serious analytical delays
for the GC/FID and GC/MS analyses. These delays occurred for many reasons,
including:
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The occurrence of unidentified aliphatic (CIO) compounds in the
sample matrix, necessitated two hour retention time screening runs
for all GC/FID and GC/MS analyses. Prior to completion of these
sample screening analyses dilution ratios and surrogate compound
spiking concentrations could not be determined. This lengthy
turnaround time for each sample resulted in analytical delays.
The complex sample matrix resulted in data reduction complications
as well as exaggerated equipment maintenance and repair demands,
including; frequent column replacement, syringe failure and
autosampler malfunctions. Also, a fault in the software of the
GC/MS volatile organic instrument resulted in a period of
instrument downtime.
All semivolatile organic samples were subjected to screening
analyses to determine dilution ratios and surrogate compound
spiking concentrations. Screening was necessary due to the
expected variability in the samples based on the color range of
the samples from red to yellow to black. This screening to
determine spike levels is not usually required for semivolatile
organics analyses and resulted in analytical delays.
Frequent reanalysis of samples was required when unacceptable
surrogate spike recoveries were identified, particularly for some
of the phenolic semivolatile organics. Also, retention time
shifts due to matrix effects made quantitation of sample results
difficult, and caused additional delays.
The highly organic nature of the sludge samples and the
corresponding very low sediment content required a more extensive
sample preparation, screening and dilution approach.
Internal GCA corrective action investigations (CA No. 063) were pursued
concurrent with the activities required to respond to the conditions
identified above. The extensive QC sample load in this field program provides
some insight into the precision and accuracy of the analytical work. The
effects of the analytical delays incurred are not, however, separable from
these overall precision and accuracy estimates.
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