O EPA
United States
Environmental Protection
Agency
Office of Solid Waste
Washington DC 20460
December 1990
Hazardous Waste Incineration
EMISSIONS TESTING OF A
WET CEMENT KILN AT
HANNIBAL, MISSOURI
DRAFT FINAL REPORT
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Emissions Testing of
a Wet Cement Kiln
at Hannibal, Missouri
For U.S. Environmental Protection Agency
Office of Solid Waste
Waste Treatment Branch
Washington, D.C. 20460
Work Assignment Manager: Mr. Shiva Garg
December 1990
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ACKNOWLEDGEMENIS
This document was prepared by the EPA’s Office of Solid Waste under the
direction of Mr. J. Robert Holloway, Chief of the Combustion Section, Waste
Treatment Branch, Waste Management Division, and Shiva Garg, also of the
Combustion Section. Field testing and technical support in the preparation of
this document were provided by Midwest Research Institute (MRI) under Contract
No. 68-01—4463. MRI staff who assisted with field sampling, laboratory
analysis, and preparation of the report were Mr. Scott Klamm, Mr. Dan March,
Mr. Jon Onstot, Dr. Andres Romeu, and Mr. Andrew Trenhoim.
iii
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CONTENTS
Page
Acknowledgement iii
List of Figures ... .. . vii
List of Tables ........ ....... . . viii
1. Introduction..... . . . . . . . •.... . . . . •... 1—i
2. Conclusions 2—1
3. Project Description. . . . . . . . . . . . . 3—1
3.1 Project objectives 3-1
3.2 Process description . . . . 3—2
3.3 Test description 3—4
4. Discussion of Results 4—i
4.1 Process operation 4—2
4.2 Organic compound emissions 4-6
4.3 ChlorIde, potassium, and ammoniuni emissions....... 4—33
4.4 Process samples 4—39
5. References.. . . . . . . . . . . . . . . 5—1
Appendices
Appendix A——Sampling and Analysis Procedures A—i
A—i Sampling Procedures . A—9
A—2 SampleHandlingandAnalysls...... . . .. A—37
A—3 Volatiles Analytical Methods .. ..... A—49
A-4 Semivolatiles Analytical Methods.., A-8i
A—5 TOC Analysis Methods. . . . . . . . . . . . . .. . . . . . A—ill
AppendixB——SaniplingandAnalys lsData... . . B—i
B-i Process Data Measured by Continenl:al B-5
B—2 Solid Waste Characterization . B—4i
B-3 CEM Data Measured by MRI 8-45
B—4 Organic Mass Data B—55
B-5 Total Hydrocarbon and Total Organic Mass Data B-85
B—6 Volatile Organics Data... ....... . ... . ... . .... . B—ill
B—7 Semivolatile Organics Data ..... B—l43
B—8 GalbraithLabAnalysisResults . B—l83
B—9 HC1 Data... B—193
B-b TOC Analysis Results B—249
V
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CONTENTS (Contl nued)
Page
Appendix C——QA/QC... .. . . ..... C—i
Appendix D——Risk Assessment Calculations by Radian D—i
vi
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FIGURES
Number Page
3—1 Process flow diagram 3-3
3—2 Detaileddrawingofsamplingports . 3—10
4—1 Dlstrlbutionoforganicmass . 4—10
4—2 ComparisonofT0MandHClevels . 4—14
4—3 Total PCDO’s and PCDF’s compared to the 2,3,7,8—Equivalents... 4—29
vii
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TABLES
Number Page
3—1 Test matrix . . • • 3—6
3—2 Test overview 3—7
4—1 Average values for process operating parameters 4-3
4—2 MRI CEM average data. . . . . . . . . . . . . . . . . . . . . . 4—4
4—3 Organic mass data for Run 4.. ...... 4—8
4—4 Organic mass distribution . 4—9
4—5 Average organic mass for each test condition. 4—12
4—6 HC and TOM emissions 4—13
4—7 C 1 and C 2 emissions 4—15
4—8 Semivolatlle compounds targeted in GC/MS screen 4-17
4—9 Semivolatile PlC screening data 4-18
4—10 Average semivolatile PlC concentration by operating
condition 4—19
4—11 Volatilescreentargetllst... . ..... 4—20
4—12 VolatilePiCanalysisdatabyruns..... ................ 4—21
4—13 VolatIle PlC concentrations by operating condition.. .. 4-22
4—14 Comparison of continental cement kiln and incinerator PlC
concentrations 4—24
4—15 Additional PICs detected in the kiln emissions 4-25
4—16 Dloxin/furan results for MM5 samples 4-26
4—17 2,3,7,8-Substituted dioxin/furan for MM5 samples 4-27
4—18 2,3,7,8 TCDD equivalent emissions. 4-28
viii
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TABLES (Continued)
Number Page
4-19 Calculation of overall TOC for lime slurry samples 4-31
4-20 Calculation of TOC input to total HC output ratio 4-32
4—21 lonpercentages found in sampling trains.......... 4—34
4-22 Comparison of HC1 monitor and stack sampling train results.... 4-37
4-23 Summary of chlorine and hydrogen chloride emissions 4-38
4-24 Waste feed analysis results 4-40
4—25 Cement qual ity. . . . . . . . . . . . 4—40
ix
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SECTION 1
INTRODUCTION
The Environmental Protection Agency, Office of Solid Waste (EPA/OSW) is
developing regulations to control emissions of products of incomplete combus-
tion (PICs) from cement kilns. The emission parameters planned for use in
this regulation are total hydrocarbons (HCs) and carbon monoxide (CO). To
investigate the use of these parameters as surrogates for PICs, more
information from full-scale testing of wet cement kilns is needed. Data are
also needed for development of regulations to control emissions of hydrogen
chloride (HC1). As a part of this data—gathering effort, a test was conducted
at the Continental Cement Company In Hannibal, Missouri. One reason that
Continental was selected by EPA for the test. Is that the facility uses a wet
process kiln and also burns both liquid and solid (powdered) hazardous waste
as supplementary fuels in the kiln. All tEst activities were conducted for
and under the direction of EPA/OSW, Waste Treatment Branch.
The remaining sections of this report present a detailed description of
the test. Section 2 presents the conclusions drawn from the test. Section 3
presents a description of the project including the project objectives,
facility operations, and test activities. A discussion of the results of this
study is provided in Section 4.
Three appendices contain additional information as follows: Appendix A
presents a detailed discussion of the sampling and analysis methods used in
the study, Appendix B provides the experimental data from the study, and
Appendix C is a review of quality as;urance/quality control (QA/QC)
activities.
1—1
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SECTION 2
CONCLUS IONS
This section contaIns brief statements of the major conclusions based on
analysis of the data generated during this project. Further discussion of
these conclusions and other aspects of the data are presented in Section 4.
1. Total organic mass (TOM) levels during waste-burning conditions were
marginally higher than those mea5ured during the coal—plus—diesel
fuel baseline tests. C 7 -C 17 hydrocarbon levels were higher when
burning waste, but the > C 1 ., hydrocarbon levels were lower. The
baseline (coal-only) TOM was significantly lower, although process
upsets with high 02 levels during 1:hls test run may have contributed
to this effect.
2. The TOM, hot hydrocarbon (hot HC), and cold hydrocarbon (cold HC)
levels generally maintained a consistent relationship to each other
for all six test runs. The TOM levels were highest, with hot HC
within 25% of the TOM value. Cold HC levels were about 50% to 70%
of the hot HC readings.
3. EmissIon levels for both volati le and semivolatile products of
incomplete combustion (PICs) were similar between coal—plus—waste
and baseline (coal-plus-diesel) conditions. The baseline
(coal—only) emissions were considerably lower than either of the
above two conditions, although the process conditions in Run 1 most
likely contributed to this effect. A comparison of the kiln PLC
emissions to typical hazardous waste Incinerators showed the kiln
PICs to generally be at higher levels, although levels of some mdi-
vidual PICs were lower.
2-1
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4. Dioxin/furan emissions followed trends similar to PICs. Run 1
(baseline coal—only) emission rates were lower than either of the
other two test conditions. Coal-plus-waste and baseline (coal-plus-
diesel) conditions both saw higher emissions at nearly the same
levels. Total dioxin/furan emissions were on the order of 100 to
900 ng/dscm. The emissions of 2,3,7,8 dioxln/furan isomers and the
2,3,7,8 TCDD equivalent concentrations followed the same trend from
run to run as the total dioxin/furan emissions.
5. The input rate of total organic carbon (TOC) in the kiln feed
materials, mostly in the shale, ranged from 11 to 99 times the stack
emission rate of hydrocarbons. Thus, TOC in the feed materials
potentially contributed to the hydrocarbon emissions. Hydrocarbons
originating from the TOC, however, could not be distinguished in
this test from hydrocarbons originating from combustion of coal or
waste In the kiln. Pyrolysis—GC/MS analysis of the shale showed
most of the TOC was alkanes with 9 to 16 carbons.
6. Ammonia (NH 3 ) and hydrogen chloride (HC1) in the stack gases
apparently react stoichiometrically to form animonium chloride
(NH Cl). At the stack gas temperature of about 300°F and the HC1
sampling train filter temperature of 250°F, the NHkC1 would be
dissociated into NH 3 and HC1. These gases pass the sampling train
filter and reform NHI C1 in the train impingers. Thus, analysis of
the impinger contents measures the chloride ion in NH Cl as HC1.
7. Results of the HC1 dilution sampling train were not conclusive, but
the results tended to show more condensed NHkC1 particles on the
ambient temperature filter than were observed on the heated filter
In the stack HC1 sampling train. This suggests that NH Cl condenses
as the hot stack gases leave the stack and mix with and are cooled
by ambient air.
2—2
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8. The HC1 monitor results agreed with the stack HC1 sampling train
results corrected for any HC1 that could have reacted with NH 3 . It
is likely that NH 4 C1 particles cordensed and deposited in the cool
sampling line to the monitor.
2-3
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SECTION 3
PROJECT DESCRIP1 ION
This section presents the project objectives, a description of the
Continental Cement Co. facility operations, the test design, and a summary of
the sanipling and analysis perfornied for these tests.
3.1 PROJECT OBJECTIVES
The test at the Continental Cement kiln as originally designed to gather
emission data during two modes of process operation: one with no waste feeds
(baseline coal—only) and, a second with powdered (solid) and liquid hazardous
wastes fed to the kiln with the coal. Difficulties in operating the kiln
under coal-only baseline conditions led to establishing a second set of
baseline conditions firing both coal and diesel fuel. Data-gathering
objectives were to characterize these modes of operation as follows:
1. Measure and compare emission level5 of HCs (using both a heated and
unheated hydrocarbon monitor system) and total organic mass as
measured by field GC and the gravimetric fraction of the MM5
(semivolatiles) train.
2. Measure the levels of carbon monodde (CO), carbon dioxide (CO 2 ),
and oxygen (02) in the stack gas.
3. Measure PlC emissions, including dioxins, furans, and low molecular
weight hydrocarbons, for comparison to historical data from other
hazardous waste combustion devices.
4. Measure the emission levels of hydrogen chloride (HC1) using both an
M5—style sampling train and a continuous HC1 monitor for comparative
purposes.
3—1
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5. Determine if chloride emissions are in particulate form (e.g.,
ammonium chloride particles) or gaseous form (e.g., HC1) or both,
after dilution and cooling with ambient air.
6. Measure the levels of total organic carbon (TOC) in the cement kiln
lime slurry feed for comparison to total hydrocarbon emissions
measured in the stack.
7. ObtaIn data on process operating conditions, as monitored by the
facility and data from the facility that characterizes the fossil
fuels and hazardous waste fed to the kiln.
3.2 PROCESS DESCRIPTION
The test site selected for the field sampling program was a wet process,
coal and waste-fired cement kiln. A simplified flow diagram of this cement
manufacturing facility Is shown In Figure 3—1. The plant produces approxi-
mately 1,800 tons/d of cement clinker product from the kiln.
The facility consists of an Allis Chalmers rotary kiln which is designed
to handle approximately 3,000 tons/d of wet slurry feed. The feed material
consists of approximately 85% limestone and 15% shale (dry basis), in a slurry
containing approximately 25% to 30% water. The refractory-lined kiln is
622 ft long with a diameter of 18 ft at the entrance (feed) and 16 feet at the
exit (product). The feed material reaches a temperature of approximately
2800°F in the fuel combustion zone.
Normal coal feed rates are about 18 to 22 tons/h with a maximum of
24 tons/h. The coal feed Is a mixture of high and medium sulfur-coals (and
some petroleum coke). The coal sulfur content ranges from approximately 2.5%
to 3.3%.
Liquid wastes, typically waste solvents and thinners, are also fired in
the kiln, injected axially through the center of the single pulverized coal
3-2
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Flue Gas
(3 = Sampling Location for Test
Limestone
and Shale
Cyclone
(A)
Induced
Draft Fan
Cement
go 3 V dn I
FIgure 3—1. Process flow diagram.
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burner. Liquid waste firing rates are limited by the facility to a maximum of
40 gpm and a maximum chlorine content of 10%. Solid (powdered) waste is
injected into the kiln every 2-3 minutes in charges of about 10 gallons
each. Total wastes are typically fired at a rate corresponding to about 20%
of the total heat Input to the kiln, with chlorine contents normally ranging
from 1% to 4%. Wastes can be fired at a rate up to 50% of the total heat
input to the kiln.
The kiln gases pass through the length of the kiln and dry the incoming
feed slurry stream. The kiln gas exits the kiln, passes through a cyclone for
dust recycle, and enters the electrostatic precipitator (a 4 fIeld ESP
manufactured by American Air Filter). Gas temperatures at the ESP are roughly
500° to 600°F. The flue gas then exits the ESP to an Induced draft fan and is
exhausted to the 150-ft—tall stack. Stack temperatures ranged from 400° to
500°F.
The kiln is equipped with an automatic process control system that
monitors key operating variables. These include slurry, coal, and waste feed
rates; burner zone temperatures; and kiln gas 02, C0 2 , and CO
concentrations. The kiln operates 24 h/day, 7 days/week, except for
maintenance shutdowns, averaging about 330 days of operation per year.
3.3 TEST DESCRIPTION
This section provides a description of the test program. The test
objectives, sampling and analysis activities, and process monitoring are
described. Appendix A provides complete descriptions of the sampling and
analysis methods used for the test.
3.3.1 Test Matrix/Process Operations
The test program Initially projected a matrix of five 2-h test runs at
two defined kiln operating conditions. The first test condition (baseline)
was to involve two test runs conducted at baseline operating conditions. The
kiln was to be operated at essentially stable conditions with no waste feed to
3-4
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the system. Coal was to be the only fuel fired. The second test condition
(coal-plus-waste) was to replace about half of the BTU input from coal with
waste.
Actual field testing demonstrated that :he Initial choice of a coal-only
baseline provided a relatively unstable and difficult to control process.
Normal operations at Continental involve cofiring coal with hazardous waste.
Consequently, the plant purchases lower—grade coal which proved to be a poor
fuel when burned alone. Kiln temperaturE and oxygen levels continually
fluctuated throughout the coal-only baseline test, while the facility normally
maintains steady operations on both of the!;e parameters. A poorer quality
cement was also made during this run. As such, only one coal-only baseline
test was actually performed. A different type of baseline condition was
established in which coal and diesel fuel were both fired to the kiln without
any hazardous waste. Two baseline tests wer performed using coal and diesel
fuel, thereby expanding the overall test program to six 2-h test runs.
Table 3-1 shows the test matrix.
Wastes were fed during the second test. condition, and three replicate
test runs were performed at this condition. The kiln was operated at stable
conditions with the maximum possible feed rate of solid wastes (powdered
solids). Liquid waste was also cofired at. a rate such that the combined
liquid and solid waste heat input was 50% of the heat Input to the kiln.
In addition to the three conditions described above (Baseline Coal-Only,
Baseline Coal—plus-Diesel, Coal-plus-Waste Feeds), a 2-h HC1 test was also
performed under liquid waste plus coal burning conditions. No powdered wastes
were fed during the special HC1 test. Sampling activities during this special
HC1 test included only waste feeds, HC1 train, HC1 dilution air train, and HC1
continuous monitoring.
Process data measured by Continental’s process monitors were manually
recorded every 15 mm throughout each test run. Sampling activities were
temporarily halted during any significant process upsets or Instabilities.
3—5
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Table 3—1. TEST MATRIX
Run Condition
1 Baseline coal-only
2 Coal—plus-wastes (liquid and solid)
3 Coal—plus-wastes (liquid and solid)
4 Coal—plus-wastes (liquid and solid)
5 Baseline coal-plus-diesel fuel
6 Baseline coal-plus-diesel fuel
HC1 test Coal—plus-waste (liquid only)
3.3.2 Summary of Sampling and Analysis
Table 3-2 provides a summary of the test objectives and the measurement
techniques used to meet those objectives. As shown in the table, more than
one measurement technique was used In some cases to meet a single objective.
Conversely, a single technique may have been used to meet more than one
objective.
The frequency, number, type, and size (or quantity) of all samples
collected during each run is presented In Table 3—3. The table also lists the
sampling and analytical method(s) used for each sample. The matrix presented
in Table 3—3 represents the sample collection scheme for one test run; i.e.,
the number of samples collected during a single 2-h test. Figure 3-1 shows
the location of each sampling point. Combustion gases were sampled at either
the stack or transition duct between the ESP and stack, as noted in Table 3-3
and shown in more detail in Figure 3—2.
Sumary descriptions of the sample collection procedures are presented In
Appendix A of this report. A summary of the sample preparation and analytical
methods is presented in Appendix B.
3-6
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TABLE 3-2. TEST OVERVIEW
Sampling and analysis objective Measurement technique
• Measure HC with heated and unheated • Modified EPA Method 25Aa
systems
• Measure organic mass • Method oDiob__soivent
extraction, evaporation and
weighing
• Field GC/FIDC analysis
• Measure CU, CU 2 , and 02 CO-—Method 10
• 02, C0 2 ——Method 3A
• Organic screen (PlCfdetermlnation) ‘ M thod oolob__Gc,MSd analysis
including PCDD/PCDF • VOST —-GC/MS analysis
• C 1 and C 2 hydrocarbons • Tedlar bag__GC/FIDC analysis
• Measure HC1 HC1 sampling train, HC1
dilution train, and HC1
continuous monitor
• Determine b c t ’ in lime slurry • Solids-—Combustion in LECO
and process water furnace and measurement of CO 2
evolved
• Liquids--Catalytic combusion
and measurement of CO 2 evolved
Note: The analytical methods associated with the above measurement techniques
are defined in Table 3-3.
a HC measured using EPA Modified Method 25A systems equipped with flame
b ionization detector.
SW—846 Method 0010 modified per Appendix A.
GC/FID--Gas chromatography/flame lonizaticin detector.
GC/MS—-Gas chromatography/mass spectrometry.
VOST--Volatile organics sampling train (SW-846 Method 0030).
PCDD/PCDF—-Polychlorinated dibenzodloxin/polychlorinated dibenzofuran.
Methane, ethane, ethylene, and acetylene.
TOC--Total organic carbon.
3-7
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TABLE 3—3. SUMMARY OF SAMPLING AND ANALYSIS ACTIVITIES
1 2—h composite per
run
1 2—h composite per
run
2 2-h composite per
run
2 Three trap pairs
at 30 mm per
pair
ContInuous 2 h
1 Sample injected
every 10—15 mm
C
Method 0010 50—70 ft 3
4-9 ft 3 of
stack gas
VOST ( 0030 )h - 10 L per
train pair
Field GC
Method 10
MM25A
Method 3A
Method 3A
MM25A
PCDO,PCDFd
> Cli organic
mass
Organic screen
Moisture
Temperature
Velocity
Chlorides
Potassium ion
Ammonium Ion
Chlorides
Potassium ion
Ammonium ion
Organic screen
CI - Cl i
Organic mass
CO
HC (cold)
CO 2
0
H (hot)
HC I
Solvent extraction
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
CC/MS
Grav lmetr Ic
Thermocouple
Pitot tube
Ion chromatography
(D4327—84)
I cP—AES
Selective ion
Ion chromatography
(D4327—84)
I CP—AES
Selective ion
Field GC/FID
EPA Method 10
EPA MM25A
EPA Method 3A
EPA Method 3A
EPA MM25A
Gas filter
correlation
Sample
Sample locatlona
Sampling
frequency
for each run
Sampling Analytical
method Sample size parameters
Preparation
method Analytical methodb
Solvent extraction
Solvent extraction
9
HCI train 52—54 ft 3
GC/MSe
Grav lmetric
Stack gas
Lime slurry
HCI dilutIon
train
Integrated
gas sample
(Tedlar bag)
C 1 and C
HydrocJbons
Thermal desorpt ion CC/MS
NA GC/FID
1 Continuous
3 One grab sample
taken every
30 mm, compos—
ited into one
sample per run
3—15 L
(dry)
(Total)
1000 mL,
50 inL each
grab
Scoop (S007)
Total organic
carbon
F ii tered
into solid
and water
fractions
Combustion b
Leco furnace
(solids) and
Method 415.1
(liquids),
measurement of
C O 2 evolved.
(continued)
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TABLE 3—3 (concluded)
Sample
Sample
location 8
Sampling
frequency
for each run
Sanipi Ing
method
Sample size
Analytical
parameters
Preparat ,on
method
b
Analytical method
Powdered waste
4
One grab sample
from each con—
tamer, compos—
ited Into one
sample per run
Trier
500 g
each
grab
HHV
Chlorine
NA
NA
Calorimeter
(02015—77)
Chlorine (D808—81
and D4327j 84) or
(E44281)
Liquid waste
5
One grab sample
taken every
30 mm, compos—
Ited into one
sample per run
Tap (S004)
(Total)
1000 mL,
50 ml each
grab
HHV
Chlorine
NA
NA
Calorimeter
(02015—77)
Chlorine (0808—81
and D4327j-84) or
(E442—81)’
a Sample location as indicated in Figure 3—1.
b Sample preparation and analytical methods, as referenced in the A. 0. Little, EPA 600. and SW—846 methods. Also draft EPA HCI
C t ) sample protocol.
0
c Exact volume of gas sampled dependent on lsokinetic sampling rate.
d +...i., ...i .-..., .- I A
,—‘. . . . ‘ .,.—. •, —‘,
e Gas chromatography/mass spectrometry.
HCI train——HCI sampling train based on the EPA “Draft Method for the Determination of HCI Emissions from Municipal and Hazardous
Waste Incinerators” (USEPA, QAD, July 1988).
Runs 1 and 2 were operated at lower sampi Ing rates, sampling only 7—9 ft 3 for those two runs.
h Volatile organic sampling train (EPA Method 0030).
Methane, ethane, ethylene, and acetylene only.
MM25A——Modified Method 25A.
k University of Texas A&M, Geochemical and Environmental Research Group, SOP—8907.
E442—81 is used for samples with high (> 0.1%) concentrations, and 0808—81 and D4327—84 are used for samples with low
concentrations.
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Flue Gas
+
Sampling Point #2
(Used for VOST and
HCI Dilution Train)
Figure 3-2.
Detailed drawing of sampling ports.
T
75
•4-4” 0 Ports @ 900
(Sampling Point #1)
ity
Monitor
Q 49S VkJ.,, IO29 O
3-10
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3.3.3 HC and Organic Mass
HC emissions were measured using both a heated and unheated EPA Modified
Method 25A (M25A) sampling systems, equipped with flame ionization detectors
(FIOs). As a source of comparison to the HC measurements, organic carbon mass
emissions were measured using a Method 0010 sampling train (I.e., SW—846
Method 0010) and a field gas chromatograph (CC). Samples from the Method 0010
train were analyzed gravimetrically after extraction and evaporation to
determine the carbon fraction greater than C17 (> 300°C boiling point). The
GC, equipped with an FID, was used to analyze syringe grab samples and
determine Cl through C17 carbon fractions (up to 300°C boiling point). Summed
together, the gravimetric and GC fractions provide a total organic mass value
which can be quantitatively compared to the Modified M25A HC values. The com-
parison was made on the basis of HC emissions calculated as propane.
The organic mass sampling was modified from the existing EPA Level 1
testing protocols, as defined in the Level 1 Source Assessment Manual,
IERL-RTP Procedures Manual: Level 1 Environirnental Assessments (2nd Edition),
EPA 600/7-78-201.
3.3.4 Organic Screen
The organic screen provides semiquantit tive characterization of organic
compounds, or PICs, present in exhaust gases. Volatile organics were deter-
mined using a volatile organic sampling train (VOST) as described in SW-846
Method 0030. VOST samples were analyzed by gas chromatography/mass spectrom-
etry (GC/MS). Semivolatile organics were determined using the SW—846
Method 0010 samplIng train (previously referenced above for organic mass
determinations). Samples were analyzed by GC/MS. The screen provided a semi-
quantitative analysis of priority pollutants and the five largest additional
GC peaks.
As a part of the organic screen, total polychlorinated dlbenzodioxin and
polychiorinated dibenzofuran (PCDD/PCDF) concentrations were determined in
stack gas for samples from four of the six test runs. PCDDs/PCDFs were
analyzed from a separate split of the extract from the above-referenced
3—11
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Method 0010 sample train, as subsequently described In Appendix A-2 of this
report.
3.3.5 C 1 and C 2 Hydrocarbons
An Integrated stack gas sample for volatiles was collected using Tedlar
gas bags. A 3— to 15-L sample was collected over the duration of each test
run at a sampling rate of approximately 30 to 70 mL/min. Analysis of the bag
sample was conducted for C 1 and C 2 hydrocarbons (methane, ethane, ethylene,
and acetylene) by GC/FID, on site, at the end of each test run.
3.3.6 Hydrogen Chloride
Total HC1 was determined in stack gas using an HC1 sampling train.
Samples were collected and analyzed based on the EPA’s “Draft Method for the
Determination of HC1 Emissions from Municipal and Hazardous Waste Inciner-
ators” (IJSEPA, Source Branch Quality Assurance DivisIon, July 1988). The
filter and impingers in the HC1 train were analyzed separately for chloride
ion to distinguish between particulate and gaseous chlorides. These samples
were also analyzed for ammoniurn and potassium Ions.
A second sampling train collected a stack gas sample which was diluted
with ambient air before collection in the impingers. This train will be
referred to as the “HCl Dilution Train.” The filter and impingers in the HC1
dilution train were analyzed separately for chloride ion to distinguish
between particulate and gaseous chlorides. These samples were also analyzed
for anunonium and potassium Ions. Appendix A more fully describes the HC1
dilution train.
An HC1 continuous monitor was used for analysis of stack gases during
run 5 and the special 2-h HC1 test. The HC1 monitor was operated concurrently
with the HC1 sampling trains In order for data comparisons to be made.
The HC1 calculations (Appendix B-9) contain footnotes on data that are
associated with estimates of several probe rinse and one run’s impinger
volumes. The actual volumes are not available. Approximations of the volumes
3—12
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were made by measuring the sample volume and estimating how much was used In
the chemical analysis. These estimates should be within 5 mL (10% of the
actual volumes), which does not affect thi? usefulness of the final data.
Additionally, note that the rinse volume estimations will only affect front—
half data.
3.3.7 ContInuous Emissions Monitors
CO, C0 2 , and 02 were continuously monitored throughout the tests. CO was
sampled and analyzed following EPA Reference Method 10. Co 2 and 02 were
sampled and analyzed according to procedures In Appendix B—3. HC1 was
monitored during run 5 and the HC1 test as mentioned above in Section 3.3.6
using a separate sample line.
3.3.8 Total Organic Carbon
Lime slurry feed to the kiln was sampled and analyzed for TOC. Lime
slurry samples were filtered prior to tnalysis into solid and liquid
fractions. Solids were treated with hydrochloric acid to remove carbonate
carbon, then combusted in a Leco furnace according to University of Texas A&M,
Geochemical and Environmental Research Group, SOP-8907. Water samples were
combusted according to EPA Method 415.1. In both cases, measurement by
continuous monitor of the CO 2 evolved determined the TOC present.
3.3.9 Waste/Fuel Characterization
Liquid waste grab samples were collected about every half hour during
runs 2, 3, and 4 of the test series as well as during the special HC1 run.
Each grab sample was about 50 to 100 mL, composited into one sample for each
run. Samples were stored with Ice and analyied for higher heating value (HHV)
and chlorine content by Gaibralth Laboratorl s, Knoxville, Tennessee.
One powdered waste grab sample per run (runs 2, 3, and 4) was collected
by Continental personnel for MRI. The samples were collected using a trier,
being taken from the unloading truck prior 1.o filling the powdered waste feed
hopper. Samples were stored with ice and analyzed for higher heating value
(HHV) and chlorine content by Galbraith Laboratories, Knoxville, Tennessee.
3-13
-------
One pulverized coal grab sample per run was collected from the chute
directly feeding to the kiln. Samples were stored with ice and archived.
Diesel fuel samples were collected in runs 5 and 6 and composited
identically to the liquid waste samples. Samples were stored with ice and
archived.
3.3.10 ESP Dust Sampling
Two dust grab samples were collected from each run, one of recycle dust
(typically ESPs 1 and 2) and one of waste/landfill dust (typically ESPs 3
and 4). These samples were stored with Ice and archived.
3—14
-------
SECTION 4
DISCUSSION OF RESULTS
This section discusses the test re5;ults relative to the project
objectives. The section is divided Into three subsections. The first
discusses process data and operation of t ie kiln. The second subsection
discusses organic compound emissions, and the third discusses inorganic
compound emissions.
4-1
-------
4.1 PROCESS OPERATION
Table 4—1 presents average values of the principal process operating
parameters for each test run. Raw data and mm/max values for process data
are In Appendix B-i, along with pertinent graphs and other Information.
Process operation was replicated closely from run to run, except for planned
variations in the feed of coal, waste, and diesel fuel to the kiln for each
test condition. Raw material (lime slurry) feed rate to the kiln was within
126 to 132 tons/h, except for run 1, whIch was 95 tons/h. Burner zone
temperature (BZT), measured about 60 ft downstream of the kiln burners, ranged
from 2260° to 2450°F.
Run 1 was conducted with the kiln firing coal only—-no hazardous wastes
or auxiliary fuels of any kind. Due to the relatively poor quality of coal
available, plant operations during run 1 were unstable, requiring more
frequent adjustments of kiln controls by the operator. Kiln rotational speed,
lime slurry feed rate, dust feed rate, coal feed rate, and kiln temperatures
were all considerably different during run 1 than in runs 2 to 6. Differences
were also reflected in the ID fan amps and kiln amps.
Dust from the four-stage ESP is either recycled to the kiln entrance or
disposed of as waste. Under normal operations, dusts from ESP stages 1 and 2
are recycled, while dust from stages 3 and 4 are treated as wastes. The rate
monitored by process Instruments is the recycled dust. The higher dust rates
seen during the baseline tests (runs 1, 5, and 6) are because of the higher
dust recycle necessary for process stability. Dust recycle was used for
additional control of kiln temperatures.
Fuel/feed ratios were calculated for each run. For these calculations,
fuel is the sum of coal and hazardous waste feeds In tons per hour. Feed is
the sum of lime slurry and dust rates. The facility uses the fuel/feed ratio
as an indicator of overall plant operations. Relative consistency was
observed between the three replicate waste feed tests (runs 2, 3, 4) and again
for the two baseline tests with diesel fuel (runs 5, 6).
4—2
-------
TABLE 4-1. AVERAGE VALUES FOR PROCESS OPERATING pARAMETERSa
Process cond
ition
Baseline
Bas
eline
Parameter
(coal only)
Run 1
Waste fired
(coal & diesel)
Waste fired
Run 5
Run 6
I-ICl test
Run 2
Run 3
Run 4
Lime slurry feed rate, tons/h
95
129
132
132
126
127
110
Dust recycle rate, tons/h
18
3
4
2
9.5
9.9
2
Coal feed rate, tons/h
19
11.4
11.6
11.9
11.8
13.1
8.7
Diesel fuel feed rate, tons/h
NA
NA
NA
NA
4.9
3.8
NA
Jaske ’fuel, tons/h equivalentsu
NA
10.5
11.5
11.5
NA
NA
6.0
Liquid hazardous waste, tons/h
NA
7.9
9.2
10.0
NA
NA
6.2
Powdered hazardous waste, tons/h
Fuel/feed ratioC
NA
0.171
4.6
0.166
4.0
0.170
3.9
0.174
NA
0.144
NA
0.140
-
0.131
Kiln rotational speed, rev/h
51
67
70
70
66
66
57
Kiln amps
926
1136
1034
1005
1066
1041
1088
Burner zone temperature, °F
2447
2293
2274
2272
2261
2290
2244
Chain section temperature, °F
1619
1700
1766
1785
1590
1600
1693
Feed end temperature, °F
491
577
600
600
544
553
571
ESP inlet temperature, °F
443
502
540
540
469
480
494
ESP Inlet O , %
ESP inlet SO 2 , ppm
ESP inlet N0 , ppm
ID fan draft, in’H 2 O
ID fan % open
3.1
805
916
-2.0
37
1.9
223
619
—3.5
66
2.0
422
939
-3.7
83
1.9
939
1102
—3.6
78
2.0
277
344
—4.1
65
2.0
332
152
-3.8
57
3.5
365
194
—2.9
52
ID fan % of max. rotation
59
60
60
60
60
60
60
ID fan amps
65
73
76
77
75
76
70
Opacity, %
13
25
33
39
16
15
10
Stack temperature, °F
448
527
557
551
505
517
NA
Stack flow rate, dcsm/mln
2710
2910
3000
3480
3150
3430
NA
NA = not applicable or not available
a All data are read directly or calculated from the facility’s process control monitors, except stack
temperature and stack flow rate, which are taken from MRI sampling data.
b These values are calculated by the plant and represent the coal Btu equivalent of waste feed in tons/h.
c Fuel/feed ratio is calculated using fuel = Coal + Waste fuel; feed = Lime slurry + Dust.
S
C
(A.)
-------
Supplemental fuel feed rate Is the measure of either liquid hazardous
waste (runs 2, 3, 4) or diesel fuel (runs 5, 6) used during the test. Neither
type of feed was used during run 1, which fired coal only.
Process temperatures were measured at four separate locations. Burner
Zone Temperature (BZT) measures temperature In the first 60 ft of the kiln.
The chain section of the kiln begins about two thirds and ends about three
fourths of the kiln length from the burners. Chain section temperature is
monitored within this region. Feed end temperature is measured on the high
end of the kiln, where lime slurry feed enters the kiln. ESP inlet
temperature is monitored in the duct immediately upstream of the first ESP
unit. Temperatures In each section were fairly consistent during replicate
tests (runs 2, 3, 4, and runs 5 and 6, respectively). Temperatures were
slightly higher during waste—burning test conditions (runs 2, 3 and 4).
Plant oxygen levels, monitored in the duct just upstream of the ESPs were
kept near 2% for all tests except run 1 and the HCl test. Process
instabilities during run 1 resulted in an average of 3.1% for that condi-
tion. MRI’s continuous monitor data measured at the stack are shown in
Table 4-2 (and Appendix 8-3). Stack 02 levels were consistently 2% to 3%
higher than the facility’s data, likely due to air inleakage in the process
between the two locations. The higher 02 levels for runs 1 and the HC1 test
were also observed at the stack. Notice that CO 2 values include CO 2
contributed from the limestone as well as combustion products.
TABLE 4-2. MRI CEM AVERAGE DATAa
Parameter
Units
Run 1
Run 2
Run 3
Run 4
Run 5
Run 6
02
%
5.9
3.9
4.2
4.1
4.4
4.5
CO 2
%
20.7
23.2
22.3
22.7
22.1
22.5
CO
ppm
198.4
279.5
326.3
264.8
271.1
243.1
a All are on a dry basis.
4-4
-------
The plant CO monitor was not functional during the test series.
Plant SO 2 and NO monitors were located just upstream of the ID fan.
Readings taken were instantaneous and not iiitegrated over time, so there is
considerable scatter in the data. Table 4-1 shows the average values for each
run.
ID fan draft, fan % open (damper), fan % of maximum rotational speed, and
fan amps were all monitored as indicators of fan operations. Operation was
consistent for all runs except run 1 when tFie overall process throughput was
somewhat lower.
Kiln amps were monitored as an Indicator of solids buildup and clinker
product within the kiln. Again, readings were fairly consistent with the
exception of run 1, when product throughput rate was somewhat lower.
Opacity was measured in the stack and averaged below 40% for all test
runs. All three of the baseline tests runs 1, 5, and 6) had average
opacities of 16% or less. For 10 mm In run 5, opacity increased to 100% when
a CO excursion triggered an ESP cutoff.
4-5
-------
4.2 ORGANIC COMPOUND EMISSIONS
This section presents a discussion of organic compound emissions.
Included are a description of: (1) total hydrocarbon (HC) arid total organic
mass (TOM) emissions; (2) emissions of semivolatile products of incomplete
combustion (PIC5); (3) the emissions of volatile PICs; (4) dioxin/furan
emissions results; and (5) the total organic carbon content (TOC) of the raw
material feed (I.e., crushed limestone and shale).
4.2.1 TOM and HC Emissions
Organic carbon mass emissions were quantified within boiling point ranges
which roughly equate to ranges in the number of carbon atoms in organic
compounds. Nonvolatile organic mass was measured using a SW—846 Method 0010
sampling train, and a field gas chromatograph (GC) was used for volatiles and
semivolatiles. Samples from the Method 0010 train were analyzed gravimetri-
cally following extraction and evaporation to determine the carbon fraction
greater than C 1 ., (> 300°C boiling point). The GC, equipped with an FID, was
used to determine the C 1 through C 1 ., carbon fraction (up to 300°C boiling
point). GC samples were taken from the hot HC (subsequently defined) sample
line. Summed together, the gravimetric and GC values provided a total organic
mass (TOM) value which was compared to total hydrocarbon (HC) values. This
comparison was made by converting the organic mass values to propane
equivalent concentrations, since HC emissions are measured as propane.
HC emissions were measured by two different techniques identified here as
hot and cold HC. The primary difference was that the hot HC measurement used
a sample line and instrument heated to 150°C and the cold HC measurement used
an ice cooled condensate trap near the duct sampling port and an unheated
sample line. Both used a flame Ionization detector (FID) as did the organic
GC analyses. Both techniques are described In Appendix A-i, along with the
field GC technique. The cold HC technique is more closely representative of
historical HC monitoring techniques. The hot HC technique is under
consideration as a measurement technique for regulation of hazardous waste
incinerators, boilers, and industrial furnaces.
4-6
-------
The following discussions of TOM and HC emission measurements is divided
into two subsections. The first presents the total organic mass results
determined by the gravimetric and GC sampling systems. The second presents
the HC measurements and compares this data to TOM measurements.
4.2.1.1 TOM Emissions—-.
TOM was determined as three major organic fractions: C 1 —C 7 volatile
compounds, C 7 -C 1 ., semivolatile compounds, ‘nd > C 17 nonvolatile compounds.
The average C 1 —C 7 and C 7 -C 17 fractions were calculated from Individual GC
samples. An average value for the > C 1 , fraction was generated from the
gravimetric analysis of the Method 0010 sampling train. The reported total
mass was calculated by summing the fractional carbon masses. All organic
masses were calculated as propane on a dry basis. Appendix B-4 contains the
analytical data for each GC sample.
A limited number of discrete or instantaneous GC samples were analyzed
for TOM during each test run. These discrete samples may or may not have
coincided with emissions peaks. If the GC samples were collected during short
term emissions peaks, the TOM values would be biased high (or vice versa) for
the respective run. Comparison of the sample times with the continuous HC
data suggest any bias is probably small, except possibly for run 4. During
run 4 there were two discrete GC samples that showed high C 7 -C 11 values (253.9
and 76.5 ppm). These two values quadrupled the semivolatile run averages.
The samples were collected during periods when the presence or absence of a HC
peak could not be confirmed, but, the highest value was near an ESP
shutdown. Table 4-3 presents the GC data for the samples collected during
run 4. The GC results for the remaining test runs are contained in
Appendix B—4.
The distribution of the TOM among the three fractions is given in
Table 4-4 and Is illustrated graphically in Figure 4—1. Run 1 TOM levels were
significantly lower than those measured during the remaining runs, but plant
operating conditions varied throughout run 1. The plant does not normally
operate under coal-firing alone conditions. Variations in the Btu value of
the coal, combined with dust recycle problems, caused a series of high
4-7
-------
TABLE 4-3. ORGANIC MASS DATA FOR RUN 4
Sample no.
Organic fractions (ppm propane, dry)
Total mass
(TOM, ppm
propane, dry)
Time
C 1 -C 7
C 7 C 17
>
C 17
R4SS1
1053
36.2
1.3
R4SS2
1112
49.6
1.5
R4SS3
1130
19.3
253.9
R4SS4
1148
45.7
24.4
R4SS5
1207
33.6
39.1
R4SS7
1232
43.9
4.8
R4SS8
1251
61.5
2,5
R4SS9
1309
43.2
1.0
R4SS1 O
1327
355
76.5
R4SS12
1346
39.4
7.9
R4SS13
1404
647
4.5
R4SS14
1422
683
32
Run Average =
45 1
35.0
5.62
85 7
Note Off-scale peak in C7-C17 region during 1130 sample, due to ESP shutdown.
Note. R4SS6 was taken during calibration and there was no R4SS1 1
MRI.MI,8913 TAB 4-8
-------
A
mass
verage organic
(ppm propane,
dry)
Total
ma ;s
(TOM)
Distribution
percent of
total mass
Run
C 1 -C 7
C 7 C 17
>
C 17
C 1 C 7
C 7 C 1 ,
> C 1 ,
1
17.7
3.2
1.73
22.6
78%
14%
8%
2
78.5
14.1
3.54
96.1
82%
15%
4%
3
67.0
20.5
5.31
92.8
72%
22%
6%
4
45.1
35.0
5.62
85.7
53%
41%
7%
5
72.3
5.0
8.22
85.5
85%
6%
10%
6
67.8
3.5
9.56
80.9
84%
4%
12%
Run 1--Baseline coal-only
Run 2,3,4--Coal-plus-waste feeds
Run 5,6--Baseline coal-plus-diesel fuel
Note: The run 4 C,-C 1 , value may be biased high (see te t),
MRI.M/,8913 TAB 4-9
-------
DISTRIBUTION OF ORGANIC MASS
Run Number
Figure 4-1
1
I D
0
0
0
U)
C’,
>
E
0
( 1
C
0
C’,
I-
C
0
C
0
0
1 2 3 4 5 6
-------
temperature spikes within the kiln. The temperatures were cooled by intro-
duction of air to the kiln, thus raising oygen levels to 5 to 6% from the
normal 2%. These higher oxygen levels potentially led to better combustion of
the coal and lower TOM levels. However, the free lime measured In the clinker
product was higher for run 1 (shown later in this section, Table 4—24), which
may indicate a poorer quality cement produced.
Table 4-5 presents the average TOM de:ermined for each process condi-
tion. The TOM levels measured during coal-plus—waste burning was slightly
higher than those measured during coal—plus-diesel burning. This increase was
primarily related to an increase In the C 7 —C -, fraction that was not equaled
by a decrease in the > C 1 ., fraction.
4.2.1.2 HC and TOM Emissions-—
Table 4-6 shows the results for HC and TOM emissions measured in the
stack. The results are shown for each of the three process conditions. The
TOM results are presented as the mass in each of three fractions described
earlier and as total mass. HC results are shown for both the hot and cold
monitoring systems.
Figure 4—2 shows that the TOM, hot HC, md cold HC values generally were
proportionally consistent to each other for all six test runs. The hot HC
values were withIn 25% of the measured TOM ‘alues, except for run 4. During
run 4, two C . ,—C 1 . , fraction spikes occurred while the THC monitor was off-line,
thus possibly resulting in a biased TOM value. Flowrate to the GC was not
steady during run 4, which could have contributed to any sample bias. The
cold HC results were consistently lower than the other two measures, with the
cold being 50% to 70% of the hot HC. Loss of organic compounds in the
condensate trap on the cold HC sampling lln is the most likely explanation
for the lower cold HC values.
Table 4-7 shows the results of analyzing the grab bag samples collected
during each run for C 1 —C 2 compounds. Nobe that ethylene (C 2 H ) is not
listed. Ethylene and ethane could not be resolved under field conditions.
Bag samples from runs 2 to 6 were reanalyzed back at MRI’s laboratory using
the field GC and cryofocusing (cryogenically concentrating the sample). The
4-11
-------
TABLE 4-5. AVERAGE ORGANIC MASS FOR EACH TEST CONDITION
Average organic
mass (ppm propane,
dry)
Total mass
Run
C 1 -C 7
C 7 -C 17
> C 17
(TOM)
Baseline with
coal only
(Run 1)
17.7
3.2
1.73
22.6
Hazardous waste
and coal
(Runs 2-4)
63.5
23.2
4.82
91 .6
Baseline with
diesel and coal
(Runs 5 & 6)
70.1
4 3
8.89
83.2
MRJ.Mh8913 TAB 4-12
-------
TABLE 4-6. HC AND TOM EMISSIONS
Run
TOM,
ppmv dry
as propane
HC,
as
ppmv dry
propane
C 1 -C 7
mass
C 7 -C 17
mass
> C 17
mass
Total
mass
Hot
Cold
Coal only
1
17.7
3.2
1 73
22.6
17.3
8.3
Hazardous
2
78.5
14.1
354
96.1
71.9
52.6
waste and
3
67.0
20.5
531
92.8
70.1
47.5
coal
4
45.1
35.0
562
85.7
42 6
27.1
Baseline with
5
72.3
5.0
822
85.5
74.1
41.3
diesel and coal
6
67.8
3.5
956
80 9
77 5
42.2
MRI-M/r8913 .TAB 4-13
-------
COMPARISON OF TOM AND HC LEVELS
Run Number
Figure 4-2
1
a)
C
0
0
0
C l )
-D
>
E
0
L2
C
0
1
C
C)
C
0
0
1 2 3 4 5 6
-------
TABLE 4-7. C 1 AND C 2 EMISSIONS
Run
tota ° ass
(ppmv,dry)
CH
C 2 H 2
C 2 H 6
C 1 and C 2 combined
ppmv,dry % of
TOM
ppmv,dry
%
of
TOM
ppmv,dry
%
of
TOM
ppmv,dry % of
TOM
Coal only
1
22.6
1.6
7
2.7
12
1.1
5
5.4
24
Hazardous
2
96.1
14.8
15
16.9
18
5.4
6
37.1
39
waste and
3
92.8
11.6
13
15.6
17
5.6
6
32.8
35
coal
4
85.7
6.4
7
9.8
11
4.4
5
20.6
24
Baseline
5
85.5
7.6
9
10.7
13
2.3
3
20.6
24
with diesel
6
80.9
10.7
13
16.6
21
3.3
4
30.6
38
and coal
Note: C 2 H 1 , was not detected.
-------
results showed virtually no ethylene present. The existing peaks were
therefore quantified as ethane. The C 1 and C 2 fraction accounts for 24% to
39% of the measured TOM.
4.2.2 Semivolatile Organic Emissions Screen
Qualitative screening of the Method 0010 samples by GC/MS analysis was
conducted to characterize the semivolatile organic compounds emitted as
products of incomplete combustion (PICs). The GC/MS analyses were
semiquantitative and were targeted to identify the compounds listed in
Table 4-8. Table 4-9 presents the concentrations of compounds detected by
these analyses. A blank entry indicates that the compound was not detected;
detection levels were on the order of a few micrograms per dscm.
Table 4—10 presents the average concentrations of the compounds by test
condition. During run 1, when only coal was being fired, the total number of
compounds detected was lower than the other two test conditions. This may be
attributed to the higher oxygen levels in the kiln during this run. Emission
levels were very similar between the other two test conditions.
4.2.3 Volatile Organic Emissions
GC/MS analyses of the VOST Method 0030 samples were conducted to
characterize the volatile organic compounds emitted as PICs. Although not
formally required for this study as per the test plan, calibration curves were
generated for all the PlC compounds contained in Table 4-11. Table 4-12
presents the concentrations of compounds detected by these analyses. A blank
entry indicates that the compound was not detected; quantitation levels were
about 2 to 5 ng/L for most compounds.
Table 4-13 presents the average concentrations of the compounds by test
condition. Emission levels tend to be slightly lower during run 1 (baseline,
coal only) for the majority of the compounds included in the analyses. As
with the semivolatile emissions, levels are very similar for the other two
test conditions.
4-16
-------
TABLE 4-8. SEMIVOLATILE COMPOUNDS TARGETED IN GC/MS SCREEN
phthal ate
1 N—Nltrosodlrnethylaniline
2 Bis(2-chloroethyl) ether
3 Phenol
4 2—Chiorophenol
5 N—Nltroso-dl-n-propylaniine
6 1,3-Dlchlorobenzene
7 1,4-Dlchlorobenzene
8 1,2-Dlchlorobenzene
9 Bls(2-chloroisopropyl) ether
10 Hexachioroethane
11 Nltrobenzene
12 Isophrone
13 2—Nitrophenol
14 2,4-Dlmethylphenol
15 BIs(2-chloroethoxy)methane
16 2,4-Dlchiorophenol
17 1,2,4-Trichlorobenzene
18 Naphthalene
19 Hexachloro-1,3-butadlene
20 4-Chloro—3-niethylphenol
21 Hexachlorocyclopentadlene
22 2,4,6-Trlchlorophenol
23 2,4,5-Trichiorophenol
24 2—Chloronaphthalene
25 2,6-Dlnitrotoluene
26 Dimethyl phthalate
27 Acenaphthylene
28 Acenaphthene
29 2,4—Dlnitrophenol
30 Dlbenzofuran
31 4—Nitrophenol
32 2,4-Dinitrotoluene
33 2—Methylnaphthalene
34 Benzyl alcohol
35 Azobenzene
36 Fluorene
37 4-Chlorophenyl phenyl ether
38 Diethyl phthalate
39 4,6—Dinitro—2-methylphenol
40 Benzoic acid
41 N-Nltrosodiphenylamlne
42 4-Bromophenyl phenyl ether
43 Hexachlorobenzene
44 2-Methyl phenol
45 4-Methyl phenol
46 Pentachlorophenol
47 Phenanthrene
48 Anthracene
49 Di-n-butyl phthalate
50 Aniline
51 Fluoranthene
52 Benzidlne
53 Pyrene
54 Benzyl butyl
55 Chrysene
56 3,3’—Dichlorobenzidine
57 Benz [ a J ant hracene
58 Bis(2—ethylhexyl) phthalate
59 Dl—n-octyl phthalate
60 Benzo [ blfluoranthene
61 Benzolk]fluoranthene
62 Benzo [ alpyrene
63 Dl benz [ a,h] ant hracene
64 Benzo(g,h,tjperylene
65 Indenol 1,2,3-c,d]pyrene
66 4-Chioroaniline
67 2-Nltroaniline
68 3-Nitroaniline
69 4-Nitroanillne
4-17
-------
TABLE 4-9. SEMIVOLATILE PlC SCREENING DATA
Stack gas concentrations, ng/L or lAgldscm
Baseline Baseline
coal only Hazardous waste and coal diesel and coal
Run 1 Run 2 Run 3 Run 4 Run 5 Run 6
Benzyl alcohol 700’ 600’ 500’ 400’ 600’ 400’
Benzoic acid 1000’ 600’ 1000’ 1000’ 600’ 200°
Phenol 77 169 54 67 137
2-Chlorophenol 9
2-Methylphenol 1 5
4-Methylphenol 52 53 61 62 56
Naphthalene 145 600’ 600’ 600’ 600° 500’
2-Methylnaphthalene 52 101 152 89 145 100’
2,4,6-Trtchlorophenol 26 32
Acenaphthylene 95 117 72 106 86
Dibenzofuran 101 146 94 129 91
Diethyl phthalate 26
Fluorene 26 29 42 38
Phenanthrene 21 100° 158 83 162 100’
Anthracene 13 15 23 25
Fluoranthene 46 47 62 51
Pyrene 29 28 49 45
Benz [ a]anthracene 10
Chrysene 23 22 32 32
Bis(2-ethylhexyl) phthalate 53 27
‘Response was higher than the highest calibration point, value is an estimate only.
MRJMft8913 i u 4-1 8
-------
TABLE 4-10. AVERAGE SEMIVOLATILE PlC CONCENTRATION BY
OPERATING CONDITION
Stack gas concentrations, ng/L or 1 . g/dscm
Hazardous Baseline diesel
Baseline waste and coal and coal
coal only average average
Benzyl alcohol 700 500 500
Benzoic acid 1000 900 400
Phenol 100 102
2-Chlorophenol 3
2-Methy lphenol 8
4-Methy lphenol 55 59
Naphthalene 145 600 550
2-Methylnaphthalene 52 114 123
2,4,6-Trichloropheno l 19
Acenaphthy lene 95 96
Dibenzofuran 114 110
Diethyl phthalate 9
Fluorene 18 40
Phenanthrene 21 114 131
Anthracene 9 24
Fluoranthene 31 56
Pyrene 19 47
Benz [ a]anthracene 5
Chrysene 15 32
Bis(2-ethylhexyl) phthalate 40
Note: If the compound was not detected in one run, the value of zero was
used in calculating the condition average.
URI-M/r8913 TAE 4-19
-------
TABLE 4-11. VOLATILE SCREEN TARGET LIST
1 Acetone
2 Acroleln
3 Acrylonitrile
4 Benzene
5 Bromodichioromethane
6 Bromoform
7 Carbon tetrachioride
8 Chloroform
9 Chlorobenzene
10 Dlbroniochioromethane
11 1,1-Dichioroethane
12 1,2-Dichioroethane
13 1,1-Oichloroethene
14 t—1,2—Dichloroethene
15 1,2-Dichioropropane
16 t—1,3—Dichloropropene
17 Diethyl ether
18 1,4—Dioxane
19 Ethylbenzene
20 Methylene chloride
21 Methyl ethyl ketone
22 1,1,2,2-Tetrachloroethane
23 Tetrachioroethene
24 Toluene
25 1,1,1—Trichloroethane
26 1,1,2—Trichioroethane
27 Trichioroethene
4-20
-------
TABLE 4-12. VOLATILE PlC ANALYSIS DATA BY RUNS
Stack gas concentrations, ng/L
Baseline
Baseline
coal only
Hazardous waste
and coal
diesel and coal
Run 1
Run 2
Run 3
Run 4
Run 5
Run 6
Acroleiri
160
240
87
130
750
570
1,1-Dichloroethene
2.4
0.6
0.1
0.1
Acetone
210
510
480
390
960
830
Methylene chloride
728
2608
12
10
14
4.1
Acrylorutrile
270
410
550
620
380
540
t-1,2-Dichloroethane
0.04
0.1
0.1
0.3
0.1
11-Dichloroethane
02
26
2.0
1.0
2.7
Methyl ethyl ketone (MEK)
43
110
160
110
130
180
Chloroform
9.0
5.2
2.6
6.2
14
11
1,1,1-Trichloroethane
7.8
14
21
0.7
Carbon tetrachloride
0.5
2.3
Benzene
510
1800
2800
1400
2100
2100
1,2-Dichloropropane
3.5
16
38
0.1
0.1
Trichloroethene
3.6
2.3
2.1
1.6
3.6
32
1,2-Dichloropropane
05
3.0
2.1
1.7
2.5
2.7
p-Dioxane
Bromodichloromethane
Toluene
27
5.1
160
2.5
580
24
910
0.6
2.3
450
8.0
4.0
950
0.6
960
t-1 ,3-Dich loropropene
0.3
5.7
5.8
6.4
12
12
1,1 ,2 .Trichloroethane
3.5
24
8.1
2.1
5.7
Tetrachloroethene (Perc)
1.8
0.7
4.5
2.3
0.4
0.3
Dibromochloromethane
0.6
0,4
0.6
0.05
0.03
Chlorobenzene (MCB)
33
50
62
42
33
33
Ethylbenzene
26
170
190
75
200
200
Bromoform
1.1
0.1
0.5
1,1 ,2,2-Tetrachloroethane
10
18
12
14
14
14
High value may be due to laboratory contamination.
MRI .M/r8913 TAB
4-21
-------
TABLE 4-13. VOLATILE PlC CONCENTRATIONS BY OPERATING CONDITION
Stack gas concentrations, ng/L or gIdscm
Baseline Hazardous waste Baseline diesel
coal only and coal average and coal average
Acrolein 160 150 660
1,1-Dichloroethene 1.0 0.1
Acetone 210 460 890
Methylene chloride 728 958 8.8
Acrylonitrile 270 530 460
t-1 ,2-D,chloroethene 0.04 0.2 0.1
1,1-Dichloroethane 0.2 1.5 1.9
Methyl ethyl ketone (MEK) 43 120 160
Chloroform 9.0 4.6 13
1,1,1-Tnch loroethane 7.8 5.7
Carbon tetrachtoride 0.5 0.8
Benzene 510 2000 2100
1,2 -Dich loroethane 3.5 18 0.1
Trichloroethene 3.6 2.0 3.4
1,2-Dichloropropane 05 2.3 26
p-Dioxane 27 0.2 8.0
Bromodictiloromethane 5.1 24 2.3
Toluene 160 640 960
t-1 ,3-Dichloropropene 0.3 6.0 12
1,1 ,2-Trichloroethane 3.5 11 3.9
Tetrachloroethene (Perc) 1.8 2.5 0.3
Dibromoch loromettiane 0.6 0.3 0.03
Chlorobenzene (MCB) 33 51 33
Ethylbenzene 26 140 200
Bromoform 1.1 0.2
1,1 ,2,2-Tetrachloroethane 10 15 14
High value may be due to laboratory contamination.
MR I-M/18913TAD 4.2
-------
Table 4—14 provides a comparison of the PICs measured in the stack gas
for this project to the PICs historically detected in stack gases from
hazardous waste Incinerators. The incinerator data include the most common
PICs that were detected during tests at eight. Incinerators. Comparison of any
individual compound concentrations should be made with caution, since only one
kiln test is compared to a series of incinerator tests. Table 4—14 Indicates
that several compounds are common to combw;tlon of waste in both kllns and
incinerators. It also shows that the concentrations of PICs In the kiln stack
gas were generally greater than those metsured in the incinerator stack
gases. As can be seen in Table 4—15, many additional compounds were detected
in the kiln stack gas.
4.2.4 Dioxin/Furan Emissions
Dioxin and furan analysis was performed on MM5 samples from runs 1, 3, 4,
and 5 of the test series. Table 4-16 presents the dioxin and furan results by
hornologs from analysis of the MM5 samples and the total dioxins and furans for
each run. Quantities found below detection limits (< value) were considered
to be at the detection limit to calculate the worst-case total emission
values.
Table 4—17 presents dioxin and furan data for the 2,3,7,8-substituted
isomers. Using these data and the toxic equivalents (Reference 1) for each
Isomer, Table 4—18 was generated. Toxic equivalencies were then summed into a
single 2,3,7,8—TCDD equivalence values for each run. Results are presented In
both concentration and mass emission rate units. Figure 4-3 compares the
total PCDDs/PCDFs and 2,3,7,8-TCDD equivalents for each run.
4.2.5 Total Organic Carbon (TOC) Results
Total organic carbon (TOC) was measured in the raw feed materials for
comparison to the total hydrocarbon emissions from the stack. Raw material
samples collected included shale, limestone, and the lime slurry (a mixture of
the shale, limestone and water). Shale and limestone samples were collected
during a site survey prior to the test series, and lime slurry samples were
collected during the actual test series. The slurry samples were filtered In
4-23
-------
TABLE 4-14. COMPARISON OF CONTINENTAL CEMENT KILN AND
INCINERATOR P lC CONCENTRATIONS
Range of
concentrations,
ng/L
Kiln
Incineratorsa
Benzene
510
- 2800
12 - 670
Bromodlchioromethane
1
- 5
3 - 92
Bromoform
0
- 1
1 - 24
Chlorobenzene (MCB)
33
- 62
1 - 10
Chloroform
3
- 14
1 - 1300
Dibromochioromethane
0
- 1
1 - 12
Hexachlorobenzene
b
1 - 7
Methylene chloride
4
- 260 c
2 - 27
Naphthalene
150
- 760
5 - 100
2—Nitrophenol
b
25 - 50
Phenol
0
- 170
4 - 22
Tetrachioroethene (PERC)
0
- 5
1 - 3
Toluene
160
- 960
2 - 75
1,1,1-Trichioroethane
1
- 14
1 - 2
a “Performance Evaluation of Full—Scale Hazardous Waste
Incinerators, Volume 2,” EPA—600/2-84-181b, P685-129518,
November 1984.
b BDL = below detection limits
C High value in range may be due to laboratory contamination.
4-24
-------
TABLE 4-15. ADDITIONAL PICs DETECTED IN THE KILN EMISSIONS
Range of concentrations
(ng/L)
Acenaphthylene 0 117
Acetone 212 - 963
Acrolein 87 - 750
Acrylonitrile 268 - 623
Anthracene 0 - 25
Benzoic acid 152 - 1400
Benzyl alcohol 443 - 691
Benz [ a]anthracene 0 - 10
Bis(2 -ethylhexyl) phthalate 0 - 53
Carbon tetrachloride 0 - 2.3
2-Chlorophenol 0 - 9
Chrysene 0 - 32
Dibenzofuran 0 - 146
1,1-Dich loroethane 0.2 - 2.7
1,1-Dich loroethene 0 - 2.4
1,2-Dich loroethane 1 - 37.5
1,2-Dichtoropropane 0.5 - 3
t-1 2-Dichloroethene 0.04 - 0.3
t-1,3-D ichloropropene 0.3 - 12
Diethyl phthalate 0 - 26
p-Dioxane 0 - 27
Ethylbenzene 26 - 205
Fluoranthene 0 - 62
Fluorene 0 - 42
2-Methylnaphthalene 52 - 152
2-Methylphenol 0 - 15
4-Methylphenol 0 - 62
Methyl ethyl ketone (MEK) 43 - 178
Phenanthrene 21 - 162
Pyrene 0 49
Trichloroethene 2 - 4
1,1,2,2-Tetrachloroethane 10 - 18
1,1,2-Trichloroethane 0 - 24
2,4,6-Trichlorophenol 0 - 32
URIM/r8913.TAB 4-25
-------
TABLE 4-16. DIOXIN/FURAN RESULTS FOR MM5 SAMPLES
Blank
Analyte train Run 1 Run 3 Run 4 Run 5
Sample volume (dscm) 1.447 1.714 1.805 1.788
Stack flow rate (dscm/m) 2700 3000 3500 3100
Dioxins (øa )
TCDD 1,530 12,100 53,100 121,000 52,600
PeCDD 1,340 17,100 151,000 284,000 531,000
HxCDD 3,150 82,100 276,000 615,000 1,010,000
HpCDD 845 9,490 25,300 48,100 87,300
OCDD 2,160 5,360 16,900 19.500 15,800
Total (pg) 9,030 126,200 522,000 1,088,000 1,700,000
Total (ng/dscm) 87.2 305 603 951
Total ( .ig/min) 237 916 2100 3000
Furans (øn )
TCDF 2,280 16,900 164,000 322,000 99,100
PeCDF 568 5,810 38,300 179,000 70,600
HxCDF 240 2,510 14,200 21,500 11,900
HpCDF ND 3,400 8,850 8,400 2,470
O C DF 228 <7 < 10 < 27 <4
Total (pg) 3,316 28,600 225,000 531,000 184,100
Total (ngfdscm) 19 8 131 294 103
Total ( g/min) 53 7 394 1020 324
Total dioxin/furan’s (ng/dscm) 107 436 897 1050
Total dioxin/furan’s ( .ig/min) 291 1310 3120 3320
MRI-Mf ,8913 TAB 4-26
-------
TABLE 4-17. 2,3,7,8-SUBSTITUTED DIOXIN/FURAN FOR MM5 SAMPLES
Analyte Run 1 Run 3 Run 4 Run 5
Sample volume (dscm) 1 .447 1 .714 1 .805 1 .788
Stack flow rate (dscm/m) 2700 3000 3500 3100
Dioxins (ixi )
2,3,7,8-TCDD 7 6 < 14 7
1,2,3,7,8-PeCDD 255 3,240 4,520 5,220
1,2,3,4,7,8-HxCDD 550 4,580 7,170 9,280
1,2,3,6,7,8-HxCDD 647 3,750 7,040 11,100
1,2,3,7,8,9-HxCDD 520 4,980 7,880 9,150
1,2,3,4,6,7,8-HpCDD 4,140 ‘12,400 21,300 36,000
1 ,2,3,4,6,7,8,9-OCDD 5,360 : 16,900 19,500 1 5,800
Total (pg) 11,480 45,900 67,400 86,600
Total (ngldscm) 7.93 26.8 37.3 48.4
Total (ng/min) 21,500 80,400 130,000 152,000
Furans (pc )
2,3,7,8-TCDF 9 210° < 10 < 21
1,2,3,7,8-PeCDF 6 6,490 < 10,400 < 3,720
2,3,4,7,8-PeCDF 2,320 14,900 < 27,400 10,800
1,2,3,4,7,8-HxCDF 1,140 4,970 7,440 3,720
1,2,3,6,7,8-HxCDF 571 2,350 3,960 2,000
1,2,3,7,8,0-HxCDF 137 565 < 741 275
1,2,3,4,6,7,8-HpCDF 2,050 4,750 4,860 1,400
1,2,3,4,7,8,9-HpCDF 356 546 624 190
1,2,3,4,6,7,8,9-OCDF 1,660 < 3,530 < 3,040 < 469
Total (pg) 8,500 < 39,000 < 60,200 < 23,800
Total (ng/dscm) 5.87 22 8 < 33.4 < 133
Total (ng/min) < 15,900 68,300 < 116,000 < 41,900
Notes: Less than (<) is dropped from totals where the total values below detection limits are
less than 1 0% of the total
Run 4 data is questionable due to low surrogate recoveries
a Based on pql rather than detection limit due to analytical difficulties
MRJ-M/,89 13 TAB 4-27
-------
TABLE 4-18 2,3.7.8 TCDD EQUIVALENT EMISSIONS
Total 2,3 ,7,8-TCDD
equivalent concentration lng/dscm) = 1 190 3 323 5 910 343
Emission (ng/min) = 3.228 9.980 20.550 10.790
EmissIon lg/hr) = 0002 - 0006 0012 .0006
Run I
Run 3
Run 4
Run 5
Sample volume (dscm) 1 714
Sample volume (decm) 1 805
Sample volume (dscm) 1 447
Sample volume (dscm) 1.788
Analyte
EPA
equlv
faclo,
Stack flow rate ldscm/m) 2.713
Stack flow rate (decm/m) 3.004
Slack flow rate (decmlm) 3.478
Stack flow rate (decm/m) 3.147
Total Equiv
(p9) lng/dscm) lng/dscrn)
Total Equlv
p9) lng/dscml lng/dscml
Total Equ lv
lpg) lngldscml lng/decm)
Total Equ lv
(pg) lng/dscm) lng/decm)
Dloxlns
2,3 ,7,8TCDD
1
7
00660
00660
6
00210
00210
14
0008
0008
7
00151
00151
1,2,3,7,8-PeCOD
0 6
255
0 0518
0 0258
3.240
0 942
0 471
4.520
1 31
0 655
5.220
1.45
0.727
1 ,2 ,3,4 ,7,8-H CDD
0 1
550
00843
0 00840
4.580
00497
000497
7.170
2 08
0208
9.280
2 59
0 259
1.2.3.6,7.8 HXCDD
0 1
647
0 447
00447
3.750
1 09
0 109
7.040
2 04
0 204
11,100
309
0 309
1.2.3,7,8.9 HSCDD
0 1
520
0 359
00359
4.980
1 45
0 145
7,880
2 28
0228
9.150
255
0255
1,2,3,4,6,7,8 HpCD
0 01
4.140
2 86
0 0286
12.400
3 60
00361
21.300
6 17
0 0617
36.000
10.0
0 100
OCDD
0 001
5.360
3 70
0 0037
16,900
4 91
0 00491
19,500
5 65
0.00565
15.800
440
000440
.
Fu,an
2,3,7,8.TCDF
1,2.3.7,8 PeCDF
0 1
0 05
9
6
0 138
0 004
0 0138
0 00021
NC
6,490
0 0
1 89
000
0 0943
10
10,400
0 00
3 01
0000
0.151
21
3,720
0.01
1 04
0 001
0.0618
2,3.4.7,8 PeCDF
0 5
2.320
1 60
0802
14,900
4 33
2 17
27,400
7 94
3 97
10.800
301
1.61
1,2,3,4,7,B’hI sCDF
0 1
1,140
0788
0 0788
4.970
1 44
0 146
7,440
2 16
0216
3.720
1 04
0.104
1,2,3,6,7,9 l-1aCDF
0 1
571
0 395
00395
2.350
0 683
00683
3.960
1.15
0 115
2,000
0557
0.0560
2.3.4,6,7.8 HxCDF
0 1
225
0 155
00155
884
0 257
0 0257
1.720
0498
0 0498
1.250
0 35
0035
1,2,3,7,8,9-HxCDF
0 1
137
0 0968
0 00968
565
0 164
00164
741
0 215
00215
275
00766
0.00770
1,2,3,46,7,8 HpCO
0 01
2.050
1 42
0 0142
4.750
1 38
0 0138
4,860
1 41
0 0141
1,400
0 390
000390
1,2.3,4,7,8,9HpCD
001
356
0246
000246
546
0159
000159
624
0181
000181
190
00529
0000500
OCOF
0001
1.660
115
000115
3.530
103
000103
MR1.Mhe913 TAB
-------
Total PCDD’s
and PCDF’s
Compared to the 2,3,7,8-Equivalents
Run4
Test Condition
Total D/F’s 2,3,7,8-Equiv. I
0
1050
0
(I )
D
0)
0
ci
RQ7
1200
1000
800
600
400
200
0
Runi Run3
Run5
Figure 4-3.
-------
the laboratory to allow separate analysis of the solid dried filter cake and
the water fraction by different methods. Analytical methods (Appendix A) were
combustion in a Leco furnace (solids) and EPA Method 415.1 (water fraction).
Table 4-19 presents the combined results. Calculations are in
Appendix B-1O. Analysis of the shale and limestone samples showed TOC levels
of 1.8% and below detection limits, respectively.
The bC, or organic carbon, input rates were compared to the stack
emission or output of organic carbon based on the HC measurements. Percent
TOC in the feed was converted into a mass input rate of carbon, while the hot
HC emission rate (as ppm propane) was converted into carbon output rates. The
ratio of carbon input to carbon output ranged from 11 to 99 as shown in
Table 4-19. Thus, the carbon input was sufficient to account for the HC
output from the stack.
In addition to the TOC analysis, a pyrolysis-GC/MS analysis was performed
on the shale and limestone samples. These analyses provide information on the
organic compounds which compose the TOC within each material. These samples
presented some problems to the analyst due to inhomogeneity, and results may
not be representative.
The pyrolysis analysis of the shale showed that the organics were
aliphatic in nature, having 30 or fewer carbons. The most abundant aliphatic
species observed correspond to normal and branched alkanes having between 9
and 16 carbons. Some aromatics, such as xylene, were detected in small
quantities. Replicate analyses were performed on the one shale sample to
verify compounds detected. Shale comprises about 15% of the solids fed to
make the lime slurry.
The limestone sample was fairly inhomogeneous, part of it being fine and
sandy, part being rocky. In general, the limestone showed relatively little
organic material. Benzoic acid and acetic acid were detected, along with a
few alkanes. However, the total of these compounds was far less than those
detected in the shale. Limestone comprises about 85% of the solids fed to
make the lime slurry. Appendix B-b contains the raw data for the pyrolysis—
GC/MS analysis.
4-30
-------
TABLE 4-19. CALCULATION OF OVERALL TOC FOR LIME SLURRY SAMPLES
2 Solid
Liquid
Total
3 Solid
Liquid
Total
4 Solid
Liquid
Total
5 Solid
Liquid
Total
6 Solid
Liquid
Total
59.3
40.7
51.6
48.4
66.1
33.9
70 1
29.9
68.6
31.4
0.3262
0.0001
0.3263 0.326
1 .5686
0.0003
1.5689 1.57
0.3636
0.0002
0.3638 0.364
0.6 169
0.0002
0.6171 0.617
0.2264
0 0003
0 2267 0.227
Lime slurry
composition
Run Fraction (%
solids/liquids)
1 Solid
Liquid
Total
61.0
39.0
Overall
slurry
TOC
(%)
TDC in each
fraction (mg/i OOg)’
0.0732
0.0002
0.0734
0.073
0 Basis of 100 g sample of lime slurry, water density of 1 g/mL.
MRI-Ml O9I3 TAB
4-31
-------
TABLE 4-20. CALCULATION OF TOC INPUT TO TOTAL HC OUTPUT RATIO
TOC
Input
TOC
in lime
Lime
slurry
slurry
Run feed (%)
feed rate
(ton/h)
ICC
input
rate
in
lime
slurry
(ton/h)
(g/h)
1 0.073 95 0.0694 63,000
2 0.326 129 0.4205 382,000
3* 1.570 132 2.0724 1,880,000
4 0.364 132 0.4805 426,000
5 0.617 126 0.7774 706,000
6 0.227 127 0.2883 262,000
Total HC Emissions
Total HC
Hot HC, dry HC conc. Stack flow emission
Run ppm propane (pg/L) (dscm/min) (g/h)
1 17.3 26 2700 4200
2 71.9 108 2900 19000
3 70.1 105 3000 19000
4 42.6 64 3500 13000
5 74.1 111 3100 21000
6 77.5 116 3400 24000
Overall Summary
Ratio of input
Run Input (g/h) Output (g/h) to output
1 63,000 4200 15
2 382,000 19000 20
3 1,880,000 19000 99
4 436,000 13000 33
5 706,000 21000 34
6 262,000 24000 11
Note: All ppm to concentration conversions assumed weight of
carbon alone, for a correction factor of 1.5.
* TOC In lime slurry feed from run 3 is significantly higher than for the
other runs. This could have been caused by inhomogeneity of the
sample. No analytical explanation was observed by the laboratory.
4-32
-------
4.3 CHLORIDE, POTASSIUM, AND AMMONIUM EMISSIONS
This section presents data from the HC1 and HC1 dilution air sampling
trains and the HC1 continuous monitor. The HC1 train and monitor sampling
were on the stack, while space limitations required the HC1 dilution train to
be operated from the base of the stack (same location as the VOST
apparatus).
Analyses were performed for three separate species (CV, K+, and NH 3 ) on
each of the four train components (probe rins’ , filter, acid impinger, caustic
impinger) of the two sampling trains. CF analysis was by ion chromatograph,
K analysis was by ICP—AES, and NH 3 analysis was by selective ion
monitoring. Appendix B-9 contains the supporting data and calculations.
Table 4—21 presents the results, including a comparison of front half/back
half results.
It should be noted that the HC1 dilution train was an experimental design
without any validation testing. The purpose of the train was to provide
information on the front half/back half splits of the CF. K , and NH Ions
after the stack gases are diluted and coo ed with ambient air. A direct
quantitative comparison of the data from the two trains, designed and operated
differently, is not appropriate. Some loss of chlorides in the dilution train
probe was suspected.
The HC1 train potassium ion results shDw that it is unlikely that fine
particles can pass through the filter, the majority of the potassium being
detected in the front half. Formation of potassium chloride salts was likely,
and these salts would be in the form of fine solid particles.
Ammonium (NH , , ) ions were detected as a large percentage in the back
half, indicating that most of the NH 4 compo’ nds passed the filter in gaseous
form. Ammonia or ammonlum chloride are wo possibilities. Any ammonia
present in the gas stream would easily pass through the filter and be captured
in the impinger solutions. This is one pos;ible way to explain the presence
of ammonlum Ion in the Impingers. However, ammonia and hydrogen chloride are
highly reactive,
4-33
-------
TABLE 4-21 ION PERCENTAGES FOUND IN SAMPLING TRAINS
Dilution Train
Stack HCI Train
CL-
emission
(9 1mm)
K÷
emission
(9/mm)
NH3
emission
(9/mm)
CL-
emission
(gimmn)
K+
emission
(g/mmn)
NH3
emission
(g/miri)
Run 1
Front Half
73.44
17.044
21.04
74.1°,
1.23
50.09.1
NA
NA
NA
NA
NA
NA
Back Half
Acidic
321.93
74.40,1
7.35
25.99’
1.23
500°A
NA
NA
NA
NA
NA
NA
Caustic
37.04
8.6°A
NA
NA
Total
432.41
28.39
2.46
108043
71.43
17.54
Run 2
Front Half
28 09
4.8°A
56 18
9639’
1.36
555%
NA
NA
NA
NA
NA
NA
Back Half
Acidic
16.81
2.9°A
2 18
3 7°.A
1 09
4459.1
NA
NA
NA
NA
98.69.’
NA
NA
Caustic
544.81
92 4°A
NA
NA
Total
589.71
58.36
2.45
387 00
4.42
38.66
Run 3
Front Half
25 80
5.3°A
74 02
94 2°/
0 14
5 5%
3.73
0.39.1
83.04
055
1.8°il
Back Half
Acidic
297.54
60 8°A
4 59
5 89.4
246
94 5°,4
717.19
62.8°A
1.22
1.4°i
29.82
98.2°A
421.93
36.90,4
Caustic
166.23
34 0°A
Total
489.57
7861
260
1142.85
84.26
30.37
Run 4
Front Half
31.75
2.7°A
101.60
97 8°A
1.47
32.09’
32.28
2 29.4
152.89
99.3°i
0.81
3.09.1
Back Half
Acidic
848.72
73.0°A
2 31
2 2°A
3.13
68.0°,
1005 50
69.9°A
1.05
0.7°,
2654
97.0°A
Caustic
282.69
24 3°A
401.00
27.9°A
Total
1163.16
103.91
460
1438.78
153.94
27.35
Run 5
Front Half
33.90
33 7°i
43.21
93 6°A
4 39
80.39’
39.15
NA
68.20
NA
2.76
NA
Back Half
Acidic
52 23
51 90
2.96
6 4°A
1.08
19 7°i
16234
NA
0.59
NA
40.68
NA
NA
NA
Caustic
14.54
14.40,...
54.0°!
Total
100.67
46.17
5.47
NA
NA
NA
27.09
935°A
311
2.4°i
13.06
3.9°A
35.91
58.3°i
5.64
13.69.4
Run6
Front Half
19.50
Back Half
Acidic
11.10
30.8°i
187
65°A
126.97
97.6°i
151.18
4559.4
25.69
41.7°,
35.90
864°A
Caustic
5 48
15 2°i
168.10
50.6°A
Total
36 08
28.96
13008
332.34
61.60
41.54
HCL Run
Front Half
2351
20 0°i
20.00
81 0°A
020
11.1%
1.93
1.0°A
92.29
99 1°,
009
0.9°A
Back Half
Acidic
76 49
65.2°i
4.68
19 0°A
1 57
88 9%
194.82
96 3°A
0.84
0 9°i
10.07
99.1°A
Caustic
17.37
14 8°i
5 46
2 7°A
Total
117.37
2468
177
20221
93.13
10.16
NOTES 1 Shading indicates a complete data set
2 NA=Not Available due to lost samples or data, see Appendix B-9
3 Data for the front half rinse was lost for the dilution train Runs 2 and 3. thus, the front hatf values are tow
The rinse, however, usually contained a small fraction of the total front halt mass, see Appendix B-9
-------
and if both are present they would likely react to form animonium chloride. A
more reasonable explanation is that v tpor1zed aninionlum chloride (or
dissociated aninionium chloride) passes the filter. The vapor pressure of
animonium chloride at the filter temperature of 250°F is 0.089 m of mercury
(Reference 2). This vapor pressure can account for the existence of up to
120 ppm of ammoniuni chloride, as vapor, in he sampled gas stream. Thus, it
is possible for sufficient ammonium chloride vapor to pass through the filter
at levels well above those measured in the inipingers.
Literature sources indicate that animoniiim chloride is a crystalline solid
which sublimes without melting and Is airiost completely dissociated into
ammonia and hydrogen chloride in the vapor phase (References 3 and 4). At
average stack gas temperatures (300°F) and stack gas concentrations (2 to
10 ppm HC1; equivalent to 3 to 15 ppm NH Cl), essentially all of the animonium
chloride would be vaporized and dissoci Lted into ammonia and hydrog J
chloride.
The above data lead to the conclusion that when HC1 and ammonia are
present In the stack gas they will react to form amnionium chloride. The
amnionluni chloride will be in the form of particles at low temperatures and
will be dissociated at higher temperatures. The ammonium chloride will pass
through a heated filter and be collected in the sampling train impingers and
measured as HC1.
Table 4-21 also shows data from the Cl dilution train In a fashion
similar to the data for the HC1 stack tr Lin. Data from this train were
evaluated to determine If the dilution and cooling, as happens to the stack
gas after it is emitted, would condense tmmonium chloride particles. If
particles form, they should be collected on t.he filter at ambient temperature;
i.e., the ammoniuni ion should be found on t.he filter, not In the impingers.
The results were highly variable, although higher percentages of the aninionium
ion were generally found on the filter th rn for the stack HC1 train. It
should be noted that this experiment was only a rough approximation of the
process of mixing stack gases with the atmosphere, thus firm conclusions are
not possible.
4-35
-------
Table 4-22 compares the HC1 continuous monitor data with the stack HC1
train, which were operated concurrently during two runs (HC1 test and
run 5). Stack gas sample for the continuous monitor was pulled through a
sampling probe fitted with a heated filter, a heated Permapure membrane to
remove moisture, then a 50-ft length of unheated 1/4-in diameter Teflon tubing
to the monitor. This unheated sampling line would cause the stack gas to cool
and would allow for deposition of condensed ammonium chloride on the walls of
the line. These data indicate that the monitor results closely matched the
sampling train results, after excluding any chloride that could have reacted
with the ammonlum ions present In the stack gas. It is likely that ammonium
chloride condensed In the unheated sampling line and deposited on the walls of
the line.
Table 4-23 summarizes the chlorine and hydrogen chloride emissions from
the stack HC1 train. The chlorine concentrations can be compared to HC1
concentrations with and without an adjustment for formation of ammonium
chloride.
4-36
-------
Measured
stack emissions
C 1 NH 4
Run g mol/mun g md/mm
5 4.58 2.39 2.19 79.96 71.16
HCI 5.5 0.59 4.91 179.3 159.6
(a) Excluding chloride which could have reactei with the NH 4 present in
the stack gas.
after formation
Equivalent
of NH 4 CI
HCI (a)
Monitor HCI
g mol/mmn
g/min
9/mm
TABLE 4-22. COMPARISON OF HCI MONITOR AND STACK SAMPLING
TRAIN RESULTS
Sampling train
MRJMI,8913 TAB
4-37
-------
TABLE 4-23. SUMMARY OF CHLORINE AND HYDROGEN CHLORIDE EMISSIONS
Conc. HCI excluding
Conc. HCI (a) potential formation of Conc. Cl 2 (b)
Run (ppm) NH 4 CI (ppm) (ppm)
3 162 148 47.7
4 196 185 39.1
5 35.0 16.7 (c)
6 29.9 15.1 16.6
HCI 41.3 36.9 0.56
Note: Data not available for Runs 1 and 2 (see appendices calculations)
(a) These values assume that all Cl ions collected in the acidic solution were in the
form of HCI.
(b) Determined by the Cl ions collected in the caustic impinger in the MM5 sampling
train.
(c) Sample container was broken during shipment.
MRI.M/r8913 i 438
-------
4.4 PROCESS SAMPLES
Samples of the liquid organic waste and powdered waste from runs 2, 3, 4,
and the HC1 test were analyzed for % Cl find higher heating value (HHV).
Table 4—24 presents the results.
Data on cement quality (free lime) is ‘;hown in Table 4-25. These data
were obtained from the facility’s laboratory for the time periods of each
run. Note that the free lime for run 1 is high compared to the other runs,
possibly due to the unstable process conditioiis during that run.
4—39
-------
TABLE 4-24. WASTE FEED ANALYSIS RESULTS
Run 2
Run 3
Run 4 a
HC1 test
% Cl
Liq. org.
waste
1.83
1.57
1.69/1.62
1.72
Powdered
waste
1.01
1.35
1.69/1.51
NA
HIIV
(Btu/lb)
Liq. org.
waste
10,498
9,837
10,713/10,396
12,630
Powdered
waste
7,828
8,158
8,709/8,932
NA
NA = not applicable
a Replicate analysis.
TABLE 4—25. CEMENT QUALITY
Run
Run time
Sample time
Free lime
1
1118-1448
1200
1400
0.67
0.78
2
1230—1546
1400
1600
0.22
0.50
3
1135-1720
1400
1600
1800
0.39
0.39
0.34
4
1055—1435
1200
1400
0.22
0.28
5
1047—1535
1200
1400
1600
0.50
0.45
0.34
6
1900-2152
2000
2200
0.45
0.39
HC1
1647-1847
1800
0.17
4-40
-------
SECTION 5
REFERENCES
1. Interim Procedures for Estimating Risks Associated With Exposures to
Mixtures of Chlorinated Dibenzo-p-diox ins and Dibenzofurans (CODs and
CDFs) and 1989 Update. EPA/625/3—89/016. March 1989.
2. International Critical Tables. Volume I, First Edition. McGraw-Hill
Publishers, 1928. p. 207.
3. Mellor, J. W. Inorganic and Theoretic 1 il Chemistry. Volume II. 1946.
p. 566.
4. Goldfinger, L., and G. Verhaegen. Stability of Gaseous Amnonium Chloride
Molecule. J. Chemical Physics, 50(3):1457, 1969.
5. IERL-RTP Procedures Manual: Level I Environmental Assessment (2nd
Edition) EPA 600/7—78—201, NTIS NO. PB293—795 (10/78).
5—1
-------
APPENDIX A
SAMPLING AND ANALYSIS PROCEDURES
Test objectives were met by the samplin i and subsequent analysis of stack
gases, lime slurry, process water, fuel oil, solid, and powdered wastes. This
appendix summarizes the sampling and analysis procedures used during the test
burn. Preparation of the sampling equipment, sampling procedures, and
equipment calibration are addressed in Appendix A. The Project QAP more
specifically addresses equipment calibration. Sample handling (transport and
storage) and sample analysis procedures are &ddressed in Appendix A-2.
The attached memo from July 24, 1990 briefly summarizes the day to day
sampling activities of the test series.
A-i
-------
July 24, 1990
TO: Shiva Garg
FROM: Drew Trenholm, Scott Klarnm
SUBJECT:
Daily History of Continental Cement Kiln Field Test
June 18—July 5, 1990
Testing of the Continental Cei ent Wet Process Kiln in
Hannibal, Missouri, took place June :L8-July 5, 1990. The kiln
typically burns pulverized coal (60-80% of BTU load) cofired with
liquid arid powdered hazardous wastes (20-40% of BTU load). The
test series was designed to allow testing of the kiln under
“baseline” conditions——coal fired only, and “waste burning”
conditioris--50% coal, 50% hazardous waste. Dust from the plant’s
four ESP cells is typically split: 1&2 are recycled to the kiln,
3&4 are disposed of as waste.
June 18 -- Setup day
No testing was performed. Equipment was set up and prepared.
June 19 —— No test
Plant fuels were switched over to coal (only) to allow
baseline testing. Plant conditions were unstable and testing was
postponed.
June 20 —- Run 1, Baseline
A baseline test using coal (only) was performed. The process
was not very stable throughout most of the run. Normally, the
plant burns a mixture of coal and hazardous waste, and has operated
in this manner for several years. As a consequence, high grade
coal is no longer purchased by Continental. Upon attempting to
operate firing coal alone, the low grade coal presently available
provided poor process stability. Resultant instabilities caused a
series of temperature spikes and fluctuating oxygen levels within
the kiln. Dust from ESP cells 1,2,and 3 were recycled during Run
1 as an attempt to achieve greater stability. ESP 4 dust was still
disposed of separately.
No sampling equipment failures or nalfunctions occurred during
the test, with the exception of the HC1 continuous monitor. It was
identified that the monitor’s pressure transducer had failed,
prohibiting data collection by the instrument. At that time it was
unknown how to fix the monitor.
A- 3
-------
Mr. Shiva Garg
July 24, 1990
Page 2
June 21 -- Run 2, Waste Burning
Liquid and powdered hazardous wastes were cofired with coal at
50% of the total kiln BTU rate. Process conditions were relatively
stable throughout the test. No significant upsets ocurred.
The HC1 analyzer was still not operational. The manufacturer,
TECO, was contacted for suggestions without success. It became
clear that, as a minimum, a new pressure transducer was necessary
to get the monitor operational, but was not available on short
notice.
June 22 -- Run 3, Waste Burning
Wastes cofired with coal. Again, the waste firing rate was
50% of total kiln BTU input. The process was again stable with one
exception noted below.
During the run, moisture was detected in the hot THC line and
rotameter. All sampling activities were stopped for 20 minutes
(1255—1315) to clean out the lines.
At 1331, the plant switched waste feed tanks. Such action
causes a temporary instability and fluctuations in
temperature/oxygen levels for about 30-45 minutes until the BTTJ
value of waste from the new tank is established. Although this is
a common occurrance for the plant, it was felt that such
instability presented a significant bias in the data given a 2-4
hour test period. Sampling activities were, therefore, stopped
from 1331—1519.
A broken probe liner in the HC1 sampling train invalidated any
sample collected by the train prior to 1331. When sampling
activities were stopped at 1331, the broken liner was discovered
and corrected. The HC1 train was rebuilt and began a 2-hour
sampling phase at 1519. Continuation of other sampling activities
was held until the HC1 train had restarted, allowing coincidental
samples to be taken.
June 23 -- Run 4, Waste Burning
Wastes cofired with coal. Again, the waste firing rate was
50% of total kiln BTU input. The process was again stable.
A- 4
-------
Mr. Shiva Garg
July 24, 1990
Page 3
The MM5 sampling train suffered a broken probe liner as it was
removed from the stack following th€ 3rd traverse. The train
therefore failed its final leak check, but all indications show the
sample as valid. The broken liner was replaced for use in the 4th
traverse.
Again, the HC1 continuous monitor was not operational.
June 24 -- No Testing. Day off for test crew.
June 25 to July 1 No testing.
The kiln was shut down due to “hot spots” on the.shell. Upon
shutdown it was discovered that about 25 feet of refractory within
the kiln needed replacement.
July 2 -- HC1 Test Run
Attempts to operate the kiln on coal (alone) were
unsuccessful. Testing would have provided a second baseline test
identical to that performed on June 20. It was decided that a more
typical, stable baseline test would require another fuel source in
addition to the coal. Diesel fuel would be made available by
Continental for such a baseline test on the 5th of July.
After aborting the coal (only) run on July 2, the plant
switched fuels back to coal plus hazardous waste. After a two hour
“purge time” MRI performed an HC1 test involving waste feed
sampling, MCi continuous monitoring (now operable), HC1 train, and
HC1 dilution train. The test was twD hours long. Wastes were
cofired, but at a slightly lower rate than for the previous tests
(about 40% of BTTJ input). The 40% r tte is more normal of plant
operations.
July 3 and 4 -- No testing.
July 5 —- Run 5, Baseline with Diesel Fuel and Coal
The plant was operated with coal and diesel fuel. No
hazardous wastes were fed. The process was generally stable,
although not as stable as the coal plus hazardous waste runs.
Diesel fuel is a “hotter” fuel (higher BTU value) than the liquid
wastes, so it was a bit trickier for the operators to fine tune and
tweek the system. Occasional oxygen and temperature blips happened
A- 5
-------
Mr. Shiva Garg
July 24, 1990
Page 4
during the run, but nowhere near the instability of Run 1 (Baseline
with coal only).
Equipment failure on the MN5 sample train invalidated sample
collected during the first traverse (1115). All sampling
activities were put on hold to allow rebuilding the train.
At 1120 the plant saw high Co levels, triggering the ESP’s to
shut of f. Particulate levels rose significantly and opacity read
100%. Sampling equipment was not operating. However, CEM probes
were still within the stack. Some pluggage of CEM lines was later
experienced.
By 1220, the MM5 train was again operational. Sampling of all
systems was restarted. The remainder of the run w s completed
without incident.
July 6 -- Run 6, Baseline with Diesel Fuel and Coal
A baseline test with coal and diesel fuel, no hazardous wastes
was conducted. Process stability was essentially the same as for
Run 5.
Prior to beginning the test, the HC1 monitor was dead; a
victim of pluggage due to lime dust. The filtering system for the
monitor was probably overloaded when the ESP’s went down during Run
5.
At 1943, a minor process upset occured. The main fan feeding
coal to the kiln went dead. 02 lsvels immediately rose up to 6%.
The fan was restarted within two minutes and sampling activities
were not interrupted.
Throughout most of this test, dust from ESP’s 2,3,and 4 was
recycled. ESP #1 was not operable.
A- 6
-------
This appendix contains brief descriptions of the sampling and analytical
procedures used during the testing at Continental Cement Company, Hannibal,
Missouri.
Content Page
A—i Sampling Procedures A—9
A—2 SampleHandlingandAnalysis ... ..... A—37
A—3 Volatiles Analytical Methods A—49
A—4 Semivolati les Analytical Methods....,. . . . .. . . . . . A—81
A—5 TOC Analytical Methods . . . . . . . A—ill
A- 7
-------
APPENDIX A—I
SAMPLING PROCEC’URES
A-9
-------
APPENDIX A-I
SAMPLING PROCEDuRES
Test objectives were met by the sampling and subsequent analysis of stack
gases, lime slurry, process water, fuel oil, solid, and powdered wastes. This
appendix summarizes the sampling and analyst; procedures used during the test
burn. Preparation of the sampling equipment, sampling procedures, and
equipment calibration are addressed In Appendix A. The Project QAP more
specifically addresses equipment calibration. Sample handling (transport and
storage) and sample analysis procedures are addressed in Appendix A-2.
1.0 STACK GAS TESTING
The following sampling systems were u!ed to collect stack gas samples
during the test:
• Method 0010 sampling train—-Used to determine PCDD/PCDF emission
concentrations to determine an organic mass fraction, and to screen
for a specific array of semivolatile organics.
• HC1 train--Used to determine HC1 emission concentrations. Ammonium
and potassium ion concentrations were also determined In these
samples.
• HC1 dilution train-—Used to determine HC1 emission concentrations
following a dilution with ambient air. Ammonium and potassium ion
concentrations were also determined in these samples.
• yOST-—Used to screen for a specific: array of volatile organics.
• Field GC system--Equipped with Eli). Used to determine an organic
mass fraction.
• Tedlar bags—-Used to collect gas samples for quantitation of C 1 and
C 2 hydrocarbons by GC/FID.
• Continuous emission monitors (CEMs)——Used to monitor hot and cold
HCs using Modified Method 25A systems equipped with FIDs. CO, C0 2 ,
and 02 emission concentrations also measured following EPA Reference
Method 10 and 3A. HC1 monitoring was performed for purposes of
comparison to the HC1 train.
• Orsat——Method 3 sampling system used to determine 02 and CO 2
emission concentrations using an Orsat analyzer.
A-li
-------
These sampling systems are further defined In the subsequent discussion.
1.1 Method 0010 Train
The Method 0010 sampling train was used to measure carbon fractions
greater than C17 (i.e., organic mass fraction) and to define specific semi—
volatile organics (i.e., organic screen analysis). The carbon fraction was
determined by gravimetric analysis; semivolatile organics were determined by
GC/MS analysis. This train was also used to measure PCDDs/PCDFs.
The sampling procedure consists of isokinetically sampling a volume of
the exhaust gas. Due to the short test period, only — 60 ft of gas,
corrected to dry standard conditions, was collected rather than the 105.9 ft
prescribed by Method 0010. In general, the sampling procedures parallel those
specified in 40 CFR 60, Methods 1 through 5, for particulate analysis.
The design of the Method 0010 sampling train was based on the apparatus
described in SW-846, Method 0010 (September 1986 edition). The train con-
sisted of a stainless steel nozzle, a heated borosilicate glass probe liner,
and a borosilicate filter. The control module used to control the gas
sampling rate and monitor the stack gas parameters contained a leakiess vacuum
pump; a dry gas meter; an orifice meter; and the appropriate valves, gauges,
temperature controllers, and associated hardware. The impingers and their
contents are described below:
• The first impinger is a spiral condenser to cool the sample gas.
• The second impinger is an MRI-designed XAD module containing 70 g of
XAD.
• The third impinger is a modified Greenburg-Smith (GBS) containing
100 mL of double-distilled—in-glass water to catch any carryover
from the first two impingers.
• The fourth impinger is a GBS and will contain 100 mL of double—
distilled—in-glass water.
• The fifth impinger is an empty modified GBS.
• The sixth impinger is a modified GBS, containing approximately 200 g
of blue indicating silica gel.
All glass—to-glass connections are made from threaded glass and Teflon
ferrules. Schematics of the train are shown in Figures Al—i and Al—2.
Calibration--The sampling equipment was calibrated, checked for proper
operation, and cleaned for use prior to arrival on-site.
As a minimum, the following equipment will be calibrated:
1. Dry gas meter/orifice
2. Stack temperature thermocouple
A- 12
-------
Quartz/Glass Liner
Filter
T/C T/C Fine Control
Valve
I— .
t )
L
1 Condenser
2 XAD module, 70 g XAD
3 Modified Greenburg-Smilh, 100 mL double-distilled H 2 0
4 Greenburg-Smith, 100 mL double-distilled H 2 0
5 Modified Greenburg-Smith, empty
6 Modified Greenburg-Smith, silica gel
I? SfV
Pitot Tube
T/C
Check
Valve
Manometer
Heater
Ice Bath
r
Orifice
Vacuum
Line
Airtight
Pump
Figure Al-i. Diagram of MM5 train.
-------
Thi rmoc up .
Wt I
Figure A1—2. MM5 condenser and KAD resin cartridge.
From
F ter
Subme&bIe
Pump
Water In
ro
mping.r
Wcret Cur
Ice
Conden .r XAD-2
A-14
-------
3. Filter oven thermocouple
4. Thermocouple and pyrometer for gas meter
5. Probe nozzles
6. Pltot tube (by comparison to pitot tube in wind tunnel)
Copies of all calibration data will be placed In the project calibration
data file. The calibration procedures used are from the “Quality Assurance
Handbook for Air Pollution Measurement Systems: Volume 111—-Stationary Source
Specific Methods,” USEPA 600/4—77—027b.
All surfaces in the sampling train that came into contact with the sample
gas stream were thoroughly cleaned. The cleaning procedure is discussed in
more detail later in this section. To minimize the potential for
contamination of sampling train glassware 1 all glassware components were
sealed with aluminum foil prior to being packed for storage and transport.
All remaining sampling train components were cleaned and prepared in
accordance with EPA Method 5 procedures.
Sample collection——Sample collection, including leak-checking, was
conducted in accordance with EPA Method 5 procedures. The samples were col-
lected isokinetically over a complete traver ;e of the stack. Twelve traverse
points were sampled using two sample ports located across the width of each
duct. About 60 ft were collected at a sampling rate of — 0.75 ft 3 /min. Two—
hour samples will be collected.
Sample recovery--At the end of a test run after the final leak check, the
sampling train was disassembled into two parts, the probe and the sample box,
which were transferred to the field laboratory for recovery. The inlet to the
sample box was covered, and both ends of the probe were sealed to prevent
sample loss and contamination. In a dE signated section of the field
laboratory, sample components were recovered from the sample box and the
nozzle. The sample component from the probe was recovered In a clean,
ventilated area. All liquid sample compoiients were transferred to amber
glass, precleaned bottles. Sample components were recovered as follows.
o Container 1—-Filter. Use Teflon—coated or stainless steel forcepts
to recover the filter; place the filter in the labeled glass petri
dish.
o Container 2-—XAD—2 resin. Cap the XAD-2 resin module with threaded
glass plugs (Teflon ferrules).
o Container 3—-Front—half rinse. Rinse and brush the probe nozzle,
probe, and all glassware up to and including the front—half of the
filter with methanol, methanol/methylene chloride, and toluene;
three times each. Retain the rinse.
A- 15
-------
• Container 4——Back-half rinse. Rinse all glassware from the filter
back-half up to the XAD resin cartridge including the condenser with
methanol, methanol/methylene chloride, and toluene; retain the
rinse.
• Container 5——Condensate. After weighing, collect the first, second,
and third impinger condensates. Record the total final volume of
condensate. Rinse all impingers three times with methanol,
methanol/niethylene chloride, and toluene, and add these rinses to
the condensate container.
Cleaning glassware--All glass parts of the train including the empty XAD
sorbent tube were cleaned in MRI’s laboratory prior to use as follows:
1. Scrub and soak in hot, soapy water.
2. Hot water rinse.
3. Distilled water rinse.
4. Methanol.
5. Methanol/methylene chloride rinse.
6. Toluene rinse.
7. Bake In 100°C oven until dry.
8. Cap ends in methanol/methylene chloride rinsed aluminum foil (dull
side in).
9. Store.
Note: Chromic acid rinse to remove grease was not required because all
fittings are designed as greaseless and have never been used with grease.
Blank train—-A blank train was fully assembled in the field, heated, leak
checked, and then recovered using the same procedures as a normal sample
recovery.
1.2 HC1 Sampling Train
HC1 present in exhaust gas was collected using an HC1 sampling train.
The sampling procedure consisted of sampling a predetermined volume of stack
gas using the proposed sampling procedures specified in EPA’s “Draft Method
for the Determination of HC1 Emissions from Municipal and Hazardous Waste
Incinerators” (USEPA, QAD, July 1988), adapted for use with an M5 train.
The HC1 sampling train consisted of a heat—traced borosilicate glass
probe. A heated quartz fiber filter holder is located at the back end of the
probe. A flow control module was used to permit control and monitoring of the
gas sample. The module contained a leakless vacuum pump; a dry test meter;
A- 16
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and the appropriate valves, gauges, temperature controllers, and associated
hardware. The impingers and their contents are described below:
• The first and second GBS impingers contained 50 niL of 0.1 N H 2 S0
each. These impingers were used to collect condensate and HC1.
• The third and fourth modified impingers contained 50 niL of 0.1 N
NaOH. These Inipingers were used to absorb Cl 2 .
• The fifth modified impinger was filled with blue-indicating silica
gel.
All glass—to-glass connections were glas; and Teflon. A schematic of the
HC1 train is shown In Figure A1-3.
Calibration--The HC1 sampling equipment was calibrated, checked for
proper operation, and cleaned for use prior to arrival on-site.
As a minimum, the following equipment wa; calibrated:
1. Dry gas meter/orifice
2. Stack temperature thermocouple
3. Filter oven thermocouple
4. Thermocouple and pyrometer for gas meter
5. Probe nozzles
6. Pltot tube (by comparison to pitot 1:ube in wind tunnel.)
Copies of all calibration data will be placed in the project calibration
data file. The calibration procedures used are from the “Quality Assurance
Handbook for Air Pollution Measurement System’;: Volume 111--Stationary Source
Specific Methods,” USEPA 600/4-77-027b, and/cr from the previously referenced
EPA draft method for the determination of HC1 emissions.
All surfaces in the HC1 sampling train that came into contact with the
sample gas stream were thoroughly cleaned. The cleaning procedure is
discussed in detail below. To minimize the potential for contamination of
sampling train glassware, all glassware compiDnents were sealed with aluminum
foil prior to being packed for storage and transport. All remaining sampling
train components were cleaned and prepared in accordance with appropriate EPA
reference procedures (i.e., EPA Method 5).
All glassware, rinse bottles, and associated apparatus used for in-field
sampling and recovery were thoroughly cleaned and conditioned. All sample
containers were polyethylene.
A- 17
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/
STACK WAIL
HEATED
PROBE
HEAT
TAPE -
PURGE
*
GLASS WOOL
PLUG
THREE WAY , , /” ”
GLASS
STOPCOCK
THEFUviOMETER
o iN
H 2 S0 4
SILICA GEL
G Sampling (Flç ire IC)
Venting (Figure 113)
Purging (Figure IA)
VACUUM
GAUGE
NEEDLE
VALVE
SURGE
TANK
Figure A1—3. Schematic of the HC1 train.
-------
Cleaning glassware——All glass parts of the train were cleaned In MRI’s
laboratory prior to use as follows:
1. Scrub and soak in hot, soapy water.
2. Rinse In hot water.
3. RInse in distilled water.
4. Rinse in acetone.
5. Bake in 100°C oven until dry.
6. Cap ends in acetone—rinsed aluminum foil (dull side In).
Sample bottles-—All sample bottles required for recovery of HC1
condensate were polyethylene. The sample bottles were rinsed with distilled
water.
Sample collection——Sample collection, including leak—checking, was
conducted in accordance with the procedures described In the EPA draft proto-
col, “Draft Method for the Determination of HC1 Emissions from Municipal and
Hazardous Waste Incinerators.” Even though this draft method is directly
applied to Incineration systems, the proposed methods may be equally applied
to other Industrial combustion systems, such as the cement kiln.
Samples were collected at a single point in the duct. A sampling rate of
approximately 10 L/min was maintained through a 2—h sample period.
Sample recovery—-At the end of the test after the final leak check, the
sample train was taken to the laboratory to recover the sample. The samples
from the HC1 train were recovered as follows:
• Container 1——Condensate, HC1, and rinsate. Comb ine contents of
impingers 1 and 2. RInse these ilnpingers with water, and add the
rinsate to the combined impinger volume.
• Container 2—-Caustic, Cl 2 , and rinsate. Combine contents of
impingers 3 and 4. Rinse these irnpingers with water, and add the
rinsate to the combined impinger volume.
1.3 Dilution HC1 Train
MRI designed and built a dilution HC1 system (Fig. A1—4) to generate and
collect combustion gas samples that have been mixed with ambient air in a way
that is similar to the mixing which occurs for combustion gas leaving a
stack. EPA wanted to consider the possible formation of ammonium chloride
particles after being emitted from a wet cement plant stack. The dilution HC1
train was designed to dilute the combustion gas sample with ambient air so as
to achieve a temperature approximately 10°F above ambient. The diluted gas
was filtered through a quartz glass filter at ambient temperature and bubbled
sequentially through solutions of 0.1 N H 2 S0 and 0.1 N NaOH. The filter,
A- 19
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Orifice __J
Manometer
Stack
Gas
— Dilution Air Inlet
• M5 Style Filter Holder
Borosilicate
Glass Tube
Orifice
Ambient Air Distribution Manifold
_ ,L
/
Condensate
Drain Tube
Flexible
Teflon
Sample Line
Standard
HCI Impinger /
Train and
Console
Figure A1-4. HC1 dilution probe system.
90-55 SEV kiamm sd,em C II 1490
-------
both Impinger solutions, and rinse water were each analyzed for CV and for
ammoniuni Ion (NH .) and potassium ion (K ).
The HC1 dilution train’s experimental design may have contributed to some
loss of chlorides or other ions within the probe Itself. Dilution air was
mixed with stack gas along the length of I.he probe, with gas temperatures
dropping from about 400°F to near ambient (85°F). A condensate drain tube was
fitted to one end of the probe, but there was no visible accumulation of
condensate during any of the tests. Trace condensation may have occurred
inside the probe itself, possibly contributing to low results for the train.
Nonetheless, the train’s purpose of displaying front half/back half splits of
the three ions is still valid.
A dilution factor of approximately 20:]. was used in preliminary design
calculations, but air temperature was the target parameter of the dilution
process. Airflow volume through the samplinq system was measured using a dry
test meter. Airflow rate through the probe was measured using an orifice and
manometer (Fig. A1-5). Materials that are nonreactive to lCl were used in
construction of the sampling system. The probe was constructed of
borosilicate glass and the manifold of polyvinyl chloride and Teflon.
Stainless steel thermocouples were used to monitor the temperature gradient in
the manifold. All other parts of the system were glass or Teflon except the
quartz fiber filter.
Combustion gas was drawn through the probe into the centerline manifold
as shown in Figure A1—6. The Teflon tube al0ng the centerline acts as an air
distribution manifold with twenty 7/64-in diameter holes arranged in 5 sets of
4 through which ambient dilution air is supplied. Temperature Is monitored in
the probe, at the entrance of the probe to the manifold, at six equidistant
points downstream of the manifold inlet, at bhe outlet of the manifold to the
filter, and at the dilution air Inlet.
The manifold was 44.25 in long and made of 2-in i.d. PVC pipe.
Combustion gas at approximately 550°F and 35% moisture was observed to cool to
ambient temperature at a 20:1 dilution rate within the first 8 in of the
manifold during construction of the system. The manifold was insulated with a
blanket of refractory fiber for the first 20 in and the combustion gas cooled
to ambient at a 35:1 dilution rate at the ‘ x1t of the manifold. The glass
probe was heat-traced and insulated with refractory fiber. The probe was
maintained at approximately 550°F; the flue gas temperature.
Calibration--Before and after each test run, the system was calibrated In
the following manner:
1. The dilution inlet was plugged, and combustion gas was drawn through
the system at a H of approximately 1.5 in H 2 0.
2. The volume was measured for 2 mm, and a flow rate was calculated.
3. The dilution inlet was opened and he combustion gas flow (AH) into
the system was adjusted to that observed in step 1.
A-21
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Stack Gas
Borosilicate Glass Tube
Figure A1-5. Schematic of HC1 dilution probe.
To Inlet of
N .)
Wrap with Heat Tape
2-ft 104 Watts and Insulate
I ”
Orifice Manometer
$
55 5EV th,nm sd,em I I I4 )
-------
Detail of Dilution Air System.
— Dilution
Air Inlet
-Quartz Filter with
Teflon Covered
Metal Support Screen
All 20 Holes = 7/64” DIA
T C.
T.C.
2 5
Moisture
Collector Vent
T.C
5.5”
2” ID
TC
8 5
T.C-
11.5
TC.
145”
T.C
17.5”
Figure A1-6.
-55 5EV W.,,,,, b I I IISE
-------
4. The volume was measured, and a flow rate was calculated.
5. A dilution factor (OF) was calculated for each run by the equation:
OF - VO 1 C - VO 1 CG
— VOlCOm
where: VOlCom = volume of air through probe and dilution air combined
VO 1 CB = volume of air (combustion gas) through probe
Sample Collection-—The HC1 dilution train was operated at a single point
in the duct. Isokinetic sampling was not possible with this system. The
train was operated for a 2-h period, maintaining the H at all times roughly
at the calibrated H. Post-test calibrations of a different AH were performed
as necessary. The HC1 dilution train used the same port as the VOST, due to
availability of sample ports.
During run 1 the HC1 train was operated using midget inipingers, VOST
console, and low sampling volume (— 9 ft3). In run 2 the train used standard
MS-style impingers but again collected a low comple volume (— 7 ft3). Runs 3
through 6 and the special HC1 test all used M5—style impingers and a higher
sampling rate (52 to 54 ft total value).
Combustion gas temperature ranged from 5200 to 557°F and the moisture
ranged from 30% to 37.7%. Daily dilution factors ranged from 33:1 to 42:1
during the seven test runs. Ambient temperature ranged from 81° to 96°F, and
the final temperature of the diluted gas in the manifold ranged from 99° to
105°F.
Sample Recovery--Sample recovery was identical to the standard HC1 train.
Glassware cleaning——Glassware preparation was identical to the standard
HC1 train.
1.4 Volatile Organics Sampling Train
Volatile organics were collected from exhaust gases using a VOST. VOST
samples were collected from a single point in the duct at the stack base.
The VOST method involved collecting a 10-L exhaust gas sample at a flow
rate of approximately 0.33 L/min. The gas sample was cooled to 20°C by
passage through a water-cooled condenser, and volatiles were collected on a
pair of sorbent resin traps. Liquid condensate was collected In a catch flask
placed between the two resin traps. The first resin trap (front trap) con-
tained approximately 1.6 g of Tenax, and the second trap (back trap) contained
approximately 1 g each of Tenax and petroleum-based charcoal, 2:1 by volume.
A diagram of the VOST component arrangement is presented in
Figure A1-7. The sample goes from the probe to a valve train, a water—cooled
A-24
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Sample Charcoal
Valve Tube Valve
r Teflon Tubing
N . )
(TI
Fittings A, B, C, and D
are Viton 0-ringed
Nickel Plated Fittings
——
Purge
Valve
Stock
Gas In
Charcoal
Filter
Latex Tubing
Silica Gel
Te flax / Charcoal
Trap
Catch Flask
Sampling
Console
TcL1
Remote Ice Both
with Submersible
Pump
Figure A1-7. Volatile organic sampling train (yOST).
-------
glass condenser, a sorbent cartridge containing Tenax (1.6 g), an empty catch
flask for condensate removal, a second water-cooled glass condenser, a second
sorbent cartridge containing Tenax and petroleum-based charcoal (2:1 by
volume, approximately 1 g of each in separate layers), a silica gel drying
tube, a rotameter, a sampling pump, and a dry gas meter.
- The gas pressure during sampling and for leak-checking was monitored by
pressure gauges which are in line with and downstream of the silica gel drying
tube.
The probe is constructed of borosilicate glass or Teflon in a stainless
steel outer sheath. The temperature of the probe was maintained above 135°C
but low enough to ensure a resin temperature of 20°C.
An isolation valve was used to isolate the VOST apparatus from the sample
probe. The isolation valve consisted of a greaseless stopcock and sliding
Teflon plug. The charcoal tube valve was also used to direct a hydrocarbon-
free gas (charcoal-filtered air) to the inlet of the sample train. This gas
was used to prevent contamination during leak—check procedures.
The condensers were of sufficient capacity to cool the gas stream to 20°C
or less prior to passage through the first sorbent cartridge.
The sorbent cartridges for the VOST were of the inside-inside (I/I) con-
figuration in which only a single glass tube was used for each of the two
tubes. The second sorbent cartridge was placed in the sample train so that
the sample gas stream passed through the Tenax layer first and then through
the charcoal layer. The sorbent cartridges were glass tubes with approximate
dimensions of 10 cm (long) by 1.6 cm i.d. The resin was held in place by
Teflon—coated stainless steel screens and clips at each end of the resin
layer. Threaded end caps were placed on the sorbent cartridges after packing
with sorbent to protect the sorbent from contamination during storage and
transport.
The metering system for VOST consisted of vacuum gauges, a leak-free
pump, a rotameter for monitoring the gas flow rate, a dry gas meter (low
volume) with 2% accuracy at the required sampling rate and related valves and
equipment. All sample transfer lines used with the VOST up to and including
the second resin cartridge were Teflon or glass with connecting fittings that
were capable of forming leak—free, vacuum-tight connections without the use of
sealing grease.
Calibration--All VOST equipment was calibrated, checked for proper
operation, and cleaned for use prior to arrival on-site. The gas meter and
condenser thermocouple were calibrated before and after the test.
The gas meter was calibrated against a wet test meter. The thermocouple
was calibrated against a mercury-in—glass thermometer. The calibration pro-
cedures are presented In the QAP.
Glassware cleaning-—All glass parts of the VOST train were cleaned as
follows:
A- 26
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• Washed with Alconox and hot water.
• Rinsed with tap water.
• Rinsed with distilled water.
• Oven—dried at 150°C for 2 h.
• Capped with aluminum foil or Teflon caps until used.
Tenax preparation--The sorbent tube cartridges were packed with Tenax and
conditioned by flowing, organic—free nitrogen (30 niL/mm) through the resin
while heating to 175°C for at least 4 h.
During the thermal conditioning, the Tenax cartridges were installed in a
specially designed manifold which permits the nitrogen purge from the traps to
be individually monitored by an FLU. The conditioning was continued until the
FLU response indicates the traps are clean (less than 5 ppb total hydrocarbon
as propane). If after 24 h of purging the trap was still contaminated, It was
discarded.
Charcoal (SKC petroleum base or eguivaler —-Procedures for recondition-
ing charcoal are the same as those described for Tenax above.
Sample cartridges——”Primary ” VOST cartridges were packed with 1.6 to
1.8 g of prepared Tenax, and “secondary” cartridges were packed with
approximately 1 g each of prepared Tenax and prepared petroleum-based charcoal
(SKC Lot 104 or equivalent), 2:1 by volume. The packed cartridges were condi-
tioned as described above.
After the tubes were conditioned, the tubes were capped and placed into a
steel can which was sealed for shipment. The can contained a small amount of
charcoal for shipment. During each test each tube was marked directly with an
identifier.
VOST sample collection——Sample cQllection was conducted in accordance
with procedures described in the USEPA document SW-846, Method 0030, except as
noted below. Samples were collected from each exhaust duct at a single sample
point for three 40—mm sample periods during each test condition.
The following are exceptions and/or additions to the procedures in the
above-referenced document.
1. After collection of the 20-L sample, the two sorbent cartridges were
removed from the train, capped at the ends, and placed into the metal trans-
port can which contains charcoal. The cans, were stored and transported in
insulated containers packed with ice to maintain temperature of the tubes
below 20°C at all times.
2. Field blanks, trip blanks, and other conditioned (clean) sorbent
tubes were stored and transported as described above for the sample tubes.
A-27
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The volatile organic sample train was assembled as shown in
Figure A1-7. A leak check of the train was made at 250 nimHg with the sample
valve at the inlet from the probe to the condenser closed. After all leak
checks, the vacuum was released by admitting charcoal—filtered air through the
charcoal-tube valve.
The probe was next purged with stack gas by drawing stack gas through the
probe via the purge valve with a pump. After this purge of the probe, the
sample was collected following these steps:
• Record the dry gas meter reading.
• Position the valve train to connect the condenser with the probe.
• Turn on the pump and open the coarse metering valve.
• Operate the train at the sampling rate of 0.33 L/min for the next
30 mm.
• Collect readings as required by the VOST data sheet each 5 mm
throughout the run.
• Ensure the sampling rate remains constant throughout the run.
• Ensure the temperature of the gas entering the first sample tube
remains below 20°C throughout the run.
• Ensure the probe remains above 135°C throughout the run.
• At the end of the sampling period, turn off the pump and close the
sampling valve.
After the sample was collected, the final meter volume was recorded and a
final leak check done at the highest vacuum recorded during the sampling
period. The cartridges just used were removed and replaced with fresh
cartridges. No cleaning of the condenser or other VOST equipment was required
between subsamples. A new pair of traps was installed in the system, and
sampling was continued as described above.
One set of field blanks was obtained by removing the end caps from a pair
of traps and exposing them to the atmosphere while placing a pair of sample
traps into the VOST train and again while removing the sample traps from the
VOST train.
A set of trip blanks were retained for analysis from the set of tubes
used during the test.
Condensate collected In the catch flask was transferred to a VOA
(volatile organic analysis vial) following each run; or as traps were changed
out during the run as necessary if a significant volume was collected.
A-28
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VOST sample recovery--The VOST traps and VOA vials used in the sample
train were immediately capped. A label was placed on the end cap or VOA
bottle to indicate the sample run number for ease in identification. Each
trap tube was permanently marked with a unique identification number. This
identification number was recorded on the d ta form and sample traceability
form to ensure proper sample identification. This trap number was used as the
primary sample Identification number.
The sealed trap was replaced in the trap storage/transport can and
labeled V0A bottle appropriately wrapped. All samples to be analyzed
volatile organics were kept in a cooler with ice during the duration of
test and during storage on-site.
V0A vials used to collect train condensate were capped, stored, and
shipped at 4°C. Partially full vials were weighed and topped off with
deionized water and weighed again.
1.5 Field GC
The field CC was utilized to identify Cl through C17 carbon fractions.
CC samples were split directly off
sampling lines under positive pressure.
checked as a unit.
The standard were nominal 100-ppm, 50-ppm
cylinders. All results were reported as
equivalent. A separate analysis of a mixture
analyzed to establish retention times for these
The CC conditions were as follows:
Analyzer:
Column:
Temperature program:
Detector temperature:
Carrier gas:
Sample loops:
Valve temperature:
Two of the three propane standard concentrations were analyzed each
day. The lower of the two concentration propane standards was analyzed prior
to each test run to check instrument linearity. The higher propane standard
was analyzed prior to and after each test run to generate an average response
factor. The average response factors were used to calculate the Cl-C7 and
C7—C17 carbon fractions.
the
for
the
the hot HC pump exit, placing the CC
The entire sampling system was leak-
and 20-ppm propane EPA
parts per million of
containing C7 and C17
protocol
propane
will be
compounds.
Shimadzu CC with dual FID
30-m DB—1, 5.0-NM megabore
100°C to 250°C at 20°C/mm, hold for
6 miri at 250°C.
275°C
He, 7 to 10 mLJmin
Approximately I mL
150°C
A-29
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1.6 Integrated Gas Bag Sampling for Volatile Organics
A Tedlar Bag was used during each test run to collect an Integrated bag
sample for C 1 -C 2 analysis. The samples were collected from an available exit
on the CEM manifold. Various gauge needles were used to restrict sample flow
to within a 30 to 70 mL/mln range. A 3- to 15-L bag sample was collected over
the duration of each test period. A blank bag was filled with prepurifled
nitrogen and placed near the sampling location. The blank bag was analyzed
along with and in the same manner as the sample bags. When sampling was
completed, the blank and sample bags were analyzed on—site within 24 hr. All
sample bags were leak-checked in the laboratory prior to shipment to the test
site.
Tedlar bag samples and blanks were analyzed by GC—FID within 24 h of
sample collection. The Injection volume for the gas samples was 0.5 mL. The
GC conditions for C 1 -C 2 analysis (bag fraction) were as follows:
Analyzer: FID
Column: 30-m GS—Q megabore
Temperature program: 40°C to 120°C at 6°C/mm
Detector temperature: 275°C
Injector temperature: 100°C
Carrier gas: Helium at 7 to 10 mL/min
Make-up gas: Helium at 20 mL/min
Tedlar bags were used for the collection of the integrated sample. They
were 15-L bags and are used only once. Before use, the bags were purged
three times with prepurified nitrogen. Blank bags were always employed
for each run to measure any contamination that may have occurred
1.7 Continuous Emission Monitoring
Samples were collected at each exhaust duct to measure CO, C0 2 , 02, and
hot and cold HC, and HC1.
1.7.1 HC Measurement—-
HC emissions were measured using EPA MM25A sampling systems, equipped
with FIDs. This HC measurement was compared to an organic mass measurement
(subsequently discussed).
Heated and unheated HC emission concentrations were measured using the
MM25A systems. This method essentially measured hydrocarbons expressed in
terms of propane.
To measure heated HC concentrations, the following changes were made to
the MM25A system:
• The entire sample system from probe to detector was heated to
> 300°F (150°C).
• A Beckman 402 HC analyzer or equivalent was used.
A- 30
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• Propane was used as the calibration gas.
• EPA protocol 1 cylinder standards of 5, 10, 20, 50, and 100 ppm
propane in nitrogen were available; the three cylinders that best
covered the sample concentration were used.
In measuring unheated HC concentrations,, the following changes were made
to the M25A system:
• An ice—cooled water knockout trap was used to remove condensibles.
• An unheated Teflon sample line was used to conduct the sample
through a stainless steel pump to the FID.
• Propane was used as the calibration gas.
• EPA protocol 1 cylinder standards of 5, 10, 20, 50, and 100 ppm
propane In nitrogen were available; the three cylinders which best
covered the native sample concentration were used.
Figure A1—8 Illustrates the general con1 iguration of the HC gas sampling
system. At each sample point (i.e., exhaust duct), combustion gas was sampled
using a single probe with a sintered metal filter. Immediately after
extraction, the gas sample was split Into “heated” and “unheated” sample
fractions. The heated sample fraction was transferred to a hot HC analyzer
via a heated sample line. The sample line, along with in-line tees and
valves, were maintained at over 300°F (150°C). Pumps were used to maintain
constant purging of all sampling lines.
The unheated sample fraction was passed through a condensate trap (i.e.,
a modified GBS impinger placed In an ice bach) which was located adjacent to
the sample port. Using a Teflon sample line, the sample was then transferred
to the FID, carbon monoxide, carbon dioxide, and oxygen analyzers.
During the test the condensate trap was operated at “contact” and
“noncontact” conditions. Contact conditions were characterized by the sample
gas bubbling through collected condensatE. Noncontact conditions were
achieved early in the day’s test and were characterized by the sample gas
passing through the condensate trap without contact with collected condensate.
The HC monitors used Included a Beckman 400 series model and a comparable
MRI in-house designed model. A data logger was used to record all necessary
information. The monitors were spanned and zeroed prior to and/or immediately
following each run with 99.26 ppm propane, NBS—traceable EPA protocol 1 gas,
and prepurified nitrogen. A linearity check was conducted In the field prior
to initiating the first test run using 49.09 ppm propane and 20.35 ppm propane
NBS—traceable EPA protocol 1 gases. Monitor response times also were checked
(90% of full scale).
A- 31
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Es? E I
3’
en .v e— —
Figure Al—B. HC and CEM equipment layout associated with each exit duct.
-------
1.7.2 Carbon Monoxide, Carbon Dioxide, and Oxygen Measurement--
Figure Al-B is a schematic of the CEM ;ystem. As illustrated, CEM sam-
ples were split from the cold HC MM25A saniple line. In the MM25A system,
Immediately after extraction, the gas sample was passed through a condensate
trap. The sample was then transferred via TFE Teflon sample line and split
for C0 2 , 02, CC, and cold HC analysis. CO; was independently monitored and
used to volume-correct the CO reading to ccount for the CO 2 removed. A
Horiba Model PIR-2000S nondispersive infrared (NOIR) analyzer was used to
measure CO 2 . 02 was also independently monitored and was used to correct the
Co reading to 7% oxygen concentrations. A Horiba PMA-200 paramagnetic sensor
and a Teledyne Model 320AX polarographic sensor were used to measure 02. Each
manifold maintained a constant purge of the two cold IFE sample lines.
Total CO concentration was determined using Horiba Model PIR-2000L
NDIRs. After a CO sample was split from the cold HC MM25A sample line, it
passed through an ascarite/silica gel cartridge containing approximately 200 g
of ascarite and 20 g of silica gel. The ascatrite trap removes carbon dioxide,
which Is an interference to the CO monitor,, and the silica gel removes the
last traces of moisture prior to the monitor. The sample fraction was then
pumped to the NDIR analyzer.
Zero drift was determined by checking the zero calibration before and
after each run and comparing the two. Calibration drift was determined by
checking the span gas calibration before and after a given period of time
(usually the same time as the zero drift w s done). The response time was
determined by adding a calibration gas while the instrument was at the zero
calibration in the end of the probe and determining the length of time for the
instrument to reach 90% of the correspondling span value. The calibration
error (usually referred to as the linearity check) was done by zeroing and
spanning the instrument and then adding a midlevel calibration gas and
comparing the instrument value with the real gas value. Zero and calibration
drift must be less than ±3% of the span value, while the calibration error
must be less than ±5% of the calibration gas value.
Possible bias from organics retained on the sampling lines was also
checked by Introducing zero gas at the sample probe before and after each run
(HC only). Also after each run, each NC monitor was switched to obtain
ambient air readings from just outside the trailer.
The performance checks for the analyzers are summarized below:
Zero drift: 3% of span
Span drift: 3% of span
Linearity checks: 5% of cylinder gas value
Leak checks: < 4% of normal flow, before and after each run
Nominal gas concentrations:
Linearity
HC—-span 100 ppm propane 50, 20 ppm
C0——800 ppm 400, 200 ppm
C0 2 —-14% 7%
02 ”14% 7%
A-33
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1.7.3 HC1 monitoring-—
HC1 continuous monitoring was performed by a Thermo—electron Model 15 gas
filter correlation Infrared unit. The Instrument used its own heated Teflon
sample line and conditioning system. Stack gas was dried using a Perniapure
dryer.
The system was leak-checked before each run. The monitor was zeroed
using prepurif led nitrogen and spanned using the lowest calibration gas
available, as historical data from the facility showed quite low levels of HC1
present. Operation of the monitor was checked hourly and fed span gases to
verify response as necessary. Following each run, a final zero and span were
performed and the monitor was purged for at least 30 mm with nitrogen before
shutting down. Zero drift, span drift, and response times were measured
identically to the CO, C0 2 , and 02 monitors (Section 1.7.2). A linearity
check was performed using the mid—level calibration gas the first day only.
The system was within 10% agreement of the gas true value.
1.8 Orsat
An integrated multipoint stack gas sample was taken during each test run
and subsequently analyzed for percentage oxygen (02) and carbon dioxide (C0 2 )
according to EPA Reference Method 3 (40 CFR 60). The sample was taken from a
connection at the exhaust from the Method 0010 sampling console. This
provided a sample from which particulate and moisture have already been
removed in the Method 0010 samplIng train, and automatically provided a
multipoint Integrated sample.
The integrated sample was taken over the entire 2—hr sampling period,
simultaneously with the Method 0010 sampling.
The sampling systems leak checks required in Method 3 were conducted
prior to sampling. These include:
1. Leak check of bags.
2. SamplIng system leak check.
All bags were leak checked in the laboratory prior to being shipped to the
field. The bag sample collected was analyzed within 4 hours using an Orsat
analyzer.
2.0 FEED STREAM SAMPLING
The lime slurry liquid waste was sampled once every 30 nun during each
test run. Grab samples of 100 niL were coniposited into a single sample for
each run. Upon return to MRI, samples were filtered Into their solid and
water fractions and sent to separate labs for TOC analysis.
Sample containers for lime slurry samples were purchased from 1-Chem.
All such glassware was certified precleaned by 1-Chem for organics sampling
usage. All bottles used for samples were made of polyethylene or glass.
A- 34
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Powdered waste was sampled from each feed truck as it is unloaded to the
secured containment hopper. The facility provided these samples to MRI.
Precleaned sample containers were purchased from 1—Chem to contain these
samples.
Liquid waste samples were collected every 30 mInutes along the line which
feeds directly to the kiln. The collection point was just downstream of the
feed pump. Grab samples of 100 mL were coniposited into a single sample for
each run. All glassware used was purcha ed precleaned and certified by
1—Chem.
A- 35
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APPENDIX A—2
SAMPLE HANDLING AND ANALYSIS
A- 37
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APPENDIX A—2
SAMPLE HANDLING AND ANALYSIS
The following sections briefly describe the procedures employed during
the analysis of the samples collected during this project. These procedures
cover the analysis of all emission samples, lime slurry samples, and waste
samples.
1.0 METHOD 0010 SAMPLES
The following sections summarize the procedures utilized in analyzing
Method 0010 samples for estimates of semivolatile compounds, quantitation of
dioxins and furans, and gravimetric analysis to combine with GC/FID data for
total organic mass.
1.1 Sample Handling
All samples were sealed, labeled, and stored in insulated containers in
the field and during transport. All samples that were to undergo organic
analysis were stored on ice in the field and during transport. Upon receipt
in the laboratory the samples were removed from the insulated containers and
were placed In cold storage (< 4°C). Each of the samples included the
following fractions:
1. Filter
2. Sorbent trap
3. Front—half organic rinse
4. Back-half organic rinse
5. Condensate (first and second impinger contents and rinse)
1.2 Sample Analysis
Figure A2-1 presents a schematic of the analytical scheme of the samples
for semivolatiles, PCDDs/PCDF5, and gravimetric analyses. Prior to
extraction, each component was spiked with PCDD/PCDF Internal standards. The
PCDD/PCDF internal standards are listed in Table A2-1. The semivolatile
surrogates Included 2,4,6—tribromophenol and D10-pyrene.
Each train component was triple-extracted using methylene chloride,
methyl t—butyl ether, and toluene. The so vent fractions generated through
the extraction and concentration process were then ultimately combined,
concentrated to a 10—mL final volume, and sp1 it into analytical aliquots.
A-39
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Front Half. Back Half, and Condensate
Spike Some Runs with Surrogate 1
Extract with MeCI 2 , pH Neutral
• Combine extract from each component extraction
including Front 1/2, Back 1/2, and condensate.
1 Each component is extracted separately
I - - - using an identical procedure.
Filter XAD
Spike Some
Runs with Surrogate
Extract
with MeCI 2 ]
Spike Some Runs
with Surrogate
J Extract with
MeCI 2
Extract with Methyl-t-Butyl ether Extract with Methyl-t-Butyl ether
I I
Extract with Toluene Extract with Toluene
Change pH to 12
Extract with MeCI 2
Change pH to 2
Extract with MeCI 2
Change pH to 7
Combine and
Concentrate *
Concentrate to 10 ml Final Volume
Extract with Methyl-t-Butyl ether
Sample Split
- _Extract_with Toluene
I I
2.5 ml Concentrate
Cleaned Up and
Analyzed by 8290 for
Total and Specific
PCD 0/PC OF
2 5 ml Concentrate
to 1 ml for SVOC
Screen
5m 1
G ravimetric
Analysis
SEW ki .n .,, fi O6O89
Figure A2—1. Sample analysis flow.
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TABLE A2—1. SEMIVOLATILE COMPOUNDS TARGETED IN GC/MS SCREEN
phthal ate
1 N-Nitrosodimethylaniline
2 Bls(2-chloroethyl) ether
3 Phenol
4 2-Chiorophenol
5 N-Nitroso-di-n-propylamine
6 1,3—Dlchlorobenzene
7 1,4—Dichlorobenzene
8 1,2—Dichlorobenzene
9 Bls(2-chloroisopropyl) ether
10 Hexachloroethane
11 Nltrobenzene
12 Isophrone
13 2-Nitrophenol
14 2,4—Dirnethyiphenol
15 BIs(2-chloroethoxy)methane
16 2,4-Dichiorophenol
17 1,2,4—Trichlorobenzene
18 Naphthalene
19 Hexachloro-1,3-butadlene
20 4-Chloro—3-niethylphenol
21 Hexachlorocyclopentadiene
22 2,4,6-Trichiorophenol
23 2,4,5-Trichiorophenol
24 2-Chloronaphthalene
25 2,6—Dlnitrotoluene
26 Dlmethyl phthalate
27 Acenaphthylene
28 Acenaphthene
29 2,4-Dlnltrophenol
30 Olbenzofuran
31 4-Nitrophenol
32 2,4—Dinitrotoluene
33 2-Methylnaphthalene
34 Benzyl alcohol
35 Azobenzene
36 Fluorene
37 4-Chiorophenyl phenyl ether
38 Diethyl phthalate
39 4,6—Dinltro—2-methylphenol
40 Benzoic acid
41 N-Nitrosodiphenylamlne
42 4-Bromophenyl phenyl ether
43 Hexachlorobenzene
44 2-Methyiphenol
45 4-Methyiphenol
46 Pentachiorophenol
47 Phenanthrene
48 Anthracene
49 Di-n-butyl phthalate
50 Aniline
51 Fluoranthene
52 Benzidine
53 Pyrene
54 Benzyl butyl
55 Chrysene
56 3,3’—Dlchlorobenzidine
57 Benz [ a lanthracene
58 Bis(2—ethylhexyl) phthalate
59 Di-n-octyl phthalate
60 Benzo [ bjfluoranthene
61 Benzo(k]fluoranthene
62 Benzo [ aJpyrene
63 Diberiz [ a,h]anthracene
64 Benzo [ g,h, Iperylene
65 Indenol 1,2,3-c,d]pyrene
66 4-Chioroaniline
67 2-Nitroanlline
68 3-Nitroaniline
69 4-Nitroaniline
A-41
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The Method 0010 samples from test runs 1, 3, and 4 were split for
semivolatile organics analysis, PCOD/PCDF determination, and gravimetric
analysis. Samples from the blank train and test runs 2 and 5 were split for
semivolatile organics analysis and gravimetric analysis.
A 2.5—mL to 5.O—mL aliquot was separated for the seniivolatile organic
screen. A 2.5-mL aliquot was separated for PCDD/PCDF determination, and a
5.0-mL aliquot was separated for gravimetric analysis. Detailed Standard
Operating Procedures are included in Appendix A-4.
1.2.1 Sample Preparation and Analysis for Semivolatile Organics—-
The semivolatile (SV) extraction procedures for rinses and condensates
were adopted from SW-846, Methods 0010 and 3510 (separatory funnel
extraction). The SV extraction procedures for the XAD and filter components
were adopted from SW—846, Methods 0010 and 3540 (Soxhlet extraction). The
extracts did not undergo column cleanup, because an organic screen was
required.
SV analysis was conducted following SW-846, Method 8270, guidelines.
This method is a capillary column full-scan GC/MS method applicable to a
variety of semivolatile compounds. Table A2—2 lists the compounds screened in
the SV analysis. A 5-point calibration curve using standards containing the
target compounds in the EPA Contract Laboratory Program (CLP, 1990 Statement
of Work) was analyzed. Continuing calibration checks were made by analyzing
daily mid-level standard verification (±30%). Quantification was accomplished
by the internal standard method, using a relative response factor from the
calibration curve.
1.2.2 Sample Preparation and Analysis for PCDD/PCOFs--
The final 2.5-niL aliquot for PCDD/PCOF analysis was solvent-exchanged to
hexane and cleaned up according to SW-846 Method 8280 and analyzed for tetra
through octa PCDD and PCDF congener groups. Samples were analyzed by high
resolution gas chromatography mass spectrometry (HRGC/MS), using SW-846 Draft
Method 8290. A 60-rn x 0.25-rn 06-5 fused silica capillary column (FSCC) was
utilized.
The levels of dioxins and furans were calculated by comparison of the
response samples to calibration standards (listed in Table A2—2). Isomer-
specific quantitation was not completed; total concentrations of each congener
group were determined. Congeners were tabulated (by comparison to the
appropriate response factor determined from the calibration curve. Table A2—2
lists the analytes, standard compounds, and surrogates used in PCDD/PCDF
analysis.
1.2.3 Sample Preparation for Gravimetric Analysis—-
Semivolatile and nonvolatile sample extraction were performed following
the procedure given In “POHCs and PICs Screening Protocol” (Southern Research
Institute), Section III.C. As mentioned in Section 5.1, all solvent rinses,
filter, and XAD were combined and extracted with methylene chloride, again
with methyl t—butyl ether, and a third time with toluene.
A-42
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TABLE A2-2. LIST OF ANALYTES, ST! NDARDS, AND SURROGATES
FOR DIOXIN/FURAN ANALYSES
Analyte
Compounds in
calibration
standard
Internal sl.andard
Recovery standardb
Tetra—COD
2,3,7,8—TCDD
‘ C 1 2 —2,3,7,8—TCDD
‘ C 1 2 —1,2,3,4—TCDD
Tetra—COF
2,3,7,8—TCDF
‘ C 1 2 —2,3,7,8—1CDF
Penta-CDD
1,2,3,7,8-PCDD
Penta—CDF
1,2,3,7,8-PCDF
2,3,4,7,8—PCDF
‘ C 1 2 —1,2,3,7, —PCDD
‘ C 1 2 —1,2,3,7,E:—PCDF
Hexa—CDD
Hexa—CDF
1,2,3,4,8,9—HxCDD
1,2,3,4,7,8—HxCDD
1,2,3,6,7,8—HxCDD
1,2,3,7,8,9 —HxCDF
2,3,4,6,7,8—HxCDF
1, 2,3, 6,7 , 8—HxCDF
1, 2,3, 4,7, 8—HxCDF
‘ C 12 —1,2,3,6,7,8—HxCDD
‘ C 1 2 —1,2,3,5,7,8—HxCDF
‘ 3 C 12 —1,2,3,6,7,8—HxCDD
Flepta-CDD
1,2,3,4,6,7,8-HpCDD
Hepta—CDF
1,2,3,4,6,7,8—HpCDF
1,2,3,4,7,8,9—HpCDF
‘ C 1 2 —1,2,3,4, ,7,8—HpCDO
‘ C 12 —1,2,3,4, ,7,8—HpCDF
OCDD
Octa-CDO
‘ C 12 -OCDD
OCOF
Octa—CDF
a Added to sample prior to extraction and used for quantitation of dioxins/furans
in sample.
b Added to extract at time of injection into GCj’MS.
A-43
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The methylene chloride, t—butyl methyl ether, and toluene extracts from
the train components were combined and gravimetrically analyzed without
deviation in accordance with the procedure In Section III.F. of “POHCs and
PICs Screening Protocol.” The precision and accuracy of duplicate analyses
were based on two criteria:
• Duplicate sample weights were to be within ±20% of the average
sample weight.
• The difference between replicate weights were to be < 0.1 mg (the
required extent of accuracy).
A sample could fail the first test but still be within the limits of
required accuracy; hence a sample was reanalyzed only if it did not pass the
second test.
The respective method blank was subtracted from each sample. The
remainder was then multiplied by a numerical factor to obtain the total pg per
sample. Dividing by the dry standard sample volume allowed for pg/L
calculation based on the air sampled. To obtain the ppm propane equivalent,
it was assumed that half of the sample molecular weight had no FID response;
thus ppm propane was calculated as follows:
(pg of sample/L of air sampled).(0.5)•(24.1 pL per pmol of gas/44 p propane
per pmol propane)
2.0 METHOD 0030 SAMPLES
Volatile compounds present in stack gases were collected on Tenax and
Tenax/charcoal sorbent cartridges using a volatile organic sampling train
(yOST). Methods 5040 and 8240 in SW—846, third edition, describe in detail
procedural steps required to desorb VOST cartridges and analyze the effluent
gas stream for volatile organic compounds. Modifications to these methods are
contained in Table A2—3. An SOP is also provided in Appendix A-3 that
basically follows Methods 5040 and 8240, but only addresses the quantitation
of one each POHC, surrogate, and internal standard. The VOST samples were
analyzed for the compounds listed In Table A2—4. Identification of target
analytes in the VOST samples was performed using the Target Compound Analysis
(TCA) procedure. The ICA program uses experimentally determined retention
times and response factors to locate and quantitate any target analyte.
The contents of the sorbent cartridges were spiked with an internal stan-
dard and thermally desorbed for approximately 10 mm at 180°C with organic—
free nitrogen or helium gas (at a flow rate of 40 mL/min), bubbled through a
tower to impinger water desorbed from the cartridges. Target analytes were
trapped on an analytical adsorbent trap. After the 10—mm desorption, the
analytical adsorbent trap was rapidly heated to 180°C with the carrier gas
flow reversed. Volatile organic compounds were desorbed from the analytical
trap and vented directly to the gas chromatograph. The VOCs were separated by
temperature-programmed gas chromatography and detected by low-resolution mass
spectrometry. Concentrations of the POHC were calculated using the internal
standard technique. PlC compounds were quantitated using a single—point
calibration and by internal standard method using RRFs equal to 1.0.
A-44
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TABLE A2-3. MODIFICATIONS FROM SW-846 METHODS
11.1 METHOD 8240 “GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE
ORGANICS”
METHOD 8240
SECTION NO. MODIFICATION
4.12.3 100 ng of BFB is injected rather than 50 ng. This
5.5 gives better instrument response on the lower
7.2.2 intensity ions.
7.3.1
5.1.3 Purlties < 100% (or 99+%) are corrected.
5.3 Concentrations of stock solutions will vary
5.4 according to analysis needs. Usually, surrogate
5.7 and RIS solutions are such that 100 ng per analysis
is achieved. RIS and surrogal.es are prepared as a
mix for yOST, water samples, and system blanks.
A three point calibration curve is acceptable.
5.6 Calibration standards are prepared in methanol rather
than reagent water and they are used until signs of
degradation become evident.
5.8 standard solutions are stored In clear vials and placed
In a closed container to protEct from light.
6.1 New bottles and vials are cleaned according to
Introductory Chapter, Section 4.1.2. Sample bottles
and vials are not reused, thea’ are decontaminated with
methanol and disposed of. Reactivials and volumetric
flasks are decontaminated aftEr use, then cleaned as
in Section 4.1.2.
7.2.5 CalIbration standards are prepared as a mix which
Includes analytes, surrogates, and RIS. This standard is
spiked directly into the glass syringe containing 5.0 mL
VOA water, mixed, and added tc the purge tower.
7.2.9 The GC/MS data system (INCOS) uses n rather than n-i for
%RSD calculations. If a %RSD falls within 3% of the
cut—off value, then this %RSD is recalculated manually
using n—i to achieve a more ac:curate value.
7.4.1 Water samples are not pre-screened as they generally
contain a very low concentration of analytes.
7.4.1.5 Purge gas is nitrogen at 40 mI/mm. Carrier gas is helium
at 30 cm/sec.
A-45
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TABLE A2-3 (continued)
7.4.1.7.3 Only one aliquot for analysis is taken from any given VOA
vial. If replicates are required, then these aliquots
are taken from individual VOA vials. If dilutions are
necessary, then an aliquot is taken from a fresh VOA vial.
7.5.2 Quantitation for PICs and unknowns will be by the internal
standard method using RRFs of 1.000 (or historical) rather
than RRFs generated by standard injections.
8.5.1 ConcentratIons of analytes will vary depending on
8.5.2 the analysis needs.
A-46
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TABLE A2-4. VOLATILE SCREEN TARGET LIST
1 Acetone
2 Acrolein
3 Acrylonitrile
4 Benzene
5 Bromod lchloromethane
6 Bromoforrn
7 Carbon tetrachioride
8 Chloroform
9 Chlorobenzene
10 Dibromochloromethane
11 1,1-Oichloroethane
12 1,2-Oichloroethane
13 1,1-Cichloroethene
14 t—1,2—Dichloroeth!ne
15 1,2-Dichloropropane
16 t— 1,3-01 ch 1 oropropene
17 Diethyl ether
18 1,4-Dioxane
19 Ethylbenzene
20 Methylene chloride
21 Methyl ethyl ketone
22 1,1 , 2, 2-Tetrach 1 oroethane
23 Tetrachioroethene
24 Toluene
25 1,1,1—Trichloroethane
26 1,1,2-Trichioroethane
27 Trichioroethene
A- .47
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3.0 HC1 TRAIN SAMPLES
The contents of the condensate impingers from the HC1 and HC1 dilution
trains were analyzed for HC1 using ion chromatography, ASTM Method 04327—84.
Concentrations as low as 0.1 mg/L can be determined.
In the analysis, a filtered aliquot of the sample is injected into an ion
chromatograph. The sample is pumped through three different ion exchange
columns and into a conductivity detector. The first two columns, a precolumn
and separator column, are packed with a low-capacity anion exchanger. Ions
are separated based on their affinity for the exchange sites of the resin.
The last column is a suppressor column that contains cation exchange resin in
the hydrogen form. The suppressor column reduces the background conductivity
of the eluent to a low or negligible level and converts the anions in the
sample to their corresponding acids. The separated anions in their acid form
are measured using an electrical-conductivity cell. Anions are identified
based on their retention times compared to known standards. Quantitation is
accomplished by measuring the peak height or area and comparing it to a
calibration curve generated from known standards.
The HC1 and HC1 dilution samples were also analyzed for potassium using
inductively coupled plasma-atomic emissions spectrometry (ICP-AES). The
samples were analyzed for ammonium using gas chromatograph/mass spectrometry—
selective ion measurement (GC/MS-SIM). Galbraith Laboratories, Knoxville, TN
performed these analyses.
4.0 LIME SLURRY AND WASTE FEED SAMPLE HANDLING
Lime slurry samples were split in MRI’s labs into their solid and water
fractions. Solids were dried and sent to the Geochemical and Environmental
Research Group (GERG), College Station, TX for TOC analysis using a LECO
furnace and GERG SOP-8907. Water fractions were analyzed for TOC by Galbraith
Laboratories, Knoxville, TN, using EPA Method 415.1.
Powdered and liquid waste samples were analyzed for Higher Heating Value
(HHV) and chlorine content by Gaibraith Labs, using ASTM methods D2015—77 and
D808-81/D4327-84/E442-81 respectively.
A- 48
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APPENDIX A-3
VOLATILES ANALYTICAL METHODS
A- 49
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The analytical procedures used by MRI for volatile organic analysis are
based on EPA SW—846 Method 5040, “Protocol for Analysis of Sorbent Cartridges
from Volatile Organic Sampling Train” and Method 8240, “Gas Chromatography!
Mass Spectrometry for Volatile Organics.” Any deviations from these SW—846
methods normally used by MRI are noted in the procedures.
A- 51
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1.0 GLASSWARE PREPARATION
1.1 FIELD SAMPLING
1.1.1 All containers for field sampling are glass and have Teflon—
lined caps or Teflon—lined septa. Samples for volatile organic analysis (VOA)
are protected from light as much as possible to avoid degradation of halo-
genated compounds. Amber bottles are useful for this purpose. If amber bot-
tles are not used, the sample bottle can be wrapped with foil or stored in a
container to protect from light.
1.1.2 When possible, 40-niL screw cap septum vials (VOA vials) that
have been manufacturer precleaned according to EPA protocol are used for the
collection of water and waste samples. However, these vials are currently
available in clear glass only. If contract specifications require amber VOA
vials, these must be prepared according to the procedure in Section 1.2.
1.1.3 Other containers may be required for VOA sampling and these
will be specified by the field programs crew chief prior to each burn. If
other containers are required, they are also be prepared according to the pro-
cedure in Section 1.2.
1.1.4 Water field blanks are prepared for each field sampling trip
by adding VOA water (see Section 2.1 for prep of VOA water) to clean VOA vials
and sending them to the field with the other containers. These field blanks
demonstrate that no contamination of samples has occurred due to ambient con-
ditions at the site or during shipment.
1.2 GLASSWARE CLEANING
1.2.1 Preparation of glassware to be used in the collection or prep-
aration of samples for volatile organic analysis (VOA) is performed in a
laboratory free from organic solvents other than methanol.
1.2.2 All glassware (amber VOA vials, sampling bottles, compositing
bottles, volumetric flasks, etc.) is prepared according to the following pro-
cedure:
1.2.2.1 Wash in hot soapy water using Micro (or equivalent) and a
clean brush.
1.2.2.2 RInse thoroughly in tap water (3 x), deionized water (3 x),
and distilled—in—glass methanol (B&J or equivalent).
1.2.2.3 Any glassware that does not appear to be clean, i.e., does
not “sheet” when rinsed with water or methanol, is cleaned by soaking In con-
centrated sulfuric acid, then rinsed as in Section 1.2.2.2.
1.2.2.4 Allow the glassware to air dry and then place In a clean
glassware drying oven at — 110°C for at least 1 h.
A- 52
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1.2.2.5 After removing bottles from the oven, allow to cool to room
temperature, then cap with Teflon lined lids. If glassware is not used
immediately, cover the open ends with methanol rinsed aluminum foil and store.
1.2.3 Rinse Teflon liners and Teflon-lined septum thoroughly with
distilled-In-glass methanol. Allow to either air dry or bake at — 110°C for
no longer than 1 h.
1.2.4 New reactivials and 2—dram screw cap vials are rinsed with
methanol and baked at 110°C for at least 1 h. After removing from the oven,
they are allowed to cool and then capped with Teflon lined lids.
1.2.5 Syringes should be thoroughly cleaned with methanol. This Is
done as soon as possible after use to avoid contamination of the syringe.
Syringes are not routinely baked because high temperatures will weaken the
adhesive used to affix the needle to the barrel.
2.0 REAGENTS
2.1 REAGENT WATER (VOA WATER)
2.1.1 Reagent water is defined as a water in which compounds that
interfere with the analytes are not observed at the method detection limit.
2.1.2 Reagent water is prepared by pouring Milli-Q (or equivalent)
through a carbon bed into a chromatography column. The column is maintained
at a temperature of approximately 50°C with a gentle flow of prepurifled
nitrogen. Other methods of generating reagent water can be found in SW-846
method 8240 “GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE ORGANICS.”
2.1.3 Reagent water is used to prepare matrix spikes, field blanks,
and system blanks for the GC/MS system.
2.2 METHANOL
2.2.1 Only distilled—in-glass (pesl.iclde quality, B&J or equivalent)
methanol is used for glassware prep, preparal.lon of standards, and preparation
of samples.
2.2.2 Store niethanol in an area nol. contaminated by solvent vapors.
2.2.3 Bulk methanol may be used for decontamination of bottles and
vials prior to disposal and decontamination of glassware prior to cleaning for
re-use.
2.3 TENAX AND TENAX/CHARCOAL TRAPS
2.3.1 VOST traps of tenax and tenax/charcoal are prepared by field
sampling personnel. Details on preparation of traps are available in the ap-
propriate field sampling standard operating procedures (SOP) documents.
A—53
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2.4 SCREENING AND BLANKS
2.4.1 To ensure that no contaminants are present in the reagents,
blanks of each matrix type are analyzed by the appropriate GC/MS method.
3.0 SAMPLE TRACEABILITY AND CHAIN-OF—CUSTODY
3.1 SAMPLE TRACEABILITY
3.1.1 Each sample taken in the field is given a unique number by
field personnel. In the case of Volatile Organic Sampling Train (VOST) sam-
ples and gas bags, this number is carried throughout field sampling and anal-
ysis. Water and waste samples are also given a unique number by field per-
sonnel. However, these samples are composited In the laboratory prior to
analysis. Afterwards, the sample composite is given a new number by labora-
tory personnel. A record of sample composition and their new numbers are
recorded in the appropriate laboratory notebook.
3.1.2 A record of who was responsible for each sample and where the
sample was during the sampling and analysis procedures is kept using the forms
in Figures A3-1 and A3-2.
3.1.2.1 Figure A3—1 is the form used by the field sampling per-
sonnel. This form contains sampling information as well as the field sample
numbers. This form accompanies the samples from the time they are taken in
the field until their receipt by analytical personnel.
3.1.2.2 Figure A3-2 Is the form used by analytical personnel. This
form is used to transfer samples within the analytical sections or to in-
strument facilities.
3.2 CHAIN-OF-CUSTODY
3.2.1 In the event a contract requires chain-of-custody, the samples
are stored in a locked cold room which has restricted access. During the sam-
ple preparation or analysis, the samples must be within the sight of the per-
son who has custody, in a locked container, or in a container sealed with
evidence tape which has been appropriately signed and dated.
3.2.2 The forms in Figures A3—1 and A3—2 are appropriate for chain-
of—custody so long as this is noted on the form.
4.0 SAMPLE RECEIPT
4.1 Volatile samples are usually shipped daily from the field site.
These can be shipped by an overnight delivery service such as Federal Express
or by airport counter-to—counter service. The samples are shipped with suf-
ficient quantities of wet ice or “blue Ice” to keep the samples cool. Dry ice
is not recommended for water samples due to freezing of the samples which
will, in turn, break the vials.
A-54
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P.11. 1 .1.1.1 pl •— . —_________ ..I.,,I.. — •...I.... 1 . s.. . -— - • .i.,,,.. —
I isvosi( ry II.., k
J Coapin a
Figure A3-1. Sample traceability record.
-------
LABORATORy CHALN OF CJS ODY O T ACZA3ILIT’f R.ECORD
C Cha.n of Custody eco d
C Project Number ___________
Locat .on -
C Conta er Type —
Traceability Log
Date of Labora:orj Check-In _________
Type of Samtles _____________________
Custody Office Storage Location
SamD le
r 1d Sam 1e No . Desction
Figure A3—2
.aboratorv Sam le No.
- Amount of
Sample Removed
( ve date)
Coen ts
r _
r
.
Reiinqui.shed
Laboratory/Area (signature)
Custody Office
by: Received by:
Date/Time (signature)
I_______________
Date/Time
Sample Preparat.ioc.
etals J
;s
I______________
-
Other
(Ident ity)
—
—
—
I
Notebook Reference Pages 1
Analyst Co ents _________
] Notebook No.
I I
A-56
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4.2 Once the samples arrive, they are inventoried and examined for
breakage as soon as possible. In the event the samples cannot be inspected
right away, they are stored In a cold room in the shipping container until
such time as the Inspection can be accomplished.
4.3 The inventory of the samples is performed in a volatile free labora-
tory and Includes the following items:
4.3.1 The temperature of the ship ing container is observed. The
samples should still feel cool. If they are found to be above room tempera-
ture, this Is noted either on the traceability sheet or in the appropriate
laboratory notebook.
4.3.2 The samples are inventoried gainst the enclosed traceability
sheets. If no traceability sheets accompany the samples, then the inventory
is recorded in the appropriate laboratory notebook. During the inventory, the
condition of the samples is noted as well as the labeling information. The
label should be legible and contain the sample number as well as sample col-
lection information.
4.3.3 After inventory, the samples are stored in a cold room to
maintain sample integrity.
5.0 PREPARATION OF CALIBRATION STANDARDS, SPIKING SOLUTIONS, MATRIX SPIKES,
AND MATRIX BLANKS
5.1 PRIMARY STANDARD SOLUTIONS
5.1.1 Standards may be prepared from the purest available standard
materials or purchased as certified solution .
5.1.2 The name, manufacturer, lot number, and purity of each
compound used to prepare primary stock solutions is recorded in the
appropriate laboratory notebook.
5.1.3 The following gravimetric method of standard preparation is
used to prepare primary standard solutions:
5.1.3.1 With an analytical balance accurate to 0.0001 g, obtain
initial and final weights.
5.1.3.2 Calibrate the balance using class “S” weights if avail-
able. This calibration should bracket the expected working range of the stan-
dards. Record the calibration in the appropriate laboratory notebook.
5.1.3.3 Place about 9.0 mL methanol in a clean 10.0 mL class “A”
volumetric flask. Allow the flask to stand until all methanol wetted surfaces
have dried. Stopper the flask and obtain an Initial weight.
5.1.3.4 LIQUIDS: Determine the target concentration for the stock
solution and use the density of the chemical to determine an approximate
volume to add to the flask. Add the appropriate amount of the standard
A- 57
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material to the flask using a syringe. The liquid must fall directly onto the
surface of the methanol without touching the neck of the flask. Also, care
should be taken to not touch the surface of the methanol with the end of the
syringe as this would change the initial weight of the methanol and the
flask. The flask is immediately restoppered.
5.1.3.5 GASES: To prepare standards for any compounds that boil
below 30°C (e.g. bromomethane, chioroethane, chioromethane, and vinyl
chloride), fill a 5.0 mL valved gas—tight syringe with the reference standard
to the 5.0 mL mark. Lower the needle to 5 nmi above the methanol meniscus.
Slowly introduce the reference standard above the surface of the liquid. The
heavy gas will rapidly dissolve in the methanol. Standards may also be pre-
pared by using a lecture bottle equipped with a Hamilton Lecture Bottle Septum
(#86600). Attach Teflon tubing to the side-arm relief valve and direct a
gentle stream of gas into the methanol meniscus. Immediately restopper the
flask.
5.1.3.6 Obtain a final weight on the flask. Dilute to volume,
stopper, and mix by inverting the flask several times. Calculate the concen-
tration in mg/mL from the net gain in weight. Unless the compound purity is
stated to be 99+%, then the concentration must be corrected for compound
purity.
5.1.4 The primary stock solution is transferred to a clean (see
Section 1.2.4) 2-dram vial, capped with a Teflon lined lid, and sealed with
Teflon tape. The vial is filled so that a minimum amount of headspace remains
in the top of the vial. The vial is labeled with the name of the compound,
concentration, solvent, date prepared, initials of person preparing, and the
notebook reference for preparation. Store the vial at -10° to —20°C and
protect from light.
5.1.5 Prepare fresh standards every two months for gases.
compounds such as 2—chloroethyl vinyl ether may need to be prepared
quently. All other standards must be replaced after six months, or
comparison with check standards indicates a problem.
5.2 INTERMEDIATE DILUTION STANDARDS
Reactive
more fre-
sooner if
5.2.1 Using primary stock solutions, prepare intermediate dilution
standards in methanol either singly or as a combined mix.
5.2.2 Use volumetric glassware and syringes for all dilutions.
5.2.3 Allow the primary stock to
paring the intermediate solution. Check
degradation or evaporation. The level of
after each use, If possible, therefore once
perature the meniscus should match the mark
by inversion prior to removing an aliquot of
reach room temperature before pre—
the stock solution for signs of
the liquid in the vial is marked
the solution has reached room tern—
on the vial. Gently mix the vial
the primary stock.
A- 58
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5.2.4 Add a small amount of methanol to the volumetric flask. Then
add the appropriate amount of primary stock solution(s). Dilute to volume,
stopper, and gently mix by inversion.
5.2.5 Transfer and store intermediate dilutions as described for
primary standard solutions (see Section 5.1.4).
5.3 CALIBRATION STANDARDS
5.3.1 Calibration standards containing the POHCs, surrogates, and
internal standards at a minimum of three concentration levels are prepared
from intermediate or primary stock solutions (Sections 5.1 and 5.2). Prepare
these solutions in methanol according to the procedure outlined in Section 5.2
for preparation of intermediate stock solution. Transfer an aliquot to a
reactivial with minimum headspace, cap with a mininert valve and label.
Transfer and store the remainder as in Section 5.1.4.
5.3.2 One of the concentration levels should be at a concentration
near, but above, the method detection limi t (usually 10 ng total). The
remaining concentration levels should correspond to the expected range of con-
centrations found in real samples or should not exceed the working range of
the GC/MS system. Each standard contains all analytes for detection by this
method. In addition, the recovery Internal standards (RIS) and surrogates are
included In the calibration standard mixes.
5.3.3 The calibration standards arE replaced when signs of degrada-
tion are evident (typical replacement time is 2 weeks). If the standards fail
to pass the established curve or fail to pass the other calibration require-
ments (see Section 8.5), then the calibrations standards are reprepared.
5.4 SURROGATE AND RECOVERY INTERNAL STANDARD (RIS) SPIKING SOLUTIONS
5.4.1 Surrogates are organic compounds which are similar to analytes
of interest in chemical composition, extraction, and chromatography, but which
are not normally found in environmental samples. These compounds are spiked
into all blanks, standards, samples, and spiked samples prior to analysis.
Percent recoveries are calculated for each surrogate and should not vary from
the expected values by more than ±35%. d8-Toluene, 4—bromofluorobenzene, and
d4-1,2-dichloroethane are typically used as surrogate compounds, as recorn—
mended by SW-846 method 8240.
5.4.2 Recovery Internal standards (RIS) are compounds added to all
standards, blanks, and samples which are used to quantitate the analytes. The
RIS chosen should be similar In analytical behavior to the compounds of
interest. It must be demonstrated that the measurement of the internal
standard is unaffected by method or matrix Interferences. Brornochioromethane,
1,4-difluorobenzene, and d5—chlorobenzene are recommended by method 8240 as
RIS compounds. (Bromochioromethane, however, is sometimes found as a “native”
in samples, in which case Its value as a surrogate is limited.) Method 5040,
“PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC SAMPLING
TRAIN” requires d6—benzene as a RIS for VOST analysis. Other compounds may be
used depending on the analysis requirements. D6—benzene may be used as the
RIS for all sample types.
A- 59
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5.4.3 A spiking solution containing each of the RIS and surrogate
compounds is prepared in methanol according to the procedure in Section 5.2,
INTERMEDIATE STOCK SOLUTIONS. Transfer an aliquot to a reactivial with a
mininert valve and continue as in Section 5.1.4. The final concentrations of
each surrogate and RIS are approximately 50 ng/pL). Two inicroliters (2 L)
are used to spike each VOST trap, gas bag sample, water sample, and system
blank prior to analysis. This will yield 100 ng total per analysis for each
surrogate and RIS. Alternate spiking volumes and concentrations may be used
but will still yield approximately 100 ng total per analysis.
5.5 BROMOFLUOROBENZENE (BFB) FOR INSTRUMENT TUNING
5.5.1 A solution of 4—bromofluorobenzene in methanol with a concen-
tration of 50 ng/uL is prepared according to the procedure in Section 5.2.
This solution is used to tune the mass spectrometer according to SW-846 method
8240 specifications. (See Section 7.5.2.)
5.6 MATRIX SPIKING STANDARDS
5.6.1 Matrix spiking standards, if applicable, are prepared in
methanol from compounds representative of those being investigated. This
solution is used to prepare check samples and matrix spikes. No internal
standards or surrogates are added to this mix as these are added to these
samples during the routine prep of the samples. This solution is prepared
according to the procedure outlined in Section 5.2.
5.7 QC CHECK SAMPLES
5.7.1 A QC check sample Is analyzed during the initial GC/MS
calibration (see Section 7.5.8) to verify the ratio of instrument response to
analyte amount. Analysis of this sample also serves to verify the preparation
of the calibration standards. This solution is prepared independently of the
intermediate stocks used to prepare the calibration standards. The final con-
centrations of the analytes should fall within the calibration curve. This
solution is prepared according to the procedure outlined in Section 5.2. It
contains all analytes of specific quantitative interest.
6.0 PREPARATION OF SAMPLES, BLANKS, CHECK SAMPLES, MATRIX SPIKES, AND
RE P LI CATES
6.1 HOLDING TIMES
6.1.1 Unless otherwise specified by the trial burn plan, QA plan, or
the project leader, the holding time from date of sampling to date of analysis
for VOST samples is 2—6 weeks (see SW—846 method 5040 Section 6.2), and for
water samples, the holding time is 10 days.
6.2 VOST AND INTEGRATED GAS BAG SAMPLES (for analysis by purge and trap
desorptlon GC/MS)
6.2.1 VOST traps are glass tubes filled with either Tenax (2,6-di-
phenylene oxide polymer) only or one half each Tenax and charcoal. The ends
A—60
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of these tube are tightly capped. One trap of each type constitutes a
“pair.” There are generally three or four sample “pairs” per run. Each trap
is analyzed separately. In addition, the field sampling crew prepares a field
blank pair for each run and a trip blank pair for each shipment container.
The field blank pair Is opened briefly In the field. These samples are used
to demonstrate that there is no contaminaticn from ambient conditions at the
site. The trip blank pair is never opened and accompanies each respective
sample batch of samples returning to the l boratory. These samples are to
demonstrate that there is no contamination from the shipping process.
6.2.2 The VOST samples need no preparation prior to analysis. These
samples are stored in the cold room until analysis and are spiked with a mixed
RIS and surrogate solution by the GC/MS analyst Immediately prior to
analysis. A daily system blank is analyzed (see Section 8.5.3) by spiking a
clean trap with the RIS/surrogate solution. This is to ensure the cleanliness
of the GC/MS system and also serves as a blank sample for each day’s
analysis. Each VOST trap is only valid for one analysis, therefore replicate
analyses and matrix spikes cannot be performed.
6.2.3 After analysis, the spent VOST traps and gas bags are returned
to field programs where they will be recycled.
6.3 WATER AND VOST CONDENSATE SAMPLES (for analysis by purge and
trap GC/MS)
6.3.1 Water samples are samples taken of various water streams as
specified by the trial burn plan for each project. These are usually called
scrubber waters and are usually of two types, inlets and outlets. Occa-
sionally other types of water samples are taken, for example, VOST con-
densates, but they are prepared in the same manner.
6.3.2 The preparation of the w ter samples is performed in a
volatile free laboratory (VOA lab).
6.3.3 Water samples are sampled at either 15- or 30-mm intervals
during each field test and are typically composited prior to analysis.
6.3.4 The samples are sorted according to run number and type.
Then, all of the VOA vials of each run and type are composited by pouring the
contents of the vial into a larger clean compositing bottle. The composite is
gently mixed and the composited sample is r?turned to the original VOA vials
filling them In such a manner as to have no headspace In the vials. This is
done as quickly as possible to avoid loss of volatile compounds. The vials
are labeled as having been composited. Eac , vial Is typically used for only
one analysis, with different VOA vial of the composited sample being used for
each replicate analysis. The remainder of the vials are stored In the cold
room (4°C).
6.3.5 Replicate analyses of samples should be performed at least
once every 20 samples. The project QA plan should be consulted for specific
requirements.
A-61
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6.3.6 Laboratory blanks for the water samples are performed using
VOA water with the addition of mixed surrogate and RIS spiking solution. This
is done on a daily basis and also functions as the “system blank” for the
GC/MS system. In addition, the water field blanks (Section 1.1.4) shipped
with the samples are analyzed.
6.3.7 Five milliliters (5.0 mL) of each composited sample is
analyzed by GC/MS purge and trap. The GC/MS analyst spikes each sample with
the mixed RIS and surrogate spiking solution immediately prior to analysis.
7.0 GC/MS ANALYSIS OF WATER SAMPLES BY PURGE AND TRAP
7.1 SUMMARY OF METHOD
7.1.1 Five milliliters (5 mL) of the sample is poured into a glass
syringe, spiked with surrogate and RIS, then added to a glass purge tower. An
inert gas is bubbled through the solution at ambient temperature and the
volatile components are efficiently transferred from the aqueous phase to the
vapor phase. The vapor is swept through a sorbent column where the volatile
components are trapped. After purging is completed, the sorbent column is
heated and backflushed with Inert gas to desorb the components onto a gas
chromatographic column. The volatile POHCs are separated by temperature pro-
grammed gas chromatography and detected by mass spectrometry. The concentra-
tions of the POHCs are calculated using the internal standard technique.
7.1.2 Refer to SW—846 method 8240 “GAS CHROMATOGRAPHY/MASS SPECTROM—
ETRY FOR VOLATILE ORGANICS” for complete details of this analytic method. Any
deviations from SW-846 are listed in Section 11.0 of this document.
7.2 PURGE AND TRAP DEVICE
7.2.1 The purge and trap device consists of three separate pieces of
equipment: the sample purger, the analytic trap, and the desorber. It is
recommended that any surface to come in contact with the samples be con-
structed entirely of glass and Teflon.
7.2.2 The recommended purging chamber is designed to accept 5-mL
samples with a water column at least 3 cm deep. The gaseous headspace between
the water column and the trap must have a total volume of less than 15 mL.
The purge gas must pass through the water column as finely divided bubbles
with a diameter of less than 3 mm at the origin. The purge gas must be
introduced no more than 5 mm from the base of the water column. The sample
purger, illustrated in Figure A3-3 meets these design criteria. Alternate
sample purge devices with 20—25 mL headspace may also be utilized. These have
been demonstrated to yield equivalent sample recoveries and are useful for
analysis of waste samples dispersed in PEG since line contamination is mini-
mized.
A-62
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‘h Inca 0. 0. Exit
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OPTIONAL
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A-63
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7.2.3 The trap must be at least 25 cm long and have an inside diam-
eter of at least 0.105 in. Starting from the inlet, the trap is packed with
the following: 1.0 cm of methyl silicone coated packing (3% SP2100 on 60/80
Chromosorb WAW or equivalent to prolong the life of the trap); 15 cm 2,6-di-
phenylene oxide polymer 60/80 mesh chromatographic grade (Tenax GC or equiva-
lent); 8 cm silica gel 35/60 mesh (Davison, grade 15 or equivalent). If anal-
ysis for dichiorodifluoromethane or other fluorocarbons of similar volatility
is required, then the trap should be packed with equal parts of coconut char-
coal, Tenax, and silica gel with 1.0 cm of methyl silicone coated packing at
the inlet. The coconut charcoal is prepared from Barnebey Cheney, CA-580-26
lot #M-2649 by crushing through 26 mesh screen. If only compounds boiling
above 35°C are to be analyzed, then the trap should be packed with only the
methyl silicone packing and Tenax. Before initial use, the trap should be
conditioned overnight at 180°C by backflushing with an inert gas flow of at
least 20 mL/min. Vent the trap effluent to the room, not to the analytical
column. Prior to daily use, the trap should be conditioned for 10 mm at
180°C with backflushlng. The trap may be vented to the analytical column
during daily conditioning, however, the column must be run through the
temperature program prior to analysis of samples.
7.2.4 The desorber should be capable of rapidly heating the trap to
180°C for desorption. The polymer section of the trap should not be heated
higher than 180°C and the remaining sections should not exceed 220°C during
bake-out mode. The desorber design in Figure A3-4 meets these criteria.
7.2.5 The purge-and—trap device may be assembled as a separate unit
or may be coupled to a gas chromatograph as shown in Figures A3—5 and A3-6.
7.3 GAS CHROMATOGRAPHY/MASS SPECTROMETRY SYSTEM
7.3.1 GAS CHROMATOGRAPH: An analytical system complete with a tem-
perature programmable gas chromatograph and all required accessories including
syringes, analytical columns, and gases.
7.3.2 COLUMN: 6 ft x 0.1 in i.d. glass, packed with 1% SP 1000 on
Carbopak-B, 60/80 mesh, or equivalent. In some cases, an 8 ft column with
similar packing provides better resolution of coeluting compound such as car-
bon tetrachioride and 1,1,1-trichioroethane. Alternatively, a 30-rn DB—624
niegabore capillary column can be used. This column has resolution and reten-
tion order comparable to the SP 1000, however, analysis time is shortened.
(This column was not commercially available at the time SW-846 was published.)
7.3.3 MASS SPECTROMETER: Capable of scanning from 40-260 amu every
3 s or less, using 70 electron volts (nominal) electron energy in the electron
impact mode and producing a mass spectrum that meets all the criteria In
Table A3—1 when 100 ng of 4-bromofluorobenzene (BFB) are injected through the
gas chrornatographic inlet. Typically a MAT CH4, or Finnigan OWA, or
Varian 312A is used.
A-64
-------
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Packiriq P Curt
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A—65
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Schematic of purge-and-trap device-—purge mode.
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Figure A3-6.
Schematic of purge—and—trap device--desorb mode.
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A-66
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7.3.4 GC/MS INTERFACE: Any GC-to—MS interface that gives acceptable
performance criteria may be used. GC-to-MS Interfaces constructed entirely of
glass or of glass-lined materials are recommended. Glass can be deactivated
by silanizing with dichlorodimethylsilane.
7.3.5 DATA SYSTEM: A computer system that allows the continuous
acquisition and storage on machine—readable iriedia of all mass spectra obtained
throughout the duration of the chromatographic program must be interfaced to
the mass spectrometer. The computer must have software that allows searching
any GC/MS data file for ions of a specified mass and plotting such Ion abun-
dances versus time or scan number. This type of plot is defined as an
Extracted Ion Current Profile (EICP). Software must also be available that
allows Integrating the abundances in any EIC between specified time or scan-
number limits. The most recent version of the EPA/NIH Mass Spectral Library
should also be available.
7.4 GC/MS OPERATING CONDITIONS
Electron energy:
Mass range:
mass spectrometer)
Scan time:
exceed 7 s/scan.
Initial column temperature:
Initial column holding time:
Column temperature program:
Final column temperature:
Final column holding time:
Injector temperature:
Source temperature:
specifications
Transfer line temperature:
Carrier gas:
Purge flow:
7.5 INITIAL CALIBRATION
70 electron volts (nominal)
40-260 (40—280 amu for the MAT CH4
To give 5 scans per peak but not to
45°C
3 mm
8°C/mi n
220°C
Analyte and matrix dependent
200-225°C
According to manufacturer’s
250-300°C
Helium at 30 cm/sec
Nitrogen at 40 mL/min
7.5.1 Each mass spectrometer will be calibrated for mass scale using
perfluorokerosene (PFK) or perfluorotrlbutylamine (FC-43) according to
manufacturer’s specifications.
7.5.2 Each GC/MS system must be hardware tuned to meet the criteria
in Table A3-1 for a 100 ng injection of BFB (see Section 5.5). Analysis must
not begin until these criteria are met.
7.5.3 A system blank consisting of five milliliters (5.0 mL) reagent
(VOA) water spiked with the surrogate/RIS solution will be analyzed (as
outlined in Sections 7.5.4.1 through 7.5.4.5 to ensure that the GC/MS system
Is contaminant free. This shall be done Immediately before and after the
calibration curve Injections. Should the system prove to be contaminated,
then the following measures are taken.
A-67
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TABLE A3-1. BFB ION ABUNDANCE CRITERIA
Mass Ion abundance criteria
50
15% to 40% of mass 95
75
30% to 60% of mass 95
95
Base peak, 100% relative
abundance
96
5% to 9% of mass 95
173
Less than 2% of mass 174
174
Greater than 50% of mass
95
175
5% to 9% of mass 174
176
Greater than 95% but less
than 101%
of
mass
174
177
5% to 9% of mass 176
A-68
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7.5.3.1 Perform a “bake-out” of the analytic system by running
through the temperature program and heating the analytic trap. Occasionally,
an overnight bake—out of the system may be necessary to rid the system of
gross contamination.
7.5.3.2 Ensure that the purge towers and syringes have been
properly cleaned.
7.5.3.3 Obtain fresh VOA water to rule out contaminated water.
7.5.3.4 If necessary, the spiking solution will be reprepared
to rule out contamination during the preparation.
7.5.3.5 If these measures prove to be unsuccessful in elim-
inating the contamination, then the GC/MS supervisor or project leader should
be consulted for further action to be taken.
7.5.4 A five—point calibration curve will be established using the
following procedure:
7.5.4.1 After allowing the standards to warm to room tempera-
ture, spike the calibration standards (see Section 5.3) into an all glass
syringe containing 5 mL VOA water. Be sure the standard solution is expelled
beneath the surface of the water and aw.iy from the delivering syringe
needle.
7.5.4.2 This solution is then mixed by inversion and added to
the purge tower. Purge the standard for 11.0 mm at ambient temperature.
7.5.4.3 At the conclusion of the purge time, desorb the
analytic trap, begin the GC temperature program, start the GC/MS data acquisi-
tion. Concurrently, introduce the trapped miterials to the column by rapidly
heating the trap to 180°C whIle backflushing the trap with inert gas between
20 and 60 niL/mm for 4 mm.
7.5.4.4 WhIle the trap is being desorbed into the GC, empty
the purge tower. Wash with a minimum of two 5 mL flushes of reagent water (or
methanol followed by reagent water) to avoid carryover into subsequent
analyses.
7.5.4.5 After desorbing the standard for 4 mm, recondition
the trap by returning the purge-and-trap device to the purge mode. Maintain
flow through the trap. The trap temperature should be maintained at 180°C.
Trap temperatures up to 220° may be employed, however, the higher temperatures
will shorten the useful life of the trap. After approximately 7 mm, turn off
the trap heater and open the valve to stop the gas flow through the trap.
When cool, the trap Is ready for the next sarriple.
7.5.5 Tabulate the area response of the characteristic ions (see
Table A3-2) against concentration for each organic compound of Interest,
surrogate, and each internal standard. This; is calculated for each point in
the curve. Calculate response factors (RE) for each compound relative to the
internal standard.
A- 69
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TABLE A3-2.
RETENTION TIMES AND CHARACTERISTIC IONS FOR
VOLATILE COMPOUNDS
Reten
Compound time
tion Secondary
(mm) Primary ion ion(s)
Acetone
43
58
Acrolein
——
56
55,
58
Acrylonitrile
——
53
52,
51
Benzene
17.0
78
52,
77
Broniodichioromethane
14.3
83
85,
129
Bromoform
19.8
173
171,
175, 252
Carbon tetrachloride
13.7
117
119,
121
Chlorodibromomethane
--
129
208,
206
2-Chioroethyl vinyl ether
18.6
63
65,
106
Chloroform
11.4
83
85,
47
1,1-Dichioroethane
——
63
65,
83
1,2-Dichioroethane
——
62
64,
98
1,1-Dichioroethene
9.0
96
61,
98
trczns-1,2-Dichloroethene
10.0
96
61,
98
1,2—Dichioropropane
15.7
63
62,
41
cLs—1,3—Dichloropropene
15.9
75
77,
39
trans-1,3-Dichloropropene
17.2
75
77,
39
Diethyl ether
Ethylbenzene
26.4
106
91
Methylene chloride
6.4
84
49,
51, 86
Methyl ethyl ketone
1,1,2,2—Tetrachloroethane
22.1
83
85,
131, 133
Tetrachloroethene
22.2
164
129,
131, 166
Toluene
23.5
92
91,
65
1,1,1-Trichloroethane
13.4
97
99,
117
1,1,2-Trichioroethane
17.2
97
83,
85, 99
Trichioroethene
16.5
130
95,
97, 132
Trichiorofluoroniethane
8.3
101
103,
66
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The RF Is calculated as follows:
RF = (AxCis)/(AisCx)
where:
Ax = Area of the characteristic ion for the compound being
measured.
Ais = Area of the characteristic ion for the specific internal
standard.
Cis = Amount (ng) of the specific internal standard.
Cx = Amount (ng) of the compound being measured.
7.5.6 Tabulate the area response oF the characteristic ions of each
organic compound of interest and surrogate against the concentration of the
internal standards as described in Section 7.5.5.
7.5.7 Calculate the average RF for each compound. If the RF value
over the working range is a constant (±20% RSO), the RF can be assumed to be
invariant, and the average RF can be used for calculations. This variability
range may be expanded to ±30% RSO with the approval of the project leader.
The ability to meet this criteria is dependent upon the concentration range of
the calibration standards; i.e., a wider rang’? will have a larger RSD. Alter-
natively, the results can be used to plot a calibration curve of response
ratios As/Als versus RF.
7.5.8 Analyze a QC check sample by the procedure described
beginning in Section 7.5.4.1. The recoveries should fall within ±20% of the
expected value.
7.6 DAILY CALIBRATION
7.6.1 Perform the calibration steps as described in Sections 7.5.1
and 7.5.2 on a daily basis. In addition, the BFB tuning requirement must be
demonstrated every 12 h during extended work Jays.
7.6.2 Analyze an aliquot of reagent water. This will serve as both
a system blank and a reagent blank.
7.6.3 Daily calibration checks are performed by analyzing the
midrange standard at least once every 12 h.
7.6.3.1 The Internal standarJ responses are examined for re-
tention time shifts. If the retention times have shifted more than 30 s from
the last calibration check, the chromatographic system must be inspected for
malfunctions and corrections made.
7.6.3.2 If the EICP area for any of the internal standards
changes by a factor of two from the last daily calibration check standard, the
mass spectrometer must be inspected for malfunctions and corrections made as
appropriate.
A-il
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7.6.3.3 When corrections are made, reanalysis of samples ana-
lyzed while the system was malfunctioning are necessary.
7.7 ANALYSIS OF WATER SAMPLES
been met,
7.7.2 An aliquot of the well mixed water sample prepared in
Section 6.3 is poured into an all glass syringe. The volume of the water
sample is adjusted to 5.0 mL. The sample is then spiked with the
surrogate/RIS spiking solution and mixed by inversion.
7.7.3 Analysis then continues as described in Section 7.5.4 using
5.0 mL of sample and spiking with the RIS/surrogate solution.
7.7.4 If analysis of the sample shows any analyte to be outside the
calibration range of the instrument, this sample must be diluted as described
in 7.7.4.1 and 7.7.4.2. If the high level sample saturates any of the quan-
titation ion, a system blank must be analyzed to assure no carryover to the
next analysis.
7.7.4.1 Dilutions are made from a different VOA vial of the
composited sample than was used for the first analysis whenever possible.
7.7.4.2 Allow the water sample to be diluted and the VOA water
to reach room temperature. Add an aliquot of the sample to a volumetric flask
and dilute to volume with the VOA water. An aliquot of this dilution is ana-
lyzed as In Section 7.5.4 usIng 5.0 mL of the diluted sample and the RIS/sur-
rogate solution.
7.7.5 Surrogate recoveries must be ±35% from the expected value.
Reanalysis of the sample is necessary if recoveries fall out of this range.
7.7.6 A replicate analysis is performed for every 20 samples unless
otherwise specified by the project specific trial burn plan or the QA plan.
8.0 GC/MS ANALYSIS OF VOST SAMPLES
8.1 SUMMARY OF METHOD
8.1.1 The traps are spiked with an internal standard solution using
the flash evaporation technique. They are then thermally desorbed for 11 mm
at 180°C with organic-free nitrogen, bubbled through 5 mL of organic-free
water, and trapped on the analytical trap. After the 11-mm desorption, the
analytical trap is rapidly heated to 180°C with the carrier gas reversed so
that the effluent flow from the analytical trap is directed into the GC/MS.
The volatile POHCs are separated by temperature—programmed gas chromatography
and detected by low-resolution mass spectrometry. The concentrations of the
volatile POHCs are calculated using the Internal standard technique.
7.7.1 Once the initial and/or daily calibration requirements have
analysis of samples may begin.
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8.1.2 Refer to SW-846 method 5040 “PROTOCOL FOR ANALYSIS OF SORBENT
CARTRIDGES FROM VOLATILE ORGANIC SAMPLING TRAIN” for complete details of this
analytic method. Deviations are listed in Section 11.0 of this document.
8.2 APPARATUS
8.2.1 Trap spiking apparatus:
8.2.1.1 Internal standards are introduced Into each VOST trap
prior to analysis using a special accessory. This consists of a trap holder,
a heated GC—type septum injector, and a supply of helium gas. The injector is
maintained at a temperature of 220°C and the helium flow is about 50 mL/min.
8.2.2 Thermal desorption unit:
8.2.2.1 The thermal desorpticn unit
traps to 180°C with flow of organic-free nitrogen
inside/inside VOST traps, use the Supelco
inside/outside VOST traps, a user fabricated heater
8.2.3 Purge and trap device:
8.3 GC/MS SYSTEM
8.3.1 The GC/MS system is as described in Section 7.3.
8.4 GC/MS OPERATING CONDITIONS
8.4.1 The GC/MS operating conditions are as described in Sec-
tion 7.4.
8.5 INITIAL CALIBRATION
8.5.1 Each mass spectrometer will be calibrated for mass scale
using perfluorokerosene (PFK) or perfluorotributylamlne (FC-43) according to
manufacturer’s specifications.
8.5.2 Each GC/MS system must be hardware tuned to meet the criteria
in Table A3-1 for a 100—ng injection of BFB (see Section 5.5). Analyses must
not begin until these criteria are met.
8.5.3 A system blank is perforifed immediately before and after
of the calibration curve standards iccording to the following proce—
8.5.3.1 Turn the helium flow on. Insert a clean trap Into the
spiking accessory and seal with the knurled nut.
Section 7.2.
is capable of heating
through the traps.
“clamshell” heater;
is required.
8.2.3.1 The purge and trap unit is as described
the
For
f or
in
analysis
dure:
A-73
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8.5.3.2 Using an exact volume technique, slowly inject the
internal standard solution into the vaporizing port of the spiking acces-
sory. After 15 seconds, shut off the gas flow, and remove trap. The total
flow of gas through the trap during addition of internal standards should be
25 mL or less.
8.5.3.3 Place the spiked trap into the thermal desorption unit
and attach the ticlajishellil heater. Check the flow to ensure a 40-mL/min
nitrogen flow rate. Heat trap and desorb for 11 mm.
8.5.3.4 The desorbed components pass into the bottom of the
water column, are purged from the water, and are collected on the analytic
trap. After the li-mm desorption period, the compounds are desorbed from the
analytical trap into the GC/MS system by rapidly heating the analytic trap and
backflushing with inert gas for 4 mm.
8.5.3.5 If the system proves to be contaminated, then the cor-
rective action outlined in Section 7.5.3 is initiated.
8.5.4 A minimum of calibration standards at three levels are used
to prepare the calibration curve. Each standard is analyzed on three Tenax
traps spiked with calibration standards to establish a calibration curve.
These traps are spiked and analyzed as described beginning in Section 8.5.3.1.
8.5.5 Tabulate the area response of the characteristic ions of each
analyte (surrogate and compound of interest) against the concentration of the
internal standards as described in Section 7.5.5.
8.5.6 Calculate the average RF for each compound. If the RF value
over the working range is a constant (±20% RSD), the RF can be assumed to be
invariant, and the average RF can be used for calculations. This variability
range may be expanded to ±30% RSD with the approval of the project leader.
The ability to meet this criteria is dependent upon the concentration range of
the calibration standards; I.e., a wider range will have a larger RSD. Alter-
natively, the results can be used to plot a calibration curve of response
ratios As/Als versus RF.
8.5.7 Analyze AQC check sample by the procedure described beginning
in Section 8.5.3.2. The recoveries should fall within ±20% of the expected
value.
8.6 DAILY CALIBRATION
8.6.1 Perform the calibration steps outlined in Sections 7.5.1 and
7.5.2. In addition, the BFB tuning requirement must be demonstrated every
12 h during extended work days.
8.6.2 A system blank is analyzed as outlined in Section 8.5.3.
8.6.3 A daily calibration check is performed by spiking a Tenax
trap with the mid range calibration standard. The response factors calculated
from this injection must not vary by more than ±20% for any analyte. This
A-74
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variability range may be expanded to ±30% with the approval of the project
leader.
8.7 ANALYSIS OF VOST SAMPLES
8.7.1 Each sample trap, field bl Lnk trap, and trip blank trap is
analyzed by the procedure described beginning In Section 8.5.3.
8.7.2 If analysis shows any analy e to be outside the calibration
range of the instrument, then a higher level ‘;tandard is prepared and analyzed
to bracket that sample.
8.7.3 If samples are encountered that have concentrations of
analytes above the highest point in the calibration curve, the cleanliness of
the system must be proved by analyzing a system blank as in Section 8.5.3. If
this system blank proves to be clean, this establishes a new lower limit for
the analysis of system blanks. If, on subsequent analyses, a sample is en-
countered that is above this new limit, a system blank must be analyzed. Once
again, if this proves the system to be clean, then this higher limit is estab-
lished. This continues until an amount of analyte is found that does not
clean up from the system during the usual operating procedure. When this
occurs, a longer bake—out of the system is required.
9.0 DATA INTERPRETATION
9.1 QUALITATIVE ANALYSIS
9.1.1 An analyte Is identif led by comparison of the sample mass
spectrum with the mass spectrum of a standard of the suspected compound (stan-
dard reference spectrum). Mass spectra for standard references are obtained
on the user’s GC/MS within the same 12 h as the sample analysis. These
standard reference spectra may be obtained through analysis of the calibration
standards. Two criteria must be satisfied to verify identification: (1) elu-
tion of sample component at the same GC relative retention time (RRT) as those
of the standard component; and (2) correspondence of the sample component and
the standard component mass spectrum.
9.1.2 The sample component RRT must compare within ±0.06 RRT units
of the RRT of the standard component. For reference, the standard must be run
within the same 12 h as the sample. If coE!lutlon of interfering components
prohibits accurate assignment of the sample component RRT from the total ion
chromatograin, the RRT is assigned by using extracted Ion current profiles for
ions unique to the component of Interest.
9.1.3 Every ion plot and mass spectrum will be visually inspected
to ensure that (1) All ions present in the standard mass spectra at a relative
intensity greater than 10% (most abundant Ion in the spectrum equals 100%)
must be present in the sample spectrum. (2) The relative Intensities of ions
specified in (1) must agree within ±20% between the standard and sample
spectra. (Example: for an ion with an abundance of 50% in the standard
spectra, the corresponding sample abundance must be between 30% and 70%.)
These criteria may be relaxed slightly if, In the best professional judgment
A- 75
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of the data analyst, a compound lacking all criteria is still deemed to be a
“hit.
9.1.4 If the project specific trial burn plan indicates that com-
pounds other than the analytes of interest (i.e., PICs or unknowns) are to be
identified, this work is performed by personnel experienced In mass spectral
interpretation. A computer search of the NBS mass spectral library is
obtained for each unknown spectrum, followed by manual evaluation of the
spectra and search results. Manual searches of mass spectral libraries are
also used to facilitate Identifications. In some cases it is not possible to
identify a compound based on its electron impact mass spectrum alone. To the
extent possible, these compounds will at least be characterized by class; for
example, as “hydrocarbon”, “amine”, etc. Unknown and PlC compounds may also
be semiquantitated by calculating ng amounts as outline in Section 7.5.9 usIng
total ion areas for both unknown and internal standard and assuming a response
factor of 1.000.
9.2 QUANTITATIVE ANALYSIS
9.2.1 SpecIfic quantitation information based on response factors
for compounds (Section 9.5.6) will be done for surrogates and POHCs only.
Quantitation for PICs and unknowns will be calculated using RFs of 1.000 or
historical response factors if available.
9.2.2 When a compound has been identified, the quantification of
that compound will be based on the integrated abundance from the EICP of the
primary characteristic Ion. For VOST samples only, if the primary ion is
saturated or has an interference, then a secondary ion is used for quantifica-
tion. However, a new RF should be established for the secondary ion. Quanti-
fication will take place using the internal standard technique.
9.2.3 Calculate the total ng per analysis of each identified
analyte in the sample as follows:
total ng = [ Aa/AisJ x ICis/RFa]
where:
Aa = Area of the characteristic ion for the analyte to be
measured.
Ais = Area of the characteristic ion for the specific
internal standard.
Cis = Amount (ng) of the specific internal standard.
RFa = Calculated average response factor for the analyte.
9.2.4 The “ICA” quantitation report values may be used in place of
manual calculations for the total ng per analysis.
9.2.5 VOST samples are reported as total ng per trap or total ng
per pair.
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9.2.6 Water samples are reported in ng/mL by the following:
pg/L = ng/mL = total ng found / purge volume (5.0 mL)
9.2.7 Waste feeds are reported in i’g/g by the following:
pg/g = [ pg found/injection volume (niL)1 x [ dilution (mL)/sample wt(g)]
9.2.8 Report results without correction for recovery data. When
duplicates, matrix spikes, and check samples are analyzed, report all data
with sample results.
10.0 QUALITY CONTROL
Specific QC requirements are included In the section where appropriate,
however, a summary of the QC performed with sample preparation and analysis is
summarized in this section.
10.1 BLANKS
10.1.1 Field blanks are analyzed to ensure that no contamination of
the samples has occurred during the sampling and shipping processes. Trip
blanks are a specific type of field blank and are utilized for VOST analysis
to segregate the sampling process from the shipping process. See Sec-
tion 6.2.1 for further explanation of VOST trip and field blanks. The
preparation of water field blanks is outlined in Section 1.1.4.
10.1.2 System blanks for the GC/MS system are performed on each in-
strument on a daily basis. These analyses re to demonstrate that the GC/MS
system is free from contaminants. These may also function as reagent blanks
(Section 10.1.3).
10.1.3 Reagent blanks are perform€d by spiking the various reagents
with RIS and surrogate and are analyzed acc:ording to the procedure for that
type of sample. This is done for each batch or lot number of reagent.
10.2 SAMPLE QA REQUIREMENTS
10.2.1 For all water samples spiked with surrogates. Recoveries
are calculated for all these samples and must. fall within ±35%.
10.2.2 Replicate analyses water samples are performed at least once
per 20 samples. However, the project specific QA plan is consulted for addi-
tional replicate analyses.
10.3 INITIAL INSTRUMENT CALIBRATION REQUIREMENTS
10.3.1 Each instrument Is calibrated for mass scale using PFK or
FC-43 according to manufacturer’s specifications prior to the initial calibra-
tion curve.
10.3.2 Each instrument is tuned to meet the criteria in Table A3-1
for a 100—ng injection of BFB.
A- 77
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10.3.3 A calibration curve Is established and acceptable per-
formance demonstrated prior to the analysis of samples. Initial calibration
procedures are dependent on sample type and are outlined in Sections 7.5, 8.4,
and 8.5.
10.4 DAILY INSTRUMENT CALIBRATION REQUIREMENTS
10.4.1 Each instrument is calibrated for mass scale with PFK or FC—
43 on a daily basis.
10.4.2 The BFB performance criteria in Table A3—1 must be
demonstrated every 12 h.
10.4.3 Daily calibration requirements are dependent on sample type
and are outlined in Sections 7.6 and 8.6.
11.0 MODIFICATIONS FROM SW-846 METHODS
11.1 METHOD 8240 “GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE
ORGANICS”
METHOD 8240
SECTION NO. MODIFICATION
4.12.3 100 ng of BFB is injected rather than 50 ng. This
5.5 gives better instrument response on the lower
7.2.2 Intensity ions.
7.3.1
5.1.3 Purities < 100% (or 99+%) are corrected.
5.3 Concentrations of stock solutions will vary
5.4 according to analysis needs. Usually, surrogate
5.7 and RIS solutions are such that 100 ng per analysis
is achieved. RIS and surrogates are prepared as a
mix for yOST, water samples, and system blanks.
A three point calibration curve is acceptable.
5.6 Calibration standards are prepared in methanol rather
than reagent water and they are used until signs of
degradation become evident.
5.8 standard solutions are stored in clear vials and placed
In a closed container to protect from light.
6.1 New bottles and vials are cleaned according to
Introductory Chapter, Section 4.1.2. Sample bottles
and vials are not reused, they are decontaminated with
methanol and disposed of. Reactivials and volumetric
flasks are decontaminated after use, then cleaned as
in Section 4.1.2.
A-78
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7.2.5 CalibratIon standards are prepared as a mix which
includes analytes, surrogates, and RIS. This standard Is
spiked directly into the glas1 syringe containing 5.0 mL
VOA water, mixed, and added to the purge tower.
7.2.9 The GC/MS data system (INCOS) uses n rather than n—i for
%RSD calculations. If a %RSD falls within 3% of the
cutoff value, then this %RSD s recalculated manually
using n-i to achieve a more accurate value.
7.4.1 Water samples are not prescreened as they generally
contain a very low concentration of analytes.
7.4.1.5 Purge gas is nitrogen at 40 mL/min. Carrier gas is
helium at 30 cm/s.
7.4.1.7.3 Only one aliquot for analysis is taken from any given VOA
vial. If replicates are required, then these aliquots
are taken from individual VOA vials. If dilutions are
necessary, then an aliquot is taken from a fresh VOA
vial.
7.5.2 Quantitation for PICs will be performed via internal standards
method, using RFs generated from a single—point composite
standard analysis. Unknowns will be quantified by using RRF5
of 1.000.
8.5.1 Concentrations of analytes will vary depending on
8.5.2 the analysis needs.
11.2 METHOD 5040 “PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES
FROM VOLATILE ORGANIC SAMPLING TRAIN”
METHOD 5040
SECTION NO. MODIFICATION
5.3.2 Stock solutions are maintained for 2 months for
reactive compounds and gases, 6 months for all others.
They are replaced sooner if signs of degradation are
evident. (per method 8240)
5.5 100 ng BFB used for better instrument response on 7.1 the
lower intensity ions.
5.6 Concentrations of stock solutions will vary depending
on analysis needs.
7.2.3 Internal standard amounts are typically 100 ng per
analysis.
8.4.1 Acceptable range for internal standard areas is ±35% from
run to run, or a factor of two (-50% to +100%) from the
last daily standard per method 8240.
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APPENDIX A—I
SEMIVOLATILES ANALYTICAL METHODS
A-81
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APPENDIX A—4
SEMI VOLATILES ANALYTICAL METHODS
1.0 GLASSWARE PREPARATION
1.1 Standard Procedures
All glassware for field sampling and analysis of semivolatile organic
compounds is prepared according to the follo dng procedures.
1.1.1 Wash all glassware in hot, soiLpy water (use ISOCLEAN nonionic
soap, Micro, Alconox, or equivalent synthetic detergents and a clean brush).
1.1.2 Rinse with tap water (5X), deionized water (3X), and bulk acetone
(2X).
1.1.3 Air dry and cover open ends of glassware with solvent-rinsed
aluminum foil and store in appropriate drawers.
1.1.4 Any glassware that gives an Indication of still being dirty, i.e.,
the water and acetone rinses do not “sheet,” should be recleaned by soaking in
concentrated sulfuric acid overnight then rinsed as In Section 1.2.2.2.
1.1.5 Before actual use, clean glassware and Teflon liners from storage
drawers should be rinsed with high purity acetone followed by a 2X rinse with
the appropriate solvent to be used in t ie method. Glassware for field
sampling should be rinsed a final time with niethylene chloride (DCM).
1.1.6 Glassware used for extraction, concentration, and cleanup
procedures are numbered as a set. Such glas1.ware is to be used in a set.
1.1.7 A final rinse of the glassware sets with the appropriate solvent
should be collected in a vial, labeled to note glassware type and set, and
archived as a glassware rinse.
1.1.8 The dram vials, reacti-vials, and autosampler vials are rinsed 2X
with the solvent to be used and allowed to air dry.
1.1.9 When required, dram vials may be precalibrated by dispensing a
measured volume of the appropriate solvent into the vial and etching the glass
at the bottom of the miniscus. Precalibrated vials are to be rerinsed with
the appropriate solvent and allowed to dry.
1.1.10 VIal caps are to be lined with ‘;olvent—rinsed Teflon liners.
A-83
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1.1.11 After use, glassware is to be rinsed once with extraction solvent
and once with bulk acetone before detergent washing.
1.2 SW—846 Method Modifications, Deviations, and Enhancements
The following modifications, deviations, and enhancement from SW—846 and
other standard methods will be employed during this study. None are expected
to impact the quality of the results submitted. The glassware cleaning
procedure deviates from SW-846, Chapter 4 recommended method, as follows.
1.2.1 SW-846 recommends using methanol rather than bulk acetone in
Steps 1.1.2 and 1.1.11.
1.2.2 SW-846 suggests using a hot ( 50°C) soap water soak and a hot
water rinse.
1.2.3 SW-846 recommends a soak with hot chromic acid solution to destroy
traces of organic compounds.
2.0 SORBENT CLEANUP AND PREPARATION
2.1 XAD—2 Cleanup and Trap Preparation
2.1.1 Extraction and Fluidation——A batch of XAD-2 adsorbent (Ailtech
Assoc./Applied Science, 20/50 mesh, 90 A pore size, precleaned) is placed into
a Soxhlet extraction apparatus and extracted for 22 h with methylene chloride
(DCM) as outlined in Section 2.3.2.
The XAD-2 is then placed into an evaporating dish lined with niethylene
chloride—rinsed aluminum foil, placed In a hood and dried for 12 h. The
evaporating dish is lined with aluminum foil to prevent possible contamination
of the XAO-2 resin from the dish. Prerinsed aluminum foil is placed over the
XAD—2 to keep particulate matter from falling into the evaporating dish during
drying.
Glass wool (preextracted with methylene chloride as outlined in
Section 2.4.1) is placed In the bottom of a 1—L continuous extraction
column. The XAD—2 adsorbent is next placed into the column (.. 1,000 gf
extraction column). A stream of high purity gaseous nitrogen is passed for
16 h through a bed of 50% activated carbon/50% molecular seive and then
through the extraction column. The rate of N 2 flow should gently dry the
resin. Excessive fluidation may cause the XAD—2 particles to break up. The
activated charcoal/molecular sieve trap consists of a 8 x 1 1/2 in stainless
steel case with stainless steel frits on the inlet and outlet. All lines
connecting the N 2 tank to the column should be Teflon or precleaned copper
tubing.
2.1.2 Storage of Extracted XAO-2——Precleaned XAD-2 resin not to be used
immediately (within 2 weeks) should be stored under high purity methanol.
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2.1.3 Packing the XAD Trap-—
2.1.3.1 Dry method—-Place a wad of glass wool (preextracted with
niethylene chloride) into the bottom of a precleaned XAD-2 cartridge. The XAD
trap is packed just prior to use in the field (not to extend longer than
2 weeks prior to use). Use just enough glass wool to cover the glass frit.
Add XAD—2 resin to fill the cartridge to the top of the curved section. Do
not tap the cartridge . Packing the resin too tightly may plug the sample
train during sampling. Add enough glass wool (preextracted) into the top of
the cartridge to ensure the resin will not leak out. Cover both ends of the
cartridge tightly with methanol-rinsed alumirum foil. Wrap the cartridge with
bubble pack and tape to ensure safe delivery to the field site.
2.2 Cleanup and Preparation of Solid Materials Used in the Analytical
Procedures
2.2.1 The following adsorbents are to be extracted in the giant Soxhiet
extractor.
• Na 2 S0 (anhydrous, granular, Fisher Scientific or equivalent)
• Florisil (pesticide grade, 60/100 mesh)
2.2.2 Soxhiet Extraction Procedure for the ]2—L Giant Soxhiet-—
2.2.2.1 Charge the Soxhlet by adding 6 L 0CM in the 12-L round bottom
flask.
2.2.2.2 Add boiling chips (silicon c rbide) to the 12-L round bottom
flask.
2.2.2.3 Place preextracted regular glass wool in bottom of Soxhiet
extractor to prevent solids from entering inl.o the Soxhlet arm. Add the solid
material and wet with 1 L 0CM.
2.2.2.4 Extract overnight, 16 to 22 h at a turnover rate of 2 cycles/h.
2.2.2.5 Remove the solid material from the extractor and air dry in
methylene chloride-rinsed aluminum foil—lined evaporating dishes until solvent
odor is no longer detected (— 4 h).
2.2.3 Adsorbent and Drying Agent Activation Procedure—-
2.2.3.1 Na 2 SOk-—Ensure that the Na 2 SOIf is dry. Transfer the air—dried
Na 2 SOk to small tvaporating dishes and heat in a muffle furnace at 400°C for
4 h.
Store the Na 2 SOk in a clean glass jar covered with methylene chloride-
rinsed foil in an oven at 130°C.
2.2.3.2 Florisil—-Actlvate a batch of Florisil by heating at 130°C for
16 h. Store in a desiccator.
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2.2.3.3 Carbopak C/Cellte 545——Prepare by mixing 3.6 g of Carbopak C
(80/100 mesh) and 16.4 g of CelIte 545 in a 40—mL vial (different amounts may
be mixed in the same proportions). Place sorbent mixture on rock tumbler and
tumble for 3 h. Activate at 130°C for 6 h. Store in a desiccator.
2.3 Cleanup and Preparation of Glass Wool and Boiling Chips
2.3.1 Glass Wool (Soxhiet Extraction)--
2.3.1.1 Add approximately 6 L of methylene chloride to a 12-L round
bottom flask. Add boiling chips (silicon carbide) to the 12—L round bottom
flask.
2.3.1.2 Place regular or silanized glass wool in Soxhlet and wet with
1 L methylene chloride.
2.3.1.3 Extract overnight, 16 to 22 h at a rate of 2 cycles/h.
2.3.1.4 Air dry on methylene chloride-rinsed aluminum foil.
2.3.1.5 Store on bench in clean glass jar with Teflon—lined screw cap.
2.3.2 Boiling Chips——
2.3.2.1 Silicon carbide boiling chips (Soxhiet extraction)— —
2.3.2.1.1 Add approximately 500 mL of methylene chloride to a 1-L
round bottom flask. Add boiling chips (silicon carbide) to the round bottom
flask.
2.3.2.1.2 Place preextracted regular glass wool in the bottom of a
71/60 Soxhlet extractor. Add the silicon carbide boiling chips to be
extracted and wet with approximately 200 niL of methylene chloride.
2.3.2.1.3 Extract overnight, 16 to 22 h.
2.3.2.1.4 Air dry on methylene chloride-rinsed aluminum foil.
2.3.2.1.5 Store on bench in a clean glass jar with a Teflon—lined
lid.
2.3.2.2 Ben saddle boiling chips--Simply crush the Berl saddles to
small pieces and store in a methylene chloride-rinsed vial or jar with Teflon-
lined lid.
2.4 SW-846 Method Modifications, Deviations, and Enhancements
The following modifications, deviations, and enhancement from SW-846 and
other standard methods will be employed during this study. None are expected
to Impact the quality of the results submitted.
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2.4.1 Appendix A of SW—846 Method 0010 suggests two XAD—2 cleanup
methods.
2.4.1.1 Initial rinse of XAD-2 resin in Type II water (2X) in a beaker,
followed by Soxhiet extraction with water (8 h), methanol (22 h), and two
separate methylene chloride extractions, each for a duration of 22 h.
2.4.1.2 Using an XAD—2 cleanup extraction apparatus which includes a
three-necked flask, air-jacketed Snyder distillation column, and an XAD—2
canister in which the resin is held light spring tension between a pair of
coarse and fine screens. Solvent is refluxed through the Snyder column, and
the distillate is continuously cycled upward l.hrough the XAD-containing canis-
ter for extraction and returned to the flask. The resin is first water-washed
by pumping 20 L of distilled water upward through the canister. The resin Is
then solvent-rinsed with methanol and methylene chloride (2X) for 10 to 20 h
using the described distillation apparatus.
2.4.1.3 MRI will extract the XAD—2 for 22 h using methylene chloride
(Section 2.1.1). The resin purchased wil I have been precleaned by the
manufacturer. A subsample of the cleaned resin will be solvent extracted and
analyzed by GC/MS to ensure that the resin ha been efficiently cleaned.
2.4.2 Appendix A of Method 0010 sugge ts two XAD-2 drying techniques.
MRI will use a method similar to the second option recommended, modified as
follows. The high purity nitrogen will be passed through a stainless steel
case (approximately 200 cm 3 capacity) containing a mix of activated carbon and
molecular sieve (In equal proportions).
2.4.3 Method 0010 recommends that cleaned XAD-2 be stored in an
airtight, wide-mouth amber jar or in one of the glass sorbent modules sealed
with Teflon film and elastic bands for no more than 4 weeks. MRI will modify
this procedure by storing the precleaned rEsin in a jar under high purity
methanol if it will not be used within 2 week; after preparation.
2.4.4 Method 0010 recommends the use of Teflon boiling chips for all
sample preparation procedures (Soxhlet extraction, Kuderna Danish volume
reduction). MRI will use silicon carbide or Ben saddle boiling chips
instead.
3.0 EXTRACTION OF FIELD SAMPLES FOR SEMIVOLA ILE ORGANIC COMPOUNDS
3.1 Sample Train and Aqueous Sample ExtractiDn
The components of the Modified Method 5 (MM5) sampling train that need to
be extracted are as follows:
• Particulate filter/probe rinse
• XAD—2 resin/back half rinse
• Condensate water
These and several other additional aqueous samples (e.g., scrubber water, lean
water) from the trial burns will be spiked with a method internal standard
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(i.e., surrogates) compounds and solvent extracted.
be solvent-extracted using procedures consistent
while the additional aqueous and ash samples will
3500—series methods.
The MM5 components will
with SW-846 Method 0010,
be extracted using SW—846
The extracts from the MM5 sampling train components may be combined into
a single extract, thus generating a new composite, as described below.
Because they will be composited, only the particulate/XAD resin extracts will
be spiked with method internal standards.
3.1.1 Extraction of Probe Rinse and Back Half Rinse--
The probe rinse and back half rinse are treated separately but in the
same way. Each is composed of combined acetone and toluene rinses which may
contain water.
3.1.1.1
fiber filter
drains into a
in the lab
archive.
The filter and
and XAD-2 resins
the filter, if
3.1.1.3 Rinse the sample container with toluene and pour the rinsates
into the separatory funnel.
3.1.1.4 Back extract the rinses by
separatory funnel so that its volume is
rinses. Drain the acetone/water layer
funnel and save (see 3.1.1.5). Drain the
bottle.
3.1.1.5 Pour the acetone/water
extract two more times with toluene.
toluene extract from step 3.1.1.4.
adding enough reagent water to the
3X the volume of the field sample
from the bottom of the separatory
toluene phase into a separate clean
3.1.1.6 Save this extract for combination with the particulates, XAD,
and condensate extracts and proceed to Section 4.0.
3.1.1.7 At least one method blank (consisting of 1 L of reagent water
spiked with the method internal standards) is to be extracted with each set of
samples extracted by this method.
3.1.2 Extraction of Particulate Filters and XAD Resin--
3.1.2.1 Set up a i55/50 Soxhlet extraction apparatus with 200 mL toluene
in a 500-mL boiling flask along with several boiling chips. Record the
identification numbers of glassware and lot numbers of the solvent used in the
lab record book (LRB). Collect all glassware rinses and archive.
If the rinse sample contains particulate matter, set up a glass
folded in quarters and held with a powder funnel such that it
separatory funnel. Record the glassware identification numbers
record book (LRB), collect all proper glassware rinses, and
3.1.1.2 Filter the sample into the separatory funnel.
filter catch will be extracted with the particulate filter
(Section 3.1.2). Rinse the powder funnel (used to hold
applicable) with toluene into the separatory funnel.
phase back into the separatory funnel and
Combine these toluene extracts with the
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3.1.2.2 Put preextracted regular glass wool in the bottom of the Soxhiet
extractor to prevent partlculates from entering the Soxhlet arm. Confirm that
the probe rinses do not contain any particulate matter (refer to
Section 3.1.2.1). If the probe rinses contain particulates, add the filter
containing the particulates to the Soxhiet extractor.
3.1.2.3 Carefully fold the MM5 train Filter in half. Do not allow any
particulate material to be lost from the filter. Add the particulates sample
to the Soxhlet extractor using tweezers, being careful not to lose any
particulate material from the filter. Rinsi the sample container with three
5—mL portions of toluene and add to the boil ng flask.
3.1.2.4 Add the entire contents of th XAD—2 resin module (±75 g) from
the sampling train to the Soxhlet extractor. Cover the XAD-2 resin with
preextracted glass wool to ensure that the resin is held in the extractor.
Soxhlet extractors should not be filled more than one half full with resin.
Rinse the resin module thoroughly with toluerie into the Soxhlet extractor.
3.1.2.5 Spike the sample with the method internal standards (surrogate)
solution (see Tables 3 and 5).
3.1.2.6 Extract the sample for at least 16 h at a solvent cycling rate
of 3 cycles/h.
3.1.2.7 Drain the solvent extract into the boiling flask. If there is
an aqueous layer in the extract, transfer thE extract into a separatory funnel
and drain the water layer off.
3.1.2.8 Save the solvent extracts for c:ombining with the condensate, the
front half, and back half rinse extracts and proceed to Section 4.0.
3.1.3 MM5 Train Condensates--Each of the tqueous samples will be extracted
according to SW-846 3500-series methods as described below. The MM5 train
condensate samples will be extracted using 1;oluene and will be combined with
the filter, front half, and back half rinse Extracts.
3.1.3.1 Separatory funnel extraction (SW—84 —3510)- —
This method is designed to quantitati’ ely extract semivolatile organic
compounds from aqueous samples using a s!paratory funnel. If emulsions
present a significant problem during sample extraction, the sample will be
drained into a continuous liquid-liquid extractor (Section 3.1.3.2) and the
extraction continued.
3.1.3.1.1 The liquid samples will be extracted using a 2.-L separatory
funnel. Record the glassware identificatioi numbers in the LRB and collect
the appropriate glassware rinses for archiving.
3.1.3.1.2 Mark on the sample bottle the level of the meniscus for
subsequent determination of total sample volume.
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3.1.3.1.3 Shake the sample container for 30 s and pour a 1-L portion of
the sample into a graduated cylinder. Add the 1-L portion to the separatory
funnel. If the sample exhibits two separate phases, transfer the balance of
the sample to the separatory funnel. Drain each phase Into separate con-
tainers. The aqueous phase will be transferred back to the original sample
container. The organic layer will be drained into a clean bottle and treated
as described in Section 4.0.
3.1.3.1.4 Mark the level of the rneniscus on the side of the sample
container for determination of the aqueous phase volume. Measure a 1-L
portion of the aqueous phase and pour it back into the separatory funnel.
3.1.3.1.5 Spike the sample with the method internal standards mix (see
Tables 3 and 5) and gently swirl the solution. DO NOT SPIKE CONDENSATE
SAMPLES FROM THE 1 tl5 SAMPLING TRAIN WITH METHOD INTERNAL STANDARDS .
3.1.3.1.6 Check the pH of the aqueous sample using a glass stirring rod
to apply several drops of the sample to a piece of multirange pH paper.
3.1.3.1.7 Adjust the pH of the sample to about 8 using either a 6N NaOH
solution for acidic samples or a 6N H 2 S0 4 solution for alkaline samples. Add
the acid or base, swirl the contents of the separatory funnel, check the pH,
and readjust as necessary until a neutral pH is attained.
3.1.3.1.8 Add 60 mL of the extraction solvent to the original sample
container, cap, and shake 30 s to rinse it.
3.1.3.1.9 Transfer the solvent rinse to the separatory funnel and
extract the sample by shaking vigorously for 2 nun with periodic venting to
release excess vapor pressure. Record solvent lot number in the LRB.
3.1.3.1.10 Allow the organic layer to separate from the aqueous phase.
When using methylene chloride as a solvent, drain the organic phase into a
clean bottle. If the solvent employed is toluene, drain the aqueous phase
into the original sample bottle, and drain the organic phase into a clean
bottle. Transfer the aqueous phase back to the separatory funnel.
3.1.3.1.11 Repeat steps 3.1.3.1.8 to 3.1.3.1.10 two more times,
combining each of the three extracts In the same bottle and proceed to
Section 4.0.
3.1.3.1.12 At least one method blank (consisting of 1 L of reagent water
spiked with the method internal standards) is to be extracted with each set of
samples extracted by this method.
3.1.3.1.13 Measure the volume of the aqueous phase and of the total
sample described above by adding water to the sample bottle to the marks
made. Pour the water into a graduated cylinder and record the volume of
sample extracted.
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3.1.3.2 Continuous liquid extraction (SW-846-3520)—-
This method is designed to quantitatively extract semivolatile organic
compounds from aqueous samples using a continuous liquid—liquid extractor.
This method Is to be used only for samples that form emulsions when extracted
using a separatory funnel. The samples that form emulsions during
step 3.1.3.1.9 should be transferred directly to the continuous liquid
extractor and the extraction continued using the device.
3.1.3.2.1 The liquid samples will be extracted using a continuous
liquid-liquid extractor. Record the glassware identification numbers in the
LRB and collect the appropriate glassware rinses for archiving.
3.1.3.2.2 Assemble the device and add 200 mL of the appropriate solvent
to the extractor. Add 300 mL of the appropriate solvent to the 500 mL boiling
flask together with several boiling chips and install on the device.
3.1.3.2.3 Measure 1 L of sample into a 1-L graduated cylinder. If the
sample to be extracted by this method is from the separatory funnel method
described above, transfer the entire sample into the continuous liquid—liquid
extractor, rinse the separatory funnel 3X with 25 mL of solvent and proceed to
step 3.1.3.2.8.
3.1.3.2.4 Spike the sample with the method internal standards mix (see
Tables 3 and 5) and gently swirl the solu tion. DO NOT SPIKE CONDENSATE
SAMPLES FROM THE 1415 SAMPLING TRAIN WITH METHOD INTERNAL STANDARDS .
3.1.3.2.5 Check the pH of the aqueous sample using a glass stirring rod
to apply several drops of the sample to a piece of multirange pH paper.
3.1.3.2.6 Adjust the pH of the sample to about 8 usIng either a 6N NaOH
solution for acidic samples or a 6N H 2 SOk solution for alkaline samples. Add
the acid or base, swirl the contents of the separatory funnel, check the pH,
and readjust as necessary until a neutral pH is attained.
3.1.3.2.7 Transfer the sample to the extractor. Rinse the graduated
cylinder 3X with 30 mL of solvent and add to the extractor.
3.1.3.2.8 Turn on the cooling water to the condenser and the heating
mantle and extract the sample for at least 16 h.
3.1.3.2.9 Treat the sample extract as cescribed in Section 4.0.
3.1.3.2.10 At least one method blank (consisting of 1 L of reagent water
spiked with the method internal standards) i to be extracted with each set of
samples extracted by this method.
3.2 SW-846 Method Modifications, Deviations 1 and Enhancements
The following modifications, deviations 1 and enhancements from SW-846 and
other standard methods will be employed during this study. None are expected
to impact the quality of the results submittEd.
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3.2.1 SW—846 Method 3510 and 3520 require that samples extracted from an
aqueous matrix be extracted first under basic conditions and subsequently
under acidic conditions. Because of the nature of the target analytes,
performing the extractions under nonneutral pH conditions may result In their
degradation. Furthermore, the analysis is not directed toward base/neutral
and acidic compounds, but rather to neutral compounds only.
3.2.2 SW—846 Method 0010 specifies that methylene chloride be used as
the organic solvent for extraction of MM5 components. However, during the
conduct of Independent studies to test the effectiveness of various solvents
in extracting PCDD/PCOFs from dynamically spiked MM5 train components, MRI
scientists discovered that toluene is a more effective solvent. Therefore,
toluene will be used as the preferred organic solvent for extracting MM5
components.
3.2.3 SW-846 Method 0010 specifies that each individual MM5 sampling
train component be spiked with surrogates (i.e., method internal standards)
prior to solvent extraction. Analysis of each MM5 component separately would
increase analytical costs significantly. Furthermore, independent studies
conducted by MRI scientists on dynamically spiked MM5 sampling trains
indicated that the bulk of the organic analytes recovered from MM5 sampling
trains is found in the particulate filter catch and XAD-2 trap. Therefore,
the particulate filter catch will be coextracted with the XAD-2 resin
components, and only this sample will be surrogate-spiked.
3.2.4 SW—846 Method 0010 specifies that the train solvent rinses are
treated as a single sample during extraction. MRI will treat the probe and
back half rinses separately.
3.2.5 SW—846 Method 0010 specifies that, during liquid-liquid extraction
of MM5 train solvent rinses and condensate, the sample be initially extracted
under acidic conditions and subsequently under basic conditions. Since the
analytes of interest (PCDD/PCDFs, PCBs) are neutral, the samples will be
extracted under neutral conditions.
4.0 EXTRACT CONCENTRATION AND COLUMN CLEANUP FOR SEMIVOLATILE ORGANIC
COMPOUNDS
Each of the sample extracts from the various extraction procedures will
be concentrated for GC/MS analysis. Depending on the type of compounds to be
analyzed, concentration of the samples may be followed by a column cleanup
procedure and then further concentrated. Column cleanup procedures for
analysis of PCDD/PCDFs are based on those described in SW-846 Draft
Method 8290. Method 0010 for the analysis of MM5 sampling train components
has no provisions for extract cleanup. However, through long experience with
the analysis of PCDD/PCDFs, MRI chemists have determined that the MM5 samples
have sufficient Interferences that make extract cleanup compulsory.
4.1 KD Concentration of Extracts
4.1.1 Place a small plug of preextracted silanized glass wool In a
powder funnel and fill with approximately 20 g of preextracted anhydrous
granular Na 2 S0 .
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4.1.2 Transfer sample from the original extract container via the sodium
sulfate packed funnel to a 500-mL KO flask fitted with a 25-mL graduated
concentrator tube containing two clean boiling chips. Make sure the concen-
trator tube is firmly in place (with clamp or elastic bands) in order to avoid
loosing sample or allowing steam to condense in the sample. Pour In enough
sample extract to fill the KO flask no more than one—half full. Since the
volume of the MM5 sampling train extracts will likely exceed the capacity of
the KD flask, several transfers to the KD flask may be necessary.
4.1.3 Attach a 3-ball Snyder column to the KD flask and rinse with 1 mL
of the appropriate solvent.
4.1.4 Place the KD apparatus on a steam bath outlet such that the entire
lower rounded surface of the KD flask is bELthed with steam. At the proper
rate of distillation, the balls in the Snyder column will constantly chatter,
but the chambers will not flood with condensed solvent.
4.1.5 When all of the contents of the original extract containers have
been added to the KD flask, rinse the containers three times with 25 mL of the
appropriate solvent and add the rinses to the KO flask through the sodium
sulfate packed funnel.
4.1.6 Concentrate the extract to a final volume of 5 mL.
4.1.7 Add 50 mL of hexane to the KD f ask, add a fresh boiling chip to
the flask, reattach the Snyder column, and c:oncentrate the sample extract to
approximately 5 mL.
4.1.8 RInse the flask and lower joint of the KD apparatus with two 5-niL
portions of hexane and adjust the final extract volume to 20 mL.
4.1.8.1 If the sample is to be analyzed for both PCBs and
PCDO/PCOFs (composited MM5 sampling train extracts), the sample extract will
be split into two 10-mL portions. Dispense 10 niL of the extract into two
separate vials.
4.1.8.2 If the sample is to be analyzed for PCBs only (ash,
scrubber effluent, lean water samples), the ‘volume is further reduced to 10 mL
and stored in a vial.
4.2 Column Cleanup Procedures
The following column cleanup procedure is based on the methods described
in SW-846 Draft Method 8290.
4.2.1 Transfer the 10—mL aliquot of tI,e extract slated for analysis of
PCDD/PCDFs into a 125—mL separatory funnel.
4.2.2 Add 40 mL of a 20% (w/v) aqueous KOH solution to the extract.
Shake the contents for 2 mm and rapidly drain and discard the aqueous
(bottom) phase. Repeat the base washing until no color is visible in the
aqueous layer to a maximum of four washings. Strong base is known to degrade
certain PCDD/PCDFs, so contact time with the base must be minimized.
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4.2.3 After the aqueous phase of the last base washing has been drained,
add 40 mL of a 5% (w/v) aqueous NaC1 solution. Shake for 2 mm. Drain and
discard the aqueous phase.
4.2.4 Add 40 mL concentrated H 2 S0 to the sample extract. Shake for 2
mm. Drain and discard the sulfuric acid (bottom) phase. Repeat the acid
washing until no color is visible in the acid layer to a maximum of four
washings.
4.2.5 After the acid phase of the last acidic washing has been drained,
add 40 mL of a 5% (w/v) aqueous NaC1 solution. Shake for 2 mm. Remove and
discard the aqueous (bottom) layer.
4.2.6 Transfer the extract to a 50—mL boiling flask by passing it
through a powder funnel packed with anhydrous granular Na 2 SOk as described
above. Rinse the sodium sulfate with two 15-mL portions of hexane into the
boiling flask, and concentrate the sample extract to near—dryness using a
rotary evaporator (35°C water bath), making sure that all traces of toluene
(when applicable) have been removed.
4.2.7 Dry pack a gravity column (glass,. 300 mm x 10.5 mm) fitted with a
PTFE stopcock in the following manner:
4.2.7.1 Insert a precleaned plug of silanized glass wool in the
bottom of the column.
4.2.7.2 Add a 4—g layer of sodium sulfate to the column.
4.2.7.3 Add a 4-g layer of Woelm Super I neutral alumina and tap
the top of the column gently. Woelm Super I neutral alumina does not need to
be activated or cleaned prior to use, but it should be stored at all times in
a sealed desiccator.
4.2.7.4 Add a 4—g layer of anhydrous granular sodium sulfate to
cover the alumina.
4.2.7.5 Elute the column with 10 mL hexane and close the stopcock
just before the level of the solvent reaches the top layer of sodium
sulfate. Discard the eluate and check the column for channeling. If
channeling is present, discard the packing and repack the column.
4.2.8 Adjust the volume of the acid and base washed extract to 2 mL with
hexane and gently apply the extract to the top of the column. Open the
stopcock to draw the sample into the column and close the stopcock. Rinse the
sample container with three 1-mL portions of hexane and add to the column,
always drawing the rinse Into the column before applying the next rinse.
Discard the eluate.
4.2.9 Elute the column with 10 mL of an 8% (v/v) methylene chloride in
hexane solution. Collect this fraction and archive.
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4.2.10 Elute the PCDD/PCDFs from the column using 15 mL of a 60% (v/v)
niethylene chloride In hexane solution. Collect this fraction in a 15—mL
conical vial.
4.2.11 Pack a carbon column for further cleanup of the sample as
follows:
4.2.11.1 Cut off both ends of a 10—mL disposable serological pipet
such that a 4—in column remains.
4.2.11.2 Insert a preextracted silanized glass wool plug at one end
of the column and pack the column with 0.64 g of the activated Carbopak
C/Celite 545 mixture to form a 2-cm-long adsorbent bed. Cap the packing with
another silanized glass wool plug.
4.2.12 Concentrate the alumina column eluate (step 4.2.1.10) using a
nitrogen evaporator as follows:
4.2.12.1 Rinse the disposable pipEttes to be used as needles in the
N 2 evaporator with hexane.
4.2.12.2 Insert the sample vial in the rack and direct the flow of
N 2 into the sample. Adjust the flow such that gentle waves are noticeable on
the surface of the sample extract.
4.2.12.3 Concentrate the sample e>.tract to < 1 niL, add 5 mL hexane,
and concentrate to 2 mL.
4.2.13 Rinse the Carbopak C/Celite 545 column with the following
solvents:
• 5 mL toluene
• 2 mL of a 75:20:5 (v/v) methylene c:hloride/methanol/ benzene mix
• 1 mL of a 1:1 (v/v) cyclohexane/mel.hylene chloride mix
• 5 mL hexane
4.2.14 The flow rate should be les; than 0.5 niL/mm. Discard the
rinsates.
4.2.15 While the column is still wet with hexane, add the sample
concentrate to the top of the column. Rinse the sample extract container
twice with 1—mL hexane portions and add the rinsates to the top of the
column. Elute the column sequentially with:
• Two 2—mL portions of hexane
• One 2-mL portion of a 1:1 (v/v) cyclohexane/methylene chloride mix
• One 2—mL portion of a 75:20:5 (v/v) methylene chloride!
methanol/benzene mix
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4.2.16 These eluates can be collected in the same container. Archive
these the combined eluates for checks on column efficiency.
4.2.17 Invert the column and elute the PCDD/PCDF fraction with 20 niL
toluene into a 50-mL boiling flask. Verify that there are no carbon fines in
the eluate.
4.2.18 Concentrate the toluene fraction to about 1 mL on a rotary
evaporator (water bath at 50°C). Carefully transfer the sample into a
graduated 1-niL conical vial, and reduce the volume to about 100 L using a
nitrogen evaporator. Rinse the boiling flask three times with 300 L of a 1%
(v/v) toluene in methylene chloride solution and add to the cleaned-up
extract. Reduce the volume to 100 pL once again.
4.2.19 Store the sample at room temperature in the dark.
5.0 PREPARATION AND USE OF CALIBRATION STANDARDS, METHOD INTERNAL STANDARDS
(SURROGATES), AND RECOVERY INTERNAL STANDARDS
Recovery internal standards are compounds added to the native sample
matrix just prior to SC/MS analysis to determine the recovery of method inter-
nal standards and relative response factors of the calibration standards.
Method internal standards (surrogates) are compounds added to the native
sample matrix prior to sample extraction to determine if any sample matrix
effects and extraction problems prevent good recovery of the compounds from
the sample.
5.1 General Procedures for Standard Preparation
5.1.1 Preparation and/or acquisition of accurate calibration standards,
method internal standards, and recovery internal standards are extremely
crucial in achieving accurate quantification of sample components and
determination of analytical quality. It is also important that the standards
be prepared in the correct solvent, since the standards are used both for
direct analysis and for spiking.
5.1.2 As many as possible of the pure compounds and diluted calibration
standards will be obtained from the EPA Quality Assurance Branch, EMSL/CI, and
the Reference Standards Repository EPA/RIP.
5.1.3 The source, lot number, and purity of all standards will be
recorded in the LRB. All standard solutions will contain the following infor-
mation on its respective vial:
° Concentration of standard
o Date of preparation
o Solvent used
o Project number of sample ID
o InitIals of person preparing solution
° Expiration date of solution
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5.1.4 Primary stock solutions of the various target analytes will be
prepared. All neat standards will be weighed on an analytical balance and
diluted to the mark in a Class A volumetric flask with the appropriate
solvent. Secondary standard mixes will be prepared by combining the
appropriate volumes of the primary stock solutions in a Class A volumetric
flask and diluting to the mark with the appropriate solvent.
5.1.4.1 Calibrate the analytical balance prior to weighing
standards by using certified Class S weights which are in the range of the
standard weighings.
5.1.4.2 Dilutions of the secondary standard mixed solutions will be
prepared by serial dilution. Preparation of final working solutions will be
recorded and dilution records maintained.
5.1.4.3 The various standard solutions will be stored at 4°C in a
Teflon-lined screw-cap amber vial with the solution level marked on the vial.
5.2 Standards Used in the Analysis of PCDD/PCDF Organic Compounds
The semivolatile organic compounds con lst of liquids and solids. The
solid and liquid compounds will be weighed and diluted to volume in Class A
volumetric flasks. Wash all glassware used in the standard preparation as
outlined in Section 1.2.2 of Section 1.0. ll standards are stored at 4°C
in amber vials with Teflon—lined screw cap.
Recovery internal, method internal (surrogate), native calibration and GC
performance check standard solutions for PCDD/PCDF analysis should be obtained
from the MRI repository of dioxin/furan s:andards. See Table A4-1 for a
complete list of dioxin/furan analytes, method internal standards, and
recovery internal standards. Dioxin/furan native calibration standard, method
internal standard (surrogate) and recovery internal standard solutions will
be:
• Dissolved in anisole or toluene and diluted with tridecane for
analysis by GC/MS. The method inl.ernal standards will be prepared
in isooctane for spiking into samples.
• Prepared in quantities of at lea;t 1 mL. Prepare enough method
internal standard to last the entire project.
• Prepared in concentrations listed in Table A4-2. Each working
standard solution will be prepared to contain the same concentration
of each of the isotopically stable labeled method internal standards
but a different concentration of native calibration standards. The
ratio of native calibration stanthirds to method internal standards
will range from 0.05 to 4.
• Replaced after 6 months or sooner if comparison with quality control
check samples indicates compound degradation or concentration
change.
The GC performance check mixture will be per Table A4-3 with each isomer
at a concentration equivalent to DF5O from T tble A4-2.
A-97
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TABLE A4-1. LIST OF ANALYTES, METHOD INTERNAL STANDARDS (SURROGATES), AND RECOVERY
INTERNAL STANDARDS FOR DIOXIN/FURAN ANALYSIS
Analyte
Compounds in
calibration standard
Method
internal standarda
Recovery
internal standardb
Tetra—COD
Tetra—CDF
2,3,7,8-TCDD
2,3,7,8—TCDF
‘ C 12 —2,3,7,8—TCDD
‘3C 12 —2,3,7,8—TCDF
13C 12 _1,2,3,4_TCDDc
Penta—CDD
Penta—CDF
Penta CDF
1,2,3,7,8—PeCDD
1 ,2,3,7,8—PeCDF
2,3,4,7,8—PeCDF
‘ C 1 2 1 ,2,3,7,8—PeCDD
‘ C 1 2 1 ,2,3,7,8—PeCDF
Hexa—CDD
Flexa—CDD
Hexa-CDD
Hexa-CDF
Hexa-CDF
Hexa-CDF
Hexa-CDF
1,2,3,4,7,8—HxCDD
1,2,3,6,7,8—HxCDD
1,2,3,7,8,9—HxCDD
1,2,3,4,7,8—HxCEJF
1,2,3,6,7,8—HxCDF
2,3,4,6,7,8—FIxCDF
1,2,3,7,8,9-HxCDF
‘3C 12 —1,2,3,6,7,8—HxCDD
‘ C 12 —1,2,3,4,7,8—HxCDF
13C 12 _1,2,3,7,8,9_HXCDDC 1
Hepta-CDO
Hepta—COF
Hepta—COF
1,2,3,4,6,7,8—HpCDD
1,2,3,4,6,7,8—HpCDF
1,2,3,4,7,8,9—HpCDF
‘3C 12 -1,2,3,4,6,7,8—HpCDD
‘3C 12 —1,2,3,4,6,7,8—HpCDF
Octa—CDO
Octa-CDF
OCDD
OCDF
‘ C 12 —OCDD
a Added to sample prior to extraction.
b Added to sample at time of injection into GC/MS.
C Used for recovery determinations of TCDD, TCDF, PeCDD, and PeCDF method internal
standards.
d Used for recovery determinations of HxCDD, HxCDF, HpCDD, HpCOF, and OCDD method
Internal standards.
A-98
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TABLE A4-2. SUGGESTED CONCENTRATIONS OF CONGENERS IN TCOD/TCDF-OCDD/OCDF
CALIBRATION STANDARDS, METHOD INTERNAL STANDARDS (SURROGATES), AND RECOVERY
INTERNAL STANDARDS FOR SIM ANALYSIS
Concentration (pg/pL)
Compound DF2.5 0F5 OF1O DF5O 0F200
Unlabeled Analytes
23,7,8—TCDD 2.5 5 10 50 200
2,3,7,8—TCDF 2.5 5 10 50 200
1,2,3,7,8—PeCOD 2.5 5 10 50 200
1,2,3,7,8—PeCDF 2.5 5 10 50 200
2,3,4,7,8—PeCDF 2.5 5 10 50 200
1,2,3,4,7,8—HxCDD 6.25 12.5 25 125 500
1,2,3,6,7,8—HxCDD 6.25 12.5 25 125 500
1,2,3,7,8,9—HxCDD 6.25 12.5 25 125 500
1,2,3,4,7,8—HxCDF 6.25 12.5 25 125 500
1,2,3,6,7,8—HxCDF 6.25 12.5 25 125 500
1,2,3,7,8,9—HxCDF 6.25 12.5 25 125 500
2,3,4,6,7,8-HxCDF 6.25 12.5 25 125 500
1,2,3,4,6,7,8-HpCDD 6.25 12.5 25 125 500
1,2,3,4,6,7,8—HpCDF 6.25 12.5 25 125 500
1,2,3,4,7,8,9-HpCDF 6.25 12.5 25 125 500
OCDD 12.5 25 50 250 1,000
OCDF 12.5 25 50 250 1,000
Internal Standards
‘3C 12 —2,3,7,8—TCDD 50 50 50 50 50
‘3C 12 —2,3,7,8—TCDF 50 50 50 50 50
‘3C 12 —1,2,3,7,8—PeCDD 50 50 50 50 50
‘3C 12 —1,2,3,7,8—PeCDF 50 50 50 50 50
‘3C 12 —1,2,3,6,7,8—HxCDO 125 125 125 125 125
‘3C 12 —1,2,3,4,7,8—HxCDF 125 125 125 125 125
‘3C 12 —1,2,3,4,6,7,8—HpCDD 125 125 125 125 125
‘3C 12 —1,2,3,4,6,7,8—HpCDF 125 125 125 125 125
‘ C 12 —OCDD 250 250 250 250 250
Recovery Standards
13C 12 _1,2,3,4_TCDDa 50 0 50 50 50
13C 12 _1,2,3,7,8,9_HXCDDb 125 125 125 125 125
a Used for recovery determinations of TCDD, TCOF, PeCDD, and PeCDF internal
standards.
b Used for recovery determinations of HxCDD, HxCOF, HpCDD, HpCDF, and OCDD
internal standards.
A-99
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TABLE A4-3. PCDD AND PCDF CONGENERS PRESENT IN THE GC PERFORMANCE
EVALUATION SOLUTION AND USED FOR DEFINING THE HOMOLOGOUS GC
RETENTION TIME WINDOWS ON A 60-rn DB-5 COLUMNa
No. of
chlorine
atoms
PCDD—positional isomer
PCDF-posltlonal isomer
Early eluter
Late eluter
Early eluter
Late eluter
4 b
1,3,6,8
1,2,8,9
1,3,6,8
1,2,8,9
5
1,2,4,6,8/
1,2,4,7,9
1,2,3,8,9
1,3,4,6,8
1,2,3,8,9
6
1,2,3,4,6,8
1,2,3,4,6,7
1,2,3,4,6,8
1,2,3,4,8,9
7
1,2,3,4,6,7,8
1,2,3,4,6,7,9
1,2,3,4,6,7,8
1,2,3,4,6,7,9
8
1,2,3,4,6,7,8,9
1,2,3,4,6,7,8,9
a Tetra— and penta-CDD and CDFs will be at 50 pg/uL, hexa- and hepta—
CDD and CDFs will be at 125 pg/pL, and octa-CDD and CDFs will be at
250 pg/uL.
b In addition to these two PCDD isomers, the 1,2,3,4—, 1,2,3,7—, 1,2,3,8—,
2,3,7,8—, ‘ C 12 —2,3,7,8—, and 1,2,3,9—TCDD isomers must also be
present.
A-100
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6.0 GC/MS ANALYSIS OF PCDD/PCDFs
Analysis for PCDD/PCDFs will be performEd in accordance to SW-846 Draft
Method 8290. This method employs high resolution gas chromatography! high
resolution mass spectrometry techniques to measure parts-per--trillion and
lower levels of PCDD,1PCOFs in soil, sediment, and aqueous samples. MRI has
adapted the method for analysis of PCDD/PCDFs in MM5 sampling train
components.
MRI will use in-house developed softw tre to reduce and quantify the
results for all samples. In addition, the data from a selected number of
samples will be reduced manually to validate t.he results obtained from the MRI
developed software.
6.1 Instrument Requirements and Operating Conditions
The following analytical instrument requiirements and operating conditions
will be used for the analysis of PCDD/PCDFs by GC/HRMS.
• Mass spectrometer--double focusing, capable of maintaining static
resolving power at a minimum of 10,000 (10% valley). Should be
operated in the electron impact mode at a nominal electron energy of
70 eV. The mass spectrometer must be operated in the selected ion
monitoring (SIM) mode. System must be capable of acquiring data at a
minimum of 10 ions per scan.
• Scan time--i s or less (including voltage reset time).
• Scan range-—202 to 472 amu, SIM mode monitoring the ions listed in
Table A4-4.
• Resolution—-i0,000.
• Analytical column—-IJB—5, 60—rn x 0.32--mm ID, 25—urn film thickness.
• Carrier gas—-Helium, 20 to 40 cm/s.
• Injector——Grob type, splitless mode 1 it 270°C, splitless valve time of
45 s.
• Injection volume—-i to 2 pL, same volume used for all standards and
samples.
• Transfer line temperature--350°C.
• Temperature progran--200°C (2-mm hold), increase to 220°C at 5°C/mm
(16-mm hold), increase to 235 at 5°C/mm (7-mm hold), increase to
330°C at 5°C/mm (5—mm hold).
A— 101
-------
TABLE A4—4. IONS MONITORED FOR HRGC/HRMS ANALYSIS OF PCDD/PCOFs
(S = INTERNAL/RECOVERY STANDARD)
Accurate(a)
Mass
303.9016’
305.8987
315.9419
317.9389
319.8965
321.3936
331.9368
33.3.9339
375.8364
[ 354.9792]
Ion Elemental
ID Composition
H C 12 H 4 35 C . 4 0
M+2 C 12 H 4 35 C1 3 37 C10
H 3 C 12 H 4 35 Cl 4 0
P1+2 13 C 12 H 4 35 C]. 3 37 C10
N C 12 H 4 35 C1 4 0 2
N+2 C 12 H 4 35 C1 3 37 C10 2
N 13 C 12 H 4 35 C1 4 0 2
P1+2 13 C 12 H 4 35 C1 3 37 C10 2
P1+2 C 12 M 4 35 C1 6 0
LOCK C 9 F 13
T DF
ZCDF
TCDF CS)
TCDF (5)
TCDD
TCDD
TCDD (s)
TCDD (S)
HxCDFE
?FK
C 12 H 3 35 ci 4 37 cio
,- 35.— 37 _,
12”3 3 2
13 C 12 H 3 35 C1 4 37 0] .O
13 35 37
C 12 M 3 Cl 3 C1 2 0
C 12 H 3 35 C1 4 37 C1.0 2
C 12 H 3 35 C’ 3 37 C’ 2 0 2
13,- H
12 3 4
13 c H 35 ci. pci. o
12 3 3 2 2
C 12 H 3 25 C1 7 0
PeCDF
PeCDF
PeCDF
PeCDF
PeCDD
PeCDD
FeCDD (5)
PeCDD (S)
HpCD FE
(Coacinucd)
Descriptor
1
Analyts
2 339.8597
P1+2
341.8567
Mr4
351.9000
P1+2
353.8970
P1+4
355.8546
P1+2
357.8516
N+4
367.8949
P1+2
369.8919
P1+4
409.7974
P1+2
(5)
Cs)
(35 4.9792J
LOCK C 9 F 13
A-102
-------
TABLE A4—4 (continued)
Ac ura :e
Nass
373.8208
375.8178
383.8642
385.8610
389.8.156
391.8127
431.8559
403.8529
645.7555
[ 354.979z LOCK
407.7818
409.7789
417.8253
419.8220
423.7766
425. 7737
435.8169
437.8140
479. 7165
[ 430.9728)
El e men: a 1
Comoos I tion
C 12 R 2 35 C 1 5 37 C1 0
C 12 H a 35 d1 4 37 c1 2 0
13 C 12 H 2 35 c1 6 o
Cl 5 dO
C 1 2 11 2 35 C1 5 37 C10 2
C 12 H 2 35 C 1 4 37 C1 2 o 2
13 35 37
C 12 11 2 Cl 5 C_C 2
13 35 37
C 12 }i 2 Cl 4 C1 2 0 2
C 12 11 2 35 C1 6 37 C1 2 0
Cl 2 1 35 Cl 6 37 Cl0
C 12 H 35 C1 5 37 C1 2 0
l 3 c’ a 35 c l 7 o
13 c 12 a 35 c1 6 37 c 10
C 12 H 35 C1 6 37 C10 2
C 12 H 35 C1 5 37 C 1 2 0 2
13 c 12 H 35 cl 6 cio 2
13 35 37
C 12 H Cl 5 C1 2 0 2
C 12 M 35 C1 7 37 ci.,o
C 9 F 17
Analy te
xCDF
RxCD F
HxCDF (5)
HxCDF (S)
lixCDD
lixCDD
lixCDD (S)
lixCDD (5)
OCDFE
PFK
HpCDF
lipCDF
lip CD F
lip CDF
lip CDD
MpCDD
IIpCDD
lip CDD
NCDPE
PFK
(Continued)
Descriptor
Ion
ID
fl+2
M+4
M+2
M+ 2
M+4
N +4
N+4
3
4
C 9 F j 3
N+2
N
N+2
M+2
N+4
M+4
LOCK
(S)
(5)
(5)
(5)
A-103
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TABLE A4-4 (continued)
Accurate
Mass
441.7428
“3.7399
457.7377
459. 7348
469.7779
471.7750
513.6775
(a)The following nuclidic
H — 1.007825
C — 12.000000
13C — 13.003355
Analyt e
OCDF
OCOF
OCD D
OCDD
OCDD
CCDD
DCDPE
PFK
Descriptor
5
Ion
ID
N+2
M+4
M+2
M+4
M+2
M+4
LOCK
Elemental
Composition
c 12 35 c1 7 37 c 10
C 12 35 c1 6 37 C 1 2 0
C 12 35 C1 7 37 c1o 2
C 12 35 C1 6 37 C 1 2 0 2
13 35 37,
C 12 Cl 7 C 4 .0 2
13 .35 37
C 12 Cl 6 C1 2 0 2
C 12 35 C 1 8 37 C 1 2 0
C 9 F 17
(s)
(5)
masses
0
35 C].
37 c1
were used:
— 15.994915
— 34.968853
— 36.965903
A-104
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6.2 Instrument Tuning and Calibration
The GC/MS must be tuned and calibrated every day during which samples are
to be analyzed. The following tests must be performed at the beginning and
end of each 12—h period (except as specified below) of sample analysis.
6.2.1 Mass Calibration--
The following tests are used to check the mass spectrometer’s resolving
power and mass accuracy. These tests are conducted because the mass of the
ions monitored are exact (to four decimal places), and even slight instru-
mental drift may result in incorrect masses being monitored. These tests are
to be performed at the beginning and end of each 12—h period of consecutive
analysis.
6.2.1.1 Introduce a small amount of PFK (perfluorokerosene) into the
system by molecular leak. The level of PFK introduced into the system should
be adjusted so that the amplitude of the m’Dst intense lock-mass ion signal
does not exceed 10% of the full-scale deflection.
6.2.1.2 The mass resolution check is a’:complished by recording the peak
profiles of m/z 304.9824 and 380.9760 of PFK on a calibrated mass scale
(horizontal axis, amu or ppm per division) and measuring the width of the
latter peak at the 5% abundance level over a 200-ppm range. The peak width
must not exceed 100 ppm (or 0.038 amu).
6.2.1.3 Confirm that the exact mass of m/z 380.9760 is within 5 ppm of
the required value.
6.2.2 GC Column Performance Check—-
A GC column performance check mixture c:ontains the known first and last
chromatographic eluters for each group of PCDO/PCDF congeners, such that all
of the congeners within a homologous series will elute between the first and
last eluters. In addition, the GC performance check mixture contains 2,3,7,8-
TCOD and several other TCDD congeners which elute close to 2,3,7,8-ICOD. This
solution is analyzed to establish the retention times at which the ions
monitored will be switched to a different set of ions, and also to determine
the chromatographic resolution between 2,3,7,8—TCDD and the closest eluting
TCDO congener. The GC column performance mix will be analyzed once at the
beginning of each 12-h analysis, after performing the mass resolution and
accuracy test described above.
6.2.2.1 Inject 2 pL of the GC perforniance check mixture (Table 3) and
acquire SIM data as described in Table 4.
6.2.2.2 Determine the chromatographic resolution between 2,3,7,8-TCDO
and the closest eluting TCOD peak. This is accomplished by the following
equation:
A-105
-------
Resolution (% valley) = (x ÷ y) x 100
where: x = total height of the valley (from baseline) separating
2,3,7,8—TCDD and the closest eluting TCDD
y = total peak height (from baseline) of 2,3,7,8—TCDD
6.2.2.3 The resolution must be 25%.
6.2.2.5 Allowable tolerance on the daily verification of the GC per-
formance check mixture will be ±10—s drift on the absolute retention times of
all components.
6.2.3 Instrument Calibration--
Before any samples can be analyzed, an initial five—point calibration
will be performed. This calibration will be verified at the beginning and end
of each 12—h period of sample analysis.
6.2.3.1 Initial calibration—-Initial calibration is required before any
samples may be analyzed, but after all of the tests described above have been
successfully completed. Initial calibration is also required if any
continuous calibration check is not successful.
6.2.3.1.1 Analyze 2 pL of each of the five calibration solutions.
Note that prior to analysis, each solution must be spiked with the appropriate
amount of the recovery Internal standards mix (50 py/uL of ‘ C-1,2,3,4-TCOD
and 125 pg/ijL of ‘3C—1,2,3,7,8,9—HxCDD).
6.2.3.1.2 Confirm that the ratio of the areas for each of the two
ions monitored for each homologous set of congeners and for the ‘ 3 C-labeled
internal standards are within the control limits indicated in Table A4-5.
6.2. 3. 1.3
target compound is
Confirm that the signal-to-noise (S/N) ratio for each
> 2.5.
6.2.3.1.4 Calculate the relative response factors (RRF) for each of
the 17 unlabeled PCDD/PCDF target analytes relative to the appropriate method
internal standards (surrogates) and for each of the 9 labeled PCDD/PCDF
internal standards relative to the appropriate recovery internal standards.
RRF and the
compound.
average RRFs
relative
initial
20%.
6.2.2.4 Determine the retention time (or scan number) of the first and
last eluter for each homologous series. Print out an RIC (reconstructed ion
chromatogram) for each of the five homologous series (CL, to Cl 8 ) and label
each peak together with an “F” for the first eluter and an “L” for the last
eluter in the series. These retention times will be used to establish the
switching times for the SIM descriptors.
6.2.3.1.5 Calculate the average
standard deviation (RSD) for each target
calibration to be acceptable, the % RSD of the
percent
For the
must be <
A-106
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TABLE A4—5. THEORETICAL ION ABUNDANCE RATIOS AND THEIR
CONTROL LIMITS FOR PCODs AND PCDFs
Number
of
C 1orine
Atou s
Ion
Type
Theoretical
Ratio
Control
Li iits
lower
upper
H
4 0.77 0.65 0.89
M+2
5 1.55 1.24 1.86
H+4
6 1.2’ . 1.05 1.43
H
6(a) —— 0.51 0.43 0.59
H
7(b) 0.4i 0.37 0.51
N+2
7 —— 1.04 0.88 1.20
H+4
Z1+2
8 0.89 0.76 0.89
fl+4
(a)Used only for 13 C—HxCDF (IS).
(b)used only for 13 C—HpCDF (IS).
A-107
-------
6.2.3.2 Continuing calIbration-—Continuing calibration must be conducted
at the beginning of each 12—h period of analysis after successful mass
accuracy and resolution GC resolution performance checks. Continuous
calibration is also required at the end of a 12—h shift, before the final mass
resolution and accuracy check. If the continuing calibration does not meet
criteria, the initial calibration must be repeated and the samples reanalyzed
except as noted below.
6.2.3.2.1 Analyze 2 L of the midlevel calibration
that prior to analysis, each solution must be spiked with
amount of the recovery internal standards mix (50 pg/pL of
and 125 pg/pL of ‘3C—1,2,3,7,8,9—HxCDO).
6.2.3.2.2 Confirm that the ratio of the areas for
ions monitored for each homologous set of congeners and for
internal standards must be within control limits.
solutions. Note
the appropriate
‘3C-1,2,3,4—TCDD
each of the two
the ‘ 3 C-labeled
6.2.3.2.3 Calculate the relative response factors (RRF) for each of
the 17 unlabeled PCOD/PCDF target analytes relative to the appropriate method
internal standards (surrogates) and for each of the 9 labeled PCDO/PCDF
internal standards relative to the appropriate recovery internal standards.
6.2.3.2.3.1 For the continuing calibration to be acceptable,
the RRFs must be within ±20% of the average RRF from the initial calibration.
6.2.3.2.3.2 If the end—of-the-day continuing calibration check
standard has RRFs that are not within 20% but are within ±25% of the average
RRF from the curve, samples analyzed during that 12-h period will be calcu-
lated using the average RRF from the beginning-of—day and the end-of—day stan-
dards.
standard has
all positive
be reanalyzed.
6.2.3.2.3.3 If the end-of-day continuing calibration check
RRFs that are not within 25% of the average RRF from the curve,
samples analyzed during that 12-h period are invalidated and must
6.3 Sample Analysis
Samples may be analyzed
requirements have been met.
before any samples can be injected.
only after the initial tuning and calibration
In addition, a solvent blank must be analyzed
6.3.1 Adjust the volume of each sample to be analyzed to the final
amount.
6.3.2 Add recovery internal standards to each sample
such that there are 50 pg/pL of ‘ C-1,2,3,4—TCDD and
1,2,3,7,8,9-HxCDD.
Inject 2 L of a hexane solvent blank. If the the blank contains
2,3,7,8—substituted congeners at more than 10% of the detection
results of all positive samples analyzed on that 12-h shift are
and will require reanalysis.
6.3.3
any of the
limit, the
invalidated
or portion thereof
125 pg/pL of ‘IC—
A-108
-------
6.3.4 Analyze 2 pL of each sample.
6.4 Data Reduction
Data reduction of each sample run con5ists of confirmation of target
compounds identification and quantification of the compounds detected.
6.4.1 DocumentatIon—-
For each sample analyzed, the following documentation must accompany
analytical results for the purpose of their v ulidation.
6.4.1.1 Reconstructed ion chromatogram (RIC) with a header
identifying the sample or standard by a uniqw laboratory designator.
6.4.1.2 Extracted current ion profiles (EICPs) for each compound
detected within the appropriate retention time window. For each compound,
there must be one EICP page which will include the name of the compound
monitored in the page header, and the following information. All peaks must
include scan numbers and areas found. The primary and secondary quantitation
ions must be printed together with the appropriate PCDPE interferent ion.
6.4.2 Compound Identification Criteria-—
For a GC peak to be positively identified as a PCDD/PCDF, it must meet
all of the following criteria:
6.4.2.1 For 2,3,7,8-substituted congeners which have an equivalent
‘ 3 C-labeled method or recovery internal standard In the sample extract, the
retention times of the unlabeled congeners m’jst be within —1 and +3 s of the
retention time of the equivalent ‘IC-labeled congener.
6.4.2.2 For 2,3,7,8-substituted congeners that do not have an
equivalent ‘ 3 C-labeled congener in the sample extract, the relative retention
time (RRT) of the unlabeled congener must be within the established GC reten-
tion window for its homologous series.
6.4.2.3 For non-2,3,7,8—substituted congeners, the retention time
must be within the established GC retention window for its homologous series.
6.4.2.4 The ion current responses for the primary and secondary ions
used for confirmation and quantification purposes must reach their apex within
±2 s of each other.
6.4.2.5 The ion abundance ratios of both ions used for quantitative
purposes must be within the tolerance llmizs for the homologous series to
which the peak is assigned.
6.4.2.6 Signal—to—noise ratios must be 2.5 for compounds
tentatively identified.
A-log
-------
6.4.2.7 Because polychiorinated dlphenyl ethers (PCDPE) are a common
interferent for analysis of PCDFs, the extracted ion current plot of the
corresponding PCDPE must have a S/N ratio < 2.5.
6.4.3 QuantifIcation--
The amount of each 2,3,7,8-substituted congener included in the
calibration standards will be calculated together with total tetra— to octa-
PCDD/PCOFs using the formula:
— ( area guantitation x amount internal standard [ j g )
x — (area internal standard X RRF average x amount extracted [ g or LI)
where: Cx = concentration [ pg/g or pg/LI or total amount [ pgj
found in the sample. If convenient, the units may be changed
to reflect the magnitude of the value of Cx.
RRFaverage is the average RRF for each individual congener
the calibration mixtures or is representative of the RRF for
that homologous group of congeners.
• For congeners that belong to a homologous series con-
taining only one isomer (i.e., OCOD and OCDF) or only one
2,3,7,8—substituted congener (TCDDs, PeCDDs, HpCODs and
TCDFs), the average RRF to be used will be the same as
that used for the individual compounds.
• For congeners that belong to a homologous series con-
taining more than one 2,3,7,8—substituted congener (I.e.,
HxCDD, PeCDF, HxCOF, and HpCDF), the average RRF to be
used will be the mean of the average RRFs calculated for
the 2,3,7,8-substituted congeners representative of that
homologous series analyzed during calibration.
• Please be sure to note Sections 6.2.3.2.3.1 to 6.2.3.2.3.3
for specific cases in which the average RRF from the curve
will not be used.
6.5 SW—846 Method Modifications, Deviations, and Enhancements
The following modifications, deviations, and enhancements from SW—846 and
other standard methods will be employed during this study. None are expected
to impact the quality of the results submitted.
6.5.1 Method 8290 specIfies that before any samples are analyzed, a
method blank associated to the samples be analyzed. MRI will instead analyze
a solvent blank to confirm that there is no carryover in the chromatographic
system. If any method blank presents contamination problems, the specific
causes of the problem will be investigated and reported.
A-lb
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APPENDIX A—5
bC ANALYSIS METHODS
A-ill
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Geochemical and Environmental Research
Group
Page 1 of 6
STANDARD OPERATING PROCEDURES
SOP- 8907
TOTAL ORGAMC AND CARBONATE
CARBON
CONTENT OF
SEDIMENTS
1.0 INTRODUCTION
Precise measurements of total organic arid carbonate carbon are
necessary for interpreting trace organic contamination. Carbon
concentrations are determined on freeze-d ded (or oven-dried at 40°
to 50°C) sediment using a LECO Model 523-300 induction furnace (or
equivalent) to burn samples in an oxygen atmosphere. The carbon
dioxide that is produced is swept out of the furnace’s combustion
chamber by the oxygen flow. The gases then pass through a dust trap
and two reaction tubes. The first of these Is a two-stage chamber with
the first stage consisting of manganese dioxide. The manganese
dioxide absorbs the sulfur oxides that may have formed during
combustion. The second stage Is made of anhydrone which removes
water vapor from the gas stream. The second tube, filled with
platinized silica, is maintained at an elevated temperature by an
external heating case. The contents of this tube act as a catalyst to
convert any carbon monoxide present into carbon dioxide. Carbon
dioxide is detected and quantified with a Horiba PIR-2000 Infrared
detector. The output signal from the Horiba is sent to a HP 3396A
integrator which reports the quantity of carbon dioxide as a peak area.
Total organic carbon Is determined after sample acidification.
Carbonate carbon is determined as the diffemence between total carbon
and total organic carbon.
2.0 SAMPLE COLLECTION, PRESERVATION AND STORAGE
2.1 Sample Collection
Sediment should be collected in precleaned and/or pre-
combusted (400°C) glass jars, or core liners and frozen (-20°C) In the
field.
2.2 Sample Preservation and Storage
Sediment samples are shipped frozen to the laboratory and
stored at -20°C until analysis. After subsampling excess sample is
archived at -20°C in the dark.
Rev. 1 November 1989
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STANDARD OPERATING PROCEDURES SOP-8907
3.0 APPARATUS AND MATERIALS
3.1 Labware and Apparatus
The following labware and equipment is needed to perform the
total organic carbon and total carbon analyses:
Freeze Drier: Capable of freeze drying sediment at -40°C.
Mortar and Pestal: 500-mi mortar or other suitable container.
LECO Model 523-300 Induction Furnace
Horiba PIR-2000 Infrared Detector: Or other suitable detector.
HP 3396A Integrator: Or other suitable recorder/integrator.
Glass Measuring Scoop
Drying Oven: Capable of maintaining 400 to 50°C.
AnRlytical Balance: Capable of weighing to 1 mg.
Rotanieter: Part No. 112-02, Cole-Parmer, Inc.
Flow Controller: Part No. 42300513, Veriflo Corp.
Note: Volumetric glassware for accelerator measurement and
analytical balances must be calibrated.
3.2 Reagents
The following reagents are required:
10% HC1 in Methanol (V:V)
LECO Iron Chip Accelerator: Part No. 501--077, Leco Corp.
LECO Copper Metal Accelerator: Part No. 50 1-263. Leco Corp.
LECO Combustion Crucibles
LECO Pin and Ring Carbon Standards: Range: 0.1 to 1.0% carbon.
Rev. 1
November 1989
A-114
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Geochemical and Environmental Research Group Page 3 of 6
STANDARD OPERATING PROCEDURES SOP-8907
4.0 PROCEDURE
4.1 Leco System Preparation
The first step in operating the LECO furnace is to turn It on by
flipping all switches on the front panel to the “ON” (up) position. The
“Grid Tap Switch” should be set to the “MED” position. The
instrument then needs a warm-up period of at least 30 minutes. When
the furnace has had time to warm-up, close the oven on the right side
of the instrument (pedestal up) and open the valve on the oxygen tank;
set the regulator pressure to 40 psi. Open the toggle valve and allow
oxygen to flow through the system for 15 seconds and then check the
flow rate using the rotameter. Set to the 150 mark on the rotameter
tube with the knob on the flow controller to the right of the
rotameter. After 30 seconds of correct flow, zero the panel meter on
the front of the Horiba Infrared Analyzer. Set the Horiba Infrared
Analyzer detector range to 3, and the span to 0.
4.2 Total Carbon Determination
4.2.1 Sample Preparation
Weigh 10 to 500 mg of freeze dried (or oven dried) sediment
into a tared crucible. The amount of sample depends upon the
expected carbon concentration. Ideally between 0.5 mg and 8.6 mg of
carbon should be combusted to fall within the range of the standard
curve.
Add one scoop each of the copper and iron chip accelerators to
all the weighed crucibles containing samples. All crucibles should be
kept covered with aluminum foil prior to analyses.
4.2.2 Sample Analyses
Place the crucible on the oven pedestal. Close the oven and start
the oxygen flow. Allow the oxygen to flow for 15 seconds and then
check the flow rate on the rotameter and adjust the flow, if needed.
After 15 seconds of correct flow, push the pedestal lever in to start
the induction furnace. At the same time push the “START’ button on
the HP integrator. About 20 seconds after the furnace is activated the
metals should begin to burn. After about another 20 seconds the
detector should begin to register carbon dioxide in the gas flow and
the integrator should begin to show a peak. At this point carefully pull
the lever out to turn the furnace OFF -- be sure that you don’t open the
Rev. 1 November 1989
A—115
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Geochemical and Environmental Research Group Page 4 of 6
STANDARD OPERATING PROCEDURES SOP-8907
combustion chamber. Once the integrator has returned to baseline,
carefully open the oven and press STOP on the integrator. Use a pair
of large tweezers or tongs to take the hot crucible off the oven
pedestal and place it on a non-flammable heat-resistant surface to cool.
Repeat this procedure for all crucibles to be run.
4.2.3 Standard Analyses
Stardard Leco pin and ring carbon standards are placed into an
empty crucible with one scoop of the copper accelerator. Standards
are analyzed per the identical procedure as outlined in Section 4.2.2.
4.3 Total Organic Carbon Determination
4.3.1 Sample Preparation
Weigh an appropriate amount of freeze dried (or oven dried)
sample as per step 4.2.1 into a tared crucible. Add small amounts of
10% HC1 in methanol solution slowly to the sample until all bubbling
stops. Use a minimal amount of acid. Dry the treated samples
overnight at 50°C in the drying oven.
4.3.2 Sample Analyses
Combust and analyze as indicated in Section 4.2.2.
4.3.3 Standard Analyses
Standards are analyzed per the identical procedure as outlined
in Section 4.2.3.
4.4 Total Carbonate Carbon Content
Carbonate content Is determined by subtracting the total organic
carbon concentration from the total carbon concentration. To express
as percent calcium carbonate, instead of total carbonate carbon
content, multiply this result by 8.33.
5.0 STANDARDIZATION AND CALCULATIONS
Prior to combusting samples, a set of standards is run to
determine a standard curve. Standard curves vary slightly from day to
day.
Rev. 1 November 1989
A-116
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Geochemical and Environmental Research Group Page 5 of 6
STANDARD OPERATING PROCEDURES SOP-8907
5.1 To determine the curve, combust a set of five standards at
varying concentrations. Several standard rings and/or pins may need
to be run initially to bring the system to correct operating conditions;
the data collected will be discarded. The values of the standards in
the set should be selected to cover the 0.1 to 1.0% carbon range (1
gram basis).
5.2 A graphics package on a Macintosh (such as Kaleidagraph)
is used to make a graph of carbon percentage vs. integrator counts.
This software is used to determine a best fit equation for the data. R
should be no less than .99 or the data set should be discarded and
another set of five calibration points should iDe run and plotted. This
equation will be used to determine the carbon percentage of samples
for that day.
5.3 The counts reported by the Integrator for a sample are
simply entered for X in the equation and Y becomes an intermediate
value. The Y value Is divided by the sample weight in grams to
determine the percent carbon.
6.0 QUALITY CONTROL
Quality control samples are processed in an identical manner as
the actual samples.
6.1 A method blank is run with every 20 samples, or with
every sample set, whichever is more frequent. Blank levels should be
no more than 3x method detection limit (MDL).
6.2 Duplicate samples are run every 20 samples, or with every
sample set. Duplicates should be ± 20% for low level (<1.0% carbon)
samples and ± 10% for normal/high level (>1.0% carbon) sample.
Duplicates may be somewhat less precise for very inhomogeneous
samples (i.e., peats, samples containing twigs, grasses, etc.).
6.3 Reference Materials: Leco pin and ring carbon standards
are run as reference materials and standards.
Rev. 1 November 1989
A-117
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Geochemical and Environmental Research Group Page 6 of 6
STANDARD OPERATING PROCEDURES SOP-8907
7.0 REPORTNG AND PERFORMANCE CRITERIA
7.1 ReportIng Units
Reporting units are percent organic carbon (on a dry weight
basis) and percent carbonate carbon (on a dry weight basis).
7.2 MinImum Method Performance Criteria
The minimum method performance standard for the method is
detection of 0.02 percent carbon in a sample.
7.3 SIgnificant Figures
Results are reported to two (2) significant figures.
7.4 Duplicate Analyses
All duplicate analyses are reported. Duplicate analyses are run at
least every 20 samples.
7.5 Reference Materials
Leco pin and ring carbon standards are analyzed as reference
materials and standards.
Rev. 1 November 1989
A- 118
-------
, oM:IML COI1O 9 G Station ,TX To: 8167E38420 M Y 9, 19S 9:49AM P. 2
ORGANIC CARBON, TOTAL
Method 415,1 (Combustion or OxidRtlon)
STOREr NO. Total 00680
Dissolved 00681
Scope and Application
1.1 This method includes the measurement of organic carbon iii drinking, surface and saline
waters, domestic and industrial wastes. Exclusions are noted under Definiiions and
Interferences
1.2 The method is most applicable to measurement of organic carbon above I mg/I.
2. Summary of Method
2.1 Organic carbon in a sample is converted to carbon dioxide (CO,) by catalytic combustion
or wet chemical oxidation, The CO 2 formed can be measured directly by an infrared
detector or converted to methane (Cl-i 1 ) and measured by a flame ioniTation detector.
The amount of CO 7 or CI I I is directly proportional to the concentration of carbonaceous
material in the sample.
3. Definitions
3.1 The carbonaceous nnaly7er measures all of the carbon in a sample. Because of various
properties of carbon-containing compounds iii liquid samples, preliminary treatment of
the sample prior to analysis dictates the definition oIthc carbon as it is measured. Forms
of carbon that are measured by the method are
A) soluble, nonvolatile organic cai bon. for in Lance. natural sugars.
B) soluble, volatile organic carbon; for instance, mercaptans
C) insoluble, partially volatile carbon, for jns ancc, oils.
D) insoluble, particulate carbonaceous materials, for instance: cellulose fibers
E) soluble or insoluble caibonaceous materials adsorbed or entrapped on insoluble
inorganic suspended matte ,, for instance, oily matter adsorbed on silt particles,
3.2 The final usefulness of the carbon measurement is in assessing the potential oxygen.
demanding load of organic material on a r ceivtng stream. This statement applies
whether the carbon measurement is made on a ;ewage plaiit emuent, industrial waste, or
on water taken directly from the stteam, In thn. light, carbonate arid bicarbonate carbon
are not a part of the oxygcn demand in the streim and therefore should be discounted in
the final calculation or removed prior to analysis The manner of preliminary treatment
of the sample and instrument settings defines Lhe types of carbon which arc measured.
Instrument manufacturc(s instructions should he followed
Approved for NZ’DE.S
Issued 1971
ditorial revision 1974
415 I-i
A—119
Preceding page blank
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OM:IML Colle 9 e Statiori,TX To: 916753942 M Y 9, j99 9:5 M P.03
4. Sample Handling nd Preservation
4.1 Sampling and storage of samples in glass bottles is preferable Sampling and storage in
plastic bottles such us conventional polyethylene and cubitainers is permissible if it is
established that the containers do not contribute contaminating organics to the samples.
NOTE 1; A brief study performed in the EPA !...ahoratory indicated that distilled water
stored in new, one quart c’ubitniners did not show any increase in organic carbon after
two weeks exposure.
4.2 Because of the possibility of oxidation or bacterial decomposition of some components of
aqueous samples, the lapse of time between collection of samples and start of analysis
should be kept to a minimum. Also, samples should be kept cool (4 and protected
front sunlight and atmospheric oxygen.
4.3 In instances where analysis cannot be performed within two hours (2 hours) from time of
sampling, the sample is acidified (pH 2) with HCI or !-{ SO 4 .
5. Interferences
5.1 Carbonate and bicarbonate carbon represent an interference under the terms of this test
and must be removed or accounted for in the final calculation.
5.2 This procedure is applicabk only to homogeneous samples which can be injected into the
apparatus reproducibly by means of a microliter type syringe or pipette. The openings of
the syringe or pipette limit the maximum size of particles which may be included in the
sample.
6 Apparatus
6.1 Apparatus fot blending or homogenizing samples: Generally, a Waring-type blender is
satisfactory.
6 2 Apparatus for total und dissolved organic carbon:
6.2.1 A number of companies manufacture systems for measuring carbonaceous
material in liquid samples. Considerations should be made as to the types of
samples to be analyzed, the expected concentration range, and forms of carbon to
be measured.
6 2 2 No specific analyzer is recommended as superior.
7. Reagents
7.1 Distilled water used in preparation of standards and for dilution of samples should be
ultra pure to reduce the carbon concentration of the blank Carbon dioxide-free, double
distilled water is recornntended Ion exchanged waters are not recommended because of
the possibilities of contamination with organic materials from the resins.
7.2 Potassium hydrogen phthalate, stock solution, 1000mg carbon/liter Dissolve 0.2128 g
of potassium hydrogen phihalate (Primary Standard Grade) in distilled water and dilute
to 100.0 ml.
NOTE 2: Sodium oxalate and acetic acid are not recommended as stock solutions.
7.3 Potassium hydrogen phthalate, standard solutions Prepare standard solutions from the
stock solution by dilution with distilled water.
7.4 Carbonate-bicarbonate, stock solution, 1000 iug carbon/liter, Weigh 0.3500g of sodium
bicarbonate antI 04418 g of sodium carbonate and transfer both to the same 100 ml
volumetric flask. Dissolve with distilled waier
415 1-2
A- 120
it -,
-------
‘ J I l L .. LO1 i tat .ion, ix lri’Y , rii i r. i’i
75 Caibonaie.hicarbonate, standard soltition: Prepare a series of standards similar to step
7.3.
NOTE 3: This standard is not required by some instruments.
7.6 Blnuk solution: Use the same distilled water (or similar quality water) used for the
preparation of the standard solutions.
8 Procedure
R.l Follow instrument manufacturer’s instructIons for calibration, procedure, and
calculations,
R.2 For calibration of the instrument, it is recommended that a series of standards
encompassing the expected concentration range ofthe samples be used.
9. Precision and Accuracy
9 I Twenty-eight analysts in twenfy-one laboratories analy2ed distilled water solutions
containing exact increments of oxidizable org nic compounds, with the following results:
increment ac Precision as Accuracy as
bC Standard Deviation liias. Bias,
mg/liter TOC, mg/liter mg/liter
4.9 3.93 + IS 27 +075
107 8.32 .4 1.01 +108
(FWPCA Method Study 3, Demand Analyses)
BIbliography
Annual Book of ASTM Standards, Part 31. “Waler”, Standard D 2574—79, p469 (1976).
2. Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 532,
Method 505, (1975).
415 3-3
A-121
I1Ic
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APPENDIX B
SAJIPLING AND AHALY IS DATA
B—i
-------
This appendix presents data collected during the test at the Continental
Cement wet kiln in Hannibal, MO. Data are presented as follows:
Content Page
B-i Process Data Measured by Continental B—5
B—2 Solid Waste Characterization B.-41
B-3 CEM Data Measured by MRI 8—45
B-4 Organic Mass Data 8—55
B-5 Total Hydrocarbon and Total Organic Mass Data B—85
B-6 Volatile Organics Data B—ill
8-7 Semivolatile Organics Data 8—143
B-8 Gaibraith Lab Analysis Results B—i83
B—9 HC1 Data B—i93
B-lU TOC Analysis Results B—249
6-3
-------
APPENDIX B-i
PROCESS DATA MEASURED BY CONTINENTAL
This appendix contains process data obtained from the facility’s process
control instruments.
B- 5
-------
The following terms are used in the process data tables to
note readings of the various monitors
Speed - Rotational speed of the kiln in revolutions per hour.
Feed - Lime slurry feedrate to the kiln in tons per hour.
Dust - Recycle rate of dust from ESP’s to the kiln in tons per
hour.
Coal - Feedrate of coal to the kiln in tons per hour.
Waste Fuel - Total waste feedrate (so Lid plus liquid) expressed
as equivalent tons per hour of coal based on heating
value.
Fuel/Feed - Ratio of total fuels to total feeds. Fuel is the
sum of Coal and Waste Fuel. Feed is the sum of Feed
and Dust.
Supp.Fuel - Supplemental fuel feedrate in pounds per minute.
Supplemental fuel is either liquid waste or diesel fuel
for this test program.
KSWF — Kiln Solid Waste Fuel feedr te expressed as equivalent
tons per hour of coal based on heating value.
KSWF (chart) — Kiln Solid Waste Fuel expressed as a numerical
value which allows reading calibration graph to
determine solid waste feedrate in tons per hour.
BZT - Burner Zone Temperature is the temperature in
Fahrenheit measured at the low (burner) end of the kiln
where wastes are fed.
Feed End - Temperature in Fahrenheit of the high end of the kiln,
where lime slurry feed is introduced.
Chain - Temperature in Fahrenheit of the chain section of the
kiln, located about 2/3 to 3/4 of the way up the kiln.
ESP Inlet - Temperature in Fahrenheit of the inlet to the ESP’s.
02 - Plant oxygen levels in percent. Monitored just upstream
of ESP’s.
CO - Plant carbon monoxide levels in ppm. Monitor
inoperable during all tests conducted.
S02 - Plant sulfur dioxide levels in ppm. Monitored just
upstream of the ID fan.
MOx - Plant nitrogen oxides levels in ppm. Monitored just
upstream of the ID fan.
B-7
-------
ID Draft - Draft of the ID fan measured in inches of water.
ID % Open - Percent open of the damper on the ID fan.
ID Fan % - Percent of full speed for the ID fan.
ID Fan Amps - Amperage drawn by operation of the ID fan.
Kiln AmpS - Total amperage drawn by two motors which turn the
kiln.
Opacity - Percent opacity measured by transmissometer on the
stack.
B-B
-------
Table 1 Summary ot Process Data
Run # Speed Feed Dust Coal Waste Fuel Fuel/Feed Supp Fuel KSWF
(rph) (tph) (tph) (tph) (lb/mn)
Run 1
Avg 51 95 18 19.0 0 0171 0 0
M m. 45 82 0 143 0 0.108 0 0
Max 60 110 24 20.7 0 0204 0 0
Run 2
Avg 67 129 3 11 4 105 0166 264 2
Mm. 67 126 1 105 105 0152 242 2
Max 67 129 168 121 10.5 0174 276 2
Run 3
Avg 70 132 4 11 6 11 5 0170 306 2
Mm 70 132 1 11 3 11 5 0164 281 2
Max 70 132 8 122 11.5 0178 335 2
Run 4
Avg 70 132 2 11 9 11 5 0174 334 2
Mm. 70 132 2 11 5 11 5 0172 326 2
Max 70 132 5 122 11 5 0 177 341 2
Pun 5
Avg 66 126 95 11 8 8 0144 162 0
Mm 66 126 95 111 7 0141 115 0
Max 66 126 95 128 8 0.151 200 0
Run 6
Avg 66 127 99 13.1 6 0140 126 0
Mm 66 126 95 126 6 0135 110 0
Max 66 128 12 13.8 6 0144 145 0
HCI Run
Avg 57 110 2 87 6 0131 207 0
Mm 50 98 2 49 6 0109 150 0
Max 66 126 2 127 6 0152 235 0
B-9
-------
Run KSWF(chart) BZT Feed End Chain ESP Inlet 02 CO S02
(F) (F) (F) (F) (%) (ppm) (ppm)
Run 1
Avg 0 2447 491 1619 443 31 0 805
Mm 0 2240 420 1590 410 1 9 0 274
Max 0 2530 550 1650 470 54 0 1669
Run 2
Avg 109 2293 577 1700 502 1 9 0 223
M m 96 2230 560 1700 500 1 5 0 130
Max 116 2340 590 1700 510 21 0 304
Run 3
Avg 76 2274 600 1766 540 20 0 422
Mm 30 2200 600 1750 540 1 8 0 282
Max 88 2375 600 1800 540 28 0 572
Run 4
Avg 75 2272 600 1785 540 1 9 0 939
Mm 72 2230 600 1760 540 1 7 0 622
Max 78 2340 600 1800 540 2 0 1180
Run 5
Avg 0 2261 544 1590 469 20 0 277
Mm 0 2225 530 1590 450 1 6 0 205
Max 0 2300 560 1590 480 26 0 352
Run 6
Avg 0 2290 553 1600 480 20 0 332
Mm 0 2250 550 1600 480 1 4 0 220
Max 0 2330 560 1600 480 23 0 458
HCI Run
Avg 0 2244 571 1693 494 35 0 365
Mm 0 2180 560 1660 480 1 6 0 215
Max 0 2380 580 1740 500 6 0 728
B- 10
-------
Run # NOx ID Draft ID % Open ID Fan % ID Fan Amps Kiln Amps Opacity
(ppm) (in H20) (%)
Run 1
Avg 916 —20 37 59 65 926 13
Mm 40 —2 4 24 56 63 800 4
Max 2084 —1.2 46 60 68 980 20
Run 2
Avg 619 —35 66 60 73 1136 25
Mm 291 —38 56 58 70 1050 18
Max 1043 —32 78 60 75 1200 48
Run 3
Avg 939 —37 83 60 76 1034 33
Miii 273 —4 76 60 75 960 22
Max 2039 —38 90 60 77 1100 53
Run 4
Avg 1102 —36 78 60 77 1005 39
Miii 817 —38 70 60 75 960 31
Max 1591 —34 82 60 77 1050 46
Run 5
Avg 344 —41 65 60 75 1066 16
Miii 37 —42 56 60 75 1000 0
Max, 2017 —38 70 60 78 1200 100
Run 6
Avg. 152 —38 57 60 76 1041 15
Mm 48 —4 54 60 75 1000 6
Max 487 —37 58 60 78 1150 22
HCI Run
Avg 194 —29 52 60 70 1088 10
Mm 23 —32 42 60 65 1040 3
Max 1237 —24 60 60 75 1150 22
B-il
-------
Run 1 Process Data
4th Travers e
1415
1430
1445
1500
Avg Try 1—3
Average=
Min=
M ax=
Avg Try 4
Average=
Min=
M ax=
Overall Run
Average=
Min=
Max=
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Time
Speed Feed
Dust Coal Waste Fuel Fuel/Feed Supp Fuel
lst—3rdTra V
1115
1130
1145
1200
1215
1230
1245
1300
1315
1330
1345
1400
49
92
125
197
0
0189
49
92
0
188
0
0204
49
90
8
188
0
0192
49
92
15
20
0
0187
50
92
16
20
0
0185
49
93
16
20
0
0183
50
92
20
20.5
0
0183
50
92
20
207
0
0185
56
102
20
19.6
0
0
161
56
102
22
196
0
0158
56
102
24
179
0
0142
60
110
24
172
0
0128
60
110
22
143
0
0108
50
94
22
177
0
0153
45
84
22
18.9
0
0178
45
82
22
206
0
0198
52
96
16
194
0
0175
49
90
0
17.2
0
0128
60
110
24
207
0
0204
50
93
22
179
0
0159
45
82
22
14.3
0
0108
60
110
22
206
0
0198
51
95
18
19.0
0
0171
45
82
0
143
0
0108
0
0
0
B- 12
-------
Time KSWF BZT Feed End Chain ESP Inlet 02 CC
1 st—3rd Tra
1115 0 2400 510 1620 460 2 NA
1130 0 2450 490 1620 450 22 NA
1145 0 2400 480 1620 440 27 NA
1200 0 2440 480 1620 440 21 NA
1215 0 2460 480 1620 435 1 9 NA
1230 0 2460 490 1620 440 23 NA
1245 0 2425 510 162C 450 3 NA
1300 0 2490 540 162C 460 29 NA
1315 0 2500 550 162C 470 26 NA
1330 0 2530 540 164C 470 26 NA
1345 0 2475 520 1650 470 4 1 NA
1400 0 2525 470 1650 450 26 NA
4th Travers
1415 0 2525 440 l6 OC i 420 54 NA
1430 0 2505 420 160C ’ 410 5 1 NA
1445 0 2240 450 159(1 410 42 NA
1500 0 2320 490 159(1 420 4 NA
Avg Trv.1—3
Average= 0 2463 505 1627 453 2 6 0
Min= 0 2400 470 1620 435 1 9 0
Max= 0 2530 550 1650 470 41 0
Avg Try 4
Average= 0 2398 450 159 415 4 7 0
Min= 0 2240 420 1590 410 4 0
Max= 0 2525 490 1600 420 54 0
Overall Run
Average= 0 2447 491 1619 443 3 1 0
Min= 0 2240 420 1590 410 1 9 0
Max= 0 2530 550 1650 470 54 0
B- 13
-------
Time S02 NOx ID Draft ID % Open ID Fan % ID Fan Amps Kiln Amps
1 st—3rd Tra
1115 850 1554 —1.8 32 60 65 960
1130 1669 1149 —1 6 30 60 63 960
1145 1096 704 —1 9 38 58 65 960
1200 763 1469 —1 8 32 56 65 960
1215 862 2084 —1 8 35 60 65 960
1230 898 1534 —21 40 60 65 960
1245 896 1035 —21 42 59 65 960
1300 794 1455 —2 38 60 65 980
1315 724 1277 —2 38 58 65 960
1330 1083 1330 —21 40 59 65 900
1345 593 314 —2.4 46 59 65 880
1400 1259 445 —1 2 24 60 63 880
4th Travers
1415 498 75 —22 40 60 65 900
1430 342 40 —21 38 59 68 910
1445 275 78 —2.1 38 59 65 800
1500 274 112 —22 40 59 65 880
Avg Try 1—3
Average= 957 1196 —1 9 36 59 65 943
Min= 593 314 - 24 24 56 63 880
Max= 1669 2084 —1 2 46 60 65 980
Avg Try 4
Average= 347 76 —2 2 39 59 66 873
Min= 274 40 —2.2 38 59 65 800
Max= 498 112 —21 40 60 68 910
Overall Run
Average= 805 916 —2 0 37 59 65 926
Min= 274 40 —2 4 24 56 63 800
Max= 1669 2084 —1.2 46 60 68 980
8-14
-------
Time Opacity
1 st—3rd Tra
1115 13
1130 10
1145 14
1200 18
1215 14
1230 17
1245 19
1300 20
1315 19
1330 19
1345 15
1400 8
4th Travers
1415 4
1430 4
1445 6
1500 9
Avg Try 1 —3
Average= 16
Min= 8
Max= 20
Avg Try 4
Average= 6
M in= 4
Max= 9
Overall Run
Average= 13
Min= 4
Max= 20
B—15
-------
Run 2 Process Data
Time Speed Feed Dust Coal Waste Fuel Fuel/Feed Supp Fuel
Try 1
1230 67 126 3 11.8 10.5 0173 242
1245 67 128 16.8 11 5 105 0152 249
1300 67 128 4 111 105 0164 252
Try 2—4
1315 67 129 3 105 105 0159 271
1330 67 129 3 108 105 0 161 250
1345 67 129 1 11 1 105 0166 264
1400 67 129 1 12 1 105 0174 266
1415 67 129 3 11 105 0163 264
1430 67 129 4 11 8 105 0.168 269
1445 67 129 1 11 8 105 0172 273
1500 67 129 1 10.8 105 0164 274
1515 67 129 1 11 5 10.5 0.169 275
1530 67 129 1 117 105 0171 271
1545 67 129 1 11 4 105 0168 276
Avg Try 1
Average= 67 127 79 11 5 105 0163 248
Min= 67 126 3 11 1 105 0152 242
Max= 67 128 168 11 8 105 0173 252
Avg Try 2 —4
Average= 67 1 29 1 8 11 3 10 5 0 167 268
Min= 67 129 1 105 105 0 159 250
Max= 67 129 4 12 1 105 0174 276
Overall Ru n
Average= 67 129 3 11 4 105 0166 264
Min= 67 126 1 105 105 0152 242
Max= 67 129 168 12 1 105 0174 276
B- 16
-------
Time KSWF KSWF(chart) BZT Feed End Chain ESP Inlet 02
liv 1
1230 2 116 2340 5Th 1700 500 1 9
1245 2 116 2325 575 1700 500 1 9
1300 2 114 2325 560 1700 500 1 8
Try 2—4
1315 2 96 2300 560 1700 500 1 9
1330 2 101 2290 560 1700 500 1 9
1345 2 112 2320 565 1700 500 21
1400 2 112 2290 570 1700 500 21
1415 2 106 2325 575 1700 500 1 6
1430 2 110 2310 585 1700 500 1 5
1445 2 115 2280 590 1700 500 1 8
1500 2 105 2280 590 1700 500 1 6
1515 2 105 2250 590 1700 510 1 9
1530 2 105 2240 590 1700 510 1 9
1545 2 107 2230 590 1700 510 2
Avg liv 1
Average= 2 115 2330 5 0 1700 500 1 9
Min= 2 114 2325 560 1700 500 1 8
Max= 2 116 2340 575 1700 500 1 9
Avg Try 2
Average= 2 107 2283 579 1 700 503 1 8
Min= 2 96 2230 530 1700 500 1 5
Max= 2 115 2325 590 1700 510 2 1
Overall Ru
Average= 2 109 2293 577 1700 502 1 9
Min= 2 96 2230 530 1700 500 1 5
Max= 2 116 2340 5 O 1700 510 21
B- 17
-------
Time CO S02 NOx ID Draft ID % Open ID Fan % ID Fan Amps
Try 1
1230 NA 217 587 —36 59 60 70
1245 NA 241 443 —3.4 56 59 70
1300 NA 257 851 —35 58 58 70
Try 2—4
1315 NA 173 415 —34 56 60 70
1330 NA 130 568 —32 56 60 72
1345 NA 204 291 —34 60 60 72
1400 NA 282 471 —35 60 60 72
1415 NA 225 589 —35 62 60 75
1430 NA 213 922 —38 72 60 75
1445 NA 194 1043 —38 78 60 75
1500 NA 206 789 —38 78 60 75
1515 NA 228 946 —36 78 60 75
1530 NA 248 439 —34 78 60 75
1545 NA 304 317 —36 78 60 75
Avg Try 1
Average= 0 238 627 -3 5 58 59 70
Min= 0 217 443 —36 56 58 70
Max= 0 257 851 -3 4 59 60 70
Avg liv 2
Average= 0 219 617 —35 69 60 74
Min= 0 130 291 —38 56 60 70
Max= 0 304 1043 —32 78 60 75
Overall Ru
Average= 0 223 619 —3 5 66 60 73
Mfl= 0 130 291 —38 56 58 70
Max= 0 304 1043 —32 78 60 75
B- 18
-------
Time Kiln Amps Opacity
Tr’i 1
1230 1200 18
1245 1200 20
1300 1200 27
Tr’i 2—4
1315 1200 27
1330 1200 20
1345 1200 21
1400 1200 22
1415 1150 25
1430 1050 24
1445 1050 27
1500 1050 23
1515 1050 25
1530 1100 27
1545 1050 48
Avg. Ti ’. ’ 1
Average= 1200 22
Min= 1200 18
Max= 1200 27
Avg Try 2
Average= 1118 26
Min= 1050 20
Max= 1200 48
Overall Ru
Average= 1136 25
Min= 1050 18
Max= 1200 48
8-19
-------
Run 3 Process Data
70 132
70 132
70 132
4 116
1 113
8 122
115 0170
115 0164
115 0178
306
281
335
Time
Speed Feed
Dust
Coal Waste Fuel
Fuel/Feed Supp.FueI
1145
70
132
8
11
5
115
0164
281
1200
70
132
8
11
4
11 5
0164
284
1215
70
132
6
11
3
11 5
0165
296
1230
70
132
6
11
6
11 5
0167
287
1245
70
132
6
11
5
11 5
0167
291
1300
70
132
4
11
6
11 5
0170
286
1315
70
132
4
11
4
11 5
0168
282
1330
70
132
3
11
4
11.5
0170
314
1345
70
132
3
11
5
11.5
0170
335
1400
70
132
4
11
5
11 5
0.169
308
1415
70
132
4
11
6
11 5
0170
299
1430
70
132
4
11
6
11 5
0170
314
1515
70
132
3
11
4
115
0170
307
1530
70
132
1
11
9
11.5
0.176
331
1545
70
132
1
12
1
11 5
0 177
322
1600
70
132
1
122
115
0178
315
1615
70
132
5
12
1
11 5
0172
319
1630
70
132
5
11
7
11 5
0169
323
1645
70
132
6
11
6
11 5
0167
312
1700
70
132
6
11
6
11 5
0167
312
1715
70
132
6
11
8
11 5
0169
301
Average=
Min=
Max=
B-20
-------
Time KSWF KSWF(chart) BZT Feed End Chain ESP Inlet 02
1145 2 87 2240 600 1760 540 1 9
1200 2 87 2270 600 1780 540 1 9
1215 2 85 2270 600 1760 540 2
1230 2 79 2240 600 1760 540 2
1245 2 69 2240 600 1760 540 21
1300 2 71 2240 600 1760 540 2 1
1315 2 71 2260 600 1750 540 2 1
1330 2 44 2260 600 1760 540 28
1345 2 30 2280 600 1760 540 26
1400 2 77 2275 600 1760 540 21
1415 2 79 2250 600 1760 540 2
1430 2 79 2275 600 1760 540 1 9
1515 2 79 2210 600 1760 540 2
1530 2 79 2220 600 1760 540 1 9
1545 2 79 2200 600 1760 540 1 8
1600 2 79 2275 600 1760 540 1 8
1615 2 83 2310 600 1760 540 1 8
1630 2 84 2360 600 1780 540 1 8
1645 2 82 2360 6C0 1800 540 2
1700 2 83 2375 6C0 1800 540 2
1715 2 88 2340 600 1780 540 21
Average= 2 76 2274 6C0 1766 540 20
Min= 2 30 2200 6C0 1750 540 1 8
Max= 2 88 2375 6C0 1800 540 28
B- 21
-------
Time CO S02 NOx ID Draft ID % Open ID Fan % ID Fan Amps
1145 NA 295 1538 NA 76 60 75
1200 NA 422 1563 -38 78 60 75
1215 NA 406 838 —38 80 60 75
1230 NA 455 749 -39 86 60 75
1245 NA 374 925 —39 86 60 75
1300 NA 421 717 —39 86 60 75
1315 NA 298 703 —39 86 60 75
1330 NA 374 354 -4 86 60 75
1345 NA 439 273 -4 90 60 75
1400 NA 472 776 —38 86 60 75
1415 NA 350 1538 —39 82 60 77
1430 NA 357 2039 —39 82 60 77
1515 NA 282 764 -4 82 60 77
1530 NA 310 659 -4 82 60 77
1545 NA 477 763 —38 82 60 77
1600 NA 438 789 —38 82 60 77
1615 NA 502 1280 -4 82 60 77
1630 NA 572 1356 -38 80 60 77
1645 NA 501 736 —38 82 60 77
1700 NA 558 707 -38 82 60 77
1715 NA 567 648 —38 80 60 77
Average= 0 422 939 —3 7 83 60 76
Miri= 0 262 273 —4 76 60 75
Max= 0 572 2039 —3 8 90 60 77
B- 22
-------
Time Kiln Amps Opacity
1145 960 30
1200 1050 31
1215 1050 34
1230 1040 38
1245 1040 32
1300 1000 35
1315 1050 43
1330 1040 33
1345 1040 26
1400 1040 53
1415 960 34
1430 1000 25
1515 1040 28
1530 1050 28
1545 1020 22
1600 1100 27
1615 1050 46
1630 1040 33
1645 1060 30
1700 1050 29
1715 1040 28
Average= 1034 33
Min= 960 22
Max= 1100 53
B—23
-------
Run 4 Process Data
1100
1115
1130
1145
1200
1215
1230
1245
1300
1315
Speed Feed
70 132
70 132
70 132
70 132
70 132
70 132
70 132
70 132
70 132
70 132
2 117
2 117
2 115
2 12
2 12
2 119
2 122
2 118
2 122
2 115
115 0173
115 0173
11.5 0172
115 0175
115 0175
11.5 0175
115 0177
115 0174
115 0177
115 0172
340
341
326
338
329
330
336
334
341
330
Time
Dust
Coal Waste Fuel
Fuel/Feed Supp Fuel
1400
70
132
2
11
9
11
5
0
175
337
1415
70
132
2
121
11.5
0176
329
1430
70
132
5
12
1
11
5
0
172
328
Average=
70
132
2
11
9
11
5
0
174
334
Min=
70
132
2
11
5
11
5
0
172
326
Max=
70
132
5
12
2
11
5
0
177
341
8-24
-------
Time KSWF KSWF(chart) BZT Feed End Chain ESP Inlet 02
1100 2 74 2275 600 1760 540 2
1115 2 73 2260 600 1760 540 2
1130 2 73 2260 600 1780 540 2
1145 2 72 2250 600 1780 540 2
1 200 2 73 2250 600 1780 540 2
1215 2 74 2240 600 1780 540 2
1230 2 75 2230 600 1780 540 2
1245 2 76 2260 600 1780 540 1 9
1300 2 75 2280 600 1800 540 1 8
1315 2 75 2275 600 1800 540 2
1400 2 76 2290 600 1800 540 1 8
1415 2 75 2340 600 1800 540 1 8
1430 2 78 2320 600 1800 540 1 7
Average= 2 75 2272 600 1785 540 1 9
Min= 2 72 2230 600 1760 540 1 7
Max= 2 78 2340 600 1800 540 2
B- 25
-------
Time CO S02 NOx ID Draft ID % Open ID Fan % ID Fan Amps
1100 NA 1075 1247 -36 82 60 77
1115 NA 949 1264 —38 80 60 77
1130 NA 855 1217 —36 80 60 77
1145 NA 954 1061 —36 82 60 77
1200 NA 622 919 —36 82 60 77
1215 NA 917 961 —38 82 60 77
1230 NA 782 817 -36 78 60 77
1245 NA 984 1043 -36 78 60 77
1300 NA 841 1591 —36 78 60 77
1315 NA 1078 892 —36 78 60 77
1400 NA 1180 951 —34 72 60 75
1415 NA 791 930 -36 70 60 75
1430 NA 1174 1432 -37 72 60 75
Average= 0 939 1102 -36 78 60 77
Min= 0 622 817 —38 70 60 75
Max= 0 1180 1591 —34 82 60 77
B -26
-------
Time Kiln Amps Opacity
1100 1000 39
1115 1000 37
1130 1040 39
1145 1040 39
1200 1040 46
1215 960 43
1230 1050 40
1245 960 36
1300 960 43
1315 960 35
1400 1050 36
1415 1040 31
1430 960 45
Average= 1005 39
Min= 960 31
Max= 1050 46
B -27
-------
Run 5 Process Data
Time
Speed Feed
Dust
Supp Fuel
8 0144 162
7 0141 115
8 0151 200
L: ie > ( i - ,
Coal Waste Fuel Fuel/Feed
1045
1100
1115
1130
1215
1230
1245
1300
1315
1330
1345
1400
1415
1430
1445
1500
1515
1530
Average=
Min
Max=
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
66 126
95
95
95
95
95
95
95
95
95
95
95
95
9.5
95
95
95
95
95
95
95
95
7 0141
7 0145
7 0146
7 0145
8 0147
8 0141
8 0144
8 0145
8 0144
8 0144
8 0144
8 0144
8 0.143
8 0144
8 0151
8 0143
8 0143
8 0143
12 1
126
128
126
11 9
11 1
11 5
11 6
11 5
11 5
11 5
11.5
11 4
11 5
124
11 4
11 4
114
11 8
11 1
128
149
160
148
182
158
170
169
115
200
155
175
154
158
165
172
161
171
160
B- 28
-------
Time KSWF BZT Feed End Chain ESP Inlet 02 CO
1045 NA 2300 550 1590 470 1 8 NA
1100 NA 2250 530 1590 470 1 7 NA
1115 NA 2225 530 1590 460 1 6 NA
1130 NA 2240 530 1590 460 26 NA
1215 NA 2260 550 1590 470 1 8 NA
1230 NA 2240 560 1590 480 1 8 NA
1245 NA 2280 550 1590 480 2 NA
1300 NA 2280 550 1590 480 22 NA
1315 NA 2275 550 1590 480 1 6 NA
1330 NA 2280 550 1590 480 22 NA
1345 NA 2260 550 1590 470 2 NA
1400 NA 2240 550 1590 470 21 NA
1415 NA 2260 550 1590 470 24 NA
1430 NA 2250 550 1590 470 24 NA
1445 NA 2260 550 1590 470 1 8 NA
1500 NA 2280 540 1590 470 21 NA
1515 NA 2250 530 1590 450 1 6 NA
1530 NA 2275 530 1590 450 1 8 NA
Average= 0 2261 544 1590 469 20 0
Mtn= 0 2225 530 1590 450 1 6 0
Max= 0 2300 560 1590 480 26 0
B- 29
-------
Time S02 NOx ID Draft ID ¾ Open ID Fan % ID Fan Amps Kiln Amps
1045 297 209 —41 58 60 75 1000
1100 278 587 —41 58 60 75 1150
1115 217 2017 —4 58 60 75 1040
1130 219 1212 —42 64 60 75 1150
1215 205 230 —42 70 60 75 1000
1230 274 161 -42 70 60 75 1040
1245 251 78 —4 70 60 75 1000
1300 285 118 -41 70 60 75 1000
1315 279 285 —4.2 70 60 75 1000
1330 283 125 —41 70 60 75 1000
1345 313 137 —39 70 60 75 1100
1400 352 91 —41 70 60 75 1100
1415 313 57 —4 70 60 75 1150
1430 274 37 —42 70 60 78 1050
1445 314 82 —39 60 60 75 1200
1500 288 197 —3.9 58 60 77 1050
1515 281 252 —38 56 60 75 1050
1530 255 324 —39 58 60 75 1100
/
Average= 277 3 4 —4 1 65 60 75 1066
Min= 205 37 —42 56 60 75 1000
Max= 352 2017 —38 70 60 78 1200
8-30
-------
Time Opacity
1045 12
1100 25
1115 16
1130 100
1215 9
1230 6
1245 0
1300 0
1315 6
1330 0
1345 0
1400 18
1415 6
1430 12
1445 20
1500 16
1515 20
1530 24
Average= 16
Min= 0
Max= 100
B-31
-------
Run 6 Process Data
Dust Coal
j ic e( •j t
I t:;
Time
Sceed Feed
Waste Fuel
Fuel/Feed Supp Fuel
1900
66
128
95
138
6
0
144
139
1915
66
128
95
131
6
0139
110
1930
66
128
95
132
6
0140
116
1945
66
126
95
133
6
0
142
128
2000
66
126
95
13
6
0
140
131
2015
66
126
95
13
6
0
140
125
2030
66
126
95
13
6
0
140
120
2045
66
126
95
128
6
0
139
145
2100
66
126
95
131
6
0141
120
2115
66
126
95
131
6
0141
130
2130
66
126
12
127
6
0136
127
2145
66
126
12
126
6
0135
124
66
66
66
127
126
128
99
95
12
13.1
12.6
138
6
6
6
0
0140
0135
144
126
110
145
Average=
Min=
Max =
B-32
-------
Time KSWF BZT Feed End Chain ESP Inlet 02 CO
1900 NA 2300 560 1600 480 1 4 NA
1915 NA 2310 560 1600 480 2 1 NA
1930 NA 2250 560 1600 480 22 NA
1945 NA 2260 550 1600 480 2 NA
2000 NA 2280 550 1600 480 22 NA
2015 NA 2280 550 1600 480 23 NA
2030 NA 2290 550 1600 480 2 NA
2045 NA 2300 550 1600 480 2 NA
2100 NA 2310 550 1600 480 22 NA
2115 NA 2275 550 1600 480 2 NA
2130 NA 2330 550 1600 480 2 NA
2145 NA 2300 550 1600 480 2 NA
Average= 0 2290 553 1600 480 2 0 0
Min= 0 2250 550 1600 480 1 4 0
Max= 0 2330 560 1600 480 23 0
8-33
-------
Time S02 NOx ID Draft ID % Open ID Fan % ID Fan Amps Kiln Amps
1900 220 487 —4 58 60 75 1000
1915 275 250 —4 58 60 75 1000
1930 307 141 —4 58 60 78 1150
1945 316 301 —38 56 60 78 1000
2000 281 103 —38 56 60 75 1040
2015 308 74 —4 56 60 78 1050
2030 299 120 —3.8 58 60 75 1150
2045 311 70 —3.7 58 60 77 1000
2100 428 69 —38 56 60 77 1000
2115 458 88 —37 56 60 75 1050
2130 373 48 —37 54 60 75 1000
2145 402 73 —3.7 54 60 75 1050
Average= 332 152 —3.8 57 60 76 1041
Min= 220 48 —4 54 60 75 1000
Max= 458 487 —37 58 60 78 1150
8-34
-------
Time Opacity
1900 17
1915 6
1930 10
1945 19
2000 14
2015 12
2030 8
2045 22
2100 15
2115 18
2130 16
2145 19
Average= 15
Min= 6
Max= 22
B-35
-------
HCI Test Process Data
1645
1700
1715
1730
1745
1800
1815
1830
1845
Speed Feed
66 126
66 124
50 98
53 100
53 102
55 106
55 106
57 110
61 116
2 127
2 84
2 49
2 59
2 64
2 92
2 97
2 11
2 10
6 0146
6 0114
6 0109
6 0117
6 0119
6 0141
6 0145
6 0152
6 0136
233
202
216
226
230
235
150
195
175
57 110
50 98
66 126
2 8.7
2 4.9
2 127
6 0131
6 0109•
6 0152
207
150
235
Time
Dust
Coal Waste Fuel Fuel/Feed Supp Fuel
Average=
Min=
Max=
B -36
-------
Time KSWF BZT Feed End Chain ESP Inlet 02 CO
1645 NA 2290 575 1740 500 1 6 NA
1700 NA 2380 575 1740 500 38 NA
1715 NA 2280 570 1720 500 6 NA
1730 NA 2280 580 1700 500 5 NA
1745 NA 2190 580 1700 500 4 1 NA
1800 NA 2190 570 1660 490 26 NA
1815 NA 2180 570 1660 490 32 NA
1830 NA 2180 560 1660 490 24 NA
1845 NA 2225 560 1660 480 28 NA
Average= 0 2244 571 1693 494 35 0
Min= 0 2180 560 1660 480 1.6 0
Max= 0 2380 580 1740 500 6 0
B—37
-------
Time S02 NOx ID Draft ID % Open ID Fan % ID Fan Amps Kiln Amps
1645 728 1237 —32 60 60 70 1150
1700 531 190 —32 60 60 75 1150
1715 292 73 —32 60 60 73 1100
1730 321 41 —24 42 60 68 1050
1745 254 23 -26 42 60 65 1100
1800 215 67 —26 50 60 70 1050
1815 309 37 -28 52 60 70 1040
1830 324 32 —3 52 60 70 1100
1845 309 43 —3 54 60 70 1050
Average= 365 194 -29 52 60 70 1088
Min= 215 23 —32 42 60 65 1040
Max= 728 1237 —24 60 60 75 1150
B -38
-------
Time Opacity
1645 22
1700 12
1715 8
1730 7
1745 7
1800 10
1815 3
1830 9
1845 13
Average= 10
Min= 3
Max= 22
B—39
-------
U i X 10 IC) INCtI x io u4C$It
KEUIFEL & ES ER CO. ADt 46 1320
SOLID WASTE FUEL FEEDER MODEL 105Z-N
-------
APPENDIX B—2
SOLID WASTE CHARACTERIZATION
This appendix contains solid waste feed data supplied to MRI by
Continental.
B-41
-------
190
‘r’ .c r
Sucoca / or ‘ cei “‘ a cnro ;c as
Il .. i I
U I I
lmagin ering A Clear r World
‘ir. Scott: Kl irr i
1 d’ est Research Inst tute
425 \oll:er Bouleard
L:ansas City, O 641:0
Dear Scott:
The fo11o irt taole is the l ,sts o oo dered fuels feJ to
Continental Cement during the testing da ’. Densities are also
included. Rotat ona1 s eed chart ‘ ersits feed rate s not t e onl’
parameter Contt:nental Cement relies on for feed n the pcuders.
Instead, they trade one ton eqtii’alent of ccal for one ton o soi d
fuel and make adjustments as neeced based or’. kiln opera:lng
paran ieters.
>lobay
IFR
Mo bay
IFE
Mo bay
IFR
Mob a y
IFR
SoL r Fuels
Weight .
44,150
3, 780
42,550
14,450
46.750
22,140
I— 1
33, 20
Density
• 724
• 744
.690
.721
.656
.790
—
• I ‘ ,
• 603
1.0
‘.3
1.5
2.3
1.0
1.0
Sincerely,
Resource Reco’. err, Inc.
Chris Schre ber
Facility En ineer
cc: B l1 elson
CHS/c jc
Riedel Industrial Waste Management
Latser & Schreiber, Inc Solvent Recovery Corp
22c E . 30 L
L ’
(C—l0 i —A S 3—-.
24.hour kotline I 800.334.0004
B-43
Resource Recovery, Inc
—; ‘ ;C 0- :
i_Il .‘.J
6/21
6/22
7/06
7/07
lbs.
Feed Rate
2.0
20
-------
APPENDIX B—3
CEM DATA MEASURED BY MRI
This appendix contains a description of the MRI CEM system used during
the test series, gases used for calibration, QA/QC checks and minute-by—minute
readings of each instrument.
B-45
-------
Continuous emission monitoring (CEM) da a were collected during all six
test runs at the Continental Cement Company from June 20 to July 5, 1990. An
additional run was conducted July 2 for hydrochloric acid (HC1) only. All
sampling runs were of 2-h duration in conjunction with semivolatile, volatile,
and HC1 sampling at other points in the system. The CEM probe was inserted in
the east or north port of the stack at the 75 ft level for all sampling.
Heated and unheated HC emissions were measured using EPA M25A sampling sys-
tems, equipped with FIDs. This method e;sentially measures hydrocarbons
expressed in terms of propane.
To measure heated HC concentrations, the following changes were made to
the M25A system:
• The entire sample system from probe to detector was heated to 250°F.
• An MRI designed HC analyzer with a GOW—MAC electrometer was used.
• Propane in air was used as the calibration gas. EPA protocol 1
cylinder standards of 19.84, 50.11, and 99.44 ppm were used.
In measuring unheated HC concentrations, the following changes were made
to the M25A system:
• An ice-cooled water knockout trap as used to remove condensibles.
• An unheated Teflon sample line was used to conduct the sample
through a stainless steel pump to the FID.
• Propane in air was used as the ‘:alibration gas. EPA protocol 1
cylinder standards of 19.84, 50.11, and 99.44 ppm were used.
At the sample point (i.e., stack), combustion gas was collected using a
single probe with a sintered metal filter. Immediately after extraction, the
gas sample was split into “heated” and “unheated” sample fractions. The
heated sample fraction was transferred to a hot HC analyzer via a heated
sample line. The sample line, along with in—line tees and valves, was main-
tained at over 250°F. Pumps were used to maintain constant purging of all
sampling lines. The entire sampling system from the probe to the manifold was
leak checked each day before and after the t !st run.
The unheated sample fraction passed through a condensate trap (i.e., a
modified GBS impinger placed in an ice bath) which was located adjacent to the
sample port. Using a Teflon sample line, 1;he sample was transferred to the
F ID.
During the test the condensate trap was operated at a ‘noncontact”
condition. The noncontact condition is :haracterized by the sample gas
passing through the iced condensate trap without contact with collected
condensate.
The HC monitors used included two MRI in-house designed models. A data
logger was used to record all necessary information. The monitors were
B-47
-------
spanned and zeroed prior to and immediately following each run with 99.44 ppm
propane, N8S—traceable EPA protocol 1 gas, and prepurified nitrogen. A
linearity check was conducted each day using 50.11 ppm propane and 19.84 ppm
propane NBS—traceable EPA protocol 1 gases. Monitor response times were also
checked before the first run.
CU, CO. 2 , and 02 samples were split from the hot NC M25A sample line. The
sample was transferred via a heat traced TFE Teflon sample line and split for
CU 2 , 02, CU, and hot NC analysis. CO 2 was independently monitored and used to
volume—correct the CO reading to account for the CO 2 removed. A Horiba
Model PIR-2000S riondispersive infrared (NOIR) analyzer was used to measure
CO 2 . 02 was independently monitored and used to correct the CO and hot and
cold HC readings to 7% 02 concentrations. A Horiba PMA-200 paramagnetic
sensor was used to measure 02.
Total CO concentration was determined using a Horiba Model PIR-2000L
NDIR. After the CO sample was split from the hot HC M25A sample line, It was
passed through an ascarite/silica gel cartridge containing approximately 200 g
of ascarite and 20 g of silica gel. The ascarite trap removed carbon dioxide,
which is an interference to the CO monitor, and the silica gel removed the
last traces of moisture prior to the monitor. The sample fraction was then
pumped to the NDIR analyzer.
Zero drift was determined by checking the zero calibration before and
after each run and comparing the two. Calibration drive was determined by
checking the span gas calibration before and after each run. The response
time was determined by adding a calibration gas while the instrument is at the
zero calibration in the end of the probe and determining the length of time
for the instrument to reach 90% of the corresponding span value. The cali-
bration error (usually referred to as the linearity check) was performed by
zeroing and spanning the instrument and then adding a midlevel calibration gas
and comparing the instrument value with the real gas value. Zero and calibra-
tion drift were less than ±3% of the span value, while the calibration error
(linearity check) was less than ±5% of the calibration gas value for each run.
Possible bias from organics retained on the sampling lines was checked on
Run 3 by introducing zero gas at the sample probe after the run (NC only). No
organics were found.
The performance checks for the analyzers are summarized below:
Zero drift: 3% of span
Span drift: 3% of span
Linearity checks: 5 of cylinder gas value
Leak checks: < 4% of normal flow, before and after each run
Nominal gas concentrations:
B -48
-------
Li near ity
HC--span 99.84 ppm propane 50.11, 19.84 ppm
CO--786.7 ppm (392.8 ppm for run 1) 201.4 ppm
C0 2 -—11.93% 5.95%
O -11.89% 6.04%
HC1—-span 513.3 ppm 204.9, 103.1 ppm
HC1 continuous monitoring was
filter correlation infrared unit.
sample line and conditioning system.
dryers in sequence.
The system was leak-checked before and after each run at less than
200 rnmHg. The monitor was zeroed using prepurified nitrogen and spanned using
the lowest calibration gas available. Operation of the monitor was checked
hourly and fed span gases to verify response as necessary. Following each
run, a final zero and span was performed and the monitor purged for at least
30 mm with nitrogen before shutting down, Zero drift, span drift, and
response times were measured identically to the CO, C0 2 , and 02 monitors. A
linearity check will be performed using the ifidlevel calibration gas the first
day only. The system will be within 10% agreement of the gases true value.
Raw data from the field CEM print outs ‘here reviewed for comp
any notations of the operator. Data presented here were collected
semivolatile sampling on the stack. Invalid data periods due to
activities on the sampling system have also been removed from
tables. Runs 5 and 6 have noticeable gaps of some monitors but al
were above the 80% data recovery target selected for this project.
data from short intervals when the semivolatile trains were not
included. Carbon monoxide and hot and cold hydrocarbons have been corrected
to 7%. The correction is by the equation:
Raw Conc.(ppm) X
Additionally, the INC-H has been corrected for moisture content by the
equation:
Raw Conc. x 100 = Conc.
(ppm, wet) 100 - % Moisture (ppm, dry)
The percent moisture of the stack gas was calculated from the Method 0010
semivolatile train. Run 5A (HC1 test) moisture content is an average of the
other six runs since no moisture train was run that day. 02, CO 1 and CO 2 are
all expressed in dry units in the raw data and no moisture correction is
necessary. The same holds true for the hydrochloric acid and cold hydrocarbon
monitors.
performed by a Therno—electron Model 15 gas
The instrument used its own heated Teflon
Stack gas was dried using two Permapure
leteness and
only during
maintenance
these data
1 test runs
Some extra
sampling is
21 — 7
21 - 02 Conc.
= COflC.( 7% 02)
B -49
-------
STANDARD GASES [ BALANCE IS N 2 UNLESS SPECIFIEDI
Gas
Source
ID
No.
Conc. (ppm)
Expiration
date
HC1
Scott
Specialty
Gases
AD
17710
103.1
5% nonpro
HC1
Scott
Specialty
Gases
AD
17721
204.9
5% nonpro
HC1
Scott
Specialty
Gases
AD
17719
513.3
5% nonprok
HC1
Scott
Specialty
Gases
AD
13227
955.3
5% nonpro
02
Scott
Specialty
Gases
ALm
29D4
6.044%
9/29/90
02
Scott
Specialty
Gases
ALM
4752
11.885%
3/1/91
CO (A)
Scott
Specialty
Gases
ALM
10517
2D1.4
7/23/90
CO (A)**
Scott
Specialty
Gases
ALM
2211
392.8
1/6/91
CO
Scott
Specialty
Gases
AAL
9967
786.7
11/19/90
CO
Scott
Specialty
Gases
AAL
3453
5.96%
9/30/90
CO 2
Scott
Specialty
Gases
AAL
12906
11.93%
3/1/91
Propane
(A)**
Scott
Specialty
Gases
ALM
9901
19.84
6/28/91
Propane
(A)**
Scott
Specialty
Gases
ALM
9898
50.11
6/28/91
Propane
(A)**
Scott
Specialty
Gases
ALM
8883
99.44
7/23/91
Propane
(A)**
Scott
Specialty
Gases
ALM
99D2
10.12
7/23/91
Propane
(A)**
Scott
Specialty
Gases
ALM
9890
4.99
7/23/91
* Protocol cylinders not available. Within 5%.
** Air.
B-SO
-------
ANALYZERS
MR I
Analyzer type
Manufactur2r
prop
erty No.
THC-H electrometer
GOW-MAC
SN
045401*
THC-C electrometer
GOW-MAC
SN
C44904*
Hydrochloric acid
Therino
Electron
Co.
10329
Carbon monoxide
Horiba
10361
Carbon dioxide
Horiba
9685
Oxygen
Horiba
10363
* GOW-MAC serial number.
B-5 1
-------
SUMMARY OF CEM QC CHECKS
(HC1
Run 1 Run 2 Run 3 Run 4 Run
test)
SA Run 5 Run 6 a
Leak check initiaib P P P P P P P
Leak check final P P P P P P P
Oxygen
Span drift 0.9 0.2 1.1 0.1 - 1.6 0.3
Zero drift 0.5 0.8 3.4 1.7 - 2.8 1.1
Linearity —0.8 —3.0 1.1 1.2 — —1.4 same as 5
Carbon Dioxide
Span drift 1.1 0.7 0.8 0.9 1.5 0.2
Zero drift 0.5 0.7 0.5 0.2 0.6 0.1
Linearity —13.2 3.4 2.9 2.6 2.7 same as 5
Carbon Monoxide
Span drift 0.4 0.6 0.6 0.4 0.2 0.2
Zero drift 0.4 0.3 0.04 0.3 0.3 0.4
Linearity 1.5 1.7 0.8 1.5 0.5 same as 5
Hydrocarbon Hot
Span drift 0.2 0.5 4.4 0.7 - 0.2 0.5
Zero drift 1.0 3.8 2.0 0.2 - 0.4 0.1
Linearity —1.8 3.4 3.2 -2.6 — —2.0 same as 5
Hydrocarbon Cold
Span drift 0.03 2.0 1.1 2.2 - 0.3 0.5
Zero drift 0.2 0.3 0.2 0.2 - 0.6 0.1
Linearity —3.2 —3.6 -3.6 —3.6 - —1.8 same as 5
Hydrochloric Acid
Span drift - 3.1 0.2
Zero drift - 1.3 0.7
Linearity - -0.2 2.1
a Run 6 conducted same day as Run 5.
b Equal to or greater than 15 inHg.
C Equal to or greater than 200 mrnHg.
P = Pass
B- 52
-------
MOISTURE PERCENT OF STACK GAS
Run 1
Run 2
Run 3
Run 4
(HC1 test)
Run 5A
Run 5
Run 6
Percent
Oxygen
moisture
32.4
6.3
37.7
3.9
35.7
4.2
31.5
4.1
35.O
6.3’S’
36.3
4.5
36.3
4.8
a Average of other six runs. No moisture train was run that day.
b Determined by Fyrite.
B- 53
-------
CEM DATA REDUCTION
Raw data were refined, as follows, to generate final data values (i.e.,
averages, etc.).
• The CEM raw data were first converted from percent of full-scale
values to percent (02 and C0 2 ) or ppm (CO and THC values using a
data logging program. This conversion was based upon the average of
initial and final zero and span calibration data.
• Hot THC data were corrected from a wet to a dry basis following
applicable EPA Method 4 (40 CFR 60) protocols. The volume of
moisture collected in the Method 0010 seniivolatiles sampling train
and the associated dry gas metered volume were used to determine a
moisture content during each run.
• CO, hot THC, and cold THC data were corrected to 7% oxygen
conditions using the following formula: (uncorrected value) x
(14/ [ 21—021) = corrected value. Oxygen data collected during each
run was used to make this correction.
• At various points during each test, the THC analyzers were taken
off—line to zero and span the instrument. Available data points
within the sample period were utilized to interpolate 1-mm rolling
averages, if necessary.
B- 54
-------
APPENDIX 8—4
ORGANIC MASS DATA
This appendix contains a summary of each run’s organic mass data as
measured by the field GC and gravirnetric fraction of the semivolatiles
train. Individual syringe injection times and values are reported.
8-55
-------
For the field GC data analysis, areas integrated under each peak were
summed to give a total peak area for each run. This value was then divided by
the average daily reference factor for propane, resulting in a total organics
concentration for ppm propane equivalent. The average daily reference factor
was obtained from an average of peak areas For a standard propane sample of
known concentration.
Carbon fractions (i.e., Cl - C7 and C7 — Cl7 fractions) were determined
by comparing sample peak retention times to standard peak retention times.
Aliquots of a C17 in a C7 solution were analyzed to establish standard
peak retention times. The following standard retention time ranges were
determined in the test:
C1-C7: O—132s C7-C17: 133-556s
For gravimetric data reduction, method blank weight was subtracted from
each sample analysis value to determine a net gravimetric value. This net
value was then multiplied by a numerical factor to obtain the organic mass in
iig per sample. The dry standard sample volume was then utilized to generate a
ig/L emission concentration. The ppm propane equivalent was then calculated
by assuming that half of the sample molecular weight has no FID response;
calculated as follows:
%lg of sample 0.5 24.1 pL gas per 1 mcl of gas = ppm propane equivalent
L of air sampled 44 L propane per umol propane
B- 57
-------
TABLE B-4-1. ORGANIC MASS DATA FOR RUN 1
Total
RunTime
Sample
Carbon fractions (ppm propane)
mass
C1-C7 C1-C7 C7-C17 C7-C17
>C17
(TOM)
(24—h)
No Time
(wet) (dry) (wet) (dry)
(dry)
(dry)
1118—1448
620SS1 1114
620SS2 1132
R1ASS3 1151
R1ASS4 1209
R1ASS5 1228
R1ASS6 1246
R1ASS7 1305
R1ASS8 1324
R}ASS9 1343
R1ASS1O 1402
R1ASS11 1422
R1ASS12 1440
132 195 09 13
155 229 33 49
11.0 163 14 21
131 194 12 18
128 189 1.5 2.2
84 124 08 1 2
139 206 11 16
150 222 1 4 2 1
150 222 9 1 135
148 21 9 26 38
69 102 1 5 22
40 59 1 3 ii
Run Average =
17.7 3 2
1 73
22 6
TABLE B-4-2.
ORGANIC MASS DATA FOR RUN
2
Total
RunTime
Sample
Carbon fractions (ppm propane)
mass
C1-C7 C1—C7 C7-C17 C7-C17
>C17
(TOM)
(24—h)
No Time
(wet) (dry) (wet) (dry)
(dry)
(dry)
1230—1546
R2SS1 1228
R2SS2 1246
R2SS3 1305
R2SS4 1324
R2SS5 1343
R2SS6 1402
R2SS7 1421
R2SS8 1439
R2SS9 1458
R2SS1O 1516
R2SS11 1535
399 640 1.6 26
47 1 75 6 3.5 5 6
616 989 27 43
375 602 628 1008
40.2 645 50 80
652 104.7 29 47
49.7 79 8 4 7 7 5
57 2 91 8 4 9 7 9
626 100.5 40 64
357 573 23 37
41.1 660 22 35
Run Average =
785 14 1
354
96 1
File TOMS By PSM Date. 10/29/90
B -58
-------
TABLE B-4-3. ORGANIC MASS DATA FOR RUN 3
Total
Carbon fractions (ppm
propane)
mass
RunTime Sample 01-07 C1-C7 C7-C17
07-017
>017
(TOM)
(24—h) No Time (wet) (dry) (wet)
(dry)
(dry)
(dry)
1135—1720 R3SS1 1133 616 958 3.7
58
R3SS2 1151 588 914 21
33
R3SS3 1209 345 537 23
36
R3SS4 1227 330 513 17
26
R3SS5 1246 357 555 22
34
IR3SS6 1309 393 611 57
89
A3SS7 1328 230 358 08
12
R3SS8 1518 682 1061 53
82
R3SS9 1536 385 599 9,2
143
R3SS1O 1559 563 876 25
39
R3SS11 1617 488 759 23
36
R3SS12 1636 511 795 31
48
R3SS13 1654 36.8 572 1 2
1 9
R3SS14 1713 179 278 1420
2208
Run Average = 67 0
20 5
5 31
92
8
Note Off—scale peak in 01—07 region during 1518 sampe
TABLE B-4-4. ORGANIC MASS DATA
FOR RUN
4
Total
Carbon fractions (ppm
propane)
mass
Run Time Sample 01—07 C1-C7 C7-C17
C7—C17
>017
(TOM)
(24—h) No Time (wet) (dry) (wet)
(dry)
(dry)
(dry)
1055—1435 R4SS1 1053 248 362 09
13
R4SS2 1112 340 496 10
15
R4SS3 1130 132 193 1739
2539
R4SS4 1148 31.3 457 167
244
R4SS5 1207 230 336 268
391
R4SS7 1232 301 439 33
48
R4S 58 1251 421 61 5 1,7
25
R4SS9 1309 29 6 43 2 0.7
1 0
R4SS1O 1327 24 3 35 5 524
76 5
R4SS12 1346 270 394 54
79
R4SS13 1404 443 647 3 1
4 5
R4SS14 1422 468 683 22
32
Run Average = 45 1
35 0
5 62
85
7
Note Off—scale peak in 07—017 region during 1130 sarr pie, due to ESP shutdown
Note R4SS6 was taken during calibration and there was no R4SS1 1
File TOMS By PSM Date 10/29/90
8-59
-------
TABLE B-4-5. ORGANIC MASS DATA FOR RUN 5
Total
Carbon fractions (ppm propane)
mass
RunTime Sample C1-C7 C1-C7 C7-C17 C7-C17
>C17
(TOM)
(24—h) No. Time (wet) (dry) (wet) (dry)
(dry)
(dry)
1047—1535 R5SS1 1046 381 598 25 39
R5SS2 1105 843 132.3 11.4 179
R5SS3 1123 295 463 3.1 49
R5SS4 1220 616 967 40 6,3
R5SS5 1245 472 74.1 1 9 3.0
R5SS6 1303 36 9 57 9 2.1 3 3
R5SS7 1322 66 6 104 6 3 5 5 5
R5SS8 1341 48.1 755 29 46
R5SS9 1359 41 5 65.1 2 7 4 2
R5SS1O 1418 179 281 05 08
R5SS11 1436 379 595 20 31
R5SS12 1457 411 645 2 1 33
R5SS13 1515 484 760 25
Run Average = 72.3 5 0
8 22
85
5
Note Off—scale peak in Cl —07 region during 1105 sample
TABLE B-4-6. ORGANIC MASS DATA FOR RUN 6
Tota’
Carbon fractions (ppm propane)
mass
Runlime Sample C1-C7 C1-C7 C7-C17 C7-C17
>C17
(TOM)
(24—h) No. Time (wet) (dry) (wet) (dry)
(dry)
(dry)
1900—2152 R6SS1 1900 79.8 1253 59 93
R6SS2 1918 267 419 23 36
R6SS3 1937 408 64 1 1 4 22
R6SS4 2003 49 7 78 0 1 6 2 5
R6SS5 2022 46 3 72 7 1 8 2 8
R6SS6 2040 46 4 72 8 2 4 3 8
R6SS7 2059 45 8 71 9 2 6 4.1
R6SS8 2118 187 294 1.1 1.7
R6S 59 2136 347 545 12 19
Run Average = 67 8 3 5
9 56
80
9
File TOMS By PSM Date 10/29/90
8-60
-------
Filename: RU Ni
Name: RUN I
Date:06-20-19 9 O
Location: HAN NIBAL,MO
Project:91 02 - 63 -l 3
OperatorBG
VERSION =05/07/90
CO THCH THCC
Time 02 C02 CO THCH THCH THCC 7% 02 @ 7% 02 @ 7% 0
(%. (%, (ppm, (ppm, (ppm (ppm (ppm, (ppm, (ppm,
dry) dry) dry) wet) dry) dry) dry) dry) dry)
1118 3.9 23.7 203.1 18.6 27.5 9.5 165.8 22.5 7.8
1119 4.1 23.1 208.3 15.9 23.5 10.2 172.8 19.5 8.5
1120 4.6 22.6 213.0 13.3 19.7 10.8 181.4 16.8 9.2
1121 4.3 22.6 214.6 13.0 19.2 11.4 179.7 16.1 9.5
1122 4.0 22.9 215.0 14.3 21.2 11.4 176.5 17.4 9.4
1123 3.9 23.0 215.3 15.2 22.5 10.8 176.2 18.4 8.8
1124 3.7 23.1 213.8 18.3 27.1 10.5 172.7 21.9 8.5
1125 3,8 23.0 2122 17.5 25.9 10.8 172.3 21.0 8.8
1126 4,2 226 211.5 19.7 29.1 11.2 176.1 24.3 9.3
1127 4.6 223 210.4 10.6 15.7 11.8 179.2 13.4 10.0
1128 4.6 222 209.3 16.7 24.7 12.2 178.9 21.1 10.4
1129 4.3 22.5 208.4 17,7 26.2 11.8 175.0 22.0 9.9
1130 4.2 22.6 208.4 16.7 24.7 11.3 174.1 20.6 9.4
1131 4.6 22.3 209.2 16.2 24.0 10.9 178.2 20.4 9.3
1132 4.5 22.4 208.4 19.0 28.1 10.6 177.1 23.9 9.0
1133 4.4 22.5 207.1 19.9 29.4 10.5 174.8 24.8 8.9
1134 4.3 22.6 205.6 19.1 28.3 10.2 172.8 23.7 8.6
1135 4.5 214 204.8 15.5 22.9 9.9 173.2 19.4 8.4
1136 4.6 22.3 204.2 11.4 16.9 9.7 174.1 14.4 8.3
1137 4.5 22.4 203.4 15.0 22.2 9.6 172.4 18.8 8.1
1138 4.6 22.3 202.5 15.0 22.2 9.5 173.3 19.0 8.1
1139 5.5 21.4 204.4 13.5 20.0 9.4 184.7 18.0 8.5
1140 6.4 20.6 205.6 12.6 18.6 9.3 197.3 17.9 8.9
1141 6.4 20.6 204.9 12.3 18.2 9.3 195.9 17.4 8.9
1142 6.3 20.6 204.6 11.9 17.6 9.0 195.0 16.8 8.6
1143 6.5 20.6 204.5 11.6 17.2 8.7 196.9 16.5 8.4
1144 6.3 20.9 203.0 11.5 17.0 8.2 193.6 16.2 7.8
1145 5.9 21.6 200.0 11.8 17.5 7.9 185.6 16.2 7.3
1146 5.7 21.8 197.4 11.9 17.6 7.5 180.9 16.1 6.9
1147 5.4 22.2 193.5 12.6 18.6 7.3 173.5 16.7 6.5
1148 5.0 22.4 188.4 13.1 19.4 7.2 164.9 17.0 6.3
B- .61
-------
Port change
1214 4.1 22 .4 202.9 16.3 24.1 11.0 167.9 20.0 9.1
1215 4.1 22.4 204.4 15.0 22.2 11.0 169.3 18.4 9.1
1216 4.0 22.7 204.8 15.9 23.5 11.0 168.5 19.3 9.0
1217 3.9 23.1 205.7 17.1 25.3 11.0 168.0 20.7 9.0
1218 4.0 23.0 207.0 16.6 24.6 11.0 170.6 20.2 9.1
1219 4.1 22.6 209.4 14.4 21.3 11.1 173.8 17.7 9.2
1220 4.2 22.7 209.7 13.7 20.3 11.5 174.2 16.8 9.6
1221 4.3 22.6 211.4 13.3 19.7 11.7 176.9 16.5 9.8
1222 4.2 22.7 212.5 13.2 19.5 11.8 177.1 16.3 9.8
1223 4.1 23.0 212.5 14.2 21.0 11.8 176.2 17.4 9.8
1224 4.0 23.1 213.1 14.8 21.9 11.6 175.8 18.1 9.6
1225 4.2 22.7 214.5 13.9 20.6 11.5 178.9 17.1 9.6
1226 4.1 22.9 214.9 12.9 19.1 11.5 178.4 15.8 9.5
1227 4.3 22.8 215.5 11.8 17.5 11.6 180.2 14.6 9.7
1228 4.3 22.8 215.7 12.6 18.6 11.5 181.0 15.6 9.7
1229 4.2 23.1 215.2 13.4 19.8 11.5 179.5 16.5 9.6
1230 4.2 23.1 215.6 13.2 19.5 11.4 180.0 16.3 9.5
1231 4.2 23.2 215.7 13.4 19.8 11.3 179.9 16.5 9.4
1232 4.7 22.7 216.9 12.3 18.2 11.3 185.8 15.6 9.7
1233 4.8 22.5 217.6 12.5 18.5 11.3 187.5 15.9 9.7
1234 4.8 22.5 217.4 13.1 19.4 11.3 187.8 16.7 9.8
1235 4.8 22.5 217.2 13.1 19.4 11.0 187.1 16.7 9.5
1236 4,8 22.5 217.0 13.1 19.4 10.6 187.0 16.7 9.1
1237 4.9 223 217.4 12.9 19.1 10.3 188.5 16.5 8.9
1238 5.3 21.8 218.7 11.3 16.7 9.9 195.3 14.9 8.8
1239 5.4 21.7 218.3 10.5 15.5 9.6 195.9 13.9 8.6
1240 5.3 22.0 217.1 10.7 15.8 9.4 193.8 14.1 8.4
1241 5.2 22.1 216.6 10.8 16.0 9.1 192.2 14.2 8.1
1242 5.2 21.9 217.0 10.6 15.7 8.8 192.3 13.9 7.8
1243 5.7 21.5 217.6 10.4 15.4 8.7 198.9 14.1 8.0
1244 5.3 21.8 216.3 11.2 16.6 8.6 192.8 14.8 7.7
Port change
1308 4.6 21.8 195.2 12.9 19.1 7.7 166.1 16.2 6.6
1309 4.6 21.8 195.3 13.3 19.7 7.8 166.3 16.8 6.6
1310 4.4 22.1 194.5 14.2 21.0 7.9 164.2 17.7 6.7
1311 4.4 222 194.5 14.6 21.6 8.0 164.2 18.2 6.8
1312 4.8 21.7 196.4 12.8 18.9 8.1 169.8 16.4 7.0
1313 4.8 21.8 196.7 13.0 19.2 8.2 170.1 16.6 7.1
1314 4.9 21.7 197.9 12.8 18.9 8.4 171.8 16.4 7.3
1315 4.8 21.8 198.1 12.6 18.6 8.5 171.1 16.1 7.3
1316 4.9 21.7 199.3 9.8 14.5 172.8 12.6 7.4
1317 4.9 21.7 200.1 9.7 14.3 8.4 174.2 12.5 7.3
B-62
-------
1318 4.8 21.9 200.8 10.1 14.9 8.2 174.0 12.9 7.1
1319 4.8 22.0 201.2 10.4 15.4 8.1 173.3 13.3 7.0
1320 4.8 22.0 202.4 11.0 16.3 8.0 174.7 14.0 6.9
1321 4.6 22,3 202.8 12.2 18.0 7.9 173.1 15.4 6.7
1322 4.7 22.4 204.3 12.1 17.9 7.9 175.4 15.4 6.8
1323 4.6 22.6 205.6 13.0 19.2 7.9 175.9 16.5 6.8
1324 4.7 22.2 207.3 13.1 19.4 8.0 178.3 16.7 6.9
1325 4.8 22.2 208.9 12.9 19.1 8.1 180.4 16.5 7.0
1326 4.8 22.1 210.1 13.1 19.4 8.1 181.1 16.7 7.0
1327 4.8 22.1 211.3 13.1 19.4 8.1 182.2 16.7 7.0
1328 5.0 22.3 211.6 13.4 19.8 8.0 184.9 17.3 7.0
1329 5.0 22.1 213.2 12.6 18.6 8.0 187.0 16.4 7.0
1330 5.5 21.4 215.5 10.8 16.0 8.0 195.0 14.5 7.2
1331 6.6 20.4 218.6 9.7 14.3 7.9 212.8 14.0 7.7
122 ’ ) lfl Ifl2
jJJ ,tJ £ tJ.J . . . .
1333 7.0 20.3 220.1 8.7 12.9 7.8 220.4 12.9 7.8
1334 6,6 20.7 219.4 9.1 13.5 7.6 213.2 13.1 7.4
1335 6.7 20.6 219.7 9.3 13.8 7.2 215.4 13.5 7.1
1336 7.0 20.1 221.1 9.1 13.5 7.0 220.3 13.4 7.0
1337 7.2 19.9 221.1 9.2 13.6 6.7 223.7 13.8 6.8
1338 7.4 19.5 222.0 9.2 13.6 6.5 228.2 14.0 6.7
Port change
1418 11.1 15.1 213.5 7.9 11.7 4.9 302.8 16.6 7.0
1419 11.1 15.4 212.5 8.0 11.8 4.8 300.5 16.7 6.8
1420 11.0 15.3 212.2 8.1 12.0 4.8 296.2 16.7 6.7
1421 10.9 15.1 210.8 7.7 11.4 4.7 293.1 15.8 6.5
1422 10.9 14.9 209.1 8.4 12.4 4.7 290.4 17.3 6.5
1423 11.1 14.6 206.7 7.6 11.2 4.7 293.2 15.9 6.7
1424 11.4 14.3 204.0 7.9 11.7 4.7 298.7 17.1 6.9
1425 11.3 14.5 199.8 8.2 12.1 4.7 289.6 17.6 6.8
1426 10.3 15.7 192.6 8.4 12.4 4.7 251.1 16.2 6.1
1427 9.4 16.2 187.5 7.4 10.9 4.7 225.9 13.2 5.7
1428 &9 16.6 182.9 7.5 11.1 4.7 210.9 12.8 5.4
1429 &4 16.9 178.2 7.5 11.1 4.7 198.3 12.3 5.2
1430 &3 16.9 174.4 7.7 11.4 4.7 191.6 12.5 5.2
1431 8.1 17.1 170.4 7.1 10.5 4.7 185.2 11.4 5.1
1432 8.1 17.1 167.4 6.5 9.6 4.7 181.4 10.4 5.1
1433 8.1 17.4 163.1 6.7 9.9 4.7 176.5 10.7 5.1
1434 8.2 17.3 160.0 6.9 10.2 4.7 174.7 11.1 5.1
1435 8.4 17.1 157.0 7.1 10.5 4.7 174.4 11.7 5.2
1436 8.7 16.6 154.3 7.2 10.7 4.7 175.6 12.1 5.3
1437 &7 16.6 150.9 7.7 11.4 4.7 171.9 13.0 5.4
1438 8.3 16.5 148.2 7.6 11.2 4.7 169.9 12.9 5.4
B-63
-------
1439 8.9 16.2 145.5 7.3 10.8 4.7 168.8 12.5 5.5
1440 8.6 16.3 142.1 6.5 9.6 4.6 161.0 10.9 5.2
1441 8.9 16.4 139.1 6.2 9.2 4,6 160.7 10.6 5.3
1442 17.0 135.1 6.3 9.3 4.5 154.8 10.7 5.2
1443 &5 17.0 132.7 6.4 9.5 4.5 148.6 10.6 5.0
1444 7.8 17.3 129.2 6.5 9.6 4.4 137.1 10.2 4.7
1445 7.1 18.7 124.7 6.9 10.2 4.4 125.6 10.3 4.4
1446 6.8 19.1 121.5 7.2 10.7 4.4 119.6 10.5 4.3
1447 7.0 18.9 119.4 7.3 10.8 4.3 119.1 10.8 4.3
1448 7.1 18.7 117.6 ‘7.2 10.7 4.2 118.4 10.7 4.2
AVG = 5.9 20.7 198.4 11.7 17.3 8.3 187.3 15.9 ‘7.6
MIN = 3.7 14.3 117.6 6.2 9.2 4.2 11&4 10.2 4.2
MAX = 11.4 23.7 222.0 19.9 29.4 12.2 302.8 24.8 10.4
02 Oxygen
C02 = Carbon Dioxide
CO Carbon Monoxide
THCH = Hydrocarbons-Hot line
THCC = Hydrocarbons-Cold line
B -64
-------
Filename: RUN2
Name: RUN2
Date:06-21 -1990
Location: HANNIBAL,M0
Project 9102-63-13
Operator BC
VERSION = 05/07/90
CO THCH T}-iCC
TIME 02 C02 CO THCI-1 THCFI THCC @ 7% 02 @ 7% 0 @ 7% 0
(%, (%, (ppm, (ppm, (ppm, (ppm, (ppm, (ppm, (ppm,
dry) dry) dry) wet) dry) dry) dry) dry) dry)
1230 4.3 22.8 293.8 37.2 59.7 40.4 246.9 50.2 33.9
1231 4.3 22.7 294.8 33.2 53.3 41.6 246.8 44.6 34.8
1232 3.9 23.4 293.1 35.9 57.5 41.8 240.2 47.2 34.3
1233 4.1 23.2 295.0 37.7 60.5 42.0 243.8 50.0 34.7
1234 3.6 23.6 294.9 45.6 73.2 41.8 237.5 59.0 33.7
1235 3.5 23.7 295.8 48.4 77.7 41.8 237.2 62.3 33.5
1236 3.7 23.4 29&5 45.8 73.5 42.1 242.1 59.6 34.1
1237 3.9 23.3 299.7 40.3 64.7 42.0 245.8 53.1 34.4
1238 4.1 23.0 302.1 39.4 63.2 42.2 250.6 52.5 35.0
1239 3.7 23.4 301.0 44.9 72.1 42.4 244.1 58.5 34.4
1240 4.3 22.8 304.4 35.0 56.2 418 254.7 47.0 35.S
1241 4.3 23.0 304.2 38.7 62.1 43.2 254.7 52.0 36.2
1242 4.5 226 306.2 32.5 52.2 43.5 259.8 44.3 36.9
1243 4.1 23.2 303.9 37.2 59.7 44.1 252.3 49 6 36.6
1244 4.2 23.0 305.3 39.2 62.9 45.9 254.4 52.4 38.3
1245 3.7 24.1 301.6 51.1 82.0 45.3 244.1 66.4 36.7
1246 3.5 24.6 300.0 58.4 93.7 44.5 239.5 74.8 35.5
1247 4.1 23.1 305.7 43.3 69,5 44.9 252.8 57.5 37.1
1248 3.9 23.2 306.1 42.4 68.1 46.4 250,2 55.6 37.9
1249 3.9 23.2 305.1 40.2 64.5 48.7 249.8 52.8 39.9
1250 3.8 23.3 304.8 43.2 69.3 46.7 248.4 56.5 38.1
1251 4.3 23.1 305.8 38.1 61 2 49.5 256.1 51.2 41.4
1252 4.0 23.0 305.8 37.3 59 9 49.2 2520 49.3 40.5
1253 4.0 23.0 305.5 36.7 58 9 49.0 251.6 48.5 40.4
1254 4.0 22.9 305.5 34.7 55 .7 48.4 251.3 45.8 39.8
1255 3.9 22.9 304.7 37.9 60.8 47.6 249.5 49.8 39.0
1256 3.6 23.3 303.5 41.6 66.8 47.0 244.8 53.8 37.9
1257 3.6 23.5 302.8 43.1 69.2 46.2 243.6 55.7 37.2
1258 3.7 24.0 300.4 53.5 85.9 46.0 243.1 69.5 37.2
1259 3.5 23.9 299.9 57.1 91.7 46.4 239.9 73.3 37.1
1300 3.8 23.5 300.8 52.9 84.9 47.5 245.3 69.2 38.7
B-65
-------
Port change
1319 3.8 23.7 289.1 53.0 85.1 56.5 235.9 69.4 46.1
1320 3.5 23.9 286.9 56.8 91.2 56.6 229.7 73.0 45.3
1321 3.8 23.9 285.4 43.6 70.0 56.3 231.8 56.8 45.7
1322 3.5 24.0 283.7 53.1 85.2 56.8 227.5 68.3 45.5
1323 4.0 23.2 285.2 47.4 76.1 57.7 235.4 62.8 47.6
1324 3.8 23.4 282.9 49.2 79.0 58.7 230.7 64.4 47.9
1325 3.9 23.3 281.9 49.9 80.1 59.3 230.5 65.5 48.5
1326 4.3 219 281.7 45.5 73.0 59.4 236.6 61.3 49.9
1327 3.8 23.5 278.4 41.0 65.8 58.9 226.5 53.5 47.9
1328 3.8 23.4 277.5 24.4 39.2 58.7 225.9 31.9 47.8
1329 3.8 23.4 276.7 19.9 31.9 58.0 225.0 26.0 47.2
1330 4.1 23.0 277.5 21.4 34.3 57.8 229.9 28.5 47.9
1331 3.8 23.5 275.4 40.0 64.2 58.2 224.4 52.3 47.4
1332 3.9 23.3 275.1 41.9 67.3 58.8 224.7 54.9 48.0
1333 3.9 23.3 275.1 47.2 75.8 58.8 225.1 62.0 48.1
1334 3.8 23.4 274.6 56.8 91.2 58.4 222.9 74.0 47.4
1335 3.7 23.5 273.8 57.0 91.5 5&3 221.7 74.1 47.2
1336 3.5 23.8 272.5 55.1 88.4 57.8 218.2 70.8 46.3
1337 3.7 23.6 273.5 58.2 93.4 57.3 221.2 75.6 46.3
1338 3.8 23.4 273.7 52.5 84.3 57.4 222 .8 68.6 46.7
1339 3.9 23.3 274.0 53.4 85.7 58.1 223.9 70.1 47.5
1340 4.7 22.3 277.1 44.8 71.9 58.6 237.7 61.7 50.3
1341 4.0 23.2 273.4 45.1 72.4 58.5 224.8 59.5 48.1
1342 4.1 23.0 274.0 44.9 72.1 58.2 227.5 59.8 48.3
1343 4.5 22.5 275.7 40.3 64.7 57.4 233.5 54.8 48.6
1344 4.1 22.8 274.3 43.5 69.8 56.5 226.6 57.7 46.7
1345 4.2 226 274.8 42.8 68.7 55.9 228.5 57.1 46.5
1346 4.2 22.5 275.1 42.9 68.9 54.9 229.3 57.4 45.8
1347 4.9 21.6 277.5 34.1 54.7 53.9 240.7 47.5 46.8
1348 4.7 22.0 275.2 35.4 56.8 53.2 236.2 48.8 45.7
1349 4.6 22.1 273.3 35.0 56.2 52.4 233.2 47.9 44.7
Port change
1410 3.4 24.2 278.6 59.6 95.7 56.7 221.4 76.0 45.1
1411 3.3 24.1 280.5 60.6 97.3 59.2 221.5 76.8 46.7
1412 3.3 24.1 283.8 57.4 92.1 60.2 224.5 72.9 47.6
1413 3.5 23.8 286.8 52.6 84.4 60.9 22.8.8 67.4 48.6
1414 3.7 23.6 285.3 46.8 75.1 61.4 230.6 60.7 49.6
1415 3.7 24.0 282.7 52.0 83.5 61.5 228.1 67.4 49.6
1416 3.7 24.1 283.0 52.1 83.6 60.9 22&5 67.5 49.2
1417 3.6 24.0 283.7 49.8 79.9 60.0 227.6 64.1 48.1
1418 3.5 24.0 283.3 53.8 86.4 59.7 226.8 69.1 47.8
1419 3.7 23.9 284.2 50.5 81.1 59.6 229.7 65.5 48,2
B-66
-------
1420 3.7 23.9 282.9 49,7 79.8 59.3 228.7 64.5 47.9
1421 3.8 23.8 221.5 47.7 76.6 59.1 229.7 62.5 48.2
1422 3.8 24.1 279.3 46,8 75: 58.7 226.8 61.0 47.7
1423 4.1 23.6 280.1 42.3 67.9 58.1 232.2 56.3 48.2
1424 3.8 24.0 276.6 46.3 74.3 57.5 225.7 60.6 46.9
142.5 3.8 24.0 275.0 46,5 74.6 56.9 223.8 60.8 46.3
1426 3.6 24.1 273.1 49.0 78.7 56.2 220.2 63.4 45.3
1427 3.8 23.8 272.5 47.6 76.4 55.4 221.5 62.1 45.0
142.8 3.4 24.5 268.3 54.5 87.5 54.9 212.8 69.4 43.5
1429 3.3 24.4 267.7 57.1 91.7 54.9 2121 72.6 43.5
1430 3.5 24.2 267.2 54.7 87.3 55.0 214.0 70.3 44.1
1431 3.5 24.1 266.6 54.8 88.’) 55.6 213.5 70.4 44 ,5
1432 3.7 24.4 264.7 52.9 84.9 56.8 214.0 68.6 45.9
1433 3.9 23.9 266.0 48.2 77.4 57.5 217.7 63.3 47.0
1434 4.0 23.7 266.0 46,7 75.’) 58.1 219.4 61.8 47.9
1435 3.9 23.9 265.2 49.8 79.9 58.4 216.6 65.3 47.7
1436 3.9 23.8 265.3 48.8 78.3 58.1 216.8 64.0 47.5
1437 3.4 24.2 263.7 56.2 90.2 57.6 209.9 71.8 45.8
1438 3.4 24.0 264.6 50.6 81.2 57.3 209.9 64.4 45.5
1439 3.4 23.9 265.2 53.5 85.9 57.1 211.2 684 45.5
1440 3.9 23.6 266.8 50.6 81.2 57.6 218.1 66.4 47.1
Port change
1510 4.1 22.9 259.3 45.5 73.0 54.0 214.8 60.5 44.7
1511 4.3 22.6 260.3 38.3 61.5 54.1 217.7 51.4 45.2
1512 4.1 22.8 260.0 43.6 70.0 54.1 215.8 58.1 44.9
1513 3.9 22.8 259.8 45.4 72.9 53.5 213.0 59.7 43.9
1514 3.8 23.0 259,5 43.8 70.3 52.7 211.5 57.3 419
1515 3.3 23.5 25&4 50.7 81.4 520 204.8 64.5 41.2
1516 4.3 22.3 262.4 40.9 65.7 51.7 220.1 55.1 43.4
1517 4.1 22.7 260.7 37.4 60.0 51.7 215.5 49.6 42.7
1518 3.6 23.2 259.7 46.4 74.5 52.5 208.7 59.9 42.2
1519 5.0 21.5 265.2 33.0 53.0 52.8 231.8 46.3 46.1
1520 4.6 22.1 263.2 34.4 55.2 51.8 224.0 47.0 44.1
1521 4.8 21.7 264.8 30.0 48.2 51.9 229.1 41.7 44.9
1522 4.0 22.6 262.0 38.3 61.5 51.5 216.1 50.7 42.5
1523 4.3 22.3 263.9 36.2 58.1 50.1 221.6 48.8 42.1
1524 4.3 22.5 263.0 35.1 56.3 48.8 220.9 47.3 41.0
1525 4.0 22.7 262.5 38.8 62.3 48.0 215.8 51.2 39.5
1526 4.2 22.4 264.2 42.7 68.5 47.9 220.7 57.3 40.0
1527 4.1 22.7 263.5 41.2 66 1 47.3 218.0 54.7 39.1
1528 4.0 22.7 264.3 43.9 70 5 46.9 217.7 58.0 38.6
1529 3.9 23.0 263.5 44.0 70.6 46.8 215.4 57.7 38.2
1530 3.7 23.1 263.6 45.3 72.7 46.5 212.9 58.7 37.6
B -67
-------
1531 3.5 23.3 263.6 46.1 74.0 46.5 211.1 59.3 37.2
1532 3.7 22.9 265.3 48.2 77.4 47.0 215.2 62.8 38.1
1533 3.9 22.8 266.0 41.2 66.1 47.5 217.4 54.0 38.8
1534 3.9 22.7 266.9 48.6 78.0 48.7 219.0 64.0 40.0
1535 4.2 22.3 269.0 46.1 74.0 49 ,7 224.2 61.7 41.4
1536 4.4 22.1 270.0 42.2 67.7 50.1 227.0 57.0 42.1
1537 4.0 22.6 269 ,2 42.0 67.4 50.4 222.0 55.6 41.6
1538 3.9 22.6 269.5 45.2 72.6 50.1 220.5 59.4 41.0
1539 4.2 22.1 272.3 35.8 57.5 49.0 227.2 47.9 40.9
1540 4.1 22.1 272.8 35.5 57.0 48.3 226.4 47.3 40.1
AVG = 3.9 23.3 279.5 44.8 71.9 52.6 229.0 58.8 43.1
MIN = 3.3 21.5 258.4 19.9 31.9 40.4 204.8 26.0 33.5
MAX = 5.0 24.6 306.2 60.6 97.3 61.5 259.8 76.8 50.3
02= Oxygen
C02 = Carbon Dioxide
CO = Carbon Monoxide
TI-ICH = Hydrocarbon Hot-line
THCC = Hydrocarbon Cold-line
B -68
-------
Filename: RUN3
Name:RUN3
Date:06-22-1990
Location: HANN1BAL,M0
Project :9102-63-13
Opera tor BG
VERSION = 05/07/90
CO TI-ICH TI-ICC
TIME 02 C02 CO TNCH THCH THCC @ 7% 02 @ 7% 02 @ 7% 02
(%, (%, (ppm, (ppm, (ppm, (ppm, (ppm, (ppm, (ppm,
dry) dry) dry) dry) dry) dry) dry) dry) dry)
1135 3.7 23.7 244.0 69,5 108.1 50.1 196.9 87.2 40.4
1136 3.9 23.2 29&4 56.7 3&2 50.7 243.9 711 41.4
1137 4.2 23.0 307.8 55.3 .96.0 52.5 255.9 71.5 43.6
1138 4.2 219 298.8 54.9 .35.4 55.0 248.9 71.1 45.8
1139 4.1 22.9 302,9 54.3 .34.4 56.1 250.5 69.8 46.4
1140 4.0 23.1 291.8 61.0 94.9 56.3 240.2 78.1 46.3
1141 4.2 22.5 323.3 44.1 ‘58.6 56.1 268.8 57.0 46.6
1142 4.5 22.6 320.5 45.4 70.6 55.9 271.6 59.8 47.4
1143 4.4 219 3018 49.6 77.1 55.9 254.9 64.9 47.1
1144 4.5 22.4 331.7 424 65.9 55.0 281.1 55.9 46.6
1145 4.6 22.6 315.4 57.0 88.6 54.2 268.6 75.5 46.2
1146 4.5 22.7 310.6 60.5 94.1 54.5 263.7 79.9 46.3
1147 4.4 22.9 298.7 62.3 96.9 53.7 251.8 81.7 45.3
1148 4.0 23.1 273.3 61.0 94.9 53.1 224.8 78.0 43.7
1149 3.8 23.1 269.5 61.4 95.5 52.7 218.9 77.5 42.8
1150 4 O 22.5 285.9 44.9 69.8 52.7 234.8 57.3 43.3
1151 4.2 227 304.8 45.1 70.1 53.7 253.4 58.3 44.6
1152 4.1 22.7 309.0 47.2 73.4 54.7 256.6 61.0 45.4
1153 4.2 22.3 309.9 44.2 68.7 54.7 258.7 57.4 45.7
1154 4.2 223 320.5 47.1 73.3 54.1 267.2 61.1 45.1
1155 4.2 228 317.1 55.9 86.9 53.4 264.4 72,5 44.5
1156 4.1 22.8 303.7 55.3 86.0 52.1 251.4 71.2 43.1
1157 3.7 23.1 296.6 67.7 105.3 50.7 239.9 85.2 41.0
1158 3.7 22.9 277.6 62.3 96.9 50.3 224.8 78.5 40.7
1159 4.0 22.6 283.3 41.0 63.8 50.3 233.2 52.5 41.4
1200 4.2 22.4 306.7 44.4 69.1 51.3 255.0 57.4 42.6
1201 4.3 22.3 3225 4.8.7 75.7 52.5 270.0 63.4 44.0
1202 4.2 22.5 326.2 50.6 7&7 52.9 271.7 65.5 44.1
1203 4.3 22.4 315.6 51.2 79.6 52.6 264.3 66.7 44.0
1204 4.1. 22.7 322.9 61.8 96.1 52.2 267.6 79.7 43.3
1205 4.2 22.3 314.6 56.2 87.4 51.5 2626 73.0 43.0
B-69
-------
Port change
1223 4.1 22.5 318.2 57.4 89.3 40.4 263.0 73.8 33.4
1224 4.1 22.2 323.5 56.9 88.5 40.5 268.3 73.4 33.6
1225 4.5 21.8 331.1 51.8 80.6 41.2 280.9 68.4 35.0
1226 4.3 22.1 335.2 39.0 60.7 41.9 280.3 50.7 35.0
1227 4.3 21.9 334.1 35.1 54.6 42.7 280.3 45.8 35.8
1228 4.1 22.6 342.3 44.2 68.7 42.9 283.9 57.0 35.6
1229 4.2 22.5 338.7 48.0 74.7 42.4 281.6 62.1 35.2
1230 4.1 22.6 320.1 41.1 63.9 41.7 265.5 53.0 34.6
1231 4.1 22.4 330.2 38.8 60.3 41.1 274.2 50.1 34.1
1232 4.4 22.0 336.9 34.7 54.0 40.5 284.8 45.6 34.2
1233 4.3 22.3 343.4 43.9 68.3 42.8 287.7 57.2 35.9
1234 4.2 22.4 343.8 47.5 73.9 43.5 286.5 61.6 36.3
1235 4.3 22.3 337.1 45.7 71.1 43.2 283.1 59.7 36.3
1236 4.5 22.0 336.6 38.6 60.0 43.0 285.4 50.9 36.5
1237 4.3 22.5 33&1 41.8 65.0 43.3 283.3 54.5 36.3
1238 4.2 22.6 338.1 47.4 73.7 43.6 282.3 61.5 36.4
1239 4.2 22.6 332.0 54.2 84.3 43.3 276.7 70.2 36.1
1240 4.3 22.4 334.3 48.5 75.4 43.4 280.4 63.3 36.4
1241 4.5 22.2 333.1 41.9 65.2 43.9 282.3 55.2 37.2
1242 4.3 22.3 338.9 39.5 61.4 44.9 284.4 51.6 37.7
1243 4.4 22.3 334.6 37.6 58.5 45.3 281.7 49.2 38.1
1244 4.3 22.3 341.4 41.7 64.9 45.3 286.5 54.4 38.0
1245 4.3 224 338.1 44.2 68.7 45.3 283.8 57.7 38.0
1246 4.6 22.0 337.9 41.3 64.2 45.2 287.7 54.7 38.5
1247 4.3 22.5 345.2 45.8 71.2 45.3 288.7 59.6 37.9
1248 4.3 22.4 344.8 44.2 68.7 45.1 288.7 57.6 37.8
1249 4.4 221 332.9 35.3 54.9 44.3 281.4 46.4 37.5
1250 4.6 21.9 345.8 A A 43.9 294.5 A 37.4
1251 4.5 22.1 352.1 A A 44.0 298.6 A 37.3
1252 4.6 22.1 350.9 A A 43.5 298.6 A 37.0
1253 4.6 22.2 344.7 A A 42.6 293.7 A 36.3
Port change
1314 4.2 222 347.2 49.1 76.4 42.6 289.7 63.7 35.5
1315 4.3 22.0 344.0 50.3 7&2 427 2.88.4 65.6 35.8
1316 4.2 21.9 345.2 46.6 72.5 43.3 288.4 60.5 36.2
1317 4.5 21.5 346.7 38.5 59.9 43.8 293.8 50.7 37.1
1318 4.7 21.4 348.0 35.7 55.5 43.8 298.5 47.6 37.6
1319 4.6 21.5 355.0 34.5 53.7 43.3 302.1 45.7 36.9
1320 4.7 21.3 365.0 33.7 52.4 42.2 313.1 45.0 36.2
1321 4.6 21.5 365.4 36.7 57.1 40.7 312.1 48.8 34.8
1322 4.5 21.5 360.7 37.8 5&8 39.6 305.9 49.8 33.6
1323 4.7 21.2 351.6 34.3 53.3 38.0 302.5 45.9 32.7
B-70
-------
1324 5.0 20.8 362.1 30.5 47.4 37.0 317.4 41.6 32.4
1325 5.0 21.0 357.5 30.6 47.6 36.4 3122 41.6 31.8
1326 4.8 21.7 350.0 35,1 54.6 35.6 302.8 47.2 30.8
1327 4.8 21.3 349.2 34.7 54.0 34.3 302.2 46.7 29.7
1328 5.1 20.9 353.4 31.4 48.8 33.2 310.8 42.9 29.2
1329 5.1 20.8 349.8 22.5 35.0 33.0 307.0 30.7 29.0
1330 4.9 21.2 349.7 25.5 39.7 33.2 304.1 34.5 28.9
1331 5.5 20.6 358.8 23.4 36.4 32.5 324.3 32.9 29.4
1332 4.8 21.4 356.0 26.2 0.7 31.6 306.7 35.1 27.2
1333 4.6 21.6 353.7 23.6 26.7 31.2 301.4 31.3 26.6
Plant changing feed tanks
1540 3.4 22.8 326.1 53.2 82.7 51.6 259.4 65.8 41.0
1541 3.4 22.6 322.4 55.9 86.9 51.2 256.3 69.1 40.7
1542 3.5 22.6 319.5 62.0 96.4 50.9 255.2 77.0 40.7
1543 3.5 22.5 317.7 55.1 85.7 51.3 254.2 68.6 41.0
1544 3.6 22.4 317.3 52.8 82.1 51.9 255.0 66.0 41.7
1545 3.6 22.4 317.2 49.6 77.1 52.1 255.4 62.1 41.9
1546 3.7 22.4 318.3 51.4 79.9 52.2 257.7 64.7 42.3
1547 3.9 22.2 319.5 43.0 66.9 52.4 261.6 54.8 42.9
1548 4.0 22.0 320.7 39.5 61.4 52.5 264.7 50.7 43.3
1549 3.7 22.4 319.2 50.2 7&1 52.0 258.0 63.1 42.0
1550 3.7 22.4 319.1 47.4 ‘13.7 51.6 258.2 59.7 41.8
Port change
1615 3.7 22.5 309.1 48.6 75.6 48.2 250.6 61.3 39.1
1616 3.7 225 308.9 44.3 68.9 47.9 250.0 55.8 38.8
1617 3.7 22.6 302.7 48.8 ‘75.9 47.9 244.5 61.3 38.7
1618 3.8 22.5 311.7 57.2 89.0 48.5 253.4 72.3 39.4
1619 3.9 22.1 3228 57.8 89.9 49.4 264.0 73.5 40.4
1620 3.8 22.4 314.8 56.3 87.6 50.0 256.8 71.4 40.8
1621 3.6 23.0 289.6 60.2 93.6 50.4 233.5 75.5 40.6
1622 3.7 22.5 301.5 53.2 32.7 50.0 244.4 67.1 40.5
1623 3.8 22.5 312.1 50.1 77.9 50.1 254.0 63.4 40.8
1624 3.8 22.4 321.8 54.3 34.4 51.0 261.6 68.7 41.5
1625 3.8 22.4 330.3 48.1 74.8 51.7 268.4 60.8 42,0
1626 3.8 22.5 320.5 49.4 76.8 52.0 261.2 62.6 42.4
1627 3.9 22.2 325.3 45.9 71.4 52.1 265.6 58.3 42.5
1628 3.9 22.1 329.8 46.5 72.3 51.7 269.9 59.2 42.3
1629 3.9 22.2 342.4 36.2 56.3 51.6 281.0 46.2 42.3
1630 4.0 22.1 341.0 37.0 57.5 51.4 281.2 47.4 42.4
1631 4.0 22.3 323.8 51.2 79.6 50.6 266.0 65.4 41.6
1632 3.9 22.3 3126 49.8 77.4 50.0 256.1 63.4 41.0
1633 3.8 22.7 304.2 52.6 81.8 49.2 247.5 66.5 40.0
1634 3.7 22.4 312.7 47.7 74.2 49.4 253.5 60.1 4 .0.0
B-7 1
-------
1635 3.9 22.3 319.6 53.0 82.4 50.2 261.2 67.4 41.0
1636 3.9 22.4 302.8 54.2 84.3 51.2 247.2 68.8 41.8
1637 3.8 22.8 300.0 56.7 88.2 51.3 243.6 71.6 41.7
1638 3.8 22.8 330.4 35.5 55.2 51.4 268.6 44.9 41.8
1639 3.8 23.0 329.4 45.5 70.8 52.1 268.3 57.6 42.4
1640 3.9 23.0 337.0 42.3 65.8 52.8 275.1 53.7 43.1
1641 4.1 22.7 352 .3 41.5 64.5 52.5 291.5 53.4 43.4
1642 4.2 22.3 344.9 48.1 74.8 52.1 282.1 62.5 43.5
1643 4.3 22.6 347.6 50.6 78.7 51.2 290.5 65.8 42.8
1644 4.3 22.4 359.3 41.8 65.0 49.6 301.2 54.5 41.6
1645 4.3 22.5 353.0 420 65.3 48.3 295,9 54.8 40.5
AVG = 4.2 22.3 326.3 45,1 70.1 47.5 271.8 60.1 39.4
MIN = 3.4 20.6 244.0 14.3 35.0 31.2 196.9 26.6
MAX = 5.5 23.7 365.4 69.5 108.1 56.3 324.3 87.2 47.4
02 = Oxygen
C02 = Carbon Dioxide
CO = Carbon Monoxide
THCH = Hydrocarbon Hot-line
THCC = Hydrocarbon Cold-line
B-7 2
-------
Filename: RUN4
Name:RUN4
Date:06-23-1990
Location: HANNIBAL,M0
Project: 9102-63-13
OperatorBG
VERSION = 05/07/90
CO THCI-I TI-ICC
TIi ’vlE 02 C02 CO THCI-I THCE-i THCC @ 7% 02 @ 7% 02 @ 7% 02
(%, (%, (ppm, (ppm, (ppm, (ppm, (ppm, (ppm, (ppm,
dry) dry) dry) wet) dr’i) dry) dry) dry) dry)
1055 4.5 22.5 271.0 32.3 7.2 24.7 229.2 39.9 20.9
1056 4.4 22.6 274.3 31.6 L 6.1 24.8 230.9 38.8 20.9
1057 4.2 22.6 267.5 29.3 42.8 24.8 223.4 35.7 20.7
1058 4.4 22.5 264.3 29.1 42.5 24.7 222.8 35.8 20.8
1059 4.3 27_S 273.6 28.6 41.8 24.7 229.8 35.1 20.7
1100 4.2 22.9 265.3 33.6 49.1 25.1 221.2 40.9 20.9
1101 4.2 22.6 274.5 30.8 45.0 24.9 228.9 37.5 20.8
1102 4.2 22.6 269.7 30.1 43.9 24.8 224.5 36.6 20.6
1103 4.2 22.7 268.9 31.3 45.7 25.5 223.8 38.0 21.2
1104 4.4 22.3 270.9 28.9 42.2 26.3 228.5 35.6 22.2
1105 4.6 22.2 273.0 27.3 39.9 26.8 233.0 34.0 22.9
1106 4.3 22.7 275.7 31.0 45.3 27.3 231.5 38.0 22.9
1107 4.4 22.4 271.2 27.1 39.6 27.1 228.2 33.3 22.8
1108 4.4 22.6 268.0 30.2 44.1 26.2 226.4 37.2 27_I
1109 3.9 23.9 240.9 41.7 SO.9 25.7 197.1 49.8 21.0
1110 4.0 23.0 251.9 33.5 4&9 25.3 206.8 40.2 20.8
1111 4.0 22.7 264.0 30.4 44.4 25.3 217.8 36,6 20.9
1112 4.2 22.6 266.2 29.1 42.5 27.6 222.0 35.4 23.0
1113 4.2 22.6 263.0 28.9 42.2 29.2 218.9 35.1 24.3
1114 4.3 22.4 264.3 30.1 43.9 29.3 221.7 36.9 24.6
1115 4.3 22.6 264.4 31.7 46.3 2&9 221.0 38.7 24.2
1116 4.2 22.5 266.8 30.1 43.9 28.4 222.9 36.7 23.7
1117 4.1 22.8 263.7 33.5 48.9 27.7 219.0 40.6 23.0
1118 4.1 22.6 267.3 27.9 40.7 27.5 222.0 33.8 22.8
1119 4.1 22.6 267.0 26.0 3&0 26.9 221.6 31.5 22.3
1120 4.2 22.4 265.8 25.6 37.4 26.9 221.8 31.2 22.4
1121 4.3 22.5 261.6 27.2 39.7 27.0 219.4 33.3 22.6
1122 4.3 23.1 272.9 32.1 46.9 26.6 228.1 39.2 22.2
1123 4.2 216 269.7 27.7 40.4 26.1 224.6 33.7 21.7
1124 4.3 22.4 263.7 24.8 36.2 25.5 221.5 30.4 21.4
1125 4.4 22.6 270,2 25.0 36.5 25.5 227.5 30.7 21.5
8-73
-------
Port change
1140 4.2 22.7 256.0 27.9 40.7 26.5 213.1 33.9 22.1
1141 4.2 22.5 256.0 25.4 37.1 25.7 213.2 30.9 21.4
1142 4.1 22.6 255.7 25.7 37.5 25.2 212.3 31.2 20.9
1143 4.1 22.5 250.3 22.3 32.6 25.2 207.8 27.0 20.9
1144 4.2 22.6 250.2 23.8 34.7 25.1 208.1 28.9 20.9
1145 4.2 226 251.5 25.1 36.6 24.5 209.3 30.5 20.4
1146 4.2 22.6 256.2 24.5 35.8 24.1 213.2 29.8 20.1
1147 4.2 22.4 254.7 23.6 34.5 23.7 212.1 28.7 19.7
1148 4.3 22.6 252.7 25.4 37.1 23.8 211.2 31.0 19.9
1149 4.3 22.7 251.6 26.2 38.2 23.8 210.9 32,1 20.0
1150 4.3 22.5 252.4 24.0 35.0 23.4 211.6 29.4 19.6
1151 4.5 22 ,2 248.9 21.0 30.7 23.1 210.9 26.0 19.6
1152 4.4 22.3 249.6 21.6 31.5 23.0 210.5 26.6 19.4
1153 4.2 22.7 250.2 23.9 34.9 23.0 208.0 29.0 19.1
1154 4.3 22.4 250.9 20.3 29.6 226 210.5 24.9 19.0
1155 4.6 22.0 251.8 18.8 27.4 22.0 215.0 23.4 18.8
1156 4.1 22.5 253.7 23.9 34.9 21.8 210.7 29.0 18.1
1157 4.1 22.7 249.7 26.9 39.3 22.0 207.1 326 18.2
1158 . 4.2 225 254.8 28.8 42.0 21.8 211.8 35.0 18.1
1159 4.1 22.5 254.4 26.0 3&0 21.9 211.0 31.5 18.2
1200 4.2 22.3 254.9 25.6 37.4 22.4 212.4 31.1 18.7
1201 4.2 22 .2 259.9 25.9 37.8 23.1 216.7 31.5 19.3
1202 4.1 22.5 261.4 25.6 37.4 23.6 215.9 30.9 19.5
1203 4.0 22.3 256.4 25.1 36.6 23.7 211.5 30.2 19.6
1204 4.1 22.3 25&2 26.2 38.2 23.6 213.4 31.6 19.5
1205 4.2 22.3 261.2 24.6 35.9 23.8 217.9 30.0 19.9
1206 4.0 22.5 260.1 23.5 34.3 24.1 214.6 28.3 19.9
1207 4.0 22.3 258.2 24.5 35.8 24.3 212.5 29.4 20.0
1208 4.2 22.1 256.6 25.8 37.7 24.4 214.3 31.5 20.4
1209 4.2 22.1 256.4 25.1 36.6 24.5 213.7 30.5 20.4
1210 4.1 22.4 259.1 27.5 40.1 24.5 214.9 33.3 20.3
Port change Conducted zero and span of THC units
1224 4.4 22.2 254.2 A A A 214.0 A 84.6’
1225 4.4 22.2 254.0 A A A 214.6 A 84.9
1226 4.3 227 248.0 A A A 20’7.9 A 84.3’
1227 4.3 22.8 244.9 A A A 205.6 A 84.4*
122.8 4.0 229 246.3 A A A 2022 A 82.5’
1229 4.2 22.4 253.0 A A A 210.3 A 60.4’
1230 4.2 22.7 256.4 28.7 41.9 20.3 213.3 34,9 16.9
1231 4.4 22.2 257.4 20.8 30.4 20.7 216.6 25.5 17.4
1232 4.3 22.5 259.4 26.1 38.1 22.0 217.9 32.0 18.5
1233 4.1 22.9 253.7 32.1 46.9 222 209.8 3&8 18.4
8-74
-------
1234 3.9 23.1 241.7 37.1 54.2 22.5 198.0 44.4 1&4
1235 3.9 23.1 240.8 35.1 51.2 22.5 197.3 42.0 18.4
1236 4.1 22.9 254.3 28.9 42.2 22.7 210.2 34.9 18.8
1237 3.9 23.2 251.2 31.3 45.7 23.6 205.8 37.4 19.3
1238 3.9 23.1 252.2 26.0 8.O 25.0 206.5 31.1 20.5
1239 3.9 23.0 250.5 25.7 37.5 26.2 204.8 30.7 21.4
1240 3.8 23.3 242.2 32.7 47.7 26.8 196.6 3&7 21.8
1241 3.8 22.8 247 ,9 33.1 48.3 27.5 201.7 39.3 22.4
1242 3.8 22.9 24.6.5 33.0 48.2 27.9 200.6 39,2 22.7
1243 4.0 22.6 251.5 29.5 43.1 28.3 206.6 35.4 23.3
1244 4.0 22.5 249.2 26.7 39.0 29.0 205.3 32.1 23.9
1245 4.1 22.5 251.0 21.1 30.8 29.5 207.7 25.5 24.4
1246 4.0 22.8 251.7 25.5 37.2 29.4 207.3 30.7 24.2
1247 3.9 23.3 249.0 29.8 43.5 28.8 203.6 35.6 23.6
1248 4.0 22.6 256.7 28.5 41.6 28.1 211.5 34.3 23.2
1249 4.0 22.5 258.9 27.0 39.4 27.7 213.7 32.5 22.9
1250 3.9 23.1 245.1 35.0 51.1 27.8 200.5 41.8 22.7
1251 3.9 23.0 245.5 33.6 49.1 28.2 200.5 40.1 23.0
1252 3.9 22.7 245.5 33.6 49.1 28.1 200.6 40.1 23.0
1253 3.9 22.6 249.2 29.9 43,6 28.0 203.8 35.7 22.9
1254 4.0 22.5 247.8 32.2 47.0 28.7 204.4 38.8 23.7
Port change
1405 4.0 23.0 295.1 32.8 47.9 28.0 242.6 39.4 23.0
1406 4.0 23.1 288.3 32.1 46.9 29.8 237.6 38.6 24,6
140’7 4.2 22.5 301.4 26.1 3&1 30.9 251.6 31.8 25.8
1408 4.0 23.7 281.5 32.2 47.0 31.2 231 ,6 38.7 25.7
1409 3.8 23.0 290.6 27.1 39.6 31.8 236.8 32.2 25.9
1410 4.0 22.5 297.5 24.0 35.0 31.1 245.4 28.9 25.7
1411 4.2 22.7 298.8 26.1 38.1 31.8 248.3 31.7 26.4
1412 4.2 22.4 294.2 24.9 36.4 31.9 245.2 30.3 26.6
1413 4.3 22.8 292.1 31.1 45.4 31.1 244.7 38.0 26.1
1414 4.0 23.0 293.3 33.9 49.5 29.9 241.7 40.8 24.6
1415 4.1 22.9 294.6 31.3 45.7 29.0 243.8 37.8 24.0
1416 4.1 23.0 277.1 42.3 61.8 28.3 229.0 51.0 23.4
1417 3.8 23.3 265.9 46.3 67.6 28.3 216.4 55.0 23.0
1418 3.7 23.5 281.5 39.1 57.1 28.3 228.1 46.2 22.9
1419 3.8 23.2 287.0 28.7 41.9 28.8 234.0 34.2 23.5
1420 4.0 22.7 296.2 24.8 36.2 30.7 243.8 29.8 25.3
1421 4.1 22.8 286.3 27.3 39.9 31.9 237.0 33.0 26.4
1422 3.9 23.1 277.4 32.1 46.9 32.1 227.2 38.4 26.3
1423 3.7 23.7 252.0 42.6 62.2 31.5 203.3 50.2 25.4
1424 3.4 23.7 254.0 43.3 63.2 31.0 202.4 50.4 24.7
1425 3.4 23.5 258.8 43.1 62.9 30.9 205.9 50.0 24.6
B-75
-------
1426 3.7 23.3 280.5 3&7 56.5 32.3 226.3 45.6 26.1
1427 3.9 23.0 291.2 32.6 47.6 34.3 237.9 38.9 28.0
1428 3.9 23.1 295.6 30.3 44.2 36.0 242.6 36.3 29.5
1429 3.9 23.1 293.8 31.0 45.3 36.9 240.0 37.0 30.1
1430 3.8 23.3 278.7 35.1 51.2 36.8 227.2 41.8 30.0
1431 3.9 22.9 289.8 29.6 43.2 36.1 236.6 35.3 29.5
1432 4.0 22.9 292.5 29.8 43.5 35.3 240.3 35.7 29.0
1433 4.1 22.9 299.9 31.1 45.4 34.9 247.7 37.5 28.8
1434 4.0 22.9 299.7 29.2 42.6 34.6 247.1 35.1 28.5
1435 4.1 22.8 298.1 30.5 44.5 33.6 246.8 36.9 27.8
1436 4.1 22.7 294.2 25.4 37.1 32.6 243.3 30.7 27.0
AVG= 4.1 22.7 264.8 29.1 42.6 27.1 219.4 35.2 21.3
M1N= 3.4 22.02 240.8 18.8 27.4 20.3 196.6 23.4 16.9
MAX= 4.6 23.87 301.4 46.3 67.6 36.9 251.6 55.0 30.1
02= Oxygen
C02 = Carbon Dioxide
CO = Carbon Monoxide
THCH = Hydrocarbon Hot-line
THCC = Hydrocarbon Cold-line
A Span gas in line. Invalid data. Turned back to stack gas at 12.29.
B- 76
-------
Filename:RUNS
Name:RUNS
Date: 07-05-1990
Location:HANNIBAL, MO
Projecr.91 02-63-13
Operator.BG
VERSION = 05/07/90
CO TI-ICI-I THCC
TIME 02 C02 CO THCH THCH THCC @ 7% 02 @ 7% 0 @ 7% 0
(%, (ppm, (ppm, (ppm, (ppm, (ppm, (ppm, (ppm,
dry) dry) dry) wet) dry) dry) dry) dry) dry)
1220 4.2 22.8 A 64.6 1C’1.4 48.1 A 84.5 40.1
1221 3.8 23.5 A 79.0 124.0 49.6 A 100.8 40.3
1222 3.9 23.4 A 67.1 105.3 50.3 A 86.0 41.1
1223 4.1 22.9 A B B 50.9 A B 42.2
1224 4.3 22.8 A B B 52.5 A B 44.1
1225 4.2 23.1 A B B 54.4 A B 45.3
1226 3.8 23.4 A 69.3 10&8 54.1 A 88.6 44.1
1227 3.7 23.8 175.5 82.5 129.5 52.7 1414 105.1 42.7
1228 3.9 23.2 234.7 65.1 102.2 53.0 1922 83.7 43.4
1229 4.4 23.0 265.6 5&6 92.0 55.9 223.9 77.5 47.1
1230 4.5 22.9 263.3 60.2 94.5 5&7 222.9 80.0 49.7
1231 4.4 23.0 251.5 B B 59.2 212.1 B 49.9
1232 4.2 23.2 - 253.4 B B 57.0 211.5 B 47.6
1233 4.3 23.0 268.6 B B 54.8 225.2 B 45.9
1234 4.6 22.8 269.9 B B 53.9 230.3 B 46.0
1235 C C C C C C C C C
1248 4.4 22.8 255.3 52.1 81.8 421 215.4 69.0 35.5
1249 4.3 22.7 252.1 47.6 74.7 42.4 211.0 62.5 35.5
1250 4.6 22.6 274.1 61.7 96.9 43.5 233.8 82.6 37.1
1251 4.5 22.6 264.6 46.5 73.0 43.5 224.6 62.0 36.9
1252 4.6 22.7 283.7 37.1 58.2 44.6 242.0 49.7 38.0
1253 3.7 23.6 217.3 77.6 IZI.8 43.8 175.6 98.5 35.4
1254 3.2 2.3.9 153.4 92.3 144.9 43.8 120.8 114.1 34.5
1255 3.9 23.3 201.0 67.4 105.8 43.5 164.7 86.7 35.6
1256 4.8 22.4 275.9 46.4 72.8 46.2 237.7 62.8 39.8
1257 4.8 22.3 287.4 50.2 78.8 50.6 248,8 68.2 43.8
1258 4.5 22.5 282.4 38.4 60.3 52.4 240.2 51.3 44.6
1259 5.0 21.9 266.3 31.2 49.0 50.8 233.3 42.9 44.5
1300 5.0 22.0 264.6 31.1 48.8 48.7 230.9 42.6 42.5
1301 4.9 22.0 280.8 38.1 59.8 47.6 243.7 51.9 41.3
B—77
-------
1302 4.7 221 283.8 46.4 72.8 45.7 243.9 62.6 39.3
1303 4.7 22.1 282.4 35.9 56.4 43.7 242.3 48.3 37.5
Port change
1319 3.4 23.1 253.8 85.6 134.4 50.8 201.9 106.9 40.4
1320 5.8 20.1 228.6 32.4 50.9 49.6 210.7 46.9 45.7
1321 5.1 21.4 221.6 35.3 55.4 50.2 195.1 48.8 44.2
1322 4.7 21.9 24.8.6 53.3 83.7 53.1 212.9 71.6 45.5
1323 4.5 21.9 259.7 55.9 87.8 52 .0 220.1 74.4 44.1
1324 4.4 22.0 257.9 54.9 86.2 50.1 217.4 72.6 42.2
1325 4.5 22.0 259.1 41.1 64.5 48.9 219.7 54.7 41.5
1326 4.6 21.7 261.9 40.2 63.1 48.3 224.0 54.0 41.3
1327 4.7 21.5 265.7 37.1 58.2 47.5 227.5 49.9 40.7
1328 4.7 21.6 269.8 40.6 63.7 46.8 231.9 54.8 40.2
1329 4.9 21.6 276.0 38.6 60.6 45.8 239.9 52.7 39.8
1330 4.8 21.3 282.1 44.0 69.1 44.5 243.6 59.7 38.4
1331 4.8 21.4 285.5 37.8 59.3 43.2 247.0 51.3 37.4
1332 4.4 221 283.7 49.8 78.2 42.2 239.1 65.9 35.6
1333 4.2 21.9 281.3 52.2 81.9 41.5 234.4 68.3 34.6
1334 4.4 21.8 278.5 47.7 74.9 40.2 235.4 63.3 34.0
1335 4.5 21.8 278.8 48.7 76.5 40.6 236.6 64.9 34.4
1336 4.3 21.9 272.3 53.1 83.4 41.9 227.6 69.7 35.0
1337 3.9 22.4 262.6 63.1 99.1 41.8 215.1 81.1 34.2
1338 3.8 22.4 259.6 57.4 90.1 41.5 210.9 73.2 33.7
1339 4.3 21.9 263.5 41.9 65.8 41.7 221.0 55.2 35.0
1340 4.5 21.7 266.4 43.1 67.7 426 225.6 57.3 36.1
1341 4.5 21.8 268.5 48.3 75.8 44.6 227.4 64.2 37.8
1342 4.8 21.5 267.1 42.8 67.2 45.1 230.8 58.1 39.0
1343 4.6 21.5 263.6 42.8 67.2 44.3 225.6 57.5 37.9
1344 4.5 21.8 260.0 45.4 71.3 43.9 220.2 60.4 37,2
1345 5.4 20.6 264.2 32.8 51.5 42.7 237.1 46.2 3&3
1346 5.3 21.0 264.2 33.6 52.7 41.7 235.0 46.9 37.1
1347 4.3 21.9 264.1 44.2 69.4 41.0 221.0 58.1 34.3
1348 4.8 21.3 270.1 37.5 58.9 39.8 233.4 50.9 34.4
Port change
1408 5.1 21.0 280.7 33.1 520 34.2 246.5 45.6 30.0
1409 5.4 20.9 282.6 27.0 424 34.8 253.0 37.9 31.2
1410 5.4 20.9 283.1 31.2 49.0 35.1 253.7 43.9 31.5
1411 4.8 21.6 282.2 41.3 64.8 35.2 243.6 56.0 30.4
1412 4.7 21.4 282.0 43.3 68.0 34.5 242.7 58.5 29.7
1413 4.7 21.3 283.0 44.1 69.2 33.5 243.7 59.6 28.8
1414 4.9 21.4 284.8 47.7 74.9 33.6 247.0 65.0 29.1
1415 5.3 20.9 286.8 23.0 36.1 33.5 255.1 32.1 29.8
1416 5.1 21.1 285.9 35.9 56.4 34.0 251.4 49.6 29.9
8-78
-------
1417 5.1 21.0 285.8 33.3 52.3 35.9 251.0 45.9 31.5
1418 4.7 21.5 283.1 41.0 64 .4 36.6 243.3 55.3 31.5
1419 4.7 21.6 282.4 41.5 65.1 34.7 242.7 56.0 29.8
1420 4.7 21.5 282.2 40.1 63.0 33.9 242.7 54.1 29.2
1421 4.6 21.6 282.1 39.3 61.7 33.2 241.0 52.7 28.4
1422 4.7 21.4 283.5 40.3 63.3 33.2 242.9 54.2 2.8.4
1423 4.8 21.4 284.3 40.4 63.4 33.3 245.4 54.7 28.7
1424 5.0 21.2 285.3 40.4 63.4 33.6 250.1 55.6 29.5
1425 5.2 21.1 285.5 39.5 62.0 33.8 252.7 54.9 29.9
1426 5.0 21.2 284.2 35.3 55.4 33.9 248.8 48.5 29.7
1427 5.3 20.9 285.3 33.3 52.3 33.6 253.8 46.5 29.9
1428 5.0 21.1 283.8 36.4 57.1 33.0 248.6 50.1 28.9
1429 5.2 21.0 285.0 3&8 60.9 32.8 252.5 54.0 29.1
1430 4.9 21.3 284.2 37.7 59.2 32.4 247.0 51.4 28.2
1431 4.7 21.4 284.2 42.1 66.1 32.0 244.2 56.8 27.5
1432 4.7 21.6 284.1 47.6 ‘24.7 31.7 243.9 64.1 27.2
1433 4.5 21.8 284.3 50.4 ‘ 29.1 31.5 241.5 67.2 26.8
1434 4.6 21.6 285.1 47.4 ‘24.4 31.7 2429 63.4 27.0
1435 4.6 22.0 283.4 51.3 80 .5 32.3 241,2 68.5 27.5
1436 4.5 21.8 282.6 52.4 82.3 33.0 239.9 69.8 28.0
1437 4.7 21.6 282.5 53.2 83.5 34.0 242.6 71.7 29.2
1438 4.7 21.6 2.82 .9 34.2 53.7 34.7 243.4 46.2 29.9
Port change
1455 C C C C C C C C C
1456 C C C C C C C C C
1457 4.6 22.1 249.3 47.3 74.3 17.4 212.4 63.3 14.8
1458 4.7 21.8 281.9 43.2 67.8 220 2427 58.4 18.9
1459 4.6 22.3 284.2 50.2 78.8 28.0 242.2 67.2 23.9
1500 4.5 22.4 277.5 48.6 76.3 32.0 235.3 64.7 27.1
1501 4.3 22.6 278.2 57.0 89.5 33.2 2327 74.8 27.8
1502 4.4 22.5 268.5 58.2 91.4 33.9 225.8 76.8 28.5
1503 4.6 22.0 277.9 50.5 ‘19 ,3 34.7 236 9 67.6 29.6
1504 4.2 22.6 278.1 51.6 81.0 35.6 231.9 67.5 29.7
1505 4.5 22.1 2.83.7 37.9 59.5 36.7 240.9 50.5 31.2
1506 4.5 22.1 283.9 37.2 5&4 36.9 241.0 49.6 31.3
1507 4.5 22.4 287.2 40.3 63.3 37.4 243.1 53.5 31.7
1508 4.4 224 278.5 46.0 ‘72 ,2 37.9 234.5 60.8 31.9
1509 4.7 220 280.1 41.0 64.4 37.9 240.9 55.4 32.6
1510 4.5 22.2 281.7 46.0 72.2 38.0 238.6 61.2 32.2
1511 4.3 22.6 2.820 54.7 35.9 38.2 236.8 72.1 32.1
1512 4.1 22.8 275.5 57.4 90.1 38.0 228.4 74.7 31.5
1513 4.1 22.7 273.1 50.6 79.4 37.3 226.8 66.0 31.0
1514 4.0 22.9 270.7 51.0 30.1 37.2 222.9 65.9 30.6
3-19
-------
1515 4.1 22.6 268.0 51.9 81 ,5 37.9 221.9 67.5 31.4
1516 4.4 22.4 274.9 47.5 74.6 39.5 232.0 62.9 33.3
1517 4.5 22.4 280.1 48.4 76.0 40.9 237.5 64.4 34.7
1518 4.4 22.4 283.9 54.5 85.6 42.2 239.4 72.2 35.6
1519 4.3 22.5 286.7 39.9 62.6 42.6 240.9 52.6 35.8
1520 4.3 22.4 287.7 38.0 59.7 42.5 240.9 50.0 35.6
1521 4 3 22.6 284.0 37.9 59.5 42.1 237.4 49.7 35.2
1522 4.2 22.7 285.3 42.3 66.4 41.6 237.2 55.2 34.6
1523 4.0 22.9 283.6 49.3 77.4 41.5 233.7 63.8 34.2
1524 4.1 22.5 272.6 53.6 84.1 41.3 225.8 69.7 34.2
1525 3.9 22.9 281.8 64.3 100.9 41.6 231.3 82.8 34.1
AVG 4.4 22.1 271.1 47.2 74.1 41.3 231.1 62.7 35.1
MIN 3.2 20.1 153.4 23.0 36.1 17.4 120.8 32.1 14.8
MAX 5,8 23.9 287.7 92.3 144.9 59.2 255.1 114.1 49.9
02= Oxygen
C02 = Carbon Dioxide
CO = Carbon Monoxide
THCH = Hydrocarbon Hot-line
THCC = Hydrocarbon Cold-line
A Replacing ascarite filter. Invalid data.
B Lost THCH flow. Invalid data.
C Blowback of system. Invalid data.
B-80
-------
Filename:RUN6
Name:RUN6
Da te:07-05-1 990
Location:HANNIBAL, MO
Projecc 9102-63-13
Operator: BC
VERSION =05/07190
CO THCE-1 THCC
TIME 02 C02 CO THCH THCEI THCC @ 7% 02 @ 7% 02 @ 7% 02
(%, (ppm, (ppm, (ppm. (ppm, (ppm, (ppm, (ppm,
dry) dry) dry) wet) dry) dry) dry) dry) dry)
1900 3.7 23.8 213.7 83.6 131.2 60.1 173.1 106.3 48.7
1901 3.7 23.8 194.1 86.2 135.3 59.8 156.9 109.4 4&3
1902 3.7 23.8 190.5 74.1 116.3 60.5 154.2 94.1 49.0
1903 4.0 23.4 189.5 59.2 92.9 62.3 156.0 76.5 51.3
1904 4.3 23.0 210.1 53.6 84.1 64.1 176.4 70.7 53.8
1905 4.2 23.2 224.7 60.6 95.1 65.4 187.3 79.3 54.5
1906 4.6 229 227.0 47.5 74.6 65.4 193.2 63.5 55.7
1907 4.8 22.4 236.3 42.2 66.2 64.1 203.8 57.1 55.3
1908 4.8 225 2466 43.1 67.7 62.4 212.8 58.4 53.9
1909 4.5 22.6 250.8 53.0 83.2 59.8 213.2 70.7 50.8
1910 4.0 23.4 249.3 74.0 116,2 56.9 205.2 95.6 46.8
1911 3.7 23.7 235.0 74.9 117.6 53.4 190.3 95.2 43.2
1912 4.4 229 204.3 57.2 89.8 51.2 171.9 75.5 43.1
1913 4.2 23.1 201.9 52.6 826 51.6 167.9 6&6 42.9
1914 4.0 23.4 226.1 57.0 89.5 54.4 186.2 73.7 44.8
1915 4.2 23.1 225.1 61.9 97,2 55.2 187.5 80.9 46.0
1916 4.6 22.6 219.0 54.9 86.2 54.5 186.4 73.3 46.4
1917 4.9 22.2 232.9 45.5 71.4 55.1 202.9 62.2 48.0
1918 5.3 21.7 245.6 37.0 5&1 55.8 219.4 51.9 49.9
1919 5.2 21.8 252.7 43.1 677 55.1 223.8 59.9 48.8
1920 5.1 22.0 254.4 44.4 69 7 52.8 223.3 61.2 46.3
1921 5.1 22.0 251.8 46.0 72,2 49.5 221.2 63.4 43.5
1922 4.7 22.4 250.0 55.6 87.3 46.4 214.6 74.9 39.8
1923 4.2 22.8 247.1 66.7 104,7 44.9 206.4 87.5 37.5
1924 4.2 22.6 242,2 74.7 117.3 43.6 201.8 97.7 36.3
1925 4.8 22.0 241.2 A A 43.1 208.7 A 37.3
1926 4.4 22.6 241.2 A A 43.9 203.8 A 37.1
1927 4.3 22.6 250.2 A A 45.1 209.9 A 37.8
1928 4.4 22.6 2426 A A 45.3 204.1 A 3&1
1929 4.6 22.3 241.3 A A 45.7 205.4 A 38.9
B-81
-------
1930 5.1 21.8 242.4 A A 46.8 214.0 A 41.3
Port change
1940 4.8 22.1 244.4 58.8 92.3 38.7 210.8 79.6 33.4
1941 A A A A A 38.6 A A 25.7
1942 A A A A A 39.2 A A 26.1
1943 3.8 23.4 236.1 B B 40.5 191.6 B 32.9
1944 4.1 23:0 214.7 54.6 85.7 38.9 177.9 71 32.2
1945 4.1 22.8 184.1 56.0 87.9 37.2 152.5 72.8 30.8
1946 4.3 22.5 207.5 52.1 81.8 40.6 174.3 68.7 34.1
1947 4.3 22.9 222.4 59.7 93.7 42.9 186.7 78.7 36.0
1948 4.3 22.8 231,5 59.2 92.9 44.0 194.5 78.1 37.0
1949 4,3 22.9 235.4 56.9 89.3 44.2 197.1 74.8 37.0
1950 4.2 23.1 237.1 53.3 83.7 44.5 197.8 69.8 37.1
1951 4.8 22.7 240.3 51.0 80.1 44.7 207.0 69.0 38.5
1952 4.7 22.5 2425 52.3 82.1 45.3 208.7 70.6 39.0
1953 4.3 23.2 254.4 63.1 99.1 46.0 213.7 83.2 38.6
1954 4.3 23.0 252.7 67.3 105.7 45.3 211.8 88.6 38.0
1955 4.2 23.1 243.2 6&0 106.8 44.5 203.0 89.1 37.1
1956 C C C C C 45.0 C C 30.0
1957 C C C C C 45.8 C C 30.5
1958 C C C C C 46.4 C C 30.9
1959 C C C C C 45.1 C C 30.1
2000 C C C C C 39.2 C C 26.1
2001 C C C C C 34.3 C C 22.9
2002 C C C C C 30.1 C C 20.1
2003 C C C C C 27.9 C C 18.6
2004 4.2 23.4 234.9 57.8 90.7 29.3 195.6 75.6 24.4
2005 4.2 23.3 232.6 57.7 90.6 31.6 193.8 75.5 26.3
2006 4.6 22.8 232.5 51.0 80.1 34.2 198.0 68.2 29.1
2007 4.7 22.7 234.8 45.1 70.8 36.7 201.9 60.9 31.6
2008 3.7 23.9 242.5 91.6 143.8 38.8 196.1 116.3 31.4
2009 4.2 23.3 208.8 66.4 104.2 39.5 173.7 86.7 32.9
2010 4.3 23.2 209.1 53.2 83.5 39.3 175.5 70.1 33.0
Port change
2019 4.8 22.6 246.6 38.8 60.9 39.8 213.2 52.7 34.4
2020 4.9 22.5 250.1 39.0 61.2 39.6 217.3 53.2 34.4
2021 4.6 22.9 252.2 49.7 78.0 39.0 215.3 66.6 33.3
2022 4.4 23.0 250.4 57.8 90.7 38.3 211.1 76.5 32.3
2023 4.7 22.5 250.0 54.3 85.2 38.0 215.3 73.4 32.7
2024 4.7 226 244.2 30.6 48.0 38.3 209.9 41.3 32.9
2025 4.7 22.6 247.2 37.9 59.5 39.6 212.8 51.2 34.1
2026 4.5 22.6 253.0 47.9 75.2 40.3 215.1 63.9 34.3
2027 4.7 22.5 251.0 45.2 71.0 40.2 215.8 61.0 34.6
B-82
-------
2028 4.0 23.1 248.4 70.1 110.0 39.8 204.9 90.8 32.8
2029 4.1 23.2 239.6 66.1 103.8 39.8 198.1 85.8 32.9
2030 4.1 23.1 231.0 66.0 103.6 39.6 191.4 85.8 32.8
2031 4.1 23.2 233.7 60.7 95.3 41.4 193.1 78.8 34.2
2032 4.5 22.8 230.3 38.6 60.6 43.8 195.1 51.3 37.1
2033 4.8 22.4 234.4 42.2 66.2 45.6 202.3 57.2 39.4
2034 5.0 220 248.0 41.5 65. 1 47.1 217.4 57.1 41.3
2035 5.0 22.2 256.2 44.7 70.2 47.3 224.3 61.4 41.4
2036 4.5 22.6 253.1 55.9 87.8 46.0 214.8 74.5 39.0
2037 4.4 22.8 249.0 52 .5 82.4 44.2 209.4 69.3 37.2
2038 4.4 22.7 243.2 48.9 76.8 42.2 204.7 64.6 35.5
2039 4.4 22.7 242.8 45.2 71.i) 42.0 204.5 59.8 35.4
2040 4.4 22.9 243.0 43.8 68.3 42.1 204.8 58.0 35.5
2041 4.5 22.8 243.3 43,2 67.3 42.3 205.9 57.4 35.8
2042 4.5 22.7 244.5 42.6 66.’) 42.7 207.3 56.7 36.2
2043 5.0 22.0 249.5 41.4 65.’) 43.3 217.8 56.7 37.8
2044 5.3 21.7 251.4 38.5 60.4 43.7 223.9 53.8 38.9
2045 5.1 221 260.9 429 67.3 43.5 229.6 59.3 38.3
2046 4.2 23.0 259.8 48.1 75.5 42.2 216.0 62.8 35.1
2047 4.2 23.0 247.6 49.4 77.5 40.3 206.3 64.6 33.6
2048 4.9 22.1 238.0 37.6 59.0 39.0 206.3 51.2 33.8
2049 5.2 21.8 249.4 36.5 57.3 40.5 221.0 50.8 35.9
Port change
2122 4.7 22.3 256.3 41.4 65.0 36.8 220.0 55.8 31.6
2123 4.6 22.2 255.5 29.1 45.7 35.8 218.2 39.0 30.6
2124 4.9 22.0 258.7 31.6 49.6 35.0 224.4 43.0 30.4
2125 4.9 22.3 258.1 37.9 59.5 34.2 224.7 51.8 29.8
2126 5.5 21.4 260.7 29.1 45.7 33.6 235.6 41.3 30.4
2127 5.0 22.2 257.6 35.5 55.7 327 225.8 48.9 28.7
2128 4.7 22.8 253.6 46.5 73.0 320 217.3 62.5 27.4
2129 4.6 229 253.9 30.0 47.1 30.9 216.3 40.1 26.3
2130 4.8 22.6 254.4 29.0 45.5 30.0 220.0 39.4 25.9
2131 4.8 22.6 255.3 37.7 59.2 30.1 221.2 51.3 26.1
2132 4.7 22.8 255.0 41.7 65.5 30.8 219.0 56.2 26.5
2133 5.0 22.4 256.9 39.1 61.4 31.0 224.1 53.5 27.0
2134 4.5 22.9 254.2 46.8 73.5 30.8 215.4 623 26.1
2135 4.5 22.8 251.1 45.6 71.6 30.9 213.6 60.9 26.3
2136 4.6 22.8 253.5 47.6 74.7 31.1 216.4 63.8 26.5
2137 4.7 22.6 255.5 27.1 42.5 31.5 219.2 36.5 27.0
2138 4.7 225 257.9 34.3 53.8 32.1 221.0 46.1 27.5
2139 4.6 22.6 256.0 32.5 51.0 32.6 218.1 43.5 27.8
2140 4.6 22.6 258.4 37.0 58.1 32.8 221.1 49.7 28.1
2141 4.6 226 258.8 44.1 69.2 32.9 220.9 59.1 28.1
B-83
-------
2142 4.6 22.7 258.6 43.5 68.3 33.3 220.5 58.2 28.4
2143 4.7 22.6 260.5 42.7 67.0 33.3 223.7 57.6 28.6
2144 4.5 22.8 263.0 47.1 73.9 33.5 223.4 62.8 28.5
2145 4.7 22.6 261.6 46.3 72.7 33.8 224.1 62.3 29.0
2146 4.7 22.4 259.6 515 82.4 33.9 223.1 70.8 29.1
2147 4.7 22.4 261.5 31.6 49.6 34.2 225.0 42.7 29.4
214.8 4.7 22.5 264.0 33.6 52.7 34.6 226.2 45,2 29.6
2149 4.8 22.5 263.8 32.5 51.0 34.5 227.8 44.1 29.8
2150 4.7 22.6 260.4 40.9 64.2 34.3 223.7 55.1 29.5
2151 4.6 22.7 258.1 44.8 70.3 34.4 220.5 60.1 29.4
AVG 4.5 22.5 243.1 49.4 77.5 422 206.6 65 ,5 35.3
MIN 1.9 4.4 184.1 27.1 42.5 27.9 157.5 36.5 1&6
MAX 5.5 23.9 318.2 91.6 143.8 65.4 235.6 116.3 55.7
02 = Oxygen
C02 = Carbon Dioxide
CO = Carbon Monoxide
THCH = Hydrocarbon Hot-line
THCC = Hydrocarbon Cold-line
A = Lost sampling flow. Invalid data.
B = Lost THCI-I flow. Invalid data.
C = Backflow of system. Invalid data.
B -84
-------
APPENDIX B-5
TOTAL HYDROCARBON AND TOTAL ORGANIC MASS DATA
This appendix contains minute—by—minute readings of both the hot and cold
hydrocarbon analyzers. Also included are plots of each run’s HC readings, hot
and cold, along with each organic mass measurement determined by field GC. Note
that the HC monitors were taken off line about once every hour for calibration
purposes.
B-85
-------
Fileriame.RUN1
Name:RUN1
DateO6-20- 1990
Location:HANNIBAL,M0
Project9lO2-63- 13
Operator•
VERS ION O5/07/90
Time Decimal Decimal HCM THCC Tori
Time Time (ppm (ppm (ppm
x 100 dry) dry) dry)
1114 11.23 1123 22.6
1118 11.30 1130 27.5 9.5
1119 11 32 1132 23 5 10.2
1120 11.33 1133 19 7 10.8
1121 11.35 1135 19.2 11.4
1122 11.37 1137 21.2 11.4
1123 11.38 1138 22.5 10.8
1124 11.40 1140 27 1 10.5
1125 11.42 1142 25.9 10.8
1126 11.43 1143 29.1 11.2
1127 11.45 1145 15.7 11.8
1128 11.47 1147 26.7 12.2
1129 11.48 1148 26.2 11.8
1130 11 50 1150 24 7 11 3
1131 11 52 1152 24 0 10.9
1132 11.53 1153 28 1 10 6 29 5
1133 11.55 1155 29 4 10 5
1131. 11 57 1157 28 3 10.2
1135 11 58 1158 22 9 9.9
1136 11.60 1160 16 9 9.7
1137 11.62 1162 22 2 9 6
1138 11.63 1163 22.2 9 5
1139 11.6S 1165 20.0 9.4
1140 11.67 1167 18 6 9.3
1141 11.68 1168 18.2 9.3
1142 11 70 1170 17 6 9 0
1143 11.72 1172 17.2 8 7
1144 11.73 1173 17 0 8 2
1145 11.75 1175 17.5 7.9
1146 11.77 1177 17 6 7.5
1147 11.78 1178 18 6 7.3
111.8 11.80 1180 19 4 7.2
1149 11 82 1182
1151 11 85 1185 20 1
1209 12 15 1215 22.9
1213 12 22 1222
1214 12.23 1223 24 1 11.0
1215 12.25 1225 22 2 11.0
1216 12 27 1227 23 5 11 0
1217 12 28 1228 25.3 11 0
1218 12.30 1230 24 6 11 0
1219 12 32 1232 21 3 11 1
B-87
-------
Run 1, continued
Time Decimal Decimal IHCH THCC TOM
Time Time (p o (p ii (ppn
x 100 dry) dry) dr))
1220 12 33 1233 20.3 11.5
1221 12.35 1235 19.7 11.7
1222 12.37 1237 19.5 11.8
1223 12.38 1238 21.0 11.8
1224 12.40 1240 21.9 11.6
1225 12.42 1242 20.6 11.5
1226 12.43 1243 19.1 11.5
1227 12.45 1245 17.5 11.6
1228 12.67 1247 18.6 11.5 22.9
1229 12.48 1248 19.8 11.5
1230 12.50 1250 19 5 11.4
1231 12.52 1252 19 8 11.3
1232 12.53 1253 18 2 11.3
1233 12 55 1255 18 5 11.3
1234 12.57 1257 19 4 11.3
1235 12.58 1258 19.4 11.0
1236 12.60 1260 19 4 10.6
1237 12.62 1262 19.1 10.3
1238 12.63 1263 16.7 9.9
1239 12.65 1265 15.5 9.6
1240 12.67 1267 15 8 9.4
1261 12.68 1268 16.0 9.1
1242 12 70 1270 15 7 8.8
1243 12.72 1272 15.4 8.7
1244 12 73 1273 16.6 8.6
1245 12 75 1275
1246 12.77 1277 15.3
1305 13.08 1308 23.9
1307 13.12 1312
1308 13.13 1313 19.1 7.7
1309 13.15 1315 19.7 7.8
1310 13.17 1317 21.0 7.9
1311 13.18 1318 21.6 8.0
1312 13 20 1320 18 9 8.1
1313 13 22 1322 19.2 8.2
1314 1323 1323 18.9 8 4
1315 13 25 1325 18 6 8.5
1316 13.27 1327 14 5 8.5
1317 13.28 1328 14 3 8 4
1318 13 30 1330 14 9 8 2
1319 13.32 1332 15 4 8 1
1320 13.33 1333 16 3 8 0
1321 13 35 1335 18.0 7 9
1322 13 37 1337 17 9 7 9
1323 13.38 1338 19 2 7 9
1324 13 40 1340 19 4 8 0 26 0
1325 13.62 1342 19 1 8.1
1326 13.63 1343 19 1. 8.1
1327 13 65 1345 19.4 8.1
1328 13 47 1347 19 8 8.0
8-88
-------
Run 1 continued
Time Dectm L Decimal THCH THCC TOM
Time Time (ppll (ppm (ppm
x 100 dry) dry) dry)
1329 13 48 1348 18 6 8.0
1330 13.50 1350 16.0 8.0
1331 13.52 1352 14.3 7.9
1332 13.53 1353 13.5 7.9
1333 13.55 1355 12.9 7.8
1334 13.57 1357 13.5 7.6
1335 13.58 1358 13.8 7.2
1336 13.60 1360 13.5 7.0
1337 13.62 1362 13.6 6.7
1338 13.63 1363 13.6 6.5
1337 13 62 1362
1343 13.72 1372 37 4
1402 14.03 1403 27.5
1417 14 28 1428
1418 14.30 1430 11.7 4.9
1419 14.32 1432 11 8 4,8
1420 14.33 1433 12.0 4.8
1421 14.35 1435 11.6 4.7
1422 14.37 1437 12.4 4.7 15.2
1423 14.38 1438 11.2 1. 7
1424 14.40 1440 11.7 4.7
1425 14.42 1442 12.1 4.7
1426 14 63 16 3 12.4 4 7
1427 14 45 1465 10.9 4.7
1428 14.47 1447 11.1 4.7
1429 14 68 1468 11 1 4.7
1430 14.50 1450 11 4 4.7
1431 14.52 1452 10.5 4.7
1432 14.53 1453 9.6 4.7
1433 14.55 1455 9.9 4.7
1434 14.57 1457 10 2 4 7
1635 14.58 1658 10.5 4.7
1436 14 60 1460 10.7 4 7
1437 11. 62 1462 11.4 4 7
1438 14 63 1463 11 2 4 7
1439 14 65 1465 10 8 4 7
1460 11. 67 1467 9 6 6 6 9.6
1441 14.68 1468 9 2 4.6
1662 16.70 1470 9 3 4 5
1463 14 72 1472 9 5 4.5
1444 14 73 1473 9 6 4 4
1445 14.75 1475 10 2 1. 4
1446 14.77 1477 10 7 4 4
1447 14.78 1678 10 8 4.3
1448 14.80 1480 10.7 4 2
8-89
-------
RUN 1 - HOT AND COLD HC CONCENTRATIONS
AND TOTAL ORGANIC MASS
± Organic Mass
I I I
I I
Time (24 hour)
—--- ----—
1400
±
0
cD
±
U)
(U
0.
0
I.-
ci
(I)
CU
-o
>
E
0.
0
Co
I-
4-a
C
1)
0
C
0
0
40--—
35-
30-
25-
20-
15-
10-
5-
0-—
1100
±
±
±
±
±
/\/‘
I
±
1500
Hot HC
Cold HC
-------
Filename: RUN2
Naine:RUN2
Date:06-21 -1990
Locat ion HANNIBAL MO
Project
Operator• BG
VERSIO I4rO5/07/90
Time Decimal Decimal THCH THCC TOM
Time Time Cpp i, (ppii, (ppn,
x 100 dry) dry) dry)
1228 12.47 1247 70.2
1230 12.50 1250 59 7 40.4
1231 12.52 1252 53 3 41 6
1232 12 53 1253 57 6 41 8.
1233 12.55 1255 60.5 42 0
1231. 12.57 1257 73.2 61 8
1235 12.58 1258 77.7 41.8
1236 12.60 1260 73.5 62.1
1237 12.62 1262 64.7 62 0
1238 12.63 1263 63.2 42.2
1239 12.65 1265 72.1 42.4
1240 12.67 1267 56.2 42.8
1241 12.68 1268 62.1 43.2
1242 12.70 1270 52.2 63.5
1243 12.72 1272 59.7 64.1
1244 12.73 1273 62.9 45 9
1245 12.75 1275 82.0 45 3
1246 12.77 1277 93.7 44 5 84 8
1247 12.78 1278 69.5 44.9
1248 12.80 1280 68.1 46.4
1249 12.82 1282 64.5 48.7
1250 12.83 1283 69.3 46.7
1251 12 85 1285 61.2 49 5
1252 12 87 1287 59 9 49 2
1253 12 88 1288 58.9 49 0
1254 12.90 1290 55.7 48 4
1255 12 92 1292 60 8 47 6
1256 12 93 1293 66 8 47 0
1257 12 95 1295 69 2 46 2
1258 12 97 1297 85 9 66 0
1259 12 98 1298 91 7 46 4
1300 13 00 1300 84.9 67 5
1305 13 08 1308 106.8
1319 13 32 1332 85.1 56.5
1320 13.33 1333 91.2 56.6
1321 13 35 1335 70.0 56.3
1322 13.37 1337 85.2 56.8
1323 13.38 1338 76.1 57 7
1324 13.40 1340 79.0 58.7 164.5
1325 13.42 1342 80.1 59 3
1326 13 43 1343 73.0 59 4
1327 13 45 131.5 65 8 58 9
B-91
-------
Run 2. continued
Time Decimal Decima’ THCH THCC TOM
Time Time (p n, (ppm, (ppm,
x 100 dry) dry) dry)
1328 13 47 1347 39.2 58.7
1329 13.48 1348 31.9 58.0
1330 13.50 1350 34.3 57.8
1331 13.52 1352 64.2 58.2
1332 13.53 1353 67.3 58.8
1333 13.55 1355 75.8 58.8
1334 13.57 1357 91.2 58.1.
1335 13.58 1358 91.5 58.3
1336 13.60 1360 88.4 57.8
1337 13 62 1362 93.4 57.3
1338 13.63 1363 84.3 57.4
1339 13 65 1365 85.7 58 1
1340 13.67 1367 71.9 58.6
131.1 13.68 1368 72 4 58 5
1342 13.70 1370 72.1 58.2
1343 13.72 1372 64.7 57.4 76.1
1344 13.73 1373 69.8 56.5
1345 13.75 1375 68.7 55.9
1346 13.77 1377 68.9 54.9
1347 13.78 1378 54.7 53.9
1348 13.80 1380 56.8 53.2
1349 13.82 1382 56.2 52 4
1402 14 03 1403 . 112.8
1410 14.17 1417 95 7 56 7
1411 14.18 1418 97 3 59.2
1412 14 20 1420 92 1 60.2
1413 16.22 1422 84 4 60.9
1414 14.23 1423 75.1 61.4
1415 14.25 1425 83.5 61.5
1416 14.27 1427 83.6 60.9
1417 14.28 1428 79.9 60.0
1418 16.30 1430 86 4 59.7
1419 14 32 1632 81.1 59.6
1420 14.33 1633 79.8 59.3
1421 14 35 1635 76.6 59.1 90.9
1422 14.37 1437 75.1 58.7
1/.23 14.38 1438 67 9 58.1
1424 14.40 1640 74.3 57.5
1425 14 42 1442 74.6 56.9
1426 14.63 1443 75.7 56.2
1427 14 45 1445 76.4 55.4
1428 14 47 1447 87.5 54.9
1429 14.48 1445 91.7 54 9
1430 16 50 1450 87 8 55 0
1431 14 52 1452 88.0 55 6
1432 14.53 1453 84 9 56 8
1433 14 55 1455 77.6 57.5
1434 14.57 1457 75.0 58 1
1435 14 58 1458 79.9 58 4
1436 14 60 1460 78.3 58.1
B-92
-------
Run 2, continued
Time Deciniat Decimal THCH THCC TOM
Time Time (ppii, (p n, (p n,
x 100 dry) dry) dry)
1437 14 62 1662 90 2 57.6
1438 14 63 1463 81 2 57.3
1439 14.65 1465 85.9 57.1 103.2
1440 14.67 1467 81.2 57.6
1458 14.97 1497 110.4
1510 15.17 1517 73.0 54.0
1511 15 18 1518 61.5 54.1
1512 1520 1520 70.0 54.1
1513 15.22 1522 72.9 53.5
1514 15 23 1523 70 3 52.7
1515 15 25 1525 81 4 52.0
1516 15 27 1527 65.7 51.7 64.5
1517 15 28 1528 60.0 51.7
1518 15.30 1530 74.5 52 5
1519 15.32 1532 53.0 52.8
1520 15.33 1533 55 2 51.8
1521 15 35 1535 48.2 51 9
1522 15.37 1537 61.5 51.5
1523 15.38 1538 58.1 50.1
1524 15.40 1540 56.3 48.8
1525 15.42 1542 62.3 48.0
1526 15 43 1543 68 5 47.9
1527 15.45 1545 66.1 47.3
1528 15.47 1547 70.5 46.9
1529 15.48 1548 70.6 46.8
1530 15.50 1550 72.7 46.5
1531 15.52 1552 74.0 46.5
1532 15.53 1553 77.4 47.0
1533 15.55 1555 66.1 47.5
1534 15.57 1557 78.0 48.7
1535 15.58 1558 74.0 49.7 73.0
1536 15 60 1560 67 7 50.1
1537 15.62 1562 67.4 50.4
1538 15 63 1563 72 6 50.1
1539 15 65 1565 57.5 49 0
1540 15 67 1567 57 0 48 3
B-93
-------
RUN 2- HOT AND COLD HG CONCENTRATIONS
AND TOTAL ORGANIC MASS
180
160-
140-
120
ioa
80-
60-
40-
20-—
1200
I I 1300 1400 1500 I
Time (24 hour)
1600
±
C
0
0
0
U)
Co
>
E
0.
0
C
0
4-
Co
4-
C
a)
0
C
0
0
±
+
±
±
4-
/ _.____/_
Hot HO
Cold HO
± Organic Mass
-------
FiLename RUN3
Name RUN3
Date 06-22-1990
Locaflon. HANMIBAL,MO
Proj ect
Operator. BG
VERSION O5/O7/90
TIME DECIMAL DECIMAL THCH THCC TOM
TIME TIME (ppm, (ppm, (ppm,
X 100 dry) dry) dry)
1133 11.55 1155 106.9
1135 11.58 1158 108.1 50 1
1136 11.60 1160 88.2 50.7
1137 11 62 1162 86.0 52.5
1138 11 63 1163 85.4 55.0
1139 11 65 1165 84.4 56.1
1140 11.67 1167 94.9 56.3
1141 11.68 1168 68.6 56.1
1142 11.70 1170 70.6 55.9
1143 11.72 1172 77 1 55.9
1144 11.73 1173 65.9 55.0
1145 11.75 1175 88 6 54.2
1146 11.77 1177 94.1 54.5
1147 11 78 1178 96.9 53.7
1148 11 80 1180 94.9 53.1
1149 11.82 1182 95.5 52.7
1150 11.83 1183 69.8 52 7
1151 11 85 1185 70.1 53.7 100
1152 11.87 1187 73.4 54.7
1153 11.88 1188 6&7 56.7
1154 11.90 1190 73.3 54.1
1155 11.92 1192 86.9 53.4
1156 11 93 1193 86.0 52.1
1157 11 95 1195 105 3 50.7
1158 11 97 1197 96 9 50.3
1159 11 98 1198 63 8 50.3
1200 12 00 1200 69 1 51.3
1201 12 02 1202 75 7 525
1202 12.03 1203 78 7 529
1203 12 05 1205 79 6 52 6
1204 12 07 1207 96 1 52 2
1205 12 08 1208 87 4 51 5
1209 12.15 1215 62.5
1223 12 38 1238 89 3 40 4
1224 12 40 1240 88 5 40.5
1225 12.42 1242 80.6 41 2
1226 12.43 1243 60 7 41.9
1227 12.45 1245 54.6 42.7 59.3
1228 12 67 1247 68.7 42.9
1229 12.48 1248 74.7 42.4
1230 12.50 1250 63.9 41.7
1231 12.52 1252 60.3 41.1
B-95
-------
Run 3, continued
TIME DECIMAL DECIMAL THCR THCC TON
TIME TIME (ppm, (ppm, (ppm,
X 100 dry) dry) dry)
1232 12.53 1253 54.0 40.5
1233 12.55 1255 68.3 42.8
1234 12.57 1257 73.9 43.5
1235 12.58 1258 71.1 43.2
1236 12.60 1260 60 0 43.0
1237 12 62 1262 65.0 43 3
1238 12.63 1263 73.7 43.6
1239 12.65 1265 84.3 43.3
1240 12.67 1267 75.4 43.4
1241 12.68 1268 65 2 43.9
1242 12.70 1270 61 4 44.9
1243 12.72 1272 58.5 45.3
1244 12.73 1273 64.9 45.3
1245 12.75 1275 68.7 45.3
1246 12.77 1277 64.2 45.2 64.3
1247 12.78 1278 71.2 45.3
1248 12.80 1280 68 7 45.1
1249 12.82 1262 54.9 44.3
1250 12.83 1283 43.9
1251 12.85 1285 44.0
1252 12.87 1287 43.5
1253 12.88 1288 42.6
1309 13.15 1315 75.3
1314 13.23 1323 76.4 42.6
1315 13.25 1325 78.2 42.7
1316 13.27 1327 72.5 43.3
1317 13.28 1328 59 9 43 8
1318 13.30 1330 55.5 43.8
1319 13.32 1332 53.7 43.3
1320 13.33 1333 52.4 42.2
1321 13.35 1335 57.1 40.7
1322 13.37 1337 58 8 39.6
1323 13.38 1338 53.3 38.0
1324 13 40 1340 47.4 37 0
1325 13 42 1342 47.6 36 4
1326 13.43 1343 54 6 35 6
1327 13 45 1345 54 0 3/. 3
1328 13.47 1347 48.8 33.2 42.3
1329 13.48 1348 35.0 33.0
1330 13.50 1350 39 7 33 2
1331 13.52 1352 36.4 32.5
1332 13.53 1353 40.7 31.6
1333 13 55 1355 36.7 31.2
1518 15.30 1530 119.6
1536 15.60 1560 79.5
1540 15.67 1567 82.7 51 6
1541 15.68 1568 86.9 51.2
1562 15.70 1570 96.4 50.9
1543 15.72 1572 85.7 51.3
1544 15.73 1573 82.1 51.9
B -96
-------
Run 3, continued
TIME DECIMAL DECIMAL THCH THCC TOM
TIME TIME (ppm, (ppm, (ppm,
X 100 dry) dry) dry)
1545 15 75 1575 77.1 52 1
1546 15 77 1577 79.9 52 2
1547 15 78 1578 66 9 52.4
1548 15.80 1580 61 4 52.5
154 15 82 1582 78.1 52.0
1550 15 83 1583 73.7 51.6
1559 15.98 1598 96.8
1615 16 25 1625 75.6 48 2
1616 16.27 1627 68 9 47.9
1617 16 28 1628 75.9 47.9 84.8
1618 16 30 1630 89 0 48.5
1619 16.32 1632 89 9 49 4
1620 16.33 1633 87.6 50 0
1621 16.35 1635 93.6 50 4
1622 16.37 1637 82.7 50.0
1623 16.38 1638 77.9 50.1
1624 16.40 1640 84 4 51.0
1625 16.42 1642 76.8 51.7
1626 16.43 1643 76.8 52.0
1627 16 45 1645 71.4 52.1
1628 16 47 1647 72.3 51.7
1629 16.48 1648 56.3 51 6
1630 16.50 1650 57.5 51 4
1631 16 52 1652 79.6 50 6
1632 16.53 1653 77.4 50 0
1633 16 55 1655 81 8 49 2
1634 16.57 1657 74.2 49 4
1635 16.58 1658 82 4 50.2
1636 16.60 1660 84.3 51.2 89.6
1637 16.62 1662 88.2 51.3
1638 16 63 1663 55.2 51 4
1639 16 65 1665 70.8 52 1
1640 16 67 1667 65.5 52 8
1641 16.68 1668 61. 5 52 5
1642 16.70 1670 71. 3 52 1
1643 16.72 1672 78 7 51 2
1644 16 73 1673 65 0 49 6
1645 16.75 1675 65 3 48.3
1656 16.90 1690 64.4
B-97
-------
RUN 3-
HOT AND COLD HO CONCENTRATIONS
AND TOTAL ORGANIC MASS
120-
100-
80-
60-
40-
20-
0 --—T
1100
I 1200 ‘ 1300
Time (24 hour)
-!————-I —— I I I I I I I I
1500 1600
140
t’o
±
c
0
0
0
(I)
>
D
>
E
0
0
c
0
4-.
4-.
C
c i)
C-)
C
0
0
/ 1
1700
Hot HG
Gold HG
± Organic Mass
-------
Filename RUN4
Name RUN4
Date:06-23 ’ 1990
Location HANNI6AL ,MO
Project
Operator 80
VERS ION =05/07/90
TIME Decimal Decimal INCH THCC TOM
Time Time (ppm, (ppm, (p n,
x 100 dry) dry) dry)
1053 10.88 1088 63.1
1055 10.92 1092 47.2 24.7
1056 10 93 1093 66.1 26 8
1057 10.95 1095 42.8 24.8
1058 10.97 1097 42.5 24.7
1059 10.98 1098 41.8 24.7
1100 11.00 1100 49.1 25.1
1101 11.02 1102 45.0 24.9
1102 11 03 1103 43.9 24 8
1103 11.05 1105 65.7 25.5
1104 11.07 1107 42.2 26.3
1105 11 08 1108 39.9 26.8
1106 11.10 1110 45.3 27.3
1107 11.12 1112 39.6 27.1
1108 11.13 1113 44.1 26 2
1109 11 15 1115 60.9 25 7
1110 11 17 1117 48.9 25 3
1111 11 18 1118 44 4 25.3
1112 11 20 1120 42 5 27 6 56 7
1113 11 22 1122 42.2 29.2
1114 11.23 1123 43.9 29.3
1115 11.25 1125 46.3 28.9
1116 11.27 1127 43.9 28.4
1117 11.28 1128 48.9 27.7
1118 11.30 1130 40.7 27.5
1119 11.32 1132 38.0 26.9
1120 11,33 1133 37.4 26.9
1121 11.35 1135 39.7 27.0
1122 11.37 1137 46.9 26.6
1123 11.38 1138 40.4 26.1
1124 11.40 1140 36.2 25 5
1125 11 42 1142 36.5 25.5
1130 11 50 1150 278 8
1140 11 67 1167 40.7 26 5
1141 11 68 1168 37.1 25.7
1142 11 70 1170 37.5 25.2
1143 11 72 1172 32 6 25.2
1144 11 73 1173 34.7 25.1
1145 11 75 1175 36.6 24.5
1146 11.77 1177 35.8 24 1
1147 11.78 1178 34.5 23.7
1148 11.80 1180 37.1 23 8 75 7
B-99
-------
Run 4, continued
TIME DecimaL Oecima THCH THCC TOM
Time Time (ppei, (ppit, (ppm,
x 100 dry) dry) dry)
1149 11 82 1182 38.2 23.8
1150 11.83 1183 35.0 23.4
1151 11.85 1185 30.7 23.1
1152 11.87 1187 31.5 23.0
1153 11.88 1188 34.9 23.0
1154 11 90 1190 29 6 22 6
1155 11.92 1192 27.4 22.0
1156 11.93 1193 34.9 21.8
1157 11.95 1195 39.3 22.0
1158 11.97 1197 42.0 21.8
1159 11.98 1198 38.0 21.9
1200 12.00 1200 37.4 22.4
1201 12.02 1202 37.8 23.1
1202 12 03 1203 37.4 23 6
1203 12.05 1205 36.6 23.7
1204 12.07 1207 38.2 23.6
1205 12 08 1208 35 9 23 8
1206 12.10 1210 34.3 24 1
1207 12.12 1212 35.8 24.3 P78.3
1208 12.13 1213 37.7 24.4
1209 12.15 1215 36.6 24.5
1210 12.17 1217 40 1 24 5
1211 12.18 1218
1224 12.40 1240
1225 12.42 1242
1226 12.43 1243
1227 12.45 1245
1228 12.47 1247
1229 12.48 1248
1230 12.50 1250 41.9 20.3
1231 12 52 1252 30.4 20.7
1232 12.53 1253 38.1 22.0 54.4
1233 12.55 1255 46.9 22.2
1234 12.57 1257 54.2 22.5
1235 12.58 1258 51 2 22.5
1236 12.60 1260 422 22.7
1237 12 62 1262 45 7 23.6
1238 12.63 1263 38.0 25 0
1239 12 65 1265 37 5 26.2
1240 12 67 1267 47 7 26.8
1241 12.68 1268 48 3 27.5
1242 12.70 1270 48.2 27 9
1243 12.72 1272 43 1 28 3
1244 12 73 1273 39 0 29 0
1245 12.75 1275 30.8 29 5
1246 12 77 1277 37 2 29.4
1247 12.78 1278 43 5 28 8
1248 12.80 1280 41.6 28.1
1249 12 82 1282 39.4 27 7
1250 12.83 1283 51.1 27 8
B-100
-------
Run 4, continued
TIME Decimal Decimal THCH 114CC TOM
Time Time (ppm, (ppm, (ppm,
x 100 dry) dry) dry)
1251 12.85 1285 49.1 28.2 69.6
1252 12.87 1287 49 1 28.1
1253 12.88 1288 43.6 28.0
1254 12.90 1290 47.0 28.7
1309 13.15 1315 49.9
1327 13.45 1345 117.6
1346 13.77 1377 52.9
1404 14.07 1407 74 8
1405 14.08 1608 67.9 28 0
1406 14.10 1410 46.9 29.8
1407 14 12 1412 38.1 30.9
1408 14.13 1413 67.0 31.2
1409 14 15 1415 39 6 31.8
1410 14.17 1417 35.0 31.1
1411 14.18 1418 38 1 31.8
1612 14.20 1620 36.6 31.9
1413 14.22 1422 45.4 31.1
1414 14.23 1423 49.5 29.9
1415 14.25 1625 45.7 29.0
1416 14.27 1427 61.8 28.3
1417 14.28 1428 67.6 28.3
1418 14.30 1430 57.1 28.3
1419 14 32 1432 41.9 28.8
1420 14.33 1433 36.2 30.7
1421 14 35 1435 39.9 31 9
1422 16 37 1437 46.9 32.1 77 2
1423 14.38 1638 62.2 31.5
1624 14.40 1440 63.2 31.0
1425 14.42 1442 62.9 30.9
1426 14.43 1443 56.5 32.3
1427 14.45 141.5 47 6 31. 3
1428 14 47 1447 44 2 36.0
1429 16 48 1448 45 3 36 9
1430 14 50 1450 51 2 36 8
1631 14.52 1652 63 2 36 1
1432 14.53 1453 43 5 35 3
1433 14.55 1655 45 4 34.9
1434 14 57 1457 42.6 34.6
1635 14 58 1458 44.5 33.6
1436 14 60 1460 37 1 32.6
8-101
-------
RUN 4- HOT AND COLD HO CONCENTRATIONS
AND TOTAL ORGANIC MASS
300- -
±
150-
I - .
0
N)
I 100- ± ± + ±
! I I T
1000 1100 1200 1300 1400 1500
Time (24 hour)
Hot HO Cold HO + Organic Mass
-------
Filename RUN5
Name RUNS
Date 07-05-1990
Location.HANNl8AL MO
Project .9102-63-13
Opera tor:8G
VERSION 05/O7/9O
TIME Decimal Decimal THCH THCC TOM
Time Time (p 1i, (ppil, (ppii,
x 100 dry) dry) dry)
1046 10 77 1077 72
1105 1108 1108 158 5
1123 11 38 1138 59 4
1220 12.33 1233 101.4 68.1 111 2
1221 12.35 1235 124.0 49 6
1222 12.37 1237 105.3 50.3
1223 12.38 1238 50.9
1224 12 40 1240 52.5
1225 12.42 1242 54.4
1226 12.43 1243 108.8 54.1
1227 12.45 1245 129.5 52.7
1228 12.47 1247 102.2 53.0
1229 12.48 1248 92.0 55.9
1230 12.50 1250 94 5 58 7
1231 12 52 1252 59 2
1232 12 53 1253 57 0
1233 12 55 1255 54 8
1234 12.57 1257 53.9
1235 12 58 1258
1245 12.75 1275 85.3
1248 12 80 1280 81 8 42 1
1249 12 82 1282 74.7 42.4
1250 12 83 1283 96.9 ‘.3_S
1251 12.85 1285 73.0 63.5
1252 12.87 1287 58.2 44 6
1253 12 88 1288 121 8 63.8
1254 12.90 1290 144 9 43 8
1255 12.92 1292 105 8 ‘.3.5
1256 12.93 1293 72.8 46.2
1257 12 95 1295 78.8 50.6
1258 12 97 1297 60 3 52 4
1259 12 98 1298 49 0 50.8
1300 13 00 1300 68 8 48.7
1301 13 02 1302 59 8 47 6
1302 13 03 1303 72.8 45 7
1303 13.05 1305 56.6 43.7 69 4
1304 13.07 1307
1319 13.32 1332 134 4 50.8
1320 13 33 1333 50 9 49 6
1321 13.35 1335 55.4 50 2
1322 13.37 1337 83 7 53 1 118 3
B-103
-------
Run 5, continued
TIME DecimaL Decimat P 1CM P4CC TOM
Time Time (ppm, (ppm, (ppm,
x 100 dry) dry) dry)
1323 13 38 1338 87.8 52.0
1324 13.40 1340 86 2 50 1
1325 13.42 1342 64.5 48.9
1326 13 43 1343 63.1 48.3
1327 13.45 1345 58.2 47.5
1328 13.47 1347 63.7 46.8
1329 13 48 1348 60 6 45.8
1330 13.50 1350 69.1 44.5
1331 13.52 1352 59.3 43.2
1332 13.53 1353 78.2 42.2
1333 13.55 1355 81.9 41.5
1334 13.57 1357 74.9 40.2
1335 13.58 1358 76.5 40.6
1336 13.60 1360 83.4 41.9
1337 13.62 1362 99.1 41.8
1338 13.63 1363 90.1 41.5
1339 13.65 1365 65.8 41.7
1340 13.67 1367 67.7 42.6
1361 13.63 1368 75.8 44.6 88.3
1342 13.70 1370 67.2 45.1
1343 13.72 1372 67.2 44.3
1344 13.73 1373 71.3 43.9
1345 13.75 1375 51.5 42.7
1346 13 77 1377 52.7 41 7
1347 13 78 1378 69 4 41 0
1348 13 80 1380 58.9 39 8
1359 13 98 1398 77 6
1408 14.13 1413 52 0 34 2
1409 14.15 1415 42.4 34.8
1410 14.17 1417 49.0 35.1
1411 14.18 1418 64.8 35.2
1412 14 20 1420 68.0 34 5
1413 14.22 1422 69 2 33.5
1414 14 23 1423 74.9 33.6
1415 14.25 1425 36.1 33.5
1416 14.27 1427 56.4 34 0
1417 14 28 1628 52.3 35 9
1418 14.30 1430 64.4 36.6 37.1
1419 14 32 1432 65 1 34.7
1420 14 33 1433 63.0 33 9
1421 14.35 1435 61 7 33.2
1422 1437 1437 633 332
1423 14 38 1438 63.4 33.3
1424 14.60 1440 63.4 33.6
1425 14.42 1442 62.0 33.8
1426 14.43 1443 55.4 33 9
1427 14.45 1465 52 3 33.6
1428 14.47 1647 57.1 33.0
1429 1448 1448 609 328
1630 14.50 1450 59.2 32 4
B-104
-------
Run 5, continued
TIME Decimal Decimal THCH THCC TOM
Time Time (ppm, (ppm, (ppm,
x 100 dry) dry) dry)
1431 14 52 1452 66 1 32 0
1432 14 53 1453 74.7 31.7
1433 16 55 1455 79.1 31.5
1434 14.57 1457 74.4 31.7
1435 14 58 1458 80.5 32.3
1436 16.60 1460 82.3 33.0 70 9
1437 14.62 1462 83.5 34.0
1438 14.63 1463 53.7 34.7
1439 14.65 1465
1655 14.92 1492
1456 14 93 1493
1457 16.95 1495 74 3 17 1. 76
1458 14 97 1497 67.8 22.0
1459 14.98 1498 78 8 28.0
1500 15.00 1500 76.3 32.0
1501 15 02 1502 89.5 33.2
1502 15 03 1503 91.4 33.9
1503 15.05 1505 79.3 34.7
1504 15.07 1507 81.0 35.6
1505 15.08 1508 59 5 36.7
1506 15.10 1510 58.4 36.9
1507 15.12 1512 63 3 37 4
1508 15 13 1513 72 2 37 9
1509 15.15 1515 64.4 37.9
1510 15.17 1517 72.2 38.0
1511 15.18 1518 85.9 38.2
1512 15.20 1520 90.1 38.0
1513 15.22 1522 79.4 37.3
1514 15.23 1523 80.1 37.2
1515 15.25 1525 81.5 37.9 88.1
1516 15.27 1527 74.6 39 5
1517 15.28 1520 76 0 40 9
1518 15 30 1530 85 6 62 2
1519 15.32 1532 62.6 42 6
1520 15.33 1533 59 7 62.5
1521 15.35 1535 59 5 42.1
1522 15.37 1537 66 4 41 6
1523 15.38 1538 77 6 41 5
1524 15 40 1540 84 1 41 3
1525 15 2 1542 100 9 41 6
B —lOS
-------
RUN 5- HOT AND COLD HC CONCENTRATIONS
AND TOTAL ORGANIC MASS
18O
16O ±
C
C 3
°- 14O
0
I —
0
U)
12O
*
>‘
D 100-
>
I - . 0 80
C ±
0
60 +
Co
4-.
I.’
4ft
C-)
C
0
o 2ft
I I I I
1000 1100 1200 1300 1400 1500 1600
Time (24 hour)
Hot HC Cold HO ± Organic Mass
-------
Fi 1ertame: UN6
Name:RUN6
Oate:07-O5-1990
location:HANNIBAL, MO
Project:9102-63- 13
Operator: BG
VERS1ON O5/07/9O
TIME Decimal Decimal THCH 1)1CC TOM
Time Time (ppm, (ppm, (ppm,
x 100 dry) dry) dry)
1900 19 00 1900 131.2 60.1 144.1
1901 19.02 1902 135.3 59 8
1902 19.03 1903 116.3 60 5
1903 19.05 1905 92 9 62 3
1904 19 07 1907 86.1 64 1
1905 19.08 1908 95.1 65.’.
1906 19.10 1910 74 6 65.4
1907 19.12 1912 66 2 64 1
1908 19.13 1913 67.7 62.4
1909 19.15 1915 83.2 59.8
1910 19.17 1917 116.2 56.9
1911 19.18 1918 117.6 53.4
1912 19.20 1920 89.8 51.2
1913 19.22 1922 82.6 51.6
1914 19.23 1923 89.5 54.4
1915 19.25 1925 97.2 55.2
1916 19.27 1927 86.2 54.5
1917 19.28 1928 71.4 55.1
1918 19 30 1930 58.1 55.8 55.1
1919 19.32 1932 67.7 55.1
1920 19.33 1933 69.7 52.8
1921 19.35 1935 72.2 49 5
1922 19 37 1937 87.3 46.4
1923 19 38 1938 104 7 44 9
1924 19 40 1940 117 3 43 6
1925 19 42 1942 43 1
1926 19 43 1963 43 9
1927 19 45 1945 3.1
1928 19.47 1947 45 3
1929 19.48 1948 45 7
1930 19 50 1950 6 8
1937 19 62 1962 75 8
1940 19.67 1967 92.3 38 7
1941 19.68 1968 38.6
1942 19.70 1970 39.2
1943 19.72 1972 40.5
1944 19.73 1973 85 7 38.9
1945 19 75 1975 87.9 37.2
1946 19.77 1977 81.8 40.6
1947 19.78 1978 93.7 42.9
1948 19.80 1980 92.9 44.0
B -107
-------
Run 6, continued
TIME Decimal Decimal 114CM THCC TOM
Time Time (p n, (p n, (p n,
x 100 dry) dry) dry)
1949 19 82 1982 89.3 44.2
1950 19.83 1983 83.7 44 5
1951 19 85 1985 80.1 44.7
1952 19.87 1987 82 1 45 3
1953 19.88 1988 99. 46.0
1954 19.90 1990 105.7 45 3
1955 19.92 1992 106.8 44 5
1956 19.93 1993 45.0
1957 19.95 1995 45.8
1958 19 97 1997 46.4
1959 19.98 1998 45.1
2000 20.00 2000 39.2
2001 20.02 2002 34.3
2002 20.03 2003 30.1
2003 20.05 2005 27.9 90.1
2004 20.07 2007 90.7 29.3
2005 20.08 2008 90.6 31 6
2006 20.10 2010 80.1 34.2
2007 20.12 2012 70.8 36.7
2008 20.13 2013 163.8 38.8
2009 20.15 2015 104.2 39.5
2010 20.17 2017 83.5 39.3
2011 20.18 2018
2019 20 32 2032 60 9 39.8
2020 20 33 2033 61 2 39 6
2021 20.35 2035 78 0 39 0
2022 20.37 2037 90 7 38 3 85.1
2023 20.38 2038 85.2 38.0
2024 20.40 2040 48.0 38.3
2025 20.42 2042 59.5 39.6
2026 20.43 2043 75.2 40.3
2027 20.45 2045 71 0 40.2
2028 20.47 2047 110.0 39.8
2029 20.48 2068 103.8 39.8
2030 20.50 2050 103 6 39 6
2031 20.52 2052 95.3 41.4
2032 20 53 2053 60.6 43.8
2033 20.55 2055 66.2 65 6
2034 20 57 2057 65 1 47 1
2035 20.58 2058 70.2 47 3
2036 20.60 2060 87 8 46 0
2037 20 62 2062 82 4 44.2
2038 20.63 2063 76.8 42 2
2039 20 65 2065 71.0 42 0
2040 20 67 2067 68.8 42.1 86.2
2041 20 68 2068 67.8 42.3
2062 20.70 2070 66.9 42.7
2043 20.72 2072 65.0 43.3
2044 20.73 2073 60.4 43.7
2045 20 75 2075 67.3 43.5
8-108
-------
Run 6, continued
TIME Decimal Decimal INCH THCC TOM
Time Time (ppm, (ppm, (ppm,
x 100 dry) dry) dry)
2046 20.77 2077 75 5 42.2
2047 20 78 2078 77.6 40.3
2048 20.80 2080 59.0 39 0
2049 20.82 2082 57.3 40.5
2059 20.98 2098 85 5
2118 21.30 2130 40.6
2122 21.37 2137 65.0 36.8
2123 21.38 2138 45.7 35.8
2124 21.40 2140 49.6 35.0
2125 21.42 2142 59.5 34.2
2126 21.43 2143 45.7 33.6
2127 21.45 2145 55.7 32.7
2128 21.47 2147 73.0 32.0
2129 21.48 2148 47.1 30.9
2130 21.50 2150 45.5 30.0
2131 21.52 2152 59.2 30.1
2132 21.53 2153 65.5 30.8
2133 21.55 2155 61.4 31.0
2134 21.57 2157 73.5 30.8
2135 21 58 2158 71 6 30 9
2136 21.60 2160 74.7 31.1 65.9
2137 21.62 2162 42.5 31.5
2138 21 63 2163 53 8 32.1
2139 21 65 2165 51 0 32.6
2140 21 67 2167 58.1 32.8
2141 21.68 2168 69.2 32.9
2142 21.70 2170 68.3 33.3
2143 21 72 2172 67.0 33.3
2144 21.73 2173 73 9 33.5
2145 21.75 2175 72.7 33.8
2146 21.77 2177 82.4 33.9
2147 21.78 2178 49.6 34 2
2148 21.80 2180 52.7 34.6
2169 21.82 2182 51.0 34.5
2150 21.83 2183 64.2 34.3
2151 21.85 2185 70.3 34.4
B-109
-------
RUN 6- HOT AND COLD HC CONCENTRATIONS
AND TOTAL ORGANIC MASS
1
cx
I-
I :’)
C
(0
0
0
0
(I)
(0
>,
0
>
E
0
0
C
0
4-.
(0
4-.
C
a)
0
C
0
0
Time (24 hour)
2200
Hot HG
Cold HO
± Organic Mass
-------
APPENDIX B—S
VOLATILE ORGANICS DATA
This appendix presents a summary of VOST data, laboratory techniques and
QA/QC checks performed.
B-ill
-------
ADJUSTED y OST VOLUr 1E
T Iap
V ’ 1une
carnp lec l t&tcc. ‘
‘ C ]
1
i
1 959 340 2916’ 1013
2 982 :50 ; 2916 10131 9191
3 10101 35o! 2315 ! c1: ,
2 I
1 1012 t 4 0 ?934 1 313 929
2 ;
21 9 8 46) 1 2934 13131 992;
2;
2
3 !
o;
4
31 985 1 4801 2934 1 1013! 39 1
1 1057 373 2918 1013 9 37
2! 10631 oso .: 2918; 10131 92 1
S I 558; 400 ! 2918 1)13’
1 1015 040 ,292a’ i3i3 1 9 0,
4;
4;
01
2; 10091 350
31 1000; 3 0
1 936 1 390
292a; io’j
29 : 4 101 21 9 6I
2942 lo is ! 8.76)
sI
5!
5 ’
L i
6
6
2 948
3 975
4} 969
I 924
2’ 9.50
3 [ 937
410
440
450
390
400
40.0
2942
2942
:2942
2942
2942
2942
10131 891
1013; 393i
1012 $854
1013 2.64
1013 $96
1013
B-113
-------
VOLATILE ORGANICS ANALYSIS DATA SUMMARY
This Data Summary describes the analysis of volatiles samples collected
from the Continental Cement Wet Kiln in Hannibal, MO. Two sample types were
analyzed: VOST (Tenax and Tenax/Charcoal cartridges) and VOST condensates.
Analysis of reportable data began on June 22, 1990 and proceeded until July
16. Procedures used for the analysis of the volatiles samples are described In
“Draft Test and QA Plan--Continental Wet Kiln, Hannibal, MO” (June 8, 1990).
The analysis procedures described in the test plan were derived from SW—846
Methods 8240 and 5040; however, a number of modifications to these methods were
employed by MRI for this study. These modifications are listed in Sections 11.1
and 11.2 of the test plan. Two modifications were made to the purge—and—trap
apparatus which were not listed in the test plan. These modifications are
described in a later section of this memo.
1.0 SAMPLE ANALYSIS
Twenty—seven volatile “Products of Incomplete Combustion” (P lC) compounds
were selected for analysis in this study. The list of compounds actually used
is slightly different than that provided in the test plan because three
compounds were not included in the composite standard mixture purchased from
Supelco. The three compounds not included in the analysis are cis—1,3—
dichioropropene, 2-chioroethylvinyl ether and trichiorofluoromethane. In
addition, two compounds were analyzed in this study that were not included in
the original list (chlorobenzene and p—dioxane).
Two internal standards (d 6 -benzene and 1,4-difluorobenzene) and four
surrogates (d —1,2—dichloroethane, d 5 —chlorobenzene, d 8 -toluene and
bromofluorobenzene) were added to the samples immediately prior to analysis.
Surrogate and target analyte concentrations were determined by the internal
standard method using 1,4—difluorobenzene as the reference internal standard.
The second internal standard compound, d6—benzene, was not used as a reference
due to problems associated with the sample matrix (this problem is described in
a later section of this appendix). Separate calibration curves were generated
for the VOST samples and VOST condensate samples.
2.0 OATA ORGANIZATION
Results of this analysis are available in two forms: summary report and
t ie “raw” GC/MS data. The summary reports are contained in this appendix and
the raw data has been appropriately stored for possible future reference. The
contents of each of these data forms are outlined below:
A. Summary Reports
1. Calibration Curve Summary
2. MRI QA Performance Sample Analysis Summary
3. Daily Blanks Analysis Summary
4. Daily Standards Analysis Summary
5. VOST Sample Analysis Summary
6. VOST Condensate Analysis Summary
B- 114
-------
B. Raw Data
1. Tentatively Identified Compounds (TIC) Summaries
2. Total characterization of unidentified peaks in a VOST sample
pair (Tenax and Tenax/Charcoal)
3. Reconstructed ion chromatograms (RICs) of VOST samples
4. PFK spectrum and mass listing
5. BFB spectrum, mass listing, and BFB QA summary
6. PARA printouts
7. QUAN quantitation report printuts
8. RIC and ion plots
9. Photocopies of all pertinent laboratory notebook pages
10. Calibration curve printouts, including RESP curves, EDRL
listings, and average relative response factors
11. Sample Traceability forms
3.0 ADDITIONAL NOTES REGARDING THIS ANALYSIS
3.1 All the samples were analyzed within the 14 day holding time specified
in the test plan (holding times for VOST condensates were not specifically
mentioned in the test plan.)
3.2 Although not formally required for this study as per the test plan,
calibration curves were generated for all of the PlC compounds and appropriate
quality assurance procedures were followed. It was felt that a true calibration
curve would provide more accurate quantitative information than the procedure
recommended in the test plan (using either response factors of 1.0 or
“historical” response factors for quantitation of PlC’s). Three calibration
curves were generated during the course of the study: two calibration curves
for the analysis of VOST samples and a s?parate calibration curve for the
analysis of the VOST condensates.
3.3 Relative standard deviations (RSD’s) for the PLC response factors
(Rfs) in the three calibration curves were ’ generally within ±30%, with the
exception of some early eluting (i.e. very volatile) compounds in the VOST
calibration curves, which was attributable to the method in which the standards
were introduced into the GC/MS. A single st ndard solution containing 50 ng/ul
of each PlC compound was used. In order to ;enerate a multi-point calibration,
increasing volumes of the standard solution were spiked onto a clean VOST trap
and thermally desorbed onto the analytical trap. As a result, the high point of
the calibration curve required injecting a relatively large volume ( 2 Oul) of PlC
standard onto the VOST trap. It is believed that the large amount of solvent
(methanol) injected onto the trap “flushed” the more volatile compounds through
the trap without being absorbed onto the Tenax. By contrast, the effect was not
observed in the waters analysis, where the PlC standard was injected directly
into 5m1 of water which was then purged onto the analytical trap. The flushing
effect is not relevant to the analysis of the VOST samples themselves, since no
large volumes of solvent were spiked onto the sample traps. Response factors
for the high levels of affected compounds were discarded when call curve average
RFs were computed.
B-115
-------
3.4 Two modifications to Method 8240 were employed for the purge-and-trap
portion of the analysis apparatus. The first modification involved heating the
purge tower water to ca. 40°C using a heating jacket around the purge tower for
the VOST condensate analysis. This was done to improve the purging efficiency
of the system for the more water soluble PLC compounds (notably methyl ethyl
ketone and p—dioxane). The second modification involved removing the water from
the purge tower altogether for the analysis of the VOST samples. tn this
configuration, the purge tower simply acted as a dry water trap in case large
amounts of water were collected in the VOST cartridges during sampling. As can
be seen in the attached Calibration Curve and Daily Standards Analysis
Summaries, the dry—purge tower setup was effective in providing good
reproducibility for all PLC compounds in the VOST analysis, including those
which were water-soluble. In the VOST condensate analysis however, the purging
efficiency of p-dioxane from the purge water was poor, even though the purge
water was heated.
3.5 Although not specifically required by either the test or QA plan, a QA
Performance Sample was analyzed for both the VOST and VOST condensate
analyses. Results of the QAP saniple are attached. PLC recoveries for the VOST
condensate analysis were all within ±25% with the exception of chloroform (36%
recovery), which had an actual concentration approximately ten times the highest
point of the calibration curve. Recoveries of PLC’s in the VOST QAP sample
analysis were not as good, although it is suspected that this was due to the
fact that the sample was analyzed immediately following the high level
calibration standard and some carry-over may have occurred (all the reported
recoveries had a high bias). The problem was noted by the QA officer on the
attached QA Performance Sample Request and Reporting Form and no further action
was taken.
3.6 As expected, the VOST samples contained very high levels of some
PlC’s, notably benzene, toluene, acetone, acrylonitrile and ethylbenzene. In
some cases, PlC levels were so high that the primary quantitation ion was
saturated. In such cases, quantitation was performed using an alternate
quantitation Ion of lower intensity. Unfortunately, the range of the
calibration curve was usually exceeded in such cases but the reported values
should still provide a reasonable estimate of the PLC concentration. Previous
analyses of this type have indicated that compounds may be accurately
quantitated outside a calibration curve range as long as the quantitation ions
used are not saturated, although the calculated amounts should still only be
regarded as semi-quantitative.
3.7 Limits of detection and limits of quantitation were not determined for
this study. Therefore, no amounts were “filtered out”. As a precaution, PLC
amounts which fall below the lowest level of their respective calibration curve
should only be regarded as semi—quantitative.
3.8 As stated previously, six reference compounds (two internal standards
and four surrogates) were added to the sample immediately prior to analysis. A
relatively large number of reference compounds were used in this study to
provide redundancy in case interferences prevented accurate quantitatlon of one
or more of them. The problem of sample matrix interference was described in a
previous report (“Applicability of the VOST Method for Measuring Cement Kiln
B— 116
-------
Emissions During Firing of Hazardous Wastes”, prepared for U.S. E.P.A. by Radian
Corp., May 16, 1988). As was seen in that study, the high levels of native
benzene observed in the VOST samples severely interfered with the quantitation
of the d 6 -benzene internal standard, and as a result d 6 —benzene was not used as
a reference compound In quantitative de erminations. Similarly, d -1,2-
dichioroethane was also severely affected by matrix interference, as can be seen
in the attached VOST Sample Analysis Summary. Relative standard deviations for
the recovery of df-benzene and dk—1,2-dlchloroethane in the VOST samples were
determined to be 59% and 51%, respectively. In contrast, recovery RSD’s for the
same compounds in the daily standards was determined to be 102% and 97%,
respectively. No major interferences were observed In the VOST samples for the
remaining four reference compounds; recovery RSD’s for the surrogates
d 8 —toluene, bromofluorobenzene and d -chlorobenzene were 4%, 15% and 6%,
respectively (recovery is not applicable to the fourth compound, 1,4-
difluorobenzene, which served as the internal standard). No interferences were
observed in the VOST condensate samples.
3.9 In addition to the PlC compounds, a number of other compounds were
observed in the VOST samples, Including large numbers of alkanes, alkenes,
cyclic hydrocarbons, benzaldehyde, benzofuran, benzonitrile and methyl styrene,
to name a few. Two sets of data relating to these other compounds are available
for possible future reference. The first set includes tentative identifications
and quantitations of the ten largest peaks In each of the VOST sample runs. The
test plan originally specified that only five peaks were to be Identified,
however due to the large number of observed peaks, it was felt that an
additional effort in this area might be appropriate. The second set of data
extends that concern to include a complete characterization of all major peaks
in a single VOST sample (Tenax and Tenax/charcoal traps). This complete
characterization may be considered an example of the types of compounds that
were present in the other VOST samples. Identification of unknown peaks were
performed using a computerized mass spectral library search program (LIBR,
Finnigan/MAT Corp.) which compared the unknown spectra to 42222 reference mass
spectra contained in the NBS/EPA mass spectral database. The library results
were then reviewed and corrected by a mass spectrometrist experienced in mass
spectral Interpretation.
B-117
-------
CALIBRATION CURVE SUMMARY
Response Factor (vs total ng)
100 200 500 1000
calibration Curve Date: 6122/90
Instrument: 31 2
Index Comcound Name Ref
Analysis Method: CS
mlz 50
Avg
D
INOO1 d6-Benzene (IS.) 1N002
84
1.076
1.079
1.058
1.039
.988
1.048
4
1N002 1,4-Difluorobenzene (I.S.) 1N002
114
1.000
1.000
1.000
1.000
1.000
1.000
100
1N003 d4-1,2-Duchloroethane (Surr. 1N002
65
.291
.293
.296
.304
.317
.300
4
1N004 d8-Toluene (Surr) 1N002
98
1.177
1.227
1.231
1.225
1.206
1.213
2
1N008 Bromofluorobertzene (Surr.) 1N002
174
.363
.387
.390
.390
.406
.387
4
1N009 d5-Chlorobenzene (Surr.) 1N002
117
.770
.810
.800
.781
.745
.781
3
1N026 Diethyl ether 1N002
74
.118
.120
.112
.048
.100
35
1N027 Acroleiri 1N002
56
.085
.093
.094
.052
.081
25
1N028 1,1 -Dichloroethene 1N002
61
.388
.400
.250
.114
.288
47
1N029 Acetone 1N002
58
.146
.159
.163
.129
.149
10
1N030 Methylene chloride 1N002
84
.229
.249
.272
.231
.245
8
1N031 Acrylonitrile 1N002
53
.259
.296
.322
.281
.227
.277
1 3
1N032 t-1,2-Dichloroethene 1N002
61
.464
.490
.529
.447
.483
7
1N033 1,1-Dichioroethane 1N002
63
.535
.581
.647
.550
.338
.530
22
1N034 Methyl ethyl ketone (MEK) 1N002
72
.152
.165
.173
.149
.138
.155
9
1N035 Chloroform 1N002
85
.289
.313
.346
.315
.321
.317
6
1N036 1,1,1-Trichloroethane 1N002
97
.315
.343
.357
.317
.254
.317
12
1N037 Carbon tetrachloride lNOO2
117
.261
.288
.309
.269
.234
.272
10
1N038 Benzene 1N002
78
1.007
1.046
1.080
.991
.860
.997
8
1N039 1,2-Dichloroethane 1N002
62
.300
.312
.335
.303
.283
.307
6
1N040 Trichloroethene lNOO2
95
.345
.380
.402
.466
.371
.393
1 2
1N041 1,2-Dichloropropane lNOO2
63
.469
.507
.533
.499
.493
.500
5
1N042 p-Dioxane 1N002
88
.160
.158
.178
.151
.159
.161
6
1N043 Bromodichioromethane 1N002
83
.415
.451
.483
.456
.443
.450
5
1N044 Toluene 1N002
92
.635
.687
.702
.647
.572
.649
8
1N045 t-1,3.Dichloropropene 1N002
75
.293
.337
.365
.350
.355
.340
8
1N046 1,1,2-Trichioroethane 1N002
83
.308
.365
.381
.361
.347
.352
8
1N047 Tetrachioroetherie (PERC) 1N002
1 64
.236
.260
.270
.252
.244
.252
5
1N048 Dibromochloromethane 1N002
129
.352
.391
.422
.404
.388
.391
7
1N049 Chlorobenzene (MCB) 1N002
112
.684
.729
.754
.718
.586
.694
9
1N050 Ethylbenzene 1N002
106
.325
.374
.391
.364
.348
.360
7
INOS1 Bromoform 1N002
173
.296
.358
.382
.364
.345
.349
9
1N052 1,1,2,2-Tetrachloroethane 1N002
83
.712
.808
.841
.776
.615
.751
12
1N053 Benzene (m/z 51) 1N002
51
1.877
1.074
.669
.402
.310
.866
74
1N054 Benzene (m/z 79) 1N002
79
.048
.055
.062
.059
.059
.057
9
1N055 Toluene (m/z 65) 1N002
65
.189
.202
.206
.184
.170
.190
8
1N056 Acetone (m/z 42) 1N002
42
.032
.036
.042
.032
.035
1 4
1N057 Acrylonitrile (mlz 51) 1N002
51
.101
.108
.117
.102
.096
.105
8
1N058 Benzene (m/z 74) 1N002
74
.060
.053
.055
.049
.048
.053
9
1N059 Toluene (mlz 90) 1N002
90
.012
.015
.016
.016
.015
14
1N060 Ethylbenzene (mhz 92) 1N002
92
.077
.092
.101
.093
.088
.090
10
B-118
-------
CALIBRATION CURVE SUMMARY
Calibration Curve
Date: 7/5/90
Analysis
Method: \.CS
Instrument: 312
Index CornDoundName
Ref rn/i
50
Resoonse
100
Factor
200
(vs
total
500
r19)
1000
Ave I D
1N002 1,4-Difluorobenzene (LS.) 1N002
114
1.000
1.000
1.000
1.000
1.000
1.000
100
1N003 d4-1,2-Dichloroethane (Surr. 1N002
65
.310
.308
.317
.328
.336
.320
4
1N004 d8•Toluene (Surr) 1N002
98
1.187
1.187
1.201
1.183
1.170
1.186
1
1N008 Bromofluorobeniene (Surr.) 1N002
174
.403
.404
.412
.408
.409
.407
1
1N009 d5-Chlorobenzene (Surr.) 1N002
117
.791
.780
.789
.771
.745
.775
2
1N026 Diethyl ether 1N002
74
.128
.129
.122
.052
.108
35
1N027 Acrolein 1N002
56
.060
.065
.064
.035
.056
25
1N028 1,1 -Dichioroethene 1N002
61
.433
.445
.365
.134
.344
42
1N029 Acetone 1N002
58
.165
.159
.149
.110
.146
17
1N030 Methylene chloride 1N002
84
.281
.275
.274
.129
.240
31
1N031 Acrylonhtrile 1N002
53
.292
.299
.299
.284
.216
.278
13
1N032 t-1,2-Duchloroetherie 1N002
61
.504
.519
.504
.464
.138
.426
38
1N033 1,1-Dichloroethane 1N002
63
.579
.600
.584
.556
.256
.515
28
1N034 Methyl ethyl ketone (MEK) 1N002
72
.169
.168
.164
.155
.137
.159
9
1N035 Chloroform 1N002
85
.337
.355
.354
.344
.332
.344
3
1N036 1,1,1-Trichioroethane 1N002
97
.376
.386
.398
.361
.267
.357
15
1N037 Carbon tetrachionde 1N002
117
.316
.342
.349
.312
.251
.314
12
1N038 Benzene 1N002
78
1.123
1.092
1.051
1.011
.881
1.032
9
1N039 1,2-Dichioroethane 1N002
62
.363
.367
.362
.353
.325
.354
5
lN040 Trichloroethene 1N002
95
.396
.406
.404
.401
.381
.397
3
1N041 1,2-Dichioropropane 1N002
63
.497
.515
.509
.499
.479
.500
3
lN042 p-Dioxane 1N002
88
.095
.131
.151
.176
.168
.144
23
1N043 Bromodichiorometharie 1N002
83
.481
.492
.494
.488
.471
.485
2
1N044 Toluene 1N002
92
.762
.712
.691
.664
.585
.683
10
1N045 t-1,3-Dichloropropene 1N002
75
.347
.361
.364
.366
.361
.360
2
1N046 1,1,2-Trichioroethane 1N002
83
.352
.378
.371
.363
.343
.361
4
1N047 Tetrachloroethene (PERC) 1N002
1 64
.284
.289
.285
.276
.263
.279
4
1N048 Dibromochioromethane INOO2
129
.429
.449
.447
.446
.424
.439
3
1N049 Chlorobenzene (MCB) 1N002
112
.766
.794
.781
.762
.618
.744
10
1N050 Ethylbenzene 1N002
1 06
.391
.400
.391
.380
.355
.383
5
1N051 Bromoform 1N002
173
.385
.413
.405
.403
.378
.397
4
lN052 1 ,1,2,2-Tetrachloroethane 1N002
83
.857
.851
.822
.804
.640
.795
11
1N053 Benzene (rn/i 51) 1N002
51
1.806
1.022
.636
.394
.965
64
1N054 Benzene (rn/i 79) 1N002
79
.055
.057
.057
.059
.057
.057
2
1N055 Toluene (rn/i 65) 1N002
65
.222
.209
.196
.184
.169
.196
11
1N056 Acetone (mhz 42) 1N002
42
.036
.037
.041
.031
.037
12
1N057 Acrylonitrile (rn/i 51) 1N002
51
.109
.1IB
.108
.105
.087
.106
11
1N058 Benzene (mhz 74) INOO2
74
.064
.059
.056
.052
.050
.056
1 0
lN059 Toluene (m/z 90) 1N002
90
.012
.016
.017
.016
.015
13
INO6O Ethylbenzene (rn/i 92) INOO2
92
.096
.099
.102
.098
.091
.097
4
B—119
-------
CALIBRATION CURVE SUMMARY
Response Factor (vs total ng)
50 100 200 500 1000 Ava D
Calibration Curve Date: 7/2/90
Instrument: 312
Index Comoound Name Ref mlz
Analysis Method: WAT
INOO1 d6-Berizene (I.S.) 1N002
84
1.049
1.045
1.041
1.017
.970
1.024 3
1N002 1,4-Difluorobenzena (I.S.) 1N002
114
1.000
1.000
1.000
1.000
1.000
1.000 100
1N003 d4-1,2-Dichloroethane (Surr. 1N002
65
.296
.297
.315
.311
.326
.309 4
1N004 d8-Toluene (Surr) 1N002
98
1.206
1.182
1.193
1.195
1.185
1.192 1
1N008 Bromofluorobenzene (Surr.) 1N002
174
.417
.412
.437
.422
.415
.421 2
1N009 d5-Chlorobenzene (Surr.) 1N002
117
.799
.790
.818
.779
.742
.786 4
IN026 Diethyl ether 1N002
74
.592
.604
.661
.483
.470
.562 1 5
1N027 Acrolein 1N002
56
.024
.029
.032
.027
.028
.028 9
1N028 1,1-Dichloroethene 1N002
61
.386
.408
.406
.361
.377
.388 5
1N029 Acetone 1N002
58
.025
.025
.027
.022
.022
.024 1 0
1N030 Methylene chloride 1N002
84
.235
.247
.264
.220
.240
.241 7
1N031 Acrylonitrile 1N002
53
.117
.124
.124
.101
.103
.114 10
lN032 t-1,2-Dichloroethene INOO2
61
.429
.454
.461
.394
.405
.428 7
1N033 1,1-Dichioroethane 1N002
63
.498
.527
.657
.468
.496
.529 14
1N034 Methyl ethyl ketone (MEK) INOO2
72
.053
.067
.056
.045
.047
.053 1 6
1N035 Chloroform 1N002
85
.347
.364
.384
.328
.361
.357 6
1N036 1,1,1-Trichloroethane INOO2
97
.383
.391
.390
.360
.389
.383 3
1N037 Carbon tetrachloride 1N002
117
.306
.334
.335
.298
.328
.320 5
IN038 Benzene 1N002
78
1.133
1.140
1.157
.985
.878
1.058 12
1N039 1,2-Dichloroethane 1N002
62
.356
.361
.389
.326
.335
.353 7
lNO4O Trichioroethene INOO2
95
.418
.444
.449
.395
.408
.423 5
1N041 1,2-Dichioropropane INOO2
63
.543
.557
.580
.496
.522
.540 6
1N042 p-Dioxane INOO2
88
.000
.001
.000
.000
.000
.000 107
1N043 Bromodichioromethane 1N002
83
.488
.514
.545
.467
.503
.503 6
1N044 Toluene 1N002
92
.740
.735.
.736
.635
.605
.690 9
1N045 t-1,3-Dichloropropene 1N002
75
.370
.378
.424
.354
.380
.381 7
1N046 1,1,2-Trichloroethane lN002
83
.387
.402
.439
.356
.369
.390 8
1N047 Tetrachloroethene (PERC) INOO2
164
.286
.298
.293
.263
.265
.281 6
IN048 Dibromochioromethane 1N002
129
.445
.467
.518
.428
.439
.459 8
1N049 Chlorobenzene(MCB) 1N002
112
.832
.847
.869
.739
.639
.785 12
1N050 Ethylbenzene 1N002
106
.417
.425
.428
.371
.370
.402 7
lNO5l Bromoform 1N002
173
.392
.426
.485
.393
.401
.419 9
1N052 1,1,2,2-Tetrachloroethane 1N002
83
.837
.865
.939
.753
.646
.808 14
1N053 Benzene (mhz 51) 1N002
51
1.821
1.051
.700
.392
.320
.857 71
1N054 Benzene (m/z 79) 1N002
79
.091
.091
.070
.063
.065
.076 1 8
IN055 Toluene (mhz 65) 1N002
65
.220
.216
.209
.177
.177
.200 10
B-120
-------
P [ I t AI SA RI. 1 R I lN
£
To be completed by project personnel:
Project No.i g,, -
Requested byt . J ph Oh ,4fr
Approved by: ______________________
Analysis lype:
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Analysis Results
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Stotage Conditions: —
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Projecl No. :_ jIO.2, —
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Request date! _______________
Expected Analysis dale: L/zL/fp
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ACRYLONI TR I LE
1 . 1—DICHLOROETHENE ___
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-------
clank Analysis Summary • Hannibal 8912-3115
Amount (ng)
Ouan Ffl.n,m. F25Y03 F25YQ4 F26Y03 F26Y04 F26YQ5 F26YQ8 F27Y03 F27Y04 F20Y03 F28Y04 F2OYQI
Ion 0 0 0 0 0 0 0 0 0 0 0
No. Compound (m/z) 81K BUC 81K BU( 01K BUC BLK BtJ( BUC 81K BUC
I dB-Benzene (Alt. IS.) 84 105 105 107 108 106 102 106 100 108 105 108
2 L4-Difluorobnnzone (U.S.) 114 100 100 100 100 100 100 100 100 100 100 100
3 d4-1.2-Olchloroethane (Alt. U.S.: 65 106 105 103 105 112 99 112 96 108 111 122
4 d6-Toluene (Surr.) 98 105 104 104 105 102 96 104 102 105 103 103
5 Bromolluorobenzene (Burr.) 174 109 107 106 106 108 104 101 107 102 105 104
6 dS-Chlorobenzeno (Suir.) 117 i09 107 109 108 107 100 108 108 107 106 107
7 DIethyl ether 74
8 Acroleln 58
9 1.1-Dichioroetherie 61
10 Acetone 58
ii Methylens ChlorIde 84 .c
12 Acrylonltrilo 53
13 t-1 2-Dichioroetheno 61
14 1,1-Dlchioroethane 83 . .<
15 Methyl ethyl ketone (MEK) 72 .c .c
16 Chloroform 85
17 1 1 1-Trichtoroethene 97
Carbon Tetrachloride 117
19 Denzeno 78 127 248
‘20 1,2.Dichtoroethane 62
21 Trlchioroethene 95
2 i,2-D;i pp R i
23 p-Dloxene 88 714 766 73 660
24 Bromodlchloromethane 83
25 Toluene 92 74
26 t-l.3.Dichtoropropene 75
27 1,1 ,2-Trlchioroethane 83
28 Tetrachtoroethene (PERC) 164
29 Dibromochloromothane 129
30 Chtorobenzene (MCB) 112
31 Ethylbenzene 106
32 Bromoform 173
33 1,I,2,2-Tetrachtoroothane 83
a. Values for surrogates and alternale internal standards are percent recoveries.
b. Actual amt. - 5x nominal amt. —
c. VER — Daily Initial verification aId.
flN — Daily Ilnal etd.
BLK - Blank
ci. — P4o 1 detected at ieveis above the lowest calibration standard.
-------
flank Analysis Summary
• Hannibal 8912-3115
- Amount (ng)
a. Values for eurfogates and alternate internal
b. Actual amt. 5* nomfnal amt.
c. VEfl — Daily Initial verification aId.
FIN — Daily final std.
Blank
d. < Not detected at levels above the lowest
A L fov6io
/ f,1df ,‘ .
Cuan
.n.m. 603Y03
G03Y05
003Y06
GO5YQ7
G05Y08
GOGYO3
G06Y04
010Y03
G1IYQ3
G1IYQ4
G1IVOS
POfl
Am (n )
0
(P
0
0
0
0
0
0
0
0
0
No. Compound (mu)
,,,. ‘ 91K
9*J(
BU(
91K
01K
OLK
BLJ(
BU(
BU(
91K
91K
I
d6-Benzene (Alt. i.S.)
84
102
104
104
104
100
99
104
102
103
103
101
2
1,4-Dllluorobenzene (i.S.)
114
100
100
100
too
ioo
100
100
100
100
100
100
3
d4.I 2-DIchloroethane (Alt.
l.S.
65
94
95
94
97
95
96
97
97
98
98
96
4
d8 .Tolueno (Surr.)
08
09
101
101
100
100
90
102
100
101
100
102
5
Bromolluorobenzone (Surr.)
174
98
101
100
98
0
0
103
96
99
97
103
6
1
d5-Chlorobenzene (Surr.)
Diethyl ether
111
14
101
dj
103
<
103
<
103
<
103
<
102
<
105
<
103
<
105
<
103
<
105
<
8
Acroleln
56
<
<
<
<
<
<
<
<
<
<
.
9
1,1-Dichloroethene
81
<
<
<
<
<
<
<
<
10
Acetone
58
<
<
<
<
.<
.<
<
<
<
Ii
Mothylene Chloride
84
<
c
c
c
c
.c
<
c
c
c
1 2
Acrylonlirlle
53
c
<
<
<
<
<
<
<
<
<
<
13
t-1,2-Dlchloroethene
61
<
<
<
<
<
<
<
.
<
<
14
1,1-Dlchioroethano
63
<
<
<
<
<
<
<
<
<
<
I 5
Methyl ethyl ketone (MEK)
72
c
<
c
c
c
<
<
c
c
<
IS
Chloroform
85
<
<
<
<
<
<
.<
<
<
.(
<
—
17
I 8
1,1,1-Trichloroothane
Carbon Tetrachiorlde
97
11 7
<
<
<
<
<
<
<
<
c
<
<
<
<
<
<
.<
<
<
<
I9
Benzene
78
<
<
<
<
<
<
c
<
<
84
20
1,2-Dlchioroethane
62
<
<
<
<
<
<
,<
<
<
<
<
21
Trlchioroethene
95
<
<
<
<
<
<
<
<
<
<
22
1,2-Dichloropropene
63
<
<
<
<
<
<
.<
<
<
<
<
23
p-Dloxane
88
<
<
<
488
<
592
<
322
338
<
<
24
Brornodicliloromethane
83
<
<
c
c
c
c
c
c
.c
25
Toluene
92
<
<
<
<
<
<
<
<
<
26
t1 ,3-Dlchtoropropene
75
<
<
<
<
<
<
<
.<
<
<
27
1,1,2-Trichloroethane
83
c
c
<
<
c
c
c
c
c
c
c
28
Telracliloroethene (PERC)
164
c
<
c
c
c
c
c
<
c
29
Dibromochloromethane
129
<
<
<
<
<
<
<
<
<
<
<
30
Chlorobenrene (MCB)
112
<
<
<
<
<
<
<
<
<
<
31
Ethylbenzene
lOB
<
<
<
<
<
<
<
<
<
<
32
Bromoform
173
<
<
c
<
<
<
<
<
<
c
<
33
1,1,2,2-Tetrachloroothane
83
<
<
<
<
<
<
<
<
<
-------
Blank Analysis Summary - Hannfbal 8912-3115
Amount (ng) 6.1
Ouan Ffl.n.n. G12Y04 GI3YQ3 013Y04 G13Y05 G13YQB GI3YQ7 G16YO3 Avg
Ion Ani 0 0 0 0 0 0 0 Recovery
No. Compound (mlz) Typ. 5 ’ B1J BU( 81K BU( BUC BU( 81K (%)
I d6-Benzene (Alt. I.S.) 84 104 100 99 99 99 99 101 103
2 1•4-Dlffuorobenzene (IS.) 114 100 100 100 100 100 100 100 100
3 d4-1,2-Dfchloroethano (Alt. i.s.: 65 92 93 94 92 92 92 99 100
4 d8-Toluene (Surt.) 08 104 97 100 100 99 101 99 101
5 Uromofluoroberizene (Surr.) 174 124 92 103 91 103 101 98 96
6 d5-Chiorobenzene (Suit.) 117 123 99 104 103 103 104 101 105
7 Diethyt ether 74 <4/ <
8 Acroleln 58
9 1,1-Dichloroethene 61
10 Acetone 58 <
11 Methylene Chloride 04 < < < < <
12 Acrylonitrile 53 < .<
13 t-1 ,2-Dlchlorootherie 81 <
14 1,1-Dlchtoreethane 63
IS Methyl ethyl ketono (MEK) 72
IS Chloroform 85 <
I7 1 ,1,1-Trlchloroethano 97
,.L 16 Carbon Tetrachforldo 117
19 Bon one 78 81 < 146 i O O 67
20 1,2-Dichloroethono 62
21 Trlchioroethene 95
22 1,2-Olcrnoiopropane 63
23 p-Dtoxonn 88 331 848
24 Bromodlchioromethano 83
25 Totuono 92
20 t-l,3-Dlchloropropeno 75 <
27 1,1,2-Trlchioroethane 83
28 Totrachloroethene (PEAC) 164
29 Dlbromochloromethana 129
30 Chforobonzane (MCB) 112
31 Ethylbenzone 106
32 Bromoform 173 < <
33 1,1,2,2-Tatreehloroothan , 83
a. Values for aurro atea and alternate Internal
b. Adual amt. 5* nomInal amt.
c. VEFI — Daily initial verification etd.
FIN Daily finat aId.
9 1K Blank
d. < — Not detected at Ieve a above the lowest
-------
Standards Analysis Summary - Hannibal 8912-3115
Percent Recovery (%)
Quan Filenan F25YQ2 F25YQ5 F26YQ2 F2OYQ7 F27YQ2 F27YQ5 F2OYQ2 F28YQ5 F29YQ3 F29YQ5
ion * 200 200 200 200 200 200 200 200 200 200
No. Compound (mu) Typs VER FIN VER FIN VER FIN VER FIN VER FIN
1 d6-Benzene (Alt. P .S .) 84 102 104 103 78 105 74 109 106 105 102
2 1 4-Di1Iuorobenzene (IS.) 114 100 100 100 100 100 100 100 100 100 100
3 d4•1 2•DIchIoroethane (All. i.S. 65 104 100 101 84 112 64 108 119 118 0
4 dB-Totuene (Surr.) 98 104 103 100 102 105 101 106 91 103 104
5 Bromofluorobenzene (Surr.) 174 103 107 100 108 102 108 98 59 104 0
6 d5.Chiorobenzene (Surr.) 117 105 105 103 103 107 104 108 78 105 0
7 Diethyl ether 74 128 128 132 lii 134 35 130 133 120 114
8 Acrolein 56 101 109 lii 70 112 52 110 80 95 0
9 1 .1-Dlchioroethene 61 132 132 138 137 148 59 144 165 151 143
10 Acetone 58 105 110 111 92 114 75 117 48 107 104
11 Melhyleno Chloride 84 108 118 118 96 118 89 123 118 112 99
12 Acrylonltrile 53 108 118 116 101 107 101 115 85 110 108
13 1-1 .2-Dlclitoroethene 61 103 112 114 90 113 88 108 105 tOO 94
14 1 1-Dichloroelhane 63 112 113 115 98 123 94 121 112 106 97
15 Methyl ethyl ketone (MEK) 72 104 111 113 88 109 89 125 69 92 115
16 Chlorolorm 85 105 112 110 78 112 76 113 128 121 110
. 17 1 .1 .1-Trichloroolhane 97 108 115 115 86 128 72 128 132 133 120
‘\ 18 Carbon Tetrachioride 117 110 117 113 83 128 79 123 132 133 120
0119 flenzene 78 107 112 112 88 115 110 119 117 113 106
20 1 .2-Dichioroethano 82 108 115 110 72 127 87 119 138 128 122
21 Trtchloroethena 95 99 104 103 103 107 102 112 110 105 97
22 1,2-Dichloropropane 63 102 108 107 109 108 108 114 105 105 99
23 p-Dioxane 88 49 55 105 23 50 4 52 0 58 0
24 flromodlchloromethane 83 101 107 106 106 114 105 113 116 111 104
25 Toluene 92 106 111 109 111 115 120 114 105 110 104
26 1-1,3-Dichloropropene 75 102 107 104 109 110 111 116 104 114 108
27 1,1,2-Trichloroethane 83 102 108 100 108 109 108 108 93 102 95
28 Teirachloroethene (PERC) 164 102 110 107 108 111 108 105 102 107 98
29 Dtbromochioromethane 129 102 110 106 107 109 109 104 96 110 105
30 Chlorobenzene(MCB) 112 107 115 111 115 112 114 108 88 112 112
31 Ethyibenzene 106 106 110 109 111 114 112 118 77 110 105
32 flromoform 173 103 113 107 110 113 116 112 71 114 109
33 1,1,2,2-Toirachloroethane 83 109 114 113 116 108 119 108 50 108 0
34 Benzone (mIz 51) 51 80 82 80 54 83 59 83 85 84 82
35 Denzeno (m/z 79) 79 120 109 114 160 179 223 119 170 184 144
38 Toiueno (mIz 65) 65 lOB 113 112 111 117 124 120 104 100 106
a. Actual amt. — 5x nominal ami.
b. VER — Daily Initial verification std.
FIN — Daily final std.
81K — flank
-------
Standards Analysis Summary - Hannibal 8912-3115
Percent Recovery (%)
OUafl Filename GO3YQ2 GO3YO7 G05Y09 GO6YQ2 006Y06 G1OYQ2 G1OYQ4 G11YQ2 G1IYQB G12Y02
Ion M I (ng) 200 200 100 200 200 100 100 100 100 100
No. Compound (mu) VEIl FIN FIN VEIl FIN VEIl FIN VEIl FIN VEIl
I dB-Ronzone (Alt. IS.) 84 104 103 100 103 100 102 102 102 100 102
2 1,4-Difluorobenzone (l.S.) 114 100 100 100 100 100 100 100 100 100 100
3 d4-1.2-Dlchloroethane (Alt. is.: 85 97 96 95 97 98 97 101 98 98 96
4 d8-Totuone (Sun-.) 98 100 102 100 103 103 99 101 99 101 99
5 Brümotluorobenzene (Surr.) 174 100 100 0 0 106 96 99 97 98 93
6 d5-Chlorobenzene (Surr.) 117 100 102 104 105 106 101 103 103 104 101
7 Dlethyl other 74 21 20 91 117 98 120 116 117 85 112
8 AcroleIn 56 107 41 78 111 90 101 99 99 78 89
9 1,1-Dlchloroethono 61 107 98 101 118 108 125 122 117 98 116
10 Acetone 58 109 79 81 98 83 105 108 98 87 94
11 Methylono ChlorIde 84 122 97 82 108 89 109 108 105 85 99
12 Acrylonltrilo 53 127 83 83 102 88 97 105 97 86 92
13 t.1.2-Dlchloroethono 61 126 99 90 118 96 121 121 116 95 110
14 1,1-Dlchioroethano 63 120 116 87 110 92 115 116 112 89 107
15 Methyl ethyl ketono (MEK) 72 101 78 79 100 84 104 104 101 83 94
16 Chloroform 85 102 99 88 99 96 100 100 99 84 92
17 1,1 ,1-Trichloroethane 97 101 96 103 109 111 109 108 106 104 100
,L18 Carbon Tolrachioride 117 103 101 101 108 110 108 108 106 103 96
t i9 Denzone 78 104 102 128 100 132 102 104 100 114 94
20 1 ,2-Dichloroothano 62 101 98 98 97 103 101 102 98 100 93
21 Tr!chloroethene gç 100 98 97 96 101 100 100 98 99 92
22 1,2-Dichloropropane 63 100 98 96 96 101 99 101 98 100 91
23 p -Dloxane 8$ 477 196 30 65 4 51 85 93 59 53
24 Dromodichloromethane 83 99 97 95 100 101 98 100 97 98 91
25 Toluone 92 103 101 107 100 109 104 103 101 112 95
26 t.1,3-Dichloropropeno 75 98 96 97 100 104 96 97 95 95 86
27 1,1,2-Trichloroetheno 83 100 98 99 100 105 101 102 99 100 91
28 Tetrachloroetheno (PERC) 184 105 101 98 100 103 102 100 99 99 91
29 Dibromochioromethane 129 100 97 94 98 104 96 97 98 95 86
30 Chlorobonzeno(MCB) 112 105 102 103 103 108 104 103 103 103 94
31 Ethylbenzene 106 102 100 101 100 107 98 100 98 100 90
32 Bromoform 173 101 97 94 99 107 91 98 91 90 80
33 1 ,1 ,2,2.Totrachloroothane 83 106 102 0 0 111 98 102 100 100 89
34 Benzeno (m/z 51) 51 78 77 110 68 73 105 108 106 108 103
35 Benzono (mfz 79) 79 87 86 162 100 162 99 103 99 195 91
38 Totuene (m/z 65) 65 103 101 107 99 107 105 108 102 114 98
a. Actual amt. — 5x nominal amt.
b. VEIl — Daily Initial verification std.
FIN — Daily final std.
BLK — Blank
-------
Standards Analysis Summary - HannIbal 8912-3115
Percent Recovery
Quan Filiname G12YQ5 G13Y02 G13YOD 016YQ2 GI6YQS Avg
ton Ai 4 (nUp 100 100 100 200 200 Recovery
No. Compound (mit) Typ. f FIN VEIl FIN VEIl FIN
I dS•Benzena (Alt. LS.) 84 108 102 107 97 98 102
2 1,4 -Ditluoroberixane (P.S.) 114 100 100 100 100 100 100
3 d4-1,2-Dichloroethano (Alt. I.S. 65 96 97 95 101 103 97
4 dO-Toluene (Sun.) 98 115 99 93 99 100 101
5 Bromolluorobenzan (Surr.) 174 125 92 135 101 100 93
8 d5-Chlorobonzeno (Surr.) 117 122 100 128 103 102 103
7 Dfethyl ether 74 125 127 103 21 22 98
8 Acrolein 58 86 105 75 73 65 85
9 1.1-Dichloroetheno 61 134 131 113 101 108 122
10 Acetone 58 83 109 70 116 97 96
11 Methyleno Chloride 84 115 116 104 109 103 106
12 Acrylonitrllo 53 105 102 105 119 92 102
13 t-1.2-Dichlorootheno 61 121 125 118 120 108 108
14 1,1-Dlchloroothano 83 117 121 116 117 109 109
15 Methyl ethyl ketone (MEK) 72 101 105 101 99 85 97
• IS Chloroform 85 99 104 96 103 105 101
17 11,1-Trichioroothane 97 111 113 102 103 105 109
10 Carbon Tetrachloride 117 106 111 104 102 105 108
19 Donzene 78 120 106 144 101 105 114
20 1.2-Dlchtoroethane 62 97 104 95 104 106 105
21 Trichloroothono 95 108 103 91 100 102 101
22 1,2-Dichloropropane 83 108 105 85 97 100 102
23 p-Dloxane 88 1 49 0 921 465 244
24 Dromodichloromathane 83 107 104 79 103 103 102
25 Toluone 92 124 108 110 102 105 108
26 t-1 ,3-Oichloropropeno 75 109 98 107 101 102 103
27 l,1 ,2-Trlchloroethano 83 115 106 115 100 101 103
28 Tetrechtoroothano (PERC) 184 119 106 119 103 104 104
29 Dibromochforomethano 129 109 99 109 103 102 102
30 Chlorobenzene (MCD) 112 124 107 127 104 106 108
31 Ethylberizono 108 120 102 127 99 103 105
32 Bromoform 173 102 94 115 105 101 101
33 I.1,2,2-Tetrachioroethane 83 131 101 135 104 102 93
34 Benzeno(mfz5l) 51 108 107 113 75 77 91
35 Benzone (mix 79) 79 143 103 188 88 84 135
36 Toluene (mI x 65) 65 117 110 100 100 106 107
a. Actual amt. — Sx nominal ami.
b. VER — Daily Initial verification aid.
FIN — Daily final sid.
81K — Blank
-------
VOST Sample Analysäs Summary - Hannibai 8912-3115
_____________ __________RUN I (total ng ) _____________ _____________
Quan Pair 2 Pair 3 Pair 4 Field Blank Trip Blank
Ion Tenax TIC Tenax TIC Tenax T/C Tenax TIC Tenax TiC
No. Compound (m/z) 1082 1083 1084 1085 1086 1087 1090 1091 1092 1093
1 d6-Benzene (Alt. IS) 84 52 103 46 100 53 96 106 107 105 104
2 1 ,4-Dllluorobenzene (iS) 114 100 100 100 100 100 100 100 100 100 100
3 d4-1,2-Dlchloroetharie (All IS 65 36 106 34 110 34 95 106 106 103 104
4 d8-Toluene (Sun.) 98 103 106 98 104 106 102 105 104 102 105
5 Bromofluorobenzene (Sum.) 174 99 111 101 111 102 98 113 108 94 108
6 d5.ChIorober zene (Surr.) 117 97 112 95 110 97 103 110 108 104 111
7 Dlethyl ether 74 0 0 0 0 0 0 0 0 0 0
8 AcroleIn 56 1595 536 621 510 469 773 0 0 0 0
9 1 1-Dichloroethene 61 0 0 0 0 0 0 0 0 0 0
10 Acetone (b) 58 1378 442 1556 391 1545 593 55 0 22 0
11 Methytene Chloride 84 41 61 1799 26 45 25 27 0 3 0
12 Acrylonitrlle (b) 53 2417 449 1843 294 2048 419 0 0 0 0
13 t-1.2•Duchloroethene 61 0 0 1 0 0 0 0 0 0 0
14 1,1-Dlchloroethane 63 0 0 6 0 0 0 0 0 0 0
1 5 Methyl ethyl ketone (MEK) 72 644 29 0 25 456 46 1 5 1 0 7 1 0
16 Chloroform 85 72 0 75 0 62 41 0 0 0 0
17 1,1,1.Tnlchloroethane 97 118 19 74 2 5 0 0 0 0 0
1 8 Carbon Tetrachlonde 11 7 5 0 8 0 0 0 0 0 0 0
19 Benzene (b) 78 3859 188 4982 103 4832 140 80 40 22 10
20 1,2-Dlchioroethane 62 0 4 90 0 0 4 0 0 0 1
21 Tnichloroethene 95 14 0 71 0 13 1 0 0 0 0
22 1,2-Dlchloropropane 63 0 0 11 0 0 1 0 0 0 0
23 p-dloxane 88 32 91 233 36 131 220 70 22 0 54
24 Bromodichloromethane 83 43 9 38 0 40 1 2 0 0 0 0
25 Toluena (b) 92 1423 58 1552 13 1345 9 36 4 13 7
26 t-1,3-Dlchloropropeno 75 2 0 5 0 0 0 0 0 0 0
27 1,1,2-Tnichloroethane 83 96 3 0 0 0 0 0 0 0 0
28 TeU-achloroethene (PERC) 164 3 0 46 0 2 0 0 0 0 0
29 Dibromochloromethane 129 1 0 0 7 0 0 0 0 0 0 0
30 Chlorobenzene (MCB) 112 300 0 317 0 309 3 0 0 0 0
31 Ethylbenzenie (b) 106 262 4 230 2 215 2 0 0 0 0
32 Bromoform 173 7 0 5 0 5 13 0 0 0 0
33 1 ,1,2,2.Tetrachloroethane 83 144 0 127 0 0 15 0 0 0 0
a. Amounts calculated usIng 1 ,4-Dltluorobenzene as Internal standard.
Values for surrogates and alternate Internal standards are percent recoveries.
b. Alternate quantitatlon Ion may have been used In determining amiunt.
Acetone: 0-2000 ng m/z 58 ; >2000 ng m/z 42
Acrylonltrile: 0-2000 ng mlz 53; >2000 ng m z 51
Benzene: 0-1000 m/z 78; 1000-2200 ng mtz 79; > 2200 ng rn/z 74
‘roluene: 0-1000 ng infz 92; 1000-2000 ng mhz 65; >2000 19 mn?z 90
Ethylbenzene: 0-1000 D rrdz 106; >1000 ng m/z 92
B-129
-------
VOST Sample Analysis Summary - Hannibal 8912-3115
_____________ RUN 2 (total ng ) _____________
Quan Pair 1 Pair 2 Pair 3 Field Blank
Ion Tenax TIC Tenax TFC Tenax TIC Tenax TIC
p.io. Compound (mIZ) 2080 2081 2082 2083 2084 2085 2090 2091
1 d6-Benzene (Alt. IS) 84 125 103 0 101 0 104 104 103
2 1 ,4-DifluorobeflZefle (IS) 114 100 100 100 100 100 100 100 100
3 d4.1,2-D lchloroethane (Alt. IS 65 10 97 12 105 8 108 115 113
4 d8-Toluene (Surr.) 98 95 103 88 104 92 106 105 104
5 Bromofluorobenzene (Surr.) 1 74 98 1 08 1 00 110 87 111 89 105
6 d5.Chlorobenzene (Surr.) 117 96 105 97 108 90 110 105 108
7 Diethyl ether 74 0 0 0 0 0 0 0 0
8 Acrolein 56 0 1621 0 772 0 4164 0 0
9 1 ,1-Dichloroethene 61 21 0 26 0 17 0 0 0
10 Acetone (b) 58 3216 887 3306 1053 3225 2079 28 5
11 Methylene Chloride 84 208 105 466 10 6306 51 39 0
12 Acrylonltrile (b) 53 2791 842 2204 1407 2777 1198 0 0
1 3 t-1 ,2-Dichloroethene 61 0 0 2 0 1 0 0 0
14 1.1-Dichloroethane 63 0 0 42 0 29 0 0 0
1 5 Methyl ethyl ketone (MEK) 72 858 479 834 0 748 0 0 6
16 Chloroform 85 61 0 38 0 41 0 0 0
17 1,1,1-Trichloroethane 97 134 257 0 0 0 0 0 0
1 8 Carbon Tetrachloride 117 0 46 0 0 18 0 0 0
19 Benzene (b) 78 14756 166 18572 70 14900 81 28 13
20 1,2-Dichloroethane 62 0 5 429 0 0 0 0 0
21 Trichloroethene 95 18 0 23 0 22 0 0 0
22 1,2-Dichloropropane 63 26 1 33 0 22 0 0 0
23 p-dioxane 88 0 0 0 0 0 0 2 11 5
24 Bromodichloromethane 83 0 10 37 9 0 12 0 0
25 Toluene (b) 92 4471 77 6186 7 4901 5 4 1
26 t.1,3-Dichloropropene 75 47 0 64 0 45 0 0 0
27 1,1,2-Trichloroethane 83 204 15 191 25 193 12 0 0
28 Tetrachloroethene (PERC) 164 5 0 3 0 1 0 0 0 0
29 Dibromochloromethane 129 4 0 4 0 3 0 0 0
30 Chlorobenzane (MCB) 112 392 2 509 0 455 0 0 0
31 Ethylbenzene (b) 106 1413 5 1682 0 1414 0 0 0
32 Bromolorm 173 2 0 1 0 1 0 0 0
33 1,1,2,2-Tetrachloroethane 83 159 0 166 0 160 0 0 0
a Amounts calculated using I .4-Difluoro
Values for surrogates and alternate lr
b. Alternate quantitation Ion may have bi n / /
Acetone: 0-2000 ng m/z 58 ; >2000 A 1 ); 2/?k2 ‘ _ / -
Acrylonitiile: 0-2000 ng mlz 53; : “ ‘ - I
Benzene: 0-1000 — m/z 78; 1000-22
Toluene: 0-1000 ng mlz 92: 1000
Ethylbenzone: 0-1000 — m/z 106; >
B-130
-------
VOST Sample Analysis Summary Hannibal 8912-3115
___________ RUN 3 j I Tm ) ___________
Quwi Pair 1 Pair 2 Pair 3 Field Blank
Ion Tenax TIC Tenax T/C Tenax TIC Tenax T/C
No. Compound (mIZ) 3060 3081 3082 3084 3085 3090 3091
1 d6-Benzene (Alt. IS) 84 0 105 0 103 0 101 101 109
2 1,4.Dlf luorobenzone (IS) 114 100 100 100 100 100 100 100 100
3 d4.1,2-Dichloroethane (Alt. IS 65 16 102 18 97 40 96 121 124
4 d8-Toluene (Surr.) 98 100 99 100 103 80 102 102 106
5 Bromofluorobenzene (Surr.) 174 95 101 89 102 0 104 110 99
6 d5-Chlorobenzene (Surr.) 117 96 102 92 105 133 106 107 111
7 Duethyl ether 74 0 0 0 0 0 0 0 0
8 Acroleln 56 0 0 0 962 0 1532 0 0
9 1,1.Dlchloroethene 61 0 0 17 0 0 0 0 0
10 Acetone (b) 58 6340 0 4770 890 0 1707 68 4
11 Methylene Chloride 84 173 0 123 32 0 18 0 0
12 Acrylonitrlle (b) 53 6570 432 5726 422 1924 737 0 3
13 t-1,2-Dlchloroethene 61 0 3 0 0 0 0 0 0
14 1,1-Dichloroethane 63 0 0 0 0 0 0 0 0
1 5 Methyl ethyl ketone (MEK) 72 1562 0 1485 0 1447 0 0 0
16 Chloroform 85 17 0 32 0 25 0 0 0
17 1,1,1-Trichloroethane 97 0 57 0 3 0 0 0 0
1 8 Carbon Tetrachloride 11 7 0 0 0 0 0 0 0 0
19 Benzene (b) 78 29586 39 26088 53 24163 45 19 9
20 1,2-Dichloroethane 62 595 0 0 0 476 0 0 0
21 Trschloroethene 95 25 0 20 2 14 0 0 0
22 1,2-Dichloropropane 63 32 0 25 2 0 0 0 0
23 p-dioxane 88 0 0 0 0 0 0 0 0
24 Bromodlchloromethafle 83 31 0 29 8 0 0 0 0
25 Toluene (b) 92 10828 32 7814 25 7207 8 1 1
26 1-1,3-Dichloropropene 75 40 1 100 1 24 0 0 0
27 1,1,2.Trichloroetharie 83 197 3 0 6 24 0 0 0
28 Te ’achIoroethene (PERC) 1 64 42 0 40 2 46 0 0 0
29 Dibromochloromethafle 129 3 0 4 4 5 0 0 0
30 Chlorobenzene (MCB) 112 635 0 529 6 604 0 0 0
31 Ethylbenzene (b) 106 2233 1 1499 5 1755 0 0 0
32 Bromoform 173 2 0 2 11 0 0 0 0
33 1.1,2,2-Tetrachloroethane 83 165 0 158 27 0 0 0 0
a. Amounts calculated using I ,4-Dtfluoro
Values for surrogates and alternate lr
b. Alternate quantitation Ion may have b€
Acetone: 0-2000 ng - m/z 58 ; >2000
Acrylonitrlle: 0-2000 ng — rn/i 53;
Benzene: 0-1000 — nVz 78; 1000-22
Toluene: 0-1000 ng — mfz 92; 1000
Ethylbenzene: 0-1000 — m/z 106; >
B—131
-------
VOST Sample Anaiysis Summary Hannibai 8912-3115
____________ RUN 4 (total ng ) _____________ _____________
Quw Pair 1 Pair 2 Pair 3 Field Blank Trip Blank
Ion Tenax TIC Tenax T/C Tenax TIC Tenax TIC Tenax T/C
No Compound (mhz) 4080 4081 4082 4083 4084 4085 4090 4091 4092 4093
1 d6-Benzene (Alt. IS) 84 0 99 0 97 0 98 102 102 102 103
2 1,4-Dllluorobenzene (IS) 114 100 100 100 100 100 100 100 100 100 100
3 d4.1,2-Dichloroethane (Alt IS 65 17 96 32 96 12 97 96 96 97 96
4 dB-Toluene (Surr.) 98 101 100 101 101 100 101 101 100 100 101
5 Bromotluorobenzeno (Surr.) 174 89 103 96 102 99 98 98 98 99 91
6 d5.Chlorobenzene (Sun.) 117 94 104 97 105 98 103 103 102 103 103
7 Diethyl ether 74 0 0 0 0 0 0 0 0 0 0
8 Acrolein 56 0 869 0 1190 0 1686 0 0 0 0
9 1,1-Dichloroethene 61 0 0 0 1 3 0 0 0 0 0
10 Acetone (b) 58 3348 201 3211 266 3218 752 55 0 49 0
11 Methylene Chloride 84 77 17 74 14 86 25 9 0 17 0
12 Acrylonitrlle (b) 53 5600 570 4952 551 5442 592 0 0 0 0
13 t.1,2-Dichloroethene 61 3 0 3 0 2 0 0 0 0 0
14 1,1-Dichloroethane 63 20 0 16 0 20 0 0 0 0 0
15 Methyl ethyl ketone (MEK) 72 1056 0 985 0 985 0 9 0 0 8
16 Chlorotorm 85 52 0 64 0 60 0 0 0 0 0
17 1,1,1-Trichloroethane 97 8 12 0 0 0 0 0 0 0 0
1 8 Carbon Tetrachloride 11 7 0 0 0 0 0 0 0 0 0 0
19 Benzene (b) 78 13694 55 11757 48 14267 180 35 0 37 12
20 1,2-Dichloroethane 62 0 0 0 0 0 0 0 1 0 1
21 Trichloroethene 95 17 0 15 0 14 0 0 0 0 0
22 1,2-Dichloropropane 63 17 0 15 0 16 0 0 0 0 0
23 p-dioxane 88 1 6 0 0 0 0 0 2 105 5 11
24 Bromodichloromethafle 83 28 4 25 6 0 5 0 0 0 0
25 Toluene (b) 92 5008 18 2902 6 4905 8 6 4 6 4
26 t-1,3.Dlchloropropene 75 63 0 55 0 63 0 0 0 0 0
27 1,1 .2-Trichloroethane 83 0 0 0 0 0 0 0 0 0 0
28 TeUachloroethene (PERC) 164 23 0 22 0 21 1 0 0 0 0
29 Dibromochloromethafle 129 1 0 0 0 0 0 0 0 0 0
30 Chlorobanzeno (MCB) 112 427 0 368 0 401 0 0 0 0 0
31 Ethylbenzene (b) 106 756 2 591 0 781 2 0 0 0 0
32Bromolorm 173 0 0 0 0 0 0 0 0 0 0
33 1.1.2,2-Tetrachloroethafle 83 138 0 128 0 126 0 0 0 0 0
a Amounts calculated using 1,4-Dilluoro
Values br surrogates and alternate Ir
b. Alternate quantitatlon Ion may have bs
Acetone: 0-2000 ng mhz 58 ;>2000
Acrylonitnle: 0-2000 ng — mIz 53;
Benzene: 0-1000 — m/z 78; 1000-22
Toluene: 0-1000 rig — mfz 92; 1000
Ethylberizene: 0-1000 — mhz 106; >
B-132
-------
yOST Sample Analysis Summary - Hannibal 8912-3115
RUN 5 (total ni _ _____________
Quan Pair 2 Pair 3 Pair 4
Ion Tenax TIC Tenax TIC Tenax TIC
, .comoound (mlz) 5082 5083 5084 5086 5087
1 d6-Benzefle (Alt. IS) 84 0 102 0 102 0 101
2 1,4_DIlluorObeflZefle (IS) 114 100 100 100 100 100 100
3 d4.1.2 Dlchloroethafle (Alt. IS 65 15 96 9 96 14 96
4 d8-Toluone (Surf.) 98 95 102 95 101 92 101
5 Bromofluorob eflZefle (Surr.) 174 97 103 85 103 90 103
6 d5-Chlorobeflzefle (Sun.) 117 99 106 92 104 92 105
7 Diethyl other 74 0 0 0 0 0 0
8 Acrololn 56 0 6818 0 5632 0 7326
9 1,1.Dichloroethefle 61 0 0 0 0 0 2
10 Acetone (b) 58 6274 1552 4341 2526 6370 4601
11 Methyfene ChlorIde 84 132 106 0 53 0 71
12 Acrylonltnile (b) 53 363 1022 2848 1096 3370 1393
13 t.1,2 -DlchiOrOethefle 61 0 0 3 0 0 0
14 i,1.Dachloroethane 63 0 0 28 0 0 0
15 Methyl ethyl Icetone (MEK) 72 0 0 1535 0 2021 0
16 Chloroform 85 80 0 106 0 199 0
1 7 1,1,1 -Trichloroethane 97 0 0 0 0 0 0
1 8 Carbon Tetrachlorlde 11 7 0 0 0 0 0 0
19 Benzene (b) 78 21477 38 15750 52 19729 52
20 1,2-Dichloroethane 62 0 2 0 0 0 0
21 Trschloroelhene 95 30 0 26 0 41 0
22 1,2-Dlchloropropane 63 24 0 18 0 24 1
23 p.dioxane 88 0 0 0 213 0 0
24 Bromodichloromethafle 83 0 7 85 7 0 7
25 Toluene (b) 92 10355 23 6959 6 8040 7
26 t.1.3.Dlchloropropene 75 128 0 87 0 99 0
27 1,1,2-Trlchloroethane 83 0 7 0 16 14 19
28 Tetrachloroothene (PERC) 1 64 3 0 3 0 5 0
29 Dlbnomochloromethane 129 0 0 0 0 1 0
30 Chlorobenzene (MCB) 112 301 0 266 0 303 0
31 Ethylbenzene (b) 106 2096 2 1464 0 1774 0
32 Bromoform 173 0 0 0 0 0 0
33 1.1,2,2.Tetrachloroethafl o 83 125 0 119 1 127 0
a Amounts calculated using 1,4-Difluoro
Values br surrogates and alternate Ir
b. Alternate quantitation Ion may have bE
Acetone: 0.2000 ng - m/z 58 >2000
Acrylonltrile: 0-2000 ng rnlz 53;
Benzene: 0-1000 = m z 78; 1000-22
Toluene: 0-1000 ag s mu 92; 1000
Ethylbenzene: 0-1000 — mlz 106; >
B—133
-------
VOST Sample Analysis Summary - Hannibal 8912-3115
___________ RUN 5, cont. (total ng ) ___________
Quw Field Blank Trip Blank Pr3 Field Bik Pr4 Field Bik
Ion Tenax TIC Tenax T/C Tenax TIC Tenax T/C
No. Compound (m/z) 5090 5091 5092 5093 5094 5095 5096 5097
1 d6-Benzene (Alt. IS) 84 103 103 101 103 103 102 103 104
2 1 ,4-D lfluorobenzene (IS) 114 100 100 100 100 100 100 100 100
3 d4-1 ,2-Dlchloroethane (Alt. IS 65 98 99 97 98 98 99 99 99
4 d8-Tolusne (Sun.) 98 101 100 98 99 100 101 100 100
5 Bromolluorobenzene (Surr.) 174 94 100 100 99 97 95 98 101
6 d5-Chlorobenzene (Surr.) 117 103 104 103 102 103 103 103 104
7 Diethyl ether 74 0 0 0 0 0 0 0 0
8 Acrolelri 56 0 0 0 0 0 0 0 0
9 1,1-Dichloroethene 61 0 0 0 0 0 0 0 0
1 0 Acetone (b) 58 26 0 1 6 0 18 0 31 0
11 Methylene Chloride 84 8 3 6 0 0 0 41 0
1 2 Acrylonltrile (b) 53 0 0 0 0 0 0 0 0
13 t-1,2-Dichloroethene 61 0 0 0 0 0 0 0 0
14 1,1-Dichloroethane 63 0 0 0 0 0 0 0 0
1 5 Methyl ethyl ketone (MEK) 72 1 0 0 11 0 0 0 0 1 0
1 6 Chloroform 85 0 0 0 0 0 0 0 0
17 1,1,1-Trlchloreethane 97 0 0 0 0 0 0 0 0
1 8 Carbon Tetrachloride 11 7 0 0 0 0 0 0 0 0
19 Benzene (b) 78 31 26 20 8 19 16 47 17
20 1,2-Dichloroethane 62 0 0 0 0 0 0 2 0
21 Trlchloroethone 95 0 0 0 0 0 0 0 0
22 1 .2-Dichloropropane 63 0 0 0 0 0 0 0 0
23 p.dloxane 88 5 0 35 14 0 11 0 33
24 Bromodichloromethane 83 0 0 0 0 0 0 0 0
25 Toluene (b) 92 5 6 4 3 4 4 8 3
26 t-1,3-Dlchloropropene 75 0 0 0 0 0 0 0 0
27 1,1,2-Tnichloroethane 83 0 0 0 0 0 0 0 0
28 Tetrachloroethene (PERC) 1 64 0 0 0 0 0 0 0 0
29 Dlbromochlorometflane 129 0 0 0 0 0 0 0 0
30 Chlorobenzene (MCB) 11 2 0 0 0 0 0 0 0 0
31 Ethylbenzene (b) 106 0 0 0 0 0 0 0 0
32 Bromoform 173 0 0 0 0 0 0 0 0
33 1 ,1,2,2-Tetrachloroethane 83 0 0 0 0 0 0 0 0
a. Amounts calculated usIng 1 ,4-DUluoro
Values for surrogates and alternate Ir
b. Alternate quantltatlon Ion may have bE
Acetone: 0-2000 ng = m/z 58 ; >2000
Acrylonitiile: 0.2000 ng — m/z 53:
Benzene: 0-1000 — m/z 78; 1000-22
Toluene: 0-1000 ng — mIz 92: 1000
Ethylbenzene: 0-1000 — m/z 106; >
B-134
-------
VOST Sample Analysis Summary - Hannibal 8912-3115
____________ RUN 6 (total n ) _____________ Surrogate
Quan Pair 1 Pair 2 Pair 3 Field Blank Recovery
Ion Tenax T/C Tenax T/C Tenax TIC Tenax TIC Avg RSD
( mix) 6080 6081 6082 6083 6084 6085 6090 6091 ( ng) (% )
1 d6-Benzene (Alt. IS) 84 0 102 0 102 0 102 104 103 75 50
2 1 ,4.Difluorobenx efle (IS) 114 100 100 100 100 100 100 100 100 100 0
3 d4.1,2.Dichloroethane (Alt. IS 65 14 96 13 97 21 93 98 98 76 51
4 d8-Toluene (Surr.) 98 97 101 102 101 98 101 100 101 100 4
5 Bromofiuorobenzane (Surr.) 174 100 99 95 94 93 100 100 102 98 15
6 d5-Chlorobenzene (Sun.) 117 98 103 97 100 95 105 102 105 103 6
7 DIethyl ether 74 0 0 0 0 0 0 0 0
8 Acrolein 56 0 3967 0 5936 0 4928 0 0
9 1,1.Dlchloroethene 61 0 0 0 0 0 0 0 0
10 Acetone (b) 58 6793 954 6702 0 5108 2107 43 4
11 Methylene Chloride 84 0 33 0 36 0 39 21 4
1 2 Acryionhtrlle (b) 53 41 02 454 4009 809 4043 678 0 0
13 t-1,2-Dichloroethene 61 0 0 0 0 0 0 0 0
14 1,1-Dichloroethane 63 41 0 30 0 0 0 0 0
15 Methyl ethyl ketone (MEK) 72 1588 0 1526 0 1559 0 0 0
16 Chloroform 85 98 0 83 0 99 0 0 0
17 1,1,1 -Tnichloroethane 97 0 0 0 0 0 0 0 0
1 8 Carbon Tetrachloride 11 7 0 0 0 0 0 0 0 0
19 Benzene (b) 78 19649 56 18711 40 17619 42 90 30
20 1,2-Dichloroethane 62 0 0 0 0 0 2 0 0
21 Trichioroethene 95 26 0 31 0 27 0 0 0
22 1,2.Dichloropropane 63 23 0 25 0 23 0 0 0
23 p-dioxane 88 0 0 0 0 0 0 27 5
24 BromodichiorOmothane 83 0 6 0 6 0 4 0 0
25 Toluene (b) 92 9012 9 8189 5 7912 5 7 5
26 t-1,3.Dichloropropene 75 117 0 103 0 97 0 0 0
27 1,1.2.Trichloroethane 83 0 1 141 4 0 5 0 0
28 Te achIoroethene (PERC) 164 3 0 2 0 2 0 0 0
29 Dibromochioromethafle 129 0 0 0 0 0 0 0 0
30 Chlorobenzene (MCD) 112 305 0 278 0 272 0 0 0
31 Ethylbenzene (b) 106 1930 1 1760 0 1676 0 0 0
32 Bromolorm 173 0 0 0 0 0 0 0 0
33 1,1,2,2-Tetrachloroethane 83 132 0 126 0 118 0 0 0
a Amounts calculated using 1 .4-Dlfluoro
Values for surrogates and alternate Ir
b. Alternate quantitation Ion may have b€
Acetone: 0-2000 ng — mix 58 : >2000
Acrylonltnile: 0-2000 rig — m/x 53;
Benzene: 0-1000 — m/x 78; 1000-22
Toluene: 0-1000 rig — miz 92: 1000
Ethylbenzene: 0-1000 — mix 106; >
B-135
-------
VOST Condensate Sample Analysis Summary - Hannibal 8912-3115
Qimn Amount ( igfL H2O)
Ion GO3Y1 G03Y2 G03Y3 G03Y4 G03Y5 G1GY1 G16Y2
No. Compound (mlz) 1037 2037 3037 3055 4037 5037 6037
1 d6-Benzene (Alt. l.S.) 84 1 02 1 04 1 02 1 03 1 03 99 1 00
2 1,4-Difluorobenzene (l.S.) 114 100 100 100 100 100 100 100
3 d4-1,2-Dichloroethane (Alt. l.S.) 65 95 95 96 94 94 99 99
4 d8-Toluene (Surr.) 98 101 101 100 101 101 98 99
5 Bromofluorobenzene (Surr.) 174 98 99 98 100 100 99 100
6 d5-Chlorobenzene (Surr.) 117 1 03 1 02 1 02 1 03 1 03 1 03 103
7 Diethyl ether 74 0 0 0 0 0 0 0
8 Acrolein 56 0 23 45 0 0 30 117
9 1,1-Dichloroethene 61 0 0 0 0 0 0 0
10 Acetone 58 158 356 634 238 233 500 671
11 Methylene Chloride 84 0 97 1 289 2 1 0
12 Acrylonltrile 53 0 5 12 23 0 7 17
13 t .1,2-Dichloroethene 61 0 0 0 0 0 0 0
14 1,1-Dichloroethane 63 0 0 0 0 0 0 0
15 Methyl ethyl ketone (MEK) 72 0 0 0 0 0 0 0
16 Chloroform 85 0 0 0 0 0 0 0
17 1,1,1-Trichloroethane 97 62 0 0 0 0 0 0
1 8 Carbon Tetrachloride 117 11 0 0 0 0 0 D
l9Benzene 78 0 0 0 2 0 0 0
20 1,2-Dichloroethane 62 0 0 0 0 0 0 0
21 Trichloroethene 95 0 0 0 0 0 0 0
22 1,2-Dichloropropane 63 0 0 0 0 0 0 0
23 p-dioxane 88 0 0 0 0 0 0 0
24 Bromodichloromethane 83 0 0 0 0 0 0 0
25 Toluene 92 168 2 0 11 0 0 0
26 t-1,3-Dichloropropene 75 0 0 0 0 0 0 0
27 1,1,2-Trichloroethane 83 0 0 0 0 0 0 0
28 Tetrachloroothene (PERC) 1 64 0 0 0 0 0 0 0
29 Dibromochloromothane 129 0 0 0 0 0 0 0
30 Chlorobenzene (MCB) 112 0 0 0 0 0 0 0
31 Ethylbenzene 1 06 0 0 0 0 0 0 0
32 Bromoform 173 0 0 0 0 0 0 0
33 1,1,2,2-Tetrachloroethane 83 0 0 0 0 0 0 0
a Amounts calculated using 1,4-Difluoroberizene as internal standard.
Values for surrogates and alternate internal standards are percent recoveries.
B-136
-------
VOST ANALYSIS RESULTS - RUN 1
Pair No
1
Pair No.
2
Pair No.
3
Field
Blank
Trip Blank
Avg Conc.
(ng/L or
Analyte
Emission
T
TIC
I
TIC
I
T/C
T
T/C
I
TIC
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
ug/dscm)
(mg/mm)
1082
1083
1084
1085
1086
1087
1090
1091
1092
1093
Gas Sample Volume (L) = 9.13 9.19 9 50
Diethyl ether
Acrolemn 1595 536 621 510 469 773 161.92 438 80
1 ,1 —Dichloroethene
Acetone (b) 1378 442 1556 391 1545 593 55 22 212.23 575.15
Methylene Chloride 41 61 1799 26 45 25 27 3 71.74 194 41
Acrylonitrile (b) 2417 449 1843 294 2048 419 268.47 727.56
t—1 ,2—Dichloroethene 1 0.04 0 11
1,1—Dichloroethane 6 0.22 060
Methyl ethyl ketone (MEK) 644 29 25 456 46 15 10 7 10 43.11 11683
Chloroform 72 75 62 41 8.97 24.30
1,1,1—Trichloroethane 118 19 74 2 5 7.80 21.13
Carbon Tetrachloride 5 8 0.49 1.32
Benzene (b) 3859 188 4982 103 4832 140 80 40 22 10 506.98 1373.92
1,2—Dictiloroethane 4 90 4 1 3.52 9.53
Trichloroethene 14 71 13 1 3.56 9.65
1,2—Dichloropropane 11 1 0.46 1.24
p—dioxane 32 91 233 36 131 220 70 22 54 26.71 72.39
Bromodichloromethane 43 9 38 40 12 5.10 13.81
Toluene (b) 1423 58 1552 13 1345 9 36 4 13 7 158.16 428.62
t—1 ,3—Dichloropropene 2 5 0.26 0.69
1,1,2—Trichloroethane 96 3 3.53 9.56
Tetrachioroethene (PERC) 3 46 2 1.82 4.92
Dibromochloromethane 10 7 0.63 1.70
Chlorobenzene (MCB) 300 317 309 3 33 39 90 48
Ethylbenzene (b) 262 4 230 2 215 2 25.70 69 64
Bromoform 7 5 5 13 1.08 292
1,1,2,2—Tetrachloroethane 144 127 15 1026 27.81
File VOST2 By PSM Date. 10\22\90
-------
VOST ANALYSIS RESULTS - RUN 2
Pair No
1
Pair
No.
2
Pair No.
3
Field
Blank
Avg Conc
(ng/L or
Analyte
Emission
T
TIC
T
TIC
T
T/C
I
T/C
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
ug/dscm)
(mg/mm)
2080
2081
2082
2083
2084
2085
2090
2091
Gas Sample Volume (L) = 9 29 8 92 8.93
Diethyl ether
Acrolein 1621 772 4164 241.60 70304
1,1—Dichloroethene 21 26 17 236 6.86
Acetone (b) 3216 887 3306 1053 3225 2079 28 5 507.23 1476 05
Methylene Chloride 208 105 466 10 6306 51 39 263.30 766.21
Acrylonitrile (b) 2791 842 2204 1407 2777 1198 413.39 1202.96
t—1,2—Dichloroethene 2 1 0.11 0.31
1,1—Dichloroethane 42 29 2.63 7.66
Methyl ethyl ketone (MEK) 858 479 834 748 6 107 55 312 96
Chloroform 61 38 41 5.17 15.04
1,1,1—Trich loroethane 134 257 14.40 41.91
Carbon Tetrachloride 46 18 2.34 6.80
Benzene (b) 14756 166 18572 70 14900 81 28 13 1788.68 5205.06
1,2—Dichloroethane 5 429 15.99 46.52
Trichloroethene 18 23 22 2.31 6.72
1 ,2—Dichloropropane 26 1 33 22 3.01 8.76
p—dioxane 2 115
Bromodichloromethane 10 37 9 12 2.48 7.22
Toluene (b) 4471 77 6186 7 4901 5 4 1 576.53 1677.71
t—1.3—Dichloropropene 47 64 45 5.74 16.69
11,2—Trichloroethane 204 15 191 25 193 12 23.54 6850
Tetrachloroethene (PERC) 5 3 10 067 1.95
Dibromochtoromethane 4 4 3 0.42 1 22
Chlorobenzene (MCB) 392 2 509 455 50.01 145 54
Ethylbenzene (b) 1413 5 1682 1414 166.32 483 99
Bromoform 2 1 1 0.15 043
11,2,2—Tetrachloroethane 159 166 160 1787 5200
File VOST2 By PSM Date 10\22\90
-------
VOST ANALYSIS RESULTS - RUN 3
Pair No.
1
Pair No.
2
Pair No.
3
Field
Blank
Avg Conc.
(ngIL or
Analyte
Emission
I
TIC
T
TIC
T
TIC
T
TIC
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
ugldscm)
(mg/mm)
3080
3081
3082
3083
3084
3085
3090
3091
Gas Sample Volume (L) = 9 87 9.86 8.86
Diethyl ether
Acrolein 962 1 532 87.24 261 72
1 ,1 —Dichloroethene 17 0.59 1.77
Acetone (b) 6340 4770 890 1707 68 4 479.43 1438.29
Methylene Chloride 173 123 32 18 12.09 36.26
Acrylonitrile (b) 6570 432 5726 422 1924 737 3 553.01 1659.03
t—1,2—Dichloroethene 3 0.11 034
1 1 —Dichloroethane
Methyl ethyl ketone (MEK) 1562 1485 1447 157 16 471.47
Chloroform 17 32 25 2.59 7.76
1,1,1—Trichloroethane 57 3 2.09 6.27
Carbon Tetrachloride
Benzene (b) 29586 39 26088 53 24163 45 19 9 2797.26 8391.79
1 2—Dichloroethane 595 476 37.47 112.42
Trichloroethene 25 20 2 14 2.11 6.34
1,2—Dichloropropane 32 25 2 2.06 6.19
p—dioxane
Bromodichloromethane 31 29 8 2.40 7.19
Toluene (b) 10828 32 7814 25 7207 8 1 1 906.41 2719.23
t—13—Dichloropropene 40 1 100 1 24 5.80 17.40
1,1 ,2—Trichloroethane 197 3 8 24 8 09 24.26
Tetrachioroethene (PERC) 42 40 2 46 4 54 13 62
Dibromochloromethane 3 4 4 5 056 1.67
Chlorobenzene (MCB) 635 529 6 604 62.00 18600
Ethylbenzene (b) 2233 1 1499 5 1755 192.12 576 35
Bromoform 2 2 11 0 50 1 51
11,2,2—Tetrachloroethane 165 158 27 12.24 36.71
File. VOST2 By PSM DateS 10\22\90
-------
VOST ANALYSIS RESULTS - RUN 4
Pair No
1
Pair No
2
Pair No
3
Field
Blank
Trip Blank
Avg. Conc.
(ngIL or
Analyte
Emission
T
TIC
T
TIC
T
TIC
I
T/C
T
TIC
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
ugldscm)
(mg/mm)
4080
4081
4082
4083
4084
4085
4090
4091
4092
4093
Gas Sample Volume (L) = 9.60 9.47 9 36
Diethyl ether
Acrolein 869 1190 1686 131.71 45915
1,1—Dmchloroethene 1 3 0.13 0.44
Acetone (b) 3348 201 3211 266 3218 752 55 49 38672 1348.11
MethyleneChioride 77 17 74 14 86 25 9 17 1030 35.89
Acrylonitrile (b) 5600 570 4952 551 5442 592 622.82 2171.14
t—1,2—Dichloroethene 3 3 2 0.30 1.05
1 ,1 —Dichloroethane 20 16 20 1.98 6 92
Methyl ethyl ketone (MEK) 1056 985 985 9 8 106.45 371 .09
Chloroform 52 64 60 6.17 21 51
1,1,1—Trmchloroethane 8 12 0.72 2.51
w Carbon Tetrachioride
Benzene (b) 13694 55 11757 48 14267 180 35 37 12 1406.95 4904.62
1 ,2—Dichloroethane 1 1
Trichloroethene 17 15 14 1.59 5.53
1 2—Dichloropropane 17 15 16 1.69 590
p—dioxane 16 2 105 5 11 0.58 2.01
Bromodichloromethane 28 4 25 6 5 2.34 8 17
Toluene (b) 5008 18 2902 6 4905 8 6 4 6 4 451.89 1575.30
t—1 ,3—Dmchloropropene 63 55 63 6 39 22.27
1 ,1 ,2—Trichloroethane
Tetrachioroethene (PERC) 23 22 21 1 2.32 8.09
Dibromochloromethane 1 0.05 0.17
Chlorobenzene (MCB) 427 368 401 42 03 146 51
Ethylbenzene (b) 756 2 591 781 2 7496 261.30
Bromoform
1 ,1,2,2—Tetrachtoroethane 138 128 126 13.77 47.99
File VOST2 By PSM Date. 10\22\90
-------
VOST ANALYSIS RESULTS - RUN 5
Pair No.
2
Pair
No.
3
Pair No.
4
Field Blank
Trip Blank
Avg. Conc.
(ng/L or
Analyte
Emission
T
TIC
T
TIC
I
T/C
T
T/C
I
T/C
(ng)
(ng)
(ng)
(ng)
(ng)
(rig)
(ng)
(ng)
(ng)
(ng)
ug/dscm)
(mg/mm)
5082
5083
5084
5085
5086
5087
5090
5091
5092
5093
Gas Sample Volume (L) = 8 81 8.98 8.86
0 methyl ether
Acrolein 6818 5832 7326 749.56 2361.11
1,1—Dichloroethene 2 0.06 0.19
Acetone (b) 6274 1552 4341 2526 6370 4601 26 16 963.00 3033.46
Methylene Chloride 132 106 53 71 8 3 6 13.57 42.75
Acrylonitrile (b) 363 1022 2848 1096 3370 1393 378.68 1192.84
t—1,2—Dichloroethene 3 0.10 0.32
1 , 1 —Dichloroethane 28 1.04 3 27
Methyl ethyl ketone(MEK) 1535 2021 10 11 133.45 420.36
Chloroform 80 106 199 14.44 45.47
1,1 ,1—Trichloroethane
Carbon Tetrachloride
‘ - Benzene (b) 21477 38 15750 52 19729 52 31 26 20 8 2142.50 6748.87
1,2—Dichloroethane 2 0.06 0.19
Trichloroethene 30 26 41 3.65 11.49
1,2-Dictiloropropane 24 18 24 1 2.54 8.00
p-dioxane 213 5 35 14 7.99 25.16
Bromodichloromethane 7 85 7 7 4.01 12.62
Toluene (b) 10355 23 6959 6 8049 7 5 6 4 3 953.05 3002.11
t—1,3—Dich!oropropene 128 87 99 11.80 37.19
1,1,2—Trich loroethane 7 16 14 19 2.12 6.67
Tetrachioroethene (PERC) 3 3 5 0.42 1 34
Dibromochloromethane 1 0.03 0.11
Chlorobenzene (MCB) 301 266 303 32 61 102.73
Ethylbenzene (b) 2096 2 1464 1774 200.18 630.56
Bromoform
1,1,2,2—Tetrachloroethane 125 119 1 127 __________ __________ 14.00 44.09
Note Pair No 1 was not analyzed, due to possible contamination from a concrete curing procedure
occurring upwind of the sampling location
File VOST2 By PSM Date 10\22\90
-------
VOST ANALYSIS RESULTS - RUN 6
Pair No.
1
Pair
No
2
Pair No
3
Field
Blank
Avg Conc
(ngIL or
Analyte
Emission
T
TIC
I
TIC
T
TIC
I
T/C
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
(ng)
ug/dscm)
(mg/mm)
6080
6081
6082
6083
6084
6085
6090
6091
Gas Sample Volume (L) = 8.64 8 86 8.73
Diethyl ether
Acrolein 3967 5936 4928 565.42 1939.39
1,1 —Dmchloroethene
Acetone (b) 6793 954 6702 5108 2107 43 4 825.95 2833.01
Methylene Chloride 33 36 39 21 4 4 09 14.04
Acrylonitrile (b) 4102 454 4009 809 4043 678 537.33 1843.03
t—1 .2—Dichioroettiene
1,1—Dichloroethane 41 30 2.67 917
Methyl ethyl ketone (MEK) 1588 1526 1559 178.14 611.02
Chloroform 98 83 99 10 68 36.63
1,1 , 1 —Trichloroethane
Carbon Tetrachioride
Benzene (b) 19649 56 18711 40 17619 42 90 30 213938 7338.08
1 ,2—Dmchloroethane 2 0.06 0 20
Trichloroethene 26 31 27 3.19 10.96
1,2—Dichloropropane 23 25 23 2.70 9.25
p—dmoxane 27 5
Bromodichloromethane 6 6 4 0.61 2.09
Toluene (b) 9012 9 8189 5 7912 5 7 5 958.12 328634
t—1,3-Dichloropropene 117 103 97 12.07 41.41
1,1,2—Trmchloroethane 1 141 4 5 5.73 19.65
Tetrachioroethene (PERC) 3 2 2 0 25 0 86
Dmbromochloromethane
Chlorobenzene (MCB) 305 278 272 32.58 111 .74
Ethylbenzene (b) 1930 1 1760 1676 204.61 701.80
Bromoform
1,1,2,2—Tetrachloroethane 132 126 118 14.33 4917
File VOST2 By PSM Date 10\22 90
-------
APPENDIX B-7
SENIVOLATILE ORGAN ICS DATA
B-143
-------
Note: No significant problems were encountered with the Method 0010 trains.
All test runs fell within the acceptable range for isokinetic performance, and
all leak checks were passed.
B-145
-------
SUMMARY OF MM5 DATA
Stack
Run
Sample
time (mm)
Sample
vol. (dscm)
Isokinetic
(%)
02 (%)a
CO 2 (%)a
H 2 0(%)
flowrate
(dscm/min)
1
120
1.447
96.9
6.3
19.1
32.4
2700
2
120
1.682
104.9
3.9
23.3
37.7
2900
3
120
1.714
103.7
4.2
22.3
35.7
3000
4
120
1.805
94.3
4.1
22.7
31.5
3500
5
120
1.788
99.2
4.5
22.0
36.3
3200
6
120
1.969
100.3
4.8
21.9
36.3
3400
a Analysis by Orsat.
B-146
-------
FILE NAME — 9 IO2RUN1
RUN 4 - RUN 1
LOCATION - CONTINENTAL CEMENT STACK
DATE - 6—20—90
PROJECT - 9102—t:.—13
Initial Meter Volume (Cubic Feet)=
Final Meter Volume (Cubic Feet )=
Meter Factor=
Final Leak Rate (Cu ft/min)=
Net Meter Volume (Cubic Feet )=
Gas Volume (Dr ’ Standard Cubic Feet)=
Barometric Pressure (in Hg)=
Static Pressure (Inches H20)=
Percent O>ygen=
Percent Carbon Dioxide=
Moisture Collected (ml)=
Percent Jater=
Dry Molecular Weight=
L.Jet Molecular Lieight=
Average Square Root of Delta P (in H20)=
% Isokinetic=
Pitot Coefficient=
Sampling Time (Minutes)=
Nozzle Diameter (Inches)=
Stack Axis 4l (Inches)=
Stack Axis 1$2 (Inches)=
Circular Stack
Stack Area (Square Feet)=
Particulate Loading — Front Half
Particulate L.Jeight (g)=
Particulate Loading, Dry Std. (gr/scf)=
Particulate Loading, Actual (gr/cu ft)=
Emission Rate (lb/hr )=
No Back Half Analysis
.300
B68 .21
1 .096
0.003
54.710
51 .091
29.09
-0 .50
‘ •_)
‘ -F
19.1
520 . 1
32.4
31 .31
27.00
0.5028
96.9
0 .83
120.0
0.302
141.0
141.0
108 .43
0.0000
0.0000
0.0000
0.00
AveraQe
Meter
Temperature
(F)
91
Average
Delta
H (in H20)=
0.72
Average
Delta
P (in H20)
0.256
Average
Stack
Temperature
(F)=
448
PROG.=VER 06,’09/89
07—11-1990 15:26:58
Corr. to 7% 02 & 12% 002
0.0000 0.0000
Stack
Velocity (Actual,
Feet/min)
2,314
Flow
Rate
(Actual, Cubic
ft/min)=
250,886
Flow
rate
(Standard, Wet,
Cubic
ft/min)
141,722
Flow
Rate
(Standard, Dry,
Cubic
ft/min)
95,792
B-147
-------
* * METRIC UNITS * *
FILE NAME — 91O2RUN I
RUN - RUN 1
LOCATION — CONTINENTAL CEMENT STACK
DATE - 6—2O- O
PROJECT — 9102-63—13
Initial Meter Volume (Cubic Met.ers)=
Final Meter Volume (Cubic Meters)=
Meter F3ctor=
Final Leak Rate (cu m/min)=
Net Meter Volume (Cubic Meters)=
Gas Volume (Dry Standard Cubic Meters)=
Barometric Pressure (mm Hg)=
Static Pressure (mm H20)
Percent Oxygen=
Percent Carbon Dioxide=
Moisture Collected (m!)=
Percent Water=
Dry Molecular kjeight=
Wet Molecular 1.Jeight=
Average Square Root of Delta P (mm H20)
% Isokinetic=
Pitot Coefficient=
Sampling Time (Minutes )=
Nozzle Diameter (mm)=
Stack Axis l (Meters )=
Stack Axis 2 (Meters )=
Circular Stack
Stack Area (Square Meters)=
Particulate Loading — Front Half
23.737
25.151
1.096
0.0001
1 549
1 .447
739
—1 )
s — I
6.3
19.1
520 - 1
32.4
33
16.4
6.5
231
31.31
27.00
2.5341
96.9
0.83
120.0
7.67
3.581
3.581
10.074
0.0000 Corr. to 7% 02 & 12% C02
0.0 0.0 0.0
0.0
0.00
PROG.=VER 06/09/89
07—11-1990 15:27:00
Aver aje
Average
Average
Average
Meter Temperature (C)=
Delta H (mm H20)=
Delta P (mm H20)=
Stack Temperature (C)=
Stack
Velocity (Actual,
m/min)=
705
Flow
rate
(Actual, Cubic
m/min)=
7,104
Flow
rate
(Standard, Wet,
Cubic
m/min)=
4,013
Flow
rate
(Standard, Dry,
Cubic
m/min)=
2,713
Particulate Weight (g)=
Particulate Loading, Dry Std. (mg/cu m)
Particulate Loading, Actual (mg/cu m)=
Emission Rate ( kg/hr )=
No Back Half Analysis
B-148
-------
FILE NAME - 91O2RUN1
RUN $t - RUN 1
LOCATION - CONTINENTAL CEMENT STACK
DATE - 6-20—90
PROJECT #
- 9102-63-13
Fraction Final Lit. Tare Lit.
(9) (9)
PROBE RINSE 0.0000 0000 0
IMPINGERS 0.0000 0.0000
Probe Rinse Blank (mg/ml)= 0.0000
Impinger Blank (mg/ml)= 0.0000
PROG .=VER 06/09/89
07—11-1990 15:27:02
Point
Delta
P
Delta
H
Stack
1
Meter
T
(in. H20)
(in. H20)
(F)
In(F)
Out(F)
1
0.210
0.57
470
77
77
2
0.200
0.56
461
76
76
3
0.260
0.70
460
81
77
4
0.250
0.70
455
85
81
5
0.240
0.69
454
87
82
6
0.250
0.70
452
89
84
7
0.230
0.65
440
87
87
8
0.230
0.66
440
88
88
9
0.300
0.85
445
90
89
10
0.330
0.90
449
92
89
11
0.340
0.95
450
95
90
12
0.290
0.80
453
96
91
13
0.230
0.67
439
90
90
14
0.240
0.67
473
90
91
15
0.310
0.85
480
93
91
16
0.320
0.88
485
97
92
17
0.320
0.90
484
100
94
18
0.300
0.85
483
100
94
19
0.140
0.40
428
93
92
20
0.130
0.40
379
94
93
21
0.260
0.75
416
99
95
22
0.250
0.75
415
102
96
23
0.270
0.80
415
104
97
24
0.240
0.75
417
105
98
Fraction
DRY CATCH
FILTER
Final
(9)
0.0000
0.0000
Lit. Tare Lit.
(g)
0.0000
0.0000
Blank Lit.
( 9 )
0.0000
0.0000
Vol
(rn..)
0.0
0.0
Net Lit.
(9)
0 .0000
0.0000
Net Lit.
(9)
0.0000
0.0000
B-149
-------
FILE NAME - 9 102RUN2
RUN - RUN2
LOCATION — CONTINENTAL CEMENT STACK
DATE — 6-21-90
PROJECT - 9102—63-13
Initial Meter Volume (Cubic Feet)=
Final Meter Volume (Cubic Feet)=
Meter Factor=
Final Leak Rate cu ft/min)=
Net Meter Volume (Cubic Feet)=
Gas Volume (Dry Standard Cubic Feet )=
Barometric Pressure (in Hg)=
Static Pressure (Inches H20)=
Percent Oxygen=
Percent Carbon Dioxide=
Moisture Collected (ml)=
Percent l4ater=
Dry Molecular Weight=
Wet Molecular Weight=
Average Square Root of Delta P (in H20)=
Isokinetic=
Pitot Coefficient=
Sampling Time (Minutes)=
Nozzle Diameter (Inches)=
Stack Axis l (Inches)=
Stack Axis 2 (Inches )=
Circular Stack
Stack Area (Square Feet)=
Stack Velocity (Actual, Feet/min)=
Flow Rate (Actual, Cubic ft/min)=
Flow rate (Standard, Wet, Cubic ft/min)=
Flow Rate (Standard, Dry, Cubic ft/min)=
Particulate Loading — Front Half
Particulate Weight (g)=
Particulate Loading, Dry Std. (gr/scf)=
Particulate Loading, Actual (gr/cu ft)=
Emission Rate (lb/hr )=
No Back Half Analysis
890 .328
949 .323
1 .096
0 003
64.659
59.397
29 .27
-0.50
3-9
23.3
763 .2
37 . 7
31 .88
26.65
0.6052
104.9
0.83
120.0
0.302
141.0
141.0
108.43
2,914
315 ,943
165,122
102 ,867
0.0000
0.0000
0.0000
0.00
Average
Meter
Temperature
(F)=
104
Average
Delta
H (in H2O)
1.02
Average
Delta
P (in H20)=
0.379
Average
Stack
Temperature
(F)=
527
PROG .=VER 06/09/89
07—11—1990 15:30:34
Corr. to 7% 02 & 12% C02
0.0000 0.0000
B- 150
-------
* * METRIC UNITS * $z
FILE NAME - 9102RUN2 PROG.=VER 06/09/89
RUN t - RUN2 07—11—1990 15:30:36
LOCATION - CONTINENTAL CEMENT STACK
DATE — 6-21-90
PROJECT 4 - 9102—63-13
Initial Meter Volume (Cubic Nleters)= 25.211
Final Meter Volume (Cubic Meters) 26.881
Meter Factor= 1.096
Final Leak Rate (cu m/min)= 0.0001
Net Meter Volume (Cubic Meters)= 1.831
Gas Volume (Dry Standard Cubic Meters)= 1.682
Barometric Pressure (mm Hg) 743
Static Pressure (mm H20)= —13
Percent Oxygen= 3.9
Percent Carbon Dioxide 23.3
Moisture Collected (ml)= 763.2
Percent L4ater= 37.7
40
26.0
9.6
275
Dry Molecular Weight= 31.88
Wet Molecular Weight= 26.65
Average Square Root of Delta P (mm H20)= 3.0499
% Isokinetic 104.9
Pitot Coefficient 0.83
Sampling Time (Minutes)= 120.0
Nozzle Diameter (mm)= 7.67
Stack Axis #1 (Meters)= 3.581
Stack Axis 2 (Meters)= 3.581
Circular Stack
Stack Area (Square Meters)= 10.074
Stack Velocity (Actual, m/min)= 888
Flow rate (Actual, Cubic m/min) 8,947
Flow rate (Standard, Wet, Cubic m/min)= 4,676
Flow rate (Standard, Dry, Cubic m/min) 2,913
Particulate Loading — Front Half
Particulate Weight (g) 0 0000
Particulate Loading, Dry Std. (mg/cu m) 0.0
Particulate Loading, Actual (mg/cu m)= 0.0
Emission Rate (kg/hr )= 0.00
No Back Half Analysis
Average
Average
Average
Average
Meter Temperature (C)=
Delta H (mm H20)=
Delta P (mm H20)=
Stack Temperature (C)=
Corr. to 7 02 & 12% C02
0.0 0.0
B—151
-------
Fraction Final L.Jt. Tare 14t
(g) (g)
PROBE RINSE 0.0000 0.0000
IMPINGERS 0.0000 0.0000
Probe Rinse Blank (mg/ml)= 0.0000
Impinger Blank (mg/ml)= 0.0000
Net L.Jt.
(9)
0.0000
0.0000
FILE NAME — 9102RUN2
RUN - RUN2
LOCATION - CONTINENTAL CEMENT STACK
DATE - 6-21—90
PROJECT — 9102-63-13
Point
PROG.=VER 06/09/89
07-11-1990 15:30:37
Delta
P
Delta
H
Stack
1
Meter I
(in. H2O)
(in. H20)
(F)
In(F)
Out(F)
1
0.230
0.63
508
94
94
2
0.240
0.65
509
94
93
3
0.250
0.65
530
96
93
4
0.250
0.66
534
99
94
5
0.250
0.66
532
100
95
6
0.250
0.67
533
101
96
7
0.230
0.65
498
99
98
8
0.240
0.66
503
100
99
9
0.520
1.40
527
103
100
10
0.560
1.50
530
105
101
11
0.570
1.50
528
109
103
12
0.540
1.50
529
115
105
13
0.250
0.69
504
104
103
14
0.250
0.70
511
106
104
15
0.480
1.30
533
108
105
lb
0.560
1.50
536
112
106
17
0.570
1.55
539
113
106
18
0.580
1.59
542
116
107
19
0.260
0.71
530
104
103
20
0.240
0.66
500
103
103
21
0.420
1.10
547
106
104
22
0.460
1.20
549
114
106
23
0.450
1.20
549
116
108
24
0.450
120
549
116
109
Fraction
Final 14t.
Tare L4t. Blank t4t. Net L Jt
(9)
(9)
(9)
(9)
DRY CATCH
0.0000
0.0000
0.0000
0.0000
FILTER
0.0000
0.0000
0.0000
0.0000
Vol.
(ml)
0.0
0.0
B- 152
-------
FILE NAME — 9102RUN2
RUN $ - RUN3
LOCATION - CONTINENTAL CEMENT STACK
DATE - 6-22—90
PROJECT U - 9102-63—13
Initial Meter Volume (Cubic Feet)=
Final Meter Volume (CUDLC Feet)=
Meter Factor=
Final Leak Rate (cu tt/min)=
Net Meter Volume (Cubic Feet )
Gas Volume (Dry Standard Cubic Feet)=
50.558
1009 .020
1.096
0 004
64.074
60 531
PROC .=VER 06/09/89
07—11—1990 15:32:38
Barometric Pressure (in Hg)=
Static Pressure (Inches H20)=
Percent Oxygen=
Percent Carbon Dxoxide=
Moisture Collected (ml)=
Percent I.Jater=
Dry Molecular Weight=
Wet Molecular Weight=
Average Square Root of Delta P (in H20)
% Isokinetic=
Pitot Coefficient=
Sampling Time (Minutes)=
Nozzle Diameter (Inches)=
Stack Axis #1 (Inches)=
Stack Axis U2 (Inches)=
Circular Stack
Stack Area (Square Feet)=
Stack Velocity (Actual, Feet/min)
Flow Rate (Actual, Cubic ft/min)=
Flow rate (Standard, Wet, Cubic ft/min)=
Flow Rate (Standard, Dry, Cubic ft/min)=
Particulate Loading — Front Half
Particulate Weight (g)
Particulate Loading, Dry Std. (gr/scf)=
Particulate Loading, Actual (gr/cu ft)=
Emission Rate (lb/hr )=
No Back Half Analysis
29 . 1 1
-0 .50
4.2
22.3
712.3
35 - 7
31.74
26.84
0.6171
103.7
0.83
120.0
O . 302
141.0
141 .0
108.43
3,013
326,714
64,868
106,076
0.0000
0.0000
0.0000
0.00
Average
Meter
Temperature
(F)=
85
Average
Delta
H (in H20)=
0.98
Average
Delta
P (in H20)=
0.387
Average
Stack
Temperature
(F)=
557
Corr. to 7% 02 & 12% C02
0.0000 0.0000
B—153
-------
* * METRIC UNITS * *
FILE NAME - 9102RUN3
RUN - RUN3
LOCATION - CONTINENTAL CEMENT STACK
DATE — 6—22-9C
PROJECT - 9102-63-13
Initial Meter Vo ume (Cubic Meters)= 26.916
Final Meter Volume (Cubic Meters)= 28.571
Meter Factor= 1.096
Final Leak Rate (cu m/min)= 0.0001
Net Meter Volume (Cubic Meters)= 1.814
Gas Volume (Dry Standard Cubic Meters)= 1.714
Barometric Pressure (mm Hg)=
Static Pressure (mm H20)=
Percent Oxygen= 4.2
Percent Carbon Dioxide= 22.3
Moisture Collected (ml)= 712.3
Percent L.Jater= 35.7
29
24.8
9.8
292
Dry Molecular t.Jeight= 31.74
4et Molecular Weight= 26.84
Average Square Root of Delta P (mm H20)= 3.1100
Isokinetic= 103.7
Pitot Coefficient= 0.83
Sampling Time (Minutes)= 120.0
Nozzle Diameter (mm)= 7.67
Stack Axis 1 (Meters)= 3.581
Stack Axis 2 (Meters)= 3.581
Circular Stack
Stack Area (Square Meters )= 10.074
Stack Velocity (Actual, m/min)= 918
Flow rate (Actual, Cubic m/min)= 9,252
Flow rate (Standard, L.Jet, Cubic rn/min)= 4,669
Flow rate (Standard, Dry, Cubic m/rnin)= 3,004
Particulate Loading — Front Half
Particulate L Jeight (g)= 0.0000
Particulate Loading, Dry Std. (mg/cu m) 0.0
Particulate Loading, Actual (mg/cu m)= 0.0
Emission Rate (kg/hr) 0.00
No Back Half Analysis
739
-13
Average
Average
Aver age
Average
Meter Temperature (C)=
Delta H (mm H20)=
Delta P (mm H20)=
Stack Temperature (C)=
PROG .=VER 06/09/89
07-11—1990 15:32:39
Corr. to 7% 02 & 12% C02
0.0 0.0
8-154
-------
FILE NAME - 9102RUN3 PROG.=VER 06/09/89
RUN $t — RUN3 07—11-1990 15:32:41
LOCATION - CONTINENTAL CEMENT STACK
DATE — 6—22—90
PROJECT — 9102—63-13
Delta H Stack
) (in. H20) (F)
0.90 549
0.75 553
0.90 559
0.93 560
1.00 560
1.00 560
0.95 546
1.10 545
1.50 553
1.10 556
1.00 558
1.10 559
0.77 547
0.61 550
0.60 559
0.65 561
0.70 560
1.40 565
0.71 550
0.74 553
1.10 563
1.30 565
1.30 565
1.30 565
Fraction Final Lit. Tare Lit.
(g) (9)
PROBE RINSE 0.0000 0.0000
IMPINGERS 0.0000 0.0000
Probe Rinse Blank (mg/ml) 0.0000
Impinger Blank (mg/ml)= 0.0000
Point # Delta P
(in. H20
1 0.370
2 0.350
3 0.360
4 0.370
5 0.400
6 0.400
7 0.370
8 0.410
9 0.580
10 0.430
11 0.410
12 0.420
13 0.300
14 0.240
15 0.240
16 0.250
17 0.270
18 0.570
19 0.280
20 0.290
21 0.440
22 0.510
23 0.510
24 0.520
Fraction
DRY CATCH
FILTER
Meter T
In(F) Out(F)
76 76
77 76
80 76
83 77
85 79
68 81
81 81
51 82
84 82
59 63
91 85
92 86
84 84
86 86
68 86
90 87
91 88
84 85
84 83
85 85
88 85
94 87
96 88
100 90
Blank Lit. Net Lit.
( ) (g)
0.0000 0.0000
0.0000 0.0000
VDl. Net Lit.
(ml) (g)
0.0 0.0000
O.D 0.0000
Final Lit. Tare Lit.
(g) (g)
0.0000 . 0.0000
0.0000 0.0000
B-155
-------
FILE NAME — 9102RUN4
RUN 4 — RUN4
LOCATION - CONTINENTAL CEMENT STACK
DATE - 6-23-90
PROJECT - 9102-63-13
Initial Meter Volume (Cubic Feet)= 10.261
Final Meter Volume (Cubic Feet)= 71.940
Meter Factor= 1.09o
Final Leak Rate (cu ft/min)= 0.006
Net Meter Volume (Cubic Feet)= b7.bOO
Gas Volume (Dry Standard Cubic 63.745
Barometric Pressure (in Hg)= 29.17
Static Pressure (Inches- H20)= -0.50
Percent Oxygen= 4.1
Percent Carbon Dkoxide= 22.7
Moisture Collected (ml)= 623.1
Percent Water= 31.5
Average Meter Temperature (F)= 87
Average Delta H (in H20)= 1.11
Average Delta P (in H20)= 0.465
Average Stack Temperature (F)= 551
Dry Molecular L4eight= 31.80
Wet Molecular Weight= 27.45
Average Square Root of Delta P (in H20)= 0.6764
% Isokinetic= 94.3
Pitot Coefficient= 0.83
Sampling Time (Minutes)= 120.0
Nozzle Diameter (Inches)= 0.302
Stack Axis 41 (Inches)= 141.0
Stack Axis 42 (Inches)= 141.0
Circular Stack
Stack Area (Square Feet)= 108.43
Stack Velocity (Actual, Feet/min)= 3,254
Flow Rate (Actual, Cubic ft/rnin)= 352,840
Flow rate (Standard, Wet, Cubic ft/min)= 179,368
Flow Rate (Standard, Dry, Cubic ft/min)= 122,821
Particulate Loading — Front Half
Particulate Weight (g)= 0.0000
Particulate Loading, Dry Std. (gr/scf)= 0.0000
Particulate Loading, Actual (gricu ft)= 0.0000
Emission Rate (lb/hr )= 0.00
No Back Half Analysis
Feet )=
PROG .=VER 06/09/89
07—11—1990 15:35:22
Corr. to 7 02 & 12 CO2
0.0000 0.0000
B— 156
-------
METRIC UNITS
FILE NAME - 9102RUN4
RUN # - RUN4
LOCATION - CONTINENTAL CEMENT STACK
DATE - 6-23—90
PROJECT - 9102-63—13
Initial Meter Volume (Cubic Meters)= 0.291
Final Meter Volume (Cubic Meters)= 2.037
Meter Factor= 1 .09b
Final Leak Rate (Cu m/min)= 0.0002
Net fieter Volume (Cubic Meters)= 1.914
Gas Volume (Dry Standard Cubic Meters)= 1.605
Earometric Pressure (mm Hg) 741
Static Pressure (mm H20) -13
Percent Oxygen= 4.1
Percent Carbon Dioxide= 22.7
Moisture Collected (ml)= 623.1
Percent L.Jater= 31.5
31
28.3
11.8
289
Dry Molecular Weight= 31.80
Wet Molecular L4eight 27.45
Average Square Root of Delta P (mm H20)= 3.4091
% Isokinetic= 94.3
Pitot Coefficient= 0.83
Sampling Time (Minutes)= 120.0
Nozzle Diameter (mm)= 7.67
Stack Axis #1 (Meters)= 3.581
Stack Axis 2 (Meters)= 3.581
Circular Stack
Stack Area (Square Meters)= 10.074
Stack Velocity (Actual, m/min)= 992
Flow rate (Actual, Cubic rn/min) 9,991
Flow rate (Standard, Wet, Cubic m/min) 5,079
Flow rate (Standard, Dry, Cubic m/min) 3,478
Particulate Loading — Front Half
Particulate Weight (g) 0.0000
Particulate Loading, Dry Std. (mg/cu m)= 0.0
Particulate Loading, Actual (mg/cu m)= 0.0
Emission Rate (kg/hr)= 0.00
No Back Half Analysis
Average
Average
Average
Average
Meter Temperature (C)=
Delta H (mm H20)=
Delta P (mm H20)=
Stack Temperature (C)=
PROG .=VER 06/09/89
07—11—1990 15:35:24
Corr. to 7 02 & 12% C02
0.0 0.0
B—157
-------
FILE NAME — 91O2RLJN4
RUN 4 - RUN4
LOCATION — CONTINENTAL CEMENT STACK
DATE - 6—23—90
PROJECT 4
— 9102-63—13
Fraction Final 14t. Tare 14t.
(9) (9)
PROBE RINSE 0.0000 0.0000
IMPINGERS 0.0000 0.0000
Probe Rinse Blank (mg/ml)= 0.0000
Impinger Blank (mg/ml)= 0.0000
PROG . =VER 06/09/89
07—11—1990 15:35:25
Point 4
Delta
P
Delta
H
Stack
T
Mete.-
I
(in.
H20)
(tn. H20)
(F)
In(F)
Out(F)
1
0.330
0.78
553
75
75
2
0.320
0.77
544
76
75
3
0.470
1.10
551
79
75
4
0.520
1.20
553
84
77
5
0.510
1.20
554
88
80
6
0510
1.20
554
90
81
7
0.400
0.98
545
85
83
8
0.410
1.00
549
88
85
9
0.560
1.30
556
92
87
10
0.600
1.40
557
92
87
11
0.600
1.40
558
96
89
12
0.570
1.40
556
97
90
13
0.360
0.90
540
90
89
14
0.370
0.90
545
91
90
15
0.540
1.30
556
93
91
16
0.610
1.50
559
96
91
17
0.620
1.50
561
98
92
18
0.620
1.50
561
100
93
19
0.260
0.64
537
83
83
20
0.230
0.57
526
83
83
21
0.420
1.00
553
86
84
22
0.430
1.00
554
91
86
23
0.450
1.10
555
94
87
24
0.450
1.10
555
97
89
Fraction
DRY CATCH
FILTER
Final
(g)
0.0000
0.0000
Wt. Tare 1.Jt.
(g)
0.0000
0.0000
Blank Wt.
(g)
0.0000
0.0000
Vol -
(ml)
0.0
0.0
Net L.Jt.
(9)
0.0000
0.0000
Net L.Jt
(9)
0 0000
0.0000
B—158
-------
FILE NAME — 9102RUN5
RUN # - RUN5
LOCATION - CONTINENTAL CEMENT STACK
DATE - 7—5-90
PROJECT # - 9102—63—13
Initial Meter Volume (Cubic Feet)
Final Meter Volume (Cubic Feet)=
Meter Factor=
Final Leak Rate (cu ft/min)=
Net Meter Volume (Cubic Feet )=
Gas Volume (Dry Standard Cubic Feet)=
Barometric Pressure (in Hg)=
Static Pressure (Inches H20)=
Percent Oxygen=
Percent Carbon Dioxide=
Moisture Collected (ml)=
Percent Water=
Dry Molecular L4eight=
l4et Molecular Weight=
Average Square Root of Delta P (in H20)=
Isokinetic=
Pitot Coefficient=
Sampling Time (Minutes)=
Nozzle Diameter (Inches)=
Stack Axis i (Inches)=
Stack Axis t2 (Inches )=
Circular Stack
Stack Area (Square Feet )=
Stack Velocity (Actual, Feet/min)=
Flow Rate (Actual, Cubic ftimin)=
Flow rate (Standard, I4et, Cubic ft/min)=
Flow Rate (Standard, Dry, Cubic ft/min)=
Particulate Loading - Front Half
Particulate Weight (g)=
Particulate Loading, Dry Std. (griscf)=
Particulate Loading, Actual (gr/cu ft)=
Emission Rate (lb/hr )=
No Back Half Analysis
94.040
57.590
1 .096
0.005
b9 651
63.143
29.34
-0.50
4.5
22.0
763.3
36.3
31 .70
26.73
0.6323
99.2
0.83
120.0
0.308
141.0
141.0
108.43
3,003
325 ,577
L74 ,415
111 ,137
0.0000
0.0000
0.0000
0.00
Average
Meter
Temperature
(F)=
113
Average
Delta
H (in H20)
1.17
Average
Delta
P (in H2O)=
0.408
Average
Stack
Temperature
(F)=
505
PROG .=VER 06/09/89
07—12—1990 10:42:17
Corr. to 7% 02 & 12% CD .
0.0000 0.0000
B—169
-------
* METRIC UNITS * *
FILE NAME — 9102RUN5
RUN 4 — RUN5
LOCATION — CONTINENTAL CEMENT STACK
DATE — 7—5—90
PROJECT 4 — 9102-63-13
Initial Meter Volume (Cubic Meters)=
Final Meter Volume (Cubic Meters)=
Meter F ctor=
Fine! Leak Rate (Cu m/min)=
Net Meter Volume (Cubic Meters )=
Gas Volume (Dr’/ Standard Cubic Meters)=
Dry Molecular L.Jeight=
I4et Molecular I4eight=
Average Square Root of Delta P (mm H20)
Isokinetic
Pitot Coefficient=
Sampling Time (Minutes)=
Nozzle Diameter (mm)=
Stack Axis #1 (Meters)=
Stack Axis #2 (Meters)=
Circular Stack
Stack Area (Square Meters )=
Particulate Loading — Front Half
Particulate Weight (g)=
Particulate Loading, Dry Std. (mg/cu m)=
Particulate Loading, Actual (mg/cu m)=
Emission Rate ( kg/hr )=
No Back Half Analysis
2 .663
4.462
1.096
0.0001
1.972
1 .788
745
_1 )
.1. ‘.1
4.5
22.0
763 .3
-.“ -
45
29.6
10.4
31 .70
26.73
3.1867
99 . 2
0.83
120.0
7.82
3.581
3.581
10.074
0.0000
0.0
0.0
0.00
Barometric Pressure (mm Hg)=
Static Pressure (mm H20)=
Percent Uxygen=
Percent Carbon Dtoxide=
Moisture Collected (ml)=
Percent L.Jater=
Average
Aver age
Average
Average
Meter Temperature (C)=
Delta H (mm H20)=
Delta P (mm H20)
Stack Temperature (C)=
PROG .=VER 06/09/89
07—12—1990 10:42:19
Corr. to 7% 02 & 12% C02
0.0 0.0
Stack
Velocity (Actual,
m/min)=
915
Flow
rate
(Actual, Cubic
m/min)=
9,219
Flow
rate
(Standard, Wet,
Cubic
m/min)=
4,939
Flow
rate
(Standard, Dry,
Cubic
m/min)=
3,147
B -160
-------
FILE NAME - 9102RUN5
RUN # - RUN5
LOCATION - CONTINENTAL CEMENT STACK
DATE - 7-5—90
PROJECT # — 9102-63-13
Fraction Final Wt. Tare Wt.
(g) (9)
PROBE RINSE 0.0000 0.0000
IMPINGERS 0.0000 0.0000
Probe Rinse Blank (mg/ml)= 0.0000
Irnpinger Blank (mg/ml)= 0.0000
PROG .=VER Ob/09/89
07—12—1990 10:42:20
Point
Delta
P
Delta
H
Stack
T
Meter I
( in. H2O)
( in - H20)
( F
)
I n( F
) Out( F
1
0.280
0.81
501
103
101
2
0.280
0.80
504
104
102
3
0.460
1.30
516
108
104
4
0.490
1.40
518
113
105
5
0.510
1.40
516
106
106
6
0.480
1.30
51
114
107
7
0.300
0.86
504
109
106
8
0.330
0.94
504
110
108
9
0.470
1.30
510
115
109
10
0.500
1.40
512
120
111
11
0.530
1.50
510
123
114
12
0.510
1.50
512
125
115
13
0.290
0.65
495
112
110
14
0.300
0.88
493
111
111
15
0.520
1.50
509
116
112
16
0.560
1.60
511
121
114
17
0.560
1.60
512
124
115
18
0.530
1.50
511
126
116
19
0.220
0.65
495
112
109
20
0.210
0.61
491
112
109
21
0.330
0.96
497
115
112
22
0.370
1.10
497
119
114
23
0.380
1.10
497
122
115
24
0.380
1.10
496
123
115
Fraction
DRY CATCH
FILTER
Final
(9)
0.0000
0.0000
L4t. Tare 14t.
(9)
0.0000
0.0000
Blank 14t.
( g )
0.0000
0.0000
Vol
(m]
0.0
0 . C)
Net L.Jt.
(9)
0.0000
0.0000
Net 14t.
(g)
0.0000
0.0000
B—161
-------
FILE NAME - 9102RUN6
RUN t - RUNb
LOCATION - CONTINENTAL CEMENT STACK
DATE - 7—5-90
PROJECT - 9102-63—13
Initial Meter Volume (Cubic Feet)
Final Meter Volume (Cubic Feet )=
Meter Factor=
Final Leak Rate (cu ft/min)=
Net Meter Volume (Cubic Feet)=
Gas Volume (Dry Standard Cubic Feet )=
158 .750
227 .840
1 tsr , ,
I .‘J O
0.002
75.723
69.552
PROG .=VER 06/09/89
07—12—1990 10:44:21
Barometric Pressure ( n Hg)=
Static Pressure (Inches H20)=
Percent Oxygen=
Percent Carbon Dioxide=
Moisture Collected (ml)=
Percent L.Jater=
Dry Molecular Weight=
Wet Molecular Weight=
Average Square Root of Delta P (in H20)
% Isokinetic=
Pitot Coefficient=
Sampling Time (Minutes)=
Nozzle Diameter (Inches)=
Stack Axis #1 (Inches)=
Stack Axis 2 (Inches)=
Circular Stack
Stack Area (Square Feet )=
Stack Velocity (Actual, Feet/rnin)=
Flow Rate (Actual, Cubic ft/min)=
Flow rate (Standard, Wet, Cubic ft/min)=
Flow Rate (Standard, Dry, Cubic ftimin)=
Particulate Loading — Front Half
Particulate Weight (g)=
Particulate Loading, Dry Std. (gr/scf)=
Particulate Loading, Actual (gr/cu ft)=
Emission Rate (lb/hr )=
No Back Half Analysis
29.34
-0.50
4.8
21.9
840.3
36.3
31 70
26.73
0.6934
100.3
0.83
120.0
0.308
141.0
141.0
108 .43
3,313
359 ,228
190 ,087
121 ,148
0.0000
0.0000
0.0000
0.00
Average
Meter
Temperature
(F)=
105
Average
Delta
H (in H20)=
1.36
Average
Delta
P (in H20)=
0.484
Average
Stack
Temperature
(F)=
517
Cor’r. to 7% 02 & 12% C02
0.0000 0.0000
B-162
-------
* * METRIC UNITS *
FILE NAME - 9 102RUN6
RUN - RUN6
LOCATION - CONTINENTAL CEMENT STACK
DATE - 7-5-90
PROJECT - 9102-63-13
Initial Meter Volume (Cubic Meters )= 4.4 5
Final Meter Volume (Cubic Met.ers)= 6.452
Meter Factor= 1.096
Final Leak Rate (cu m/min)= 0.0001
Net Meter Volume (Cubic Meters)= 2.144
Gas Volume (Dry Standard Cubic Meters)= 1969
Barometric Pressure (mm Hg)=
Static Pressure (mm H20)=
Percent Oxygen= 4.8
Percent Carbon Dioxide= 21.9
Moisture Collected (mi)= 840.3
Percent L4ater= 36.3
41
34.5
12.3
270
Dry Molecular Weight= 31.70
Wet Molecular Lieight= 26.73
Average Square Root of Delta P (mm H20)= 3.4945
Isokinetic= 100.3
Pitot Coefficient= 0.83
Sampling Time (Minutes) 120.0
Nozzle Diameter (mm)= 7.82
Stack Axis $ 1 (Meters)= 3.581
Stack Axis 42 (Meters)= 3.581
Circular Stack
Stack Area (Square Meters)= 10.074
Stack Velocity (Actual, m/min)= 1,010
Flow rate (Actual, Cubic m/min)= 10,172
Flow rate (Standard, Wet, Cubic m/min)= 5,383
Flow rate (Standard, Dry, Cubic m/min)= 3,431
Particulate Loading - Front Half
Particulate Weight (g)= 0.0000
Particulate Loading, Dry Std. (mg/cu m)= 0.0
Particulate Loading, Actual (mg/cu m)= 0.0
Emission Rate (kg/hr )= 0.00
No Back Half Analysis
745
_1 )
A. d
Aver age
Average
Aver age
Aver age
Meter Temperature (C)=
Delta H (mm H20)=
Delta P (mm H20)=
Stack Temperature (C)=
PROG .=VER 06/09/89
07-12—1990 10:44:22
Corr. to 7% 02 & 12% CD:
0.0 0.0
B—163
-------
FILE NAME - 9102RUN6
RUN - RUN6
LOCATION — CONTINENTAL CEMENT STACK
DATE - 7—5—90
PROJECT - 9102-63-13
PROG . =VER 06/09/89
07-12—1990 10:44:24
Fraction Final
(g)
PROBE RINSE 0.0000
IMPINIGERS 0.0000
Probe Rinse Blank (mg/mi )=
Impinger Blank (mg/ml)= 0
14t. Tare L4t.
(g)
0.0000
0.0000
0 0000
.0000
Point
Delta
P
Delta
H
Stack
T
Meter T
in. H20)
(in.
H20)
(F)
In(F)
Out(F)
1
0.440
1.20
532
94
93
2
0440
12 0
521
92
91
3
0.460
1.20
521
97
92
4
0520
140
521
101
93
5
0540
150
520
106
95
e
0.500
1.40
519
109
97
7
0.450
1.20
518
104
101
8
0.540
1.50
521
107
103
9
0.580
1.60
519
112
104
10
0.610
1.70
519
115
106
11
0.620
1.80
517
117
106
12
0.560
1.60
515
117
108
13
0.420
1.20
515
109
107
14
0.520
1.50
516
110
108
15
0.540
1.50
517
114
108
16
0.580
160
517
117
110
17
0.590
1.70
516
118
110
18
0.400
1.20
515
119
111
19
0.390
1.10
515
100
100
20
0.390
1.10
515
102
102
21
0.380
1.10
513
106
103
22
0.390
1.10
512
109
103
23
0.380
1.10
510
111
104
24
0.380
110
510
112
105
Fraction
DRY CATCH
FILTER
Final
(g)
0.0000
0.0000
14t. Tare Wt.
(g)
0.0000
0.0000
Blank L4t.
(g)
0.0000
0.0000
Vol.
(ml)
0.0
0.0
Net L.Jt.
(g)
0.0000
0.0000
Net L.Jt.
(9)
0.0000
0.0000
B-164
-------
MET HODS
ire rH’b c&ITIpJ es for semi —•ioi ati see. rLL’lJ’FLUFE r n
ara’nretric an iv ’ t i uare preparea accorjino to EF— -i E,La -ci ie
methoris ‘ 9itn TIcaJ t i c;ti one aescribea pre”iouss v in tfli s
appendi”.Fhe ti\.e comoonen c of the sempirQ train ront—na]r
rinse. filter. o;c —naJf rinse. XAD era corsoerse e were e€ cn
extractea eeparneiv. li samp es were treated similarly. 1-nor
to extr;ctinn of the f iter, the -front—half rinse was filtereo to
remo”e any parcic’lates. mis filter eno solicis ratcn ec
comoinen witfl the r IMS filter ano e, tractec.
irn”lOLtas sampiina tr.tn components t dere soilea witn
surroaate compounas before so lvent extraction as descnioed below:
Component soued Run No.
witn surrociate
m i
‘semi—vol. D ,F
I-iiter 1. 5 , —t. S
Front half rinse
? AD
Sad half rinse 4 No
Londensate No
ihe filtenisolias catch and X iD samales were extracted
initially witn dicnloromethane -for I a — 22 hrs. The solvent was
removed. ana tne sample was extracted for an additional I a —
hrs with tc.luene. A third solvent. rnethyl—t—butyl ether was usea
to extract tne samples for a final It — 22 hrs. The tnree solvent
extracts were comoined and saved.
A similar three solvent extraction scheme was usea for the
tront—hal f • bac ’—hal f and condensate comoonents of the riMS trei n.
The ph of eacn of these components was inittallq adjusted to 7—8.
usinci I N NaOH or 1:1 H2S04:H20. EEch sample was extracted three
times witn aichloroinethane in a separatorv funnel. The sample ph
was adjusted to il using I N NaGH £nd the sample was e , tracted
tnree more times witn dichioromethane. the ph of tne sample was
ad3usted oac to —8 and the samples was extracted with toluene
and methyl—t—butyl ether, respectively. The dichloromethane.
toluene and metnvl—t—hutvl etner e tracts were comoined and
saved.
Ihe five component e. tracts from each train were comosned.
concentrated tO 1C’mi and split for semi—volet le. PCOU’F-CDF ana
Qravi metric analysis as snown below. The semi—volatile portion
8-165
-------
w concsr,trated to .tml orior -cc analysis. The FCDU’F’ DF çiorton
cleaneo uo accordin. to EP t ,lAJ--84 Method j ’: prior to
& n 1 ‘/51 5.
H an Method 1etr ocl Fur Fun Fur run r’irc Fur
u1cri Train l ian 131 en 1 4 5 a
,- na1 ‘ is is cmi in traction’
Et—acti on
= - - - = = -
-mi— ’ .oi. .... m± _ .‘ .J ’ : ... ._, —
i-cw:’’PLDF ::.5nl u 5 2.5
tra inetrtc 5 C’m1 5...’ 5.’ ) V f. ’: S .C S .’: 5.C’
The fol low’ no 1 aooratorv [ ‘C samples were carerstec Aor f-CDE’ ECL iF
analysis to monitor the precision and accuracy ot the anasytical
results These nine sampie u lere prepRrRCl anc an lv2ea s
oescribea previousiy. ir,e oian samples were aiso ana-i’;:eo for
semi —“olati 1es
Filter
riatri” ‘mpile $
Matri; Spile Duplicate I
131 ani
Deviations from sample preparation protocol:
The sample ana iysis r ,oid]nQ times were not met for all
sampi es.
5ix Nt i S trains were collected between June :c’ ano July a .
jpQ - 1 Solvent extraction of the samoles wa oone in two
separate sets or June :5 aro July . Therefore. e”traction
o-f cl i samples was startea Lautnin a c]avs ai-ter samp ling. ana
alt c -traction hoiding times were met.
Sample anal “sis for the semt—volatiie screen wa starteo or’
wuqust Ia . l ’5, wr,icn is 31 clays as-ter preparation or tr e
first set ot samplee and 3 cays after preparation ot tne
second set or samples. Fheretore, anai’,sis nolotnc times ot
41 cays a ter sample preparation were not met -for samples
collected dur-t rig Funs I through 4. The reasons for this
have been investi’jated ana corrective action will he ta en.
t sna1ysis holdin’a times for FCDD,FCDF analysis ca months
after sample preparationi were met.
B-165
-------
In c s d \.enh: r eser”oi r ‘ ‘ent or, rjurino tre m tn ’-’ I —t 0’ ‘t \ £
oyh, r ‘traction CT cTp1e 4C ’ bun 4 u’ . his as oue
to urcontrol led iater temper at’Are i r the sovhl et conoen er
Lorrerti “e cotton t c en to pre’.’ent tri S in tne 4 ture
Involved movin Ec’J.’/ent e>’traction operationa to tre routine
eemc’le preparation iso hicr has cri lled water tor the
coroersers
ihe svrLrae usea to add the s’rrogate mixture to tne ol cr1
train sampice apparently did not retain the o1ume s np]eo.
ire sampi e preparation super i sor has oi scaroed sucr
svr i naes.
Saap)e 5CC’) Run 5 Xr E/ had woe resin breal trrouor past
the Soxhiet sample reserv’oir into the boiling -fles . In
addition. a small loss of solvent was observed. ihe resin
was filtered out c-f tne solvent reservoir and recombined
with the bul of tre AD in trce samol e reservoir be-fore
extraction wttn methvl—t—h.ttvl etner.
8-167
-------
P EULTS
aole I sumilcarizes tre FCcJu/F:DF anat yticai res’’its in tne
Hannitnal Cement tin se,in tee. Tab tnrouah 5 rr er,t toe
resui te o an s i vsi S Of the qua] ity assurance sacnp see ‘iFethCo
blame, m a cri ’ spites and ,natri ’ spite duplicates’ burroo;ts
reco’eri cc for FC ’ue ano F’.,UFs are St 50 inc Ludea on tnese tao Lee.
Fositive iciencification cf tne PCUD and PCO’- conuener was
nasea on reter.r inn time ano theoretical ractoc. or areas m a’ ’red
for e cn of the c’ ,o ioni mont’:ored ‘ I5 ’ ’ ‘ Li ca ihration
cri cert a were m t rJt’ri r,g are t yct s Or tr,ese sr.mp C s as speci r tea
in ¶‘t i—2 o Iet nod u2 -: ,, inst jainr tn ’ s rodi cetionc ciescri ord
pre ‘icLe
ne simi c c ct oetecriorl qtven in lable I are Dasco On
Ei matci L’erec i on Limi r ‘EL’L ‘. ire EUL s cai c’’i ataci rom Dn
amount ot nr.3 cc detected at the e ’ pecteo reten c ion t i me at-
target compound. The EUL was also applied to non—u, :. 7. -C tiC’
end FCUF i somers i r, determint nq . nicn isomers to a.nc ude in tne
calc’lati one of total PCI’D’F’CL’F romo] oos.
Comments on PCDD/PCDF Results
FCDD’PCDF results reported icr tun 4 and tne Btsn irain ate
suspect oecause 0 + low surroucte recoveries tor ai I I - oeled
ccmpounas spited into the sample before c /traction ‘see
T , nlp U. Similarly low surrogate r crjver1 were also
oetecteo in one of tne wster matrix spites Tar ,ie 3’, eno
maw’ be related to the syringe used for spi I in c see item
acove in method deviations -
In c o”ers I. F’CDOIFCc,F surrogate recovery avereoc was 7T:. 4?.
‘n=l determinat one. 4 samples an&ty:ed, :..:?. RSL’’, but
if tne three sampi cc wfl] c i had low surrogate reco\er i cc are
discounted ie., reporteo as suspect’. the overalL average
s”rrocate recovery increases to EC.8?. determinations.
l samples anaiy:ed, : 1. 1?. RSEn. In ooth cases, the
precision quality control oh ective of was met.
ijqer l 1 , :5 FCE®’FCDF surrogate deterininati one, out or 5
totaL o ld determinations. ‘ere outside accurac criteria
o 4u—L: . This inntcates that: Bt.IS. ot tne osterminations
were witnin acceptance criteria, which is ‘41 thin the
req’.’ireo compLeteness quasity control orijecti’/es ‘.ULUS)
Di scot’nti ng tne three samples with low surrogate recoveries.
5 out of 9 c m ? . , ’ determinations were wtnin ‘:‘Los.
Overall. 102 matrix spi’ e recovery determinations were maoe,
of wnicn 7’.’.&/. were within quality control oo ecttves of 4:—
fl )?. reco”ery. ihis included one matrix spiLe wnose
surrocate recovery suggest suspect data. Exci udi ng tni s
B-168
-------
c Hperr c mnLe, •-,-4, ‘•‘- Cn t= :.rflc-inir C ri;cr
recover / Oscar Ti) nati ‘ fi I ?’- i t it t O) fi tr 1 cDJ Ctt JOE ..
z.rr1, scu e recc .er cecernur;ti ns t isre maa in n’’piic .te
for eac c+ tne tnree mi.tric:es ‘tEC O ‘i - i 1te :(. p , watsr
Er ic ludtnr tree m-’crt spi C Witfl suspect resu i ts O .
c i- tne oeter’TRnktt0fi2 ‘n=51 ware t-n tnin preci si on
rj i ri.e E If cr c s’specc se-npie is e c1uaeci, Eui . n ’J ’
C-.t bfl9 aeterri nat:i ons were - run cri ceri a-
r etriocl b’ sn’ 5 were nor are 1-CCJ concurreric I wi cn a; I tne
sampies. Inc metnc’d nients th t were eycractea -‘ere preparea
L incler represent;tiJe laboratory coroiticns,, using t he same
set at reaaents as were used for tne i-i da sampies. In tnis
context, tre r Ian c aralyzeo snc’ulo be cofisiderea to be
met nod blarvs for samp les that were cc .—e’ tracteo, reecent
hia.nls for a u ol-rers, and hian s representative ot typical
laboratory cOnOit)-_JnE.
Table a sumrart:es crc semi—’.ciatile screening results in
the Hannioal Cement I)in samples - Tnis table includes tne results
ot anajysis of tne metnoo bI ani a and bl am tra n. Surrc’c;ate
recoveries tar L)i—p/rene and .4.o—tribromopnen’Dl are also
incluoed on this teole. Table 7 presenti. the idcnti+ ,cat c’fi ani
estimated concentration tar tentatlveiY ioenttrtea compounos
netected in tnese samples.
All mass cajioration criteria relatec to L’Fi”rF tuning ee
verit lea prior to analysis at c;mples Prior to tne GL’rlr 52m1
oiatt1e screening o+ tress samp les. a ca libration curve
concai nino ai or the L SEEA—L1 P taroet analytea was prep re i -
irese —esponses were i’se- to contirm tnat tne instrument response
was stil l yaijd anc to quantity tns concentration 0+ the CLF
natytes in tne samples.
Comments on Semi—volatile screeninç results:
Each sample was spiked w tn ‘ o’mL of tne internal
scandarde rather than the oriçinaily specifiec 4-’ mL .
fhe u g’mL spive was consistent with the requirements for
EFAs Contract Laboratory Frogracn cLLP’. This modt+ca-tlon
was approved because the samples were analyzed for semi—
volatile organic compoun’is using the CLP calibration curve.
The BC conditions were somewhat different crom tnose
originally specified in the method. The BC conditions
appropriate for the CLF samples were used in order to
minimize the impact on retention time oata.
Two semi -vol an 12 surrogate cc impounos rnere used, Di’j—pyrene
snô :, 4, .s—trioromophenol ihe recovery for DIC’—p yrene was
B-169
-------
,nrhtr the 04t5 C ]kl= i-Li-v rc ipri -iy rerq€ ot ‘i- L_.i . + r i1
£ mpies Ire reccvery for , 4. —rr ) rroiiicpfler I no e tne
L;c . ODJCCC1VE tar Sev’ereL ot the ifl % VEeS 1 rowever- tfl e
recovery v’ M t t ni n the ohj ect ec t id . :s.
B-170
-------
SEMIVOLATILE ANALYSIS RESULTS
Blank
Weight
Run 1
Run 2
Run 3
Weight
Coric
Analyte
Weight
Conc
Analyte
Weight
Conc
Analyte
Found
Found
(ugldscm
Emission
Found
(ug/dscm
Emission
Found
(ug/dscm
Emission
(ug)
(ug)
or ng/L)
(mg/mm)
(ug)
or ng/L)
(mg/mm)
(ug)
or ngIL)
(mgfmln)
Gas Sample Volume = 1 447 1 682 1.714
Stack Gas Flowrate (dscm/min) = 2710 2910 3000
POL (total ug) = 40 40 20 40
Benzyl alcohol 140 lOOO 700 2000 lOOO 600 2000 800: 500 2000
Benzoicacid 2000 q 1000 3000 lOOO 600 2000 2000 1000 3000
Phenol 130 77 225 290 169 508
2-Chiorophenol
2-Methyl phenol
4-Methylphenol 874 52 151 90 53 158
Naphthalerie 210 145 393 1000 600 2000 1000 600 2000
2-Methyl naphthalene 75 52 140 170 101 294 260 152 455
2,4,6-Tr luikiupheiioi 44 26 76
Acenaphthylene 160 95 277 200 117 350
Dibenzofuran 170 101 294 250 146 438
Diethyl phthalate
Fluorene 44 26 76 50 29 88
Phenantlirene 30 21 56 200 1O0 4 300 270 158 473
Arithracene 22 13 38 25 15 44
Fluoranthene 77 46 133 80 47 140
Pyrene 49 29 85 48 28 84
Benz(ajanthracene
Chrysene 38 23 66 38 22 67
Bis(2-ethylhexyl)phthalate
File SVOL By PSM Date 11/29/90
-------
SEMIVOLATILE ANALYSIS RESULTS (con’I)
Run4
Run5
Run6
Weight
Conc
Analyte
Weight
Conc
Analyte
Weight
Conc
Analyle
Found
(ug/dscm
Emission
Found
(ug/dscm
Emission
Found
(ug/dscm
Emission
(ug)
or ngIL)
(mg/mm)
(ug)
or ngIL)
(mg/mm)
(ug)
or ng/L)
(mglmin)
Gas Sample Volume =
1 805
1 788
1 969
Stack Gas Flowrate (dscm/mmn) =
3486
3150
3430
PQL (total ug) =
40
40
20
Benzyl alcohol
Berizoic acid
800
2000
400
1000
1000
3000
lOOO
1000
600
600
2000
2000
700
300
400
200
1000
700
Phenol
98
54
189
120
67
211
270
137
470
2-Chlorophenol
16
9
31
2-Methyl phenol
30
15
52
4-Methylphenol
110
61
212
110
62
194
110
56
192
Naphthalene
1000
600
2000
iOOO
600
2000
1000’
500
2000
2-Methyl naphthalene
160
89
309
260
145
458
200
100
300
2,4,6-Trichlorophenol
58
32
112
Acenaphthylene
130
72
251
190
106
335
170
86
296
Dibenzofuran
170
94
328
230
129
405
180
91
314
Diethyl phthalate
47
26
91
Fluorene
75
42
132
75
38
131
Phenanthrene
150
83
290
290
162
511
200
100
300
Anthracene
41
23
72
49
25
85
Fluoranthene
110
62
194
100
51
174
Pyrene
87
49
153
88
45
153
Benz [ ajanthracene
20
10
35
Chrysene
57
32
100
63
32
110
Bis(2-ethylhexyl)phthalate
94
53
166
53
27
92
N)
€2 .s e ‘.‘ac ..- The’,. tim, h ( i/i b ’ h 74;7 €‘ /v
&,T é’5 ” i: -
File SVOL By PSM Date 11
-------
The following compounds represent the semivolatile analytes that were not
detected above the POL in any of the MM5 sampling train samples
ANILINE
AZOBENZENE
BIS(2-CHLOROETHYL)ETHER
1 ,3-DICHLOROBENZENE
1 ,4-DICHLOROBENZENE
1 ,2-DICHLOROBENZENE
2-METHYL PHENOL
2,2’-OXYBIS(l -CHLOROPROPANE)
N-NITROSO-DI-N-PROPYLAMINE
HEXACHLOROETHANE
NITROBENZENE
ISOPHRONE
2-NITROPHENOL
2,4-DIMETHYL PHENOL
BIS(2-CHLOROETHOXY)METI- IANE
2,4-DICHLQROPHENOL
1 ,2,4-TRICHLOROBENZENE
4-CHLOJROANILINE
HEXACHLORO- 1,3- BUTADIENE
4-CHLORO-3-METHYL PHENOL
HEXACHLOROCYCLOPENTADIENE
2.4,5-TRICHLOROPHENOL
2-CHLORONAPHTHALENE
2-NITROANILINE
DIMETHYL PHTHALATE
2,6-DIN TROTOLUENE
3-NITROANILINE
ACENAF HTHENE
2,4-DIN ITROPHENOL
4-NITROPHENOL
2,4-DIN ITROTOLUENE
4-CHLCIROPHENYL-PHENYL ETHER
4-NITROANILINE
4,6-DINITRO-2-METHYL PHENOL
N-NITRDSO-DIPHENYLAMINE
4-BROMOPHENYL-PHENYL ETHER
HEXACHLOROBENZENE
PENTACHLOROPHENOL
CARBA OLE
BENZYI. BUTYL PHTHALATE
3,3’-DICHLOROBENZIDINE
B ENZ(A]ANTH RAC EN F
DI-N-OCTYL PHTHALATE
BENZO BIFLUORANTHENE
BENZO KJFLUORANTHENE
BENZO AJPYRENE
INDENOI1 ,2,3-C,DJPYRENE
DIBEN2 IA,HIANTHRACENE
BENZOIG,HIJPERYLENE
B-173
File SVNOHITS By. PSM Date. 11/29/90
-------
TABLE I PCDDIPCDF RESULTS FOR HANNIBAL CEMENT KILN EMISSIONS
______________ RUNII RUN3I RUN4I RUN5IBLANKTRAIN
2,3,1,8.TCDF <8.46 <210(b) <9.11 <20.9 <42 5
2.3,7,8.TCDD <6.61 <6.08 <14 <7.23 88.8
1 .2,3,7,8.PcCDF <6.16 <6490(a) <10400(a) <3720(a) <116(a)
2,3,4,7.8-PcCDP <2320(a) 14900 <27400(a) 10800 153
1,2 .3,7,8-PeCDD 255 3240 4520 5220 103
1 .2,3,4,7,8-HxCDF 1140 4970 7440 3720 118
1 .2,3,6,7,8-HxCDF 571 2350 3960 2000 <65.5 (a)
2,3,4,6,7,8-HxCDP 225 884 1720 1250 72.9
1 .2,3,7,8$-HxCDF <137 565 <741 275 19.4
1,2.3,4,7,8-I- 1xCDD 550 4580 7170 9280 118
1,2,3,6,7,8.HxCDD 647 3750 7040 11100 <100(a)
1,2,3 7,8,9-HxCDD 520 4980 7880 9150 <141(a)
1.2,3,4.6,7,8.HpCDP 2050 4750 4860 1400 <124(a)
1,2,3.4,7,8,9-HpCDF 356 546 624 190 <14.9(a)
1,2,3,4,6,7,8 .HpCDD 4140 12400 21300 36000 453
OCDF <1660(a) <3530(a) <3040(a) <469(a) 228
OCDD 5360 16900 19500 15800 2160
TCDF
TCDD
PeCDF
PcCDD
HXCDF
HxCDD
HpCDF
HpCDD
OCDF
OCDD
16900 164000 322000 99100 2280
12100 53100 121000 52600 1530
5810 38300 179000 70600 568
17100 151000 284000 531000 1340
2510 14200 21500 11900 240
82100 276000 615000 1010000 3150
3400 8850 8400 2470 <28.7
9490 25300 48100 87300 845
<6.99 <10.3 <26.5 <4.22 228
5360 16900 19500 15800 2160
SURROGATE RECOVERY
(%)
13C-TCDF
13C.TCDD
13C .PcCDF
13C-PcCDD
13C .HxCDF
13C-HxCDD
13C-HpCDF
13C-HpCDD
13C .OCDD
68.5
74
66.1
82.7
62.4
69.2
73.4
66.5
72.9
62.8
91.8
107
112
68.5
75.5
82.6
877
79
39.2
444
48.4
45.1
34.3
33.6
38.5
41.4
35.9
28
80.3
105
104
79.5
903
96.7
98.3
79.5
28.2
31
44.6
32.5
24.4
25.1
32.7
349
243
(a) THE NUMBER PRESENTED REPRESENTS MAXIMUM POSSIBLE CONCENTRATION
(b) VALUE PRESENTED IS A PRACTICAL QUANTITATION LIMfl ; ABSENCE OF NOISE
PRECLUDED CALCULATION OF ESTII 1ATED DETECTION LIMif
B-174
-------
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NP N ‘.4 N 97 623 b2.r: I.3e0 a029 i7L z
2,:, 4,1 ,E_CCC N N NA N 250 3 lIlt 4280 5fl 7l, t ‘ it
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P P C \ :2 1 w C18 .7Z 278 _n:ls C177 .i .
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B-175
-------
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‘A NA 1 ’ 5c72 : . ;;. 5078 ii it 74.
‘44 :6 ,. ::. Ut , 8 ’ 2 18 1 6)t
N P N NA NA i1 ’ 5 3 5973 1 S ,4 s :t
‘.A N r . A. 3 :5. . 5 ’ &.S3 3._Z 7. Z
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NP N 36 4C 1 :51 243.. : 1,6e:: Th.TX
N A ‘4 NP M 25’ . : :ss 2i3. 19Y 1 Tha 97S. Th5Z
1 .2.3,7,8 .:_HcDD NA \ NA N4 :653i 2t ::c.F: 16 ’ ) 15:66 11,L7t :.:t
NA NA ‘ A 4:30 ‘ , 32.:% 177O’ 15 :2 :1E.V. s:.c
NA 4:2 O ’ :5 f l! :87, ,; EZa3 i5O 122.:Z ; ‘ , ‘;
1 V N A 5cm; 193 :3 .5’ li)O. 14 9 1 Th.’.
cc2r N A ‘J NA : 842 ‘n 3c 2 :77 t : c : : a 1:a.7 . 72.E
cc:r NA hA NA : ;c 2: .;t 3O 9 : i2 :‘ ; s:.::
PE CE % SIJ 6VE RECC:E :E!
— — 3.5 — - E. — — —
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— — li’ 7 — - ci . 3 - — -
P . , — , , F’,’ c
IL 1 “ I — — — — CO..i — — —
IF • ‘ fl’ — —
I L — — U . 1 — —
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ND .D - — 2 — - ‘34. — - -
in — — a. — — OLE — — -
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N:rDt s i ed NA:not ar,u1 7 :ed c :ete:tad, ND: ;t JEt2:tei: fl:oE:e:ted, but a iavel i342r tran the qLar:_ta:_r 1_in
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B—176
-------
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‘ . NA N 5q 73 1:L 55 5c7 9 9C,
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B—178
-------
l cr n dat4 E i , ”. T ‘Cf E )1 P 5 tfl
LE t c.: 4i i . ,1 hl ’i4 f ’i ,ri 4i ‘ ‘i 4Ic ,p . ’
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i &ET IF0UN [ ,5
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iL1 E ‘ 4” 2 ’ ‘ 2’’ 4& ‘ 2’ 4” ‘ ‘ 40 ‘ 2 0
BErG & HL’ )1 41 JL 14’’ Ia 14’’ loo’ ’ l’)’ ” 8o ’$ t, ,cw; 7’i0
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£—LdL ’i 0PHENCJL ‘ 4 ’ . ’ ‘, 2’ ‘. 20 ‘ 4v ‘. 2” ‘. 40 ‘. ‘. 40 ‘. 2”
—Ui1t 4L0R0 EML NE 41 * 20 2” ‘ 4 o ‘ 2’ 4’’ 4o ‘ 4” 2’’
1, — ‘iCHiURUBE 1iENE ‘ 40 ‘, 2” 2” ‘ 4o ‘ ‘ 4’) S 4o ‘ 4u ‘,
1. 2— ’ .HL0RJ 2E ‘ 40 2’ ‘. 2” 4” ‘. 2’.’ 40 ‘ Li,’ * 4i
2—HEThcL PHE14UL 4o ‘, 2” ‘. 2o ‘ 40 ‘ 2 ’ 40 4’ 4o 3,.
2.2’ — U —CHLOPOPPOP NE’ 4o ( 2o 2” ; “ 2” ‘. 4o c 4u 4,’ ‘
A— EI L HE OL ‘ 4o ‘ 2’ ‘, 2o 40 87 ‘ , ‘ 110 liv 110
—t1ITR—0i— —PPOP’ LAN1 E 4 o 2’ , 2” (4’, ( 2 ’I ‘ 4” ‘ 4” ‘ 4o c
HE C 10 OE1Hk E ‘ 40 ‘ 2 o ‘ 2 ’. ‘. 4’, (2’) ‘ 4 , ‘, 4o ‘ 4 0 c 2”
N1TR0 E?l1EI E 41, (20 ‘ 2 o “ 40 ‘, 2’.’ ‘ o ‘ 4’, 4o I
1SUPFI ONE ‘ 4,.’ ‘ “ 2 ’ . 4o ‘ 2’ ‘ 4 ‘. 4u ‘. 40 ‘ 20
2—NUROPHEN’k ‘, 40 2” (20 ‘ 40 c 2’. (4” ‘ 4” ‘. 40 ‘ 2’.’
2,4—E’! E1H L PHENOL ‘ 4u ‘ 2’.’ ‘ 2” ‘ 40 ‘ 2v 4v ‘ 4” 40 • 2v
BI5 2-CHLOROEiHOX ETHA E ‘. 4 ’ .’ (20 ‘. 2” 4” “ 2” 4”' 4( 4 ‘. 2v
2,4—1 ’iC L0RUPHEHOL ‘ 40 ‘, 2o ‘ 2” ‘ 40 ‘, 2” ‘ 4v ‘ 4” * 4,) ‘,
i,2,4-TRI ’hLORO9EN ENE ‘ 4o 2’.’ 2)) ‘ 4u ‘. 2’.’ 4o ‘.4’) ‘. 40 ‘ 2o
NAPNTdALEME ‘, 40 ‘, 20 ‘. 2” 21v boO; 1 ’ ’Ov* lv ”Ot iovO4 buv0
4-CHLORO Mft1l E ‘. 4v 20 ‘ 20 (4’.’ (20 4’.’ 4’, 4’.’ ‘.2))
E ’ .HCHL0RO-i ,3—8UThD1ENE 40 •. 20 ‘, 2 ‘ 40 (20 ‘ 4( 4’.’ ‘40 2”
4-C i.ORO-3-flETHYL PHENOL c 40 ‘ . 2’.’ (2’) ‘. 4” 2” 4v ‘ , 4v ‘ 4” ‘, 2”
2-biEiH L N PHTHALENE c 40 20 (7o 75 i7o 2a0 Lao 2oo 15v
HEXACHLOROC CLUPENTHD1ENE 40 (2” ‘. 2” 4” c 2” ‘4’S’ ‘ 4” 40 ‘ 2v
2,4,b-IR ICHLOROPHEHC ’L ‘ 4v ‘. 2’.’ ‘. 2’) 4v 44 4’.’ 58 • 40 ‘ 2”
2,4. 5—TRICHL OPOPHENOL ‘ 4o ‘. 2” 7’, ( 4i ( 2’I 4’ ‘ , 4’ (4,) ‘, 2’.’
2CHLOPONAPHTHftE E ‘ 4 ) ‘ , 2o ‘ i v 4o ‘. 20 ‘, 40 ‘ 4o 40 ‘ 2”
2—4 ITROH 14 IL IME ‘. 4o (2’.’ ‘ 2’’ ‘. 4u 2” ‘. 4’ ) ‘. 4’.’ ‘ 4” (2”
OIMETWft PNTHAL TE ‘, 40 • , 2 ’ 2” ‘. 40 ‘. 2’ 4’.’ ‘ 4” ‘ 4o ‘
CEF4 FHTHftE E • 40 •: 20 ‘20 ‘. 40 Ia” 2 o 13” t9’ ’ Li ”
2. —1iROIt’L’iE E 40 ‘ 2” ‘ 2’.’ 4Q ‘ 20 ‘, 4” ‘. 4’.’ 40 ‘. 2’.’
4’.’ ‘ 2’.’ ( 2’.’ (4” c 2” 4” Lu ( 41’ c 2o
CEM F HTHE4E ‘ ‘ . ‘ ‘, 2” ‘, 2o 40 21, 4” ‘. 4’.’ c 4” ‘S 2’.’
2.4—01Mb fRUPHE UL 40 • 2” ‘ 2v 4’.’ 2’ . ’ 4v 4’’ 4” 20
4-HiiR P iENOL 40 ‘ 2’.’ ‘ 2” 4u ‘. 2’.’ ‘ 4’.’ ‘ 4u ‘ 4o ‘, 2u
Di E I0FuRkN 4’.’ “ 2v ‘, 2’.’ ‘ 4o 17’.’ 250 17” 23” 18’.’
2,4— i 1TRUTOLUEkE 40 ‘, 2” ‘, 2” ‘ 4v ‘. 2’) ‘. 40 ‘. L ’ , ‘ 4k . ’ ‘. 20
DIETHL PHTHAL TE < 4 ’ 2’) (2’.’ 140 •: 2” ‘ 4 • 4’, 2 ’ .’
4—CHLUP0FH [ N L-PHEMTL EIHEP ‘. 4’.’ ‘. 2o ‘, 2v ‘. 4o ‘ 2’.’ ‘. 4” ‘ 4” c 4o ‘,
FL’JO E ME (4” ‘. 2” •:io ( 41 44 5’, 4 15 75
B-179
r3ae I
-------
iaot . GC ,MS !creen data s’mtani tor C& ert Pains 2 Hanntoa1
8C;rlE FILE ho.: H1 1 HkM2 Mk 3 NI Ø Hths 5 Nt so Hiah i Hk 8 j 49
mcte naa& BLANk TR4IN s E TH. SETH. RUN I RUN 2 RUN 3 RUu 4 RUN 5 RUN
BL N EL,)(4
r 1o.ot i itE : 4 2 2 4 4 2
Oetecticn imit ‘tout uqi: 4” 2” 7” 4’) 2’ 4v “ 4t’ 2”
Coeoo’ine
4(’ 2’) L ) 40 ‘ 21 ? 4 0 ,‘ ‘ 4o ‘
4.e—01t4i iRc ’—z— ETd L PHENOL ‘4” 2” 2” ‘ 4” ‘ 2u 4o 4” 4” 2o
N—r4IiPO6U—0! Fh’EN’ LsMiNE ‘ 4” 2” 7” ‘, 4v 2 0 40 4’’ ‘ 4” 2”
4—HH0 )J?HEf4rL—PH€N1L EiHE 4u 2” ‘. 1” 4” 2o 4” 4’) ‘ 40 2”
NE ’ C HLUR& 8Et4iENE 4” £ 2” ‘ 2” ‘ 8v 2” 4 ’ ‘ 4’ ;
FE N 1 AC HL6 0FH wOL 4” / 2” 2’’ 4” 2” 4’’ 4’’ 4” ‘ 2’’
KN $T HRENE 4u 2” ‘ 2’’ ‘ 4” 7’’u 1 27” 15” 29” 2”o;
4NTHR CENE 4 ” 2” ‘, 2” 4u 22 4 ” ‘, 4u 4j 49
C E ’i iOLE ‘ 4 ’ ‘ £“ ‘. 2” ‘ 40 ‘ 2” ‘ 4 ‘ 4 ” 4” ‘.
0i—N— UT iL PHTHk TE ‘ 4 ’ , ‘ 2” ‘ 2 ” ‘ 40 ‘, 2” ‘ 40 ‘ 4’ ‘ 4” ‘ 2u
FLUORAIJTHENE ‘ 4” ‘ 2 ” ‘ 2’’ ‘ 49 77 Ru ‘ 8 ” 1 1’) 100
PYRENE ‘ 4)) ‘ 2 ” ‘. 2” ‘ 4” 41 48 ‘ 4 ’.’ a7 B R
BEN2TL SUTt PHTH LkTE ‘ ‘ 2’.’ ‘, 2” ‘ 4” M i ’ ‘ 4o ‘ 4” ‘ 40 ‘, 2o
3.3’ —O!CHLOPOBEN2 IBINE 4 ’. ’ 2” ‘ 2’’ ‘ 4’.’ ‘. 2’) ( 4 ” ‘4° ‘ 4’’ 20
BEN EIA]ANTHRACENE ‘ 40 ‘. 2” ‘ 2” ‘ 4’ ,’ ‘ 2” ‘, 40 ‘, 4” 4’) 7”
£HR’SENE ‘ 4o ‘. 2” ‘. 20 ‘. 4’.’ 38 “41) (40 57 b)
BIstz—ETHTLKE XYL:’RHTHNLATE ‘ 4’. ’ 37 4o ‘,I OV’ ‘ 1”v’ ‘.lou’ ‘ Io0 ‘ 100 ’ ‘ I o0
E’I—W—GCTeL PHTH LATE 4 ” ‘. 2o (2’) ‘. 4o c 2” ‘. 4o ‘. 4o c 40 “ 20
BEN2U IB)FLUORRNTHENE ‘ 4” ‘ 20 (20 ‘40 ‘ 20 ‘ 40 ‘ 40 4 O ‘. 20
BENZOU )RUQRANTHENE ‘ 4’,’ “ 70 ‘. 2’’ (40 “ 2’’ ‘ 4 ’ ’ ‘ 40 ( 4’’ K 2o
E N2O(MP \RENE ‘ 4 ” ‘, 20 ‘. 2” 40 ‘, 2” ‘, 40 ‘. 4” 4v ‘ 2 0
INDEN O I l 2, 3—C.O1P RENE ‘ , 4” ‘ 2’’ c 2” 40 ‘ 2’) ‘, 40 ‘, 4’’ ‘ 40 ‘ 2’)
OIBENZIA,H IANTHR ACENE ‘ 4’. , ‘ 2’) ‘ 2” ‘, 40 ‘ 2 )) ‘ 4 ,, ‘ “ ‘ 4o ‘ 2”
BENZO(6, H. (IPEPYLENE ‘, 4o ‘, 20 ‘, 2” c 40 ‘ 20 ‘ , 4” 4” ‘ 4” c 20
i Resnonse orsater than caliDr&ttcn curve. aiue is estimate onty.
B-180
-------
1 aoie . lentativety iaentitie L’311 0cjn27 in Hanrunal £eient un Eaiesicn
R(,tjS rILL No.: Hl6H1 H16H2 d1a 4 dIb,45 R 16t6 Hl& 7 Hloi* Hl6t4
Saaoie na,e: 8L4N TRftIN I IETH. HETH. RUN I RUN 2 RUN 3 UN 4 UN 5 RUN 6
ft NK ELIffik
No.otEci ltn: 4 2 2 4 2 4 4 2
Detecuon 1i it itotat u i: I I 1 1 I 1
N’Th-T R6ET N JUR5 local athount in uc
Name Scar Range
socy ano enzene 1 54
£‘ioec. oen:ene 3s9 252 157 54
( i berizene 388 i3 2
5uo c. ceozene 395 Se
122 44 476 22s 25 8
Suost. oenzene 42a L B S
‘Jr tno ”r 37
Un enown 52A 94
Pntr,elic annyorice 553 1i2
CI naontneiene Q 1
I ne 5 5 5
(2 naphtnaLene 515 55
(2 neonthelene t42
Sijbct. oen:ene h5’i 64
(2 rapntnatene t ni ane e57 o61 14” i v 133 1 6’ “
Suost. oenzene 678 o81 164 73 18’) ia 152 95
h l kane e68 lv
(3 naontna lene 7 2e 15 5
Naphtnaier,ecsrooxaidenyde 731 737 14 lBo 138 1i
Sunec. ben:ene 739 1’Z
roeiccnIorinateo unv nowr, ‘63 53
U naonthaiene 4 ni cornea ‘68 7’l 132 152 74
2nhr ,Owfl 82e 54
Au’ane 848 849 l aB 178
i ane l4
P nenantnrene ione 922 923 127 238 22’) 184
Phenaier,ore + 1 ane z ’46 lo2
Mlk ne 1228 18
‘ukane 1 S t ? 33
H Ir ane 18
B-181
-------
APPENDIX B-8
GALBRAITH LAB ANALYSIS RESULTS
B -183
-------
HARRY W GALBRAITH PH D KENNETH S WOODS GAIL R HUTCHENS VELMA N RUSSELL
CHAIRMAN OF THE EOARO PRC3IOEMT EXECUTIVE VICE PRE5IDEMT SECRETARY/TREABURER
GALER9HTH
_raLo’ ato’u ,
QUANTITATIVE MICROANALYSES
P.O. BOX 51610 ORGANIC — INOR I3ANIC 2323 SYCAMORE DR.
KNOXVILLE, TN 37950-1610 815/546-1335 KNOXVILLE. TN 37921-1750
Mr. Dan March August 1, 1990
Mid st Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110 Received: July 20th
f #114195
Dear Mr .March:
na1ysis of your caiiFounds gave the following results:
Your #, Our #, ny/liter ICC,
RuriP 1006 M6687 6
2 2006 M—6688 3
3 3006 M—6689 6
WAi14 ç CTI.rJ
f 4006 M—6690 6
6 of Lim( Skirly
5006 M—6691 8
6006 M—6692 8
B-185
LETTER AND SHIPMENTS BY U.S MAIL - P 0 BOX 31610. KNOXVILLE. TN 37930-1610 C THER CARRIERS 2323 SYCAMORE DR. KNOXVILLE. TN 3792 1 1750
ESTABLISHED 1950
-------
Mr.Dan March
Page 2
August 1, 1990
Your
#,
CAir #,
R’-h 1 2.
2004
M—6693
3
3004
M—6694
2
2008
M—6696
3
3008
M—6697
Sf
4008
M—6698
I4(l’P 4
5045
M—6699
Saxrple 4004 will be
BT(J/rourid,
10498 •)
j’ Uaus WASYf
9837 )
7828
8158 pe, I,ve4w sre
8709
8932
12630 t.i ID WA T
Sincerely yours,
G LBR ITh I BDPAaORflS, INC.
/ (
Gail R. Hutchens
F cec .Vice-President
H:np
% Cl,
1.83
1.57
1.01
1.35
1.69
1.51
1.72
ready later.
B-186
GALBRAITH LABORATORIES. INC.
-------
HC1 S m 1e Su
HC1 Train L Lution Train
Run 1
Caustic 1032 1020
Acidic 1033 1021
Rinse 1035 1024
Filter No filter 1025
Run 2
Caustic 2032 2020
Acidic 2033 2021
Rinse No rtnEe No rinse
Filter No filter 2025
Run 3
Caust.c 3032 3020
Acidic 3033 3021
Rinse 3034 No rinse
Filter 3035 3025
Run 4
Caustic 4032 4020
Acidic 4033 4021
Rinse 4052 4024
Filler 4035 4025
Run 5
Caustic 5fl32 5020
Acidic 5033 5021
Rinse 5034 5024
Filter 5035 5025
Run 6
Caustic 6032 6020
Acidic 6033 6021
Rinse 6034 6024
Filter 6035 6025
HC1 Test
Caustic 5045 5019
Acidic 5046 5050
Rinse 5047 5051
Filter 5048 5052
B-187
-------
HARRY W GALORAITH Pt .. 0
C AIRMAH OF YIIC BOARD
KENNETH S WOODS
PRCSIOENT
GAIL p HUTCHENS
XECUTiv( vICC PR 5ID HT
VELMA M RUSSELL
S CRCTARY/TREARURER
GALER9HTH
L 7 ago to ‘ri ,
QUANTITATIVE MICROANALYSES
ORGANIC — INORGANIC
615/546-1335
2323 SYCAMORE DR.
KNOXVILLE, TN 37921-1750
Mr. Dan March
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri
64110
Dear Mr.March:
Analysis of your compounds
Your #, Our #,
1020
1021
1024
1032
1033
5049
1035
1050
1051
1052
1048
1049
2020
2021
5050
2032
LETTER AND SHIPMENTS BY U S MAIL
M—6000
M—6001
M—6002
M—6004
M—6005
M—6003
M—6006
M—6007
M—6008
M—6009
M—6010
M—6011
M—6012
M—6013
M—6014
M—6015
gave the following results:
NH3 as N, K, C1
mg/liter ppm mg/liter
0.3 0.9 145
0.3 2.9 10
1.3 <0.6 101
9.0 32.6 613
6.3 31.3 378
0.3 <0.6 29
1.9 6.2 38
0.5 0.7 405
1.7 <0.6 248
1285 1.0 1034
1.3 11.2 <0.4
0.4 110 <0.4
0.3 <0.6 9
0.3 0.6 159
0.4 1.4
15.1 <0.6
P.O. BOX 51610
KNOXVILLE. TN 37950-1610
August 3, 1990
Received: July 17th
PC #1141 95
B-188
P 0 BOX 51610. KNOXVILLE. TN 37950-1610 OTHER CARRIERS 2323 SYCAMORE DR KNOXVILLE, TN 37921 1750
ESTABLISHED 1950
-------
Mr.Dan March Page 2 August 3, 1990
Your #, Our #, NH as N, K, Cl
mglliter ppm mg/liter
2033 M—6016 0.3 1.9 1
3020 M—6017 1.2 <0.6 230
3021 M—6018 0.6 2.5 54
5051 N1—6019 0.3 <0.6 <0.4
3032 M—6020 22.2 0.6 837
3033 M—6021 15.2 1.0 297
3034 M—6022 2.6 31.0 14
5045 M—6023 1.3 <0.5 164
4020 M—6024 0.9 <0.5 408
0.8 <0.6 424
4021 M—6025 0.6 <0.6 75
0.8 <0.6 71
4024 M—6026 0.4 2.1 2
0.4 2.1 2
5046 M—6027 28.1 0.8 9
4032 M—6028 17.6 <0.6 842
17.5 <0.6 861
4033 M—6029 9.9 <0.6 315
9.4 <0.6 358
4052 r 1—6030 4.1 39.6 5.9
3.2 40.2 5.8
5047 M—6031 0.2 302 2.4
5020 M—6032 <0.1 0.2 15.3
5021 M—6 033 0.3 0.7 2.5
5024 M—6034 2.8 <0.6 <0.4
6034 M—6035 1.0 15.5 7.7
5032 M—6036 42.1 <0.6 168
5034 M—6037 0.5 17.8 10.6
B-189
GALBRAITH LABORATOmIES. INC
-------
Mr.Dan March
Page 3
Your #,
6033
6020
6021
6024
6032
6025
5035
5025
6035
1025
2025
3025
5052
3035
4025
4035
5048
Our #,
M—6038
M—6039
M—6040
r4—6041
M—6 042
M—6043
M—6044
M—6045
M—6046
M—6047
M—6048
M—6049
M—6050
M—6051
M—6052
M—6053
M—6054
N I- s 3 as N,
14.8 mg/liter
<0.1 mg/liter
84.3 mg/Liter
7.6 mg/Liter
23.0 mg/liter
26.1 rig/fiLter
1248 g/fiLter
43.2 }Jg/f iLter
2410 pg/filter
40.5 pg/filter
87.2 pg/fiLter
8.7 pg/filter
52.3 pg/filter
32.6 pg/fiLter
64.8 pg/filter
73.8 pg/filter
29.6 pg/filter
26.8 pg/fiLter
31 .4 pg/fi Iter
Potassi urn,
14.6 mg/liter
<0.6 ppm
<0.6 ppm
<0.6 ppm
14.1 ppm
‘1860 pg/filter
30050 pc/fiLter
1575 pg/filter
14775 pg/filter
1525 pg/filter
3610 pg/filter
4515 pg/filter
1005 pg/filter
37950 pg/fiLter
6100 pg/filter
6060 pg/filter
62000 pg/filter
62500 pg/fiLter
24500 pg/fiLter
Chloride,
126 mg/liter
7.0 mg/liter
1.8 mg/liter
<0.4 mg/liter
133.6 mg/liter
1343 pg/filter
17201 pg/filter
1239 pg/filter
5250 pg/filter
1253 pg/fiLter
1805 .ig/filter
1574 pglfilter
1185 pg/filter
543 pg/filter
1835 pg/fiLter
1855 pg/fiLter
13276 pg/fiLter
13436 1 g/fiLter
729 pg/fiLter
SincereLy yours,
GALBRAITH LABORATORIES, INC.
R.
Gail R. I-kitchens
Exec .Vice—President
G H:np
B-190
August 3, 1990
GALBRAITH LABORATORIES. INC.
-------
HARRY W GALBRAITH PH 0
CHAIRMAN OF THE ROARD
KENNETH S WOODS
PRESIDENT
GAIL R HUTCHENS
EXECUTIVE VICE PRESIDENT
VELMA M RUSSELL
SECRETARY/TREASURER
GALf R9HTH
P.O. BOX 51610
KNOXVILLE, TN 37950-1610
QUANTITATIVE MICRC)ANALYSES
ORGANIC — INORGANIC
615/546-1335
Mr. Dan March
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
Dear Mr - March:
Analysis of your cat pound gave the following results:
Your f,
4004
Our#,
% Cl, ffJYJ/pound,
M—6695 1.69 10713
1.62 10396
August 2, 1990
Received: July 20th
jIf LI MIDWA$1C
Sincerely yours,
GALBPAITH
U RA PI , INC.
R. —1 - -
Gail R. Thitchens
E ec .Vice-President
GPH:np
B-191
LETTER AND SHIPMENTS BY U S MAIL P 0. BOX 5t6 10. KNOXVILLE. TN 37950-1610 O HER CARRIERS - 2323 SYCAMORE DR KNOXVILLE, TN 37921-1750
2323 SYCAMORE OR
KNOXVILLE, TN 37921-1750
ESTABLISHED 1950
-------
APPENDIX B-9
HC1 DATA
B-193
-------
Tables 1-7 of this appendix summarizE’ the data from the HC1 and HC1
dilution trains for each ion. A QA/QC dita table is also included. The
appendix also contains raw data on the HC1 CEM, HC1 dilution train and HC1
train. Note that the HC1 train used a VOST console and dry gas meter for run 1,
but was switched to a standard M5—style meter box and dry gas meter for the
remaining runs.
B-195
-------
TABLE 1 CHLORIDE ANALYSIS RESULTS FOR STACK MM5-HCI SAMPLING TRAIN
Total (b)
2 Front halt Rinse (c)
Filter (a)
Back hail Acidic
Caustic
10286
0258 2.710
0 3987
108043 30 475
3 Front halt Rinse (d)
Filter
Back halt Acidic
Caustic
14 0092 129k 1833
NA NA os43
837 04210 35238 3524
594 03490 20731 2073
1474 00012
02391
01406
1503 00124
00515
3,000 373 0105
71719 20229
42193 11901
16234 4579
NA = Not Applicable
a Sampling train was assembled without a filter
b Because the train was assembled without a filter, result can only be reported for the train as one component
c Sample was not collected during tab recovery of the sampling train
d Rinse volume is estimated as the sample volume remaining after analyses plus the estimated volumes removed by Galbraith
for these analyses
a Sample container was broken during shipment
I The stack ftowrato 013200 dscm/m is an estimate Measurement not performed during sampling
CL—
Stack gas
CL-
Impinger
Quantity
Total
sample
Stack
CL—
CL—
conc
volume
found
CL—
volume
CL—
flow
emission
emission
Run Train Component (mg/L)
(L)
(mg)
(mg)
(dscm)
(g/dscm)
(dscmlm)
(g/min)
(mol/min)
Front hatf Rinse
Filter (a)
Back halt Acidic
Caustic
38 00644
(a) (a)
613 01054
756 0 0947
(c) (c)
(a) (a)
152 01778
2 01041
2 45
(a)
6461
71 59
(c)
(a)
2703
021
Total (b)
0204 2.910
0 1330
27 13
38700 10916
4
Front halt
Rinse (d)
59
0086
051
1387
1 495
00093
3,480
32 28
0 910
Filter
NA
NA
133561
Back halt
Acidic
Caustic
852
674
05070
02556
431 96
17227
4320
17227
02889
01152
1005 50
401 00
28 361
11 311
5
Front half
Rinse
Filter
106
NA
0 1400
NA
1 48k
17201
18 68
3,150
39 15
1104
Back halt
Acidic
Caustic (a)
168
(a)
04611
(e)
7746
(a)
7746
(a)
6
Front half
Rinse (d)
Filler
77
NA
00610
NA
0
5 25 ’
572
1 502
00038
3.430
1306
0368
Back halt
Acidic
Caustic
1336
252
04955
02921
6620
7361
6620
7361
00441
00490
151 18
16810
4264
4741
HCI ( I)
Front half
Rinse
Filter
24
NA
0 0566
NA
0 14
0 729
0869
1 442
00006
3.200
1 93
0 054
Back halt
Acidic
Caustic
164 0
18
0 5353
01367
8779
246
8779
246
0 0609
00017
19482
546
5495
0154
B-196
-------
TABLE 2 POTASSIUM ANALYSIS RESULTS FOR STACK MMS-HCI SAMPLING TRAIN
K+
Slack gas
K’s ’
Impinger Quantity
Total
sample
Stack
K’s’
K’s.
conc
volume
found
K+
iolume
K+
flow
emission
emission
Run Train Component (mg/L)
(L)
(mg)
(mg)
(dscm)
(gldscm)
(dscm/m)
(g/min)
(mol/min)
1 Front halt Rinse 62 00644 040 0 258 2.710
Fitter (a) (a) (a) (a)
Back halt Acidic 326 0 1054 344
Caustic 31 3 0 0947 2 96
Total (b) 68 0 0264 71 43 1 827
2 Front halt Rinse (c) (c) (c) (c) 0204 2,910
Filter (a) (a) (a) (a) (
Back halt Acidic 06 0 1778 0 11
Caustic 1 9 0 1041 0 20
Total(b) 031 00015 442 0 113
3 Front halt Rinse (d) 31 0 0092 2 85 40 8 1 474 00277 3 000 83 04 2 124
Filler NA NA 37 95
Back halt Acidic 06 04210 0 25 06 00004 1 22 0031
Caustic 10 03490 035f
4 Front halt Rinse (d) 399 0086 343 6568 1 495 00439 3,480 152 89 3 910
Filter NA NA 62 25 f
Back halt Acidic 06 0 5070 0 30 0 45 00003 1 05 0 027
Caustic 06 02556 0 15
5 Front hall Rinse 1780 01400 249 3254 1 503 00217 3,150 6820 1 744
Filter NA NA 30 05 ç
Backhalt Acidic 06 04611 028 028 00002 059 0015
Caustic (e) (e) (e) (e) (e)
8 Front halt Rinse (d) 1550 00610 095 15725 1 502 00105 3,430 3591 0 918
Filter NA NA 14 775f
Back halt Acidic 14 1 0 4955 699k 11 25 0 0075 25 69 0 657
Caustic 146 02921 426ç
HCI (U Front halt Rinse 302 0 0566 1709 1 41 59 1 442 0 0288 3200 92 29 2 360
Filler NA NA 24 5
Back halt Acidic 0 5 0 5353 027 1 0 38 0 0003 0 84 0 022
Caustic 0 8 0 1367 0 11 ç
NA Not Applicable
a Sampling train was assembled without a filter
b Because the train was assembled without a filler, result can only be reported br the train as one component
c Sample was not collected during lab recovery ot the sampling train
d Rinse volume is estimated as the sample volume remaining after analyses plus the estimated volumes removed by Galbraiih
for these analyses
a Sample container was broken during shipment
The stack flowrate ot 3200 dscm/m is an estimate Measurement not performed during sampling
B-197
-------
TABLE 3 AMMONIUM ANALYSIS RESULTS FOR STACK MM5-HCI SAMPLING TRAIN
NM3
Stack gas
Nl-13
Impinger
Quantity
Total
sample
Stack
NH3
NH4+
conc
volume
lound
NH3
volume
NN3
110w
emission
emission
Run Train Component (mg/L)
(L)
(mg)
(mg)
(dscrn)
(gldscm)
(dscm/m)
(91mm)
(mat/mm)
1 Front half Rinse 1 9 00644 0 12 0258 2 710
Filter (a) (a) (a) (a)
Back hail Acidic 9 0 1054 0 95
Caustic 63 0 0947 0 60
Total (b) 1 67 0 0065 17 54 1 030
2 Front half Rinse (c) (c) (c) (c) 0204 2,910
Filter (a) (a) (a) (a)
Back halt Acidic 15 1 0 1778 2 68
Caustic 03 01041 003
Total(b) 271 00133 3866 2270
3 Front half Rinse (d) 26 0 092 0 24k 0 2726 1 474 00002 3 000 0 65 0 033
Filter NA NA 0 03265
Back half Acidic 222 04210 1465 00099 2982 1751
Caustic 152 0 3490 5 305
4 Fronl hall Rinse(d) 37 0086 032k 0 3482 1 495 00002 3,480 081 0048
Filter NA NA 0 02825
Back half Acidic 176 0 5070 8 92 1 11 4 00076 26 54 1 558
Caustic 9 7 02556 2 485
5 Front half Rinse 050 0 1400 0 1 318 1 503 00009 3.150 2 76 0 162
Filter NA NA 1 248
Backhalt Acidic 421 04611 1941 1941 00129 4068 2389
Caustic (e) (c) 0 3367 Cc)
6 Front half Rinse(d) 1 00 00610 0 061 2 47 1 502 00016 3.430 564 0331
Filter NA NA 241 5
Backhalt Acidic 23 04955 1140k 1572 00105 3590 2108
Caustic 148 02921 432j
MCI (f) Front half Rinse 020 00566 001 00414 1 442 0 00003 3 200 0 09 0005
Filter NA NA 003145
Back half Acidic 1 3 05353 069591 4 536 00031 1007 0591
Caustic 28 1 0 1367 384
NA Not Applicable
a Sampling train was assembled without a filter
b Because the train was assembled without a fitter, result can only be reported for the train as one component
c Sample was not collected during lab recovery of the sampling train
d Rinse volume ie estimated as the sample volume remaining alter analyses plus the estimated volumes removed by Galbraith
for these analyses
o Sample container was broken during shipment
I The stack flowrate of 3200 dscmlm is an estimate Measurement not performed during Sampling
B-198
-------
TABLE 4 CHLORIDE ANALYSIS RESULTS FOR l)ILUTION SAMPLING TRAIN
CL— Stack gas
CL— Impinger Quantity Total sample Stack CL— CL—
conc volume found CL— volume CL— flow emission emission
Run Train Component (mg/L) (L) (mg) (rn )) (dscm) (g/dscm) (dscmlm) (g/min) (mol/min)
1 Fronthalf Rinse(b) 101 00410 414’ 539 0199 00271 2710 7344 2072
Filter NA NA 1 253J
Back half Acidic (a) 145 0 1830 2384 2384 0 1188 321 93 9 081
Caustic (a) 20 0 1360 272 272 00137 3704 1 045
2 Front half Rinse (c) (c) (c) 1 81 0 187 00097 2,910 2809 0792
Filter NA NA 1 805
Back half Acidic 9 01199 108 108 00058 1681 0474
Caustic 318 01101 3501 3501 01272 54481 15367
3 Front half Rinse (c) (C) (c) 1 57 0 183 00086 3.000 2580 0 728
Filter NA NA 1 574
Back half Acidic 233 00789 18 15 18 15 00992 29754 8393
Caustic 108 00939 1014 1014 00554 16623 4689
4 Front half Rinse (b) 2 0039 008k 1 93 0211 00091 3.480 31 75 0896
Filter NA NA 1 845 J
Backhalf Acidic 418 01237 5148 5146 02439 84872 23939
Caustic 146 01174 1714 1714 00812 28269 7974
5 Front half Rinse (b) 04 0043 002 1 26 0 117 00108 3,150 3390 0956
Filtor NA NA 1 239 ç
Back half Acidic 153 0 1269 1 94 1 94 00166 5223 1 473
Caustic 50 01084 054 054 00046 1454 0410
6 Front half Rinse 0 4 0 0250 001 1 35 0238 00057 3.430 1950 0 550
Filter NA NA 1 3 4Sf
Back half Acidic 70 01095 077 077 00032 1110 0313
Caustic 36 01044 038 038 00016 548 0154
HCI (d) Front half Rinse (b) 04 00400 002 1 21 0 164 00073 3.200 2351 0663
Filter NA NA 1 185J’
Back half Acidic 290 0 1350 392 392 00239 7649 2 157
Caustic 80 01111 089 089 00054 1737 0490
NA Not Applicable
a lmpinger volumes were estimated as the sample volume remaining after analyses plus the estimated volumes removed by
Galbraith for these analyses
b Rinse volume is estimated as the sample volume remaining after analyses plus the eslimated volumes removed by Galbraith
for these analyses
c Sample was not collected during lab recovery of the sampling train
d The stack flowrate 013200 dscm/m is an estimate Measurement not performed during sampling
B-199
-------
TABLES OTASSUM ANALYSIS RESULTS FOR DILUTION SAMPLING TRAIN
K. Stack gas
K. Impinger Cuaniity Total sample Stac K. K.
COnc volume found K+ volume K+ flow emission emission
Run Train Component (mg/LI (L) (mg) (mg) (dscmj (g/dscm) (dscm mi (g/min) (mol/min)
1 Front hail Rinse(b) 06 0 0410 002 1 55 0 199 0 0078 2 70 21 04 0 538
Filler NA NA 1 525
Back half Acidic (a) 0 9 0 1630 0 15 0 54 00027 7 35 0 188
Caustic (a) 2 9 0 1360 0 39 f
2 Front half Rinse (ci (c) (c) (c) 361 0 187 00193 2 910 56 18 1 437
Filter NA NA 3 61
Back halt Acidic 06 01199 007 014 00007 218 0056
Caustic 06 01101 007
3 Front half Rinse (c) (ci (c) (c) 4 52 0 183 00247 3 000 74 02 1 893
Filter NA NA 4515
Back hall Acidic 06 00789 005 028 00015 459 0 117
Caustic 2 5 00939 0 23 ç
4 Front half Rinse(b) 2 1 0039 008 6 18 0 211 00292 3 480 101 60 2 598
Filter NA NA 608
Back half Acidic 06 01237 007 0 14 00007 2 31 0059
Caustic 0 8 0 1174 007 f
5 Front hall Rinse (b) 060 0043 003 1 61 0 117 00137 3.150 43 21 1105
Filler NA NA I 575
Back half Acidic 0 2 0 1269 0 03 0 11 0 0009 2 96 0 076
Caustic 070 0 1084 008 f
6 Front half Rinse 060 00250 002 1 88 0 238 00079 3 430 2709 0693
Filler NA NA 1 86 f
Back hall Acidic 060 0 1095 007 0 13 00005 1 87 0048
Caustic 060 01044 006 f
NCI (d) Front half Rinse (b) 060 00400 002 1 03 0 164 0 0063 3 200 2000 0 511
Filter NA NA 1 005
Back half Acidic 0 6 0 1350 008 024 00015 4 68 0 120
Caustic 1 4 01111 016
NA = Not Applicable
a Impinger volumes were estimated as the sample volume remaining alter analyses plus the estimated volumes removed Dy
Galbrailh for these analyses
b Rinse volume is estimated as the sample volume remaining after analyses plus the estimated volumes removed by Galbraith
for these analyses
c Sample was not ccllected during lab ecovery of the sampling train
d The stack flowrate 013200 dscm/m is an estimate Measurement not performed during sampling
B-200
-------
TABLE 8 AM .1CNIUM ANALYSIS RESULTS FOR DILUTION SAMPLING TRAIN
NH3
Impinger
NH3
Cuaritily
ToIaI
Slick gas
ssmple
Slack
NH3
Nl-44+
COnc
volume
found
NH3
vDlume
Nk3
flow
emission emission
Run Train Component (mg/L)
(L)
(mgi
(mg)
(.iscm)
(g/dscm)
(dscmfmj
(9/mm)
(mol/min)
1 Front half Rinse (b) 1 3 00410 0 05 009 0 199 00005 2 710 1 23 0072
Filler NA NA 0 0405 f
Back half Acidic (a) 0 3 0 1630 0 05 0 09 0 0005 1 23 0 072
Caustic (a) 0 3 0 1360 0 04 f
2 Front half Rinse (C) (c) (c) (C) 009 0 187 00005 2 910 1 36 0080
Filter NA NA 0 0872
Back half Acidic 03 0 1199 0 04 0 07 0 0004 1 09 0 064
Caustic 03 01101 003 f
3 Front half Rinse (c) (c) (c) (c) 0 01 0 183 000005 3.000 0 14 0008
Filter NA NA 0 0087
Back half Acidic 1 2 00789 0 09 1,, 0 15 0 0008 2 46 0 144
Caustic 0 6 00939 0 06
4 Front hall Rinse (b) 04 0939 0 02 009 0 211 00004 3 480 1 47 0 086
Filter NA NA 0 0693
Back halt Acidic 09 01237 011 ‘ 019 00009 313 0184
Caustic 07 01174 008
5 Front half Rinse (b) 2 80 0043 0 12 ‘k 0 16 0 117 00014 3 150 439 0258
Filter NA NA 0 0432 f
Back half Acidic 0 1 0 1269 0 01 0 04 00003 1 08 0 063
Caustic 0 30 0 1084 0 03
6 Front half Rinse 760 00250 0 19 022 0 238 0 0009 3.430 3 11 0 183
Filter NA NA 0 0261
Back halt Acidic 0 10 0 1095 0 01 8 81 00370 12697 7 455
Caustic 84 30 0 1044 8 80
HCI (d) Front half Rinse (b) 0 30 00400 0 01 006 0 164 00004 3,200 1 22 0 071
Filter NA NA 0 0523 f
Back halt Acidic 0 3 0 1350 0 04050 1,, 008 00005 1 57 0 092
Caustic 04 01111 004 J
NA = Not Applicable
a lmpinger volumes were estimated as the sample volume remaining after analyses plus the estimated volumes removed Dy
Gaibraith l r these analyses
b Rinse volume is estimated as the sample volume remaining after analyses plus the estimated volumes removed by Galbrailh
for these analyses
C Sample was not collected during lab recovery of the sampling train
d The stack flowrale of 3200 d cm/m is an estimate Measurement not performed during sampling
B-201
-------
r.’)
TABLE 7 ION PERCENTAGES FOUND IN SAMPLING TRAINS
(Shading indicates a complete data set
Dilution Train
Stack HCI Train
CL-
emission
(g/min)
K+
emission
(glmin)
NH3
emission
(glrnin)
CL-
emission
(g/min)
K+
emission
(9/mm)
NH3
emission
(glmrn)
Run 1
Front Half
73 44
17.0°!
21 04
74 1°!
1.23
500%
NA
NA
NA
NA
NA
NA
Back Half
Acidic
321.93
74 4°!
7.35
25 9°A
1 23
500%
NA
NA
NA
NA
NA
NA
Caustic
37 04
8 6°!
NA
NA
Total
43241
2839
246
108043
7143
1754
Run 2
Front Hall
28 09
4 8°!
56 18
96 3°i
1 36
55 5%
NA
NA
NA
NA
NA
NA
Back Half
Acidic
16 81
2 9°!
2 18
3 7 /
1 09
44 5%
NA
NA
NA
NA
NA
NA
Caustic
544 81
92 4°!
NA
NA
Total
589 71
58 36
2 45
387 00
4 42
38 66
Run 3
Front Half
25 80
5 3°i
74 02
94 2°i
0 14
5 5%
3 73
0 3°i
83 04
98 6°!
0 55
1 8°A
Back Half
Acidic
297 54
60 8°i
4 59
5 8°i
246
94 5%
717 19
62 8°i
1 22
1 4°!
29 82
•
98 2°!
Caustic
166 23
34 0q
421 93
36 90/
Total
48957
7861
260
114285
8426
3037
Run 4
Front Half
31 75
2 7°!
101.60
978°!
1 47
320%
32 28
2 2°/
15289
99 3°!
081
3 0°!
Back Half
Acidic
848 72
73 O°i
2 31
2 2°!
3 13
680%
1005 50
69 9°i
1 05
0 70!
2654
97 0°!
Caustic
282 69
24 3°!
401 00
27 9°i
Total
116316
10391
460
143878
NA
15394
2735
Run 5
Front Half
33 90
33 70i
43 21
936°!
4 39
803%
39 15
68 20
NA
2 76
NA
Back Half
Acidic
52 23
51 9°!
296
6 40!
1 08
197%
162 34
NA
059
NA
4068
NA
Caustic
14 54
14 4°!
NA
NA
Total
100.67
46 17
5 47
NA
3901
NA
NA
Run 6
Front Half
1950
54 0°i
27.09
935°!
3 11
24%
1306
3591
58 30!
564
136°!
Back Half
Acidic
11 10
308°!
1 87
6 5°A
126 97
976%
151 18
45 5°i
25 69
41 7°!
3590
864°!
Caustic
5 48
15.2°!
168 10
50 6°!
Total
3608
2896
13008
33234
6160
4154
HCL Run
Front Half
23 51
20 0°
20 00
81 0°!
0 20
111%
1 93
1 0°!
92 29
99.1 °.4
0 09
0 9°!
Back Half
Acidic
76 49
65 2°!
4 68
19 0°!
1 57
889%
194 82
96 3°i
084
0 9°!
1007
99 10/
Caustic
17 37
14 8°!
5 46
2 7°!
Total
11737
2468
1.77
20221
9313
1016
NA = Not Available (See Tables 1 through 6), Front hall/back half comparisons not possible without filter, or broken sample bottle prohibits comparison
-------
SUMMARY OF HCI QAJQC SAMPLES
QNQC Samples
Sample
Prepared
Measured
Percent
No.
Ion
Value
V Iue
Error
1048
K+
100 ppm
110
100
1049
K+
10 ppm
11.2
12.0
1050
Cl—
400 mg/L
405
1 3
1051
Cl—
200 mg/L
248
24 0
1052
CI—
1000 mg/L
1 034
3 4
Replicate Samples(a)
Sample
No. NH3(mg/L) K(ppm) Cl(rngIL)
4020 09 <0.5 408
(acid) 0 8 <0.6 424
4021 06 <06 75
(caustic) 0 8 <0 6 71
4024 04 21 2
(rinse) 0.4 2.1 2
4025 648 6100 1835
(filter) 73 8 6060 1855
4032 17.6 <0.6 842
(acid) 17 5 <0.6 861
4033 99 <0.6 315
(caustic) 9 4 <0.6 358
4052 41 396 5.9
(rinse) 3 2 40.2 5.8
4035 296 62000 13276
(filter) 26.8 62500 13436
(a) — All samples are from Run 4; 4020—4025 HCI Dilution,
4032—4052 HCI train
Note — All fitters are in total ug/filter, not mg/L or ppm
B-203
-------
B-204
-------
HC1 DILUTION TRAIN RATIOS
Run Dilution ratio
1 31.4
2 35.1
3 42.1
4 33.2
5 32.5
6 24.9
HC1 42.4
B—205
-------
HC1 Continuous Honitor
B-207
-------
Filename:RUNS
Name: RUNS
Date:07-05-1990
Location:HANNIBAL, MO
Project9 lO2-63-13
Operator.BG
VERSION =05/07/90
TIME HCI
1- 10 @7%02
(ppm,dry) (ppm,dry)
1220 18.9 15.7
1221 15.8 118
1222 15.1 12.3
1223 15.6 12.9
1224 16.1 13.5
1225 14.4 120
1226 12.5 10.2
1227 12.6 10.2
1228 12.5 10.2
1229 21.0 17.7
1230 27.5 23.3
1231 21.6 1&2
1232 16.1 13.4
1233 1&4 15.4
1234 25.4 21.7
1235 30.5 20.3
1236 25.1 16.7
1237 15.4 10.3
1238 16.5 11.0
1239 14.4 9.6
1240 12.6
1241 11.2 7.5
1242 10.3 f 9
1243 13.2
1244 16.7 11.1
1245 13.7 9.1
1246 16.3 10.9
1247 24.2 20.2
1248 21.6 1&2
1249 29.8 24.9 8-209
-------
1250 21.6 1&4
1251 13.0 11.0
1252 12.6 10.7
1253 11.4 9.2
1254 15.6 12.3
1255 13.2 10.8
1256 12.5 10.8
1257 10.3
1258 11.9 10.1
1259 15.8 13.8
1300 13.3 11.6
1301 13.9 12.1
1302 14.2 12.2
1303 13.3 11.4
Port change
1319 12.8 10.2
1320 13.2 12.2
1321 12.1 10.7
1322 12 .5 10.7
1323 11.4 9.7
1324 14.4 12.1
1325 12.5 10.6
1326 11.6 9.9
1327 11.4 9.8
1328 14.4 12.4
1329 19.5 16.9
1330 14.2 12.3
1331 10.9 9.4
1332 12.5 10.5
1333 12.5 10.4
1334 16.3 13.8
1335 15.6 13.2
1336 14.0 11.7
1337 11.9 9.7
1338 15.4 12.5
1339 21.7 1&2
1340 14.4 12.2
1341 11.9 10.1
1342 13.2 11.4
1343 11.1 9.5
1344 10.5 &9
1345 ii.g 10.6
1346 14.7 13.1 B-210
-------
1347 13.9 11.6
1348 13.2 11.4
Port change
1408 8.9 7.8
1409 9.1
1410 9.3
1411 7.1
1412 8.1 7.0
AVG= 12.2
MIN = 6.9
MAX= 24.9
HO = Hydrochloric acid
B—211
-------
Filename:RUN5A
Name:RUNSA
Date: 07-02-1990
Location:HANNIBAL, MO
Projec 91 02-63-13
Operator: BG
VERSION =05/07/90
HO
TIME HO @7%O2
(ppm, dry) (ppm, dry
1647 57.0 54.3
1648 51.2 48.8
1649 61.2 5&3
1650 76.3 72.7
1651 47.7 45.4
1652 61.9 59.0
1653 49.8 47.4
1654 51.9 49.4
1655 4&4 46.1
1656 53.5 51.0
1657 57.9 55.1
1658 65.6 62.5
1659 61.4 58.5
1700 51.9 ‘494
1701 48.1 45.8
1702 61.9 59.0
1703 63.0 60.0
1704 55.6 53.0
1705 46.5 44.3
1706 43.3 41.2
1707 41.2 39.2
1708 44.2 42.1
1709 57.4 54.7
1710 62.6 59.6
1711 57.2 54.5
1712 45.8 43.6
1713 44.4 42.3
1714 52.6 50.1
1715 42.1 40.1
1716 39.8 B-212
-------
1717 35.8 34.1
1718 33.0 31.4
1719 37.4 35.6
1720 30.2 28.8
1721 30.0 28.6
1722 36.7 35.0
1723 47.7 45.4
1724 41.9 39.9
1725 34.2 32.6
1726 30.9 29.4
1727 30.5 29.0
1728 32.3 30.8
1729 29.3 27.9
1730 28.6 27.2
1731 26.0 24.8
1732 28.1 26.8
1733 56.1 53.4
1734 41.6 39.6
1735 45.4 43.2
1736 38.4 36.6
1737 34.4 32.8
1738 27.9 26.6
1739 24.7 23.5
1740 33.3 31.7
1741 36.7 35.0
1742 30.5 29.0
1743 30.9 29.4
1744 26.5 25.2
1745 26.0 24.8
1746 23.7 226
1747 46.7 44.5
174.8 47.0 44.8
1749 38.6 36.8
1750 37.7 35.9
1751 28.4 27.0
1752 26.7 25.4
1753 27.2 25.9
1754 30.9 29.4
1755 30.0 2.8.6
1756 24.7 23.5
1757 25.1 23.9
1758 27.4 26.1
1759 27.9 26.6
B-213
-------
1800 21.9 20.9
1801 29.3 27.9
1802 22.8 21.7
1803 21.9 20.9
1804 18.4 17.5
1805 20.9 19.9
1806 39.3 37.4
1807 30.7 29.2
1808 27.4 26.1
1809 25.4 24.2
1810 17.4 16.6
1811 21.9 20.9
1812 25.6 24.4
1813 22.6 21.5
1814 29.1 27.7
1815 24.0 22.9
1816 24.2 23.0
1817 24.2 23.0
1818 26.3 25.0
1819 20.9 19.9
1820 16.3 15.5
1821 19.1 1&2
1822 16.7 15.9
1823 20.7 19.7
1824 1&8 17.9
1825 18.6 17.7
1826 17.9 17.0
1827 16.5 15.7
1828 20.2 19.2
1829 14.2 13.5
1830 15.1 14.4
1831 21.4 20.4
1832 17.7 16.9
1833 15.6 14.9
1834 12.8 12.2
1835 12.1 11.5
1836 9.5 9.0
1837 9.5 9.0
1838 9.5 9.0
1839 14.9 14.2
1840 28.6 27.2
1841 21.2 20.2
1842 24.2 23.0
B-214
-------
1843 16.0 15 ,2
1844 11.4 10.9
1845 17.9 17.0
1846 12.8 12.2
1847 14.4 13.7
AVERAGE= 31.4
MINIMUM = 9.0
MAXIMUM= 72.7
AVERAGEO2= 6.3
B—215
-------
HC1 Dilution Probe Raw Data
B-217
-------
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B-229
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H-c i T k/’
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Ce, o,rl-
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Opera t or
Test No.
Pressure
( .s1
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Desired Flow Rote (cc/min)_
9___
Total Sampling Time ________
Average Flow Rote (cc/mm, l/min
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Estimated Actual Volume (liters) 2.66. 7g 5
Time
24 Hr Clock
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-------
FIELD \TA
NOZZLE DIA ____________
ASSUMED MOISTURE S —
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—
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SITE TO BARO ELEVATION (II
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SCHEMATIC OF TRAVERSE
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-------
MIDWEST RESEARCH INSTITUTE
Run Nunther ______________ Project Number / C2 6J—i3
, -)_, —
Date -‘ - •;iC
Plant ( c .e ,/? /
Sampling
Location c
FIELD CREW
Crew Chief __________
Testing Engineer ___________
Assistant Testing
Engineer ____________
Process Engineer ___________
Other ___________
B-234
-------
RUN NO
PROJECTNO c)/p 1 ?
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MIDWEST RESEARCH IN ;TITUTE
Run Nu tber 9 Project Number 6 L
Date 6 2-39O
Plant ( h’/
Sa mpling
Location ________________________
FIELD CREW
Crew Chief ________
Testing Engineer ___________
Assistant Testing
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Process Engineer ___________
Other ____________
B-237
-------
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MIDWEST RESEARCH INSTITUTE
Run Number _____
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Crew Chief
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Assistant Testing
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Process Engineer
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Plant
B-240
-------
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-------
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/ -
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B-243
-------
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-------
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-------
MIDWEST RESEARCH INSTITUTE
Ru n Number
Project Number _____________
Sampling
Location
Crew Chief
Testing Engineer
Assistant Testing
Engineer
flo p_i f\o R,C
R ft
Process Engineer
Other
sco 1 ±- )dc- w
Date
Plant __
/
FIELD CREW
B-246
-------
SAMPUNG LOCATION S+c _ c _ t( 0 I
PROJECTNO. qlol— (. 3-(3
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DATE
SAMPLING LOCATION 5 t’ _ cj( _ . t, .4
SAMPLE TYPE J t C. L
OPERATOR , .i K. G . (L .
FILTER NO Pt
RECORD DATA EVERY _________ W IN
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PROBE No _______________
PROSE LENGTH AND 1YPE •7 2 ’
SAMPLE BOX NO _____________
METER BOX NO L /
TEMP. OONTROUIR NO _____
TEMP. METER NO. ____________
THERMOCOUPLEID NO
UMBILICAL. CORD I 0. NO
UMB 1UCAI. CORD ID NO
NOZZLE NO ______
FIELD P A TA
____ NOZZLE DIA ____________
D S ASSUMED MOISTURE % ______________
METERAHO I. SC )
______ METER CORRECTION
______ ________ PITOT NO. ___________________________
_______ PITOT COEFFICIENT __________________
_______ BAROMETRIC PRESSURE ________________
( A _____ SITE TO BARO EI.EVATION II 0
CORBECTEDBP(0I il1OOIIJ
_______________ STATIC PRESSURE S
PIlOT LEAK CHECK , 3” II O
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FINAL
TIME (24 lir)
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TIME (24_lv)
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TIME (24 Iii)
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FINAL
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L I
INITIAL VOLUME ______
FINAL VOLUME ________
E.LAXCHECKVOLUME
ADJUSTED FINAL VOLUME
COMMENTS
nt%*m ii/lIlfl
-------
APPENDIX B-b
bC ANALYSIS RISULTS
This appendix contains results of TOC analysis on the lime slurry samples
and calculations of total TOC. A brief summary of the pyrolysis GC/MS analysis
is also included.
Slurry density and % water were calcul Lted by MRI’s labs. Known aliquots
of slurry were weighed to determine the density. Solid and liquid fractions
were obtained by filtering the aliquot, drying the filter cake, and weighing to
allow calculation of % solids.
B -249
-------
Calculation of Overall TOC for Lime Slurrys
Lime Slurry
Composition Measured Measured TOC Quanti Overall
Pun Fraction (¾ solid/liq) TOC(%) bC (mg/L) (mg) TOC (¾)
1 Solid 61 0 0 12 0 0732
Liquid 39 0 6 0 0002
Total 0 0734 0 073
2 Solid 59 3 0 55(b) 0 3262
Liquid 40 7 3 0 0001
Total 0 3263 0 326
3 Solid 51 6 3 04(c) 1 5686
Liquid 48 4 6 0 0003
Total i 5689 1 57
4 Solid 66 1 0 55 0 3636
Liquid 33.9 6(b) 0 0002
Total 0 3638 0 364
5 Solid 70 1 088 06169
Liquid 29 9 8 0 0002
Total 06171 0617
6 Solid 68 6 0 33 0 2264
Liquid 31 .4 8 0 0003
Total — 0 2267 0 227
(a) — Basis of 100 g sample total, water density of 1 g/mL
(b) — Average of two replicates
(C) — Duplicate analysis performed to verify measured value
B-251
-------
U E Geochemical and Environmental Research Group
I Ten South Graham Road
L A College Station, Texas 77840
TEXAS A&M UNIVERSITY
Telephone (409) 690-0095
FAX (409) 690-0059
TELEX. 910-380-8722 1 August 1990
Scott Klamm
Midwest Research Institute
425 Volker Blvd.
Kansas City, MO
Dear Scott:
Enclosed are TOC analysis results for the Industrial cement kiln
study (per GERG SOP-8907). These samples were particularly difficult
to analyze and the following comments should be noted. A number of
samples could not be dried even after several days of exposure in a
recirculating oven at 50°C. This affected our ability to obtain an
accurate sample weight and apparently the samples were moist with
something other than water. The values on many samples approach
the detection limit of the method (—0.05%). The samples were
inhomogenous causing more than usual scatter In replicate analyses.
Average TOC values are reported for each sample with replicates
provided for the samples as requested. If you have any questions,
please call.
Sincerely yours,
Mahlon C. Kennicutt II. Ph.D.
Associate Research Scientist
MCK/dep
enclosure
B-252
-------
Table 1. Total organic carbon content of Industrial cement kiln
samples.
• Sample I.D. TOC (%)
Rw,J I 1006 0.12 €o ID: .- crp.il
2006 0.85, 0.25 f
3 3006 3.04
V 4006 0.55 L.me Sku’ry
5006 0.88
6 6006 0.33
B—253
-------
—. (
U E I Geochemical and Environmental Research Group
I J Ten South Graham Road
L — College Station, Texas 77845
TEXAS A&M UNIVERSITY
Telephone (409) 690-0095
FAX (409) 690-0059
TELEX 910.380-8722
November 29, 1990
Scott Klamm
Associate Environmental Engineer
Midwest Research Institute
425 Volker
Kansas City, MO 64110
Dear Scott,
We have analysed the two samples which you sent to us earlier
this month. The shale sample contained 1.8 % TOC while the limestone
sample was below our level of detection. The anaysis was performed on
a Leco furnace using the same procedure as we used on previous samples.
If I can be of further assistance, please feel free to contact me.
Sinci
Research Associate
B-254
-------
HARRY W GALBRAITH Pn 0 KENNETH 5 WOODS GAIL R HUTCHENS VELMA M RUSSELL
CHAIRMAN O THC BOARD PRESIDENT EXECUTIVE VICE PRESIDENT SECRETARY/TREASURER
GAL1 R91I{FfH
_‘ago’7aLow .4,
QUANTITATIVE MICRC)ANALYSES
P.O. BOX 51610 ORGANIC — INOR’ ANIC 2323 SYCAMORE DR.
KNOXVILLE, TN 37950-1610 615/546-1335 KNOXVILLE. TN 37921-1750
Mr. Dan March August 1, 1990
Midwest Research Institute
425 Vofl(er Boulevard
Kansas City, Missouri 64110 Received: July 20th
PO 114195
Dear Mr .March:
Analysis of your xiTpounds gave the fo1lo ing results:
Your 4 , Our 4t, i g/liter ¶1tx2,
JJ 1006 M—6687 6
2006 M—6688 3
3 3006 M—6689 6 W# ’IER Fq C1I.SJ
4’
‘f 4006 N-6690 6 1..IM(. S vrvyS
5 5006 M—6691 8
4 6006 M—6692 8
B-255
LETTER AND SHIPMENTS BY U S MAIL - P 0 BOX 51610. KNOXVILLE. TN 37950-1610 CTHER CARRIERS - 2323 SYCAMORE DR KNOXVILLE. TN 37921 1750
ESTABLISHED I95
-------
SUMMARY OF PYROLYSIS ANALYSIS OF SHALE ANO LIMESTONE SAMPLES
Each of the two solid materials was analyzed by the technique of thermal
desorption-GC/MS. Small aliquots (approximately 10 mg) of the material was
placed in a quartz sample tube. For the limestone sample, the material appeared
rather heterogeneous, so care was taken to include some of the sandy portion of
the material as well as some chunks of the rocky portion.
Thermal desorption-GC/MS analysis of the samples was conducted using the
conditions listed in Table 1. A typical experiment is begun by mounting the
sample in the pyrolysis probe, inserting the probe Into the interface to the GC
and initiating the heating cycle. Once the thermal desorption event is
concluded, the probe is removed and the GCIMS analysis Is started. Analytical
data is acquired in the conventional full-scan GC/MS mode.
The CC/MS instrumentation was calibrated daily for mass assignment. A
blank, consisting of an empty sample tube, was analyzed prior to the analysis of
the samples. Replicate analysis of the shale material was conducted.
For each material, the major CC/MS peaks were tabulated and tentatively
identified based upon their mass spectral library search results. The abundance
of each GC/MS peak relative to the other identified peaks was computed. In
addition, specific mass chromatograms were plotted to determine the overall
characteristics of the materials. Results are tabulated overleaf.
B-256
-------
Table 1. Experimental parameters for therrnal desor’ption-GCIMS analysis
of shale, limestone, and raw meal composite.
Mass Si,ectrometi-v
Instrument: Finniga JMAT 4000
Ionization Mode: 70 eV electron ionization
Source ionizer temperature: 170°C
Resolution: unit
Scan rate: 1.0 s/scan
Scan range: 40-500 amu
Data system: Finnigan/MAT INCOS
Gas Chromatoeraphv
Instrument: Hewlett-Packard 5890
Column: DB-5 (J & W Sthentific)
30 m x 0.25 mm i.d.
Injector Temperature: 270°C
GC/MS interface type: Direct coupling
Interface temperature: 280°C
Carrier gas: He at 7psi
Temperature program: 40°C - 00°C at 10°C/mm,
initial hold for 4 minutes
Thermal Desorption
Instrument: Chemical Data Systems Model 122
Extendsd Pyroprobe
Probe type: Pt coil probe
Desorption temperatures: 500°C
Desorption time: 1 rninu e
Sample split: 30:1
TD-GC interface temp.: 250°C
B-257
-------
Results from duplicate analyses of shale samples.
% Total Peak
Area _
Run#2
%RD 3
Tentative Identification 1 Scan No. Run#1
Air 18 -
-
-
Air 65 -
-
-
Cycloalkane 218 1.0
0.9
12
Alkane 246 2.6
1.4
59
Cycloalkane 5 6.0
3.5
52
Unknown 310 2.9
0.8
117
Xylene 340 3.4
4.5
27
Alkane 378 5.7
7.2
Z3
Alkane 430 4.6
5.4
17
Alkene 448 3.8
3.5
8
Alkane 468 2.8
3.5
Alkane 500 6.3
10.2
48
Alkane 526 6.9
6.2
10
Alkane 552 1.6
1.5
5
Alkane 565 2.9
2.6
12
Alkane 588 1.6
1.8
U
Alkane 610 7.0
8.3
17
C4-Aikylbenzene 665 3.1
6.1
65
Alkane 708 6.3
6.5
3
Alkane 721 3.8
3.3
13
Alkane 775 2.9
2.6
12
Alkane 799 7.7
6.5
16
Alkane 884 3.9
4.6
16
Alkane 934 1.6
0.1
181
Alkane 963 3.7
3.1
17
Alkane 1039 3.0
1.1.
93
Alkane 1074 0.6
1.4
80
Alkane 1110 1.4
1.1
27
Alkane 1115 1.1
1.0
14
Alkane 1177 0.7
0.5
25
Alkane 1242 0.5
0.4
24
Alkane 1303 0.5
0.3
43
1. Tentative identification given to GC1MS peak.
2. Percent of the total area for the peaks in this table.
3. %RD=percent relative difference.
B -258
-------
Results for thermal desorption-GCIMS of limestone.
Tentative Identificationl Scan No. Peak Area % Total Area 2
Air 6 151680 -
Air 66 178352 -
Acetic acid 216 35472 14.7
Benzoic acid 673 124016 51.4
Unknown 37
Phthalate ester 1034 28352 11.7
Alkane 1173 8776 3.6
Alkane 1518 17424 7.2
Alkane 1566 5408 2.2
Diphenylbutanone 2243 13088 5.4
1. Tentative identification given to GCIMS p ak.
2. Percent of the total area for the peaks in this table.
B-259
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APPENDIX C
QAIQC
MRI M\R8913 36APC C1
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APPENDIX C
SUMMARY OF QUALITY AS5;URANCE AUDITS
This appendix describes the audits conducted during the course of the experimental
activities associated with this demonstration tesi. Audits were conducted by T. Dux,
the primary Quality Assurance Coordinator (QAC:) for this project, and D. Hooton. All
audits were reported to the project leader (D. Tienholm), the MRI Corporate Quality
Assurance Unit (C. Green had oversight for this project) and appropriate line
management and individual task leaders.
1.0 OVERALL AUDIT SUMMARY
A comprehensive auditing program was planned and conducted for this demonstration
test. This program included an on-site technical systems audit and a comprehensive
audit of data quality for measurement processes. During each audit the following
general areas were addressed:
1. Adherence to test plan and referenced m9thods.
2. Implementation of all planned quality control (QC) procedures.
3. Satisfying the criteria for data quality indicators and calibration procedures.
4. Sufficient documentation to support test results.
5. Validation of all test results.
6. Verification of the accuracy of calculations.
7. Proper discussion in the final report of all data quality problems affecting test
objectives.
The overall results of the audit indicate:
1. Test results were obtained as indicated ri the test report.
2. All data quality problems were reviewed by project management and pertinent
issues are discussed in the test report.
3. The majority of data quality indicators met the criteria of the test/QA plan or
applicable reference method.
4. Data quality should be sufficient to meet the test objectives.
MRIM R891336APC C-3
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The remainder of the report documents the specific activities for each audit and any
data quality problems noted by the auditor which could affect sample results. Where
appropriate, the problems and its affect on data quality are discussed in the relevant
sections of the final report.
2.0 AUDITS OF FIELD ACTIVITIES
There were five audits of activities directly associated with field sampling and field
analyses. First, a technical systems audit of field operations was conducted. Second,
an audit of data quality associated with the field operations was done by reviewing
the supporting records. Third, fourth and fifth, similar audits were done for the
continuous emission monitors, hydrogen chloride determinations and field GC sampling
and analysis.
2.1 Technical Systems Audit of Field Operations
The audit was conducted on June 21, 1990, Run Number 2; the QAC was present
from initial set up to final disposition of samples. During the audit, the QAC compared
actual field operations to the specifications in the applicable procedures and the draft
test/QA plan. Specific audit forms with applicable questions/observations were
generated for this audit from the test plan and associated methods.
The following operations were observed:
- Sampling of lime slurry, liquid waste, process water, and coal.
- Delivery of waste feed both solid and liquid.
- VOST sampling by Method 0030.
- SVOST sampling by Method 0010.
- Sampling for hydrogen chloride (both trains).
- Sampling, calibration, and analysis by field GC.
- Operation and calibration of CEMS.
- Disassembly and storage of the MM5 train components.
- Disassembly and storage of VOST condensate and cartridges.
In general most field operations were conducted in accordance to the methodology
and the draft test/QA plan. Personnel appeared to be well trained and competent.
There was sufficient information recorded in most cases to completely support the
data generated during this demonstration test. Most calibration, leak checks and
associated QC procedures and information were well within criteria.
The following topics were noted during the audit:
1. This project was in a state of flux resulting numerous changes in conditions and
specifications for the trial burn. The draft sampling plan does not completely
reflect the work conducted during demonstration test. hi addition, problems
MRI M R8913 36 APC C-4
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developed during the run which required corrective action. Therefore, the
activities in the test report in some cases do not exactly match what was
indicated in the test plan. Major changes in the test plan and data quality
problems were communicated to EPA personnel on a “real-time” basis to assure
proper resolution.
The following minor difficulties and differences between the test plan and the
actual conduct of the work were noted for Run 2:
- A different sampling port was required for yOST.
- A different sampling set up was used for the bag sampling.
- The nitrogen bias check of sampling lines for the CEMS and
field GC was not done.
- A different filter was needed for the chloride train.
- A different sampling rate was used for chloride.
- A different sampling rate and sample volume was needed for
yOST.
- Water was noted condensing in the unheated THC lines.
None of these items prevented achieving the project objectives.
2. Due to a change in the schedule for this test, the MRI HCI monitor was in use
on another project and a monitor was borrowed from the EPA. The EPA
monitor was received on-site and was nol functioning.
3. Some process and waste feed sampling was conducted by facility personnel.
The test plan indicated that MAt was to conduct all sampling, however, on
some days facility personnel would not allow MRI samplers access to plant
equipment (e.g., sampling ports and valves.) In these cases, an MRI technician
observed all sampling except for powdered waste feed. Since powdered waste
feed sampling was not done or observed by MRI personnel, the traceability and
integrity of the sample cannot be MRI’s rEsponsibility.
2.2 Audit of the Data Quality of Field GC Sarripling and Analysis
The QAC reviewed the conduct of the work as documented in the records and
compared it to the test plan to assure that it met project requirements. The analyses
and results for Run 4 were completely traced and selected results were verified.
The project records were complete and well organized. Results were traceable to raw
data. All QC procedures were implemented, all QC results were calculated and met
criteria. Two items noted during the audit are pre ented below and are discussed with
the data in the final report.
MRI M R8913-36 APC C-5
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1. The ethylene analysis was not possible in the field due to its coelution with
ethane. This was done later in the laboratory, thus, the 24 h holding time by
the plan for these samples could not be met. No ethylene was detected.
2. The field notebook indicated a flow rate problem with the Tedlar bag sample
(C 1 /C 2 determination) which may have resulted in a sample not representative
of the entire Run 4.
2.3 Audit of the Data Quality of Field Sampling as Indicated by the Field Records
The QAC reviewed the field records (raw data, observations and calibration data) and
traced the activities associated with Run 4. This was done to assure that the test
plan and associated methods were conducted as planned, that valid field samples were
obtained and that results for field sampling and calibration activities were traceable.
The audit indicated that most data was traceable and most QC checks met the
appropriate criteria. The following topics were noted during the audit.
1. The MM5 train for run 4 failed the final leak check because the probe cracked
while removing it from the port. The sample was judged to be valid.
2. A few final calibration records are incomplete for pyrometer, thermocouple,
pitot tube, and VOST console data. This did not have significant impact on
data quality.
2.4 Hydrogen Chloride Analyses
The QAC reviewed the raw data and final results for the HCI data associated with
sampling trains. The results of the work were compared to the requirements of the
test/QA plan. Selected samples were traced through the raw data and results were
verified by the QAC.
The audit indicated that some work was not conducted according to the test plan and
as a result some sample results are estimates and a few could not be reported.
Evaluation of the data indicated that the estimated results, should be usable and that
sufficient data were obtained to meet the overall needs of the project. The specific
problems and impact are presented in the test report in the discussions of both
sampling and final results.
2.5 Continuous Emission Monitors (CEMS)
The data were reviewed for general traceability, accurate representation, and
compliance to the “Draft Test and QA Plan, Continental Cement Wet Kiln, Hannibal,
Missouri.” The following minor comment was noted.
MRIM R891336APC C6
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Some loss of data was noted for Runs 5 and 6 due to technical problems during
sampling, but these appear to be less than 10% of total sampling time.
3.0 AUDITS OF LABORATORY ACTIVITIES
There were three primary analyses conducted aller the test; analysis of the Volatile
Organic Sampling Train (VOST) for volatile organic compounds, analysis of the
Modified Method 5 (MM5) sampling train for polychlorinated dibenzodioxins and
dibenzofurans (PCDD/F) and analysis of the MM5 sampling train for semivolatile
analytes.
3.1 Volatile Organic Sampling Train Analysis
The QAC reviewed the raw data, final results and summary memo. The results of the
work were compared to the requirements of the :est and QA plan. Selected samples
were traced through the raw data and results were verified by the QAC.
The audit indicated that experimental work was conducted according to the test plan.
The raw data package was organized and complete. Sample data were traceable and
results were verifiable. The following topics were noted during the audit.
1. The 1 ,4-Dioxane results are suspect due 10 these two difficulties:
a. At least one-third of the blanks had significant levels of the analyte with
an average level of 560 ng. Many sample results are beneath the blank.
b. The daily standard results were erratic. The recovery of the analyte in
the daily standards ranged from the analyte not being detected to 920%
of the actual concentration.
2. Two tubes (Run 1 Pair 3 Tenax and Run 2 Pair 3 Tenax) were received cracked
and the contents were switched to anoiher VOST tube for analysis. The
samples have significantly higher levels of methylene chloride (10 to 20 times)
than any of the other samples associated with those runs. There is a high
probability that the methylene chloride is a result of laboratory contamination
occurring during the switching of the packing material and methylene chloride
levels for these two samples should not b used in engineering assessments.
3.2 PCDD/F Analysis of MM5 Samples
The QAC reviewed the raw data, final results and summary memo. The results of the
work were compared to the requirements of the test and QA plan. Two samples (run
4 and blank train) were traced through the raw data and selected results were verified
by the QAC. The following topics were noted during the audit.
MRIM R891336APC C-7
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1. There is a surrogate recovery objective of 40% to 120%. This was not met for
the majority of the analytes in Run 4, the blank train and one water matrix
spike. In these cases surrogates were all low, around 25% to 35%. PCDD/F
results from Run 4 have been flagged in the final report.
In addition, the matrix spike for Run 4 shows high recoveries for all the native
PCDD/F, the other matrix spike gave generally acceptable surrogate and native
recoveries. This indicates that the sample might have been incorrectly spiked
with surrogates.
2. Elevated matrix spike recoveries occurred for the homolog data for HxCDD,
HxCDF, HpCDF, and PeCDF. Appendix B-7 explains this more thoroughly.
3. The majority of the field samples (Runs 1, 2, 3, and 4) were processed without
a method blank. Method blanks were run with the next batch of samples
(Run 5 and spikes). This means that the majority of the samples are not
directly associated with a blank. In addition, the blank train was extracted
alone and appears to have consisted of only an XAD and filter. See Appendix
B-7 for more information.
3.3 Semivolatile Analysis of MM5 Samples
The QAC reviewed the raw data, final results and summary memo. The results of the
work were compared to the requirements of the test and GA plan. Two samples
(Runs 4 and 6) were traced through the raw data and selected results were verified
by the QAC. The audit of sample preparation activities are reported above with the
audit on PCDD/F analyses.
In general sample results were traceable and generated according to the test and GA
plan. Quality control procedures were implemented and most were within QC criteria.
Following is a discussion of QA/QC topics from the audit.
1. Extraction holding tames were met for all samples. Analysis holding times (40
days past extraction) were not met (exceeded by 11 days) for Runs 1, 2, 3, 4,
and the blank train. Only Runs 5 and 6 met the analysis holding times.
2. There is a data quality objective of 70% to 130% recovery for the two
surrogates. Each train had a different fraction spiked. The recoveries of
d 10 -pyrene were within the objectives and the average recovery for all six runs
was 99% ± 6 (s). The surrogate 2,4,6-tribromophenol had some recoveries
above the objectives, however, the average recovery was 1 28% ± 38 (s)
which is within the objective.
MRIM\R89 336APC C-B
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3. The ether extraction for Run 4 evaporated to dryness during the night due to
insufficient cooling capacity of the condensers. The impact upon sample results
appears to be negligible since Run 4 data are comparable to other run’s results.
4. Bis-2-ethylhexylphthalate was present in the blanks at levels between 20 to
50 .tg, and present in samples at levels between 20 to 90 ng. This compound
is a common laboratory contaminant and any result less than two times the
blank level (e.g. < 100 ng) should be considered suspect.
36 APC C9
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APPENDIX U
RISK ASSESSMENT CALCULATIONS BY RADIAN
This appendix contains results of an independent risk assessment
performed by RADIAN Corporation. These calculations were based on preliminary
PCDD/PCOF data which is slightly different than the final data published in
this report. Variations in the final data are less than 3%, however,
minimizing any impact on these risk assessment calculations.
D—1
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HEALTH RISK ASSES:;MENT FOR
THE CO TINE ’ITAL CEHENT KILN,
HANNIBAL, MISSOURI
prepared by,
RADIAN CORPORATION
Roger Christrnan Project Manager
Lori Lee Stoll, Proje:t Director
Steven T Cragg, To ico1ogjst
Daryl Grassick, Ait Modeler
November 199)
D-3
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TABLE OF CONTENTS
Pa .e
EXECUTIVE SUMMARY i
1 0 INTRODUCTION 1
2 0 APPROACH 2
3 0 CHEMICAL OF CONCERN SELECTION 4
4 0 CHEMICAL MIGRATION PATHWAYS AND ROUTES OF EXPOSURE 5
5.0 POTENTIAL RECEPTORS 6
6 0 EXPOSURE ASSESSMENT 7
6.1 Model Selection 7
62 LandUse 8
6.3 Meteorological Data 8
6 4 Receptors 9
6 5 Emission Data 10
6,6 GEP Analysis 13
6 7 Modeling Results 15
7.0 TOXICITY AND FATE ASSESSMENT 20
7 1 Physicochemical and Ocher Characteristics of Dioxin 20
7.2 Environmental Fate of Dioxin 21
7 3 Toxicity of Dioxins 24
8 0 RISK CHARACTERIZATION 26
8 1 Results 26
8.2 Assumptions and Uncertainty 26
8.3 Summary 28
REFERENCES 30
D- 4
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LIST OF TAE LES
Page
Table 6-1 Discrete Receptors included in Modeling Analysis 11
Table 6-2 Stack Parameters and Source Data for che 12
Continental Cement Facility
Table 6-3 GEP Analysis 14
Table 6-4 Maximum Predicted Impacts for Reference Polar 16
Receptor Network
Table 6-5: 4aximum Predicted Impacts at DLscrete Receptors 17
Table 6-6 Emission Rates and Maximum Predicted Concentrations 19
in TCDD-Equivalencs
Table 8-1 Excess Lifetime Cancer Risk from the Continental 27
Cement Kiln Facility
D-5
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EXECUTIVE SU &ARY
Radian Corporation was asked by the Office of Solid Waste of the Environmental
Protection Agency (EPA) to conduct a risk assessment for dioxin emissions from
the Continental Cement Kiln in Hannibal, Missouri Results were based on
dioxin stack analyses from four different incineration ‘runs,” where different
materials were burned in the kiln for each run The first and fifth runs
represented baselines where coal and coal/diesel fuel, respectively, were the
only materials incinerated In the third and fourth runs (a second run was
apparently aborted) , hazardous waste material was burned
Ambient air concentrations of dioxins and furans resulting from measured kiln
emissions at the stacktop were estimated within a 10,000 meter radius using
SCREEN and ISCLT air dispersion models TCDD-equivalent concentrations
projected by the models at various “receptor” locations were converted to
excess cancer risks using the EPA Cancer Potency Slope (a.k a , the “unit
risk” factor) for the dioxin isomer, 2,3,7,8-tetrachlorodibenzo-p-dioxin
(TCDD) In addition to a poLar array of 360 receptors, the receptor network
included 31 receptors to assess risks at specific locations, such as resi-
dences and public gathering places (e.g , schools, hospitals, government
buildings, and recreational areas). The impact to the most exposed individual
(MEl) location was also evaluated. The MEl location comprises that location
on the ground where maximum annual average dioxin concentrations would occur
Using conservative assumptions, cancer risks exceeded 1 chance in 1,000,000
only at the MEl and one of the elevated terrain locations for any of the runs
At present, no humans are located at either of these locations MEt baseline
cancer risks for a coal-only run (run l) were 0 67 chance in 1,000,000 and
were 2 3 in 1,000,000 for the coal and diesel fuel run (run 5) Risks to the
MEl for the two kiln runs where hazardous waste was burned, produced risks of
approximately 2 in 1,000,000 and 4 in 1,000,000 (runs #3 and #4, respective-
ly). Risks at the elevated terrain location were approximately half that for
the MEl for all runs. Results from the second hazardous waste run (run #4)
are suspect due to low surrogate recoveries during chemical analysis
D- 6
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1.0 INTRODUCTION
Radian conducts risk assessments for sites in accordance with procedures set
forth in the US EPA Risk Assessment Cuidarce for Suoerfuncl, Volume 1, Human
Health Evaluation 1anua1 (Part A ) (EPA, 1989a) Other guidance documents
include, but are not Limited to, The Risk Assessment Cu delires for 1986 (EPA,
1987a), and the Superfund Exposure Assessm rt Marual (EPA, 1988a)
The overall objectives of any risk assessment are listed below
o Identify contaminants of concern (i.e , indicator chemicals) from
existing site data.
o Characterize on-site exposure pathways by which chemicals might
migrate through environmental media.
o Identify locations where contact wit.h humans or other receptors might
occur.
o Estimate contaminant concentrations at probable contact points
o Compare concentrations at contact points with appropriate guidelines
and standards.
o Define those receptors (human and environmental) who might be exposed
at the contact points.
o Calculate human and other receptor exposures aL the contact points
o Evaluate the potential noncarcinogenic and carcinogenic health impacts
associated with estimated receptor exposure levels
For this risk assessment, the first two of these objectives are already
defined Specifically, dioxin is the sole chemical of concern and air is the
pathway of concern
D-]
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2 0 Anproach
The following is a generalized description of the approach used to evaluate
potential public health and environmental impacts There are four basic
phases of a risk assessment that incorporate the objectives listed above
Analytical Chemistry Evaluation and Selection of Chemicals of Concern The
quality of the risk assessment depends on the accuracy and completeness of the
data upon which it is based Chemical sampling and analysis of the site must
be extensive enough to support the calculation of average concentrations
representative of site contamination This information must be of sufficient
quality so that chemicals contributing the major risks may be identified along
with their migration pathways, contact locations, and critically impacted
receptors. Off-site concentrations must be characterized so that only
chemicals that are specifically associated with the site influence risk
calculations Finally, analytical detection limits must allow sufficient
sensitivity to quantify risks for the more potent chemicals
Dioxins are the chemicals of concern for this assessment The term “dioxins’
comprises a class of polychlorinated dibenzo-p-dioxins and, often, the related
class of chemicals chlorinated dibenzofurans. 2,3,7,8-Tetrachlorodibenzo-p-
dioxin (2 ,3,7,8-TCDD) is considered the most toxic and carcinogenic isomer of
either the dioxin or furan class r, fl en “dioxins” are not speciated (i e
when the individual isomers within each class are not quantified separately)
it is the conservative practice to assign the toxicity of 2,3,7,8-TCDD to the
entire class This may markcdly overestimate carcinogenic risks depending on
the ratio of isomers actually present.
Exposure Assessment . The exposure assessment describes the on- and off-site
movement of the chemicals and identifies and characterizes potentially exposed
populations Exposure pathways through which chemicals may contact human or
environmental receptors are identified The concentrations of indicator
chemicals at receptor points are measured analytically or they are predicted
D- 8
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by mathematical modeling At this point, concentrations in the various media
at contact points are compared to Applicable or Relevant and Appropriate
Requirements (ARARs) Since ro Federally mandated ARARs exist for dioxin in
air, the uptake and absorption of this chenical by humans and critical
environmental receptors is calculated to determine dosage or uptake
In this assessment for the Continental faclity, it is not necessary to
calculate a dosage since EPA requested evaluation of only one contaminant
migration pathway (air) and only one route of exposure (inhalation) Thus, it
is sufficient to calculate exposure concentrations
Toxicity Assessment The intrinsic toxicity of the indicator chemicals is
described in this phase Major target organs are identified and other
effects, such as possible reproductive hazards or cancer-causing potential,
are described. Indicator chemical reference doses (RfDs) which represent
acceptable daily intakes for non-carcinogenic effects are identified, as are
cancer potency slopes (CPS’s) if the chemical is capable of causing cancer
If RfDs or cancer potency slopes have not been derived by EPA or other appro-
priate scientific authorities, they may have to be derived from appropriate
animal or human toxicity data Relevant physical and chemical properties of
the contaminants are also presented which might influence the likelihood of
exposure
Risk Characterizatiorr In this phase, the exposure and toxicity assessments
are integrated. The ground level concentrations estimated in the exposure
assessment are compared with health-based concentrations described or d vel-
oped in the toxicity assessment, in order to estimate the potential for non-
cancer public health or environmental impacts In addition, excess cancer
risks are calculated by multiplying est1rnate exposure concentrations by the
unit risk factor for djoxins and furaris (as Z,3,7,8-TCDD equivalents), the
chemicals of concern in this risk assessment. The risk characterization phase
also includes a summary of the assumptions umed in the assessments and
explains the resulting uncertainties and limLtations of the risk assessment
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3 0 CHEMICAL OF CONCERN SELECTION
The chemical of concern at this facility is dioxin, generated during the
con bustion of fuels and feed materials for the production of cement The
dioxin emissions have been speciated to characterize the various proportions
of dioxin isomers Thus, it is not necessary to assume that all of the
dioxins were 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) This is
important since other dioxin isomers closely related to 2,3,7,8-TCDD have
relative cancer potencies ranging from one halE to one thousandth that of
2, 3,7,8-TCDD.
D- 10
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4.0 CHEMICAL MIGRATION PATHWAYS .kND ROUTES OF EXPOSURE
Air is the rtmary medium through which dioxins migrate from their release
point (the facility stack) Although indirect (i e , non-inhalation) pathways
would contribute to exposure, assessment of indirect pathways is beyond the
scope of this assessment and is not evaluated.
D-11
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5 0 POTENTIAL RECEPTORS
Human receptors are considered of primary importance in this risk assessment
The evaluation of receptors such as wildlife, while important, is beyond the
scope of this risk assessment Dioxin impacts are evaluated for the maximum
exposed individual (MEl) The MEl is assumed to reside at the location of
maximum ground-level dioxin concentration, determined by mathematical modeling
(see Section 6) The mathematical modeling produces an estimate of ground-
level dioxin concentrations for an array of receptors including discrete
receptors The MEl location is identified which may not correspond to an
actual receptor Discrete receptor locations include churches, schools,
hospitals, and individual nearby residences identified from U.S Geological
Survey (USGS) topographical maps Receptor locations are defined in the
(following) Exposure Assessment section
0-12
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6 0 EXPOSURE ASSESSMENT
An exposure assessment for dtoxin emissions from the Continental Cement facil-
ity was conducted using EPA-recommended dispersion models These models were
e uloyed to estimate ambient dioxin concentrations given facility emission
data, stack characteristics, and rneteorologLcal data Predicted ground-level
dioxin concentrations will be used to asses ; the potential health impacts in
communities south and west of the facility, including the city of Hannibal to
the north Initial modeling results reflect the application of a unit emis-
sion rate Actual dioxin emission rates ar calculated and applied to these
unit emission rate results later in this section
Two models were chosen in conducting this analysis The SCREEN model was used
to locate “worst-case’ maximum concentrations under a variety of meteorologi-
cal conditions and terrain heights Results from the SCREEN model were used
primarily to help design a receptor network applied in the modeling analysis
in which the ISCLT model was employed The following sections discuss the
assumptions and applications of the models :hosen and the niethodology employed
including the results of the exposure assessment for dioxins
6.1 Model Selection
The SCREEN model was selected to help desigi the receptor network used in the
modeling analysis This model was also used to determine stable plume heights
for potential complex terrain assessments by which the potential for maximum
impacts occurring in complex terrain is evaLuated The appropriate model was
selected based on the averaging time pertaiiing to the exposure limit for
dioxin. Given annual averaged meteorologicsl conditions represented by a
joint frequency distribution, the ISCLT model can be applied to predict annual
average dioxin concentrations. The combination of averaging period, potential
for building downwash, and terrain relief (comprised of elevations from below
stack, up to intermediate heights throughout the modeling domain), make the
ISCLT model appropriate for this analysis. The latest version of the EPA
approved UNAHAP Version 6 Industrial Source Complex Long-Term (ISCLT) model
0-13
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was selected The EPA guidelines (EPA, 198Gb) , recommend using ISC to model
industrial sources located in urban or rural areas where the maximum terrain
elevation does not exceed stack top elevation The ISCLT model uses the
generalized Briggs plume rise equations to calculate plume rise as a function
of downwind distance, and adjusts the observed wind speed from the anemometer
measurement height to the emission height
The SCREEN model can be applied to assess terrain elevations greater than the
stack top. Terrain elevations greater than stack top fall into two catego-
ries, intermediate and complex terrain Based on initial SCREEN model runs,
terrain heights greater than stack top fell into the intermediate category
The high stable plume height elevation, to which comparisons were made, was
1,100 feet SCREEN was applied to determine if a more refined model was
necessary to evaluate impacts on intermediate terrain receptors As discussed
in the following sections, a further analysis with a more refined model (e g
VALLEY, using annualized meteorological data), was not necessary
6 2 Land Use
Land use characteristics must be identified to determine the fraction of both
urban and rural land use types that exist within a 3-kilometer radius of the
facility under evaluation The land use, based on the information for that
particular area, is classified as urban or rural, and this enables the selec-
tion of appropriate dispersion coefficients for input to the ISCLT model The
land use typing scheme normally employed is that of Auer (Auer, 1978) A
brief examination of the Hannibal East-Ill quadrangle map shows that the land
use within 3 kilometers of the plant is classified as rural Therefore, rural
dispersion coefficients were chosen.
6 3 Meteoro1o ical Data
eteorological data applied in the SCREEN model includes prescribed “worst-
case” meteorological conditions Each meteorological condition represents a
particular plume description characteristic
0-14
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Five years of meteorological data were appled in the ISCLT modeling analysis
The meteorological data for each year was processed and converted into a Joint
frequency distribution 3ecause the facility is situated in a rural environ-
merit, the meteorological data were obtained from a National Weather Service
(NWS) station located in a rural environment: The Springfield, Illinois NWS
station was chosen for obtaining meteorologLcal data because of the proximity
to the Continental Cement Company along with similarities of the environment
between the two sites
Sequential hourly surface meteorological data collected at the Springfield,
Illinois NWS station for the five-year period, 1984 to 1988, were selected for
the analysis. Hourly meteorological data were compiled and processed, creat-
ing a STAR data file (joint frequency distrLbution of wind speed and direction
by atmospheric stability class) for input to the ISCLT model
Other meteorological data required as input to the ISCLT model include annual
average mixing height and surface temperature for each stability class, and
wind speed profile exponents These data were based on annual average values
for the Northeast portion of Missouri found in Holzworth (Holzworth, 1972)
6.4 Receptors
For the purpose of assessing potential maximum impacts on intermediate terrain
receptors, using the SCREEN model, the five highest near-field terrain heights
were selected as discrete receptors They Lnclude the following
. MSL Height (ft Distance 1 Direction
760 1,846 SW
780 1,942 SW
800 2,346 SW
820 2,615 SE
840 3,000 SE
A receptor network compatible for use in the ISCLT model was designed and
consisted of a prescribed polar-type receptor network with discrete receptors
positioned at arbitrary locations throughout the network Receptor points on
0-15
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the reference network are identified by polar coordinates (radial distance and
azimuth bearing) Discrete receptor points are identified by cartesian
coordinates (UTM easting (X) and northing (Y) positions) The reference
network consists of 360 receptors identified by 10 radial distances and 36
directions spaced at 10-degree intervals Since no information was given
defining property fence lines or boundaries, the closest receptor ring
distance modeled, 100 meters, provides near-field estimated concentrations
The 50-meter ring distance was too close to be modeled This distance is
within the “ 3 Hb” (i e , 3 times the building height) limit, wherein ISCLT will
not calculate concentrations The area within this limit is where building
downwash occurs within the cavity region and the ISCLT model is not applicable
to cavity effects No residents have been identified within 50 meters of the
stack. The remaining ring distances include 200, 400, 800, 1500, 2200, 3000,
6000, and 9000 meters Discrete receptor points are associated with locations
accessible to the public, such as schools, hospitals, churches, and municipal
buildings. Other discrete receptors included residential areas and potential
maximum impact locations Table 6-1 lists the discrete receptors evaluated in
the analysis
Receptor point elevations were identified by means of the USGS topographical
map system. Mean sea level (MSL) elevations were determined for each receptor
for the reference polar receptor network by locating the highest elevation
within an area centered on each receptor point The area is a sector that
extends half the distance to neighboring radials and rings MSL elevations
for each discrete receptor were identified at each receptor location
6.5 Emission Data
Source data was obtained from documentation provided from stack tests conduct-
ed by Midwest Research Institute (MRI) (see Appendix A). The Continental
Cement plant source consists of one stack located near several electrostatic
precipitators. The stack is cylindrical in shape and extends 150 feet above
the base. Stack parameters are listed in Table 6-2
D— 16
-------
TA3LZ 6-1 DISCRETE RECEPTORS INCLLDED I’4 MODELING ANALYSIS
DATE 11/19/90
Receptor
tJSCS
Receptor Location,
(in kiloc,eters)
Receptor
0 Lstance
From
Stack
Receptor
£jevatio-t
# Receptor DescriptIon X
Y
(kn)
(Er)
1 Monkey Run Residence I
2 Monkey Run Residence II
3 Ilasco Residence I
4 Ilasco Residence II
5 Local. Residence I
6 Local Residence TI
7 Le8aucie Cave Residence
8 Residence Near 607’ TerraIn Point
9 ResIdence In South DLrectIo ’i
10 Stacktoo 2eI r :.oca:io-
11 Elevated Terralt LocatIon I
12 ELevated Terrain LocatIon II
13 Elevated Terrain Location III
14 BLesSed Sacramete School
15 St Thomas Seminary
16 Mark Tvain School.
17 Court Nouse
18 City Hall
19 Central School
20 Pettibone School
21 St Jonn Scnooi
22 Field School
23 Ant ioch Church
24 Hospital ALong Route 61
25 HospItal ALong Route 36
26 SchooL Near Oakvood
27 Church Near Saverton
28 High School sear Mason
29 Turner School (Ely Road)
30 School SE of Hannibal Terrace Av
31 3 Church/i SchooL Rrs 61/36
? I LOCATION
644
32
4393
24
0
20
670
645
60
4392
60
1
24
500
645
58
4392
67
1
19
520
645
01
4392
56
0
81
470
645
58
4392
38
1
68
480
664
57
4393
10
0
11
595
643
62
4393
05
1
11
610
644
33
4393
95
0
77
500
643
28
4392
61
0
87
600
666
50
4392
20
1
00
510
644
25
4393
23
0
27
740
544
52
4393
07
0
13
520
644
51
4393
04
0
16
640
664
26
4393
03
0
25
700
639
05
4395
87
6
09
570
638
60
4396
13
6
61
640
638
52
6396
30
6
75
610
660
25
4396
25
5
25
510
660
80
4396
54
5
00
490
640
23
6396
40
5
35
570
640
35
4396
75
5
48
630
639
20
4395
80
5
39
520
639
67
4395
70
5
66
520
641
67
4390
83
3
71
800
639
65
4395
82
5
53
540
638
83
4395
93
5
31
540
637
30
4393
95
7
25
550
648
33
4390
30
4
79
480
638
00
6397
85
8
01
640
635
43
4396
50
9
67
760
641
50
4395
67
3
90
530
640
15
4396
10
5
24
510
D- 17
-------
TABLE 6-2 STACK PARAMETERS AND SOURCE DATA FOR THE
CONTINENTAL CENENT FACILITY
Units
Parameters Metric English
Source EmLssion Rate — 1 gm/sec
Stack Coordinates X — 644520 m
Stack Base Elevation 590 ft
Stack
Height
45.72
m
150.00
ft
Stack
Gas Exit
Temperature
544 10
Dog K
520 00
Deg F
Stack
Gas Exit
Velocity
15,24
rn/sec
50.00
ft/sec
Stack
Inside Exit Diameter
3 58
m
11 74
ft
Y — 4393200 in
D-18
-------
A unit emission rare of 1 gram per second w as assumed in the modeling analy-
sis The resulting modeled concentrations :eElect a concentration value
“Chi/Q” where Chi represents a concentration in ug/m 3 and Q denotes an emis-
sion rate of 1 gm/sec. Thus, actual stacktop emissions in g/sec may be multi-
plied by Chi/Q to obtain modeled concentratLons at various receptor locations
6 6 GEP Analysis
A Good Engineering Practice (GEP) stack height analysis was performed to
determine if building-induced wake effects on ground-level impacts should be
included as part of the modeling analysis The GEP analysis is required as
part of an EPA rulemaking governing stack height regulations (see the July 8,
1985, Federal. Register ) The analysis includes a formula that defines the
stack height necessary to ensure that emissions from the stack do not result
in excessive concentrations in the immediate vicinity of the source as a
result of aerodynamic effects created by nearby structures or terrain obsta-
cles.
The formula consists of the height of the nearby structure plus 1 5 times the
height or projected width of the structure, whichever is less “Nearby” is
defined as that distance within five times the lesser of the height or width
dimensions of a structure but not greater tnan one-half mile. Both the height
and width of the structure are determined from the frontal area of the struc-
ture projected onto a plane perpendicular to the wind
For the Continental Cement plant, the GE? stack height was calculated based on
estimates of the ESP structures and their proximity to the stack The current
stack height, 150 fe, is below the GEP formila height of 200 ft as shown in
Table 6-3 However, since the stack height is higher than the calculated
cavity height - the structure height plus 0 5 times the lesser dimension -
only Huber-Snyder wake effects were considered as part of the ISCLT modeling
analys is
0-19
-------
TABLE 6-3 GEF ANALYSIS
GEP Formula H 5 [ - + 1 5L
HB Height of nearby structure
L — Lesser dimension, height or projected width
SL — Nearby distance, or one-half a mile, whichever is less
Stack Height 150 feet
80 feet
L 80feec
H 5 — 2.5(80) — 200 feet
5L - 5(80) — 600 feet
Distance from stack to nearby ESP structure 30 feet
ES? structure is, therefore, within influence
Cavity height below which Schulman/Scire downwash algorithm is employee
H 5 +05L
H 5 1.5(80) 120 feet
Sujrumarv
Stack height < GE? height
Stack height > Cavity height
Huber-Snyder wake effect algortthm will be applied in the ISGLT analysis
0-20
-------
6 7 Modeling Results
Both SCREEN model results for intermediate terrain and results from the ISCLT
model were analyzed in order to verify that maximum predicted impacts occurred
for terrain heights equal to or below stack height The SCREEN model calcula-
tions included a ‘simple terrain” (terrain L teighcs limited to stack height)
analysis and a complex terrain (actual terrain heights) analysis The maximum
from each analysis was selected The SCREE model results using this approach
represent 24-hour average concentrations ro obtain annual average concentra-
tions, the 24-hour value was multiplied by a conversion factor of 0 4 For
the SCREEN model, the maximum predicted annual average concentration was 0 287
ug/m 3 (based on a 1 gm/sec emission rate) and occurred 1,846 meters to the
southwest of the facility It should be noted that this conversion from a
short-term to a long-term average is very conservative since it does not
consider the annual fluctuations of wind speed, direction, and atmospheric
stability.
A refined analysis using the VALLEY model for intermediate terrain was not
required since the maximum predicted impact from the SCREEN model results,
0 287 ug/m 3 (based on a unit emission facto’ ), is less than the maximum
predicted impact, 0 38 ug/m 3 , from the ISCLT model results The latter, more
health-protective modeling results were used in this report
Annual averaged relative concentration estimates based on a unit emission rate
are presented in Tables 6-4 through 6-6 Maximum predicted concentrations for
the reference receptor network are presented in Table 5-4 for each year
modeled Using the ISCLT model, the maximum annual average impact, based on
1984 meteorological data, for the reference polar receptor network is 0 3804
.ug/m 3 and is predicted to occur 200 meters Qesc of the Continental Cement
plant Table 6-5 shows the maximum annual average impact based on an emission
rate of 1 gm/sec for each discrete receptor along with the appropriate year of
meteorological data. The maximum impact at the MEl location is 0 38 ug/m 3 per
1 gm/sec (a k.a., “Chi/Q”)
D-2 1
-------
TABLE 6-4 MAXI {UM PREDICTED IMPACTS FOR REFERENCE POlAR RECEPTOR NETWORK
STAR Data
Year
Annual Predicted
Impact (Chi/Q)*
(xE-02)
Ring
Distance
(m)
Direcrion
(Deg)
1984
38 04
200
280
1985
23 04
200
260
1986
21 56
200
280
1987
31.84
200
260
1988
16 90
200
280
* “Chi’ denotes concentration (ug/rn 3 ), and TIQ I denotes emission rate (gm/sec)
D- 22
-------
TA3LE 6-5 MAXI”UM PREDICTED t’ ACTS AT DISCRETE REZEPTORS
DATE 11/19/90
Receptor
AnnuaL Irnpact
(Chi/Q)*
STAR
Data
x E-02
Year
1 Monkey Run Residerce I 0 17 84
2 Monkey Run Residence Ii 0 1? 84
3 fiasco Residence 1 0 05 84
4 ILa..gco Residence II 0 21 84
5 LocaL Residence I 0 47 84
6 LocaL Residence II 0 3’) 84
7 Le8au e Cave ResIdence 0 07 84
8 Residence Near 607’ Terrain Point 0 13 84
9 Residence In South Direction 0 17 86
10 Stacktop Height LocatIon 22 5) 84
11 Elevated Terrain Location I 2 87 84
12 Elevated Terrain Location II 4 92 84
13 Elevated Terrain Location III 7 54 87
14 Sleased Sacrament SchooL 0 34 84
15 St Thomas Seminary 0 4? 84
16 Mark Twain SchooL 0 42 84
17 Court House 0 2? 38
18 City HalL 0 31 S8
19 CentraL School 0 35 83
20 Pettlbone School 0 43 84
21 St John School 0 27 84
22 Field SchooL 0 27 84
23 Antioch Cl’urch 0 82 87
24 Hospital Along Route 61 0 3) 84
25 Hospital ALong Route 36 0 3) 84
26 School Near Oakwood 0 33 84
27 Church Near Saverton 0 34 88
28 High ScnooL Near Mason 0 45 86
29 Turner School (Ely Road) 0 6? 84
30 School SE of Hannibal Terrace Av 0 35 88
31 3 Churcn/l Sc ool Rt, 61/36 0 23 88
* ChL denotes roncentrat on lug/ma c I). and “Q de-ictes emission rate (gn/sec)
D- 23
-------
Table 6-6 shows maximum impacts in terms of actual TCDD-equivalent emission
rates and TCDD-equivalent ground level concentrations at the MEl and other
receptor locations Actual. TCDD-equivalent emission rates for the four runs
at the Continental facility are given in the M.RI report in Appendix A The
maximum predicted annual average impact among discrete receptors having
regular public access is predicted to occur at the Antioch Church 3 71
kilometers west of the facility
D-24
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TABLE 6-6 EMISSION R TES AND MAXIMUM PREDICTED CONCENtRATIONS IN TCDD-EQUIVALEIITS
DATE 11/19/90
Run 1 Run 3 Run 4 Run S
1 s/sec
-based
Actual
TCDD-Equiv
Emls3iOn
TCDD-Equiv
Modeled
Ground-Level
Actual
TCD0-Ec uLv
Emission
TCDD-Equiv
Modeled
Ground-Level
Actual
TCDD-Equtv
Emission
TCDD-Equlv
Modeled
Ground-Level
Actual
TCDD-Equiv
F.misslon
tCDD-L , u1v
Modeled
Ground-Level
RECEPTOR
RECEPTOR
Annual Imiact
Rate
Concentration
Rare
Concentration
Rate
Concentration
Rate
Concentration
I
DESCRIPTION
(Chl/Q)a
(g/sec)
(uglm3)
(gfsec)
(ug/mi)
(glsec)
(ug/in3)
(g/src)
(ug/m3)
MET LOCATION 3 SUE-Cl 5 50E-08 2 09E-08 1 67E-0? 6 34E-O8 3 SOE-Ol 1 331-0? 1 SiR-U? 6 B9E-O8
1 Monkey Run Residence I I 7OE-03 5 SUE-OS 9 351-11 1 67E-07 2 83E-10 3 SUE-U) S 95E-10 1 81E-07 3 081-10
2 Monkey Run Residence II 1 90E-03 5 SUE—Os I 04E-10 1 67E-U? 3 17E-10 3 SUE-U i 6 641-10 1 811-01 3 44E-10
3 Ila,co Residence I S OOE—04 5 SUE—OS 2 75E—1I 1 67E-O7 8 33E-l1 3 SOP-U i 1 JSE-10 1 81E-O7 9 U SE- I l
A I lasco Residence 11 2 1OE-03 5 50E—08 I 1SE-lO 1 67E-O ) 3 50E-I0 3 SOE-0i 7 34E-10 1 511-01 3 801-10
S Local Residence I 4 ?OE-03 5 SOE-08 2 SUE-b 1 67E-07 7 83E—1U 3 SOE-07 1 64E—09 1 BIE-O7 8 SIE-lO
6 Local Residence II 3 OOE-03 S 50E-08 1 6 5E10 1 6?E07 5 UOL1U 3 50E07 1 05E09 1 s iR-UI s 43E-i0
7 LeBaume Cave Residence I DOE-CA 5 SUE—OH 3 8 5E-11 1 67E-07 I 1)1-10 3 501U7 2 45E11J 1 81E0 / 1 21110
8 Residence near 60?’ Ter.aln Point 1 SUE-Ui S SUE-OH 8 25E—1] 1 67E-Ul 2 SOE-1O 3 SUE-U? 5 2 5E—10 1 81E-0? 2 /2E-i0
9 Residence In South Directlrn 1 7OE—03 5 SOE-O8 U ISP-I l 1 67E-O7 2 83E-I0 3 SUE-U? S 9 5E-1O 1 81E-O ? 3 08E-lO
10 Stacktop Height Location 2 25E-O1 S SUE-OH 1 24E-08 1 6 )EU ) 3 JSE-08 3 5U10? 1 8?L-08 1 SIR-U? 4 0?E-08
11 Elevated Terrain Location 1 2 BJE-02 S SUE-OR I S8E-09 1 67E-U7 4 78E-09 3 SUE-Ui 1 ODE-OR 1 81E-07 S 20E-09
12 Elevated Terrain Location II 4 92E-02 S SUE-OS 2 701-09 1 6?E-07 8 20E-09 3 SUE-Cl 1 72E-08 1 SiC-U) B 91E-09
p j 13 Elevated Terrain Location III F 54E—02 5 50E—O8 4 141—09 1 67E-O7 1 26E-08 3 50E-07 2 64E-08 1 81E-0l 1 lIE-OH
(11 14 Blessed Sacrament School 3 40E-03 5 5UE08 I 87E10 1 61E-0? 5 67E-1O 3 501-07 1 19E-09 1 811-0? 6 lIE-lU
S,. Tno y , 13 5 50E25 2 50E10 I S’EO’ B 1’E-lO I 50E0’ 1 ‘1E0° 1 S1E—’)’ ? Pun
16 Mark Twain SchooL A 2OE-O3 5 SUE—OH 2 31E-10 1 61E07 7 OOE-10 3 SUE-U? I AlE-OS 1 81E-01 / 61E-I0
1) Court house 2 9OE-03 5 SUE—OH I 59E-10 1 67E-0? 4 83E-10 3 SUE-C? 1 O1E—09 1 81E-O? 5 25E-10
18 City Hall 3 10E03 5 SOE-08 1 70E10 1 67E-Oi S 111I0 3 SOE-0l 1 U8E09 1 81E0? S liE -lU
19 Central School 3 SOE-03 S SUE—OS 1 92E-l0 1 67E-07 S 83E-10 3 SUE-U/ 1 22E-o9 1 811-0) 6 341-10
20 Pettibone School 4 8OE03 5 50EO8 2 64E-1O 1 67E01 8 UOE1O 3 SUE-Ui 1 68E-09 1 81E07 B 69E-10
21 St John School 2 ?0E03 S SOE-O8 1 48E10 1 67E07 4 SOE-1O 3 SUE-Ui 9 44E-10 1 81E01 4 89E10
22 Field School 2 ?OE-03 5 SUE-O8 1 48E-iO 1 67E-07 4 SUE-lU 3 SUE-C? 9 44E-1O I 81E-0i 4 69E-1U
23 Antioch Church 8 2OE-03 S SUE—O8 4 SIE-lO 1 67E-Ul 1 31E-U9 3 SUE-U? 2 87E-09 1 811-01 1 49E-09
24 Hospital Along Route 61 3 UOE-03 5 50E—O8 1 65E-1O 1 67E-07 5 OOE-l0 3 SUE-Cl 1 USE-U’) I 81E-U1 S 43 1-IC
25 hospitaL Along Route 36 3 OOE-03 5 501-08 1 65C-l0 1 67E-O? 5 OOE-IU 3 SUE-U? 1 OSE-09 1 8 1E-Ol 5 43E-1U
26 School Near Oakuood 3 80E-U3 5 SOE-O8 2 09E-1O 1 6?E—U ) 6 33E-1O 3 SOR-Ol 1 lIE-OS 1 811-07 6 881-10
27 Church Near Saverton 3 40E-U3 S SOE-OR 1 RIE-lO 1 6?E-0l S 61E-10 3 SUE-C? 1 ]41E-U9 1 811-07 6 16E-l0
28 High School Near Mason 4 6OE-03 5 SUE—OR 2 S IR-iC 1 67E-0? 7 67E-10 I SUE-U i 1 61E-09 1 SiR-Ui 8 lIE-lU
29 Turner School (Ely Road) 6 90E-03 S 50E—O8 3 751-10 1 67E-O? 1 15E-09 3 SOE-07 2 41E-09 I SiR-U? 1 25EU9
30 School SE of Hannibal 8 Terrace A ’, 3 SOE-03 5 SUE—Os i 921-10 1 67E-U? S 83E-l0 3 SUE-U? I 22E-09 1 SiR-U? 6 34E- IU
31 3 Church/1 School I Rts 61/36 2 8OE-03 5 SUE—Os 1 541-10 1 6?E-0 ) 4 671-10 3 SUE-Ui 9 ?9E-1U 1 811-07 S 07E-10
a ChLIQ Chi denotes concentration (uglm3); and Q denotes emission rate (gm/sec)
Run 1. BaselIne v/coal (only)
Run 3, Waste Fired
Run 4, Waite hired
Run 5, Baseline v/coal and diesel fu i
19
-------
7 0 TOXICITh ’ AND FATE ASSESSMENT
Although much of the following inforiration pertains specifically to 2,3,7,8-
terrachlorodibenzo(p)dioxin (2,3,7,S-TCDD), this profile is intended to
reflect the fate and toxicity of all dioxins and furans which are potentially
being emitted from the Continental facility Data on 2,3,7,8-TCDD is empha-
sized because this isomer is the most studied of the dioxins or furans In
this regard, the profile may tend to overstate the toxicity of dioxin/furari
emissions, since 2,3,7,8-TCDD is easily the most toxic isomer of all the
dioxins or furans Data were taken from several references (Sax, 1989, RTECS,
1990, HSDB, 1990; IRIS, 1990, and several EPA documents, 1986, 1988, 1989)
7.1 Physicochemical and Other Characteristics of Dioxirts
here individual parameters are noted, such as boiling point, they refer to
2,3,7,8, -TCDD specifically.
Class Name Dioxins, Polychlorinated Dibenzo-p-dioxiris
Soecific Isomer Na ne/Svnonvn’s
2,3,7,8 -Tetrachlorodiberizo-p-dioxin,
2,3,7,8-Tetrachlorodibenzo(l,4)diox in,
2,3,7,8 -Tetrachlorodibenzo(b , d) (1 ,4)dioxin,
2.3.7 ,8-TCDD ; TCDD, TCDBD, Dioxin, Dioxine, etc.
CAS RN 1746-01-6 NIOSH N HP 3500000
Chemical Farnilv Chlorinated Hydrocarbon Chemical Formula C 12 H 4 Cl O 2
Molecular Weitht 321 96 Boilirg Point 305°C
Soecific Gravity 1 326 @ 20°/4° Vaoor Pressure —1 OE-09 mrn.Hg @ 25°C
water Solubilitv . 8 to 19 ng/L @ —25°C 4E+06 to 1SE÷06 @—25°C
Herurv’s Law Constant . 3 60-03 atm-m 3 /mol 3 3E+06 ml/g
Fish Bioconcentration Factor 5,000 L/kg
Half-Life 3500-4500 days (soil), 350-700 days (surface water), Air -
N/A
D-26
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7 2 Environnental Fate of Dioxir
Sources Dioxins are formed as pyrolysis producr.s during the combustion of
chlorine-containing organics They are not known to occur naturally Incin-
erariom processes constitute a major source of dioxin production, where
dioxins may occur in emissions at concentrations generally in the parts per
trillion range (HSD3, 1990) The concentration depends upon chlorine content
of the feed material, combustion conditions, and pollution control The
exhaust of engines using leaded gasoline (containing ethylene dichioride as a
lead scavenger) constitutes another major 3ource of dioxins (ibid) Dioxins
also may be formed as by-products during the synthesis of chlorine-containing
chemicals including, particularly, chlorinated phenols Dioxin has been
widely recognized as a contaminant of the chlorinated phenoxy acetic acid
defoliant, 2,4,5-T (the active ingredient in Agent Orange), and its precursor,
trichiorophenol, although modern manufacturing practices have minimized the
occurrence of dioxin contamination in the manufacture of these chemicals
r Most major sources release dioxins diiectly into air (e g , incinerators
and cai exhaust), ien released from these sources, most of the dioxins are
tightly bound to particulate, such as fly ash, but some are in the vapor
phase Most dioxins are associated with particulate emissions due to their
very low vapor pressure and their strong tendency to adsorb to solid materi-
als. In the bound form, dioxins may be rapifly removed from the atmosphere by
rainfall or dry deposition, ultimately distributing in soils or sediments
Dioxins in the vapor phase are resistant to photochemacal degradation with a
half-life estimated at 8 3 days (HSDR, 1990) Dioxin concentrations near
Superfund sites have been measured in the range of 1 picogram per cubic meter
of air Ambient air sa p1es from Sweden sho ’ ed dioxin levels ranging from
o 02 to 0.08 pg/rn 3 . The empirical evidence s ows that the rate of migration
of dioxins from other media into air is low This is consistent with the very
low vapor pressures and Henry’s law constants of all the dioxin/furan conge-
ners.
0-27
-------
Soil Dioxin levels in U.S soil considered to be “uncontaminated’ (i e
rural) are usually below the analytical detection limit of 0 2 ng/kg (HSDB,
1990) However, urban soil concentrations, with no known source of dioxin
contamination, have been found to range up to 9 4 ng/kg Soils in the Times
Beach area of Iissouri, a site of dioxin contamination, were measured as high
as 382 micrograms per kg soil (ibid) Dioxin binds strongly to organic carbon
in soil This characteristic, combined with its very low water solubility,
reduces dioxin mobility. Thus, dioxins do not readily leach into ground
water Because of their strong soil-binding tendencies and very low vapor
pressure, dioxins do not readily evaporate into the air At the Seveso, Italy
release site, dioxins in the upper 8 to 10 cm of soil slowly volatilized,
showing a persistence half-life of 1 to 3 years while deeper soils exhibited
haif-lifes of 12 years Dioxins persist in the soil for long periods of time
not only due to their strong absorptive properties and low volatility, but
also due to the stable nature of the dioxin molecular structure, resulting in
chemical and biological half-life values in soil on the order of years to
decades (ibid) Despite the slow removal of dioxins from soil by this
mechanism, volatilization is, perhaps, the major mechanism of dioxin transfer
from soil to air, and is appreciably faster in the warmer summer months than
in winter (EPA, 1988).
Water : This medium may be contaminated directly via aqueous effluent dis-
charges from plants whose manufacturing processes produce dioxins as by-
products Indirectly, particulate deposition from incinerators and other
combustion devices c.ay transfer dioxins from air to surface waters In
addition, soil erosion may contribute to dioxin levels in the aqueous envirr’-
merit. Dioxins have not been detected in U S drinking waters but have been
found in measurable concentrations in 0 2 percent of STORET data on surface
waters (HSDB, 1990) In leachate samples from a contaminated dump-site,
dioxins were detected at a concentration of 60 ug/L In the aqueous environ-
ment, dioxins are predominantly associated with sediments and suspended
particulate In this bound form, dioxins may persist in sediments and the
water column for long periods of time due to the very low rates of release
D- 28
-------
from particle surfaces into the aqueous pha5e as well as the low rates of
biodegradation. Solubilizec dioxins may be removed from the water column by
evaporation and phocolysis at a relatively rapid rare. The overall race of
removal is slow, however, because the predominant direction of c e equilibrium
is toward the bound phase Removal is even slower in deeper water bodies Ac
the water’s surface, solubilized dioxins ma be removed by photolysis and
evaporation at a half-life rate of 10’s to 100’s of hours In an actual pond
environment, haif-lifes are on the order of years
Biota In earlier studies, TCDD was determined nor to bioconcentrate in
aquatic organisms to the same degree as other chlorinated hydrocarbons, such
as DDT, Heptachlor, Chlordane, etc (I-ISDB, 1990) Bioconcentracion factors
(BCFs), representing the ratio of water to Drganism dioxin concentrations (in
L/kg), reported in the earlier literature, were —20,000 for snails and
daphnia, —5,000 for catfish, —6,000 for fatiead minnows, and 3-8,000 for
rainbow trout (ibid). The 1986 Superfund Public Health Evaluation Manual
lists a BCF for TCDD of 5,000 L/kg (EPA, 1986). However, more recent studies
have indicated higher BCFs for TCDD 66,000 for carp and 100-160,000 for
fathead minnows (EPA, 1988)
More recently, sediment to organism concentration ratios, rather than water to
organism BCFs, have been used to estimate dioxin concentrations in aquatic
organisms (EPA, 1988) This is due to the difficulty of measuring low dioxin
concentrations in water required for determination of a water/organism BCF A
ratio of I to 10 (sediment to organism) ratio has been used recently to
estimate aquatic organism concentrations (ibid). TCDD has not been found to
biomagnify up the food chain, and does not concentrate in the top predatory
species such as rapiers (HSDB, 1990) Studies in cattle suggest a soil to
milk fat concentration ratio of 5 or less (EPA, 1988).
0-29
-------
7 3 Toxicity of Dioxins
TCDD is one of most toxic chemicals known, either from acute (single) or
chronic (longrerm/repeated) exposure Single lethal doses are less than 1
mg/kg for most species tested For the guinea pig, an oral LD-50 of 0 6 ug/kg
has been reported Even in the least sensitive species, hamsters, the oral
L.D-50 was approximately 1 mg/kg, still in the “Supertoxic” category as cefined
in Casarett & Doull (Klaassen, 1986). The 2,3,7,8-tetrachlorodibenzo-p-
dioxin, to which the above toxicity information pertains, is the most toxic of
the dioxin isomers The more highly chlorinated dioxins are also supertoxic,
having oral LD-50’s less than 1 mg/kg (Sax, 1989) Symptoms obser’. ed in
animals treated with dioxins include, loss of appetite, porphyria, and
wasting/loss of body fat The mechanism by which dioxins exert their toxic
effects is unknown Chronic effects in animals include, liver damage, thyroid
atrophy (one of most sensitive indicators), fetotoxic/teratogenic and repro-
ductive effects, immune suppression, tissue wasting/loss of body fat, liver
enzyme induction, and cancer
Toxic effects have been observed in humans overexposed to dioxins during
industrial accidents Findings observed in such workers are, chloracne, liver
damage, polyneuropachy, and psychiatric disturbances Members of the general
population have been exposed when industrial accidents (e g , Seveso, Italy)
or inappropriate disposal methods (e g , Times Beach, Missouri) have caused
dioxins to be released into the environment In addition, U.S. military
personnel and civilians were exposed to the dioxin-contaminated defoliant,
Agent Orange, in Viet Narn. Most epidemiological studies of such individuals
have not shown a conclusive association between exposure and adverse health
effects, although much controversy surrounds the studies A Swedish/American
study reported an increased incidence of soft tlssue sarcomas in individuals
exposed to phenoxy herbicides (Murphy, 1986) A study conducted in New
Zealand found a statistical association between phertoxy herbicide exposure and
congenital defects of the foot and urethral openings, but no increase in other
congenital abnormalities (ibid)
D-30
-------
No reference dose for noncarci.nogenic effec:s has been established for ary of
the dioxin isomers A cancer potency slope of 156,000 (rng/kg-dayy 1 has been
generated by EPA for 2,3,7,8-TCDD (EPA, 1985, HEAS1’, 1990) as well as a slope
of 6200 (mg/kg-dayY’ for hexachlorodibenzo-p-dioxin mixture (IRIS, 1990)
No potency factor is reported currently for TCDD in IRIS EPA has revised a
procedure, the “toxicity equivalence” factor (TEF) approach, which assigns
potency factors to non-TCDD dioxin and furat isomers which are some fraction
of that for TCDD (EPA, 1989) This scheme assigns fractional potency factors
only for isomers which have chlorine atoms in the 2,3,7,8- position (ibid)
The higher chlorinated isomers without chiorines in these positions are
assigned potency values of zero Mono-, di-, and tn-chlorinated DDs/DFs also
are not considered carcinogenic (ibid) Briefly, 2,3,7,8-PentachloroDDs are
assigned TEFs of 0.5; 2,3,7,8-HexachloroDDs - 0.1; and 2,3,7,8-OctachloroDD is
0 1 (ibid). 2,3,7,8-TCDFs have TEFs of 0 1, l,2,3,7,8-PeCDF - 0 05, 2,3,4,-
7,8-PeCDF - 0.5, 2,3,7,8-HxCDFs - 0 1, 2,3,7,8-HepCDFs - 0 01, and OctaCDF is
0.001 (ibid)
Risk Specific Concentrations (RSCs), corresponding to various probabilities of
contracting cancer, are derived from cancer potency slopes using the followirg
formula;
RSC (ug/rn3) — (1 OE-06/l.53E÷05) x 70 kg x 1,000 ug/mg x 1/20 m /day x 0 75
where 1 OE-06 is the risk level, 1 53E+05 (mg/kg-day) is the slope factor,
70 kg is average adult body weight, 20 m 3 i; the inhalation rate for an
average adult, and 0.75 is the fraction absorbed during each breath The RSC
corresponding to a I in 1,000,000 excess lifetime cancer risk, is 3 OE-08
ug/m 3 For a 1 in 100,000 risk, the concentration is 3 OE-07 ug/m 3 , and for a
1 in 10,000 risk, is 3.OE-06 ug/m 3 The “u-ut risk” factor for 2,3,7,8-TCDD
3 — 3 —1
is 3 3E-05 (pg/rn ) - or 33 (ug/m )
0—31
-------
8 0 RISK CHARACTERIZATION
8 1 Results
Table 8-1 shows the excess lifetime cancer risk from the Continental Cement
Kiln facility The figures In the first four columns represent the concentra-
tions in TCDD-equivalencs for each receptor A discussion of TCDD-equivalents
is included in the Section 6 0 of this report Multiplying these values by
the cancer potency slope for 2,3,7,8-TCDD yields the cancer risk to the
receptors The last four columns correspond to cancer risks for the different
sampling “runs,” wherein different feed materials were burned in the incinera-
tor. Run l reflects baseline conditions where only coal was burned Runs 3
and #4 represent runs where hazardous wastes were fed into the incinerator,
and run 5 represents another baseline where both coal and diesel fuel were
burned. For the MEL, baseline risks for run #1 (coal only) and run #2 (coal
and diesel fuel) were 0.7 and 2 3 chances in 1,000,000, respectively Runs #3
and 4, where hazardous waste was burned, yielded risks to the MEl of 2 1 and
4 4 in 1,000,000, respectively In this analysis, no individuals resided or
worked near the MEl location (i e , the MEl location was unoccupied) The
only other location where slightly lower cancer risks exceeded 1 chance in
1,000,000 was at a stacktop height location on a hillside approximately 2,700
meters downwind. This location is also unoccupied by any receptor at present
Cancer risks to other locations (such as the elevated locations) and risks to
discrete, non-theoretical receptors (i e., where humans are actually located)
were all less than 1 in 1,000,000
8 2 Assurirntjons and Uncertainty
Many assumptions were made in this risk assessment in the face of uncertainty
which tend to overestimate exposures and health impacts in order to err on
the side of protecting human health The exposure estimates and resulting
cancer risks assumed that all receptors are exposed continuously for a 70-year
lifetime This means that residents and occupants of any institutional or
hou1.d b noted that surrogate recoveries during the chemical a - aLy is for ru 4 vere Low (approxi-
mately one-half char for the other runs) Thus, the resuLt, from r- n 4 are suspect
D-32
-------
TABLE B- I EXCESS LIFETIME CANCER RISK FROM TIlE CONTINENTAL CEMENT KILN FACILITY
TCOU
I nh a tat ton
DATE 11/19/90
RECEPTOR RECEPTOR
U DESCRIPTION
MODELED
RUN 1
(uglcn3)
TCJJD-EQIJJVALENT
GROUND-LEVEL CONCFNTR.ATTON
RUN 3 RUN 4
(ugim l) lu g / n ’ 3)
RUN S
(ug/m3)
Cancer
Potency
Slope
(t.g/m3)-l
RUM 1
EXCFSS LIFET IME
RUN 3
CANCER RISK
RUN 4
RUN S
MEt LOCAT iON
2 O lE-OS
6 34C-O8
1 31-07
6 9E-O8
33
6 9E-O1
2 1E-Oo
4 4K-O6
2 3E-06
10
Sracktop Height Location
1 24K-OS
3 75K-OS
7 SE-OS
4 1E-08
33
4 1E-07
1 2E—O6
2 6E-06
I 3K-OK
1 1
Elevated Terrain Location I II
4 14 1-09
1 26E-08
2 6 1-0 5
1 4K-OS
33
1 4K-C?
4 11-07
8 1K-Of
4 5E-O?
12
Elevated Terrain Location II
2 /01-09
5 20K-ag
1 71-05
8 9E-09
33
S 9K—OS
2 7K-Cl
5 7K-UI
2 9K-U?
11
Elevated Terrat, , location 1
1 SBE-O9
4 781-09
I CE-OS
S 2E09
33
5 2E-0S
1 6K07
3 3K -Cl
1 7E07
23
Antioch Chutc lt
6 511-10
1 3?E-09
2 91-09
1 5E-O9
33
i SE-O S
4 5 1-03
9 SE-OS
4 9K-OS
29
Turner School (Ely Road)
3 79K-lU
1 i5EQ9
2 4K-OS
1 2K-a c
33
1 3K-CO
3 SE-OR
S OK-OS
4 1K-OS
15
St Thomas Seminary
2 69E10
8 17E10
1 7E09
S 9E10
33
S 9E09
2 7E08
S 1EOO
2 9E-OS
20
Pett lttone SchooL
2 6 41-10
5 CUE- lB
1 7K-OS
B 7K-ID
33
8 7E-09
2 6K-Os
S 5K-OS
2 9E-02
S
Local Residence I
2 SUE-lU
1 53K-lU
I 6E-09
U SC-b
33
5 SE-DO
2 6K—OS
S 4K-US
2 SE-OS
25
HIgh School Near Maaon
2 53E-lO
1 67K-tO
1 61-09
5 31-10
33
8 31-09
2 SE-OS
S 3K-OS
2 7K-OS
16
Mark Twain SchooL
2 31 1-10
7 00K-l U
1 SE-09
1 6E-30
33
7 6K-ac
2 3K-OS
4 HE-US
2 SE-OS
26
School Near Cakwood
2 09E10
6 33E-l0
1 31-09
6 9E10
33
6 9K-GO
2 ItrOS
4 4K-OS
2 3E0S
19
Central School
1 92E-lO
S 53K-lU
1 21-09
6 3K-l U
33
6 3K-Dc
1 cE-OS
4 SE-OS
2 IE-OS
30
School SE of hannibal I ! Terrace Ave
1 921-10
5 S3E-1O
2E-O9
6 3K-ID
33
6 3K-09
1 SE-OS
4 OF-OS
2 1K-OS
14
Blessed Sacrament School
I 5 )1-10
5 6 7K-i D
I 21-09
6 2F-lO
33
6 2K- DC
1 1.i- 3
3 41-us
2 OK-OR
2’
C ’t-ro’-, Ncr.r C ;crt ,
I O I L- lU
5 67E10
1 2z-C9
6 21-10
33
6 1K-09
1 9K—Ui)
3 9K-OS
2 OK-OS
18
City Hall
1 10 1- 10
5 13E-I0
1 11-09
S 6K- b
33
5 61-09
I 7E-U5
3 61-05
1 9K-OS
6
Incal }Iestdtnce I I
3 6 1 1-10
5 ODE-l U
1 CE-OS
S 4K-tO
33
5 4K- e Q
1 6K-OS
3 SE-OS
1 BK-Oh
24
Hospital Along Route 61
1 OSE- lO
S ODE-ia
i 0E09
5 4E-10
33
5 41-09
1 6K-OS
3 SE-OS
1 SE-OS
25
Hospital Along Route 36
1 65K-ID
S OOE-l0
I CE-OS
S 4K-tO
33
5 4K-OS
I 6K-Us
3 5K-OS
1 SE-OS
17
Court House
1 59K-tO
4 S3E10
1 OE-09
5 3E10
33
5 3K-OS
1 6K-OS
3 3K-OS
1 7 1-OS
31
3 Church/l School € Rts 61136
1 S4E-1O
4 6 1K-lU
9 51-10
5 11-30
33
S 11-09
1 SE-OS
3 2K-OS
1 7K-OH
22
Field School
1 4SE-10
4 50 1-10
9 4K-lU
4 9K- b
33
4 SE-Cc
I SE-OS
3 1K-OS
I 6K-OS
21
St Joint School
1 451-30
4 SUE-l a
9 4K-iC
4 9K-IC
33
4 9K-09
1 5K-OS
3 bE-OS
1 6K-OS
4
Ilasco Residence II
I 15K-lU
3 50K-to
,‘ 3K-lU
3 SKIO
33
3 8KO9
1 2K-OS
2 41-08
1 3E-OS
2
Monkey Run Residence II
1 OiK-bO
3 17 1-10
& 61-10
3 4E-I0
33
3 4E-09
I CK-O5
2 2K-Os
1 IE-OS
9
Residence In South D Irection
9 351-11
2 53K-iD
S 9K—lU
3 1K-IC
33
3 11-09
9 3K—OS
2 OK-OR
1 OK-OS
1
Monkey Run ResIdence 1
9 35K-li
2. 53K- lB
S 9K- ID
3 11-10
33
3 11-09
9 3E-O9
2 OK-OS
1 OK-US
S
Residence near 60.’ TerraIn Point
S 25K-li
2 50K-iS
5 2 1-10
2 7K-b
33
2 /K-09
S 2 1-09
1 7K-OS
9 UK-Dc
7
LeBaume Cave Residence
3 051-11
1 17K-tO
2 4E10
1 IF- tO
33
1 3E-O9
3 SE-OS
S 1K-DO
4 2K-Dc
3
fIasco Residence 1
2 75K-il
S 33 1-11
1 7E-lO
9 11-11
33
9 1 1-10
2 71-09
S 51-09
3 OK-OS
Baseline u/coal (onlyl
Waste Fired
Waste Fired
Baseline u/coal and dIesel fuel
Run 1.
Rnn 3,
Run 4.
Run 5;
2 1
-------
commercial structures were always at the receptor location for a seventy-year
lifetime (never leaving), 24 hours per day. In reality, receptors, particu-
larly in institutional or commercial facilities (e g , churches, hospitals,
offices), would not be exposed continuously for a 70-year lifetime In addi-
tion, it was conservatl\.?ly assumed that estimated concentrations inside such
structures were equal to o .;tdoor concentrations The air dispersion model
used to project downwind concentrations of dioxin did not use local meteoro-
logical data, but, instead, conservatively assumed that a receptor (wherever
its location) was always directly downwind from the stack
Finally, the cancer potency slope (CPS), from which the excess lifetime cancer
risks were estimated, is a 95% upper-bound estimate of the slope of the dose-
response curve for TCDD-induced cancer In deriving the CPS, EPA uses data
from high-dose animal studies to extrapolate the probability of contracting
cancer at very low doses in humans (it is not practical to conduct experiments
on the extremely large numbers of animals that would be necessary to detect an
increased cancer incidence at much lower, more realistic dose levels, mlllions
of animals per dose might be required) The linearized multistage model,
which EPA generally uses to estimate the slope of the cancer dose-response
curve at low doses, is not capable of accounting for bodily defense mechanisms
which are overwhelmed at high doses but which might prevent cancer at lower
doses, which the model tries to predict Thus, the cancer-based, risk-
specific acceptable concentrations are intentionally health-protective in that
they tend to overestimate the cancer risk which would result from lifetime
exposure. It is not possible at this time to estimate the degree oE conserva-
tism provided by the risk specific concentrations
8 3 Summary
TCDD-equivalent dioxin concentrations were modeled for the most exposed
individual (MEl) and several discrete downwind receptors using conservative
modeling techniques Only risks to the MEl and the “stacktop height’ receptor
exceeded the 1 in 1,000,000 risk level. No actual receptors are located at
either of these locations at the present time. Baseline risks for a coal-only
0-34
-------
run was 0 67 chances in 1,000,000 for the MEl and 2 3 in l,000,00C for a
coal/diesel fuel run Risks to the MEl for two incineration “rur ,” where
hazardous waste was burned, produced risks cf approximately 2 in 1,000,000 ant
4 in l,000,C00 Risks for stacktop height location were approximately half
those for the MEl location For the second hazardous waste run (run p4), low
surrogate recoveries render the results of this run questionable Cancer
risks from baseline (fuel only) runs, when compared to risks from hazardous
waste runs, are roughly comparable (i e , are within an order of magnitude of
each other).
D- 3
-------
REFERENC ES
Auer,A H ,Jr 1978 “Correlation of Land Use and Cover with Meteorological
Anomalies Journal of Apnlied Meteorology 17 636-643
EPA, 1985 Guideline for Determination of Good En ineer ng Practice Stack
Height (Technical Support Documer’t for the Stack Height Reguletions) , Revised
EPA Publication No EPA-450/4-80-023R. US EPA, Research Triangle Park, NC
EPA, 1986a Superfund Public Health Evaluation Manual , Office of Emergency
and Remedial Response EPA54O/l-86/060
EPA, 1986b. Guideline on Air Cualicv Models (Revised) , EPA Publication No
EPA-450/2-78-027R. US EPA Research Triangle Park, NC
EPA, 1987a. The Risk Assessment Guidelines of 1986 Office of Health and
Environmental Assessment EPA/60 0/8 -8 7/045
EPA, l987b. Suoplement A to the Guideline on Air Quality Models (Revised)
EPA Publication No EPA-450/2-78-027R ,Supplernent A
EPA, 1988a Draft Superfund Exposure Assessment Manual , OSWFR Directive
9285 5-1.
EPA, 1988b Estimating Exposures to 2 3 7 8-TCDD , Office of Health and
Environmental Assessment. EPA/600/6-88/005A,
EPA, 1989a Risk Assessment Guidance for Superfund Volume I Human Health
Evaluation Manual (Part ) Interim Final. Office of E tergency and Remedial
Response, EPA/540/l-89/002.
0-36
-------
EPA, 1989b Interim Procedures for Estimating Risks Associated with Exposures
to Mixtures of Chlorinated Dibertzo-o-Dioxins and -Dibenzofurans (CDDs and
CDFs) and 1989 Update Risk Assessment Forum, U S EPA EPA/625/3-89/016
HEAST, 1990 Health Effects Assessment Swpmarv Tables Third Quarter, 1990
EPA OERR 9200 6-303-(90-3)
Holzworch,G C 1972 Mixing Heights, Wind Speeds and Potential for Urban Air
Pollution Throughout the Contiguous United States EPA Publication No AP-
101 US EPA, Research Triangle Park, NC.
HSDB, 1990. Hazardous Substances Data Base On-line computerized EPA data
base available through the National Library of Medicine, Bethesda, MD.
Industrial Source Complex Model (ISC). Environmental Protection Agency, 1986
Industrial Source Complex CISC) Disoersion Hodel User’s Guide , Second Edition,
Volumes 1 and 2 Publication t4os EPA-450/ 1 u-86-005a, and -005b US EPA,
Research Triangle Park, NC (NTIS PBS6 2342 9 and P386 234267)
IRIS, 1990. Integrated Risk Information Sv E . On-line computerized data
base compiled by EPA and available through the National Library of Medicine,
Bethesda, MD.
Klaasseri, C.C , 1986. “Principles of Toxicology Chapter 2 in Casaretc and
Doull’s Toxicology, The Basic Science of Poisons (3d Ed ) (C D Klaassen, M 0
Aindur, and J Doull, Eds). Macmillan Publishing Co. New York
Murphy, S D , 1986 “Toxic Effects of Pesticides “ Chapter 18 in Casaretr and
Doull’s Toxicology, The Basic Science of Poisons (3d Ed ) (C U Klaassen, M 0
Amdur, and J.Doull, Eds). Macmillan Publishing Co. New York
RTECS, 1990. Registry of Toxic Effects of Chemical Substances On-line
computerized data base compiled by the National Institute for Occupational
D-37
-------
Safety and Health (NIOSH) available through the National Library of 1edLcLne,
Bethesda, MD
Sax, 1989 Dangerous ProtertLes of Industrial Materials (7th Ed ) Van
Nostrand Reinhold Co , New York
D-38
-------
APPENDIX A
TCDD-Equivalent Emission Rates for the Continental Facility
from a rep t: by
Mid .’est Research :nstitute
D- 39
-------
Iable 3 3 /.8 ICIM) EaUIVM Effi EMIS 2IONS
A iaIy1
C P A
flIuiv
) ) iti I
S411%IIu i olii,iu ( seili) = I .14?
St. .k how •.iiO (d i 1)/ni) 2 / 3
Tol gi Ei 1 iii
(j9> in) (Il .jhhbcIlm)
hIjii 3
S.iii.gilo vOh lirliti (il .ciii} I 714
la 1. Ihiw I sin { .I s ill/ill) 3 004
l i il . il E II IV
(pij) (i 1(l/Il5C1I%i s1tl/.ii uisl)
) ),ii .1
S.s ssip lo vohisiin (sist In) = I 1105
Sho ._k Il.w foI .i ( .b . iii1ii .) 3 418
I ol.sl I .puuv
);, )J) (iij/iI cisi) (,s . lii. i is)
liii 5
5lrIi(JI .1 v .,Itisiin (iI t is) I 788
8 Iliw 14 1u (,l Lsu1/sul .1 141
011.11..
(i’o) ( .t /i l . .csss) (i 1901 ..cIis)
F..s ins
23 7 B—ICDf
I 2 3 1 B—PoCDF
2 3 4 7 8-PuCDF
I 2 3 4 7 8- 14 .COF
I 2 36 7
234678-I IxCl)F
C) 123 780-I4 . .CDF
I 2 34 6 1 6—hIpCO
I 2 3 4 1 8 iJ- )1 1 ,CO
ocoI
Dsox s s
2378-ICOI) 1
131
00660
00660
106
00210
00210
219
0)2)
0121
121
00151
0015)
I 237 8-P.,C0L) 05
255
00516
0 0258
3740
0942
0471
4520
I 3)
0 655
•
5 220
I 45
0 727
1 2 34 78 IIMCDO 0 I
5 50
00643
000540
‘I 550
00497
000497
7 110
2 08
0 208
0280
2 50
0 2513
I 23 67 8-hIxCUD 0 I
647
0 447
0 ()n1F
3750
I 09
0 100
7040
201
0201
II 100
3 09
0 309
I 23 / B 9-hixCDO 0 I
520
0 359
0 0359
4 ( iOU
I 45
0 145
7 8110
2 28
0 228
9 I SO
2 55
0 255
I 2346 / C-IhpCt) 001
4 140
2 8)8
00286
12 100
360
00361
21 .100
6 Il
00611
36000
I O U
0 100
CCI ) ) ) 0 001
5380
3 10
(50(137
lb 000
4 SI
0 00401
Ii) 500
565
0 00505
19800
4 40
000440
01
144
0 138
0uI33
210
01
001
3311
010
0010
412
1113
0013
01)5
149
0103
0iJ05 15
6490
69
00943
10400
301
0 151
1 720
104
005)8
05
2320
I SO
080.’
14900
433
217
27400
794
397
10800
30)
15)
0 1
1 140
0 7811
00/58
4 9)0
I 44
0 145
7 140
2 16
0216
3 /20
11)4
0 104
01
57)
0395
00305
2350
06113
00683
3900
I IS
0116
2000
055/
00560
0 I
531
0 ib)
0 0269
884
0 25?
00257
I 720
0 498
0 (J1’J8
:so
0 35
0035
0)
381
009)89
000068
5 05
0164
00184
741
02)5
00215
. 1 1 )3
00044
0001140
001
2 050
I 42
00142
4 756
1 38
0 0138
4 860
I 41
00141
I 4(113
031)0
000390
00)
356
0246
000248
5l
01513
000159
643
0 186
000185
256
001s3
0000700
0001
1 660
I IS
000115
3530
I 03
000103
3 0 0
0881
00005110
sO s
0 161)
0000170
TolnI 2 3 / 0-I COD
us )sIiv.sh .siII Ci ii itIiIl .ihls)ii ( 1 19/iIsCIfl)
3329
13033
3 45
Es, ii.,siOss (isijOlOil)
3 299
10000
20 0110
10 880
t:ssII .SII5 (.;/Iii)
(10001979
00006000
00(11255
0 00061 i2
Null Iii La )CIII.lli 5I1J 2 3 7 8—ollIllydI . Ills Iii I5I)lIiUI5 ) 5ll1i )W du1o lii.iis l innIx I)io iJ.lI i_lisspi Iiii iil W.IS si JtI
FIle 237BEQUIV Dale 11/7/90 Dy PSM
------- |