EPA/540/2-89/011
SUPERFUNDTREATABILITY
CLEARINGHOUSE
Document Reference:
Shirco Infrared Systems. "Final Report: On-Site Incineration of Shirco Infrared
Systems Portable Pilot Test Unit, Times Beach Dioxin Research Facility, Times Beach,
Missouri." Technical report prepared for U.S. EPA. Approximately 200 pp.
November 1985.
EPA LIBRARY NUMBER:
Superfund Treatability Clearinghouse - EUTR
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SUPERFUND TREATABILITT CLEARINGHOUSE ABSTRACT
Treatment Process:
Media:
Document Reference:
Document Type:
Contact:
Site Name:
Location of Test:
Thermal Treatment - Infrared Incineration
Soil/generic
Shirco Infrared Systems. "Final Report: On-Site
Incineration of Shirco Infrared Systems Portable
Pilot Test Unit, Times Beach Dioxin Research
Facility, Times Beach, Missouri." Technical report
prepared for U.S. EPA. approx. 200 pp. November
1985.
Contractor/Vendor Treatability Study
U.S. EPA - Region VII
726 Minnesota Avenue
Kansas City, KS 66101
913-236-2800
Times Beach Dioxin Research Facility, MO (NPL)
Times Beach, MO
BACKGROUND; During the period of July 8 - July 12, 1985, the Shirco
Infrared Systems Portable Pilot Test Unit was in operation at the Times
Beach Dioxin Research Facility to demonstrate the capability of Shirco's
infrared technology to decontaminate silty soil laden with 2,3,7,8-
tetrachlorodibenzo-p-dioxin (TCDD) at a concentration range of 156 to 306
ppb. Emissions sampling and final analysis was performed by Environmental
Research & Technology, Inc. (ERT), while laboratory analysis of the
emissions and soil samples was performed by Roy F. Weston Inc. Shirco
Infrared Systems prepared the testing procedure protocol and operated the
furnace system.
OPERATIONAL INFORMATION; A singe 55 gallon drum of contaminated road bed
soil which had been screened through 1/2 inch mesh and homogenized in a
mixer was used. Two primary furnace solid phase residence times were
evaluated: 30 minutes and 15 minutes. Emissions and soil sample testing
accompanied both of these tests. A consistent furnace feed rate averaging
47.7 Ib/hr at a 1 inch bed depth was maintained during the 30 minute
residence time test. The feed rate during the 15 minute residence time
test averaged 48.1 Ib/hr with a 0.75 inch bed depth.
An important process parameter during testing was chamber temperature,
in both the primary and secondary chambers. Over the effective process
length of the primary chamber, temperature was controlled in two equal
length zones. During the 30 minute residence time test, the feed end zone
maintained a nominal temperature of 1560°F and the discharge end zone
maintained a nominal 1550°F. For the 15 minute residence time test, the
respective temperatures were both 1490°F. The secondary combustion chamber
was heated by a propane burner and its temperature was maintained above
2200 F during both tests. The nominal secondary chamber temperatures were
3/89-6 Document Number: EUTR
NOTE: Quality assurance of data may not be appropriate for all uses.
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2250°F and 2235°F, respectively, for the 30 and 15 minute primary chamber
residence time tests.
PERFORMANCE! For both tests, the soil discharge concentration of
2,3,7,8-TCDD was less than 38 parts per trillion. Based upon the expected
detection limit of 50 picograms of 2,3,7,8-TCDD as measured by the Weston
GC/MS system and the sampling volume capability of the ERT emissions test
equipment, the feed rates were more than adequate to confirm the required
99.9999% Destruction Removal Efficiency (DRE). Particulate emissions were
well below the standard of .08 gi/SCF @ 7% 02- Laboratory QA/QC procedures
are discussed in the report.
CONTAMINANTS;
Analytical data is provided in the treatability study report. The
breakdown of the contaminants by treatability group is:
Treatability Group CAS Number Contaminants
W02-Dioxins/Furans/PCBs 1746-01-6 Tetrachlorodibenzo-p-
dioxin (TCDD)
3/89-6 Document Number: EUTR
NOTE: Quality assurance of data may not be appropriate for all uses.
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FINAL REPORT
ON-SITE INCINERATION TESTING
OF
SHIRCO INFRARED SYSTEMS PORTABLE PILOT TEST UNIT
TIMES BEACH DIOXIN RESEARCH FACILITY
TIMES BEACH, MISSOURI
REPORT NO. 815-85-2
NOVEMBER 14, 1985
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SUMMARY
During the period of July 8 through July 12, 1985, the Shirco Infrared Systems
Portable Pilot Test Unit was in operation at the Times Beach Dioxin Research
Facility to demonstrate the capability of Shirco's infrared technology to suc-
cessfully decontaminate soil laden with 2,3,7,8 tetrachlorodibenzo-p-dioxin
(TCDD). Equipment set-up, preliminary operation, test operation, decon-
tamination, and takedown were performed during this period. Operation of the
furnace system to decontaminate the dtoxin-laden soil, and sampling of stack
emissions, feed, and discharge streams were accomplished on July 10 and 11.
The Missouri Department of Natural Resources Environmental Division coordinated
the site preparation. Emissions sampling and final analysis was performed by
Environmental Research & Technology, Inc., (ERT) while laboratory analysis of
the emissions and soil samples was performed by Roy F. Weston Co. Shirco
Infrared Systems prepared the test protocol and operated the furnace system.
The testing was planned such that adequate material quantity would be processed
and adequate samples of emissions and soil would be taken to assure that maximum
soil decontamination and destruction efficiency levels would be demonstrated.
Two (2) primary furnace solid phase residence times were evaluated: 30 minutes
and 15 minutes. Emissions and soil sample testing accompanied both residence
time tests. A consistent furnace feedrate averaging 47.7 Ib/hr at a 1 inch bed
depth was maintained during the 30 minute residence time exposure. The feedrate
during the 15 minute residence time test averaged 48.1 Ib/hr with a 0.75 inch
bed depth. Based upon the expected detection limit of 50 picograms of
2,3,7,8-TCDD as measured by the Weston GC/MS/MS system and the sampling volume
capability of the ERT emissions test equipment, the feedrates were more than
adequate to confirm the required 99.9999 % destruction efficiency.
An important process parameter during testing was chamber temperature, in both
the primary and secondary chambers. Over the effective process length of the
primary chamber, temperature was controlled in two equal length zones. During
the 30 minute residence time test, the feed end zone maintained a nominal tem-
perature of 1560°F and the discharge end zone maintained a nominal 1550°F. For
the 15 minute residence time test, the respective temperatures were both 1490°F.
The secondary combustion chamber was heated by a propane burner and its tem-
perature was maintained above 2200°F during both tests. The nominal secondary
chamber temperatures were 2250°F and 2235 °F, respectively, for the 30 and 15
minute primary chamber residence time tests. The temperature of the exhaust gas
leaving the wet gas scrubber and discharging into the atmosphere was nominally
165°F over the entire test duration.
The emissions test sampling performed by ERT was accomplished using a modified
EPA Method 5 with XAD-2 resin to capture any dioxin present in the exhaust
gases. The procedures, results and quality control for these tests are
explained in the Appendix A report submitted by ERT.
The analysis of the emissions, feed soil, and discharged soil samples were per-
formed at the EPA-approved Weston laboratory located at the Riedel Environmental
Services Office in Chesterfield, Missouri. The test procedures, results, and
quality control are presented in their report presented in Appendix B.
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In summary, these two appendices report:
Composite feed soil
2,3,7,8-TCDD concentration
Composite discharge soil
2,3,7,8-TCDD concentration
Participate emissions
at 7% 02
Gas Phase ORE of
2,3,7,8-TCDD
EPA
STANDARD
N/A
<1 ppb
0.08 gr/dscf
>99.9999%
30 MINUTE
RESIDENCE
227 ppb
Not detected
at 38 ppt
0.001 gr/dscf
>99.999996%
15 MINUTE
RESIDENCE
156 ppb
Not detected
at 33 ppt
0.0002 gr/dscf
>99.999989%
In conclusion, the testing performed by Shirco Infrared Systems using the
Portable Pilot Test Unit has proven the process and technology to be a success-
ful method of decontaminating the dioxin-laden soil present at Times Beach,
Missouri. The following report discusses the equipment, feed material, and pro-
cedures used in the test program, and results of that program.
The Appendix A and B reports present in detail the emissions sampling and sample
analysis results and procedures. '
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TABLE OF CONTENTS
Summary
1.0 Introduction
2.0 Test Equipment
2.1 General
2.2 Material Feed
2.3 Primary Chamber
2.4 Secondary Chamber
2.5 Combustion Air System
2.6 Offgas Handling System
2.7 Control System
2.8 Data Acquisition System
2.9 Heating Element Power Centers (HEPC's)
Figure 2-1 Portable Pilot Test Unit
Figure 2-2 Equipment Layout
3.0 Safety Procedures and Equipment
3.1 General
3.2 Protective Equipment
3.3 Personnel Training
3.4 Emergency Procedures
3.5 Stress Monitoring and Breaks
3.6 Protective Equipment Application and Decontamination
3.7 Furnace Operating Safety
3.8 Process and Testing Equipment Decontamination
4.0 Site and Test Material Description
4.1 Site Description
4.2 Test Material
5.0 Test Conduct and Procedures
5.1 Operational History
5.2 Equipment Set-Up
5.3 System Heat-Up
5.4 Contaminated Soil Feed
5.5 Scrubbing System
5.6 Operating Data Log
5.7 Operating Conditions
5.7.1 Test Condition Matrix
5.7.2 Primary Chamber Temperature
5.7.3 Primary Chamber Residence Time
5.7.4 Secondary Chamber Temperature
5.7.5 Primary and Secondary Chamber Combustion Air
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5.7.6 Contaminated Soil Feed Rate
5.7.7 Furnace Draft
5.8 Emissions Testing
5.8.1 General
5.8.2 Sample Procedures
5.9 Soil Sampling
5.10 Soil and Emissions Sample Analysis
Table 5-1 Test Condition Matrix
6.0 Test Results/Conclusions
6.1 General
6.2 Feed Material
6.2.1 Material Properties
6.2.2 Soil Feed Rate
6.3 Soil Decontamination
6.4 Stack Emissions/DRE
6.4.1 2,3,7,8-TCDD Emissions
6.4.2 Particulate Emissions
6.5 Scrubber Effluent Analysis
6.6 Equipment Operation
6.7 Process Temperatures
6.8 Power Usage
Figure 6-1 Feed History - 30 Minute Residence Time
Figure 6-2 Feed History - 15 Minute Residence Time
Figure 6-3 Temperature Recorder Chart - July 9, 1985
Figure 6-4 Temperature Recorder Chart - July 10, 1985
Figure 6-5 Temperature Recorder Chart - July 11, 1985
Table 6-1 Test Data Summary
Table 6-2 Furnace Feed History - 30 Minute Residence Time
Table 6-3 Furnace Feed History - 15 Minute Residence Time
Table 6-4 Operating Power Consumption
7.0 References
Appendix A ERT Emissions Sampling Report
Appendix B Weston Laboratory Analysis Report
Appendix C Site Safety Plan
Appendix D Test Site Description
Appendix E Operating Logs
Appendix F UMC Laboratory Analysis Report
Appendix G Personnel health Monitoring Data
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1.0 INTRODUCTION
Dioxin contamination of Times Beach, MO, and the community's subsequent
evacuation, closing, and disincorporate have been well-documented and
publicized. Today, an estimated 200,000 tons of dioxin-contaminated soil
exists within the city limits, which have been sealed off to unauthorized
entry.
The Missouri Department of Natural Resources (MDNR) has set up a Dioxin
Research Facility within the city. MDNR's mission is to investigate means
of decontaminating the soil, including thermal destruction. Concurrently,
the U.S. EPA has extended the Resource Conservation and Recovery Act (RCRA)
to require incineration of dioxin-bearing materials to achieve a destruc-
tion and removal efficiency (DRE) of 99.9999 percent of the dioxin. During
July, 1985, Shirco Infrared Systems, Inc. (Shirco), and its Portable Pilot
Test Unit became the focal point for DNR's investigation of on-site thermal
destruction of dioxin.
Shirco Infrared Systems has perhaps the only mobile pilot waste thermal
processing system available. This system is comprised of a belted electri-
cally powered primary furnace, a propane fueled secondary chamber, a com-
bustion air supply system, a single venturi wet gas scrubber, and a process
monitoring and control system. During the week of July 8, 1985, tests were
performed at the Dioxin Research Facility for the process of determining
the ability of the Shirco Portable Pilot Test Unit to meet the EPA
emissions and soil decontamination standards for dioxin incineration. The
test program consisted of three (3) days of thermal processing, of which
two (2) were.spent accumulating emissions and soil samples. The remaining
time was devoted to equipment set-up, decontamination and take-down.
MDNR requested the incineration test and coordinated site preparation. The
emissions and soils sampling was performed by Environmental Research and
Technology, Inc. (ERT), with subsequent laboratory analysis by Roy F.
Weston Co. (Weston). Shirco provided the portable incineration pilot
system and coordinated the test operations. In order to evaluate the test
and its results, presented herein is a description of the portable pilot
incineration system, safety procedures, test procedures, and results.
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2.0 TEST EQUIPMENT
2.1 General
The Shirco Portable Pilot Test Unit (Figures 2-1, 2-2) is designed to
demonstrate the performance of the Shirco Infrared "Furnace in a
variety of thermal processing applications. The system consists of a
feed metering conveyor, infrared primary chamber, gas-fired secondary
chamber, offgas handling, data acquisition and control equipment, and
heating element power centers (HEPC's). The system is housed in a 45'
van trailer.
2.2 Material Feed
Material to be processed is fed onto a metering conveyor located at
the feed end of the furnace by manual dumping. The metering belt is
synchronized with the furnace conveyor to control the material feed rate.
A feed hopper is mounted above the conveyor belt. The conveyor is
shrouded and equipped with rubber skirts to minimize inleakage of air
or escape of furnace gases. An adjustable guillotine-type gate is
provided at the conveyor discharge. The gate levels the material and
distributes it across the width of the metering belt. The gate and
the material behind it complete the furnace sealing feature. Final
feed area sealing is provided by an additional adjustable knife gate
in the feed chute into the furnace.
The metering conveyor drive is interlocked with the secondary chamber
temperature monitoring system. If the secondary chamber temperature
should fall below a preset value, feed to the primary chamber is auto-
matically shut off.
2.3 Primary Chamber
The primary chamber consists of a rectangular cross section "box"
fabricated from carbon steel and lined with layers of ceramic fiber
blanket mounted on stainless steel studs, and retained with ceramic
fasteners. The material to be processed is conveyed through the fur-
nace on a woven wire belt which is supported on high-temperature alloy
rollers. The rollers are, in turn, supported by external flange-mount
bearings. A friction drive system is used to pull the belt through
the furnace. When the processed material reaches the discharge end of
the furnace it drops off of the belt through a chute and into an
enclosed hopper. The hopper contains a residue sampling drawer and
seal gate for collection of "grab" samples of ash during processing.
Infrared energy is provided by transversely-mounted heating elements.
The elements are silicon carbide rods, with external electrical con-
nections at both ends. Access to the connections is gained by
removing sheet metal wireway covers. The elements are grouped into
two (2) control zones, with each zone being powered by a heating ele-
ment power center (HEPC).
The primary chamber has nominal external dimensions of 2.5 ft wide x
9.0 ft long x 7.0 ft high, and an installed weight of 3000 pounds.
Its process capabilities include 500 - 1850°F process temperature,
with material residence time variable between ten and one hundred
eighty minutes (10 - 180 min). Oxidizing, reducing, or neutral
atmospheres can be provided.
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For the test conducted at the Times Beach facility, the primary
chamber was operated in the incineration mode.
2.4 Secondary Chamber
The secondary chamber is similar in construction to" the primary
chamber and also uses ceramic fiber blanket insulation. A propane-
fired burner is used to ignite combustible gases present in the
exhaust, and burn them at a predetermined temperature. Propane is
supplied from a gas bottle located outside the system trailer. The
chamber is sized to provide the required combustion residence time for
the gases at setpoint temperature (typically 1.5 to 2.2 seconds). It
has external dimensions of 3.0 ft wide x 9.0 ft long x 3.0 ft high, a
weight of 1,500 pounds, and process capabilities of 2300°F, 2.2
seconds gas residence time, and 0-100% excess air. The burner is
mounted in the chamber end plate, with the flame pattern intercepting
incoming primary chamber exhaust gases at a 90° angle. A pilot and
electronic flame monitoring are provided as safety measures. Chamber
operating temperature is controlled by adjusting the manual gas valve
and air registers. Temperature is measured by a thermocouple located
at approximately 1/3 of the chamber length from the burner outlet.
The secondary chamber served as a gas-fired afterburner in this test.
It was used to raise the primary chamber exhaust to a minimum 2200°F
temperature before discharging those gases to the scrubbing system.
2.5 Combustion Air System
Combustion air for the primary and secondary chambers is supplied by a
blower with manual adjustment of airflow rate and distribution. A
splitter manifold with dampers at the blower outlet allows control of
airflow to both chambers.
In the primary chamber, air is injected at various points along the
length of the chamber through a manifold system. Adjustment of the
flow to an injection point is by means of manually-adjusted blast gate
valves.
In the secondary chamber, air is injected through the chamber top and
sides directed at the interface of the burner flame pattern and
exhaust gas inlet flow. Adjustment of flowrate is by means of a blast
gate valve and the burner air registers.
2.6 Offgas Handling System
Exhaust gases from the secondary chamber pass through a venturi
scrubber section containing water sprays, and a separator tower. A
manually-adjustable cone-type damper located in the venturi section is
used to control scrubber pressure drop.
The sprays in the venturi inject a fine water mist into the exhaust
stream. The water droplets are sized to "capture" particulate grains
by having the grains impact the droplets as they pass through the
sprays. The larger and heavier water-covered particulate grains are
then removed from the air stream in the separator tower by gravity,
centrifugal force, and additional water sprays. In addition to
removing particulate, the scrubber cools the gases from their incoming
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temperature (1000°F - 2200° depending on system configuration) to
saturation temperature, usually about 180°F. Subcooling to a lower
temperature can be performed if required, but consumes substantially
more water than cooling to saturation temperature.
A sump tank with recirculation system is uncluded in the scrubbing
system. The sump has a nominal 30 gallon capacity with provisions for
water makeup, system blowdown, and water sample acquisition. The
recirculation system was used during the Times Beach test to minimize
total scrubber water discharge.
An induced draft exhaust blower is located on the discharge side of
the scrubber. The blower is capable of exhausting the primary and
secondary chambers, producing a slight (typically 0.01 in. WC) draft
on the system, while overcoming the 10.0 in. WC pressure drop of the
scrubber. A butterfly damper is located on the outlet side of the
blower. The damper provides a means of manually adjusting the induced
draft gas flow.
A removable exhaust stack is installed through the trailer roof. The
stack extends 10 feet above the trailer roof, and is equipped with two
(2) standard sampling ports. Access to the sampling ports is provided
by scaffolding or a lift platform installed alongside the trailer.
2.7 Control System
A master control panel contains the following control devices:
Primary chamber zone temperature controllers
Alarm Lights
Hand-Off-Auto switches for mechanical components
Alarm lights are provided for the following mechanical and process
conditions:
Furnace temperature high
Wireway cover open
SCC temperature high
SCC temperature low
SCC purge
High stack temperature
Low scrubber water pressure
2.8 Data Acquisition System
The control panel contains the following devices for process data
recording and monitoring:
Multi-point temperaure recorder (6 points)
Digital thermocouple reading display (12 points)
Furnace running time totalizer
Primary chamber zone/secondary chamber power
consumption totalizers and indicators
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In addition, operating parameters can be monitored at the following
system components:
Scrubber (pressure drop)
Scrubber venturi (water flowrate and pressure)
Scrubber separator (water flowrate and pressure)
Primary chamber exhaust (draft)
Secondary chamber exhaust (draft and residual oxygen)
2.9 Heating Element Power Centers (HEPC's)
Heating elements in the two primary chamber zones are powered by a 10 KVA
heating element power center to control the flow of electricity to the
heating elements. Primary power input required for each power center is 3
phase, 60 Hz, 480 volts at 12 KVA. A similiar HEPC will be installed for
the secondary chamber at a later date. Each power center consists of a
solid-state power controller driving the heating elements through a tapped
step down transformer, mounted in a NEMA 3R (ventilated) enclosure.
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3.0 SAFETY PROCEDURES AND EQUIPMENT
3.1 General
Safety precautions comensurate with this operation were taken for per-
sonnel and equipment protection. Responsibility for safety was shared
so that each company or government agency involved provided its own
equipment. However, the Missouri DNR Emergency Response Team was
responsible for assuring that all safety procedures used complied with
the requirements of the Appendix C safety plan and that all personnel
protection equipment was correctly worn and maintained. Riedel
Environmental Services (RES), under contract to MDNR, provided a
safety briefing prior to the start of testing. RES also provided a
qualified registered nurse who monitored each individual's vital
signs during rest breaks.
3.2 Protective Equipment
The guidelines for personnel protection presented in the safety plan
were adhered to for this test program. In summary, the personnel pro-
tection equipment included:
1. All equipment complied with NIOSH Class C specifications and
requirements. ,
2. Respiratory protection including a full face respirator with orga-
nic vapor/acid cartridges and dust filters.
3. Dermal protection including Tyvek full body suit, inner light-
weight PVC or latex gloves, buna nitrile rubber outer gloves, and
steel-toed, shanked neoprene work boots.
3.3 Personnel Training
To assure correct use of the protective equipment and facilities, mem-
bers of both the MDNR Emergency Response Team and RES presented a
safety briefing. This briefing included a demonstration of the use
and application of the protective equipment, a description of the site
including the area where safety equipment must be worn and the decon-
tamination and rest areas.
3.4 Emergency Procedures
MDNR set up a minor injury first aid station in the rest area. The
nurse in this area was capable of providing first aid for minor
injuries and the effects of minor heat stress. As noted in Appendix
C, emergency phone numbers were posted at the guard gate entrance to
Times Beach.
3.5 Stress Monitoring and Breaks
The stress monitoring procedures presented in Appendix C were strictly
enforced. The registered nurse measured and recorded the ambient Wet
Bulb Globe Temperature (WBGT) at one hour intervals. Prior to
entering and immediately upon exiting the contaminated area, the nurse
measured the worker's oral temperature, blood pressure, and pulse
rate. Based upon the wet bulb temperatures, which ranged from 80 to
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95°F, the nurse recommended that the person's time in the contaminated
area be kept between 15 and 30 minutes. Subsequent to each period a
worker spent attired in the safety gear, a rest period was taken in
accordance with the safety plan.
3.6 Protective Equipment Application and Decontamination
The Missouri DNR marked the designated site areas where protective
equipment was required, and where such protective equipment could be
removed for rest breaks. The designated contaminated zone was inside
the fenced research area (see map in Appendix D). The research area
was a 50 foot by 60 foot fenced plot with a gravel ground cover. The
pilot trailer was located parallel to and 15 feet from the 50 foot
fence. In addition, MDNR set up an area for application, removal, and
decontamination of the protective equipment. The decontamination pro-
cedures presented in the Appendix C safety plan were followed.
The rest area was set-up outside the fence of the research area. The
rest area was located under trees to provide shade to allow personnel
to cool off after work periods in the contaminated area.
Before entering the contaminated area, a worker first put on a Tyvek
suit. Neoprene boots were then put on and tape applied to seal bet-
ween the boots and the suit. A latex inner glove was put on fallowed
by a buna nitrile outer glove. Tape was applied to seal the outer
glove to the suit arms. Finally, a full face respirator was put on
and its seal checked. The worker was then cleared to enter the con-
taminated area.
Two wash tubs were placed inside the contaminated area near its exit.
When ready to exit the contaminated area, a worker stepped into the
first tub which contained soapy water. Using a scrub brush, the boots
and outer gloves were washed. Then the boots and gloves were rinsed
by stepping into the second bucket and using the rinse scrub brush.
The worker then removed the outer gloves and placed them on a table at
the edge of the contaminated area to dry.
Before removing the respirator the person would exit the contaminated
area. After removing and wiping off the respirator with clean paper
towels, the inner gloves were removed. However, prior to the removal
of the gloves the person would tear off the Tyvek suit if it were
dirty, or torn. The inner gloves and suit were discarded in a special
container located just inside the contaminated area. At this time,
the worker proceeded to the rest area for a measurement of vital
signs.
While working in the area designated for protection equipment person-
nel did not remove any portion of his protective equipment. As noted
in Appendix C, any damage to that equipment required the worker to
pass through the decontamination area, remove the damaged article,
wash accordingly, and put on an undamaged replacement before returning
to the contaminated area.
During the work day workers took required rest breaks by removing only
their respirators and gloves in the decontaminating area. When
leaving the area for an eating break, equipment was removed and
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a shower taken to prevent any possibility of ingesting the contaminated
dirt or transporting it to an uncontaminated area.
Precautions were taken during furnace operation to assure personnel in
the vicinity were not subjected to any health danger. The safety
equipment discussed in preceeding sections was worn and kept in good
condition at all times. The organic vapor/acid cartridges and dust
filters in the respirators were changed each operating day. Used
cartridges and filters turned over to the MDNR Emergency Response
Team for proper disposal.
3.7 Furnace Operating Safety
Procedures for obtaining transporting, and feeding the contaminated
dirt to the furnace primary chamber minimized dust agitation. When
loading transport containers from the contaminated dirt storage drums
personnel located themselves upwind of the drum. Dirt was removed
from the drums using a shovel. The dirt in the drums was not agitated
or tossed, but removed and transported carefully.
Considering the potential health hazards, the primary concern during
operation was not to pollute the atmosphere. This pollution could
occur by allowing unburned gases to be released from the furnace or
exhaust stack ifthe secondary chamber temperature were allowed to fall
below approximately 2100°F.
In order to prevent local atmospheric pollution, the operators con-
tinuously monitored the secondary chamber temperature to assure it
remained above 2100°F. During the test program secondary chamber tem-
perature did not fall below 2100°F and the residual oxygen did not
fall below pre-determined safe levels.
3.8 Process and Testing Equipment Decontamination
For this decontamination, soap, water, hoses, and spray wand were
supplied by MDNR. Also, MDNR and RES supplied qualified persons to
aid in the decontamination and serve as supervisors.
At the completion of material processing, the primary chamber was
baked out at 1600°F in both control zones in order to volatilize any
dioxin potentially remaining. This bake-out was performed for four
(4) hours. During bake-out the temperature near the feed module floor
was spot-mom'to red and recorded. The secondary combustion chamber was
operated at 2200°F during bake-out to assure no spread of dioxin to
the offgas handling system or atmosphere. The system was then suf-
ficiently cooled overnight before the trailer was disconnected from
utilities.
At the conclusion of the bake-out a sample of insulation was removed
through a one-inch diameter port located in the coolest expected loca-
tion in the material feed end of the furnace. The sample was taken
from this location because any soil which may have fallen off the belt
below the feed chute would collect there. If a subsequent analysis
found excessive levels of dioxin (greater than 1 ppb) the feed half of
the furnace would have to be cleaned internally and the outer
(exposed) layer of insulation removed. The sample was delivered to
the Weston TAGA Van, located at the RES office, for analysis. An
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overnight analysis found no TCDD to a detection limit of 0.20 ppb.
Consequently, no decontamination of furnace internal surfaces or com-
ponents was required.
The portable pilot equipment decontamination and research area cleanup
was conducted with participating personnel in Class-C gear. The
exhaust stack and all loose equipment were transported to the
designated decontamination area near research facility office. Then
all trash (Tyvek suits, gloves, tape, sheet plastic, and paper towels)
were bagged, barreled, and correctly labeled as hazardous waste.
After the area was cleaned, the pilot trailer was moved to the decon-
tamination area.
The furnace feed metering conveyor was the only item which required
removal from the system for decontamination. The conveyor was removed
and sufficiently disassembled to enable it to be thoroughly washed
with a high pressure water spray. After decontamination of the
trailer, the conveyor was loaded for transport to Shirco's shop
facility where it was re-assembled and installed on the furnace.
The external surfaces of all equipment and the walls, ceiling, and
floor of the trailer were decontaminated next. First the furnace
discharge chute and hopper internal surfaces were vacuumed with a
HEPA type vacuum cleaner. Then the external surfaces of the primary
chamber, exhaust ducting, secondary chamber, control panel, scrubber,
and power distribution system were vacuumed. After all surfaces were
vacuumed a fine spray wand was used to wash down the walls and floor
of the trailer. Care was taken not to get the control panel and power
distribution systems wet. The wand was then used to rinse the walls
and floor of the trailer. After this was completed, the equipment and
inside of the trailer were considered decontaminated.
The fluorescent light bulbs in the trailer were removed next. These
were carefully washed with soap and water and placed in their boxes.
While the vacuuming of the trailer was in process the loose equipment
such as tools, exhaust stack, portable stairs, ladder, drain hose,
etc., were washed with soap and the high pressure water spray. All
auxiliary equipment was then placed back in the trailer in preparation
for transport.
When all equipment was in the trailer, its doors were locked. Then
the external surface of the trailer was washed with water using the
spray wand. Immediately upon completion of this washing the trailer
was removed from the Times Beach site.
In addition to the Shirco equipment, all ERT emissions test equipment
used at the test area was decontaminated by washing with soap and
water or methyl chloride.
After each operating day, the scrubber sump was drained and refilled.
MDNR ground disposal facilities were used to dispose of the water. A
scrubber water sample analyzed at the conclusion of testing showed no
dioxin present, to a detection limit of 1 ppb. Based on this analy-
sis, it was determined that disassembly and cleaning of the scrubber
were not required.
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4.0 SITE AND TEST MATERIAL DESCRIPTION
4.1 Site Description
Times Beach is a city in St. Louis county, Missouri. A description of
the location, history, and contamination is presented in Appendix D.
The city made arrangements in 1972 to have oil spread on its dirt
roads for dust control. The used oil that was applied contained quan-
tities of 2,3,7,8 Tetrachlorodibenzo-p-dioxin (TCDD) which was later
found to be a hazardous material. As a result, the city was eva-
cuated, purchased by the U.S. EPA, and a research facility built to
study means of decontaminating the area.
The research area referred to in this report is a nominal 50 foot by
60 foot plot parallel to the Laurel Road research plots and approxima-
tely 100 yards from Beach Drive (see map in Appendix D). This plot is
covered with gravel and fenced on all sides. For this test MDNR
contracted to have electrical power run from the existing transformer
in the research area to a breaker box. This breaker box would supply
480 volt/60 amp/3 phase power for system operation. In addition, 120
volts/60 Hz/1 phase receptacles were installed for trailer lighting
and emissions test equipment operation. Water to fill the system wet
gas scrubber recycle tank was made available from a standard outdoor
hydrant located just inside the research plot fence. Outside the
fenced research area is a gravel parking lot and drive leading to
Main Road.
4.2 Test Material
The soil used for the thermal process testing was acquired from the
road beds in the city. A description of the soils and geology of the
city is presented in Appendix D. A single 55 gallon drum of con-
taminated soil was used for this test program. The soil had been
acquired from one of the more highly contaminated roads in the city.
The road bed soil had earlier been screened with a lyfc inch mesh and
homogenized in a mixer.
The original laboratory analysis to define the 2,3,7,8-TCDD con-
centration in the drum of soil was performed by the Environmental
Trace Substances Research Center at the University of Missouri
-Columbia. A concentration of 248 ppb was found. As a check, an ana-
lysis was performed on July 8 at the Weston TAGA van located at the
Spirit of St. Louis Airport in Chesterfield, MO. The sample analyzed
was soil from the top of the drum. This analysis found a con-
centration of 260 ppb.
Although the soil was not analyzed for moisture and combustible con-
tent, estimates based upon visual inspection were that the moisture
content ranged from 15 to 20 percent and the combustible content was
approximately 5 percent on a dry basis. Based upon compaction in the
full drum, the density was estimated at between 90 and 100 lb/ft3.
When removed from the drum and broken, the soil density more nearly
ranged from 60 to 70 Ib/ft^. At the low moisture content, this soil
was not clay-like but tended to crumble easily.
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5.0 TEST CONDUCT AND PROCEDURES
5.1 Operational History
The first day of material processing was conducted on Tuesday, July 9.
The heat-up of the unit began at 0600 hrs. Prior to initiating feed a
problem developed with a primary chamber zone 2 power control signal.
This was successfully remedied and the first soil was fed to the fur-
nace at 1245 hrs. At this time the primary and secondary chamber tem-
peratures were stable at 1600°F and 2300°F, respectively. The test
plan, based upon a conservative 2,3,7,8-TCDD laboratory detection
limit estimate and the contaminant concentration in the feed soil, was
to acquire an emissions sample over a seven (7) hour period. This was
to ensure that the required 99.9999 percent destruction efficiency of
the 2,3,7,8-TCDD in the stack emissions could be demonstrated.
The emissions sampling was initiated at approximately 1330 hrs. All
operation and sampling preceded well until 1500 hrs. At this time a
fuse blew at the site power source breaker. While the problem was
being investigated, adequate draft was maintained on the primary and
secondary chambers to prevent the escape of emissions into the
trailer. The secondary chamber temperature remained high for over one
primary chamber residence time, thus no atmospheric pollution was
assumed to have occurred. Because of the late sampling start and the
electrical system upset, it was decided to restart the sampling the
next day.
The first of two (2) full days of test started on July 10, 1985. The
furnace heat-up began at 0300 hrs. With the primary chamber and
secondary chambers at operating temperature, soil feed began at 0720
hrs. The belt speed in the primary chamber was adjusted to a resi-
dence time of 30 minutes. As can be seen by reviewing the Appendix C
operating logs and temperature charts the system operation remained
steady throughout the day. Because the wet gas scrubber system uti-
lized recycled water the stack gas temperature was nominally 170°F.
This temperature resulted in a 30% (by volume) moisture content which
required some adjustment of heaters on the emissions sampling probes.
By 1015 hrs the ERT crew had made the adustments needed for this
operation and the emissions sampling began. For the next seven hours
until 1715 the system and emissions sampling ran consistently without
need for adjustments. System shutdown began at 1716 hrs with the
stoppage feed dumping and start of equipment cool down 30 minutes
later. The data logs were maintained, material fed, feed and
discharge samples taken, and the system operation monitored throughout
the day as described in the following sections.
On the second day of testing, the purpose was to obtain data for
operation with a 15 minute material residence time in the primary
chamber. The system heat-up began this day at 0300 hrs. The test
options this day were to process either the 260 ppb-contaminated
material that remained for a short duration, or the next highest con-
tamination level material (117 ppb) available for a longer duration.
ERT's calculations showed that, with the 260 ppb material, approxima-
tely two hours of sampling was needed to potentially capture enough
dioxin to verify a minimum 99.9999 % destruction efficiency. Based
upon a pre-test weighing of the barrel of 260 ppb-contaminated soil,
approximately 180 pounds remained after the previous two days of
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operation. It was determined that the most viable option would
include a change in only the residence time variable. Thus, the 260
ppb contaminated soil was used for the second day of testing.
In order to establish the feed rate at the 15 minute residence time,
the 117 ppb material was initially fed. The feed depth was set 0.75
inches, consistent with primary chamber process power capacity.
However, at this rate, some clogging of the feed gate was experienced
due to rocks and dirt chunks in the material. This required more
operator attention to prevent feed blockage. After one hour of feeding
the 117 ppb material, feed of the 260 ppb material feed was initiated.
The soil remaining in the barrel contained more moisture toward the
bottom of the barrel. Consequently, it had a tendency to aglomerate
and clog at the gate somewhat like the 117 ppb material. In order to
provide a consistent feed to the furnace, an operator monitored and
prepared the soil as required to prevent clogs during the entire
emissions test period. The emissions and soil sampling began at 1058
hrs and continued until the last 260 ppb material was fed at 1320
hours. After the sampling was completed the soil was given time to
clear the furnace.
At approximately 1400 hours the system decontamination bakeout was
initiated, as described in Section 3 of this report. The system was
prepared for transport to Shirco's Dallas, TX, facility on the evening
of July 12 and morning of July 13.
Presented in the following sections are more detailed descriptions of
test and operating procedures and parameters for individual system
components.
5.2 Equipment Set-Up
The Portable Pilot Test Unit trailer arrived at the test site at 0830
hrs on July 8, 1985, and was driven to and positioned in the research
area by 1030 hrs. The equipment and supplies stored in the trailer
for transport were removed. Spare parts and supplies not readily
needed that might be subject to rain damage were taken to the decon-
tamination area and placed in the facility office trailer. This
trailer was also used by the ERT emissions test personnel for sample
train recovery and sample storage.
All MDNR, ERT, RES, and Shirco personnel gathered at the site at 1400
hrs to begin the equipment set-up. Midway through the set-up a break
was taken for all participants to receive a safety briefing presented
by MDNR and RES. A total of nine (9) personnel were involved in the setup
(and subsequent decontamination and teardown) of the test equipment.
The ERT personnel set up their sampling equipment while the MDNR, RES,
and Shirco personnel mounted the exhaust stack above the trailer. A
scaffold was set up alongside the furnace trailer to provide access to
the stack for emissions sampling.
The area designated for use of the class C safety gear was set-up by
MDNR and RES. RES also connected wiring from the trailer to the
breaker panels, and connected the scrubber water supply hose. Shirco
personnel installed the primary chamber heating elements, the secon-
dary chamber baffles, the control panel instruments, the ash discharge
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receiving barrel, the scrubber drain hose, and the trailer inside
lights. By 2000 hrs all equipment had been made operational.
With pilot system and emissions test equipment set-up along with the
contaminated, decontamination, and rest areas, the individual system
components were operated as the final check point i-n the set-up proce-
dure. The system was then declared ready for operation the following
day.
5.3 System Heat-Up
Approximately four hours prior to initiating contaminated soil feed to
the primary chamber, heatup was initiated. Temperature setpoints of
1600°F were used for both control zones. After the primary chamber
temperature reached 1000°F, the secondary chamber heat-up was ini-
tiated. The propane fuel flow rate was initially set at the maximum
to minimize time required to reach operating tmepenature.
5.4 Contaminated Soil Feed
Contaminated soil was transferred from the drum to the furnace feed
conveyor in approximate 20 Ib increments. The soil was shoveled from
the drums to a 5 gallon plastic bucket. Care was taken by the Shirco
operator to minimize dust agitation. The plastic bucket was weighed
prior to filling, and the corresponding tare set on the scale. After
filling the 5 gallon bucket, it was weighed and the exact weight
recorded. Thus the recorded weight included only the soil. The time
of depositing the weighed soil into the feed hopper was also recorded.
The feed container was then positioned on top of the feed conveyor
hopper and approximately one-half of the soil transferred to the
hopper. Approximately 15 minutes later the remaining contents of the
bucket were dumped into the hopper. The feed hopper cover remained in
position except when depositing soil in the hopper.
5.5 Scrubbing System
The wet gas scrubbing system was adjusted to produce a nominal
pressure drop of 9 inches w.c. The venturi water flow was set to 1
gpm while the venturi quench and seperator tower sprays were adjusted
to produce a nominal stack temperature of 170°F.
The scrubber liquid was a recirculating water flow from the sump tank
located below the venturi tower. The operator drained and refilled
the reservior each day of testing. The 30 gallons of wastewater were
drained onto the ground outside the research area, as directed by
MDNR. During operation, the operator regularly checked the water
level in the sump tank. There was no need for make-up water.
5.6 Operating Data Log
The Shirco operators maintained the operation log presented in
Appendix E. Data was recorded at one hour intervals. Comments rela-
tive to changes in the system operations, interruptions, and per-
tinent observations were recorded as they occurred.
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5.7 Operating Conditions
5.7.1 Test Condition Matrix
The test condition matrix used for this test-program is pre-
sented in Table 5-1.
5.7.2 Primary Chamber Temperature
The soil contaminant dioxin, 2,3,7,8-TCDD, is known to volati-
lize between 800°F and 1000°F (Reference 1). Also, it has been
found by testing in the U.S. EPA's mobile incinerator that
acceptable processing of 2,3,7,8-TCDD-contaminated soil is
obtained at primary chamber temperatures between 1600°F and
1700°F (Reference 2).
For this test of the Shirco system, the primary chamber Zone A,
(drying and initial volatilization zone) and Zone B (high tem-
perature volatilization and oxidation zone) were both
controlled at a setpoint temperature of 1550°F. These tem-
peratures were maintained by adjusting the controller for each
zone to that setpoint value. A thermocouple probe extending
into the process chamber at the mid-point of the control zone
provided the feedback signal on which the control was based.
Electric power was supplied by the individual zone power center
in response to the controller output signal.
5.7.3 Primary Chamber Residence Time
Test condition #1 used a primary chamber soil residence time of
30 minutes. The condition #2 residence time was 15 minutes.
These residence times are based upon a furnace effective length
of 66.5 inches. The residence time was set by adjusting the
furnace belt speed control dial on the variable speed drive
motor. The rotational speed of the primary chamber end drum
was measured by stop watch. The drive speed was then adjusted
to produce the desired rotational speed.
5.7.4 Secondary Chamber Temperature
EPA research results performed prior to this test suggested
that the complete destruction of dioxin is accomplished at a
gas residence time of 2.2 seconds and a temperature of 2200°F
(Reference 2). In accordance with these conditions and other
data acquired during the EPA mobile incineration system testing
at Denney Farms, the secondary combusiton chamber temperature
was maintained between 2100°F and 2250°F for all test con-
ditions.
The secondary chamber was heated by a propane burner with
manual control. The chamber temperature was set during heat-up
at the maximum fuel flow. The adjustment was made by a hand
valve upstream of the burner. As the chamber temperature
approached the setpoint temperature the operatior incrementally
decreased the fuel rate. This adjustment procedure covered
nominally a 30 minute period after which the chamber tem-
perature would remain constant at a steady fuel flow rate.
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Upon Initiation of soil feed the operator would make minimal
adjustments in the input fuel rate to maintain the setpoint
temperature. Due to the steady soil feed rate and consistent
soil properties, very few fuel flow adjustments were required
while processing soil.
5.7.5 Primary and Secondary Chamber Combustion Air
The air injected into the primary chamber was supplied at a
flow rate estimated to be adequate to oxidize any combustible
material in the soil. An air-to-fuel ratio of 8.0 Ib air/lb
combustibles was used, along with a moisture content of 15% and
combustible solids content of 5% (dry basis). Fifty percent
excess air was supplied.
Combustion air for the secondary chamber was set based upon the
residual oxygen concentration measured in the secondary chamber
exhaust stream. The portable unit was designed to process a
wide range of waste materials. When processing a waste with
low moisture and combusible content, waste gas velocity rather
than residual oxygen content becomes the important air control
parameter. The combustion air blower damper was adjusted to
produce a nominal residual oxygen content in the secondary
chamber exhaust gases of 1%. This value was based upon the
volumetric flow rate of gas in the secondary chamber needed to
produce adequate mixing.
5.7.6 Contaminated Soil Feed Rate
The feed rate of contaminated soil to the primary furnace was
controlled by the furnace belt speed setting and the gap
opening of the feed conveyor guillotine gate. The speed of the
feed conveyor and furnace conveyor belts are synchronized.
Both are driven by the same drive motor and are geared accor-
dingly. The guillotine to belt gap was 1.0 inch for test #1
and 0.75 inches for test #2. It is estimated that the bulk
density of the contaminated soil was 70 Ib/ft^. The resulting
feed rates for the 30 and 15 minute residence times were 46 and
70 pounds per hour, respectively. However, the feed rate on
the second day was limited to 48.1 Ib/hr to eliminate potential
clogging of the feed inlet.
5.7.7 Furnace Draft
Both the primary and secondary chambers were operated under a
slight negative pressure to prevent contaminants being emitted
into the atmosphere through system pressurization. The draft
pressure in the primary chamber was maintained at approximately
-0.015 inches w.c. above the processed soil discharge chute.
The secondary chamber was adjusted to approximately -0.06
inches w.c. These adjustments were made using the exhaust
blower, scrubber venturi, and primary chamber exhaust duct dam-
pers.
The procedure used is based on opening the exhaust blower damper
enough to allow the desired primary and secondary chamber
drafts to be maintained while adjusting the scrubber venturi
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damper to produce a scrubber pressure drop in excess of -10
inches w.c.
5.8 Emissions Testing
5.8.1 General
During both the 30 and 15 minute primary chamber residence
time operations the stack gas was sampled for 2,3,7,8-TCDD and
particulates. A modified U.S. EPA Method 5 sampling train was
used for the sampling. Two sampling trains were used for each
test condition. This provided a duplicate back-up sample.
The sampling test duration was based upon the concentration of
2,3,7,8-TCDD in the soil and the detection limit available in
the Weston laboratory. The pre-test indication from Weston
was that a 1 picogram/microliter detection limit of 2,3,7,8-
TCDD was practical. Since a 50 microliter sample was used for
gas chromatograph/mass spectrometer analysis, the stack
sampling would have to be of a duration that could potentially
catch 50 picograms. Given the sampling volume flow rate and
the estimated stack volumetric flow rate, a sampling duration
was calculated for each residence time condition. Because the
possibility existed that the sample analysis might have ,to be
performed by a laboratory with a detection limit of 250
picograms, the final sampling duration was based on that
detection limit and calculated to be 7 hours.
To provide some understanding of how the test duration was
calculated, an example of calculations and other procedures
used to this duration for the 30 minute residence time test
condition follows.
5.8.2 Sample Procedures
Estimated stack sampling rate : 40 scfh
Calculated stack gas flow rate: 6000 scfh
Soil dioxin concentration: 260 ppb
Primary chamber feed rate: 46 Ib/hr (20,884 g/hr)
Total dioxin processed:
Mdioxin s 20,884 g/hr X 260 X 10'9 g/g
= 5.42984 X ID'3 g/hr
Total dioxin emitted at 99.9999 % ORE
^emitted = 5.42984 X 10-3 x (1 - 0.999999)
* 5.4298 X 10-9 g/nr
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Stack dioxin concentration:
= 5.4298 X 1Q-9 g/hr
6000 ft3/hr
= 9.04973333 X 10'13 g/ft3
If laboratory detection limit is 250 X 10"12 grams for a 50
microliter injection, the total sample volume required is:
^sample = 250 X 1Q-12 grams
9.04973333 X lO'*3 g/ft3
= 276.25 ft3
At a sampling rate of 40 ft3/hr, the duration of sampling must
be:
Sampling * 275.25 ft3
40 ft3/hr
<
= 6.9 hrs
Accordingly, a sampling duration of seven hours was used.
5.9 Soil Sampling
Composite feed and discharged soil samples were taken during each
test condition. The soil sampling was performed over the entire
emissions sampling duration. Each composite had a volume of one (1)
liter. Each time material was fed to the feed hopper, approximately
50 milliters was added to the sample jar.
At approximately 30 minute intervals the discharge chute sampling
tray was emptied into the sample jar. For test #2 the amount of
material added to the sample jar was doubled.
Extreme care was taken to prevent contamination of the product soil
sample. The discharge chute sample drawer was sterilized in a 2000°F
muffle furnace prior to being taken to the site. Clean gloves were
used to remove the sample drawer and deposite the sample into the
container. The sample drawer was not placed on potentially con-
taminated surfaces during the transfer process. A product sample was
not acquired while a feed transfer was in process. At the conclusion
of each operating day the feed and discharge samples taken were tran-
ferred to the office trailer in the decontamination area. An ERT
representative transferred the samples to the Weston laboratory at
the end of the two days of testing.
5.10 Soil and Emissions Sample Analysis
The laboratory analysis of the feed soil, discharged soil, and
emissions samples were performed by Weston using their York/Weston
REM-MS2 mobile GC/MS/MS laboratory. This laboratory was located at
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the RES office in Chesterfield, Missouri, where it was condcting work
under another contract from the U.S. EPA.
In addition to the Weston analysis, the University of Missouri at
Columbia laboratory analyzed a duplicate feed soil and discharged
soil for MDNR in keeping with their policy of verifying the results
of a decontamination test. Along with the soil samples the UMC
laboratory analyzed a scrubber effluent sample. The specific test
procedures used by the two laboratories are presented in detail in
Appendices B and F for Weston and UMC, respectively.
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TABLE 5-1
TEST CONDITION MATRIX
Condition
Number
1
2
Date
7/10
7/11
Primary
Chamber
Residence
Time (min)
30
15
Contaminated
Soil
Feed Rate
(Ib/hr)
46
70
Temperatures
Primary Chamber
Zone 1
1600
1600
Zone 2
1600
1600
Secondary
Chamber
2200
2200
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6.0 TEST RESULTS/CONCLUSIONS
6.1 General
The primary objectives of the test program were to confirm the ability
of the Shirco Infrared Systems process to decontaminate dioxin-laden
soil and to incinerate the dioxin at a verified destruction and remo-
val efficiency (ORE) of 99.9999 % or greater.
The data from emissions and discharged soil sampling, and subsequent
analysis of that data, form the basis for determining whether or not
those objectives were met. A discussion of the data and analysis
results is contained in following sections. In addition, the equip-
ment operating data is of interest with respect to the conditions
under which the decontamination results were obtained.
6.2 Feed Material
6.2.1 Material Properties
Standard procedures for testing performed by Shirco Infrared
Systems include having the feed material analyzed for moisture,
combustibles, and contaminant content along with density and
calorific value. However, the laboratories used to measure the
dioxin contamination concentrations were not equipped to ana-
lyze for the other properties.
Since the performance of the system with respect to dioxin
destruction was a main purpose of the test program, furnace
operating conditions were specifically adjusted to assure maxi-
mum destruction efficiency. A visual estimate of the material
properties provided the information needed to estimate furnace
operation settings. Therefore, more accurate material physical
properties were not necessary and were not determined. The
estimates presented in Section 3.0 are the basis for further
evaluations of system performance.
Composite feed samples taken during the 30 and 15 minute pri-
mary chamber residence time tests were analyzed by Weston
(Appendix B) and found to contain 227 ppb and 156 ppb of
2,3,7,8-TCDD, respectively. The UMC (Appendix F) analysis
yielded a higher concentration of 306 ppb.
Since lower concentrations would require smaller quantities of
dioxin in offgas samples to confirm the 99.9999 % destruction
efficiency, the Weston results were used by ERT to calculate
the destruction efficiencies. Calculations based on the UMC
data would yield slightly higher DRE's than those noted in
Section 6.4.1.
6.2.2 Soil Feed Rate
The feed rate history for the testing is noted in the Appendix
E operating logs, Tables 6-2 and 6-3, and Figures 6-1 and 6-2.
For both the 30 and 15 minute primary chamber residence time
conditions, the plots show a reasonably steady feed rate. The
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average feed rate for the two tests were 47.7 Ib/hr and 48.1
Ib/hr, respectively.
6.3 Soil Decontamination
Procedures and results for discharged soil sample analysis are con-
tained in Appendix B, and the results are summarized in Table 6-1.
The Weston analysis found the samples from the 30 minute and 15 minute
residence time tests to be free of residual dioxin, to detection
limits of 38 and 33 parts per trillion (ppt), respectively. The UMC
confirmed these results, but to a less rigorous detection limit of 1
ppb.
Shirco has determined that disposal of residual material (soil, in
this case) can be a significant area of operating cost for on-site
incineration. In order to minimize this cost, it is important that
the residual material be suitable for deli sting as hazardous waste
under U.S. EPA regulations 40 CFR 260.20 and 40 CFR 260.22, and for
inclusion in Appendix XI of 40 CFR 261.
A delisting petition for residual soil produced by a similar operation
was recently approved by U.S. EPA (Reference 3). The detection limit
for residual dioxin contained in this petition was 90 ppt, con-
siderably higher than that used for the test of Shirco's equipment.
This indicates that residual soil from on-site incineration of dioxin-
laden soil is suitable for delisting, provided suitable test data is
obtained and the incineration process is properly maintained and moni-
tored. It should be noted that approval of such delisting petitions
may be denied based on the presence of other hazardous components such
as Teachable metals.
These findings show that not only can the Shirco process effectively
remove 2,3,7,8-TCDD from contaiminated soils, but that the resulting
residual material can be classified as non-hazardous with respect to
dioxin. This classification can reduce the overall operating cost for
on-site incineration by simplifying final disposition of the residual
soil.
6.4 Stack Emissions/DRE
6.4.1 2,3,7,8-TCDD
Analysis procedures and results of stack emissions testing are
reported in Appendices A and B, with results summarized in
Table 6-1.
The data for 2,3,7,8-TCDD testing shows that the required
99.9999 % ORE was exceeded by an order of magnitude for the 30
minute residence time test, and comfortably exceeded for the 15
minute test. Actual DRE's were >99.999996 %, and >99.999989 %,
respectively. In Weston's analysis of laboratory procedures
used in determining expected dioxin quantities in the emissions
samples, calculations indicated that detection limits were 14
picograms and 8.4 picograms. These detection limits were used
by ERT in calculating DRE's.
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These results show that the Shirco process is capable of
exceeding the incinerator performance requirements (ORE) of
U.S. EPA regulation 40 CFR 264.343(a), for dioxin-bearing
materials.
6.4.2 Particulate Emissions
A U.S. EPA Modified Method 5 sampling technique was used to
determine particulate emissions from the system. The results
of this testing and subsequent analysis are summarized in Table
6-1.
For the 30 minute residence time test the particulate emissions
were 0.001 grains/dry standard cubic ft (gr/dscf), and 0.0002
gr/dscf for the 15 minute residence time test. These rates are
well below the 0.08 gr/dscf standard contained in U.S. EPA
regulation 40 CFR 264.343(c).
The inherently low particulate emissions of the Shirco infrared
furnace are graphically demonstrated by these results. Compli-
ance with particulate emissions standards has historically been
a problem for hazardous waste incinerators processing con-
taminated soils. Units using mechanical agitation or induced
air turbulence to achieve adequate DRE's have significant dif-
ficulty in complying with such standards. The emissions levels
measured during this test indicate that particulate emissions
from a Shirco incinerator processing contaminated soils are not
a source of concern.
In addition to simplifying design, operation, and maintenance
of pollution control equipment, lower particulate emissions
will also result in significantly smaller amounts of scrubber
solid residues for disposal. It should be noted that the
delisting concerns noted in Section 6.3 also apply to scrubber
residues.
6.5 Scrubber Effluent Analysis
MDNR secured a scrubber effluent sample during the 15 minute residence
time emissions test, to determine its dioxin contamination level. The
procedures used in the analysis are presented in the Appendix B
report. The finding was that 2,3,7,8-TCDD was not present to a detec-
tion limit of 1 ppb.
The Reference 2 delisting petition for the U.S. EPA mobile incinerator
operation showed that no 2,3,7,8-TCDD was found in scrubber effluent
to a detection limit of 3.9 ppt, considerably lower than that used in
this test. The ability to delist the scrubber effluent from any unit
except the EPA system has not been demonstrated. However, the failure
to find TCDD in the effluent from this test suggests that dioxin is
not present at a level which would prevent delisting of the effluent,
with subsequent disposal as a non-hazardous waste.
6.6 Equipment Operation
The portable pilot set-up, dismantling, and decontamination were
described in previous sections. As noted, these activities proceeded
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smoothly and in a timely manner. Set-up was completed in six hours.
The dismantling, decontamination and packing for transport were
completed in twelve working hours. With the exception of the blown
main power breaker fuse, which occurred on July 9, all equipment
operated without difficulty throughout the test cycle.
6.7 Process Temperatures
Also presented in the Appendix E operating logs are temperatures in
the portable pilot system recorded from the control panel digital
display. Presented on Figures 6-3, 6-4 and 6-5 are copies of the
control panel temperature recorder chart for July 9, 10, and 11. The
temperatures in primary chamber zone thermocouples Aj and A2, primary
chamber exhaust, and scrubber stack are recorded. Errors in the
signal to the recorder for the thermocouples in primary chamber Zone B
and the secondary chamber were experienced during this program. Thus,
these two temperatures are not recorded; however, the digital readout
signal was functioning, allowing the operator to make a written
recording each hour.
During the 30 minute residence time test performed on July 10 the pri-
mary chamber was maintained at a nominal temperature of 1560°F in the
drying/volatilization zone and 1550°F in the volatilization/bakeout
zone. The secondary chamber maintained a nominal 2250°F temperature.
During the 15 minute residence time test on July 11 the primary
chamber temperture was nominally 60°F lower. A review of Figure 6-5
shows the effect of the increasing moisture content of the feed soil
as the soil container was emptied. However, during the emissions
sampling period for this condition the primary chamber temperture was
relatively stable at 1490°F in both control zones. The nominal secon-
dary chamber temperature was 2235°F.
Thus, the soil decontamination was accomplished at primary chamber
temperatures as low as 1490°F and secondary chamber temperatures bet-
ween 2200°F and 2250°F.
6.8 Power Usage
Input power to the two temperature control zones in the primary fur-
nace chamber was measured by totalizers for each zone. The totalizer
readings were recorded on the Appendix E operating log at nominal one
hour intervals. Table 6-4 presents cumulative power usage as a func-
tion of time for each of the three operating days.
Process power consumed includes that required to overcome heat losses
from the furnace shell. In the pilot test unit, the heat losses per
unit of effective belt surface area are substantially greater than for
a full scale system, as shown in Figure 6-3. Consequently, the speci-
fic power consumption data presented here for the portable pilot unit
should not be used to estimate power required to decontaminate simi-
liar soil in a full-scale system. This data is presented here for
information purposes only.
During the emissions test period for the 30 minute residence time con-
dition on July 10, the primary chamber power usage rate was 16.7 KW.
Using the average soil feed rate of 47.7 Ib/hr, the specific power
usage was 0.35 KW/lb feed. During the 15 minute residence time expo-
-------
sure, the average power usage rate was 16.9 KW. For the 48.1 Ib/hr
soil feed rate during this test, the specific power usage rate was
again 0.35 KW/lb feed.
Both of these test conditions required the use of the maximum power
available in the portable system, since the soil had very little heat
value and the feed rate, by design, was the maximum the unit could
process with the available power.
Since contaminated soil will likely have varied, site-specific charac-
teristics, a general estimate of operating power usage with a full-
scale system should not be made from the test data.
-------
-------
FIGURE 6-3
TEMPERATURE RECORDER CHART - JULY 9, 1985
IfOO
1300
0700
-------
FIGURE 6-4
1160
1000
0100
TEMPERATURE RECORDER CHART
0700
JULY 10, 1985
0600 0500
OtOO
-------
0100
RE
TEMPERATURE RECORDER CHAR'i - JULY 11, 1985
0100 0700 OtOO 0500
-------
TABLE 6-1
TEST DATA SUMMARY
Date
9/9/85
9/10/85
9/11/85
Test
Condition
1
1
2
Emissions
Test No.
1
2
3
Primary
Chamber
Residence
Time (min)
30
30
15
Average
Soil
Feedrate
(Ib/hr)
30(appr)
47.7
48.1
Nominal Test Temperature
Primary
Chamber
Zone A
1600
1560
1490
Zone 8
1580
1550
1490
Secondary
Chamber
2300
2250
2235
Table 6-1, Cont.
Emissions
Test No.
1
2
3
Average
Primary
Power Usage
(kw/lb feed)
-
0.35
0.35
Average
Secondary
Energy Usage
(BTU/lb feed
-
2850
2900
Feed Soil
Dioxin Level
(ppb)
N/A
227
156
Emissions
Destruction
Efficiency
(%)
N/A
99.999996
99.999989
Participate
Emissions
(gr/dscf)
N/A
0.001
0.0002
Table 6-1, Cont.
Emissions
Test No.
1
2
Discharged Soil Dioxin Level
(parts per trillion)
N/A
<38
<33
Scrubber Effluent Dioxin Level
(parts per billion)
N/A
N/A
-------
TABLE 6-2
FURNACE FEED HISTORY
30 MINUTE RESIDENCE TIME
July 10, 1985
Time
0720
0810
0932
1020
1053
1134
Unk
1248
1335
1412
1517
1559
1632
Weight Feed
(lb)
35
33.3
31
31.75
33.5
30
32.5
33.75
33.5
33.25
38
32.25
35.25
Cumulative Feed
(lb)
35
68.3
99.3
131.05
164.55
194.55
227.05
260.8
294.3
327.55
365.55
397.8
433.05
NOTE: Based on this table and Figure 6-1, a total of 333.75 pounds of material
were fed between 0932 hrs and shutdown at 1716 hrs. The average feed
rate during this period was 47.7 Ib/hr. The emissions sampling tests
were conducted between 1016 and 1720.
-------
TABLE 6-3
FURNACE FEED HISTORY
15 MINUTE RESIDENCE TIME
July 11, 1985
Time
0904
1009
1055
1141
1231
Weight Feed
Mb)
55*
44.25**
37.75
37.15
39
Cumulative Feed
(lb)
55
99.25
137
174.15
213.15
NOTES: * Material containing 117 ppb of 2,3,7,8-TCDD
** Material containind 260 ppb of 2,3,7,8-TCDD (fed for remainder of
testing)
Emissions testing conducted between 1009 hrs and 1231 hrs.
-------
TABLE 6-4
OPERATING POWER CONSUMPTION
July 9, 1985
Time of Day
0900
1045
1145
1230
1315
1405
0610
0730
0810
8646
0940
1020
1100
1130
1230
1330
1440
1535
1630
1730
Cumulative Time
(hrs)
. 0
1.75
2.75
3.50
4.25
5.05
__-______-_._-_.. Inl v 1
0
1.33
2.00
2.60
3.50
4.17
4.83
5.33
6.33
7.33
8.50
9.42
10.34
11.34
Cumulative Power Usage
Zone A
Q 1QRR_._-_-
.0
14.9
24.0
28.3
33.8
40.3
01 QftR..-.-.
0
11.7
18.2
23.7
31.6
38.0
4.0
48.3
57.1
66.2
76.7
85.2
93.3
104.9
Zone B
0
14.5
22.6
27.0
33.2
40.1
0
10.2
15.9
20.7
27.5
33.0
38.2
41.9
49.6
57.4
6.55
73.8
80.8
90.9
Total
.0
29.4
46.6
55.3
67.0
80.4
0
21.9
34.1
44.4
59.1
71.0
82.2
90.2
106.7
123.6
143.2
159.0
174.1
195.8
-------
TABLE 6-4, CONTINUED
Time of Day
0810
0905
1030
1135
1205
1231
Cumulative Time
(hrs)
0
.92
2.33
3.42
3.92
4.3
Cumulative Power Usage
Zone A
Ul QRti_____
0
8.2
21.2
30.9
35.9
39.6
Zone B
0
7.2
18.6
26.7
31.1
34.3
Total
0
15.4
39.8
57.6
67.0
73.9
-------
7.0 REFERENCES
1. NIOSH Current Intelligence Bulletin 40, "2,3,7,8 Tetrachlorodibenzo-p-
dioxin (TCDD, "dioxin")", U.S. Department of Health and Human Services,
January 23, 1984.
2. Federal Register, Volume 50, Number 108, pages 23721-23728, "Hazardous
Waste Management System; Identification and Listing of Hazardous
Waste", U.S. Government Printing Office, June 5, 1985.
3. Federal Register, Volume 50, Number 143, pages 30271-30274, "Identifi-
cation and Listing of Hazardous Waste; Mobile Incineration System",
U.S. Government Printing Office, July 25, 1985.
-------
APPENDIX A
ERT EMISSIONS SAMPLING REPORT
-------
Document C-S044
January 1986
Final Report
Thermal Destruction of
Dioxin Contaminated Soils
Employing a Shirco-Infrared
Incinerator Pilot Unit -
The Times Beach, Missouri
Monitoring Program
EBT
A RESOURCE ENGINEERING COMPANY
-------
TABLE OF CONTENTS
Page
1. INTRODUCTION 1-1
2. SUMMARY OF RESULTS 2-1
3. FIELD SAMPLING PROGRAM 3-1
4. LABORATORY ANALYSIS 4-1
5. QUALITY CONTROL PROTOCOLS 5-1
APPENDIX A FIELD CALIBRATION DATA
APPENDIX B ROY F. WESTON ANALYTICAL PROGRAM-
ANALYSIS OF COMBUSTION PRODUCTS FOR
2,3,7,8-TETRACHLORODIBENZODIOXIN (TCDD)
APPENDIX C TECHNICAL WORK SCOPE FOR THE ANALYTICAL
PROGRAM PROVIDED TO ROY F. WESTON BY ERT
APPENDIX D DRAFT ASME SAMPLING PROTOCOL
-------
1. INTRODUCTION
Environmental Research & Technology, Inc. (ERT) of Concord,
Massachusetts and Shirco Infrared Systems of Dallas, Texas jointly
sponsored an incineration test program at the Dioxin Research Facility
located in Times Beach, Missouri on July 10 and 11, 1985. The test
program was conducted using a Shirco pilot mobile incinerator for the
thermal treatment of a dioxin contaminated soil feed. The primary
objective of this test program was to provide a preliminary evaluation
of the Shirco Infrared Technology for use in the thermal
decontamination of dioxin contaminated soils.
The actual demonstration program consisted of two test runs while
the pilot incinerator was treating Times Beach soil contaminated with
approximately 200 ppb of 2,3,7,8-tetrachlorodibenzo dioxin. Sampling
of the requisite influent and effluent test streams was performed by
ERT personnel. During each of the two test series, samples were
collected from each of four process streams as follows: contaminated
soil feed, incinerator ash (treated soil), flue gas (combined
vapor/particulate) and scrubber slurry. Laboratory analyses of the
requisite samples for 2,3,7,3-TCDD were performed by .Roy F. Weston of
Westchester, PA employing a tandem GC/MS/MS system situated in the
vicinity of the Times Beach site.
The report to follow, which was prepared by ERT, addresses the
critical features of the incinerator monitoring program itself. A
summary of the pertinent sampling and analysis procedures are
contained in Sections 3 and 4, respectively. Calibration data
pertinent to the field sampling activities are provided in
Appendix A. The complete text of the analytical report provided to
ERT by Roy F. Weston is provided in Appendix B. These analyses were
conducted in accordance with technical specifications contained in the
ERT scope of work provided in Appendix C. A summary of the quality
control features of the monitoring program are contained in
section 5. A summary of results for each of the two test series
including the calculated destruction/removal efficiencies for
2,3,7,8-TCDD are provided in Section 6.
1-1
6956P C-3044-A
-------
2. SUMMARY OF RESULTS
The presentation to follow contains a summary of-2,3,7,8-TCDD
test data provided to ERT by R.F. Weston and the University of
Missouri as well as pertinent field data collected during each of
ERT's field test series.
Analytical test results for each of the requisite sample matrices
are provided in Table 2-1. While results are provided for TCDD only,
it has been assumed for the purposes of this test program that all of
the TCDD is present as the 2,3,7,8-TCDD analogue. As shown no
2,3,7,8-TCDD was detected in the treated soil from either test run at
levels ranging from 0.033 ppb to 0.038 ppb. Similarly, no
2,3,7,8-TCDD was detected in the flue gas from either test series at
conci
Pg).
concentrations ranging from 0.002 ug/m (14 pg)to 0.003 ug/m (8.4
These data in conjunction with pertinent waste feed and stack
flow rates were used to derive destruction and removal efficiency data
for each of the two test series. These calculations, as shown in
Table 2-2, are in excess of the 99.9999% criteria stipulated by the
Environmental Protection Agency for the effective decontamination of
dioxin contaminated soils.
A summary of physical and chemical parameters monitored during
each of the two test series are contained in Table 2-3. These data
include critical physical features of the flue gas sampling system as
well as physical and chemical characteristics of the flue gas, itself.
Particulate emissions data (grain loadings) for each of the two
test series are also provided in Table 2-3. It should be noted that
the particulate emission results presented in this table represent
loadings from only the filter samples from each of the test runs. Due
to an oversight, gravimetric determinations were not conducted on the
particulates rinses prior to organic extraction, rather each dried
probe rinse was submitted directly in combination with the
corresponding particulate filter for extraction and eventual TCDD
analyses. We contend that the mass of particulate matter associated
with these sample would in no way be sufficient to effect the units
compliance status with the incinerator performance status of 0.08
gr/dscf
1429J C-3044 2-1
-------
TABLE 2-2
DESTRUCTION AND REMOVAL EFFICIENCY
CALCULATIONS FOR 2,3,7,8-TCDD
Test Series
Parameter
Waste feed concentration
Waste feed rate
Mass rate in
Pollutant mass out
Flue gas concentration
Mass rate out
Destruction and removal efficiency
EPA Destruction and removal efficiency
Performance standard
Units
2A
3A
ug/kg
Ib/hr
ug/hr
P8
ug/m
ug/hr
percent
percent
227
47.67
4908
<14
<2xlO"6
<1.93xlO~4
>99. 999996
99.9999
156
48.12
3405
<8
<3xlO~6
<3.59xlO~4
>99. 999989
99.9999
2-3
-------
,, PHYSICAL A"° CHEMICAL CHARACTERISTICS
THE FLUE GAS AND THE SAMPLE COLLECTION SYSTEM
RESULTS OF FLOWRATE AND IBOKINETIC CALCULATION
RUN NUMBER «•*«••
DATE OF RUN *•»•••
CLOCK TIMEt INITIAL **•»»»
CLOCK TIMEl FINAL «•»»«*
K>
AVG. STACK TEMPERATURE
AVG. SQUARE DELTA P
NOZZLE DIAMETER
BAROMETRIC PRESSURE
SAMPLING TIME
SAMPLE VOLUME
AVG. METER TEMP.
AVG. DELTA H
DGM CALIB. FACTOR CY1
WATER COLLECTED
CO 2
O 2
CO
N 2
STACK AREA
STATIC PRESSURE
PI TOT COEFFICIENT
SAMPLE VOLUME DRY
WATER AT STD.
MOISTURE
MOLE FRACTION DRY GAS
MOLECULAR WT.DRY
EXCESS AIR
MOLECULAR WT. WET
STACK GAS PRESSURE
STACK VELOCITY
VOLUMETRIC FLOWRATE, DRY STD.
VOLUMETRIC FLOWRATE, ACTUAL
ISOKINETIC RATIO
DEGREES F
INCHES H2O
INCHES
IN. HG.
MIN.
CUBIC FEET
DEGREES F
IN. H20
«••«•*
MILLITERS
PERCENT
PERCENT
PERCENT
PERCENT
SQUARE INCHES
INCHES WG.
*••*••
DSCF
SCF
PERCENT
*»••**
LB/LB MOLE
PERCENT
LB/LB MOLE
INCHES HG.
AFPM
DSCFM
ACFM
PERCENT
2A
IOJULBS
1011
1711
167.0
O.6
0.3
30.0
3B9.O
268.0
116.0
1.5
1.0
2871.O
3.8
14.4
0.0
81.8
7.1
0.4
0.8
249.5
135.4
35.2
O. 6
29.2
200.1
25.2
30.0
2129.5
57.2
IO4.6
105.0
3A
11JUL85
1O59
132O
169.0
0.7
0.3
29.9
130.0
114.5
11O.O
2.5
1.0
1263.4
3.0
1O.O
O.O
87. O
7.1
0.4
O.8
1O7.5
59.6
35.7
O.6
28.9
77. 1
25.0
29.9
2889.7
76.5
141.9
101.2
CALCULATIONS FOR BRAIN LOADING AND EMISSION RATES
FRONT HALF TOTAL (Filter Only)
PAR1'CUt-ATE
• A ULA1E AT 7 7. O2
-------
TABLE 2-1
SUMMARY OF RESULTS - TCDDC ANALYSES
Sample Stream TCDD
Waste Feed (ng/g)a
Run 2 227
Run 3 156
Incinerator Ash/Treated
Soil(ng/g)a
Run 2 <0.038
Run 3 <0.033
Scrubber Effluent (ug/1)
Run 2
Run 3
Flue Gas (Total pg)
Run 2 <14
Run 3 <8.4
Field Biased Blank <22
Analyses conducted by Roy F. Weston at their Times Beach laboratory
b
Analyses conducted by the University of Missouri.
Assumed to be the concentration of the 2,3,7,8-TCDD analogue
reported as total TCDD.
2-2
-------
3. FIELD SAMPLING PROGRAM
As discussed previously samples were collected from each of four
incinerator influent/effluent streams during each of the two test
series. These included the following types of samples: flue
gas/waste feed, incinerator ash and scrubber effluent. Additional
details pertinent to the collection of each of the four matrices are
provided below.
Waste Feed
Samples of the contaminated Times Beach soil were collected from
the feed hopper to the incinerator in conjunction with each of the
test runs. Three to four grab samples were collected during each run
and composited to a single sample in a pre-cleaned 1000 ml amber glass
container for subsequent analysis.
Incinerator Ash
Samples of incinerator ash were collected during the course of
each test run by means of an access port located in the ash hopper.
Four to five grab samples were collected during each run and
composited to a single sample in a pre-cleaned 1000 ml amber glass
container for subsequent analysis.
Scrubber Effluent
Samples of the scrubber effluent water were collected at 30
minute intervals throughout each test run. The samples from the
recirculating system were collected from the blowdown tank and
composited to provide a single, one liter sample for each run.
1375J C3044-A
-------
Flue Gas Sampling
A modified U.S. EPA Method 5 sampling train was us.ed to quantify
particulate and semi-volatile emissions from the unit. A schematic of
the sampling train used is presented in Figure 3-1.
In accordance with the specifications of EPA Method 5 and the
ASME dioxin protocol contained in Appendix D, flue gas samples were
collected isokinetically using a single sampling point placed in the 3
inch stack. In addition full system leak checks of the sampling train
were performed prior to and at the completion of each test series.
Stack velocity and cyclonic flow check measurements were also taken
just prior to the commencement of each test series.
The sample train consisted of a glass-lined heat-traced probe
with a stainless steel button hook nozzle and attached thermocouple
and pitot tubes. After the probe, the gas passed through a heated
glass fiber filter (Reeve Angel 934 AH filter paper). Downstream of
the heated filter, the sample gas passed through a water-cooled
module, then through a sorbent module that contained approximately 25
grams of XAD-2 resin. The XAD module was followed by a series of four
impingers. The first impinger, acting as a condensate reservoir
connected to the outlet of the XAD module, was modified to have a
short stem so that sample gas would not bubble through the collected
condensate. The second and third impingers each contained 100 ml of
1.0 NaOH water for the collection of HCl followed by a pump, dry gas
meter, and a calibrated orifice.
At the conclusion of each of the test runs, the sample train was
removed to a designated clean area for sample recovery activities.
(This consisted of an organic free recovery trailer provided by the
Missouri Department of Natural Resources).
The particulate filter was removed from its housing and
transferred to its original glass petri dish. The container was
sealed with Teflon tape and labeled as: -M5/FF. Run number precedes
all sample codes (e.g., 1-M5/PF).
The front half of the sampling train was rinsed three times with
1:1 methylene chloride and acetone. The rinse was recovered into an
amber glass container and labeled as: -M5/FH.
1375J C3044-A 3_2
-------
Rccirculation Pump
Tharmomatart
Tamparatura
Probe
Ravarsa Type
Pitot Tub*
Vacuum Line
Dry Gas Matar
Air Tight
Pump
IMPINGERS
1 CondartMta Trap (Empty)
2 1NN«OH|100ml)
3 INNaOHdOOml)
4 Silica Gal
*First impinger which serves as condensate crap has a very short
stem that does not extend into the condensate.
Figure 3-1 Schematic of the Modified Method 5 Train Employed for
Flue Gas Sampling During the Times Beach Demonstration
Program.
3-3
-------
The volume of condensate collected in the first impinger was
measured in a pre-cleaned glass graduated cylinder and transferred to
an amber glass bottle. The sample was then preserved by adding a
predetermined amount of methylene chloride (30% of the total sample
volume). A methylene chloride rinse of the condensing coil and
impinger were also added to the sample which was then labeled as
-MS/CD.
The sorbent trap containing the XAD-2 resin was sealed using
ground glass fittings and labeled as: -M5/XR. The volume of water
collected in the second and third impingers and weight gain of the
desiccant contained in the final impinger were determined and recorded.
All containers were inspected to ensure integrity of the samples
and logged on chain of custody tracking sheets.
The number and type of samples collected during the field program
are listed in Table 3-1.
Copies of all calibration and field data sheets are presented in
Appendix A.
Combustion Gas Analysis - ORSAT Measurements
Combustion gas measurements for CO., O and CO were taken
during each of the two test series. These measurements were conducted
in accordance with EPA Method 3 employing an ORSAT. (Federal Register
40 CFR Part 60 Appendix A July 1, 1985).
1375J C3044-A , .
3-4
-------
TABLE 3-1
SAMPLES COLLECTED DURING THE TIMES BEACH DEMONSTRATION PROGRAM
Sample Type
Source
Number
Collected
Container Type
Modified Method 5 train
Particulate filter
Particulate rinses (Probe)
XAD-2 resin
Condensate catch
Impinger catch (IN NaOH)
Solvent rinses of train
(methylene chloride/acetone)
Train
Train - Front half rinse
XAD-2 tube
First impInger
Second/third impingers
Back-half rinse
2
2
2
2
2
2
2
Glass petri dish
500 mL amber glass
Glass sorbent trap
500 mL amber glass
500 mL amber glass
500 mL amber glass
500 mL amber glass
Method blanks
XAD-2 resin blank
Filter lot blank
Methylene chloride blank
Acetone blank
Impinger water blank
IN NaOH
XAD-2 lot
Filter lot
CH2C12 lot
Acetone lot
Organic- free
laboratory water
NaOH lot
1
1
1
1
1
1
1
Glass sorbent trap
Glass petri dish
500 mL amber glass
500 mL amber glass
500 mL amber glass
500 mL amber glass
500 mL amber glass
Other
Contaminated soil feed
Incinerator Ash
Scrubber effluent
Waste feed hopper 6-8
Access Port-Ash Hopper 8-10
Slowdown tank 6
1000 mL amber glass
1000 mL amber glass
1000 mL amber glass
-------
4. LABORATORY ANALYSIS
As discussed previously, samples from each of the two test series
were transferred to Weston's Times Beach Laboratory for the analysis
of 2,3,7,8-tetrachlorodibenzodioxin. The requisite analyses were
performed using the rapid method developed by Weston employing a gas
chromatograph coupled with tandem mass spectrometry (GC/MS/MS).
The analytical methodology employed by Weston has been accepted
by the EPA for use in performing TCDD analyses of Times Beach soil in
support of an existing contract at the site. The current version of
the analytical protocol is presented as part of the Weston Report for
this test program which is provided in Appendix B. Certain deviations
from the analytical protocol have been used in order to accommodate
the nature of the collected samples. Sample preparative procedures
peculiar to this test program, and not contained in Appendix B, are
described 'below.
Solid Samples
The analytical methodology for the feed stock and ash samples is
as described in the EPA method.
Flue Gas Samples
The sampling train was received in the form of four different
samples consisting of a condensate sample, front half rinse, a
particulate filter, and an XAD-2 trap. While we were interested in
determining the total amount of TCDD in the train, the four components
needed to be prepared separately. The treatment of each is described
below.
a. Condensate Sample
The condensate was placed in a separatory funnel and extracted
three times with 100 mL of dichloromethane by shaking the mixture and
allowing the phases to separate. The dichloromethane phase from each
of the extractions was filtered through anhydrous sodium sulfate into
1377J C3044-A
-------
a beaker. The combined condensate extract was evaporated gently on a
hot plate maintained at a low heat with a stream of nitrogen. When
the volume of extract solution was approximately 10 mL", the beaker was
removed from the hot plate, and the solution retained until the
corresponding extracts from the same train were available.
b. Particulate Filter Sample
Initial gravimetric determinations were conducted on the
particulate filters in accordance with the requirements of US EPA
Reference Method 5.
The particulate filter was cut into pieces and placed in an
extraction jar. Approximately 100 mL of acetonitrile-dichloromethane
(2:1 by volume) were added, and a magnetic stirring bar was placed in
the jar. The sample was continuously stirred for about 2 hours.
At the end of the extraction period, the solvent was passed
through a filter into a separatory funnel and 900 mL of distilled
water were added. The mixture was shaken to transfer the acetonitrile
from the organic phase into the aqueous phase. The layers were
allowed to separate, and the dichloromethane layer was passed through
anhydrous sodium sulfate into the same beaker containing the extracts
from the condensate and front half rinse samples. The solution was
concentrated to a volume of about 10 mL.
c. Front Half Rinse Sample
The front half rinse was added to a separatory funnel containing
approximately the same volume of water as the volume of the rinse.
The mixture was allowed to separate, and the lower phase removed. The
aqueous upper phase was discarded.
The process was repeated, taking the retained lower phase and
adding it to water so that the water soluble portion of the solvent
could be removed.
1377J C3044-A 4~2
-------
The organic phase was passed through anhydrous sodium sulfate
into the same beaker containing the condensate extract. The solvent
was evaporated on a hot plate with a stream of nitrogen, until the
final volume of solution was about 10 mL.
d. XAD-2 Trap Sample
The resin was transferred into an Erlenmeyer flask and was spiked
with 10 uL of the spiking mixture containing 0.5 ng/uL of the internal
standard and 0.1 ng/uL of the surrogate compound.
The spiked resin was treated with 100 mL toluene and placed on a
stirring hot plate. The mixture was stirred and heated for two
hours. At the end of the extraction time, the solution was filtered
while still hot into the beaker containing the extracts from the other
portions of the sampling train. The mixture was gently evaporated to
dryness using heat and under a flow of nitrogen gas. '
The combined extract was redissolved in about 10 mL of
dichloromethane and the solution was transferred into a vial. The
solvent was exchanged to cyclohexane following the procedures
described in Appendix B. The extract was taken through both clean-up
steps described in the Appendix. After the second clean-up step, the
extract was concentrated to a final volume of 100 uL. Attempts to
concentrate it further proved unsuccessful, since the solution became
rather viscous.
The extract was then ready for GC/MS/MS analysis as described in
the EPA methodology contained in Appendix B.
Scrubber Effluent Samples
The analysis of the scrubber effluent samples was conducted by
the University of Missouri. Documentation pertinent to these analyses
is presented in the companion document to this report. Final Report.
On-site Incineration Testing of the Shirco Portable Pilot Test Unit.
Times Beach. Missouri. Shirco Report No. 815-85-2, Nov. 1A, 1985.
1377J C3044-A
4-3
-------
5. QUALITY CONTROL PROTOCOLS
Quality control protocols for this program included a number of
control elements common to flue gas monitoring programs for trace
organic constituents. These included quality control measures
associated with both the field sample collection activities conducted
by ERT, as well as the analytical measurements performed by Roy F. Weston.
Further details on some of the more prominent features of the quality
control program are provided in the discussion to follow.
Chain-of-Custody
Samples were collected on July 10 and 11, 1985 and transferred
under Chain-of-Custody to Roy F. Weston's Times Beach laboratory on
July 12, 1985. A copy of this chain-of-custody documentation is
provided in Appendix B of this report.
Field Sampling Activities
The sampling methodology and associated quality control protocols
v for the collection of the flue gas samples were consistent with those
contained in the ASME methodology entitled Sampling for the
Determination of Chlorinated Organic Compounds in Stack Emissions
(Draft EPA 450/4-84-014c).
This approach is presently in use for source sampling of Tier 4
combustion sources in support of EPA's National Dioxin Study. A copy
of this protocol (Draft) is provided in Appendix D of this report.
Quality control measures prescribed in the ASME methodology and
incorporated into ERT's field sampling program included but were not
limited to the following: replicate trains, field blanks, method
blanks, XAD-2 sorbent pretreatment and QC acceptance criteria, and
sampling train leak check procedures. For example a complete sampling
train was assembled and dismantled in the field during the test
program to serve as a field biased blank. The components of this
sample train accompanied the actual sample set during storage and
5-1
1433J-C3044-A
-------
transport to Roy F. Weston's laboratory. The analytical results for
this field biased blank train are contained in Appendix B of this
report.
Analytical Measurements
Quality control features of the analytical program were
consistent with the EPA dioxin methodology employed by Roy F. Weston
at their Times Beach laboratory. Actual QA/QC features of the
analytical program were implemented in accordance with the EPA
methodology contained in Appendix B of this report as well as
requirements of the ERT Work Scope provided to Roy F. Weston at the
outset of the program. (A copy of these specifications are provided
in Appendix C of this report). These included but were not limited to
the following types of quality control measures: performance check
samples, replicate analyses, and the use of isotopically labeled
surrogate compounds placed in each program sample.
Further details on each of these quality control elements is
provided in the discussion to follow. This includes a summary and
evaluation-of each data category. The data evaluation will also
discuss any perceived anomalies in the quality of the reported data.
Matrix Spikes
Results are provided for a single soil sample spiked with a 1 ppb
spike of native TCOO (assumed to be 2,3.7,8 TCOD or 1,2,3,4 TCDD). A
recovery of 99.0% (0.99 ppb) was reported. This value is consistent
with performance criteria contained in the EPA protocol.
Replicate Analyses
No results are provided for replicate analyses of any of the
media. It can only be assumed that sample replicate analyses were not
performed as part of the quality assurance protocol. It appears,
however, that mandatory replicate analyses are not a provision of the
EPA TCDD protocol used by Weston in the analyses of the ERT/Shirco
samples.
5-2
1433J-C3044-A
-------
Surrogate Spikes
Surrogate data contained in the Western report (Appendix B pg. 8)
satisfy all of the requisites specified in the Scope of Work provided
37
to them by ERT with two exceptions. The % recovery data for Cl
- 2,3,7,8 TCDD contained in the report for both the ash samples and
the flue gas samples are in compliance with the acceptance criteria
provided by EPA as part of their TCOD protocol. Surrogate recovery
data for the two ash samples ranged from 92-109%, while recovery data
for the three flue gas samples ranged from 99-105%. All of these data
are within the acceptance range provided by EPA as part of the TCDD
protocol (60-140%).
Surrogate recovery data for the two soil feed samples, however,
were well beyond the upper acceptance limit specified in the
protocols. Recovery values of 473.9% and 378% were reported (pg.8)
for Runs 2 and 3, respectively. Despite the 4x (four times)
enhancement in the expected surrogate recoveries, in our judgement, we
do not feel that the native TCDD data for these samples has been
compromised.
The apparent enhancement in recovery of the Cl. - 2,3,7,8
TCDD isomer was not actually caused by a 4x increase in the amount of
surrogate present, but rather by a signal enhancement for those ions
used to quantitate the surrogate species. More simply, the presence
of elevated concentrations of native TCDD in the soil feed samples
(156-227 ng/g or ppb) has provided a positive interference to those
ions normally used to quantitate the isotopically labeled surrogate.
The EPA TCDD protocol employed by Weston in fact contains the
following excerpt pertinent to this issue:
[Native 2,3,7,8-TCDD contains an innate quantity of 3 C14 -
2,3,7,8-TCDD.* Except at high concentrations of native 2,3,7,8-TCDD,
this contribution is too small to significantly affect the calculated
concentration of surrogate Cl -2,3,7,8-TCDD. The theoretical
correction is calculable on the basis of isotope distribution and
^Naturally occurring elemental chlorine is comprised of both
1?C135 (75.53%) and 17C137 (24.47%).
5-3
1433J-C3044-A
-------
amounts to 1.08% of the m/z 257 peak. (This correction should be
checked at low resolution by analyzing about 200 pg/ul of unlabeled
2,3, 7 ,8-TCDD. ) On this basis, the correction to the area count of the
surrogate, is made as follows:]
A263 = A263 - 0.0108
Calculate the analytical percent recovery of the surrogate
standard.
Surrogate amount measured (nanograms) x 100
Analytical = 5 ng
Percent Recovery
In any case, it should be emphasized that this anomaly has not
comprised the data reported for native TCDD in each of the two feed
samples. In fact, TCDD values of 227 ppb and 150 ppb reported for
Runs 2 and 3, respectively are corroborated by results provided by
the State of Missouri. The latter analyses conducted on replicate
aliquots of the ERT incinerator feed samples were in fact somewhat
higher than the values reported by Weston in this report. Hence, the
Weston data can be construed as providing a more conservative estimate
of the TCDD destruction efficiency (%) achieved by the Shirco Infrared
incinerator.
Calibration Data (GC/MS/MS)
As specified in the EPA TCDD protocol, results are provided for
both a daily calibration check sample (pg.9, Table 4) as well as a
3-point standing calibration curve (pg. 4, Table 1). All of the
response factors provided here are within the prescribed acceptance
range of 1.630-1.993. Furthermore, the instrument calibration checks,
as stipulated by the EPA dioxin methodology, were run within the
8-hour elapsed time criteria between actual samples and calibrant.
The samples themselves were run early in the morning of August 6 ,
1985, while the requisite system calibrants were run late on August 5.
5-4
1433J-C3044-A
-------
Additionally, copies of the computer derived quantitation reports
are provided in Appendix B. Data pertinent to the generation of the
August 03 standing calibration curve including response factor data
are provided in Table 1 (pg.4) of the Weston report. In general, the
calibration documentation are presented in accordance with the data
reporting requirements of the EPA protocol. A copy of these data
reporting requirements are provided in Appendix B of this report.
Further details including documentation pertinent to the above
categories of quality control data are contained in Roy F. Weston's
analytical report provided in Appendix B. The reader is referred to
this document for other critical QC features of the TCDD analytical
program not addressed in the preceding discussion.
5-5
1433J-C3044-A
-------
APPENDIX A
FIELD CALIBRATION DATA
1. Run Data Forms - Particulate Test Field
Data Sheets
2. Temperature Sensor Calibration Form
3. Dry Gas Meter Calibration Data
4. Pitot Tube Calibration Data
1430J C3044-A
-------
A /I
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-------
APPENDIX B
WESTON LABORATORY ANALYSIS REPORT
-------
7720 LORRAINE AVENUE
SUITE »102
STOCKTON. CA 95210
PHONE (209) 957-3405
ANALYSIS OF COMBUSTION PRODUCTS FOR
2, 3, 7, 8-TETRACHLORODIBENZODIOXIN (TCDD)
-------
ANALYSIS OF COMBUSTION PRODUCTS FOR 2,3,7,8-TETRACHLORCDIBENZODIOXIN (TCDD)
1.0 INTRODUCTION
In support of Shirco Infrared Systarts, WESTON undertook to perform ana-
lyses of samples collected during a demonstration of a combustion system for
the destruction of 2,3,7,8-tetrachlorodibenzodioxin (TCDD). The analyses
were performed using the rapid method developed by WESTON and which employs
gas chromatography coupled with tandem mass spectrcmetry.
The analytical methodology has been accepted by the EPA and the current
version of the analytical protocol is presented in Appendix A. Certain
deviations from the analytical protocol have been used in order to accommodate
the nature of the collected samples. A discussion of the deviations will be
presented in Section 3.0.
The results of the analyses for two runs are summarized below:
Component TCDD Found
Run 2 Run 3
Feed 227 ng/g 156 ng/g
Sampling train (Composite) <14 pg (total)
-------
The sampling train was received in the form of four different
samples consisting of a corelensate sample, front half rinse, a particulate
filter, aid an XAD-2 trap. While we were interested in determining the
total amount of TCDD in the train, the four components needed to be
treated separately. The treatment of each is described below.
a. Condensate Sample
The condensate was placed in a separatory funnel and extracted
three times with 100 ml of dichloromethane by shaking the mixture and
allowing the phases to separate. The dichloromethane phase from each
of the extractions was filtered through anhydrous sodium sulfate into
a beaker.' The combined condensate extract was evaporated gently on a
hot plate maintained at a low heat with a stream of nitrogen to help
remove the vapors. When the volume of extract solution was approximately
10 mL, the beaker was removed from the hot plate, and the solution retained
until the other extracts from the same train were ready.
b. Front Half Rinse Sample
The front half rinse was added to a separatory funnel containing
approximately the same volume of water as the volume of the rinse. The
mixture was allowed to separate, and the lower phase removed. The aqueous
upper phase was disposed of.
The process was repeated, taking the retained lower phase and
adding *'it to water so that the water soluble portion of the solvent could
be removed.
The organic phase was passed through anhydrous sodium sulfate
into the same beaker containing the condensate extract. The solvent was
evaporated on a hot plate with a stream of nitrogen, until the final volume
of solution was about 10 mL.
c. Particulate Filter Sample
The particulate filter was cut into pieces and placed in an
extraction jar. Approximately 100 mL of acetonitrile-dichloromethane
(2:1 by volume) were added, and a magnetic stirring bar was placed in the
jar. The sample was continuously stirred for about 2 hours.
At the end of the extraction period, the solvent was passed
through a filter into a separatory funnel and 900 mL of distilled water
were added. The mixture was shaken to remove the acetonitrile from the
organic phase into the aqueous phase. The layerc were allowed to separate,
and the dichloromethane layer was passed through anhydrous sodium sulfate
into the same beaker containing the extracts from the condensate and front
half rinse samples. The solution was concentrated to a volume of about
10 mL.
-------
d. XAD-2 Trap Sample
The resin was transferred into an Erlenmeyer flask and was
spiked with 10 uL of the spiking mixture containing 0.5 ng/uL of the
internal standard and 0.1 ng/uL of the surrogate compound. For soils
the amount of spiking mixture that is normally added is 50 uL; however,
it is known that the spiking mixture contains a small amount of native
TCDD. Because of this, the volume of spiking mixture that was added
was reduced, so that its contribution to any native TCDD would be mini-
mized.
The spiked resin was treated with 100 ml toluene and placed
on a stirring hot plate. The mixture was stirred and heated for two
hours. At the end of the extraction time, the solution was filtered
while still hot into the beaker containing the extracts from the other
portions of the sampling train. The mixtrue was gently evaporated to
dryness using heat and under a flow of nitrogen gas.
The combined extract was redissolved in about 10 mL of dichloro-
methane and the solution was transferred into a vial. The solvent was
exchanged to cyclohexane following the procedures described in Appendix
A. The extract was taken through both clean-up steps described in the
Appendix. After the second clean-up step, the extract was concentrated
to a final volume of 100 uL. Attempts to concentrate it further proved
unsuccessful, since the solution became rather viscous.
The extract was then ready for GC/ttS/MS analysis as described in
Appendix A.
4.0 RESULTS
a. Calibration Curve
The calibration curve was constructed using EPA supplied mixed
standards. Each standard solution was prepared as described in the protocol
of Appendix A, then concentrated by a factor of 10. Two uL injections were
made. The initial calibration curve associated with these samples was
obtained on August 3, 1985. The data are shown in Table 1. The single ion
traces for the four monitored ions are shown in Appendix C.
Based on the calibration curve, the ratio of the areas for the
ions of native TCDD will be acceptable if it falls in the range 0.861 -
1.053. The response factor for the native TCDD, RFn, in the daily calib-
ration is acceptable in the range 1.630 - 1.993.
-------
TABLE 1
CALIBRATION CURVE DATA
Filename
AUG0324
AUG0325
AUG0326
Concentration, ng/L
Raw Area Counts
Ratio
RF_
RF0
AUG0327
AUG0328
AUG0329
AUG0330
AUG0331
AUG0332
Native
1
1
1
5
5
5
25
25
25
Surrogate
0.3
0.3
0.3
0.6
0.6
0.6
1.0
1.0
1.0
I.S.
5
5
5
5
5
5
5
5
5
A257
8
9
9
28
24
27
165
181
168
,967
,050
,169
,075
,515
,981
,402
,270
,035
A259
9,345
9,361
10,003
Mean
Standard
29,664
27,144
28,121
Mean
Standard
167,820
186,731
173,355
Mean
Standard
> A263 A268
6,
6,
6,
508 48
150 48
464 51
,865
,753
,300
Deviation
8,
1,
7,
648 33
610 30
233 29
,906
,019
,465
Deviation
16,
18,
16,
274 39
454 41
962 36
,185
,010
,898
Deviation
Overall Mean
Overall Std.
Deviation
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.9596
.9668
.9166
.9477
.0271
.9464
.9031
.9950
.9482
.0460
.9856
.9708
.9693
.9752
.0090
.9570
.0303
1
1
1
1
0
1
1
1
1
0
1
1
1
1
0
1
0
.8737
.8882
.8686
.8768
.0102
.7029
.7209
.9040
.7759
.1113
.7008
.7947
.8505
.7820
.0757
.8116
.0834
2
2
2
2
0
2
2
1
2
0
1
2
2
2
0
2
0
.1922
.0746
.0733
.1134
.0683
.0634
.0513
.9744
.0297
.0483
.8866
.0510
.0936
.0104
.1093
.0512
.0836
-------
b. Blank Response
The blank response is used to derive the detection limit (L.O.D.)
and the correction factor. The blank consists of the same spiking mixture
used to introduce the surrogate and internal standard into the samples, but
this mixture is simply prepared in solution to yield concentrations that
approximate the concentrations of these two compounds in the final extract.
The need for the measurement of the blank response has arisen
due co the fact that the surrogate compound contains a small amount of
a component normally found as part of the native TCDD, specifically it is
that component which gives rise to the daughter ion of mass 259. Since
the area of the daughter ion of mass 257 is hardly affected, the average
value of this area has been used in measuring the noise level.
The raw data and the calculated parameters from the blank res-
ponse are shown in Table 2. The single ion traces of these data are in
Appendix D.
Based on the blank response data, the detection limit for a
five gram sample of solid material (soil or ash) is 0.038 ppb. For samples
the weight of which is different than 5.0 g, the above value must be
multiplied by the factor 5.0/W where W is the actual weight of the sample.
The calculation of the detection limit in absolute quantity,
needed for the evaluation of the quantity of TCDD in the sampling train,
is more complex. This is so because the protocol itself is designed to
handle ratios of area counts to internal standard area count, but in
deriving an absolute detection limit, the real quantities injected must be
known. The following assumptions were made in deriving the absolute
detection limit:
1. The instrumental response to 1 pg of native TCDD measured
as the area of the daughter ion of mass 257 is the same
as the instrumental response to 1 pg of the internal stan-
dard measured as the area of the daughter ion of mass 268.
2. The detection limit is three times the noise level.
In preparing to obtain the blank response, the spiked solution
was concentrated by a factor of thirty; hence, the concentration of the
internal standard was 450 pg/uL. Each injection into the instrument was
of 2 uL; thus introducing a total of 900 pg of the internal standard.
The mean area count for the ion of mass 268 was 150,000. Therefore, the
instrumental response is 167 counts/pg.
The average response for the native ion of mass 257 was 466,
and is assumed to be instrumental noise. The detection limit is taken
as three times the detection limit, corresponding to an area count of
1398. Hence, the absolute detection limit is 1398/167 = 8.4 pg.
-------
TABLE 2
BLANK RESPONSE DATA
Filename
AUG0303
AUG0304
AUG0305
AUG0306
AUG0307
AUG0308
AUG0309
AUG0310
AUG0311
AUG0312
AUG0313
AUG0314
AUG0315
AUG0316
AUG0317
AUG0318
AUG0319
AUG0320
AUG0321
AUG0322
Raw Area Counts
RF
B
A257 A259
332
424
518
1,454 1,
0
782 1,
565
0
523
287
244
272 1,
486
803
1,073 1,
354
795 1,
121
0
284
Mean
Standard
93
619
708
063
789
059
851
454
113
619
800
196
667
0
116
329
314
215
100
178
A263
36,480
77,740
63,393
68,709
72,333
75,769
66,324
67,378
70,517
63,532
67,932
61,605
58,429
59,874
62,743
.-61,855
'66,508
61,007
51,336
62,474
A268
81,602
183,842
155,264
166,342
172,757
176,403
161,669
166,685
172,301
154,263
165,791
150,693
148,475
142,669
154,739
151,378
165,254
157,302
123,048
149,615
Deviation
°
2.2352
2.1143
2.0415
2.0653
2.0935
2.1476
2.0512
2.0211
2.0463
2.0592
2.0487
2.0441
1.9676
2.0984
2.0274
2.0431
2.0123
1.9392
2.0860
2.0878
2.0615
0.0627
0.0052
0.0057
0.0079
0.0151
0.0046
0.0104
0.0088
0.0027
0.0037
0.0059
0.0063
0.0097
0.0078
0.0056
0.0141
0.0045
0.0128
0.0021
0.0008
0.0031
0.0068
0.0040
0.0144
0.0157
0.0218
0.0417
0.0127
0.0287
0.0243
0.0075
0.0102
0.0163
0.0174
0.0268
0.0215
0.0155
0.0389
0.0124
0.0353
0.0058
0.0022
0.0086
0.0189
0.0110
C.F.
L.O.D.
0.0068
0.0378 ng/g
-------
In determining the absolute detection limit in each of the
analyzed sampling trains, the actual internal standard recovery must be
known. It is expected that in the clean-up steps some loss could occur.
Since the extract from each of the trains contains a maximum of 50 pg/uL
of internal standard, and since 2uL are injected, the maximum area for
the ion of mass 268 is 16,700. Hence, to obtain the detection limit in
each of the measurements, the factor 8.4 must be multiplied by the
ratio 16,700/^258•
c. Results of Sample Analysis
The results of the sample analyses are shown in Table 3. The
ion traces for the samples are found in Appendix E.
The surrogate recovery for the feed stocks appears much higher
than is acceptable. The reason for this phenomenon is that the native
TCDD, containing approximately 1% of the surrogate compound, as calculated
on the basis of isotope distribution in nature, overwhelms the amount
spiked. Thus, a sample that contains 250 ppb native, when spiked with
1 ppb surrogate, would appear to contain 3.5 ppb surrogate, or 350%
surrogate recovery. Hence, for high levels of native TCDD in the sample
the surrogate recovery as defined in the protocol is not applicable.
d. QA/QC Sample Analysis
Table 4 shows the daily calibration run for the period of the
sample analysis on August 5-6, 1985.
Table 5 lists the results for the method blank run for the
same period, and Table 6 shows the results for a 1 ppb spike of native
TCDD into uncontaminated soil.
The initial traces for these runs are in Appendix F.
e. Miscellaneous Measurements
For the sampling trains, volumes of condsate and weights of
particulate filters were obtained.
Sample Description Sample No. Sample Wt., g Sample Vol., ml
Particulate Filter, Run 2A E426 0.6712
(TB-08)
Particulate Filter, Ron 3A E434 0.6623
(TB-10)
Particulate Filter, Blank E437 0.6598
(TB-09)
Condensate, Run 2A E424 - 2,570
Condensate, Run 3A E432 - 930
-------
Filename
AUG0605
AUG0606
AUG0603
AUG0604
AUG0620
Sample I.D.
Feedstock
Feedstock
Ash Run 2
Ash Run 3
Run 2 (E439)
Run 3 (E440)
(E441)
(E442)
Sample
Wt., g
5.10
5.62
4.96
5.70
Sampling Train Run 2A
TABLE 3
RESULTS OF SAMPLE ANALYSES
Raw Area Counts
A257
2,190,010
2,031,298
277
0
0
A259
2,286,855
2,122,987
661
0
0
A
123
119
59
73
4
263
,131
,297
,262
,943
,166
A268
53,323
65,187
133,176
171,762
10,221
• TCDD
227
156
< 38
< 33
< 14
Units Ratio
ng/g 0.9581
ng/g 0.9568
pg/g
pg/g
pg
(S
Surrogate
Rec., %
473
378
109
92
99
(E424 + E425 + E426
+ E427)
AUG0621 Sampling Train Run 3A
(E432 -I- E433 + E434
+ E435)
AUG0617 Field Biased Blank
(E436 + E437 + E438)
7,093 17,090 < 8.4 pg
2,684 6,214 < 22
P9
101
105
-------
Filename Concentration, ng/L
Native Surrogate I.S.
AUG0502 1 0.3
TABLE 4
DAILY CALIBRATION
Raw Area Counts
Ratio
RFV
RFV
A257
A259 A263 A268
11,092 10,666 9,902 58,520 1.0399 1.8250 2.7917
-------
TABLE 5
METHOD BLANK
Filename
Sample I.D.
Sample
Wt., g
A257
Raw Area
A259
Counts
A263
A268
TCDD
Units
Ratio
Surrogate
Rec., %
AUG0508 Method Blank
5.0
901 1,323 50,142 110,289 <38 pg/g
115
-------
TABLE 6
SPIKE RECOVERY
Amount Sample TCDD Spike Surrogate
Filename Spiked Units Wt., g Raw Area Counts Found Units Rec., % Ratio Rec.r %
A257 A259 A263 A268
AUG0506 1.0 ppb 5.13 24,486 26,098 60,431 134,139 0.996 ppb 99.6 0.9382 107
-------
APPENDIX A
ANALYTICAL PROTOCOL
-------
APPENDIX B
CHAIN OF CUSTODY
-------
Field Sheet and Chain of Custody Record
CToJJec tor's Name an
l*\ -.Af, ftVr .,
Sample
No.
R. ,v r) /
r -h;
, ••
I' '()•;
•• 'i :.••
t. U * 7
!. 'i ,'•
d Affiliation (Please Print)
~i v i r* j-\n )
Sample Description
\
(,-•-,(
T, , •
VM,
.. _,,
..,,,7, '.,.-
f' (\,J (' ^ !•-»•> "
, r. ,- 1, 1 ,
-,
V 7"i' ,^
. . t/)
-ol,,K^
rtuv/ &***hln lf*JLl
Received fly/
D Sealed
Received By
D Sea Jed
Recei ved By
Date
7/'2/Q
•
Time
70/7
eale
d
Field Analyses
?«t
^
i/
v/
/
If Shipped
Carrier
Carrier
Carrier
Carrier
to/
^
y
Delivered
Date
Time
Sample
Category
Picked Up
Date
Time
-------
MISSOURI DEPARTMENT OF-JUOURAL RESOURCES
pfyf.fan of EnjfjjfOMxyittt^ffuaJJ. ty
Field Sheet and Chain of Custody Record
Collector's
Sample
No.
.- ,, : »
;,.- './-
. '/ • <
. '/•/'
-. •;>'
1 f ' '• ''
r '/ • <•
Name and Affiliation (Please Print)
1 -< — ^ — •
Sample Description
i
•f^r h
<:,-!-.,./.
r^
r •
.y ,
r//-,-t IV.
r v v. - ,.
» Chain of Custtdr^ ffeoe
1
rd
, ,, ^
f.t4-
' "' ' . ' ^ .
r,, r, ^
(jL How Scale
Collected
Date
\
Tine
Analyses Requested
/Wjirj^u-is/ied fly \' / x V
D Sealed' """ U Shipped
Relinquished Ou
LJ SeaJed G Shi
d
[ | <-
-------
Di vi»lon of-gitv-iT onrogiitaJUguaJi ty
Field Sheet and Chain of Custody Record
Collector's
K..I- 1
Sample
No.
r ' / v;
IMv J.
r -MV)
r- 'Uitl
Hr.fY'*" •
r 'i'i|
C '/'/,'
Name and Affiliation (Please Print)
v ,,S. fcivr )
Sample Description
vN^-'i- T«x.i,ftlfc,;y
p- ,-^1
iV.^*^-
/x,,^^
' i'
i
1 -. v^ J
• » -^ -1 *
/•~»;/\ -^
<; ^ ^
i's'. '/I '
. Chain' of Custodj* Record
gv4^--vt c -\ i.
^D Sealed Q Shipped
Relinquished ny
LJ Sealed D Shipped
Relinquished By
D .'•tMJerf D Shipped
We lirwuished B\,
Description of Shipment No. of Samples &L3
No. of Container
Collected
Date
Time
S 23 How S
AnaJyses Requested
3,3,1,S--nii&
n
M
//
1
K^C^ptea By./
rg^MYpn^* y_
LJSeflJed (fa/X.l}te>&*1faLr&'*/S
Received Byf/ '
D Sealed
Received By
D Sea Jed
Received By
Date
?M
*
Time
V&^
eale
d
Field Analyses
J/ Shipped
Carrier
Carrier
Carrier
Carrier
Delivered
Date
Time
Sample
Category
Picked Up
Date
Time
-------
APPENDIX C
CALIBRATION CURVE RAW DATA
-------
3.400 3.533
322 MAX 1200
2.767
2.980
3.888
3.188
3.288
3.380
3.480
3.533
8
328 MAX 5480S
2.767
2.980
3.000
3.100
3.200
3.380 3.400 3.533
332 MAX 129806
0H
«
SY
Gl
G2
63
Z.767
3-AJG-95
220
0.000
0.000
0.0000
SPF 8.8
DTV 8.880
2.
SE
IT
I_T
DT
GR
ST
T • — • •— •-
900 3.
17:49:27
0
*Mc»a**Ma«
•ataiataiatak
0.000
0.01
» »j»j»-»"»»
~i — r~~r
080
OP
c
DI
DIV
IN
OR
R0
— i — 1---| — i — T— r—
3.100
T>f»
10
0.080
-0.041
0.00
0.00
-38.08
WTL
MCL
IQ
DM1
RE1
Rl
3.200
0.0500
1260
-5.00
0. 0080
75.00
-15.00
3.300 3
STEP
TH
MO
CGT
CG
R2
0.2588
158
-1.888
94.9
OFT
-55.88
i •
.488
PE
TT
FP
MU
DM3
RE3
R3
3.533
8. 88
8.75
-20.00
-3600.0
0QGtdCk
• OI0O0
85.80
-65.00
17:49:27
G2-37.5; DI —1.75; TT-. 75; CG-PR
320 257
322 259
328 263
268
-------
1 MIMI TCDD 11X5 C20 SHOT ZERO CflllBRflTTQrO JQ
SS 1 ES 176 BO e TO lie GR U*F SE 88
ni 2S7.ee re 259.ee MB 263.ee m 2&8.ee SR as TI 00:03:06
FI 32e.ee FZ 322.ee F3 328.ee F4 332.ee ER ee IN 73000
110"3 * > > &2 3 209 3 '-CjS -^^ MPX 1000
•^^^^N^
2.758 2.900 3.888 3.188 3.288 3.300 3.400 3.517
11B* 2.992 J/Y^*3.186 3.243 3.341 322 Mf* 1088
K/xJS/VtyA^Vu—vyWvWv' NT\\/yVV"\/A/v/A/-v/v—^vu-
2.75B 2.900 3.000 3. lee ' 3.200 ' ' 3.300 ' ' 3.400 3.517
328 MftX 37208
e
110-
2.758 2.900 3.000 3.100 3.200 3.388 3.400 3.517
332 MRX 86992
«»~l
*
SY
Gl
c^
4aC
G3
SPf
nrv
».7se
s-fllG-es
228
e. eee
0CWI
e.eeee
e.e
B.acw
2
1
SE
IT
I T
l_ 1
DT
GR
or
.900
17:54:13
e
e.eee
e.ei
«««,»«<0«
3.eec
OP
c
DI
I%TW
WAV
IN
OR
RB
5 3.1
T>P
ie
e.eee
— n A^e
e.ee
8.88
-3S.00
30
MTL
MO-
Tft
JLW
DM1
RE1
Rl
3. zee
0.0500
1260
— ^ cm
D. 1010
e.eeee
75.ee
-i5.ee
3
STEP
TH
MO
CGT
CG
R?
.300
0.2500
158
-1.000
40.6
OFF
-«^ nn
3.40e
PE
TT
FP
DM3
RE3
m
> 3.517
e.ee
e.75
-ze.ee
~^nr+ n
~JUUU. o
e. eeee
85.88
-A<; on
17'54'13
G2-37.5;DI—1.75;TT-.75;CG-flR
328 257
322 259
328 263
-------
flUGB318 1 MIMI TCDD IIXS C20 SHOT ZERO CflLIBRflTIONI ^
SS1 ES162 BO 0TO 118 GRUHNP SE 81
ni 257.ee M2 25s.ee MS 263.ee cvt 26e.ee SR ei TI ee:ez:5B
ri 32e.ee F2 322.ee FS 328.ee F4 332.ee ER ei IN see
2.707 . A 7*Y 320 mx ieee
) V-^-^/Ar>rYVA'S^^^
2.650 2.900
110:
2.650 2.800
110:
2.900
2.900
3.000
, /
3.000
3.100
A t,
( \* /
' G- r
f •>
3.100
3.200
c
^
1 t 1 — T
3.200
328
3.367
MAX 55400
'3.'367
332 MftX 127792
/\ / s* y -> ~3.&
2.650 2.800
3-AUG-eS 17:39:53
SY Z20 SE 0
GI 0.eee IT *X**XMC*
G2
0aaa i T m ».^-«, *-*••*
G3 e.eeee DT 0.000
SPF 0.0 GR 0.01
DTV 0.000 ST Jtatatotatotott
2.900
OP T>P
C 10
DI e.eee
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IN 0.00
OR 0.00
R0 -3H. en
/
3.000
MTL
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3.100
0.0500
1260
-s.ee
e.eeee
75.ee
^4 c CICI
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7^
3.200
0.2500
150
-1.000
105.6
OFF
— ^^ aa
PE
TT
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MU
DM3
RE3
DO
3.367
0.00
0.75
-20.ee
-3600.0
0.0000
85.00
—Cf nra
17:39:53
G2-37.5; DI—1.75; TT-.75;CG-flR
320 2S7
322 259
328 263
332 268
-------
Mini
TCDD 11x5 C20 SHOT ZERO CPLTBRQTTQN1
-10
SS
Ml
Fl
iio-q
257.ee
32e.ee
ES
M2
F2
172
259.ee
322.ee
2.938
BO
M3
F3
e
263.ee
328.ee
TO
M4
F4
lie
268.ee
332.ee
GR
SR
ER
86
86
2.769 2.938 A » /P.T3.223 3.321
v^--A/^^y^/v^^/^^
SE 86
TI 00:03:05
IN 1000
320. MPX ieee
3.300
3.400 3.517
322 MRX 1200
2.733
2.900
3.000
3.100
3.200
3.300
3.400 3.517
328 MPX 50406
2.733
110-1
2.900
3.000
3.100
3.200
*"**•/
3.300
3.400 3.517
332 MPX IIZS
2.733
3-PUG-85
SY 220 SE
GI e.eee IT
G3 0.0000 DT
SPF e.e GR
DTV e.eee ST
2.900
17:44:49
0
e.eee
e.ei
3.000
OP
c ie
DI e.eee
DIV -0.044
IN 0.00
OR 0.00
R0 JP« 00
3.100
3.200
3.300
3.400
3.517
MTL
MCL
IQ
DM1
RE1
Rl
0.0500
1260
-5.00
e.eeeo
75.ee
-is.ee
STEP
TH
MO
CGT
CG
R2
0.2500
150
-1.000
108.1
OFF
-55.00
G2-37.5; DI — 1.75; TT-. 75; CG-PR
320 257
322 259
328 263
268
PE 0.00
TT 0.75
FP -20.00
MU -3600.0
DM3 0.0000
RE3 85.00
R3 -65.00
17:44:49
-------
c&aa
Ml
Fl
10-,
1
257.00
320.00
ES
M2
F2
172
259.
322.
00
00
BO
M3
F3
0
263.00
328.00
•a
TO
M4
F4
nera
110
268.00
332.00
011
GR
SR
ER
•7
LNNP
86
86
SE 86
TI 00:02:59
IN 800
320 MAX 1000
; ^^-J^J\T^^
_ ^^^—-•^-^•^^^^••^••^^^^^^^^^••^^•^^^^•••••^^^^^^^^^•^^^•^^^••^^—^^•••••^^^^^^^-^^^^^^^^^^^•^^'•-•^••^^•••^••"qi^^^"^
3.T00
2.650
2.900
3.000
3.200
3.300 3.400
322 MAX 1200
3.300 3.400
332 MRX 109008
/
0H
*
SY
/"• 4
Gl
f+^*
GZ
G3
Sff
DTV
2.650
3-«JG-95
220
0O0O
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0.0000
0.0
0.000
SE
TT
1 1
1 T
L.I
DT
GR
ST
2.800
17:34:01
0
0.000
0.01
2.90
OP
C
DT
vx
IN
OR
R0
0 3.(
TT-P
10
0000
• ^JKJKJ
0.00
0.00
-36.00
900
MTL
MCL
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A^M
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Rl
3.100
0.0500
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—5 00
«/ • %M^
0.0000
75.00
-15.00
«
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1.200
0.2500
150
-1.000
8.1
OFF
-55.00
3.3
PE
TT
FP
MLJ
DM3
RE3
R3
130 3.400
0.00
0.75
-20.00
0.00O0
85.00
-65.00
17:34:01
G2-37. 5; DI— 1 . 75; TT- . 75; CG-flR
320 257
322 259
328 263
332 268
-------
1 MIMI _ TCDD 1 1X5 C2B SHOT ZERO CPLIBRflTION] _ IfJ
SS 1 ES 174 BO 8 TO 110 GR LNNP SE 87
ni 257.ee M2 259.00 MS 263.ee m 26e.ee SR 87 TI 00:33:05
Fl 32B.ee F2 322.ee F3 328.ee F4 332.00 ER 87 IN 89616
. Art %&^ 320 MRX l000
^H\fJ^JW^^^
7se 2. see 3.000 3.100 3.300 3.300 3.400 3.517
^L^A^v
2.750 2.900 3.000 3.100 3.200 3.300 3.400 3.517
110-1
0
328 MfiX 50886
2.750 2.900 3.000 3.100 3.200 3.300 3.400 3.517
H0-,
332 MRX 118000
2.750 2.900 3.000 3.100 3.200 3.300 3.400 3.517
3-«JG-e5 17:27:48 OP TVP MTL 0.0500 STEP 0.25OO PE O-OB
SY 220 SE 0 C 10 MCL 126O TH ISO TT O.75
GI e.eee IT ******* DI e.eee MO -1.000 FP -20.00
G2 e.eee LT *«»*»*« DIV -0.044 IQ -5.ee MU -3600.0
G3 0.0300 DT 0.000 IN O.Oe DM1 0.0000 CGT 97.4 DM3 0.0000
SPIF e.o GR e.oi OR e.oe REI 75.00 CG OFF RES 85.ee
DTV 0.000 sr ******* p0 -3e.ee RI -is.ee R2 -55.ee RS -es.ee
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APPENDIX D
BLANK RESPONSE DATA
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GR 0.81 OR
3 1 TiWJtviiJKTT* MO
3.
3.
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18
8.888
-8.842
8.88
8.88
-3e.ee
188 3.200
1 " * *,* 1 *
188 3.288
MTL 8.8588
MO. 1268
IQ -5.88
DM1 8.0888
RE1 75.00
Rl -15.ee
3.388 3.488 3.517
332 MAX 29284
?r
•••|»..»|T
3.388 3.408
STEP 8.2500 PE
TH 158 TT
MO -1.880 FP
3.517
0.00
0.75
-20.00
ML) -3600.0
CGT 105.6 DM3
CG OFT RES
R2 -55.ee R3
0.0000
85.80
-65.ee
19:80:32
G2-37.5; DI—1.75; TT-. 75; CG-PR
328 257
322 259
328 263
332 268
-------
DCflL 3 CFOR
CflLIBRflTION3
-IB
SS 1 ES
Ml 257.00 M2
Fl 320.00 F2
110-a
166 BO
259.00 M3
322.00 F3
0
263.00
328.00
TO
M4
F4
110
268.00
332.00
GR
SR
ER
LM*=»
63
63
0
A
SE 83
TI 00:02:59
IN 600
32B MflX
2.650
110-3
2.800 2.900 3.000 3.100 3.200 3.367
322 MRX 147232
2.650
2.800
3.200
3.367
332 MAX 32004
2.650
3-«JG-85
SY 220
Gl 0.000
G2 0.000
G3 0.0000
SPF 0.0
DTV 0.000
2.800
2.900
3.000
3.100
3.200
3.367
0.0500
1260
-5^00
0.0000
75.00
-15.00
STEP 0.2500
TH 150
MO -1.000
CGT
CG
R2
11.9
OFF
-55.80
PE 0.00
TT 0.75
FP -20.00
MU -3600.0
DM3 0.0000
RE3 85.00
R3 -65.00
18:54:57
G2-37.5; DI —1.75; TT-. 75; CG-flR
320 257
322 259
328 263
332 268
-------
fiUG0330
SS
Ml 257.
Fl 320.
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2.733
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3.000
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90
90
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IN
320 MRX
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322 MAX
800
133216
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3.517
139400
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ff
W-P— • • • • • • « ( • • • • 1 1 • • 1 p— i r— »— i , 1 1 , , , , , , , , , ,_
2.733 2.900 3.000 3.100 3.200 3.300 3.400
110-q
328
MPX
3.517
14002
2.733 2.900 3.000 3.100 3.200 3.300 3.400 3.517
110-]
332 mx 32004
2.733 2.900 3.000 3.100 3.200 3.300 3.400 3.517
3-flUG-e5 18:48:43 OP TKP . MTL 0.0500 STEP 0.2500 PE 0.00
SY 220 SE 0 C 10 MCL 1260 TH 150 TT 0.75
Gl 0.000 IT »»•«"•«.«« DI 0.000 MO -1.000 FP -20.00
G2 0.000 LT •»«•»»« DIV -0.044 IQ -5.00 MU -3600.0
G3 0.0000 DT 0.000 IN 0.00 DM1 0.0000 CGT 47.5 DM3 0.0000
SPF 0.0 GR 0.01 OR 0.00 R£l 75.00 CG OFF RE3 85.00
DTV 0.000 ST •»»•»•» R0 -38.00 Rl -15.00 R2 -55.00 R3 -65.00
18:48:43
G2-37.5; DI —1.75; TT-. 75; CG-fiR
1 320 257
322 259
328 263
332 268
-------
SS 1
Ml 257.80
Fl 320.00
2.658
2.658
18-3
•
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2.658
2.658
SV 228
/~? n cnci
laC 10. clDlo
G3 8.8000
SPF 0.0
DTV 0.000
ES 176
M2 259.00
F2 322.08
2.880
2.800
2.800
2.800
18:42:45
SE 0
TT itf **i»i*,,i-
1 T *-*-»»»-»»
DT 0.000
GR 8.81
ST <"*« '«.*.««
BO
«3
F3
2.988
2.988
* 1 *
2.988
2.988
OP
c
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L*XV
IN
OR
R8
8 TO 118
263.80 M4 268.88
328.80 F4 332.88
*!•
3.808 3.188
A**
3.888 3.188
.. A7f
3.888 3.188
A?**
3.880 3.188
TVF MTL 8.8588
10 MCL 1268
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8.88 DM1 0.8888
0.88 RE1 75.88
-38.88 Rl -15.88
GR LJ^P SE
SR 88 TI 82
ER 88 IN
320 f
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3.280 3.300
322 f
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3.200 3.300
STEP 0.2588 PE
TH 158 TT
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CGT 89.9 Dt13
CG OFF RES
R2 -55.80 R3
88
1:82:59
600
KX 26204
1 1 f T |
3.417
BX 28604
3.417
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3.417
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3.417
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8.75
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0.03QB
85.08
-65.80
18:42:45
G2-37.5; DI — 1.75; TT-. 75; CG-«R
320 257
322 259
328 263
332 268
-------
NEK QPLIBRQTION3
ss
Ml
Fl
1101
1
257.00
320.00
ES
M2
F2
162
259.00
322.00
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0
263.00
328.00
TO
M4
F4
110
268.
332.
n
00
00
GR
SR
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U***
81
81
SE 81
TI 00:02:58
IN 600
320 MRK 233
T
2.650 2.800 2.900 3.000 3.100 3.200 3.350
110^, . 322 MAX 25604
2.650 2.800 2.900 3.000 3.100 3.200 3.333
H0-. 328 MfiX 7401
2.650 2.800 2.900 3.000 3.100 3.200 3.350
H0-3 332 MRX 26204
0-
SY
Gl
G3
DTV
2.650 I
3-AUG-85 1
220 SE
0.000 IT
0.0000 DT
0.0 GR
0.000 ST
i '' i ' ' — r ' ' '
2.800 2.900
8:37:44 OP , TW
0 C '10
«u>.» »«•«•* DI 0.000
«. .» «. .a «i +•*, nrw _ci e\^d
0.000 IN 0.00
0.01 OR 0.00
3.00Q
MTL
MCL
TQ
DM1
RE1
Rl
3.
0.0500
1260
0.0000
75.00
-15.00
100
STEP
TH
MO
CGT
CG
R2
' *" l
3.20C
0.2500
150
-1.000
13.7
OFF
-55.00
9
PE
TT
FP
MU
DM3
RE3
R3
3.350
0.00
0.75
-20.00
-3600.0
0. CTomd
85.00
-65.00
18:37:44
G2-37.5; DI—1.75; TT-. 75; CG-flR
320 257
322 259
328 263
332 268
-------
P«tfP7 * MTMI DCflL 2 CFOR N^" CPL
SS^ 1 ES 176 BO
Ml 257.00 M2 259.00 M3
Fl 320.00 F2 322.00 F3
1107
«
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110-:
»[750 ^ 2.900 3.000
2.750 2.900 3.000
0 TO 110
263.00 M4 268.00
328.00 F4 332.00
/\JK
3.100 3.200
A* '*
3.100 3.200
IBRfiTIOm
GR LhTP SE
IM
88
SR 88 TI 00:03:06
ER 88 IN
320 rax
3.300 3.400
322 rax
Y
3.300 3.400
800
24804
3.517
25004
3.517
ll&l
328 nPX 7201
2.750
1101
2.900
3.000
3.100
3.200
3.300 3.400 3.517
332 MAX 27004
U;
SY
Gl
G2
G3
>.750
3-AUG-85
220
0.000
0.000
0.0000
SPF 0.0
DTV 0.000
2.900
SE
IT
l_y
DT
GR
ST
18:31:55
0
•n-t + ttt
«3»0«0»0«G«0«t
0.000
0.01
JO******
3.000 3.100
OP
C
DI
DIV
IN
OR
R0
THP
10
0.000
-0.042
0.00
0.00
-38.00
MTL
MCL
IQ
DM1
RE1
Rl
3.200
0.0500
1260
-5.00
0 • 0000
75.00
-15.00
3.
STEP
TH
MO
CCT
CG
R2
300
0.2500
150
-1.000
50.0
OFF
-55.00
3.400 3.517
PE
TT
FP
MU
DM3
RE3
R3
0.00
0.75
-20.00
-3600.0
0* 0000
85.00
-65.00
G2-37. 5; DI—1.75; TT". 75; CG-PR
320 257
322 259
328 263
268
18:31:55
-------
PUG0326 1
SS
Ml
Fl
1
257.88
328.88
MIMI
ES
M2
F2
164
259.88
322.88
BO
M3
F3
DCflL 1
8
263.88
328.88
CFOR
TO
M4
F4
NEU CflLTBRPTIONI
118
268.88
332.ee
GR
SR
ER
LM*»
82
82
SE
TI
IN
IM
82
80:82:59
648
llBn
v
328 MPX 7372
2.667 2.800 2.988 3.880 3.100 3.280 3.358
118-;
322 MfiX 7535
2.667 2.800 2.900 3.880 3.100 3.208 3.358
ne-
328 MAX 5887
2.667 2.888 2.988 3.888 3.188 3.288 ' 3.353
332 MRX 37Q17
>'•"?P
18
0aoot
. n
— 3UBB. 0
8.0000
85.00
-65.88
18:26:21
G2-37.5; DI—1.75; TT-. 75; CG-flR
328 257
322 259
328 263
332 268
-------
OLG
ss
Ml
Fl
1101
257.
320.
1
1
00
00
MIMI
ES
re
F2
164
259.00
322.00
BO
M3
F3
DCflL 1
0
263.00
328.00
CFOR
TO
M4
F4
NEW C«_IBRfiTIONl
110
268.00
332.00
/\
GR
SR
ER
LNNP
82
82
in
SC 82
TI 00:02:59
IN 724
320 MAX 7535
2.667 2.800 2.900 3.000 3.100 3.200 3.350
322 MAX 7859
2.667 2.800 2.900 3.000 3.100 3.200 3.350
110_ 328 MAX 5268
0-j
2.667
2.800
2.900
3.000
3.100
3.200
3.35C
110_j 332 MBX 35940
f\ • s~t
- 7 $3
0-
SY
Gl
G3
SflF
r\T\
'.667
3-flUG-e5
220
0.000
0.0000
0.0
r» nfif%
2.
1
SC
IT
DT
GR
CT
800
8:20:48
0
0.000
0.01
2.9C
OP
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DI
BTV
IN
OR
oa
90 3
TVP
10
0flW3l
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0.00
0.00
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1.000
MTL
MCL
TO
DM1
RC1
D1
3.1
0.0500
1260
—5 00
0.0000
75.00
-1^ on
00
STEP
TH
t^\
i *j
CGT
CG
t39
3.200 3.350
0.2500 PE 0.00
150 TT 0.75
MLJ -3600.0
56.8 DM3 0.0000
OFF RE3 85.00
-^c; on en -AS cva
18:20:48
G2-37.5; DI —1.75; TT-. 75; CG-fiR
320 257
322 259
328 263
332 268
-------
ftUG03g4
SS
m
Fl
1 MIMI
1 CS
257.80 «2
328.88 F2
152 BO
259.80 M3
322.08 F3
8 TO
263.00 M4
328.88 F4
118 GR
268.88 SR
332.88 ER
76
76 TI 80:82:57
76 IN 619
328 MPX 8859
2.658
2.888
2.988
3.888
3.188
3.288 3.283
322 MRX 7878
2.658
118-)
2.888
2.988
3.888
3.188
3.288 3.283
328 MPK 5534
2.658
1187,
2.888
2.988
3.888
3.188
3.288 3.283
332 MRX 37965
0-1
2.650
SY
Gl
G2
G3
SPF
DTV
3-AUG-65
228
0* 000
8.888
8.8000
0.8
8.880
S£
IT
LT
DT
GR
ST
* * I *
2.880
18:15:36
0
«•»•»
4010)010)010*
0.000
0.01
4ctataK*a|o*
OP
c
DI
DIV
IN
OR
R0
2.980
TVP
10
0. 088
-8.842
0.00
0.08
-36.00
1 * *
3.800
MTL
MCL
10
Dfll
RE1
Rl
0.0588
1268
-5.88
8.8888
75.08
-15.00
3.108
STEP
TH
MO
CGT
CG
R2
8.2500
158
-1.888
184.3
OFF
-55.88
* " ' "1
3.200 3.263
PE
TT
FP
ML)
0(13
RE3
R3
8. 88
8.75
-28.88
-3688.8
8.8888
85. DC
-65.88
G2-37.5;DI—1.75; TT-.75;CG-PR
328 257
322 259
328 263
268
18:15:36
-------
OUG0503 1
SS 1
Ml 257.80
Fl 320.00
110:
MTMT DCflL 1
ES
«2
F2
192
259.00
322.00
DO
«3
F3
C BEGINNING OF ^IFT CfiLIBRftTION OEOO IM
0
263.80
328.00
TO
H4
F4
110
268.00
332.80
GR
SR
ER
LNNP
96
96
SE
TI
IN
96
80:83:84
1488
320 MPK 9602
2.788 2.800
110-a
2.980
3.000
3.188
3.208
3.300 3.450
322 MPX 9802
Of ' • y. r .
2.700 2.800
2.988
3.888
3.188
3.
118l
3.388 3.458
328 MflX 9882
3.208
3.380 3.450
332 MAX 43208
2.700 2.800
5-PUG-85
SY 220 SE
61 0.808 IT
62 8.000 LT
63 0.0888 DT
SPF 8.8 GR
DTV 8.888 ST
2.908
22:44:53 OP
0
3.800
3.100
3.200
3.380
3.450
THP HTL 0.8500 STEP 0.2500 PE
8.88
10
8.888
-8.836
8.88
8.88
-38.88
MCL 1260 TH
MO
10 -5.88
DM1 8.8888 C6T
RC1 75.88 CG
Rl -15.88 R2
158
-1.
62-37.5; DI—1.75; TT-. 75; C6-flR
2S7
259
263
TT 0.75
FP -20.88
MU -3600.0
2.5 DM3 0.8880
OFF RE3 85.88
R3 -65.80
22:44:53
-------
ss
Ml
Fl
257.
320.
I
1
00
00
mm
ES
M2
F2
178
259.00
322.00
/
BO
M3
F3
\
PE sflMPL
0
263.00
328.00
£
TO
M4
F4
r ^
1563G8420S-XP
110 GR
268.00 SR
332.00 ER
i »
5.13g
LNNP
89
89
SE
TI «
IN
320
TM
89
ne;4c*:4c*
1800
MRX 19004
-1437.067
-1436.800
-1436.600
-1437.067
110-1
-1436.317
322 MRX 20004
-1436.800
-1436.600
-1437.067
110-j
-1437.067
S-flUG-85
-1436.317
328 MRX 43208
-1436.600
-1436.317
332 MRX
-1436.800
-1436.600
5V 220 SE
Gl 0.000 IT
G2 0.000 LT
G3 0.0000 DT
SPT 0.0 GR
DTV Q.000 ST
23:57:35 OP
0
TJ-P MTL 0.0500 STEP 0.2500 PE
10
0.000
-0.044
0.00
0.00
-38.00
MO. 1260 TH
MO
IQ -51gg
DM1 0.0000 CGT
RE1 75.00 CG
Rl -15.00 R2
-1436.317
0.00
G2-37.5;DI—1.75;TT-.75;CG-PR
320 257
322 259
328 263
150 TT 0.75
-1.000 FP -20.00
MU -3600.0
17.5 DM3 0.0000
OFF RE3 85.00
-55.00 R3 -65.00
23:57:35
-------
TCDD IIXS C20 SHOT ZERO CPLIBRflTIONl
-ID
SC 87
TI 00:03:06
IN 7601
320 WtX. 1000
3.400 3.517
MAX 1200
2.750
2.900
3.000
3.100
3.200
3.300
110H
3.400 3.517
328 MAX 51208
2.750
2.900
3.000
3.100
3.200
3.400 3.517
332 MAX 118992
0H
•
SY
Gl
G2
G3
'.750
3-«JG-85
220
0.000
0.000
0.0000
SAT 0.0
DTV 0.000
2.900
SE
IT
LT
DT
GR
ST
17:59:11
0
*******
*******
0.000
0.01
*******
3.000
OP
c
DI
DIV
IN
OR
R0
3.100
TI-P
10
0.000
-0.042
0.00
0.00
-38.00
MTL
MCL
IQ
DM1
RE1
Rl
3.200
0.0500
1260
-5.00
0.0000
75.00
-15.00
3.
STEP
TH
MO
CGT
CG
R2
T — • — • — •"
300
0.2500
150
-1.000
31.2
OFF
-55.00
3.400 3.517
PE
TT
FP
MU
DM3
RE3
R3
0.00
0.75
-20.00
-3600.0
0.0000
85.00
-65.00
G2-37.5; DI—1.75; TT-. 75; CG-PR
320 257
322 259
328 263
332 268
17:59:11
-------
APPENDIX E
SAMPLE ANALYSIS DATA
-------
ss
Ml
Fl
1
257.00
320.00
ES
M2
F2
176
259.00
322.00
BO
M3
F3
0
263.00
328.00
TO
M4
F4
110
268.00
332.00
GR
SR
ER
LNNP
88
88
SC
TI 80:
IN
. 320 MRX
88
83:16
1610
1225740
2.917 3.000
3.100
3.200
3.300
3.400
T
2.917 3.000"
3.100
3.500 3.667
322 MftX 1283614
3.200
3.300
3.400
T
2.917 3.000
3.100
3.500 3.667
328 MRX 74791
3.200
0-
3.300
r//-
3.400 3.500 3.667
332 MRX 39948
2.917 3.000
3.100
3.200
3.300
3.400
3.500
3.667
6-AUG-85
SY 220
Gl 0.000
G2 0.000
G3 0.0000
SPF 0.0
DTV 0.000
03:14:16
SC 0
XT *******
l_T *******
DT 0.000
GR 0.01
ST
OP
c
DI
DIV
IN
OR
R0
TT-P
10
0.000
-0.044
0.00
0.00
-38.00
MTL
MCL
0.0580
1260
10 -5.00
DM1 0.0000
RE1 75.80
Rl -15.08
STEP 0.2500
TH 150
MO -1.800
CGT
CG
R2
3.1
OFF
-55.00
G2-37.5; DI—1.75; TT-. 75; CG-flR
320 257
322 259
328 ' 263
332 268
PC 0.00
TT 0.75
FP -20.00
MU -3600.0
DM3 0.00GB
RE3 85.00
R3 -65.00
83:14:16
-------
w
e
«JG0605 1
SS
Ml
Fl
1
257.00
320.00
MIMI
ES
M2
F2
166
259.00
322.00
BO
M3
F3
SHIRCO SAMPLE: sws-3-**-
0
263.00
328.00
/•N
TO
M4
F4
110
268.00
332.00
GR
5R
ER
LNNP SE
83 TI 00:
83 IN
320 MAX
IM
83
03:09
1419
1326519
2.817 2.900
110T1
3.100
3.000
3.200
3.300
3.000
3.400 3.500
322 MAX 1362566
3.100
2.817
110-1
2.900
3.200
2.817 2.900
3.300 3.400 3.500
328 MAX 74979
3.000
3.100
3.200
3.300
3.400
332
3.500
3Z346
2.817 2.900
3.000
3.100
6-«JG-85
SY 220
Gl 0. 000
G2 0.000
G3 0.0000
Sff 0.0
DTV e.aae
03:04:01 OP
SE 0 C
IT ******* DI
LT ******* DIV
DT 0.000 IN
GR 0A OR
ST ***"*"«»* R0
10
0.000
-3.044
0.00
0.00
-38.00
MTL
M0_
3.200
0.0500
1260
IQ -5^00
DM1 0.0000
RE1 75.00
Rl -15.00
3.300
STEP 0.2500
TH 150
MO -1.000
CGT 10.6
CG OFF
R2 -55.00
3.400
3.530
G2-37.5; DI—1.75; TT-. 75; CG-«R
320 257
322 259
328 263
268
PE 0.00
TT 0.75
FP -20.00
MU -3600.0
DM3 0.0000
RE3 85.00
R3 -65.00
03:04:01
-------
1 MIMI
ss
Ml
Fl
1 E5
257.00 M2
320.00 F2
180 BO
259.00 M3
322.00 F3
SHIRCC
0 TO
263.00 M4
328.00 F4
0-
110 GR
268.00 SR
332.00 ER
3.434
IM
gr 90
90 TI 00:03:16
90 IN 2219
320 MAX 876
k.
r
u
r
2.917 3.000
3.100
3.200
1101
3.300 3.400 3.500 3.667
3.318 3.384 3.443 322 MRX 1038
2.917 3.000
3.100
3.200
3.300
3.400
2.917 3.000
3.100
110H
3.500 3.667
328 MfiX 36938
3.400 3.500 3.667
332 MAX 81399
I
I
I
I
I
I
I
2.917 3.000
6-«JG-e5
SY 220 SE
G2 0!000 LT
G3 0.0000 DT
SAT 0.0 GR
DTV 0.000 ST
3.100
02:41:16
0
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3.200
3.300
3.400
3.500
3.667
0.000
0.01
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C
DI
DIV
IN
OR
R0
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10
-0.044
0.00
0.00
-38.00
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MCL
IQ
DM1
RE1
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0.0500
1260
-5.00
0.0000
75.00
-15.00
STEP 0.2500
TH 150
MO -1.000
CGT
CG
R2
1.2
OFF
-55.00
G2-37.5;DI—1.75;TT-.75;CG-flR
32O 257
322 259
328 263
332 268
PE 0.00
TT 0.75
FP -20.00
MU -3600.0
Dt13 0.0OOO
RE3 85.00
R3 -65.00
02:41:16
-------
A*
1 HIHI _ SHIRCO SflfPLE LlHLi ft Xft
1 ES 180 BO 0 TO 110 GR LN*» SE 98
Ml 257.00 M2 259.00 K3 263.00 M4 268.00 SR 90 TI 00:03:16
Fl 320.00 F2 322.00 F3 326.00 F4 332.00 ER 90 IN 1600
H0-, A A A A I AA * 320 MftX 1000
LyWMyrwuwv^nAy^-*^^
2.900 3.000 3.100 3.200 3.300 ' 3.400 '• 3.500 3.600 3.683
116H . 3.187 3.36 3.504 322 MBX 1200
/^^^AAAA^^/V^/^
2.900 3.000 3.100 3.200 3.300 3.400 3.500 3.600 3.683
328 MAX 50600
2.900 3.000 3.100 3.200 3.300 3.400 3.500 3.600 3.683
110_
332 MAX 116592
O | ' • • •
2.900 3.
6-«JG-85
SY 220
Gl 0.000
62 0.000
G3 0.0000
SPF 0.0
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3.100 3
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0.000 IN
0.01 OR
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3.300 3.400
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MCL 1260 TH
MO
IQ -5.00
DM1 0.0000 CGT
RE1 75.00 CG
Rl -15.00 R2
3.500 3.600 3.683
0.2500 PE 0.00
150 TT 0.75
-1.000 FP -20.00
MU -3600.0
1.2 DM3 0.0003
OFF RES 85.00
-55.00 R3 -65.00
02:55:20
G2-37.5; DI — 1.75; TT-. 75; CG-flR
320 257
322 259
328 263
332 268
-------
12-61*40
00-29- Ea 00*22- Z&
00*28 E3d JJO 30
0000*0 EMC 2*1 13D
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00*21- Id 00'8£- 0d ******* IS 000-0 Aid
00*24 T3a 00*0 ao T0-0 af> 0-0 Jbs
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-------
ss i es
Ml 257.00 «2
Fl 320.00 F2
115 BO
259.00 M3
322.00 F3
3.
0 TO
263.00 M4
328.00 F4
110 GR
268.00 SR
332.00 ER
69
89
SE 69
TI 00:03:10
IN 1350
320 MAX 2854
3-285 3.329
2.917
110-
2.936
3.000 3.050 3.100 3.150
3.005 3-068
3.200 3.250 3.300 3.350
322 MAX 2263
— 3.265 3.321
2.917
3.000 3.050 3.100 3.150 3.200 3.250 3.300 3.358
328 MRX 4967
2.917
110-1
3.000 3.050 3.100 3.150 3.200 3.250 3.300 3.350
332 MAX 10199
2.917
3.000
3.058 3.108
3.158
SY
Gl
220 SE
0.080 IT
0.000 LT
G3 0.0000 DT
SPF 0.0 GR
DTV 0.000 ST
07:32:57 OP
0
3.288 3.258 3.300 3.350
0.00
TH3 MTL 0.8580 STEP 0.2580 PE
0.000
0.01
c
DI
DIV
IN
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1
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-8.045
0.00
0.80
-38.80
MO.
IQ
DM1
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MO
-5180
8.8888 CGT
75.80 CG
-15.80 R2
G2-37.5; DI—1.75; TT-. 75; CG-flR
320 257
322 259
328 263
332 268
158 TT 8.75
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MJ -3600.0
1.2 DM3 0.0880
OFF RES 85.88
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07:32:57
-------
APPENDIX F
QVQC DATA
-------
893
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2.1969715
-------
APPENDIX C
TECHNICAL WORK SCOPE FOR
THE ANALYTICAL PROGRAM PROVIDED TO
ROY F. WESTON BY ERT
1427J C3044
-------
A COMSAT COMPANY
ENVIRONMENTAL RESEARCH & TECHNOLOGY. INC.
69»; VIRGINIA ROAD CO'JCQRD MASSACHUSETTS 01742 USA (6!7) 369-8910 TELEX 923 325 ENVIRQRES CNCM CABLE
EAS-5242
ERT Document No. C-3044
July 17, 1985
Dr. Kay Jones
R.F. Weston
Weston Way
WestChester, PA 19380
Dear Dr. Jones:
This is to confirm our recent telephone conversation regarding
the analysis of samples from the recent field activities with Shirco
Infrared Systems at the Times Beach Dioxin Research facility.
Two test runs, designated as Runs 2 and 3, were conducted with
the unit firing contaminated soil. The following samples were
collected and submitted to Earl Hansen on 12 July, 1985:
Waste Feed
Run Designation
2
3
Samole Number
E-439
E-440
Hopper Ash
2
3
E-441
E-442
Fl-ue Gas
(Consisting of
particulate filter,
front half rinse,
XAD-2 resin and
condensate)
2a
2b
3a
Field Biased Blank
E-424 through E-427
E-428 through E-431
E-432 through E-435
E-436 through E-438
-------
Technical Specifications for Dioxin Analysis
Times Beach
Analytical Protocols
Sample preparation protocols for each of the two solid matrices
(waste feed, hopper ash) should be consistent with those presently
employed by R.F. Weston as part of the EPA sponsored dioxin soil analysis
program presently in progress at the Times Beach site. It is our under-
standing that these protocols represent an updated version of the EPA/CLP
dioxin protocol pertinent to the analyses of 2,3,7,8 TCDD in soil and
sediment samples tailored to the use of MS/MS technology.
^
Sample preparation protocols for the flue gas samples should be
consistent with those outlined in Sampling and Analysis Methods for
Hazardous Waste Incineration (first edition), February 1982 and employed
by Roy F. Weston during an earlier field demonstration program of dioxin
destruction using the J.M. Huber advanced electric reactor. The individual
components from the sampling trains (particulate filter, front half
rinse - 1:1 MC/AC, condensate and XAD-2 resin) will be combined in a
manner consistent with this protocol to provide a single sample extract
for each train. Actual GC/MS analyses of all sample extracts should be
conducted in accordance with the existing EPA protocol followed by R.F.
Weston at the Times Beach site.
It is our understanding that these analyses will be conducted using
an IIS/MS system fitted with a fused silica capillary column.
Results
Results for the flue gas extracts are to be provided in units of
total picograms (pg) per sample. The results from the solid samples
will be reported as parts per billion (ppb), in units of ng/g or ug/kg.
It is assumed that all reported data points will reflect method blank
corrected values. Results for all samples should be reported as both
total tetrachlorodibenzo dioxin isomers (TCDD) as well as 2,3,7,8 TCDD.
It is our further understanding that an absolute detection limit of
less than 10 pg will be achieved for 2,3,7,8 TCDD in each of the flue
gas samples. Detection limits of less than 0.25 ppb will be required
for both the hopper ash and soil or waste feed samples.
Quality Control Requirements
These again must be consistent with the QA/QC requirements of the
EPA sponsored dioxin analysis program presently in progress at the Times
Beach site. These should include, at a minimum, the use of method
blanks, laboratory performance check solutions, laboratory fortified
spike samples, laboratory replicates, instrument tuning and performance
reference materials and isotopically labeled surrogates and internal
standards in each and every sample.
-------
Dr. Kay
EAS-5242
Page Two
As discussed in our conversation, we will require the following
analyses:
o Gravimetric determinations for the collected
particulate samples from each test run.
o Volumetric determinations for the collected
condensate samples from each run.
o Dioxin analysis of duplicate samples of hopper
ash and waste feed from Runs 2 and 3.
o Dioxin analysis of the collected flue gas samples
from the field biased blank and Runs 2a and 3a.
We will authorize the analysis of the flue gas
samples from Run 2b only after receipt of prelim-
inary results for the other two samples.
Technical specifications to this program, including reporting
requirements and deliverables , are provided as an attachment to this
letter. These specifications also serve to confirm specific analytical
protocols and requisite detection limits, as discussed with yourself
and Dr. David Ben Hur.
We understand that the final data will be available by 2 August.
If we can provide any additional information in this regard, please
contact either myself or Gary Hunt at (617) 369-8910.
Sincerely,
^.o- v. \\\('( T.
Mark McCabe
Senior Scientist
Engineering and Analysis Staff
MM/sj
Enclosures
cc: K. Johansen, Shirco
R. Dunla ER1
-------
U S ENVIRONMENTAL PROTECTION AGENCY
Contract Laboratory Program
SAMPLE MANAGEMENT OFFICE
MEMORANDUM
» •
DATE: 3une 10, 1985
TO: Solicitation Community for SAS No. 1563-G
FROM: Roch A. Mongeon ^E^Vu—
Analytical Services Coordinator
THRU: Linda Haas Boynton
Analytical Services Group Leader
: SUBJECT: SAS No. 1563-G, Quail Run and Related Sites
I
Region VII has notified the Sample Management Office (SMO) that operational
• MS/MS analytical support for SAS No. 1563-G, Remedial Action at Quail Run and
I Related Dioxin Sites, is needed by 3uly 8, 1985. Attached are:
A. Definitions and Criteria for Laboratory Solicitation and Award
B. Major Administrative and Procedural Terms for inclusion in the SAS 1563-G
Specific Scope of Work (SOW).
' C. Terms of Contractor Default and Termination
I D. Government-Furnished Supplies and Services
E. June 1985 Draft, MS/MS Protocol, Region VII
j These attachments, along with the previously supplied SAS Standard SOW,
constitutes the solicitation package for this SAS. The major issues raised at the May
23rd Pre-Solicitation Meeting are addressed in this package and the terms stated herein
j are not negotiable. Please cajr fully r^vif ftLthe-iolicliatiqn Packf*ft^ *nrf submit your bids
' to the SMO no later tharffiOO p.m.. EST. on Thursday, June 13, 1985^ Bids received later
than this time will not be~considered. It is expected that bid results will be announced by
I Friday, 3une U, 1985. '
. cc: W. Keffer, Region VII
I R. Kleopfer, Region VII
C. Hensley, Region VII
J. Woods, Region VII
I M. Carter, HRSD
1 D. Thacker, SMO
-------
Attachment A
Solicitation: SAS No. 1563-G - Quail Run
Definitions and Criteria for Laboratory Solicitation and Award
1. Solicitation Community
Those laboratories with an identified GC/MS/MS capability and appropriate
backup capabilities that can be located and operational within two hours
driving distance of the Quail Run Dioxin Site (Grey Summit, MO).
2. Competitive Community
The community shall consist of either the following (a) or (b), as appropriate:
(a) At least three CLP laboratories which have submitted responsive bids.
All non-CLP bidders shall be considered nonresponsive.
OR
In the event that fewer than three CLP laboratories submit qualified
bids:
(b) Bids from all solicited laboratories (CLP and non-CLP) shall be consi-
dered and evaluated for award.
3. BidD* iline
Firm, xed per-sample price bids must be submitted to SMO by 5:00 p.m. EST
on Thursday, June 13, 1985.
-------
Attachment B
Solicitation: SAS No. 1563-G — Quail Run
Major Administrative and Procedural Terms for Inclusion in
SAS No. 1563-G. Specific Scope of Work
1. Type of Contract; Indefinite Quantity and Funding
This is a firm, fixed per-sample price, indefinite quantity contract for
supplies or services specified in the SAS No. 1563-G contract, with penalties
for late delivery of data.
2. Project Scale - Government's Minimum Obligation
The minimum services the Government is obligated to purchase under this
contract will be equivalent to the per-sample price bid by the contractor
times 70, or $ , ..
The term of this contract is 70 consecutive days, beginning on the first day
that samples are received (not including samples received under the pre-
award validation option). See Attachment A, item 5.
Region VII anticipates taking at least 700 samples within 70 days. The
Region also indicates that the total demand could reach 2,500 total samples
within this timeframe.
3. Sample Delivery to Laboratory
Samples may be delivered to and must be accepted by the laboratory at any
time between 6:00 a.m. and 6:00 p.m., Monday - Saturday, during the term of
this contract. A minimum of 0, to a maximum of 50 samples per day will be
delivered to and accepted by the laboratory for analysis.
it. Data Turnaround
(a) Primary Data Turnaround; Primary data (consisting of items 1 - 17, 21)
section XIV, Data Reporting of the Dune Draft Protocol) by EPA Sample
No., for each sample received before 12;00 p.m. (noon) on any one day
is due by 6:00 a.m. on the following day at Tfte designated receipt point.
Primary data for samples received after 12:00 p.m. (noon) on any one
day is due by 6:00 a.m. on the second^ calendar day thereafter.
(Exception: preliminary hardcopy data for all samples received at
laboratory on zTSaturdav are due by 6:00 a.m. on the following Monday.)
(b) Secondary Data Turnaround; Secondary hardcopy data, consistent with
item 18. of Section XIV of the 3une Draft Protocol are due seven (7)
days from the original primary hardcopy data due date.
-------
-2-
The Pre-Award Validation Analysis must be completed on the same
GC/MS/MS instrument(s) and on the same GC/MS/MS or LRMS instrument(s)
and data production system that will be used as the primary and secondary*/^'*"/
(backup) instruments at the on-site facility (should the laboratory be awarded^'***;
SAS No. 1563-G).
During performance of the Pre-Award Validation Analysis, laboratories shall 0
be granted two attempts (within a single period of 15 days) to meet the
QA/QC and data turnaround requirements of this SAS. Upon failing the
second attempt to meet these requirements, laboratory shall be considered
not qualified for award for this SAS, and the second lowest bidder will then
be considered for the award.
6. On-Site and Operational Due Dates
Laboratory must be on-site and operational (i.e., capable of performing
according to all technical and administrative terms of the SAS No. 1563-G
contract) within 15 days of notification of award from SMO.
-------
Attachment C
Solicitation: SAS No. 1563-G — Quail Run
Terms of Contractor Default and Termination
Bidders are hereby notified that, for the purposes of this contract, any or all of the
following shall constitute default:
1. Failure to maintain a capability to perform the required number of analyses
according to the SOW for the SAS No. 1563-G contract.
2. Failure to meet delivery, and documentation requirements.
3. Failure to meet the minimum QA/QC criteria required by the SAS No. 1563-
. C contract.
These conditions will endanger performance of the contract in accordance with its
terms. Therefore, if such conditions persist beyond the limits established in
Schedules 1. and 2. below, the contract may be terminated for default.
Schedules
1. Failure to analyze the required sample load of up. to fifty (50) samples per
day and the deliverable submitted within the time specified by the contract
on:
(a) Twenty percent (20%) or more of total sample receipts at any time
during the term of this contract, or
(b) Two or more consecutive batches of samples for analysis.
2. Failure to meet the minimum analytical quality control (QC), instrument
tuning and calibration, detection limit, and reporting requirements of the
analytical protocol for this contract on:
(a) Greater than or equal to 20% or more of the total sample receipts at
any time during the term of this contract, or
(b) On two (2) or more consecutive batches of samples for analysis.
-------
Attachment D
Solicitation: SAS No. 1563-G — Quail Run
Government-Furnished Supplies and Services
1. Samples for Analysis — Consisting of 30 - 300 g portions of soil or
vegetation in individual collection containers.
2. For the purposes of electronic submission of primary data, the EPA will
provide a portable IBM-XT personal computer.
3. EPA is currently negotiating for a location to make available to the labortory
contracted for services under SAS No. 1563-G that will meet the geo-
graphical constraints of the contract.
Note however, that there is not currently such a site available (i.e., supplied
by EPA) and that labortory should consider it their responsibility to provide
themselves with a site within two hours drive of the Quail Run site in Grey
Summit, Missouri.
-------
-2-
5. Point of Data Delivery
Primary data will be delivered via electronic submission to the Region VII /
Laboratory in Kansas City, Kansas. /
5. Adjustment/Penalty Schedule
(a) Primary Hardcopy Data; Two percent (2%) of the SAS per-sample bid
price for each hour late.
At the end of 50 hours, one-hundred percent (100%) of the SAS per-
sample price will be withheld. At the end of the 24th hour after the
time that primary hardcoov data is due, forty-eight percent (48%) jaf
the SAS per-sample price will be withheld and the Region shall cease
sending samples to the laboratory to conduct an on-site^ audit of the
facility to determine the cause for late data delivery. Once the cause
for the late data is remedied, the Region shall resume sending samples
for analysis to the laboratory. If late data delivery is not remedied,
this contract may be terminated. See Attachment C.
(b) Secondary Hardcopy Data; Two percent (2%) of the SAS per-sample bid
price for each day late.
(c) Example of Penalty Assessment
Following Is an example of assessment of penalties based on primary
and secondary late data penalty schedules.
Per-Sample Price $100.00
Sample A Primary Data: Two Hours Late
Sample A Secondary Data: Two Days Late
o Late Primary Data Penalty assessment at two percent (2%) per hour
late.
$100.00 X .02 X 2 Hours = $4.00 Penalty
o Late Secondary Data Penalty assessment at two percent (2%) per
day late, based on SAS per-sample price:
$100.00 X .02 X 2 Days = $4.00 Penalty
o Amount of per-sample price due laboratory, after adjustments for
primary and secondary late data penalties:
$100.00 - $8.00 = $92.00 Due to Laboratory
-------
-3-
6. Instrumentation
GC/MS/MS is the required primary instrumentation for supplying services for
SAS No. 1563-G. In the event of failure of the primary GC/MS/MS
instrument(s), backup instrumentation (either GC/MS/MS or LRMS) must be
available to supply a continuum of analytical support in full compliance with
all terms of the SAS No. 1563-G contract.
Note that LRMS does not constitute an acceptable long-term substitute for
GC/MS/MS for provision of services under this SAS. LRMS may only be used
as a backup when primary instrumentation has failed, as defined below, for no
7 longer than^wo days of laboratory analysis in a row, and/or for no more than
twenty percent (20%) of the total sample receipts at any time during the
term of this contract.
GC/MS/MS Failure
GC/MS/MS failure is defined as malfunction of the instrument which prevents
consistent compliance with any or all of the QA/QC requirements of the
analytical protocol.
'A>«v // »»>^« «>^ *t r&*^f*e.e. tobLA
IS jt^st+H+£j &J 7^>»ff or/rHajLj ^t
-------
JUNO 5 198
RAPID DETERMINATION OF TCDD IN SOIL AND SEDIMENT
USING GAS CHROMATOGRAPHY AND TANDEM MASS SPECTROMETRY
June 1985
U. S. ENVIRONMENTAL PROTECTION AGENCY
REGION VII
-------
JUNO 5 198!
TABLE OF CONTENTS
~~" ~ ^
Page
I. SCOPE AND APPLICATION 1
i
II. SUMMARY 1
III. INTERFERENCES 2
•
IV. SAFETY 2
V. APPARATUS AND MATERIALS 4
VI. REAGENTS 5
VII. CALIBRATION 7
VIII. QUALITY CONTROL REQUIREMENTS 11
IX. SAMPLE COLLECTION, PRESERVATION, AND HANDLING 13
X. SAMPLE EXTRACTION 14
XI. CLEANUP .'. 15
XII. GC/MS/MS ANALYSIS 17
XIII. METHOD PERFORMANCE 19
XIV. DATA REPORTING 22
-------
I. SCOPE AND APPLICATION JfN 05 1985
This method 1s for use In the rapid determination of 2,3,7,8-Tetrachloro-
d1benzo-p-d1ox1n (2,3.7,8-TCDD) In soil and sediment, when 2,3,7,8-TCDD 1s
known to be the principal or only tetrachlorod1benzod1ox1n Isomer present.
The method Is not specific for the 2,3,7.8-TCDO Isomer, unless a capillary
column which separates that Isomer from the other 21 TCOO 1 sowers Is employed.
The method Is applicable 1n the concentration range of 0.3-25 ug/kg.
The method employs a tandem quadrupole mass spectrometer (MS/MS) as the
final detector. The specificity of detection Inherent In such a system
significantly reduces the need for sample cleanup. This, 1n turn, Improves
productivity and cost-effectiveness relative to other high resolution and low
resolution GC/HS analysis techniques. The apparatus and methods described
are designed for use in a mobile laboratory, which permits on-slte analyses.
•
The method 1s Intended to be used when analytical results are required
rapidly, such as when site cleanup operations are 1n progress. Since the
method is not isomer specific, false positives, Including isomers other than
2,3,7,8-TCDD, may occur. But errors in this regard would be on the side of
safety. Emphasis in the method 1s placed on avoiding false negatives, as
this is a more critical consideration when public health is to be protected.
This method 1s restricted to use only by or under the supervision of
analysts experienced in the use of gas chromatography/triple quadrupole mass
spectrometers and skilled in the interpretation of mass spectra.
Because of the extreme ';oxicity of this compound, the analyst must
prevent exposure to himself, or to others, by materials known or believed to
contain 2,3,7,8-TCOD. Section IV of tnis method contains guidelines and
protocols that serve as minimum safe-handling standards in a limited access
laboratory.
Analyte CAS Number
2,3.7,8-TCOO 1746-01-6
II. SUMMARY OF METHOD
Five (5) grams of anhydrous sodium sulfate 1s placed 1n a 10 ml serum
vial and the vial with cap and septum is weighed. Approximately 5 grams of a
soil sample is added and the vial is re-weighed. The sample is spiked with
internal and surrogate standards of Isotopically labelled 2,3,7,8-TCOD. The
sample is mixed by shaking, and extracted with acetonitrile/dichloromethane
in the closed vial. An aliquot of the extract 1s taken and, after separation
from acetonitrile, the dichloromethane is used directly for GC/MS/MS analysis.
Clean-up should usually not be necessary, but a clean-up procedure is included
for those samples which do not meet quality assurance criteria. Concentration
of the extract may be done to lower the minimum detectable concentration.
Capillary column GC/MS/MS conditions are described which allow for separation
of TCDO from the bulk sample matrix and measurement of TCDD 1n the extract.
-------
Quantification Is based on the response of native TCOO relative to the isotopic^
labelled TCOD Internal standard. Performance Is assessed based on the results fi
surrogate standard recoveries, EPA performance evaluation samples, spike recover
tests, and method and field blanks.
III. INTERFERENCES
, Method Interferences may be caused by contaminants In solvents, reagents,
glassware and other sample processing hardware that lead to discrete artifacts
and/or elevated backgrounds at the Ions monitored. All of these materials
must be routinely demonstrated to be free from Interferences under the
cpnditions of the analysis by running laboratory method blanks as described
In Section VIII.
The use of high purity reagents and solvents helps to minimize interference
problems. Purification of solvents by distillation In all-glass systems may
be required.
Matrix interferences may be caused by contaminants that are co-extracted
from the sample. The extent of matrix Interferences will vary considerably
from source to source, depending upon the nature and diversity of the sample.
2,3,7,8-TCDD is often associated with other interfering chlorinated compounds
which are at concentrations several magnitudes higher than that of 2,3,7,8-TCDD.
The use of a triple quadrupole mass spectrometer as the detector serves
to minimize the influence of many of these Interferents.
IV. SAFETY
The following safety practices are excerpted directly from EPA Method
613, Section 4 (July 1982 version): See following page.
-------
• 4 4.« ,w*rvnf (X
••eh njagent used in this method he
not been precisely defined; however.
••ch chemical compound should be
treated •• • potential health hazard.
From this viewpoint. eiposur* to these
Chemicals mult b« reduced to the
lowest possible level by whatever
me»ns available. The laboratory •
responsible for maintaining • current
awareness M« of OSHA regulations
regarding the safe handling of the
chemicals specified in this method. A
rtft.
Benzene and 2.3.7.8-TCDD have been
identified as suspected human or
mammalian carcinogens.
4.2 Each laboratory must develop a
strict safety program for handling of
2.3.7.8 TCDO. The following labora-
tory practices are recommended:
4.2.1 Contamination of the labora-
tory will be minimn ad by conducting alt
manipulations in a hood.
4.2.2 The' effluents of sample
splitters fo> the gss chiometograph end
toughing pumps on the GC/MS should
pass through either a column of
activated charcoal or be bubbled
through a trap containing oil Of high-
boding alcohols.
4.2, J Liquid waste should be
dissolved in methanol or ethanol and
irrad>ated with ultraviolet light with
wavelength greater than 290 nm for •
several days. (Use f 40 81 lamps or
equivalent.) Analyze liquid wastes and
dispose of the solutions when
2.3.7.8-TCDD can no longer be
detected.
4.3 Dow Chemical U S A has issued
the following precautions (revised
11/78) for safe handling of
2.3.7.8-TCDO in the laboratory:
4. J. f The following statements on
safe handling are as complete as
possible on the bens of available
toiico'og-cal information. The
precautions for safe handling and uee
are necessarily general in nature smce
detailed, specific recommendations can
be made only for the particular eiposure
and circumstances of each individual
use. Inquiries about specific operations
or uses may be addressed to the Dow
Chtrmcai Company Assistance •»
evaluating the health hazards of
particular plant conditions may be
obtained from cenem consurt*o
labo»atones and from State Depart-
ments of Health or of Labor, many of
which have an industrial health service.
2.3.7.8 TCDD « extremely lo«iC to
f'Mj
0 5 /g
laboratory animals. However, rt has
b«tn handled for years without injury In
enalyt
-------
V. APPARATUS AND MATERIALS
All glassware Is Initially cleaned with aqueous detergent and then rinsed
with tap water, delonlzed water, acetone, toluene and methylene chloride.
Other cleaning procedures may be used as long as acceptable method blanks are
obtained.
•
Electronic balance, capable of weighing at least 50 g, with an accuracy
of at least +. O.OS g.
Shaker, vortex-type or equivalent
Centrifuge, 4UOO rpm, capable of handling 25 mm diameter vials
Centrifuge tubes
1U ml serum vials; with teflon faced septa and aluminum caps (Chrompak
•10204 and 10213 or equivalent)
1 ml serum vials; with teflon faced septa and aluminum caps (Chrompak .
10201 and 10211 or equivalent)
Crimper for 10 ml serum vial (Chrompak 10233 or equivalent)
Crimper.for 1 ml serum vial (Chrompak 10231 or equivalent)
Disposable teflon 0.45 micron filters (Millipore.SLHV025 HB, or equivalent
5 ml disposable Glaspak syringes (Sargent Welch S-79401-B or equivalent)
18 gauge disposable syringe needle (Sargent Welch S-79402-G or equivalent)
Disposable pipets, 5 3/4 inches x 7 mm o.d.
Glass wool, silanized
Nitrogen blowdown apparatus
Gas chromatograph - an analytical system with all required accessories
including syringes and analytical columns. The injection port must be designed
for capillary columns and splUless Injection.
Triple quadrupole mass spectrometer with GC transfer line and glow
discharge ion source (TAGA* 6000, SCIEX®, Thornhill, Ontario. Canada)
Compressed Gases: Zero Grade Air (from distillation, not water
hydrolysis)
Ultra High Purity Nitrogen
Ultra High Purity Argon
Column: 15 m long, wide bore fused silica capillary (eg. U.32
mm I.D.)
DB-5 1.0 micron film thickness.
-------
JUNO 5 ijt
VI. REAGENTS
Stock Standard Solutions^
Stock standard solutions correspond to three toluene solutions containing
unlabelled 2,3,7.8-TCOD at varying concentrations, and iJCi2-2,3,7,8-TCDD
(Internal standard, CASEIN 80494-19-5) at a constant concentration. These
Solutions also contain 37Cld-2,3.7,8-TCDD (surrogate compound, CASRN 85508-
50-5) at varying concentrations. These stock solutions are to be used 1n
preparing the calibration standard solutions, and are to be obtained from the
Quality Assurance Division, USEPA, Environmental Monitoring Systems Laboratory
(EMSL-LV), Las Vegas, Nevada. If not available from EMSL-LV, stock standard
solutions may be prepared from commercially available standards. However,
'the accuracy of these solutions must be checked against EPA supplied standard
solutions.
The three stock solutions Mill have the following concentrations of
unlabelled, Internal and surrogate standards.
Stock Solution II (CC1)
Uqlabeled 2,3,7,8-TCDO - 0.2 ng/ul
J;Cl2-2,3,7,8-TCDD - 1.0 ng/ul
37CTj-2,3.7.8-TCDO - 0.06 ng/ul
Stock Solution 12 (CC2)
Uqlabeled 2,3,7,8-TCOO - 1.0 ng/ul
i;Ci2-2.3,7,8-TCDO - 1.0 ng/ul
37CTj-2.3,7,8-TCDD - 0.12 ng/ul
Stock Solution 13 (CCS)
Uqlabeled 2,3,7,8-TCDD - 5.0 ng/ul
"C12-2.3.7.8-TCDD - 1.0 ng/ul
37CtJ-2,3,7,8-TCOD - 0.2 ng/ul
NOTE: Store stock solutions In 1 ml amber m1ni-v1als under refrigeration.
Calibration Standard Solutions
Calibration standard solutions are prepared to simulate the conditions
of sample analysis as nearly as possible. Three calibration standard solutions
are prepared from the stock standard solutions so as to contain constant
amounts of Internal standard (5 ug/kg equivalent) with variable amounts of
unlabeled standard (1,5, and 25 ug/kg equivalent) and surrogate standard
(0.3, 0.6, and 1.0 ug/kg equivalent). The equivalent concentrations are
based on the use of 5-gram samples, extraction with 5 ml of 2:1 acetonitrile:
dichloromethane. and a final extract volume of approximately 1.66 ml dichloro-
methane after removal of acetonitrile, as called for 1n the procedure.
-------
UN 05 198
Low Level
Add 75 ul of stock solution fl to a 5 ml volumetric flask and bring to
volume-with dlchloromethane. Mix well. This solution-contains an equivalent
concentration of 1 ug/kg of 2,3,7.8-TCDD, 5 ug/kg of 13C12-2,3.7.8-TCDD, and 0.3
ug/kg of 37Cl4-2,3,7,8-TCDD.
Medium Level
< Add 75 ul of stock solution 12 to a 5 ml volumetric flask and bring to
volume with dlchloromethane. Mix well. This solution-contains an equivalent
concentration of 5 ug/kg of 2.3.7,8-TCDD, 5 ug/kg of 1JC12-2,3,7,8-TCDD, and 0.6
ug/kg of 37C14-2,3,7,B-TCDD.
«
High Level
Add 75 ul of stock solution 13 to a 5 ml volumetric flask and bring to
volume with dichloromethane. Mix well. This solution contains an equivalent
concentration of 25 ug/kg of 2,3.7,8-TCDD, 5 ug/kg of 1<3C12-2,3,7,8-TCDD, and 1.
ug/kg of 37Cl4-2,3,7.8-TCDD.
NOTE 1: Although the surrogate. 37Cl4-2,3,7,8-TCDD, is present in all thre
level calibration solutions, only the high level solution is used for calculatin
the relative response factor for the surrogate.
NOTE 2: All calibration standard solutions must be stored in an Isolated
refrigerator and protected from light. Check these standard solutions frequen
for signs of evaporation.
Sample Spiking Solution
The sample spiking solution 1s also to be obtained from the Quality
Assurance Division, U. S. EPA Environmental Monitoring Systems Laboratory
(EMSL-LV), Las Vegas. Nevada. The spiking solution will have the following
concentrations of internal and surrogate standards.
HC12-2.3.7.8-TCOD - 0.5 ng/ul
37CTi-2,3.7,8-TCDO - 0.1 ng/ul
When 50 ul of this solution is spiked in 5 g of soil, the resulting
concentrations in the soil are 5 ug/kg and 1 ug/kg of internal and surrogate
standard, respectively.
It is recommended that approximately 2.5-5 ml of the spiking solution be
transferred to a 5 ml serum vial and sealed with a septum and cap prior to
each day's work for use In spiking samples that day.
NOTE: It is very Important that no evaporation of sample spiking solution
be allowed to occur, since the accuracy of results are directly dependent on
the addition of a known amount of internal standard.
-------
Field Blank Spiking Solution
The field blan* spiking solution 1s also to be obtained from the Quality
Assurance Division, U. S. EPA, Environmental Monitoring Systems Laboratory
(EMSL-LV), Las Vegas, Nevada. The spiking solution will have the following
concentrations of unlabelled, Internal, and surrogate standards:
2«3,7,8-TCDD - 0.1 ng/ul
"c12-2,3.7,8-TCDD - 0.5 ng/ul
37CTj-2,3,7,8-TCDO - 0.1 ng/ul
When 50 ul of this solution 1s spiked 1n 5 grams of soil, the resulting
concentrations 1n the soil are 5 ug/kg of Internal standard and 1 ug/kg each
of unlabelled and surrogate standard.
NOTE: It 1s very Important that no evaporation of field blank spiking
solution be allowed to occur, since the accuracy of results are directly
dependent on the addition of a known amount of internal standard.
Sol vent
All solvents should be pesticide grade or equivalent. The following
solvents will be needed:
Acetonitrile
Dichloromethane
Cyclohexane
Toluene
Benzene
Methanol
Silica Gel
Type 60, 70-230 mesh. Soxhlet extracted with dichloromethane for 24 hours,
then activated for 24 hours at 130°C.
Acid Alumina
AG 4, 100-200 mesh, soxhlet extracted with dichloromethane for 24 hours,
then activated for 24 hours at 190°C.
Carbopack C
CelUe S4S
Sodium Sulfate
(ACS) granular, anhydrous.
VII. CALIBRATION AND LIMIT OF DETECTION DETERMINATIONS
Calibration must be done using the Internal standard technique. In this
case, the internal standard 1s an Isotope of the compound-of-Interest, and
-------
therefore, the technique 1s also referred to as 1sotope-d11ut1on-mass spectro-
metry. The three calibration standard solutions described In section VI are
required.
Inject 1-2 ul of each of the calibration standard solutions and acquire
selected reaction monitoring data for the following parent- daughter tons:
m/z « 320 *257
m/z » 322 -*259
m/i - 328 ->263
m/z « 332 ^268
t
For simplicity in subsequent sections, we will refer only to the daughter
Ions, since quantltatlon 1s based on daughter Ion response.
Relative response factors for unlabelled 2,3,7,8-TCDD vs the Internal
standard for triplicate determinations of each of the three calibration
standard solutions are calculated.
Equation I: Relative Response Factor (RRFs) for 2,3,7,8-TCDD
RRFs - (AsCis)/(AisCs')
where As * the sum of the area responses for the ions, m/z 257 and 259,
corresponding to the unlabelled standard, 2,3,7,8-TCDD.
AJS « the area response of,the ion m/z 268, corresponding to the
. internal standard, i<5C12-2,3,7,8-TCDD.
Cs « the concentration of the unlabelled standard, 2,3,7,8-TCDD
CjS « the concentration of the Internal standard, ^C12*2,3,7,8-TCDD.
In the case of the unlabelled 2,3,7,8-TCDD each of the calibration
standard solutions must be analyzed in triplicate, and the variation of the
RRF values for each compound at each concentration level must not exceed 101
RSD. If the three mean RRF values for each compound do not differ by more
than +_ 10%, the RRF can be considered to be independent of analyte quantity
for the calibration concentration range, and the mean of the three mean RRFs
shall be used for concentration calculations. The overall mean is termed a
calibration factor.
Similarly, relative response factors for the surrogate standard vs the
internal standard for the triplicate determinations of the high level calibration
solution are also calculated.
Equation II; Relative Response Factor (RRFSS) for 37Cl4-2,3,7,8-TCDD
RRFS$ - (A$$C1$)/(A1$C$S)
where Ass • the area response of the.daughter ion, m/z 263, corresponding to
the surrogate standard, <3/Cl4-2,3,7,8-TCDD.*
* Subtract 0.0108 of any 257 response from the 263 response to correct for
contributions of 2,3,7,8-TCDD to the 263 response.
-------
l'rf 05 IS
i of.the 1on m/z 268, <
I. l3C12-2.3,7,8-TCOO.
- the area response othe 1on m/z 268, corresponding to the
Internal standard,
Css « the concentration of the surrogate standard, 3 014-2,3,7,8-TCDD.
and Cjs « the concentration of the Internal standard, Ci2-2,3,7,8-TCDO.
In the case of the surrogate standard, 37Cl4-2,3,7,8-TCDD, the variation
of the three RRF values for the high level calibration solution should not
exceed 101 RSO. If this 1s the case, the mean of the three RRFs shall be
used for concentration calculations. The overall mean Is termed a calibration
factor.
The calibration factor for the unlabelled 2,3,7,8-TCDD must be verified on
each work shift of 8 hours or less by the analysis of a low level calibration
standard. If the RRF for the low level calibration differs from the calibration
factor by more than 101, the entire calibration must be repeated and a new
calibration factor determined. The most recently verified calibration factor
must be used in all calculations. This verification Is only required for the
unlabelled standards. There 1s no need to check the surrogate calibration
factor unless the surrogate recoveries appear biased or consistently fall outside
the 60-140% control limits.
The theoretical ratio of the m/z 257 to 259 ions for native 2,3,7.8-TCDD
is 1.02. However, in practice this ratio will differ from the theoretical due
to the very low resolution used in both analyzing quadrupoles for this type of
analysis. The'ratio must therefore, be determined empirically as follows:
Equation Hit (Ratio of native TCDO daughter Ions)
Ratio • A257/A259
where *2S7 * Area response for ion m/z 257
A259 * Area response for ion m/z 259
The mean of the ratios calculated for each of the nine calibration
solutions is used for comparison purposes for qualitative identification of
2,3.7,8-TCDO.
It has been found that the sample spiking solution also gives responses
for the 257 and 259 daughter ions corresponding to 2,3,7,8-TCDD. These
contributions must be subtracted out for each sample. In order to determine
this correction factor, add 150 ul of the sample spiking solution to a 5 ml
volumetric flask and bring to volume with dlchloromethane. Twenty 1-2 ul
Injections of this solution must be made and the ratio of the area responses
for the sum of the m/z 257 and 259 Ions vs the m/z 268 1on must be calculated.
Twenty separate ratios must be determined.
-------
-'"" 05 i98.
Equation IV: Blank Response (B) of Sample Spiking Solution
B »Ab/A1s
>
where Ab • the sum of the area responses for the Ions, m/z 257 and 259,
obtained with the spiking solution
and AfS « The area response of the 1on m/z 268, corresponding to the
Internal standard l
-------
W « 5 grams (the weight of Met soil used for each sample)
The standard deviation of the blank responses (1n concentration units)
must then be calculated.
Equation VII; (Standard Deviation of The Blank Responses)
1 SD • (r Cb2) - (I Cb)2/n
n-1
' where Sb • standard deviation of the blank responses (In units of ug/kg)
Cb • blank response 1n concentration units (calculated using
Equation VI)
n « number of replicate blank results used (20 are required)
Finally, the limit of detection must be calculated from the standard
deviation of the blank.
Equation VIII; {Limit of Detection Based on "Well-Known" Blank)*
LOO « 2 t Sb
where LOD « Limit of Detection
t • the 10% point of the t statistic for a double-sided table
with n-1 degrees of freedom (where n 1s equal to the number
of blank results used). NOTE: The LOD must be calculated
based on at least 20 replicate blank (I.e. spiking solution)
analyses. For n « 20, t • 1.72.
The limit of detection calculated from equation VIII should be less than
the required limit of detection of 0.3 ug/kg.
VIII. QUALITY CONTROL REQUIREMENTS
The following quality control (Q.C.) requirements are listed In the
order that they must be run. Requirements 1 and 2 are to be run Initially
before any other samples. Requirements 3 through 7 are the Q.C. samples to
be Included with each batch of real samples (requirement 18) that 1s run In
one 8-hour time period or on each shift. The requirements 3 through 8 are to
be run 1n the order as they appear In the list below on each shift.
* Reference - Currle, Lloyd A. "Limits for Qualitative Detection and
Quantitative Determination' Anal, Chem., 40, 3, 586-S93, 1968
11
-------
^ U5 191
1. An Initial calibration must be performed using calibration standard
solutions with varied (1,5, and 25 ug/kg equivalent) native TCDO and 5 ug/kg
equivalent Internal standard. Calibration for the surrogate standard will
be based only on the high level standard (1 ug/kg equivalent). The criteria
given 1n Section VII must be met or the calibration must be repeated.
2. Initially, 20 replicate determinations of the spiking solution must
be run and area responses for the sum of m/z 257 and 259 Ions vs the m/z 268
1op must be calculated. Twenty separate ratios must be determined (Equation
IV) and used 1n calculating the mean correction factor (Equation V).
3. A 1-point check verification using the 1 ug/kg equivalent native
TQDO and 5 ug/kg equivalent Internal standard must be run once every 8 hours or
on every shift. If the RRF values from this calibration check differ by more
than + 10% from the previously determined mean relative response factor (RRFs),
the 3~point calibration must be repeated. The calibration check for
the surrogate is not necessary unless the surrogate recoveries appear biased
and/or consistently fall outside the 60-140% control limits.
4. A laboratory "method blank" must be run along with each batch of 24
or fewer samples. A method blank is performed by executing all of the
specified extraction steps, except for the introduction of a 5 gram sample.
The method blank is also dosed with the internal standard and surrogate
standard. Results for the method blank must be calculated the same way as
samples. This includes correction for the spiking solution contribution as
indicated in Equation IX. A positive response ^ LOD (Equation VlII)must be
followed by reinjection. If still positive, re~extraction and reanalysis of
all related samples must be done.
5. "Field blanks" will be provided to monitor for possible cross-
contamination of samples 1n the field. The "field blank" will consist of
uncontaminated soil (background soil taken off-site). A positive response >.
0.1 ug/kg native TCOD must be followed by reinjection. If still positive, "
all samples associated with the field blanks must be re-extracted and reanalyzed.
6. One sample, designated by EPA, must be spiked with native 2,3,7,8-TCDD
at a level of 1 ug/kg for each set of 24 or fewer samples. The Field Blank
Spiking Solution (Section VI) should be used to spike the designated sample.
The recovery must be 0.6 to 1.4 ug/kg or the analysis stopped and all related
samples must be re-extracted and reanalyzed.
7. The laboratory will be given performance evaluation samples by EPA
to run with each batch of samples. The results from these performance evaluation
samples will be evaluated by EPA. If a result Is not within the acceptance
criteria set by EPA, all samples in the batch associated with that PE sample
must be reanalyzed.
8. Each sample must be dosed with 50 ul of the sample spiking solution
containing internal standard (equivalent to 5.0 ug/kg) and surrogate standard
(equivalent to 1.0 ug/kg). The surrogate recovery must be 0.6 to 1.4 ug/kg
or the sample must be reanalyzed.
12
-------
9. The following qualitative requirements must be met 1n order to
confirm the presence of native 2,3,7,8-TCOD:
>
a. The retention time must equal (within 3 seconds) the retention
time for the Internal standard.
b. The 257/259 ratio must be within the range 1 101 of the value
of the ratio determined in Section VII, (Equation III). ~~
' c. The ion responses at 257 and 259 must be present and maximize
together. The signal to mean noise ratio must be 2.5 to 1 or better for both
daughter Ions. (Determine the noise level by measuring the random peak to
valley signal present on either side [within 20 scans] of the 2,3,7.8-TCDD
detention window. The 2,3,7,8-TCDD signal must be at least 2.5 times larger
than this.)
d. For those samples giving non-detect results, the result must be
less than the 0.3 ug/kg required limit of detection. Otherwise the analysis
must be stopped and interferences identified and corrected until the 0.3
ug/kg required limit of detection is met.
e. For each sample, the Internal standard must be present with at
least a 10 to 1 signal to noise ratio based on the m/z 268 ion response.
IX. SAMPLE COLLECTION, PRESERVATION AND HANDLING
•
The procedures for sample collection, shipping and handling will be
specified by the EPA Regional Office responsible for the monitoring exercise.
The sampling team will be provided with an 8 ounce glass jar, and 30-300 grams
of soil will be collected. When received in the laboratory, the sample should
be thoroughly mixed in the jar for a minimum of 3 minutes, using a stainless
steel spatula. The spatula should be used to break up large clumps of soil
while mixing to achieve a homogeneous sample.
A 5 gram aliquot sample should be taken and placed in a pre-weighed 10 ml
serum vial containing approximately 5 grams of anhydrous sodium sulfate
together with a Teflon-faced septum and cap (The entire vial, NagSO^ septum
and cap is pre-weighed and labelled). The 5 gram aliquot sample should be
representative of the entire sample. Thus, large stones or other particles
which are uncharacteristic of the sample, should not be included in the
aliquot.
Samples may be stored under ambient conditions as long as temperature
extremes (below freezing or above 90°F) are avoided. Samples must be protected
from light to avoid photodecomposition.
All samples must be extracted and completely analyzed within 24 hours.
Extracts must be held for 6 months prior to disposal.
-------
X. SAMPLE EXTRACTION
CAUTION: Although the sample and standards are sealed throughout the
extraction procedure, there is always the possibility of leakage and breakage
(especially during the sample spiking and centHfuging steps). The analyst
should, therefore, be fully protected by wearing plastic gloves and laboratory
jacket (a face protector 1s optional). See Section IV for details on specific
safety requirements.
1. Prepare extraction solvent by mixing two volumes acetonltrile with one
volume dichloromethane. Mix solvents thoroughly.
2. Weigh the sample vial and determine the net weight of sample (to 3
significant figures).
3. Add 50 ul of the sample spiking solution (containing both internal
and surrogate standards). The solution will contain 0.5 ng/ul of internal
standard and 0.1 ng/ul of surrogate standard. Add the 50 ul solution directly
to the soil, spreading 1t over several sites on the surface of the soil.
4. Attempt to mix the soil and sodium sulfate by shaking. (Extremely
wet samples may not mix well, but DO NOT open the vial to stir the contents.)
Additional anhydrous sodium sulfate should be added if needed.
5. Pierce the septum with a disposable needle and leave the needle in
place to vent -the contents while the extraction solvent Is Introduced.
• 6. Add 5 ml of the 2:1 acetonltrile: dichloromethane extraction solvent
using a 5 ml syringe and disposable needle. Retain the syringe for solvent
additions only.
NOTE: Additional extraction solvent can be added 1f the analyst judges
this necessary to achieve efficient extraction on a particular sample.
7. Remove the syringe and both needles (they should be treated as
though contaminated). Dispose of both needles.
8. Shake the vial vigorously on a vortex mixer for 2 minutes.
9. Centrifuge the vial and contents at 4000 rpm for 2 minutes. Remove
carefully so as not to disturb the sediment.
10. Insert a needle through the septum so that it just breaks the surface
of the septum Inside the vial. Using a clean disposable syringe and needle,
withdraw approximately 1 ml of the extract; NOTE: The other needle through the
septum serves to equilibrate the pressure upon withdrawal of the extract.
11. Invert the syringe and withdraw the plunger to remove the extract
from the needle. Dispose of the needle (1t 1s contaminated).
12. Place a 0.45 micron disposable Teflon filter on the syringe and •
the extract into a clean 10 ml serum vial containing 9 ml distilled water.
Dispose of the syringe and the filter.
-------
05 19
13. Using a Teflon lined septum ind an aluminum cap, cover and crimp the
vial containing the Mater-extract mixture.
14. Manually shake the vial vigorously for about one minute.
15. Centrifuge the vial to separate the dichloromethane phase from the
water/acetonltrlle phase. The dichloromethane phase will appear as a small
bubble at the bottom of the vial.
16. Prepare a miniature drying tube as follows:
a. Plug the tip of a disposable plpet with a small amount of silanized
glass wool.
b. Add approximately 1/2 cm anhydrous sodium sulfate.
17. With a disposable syringe and needle, remove the dlchloromethane phase
from the vial (step IS) as completely as possible.
18. Transfer the dlchloromethane phase through the drying tube Into a clear
1 ml serum vial.
19. Rinse the drying tube with one-half ml dlchloromethane, and collect
1n the same 1 ml serum vial.
20. Under a stream of nitrogen, evaporate the solvent gently until the
volume of solution remaining in the serum vial 1s 0.05-0.1 ml.
21. Seal the 1 ml serum vial with a Teflon lined septum and cap. Label the
vial appropriately.
XI. CLEANUP
The need for cleanup 1s indicated when a particular extract does not meet
the QC criteria for the coelution of all four monitored ions, surrogate recover
or the ratio A257/A250. Two cleanup procedures are given below.
A. Modified Option A Cleanup
1. Plug the tip of a disposable plpet with a small amount of silanized
glass wool.
2. Place approximately a 1 cm layer of silica gel over the glass wool.
3. Place approximately a one-half cm layer of anhydrous sodium sulfate
over the $111ca gel.
4. Plug the tip of • second disposable plpet with a small amount of
silanized glass wool.
5. Place approximately 0.5 cm add alumina over the sllanired glass wool.
6. Place approximately 0.5 cm anhydrous sodium sulfate over the alumina.
15
-------
7. Arrange the two columns so that the silica gel column will elute onto
the alumina coluon, and the alumina column drippings will be collected
In a vial.
B. Rinse the two columns with 0.5 ml cyclohexane and discard the eluate.
9. Open the vial containing the extract and add 1 ml cyclohexane to the
extract.
»
( 10. Under a stream of nitrogen, carefully evaporate the dichloromethane fro
the extract vial (the volume of the remaining solution should be just
under 1 ml).
11. Transfer the entire contents of the extract vial onto the silica column
arranged as specified in step 7.
12. When the solution just reaches the surface of the sodium sulfate layer
In the silica gel column, add 0.5 ml cyclohexane.
13. Repeat step 12 a second time. Allow the solution to drip completely
after the second addition of cyclohexane.
14. Discard the silica gel column.
15. Rinse the alumina column with an additional 1 ml cyclohexane. Discard
the accumulated eluates in the vial beneath the column.
16. Place a clean 1 ml serum vial under the alumina column.
17. Elute the alumina column with three successive portions of 0.5 ml each
of 15% by volume dichloromethane 1n cyclohexane, collecting the eluate
in the clean vial.
18. With gentle heating and under a stream of nitrogen, evaporate the solv<
until the volume in the vial 1s 0.05-0.1 ml.
19. Seal the serum vial with a teflon lined septum and cap. Label the vial
appropriately. NOTE: If 1t is a priori known that the second step of
cleanup is required, evaporate the sample in stage 18 to just below
1 ml and Immediately proceed with a second cleanup as described below.
B. Option D Cleanup
1. In advance, prepare a mixture of 3.6 g Carbopack C with 16.4 g Celite
545. Activate the mixture at 130°C for 6 hours.
2. Plug the tip of a disposable pipet with a small amount of silanized gl<
wool.
3. Place 2 cm layer of the carbopack-Celite mixture over the glass wool
plug, using suction to pack the column.
16
-------
4. Rinse the column sequentially with 2 ml toluene. 1 ml dlchloromethane-
methanol-benzene (75:20:5 by volume), 1 ml cyclohexane-dlchloromethane
1:1 by volume), and finally 2 nl cyclohexane. Collect the eluate 1n a
vial and discard the eluate.
5. Dilute the extract which has been cleaned up by the Modified Option A
procedure to 1 ml with cyclohexane.
•
t 6. Maintaining a discard vial under the column. Introduce the extract
onto the column.
7. After the solvent has drained, rinse the column successively with 2 ml
cyclohexane, 1 ml cyclohexane-dichloromethane mixture (1:1 by volume)
and 1 ml dlchloromethane-methanol-benzene mixture (75:20:5 by volume).
8. Allow the column to drain completely and discard the accumulated eluate
9. Place a clean serum vial under the column.
10. Elute the dloxin from the charcoal with 2 ml toluene.
11. With gentle heating and under a stream of nitrogen, concentrate the
extract to a volume of 0.05-0.1 ml.
12. Seal the serum vial with a Teflon lined septum and cap. Label approprij
XII. GC/MS/MS ANALYSIS
1. Table 1 summarizes the 15 m D8-5 gas chromatographic capillary
column and operating conditions. The 15 m DB-5 column has been us«d for
chromatography which Is not Isomer specific (no valley 1s observed between the
1,2,3,4-TCDD and 2.3,7.8-TCDD Isomers).
2. Standards and samples must be analyzed under Identical MS/MS
conditions. Selected Reaction Monitoring (SRM) scans are used, using a scan
time to give at least five points per chromatographic peak. Recommended
MS/MS conditions are given 1n Table 2.
3. Verify the Calibration of the system daily as described 1n Section
VII. The volume of calibration standard Injected should be approximately the
same as all sample injection volumes. The requirements described In Section
VIII. Parts 9b and 9c must be met for all calibration standards.
- 4. Inject a 1 to 2 ul aliquot of the sample extract.
•
5. The presence of TCOO Is qualitatively confirmed If the criteria of
Section VIII, Part 9, are achieved.
6. For quantltatlon, measure the area response of the m/z 257 and
peaks for 2.3.2.8-TCDD; the m/z 268 peak for "Cl2-2.3,7,8-TCOO. and the
263 peak for */Cl4-2.3.7,8-TCOO. Calculate the concentrations df nativi
259
the m/z
ve and
surrogate standards using the following equations:
17
-------
05
Equation IX: (Calculation of concentration of native 2,3,7,8-TCDD)
«) - C.F.)
RRFs x M
where Cs » The concentration of native 2,3,7,8-TCDD in ug/kg
AS * the sum of the area responses for the Ions, m/z 257 and 259
• the area response for the ion m/z 268
C.F. • correction factor for spiking solution (blank) previously determined
(Equation V)
Qfs • quantity (1n nanograms) of 13Ci2"2.3,7,8-TCDD added to the sample beft
extraction
RRFS « Relative response factor for 2,3,7,8-TCDO calculated previously
(Equation I)
W * weight (fh grams) of wet soil or sediment sample.
In evaluating the results* a distinction must be made between quantitative
measurement and qualitative Identification of 2,3,7,8-TCDO. The following steps
must be followed In the treatment of all sample results:
1. Calculate the concentration of native 2,3,7,8-TCDD using equation IX.
2. Determine 1f all of the qualitative Identification criteria are met.
3. If all qualitative Identification criteria are met, report the
concentration found by equation IX, regardless of concentration.
4. If the qualitative Identification criteria are not met, and the
concentration calculated by equation IX 1s less than the required limit of
detection of 0.3 ug/kg, report the concentration as less than 0.3 ug/kg (I.e.
<0.3 ug/kg).
5. If the qualitative Identification criteria are not met, and the
concentration calculated by equation IX 1s greater than the required limit of
detection of 0.3 ug/kg, the extract must be reinjected. If the qualitative
Identification criteria are still not met and the result 1s still greater than
0.3 ug/kg, the extract must be cleaned up or the sample reanalyzed until a
satisfactory result 1s obtained, (i.e. positive result or negative result
below 0.3 ug/kg).
NOTE: In reporting results for sample analysis, a comparison is made with
the required Unit of detection. The limit of detection based on the blank
(Equation VIII) might also be used, but interferences may be present and
introduce false positives in some cases. However, as explained 1n Section
VII, the empirical limit of detection based on the blank must be less than
the required limit of detection of 0.3 ug/kg.
18
-------
Equation X: (Calculation of concentration of surrogate standard, 37Cla-
~* 2.3,7,8-TCOO)
Ass x Q1s
^SS • 5,5, JT
AJJ x RRFjj x W
where Css « the concentration of surrogate standard 37Cl4-2,3,7,8-TCDD
in ug/kg.
Ass « the area response for the 1on m/z 263*
*is * tne area response for the ion m/z 268
"'•I
37,
- quantity (in nanograms) of 13C12-2,3,7,8-TCDD added to the
sample before extraction.
RRFSS » Relative response factor for C14-2,3,7.8-TCDD calculated
previously (Equation II). _ .
W « Weight (in grams) of wet soil or sediment sample.
* Subtract 0.0108 of any 257 response from the 263 response to correct for
contributions of any 2,3.7,8-TCDD to the 263 response.
Native 2,3,7,8-TCOO contains an innate quantity of 37Cl4-2,3,7,8-TCDD.
Except at high concentrations of native 2,3,7,8-TCDD, this contribution is
too small to significantly affect the calculated concentration of surrogate
Cl4-2,3,7,8-TCDD. The theoretical correction Is calculable on the basis of
isotope distribution and amounts to 1.08% of the m/z 257 peak. (This correction
should be checked at low resolution by analyzing about 200 pg/ul of unlabelled
2,3,7,8-TCDD.) On this basis, the correction to the area count of the surrogate
is made as follows:
A263 « *263 ' °-0108 A257
Calculate the analytical percent recovery of the surrogate standard.
Surrogate amount measured* (nanograms) X 100
Analytical « 5 ng
Percent Recovery
* NOTE: The amount measured is equal to the concentration found by
equation X multiplied by the weight of soil used for the sample (I.e., Css x
W).
XIII. METHOD PERFORMANCE
The required detection limit for this method 1s 0.3 ug/kg. For certain
samples, this detection limit may not be achievable because of Interferences.
These samples require cleanup as described in Section XI. This method has
been compared with the EPA-IFB GC/MS Method for 2,3,7,8-TCDD and found to be
applicable to analyses of soils where 2,3.7,8-TCDD 1s the only tetrachloro
isomer known to be present.
19
-------
> TABLE I
OPERATING CONDITIONS FOR DB-5 GAS CHROMATOGRAPHY COLUMN
COLUMN
Length
I. D.
Film Thickness
2,3.7,8-TCDD R. T. (approx.)
Carrier gas
•»
Initial Temperature
Initial Time
Splitless Time
Program Rate
Final Temperature
Split Flow
Se urn Purge Flow
Capillary Head Pressure
Transfer Line Temperature
DB-5
15 m
0.32 mm
1.0 micron
5-6 min.
N2
150°C
l.U min.
1.0 min.
20°C/min.
240»C
20 ml/min.
0.6 ml/min.
8 psi
240°C
20
-------
TABLE 2
MS/MS OPERATING CONDITIONS
Instrument
Ion Source
CI Reagent Gas
Reagent Gas Flow
Source Temperature
Discharge Current
Ql Resolution
Q3 Resolution
Collision Energy (LAB)
Collision Gas
Collision Gas Thickness
TAGA* or TAGA« 6000E
Townsend/glow discharge CI
Zero grade air (H? and He free)
35 ^ ml/min.
200 *C
•1 mA
3 amu at 501 peak height at m/z * 320 (singl<
3 amu at 501 peak height at m/z * 320 (singl<
55eV [(OR * GR)/2-R2] or 55eV (OR - R2)
Ar
400 x 1012 molecules/cm2
Ions Monitored:
320 257 (native-TCOD) '
322 259 (native-TCDD)
328 263 (surrogate standard)
332 268 (internal standard)
21
-------
XIV. DATA REPORTING
Report all data 1n units of mlcrograms per kilogram of wet soil. Use
three significant figures at concentrations above 1 ug/kg and 2 significant
figures at concentrations below 1 ug/kg. The data package must Include the
following Information:
1. Individual and mean response factor for the three-point calibration
of unlabelled 2,3,7,8-TCDD. (Based on High level standard only).
2. Individual and mean response factors for the Isotopic surrogate
standard (based on high level standard only).
3. The Individual ratios of the sum of areas 257 and 259 ions to the
268 ion for 20 replicate measurements of the blank (I.e.. sample spiking
solution), and the mean Correction Factor based on these ratios.
4. The empirical limit of detection based on the 20 blank measurements
5. The daily or shift verification of the mean response factors.
6. The percent accuracy I.e., (analytical percent recovery) for the
surrogate standard.
7. The result for the method blank.
8. The percent recovery of native TCDO from the spiked sample.
9. The result- for the PE sample
10. The result for the field blank.
11. The data filename (to facilitate data retrieval).
12. The sample identification number (as assigned by the field samplin
team).
13. Analytical date and time.
14. The area responses for ions 257, 259, 263, and 268.
15. The observed response ratio of Ions 257/259 for the sample.
16. The calculated value for native 2,3,7,8-TCDD. (Values above or
below 0.3 ug/kg are to be reported only If qualitative Identification criter
are met.)
17. If no 2,3,7,8-TCDD was detected, report "not detected" or N.D. and
the 0.3 ug/kg required detection limit.
18. The mass chromatograms for all samples and standards. Include t
the real-time display data and reduced data showing limits of integration.
Include any computer generated response tables.
-------
5 1981
19. The weight of the original wet sample aliquot.
20/* Documentation on the source and history of the native and labelled
2,3,7,8-TCDO standards used.
21. Any other supporting documentation. An example of the required
.data format follows:
23
-------
INITIAL CALIBRATION SUMMARY \
Data
File Name
Sample
I.O.f
Analysis
Date 1 Time
Un labeled (Native)
2,3.7,8-TCDO
Equiv. I
Cone" 1 RF
Mean
RF
Surrogate . •
2,3,7.8-TCDD
Equiv.
Cone"
RF
Mean
RF
-------
DAILY OR SHIFT CALIBRATION VERIFICATION
Data
File Name
Sample
I.D.I
Analysis
Date I Time
Unlabeled (Native)
2,3,7,8-TCDD
RF
l Difference
from Mean RF
25
-------
BLANK RESPONSE SUMMARY
Number
Data
File Name
Sample
I.D.I
Analysis
Date Time
Response Areas
257 | 259 | 268
Blank Response (B)
257 * 259
26B
Equivalent tone"
of 2.3.7.8-TCDD"
c
c
2
C
cr
-------
Calculations;
* Note: The equivalent concentrations of 2,3,7,8-TCOO (last column) are calculated using Equation VI
CD ' *b * Qls
Other calculations required are:
1. Equation V: Correction Factor (C.F.) for Blank Contribution
C. F. • r B
n
2. Equation Vll; (Standard Deviation of the Blank Responses)
SD • ( t Cb2 ) - (E Cb)2/n ' '
n-1
3. Equation VIII; (Limit of Detection based on "Well Known" Blank)
LOG - 2 * t " SD • .
27
cn
CO
00
-------
TCDD DATA REPORT FORN
Lab:
Case No.:
Report Date:
Data
File Name
Analysis
Date Time
Aliquot Response Areas
£
Ib
Wet *t. (q) Z57 259 263 268 257/259 uq/kq TCDD
Surrogate
ug/kq tAcc. Comments
MB - Method Blank
FB • Field P
N - Native TCUO Spike
DL « DeterMon Limit
Nn • Nnt »rt**rf
cn
CD
CX7
-------
Add i 1 1 'Mini r rcnti 1 1 cHrnt s must furtmlr I'll- usi1 ->r fdrrt.il ch.iiti
n(' custody nn
-------
APPENDIX D
DRAFT ASME SAMPLING PROTOCOL
•SAMPLING FOR THE DETERMINATION OF CHLORINATED ORGANIC
COMPOUNDS IN STACK EMISSIONS-
DRAFT, OCTOBER 1984
1430J C3044-A
-------
SAMPLING FOR THE DETERMINATION OF CHLORINATED
ORGANIC COMPOUNDS IN STACK EMISSIONS
1. PRINCIPLE AND APPLICABILITY
1.1 Principle; Stack gases that may contain chlorinated
organic compounds are withdrawn from the stack using a
sampling train. The analyte is collected in the sampling
train. The compounds of interest are determined by
solvent extraction followed by gas chrooatography/mass
spectroscopy (GC/MS).
1.2 Applicability; This method is applicable for the deter-
mination of chlorinated organic compounds in stack emis-
sions. The sampling train is so designed that only the
total amount of each chlorinated organic compound in the-
stack emissions may be determined. To date, no studies
have been performed to demonstrate that the particulate
and/or -gaseous chlorinated organic compounds collected in
separate parts of the sampling train accurately describes
the actual partition of each in the stack emissions. If
separate parts of the sampling train are analyzed separ-
ately, the data should be included and so noted as- in
Section 2 below. The sampling shall be conducted by
competent personnel experienced with this test procedure
and cognizant of intricacies of the operation of the
prescribed sampling train aod constraints of the analyti-
cal techniques for chlorinated organic compounds, especi-
ally PCDDs and PCDFs.
Note: This method assumes that the XAD-2 resin collects
all of the compounds of interest from the stack emissions.
Since the method at the present time has not been vali-
dated in the presence of all the other components present
(HC1, high organic load) in the stack emission, it is
recommended that appropriate quality control (QC) steps be
employed until such validation has been completed. These
QC steps aay include the use of a backup resin trap or the
addition of a representative labeled standard (distin-
guishable from the internal standard used for quantita-
tion) to the filter and/or the XAD-2 in the field prior to
the start of sampling. These steps will provide informa-
tion on possible breakthrough of the compounds of inter-
est.
2. REPORTABILITT
Recognizing that modification of the method may be required
for specific applications, the final report of a test where
changes are made shall include: (1) the exact modification;
(2) the rationale for the modification; and (3) an estimate of
the effect the modification will produce on the data.
-------
i
i
t
DR
3. RANGE OF MINIMUM DETECTABLE STACK GAS CONCENTRATION
jj The range of the analytical method may be expanded consider-
,T* ably through concentration and/or dilution. The total method
• sensitivity is also highly dependent on the volume of stack
M gas sampled and the detection limit of the analytical finish.
.^ The user shall determine for their system the minimum detect-
able stack gas concentration for the chlorinated organic con-
• pounds of interest. The minimum detectable stack gas concea-
Tj tration should generally be in the ng/m or lower range.
4. INTERFERENCES
;/f. Organic compounds other than the compounds of interest may
interfere with the analysis. Appropriate sample clean-up
; ' steps shall be performed. Through all stages of sample
II handling and analysis, care should be taken to avoid contact
~ of samples and extracts with synthetic organic materials oth
• than polytetrafluorethylene (TPE*). Adhesives should not be
;-| used to hold TFE* liners on lids (but, if necessary, appro-
3 priate blanks must be run), and lubricating and sealing
greases must not be used on the sampling train.
J 5. PRECISION AND ACCURACY
Precision and accuracy measurements have not yet been made
j| PCDD and PCDF using this method. These measurements are
1 needed* However, recovery efficiencies for source.samples
spiked with compounds have ranged from 70 to 120Z. '
6. SAMPLING RONS. TIME, AND VOLUME
6.1 Sampling Runs; The number of sampling- runs must be
sufficient to provide minimal statistical data and in no
case shall be less than three (3).
6.2 Sampling Time; The sampling time must be of sufficien
length to provide coverage of the average operating conditi
of the source. However, this shall not be less than three
hours (3).
6.3 Sample Volume; The sampling volume must be sufficient
provide the required amount of analyte to aeet both the HDL
the analytical finish and the allowable stack emissions. I
may be calculated using the following formula:
, „ , . 100 100 1
Sample Volume -Ax - x-—r— x TT
A • The analytical MDL in ng
B - Percent (Z) of the sample required per analytical f
run
C » The sample recovery (Z)
A-2
-------
DRAFT
D - The allowable stack emissions (ng/m )
Example: A - 0.050 ng; B - 10Z; C - 50Z; and D - 1 ng/m
« «c 100 100 1 . 3
SV - 0.05 x -JQ x -^ x y - 1m
7. APPARATUS
Sampling Train: The train consists of nozzle, probe, heated
particulate filter, and sorbenc module followed by four impiogers
(Fig. 1). Provision is made for the addition of (1) a cyclone in
the heated filter box when testing sources emitting high concen-
trations of particulate matter, (2) a large water trap between the
heated filter and the sorbent module for stack gases with high
moisture content, and (3) additional implngers following the
sorbent module. If one of the options is utilized, the option
used shall be detailed in the report. The train may be construct-
ed by adaption of an EPA Method 5 train. Descriptions of the
sampling train components are contained in the following sections.
7.1.1 Nozzle
The nozzle shall be made to the specifications of EPA Method
5. The nozzle may be made of nickel plated stainless steel,
quartz, or boro-silicate glass.
7.1.2 Probe
The probe shall be lined or made of TFE*, borosilicate, or
quartz glass. The liner or probe extends past the retaining nut
into the stack. A temperature controlled jacket provides protec-
tion of the liner or probe. The liner or probe shall be*equipped
with a connecting fitting that Is capable of forming a leak-free,
vacuum-tight connection without sealing greases.
7.1.3 Sample Transfer Lines (optional)
The sample transfer lines, if needed, shall be heat traced,
heavy walled TFE9 (1.3 cm [1/2 la.] O.D. x 0.3 cm [1/8 In.] wall)
with connecting fittings that are capable of forming leak-free,
vacuum-tight connections without using sealing greases. The line
should be as short as possible and must be maintained at 120°C.
7.1.4 Filter Holder
Borosilicate glass, with a glass frit filter support and a
glass-to-glass seal or TFE* gasket. A rubber gasket shall not be
used. The holder design shall provide a positive seal against
leakage from the outside or around the filter. The holder shall
be attached immediately at the outlet of the probe (or cyclone, if
used).
A-3
Rr ...
-------
Vi.
.
.^—. Nt.n — -.«.Z_^L
I
I »
DP'
i
I
i
(~,~.)
> *_ \
•fL-, *^« \';'T'*-i-iip.
J.^.../.....V^4i
L~1=sru''BL «•
w^
Z?F
Fif. 1 Modified E?A Method 5 Train'for Ori»nics Saspliag
Source: Kechoda Manual Saopliof and Analysis Procedure*
for Assessing Organic* Inissiena froa Stationery Con-
bust ion Sources in Exposure lvalo»tion Division
Studies, U.S. Znvironaental Protection Agency
leport Ko. r?A-560-82-OlA (January 1982).
A-4
-------
F
7.1.5 Cyclone in Filter Box (optional)
The cyclone shall be constructed of borosilicate glass with
connecting fittings that are capable of forming leak-free,
vacuum-tight connections without using sealing greases.
7.1.6 Filter Heating System
The heating system must be capable of maintaining a tempera-
ture around the filter holder (and cyclone, if used) during sampl-
ing of 12(H14°C (248+25°F). A temperature gauge capable of
measuring temperature to within 3°C (5.4°F) shall be installed so
that the temperature around the filter holder can be regulated and
monitored during sampling.
7.1.7 Solid Sorbent Module
used as the sorbent. The sorbent module shall be made of glass
with connecting fittings that are able to fora leak-free, vacuum-
tight seals without use of sealant greases (Figs. 2 and 3). The
XAD-2 trap must be in a vertical position. It is preceded by a
coil-type condenser, also oriented vertically, with circulating
cold water. Gas entering the sorbent module must be maintained at
<_20°C (68°F). Gas temperature shall be monitored by a thermo-
couple placed either at the inlet or exit of the sorbent trap.
The sorbent bed* must be firmly packed and secured in place to
prevent settling or channeling during sample collection. Ground
glass caps (or equivalent) must be provided to seal the sorbent-
filled trap both prior to and following sampling. All sorbent
aodules must be maintained in the vertical position during sampl-
ing.
7.1.8 lapingers
Four or more impingers with connecting fittings able to fora
leak-free, vacuum-tight seals without sealant .greases when con-
nected together, shall be used. All impingers are of the
Greenburg-Smith design modified by replacing the tip with 1.3 cm
(1/2 in.) ID glass tube extending to 1.3 cm (1/2 In.) from the
bottom of the flask.
7.1.9 Metering System
The metering system shall consist of a vacuum gauge, a leak-
free pump, thermometers capable of measuring temperature to within
3 C (-5 F), a dry gas meter with 2 percent accuracy at the
required sampling race, and related equipment, or equivalent.
7.1.10 Barometer
Mercury, aneroid, or other barometers capable of measuring
atmospheric pressure to within 2.2 Eg (0.1 in. Eg) shall be used.
A-5
-------
D
ru
!• I/a m I
OS •«.?••'71-4 •• I
tfri 2f. Aeetpeablc iorbenc codulc design
-------
Flow DIrtcllon
».. -,
-------
DR
./'A
1 7.2 Sanple Recovery, Supplies, and Equipment
'4 7.2.1 Ground Glass Caps or Hexane Rinsed Aluminum Foil
% ^^^^^ ^^"^^ ™^~^^ - — - ' ^^—^»™«
* To cap off adsorbent tube and the other sample-exposed por-
tions of the train. If TFE* screw connections are used, Chen TFE*
screw caps shall be used.
** 7.2.2 Teflon FEP* Wash Bottle
| :
r4 Three 500 ml, Nalgene No. 0023A59, or equivalent.
•4 7.2.3 Probe and Transfer Line Brush
I Inert bristle brush with stainless steel rod-handle of suffi-
cient length chac is compatible with the liner or probe and trans-
fer line.
1
.-* 7.2.4 Filter Storage Containers
Sealed filter holder or precleaned, wide-mouth amber glass
containers with TFE*-lined screw caps or wrapped in hexane rinsed
aluminum foil.
7.2.5 Balance
Triple beam, Ohaus model 7505, or equivalent.
7.2.6 Aluminum Foil
Heavy duty, hexane-rinsed.
7.2.7 Preeleaned Metal Can
To recover used silica gel.
7.2.8 Preeleaned Graduated Cylinder, e.g., 250 ml
250 ml, with 2 ml graduations, borosilicate glass.
7.2.9 Liquid Sample Storage Containers
Frecleaaed nmber glass bottles or clear glass bottles vrapped
in opaque material, 1 L, with TFE*-lined screw cape.
8. REAGENTS
8.1 Sampling
8.1.1 Filter — Fiberglass Reeve-Angel 934 AH or Equivalent
Prior co use la Che field, each lot of filters shall be sub-
jected co precleaning and a quality control (QC) contamination
check co confirm chac there are ao contaminants present that will
A-8
-------
Tl DRAFT
interfere with the analysis of analyte at the target detection
limits.
If performed, filter precleaning shall consist of Soxhlet
extraction, in batches not to exceed 50 filters, with the sol-
vents) to be applied to the field samples. As a QC check, the
extracting solvent(s) shall be subjected to the same concentra-
tion, cleanup and analysis procedures to be used for Che field
samples. The background or blank value observed shall be con-
verted to a per filter basis and shall be corrected for any
differences in concentration factor between the QC check (CFQC)
and the actual sample analysis procedure (CF ) . "
where:
CF - Initial volume of extracting solvent
Final Volume of concentrated extract
The quantitative criterion for acceptable filter quality will
depend on the detection limit criteria established for the field
sampling and analysis program. Filters that give a background or
blank signal per filter greater than or equal Co the target detec-
tion limit for the analyte(s) of concern shall be rejected for
field usel Note that acceptance criteria for filter cleanliness
depends not only on the inherent detection limit of Che analysis
method but also on Che expected field sample volume and on the
desired limit of detection in Che sampled stream.
If the filters do not pass Che QC check, they shall be re-
excracced and Che solvent extracts re-analyzed until an acceptably
low background level is achieved.
8.1.2 Amberlite XAD-2 Resin
The cleanup procedure may be carried out in a giant Soxhlec
extractor, which will contain enough Amberlite XAD-2* resin
(XAD-2) for several sampling traps. An all glass Chimble 55-90 mm
OD x 150 mm deep (top Co frit) containing an excra coarse frit is
use£—fret—e*A^«ccion of XAD-2. The fric if recessed 10-15 mm above
renelateduring at Che bottom of the Chimble Co facilieaee
drTluajje. The XAD-2 muse be carefully retained ia Che extractor
cup with a glass wool plug and stainless steel screen since it
floacs on methylene chloride. This process involves sequencial
excraccion in che following order.
Solvent Procedure
Wacer Inieial rinse with 1 L H-0 for 1 cycle,
Chen discard HO
A-9
'v'?'^> \
-------
DHf;
^f i \
ivr
Water
Methyl alcohol
Methylene chloride
Hexane
Extract with H-0 for 8 hr
Extract for 22 hr
Extract for 22 hr
Extract for 22 hr
The XAD-2 must be dried by one of the following techniques.
(a) After evaluation of several methods of removing residual
solveot, a fluidized-bed technique has proven to be the caszssc
and most reliable drying method.
A simple column with suitable retainers as shown in Fig. 4
will serve as a satisfactory column. A 10.2 ca (4 in.) dianeter
Pyrex pipe 0.6 m (2 ft. long) will hold all of the XAD-2 from the
Soxhlet extractor, with sufficient space for fluidizing the bed
while generating a minimum XAD-2 load at the exit of the coluan.
The gas used to remove the solvent is the key to preserving
the cleanliness of the XAD-2. Liquid nitrogen from a regular
commercial liquid nitrogen cylinder has routinely proven to be a
reliable source of large volumes of gas free from organic concaa
nants. The liquid nitrogen cylinder is connected to the column
a length of precleaned 0.95 ca (3/8 in.) copper tubing, coiled
pass .through a heat source. As nitrogen is bled from the cyll
der, it is vaporized in the heat source and passes through the
column. A convenient heat source is a water bath heated from a
steam line* The final nitrogen temperature should only be war:
the touch and not over 40 C. Experience has shown that about 5
g of XAD-2 may be dried overnight consuming a full 160 I. cylind
of liquid nitrogen*
As a second choice, high purity tank nitrogen may be used c
dry the XAD-2. The high purity nitrogen must first be passed
through a bed of activated charcoal approxiaately 150 mL in
volume. With either type of drying method, the rate of flow
should gently agitate the bed. Excessive fluidation may cause
particles to break up.
(b) A* an alternate, if the nitrogen process is not available,
XAD-2 aay be dried in a vacuum oven, if the temperature never
exceeds 20°C.
The XAD-2, even if purchased clean, mast be checked for *>'
methylene chloride and hexane residues,"plus noraal blanks be
use.
(c) Storage of Clean XAD-2: XAD-2 cleaned and dried as press
above is suitable for iaaediate use in the field, provided "
passes the QC contamination check described in (d), below.
ever, precleaned dry XAD-2 aay develop unacceptable levels o
A-10
-------
u
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contamination if scored for periods exceeding a few weeks
If precleaned XAD-2 is not to be used immediately, it shall b<
stored under distilled-in-glass methanol. No more than two weeks
prior to initiation of field sampling, :he excess methanol shall
be decanted; the XAD-2 shall be washed with a small volume of
methylene chloride and dried with clean nitrogen as described in
(b) above. An aliquot shall then be taken for the QC contamina-
tion check described in (d), below.
If the stored XAD-2 fails the QC 'check, it may be recleaned b;
repeating the final two steps of the extraction sequence above:
sequential methylene chloride and hexane extraction. The QC
contamination shall be repeated after the XAD-2 is recleaned and
dried.
(d) QC Contamination Check: The XAD-2, whether purchased, "pre-
cleaned", or cleaned as described above, shall be subjected to a
QC check to confirm the absence of any contaminants that might
cause interferences in the subsequent analysis of field samples.
An aliquot of XAD-2, equivalent in size to one field sampling tub
charge, shall be taken to characterize a single batch of XAD-2.
The XAD-2 aliquot shall be subjected to the same extraction.
concentration, cleanup, and analytical procedure(s) as is (are) t
be applied to the field samples. The quantitative criteria for
acceptable XAD-2 quality will depend on the detection limit cri-
teria established for the field sampling and analysis program.
XAD-2 which yields a background or blank signal greater than or
equal to that corresponding to one-half the MDL for the analyteCs
of concern shall be rejected for field use. Note that the accept
anee limit for XAD-2 cleanliness depends not only on the inherent
detection limit of the analytical method but also on the.expected
field sample volume and on the desired limit of detection in the
sampled stream.
8.1.3 Class Wool
Cleaned by thorough rinsing, i.e., sequential immersion in
three aliquots of hexane, dried in a 110°C oven, and stored in a
hexane-washed glass jar with TFE*-lined screv cap.
8.1.4 Water
Deionized, then glass-distilled, and stored in hexane-rinsed
glass containers with TFE*-lined screw caps.
8.1.3 Silica Gel
Indicating type, 6-16 mesh. If previously used, dry at 175;.-
for 2 hr. New silica gel may be used as received.
8.1.6 Crushed Ice
-------
D
PA F
{ v. /"I'
Place crushed ice in the water bath around the impingers
during sampling.
9. SAMPLE RECOVERY REAGENTS
9.1 Acetone
Pesticide quality, Burdick and Jackson "Distilled in Glass" or
equivalent, stored in original containers. A blank must be
screened by the analytical detection method.
Distilled in Glass'
A blank must be
or
9.2 Hexane
Pesticide quality, Burdick and Jackson '
equivalent, stored in original containers.
screened by the analytical detection method.
10. PROCEDURE
Caution: Sections 10.1.1.2 and 10.1.1.3 shall be done in the
laboratory.
10.1 Sampling
10.1.1 Pretest Preparation
All train components shall be maintained and calibrated
according-to the procedure described in APTD-0576 unless otherwise
specified herein.
Weigh several 200 to 300 g portions of silica gel in air-tight
containers to the nearest 0.5 g. Record the total weight of the
silica gel plus container, on each container. As an alternative,
the silica gel may be weighed directly in its impinger or sampling
holder just prior to train assembly.
Check filters visually against light for irregularities and
flaws or pinhole leaks* Pack the filters flat in a precleaned
glass container or wrapped hexane-rinsed aluminum foil.
10.1.1.1 Preliminary Determinations
Select the sampling site and the minimum number of sampling
points according to EPA Method 1. Determine the stack pressure,
temperature, and the range of velocity heads using EPA Method 2;
it is recommended that a leak-check of the pitot lines (see EPA
Method 2, Sec. 3.1) be performed. Determine the moisture content
using EPA Approximation Method 4 or its alternatives for the
purpose of making isokinetic sampling rate-settings. Determine
the stack gas dry molecular weight, as described in EPA Method 2,
Sec. 3.6; if integrated EPA Method 3 sampling is used for molecu-
lar weight determination, the integrated bag sample shall be taken
simultaneously with, and for the same total length of time as, the
EPA Method 4 sampling.
A-13
-------
DF,
Select a nozzle size based on the range of velocity heads,
such that it is not necessary to change the nozzle size in order
to maintain isokinetic sampling rates. During the run, do not
change the nozzle size* Ensure that the proper differential
pressure gauge is chosen for the range of velocity heads
encountered (see Section 2.2 of EPA Method 2).
Select a suitable probe length such that all traverse points
can be sampled. For large stacks, consider sampling from opposite
sides of the stack to reduce the length of probes.
Select a total sampling time greater than or equal to the
minimum total sampling time specified in the test procedures for
the specific industry such that (1) the sampling time per point is
not less than 2 min.. and (2) the sample volume taken (corrected
to standard conditions) will exceed the required minimum total gas
sample volume determined in Section 6.3. The latter is based on
an approximate average sampling rate.
It is recommended that the number of minutes sampled at each
point be an integer or an integer plus one-half minute, in order
to avoid time-keeping errors.
10.1.1.2 Cleaning Glassware
All glass parts of the train upstream of and including the
sorbent medule and the first impinger^T should be cleaned as
described in Section 3A of the 1980 issue of "Manual of Analytical
Methods for the Analysis of Pesticides in Humans and Environmental
Samples." Special care should be devoted to the removal of resi-
dual silicone grease sealants on ground glass connections of used
glassware. These grease residues should be removed by soaking
several hours in a chromic acid cleaning solution prior to routine
cleaning as described above.
10.1.1.3 Amberlite XAD-2 Resin Trap
Use a sufficient amount (at least 30 gms or 3 gms/m of stack
gas to be sampled) of cleaned XAD-2 to fill completely the glass
sorbent trap which has been thoroughly cleaned as prescribed and
rinsed with hexane. Follow the XAD-2 with hexane-rinsed glass
wool and cap both cads. These caps should not be removed until
the trap is fitted iato the train. See Fig. (3)£or details. ——
The dimensions and XAD-2 capacity of the sorbent trap, and the
volume of gas to be sampled, should be varied as necessary to
ensure efficient collection of the species of interest. Some
illustrative data are presented la Table 1.
10.1.2 Preparation of Collection Train
During preparation and assembly of the sampling train, keep
all traia openings where contamination can enter covered until
-------
:ifl
TABLE 1
*ff-$\
5$J SAMPLE B1ZB AND PLOW RATE COMPARISON POtt SEVERAL SORBIiNT TRAP DESIGNS r
•w3
•>( ijj
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I.'W
-•Itf
. *•>'
*<$
ri
P*&
v- '
'.-!&
7$
m
in
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^
&
ibw
%£
l:w'-
V&
F$
1*1
^
^
Charge
nimcnslon. (w») of XAD-2 Plow Equivalent
Trap Depth Diameter Resin (B) to 43 cm/acc
BASS 70 90 130 ' »65 Lpm
8ASS /U (5.9 cfm)
u!SS)
••«•»• » 3° " («:«iSf.)
'upper liait beyond vhich collection efficiency drops off.
^ bColcul«ted fro. VgT for SOX breakthrouBh. Specified value includes a
i
/ 3
Max. Cnmple Sire \c|O^
for Efficient Capture of
FollouinR Compoundob
Octane Denzcnc Phenol
150 3.0 240
45 0,9 74
22 0.4 35
•
aafety factor of 2.
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just prior co assembly or until saopling is about to begin.
Caution: Do not use sealant greases in assembling the train.
Place approximately 100 gas of water in each of the first two
irapingers with a graduated cylinder, and leave the third impinger
empty* Place approximately 200 to 300 g or more, if necessary, of
silica gel in the last impinger. Weigh each impinger (stem
included) and record the weights en the iapingers and on the data
sheet .
Assemble the train as shown in Fig. 1.
Place crushed ice in the water bath around the iapingers.
10.1.3 Leak Check Procedures
10.1.3.1 Initial Leak Cheek
The train, including the probe, will be leak checked prior to
being inserted into the stack after the sampling train has been
assembled. Tarn on and set (if applicable) the heating/cooling
system(s) to cool the sample gas yet remain at a temperature
sufficient to avoid condensation in the probe and connecting line
to the first impinger (approximately 120 C). Allow time for the
temperature to stabilize. Leak check the train at the sampling
site by plugging the nozzle with a TFE* plug and pulling a 330 ma
Rg (12 in. Hg) vacuum. A leakage.rate in excees of 42 of the
average sampling rate or 0.0057 m /min (0.02 cfm) whichever is
less, is unacceptable. Sampling must cease if pressure during
sampling exceeds the leak check pressure.
*
The following leak cheek instruction for the sampling train
described in APTD-0576 (2) and APTD-0581 (4) may be helpful.
Start the pump with bypass valve fully open and coarse adjust
valve completely closed. Partially open the coarse adjust valve
and slowly close the bypass valve until 380 mm Hg (12 in. Hg)
vacuum is reached. Do not reverse the direction of the bypass
valve. This will cause water to back up into the probe. If 380
mm Hg (12 la. Eg) is exceeded during the test, either leak check
at this higher vacuum or end the leak check as described belov and
start the test over.
When the leak check Is completed, first slowly remove the TFE*
plug from chc inlet to the probe then immediately turn off the
vacuum pump. This prevents the water In the Impingers from being
forced backward Into the probe.
10.1.3.2 Leak Checks During a Test
A leak check shall be performed before and after a change of
port during a test. A leak check shall be performed before and
after a component (e.g., filter or optional water knockout trap)
is changed during a test.
-------
DRAF!
Such leak checks shall be performed according to the procedure
In Section 10.1.3.1 of this method except that it shall be
performed at a vacuum equal to or greater than the highest value
recorded up to that point in the test.. If the leakage rate is
found to be no greater than 0.00057 m /min (0.02 ft /min) or 4Z of
the average saopling rate (whichever is smaller) the results are
acceptable. If, however, a higher leakage rate is observed, the
tester shall either: (1) record Che leakage rate and Chen correct
the volume of gas sampled since Che last leak check as shown in
Section 10.1.3.4 of this method, or (2) void Che test.
10.1.3.3 Post-Test Leak Cheek
A leak check is mandatory at the end of a test. This leak
check shall be performed in accordance with Che procedure given in
Section 10.1.3.1 except that it shall be conducted at a vacuum
equal Co or greater Chan Che highest value recorded during Che . . _
test. If the leakage rat e (^>Tound Co be no greater Chan 0.00057
a /min (0.02 ft /min) or 4Z of Che average sampling race (which-
ever is smaller), Che results are acceptable. If, however, a
higher leakage race is observed, Che tester shall either: (1)
record che leakage race and correcc che volume as gas sampled
since che last leak check as shown in Section 10.1.3.4 of this
method, or (2) void Che Cesc.
10.1.3.4 Correcting for Excessive Leakage Rates
The equation given in Section 11.3 of this method for calcu-
jting V (scd), Che corrected volume of gas sampled, can be used
is written unless che leakage race observed during any leak check
tfcer che scare of a test exceeded L , the maximum acceptable
leakage rate (see definitions below). If an observed leakage rate
exceeds L , then replace V in Che equation in Section 11.3 with
:he following expression:
•here :
V • Volume of gas sampled a* measured by the dry gas
mecer (dscf).
I*m - Maximum acceptable leakage rate equal Co 0.00057 m /min
(0.02 fc /Bin) or 4Z of che average sampling race,
whichever la smaller*
L • Leakage race observed during che post-test leak check.
p m-Vmin (fc^/min).
L. • Leakage race observed during Che leak check performed
prior co che ~i th' leak check (i - 1,2,3. ..n), in /ain
(fc3/min).
A-17
-------
BJ - Sanpllag time interval between two successive leak checks
beginning vith the interval between the first and second
leak checks, min.
9 • Sampling time interval between the last (n th) leak check
P and the end of the test, min.
Substitute only for Chose leakages (L. or L ) which exceeded L .
ip a
10.1.3.5 Train Operation
During the sampling run, a sampling rate within 10Z of the
selected sampling rate shall be maintained. Data will be con-
sidered acceptable if readings are recorded at least every 5 min.
and not aore than 102 of the point readings are ^n} excess of ^.lOZ
and the average of the point readings is within VlOZ. During the
run, if ie becomes necessary to change any system component ia any
part of the train, a leak check must be performed prior to
restarting.
For each run, record the data required on the data sheets. An
example is shown in Fig. 4. Be sure to record the initial dry gas
aeter reading. Record the dry gas meter readings at the beginning
and end of each sampling time increment and when sampling is
halted.
To begin sampling, remove the nozzle cap, verify (if applic-
able) that the* probe and sorbent module temperature control sys-
tems are working and at temperature and Chat the probe is properly
positioned. Position the probe at the sampling point. Immedi-
ately start the pump and adjust the flow rate.
If Che stack is under significant sub-ambient pressure (height
of impinger stem), take care to close the coarse adjust valve
before inserting the probe into the stack to avoid water backing
into the probe. If necessary, the pump may be turned on with the
coarse adjust valve closed.
During the test run, make periodic adjustments to keep the
probe temperature at the proper value. Add more ice and, if
necessary, sale to ch« lee bath. Also, periodically check the
level and zero of the manometer and maintain the temperature of
sorbent module at or less than 20°C but above 0°C.
If the pressure drop across the train becomes high enough to
make the sampling rat* difficult Co maintain, the east run shall
be terminated unless the replacing of the filter corrects the
problem. If the filter ia replaced, a leak check shall be
performed*
At the end of Che sample run, turn off the pump, remove the
probe and nozzle from the stack, and record Che final dry gas
meter reading. Perform the post test leak check.*
*With acceptability of the test run to be based on the same
criterion as in 10.1.3.1.
-------
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10.2 Sataple Recovery
Proper cleanup procedure begins as soon as the probe is
removed from the stack at the end of the sampling period.
When the probe can be safety handled, wipe off all external
particulate matter near the tip of the probe. Remove the probe
from the train and close off both ends with hexane-rinsed aluminua
foil. Seal off the inlet to the train with a ground glass cap or
hexane-rinsed aluminum foil.
Transfer the probe and inpinger assembly to the cleanup area.
This area should be clean and enclosed so that the chances of
contaminating or losing the sample will be minimized. No sacking
shall be allowed.
Inspect the train prior to and during disassembly and note an?
abnormal conditions, e.g., broker/filters, color of the iapinger
liquid, etc. Treat the samples as follows:
10.2.1 Container Ho. 1
Either seal the ends of the filter holder or carefully remove
the filter from the filter holder and place it in its identified
container. Use a pair of precleaned tweezers to handle the
filter. If it is necessary to fold the filter, do so such that
the particulate cake is inside the fold. Carefully transfer to
the container any particulate matter and/or filter fibers which
adhere to the filter holder gasket, by using a dry inert bristle
brush and/or a sharp-edged 'blade. Seal the container.
10.2.2 Sorbent Modules
Remove the sorbent module from the train and cap it off.
10.2.3 Cyclone Catch
If the optional cyclone is used, quantitatively recover the
particulate into a sample container and cap.
10.2.4 Sample Container No. 2
Quantitatively recover material deposited in the nozzle,
probe, transfer line, the front half of the filter holder, and the
cyclone, if used, first by brushing and then by sequentially
rinsing with acetone and then hexane three times each and add all
these rinses to Container No. 2. Mark level of liquid on con-
tainer.
10.2.5 Sample Container Wo. 3
Rinse the back half of the filter holder, the connecting line
between the filter and the condenser and the condenser (if using
the separate condenser-sorbent trap) three tiaes each with acetone
-------
unMf
and hexane collecting all rinses in Container 3. If using the
combined condenser-sorbent trap, the rinse of the condenser shall
be performed in the laboratory after reaoval of the XAD-2. If the
optional water, knockout trap has been eoployed, it shall be
weighed and recorded and its contents placed in Container 3 along
with the rinses of it. Rinse it three times each with acetone,
and hexane. Mark level of liquid on container.
10.2.6 Sample Container No. A
Remove the first impinger. Wipe off the outside of the
impinger to remove excessive water and other material, weigh (stem
included), and record the weight on data sheet. Pour the contents
and rinses directly into Container No. 4. Rinse the impinger
sequentially three times with acetone, and hexane. Mark level of
liquid on container.
10.2.7 Sample Container No. 5
Remove the second and third impingers, wipe the outside to
remove excessive water and other debris, weigh (stem included) and
record weight on data sheet. Empty the contents and rinses into
Container No. 5. Rinse each with distilled DI water three times.
Mark level of liquid on container.
10.2.8 Silica Gel Container
•
Remove the last impinger, wipe the outside to remove excessive
water and other debris, weigh (stem included), and record weight
on data sheet. Place the silica gel into its marked container.
11. CALCULATIONS
Carry out calculations, retaining at least one extra decimal
figure beyond that of the acquired data. Round off figures after
final calculations.
11.1 Nomenclature
G - Total weight of chlorinated organic compounds in
stack gas sample, ng.
C* • Concentration of chlorinated organic compounds in
stack gas, US/° > corrected to standard conditions
of 20°C. 760 am Hg (68°F, 29.92 in. Hg) on dry
basis .
A - Cross-sectional area of ndzzle, m (ft ).
B " Water vapor la tnc gas stream, proportion by volume.
I • Percent of isokinetic sampling.
M - Molecular weight of water, 18 g/g-mole (18
w Ib/lb-mole)
A-21
-------
.
D
.
*
i
I
- Barometric pressure at the saopling site, mm Hg
(in. Hg).
- Absolute stack gas pressure, ma Eg (in. Hg ) .
- Standard absolute pressure, 760 ma Hg (29.92 in.
_ »
Hg).
.
s to.
R » Ideal gas constant. 0.06236 mm Hg-m / K-g-mole
(21.83 in. Kg-ft3/6R-lb-mole).
T • Absolute average dry gas meter temperature °K. (°R).
T • Absolute average stack gas temperature °K (°3.) .
Tstd - Standard absolute temperature, 293°K (68°F).
-. Total eass of liquid collected in iapingers and
silica gel.
V • Voluae of gas saaple as aeasured by dry gas aeter,
dca (dcf) •
V (std) - Volume of gas sample measured by the dry gas meter
'corrected to standard conditions, dsca (dscf).
Vtf(std) » Volume of vater vapor in the gas saaple corrected t
standard conditions, sea (scf).
v • Stack gas velocity, calculated by combustion calcu-
lation, m/sec (ft/sec).
.
T
AH
• Meter box correction factor.
• Average pressure differential across the orifice
aeter, aa H-0 (in. H.O).
8
13.6
60
100
• Density of vater, 1 g/al (0.00220 Ib/al).
• Total saapling tiae, min.
• Specific gravity of aercury
• Sec/ain.
• Conversion to percent.
11.2 Average Drv Gas Meter Teaperature and Average Orifice
Pressure Drop
See data sheet (Tig. A).
-------
1F1
Uh'Ar i
11.3 Dry Gas Volume
Correct the sample volume measured by the dry gas meter to
standard conditions [20°C, 760 ^mm Hg (68;rF, 29.92 in. HG ) ] by
using Equation 1.
where:
a std T ...
a (1)
,-y0.3855 °K/mm Hg for metric units
• 17.65 °R/in. Hg for English units
11.4 Volume of Water Vapor
RT ' (2)
V (std) - nL M Std - K m
w ~lc « x P 2 Ic
where:
K. « 0.00134 B /ml for metric units
• 0.0472 ft3/al for English units
11.5 Moisture Content
B
ws Vm(.td)
If liquid droplets are present in the gas stream assume the
stream to be saturated and use a psychrometric chart to obtain an
approximation of the moisture percentage.
11.6 Percent Isokinetie Sampling
»Tv
100
I
60ev»P3 An
where:
K4 " 0.003454 me Hg - m /ml - °K for metric units
- 0.002669 in Hg -.fC3/al - °R for English units
11,7 Concentration of Chlorinated Organic Compounds in Stack Gas
Dcceraine the concentration of chlorinated organic compounds
is the stack gas according to Equation 5.
A-23
-------
I
4
I
I
f
I
i
I
I
I
DP'
G
C - K S
s "5 V(std) (5)
where:
* 33
K5 - 35.31 ffVn
12. QUALITY ASSURANCE (QA) PROCEDURES
The positive identification and quantification of specific
compounds in this assessment of stationary conventional combustion
sources is highly dependent on the integrity of the samples
received and the precision and accuracy of all analytical proce-
dures employed. The QA procedures described in this section were
designed to monitor the performance of the sampling methods and to
provide information to take corrective actions if problems are
observed.
Field Blanks
The field blanks should be submitted as pare of the samples
collected at each particular testing site. These blanks should.
consist of materials that are used for sample collection and
storage and are expected to be handled with exactly the saae
procedure as each sample aedium.
Blank Train
For each series of test runs, set up a blank train in a manne
identical to that described above, but with the probe inlet cappe<
wich hexane-rinsed aluminum foil and the exit end of the last
iapinger capped with a ground glass cap. Allow the train to
remain assembled for a period equivalent to one test run. Recove
the blank sample as described in Sec* 7.2.
-------
DP/* P
REFERENCES
1. Cooke, M., DeRoos, F., and Rising, B., "Hot Flue Gas Spiking
and Recovery Study for Tetrachlorodibenzodioxins (TCDO) Using
Method 5 and SASS Sampling with a Simulated Incinerator", EPA
Report, Research Triangle Park, NC 27711 (1984).
2. Roa, J.J., "Maintenance, Calibration and Operation of Isokine-
tic Source-Sampling Equipment", EPA Office of Air Programs,
Publication No. APTD-0576 (1972).
3. Sherma, J., and Beroza, M., ed., "Analysis of Pesticides in
Humans and Environmental Samples", Environmental Protection
Agency, Report No. 600/8-80-038 (1980).
4. Martin, Robert M., "Construction Details of Isokinetic Source
Sampling Equipment", Environmental Protection Agency, Air
Pollution Control office, Publication No. APTD-0581 (1971).
5. Taylor, M.L., Tiernan, T.O., Garrett, J.H., Van Ness, G.F.,
and Solch, J.G., "Assessments of Incineration Processes as
Sources of Supertoxic Chlorinated Hydrocarbons: Concentra-
tions of Polychlorinated Dibenzo-p-dioxins/dibenzo-furans and
Possible Precursor Compounds in Incinerator Effluents",
Chapter 8-Chlorinated Dioxins and Dibenzofurans in the Total
Environment-, Buttervorth Publishers, Woburn, Mass. (1983).
A-25
--i «f
*
-------
APPENDIX C
TIMES BEACH DIOXIN RESEARCH AREA
SITE SAFETY PLAN
-------
TIKES BEACH DIOX1N RESEARCH AREA
SITE SAFETY PLAN
Current data indicates that soils at the research area ere
contaminated with 2,3,7,6-TCDD up to 2 ppm (2000 ppb). Detailed
information on the hazards of exposure to this pollutant are
contained in ^ggt-i.on f>. the Health Effects Chapter of Dioxins..
USEPA. IERL. published late in 1980. The introductory paragraph
of Section 6 is reproduced below: On a molecular basis
2,3,7,6-TCDD is perhaps the most poisonous synthetic chemical.
Only bacterial exotoxins are more potent poisons. Not only is
this TCDD isomer extremely poisonous but it also has extremely
high potential for producing adverse effects under conditions of
chronic exposure. Human exposure to 2,3,7,8-TCDD has induced
chloracne (an often disfiguring and persistent dermatologic
disorder), polyneuropathy (multiple lesions of peripheral
nerves), nystagmus (involuntary rapid movement of the eyeball),
and liver dysfunction*as manifested by hepatomegaly (increase in
liver size) and enzyme elevations (Pocchiari, Silano, and
Sampieri 1979). In animals, this compound has been shown to be
teratogenic, embryotoxic, carcinogenic, and cocarcinogenic
(Neubert and Dill man 1972; Courtney 1976; Kociba et al. 1976,
and Kouri et al. 1976). It has been established that under
certain conditions ', 7;3 ,7 ,8-TCDD tan -enter—t-he--hwnan body f.ro.m a
2,H,5,7-T-treated food chain and can accumulate in the fatty
tissues and secretions, including milk (Galston 1979). The
available data indicates significant risks associated with the
use of dioxin-contaminated herbicides. Based upon the work of
Van Miller et el., estimates done by accepted risk assessment
procedures indicate that daily human exposure to 0.01 ug (10 ng)
of 2,3,7,6-TCDD is the dosage expected to result in "incipient
carcinogenic!ty". Additionally, daily human exposure to 4 ug
2,3,7,6 TCDD would be expected to result in a shortened
lifespan, and daily exposure to 290 ug would result in acute
toxicity (Colston 1979)."
In addition to the dioxin contamination in the soil being worked
with there may be several other chemicals of concern encountered
in decontamination or sample packaging. These chemicals
include:
1. Inhibited chloroform 1,1,1. Trichloroethane. The TLV-TWA
for this chemical substance is 350 ppm. This volatile substance
can enter the body t-hru inhalation," ingestion and contact and
may cause a variety of effects beginning with headache, general
lassitude, poor equilibrium and eye or skin irritation.
2. Ethyl Alcohol. The TLV-TWA for'this chemical is 1,000 ppm.
This volatile substance can enter the body thru inhalation,
ingestion and skin contact and may cause a variety of effects
beginning with eye irritation, headaches, drowsiness, nausea and
vomiting.
-------
3. Vermiculite. The vermiculite packaging materiel is a
potential eye irritant and contains a small percentage of
asbestos. Asbestos fibers larger than 5.0 microns can represent
a cancer risk if inhaled.
The very nature of the business operated by the spiller who
created the St. Louis area dioxin contamination problem
indicates that there is a substantial opportunity for the
presence of a wide variety of additional organic chemicals in
the contaminated soil where 2,3,7,8-TCDD has been confirmed.
Previous investigations have already disclosed the presence of a
number of volatile organics, PCB's and some of the process
chemicals from which the dioxin was created. Analyses have not
been conducted of the research areas to either confirm or
discount the presence of other contaminants.
Personnel Health Monitoring
•
Physical Examinations - Personnel working on any suspected or
confirmed site must have completed a baseline physical exam
meeting the guidelines listed below for hazardous waste work
within 12 months prior to the site work. Personnel who have not
had such a physical may not be authorized to enter the site.
Physical Examination Guidelines for Hazardous Waste Vork
ried'Jcal/Occupyffr^nal --Quest-icmnair* . ..
Full Physical Examination by Physician-
Vitals (height, weight, blood pressure, pulse)
Screening Audiametric Test with Otoscopic Exam for Wax
Pulmonary Function Test (Spirometry)
Resting ECC, Reed by Board-Certified Cardiologist
Chest X-Fay (PA) Read by Board-Certified Radiologist (once
per 2 year*)
Laboratory Analysis
•Blood Chemistry Profile
• Complete Blood Count with Differential
•
Urinalysis with Kicrospoic Examination
Zinc Protoporphyrin
Urinary Arsenic
Urinary Mercury
Urinary Cadmium
-------
•Blood Chemistry Profiie
Calcium Direct Bilirubin SGPT
Phosphorus Indirect Bilirubin CCT
Clugose Alkaline Phosphatase Creatinine
BUN LDH Tri£lycerides
Uric Acid SCOT Osnolality
Cholesterol Sodium Bun/Creatinine
Ratio
Total Protein Potassium Globulin
Albumin Chloride A/G Ratio
Total Bilirubin CPK Beta Cholesterol
(LDL)
To gain entry to the research area all researchers shall provide
a statement from their examining physician to the MDNR that
there are no medical impairments which would prevent use of
respiratory equipment for performance of work under the
conditions at the research area.
-Personnel -Pret-ective Equipment
i
Respiratory Protection:
Personnel within the contaminated area are required to wear a
f_uli face respirator equipped with combination organic vapor,
high efficiency participate cartridges or canisters. Corrective
vision inserts are required for those who normally wear
glasses. No facial hair interfering with the face to mask seal
will be allowed. Researchers must pass a qualitative fit test
for their chosen mask before entering the research area.
George Carson, a Certified Industrial Hygienist with NIOSH, in a
January 15, 1983 release stated:
"If the sites to be investigated are similar to those at Times
Beach, Missouri, in that the contaminant was sprayed on the soil
along with waste oil some ten years ago, during which time the
potential for Dioxin. to volatize has been virtually eliminated
and the fact that the only potential exposure to Dioxin is by
disturbing and aerosolizing the soil particles, to which it may
be attached, we would recommend that adequate respiratory
protection would be afforded by the. use of air purifying
respirators in a complete respiratory protection program."
-------
Dermal Protection
1. Personnel within the contaminated area are required to veer
a full-body, one-piece coverall suit manufactured from
saran-coated spun bonded olefin. Uncoated spunbonded olefin may
be worn during certain conditions (see Section 3 of this plan,
Health Monitoring).
In a test conducted by the Southwest Research Institute in San
Antonio, Texas, it was confirmed that Tyvek, a spun bonded
olefin, consistently stopped particulate permeation.
2. All personnel working on site are required to wear an inner
glove of lightweight PVC or latex accompanied by an outer glove
of buna nitrile rubber. External work gloves of cotton or
leather which provide additional thermal protection, enhance a
worker's grip, and protect rubber gloves from physical damage
may be used to meet individual preferences.
3. Clove to coverall seam and boot to coverall seams will be
sealed with duct tape to prevent dirt from entering at those
areas. In the event clothing is ripped or torn, the clothing is
to be removed and replaced at once.
t4. In compliance with OSHA standard 1910.136, all personnel
will wear neoprene steel-toed, steel-shanked work boots.
5. In compliance with OSHA standard 1910.135, hard hats will be
worn when operating overhead equipment. -
6. In the event of direct skin contact, the affected area is to
be washed immediately with soap and water. All clothing
provided for on-site use is to be considered disposable and
handled as contaminated trash before personnel may leave the
designated work area.
De contamination
Cross contamination must be cleaned from all equipment before on
site storage by using a thorough water rinse at the wash station
provided. Additionally workers' boots, gloves and any other
heavily contaminated articles must be cleaned with the same
procedure before going into the support area.
All equipment and gear must be thoroughly steam cleaned or
washed with soap and water then rinsed before leaving the site.
Decontamination must.be suf f icient';to prevent transport of
contamination off site.
Personnel decontamination will consist of removal of
contaminated clothing with its subsequent storage in 55-gallon
metal drums with ring seal lids. Footwear may be temporarily
stored in the contamination reduction area.
Following removal of clothing, personnel shall take a thorough
cleansing shower prior to redress and departure from the site:
-------
Procedures
In the case of physical injury to any personnel the DNR
representative is to stop all work immediately and provide Tor
medical attention for the injured person as the highest
priority. A list will be posted by DNR with the following
emergency numbers:
Times Beach Police
Eureka Fire Department
Ambulance Service
Stress Monitoring
There are no known personnel exposure routine monitoring
procedures for 2 ,3 ,7 ,BrTCDD. Protective clothing standards and
decon procedures are established and enforced to minimize the
potential for exposure to this contaminant.
In site specific situations where other contaminants may involve
'additional screening, monitoring services and equipment are
available. Where site history indicates that problems may
exist, specific guidance for upgrading personnel monitoring will
be provided in the site study plan.
Weather Variations: During cold weather, employees are provided
with insulated safety footwear and oversized impervious suits to
facilitate additional clothing required for thermal protection.
It is recommended that during site operation periods where
ambient daily maximum temperatures exceed 70 degrees Fahrenheit,
the researchers should implement measurements of Wet Bulb Globe
Temperature Index (WBCT) as described in TLVs, Threshold Limit
Values for Chemical Substances in Work Air Adopted by ACCIH for
1962. Due to the levels of protective clothing worn by all
personnel, the researchers should calculate the WBCT at 1 hour
intervals whenever the daily maximum temperature exceeds 70
degrees Fahrenheit. All measurements and calculations should be
recorded. Where possible, work hours are to be changed to
cooler periods of the day to avoid unnecessary heat stress on
personnel.
From the heat stress monitoring data that has been collected
during the summer investigations, the following guidelines have
been suggested concerning the work/rest regimen for dioxin
samplers wearing Level C protection:
1. With WBCT's from 75-65 degrees Fahrenheit, workers shall not
be allowed to work more than one hour without taking at least a
15 minute break.
2. With WBCT's from 85-95 degrees Fahrenheit, workers should
not be allowed to work more than H5 minutes without at least a
15 minute break.
-------
3. With VBCT's exceeding 95 decrees Fahrenheit, workers should
not be allowed to work more than 15 minutes without at least a
15 minute break.
n. Individuals definitely have variable limits as to the amount
of heat they can tolerate. Employees should be informed that
they are responsible for their own physical well-being.
Monitors can only judge heat stress by what they see. Only the
individual knows how he feels and what his limits are.
It is recommended that at the end of each work period the
workers shall remove their protective clothing and do the
following:
1. Take their oral temperature and proceed as below:
a. 99 degrees Fahrenheit - no action.
*
b. 99 degrees Fahrenheit and 99.7 - cool them off with a
water spray and do not allow a return to work unless their
temperature is 99 degrees Fahrenheit at the end of the rest
period..
c. 99.7 degrees Fahrenheit and 100.U - cool them off with a
water spray, double their rest period, and do not allow a return
to work unless their temperature is 99 degrees Fahrenheit. If
liBdt'-exhaustien or* heat stro-k-e—symptoms are present., _.s_e.e.k
medical attention.
d. 100.4 degrees Fahrenheit - cool them off immediately
with a water spray, begin standard first-aid procedures, and
seek medical attention.
2. Check each worker carefully for symptoms of heat illness and
react accordingly.
3. Drink slowly, cool but not cold, eight (8) ounces of water,
six (6) ounces of water plus two (2) ounces of a natural
unsweetened fruit juice, or eight (6) ounces of 0.1% saline
solution. They can drink more if desired. Do not use Catorade,
it depletes potassium.
Personnel Training
All personnel shall be provided with a copy of this plan and
they must be familiar with its contents before entering the
research area. All personnel must be fully familiar with the
use of respiratory protective devices and protective clothing.
Site Safety
1. Access - Only authorized personnel conducting business will
be allowed to enter Times Beach. Personnel must sign any
release required by the City and follow all rules established by
the City. Personnel must use designated travel routes only.
2. No one shall be permitted to eat, drink or smoke within the
site, and shall thoroughly wash hands and face with soap and
water before doing so outside the site. Individuals must wash
-------
3. Under no conditions are personnel to be authorized to enter
any alleged contaminated site without a work partner and one
additional person stationed outside the contaminated area in
constant visual or radio contact with the work party.
H. In order to facilitate removal of any injured personnel, the
site vehicle must must be parked near to the research activity
and facing the support area at all times.
ACKNOWLEDGMENTS
Content of this plan is modified from a document prepared by the
USEPA Region VII. The MDNR wishes to acknowledge the following
people:
William Keffer, USEPA Lab Region VII
Daniel Harris, USEPA Lab Region VII
Dennis .Howard, Veston TAT Region VII
Dr. George A. Carson, CIH, N10SH Region VII
Dr. George D. Kleopfer, USEPA Lab Region VJI
Dr. Steven Gertz, Roy P. Ueston, Inc., Vest Cheater, Penn.
REFERENCES
Occupational Safety and Health Administration, 2981 (Rev.).
OSHA Safety and Health Standards. General Industry Standards.
2206. United States Department of Labor, Washington, D.C. p.
297.
United States Environmental Protection Agency, 1962 (Rev.).
Interim Standards Operating Safety Guides. Washington, D.C.
Sec. 5, pp 1-12.
Carson, George A., Ph.D., CIH. Jan 1983 Statement of
Respiratory Protection. NIOSH Region VII release. Kansas City,
Missouri. 1 p
Chemical & Engineering News, June 1963. Dioxin. C&EN,
Washington, D.C. 66 pp
Hageman, John P., Kay 1962. Evaluation of Anticontamination
Clothing Material to Protect Aeainst Radioactive Contamination.
Southwest Research Institute. San Antonio, Texas, 7 pp
-------
APPENDIX D
TEST SITE DESCRIPTION
-------
TIMES BEACH
location
Legal Description: Floodplaln of the Meremec
River, principally W 1/2. Sec. 32,
and I 1/2, E 1/2. Sec. 31, 7.44 N.,
N., R. 4 E., 5th P.M.
Manchester Quadrangle
St. Louis County
Latitude: 38° 30' 33"
Longitude: 90° 36' 08"
Population 2,061 (None at Present)
Accessibility
Times Beach can be'entered by any of three routes. Interstate 44 exits
onto a northern outer road which goes Into the City. Lewis Road from the
north also connects with the 1-44 outer road. The third access route is
from the City of Eureka south of 1-44 onto Times Beach Service Road.
History -Summary-
•i- - -
In June 1972, a dty ordinance was passed to contract with a waste oil
hauler to spray the roads for dust control. Apparently all of the grevel
streets were oiled that sunmer twice and a third time where needed, as re-
called by residents. In 1973, the roads were again sprayed by contract.
The agreement was to have approximately ten miles of road oiled. Five
additional streets had been paved so less oiling was done that year. EPA
sampled the roads and right-of-ways In November and December 1982, and
found 2,3,7,8-TCDD levels up to 127 ppb. In December 1982, the Meramec
River flooded the town. EPA sampling in January 1983 following the flood
showed that the contaminated soil remained quite immobile throughout the
flooding. On February 22, 1983, the EPA Administrator announced a $33
million pledge from superfund to purchase the Times Beach property under
a relocation plan to be developed and implemented by the Federal
Emergency Management Agency (FEKA). EPA is planning to have a feasi-
bility study conducted to determine the scope and costs of cleanup
alternatives. The city is on the National Priorities List.
Site Description (see maps) -
Times Beach 1s principally bounded by the Meramec River, Interstate 44,
and the Burlington Northern Railroad tracks. Being 1n the 100-year
fjoodplain, the area is relatively flat. The majority of the city's 28
miles of paved and gravel road, shoulders, and ditches are contaminated.
Maximum levels of 2,3,7,8-TCDD are shown on the city map. Contamina-
tion has been found down to at least two feet below the surface. The
City of Eureka, population 3,862 lies immediately to the south and west
of Times Beach. None of Eureka's streets were oiled and no contamination
has been found within the city. Results of all groundwater sampling in
the area have been negative.
-------
Geologic and Soils Description
Times Beach is on an alluvial setting, underlain by alluvial silt to a
depth of more than 5 feet. Below the alluvial silts; sand, gravel, and a
mixture of silt, sand, and clay would be expected to a depth of from 40
to 50 feet where bedrock is encountered. The water table would be expect-
ed to be about at the Meramec River level, between 10 and 20 feet from
the surface in most of the area.
The alluvial silt has a relatively low permeability and would be expected
to be wet natured in that 1t does not readily or rapidly drain water.
Due to this and the screening effect of the silt, it 1s not likely that
soil particles contaminated with dioxin would move down into the water
table. ~
It can be assumed that the contaminated material consists of road bed
material plus native soil where the contamination has eroded into the
ditches. .
-------
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-------
TIMES BEACH, MISSOl Rl
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REGION 7 - KANSAS CITY
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-------
TIMES BEACH DIOXIN RESEARCH FACILITY
One oT the conclusions of the Missouri Dioxin Task Force
was that further research needs to be conducted to determine
dioxin destruction methods. As a result, the Missouri
Department of Natural Resources (MDNR) assisted in
establishing a dioxin research group. This group consists of
governmental agencies (MDNR, EPA, Missouri Division of
Health), industry and the University of Missouri. This group
then concluded that in-situ research at Times Beach, Missouri,
would be of great help in determining destruction methods for
dioxin contaminated soils. Based on the group's conclusions,
the MDNR solicited proposals for conducting in-situ research
on dioxin contaminated soil at Times Beach, Missouri,
beginning during the summer of 198M.
The objectives of this project are twofold. The first is
to isolate those technologies that have potential to detoxify
dioxin contaminated material. The second objective is to
compare different successful technologies for application to
solve the crisis. Once potential technologies have been
identified, long-tern funding mechanisms can be looked at for
those processes by the regulatory agencies.
Laurel Road in Times Beach, Missouri, was selected as the
area for conducting in-situ dioxin destruction
investigations. The street is bounded on the west and east
sides by Orchid Drive and Beach Drive, respectively (see
map). The concentration of dioxin in soils is in the range of
100-300 ppb.
-------
The MDNR, acting on the suggestions of the research croup,
set up the program by excavating a two block portion of Laurel
Road. The soil and gravel were homogenized by mixing them
thoroughly. The soil was then screened to remove the larger
gravel and rocks, laid back into stainless steel bins six feet
by eight feet by two feet deep and compacted back to the
original density. A bottom liner was installed to drain
liquids seeping through the soil. Water and power outlets are
provided at each plot. An on-site soils laboratory is
available. Security arrangements such as lockers and a
•
decontamination facility are also available. A full-time MDNR
on-site coordinator is available to oversee operations and
ensure that security is maintained. Emergency services are
also available.
A comprehensive sampling and analysis program was
conducted to determine initial reference levels prior to
implementing research proposals. The plots are currently
available for in-situ investigations. The group has decided
that at least three units be made available per research
group. This would give the researcher an opportunity to
create a standard reference unit and vary parameters as
necessary in the other two units. Standardized soil could be
made available for in-house research, if the researcher
demonstrates that he has the resources for in-house management
of dioxin.
-------
\
- During the investigation, close monitoring will be
maintained by the research group to assess the progress. At
the end of the investigation, the group will review the
project's accomplishments and will take the appropriate
actions such as disbursing the information or recommending
that the process be applied at a given site.
Funding mechanisms for the program are being evaluated.
It is anticipated that the majority of the proposers would be
self-funded industrial entities. The cost for leasing a plot
(set of three units) is $16,500 to be paid initially. This
one time fee is essentially the cost of preparation of the
plot along with sampling and analysis costs before and after a
research project is complete. This sampling and analysis will
provide MDNR verification of a project's success.
To date, three sets of plots have been leased to companies
doing various types of research. The three companies are
Monsanto, doing fate and transport studies on dioxin in the
environment; Agro-K Corporation, doing tests on enzymatic
degradation of dioxin; and PPM, doing two separate degradation
studies using a sodium based compound and biological
organisms. In addition, two experiments have been performed
at the facility without the use of the research plots. J. M.
Huber Company brought in a pilot version of their Advanced
Electric Reactor to incinerate contaminated soil, and Agro-K
sponsored research by the RMC Corporation where a dilute
solution of hydrezine was applied to contaminated soil.
Following is a brief description of each of these projects.
-------
flonsanto; The purpose of Monsanto's research is to determine
how dioxin in the environment behaves. They hope to establish
whether dioxin gradually degrades naturally. First round
sampling on their plots is inconclusive at this time.
Agro-K; Currently, Agro-K is applying a solution of enzymes
to their plots to determine if the enzymes are capable of
digesting dioxin. First round sampling on this process is
inconclusive. Agro-K has also sponsored research proposed by
RMC Corporation to determine if a dilute solution of hydrazine
, • •
applied to the soil is effective at destroying dioxin.
Hydrazine solution was applied to trays of soil over a period
of several days. First round results indicate no significant
reduction in dioxin levels. A second round of treatment with
hydrazine solution is currently underway.
J. M. Huber; The Advanced Electric Reactor, which was
demonstrated in November of 196M, successfully reduced the
level of dioxin in contaminated soil to well below the 1 ppb
safety level designated by the Centers for Disease Control
(COO. The original level of contamination in the soil was
120 ppb.
PPM; This company's research using both a sodium based
compound and biological organisms has also been inconclusive
to date.
-------
APPENDIX E
OPERATING LOGS
-------
SH1RCO MOBILE PILOT
' OPERATING LOG
USTOMER: ~) r A 1
TDIE METER J<* 7/HRS Q_
OPERATOR:
TIME
OF
DAY
(HR)
BELT SPEED
SETTING
BELT SPEED
(oin/rev)
l-Zonc At
2-Zone A}
3-Zone Bl
TEMPERATURES (*F)
-Zone D2
5-Dtsc.Cht
6-Furn.Exh.9-Scrub.Exh.
'-Aftbrn.
8-Aftbrn Exh
10- 2 A s>' Zone A RUHR Volts.
12- it , , 3 .• ' ' Zone B KUHR
POWER
Zone A HEPC
T
oups
Zone D HEPC
Volts
amps
I.
PRESSURE (IN. WC)
FURN. DRAFT
FURN. EHI.
AFTER3UPJJER
AFTB?»I. EXH.
SCRUBBER d P
COMB. DLR OUT
FURN. COMB AIR
AFTBRN. COMB. AIR
JET STATIC
Zone
Zone
Zone ;
Zone It
tone
SC BURNER
NAT. CAS
SCWJBBCT
VENTURI
H20
TOWER
H20 (PS1)
:S
tj
HtCC |3Z
4'7-
IL-CL'
IxQ^
H >
AI
1^
((>*(
c'' 6
C
.cc\
/*.<>
140- 1
50
(.•C
4t
-
1ST?
467.
II
S-
c
Gt
/C
l.U
7 (-» ^
*// .v
V
.1
-------
SIIIRCO MOBILE PILOT
OPERATING tOC
STOKER:
NNINC TDK HETER
MRS 0
DATE:
OPERATOR:
/o
IME
if
>At
HR)
BEU STEED
SETTING
BELT SPEED
(ain/rev)
-Zone Al
2-Zon« A2
3-£one Bl
TEMPERATURES (*F)
-Zone 02
5-Disc.Cht
6-Furn.Exh 9-Scrub.Exh.
7-Aftbrn.
B-Aftbrn Exh
10-7fl
Zone A KURD
n=-
Zone * KWHR
1
POWER
Zone A HEPC
/olts I a-nps
Zone n HEPC
VSTts
PRESSURE (IN. WC)
FURN. DRAFT
FURM. EXH.
AFTERSUPJiER
AFTBP.M. EXH.
SCRUBBER 4 P
COMB. BLR OUT
FURN. COMB AIR
AFTBRN. COMB. AIR
JET ST
Zone 1
Zone
Zone 3
JIC
Zone
-------
-------
SIIIRCO MOBILE PILOT
OPERATING LOG
CUSTOMER:
RUNNING TDK METER
MRS 0
DATE:
OPERATOR:
/
+.O
TIME
OF
DAT
(HR)
ELT STEED
SETTING
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SIIIRCO MOBILE PILOT
OPERATING LOG
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SltlRCO MOBILE PILOT
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MRS
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BELT SPEED
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SIIIRCO MOBILE PILOT
OPERATING LOG
CUSTOMER:
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DATE: <-
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« I
TIME
or
DAT
(HR)
BELT STEED
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SH1RCO MOBILE PILOT
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CUSTOMER:
RUNNING TDE IIETER
DATE: VUN l\
OPERATO*: jW, i
TIME
OF
DAT
(HR)
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SHIRCO MOBILE PILOT
OPERATING LOG
CUSTOMER:
RUNNING TIME METER
HRS
DATE:
OPERATOR:
TIME
or
DAY
-------
H.OU
HE
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MATERIAL
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COKHEOTS
.
•
-------
APPENDIX F
UNIVERSITY OF MISSOURI, COLUMBIA
LABORATORY ANALYSIS REPORT
-------
Environmental Trace Substances Research Center
Route 3 Sinclair Road
UNIVERSITY OF MISSOURI SSX
August 8, 1985
Robert J. Schreiber, Jr.
Director
Division of Environmental Quality
Missouri Department of Natural Resources
P.O. Box 1368
2010 Missouri Blvd.
Jefferson City, MO 65102
Dear Mr. Schrieber:
The results of tetrachlorodibenzo-p-dioxin residue analysis of three
samples are enclosed. Please feel free to contact me for any questions you
have regarding these analysis.
Sincerely,
. Kapila, Ph.D.
Group Leader
SK:ds
Enclosure
COLUMBIA KANSAS CITY ROLLA ST. LOUIS
«n «qu*l ootxxlinty nstKuien
-------
Customer:
Robert Schreiber, Jr. - DNR
ETSRC ID:
85070717 - 85070719
The attached pages, have been checked and vetitled.
Date
Date
Dace
-------
, sis summary "*et_
ML 0
5-0276
5-0277
5-0988
5-0276
-
ETSRC t
85070717
85070718
85070719
8507071 7Du
Reagent
Blank
-
•
'
•
SML Wet
Weight
10.0
10.0
• 10.0
i 10.0
-
•
• . -•
•
Cone
R/KC
<1.0
306.0
<1.0
<1.0
<1.0
Z Rec.
70.9
89.0
104.3
99.0
90.1
:.
Ion Count (Area)
257
B
99438
1190
B
B
-
•
. •
320
B
177182
B
B
B
-
i
322
135
229828
B
B
B
•
•
328
1289
2946
1601
2083
1403
332
3329
4668
5145
4631
4409
334
4363
5507-
6403
6093
5546
Ratio
320/322
- •
0.77
•_-
-
-
•
Comments
Data File:
TCDDSMLl
Date File: TCDDSML
Data File: TCDDSML
Data File: TCDDSML
Data File: TCDDSML
•
-------
RESULT SUMMARY
Analyte: 2,3,7,8 Tetrachlorodibenzo-p-dioxin
Sample Matrix: Soil and Soil + Water
Sample Source: Missouri Department of Natural Resources
Date Analyzed: August 5, 1985
Analyst: S. Kapila
Sample * ETSRC ID 2,3,7,8 TCDD Cone.
85-0276 85070717 <1.0
85-0277 85070718 306.0
85-0988 85070719 <1.0
Reagent Blank Analysis
Duplicate Analysis
85-0276 <1.0
85-0276 Duplicate <1.0
Z Rel. Dif. 0.0
-------
Environmental Trace Substances Research Center
INITIAL QC CALIBRATION DATA
.
2,3,7,8 Tetrachlorodibenzo-p-dioxin
Quantltation Mass 322
2,3,7,8 Tetrachlorodibenzo-p-dioxin
Cl-37
•
•
.
i
i
i
I
.
t
. RT
17. 47
17.47
-
•
R 150
3385
26. 942
b
. R 400
10199
123111
'
b
R 1000
28395
.
•
c
~RF
25.4
24.6
26.9
•
ccd
0.9997
Notes:
a RT Is the average . retention time
b R is the response at the level indicated
J.150, 400 and 1000 picograms)
c ' RT is the average response factor
d CC is the correlation coefficient of the multilevel calibration
data for each compound .
1 500 picograms
2 100 picograms • ,
-------
1C5-
INITIAL CALIBRATION
1
I :
• i
'..I. ..
: _ L __
i
t p
..i.l
•|:|
1 I ['
........
..DATE
1 '1. V
"••[li1
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: "
JA
A
ITITATI
ANALYS
lg.
2,
T1
: '; j
ON
T:
'8.
! 1
VIA
. £
> -
SS
.K
A
• '
' ! t
: 3
.,,
1 l
UR-i
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22
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i • ' !
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i . i
1 ! .
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10
2
10-
AMI. INJ (PICOGRAMS)
-------
Environmental Trace Substances Research Center
ONGOING QC DATA '
Name
2 ^,7,8 Tetrachlorodibenzo-p-diox
'
.
...
a
RF
Aup.. 5:85-1
.n 28. A-
i
RF on Given Date
A
Aug. 5:85-1
28.5 •
•
-
D
•
•
•
C
•
-
D
,
E
Notes:
RF is response factor from Che most recent
initial calibration.
Report the date the RF was obtained, and the data file name.
Use letters (A, D, C, etc.) for more than one data point on a
'single day.
-------
Hnvironmcn tnl Trace Substances Research Cetitcr
IA - CC/N5 PERFORMANCE STANDARD - D«caf luototrlph«ny lpho»phiQ«
Data 8/5/85 Run no. DFTPP1 An*ly»t SK
-/•
31
68
70
127
197
198
199
273
363
441
442
443
Ion Abundanc* Crit*ri*
30-601 of MIS 198
!«•• than 21 of iu«« 69
•
!«•• than 21 of- BAB* 69
40-60X of «*•• 198
ICCB ttvaa IX of »«•• 198
b«i« p«*k, 1001 r«l«ci.T* abundAoe*
3-91 of MSC 198
10-301 of •*•• 198
greater than 1Z of m*»t 198
!••• thaa »*•• 443
gr«*car thaa. 40X of •*•• 198
17-23X of »..• 442
SPEC /
A4.2
0
0
42.3
0.75
100
6.8
21.6
2.2
14.9 ^^
x/9.3
62.4
19. 1^^
^x^^ 11.9
SPTC /
•
SPEC 1
•
Coaa«nta i
•
Column description 30 M. _DB-5
T««p«r«tur. 120-260°
Scan Time 0-5 sec.
laoth* ma 1
Tailing Factor
8 per n>in.
Base/Neutral
Benzidine
Acids
Pcntachlorophenol
-------
APPENDIX G
PERSONNEL HEALTH MONITORING DATA
-------
RIEDEL
ENVIRONMENTAL
SERVICES
Health Line
E MEAUM S£*VC£S
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-------
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ENVIRONMENTAL
) SERVICES
Employee Name
Health Line
KA4JM SEtWCCS
A Sonrtce of SI Loult Univeriity Medical Center
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-------
ma RIEDEL
ENVIRONMENTAL
SERVICES
Employee Name
Date "7/9/36 Project Site
Health Line
. >«*.TH SERVCCS
t1 A Service ol St Louis University Medical Center
Medical Staff
Time .
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-------
D«te
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ENVIRONMENTAL
SERVICES
Employee Name
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-------
Date
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SERVICES
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