EPA-450/4-84-014c
DRAFT
National Dioxin Study Tier 4
Combustion Sources
Sampling Procedures
By
Radian Corporation
Research Triangle, IMC 27709
Contract No. 68-02-3513
EPA Project Officer: William H. Lamason
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office Of Air And Radiation
Office Of Air Quality Planning And Standards
Research Triangle Park, NC 27711
October 1984
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This report has been reviewed by the Office Of Air Quality Planning And Standards, U.S.
Environmental Protection Agency, and approved for publication as received from the contractor.
Approval does not signify that the contents necessarily reflect the views and policies of the
Agency, neither does mention of trade names or commercial products constitute endorsement
or recommendation for use.
EPA-450/4-84-014c
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TABLE OF CONTENTS
Section
page
DISCLAIMER ........ . .. ..... . ............. ii
LIST OF TABLES .............. . ............ vj
LIST OF FIGURES ........................... v1i
1.0 INTRODUCTION .......... . ......... 7 ..... 1
1.1 APPROACH ............ ... .......... 3
1.2 SPECIAL TERMINOLOGY. . ......... ...... ... 4
2.0 PRETEST SITE SURVEYS ..................... . 5
2.1 GENERAL .......................... 5
2.2 INITIAL SITE SELECTION AND SCREENING . . ......... 5
2.3 FINAL SITE SELECTION ......... ' .......... 9
2.3.1 General. .................... 9
2.3.2 Sampling for Gaseous and Participate
Emissions from the Combustion Device and
Control Device ...... .......... 15
2.3.3 Liquid and Slurry Sampling ... ........ 16
2.3.4 Solid Sampling . .'. .............. 17
2.3.5 Soil Sampling .................. 17
2.3.6 Pretest Survey Forms and Reporting ..... . . 18
3.0 GASEOUS STREAMS - SAMPLING AND ANALYSIS ...... ....... 20
3.1 GASEOUS EMISSIONS SOURCES ................. 20
3.2 RECOMMENDED SAMPLING TECHNIQUES ............ . . 20
3.2.1 Ambient Techniques ..... .......... 23
3.2.2 Manual Techniques ............. ... 25
3.2.3 Continuous Monitor Techniques .......... 27
3.3 DESCRIPTION OF SAMPLING TECHNIQUES ............ 28
3.3.1 Manual Sampling Methods ............. 28
3.3.2 Continuous Gas Monitoring ............ 32
3.4 CLEANING PROCEDURES. ... ............ .... 33
3.5 SAMPLE FREQUENCY ....... . ......... .... 36
3.6 REPORTING FORMAT ........... . ......... 35
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TABLE OF CONTENTS (CONTINUED)
Section
Page
4.0 SAMPLING LIQUIDS AND SLURRIES .......... 39
4.1 SOURCES OF TYPICAL LIQUID/SLURRY STREAMS . . 39
4.2 RECOMMENDED SAMPLING METHODS . 41
4.3 DESCRIPTIONS OF LIQUID SAMPLING TECHNIQUES . 42
4.3.1 Tap Sampler 42
4.3.2 Dipper Sampling 46
4.3.3 The Coliwasa Sampler 48
4.3.4 Weighted Bottle Sampler 48
4.4 SAMPLE SIZE, TYPE, NUMBER, AND STORAGE 51
4.5 CLEANING PROCEDURES 53
4.6 DATA REPORTING FORMAT 56
5.0 SAMPLING OF SLUDGES, SOLIDS, AND SOILS 58
5.1 SOURCES OF TYPICAL SLUDGE/SOLID/SOIL SAMPLES 58
5.2 RECOMMENDED SAMPLING METHODS 60
5.3 DESCRIPTION OF SAMPLING TECHNIQUES 65
5.3.1 ASTM "Stopped-Belt Cut" Method (D2234-76). ... 65
5.3.2 Thief, Trier, Auger, or Bulb Sampling
of Stationary Materials (ASTM D2234-76,
D2234-76, C311-77, D346-78) 69
5.3.3 Dipper/Scoop 72
5.4 SAMPLE SIZE, NUMBER, AND COMPOSITING 73
5.5 CLEANING PROCEDURES 75
5.6 REPORTING FORMAT • • 75
6.0 ACQUISITION OF DESIGN AND OPERATING DATA . 80
6.1 INTRODUCTION 80
6.2 DESIGN AND OPERATING DATA . . 80
6.2.1 Design Data 80
6.2.2 Operating Data 84
6.3 SCHEDULE FOR OBTAINING OPERATING DATA 88
IV
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TABLE OF CONTENTS (CONTINUED)
Section
7.0 SAFETY ........... 91
7.1 SITE SAFETY 91
7.2 LABORATORY SAFETY . . . 93
8.0 QUALITY ASSURANCE AND CONTROL 96
8.1 SAMPLE IDENTIFICATION 96
8.2 THE QA/QC PLAN 96
9.0 SITE SPECIFIC TEST PLAN OUTLINE 110
Appendices
Appendix A - Draft ASME Sampling Protocol
Appendix B - Draft ASME Analytical Protocol
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LIST OF TABLES
Number
1-1
2-1
2-2
3-1
3-2
3-3
4-1
4-2
4-3
4-4
4-5
5-1
5-2
5-3
5-4
6-1
6-2
6-3
Combustion Sources Listed in Order of Decreasing
Probability as Dioxin Emission Sources
Page
2
Recommended Sample Sources for Characterization
of Typical Combustion Sources
Pretest Site Survey Form ................. 10
Parameters to Measure in Gaseous Streams ......... 22
Recommended Continuous Monitors for Testing Tier 4
Combustion Sources ................... 24
Pretest Equipment Cleaning Procedure for Sampling
Containers ....................... 35
Summary of Liquid Sampling Techniques ........... 43
Recommended Approach to Sampling Liquid Streams ...... 44
Total Number of Liquid or Slurry Samples Required
for the Example Scenario . . . ............. 54
Pretest Equipment Cleaning Procedure for Sampling
Containers ....................... 55
Proposed Results Format .................. 57
Recommended Sampling Method Applications ......... 64
Hypothetical Solid and Sludge Sample Requirements ..... 76
Pretest Equipment Cleaning Procedure for Sample
Containers ....................... 77
Proposed Results Format .................. 79
Design Data Needs for Combustion Sources ......... 81
Example Operation Parameters to be Recorded for a Black
Liquor Recovery Boiler During Performance Tests ..... 86
Example Operating and Monitoring Parameters for Control
Devices ......................... 89
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LIST OF FIGURES
Number Page
3-1 Gaseous Streams Associated with Combustion Sources .... 21
3-2 Schematic diagram of the ambient XAD sample train 26
3-3 Gas Conditioning 34
3-4 Formats for Reporting Individual Data from Stack
Samples 37
3-5 Data reporting format for dioxin analysis 38
4-1 Hypothetical Plant with Liquid/Slurry Streams 40
4-2 Schematic of Tap Sampling 45
4-3 Dipper Sampler 47
4-4 Composite Liquid Waste Sampler 49
4-5 Weighted Bottle Sampler 50
4-6 Sample Compositing Scheme 52
5-1 Generic Plant with Sludge and Solid Sampling Sites .... 59
5-2 Vacuum Ash Handling System . . 61
5-3 Air Pressure Ash Handling System 62
5-4 Limestone Wet Scrubber 63
5-5 Sampling Trough. 66
5-6 Sample Auger 66
5-7 Sample Triers 67
5-8 Sample Probe or Thief 67
5-9 Dredge Samplers (Ekman, Ponar) 68
5-10 Dipper 68
5-11 Example Sampling Grid 70
5-12 Conceptual Design of Sample Compositing Method ...... 74
VI 1
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Number
8-1
8-2
8-3
9-1
LIST OF FIGURES (CONTINUED)
Example of Label and Sample Identification Code.
Example Organization Chart
Chain-of-Custody Tag (Versar, 1984)
Outline of the Test Plan
Page
97
101
104
111
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.1.0 INTRODUCTION
This document is one component of Tier 4 of the National Dioxin Study.
The Tier 4 effort is concerned with combustion sources. The primary
objective of the Tier 4 study is to determine if combustion sources emit
significant dioxins to the atmosphere. If they do, then the secondary
objectives are to quantify these emissions and determine the exposure and
risk of living in the proximity of these sources.
This document describes the procedures that will be followed to acquire
samples from combustion sources that are sampled as part of the Tier 4
effort. The combustion sources that may be sampled are presented in
Table 1-1 and ranked according to their probability of emitting dioxin.
Because of the diversity of sources listed and because of the wide variety
of sample media (gases, liquids, solids, sludges, and soils) that may be
encountered, the exact set of sampling protocols that will be followed at
each test cannot be specified at this time. However, the list of approved
or applicable protocols for all likely media to be encountered has been
developed and is presented in this document.
The purpose of this document is to specify the applicable sampling
protocol for each media. These sampling protocols will be used throughout
the Tier 4 study. A uniform set of procedures is needed in order to
minimize variability introduced by sampling methods. Since many different
media will be encountered and a diverse number of sampling locations are
available at any combustion source, this document attempts to outline
procedures for selection of preferred sampling locations and also outlines
preferred sample acquisition methods.
The document does not present or discuss any procedure in sufficient
detail to be used as a training manual or step-by-step set of instructions
for the following reasons:
1. The sampling methods described are based upon previously developed
protocols or methods. Step-by-step instructions for each of these methods
can be found in the applicable references.
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TABLE 1-1. COMBUSTION SOURCES LISTED IN ORDER OF DECREASING
PROBABILITY AS DIOXIN EMISSION SOURCES (NOVEMBER 1984)'
Rank A Source Categories
Sewage Sludge Incinerators
Black Liquor Boilers
Rank B Source Categories
Industrial Incinerators
PCP Sludge Incinerators
Carbon Regeneration (industrial)
Wire Reclamation
Wood Boilers (firing PCP treated or salt-laden wood)
Rank C Source Categories
Charcoal Manufacturing
Wood Stoves
Mobile Sources
Small Spreader-stoker Coal Boiler
Chlorinated Organic Waste Incinerators
Lime-Cement Kilns Cofired with Chlorinated Organic Wastes
Commercial Boilers Firing Fuels Contaminated with Chlorinated Organic
Wastes
Forest Fires
Apartment House Flue-fed Incinerators .
Agricultural Burning
Landfill Flares
Residential Oil Burners Burning Waste Oil
Rank D Source Categories
Municipal Solid Waste (MSW) Incinerators
Industrial Boilers Cofiring Wastes
*&
PCP = polychlorinated phenols
*This list of source categories undergoes constant review and revision and
is subject to change.
Rank A - Large source categories (greater than 1 million tons of fuel
and/or waste burned annually) with elevated dioxin precursor
contamination or feed/fuel. These categories have a high
potential to emit TCDD, and population exposure is expected to be
relatively high compared to other source categories.
Rank B - Small source categories (less than 1 million tons of fuel and/or
waste burned annually) or source categories with limited dioxin
precursor contamination of feed/fuel. These categories have a
high potential to emit TCDD, but population exposures are expected
to be low.
Rank C - Source categories less likely to emit 2,3,7,8-TCDD.
Rank D - Source categories which have been tested three or more times.
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2. It is assumed that the testing crew already has a working
knowledge of all of the methods presented within. The document does present
sufficient information to allow the user to select an appropriate sampling
method during the development of the site-specific source test plan. The
document allows the reviewers to follow the rationale used for selection of
the location and sampling method.
Several other documents are being developed in conjunction with this
sampling procedures document. These include a QA/QC Project Plan for the
sampling effort, the Ash Sampling Program document, and site-specific test
plans. Elements of each of these are addressed briefly in the following
chapters.
1.1 APPROACH
This manual presents guidelines in several areas which are broken down
into separate sections. First, the pretest site survey is discussed. The
survey is where site-specific data is gathered prior to conducting the test.
Next, specific sampling methods and some analysis methods, are presented in
Sections 3 through 5. These are broken down based on the physical form of
the stream - gases, liquids and slurries, solids, sludges, and soils.
Design and operating data will also be necessary, and these
requirements are presented in Section 6. A general approach to safety is
contained in Section 7. Section 8 discusses QA/QC. Since a separate QA/QC
plan will be prepared as part of the overall test program, this section
presents the components of the plan but not a detailed compilation of the
various techniques and forms that will be used. Similarly, a test plan will
also be prepared for each specific source test, and Section 9 presents the
specific features that will make up the test plan.
This document attempts to be as specific as possible when discussing
techniques and making recommendations. However, so many decisions depend on
the specific layout and operations of the facility that it is impossible to
be completely specific. Obviously, there is judgment necessary that
requires firsthand knowledge of the site. These kinds of decisions will be
made in the test plan which is site specific. The purpose of this document
is to provide guidance in making these judgment.
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1.2 SPECIAL TERMINOLOGY
In the course of developing this manual of procedures for dioxin
testing under Tier 4 of the National Dioxin Study, several terms unique to
the study have been used. These terms are important to the understanding of
the Tier 4 effort and the discussion of testing procedures applicable to
combustion sources presented in the remainder of this document. Some of
these important terms are defined below.
Troika - During the course of the National Dioxin Study, a number of
dioxin analyses will be needed on a variety of samples. The EPA's Office of
Research and Development (ORD) has been given the responsibility for all
sampling and analytical guidance during the study. Furthermore, ORD will do
the majority of the analytical work on the samples. To accomplish this
task, three EPA laboratories have been chosen to conduct dioxin analyses.
These laboratories are ERL-Duluth, ECL-Ba'y St. Louis, and EMSL-Research
Triangle Park. Troika is the name chosen to refer to these three
laboratories as a collective unit.
Sample Control Center (SCC) - All the tiers of the National Dioxin
Study will be assisted in their scheduling and analysis activities by the
Sample Control Center (SCC). Versar, Inc., 6850 Versar Center, Springfield,
Virginia 22151, is the coordinator of the SCC. The SCC will provide episode
numbers, track samples through the Troika, and provide assistance in
shipping samples to the Troika.
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2.0 PRETEST SITE SURVEYS
2.1 GENERAL
Prior to testing any facility, it,is necessary to determine if testing
is feasible and justified. This will occur during the pretest activities
described in this section. The initial site screening phase will eliminate
the obviously unsuitable sites from the overall list. Then a pretest survey
of the remaining sites will be conducted to determine firsthand if the site
can be adequately tested and to gather all information necessary to prepare
a site-specific test plan.
The Tier 4 Project Plan identified eight general sample types that
should be taken to characterize a given combustion source. These are listed
in Table 2-1. One aspect of the pretest survey is to identify the specific
sampling locations to be used during the test to acquire the sample types
listed in Table 2-1, and to provide input for the selection of the
appropriate sampling method. A second aspect is to develop information for
the Sampling Control Center (SCC). The number and type of samples to be
taken at a site must be provided to the SCC prior to initiating a test.
Also, the Sample Control Center will assign an identification number based
on the number and type of samples and inform Troika of any dioxin homolog
analysis that will be needed. The QA/QC contractor also needs to know the
number and type of samples to be taken in order to prepare and provide the
correct number and type of control samples prior to the test.
The following sections describe how candidate sites will be identified
and also discusses details of the pretest site survey.
2.2 INITIAL SITE SELECTION AND SCREENING
An initial list of sites will be compiled based upon in-house data
compiled by Radian and inputs from the States and Regional EPA offices.
Sources for the data compiled by Radian will include background
information and source category survey documents for several source
categories and lists of contacts in various industries and trade groups.
The background information documents combine data on source characteristics,
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TABLE 2-1. RECOMMENDED SAMPLE SOURCES FOR CHARACTERIZATION
OF TYPICAL COMBUSTION SOURCES
Source of Sample
Precombustion Air
Feed/Fuel
Stacks (before control)
Stacks (after control)
Bottom Ash
Ash from Pollution Control Device
Quench Water Effluent
Soils (in vicinity)
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types of pollution control devices, source size, and location. Industry and
trade group contacts can be used to identify facilities which may be
interested in participating in the sampling program.
During the preparation of the initial list, the following factors will
be considered:
1. The type of combustion device;
2. The waste materials or other fuels burned;
3. The size and age of the device; and
4. The current name, address, and telephone number.
After the initial list has been prepared, the candidate sites will be
screened. The screening will focus on looking for combustion sources with
the following broad characteristics.
1. The site or combustion source should be representative of the
source category. For example, the combustion device should be combusting
the same kind of waste fuel as the majority of the source category and
should not be an outlier in terms of population and operating
characteristics (age, size, design type, operating mode, etc.). . Information
concerning specific source characteristics will be compared to broad
population characteristics which will be developed as part of the site
selection process.
2. The combustion source should be testable without a lot of special
equipment or modifications to the source. This includes appropriate
sampling locations for all streams.
3. The combustion source (and control device) should be well
instrumented. Key instrumentation would include methods to monitor and
record fuel flow (waste and auxiliary fuel), combustion air flow or firebox
oxygen content, firebox or bridgewall temperature, and steam or heat output.
The pollution control device, if present, should be instrumented with
respect to parameters which affect its operation, for example, scrubber
pressure drop, liquor flow rate, etc.
4. The owners or operators of the facility should be willing to allow
a test to be performed. This facilitates scheduling and data acquisition.
5. The presence of a pollution control device.
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After screening the remaining candidate sites of interest will be
contacted by phone to determine if they tentatively meet the characteristics
listed above. In addition, the various regional and State offices where the
sites are located will be contacted in order to gather as much additional
information on each site as possible prior to the visit. It is anticipated
that numerous sites will be dropped from further consideration based upon
this preliminary screening. The preliminary list of candidate test sites
will be constantly updated as the pretest planning and data gathering takes
place. Additional candidate sites will be added as the need arises.
Initial efforts will concentrate on identifying candidate Group A sites
(black liquor boilers, sewage sludge incinerators) and gathering data for
them. The State and regional EPA offices' inputs will be important to
provide a preliminary list of potential candidates to be screened.
Once a site or group of sites have been identified as being potential
test sites and have passed all of the preliminary checks for representative-
ness, etc., the pretest survey will be scheduled. It is anticipated that
three to four pretest surveys will be scheduled within a given week. This
requires close cooperation between the facilities to be surveyed, Radian,
and the Regional EPA office during the development of the survey schedule.
In addition, site location and accessibility are important.
At the time of scheduling, a letter will be written to the facility
operator. This letter will discuss the background and objective of the
program, survey dates and will contain a list of typical information needs
that will be sought at the survey.
Before traveling to a facility to be surveyed, survey personnel will
review all readily available information on the facility and become familiar
with the combustion device that is to be sampled and the nature of the waste
or fuel being burned. This involves understanding the design and operating
characteristics of the combustion device and the chemistry and operating
characteristics of the process generating the waste streams being burned.
An understanding of all phases of the facility operation will permit the
team leader to make an initial selection of specific sampling locations.
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Familiarization with the process is also necessary so that a checklist of
the requisite data can be developed, including temperatures, pressures, flow
rates, and variations of stream conditions with time, for the pretest
survey.
2.3 FINAL SITE SELECTION
2.3.1 General
After establishing the necessary process data needs and selecting a
tentative set of sampling points, a pretest site survey should be performed.
The pretest site survey team will typically consist of two people,
usually an engineer and field testing specialist that are familiar with all
the testing procedures and data needs and program objectives. At the test
site, the team will meet with the plant engineer to verify the accuracy of
the existing information and arrange for the acquisition of any missing
data. A large facility may have several combustion devices operating
simultaneously. The operating and design characteristics of each unit will
be discussed with the plant engineer and the appropriate unit selected. In
order to ensure that all of the data needed for evaluation of each candidate
site is obtained during the pretest survey, a pretest survey form has been
developed. A blank copy of this form is contained in Table 2-2. Prior to
the survey, the form will be partially filled out with the site specific
information available. All of this information will be reviewed with the
facility engineer during the survey, and any data gaps will be filled.
Using the information obtained from the plant engineer along with
detailed process flow diagrams, the survey team.will then proceed to select
the actual sampling sites with the following criteria in mind:
1. The sampling points must provide representative samples that can
be handled by the standard sample acquisition and analysis hardware.
2. When possible, each sampling point should provide a representative
sample of the streams. In some instances, streams from several combustion
sources at a facility may be combined. Only one of the combustion sources
may be the focus of the sampling program and, in this case, sample ports
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TABLE 2-2. PRETEST SITE SURVEY FORM
page 1
GENERAL
Plant.
Address.
P h o n e
Latitude/Longitude or UTM.
Plant Personnel
Radian Personnel
Other Personnel
.Date of Survey.
Primary Plant Contact.
Phone (If dlfferent)__
SITE DESCRIPTION
Type of process.
Operating Schedule.
Best Time to Test.
Working Hours
Shift Changes
FACILITY DESCRIPTION
Combustion Device.
Manufacturer
Start-up Date '.
Operating Schedule
Capacity (Ib steam/hr, Btu/hr, etc.)
Fuel
What Fuels are Burned.
Fuel Source(s)
Does Fuel Vary (how, how much, how often).
Potential for Fuel Contamination with Precursors.
Other Material Burned.
Typical Operating Conditions (flows, temperatures,etc.).
Duty Cycle
Are there variable operating conditions or feed materials.
If yes, what are they ,
Is the feed containing the precursors continuous or
or Intermltant
Pollution Control Equipment Present.
10
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TABLE 2-2. PRETEST SITE SURVEY FORM (CONTINUED)
page 2
Description of Ash Handling System.
Special Considerations, Operating History, Problems, Etc._.
AVAILABLE
Access
Access
Can we
PROCESS DATA
to Design Data
to O&M Logs
get bIank coples
of operator I ogs.
Data Available From the Plant Instrumentation
Combustion Device
Pollution Control Device.
How often Is data entered Into the operating log.
DRAWINGS
A separate page will be provided for each of the drawings
I Isted below.
Elevation drawing of the facility with d ImensIons shown
Plot plan of the facility with dimensions shown
Plot plans for soil and pond sampling
Map (plot plan) showing surrounding Industry
Dimensioned sketches of sampling locations and hardware (as requ
FLOW DIAGRAMS
Flow diagram of combustion
This should Include, at
fuel, waste feeds, ash,
blowdown.
device.and PCD showing sample locatlo
a minimum, sample locations for
flue gas, quench water and scrubber
LIST OF SAMPLING
MM5 I n I et
MM5 Outlet
CEM
LOCATIONS
Process Streams :
11
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TABLE 2-2. PRETEST SITE SURVEY FORM (CONTINUED)
page 3
MM5 SAMPLE POINT LOCATIONS AND DESCRIPTIONS
Sample point description
LocatI on
Stack diameter (ft) .
Gas temperature
Gas static pressure
Availability of sampling ports
Diameter of sampling ports__
Nearest upstream disturbance (ft).
Nearest downstream disturbance (ft).
Power aval lab I IIty
Scaffolding availability
Lighting aval labl 1 Ity.
Compressed air availability
Special space considerations.
Sample point description
LocatIon
Stack diameter (ft)
Gas temperature
Gas static pressure
Aval IabI IIty of samp
Diameter of sampling
Nearest upstream disturbance
Nearest downstream
Power availability
Scaffolding availability
Lighting availability
Compressed air avaI IabI I Ity_
Special space considerations
Ing ports.
ports.
(ft)
disturbance (ft).
PROCESS SAMPLE POINT LOCATIONS AND DESCRIPTIONS
Sample Point Description (what Is sampled, etc.)__
LocatIon
Process Stream
Type of Material (gas,
Approximate % V/ater
Physically, what Is the sampling hardware(port, valve, nothing)
and what Is the size of the hardware
liquid, slurry, sludge, solid).
Approximate Temperature and Pressure.
12
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TABLE 2-2. PRETEST SITE SURVEY FORM (CONTINUED)
page 4
Sample Point Description (what Is sampled, etc.).
LocatI on
Process Stream
Type of Material (gas, liquid, slurry, sludge, solid) "
Approximate % Water
Physically, what Is the sampling hardware(port, valve, nothing)
and what Is the size of the hardware
Approximate Temperature and Pressure.
Sample Point Description (what Is sampled, etc.).
Locat Ion
Process Strea m
Type of Material (gas, liquid, slurry, sludge, solid)
Approximate % Water.
Physically, what Is the sampling hardware(port, valve, nothing)
and what Is the size of the hardware
Approximate Temperature and Pressure.
Sample Point Description (what Is sampled, etc.).
Locat I on
Process Stream
Type of Material (gas, liquid, slurry, s I udge, sol Id) ~
Approximate % Water.
Physically, what Is the sampling hardware(port, valve, nothing)
and what Is the size of the hardware
Approximate Temperature and Pressure.
Sample Point Description (what Is sampled, etc.).
LocatI on
Process Strea m \
Type of Material (gas, liquid, slurry, sludge, solid)
Approximate % Water _]
Physically, what Is the sampling hardware(port, vaIve, noth I ng)
and what Is the size of the hardware
13
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TABLE 2-2. PRETEST SITE SURVEY FORM (CONTINUED)
page 5
Approximate Temperature and Pressure.
CONTINUOUS MONITORING CONSIDERATIONS
LocatI on(s)
Gas Temperature.
Gas Pressure.
Length of sample line necessary.
Expected concentration ranges:
CO:.
C02:.
S02
NOx:.
02:_
THC:.
MOBILE LAB AND OTHER SUPPORT FACILITIES
Space Available (where, how much, show on plot plan drawing).
Avallable UtIIItles
Electrical (voltage, amperage, phase for each circuit).
Other.
Generator operation OK?
Area for temporary equipment and sample storage.
Other Support Facilities
Phone available
Number.
Access to Copier
Access to Office Space.
SPECIAL REQIREMENTS AND SITUATIONS
Scaffolding Requirements
Other Special Access Requirements.
Special Safety Requirements.
What Is required to obtain access to plant (letters, agreements,
Confidentially Issues.
Other.
.14
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downstream of where the streams combine will'be of no value. Provisions for
installing additional sampling points will be discussed with plant personnel
at this time.
3. The sampling site must have a reasonably favorable working
environment. The survey personnel must consider what the temperature and
noise levels are in the sampling areas; if protection from rain, snow or
strong winds exists; and whether scaffolding, ladders, pulleys, etc., exist
and are safe.
The identification of support facilities and services is an essential
aspect of the site survey. In an effort to minimize the requests made upon
the operators and to minimize scheduling problems for these support
services, it is desirable that the on-site laboratory operate completely
independently of external support facilities. The pretest site survey form
will specifically request this information; e.g., the availability of
electrical service.
The results of £he pretest site survey must be sufficiently detailed so
that the correct process stream, the proper sampling location and, the
appropriate methodology will be completely defined prior to arrival of the
field test team at the source site. For this reason, the following sections
detail information that will be obtained during the survey for each sampling
location.
*
2.3.2 Sampling for Gaseous and Particulate Emissions from the Combustion
Device and Control Device
During the pretest survey, the surveyor will perform the following
steps:
1. Trace the flow of combustion gases from the combustion device
through the heat recovery devices and control devices. This involves a
physical inspection of the ductwork from the combustion device to the stack.
2. Locate and itemize control devices, stacks, and sampling
locations.
3. Record the physical parameters of the gas streams in as much
detail as possible. For example, these can include temperature pressure,
physical nature, flowrate, flow disturbances, etc.
15
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4. Prepare sketches of the overall area. Include elevation and plot
plan with dimensions.
In performing the pretest site survey, the crew will verify the
existence of the following requirements for stack gas sampling:
1. The sampling ports: To accommodate the sampling probe, the port
must have an opening of at least 2-1/2 inches. A 3-inch nipple welded to
the stack is usually the best way to obtain access.
2. The test platform: The size of the test platform, which supports
the sampling equipment and test personnel, depends on the length of the
probe to be used. However, a platform of normally 5 ft x 4 ft is usually
adequate. Also, there should be a clearance of 1.5 to 2.0 stack diameters
out from the sampling point to accommodate the sampling probe.
3. Electrical power: Power is required for the probe and oven heaters
and for the vacuum pumps. To operate the entire system, a total of two
20-amp circuits adjacent to the sampling locations and one 20-amp circuit by
the mobile Jab parking area are required.
2.3.3 Liquid and Slurry Sampling
The liquids and slurries that may have to be sampled include auxiliary
fuels, waste materials that are combusted, make-up water, scrubber water,
ash sluice water, and ash slurries. The number and type of liquid or slurry
streams that have to be sampled will differ from site to site.
The same general criteria for locating a gas sampling point can be
applied to locating sampling sites for liquid samples. A review of those
criteria and procedures is contained in Section 2.3.2 of this chapter.
While the site selection criteria for gas and liquid sampling are
generally the same, the test personnel must be aware of the problems
associated with the sampling of liquids and how these factors affect the
choice of a sampling site. Two factors will affect the selection of a
sampling site for liquid/slurry streams:
1. Stream homogeneity: This is the most important problem that must
be addressed by the site survey crew. Unlike gas streams, which mix fairly
evenly, liquid streams tend to be more stratified because of lower thermal
agitation and higher fluid viscosities.
16
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2. Stream flow rate: Large, slow-moving streams will offer more of a
chance for stratification to occur. This factor is especially important in
large pipes or open sluices and ditches.
Based on the stream properties, primarily whether it is a homogeneous
liquid or a slurry, the site survey should determine if the sampling
provisions are sufficient. For example, for a slurry stream it should be
located in a well-mixed zone such as after a pump. This decision will vary
from site to site and should be made on the basis of good technical
judgment.
2.3.4 Solid Sampling
Solid input and output streams in most combustion devices consist of
wastes used as fuels, bottom ash, and collected particulates. These solids
range from very fine powders to very coarse lumps depending upon the
combustion device and the control device. This variation in sample
consistency influences the sampling technique to be used, which must be
established in the pretest site survey. For purposes of the pretest site
survey, therefore, the following questions must be answered:
1. Can the material be sampled as it enters or leaves the process, or
must it be sampled in its stored or piled form?
2. If material can be sampled as it enters or leaves the process,
what is the nature of the conveyor system (belt, worm screw, pan), and what
is the closest available sampling location to process entry?
3. What is the consistency of the material (powder, coarse grain,
lump), and what is the apparent (visual) variance within this consistency?
4. What is the approximate size of the storage reserve, and what is
the method of access to said reserve?
2.3.5 Soil Sampling
Soil sampling will be conducted at all sites selected for full scale
testing. As part of the pretest survey, a plot plan of the facility will be
obtained. This' plot plan will be used to develop the soil sampling grid.
During the pretest survey, observations will be made of the soils adjacent
to the fuel/waste storage and ,ash disposal areas. Any contamination or
spillage should be noted.
17
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2.3.6 Pretest Survey Forms and Reporting
After the pretest site survey, a brief trip report will be prepared
that describes the design and operation of the combustion source. The
purpose of the report is to document the pretest survey and to provide
recommendations concerning the suitability of the site for testing. The
completed pretest survey forms will provide the basis of the report.
Despite individual variations, all trip reports must address key information
areas. The headings listing below should be used as a checklist to ensure
that all relevant items are reported:
1. Site visited - name, location, type (e.g., black liquor boiler,
wire reclamation incinerator);
2. Inclusive dates of visit;
3. Persons conducting survey, persons interviewed, or otherwise
supplying data or information (name, title, telephone number);
4. Facilities, processes, and equipment observed;
5. Information acquired on the combustion process:
Source of fuel and waste materials combusted;
Design data, age, size, manufacturer, type of device;
Operating conditions;
Operating history;
Process parameters;
Characteristics of streams to be sampled (physical form,
temperature, pressure);
Operating schedule including schedule outages and abnormal
operations;
Emission rates, controlled and uncontrolled; and
Pollution control system(s) - operating parameters,
efficiencies achieved, and data from relevant past tests.
6. Recommendations concerning testing.
At the conclusion of the pretest survey,, the facility will be asked to
identify any inaccuracies or confidential data included in the pretest
survey form. If none of the information supplied by the facility is
confidential, it will be indicated as such in the trip report.
18
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Following the pretest survey, each site will be evaluated for its
appropriateness for inclusion as a test site. It is possible that sites
will be selected prior to completion of all pretest surveys. Selection of
sites will be made in conjunction with the EPA Project Officer.
Following selection, candidate sites will then be notified and test
dates will be scheduled. A site specific source test plan will be prepared
for each site. This will include a table detailing the number and type of
samples to be taken. The Sample Control Center will be sent a copy of the
sample matrix and will be asked to supply an episode number. Sample
identification numbers will then be assigned by Tier 4 EPA personnel.
19
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3.0 GASEOUS STREAMS - SAMPLING AND ANALYSIS
This section describes the sampling techniques that will be used to
measure specific gaseous and particulate emissions from combustion sources
as part of the Tier 4 sampling program. Section 3.1 discusses the types of
streams that are anticipated. Section 3.2 presents the recommended sampling
techniques and instrumentation. The techniques are described in more detail
in Section 3.3.
3.1 GASEOUS EMISSIONS SOURCES
There are three primary gaseous streams of interest to the program.
These are (a) ambient air which will be used to provide air for combustion,
(b) the gaseous exhaust from the combustion device prior to control, and
(c) the gaseous exhaust from the pollution control device (PCD). The
gaseous streams from a typical combustion device are illustrated in
Figure 3-1. The parameters to be measured for each of these three streams
are listed in Table 3-1.
In addition to taking grab samples of gases for PCDD and other
analyses, continuous monitoring of the combustion gases will be performed.
Depending on the specific type of combustion source and fuels utilized, the
parameters monitored may vary slightly.
3.2 RECOMMENDED SAMPLING TECHNIQUES
A variety of gaseous sampling techniques will be necessary including
manual sampling from stacks, continuous monitoring (CEM) from stacks and
high volume sampling of the ambient (combustion) air. The variables to be
measured with the recommended sampling and analysis techniques are presented
in Table 3-1. Outlet streams will be sampled for the presence of dioxins.
In addition, 02 will be measured at the outlet of the combustion device.
The combustion air will be sample for dioxins and precursors if they are
suspected to be present.
As shown in the table the stack will be analyzed for several additional
compounds. Some of these shown are only applicable for some sources since
they provide information on the process performance but do not directly
20
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Stack
Ambient Air
for
Combustion
Combustion Device
APCD
Sample Points
A - Ambient air
B - Uncontrolled gaseous emissions
C - Controlled gaseous emissions
Figure 3-1. Gaseous streams associated with combustion sources.
21
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TABLE 3-1. PARAMETERS TO MEASURE IN GASEOUS STREAMS
Stream
Precombustion Air
Combustion Device Outlet
Stack Exhaust5
Parameter
Dioxin1'2 2
Precursors
Dioxin
Moisture 2
Particulate
Molecular weight
Volumetric flow
HC1
CO
C09
°2 2
Sulfur oxides 2
Nitrogen oxides
Total Hydrocarbon
Dioxin ?
Particulate
Volumetric Flow
Molecular Weight
Moisture
HC"r
Sample Collection
Method
Ambient XAD Train,
Ambient XAD Train"3
MM5T4
EPA Method 4
EPA Method 5
EPA Method 3
EPA Method 2
Acid Train
Continuous Monitor
Continuous Monitor
Continuous Monitor
Continuous Monitor
Continuous Monitor
Continuous Monitor
"MM5T
EPA Method 5
EPA Method 2
EPA Method 3
EPA Method 4
Acid Train
Dioxin - 2,3,7,8 TCDD plus homologues (polychlorinated dibenzo-p-dioxins
with three to eight chlorines).
p
Where applicable, see text.
3
Ambient XAD train - an ambient air sample train used in conjunction with
an XAD-2 trap.
MM5T - a modified EPA "Method 5" train as defined in the ASME protocol.
In some cases, similar measurements may not be made at both the combustion
device outlet and the stacks exhaust. In these cases some of the stack
exhaust measurements will not be made.
22
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assess dioxin emissions, but are commonly gathered during CEM programs.
HC1, SO and NO are often measured, but have no direct relationship with
A X
dioxin emissions and are fuel dependent.
Table 3-1 shows that measurement of SO. NO , and particulate will be
X X
made where useful. These components are often measured, but do not always
provide useful information for all combustion sources. NO can be an
indicator of combustion conditions; however, if the fuel nitrogen varies
substantially it is difficult or impossible to compare firing conditions on
the basis of NO . A rough indicator of particulate concentration is
X
obtained with MM5; however, if very accurate measurements are desired, the
regular EPA Method 5 should be used. HC1 is shown as required since
chlorine concentrations may give some clues toward evaluating dioxin
formation. However, there may be situations, such as downstream from a
scrubber, that this measurement may not be useful and, in these cases, the
HC1 measurement can also be considered optional. Therefore, it is
recommended that the measurement of these compounds be decided for each
source test based on the value of the data collected.
For continuous monitoring the recommended sampling technique is to
extract gas with a heated sample line and condition it prior to introducing
it to the instruments. This is described in more detail in Section 3.3.
The recommended analytical techniques for the CEM system are shown in
Table 3-2. In general, there are three areas of gaseous sampling techniques
that will be utilized in the program. These are manual techniques,
continuous monitoring techniques, and ambient techniques. The general
application of each of these techniques will be discussed in this section.
3.2.1 Ambient Techniques
There is only one ambient sampling technique that will be used in the
sampling program. This technique will be used to sample combustion air at
sites where the ambient air potentially contains detectable levels of dioxin
or its precursors. The sample will be collected on an XAD sorbent trap
using a sampling train similar to Modified Method 5.
23
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TABLE 3-2. RECOMMENDED CONTINUOUS MONITORS FOR TESTING
TIER 4 COMBUSTION SOURCES
Pollutant
Species
Model
Operating Principle
°2
NO
x
THC
SO,
CO/CO,
Molecular weight
Beckman No. 755 or 752
(or equivalent)
Teco Model No. 10
(or equivalent)
Beckman Model No. 406
(or equivalent)
Teco Model No. 40
(or equivalent)
Anard Model No. 702
(or equivalent)
Shimadzi 3BT
(or equivalent)
Paramagnetic
Chemiluminescence
Flame ionization
Pulsed fluorescence
Nondispersive Infrared
Gas Chromotography -
Thermoconductivity
Dectector
Note - Pulsed fluorescence measurements are affected by 02 and C02 in
the flue gas. Therefore, these instruments should be calibrated
with gases that contain 02 and C02 concentrations similar to the
source. Alternatively, an instrument specific equation can be
used, if available.
24
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A schematic diagram of the "ambient XAD" sample train is shown in
Figure 3-2. The train consists of a probe, condenser/sorbent tube, water
knockout trap, silica gel container, transfer line, pump, and dry gas meter.
Ambient air will be drawn into the sorbent module, where it will be cooled
to 68°F or lower, and the organic constituents will be adsorbed by the XAD
resin. The gas will then be dried with the silica gel and the sample volume
measured by the dry gas meter. Two separate sample trains will be run
simultaneously. One of the XAD tubes will be analyzed by Troika for total
TCDD, and the other tube will be analyzed for dioxin precursors at Radian's
RTF laboratory.
The entire ambient XAD sample train will be leak tested before and
after each test run at 10 inches H20 to ensure that the total leakage is
less than 0.02 cfm. The ambient XAD sample train will be operated during
the same time periods that the MM5 samples are being collected. However,
the same set of ambient XAD traps will be used for all three MM5 test runs,
thus providing a composite combustion air sample for each site. The reason
for doing this is that ambient concentrations are very low, and this
approach will allow very low concentrations to be measured. In addition, it
reduces the overall analytical load by requiring only a single extraction
and analysis. The dry gas meter reading will be recorded twice daily at the
beginning and end of each test period. The dry gas meter temperature,
pressure, and volume will be recorded at least once per hour during the
sampling periods. Since the XAD trap has a limited capacity, it will be
necessary to calculate a maximum throughput based on conservative
assumptions of the ambient TCDD and dioxin precursors. Each of the three
test runs will involve pulling one-third of this calculated volume through
the XAD trap.
3.2.2 Manual Techniques
There are several manual testing techniques that will be used in the
Tier 4 sampling program. Each technique is designed to measure a specific
parameter. The stack techniques to be used in the Tier 4 sampling program
are ASTM-MM5T, EPA Reference Methods 1-5 and a HC1 Acid Sampling train. The
25
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AMBIENT XAD TRAIN
Figure 3-2. Schematic diagram of the ambient XAD sample train.
26
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application of each specific train to the stack sampling ports will be
discussed in the site specific test plan. Variations of modifications to
the referenced methods will be thoroughly documented there.
The selection of an adequate sample location is extremely important in
the representativeness of the resultant sample. Selection of the sample
location will be made based on the pretest survey trip report as discussed
in Section 2. All sample location selection for stack sampling techniques
will be based upon EPA Reference Method 1 citing criteria whenever possible.
The stack must have two ports (for particulate and dioxin measurements)
located 90° apart, at least 2 diameters downstream from the last flow
disturbance (8 diameters is preferred), and at least 1/2 diameter upstream
from a flow disturbance (2 is preferable).
If the preferred sample location siting criteria are'not met,
unrepresentative data may result, especially with particulate matter.
Stratification of particulate matter can be significant, leading to
nonrepresentative samples. If sampling is performed prior to a pollution
control device (PCD), stratification is of greater concern since this can
affect the performance of the PCD. The use of an optional cyclone in the
particulate and dioxin sampling trains is advisable if particulate loading
is expected to exceed 0.05 grains/dscf (0.11 grams/dscm).
A brief description of the commonly utilized stack sampling techniques
will be discussed in the sections with follow. A more detailed discussion
of the ASME-MM5T will also be highlighted in order to draw attention to
recent improvements to the methodology which are necessary in order to
minimize data variability.
3.2.3 Continuous Monitor Techniques
Continuous monitoring of several flue gas components will be necessary
in order to document process conditions which may lead to the formation of
dioxin. The following parameters may be monitored continuously at all
sites: CO, C00, THC, and 00. In addition, SOV and NOV may be monitored
C. <- X A
continuously where appropriate. A specific list of parameters will be
finalized in each site specific test plan. The ASME conference on
development of dioxin test methods for energy from solid waste combustion
27
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plants suggested that, in addition to the parameters listed above, water and
opacity be continuously monitored. However, these parameters will not
provide useful information for most Tier 4 sources. They will be difficult
to measure at sites where limited suitable sample locations are availabe for
temporary monitors. This is often the case. For sources equipped with
permanent, in-stack monitors for opacity and hLO, copies of the chart
records will be obtained for the test period. Where these are not
available, the gas phase hUO concentration will be determined from the MM5
results. The types of recommended continuous monitors that are recommended
are shown in Table 3-2.
The operation of the continuous monitors is further discussed in
Section 3.3. The detailed specifics of operation will be further defined in
the site-specific test plan, once details of the sample stream are
determined.
3.3 DESCRIPTION OF SAMPLING TECHNIQUES
3.3.1 Manual Sampling Methods
This section contains a brief narrative of each manual sampling method
anticipated for Tier 4 gaseous sampling. Where applicable, special notes
are included in italics to indicate a particular caution or advisable
modification. If more detailed description of the individual methods are
required, the citation listed in the Federal Register should be consulted.
EPA Reference Method 1
The criteria described in EPA Reference Method 1 (Sample and Velocity
Traverses for Stationary Sources, Federal Register 42 FR 41754, August 18,
1977) will be used to select appropriate sampling sites whenever possible.
The 8 diameters and 2 diameters rule, upstream and downstream respectively,
of any flow disturbance is the primary criteria needed to be met. The
minimum allowable is 2 diameters upstream and 0.5 diameters downstream.
EPA Reference Method 2
EPA Reference Method 2 (Determination of Stack Gas Velocity and
Volumetric Flow Rate, Federal Register 42 FR 41759, August 18, 1977) will be
followed to determine flue gas velocity, stack temperature, stack pressure,
28
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and volumetric flow rate. All flue gas volumetric flow rates will be
reported for both actual and standard conditions. Standard conditions will
be 68°F and 29.92 inches of mercury (Hg). Equipment utilized by this method
(Type S - pitot tube, differential gauge, barometer and temperature gauge)
will meet or exceed the specifications called for in the reference document.
Appropriate calibration procedures will be executive on all equipment
utilized prior to use in the field.
EPA Reference Method 3
EPA Reference Method 3 (Gas Analysis for Carbon Dioxide, Oxygen, Excess
Air, and Dry Molecular Weight, Federal Register 42 FR 41768, August 18,
1977) will be utilized to characterize the stationary gas analysis. As
permitted under Section 1.2, paragraph 2 of the referenced document, a
modification to the sampling procedures and use of an alternative analytical
procedures will be implemented. A single point integrated sample is
anticipated. In lieu of an Orsat analyzer, a gas chromatograph with a
thermal conductively detector (GC/TCD) will be utilized to measure the
concentrations of oxygen (02), carbon dioxide (C02), nitrogen (N2), and
carbon monoxide (CO) in the integrated bag sample. Previous test programs
have demonstrated the acceptability of this substitution. This alternative
analytical method offers acceptable accuracy and a permanent hard copy
record of the analysis. The data will be reported in units of percent by
volume for 0?, N?, and CO. Dry molecular weight will be calculated by
Equation 3-2 of the referenced document and reported in units of grams per
gram-mole (g/g-mole).
EPA Reference Method 4
EPA Reference Method 4 (Determination of Moisture Content in Stack Gas,
Federal Register 42 FR 41771, August 18, 1977) will be utilized to measure
volumetrically the moisture (FLO) content of the flue gas streams. The
sampling train specified in EPA Method 5 will be utilized to measure
moisture in conjunction with particulate matter determinations. This is an
acceptable procedure under Section 2, paragraph 1 of the referenced
document. All components shall be maintained and calibrated according to
the procedure outlined in Method 5. The moisture content (BWS) will be
29
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reported in units of proportion of water vapor, by volume, in the gas stream
according to Equation 4-4 of the referenced document.
HC1 Acid Sampling Method (Gaseous)
The sampling procedure developed for the determination of hydrogen
chloride emissions from stationary sources is basically a modification of
the standard procedure for S02 determination (EPA Reference Method 6). The
HCL method utilizes the same equipment (i.e., probe, glassware, pump, dry
gas meter, etc.) with the exception that a regular midget impinger is used
for the first impinger in place of the midget bubbler used in Method 6. (At
the option of the tester, regular size Method 5 glassware may be utilized.)
Dilute sodium hydroxide (O.lm NaOH) is used as the absorbing solution
in the impingers. (If higher levels of C02 (<15 percent are expected for
sample periods greater than 1 hour in duration, the tester may choose to
replace the NaOH, with sodium acetate, in order to prevent plugging of the
impingers due to formation of carbonate precipitate.
A heated glass lined probe is used with the temperature maintained at
300°F or at stack temperature whichever is greater. A pyrex wool plug is
inserted in the inlet end of the p'robe in the same manner as required by
Method 6. It is important to note that if this method is used downstream of
a wet scrubber that the probe and filter must be heated to avoid
condensation. This temperature should be 25° to 50°C above the dewpoint.
The impinger train is immersed in an ice bath during sampling. The
impingers containing the absorbing solution are connected to the probe with
glass connectors and U-tubes held in place with standard pinch clamps. The
first two impingers contain the absorbing solution. The third impinger is
empty, and the fourth impinger contains silica gel to remove moisture. A
standard umbilical line is used to connect the impingers to a standard
control module containing the pump and dry gas meter.
Samples collected in this manner will be analyzed remotely by ion
chromatograph. The analysis results in conjunction with the dry gas meter
reading can be used to determine the gas phase concentration.
30
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ASME-MM5T
EPA Method 5 is the basis for the ASME train for sampling for dioxin.
There are a variety of modifications to the standard Method 5 sampling
train, each of which has a selected objective in mind. The ASME-MM5T that
will be utilized for Tier 4 reflects the latest draft of the ASME dioxin
sampling protocol which is attached as Appendix A.
The ASME-MM5T consists of the following components:
probe,
cyclone (optional),
glass filter holder with Teflon seal,
glass condenser coil,
sorbent trap (XAD-2),
water knock out trap (optional),
two water filled impingers,
empty impinger,
silica gel impinger, and
pump and dry gas meter.
The front half of the sampling train (probe and filter) should be
maintained at 248°F to prevent moisture condensation and to allow for a
determination of dioxin in the front half particulate matter if desired.
All connections of glassware must be made grease-free. (If the glassware
had been previously used with grease, a special cleaning procedure must be
followed in order to prevent interferences in the analytical screening.)
Acceptable materials of construction for any part of the sampling train
that contacts the sample may be either glass or TFE Teflon. (Stainless
steel is not regarded as an acceptable material for either the probe or
filter housing, if avoidable.)
The sampling train should be operated isokinetically at a sample
location which meets EPA Method 1 siting criteria for particulate matter
determinations. The sample location should be traversed following normal
particulate sampling protocol as specified in EPA Method 5. The gas flow
rate through the sample train should range between 0.014 to 0.028 cm/min
(0.5-1.0 cfm), by selection of appropriate sized sampling nozzle. The ASME
31
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Committee responsible for development of the dioxin sampling method (MM5T)
has recommended a sampling time of eight hours which is equivalent to sample
volume of approximately 13 dscm. The intent is to produce enough sample to
allow detection of 1 ng of dioxin in the train. Extended periods of
sampling will be required (^ 8 hours), exclusive of setup and sampling
recovery.
Precautions in leak checking the train must be taken. If the leak free
operation cannot be achieved on the first attempt, a filtering apparatus to
clean the ambient air being drawn into the sample train during the leak
check should be considered. The ambient organics concentration at some
industrial locations may be greater than those found in efficiently operated
combustion sources and, therefore, be a potential source of contamination.
Sealing greases should not be used on the sample train during operation
or cleanup.
Hexane rinsed aluminum foil should be used to cap off all connections
prior to and after sampling. Contact with unwashed surfaces must be
avoided.
3.3.2 Continuous Gas Monitoring
Continuous monitoring sampling system for the following flue gas
parameters will be conducted during each test period: CO, COP, CL, NO , and
£ L- X
total hydrocarbons (THC). These and other parameters were recommended by
the ASME consensus committee, and will be used to indicate combustion
conditions during the period of the test. For example combustion efficiency
can be calculated using CO & C02, and stack oxygen levels can be used as an
indication of the amount of Op available for combustion.
This section describes suggested continuous monitors for application to
the National Dioxin Study at combustion sources within Tier 4. The previous
section listed recommended monitors for all purposes of the study.
Additional continuous monitoring of the flue gas may be appropriate for
specific sites where information exists which indicates additional
parameters are warranted. An example is SO where high levels of sulfur are
/\
present in the feed or fuel. Additions or substitutions to this list of
continuous monitors will be discussed and justified in the site-specific
test plan for individual combustion sites.
32
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Figure 3-3 is an example schematic of an acceptable continuous emission
monitor system (CEMS) for installation during the test program. A
separately installed continuous monitor system will be used during the test
program. The site-specific test plan will include a schematic diagram
similar to the one shown in Figure 3-2 which indicates the sampling
location(s) and means of transport and introduction of sample to the
analyzers. For gas conditioning, a TECO Model 600D is recommended.
There are several areas of concern which should be addressed in the
site-specific test plan regarding the design of the continuous monitor
system. These include the following:
The heating capacity of .the sample line (300°F recommended);
Cleaning of the heat-traced sample line;
The uptake of all the analyzers and the capacity of the sampling
line and gas conditioner to supply sufficient volume to the same manifold.
The recommended list of analyzers requires that heat-traced sample line be
of at least 3/8-inch diameter;
The expected concentration of each species at each sample location
in order to specify suitable gas calibration standards and instrumental
ranges.
The certification/calibration procedures which will be used
on-site to qualify the recorded data; and
The data handling and recording system.
3.4 CLEANING PROCEDURES
The sampling containers and sampling equipment should be cleaned prior
to the test by the procedures listed in Table 3-3. The cleaned containers
p
will be transported to the sampling location with the Teflon lids tightly
in place. Once the sample is introduced to the container, the lid shall be
p
replaced and wrapped with clean Teflon tape, wrapped in cleaned foil, and
transported to the analytical locations.
Sampling equipment for each test will be precleaned, capped with
aluminum foil, and packaged for transportation to the field. New,
precleaned train components including the filter holder and the XAD-2 trap
33
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s —
I
in
e
— w
*-
^-
si
5
si
* S
0 i
en
e
-a
c
o
o
in
ta
ro
i
CO
cu
S_
3
CD
34
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TABLE 3-3. PRETEST EQUIPMENT CLEANING PROCEDURE FOR
SAMPLING CONTAINERS
NOTE: USE DISPOSABLE GLOVES AND ADEQUATE VENTILATION
1. Soak all glassware in hot soapy water (Alconox) 50°C or higher.
2. H20 rinse (X3)
3. Distilled/deionized H0 rinse (X3),
4. Chromerge rinse if glass, otherwise skip to 6.
5. Distilled/deionized H90 rinse (X3).
6. Acetone rinse (X3), (pesticide grade).
7. Hexane rinse (X3), (pesticide grade).
8. Oven dry (110°C). :
9. Cap containers with Teflon lids. Foil wrap the sampling equipment.
35
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2.
3.
4.
5.
6.
will be used for each test. When going to a new location, the cleaning of
nonreplaceable components such as the probe and condenser shall consist of:
1. Removal of loose sample,
H20 Rinse (x3),
Acetone rinse (x3) (pesticide grade),
Hexane rinse (x3) (pesticide grade),
Air dry in a clean environment, and
Foil wrap (hexane rinsed).
Between sampling at the same location, no extra cleaning is necessary.
3.5 SAMPLE FREQUENCY
These are recommended frequencies for planning purposes. However, if
more frequent samples can be obtained and are justified, it is reasonable to
change the sample frequency.
3.6 REPORTING FORMAT
In order to aid consistency between the various tests, a standard
format is recommended for reporting the results. For gaseous analyses, it
is recommended that,the report consist of a table as shown in Figures 3-4
and 3-5. Similar tables should be prepared for each sample point.
Additional forms of reporting, such as hourly and daily averages or a
summary of dioxin measurements at each location should also be considered.
The results should also be reported on the basis of plant throughput, e.g.,
kg per ton of feed or kg per million Btu of heat input. The specific format
and method of calculating this value will depend on the type of process
being evaluated.
A more detailed description of the reporting guidelines can be found in
the publication National Dioxin Study Tier 4 - Combustion Sources Dioxin
Source Test Reporting Format Guide, EPA-450/4-84-014f, November 1984, Draft.
36
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4.0 SAMPLING LIQUIDS AND SLURRIES
Liquids and slurries will account for a number of samples at many
combustion devices/facilities. Liquids are defined as sample streams having
a moisture percent greater than 90 percent. Slurries are defined as samples
with moisture content greater than 70 percent but less than 90 percent and
having visible suspended solids. Slurries can be thought of as an easily
flowing material with entrained particulate matter.
Different sampling techniques are used for collecting liquids than for
slurries. Since there may be some particulate matter in a liquid sample, it
should be taken from a point in the stream where there is good mixing.
Stratification of the stream is usually not a problem if the stream is
moving. Slurries, on the other hand, can stratify on impact with the walls
in the elbows or bends in piping. Care must be taken to obtain these
samples at straight pipe runs where the mixing is good (Reynolds
Number >2500).
In order to obtain a representative sample of liquids/slurries, three
main objectives must be met:
Choose a sample point which will allow the most representative
sample to be obtained;
Choose a sampling technique appropriate to the sample point; and
Prepare composite samples based on the conditions of the stream
and flow.
These main objectives will be discussed in the following subsections.
4.1 SOURCES OF TYPICAL LIQUID/SLURRY STREAMS
Figure 4-1 shows a schematic of a hypothetical plant to be sampled for
this study. The figure shows more sample points than would be present on a
real plant, but they are put in here to show the possible liquid/slurry
streams and the sample locations. The actual streams to be sampled should
be determined as part of the preliminary evaluation of the process streams
during the pretest survey. Similarly, decisions as to whether the existing
39
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sample locations are adequate or new ones are needed should be made at this
time. It is unlikely, however, that the plant operator will provide
additional sampling facilities.
There are three general locations for sampling liquids or slurry
streams. These are: (1) taps or ports in a pipe, (2) as point of discharge
of the pipe or channel into the combustion device or storage container, and
(3) the storage tank or pond. Sampling from taps is most desirable, and
sampling from storage containers is least desirable for obtaining a
representative sample. Liquid/slurry streams are primarily moved by pipes
rather than open channels. Most of the streams flowing in pipes will have
an existing sample tap which can be used for sampling in this program. Taps
will probably be used for fuel oils, liquid fuels or wastes, and scrubber
water. If no sampling tap exists, a sample can be taken at the point of
discharge of the pipe. For example, some liquid streams like scrubber
blowdown may be sampled where they discharge into the treatment facility or
sewer system. Some of the nonhazardous streams may empty directly to a
storm sewer where it is combined with water runoff from the plant. It is
desirable to obtain these samples prior to entry in the storm drains. The
best location to sample is the point where the sample stream leaves the pipe
and enters the drain as a very representative sample can be obtained and
flow monitored at the same time. Also, when sampling the fuel, a sample
could be obtained at the storage tank; however, it is preferable to take the
sample just prior to the burner as stratification could occur in the storage
tank and not all of the tank will be utilized during the test. Similarly,
it is desirable to obtain a waste product prior to combination with other
streams or entry to lagoons or settling ponds.
4.2 RECOMMENDED SAMPLING METHODS
The following subsection describes the recommended sampling methods for
liquids and slurries. The methods presented are grab and composite grab
sampling methods and are intended to provide a sample that can be used to
characterize the combustion device or control device inputs and outputs in
sufficient detail to fulfill the requirements of the program. More
41
-------
sophisticated sampling acquisition schemes, for example, integrated grab or
continuous sampling schemes, are not needed to fulfill the needs of the
program.
However, the methods which are recommended here are tried and proven
discreet sampling techniques which are employed at selected sample points
and times to yield a representative composite sample. Table 4-1 gives a
brief overview of the methods presented and their application.
Since most of the streams to be sampled are contained in pipes and the
objective is to obtain as representative a sample as close to the combustion
process as possible, the recommended sampling procedures to be utilized will
be the tap sampler, dipper, and pump sampler. Only in cases where there is
no other suitable sampling procedure will the Coliwasa or weighted bottle
sampler be utilized. Figure 4-1 numbered the sample points in the process,
and they are reproduced in Table 4-2 along with the proper sampling
technique.
If, for some reason, the preferred sample point is not available,
•alternate techniques should be used. Usually, this means that the only
available sample source is a lagoon, pond, or tank. In this event, the
weighted bottle, dipper, or Coliwasa sampler is the preferred method.
Obviously, these recommendations are not absolute, and some judgment
should be used when selecting methods for the actual test site. This is one
of the reasons for preparing a site-specific test plan for each facility
tested. As an aid in making these judgments, each of the sampling methods
is described in the sections which follow. These descriptions are not
intended to be procedural guidelines, but rather to guide the selection of
the proper technique when special situations are encountered.
4.3 DESCRIPTIONS OF LIQUID SAMPLING TECHNIQUES
4.3.1 Tap Sampler
Tap sampling, Figure 4-2, is the appropriate method for sampling moving
liquids in pipes or ducts. Slurries in motion are sometimes sampled by tap,
but this is unreliable if the solids content is much greater than
10 percent.
42
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TABLE 4-1. SUMMARY OF LIQUID SAMPLING TECHNIQUES
Technique
Description
Tap Sampler
Dipper
Appropriate for homogeneous flowing liquids in
pipes or ducts.
Surface liquid sampling device or outflow of pipe
or sluiceway.
Coliwasa
Sampler which will collect liquid from standing
liquids contained in drums, tanks, pits, or
lagoons.
Weighted Bottle
Subsurface liquid sampling device.
43
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TABLE 4-2. RECOMMENDED APPROACH TO SAMPLING LIQUID STREAMS
1.
2.
3.
4.
5.
6.
7.
8.
9.
Source
Liquid fuel
Ash slurry
Makeup water
Process/Cooling water
Makeup water
Quench water
Makeup water
Scrubber blowdown
Demister blowdown
Preferred
Location
Pipe
Pipe
Sluiceway
Pipe
Pipe
Pipe
Pipe
Pipe
Pipe
Pipe
Preferred
Sample Point
Tap
Tap
Open drain
Tap
Tap
Tap
Tap
Tap
Tap
Tap
Preferred
Sample
Technique
Tap
Pump
Di pper
Tap
• Tap
Tap
Tap
Tap
Tap/ Pump
Tap
44
-------
LINE
OR
TANK
WALL
6.4 mm
(V4 in.)
Figure 4-2. Schematic of tap sampling.
45
-------
To acquire a tap sample, the outlet of the valve or stopcock used for
p
sample removal is fitted with a length of precleaned Teflon tubing
sufficiently long to reach the bottom of the sampler container. After the
TeflonR conduit line has been placed in .the sample container, the tap is
opened to admit a moderate flow of liquid. The conduit line, but not the
sample container, should be flushed before the sample is actually taken.
Flushed material should be returned to the process.
If the sample temperature is above about 50°C, the sample should be
cooled before being placed in a sample container. Cooling the sample can be
D
affected by using a longer length of Teflon conduit line, coiling it, and
placing it in an ice-water bath. Again, the tap is opened, and the liquid
is discharged until possible sediments and gas have been flushed. Then the
sample container is filled.
A moving liquid stream, known to contain particulate matter or
immiscible phases, will be considered stratified. The optimum location for
a sampling tap will be after a bend or constriction which will induce
turbulence or at least promote mixing. Only the main pipe or stream flow
should be sampled. Taps in vents or slipstreams are not recommended because
solids can accumulate.
4.3.2 Dipper Sampling
The dipper or pond sampler is used to acquire samples of liquids in
ponds, sluices, pits, lagoons, and tanks with open tops. It can also be
used to catch samples of the end of a discharge pipe. A typical dipper
sampler is shown schematically in Figure 4-3. Dipper samplers are not sold
commercially but can be readily fabricated. The figure indicates that the _
pole should be capable of extending to 4.5 meters (15 ft). Samples as far
as 3.5 meters from shore can thus be taken.
To take a sample, the dipper is inverted and lower slowly into the
liquid to be sampled. At the desired sampling point, the dipper is righted,
releasing trapped air and filling with sample. The dipper is then slowly
removed from the pond. After removal, the outside is carefully wiped with a
disposable rag or cloth, and the sample is placed into an appropriate
container.
46
-------
VARIGRIP CLAMP
)
BOLT HOLE
BEAKER, 25 ML TEFLON OR GLASS
TELESCOPING ALUMINUM POLE, HEAVY DUTY,
2,5 TO 4,5 M (8 TO 15 FT)
Figure 4-3. Dipper sampler
47
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4.3.3 The Coliwasa Sampler
The preferred sampling method is to use taps and end-of-pipe sampling.
Howevers there may be circumstances under which the Coliwasa sampler should
be used. The Coliwasa is employed to sample free-standing liquids and
slurries contained in drums, shallow open-top tanks, pits, and similar
containers. It is particularly useful for sampling wastes which consist of
immiscible phases. It is easy to use, and samples may be taken quite
rapidly, thereby minimizing exposure of the sampling personnel to the
wastes.
Any Coliwasa used for this program should be made of glass with either
glass or Teflon fittings. The sampler consists of a tube which is equipped
with a closure and the other end of which has a control for the closure.
Figure 4-4 is a schematic, and fabrication details have been documented (de
Vera et al., 1980).
To take a sample with the Coliwasa, the end closure is first opened.
Then the sampler is slowly lowered into the container holding the waste to
be sampled. The speed of insertion should be such that the liquid levels on
the inside and outside of the tube are the same. When the sampler reaches
the bottom of the container, the tube is pushed down to close the end; the
stopper is locked by turning the T-handle until it is upright and one end
rests on the locking block. The Coliwasa is th.en withdrawn from the waste
container. The outside is wiped with a disposable rag or cloth, and the
sample is discharged slowly into an appropriate container.
When constructed as recommended, a Coliwasa cannot sample liquids more
than 1.5 m depth. Consequently, its use will be limited to sampling drums
and other shallow containers.
4.3.4 Weighted Bottle Sampler
The weighted bottle method, Figure 4-5, is used for sampling liquids or
free-flowing slurries in tank trucks/cars and tanks. It can also be used
for ponds, lagoons, etc., which are too deep for sampling by Coliwasa.
Sufficient details for construction are given in ASTM (1975) Method D-270
and ASTM (1973) Method E-300.
48
-------
STOPPER
6.35cm (2-1/2")
T HANDLE
LOCKING
BLOCK
152 cm (60")
2.86cm(l-l/8")
17.3 cm (7")
10.16 cm (4")
•PIPE
4.13 cm (1-5/8") 1.0.
4.26cm(l-7/8")0.0.
STOPPER ROD
0.95cm (3/8") 0.0.
SAMPLING POSITION
CLOSED POSITION
STOPPER
0.95 cm (3/8") LOCK NUT
AND WASHER
Figure 4-4. Composite liquid waste sampler. ^
(All materials are either glass or Teflon .)
49
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1 QUART WEIGHTED BOTTLE CATCHER
(CAN BE FABRICATED TO FIT ANY SIZE BOTTLE)
Figure 4-5. Weighted bottle sampler.
(All materials except cage and chains
are either glass or Teflon®.)
50
-------
The weighted bottle sampler usually consists of a glass bottle, a metal
bottle basket or sinker, a bottle stopper, and one or two lines to raise and
lower the basket, as well as :open the bottle when the sampler is at the
desired depth. To acquire a sample, the stoppered bottle is lower to the
appropriate depth, the cap is raised, and the sampler is then withdrawn.
The bottle usually serves as the sample container; thus, once out of the
waste, the bottle is capped, rinsed, and labeled. Weighted bottle samplers
should be constructed of materials compatible with the waste being sampled.
4.4 SAMPLE SIZE, TYPE, NUMBER, AND STORAGE
In addition to choosing a proper sample point and matching it to the
sample technique, the sample must be of sufficient quantity to match the
analyst's needs. It will be composited so as to minimize the number of
analyses and to obtain as representative sample as possible. Figure 4-6
outlines the compositing scheme to be utilized during this program. It is
recommended that three replicates of each sample be prepared. In order to
generate the three samples a large sample will be collected, mixed, and then
split. Where appropriate, the large sample will be a composite prepared by
combining several smaller samples taken at regular intervals. Of the three
replicate or final samples, one will be sent to Troika for dioxin analysis,
one will be given.to the plant for their use, and one will be kept as a
spare and used for analysis by a non-Troika lab as appropriate.
Manually prepared proportional composites (collected and mixed by hand)
are recommended for this program where applicable. The total sample size
will be determined by the analytical needs of the Troika. Past experience
has shown this is not likely to exceed approximately 4 liters (1 gal). The
size of the Troika, plant, and the spare samples will be the same and be
taken from the compositing container. Therefore, the composite sample
should be about 16 liters (4 gal). The material in the container should be
mixed prior to splitting the composite to ensure that each sample is
representative.
If the flow is steady, the sample size can be determined by dividing
the number of individual samples into the total composited volume needed
51
-------
Time,
Hrs
• oD
,.5 a
1.0
1.5
TROIKA
SPARE
PLANT
Individual Samples
0.5 litre each
Amber glass bottles
with Teflon lid
Composite Sample
5 gal (20 L)
Glass with Teflon
lined lid
Final Samples
1 gal (4L)
Amber glass with
Teflon lid
1.
2.
3.
Example shown is for eight samples over four hour period. Actual
number, frequency and size may vary as judged necessary by the test
plan.
If flow is constant, equal sample volumes will be used to make the
composite.
If flow is irregular, the individual samples will be proportioned
to the flow and added. The sample size will be determined by the
analytical needs of TROIKA. The spare sample and the plant •
sample will be of equal size.
Figure 4-6. Sample compositing scheme.
52
-------
which will yield the minimum sample to be taken. If the flow is irregular,
an average flow will be used to determine the average size of the discreet
sample. The amount taken in each sample will be in proportion to the flow.
If this information is not available until after the test, an excess
individual sample will be collected, but only the composite will be
specified by flow. If the flows are not known, individual samples of equal
volume should be taken.
The number of liquid or slurry samples to be taken will vary from site
to site based on factors such as the number of streams to be sampled, the
number of separate analyses desired, and the number of remote labs involved.
In the examples presented in this section, we have assumed seven distinct
streams, one sample of analysis, and one remote lab (Troika). The total
number of samples required for this situation is presented in Table 4-3. A
similar approach can be used to determine the total number of samples to be
taken at each facility. This should be done prior to arriving at the test
site since sample numbers have to be assigned in advance for those sent to
Troika.
4.5 CLEANING PROCEDURES
The sampling containers and sampling equipment should be cleaned prior
to the test by the procedures listed in Table 4-4. The cleaned glassware
will be transported to the sampling location with the TeflonR lids tightly
in place. Once the sample is introduced to the container, the lid shall be
replaced and wrapped with Teflon tape, wrapped in cleaned foil, and
transported to the analysis locations. Between sampling at the same
location, no extra cleaning is necessary. When going to a new location with
the same equipment, the cleaning shall consist of:
1. Removal of loose sample,
H20 Rinse (x3),
Acetone rinse (x3) (pesticide grade),
Hexane rinse (x3) (pesticide grade),
Air dry in a clean environment, and
Foil wrap (hexane rinsed).
2.
3.
4.
5.
6.
53
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TABLE 4-3. TOTAL NUMBER OF LIQUID OR SLURRY SAMPLES REQUIRED
FOR THE EXAMPLE SCENARIO
(Refer to Figure 4-1 for Sample Locations)
Source
Number of
Final Samples
Number of
Analyses
1. Liquid fuel
2. Ash slurry
3. Makeup water
4. Process/cooling water
5. Quench water
6. Scrubber blowdown
7. Demister blowdown
TOTAL
3
3
3
3
3
3
3.
21
54
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TABLE 4-4. PRETEST EQUIPMENT CLEANING PROCEDURE FOR
SAMPLING CONTAINERS
NOTE: USE DISPOSABLE GLOVES AND ADEQUATE VENTILATION
1. Soak all glassware in hot soapy water (Alconox) 50°C or higher.
2. H20 rinse (X3).
3. Distilled/deionized H0 rinse (X3)
4. Chromerge rinse.
5. Distilled/deionized HO rinse (X3).
6. Acetone rinse (X3), (pesticide grade),
7. Hexane rinse (X3), (pesticide grade).
8. Oven dry (110°C).
9. Cap containers with Teflon lids. Foil wrap the sampling equipment.
55
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4.6 DATA REPORTING FORMAT
The reporting format for liquid analyses will be total micrograms of
TCDD per sample submitted (with the size of the analyzed sample shown).
This analytical data should be combined with the process data obtained
during the testing period. The sample stream flow rate should also be
listed. The total TCDD emissions will, be calculated by subtracting the
inlet liquid stream totals from the outlet stream totals. An example data
reporting format is shown in Table 4-5. Also, where appropriate the
emissions should be related to the process throughput, e.g., kg emitted per
ton of sludge input or kg emitted per million Btu fired. The specific
method of doing this will depend on the type of process tested.
56
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5.0 SAMPLING OF SLUDGES, SOLIDS, AND SOILS
Sludges are defined as material which contains at least 20 percent
moisture but do not flow. They do not move freely as a slurry would and do
not mix well when stored or contained. Solids are defined as material which
contains less than 20 percent moisture. Solids, dependent upon the physical
state, may or may not mix well or flow well. The sampling methods utilized
during this program will depend upon the physical state of the material and
the sampling points of the material. As noted in Section 4.0, the
objectives of the sampling program are:
1. Choose a sampling point or points which will allow the most
representative sample to be obtained.
2. Choose a sampling technique appropriate to the sampling point(s).
3. Prepare and composite the sample based on the conditions of the
sample point or points.
5.1 SOURCES OF TYPICAL SLUDGE/SOLID/SOIL SAMPLES
The most typical sludge/solid streams will be bottom ash, pollution
control device solids, and soils from the plant site. Also, some combustion
devices may burn materials falling into these categories, for example,
sewage sludge incinerators and wood fuel boilers.
Figure 5-1 illustrates a hypothetical plant to be sampled for sludges
or solids. There are more sampling locations on the hypothetical plant than
are present on most plants in order to illustrate all the possible sample
points. The actual sample locations will be determined during the
preliminary evaluation of the process or during the pretest survey. The
decisions as to whether the existing sample locations are adequate or a new
approach is needed will be made during the pretest survey based upon good
technical judgment.
As opposed to liquids, sludges and solids are more difficult to handle
and it is more difficult to obtain a sample representative of the test
material during the time of the test. It is imperative that only waste
streams which provide a known and definable origin be chosen for sampling.
58
-------
Process
J/ ^*^
^tr
Sludge—*
©
Solid $
T
Process
Combu
Dev
«:tinn
ice
©
*•" *
Bottom Ash/
SI
^
ag
Truck/
Holding Area
^
f
Cyclone/
Baghouse
C/D #1
1
0
Fly
Ash
,
f
Pile
Scrubt
Fcr
C/D *
1
)er/
3
12
ESP
©
Scrubber
Sludge
©
Stack
t
Fly
Ash
f
Pile
Holding Pond
»
Pile
Landfill
*This sampling location could be extremely hot. Care should be taken if
bottom ash is to be taken directly upon leaving the combustion device.
Figure 5-1. Generic plant with sludge and solid sampling sites.
59
-------
This is sometimes difficult as disposal of solid waste occurs during
intermittent shifts and by a batch process. It is not unusual to sample for
solids 24 hours after the gaseous sampling in order to provide a sample
which relates to the combustion process.
Figures 5-2 through 5-4 show recommended sampling locations for some
pollution control devices that may be encountered. In addition to these
locations, there may be solid/sludge feed systems to the combustion device.
It is desirable to obtain the samples as close as possible to the combustion
or control device being evaluated. This would eliminate.mixing of streams
and other problems associated with unrepresentative sampling.
Soil samples should be obtained from the battery limits of the facility
being tested. The area selected should be actual soil and not dirt or other
material that overlays a foundation or the like. It is likely that most
plants will have areas of soil that can be sampled.
5.2 RECOMMENDED SAMPLING METHODS
The choice of a sampling method is dependent upon several factors
including:
1. Is the material a solid, sludge, or soil?
2. Is it free flowing, sticky, or other?
3. What kind of access is available to the material to be sampled?
Open conveyor, pipe, dump truck, etc.
4. Can the material be expected to be homogeneous?
Obviously, the only approach to selecting a sampling method is to consider
these and other factors and use good judgment. In this section,
recommendations and guidelines are presented where one sampling method is
preferable. Since the physical nature of the streams is not known, it is
not possible to make firm selections as to which method is most appropriate.
The methods recommended for use in this study are listed in Table 5-1 along
with comments on the applicability of each to solids or sludges. Using this
table, the descriptions which follow, and good judgment, the proper sampling
technique can be selected.
60
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TABLE 5-1. RECOMMENDED SAMPLING METHOD APPLICATIONS
Method
Stopped belt cut
Thief
Trier
Auger
Dredge
Trough
Dipper/scoop
Bulb planter
Solids
X
X
X
(X)
(X)
X
X
Applicable to
Sludges Soils
X
Comments
For conveyer systems
For flowable, granul
material
ar
For granular material
X X
X (X)
X
X
X
For hard, solid
material
For sludge pits
For end of conveyer
For end of pipe
sampling
For soils or soil-li
material
ke
X = Applicable.
64
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5.3 DESCRIPTION OF SAMPLING TECHNIQUES
Included for each procedure is (1) a description of the scope and
application of the method, (2) a summary of the method, (3) general
considerations which are applicable to that method, (4) apparatus and
equipment needed, and (5) sample handling provisions specific to each
method. For more detailed step-by-step procedures, the sampling team will
refer to the referenced standard method. Illustrations of typical classes
of sampling apparatuses are provided in Figures 5-5 through 5-10. These
illustrations by no means represent all possible types or configurations but
are intended to aid in understanding sampling methods described in the
following subsections.
5.3.1 ASTM "Stopped-Belt Cut" Method (D2234-76)
This method covers sampling of solid materials transported on conveyor
belts that can be stopped for an appreciable amount of time without
disrupting plant operations (i.e., several minutes). This sampling method
can be applied to feed solids, dry bottom ash, char or slag, and sludge.
This is the most favorable method for obtaining a representative sample
of material on a conveyor belt. With the belt stopped, a full-stream cut is
obtained from the belt with a shovel and brush (for fine material). The
width of the cut must be at least three times the diameter of the largest
particle or 1.25 inches, whichever is greater. Also, the sides of the cut
must be as nearly parallel as possible. The sample material can be placed
into a storage container for transport to the lab or may be put directly
into sample bottles if no other processing is required.
For measuring the width of the cut required, the diameter of the top
size particles must be known (to set the minimum width allowable, as
described above). A measuring tape can be used to mark off the correct
width. Sample material can be removed with a shovel or with a dustpan and
brush for fine-grained material. Samples can be transferred to large
buckets or boxes with a large funnel or scoop. The sampling equipment must
be clean and dry before use.
The sampling point(s) selected should allow complete access to either
sides of the belt and should be close to a floor or platform to facilitate
65
-------
AmiCATIOH
• END Of CONVEYOH KIT
Figure 5-5. Sampling trough.
AWUCAT10N
• HAUtTBUCXS
• STORAGE PILES
Figure 5-6. Sample auger.
66
-------
•OS
• rroiuss f II.ES
• UMTIING PORTS
• nut HOUS
Figure 5-7. Sample triers.
Af»LICAT70«
• STQUASE PIIK
• SAWfllNC WRIS
• fOKEHOUS
Figure 5-8. Sample probe or thief.
67 - .
-------
APPLICATION
• UTTL1N6 IASIMS
• THICXENEflS. ClARIf IIRS
• HVOROIINS
Figure 5-9. Dredge samplers (Ekman, Ponar)
VMI6XWCUUMT
ICAKCII
TtLEScof me 4LUMi»uM rau
AW.ICAT10H
« WO Of MM SAMFUNQ
• THICXENtm
• urniM ttatta IIOTTOMI
Figure 5-10. Dipper.
68
-------
moving and storing sample containers and equipment. There should be
sufficient work space so that sampling personnel can shovel solids or sludge
directly from the belt into containers. There should also be adequate space
for personnel to stand clear of the belt if it is accidentally started.
5.3.2 Thief, Trier, Auger, or. Bulb Planter Sampling of Stationary
Materials (ASTM D2234-76, D2234-76, C311-77, D346-78
These methods cover sampling of solid materials that may be located in
hoppers, storage piles, rail cars or trucks, or other stationary containers.
The methods apply to feed solids, bottom ash/slag, fly ash, and soil.
Three possible methods are available for sampling stationary materials:
D2234-76 for solids and other lumped materials, D346-78 for solids or any
material in hopper cars or trucks, and C311-77 for fly ash and other
granular materials (except pulverized coal).
The first method involves taking a prescribed number of increments of
the material from systemically or randomly located points throughout the
volume of the pile or hopper. Points that are selected systematically are
preferred. The material can be shoveled from the pile, but augers or
slotted pipes (thiefs) are more useful when it is necessary to remove
material from the interior of a pile.
Method D346-78 is very similar to D2234-76 but also includes a useful
diagram for selecting sampling points in a loaded hopper car or dump truck
(see Figure 5-11). It is expected that access to certain waste materials
may be restricted until after they are loaded into rail cars or trucks.
Therefore, this method may be use to selected sampling points on any
material so stored.
Method C311-77 involves taking grab or composite samples of granual
material in bulk storage or in rail cars or trucks. Samples are to be
withdrawn from the entire volume of material from "well-distributed" points
over the area of storage. Samples of dust or sand-like material are
probably the easiest to obtain with a thief or auger. Particular care
should be taken to sample points on the outside of the pile (or surface of
the container) first, since climbing on the material to obtain interior
samples will disturb the outer layers.
69
-------
L
To
L
To
L
To
L
To"
L » i
*. —
1 L
To
-encth
L
To
Of C32
L
To
L
To
— —
L
To
— —
L
To-
i
W/6
4
W/3
T/
» -
4
C
W/3
#
W/6
A
Width of
Car
Figure 5-11. Example sampling grid.
70
-------
Equipment needs for sampling stationary materials will be a function of
the way the material is being stored. Material in piles can be sampled with
shovels (small piles), borers, augers, or thiefs. A bucket or box will be
needed to composite the material and take it back to the lab. Material in
bins or hoppers can sometimes be drawn directly from an outlet, requiring
only a sample container. Otherwise, a thief or borer (on an extension, if
necessary) should be used from the access door. Material in rail cars or
trucks can be sampled with shovels or borers.
Hhere possible the materials of construction of the sampling and
P
transfer devices should be either glass or Teflon . If this is not
D
feasible, then glass or Teflon lined components should be used. If this is
not possible, stainless steel components should be used. All components
should be thoroughly cleaned prior to use according to the procedures
described subsequently in Section 5.5.
The sampling protocol for stationary material will depend largely on
the configuration of the material and its location. Material that is stored
in piles will be the easiest to sample, simply because access to.all
portions of the pile is unrestricted. In certain cases, solid waste streams
may not be accessible within the plant, so the best sample of definable
quality may be obtained from the haul vehicles at the time they discharge
their loads at disposal sites. A systemic sampling plan that will obtain
material from the entire volume of the pile (not just the surface) must be
designed. Also, the size of the particles must be taken into account so
that the diameter of the sampling device exceeds the top size by at least
2 1/2 times. Consideration should be made of the weathering conditions
undergone by material, especially if the pile is outside. Every effort
should be made to sample material that has been recently generated.
Selection of sampling points for materials in hoppers or bins may be
more difficult because of access restrictions or the limitations of sampling
equipment. Therefore, a representative volume may have to be drawn from the
hopper outlet (ASTM C311-77).
Sampling of materials from rail cars or trucks should be similar to
sampling of storage piles, except that the selection of points is
71
-------
constrained by the dimensions of the container. A sampling plan, similar to
that outlined in ASTM D346-78, will have to be designed for each different
kind of container (e.g., a dump truck vs. a 40-ft bulk trailer). Typical
sample points in a rail car or other rectangular container would be selected
as shown in Figure 5-11. Samples should be taken approximately 1 foot below
the surface of the material in the container using an auger or similar
coring-type device.
A similar approach should be taken for sampling soils. With soils,
however, it will first be necessary to select a sampling site. The area
selected was chosen visually as the area most likely to contain dioxin
contamination. For example, soils adjacent to a waste handling area may be
a good candidate. The selected area should be conceptually sectioned into
grids and a composite sample made by taking material from each section and
combined to make a composite. This approach is similar to that shown in
Figure 5-11, rectangular rail cars.
The appropriate methods for soils are the bulb planter and auger. The
bulb planter, while not illustrated here, is the common bulb planter
available from garden tool suppliers. The bulb planter should be used to
obtain surface samples (1" to 4" deep) while the auger should be used to
obtain deeper samples. The composite, if possible, should be composed of
both surface and subsurface samples.
5.3.3 Dipper/Scoop
Grab samples of sludge material may be collected if access to a
sluiceway is available. The grab sample should be collected with a modified
dipper. This method may also be applicable if access to an underground pipe
through manholes or other access points is available.
Grab sampling with a dipper should be used for collection of sludge
samples of sludge wastes are pumped from a thickener to a settling pond.
With this method, randomly chosen grab samples are collected from sludge
waste streams. Several samples from different locations in the sluiceway
should be collected to obtain a representative cross-section.
The dipper used for grab sampling is constructed of a wide mouthed
n
Teflon or glass container (1 liter volume) attached to an end of a
72
-------
telescoping aluminum or fiberglass pole. The dipper collects sludge samples
directly from the sludge waste stream, and the sample is then transferred to
an appropriately sized temporary storage container.
To take a grab sample with a dipper, the dipper is cleaned, mounted on
a telescoping pole, and inserted into the stream at the desired depth with
the mouth of the container down. The dipper should be turned over to an
upright position, allowing the container to fill completely. The dipper can
then be removed from the sludge, and the sample transferred to a temporary
storage container. This process should be repeated until sufficient
increments have been collected.
Precaution should be taken to avoid sampler loss if the waste stream is
moving at a high velocity.
5.4 SAMPLE SIZE, NUMBER, AND COMPOSITING
It will be necessary to prepare composites of each stream sampled.
Figure 5-12 illustrates the general procedure. The size of the individual
samples should be selected so that each final, composited sample is about
4 liters or 5 pounds.
With solids, sludges, and soils, two types of compositing methods can
be used. Where the solids are relatively dry, single samples can be taken
at each interval and then ground, combined, and stirred, prior to splitting
into the final samples. Wood chips are a good example of where this
compositing technique is appropriate.
In other cases where the material is sticky, the above technique is not
appropriate. Sewage sludges are an example. Mixing these samples would
require a lot of transfer and contact, thereby allowing for dioxin
adsorption into surfaces. For these materials, the preferred compositing
technique is to add an individual sample to each of the final sample
containers at every interval. In the example shown in Figure 5-11, this
would involve taking the three final sample containers to the sample point,
adding 0.7 liter or 0.7 Ib to each and repeated at regular intervals until
73
-------
Mix or Stir
Well
TROIKA
SPARE
PLANT
Individual Samples
2.0 Litre each
~ 2 Ib each (1 kg)
Amber glass bottles
with Teflon lid
Composite Sample
5 gal (20 L)
Glass with Teflon
lined lid
Final Samples
1 gal (L) or 5 Ibs.
Amber glass with
Teflon lid times 3
1.
Example shown is for eight samples from different locations or
differing time periods. Actual number, frequency and size may vary
as judged by the the test plan.
Figure 5-12. Conceptual design of sample compositing method.
74
-------
eight individual samples had been taken. For consistency, each of the three
individual samples in the example should be taken in close proximity to one
another.
The results of this compositing effort will produce three samples of
each stream, one or more of which will be analyzed. For the hypothetical
example presented in this section, this will result in sample requirements
shown in Table 5-2. The actual requirements will probably vary with each
site, and a similar table will be prepared as part of each site-specific
test plan.
5.5 CLEANING PROCEDURES
The sampling containers and sampling equipment shall be cleaned prior
to the test by the procedures listed in Table 5-3. The cleaned glassware
D
will be transported to the sampling location with the Teflon lid tightly in
place. Once the sample is introduced to the container, the lid shall be
D
replaced and wrapped with Teflon tape.
The sampling equipment should be precleaned as noted in Table 5-3,
wrapped in cleaned foil and transported to the sampling locations. Between
sampling at the same location, no extra cleaning is necessary other than
washing off the residual material. When going to a new location with the
same equipment, the cleaning shall consist of:
1. Removal of excess sample,
2. H20 rinse (X3),
3. Acetone rinse (X3) (pesticide grade),
4. Hexane rinse (X3) (pesticide grade), and
5. Air dry and wrap in foil.
5.6 REPORTING FORMAT
The reporting format for solid/sludge/soil analysis shall be total
micrograms of TCDD per sample submitted (with blanks having been analyzed
and subtracted from the delivered number). The final results will be
expressed as ug TCDD/kg for each liter of sample and ug TCDD/hr for each
sample point. The report should relate dioxin emissions on the basis of
75
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TABLE 5-2. HYPOTHETICAL SOLID AND SLUDGE SAMPLE REQUIREMENTS
Sample #
1
2
3
4
5
6
Source
Sludge Feed
Solid Feed
Bottom ash/slag
Fly ash (cyclone)
Scrubber sludge
Fly ash (ESP)
Type
Sludge
Solid
Solid
Solid
Sludge
Solid
TOTAL
# Taken
3
3
3
3
3
1
18
# Analysis
1
1
1
1
1
1
6
1) These figures are derived from the generic site (Figure 4-1) and are only
approximate for a source containing a maximum number of liquid streams.
Each site-specific test plan will incude its own requirements for samples
to be taken and analyzed.
76
-------
TABLE 5-3. PRETEST EQUIPMENT CLEANING PROCEDURE FOR
SAMPLING CONTAINERS
NOTE: USE DISPOSABLE GLOVES AND ADEQUATE VENTILATION
1. Soak all glassware in hot soapy water (Alconox) 50°C or higher.
2. H20 rinse (X3).
3. Distilled/deionized H0 rinse (X3).
4. Chromerge rinse if glass, otherwise skip to 6.
5. Distilled/deionized H90 rinse (X3).
6. Acetone rinse (X3), (pesticide grade)
7. Hexane rinse (X3), (pesticide grade).
8. Oven dry (110°C - HR).
9. Cap containers with Teflon lids. Foil wrap the sampling equipment.
• 77
-------
plant throughput where appropriate, e.g., pg/kg sewage feed. These units
would not be appropriate for soils. An example of this format is shown in
Table 5-4.
78
-------
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79
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6.0 ACQUISITION OF DESIGN AND OPERATING DATA
6.1 INTRODUCTION
An important aspect of the source test effort is acquisition of
operating and design data for the combustion device and control device being
tested. This data will be used in the preparation of the source test report
and in the evaluation and interpretation of the test results for that
facility. In addition, certain operating and design data will be needed in
order to evaluate the results of the entire Tier 4 sampling effort and to
extrapolate the results to other combustion sources.
Specifically, we will determine if the operation is typical of the
population in general by comparing the operating data with those from other
units. Also, if dioxin compounds are found, these data may provide
information on the effect, if any, of operating conditions on dioxin
emissions.
The following subsections describe the operating data and design data
that will be obtained during the test. The first presents the types of data
that will be collected and is split between design and operaing data.
Finally, a proposed data acquisition schedule is presented.
6.2 DESIGN AND OPERATING DATA
6.2.1 Design Data
Design information on the combustion device and associated pollution
control device should be obtained as part of the source test. This
information will be used to prepare the process description section of the
source test report. It will also be used during the analysis of all of the
Tier 4 emissions data to make comparisons and draw conclusions between
sites. Some design information (stack parameters) is also needed as inputs
to the modeling portion of the risk analysis.
Table 6-1 presents a list of information needs for a typical combustion
source. This list was derived from the ASME protocol. Much of this data
will be requested for the source during the pretest survey and will be used
as inputs to the site selection process.
80
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TABLE 6-1. DESIGN DATA NEEDS FOR COMBUSTION SOURCES
SOURCE IDENTIFICATION
1. Source Category:
NEDS/SCC Number: _
Site Name:
Address:
Four Digit SIC Number:
Contact Name:
Title:
Phone
2. Longitude and latitude of stack.
3. Plot plan of facility showing combustion devices, control devices, fuel
storage, ash storage and disposal, and plant boundaries.
4. Type/design of combustion device (e.g., multiple hearth, fluidized bed,
etc.):
Number of combustion sources at facility and designation of source
tested:
Size of sources (MMBtu/hr, heat input, or tons fuel/waste/year:
Fuel types used (list each fuel and percent contribution to total for
source to be tested:
1 V 9 V "5 °/
1 • la £.. /a 3, la
5. Describe waste and process or source generating waste (e.g., primary
sewage sludge treatment, black liquor from kraft process).
6. Describe waste fuel preparation method if appropriate (e.g., dewatering.
of sludge to X% moisture using centrifuge).
7. Describe source of chlorine or precursor contamination (e.g., chlorine in
bleach plant effluent combined with black liquor).
8..Design steam production rate and conditions:
Ibs/hr at °F,
(if saturated)
_quaiity.
_psig, and
81
-------
9.
10.
TABLE 6-1. DESIGN DATA NEEDS FOR COMBUSTION SOURCES (CONTINUED)
Waste feed properties for which unit was designed:
- Range of heating valves to
- Range of moisture contents '
- Range of ash contents
to
to
_Btu/lb
_wt.«
wt %
Please provide a cross-sectional diagram of the facility, preferably to
scale, showing the spatial relationship between the major elements of
the process train, including: the waste feed system to the grate, the
grate and residue removal system, shape of the furnace, primary and
secondary combustion air ports, the boiler and its flue gas passages,
soot blowers, major heat transfer surfaces, economizer, air pre-heater
(if appropriate), air pollution control system, induced draft fan, and
stack. Indicate locations of temperature detectors also.
11. Description of the boiler:
- Supplier
- Furnace Volume (ft )
- Firebox dimensions (ft) L
- Kind of soot blowers
W
- Soot blowing schedule (approximate times)
12. Type of combustion (e.g., excess air, starved air)
13. Overfire and underfire air distribution
- Describe design and type of all air ports
- Describe how total combustion air and air distribution is controlled.
14. Type of draft
How is draft regulated?
15. Description of waste fuel feeding and stoking system.
- How is feeding rate controlled?
- Frequency and length of feed ram stroke.
82
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TABLE 6-1. DESIGN DATA NEEDS FOR COMBUSTION SOURCES (CONTINUED)
16. Describe the overall plant control system logic (e.g., what
measurements are used as the basis for controlling firing rate?)
17. Stack height (ft)
Stack diameter at top (ft)
18. Describe ash handling systems (e.g., bottom ash, wet sluiced
19. Type of air pollution control system
20. If Electrostatic Precipitator
- Specific collection area (ft2/l,000 ACFM)
- Design temperature at inlet (°F)
- Number of independent bus sections ^
- Number of independent bus sections in service during emission
sampling
- Design particulate loading at inlet _
at outlet"
- Rapping frequency
jgrains/dscf
"grains/dscf
21. If Fabric Filter
- Air-to-cloth ratio (ACFM/ft*)
- Design pressure drop across bags (in., W.G.)
- Design gas temperature at inlet (°F)
- Total number of bags
- Actual number of bags in service at time of sampling
- Bag cleaning method
22. Which flue gas components are regularly measured?
Oxygen
Carbon monoxide
Hydrocarbons
Other (specify)
Is flue gas opacity regularly monitored?
23. Description of existing temperature monitors.
Locations
Type of temperature detector(s)
Manufacturer and model number
83
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6.2.2 Operating Data
Operating data will be collected during the test and will include both
the combustion device and any associated pollution control equipment.
During the pretest survey, the available facility instrumentation will
be identified, and copies of operation logs will be obtained. Prior to the
test, the test contractor should decide what instrument readings will be
taken. For the purpose of the Tier 4 test program, the prime concern is to
record combustion device and control operating parameters that potentially
could affect dioxin formation. These parameters will indicate the operating
status of the unit in terms of load and combustion conditions.
Examples of operating conditions that should be recorded are steam flow
O
(10 Ib/h), flue gas oxygen (%), flue gas CO (ppm), and flue gas temperature
(°F). The values will be used to determine if the combustion device is
'operating at normal production levels and to compare the current operating
conditions with target and design conditions. Major deviations from normal
values will later be evaluated in relation to their potential impact on
combustion device and control device performance and .dioxin and particulate
emission levels. Continuous emission monitoring data will also be recorded
(see Section 3) since parts of this data are also considered operating data;
e.g., flue gas flow rate.
Combustion device operating data that should be measured during a
source test are plant specific. Each combustion device is usually custom
designed and erected with a unique instrument and control system package.
The level of instrumentation is specified by the design engineer and
purchaser (plant engineering department). Based on the type of combustion
device, the mode of heat recovery, the fuel and waste combusted, the size of
the boiler, its cost, and the experience of the purchaser, the instrument
package may range from an extremely straightforward package to one that'is
quite complex. In general, a minimum amount of instrumentation is necessary
to safely operate the boiler, and this level of instrumentation will be
present in all facilities. More complex instrument packages can include an
automated computer control system that allows the source to optimize
84
-------
combustion and increase the overall efficiency of the operation. Typically,
the instruments will, at a minimum, indicate the flows, temperatures, and
pressures of major streams.
The most critical boiler parameters are recorded on continuous strip
charts or circular chart records, and copies may be obtained after the stack
test (at the end of the day) to provide the necessary documentation. Most
facilities require the boiler operator to record key parameters at set
intervals on a log sheet or in a log book. The log sheet is typically
divided into the following general measurement areas: waste materials used
as fuels (e.g., black liquor), auxiliary fuels, forced air, furnace drafts,
gas temperatures, feedwater, steam, and miscellaneous items. These are
typically recorded every 2 hours.
Table 6-2 lists the items or conditions that should be recorded during
the stack test. The list is based on a typical black liquor boiler and will
require adjustment for individual installations and for different fuel
types.
Integrator readings should also be recorded at the beginning and ending
of each test run for the following parameters:
3
Waste materials used as fuels [e.g., black liquor flow (10 Ib or
gal)];
Steam flow (Ib);
Steam used in soot blowing (Ib);
Oil flow (Ib or gal); and
Natural gas flow (103 ft3).
Based on data obtained from the log, steam tables, integrator readings,
and boiler design data, the following values can be calculated:
Average steam flow for each run;
Average waste fuel fired (10 Ib/h) for each test run;
Average waste composition (e.g., black liquor, solids) for each
run;
Heat input (10 Btu/h) to the boiler for each test run for each
fuel fired (waste, oil, natural gas);
Average boiler output (10 Btu/h) for each test run;
85
-------
TABLE 6-2. EXAMPLE 'OPERATION PARAMETERS TO BE RECORDED FOR A
BLACK LIQUOR RECOVERY BOILER DURING PERFORMANCE TESTS
Parameter
Variable
Units
Black liquor (for other
devices, substitute
appropriate parameters
to monitor quantity and
quality of waste fuel
being fired; e.g.,
gallons sewage sludge
and moisture content.
Auxiliary fuels
Forced air
Liquor flow
Black liquor pressure
Gun size
Number of guns
Black liquor temperature
BLS to guns
BL flow to ESPa
BLS to ESPa
BL flow to evaporator3
BLS to evaporator3
Oil flow
Number of guns
Oil pressure
Oil temperature
Natural gas rate
Primary air flow
Primary air pressure
Primary air temperature
Secondary air flow
Secondary air pressure
Secondary air temperature
Tertiary air flow
Tertiary air pressure
Tertiary air temperature
Total air flow
gal/min
(103 Ib/h)
psig
None
None
°F
%
gal/min
Of
10
gal/min
(103 Ib/h)
%•
gal/h
None
psig
°F
103 ft3/h
scf/min
in. H20
°F
scf/min ,
in. HpO
°F
scf/min
Psig
°F
scf/min
86
Continued
-------
TABLE 6-2.' EXAMPLE OPERATION PARAMETERS TO BE RECORDED FOR A
BLACK LIQUOR RECOVERY BOILER DURING PERFORMANCE TESTS
(CONTINUED)
Parameter
Variable
Units
Furnace drafts
Furnace
Boiler inlet
Boiler outlet
Economizer outlet
ID fan inlet
Precipitator inlet
in. H20
in. H20
in. H20
in. H20
in. H20
in. H20
Gas temperatures
Boiler outlet
Economizer outlet
Evaporator outlet
ID fan outlet
ESP inlet
°F
°F
°F
°F
°F
Feedwater
Flow
Pressure
Temperature
Ib/h)
psig
°F
Steam
Flow
Drum pressure
Superheater temperature
(HT Ib/h)
psig
°F
Chemicals
Salt cake makeup
Ib/min
Miscellaneous
Flue gas oxygen (boiler outlet) %
Black liquor heat value Btu/lb BLS
To be used with correction factors to calculate BLS to guns where not
measured directly.
87
-------
Boiler thermal efficiency (heat output/heat input) for each test
run; and
Boiler excess air (percent).
Acquisition of combustion device operating data will depend upon
available facility instrumentation. Additional process instrumentation,
cannot be supplied by the test contractor. For this reason, close attention
should be paid to the amount of instrumentation available at the facility
during the pretest survey and the amount of data routinely recorded by the
boiler operator.
In addition to monitoring and recording key operating parameters for
the combustion device, it is also necessary to monitor and record operating
data for the pollution control device. Anomalies in the recorded data over
the period of the test should be noted in the source test report and will
help interpretation of results.
The aquired control device operating data should reflect those
variables which affect control device performance. These variables will
vary from control device to control device. In addition, the existing
instrumentation will vary from facility to facility depending upon the size
and complexity of the control device. Table 6-3 indicates some variables
that can be monitored for the control devices which are expected to be used
at the combustion sources under study. The majority of the devices of
concern are anticipated to be particulate control devices. However, some
combustion sources may employ other devices, such as afterburners, etc.;
and many companies have more than one device; for example, an ESP and then a
scrubber. Decisions regarding which control device parameters to be
monitored should be made following the pretest survey.
6.3 SCHEDULE FOR OBTAINING OPERATING DATA
The schedule for obtaining operating data will be specified in the test
plan and will be based on the length of the test, plant operating schedules,
and the data available from existing operating logs. The simplest method of
getting this data is to make copies of the operating logs. These are
recorded by the plant operators typically at 2-hour intervals. It is not
likely, however, that this alone will be sufficient.
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TABLE 6-3. EXAMPLE OPERATING AND MONITORING PARAMETERS
FOR CONTROL DEVICES
Device
Operating Parameters
ESP
Power level (for all chambers)
- Primary current
- Primary voltage
- Secondary current
- Secondary voltage
Spark rate
Opacity
Scrubber
Scrubber pressure drop
Scrubber liquor flow rate
Fabric filter
Pressure drop across bags
Opacity
Afterburners
Fuel flow rate
Inlet and outlet.temperature
Opacity
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The recommended schedule for this program is that the data be recorded
hourly. The plant operators may be willing to.record instrument readings
more frequently while the test is in progress. It is also likely that not
all of the desired information will be contained on the operator logs. Once
again, the plant operators may be able to do this during the test program.
The option of having the plant increase the level and frequency of data
recording should be discussed during the pretest site survey. If such
arrangements are not possible, then one of the test crew personnel will be
assigned the job of recording process measurements every hour.
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7.0 SAFETY
Dioxins, most notably 2,3,7,8-TCDD, are toxic and can pose health
hazards to humans even at low levels of exposure. For this reason,
site-specific health and, if applicable, safety plans should be prepared
prior to conducting sampling at Tier 4 facilities. Even if no 2,3,7,8-TCDD
is suspected at a facility, other compounds may be present in several media
(i.e., fuel, waste being burned, soil) and may present an exposure risk to
the samplers.
A site-specific test plan will be prepared as part of each test plan.
The need for attention to safety will be assessed as a result of information
gathered as part of the pretest site survey. In some cases, the safety
requirements may be the use of standard protective equipment without the
need for the more rigorous safety procedures. The final decision on what
safety requirements are necessary will be made by the Safety Officer of the
test contractor after discussing the site-with pretest survey personnel.
The Tier 4 test sites represent substantially less danger than most
other sites in the study. The safety considerations presented here were
developed from those developed for the overall dioxin assessment program.
Due to the nature of the Tier 4 sites, it is anticipated that many of the
procedures presented here can be relaxed or eliminated entirely. This is
the purpose of the review by the Safety Officer.
7.1 SITE SAFETY
The following items represent the items that should be considered at a
site where there is a strong chance of contact with dioxin or other
hazardous materials. It is given here as a worst case for Tier 4 sites,
since these sites are expected to have fewer exposure problems than other
test sites in the program. The testing crew's Safety Officer will determine
if these precautions are warranted or can be modified or eliminated. The
results of this evaluation will provide the framework of the safety plan in
the test plan.
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1. Access - To reduce interferences with the test crew and reduce any
safety risks, the number of test observers should be kept to a minimum. No
personnel should be permitted near the test area without the consultation of
the field crew chief. None of the test crew or observers should be allowed
to wander around the site without the knowledge of the field crew chief or
plant manager.
2. Physical Examinations - EPA and contractor personnel should have
received a complete physical examination within the past year.
3. Personal Hygiene - No one should be permitted to eat, drink, or
smoke within the site. All personnel should thoroughly wash hands and face
with soap and water before leaving the site. Individuals should wash hands
with soap and water before urinating. All footwear, once worn inside the
site, must remain on-site until completion of the field work. At the end of
each day, any disposable clothing, if used, should be removed and disposed
of in SB-gallon metal drums. Individuals are expected to thoroughly shower
as soon as possible after leaving the job site at the end of the day.
4. Personnel Exposure - In the event of direct skin contact with
sample material, the affected area should be washed immediately with soap
and water. If a decontamination is needed, there will be a person stationed
in the decontamination area to assist in helping people on and off with
their protective clothing.
5. Hospital - At least one non-sampling person should know the
quickest route to medical facilities. The test plan should contain the
phone numbers of the nearest ambulance and hospital.
6. Decontamination - If necessary, a 20 by 20 foot area located next
to the site will be provided as a decontamination area. Individuals within
the site should remove all their disposable clothing before exiting the
area. All disposable items should be placed in large plastic bags located
within this area, and the items should be properly disposed of.
In an effort to reduce the volume of contaminated trash and rinse
water, team members are to make a conscious effort to minimize the amount of
equipment and supplies brought into the site. It is highly advisable to use
only disposable protective clothing (including booties) when sampling for
dioxin in areas of suspected contamination at ppm or greater levels.
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7. Disposal of Mash and Rinse Solution - All wash and rinse water
should be disposed of at the end of each working day on the working site.
Rinse solvents should be allowed to evaporate.
Regardless of the Safety Officer's assessment of the above procedures,
minimum recommended safety requirements are the use of the following safety
equipment:
hardhat,
safety shoes,
eye protection,
respirator (as needed), and
gloves (as needed).
7.2 LABORATORY SAFETY
All dioxin analyses will be done by Troika; however, precursor analyses
will be done in remote Radian laboratories. Composites of the potentially
contaminated material will be done on-site. The following laboratory
procedures are recommended. Here, also, these should be reviewed by the
Safety Officer and amended where appropriate. The resulting list of safety
procedures should appear in the test plan.
1. Protective Equipment - Use throw-away plastic gloves, apron or lab
coat, safety glasses, and lab hood adequate for radioactive work.
2. Training - Workers must be trained in the proper method of
removing contaminated gloves and clothing without contacting the exterior
surfaces.
3. Personal Hygiene - Thoroughly wash hands and forearms after each
manipulation and before breaks (i.e., coffee, lunch, and shift).
4. Confinement - Isolate the work area with posted signs, segregated
glassware and tools, and plastic-backed absorbent paper on benchtops.
5. Waste - Good technique includes minimizing contaminated waste.
Plastic bag liners should be used in waste cans.
6. Disposal of Wastes - 2,3,7,8-TCDD decomposes above 800°C.
Low-level waste such as absorbent paper, tissues, animal remains, and
plastic gloves may be burned in a good incinerator. Gross quantities
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(milligrams) should be packaged securely and disposed of through commercial
or governmental channels which are capable of handling high-level
radioactive wastes or extremely toxic wastes. Liquids should be allowed to
evaporate in a well-ventilated hood or placed inside a disposable container.
Residues can then be handled as above.
7. Decontamination - Personnel should use mild soap with plenty of
scrubbing action. For glassware, tools, and surfaces, Chlorothene NU
Solvent (Trademark of the Dow Chemical Company) is the least toxic solvent ;
shown to be effective. Satisfactory cleaning can also be accomplished by
rinsing the Chlorothene, then washing with any detergent and water.
Dishwater can be disposed to the sewer. It is prudent to minimize solvent
wastes because they may require special disposal through commercial sources
which are expensive.
8. Laundry - Clothing known to be contaminated should be disposed of
with the precautions described under "Disposal of Wastes." Lab coats or
other clothing worn in 2,3,7,8-TCDD work areas can be laundered. Clothing
should be collected in plastic bags. Persons who convey the bags and
launder the clothing should be advised of the possible hazard and trained in
proper handling. The clothing can be put into a washer without contact if
the launderer knows the problem. The washing machine should be run through
a cycle before being used again for other clothing.
9. Wipe Tests - A useful method of determining cleanliness of work
surfaces} equipment, and tools is to wipe the surface with a piece of filter
paper. Extraction and analysis by gas chromatography can achieve a limit of
sensitivity of 0.1 ug per wipe. Less than 1 ug 2,3,7,8-TCDD per sample
indicates acceptable cleanliness; anything higher warrants further cleaning.
More than 10 ug on a wipe sample indicates an acute hazard and requires
prompt cleaning before further use of the equipment or work space and also
indicates that unacceptable work practices have been employed in the past.
10. Inhalation - Any procedure that may produce airborne contamination
must be done with good ventilation. Gross losses to a ventilation system
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should not be allowed. Handling of the dilute solutions normally used in
analytical and animal work presents no inhalation hazards except in case of
an accident.
11. Accidents - Remove contaminated clothing immediately taking
precautions not to contaminate skin or other articles. Wash exposed skin
vigorously and repeatedly until medical attention is obtained.
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8.0 QUALITY ASSURANCE AND CONTROL
Quality assurance and control (QA/QC) is a separate and necessary
component of the Tier 4 sampling and analysis efforts. There are several
QA/QC components that should be considered. This section presents two of
the main components - sample identification and the QA/QC plan. The section
on sample identification presents an approach to assigning sampling numbers
that ensures that all pertinent data are included in the sample number. The
section on the QA/QC plan presents and describes the organization of a QA/QC
plan. This section is not intended to be a detailed procedural guideline on
how to prepare a QA/QC plan, but rather a list of the necessary components.
The QA/QC plan is typically as complex and detailed as the test plan and
should be prepared in advance of any test plans. Since the test procedures
will vary little from site to site, a single, well written QA/QC plan can be
used for the whole project. It is assumed that the test contractor is
already familiar with how to prepare a deta-iled QA/QC plan. Procedural
details can be found in Interim Guidelines and Specifications for Preparing
Quality Assurance Project Plans, QAMSO-005/80.
8.1 SAMPLE IDENTIFICATION
All samples taken should receive a unique sample code. This code is
separate from the identification numbers that are assigned by the Troika for
their analysis. This is necessary since there may be samples that are not
analyzed by Troika. In addition, there should be a constituent labeling
format. This organization allows quick and accurate association of analysis
results with process and other data. The label and sample code format is
presented in Figure 8-1.
8.2 THE QA/QC PLAN
The U. S. Environmental Protection Agency policy stipulates that every
monitoring and measurement project must have a written and approved Quality
Assurance (QA) Project Plan. Sixteen essential elements must be considered
and addressed in the QA Project Plan. These elements of the QA Project Plan
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P.O. Box 9948/Austin. Texas 78766
PRELIM. NO:
SAMPIE TYPE:
LOCATION:
DATE: __
REMARK:
Sample Code
Ex. Riv - 0614 - M17 - 1300/1'
Plant
Designation
(Riverside)
t \
ant Date
Type Time
of of
Sample Day
(Method 17)
CONTRACT:
_ FINAL WT:.
TARE :
SAMPLE WT:
Sample
Location
Figure 8-1. Example of label and sample identification code.
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are listed below. The first 16 sections are the essential elements.
Section 17 and 18 shown below may be used as needed. Additional sections
may also be included in the QA Project Plan as appropriate.
Section 1 Title Page
Section 2 Table of Contents and Distribution
Section 3 Project Description
Section 4 Project Organization and Responsibility
Section 5 QA Objectives for Measurement Data in Terms of
Precision, Accuracy, Completeness, Representativeness,
and Comparability
Section 6 Sampling Procedures
Section 7 Sample Custody
Section 8 Calibration Procedures and Frequency
Section 9 Analytical Procedures
Section 10 Data Reduction, Validation, and Reporting
Section 11 Internal Quality Control Checks
Section 12 Performance and System Audits
Section 13 Preventive Maintenance
Section 14 Specific Routine Procedures Used to Assess Data
Precision, Accuracy, and Completeness
Section 15 Corrective Action
Section 16 Quality Assurance Reports to Management
Section 17 References
Section 18 Appendices
Additional details giving the contents that need -;o be considered for
inclusion in each section is discussed below for dioxin sampling. Many of
the details given are generic and should be included in any QA Project Plan.
Each page of the QA Project Plan carries document control information in the
upper right hand corner of the page. The information gives the section
number, the Revision No. (the first draft is revision number zero), the date
and the page number, usually given as "Page of pages."
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Section 1 - Title Page
The title page, in addition to the title "Quality Assurance Plan for
... (Project Name)," must have the signatures of the project organization's
Project Manager and Quality Assurance Official and the funding
organization's Project Officer or Task Manager and QA Officer. In addition,
the title page may include the project organization's name and address.
Section 2 - Table of Contents
The table of contents includes a listing of all the section numbers and
their titles, the number of pages per section, the revision number, and the
revision date for each section. As noted above, all the pertinent
references and appendices with the title of each appendix should be listed.
The table of contents also gives an official list of copy holders and will
include as a minimum those who sign the title page.
Section 3 - Project Description
A general description of the project is provided. Background
information gives the purpose of the test and the intended use of the data.
The experimental design along with appropriate flow diagrams, equipment
sketches, tables and graphs should be included. Anticipated start and
completion dates for the various parts of the project test plan form part of
the project description. A description of the equipment, the test design, a
list of the measurements to be taken, and a description of the data analysis
to be done are all components of the project description.
For sampling combustion sources, a minimum of three replicate samples
is required. Simultaneous collection will be made of at least the
following:
1. Auxiliary fuel,
2. Waste fuel material,
3. Ash discharge from combustion device,
4. Flue gas exiting the pollution control device — the sampling
train being developed by ASME shall be used,
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5. Pollution control device(s) — influent and effluent streams (if
any), and
6. Particulate from particulate control device (if separate from
scrubber.
The test design should cover the normal range of operation of the
combustor and the associated emission control equipment insofar as fuel flow
rate, loading, etc. Stack gases will also be monitored for 02, C02, CO, and
NOX. : Key operating variables of combustion device and control device also
will be recorded.
Section 4 - Project Organization and Responsibility
The primary responsibility and roles of each member of the project team
are summarized in a project organization chart. Where possible, persons
should be named to fill the key positions. The chart shows lines of
authority and communications. It is important that the QA Manager of a
project reports not only to the Project Manager, but also to levels of
corporate management independent of the project itself. The QA Manager of
the project should be independent of the routine sampling and analytical
duties and procedures. An example is shown in Figure 8-2.
Section 5 - Quality Objectives
In this section, the objectives for the data quality are listed in
terms of precision, accuracy, completeness, and representativeness. Goals
for precision and accuracy are based on previous experience of the project
organization in the types of measurements given or from values of precision
and accuracy reported in the literature from other organizations or
laboratories. Sampling and analytical procedures are designed to assure
representativeness of the measurements.
For combustion systems, the concentration and emission rate of a target
compound (or target compounds), e.g., PCDD, is of interest. Sample sizes
are selected to produce samples having concentrations greater than the
expected minimum detection limit. Precision of analytical measurements with
the GC/MS are probably no more than ± 30 percent when analyzing PCB's or
dioxins, when they are derived from a sludge or solid waste matrix. With
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Offsite
Operations
EPA Project Officer
Contractor Program Manager
RTI QA/QC
Coordinator
Project Director
Contractor QA/QC
Coordinator
Field Operations
Director
Sampling and
Analysis Task
Leader
Special Studies
Task Leader
Figure 8-2. Example Organization Chart,
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liquids having a multicomponent matrix, precisions of ± 25 percent may be
the quality objectives. For these matrices, it may not be possible to set
the accuracy. For samples that are "spiked" with a dioxin, recoveries
(sometimes taken as accuracy) may range from 85 to 115 percent.
Section 6 - Sampling Procedures
A detailed description of the sampling procedure for each measured
parameter must be given in this section. Where standard procedures are
outlined in detail elsewhere, they may be included by reference, but any
deviation from a standard procedure or any nonstandard procedure must be
described in detail. Charts, flow diagrams, and equipment diagrams
describing sampling points, data, sample, or material flows should be given.
Descriptions are given of sample containers and procedures to clean the
containers and sampling equipment and sample preservation, transport, and
storage methods. Section 6 also contains a description of the documentation
procedures, including notebooks, data logging, sample labeling,
chain-qf-custody, and QA procedures for independent checks of the data
logging information. Examples of all standard forms and-formats should be
included.
Principles of test methods and rationales for their applicability
should be given. Particular attention should be focused on a consideration
of the expected range of the measurement including the minimum detection
limit, interferences, precision, and accuracy. A detailed description of
test equipment includes a diagram and a discussion of the procedure used to
prepare the equipment for sampling (i.e., cleaning procedure) and a
discussion of how the sample is collected and prepared for shipment or
transfer to the laboratory.
Preparation of the equipment for taking a sample includes a description
of how the equipment is cleaned. If the equipment contains adsorbent beds,
a description of how the bed and resin are to be cleaned and assembled is
essential. Sampling equipment and sampling trains must be assembled and
checked for leaks. A description is given for the operation of the sample
train during the period the sample is being taken, how the sampling period
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is ended, and the sample is prepared for shipment. Field data sheets are
prepared in advance and included in Section 6 of the QA Project Plan. If
any calculations or data processing are done during the sampling phases of
the project, the details of the calculations including the equations are
included in this section.
The apparatus for stack gas sampling consists of a modified EPA
Method 5 train (ASME, 1984). A large (30-gram) XAD-2R adsorbent trap is
added to the Method 5 train before the normal water-filled and empty
D
impingers. Once the XAD-2 module is removed from the train, it is spiked
in the laboratory with a labeled compound before extraction. A blank sample
train may be used to assure that the train and, in particular, the
adsorbent, are not being unduly contaminated by the ambient air rather than
the stack gas. If used, a blank train is set up for each series of tests,
and the probe and the exit of the last impinger are capped. The train
remains assembled for the duration of a test. Recovery of samples from the
blank train and subsequent spiking, extraction, and analysis follow the same
procedure as with the regular stack sampling train.
Section 7 - Chain of Custody
An accurate written record will be maintained which can be used to
trace possession of the sample from the moment of its collection until it
has been analyzed. A chain-of-custody tag (Figure 8-3) will be placed on
all coolers in which samples are stored and shipped. Appropriate spaces for
signatures are needed when the sample is transferred from one person to
another. The date and time at which the custody is transferred should be
indicated on the tag.
Section 8 - Calibration Procedures and Frequency
This section requires that for each measured parameter, the standard
operating procedure for the measurement is described in detail. A written
description of the calibration method is required for this section, listing
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CHAIN OF CUSTODY RECORD
SAMPLERS «
Rcfinquahad by:
•""•"••~—«•».^_^,
R«ttxiui«h«d by:
Received by:
Recaivad by:l
R^povsd by:
Dapatchad by:
of Shipmwie
OatB/TIme R«cwv«d tor Laboratory by
Figure 8-3. Chain-of-custody tag (Versar,
1984)
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also the frequency of recalibration. Any standard reference material that
is to be used in the project must be listed, including its source and
traceability to a primary standard.
Five-point calibration curves are prepared to span the expected range
of concentration. Identification of the standard by lot number source and
purity is part of the permanent record of the project. A minimum of three
replications of each calibration point, including solvent blanks is
recommended. Daily calibration checks throughout the project will be run at
two concentrations; a "blank determination" will be made daily as well.
Individual readings of the calibration checks should fall within the
95 percent confidence interval of the calibration curve.
Section 9 - Analytical Procedures
Officially approved EPA analytical procedures are used when available.
Detailed descriptions of the EPA procedures need not be included in the QA
Project Plan but may be cited by reference. Other standard procedures, such
as ASTM procedures, may also be cited by reference, assuming that the
reference is universally available. All nonstandard and developing
analytical methods are to be described in detail. Topics for discussion
needed in this section include the principle and applicability of the
method, known interferences, sample preparation, and the range of
detectability. If the analytical precision and accuracy are known for this
method, it will be reported in the section. A description of the apparatus,
the reagents, other chemicals used, and any special cleaning requirements
for the apparatus is needed. Quality control and quality assurance
procedures used in the analytical laboratory are also described in this
section.
Generally, samples are spiked with a known quantity of a noninterfering
compound in order to have an interval measure of the expected recovery of
the spike throughout the analytical procedure. It may be necessary to spike
the sample at more than one point in the analysis in order to check on the
validity and the integrity of each step in the analytical procedure.
Quality control checks are generally conducted to monitor the recovery of
the spike with each sample in order to assure that the analytical procedure
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is in control. Interval standard spikes may also be used at the point of
analysis (e.g., injection of the sample into a 6C/FID), and quality control
charts again monitor the "control" at the time of injection.
Part of the experimental design includes the specification of the
number of replications that are needed to determine the precision of the
measurements. The description of the method for determining the accuracy of
the measurements is included in this section. A common analytical quality
control procedure is the daily analysis of a calibration standard.
Frequently, a "blank" is run as a daily calibration check. In this case, a
control chart is maintained should the blank produce a signal so that a
check can be kept on instrument drift or sample carryover from one analysis
to another.
Section 10. Data Reduction, Validation, and Reporting
The data reduction scheme for each major measured parameter is
described in this section. The description includes all the equations used
to calculate each reported parameter. The methods used to treat outliers
and the criteria-used to validate the data are described. It may be
desirable to present a graphical data flow scheme from collection of the
data through storage of the validated compositions.
Separate descriptions are generally needed for data validation
procedures for field and laboratory operations.
Section 11 - Internal Quality Control Checks
All of the quality control checks applied in the field and laboratory
operations are described in this section. The equations used to drive the '
quality control checks and the criteria used to determine whether the
procedure is in control are described. The criteria used to check the
control of any measurement are included (e.g., the acceptable pressure
change for a leak-check determination).
When a daily calibration check is made, either a quality control chart
is maintained or a confidence interval is established in advance in order to
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specify the acceptability of the calibration check reading. In case the
calibration check fails the acceptability limits, the procedure used to
correct such an occurrence is described.
Section 12 - Performance and System Audits
Internal and external procedures to measure the overall system
performance are described in this section. It is necessary not only to
audit the measurements but also the record-keeping activities of the
personnel on the project periodically throughout the course of the project.
Section 13 - Preventive Maintenance
In the QA Project Plan, a schedule of Preventive maintenance tasks is
given before and during the duration of the project. A list of critical
spare parts needed for both field and laboratory operations is listed in
this section. The concern addressed in this section is the effort expended
to minimize any possible downtime because of failure of instrument or
apparatus. •
Section 14 - Procedures Used to Assess Data Precision, Accuracy, and
Completeness
For each measured parameter, the QA Project Plan describes the
procedures used to assess the precision, accuracy, and completeness of the
data. This section describes all the statistical and other mathematical
methods to describe the calculations of central tendency, measures of
variability (for precision), and tests of significance. Calibration data
most frequently fit a linear model. Equations used to fit the calibration
curve are generally derived by the method of least squares. It is then
possible to derive equations for the confidence interval for any particular
calibration measurement. The 95 percent confidence interval is most
frequently used although the 99 percent interval may be more appropriate.
Equations may also be given to test the calibration curve for linearity.
Tables and equations required to test data for outliers may be included
in this section. Should an analysis of variance be appropriate for the
data, the models and equations for these operations are included in this
section.
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When using control charts for routine operations, analyses, etc., the
equations used to derive the upper and lower control limits are given, along
with the criteria used to detect control.
Section 15 - Corrective Action
Corrective action procedures include tabulations of the predetermined
limits beyond which corrective action is required. The type of corrective
action and the person who "initiates" the corrective action must be
identified. The corrective action taken must be noted in the permanent
record of the project, and the person who endorses and approves the action
must be noted in the QA Project Plan.
Corrective action may be initiated as a result of:
Performance audits,
System audits,
Laboratory/interfield comparison studies,
Out-of-control condition on a quality control chart, or
Other QC control conditions defined' in the QA Project Plan.
Since a corrective action cannot be anticipated for every cause of
corrective action, they frequently involve consultation for each case with
the Program Manager, Laboratory Manager, and/or the Quality Assurance
Officer.
Section 16 - Quality Assurance Reports to Management
QA Project Plans identify minimum report requirements for the project;
e.g., weekly, monthly, quarterly, etc. Part of these reports should
identify at least the following:
Periodic assessment of measurement of data accuracy, precision,
and completeness;
Results of performance audits;
Results of system audits; and
Significant QA problems and recommended solutions.
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In addition, any time a critical QA problem arises, it should be brought to
the attention of the sponsoring authority, along with the recommended
solution. A section of the final report of any project must summarize the
QA actions and results for the entire project.
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9.0 SITE SPECIFIC TEST PLAN OUTLINE
It is standard practice to prepare a test plan prior to conducting any
source test, and such a plan will be a component of this program. The test
plan is specific to a particular site and contains detailed information on
how to set up the equipment, conduct the test, maintain records, and reduce
the data. It also contains details on what QA/QC procedures will be
included with the tests. The purpose of the test plan is two-fold: (1) as a
reference for the field test team, and (2) to ensure that all details are
thought out in advance. It also gives the EPA an opportunity to verify that
the testing approach is consistent with the program's objectives. It is
intended to be used in conjunction with the QA/QC Project Plan.
Several sites will be tested, and it will be necessary to prepare a
test plan for each. Since the test objectives and approach are the same for
each site, the test plans will be very similar. This section presents a
generic test plan that includes all of the standard items and procedures.
The details of what will be necessary to use the existing stack port "will be
different for each site-, however, the use of this outline keeps the
documents consistent from test to test and allows them to be prepared
quickly after the pretest site survey.
Figure 9-1 presents a detailed outline for the test plan. It is
important that the test plan contain as much detail as possible. This
includes detailed diagrams of where and how to set up equipment, data
recording forms, equations used to reduce the data, etc. This will avoid
repetitive work later on. It is recommended that the test plan be prepared
during the initial screening phases of the project so that it can be
reviewed and approved prior to the field operations. This will allow any
deficiencies to be detected and corrected.
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1.0 INTRODUCTION
2.0 SUMMARY
3.0 PROCESS DESCRIPTION
4.0 TESTING PROCEDURES
4.1 DESCRIPTION OF SAMPLING LOCATIONS
4.1.1 Gaseous Samples
4.1.1.1 Precombustion Air
4.1.1.2 Combustion Device Outlet
4.1.1.3 Pollution Control Device Outlet
4.1.1.4 Feed Streams
Fuels
Waste streams
4.1.2 Liquid and Slurry Samples
4.1.2.1 Feed Streams
Fuels
Wastes
4.1.2.2 Make-up Water
4.1.2.3 Sluiced Ash
4.1.2.4 Quench/Cooling Water Slowdown
4.1.2.5 Scrubber Slowdown
4.1.2.6 Demister Drain
4.1.3 Solid and Sludge Samples
4.1.3.1
Feed Streams
Fuels
Wastes
4.2
4.1.
4.1.
SAMPLING
4.2.1
4.2.
4.2.
3.2 Ash
3.3 Soil
PROCEDURES
Gases
1.1 CEM
1.2 Mana
4.2.2
4.
4.
CEM Sampling Train
Methods
Flow rate
Moisture
Particulates
Liquids and Slurries (include only methods appropriate
to the site)
2.1 Tap
2.2 Dipper
4.2.2.3 Coliwasa
4.2.2.4 Weighted Bottle
Figure 9-1. Recommended outline of a site specific test plan for Tier 4.
1 111
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4.2.3 Solids and Sludges (include only methods appropriate to
the site)
4.2.3.1 Thief
4.2.3.2 Trier
4.2.3.3 Shovel
4.2.3.4 Auger
4.3 SAMPLE PRESERVATION AND ANALYTICAL PROCEDURES
4.3.1 Sample Preservation
4.3.3.1 Samples for Remote Laboratory Analysis
4'.3.3.2 Samples for Archive Purposes
4.3.2 Analytical Procedures
4.3.2.1 Gases
CEM
Manual Methods
4.3.2.2 Liquids and Slurries
4.3.2.3 Solids and Sludges
4.4 QUALITY ASSURANCE AND QUALITY CONTROL
4.4.1 Calibration Procedures
4.4.2 Documentation for Audit Control
4.4.3 Internal Quality Control Checks
5.0 FIELD TESTING SCHEDULE
5.1 GENERAL SCHEDULE
5.2 SPECIFIC SCHEDULED ACTIVITIES
5.2.1 Equipment Set-up
5.2.2 Daily Activities During Source Test
5.2.3 Equipment Take-down
5.3 PLANT SPECIFIC SCHEDULE AND DATA NEEDS
6.0 DATA HANDLING
6.1 GENERAL PROCEDURES (FIELD LOG BOOKS, ETC.)
6.2 WORK-UP OF CEM DATA
6.3 VOLUMETRIC FLOW RATE DETERMINATION
6.4 MOLECULAR WEIGHT DETERMINATION
6.5 MOISTURE DETERMINATION
Figure 9-1. Continued.
112
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7.0 SAFETY
6.6 PARTICIPATE LOADING DETERMINATION
6.7 PROCESS DATA REDUCTION
7.1 SITE CONSIDERATIONS
7.2 SAFETY PROCEDURES WHILE SAMPLING
7.3 LABORATORY SAFETY
7.4 SAFETY INFORMATION FORM
7.4.1 Emergency Telephone Numbers
7.4.2 Basic Safety Equipment Checklist
7.4.3 Standard Procedures
Figure 9-1. Concluded.
113
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APPENDIX A
ASMS MM5 SAMPLING METHODOLOGY
FOR CHLORINATED ORGANICS
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SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 1 OF 26
SAMPLING FOR THE DETERMINATION OF CHLORINATED
ORGANIC COMPOUNDS IN STACK EMISSIONS
PRINCIPLE AND APPLICABILITY
1.1 Principle: Stack gases that may contain chlorinated organic
compounds are withdrawn from that 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
chromatography/mass spectroscopy (GC/MS).
1.2 Applicability: This method is applicable for the determination of
chlorinated organic compounds in stack emissions. The sampling
train is so designated 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 separately, 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 and constraints of the analytical techniques for
chlorinated organic compounds, especially PCDDs and PCDFs.
Note: This method assumed 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 validated 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 may include the use of a backup resin trap or the addition
of a representative labeled standard (distinguishable from the
internal standard used for quantitation) to the filter and/or the
XAD-2 in the filed prior to the start of sampling. These steps
will provide information on possible breakthrough of the compounds
of interest.
REPORTABILITY
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 modifi-
cation; and (3) an estimate of the effect the modification will produce
on the data.
A-l
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SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 2 OF 26
3. RANGE OF MINIMUM DETECTABLE STACK GAS CONCENTRATION
The range of the analytical method may be expanded considerably through
concentration and/or dilution. The total method sensitivity is also
highly dependent on the volume of stack gas sampled and the detection
limit of the analytical finish. The user shall determine for their
system the minimum detectable stack gas concentration for the
chlorinated organic compounds of interest. The minimum detectable stack
gas concentration should generally be in the ng/m or lower range.
4. INTERFERENCES
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 handling and analysis, care should be taken
to avoid contact of samples and extracts with synthetic organic materials
other that polytetrafluorethylene (TFE ^) . Adhesives should not be used
to hold TFE ® liners on lids (but, if necessary, appropriate blanks must
be run), and lubricating and sealing greases must not be used on the
sampling train.
5. PRECISION AND ACCURACY
Precision and accuracy measurements have not yet been made on PCDD and
PCDF using this method. These measurements are needed. , However,
recovery efficiencies for_source samples spiked with compounds have
ranged from 70 to 120%. '5 .
6. SAMPLING RUNS, 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 sufficient length to
provide coverage of the average operating conditions of the source.
However, this shall not be less than three hours (3).
6.3 Sample Volume; The sampling volume must be sufficient to provide
the required amount of analyte to meet both the MDL of the analytical
finish and the allowable stack emissions. It may be calculated using
the following formula:
Sample Volume
100 100
B
D
A = The analytical MDL in ng
B = Percent (%) of the sample required per analytical finish run
C - The sample recovery (%) „
D = The allowable stack emissions (ng/m )
A-2
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7.
Example: A
SV
APPARATUS
SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 3 OF 26
0.050 ng; B = 10%; C = 50%; and D = 1 ng/m3
n n, 100 100 1 .3
0.05 x x x — = 1m
10
50
Sampling Train: The train consists of nozzle, probe, heated particulate
filter, and sorbent module followed by four impingers (Fig. 1). Provision is
made for the addition of (1) a cyclone in the heated filter box when testing
sources emitting high concentrations 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 impingers following the sorbent
module. If one of the options is utilized, the option shall be detailed in
the report. The train may be constructed 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 borosilicate
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 protection 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)
/5?he sample transfer lines, if needed, shall be heat traced, heavy walled
TFE ^ (1.3 cm [1/2 in.] 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
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SECTION NO.: Appendix A
REVISION NO: Radian 1
DATE: October 25, 1984
PAGE 4 OF 26
(O
in
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to
CD
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OO
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SECTION NO.: Appendix A
REVISION NO.: Radian 1
DATE: October 25, 1984
PAGE 5 OF 26
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 temperature around
the filter holder (and cyclone, if used) during sampling of 120±14°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
Amberlite XAD-2 ^resin (XAD-2), confined in a trap, shall be used as
the sorbent. The sorbent module shall be made of glass with connecting
fittings that are able to form 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. [NOTE: Radian has found that a horizontal coil
in conjunction with a vertical resin trap operates as well as a vertical
coil.] Gas entering the sorbent module must be maintained at <20°C (68°F). •
Gas temperature shall be monitored by a thermocouple 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 channelling 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 modules must be
maintained in the vertical position during sampling.
7.1.8 Impingers
Four or more impingers with connecting fittings able to form leak-free,
vacuum-tight seals without sealant greases when connected together, shall be
used. All impingers are to 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 systems 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 rate, and related
equipment, or equivalent.
7.1.10 Barometer
Mercury, aneroid, or other barometers capable of measuring atmospheric
pressure to within 2.5 cm Hg (0.1 in. Hg) shall be used.
A-5
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?S
I
SECTION NO.: Appendix A
REVISION NO: ASME Draft 4
DATE: October 1984
PAGE 6 OF 26
Figure 2. Acceptable sorbent module design #1.
A-6
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SECTION NO.: Appendix A
REVISION NO.: Radian 1
DATE: October 25, 1984
PAGE 7 OF 26
CONDENSER COIL
28/12
XAD-2
TRAP'
COARSE FRIT-
C^ ^"^ 28'12
Figure 2-A. XAD-2 trap and condenser coil.
A-7
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SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 8 OF 26
!• 1/3
QO • 4.7 cm I? 1-« •»
Figure 3. Acceptable sorbent module design #2.
A-8
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SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 9 OF 26
7.2 Sample Recovery, Supplies, and Equipment
7.2.1 Ground Glass Caps or Hexane Rinsed Aluminum Foil
To cap off^adsorbent tube and the other sample-exapsed portions of the
train. If TFE ^ screw connections are used, then TFE ^ screw caps shall be
used.
7.2.2 Teflon FEP ^Wash Bottle
Three 500 ml, Nalgene No. 0023A59, or equivalent.
7.2.3 Probe and Transfer Line Brush
Inert bristle brush with stainless steel rod-handle of sufficient length
that is compatible with the liner or probe and transfer line.
7.2.4 Filter Storage Containers
filter holder or precleaned, wide-mouth amber glass containers
with TFE Alined 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 Precleaned Metal Can
To recover used silica gel.
7.2.8 Precleaned Graduated Cyclinder, e.g., 250 ml
250 ml, with 2 ml graduations, borosilicate glass.
7.2.9 Liquid Sample Storage Containers
Precleaned amber glASS bottles or clear glass bottles wrapped in opaque
material, 1 L, with TFE Alined screw caps.
8. REAGENTS
8. 1 Sampling
A-9
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SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 10 OF 26
8.1.1 Filter — Fiberglass Reeve-Angel 934 AH or Equivalent
Prior to use in the field, each lot of filters shall be subjected to
precleaning and a quality control (QC) contamination check to confirm that
there are no contaminants present that will 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 solvent (s) to be applied to the
field samples. As a QC check, the extracting solvent(s) shall be subjected
to the same concentration, cleanup and analysis procedures to be used for the
field samples. The background or blank value observed shall be converted to
a per filter basis and shall be corrected for any differences in concentration
factor between the QC check (CF ) and the actual sample analysis procedure
(CF ). QC
Blank value per filter =
where:
Apparent ug of analyte CF
X
CFs
QC
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 to the target detection limit for the analyte(s) of concern
shall be rejected for field use. -Note that acceptance criteria for filter
cleanliness depends not only on the inherent detection limit of the analysis
method but also on the expected field sample volume and on the desired limit
of detection in the sampled stream.
If the filters do not pass the QC check, they shall be re-extracted and
the 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 sut in a giant Soxhlet extractor,
which will contain enough Amberlite XAD-2 resin (XAD-2) for several
sampling traps. An all glass thimble 55-90 mm OD x 150 mm deep (top to frit)
containing an extra coarse frit is used for extraction of XAD-2. The frit is
recessed 10-15 mm above a crenelated ring at the bottom of the thimble to
facilitate drainage. The XAD-2 must be carefully retained in the extractor
cup with a glass wool plug and stainless steel screen since it floats on
methylene chloride. This process involves sequential extraction in the
following order.
A-10
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SECTION NO.: Appendix A
REVISION NO.: ASME Draft
DATE: October 1984
PAGE 11 OF 26
Solvent
Water
Procedure
Initial rinse with 1 L HO for 1 cycle, then discard
Water
Methyl alcohol
Methylene chloride
Hexane
Extract with HO 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 solvent, a
fluidized-bed technique has proven to be the fastest 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 cm (4 in.) diameter 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 column.
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 contaminants. The liquid nitrogen cyclinder
is connected to the column by a length of precleaned 0.95 cm (3/8 in.) copper
tubing, coiled to pass through a heat source. As nitrogen is bled from the
cylinder, 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 warm to the touch and not over 40°C.
Experience has shown that about 500 g of XAD-2 may be dried overnight
consuming a full 160 L cylinder of liquid nitrogen.
As a second choice, high purity tank nitrogen may be used to dry the
XAD-2. The high purity nitrogen must first be passed through a bed of
activated charcoal approximately 150 mL in volume. With either type of
drying method, the rate of flow should gently agitate the bed. Excessive
fluidation may cause the particles to break up.
(b) As an alternate, if the nitrogen process is not available, the XAD-2 may
be dried in a vacuum oven, if the temperature never exceeds 20°C.
The XAD-2, even if purchased clean, must be checked for both methylene
chloride and hexane residues, plus normal blanks before use.
A-ll
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SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 12 OF 26
0.55
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SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 13 OF 26
(c) Storage of Clean XAD-2: XAD-2 cleaned and dried as prescribed above is
suitable for immediate use in the field, provided it passed the QC
contamination check described in (d), below. However, precleaned dry XAD-2
may develop unacceptable levels of contamination if stored for periods
exceeding a few weeks.
If precleaned XAD-2 is not to be used immediately, it shall be stored
under distilled-in-glass methanol. No more than two weeks prior to
initiation of field sampling, the 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 contamination check described in (d), below.
If the stored XAD-2 fails the QC check, it may be recleaned by 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, "precleaned", 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 tube 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) to be applied to the field
samples. The quantitative criteria for acceptable XAD-2 quality will depend
on the detection limit criteria 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 of the MDL for the analyte(s)
of concern shall be rejected for field use. Note that the acceptance 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 Glass Wool
Cleaned by thorough rinsing, i.e., sequential immersion in three
aliquots of hexane^g-dried in a 110°C oven, and stored in a hexane-washed
glass jar with TFE Alined screw cap.
8.1.4 Water
Deionized, then«elass-distilled, and stored in hexane-rinsed glass
containers with TFE ^-lined screw caps.
A-13
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SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 14 OF 26
8.1.5 Silica Gel
Indicating type, 6-16 mesh. If previously used, dry at 175±5C for 2 hr.
New silica gel may be used as received.
8.1.6 Crushed Ice
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.
9.2 Hexane
Pesticide quality, Burdick and Jackson "Distilled in Glass" or equivalent,
stored in original containers. A blank must be 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
A-14
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SECTION NO.; Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 15 OF 26
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 molecular 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.
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 if 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 an including the sorbent module
and the first impinger 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 residual 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
O
Use a sufficient amount (at least 30 gms or 5 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 ends. These caps should not
be removed until the trap is fitted into the train. See Fig. 2 for details.
A-15
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SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 16 OF 26
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 in Table 1.
10.1.2 Preparation of Collection Train
During preparation and assembly of the sampling train, keep all train
openings where contamination can enter covered until just prior to assembly
or until sampling is about to begin. Caution: Do not use sealant greases in
assembling the train.
Place approximately 100 gms of water in each of the first two impingers
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 on the
impingers and on the data sheet.
Assemble the train as shown in Fig. 1.
Place crushed ice in the water bath around the impingers.
10.1.3 Leak Check Procedures
10.1.3.1 Initial Leak Check
The train, including the probe, will be leak checked prior to being
inserted into the stack after the sampling train has been assembled. Turn 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, /feeak check the train at the sampling site by
plugging the nozzle with a TFE ^plug and pulling a 380 mm Hg (12 in. Hg)"
vacuum. -A leakage rate in excess of 4% 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 check 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 in. Hg) is exceeded during the test, either leak check at this higher
vacuum or end the leak check as described below and start the test over.
dO
When the leak check is completed, first slowly remove the TFE ^ plug
from the 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.
A-16
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SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 17 of 26
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-------
SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 18 OF 26
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.
Such leak checks shall be performed according to the procedure given 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 poinlj in the
test. If the leakage rate is found to be no greater than 0.00057 m /min
(0.02 ft /min) or 4% of the average sampling rate (whichever is smaller) the
results are acceptable. If, however, a higher leakage rate is observed, the
tester shall either: (1) record the leakage rate and then correct the volume
of gas sampled since the last leak check as shown in Section 10.1.3.4 of this
method, or (2) void the test.
10.1.3.3 Post-Test Leak Check
A leak check is mandatory at the end of a test. This leak check shall
be performed in accordance with the procedures given in Section 10.1.3.1
except that it shall be conducted at a vacuum equal to or greater than the
highest value recorded during the test... If the leakage rate is found to be
no greater than 0.00057 m /min (0.02 ft /min) or 4% of the average sampling
rate (whichever is smaller), the results are acceptable. If, however, a
higher leakage rate is observed, the tester shall either: (1) record the
leakage rate and correct the volume as gas sampled since the last leak check
as shown in Section 10.1.3.4 of this method, or (2) void the test.
10.1.3.4 Correcting for Excessive Leakage Rates
The equation given in Section 11.3 of this method for calculating Vm
(std), the corrected volume of gas sampled, can be used as written unless the
leakage rate observed during any leak check after the start of a test
exceeded L , the maximum acceptable leakage rate (see definitions below).
an observef leakage rate exceeds L , then replace V^ in the equation in
Section 11.3 with the following expression:
If
m
V
where:
V » Volume of gas sampled as measured by the dry gas meter (dscf).
m
2
L = Maximum acceptable leakage rate equal to 0.00057 m /min.
a (0.02 ft /min) or 4% of the average sampling rate, whichever is
smaller.
3
L » Leakage rate observed during the post-test leak check, m /min
p (ft3/min).
A-18
-------
SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 19 OF 26
L = Leakage rate observed during the leak check performed prior to
"i th" leak check (i = l,2,3...n), m /min (ft /min).
the
0. = Sampling time interval between two successive leak checks beginning
• with the interval between the first and second leak checks, min.
0_ = Sampling train interval between the last (n th) leak check and the
" end of the test, min.
Substitute only for those leakages (L. or L ) which exceeded L .
ip a
10.1.3.5 Train Operation
During the sampling run, a sampling rate within 10% of the selected
sampling rate shall be maintained. Data will be considered acceptable if
readings are recorded at least every 5 min. and not more than 10% of the
point readings are in excess of ±10% and the average of the point readings is
within ±10%. During the run, if it becomes necessary to change any system
component in 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. 5. Be sure to record the initial dry gas meter reading.
Record the dry gas meter readings at the beginning and each of each, sampling
time increment and when sampling is halted.
To begin sampling, remove the nozzle cap, verify (if applicable) that
the probe and sorbent module temperature control systems are working and- at
temperature and that the probe is properly positioned. Position the probe at
the sampling point. Immediately start the pump and adjust the flow rate.
If the 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, salt to the
ice 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 rate difficult to maintain, the test run shall be terminated unless
the replacing of the filter corrects the problem. If the filter is replaced,
a leak check shall be performed.
A-19
-------
SECTION NO.: Appendix A
REVISION NO.: Radian 1
DATE: October 25, 1984
PAGE 20 OF 26
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A-20
-------
SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 21 OF 26
At the end of the sample run, turn off the pump, remove the probe and
nozzle from the stack, ang record the final dry gas meter reading. Perform
the post test leak check.
10.2 Sample 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 safely 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 aluminum foil. Seal off the inlet to the
train with a ground glass cap or hexane-rinsed aluminum foil.
Transfer the probe and impinger 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 smoking shall be allowed.
Inspect the train prior ,to and during disassembly and note any abnormal
conditions, e.g., broken filters, color of the impinger liquid, etc. Treat
the samples as follows:
10.2.1 Container No. 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 container.
With acceptability of the test run to be based on the same criterion as in
10.1.3.1.
A-21
-------
SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 22 OF 26
10.2.5 Sample Container No. 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 times each with acetone 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 removal of
the XAD-2. If the optional water knockout trap has been employed, 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. 4
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
n
= Total weight of chlorinated organic compounds in stack
gas sample, ng.
= Concentration of chlorinated organic compounds in stack
gas, yg/m , corrected to standard conditions of 20°C,
760 mm Hg (68°F, 29.92 in. Hg) on dry basis.
2 2
= Cross-sectional area of nozzle, m (ft ).
A-22
-------
ws
M
w
"bar
'std
R
m
std
m
Ic
V
m.
V (std)
m
V (std)
w
v
s
Y
AH
0
13.6
60
100
SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 23 OF 26
= Water vapor in the gas stream, proportion by volume.
= Percent of isokinetic sampling.
= Molecular weight of water, 18 g/g-mole (18 Ib/lb-mole).
= Barometric pressure at the sampling site, mm Hg (in. Hg).
= Absolute stack gas pressure, mm Hg (in. Hg).
= Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
3
= Ideal gas constant, 0.06236 mm Hg-m /°K-g-mole
(21.83 in. Hg-ft /°R-lb-mole).
= Absolute average dry gas meter temperature °K (°R).
= Absolute average stack gas temperature °K (°R).
= Standard" absolute temperature, 293°K (68°F).
= Total mass of liquid collected in impingers and silica
gel.
= Volume of gas sample as measured by dry gas meter, dcm
(dcf).
= Volume of gas sample measured by the dry gas meter
corrected to standard conditions, dscm (dscf).
= Volume of water vapor in the gas sample corrected to
standard conditions, scm (scf).
= Stack gas velocity, calculated by combustion calculation,
m/sec (ft/sec).
= Meter box correction factor.
= Average pressure differential across the orifice meter,
mm H20 (in. H20).
= Total sampling time, min.
= Specific gravity of mercury.
= Sec/min.
= Conversion to percent.
A-23
-------
SECTION NO.: Appendix A
REVISION NO,: ASME Draft 4
DATE: October 1984
PAGE 24 OF 26
11.2 Average Dry Gas Meter Temperatures and Average Orifice Pressure Drop
See data sheet (Fig. 4).
11.3 Dry Gas Volume
Correct the sample volume measured by the dry gas meter to standard
conditions [20°C, 760 mm Hg (68±F, 29.92 in. HG)] by using Equation 1.
. AH „ „ „ AH
V (std) = Y V
m m
std +
13.6 = KlVm
m
'std
•bar + 13.6
m
(1)
where:
0.3855 °K/mm Hg for metric units
17.65 °R/in. Hg for English units
11.4 Volume of Water Vapor
RT
Vw(atd)
std
M x P _.
w std
K2mlc
where:
K2 = 0.00134 m /ml for metric units
3
= 0.472 ft /ml for English units
11.5 Moisture Content
B
V
ws
w(std)
V (std) + V , ,,
nT ' w(std)
(2)
(3)
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 Isokinetic Sampling
100
[K
(Vm Km)
. 6)1
(4)
60 0 PA
vs s n
where:
K
:, = 0.003454 mm Hg - m /ml - °K for metric units
0.002669 in Hg - ft3/ml - °R for English units
A-24
-------
SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 25 OF 26
11.7 Concentration of Chlorinated Organic Compounds in Stack Gas
Determine the concentration of chlorinated organic compounds in the
stack gas according to Equation 5.
C = K, Gs
s 5
V (std)
m
(5)
where:
= 35.31 ft3/m3
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 procedures 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 part 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 same procedure as each sample medium.
Blank Train
For each series of test runs, set up a blank train in a manner identical
to that described above, but with the probe inlet capped with hexane-rinsed
aluminum foil and the exit end of the last impinger capped with a ground
glass cap. Allow the train to remain assembled for a period equivalent to
one test run. Recover the blank sample as described in Sec. 7.2.
A-25
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SECTION NO.: Appendix A
REVISION NO.: ASME Draft 4
DATE: October 1984
PAGE 26 OF 26
REFERENCES
1. Cooke, M., DeRoos, F., and Rising, B., "Hot Flue Gas Spiking and
Recovery Study for Tetrachlorodibenzodioxins (TCDD) Using Method 5 and
SASS Sampling with a Simulated Incinerator", EPA Report, Research
Triangle Park, NC 27711 (1984).
2. Rom, J.J., "Maintenance, Calibration and Operation of Isokinetic 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: Concentrations of Polychlorinated
Dibenzo-p-dioxins/dibenzo-furans and Possible Precursor Compounds in
Incinerator Effluents", Chapter 8-Chlorinated Dioxins and Dibenzofurans
in the Total Environment, Butterworth Publishers, Woburn, Mass. (1983).
A-26
-------
APPENDIX B
DRAFT ASME ANALYTICAL PROTOCOL
"ANALYTICAL PROCEDURES TO ASSAY STACK EFFLUENT SAMPLES AND RESIDUAL
COMBUSTION PRODUCTS FOR POLYCHLORINATED DIBENZO-P-DIOXINS (PCDD)
AND POLYCHLORINATED DIBENZOFURANS (PCDF) •
DRAFT, SEPTEMBER 18, 1984
-------
-------
DRAFT
ANALYTICAL PROCEDURES TO. ASSAY STACK EFFLUENT
SAMPLES AND RESIDUAL COMBUSTION PRODUCTS FOR POLYCHLORINATED
DIBENZO-p-DIOXINS (PCDD) AND POLYCHLORINATED DIBENZOFURANS (PCDF)
Prepared By
.. -GROUP C - ENVIRONMENTAL STANDARDS WORKSHOP
Sponsored By
THE AMERICAN SOCIETY OF MECHANICAL ENGINEERS, U.S. DEPARTMENT
OF ENERGY AND U.S. ENVIRONMENTAL PROTECTION AGENCY
SEPT. 18, 1984
B-l
-------
DRAFT
1. Scope and Applicability of Method
• The analytical procedures described here are applicable for the
determination of polychlorinated dibenzo-p-dioxins(PCDD) and dibenzo-
furans(PCDF) in stack effluents from combustion processes. These methods
are also applicable to' residual combustion products such as bottom and
precipitator ash. The methods presented entail addition of isotopically-
labeled internal standards to all samples in known quantities, extraction
of the sample with appropriate organic solvents, preliminary fractionation
and cleanup of the extracts, using a sequence of liquid chromatography
columns, and analysis of the processed extract for PCDD and PCDF using
coupled gas chromatography - mass spectrometry (GC-MS). Various '
performance criteria are specified herein which the analytical data
must satisfy for quality assurance purposes. These represent minimum
criteria which must be incorporated into any program in which PCDD
and PCDF are determined in combustion product samples..
The method presented here does not yield definitive information on
the concentration ,of individual PCDD/PCDF isomers, except for 2,3,7,8-
Tetrachlorodibenzorp-dioxin (TCDD) and 2,3,7,8-Tetrachlorodibenzofuran
(TCDF). Rather, it is designed to indicate the total concentration of
the isomers of several chlorinated classes of PCDD/PCDF (that is, total
tetra-, penta-, hexa-, hepta-, and octachlorinated dibenzo-p-dioxins and
dibenzofurans). Of the 75 separate PCDD and 135 PCDF isomers, there
are 22 TCDD, 38 TCDF, 14 PeCDD, 28 PeCDF, 10 HxCDD, 16 HxCDF, 2 HpCDD,
4 HpCDF, 1 OCDD and 1 OCDF.a
The analytical method presented herein is intended to be applicable
for determining PCDD/PCDF present in combustion products at the ppt to
ppm level, but the sensitivity which can ultimately be achieved for-a
given sample will depend upon the types and concentrations of other chemical
compounds in the sample.
'The method described here must be implemented by or under the
supervision of chemists with experience in handling supertoxic materials
and analyses should only be performed in rigorously controlled, limited
access laboratories. The quantitation of PCDD/PCDF should be accomplished
only by analysts experienced in utilizing capillary-column gas chromatography.
mass spectrometry to accomplish quantitation of chlorocarbons and similar
compounds at very low concentration.
B-2
-------
DRAFT
The toxicological data which are available for the PCDD and PCDF are
far from complete. That is, the toxicological properties of all of
the isomers comprising the 75 possible PCDD and 135 possible PCDF are
not presently known. However, a considerable body of toxicologacal
data exists for 2,3,7,8-TCDD which indicates that, in certain animal
species, this compound is lethal at extraordinarily low does and causes
a wide range of systemic affects, including hepatic disorders, carcinoma
and birth defects. While much less data is available regarding the
toxicology of 2,3,7,8-TCDF, sufficient data is available to form the
basis for the belief that 2,3,7,8-TCDF is similar in its toxicological
properties to 2,3,7,8-TCDD. Relatively little is known about the toxi-
cology of the higher chlorinated PCDD and-PCDF (that is, penta through
octachlorinated PCDD/PCDF), although there is some data to suggest that
certain penta-, hexa-, and hepta- PCDD/PCDF isomers are hazardous. In
view of the extraordinary toxicity of 2,3,7,8-TCDD and in view of the
exceptional biological activity of this compound (on the basis of enzyme
induction assays ) and'of compounds having similar molecular structures,
extensive precautions are required to preclude exposure to personnel
during hand!ing.and analysis of materials containing these compounds and to
prevent contamination of the laboratory. Specific safety and handling
procedures which are recommended are given in the Appendix to this protocol.
a.
The abbreviations which are used to designate chlorinated -dibenzo-p-
dioxins and dibenzofurans throughout this document are as follows:
PCDD - Any or all of the 75 possible chlorinated dibenzo-p-dioxin isomers
PCDF - Any or all of the 135 possible chlorinated dibenzofuran isomers
. TCDD - Any or all of the 22 possible tetrachlorinated dibenzo-p-dioxin isomers
T.CDF - Any or all of the 138 possible tetrachlorinated dibenzofuran .isomers
PeCDD - Any or all of the 14 possible pentachlorinated dibenzo-p-dioxin isomers
PeCDF - Any or all of the 28 possible pentachlorinated dibenzofuran isomers
HxCDD - Any or all of the 10 possible hexachlorinated dibenzo-p-dioxin isomers
HXCDF - Any or all of the 16 possible hexachlorinated dibensofuran isomers
HpCDD - Any or all of the 2 possible heptachlorinated dibenzo-p-dioxin isomers
HpCDF - Any or all of the 4 possible heptachlorinated dibenzofuran isomers
OCDD - Octachlorodibenzo-p-dioxin
• OCDF - Octachlorodibenzofuran
Specific Isomers. - Any of the abbreviations cited above may be converted to
designate a specific isomer by indicating the exact positions (carbon atoms)
where chlorines are located within the molecule. For example, 2,3,7,8-TCDD
refers to only one of the 22 possible TCDD isomers - that isomer which is
chlorinated in the 2,3,7,8 po'B ns of the dibenzo-p-dioxin ring structure.
-------
DRAFT
2. Reagents and Chemicals
The following reagents and chemicals are appropriate for use in these
procedures. In all cases, equivalent materials from other suppliers
may also be used.
2.1 Potassium Hydroxide, Anhydrous,'Granular Sodium Sulfate and
Sulfuric Acid (all Reagent Grade): J. T. Baker Chemical Co. or Fisher
Scientific Co. The granular sodium sulfate is purified prior to use
by placing a beaker containing the sodium sulfate in a 400°C oven for
four hours, then removing the beaker and allowing it to cool in a desiccator.
Store the purified sodium sulfate in a bottle equipped with a Teflon-
lined screw cap... ..
2.2 Hexane, Hethylene Chloride, Benzene, Methanol, Toluene,
Isooctane: "Distilled in Glass" Burdick and Jackson.
2.3 Tridecane (Reagent Grade): Sigma Chemical Co.
2.4 Basic Alumina (Activity Grade 1, 100 - 200 mesh): ICN
Pharmaceuticals. Immediately prior to use, the alumina is activated by
heating for at least 16 hours at 600°C in a muffle furnace and then
allowed to cool in a desiccator for at least 30 minutes' prior to use.
Store pre-conditioned alumina in a desiccator.
' 2.5 Silica (Bio-Sil A,100/200 mesh): Bio-Rad. The following
procedure is recommended for conditioning the Bio-Sil A prior to use.
Place an appropriate quantity of Bio-Sil A in a 30 mm x 300 mm long
glass tube (the silica gel is held in place by glass wool plugs) which
is placed in a tube furnace. The glass tube is connected to a pre-
purified nitrogen cylinder, through a series of four traps (stainless
steel tubes, 1.0 cm 0.0. x 10 cm long)6: 1) Trap No. 1 - Mixture
comprised of Chromosorb W/AW (60/80 mesh coated with 5% Apiezon L),
Graphite (UCP-1-10Q), Activated Carbon (50 to 200 mesh) in a 7:1.5:1,5
ratio (Chromosorb W/AW, Apiezon L obtained from Supelco, Inc., Graphite
obtained from Ultracarbon Corporation, 100 mesh, 1-M-USP; Activated
Carbon obtained from Fisher Scientific Co.); 2) Trap No. 2 - Molecular
Sieve 13 X (60/80 mesh), Supelco, Inc.; 3) Trap No, 3 - Carbosieve S-
(80/100 mesh), obtained from Supelco, Inc.; 4) The Bio-Sil A is heated
in the tube for 30 minutes at 180°C while purging with nitrogen (flow
rate 50-100 mL/minute), and the tube is then removed from the furnace
and allowed to cool to room temperature. Methanol (175 mL) is then
passed through the tube, followed by 175 ml .methylene chloride. The
tube containing the silica is then returned to the furnace, the nitrogen
purge is again established (50-100 ml flow) and the tube is heated at-
50°C for 10 minutes, then the temperature is gradually increased to
180°C over 25 minutes and maintained at 180°C for 90 minutes. Heating
is then'discontinued but the nitrogen purge is continued until the tube
B-4
-------
DR/\H
cools to room temperature. Finally, the silica is transferred to a clean,
dry, glass bottle and capped with a Teflon-lined screw cap for storage.
2.6 Silica Gel Impregnated With Sulfuric Acids Concentrated sulfuric
acid (44 g) is combined with 100 g Bio-Si! A (conditioned as described
above) in a screw capped bottle and agitated to mix thoroughly. Aggre-
gates are dispersed with a stirring rod until a uniform mixture is .obtained
The HSO-silica gel is stored in a screw-capped bottle (Teflon-lined cap).
2.7 Silica Gel Impregnated with' Sodium Hydroxide: IN Sodium
hydroxide (39 g) is combined with 100 g Bio-Si! A (conditioned as
described above) in a screw capped bottle and agitated to mix throughly.
Aggregates are dispersed, with a stirring rod until a uniform mixture is
obtained. The NaOH-silica gel is stored in a screw-capped bottle
(Teflon-lined cap).
2.8 Carbon/Celite:
Carbon: . Amoco P.X-21
Celite 545: Fisher Scientific Co
Combine Amoco PX-21 carbon (10.7 g) with Celite 545 (124 g) in a
250 ml glass bottle fitted with a Teflon-lined cap.. Agitate the mixture
to combine thoroughly. Store in the screw-capped bottle.
2.9 Sepralyte Diol (40y): Analytichem International
2.10 Nitrogen and Hydrogen (Ultra High Purity): Matheson Scientific
3. Apparatus and Materials -
Th'i following apparatus and materials are appropriate for use in these
procedures. In all cases, equivalent items from other suppliers may
also be used.
3.1 Glassware used in the analytical procedures (including the
Soxhlet apparatus and disposable bottles) is cleaned by rinsing successively
three times with methanol and then three times with methylene chloride,
and finally drying it in a 100°C oven. Bottles cleaned in this manner
are allowed to cool to room temperature and are then capped using Teflon-
lined lids. Teflon cap liners are rinsed as' just described but are
allowed to air-dry. More rigorous cleaning of some glassware with
detergent may be required prior to the solvent rinses, for example, the
glassware employed for Soxhlet extraction of samples.
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DRAFT
3.1.1 Sample Vessels: 125 ml and 250 ml flint glass bottles fitted
with screw caps and teflon cap liners, and glass test tubes, VWR-Scientific.
3.1.2 Teflon Cap Liners: Scientific Specialities Service, Inc.
*
3.1.3 Soxhlet Apparatus: Extraction apparatus, Allihn condenser,
Kirnax Brand, American Scientific Products Cat. No. E6252-2A.
3.1.4 Gravity Flow Liquid Chromatographic Columns: Custom
Fabricated (Details of.the columns are provided in later sections).
3.1.5 Micro-vials (3.0 mL): Reliance Glass.
3.2 Capillary Gas Chromatographic Columns: Two different columns are
required if data on both 2,3,7,8-TCDD and 2,3,7,8-TCDF, as well as on
the total PCDD/PCDF by chlorinated class,are desired. The appropriate
columns are: 1) A fused silica column (60 M x 0.25 mm I.D.) coated
with DB-5 (0.25 y film thickness), J & S Scientific, Inc., Crystal
Lake, IL is utilized to separate each of the several tetra-through
octachlorinated CDDs and CDFs, as a group, from all of the other groups.
While this column does not resolve all of the isomers within each
chlorinated group,, it effectively resolves each of the chlorinated
groups from all of .the other chlorinated groups and therefore provides
data on the total concentration of each group (that is, total te'tra-,
penta-, hexa-, hepta- and octa CDDs and CDFs). This column also
resolves 2,3,7,8-TCDD from all of the other 21 TCDD isomers and this
isomer can therefore be determined quantitatively if proper calibration
procedures are applied as described further in a later section. This
column does not completely resolve 2,3,7,8-TCDF from the other TCDF
isomers, and if a peak corresponding in retention time to 2,3,7,8-TCDF
is observed in the analysis using this column, then a portion of the
sample extract must,be reanalyzed using the second GC column described
below if isomer - specific data on 2,3,7,8-TCDF is desired. 2) A
fused silica column (30 M x 0.25 mm I.D.) coated with DB-225 (0.25 y
film thickness,), 0 & S Scientific, Inc., Crystal Lake, IL, must be
utilized to obtain quantitative data on the concentration of 2,3,7,8-
TCDF, since this column adequately resolves 2,3,7,8-TCDF. from the other
TCDF isomers. ' ''
3.3 Balance: Analytical Balance, readibility, 0.0001 g.
3.4 Nitrogen Slowdown Concentration Apparatus
Evaporator Model III, Organomation Associates Inc.
N-Evap Analytical
3.5 Tube Furnace: Lindberg Type 59344.
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4. Instrumentation
DRAFT
The
Gas Chromatograph-Mass Spectrometer-Data System (GC/MS/DS):
instrument system used to analyze sample extracts for PCDD/PCDF
comprises a gas chromatograph (fitted for capillary columns) coupled
directly or through an enrichment device to a mass spectrometer which is
equipped with a computer-based data system. The individual components
of the GC/MS/DS are described below.
4.1 .Gas Chromatograph (GC): The chromatograph must be equipped
with an appropriate injector and pneumatic system to permit use of the
specified glass or fused silica capillary columns. It must also incor-
porate an oven which can be heated in a reproducible, programmed
temperature cycle. The injector should be configured for splitless/
split injections. The GC column performance should be verified at the
beginning of each 8 hour work period or at the beginning of each series
of analyses.if more than one set of"samples is analyzed during an 8
hour shift. Extracts of complex combustion products and effluents may
contain numerous organic residues even after application of the exten-
sive prefractionation/cleanup procedures specified in this method.
These residues may result in serious deviation of GC column perfor-
mance and therefore, frequent performance checks are desirable. Using
appropriate calibration mixtures, as .described below, the retention
time windows for each chlorinated class of CDDs/CDFs must be verified.
In addition, the GC column utilized must be demonstrated to effectively
separate 2,3,7,8-TCDD from all other TCDD isomers if data on 2,3,7,8-
TCDD alone is desired with at least 20% valley definition between the
2,3,7,8- isomer and the other adjacent-eluting TCDD isomers. Typically,
capillary column 'peak widths (at half-maximum peak height) on the order
of 5-10 seconds are obtained in the course of these analyses. An
appropriate GC temperature program for the analyses described herein
is discussed in a later section (see Table 1).
4.2 Gas Chromatograph-Mass Spectrometer Interface: The GC-MS
interface can include enrichment devices, such as a glass jet separator
or a silicone membrane separator, or the gas chromatograph can be
directly coupled to the mass spectrometer source, if the system har,
adequate pumping of the source region. The interface may include a
diverter valve for shunting the column effluent and isolating the
mass spectrometer source. .All components of the interface should be
glass or glass-lined stainless steel. The interface components must be
compatible with temperatures in the neighborhood of 250°C, which is the
temperature at which the interface is typically maintained throughout
analyses for PCDD/PCDF. The GC/MS interface must be. appropriately
configured so that the separation of 2,3,7,8-TCDD from the other TCDD
isomers which is achieved in the gas chromatographic column is not
appreciably degraded. Cold spots and/or active surfaces (adsorption
sites) in the GC/MS interface can cause peak'tailing and peak .broadening.
If the latter are observed, thorough cleaning of the injection port,
interface and connecting lines should be accomplished prior to pro-
ceeding. •
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DRAFT
4.3 Mass Spectrometer "(MS): The mass spectrometer used for the
analyses described here is typically a double-focusing sector or
quadrupole instrument equipped with an electron impact source (70 ev),
maintained at 250°C, and a standard electron multiplier detector.
If possible, it is desirable to have both low and high resolution
capability with the mass spectrometer used, since confirmation ef
data obtained by low resolution MS using high resolution MS is sometimes
desirable. Alternatively, a combination of mass spectrometers can be
used for this purpose. The static resolution of the instrument must
be maintained at a minimum of 1:500 (with a 10% valley between adjacent
masses) if operating in the low resolution MS mode, and a minimum
resolution of 1:10,000 is desirable for operation in the high resolution
mode. The mass spectrometer must also be configured for rapid computer-
controlled selected-ion monitoring in both high and low resolution
operating modes. At a minimums two ion-masses characteristic of each
class of chlorinated dioxins should be monitored, and these are two
ions in the molecular ion isotopic cluster. It is desirable for
increased confidence in the data to also monitor the fragment ions
arising from the loss of COC1 from the molecular ion. In order to accomplish
the requisite rapid multiple ion monitoring sequence during the time
period defined by a typically capillary chromatographic^peak (the base
of the chromatographic peak is typically 15-20 seconds in width),^the
following MS performance parameters are typically required (assuming
a 4-ion monitoring sequence for each class of PCDD/PCDF): dwell time/
ion-mass, =100 msec.; minimum number of data points/chromatographic^
peak, 7 . The mass scale of the mass spectrometer is calibrated using
hiqh boiling perfluorokerosene and/or some other suitable mass standard
depending upon the requirements of the GC-MS-DS system utilized. The
actual procedures utilized for calibration of the mass scale will be
unique to the particular mass spectrometer being employed. A list OT
the appropriate ions to be monitored in the PCDD/PCDF analyses described
herein is presented in a later section (see Table 1).
4 4 Data System: A dedicated computer-based data system, capable
of providing the data described above, is employed to control the rapid
selec?ed-ion monitoring sequence and to acquire the data Both digital
data (peak areas or peak heights) as well as peak profiles CJ«pl4ys of
intensities of ion-masses monitored as a function of time) should be
acquired during the analyses, and displayed by the data system. This
rawdata (mass chromatograms) should be provided in the report of the data.
5. Calibration Standards
A recommended set of calibration standards to be used in the analyses
described herein is presented below. Stock standard solutions of the
various PCDD and PCDF isomers and mixtures thereof are preparedin a
glovebox, using weighed quantities of the authentic isomers. These
stock solutions are contained in appropriate volumetric flasks and are
stored tightly stoppered, in a refrigerator. Aliquots of the stock
standards are removed for direct use or for subsequent serial dilut ons
to prepare working standards. These standards must be checked regularly
(by comparing instrument response factors for them over a period of
B-8
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DRAFT
time) to ensure that solvent evaporation or other losses have not occurred
which would alter the standard concentration. The several recommended
standard solutions are as follows. •
5.1 Standard Mixture A: Prepare a stock solution containing the
following isotopically-labelled PCDD and PCDF in isooctane at the
indicated concentrations: 2.5ng./yl13Ci2-2,3,7,8-TCDD, 2.5ng/yl37CU-
2,3,7,8-TCDF, 25ng/yL13Ci2-1,2,3,4,7,8-HxCDD, 25ng/yL13Ci2-l,2,3,4,7,8-
HxCDF, 25ng/yL13Ci2-OCDD/ and 25ng/yL13Ci2-OCDF. Portions of this
isomer mixture are added to all samples prior to analyses and serve
as Internal standards for use in quantitation. Recovery of these
standards is also used to guage the overall efficacy of the analytical
procedures. '
5.2 Standard B: Prepare a stock solution containing 1.0 ng of
37Cli»-2,3,7,8-TCDD/yL of isooctane. This standard can be coinjected
if desired, along with aliquots of the final sample extract to reliably
estimate the recovery of the 13d2-2,3,7,8-TCDD surrogate standard.
5.3 Standard Mixture C: Prepare a.stock solution containing
100 ng/yL of isooctane of each of the following PCDD and PCDF:
2,3,7,8-TCDF; 2,3,7,8-TCDD; 1,3,4,6,8-PeCDF, 2,3,4,6,7-PeCDF; 1,2,4,7.9-
PeCDD; 1,2,3,8,9-PeCDD; 1,2,3,4,6,8-HxCDF; 2,3,4,6,7,8-HxCDF; 1,2,3,4,5,8-
HxCDD, 1,2,3,4,6,7-HxCDD; 1,2,3,4,6,7,8-HpCDF; 1,2,3,4,7,8,9-HpCDF;
1,2,3,4,6,7,8-HpCDD; 1,2,3,4,6,7,9-HpCDD; OCDF: and OCDD. This isomer
mixture is used to define the gas chromatographic retention time
intervals or windows for each of the penta-, hexa-, hepta-, and
octachlorinated groups of PCDD and PCDF; Each pair of isomers of a given
chlorinated class which is listed here corresponds to the first and
last eluting isomers of that class on the DB-5 capillary GC column
(except for TCDD and TCDF). In addition, this isomer mixture is used
to determine GC-MS response factors for representative isomers of each
of the penta-, hexa-, hepta-, and octachlorinated groups of PCDD and
PCDF. The later data are used in quantitating the analytes in unknown
samples.
5.4 Standard Mixture D: Prepare a stock solution containing
50 pg/yL of isooctane of each of the following TCDD isomers: 1,3,6,8-
TCDD; 1,2,3,7-TCDD; 1,2,3,9-TCDD; 2,3,7,8-TCDD; and 1,2,8,9-TCDD. Two of the
isomers in this mixture are used to define the gas chromatographic
retention time window for TCDDs (1,3,6,8-TCDD is the first eluting TCDD
Some of the PCDD/PCDF isomer standards recommended for this method
are available from Cambridge Isotope Labora-fories, Cambridge, Massachusetts.
Other PCDD/PCDF standards are available from the Brehm Laboratory, Wright
State University, Dayton, Ohio, from the U.S. EPA Standard Repository
at Research Triangle Park, North Carolina and possibly from other laboratories.
Not all of the indicated isotopically-labelled PCDD/PCDF internal standards
recommended here are presently available in quantities sufficient for
widespread distribution, but these are expected to be available in the near
future.
B-9
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DRAFT
isomer and 1,2,8,9-TCDD is the last elating TCDD isomer on the DB-5
GC column). The remaining isomers serve to demonstrate that the 2,3,7,8-
TCDD isomer 1s resolved from the other nearest eluting TCDD isomers,
and that the column therefore yields quantitative data for the 2,3,7,8-
TCDD isomer alone. *
5.5 Standard Mixture E: Prepare a stock solution containing 50 pg/yL
of isooctane of each of the following TCDF isomers: 1,3,6,8-TCDF; 2,3,4,8-
TCDF; 2,3,7,8-TCDF, 2,3,4,7-TCDF; and 1,2,8,9-TCDF. This isomer mixture
is used to define the TCDF gas chromatographic retention time window
(1,3,6,8- and 1,2,8,9-TCDF are the first and last eluting TCDFs on the
DB-5 capillary column) and to demonstrate that 2,3,7,8-TCDF is uniquely
resolved from the adjacent-eluting TCDF isomers.
6. Procedures for Addition of Internal Standards and Extraction of Samples
Both .liquid and solid samples will be obtained for PCDD/PCDF
analyses as a result of the application of an appropriate stack
sampling procedure. Samples
resulting from the sampling train will include the following (these
will be provided to the analytical laboratory as separate samples in
the form indicated): 1) particulate filter and particulates thereon;
2) particulates from the cyclone (if used); 3) combined aqueous solutions
from the impingers; 4) the intact XAD-resin cartridge and the resin
therein; 5) combined aqueous rinse (if -used) solutions from rinses of
the nozzle, probe, filter holder, cyclone (if used), impingers, and
all connecting lines; 6) combined acetone rinse solutions from rinses
of the nozzle, probe,, filter holder, cyclone (if used), impingers, and
all connecting lines; 7). combined hexane rinse solutions from rinses
of the nozzle, probe, "filter, cyclone (if used), impingers, and all
connecting lines. In addition, samples of bottom ash, precipitatbr
ash, incinerator feed materials or fuel, quench liquids, and materials
from effluent control devices may also be provided for analyses.
In general, the volumes of all liquid samples received for analyses
are measured and recorded, and where appropriate, solid samples or
aliquots thereof are weighed. Any samples which are homogeneous (as
for example, a single liquid phase sample or a solid which can be
thoroughly mixed) can be split prior to analyses, if desired, provided
that this will still permit the attainment of the desired detection
limits for the analytes of interest. Samples such as particulates from
the sampling train which are generally collected in relatively small
quantity, are preferably analyzed in total. *_
6.1 Organic Liquid Samples (Acetone and Hexane Solutions)
Concentrate each of the combined organic liquids (acetone and hexane
solutions) to a volume of about 1-5 ml using the nitrogen blowdown
e-io
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DRAFT
apparatus (a stream of dry nitrogen) while heating the sample gently on a
water bath. Pop! the concentrated residues, rinsing the vessels three
times with small portions of hexane and adding these to the residues,
and concentrate to near dryness. This residue will likely contain
particulates which were removed in the rinses of the train probe and
nozzle. Combine the residue (along with three rinses of the f\nal
sample vessel) in the Soxhlet apparatus with the filter and particulates,
and proceed as described under Solid Sample below.
6.2 Aqueous Liquids
Add an appropriate quantity of the isotopically-labeled'internal standard
mixture (Standard Mixture A described earlier) to the aqueous liquid
sample (or an aliquot thereof) in a screw-capped bottle fitted with a
Teflon-lined cap. Add approximately 25% by volume of hexane to the
spiked aqueous sample, seal the bottle and agitate on a shaker for a
period of three hours. Allow the vessel to stand until the aqueous and
organic layers separate, then transfer the organic layer to a separate
sample bottle. Repeat the hexane extraction sequence two additional •
times^and combine the organic fractions with that from the first ex-
traction. Proceed with the sample fractionation and cleanup procedures
described below.
6.3 Solid Samples
Place a glass extraction thimble and 1 g of silica gel and a plug of
glass wool into the Soxhlet apparatus, charge the apparatus with toluene
and reflux for a-period of one hour. . Remove the toluene and discard it,
retaining the silica gel, or if desired, retain a portion of the toluene
to check for background contamination. For extraction of particulates,
place the entire sample in the thimble onto the bed of precleaned silica
gel (1 cm. thick), and top with the precleaned glass wool retained
from the initial Soxhlet cleaning procedure. Add the appropriate
quantity of the isotopically-labelled internal standard mixture
(Standard Mixture A described earlier) to the sample in the Soxhlet
thimble. Charge the Soxhlet with toluene and reflux for a period of .
16 hours. After extraction, allow the Soxhlet to cool, remove the
toluene extract, and transfer it to another sample vessel. Concentrate
the extract to a volume of approximately 40 ml by using the nitrogen
blowdown apparatus described earlier. Proceed with the sample fractiona-
tion and cleanup procedures described below.
7. Procedures for Cleanup and Fractionation of Sample Extracts
The following column chromatographic sample clean-up procedures
are used in the order given, although not al-1 may be required. In
general, the silica and alumina column procedures are considered to be a
minimum requirement. Acceptable alternative cleanup procedures may be
used provided that they are demonstrated to effectively transmit a
B-ll
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umn
representative set of the analytes of interest. The column chromato-
graphic procedures listed here have been demonstrated to be effective
for a mixture consisting of 1,2,3,4-TCDD, 2,3,7,8-TCDD, 2,3,6,8-TCDF,
1,2,4,8-TCDF, 2,3,7,8-TCDF, 1,2,3,7,8-PeCDD, 1,2,4,7,8-PeCDF, 1,2,3,4,7,8-
HxCDD, 1,2,4,6,7.9-HxCDF. 1,2,3,4,6,7,8-HpCDD, 1,2,3,4,6,8,9-HpCDF,
OCDD and OCDF • . .
i-
An extract obtained as described in the foregoing sections is
concentrated to a volume of about 1 ml using the nitrogen blowdown
apparatus, and this is transferred quantitatively (with rinsings) to
the combination silica gel column described below.
7.1 Combination Silica Gel Column: Pack one end of a glass
column (20 mm. O.D. x 230 mm in length) with glass wool (precleaned)
and add, in sequence, 1 g silica gel, 2 g base-modified silica gel,
1 g silica gel, 4 g acid-modified silica gel, and 1 g silica gel.
'(Silica gel and modified silica gel are prepared as described in the
Reagents sections of this protocol.) Preelute the-column with 30 ml
hexane and discard the eluate. Add the sample extract in 5 mL of hexane
to the column along with two additional 5 ml rinses. Elute the column
with an additional 90 ml of hexane and retain the entire eluate.
Concentrate this solution to a "volume of about 1 ml.
7.2 Basic Alumina Column: Cut off a 10 ml disposable Pasteur-
glass pipette at the 4 mL graduation mark and pack the Tower section with
glass wool (precleaned ) and 3 g of Woelm basic alumina (prepared as
described in the Reagent section of this protocol). Transfer the
"concentrated extract from the combination silica column to-the top of -
the column and elute the column sequentially with 15 ml of hexane,
10'mL of 8% methylene chloride-in-hexane and 15 mL of 50% methylene
chloride-in-hexane, discarding the first two eluate fractions and
retaining the third eluate fraction. Concentrate the latter fraction
to about 0.5 mL using the nitrogen blowdown apparatus described earlier.
7.3 PX-21 Carbon/Celite 545 Column: .Take a 9 inch disposable
Pasteur pipette and cut off a 0.5 inch section from the constricted tip.
Insert a filter paper disk at the top of the tube, 2.5 cm. from the
constriction. Add a sufficient quantity of PX-21 Carbon/Celite 545
(Prepared as described in the reagent section of this protocol) to the.
tube to form a 2 cm. length of the Carbon-Celite. Insert a glass wool
plug. Preelute the column in sequence with 2 mL of 50% benzene-in-ethyl .
acetate, 1 mL of 50% methylene chloride-in-cyclohexane and 2 mL of hexane,
and discard these eluates. Load the extract (in 1 mL of hexane) from
the alumina column onto the top of the column, along with 1 mL hexane
rinse. Elute the column with 2 mL of 50% methylene chloride-in-hexane
and 2 mL of 50% benzene-in-ethyl acetate and discard these eluates.^
Invert the column and reverse elute it with 4 mL of toluene, retaining
this eluate. Concentrate the eluate and transfer it to a Reacti-Vial
for storage. Store extracts in a freezer, shielded from light, prior
B-12
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. '•-,••- ;;••• — :'" --•" I
to GC-M5-ana lysis. If desired, still another column chromatograpMc Lm«"U \
clean-up step can be employed prior to concentration of the extract
as described below.
.7.4 Sllica/Diol Micro Column Cleanup: After the above clean-up
steps small amounts of highly colored polar compounds may be present in
complex samples. These are removed, If necessary, by the following
column: Push a small plug of glass wool into a disposable 6 mm i.d.
glass Pasteur pipette, followed by 3 mm of Sepralyte (Analytichem
International), 6 mm of silica gel and finally 3 mm of sodium sulfate.
The column is pre-wet with hexane, the sample is applied in 100 yL of
100% hexane and eluted with hexane, collecting 1.5 ml.
8. Procedure for Analysis of Sample Extracts for PCDD/PCDF Using Gas
Chromatography-Mass Spectrometry (GC-MS).
8.1 Sample extracts prepared by the procedures described in the
foregoing are analyzed by GC-MS utilizing the following instrumental
parameters. Typically, 1 to 5 vl portions of the extract are injected
into the GC. Sample extracts are first analyzed using the DB-5 capillary
GC column to obtain data on the concentrations of total tetra-throuqh
octa-CDDs and CDFs, and on 2,3,7,8-TCDD. If tetra-CDFs are detected .
in this analysis, then another aliquot of the sample is analyzed in
a,separate run, using the DB-225 column to obtain data on the concentration
Of 2,3,7,8-TCDF.
8.2 Gas Chromatograph :
^ ^ 8.2.1 Injector: Configured for capillary column, splitless/split
injection (split flow on 60 seconds following injection), injector
temperature, 250 C. . ' •
8.2.2 Carrier gas: Hydrogen, 30 Ib head pressure.
8.2.3 Capillary Column.!: For total tetra- through octa - CDDs/CDFs and
2,3,7,8-TCDD, 60 M x 0.25 mm I.D. fused silica DB-5; temperature pro-
grammed (see Table 1 for temperature program). Capillary Column 2:
for'2,3,7,8-TCDF only, 60 M x 0.25 mm I.D. fused silica DB-225, temperature
programmed (180°C for 1 min., then increase from 180aC to 240°C @"5°C/min.,
hold at 240°C for 1 min.)
8.2.4 Interface Temperature: 250°C
8.3 Mass Spectrometer
8.3.1 lonization Mode: Electron impact (70 eV)
B-13
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8.3.2 Static Resolution: 1:600 (10% valley) or 1:10,000 depending
upon requirements. Usually the sample extracts are initially analyzed
using low resolution MS, then if PCDD/PCDF are detected, it is desirable
to analyze a second portion of the sample extract using high resolution
MS.
EKftfi
8.3.3 'Source Temperature: 250 C
8.3.4 Ions Monitored: Computer-Controlled Selected-Ion Monitoring,
See Table 1 for list of ion masses monitored and time intervals during
which ions characteristic of each class of CDDs and CDFs are monitored.
8.4 Calibration Procedures:
8.4.1 Calibrating the MS Mass Scale: Perfluoro Kerosene, decafluoro-
triphenyl phosphine, or any other accepted mass marker compound must be
Introduced into the MS, in order to calibrate the mass scale through at
least m/z 500. The procedures specified by the manufacturer for the
particular MS instrument used are to be employed for this purpose. The
mass calibration should be rechecked at least at 8 hr. operating intervals.
8.4.2 Table 1 shows the EC temperature program typically used to
resolve each chlorinated class of PCDD and PCDF from the other chlorinated
classes, and indicates the corresponding time intervals during which ions
indicative of .each chlorinated class are monitored by the MS. .-This '
temperature program and ion monitoring time cycle must be established by
each analyst for the particular instrumentation used by injecting aliquots
of Standard Mixtures C, D. and E (See earlier section of.this protocol
for description of these mixtures). ' It may be necessary to adjust the
temperature program and ion monitoring cycles slightly based on the
observations from analysis of these mixtures. • • •
8.4.3 Checking GC Column Resolution for 2,3,7,8-TCDD and 2,3,7,8-
TCDF: Utilize the column-resolution TCDD and'TCDF isomer mixtures'
(Standard Mixtures D and £', containing 50 pg/yl, respectively of the.
appropriate TCDD and TCDF isomers) to verify that 2,3,7,8-TCDD and
2,3,7,8-TCDF are separated from the other TCDD and TCDF isomers, '
respectively. A 20% valley or less must be obtained between the mass
chromatographic peak observed for 2,3,7,8-TCDD and adjacent peaks
arising from other TCDD isomers,and similar separation of 2,3,7,8-TCDF
frpm other neighboring TCDFs.is required. Standard Mixture D is
utilized with the DBS column and Standard Mixture E with the DB-225
column. Analyze the column performance standards using the instrumental
parameters specified in Sections 8.2 and 8.3, and in Table 1. The
column performance evaluation must be performed each time a new'column
is installed in the gas chromatograph, and at least once during each 8
hour operating period. Providing that the same column is employed for a
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period of time, its performance can also be gauged by noting the peak
width (at 1/2 peak height) for 2,3,7,8-TCDD or for 2,3,7,8-TCDF. If
this peak width is observed to broaden by 20% or more.as compared to
the usual width for satisfactory operation, then the column resolution
1s suspect and must be checked. If; the column resolution is found to
be insufficient to resolve 2,3,7,8-TCDD and 2,3,7,8-TCDF from their
neighboring TCDD and TCDF isomers, respectively, (as measured on the
two different columns used for resolving these two isomers), then a
new DB-5 and/or DB-225 GC column must be installed,
8.4.4 Calibration of the GC-MS-DS system to accomplish quantitative
analysis of 2,3,7,8-TCDD and 2,3,7,8-TCDF, and of the total tetra-
through octa-CDDs and CDFs contained in the sample extract,is accomplished
by analyzing a series of at least three working calibration standards.
Each of these standards is prepared to contain the same concentration
of each of the stable-isotopically labelled internal standards used
here (Standard Mixture A) but a different concentration of native
PCDD/PCDF (Standard Mixture C). Typically, mixtures will be prepared
so that the ratio of native PCDD and PCDF to isotopically-labelled
PCDD and PCDF will be on the order of 0.1, 0.5 and 1.0 in the three
working calibration mixtures. The actual concentrations of both native
and isotopically-labelled PCDD and PCDF in the working calibration
standards will be selected by the analyst on the basis of the concen-
trations to be measured in the actual sample extracts. At the time
when aliquots of each of the standards are injected (and also when
injecting aliquots of actual sample extracts), if desired, an aliquot
of a standard containing typically 1 ng of S7CU-2,3,7,8-TCDD (Standard B)
-can. be drawn into'the micro syringe contai.ning..the calibration solution
described above (or the sample extract) and this is then co-injected
along with the sample extract in order to obtain data permitting
calculation of the percent recovery of the 13Ci2-2,3,7,8-TCDD internal
standard. Equations for calculating relative response factors from the
calibration data derived from the calibration standard analyses, and for
calculating the recovery of the 13Ci2-2,3,7,8-TCDD and the other
isotopically-labelled PCDD and PCDF, and the concentration of native
PCDD and PCDF in the sample (from the extract analysis), are summarized
below. In these calculations, as c?.n be seen, 2,3,7,8-TCDD is employed
as the illustrative model. However, the calculations for each of the
other native dioxins and furans in the sample analyzed are accomplished
in an analgous manner. It should be noted that in view of the fact
that stable-isotopically labelled internal standards corresponding to
each tetra- through octachlorinated class are not used here (owing
to limited availability at this time) the following approach is adopted:
For quantitation of tetrachlorinated dibenzofurans 13Ci2-2,3,7,8-TCDF
is used as the internal standard. For quantitation of tetrachloro-
dibenzo-p-dioxins, 13Ci2-2,3,7,8-TCDD is used as the internal ..standard.
For quantitation of PeCDD, HxCDD, PeCDF, and-HxCDF, the corresponding
stable-isotopically labelled HxCDD and HxCDF internal standards are used.
For quantitation of HpGDD, OCDD, and HpCDF, OCDF, the isotopically-
labelled OCDD and OCDF, respectively, are used. Inherent in this
approach is the assumption that the response factors for each of the isomers
B-15
DRAFT
-------
0f/uCh.chlSrinated class are the same> and in the case of the Dent*
Equation 1
RRF
,,,
for.native 2,3,7,8-TCDD using
as an internal standard.
where: A_ =
SIM response for 2,3,7,8-TCDD ion- at m/z 320 + 322
ion
13C"-2'3'7'8-TCDD internal standard
C1s =
C «
Concentration of the internal standard (pg./uL.j
Concentration of the 2,3,7,8-TCDD (pg./pL.)
Equation 2: .. Response. Factor^RRF)
the. co-injected.
RRF
where: A-s
SIM response for 13C12-2,3,7,8-TCDD internal
standard ion at m/z 332
SIM response for co-injected 37CU-2,3,7,8-TCDD external
009 (SIM
Cis = Concentration of the internal standard (pg./uL.)
Cfis = Concentration of the external standard (pg./yL.)
B-16
-------
Equation 3t Calculation of concentration of native 2,3,7,8-TCDD using fJ/Tr4l I
•.18Cj.2-2,3,7,8-TCDD as internal standard ' M " «
Concentration, pg./g. «= (As) (Is)/(A1s)(RRFd)(W)
where: AS * SIM response for 2,3,7,8-TCDD ion at m/z 320^ + 322
Aj = SIM response for the iaCi2-2,3,7,8-TCDD internal
standard ion at m/z 332
Is * Amount of internal standard added to each sample (pg.)
W * Weight of soil or waste in grains
* Relative response factor from Equation 1 . -
Equation 4: Calculation of % recovery of 18Ci2-2t3,7,8-TCDD internal standard
% Recovery = 100(A-s)(Es)/(Aes)(I1)(RRFf)
A- = SIM response for 13Ci2-2,3,7,8-TCDD internal standard
'is
ion at m/z 332
A = SIM response for 37Cl>t-2,3,7,8-TCDD external standard
ion at m/z 328 - 0.009 (SIM Response for native
• 2,3,7,8-TCDD at m/z 322)
E —Amount of 37C1 ^-2,3,7,8-TCDD external standard
co-injected with sample extracting.)
" I.. - Theoretical amount of 13Ci2-2,3s7,8-TCDD internal
standard in injection . .'
»
RRF-: = Relative response factor from Equation 2
As noted above, procedures similar to these are applied to calculate
analytical results for all of the other PCDD/PCDF determined in this method.-•
8.5 Criteria Which GC-MS Data Must Satisfy for Identification of
PCDD/PCDF in Samples Analyzed and Additional Details of Calculation Procedures.
In order to identify specific PCDD/PCDF in samples analyzed, the
GC-MS data obtained must satisfy the following criteria:
8.5.1 Mass spectral responses must be observed at both the molecular
and fragment ion masses corresponding to the ions indicative of each
chlorinated class of PCDD/PCDF identified (see Table 1) and intensities
of these ions must maximize essentially simultaneously (within +. 1
second). In addition, the chromatographic retention times observed for
each PCDD/PCDF Signal must be correct relative to the appropriate
B-17 " -
-------
stable-isotopically labelled internal standard and must be consistent
with the retention time windows established for the chlorinated group to
which the particular PCDD/PCDF is. assigned.
8.5.2 The ratio of the intensity of the molecular ion (M) *• signal
to that of the (M+2)+ signal must be within + 10% of the theoretically
expected ratio (for example, 0.77 in the case of TCDD; therefore
the acceptable range for this ratio is 0.62 to 0.92).
8.5.3 The intensities of the ion signals are considered to be
'detectable if each exceeds the baseline noise by a factor of at least'
3:1. The ion intensities are considered to be quantitatively measurable
if each ion intensity exceeds the baseline noise by a factor of at
least 5:lc.
8.5.4 For reliable detection and quantisation of PCDF it is also
desirable to monitor signals arising from chlorinated diphenyl ethers
which, if present could give rise to fragment ions yielding ion masses
identical to. those monitored as indicators of the PCDF. Accordingly,
in Table 1, appropriate chlorinated diphenyl ether masses are specified
which must be monitored simultaneously with the PCDF ion-masses. Only
when the response for the diphenyl ether ion mass is not detected at
the same time as the PCDF ion mass can the signal obtained for an
apparent PCDF be considered unique.
8.5.5 Measurement of the concentration of the congeners in a
chlorinated class using the methods described herein is based on the
assumption that all of the congeners are identical to the calibration
standards employed in terms of their respective chemical and separation
properties and in terms of their respective gas chromatographic and mass
spectrometric responses. Using these assumptions, for example, the
13Ci2-2,3,7,8-TCDD internal standard is utilized as the internal
calibration standard for all of the 22 TCDD isomers or congeners.
Furthermore, the concentration of the total TCDD present in a sample
extract is determined by calculating, on the basis of the standard
procedure outlined above, the concentration of each TCDD isomer peak
(or peaks for multiple TCDD isomers, where these coelute) and these
individual concentrations are subsequently summed to obtain the concen-
tration of "total" TCDD.
c* In practice, the analyst can estimate the baseline noise by measuring
the extension of the baseline immediately prior to each of the two mass
chromatographic peaks attributed to a given PCDD or PCDF. Spurious signals
may arise either from electronic noise or from other organic compounds in
the extract. Since it may be desirable to evaluate the judgement of the.
analyst in this respect, copies of original mass chromatograms must be
included in the report of analytical results.
B-18
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DRAFT
8.6 Frequently, during the analysis of actual sample extracts,
extraneous compounds which are present in the extract (those organic
compounds not completely removed during the clean-up phase of the analysis)
can cause changes in the liquid and gas chromatographic elution characteristics
of the PCDD/PCDF (typically retention times for the PCDD/PCDF are prolonged).
Such extraneous organic compounds, when introduced into the mas.s spectro-
meter source may also result in a decrease in the sensitivity of the MS
because of suppression of ionization, and other affects s.uch as charge
transfer phenomena. The shifts in chromatographic retention times are
usually general shifts, that is, the relative retention times for the
PCDD/PCDF are not changed, although the entire elution time scale is
prolonged. The analyst's intervention in the GC-MS operating sequence
can correct for the lengthened GC retention times which are sometimes
observed due to the presence of extraneous organics in the sample
extract. For example, using the program outlined in Table 1, if the
retention time observed for 2,3,7,8-TCDD (which normally is 19.5 minutes)
is lengthened by 30 seconds or more, appropriate adjustments in the
programming sequence outlined in Table 1 can be made, that is, each
selected ion-monitoring program is delayed by a length of time propor-
tionate to the lengthening of the retention time for the 2,3,7,8-TCDD
isomer. In the case of ionization suppression, this phenomenon is
inherently counteracted by the internal.standard approach. However, '
if loss of sensitivity due .to ionization suppression is severe,
additional clean-up of the sample extract may be required in order to
achieve the desired detection limits.
9. Quality Assurance/Quality Control • • ' .
9.1 Quality assurance and quality control are ensured by the following
provisions: '' ." '
9.1.1 Each sample analyzed is spiked with stable isotopically labelled
internal standards, prior to extraction and analysis. -Recoveries
obtained for each'of these standards should typically be in the range
fr.om 60-90%. Since these compounds are used as tru^ internal standards
however, lower recoveries do not necessarily invalidate the analytical
results for native PCDD/PCDF, but may result in higher detection limits
than are desired.
9.1.2 Processing and analysis of at least one method blank sample
is accomplished for each set of samples (a set being defined as 20 samples '
or less). . •
9.1.3 It is desirable to analyze at least one sample spiked with
representative native PCDD/PCDF for each set of 20 or fewer samples. The
result of this analysis provides an indication of the efficacy of the
entire analytical procedure. The results of this analysis will be
considered acceptable if the detected concentration of each of the native
B-19
-------
DRAF
PCDD/PCDF added to the sample is within +50% of the known concentration.
(An appropriate set of native isomers to be added here is a set such
as that indicated for Standard Mixture C.)
9.1.4 At least one of the samples analyzed out of each set (of 20
samples or less) is analyzed in duplicate and the results of the duplicate
analysis are included in the report of data.
9.1.5 Performance evaluation samples prepared by EPA,or other
laboratories,which contain representative PCDD/PCDF in concentrations
approximating those present in typical field samples being analyzed
(but unknown to the analyzing lab) should be periodically distributed
to laboratories accomplishing these analyses.
9.1.6 Sources of all calibration and performance standards used in the
analyses and the purity of these materials must be specified in the data
report.
10. Data Reporting
10.1 Each report of analyses accomplished using the protocol
described herein will typically include tables of results which include
the fallowing: '
10.1.1 Complete identification of the samples analyzed (sample
numbers and source).
10.1.2 The dates and times at which all analyses were accomplished.
This information should also appear on each mass chromatogram included
with the report.
• 10.1.3 Raw mass chromatographic data which consists of the absolute
intensities (based on either peak height or peak area) of the signals
observed for the ion-masses monitored (See Table 1).
• * •
10.1.4 The calculated ratios of the intensities of the molecular
ions for all PCDD/PCDF detected.
•
10.1.5 The calculated concentrations of native 2,3,7,8-TCDD and
2,3,7,8-TCDF, and the total concentrations of the congeners of each
class of PCDD/PCDF for each sample analyzed, expressed in nanograms
TCDD per gram of sample (that is, parts-per-billion) as determined
from the raw data. If no PCDD/PCDF are detected, the notation "Not
Detected" or "N.D." is used, and the minimum detectable concentrations
B-20
-------
until-)
(or detection limits) are reported.
DRAFT
10.1.6 The same raw and calculated data which are provided for the
actual samples will also be reported for the duplicate analyses, the
method blank analyses, the spiked sample analyses and any other QA
or performance samples analyzed in conjunction with the actual sample
set(s).
10.1.7 The recoveries of the internal standards in percent.
10.1.8 The recoveries of the native PCDD/PCDF from spiked sample?
in percent.
10.1.9 The calibration data, including response factors calculated
from the three point calibration procedure described elsewhere in this
protocol. Data showing that these factors have been verified at least
once during each 8 hour'period of operation or with each separate set
of samples analyzed must be included.
10.1.10 The weight or quantity of the original sample analyzed.
*
• • 10.1.11 Documentation of the source of all PCDD/PCDF standards
used and available specifications on purity.
10.1.12 In addition to the tables described above, each report of
analyses will include all mass chromatograms obtained for all samples
analyzed, as well as for all calibration, GC column performance, and
GC "window" definition runs and results of column performance checks.
10.1.13 Any deviations from the procedures described in this protocal
which are applied in the analyses of samples will be documented in •
detail in the analytical report.
11. Typical Data Indicative of Method Performance - Precision and Accuracy.
11.1 The method described herein has typically been employed to
quantitatively determine 2,3,7,8-TCDD in combustion product samples at
concentrations as low as 10 picograms/gram and as high at 100 vg/g.
Concentrations of the other PCDD/PCDF which can be detected typically
fall within the range of 20 picograms/isomer/gram of sample, to 100
picograrns/g of sample. Of course, the limits of detection which can
be practically achieved are dependent on the quantity of sample available
B-21
-------
DRAFT
and the amount and kind of other interfering organic residues which are
present in the sample. With respect to precision, .the average deviation
of data obtained from the analyses of a number of aliquots of the same
sample containing the 2,3,7,8-TCDD isomer in the 250-300 ppb range
1s estimated to be +10% or better. Data on the precision of quantisation
of multiple PCDD/PCDF in a single sample are not as yet available. As
yet, there is inadequate interlaboratory and performance evaluation data
available to specify the accuracy which can be expected of the analytical
procedures described herein.
B-22
-------
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I
DRAFT
APPENDIX
RECOMMENDED SAFETY AND HANDLING PROCEDURES
FOR LABORATORIES CONDUCTING PCDD/PCDF ANALYSES
B-25
-------
DRAFT
Recommended Safety and Handling Procedures in Connection with Implementing
the Analytical Protocal for Determination of PCDD/PCDF in Combustion Products
1. The human toxicology of PCDD/PCDF is not well defined at present,
although the 2,3,7,8-TCDD isomer has been found to be acnegenic,
carcinogenic, and teratogenic in the course of laboratory animal
studies. The 2,3,7,8-TCDD is a solid at room temperature, and has a
relatively low vapor pressure. The solubility of this compound in
water is only about 200 parts-per-trillion, but the solubility in
various organic solvents ranges from about 0.001% to 0.1,4%. The physical
properties of the 135 other tetra-through octachlorinaed PCDD/PCDF have not
been well established, although it is presumed that the physical
properties of these congeners are generally similar to those of the
2,3,7,8-TCDD isomer. On the basis of the available toxicological
and physical property data for TCDD.'this compound, as well as the other
PCDD and PCDF, should be handled only by highly trained personnel
who are thoroughly versed in the appropriate procedures, and who
understand the. associated risks.
2. PCDD/PCDF and samples containing these are handled using essentially
the same techniques as those employed in handling radioactive or
infectious materials. Well -ventilated, control! ed-access laboratories
are required, and laboratory personnel entering these laboratories should
wear appropriate 'safety clothing, including disposable coveralls,
shoe covers, gloves,- and face and head masks.. During analytical . „ . .
operations which may give rise to aerosols or dusts, personnel should
wear respirators equipped with activated carbon filters. Eye protection
equipment (preferably full face shields) must be worn at. all times
while working in the analytical laboratory with PCDD/PCDF. Various _
types of gloves can be used by personnel, depending upon the analytical
operation being accomplished. Latex gloves are generally utilized,
and when handling samples thought to be particularly hazardous, an
additional set of gloves jre also worn beneath the latex gloves
(for example, Playtex gloves" supplied by American Scientific Products,
Cat. No. 67216). Bench-tops and other work surfaces in the laboratory
should be covered with plastic-backed absorbent paper during all
analytical processing. When finely divided samples (dusts, soils, ^dry
chemicals) are being processed, removal of these from sample containers,
as well as other operations, including weighing, transferring, and
mixing with solvents, should all be accomplished within a glove box.
Glove boxes, hoods and the effluents from mechanical vacuum pumps and
gas chroma tographs on the mass spectrometers should be vented to the
atmosphere preferably only after passing through HEPA particulate
filters and vapor-sorbing charcoal. *- .
3. All laboratory v/are, safety clothing and other items potentially
contaminated with PCDD/PCDF in the course of analyses must be carefully
secured and subjected to proper disposal. When feasible., liquid wastes
• B-26
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DRAFT
are concentrated, .and the residues are placed.in approved steel hazardous
waste drums fitted with heavy gauge polyethylene liners. Glass and
combustible items are compacted using a dedicated trash compactor used
only for hazardous waste materials and then placed in the same.type
of disposal drum. Disposal of accumulated wastes is periodically
accomplished by high temperature incineration at EPA-approved facilities.
4. Surfaces of laboratory benches, apparatus and other appropriate
areas should be periodically subjected to surface wipe tests using
solvent-wetted filter paper which is then analyzed to check for PCDD/PCDF
contamination in the laboratory. Typically, if the detectable level
of TCDD or TCDF from such a test is greater than 50ng/m2, this indicates
the need for decontamination of the laboratory. A typical action limit
in terms of surface contamination of the other PCDD/PCDF (summed) is
500ng/m2. In the event of a spill within the laboratory, absorbent .
paper is used to wipe up the spilled material and this is then placed
into a hazardous waste drum. The contaminated surface is subsequently
cleaned thoroughly by washing with appropriate solvents (methylene
chloride followed by methanol) and laboratory detergents. This is
repeated until wipe tests indicate that the levels of surface contamination
are below the limits cited.
5. In the unlikely event that analytical personnel experience skin
contact with PCDD/PCDF or samples containing these, the contaminated
skin area should immediately be thoroughly scrubbed using mild soap
and water. Personnel involved in any su'ch" a~cCtde"rit should subsequently
be taken to the nearest medical facility, preferably a facility whose
staff is knowledgable in the toxicology of chlorinated hydrocarbons.
Again, disposal of contaminated clothing is accomplished by placing, it
in hazardous waste drums.
6. It is desirable that personnel working in laboratories where
PCDD/PCDF are handled be given periodic physical examinations (at
least yearly). Such examinations should include specialized tests,
such as those for urinary porphyrins and for certain blood parameters
which, based upon published clinical observations, are appropriate for
persons who may be exposed to PCDD/PCDF. Periodic facial photographs
to document the onset of dermatologic problems are also advisable.
B-27
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TECHNICAL REPORT DATA
(Please read Instntctions on the reverse before completing)
1. REPORT NO.
EPA-450-4-84-014C
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
National Dioxin Study Tier 4
- Combustion Sources:
S. REPORT DATE
October 1984
Sampl-i.ng Procedures
6. PERFORMING ORGANIZATION CODE
7. AUTHOR
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