United States
Environmental
Protection Agency
Office of Solid Waste Office of Air Off ice of Research EPA/530-SW-87-02lf
and Emergency Response and Radiation and Development June 1987
Washington, DC 20460 Washington, DC 20460 Washington, DC 20460
&EPA
Municipal Waste
Combustion Study
Sampling and Analysis of
Municipal Waste Combustors
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DISCLAIMER
This document has been reviewed and approved for
publication by che Office of Research and Development,
U.S. Environmental Protection Agency. Approval does
not signify that the contents necessarily reflect the
views of the Agency. Nor does mention of trade names
or commercial products constitute endorsement or
recommendation for use.
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TABLE OF CONTENTS
Page
List of Tables v
List of Figures vi
I. INTRODUCTION 1
A. OVERVIEW 1
B. PURPOSE OF THIS DOCUMENT 2
C. SCOPE 2
D. USE OF REPORT 4
II. SAMPLING AND ANALYSIS STRATEGIES 5
A. PURPOSE OF DATA COLLECTION 5
B. SELECTION OF SAMPLING AND ANALYSIS METHODS 9
C. QA AND QC OVERVIEW 9
III. SAMPLING 11
A. OVERVIEW 11
B. SAMPLING METHODS FOR STACK GAS EMISSIONS 16
C. SAMPLING METHODS FOR FLUE GAS 26
D. SAMPLING METHODS FOR SOLID AND LIQUID EFFLUENTS 29
E. SAMPLING METHODS FOR WASTE FEED 31
IV. SAMPLE PREPARATION PROCEDURES 33
A. OVERVIEW 33
B. REPRESENTATIVE ALIQUOT FROM FIELD SAMPLES 33
C. RECOVERY METHODS 38
D. EXTRACTION METHOD 39
E. DRYING AND CONCENTRATING OF EXTRACTS 40
F. SAMPLE CLEAN-UP 40
G. DIGESTION 41
V. ANALYSIS PROCEDURES 42
A. OVERVIEW 42
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TABLE OF CONTENTS ,CONT.)
Page
B. PROXIMATE ANALYSIS 43
C. SCREENING ANALYSIS 44
D. DIRECTED ANALYSIS 45
VI. CONTINUOUS MONITORING METHODS 47
A. OVERVIEW 47
B. SAMPLE CONDITIONING 47
C. MONITORS FOR INORGANICS 49
D. MONITORS FOR ORGANICS 60
E. INDICATOR OR SURROGATE MONITORING 61
F. SPECIAL QA/QC CONSIDERATIONS 61
G. POTENTIAL FOR PROCESS CONTROL 63
VII. QUALITY ASSURANCE AND QUALITY CONTROL 64
A. OVERVIEW 65
B. TITLE PAGE AND TABLE OF CONTENTS 65
C. PROJECT DESCRIPTION 65
D. PROJECT ORGANIZATION AND RESPONSIBILITY 67
E. QUALITY ASSURANCE OBJECTIVES 67
F. SAMPLING PROCEDURES 67
G. SAMPLE CUSTODY 70
H. CALIBRATION PROCEDURES AND FREQUENCY 71
I. ANALYTICAL PROCEDURES 72
J. DATA REDUCTION, VALIDATION, AND REPORTING 73
K. INTERNAL QUALITY CONTROL CHECKS 73
L. PERFORMANCE AND SYSTEM AUDITS 75
iii
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TABLE OF CONTENTS (CONT.)
Page
M. PREVENTIVE MAINTENANCE 76
N. SPECIFIC ROUTINE PROCEDURES USED TO ASSESS DATA PRECISION,
ACCURACY, AND COMPLETENESS 76
0. CORRECTIVE ACTION 77
P. QUALITY ASSURANCE REPORTS TO MANAGEMENT 78
VIII. REFERENCES 80
APPENDIX A 84
APPENDIX B 8q
iv
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LIST OF TABLES
Table Page
No.
1 EXAMPLES OF POLLUTANTS THAT HAVE BEEN OF INTEREST IN RESEARCH
AND DEVELOPMENT OR OTHER SPECIAL PURPOSE PROGRAMS 6
2 STACK SAMPLING METHODS 17
3 DATA FROM 1986 TEST AT SAUGUS RESOURCE RECOVERY PLANT 20
4 SAMPLING METHODS FOR SOLID AN . _IQUID EFFLUENTS ' 30
5 SUMMARY OF SAMPLE PREPARATION METHODS 34
6 SUMMARY OF PROCEDURES FOR COMPOSITING SAMPLES 37
7 ANALYSIS METHODS FOR TRACE ORGANICS AND TRACE METALS,
APPLICABLE TO MSW COMBUSTOR SAMPLES 46
8 CONTINUOUS ANALYZERS FOR CARBON MONOXIDE 53
9 CONTINUOUS ANALYZERS FOR CARBON DIOXIDE 54
10 CONTINUOUS ANALYZERS FOR OXYGEN 55
11 CONTINUOUS ANALYZERS FOR SULFUR DIOXIDE 56
12 CONTINUOUS ANALYZERS FOR NITROGEN OXIDES 57
13 CONTINUOUS ANALYZERS FOR HYDROCHLORIC ACID 58
14 CONTINUOUS ANALYZERS FOR HYDROGEN CYANIDE 59
15 ESSENTIAL ELEMENTS OF A QA PROJECT PLAN 66
16 SUMMARY OF ESTIMATED PRECISION, ACCURACY, AND COMPLETENESS
OBJcuTIVES 69
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LIST OF FIGURES
Figure
No. Page
1 GENERALIZED MUNICIPAL SOLID WASTE INCINERATION PROCESS
SCHEMATIC 12
2 SIMPLIFIED SCHEMATIC OF A MASS BURN MSW COMBUSTOR, SHOWING
SAMPLE LOCATIONS 13
3 SIMPLIFIED SCHEMATIC OF AN RDF COMBUSTOR, SHOWING SAMPLE
LOCATIONS 14
4 SIMPLIFIED SCHEMATIC OF A STARVED-AIR MSW COMBUSTOR,
SHOWING SAMPLING LOCATIONS 15
5 SCHEMATIC OF STANDARD EPA METHOD 5 TRAIN 22
6 MM5 TRAIN SCHEMATIC DIAGRAM 23
7 SASS SCHEMATIC DIAGRAM 25
8 SCHEMATIC OF VOLATILE ORGANIC SAMPLING TRAIN 27
9 EXAMPLE OF PROJECT ORGANIZATION AND RESPONSIBILITY 68
vi
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FOREWORD
This document is intended to serve as a resource document outlining
recommended sampling, analysis and monitoring procedures for municipal solid
waste combustion facilities. The effort reported here has focused on gathering
information on probable measurement requirements and on available methods that
may meet those requirements. Critical evaluations of alternative methods and
recommendations to fill gaps in available methodology were outside of the scope
of this assignment.
The Arthur D. Little, Inc. effort is part of a major program to develop an
EPA report to Congress on Municipal Waste Combustion. The overall effort is
being directed by Radian Corporation (G. Wilkins, Project Manager). The Arthur
D. Little contribution is being performed under EPA subcontract with Dynamic
Corporation (C. Matkovich, work assignment director). L. D. Johnson is the EPA
work assignment director for the Arthur D. Little effort. Key Arthur D. Little
staff involved in this work are J. C. Harris (to whom comments should be
addressed), D. L. Cerundolo, and K. E. Thrun. The Arthur D. Little reference
numbers for this work are 55464 and 55465.
vii
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I. INTRODUCTION
A. OVERVIEW
This report is an assessment of sampling and analysis methods for municipal
waste combustors. The information presented in this report was developed during
a comprehensive, integrated study of municipal waste combustion. An overview of
the findings of this study may be found in the Report to Congress on Municipal
Waste Combustion (EPA/530-SW-87-021A). The Technical volumes issued as part of
the Municipal Waste Combustion Study include:
Municipal Waste Combustion Study:
Report to Congress
EPA/530-SW-87-021A
Municipal Waste Combustion Study:
Emissions Data Base for Municipal
Waste Combustors
EPA/530-SW-87-021B
Municipal Waste Combustion Study:
Combustion Control of Organic
Emissions
EPA/530-SW-87-021C
Municipal Waste Combustion Study:
Flue Gas Cleaning Technology
EPA/530-SW-87-021D
Municipal Waste Combustion Study:
Costs of Flue Gas Cleaning
Technologies
EPA/530-SW-87-021E
Municipal Waste Combustion Study:
Sampling and Analysis
EPA/530-SW-87-021F
Municipal Waste Combustion Study:
Assessment of Health Risks
Associated with Exposure to
Municipal Waste Combustion Emissions
EPA/530-SW-87-021G
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• Municipal Waste Combustion Study:
Characterization of the Municipal
Waste Combustion Industry EPA/530-SW-87-021H
• Municipal Waste Combustion Study:
Recycling of Solid Waste EPA/530-SW-87-021I
B. PURPOSE OF THIS DOCUMENT
The purpose of this document is to provide guidance on sampling and
analysis methods to assist federal, state, and local environmental authorities
in reviewing plans for operations and testing of MSW combustors. The sampling
and analysis procedures outlined here are intended to represent state-of-the-art
methods that may be useful in determining the regulatory compliance status of
MSW incineration facilities and in assessing their environmental impacts. These
same methods may be useful in research and development programs related to MSW
combustion technology, standard setting, etc.
C. SCOPE
This document provides an overview of available state-of-the-art methods
for sampling and analysis to address testing and monitoring of MSW combustors.
For purposes of this report, testing and monitoring are defined as follows:
"testing" means performing periodic sampling and analysis
by EPA-approved or recommended methods to: confirm compliance with any
limits that have been imposed by regulatory agencies as permit conditions;
generate data that may be used as inputs to environmental risk assessments;
and/or support research and development in municipal waste combustion.
"monitoring" means obtaining continuous instrumental measure-
ments of key process parameters and selected pollutants in the
emissions to verify that the facility continues to operate "in control".
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The testing can be expected to focus on several categories of potential
pollutants:
Criteria pollutants: particulates, CO, SC- NO ,
£. X
Acid gases: HC1, HF
Trace metals: Cr(III), Cr(VI), Cd, As, Hg, Pb, Be, etc.
Organic pollutants: chlorina " dibenzo-p-dioxins, chlorinated
dibenzofurans, and other trace level species that may be indicators of
potential environmental impacts
The parameters for which continuous monitoring may be required during
routine operation or requested as part of special purpose programs include:
temperature
opacity
carbon monoxide
carbon dioxide
oxygen
nitrogen oxides
sulfur oxides
hydrochloric acid
"total hydrocarbon"
performance "indicator" species (e.g., CO)
Procedures for measuring the above parameters in ultimate effluents from
MSW combustion facilities (stack gas, solid residues such as bottom- and
fly-ash, and liquid effluents such as scrubber water) are described in this
report. Two other aspects of MSW combustor sampling and analysis--measurements
on the MSW feed and measurements on flue gases upstream of air pollution control
devices--are also addressed, but procedures appropriate for these media are
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less well developed or defined. In both cases, the principal difficulty is in
obtaining a representative sample. MSW is highly heterogeneous and some
individual items present are so large or bulky as to preclude effective use of
compositing procedures. (See Section HIE for further discussion). Flue gas
sampling (discussed in Section IIIC) is complicated by uneven flow conditions
and by components (e.g., high particulate material and acid gas loadings) that
clog or corrode conventional sampling equipment.
This document speaks only to issues of MSW combustor source sampling and
analysis. Procedures for assessing ambient air impacts, either by dispersion
modelling or by direct ambient air sampling and analysis in the vicinity of the
facility, are not described. Sampling and analysis of fugitive emissions (e.g.,
from transfer or storage operations) are not covered in this document.
D. USE OF REPORT
It is anticipated that this report will serve as a useful reference point
for MSW combustor owner/operators and for federal, state and local authorities
involved in facility permitting process. The sampling and analysis methods
described and/or recommended here are not to be construed as representing unique
or mandatory requirements for emissions testing or continuous monitoring at MSW
combustion facilities. Inclusion in this report does not mean that a sampling
or analysis method is an official EPA method. The procedures described here
should be reviewed against those in the current Code of Federal Regulations and
in official methods manuals, such as "Test Methods for Evaluating Solid Waste"
(SW-846) , before any MSW combustor test program is finalized.
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II. SAMPLING AND ANALYSIS STRATEGIES
A. PURPOSE OF DATA COLLECTION
The principal purpose of generating data from MSW combuster sampling and
analysis is to determine the effects of emissions from a facility on health and
the environment. These data can be used to determine compliance with applicable
criteria or to perform an assessment of the health risk associated with the
emissions. In some cases, the purpose of the sampling and analysis may be
primarily to support research and development in MSW combustion technology. In
those instances, there may be a requirement for some types of measurements
(e.g., characterization of waste feed or in-furnace measurements) that are more
extensive than those needed for compliance testing or risk assessment.
Table 1 indicates some examples of the types of compounds for which
measurements have been made in various test programs. Most of these are not
regulated pollutants in stack gas emissions, and inclusion in the Table is not
meant to imply that measurement of these potential pollutants should be
required. However, this document presents methods that would be applicable to
the sampling and analysis of these types of pollutants if such measurement were
determined to be necessary or useful.
In every case, it is essential that critical decision limits for each
parameter be established in specific quantitative terms prior to selection of
sampling and analysis methods. This may require, in many cases, that a
preliminary air quality modelling run be performed in order to calculate what
stack gas concentration corresponds to a specific ambient air quality criterion.
This exercise allows calculation of the sampling and analysis method detection
limit that will be necessary to meet the project objectives.
The precision and accuracy criteria for the measurement method will also
depend on the specific uses to be made of the data. It is important to
establish whether it is each of n measurements, or the mean of n measurements,
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TABLE 1
EXAMPLES OF POLLUTANTS THAT HAVE BEEN OF INTEREST IN RESEARCH AND DEVELOPMENT OR
OTHER SPECIAL PURPOSE PROGRAMS
Volatiles:
Benzene
Carbon Tetrachloride
Chloroform
Formaldehyde
Perchloroethylene
Toluene
Metals:
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Manganese
Mercury
Nickel
Selenium
Semivolatiles: Benzo(a)pyrene
Chlorobenzenes
Chlorodibenzodioxins
Chlorodibenzofurans
Chlorophenols
Naphthalene
Phenol
Polychlorinated Biphenyls
Pyrene
Others: Hydrogen Chloride
Hydrogen Fluoride
Sulfur Dioxide
Source: Arthur D. Little, Inc., conversations with regulatory authorities.
/L Arthur D. Little, Inc.
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or the 95% confidencelimit around the mean that is to be compared with the
critical decision limit.
The general purposes of collecting data by testing and monitoring of MSW
combustors are discussed below. The specific purposes (and thus the critical
decision limits) must be established on a case-by-case basis.
Criteria Pollutants. The criteria pollutants (particulate material, carbon
monoxide, nitrogen oxides, ozone, and sulfur dioxide) are those species for
which. EPA has established primary and/or secondary National Ambient Air Quality
Standards (NAAQS). As the name implies, these standards apply to the cumulative
impact from all sources, not the source-by-source emissions, on ambient air
concentrations. However, it may be necessary to measure emissions of criteria
pollutants from an MSW combustor in order to assess its incremental contribution
to the total ambient level. This is especially likely in the case of new MSW
facilities in areas where current levels are close to or exceed the NAAQS. The
criteria pollutants are also of concern with regard to Prevention of Significant
Deterioration (PSD) determinations.
Acid Gases. In addition to SO (discussed above), hydrochloric acid and a
lesser quantity of hydrogen fluoride are acid gases that can be expected to be
present in MSW combustor off-gases. Although there are not federal EPA
standards relating to HC1 emissions from facilities other than hazardous waste
incinerators, many state environmental agencies (e.g., Maine, Massachusetts, New
Jersey, California) consider that acid gas removal from MSW incinerator
effluents represents Best Available Control Technology (BACT). Testing of stack
emissions of HC1 and HF may be required to demonstrate that a degree of acid gas
control consistent with BACT has been achieved.
Trace Metals. Trace metal species, in addition to lead, that may need to
be measured in MSW incinerator effluents include: arsenic, beryllium, cadmium,
chromium, and mercury. In general, air emissions of trace metals from MSW
sources are not currently addressed in EPA regulations, but may be of concern
with regard to potential health effects. In some cases, it may be necessary to
differentiate Cr (III) from Cr (VI) in order to assess the magnitude of health
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effects. The metals content of MSW incinerator aqueous effluents (e.g.,
scrubber or quench water) and of solid residues (e.g., bottom ash, fly ash) may
need to be ascertained in order to determine disposal status vis-a-vis NPDES or
RCRA regulations, respectively.
Organic Pollutants. Data on chlorinated dibenzo-p-dioxins and
dibenzofurans in stack gas effluents may be required as inputs to air quality
models in order to estimate whether the risk of exposure to these chemicals from
this source is within the range of acceptability. Permitting authorities may
* ,
request data on other trace organi - such as polynuclear aromatic hydrocarbons
or phenols, in order to perform similar risk calculations. Again, NPDES or RCRA
regulations may require the determination of specific organic chemicals in
aqueous effluents or solid residues, depending on "he disposal or treatment
alternatives that are to be applied to these streams. Selected organics may
also be measured during MSW combustion research and development as indicators of
the efficiency of the combustion process and/or pollution control devices.
Monitoring. Continuous monitoring of MSW combustor emissions provides a
mechanism for tracking the performance of the system in real time. The
parameters that can be monitored continuously are generally those (e.g.,
temperature, oxygen, carbon monoxide) that indicate the overall combustion
efficiency or those (e.g., opacity, SO ) that indicate air pollution control
device (APCD) performance. These measurements are important for confirming that
a facility is continuing to operate under controlled, steady-state conditions
and is in compliance with specific emissions limitations written into its
operating permits. In addition, the on-line monitor data can serve as an "early
warning system" to detect combustor/APCD system upsets due to mechanical
failures and/or gross changes in waste composition (e.g., very wet waste).
Thus, even if an on-line monitor is not sufficiently accurate or precise for
determining compliance with emissions limitations (e.g., commercially available
opacity meters do not reliably determine particulate matter emissions below 0.03
gr/dscf), data from such an instrument is nevertheless useful as an indicator of
potential upset conditions.
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B. SELECTION OF SAMPLING AND ANALYSIS METHODS
Once the uses of the data have been defined and the consequent data quality
objectives have been established, it is possible to make an informed selection
among alternative sampling and analysis (S/A) methods.
The principal criteria to be used in making this selection are the
following:
• regulatory status. Is the S/A method chosen approved by EPA for this
measurement purpose?
• sensitivity. Has the method been proven to have a detection limit
that is sufficiently low to allow accurate quantification of the
pollutant of interest at concentrations corresponding to the critical
decision limit?
• selectivity. Will other species that are likely to be present in MSW
combustor effluents interfere in the determination?
• reliability. Is the method sufficiently rugged to be applicable in
the hostile nvironment represented by MSW incineration?
It is important to emphasize that these criteria must be applied to the
overall sampling--sample preparation--analysis system, not just to the analysis
method per se.
C. OA AND PC OVERVIEW
Quality Assurance (QA) and quality control (QC) are vitally important
components of any sampling and analyses program. QC procedures, including the
analysis of standards, blanks, replicate samples, and spikes, provide on-going
confirmation that the sampling and analysis methods are "in control" and that
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the data generated are valid for the intended purpose. QA procedures ensure
that all data, including QC data, are reviewed and that any necessary corrective
actions are instituted in a timely fashion.
In order to ensure the effective implementation of QA/QC functions, it is
necessary that specific quantitative Data Quality Objectives (DQOs) be
established for each measurement. Guidance in developing a QA/QC plan for MSW
combustion testing/monitoring is discussed further in Section VII of this report
and in the EPA report, "Interim Guidelines and Specifications for Preparing
(2)
Quality Assurance Project Plans."
10
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III. SAMPLING
A. OVERVIEW
Sampling of MSW combustion facilities for purposes of determining
compliance with regulatory limitations or of assessing potential environmental
risks is usually focused primarily on air emissions (stack gas). Solid residues
(bottom ash and fly ash) are also commonly sampled. Some facilities may also
have aqueous effluents from wet scrubbing or ash quenching operations.
Figure 1 shows a generalized schematic of the MSW combustion process, with
sampling points indicated generically, Figures 2, 3, and 4 present,
respectively, schematics of a mass burn, refuse-derived-fuel (RDF), and starved
air MSW incinerator, again with generic identification of sampling locations.
Exact sampling points must be specified on a case-by-case basis for each
facility, taking into account accessibility, temperature and flow conditions,
and operational modes (e.g., batch or continuous discharge of residue).
The critical considerations in selection of a sampling method are: (1) the
representativeness of the sample and (2) compatibility of the sampling procedure
with the intended analytical finish.
To ensure representativeness, emissions samples are usually integrated over
time. A 1-4 hour time-integrated sample is usually taken to smooth out the
perturbations that occur due to the inherent variability of MSW. In the case of
stack sampling, it is often possible to accomplish this directly by adjusting
the sampling rate to cover the desired time period. In the case of liquid or
solid residues from MSW combustors, the time integration is usually accomplished
by preparing a composite sample, combining equal-sized aliquots collected at
intervals over the duration of a test. Sampling of solid waste, if requested in
a particular facility test, is usually done by compositing of subsamples, in
accordance with procedures described in SW-846. In all cases, the
representativeness of the sampling method can be checked, but not proven, by
acquiring duplicate samples representing the same time period of facility
operation.
11
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ro
Waste
Feed
Samples
Incinerator
Feed
Hopper
:*. Plant *»
* Trash ••«
Stack
Emission
Samples
Supplemental
Fuel
Steam
c^«
Separation/
Classification
J I
Flue Gas
Samples
Combustion
Chamber
Stack Gas
Treatment Train
Ash Pile
Fly «id Bottom
Ash Samples *
Bottom Ash *
Fly Ash *
Ash Transfer Hopper
*. To Landfill
FIGURE 1
GENERALIZED MUNICIPAL SOLID WASTE INCINERATION PROCESS SCHEMATIC
(Adapted from original by S-Cubed, a Division of
Maxwell Laboratories, Inc.)
*In many facilities, fly ash and bottom ash are collected in a single hopper.
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Stack
Emission
Samples
Electrostatic
Precipitator
Incinerator
Stoker
Unit
Bottom
Ash
Samples *
Fly
Ash
Samples *
FIGURE 2 SIMPLIFIED SCHEMATIC OF A MASS BURN MSW COMBUSTOR. SHOWING SAMPLE LOCATIONS
(Adapted from original by C. R. Brunner, "Incineration Systems Seminar," (198?))
*Tn
tiff* - f 1
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Material
Handling
Blower
Electrostatic
Precipitator
or
Fabric Filter
Shredder
Infeed
Conveyor
Stack
Heavy Ends
Fluidizing Blower to Disposal
FIGURE 3 SIMPLIFIED SCHEMATIC OF AN RDF MSW COMBUSTOR, SHOWING SAMPLE LOCATIONS
(Adapted from original by C. R. Brunner, "Incineration
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Stack
•Stack Emission Samples
Platform
Access
Doors
Bottom
Ash
Samples
FIGURE 4 SIMPLIFIED SCHEMATIC OF A STARVED AIR MSW COMBUSTOR, SHOWING SAMPLING LOCATIONS
(Adapted from original by C. R. Brunner, "Incineration Systems Seminar," (1982))
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Compatibility is a complex issue. Most analytical methods (e.g., GC/MS for
trace organics, AAS for trace metals) cannot be applied directly to the sample
but require extensive sample preparation. Even methods that are inherently
"on-line" procedures (e.g., continuous instrumental monitoring of CO or SO ) may
X
require sample clean-up to remove particulate material, water vapor, etc. or
other forms of sample conditioning prior to analysis. It is important that the
QAPP (quality assurance project plan) for any MSW combustion sampling and
analysis program contain procedures to assure that no unacceptable losses are
introduced by whatever procedures are required to ensure compatibility.
B. SAMPLING METHODS FOR STACK GAS EMISSIONS
Table 2 lists EPA-approved and/or recommended state-of-the-art stack
sampling methods for various pollutants and/or categories of pollutants. (Note:
Table 2 includes only extractive sampling methods. Continuous monitoring
methods are discussed in Section VI.) Most of these procedures have been
subjected to extensive method development, validation and/or round-robin
collaborative testing. Although they may not all have been validated at MSW
combustion facilities specifically, there is every reason to believe that they
will be directly applicable for the purpose of sampling MSW stack emissions.
In fact, a number of these methods have been employed in recent MSW combustion
(3 4)
sampling and analysis programs ' and appear to provide reliable data. For
example, Table 3 shows the results obtained in a series of 6 replicate stack gas
emission tests for polychlorinated dioxins and furans at one MSW combustor using
the ASTM sampling and analysis protocol (see below and Appendix B for
description).(6) These data show the precision (relative standard deviation
(RSD)) that can be achieved when sampling and analysis is carried out according
to the recommended methods by experienced personnel (in this case, Radian
Corporation for sampling and Triangle Laboratories for analysis). The RSD
values in the table reflect the combined effects of actual variations in
emissions, sampling variance, and sample preparation/analysis variability for
this test series. RSD's could be expected to be somewhat higher at lower
PCDD/PCDF emission levels. However, the data indicate that the state-of-the-art
sampling and analysis methods are workable in experienced hands. It should be
16
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TABLE 2
STACK SAMPLING METHODS
Pollutant
Criteria and Conven-
tional Parameters
Principle
Comment
Reference
Partlculate
Sulfur
Oxides
Carbon
Monoxide
Nitrogen
Oxides
Isokinetie collection of a 1 hr. sample
on glass fiber filter at 120+ 14°C.
Train includes: T-controlled probe,
optional cyclones, heated filter,
impingers, flow control and gas volume
metering system.
Visual determination of opacity
Instrumental measurement of opacity
(optical density)
Collection in isopropanol (SO,.) and
hydrogen peroxide (S0?) impingers of
M5-type train.
Integrated gas bag or direct interface
via air-cooled condenser.
Collection in evacuated flask
containing sulfuric acid and hydrogen
peroxide.
Designed to meet 0.08 gr/SCF
standard. Probably adequate
down to 0.01 gr/SCF, especially
if sampling period is increased
to 2 hrs.
EPA Meth. 5
Not reliable for quantifica-
tion at 0.03 gr/SCF or below.
Low ppm to percent
Water vapor, carbon dioxide
are interferences; need
silica gel, ascarite traps to
remove.
20-1000 ppm
Grab sample (not
time-integrated)
ppm levels
Does not differentiate
NO from NO,,
EPA Meth. 9
EPA Meth. 6,8
EPA Meth. 10
EPA Meth. 7.7A
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TABLE 2 (cont.)
STACK (FLUE GAS) SAMPLING METHODS
Pollutant
Hydrochloric
Acid
Hydrogen
Fluoride
Principle
Collection in aqueous NaOH impingers in
M5-type train.
Collection on paper or membrane (not
glass fiber) filter and aqueous
impingers in M5-type train.
Comment
ppm to percent range
Low ppm range.
Reference
(18)
EPA Meth. 13B
Trace Metals
General
Lead
oo
M5 or SASS train, glass fiber filter
and nitric acid or ammonium persulfate
impingers
Collection on glass fiber filter and
nitric acid impingers in M5-type train.
ppb to ppm levels if
is A 0.75 M
of stack gas
(18)
EPA Meth. 12
Mercury
Arsenic
Beryllium
Collection in iodine monochloride or
acidic permanganate impingers in
M5-type train.
Collection on glass fiber filter and
aqueous impingers in M5-type train.
Collection on millipore AA filter and
aqueous impingers in M5-type train.
Probe must be glass- or
quartz-lined.
ppm levels. Other reagents
also possible.
Probe must be glass or
quartz-lined.
EPA Meth. 101
EPA Meth. 108
EPA Meth. 104
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TABLE 2 (cont.)
STACK (FLUE GAS) SAMPLING METHODS
Pollutant
Principle
Comment
Reference
Trace Organics
Specific Volatile
organics
Collection on Tenax-GC
1 LPM for 20 minutes.
and charcoal at
Semi-volatile M5 train modified to include XAD-2 trap
organics, including for organic collection between filter
dioxins, furans and irapingers.
5-fold scale up of MM5 system.
ppb-ppm levels;multiple
species
ppb-ppm levels; multiple
species
sub-ppb levels for
dioxins/furans if dedicated
sample
VOST
MM5
SASS
Vinyl chloride*
Formaldehyde
Integrated gas bag
0.1-50 ppm
Collection on DNPH-coated sorbent or in ppn levels
aqueous DNPH impingers.
EPA Meth. 106
(18)
Gaseous Hydro-
carbons, total
Gaseous Hydro-
carbons, total
Integrated bag sample or direct
interface
Evacuated stainless steel or aluminum
tank behind chilled condensate trap.
ppm levels
EPA Meth. 18
EPA Meth. 25
* VOST can also be used for vinyl chloride, but collection and recovery efficiency may be low.
-------
TABLE 3
Data from 1986 Test as Saugus Resource Recovery Plant
STACK GAS (Corrected to 12% C02)
Avg cone (n = 6 HM5 runs)
DIOXINS
2,3,7,8
tetras
pentas
hexas
heptas
octa
Subtotal
ng/dscm
1.73
32
35
35
30
37
169
sd
0.65
12
12
10
12
26
49
rsd
38
38
34
30
38
68
29
monos
dis
tris
Total
1
12.
183
1
5
51
60
37
28
FURANS
2,3,7,8
tetras
pentas
hexas
heptas
octa
Subtotal
monos
dis
tris
23
182
106
69
36
18
411
1
31
136
5
49
31
20
14
25
101
1
8
26
Total 579 126
GRAND TOTALS, DIOXINS + FURANS
C14-C18
CI1-CI8
580
762
145
169
23
27
29
29
38
139
25
95
25
19
22
25
22
/fc. Arthur D. Little. Inc.
20
-------
recognized that these procedures require an exceptionally high level of quality
control to ensure that adequate recoveries and detection limits have been
achieved in each instance.
The Method 5 (M5) type train represents the principal method for sampling
of criteria pollutants, acid gases, metals, and semi-volatile organics. The
basic Method 5 train, shown schematically in Figure 5, includes a probe with
buttonhook nozzle and pitot tube, a filter section, an impinger train and a
metering system. The probe and filter sections are maintained at a temperature
of 250 F; material recovered from these train components and dried to constant
weight is defined as particulate material. For quantification or chemical
analysis of particulate material, the sampling must be done isokinetically
(i.e., gas velocity into the probe equals the gas velocity within the stack).
As noted in Table 2, the M5 train is used with minor modifications to
determine many inorganic species, such as sulfur oxides or trace metals. These
modifications do not involve substantial changes in train geometry but relate to
the use of: glass- or quartz probe liners; special filter media; or selective
reagents in the M5 impingers. For example, use of a glass lined probe, glass
fiber filter and 0.1 N nitric acid in the impingers of a standard M5 train
provides good collection efficiency for most trace metals. To quantify heavy
metals in the stack emissions, the probe catch, filter and/or impinger solutions
are digested as described in Section IV G and analyzed as described in Section V
D.
For sampling of semivolatile organics in stack emissions, a more
significant modification of the standard M5 train is required. The Modified
Method 5 (MM5) train (SW-846 method 0010), shown in Figure 6, incorporates a
condenser/cooler section and a module filled with a solid adsorbent between the
exit of the filter and the entrance to the first impinger. The adsorbent
(' ~j 8 ^
recommended is Amberlite XAD-2, which has been shown ' to give good
collection efficiency for vapor phase organic compounds with boiling points
above about 100°C. This category, "semivolatile" organics, includes many
species that are of potential interest for risk assessment (Table 1), including
chlorobenzenes, chlorophenols, polycyclic aromatic hydrocarbons, and chlorinated
21
-------
TEMPERATURE SENSOR
IMPINGER TRAIN OPTIONAL, MAY BE REPLACED
BY AN EQUIVALENT CONDENSER
CHECK
VALVE
VACUUM
LINE
THERMOMETER
FILTER HOLDER
REVERSE-TYPE
PITOTTUBE
PITOT MANOMETER
ORIFICE
THERMOMETERS
DRY CAS METER
AIR-TIGHT
PUMP
FIGURE 5 SCHEMATIC OF STANDARD EPA METHOD 5 TRAIN.
22
-------
Filter Holder
Stack Wall
Thermocouple |J probe
"S" Type
Piwt FT _—-y
w
Pilot
Ma4»o meter
^1
X!
Recirculation Pump
Water Jacketed Condenser
Thermocouple
Sorbent Trap
Thermometer
Check Valve
r
ii
f
^fi~
a
* L
\
-J *
»
«
•**• In.
•!i-
Water
Knockout
Thermometers
Orifice
I mpinger
By-Pass Valve
Dry Gas Meter Air-Tight
Pump
Vacuum Line
FIGURE 6 MM5 TRAIN SCHEMATIC DIAGRAM
-------
dibenzodioxins/furans. The MM5 train is recommended for sampling of
dioxins/furans in MSW combustion effluents in the joint ASME/EPA Environmental
Standards Workshop draft Protocol. (See Appendix B.) The MM5 approach has
also been used by other agencies involved in sampling for dioxins/furans,
including the New York State Department of Environmental Conservation (9) and
Environment Canada (10). There are some differences in configuration between
the MM5 train designs currently in use; these may produce somewhat different
distribution of collected pollutants across the train components (i.e.,
different fractional collection on filter vs. sorbent vs. condensate). However,
all contain the same basic components and should provide comparable overall
collection efficiencies.
The MM5 train, like the M5 train, is used to sample isokinetically. Also,
as with the MS, a variety of impinger reagents can be used for selective
collection of species such as trace metals (Table 2).
The Source Assessment Sampling System (SASS) (SW-846 method 0020) is an
alternative to the MM5 train. The SASS, shown schematically in Figure 7, is
essentially a fivefold scale-up of the MM5 system. Use of SASS is recommended
when calculations indicate that the sampling flow rate of the M5/MM5 train
(0.75-1.0 cu. ft. per min.) would not collect a sufficient quantity of pollutant
in a reasonable time period to meet data quality objectives for detection
limits. Note that the design criteria for the SASS train cyclones are based on
a constant sampling rate, not on a variable rate as used in true isokinetic
sampling. The SASS may therefore be most suitable for sampling semi-volatile
organics and trace metals that are present in the stack as vapor phase
materials. The variation from isokineticity may introduce errors when the SASS
is used to collect particulate material; however, the variations and any
resultant errors are generally small compared to other sources of variance in an
MSW combustor sampling and analysis program.
The operation of both the MM5 and the SASS train is described in reference
11. Note that each of these stack sampling trains generates multiple components
for subsequent sample preparation and analysis (Sections IV and V). Note also
that, while the M5-type approach can be modified to meet a number of sampling
24
-------
ISOLATION
BALL VALVE
FILTER
GAS COOLM
!\J
Ul
IMC/COO ll«
ritACC CICMENT
coiiEcron
*^
MY GAS MJ!£ It/Oil IF ICf METER
CENTRALIZED TIMPtltATURE
AND mSSURI «ADOUT
Source:
CONTROL MODULI
TWO Itth3/nwn VACUUM PUMPS
FIGURE 7 SASS SCHEMATIC DIAGRAM
IERL-RTP Procedures Manual: Level 1 Environmental Assessment
(Second Edition), El'A-600/7-78-201
-------
objectives (particulate material, trace metals, semi-volatile organics, acid
gases), it is generally recommended that one not attempt to meet more than one
(or two) of these goals with a single stack sample. In theory, for example, one
could run a MM5 train, dry the probe wash and filter to constant weight for
weighing of particulate material, then split the particulate catch--digesting
one-half for trace metal determination and extracting the other half for
semi-volatile organic analysis. In practice, such an approach is likely to
result in sample losses and in unnecessarily high limits of detection for
particular pollutants.
(12)
The Volatile Organic Sampling Train (VOST) was developed^ ' to sample
organic vapors that are too volatile for efficient collection in the MM5 or
SASS. This includes most organics with boiling points of about 100 C or lower.
This includes a number of species that may be of interest such as carbon
tetrachloride, benzene and vinyl chloride. A schematic of the VOST is shown in
Figure 8. As shown, the VOST system includes a probe, glass wool roughing
filter, a gas cooling/condensing section, and two solid adsorbent tubes in
®
series. The first tube contains 1.6g of Tenax-GC sorbent and the second
contains l.Og of Tenax backed up by l.Og of charcoal. The VOST is used to
collect a series of 20L stack gas samples at a flow rate of 1 LPM through 5
successive pairs of fresh traps. After sampling, the tubes are sealed and
returned to the laboratory for thermal desorption and analysis of volatiles by
GC/MS (Section V). A protocol for use of VOST has been published by EPA ' and
is also available in SW-846 as method 0030(1).
(12)
The VOST system has been extensively validated in the laboratory and
(14)
applied successfully in the field . In addition, EPA has sponsored the
development and testing of a series of VOST audit cylinders, containing known
mixtures of volatile organics, that are available to regulatory agencies as
checks on overall VOST sampling and analysis performance by users of the system
C. SAMPLING METHODS FOR FLUE GAS
The methods described in Section B, above, are also applicable to sampling
of flue gases upstream of air pollution control devices (APCDs). However, flue
26
-------
Glass Wool
Paniculate
Filter
STACK
(or test System)
Heated Probe
Isolation Valves
Carbon Filter
ice water
Thermocouple
—Sorbent
Cartridge
•ft
Condensate
Trap Impinger
Condenser
Backup
Sorbent
Cartridge
Vacuum
Indicator
Silica Gel
Exhaust
Dry Gas
Meter
FIGURE 8 SCHEMATIC OF VOLATILE ORGANIC SAMPLING TRAIN
(VOST)
-------
gas is typically hotter, wetter, dirtier (higher particulate loadings, higher
levels of condensable organics) and more corrosive than stack gas. Thus
modifications are frequently required to adapt stack gas methods to flue gas
sampling. For example:
• When the flue gas temperature is in excess of about 500 C, a
water-cooled jacket must be placed around the outside of the heated
probe.
• The flow conditions wit. the flue and difficulty in accessing
sampling points may preclude isokinetic sampling and/or traversing of
the duct. A preliminary velocity traverse will usually allow
selection of a fixed sampling point of "average" velocity that is away
from the walls of the flue. The probe can then be located at this
position and the sampling rate adjusted to be as close to isokinetic
as practical.
• High loadings of particulate material and/or condensable organics may
cause frequent interruptions of sampling for replacement of filters to
avoid excessive pressure drops across the train. Use of a roughing
filter (in-flue) or insertion of a cyclone component upstream of the
M5-type filter may be necessary to allow reasonably convenient
continuity of sampling.
• Glass, quartz, or Teflon liners may be required to protect all
stainless steel surfaces from corrosion.
The principal reason for sampling the flue upstream of the APCD is to allow
assessment of control device removal efficiency. An alternative approach is to
sample and analyze the material collected in the device, rather than the flue
gas challenge concentration, and compare this to the quantity emitted in the
stack gas. The efficiency can then be estimated as:
Q
. collected x 100
" 0 + Q
collected emitted
28
-------
where 0 ,, , - concentration in fly ash x rate of fly ash collection
xcollected
in APCD
0 - concentration in stack gas x volume flow rate of stack
emitted °
gas
This "mass balance" is probably comparable in uncertainty to that based on
direct flue gas measurements for "major" pollutants in MSW combustion, such as
particulate material or acid gases. It cannot be recommended for trace level
pollutants such as individual metals or organics,
D. SAMPLING METHODS FOR SOLID AND LIQUID EFFLUENTS
The methods specified in SW-846 and in "Sampling and Analysis for
Hazardous Waste Combustion (First Edition)" are generally directly
applicable to MSW combustor solid and liquid effluents. Table 4 summarizes the
relevant methods. In addition, EPA is currently in the process of developing
specific recommendations for sampling MSW combustor ash.
For both liquid and solid effluents, the sampling strategy will depend on
whether the stream is generated continuously (as in once-through scrubber water)
or in a batch process (as in a fabric filter). In the former case, composite
samples are generated by collecting equal-sized aliquots at regular time
intervals over the course of the test run (e.g., from a tap on a discharge line
(liquid) or from a conveyor (solid).) In the latter case, composite samples are
prepared from subsamples from statistically selected points that represent the
horizontal (area) and vertical (depth) extent of the batch.
Particular problems may be encountered in sampling MSW combustor bottom
ash, which may include bulky items such as metal containers. This issue should
be specifically addressed in the samp\ing and analysis plan for each test. It
must be recognized that any decision to "sample around" such bulky objects could
compromise the overall validity of the data collected, unless it could be
established that they are negligible sources of the compounds to be determined.
29
-------
TABLE 4
SAMPLING METHODS FOR SOLID AND LIQUID EFFLUENTS
Stream
Liquids in pipelines.
Liquids in sumps, tanks,
or open drain.
Wet or dry ash on
conveyors or in bins.
Dry fine ash on conveyors,
in bins or piles.
Principle
Attach TFE line to tap. Flush
container with fresh sample, then
fill.
Glass or TFE beaker on rod.
Stainless steel trowel or lab
scoop. Obtain random sample below
surface level.
Tube within a tube, rotated to
align slots for sampling.
Method
Tap
Dipper
Scoop
Thief
Wet ash in bins or
CO
o piles.
Section of tube cut in half
lengthwise. Insert into waste and
withdraw.
Trier
Reference 1
-------
E. SAMPLING METHODS FOR WASTE FEED
This stream is grossly inhomogeneous. None of the sampling techniques
promulgated for hazardous waste sampling CSW-846) is directly applicable to
MSW as-received at a mass-burn combustion facility. (Some refuse-derived-fuel
(RDF) processes may produce a waste stream that is sufficiently homogeneous and
finely divided to be amenable to scoop or trier/thief sampling.)
Researchers have chosen one of two approaches towards sampling MSW:
stratified random sampling at the source (socio-economic demography) or by
subjectively-modified random sampling at the repository, be it an incinerator or
/ 1 -I TO 1 Q\
a landfill ' ' . For purposes of evaluating the performance of an MSW
combustor, or of understanding the relationship between emissions and waste feed
characteristics, the latter is the preferred approach.
Procedures used for sampling and testing of refuse, and the resulting
variability in measurements of properties of MSW, have been summarized by
Hasselriis (20). Based on this review, it is recommended that 3 to 10 samples
of MSW should be collected over at least a 2 week sampling period. The smallest
sample should be 1 "unit" of MSW (i.e., one trash bag or barrel of domestic
waste at the source; one truck hopper load or crane bucket load at an MSW
combustor plant. Gone and quarter procedures can be applied to reduce the unit
to a manageable sample size (80-130 kg); this sample can then be shredded to
achieve a reasonably homogeneous material for analysis. As an example, the MSW
sample processing protocol reported by Bell is included in Appendix A. If
any element of subjective sampling is imposed (e.g., exclusion of bulky items or
hospital wastes) this must, at a minimum, be explicitly noted and an estimate of
the quantity of rejected material be provided.
31
-------
The EPA, Department of Energy(DOE), and American Society for Testing of
Materials (ASTM) have been collaborating in the development of protocols for RDF
sampling, including sampling accuracy, bias, and reproducibility estimates. A
draft procedure has been approved by an ASTM subcommittee and is awaiting ballot
approval by the main E-38 Committee on Resource Recovery. This protocol should
be a useful resource for designing waste sampling plans for MSW combustors in
general.
32
-------
IV. SAMPLE PREPARATION PROCEDURES
A. OVERVIEW
The sample preparation procedures for use on MSW combustor samples involve
a number of steps. In the field, the collected samples must be transferred to
appropriate, clean containers (generally glass or TFE for organic analysis /.nd
high-density linear polyethylene f,/ inorganic analysis) and appropriately
preserved and stored. In the laboratory, the sample must be converted (via
digestion, extraction, etc.) into a matrix which is compatible with the final
analysis methods needed. Table 5-presents a summary of the sample preparation
procedures that will commonly be required for MSW combustor samples. This table
indicates how samples collected by procedures in Section III are converted to
forms amenable to analysis by procedures in Section V.
In some cases (e.g., analysis of chloride in caustic impinger solutions)
the sample preparation may be minimal (e.g., diluting an aliquot to a known
volume). In other cases (e.g., analysis of dioxins/furans in an MM5 stack gas
sample) the procedures may be complex, requiring extraction of multiple
components, concentration and clean-up of extracts.
The use of surrogate or standard addition methods is strongly recommended
as a QC check on any losses in the sample preparation steps. For this purpose,
the additions should be made to the sample prior to any sample preparation.
B. REPRESENTATIVE ALIQUOT FROM FIELD SAMPLES
Combination and preparation of representative aliquots of collected samples
is appropriate for all MSW combustor solid and liquid effluent samples. The
collected sample is homogenized prior to withdrawal of aliquots for analysis.
Individual aliquots are composited to form a single sample (or replicate QC
samples) for subsequent preparation and analysis procedures. Table 6 summarizes
these procedures.
33
-------
u>
•fc-
TABLE 5
SUMMARY OF SAMPLE PREPARATION METHODS
Cross References
HS¥
Combustor
Stream
Stack Gas
Sample
Type
M5, MM5 or
SASS
For
Analysis
Of
•
Preparation
Procedure
Sampling grep Analysis
- probe wash
- filter
- probe wash
- filter
- impinger
solutions
- probe wash
- filter
- sorbent
module
- condensate
VOST
- sorbent
cartridges
- condensate
Particulate
Metals
Semivolatile
organics
Semivolatile
organics
Volatile
organics
Volatile
organics
Dry to constant weight III B
Standard addition to III B
split samples. Digest
in acidic oxidizing
medium
Add surrogate, Soxhlet III B
extract with CH_Cl
Concentrate. Clean-up
as necessary
Add surrogate III B
Liquid-liquid
extract at pH 2 and
pH 11 with CH C12,
Concentrate. Clean-up
as necessary
Spike with internal III B
standard. Thermally
desorb onto analytical
trap. Desorb this trap
into GC/MS.
Spike with internal III B
standard. Purge onto
analytical trap. Desorb
into GC/MS.
IV G
IV C-F
VD
IV C-F
VD
VD
VD
-------
Liquid
Effluents
Ul
TABLE 5
SUMMARY OF SAMPLE PREPARATION METHODS (cont.)
Cross References
MSW
Combustor
Stream
Flue Gas
Bottom Ash
and
Fly Ash
Sample
Type
M5, MM5, SASS
VOST
Composite
Grab
For
Analysis
Of
(same as for
Metals
Preparation
Procedure Sampling
stack gas) III C
Standard addition to III D
split samples. Digest
in acidic medium in
Prep Analysis
IV G VD
Composite
Grab
Semi-volatile
organics
Metals
Parr bomb.
Add surrogate. Soxhlet III D
extract with CH^Cl,
Concentrate.
as necessary,
Clean-up
Volatile
Organics
Semivolatile
Organics
Standard addition to III D
split samples. Digest
in acidic, oxidizing
medium.
Spike with internal III D
standard. Purge onto
analytical trap. Desorb
into GC/MS.
Add surrogate. Liquid III D
liquid extract at pH 2
and pH 11 with CH.Cl
Concentrate. Clean-up as
necessary.
IV C-F
IV G
IV G
IV C-F
VD
VD
VD
VD
-------
TABLE 5
SUMMARY OF SAMPLE PREPARATION METHODS (cont.)
Cross References
MSW
Combustor
Stream
Waste
Feed
Sample
Type
Composite
Grab
For
Analysis
Of
Preparation
Prpcedure
Grind or mill to
reduce particle size.
Sampling
III E
£rejj Analysis
Metals
Semivolatlle
Organics
**
Volatile
Organics
Take subsaraples.
Same as for ash
samples.
Spike with Internal
standard. Dilute in
reagent water or poly-
ethylene glycol in purge
cell. Purge, trap and
desorb into GC/MS,
IV G
IV C-F
VD
VD
VD
OJ
Gross references are to sections of this document.
**
Reference: Miller, N.G., R.W. James and W.R. Did n, "Evaulated Methodology for the Analysis
of Residual Waste," Report prepared under EPA Contract No. 68-02-1685 (December 1980).
Also see SW-846 method 8240.
-------
TABLE 6
SUMMARY OF PROCEDURES FOR COMPOSITING SAMPLES
Physical
Form
Aqueous
Homogenizing
Shake well and pour
aliquot
Compositing
Combine aliquots in
clean container and
shake to mix well.
Minimum Quantity
of Composited Sample
1 L (semi-volatile
organics)
1 L (metals)
NOTE: For volatilea analysis, composite just prior to analysis
by adding aliquota from multiple VOA bottles to purge
cell.
5 mL (volatile
organics)
Sludges/
Slurries
Solids
Stir or shake well; use
dipper to take > 3
portions.
Grind, if necessary, to
reduce particle size (20
mesh screen) using agate
or alumina equipment;
riffle through steel or
aluminum riffler.
Combine aliquots in
clean container and
stir or shake to
mix.
Combine aliquots,
cone-blend three
times, roll-blend,
cone and quarter.
100 mL (semi-vol
organics)
100 g (metals)
50 g (organics)
100 g (metals)
-------
Samples of stack (flue) gas collected with an extractive sampling train
(M5, MM5, SASS or VOST) already represent time-averaged sample collections. In
effect, the sampling approach has composited the gas on a time-weighted basis.
It is generally inappropriate to further composite such samples. However, in
some cases where ultra-low levels of detection are required (e.g., dioxin/furan
analysis), it may be necessary to pool the entire extracts from multiple
sampling runs.
C. RECOVERY METHODS
The specific sampling methods listed in Table 2 contain explicit procedures
for the physical recovery of samples from the train. However, they do not
necessarily specify procedures for monitoring the chemical recovery achieved in
the sample preparation process. There are two basic approaches that can be used
for this purpose: (1) addition to each sample of surrogate compounds, which are
chemically similar to the species of interest but not expected to be present in
the sample (e.g., for GC/MS analyses, stable isotope-labelled analogs of the
target compounds); or (2) standard addition (spiking) of the target species
themselves to selected split samples.
The spiking levels used in each instance are selected after consideration
of the target detection level for each analyte and the expected concentration of
the species in the sample. For MSW incinerator effluent samples, it is
generally desirable to select spiking levels that correspond to 2 to 10 times
the target detection limit or to 2 to 4 times the critical decision limit. The
level chosen should be explicitly stated in the QAPP for each test program.
For example, assume that the critical decision limit for a semi-volatile organic
pollutant (e.g., 2, 3, 7, 8-teterachlorodibenzodioxin, TCDD) is 1 ng/m in stack
gas, and a 5 m sample of stack gas is to be collected using the MM5 train. An
13
appropriate level of surrogate (e.g., Ci2~2> 3' 7> 8-TCDD) to be spiked into
the MM5 train components prior to extraction can be calculated as:
4x1 ng/m x 5 m - 20 ng surrogate
38
-------
Assuming that the organic extract is concentrated to a final volume of 1.0 ml,
and that 5 pL are injected into the GC/MS system, this spiking level would yield
100 pg of surrogate on-column if recovery through the sample preparation steps
were 100%, and 50-pg on column if recovery were only 50%. It must be confirmed
by analysis of calibration solutions that these levels are within the analytical
detection limit of the GC/MS system. Recovery of 60% or higher can be
( 21)
expected if the laboratory procedures are under control.
D. EXTRACTION METHODS
Solvent extraction with methylene chloride is the procedure most broadly
used to prepare samples for organic analysis. In the case of stack sampling
trains, several separate extractions (of probe wash and filter, sorbent trap,
and of condensate) will be required. It is general practice to combine these
extracts prior to analysis so that a single value is obtained for the stack gas
concentration of each species. This approach allows lower detection limits to
be achieved. Further, there is no intrinsic advantage to differentiating
between material collected in the "particulate" (front half) vs "vapor" (back
half) portions of the train, since these catches do not necessarily indicate the
/4 22 23)
particulate/vapor distribution present in the stack ' '
Liquid-liquid extraction, using a manual, separatory funnel method or a
continuous extractor, applies to: (1) spent scrubber water or other waste water
effluent from the MSW combustor and (2) aqueous condensate collected from the
stack gas effluent in the MM5 or SASS trains. The volumes of sample/extracting
solvent and any necessary pH adjustment of the sample should be as specified in
EPA Method 625 if the purpose of data collection is NPDES compliance
determination. In the case of stack gas condensate, these parameters can be
scaled down to accommodate the actual quantity of sample collected.
Soxhlet extraction applies to: (1) solid effluents from the MSW combustor
and (2) probe wash, filter and sorbent components of the MM5 or SASS trains.
Quantities of sample and extraction solvent should be as specified in Method
lamp
(D
P024 b (Sampling and Analysis for Hazardous Waste Combustion) or Method 3540
(SW-846).
39
-------
Some very wet ash samples or sludges may require alternative extraction
procedures (e.g., homogenization, Methods P022 a,b or P024 a,c). Also,
solid or slurry samples that are not suitable for direct introduction to the
purge cell of a purge-and-trap apparatus may require a micro-extraction (e.g.,
Methods P022b, P024c) prior to determination of volatiles.
If the MSW combustor test program includes evaluation of solid residues
vis-a-vis the RCRA hazardous waste characteristics, a separate sample of the
solid material must be extracted by the EP (Method 1310, SW-846) or the new TCLP
(Fed. Reg. Vol. 51, No. 114, June 13, 1986), when promulgated as a final method.
E. DRYING AND CONCENTRATING OF EXTRACTS
Unless an alternative procedure is specified in a particular analytical
procedure, solvent extracts should be passed through a short column of anhydrous
sodium sulfate into a Kuderna-Danish evaporative concentrator apparatus. In
most cases, rapid concentration to a final extract volume of 1-10 mL will
provide adequate detection limits without unacceptable losses of semi-volatile
organic species.
F. SAMPLE CLEAN-UP
For some samples, the level of interfering compounds is sufficiently high
to preclude successful analysis for the species of interest. For such samples,
one or more clean-up steps must be included in the sample preparation procedures
Because of the wide variation in sample matrices and in the physical/chemical
properties of the species that may be sought, no single method or set of methods
can be recommended for MSW combustor samples. This is one of the reasons why
use of surrogate spiking of MSW combustor samples is strongly recommended
(Section IV C). If it can be demonstrated that recovery and detectability of
the surrogate are adequate, then no clean-up steps are necessary. However, if
interferences overload the analytical column or detector and the surrogate is
not detectable, clean-up will be required. This must be established empirically
for each project. The QAPP should specify the criteria for acceptable surrogate
40
-------
recovery/detectability and corrective actions to be taken if the criteria are
not met.
Some analysis methods (e.g., Methods 8010-8250, SW-846( J) specify that
silica gel, Florisil or alumina column clean-up be applied. In some cases three
or more sequential clean-up steps may be required. For example, the ASME
methodology for analysis of dioxins and furans specifies sequential passage
of the concentrated sample extract through 1) a combination column containing
silica gel and acid and base-modified silica gel, 2) a basic alumina column, 3)
a PX21 carbon/celite 545 column and 4) a silica/diol column. Such an extensive
clean-up is usually not necessary unless the critical decision limit is in the
3
ng/mg range. However, using at least one column clean-up step (silica gel,
alumina) may significantly improve detection limits when critical concentrations
3
are in the pg/m range.
G. DIGESTION
The preparation method for all samples requiring metals analysis includes a
digestion step. Its purpose is to convert all of the metal-containing species
into inorganic form.
For most sample types, an acidic, oxidizing medium is specified for
digestion. Solid samples can be digested using HF and HNO. in a Parr bomb.
(24)
Solutions can be digested using HNO. and H«0. . In some instances, repeated
(1)
digestion using HNO, alone may give adequate recovery. For mercury in solid
materials, Method 105 (40 CFR Part 61) calls for aqua regia digestion followed
by potassium permanganate oxidation.
A relatively new development is the use of microwave energy, rather than a
conventional hot plate, for acid digestiors. This reduces the time and acid
(24)
quantity required for complete digestion
41
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V. ANALYSIS PROCEDURES
A. OVERVIEW
The overall strategy for analyzing samples from MSW combustion must reflect
the multiple possible purposes of data collection discussed in Section II A.
When the purpose of the data collection is to determine compliance with a
specific regulation concerning air, water, or solid effluents (or their
disposal) it is essential that the analysis method used be one recognized by the
appropriate agency. These include, but are not necessarily limited to:
EPA NSPS Methods 1-5 40 CFR Part 60
EPA NESHAPS Methods 101-108 40 CFR Part 61
EPA Clean Water Act Methods 40 CFR Part 136
601-612; 624, 625; 1624, 1625;
200.7
EPA RCRA Methods SW-846
7040-7951; 8010-8310
One exception to the above generalization relates to measurement of
criteria pollutants in combustor effluents. The EPA NAAQS methods for criteria
pollutants are ambient air monitoring methods that are suitable for source
monitoring only with modifications (gas conditioning; dilution). However, there
are NSPS methods applicable to direct measurement of criteria pollutants in
combustion sources.
Even when the purpose of data collection is to provide input for more
general environmental assessment, or risk assessment, rather than regulatory
compliance, the above EPA-approved methods are frequently useful. In
particular, the nearly-identical GC/MS-based methods designed for determination
of priority pollutants (624, 625; 1624, 1625) or Hazardous Substance List (HSL)
compounds (RCRA 8240, 8250, 8270) have wide applicability for organic analysis.
42
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The corresponding procedures for metals analysis by atomic absorbtion
spectroscopy (AAS) or inductively coupled plasma spectroscopy (ICP) are also
directly applicable to MSW combustor samples.
For some assessment purposes, official federal EPA methods may be
inappropriate or unavailable. In these cases, methods promulgated by ASTM and
ASME should be used if available. For example, there is at present no official
method for determination of dioxin/furan congeners that applies specifically to
MSW stack emission sample analysis. However, a procedure developed to supuort a
joint ASME-EPA project on MSW comb , -.ion is recommended . In addition,
SW-846 method 8280 may be used for homolog-specific analysis.
Similarly, there are presently no official methods suitable for screening
MSW combustor samples to identify and/or quantify other pollutants that may be
present as a result of incomplete combustion. Research in this area is underway
as well. The selection of appropriate analysis methods for such pollutants must
be established on a case-by-case. Part C of this section provides some
preliminary suggestions.
Potentially useful methods for direct analysis of selected species in MSW
combustor effluents using continuous instrumental monitors will be discussed in
Section VI of the report.
B. PROXIMATE ANALYSIS
"Proximate analysis" is a term used in "Sampling and Analysis for Hazardous
Waste Combustion (First Edition)" to describe procedures for determining the
approximate (gross) composition of hazardous waste. The methods recommended for
that purpose include:
% moisture, solid and ash determination
elemental analysis (%C, N, S, P, F, Cl, Br, I)
total organic carbon
total organic halogen
43
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heating value
viscosity
These methods are applicable to MSW.
C. SCREENING ANALYSIS
As noted above, screening analysis is intended to identify and/or quantify
species chat are present in a sample and are of potential concern with regard Co
effects on health and/or environment but were not specifically pre-selected for
analysis (see Section D, Directed Analysis). There are no official procedures
for screening analysis. In practice, the approach that has most commonly been
used in research and development programs involving waste combustion has been as
follows.
For organic species, perform full-mass range scanning (e.g., 40-500 amu)
under appropriate GC/MS conditions (usually capillary column and El ionization).
In most cases, the GC/MS conditions specified in EPA. methods 624/1624/8240 for
volatiles and in EPA methods 625/1625/8250/8270 for semivolatiles will be
applicable to screening analysis of MSW combustor samples. In addition to
providing data for directed analysis, the results of these analyses can be used
to identify unknown or unexpected compounds by comparison to a library of
reference spectra or by spectral interpretation. A typical criterion for
screening analysis is to attempt to identify the 20 most intense unknown peaks
or those peaks whose intensity exceeds 10% of the internal standard intensity
(whichever is the lesser number of unknowns).
For inorganic species, ICP analysis can be used to screen for about 20-23
metals that are known or suspected to be of environmental concern. Alternacive
approaches sometimes recommended to address a broader range of elements include:
X-ray fluorescence, neutron activation analysis, particle-induced X-ray
emission, and spark source mass spectrometrv. All of these are multielement
methods and require minimal sample preparation. However, the instrumentation
required is expensive and not widely available. Also, the methods are more
44
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amenable to qualitative screening than to quantification unless standards and
samples are carefully matched to eliminate sample matrix effects.
It is probable that screening analysis is more likely to be requested for
MSW combustor air emission samples than for liquid or solid effluents. These
methods can be applied to samples of MSW combustor stack gas collected with the
MM5, SASS or VOST (volatile organics only) after suitable sample preparation
techniques have been applied. They should also apply to liquid or solid
effluent samples after sample preparation.
D. DIRECTED ANALYSIS
As noted in the overview to this Section, analysis methods are available
for most species that are likely to be pre-selected as targets for analysis in
MSW incineration. Table 6 lists suitable analysis methods for organics and
metals that may be of concern. Specific methods for distinguishing between
species such as Cr (VI) and Cr (III), suitable for use with combustion effluent
samples, based on selective extraction of Cr (VI) by an alkaline reagent, are
under development and in the process of validation by EPA's Emission Measurement
(25}
Branch at Research Triangle Park, North Carolinav ' . In addition, SW-846 lists
methods both for Cr(VI) and for total chrome; these methods are potentially
applicable to MSW combustor samples providing that suitable procedures for
solubilization of the chromium are applied.
Note that, for organic analysis, Table 7 lists only the GC/MS alternatives.
Methods that use GC or HPLC with detection principals less specific than MS
(e.g., flame ionization (FID) or electron capture (ECD) detection for GC,
ultraviolet (UV) or refractive index (RI) for HPLC) are less likely to be useful
for MSW combustion samples, because of the variety and quantity of potentially
interfering substances likely to be present.
45
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TABLE 7
ANALYSIS METHODS FOR TRACE ORGANICS AND TRACE METALS,
APPLICABLE TO MSW COMBUSTOR SAMPLES
Species Method Reference
Volatile Organics Packed column GC/MS; full mass range 1, 15
scanning 20-260 amu.
Semivolatile Organics Capillary column GC/MS; full mass range 1, 15
scanning 40-500 amu.
Dioxins/Furans Capillary column GC/MS; selected ion 1, 5
monitoring.
Metals Flame (high levels) or furnace (low 1, 24
levels) AAS.
Inductively coupled plasma spectroscopy 1, 24
(not for mercury, lead, arsenic)
-------
VI. CONTINUOUS .MONITORING METHODS
A. OVERVIEW
Continuous monitoring systems include _in. sjLEu measurements, in which a
sensor is mounted directly in a stack or flue, and extractive methods, in which
a sample of stack or flue gas is pumped through an interface to the measuring
device. In situ monitoring offers the advantage that no alteration in flue gas
composition is introduced by the sy^'-em. Conversely, however, an in situ sensor
must be physically resistant to st, conditions (temperature, moisture,
particulate matter) and be chemically selective (blind to potential
interferents). An extractive approach is amenable to gas sample conditioning to
remove substances that might interfere with the desired measurement or damage
the instrument. It also allows instruments to be placed in a sheltered location
where maintenance and calibration are more convenient. However, this approach
provides opportunity for loss of target species in transfer lines and in
components of the gas conditioning system.
Many continuous monitors are based on rather sophisticated chemical
analysis principles. Manufacturers have aa.de considerable efforts to
"ruggedize" the commercially available systems so that they are capable of
unattended operation for periods of days to weeks and can be
maintained/calibrated by plant operating personnel. Despite these advances, it
is vital that a rigorous QA/QC program be established for continuous monitors to
ensure that misleading data are not recorded and that operating problems are not
overlooked.
B. SAMPLE CONDITIONING
An extractive sampling system interface typically includes the following
components;
* probe
» coarse filter
* transfer lines
47
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• pump
• moisture removal system
• fine filter
The probe must be located at a point in the stack or flue that allows a
representative sample to be withdrawn. A multi-port probe may be useful in this
regard. Depending on stack or flue temperature and corrosivity, materials of
construction may be stainless steel or ceramic. The coarse filter, usually
located in-stack to minimize effects of condensation, is typically sintered
metal or ceramic, depending on temperature. Ceramic is more resistant to high
temperature corrosion effects but also more susceptible to cracking. Plugging of
the probe and/or coarse filter can be a severe problem, especially when - ,;npling
flue gas upstream of particulate control devices. Backflushing the system
regularly with clean carrier gas may help but frequent replacement of the
in-stack filter will probably still be required.
The transfer lines must be constructed of inert materials that are
resistant to corrosion and do not absorb the species to be measured; ceramic
®
(probe) and Teflon are materials of choice for most applications. Stainless
steel would be an alternative if the stack or flue gas is not highly corrosive.
The pump must also be constructed of, or coated with, inert material such as
Teflon . Especially when samples are to be monitored for organics, any
potential contamination of the sample with lubricants must be avoided.
Diaphragm or bellows pumps can meet this constraint.
Moisture removal can be accomplished in several ways: adsorption (e.g.,
silica gel); condensation; dilution to below dew point; membrane permeation
system. Issues that must be addressed in selection of the drier component
include: adequate capacity for water removal given the moisture content of the
stack or flue gas; and minimal coincident losses of target species along with
the water. A condensation approach, for erample, may lead to unacceptable
losses of acid gases such as HC1 and SO .
X
The fine particulate filter is usually located close to the analyzer inlet.
It usually must achieve virtually complete removal of all particles larger than
48
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1 micron. When sampling flue gases, these filters require replacement whenever
the pressure drop across the filter approaches the limit of pumping capacity.
C. MONITORS FOR INORGANICS
The following is based on information provided by instrument suppliers and
by references 26 and 27.
Continuous temperature measurements in combustor flue or stack gases are
generally accomplished by using type J, K, or RT thermocouples. The
thermocouples must be shielded from radiation and protected against mechanical
damage and corrosion by shielding inside a ceramic or metal protection tube or
in a thermowell.
Continuous monitoring of particulate material is generally accomplished
using an in situ opacity meter. Typically, these devices measure changes in
optical density, OD (percent transmittance), due to scattering and/or adsorption
of light by particles in the stock. The OD reading obtained depends not only on
the mass loading of particulates that are present, but also on their size
distribution, the particle shape, particle composition, the system's
temperature, the presence or absence of water droplets and the configuration of
the stack. The lack of measurement specificity may render opacity monitors less
reliable at MSW combustors than at other stationary sources, as waste feeds at
MSW locations are highly variable, probably causing emission levels and
compositions to vary over time as well. Also, commercially available opacity
meters for stack monitoring may be uncertain by a factor of two or more at
particulate loadings below 0.03 gr/SCF.
Extractive sampling, rather than in situ monitoring, is most commonly used
for inorganic gases, although in situ monitors are available for CO, C02, 02,
NO , and SO . Typically, the detection of pollutant species of concern is
X X
accomplished using one of the detection principles identified in the descriptive
information presented below. There is relatively little history of application
of these instruments to MSW combuster stack gas and, especially, flue gas.
49
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for continuous monitoring at other types of
detection principle used by continuous analyzers is
Amenable for use in the determination of CO,
>y NDIR is based on the principle that each of
lers, will absorb specific signature wavelengths of
rating matched beams at the correct signature
h a clean "reference" cell while the other is
r. sample gas, and determining the difference in
beams, it becomes possible to measure the amount
Les that is present.
icomplished using devices such as a. thermistor, a
device.
f NDIR based instrumentation is the fact that it
i that the technology is applicable to a wide
Vlso, instruments are relatively rugged and
lave been in use in field monitoring situations
ire associated with this detection principle are
iecies that will absorb similar signature
nd the fact that optical systems needed to
he generated infrared light may degrade due to
No
NDUV) analyzers employ much the same philosophy
as uo cne analyzers based on NDIR absorbtion, only in this instance, the light
source emits in the ultraviolet or visible regions of the spectrum and a
reference cell is generally not used. Typically, a reference wavelength in a
50
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region where the pollutant species of interest has minimal absorptive capacity
is generated and quantitation is completed by differential analysts.
An important advantage of the NDUV analyzers is that water vapor is not an
interference, as water does not absorb light in the ultraviolet region of the
spectrum. As is the case with most extractive monitoring techniques, however,
particulates which will absorb or scatter generated light must be removed from
the sampled gas stream.
Poljirographic Analyzers
Numerous pollutant species of potential interest at MSW combustors may be
measured continuously using polarographic analyzers. Polarographic analyzers
operate on the principle of selective diffusion and chemical reaction of a
pollutant species of interest which induces a current flow that is measured
electronically. The sensing device intrinsic to the operation of all
polarographic analyzers is commonly called the electrochemical transducer.
In operation, the pollutant species of interest enters the transducer
through a selective, semi-permeable membrane. Once in the transducer, the
pollutant is oxidized or reduced by reaction with an electrolyte solution which
induces a current flow. The induced current flow is proportional to the
concentration of the pollutant species in the gas stream. The selectivity of
electochemical transducers is dependent upon the selection of membrane
materials, electrolyte, and sensing electrode chemistry or composition.
The polarographic analyzers offer several advantages over other analyzers,
including multi-pollutant capability by switching transducer, fast response and
simplicity of operation. Principle disadvantages of this technique are that
transducers must be replaced or rejuvenated periodically, and the instrument
must be frequently calibrated because the response of the transducer does
deteriorate as the electrolyte solution is consumed.
51
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Electrocatalytic Analyzers
Electrocatalytic analyzers are currently available for oxygen
determination. This type of instrumental determination is based on the
principle that current flow is induced when two solutions containing similar
materials at differing concentrations are brought into contact. Thus, by having
two cells, one a reference and the other the unknown, separated by a porous
zirconium oxide barrier (acting as both an electrolyte and catalyst), an
electron current flow can be promo" d, measured, and related directly to o>vgen
content.
Paramagnetic Oxvgen Analyzers
Oxygen content may also be determined using a paramagnetic analyzer.
Detection in a paramagnetic analyzer utilizes the fact that oxygen molecules
(and the molecules of a few other compounds) are attracted by a magnetic field.
Two different philosophies of paramagnetic detection are commonly used in
instrumentation. One, called thermomagnetic or magnetic wind instruments are
based on the principle that the magnetic attraction of oxygen decreases as
temperature increases. The second, called magneto-dynamac, uses the
paramagnetic attraction of oxygen to swing a specialty torsion balance.
Chemiluminescence
Certain inorganic pollutants, most notably nitrous oxide and ozone, may
also be detected using analyzers based on chemiluminescence. Within this type
of instrumentation, the pollutant species of interest is mixed with a second
reactant to generate light. Ideally, the generated spectrum of light produced
is specific only to the pollutant of interest, but more commonly, optical means
are used to isolate and quantitate the intensity of specific wavelength. By
measuring the intensity of the generated light, a direct estimate of the
concentration of pollutant species present in the gas sample may be obtained.
Information of currently available instrumentation for inorganic pollutant
species in MSW combuster exhausts are presented in Tables 8 through 14.
52
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Ol
GJ
TABLE 8
Continuous Analyzers for Carbon Monoxide
Detection
Principle
Nondispersive
Infrared
Polarographic
(Electrochemical)
Ranges
|0-50 PPM
|0-100 PPM
|0- 200 PPM
| 0-1000 PPM
JO- 5000 PPM
|0-1 %
|0-5 %
1
1
1
1
|0-50 PPM
| 0-100 PPM
|0-250 PPM
JO- 500 PPM
JO- 999 PPM
|0-4 %
1
1
1
1
1
Interferences Comments
| Water Vapor and
| Particulates ; other
(species with similar
| infrared absorbance
| characteristics
1
1
1
1
1
1
(Unsaturated Hydro -
| carbons and ammonia
1
1
1
1
1
1
1
1
1
Examples
In-situ or remote; |Anarad, Inc.
Water Vapor and |Dynatron
Particulates should (Horiba
be removed; corro- | Infrared Ind.
sive gases may etch |Rosemont (Beckman)
optics (Servomex
Siemens
Requires sample
conditioning to
remove particulate
and reduce tempera-
ture
Energetics Science
InterScan
Neotronics
Sensidyne
-------
TABLE 9
Detection
Principle
UI
Continuous Analyzers for Carbon Dioxide
Ranges
Interferences
Comments
Examples
|Nondispersive |0-10 PPM
Infrared | 0-100 PPM
j 0-500 PPM
(0-2500
|0-5000 PPM
|0-0.5 %
|0-2.5 %
|0-5 %
|0-20 %
|0-100 %
1
Polarographic 0-50 PPM
(Electrochemical) | 0-100 PPM
JO-250 PPM
|0-500 PPM
| 0-999 PPM
0-4 %
.
Water Vapor and | In- situ or remote;
Particulates; other | Water Vapor and
species with similar | Particulates should
infrared absorbance |be removed; corro-
characteristics |sive gases may etch
| optics
1
1
1
1
1
Unsaturated Hydro- (Requires sample
carbons and ammonia | conditioning to
(remove particulate
| and reduce tempera-
( ture
1
1
1
1
1
1
Anarad, Inc.
Dynatron
Horiba
Infrared Ind.
Rosemont (Beckman)
Servomex
Siemens
Syconex Corp.
Sensidyne
-------
TABLE 10
Continuous Analyzers for Oxygen
Detection
Principle
Ranges
Interferences
Comments
Examples
|Polarographic
(Electrochemical)
|0-5 %
(0-10 %
|0-25 %
|0-35 %
0-100 %
|Gas must be cooled [Horiba
|and particulate re- |MSA
|moved |Neutronics
Servomex
Electrocatalytic
0-10 %
0-22 %
(Good for high tern- |Anarad, Inc.
(perature applicationjDynatron
|Lynn Products
I MSA
|Servomex
jWestinghouse
Paramagnetic
|0-5 %
(0-2.5
|0-10 %
(0-25 %
|0-50 %
|0-100
I
(Horiba
(Rosemont (Beckman)
|Siemens
I
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TABLE 11
Continuous Analyzers for Sulfur Dioxide
Detection
Principle
Ranges
Interferences
Comments
Examples
|Nondispersive jO-500 PPM (Water Vapor and |In-situ or remote; |Anarad, Inc.
[Infrared JO- 2000 PPM
j | 0-10000 PPM
1 |0-1 %
|0-5 %
| |0-10 %
i |0-30 %
(0-100 %
1 1
1 1
Nondispersive |0-50 PPM
(Ultraviolet j 0-100 PPM
(0-500 PPM
|0-1000 PPM
| 0-5000 PPM
1
1
1
1
I
1
Particulates ; other (Water Vapor and (Dynatron
species with similar) Particulates should
infrared absorbance (be removed; corro-
characteristics
sive gases may etch
(optics; Generally
(selected for percent
(applications
Polarographic (0-5 PPM (Methyl and Ethyl
(Electrochemical) (0-10 PPM (Mercaptans, Hydrogen
(0-50 PPM
(0-100 PPM
1
1
1
I
1
1
1
Sulfide, Ammonia
..
Infrared Ind.
Rosemont (Beckaan)
S iemens
Syconex Corp .
Anarad , Inc .
Teco
InterScan
-------
TABLE 12
Continuous Analyzers for Nitrogen Oxides
Detection
Principle
Ranges
Interferences
Comments
Examples
|Nondispers ive
Infrared
(for NO only)
0-500 PPM
0-2000 PPM
0-10000 PPM
0-2 %
0-10 %
(Water Vapor and [Water Vapor and (Horiba
Particulates; other (Particulates should (Rosemont (Beckman)
species with similar|be removed; corro- (Siemens
infrared absorbance |sive gases may etch (Syconex Corp.
characteristics (optics
|Nondispers ive
(Ultraviolet
(for N02 only)
0-50 PPM
Anarad Inc
Po 1arographic
(Electrochemical)
(for NO only)
0-25 PPM
0-50 PPM
0-250 PPM
(Methyl Mercaptan,
(Ammonia, Nitrogen
Dioxide, Sulfur
Dioxide
(Requires sample
(conditioning to
remove particulate
and reduce tempera-
ture
Energetics Science
InterScan
Chemilumineseent
0-2.5 PPM
0-10 PPM
0-25 PPM
0-100 PPM
0-1000 PPM
0-2500 PPM
0-10000 PPM
Possible Ammonia,
Carbon Dioxide, and
Water
Need to dry and
remove particulates
from sample
Monitor Labs
Rosemont (Beckman)
Thermo Electron
-------
TABLE 13
Continuous Analyzers for Hydrochloric Acid
Detection
Principle
Ranges
Interferences
Comments
Examples
|Nondispersive
Infrared
Ul
00
(Water Vapor and |In-situ or remote; (Flakt
(Particulates; other (Water Vapor and |Syconex Corp
(species with similar|Particulates should (Teco
infrared absorbance |be removed; corro-
characteristics (sive gases may etch
(optics
Polarographic
(Electrochemical)
(0-5 PPM Chlorine gas, Methyl(Requires sample
|0-10 PPM and Ethyl mercaptan,(conditioning to
jO-20 PPM |Hydrogen Sulfide, (remove particulate
(0-50 PPM (Ammonia, Nitric Ox- (and reduce tempera-
j0-200 PPM |ide, Hydrogen Cyan- ture
| jide, and Sulfur Di-
| (oxide
I I
I I
InterScan
-------
TABLE 14
Continuous Analyzers for Hydrogen Cyanide
Detection
Principle
Ranges
Interferences
Comments
Examples
Polarographic
(Electrochemical)
|0-5 PPM
(0-10 PPM
|0-20 PPM
JO-50 PPM
(Chlorine gas, Methyl(Requires sample (InterScan
(and Ethyl mercaptan,(conditioning to (
(Hydrogen Sulfide,
(Ammonia, Nitric Ox-
(ide, Hydrochloric
(acid, and Sulfur Di-
j oxide
I
remove particulate
and reduce tempera-
ture
-------
D. MONITORS FOR ORGANICS
Total hydrocarbons (or total non-methane hydrocarbons) at ppm to percent
levels in stack gases can be monitored continuously with a flame ionization
detector (FID) or infrared (IR) detector. These detectors are relatively rugged
and are quite sensitive to hydrocarbons. The response factor is generally lower
for organics that incorporate functional groups such as haxides, hydroxyl,
carbonyl, carboxylate.
The photoionization detector (PID) is applicable to many of these organic
categories, but experience with this detector as a continuous monitor is more
limited. There is some evidence that maintenance is more of an issue with PID
than with FID or IR instruments.
The electron capture detector (ECD), which has high sensitivity and
selectivity for halogenated organics under laboratory conditions, is not rugged
enough for routine continuous monitoring in the field. Also, because these
detectors contain radioactive materials, NRG permitting regulations govern their
installation and use. The Hall detector, also specific for halogenated species,
has been used at hazardous waste incineration sites, but with difficulty.
Catalytic combustion (hot wire) and thermal conductivity detectors are also
used for continuous monitoring of organics. However, most commercially
available instruments based on these principles are generally designed for
percent level concentrations corresponding to explosive limits of combustible
gases and vapors. A few low-level instruments suitable for MSW combustion
monitoring are available, however,
Monitoring of specific organic compounds, rather than total organics,
requires that chromatographic separation be accomplished prior to detection,
Instrumental monitors that interface a gas chromatograph to an FID or PID are
commercially available. These operate in a semi-continuous basis, since the
.chromatographic separation imposes a cycle time of (typically) 5-30 minutes
between measurements.. The GC/FID or GC/PID analyzers are vulnerable to false
60
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positive interferences because the retention time is an imperfect means of
compound identification.
Instruments based on more selective detection principles (e.g., GC/MS or
GC/FTIR) are beyond the present state-of-the-art for stack monitoring, except in
research installations. Instruments using these detectors may be sufficiently
expensive to install and demanding to operate that they are not suitable for
routine continuous monitoring. Most require, for example, more stringent
control of temperature, humidity and power supply than is likely to be practical
at -.n operating MSW plant.
E. INDICATOR OR SURROGATE MONITORING
A conceptual ideal for continuous monitoring of MSW combustors would be a
inexpensive, rugged, and simple instrument that provides continuous measurement
of a surrogate parameter indicative of total system performance. Identification
of a suitable surrogate parameter, which can be reliably correlated with
emissions of any and all pollutants of potential concern, is one of the
objectives of on-going research in MSW combustion technology. At the present
time, the carbon monoxide level in the air emissions is generally regarded as
the best available surrogate for chemically-based monitoring of overall
combustion efficiency. Monitoring of combustion temperature is also relied on
as an indicator that the process is in control. Methods for monitoring these
indicator parameters are discussed in Section VI C.
F. SPECIAL QA/QC CONSIDERATIONS
All of the general provisions that will be discussed in Section VII apply
to continuous monitoring. A few special considerations are worth noting,
however.
First, calibration with zero and span gases should be performed on the
system as a whole, not just on the analyzer/detector itself. This may, however,
be literally impossible for in situ monitors; generating a stack or flue full of
calibration gas of known composition is not a realistic approach. In the case
61
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of extractive monitoring systems, provision should be made to allow introduction
of calibration gas at, or just behind, the probe. This approach to "total
system" calibration has been incorporated into all of the federally referenced
continuous monitoring methodologies that are currently applicable to stationary
sources.
The EPA has also established guidelines for instrumentation that is used to
continuously monitor sulfur dioxide, nitrogen oxides, carbon dioxide, oxygen,
and carbon monoxide emissions from stationary sources. These guidelines fall
into two categories including both strumental design criteria and performance
specifications.
Instrumental design criteria establish minimum acceptable levels for items
such as instrumental response time, interference rejection ratios and ranges.
Performance specifications are established to assure that the developed data is
accurate and precise. Specifications for calibration drift and the relative
accuracy of calibration, as well as requirements for duration of unattended
operation are established. Specific criteria applicable to monitors used to
measure CO, C02, 02, NO , and SO are provided in Title 40 Code of Federal
X &
Regulations, Part 60.13 and Appendix A and B.
Second, QA/QC procedures for continuous monitoring methods must take into
account the fact that operating personnel may have had minimal training and
experience with chemical measurements and analytical instrumentation. The
procedures must, therefore, place minimum reliance on operator judgment and be
as explicit and simple as possible concerning QC criteria and corrective
actions.
Third, the question of data reduction and data maintenance for continuous
monitor output deserves special consideration. A continuous monitor, in one
sense, generates an infinite numbe" of data points on pollutant concentration
vs. time. It must be determined in advance whether daily, weekly, monthly, etc.
data are to be archived and/or reported. Are running averages desired?
Commercially available data loggers are able to conduct these functions once
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decisions are made with respect to these parameters. How should/must short-term
excursions from average values be recorded/reported?
G. POTENTIAL FOR PROCESS CONTROL
The acquisition of continuous monitoring data affords opportunities for
process control, either by operator intervention or by use of automatic feedback
loops. In current MSW combustion practice operator intervention is the more
common response mode, but newer facilities are moving toward more automated
systems.
Catastrophic failure of the system (e.g., plugging of nozzles in a dry
scrubber or breakage of a fabric filter) is generally readily detectable by
operators even in the absence of continuous monitoring data. Temperature and,
secondarily, ojcygen data from continuous monitors can be (and are) used to
adjust process operating parameters such as MSW feed rate or over/underfire air
supply to the incinerator.
Use of chemical monitoring data for process control is more complicated,
both in theory and in practice. In general, the relationship of MSW combustion
operating conditions to the emission rates of pollutants, especially trace
organics, is not well enough understood to allow systematic process control in
response to monitoring data.
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VII. QUALITY ASSURANCE AND QUALITY CONTROL
A. OVERVIEW
A vital part of any sampling and analysis program is the provision for
procedures which maintain the quality of the data obtained throughout the
sampling and analysis exercise. These procedures, termed quality assurance and
quality control (QA/QC), serve to (a) document the quality (i.e., accuracy,
precision, completeness, representativeness and comparability) of generated
data; (b) maintain the quality of data within predetermined control limits for
specific sampling and analysis procedures; and (c) provide guidelines for
corrective actions if QC data indicate that a particular procedure is out of
control.
The following definitions, which represent interdependent activities, serve
to differentiate between the complementary activities of quality assurance and
quality control.
• Quality Assurance (QA) activities addresses the delegation of program
responsibilities to appropriate individuals, documentation, data
review, and audits. The objective of the QA procedures is to allow an
assessment of the reliability of the data.
• Quality Control (QC) activities address the maintenance of facilities,
equipment, personnel training, sample integrity, chemical analysis
methods, and production and review of QC data. QC procedures are used
continuously during a. sampling and analysis program to maintain the
quality of data within control limits. QC data should be evaluated
immediately by the analysts; if the QC data fall outside a set of
specified control limits, corrective actions, as specified in the work
plan, must be taken.
In this section, specific QA/QC procedures are described. For an individual
sampling and analysis program, these procedures and/or others may be selected to
reach the goal of obtaining high-quality data. At a minimum, the procedures
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which are selected must be consistent with the standard ooerating procedures
and/or good laboratory practices of the sampling crew and analytical laboratory
involved.
The following discussion of QA/QC procedures is based upon a. guidelines
(2)
document issued by the Office of Monitoring Systems and Quality Assurance of
the EPA Office of Research and Development. This document, QAMS 005/80,
entitled "Interim Guidelines and Specifications for Preparing Quality Assurance
Project Plans," and the references cited therein provide an extensive resource
in selecting appropriate QA/QC procedures for sampling and analysis efforts.
The QAMS-005/80 document identifies sixteen essential elements of a QA Project
Plan (QAPP). These elements are listed in Table 15 and described briefly in the
following discussion. A QAPP of some kind would generally be required for most
sampling and analysis efforts.
B. TITLE PAGE AND TABLE OF CONTENTS
These elements are self-explanatory. The title page should indicate
individuals with QA responsibility for the sampling and analysis efforts.
Approval signatures should be required prior to the start of the sampling and
analysis efforts. The Table of Contents should include a distribution list for
the QAPP.
C. PROJECT DESCRIPTION
A general description of the project, including the experimental design,
and intended use of data should be provided. The description may be brief but
should have sufficient detail to allow the individuals responsible for review
and approval, of the QAPP to perform their task. Flow diagrams, tables and
charts should be included, as appropriate. A schedule, with anticipated start
and completion dates, should also be specified.
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TABLE 15
ESSENTIAL ELEMENTS OF A QA PROJECT PLAN
1. Title Page
2. Table of Con" nts
3. Project Description
4. Project Organization and Responsibility
5. QA Objectives
6. Sampling Procedures
7. Sample Custody
8. Calibration Procedures and Frequency
9. Analytical Procedures
10. Data Reduction, Validation, and Reporting
11. Internal Quality Control Checks
12. Performance and System Audits
13. Preventive Maintenance
14. Specific Routine Procedures Used to Asses Data Precision,
Accuracy and Completeness
15. Corrective Action
16. Quality Assurance Reports to Management
Source: U.S. Environmental Protection Agency/Office of Monitoring Systems and
Quality Assurance, Office of Research and Development, Washington,
D.C., "Interim Guidelines and Specifications for Preparing Quality
Assurance Project Plans," QAMS-005/80 (December 29, 1980)
/k Arthur D. Little, Inc.
-------
D. PROJECT ORGANIZATION AND RESPONSIBILITY
A table or chart which shows the project organization and line authority
should be included. An example project organization chart is shown in Figure 9.
Key individuals who are responsible for ensuring the collection of valid
measurement data and the routine assessment of measurement systems for precision
and accuracy should be identified; the responsibilities of each individual
should also be delineated. It should be noted that the QA coordinator should be
organizationally independent of the project organization so that the risk of
conflict of interest may be minim_ 'i.
E. QUALITY ASSURANCE OBJECTIVES
For each major measurement system, numerical QA objectives for accuracy,
precision and completeness should be established. These objectives may be
generally based on previous experience in applying comparable procedures to
similar sample matrices as well as on the requirements of the program. The QA
objectives for precision, accuracy and completeness should be summarized in a
table or chart; an example of a summary table is shown in Table 16.
All measurements should be made such that results are representative of the
media (e.g., waste feed, stack emissions) and conditions being measured. Any
factors considered within the experimental design to ensure representativeness
should be described.
All data should be calculated and reported in units consistent with other
organizations reporting similar data to allow for comparability of data bases
among organizations. Units for all measurement parameters should be specified.
F. SAMPLING PROCEDURES
A detailed description of all sampling procedures to be used is an integral
part of any QAPP. Where applicable, the following information should be
included:
• Description of techniques or guidelines used to select sampling sites.
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Professional
Operations
Officer
Section Manager
Corporate Quality
Assurance Officer
Client
Co
Program Manager
Quality Assurance
Coordinator
Sampling
Coordinator
Analysis
Coordinator
Quality Control
and
Data Manager
FIGURE 9 EXAMPLE OF PROJECT ORGANIZATION AND RESPONSIBILITY
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TABLE 16
SUMMARY OF ESTIMATED PRECISION, ACCURACY,
AND COMPLETENESS OBJECTIVES3
b b c
Parameter Precision Accuracy Completeness
Flue gas dioxin/furans ± 50-100 100
(Modified Method 5)
Ash dioxins/furans + 50-100 100
Velocity/volumetric flow rate + +20 100
(EPA Method 1 & 2)
f e
Fixed gases/molecular weight ±10 +20 100
(Modified EPA Method 3)
Moisture (EPA Method 4) + 2Qd + 10d 100
f e
Flue gas SO, (continuous monitor) +20 +20 100
Flue gas temperature + 10°F + 20°F 100
(thermocouple)
Ash (NAA) ND ND 100
Particulate Mass +10 ±12 100
Flue gas HC1 (1C Analysis) +10 +10 100
Flue Gas Lead/Cadmium (AA/AAF, NAA) ND ND 100
Flue Gas Chromium/Nickel (AA/AAF, +10 +10 100
NAA, Colorimetry)
.All objectives are expressed in terms of percent (%).
Precision and accuracy estimiated based on results of EPA collaborative tests.
.Valid data percentage of total tests conducted.
Relative error (%) derived from audit analyses, where
Measured Value - Actual Value ,«„„
Percent - . „ n x 100%
Actual Value
Q
Coefficient of variation (CV) determined from daily analysis of a control
sample where
CV - Standard Deviation
Mean
Percent difference for duplicate analyses, where
o ,. First Value - Second Value iriri.
Percent - T—-—~ , ,, -, xx 100%
0.5 (First + Second Values)
ND - not determined for this method
Source: "Revised Sampling and Analytical Plan for the Marion County Solid
Waste-to-Energy Facility Boiler Outlet Salem Oregon," EPA Contract No.
68-02-4338, DCN: 86-222-124-02-05, September 16, 1986.
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• Specific sampling procedures to be used (by reference in the case of
standard procedures and by actual description of the entire procedure
in the case of nonstandard procedures).
• Charts, flow diagrams, or tables delineating sampling program
operations.
• A description of containers, procedures, reagents, etc., used for
sample collection, preservation, transport, and storage.
• Special conditions for the preparation of sampling equipment and
containers to avoid sample contamination (e.g., containers for
organics should be solvent-rinsed; containers for trace metals should
be acid-rinsed).
• Sample preservation methods and holding times.
• Time considerations for shipping samples promptly to the laboratory.
• Sample preparation (e.g., concentration, dilution, cleanup
techniques).
» Forms, notebooks, and procedures to be used to record sample history,
sampling conditions, and analysis to be performed.
G. SAMPLE CUSTODY
It is essential that adequate chain-of-custody procedures be established
for each project. The following sample custody procedures should be addressed
in the QA Project Plans:
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Field Sampling Operations:
• Documentation of procedures for preparation of reagents or supplies
which become an integral part of the sample (e.g., filters and
absorbing reagents).
• Procedures and forms for recording the exact location and specific
consideration associated with sample acquisition.
• Documentation of specific sample preservation method
• Pre-prepared sample labels containing all information necessary for
effective sample tracking.
• Standardized field tracking reporting forms to establish sample
custody in the field prior to shipment.
Laboratory Operations:
• Identification of the person responsible to act as sample custodian at
the laboratory facility who is authorized to sign for incoming field
samples, obtain documents of shipment (e.g., bill of lading number of
mail receipt), and verify the data entered into the sample custody
records.
• Provision for a laboratory sample custody log consisting of serially
numbered standard lab-tracking report sheets.
• Specification of laboratory sample custody procedures for sample
handling, storage, and dispersement for analysis.
H. CALIBRATION PROCEDURES AND FREQUENCY
For each critical measurement parameter, including all critical pollutant
measurement systems, the following information should be included:
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• Calibration procedures and information.
• Applicable standard operating procedure (SOP) or written description
of the calibration procedure(s) to be used.
• Frequency planned for recalibration.
• Calibration standards to be used and their source(s), including
traceability procedures ".nd verification of purity procedures.
I. ANALYTICAL PROCEDURES
For each critical measurement parameter, the applicable standard operating
procedure (SOP) should be referenced or a written description of the analytical
procedure(s) to be used provided. Officially approved EPA procedures should be
used when available and if applicable.
J. DATA REDUCTION. VALIDATION. AND REPORTING
For each critical measurement parameter, the following items should be
briefly addressed:
• The data reduction scheme planned on collected data.
• All equations used to calculate the concentration or value of the
measured parameter and the reporting units.
• The principal procedures that will be used to validate data integrity
during collecting, transferring (if applicable), and reporting of
data.
• The methods used to identify and treat outliers.
• The data flow or reporting scheme from collection of raw data through
storage and validation of results. A flowchart will usually be
needed.
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• Key individuals who will handle the data in this reporting scheme.
(If this has already been described under project organization and
responsibilities, it need not be repeated here.)
K. INTERNAL QUALITY CONTROL CHECKS
This section presents guidelines for the number and frequency of replicate
and spiked QC samples and calibration standards to be used, including
concentration of surrogate or spike compounds to be added to designated QC
samples. The QA plan should document the objectives for number, type, and
frequency of QC samples.
Quality control samples are analyzed in the same way as field samples and
interspersed with the field samples for analysis. The results of analyzing the
QC samples are used to document the validity of data and to control the quality
of data within predetermined tolerance limits. QC samples include blank
samples, analytical replicates, and spiked samples.
Blank Samples
These samples are analyzed to assess possible contamination from the field
and/or laboratory, so that corrective measures may be taken, if necessary.
Blank samples include:
• Field Blanks--These blank samples are exposed to field and sampling
conditions and analyzed to assess possible contamination from the
field (a minimum of one for each type of sample to be collected and
analyzed).
• Method Blanks--These blank samples are prepared in the laboratory and
are analyzed to assess possible laboratory contamination (a minimum of
one for each lot of samples analyzed).
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* Reagent and Solvent Blanks--These blanks are prepared in the
laboratory and analyzed to determine the background of each of the
reagents or solvents used in an analysis (a minimum of one for each
new lot number of solvent or reagent used),
Replicate Samples.
These samples are analyzed in order to establish control and assess the
precision of the analytical methodology. Replicate samples include:
• Field Replicates - These samples are collected in the field and
analyzed in order to assess the reproducibility of the sampling
program (a minimum of one for each sampling event per sample type and
measurement parameter).
* Laboratory Replicates - These replicate samples are prepared in the
laboratory in order to assess the reproducibility of the laboratory
procedures used (a minimum of one for each lot of samples analyzed).
In addition, replicate analyses of specific samples may be undertaken by the
analyst to check on the validity of any anomalous results. Such results could
be the result of instrument or data system malfunction, operator error,
laboratory contamination, etc. Repeat analyses of the sample in question and a.
previous "normal" sample will serve to indicate which of the possible problems
is, in fact, present.
Spiked Samples
Samples may be spiked with one or more selected surrogate compounds prior
to extraction and analysis. "Surrogate" compounds are defined as species that
are chemically similar to the compounds being determined but that are not
expected to be present in the samples (e.g., when GC/MS is the analytical method
to be used, stable-isotope labelled analogs of the compounds sought are
excellent surrogates). The data on surrogate concentrations are used to
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calculate surrogate compound recovery from each sample as one measure of the
accuracy (bias) of the sample preparation and analysis procedures. To the
extent that an analytical method (e.g., GC/MS) is consistent with use of
surrogates, this procedure allows recovery to be estimated for every sample at
trivial incremental cost to the testing. In some cases, e.g., trace metals,
GC/ECD analyses, it may be difficult to select an appropriate surrogate compound
that will mimic the behavior of the species sought but not lead to positive
interferences in the analysis.
In addition to use of surrogate spiking (if possible), selected samples
should be spiked with target analytes at a predetermined concentration level(s).
This requires that each of the selected samples be carried through the entire
sample preparation and analysis procedure twice, once unspiked and once spiked.
Also, spiked blank samples for each measurement parameter should be analyzed in
order to assess the inherent accuracy (bias) of the analytical method. To ensure
that the per cent recovery of the spike can be determined with a reasonable .
degree of confidence, the spiking level should be at least 2-3 times the
critical decision level (see Section II.A) and at least as high as the level
expected in the unspiked sample. Depending on the concentration of analyte in
the unspiked sample, these data may provide an estimate of the recovery of the
species of interest from the sample matrix.For difficult sample matrices,
multiple spiking levels may be used (method of standard additions).
L. PERFORMANCE AND SYSTEM AUDITS
Each QAPP should describe the internal performance evaluation and technical
systems audits which are planned to monitor the capability and performance of
the system(s) to be used for obtaining critical measurements.
The technical systems audit consists of an evaluation of all components of
the critical measurement systems to determine their proper selection and use.
This audit includes a careful evaluation of both field and laboratory quality
control procedures. Systems audits are normally performed before or shortly
after systems are operational; however, such audits should be performed on a
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regularly scheduled basis during the lifetime of the project of continuing
operation. The on-site technical systems audit may be a requirement for formal
laboratory certification programs.
After systems are operational and generating data, performance evaluation
audits are conducted periodically, as appropriate, to determine the bias of the
critical measurement system (s) or component parts thereof. The plan should
include a schedule for conducting performance audits for each critical
measurement parameter, including a performance audit for all measurement
systems, should the nature of the work require that a performance audit be done.
As part of the performance audit process, laboratories may be required to
participate in the analysis of performance evaluation samples.
M. PREVENTIVE MAINTENANCE
The QA project plan for a trial burn should itemize the procedures for .
preventive maintenance that are relevant to the sampling analysis and efforts
required in the project. For example, the following types of preventive
maintenance items should be considered and addressed in the QA Project Plan:
• A schedule of important preventive maintenance tasks that must be
carried out to minimize downtime of the critical measurement systems.
• A list of any critical spare parts that should be on hand to minimize
downtime.
N. SPECIFIC ROUTINE PROCEDURES USED TO ASSESS DATA PRECISION. ACCURACY. AND
COMPLETENESS
The data quality indicators (e.g., precision, bias, completeness, and
method detection limit (MDL)) should be routinely assessed for all critical
measurement parameters. Specific procedures to assess precision, bias,
completeness, and MDL on a routine basis should be described in each QA Project
Plan, as applicable to the measurement parameter and the system being measured.
The QA Project Plan should also contain and discuss any statistical or
mathematical methods used to evaluate the measurement data.
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0. CORRECTIVE ACTION
Corrective action procedures include the following elements and must be
described for each project:
• The predetermined limits for data acceptability beyond which
corrective action is required.
• Procedures for corrective action.
• For each critical measurement system, identify the individual
responsible for initiating the corrective action and also the
individual responsible for approving the corrective action, if
necessary.
Corrective actions may also be initiated as a result of other QA activities,
including:
t Performance evaluation audits.
9 Technical systems audits.
• Laboratory/interfield comparison studies.
A formal corrective action program is difficult to define for these QA
activities in advance and may be defined as the need arises.
If long-term corrective action is necessary to eliminate the cause of
nonconfonnance, the following closed-loop corrective action system may be used.
As appropriate, the sample coordinator, analysis coordinator or the program
manager, ensures that each of these steps is followed:
1. The problem is defined.
2. Responsibility for investigating the problem is assigned.
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3. The cause of the problem is investigated and determined.
4. A corrective action to eliminate the problem is determined.
5. Responsibility for implementing the corrective action is assigned and
accepted.
6. The effectiveness of the corrective action is established and the
correction implemented.
7. The fact that the corrective action has eliminated the problem is
verified and documented.
P. QUALITY ASSURANCE REPORTS TO MANAGEMENT
QA Project Plans should provide a mechanism for periodic reporting to
Management on the performance of critical measurement systems and data quality.
As a minimum, these reports should include:
9 Changes to the QA Project Plan, if any.
• Limitations or constraints on the use or applicability of the data, if
any.
• Quality programs, quality accomplishments, and status of corrective
actions.
• Results of QA systems and/or performance evaluation audits.
» Assessments of data quality in terms of precision, bias, completeness,
representativeness, and comparability.
• Quality-related training.
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The final report for each project must include a separate QA section that
documents the QA/QC activities that lend support to the credence of the data and
the validity of the conclusions.
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VIII. REFERENCES
1. U.S. EPA, "Test Methods for Evaluating Solid Waste-Physical/Chemical
Methods," SW-846, Third Edition (November 1982).
2. U.S. EPA, "Interim Guidelines and Specifications for Preparing Quality
Assurance Project Plans," QAMS-005/80 (1980).
3. Ozvacic, V., "A Review of Stack Sampling Methodology for PCDDS/PCDFS,"
Chemosohere 15 1173-1178 (1986).
Velzy, C. 0., "ASME Standard Sampling and Analysis Methods for
Dioxins/Furans," Chemosphere. 15, 1179-1185 (1986).
5. American Society of Mechanical Engineers, Draft Protocols on "Sampling for
the Determination of Chlorinated Compounds in Stack Emissions" and
"Analytical Procedures to Assay Stack Effluent Samples," (December 1984).
6. Radian Corporation, report to Massachusetts Department of Environmental
Quality Engineering, "Final Emissions Test Report. Dioxins/Furans and
Total Organic Chlorides Emissions Testing. Saugus Resource Recovery
Facility. Saugus, Massachusetts," (October 1986).
7. Gallant, R. F., J. W. King, P. L. Levins and J. F. Piecewicz,
"Characterization of Sorbent Resins for Use in Environmental Sampling,"
EPA-600/7-78-054, NTIS No. PB-284347 (March 1978).
8. Piecewicz, J. W., J. C. Harris and P. L. Levins, "Further Characterization
of Sorbents for Environmental Sampling," EPA-600/7-79-216, NTIS No.
PB80-118763 (September 1979).
9. New York State Department of Environmental Conservation, "Emission Source
Test Report, Sheridan Avenue RDF Plant, 'ANSWERS'," (1985).
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VIII. REFERENCES (cont.)
10. Cianciarelli, D. J. and B. D. Williams, "A Summary of Source Sampling
Methods Used to Evaluate the Flakt Pilot Plant at the Quebec City Mass
Burning Incinerator," Environment Canada, December 1986.
11. Schlickenrieder, L. M., J. W. Adams, K. E. Thrun, "Modified Method 5 and
Source Assessment Sampling System Operators Manual," EPA-600/8-85-003, NTIS
No. PB85-169878 (February 1985).
12. Jungclaus, G. A., P. G. Gorman, G. Vaughn, G. W. Scheil, F. J. Bergman, L.
D. Johnson and D. Friedman, "Development of a Volatile Organic Sampling
Train (VOST)," Proceedings of the Ninth Annual Research Symposium on
Incineration and Treatment of Hazardous Waste, EPA-600/9-84-015 (July
1984).
13. Hansen, E. M., "Protocol for the Collection and Analysis of Volatile POHCS
Using VOST," EPA-600/8-84-007, NTIS No. PB 84-170042 (1984).
14. Ross, R. W., F. C. Whitmore, R. H. Vocqui, T. H. Backhouse, B. M.
Cottingham and R. A. Carnes, "VOST Applications at the USEPA Combustion
Research Facility," Proceedings of the Eleventh Annual Research Symposium
on Incineration and Treatment of Hazardous Waste, EPA-600/9-85-028
(September 1985).
15. Harris, J. C., D. J. Larsen, C. E. Rechsteiner and K. E. Thrun, "Sampling
and Analysis Methods for Hazardous Waste Combustion (First Edition),"
EPA-600/8-84-002, NTIS No. PB84-155845 (February 1984).
16. Bell, J. M., "Development of a Method for Sampling and Analyzing Refuse,"
University Microfilms, Xerox University Microfilms, Ann Arbor, MI (1963).
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VIII. REFERENCES (cont.)
17. Churney, K. L., A. E. Ledford, Jr., S. S. Bruce and E. S. Domalski, "The
Chlorine Content of Municipal Solid Wastes from Baltimore County, MD and
Brooklyn, NY," U. S. Dept of Commerce, National Bureau of Standards,
National Measurement Laboratory, NBSIR 85-3213 (1985).
18. Domalski, E. S., K. L. Churney, A. E. Ledford, Jr. and S. S. Bruce,
"Monitoring the Fate of Chlorine from MSW Sampling Through Combustion Part
I: Analysis of the Waste Stream for Chlorine," National Bureau of
Standards, Chemical Thermodynamics Division, Center for Chemical Physics,
Chemosphere. 15, Nos. 9-12, pp. 1339-1354 (1986).
19. National Recovery Technologies, Inc. (NRT) DOE/SBIR Combustion Effects -
Study, Sommer, E. J., G. R. Kenny and J. A. Kearley, "Municipal Solid Waste
Profile Analyses at the Summer County Resource Authority for Week of
October 1, 1984."
20. Hasselriis, Floyd, "Refuse-derived Fuel Processing," Butterworth Publishers
(1984).
21. Cuiu, C., R. Halman, K. Li, R. S. Thomas, R. C. Lao, "Analytical Procedures
to Assay Environmental Samples for PCDD/PCDF," Chemosphere. 15. pp. 1091-98
(1986) and Stieglitz, L. , G. Zwick and W. Roth, "Investigation of Different
Treatment Techniques for PCDD/PCDF in Flyash," ibid.. pp. 1135-40 (1986).
22. Rappe, C., S. Marklund, L. Kjeller and M. Tyskland, "PCDDs and PCDFs in
Emissions from Various Incinerators," Chemosphere, Vol. 15, pp. 1213-17
(1986).
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VIII. REFERENCES (cont.)
23. Fairless, B.J., D. I. Bates, J. Hudson, R. D. Kloepfer, T. T. Holloway, D.
A. Morey and T. Babb, "Procedures Used to Measure the Amount of 2, 3, 7,
8-Tetrachlorodibenzo-p-dioxin in the Ambient Air Near a Superfund Site
Cleanup Operation," Environ. Sci. Technol., 21. pp. 550-555 (1987).
24* Wagoner, D. E., "Sampling and Analysis for Hazardous Waste Combustion," EPA
Workshop Proceedings (1986).
25. Butler, F. E., J. E. Knoll and M. R. Midgett, "Chromium Analysis at a
Ferrochrome Smelter, a Chemical Plant and a Refractory Brick Plant," APCA
Journal, 36, 581-584 (1986).
26. Bonner, T. A. et al, "Engineering Handbook for Hazardous Waste
Incineration," SW-889 (September 1981).
27. Brenchley, D. L., C. D. Turley and R. F. Yarmac, "Industrial Source
Sampling," Ann Arbor Science Publishers, Inc., Ann Arbor, Michigan (1973).
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APPENDIX A
Equipment and Procedures Used in Milwaukee Sampling Program
Overview
During the twelve-month period beginning August 3, 1959, one collection a
week was made from each sample area. The material picked up included all
garbage, ashes, combustible and n^combustible rubbish produced by the res -:ents
of the sample area.
A special City crew collected the material and separated it during
collection into three categories: ashes, combustibles, and noncombustibles.
Total weight, volume, density and moisture content determinations were made on
each of the three categories. The percent that each component contributed to
the total sample was then calculated. In addition to these physical tests,
certain chemical analyses were made on the combustible and ash portions. The
chemical tests included analyses for hydrogen, nitrogen, carbon, lipids,
potassium, and phosphorus. Subsequent calculations for percent liquid content
and C/N were also made. All tests were performed on each individual sample.
Equipment:
1. A dump truck was outfitted with a specially constructed bed to provide
separate compartments for the ash, noncombustibles, and combustibles
portions of the combined refuse. An Allis-Chalmers forage harvester (shredder)
complete with necessary appurtenances including a loading platform, a 25
horsepower electric motor, a discharge spout, and all required safety
devices was used.
it-
Adapted from Reference 16.
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2. Six 1 1/2 cubic yard steel bins complete with castors and a removable end.
3. A battery-operated fork lift.
4. A 1000 pound net-capacity platform scale rebuilt to provide an accuracy of
0.1 pounds.
6. Three 55 gallon drums.
7. A gram laboratory scale.
.8. A forced air drying oven.
9. A Wiley Mill.
10. A sand splitter.
11. Eleven drying pans.
12. A hand tamp.
13. A Parr oxygen-bomb calorimeter,
14. Air-tight sample cans.
Sampling Procedure:
1. Collected refuse from appropriate sampling area. Separated material during
collection into three separate components, ashes, noncombustibles, and
combustibles.
2. Trucked material to central testing point. A corner of one of the cities
incinerator buildings was used as this location.
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3. Broke open the combustible packages and removed the unburnable items. All
combustible material was placed in the proper movable bin and all
non-combustibles were thrown into their respective truck compartment.
4. Processing of combustibles,
a. All movable bins containing combustible refuse were weighed
and volume measurements were taken prior to running the material
through the shredder.
b. The material was processed through the shredder four times.
Two movable bins were placed under the discharge spout to halve the
material each time it went through the machine. By halving the refuse
four times the samples was reduced to one-sixteenth of its original
size.
c. The remaining material was quartered by a shovel, retaining about
enough to fill a gallon container.
d. Weight measurements were taken of all the combustible refuse prior to
disposal to determine the moisture lost during the shredding
operation. »
e. The sample was transferred from the gallon container to a drying pan
and placed in the oven.
f. Weight measurements pertinent to moisture content calculations were
recorded.
g. A sand splitter was used to quarter the sample after it was processed
through a Wiley Mill where it was reduced to a maximum size of one
millimeter. The size of the final quarter was about 100 grams.
h. Fifty grams of this were sent for certain chemical analyses and the
other 50 grams were returned to the drying oven. It was necessary to
86
-------
redry the material to eliminate moisture added during the grinding
process.
i. The calorimeter test was performed and the information recorded.
5. Processing of Noncombustibles
a. Noncombustibles were placed in the proper metal bins, weighed, and the
volume determined.
b. This material was stored in an empty bin and separated periodically
into three separate components - cans, bottles, and miscellaneous
noncombustibles. Data were recorded to enable calculation of the
percent of total weight and volume represented by each component. The
material was then thrown away.
c. Once a week a grab sample was taken from the material produced by one
classification. This sample was taken from a different area each
week, thereby each area was tested once every 10 weeks.
d. This sample was placed in a drying pan and then put into the oven.
e. Weight measurements pertinent to moisture content calculations were
recorded.
6. Processing of Ashes
a. Ashes were placed in the proper bin, weighed and volume measurements
were taken.
b. The ashes were quartered by shovel, retaining approximately a pint of
material.
c. The pint sample was placed in an air-tight container and stored until
all such ash samples for the week were placed therein.
87
-------
d. At the end of the week the sample container was emptied and the lumps
were reduced with a. hand tamp.
e. The material was quartered with the sand splitter, retaining about 2
pounds,
f. A moisture content was made by use of the drying oven and the
pertinent weight measurements were recorded,
g. The dried ash was reduced to a weight of about 400 grams with the sand
splitter.
h. Half of this was sent to Purdue for further analyses and half was
returned to the drying oven.
i. After a second drying period, a calorimeter test was performed.
88
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APPENDIX B
ASME-EPA DRAFT ENVIRONMENTAL STANDARDS
PROTOCOLS FOR SAMPLING AND ANALYSIS OF
PCDD/PCDF . _SW COMBUSTOR EFFLUENTS
89
-------
DRAI
numtut ramou. rot UOOUIRC
rt&ATiMC MIA BMIM: SAMPLINC m
nnMioM •» cftxouiuw OACAMIC OMTOVM
ui nucf nan MLUI mm OOUWMTIOM rum
1M
Tha lafara*tlaa aa. (ur»aca aparatloa which chow I 4 a*. gathara4 4urlag
(• far ttaca aalaalaa* af chtarlaata4 argaalc caaaaaaa1* !• a«Ma«rl«a4 la
following 4ata far*. It will ha Mta4 that acttMl *•!»•• whtla aaapllag
•a4arway la tha far* •( c*fU« «f «ctM«l lit If clMfU U tlM
aatlMi I* r«qtM*t«4. It
le* at tlM tt*» •< »••* •*•• •••»!!•« U actually kat«f 4a«a.
a>artaa« katw«aa tha •>r«ct*4 a^ actval valuaa aortM ••^•••§ ia a fvlAa
t* wkatlMC the ayata* waa «a«fatlaa ••raallf tidtla it «aa aalafl aaaylaJ.
tka c*«BariaMi au||««t* tka af*t«« mmj m»t kava kaa* afaratlag •»t»*Hf
lag aaayllBf. It My aa 4tf(lc«ilt ta Mllt»a4 t«a 4ata.
It will alaa ba a«ta4 that aaoa af tha r*^«ilr«4 UlarMtlaa la ta ha
ilaetaa' a* naatly c*ntl>u*w(ly aa paaalala 4urlaf aaayll*g« tkla la aa aa
Mralt Mtactlaa af chaagaa. IMaa4a4 a«4 U«a*«rt«at. nMcb nay hava
:urta4 4urt*g aaaallag. Tha acc«irra«ca or ahtaaca af a*y a«ch chaag** *• •
:tor la tatafpratlag tha taavlta af tha aaayllag.
••cocalng th* aaaaatlat lafara«ttam ahall hagla at laaat thraa haura
fora •••»!!•• ta wg«B **4 ha ca«tt«M4 tat at laaat aa howi altar aaayllag
tafa>laata4«
Tha lallowlag fan* la Iata«4a4 ta accaapaay raaa't* •• *a«Kca aaaallag
r«fn*a-ta-aaargy facllltlaa.
Naa* a*4 a44raaa af tha facility)
N.« ••<< l«l«pho«« nuabcr of •!••( f*n*r*l ••••(•r ar athar y>*r*oa ta
contact f«|ai4t*| aalaalo* •••pilag rro(raai
I. N«M «n4 t«Uphon« auvbar of aviciloa •••f>ll»| (••• >«n«|«rt
I
MM* aa4 talaah«aa auM«r at pataoa [a«ao««lbl« for Ukoratory aMlyala
af aaaylaai
DRAF1
Haa* aa4 talaahaaa Miahar af Mtaaialaglcal •OBltoil«( atatla* ••r*lcl»g
th« lacallty af tha alaatt
Baalgaatta* af tha caafetatlaa ttala actually •••»!••!
. I
»ata af aalaala* aaa»lla|>
Tlaa Mhaft aaayltag atarta4i
Tlaa whaa aaapllag taralaata4i
• • Iy»« af rafvaa aracaaalag ayataa («.§., ••••-bum. tafuaa 4afl»a4 fual)i
9. Kwacttaa rafvaa acaaaratlaa a»tho4. If apacaarlatai
10. Tya« af furaaca (e.g.. Matarvall. tafractary-vall, hybr!4)i
II.
II.
II.
la auilllary fital ragulacly flra4f If aa. nhat fuall
Bwalg* haat talaaaa rata (Matu/hr)t
•!••• aro4uctloa rata aa4 ca*41tloaai
*r. M'l. «^ C»* e«t«§rata4>
Iba/hi •
a»allcy.
fa«4 ft9f»rtl»u far which twit «•• 4ailgna4i
Aaaga •/ ha«Cl«| »»lu«» _ ta
Ranga af •olvtuta content! _ to
- kaoga oj a«h content! _ to
fttn/la
wt X
wt t
14.
ri«*aa provide • cro««-«ect loncl dl«|f»a of the facility, preferably to
• cele. •bowing the ipcllel relctlonihtp between the MJOI eleaeiit* af the
• •• -•-- ------ <--j ...,» ,„ ,h, f,mim: the
-------
DR/
DRAF
o*4 reel4uc renovel ayelen; ahepe el Ik* furnee«; prlaury e»4 aeco«4ery
conbuetloo •!( porte; the holler en4 It* flue ••• •••••!«•; coot alower*!
••jar heat lianaler eurfacee; aeo*oa>lier; elr prehceter (If epproprtete);
•Ir pollution control eyeten; I»4«ee4 4ieft fen; e»4 •tack. Indicate
locotlona of tenparatitre and fiooBiir* 4«t«ctor> •!••.
S. DoccrlptlcM of tit* grot* ojr«toai
- (wf oil or i __^
T»p« (•••-, t«eloroe«tl«i. rolUt. tra««ll«|. rotary)!
•uaoor of st«f MctloM (If «f>f rof rl*ta)t _
Croto »r«o (ft ) (or
•. •••crlptloo of tb« holler i
vol
(ftj)l
olMMloo* (ft)i L
of coot »low*r*i
toot
(•ppro«laot« tlM*)l
of cMbu*tlo« (e.g.. OBCOSO air, atar*«4 atr)i
II. Owrfira and u«4arflra air
Baacrlo* a«*ifo tut Ijr* •*
aortat
Oaacrlba »o» total cooAoattoo air ao4 air aletrlbottoo la co«trolled
Vailfy that air *l»trlkutlo« ayataa* ara operating aa
19. Tf»« of 4tafti
•aw is draft ragulataa:
20. ftaecrlptleo of aalld neate feed lag and etokUg ayaten:
- low la fending late controlled!
- frequency and length of feed ren atrakei
21. B«acrl»a tba overall pleat control eyeteo logic (e.g.. vket aaaaur
ara «aa4 aa tko aaela for controlling firing ratet)t
ota
II. Stack height (ft)i
•tack 4lan*tat at tap (ft)l
23. Tjpa of atr pollution control ayatani
24. If alactroatattc praclpltatori
•pacific collection area (ft'/IOOO ACrn)j
- Boalgn taaparatnra at Inlet (*f)i
ir of In4epan4ant hue aectlanai
Which In4apon4ant hue aactlona were In aarvlce oWlng enieelon
•aapltngf
- bealgn partlculate loading at Inlati
at antlett
Kapplng frequencyi
II. If fahrlc flltari
rahrtc type Valght Weave
gralna/4acf
gralna/4acf
rinlah
lag cleaning o*tho4 an4 frequency i
Alr-to-cloth retlo (ACTN/ft')s
•oatgn praaaura 4rop acroea beg* (la., W.C.):
Dealgn gee tenperature et Inlet (*F)i
Total nunber of he|t:
-------
Actual o«»bor *f baga io **r*lc« at tta« ol aaopllagt
bug* in preaaura 4roff> acroaa baga Aufiog taatlatgi __
IIMcfe fl«a •'* eooatooaoto *t* regularly o*aautaa't Indicate locatte* *{
•miter t
IM t n*M>t
Iteoot
tocatioi
Unit Serve*
j tkia Hoolter
C«I|MM HOOD* 1eretur«a cod location*: *F,
- Attach eue-uiry record of furnace temperature o*aeuree»nta duii«g
-------
Attack atrip dkart near* *f taaawratura *t top af furnace, Im fra«t
af a cram twaaa - •<•« lh* aaqallag aarta* Ctl t«cot4« «r«
f*r mmt» ck«a •••
their l*c«ti*M)
41. flw* ga»
Attach atrtf durt nc*r«* (*' c««c«mtt«tt«M «f ths f«li*»ia§ !!«•
t««at*. aBawifAi *»*r tM •••pliBf p«ri*tfs car boa
, carba* 41aalaa. *Ky|aa, altrafaa amlaa, auKvr aloxlaa.
tacal hyaracaraaaa, watar *aa«<> ••* (&•• ••• fl«M
- Attack atrip cKart mcarJ lar la-atack aa«city a»ar Cha
42. Uiclu4a • capr af tha oaaratar'a lag far tha aarl«4 af tka taat.
-------
SAHFLINC P0ft INI 0STHMINAT10N or CUIOIINATCD
OIGAN1C COHP0NNBS IN STACK MISSIONS
jpri.iGAiil.ITf
DRAF
DRAFi
I.I Ptiaclpjat Stack ga»aa tkat say caatala cfclarlaatal
avgaatc caapaiiaaa •(* ttltkataiia fraa tka •(•cfc walag •
•••pliag ttala. Tka aaalyta la ealiaetad la tka caapllag
trata. tfca c*»pvu»4« af lataraat *rt 4«t*ral*«4 ky
a*l*aat aitracttaa falla«»a4 ky §aa cktaa>ata(f ayhy/aaaa
aaactraaeapy (GC/MS).
l.l Aaal |cafcy I |f t tfcla aatba* I* appllcakl* 1*' *»* 4atat-
a>laatta>a af eklarlaatatf atgaalc caapana4« I* •tack ••!•-
•!•••. Tk* ••apltag trata la ** iaalgaad »k«t aaly tfca
tatal aaanat *f aaefc eklactaata* argaaic ea«p»n«4 !• tka
•tack aataala** «ay k* aatar*laa4« T» ••(•, •*
k>»* k*a« f«rf»r««4 «• ••••••tr>t« tkat tk«
ckl«rlaat«4 *i§a*lc c ••••«••• c*ll*«l.ai !•
*f ik* ••••Hag trala *cc*tal*ly •••crtk««
tk« actual aartltla* •! aack la (ka ataek ••Icalaaa. If
aapatata aacta af tfca •••alias (**!• *i« aaalf*a4 ••>•»-
acaly, tka iaia akanl4 ka lacliiaai aa4 aa aata4 aa la
Sacklaa 1 kala*. tka aasfliag akall ka c*aa«et«4 ky
caaavtaat fataaaaal a«ya«laaea4 wick Ckia taat ptaca^nta
••4 cagalcaat af lairlcaclaa af tka aparatiaa •' *••
pr««ctlka4 •••pliag Ctala *a4 coaatratata ml tka aaalytt-
cat tcckalavaa fat cklatiaatad ar§aalc caaaawatfa, aapacl-
ally P»»a ••< PC»f«.
tANCj Of MllilMUH UTiGTAStt STACK CAS COHCSIITiATION
Tfca raafa af tka aaalyclcal *«tkaJ ..r ». .,MH«a4 caaalaar-
akly tk*a«fk caacaattatlaa mmilmt «tl.tiB.. fh, total Matk»4
•aaaltlvlty la alaa fcl|kly iap«ai«at aa tki valuaa af atack
|aa •••pl«4 aa4 tka aatacttaa Halt of tk« «*alytlcal flalak,
Tfca aaat akall aataialaa far tkali •y*t«. ih. .i.i.M. aatact-
afcla atack |aa caacaatrat laa f«r tfca cklaria«ta4 araaalc ca«-
aanaaa af lataraat. Tfca »lalaua ••••ct.kl. atach «•• caaca*-
ttatlaa akaiiM faaatally ka la tka as/a1 (••aograa/cvklc
•ataii at lavac faaga.
*•
•atai Tkla •«tk»4 •••»••• th«t all *f (k« caaaavaaa af
lataiaat ata «allacta4 altkar *a tka 1*0-1 raala at ia
wpatiaa* ••••!!•( tvala caap/aaaata. Blae* tka *atk*4 at
•ka araaaat tl*a ka* aat kaaa *ail4ata4 ia tka ftaaaaca af
all tka atkac eaaaaaaata ptaaast fICI, klfk *r|aaic laaa)
I* tka ataek a«l*al*a, tt la racaaa«aa«4 tkat aaataprlata
^•ality aaatral («C) ataaa ka «*»l*f«4 **tll avek ••!!••-
claa kaa fcaaa aa*alataa. Tkaaa QC atapa *ay Iacln4a tka
••• at a ka«k«p taala trap ar tka aadltlaa af a ra«i«««a-
tatlva lakalad ataa4ar4 f ilatlafulakakla fr»a tka tataraal
• taaaati aaai tat a.ttaatltatlaal ta tka flltat aai/ai tka
SAB-t ta tka flaM prlat ta tka ctart af •••aliaf. Tkaaa
•(•»• bill aravlaa lafataatlaa aa paaalkla kt*aktkvaa|k af
tka caaaaaaia af latataat*
• iPOSTASll-lTI
• •cognlilut tk«t *04tftc*tlaa af tk« •*tk*4 a*y k* r«^»ilr«4
lor »p«clfic apallcattaaB. tka flacl r«p«rt af • t*«t vkata
ck>..|.« •!• •••• skall Iacln4«i (I) tka *«*ct mo4t I icat laa;
(2) the r»ilo«»l« I"' th* aoal f lot loa; *ai (1) •• «»tla»t« of
tit* *ff«c( tfca •o«lllc»lio« Mill pfniiic* om tk* «•(••
Orgvatc caaaanaaa atfcar tkaa tha ceapau«4a af iataraat »ay
latacfata ultfc tfca aaalyala. Appcaatlata aaapla claaa-af
•tap* akall ka p*tfar*aa. Thr«y|k •!! •!•)•• •( ••••!«
kaaallag aa4 aaalyala, caia •kawld ka !•••• ta a*ai4 caatact
af aa«plaa aai aatracta with ayathstlc argaate aatatlala atkac
tkaa aalytatraf laaratfcy tan* (tri*). Aakaatva* «h«ul4 aat ka
•••4 ta k*14 TPt* tlaat* o 114* (fcvt, If *«e«*aary, appra-
fllata klaaka aaat ka taai . *4 lakclcatlag aa4 •••Itag
|**aaaa muft aat ka aaa4 aa tka ••apliag trala.
J. fSIClSION Aii ACCJIACT
Piaclalaa aai acearaey ••••ur«a*at« fc«*« not yat kaaa kaaa aa
PCM aai PCDP natal tfcl* aatkaa. Thaaa aaaavraaaata ara
•••4«4. lavavar, tacavary afflclaaclaa far aaurc* aaa>plaa
' aplkai wltk caapaaa4a bava taaga* lr»a 10 ta 1IOS.'*
•• aAMPUNg SUMS. TIMS. AMP tOtUMI
*.l S»aplt«i Iua« i Tba •«••»• r af aa*pllag ritaa auat k*
•afftclaat ta ara«!4a •taiaal ctatlatlcal aata *«4 la aa
eaaa akatl ka laaa tkaa Cfccaa
-------
C - ?ha aaaipia race-wary (I)
• - tke allowable etack aalaeleea (ag/e> )
DRAF1
•lack Wai
DRAF1
lia.plei A - O.OJO eg; • - lOlj C * J0t| aad 0 - I a|/ai
•f - O.OS ,
ti«*n«t -"
I. AffABATUS
Ce*d*«ae« t
Naele Cat It Idea
• a«pll*)g Tralai Ik* trate caeelate ef aosile, probe, boated
parttculata filter, aed eerbaat eiadula followed by fear leplagere
(fig. I). »r**t*fe« te e>ade let tke addlllea ml (I) • cycles* la
tke h«*t*4 filter b*i wk«» t«*tl»g •••rc«i **i(cl*( Iklgli c*«c««-
cr*tl««« *f parttcwlat* ••ttar. (I) * l«rf« water trap b*twa*a the
M«t*4 filter mm* the eerba*t aeettl* far eteck geee* vttli kigk
•ol«lHr« c*me*t. »«4 O) »4te are «eetetae4 la tke lellewtag aect !•<••.
i.l.l
tke *e»«le ekall ke mmtm te tke epeclf Icet leee *f IP* Metke4
The **««le »ey ke *a4e ef elckel plated atalalaaa eteel,
or koroi lllcata glata.
S.
1.1.2 Probe
the pteke ehall ka lleei er ••«• ef T««, kerael llcata , or
fuart* glaee* The liner er probe e*te*4a peet tka reteleleg »«t
late the etech. A ta*petatere ce»trelle4 Jeckat pievl4aa pcetec-
tlo« af the lifter or probo. Ike lleer er peek* ahall ka efelpped
wltk a coaeectiat flttleg that la capakle ef fara)l*g e leak-fee*.
vacMuat-tlgkC eeeaoetloa Mlthewt eeallag graaeaa.
I.I.I £a«ple Traatfar Llgaa (eptloaal)
the eaaple traeafer lleea. If •••«o4. ahall b* heat traced,
heavy veiled Tri* (1.1 «• fl/l l«.| O.K. » 0.1 cm |l/l te.| veil)
with ceaaectlag flttlega that are capable of foralag leak-free,
*acitu*-tlgkt ceeeectfeea vltheet H*lag eealleg gteaeee. Tk* lie*
ekewld ke *e ekett ea peeelkle aei •«•( be •atatelaed et ltO*G.
1.1.4 tllter II el it I
lereelllcate glaae, wltb a glaaa frit flltar avppert aei e
|laaa-te-glaae eeal or Iff* gaakat. A twbbar |a*ket ahall eat be
ua*4. the holoor 4*al|a ehall prevlec a poaltlve aaal agalaat
leakage tiom th* outald* er areviii I h« fllt«r. The holder akatl
bt artachod le.**dlat*ty at tka ewtlat ol the probe (er cycloee, If
el* *l the Uodlllad ttfeeattote-Saillfc lype
1 e»d I Caalala 100 erf Walei •'.
ef 4 Coal a to* BOO'SOO Oiaiaa SIMca Bel
t le lha Ha«ia*>fltae*d Back-Up le Ike flaal* Catltldpa
T) • Tfceiei*ca«plo lecell**
fig. 1. Modified W* Hethod 5 Train for Orf*n!c* S*-pIln|
Source: Method*
lor A»*«a»in| Oi|*nlc«
Soulc*! In C>pO*U[t Ev«lu«C|oa DIvltlOB Siulll*
-------
I.I.S
filter
(opttoeal)
DRAFT
Tke cycleae •hall be cea>atr«ct*4 *f baroalllcat* giaea «ltk
g flttlaga (list a>re capable »f f«rat«| leak-free.
*«c*«»-t Ifkt c**«j*ctl»*c *)itk*Mt walajg aaallag (raaaaa.
1. 1.* filter
irate*
Tke baatlag •yet** •••t k* capable ef oialst alnle| • tee>p«-re-
ture *tm*m* tk* Illter keltfer f*«** « .*»•. if «a*4) imliig •••pl
1*1 »f 110*14 C fl4l*IS*r}. A t**p*f«(«|> ••••• c«p«bl* of
•••••trial ?*ap*r**«r* t* vlthl* 3*C <5.4 F> *k«ll fee {••tailed ••
4 tfca filtac
4S.t *•>
Itr IB.I
•• tk* •*rfc**t
. c**llMi !• a itsp, ak*l)
ffk* ••*•••( ••4«la •••!! »• vad* •( glc
vlth c*Mft*ctl«§ llt(taj|« tk*t *f* ••!• t« !»(» l**k-lt**»
ti|kl *««!• •ltk*«t ••• *l •••!••! gf««*«a {tl|*. i Mi J).
•*•-! ttap •>«•» k* !• • vertical p**ttl««. It |« ai(*c«4a4 kf
c*ll-cyp« c**4«*»«i, *!•* *fl«Bt«4 **rtlc*llf. vltk clrcvlatl
c»l| v*t«|. £•• *ajtatl*| tk« **vk**t •*4nl« mttft k«
<10 C {••§}. «•• t«ap«r«t
(tap k«tk
k*
•«•! k*
(• *••! tk* ••r»«»t-
DR
tk« vartlcal p*»ltla*
rout *t ••!• ta)fl»g«r* «llk c*a*«cttii| fitting* abl* t* tar*
laak-lra*. vaCMua-tlgkt •••!• «l(fc««t acalcat |taaa«« wk*a CCH-
••ct*4 t«g«tk«c, akall •• «*«4. All (••t«f*r« «r* cf cfc*
6>B*«kHfg-Sattk •••!•• **iifl«4 kr raplactag tka t If wttk 1.1 cm
(I/a la.} 1» gl»«« tMk* ••t«*il*| t* 1.) c» (1/1 !••) tt»m (fa
•! tk* fleck.
1.1,1 Matarl«M tl«t««
Tka ••!•(!•! ay«t«03 *k«ll caaatit ml • vacima g«u§«, • l«ak-
fr*« P«"P, tkai«BOia*«»» capable *f •••••(lag tanparatvia t* *itbla
3*C (-i*»). a 4ry gaa »)atar vltb I p«tea«t •cc»r»ef at th«
i«^ut<*4 •••plt>| i«t«, aa4 r*lat«a a^wlpataat, or a^ulvalvat.
7.1.10 «roa>at«r
f*
.• CM
I/I In. I
or «lh«r b«ro»*t*r» capable el aieaewrliig
Ic ft»»matm (0 wltkla 2.3 Hg (O.I 1*. Mg > ckall be
oo. 4.r
la 1/4 i
-------
DRA
ta.ulto.aat
1
0)
' S^
^
:'-;!*£
1 °
1
u
•
5
1
1
m
9
I
3
o
o
Ci»jt»4
or it«ooa
rail
To c*f off •4>«rb«nt (ub« a«4 tk« «tlt*r ••
tto«« •! Ik* teal*. If TfK* *ci*w c«aa«ctlea« «t«
•c(«» cap* ahalt •«
jottli
Iff
Tkr«« JOO •!. ••!(••• •• . 0011AS*. «r •^
.» froM ••< Tt«««l«r H«« imgfc
of aulll-
ctoat loagtli Ifcat t« coapatlklo «ltk Ch« llaar or *r«»o a«4 traoa
fac ll«a.
»t»r«jt
• ••1*4 flltar koldar or practaaaaa1. vl4a-aoutk aaioar glaaa
caatalaara wick Ife*-ll«a4 aciaM ca»a or Mrapaa4 !• kaaaaa claaa4
1*11.
•» •»!••<•
tiiflo kaaa. Okaua >o4al ISO), or
.i AU»iiiii» rat!
J.J.I fiacl»»aa4 Matai Ca»
To raeavar »aa4 alllca |al.
I.I.I >t»claa»a4 Cra4aata4 Crltaaar. a .1 . . 2SO
2)0 •!, «itk I •! (coovatloas. koroalllcata |laaa.
1.2.9 tttutj jaaula »tora«a Co»taio»fi
•••at (laaa kottlo* or claar (laaa kottlo* vraf»a<
!• apa^va aiatallal, I L. vlth Tf£*-J*aa< acrav capa.
i.l.l
— rtbarilaaa »aawa-*ajal
AH or Ia.ul»ajaa|
filer to uaa la th* ll«la. aaclt lot al filter* ahalt •« auk-
to pracl«anlo| and a ^uatlty coatroi (QC) coat ••ln«( 1»»
chack to conflra tkat thara ara no contaolnanta piaacnt tkat «ll
-------
t*rf*r* «itk tfc*
• It*.
*'
**
t*tf*t 4*t*cti*a
If p*rf*r*«4. flll«r pi*cl**«l*g *b*ll c***l*t *l g«ibl*t
rr«cll*«, 1* k*lch** »*t *• ••£••4 SO filler*, nick tb* *»i-
)•((•) t* b« *pplt«4 t* Ik* M*I4 **«pl**. A* • QG ek*ck, tk*
ttr«ctl*g ••!•••«(•) *h*ll k* *Mkj*ct*4 t* tk* •*•* **»e**tt«-
• *. cl***«p **>4 ***ly*i* pr*c*4«t** t* k* n**4 f*r Ik* 11*14
>•*!*•• Tk* k*ekgr*«»4 »l fcl**h *•!«• *k**t**4 *k*ll k* «*•-
irt*4 (* * f*| it it II k**l* **4 *k*ll k* c*rr«cl*d fat **y
iff*r«*c** I* c**e«att*ti»« f*ct*i ••!«•••• tk* <)C ck*ck
1 4 tk* *ctu*l •*•*!• ***ly*l* *(*c**i>(*
M*t*» t*tr*ct Kith lo tot I hr
M«tkyi *lc*k*l litr.ct f*r 12 hr
M*tkyl*** «,bi*ri4* Bitr*ct t*r 21 hr
•*•*** g»tr*ct f*r 22 hr
Ik* IAD-1 •«*! k* 4ri*4 ky *•* *f tk* tullawtmg t*ck*t>u**,
*f
.,,. .
ot
Cf
ilt*r •**l«*tl*>« «|
• •l***t, * f lMMi«*4-k*4 t*ck«l*,»* k**
•k*r*i
Cf - inltjjl
rt**l
*i *pjfl»«tiit, *olv**t
t* k* tk* t«*t«*t
A ...pi. ..!.« ...» *.lt.kl. ....
•111 **r»* ** * ••ti*(*et*ry c*lu>*. A 10.2 cm (4 !•,) «l*«*t*c
ffyr*« pip* •.§ • (2 ft. la«f) wltt k*14 *lt «f tk* 1AB-2 ft** tk*
•••kl*t ••tv*ct*(. Mltk *«fflci**t *p*c* |*r flut*l«tag tk* k«4
Mktl* t***r*tl*| « •!•&•!•• IAK-2 l»*i «t tk* *«lt *l tk* c* !•>•>*.
c**c**tc*t*4 *iti*ct
Tb* *.u**tit*tt*« crlt*ri*M f*r *cc*pt*kl« Iilt*r *.**Uty will
•p**4 •• tk* **t«etl** Halt crttcrt* «*t*kl<«k*4 f*f tk* 11*14
••pli*g *»4 ***l»«i* pt*g»*«- fllt*t* tk*t gl«* * k*ckgc*w*4 *r
Immk *lg**l per fllt*t gr*«t*r tk** *r •«•*! t* Ik* t*r|*t 4*t*c-
I** Halt fat tk* •••lyt*(*> *f e**e«t* *k*ll k* i*J*ct*4 f*r
1*14 M*«. •*!« tk*t *cc*pt**c* «tlt*fl* f*f flltcc cl***ll«**«
*p*«4* **t a*ly •• tk* l*k*t**t ••tcetl** Halt *f tk* •**ly*l*
i*tk*4 »ut *!*» •• tk* ••p*ct*4 fl*14 •••pi* **iu»* *»4 *• tk*
>**ti*4 Halt *f 4*t*eti*» I* tk* **api*4 *tt*«a.
If tk* filter* 4* **t p*** tk* QC ck*ck, tk*y *k*ll k* r«-
iBtr*ct*4 **4 tk* **l»**t *»tr*el« r*-***ly««4 N*til *• *ce*pl*kly
LOM k*ckgr*»*4 i***l i* *cki***4.
1.1.2 A*»»rilt« IAB-2 •••!»
fk* cl***up pr*c«4ur* »*f k* c*rfi*4 *ut In * |t«*t •••ki*t
i>ti*ct«r. wkick Hill c**t*l« *»evgk 4ak*rlit* IAD-2* r**i*
(1AO-J) f*r **v*r*l •••pll*| trap*. A* *il gl**» tbi»kl* SJ-tO ••
ID i ISO •* 4**p t>*ct*t
cup Mltk * gi*** N**l plug *>4 *t*l*l*** *t**l *er*** *i>c* It
fl»*t* D* **l:kyl*** ckl*rt4*. Tkl* pcec*** i**«l««* **f«**ti*l
1* tfc* following *t4*i.
fli* >(« u**4 t* !*•*•* tk* *al**«t !• tk* b*y t* pr***r«l*g
tk* cl*«*ll***« of tk* 140-2. Ltfuii *itK*g«* fr«t« • t«gul*f
c**«*ict*l lt*«14 *ltio(** cyli***r k** i*«t(B*ly *i*.«« t* k* *
r*lf*kl* **«rc* *f l*rg« *«U*«« «f g** lr*« fro* *tg*«ic c**c*«l-
•••!*. tk* It*.«14 *ltt*g«* cyll*4«r 1* c****ct*4 t* tk* c*lu** ky
* l**gtk *f pt*cl****4 O.fJ «• (1/g i*.) c*pt*i tukt*g. c*li*4 t*
p.** tki*ngk * k**t **«ic*. A* *ltr*g*« I* kl*4 (**• tk* cylia-
4*r, it i* **p*tt**4 !• tk* k«*t *«urc« **4 p***** tki*«tgk tk*
C*|M*B. A c**«**l**t •«*• •*«rc« 1* • v*t*t k*tk k**t«4 <*•• *
•!*•• !!•*. Tk* fl**l *lti*g*« t*»p*r*tnt« *ki»ul4 **ly ** mmtm to
t*« t*»ck *«4 »*t ***r 40 C. •«p«rl«*c* k** *koH* tk*t *k*«t SOO
| *f i**-2 «*y k* 4rt*4 •••(•tght c***ti«t*( * full l»0 t c*ii*4*c
ml n,w|4 *itt*g**.
** * *«C**4 ck*ic*, kigk pttrity t**h
4ry tk* SAt-2. Tk* kigk purity •!((«••• mumt flrct k* p****«
tkr*«gb * k*4 •* «ctiv*t*4 ck*rc**l *ppr*stB*t «ty 1)0 uL tm
«*!••*. Witfc *ltk*r typ* of 4tyl*g »«tko4. tk* r*t* of fl*«
*k**l4 |**tty *glt*t* tk* k*4. IBC***!** flul4«tlo* m»r c**** tk*
psctlcl** t* kr**k up.
(•) AI •• *lt*t**t*. if tk* *ltr*g** prac*** 1* not •**ll»kl*> tk«
lAt-2 »*y k* 4(1*4 i* • «*cuu* «»«*. if tk* t«*p*t*t«f« **««c
*BC*«4* 20*C.
fk* IAB-2, *«*• if putch**«d el«««. marnt k* cb«cli*4 tot koch
n*thyl*** ckl*(t4* **4 k***** t«*l4n**. plu* •«!••! *!**•• »«lor*
«.•«.
5 o I » ta I
Initial lint* with 1
L H^O
for 1 cycl*.
Storage of CJ»»» IAI>-2; IAD-I cl««n«4 mad drl.d •
*»««* t* *Hlt*bl* for l***4lal« u«« 1* th* field, jiowliti It
p«««** th* QC co»t ••ln«l torn check dticilfacd In (4), b*lo». *
miimi . •t*cl**n*4 dry IAB-2 •*? d*««la* u*«cc*ptabl* !«>•)* *f
-------
UKAI
If praelaaaa4 1*0-1 ta not ta k« u««4 l»«41at*tf, *» akall
•tara4 aadat 4tat 1 1 l*4-la-glaaa aiatkaaal. HQ .„!• lh*n t»
prlar ta taftlatlaa af II»I4 •••fling, ch« ••<••• *atka*al akatl
ka 4acaat*4( tka IAD- 2 she 11 k« •••k«i Mlth • •••!! ••!<•** *f
••tkfl«i>« ckivtii* «»4 4rl«4 vltk «!••• nltr*t«« •• 4«ccrlfe«i «•
(M ah***. *• •lif«*t phall (»•• k« tain** lor tha QC c«»ta»l«»-
tt*« chaclt 4aacil»a4 !• (4). kalav.
II Ik* atarad IAB-1 falla tk« QC ckack. It mmf ka raclaaaa4 »;
ra»aaci*| tka fl*ai t«a ataaa af tka aatiaetiaa aa««aa>c* ak««ai
••^•••tial a)*tkpl*«a cblarMa aai kaaaaa ••trsctlaa. Tka fC
caataalaattaa ekacfc akall ka tapaataJ aftac tka I*»-l I* r«cl*aa*4
QC Caataalaatlaa Ckacki Tka IAB-2, vkatkac »»refc«aa4. "pva-
claaaa«"*, ar ciaaaa4 •• tfaacrlkai *k**a. akall k« ankjaetai te a
QC ckack la eaaftr* tka akaaaca af aay caataal*aata tkat atlgkt
cawaa latarlaiaac** la tka aakaatMaat aaalyala af fl«14 •«*»!*•.
AM all^aat al lift- 1, aqaivalaat im alia ta aaa flat* ••*»ti*.f taka
ckarfa* akall ka lakaa ta ckaractatlta a >l»«la katck *f 11»-1.
Tka IAB-I allfnat akall ka aakjactal ta tka a«»a •mtiaetla*.
caacaatrattaa. claaawa. aai •••Iptlcal ptac«4ttr a(al *• ta fata) te
ka afaliaf t* tk* flala* aaapla*. Tka a,«*«ti tat I va cittacla f*i
aceaatakla IAB-I ^aalltf '11 4apaai aa tk* aatactiaa Halt ett-
tarla aatakllaka4 fat t*. ial< aa*ptlai *•* aaalyala »raft>«.
•AB-t wkiek ftalia a kackt(aaa4 at klaak alfaal gtaatar. tkaa ar
*4«al ta tkat cat raapaia t •( ta a*a-kalf tka MDL far tka aaalft«(«)
*f caacai* akall ka rajactatf far ftala* aaa . H«ta tkat tk* accapt-
aaca ll*it fat &A*-2 claaallaaaa iapaa^a aat ••!> a« tk* lakataat
4atacclaa ll*lt af tka analytical «atka4 k«t alaa ** tk* aa»acc«4
fla!4 aaapla ••!«•* aa4 *a tka 4a*ica4 Halt af 4atacti*a la tka
aaaplad atraa*.
t.l.l Ciaaa Maal
Ctaaaa4 ky tkarait|k rlaalni, l.a«. ••^uaatlal taavralae la
tkraa aliqvata af kaxaaa, itlai 1* a I IO*C avaa. mm4 atata4 la. a
ka«*aja-«a*k*4 glaaa jar >ltk IPI*-tlaai aciav cap.
•.!,* Hatat
Bal**l*a4, tkaa |laa*-ilat Iliad, a«4 atarai
caacataara vltk Tfl*>ll*aJ acraa capa.
kaxaaa-rlaaai
• . 1.5 Ulff 6fi
fig. 4 1AD-I
*pp«ratu*
Ia41eatlag typa, *-l* aiaak. If pra*la«alf «*a4, 4ry at
f*t t ki • •*• atllca gal «af ka «a«4 aa tac«i*«4.
•.l.i Cfftkaj jca
flaca ciwakai lea la i><* aatar katk *caua4 tka l*plagata
Jar lag aaapllag,
-II-
-II-
-------
jAHftt EECOVE»» fEACEMTS
DRAFT
UKAN
Acataaa
PaatlcI4a Duality. attt4lck and Jackaaa ~Dlatllla4 la Claaa'
tvalaat. at«ra4 la original caatalaara. A klaak •«•( ka
aaaa4 km tka analytical 4atactlaa aatko4.
• f
••atlcl4a Duality, Iur41ck aaa1 Jackaaa *Bt*tlll«4 !• Claaa
itvalaat. atara* la arlglaal caataiaara. A klaftk •«•( ka
••••4 ky tka analytical 4atactl*n aatka4.
MOCEPUii
Cawtloai
Sactlaaa 10. J.I. I mm* 10. 1. 1. J shall ka 4ooa I* tka
lakat atary .
.1
•' •* ftataat rraaaratlaa
All train coaipaaaata akall ka •atatalo«4 aa4 callkrata4
cor4lag to tka araca4ura 4aacllka* 1* AfTO-OS}* ••!••• atkarwlaa
actfla* karata.
Ualgk aavaral 200 ta 100 t p»rtlo»» of alllca |«l !• alr-ti|kt
•*•!••(• to tka oaataot O.J (. K«coi4 tka total waifkt o| tka
llea |«1 alua cootalaat, •• aack co>talo«r. A* •• altaraatl««.
• ctltca gal ••} »• Mal|ka4 41r«ctly !• It* la»l«|at or ••••llag
>14or jitat ptior t« trala
•alact • aoisla alca kaa*4 aa tka raa(a of valoclty kaa4a
•uck tkat It ta aat aacaaaary t* ckaaga tka oattla al«a !• or4«r
to aalatala laaklaattc •••attaf rataa. »«.(!.« tka roa 4o aat
ckaaga tka aa»Ia alaa. laaura tkat tka prapar 4Itfaraatlal
praaaura fauaa la ckaaaa for tka raaga af valaclty kaa4a
aaca««atata4 (aaa tactlaa 1.1 at IPA Hatko4 1).
•alact a avltakla aroka laagtk auck tkat all travaraa polata
cao. ka aa«pla4. Par larga atacha. caaa!4ar aa.pllag fro. a.poalta
a!4aa af tka atack ta ra4»ca tka laagtk af arakaa.
• alact a tatal aaapllag tla>a graatar tkao or a^ual to tka
• !•!•••• tatal aaaipllag ttaa apactfla4 la tka taat araca4uraa for
tk« apaclflc ta4«atry a«ck tkat (I) tka aaaaltag ttaa par polat la
••t laaa tkaa 1 •!•., a«4 (1) tka aaapla valuaa takaa (carracta4
ta ataa4ar4 caa41tlaaa) vlll aicaa4 tka ra«y|ra4 •lala.ua tatal gaa
aa*pla valuaa 4ataralaa4 la (actlaa t.l. Tka lattar la kaaa4 a a.
aa apftaBtaata avaraga aaapllag rata.
It ta racaa>aa4a4 tkat tka anakar af atautaa aaapla4 at aack
polat ka a* latagar ac a* latagat pUa aaa-kalf alavta. la ai4ar
ta aval* tl«a-kaaplag arrora.
IO.I.I.1
Clatawaia
Ckack Illtar* •lavally a|*loat ll|kt (o( I r cafular I t la«
aw* or »lnk«la loaka. faek tka Illtara flat IM a »raclaa*a4
iaaa coataiaar or wra^aad ba*aaa-rlaaa4 alualauai fall*
1. 1.1. 1 riaUataary Datgra)iaat iona
(•lact tka aaa>alla.f alta ««4 tka olnlaua auak*( af •••plla|
atata accar4laf ta «FA Natko4 I. DatarBlaa tka atack praaaura.
taiDaratura. aaa1 tka raa|a al valaclty ka*4i uato| cr* Matka4 1)
t la i«eoo»«»4a4 tkat a laak-ckack of tko pltat liaaa (aaa irA
ttko4 I. Sac. 3*1) ka aarfaraia4. Oatarailaa tka •olatura coataat
•!•( EPA Appro>l«at lea Hatko4 4 or Ita altaraactvaa far tka
itrpoaa of aaklai laoklaatlc aanpllnl r al «-•« t tlaga . bicarala*
K« atack gaa 4ry aelacular wal|kt. •• 4*«crlka4 la EPA Hatko4 2.
• c . )••; If lata|ral*4 EPA Hatko4 3 »aaiplla| la ua*4 for aolacu-
ar w*l|ht 4a(ar«laat loa. tha lata|rac«4 ka| aaapla akall ka takan
I mu 1 1 *n«ou« I y wltk. aa4 tor tka aaaia total laagtk of tla« aa . tka
f>A M.cl.od 4 aaapl »»| •
All glaaa parta af tka trala upatraaaj of aa4 lMelw4lng tka
aarkaat aia^Mla aa4 tka llrat laplagar akau!4 ka claaaa4 aa
4aacrlka4 !• lactlaa JA af tka 1*10 laaua af "Haaual af Aaalytlcal
Natka4a far tka Aaalyala af raatlc!4aa la laajaaa aa4 Eavl raaaaat al
Ia«plai.* Ipaclal car* ako«14 ka 4a«ota4 to tka raaaval at raal-
4«al alllcaaa graaaa aaalaata aa gioua4 glaaa caaaactlaaa af naa4
llaaavara. Tkaaa graaa* ra*14uaa akou!4 ka raao*a4 ky aaaklag
aa»aral kaura la a ckro»lc ac!4 claaatag aalvtlaa artar ta raattaa
claaalag aa 4aacdka4 akava.
10. 1. 1.1 Aaifcttitti IAD-1 taala Trap
Haa a auftlclaat aaouat (at laaat 10 gaia or S •••/•' of atack
gaa ta ka aaa>pla4) af claaaa4 EAK-1 to fill coaplataly tka glaaa
aackaat trap wklck kaa kaaa tkatougkly claaa«4 aa araacrlka4 aa4
rla.a*4 vttk kaaaaa. tallav tka IAA-2 wltk k«Maa«-r I*«a4 gla*a
waal aa4 cap katk aa4a . Tkaaa capa a haul 4 aot ka raajo«o4 aattl
tka trap ta fltta4 lata tka trala. Saa Pig. I l«( 4»talla.
Tka 41aaaaloaa aa4 IAO-2 capacity af tka aorkaat trap. aa4 tka
• oluaa af gaa ta ka aaaipla4. akou!4 ba *arla4 •• aacaaaary ta
aaaura afftclaat collactloa of tka apaclaa o< lataraat. Coaa
1 lluat latlva 4ata ara praaantad la takl« I.
10.1.2 Praaaratloa of Collact|qi» Ttaln
During praparatlon an4 aaacaibly ot ih« •••pllng train, keep
• 11 trala opaa.ln|* what* cont aal n«l 1 oa. can antar co«
-------
,
•» !• •«
• is s
o «•» si
o «•» ••<•
• . * • •» •
3
. 2
3 1
I
5
I*
•4 •
•8 f
s 5
! =
S M
-4 .•
1 S
•9 M
M J
! 3
Dl
Jn*t prior to •••••bly or until ••••!!•( !• about to k«gl».
Bo o.ot u«« »««t««t tc«>»«i j« •••«»blt«i th«
•••r*ila«t«ly 100 ••• of wator i* ••ch of tko flrot two
l«ol«tor« vltli • |t««u*t«4 cfliooor, ••< !••*• the third lopl«|«r
o«ftT. Ploco •••roilaotolf 100 to 300 g or «or«. If ••c*«*icf. of
• Illc* |«t !• th«
oo ttt« o«t«
•hoot,
*•••••!• tli* ttklo •• *li*Ma !• Fig. I.
•loco ctM*lio4 Ico to tko Motor both (round tho
10. I.) took Choct rrocooaroo
10. 1. 1.1 JiitUi Loofc Cfcocfc
Tho trolB. iBcluoloi tho orooo. will ho look chockod prior to
ho log locortod lot* tho otock oftor tho •••pllttg trslo hoo hoao
•o*««hlo4. fora OB oo4 oot (If oppllcohlo) tho hoot log/coollog
o«otoa(a) to cool tho ooaplo goo yot roaolo ot o tovporotoro
oofflcloot t* o*o!4 cooo«««otloo I* tho >roho o>4 cooooctlog lino
to tho flrol loplogtr ( opproilaottly 120 C). Alloo tlao for tho
toaporotoro to otohlllso. Look chock tho trolo ot tho ooospllog
•Ito hf plogglog tho ootilo «lth o Tff* plvg o«4 polllag o 110 ••
•g (II !•. Ig) «ocy«o). A lookogo.roto la ovcooo of 41 of tho
ovorogo ooBpllag roto or O.OOJ7 B /B!B (0.02 elm) ohlchovor lo
looo, to BBoccoptohlo. Sooollog Bwot coooo If ptoooor* 4ortog
ooBpllag omcoo4o tho look chock prooovro.
Tho follotilag look chock lootrvctloa for tho ooapltag trol«
4oocrlbo4 la AW-OSIt' oo4 AfT»-OJil* Boy ho holpfol. ftort tho
p«ap with hfpooo »ol»o fwlly opoa oa4 cooroo o4Juot «olvo coo-
plotoljr clooo4. tortlotly afoa tho cooroo o4juot *«lvo oo4 olovly
clooo tho hypooo «ol*o «atll HO BB Ig (12 la. Mg) VOCMMB lo
roocho4. >o apt rovoroo tho 4lroctloa of tho hypooo «*lvo. Thlo
•til coooo ••tor to hock «p tato tho probe. If 3(0 BB Ig (12 to.
•g) to o«coo4o4 4vrlog tho toot, olthor look chock ot thlo hlghor
VOCOOB or oa4 tho look chock oo 4oicrlho4 holov oa4 otort tho toot
••or.
Hhoa tho look chock lo coBploto4. flrot olovly roaovo tho TH*
plog froB tho lalot to tho probo thoo laBo4lotoly turo off tho
•OCBMB p«Bp. Thlo pro*oat* tho «otor ta tho laplagoro froB bolog
forco4 hock«or4 tato tho probo.
10.1.3.2 Look Chocfco Ourtoj o To»t
A look chock oholl ho porforao4 hoforo oa4 oftor o choogo ol
port 4«rlag • toot. A look chock oholl ho porforao4 hoforo oo4
oftor • coBpoaoat (•••-, flltor or optloool Motor kaockout tf«f)
to choago4 4«rf*g o t«»t.
-16-
-------
UKA
Suck laak ckacka akall ha parfor««4 accof4lag ta tha pioc*aur*
1*** I* tvctlaa 10.I.I.I af tbla Bathe* a»capt that It ahall ba
irl*r«*4 at * »«tuu« aa.ua 1 t* *r graataf tha* tha blgbaat valiia
>cor4«4 up ta that polat 1* tba taat. If tba laakag* rata la
>«*4 1* ba •* graatai tha* 0.000)1 *>/•!• (0.02 ft /«!*) *r 41 af
ia ***raga aaapllag tat* (Mklchavar |a aaallar) tha taault* ara
scaptabla. If. havavai, a hlghar laabaga rata la •baar»a4> tba
i*t*r ahall althari (1) r*car4 tha laakaga rata a*4 tka* correct
i* valu*« *f gaa •••pl«4 alnca th* laat laak ckack aa akawa 1*
ictlaa 10.1.1.4 »f tbta •*th*J, ar (2) *a!4 tha taat.
1.1.1.1 >«a|-taat Laak Cbach
A laak chack ta •aaa'atatjr at tha a*4 af a taat. Thla laak
hack akall ba parfar«a4 1* *cc*r4a*c« with tha ptaca4ura gt«a* 1*
•ctloa 10.1.1.1 aacapt that It ahall ba caa4uct«4 at * **cuu*
a,ual to ar graatar tha* th* blghaat ••!«•• racar4*4 4urlng tha
aat. If tha l*akaga fata 1* Iaun4 t* ba *• graatai tba* 0.000)7
/•la (0.02 ft /•!•) ar 41 af tba avaraga aa*pllag tat* (whlck-
•ar 1* an»llar). th* raculta ara acc*pt*bl*. If, havavar. a
Ighar l*aka|* t*t* la *kaar«a4, th* taatar ahall althart (1}
•cor4 tha laakaga vat* aa4 carract tb* valuta aa gaa aa*pia4
Inca tba laat laak chack *a abav* 1* lactla* It.1.1.4 af tbla
•tho4, *r (1) »a!4 th* taat.
0.1.1.4 Corr*ctlnt far t«c«»fl»« 1-aakaga iitat
Tha a^uatl** glvan In Sacttaa 11.3 af tbta •«tk«4 far calcv-
atlag V (*t4)( tb* c*rcact*4 *alu«* «f gaa •••pta4, ca* b* u««4
>a urlttan u*taaa tha taakag* rata *baar*a4 4«rlag a*y laak chaci
tftar tha atari af a taat a«c*«4«4 L^, tha •••!•»• accaptabla
i**kaga rata (aa* 4afl*ltl**a kalav). If a* *kaar*a4 laakaga r*ta
i>caa4a t , tka* raplaca W 1* tb* aa.«atlaa t* gactt** II.1 «llh
ih* f011«fll*g atpraaalani
»harai
W - Volun* of gaa •••»ta4 aa **aaura4 by tka 4ry gaa
natar (4act).
L - Ma«l*u* accaptakla laakaga tata a^ual t» O.OOOS? •/•!•.
* .« «, ltj/.l«) ar 41 *| tk.
*, * gaaatfag tlaa latar««t bctwaaa tit« aucc*»«l«a laafc ckacka
kagt**l*g ultk tka l*tat*al katwaaa tka (lot aa4 aaca*4
laak ckacka, •!*.
• • Sa«fll*g tla>a latarval katvaaa th« laat (a tk) laak ckack
p
a«4 tka a*i af tka taat, *la
• ukatltuta aaly lat tkaaa laakag**
10. I. 1.1 Tr»«« Oaaf«tla*
at tf) uklck amc.a4a4
(0.02
wkicka»ai la aaallac.
L -
tka aoafaga aa*alt*g fata,
okaatva4 4urln| ih« poat-taat laak ck*ch.
/*l*
•wrlag tka taajallag tua, a a**plt*g rata ultkl* 101 of tka
aalacta4 aa*allag tata akall ka •al*talaa4. ilata Mill ka caa-
a!4aia4 accaalakla If taa41aga ara racar4a4 at laaat a«*rf J •!*.
a*4 aat atata tkaa 101 af tka a»lat taa41aga ata ta aacaaa af *|OS
aa4 tka avaraga *f tba f«l«t raarftaga la wltkla £101. ftuflag'tka
rwa. If It kacanaa aacaaaatf ta cbaaga aay ayataat eanaaaaat la aay
• ait af tka trala. • laak ckack eiuat ka §arf*raa4 artar t*
raatartlag.
far aacfc rua, tacor4 tka 4ata r*^ult«4 on tba 4ata akaata. aa
amaa.pl* la akan* 1* ilg. 4. ta swca ta facor4 tka laltlal 4rp gaa
•atar raa4l*g. gac*t4 tka 4ff gaa «atac taa4t*ga at tka kaglaalag
a*4 a»4 af aack a**pli*g ttata lacr«*«at a*4 «kaa •••fling la
kalta4.
f* kagla •a«pll*g, raaova tka *a««la c«p. varlfy flf appllc-
akla) tkat tka ptaba aa4 a«rka*t *a4ula taaparatura caatral •»•-
taaa ara warklag aa4 at ta*par*tHra aa4 that tba praba la praparlf
paattla*a4. raaltlaa tka »raka at tka aa*pll*g palat. Ia*a41-
ataljp atert tba puap a*i *4j«at Iba flaw rala.
If tba atacb la ua4*r alg*lflca*t auk-anklaat praaaura (kalgkt
af taipl*gar ataa), taka cara t* claaa tha caaraa a4|uat ••!••
baf*r* l*aartlag tba praka iat* tba atack ta avo!4 «atar backlag
1st* tba ptaba. If *acaaa«rjr, tba pu»p *ay ba t«r*a4 a* vltfc tka
caaraa a4J*«t *al*« cl*aa4.
Ourlag tba ta*t rua, *aka parlo41c a4}uat*aata ta baap tba
prafca ta*paratnrc «t tb« pro»«r valua. «44 aara tea ••«, If
•acaaaary. aalt t* tba lea bath. Alto. parl«41cally cback tba
l«»al «a4 aar* al tba »aaa»atar aa4 *al*tala th* ta*parat«ra *f
aarbaat *a4ula at ar laaa tba* 20 C but akava 0°C.
If tka praaaura 4rap acr«aa Ika trala b«cea*a kljb aaougk to
• •ka tha aa«pll*g rata 41fftcult to ••latala, ttta test rua ckall
ba tarat**ta4 u»l«»« tba r«p^acln| of th* lllt«r coiracta tk*
proklaa. If tka ftltar !• raplac<4. • l**k ch.ck akall k«
par f »(*«d .
t - Lc*k*|*
4»rlo| tht I**fc ck«ck r*t
'* " 1,1.1.-.*).
»ln
At tba a»4 ol CK« •••pic run, turn off th* pu»p, r**o»* ih«
Bioba an4 noiil* fro* th* »t»ck. end f*cot4 th* Mnal 4ij («•
•atat raa41ng. f«i
-------
o
3
Hi
•
25
"i
r
I
i
K
i
UKAI
IO.Z leaole >eco»«ry
fraper cleanup prece4ura ke|lna •• aeon •• eh* probe to
removed frea tke etack at lh« ead of tke eaapllaf period.
Wkea tka prate cea ka aafety kaadled. Mlpe off all eateraal
partlcalat* e>etter aear tk« tif »l th« prok*. Icao** tk« pt*k«
!(•• eh* tt»l« ••< el*»a •!( kath ••«• «lth b«n«ii*-il««a4 •!••!•«
1*11. •••! »ir tk« !•!•( (• tka trsla wick • |io««4 (!••• cay «r
•«• 1*11.
Till* •»••
tk«
Hl< k« cl**B
•* !••!•( ck*
to
•ncl*««4 •• tkat tk« ck«ac«* •(
•pl« vlll k« •lnl
tk« trcla prl«r t» *a4 Jurlng 4l«a«««akly and *ot«
c«««l«l«»», •.•.. broke* flitcci, color •( tko l«ol«|«r
»te. T«oot tko ••••!•• •• lollovoi
•O.J.I fo«t>l»or PP. I
Kltk«r coal tko •••• of tk« flltor ko!4or or corol«tly roaovo
tko flltor troa tko flltor koloor oo4 oloco 1C to It* I«oaclflo4
coacoloor. ••• • pair of •rocloaoao' t*oo*ora to kao4la tfco
flltor. If K la aacaaaary to fold tko ftltor, oo ao oyek tkat
tko tortlcalato coko la I cat 4* tko fola. Carofullr traoafor to
tk« coatalaar aoy acrtlCHlat* oiattat ••a/or ftltar flkor4 vklck
•akaio to tko ftltar koloor gaakat . kf «al«| a ary loort krlatla
kraak a«4/or a akarp-a4|o4 kla4a. Soal tka cootaloar.
10. 1. 1 torkoat Mo4yloa
•••••• tko oorkoot Bo4iilo fro* tko tralo ao4 caf It off.
10. I. 3 Crcloao Cotck
If tko oftlooal cyclooa la «ao4. onaiit Itat I wolf racovor tko
partlcMlata lato o aaaola contoioor ao4 cop.
10.1.4 ianalo Coatalaot jo. I
O.«oot Itatlvoly rocovor •atotlcl 4opoalto4 la tko ooicla.
praka. traaofar ilaa, tka fraat kalf at tko flltor bolder. oa4 tka
cyclaao. If »a«4. flrat by broaklaa, aa4 tkao by eee,iteot lal ly
rlaalaf wltk acotoaa aa4 tkaa koaoao tkrao tla*a aack aa4 a44 all
tkaao tlaaoa to Coatalaor Mo. 2. Nark loval at Honl4 aa coa-
toloor.
• 0.2.5 «aa»la Cootalmr Ho. j
Klaao Cka kack kalf of tko filter bolder, tke cooaoctlef llee
kotvooa tka filter oa4 tke coaaoaeer *a4 tke coo4eeeer (If oaieg
tka aeparato ceae'eaaer-aorbeat trap) tbree tlaea aeck «ltk acetone
-JO-
-------
UIV/.I
• ana collacttag all rtnaaa In Caatataar ]. If uaiag tka
• 4 coa4a»aar-aarkaat trap, th* rt*aa af tka caa4aaaar «h«ll
faia*4 I* tka i*k*v*l*iy altar i*****l el tka IAO-1. II tka
>al watar kaeekaut trap kaa kaaa «aploy«4. It ahall »•
>4 aa4 racai4a4 aa.4 It* eaataata piac«4 1* C»«t«t««v J (long
h« rlaaaa *( It. •!••* II tfctaa »!••• aack wltk acataaa,
>••••. Mark !•••! *l l(«.u>4 mm ceatalaar.
rkar
r.«4
aaatt. Cfaf » r Ho. i
«ff th«
th*
i»ova tka lltat
t«r t* !•«*•«
!• chxt. P»ut the caattftt*
!•••• 4lt«ctly !•<* G«»t*ta«V ••* 4. •!••• tk« laplagat
itlallf thr«» (!••• with •c«toa«> ••< k«»B*. Mark t«**t ml
I *• t»«l«l»«i.
I S«i»t« CoiH»l»«r Ho. i
at4
tc
- Bara»atrl« araaauta at tka •••plin( ati«, •• Hg
C ta. Mg) .
- AaaaUta ataek gaa acaaaura, aa Hg (la. Mgi.
" StaMaid aaaaluta **aaaura. 7*0 .. M( |if.t3 |..
Hg) .
- I4«al gaa caaataat. O.Oallt •• Hg-B1/8^-.-.,!.
fll.ll I.. »g-U^*g-la-«ala), *
- Akaalnta avaraga 4ry gaa a>atat ta«patatur* *I C*»).
• AaaoUta avarag* atack gaa ta*paratiira *t C°«).
* Icaa4ai4 akaalvta taaaaratma. Jtl°I (i«°f).
*kk*t
4 ««t|kt *• 4*c« «k««t. laptf tk< «••*••!• *»i !!••*• !*(•
!••( Ma. S. •!••• aaefc vttfc 4t*tlli«4 •! ««C«r thra« ttmmm,
* fatal aaaa al
•lllca gal.
» taluaa al gaa aaapl
4c* (4cl).
callacta4 la laatagaia a«i
•aa*ur«4 ay 4tjr ga* aatar.
tka laat laplagar. wlp* tka a«ta!4a ta raaava aaeaaalva
••4 atkar 4akrla, walgk (ataa Iaclu4«4). a«d t*cor4 watgkt
ta akaat. Maca tk* alllca fat lata tea aaik«4 caatataar.
CALCULATIONS
arry ant ealculatlaaa. ratalaiag at laaat ana a*tra 4aclaal
a kayaa4 tkat al tka •*a,«t«a*> 4ata. •aua4 oil Itgntaa altar
calculattaa*.
Hoaaact»tur«
; * fetal walgkt ol ckl«rlaata4 argaalc coapou*4> la
* atack gaa aaapla. ag.
: * Coacaatralloa af cklartaata4 argaalc caaa«wa4a la
* atach gaa, Mi'» • «*rtfcta4 ta ataa4ar4 co*4tttaaa
•I 20*C, l*d *« *f (*• r, 19.92 la. Hg) •• 4ry
kaata.
l * - Cioaa-aacttonal araa af aoc*la, • (ft ).
a
I - U«t*r vapor la tka gaa •((*••, propoitloa by volo»«.
I - r*tcant ol lanklnatlc •••pi lag.
•.. »«l«ht of u»t«r. II t/f-malt (It
*B(»l4) • Valuaa af gaa aaapla •aaa«ra4 ky tha 4ry gaa aiatar
catract«4 ta ataa4ar4 caa41ttaaa, 4*ca (4acl).
*Mfati) - Valuaa af vatar vapor ta tka gaa aaapla cartacta4 ta
ataa4a(4 caa41tfaaa, «ca (act).
», " St«ck gaa valaclty, ealc«lata4 kjr caaktiatlaa caicu-
lailaa. a./aac flt/aac).
If
1*
•
II.a
•0
100
- Matat ka> carractlaa lact«v.
- Avataga araaauta 4Ilfataatlal acroaa tka arlllca
•atar, •• HjO (ta. ijO).
* fatal aaapllag tl*a, ala.
• tpactltc gravity al a«rcur*.
* lac/ala.
- Caavaralaa ta parcaat.
Avaraga Pry Gaj Jittar T«ap«r«tuc«a»4 Ayar»g« Otlllea
fraayura Drop
Saa 4ata fkaat (rig. S).
-------
II.1 Oil C».
C.rt.ct tk. •••?!• *•!••• ••••ur*4 ky Ik* dry f.« B.t.r t.
•t.«4.(4 C..4III... IIO'C. '40 M «( <»•*/. 1>.»1 I.. HC» by
M.l.| EqM.tl*. I .
jj M
f (•!') • » » T.t4 fk«r * II.* " "l*. %.t * TYT"
" ~ —
'• .14
vk.r.i
B( - O.J.J) *«/•• Hg f.r ..trie «.lt.
• 17.*) *B/I.. Hg far B.gll.k ••!(•
II.* y.ju.t .1 M.t.r t...t
„<««, -
BT
le
(1)
vk.r.i
K. - 0.00114 .'/.I f.r ..tele
- 0.0471 ft /.I f*r t.gll.k ..It.
II.}
0)
•!(••• !•
« *r« yr*»«t In Ik* ••• «tr««a •••••• the
••(•r«<«4 «*4 ••• • pcycht •••ttlc ckatc C« •bt*la
.*
1 -
(4)
- 0.0034)4 •• •(
• 0.00144* !• If
O«c»«tr«tio» a
J/«I - *K f«r mutrte <••!(•
tt'/al - *l t»t B«|ll*k ••!(•
Orj««lc C>«>»u«4» !• tt«ck
In
»t»ck
*f ckl«il««t«4
J.
-IJ-
It*/.'
IS. QHtLITf ASSUDAHCI (QA) r.OCCBUKEC
..4.
ri.u
If M.kl... ...
.,
Tk. 11.14 kl..k. .k,.!4 k. ..k.ltt.4 ..
c.ll.ct.4 .« ..ck Mr»lc«l.r (..
-------
ANALTTlCAt PROCEDURES TO ASSAY STACK (FFIUCMT
SAMPLES AND KS10UAL OMUST1M PRODUCTS FM
01RCK20-P-010IINS (PCDO) AMD POUCHUMIHATED Ollt«Ofl*AHS (WDFJ
C - CNVllQMHENTAi STANDARDS UOMCSNDf
TNC AMERICA* SK1CTT OF MECHMICAt ENCINCIRS. U.S. DCMHTlCNT
OF ENE1SY AND U.S. CNVlUMMEMTAi MOTCCTION AKCNCV
S£PT. II, ltS4
RcvtMd
0«. it. 19S4
-------
DRAFI
Scope and Applicability of Method
The analytical procedures described here an applicable for the
rmlnatlon of polychlorlnated dlbenzo-p-dloxli«(PCOO) and dlbenzo-
ns(PCOF) In stack effluents from combustion processes. These methods
also applicable to residual combustion products such as bottom and
tpltator ash. Ihe methods presented entail addition of Isotoplcally-
led Internal standards to all samples In known quantities, extraction
he sample with appropriate organic solvents, preliminary fractional Ion
cleanup of the extracts using a sequence of liquid chromatography
mns. and analysts of the processed extract for PCDO and PCOF .using
led gas chromatography • mass spectrometry (GC-MS). Various
ormance criteria are specified herein which the analytical data
satisfy for quality assurance purposes. These represent mlnU
eria which must be Incorporated Into any program In which PCOO
PCDf are determined In combustion product samples.
The toxicological data which arc available for the PCDO and PCOF arc
far from complete. That Is. the toxicological properties of all of
the Isomcrs comprising the IS possible PCOO and IIS possible PCOF arc
not presently knoMi. However, a considerable body of toxkologlcal
data exists for 2.3.7.8-TCDO which indicates that. In certain animal
species, this compound Is lethal at extraordinarily low does and causes
• wide range of systemic affects. Including hepatic disorders. carcinoma
and birth defects. Millc much less data Is available regarding the
toxicology of 2.3.7.8-TCOF. sufficient data Is available to fora the
basis for the belief that 2.3.7.8-TCDF Is stiller In Its lexicological
properties to 2.3.7.B-TCOO. Relatively little Is known about the tornI-
cology of the higher chlorinated PCOD and PCDF (that Is. pent* through
octachlortnated rtOO/KOf). although there Is sow data to suggest that
certain penU-. hexe-. and hepU- PCOO/PCOF tsomtrs are haiardous. In
view of the extraordinary toxicIty of 2.3.7.8-1COO and In view of the
exceptional biological activity of this compound (on the basis of enzjmo
Induction assays I and of compounds having similar oolecular structures.
••tensive precautions are required to preclude exposure U personnel
during handling and analysis of materials containing these compounds and to
prevent contamination of the laboratory. Specific safety and handling
procedures which art recommended are given In the Appendix to this protocol.
The method presented here does not yield definitive Information on
concentration of individual PCDD/PCOF Honors, except for 2.3.7.1-
achlorodlbenio-p-dloxin (TCOO) »M 2,3.7,0-Tetrachlorodtbenzofuran
F). Rather. U Is designed to Indicate the total concentration of
tsoeers of several chlorinated classes of PCOO/PCDF (that Is. total
a-, penta-. hexa-. hepta-. and octachlorinated dibenio-p-dloxins and
niofurans). Of tho 75 separate PCDO and 135 PCOF tloners, there
22 ICOO. 38 1COF. 14 PeCOO. » PtCDF. 10 IUCOO. 16 HxCOF. 2 HpCOO.
COF. I OCOO and I OCDf.*
The analytical ncthod presented herein Is Intended to be applicable
determining PCDO/PCDF present In combustion products at the ppt to
level, tout the sensitivity which can ultimately be achieved for a
n sanple will depend upon the types and concentrations of other chemical
ounds in the sanple.
The method described here must be Implemented by or under the •
rvlsion of chemists with experience in handling super toxic materials
analyses should only be performed in rigorously controlled, limited
ss laboratories. The quantltatlon of PCOO/PCOf should be accomplished
by analysts experienced in utilizing capillary-column gas chromatogrephy-
spectrometry to accomplish quantltatioo of chlorocarbons and similar
ounds at very low concentration.
-1-
a.
The abbreviations which are used to designate chlorinated dlbenzo-p-
dloxlns and dlbonufurans throughout this document arc as follows:
PCOO - Any or til of the 75 possible chlorinated dtbenzo-p-dtoxin Isomers
PCOF - Any or all of the 135 possible chlorinated dlbenzofuran Isomers
TCOO - Any or all of the 22 possible tetrachlorlnated dibenzo-p-dtoxtn Isomers
TCDF - Any or all of the 138 possible tetrachlortnated dlbenzofuran Isomers
PeCOO - Any or all of the 14 possible pentachlorlnated dibenzo-p-dloxln Isomers
PeCOF • Any or all of the 28 possible pentachlorlnated dlbenzofuran Isomers
HxCOO - Any or all of the 10 possible hexachlorlMted dlbenzo p-dloxln Isomers
NICDf - Any or all of the 16 possible hexachlorinated dibensofuran Isomers
HpCOO - Any or all of the 2 possible heptachlortnated dlbenzo-p-o'ioxln Isomers
NpCOF - Any or all of the 4 possible heptachlorlnated dibenzofuran Isomers
OCOO - Octachlorodibenzo-p-dtoxtn
OCDf - Octachlorodibenzofuran
Specific Isooers. - Any of the abbreviations cited above nay be converted to
designate a specific Isomer by Indicating the exact positions (carbon •!<>•*)
where chlorines are located within the molecule. For exanple, 2.3,7,8 ICOO
refers to only one of the 22 possible ICOO Isoners - that iso*er which Is
chlorinated in the 2.3.7,6 positions of the ditcn/o p-dioxin ring structure.
-------
Reagents and Chemicals
Dh/:
Ibe fallowing reagents and chemicals are appropriate for use in these
rocedures. |n all cases, equivalent materials from other suppliers
ay also be used.
2.1 Potassium Hydroxide. Anhydrous, firanular Sodium Sulfate and
4itfwic Acid (all Reagent trade): J. I. laker Cfceaiical Co, or fisher
clentlf ic Co. Ike granular sodium tulfate Is purified prior to use
iy placing a beaker containing the sodium sulfate In a 400 C oven for
our hours, then removing the healer and allowing It to cool In a desiccator.
.tore the purified sodium sulfate Im • bottle equipped Mlth a leflon-
itned screw cap.
2.2 Hexane. He thy lane Chloride, lenteM. Methanol, Toluene.
Isooctane: "Oittilled I* fless* fcirdick and Jackson.
2.3 TrJdecane (Reagent firade): Sigma Chemical to.
2.4 taste Alumina {Activity trade 1, 100 • 200 mesh): ICN
Pharmaceuticals. Immediately prior to use. the alumina Is activated by
beating for at least li hour* at fttTC IN a ewfrie furnace and then
allowed to cool f* a desiccator for at least 30 minutes prior to use.
Store pre-conditioned alumina In a desiccator.
2.S Silica (Ito-Sll A. 100/200 mesh); lio-Rad. The following
procedure Is reconmended for conditioning the fto-SIl A prior to use.
•lace an appropriate quantity of Jlo-SIl Atna30omx3QOmm long
glass tube (the silica gel Is bald In place by glass wool plugs) which <
Is placed In a tube furnace. The glass tube Is connected to a pre-
purificd nitrogen cylinder, through a series of four traps (stainless
steel tubes. 1.0 cm 0.0. • 10 at long}": 1) trap Mo. 1 - Mixture
comprised of Chrooasarb H/AM (60/M nesh coated with SS Aptcion I).
Graphite (UCP-J-IOO). Activated Carbon (SO to 200 nesh) In a I:1.S:1.S
ratio (Chromosorb U/AW. Apleion I obtained from Supelco, Inc.. Graphite
obtained fro* Ultracarbon Corporation. 100 mesh. l-N-US»i Activated
Carbon obtained fro* Fisher Scientific Co.)j 2) trap No. 2 - Molecular
Sieve 13 I (60/00 e»sb), Supelco, Inc.; 3) Irap Ho. 3 - Carbosieve S*
(80/100 mesh), obtained from Supelco. Inc.; 4} Ihe tio-Sil A Is heated
in the tube for 30 minutes at ltO*C while purging with nitrogen (flow
rate 50 100 at/minute), and the tube Is then removed from the furnace
and allowed to cool to room temperature. Nethamtl (US mi) Is then
passed through the tube, followed by US ni methyl CM chloride. Ihe
tube containing the silica is then returned to the furnace, the nitrogen
purge Is *g*ln established (&0-100 ni flow) and the tube is heated at
SQ°C (or 10 minutes, then the temperature Is gradually Increased to
in,»Sr .....r ?s Minutes »nd maintained at 180 C for SO minutes. Heating
— -- i« mntlnued until the tube
. cools to room temperature, finally. the silica Is transferred to a clean,
dry. glass bottle and capped witb a teflon-lined screw cap for.storage.
2.f Silica tcl Impregnated Utth Sulfuric Acid: Concentrated sulfurlc
acid (44 g) Is combined wit* 100 g lio-Sil 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.
Ibe M2S04-slltce gel is stored In a screw-capped bottle (teflon-lined cap).
2.1 Silica Sel Impregnated with Sodium Hydroxide: IN Sodium
hydroxide (39 gl Is combined with 100 g Ifo-Sil 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 KaOH-sflfca gel Is stored In a screw-capped bottle
(leflon-llned cap).
2.1 Carbon/Cellte;
Carbon: AI-21 Carbon. Anderson Development Co., Adrian. Nlch. 49221
Celtte S4S: fisher Scientific Co
Combine AI-21 Carbon (10.1 g) with CeMte S4S (124 g) In a
2SO ml glass bottle fitted with a Teflon-lined cap. Agitate the mixture
to combine thoroughly. Store In the screw-capped bottle.
2.9 Sepralyte Olol (40»): Analytichem International
2.10 nitrogen and Hydrogen (Ultra High Purity): M*theson Scientific
1. Apparatus and Haterla Is
1h* following appiratus and materials are appropriate for use in these
procedures. In all cases, equivalent Items from other suppliers may
also be used.
3.1 filassware 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 methylcne 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 J«t described but arc
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 simples.
-------
4. Instrumentation
OR
3.1.1 Staple Vessels: 12* ML •ml 2SO el flint glass bottles fitted
with screw caps and teflon cap liners. and glass test lubes. VWH-Sclentlf Ic.
3.1.2 leflon Cap Liners: Scientific Specialities Service. Inc.
3.1.3 Soxhlet Apparatus: Extraction apparatus. Alllhn condenser.
Kimax Brand. American Scientific Products Cat. No. £6252-2A.
3.1.4 Gravity Flow Liquid Chroootographlc Columns: Custom
Fabricated (Details of the coliMis an provided IN later sections).
3.1.S Hlcro-vlalt (3.0 at): fccltance CUM.
3.2 Capillary (as Chroma tographic Columns: TMD different coliMns art
required If data on both 2.3.7.8-TCDO and 2.3.7,8-10*. as well as on
tbe total PCOO/PCOF by chlorinated class.art desired. Ibe appropriate
coliMns are: 1) A fused silica col MM (60 M x 0.2S mm 1.0.) coated
with DB-5 (0.2S v fllai thickness). JIM Scientific. Inc.. Rancho Cordovi.
Calif.. Is utlliied to separate each of the several tttra-through
octachlorlnatcd CDOs and COfs. as • froup. fro* all of the other groups.
While this col MM docs not resolve all of the I some.* within each
chlorinated group. It effectively resolves each of the chlorinated
groups from all el the other chlorinated groups and therefore provides
data on the total concentration of each group (that Is. total tctra-.
penta-. hexa-. hepta- and ocle CDDs and COfs). Ibis column also
resolves 2.3.7.8-TCDO from all of the other 21 1COO isomers and this
isomer can therefore no determined quantitatively If proper calibration
procedures are applied as described further in a later section. This
coluMi does not completely resolve 2.3,7.1-ICDF fro* the other TCOF
tsomers. and If a peak corresponding In retention time to 2.3.7.8-1COF
is observed in the analysis using this column, then a portion of the
staple extract nust.be reanalyzed using the second £C column described
below if Isomer • specific data on 2.3.7.8-1CDF is desired. 2) A
fused silica column (30 N x 0.2S am 1.0.) coated with 08-22S (0.25 »
filet thickness). JIM Scientific. Inc., Rancho Cordova. Calif., wist be
uttilled to obtain quantitative data on the concentration of 2,3.7.8-
1COF. since this column adequately resolves 2.3.7.8-TCOf fro* the other
TCOf Isomers.
3.3 Balance: Analytical la lance, reidlbility. 0.0001 g.
3.4 Nitrogen Slowdown Concentration Apparatus: N-Evap Analytic*)
Evaporator Model III. OrganoMtion Associates Inc.
Gas Chromatograph-Nass Spectrometer-Data System (GC/HS/OS): The
instrument system used to analyie staple extracts for rCDO/rCDF
comprises a gas chromatograph (fitted for ctplllary columns) coupled
directly or through an enrichment device to a miss spectrometer which Is
•quipped with a computer-based data system. The Individual components
•f the GC/NS/OS are described below.
4.1 Gas Chromatograph (GC): The chromatogrtph must be equipped
with an appropriate Injector and pneumatic system to permit use of the
specified glass or fused silica capillary columns. It oust 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 coch scries
of analyses If more than one set of samples is analysed during an 8
hour shift. Extracts of complex combustion products and effluents may
contain numerous organic residues even after application of the exten-
sive prefractlonatlon/cleanup procedures specified In this method.
Those 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 COOs/COfs must be verified.
In addition, the GC colu* illlied must be demonstrated to effectively
separate 2.3.7.8-TCOO fro* .11 other TCOO tsomers If data on 2,3,7.8-
TCOO alone Is desired with at least 201 valley definition between the
2.3.7,8- Isomer and the other adjacent-elutlng TCOO isomers. Typically.
capillary column peak widths (at half-maximum peak height) on the order
of S-IO seconds arc obtained In the course of these analyses. An
appropriate GC temperature program for the analyses described herein
Is discussed In a later section (sec Table 1).
4.2 Gas Chroamtograph-Mass Spectrometer Interface: The GC-HS
Interface CM Include enrichment devices, such as a glass Jet separator
•r • siIIcon* membrane separator, or the gas chromatograph can be
directly coupled to the MSS spectrometer source. If the system ha*.
adequate pumplnc of tne source region. The Interface may Include a
dlverier valve for shunting the column effluent and isolating the
MSS spectrometer source. All components of the Interface should be
gloss or gloss-lined stainless steel. The interface components must be
compatible with temperatures In the neighborhood of 2SO*C. which is UM
nature at which the Interface Is typically maintained throughout
tempera
analyse
analyses for fCOO/PCOf. The GC/MS Interface must be appropriately
configured so that the separation of 2.3.7.8-TCDO from the other TCOO
isomers which Is achieved in the gas chramatographic 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 arc observed, thorough cleaning of the injection port.
Interface and connecting lines should be accomplished prior to pro-
ceeding.
3.5 lube Furnace: Llndberg Type 59344.
-6-
-------
DRA
4.3 Mass Spectrometer (MS): Ike mass spectrometer used for the
inaiyses described IMC re It typically * double-(ocwv ing sector or
•uadrupale instrument •quipped Him •* electron impact source (70 ev}.
aainlatned *t 2SO C, and • standard electron Multiplier detector.
If possible. It 1» desirable to have both IBM »M high resolution
capability with IN mass spectrometer used, since confirmation of
date obtained by low resolution MS using high resolution MS Is sometimes
desirable. Alternatively. * combination of mas* spectrometers can be
used far this purpose. Ike static resolution of the instrument Must
be maintained at • minimum of 1:SOO (with • 10» valley between adjacent
MSSCS) If operating In the IOM resolution US mode, and a minimum
resolution «f 1:10.000 Is desirable far operation I* the bloh resolution
•ode. The MIS ipcctroMter mitt also bo COM floured for rapid computer-
controlled selected-loo em I tor Ug to both hlfh end lew resolutloo
operating modes. At a minimum, two Ion-masses characteristic of *ach
class of chlorinated dteaIns should be on*tiered, aod these are two
tons 1* the molecular Ion Isotoplc cluster. It Is desirable for
Increased confidence In the data to also Monitor the fragment IMS
arising from the loss of COC1 from the molecular Ion, U order to accomplish
the requisite rapid Multiple loo monitoring sequence during the tin*
period d«fined by a typically capillary ckromatographtc peak CUM base
of the chromatographlc ooak Is typically 15-20 seconds In width), the
fallowing MS performance parameters art typically required (assuming
a 4-Ion monitor I nf sequence for oach class of PCDD/PCOf): dwell time/
ion-mass. olOO msec.; minimum number of data pototi/cbrematographtc
peak. 7 . The mass seal* of the aass spectrometer Is calibrate** uslof
hlo> boiling perfluoroaeroseno and/or some other suitable mass standard
depending upon the re*u!romMts of the K-MS-05 system vt 11 tied. The
actual procedures uttltiod for calibration of the miss scale will bo
unique to the particular mass spectrometer being employed. A list of
the appropriate IMS to bo monitored to the rCOO/KOf analyses described
herein Is presented In a laUr section (see Table 1).
4.4 Data System: A dedicated computer-bated data system, capable
of providing the data described above. Is employed to control the rapid
selected-loo monitoring sequence and to acquire the data, toth dl«U«)
data (peak areas or feak kelfkts) as well as peak profiles (f'*P''p «»
Intensities of ton-masses monitored as a function of time) should he
acquired during the analyses. tMl displayed by the data system. Ibis
raw data (mass chromatogrtms) should be provided to the report of the data.
S. Calibration Standards
A recomwnded set of calibration standards to be used In the analyses
described herein Is presented below. Stock standard solutions of the
various rtDO and KOf isomers and mixtures thereof are prepared l» *
olo*ebo», using weighed quantities of the authentic isomers." Ihese
stock solutions are contained In appropriate »alw»trlc flasks and are
stored tightly stoppered, in a refrigerator. Altquols of the *«««
standards are removed for direct use or for subsequent serial dilutions
fo pr*paft wmking standards. Ihese standards must he checked regularly
• ...-_„» IP tetanic factors for the« over a period of
tlmel to ensure that solvent evaporation or other losses have not occurred
»
-*.>.».• 1COO.
- ; r — £ia-OCOO, and 2Sng/t,lllCl,-OCOf. Portions of MIS
Isomer mixture are added to all samples prior to analyses and serve
as Internal standards fer use in quantltatlon. Recovery of these
standards Is else used to piage the overall efficacy of the analytical
procedures.
S.f Standard •: Prepare • stock solution containing 1.0 119 of
•7CU-2.3.;.i-TCOOM of Isooctane. This standard can be colnjected
If desired, alone with ailquots of the final sample extract to reliably
estimate the recovery of the "C,. 2.3.7.i-ICuO surrogate standard.
S.I Standard Mixture C: Prepare a stock solution containing
100 naM of Isooctane of each of the following PCOO and PCOF;
2.3.7.1 TCOf; 2.3.7.B 1COO; 1.3.4.i.l-PeCOf. 2.3.4.4.7 PeCOf; |.2.4.?.i-
PeCOO; l,2.).*.»-PeCOOi l.t,1.4.f,i-N*COF; 2.3.4.t,7.8 HxCOf; I.2.3.4.4.B-
MxCDD. 1.2.3.4.4.7 kxCOOi 1.2.3.4.4.7.B HpCOf; t.2.3.4.7.8.»-Hp£W;
l.2.3.4,4.7.i-HpCOOi l.2.3.4.4.7.» HptOO. OCuf: and OCOO. Ibis isemer
mixture Is used to define the gas chromstooraphlc retention tine
intervals or windows for each of the penta-. hexa-, hepta-. and
octachlorlnated groups of PCOO and PtOf. Each pair of Isomers of a liven
chlorinated class which is listed here corresponds to the first and
last elutlitf Isomers of that class on the M-S caff Mary CC column
(except fer ICBD and TCOf). In addition, this isomer mixture is used
to determine SC-MS response factors for representative tsomers of each
of the penta-. hexa-. hepta-, and octachlorlnated groups of PCOO and
PCDf. The later data are used In quantItat Ing the analytes In unknown
samples.
S.4 Standard Mixture 0; Prepare a stock solution containing
SO pg/nL ef Isooctane of each of the following ICOO isomers: l.I.f.l-
TCUD; 1.2.3.7-KDO; 1.2.3.9-UDO. 2.3.?.t-TCOO; and 1.2.B.9-TCOO. iwo of the
Isomers In this mixture are used to define the gas chromatographlc
retention time window for ICOOs (M.fi.t-TCOO Is the first eluting ICOO
*• Some of the PCQO/PCDF isomer standards recommended for this mtthod
arc available from Cambridge Isotope laboratories. Cambridge. Massachusetts.
Other PCOO/PCDf standards are available from the Irehm Laboratory, ttright
State University. Dayton. Ohio, from the U.S. [PA Standard Repository
at Research Triangle Park. North Carolina and possibly from other laboratories
Not all of the indicated isotopically-labelled PCOO/PCDf internal standards
recommended here arc presently available In quantities sufficient for
widespread distribution, but these arc expected to be available in the near
future.
-------
isaner and 1,2.8.9 1COO Is the last eluting ICDR isomer on tht 88-5
CC column). Ihe remaining Isomers serve lo demonstrate that Iht 2,3,7,1-
1CUO turner it resolved fro* the other nearest eluting 1C00 isomers,
and that the column therefore yields quantitative data (or the 2.3.7.S-
1COO isoner alone.
5.5 Standard Mixture I: Prepare * stock solution containing SO pgM
of isooctane of each of the following ICOf IsoMrs: 1.3.6.8 ICOf; 2,3.4,8-
ICUf; 2,3.?.8-UOf, 2.3.4.7 ICOf; and 1.2.8.9 ICOf. Ihis isomer mixture
Is used to define the ICOf gas chromatographtc retention time window
(I.3.6.B- and 1.2.8.9 ICOf are the first and last editing ICOfs on the
06-5 capillary column) and to demonstrate that 2.3.7,8-JCOf is uniquely
resolved treat the adjacent-tinting HOT isomers.
6. Procedures for Addition of Internal Standards and Extraction of Samples
Both liquid and solid samples will be obtained for PCDO/PCDF
analyses as a result of tht application of an appropriate stack
sampling procedure. Staples
resulting from the sampling train will include the following (these
will be provided to the analytical laboratory as separate samples in
the fore indicated): 1) particulate filter and particulates thereon;
2) particulates from the cyclone (If used); 3) combined aqueous solutions
from the impingers; *,) the intact IAD-resin cartridge and the resin
therein; 5) combined aqueous rlnte (If used) solutions from rinses of
the noizie. probe, filter holder, cyclone (if used), impingers, and
all connecting lines; i) combined acetone rinse solutions from rinses
of the noizle, probe, filter holder, cyclone (if used), impingers. and
all connecting lines; 7) combined hexanc rinse solutions from rinses
of the nonle, probe, filter, cyclone (if used), impingers, and all
connecting lines. In addition, samples of bottom ash, precipitator
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
aliquot* thereof arc 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 analyied in total. .
6,1 Organic liquid Samples (Acetone and Itexane Solution!) Combine
the acetone and henane rinse solution and concentrate to a volume of about
1-5 ml using the nitrogen blowduwn apparatus (a stream of dry nitrogen)
X!ch 2uB.Turr!;,nijji.7,B.r!^*-r-* i"< *•»""
0* he.ane and add these o he colcenlrafed <' f * "Uh ***" P0rtlo'ls
further to near dryness. Ihis reside -HI {?'" lons *nd «~*»«r«te
C.2 Aqueous Liquids
Add an appropriate quantity of the isotopically-labeled internal standard
•future (Standard Mixture A described earlier) to the aqueous liquid
sample (or an aliquot thereof) in a screw-capped bottle fitted with a
lafIon-lined cap. Add approximately 251 by volume of bexane 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-
tract ION. Proceed with the sample fractionation and cleanup procedures
described below.
63 Solid Samples
Place a glass extraction thimble and ) 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, iemove the toluene and discard ft,
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
If hours. After extraction, allow the Soxhlet to cool, remove the
toluene extract, and transfer it to another sample vessel. Concentrate
the extract ta a voli-me of approximately 40 ml by using the nitrogen
blowdown apparatus described earlier. Proceed with the sample fraction*
tion and cleanup procedures described below.
1. Procedures for Cleanup and Fractionation of Sample Extracts
The following column chromatographic sample clean-up procedures
are used in the order given, although not all may be required. In
general, the silica and alumina column procedures are considered ta be a
minimum requirement. Acceptable alternative cleanup procedures may be
used provided that they are demonstrated to effectively transmit a
-to-
-------
DRA
ipresentallwe set of the analytes of interest. Ihe column chromato-
raphic procedures listed here have been demonstrated to be effective
or • mixture consisting of 1.2.3.4 ICOO. 2.3,7,i-ICDO, 2.3,6.8-1CBf,
.2.4,i-ICuf. 2.3.M-KOf, 1,2,3.7.8 PeCOO. 1.2.4.7.8 PeCOf. 1.2.3,4,7,i-
xCOO, l,2,4.t,7.t-M«CaF, l.2.3.4.».7.8-NpCOu. M.M.M.i-HpCDf ,
COO and OCOf
An extract, obtained as described in the foregoing sections is
oncentrated to a volume of about 1 «L using the nitrogen blowdown
pparatus. and this Is transferred quantitatively (with rinsings) to
he combination silica §el column described be tow.
7.1 Combination Silica Gel Column: Pack one end of t glass
:olu*n (20 mm. 0.0. * 230 mm In length) with glass wool (precleaned)
ind add, in sequence. 1 g silica gel, t g base-modified silica gel,
I g silica gel. 4 g acid-modified silica gel, and I g silica gel.
f Silica gel and Modified silica gel are prepared as described In the
Reagents sections of this protocol.) Preelute the column with 30 mt
nexane and discard the eluate. Add the sample extract in 5 mt of mexane.
to the column along with two additional S *1 rinses, flute the coition
•fth an *ddltional M nt af hexene and retain the entire eluate.
Concentrate this solution to a VOIUM of about I •).
7.2 Basic Alumina Coliwn: Cut off a 10 *t disposable Pasteur
glass pipette at the 4 nt graduation mark and pack the lower section with
glass wool (precleaned ) and 3 g of Moelm basic alumina (prepared as
described in the Reagent section of this protocol), transfer the
concentrated extract fro* the combination silica column to the top of
the column and elutc the column sequentially with li ml of beiane,
10 ml of 81 methylene chloride- In-hcianc and IS mi of SOS methyl rue
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 slowdown apparatus described earlier.
7.3 PI-21 Carbon/Cellte 545 Column: lake 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 PI-21 Carbon/Celite 54S
(Prepared as described in the reagent section of this protocol) to the
tube to fora a 2 CM. length of the Carbon-Celite. Insert a glass wool
plug. Preelute the column in sequence with 2 ml of 501 benzene-in-*tbyl
acetate, 1 ml of 501 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 I ml hexane
rtn&e. {lute the column with 2 ml of 501 methylene chloride-in-hexane
and 2 at of SOS nentene-in-ethyl acetate and discard these eluates.
Invert the column and reverse elute it willi 4 ml o( toluene, retaining
tins «luate. Concentrate the eluate and transfer it to a Reacti-Vial
for stoiage. Store extracts in a freezer, shielded from light, prior
iMh
7.4 Silica/Blot Micro Column Cleanup-
Steps small amounts of highly colored
*»
th. K
*t>01" elM«-«P
.
column: Push a small plug of alass wool u
glass -asteur pipette, followed* by j^2 '„
International ). i m of silica oel LT it it P
In. column li - " ''
1001
8.
fo1 »«•»«§
* " ! 3*
*»«l>tichem
$ulf*te
£S£Ut5SrjL£2£: {sag- * «»«»»- -
1.1 Sample extracts prepared by the procedures described In the
foregoing are analyzed by GC-NS utilising the following instrumental
parameters. Typically, I to 5 i>L portions of the extract are Injected
Into the CC. Sample extracts are first analyied using the OB-S capillary
6C column to obtain data on the concentrations of total tetra-through
octa-COOs and COfs, and on 2.3.7.8 ICDO. If tetra-COfs are detected
In this analysis, then another aliquot of the sample is analyzed In
a separate run, using the 00-225 column to obtain data on the concentration
of 2.3.7.f-lCOf.
t.2 Gas Chromalojjraph
•-2.2 Carrier gas: Hydrogen. JO Ib head pressure.
programmed (lifl'C for 1 min.. then Increase from loblC~to"240*C'§
hold at 240*C for i min.)
8.2.4 Interface lemperature: 2&0°C
B.3 Hast Spectrometer
8.3.1 loniiation Hode: Outrun inipdct (10 eV)
-------
8.3.2 Static Resolution: 1:600 (101 valley) or 1:10,000 depending
upon requirement Usually the sample extracts are initially analyzed
using low resolution MS. then If PCOO/PCOF are detected, it is desirable
to analyze a second portion of the sample extract using high resolution
MS.
Di
8.3.3 Source lemperature:
2SO°C
8.3.4 Ions Monitored: Computer-Controlled Selected-Ion Monitoring.
See Table I for list of Ion masses monitored and time intervals during
which tons characteristic of each class of COOs and COfs are monitored.
ft.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 SOO. 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 I shows the CC temperature program typically used to
resolve each chlorinated class of KOO and PCOF 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 use-* by Injecting allquots
of Standard Mixtures C. 0. 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-TCOO and 2.3.7.8-
TCOF: Utilize the column-resolution ICOO and ICOF tsomer mixtures
(Standard Mixtures 0 and t. containing 50 pg/pl. respectively of the
appropriate ICOO and TCOF Isomers) to verify that 2.3.7.8-TCOO and
2.3,7.8-TCOF are separated from the other ICOO and TCOF isomers.
respectively. A 20J valley or less Bust be obtained between the mass
chromatographic peak observed for 2.3.7.8-ICOO and adjacent peaks
arising from other ICOO Isomers.and similar separation of 2.3.7.B-TCOF
from other neighboring TCOFs. is required. Standard Mixture 0 is
utilized with the OBS coluwi and Standard Mixture I 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 |. lite
column performance evaluation must br 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
Dfiy
period of time. Its performance can also be gauged by noting the peak
width (at 1/2 peak height) for 2.3.7.8 ICOO or for 2.3.7.8-ICOf. If
this peak width Is observed to broaden by 201 or more as collared to
the usual width for satisfactory pperatlon, then the column resolution
Is suspect and must be checked. If the colun resolution is found to
be Insufficient to resolve 2.3.7.8-1000 and 2.3.7.B-TCDF fro* their
neighboring ICOO and ICOf Isomers. respectively, (as Matured OA the
two different columns used for resolving these two Isomers). then a
new M-S and/or 08-22S CC coluwi must be Installed.
•.4.4 Calibration of the GC-MS-OS system to accomplish quantitative
analysis of 2.3.7.8-TCOO and 2.3.7.B-TCOf. and of the total tetra-
through octa-COOs and COfs contained In the sanple extract.is accomplished
by analyzing a series of at least throe working calibration standards.
fach of these standards Is prepared to contain the sane concentration
each of the stable-lsotoplcally labelled Internal standards used
here (Standard Mixture A) but a different concentration of native
PCOO/PCOf (Standard Mixture C). typically. Mixtures will be prepared
to tint the ratio of native PCOO and PCOf to Isotoplcatly-labelled
KOO and PCOf will be on the order of 0.1. O.t and 1.0 In the three
working calibration Mixtures. The actual concentrations of both native
and tsotoplcally-labelled PCOO and PCOF In the working calibration
Standards will be selected by the analyst on the basis of the concen-
trations to be Measured In the actual sanple extracts. At the tine
when allquots of each of the standards are Injected (and also when
Injecting allquots of actual sample extracts). If desired, an aliquot
•f a standard containing typically 1 ng of MCK-2,3,7.B-!CDO (Standard D)
can be drawn Into the micro syringe containing the calibration solution
described above (or the sample extract) and this is then co-injected
•long with the sample extract In order to obtain data permitting
calculation of the percent recovery of the *lC,,-2.3.7.8-TCOO internal
Standard, equations for calculating relative response factors fro* the
calibration data derived fro* the calibration standard analyses, and for
calculating the recovery of the "Ci,-2.3.7.8-FCOO and the other
tsotoplcally-labelled PCOO and PCOF, and the concentration of native
PCOO and PCOf In the sanple (fro* the extract analysis), are summarized
below. In these calculations, as can be seen, 2.3.7.8-TCOO Is employed
as the Illustrative model. However, the calculations for each of the
other native dloxlns and furans In the sample analysed are accomplished
In an analgous manner. It should be noted that in view of the fact
that stable-tsotopically 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 quant I tat ion of tetrachlorinated dibeniofurans "C,,-2.3,7.8 TCOF
is used as the internal standard. For quantitation of tetrachloro-
dlbenio-p-dloxlns, l*Cu-2.3.7.8-ICOO is used as the internal standard.
For quantitation of PeCOO. HxCOO. PeCOf. and HxCOF. the corresponding
Stablc-lsotoplcally labelled HxCOO and HxCOF internal standards are used.
For quantitation of HpCDD, OCOO. and HpCOF. OCOF. the isotopically-
labelled OCOO and OCOF, respectively, are used. Inherent In this
approach is the assumption that the response factors for each of the Isomeri
-13-
-14-
-------
f each chlorinated class are the sane, and In the case of the penta-
td nepta-COOs and COfs, the assumption is nade that the responses for
MS* two classes are equivalent to those for the tetra-lsoners and the
cta-isoners. respectively.
1.4.S Equations for Calculating Response factors. Concentration of
,3.7,1-ICOO la An Unknown Sanple. and Incovorias of Internal Standards.
quatIon 1: Response factor (RRF) for native 2.3,7.8 1CDO using
t*CM-2.3.7.t-1COB as an Internal standard.
DRAFl
•tore: A( - SIM response far 2.3.7,•-TOW Ion at mji 320 * 312
A,. * SIN response for l§C41-2.3,7.i-ICOO Internal standard
11 Ian at aVi 332
C. • Concentration of the internal standard (pf./nt..)
Ct • Concentration of the 2.3.7.I.-TCOO (pg.M.)
Equation 2: Response Factor (R*f) for "q,-2.3.7.i-ICOO, the co-injected
external standard
Mff- (*i,e.§)/(*.,cul
where: A(§ • SIN response for "Ci.^.S^.i-TCOO Internal
standard Ion at
"332
A.. • SIN response for co-Injected "CI»-2.).7.«-lCDO eiternal
** standard at m/i 321 * O.OOf (SIN response for native
2.3.7,t-KOO at mji 322)
C|g • Concentration of Ike Internal standard (pg-M-)
C * Concentration of the external standard (f»9.M.)
Equation 3: Calculation of concentration of native 2.3,7,1-rcOO usinfl
"£»a-2.3.?.l-ICOD as internal standard
Concentration. M /I- « (Ag) dt)/(*u)(Mf-)(u)
**ere: A§ • SIN response for 2.3,7.1-fCOO ion at n/j 320 * 322
*1§ * SIN response for the "C|(-2.3.7.I-1COD Internal
11 standard Ion at •/! 332
l§ * Anount of Internal standard added to each sanple (pg.)
H • Iteliht ef soil or waste In or***
ilF^ * Melatlve response factor fro* equation 1
Equation 4; Calculation of S recovery of llC»,-2.3.7.«-lCOO Internal standard
I Recovery -
A, * SIN response for **Cii-2,3.?,l-TCOO internal standard
11 IM at m/t 332
A.. * SIN response for "CI,-2.3.7.B-TCDO external standard
•* Ion at mjt 321 - 0.009 (SM Response for native
2.3.7.a-TCOO at mil 322)
f. * Aeount of "CU-2.3.7.R-TCOO external standard
* co- Injected Mitk saey»le extract (n§.)
I. * Theoretical eeaunt of "Cn-2,3.7.i-TCOO Internal
1 standard In Injection
Mf. » Relative response factor from Equation 2
As noted above, procedures similar to these are applied to calculate
analytical results for all of the other KOO/rtOf determined in this net hod.
•.S Criteria Which iC-NS Data Must Satisfy for Identification of
PCOO/FCOf la San? I as Ana ly ted and Additional Details of Calculation Procedures,
In order to Identify specific PCOO/PCOf in sanples analyied. the
6C-HS data obtained nust satisfy the foil 0-109 criteria:
•.S.I Hail spectral responses nust be observed at both the Molecular
and fragment ion nasses corresponding to the ions indicative of each
chlorinated class of PCDO/PCOF identified (see Table 1) and Intensities
of these ions nwst naxfntiie essentially simultaneously (within « I
second). In addition, the chro*utogr*phic retention tines observed for
**ch PCOO/PCOf signal Must be correct relative to the appropriate
-------
DH
stable-isotopically labelled internal standard and must be consistent
with the retention time Hindoos established lor lite chlorinated group to
which the particular PtOO/KDf is assigned.
8.1.2 Ihe ratio of the intensity of the molecular ion (M)* signal
to that of the (H«2)* signal Mist be within * 101 of the theoretically
expected ratio (for example. 0.?} In the case of irnu; therefore
the acceptable range for thli ratio Is 0.69 to O.fib).
B.5.3 Ihe intensities of the Ion signals are considered to be
detectable If each exceeds the baseline noise by a factor of it least
3:1. Ihe Ion intensities are considered ta be quantitatively measurable
tf each ion intensity exceeds the. baseline noise by • factor of at
least 5:»c.
B.S.4 for reliable detection and quant I tat ion of PCOf It Is also
desirable to awnI tor signals arising fro* chlorinated diphenyl ethers
which. If present could give rise to fragment Ions yielding Inn Masses
identical to those Monitored as indicators af the fCOf. Accordingly,
in Table I. appropriate chlorinated dtphenyl ether Masses arc specified
which awst be Monitored simultaneously with the PCOf Ion-Misses. Only
when the response for the dtphenyl ether ion Mass is not detected at
the same time the PC Of Ion Mass can the signal obtained for an
apparent PCOF be considered unique.
B.S.S HeasureMent of the concentration of the congeners in a
chlorinated class using the Methods described herein n based on the
assumption that all of the congeners are identical to the calibration
standards employed in term of their respective chemical and separation
properties and in tents of their respective gas chroMatographic and MISS
spec trwne trie responses. Using these assumptions, for example, the
l§C||-2.3.?,i'!CDD internal standard is utiliied as the internal
calibration standard for all of the 22 ICDO isomers or congeners.
Furthermore, the concentration of the total ICDO present in a sample
extract is determines by calculating, on the basis of the standard
procedure outlined above, the concentration of each KOO isomcr peak
(or peaks for Multiple ICDO isomers, where these coelute) and these
individual concentrations are subsequently suamed to obtain the concen-
tration of 'total' ICDO.
c" In practice, the analyst can estimate the baseline noise by measuring
the eiteiision of the baseline immediately prior to each of the two mass
chromatographic peaks attributed to a given PCM) or PCOf. Spurious signals
nay arise either from electronic noise or from oilier 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.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 PCDO/PCOf (typically retention times for the PCDO/PCW art prolonged).
Suck extraneous organic compounds, when introduced Into the mass spectro-
Meter source may also result in • decrease in the sensitivity of the MS
because of suppression of tonliatlon. and other affects such as charge
transfer phenomena. The shifts in chroma tographic retention times are
usually general shifts, that is, the relative retention times for the
PCDO/PCOf are not changed, although the entire elution time scale Is
prolonged. Ihe analyst's Intervention in the CC 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
••tract, far example, using the program outlined In Table 1. If the
retention time observed for 2.3.7.B-1CDO (which normally Is 19.1 minutes)
Is lengthened by 30 seconds or more, appropriate adjustments In the
programming sequence outlined In Table 1 CM be made, that If, each
selected Ion-monitoring program Is delayed by * length of time propor-
tionate to the lengthening of the retention time for the 2.3.7,B ICDO
isomer. In the case of foniiation suppression, this phenomenon Is
Inherently counteracted by the Internal standard approach. However.
if loss of sensitivity due to lonlzation suppression is severe.
additional clean-up of the sample eitract 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 fach 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
from 60-90*. Since these compounds are used as tru* internal standards
however, lower recoveries do not necessarily Invalidate the analytical
results for native PCOO/PCOf. hut 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/PCOF for each set of 20 or fewer samples. Ihe
result of this analysis provides an indication of the efficacy of the
entire analytical procedure, the results of this analysis Mill be
considered acceptable if the detected concentration of each of the native
-17-
18-
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DR
:00/PCDF added ie Ike saayle Is within *SOI of the known concentration.
In appropriate »tt of native isomers to~be added here ii • set such
t that indicated far Standard Mixture C.)
9.1.4 At least OM of the samples analyzed out of each set (of 20
ample* or less) Is amalyted In duplicate and the rttults of the duplicate
•alysls arc Included in the report *f data.
i.l.S Performance evaluation staples prepared by (PA.or other
aboratorles.Hhicb contain representative KOO/rCOf in concentrations
pproilMtlnf those present In typical field samples being enalyted
but unknoMi to the analyilnf lab) should be perledlcally distributee*
• laboratories accomplish Inn, Inns* analyses.
i.l.i Sources nf all calibration and perfonHnce standards used In the
nalyses and the purity of these Materials nust be specified In the data
•port.
I. Data Reporting
10.1 Each report of analyses accomplished using the protocol
(escribed herein Hill typically Include tables of results Mblcb Include
[be following:
(or detection Halts) are reported.
10.1.i Ihe sane raw and calculated data which arc provided for the
actual samples Mill also be reported for the duplicate analyst}, the
method blank analyses, the spiked sanple analyses and any other QA
or performance sanples analyied in conjunction with the actual sanple
tet(s).
10.I.I The recoveries of the internal standards in percent.
10.1.1 Ihe recoveries of the native KOO/KOf from spiked saeples
In percent.
10.1.9 The calibration data. Including response factors calculated
from the three point calibration procedure described elsewhere in this
protocol, bate showing that these factors have been verified at least
once during each • how period of operation or Mltb each separate set
of saaiples analyied oust be Included.
10.1.10 Ihe weight or quantity of the original sanple analyied.
10.1.11 Documentation of the source of all PCOO/PCOf standards
used and available specifications on purity.
Lln/i I
10.1.1 Complete Identification nf the sanples analyied (sample
lumbers and source).
10.1.1 Ihe dates and times at which all analyses were accomplished.
this Information should also appear an each mass chroma togram included
tilth the report.
10 1 3 Raw mass chromatographlc data which consists of the absolute
Intensities (based on either pe»k ktl»hl or «*«k *r**> •' thc
observed for the ion-masses monitored (See lable 1).
10.1.11 In addition to the tables described above, each report of
analyses Hill include all mass chromatograms obtained for all saayles
analyied, as well as for all calibration, GC column performance, and
6C SrindoH* definition runs and results of column performance checks.
10.1.13 Any deviations from the procedures described In this protoea I
which are applied In the analyses of samples Hill be documented In
detail in tbe analytical report.
11. Typical Oata Indicative of Method Performance - Precision and Accuracy.
10.1.4 Ihe calculated ratios of the intensities of tbe molecular
ions for all KOO/KOf detected.
10 I t> Ihe calculated concentrations of native 2.3,7.8-UDO and
2,3,7.8-ICOf, and the total concentrations of the congeners of nach
cl*s* of PCOO/KOf for each sample analyzed, enpressed in nanograms
1COD per gr*« of sample (that Is, parti-per-btM Ion) as determined
>,«. th» r»w dau. If no PCOOVPCDf are detected, the notation "Mot
' Me roncentr**'""'
II.I Ihe method described herein has typically been employed to
quantitatively determine 2.3.1,1-lCOO in combustion product saa^les at
concentrations as low as 10 picograms/gram and as high at 100 1*9/9.
Concentrations 0f the other PCDO/PCDf which can be detected typically
fall within the range of 20 picograns/isomer/gram of sanple. to 100
plcograms/f of sample. Of course, the Halts of detection which can
be practically achieved are dependent on the quantity of sample available
-------
-ee-
. J th unt :lnd tber rfer orga esli
present In the sanple. With respect to precision, the avenge, deviation
of data obtained fro* the analyses of a nwfcer of allquots of the MM
sw*le containing the 2.3.l,t-1COO Isoner In the 250-300 ppb range
Is estlMted to be «1M or better. Data on the precision of quantisation
of Multiple PCOO/PcBf In a finale ssaple are not as yet available. As
yet, there Is Inadequate Interlaboratory and performance evaliMtlon data
available to specify the accuracy which can be expected of the analytical
procedures described herein.
a ss as
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Safety and Hand! iitl Procedures la Connection
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