EPA/600/R-96/036
November 1996
Guidance for Total Organics
Draft Final Report
By:
Robert F. Martz
Radian Corporation
P.O. Box 13000
Research Triangle Park, North Carolina 27709
Contract Number 68-D4-0022
Work Assignment No. 08
Prepared for:
Easter A. Coppedge and Larry D. Johnson
National Exposure Research Laboratory
Air Measurements Research Division
Methods Branch
U. S. Environmental Protection Agency
Research Triangle Park, North. Carolina 27711
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Disclaimer
The information in this document has been funded wholly or in part by the United
States Environmental Protection Agency under EPA Contract 68-D4-0022 to Radian
Corporation. It has been subjected to Agency review and approved for publication. Mention
of trade names or commercial products does not constitute endorsement or recommendation for
use.
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Abstract
This document provides guidance to those wishing to determine the total organics
content of source samples. The preparation of air quality permit applications for waste
combustion units require total organics data. This document identifies specific techniques to
determine the total organics sampled from stationary sources. It describes the measurement of
total organics from stack emissions and related field sampling efforts, combining the organics
from three specific boiling point/vapor pressure classes: light hydrocarbons and volatile
organics (boiling points < 100°C), semivolatile organics (boiling points 100°C to 300°C), and
non-volatile organics (boiling points >300°C). It describes methods for measuring and
reporting the individual parameters. The document seeks to avoid the confusion about
organics measurement and eliminate the misleading and non-descriptive titles often given to
different facets of organics analysis. It also provides information about combining the
component parts of the organics analysis results into a helpful description of the data. Knowing
the amount of previously uncharacterized organic material enables more accurate risk
assessment estimates to be made. Discussions of the specific methods and operating
procedures are found in the appendices and references.
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Contents
Disclaimer ii
Abstract iii
Acknowledgments vii
Glossary of Terms viii
1 Introduction/Background 1
2 Method for Total Organics Measurement 4
3 Field Gas Chromatography (Field GC) Method and
Purge and Trap GC Method 6
4 Source Sampling and Sample Extract Preparation
for TCO and GRAV 10
5 Total Chromatographic Organic (TCO) Method 12
6 Gravimetric (GRAV) Method 14
References 16
Appendices
A. Recommended Operating Procedure for Field Gas Chromatography
B. Recommended Operating Procedure for Purge and Trap GC
C. Recommended Operating Procedure for Total Chromatographable Organics
(TCO) Analysis
D. Recommended Operating Procedure for Gravimetric (GRAV) Analysis of
Organic Extracts
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Contents, Continued
E. EPA Draft Method 0040 - Sampling of Principal Organic Hazardous
Constituents from Combustion Sources Using Tedlar® Bags
F. SW-846, Method 0010 - Modified Method 5 Sampling Train
G. Method 3542 - Extraction of Semivolatile Analytes Collected Using the
Modified Method 5 (Method 0010) Train
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List of Tables
1 Total Organics Components 5
List of Figures
1 Stationary Source Emissions 3
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Acknowledgments
This document was prepared for the US Environmental Protection Agency's National
Exposure Research Laboratory (NERL) located in the Research Triangle Park, NC. The
authors wish to thank those people who have made this work possible: Joan T. Bursey and
Raymond G. Merrill of Radian Corporation, and Larry D, Johnson of EPA.
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Acronyms and Abbreviations
AEERL - Air and Energy Engineering Research Laboratory, RTP
CH4 - Methane
C7 - Heptane
C,7 - Heptadecane
Draft Method 0040 - "Sampling of Principal Organic Hazardous Constituents from
Combustion Sources Using Tedlar® Bags"
Draft Method 3542 - "Extraction of Semivolatile Analytes Collected Using Modified
Method 5 (Method 0010) Train"
EPA - Environmental Protection Agency
FID - Flame ionization detector
Field GC - Field gas chromatography, light organics collected in Tedlar® bags and
analyzed in the field by GC/FID
GC - Gas chromatograph
GRAV - Gravimetric mass, nonvolatile organics with boiling point > 300°C
heptadecane - Straight chain hydrocarbon, saturated, 17 carbon atoms
heptane - Straight chain hydrocarbon, saturated, 7 carbon atoms
Level 1 - IERL (AEERL) Procedures Manual: Level 1 Environmental Assessment
m - Meter
Method 0010 - "SW-846, Method 0010, Modified Method 5 Sampling Train"
Method 8270 - "SW-846, Method 8270, Gas Chromatography/Mass Spectrometry for
Semivolatile Organics: Capillary Column Technique"
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Acronyms and Abbreviations, Continued
mL - Milliliter
jtg - Microgram
pL - Microliter
m3 - Cubic meter
MS - Mass spectrometry
NERL - National Exposure Research Laboratory
purge and trap - Analytical technique where the water sample is introduced to the
instrument by gas purging, trapping of the gas, and desorption from the trap
QC - Quality control
RCRA - Resource Conservation ami Recovery Act
Recoverable organics - Those organic compounds capable of being collected in a
specific sampling train (Method 0010, Draft Method 0040) and subsequently analyzed
RTP - Research Triangle Park, North Carolina
semivolatile - Compound class between the volatile and non volatile compounds,
generally defined by boiling point between 100°C and 300°C
SW-846 - Test Methods for Evaluating Solid Waste, Physical/Chemical Methods, SW-846
Manual, 3rd Edition
Tedlar® - Trade name for sampling bag material used in direct collection of air samples
total organics - Combination of Field GC, TCO, and GRAV mass
TCO - Total ehromatographable organics
volatiles - Volatile organic compounds with boiling points < 100°C
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Section 1
Introduction/Background
The characterization of stationary source emissions requires screening and analysis
procedures that identify components of several compound classes. The need to characterize
emissions containing multiple organic compounds continues to increase. Revisions to the
guidance for conducting risk assessments at Resource Conservation and Recovery Act (RCRA)
hazardous waste combustion units have recently included the requirement that total organic
carbon analysis be conducted.1,2 The uncharacterized organic portion of organic emissions that
have not been specifically identified and quantified by other methods must be measured. By
knowing the amounts of previously uncharacterized organic material, more accurate risk
assessment estimates can be made. The preparation of air quality permit applications for waste
combustion units require total organics data.
This document describes the measurement of total organics from stack emissions and
related field sampling efforts, combining the organics from three specific boiling point/vapor
pressure classes: light hydrocarbons and volatile organics (bp < 100°C), semivolatile organics
(bp 100°C-300°C), and nonvolatile organic compounds (bp>300°C). The total organics
measurements are not merely a mass measurement of carbon, soot, or particulate content
alone. The combination of the three fractions and techniques gives the analyst specific
identified organic compound classes and provides the means to analyze the components of each
boiling point class.
Field gas chromatography (Field GC) with flame ionization detection (FID) of an
integrated Tedlar® bag sample is recommended for organics of boiling points less than 100°C.
Total chromatographable organic (TCO) analysis is recommended for compounds boiling
between 100°C and 300°C. Finally, gravimetric (GRAY) techniques are appropriate for
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compounds boiling at 300°C or higher. The summary of these three techniques is shown in
Figure 1.
A combination of two sampling and four analytical techniques described in this
document gives the investigator the approximate mass of all identified and unidentified
"recoverable" organic material. The mass of organic material that remains after correction
for the identified organic compounds found using RCRA SW-846 methods is the residual
organic carbon and this quantity is used to estimate risk from unidentified organic emissions,
A description of the measurement techniques is found in the following pages. Detailed
discussions of methods and operating procedures are found in the references and appendices of
this document.
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OJ.
Stationary
Source Emissions
Sampling: Method 0010
Analysis: GRAV
> 30OX BP
Sampling: Method 0010
Analysis: TCO GC/FID
100*C - 300X BP
Analysis: Field 6C/FID
for bag
Purge & Trap GC/FID
for condensate
Sampling: Method 0040
Figure 1. Stationary Source Emissions
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Section 2
Method for Total Or games Measurement
The method for total organics measurement incorporates three distinct sets of analyses,
described in the following sections:
* First, the volatile organics are collected and measured by a technique known as
Field GC using bag sampling according to Draft Method 0040. Emphasis is
made on the identification of methane, because methane may appear in
significant quantities in stack sampling efforts and correct identification may be
vital to subsequent analysis of risk assessment of the stationary source. In
addition, the volatile organics collected in the condensate trap of Draft Method
0040 are analyzed by Purge and Trap GC/FID.
* Second, the semivolatile organic compounds are collected using Method 0010
and the dichloromethane extracts of the pooled components of the sampling train
are determined by TOO GC/FID. The marker compounds are n-heptane (C7)
and n-heptadecane (C17) because their boiling points are 98°C and 302°C,
respectively.
Finally, the non-volatile organics are determined by a gravimetric procedure
known as GRAV from the same pooled dichloromethane extract of the Method
0010 train components as the semivolatile organic compounds.
The data from these four analytical determinations are collected and added to obtain a
total organics value for the sample of choice, as shown in Table 1. The total value is then
comparable from site to site or application to application, and the end-user or researcher can
more easily compare total organics data from various sources.
This identification of known vs. unidentified organics is of benefit in subsequent risk
assessment calculations.
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Table 1. Total Organies Components
Component
Boiling Point
Vapor lYessure
Sampling
:;;;:Anyysi$
Field GC,
volatile organies
0040
GC/FID and
Purge & Trap
GC/FID
figfm?
< 100°C
> 40 mm at
22.3'C
(> heptane)
TCO,
semivolatile
organies
0010
GC/FID
figfm3
100° c
< BP < 300°C
1 mm Hg at
115°C
> VP >
40 mm at 22.3°C
GRAV,
non-volatile
organies
0010
gravimetric
M g/m3
> 300°C
< 1 mm Hg at
115°C
(< heptadeeane)
Total Organies = (Field GC + Purge and trap GC) + TCO + GRAV in units of figim3
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Section 3
Field Gas Chromatography (Field GC) Method and
Purge and Trap GC Method
The field GC portion of total organics is determined by field analysis of a bag sample
by GC with a flame ionization detector (FID). This procedure is described in this document as
Appendix A (SW-846 Method 8240 & 18) and in Appendix E (EPA Draft Method 0040). The
identified range of organics for field GC is defined by boiling point range, in this case < 100°
C. The analysis procedures are normally performed in the field to minimize sample
(compound) loss due to storage and shipping. Additionally, the condensate collected as a part
of the Method 0040 sampling train is analyzed for low boiling organics by purge and trap
GC/FID. The condensate fraction is normally transferred to a vial with no headspace and
shipped to the laboratory for analysis.
Bag Sampling/Analysis
Compounds with boiling points below 100°C are sampled into Tedlar® bags and on site
gas chromatographic analysis of the collected sample is preformed. The range of applicable
compounds is very large: methane has a boiling point of -160°C, and hexane boils at 69°C.
The reporting range for the methodology extends to 100°C. If a packed column is used to
perform all of the gas chromatographic analysis, a very judicious selection of phase and
analytical conditions must be made in order to achieve chromatographic resolution for methane
at the same time as the total analysis time is limited to no more than 15-20 minutes. Some
investigators prefer the use of two gas chromatographs, one with an appropriate column and
conditions for Cj - C4 and the second with an appropriate column and conditions for the C4 -
C6 range. A capillary column is needed to perform the analysis over the entire volatility range
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with adequate resolution. A capillary column with a length of 60 m may be required to
provide adequate resolution for the C2-hydrocarbon isomers. The gas chromatographic
analysis will primarily be separating compounds on the basis of boiling points, but in some
cases the separation will be influenced by the polarity of the compounds. Numerous
chromatographic conditions such as column temperature, ramp for temperature programming,
duration of an isothermal hold, and temperature of any transfer line will all have to be
optimized for the best chromatographic results. A flame ionization detector is needed to
perform the analysis.
The gas chromatograph must be calibrated for quantitative analysis with a normal
hydrocarbon curve. The curve is prepared using certified cylinders containing the n-alkanes
from Cj through C6. A multipoint calibration of at least three points (in duplicate) is required.
Calibration for methane (CH4) must be performed carefully so that the quantity of methane can
be determined accurately. Methane is often found in significant quantities when incinerator
stacks are sampled, and it is essential to be able to identify the compound correctly and
provide an accurate quantitative measurement when calculations of risk or regulatory
significance are being performed. The certified Ct - C6 standard gas mixture is used to
calibrate the field gas chromatograph and a point approximately in the middle of the
calibration range should be analyzed at least once per day as a calibration check. The
multipoint calibration is achieved either through the use of multiple cylinders at different
concentrations or by the use of sample loops of varying sizes.
After full calibration, sample analysis is initiated when the sample container (the
Tedlar® bag) is connected to the sampling valve and the sample gas is drawn through the valve
and sample loop. When the valve is sufficiently purged, the valve is actuated and the contents
of the loop are injected into the chromatograph. Simultaneously with the injection of the
sample, the temperature programmer and integrator/data system data acquisition are started.
Chromatograms and integrator/data system output are collected. Retention times and
responses must agree to within 5 percent relative standard deviation with the calibration curve.
Uniform FID response for varying compound classes is assumed in this methodology. The
resulting quantitative results therefore tend to be biased low for compounds which are not
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n-alkanes. In many, if not most, cases the species present are not identical to those used for
calibration of the on-site chromatograph; an exact correspondence between standard peaks and
the peaks observed in the sample chromatogram will not be achieved.
Purge and Trap Sampling/Analysis
Compounds with boiling points below 100°C are sampled by Draft Method 0040 and
some of the compounds are collected in the condenser component of the sampling train. This
condensate requires purge and trap gas chromatographic analysis of the collected water sample.
The operating procedures for this methodology is included in this document as Appendix B.
A gas chromatograph with an appropriate column and conditions for the C5 - C7 range is
required. A capillary column with a length of 60 m may be needed to provide adequate
resolution for smaller organic and hydrocarbon isomers. A flame ionization detector is needed
to perform this analysis.
The purge and trap GC must be calibrated for quantitative analysis with a normal
hydrocarbon curve. The curve is prepared using liquid alkane standards containing the n-
alkanes from C5 through C7. A multipoint calibration of at least three points (in duplicate) is
needed. The alkane mixture is used to calibrate the GC and a point approximately in the
middle of the calibration range should be analyzed at least once per day as a calibration check.
The multipoint calibration is achieved through the use of serial dilutions of the primary stock
standard mixture in methanol solution.
After lull calibration, sample analysis is initiated when an aliquot of the water sample
in the volatile organic analysis (VOA) vial is transferred to the purge flask. An inert gas is
bubbled through the aliquot and volatile components of the aliquot are transferred from the
aqueous phase to the vapor phase and swept to the sorbent trap (VOCOL®, VOCARB®, or
equivalent). When the sample is thoroughly purged from the vessel into the trap, the valve is
actuated and the trap contents are desorbed by rapid heating onto the head of the GC column
with the FID detector. The temperature programmer and integrator/data system data
acquisition are started. Chromatograms and integrator/data system output are collected.
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Uniform FID response for varying compound classes is assumed in this methodology. The
lower boiling organic compounds are not expected to be found in the condensate solutions
collected in a Draft Method 0040 sampling train. If compounds are found with retention times
prior to the C4 retention time, an appropriate response factor will be used to determine the
concentration of those components and their values are reported as C4 with the other organic
results.
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Section 4
Source Sampling and Sample Extract Preparation for TCO and GRAY
In order to obtain the sample required for TCO and GRAV analysis, the field sample
must be collected in the appropriate manner. The sample is collected using the Semivolatile
Organic Sampling Train, Method 0010, included in this document as Appendix F. This
sampling method, also known as the Modified Method 5 Sampling Train, generates a set of
sampling train components which must be carefully handled in order to preserve the
compounds of interest.
The sampling train is disassembled and "broken-down" according to the specifications
of Draft Method 3542, "Extraction of Semivolatile Analytes Collected Using Modified Method
5 (Method 0010) Train (Appendix G). There are, however, several exceptions to the method
as written which must be observed in order to obtain valid data for total organics
determinations. They are listed below:
The component parts of the sampling train are normally collected in three parts:
1) particulate matter filter and front half rinse, 2) condensate and condensate
rinse, and 3) XAD-2® and back half rinse. These components are combined
into a single pooled extract for the purposes of total organics measurements. As
in Method 3542, the three parts may be taken to final volumes of 5 mL each,
but the three extracts are then combined and taken to a final pooled volume of
no less than 5 mL. Note: At no time should any of the extracts (parts or
pooled) be reduced to volumes less than 3 mL, or loss of semivolatile
compounds may occur.
Since the extracts for total organics determinations are analyzed by GC/FID and
gravimetric techniques, none of the surrogates, isotopically-labeled standards, or
internal standards associated with GC/MS analysis (Method 8270) should be
added to the extractors or sample extracts. After the sampling train is
disassembled, the components are rinsed and extracted normally, but without
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the addition of surrogate compounds.
The final pooled extract sample volume is recorded and an aliquot is used for
the TCO GC/FID, while a duplicate aliquot is used in the GRAV
measurements.
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Section 5
Total Chromatographic Organic (TCO) Method
The TCO Method has been described in detail in the Level 1 Procedures Manual3 and
revised as an interim EPA/AEERL operating procedure (Appendix C). The identified range of
organic compounds is defined by boiling point range, in this case 100-300®C. Compounds
with boiling points between 100°C and 300°C are analyzed by GC with an FID detector after
collection using a Method 0010 sampling train. The TCO procedure is carried out by analysis
of a dichloromethane extract (a combination of the extracts from the three major components
of the sampling train). The analysis is generally performed in the laboratory after extraction
and compositing of the extracts of the individual components of the Method 0010 sampling
train.
TCO Method
The TCO Method, in its current form, is a capillary GC/FID method quantifying
chromatographable material in the 100°C to 300°C boiling point range. An aliquot of the
Method 0010 dichloromethane extract is injected onto a capillary GC column with an FID
detector, and the peak areas are summed over the retention time window that encompasses the
TCO boiling point range. The entire analysis window is established by injecting C, and Cn as
the reference peaks between which the TCO integration will occur.
Analysis may be performed using a capillary (preferred) or packed column GC. A
non-polar or slightly polar column is used to provide adequate resolution and analysis in a total
run time of approximately 45 minutes. A 15 to 30 m non-polar wide bore column (0.32 mm)
has been found to be effective for TCO analysis. As a capillary or packed column procedure,
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the GC/FID is operated iit a manner consistent with the manufacturer's recommendations for
gas flow, temperature zones, and injection volume. Analysis is performed most easily using a
GC with a liquid autosampler, so that calibrations and sample injections can be performed in a
consistent and automated fashion. The TCO value is determined from a calibration standard
curve, generated with hydrocarbon standards which fall within the TCO range, specifically
decane, dodecane, and tetradecane. An integrator or GC data system is used to record the data
points as they are obtained from the injections of calibration standards and samples. The
organics identified in the prescribed boiling point range are quantified and summed (totalled)
to obtain the TCO portion of the total organics number. Reporting units are generally in terms
of fig per sample, which is then converted to fig/m3, based on the sampling volume. The GC
used for TCO analysis is calibrated using dilutions of a specific hydrocarbon stock solution. A
multipoint calibration of at least three different concentrations in duplicate is required for this
procedure. After calibration has been performed, a daily quality control (QC) check sample is
ran to verify that the GC is performing correctly. The QC check sample is ran with a standard
in the middle of the working range of the GC calibration standards.
While it is understood that the compounds in this volatility and boiling point range
might include compounds that are not hydrocarbons, the FID detector is seen as a good all-
purpose detector for the quantification of the sample extract's.
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Section 6
Gravimetric (GRAV) Method
The third component of the total organics measurement process is called gravimetric
mass (GRAV). The GRAV Method has also been described in detail in the Level 1
Procedures Manual3 and also revised as an interim EPA/AEERL operating procedure
(Appendix D). The GRAV procedure is carried out by analysis of an aliquot of the same
dichloromethane extract from the Method 0010 sampling train as was used for TCO
determinations.
GRAV Method
The GRAV Method, in its current form, quantifies nonvolatile organic material with a
boiling point greater than 300°C. A carefully measured aliquot of the Method 0010
dichloromethane extract is placed in a precleaned and preweighted aluminum weighing pan and
allowed to dry in air at room temperature, then come to complete dryness in a room
temperature desiccator, while exposure to dust and contaminants are minimized. The residue
in the pan is weighed accurately, and the mass is recorded to determine the GRAV value. For
this procedure, the three individual dichloromethane extracts from Method 0010 are pooled
and reduced to a final volume of 5.0 mL. A volume of 1 mL of the pooled extract is used for
the GRAV determinations, which are performed in duplicate. Other final extract and GRAV
aliquot volumes may be used, but the sample extraction and concentration procedures of
Method 3542 (Appendix G) should be followed closely to avoid loss of more volatile organics.
The GRAV organics in the greater than 300°C range are measured on an analytical balance
and recorded for the GRAV portion of the total organics number. This value, in /xg, is
converted to units of fig per sample, which is then divided by sample volume to obtain ^g/m3.
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This sum is added to the previously determined TCO and field GC values to find the total
organics value, in units of micrograms per m3.
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Section 7
References
Revised Draft of Risk Assessment Implementation Guidance for Hazardous Waste
Combustion Facilities. Memorandum from Michael H. Shapiro, Office of Solid
Waste. U. S. Environmental Protection Agency, May 5, 1994,
Johnson, Larry D., M. Rodney Midgett, Ruby H. lames, Michael M. Thomason, and
and Products of Incomplete Comhnstion Journal of Air & Waste Management
Association. Vol. 39, No. 5, May 1989.
IERL-RTP Procedures Manual: Level 1 Environmental Assessment (Second Edition).
U.S. Environmental Protection Agency. EPA-600/7-78-201. October 1978.
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Appendix A
Recommended Operating Procedure for
Field Gas Chromatography
(From SW-846, Method 8240 and
Method 18 - 40 CFR Part 60, Appendix A)
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Disclaimer
This recommended operating procedure has been prepared for the sole use of the National
Exposure Research Laboratory, U.S. Environmental Protection Agency, Research Triangle
Park, North Carolina, and may not be specifically applicable to the activities of other
organizations.
Acknowledgements
Assisting in the preparation of this procedure, dated 4/95 as Work Assignment No. 8 were
Joan T. Bursey and Robert Martz, Radian Corporation, Research Triangle Park, NC, under
EPA contract 68-D4-0022. Merrill Jackson is the Project Officer for the EPA contract with
Radian Corporation.
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RECOMMENDED OPERATING PROCEDURE FOR
FIELD GAS CHROMATOGRAPHY
A.1.0 INTRODUCTION
Field analyses are performed for samples that are subject to significant
degradation if analysis is delayed even for the amount of time required to ship samples
to a laboratory, or in situations where performing analysis in the field is preferable to
handling and shipping samples such as Tedlar® bags. In determining Total Organics,
field gas chromatography is performed to determine compounds in the C, - C?
hydrocarbon range. This range encompasses alkanes, alkenes, cyclic compounds, and
functionalized organic compounds. For example, methane, chloromethane,
formaldehyde, and methanol are all Cx compounds. The methodology is applicable to Q
- €7 hydrocarbons, organic compounds boiling in the range -160°C to 1O0°C. When
performing field gas chromatographic analysis, species eluting in the specified boiling
point range are quantified as n-alkanes, The sensitivity of the flame ionization detector
varies from compound to compound, but n-alkanes as a class have a higher flame
ionization response than other classes of compounds such as oxygenated or halogenated
hydrocarbons. Therefore, using n-alkanes as calibrants and assuming equivalent
responses for all other compounds in the appropriate boiling point range tends to bias
results low. That is, if an alkane standard and a non-alkane peak have equivalent system
responses, the non-alkane peak is assigned a quantitative value equivalent to the alkane.
The non-alkane peak, however, has a poorer response to the flame ionization detector
than the alkane. The amount of non-alkane required to produce the same response as
an alkane may be several times higher than the amount of alkane, so the reported value
shows a low bias.
A2.Q SCOPE AND APPLICATION
This procedure defines the field gas chromatographic analysis of gaseous
stationary source emissions sampled into a Tedlar® bag for C, - C7 hydrocarbons, a
A-l
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chromatographic elution range defining organic compounds boiling in the range of
-160°C to 100°C.
A.3.0 SUMMARY OF METHOD
A gas sample contained in a Tedlar® bag is analyzed in the field by gas
chromatography/flame ionization detection (GC/FID). The instrument is set up in the
field with column and conditions appropriate for the analysis of Q - C? n-alkanes.
Retention times are determined and calibration is performed with a certified gaseous
standard of Q - C, alkanes in air or nitrogen. Compounds of interest are identified by
retention times or retention time ranges and quantitative analysis is performed.
A.4.0 SAMPLE HANDLING AND PRESERVATION
Samples for this analysis are contained in Tedlar® bags. These samples should be
analyzed as soon after acquisition as possible, preferably within two hours. Exposure to
extremes of light and temperature should be avoided.
A.5.0 APPARATUS AND REAGENTS
A.5.1 Gas Chromatograph
The gas chromatograph to be used for this analysis must be capable of being
moved into the field, with a flame ionization detector, temperature-controlled sample
loops of varying sizes with a valve assembly, temperature-programmable oven, and an
appropriate chromatographic column to obtain the resolution desired for the analysis.
A.5.2 Recorder/Integrator/Data System
A recorder is required. Appropriate parameters are 1 inch/min chart speed, 1
mV full scale, 1 sec full scale response time. An integrator is required. The function of
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both the recorder and integrator may be superseded by a data system, if available.
Parameters which should be specified and recorded in the instrument log include noise
suppression, up-slope sensitivity, down-slope sensitivity, baseline reset delay, area
threshold, front shoulder control, rear shoulder control, and data sampling frequency.
A.5.3 Columns
For the -C4 hydrocarbons, a packed stainless steel SP-1000® column (6 ft x
1/8 inch outer diameter), or equivalent which can be calibrated over the specified
hydrocarbon range is required. Some possible equivalent columns include PLOT8 or
TCEP® columns. If a PLOT column is used, this column could be used for the C5 to C,
hydrocarbon range as well. An alternative is to use a second gas chromatograph with a
generic nonpolar packed or capillary column for the Cs to O, range and a flame
ionization detector.
A.5.4 Gas Standard
A certified n-alkane gas standard of Ct - C, n-alkanes in air or nitrogen is
required. The concentrations of the alkanes in the certified standard may range from 5 -
100 ppm. A multipoint calibration curve at different concentrations may be obtained by
using sample loops of different sizes or multiple gas cylinders at different concentrations.
A.5.5 Cylinder Gases
Helium carrier gas, hydrocarbon free, as recommended by the manufacturer for
-operation of the detector and compatibility with the column is required. Fuel
(hydrogen), as recommended by the manufacturer for operation of the flame ionization
detector, and zero air, hydrocarbon free air for operation of the flame ionization
detector, are required.
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A.5,6 Regulators
Appropriate regulators are required for all gas cylinders for both support gases
and for certified gaseous standards,
A.5.7 Teflon® Tubing
Diameter and length determined by requirements for connection of gas cylinder
regulators and the gas chromatograph.
A.6.0 GAS CHROMATOGRAPH SETUP AND CHECK
The gas chromatograph must be completely calibrated at each new test site in the
field. Whenever the gas chromatograph is set up, the following parameters must be
verified for correct operation;
1) All support gas supplies must be at the proper pressure.
2) Verify that the carrier gas flow to the analytical column is correct (for a
packed column, the gas flow rate should be 30 ± 2 mL/min; for a
capillary column, flow rate will depend upon the column diameter and
should be adjusted according to the manufacturer's specifications for the
column). Flow rate is checked at the analytical column outlet after
disconnection from the detector. The instrument must be at ambient
temperature.
3) Verify that the hydrogen flow is appropriate for the operation of the flame
ionization detector. The flow rate is checked at the control panel on the
gas chromatograph.
4) Verify that the air flow is appropriate for the operation of the flame
ionization detector. The air flow rate is checked at the gas control panel
on the gas chromatograph.
5) Verify that the electrometer is functioning properly. The electrometer
must be balanced and the bucking controls set as required.
6) Verify that recorder/integrator/data system are functioning properly.
A-4
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A.7.0 CALIBRATION
To determine the temperature ranges for reporting the results of GC analyses for
the Cy - Cj compounds, the gas chromatograph is given a normal boiling point - retention
time calibration. The n-alkanes, their boiling points, and the data reporting ranges are
shown below.
Boiling Point,
Reporting Range,
Compound
*C
°c
Report As :
methane
-161
-160 to -100
c,
ethane
i
00
00
-100 to -50
Pi
propane
-42
-50 to 0
c3
butane
0
Oto 30
c4
pentane
36
30 to 60
c5
hexane
69
60 to 90
heptane
98
90 to 98
C,
To perform a multipoint calibration, connect the - C7 certified standard gas
cylinder to the sampling valve, and allow the gas to flow through the valve at a constant,
low, and reproducible flow rate of 20 mL/min measured at the sample valve outlet using
a bubble flowmeter. When the sample valve has purged (approximately 5 min), allow
the sample loop pressure to equilibrate to atmospheric pressure and actuate the valve
and inject the contents of the sample loop into the gas chromatograph. Simultaneously,
start the integrator and/or data system and the temperature programmer, if used.
Obtain chromatograms and integrator/data system output. Retention times and
responses shall agree to within 5% relative standard deviation. Repeat the standard
injection until two consecutive injections give area counts within 5 percent of their mean
value. The average value multiplied by the attenuation factor is then the calibration
area value for the concentration.
A-5
-------
The multipoint calibration must encompass at least three concentration levels,
with each point analyzed at least in duplicate (a minimum of six calibration data points
for each n-alkane). The different concentrations are achieved either by analysis of
standards from cylinders at three different concentrations or by use of sample loops of
different sizes with one certified gaseous standard. Prepare a plot of the concentration
versus the calibration area values, perform a regression analysis, and draw the least
squares line,
A.8.0 DAILY CALIBRATION CHECK
The Ca - Cj certified standard gas mixture will be injected and analyzed at the
start of each day, at a concentration at approximately the midpoint of the calibration
curve. Retention times and responses for each component should agree with the initial
calibration data to within ± 10 percent. If the daily calibration check meets this
specification, the full calibration need not be repeated.
A.9.0 ANALYSIS OF SAMPLES
If any doubt exists concerning the relationship between the stationary source
sample GC peaks and the GC peaks obtained from calibration, a small amount of the
calibration gas should be spiked with the sample in order to verify retention times.
To perform the analysis of gaseous samples, the chromatograph, recorder,
integrator/data system must be set up according to the manufacturer's manuals and
calibrated. Operating parameters should be confirmed. The operating parameters are to
be listed on each chromatogram, and each recorder chart should be labeled. The sample
bag should be connected to the gas sample valve, the sample loop purged with the
sample, and the contents of the loop should be injected. The integrator/data system and
recorder should be started simultaneously with injection.
A-6
-------
If any doubt exists concerning the relationship between the stationary source
sample GC peaks and the peaks obtained from analysis of the calibration standard, a
small aliquot of the calibration gas should be spiked with the sample in order to verify
retention times,
A.10.0 CALCULATIONS FOR C, - C7 HYDROCARBONS
The calibration curve for the n-alkanes is constructed in the following manner:
1) For each alkane, the average retention time and relative standard deviation
are calculated,
2) Plot boiling point of each alkane versus the average retention times (in
seconds).
3) Draw the curve, manually or by computer,
4) On the curve, locate and record the retention times corresponding to the
reporting ranges: -160°C to -100°C, -100°C to -50°C, -50°C to 0°C, 0°C -
30°C, 30DC to 60DC, 60°C to 90°C, and 90°C to 98°C.
5) Calculate average area response and relative standard deviations for the
propane calibration standard.
6) Plot response (uV/sec) as ordinate versus concentration of the standard in
mg/m3 injected as abscissa. Draw in the curve. Perform least squares
linear regression and obtain the slope (jiV/sec " m3/mg).
7) In each retention time range of the sample, sum up the peak areas.
8) Convert peak areas G"V / sec) to mg/m3 by dividing by the proper
response (slope factor).
9) Record the total concentration of material in each retention time range.
A-7
-------
Appendix B
Recommended Operating Procedure for
Purge and Trap Gas Chromatography
With FID Detection
(From SW-846 Method 8240 and Draft Method 0040)
-------
Disclaimer
This recommended operating procedure has been prepared for the sole use of the National
Exposure Research Laboratory, U.S. Environmental Protection Agency, Research Triangle
Park, North Carolina, and may not be specifically applicable to the activities of other
organizations.
Acknowledgements
Assisting in the preparation of this procedure, dated 4/95 as Work Assignment No. 8 were
loan T. Bursey and Robert Martz, Radian Corporation, Research Triangle Park, NC, under
EPA contract 68-D4-0022. Merrill Jackson is the Project Officer for the EPA contract with
Radian Corporation,
-------
RECOMMENDED OPERATING PROCEDURE FOR
PURGE AND TRAP GAS CHROMATOGRAPHY
WITH FID DETECTION
B.1.0 INTRODUCTION
As a complement to the Field Gas Chromatography analysis of total organics, the
condenser component of the Draft Method 0040 sampling train is analyzed using purge
and trap techniques and an FID detector. In determining total organics, purge and trap
gas chromatography is performed to determine compounds in the Cj - Cj hydrocarbon
range. This range encompasses alkanes, alkenes, cyclic compounds, and functionalized
organic compounds. For example, methane, chloromethane, formaldehyde, and
methanol are all Cj compounds. The methodology is applicable to Ct - C? hydrocarbons,
organic compounds boiling in the range -160DC to 100°C. In performing purge and trap
gas chromatographic analysis, species eluting in the specified boiling point range are
quantified as n-alkanes. The sensitivity of the flame ionization detector varies from
compound to compound, but n-alkanes as a class have a higher flame ionization response
than other classes of compounds such as oxygenated or halogenated hydrocarbons.
B.2.0 SCOPE AND APPLICATION
The field gas chromatographic analysis encompasses gaseous stationary source
emissions sampled into a Tedlar® bag in the sampling train. Analysis is performed for
the organic compounds boiling in the range of -160°C to 100°C. In Draft Method 0040,
the condenser, the condensate trap and the sample line from trap to the Tedlar® bag are
carefully rinsed and the combined water sample is transferred to a graduated cylinder.
After carefully measuring the sample volume, the water sample is transferred to a 20 mL
or 40 mL amber glass VOA vial with a Teflon® septum screw cap with zero void volume.
VOA vials under zero headspace conditions may be stored on ice or in a refrigerated
container until analysis. This procedure defines the gas chromatographic analysis of
gaseous stationary source emissions sampled into the condensate component of a Draft
Method 0040 train.
B-l
-------
B.3.0 SUMMARY OF METHOD
The volatile compounds are introduced into the gas chromatograph (GC) by the
purge and trap method. The components are separated via the GC and detected using a
flame ionization detector (FID), which is used to provide quantitative information.
An inert gas is bubbled through the solution at ambient temperature and the
volatile components are efficiently transferred from the aqueous phase to the vapor
phase. The vapor is swept through a sorbent column where the volatile components are
trapped. The sorbent columns of choice are a VOCOL® or VOCARB 3000® design, or
equivalent. After purging is completed, the sorbent column is heated and backflushed
with inert gas to desorb the components onto a GC column. The GC column is heated
via a temperature program to elute the components, which are detected with an FID
detector.
A volatile organic sample contained in a VOA vial is analyzed in the laboratory
by gas chromatography/flame ionization detection (GC/FID). The instrument is set up
with column and conditions appropriate for the analysis of C4 - C? n-alkanes. Retention
times are determined and calibration is performed with a liquid standard of C5 - C?
alkanes. Compounds of interest are identified by retention times or retention time
ranges and quantitative analysis is performed.
B.4.0 SAMPLE HANDLING AND PRESERVATION
Samples for this analysis are transferred from the condenser vessel to VOA vials.
These samples should be analyzed as soon after acquisition as possible, preferably within
two weeks of collection. Samples are refrigerated without headspace in the vials until
analysis. Exposure to extremes of light and temperature should be avoided.
B-2
-------
B.5.0 APPARATUS AND REAGENTS
Apparatus and reagents needed to perform the purge and trap analysis techniques
are summarized in the following paragraphs. Glassware, vials, laboratory refrigerators,
compressed gas storage, and items customarily found in an analytical laboratory are
assumed to be readily available.
B.5.1 Purge and trap device
The purge and trap device consists of three major components: a purge chamber
for the water, a trap, and a desorber capable of rapidly heating the trap. The purge
chamber should be designed to accept 5 mL samples of water with a water column of at
least 3 cm. The purge gas must pass through the water column as finely divided bubbles,
normally obtained by passing the gas through a medium porosity glass frit. The packing
material for the trap should be a commercially available sorbent material (or
combination of materials) capable of trapping and releasing low boiling (volatile) organic
compounds. VOCOL® or VOCARB 3000® (Carbopack B and Carboxen® in series)
sorbent packing materials, or an equivalent sorbent, are acceptable for the traps,
providing they adequately trap and desorb the organic components of interest. The
desorber should be capable of rapidly heating the trap to a temperature of at least 180°C
for desorption.
B.5.2 Reagent water
Reagent water for this analysis is defined as water in which interferents are not
observed at the method detection limit (MDL) of the parameters of interest. Purified
water (carbon filtration or deionized distilled water) may be used. Alternatively, water
may be boiled and subjected to a bubbled stream of inert gas, then sealed until used.
B-3
-------
B.5.3 Gas Chromatograph Setup
For the Ct -C4 hydrocarbons, a packed stainless steel SF-100G® column (6 ft x
1/8 inch outer diameter), or equivalent which can be calibrated over the specified
boiling point range is required. Some possible equivalent columns include PLOT® or
TCEP® columns. If a PLOT column is used, this column could be used for the C5 to €7
hydrocarbon range as well. An alternative is to use a second gas chromatograph with a
generic nonpolar packed or capillary column for the C5 to Oj range and a flame
ionization detector.
The gas chromatograph must be completely calibrated for use. Whenever the gas
chromatograph is set up, the following parameters must be verified for correct operation;
1) All support gas supplies must be at the proper pressure.
2) Verify that the carrier gas flow to the analytical column is correct (for a
packed column, the gas flow rate should be 30 ± 2 mL/min; for a
capillary column, flow rate will depend upon the column diameter and
should be adjusted according to the manufacturer's specifications for the
column). Flow rate is checked at the analytical column outlet after
disconnection from the detector. The instrument must be at ambient
temperature.
3) Verify that the hydrogen flow is appropriate for the operation of the flame
ionization detector. The flow rate is checked at the control panel on the
gas chromatograph.
4) Verify that the air flow is appropriate for the operation of the flame
ionization detector. The air flow rate is checked at the gas control panel
on the gas chromatograph.
5) Verify that the electrometer is functioning properly. The electrometer
must be balanced and the bucking controls set as required.
6) Verify that recorder/integrator/data system are functioning properly.
B.5.4 Regulators
Appropriate regulators are required for all gas cylinders for detector and carrier
gases.
B-4
-------
B.5.5
Liquid Standard
A set of n-alkane liquid standards of Cs - Cj n-alkanes is required. The
concentrations of the alkanes in the standard may range over several orders of
magnitude within the working range of the GC/FID. A multipoint calibration curve at
different concentrations may be obtained by using multiple dilutions of a stock standard
solution.
Calibration standards should be prepared from secondary dilution of stock
standards. The solutions should be prepared in methanol, with one of the concentrations
at a level near, but above, the method detection limit. The remaining concentrations
should correspond to the expected range of concentrations found in real samples (not
exceeding the working range of the GC/FID system). Each standard should contain the
straight chain hydrocarbons Cs to C7. The lower boiling organic compounds (C, to Cj)
are not expected to be found in the condensate solutions collected in a Draft Method
0040 sampling train. If compounds are found with retention times prior to the C4
retention time, an appropriate response factor will be used to determine the
concentration of those components and their value reported as C4 (butane) with the
other organic results.
B.5.6 Cylinder Gases
Helium carrier gas, hydrocarbon free, as recommended by the manufacturer for
operation of the detector and compatibility with the column. Fuel (hydrogen), as
recommended by the manufacturer for operation of the flame ionization detector, and
zero air, hydrocarbon free air for operation of the flame ionization detector, are
required.
B-5
-------
B.5.7 Recorder/Integrator/Data System
A recorder is required. Appropriate parameters are 1 inch/min chart speed, 1
mV full scale, 1 sec full scale response time. An integrator is required. The function of
both the recorder and integrator may be superseded by a data system, if available.
Parameters which should be specified and recorded in the instrument log include noise
suppression, up-slope sensitivity, down-slope sensitivity, baseline reset delay, area
threshold, front shoulder control, rear shoulder control, and data sampling frequency.
B.6.0 CALIBRATION
To determine the temperature ranges for reporting the results of GC analyses for
the Cs - Oj compounds, the gas chromatograph is given a normal boiling point - retention
time calibration. The n-alkanes, their boiling points, and the data reporting ranges are
shown below.
Compound
Boiling Poinu
°C
Reporting Range*
*C
Report As
methane
-161
-160 to -100
ci
ethane
-88
-100 to -50
Q
propane
-42
-50 to 0
Q
butane
0
0 to 30
C4
pentane
36
30 to 60
Q
hexane
69
60 to 90
Q
heptane
98
90 to 100
Q
To perform a multipoint calibration for purge and trap analysis, the most practical
method is to prepare liquid standards in methanol of the C5 through C7 alkanes by
dilution of a primary stock. A set of dilutions is prepared, covering the working range of
the instrument and the solutions are spiked directly into clean reagent water in VOA
vials. The purge and trap system is activated to purge the standard from the purge
B-6
-------
vessel into the trap. After trapping is complete, the desorber is activated (heated) and
simultaneously the integrator and/or data system and the temperature programmer are
started. Obtain chromatograms and integrator/data system output. Retention times and
responses shall agree to within 5% relative standard deviation. Repeat the standard
injection until two consecutive injections give area counts within 5 percent of their mean
value. Hie average value multiplied by the attenuation factor is then the calibration
area value for the concentration.
The multipoint calibration must encompass at least three concentration levels,
with each point analyzed at least in duplicate (a minimum of six calibration data points
for each n-alkane). The different concentrations are achieved by analysis of standards at
three different concentrations of liquid standards of the C5 through C? alkanes. Prepare
a plot of the concentration versus the calibration area values, perform a regression
analysis, and draw the least squares line.
1.7.0 DAILY CALIBRATION CHECK
A C5 - Cy standard mixture will be injected (purge and trap) and analyzed at the
start of each day, at a concentration at approximately the midpoint of the calibration
curve. Retention times and responses for each component should agree with the initial
calibration data to within ±10 percent. If the daily calibration check meets this
specification, the full calibration need not be repeated,
B.8.0 ANALYSIS OF SAMPLES
If any doubt exists concerning the relationship between the stationary source
sample GC peaks and the GC peaks obtained from calibration, a small amount of the
calibration standard should be spiked with the sample in order to verify retention times.
B-7
-------
To perform the analysis of condensate water samples, the chromatograph,
recorder, integrator/data system must be set up according to the manufacturer's manuals
and calibrated. Operating parameters should be confirmed. The operating parameters
are to be listed on each chromatogram, and each recorder chart should be labeled. The
sample vial should be correctly labeled and transferred to the purge vessel. After
purging and trapping, the organics are desorbed onto the head of the GC column
("injection"). The integrator/data system and recorder should be started simultaneously
with injection.
B.10.0 CALCULATIONS FOE C5 - C7 HYDROCARBONS
The calibration curve for the n-alkanes is constructed in the following manner:
1) For the alkanes C5 through C7, the average retention time and relative
standard deviation are calculated.
2) Plot boiling point of each alkane versus the average retention times (in
seconds).
3) Draw the curve, manually or by computer.
4) On the curve, locate and record the retention times corresponding to the
reporting ranges: 0°C - 30°C, 30°C to 60°C, 60°C to 90°C, and 90°C to
100°C .
5) Calculate average area response and relative standard deviations for the
hexane calibration standard.
6) Plot response (uV/sec) as ordinate versus concentration of the standard in
mg/m3 injected as abscissa. Draw in the curve. Perform least squares
linear regression and obtain the slope (jiV/sec * m3/mg),
7) In each retention time range of the sample, sum up the peak areas.
8) Convert peak areas (uV / sec) to mg/m3 by dividing by the proper
response (slope factor).
9) Record the total concentration of material in each retention time range.
B-8
-------
Appendix C
Recommended Operating Procedure for Total
Chromatographable Organics (TCO) Analysis
(This document was originally prepared for the EPA/AEERL Laboratory in RTP, NC and
developed and reviewed by the QA Program of AEERL, under the direction of Judith S. Ford,
Q A Manager of EPA/AEERL)
-------
Disclaimer
This recommended operating procedure has been prepared for the sole use of the Air
and Energy Engineering Research Laboratory, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, and may not be specifically applicable to the
activities of other organizations.
Acknowledgements
Assisting in the preparation of this procedure, dated 10/88 as Document No.
AEERL/13, were Robert F. Martz, Acurex Corporation, Research Triangle Park, NC, under
EPA Contract 68-02-4701 for on-site technical support to AEERL; and Joseph D. Evans and
Anne E. Worth, Research Triangle Institute, Research Triangle Park, NC, under EPA
Contract 68-02-4291 for Quality Assurance (QA) support to AEERL. Judith S. Ford, QA
Manager for AEERL, is the Project Officer for the QA contract with Research Triangle
Institute.
-------
TABLE OF CONTENTS
Section Page
C.l INTRODUCTION 1
C.1,1 Scope 1
C.1.2 Limitations . 1
C.1.3 Definitions 2
C.2 STARTUP 3
C.2.1 Personnel Requirements 3
C.2.2 Facilities Requirements 3
C.2.3 Safety Requirements 3
C.2.4 Apparatus 4
C.2.4.1 Equipment Needed 4
C.2.4.2 Reagents and Materials 4
C.2,4.3 Maintenance 4
C.2.4.4 Theory Of FID Detector 5
C.2.5 Interferences 5
C.3 OPERATION 6
C.3.1 Summary of Method 6
C.3.2 Samples/Sampling Procedures 6
C.3.3 Operation 8
C.3.4 Analysis 9
C.4 TROUBLESHOOTING ..... 10
C.4.1 Calibration 10
C.4.2 Method Precision and Accuracy 11
C.5 DATA REDUCTION 12
C.5.1 Calculations . 12
C.5.2 Data Reporting 12
C.6 QUALITY ASSURANCE/QUALITY CONTROL 13
C.6.1 QC Checks 13
C.6.2 QC Controls 13
C.7 REFERENCES ...... 14
-------
\ LEST OF TABLES
Page
C. 1 Instrumental Operating Conditions for Gas Chromatography 7
-------
SECTION C.l
INTRODUCTION
C.l.l Scope
This method provides semi-quantitative data for organic compounds with boiling points
between 100 and 300°C. Samples that might include organic compounds in this volatility
range are organic liquids, solid sample extracts, aqueous extracts, extracts from Source
Assessment Sampling System (SASS) and Modified Method 5 (MM5) train sorbent modules,
and liquid chromatography (LC) fractions obtained from those samples. This method is based
on separating the components of a gas or liquid mixture in a gas chromatography (GC) column
and measuring the separated components with a suitable detector.
This upper end of applicability is limited by column overloading and detector
saturation. Typical range is 1 to 20 mg/mL. The operating range can be extended by dilution
of samples with solvent (e.g., dichloromethane). The sensitivity limit shall be determined by
the minimum detectable concentration of standards.
C.1.2 T limitations
Recommended operating procedures (ROPs) describe non-routine or experimental
research operations where some judgment in application may be warranted. ROPs may not be
applicable to activities conducted by other research groups and should not be used in place of
standard operating procedures. Use of ROPs must be accompanied by an understanding of
their purpose and scope. Questions should be directed to AEERL or to project personnel listed
in the Acknowledgments.
C-l
-------
C.1.3 Definitions
• Accuracy - The degree of agreement between an observed value and an
accepted reference value. Accuracy includes a combination of random and
systematic error or bias components which are due to sampling and analytical
operations; a data quality indicator.
• Calibrate - To determine, by measurement or comparison with another
standard, the correct value of each scale reading on a meter or other device, or
the correct value for each setting of a control knob. The levels of calibration
standards should bracket the range of planned measurements.
• Calibration Standard - A substance or reference material used to calibrate the
instrument.
• Method Blank - A clean sample processed simultaneously with samples
containing an analyte of interest through all steps of the analytical procedure.
• Precision - The degree of variation among individual measurements of the same
property, usually obtained under similar conditions; a data quality indicator.
Precision is usually expressed as standard deviation, variance or range, in either
absolute or relative terms.
• Quality Control (QC) Sample - A sample prepared from substances or
materials of known composition and quantity. It is used to assess the
performance of a measurement method or portions thereof. It is intended
primarily for routine intralaboratory use in controlling precision and bias in the
method. It should be prepared from, or be traceable to, a standard other than
the calibration standard.
• Reagent Blank - A sample of reagent(s), without the target analyte, introduced
into the analytical procedure at the appropriate point and carried through all
subsequent steps to determine their contribution to error in the observed value.
C-2
-------
SECTION C.2
STARTUP
C»2«l PcrsQnncI
This ROP is written for individuals with a BS/BA degree in chemistry and at least two
years experience in gas chromatography, or equivalent.
C.2.2 Facilities Remiirempnts
This procedure requires a standard analytical chemistry laboratory with counter space,
secured areas for compressed gas storage, and electricity to operate the equipment. Flasks,
beakers, tubing, etc., customarily found in such a laboratory are also needed and assumed to
be readily available. GC tools (e.g., wrenches, screwdrivers, and spare parts, etc.) also need
to be available in the laboratory.
C.2.3 Safety Requirements
Routine safety precautions required in any analytical chemistry laboratory are
applicable here. These include such measures as no smoking while in the laboratory; wearing
safety glasses, lab coats, and gloves when handling samples; and handling organic solvents in a
fume hood, etc. Compressed gases considered to be fuels (e.g., hydrogen) must be stored on
a pad outside the confines of the laboratory. A safety shower, eye wash, first aid kit, and fire
extinguisher must be readily available inside the laboratory.
C-3
-------
C.2.4 Apparatus
C.2.4.1 Equipment Needed
• Gas chromatography: With packed column and/or capillary column
capabilities, oven temperature controller, and flame ionization detector (FID)
(e.g., Perkin Elmer Sigma 115 or Hewlett Packard 5890).
• Autosampler (optional); Capable of handling methylene chloride extracts and
appropriate wash vials.
• Autosampler vials (optional); Clear glass with Teflon® faced crimp caps,
typically 100 ixL or 1 mL size.
• Crimping tool (optional): Used to secure caps on autosampler vials.
C.2.4.2 Reagents And Materials
• Methylene chloride: Burdick and Jackson or equivalent grade.
• Syringe: 5 fib or 10 (tL, gas tight, for hand injections. Otherwise,
3 ftL or 10 fih syringes are used for autosampler injections,
• Pasteur pipettes; Disposable, used for sample transfer.
• Pipette bulbs: 1 mL, amber.
• Squeeze bottle: Teflon®, 250 mL or equivalent, used for methylene chloride
rinse of vials.
C.2.4.3 Maintenance
Glassware: Clean all glassware used in the total chromatographable organics
(TCO) analysis by the method described in Reference 1.
Gas Chromatograph: Change the GC inlet septum daily; follow this with a
column bakeout at 250°C for 20 minutes or, until the detector response is stable
and all evidence of contamination is gone (no peaks), or run an injection of
clean solvent to verify column contamination is eliminated. Repeat this
C-4
-------
procedure during the run if evidence of septum failure appears (e.g., increasing
peak elution time with each run, or major loss of sensitivity).
C.2.4.4 Theory Of FID Detector
Flame ionization detectors operate by burning organic compounds in the detector's
flame. The burning process oxidizes the carbon atoms, producing electrons and positive ions.
An anode and cathode on either side of the flame collect the charged particles, and the
resulting current is proportional to the concentration of oxidized carbon in the sample.
Instrument electronics convert the detector current to a voltage, which changes linearly with
changes in analyte concentration.
The analytical system shall be demonstrated to be free from internal contaminants on a
daily basis by running a bakeout or a QC sample. A reagent blank must be run for each new
batch of reagents used to determine that reagents are contaminant-free. This is verified by an
instrument response less than the detection limit.
If duplicate runs of a sample show increasing concentration greater than 15% or if
cross-contamination is suspected (e.g., high-level sample followed by a low-level sample), a
reagent blank shall be run to verify no contamination in the system. If contamination is
evident, the column shall be baked out at approximately 250° C for twenty minutes or until the
detector is stable, and the blank check repeated.
-------
SECTION C.3
OPERATION
C.3.1 Summary of Method
TCO analysis quantifies ehromatographable material with boiling points in the range of
100° to 300°C. This analysis is applied to all samples that might contain compounds in this
volatility and boiling point range.
For TCO analysis, a 0,9 to 3 nL portion of the extract is analyzed by gas
chromatography using a flame ionization detector (FID). Column conditions are described in
this document in tabular form in Table 3-1. The peak areas are converted to concentration
values using quantitative calibration standards.
For more information, consult Lentzen et al., IERL Procedures Manual: Level 1
(Reference 1).
C.3»2 Samples/Sampling
Samples for TCO analysis arrive or are prepared as methylene chloride (or occasionally
as methanol) extracts of environmental samples, filters, resins, or ambient sampling
components. An aliquot of the extract is transferred to a TCO vial and loaded into the
autosampler as required.
All samples will be stored in a refrigerator at or below 4°C to retard analyte
degradation. Samples will be analyzed as soon as possible after sample receipt and preparation
to avoid loss of sample due to volatilization and degradation.
C-6
-------
TABLE C-l
INSTRUMENTAL OPERATING CONDITIONS FOR
GAS CHROMATOGRAPHY
Column
Temperature
Program
Injector
Detector
Carrier Gas
Split
Injector
(optional)
Injector Volume
Solvent
Fused Silica
40°C for
300°
F.I.D.
Helium
10/1 split
Not to exceed
Dichloromethane
Capillary
3 minutes
300°
1-3 mL/min
ratio
3 mL (Typically
(pesticide grade,
Column
8°C/min
1 PL L)
distilled in glass or
(15 meters,
increase to
equivalent)
wide bore,
250°Cand
typically
hold for total
DB-1 , DB-5,
run time of
or equivalent)
45 minutes
Packed
Column
(Methyl
Silicone oil or
equivalent 1/8
in, x 6 ft.
steel)
50°C or
5 minutes
20°C/min
increase to
250°C, then
hold
300°
F.I.D.
300°
Helium at
30 mL/min
N/A
1"5 //T ir
Dichloromethane
(pesticide grade,
distilled in glass or
equivalent)
-------
C.3.3 Operation
Note: All glassware coming in contact with a sample shall be cleaned by Level 1
procedures (Ref. 1). Briefly, this entails sequential cleaning with soapy water,
deionized water, 50:50 (V/V) nitric acid/sulfuric acid, deionized water, methyl alcohol,
and methylene chloride, followed by oven drying.
Those steps that are only applicable to automatic injection are shown with an asterisk
(*).
• Start up by the manufacturer's suggested method,
* • Replace septum on auto-sampler and column.
* • Ensure injection needle is in line with injection port. The autosampler needle
should be manually "injected* through the injection port to verify alignment.
• Bakeout GC at 200°C for 20 minutes until FED response is stable and all
evidence of column contamination is gone (no peaks), or run an injection of
clean solvent as the first injection of the day to verify that column contamination
is eliminated.
* * Load auto-sampler tray with samples.
* • Check the autosampler flush by placing the autosampler in manual mode and
* flushing a vial of clean solvent through the needle assembly.
* • Set auto-sampler to inject approximately 1 fiL of samples. Capillary column
can be damaged if too great a volume is injected.
• Run a QC standard using the specified conditions to verify that the system is
operating properly. Check the TCO window (C, to C,7) to ensure the range has
not changed. (Retention times may change with column aging.) The TCO
window for calculations should be adjusted as required.
• Flush needle with solvent (dichloromethane) between injections.
• Run samples and collect data.
• Analyze data according to the method described in Section 3.4.
C-8
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• After all analyses are complete, bakeout the column at 200° C for 20 minutes, or
run clean solvent as a "sample."
• Shut down instrument by method suggested by manufacturer,
C.3.4 Analysis
The peak area (FID responseZ/iL) is summed over the TCO range window and
corresponding TCO value (mg/mL) is determined from the calibration curve. In the event that
the TCO value is outside the linear working range, the sample shall be concentrated or diluted,
depending on the requirements, and reanalyzed. If there is not enough sample to concentrate,
the values are reported as found, and an appropriate qualifying statement is included in the
analytical report.
It is important that the observed values of the total integrated area for samples be
corrected by subtracting an appropriate solvent blank, prepared in the same manner as the
samples.
C-9
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SECTION C.4
TROUBLESHOOTING
C»4»l Calibration
Quantitative calibration of the TCO procedure is accomplished by the use of mixtures
of known concentration of the normal hydrocarbons decane, dodecane, and tetradecane.
Retention time limits correspond to the TCO range of boiling points and are defined by the
peak maxima for n-heptane (C,, B.P. 98°C) and n-heptadecane (C17, B.P. 303 °C). Therefore,
integration of detector response should begin at the retention time of C7 and terminate at the
retention time of C,7. The Cj and C17 peaks are not included in this integration. By this
procedure, the integrated area will cover material in the boiling range of approximately 100°C
to 300° C. Calibrate the GC with dilutions of a stock solution, generating a
response/concentration curve. The calibration curve must be 1 and must have a correlation
coefficient greater than 0.97 to be acceptable. The preparation and dilution of the stock
solution is described below:
• Weigh approximately 100 /iL aliquots of each (heptane, decane, dodecane,
tetradecane, and heptadecane, C,, C10, C12, C„, C17) (99% + pure) into a
10 mL volumetric flask or septum-sealed vial. Weigh each hydrocarbon
successively into the vial starting from least volatile to most volatile.
• Dilute the vial contents up to approximately 3 mL with dichloromethane.
• Transfer this quantitatively to a clean, 10 mL amber volumetric flask and add
dichloromethane up to the 10 mL mark. This stock solution will have
approximately 22 mg (C, to C12)/mL and 15 mg(C14 to Cl7)/mL. Several (at
least three) dilutions of the stock solution are made to cover the linear working
range.
C-10
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Duplicate results by the same operator will be rejected if they differ by more than 15 %.
The result of a quality control sample, run daily, will be considered deficient if it differs by
more than 15% from the preparation value. If this value falls outside the accepted range, the
system must be evaluated for the probable cause, and a second standard run or a new
calibration performed over the range of interest.
C-ll
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SECTION C.5
DATA REDUCTION
C.5.1 Calculations
The peak area (FID response/^L) is summed over the TCO window and a
corresponding TCO value (mg/mL) is determined from the calibration curve.
• Construct the calibration line by fitting a linear regression equation to the results
of the analysis of the calibration standard solution. The concentration of the
standards must fall within the linear working range of the instrument and
bracket the concentration of the sample. Use the C,0 to C14 standards for
calibration.
Standard Calibration Equation:
R,-CM)Q + (B) (1)
Where Rj = FID Response (total C10 to C,4 Peaks),
Cj — Concentration mg/L (total of C10 to C,4 standards),
M = Slope of line, and
B = Intercept of line.
• Calculate the TCO value for the sample (Cu, measured value) and blank (CB,
blank value) by summing the FID response over the TCO retention time span
and calculating the concentration from the calibration equation.
It is important that the observed values of the total integrated area for samples
be corrected by subtracting an appropriate solvent blank prepared in the same
manner as the samples. The sample is corrected for the blank:
C„ corrected = CB measured - CB (2)
C.5.2 Data Reporting
The results of each TCO analysis should be reported as one number (in
milligrams), corresponding to the quantity of material in the 1006C to 300°C boiling range in
the original sample collected. If more information is available (e.g., cubic meters of gas
sampled), the mg/sample value can then be easily converted to the required reporting units.
C-12
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SECTION C.6
QUALITY ASSURANCE/QUALITY CONTROL
CXI QC Checks
If evidence of septum failure appears (e.g., increasing peak elution time with each run
or major loss of sensitivity), perform a column bakeout at 250°C for twenty minutes or until
the FED response is stable and all evidence of contamination is gone (no peaks), or run an
injection of clean solvent to verify that column contamination is eliminated,
C.6.2 QC Controls
Run a reagent sample for each new batch of reagent or lot of solvent used. If the
analysis fails to show organic contaminants to be below detection limits under identical
instrument operating conditions as used for samples, then the reagent shall be distilled in glass
and retested, or the reagent batch will be unacceptable for TCO analyses.
Prepare a QC sample that is approximately mid-way in the linear working range. Run
this QC sample daily to verify the performance of the GC. Determine the TCO value using
the calibration curve and its value plotted compared to the theoretical value. If two runs of the
QC sample differ by more than 15% of the actual value, prepare a new QC sample and repeat
the test. If the new sample fails the test, determine if there is a loose column connection,
septum, or altered split flow. After correction, run a new QC sample. If the new sample fails
the test, re-calibrate the instrument and/or perform a column change if needed.
C-13
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SECTION C.7
REFERENCES
1. Lentzen, D.E., D.E. Wagoner, E.D. Estes, and W.F. Gutknecht. IERL-RTP
Procedures Manual: Level 1 Environmental Assessment (Second Edition). EPA 600/7-
78/201, NHS No. PB 293-795, pp. 140-142, October 1978.
C-14
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Appendix D
Recommended Operating Procedure for Gravimetric (GRAV)
Analysis of Organic Extracts
(This document was originally prepared for the EPA/AEERL Laboratory in RTP, NC and
developed and reviewed by the QA Program of AEERL, under the direction of Judith S. Ford,
QA Manager of EPA/AEERL)
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Disclaimer
This recommended operating procedure has been prepared for the sole use of the Air and
Energy Engineering Research Laboratory, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina, and may not be specifically applicable to the activities of other
organizations.
Acknowledgements
Assisting in the preparation of this procedure, dated 9/86 as Document No. AEERL/12, were
Robert F. Martz, Acurex Corporation, Research Triangle Park, NC, under EPA Contract 68-
02-4701 for on-site technical support to AEERL; and Monica Nees, Research Triangle
Institute, Research Triangle Park, NC, under EPA Contract 68-02-4291 for Quality Assurance
(QA) support to AEERL. Judith S. Ford, QA Manager for AEERL, is the Project Officer for
the QA contract with Research Triangle Institute.
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D.1.0 PROCEDURAL ELEMENTS
D.l.l Scope and Application
Organic compounds with boiling points of 300°C and higher, after extraction with
methylene chloride, evaporation of the solvent, and drying to constant weight, can be
determined quantitatively by the gravimetric analysis described in the procedure.1 This method
is applicable to organic liquids, solid sample extracts, aqueous extracts, and extracts from the
Source Assessment Sampling System (SASS) or Modified Method 5 train sorbent module.
This analysis should be performed after enough of the sample extract has been concentrated to
weigh accurately.2 The suggested solvent is methylene chloride because of its good extraction
properties and high volatility. Other solvents may give different results (e.g., methyl alcohol
may extract polar compounds which would not be extracted with methylene chloride). All
samples being dried to constant weight should be stored in a desiccator.
The range of applicability is limited by the sensitivity of the balance and the organic
content of the sample. The balance must be accurate to + 0.01 mg. If a sample of five
milliliters is used for the analysis, then a sensitivity of 0.1 mg/5 mL or 0.002 mg/mL of
sample can be achieved. This sensitivity can be improved by further concentration of more
sample.
D.1.2 Definitions
• Method Blank: Provides a check on contamination resulting from sample
preparation and measurement activities. Typically run in
the laboratory after receipt of samples from the field by
preparing a material known not to contain the target
parameter. Addresses all chemicals and reagents used in a
method.
D-l
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Reagent Blank: Provides information on contamination due to specific
chemical reagents used during sample preparation, plus
any background from the measurement system.
Audit Sample: Has known "true values," but is flagged for the laboratory
as a "performance evaluation (PE) sample." Provides
information on performance, but this information must be
tempered with the understanding that the sample may be
given extra attention by the analyst. An internal PE
sample is created by the in-house analytical laboratory,
while an external PE sample is created outside of the
analytical laboratory.
Results may be biased due to contamination of the solvent, glassware, or both. A
method blank (control) shall be run in duplicate for each lot of solvent and/or set of samples to
provide a control check on the purity of the solvent and the glassware cleaning procedure. The
method blank, consisting of a solvent sample from the same lot as that used to prepare
samples, shall be prepared and concentrated in an identical manner.
Two reagent blanks shall be analyzed each day samples are run to ensure results which
are not biased due to solvent contamination. The reagent blank shall be a solvent sample from
the same lot used to prepare the samples and shall not be concentrated prior to analysis. To
minimize error in weight due to moisture condensation, the pans containing the sample must
appear visually dry before being placed in a desiccator in preparation for drying to constant
weight.
D.1.4 Apparatus
(1) Analytical Balance: Capable of weighing 0.01 mg with an accuracy of
± 0.005 mg.
D-2
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(2) Desiccating Cabinet: Seal-tight ga&keted with gum robber. (Desiccators which
use silicone sealant shall not be used because of possible contamination of the
sample. Silicone grease may interfere with subsequent analysis.)
(3) Oven: Capable of operation to 175 °C.
(4) Fume Hood: Standard laboratory.
(5) Dust Coverr Plexiglass* or equivalent: To protect samples drying in hood.
D«1.*S Reagents and
(1) Disposable Aluminum Weighing Pans: Approximately 2" in diameter, 1/2"
deep; crimped sides; weighing approximately 1.0 grams.
(2) Tweezers.
(4) Pipets: 1 to 5 mL (Class A Volumetric).
(5) Olass Beakers: 50 to 400 mL.
(6) Wash Bnftles: Teflon® or equivalent.
(7) Peionized Water.
(8) Nitric Acid/Sulfaric Acid. 50:50 (V/V): Prepared from reagent-grade acids.
(9) Methylene Chloride: Burdick and Jackson or equivalent grade.
(10) Methyl Alcohol; Burdick and Jackson or equivalent grade.
(11) Drierite® and/or Silica Gel: New Drierite? or silica gel may be used as
received. Used Drierite® or silica gel may be reactivated by drying it in an
oven for at least two hours at 175"C.
D-3
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D.1.6 Sample Handling
All apparatus that contacts either the concentrated or evaporated residue samples shall
be glass, Teflon9, aluminum, or stainless steel. Evaporation of samples shall be carried out in
an area free of airborne dust and organic vapors that could contaminate the samples.
Ordinarily, all glassware coming in contact with a sample, in either dilute or
concentrated form, must be cleaned by complete Level 1 procedures.2 Briefly, this cleaning
procedure entails sequential cleaning with soapy water, deionized water, 50:50 (V/V) nitric
acid;sulfuric acid, deionized water, methyl alcohol, and methylene chloride, foEowed by oven
drying. The use of deionized water for cleaning glassware is critical when inorganic
substances are being analyzed or heavy metal contaminants are present in high concentration in
tap water.
This ROP, however, covers only the analysis of organic constituents. Tap water can be
substituted for deionized water in glassware cleaning whenever the organic concentration
exceeds 1 mg/sample as measured by this ROP. Experience has shown that tap water adds no
measurable amount of organic contaminants to the method or reagent blanks under these
conditions.
(1) Label aluminum sample pans on the underside using a ballpoint pen or other
sharp object. Handle dishes only with clean tweezers.
(2) Clean the weighing pans by first rinsing them with deionized water, then
dipping them successively into three beakers of methyl alcohol, methylene
chloride, and, finally, methyl alcohol again.
(3) Dry the cleaned weighing pans to constant weight on a shelf lined with clean
aluminum foil in an oven heated to at least 105°C. Cool the plans in a
desiccator for a minimum of 4 to 8 hours or overnight.
D-4
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(4) Weigh pans to constant weight to an accuracy of ± 0.01 mg, recording the pan
tare weight.
(5) By pipet, transfer a 1,0 mL aliquot of the sample to the aluminum sample pan
or use 1/10 of the concentrated sample. Aliquot size must never exceed 5 mL
to avoid loss of sample through capillary action.
(6) Place the sample pan on a clean piece of aluminum foil in a clean fume hood.
Shield the pan from dust with a Plexiglas® or other cover positioned to allow for
adequate air circulation. Evaporate sample to visual dryness at room
temperature. Solvent evaporation usually takes about 30 minutes.
(7) Place sample pan in desiccator over Drierite® and/or silica gel for at least
8 hours.
(8) Weigh sample pan at approximately 4-hour intervals until three successive
values differ by no more than + 0.03 mg. If the residue weight is less than
0.1 mg, concentrate more sample in the same sample pan. If there is
insufficient sample remaining for this purpose, report the initial value obtained,
along with an explanation.
The gravimetric range organics (GRAV) is calculated in units of mg/sample as follows:
(Sample Weighty + Pan Weighty) - (FanTare Weighty)
GRAV
Aliquot Volume^/Total Concentration Sample Volume^
The calculated GRAV weight is corrected for the method blank:
Corrected GRAV mass = Measured GRAV mass - Method Blank mass
D-5
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D.i«9 Data Reporting
The results of the analysis are averaged and reported in units of mg organics/original
sample.
D.1.10 Precision
Duplicate analyses shall be ran by the same analyst and shall be rejected if results differ
by more than 20% from the average. If insufficient material is present to reran the sample,
both values will be reported with a qualifying statement.
D.l.ll Accuracy
Dry sample weight should be at least 1 mg per analysis whenever possible. Accuracy
of the analysis is ± 20% of actual value. A proficiency test should be performed by each
analyst as described in Section 2.0.
D.2.0 QUALITY CONTROL ELEMENTS
All operators should demonstrate proficiency with Gravimetric Analysis of
Organic Extracts (GRAV) prior to sample analysis. In the proficiency testing,
include a GRAV analysis of a reagent blank, a method blank, and an audit
sample. The method or reagent blank shall be less than 5 mg/mL of sample.
Results of the audit sample shall be within the precision and accuracy
specifications outlined in this ROP.
Two types of audit samples are used. The first contains 100 mg of eicosane
[CHjCCH^gCHj] in 250 mL of methylene chloride. Concentrate this solution
to 10 mL in a manner identical to that used for sample preparation prior to
GRAV analysis. The second type of audit sample can be either prepared
in-house or received from an independent laboratory. An external audit sample
must contain organic compounds with chain lengths of more than 18 carbons
(and boiling points above 300° C) in sufficient concentration to be determined
D-6
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accurately. Perform the GRAY analysis in duplicate as described in Section 1.7
of this procedure,
* Determine the GRAV value of duplicate method blanks for each new lot of
solvent and/or set of samples. Run a method blank any time contamination is
suspected. Prepare the blank using the same lot of reagent and the same
concentration procedure as that used to prepare the samples. The solvent
sample shall be a volume equivalent to that used for sample preparation. If the
blank GRAV value is unusually high (i.e., 5 mg/mL of sample), find the cause
of the contamination and repeat the method blank GRAV analysis.
* Analyze two reagent blanks for GRAV each day samples are run to ensure the
results are not biased due to solvent contamination. The reagent blank shall
consist of an aliquot of the solvent used to prepare the samples. If both reagent
blank GRAV values are high (i.e., 2 mg/mL of sample), find the cause of the
contamination and reanalyze samples and reagent blanks.
* Analyze all samples in duplicate. Samples are analyzed by the same analyst and
must agree to within 20% of the average. In the event this condition is not met,
repeat the analyses.
NOTE; If the conditions require the sample to be reanalyzed (e.g., high
blank values or poor precision) and insufficient sample remains,
then report the value obtained by the initial analysis and include a
qualifying statement.
D-7
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The following section (D.3.0, MicroGRAV) is a supplement to the original GRAV
SOP, dated 9/86.3
D.3.0 MICROGRAV
The microGRAV technique allows the analyst to use a lighter gravimetric weigh pan
and a smaller aliquot of sample extract to perform the extract weighings. All of the
procedures used in traditional GRAV analysis are used with the following exceptions:
D.3.1 Reagents and Materials
(1) Weigh pans: Disposable weigh pans are constructed using heavy duty
aluminum foil and a molding jig similar to the one shown in Figure D-l. The
jig may be constructed of any inert material (nylon, plastic, Teflon®), providing
it conforms to the general shape of the figure and the internal surfaces have
generally rounded edges for ease of molding. The foil is cut into 2 inch circles
or squares of foil, molded into shape by hand pressing, and the excess foil is cut
away from the outer edges of the pan with a sharp knife or scissors. This
produces pans weighing approximately 0.25 grams each, replacing the
commercial 1 gram weigh pans,
(2) Pipets: Positive displacement pipets, fixed volume 250 fib or adjustable volume
100-250 piL are recommended (Rainin Pipetman® or equivalent with a Teflon®
plunger internal to the pipet). Disposable tips are used as received from the
manufacturer, one per sample extract.
D.3.2 Sampling/Analysis Procedures
(1) Label aluminum foil pans by marking on the underside using a dull pencil or
toothpick. Use caution to avoid piercing through the pan.
(2) There is no need to clean the pans with solvent as long as they are kept from
contact with excess dust or moisture. Experience has shown that the homemade
pans are quite free of organic contamination indicated by the analysis of many
solvent and dust blanks.
D-8
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\
1/2
inch
2 inches
9
32
Figure D-l. Molding Jig for Construction of MicroGRAV Pans
D-9
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(3) The pans are ready to use after molding and desiccating prior to tare weighing.
No preheating or drying with an oven is necessary.
(4) Using a positive displacement disposable pipet, transfer a 0.250 mL aliquot of
sample to the microGRA V pan. If necessary for a specialized application
requiring larger aliquots, repeated transfers of 0.250 mL can be added to an
individual pan, allowing the extract to air dry in the fume hood between
transfers.
(5) AH other procedures of microGRA V analysis are identical to the traditional
GRAV techniques: carefully handle the pans with tweezers, air dry to visual
dryness in a protective fume hood prior to desiccating, weigh the sample with a
manual or digital microbalance, perform mass calculations, etc.
D.4.0 REFERENCES
1. Harris, J.C. et al. Laboratory Evaluation Level I Organic Analysis Procedure.
EPA-600/S7-82-048, NTIS PB 82-239, pp. 30-36, March 1982.
2. Lentzen, D.E., D.E. Wagoner, E.D. Estes, and W.F. Gutknecht. IERL
Procedures Manual: Level 1 Environmental Assessment (Second Edition).
EPA-600/7-78-201, NTIS PB 293-795, pp. 26-142, October 1978.
3. Assisting in the preparation of this supplement, dated 9/91 were Robert F.
Martz and David F. Natschke of Acurex Environmental Corporation, Research
Triangle Park, NC, under EPA contract 68-02-4701 in support of the multi-
laboratory Boise and Roanoke Integrated Air Cancer Program, James Dorsey
and Raymond Steiber of EPA were the technical directive managers for the EPA
contract with Acurex Environmental. Judith S. Ford was the EPA QA
Manager of record for the AEERL contract.
D-10
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Appendix E
EPA Draft Method 0040
Sampling of Principal Organic Hazardous Constituents from Combustion
Sources Using Ted la r® Bags
(This is the latest draft version of Method 0040 from SW-846.
The final version of the document when released supersedes
this one and will be inserted in its plaee)
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DRAFT METHOD 0040
1.0 SCOPE AND APPLICATION
1.1 Scope: This method establishes standardized test conditions and sample
handling procedures for the collection by time integrated evacuated Tedlar* bag of volatile
organic compounds from stationary sources, such as hazardous waste incinerators. This
method also provides specific guidelines governing the use of Tedlai® bags for sample
collection and storage.
1.2 Application
1.2.1 This method is applicable to the determination and speciation of volatile
organic compounds contained in an effluent gas sample collected from stationary
sources, such as hazardous waste incinerators and other combustion sources. Gas
chromatography/ mass spectrometry (GC/MS) is the recommended analytical
technique because of its unique ability to provide positive identification of compounds
in complex mixtures like stack gas.
1.2.2 This method is not applicable to the collection of samples in areas
where there is an explosion hazard. Substitution of intrinsically safe equipment or
procedures for the equipment or procedures described in this method will not be
sufficient to adapt this method for use in areas where there is an explosion hazard.
Additional modifications to the sampling and analytical protocols may be required.
No modification may be made to this method without prior approval from the
appropriate regulatory personnel.
DRAFT 0040- 1
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DRAFT METHOD 0040
1.2.3 This method does not employ isokinetic sampling and therefore is not
applicable to the collection of highly water soluble volatile organic compounds
contained in an aerosol of water. This method uses either constant or proportional
rate sampling, depending upon the extent of the variability of the emission flow rate.
1.2.4 This method is recommended only for use by either experienced
sampling and analytical personnel or by persons under close supervision of such
qualified personnel.
1.2.5 Applicable Compounds; Compounds for which this method can be
considered shall meet the following criteria:
1. Boiling points < 121°C;
2. Source concentration below the respective condensation point.
3. Organic compounds that exhibit a loss in a Tedlar® bag of less
than 20% over a 72-hour storage time during validation studies.
1.2.5.1 Candidate analytes (Table 1) were chosen on the basis of
demonstrated stability in a Tedlar® bag (<20% degradation after 72 hours) in
previous studies,1 Condensation points (calculated from vapor pressure) at
20°C and estimated instrument detection limits (from SW-846 Method 5041)
have been provided for each of the compounds. This method is not limited to
these compounds. However, stability and recovery shall be demonstrated
when compounds other than those listed in Table 1 are to be sampled.
DRAFT 0040- 2
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DRAFT METHOD 0040
1.2.6 Detection Limits and Source Considerations
1.2.6.1 The estimated detection limit of this method (Table 1) is
compound specific and is in the range of 0.03 to 0.9ppm. Matrix effects may cause the
individual compound detection limits to be higher.
1.2.6.2 Available stability data suggests that this method may not
perform well in sampling streams containing polar and reactive compounds
like methyl ethyl ketone,1 formaldehyde,2 methanol,2 1-butene,3 and acetone3.
The use of this method to sample these compounds needs to be evaluated
before sampling,
1.2.7 Sample Hold Time: The time lapse between sampling and analysis
shall not exceed 72 hours unless it can be justified by specific sample matrix stability
data that meets the criteria of Section 1.2.5, #3. Stability in a Tedlar® bag shall be
demonstrated by spiking analytes into inert gas in the laboratory and into stack gas in
the field. The spiking level must be at least at the level found in the samples of the
emissions matrix obtained during the pre-site survey. Compound recovery in both
laboratory and field studies must be > 80% after 72 hours for consideration of
applicability. Extended hold times should be planned and approved by appropriate
regulatory personnel before the test.
DRAFT 0040- 3
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DRAFT METHOD 0040
2.0 SUMMARY
2.1 Figure 1 shows a flow chart of the method. In this method, a representative
sample is drawn from a source through a heated sample probe and filter. The sample then
passes through a heated 3-way valve and into a condenser where the moisture and
condensable components are removed; it is then collected in a Tedlai® bag held in a rigid,
opaque container. The dry gas sample and the corresponding condensate are then transported
together to a GC/MS. A mass spectrometer is most suited for the analysis and quantitation
of complex mixtures of volatile organic compounds. The total amount of the analyte in the
sample is determined by summing the individual amounts in the bag and the condensate.
2.2 Common Problems: Problems that can invalidate Tedlar® bag sampling data
and techniques to remedy these problems are listed in Table 2.
DRAFT 0040- 4
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DRAFT METHOD 0040
INTERFERENCES
Major sources of interferences are:
1. Background hydrocarbon contamination of the Tedlar® bag arising from the
bag material. Purging the bag with air or N, may reduce the hydrocarbon
level. Exposure of the bag to direct sunlight will increase hydrocarbon levels.4
The bag must be protected from exposure to sunlight by using an opaque
container to house the bag during sampling and shipping.
2. Components of the source emissions other than the target compounds.
Interferants may be differentiated from the target compounds during mass
spectrometric analysis.
DRAFT 0040- 5
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DRAFT METHOD 0040
4.0 APPARATUS AND MATERIALS
4,1 Tedlar® Bag Sampling Train: A detailed schematic of the principal
components of the sampling train is shown in Figure 2,
4.1.1 The sampling train (Figure 2) consists of a glass-lined probe, a heated
glass or Teflon® filter holder and quartz filter attached to one of two inlets of a glass
and Teflon® 3-way isolation valve (Figures 3 and 4). The second valve inlet is
connected to a charcoal trap to filter incoming air when releasing system pressure
after leak checks. The outlet of the isolation valve is connected to a glass, water-
cooled, coil-type condenser and a glass condensate trap for removal and collection of
condensable liquids present in the gas stream. A 1/4-in. OD x 1/8-in. ID Teflon®
transfer line connects the condensate trap to a second 3-way isolation valve and the
isolation valve to a Tedlai® bag contained in a rigid, air-tight container for sampling,
storage, and shipping. The bag container is connected to a control console with
1/4-in. OD x 1/8-in. ID vacuum line by means of 1/4-in. Teflon® connectors at each
end. A charcoal trap is placed in the vacuum line between the bag container and the
control console to protect the console and sampling personnel from hazardous
emissions in case of bag rupture during sampling.
4.1.2 The vacuum required to operate this system is provided by a leak-free
diaphragm pump contained in the control console (Figure 5). When the pump is
turned on, the space between the inner walls of the bag container and the Tedlai® bag
is evacuated, placing the system under negative pressure to pull the sample through
the sampling train and into the Tedlar® bag. The sampling train vacuum is monitored
with a vacuum gauge installed in-line between the vacuum line and the coarse
adjustment valve mounted in the control console.
DRAFT 0040- 6
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DRAFT METHOD 0040
4.1.3 Sample flow rate is regulated by adjusting the coarse and fine valves on
the control console. The coarse adjustment valve controls the sample inlet volume
and rate and isolates the vacuum line, vacuum gauge, and sample train from the pump
and other console components during leak checks. Sample volume is measured with a
calibrated dry gas meter contained in the control console. Sampling rate is monitored
by a rotameter, contained in the control console, which is installed on the outlet side
of the dry gas meter.
4.1.4 The source, probe, filter, and condenser temperatures are monitored by
Type J or K thermocouples using the digital temperature readout in the control
console. Probe heater temperature is regulated by the temperature controller provided
in the control console (Figure 5).
4.1.5 The velocity pressure and temperature of the source gases are measured
using a standard or S-type pi tot tube connected to a manometer with 1/4-in.
OD x 1/8-in. ID tubing, in accordance with EPA Method 2, The source velocity
pressure and temperature must be monitored during sampling and the sampling rate
adjusted proportionally to changes in the flue gas velocity (Section 7.5.1.2).
4.2 Sample Train Components:
4.2.1 Probe Assembly: The probe assembly consists of a length of heated
and insulated borosilicate glass tube inside a length of stainless steel tubing. The
probe temperature shall be maintained between 130°C (266°F) and 140°C (284°F) in
order to prevent damage to Teflon® lines and to facilitate efficient cooling of the gases
in the condenser. Water cooling of the stainless steel sheath will be necessary when
the source temperature approaches or exceeds 140°C (284°F).
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4.2.2 Particulate Filter: Particulate matter from the sample gas stream
exiting the probe is collected on a quartz filter substrate in a heated 47-mm Teflon®
or glass filter holder. Use clean filters in order to prevent sample contamination.
The particulate matter itself is not analyzed or archived. However, removal of
particulate matter provides a cleaner sample for analysis. All connections between the
probe and particulate filter shall be heated to maintain the temperature between 130°C
(266°F) and 140°C (284°F) so that compounds remain in the volatile phase. Heat-
wrapped Teflon® unions with stainless steel nuts and Teflon® ferrules are
recommended for all heated connections.
4.2.3 Isolation Valves: A typical isolation valve is shown in Figure 3. The
isolation valves shall be constructed of Teflon® or glass with Teflon® stopcocks to
provide gas tight seals without the use of sealing greases. The probe and bag
isolation valves are of identical design and materials and are therefore
interchangeable. The probe isolation valve provides for the attachment of a charcoal
or similar purge trap to allow filtered ambient air to enter the train when returning the
train to ambient pressure after leak checks. This valve directly connects the probe
and filter assembly to the condenser inlet and must be heated to between 130°C
(266°F) and 140°C (284°F). The bag isolation valve allows the bag to be opened for
sampling or evacuation and isolated and sealed for leak checks or system purges.
4.2.4 Condenser: Use a jacketed, water-cooled, coil-type glass condenser
with a volume of at least 125 milliliter (mL). The condenser shall have sufficient
capacity to maintain the temperature of the sample gas stream between 20°C (68 °F)
and 4°C (39 °F) to ensure proper removal and collection of condensable moisture in
the effluent gas sample. The cooled sample gas stream temperature should not exceed
ambient temperature. All condenser connections must form a leak-free, vacuum-tight
seal without using sealing greases. Stainless steel fittings are not permitted, and
Teflon® unions or washers with screw caps are recommended.
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4.2.5 Condensate Trap: A glass Erienmeyer distilling flask with threaded
screw cap connections, Teflon® seals, and a minimum volume of 125 mL may be
used to trap condensate. All connections on the condenser and trap shall be sized to
accept 1/4-in. OD x 1/8-in. ID Teflon® or glass fittings. The stem from the
condenser must be positioned to within 0.5-in from the bottom of the condensate trap.
4.2.6 Sample Transfer Lines and Connection Fittings: All sample transfer
lines connecting components shall be less than 5 ft long and constructed of 1/4-in. OD
x 1/8-in. ID Teflon® tubing or glass. All sample lines upstream of the condenser and
condensate trap must be heated and the temperature maintained between 130°C
(266°F) and 140°C (284°F). Use Teflon® fittings for connections between various
train components to provide leak-free, vacuum-tight connections without the use of
sealing grease. New tubing should be used for each separate test series or condition
to prevent cross contamination of sample compounds.
4.2.7 Tedlar® Storage Bag: Choose a bag size according to the guidelines
provided in Section 7.2.4. In order to minimize wall effects, the sample volume must
fill at least 80% of the bag capacity. The recommended size range for bags is 25 L
to 35 L. Small bags (< 25 L) are easier to store and transport but may have
insufficient volume for proportional sampling. In addition, accurate volumetric
measurement is difficult with smaller bags. Large bags (> 50 L) lack portability but
may be required under certain conditions, such as during proportional sampling and
for sampling sources requiring high sample rates.
4.2.8 Evacuated Container (Bag Container); Use any rigid, air-tight metal
or plastic (e.g., PVC®/Polyethylene®/Nalgene®) drums or glass containers to house
the Tedlar® bag during sampling, storage, and transport. The container must be
constructed so that it can easily be assembled and disassembled (for bag removal).
The container must be able to hold a negative pressure of at least 10 in. HaO. The
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bag container must be at least 20% smaller than the Tedlar® bag being used but must
be large enough to hold the volume of sample required (e.g., for a sample size of
20 L, a 25-L Tedlai® bag inside a 20-L container provides sufficient volume without
danger of overinflating the bag).
Containers must not have staples, sharp edges, or metal closures which might
damage bags. The container should also be constructed of a material that shields the
sample from exposure to sunlight to protect the bag contents from ultra-violet light.
A viewing port or other means of observing the flexible bag during sampling is
desirable. During storage and transport, the viewing port shall be covered with
opaque material.
4.2.9 Vacuum Lines: Use Tygon®, Poly®, Nylon®, or similar tubing
capable of maintaining at least 10-in. H20 negative pressure without collapse as
vacuum lines. Tubing should be 1/4-in. OD x 1/8-in. ID size to minimize volume
and ensure compatibility of connection fittings throughout the train. Stainless steel
fittings and valves may be used for vacuum line connections but may not be used in
the sampling line.
4.2.10 Control Console (Meter System): The metering system required for
this method is readily available in the form of a Volatile Organic Sampling Train
(VOST, SW-846 Method 0030) control console/meter box (e.g., Nutech Model
280.01B) and shall consist of the components pictured in Figure 5.
4.2.10.1 Vacuum Gauge (Meter Pressure): Use a direct reading,
mechanical vacuum gauge capable of measuring pressures of at least 15 in. Hg
with 1-in. or smaller increments to monitor system vacuum during sampling
and leak checking the bag, the container, and the sampling train.
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4.2.10.2 Sample Flow Rate Adjustment Valves (Coarse and
Fine): The coarse adjustment valve controls volume and rate of sample flow
and isolates the control console from the sampling train and vacuum line
during leak checks. The fine adjustment valve controls sample rate and system
vacuum. Closing the valve (clockwise) increases train vacuum and sample
flow rate. Opening the valve (counterclockwise) decreases train vacuum and
sample flow rate.
4.2.10.3 Pump: Use a leak-free diaphragm pump or equivalent that
is capable of pulling and maintaining a vacuum of at least 15 in. Hg and a
flow rate of at least 1 liter per minute (Lpm).
4.2.10.4 Calibrated Dry Gas Meter: The control console contains
a calibrated dry gas meter (Singer Model 802/American Meter Model 602 or
equivalent) capable of reading 1 L per revolution with 0.1-L increments, and
provides accurate measurement of the volume of the sample collected.
4.2.10.5 Flow Meter: Use a rotometer with a glass tube and a
glass, Teflon®, or sapphire float ball of suitable range (0-5 Lpm) to measure
the sample flow rate. The flow meter shall be accurate to within 5 % over the
selected range. A range of ± 25% of the desired sampling rate is suggested
to ensure greater accuracy of readings and a better range for adjustment of the
sampling rate (proportional to the source gas stream velocity). The rotometer
is installed at the outlet of the dry gas meter in the console.
4.2.10.6 Thermocouples and Temperature Read Out Device:
Use a sufficient number and length of type J or K thermocouples. The 10-
channel (1 to 4 remote; 5 dry gas meter, 6 to 10 spares) digital thermocouple
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read-out provided in the control console displays the source, probe, filter, and
condenser temperatures.
4.2,10.7 Heat Controller: Use a rheostat or digital temperature
controller (e.g., Fuji PYZ4 or equivalent) to regulate probe heat temperatures.
4.2.11 Pitot Tube Probe: Use a standard or S-type pitot tube must be used
for pretest and post-test velocity traverses (as described in Section 2.1 of EPA
Method 2) and to monitor flow so that the sampling rate can be regulated
proportionally to the source gas velocity throughout the length of the sampling run.
4.2.12 Pressure Gauge (Manometer): Use a water- or oil-filled U-tube or
incline manometer capable of measuring to at least 10 in. H20 and accurate to within
0.1 in. H,0 for monitoring and measuring the source gas velocity (as described in
Section 2.2 of EPA Method 2).
4.2.13 Barometer: Use an aneroid or other barometer capable of measuring
atmospheric pressure to within 0.1 in. Hg of actual barometric pressure.
4.2.14 Charcoal Absorbent Traps: Use charcoal traps to absorb organic
compounds in the atmosphere at the site. One charcoal trap is attached to the probe
isolation valve and filters incoming air when releasing vacuum to prevent
contamination of the train during leak checks. A second charcoal trap is located in
the vacuum line and filters any gas exiting the sample train to protect sampling
personnel in case of bag rupture. Any readily available, ready made charcoal tube
similar to a VOST tube may be used.
4.2.15 Stopwatch: Use any stopwatch capable of measuring 1 second to
time sample collection.
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5.0 REAGENTS AND MATERIALS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise indicated,
it is intended that all reagents shall conform to the specifications of the Committee on
Analytical Reagents of the American Chemical Society, where such specifications are
available. Other grades may be used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the accuracy of the determination.
5.2 Reagents:
5.2.1 Water: Water used for sample train preparation shall be distilled and
deionized. Water used for rinses during recovery of condensate shall be prepurged
high performance liquid chromatography (HPLC) grade. Clean clear tap water may
be used as condenser cooling water.
5.2.2 Nitric Acid (10%), HN03: All HN03 used must be reagent grade.
5.2.3 Charcoal: Use SKC petroleum-base or equivalent charcoal. A mesh
size of 6-14 is recommended. New charcoal must be used for each run series or test
condition and may be reused if reconditioned using the same criteria specified in
VOST (SW-846, Method 0030), Section 3.2.
5.2.4 Methanol: Use speetrometric or equivalent grade methanol.
5.3 Field Spiking Standards: Appropriate cylinder gases containing the target
components of interest in known concentrations (highest purity available) for field spiking
must be obtained.
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SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Pretest Preparation:
6.1.1 Glassware; Before sampling, prepare the glass components of the
train as follows:
1. Clean with nonionic detergent (e.g., Aleonox) and hot water in
an ultrasonic bath.
2. Rinse three times with distilled and deionized water.
3. Rinse three times with 10% HN03.
4. Rinse three times with distilled and deionized water.
5. Dry in an oven heated to at least 130°C (266°F) for 2 hours.
6.1.2 Sample Lines and Bag Containers: Treat all Teflon® lines, fittings,
and the sample bag containers as outlined in Section 6.1.1 following steps 1 through
4. Then air dry these components in an area free of organic compounds. Use clean
Teflon® tubing for each test series or condition. Hand wash the bag containers.
6.1.3 Bag Cleaning Procedure: Ensure that all bags are clean before
using them for sampling. First, flush each bag three times with high purity nitrogen
(N2; 99.998%). Then fill each bag with the N2 and analyze the bag contents at the
highest sensitivity setting using the same analysis technique as will be used for
analyzing samples. Analyze one analytical system blank each day before constructing
the calibration curve by talcing the gas chromatograph through its analytical program
with no sample injection. Perform an analytical system blank again if carryover
between samples is indicated. Other, less stringent methods of cleaning and analysis
may be used at the risk of overlooking important contaminants. An acceptable level
of contamination will be a response less than five times the instrument detection limit
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or half of the level of concern, whichever is less. Repeat the nitrogen flush as
necessary until the acceptable level has been reached. No bag shall be used until it
has been satisfactorily cleaned.
6.2 Sample Bag Storage and Transport Procedures: To ensure sampling
integrity, perform sample recovery in a manner that prevents contamination of the bag
sample. Protect the bag from sharp objects, direct sunlight and low ambient temperatures
(below 0°C) that could cause condensation of any of the analytes. Store the bag samples in
an area that has restricted access to prevent damage to or tampering with the sample before
analysis. Analyze the bag samples within 72 hours of sample collection unless it can be
shown that significant (>20%) sample degradation does not occur over a longer period of
sample storage. Upon completion of the testing and sample recovery, check all the data
forms for completeness and the sample bags for proper identification. Store the bags in
rigid, opaque containers during all sampling, storage and transport procedures. Ship the
bags using ground transportation. Follow all hazardous materials shipping procedures.
6.3 Condensate Storage and Transport Procedures: To ensure sampling
integrity, perform sample recovery in a manner that prevents contamination of the condensate
(Section 7.6.5). Store the condensate in 40 mL vials under head-space free conditions.
Place the vials in ice or in a refrigerated container at 4°C (± 2°C) [39°F (+ 4°F)]
immediately following recovery and during transport for analysis. In addition, store the vials
in an area that has restricted access to prevent damage to or tampering with the sample
before analysis. Upon completion of the testing and sample recovery, check all the data
forms for completeness and the condensate samples for proper identification. Ship the
condensate samples using ground transportation. Follow all hazardous materials shipping
procedures.
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PROCEDURE
7.1 Pretest Survey:
7.1.1 Perform a pretest survey for each source to be tested. The purpose
of the survey is to obtain source information to select the appropriate sampling and
analysis parameters for that source. Potential interferences may be detected and
resolved during the survey. When necessary information about the source cannot be
obtained, collection and analysis of actual source samples may be required.
7.1.2 The following information must be collected during a survey before a
test can be conducted. The information can be collected from literature surveys and
source personnel, but an actual oil-site inspection is recommended. A copy of the
survey results must be forwarded to the chemist performing the sample analyses.
7.1.2.1 Determine whether the sampling site is in a potentially
explosive atmosphere. If the sample site is located in an explosive
atmosphere, use other, instrinsically safe test methods. This method is never
to be used in a potentially explosive atmosphere (Section 1.2.2).
7.1.2.2 Measure and record the stack dimensions on a data sheet
similar to the data sheet shown in Figure 6. Select the sampling site and the
gaseous sampling points according to EPA Method 1 or as specified by the
regulatory personnel.
7.1.2.3 Determine the stack pressure, temperature, and the range
of velocity pressures using EPA Method 2.
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7.1.2.4 Determine the stack gas moisture content (Section 7.7.7)
using EPA Approximation Method 4 or its alternatives. Perform the
determination when process operations are as they will be during final
sampling. If the process uses and emits ambient air, use a sling psychrometer
to measure the moisture content of the ambient air in the area of process air
uptake.
7.1.2.5 Select a condensate collection system with a minimum
volume of 50 mL, Select a sampling rate and volume that will yield a total
condensate catch at or below 50 mL, to allow recovery of the condensate into
volatile organic analysis (VOA) vials with minimum dead space.
7.1.2.6 In accordance with EPA Method 1, select a suitable probe
liner and probe length as determined by the temperature and dimensions of the
source. Determine the point within the stack that represents an average flow
and temperature of the stack. Mark the probe at the determined distance to
provide a reference point. For sample collection, insert the probe into the duct
to the predetermined point to ensure proper probe placement and collection of
a representative sample.
7.1.2.7 Determine whether the source has a constant or variable
gas flow rate. The flow rate may be considered constant if the variation over
the sampling period is no more than 20%. If the process is constant, use a
constant sampling rate (Section 7.5.1.1). If the process is not constant, use
proportional sampling (Section 7,5.1.2).
7.1.2.8 Determine approximate levels of target compounds by
collecting a pretest bag sample for analysis. This information is needed to
establish parameters for the analytical system.
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7.1.2.9 Check the sampling site to ensure that adequate electrical
service is available.
7.1.2.10 Follow all guidelines in the health and safety plan for the
test. Use appropriate safety equipment as required by conditions at the
sampling site (e.g., respirator, ear and eye protection, and a safety belt)
(Section 7.1.2.8).
7.2 Pretest Procedures
7.2.1 Assembly: Assemble the train according to the diagram in Figure 2.
Adjust the probe, filter, and valve heater controls to maintain a temperature between
130°C (266°F) and 140°C (284°F), circulate cooling water from an ice bath to the
condenser until the temperature is stabilized at or below 20°C. Allow the probe,
filter, valve, and condenser temperatures to stabilize before sampling. Mark the
probe, pitot tube, and thermocouple assembly with the proper sampling points as
determined in accordance with EPA Method 1. Before sampling, insert the pitot tube
and thermocouple probe into the stack, to allow the thermocouple readings to
stabilize.
7.2.2 Preliminary Velocity and Temperature Traverse: While the probe,
filter, valve, and condenser temperatures are stabilizing, perform a preliminary
velocity/temperature traverse in accordance with EPA Methods 1 and 2. Record the
velocity (aP) and temperature (T,°C) at each point to determine a point of average
flow and velocity and measure the static pressure at that point. Determine the
average velocity head (aP,vk) and range of fluctuation.
7.2.3 Determination of Moisture Content; Determine the moisture
content of the gas stream being sampled before (Section 7.1.2.4) or during actual
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sampling. For combustion or water controlled processes (wet electrostatic
precipitators and scrubbers), obtain moisture content of the flue gas during test
conditions from plant personnel or by direct measurement using EPA Method 4.
7.2.4 Criteria for Selection of Sample Volume and Flow Rate: The flow
rate should fill the bag to at least 80% of its capacity during the sampling period.
The following criteria should be met:
1. Minimum stack sampling time for each run should be 1 h. Data
from less than 1 h of sample collection would be an invalid test
run. Two hours of stack sampling time is recommended as
optimal.5
2. The minimum sample volume shall be no less than 15 L.
3. The minimum allowed sample flow rate shall be 250 mL/min.
Typically the average sampling flow rate is about 0.5 L/min which will yield
approximately 30 L of sample collected per hour.
7.2,4.1 Mass Emission Rate Determination: Determine whether
the final result will be presented on a concentration or mass emission basis
before sampling. If results will be presented on a concentration basis, only the
concentrations of the target analytes and the stack gas moisture content need to
be measured. If the mass emission rate of any compound is to be presented,
the volumetric flow rate of the stack gas must also be determined. The
volumetric flow rate may be determined by performing a temperature and
velocity traverse in accordance with EPA Methods 1 and 2, with actual sample
collection.
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Leak Check Procedures
7.3.1 Bag Evacuation and Bag Leak Check Procedure: Before sampling,
ensure that the Tedlaf® bag is fully evacuated and leak free.
7.3.1.1 Assemble the sample train as illustrated in Figure 2 and
described in Section 4.1.1, ensuring that all connections are tight.
7.3.1.2 Turn the probe isolation valve to position 1 and turn the
bag isolation valve to position 1 (Figure 4).
7.3.1.3 Disconnect the vacuum line from the bag container (the
quick connect has a valve to seal the line; Figure 2) and turn on the pump in
the control console (Figure 5).
7.3.1.4 Open the coarse adjustment valve and adjust the fine
adjustment valve on the control console (Figure 5) until the vacuum gauge
reads 5 in. Hg.
7.3.1.5 Turn the bag isolation valve to position 3 (Figure 4) and
open the coarse valve completely to obtain maximum flow rate.
7.3.1.6 Observe the dry gas meter and rotometer as the bag is
evacuated. The bag is completely evacuated when no flow is indicated on the
dry gas meter and the vacuum rises to 5 in. Hg (Figure 5).
7.3.1.7 Allow the rotometer float ball to drop to zero. Time and
record the leak rate using one of the following procedures.
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7.3.1.7.1 Timed Leak Rate (measured in liters per minute) -
Observe the leak rate indicated oil the dry gas meter and time for 1
min. The leak rate must be less than 4% of the sample rate (e.g.,
0.02 Lpm for a sample rate of 1 Lpm).
7.3.1.7.2 Timed Pressure Loss Rate (measured in inches Hg
drop per minute) - Close both the coarse and fine adjustment valves
and turn off the pump. Observe the vacuum gauge and time the
pressure drop. The leak rate must be less than or equal to
0.1 in. Hg/min.
7.3.1.8 If all connections are found to be leak tight and the leak
rate cannot meet the set criteria, discard the bag and test another clean bag.
7.3.1.9 Turn the bag isolation valve to position 1 (Figure 4) to seal
the evacuated bag.
7.3.1.10 Turn off the pump and turn the probe isolation valve to
position 3 (Figure 4) allowing the train to return to ambient pressure.
7.3.1.11 Return the probe isolation valve to position 1, seal the end
of the probe and reconnect the vacuum line to the bag container (Figures 2
and 4).
7,3.2 Pretest Leak Check
7.3.2.1 Before sampling and immediately after evacuating and leak
checking the bag, perform a pretest leak check of the sampling train.
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7.3.2.2 Ensure that the bag isolation valve is in position 1 (Figure
4) and the end of the probe is sealed.
7.3.2.3 Turn the probe isolation valve to position 2 (Figure 4),
turn the pump on, and open the coarse adjustment valve (Figure 5).
7.3.2.4 Allow the sample train to evacuate and adjust the fine
adjustment valve to increase the vacuum to 5 in. Hg (Figure 5).
7.3.2.5 When the rotometer drops to zero and the dry gas meter
slows to a stop, time and record the leak rate following the procedures
outlined in Section 7.3.1.7.
7.3.2.6 If the leak rate is greater than 0.1 in Hg/min or 4% of the
sampling rate, check all connections, valves, and the probe seal for tightness.
Any leak found must be corrected and the leak check repeated before sampling
collection begins.
7.3.2.7 After completing a satisfactory leak check, return the
sampling train to ambient pressure by turning the probe isolation valve to
position 3 (Figure 4) and turning off the pump (Figure 4).
7.3.2.8 When the vacuum gauge drops to zero, immediately turn
the probe isolation valve to position 1 (Figure 4).
7.3.3 Post-test Leak Cheek
7.3.3.1 A post-test leak check must be performed after each bag
sample is collected, before changing the bag and container for the next sample.
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7.3.3.2 Ensure that the bag and probe isolation valves are in
position 1 (Figure 4) and the pump is turned off when sample collection is
completed.
7.3.3.3 Remove the probe from the stack and seal the end of the
probe with a leak-tight seal. Check all connections and train components for
looseness or breakage. Do not tighten any connections. Record any abnormal
conditions.
7.3.3.4 Turn the probe isolation valve to position 2 (Figure 4) and
disconnect the quick connectors on the bag isolation valve return line from the
tee on the vacuum line (Figure 2).
7.3.3.5 Turn on the pump and adjust the fine adjustment valve
until the train vacuum reaches at least 1 in. Hg above the highest vacuum
attained during sample collection. Time and record the leak rate as previously
outlined in Section 7.3.1.7.
7.3.3.6 If the leak rate is less than 4% of the sample rate or
0.1 in. Hg/min., the sample is considered valid (Section 7.3.1.7.1 and
7.3.1.7.2).
7.3.3.7 Return the sample train to ambient pressure
(Sections 7.3.2.7 and 7.3.2.8) and disconnect the sample and vacuum lines
from the bag and container to prepare the train for the next sample.
7.3.3.8 If the post-test leak check proves invalid, discard the
invalid sample. Attach a new Tedlai^ bag, evacuate and leak check the bag,
and repeat the sample collection.
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7.4 Preparation far Sample Collection
7.4.1 Perform the pretest leak checks outlined in Section 7.3.
7.4.2 Remove the seal from the end of the probe and insert the probe into
the stack to the point of average velocity and temperature and constant flow.
7.4.3 Purge the sampling train (probe, valve, and filter assembly ONLY)
using the following procedures:
1. Cap the inlet side of the charcoal purge trap connected to the
probe isolation valve tee using a 1/4 in. cap and plug with
Teflon® ferrules for an air-tight seal (Figure 2).
2. Disconnect the vacuum line quick connect from the rigid bag
container (the quick connect has a valve to seal the line).
3. Disconnect the return line connected to the bag isolation valve
from the quick connect at the vacuum line tee (Figure 2).
4. Connect the purge line from the probe isolation valve tee to the
vacuum line tee using the quick connects (Figure 2).
5. Ensure that the bag isolation valve is in position 1 (Figure 4),
turn on the pump, and turn the probe isolation valve to position
2 (Figure 4).
6. Draw at least eight times the sample volume of flue gas, or
purge for at least 10 minutes, whichever is greater.
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NOTE: A three-way valve may be used in place of the purge quick connects
at the vacuum line tee.
7.4.4 Adjust the sample flow rate to the desired setting and check all
temperature and flow readings during the purge to ensure proper settings,
7.4.5 Purge the sampling train before and between the collection of each
sample during the test run.
7.4.6 Label each bag/container and VOA vial clearly, uniquely, and
consistently with its corresponding data form and run. Follow appropriate traceability
requirements as defined by the regulatory personnel.
7.5 Sample Collection: Start sample collection after the pretest leak check
(Section 7.3.2) and the system purge (Section 7.4). Collect the sample using proportional
rate sampling if the pretest survey measurements (Section 7.1.2.7) show that the emission
flow rate varies by more than 20% over the sampling period. Otherwise, use constant rate
sampling. Prepare for sample collection for either method by turning the bag isolation valve
to position 2 (Figure 4) while the pump is still running from the system purge.
If a viewing port has been incorporated in the bag container design, visually inspect
the Tedlai® bag frequently during the sampling run to ensure that it is filling properly and
that a sufficient sample volume is collected. This frequent inspection will also help prevent
overfilling and bursting the bag during sampling.
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7.5.1. Constant Rate Sampling:
1. Place the end of the probe at a point within the duct determined
to have the average velocity and temperature and a constant flow
rate.
2. Record the start volume from the dry gas meter and begin
timing the sample period.
3. Take flue gas velocity and temperature readings using either
EPA Method 2 A for smaller ducts (< 24 inches) with a remote
pitot tube and thermocouple or EPA Method 2 for larger ducts
(>24 inches). Utilizing a sample probe with pitot tubes and
thermocouples attached will generally ease sampling and will
provide a direct means to monitor flue gas velocity and
temperature at the sample probe inlet.
4. Record all required data upon starting, and at intervals of no
more than 5 minutes on the field sampling data form (Figure 7).
5. Adjust the sample flow rate and sampling train heating systems
to the correct levels, after every velocity and temperature
reading. The tester must closely monitor the sample train and
control console to ensure that the sample flow rate does not vary
by more than 20% during any 5-minute period.
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7.5.2. Proportional Sampling:
1. Position the probe in the center of the stack.
2. Record the start volume from the dry gas meter and begin
timing the sample period.
3. Monitor the velocity head during sampling as described in
Section 4.1.5 and maintain a constant proportion between the
sample flow rate and the flow rate in the duct. The flow rate to
be used during sampling (Section 7.2.2) is calculated using the
proportional sample rate equation in Section 7.8.4. With this
equation and the sample rate assigned to the average flow rate,
the rotometer setting can be determined after each velocity
reading and the sample rate set accordingly.
4. Record all required data upon starting, and at intervals of no
more than 5 minutes on the field sampling data form (Figure 7).
7.5.1.3 Single-Point Sampling: Collect samples from a single
point within the duct as described in Sections 7.5.1.1 and 7.5.1.2, unless
multipoint sampling has been determined necessary (Section 7.5.1.4).
7.5.1.4 Multipoint Sampling: Perform multipoint integrated
sampling only in a case where there is a possibility of effluent stratification.
Stratification of gases is less likely than of particulates. If however, multipoint
sampling is required, determine the necessary number of sample points in
accordance with EPA Methods 1 and 2.
DRAFT 0040- 27
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DRAFT METHOD 0040
7,6 Post-test Procedures:
7.6.1 Record the final volume from the dry gas meter at the end of each
sample collection period.
7.6.2 Perform a post-test leak check as described in Section 7.3.3.
7.6.3 Inspect the field sampling data form (Figure 7) and sample
identification labels for accuracy and completeness.
7.6.4 Replace the particulate filter after each sample.
7.6.5 Condensate Recovery: The condensate collated during sampling
must be recovered separately for each individual bag sample collected, using the
following procedures.
7.6.5.1 Carefully remove the condensate trap, the condenser and
the sample line (from the trap to the bag) from the sample train. Pour the
contents of the condensate trap into a clean measuring cylinder.
7.6.5.2 Rinse the condenser, the condensate trap and the sample
three times with 10 mL of HPLC grade water and add the rinsings to the
measuring cylinder containing the condensate. Record the final volume of the
condensate and rinse mixture on the field sampling data form (Figure 7). High
moisture sources (such as those with wet control devices) may require a 150-
mL or 200mL measuring cylinder while low moisture sources (such as some
rotary kilns and pyrolytic incinerators) may require only a 100-mL size.
DRAFT 0040- 28
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DRAFT METHOD 0040
7.6.5.3 Pour the contents of the measuring cylinder into a 20- or
40-mL amber glass VOA vial with a Teflon® septum screw cap. Fill the vial
until the liquid level rises above the top of the vial and cap tightly. The vial
should contain zero void volume (i.e., no air bubbles). Discard any excess
condensate into a separate container for storage and transport for proper
disposal.
7.6.5.4 Label each vial by using wrap around labels. Labels can
be preprinted or can be filled out on site.
7.7 Analytical Approach: The following description provides general guidelines
to the analytical approach rather than a comprehensive analytical protocol. The primary
analytical tool recommended for the measurement of volatile organic compounds in source
emissions is GG/MS using fused-silica capillary GC columns. Prescreening of the sample by
gas chromatography with either flame ionization (GC/FID) or electron capture detection
(GC/ECD) is recommended because it may not only be cost effective, but will also yield
information regarding the complexity and concentration level of the sample. If the smallest
feasible injection loop saturates the analytical system, dilutions of the sample can be made
into Tedlar® bags using pure N2 (99.998%) as diluent. Calculate the concentration of the
volatile organic compounds in the gaseous emissions by using the equations (14-18) in
Section 7.8.10.
7.7.1 Analysis of gaseous components; Introduce the gases into the gas
chromatograph through the use of a sample loop. Use a cryogenic trap if sample
concentration before analysis if necessary.
For most purposes, electron ionization (EI) mass spectra will be collected
because a majority of the volatile organic compounds give characteristic EI spectra.
Also, EI spectra are compatible with the NIST Library of Mass Spectra and other
DRAFT 0040- 29
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DRAFT METHOD 0040
mass spectral references, which aid in the identification process for other components
in the incinerator process streams.
To clarify some identifications, chemical ionization (CI) spectra using either
positive ions or negative ions can be used to elucidate molecular-weight information
and simplify the fragmentation patterns of some compounds. In no case, however,
should CI spectra alone be used for compound identification. For descriptions of GC
conditions, MS conditions, internal standard usage, and quantitative and quantitative
identification, refer to the SW-846 Method 8240.
7.7.2 Analysis of condensates: Refer to the SW-846 Method 8240 to
analyze condensate samples by using the purge and trap technique or by direct
aqueous injection. Use direct solvent injection if an organic phase is present distinct
from the aqueous phase. Use dilution as necessary to prevent saturation of the
analytical system.
7.8 Calculations:
7.8.1 Carry out all calculations for determining the concentrations and
emission rates of the target compounds. Round off figures after final calculations to
three significant figures.
7.8.2 Nomenclature
A
Stack/source cross sectional area, m2 (ft2)
Ab
Amount of volatile organic compound in bag (ng)
A,
Amount of volatile organic compound in condensate (ng)
DRAFT 0040- 30
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DRAFT METHOD 0040
kvol = Amount of volatile organic compound in analytical sample
<«g)
At = Total amount of volatile organic compound (ng), AB + Ac
3W, = Water vapor in the gas stream, proportion by volume
(x 100 = % H20)
CP = Type S pitot tube coefficient (nominally 0.84 ± 0.02),
dimensionless.
= Concentration of volatile organic compound in emissions
(ng/mL)
= Concentration of volatile organic compound per volume
sampled (ng/mL)
= Concentration of spiking standard in the Tedlar® bag
(ng/mL or fig/L)
= Concentration of spike standard in the stack/audit cylinder.
DVefr(sld) = Volumetric flow rate of exhaust gas, L/min, ftVm.
Kp = Pitot tube constant,
-'Emiflskxi
¦"vol
-'spike
¦"stock
34.97 m/sec
(—*_)(mmHg)
gmole
(K) (rnmHjO)
1/2
85.49 ft/sec
(
lb
lb mole
XinHg)
(°R) (inH20)
1/2
Maximum acceptable leakage rate for a leak check, either
pretest or following a component change; equal to
0.00057 L (0.02 ftVmin) or 4% of the average sampling
rate, whichever is less.
DRAFT 0040- 31
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DRAFT METHOD 0040
LDL^ = Lower detectable amount of volatile organic compound in
entire sampling train.
Lj = Individual leakage rate observed during the leak check
conducted before to the "i*" component change (i = 1, 2,
3...n) L/min,
Lp = Leakage rate observed during the post-test leak check,
L/min,
Max MassV0j = Maximum allowable mass flow rate (g/hr [lb/hrj) of
volatile organic compound emitted from the combustion
source.
Max Concvol = Maximum anticipated concentration of the volatile organic
compound in the exhaust gas stream, g/m3 (lb ft3).
Md = Stack-gas dry molecular weight, g/g-mole (lb/lb-mole).
Mfd = Dry mole fraction of the flue gas.
Ms = Wet molecular weight of the flue gas.
Mw = Molecular weight of water, 18.0 g/g-mole
(18.0 lb/lb-mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in. Hg).
Pg = Flue gas static pressure, mm H20 (in. H20).
Pk = Specific gravity of mercury (13.6)
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
Fstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Qm — Average sampling rate, L/min.
Qs = Calculated sampling rate, L/min.
Qsd — Volumetric air flow rate, (L/min, ftVmin).
DRAFT 0040- 32
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DRAFT METHOD 0040
R = Ideal gas constant, 0.06236 mm Hg-m3/K-g-mole
(21.85 in. Hg-ft3/ °R-lb-mole).
Tm = Absolute average dry gas meter temperature, K (°R).
T, = Absolute average stack gas temperature, K (°R).
= Standard absolute temperature, 293K (528°R).
VA = Analytical sample volume (mL).
VB = Bag volume (mL).
Vj = Concentration of volatile organic compound (wt %)
introduced into the combustion process.
V; cone = Anticipated concentration of the volatile organic compound
in the exhaust gas stream, g/L (lb/ft3).
Vlc = Total volume of liquid collected in the condensate
knockout trap.
Vm = Volume of gas sample as measured by dry gas meter, L.
vm(5id) — Volume of gas sample measured by dry gas meter,
corrected to standard conditions, L.
Vjpike = Volume of gaseous or liquid spiking standard (mL)
' TBC
VT
w(std)
WF
y
Minimum dry standard volume to be collected at dry gas
meter.
Train sample volume (mL)
Volume of water vapor in the gas sample, corrected to
standard conditions, L (ft3).
Stack gas velocity, calculated by Method 2, Equation 2-9,
using data obtained from Method 5, m/sec (ft/sec).
Mass flow rate of waste feed per hour, g/hr (lb/hr).
Dry gas meter calibration factor, dimensionless.
DRAFT 0040- 33
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DRAFT METHOD 0040
AH = Average pressure differential of orifice meter, inches H20.
AP = Actual velocity pressure, mm (in.) H20.
APavg = Average velocity pressure, mm (in.) H20.
pw = Density of water, 0.9982 g/mL (0.002201 lb/mL).
8 = Total sampling time, min.
— Sampling time interval from the beginning of a run until
the first component change, min.
= Sampling time interval between two successive component
changes, beginning with the interval between the first and
second changes, min.
Bp = Sampling time interval from the final (nBl) component
change until the end of the sampling run, min.
60 = Second/minute conversion.
100 = Conversion to percent.
7.8.3 Conversion Factors:
From To Multiply by
ft3 L 0.02832
7.8.4 Proportional Sample Rate Calculation. The flow rate to be used
during sampling when the velocity head varies from the average is calculated using
the following equation.
Q, - Q„ (l)
/iP A.
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DRAFT METHOD 0040
7.8.5 Dry Gas Volume: Correct the sample measured by the dry gas
meter to standard conditions (20°C, 760 mm Hg [68®F» 29.92 in. Hg]) by using the
following equation:
T , P. + AH/13.6 P. + AH/13.6
V « V -v — — = KV-v (2)
mfstif) m ' p I aa « j v '
m std m
where:
K, = 0.3858 K/mrn Hg for metric units, or
Kt = 17.64°R/in. Hg for English units.
Equation 2 can be used as written, unless the leakage rate observed during any
of the mandatory leak checks (i.e., the post-test leak check or leak checks conducted
before component changes) exceeds La. If Lp or Lj exceeds Lt, Equation 2 must be
modified as follows (with the approval of the appropriate regulatory personnel):
a. Case I (no component change made during sampling run):
Replace Vffi in Equation 2 with the expression:
v. - [
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DRAFT METHOD 0040
7.8.6 Volume of Water Vapor:
(3)
where:
K2
k2
= 0.001333 mVmL for metric units, or
= 0.04707 ftVmL for English units.
7.8.7 Moisture Content:
7.8.8 Volumetric Flow Rate Equations:
7.8.8.1 Static Pressure
7.8.8.2 Dry Molecular Weight
M4 = (% C02 X 0.44) + {% 02 X 0.32) + [<% CO + % N2) x 0.28] (6)
7.8.8.3 Dry Mole Fraction
Mfd = 1 - B,
DRAFT 0040- 36
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DRAFT METHOD 0040
7.8,8.4 Wet Molecular Weight
M, = (Md x Mfd) + <18 x B J
(8)
7.8.8.5 Flue Gas Velocity
V, = kp c, (,/ap),
•Vjg
MP.
7.8.8.6 Volumetric Flow Rate
DV^ = 60 V Mfd A
T
x
P
s
T
p-
K J
(9)
(10)
7.8.9 Concentration of a volatile organic compound In the gaseous
emissions of a combustion process;
7.8.9.1 Divide the amount of volatile organic compound
determined through analysis by the volume of sample introduced into the
analytical system to obtain concentration of the volatile organic compound ill
the bag or the condensate.
vol
" vol
(11)
DRAFT 0040- 37
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DRAFT METHOD 0040
7.8.9.2 Multiply the concentration of the volatile organic
compound (ng/mL) by the sample volume (bag or condensate) to determine the
amount of the volatile organic compound in the bag or condensate.
Ab = Cvol x VB (12)
or
Ac " Cvol x Vk (13)
7.8.9.3 Sum the amount of volatile organic compound found in all
samples associated with a single train.
At = Ab + Ac (14)
7.8.9.4 Divide the total amount found by the volume of stack gas
sampled to determine the concentration of the volatile organic compound in the
gaseous emissions.
£ - (15)
7.8,10 Concentration of the spiking standard in the Tedlar® bag:
V X c
r = __5± (16)
«pike y
7.8.11 Recovery of the spiking standard from the Tedlar® bag sample:
C
% Recovery = —— X 100 (17)
C«pikc
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DRAFT METHOD 0040
QUALITY CONTROL
8,1 Quality Assurnace/Oualitv Control Requirements Before Sampling
8.1.1 Pitot Tube Probe; Before sampling, assemble and calibrate the pitot
tube probe (described in Section 4.2.11) in accordance with the EPA Method 2. Leak
check to ± 10 in. HzO. The pitot tube assembly must be leak free (0.00 in. HzO in
1 minute).
8.1.2 Pressure Gauge (Manometer): Calibrate the pressure gauge
(described in Section 4.2.12) in accordance with the EPA Method 2. Leak check the
pitot tubes, pressure gauge, and pitot tube lines simultaneously, as a unit, before the
velocity traverse.
8.1.3 Thermocouple and Temperature Readout Device: Calibrate these
devices (desribed in Section 4.2.10.6) within 30 days of sampling and in accordance
with the EPA Method 2. The thermocouple and temperature read out must be
accurate to ± 1°C (± 2°F).
8.1.4 Metering System: Calibrate the dry gas meter contained in the
control console in accordance with the procedures outlined in Section 5.3 of EPA
Method 5. Calibrate the meter at a flow rate appropriate for the sampling rate used
during the test.
8.1.5 Probe Heater: Calibrate the probe heater before sampling collection
following procedures outlined in Section 5.5 of EPA Method 5.
DRAFT 0040- 39
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DRAFT METHOD 0040
8.1.6 Barometer: Adjust the barometer daily and before each test series to
+ 0.1 in. (25 mm) Hg of the corrected barometric pressure reported by a National
Weather Service Station located neaitoy and at the same altitude above sea level.
8.2 Number nf Sampling Runs: The number of sampling runs to be performed
shall be determined by the appropriate regulatory personnel. At least two runs (two hours of
stack sampling time) are recommended for each test series to provide minimal statistical data.
Ensure that all compounds on the analyte list have been validated for this method
prior to sampling. Perform validation as required in accordance with the EPA Method 301.6
8.3 Blanks and Field Spikes: Field, trip and laboratory blanks, contamination
checks and field spiked samples are required to monitor the performance of the sampling
method and to provide the required information to take corrective action if problems are
observed in the laboratory operations or in field sampling activities.
8.3.1 Field blanks: Take at least one field blank sample daily and per
source. Collect high purity air or N2 (99.998%) from a compressed gas cylinder in
the same manner as source emissions. Draw the air or nitrogen gas through the
sampling system and into the bag. Field blank samples shall consist of the condensate
and a bag sample. Transport and analyze this blank sample along with the stack gas
samples. When the field bland values are greater than 20% of the stack values, flag
the data. Report the field blank values with the stack gas results.
8.3.2 Trip Blanks: Take at least two Tedlar® bags labeled "trip blanks"
and filled with an inert gas to the sampling site. These bags will be treated like any
other samples except that they will not be opened during storage at the site. These
bags will be subsequently analyzed to monitor potential contamination which may
occur during storage and shipment.
DRAFT 0040- 40
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DRAFT METHOD 0040
8.3.3 Laboratory Blanks: Leave two Tedlar® bags labeled "Laboratory
blanks; in the laboratory using the method of storage that is used for field samples. If
the field and trip blanks contain high concentrations of contaminants (i.e., greater
than five times the detection limit of particular analyte), the laboratory blank shall be
analyzed to identify the source of contamination.
8.3.4. Tedlar® Bag Contamination Checks: The use of new bags for each
test series is recommended. All bags must be cleaned and checked for contamination
before being used for sampling (Section 6.1.3).
8.3.5. Field Spike Samples: Take at least one field spike sample per 10
field samples, or a minimum number of one field spike per test. Spike the chosen
bag sample with a known mixture (gaseous or liquid) of all the target pollutants using
either gaseous or liquid injection into the bag. Transport and analyze the spiked
sample with the stack gas samples. Report the spike sample recoveries with the
source test results. The compound recoveries in the spiked sample must be greater
than 80% and less than 120%. Use Equation 17 in Section 7.8.11 to calculate spiking
compound recovery.
The spiking level should be at least the level anticipated in the emissions
matrix. Use Equation 16 in Section 7.8.10 to calculate the spiking level. The
syringe volume for the gaseous injection should not exceed 200 mL to minimize
leakage through the septum after injection. For liquid injections, the volume injected
must not exceed 1 mL to ensure complete volatilization. The final volume of the
spiked gas must not exceed 1 % of the total sample volume. Use the ideal gas
equation to calculate the volume of gas generated by a liquid injection into the bag.
DRAFT 0040-41
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DRAFT METHOD 0040
8,3.5,1 Procedure for the Ipjection of Gaseous or Liquid
Standards:
1. Obtain spiking stock that is sufficiently concentrated to spike a
Tedlai® sample without exceeding 1 % volume limit. Select
appropriate analyzes, analyte homologs, or isotopieally labeled
analogs in cylinders or SUMMA® canisters for gaseous
injections or neat liquids or methanol solutions for liquid
injections.
2. Install an injection port that consists of a Swagelok® tee fitting
with a septum, in the sample line just before the 1/4-in. quick
connector on the Tedlar® bag (Figure 2). Locate this port as
close the bag as possible to minimize wall effects. Use a new
septum for each sampling run that involves spiking.
3. Perform a leak test as described in Section 7.3 with the injection
port in line.
4. Start sampling the stack as described in Sections 7.4 and 7.5.
5. In preparation for injection, clean the syringe by flushing three
times with an inert gas (high purity N2, 99.998%) for gaseous
injections, or with methanol for liquid injections. Then flush
the syringe three times with the gaseous or liquid spiking
standard.
6. After half an hour of sample collection, take up the desired
volume of the spiking standard into the syringe (for gases, allow
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DRAFT 0040- 42 June 1994
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DRAFT METHOD 0040
the standard to equilibrate to atmospheric pressure) and inject it
through the septum into the bag without interruping the
sampoing procedure. All apparatus upstream of the bag should
be under slight negative pressure.
8.4 Performance Audits: Conduct performance audits to evaluate quantitatively
the quality of data produced by the total measurement system (sample collection, sample
analysis, and data processing). Accuracy (% recovery) must be greater than 50% and less
than 150 percent. Precision (% relative standard deviation) must be less than 50 percent.
Better performance must be achieved routinely.
DRAFT 0040- 43
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DRAFT METHOD 0040
9.0 METHOD PERFORMANCE
9.1 Method Performance Evaluation: Evaluation of analytical procedures for a
selected series of compounds shall include the sample preparation procedures and each
associated analytical determination. Challenge the analytical procedures by spiking the test
compounds at appropriate levels carried through the procedures.
9.2 Method Detection Limit: Determine the overall method detection limits
(lower and upper) on a compound-by-compound basis according to the 40 CFR Part 136b for
the determination of the detection limit.7 Different compounds may exhibit different
collection efficiencies as well as instrumental minimum detection limit.
9.3 Method Precision and Bias: Determine the overall method precision and bias
(in accordance with the EPA Method 3016) on a compound-by-compound basis at a given
concentration level. Include in the method precision value a combined variability due to
sampling and instrumental analysis. The method bias is dependent upon the collection
efficiency of the train components.
No evaluation and validation data are available for this method.
DRAFT 0040- 44
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DRAFT METHOD 0040
10.0 REFERENCES
1. Howe, G.B., B.A. Pate, and R.K.M. Jayanty, "Stability of Volatile Principal Organic
Hazardous Constituents (POHCs) in Tedlai® Bags," Research Triangle Institute
Report to the EPA, Contract No. 68-02-4550, 1991.
2. Andino, J.M., and J. W. Butler, "A Study of the Stability of Methanol-Fueled
Vehicle Emissions in Tedlai® Bags", Environ, Sci. Technol. 1991, 25(9), 1644-1646.
3. Posner, J.C., and W.J. Woodfin, "Sampling with Gas Bags I: Loses of Analyte with
Time," Appendix L Industrial Hygiene, 1986, (4), 163-168.
4. Seila, R.L., W.A. Lonneman, and S.A. Meeks, "Evaluation of Polyvinyl Fluoride as
a Container Material for Air Pollution Samples," J.Environ. Sci. Health., 1976, 2,
121-130.
5. U.S. Environmental Protection Agency, Hazardous Waste Incineration Measurement
Guidance Manual, Volume III of the Hazardous Waste Incineration Guidence Series,
EPA/625/6-89/021, p5.
6. U.S. Environmental Protection Agency, Method 301, "Protocol for the Field
Validation of Emission Concentrations from Stationary sources", EPA 450/4-90-015,
February 1991.
7. U.S. Environmental Protection Agency, 40 CFR Part 136, Appendix B, "Definition
and Procedure for the Determination of the Method Detection Limit".
DRAFT 0040- 45
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DRAFT METHOD 0040
11.0 BIBLIOGRAPHY
Test Methods for Evaluating Solid Waste, 3rd ed,, SW-846. U.S. Environmental
Protection Agency. Office of Solid Waste and Emergency Response. U.S.
Government Printing Office: Washington, D.C., 1987.
U.S. Environmental Protection Agency, 40 CFR Part 60, Appendix A, Methods 1,2,
3, 4, 5, 18 and 25,
DRAFT 0040- 46
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DRAFT METHOD 0040
Table 1
Compounds For Which Applicability of the Method Has Been Demonstrated
Compound
¦XAS''-.'
No.
Boiling
Point
TO
Condensation
Point
at 20°<: (%)
Estimated
Instrument
Detection
Limit*
(ppm)
Diehlorodifluoromethane
75718
-30
Gas
0.20
Vinyl chloride
75014
-19
Gas
0.11
1,3-Butadiene
106990
-4
Gas
0.90
1,2-DichIor-l, 1,2,2-tetrafluoroethane
76142
4
Gas
0.14
Methyl bromide
74839
4
Gas
0.14
T richlorofluoromethane
353548
24
88
0.18
Vinylidene chloride
75354
31
22
0.07
Methylene chloride
75092
40
44
0.05
1,1,2 -Trichlorotrifl uoroethan e
76131
48
37
0.13
Chloroform
67663
61
21
0.04
1,1,1-Trichloroe thane
71556
75
13
0.03
Carbon tetrachloride
56235
77
11
0.03
Benzene
71432
80
10
0.16
T richloroethylene
79016
87
8
0.04
1,2-Dichloropropane
78875
96
5
0.05
Toluene
108883
111
3
0.08
Tetrachloroethylene
127184
121
2
0.03
"Since this value represents a direct injection (no concentration) from the Tedlar® bag,
these values are directly applicable as stack detection limits
DRAFT 0040- 47
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DRAFT METHOD 0040
Table 2
Problems That Can Invalidate Tedlar® Bag Sampling
Data and Suggested Remedies
Remedy
1. Condensation of the gases or water
vapor in the bag
2. Leaks developing in the bag during
testing, transport, and/or analysis
3. Hydrocarbon contamination
Sample below the condensation point of the
analytes; lower the temperature in the
condensate trap.
Use double sealed bags; perform additional
sampling runs; protect the bags from sharp
objects by sampling and shipping in rigid,
opaque containers; ship the bags in the
same containers used during sampling.
Minimize exposure of the bag to heat and
direct light, by sampling and shipping in
rigid, opaque containers; purge the bags
with ultrapure N2 in the laboratory and
establish through analysis that the
hydrocarbon levels are acceptable; use the
bags only once.
DRAFT 0040- 48
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DRAFT METHOD 0040
Applicable Source
and Analytes
Explosion Hazard Area
Compounds with Boiling
Paints > 121*C
Compounds Unstable In Bag
Use Other
Sampling Methods J
Presurvey
Measurements
Select
Condenser Trap Size
Analytical Detector
Flow Rate (Proportional vs. Constant)
Preparation
and Set-up
Assembly of the Sample Train
' Preliminary Velocity and Temperature Traverse
Determination of Moisture Content
Selection of Sample Volume and Flow Rate
Bag
Leak Check
Leak Rate > 0.1 in. Hg in t min.
or > 4% of the Sample Rate
C Discard Bag \
and Use Another J
Acceptable Leak Rate
Pre-test Train
Leak Check
Leak Rate > 0.1 in. Hg in 1 min.
or > 4% of the Sample Rate
Check All Connections
Repeat Leak Check
Acceptable Leak Rate
Insert Probe
into Gas Stream
Figure 1. Outline of Method 0040
DRAFT 0040- 49
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DRAFT METHOD 0040
Steady
Flow Rate
Source
Variable
Flow Rate
Source
Flag Invalid Test Data"*
Discard Invalid Samples
Repeat Test Run
Leak Rata > 0.1 in. Hg in 1 min.
or > 4% of the Sample Rate
Collect Sample
Using Proportional
Sampling Rate
Collect Sample
Using Constant
Sampling Rate
Purge
Probe Assembly
Post-test Train
Leak Check
Insert Probe
into Gas Stream
Acceptable Leak Rate
Sample Recovery
and Transport
Post-transport
Leak Check on Bags
In-leakage > 20%
Out-leakage > 20%
j Flag Invalid Test Data
Discard Invalid Samples J
!
Acceptable Leakage
Analysis
(within 72 Hours of
Sample Collection)
Figure I. Continued
DRAFT 0040- 50
Revision C
June 1994
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Duct
Proba
Temperature Sensor
Proba Isolation Valve
Filler Hofder
(with Filter)
Charcoal Trap
Pilot Tuba
Manometer
Purge Line
Quick Connector
ce Bath
Condenser
Glass Condensate Trap
Quick
Connectors
*
Condenser Tamp (J
D Filter Temp
5
©Probe Temp (
0 Stack Tamp |
Air Tight Container
' C
Return
Line
\=
Bag Isolation
Valve
Teflon
Bulkhead
Union
Tedlar®Bag-
injectlon Port
for Spiking
ft i 1
1,1 r-t vj—"T-r
o«*—Teflon Union
' s
t \
i \
i i
i i
\ <
v t
\ i
\ /
\ /
\ /
To
VOST Control
Console
Quick
Connectors
§
Figure 2, Schematic of the Method 0040 Sampling Train
-------
DRAFT METHOD 0040
3-Way Glass Valve
With Teflon Stopcock
00
5/16'
Valve Stem Reduced
' From 5/16" to 1/4*
00
1/4-
-r w*
(AH 3 Stems Of Equal
Length, Size, & Shape]
Heat Wrap Valve
And Heat To 13(f - 14(f C
Out
Figure 3. Isolation Valve Design
DRAFT 0040- 52
Revision 0
June 1994
-------
DRAFT METHOD 0040
0
©
***
Probe Isolation Valve Positions
© Isolation Position © Sample Position (3) Vacuum Purge Position
(Post Test) System Purge Position (Pre Tast) (Release System Pressure
After Leak Checks)
(D Isolation Position
System Purge Position (Pre Test)
Leak Check Position (Post Test)
Baa Isolation Valve Positions
©Sample Position
® Bag Evacuation Position
Bag Leak Check Position
{Pre Test)
Figure 4. Valve Operation
DRAFT 0040- 53
Revision 0
June 1994
-------
DRAFT METHOD 0040
Front Vtew
Schematic Diagram
Figure 5. Diagram of a Control Console
DRAFT 0040-54
Revision 0
June 1994
-------
DRAFT METHOD 0040
Control Console Components
1. 1/4 in. S.S. Quick Connect - Vacuum line inlet from sample train (to bag container).
2. Amphenol Receptacle - provides power through umbilical to probe heat & water pump.
3. Thermocouple Receptacles - 4 thermocouple inlets for:
1. Stack Temperature
2. Probe Temperature
3. Condenser Temperature
4. Ambient Temperature
4. 110 VAC Receptacle - auxiliary power for isolation valve heat.
5. Vacuum Gauge - 0-30 in. Hg.
6. Heat Controller
7. Digital Thermocouple Read Out - 10 channel (displays temperature readings during sampling)
(1-4 remote as listed above)
(5 dry gas meter temperature)
(6-10 spares)
S. Timer (optional)
9. Power Switches - control (on/off)
1. Main power - with separate switches for each.
2. Sample pump
3. Water pump
4. Timer
10. Meter pressure Gauge - (inches water column)
11. Fine Adjustment (Bypass) Valve
12. Coarse Adjustment (on/off) Valve
13. Dry Gas Meter
14. Rotometer (Flow Meter)
15. Charcoal Trap (Optional)
Figure 5. Continued
DRAFT 0040- 55
Revision 0
June 1994
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DRAFT METHOD 0040
1. Name of Company
Address
Contacts
Process to be sampled
Duct or vent to be sampled
II. Process description
Raw Material
Products
Date
Phone
Operating cycle
Check: Batch
Timing of batch or cycle
Best time to test
III. Sampling site
A. Description
Site description
Duct shape and size
Materials
Wall thickness
Upstream distance
Downstream distance
Size of port
Continuous
Cyclic
inches
inches
inches
.diameter
.diameter
Figure 6. Pretest Survey Data Form
Revision 0
DRAFT 0040- 56 June 1994
-------
DRAFT METHOD 0040
Temperature °C Data Source
Velocity Data Source
Static pressure inches HzO Data Source
Moisture content % Data Source
Particulate content __ Data Source
Gaseous components
Nj % Hydrocarbons ppm
Oj % ppm
CO % ppm
C02 % ppm
U/\ Of ,,,
a\J2 7b „ ppm
Hydrocarbon components
ppm
ppm
ppm
PPm
ppm
PP«n
C. Sampling considerations
Location to set up GC
Power available at duct
Plant entry requirements
Security agreements
Potential problems
Site diagrams (Attach additional sheets if required).
figure 6. Continued
Revision 0
DRAFT 0040- 57 June 1994
-------
Plant
City
Operator
Date
Run Number
Stack dia. (in.)
Sample box number
Pitot tube (Cp)
Static press
Flowmeter calib (Y)
Average (AP)
Initial flowmeter setting
Average stack temp
Barometric pressure
(in.) H20
in. H»0
liters
Dilution system: (dynamic)
emission flowsetting
diluent flowsetting
Dilution system: (statis)
emission flowsetting
Final leak check
Vacuum during leak check
Sampling point location
Total concensate volume
VOA vial size
VOA vial number
Tedlai* bag volume
Container volume
Container number
fin.) Hg
(cfa)
(in. H20)
mL
mL
liters
liters
Figure 7. field Sampling Data Form
-------
Appendix F
SW-846, Method 0010
Modified Method 5 Sampling Train
(This is the latest version of Method 0010 from SW-846.
The final version of the document when released supersedes
this one and will be inserted in its place)
-------
METHOD 0010
MODIFIED METHOD 5 SAMPLING TRAIN
1.0 SCOPE AND APPLICATION
1.1 This method is applicable to the determination of Destruction and Removal
Efficiency (DRE) of semivolatile Principal Organic Hazardous Compounds (POHCs) from
incineration systems (PHS, 1967). This method also may be used to determine particulate
emission rates from stationary sources as per EPA Method 5 (see References at the end of this
method).
2.0 SUMMARY OF METHOD
2.1 Gaseous and particulate pollutants are withdrawn from an emission source at an
isokinetic sampling rate and are collected in a multicomponent sampling train. Principal
components of the train include a high-efficiency glass- or quartz-fiber filter and a packed bed
of porous polymeric adsorbent resin. The filter is used to collect organic-laden particulate
materials and the porous polymeric resin to adsorb semivolatile organic species. Semivolatile
species are defined as compounds with boiling points > 100° C.
2.2 Comprehensive chemical analyses of the collected sample are conducted to
determine the concentration and identity of the organic materials.
3.0 INTERFERENCES
3.1 Oxides of nitrogen (NOJ are possible interferents in the determination of
certain water-soluble compounds such as dioxane, phenol, and u re thane; reaction of these
compounds with NO, in the presence of moisture will reduce their concentration. Other
possibilities that could result in positive or negative bias are (1) stability of the compounds in
methylene chloride, (2) the formation of water-soluble organic salts on the resin in the
presence of moisture, and (3) the solvent extraction efficiency of water-soluble compounds
from aqueous media. Use of two or more ions per compound for qualitative and quantitative
analysis can overcome interference at one mass. These concerns should be addressed on a
compound-by-compound basis before using this method.
6SO-049-O8-O5/mclJiOQiO/
5-15-95/jfd
0010-1
Reviiion: O
Dm; September 1986
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4.0 APPARATUS AND MATERIALS
4.1 Samplinp Train?
4.1.1 A schematic of the sampling train used in this method is shown in Figure
1. This sampling train configuration is adapted from EPA Method S procedures, and,
as such, the majority of the required equipment is identical to that used in
EPA Method 5 determinations. The new components required are a condenser coil and
a sorbent module, which are used to collect semivolatile organic materials that pass
through the glass- or quartz-fiber filter in the gas phase.
4.1.2 Construction details for the basic train components are given in
APTD-0581 (see Martin, 1971, in Section 13.0, References); commercial models of
this equipment are also available. Specifications for the sorbent module are provided in
the following subsections. Additionally, the following subsections list changes to
APTD-0581 and identify allowable train configuration modifications.
4.1.3 Basic operating and maintenance procedures for the sampling train are
described in APTD-0576 (see Rom, 1972, in Section 13.0, References). As correct
usage is important in obtaining valid results, all users should refer to APTD-0576 and
adopt the operating and maintenance procedures outlined therein unless otherwise
specified. The sampling train consists of the components detailed below.
4.1.3.1 Probe nozzle: Stainless steel (316) or glass with sharp, tapered
(30° angle) leading edge. The taper shall be on the outside to preserve a
constant I.D. The nozzle shall be buttonhook or elbow design and constructed
from seamless tubing (if made of stainless steel). Other construction materials
may be considered for particular applications. A range of nozzle sizes suitable
for isokinetic sampling should be available in increments of 0.16 cm (1/16 in,),
e.g., 0.32-1.27 cm (1/8-1/2 in.), or larger if higher volume sampling trains are
used. Each nozzle shall be calibrated according to the procedures outlined in
Paragraph 9.1.
4.1.3.2 Probe liner: Borosilieate or quartz-glass tubing with a heating
system capable of maintaining a gas temperature of 120 ± 14°C (248 ± 25°F)
at the exit end during sampling. (The tester may opt to operate the equipment at
a temperature lower than that specified.) Because the actual temperature at the
outlet of the probe is not usually monitored during sampling, probes constructed
according to APTD-0581 and utilizing the calibration curves of APTD-0576 (or
calibrated according to the procedure outlined in APTD-0576) are considered
acceptable. Either borosilieate or quartz-glass probe liners may be used for
stack temperatures up to about 480°C (900DF). Quartz liners shall be used for
temperatures between 480 and 900°C (900 and 1650°F). [The softening
temperature for borosilieate is 820° C
65Q-049-08-05/meth0010/
5-15-95/jfd
0010-2
Revimoit: Q
Out: September 1986
-------
Stack
Waff
Thermocouples
Filter
Thermocouple
Heated Box
XAD-2
"^pePitot
Check
Valve
Silica Gel
Thermocouples Conder)sate
Vacuum
Gauge
Vacuum
Line
By-pass
Valve
Main
Valve
Pump
Figure 1. Modified Method 5 Sampling Train
6SO-049-O*-Q5/metMMlO/ . , Revktao: Q
5-15-95/jfd 0010-3 Put: September 1986
-------
(1508°F), and for quartz 1500°C (2732°F).] Water-cooling of the stainless
steel sheath will be necessary at temperatures approaching and exceeding
500oC.
4.1.3.3 Pitot tube: Type S, as described in Section 2.1 of EPA
Method 2, or other appropriate devices (Vollaro, 1976), The pitot tube shall be
attached to the probe to allow constant monitoring of the stack gas velocity.
The impact (high-pressure) opening plane of the pitot tube shall be even with or
above the nozzle entry plane (see EPA Method 2, Figure 2-6b) during
sampling. The Type S pitot tube assembly shall have a known coefficient,
determined as outlined in Section 4 of EPA Method 2.
4.1.3.4 Differential pressure gauge! Inclined manometer or equivalent
device as described in Section 2.2 of EPA Method 2. One manometer shall be
used for velocity-head (AP) readings and the other for orifice differential
pressure (AH) readings.
4.1.3.5 Filter holder: Borosilicate glass, with a glass frit filter support
and a sealing gasket. The sealing gasket should be made of materials that will
not introduce organic material into the gas stream at the temperature at which
the filter holder will be maintained. The gasket shall be constructed of Teflon®
or materials of equal or better characteristics. The holder design shall provide a
positive seal against leakage at any point along the filter circumference. The
holder shall be attached immediately to the outlet of the cyclone or cyclone
bypass.
4.1.3.6 Filter heating system: Any heating system capable of
maintaining a temperature of 120 ± 14°C (248 ± 25 °F) around the filter
holder during sampling. Other temperatures may be appropriate for particular
applications. Alternatively, the tester may opt to operate the equipment at
temperatures other than that specified. A temperature gauge capable of
measuring temperature to within 3°C (5.4°F) shall be installed so that the
temperature around the filter holder can be regulated and monitored during
sampling. Heating systems other than the one shown in APTD-0581 may be
used.
4.1.3.7 Organic sampling module: This unit consists of three sections,
including a gas-conditioning section, a sorbent trap, and a condensate knockout
trap. The gas-conditioning system shall be capable of conditioning the gas,
leaving the back half of the filter holder to a temperature not exceeding 20°C
(68 °F). The sorbent trap shall be sized to contain approximately 20 g of porous
polymeric resin (Rohm and Haas XAD-2 or equivalent) and shall be jacketed to
maintain the internal gas temperature at 17 ± 3°C (62.5 ± 5.4°F). The most
commonly used coolant is ice water from the impinger ice-water bath,
constantly circulated through the outer jacket, using rubber or plastic tubing and
650-049-08-05/meih0010/
5-15-95/jfd
0010-4
Revision: O
Dtle: September I98fi
-------
a peristaltic pump. The sorbent trap should be outfitted with a glass well or
depression, appropriately sized to accommodate a small thermocouple in the
trap for monitoring the gas entry temperature. The condensate knockout trap
shall be of sufficient size to collect the condensate following gas conditioning.
The organic module components shall be oriented to direct the flow of
condensate formed vertically downward from the conditioning section, through
the adsorbent media, and into the condensate knockout trap. The knockout trap
is usually similar in appearance to an empty impinger directly underneath the
sorbent module; it may be oversized but should have a shortened center stem (at
a minimum, one-half the length of the normal impinger stems) to collect a large
volume of condensate without bubbling and overflowing into the impinger train.
All surfaces of the organic module wetted by the gas sample shall be fabricated
of borosilicate glass, Teflon®, or other inert materials. Commercial versions of
the complete organic module are not currently available, but may be assembled
from commercially available laboratory glassware and a custom-fabricated
sorbent trap. Details of two acceptable designs are shown in Figures 2 and 3
(the thermocouple well is shown in Figure 2).
4.1.3.8 Impinger train: To determine the stack-gas moisture content,
four 500-mL impingers, connected in series with leak-free ground-glass joints,
follow the knockout trap. The first, third, and fourth impingers shall be of the
Greenburg-Smith design, modified by replacing the tip with a 1.3-cm (V4-in.)
I.D. glass tube extending about 1.3 cm ('A in.) from the bottom of the outer
cylinder. The second impinger shall be of the Greenburg-Smith Design with the
standard tip. The first and second impingers shall contain known quantities of
water or appropriate trapping solution. The third shall be empty or charged
with a caustic solution, should the stack gas contain hydrochloric acid (HC1).
The fourth shall contain a known weight of silica gel or equivalent desiccant.
4.1.3.9 Metering system: The necessary components are a vacuum
gauge, leak-free pump, thermometers capable of measuring temperature to
within 3°C (5.4°F), dry-gas meter capable of measuring volume to within 1%,
and related equipment, as shown in Figure 1. At a minimum, the pump should
be capable of 4 cfm free flow, and the dry-gas meter should have a recording
capacity of 0-999.9 cu ft with a resolution of 0.005 cu ft. Other metering
systems capable of maintaining sampling rates within 10% of isokineticity and
of determining sample volumes to within 2% may be used. The metering
system must be used in conjunction with a pitot tube to enable checks of
isokinetic sampling rates. Sampling trains using metering systems designed for
flow rates higher than those described in APTD-0581 and APTD-0576 may be
used, provided that the specifications of this method are met.
650-049-O&-O5/rk(1iOO 10/
5-15-95/jW
0010-5
Siviaioit: fl
Dale: September 1986
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4*
*:
M-
28/12
Ball Joint
¦*-1-11/16" or 45 mm
^3
•v 6.5 in.
or
168 mm
-M
20/12
Sockat Joint
40 RC Glass Frit
Water Jacket
s f>
s
I
a.
&
o
Figure 2, Adsorbent Sampling System
-------
Flow Direction
8 mm Glass Cooling Coil
Retaining Spring
Glass
Wool Plug
Fritted Stainless Steel Disc —
15 mm Solv-Seal Joint
(or 20/12 Socket Joint)
28/12 Bali Joint
Glass Fritted Disc
Glass Water Jacket
a.
jjjjj
e
Figure 3, Adsorbent Sampling System
-------
, 4.1.3.10 Barometer: Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg). In many
cases the barometric reading may be obtained from a nearby National Weather
Service station, in which case the station value (which is the absolute barometric
pressure) is requested and an adjustment for elevation differences between the
weather station and sampling point is applied at a rate of minus 2.5 mm Hg
(0.1 in. Hg) per 30-m (100 ft) elevation increase (vice versa for elevation
decrease).
4.1.3.11 Gas density determination equipment: Temperature sensor and
pressure gauge (as described in Sections 2.3 and 2.4 of EPA Method 2), and
gas analyzer, if necessary (as described in EPA Method 3). The temperature
sensor ideally should be permanently attached to the pitot tube or sampling
probe in a fixed configuration such that the tip of the sensor extends beyond the
leading edge of the probe sheath and does not touch any metal. Alternatively,
the sensor may be attached just prior to use in the field. Note, however, that if
the temperature sensor is attached in the field, the sensor must be placed in an
interference-free arrangement with respect to the Type S pitot tube openings
(see EPA Method 2, Figure 2-7). As a second alternative, if a difference of no
more than 1 % in the average velocity measurement is to be introduced, the
temperature gauge need not be attached to the probe or pitot tube.
4.1.3.12 Cal ihr-ation/field-preparation record: A permanently bound
laboratory notebook, in which duplicate copies of data may be made as they are
being recorded, is required for documenting and recording calibrations and
preparation procedures (i.e., filter and silica gel tare weights, clean XAD-2,
quality assurance/quality control check results, dry-gas meter, and thermocouple
calibrations, etc.). The duplicate copies should be detachable and should be
stored separately in the test program archives.
4.2 Sample Recovery:
4.2.1 Probe liner: Probe nozzle and organic module conditioning section
brushes; nylon bristle brushes with stainless steel wire handles are required. The probe
brush shall have extensions of stainless steel, Teflon®, or inert material at least as long
as the probe. The brushes shall be properly sized and shaped to brush out the probe
liner, the probe nozzle, and the organic module conditioning section.
4.2.2 Wash bottles: Three. Teflon® or glass wash bottles are recommended;
polyethylene wash bottles should not be used because organic contaminants may be
extracted by exposure to organic solvents used for sample recovery.
4.2.3 Glass sample storage containers: Chemically resistant, borosilicate
amber and clear glass bottles, 500-mL or 1,000-mL. Bottles should be tinted to
prevent action of light on sample. Screw-cap liners shall be either Teflon® or
650-049-08-Q5/meth0010/
5-15-95/5fd
0010-8
Revision: O
Date: September 1986
-------
constructed so as to be leak-free and resistant to chemical attack by organic recovery
solvents. Narrow-mouth glass bottles have been found to exhibit less tendency toward
leakage.
4.2.4 Petri dishes: Glass, sealed around the circumference with wide (1-in.)
Teflon* tape, for storage and transport of filter samples.
4.2.5 Graduated cylinder and/or balances: To measure condensed water to
the nearest 1 mL or 1 g. Graduated cylinders shall have subdivisions not >2 mL.
Laboratory triple-beam balances capable of weighing to ±0.5 g or better are required.
4.2.6 Plastic storage containers: Screw-cap polypropylene or polyethylene
containers to store silica gel.
4.2.7 Funnel and rubber policeman: To aid in transfer of silica gel to
container (not necessary if silica gel is weighed in field).
4.2.8 Funnels: Glass, to aid in sample recovery.
4.3 Filters: Glass- or quartz-fiber filters, without organic binder, exhibiting at least
99.95% efficiency (<0.05% penetration) on 0.3-um dioctyl phthalate smoke particles. The
filter efficiency test shall be conducted in accordance with ASTM standard method D2986-71.
Test data from the supplier's quality control program are sufficient for this purpose. In
sources containing S02 or S03, the filter material must be of a type that is unreactive to S02 or
S03. Reeve Angel 934 AH or Schleicher and Schwell #3 filters work well under these
conditions.
4.4 Crushed Ice: Quantities ranging from 10-50 lb may be necessary during a
sampling run, depending on ambient air temperature.
4.5 Stopcock grease: Solvent-insoluble, heat-stable silicone grease. Use of
silicone grease upstream of the module is not permitted, and amounts used on components
located downstream of the organic module shall be minimized. Silicone grease usage is not
necessary if screw-on connectors and Teflon® sleeves or ground-glass joints are used.
4.6 Glass wool: Used to plug the unfritted end of the sorbent module. The glass-
wool fiber should be solvent-extracted with methylene chloride in a Soxhlet extractor for 12 hr
and air-dried prior to use.
5.0 REAGENTS
5.1 Adsorbent resin: Porous polymeric resin (XAD-2 or equivalent) is
recommended. These resins shall be cleaned prior to their use for sample collection.
Appendix A of this method should be consulted to determine appropriate precleaning
procedure. For best results, resin used should not exhibit a blank of higher than 4 mg/kg of
650-049-08-05/fneih0010/
5-15-95i]fd
0010-9
0
Dale: September HSft
-------
total chromatographable organics (TCO) (see Appendix B) prior to use. Once cleaned, resin
should be stored in an airtight, wide-mouth amber glass container with a Teflon®-lined cap or
placed in one of the glass sorbent modules tightly sealed with Teflon* film and elastic bands.
The resin should be used within 4 wk of the preparation.
5.2 Silica gel; Indicating type, 6-16 mesh. If previously used, dry at 175°C
(350°F) for 2 hr before using. New silica gel may be used as received. Alternatively, other
types of desiccants (equivalent or better) may be used, subject to the approval of the
Administrator.
5.3 Tmpinger solutions: Distilled organic-free water (Type II) shall be used, unless
sampling is intended to quantify a particular inorganic gaseous species. If sampling is intended
to quantify the concentration of additional species, the impinger solution of choice shall be
subject to Administrator approval. This water should be prescreened for any compounds of
interest. One hundred mL will be added to the specified impinger; the third impinger in the
train may be charged with a basic solution (1 N sodium hydroxide or sodium acetate) to
protect the sampling pump from acidic gases. Sodium acetate should be used when large
sample volumes axe anticipated because sodium hydroxide will react with carbon dioxide in
aqueous media to form sodium carbonate, which may possibly plug the impinger.
5.4 Sample recovery reagents:
5.4.1 Methylene chloride: Distilled-in-glass grade is required for sample
recovery and cleanup (see Note to 5.4.2 below).
5.4.2 Methyl alcohol: Distilled-in-glass grade is required for sample recovery
and cleanup.
NOTE: Organic solvents from metal containers may have a high-residue blank and
should not be used. Sometimes suppliers transfer solvents from metal to glass
bottles; thus blanks shall be run prior to field use and only solvents with low
blank value ( < 0.001 %) shall be used.
5.4.3 Water: Water (Type II) shall be used for rinsing the organic module
and condenser component.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Because of complexity of this method, field personnel should be trained in and
experienced with the test procedures in order to obtain reliable results.
6.2 Laboratory preparation:
6.2.1 All the components shall be maintained and calibrated according to the
procedure described in APTD-0576, unless otherwise specified.
65(M>49-08-0i/methOG 10/
5-15-95/jfd
0010-10
Reviiion:,
Dale: !
-------
6.2.2 Weigh several 200- to 300-g portions of silica gel in airtight containers
to the nearest 0.5 g. Record on each container the total weight of the silica gel plus
containers. As an alternative to preweighing the silica gel, it may instead be weighed
directly In the implnger or sampling holder just prior to train assembly.
6.2.3 Check filters visually against light for irregularities and flaws or pinhole
leaks. Label the shipping containers (glass Petri dishes) and keep the filters in these
containers at all times except during sampling and weighing.
6.2.4 Desiccate the filters at 20 ± 5.6°C (68 ± 10°F) and ambient pressure for
at least 24 hr, and weigh at intervals of at least 6 hr to a constant weight
(i.e., <0.5-mg change from previous weighing), recording results to the nearest
0.1 mg. During each weighing the filter must not be exposed for more than a 2-min
period to the laboratory atmosphere and relative humidity above 50%. Alternatively
(unless otherwise specified by the Administrator), the filters may be oven-dried at
105°C (220°F) for 2-3 hr, desiccated for 2 hr, and weighed.
6.3 Preliminary field determinations:
6.3.1 Select the sampling site and the minimum number of sampling points
according to EPA Method 1 or as specified by the Administrator. Determine the stack
pressure, temperature, and range of velocity heads using EPA Method 2. It is
recommended that a leak-check of the pitot lines (see EPA Method 2, Section 3.1) be
performed. Determine the stack-gas moisture content using EPA Approximation
Method 4 or its alternatives to establish estimates of isokinetic sampling-rate settings.
Determine the stack-gas dry molecular weight, as described in EPA Method 2,
Section 3.6. If integrated EPA Method 3 sampling is used for molecular weight
determination, the integrated bag sample shall be taken simultaneously with, and for
the same total length of time as, the sample run.
6.3.2 Select a nozzle size based on the range of velocity heads so that it is not
necessary to change the nozzle size in order to maintain isokinetic sampling rates.
During the run, do not change the nozzle. Ensure that the proper differential pressure
gauge is chosen for the range of velocity heads encountered (see Section 2.2 of
EPA Method 2.)
6.3.3 Select a suitable probe liner and probe length so that all traverse points
can be sampled. For large stacks, to reduce the length of the probe, consider sampling
from opposite sides of the stack.
6.3.4 A minimum of 3 dscm (105.9 dscf) of sample volume is required for the
determination of the Destruction and Removal Efficiency (DRE) of POHCs from
incineration systems. Additional sample volume shall be collected as necessitated by
analytical detection limit constraints. To determine the minimum sample volume
required, refer to sample calculations in Section 10.0.
65O-049-O8-O5/methOOlO/
0010-11
Revrtion: 0
D«te: September 1986
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6.3.5 Determine the total length of sampling time needed to obtain the
identified minimum volume by comparing the anticipated average sampling rate with
the volume requirement. Allocate the same time to all traverse points defined by
EPA Method I. To avoid timekeeping errors, the length of time sampled at each
traverse point should be an integer or an integer plus one-half min.
6.3.6 In some circumstances (e.g., batch cycles) it may be necessary to sample
for shorter times at the traverse points and to obtain smaller gas-sample volumes. In
these cases, the Administrator's approval must first be obtained.
6.4.1 During preparation and assembly of the sampling train, keep all
openings where contamination can occur covered with Teflon® film or aluminum foil
until just prior to assembly or until sampling is about to begin.
6.4.2 Fill the soibent trap section of the organic module with approximately
20 g of clean adsorbent resin. While filling, ensure that tire trap packs uniformly, to
eliminate the possibility of channeling. When freshly cleaned, many adsorbent resins
carry a static charge, which will cause clinging to trap walls. This may be minimized
by filling the trap in the presence of an antistatic device. Commercial antistatic devices
include Model-204 and Model-210 manufactured by the 3M Company, St. Paul,
Minnesota.
6.4.3 If an impinger train is used to collect moisture, place 100 mL of water in
each of the first two impingers, leave the third impinger empty (or charge with caustic
solution, as necessary), and transfer approximately 200-300 g of preweighed silica gel
from its container to the fourth impinger. More silica gel may be used, but care should
be taken to ensure that it is not entrained and carried out from the impinger during
sampling. Place the container in a clean place for later use in the sample recovery.
Alternatively, the weight of the silica gel plus impinger may be determined to the
nearest 0.S g and recorded.
6.4.4 Using a tweezer or clean disposable surgical gloves, place a labeled
(identified) and weighed filter in the filter holder. Be sure that the filter is properly
centered and the gasket properly placed to prevent the sample gas stream from
circumventing the filter. Check the filter for tears after assembly is completed.
6.4.5 When glass liners are used, install the selected nozzle using a Viton-A
O-ring when stack temperatures are < 260°C (SOOT) and a woven glass-fiber gasket
when temperatures are higher. See APTD-0576 (Rom, 1972) for details. Other
connecting systems utilizing either 316 stainless steel or Teflon® ferrules may be used.
When metal liners are used, install the nozzle as above, or by a leak-free direct
mechanical connection. Mark the probe with heat-resistant tape or by some other
method to denote the proper distance into the stack or duct for each sampling point.
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6.4.6 Set up the train as in Figure 1. During assembly, do not use any
silicone grease on ground-glass joints that axe located upstream of the organic module.
A very light coating of silicone grease may be used on all ground-glass joints that are
located downstream of the organic module, but it should be limited to the outer portion
(see AFTD-0576) of the ground-glass joints to minimize silicone-grease contamination.
Subject to the approval of the Administrator, a glass cyclone may be used between the
probe and the filter holder when the total particulate catch is expected to exceed
100 mg or when water droplets are present in the stack. The organic module condenser
must be maintained at a temperature of 17 ± 3°C. Connect all temperature sensors to
an appropriate potentiometer/display unit. Check all temperature sensors at ambient
temperature,
6.4.7 Place crushed ice around the impingers and the organic module
condensate knockout.
6.4.8 Turn on the sorbent module and condenser coil coolant recirculating
pump and begin monitoring the sorbent module gas entry temperature. Ensure proper
sorbent module gas entry temperature before proceeding and again before any sampling
is initiated. It is extremely important that the XAD-2 resin temperature never exceed
50*C (122°F), because thermal decomposition will occur. During testing, the XAD-2
temperature must not exceed 20°C (68°F) for efficient capture of the semivolatile
species of interest.
6.4.9 Turn on and set the filter and probe heating systems at the desired
operating temperatures. Allow time for the temperatures to stabilize.
6.5 Leak-check procedures
6.5.1 Protest leak-check:
6.5.1.1 Because the number of additional intereomponent connections in
the Semi-VOST train (over the M5 Train) increases the possibility of leakage, a
pre-test leak-check is required.
6.5.1.2 After the sampling train has been assembled, turn on and set the
filter and probe heating systems at the desired operating temperatures. Allow
time for the temperatures to stabilize. If a Viton-A O-ring or other leak-free
connection is used in assembling the probe nozzle to the probe liner, leak-check
the train at the sampling site by plugging the nozzle and pulling a 381-mm Hg
(15-in. Hg) vacuum.
(NOTE: A lower vacuum may be used, provided that it is not exceeded during
the test.)
6.5.1.3 If an asbestos string is used, do not connect the probe to the
train during the leak-check. Instead, leak-check the train by first attaching a
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carton-filled leak-check impinger (shown In Figure 4) to the inlet of the filter
holder (cyclone, if applicable) and then plugging the inlet and pulling a
381-mm Hg (15-in. Hg) vacuum. (Again, a lower vacuum may be used,
provided that it is not exceeded during the lest.) Then, connect the probe to the
train and leak-check at about 25-mm Hg (1-in. Hg) vacuum; alternatively, leak-
check the probe with the rest of the sampling train in one step at 381-mm Hg
(15-in. Hg) vacuum. Leakage rates in excess of 4% of the average sampling
rate or >0.00057 m*/min (0.02 cfm), whichever is less, are unacceptable.
6.5.1.4 The following leak-check instructions for the sampling train
described in APTD-0576 and APTD-0581 may be helpful. Start the pump with
the fine-adjust valve fully open and coarse-adjust valve completely closed.
Partially open the coarse-adjust valve and slowly close the fine-adjust valve until
the desired vacuum is reached. Do mil reverse direction of the fine-adjust
valve; this will cause water to back up into the organic module. If the desired
vacuum is exceeded, either leak-check at this higher vacuum or end the leak-
check, as shown below, and start over.
6.5.1.5 When the leak-check is completed, first slowly remove the plug
from the inlet to the probe, filter holder, or cyclone (if applicable). When the
vacuum drops to 127 mm (5 in.) Hg or less, immediately close the coarse-adjust
valve. Switch off the pumping system and reopen the fine-adjust valve. Do not
reopen the fine-adjust valve until the coarse-adjust valve has been closed. This
prevents the water in the impingers from being forced backward into the organic
module and silica gel from being entrained backward into the third impinger.
6.5.2 Leak-checks during sampling ran:
6.5.2.1 If, during the sampling run, a component (e.g., filter assembly,
impinger, or sorbent trap) change becomes necessary, a leak-check shall be
conducted immediately after the interruption of sampling and before the change
is made. The leak-check shall be done according to the procedure outlined in
Paragraph 6.5.1, except that it shall be done at a vacuum greater than or equal
to the maximum value recorded up to that point in the test. If the leakage rate
is found to be no greater than 0.00057 mVmin (0.02 cfm) or 4% of the average
sampling rate (whichever is less), the results are acceptable, and no correction
will need to be applied to the total volume of dry gas metered. If a higher
leakage rate is obtained, the tester shall void the sampling run. (It should be
noted that any "correction" of the sample volume by calculation reduces the
integrity of the generated pollutant concentration data and must be avoided.)
6.5.2.2 Immediately after a component change, and before sampling is
reinitiated, a leak-check similar to a pre-test leak-check must also be conducted.
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CROSS SECTIONAL VIEW
Leak Testing Apparatus
28/12 Male
28/12 Female
Modified Impinger
with Inverted Joint
Activated Charcoal
GC
9
•?
Figure 4. Leak-check Impinger
650-049-08-05/m«Ui001
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6.5.3 Post-test leak-check:
6.5.3.1 A leak-check is mandatory at the conclusion of each sampling run.
The leak-check shall be done with the same procedures as the pre-test leak-check,
except that it shall be conducted at a vacuum greater than or equal to the maximum
value reached during the sampling run. If the leakage rate is found to be no greater
than 0.00057 m5/min (0.02 cfm) or 4% of the average sampling rate (whichever is
less), the results are acceptable, and no correction need be applied to the total volume
of dry gas metered. If, however, a higher leakage rate is obtained, the tester shall
either record the leakage rate, correct the sample volume (as shown in the calculation
section of this method), and consider the data obtained of questionable reliability, or
void the sampling run.
6.6 Sampling-train operation;
6.6.1 During the sampling run, maintain an isokinetic sampling rate to within
10% of true isokinetic, unless otherwise specified by the Administrator. Maintain a
temperature around the filter of 120 ± 14°C (248 ± 25°F) and a gas temperature
entering the sorbent trap at a maximum of 20°C (68°F).
6.6.2 For each run, record the data required on a data sheet such as the one
shown in Figure 5. Be sure to record the initial dry-gas meter reading. Record the
dry-gas meter readings at the beginning and end of each sampling time increment,
when changes in flow rates are made before and after each leak-check, and when
sampling is halted. Take other readings required by Figure 5 at least once at each
sample point during each time increment and additional readings when significant
changes (20% variation in velocity-head readings) necessitate additional adjustments in
flow rate. Level and zero the manometer. Because the manometer level and zero may
draft due to vibrations and temperature changes, make periodic checks during the
traverse.
6.6.3 Clean the stack access ports prior to the test run to eliminate the chance
of sampling deposited material. To begin sampling, remove the nozzle cap, verify that
the filter and probe heating systems are at the specified temperature, and verify that the
pi tot tube and probe are properly positioned. Position the nozzle at the first traverse
point, with the tip pointing directly into the gas stream. Immediately start the pump
and adjust the flow to isokinetic conditions. Nomographs, which aid in the rapid
adjustment of the isokinetic sampling rate without excessive computations, are
available. These nomographs are designed for use when the Type S pitot-tube
coefficient is 0.84 ± 0.02 and the stack-gas equivalent density (dry molecular weight)
is equal to 29 ± 4. APTD-0576 details the procedure for using the nomographs. If
the stack-gas molecular weight and the pitot-tube coefficient are outside the above
ranges, do not use the nomographs unless appropriate steps (Shigehara, 1974) are taken
to compensate for the deviations.
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Plant.
Location.
Operator.
Date
Run No,
Sample Bo* No.
Meier Bo* No. _
Meter H
C Factor
Schematic of Stack Crou Section
Pilot Tube Coefficient Cp.
Ambient Temperature,
Baromelrie Preiiure _
Anumed Mouture
Probe Lengnlh, m (ft).
Nozzle Identification No,,
Avg. Calibrated Nozzle Diameter, cm (in),
Pttjbe Heater Setting
Leak Rate, in /rain (cfin) ___________
Probe Liner Material
Static Prwiure
Filter Ko,
Taveise
Point
Number
Sampling
Time
(8) min.
Vacuum
mm Ng
(in, Hg)
Stack
Temperature
CO
*C(F)
Velocity
Held
(PJ
mm (in)
HjO
fteiitire
Differential
Aero ii
Orifice
Meter mm
(HjO) in
(H,0)
Gai
Sample
Volume
ra, W)
Gat Sample
Temp. At Dry
Gat Meter
Filter Holder
Temperature
•C(*F)
Temperature
of Gu
Entering
Soitrent Tnp
*q*F)
Temperature
of Ga»
Leaving
Condenser or
Lait
Impinger
Inlet Outlet
"CfP) #C{'F)
-
Total
Ave, Ave,
Average
Figure 5. Particulate Field Data
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6.6.4 When the stack is under significant negative pressure (equivalent to the height of
the impinger stem), take care to close the coarse-adjust valve before inserting the probe into
the stack, to prevent water from backing into the organic module. If necessary, the pump may
be turned on with the coarse-adjust valve closed.
6.6.5 When the probe is in position, block off the openings around the probe
and stack access port to prevent unrepresentative dilution of the gas stream.
6.6.6 Traverse the stack cross section, as required by EPA Method 1 or as
specified by the Administrator, being careful not to bump the probe nozzle into the
stack walls when sampling near the walls or when removing or inserting the probe
through the access port, in order to minimize the chance of extracting deposited
material.
6.6.7 During the test run, make periodic adjustments to keep the temperature
around the filter holder and the organic module at the proper levels; add more ice and,
if necessary, salt to maintain a temperature of <20°C (68°F) at the condenser/silica gel
outlet. Also, periodically check the level and zero of the manometer.
6.6.8 If the pressure drop across the filter or sorbent trap becomes too high,
making isokinetic sampling difficult to maintain, the fllter/sorbent trap may be replaced
in the midst of a sample run. Using another complete filter holder/sorbent trap
assembly is recommended, rather than attempting to change the filter and resin
themselves. After a new filter/sorbent trap assembly is installed, conduct a leak-check.
The total particulate weight shall include the summation of all filter assembly catches.
6.6.9 A single train shall be used for the entire sample run, except in cases
where simultaneous sampling is required in two or more separate ducts or at two or
more different locations within the same duct, or in cases where equipment failure
necessitates a change of trains. In all other situations, the use of two or more trains
will be subject to the approval of the Administrator.
6.6.10 Note that when two or more trains are used, separate analysis of the
front-half (if applicable) organic-module and impinger (if applicable) catches from each
train shall be performed, unless identical nozzle sizes were used on all trains. In that
case, the front-half catches from the individual trains may be combined (as may the
impinger catches), and one analysis of front-half catch and one analysts of impinger
catch may be performed.
6.6.11 At the end of the sample run, turn off the coarse-adjust valve, remove
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the probe and nozzle from the stack, turn off the pump, record the final dry-gas meter
reading, and conduct a post-test leak-check. Also, leak-check the pitot lines as
described in EPA Method 2. The lines must pass this leak-check in order to validate
the velocity-head data.
6.6.12 Calculate percent isokineticity (see Section 10.8) to determine whether
the run was valid or another test run should be made.
7.0 SAMPLE RECOVERY
7.1 Preparation;
7.1.1 Proper cleanup procedure begins as soon as the probe is removed from
the stack at the end of the sampling period. Allow the probe to cool. When the probe
can be safely handled, wipe off all external particulate matter near the tip of the probe
nozzle and place a cap over the tip to prevent losing or gaining particulate matter. Do
not cap the probe tip tightly while the sampling train is cooling down because this will
create a vacuum in the filter holder, drawing water from the impingers into the sorbent
module.
7.1.2 Before moving the sample train to the cleanup site, remove the probe
from the sample train and cap the open outlet, being careful not to lose any condensate
that might be present. Cap the filter inlet. Remove the umbilical cord from the last
impinger and cap the impinger. If a flexible line is used between the organic module
and die filter holder, disconnect the line at the filter holder and let any condensed water
or liquid drain into the organic module.
7.1.3 Cap the filter-holder outlet and the inlet to the organic module. Separate
the sorbent trap section of the organic module from the condensate knockout trap and
the gas-conditioning section. Cap all organic module openings. Disconnect the
organic-module knockout trap from the impinger train inlet and cap both of these
openings. Ground-glass stoppers, Teflon* caps, or caps of other inert materials may be
used to seal all openings.
7.1.4 Transfer the probe, the filter, the organic-module components, and the
impinger/condenser assembly to the cleanup area. This area should be clean and
protected from the weather to minimize sample contamination or loss.
7.1.5 Save a portion of all washing solutions (methanol/methylene chloride,
Type II water) used for cleanup as a blank. Transfer 200 mL of each solution directly
from the wash bottle being used and place each in a separate, prelabeled glass sample
container.
7.1.6 Inspect the train prior to and during disassembly and note any abnormal
conditions.
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7.2 Sample containers;
7.2.1 Container no, 1: Carefully remove the filter from the filter holder and
place it in its identified Petri dish container. Use a pair (or pairs) of tweezers to handle
the filter. If it is necessary to fold the- filter, ensure that the particulate cake is inside
the fold. Carefully transfer to the Petri dish any particulate matter or filter fibers that
adhere to the filter-holder gasket, using a dry nylon bristle brush or sharp-edged blade,
or both. Label the container and seal with l-in.-wide Teflon® tape around the
circumference of the lid.
7.2.2 Container no. 2: Taking care that dust on the outside of the probe or
other exterior surfaces does not get into the sample, quantitatively recover particulate
matter or any condensate from the probe nozzle, probe fitting, probe liner, and front
half of the filter holder by washing these components first with methanol/methylene
chloride (1:1 v/v) into a glass container. Distilled water may also be used. Retain a
water and solvent blank and analyze in the same manner as the samples. Perform
rinses as follows:
7.2.2.1 Carefully remove the probe nozzle and clean the inside surface
by rinsing with the solvent mixture (1:1 v/v methanol/methylene chloride) from
a wash bottle and brushing with a nylon bristle brush. Brush until the rinse
shows no visible particles, then make a final rinse of the inside surface with the
solvent mix. Brush and rinse the inside parts of the Swagelok fitting with the
solvent mix in a similar way until no visible particles remain.
7.2.2.2 Have two people rinse the probe liner with the solvent mix by
tilting and rotating the probe while squirting solvent into its upper end so that all
inside surfaces will be wetted with solvent. Let the solvent drain from the
lower end into the sample container. A glass funnel may be used to aid in
transferring liquid washes to the container.
7.2.2.3 Follow the solvent rinse with a probe brush. Hold the probe in
an inclined position and squirt solvent into the upper end while pushing the
probe brash through the probe with a twisting action; place a sample container
underneath the lower end of the probe and catch any solvent and particulate
matter that is brushed from the probe. Run the brush through the probe three
times or more until no visible particulate matter is carried out with the solvent
or until none remains in the probe liner on visual inspection. With stainless
steel or other metal probes, run the brush through in the above-prescribed
manner at least six times (metal probes have small crevices in which particulate
matter can be entrapped). Rinse the brush with solvent and quantitatively
collect these washings in the sample container. After the brushing, make a final
solvent rinse of the probe as described above.
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7.2.2.4 It is recommended that two people work together to clean the
probe to minimize sample losses. Between sampling runs, keep brushes clean
and protected from contamination.
7.2.2.5 Clean the inside of the front half of the filter holder and
cyclone/cyclone flask, if used, by rubbing the surfaces with a nylon bristle
brush and rinsing with methanol/methylene chloride (1:1 v/v) mixture. Rinse
each surface three times or more if needed to remove visible particulate. Make
a final rinse of the brush and filter holder. Carefully rinse out the glass cyclone
and cyclone flask (if applicable). Brush and rinse any paniculate material
adhering to the inner surfaces of these components into the front-half rinse
sample. After all solvent washings and particulate matter have been collected in
the sample container, tighten the lid on the sample container so that solvent will
not leak out when it is shipped to the laboratory. Mark the height of the fluid
level to determine whether leakage occurs during transport. Label the container
to identify its contents.
7.2.3 Container no. 3: The sorbent trap section of the organic module may be
used as a sample transport container, or the spent resin may be transferred to a separate
glass bottle for shipment. If the sorbent trap itself is used as the transport container,
both ends should be sealed with tightly fitting caps or plugs. Ground-glass stoppers or
Teflon* caps may be used. The sorbent trap should then be labeled, covered with
aluminum foil, and packaged on ice for transport to the laboratory. If a separate bottle
is used, the spent resin should be quantitatively transferred from the trap into the clean
bottle. Resin that adheres to the walls of the trap should be recovered using a rubber
policeman or spatula and added to this bottle.
7.2.4 Container no. 4: Measure the volume of condensate collected in the
condensate knockout section of the organic module to within ± 1 mL by using a
graduated cylinder or by weighing to within ± 0.5 g using a triple-beam balance.
Record the volume or weight of liquid present, and note any discoloration or film in the
liquid catch. Transfer this liquid to a prelabeled glass sample container. Inspect the
back half of the filter housing and the gas-conditioning section of the organic module.
If condensate is observed, transfer it to a graduated or weighing bottle and measure the
volume, as described above. Add this material to the condensate knockout-trap catch.
7.2.5 Container no. 5: All sampling train components located between the
high-efficiency glass- or quartz-fiber filter and the first wet impinger of the final
condenser system (including the heated Teflon* line connecting the filter outlet to the
condenser) should be thoroughly rinsed with methanol/methylene chloride (1:1 v/v) and
the rinsings combined. This rinse shall be separated from the condensate. If the spent
resin is transferred from the sorbent trap to a separate sample container for transport,
fi3WM9-08-05/meih0010/
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the sorbent trap shall be thoroughly rinsed until all sample-wetted surfaces appear
clean. Visible films should be removed by brushing. Whenever train components are
brushed, the brash should be subsequently rinsed with solvent mixture and the rinsings
added to this container.
7*2.6 Container no. 6: Note the color of the indicating silica gel to determine
if it has been completely spent and make a notation of its condition. Transfer the silica
gel from the fourth impinger to its original container and seal. A funnel may make it
easier to pour the silica gel without spilling. A rubber policeman may be used as an
aid in removing the silica gel from the impinger. It is not necessary to remove the
small amount of dust particles that may adhere strongly to the impinger wall. Because
the gain in weight is to be used for moisture calculations, do not use any water or other
liquids to transfer the silica gel. If a balance is available in the field, weight the
container and its contents to 0.5 g or better.
7.3 Tmpinger wafec:
7.3.1 Make a notation of any color or film in the liquid catch. Measure the
liquid in the first three impingers to within ± 1 mL by using a graduated cylinder or by
weighing it to within ± 0.5 g by using a balance (if one is available). Record the
volume or weight of liquid present. This information is required to calculate the
moisture content of the effluent gas.
7.3.2 Discard the liquid after measuring and recording the volume or weight,
unless analysis of the impinger catch is required (see Paragraph 4.1.3.7). Amber glass
containers should be used for storage of impinger catch, if required.
7.3.3 If a different type of condenser is used, measure the amount of moisture
condensed either volumetrically or gravimetrically.
7.4 Sample preparation for shipment: Prior to the shipment, recheck all sample
containers to ensure that the caps are well secured. Seal the lids of all containers around the
circumference with Teflon® tape. Ship all liquid samples upright on ice and all particulate
filters with the particulate catch facing upward. The particulate filters should be shipped
unreftigerated.
8.0 ANALYSIS
8.1 Sample preparation:
8.1.1 General; The preparation steps for all samples will result in a finite
volume of concentrated solvent. The final sample volume (usually in the 1- to
10-mL range) is then subjected to analysis by GC/MS. All samples should be
inspected and the appearance documented. All samples are to be spiked with
surrogate standards as received from the field prior to any sample
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manipulations. The spike should be at a level equivalent to 10 times the MDL
when the solvent is reduced in volume to the desired level (i.e., 10 mL), The
spiking compounds should be the stable isotopically labeled analog of the
compounds of interest or a compound that would exhibit properties similar to
the compounds of interest, be easily chromatographed, and not interfere with
the analysis of the compounds of interest. Suggested surrogate spiking
compounds are: deuterated napthalene, chrysene, phenol, nitrobenzene,
chlorobenzene, toluene, and carbon- 13-labeled pentachlorophenol.
8.1.2 Condensate: The "condensate* is the moisture collected in the
first impinger following the XAD-2 module. Spike the condensate with the
surrogate standards. The volume is measured and recorded and then transferred
to a separatory funnel. The pH is to be adjusted to pH 2 with 6 N sulfuric acid,
if necessary. The sample container and graduated cylinder are sequentially
rinsed with three successive 10-mL aliquots of the extraction solvent and added
to the separatory funnel. The ratio of solvent to aqueous sample should be
maintained at 1:3. Extract the sample by vigorously shaking the separatory
funnel for 5 min. After complete separation of the phases, remove the solvent
and transfer to a Kudema-Danish concentrator (K-D), filtering through a bed of
precleaned, dry sodium sulfate. Repeat the extraction step two additional times.
Adjust the pH to 11 with 6 N sodium hydroxide and reextract combining the
acid and base extracts. Rinse the sodium sulfate into the K-D with fresh solvent
and discard the desiccant. Add Teflon® boiling chips and concentrate to 10 mL
by reducing the volume to slightly less than 10 mL and then bringing to volume
with fresh solvent. In order to achieve the necessary detection limit, the sample
volume can be further reduced to 1 mL by using a micro column K-D or
nitrogen blow-down. Should the sample start to exhibit precipitation, the
concentration step should be stopped and the sample redissolved with fresh
solvent talcing the volume to some finite amount. After adding a standard (for
the purpose of quantitation by GC/MS), the sample is ready for analysis, as
discussed in Paragraph 8.2.
8.1.3 Impinger: Spike the sample with the surrogate standards;
measure and record the volume and transfer to a separatory funnel. Proceed as
described in Paragraph 8.1.2.
8.1.4 XAD-2: Spike the resin directly with the surrogate standards.
Transfer the resin to the all-glass thimbles by the following procedure (care
should be taken so as not to contaminate the thimble by touching it with
anything other than tweezers or other solvent-rinsed mechanical holding
devices). Suspend the XAD-2 module directly over the thimble. The glass frit
of the module (see Figure 2) should be in the up position. The thimble is
contained in a clean beaker, which will serve to catch the solvent rinses. Using
a Teflon® squeeze bottle, flush the XAD-2 into the thimble. Thoroughly rinse
the glass module with solvent into the beaker containing the thimble. Add the
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XAD-2 glass-wool plug to the thimble. Cover the XAD-2 in the thimble with a
precleaned glass-wool plug sufficient to prevent the resin from floating into the
solvent reservoir of the extractor. If the resin is wet, effective extraction can be
accomplished by loosely packing the resin in the thimble. If a question arises
concerning the completeness of the attraction, a second extraction, without a
spike, is advised. The thimble is placed in the extractor and the rinse solvent
contained in the beaker is added to the solvent reservoir. Additional solvent is
added to make the reservoir approximately two-thirds full. Add Teflon® boiling
chips and assemble the apparatus. Adjust the heat source to cause the extractor
to cycle 5-6 times per hr. Extract the resin for 16 hr. Transfer the solvent and
three 10-mL rinses of the reservoir to a K-D and concentrate as described in
Paragraph 8.1.2.
8.1.5 Particulate filter (and cyclone catch); If particulate loading is
to be determined, weigh the filter (and cyclone catch, if applicable). The
particulate filter (and cyclone catch, if applicable) is transferred to the glass
thimble and extracted simultaneously with the XAD-2 resin.
8.1.6 Train solvent rinses: AE train rinses (i.e., probe, impinger,
filter housing) using the extraction solvent and methanol are returned to the
laboratory as a single sample. If the rmses are contained in more than one
container, the intended spike is divided equally among the containers
proportioned from a single syringe volume. Transfer the rinse to a sepaxatory
funnel and add a sufficient amount of organic-free water so that the methylene
chloride becomes immiscible and its volume no longer increases with the
addition of more water. The extraction and concentrations steps are then
performed as described in Paragraph 8.1.2.
8.2 Sample analysis;
8.2.1 The primary analytical tool for the measurement of emissions
from hazardous waste incinerators is GC/MS using fused-silica capillary GC
columns, as described in Method 8270 in Chapter Four of this manual. Because
of the nature of GS/MS instrumentation and the cost associated with sample
analysis, prescreening of the sample extracts by gas chromatography/flame
ionization detection (GC/FID) or with electron capture (GC/ECD) is
encouraged. Information regarding the complexity and concentration level of a
sample prior to GC/MS analysis can be of enormous help. This information can
be obtained by using either capillary columns or less expensive packed columns.
However, the FID screen should be performed with a column similar to that
used with the GS/MS. Keep in mind that GC/FID has a slightly lower detection
limit than GS/MS and, therefore, that the concentration of the sample can be
adjusted either up or down prior to analysis by GC/MS.
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8.2.2 The mass spectrometer will be operated in a full scan (40-450)
mode for most of the analyses. The range for which data are required in a
GS/MS run will be sufficiently broad to encompass the major ions, as listed in
Chapter Four, Method 8270, for each of the designated POHCs in an
incinerator effluent analysis.
8.2.3 For most purposes, electron ionization (EI) spectra will be
collected because a majority of the POHCs give reasonable EI spectra. Also, EI
spectra are compatible with the NBS Library of Mass Spectra and other mass
spectral references, which aid in the identification process for other components
in the incinerator process streams.
8.2.4 To clarify some identifications, chemical ionization (CI) spectra
using either positive ions or negative ions will be used to elucidate molecular-
weight information and simplify the fragmentation patterns of some compounds.
In no case, however, should CI spectra alone be used for compound descriptions
of GC conditions, MS conditions, and quantitative identification. Refer to
Chapter Four, Method 8270, for complete descriptions of GC conditions, MS
conditions, and qualitative and quantitative identification.
9.0 CALIBRATION
9.1 Probe nozzle: Probe nozzles shall be calibrated before their initial use in the
field. Using a micrometer, measure the inside diameter of the nozzle to the nearest 0.025 mm
(0.001 in.). Make measurements at three separate places across the diameter and obtain the
average of the measurements. The difference between the high and low numbers shall not
exceed 0.1 mm (0.004 in.). When nozzles become nicked, dented, or corroded, they shall be
reshaped, sharpened, and recalibrated before use. Each nozzle shall be permanently and
uniquely identified.
9.2 Pitot tube: The Type S pitot tube assembly shall be calibrated according to
the procedure outlined in Section 4 of EPA Method 2, or assigned a nominal coefficient of
0.84 if it is not visibly nicked, dented, or corroded and if it meets design and intercomponent
spacing specifications.
9.3 Metering system:
9.3.1 Before its initial use in the field, the metering system shall be calibrated
according to the procedure outlined in APTD-0576. Instead of physically adjusting the
dry-gas meter dial readings to correspond to the wet-test meter readings, calibration
factors may be used to correct the gas meter dial readings mathematically to the proper
values. Before calibrating the metering system, it is suggested that a leak-check be
conducted. For metering systems having diaphragm pumps, the normal leak-check
procedure will not detect leakages within the pump. For these cases the following leak-
check procedure is suggested: Make a 10-min calibration run at 0.00057 m3/min
650-0*49-08-05/me th0010/
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(0.02 cfm); at the end of the run, take the difference of the measured wet-test and dry-
gas meter volumes and divide the difference by 10 to get the leak rate. The leak rate
should not exceed 0.00057 ms/min (0.02 cfm).
9.3.2 After each field use, the calibration of the metering system shall be
checked by performing three calibration runs at a single intermediate orifice setting
(based on the previous field test). The vacuum shall be set at the maximum value
reached during the test series. To adjust the vacuum, insert a valve between the wet-
test meter and the inlet of the metering system. Calculate the average value of the
calibration factor. If the calibration has changed by more than 5%, recalibrate the
meter over the full range of orifice settings, as outlined in APTD-0576.
9.3.3 Leak-check of metering system: That portion of the sampling train
from the pump to the orifice meter (see Figure 1) should be leak-checked prior to
initial use and after each shipment. Leakage after the pump will result in less volume
being recorded than is actually sampled. The following procedure is suggested (see
Figure 6): Close the main valve on the meter box. Insert a one-hole rubber stopper
with rubber tubing attached into the orifice exhaust pipe. Disconnect and vent the low
side of the orifice manometer. Close off the low side orifice tap. Pressurize the
system to 13-18 cm (5-7 in.) water column by blowing into the rubber tubing. Pinch
off the tubing and observe the manometer for 1 min. A loss of pressure on the
manometer indicates a leak in the meter box. Leaks, if present, must be corrected,
NOTE: If the dry-gas-meter coefficient values obtained before and after a test series
differ by >5%, either the test series shall be voided or calculations for test
series shall be performed using whichever meter coefficient value (i.e., before
or after) gives the lower value of total sample volume.
9.4 Probe heater: The probe-heating system shall be calibrated before its initial
use in the field according to the procedure outlined in APTD-0576. Probes constructed
according to APTD-0581 need not be calibrated if the calibration curves in APTD-0576 are
used.
9.5 Tpmneratiirp gangi*; Each thermocouple must be permanently and uniquely
marked on the casting; all mercury-in-glass reference thermometers must conform to
ASTM E-l 63C or 63F specifications. Thermocouples should be calibrated in the laboratory
with and without the use of extension leads. If extension leads are used in the field, the
thermocouple readings at ambient air temperatures, with and without the extension lead, must
be noted and recorded. Correction is necessary if the use of an extension lead produces a
change >1.5%.
9.5.1 Impinger, organic module, and dry-gas meter thermocouples: For
the thermocouples used to measure the temperature of the gas leaving the impinger
train and the XAD-2 resin bed, three-point calibration at ice-water, room-air, and
boiling-water temperatures is necessary. Accept the thermocouples only if the readings
at all three temperatures agree to ± 2°C (3.6°F) with those of the absolute value of the
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reference thermometer.
63
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Rubber Stopper
By-pass Valve
Rubber Tubing
Vacuum Gauge
Blow into tubing
until manometer
wads 5 lo 7 inches
water column
Orifice
C osed
Main Valve
Closed
Orifice
Manometer
Air-tight Pump
Figure 6. Leak-check of Meter Box
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9.5.2 Probe and stack thermocouple: For the thermocouples used to indicate
the probe and stack temperatures, a three-point calibration at ice-water, boiling-water,
and hot-oil-bath temperatures must be performed; it is recommended that room-air
temperature be added, and that the thermometer and the thermocouple agree to within
1.5% at each of the calibration points. A calibration curve (equation) may be
constructed (calculated) and the data extrapolated to cover the entire temperature range
suggested by the manufacturer.
9.6 Barometer: Adjust the barometer initially and before each test series to agree
to within ± 25 mm Hg (0.1 in. Hg) of the mercury barometer or the corrected barometric
pressure value reported by a nearby National Weather Service Station (same altitude above sea
level).
9.7 Triple-heam balance; Calibrate the triple-beam balance before each test series,
using Class-S standard weights; the weights must be within ± 0.5% of the standards, or the
balance must be adjusted to meet these limits.
10.0 CALCULATIONS
10.1 Cany out calculations. Round off figures after the final calculation to the
correct number of significant figures.
10.2 Nmmmrialiireg
A, = Cross-sectional area of nozzle, m2 (ft?).
Water vapor in the gas stream, proportion by volume.
Cd = Type S pitot tube coefficient (nominally 0.84 ± 0.02), dimensionless.
I = Percent of isokinetic sampling.
L, = Maximum acceptable leakage rate for a leak-check, either pre-test or
following a component change; equal to 0.00057 m'/min (0.02 cfm) or
4% of the average sampling rate, whichever is less.
L; — Individual leakage rate observed during the leak-check conducted prior
to the "ia" component change (i = 1, 2, 3...n) mVmin (cfm).
= Leakage rate observed during the post-test leak-check, m3/min (cfm).
Md = Stack-gas dry molecular weight, g/g-mole (lb/lb-mole).
M,, = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-mole).
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Pta, = Barometric pressure at the sampling ate, mm Hg (in. Hg).
Pf = Absolute stack-gas pressure, mm Hg (in. Hg).
» Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 mm Hg-m3/K-g-mole
(21.85 in. Hg-ft5/°R-lb-mole).
Tm = Absolute average dry-gas meter temperature (see Figure 6), K (°R).
T, = Absolute average stack-gas temperature (see Figure 6), K (°R).
Tm = Standard absolute temperature, 293K (528°R).
Vk Total volume of liquid collected in the organic module condensate
knockout trap, the impingers, and silica gel, mL.
Vm = Volume of gas sample as measured by dry-gas meter, dscm (dscf).
Volume of gas sample measured by the dry-gas meter, corrected to
standard conditions, dscm (dscf).
Vw(-d) = Volume of water vapor in the gas sample, corrected to standard
conditions, son (scf).
V, = Stack-gas velocity, calculated by Method 2, Equation 2-9, using data
obtained from Method 5, m/sec (ft/sec).
W, = Weight of residue in acetone wash, mg.
y = Dry-gas-meter calibration factor, dimensionless.
AH = Average pressure differential across the orifice meter (see Figure 2),
mm H20 (in. H20).
pw = Density of water, 0.9982 g/mL (0,002201 lb/mL).
0 = Total sampling time, min.
0t = Sampling time interval from the beginning of a run until the first
component change, min.
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Sampling time interval between two successive component changes,
beginning with the interval between the first and second changes, min.
0p = Sampling time interval from the final (n*) component change until the
end of the sampling run, min.
13.6 — Specific gravity of mercury.
60 = sec/min.
100 = Conversion to percent.
10*3 Aysiusc liry-eafriiifiter t?nTic^ prc^surs drop* See
data sheet (Figure 5, above).
10.4 Dry-gas volume? Correct the sample measured by the dry-gas meter to
standard conditions (20°C, 760 mm Hg [68 °F, 29.92 in. Hg]) by using Equation 1:
Pk. - — - —
- vmY ^ —-!« - k,v„y _!LL a)
where:
K, = 0.385B K/mm Hg for metric units, or
Kt = 17.64°8/in. Hg for English units.
It should be noted that Equation 1 can be used as written, unless the leakage rate observed
during any of the mandatory leak-checks (i.e., the post-test leak-check or leak-checks
conducted prior to component changes) exceeds La, If Lp or L, exceeds L„ Equation 1 must
be modified as follows:
a. Case I (no component changes made during sampling run): Replace Vm in
Equation 1 with the expression:
V.-(L,-LJ
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b. Case H (one or more component changes made during the sampling run):
Replace Vm in Equation 1 by the expression:
V. - (L, - L.)6, - ± (L, - L,)8, - (L„ - Lje,
i«2
and substitute only for those leakage rates (Lt or Lp) that exceed L,.
10.5 Volume of water vapor;
P„, RT^
« Vle -f- —a = K, vk O)
1 lw r«ul
where:
K2 = 0.001333 mJ/mL for metric units, or
Kj = 0.04707 ftVmL for English units.
10.6 Moisture rnntpnf;
B = ^22 (3)
Wl y v W
m(nd) w(std)
NOTE: In saturated or water-droplet-laden gas streams, two calculations of the
moisture content of the stack gas shall be made, one from the impinger
analysis (Equation 3) and a second from the assumption of saturated
conditions. The lower of the two values of Bw shall be considered correct.
The procedure for determining the moisture content based upon assumption of
saturated conditions is given in the Note to Section 1.2 of Method 4, For the
purposes of this method, the average stack-gas temperature from Figure 6 may
be used to make this determination, provided that the accuracy of the in-stack
temperature sensor is ± 1°C (2°F).
10.7 Conversion factors:
Emm Iq Multiply by
scf m3 0.02832
g/ft3 gr/tf 15.43
g/ft3 lb/ft3 2.205 x 10'3
g/ft3 g/mJ 35.31
$50-049-0t-0S/o*eth00 i 0/
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10.8 Isokinetic variation;
10.8.1 Calculation from raw data:
100 T.
I =
K3F,
Lhsu
' b«r
AH
13.6
606V,PA
(4)
where:
K3 = 0.003454 mm Hg-m3 for metric units, or
K3 = 0.002669 in. Hg-ft3/mL-°R for English units.
10.8.2 Calculation for intermediate values:
where:
T^V0AaP 60(1-6^)
=K
T V
4 P.V.A^Cl-B^)
m
«4
K4
4.320 for metric units, or
0.09450 for English units.
10.8.3 Acceptable results: If 90% s I £ 110%, the results are acceptable. If
the results are low in comparison with the standard and I is beyond the acceptable
range, or if I is less than 90%, the Administrator may opt to accept the results.
10.9 To determine the minimum sample volume that shall be collected, the following
sequence of calculations shall be used.
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10.9.1 From prior analysis of the waste feed, the concentration of POHCs
introduced into the combustion system can be calculated. The degree of destruction
and removal efficiency that is required is used to determine the maximum amount of
POHC allowed to be present in the effluent. This may be expressed as;
(WF) (POHC; cone) (100-%DRE) + ^ p0HC ^
100 100
(7)
where:
WF = mass flow rate of waste feed per hr,-g/hr (Ib/hr).
POHCj = concentration of Principal Organic Hazardous Compound (wt %)
introduced into the combustion process.
DRE = percent Destruction and Removal Efficiency required.
Max POHC ® mass flow rate (g/hr [lb/hr]) of POHC emitted from the
combustion source.
10.9.2 The average discharge concentration of the POHC in the effluent gas is
determined by comparing the Max POHC with the volumetric flow rate being
exhausted from the source. Volumetric flow rate data are available as a result of
preliminary Method 1-4 determinations:
Max POHC. Mass
! = Max POHC; cone (g)
^^eancad)
where:
DVtfr<«D ~ volumetric flow rate of exhaust gas, dscm (dscf).
POHCj cone = anticipated concentration of the POHC in the exhaust gas stream,
g/dscm (Ib/dsef).
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10.9.3 In making this calculation, it is recommended that a safety margin of at
least ten be included:
LDLpoHc x 10 _ v
POHC. cotic ~ 780 ( )
where:
LDLponc = detectable amount of POHC in entire sampling train.
NOTE: The whole extract from an XAD-2 cartridge is seldom, if ever, injected
at once. Therefore, if aliquoting factors are-involved, the LDLpowc is
not the same as the analytical (or column) detection Emit
Vroe = minimum dry standard volume to be collected at dry-gas meter.
protffis;
1) Multiply the concentration of the POHC as determined in Method 8270 by the final
concentration volume, typically 10 mL.
Cfoiic 0*g/mL) x sample volume (mL) » amount (fig) of POHC in sample (9)
where:
Crone = concentration of POHC as analyzed by Method 8270.
2) Sum the amount of POHC found in all samples associated with a single train.
Total (jig) = XAD-2 Qxg) 4- condensate 0*g) + rinses (jxg) + impinger (p.g) (10)
3) Divide the total /ig found by the volume of stack gas sampled (m3).
(Total ptg)/(train sample volume) = concentration of POHC (j*g/m3) (11)
11.0 QUALITY CONTROL
11.1 Sampling; See EPA Manual 600/4-77-027b for Method 5 quality control.
11.2 Analysis: The quality assurance program required for this study includes the
analysis of field and method blanks, procedure validations, incorporation of stable labeled
surrogate compounds, quantitation versus stable labeled internal standards, capillary column
650-O49-Oa~05/meth0GI0/ ___ _ _ Reviiioni 0
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performance checks, and external performance tests. The surrogate spiking compounds
selected for a particular analysis are used as primary indicators of the quality of the analytical
data for a wide range of compounds and a variety of sample matrices. The assessment of
combustion data, positive identification, and quantitation of the selected compounds are
dependent on the integrity of the samples received and the precision and accuracy of the
analytical methods employed. The quality assurance procedures for this method are designed
to monitor the performance of the analytical method and to provide the required information to
take corrective action if problems are observed in laboratory operations or in field sampling
activities.
11.2.1 Field Blanks: Field blanks must be submitted with the samples
collected at each sampling site. The field blanks include the sample bottles containing
aliquots of sample recovery solvents, unused filters, and resin cartridges. At a
minimum, one complete sampling train will be assembled in the field staging area,
taken to the sampling area, and leak-checked at the beginning and end of the testing (or
for the same total number of times as the actual test train). The filter housing and
probe of the blank train will be heated during the sample test. The train will be
recovered as if it were an actual test sample. No gaseous sample will be passed
through the sampling train.
11.2.2 Method Blanks: A method blank must be prepared for each set of
analytical operations to evaluate contamination and artifacts that can be derived from
glassware, reagents, and sample handling in the laboratory.
11.2.3 Refer to Method 8270 for additional quality control considerations.
12.0 METHOD PERFORMANCE
12.1 Method performance evaluation: Evaluation of analytical procedures for a
selected series of compounds must include the sample-preparation procedures and each
associated analytical determination. The analytical procedures should be challenged by the test
compounds spiked at appropriate levels and carried through the procedures.
12.2 Method detection limit; The overall method detection limits (low and upper)
must be determined on a compound-by-compound basis because different compounds may
exhibit different collection, retention, and extraction efficiencies as well as instrumental
minimum detection limit (MDL). The method detection limit must be quoted relative to a
given sample volume. The upper limits for the method must be determined relative to
compound retention volumes (breakthrough).
12.3 Method precision and bias; The overall method precision and bias must be
determined on a compound-by-compound basis at a given concentration level. The method
precision value would include a combined variability due to sampling, sample preparation, and
instrumental analysis. The method bias would be dependent upon the collection, retention,
and extraction efficiency of the train components. From evaluation studies to date using a
6S986
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dynamic spiking system, method biases of -13% and -16% have been determined for toluene
and 1,1,2,2-tetrachloroethane, respectively. A precision of 19.9% was calculated from a field
test data set representing seven degrees of freedom that resulted from a series of paired,
unspiked Semivolatile Organic Sampling trains (Semi-VOST) sampling emissions from a
hazardous waste incinerator.
13.0 REFERENCES
1. Addendum to Specifications for Incinerator Testing at Federal Facilities, PHS,
NCAPC, December 6, 1967.
2. Bursey, J., Homoiya, J., McAllister, R,, and McGangley, J., Laboratory and Field
Evaluation of the Semi-VOST Method, Vols. 1 and 2, U.S. Environmental Protection Agency,
EPA/600/4-851/075A, 075B (1985).
3. Martin, R.M., Construction Details of Isokinetic Source-Sampling Equipment,
Research Triangle Park, NC, U.S. Environmental Protection Agency, April 1971,
PB-203 060/BE, APTD-0581, 35 pp.
4. Rom, J J., Maintenance, Calibration, and Operation of Isokinetic Source-Sampling
Equipment, Research Triangle Park, NC, U.S. Environmental Protection Agency,
March 1972, PB-209 022/BE, APTD-0576, 39 pp.
5. Schlickenrieder, L.M., Adams, J.W., and Thrun, K.E., Modified Method 5 Train and
Source Assessment Sampling System: Operator's Manual, U.S. Environmental Protection
Agency, EPA/600/8-85/003, (1985).
6. Shigehara, R.T., Adjustments in the EPA Nomography for Different Pilot Tube
Coefficients and Dry Molecular Weights, Stack Sampling News, 2:4-11 (October 1974).
7. U.S. Environmental Protection Agency, CFR 40 Part 60, Appendix A, Methods 1-5.
8. Vollaro, R.F., A Survey of Commercially Available Instrumentation for the
Measurement of Low-Range Gas Velocities, Research Triangle Park, NC, U.S. Environmental
Protection Agency, Emissions Measurement Branch, November 1976 (unpublished paper).
«SO-O49-O8-0J/me«»iO0l0/
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METHOD 0010
APPENDIX A
1.0 SCOPE AND APPLICATION
1.1 XAD-2 resin as supplied by the manufacturer is impregnated with a bicarbonate
solution to inhibit microbial growth during storage. Both the salt solution and any residual
extractable monomer and polymer species must be removed before use. The resin is prepared
by a series of water and organic extractions, followed by careful drying.
2.0 EXTRACTION
2-1 Method 1: The procedure may be carried out in a giant Soxhlet extractor.
An all-glass thimble containing an extra-coarse frit is used for extraction of XAD-2. The frit
is recessed 10-15 mm above a crenellated ring at the bottom of the thimble to facilitate
drainage. The resin must be carefully retained in the extractor cup with a glass-wool plug and
stainless steel screen because it floats on methylene chloride. This process involves sequential
extraction in the following order.
Sobasiii Procedure
Water Initial rinse: Place resin in a beaker, rinse once
with Type H water, and discard. Fill with water a
second time, let stand overnight, and discard.
Water
Extract with H2O for 8 hr.
Methyl alcohol
Extract for 22 hr.
Methylene chloride
Extract for 22 hr.
Methylene chloride (fresh)
Extract for 22 hr.
650-049-08-05/nieth0010 ,*pp
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Condenser
Distilate Take-off
0.65 cm x 0.32 cm Union
(1/4 x 1/8 in)
0.32 cm 11/8 in)
Teflon Tubing
0.32 cm Union
V
E=
n ,o
Air Jacketed
Snyder Column
V
0.32 cm Union
i
Solvent
Heating Mantle
Tefton Gasket
.Retaining Spring
'Coarse Plate
"Fine Screen
-Fine Screen
. Coarse Plate
Drain
Optional Pump
Figure A-1. XAD-2 Cleanup Extraction Apparatus
0_
f—
IX
A
6
a>
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2.2 Method 2:
2.2.1 As an alternative to Soxhlet extraction, a continuous extractor has been
fabricated for the extraction sequence. This extractor has been found to be acceptable.
The particular canister used for the apparatus shown in Figure A-l contains about 500 g
of finished XAD-2, Any size may be constructed; the choice is dependent on the needs
of the sampling programs. The XAD-2 is held under light spring tension between a
pair of coarse and fine screens. Spacers under the bottom screen allow for even
distribution of clean solvent. The three-necked flask should be of sufficient size (3-liter
in this case) to hold solvent equal to twice the dead volume of the XAD-2 canister.
Solvent is refluxed through the Snyder column, and the distillate is continuously cycled
up through the XAD-2 for extraction and returned to the flask. The flow is maintained
upward through the XAD-2 to allow maximum solvent contact and prevent channeling.
A valve at the bottom of the canister allows removal of solvent from the canister
between changes.
2.2.2 Experience has shown that it is very difficult to cycle sufficient water in
this mode. Therefore the aqueous rinse is accomplished by simply flushing the canister
with about 20 liters of distilled water. A small pump may be useful for pumping the
water through the canister. The water extraction should be carried out at the rate of
about 20-40 mL/min.
2.2.3 After draining the water, subsequent methyl alcohol and methylene
chloride extractions are carried out using the refluxing apparatus. An overnight or 10-
to 20-hr period is normally sufficient for each extraction.
2.2.4 All materials of construction are glass, Teflon®, or stainless steel.
Pumps, if used, should not contain extractable materials. Pumps are not used with
methanol and methylene chloride.
3.0 DRYING
3.1 After evaluation of several methods of removing residual solvent, a fluidized-
bed technique has proved to be the fastest and most reliable drying method.
3.2 A simple column with suitable retainers, as shown in Figure A-2, will serve as a
satisfactory column. A 10.2-cm (4-in.) Pyrex® pipe, 0.6 m (2 ft) long will hold all of the
XAD-2 from the extractor shown in Figure A-l or the Soxhlet extractor, with sufficient space
for fluidizing the bed while generating a minimum resin load at the exit of the column.
650-049-08-05/me ikOO 10.app
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0010-A-3
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Loose Weave Nylon
Fabric Cover
z
10.2 cm (4 in) ^
Pyrex Pipe
0.95 cm (3/8 in) Tubing
Liquid Take-off
Liquid Nitrogen
Cylinder
Heat Source
.*<
Fine
/Screen
Coarse
/ Support
GL
cc
A
Figure A-2. XAD-2 Fluidized-bed Drying Apparatus
6S0-O49-O8-G5/ipethOO 10 .«pp
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0010-A-4
Reviaion:
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3.3 Method t: The gas used to remove the solvent is the key to preserving the
cleanliness of the XAD-2. Liquid nitrogen from a standard commercial liquid nitrogen
cylinder has routinely proved to be a reliable source of large volumes of gas free from organic
contaminants. The liquid nitrogen cylinder is connected to the column by a length of
precleaned 0.95-cm (3/8-in.) copper tubing, coiled to pass through a heat source. As nitrogen
is bled from the cylinder, it is vaporized in the heat source and passes through the column. A
convenient heat source is a water bath heated from a steam line. The final nitrogen
temperature should only be warm to the touch and not over 40° C. Experience has shown that
about 500 g of XAD-2 may be dried overnight by consuming a full 160-liter cylinder of liquid
nitrogen.
3.4 Method 2; As a second choice, high-purity tank nitrogen may be used to dry
the XAD-2. The high purity nitrogen must be passed through a bed of activated charcoal
approximately 150 mL in volume. With either type of drying method, the rate of flow should
gently agitate the bed. Excessive fluidization may cause the particles to break up.
4,0 QUALITY CONTROL PROCEDURES
4.1 For both Methods 1 and 2, the quality control results must be reported for the
batch. The batch must be reextracted if the residual extrac table organics are >20 jtg/mL by
TCO analysis or the gravimetric residue is >0.5 mg/20 g XAD-2 extracted. (See also
Section 5.1, Method 0010.)
4.2 Four control procedures are used with the final XAD-2 to check for (1) residual
methylene chloride, (2) ex tractable organics (TCO), (3) specific compounds of interest as
determined by GC/MS, as described in Section 4.5 below, and (4) residue (GRAV).
4.3 Procedure for residual methylene chlnridp:
4.3.1 Description; A 1 ± 0.1-g sample of dried resin is weighed into a small
vial, 3 mL of toluene are added, and the vial is capped and well shaken. Five /iL of
toluene (now containing extracted methylene chloride) are injected into a gas
chromatograph, and the resulting integrated area is compared with a reference standard.
The reference solution consists of 2.5 jxL of methylene chloride in lOOmL of toluene,
simulating 100 jig of residual methylene chloride on the resin. The acceptable
maximum content is 1,000 ptg/g resin.
4.3.2 Experimental: The gas chromatograph conditions are as follows:
6-ft x 1/8-in. Stainless steel column containing 10% OV-101 on 100/120
Supelcoport;
Helium carrier at 30 mL/min;
FID operated on 4 x I0'u A/mV;
65
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Injection port temperature: 250° C;
Detector temperature: 305°C;
Program: 30°C (4 min) 40"C/mtn 250°C (hold); and
Program terminated at 1,000 sec.
4.4 Procedure for residual extraetahle organic*;:
4.4.1 Description: A 20 ± 0.1-g sample of cleaned, dried resin is weighed
into a precleaned alundum or cellulose thimble which is plugged with cleaned glass
wool. (Note that 20 g of resin will fill a thimble, and the resin will float out unless
well plugged.) The thimble containing the resin is extracted for 24 hr with 200-mL of
pesticide-grade methylene chloride (Burdick and Jackson pesticide-grade or equivalent
purity). The 200-mL extract is reduced in volume to 10-mL using a Kuderna-Danish
concentrator and/or a nitrogen evaporation stream. Five fiL of that solution are
analyzed by gas chromatography using the TCO analysis procedure. The concentrated
solution should not contain >20 fig/mL of TCO extracted from the XAD-2. This is
equivalent to 10 pg/g of TCO in the XAD-2 and would correspond to 1.3 mg of TCO
in the extract of the 130-g XAD-2 module. Care should be taken to correct the TCO
data for a solvent blank prepared (200 mL reduced to 10 mL) in a similar manner.
4.4.2 Experimental: Use the TCO analysis conditions described in the revised
Level 1 manual (EPA 600/7-78-201).
4.5 GC/MS Screen; The extract, as prepared in paragraph 4.4.1, is subjected to
GC/MS analysis for each of the individual compounds of interest. The GC/MS procedure is
described in Chapter Four, Method 8270. The extract is screened at the MDL of each
compound. The presence of any compound at a concentration > 25 ptg/mL in the concentrated
extract will require the XAD-2 to be recleaned by repeating the methylene chloride step.
4.6 Methodology for residual gravimetric determination; After the TCO value
and GC/MS data are obtained for the resin batch by the above procedures, dry the remainder
of the extract in a tared vessel. There must be <0.5 mg residue registered or the batch of
resin will have to be extracted with fresh methylene chloride again until it meets this criterion.
This level corresponds to 25 mg/g in the XAD-2, or about 3.25 mg in a resin charge of 130 g.
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METHOD 0010
APPENDIX B
1.0 SCOPE AND APPLICATION
1.1 In this procedure, gas chromatography is used to determine the quantity of
lower boiling hydrocarbons (boiling points between 90° and 300°C) in the concentrates of all
organic solvent rinses, XAD-2 resin and LC fractions - when Method 1 is used (see
References, Method 0010) - encountered in Level 1 environmental sample analyses. Data
obtained using this procedure serve a twofold purpose. First, the total quantity of the lower
boiling hydrocarbons in the sample is determined. Then, whenever the hydrocarbon
concentrations in the original concentrates exceed 75 ngftn3, the chromatography results are
reexamined to determine the amounts of individual species.
The extent of compound identification is limited to representing all materials as normal
alkanes based upon comparison of boiling points. Thus the method is not qualitative. In a
similar manner, the analysis is semiquantitative; calibrations are prepared using only one
hydrocarbon. They are replicated but samples routinely are not.
1.2 Application: This procedure applies solely to the Level 1 C7-C16 gas
chromatographic analysis of concentrates of organic extracts, neat liquids, and of LC fractions.
Throughout the procedure it is assumed the analyst has been given a properly prepared sample.
1.3 Sensitivity: The sensitivity of this procedure, defined as the slope of a plot of
response versus concentration, is dependent on the instrument and must be verified regularly.
TRW experience indicates the nominal range is of the order of 77 jiV-V*sec*/tL/ng of n-
heptane and 79 ftV-sec-ftl/ng of n-hexadecane. The instrument is capable of perhaps one-
hundredfold greater sensitivity. The level specified here is sufficient for Level 1 analysis.
1.4 Defection limit: The detection limit of this procedure as written is 1.3 ng/#tL
for a 1 fiL injection of n-decane. This limit is arbitrarily based on defining the minimum
detectable response as 100 ^v-sec. This is an easier operational definition than defining the
minimum detection limit to be that amount of material which yields a signal twice the noise
level.
1.5 Range: The range of the procedure will be concentrations of 1.3 ng/jtL and
greater.
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1.6 Limitations:
1.6.1 Reporting limitations; It should be noted that a typical environmental
sample will contain compounds which (a) will not elute in the specified boiling ranges
and thus will not be reported, and/or (b) will not elute from the column at all and thus
will not be reported. Consequently, the organic content of the sample as reported is a
lower bound and should be regarded as such.
1.6.2 Calibration limitations: Quantitation is based on calibration with
n-decane. Data should therefore be reported as, e.g., mg C8/m3 as n-decane. Since
response varies linearly with carbon number (over a wide range the assumption may
involve a 20% error), it is clear that heptane (C7) detected in a sample and quarttitated
as decane will be overestimated. Likewise, hexadecane (C-16) quantitated as decane
will be underestimated. From previous data, it is estimated the error involved is on the
order of 6-7 %.
1.6.3 Detection limitations: The sensitivity of the flame ionization detector
varies from compound to compound. However, n-alkanes have a greater response than
other classes. Consequently, using an n-alkane as a calibrant and assuming equal
responses of all other compounds tends to give low reported values.
2.0 SUMMARY OF METHOD
2.1 A mL aliquot of all 10-mL concentrates is disbursed for GC-TCO analysis.
With boiling point-retention time and response-amount calibration curves, the data (peak
retention times and peak areas) are interpreted by first summing peak areas in the ranges
obtained from the boiling point-retention time calibration. Then, with the response-amount
calibration curve, the area sums are converted to amounts of material in the reported boiling
point ranges.
2.2 After the instalment is set up, the boiling point-retention time calibration is
effected by injecting a mixture of n-C7 through n-C16 hydrocarbons and operating the
standard temperature program. Response-quantity calibrations are accomplished by injecting
n-decane in n-pentane standards and performing the standard temperature program.
2.3 Definitions
2.3.1 GC: Gas chromatography or gas chromatograph.
2.3.2 C7-C16 n-alkanes: Heptane through hexadecane.
2.3.3 GCA temperature program: 4 min isothermal at 60° C, 10°C/min from
60° to 220°C.
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2.3.4 TRW temperature program: 5 min isothermal at room temperature,
15°C/min from 30° to 250°C.
3.0 INTERFERENCES
Not applicable.
4.0 APPARATUS AND MATERIALS
4.1 Gas pfirnmatograph; This procedure is intended for use on a Varian 1860 gas
chromatograph, equipped with dual flame ionization detectors and a linear temperature
programmer. Any equivalent instrument can be used provided that electrometer settings, etc.,
be changed appropriately.
4.2 Gases:
4.2.1 Helium: Minimum quality is reactor grade. A 4A or 13X molecular
sieve drying tube is required. A filter must be placed between the trap and the
instrument. The trap should be recharged after every third tank of helium.
4.2.2 Air: Zero grade is satisfactory.
4.2.3 Hydrogen: Zero grade.
4.3 Syringe: Syringes are Hamilton 70 IN, 10 fiL, or equivalent.
4.4 Septa: Septa will be of such quality as to produce very low bleed during the
temperature program. An appropriate septum is Supelco Microsep 138, which is Teflon-
backed. If septum bleed cannot be reduced to a negligible level, it will be necessary to install
septum swingers on the instrument.
4.5 Recorder: The recorder of this procedure must be capable of not less than
1 mV full-scale display, a 1-sec time constant and 0.5 in. per min chart rate.
4.6 Integrator: An integrator is required. Peak area measurement by hand is
satisfactory but too time-consuming. If manual integration is required, the method of "height
times width at half height" is used.
4.7 Columns;
4.7.1 Preferred column: 6 ft x 1/8 in. O.D. stainless steel column of 10%
OV-101 on 100/120 mesh Supelcoport.
4.7.2 Alternate column: 6 ft x 1/8 in. O.D. stainless steel column of 10%
OV-1 (or other silicon phase) on 100/120 mesh Supelcoport.
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4.8 Svringe cleaner: Hamilton syringe cleaner or equivalent connected to a suitable
vacuum source.
5.0 REAGENTS
5.1 Pentane: 'Distilled-in-Glass* (reg. trademark) or "Nanograde* (reg. trademark)
for standards and for syringe cleaning.
5.2 Methylene chloride: "Distilled-in-Glass" (reg. trademark) or "Nanograde" (reg.
trademark) for syringe cleaning.
6.0 SAMPLING HANDLING AND PRESERVATION
6.1 The extracts are concentrated in a Kuderna-Danish evaporator to a volume less
than 10 mL. The concentrate is then quantitatively transferred to a 10 mL volumetric flask
and diluted to volume. A 1-mL aliquot is taken for both this analysis and possible subsequent
GC/MS analysis and set aside in the sample bank. For each GC-TCO analysis, obtain the
sample sufficiently in advance to allow it to warm to room temperature. For example, after
one analysis is started, return that sample to the sample bank and take the next sample.
7.0 PROCEDURES
7.1 Setup and checkout: Each day, the operator will verify the following;
7.1.1 That supplies of carrier gas, air and hydrogen are sufficient, i.e., that
each tank contains > 100 psig.
7.1.2 That, after replacement of any gas cylinder, all connections leading to
the chromatograph have been leak-checked.
7.1.3 That the carrier gas flow rate is 30 ± 2 mL/min, the hydrogen flow rate
is 30 ± 2 mL/min, and the air flow rate is 300 ± 20 mL/min.
7.1.4 That the electrometer is functioning properly.
7.1.5 That the recorder and integrator are functioning properly.
7.1.6 That the septa have been leak-checked (leak-checking is effected by
placing the soap bubble flow meter inlet tube over the injection port adaptors), and that
no septum will be used for more than 20 injections.
7.1.7 That the list of samples to be run is ready.
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7.2
Retention tin 16 cslihrittioni
7.2.1 To obtain the temperature ranges for reporting the results of the
analyses, the ehromatograph is given a normal boiling point-retention time calibration.
The n-alkanes, their boiling points, and data reporting ranges are given in the table
below:
NBP, °C
Reporting Range,
°C
Report As
n-heptane
89
90-110
C7
n-octane
126
110-14Q
C8
n-nonane
151
140-160
C9
n-decane
174
160-180
C10
n-undecane
194
180-200
€11
n-dodecane
214
200-220
C12
n-tridecane
234
220-240
C13
n-tetradecane
252
240-260
C14
n-pentadecane
270
260-280
€15
n-hexadecane
288
280-300
€16
7.2.2 Preparation of standards: Preparing a mixture of the C7-C16 alkanes
is required. There are two approaches: (1) use of a standards kit (e.g., Polyscience
Kit) containing bottles of mixtures of selected n-alkanes which may be combined to
produce a C7-C16 standard; or (2) use of bottles of the individual C7-C16 alkanes from
which accurately known volumes may be taken and combined to give a C7-C16
mixture,
7.2.3 Procedure for retention tune calibration: This calibration is performed
at the start of an analytical program; the mixture is chromatographed at the start of
each day. To attain the required retention time precision, both the carrier gas flow rate
and the temperature program specifications must be observed. Details of the procedure
depend on the instrument being used. The general procedure is as follows:
7.2.3.1 Set the programmer upper limit at 250° C. If this setting does
not produce a column temperature of 250°C, find the correct setting.
7.2.3.2 Set the programmer lower limit at 30°C.
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7X3.3 Verify that the Instrument and samples are at room
temperature.
7.2.3.4 Inject 1 of the n-alkane mixture.
7.2.3.5 Start the Integrator and recorder.
7.2.3.6 Allow the instrument to run isothermieaUy at room temperature
for five minutes.
7.2.3.7 Shut the oven door.
7.2.3.8 Change the mode to Automatic and start the temperature
program.
7.2.3.9 Repeat steps 1-9 a sufficient number of times so that the
relative standard deviation of the retention times for each peak is <5%.
7.3 Response calibration;
7.3.1 For the purpose of a Level 1 analysis, response-quantity calibration with
n-deeane is adequate. A 10-/*L volume of n-deeane is injected into a tared 10 mL
volumetric flask. The weight injected is obtained and the flask is diluted to the mark
with n-pentane. This standard contains about 730 ng n-decane per pL n-pentane. The
exact concentration depends on temperature, so thai a weight is required. Two serial
tenfold dilutions are made from this standard, giving standards at about 730, 73, and
7.3 ng n-decane per jtL n-pentane, respectively.
7.3.2 Procedure for response calibration: This calibration is performed at
the start of an analytical program and monthly thereafter. The most concentrated
standard is injected once each day. Any change in calibration necessitates a full
calibration with new standards. Standards are stored in the refrigerator locker and are
made up monthly.
7.3.2.1 Verify that the instrument is set up properly.
7.3.2.2 Set electrometer at 1 * 10"'° A/mV.
7.3.2.3 Inject 1 /xL of the highest concentration standard.
7.3.2.4 Run standard temperature program as specified above.
7.3.2.5 Clean syringe.
7.3.2.6 Make repeated injections of all three standards until the relative
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standard deviations of the areas of each standard are *5%.
7.4 Sample analysis procedure;
7.4.1 The following apparatus is required;
7.4.1.1 Gas chromatograph set up and working.
7.4.1.2 Recorder, integrator working.
7.4.1.3 Syringe and syringe cleaning apparatus.
7.4.1.4 Parameters: Electrometer setting is 1 x 1G"50 A/mV; recorder is
set at 0.5 in./min and 1 mV full-scale.
7.4.2 Steps in the procedure are:
7.4.2.1 Label chromatogram with the data, sample number, etc.
7.4.2.2 Inject sample,
7.4.2.3 Start integrator and recorder.
7.4.2.4 After isothermal operation for 5 min, begin temperature
program.
7.4.2.5 Clean syringe.
7.4.2.6 Return sample; obtain new sample.
7.4.2.7 When analysis is finished, allow instrument to cool. Turn
chromatogram and integrator output and data sheet over to data analyst.
7.5 Syringe cleaning procedure;
7.5.1 Remove plunger from syringe.
7.5.2 Insert syringe into cleaner; turn on aspirator.
7.5.3 Fill pipet with pentane; run pentane through syringe.
7.5.4 Repeat with methylene chloride from a separate pipet.
7.5.5 Flush plunger with pentane followed by methylene chloride.
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7.5.6 Repeat with methylene chloride.
7.6 Sample analysis decision criterion: The data from the TCO analyses of organic
extract and rinse concentrates are first used to calculate the total concentration of C7-C16
hydrocarbon-equivalents (Paragraph 7.7.3) in the sample with respect to the volume of air
actually sampled, i.e., #tg/m3. On this basis, a decision is made both on whether to calculate
the quantity of each n-alkane equivalent present and on which analytical procedural pathway
will be followed. If the total organic content is great enough to warrant continuing the
analysis- >500 /tg/m3 —a TCO of less than 75 pgfm3 will require only LC fractionation and
gravimetric determinations and IR spectra to be obtained on each fraction. If the TCO is
greater than 75 then the first seven LC fractions of each sample will be reanalyzed
using this same gas chromatographic technique.
7.7 Calculations:
7.7.1 Boiling Point - Retention Time Calibration: The required data for this
calibration are on the chromatogram and on the data sheet. The data reduction is
performed as follows:
7.7.1.1 Average the retention times and calculate relative standard
deviations for each n-hydrocarbon.
7.7.1.2 Plot average retention times as abscissae versus normal boiling
points as ordinates.
7.7.1.3 Draw in calibration curve.
7.7.1.4 Locate and record retention times corresponding to boiling
ranges 90-100, 110-140, 140-160, 160-180, 180-200, 200-220, 220-240,
240-260, 260-280, 280-300" C.
7.7.2 Response-amount calibration: The required data for this calibration are
on the chromatogram and on the data sheet. The data reduction is performed as
follows:
7.7.2.1 Average the area responses of each standard and calculate
relative standard deviations.
7.7.2.2 Plot response (jxvscc) as ordinate versus ng/^L as abscissa.
7.7.2.3 Draw in the curve. Perform least squares regression and
obtain slope (jtV-sec-ftL/ng).
7.7.3 Total C7-C16 hydrocarbons analysis: The required data for this
calculation are on the chromatogram and on the data sheet. The data reduction is
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performed as follows:
7.7.3.1 Sum the areas of all peaks within the retention time range of
interest.
7.7.3.2 Convert this area Q*V-sec) to ng/pL by dividing by the weight
response for n-decane (piV-sec-^L/ng).
7.7.3.3 Multiply this weight by the total concentrate volume (10 mL)
to get the weight of the C7-C16 hydrocarbons in the sample.
7.7.3.4 Using the volume of gas sampled or the total weight of sample
acquired, convert the result of Step 7.7.3.3 above to pg/m3.
7.7.3.5 If the value of total C7-C16 hydrocarbons from Step 7.7.3.4
above exceeds 75 figlm*, calculate individual hydrocarbon concentrations in
accordance with the instructions in Paragraph 7.7.5.5 below.
7.7.4 Individual C7-C16 n-ALkane Equivalent Analysis: The required data
from the analyses are on the chromatogram and on the data sheet. The data reduction
is performed as follows:
7.7.4.1 Sum the areas of peaks in the proper retention time ranges.
7.7.4.2 Convert areas (/iV*sec) to ng/^L by dividing by the proper
weight response (pV'seejiL/ng).
7.7.4.3 Multiply each weight by total concentrate volume (10 mL) to
get weight of species in each range of the sample.
7.7.4.4 Using the volume of gas sampled on the total weight of sample
acquired, convert the result of Step 7.7.4.3 above to #ig/m3.
8.0 QUALITY CONTROL
8.1 Appropriate QC is found in the pertinent procedures throughout the method.
9.0 METHOD PERFORMANCE
9.1 Even relatively comprehensive error propagation analysis is beyond the scope of
this procedure. With reasonable care, peak area reproducibility of a standard should be of the
order of 1% RSD. The relative standard deviation of the sum of all peaks in a fairly complex
waste might be of the order of 5-10%. Accuracy is more difficult to assess. With good
analytical technique, accuracy and precision should be of the order of 10-20%.
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10.0 REFERENCES
1*0 Emissions Assessment of Conventional Stationary Combustion Systems:
Methods and Procedure Manual for Sampling and Analysis, Interagency
Energy/Environmental R&D Program, Industrial Environmental Research Laboratory,
Research Triangle Park, NC 27711, EPA-600/7-79-029a, January 1979.
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Appendix G
Method 3542
Preparation of Modified Method 5 (SW-846, Method 0010)
Train Components for Analysis by SW-846 Method 8270
(This is the latest draft version of Method 3542 from SW-846.
The final version of the document when released supersedes
this one and will be inserted in its place)
-------
METHOD 3542
PREPARATION OF MODIFIED METHOD 5 (SW-846 METHOD 0010)
TRAIN COMPONENTS FOR ANALYSIS BY SW-S4G METHOD 8270
1.0 SCOPE AND APPLICATION
1.1 This method describes the extraction of semivolatile organic compounds from
samples collected by the EPA SW-846 Method 0010. This method replaces Section 8.1 of
SW-846 Method 0010 (Modified Method 5 Sampling Train, also known as SemiVOST) and
Sections 7.1 and 7.2 of SW-846 Method 8270 (Gas Chromatography/ Mass Spectrometry for
Semivolatile Organics: Capillary Column Technique), which deal with sample preparation.
These sections discuss sample preparation procedures. Section 8.1 of Method 0010 addresses
preparation of Method 0010 train components for analysis with very little detail.
Sections 7.1 and 7.2 of Method 8270 address preparation of water, soil/sediment, and water
matrices. Analytical procedures described in Section 7.3 of Method 8270 are relevant, with
the exception that the final volume of the extracts of the Method 0010 train components must
be 5 mL, with surrogate compound concentrations as indicated in this method.
Although this sample preparation technique is intended primarily for gas
chromatography/mass spectrometrie (GC/MS) analysis following Method 8270, the extracts
prepared according to this method may be used with other analytical methods. The
Method 0010 sampling train collects semivolatile organic compounds with boiling points
above 100°C. Some of these semivolatile organic compounds may not be amenable to gas
chromatography and will require the application of high performance liquid chromatography
(HPLC) for quantitative analysis. The use of HPLC coupled with mass spectrometry
(HPLC/MS) is an analytical technique that may also be applied. A solvent exchange from
methylene chloride to a more polar solvent such as acetonitrile or extraction with a solvent
other than methylene chloride will probably be required for successful application of HPLC
techniques. Some semivolatile analytes may require derivatization for successful GC/MS
analysis.
3542 -1-
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METHOD 3542
1.2 This method is restricted to use by or under the supervision of analysts
experienced in the extraction and concentration of semivolatile organic compounds from the
components of Method 0010 trains. Each analyst must demonstrate the ability to generate
acceptable results with this method.
3542 -2-
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METHOD 3542
2.0 SUMMARY OF METHOD
2,1 Samples generated by the Method 0010 Sampling Train (Method 0010
Sampling Train, Figure 2-1) are separated into six parts;
1. a particulate matter filter (labeled in Method 0010 as Container No. 1);
2. a front half rinse (labeled in Method 0010 as Container No. 2);
3. condenser rinse and rinse of all sampling train components located
between the filter and the sorbent module (labeled in Method 0010 as
Container No. 5);
4. sorbent trap section of the organic module (labeled in Method 0010 as
Container No. 3);
5. any condensate and condensate rinse (labeled in Method 0010 as
Container No. 4); and
6. silica gel (labeled in Method 0010 as Container No. 6).
The six parts recovered from the Method 0010 sampling train yield three 5 mL extracts to be
analyzed according to the analytical procedures of Method 8270. The particulate matter
filter is extracted by Soxhlet (SW-846 Method 3540, with exceptions as noted). The front
half rinse is filtered, and any filtrate is added to the particulate matter filter for Soxhlet
extraction. The front half rinse is a 50:50 mixture of methanol and methylene chloride
generated by rinsing the probe and the front half of the filter holder in the Method 0010
train. The front half rinse is extracted with methylene chloride by separatory funnel
(SW-846 Method 3510, with exceptions as noted) after sufficient HPLC-grade water (or
equivalent) has been added to make the methylene chloride separate as a distinct phase from
the methanol/water. The extracts from the filter and front half rinse are combined, moisture
is removed by filtering through anhydrous sodium sulfate (Na2SOJ, and the combined extract
is concentrated using a Kudema-Danish (K-D) sample concentrator (SW-846 Method 3540)
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METHOD 3542
Stack
Wall
Thermocouples
Filter
Condenser
Manometer
Silica Get
Thermocouples
_ condensate
Vacuum
Gauge
Vacuum
Line
By-pass
Valve
Main
Valve
Dry Gas
Meter
Figure 2-1. Method 0010 Sampling Train,
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METHOD 3542
to a final volume of 5 mL. The final sample concentration to 5 mL am be performed more
accurately by reducing the volume of the sample using a gentle stream of nitrogen or by
using a micro-K-D, The condensate and condensate rinse fractions consist of the aqueous
contents of the first impinger of the Method 0010 sampling train and the 50:50
methanol/methylene chloride rinse of the first impinger of the Method 0010 sampling train.
The condensate and condensate rinse fractions are combined and extracted with methylene
chloride using a separatory funnel after sufficient HPLC-grade water (or equivalent) has been
added to make the methylene chloride separate from the methanol/water following the
procedures of SW-846 Method 3510 (with exceptions as noted). After an initial methylene
chloride extraction without pH adjustment, the pH of the combined condensate/condensate
rinse fraction is determined. If the condensate/condensate rinse fraction is acid (pH < 7),
the pH is adjusted to a level less than 2 and the methylene chloride extraction is repeated.
The pH of the condensate/condensate rinse fraction is then made basic (pH > 12), and the
methylene chloride extraction is repeated. The methylene chloride extracts are combined,
and moisture is removed by filtration through a bed of anhydrous Na2S04. If the
condensate/condensate rinse fraction is found to be basic after the initial methylene chloride
extraction, the pH adjustment sequence is reversed: a basic extraction is performed prior to
an acid extraction, the methylene chloride extracts are combined, the moisture is removed,
and the extract is concentrated to a volume of 5 mL. The XAD-2® sampling module is
combined with the filter holder back half rinse and the 50:50 methylene ehloride/methanol
condenser rinse and extracted by Soxhlet (SW-846 Method 3540, with exceptions as noted).
Water is added to the extract to ensure the separation of methanol/water from the methylene
chloride, and a water extraction of the methylene chloride extract is performed. Moisture is
removed from the methylene chloride extract, which is then concentrated to a final volume of
5 mL for analysis. The contents of the remaining impingers are usually archived, but may
be extracted by separatory funnel. The silica gel is reused after regeneration by heating to
remove moisture. The overall sample preparation scheme is shown in Figure 2-2.
3542 -5-
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METHOD 3542
XAD-2®
(Container 3)
Analyze by GC/MS
Combine CH2Ci2 Extracts
Archive
Weigh in the Field
Concentrate to 5mL
Regenerate
Re-use
XAD-2® Extract
Soxhlet Extraction
Impinger Contents
(Impingers 2 and 3)
Remove Moisture
with Na.SO,
Spike with Surrogates (and
Isotopically-Labeled Analogs)
Add Sufficient Water
to Separate into Two
Phases; Separate
Silica Gel
(Impinger 4)
(Container 5)
Extract Water Layer with
CH2Cl2; Adjust pH and Do
Acid/Base or Base/Acid Extraction
Rinse all of Glassware Between
Back Half of Filter Holder and
XAD-2® (Filter Holder Back Half
Connector, and Condenser)
with CH2CI2/CH3OH
(Container 5)
Figure 2-2. Sample Preparation Scheme for Method 0010 Train Components.
3542 -6-
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METHOD 3542
Combine
Combine CH2CI:
Extracts
Remove Moisture with Na,SO.
Concentrate to 5mL
Analyze by GC/MS
Combine CH2Q2 Extracts
Analyze by GC/MS
Concentrate to 5mL
Remove Moisture with Na,SO.
Rinse of Impinger 1
CH,Ci,/CH,OH
Condensate H20
(Impinger 1)
(Container 4)
Soxhlet Extraction
CH ,CU
Spike with Surrogates,
Isotopicaliy-Labeled
Analogs
Save CH2CI2 Layer
(Bottom)
Particulate Matter
Filter
(Container 1)
Filter; Add Filter to
Particulate Matter Filter
Separatory Funnel Extraction
(Add H2O if necessary to
separate phases)
Spike with Surrogates and
I sotopically-Labeied Analogs
Extract Water Layer with
CH2CI2; Adjust pH and do
Acid/Base or Base/Acid
Extraction
Extract Water Layer with
CH2CI2; Adjust pH and do
Acid/Base or Base/Acid
Extraction
Separatory Funnel
Extraction
(Add H2O if necessary to
separate phases)
Front Half Rinse,
Front Half of Filter Holder,
Probe and Nozzle
CH2CI2/CH3OH
(Container 2)
Figure 2-2. Continued
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METHOD 3542
3,0 INTERFERENCES
3.1 Method interferences may be caused by contaminants in solvents, reagents,
glassware, and other sample processing hardware. All of these materials must be routinely
demonstrated to be free from interferences under the conditions of the analysis by preparing
and analyzing laboratory method (or reagent) blanks.
3.1.1 Glassware must be cleaned thoroughly before using. The glassware
should be washed with laboratory detergent in hot water followed by rinsing with tap
water and distilled water. The glassware may be cleaned by baking in a glassware
oven at 400°C for at least one hour. After the glassware has cooled, the glassware
should be rinsed three times with methanol and three times with methylene chloride.
Volumetric glassware should not be heated to 400°C. Rather, after washing and
rinsing, volumetric glassware may be rinsed with methanol followed by methylene
chloride and allowed to dry in air.
3.1.2 The use of high purity reagents and solvents helps to minimize
interference problems in sample analysis.
3.2 Matrix interferences in the analysis may be caused by components of the
sampling matrix that are extracted from the samples. If matrix interferences interfere with
the analysis, sample cleanup procedures (e.g., SW-846 Method 3620 or Method 3610) may
be employed to remove or mitigate the interferences.
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METHOD 3542
4.0 APPARATUS AND MATERIALS
4.1 Soxhlet Extractor. 40-mm I.D., with 500-mL round bottom flask and
condenser.
4.2 Boiling Chips. Teflon®, solvent rinsed with methylene chloride,
approximately 10/40 mesh.
4.3 Forceps. Rinsed with methylene chloride before use.
4.4 Separatorv Funnel. 250 mL or larger, with Teflon® stopcock.
4.5 Amber Glass .Tar. 500 mL with Teflon®-lined screw cap.
4.6 Glass Funnel. Long stem.
4.7 Kudema-Danlsh
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METHOD 3542
4.8 Glass Wool. Non-silanized, pre-cleaned by Soxhlet extraction with methylene
chloride. Air dry, store in pre-cleaned 500 mL jar.
4.9 Vials. 7-10 mL capacity, calibrated (calibrated centrifuge tubes may also be
used).
4.10 Heating Mantle. Rheostat-controlled.
4.11 Water Bath. Heated, with concentric ring cover, capable of temperature
control 80°C ± 5°C. The water bath should be used in a hood.
4.12 Gas-tight Syringe. 5-mL to 10-mL capacity. Gas-tight syringes have a glass
barrel, with a Teflon® plunger to form an effective seal. The lack of contact with metal and
the sealing properties make these syringes very useful for transferring liquid solutions.
4.13 Nitrogen Slowdown Apparatus. Analytical evaporator such as The Meyer
N-EVAP Model 111 (Organomation Associates Inc., South Berlin, MA 01549) or equivalent.
4.14 Filter. Glass- or quart-fiber filters, without organic binder. The filters should
be the same as those used in the Method 0010 sampling train.
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5.0 REAGENTS
METHOD 3542
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise indicated,
all reagents shall conform to the specifications of the Committee on Analytical Reagents of
the American Chemical Society, where such specifications are available. Other grades may
be used, provided it is first ascertained that the reagent is of sufficient purity to permit its use
without compromising the integrity of the sample.
5.2 Methanol. Pesticide quality or equivalent.
5.3 Methylene Chloride. Pesticide quality or equivalent.
5.4 Reagent Water. Reagent water is defined as water in which an interferent is
not observed at the method detection limit (MDL) of the parameters of interest. The
cleanliness of the reagent water is determined by extracting 200 mL of reagent water three
times with methylene chloride. The methylene chloride extracts are combined, moisture is
removed by filtration through Na2S04, the extract is concentrated to 5 mL, and GC/MS
analysis is preformed.
5.4.1 Reagent water may be generated by passing tap water through a carbon
filter bed containing about 400 to 500 g of activated carbon (Calgon Corporation,
Filtrasorb-300 or equivalent).
5.4.2 A water purification system (Millipore Super-Q or equivalent) may be
used to generate reagent water.
5.5 Sodium Hydroxide Solution (10 Molar): Dissolve 40 g of sodium hydroxide
(NaOH, ACS reagent grade) in reagent water and dilute to 100 mL.
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METHOD 3542
5.6 Sulfuric Acid (H-JSQj) (9 Molar). Slowly add 50 mL of concentrated 18 M
H2S04 (ACS reagent grade, specific gravity 1.84) to 50 mL of reagent water.
5.7 Sodium sulfate (Na7SO^. ACS, reagent grade, granular, anhydrous. Purify
by heating at 400°C for four hours in a shallow tray.
5.8 Surrogate Stock Solution. Either surrogate standards (e.g., the surrogate
standards used in Method 8270) or isotopically-labeled analogs of the compounds of interest
must be spiked into the Method 0010 train components prior to extraction. Both surrogate
standards and isotopically-labeled analogs may be used, if desired. A surrogate standard
(i.e., a compound not expected to occur in an environmental sample but chemically similar to
analytes) should be added to each sample, blank, and method spike just prior to extraction.
The recovery of the surrogate standard is used to monitor for unusual matrix effects or
sample processing errors. Normally three or more surrogate standards are added for each
analyte group. The surrogate stock solution may be prepared from pure standard materials
or purchased as a certified solution. Prepare the stock solution in methylene chloride, using
assayed liquids or solids, as appropriate.
5.8.1 The following compounds are the surrogate standards recommended in
SW-846 Method 8270:
5.8.2 Prepare a surrogate standard stock solution in methylene chloride that
contains the surrogate compounds at a concentration of 5000 jxg/mL for the acidic
compounds, and 2500 jxg/mL for base/neutral compounds. Prepare the stock
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Acid
2-FluorophenoI
2,4,6-Tribromophenol
Phenol-dft
Base/Neutral
2-Fluorobiphenyl
Nitrobenzene-dj
Terphenyl-di4
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METHOD 3S42
surrogate solution by accurately weighing 0.50 ± 0.05 g each of 2-fluorobiphenyl, p-
terphenyl-d(4, and nitrobenzene-d„ and 1.00 + 0.05 g each of 2,4,6-tribromophenol,
phenol-d6, and 2-fluorophenol. Dissolve the materials in methylene chloride and
dilute to volume in a 200 mL volumetric flask. When compound purity is assayed to
be 96% or greater, the weight may be used without correction to calculate the
concentration of the stock solution.
5.8.3 Transfer the stock solution into Teflon®-sealed screw-cap bottles sized
to minimize headspace. Store at 4°C and protect from light. Stock solutions should
be checked regularly for signs of degradation or evaporation, especially just prior to
preparing spiking solutions. Allow solutions to come to room temperature before use
5.8.4 Stock solutions should be replaced after one year, or sooner if analysis
indicates a problem.
5.9 Surrogate Standard Spiking Solution. Prepare a surrogate standard spiking
solution by transferring a 10-mL aliquot of the surrogate stock solution (using a 10-mL
volumetric pi pet) into a 50-mL volumetric flask containing approximately 20 mL of
methylene chloride. Dilute to a final volume of 50 mL with methylene chloride.
5.9.1 Transfer the surrogate standard spiking solution into Teflon®-sealed
screw-cap bottles appropriately sized to minimize headspace. Store at 4°C and
protect from light. Spiking solutions should be checked regularly for signs of
degradation or evaporation, especially just prior to use.
5.9.2 Surrogate standard spiking solutions should be replaced after six
months, or sooner if analysis indicates a problem.
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METHOD 3542
5.10 Isotopicaiiv-Labeled Analog Stock Solution, Either surrogate standards
(e.g., the surrogate standards used in Method 8270) or isotopically-labeled analogs of the
compounds of interest must be spiked into the Method 0010 train components prior to
extraction. Both surrogate standards and isotopically-labeled analogs may be used, if
desired. The use of isotopically-labeled analogs is optional but highly recommended.
Common isotopic labels which are used include deuterium and carbon-13; homologs and
fluorinated analogs of the compounds of interest may also be used. To assess extraction
efficiency, use of an isotopically-labeled analog of the compound of interest is essential. The
isotopically-labeled analog is spiked into the matrix immediately prior to extraction, and
losses of the spiked compound can be attributed to the sample extraction/ concentration
process. An isotopically-labeled analog stock solution can be made from pure standard
materials or purchased as a certified solution. Even though the use of isotopically-labeled
analogs is optional, each compound to be quantified must be represented by a specific
recovery standard, whether in the surrogate standard mixture (Section 5.8) or in a separate
spike.
5.10.1 Prepare an isotopically-labeled analog stock solution by
accurately weighing approximately 0.250 g of each of the materials to be used.
Dissolve in methylene chloride and dilute to volume with methylene chloride in a
200-mL volumetric flask. When compound purity is assayed to be 96% or greater,
the weight may be used without correction to calculate the concentration of the stock
solution.
5.10.2 Transfer the stock solution into Teflon®-sealed screw-cap bottles
sized to minimize headspace. Store at 4°C and protect from light. Stock solutions
should be checked regularly for signs of degradation, evaporation, or isotope
exchange, especially just prior to preparing spiking solutions from them. Allow
solution to come to room temperature before use.
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METHOD 3542
5.10.3 Stock solutions should be replaced after one year, or sooner if
analysis indicates a problem,
5.11 Isotopicallv-Labeled Analog Spiking Solution
5.11.1 Prepare the isotopically-labeled analog standard by transferring a
10-mL aliquot of the stock isotopically-labeled analog stock solution (using a 10-mL
volumetric pi pet) into a 50-mL volumetric flask containing approximately 20 mL of
methylene chloride. Dilute to volume with methylene chloride. The concentration of
the spiking solution should allow the isotopically-labeled analogs to be observed in the
final sample in approximately the middle of the calibration range for the gas
chromatograph/mass spectrometer, assuming 100% recovery.
5.11.2 Transfer the solution into Teflon®-sealed screw-cap bottles sized
to minimize headspace. Store at 4°C and protect from light. Spiking solutions
should be checked regularly for signs of degradation or evaporation, especially just
prior to use. Allow solutions to come to room temperature prior to use.
5.11.3 Spiking solutions should be replaced after six months, or sooner
if analysis indicates a problem,
5.12 Stock Method Spike Solution: A method spike consists of a spike of a clean
matrix (i.e., clean, dry XAD-2®, clean, dry filter, or water) with a solution containing the
compounds of interest (the method spike solution). The compound recoveries obtained from
a method spike demonstrate that the compounds of interest can be recovered from the matrix,
and aid in elucidating the effects of the field matrix. The method spike solution can be made
from pure standard materials or purchased as certified solutions. The compounds of interest
for the field test should be used as components of the method spike solution. A method
spike is generated by spiking clean XAD-2® or clean reagent grade water.
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METHOD 3542
5.12.1 Prepare a stock method spike solution by accurately weighing
0.05 g each of the compounds of interest. Dissolve the materials in methylene
chloride and dilute to volume in a 50-mL volumetric flask. When compound purity is
assayed to be 96% or greater, the weight may be used without correction to calculate
the concentration of the stock solution.
5.12.2 Transfer the stock method spike solution into Teflon®-sealed
screw-cap bottles sized to minimize headspace. Store at 4°C and protect from light.
Stock solutions should be checked regularly for signs of degradation or evaporation,
especially just prior to preparing spiking solutions from them.
5.12.3 Stock solutions should be replaced after one year, or sooner if
analysis indicates a problem,
5.13 Method Spike Standard Solution
5.13.1 Prepare the method spike standard solution by transferring a
25-mL aliquot of the stock method spike solution (using a 25-mL volumetric pipet)
into a 100-mL volumetric flask containing approximately 20 mL of methylene
chloride. Dilute to volume with methylene chloride.
5.13.2 Transfer the method spike standard solution into Teflon®-lined
screw-cap bottles appropriately sized to minimize headspace. Store at 4°C and
protect from light. Spiking solutions should be checked regularly for signs of
degradation or evaporation, especially just prior to use.
5.13.3 Spiking solutions should be replaced after six months, or sooner
if analysis indicates a problem.
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METHOD 3542
6.0 SAMPLE HANDLING
6.1 The six components from each Method 0010 sampling train (Figure 2-1) must
be stored at 4°C between the time of sampling and extraction. Each sample should be
extracted within 14 days of collection and must be analyzed within 40 days of extraction.
The extracted sample must be stored at 4°C.
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METHOD 3542
7.0 SAMPLE PREPARATION
7.1 The sample preparation procedure for the six parts of the Method 0010 train
will result in three sample extracts for analysis:
1. Particulate Matter Filter and Front Half Rinse;
2. Condensate and Condensate Rinse; and
3. XAD-2® and Condenser/Back Half Rinse,
7.2 Particulate Matter Filter and Front Half Rinse.
7.2.1 Filter. The filter is identified as Container No. I in Method 0010.
7.2.1.1 Using clean forceps, place about 10 Teflon® boiling chips into
the bottom of the round bottom flask of the Soxhlet extractor and connect the
Soxhlet extractor to the round bottom flask.
7.2.1.2 Using a clean syringe or volumetric pipet, add a 1-mL aliquot
of the surrogate standard spiking solution (Section 5.9) to the filter. If
isotopically-labeled analogs are being used, the isotopically-labeled analog
solution (Section 5.11) may be added at this time. If a Method Spike is being
prepared, the Method Spike Solution (Section 5.13) may be added at this time.
To ensure proper filter spiking, use a volume of approximately 1 mL of
spiking solution. Leave the filter in the petri dish, particulate material on top,
for spiking. Spike the 1 mL of spiking solution uniformly onto the
particulate-coated surface of the filter in the petri dish by spotting small
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METHOD 3542
volumes at multiple filter locations, using a syringe. Repeat the spiking
process with isotopically-Iabeled standards or method spike solution, if these
solutions are being used.
7.2.1.3 Using clean forceps, place the Particulate Matter Filter into a
glass thimble and position the glass thimble in the Soxhlet extractor, making
sure that the filter will be completely submerged in the methylene chloride
with each cycle of the Soxhlet extractor. Place a piece of pre-cleaned
unsilanized glass wool on top of the filter in the Soxhlet extractor to keep the
filter in place. Rinse the petri dish three times with methylene chloride and
add rinses to the Soxhlet,
The Front Half Rinse (Container No. 2) may contain particulate
material which has been removed from the probe. This particulate material
should be extracted with the filter. To separate particulate matter from the
Front Half Rinse, filter the Front Half Rinse. To avoid introducing any
contamination, use the same type of filter which has been used in the
Method 0010 train, from the same lot as the filter in the Method 0010 train.
Filter the Front Half Rinse, rinse Container No. 2 three times with 10 mL
aliquots of methylene chloride, and filter the methylene chloride rinses.
Transfer the filter with any particulate matter to the Soxhlet extractor with the
original filter from the Method 0010 train. Extract the two filters tpgether.
Return the liquid portion of Container No. 2 to its orignial container for
subsequent extraction or, alternatively, the Front Half Rinse can be filtered
directly into a separatory funnel for extraction of the liquid portion of the
Front Half Rinse.
7.2.1.4 Slowly add methylene chloride to the Soxhlet extractor
containing the two filters through the Soxhlet (with condenser removed),
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METHOD 3542
allowing the Soxhlet to cycle. Add sufficient solvent to fill the round bottom
flask approximately half full and submerge the thimble containing the filters.
7.2.1.5 Place a heating mantle under the round bottom flask and
connect the upper joint of the Soxhlet to a condenser, making sure that the
coolant is flowing through the condenser.
7.2.1.6 Allow the sample to extract for 18 hours, cycling
approximately once every thirty minutes.
7.2.1.7 After cooling, disconnect the extractor from the condenser.
Tilt the Soxhlet slightly until the remaining solvent has drained into the round
bottom flask.
7.2.1.8 Transfer the extract from the round bottom flask into a
500-mL amber glass bottle with Teflon®-lined screw cap. The bottle should
have been rinsed three times each with methanol and methylene chloride.
Rinse the round bottom flask three times with approximately 10-mL aliquots of
methylene chloride and transfer the rinses to the amber bottle. Store the filter
extract at 4°C until extraction of the filtered Front Half Rinse has been
completed.
7.2.2 Front Half Rinse. The Front Half Rinse is identified as Container
No. 2 in Method 0010.
7.2.2.1 Transfer the liquid contents of the filtered Front Half Rinse
sample to a separatory funnel of appropriate size for the volume of the sample
(a typical Front Half Rinse sample is 200 to 300 mL). Rinse the sample
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METHOD 3542
container three times with 10-mL aliquots of methylene chloride, transferring
the rinses to the separatory funnel after each rinse.
7.2.2.2 Because the Front Half Rinse sample consists of a mixture of
methanol and methylene chloride, sufficient reagent grade water must be added
to the separatory funnel to cause the organic and aqueous/methanol phases to
separate into two distinct layers. The methylene chloride layer will be at the
bottom of the separatory funnel. Continue to add water until the bottom layer
(methylene chloride) does not increase in volume. An increase in volume can
be monitored by marking the separatory funnel at the position of the phase
separation.
NOTE: The Front Half Rinse is not spiked with any surrogate,
isotopic analog, or method spike solutions because the
extract from the Front Half Rinse is combined with the
extract from the Particulate Matter Filter sample.
7.2.2.3 Add additional methylene chloride, if necessary, so that the
ratio of water/methanol to methylene chloride is approximately 3; I. Add
sodium hydroxide (Section 5.5) until pH of the water layer is > 11 (but
< 14). Use wide-range pH paper to determine pH. Shake vigorously for
2 minutes with rapid arm motion, with periodic venting to release excess
pressure. Allow the organic layer to separate for at least 10 minutes. Collect
the methylene chloride extract in a 500-mL amber glass bottle with Teflon®-
lined screw cap, which has been rinsed three times each with methanol and
methylene chloride.
7.2.2.4 Add a second volume of methylene chloride (approximately
the same volume as the first extraction) to the separatory funnel and repeat the
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METHOD 3542
extraction procedure, combining the methylene chloride extracts in the amber
bottle.
7.2.2.5 Perform a third extraction in the same manner.
7.2.2.6 Acidify the water to a pH <2 (but > 0) with sulfuric acid
(Section 5.6) and repeat Section 7.2.2.4 three times. Measure pH with wide-
range pH paper.
7,2.3 Concentration of Filter and Front Half Rinse Extracts. The
combined extracts and rinses of extract storage bottles will have a total volume of
1 liter or more.
7.2.3.1 Assemble a Kuderna-Danish concentrator by attaching a
10-mL concentrator tube to a 500-mL evaporative flask with clips or springs.
Using a clean pair of forceps, place about 5 Teflon® boiling chips into the
concentrator tube. If the volume of extract to be concentrated is greater than
500 mL, repeat the concentration as many times as required using the same
500-mL evaporative flask and systematically adding remaining extract. If
repeated concentrations are performed, use new boiling chips each time.
7.2.3.2 Using a clean pair of forceps, place a small portion of
precleaned unsilanized glass wool in the bottom of a long stem funnel, and
pour a 1-inch layer of cleaned sodium sulfate (Section 5.7) on top of the glass
wool (use more sodium sulfate, if possible; fill the funnel to within
approximately 0.5 inch of the top).
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METHOD 3542
7.2.3.3 Rinse the sodium sulfate contained in the funnel three times
with methylene chloride; discard the rinses. Support the funnel in a ring or
clamp above the flask to prevent tipping.
7.2.3.4 Place the funnel into the upper opening of the K-D flask and
slowly pour extracts from the Filter and Front Half Rinse through the sodium
sulfate. Rinse the amber jars containing the extracts three times, using
approximately 10 mL of methylene chloride each time. Add the rinses to the
funnel. Rinse the sodium sulfate with methylene chloride to complete the
transfer.
NOTE: During this process, monitor the condition of the sodium
sulfate to determine that the bed of sodium sulfate is not
solidifying and exceeding its drying capacity. If the
sodium sulfate bed can be stirred and is still free-
flowing, effective moisture removal from the extracts is
occurring. If the sodium sulfate bed has begun to
solidify, do not add more extract. Replace the sodium
sulfate bed, re-dry the contents of the K-D flask, and
continue drying the extracts.
7.2.3.5 Attach a three-ball macro Snyder column to the evaporative
flask. Prewet the Snyder column by adding about 2 mL of methylene chloride
to the top. Place the K-D apparatus on a hot water bath (80-85 °C) so that the
concentrator tube is partially immersed in hot water. Adjust the vertical
position of the apparatus and the water temperature as required to complete the
concentration in 20 to 30 minutes. Rinse sides of K-D during concentration
with a small volume of methylene chloride. When the apparent volume of the
liquid reaches 6-8 mL, remove the K-D apparatus from the water bath and
allow the apparatus to cool and drain for at least 10 minutes.
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METHOD 3542
NOTE: Never let the extract in the concentrator lube go to
dryness even though additional solvent is present in the
upper portion of the K-D apparatus.
NOTE: If the sample concentration is not completed within the
anticipated period of time, check the temperature of the
water bath and check the composition of the sample. If
the methanol has not been completely removed from the
methylene chloride extract by the procedures described in
Sections 7.2.2.2 and 7.2.2.3, residual methanol will
concentrate far slower than a methylene chloride extract
and analytes will be lost in the concentration step. A
sample containing methanol which has been concentrating
for a prolonged period of time cannot be recovered, but
extracts which contain residual methanol and have not
yet been concentrated can be recovered by performing
the procedures in Sections 7.2.2.2 and 7.2.2.3 again.
7.2.3.6 Remove the Snyder column and evaporative flask. With a
clean pair of forceps, add two new Teflon® boiling chips to the concentrator
tube. Attach a two-ball micro Snyder column to the concentrator tube.
Prewet the Snyder column with about 0.5 mL of methylene chloride. Place
the K-D apparatus on the hot water bath so that the concentrator tube is
partially immersed in hot water, supporting the tube with a clamp. When the
apparent volume of the liquid reaches 4-5 mL, remove the K-D apparatus from
the water bath and allow the apparatus to cool and drain for at least 10
minutes. If the volume is greater than 5 mL, add a new boiling chip to the
concentrator tube, prewet the Snyder column, and concentrate again on the hot
water bath. Transfer the extract to a calibrated vial or centrifuge tube, rinse
concentrator tube with a minimum volume of methylene chloride and add
rinses to the vial, and add methylene chloride, if necessary, to attain a final
volume of 5 mL.
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METHOD 3542
Alternatively, the final concentration may be performed by blowing the
surface of the solvent with a gentle stream of nitrogen using a glass disposable
pipet to direct the stream of nitrogen. When the nitrogen blowdown technique
is used, care must be taken to carefully rinse the sides of the vessel using a
minimum quantity of methylene chloride to ensure that analytes are in the
methylene chloride solution, not deposited on the sides of the glass container.
Perform the blowdown procedure in a calibrated via] or centrifuge tube which
does not contain boiling chips. The final extract volume must be 5 mL.
7.2.3.7 Transfer the extract to a 10-mL glass storage vial with a
Teflon®-lined screw cap. Label the extract as Front Half Rinse and Particulate
Filter, and store at 4°C until analysis (Section 7.3 and following Sections,
Method 8270). Mark the liquid level on the vial to monitor solvent
evaporation during storage.
7,3 Condensate and Condensate Rinse. The Condensate is identified as
Container No. 4 in Method 0010; the Condensate Rinse is Container No. 5.
7.3.1 Transfer the contents of both the Condensate and the Condensate Rinse
samples to a clean separatory funnel (expected volume of both containers is
approximately 500 mL). Rinse each of the sample containers with three aliquots of
methylene chloride (approximately 10 mL each), transferring the rinses to the
separatory funnel.
7.3.2 Using a clean syringe or volumetric pipet, add a 1-mL aliquot of the
surrogate standard (Section 5.9) to the liquid in the separatory funnel. If isotopically-
labeled analogs are being used, the isotopically-labeled analog solution (Section 5.11)
should be added to the separatory funnel.
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METHOD 3542
7.3.3 Perform an initial methylene chloride extraction of the combined
Condensate/Condensate Rinse which has been spiked with appropriate spiking
solution(s). Add water as needed to ensure separation of phases. After the initial
methylene chloride extraction, check the pH of the Condensate/Condensate Rinse
solution with wide-range pH paper. If the solution is acidic (pH < 7), add acid until
the pH is < 2 but > 0 and perform another methylene chloride extraction. Then
make the Condensate/Condensate Rinse solution basic (pH >11 but < 14) and
perform another methylene chloride extraction. Combine methylene chloride extracts,
remove moisture, and concentrate for analysis. If, after the initial methylene chloride
extraction, the Condensate/Condensate Rinse solution is basic, increase pH until the
pH is > 11 but < 14, and perform another methylene chloride extraction. Then
make the Condensate/Condensate Rinse solution acidic (pH < 2 but > 0) and
perform another methylene chloride extraction. Combine the methylene chloride
extracts, remove moisture, and concentrate the extract for analysis. Refer to
Section 7.2.2.2 and following sections for extraction and concentration of the
Condensate/Condensate Rinse extract.
7.4 XAD-2®
The sorbent trap section of the organic module is identified as Container No. 3 in
Method 0010. The sorbent trap section of the organic module shall be used as a sample
transport container.
7.4.1 Using clean forceps, place about 10 Teflon® boiling chips in the bottom
of the round bottom flask of the Soxhlet extractor and connect the Soxhlet extractor to
the round bottom flask.
7.4.2 Transfer the XAD-2® to the extraction thimble. Remove the glass wool
plug from the XAD-2® trap and add to the thimble of the Soxhlet extractor. If
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METHOD 3542
ground glass stoppers are used to seal the sorbent trap during shipment, these ground
glass stoppers should be rinsed with methylene chloride and the rinsate added to the
round bottom flask of the Soxhlet extractor. If the XAD-2® is dry (i.e., free-
flowing), pour the XAD-2® directly into the thimble (or directly into the Soxhlet
extractor) and rinse the trap with methylene chloride, adding the rinses to the round
bottom flask. If the XAD-2® is wet, removal from the trap may be difficult. To
accomplish the transfer, flush the resin from the trap using a Teflon® wash bottle
containing methylene chloride. Alternatively, acidic water (pH < 2) can be used to
wash the walls of the XAD-2® trap. Collect the resin and solvent in a clean 500-mL
beaker. Transfer the XAD-2®/methylene chloride from the beaker to the extraction
thimble, taking care that no solvent is lost. Alternatively, the XAD-2® can be
transferred directly to the Soxhlet extractor and the methylene chloride rinse and
transfer solvent allowed to drain through the XAD-2® to the round bottom flask.
Rinse the beaker several times with methylene chloride, pouring the rinses through
the XAD-2® bed once the extraction thimble is in the Soxhlet extractor. Be sure that
a glass wool plug is in place above the XAD-2® to ensure that the XAD-2® does not
float out of the thimble.
NOTE: Under no circumstances should methanol or acetone be used to
transfer the resin.
Alternative approaches to transfer of XAD-2® from the trap to the extraction
thimble are discussed below.
The wet XAD-2® may be transferred from the sampling module to a piece of
cleaned aluminum foil by inverting the trap (glass frit up) and tapping the trap on a
solid surface covered with the cleaned aluminum foil. This process is slow and may
result in breakage of the sampling module. If ground glass stoppers are used to seal
the sorbent trap during shipment, these ground glass stoppers should be rinsed with
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METHOD 3542
methylene chloride and the rinsate added to the round bottom flask of the Soxhlet
extractor. After the majority of the XAD-2® has been removed from the trap by
tapping, the XAD-2® on the aluminum foil may be transferred to the extraction
thimble. The sampling module should be rinsed with methylene chloride to flush the
remaining XAD-2® particles adhering to the glass wall into the extraction thimble.
After all XAD-2® has been transferred into the Soxhlet thimble, add a plug of glass
wool to the top of the XAD-2® to hold the resin in place.
Alternatively, the XAD-2® can be transferred directly to the Soxhlet extractor
and the methylene chloride rinse and transfer solvent allowed to drain through the
XAD-2® to the round bottom flask. If ground glass stoppers are used to seal the
sorbent trap during shipment, these ground glass stoppers should be rinsed with
methylene chloride and the rinsate added to the round bottom flask of the Soxhlet
extractor. To remove the XAD-2® from the sampling module, remove the glass wool
from the end of the XAD-2® sampling module. Place this glass wool in the Soxhlet
extractor to ensure thorough extraction of the glass wool. If the XAD-® is being
transferred directly to the Soxhlet extractor, place a small piece of pre-cleaned glass
wool in the side-arm of the Soxhlet extractor to ensure that no XAD-2® enters the
side-arm of the Soxhlet extractor. Invert the XAD-2® sampling module (glass frit up)
over an extraction thimble contained in a beaker, or directly over the Soxhlet
extractor with pre-cleaned glass wool in the bottom, as shown in Figure 7-1. Add
approximately 5 to 10 mL of methylene chloride above the glass frit of the sampling
module. Connect a rubber pipet filler bulb with check valve that has been fitted with
a ball joint to the XAD-2® sampling module. Using air pressure created by squeezing
the bulb, gently but firmly push the methylene chloride through the frit, forcing the
XAD-2® out of the sampling module. Avoid allowing methylene chloride to be pulled
up into the bulb, since the sample will be compromised if methylene chloride is pulled
up into the bulb and allowed to become part of the extract. This process will need to
be repeated 3 to 5 times. Use a Teflon® wash bottle containing methylene chloride to
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METHOD 3542
Rubber
Buib
M*CI2h addad to XAD-2® Trap
Gloss
Frit
XAD-2®
Tsflon®
Tub*
SovirsI®
Fitting
Ground Glasi
Ball Joint
~
O
Glass Wool
Soxhlst
Prsclaansd
Glass
Wool
Round
Bottom
Flask
Figure 7-1. Transfer of Wet XAD-2®.
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METHOD 3542
rinse the walls of the sampling module to transfer XAD-2® which has been retained
on the walls of the sampling module after transfer of XAD-2® to the Soxhlet. A
methylene chloride rinse of the walls will not remove all of the XAD-2®, but after 3
to 5 rinses of the walls of the sampling module, no more than a monolayer of
XAD-2® particles should be retained. If more than a monolayer of XAD-2® remains,
additional rinses are required,
NOTE: Under no conditions should methanol or acetone be used in the
transfer of the XAD-2®.
7.4.3 With the XAD-2® in the Soxhlet extractor and glass wool on top of the
XAD-2®, use a clean syringe or volumetric pipet to add a 1-mL aliquot of the
surrogate standard spiking solution to the XAD-2®. Be sure that the needle of the
syringe penetrates the XAD-2® bed to a depth of at least 0.5 in. If isotopically-
labeled standard solution or method spike solution is being used, these solutions
should be spiked at this time.
7.4.4 Container No. 5 contains the methylene chloride/methanol rinse of the
condenser and all train components from the back half of the filter holder to the
XAD-2® sampling module. These rinses consist of 50:50 methanol:methylene
chloride. Transfer the contents of Container No. 5 to a separatory funnel and rinse
the Container with three 10 mL aliquots of methylene chloride. Add the rinses to the
separatory funnel. Sufficient reagent water must be added to the separatory funnel to
cause the organic and aqueous phases to separate into two distinct layers. Refer to
Section 7.2.2.2 and following sections for preparation of a methylene chloride extract
from Container No. 5. Add the methylene chloride layer from the separatory funnel
directly to the Soxhlet extractor containing the XAD-2® or collect the methylene
chloride extract in a container and transfer from this container to the Soxhlet
containing the XAD-2®. Pour the methylene chloride extract of the Condenser and
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METHOD 3542
Back Half Rinses through the XAD-2® in the Soxhlet extractor; rinse the container or
separator^ funnel 3 times with approximately 10 mL aliquots of methylene chloride
and add the rinses to the Soxhlet.
7.4.4 Add additional methylene chloride to the Soxhlet extractor, if
necessary, pouring approximately 300-400 mL through the XAD-2® bed so that the
round bottom flask is approximately half-full and the XAD-2® bed is covered.
7.4.5 Place a heating mantle under the round bottom flask and connect the
upper joint of the Soxhlet extractor to a condenser.
NOTE: Start the extraction process immediately after spiking is
completed to ensure that no volatilization of organic compounds
from the resin or any spiking solutions occurs before the
extraction process is started.
7.4.6 Allow the sample to extract for at least 18 hours but not more than 24
hours, cycling once every 25-30 minutes.
NOTE: Be sure that cooling water for the condensers is cold and
circulating. Watch the extractor through two or three cycles to
ensure that the extractor is working properly.
7.4.7 After the Soxhlet extractor has been cooled, disconnect the extractor
from the condenser and tilt the extractor slightly until the remaining solvent in the
Soxhlet has drained into the round bottom flask.
7.4.8 Inspect the contents of the round bottom flask to determine whether
there is a visible water layer on top of the methylene chloride. If no water layer is
observed, transfer the extract into a 500-mL amber glass bottle with Teflon®-lined
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METHOD 3542
screw cap for storage (Section 7.2.1.8), or proceed directly with removal of moisture
and concentration of the extract (Section 7.2.3.1). If a water layer is observed in the
Soxhlet round bottom flask, transfer the contents to a separatory funnel, rinsing the
round bottom flask three times with methylene chloride and adding the rinsings to the
separatory funnel. Drain the methylene chloride from the separatory funnel and store
in an amber glass bottle. Then perform an acid/base extraction of the water layer
remaining in the separatory funnel (Section 7.3.3). Add the methylene chloride
extract from the acid/base extraction to the methylene chloride extract from the round
bottom flask in the amber glass jar. Store the extract in the amber glass bottle at 4°C
for subsequent removal of moisture and concentration following the steps outlined in
Section 7.2.3.1.
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METHOD 3542
8.0 QUALITY CONTOOL
8.1 A method blank consists of a clean filter, clean dry XAD-2®, or reagent water,
which is spiked with surrogate standards prior to extraction. The method blank is extracted
and concentrated using the same procedures as the corresponding sample matrix. One
method blank is extracted and analyzed for every ten samples.
8.2 A method spike consists of a clean filter, XAD-2®, or reagent water, which is
spiked with surrogate standards, isotopically-labeled standards if used, and method spike
solution (if used) prior to extraction. The method spike is extracted and concentrated using
the same procedures as the corresponding sample matrix. At least one method spike is
extracted and analyzed for every matrix, with a frequency of one method spike for every
twenty samples.
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METHOD 3542
9.0 METHOD PERFORMANCE
9.1 Method Performance Evaluation. Evaluation of analytical procedures for a
selected series of compounds must include the sample preparation procedures and each
associated analytical determination. The analytical procedures should be challenged by the
test compounds spiked at appropriate levels and carried through all the procedures.
9.2 Method Detection Limits. The overall method detection limits (lower and
upper) must be determined on a compound-by-compound basis because different compounds
may exhibit different collection, retention, and extraction efficiencies as well as instrument
minimum detection limit. The method detection limit must be quoted relative to a given
sample volume. The upper limits for the method must be determined relative to compound
retention volumes (breakthrough).
9.3 Method Precision and Bias. The overall method precision and bias must be
determined on a compound-by-compound basis at a given concentration level. The method
precision value would include a combined variability due to sampling, sample preparation,
and instrumental analysis. The method bias would be dependent upon the collection,
retention, and extraction efficiency of the train components. The surrogate recoveries
shown below represent mean recoveries for surrogates in all Method 0010 matrices in a field
dynamic spiking study.
Compound
Mean
Recovery
Standard
Deviation
Relative Standard
Deviation
Percent
2-fluorophenol
phenol-d5
nitrobenzene-dj
2-fluorobiphenyl
2,4,6-tribromophenol
terphenyl-dl4
74.6
77.8
65.6
75.9
67.0
78.6
28.6
27.7
32.5
30.3
34.0
32.4
38.3
35.6
49.6
39.9
50.7
41.3
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METHOD 3542
10.0 REFERENCES
1. Bursey, J., Homolya, J., McAllister, R.» and McGaughey, J., Laboratory and Field
Evaluation of the SemiVOST Method, Vols. 1 and 2, U. S. Environmental Protection
Agency, EPA/600/4-851/075A, 075B. 1985.
2. Test Methods for Evaluating Solid Waste. Physical/Chemical Methods, SW-846
Manual, 3rd ed., Document No. 955-001-0000001. Available from the
Superintendent of Documents, U. S. Government Printing Office, Washington, DC.
November, 1986.
3. Handbook. Quality Assurance/Quality Control (QA/QC) Procedures for Hazardous
Waste Incineration, EPA-625/6-89-023, Cincinnati, OH. 1990.
4. Laboratory Validation of VOST and SemiVOST for Halogenated Hydrocarbons from
the Clean Air Act Amendments List, EPA 600/R-93/123, July. 1993.
5. Field Test of a Generic Method for Halogenated Hydrocarbons, EPA 600/R-93/101.
July, 1993.
3542 -35-
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TECHNICAL REPORT DATA
1. REP"'-!T HQ.
EPA/600/R-96/036
2.
PB37-118533
HIIIIIIIMII
A. TITLE AND SUBTITLE
Guidance for Total Organics
5.REPORT DATE
6.PERFORMING ORGANIZATION CODE
-1. AUTHOR(S!
Robert F. Martz, Easter A. Coppedge,
Larry D. Johnson
B.PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
P.O. Box 13000
Research Triangle Park, NC 27709
10.PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
6B-D4-0022
12. SPONSORING AGENCY NAME AND ADDRESS
National Exposure Research Laboratory
Office Of Research and Development
U. S. Environmental Protection Agency
Research Triangle Park, NC 27711
13.TYPE OF REPORT AND PERIOD COVERED
Published Report
14. SPONSORING AGENCY CODE
IS. SUPPLEMENTARY NOTES
16. ABSTRACT
This document provides guidance to those wishing to determine the total
organics content of source samples. Writers of air quality permit applications for
waste combustion units require total organics data for their assessments. This
document identifies specific techniques to determine the total organics sampled from
stationary sources. It describes the measurement of total organics from stack
emissions and related- field sampling efforts, combining the organics from three
specific boiling point/vapor pressure classes: light hydrocarbons and volatile
organics (boiling points <100°C), semivolatile organics (boiling points 100°C to
300°C), and non-volatile organic compounds (boiling points >300°C) . It describes
methods for measuring and reporting the individual parameters. The document seeks
to avoid the confusion about organics measurement and eliminate the misleading and
non-descriptive titles often given to different facets of organics analysis. It
also provides information about combining the component parts of the organics
analysis results into a helpful description of the data. Knowing the amount of
previously uncharacterized organic material enables more accurate risk assessment
estimates to be made. Discussions of the specific methods and operating procedures
are found in the appendices and references.
n. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/ OPEN ENDED
TERMS
C.COSAT1
— .. , ... .j .
10. DISTRIBUTION STATEMENT
19. SECURITY CLASS (This
Report}
UNCLASSIFIED
21.NO. OF PAGES
223
20. SECURITY CLASS (This
Page J
UNCLASSIFIED
22. PRICE
224
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