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O , , 5w 5w Lx S{ V X X X X Y Z e e d c b b az `v _t \s Yp \m `h bb cZ aT \P UO LO ,W 5W MX RZ V^ Xc Yh Xl Vn Qo Ko 5W 5----$ O hX hX X X O O h----:8 O x x v r k c [ U P O O W W X Z ^ c h m o p p W ----$D$$Y (Z@jx'gHVhC0 $-l4U8<9X&Y$$----$D<<Ul%2@Pc y0CVgx"Dh 5a S $$S"c7 lHp&_N;(kXH:/&jS<<----$Df$f$ghkoSu {a5 hD""4GZnycP@2% #<<% &/:HXkvbO<*&Hl 7c"ySurqp$p$----$D<9<9#8 4-$ nZG4"hH'j@{Zu(okhgYf$p$qYruy&X>h#D*b<Obv# *%.L7j8hBNA3HVl6n{q(jkebb;cgm vN>q7Z**44~4----$A3J_ueC xK yT2u_J32{Tpyg`ZWVKWxZ`gp{Ce3----L$$KKx EgxaK 3 3I]rcA x K K----L$$33Kax0Rx K K zV4r]I33----L$$QKQKRU[bkxvR0334Vuzle_\[K[K----L$$3 3  gvEkb[URxQK[K\x_eluAc33----$ 0/R/R998998----$GmFFw"Z|icYK@;8300c39BAN]o\ \Fr08j>b${`eSD8C/)&c&).69AO_arV>qe@----$RRRR--  ` `  hh#(-pp2`(#=EPA/600/R96/033 `(#BMarch, 1996 #4 PP#5  Guidance for Total Organics ă ! Final Report #Xt4 PGXP# <) By: N$Robert F. Martz #Radian Corporation P$P.O. Box 13000 M Research Triangle Park, North Carolina 27709  Contract Number 68D40022 !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 M Research Triangle Park, North Carolina 27711 *     #4 PP#& Disclaimer ă #Xt4 PGXP# The information in this document has been funded wholly or in part by the United States Environmental Protection Agency under EPA Contract 68D40022 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. #4 PP#:& Abstract ă #Xt4 PGXP# 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 <100C), semivolatile organics (boiling points 100C to 300C), and nonvolatile organics (boiling points >300C). 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 nondescriptive 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. #4 PP#-& Contents ă #Xt4 PGXP#    Disclaimerp|"(#I ii  Abstractp"(#Iiii  Acknowledgmentsp"(#H vii Glossary of Termsp"(#Hviii  1` ` ` Introduction/BackgroundpL"(#I 1  2` ` ` Method for Total Organics MeasurementpL"(#I 4  3` ` ` Field Gas Chromatography (Field GC) Method and Purge and Trap GC MethodpL"(#I 6  4` ` ` Source Sampling and Sample Extract Preparation for TCO and GRAVp!(#H 10  5` ` ` Total Chromatographic Organic (TCO) Methodp$"(#H 12  6` ` ` Gravimetric (GRAV) Methodp$"(#H 14 XX Referencesp$"(#H 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 #4 P P# ! Contents, Continued ă #Xt4 P GXP# E.` ` ` EPA Draft Method 0040 Sampling of Principal Organic Hazardous Constituents from Combustion Sources Using Tedlar Bags F.` ` ` SW846, Method 0010 Modified Method 5 Sampling Train G.` ` ` Method 3542 Extraction of Semivolatile Analytes Collected Using the Modified Method 5 (Method 0010) Train #4 P P#;$ List of Tables ă #Xt4 P GXP#  &  1` ` ` Total Organics ComponentspL"(#I 5 $#4 P P# List of Figures#Xt4 PGXP# ă  %  1` ` ` Stationary Source EmissionspL"(#I 3 #4 PP#[" Acknowledgments ă #Xt4 PGXP# This document was prepared for the US Environmental Protection Agency's National Exposure Research Laboratory (NERL) located in the Research Triangle Park, NC. The authors wish to thank those people who have made this work possible: Joan T. Bursey and Raymond G. Merrill of Radian Corporation, and Larry D. Johnson of EPA. ,#4 PP# Acronyms and Abbreviations ă #Xt4 PGXP# AREAL Atmospheric Research and Exposure Assessment Laboratory, RTP AEERL Air and Energy Engineering Research Laboratory, RTP CH4  Methane C7 Heptane C17 Heptadecane Draft Method 0040 "Sampling of Principal Organic Hazardous Constituents from  FCombustion Sources Using Tedlar Bags" Draft Method 3542 "Extraction of Semivolatile Analytes Collected Using Modified Method 5 (Method 0010) Train" EPA Environmental Protection Agency FID Flame ionization detector Field GC ` ` Field gas chromatography, light organics collected in Tedlar bags and  Fanalyzed in the field by GC/FID GC Gas chromatograph GRAV Gravimetric mass, nonvolatile organics with boiling point > 300$C heptane Straight chain hydrocarbon, saturated, 7 carbon atoms heptadecane Straight chain hydrocarbon, saturated, 17 carbon atoms Level 1 ĩ IERL (AEERL) Procedures Manual: Level 1 Environmental Assessment m Meter Method 8270 "SW846, Method 8270, Gas Chromatography/Mass Spectrometry for  FSemivolatile Organics: Capillary Column Technique" #4 PP#  Acronyms and Abbreviations, Continued ă #Xt4 PGXP# Method 0010 "SW846, Method 0010, Modified Method 5 Sampling Train" mL Milliliter g Microgram L Microliter m3  Cubic meter MS Mass spectrometry purge and trap Analytical technique where the water sample is introduced to the  Finstrument by gas purging, trapping of the gas, and desorption from the trap QC Quality control RCRA Resource Conservation and Recovery Act Recoverable organics Those organic compounds capable of being collected in a  Fspecific sampling train (Method 0010, Draft Method 0040) and 7subsequently xxAanalyzed. RTP Research Triangle Park, North Carolina semivolatile Compound class between the volatile and non volatile compounds,  Fgenerally defined by boiling point between 100$C and 300$C. SW846 Test Methods for Evaluating Solid Waste, Physical/Chemical Methods, SW846 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 chromatographable organics volatiles Volatile organic compounds with boiling points < 100$C   ӊ #4 PP#%& Section 1 Introduction/Background ă #Xt4 PGXP# 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.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.,A2.Johnson, Larry D., M. Rodney Midgett, Ruby H. James, Michael M. Thomason, and M. Lisa Manier. Screening Approach for Principal Organic Hazardous Constituents and Products of Incomplete Combustion. Journal of Air & Waste Management Association. Vol. 39, No. 5, May 1989.A The 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. 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. 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, semivolatile organics, and nonvolatile organic compounds. The total organics measurements are not merely a mass measurement of carbon, soot, or particulate content alone. Total organics in this case combines the low boiling point organic compounds (Field GC and Purge & Trap GC) with the organic compounds with boiling points greater than heptane (TCO and GRAV) collected with a Method 0010 sampling train. 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. The sampling and analytical information necessary to characterize the full boiling point range of organic material encountered in source emissions is provided in this document. 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 (GRAV) techniques are appropriate for compounds boiling at 300$C or higher. The total organics are the sum of volatile organic compounds (VOC), TCO, and GRAV. The summary of these three techniques is shown in Figure 1. Total organic carbon in this document refers to the volatile organics (boiling point < 100$C) from a field GC and purge and trap GC measurement combined with organics of boiling point > 100$C collected in a Method0010 sampling train. The combination of two sampling and three analytical techniques gives the investigator the approximate mass of all identified and unidentified "recoverable" organic material. The mass of organic material that remains after correction for the identified organic compounds found using RCRA SW846 methods is the residual organic carbon and this quantity is used to estimate risk from unidentified organic emissions. A description of the measurement techniques is found in the following pages. Detailed discussions of methods and operating procedures are found in the references and appendices of this document. #%*0 x7%# Figure 1  Figure 1 y#< a3'ddfigure1.wmfrs\awma-< y#Xt4 PGXP#  #4 PP#%& Section 2 Method for Total Organics Measurement ă #Xt4 PGXP# The method for total organics measurement incorporates three distinct sets of analyses, described in the following sections: "` ` ` First, the light organics are collected and measured by a technique known as Field GC using bag sampling according to Draft Method 0040. Emphasis is made on the identification of methane, because methane may appear in significant quantities in stack sampling efforts and correct identification may be vital to subsequent analysis of risk assessment of the stationary source. In addition, the light organics collected in the condensate trap of Draft Method 0040 are analyzed by Purge and Trap GC/FID. "` ` ` Second, Method 0010 samples are collected and the extracts of the train components are analyzed. The 100$C to 300$C organic compounds, TCO, are determined by GC/FID of the dichloromethane extracts of the pooled components of the sampling train. C7 and C17 are used as marker compounds because their boiling points are 98$C and 302$C, respectively. "` ` ` Finally, the 300$C and higher boiling organics, nonvolatile organics, are determined by a gravimetric procedure known as GRAV from the same pooled dichloromethane extract of the train components as the TCO procedure. The data from these three analytical determinations are collected and added to obtain a total organics value for the sample of choice, as shown in Table 1. The value provides a benchmark of total organic content for specific identification of individual compounds, necessary for emission and/or risk assessment calculations. The total value is then comparable from site to site or application to application, and the enduser or researcher can more easily compare total organics data from various sources.The three analysis components allow the reviewer of the data to keep track of the total organics in a material balance manner. The individual boiling point ranges allow identification of organic compounds by defined classes and assist in the estimate of completeness of characterization. This identification of known vs. unidentified organics is of benefit in subsequent risk assessment calculations.   HH  & Table 1. Total Organics Components &  r ddxe'  ddxe' r &@ AA @ @ P@ AA @ @ P& ComponentMethod Units Boiling Point Range Vapor Pressure&@ @ @@@P@ @ @@@P&SamplingAnalysis&c c &Field GC, volatile organics0040GC/FID and Purge & Trap GC/FID g/m3 < 100$C> 40 mm at 22.3$C (> heptane)&, , &TCO, semivolatile organics0010GC/FIDg/m3 100$ C < BP < 300$C1 mm Hg at 115$C > VP > 40 mm at 22.3$C&C C &GRAV, non-volatile organics0010gravimetricg/m3> 300$C< 1 mm Hg at 115$C (< heptadecane)&&Total Organics = (Field GC + Purge and trap GC) + TCO + GRAV in units of g/m3   HH  #4 PP#%& Section 3 Field Gas Chromatography (Field GC) Method and OPurge and Trap GC Method ă #Xt4 PGXP# The field GC portion of total organics is determined by field analysis of a bag sample by GC with a flame ionization detector (FID). This procedure is described in this document as Appendix A and in EPA Draft Method 0040 (Appendix E). The identified range of organics for field GC is defined by boiling point range, in this case < 100$ 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 bag sampling 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$C are sampled into Tedlar bags and require on site gas chromatographic analysis of the collected sample. The operating procedure for this methodology is included in this document as Appendix A and Draft Method 0040. The range of applicable compounds is very large: methane has a boiling point of 160$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 1520 minutes. Some investigators prefer the use of two gas chromatographs, one with an appropriate column and conditions for C1 C4 and the second with an appropriate column and conditions for the C4 C6 range. A capillary column is required to perform the analysis over the entire volatility range with adequate resolution. A capillary column with a length of 60 m may be required to provide adequate resolution for the C2ĩhydrocarbon isomers. The gas chromatographic analysis will primarily be separating compounds on the basis of boiling points, but the separation will also be influenced by the polarity of the compounds in some cases. 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 required 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 nĩalkanes from C1 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 C1 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 nĩalkanes. In many, if not most, cases the species present are not identical to those used for calibration of the onsite 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 into the condensate ahead of the Tedlar bag. The operating procedure for this methodology is included in this document as Appendix B. This condensate requires purge and trap gas chromatographic analysis of the collected water sample. 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 required to provide adequate resolution for smaller organic and hydrocarbon isomers. A flame ionization detector is required 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 nĩalkanes from C5 through C7. A multipoint calibration of at least three points (in duplicate) is required. 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 full calibration, sample analysis is initiated when an aliquot of the water sample in the VOA vial is transferred to the purge flask. The purge gas is actuated, purging the vapor with an inert gas to the sorbent trap (VOCOL, VOCARB, or equivalent). When the sample is sufficiently 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. Uniform FID response for varying compound classes is assumed in this methodology. Compounds found with retention times prior to the C4 retention time are quantified with an appropriate response factor and the value reported as C4 with the other organic results.  #4 PP#%& Section 4  Source Sampling and Sample Extract Preparation for TCO and GRAV ă #Xt4 PGXP# 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 AppendixF. 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 "brokendown" 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) XAD2 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, isotopicallylabeled standards, or internal standards associated with GC/MS analysis (Method8270) should be added to the extractors or sample extracts. After the sampling train is disassembled, the components are rinsed and extracted normally, but without the addition of surrogate compounds. "` ` ` The final pooled extract sample volume is recorded and an aliquot is used for the TCO GC/FID, while duplicate aliquots are used in the GRAV measurements. #4 PP#%& Section 5 z Total Chromatographic Organic (TCO) Method ă #Xt4 P GXP# The TCO Method has been described in detail in the Level 1 Procedures ManualXÍXÍЍ.IERLRTP Procedures Manual: Level 1 Environmental Assessment (Second Edition). U.S. Environmental Protection Agency. EPA600/778201. October 1978. 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 100300C. 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 n-heptane (C7) and nĩheptadecane (C17) as the reference peaks between which the TCO integration will occur. As described in the method, heptane and heptadecane are used as retention time reference peaks for boiling point. The TCO value is determined from the calibration standard curve, generated with hydrocarbon standards which fall within the TCO range, specifically decane (C10), dodecane (C12), and tetradecane (C14). 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 g per sample, which is then converted to g/m3, based on the sampling volume. Analysis may be performed using a capillary (preferred) or packed column GC. A nonpolar 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 nonpolar wide bore column (0.32mm) has been found to be effective for TCO analysis. As a capillary or packed column procedure, the GC/FID is operated in 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 GC used for TCO analysis is calibrated using specific hydrocarbon standards. 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 run to verify that the GC is performing correctly. The QC check sample is run 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 allpurpose detector for the quantification of the sample extracts.  #4 P!P#%& Section 6 Gravimetric (GRAV) Method ă #Xt4 P"GXP# 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 is a gravimetric mass measurement of the nonvolatile (boiling point >300$C) organics found in the extract of the sampling train, which was established for the Level 1 procedures by an exhaustive study of hydrocarbon evaporative properties. The range of organics is defined by boiling point, in this case greater than 300$C. The analysis is generally performed in the laboratory after extraction and compositing of the extracts of the individual components of the Method 0010 sampling train. GRAV Method The GRAV Method, in its current form, quantifies nonvolatile organic material with a boiling point greater than 300$C. A carefully measured aliquot of the Method 0010 dichloromethane extract is placed in a precleaned 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 1mL 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 Method3542 (Appendix G) should be followed closely to avoid loss of more volatile organics. The GRAV organics in the greater than 300$C range are measured on an analytical balance and recorded for the GRAV portion of the total organics number. This value, in g, is converted to units of g per sample, which is then divided by sample volume to obtain g/m3. This sum is added to the previously determined TCO and field GC values to find the total organics value, in units of micrograms per m3.  #4 P#P#%& Section 7 %References ă #Xt4 P$GXP#  #4 %G#цAppendix A Recommended Operating Procedure for Field Gas Chromatography (From SW846, Method 8240 and Method 18 40 CFR Part 60, Appendix A)     @A-@3 RECOMMENDED OPERATING PROCEDURE FOR FIELD GAS CHROMATOGRAPHY #Xt4 P&GXP# A.1.0INTRODUCTION 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 C1 C7 hydrocarbon range. This range encompasses alkanes, alkenes, cyclic compounds, and functionalized organic compounds. For example, methane, chloromethane, formaldehyde, and methanol are all C1 compounds. The methodology is applicable to C1 C7 hydrocarbons, organic compounds boiling in the range 160$C to 100$C. When performing field gas chromatographic analysis, species eluting in the specified boiling point range are quantified as nĩalkanes. The sensitivity of the flame ionization detector varies from compound to compound, but nĩalkanes as a class have a higher flame ionization response than other classes of compounds such as oxygenated or halogenated hydrocarbons. Therefore, using nĩalkanes 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 nonalkane peak have equivalent system responses, the nonalkane peak is assigned a quantitative value equivalent to the alkane. The nonalkane peak, however, has a poorer response to the flame ionization detector than the alkane. The amount of nonalkane 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. A.2.0SCOPE AND APPLICATION This procedure defines the field gas chromatographic analysis of gaseous stationary source emissions sampled into a Tedlar bag for C1 C7 hydrocarbons, a chromatographic elution range defining organic compounds boiling in the range of -160$C to 100$C. A.3.0SUMMARY 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 C1 C7 nĩalkanes. Retention times are determined and calibration is performed with a certified gaseous standard of C1 C7 alkanes in air or nitrogen. Compounds of interest are identified by retention times or retention time ranges and quantitative analysis is performed. A.4.0SAMPLE 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.5.0APPARATUS 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, temperaturecontrolled sample loops of varying sizes with a valve assembly, temperatureprogrammable 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 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, upslope sensitivity, downslope sensitivity, baseline reset delay, area threshold, front shoulder control, rear shoulder control, and data sampling frequency. A.5.3 ` ` Columns For the C1 C4 hydrocarbons, a packed stainless steel SP1000 column (6 ft x 1/8inch outer diameter), or equivalent which can be calibrated over the specified hydrocarbon 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 C7 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 C7 range and a flame ionization detector. A.5.4 ` ` Gas Standard A certified nĩalkane gas standard of C1 C7 nĩalkanes 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. 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.7.0CALIBRATION ČTo determine the temperature ranges for reporting the results of GC analyses for the C1Ġ C7 compounds, the gas chromatograph is given a normal boiling point retention time calibration. The nĩalkanes, their boiling points, and the data reporting ranges are shown below.  ^ dd< """ dd< """^ >@ @ @ P>@ @ @ PCompoundBoiling Point, $CReporting Range, $CReport As5 5 methaneܩ161ܩ160 to 100C15 5 ethaneܩ88ܩ100 to 50C25 5 propaneܩ42ܩ50 to 0C35 5 butane00 to 30C45 5 pentane3630 to 60C55 5 hexane6960 to 90C6e   e   heptane9890 to 98C7 To perform a multipoint calibration, connect the C1 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. 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.8.0DAILY CALIBRATION CHECK The C1 C7 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. 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 C1 C7 HYDROCARBONS The calibration curve for the nĩalkanes 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$C, 30$C to 60$C, 60$C to 90$C, and 90$C to 98$C. 5)` ` ` Calculate average area response and relative standard deviations for the propane calibration standard. 6)` ` ` Plot response (V/sec) as ordinate versus concentration of the standard in mg/m3 injected as abscissa. Draw in the curve. Perform least squares linear regression and obtain the slope (V/sec * m3/mg). 7)` ` ` In each retention time range of the sample, sum up the peak areas. 8)` ` ` Convert peak areas (V / sec) to mg/m3 by dividing by the proper response (slope factor). 9)` ` ` Record the total concentration of material in each retention time range. #4 'G#цAppendix B Recommended Operating Procedure for Purge and Trap Gas Chromatography With FID Detection (From SW846 Method 8240 and Draft Method 0040)     @B-@3 RECOMMENDED OPERATING PROCEDURE FOR PURGE AND TRAP GAS CHROMATOGRAPHY WITH FID DETECTION #Xt4 P(GXP# B.1.0INTRODUCTION As a complement to the Field Gas Chromatography analysis of total organics, the condenser component of the Draft Method 0040 sampling train is analyzed using purge and trap techniques and an FID detector. In determining total organics, purge and trap gas chromatography is performed to determine compounds in the C1 C7 hydrocarbon range. This range encompasses alkanes, alkenes, cyclic compounds, and functionalized organic compounds. For example, methane, chloromethane, formaldehyde, and methanol are all C1 compounds. The methodology is applicable to C1 C7 hydrocarbons, organic compounds boiling in the range 160$C to 100$C. In performing purge and trap gas chromatographic analysis, species eluting in the specified boiling point range are quantified as nĩalkanes. The sensitivity of the flame ionization detector varies from compound to compound, but nĩalkanes as a class have a higher flame ionization response than other classes of compounds such as oxygenated or halogenated hydrocarbons. B.2.0SCOPE AND APPLICATION The field gas chromatographic analysis encompasses gaseous stationary source emissions sampled into a Tedlar bag in the sampling train. Analysis is performed for the organic compounds boiling in the range of 160$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.3.0SUMMARY 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 C7 nĩalkanes. Retention times are determined and calibration is performed with a liquid standard of C5 C7 alkanes. Compounds of interest are identified by retention times or retention time ranges and quantitative analysis is performed. B.4.0SAMPLE 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.5.0APPARATUS 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.5.3  ` ` Gas Chromatograph Setup For the C1 C4 hydrocarbons, a packed stainless steel SP1000 column (6 ft x 1/8inch 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 C7 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 C7 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.5.5  ` ` Liquid Standard A set of nĩalkane liquid standards of C5 C7 nĩalkanes 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 C5 to C7. The lower boiling organic compounds (C1 to C3) 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.5.7 ` `  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, upslope sensitivity, downslope sensitivity, baseline reset delay, area threshold, front shoulder control, rear shoulder control, and data sampling frequency. B.6.0CALIBRATION To determine the temperature ranges for reporting the results of GC analyses for the C5 C7 compounds, the gas chromatograph is given a normal boiling point retention time calibration. The nĩalkanes, their boiling points, and the data reporting ranges are shown below.  ^ dd< """ dd< """^ >@ @ @ P>@ @ @ PCompoundBoiling Point, $CReporting Range, $CReport As5 5 methaneܩ161ܩ160 to 100C15 5 ethaneܩ88ܩ100 to 50C25 5 propaneܩ42ܩ50 to 0C35 5 butane00 to 30C45 5 pentane3630 to 60C55 5 hexane6960 to 90C6e   e   heptane9890 to 100C7 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 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. The 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 C7 alkanes. Prepare a plot of the concentration versus the calibration area values, perform a regression analysis, and draw the least squares line. B.7.0DAILY CALIBRATION CHECK A C5 C7 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. 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 FOR C5 C7 HYDROCARBONS The calibration curve for the nĩalkanes 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$C . 5)` ` ` Calculate average area response and relative standard deviations for the hexane calibration standard. 6)` ` ` Plot response (V/sec) as ordinate versus concentration of the standard in mg/m3 injected as abscissa. Draw in the curve. Perform least squares linear regression and obtain the slope (V/sec * m3/mg). 7)` ` ` In each retention time range of the sample, sum up the peak areas. 8)` ` ` Convert peak areas (V / sec) to mg/m3 by dividing by the proper response (slope factor). 9)` ` ` Record the total concentration of material in each retention time range.  #X*0 x)7X#  X І#*0 x*7# Appendix C Recommended Operating Procedure for Total Chromatographable Organics (TCO) Analysis #X*0 x+7X# (This document was originally prepared for the EPA/AEERL Laboratory in RTP, NC and developed and reviewed by the QA Program of AEERL, under the direction of Judith S. Ford, QA Manager of EPA/AEERL) ! TABLE OF CONTENTS Section`!(#GPage ă  C.1` ` INTRODUCTIONp"(#I 1 ` `  ` ` C.1.1 Scopep"(#I 1 ` ` C.1.2 Limitationsp"(#I 1 ` `  ` ` C.1.3 Definitionsp"(#I 2 C.2` ` ` STARTUPp"(#J3 ` ` ` ` ` C.2.1 Personnel Requirementsp"(#I 3 ` ` ` ` ` C.2.2 Facilities Requirementsp"(#I 3 ` ` ` ` ` C.2.3 Safety Requirementsp"(#I 3 ` ` ` ` ` C.2.4 Apparatusp"(#I 4 ` ` ` ` `  C.2.4.1hh#Equipment Neededp"(#I 4 ` ` ` C.2.4.2hh#Reagents and Materialsp"(#I 4 ` ` ` ` `  C.2.4.3hh#Maintenancep"(#I 4 ` ` ` ` `  C.2.4.4hh#Theory Of FID Detectorp"(#I 5 ` ` ` ` ` C.2.5 Interferencesp"(#I 5 C.3` ` ` OPERATIONp"(#J6 ` ` ` ` ` C.3.1 Summary of Methodp"(#I 6 ` ` ` ` ` C.3.2 Samples/Sampling Proceduresp"(#I 6 ` ` ` ` ` C.3.3 Operationp"(#I 8 ` ` ` ` ` C.3.4 Analysisp"(#I 9 C.4` ` ` TROUBLESHOOTINGp`"(#I10 ` ` ` ` ` C.4.1 Calibrationp!(#H 10 ` ` ` ` ` C.4.2 Method Precision and Accuracyp!(#H 11 C.5` ` ` DATA REDUCTIONp`"(#I12 ` ` C.5.1 Calculationsp!(#H 12 ` ` C.5.2 Data Reportingp!(#H 12 C.6` ` QUALITY ASSURANCE/QUALITY CONTROLp$"(#H 13 ` `  ` ` C.6.1 QC Checksp$"(#H 13 ` ` ` C.6.2 QC Controlsp$"(#H 13 C.7` ` REFERENCESp$"(#H 14 # LIST OF TABLES ă `!(#GPageă C.1Instrumental Operating Conditions for Gas Chromatography p"(#I 7 X` hp x (#%'0*,.8135@8: