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QUALITY ASSURANCE PROJECT PLAN (QAPP)
FORTHE
REMOVAL INVESTIGATION
AT THE
WHITE SWAN LAUNDRY AND CLEANERS SITE
WALL TOWNSHIP, MONMOUTH COUNTY, NEW JERSEY
Project Officer's-Signature: ^ C x ^ ^ - ^ g ^ ^ o . Date: 1
Project Officer's Name: Diane Salkie, EnvipjHsental Scientist
Project Quality Assurance Officer's Signature: ~ j ^ ~ ^ ^ J U ^ ^ ^ l M e : ^
Project Quality Assurance Officer's Name: Pat Sheridan, QA Officer
Date Prepared: December 14, 2001
TABLE OF CONTENTS
QAPP Element Page
1.0 PROJECT DESCRIPTION , 1 1.1 Project Definition/Background 1 1.2 Project/Task Description ...2
2.0 PROJECT ORGANIZATION AND RESPONSIBILITY. 3 2.1 Project/Task Organization 3 2.2 Documentation and Records 4
3.0 QA OBJECTIVES FOR MEASUREMENT DATA (PARCC) 4 3.1 Quality Objectives and Criteria for Measurement Data 4
3.1.1 Analytical and sample collection precision 5 3.1.2 Analytical and sample collection accuracy 5 3.1.3 Data representativeness 5 3.1.4 Data completeness 6 3.1.5 Data comparability 6
4.0 SAMPLING PROCEDURES 7 4.1 Sampling Process Design ; 7 4.2 Sampling Methods Requirements 8
4.2.1 Standard operating procedures 8 4.2.2 Sample collection methodology 8 4.2.3 Sample containers, volume, preservation, and holding times....! 8 4.2.4 Field measurement data collection 9 4.2.5 Sampling equipment decontamination 9 4.2.6 Management of investigative-derived wastes (IDW) 9
5.0 SAMPLE CUSTODY '. 9 5.1 Special Training Requirements or Certifications 9 5.2 Sample Handling and Custody Requirements : 10 '
5.2.1 Sample handling and shipment 10 5.2.2 Sample custody procedures 11
6.0 CALIBRATION PROCEDURES AND FREQUENCY....: 12 6.1 Instrument Calibration and Frequency :. 12
7.0 ANALYTICAL PROCEDURES 12 7.1 Analytical Methods Requirements 12
8.0 DATA REDUCTION, VALIDATION, AND REPORTING 12 8.1 Data Review, Validation, and Verification Requirements 12 8.2 Validation and Verification Methods ; 12" 8.3 Data Acquisition Requirements : 12 8.4 Data Quality Management 12
9.0 INTERNAL QUALITY CONTROL CHECKS AND FREQUENCY 14 9.1 Quality Control Requirements 14
9.1.1 Data precision 14 9.1.1.1 analytical precision ; 14 9.1.1.2 sample collection precision 14
9.1.2 Data accuracy '. 15 9.1.2.1 analytical accuracy.. 15 9.1.2.2 sample collection accuracy.: 15
9.1.3 Data representativeness 15 9.1.4 Data comparability 16 9.1.5 Data completeness 16
TABLE OF CONTENTS (Continued)
QAPP Element Page
10.0 PERFORMANCE AND SYSTEMS 16 10.1 Assessments and Response Actions '. 16
11.0 PREVENTIVE MAINTENANCE 16 11.1 • Instrument/Equipment Testing, Procedures and
Scheduled Inspection, and Maintenance Requirements 16 11.2 Inspection/Acceptance Requirements for Supplies and Consumables 17
12.0 SPECIFIC ROUTINE PROCEDURES MEASUREMENT PARAMETERS INVOLVED 17 12.1 Reconciliation with Data Used to Assess PARCC for Quality Objectives Measurement 17
13.0 CORRECTIVE ACTION 17 13.1 Assessments and Response Actions 17
14.0 QA REPORTS TO MANAGEMENT 18 14.1 Distribution List 18 14.2 Reports to Management 18
ii
LIST OF APPENDICES
Appendix A - Site Maps
Appendix B - Eastern Research Group (ERG). March 2000. Support for NMOC/SNMOC, UATMP and PAMS Networks, Contract No. 68-D-99-007. Quality Assurance Project Plan. Morrisville, North Carolina
Appendix C - U.S. Environmental Protection Agency (EPA). January 1999. Compendium Method TO-15: Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specialty-Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) from the Compendium.ofMethods for the Determination ofToxic Organic Compounds in Ambient Air. Second Edition. Center for Environmental Research Information. Office of Research and Development. Cincinnati, OH
Appendix D - U.S. EPA. July 1995. Environmental Response Team (ERT) Standard Operating Procedure (SOP) #1704: SUMMA Canister Sampling.
Appendix E - U.S. EPA. September 1994. Environmental Response Team (ERT) Standard Operating Procedure (SOP) #170: Sample Documentation.
Appendix F- ERG's Method Detection List
Appendix G - Example Questionnaire, Example Canister Field Data Sheet and Example Chain of
Appendix H - Resident Instructions
I
ii
1.0 Project Description
1.1 Problem Definition/Background
The White Swan Laundry and Cleaners site (site) encompasses three different potential responsible parties (PRPs) in three areas. They are the former White Swan Laundry and Cleaners on 1322 Sea Girt Avenue in Wall Township; the Gulf Service Station on 1324 Sea Girt Avenue in Wall Township; arid the former Sun Cleaners on 2213 Route 35 in Wall Township. However, the name of the site is White Swan Laundry and Cleaners. See Map 1 of Appendix A for a map of the site location and Map 2C for locations of the three areas of concern.
The White Swan Laundry and Cleaners, located in Block 706, lot2, began as an ice cream parlor, the Big Scoop, in 1957. The Big Scoop was sold to Mr. Harry B. (See Map 2 of Appendix A for a site location) White in 1964 who began operations of White Swan Laundry and Cleaners and continued for 18 years. Mr. White sold the business and property to Charles J. and Mary M. Mahoney in 1982. They held the business for less than one year when they sold the property to Ocean County National Bank in 1983. The bank demolished the original building and constructed a new one. The property has continued as a bank ever since and was connected to the public sewer system in 1986 when Summit Bank purchased the property. Prior to 1986, the site used a septic system for all of its discharges. The site is in a commercial/residential area. A Gulf Service Station is located to the west, a motel is located to the north and a convenience store/hair salon is to the east. Across the street to the south is a bank and a strip mall. Residential properties are located to the northeast/east. New Jersey Department of Environmental Protection (NJDEP) conducted an investigation of the property in January of 2000 and confirmed a release of PCE to the soil and groundwater. See Map 3 of Appendix for a diagram of the site.
The Gulf Service Station, located in Block 706,- lot 1, was purchased by the Gulf Oil Corporation in 1951 as an undeveloped property from Lawrence and Helen Edwards. See Map 2A of Appendix A for a site location. From 1951 until 1986, The Gulf Oil Corp. maintained ownership of the property, but leased it to several operators who distributed gas and conducted auto repairs. In 1986, the Gulf Oil Corp. was purchased by Chevron USA, Inc. and in 1986 the property was purchased and is still owned by Cumberland Farms, Inc., but operates under the Gulf Service Station name. Prior to 1986, when the property was connected to public sewer, the facility used a septic system, located in the northeast corner of the property. Currently the facility utilized four underground storage tanks for the distribution of gasoline. There is an underground waste oil tank on the northwest side and an underground fuel oil tank in the back of the building. An underground kerosene tank was removed in 1998. NJDEP personnel discovered an unregistered underground waste tank on the east side of the building. The original gasoline tanks were removed in 1984 and replaced with fiberglass tanks. NJDEP conducted an investigation of the property in 2000 and confirmed PCE in the on-site soil and groundwater. See Map 3 A of Appendix A for a diagram of the site.
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The first records of Sun Cleaners, located in block 807, lot 1, show that it began as Circle Dry Cleaning Corporation in 1960. See Map 2B of Appendix A for a site location. They operated a dry cleaning operation for 22 years. In 1982, Sun Cleaners began operating at the facility and lasted for 9 years. In 1991, the owner, Sylvia Harte, ceased all on site dry cleaning operations and only operated as a drop-off and pick-up of dry cleaning materials. The facility is a two-story building with commercial space on the first floor. The southern portion of the first floor was used as a dry cleaning drop off service and the northern section was used for the dry cleaning of clothes. Although the facility ceased operations, the equipment remains in the building. A poly tank is located on the roof above the dry cleaning section of the building. The tank reportedly held water used in dry cleaning operations. The second floor of the building consists of two apartment units which have not been occupied for years due to unsafe conditions. A septic system was in operation until the early 1980s when the facility was connected to a public sewer system. An underground storage tank is located on the south side of the property. Located at the north end of the building are: a 55-gallon drum, 30-gallon drum and a separator discharge pipe. See Map 4 of Appendix A for a diagram of the site.
NJDEP conducted several investigations in 2000 throughout the site, specifically ground water sampling. Due to high levels of PCE and TCE in the groundwater, NJDEP also sampled air in the basements of residents in the area. This investigation proved some of the homes to have PCE, TCE and benzene contamination in the vapors of the basements. The Division of Environmental Science and Assessment (DESA), Hazardous Waste Support Branch (HWSB), Superfund Contract Support Team (SCST) has been requested by the Environmental Remedial and Response Division (ERRD) to continue sampling the vapors in the basements of the residential houses in the surrounding vicinity of the site.
Project/Task Description:
The purpose of this removal assessment is to collect valid data which are necessary and efficient to verify that contaminants exist in the residential basements surrounding the site. The sampling event will also determine whether or not an immediate threat to human health or the environment exists. The scope of the removal assessment is to:
• assess the extent of contamination in the basements of residents; and
• delineate the specific organic contaminants in the vapors in the basements of residents.
All analysis of the air samples collected during this sampling event will be performed by the Eastern Research Group, Inc. (ERG). This sampling event will use the ERG contract to supply the SUMMA™ canisters and submit them to their own laboratory for analysis. A copy of the quality assurance project plan for the contract entitled Support For NMOC/ SNMOC, UATMP, and PAMS Networks, Contract No. 68-D-99-007, Quality Assurance Project Plan can be found as Appendix D. This document will be referred to as the contractor's or ERG QAPP throughout this document. According to the QAPP, the relevant program for this sampling event is the Urban Air Toxic Monitoring Program (UATMP)
The purpose and scope of this QAPP is to specify the details related to the collection, analysis and validation of the samples collected by the USEPA Region 2, DESA, HWSB, SCST from December 20, 2001 until January 20, 2002. The activity schedule is as follows:
ACTIVITY DATE
Date of the request which initiates the project. December 06, 2001
Review and Background information December 11, 2001
Date by which the project plan will be submitted to all interested parties.
December 14, 2001
Obtain site access Prearranged by ERRD
Date by which comments on the plan are to be received by the project officer.
December 19, 2001
Date(s) of the field reconnaissance, December 20, 2001
Date(s) of the field sampling activities. December 20, 2001 -January 20, 2002
Date(s) the samples will be submitted to the laboratory for analysis.
All samples will be shipped within 24 hours of collection.
Date(s) by which all analyses are to be completed and the data submitted to the project officer.
30 days.
Date(s) the data will be entered into STORET or other computerized systems.
Not applicable.
Date of the completion of the draft interim/final project report. (Sampling Trip Report)
Within one week of the end of the sampling event
Date by which the reviewer's comments on the report(s) must be received.
Not applicable.
Date for completion of the peer review process. Not applicable.
Date for the issuance of the final project report. Within two weeks of receipt of validated analytical data.
The primary use of the data collected will be to determine the extent of air contamination, evaluate potential health risks, and determine environmental impacts. The samples results will be submitted to Agency for Toxic and Disease Registry (ATSDR) who will determine whether the contamination is significant enough to cause an adverse effect on human health.
2.0 PROJECT ORGANIZATION AND RESPONSIBILITY
2.1 Project/Task Organization
The following is a list of key personnel and their corresponding responsibilities. Due to the work breakdown structure of the project, an organization list is provided instead of a concise organization chart.
PROJECT PERSONNEL RESPONSIBILITY
Diane Salkie, Project Officer DESA/HWSB Superfund Contract Support Team
Project Management/ Sampling Operations/ Field Support
Keith Glenn, Environmental Scientist DESA/HWSB Superfund Contract Support Team
Sampling Operations/ Field Support
Michael Mercado, Environmental Scientist DESA/HWSB Superfund Contract Support Team
Sampling Operations/ Field Support
Pat Sheridan, Project Quality Assurance Officer DESA/HWSB/HWSS
Report QA
ERG provided Laboratory Laboratory Analysis, Laboratory QC, Data Processing Activities, Data Quality Review
Not Applicable Performance Auditing
Not Applicable Systems Auditing
DESA/Hazardous Waste Support Branch Overall QA
Thomas Budroe, On-Scene Coordinator ERRD/RAB
Overall Project Coordination
2.2 Documentation and Records
The data collected for the sampling activities will be organized, analyzed, and summarized in a final project report that will be submitted to the OSC according to the Project Schedule. The report will be prepared by the project officer and include appropriate data quality assessment. Standard methods and references will be used as guidelines for data reduction and reporting. All SOP data generated by the laboratory will be reported in standard deliverable format.
3.0 QUALITY ASSURANCE (QA) OBJECTIVES FOR MEASUREMENT DATA (PARCC)
3.1 Quality Objectives and Criteria for Measurement Data
To assess data quality, PARCC (Precision, Accuracy, Representativeness, Completeness, and Comparability) parameters will be utilized. This is an integral part of the overall monitoring network design. Precision and accuracy are expressed in purely quantitative terms. The other parameters are only expressed using a mixture of quantitative and qualitative terms. All of these parameters are interrelated in terms of overall data quality and they may be difficult to evaluate separately due to these interrelationships. The relative significance of each of the parameters depends on the type and intended use of the data being collected. Therefore, these essential data quality elements are delineated as follows.
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3.1.1 Analytical and sample collection precision
The measure of replicate precision is the absolute value of the difference between replicate measurements of the sample divided by the average value and expressed as a percentage as follows:
Percent difference = \X{ - X,| x 100
x ; where: X, - First measurement value
X 2 - Second Measurement value X - Average of the two values
Factors that affected the precision of the measurement are: molecular weight, water solubility, polarizability, etc. A primary influence is the concentration level of the compound. A replicate precision value of 25 percent can be achieved for each of the target compounds. For more information, refer to Compendium Method TO-15: Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specialty-Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) which can be found as Appendix C.
3.1.2 Analytical and sample collection accuracy
A measurement of analytical accuracy is the degree of agreement with audit standards. It is defined as the difference between the nominal concentration of the audit compound and the measured value divided by the audit value and expressed as a percentage as follows:
Audit Accuracy, % = Spiked Value - Observed Value X 100 Spiked Value
For more information, refer to Compendium Method TO-15: Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specialty-Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) which can be found as Appendix C. As per Method TO-15, the performance criteria for audit accuracy should be within 30 percent for concentrations normally expected within contaminated ambient air.
3.1.3 Data representativeness
As previously discussed, data representativeness will be assessed by collecting field . replicate samples. The field replicates are by definition equally representative of a given point and space and time. Representativeness is a qualitative parameter which is dependent upon the proper design of the sampling program and proper laboratory protocol. Therefore, data representativeness will be satisfied by ensuring that:
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The sampling program is followed according to:
U.S. EPA (Environmental Protection Agency). October 1989. Region I I CERCLA Quality Assurance Manual. Final Copy, Revision 1. Division of Environmental Services and Assessment, Edison, NJ.; and
U.S. EPA. December 1995. Superfund Program Representative Sampling Guidance. OSWER Directive 9360.4-10: Interim Final. EPA/540/R-95/141. Office of Emergency and Remedial Response (OERR). Washington, D.C.
Proper sampling techniques are used in accordance with:
U.S. EPA. Environmental Response Team (ERT) Standard Operating Procedure (SOP) #1704: Summa Canister Sampling; revised July 1995. The SOP is enclosed in Appendix D.
Proper analytical procedures are followed and holding times of the samples are not exceeded in the laboratory according to:
U.S. EPA. January 1999. Compendium Method TO-15: Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specialty-Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) from the Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air. Second Edition. Center for Environmental Research Information. Office of Research and Development. Cincinnati, OH which can be found as Appendix C.
3.1.4 Data completeness
Data completeness will be expressed as the percentage of valid data obtained from measurement system. For data to be considered valid, it must meet all the acceptable criteria including accuracy and precision, as well as any other criteria specified by the analytical method used. Therefore, all data points critical to the sampling program in terms of completeness will be 100% validated by ERG according to Section 15 of ERG's QAPP which can be found as Appendix B. With 100% validation, the rationale for considering data points non-critical is not required.
3.1.5 Data comparability
To ensure data comparability, sampling and analysis for all samples will be performed using standardized analytical methods and adherence to the quality control procedures outlined in the methods and this QAPP. Therefore, the data will be comparable.
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4.0 SAMPLING PROCEDURES
4.1 Sampling Process Design
As part of the Removal Assessment process, U.S. EPA Region IIDESA/HWSB/SCST personnel will collect air samples in the basements of houses in the area of the White Swan Laundry and Cleaners site. Samples will be collected with SUMMA™ canisters. SUMMA™ Canister sampling will follow methods as described in U.S. EPA/ERT SOP #1704, Appendix D.
The sampling design for the site, including the rationale for sample frequency, location, and depth was predetermined by the On-Scene Coordinator (OSC). For the purposes of this sampling event, sample location selection was determined by selecting locations of in the area suspected ground water contamination. Each location to be sampled will be chosen by the OSC prior to sampling. The resident will be notified prior to the sampling day by a telephone call and an instruction page through the mail. A copy of this page can be found as Appendix H. A map of the area can be found in Appendix A. A detailed description of sample collection methodology is presented in Section 4, Sub-section 2, Part 2: Sample Collection Methodology.
A total of one hundred and seventy three (173) samples will be collected from one hundred and fifty (150) homes and eight (8) background locations. The one hundred and seventy three (173) samples also include a maximum of 10% QA/QC (field replicate samples). All samples will be analyzed for Title I I I Clean Air Amendment List - volatile organic compounds (VOC) which can be found in Appendix F. All samples will be collected by U.S. EPA personnel and then sent to ERG contractors. The contractors are providing the canisters and submitting the samples to their own laboratory who will analyze the samples according to TO-15 which can be found as Appendix B.
The sampling and analysis protocol is listed as Table 1 on page 8.
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TABLE 1 \ \ hite Swan Laundry and Cleaners Site
Removal Investigation Sampling and Analysis Protocols
Sample Type
Number of Samples
Matrix Parameter/Fraction Sample Container
; Sample Preservation
Analytical Method 1
Method Detection
Limit
Holding Time
Residential Basements
165 Air Title III Clean Air Amendment List
Volatile Organic Compounds (VOCs)
(1) SUMMA Canister
TO-15 0.04 - 0.26 ppbv
30 days
Background Samples
8 Air Title III Clean Air Amendment List
Volatile Organic Compounds (VOCs)
(1) SUMMA Canister
TO-15 0.04 - 0.26 ppbv
30 days
Legend - ' r - 1 j < ' U S : EPA. January .1999. Compendium Method TO-15: Determination.ofVolatile•OrganicCompounds(VOCs)>:.m Air Collected in Specialty-""-Prepared Canisters and Analyzed.byGas Chromatography/Mass Spectrometry(GC/MS) from the Compendium of Methods for the Determination ofcToxic OrganicCompounds in Ambient'Air. Second Fdition
4.2 Sampling Methods Requirements
4.2.1 Standard operating procedures
As previously stated, all sampling will be in accordance with the U.S. EPA Region II CERCLA Quality Assurance Manual; and U.S. EPA Superfund Program Representative Sampling Guidance OSWER Directive 9360.4-10, Interim Final, EPA/540/R-95/141, Office of Emergency and Remedial Response (OERR), Washington, D.C. Furthermore, the specific Standard Operating Procedure (SOP) utilized for air sampling, as presented in Appendix D, is the U.S. EPA ERT SOP #1704: Summa Canister Sampling.
4.2.2 Sample collection methodology
All samples including QA/QC samples will be collected by personnel from the US EPA Region IIDESA/HWSB/SCST from the residential basements in the area of the White Swan Laundry and Cleaners site. The total number of samples includes: one hundred and fifty (150) samples in addition to: up to fifteen (15) laboratory quality control samples (i.e. field duplicates) and eight (8) background samples. Samples will be collected by placing a SUMMA™ canister in the residential basement, setting the valve for the appropriate amount of time and retrieving the canister after 24 hours.
4.2.3 Sample Containers, Volume, Preservation, and Holding Times
Sample container type, volume, preservation, and holding times are dependent upon analytical parameter and fraction and are matrix specific. The following table outlines the sample container type, volume, preservation, and holding times for samples to be collected
. on-site.
8
Analytical Parameter/Fraction i ,. Sample Container . ..>:
,, Required S Sample {• 'Volume
Sample Preservation , HoldingiTime i
Clean Air Amendment List - VOC
(1) SUMMA™ canister 6 Its. 30 days to analyze
4.2.4 Field measurement data collection
A photo-ionization detector (PID) will be used for the health and safety of the samplers. Canister Sample Data Sheets, Questionnaires and the field notebook will be completed for each sample collected. The Questionnaire will record sample location; residential information; time of sample drop off and pick up; conditions in the room; laboratory sample number; laboratory sample analysis and sample collection notes and/or observations. An example of the Questionnaire is presented in Appendix G. The Canister Sample Data Sheet will be provided by ERG and records the sample location, sampling period, initial and final pressure and comments. An example of this data sheet can also be found in Appendix G. The field notebook will be completed as provided for in Section 8.4: Data Quality Management of the QAPP.
4.2.5 Sampling Equipment Decontamination
Air samples will be collected using summa canisters. ERG will perform decontamination of the canister prior to sending them to U.S. EPA. The SUMMA™ canisters will be cleaned according to:
• Support For NMOC/SNMOC, UATMP, and PAMS Networks, Contract No. 68-D-99-007, Quality Assurance Project Plan (Appendix B);
• U.S. EPA ERT SOP #1703: Sample Documentation (Appendix E); and
• U.S. EPA Region IICERCLA Quality Assurance Manual.
4.2.6 Management of Investigative-Derived Wastes (IDW)
The wastes that are anticipated on being generated during this sampling event are personnel protective equipment (i.e. goggles, booties, etc.). The personnel protective equipment will be double-bagged and properly disposed of in on-site solid waste roll-off or off-site in properly designated containers.
5.0 SAMPLE CUSTODY
5.1 Special Training Requirements/Certification
To perform the operations of this sampling event, SCST will be dealing with the removal activities on-site. This can imminently expose SCST personnel to potential occupational environmental hazards. As a result, it is important for SCST field personnel to be familiar with:
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• Identifying methods and procedures for recognizing, evaluating and controlling hazardous substances.
• Identifying concepts, principles, and guidelines to properly protect SCST field personnel.
• Discussing regulations and action levels to ensure the health and safety of SCST field oversight personnel.
• Discussing the fundamentals needed to develop organizational structures and standard operating procedures to mitigate potential environmental hazards.
• Demonstrating the selection and use of dermal and respiratory protective equipment.
• Demonstrating the selection and use of direct-reading air monitoring instrumentation (if applicable).
In practice, not all of the potential environmental hazards which may be inherent to a site can be readily anticipated. To mitigate these circumstances, SCST field personnel must learn, follow, and enforce the published rules governing occupational health and safety. In addition, they must maintain awareness and exercise common sense and good judgement when confronting possible unsafe situations. Consequently, all divisions and offices at the Edison facility are required to provide their staff with the necessary safety training and equipment to perform their assigned duties.
For SCST personnel, all training and certification requirements are to be undertaken in accordance with the protocols set forth in the 1995 "Edison Health and Safety Manual." Specifically, this requires completion of the forty (40) hour "Hazardous Materials Incident Response Operations" training pursuant to Occupational Safety and Health Administration (OSHA) regulation 29 CFR 1910.120 and U.S. EPA Order 1440.2. This is to be supplemented by completing the twenty four (24) hour OSHA sanctioned supervised on-site operations certification training. In conjunction, SCST personnel are also to maintain certifications for:
• The supplemental eight (8) hour annual health and safety refresher training. • Fit testing for atmosphere supplying respirators (Level B) and air purifying
respirators (Level C). • Enrollment in a physician authorized medical monitoring program.
5.2 Sample Handling and Custody Requirements
5.2.1 Sample handling and shipment
Canister Sample Data Sheets, a Questionnaire and the field notebook will be completed for each sample collected. All field and sample documents will be legibly written in indelible ink. Any corrections or revisions will be made by lining through the original entry and initialing the change. The Questionnaire will record sample location; residential information; time of sample drop off and pick up; conditions in the room; laboratory sample number; laboratory sample analysis and sample collection notes and/or observations. For reference, an example of the Questionnaire is presented as Appendix G. The Canister Sample Data Sheet will be provided by ERG and records the sample location, sampling period, initial and final pressure and comments. An example of this
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data sheet can also be found in Appendix G. The field notebook will be used by field personnel to record all aspects of sample collection and handling, visual observations, and field measurements. The field notebook is a descriptive notebook detailing site activities and observations so that an accurate, factual account of field procedures may be reconstructed. The sample team or individuals performing a particular sampling activity are required to maintain a field notebook. This field notebook will be a bound weatherproof logbook that shall be filled out at the location of sample collection immediately after sampling. All entries will be signed by the individuals making them. At a minimum, the notebook will contain sample particulars including sample number, collection time, location, descriptions, methods used, daily weather conditions, field measurements, name of sampler(s), sample preservation, names of contractor/ subcontractor personnel, and other site-specific observations including any deviations from protocol.
The Canister Tag, found in Appendix G> also provided by ERG, will be securely affixed to each SUMMA™ canister and include only the sample identification number as per protocol. The sample tags will be secured to the canister itself. Custody seals will then be affixed around a bag surrounding each individual canister. Once sealed, samples will be placed back into the cardboard boxes that they were received in. Custody seals and strapping tape will then be affixed to the boxes.
Samples will be packaged and shipped in accordance with USEPA, Department of Transportation (DOT), and International Air Transport Association (IATA) procedures. All samples will be shipped within 24 hours of collection to the ERG office in North Carolina.
5.2.2 Sample custody procedures
Standard U.S.EPA Chain-of-Custody Procedures will be followed for all samples and be in accordance with the U.S.EPA Region I I CERCLA Quality Assurance Manual. The Chain of Custody Records will be maintained from the time of sample collection until final deposition. Every transfer of custody will be noted and signed for and a copy of the record will be kept for each individual who has signed it. The chain-of-custody records will include, at a minimum, sample identification number, number of samples collected, sample collection date and time, sample type, sample matrix, sample container type, sample analysis requested, sample preservation, and the name(s) and signature(s) of samplers and all individuals who have had custody. Sample labels will only include the sample identification number as per protocol to prevent any conflict of interest issues. Custody seals will demonstrate that a sample container or cooler has not been opened or tampered with. The sampler will sign and date the custody seal and affix it to the container and/or cooler in such a manner that it cannot be opened without breaking the seal.
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6.0 CALIBRATION PROCEDURES AND FREQUENCY
6.1 Instrument Calibration and Frequency
Laboratory analytical equipment calibration will follow procedures as specified under U.S. EPA, Compendium Method TO-15: Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specialty-Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) from the Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air, which can be found as Appendix C.
7.0 ANALYTICAL PROCEDURES
7.1 Analytical Methods Requirements
The analytical method, equipment and method performance requirements for analysis will be according to ERG's contract with the subcontracted laboratory. Refer to U.S. EPA, Compendium Method TO-15: Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specialty-Prepared Canisters and Analyzed by Gas Chromatography/ Mass Spectrometry (GC/MS) from the Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air, which can be found as Appendix C.
8.0 DATA REDUCTION, VALIDATION, AND REPORTING
8.1 Data Review, Validation and Verification Requirements:
Standard methods and references will be used as guidelines for data reduction and reporting. All data generated by the laboratory will be reported in standard deliverable format. ERG will be using a gas chromatograph (GC)/flame ionization detector (FID)/ mass selective detector (MSD) to analyze the samples for VOCs as stated in their QAPP which is based on TO-15. Due to ERG's vast experience with analyzing SUMMA™ canisters for VOCs, they have found this method to be the most precise and they are able to detect the compounds at unusually low concentrations. All data validation reports will be summarized according ERG's QAPP: Support For NMOO SNMOC, UATMP, and PAMS Networks, Contract No. 68-D-99-007, Quality Assurance Project Plan, Section 15 which can be found as Appendix B.
8.2 Validation and Verification Methods
All data will be validated by ERG's generic Support For NMOO SNMOC, UATMP, and PAMS Networks, Contract No. 68-D-99-007, Quality Assurance Project Plan, Section 15, which can be found as Appendix B.
8.3 Data Acquisition Requirements
Data acquisition from non-direct measurements such as data from databases or literature is not anticipated at this time. Therefore, this is not applicable.
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Data Quality Management
All project data and information must be documented in a format that is usable by project personnel. This section of the QAPP describes how project data and information will be documented, tracked, and managed from their generation in the field to final use and storage in a manner that ensures data integrity and defensibility. All field and sample documents will be legibly written in indelible ink. Any correction or revisions will be made by lining through the original entry and initialing the change.
The following field and sample documentation will be maintained.
• The field notebook is a descriptive notebook detailing site activities and observations so that an accurate, factual account of field procedures may be reconstructed. The sample team or individuals performing a particular sampling activity are required to • maintain a field notebook. This field notebook will be a bound weatherproof logbook that shall be filled out at the location of sample collection immediately after sampling. All entries will be signed by the individuals making them. At a minimum, the notebook will contain sample particulars including sample number, collection time, location, descriptions, methods used, daily weather conditions, field measurements, name of sampler(s), sample preservation, and other site-specific observations including any deviations from protocol.
• Field data sheets, i.e., Questionnaire, Canister Field Data Sheet, and corresponding sample labels are used to identify samples and document field sampling conditions and activities. The field data sheets will be completed at the time of sample collection and will include the following: sample location; residential information; drop off and pick up time; sample environment description; laboratory sample number; laboratory sample analysis; and sample collection notes and/or observations. An example of the Questionnaire and the Canister Field Data Sheet are presented in Appendix G. Sample labels will be securely affixed to the sample container and include only the sample identification number as per Protocol.
• Sample tags will be securely affixed to the sample container and include only the sample identification number as per protocol to prevent any conflict of interest issues. The sample labels will be sealed to a bag surrounding the canister sample label integrity.
• The Chain of Custody Records will be maintained from the time of sample collection until final deposition. Every transfer of custody will be noted and signed for and a copy of the record will be kept for each individual who has signed it. The chain-of-custody records will include, at a minimum, sample identification number, number of samples collected, sample collection date and time, sample type, sample matrix, sample container type, sample analysis requested, sample preservation, and the name(s) and signature(s) of samplers and all individuals who have had custody-. An example of the chain of custody that will be used at this site can be found in Appendix G.
13
Custody seals will demonstrate that a sample canister or box has not been opened or tampered with. The sampler will sign and date the custody seal and affix it to the bag or box in such a manner that it cannot be opened without breaking the seal.
• Procedures are provided for project personnel to make changes, take corrective actions and document the process through Corrective Action Request Forms. Corrective action can occur during field activities, laboratory analysis, data validation, and data assessment. For further information, refer to Section 13.0: Corrective Action.
9.0 INTERNAL QUALITY CONTROL CHECKS AND FREQUENCY
9.1 Quality Control Requirements
As previously stated, to assess data quality, PARCC (Precision, Accuracy, Representativeness, Completeness, and Comparability) parameters will be utilized. These essential data quality elements are delineated as follows.
9.1.1 Data precision
Precision is defined as a measure of the reproducibility of individual measurements of the same property under a given set of conditions. The overall precision of measurement data is a mixture of sampling and analytical factors.
9.1.1.1 An aly tical precision
The measure of replicate precision is the absolute value of the difference between replicate measurements of the sample divided by the average value and expressed as a percentage as follows:
Percent difference = ]X, - X 2 | x 100 X
where: X! - First measurement value X 2 - Second Measurement value X - Average of the two values
Factors that affected the precision of the measurement are: molecular weight, water solubility, polarizability, etc. A primary influence is the concentration level of the compound. A replicate precision value of 25 percent can be achieved for each of the target compounds. For more information, refer to Compendium Method TO-15: Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specialty-Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) which can be found as Appendix C.
Table 2 located on page 17 of this QAPP depicts the analytical precision for the analytical methods chosen in terms of estimated relative percent difference (RPD).
14
9.1.1.2 Sample collection precision
Sample collection precision will be assessed by collecting field replicate samples. The field replicates will be used to evaluate errors associated with sample heterogeneity, sampling methodology and analytical procedures. The analytical results from these samples will provide data on the overall measurement precision.
9.1.2 Data accuracy
Accuracy is defined as the degree of difference between measured or calculated values and the true value. The closer the numerical value of the measurement comes to the true value, or actual concentration, the more accurate the measurement is. It is difficult to measure accuracy for the entire data collection activity. Sources of error are the sampling process, field contamination, preservation, handling, sample matrix, sample preparation and analysis techniques.
9.1.2.1 Analytical accuracy
A measurement of analytical accuracy is the degree of agreement with audit standards. It is defined as the difference between the nominal concentration of the audit compound and the measured value divided by the audit value and expressed as a percentage as follows:
Audit Accuracy, % = Spiked Value - Observed Value X 100 Spiked Value
For more information, refer to Compendium Method TO-15: Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specialty-Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) which can be found as Appendix C.
Table 2 on page 17 located in this QAPP depicts both the analytical precision and accuracy for the analytical methods chosen in terms of estimated percent recovery.
9.1.2.2 Sample collection accuracy
Method blanks will be used to monitor possible laboratory contamination.
9.1.3 Data Representativeness
Representativeness expresses the degree to which sample data accurately and precisely represent a characteristic of a population, parameter variations at a sampling point, or and environmental condition. Representativeness is a qualitative parameter which is most concerned with the proper design of the sampling program and proper laboratory protocol. The representativeness criterion is best satisfied by making certain that sampling locations are selected properly and a sufficient number of samples are collected. Therefore, data representativeness will be assessed by collecting field replicate samples. The field replicates are by definition equally representative of a given point in space and time.
15
In addition, as previously stated, data representativeness will be satisfied by ensuring that the sampling program is followed according to the U.S. EPA Region IICERCLA Quality Assurance Manual; and the U.S. EPA Superfund Program Representative Sampling Guidance for soil, Volume 1. Also, proper sampling techniques will be used in accordance with the U.S. EPA. Environmental Response Team (ERT) Standard Operating Procedure (SOP) #1704: Summa Canister Sampling. The SOP is enclosed in Appendix D.
9.1.4 Data Comparability .
Comparability is defined as the confidence with which one data set can be compared to another. Field and laboratory procedures greatly affect comparability. Therefore, to optimize comparability, sampling and analysis for all samples will be performed using standardized analytical methods and adherence to the quality control procedures outlined in the methods and this QAPP. Therefore, the data will be compared.
9.1.5 Data Completeness
Completeness is defined as the measure of the amount of valid data obtained from a measurement system compared to the amount that was expected to be obtained under normal conditions. Data completeness will be expressed as the percentage of valid data obtained from measurement system. For data to be considered valid, it must meet all the acceptable criteria including accuracy and precision, as well as any other criteria specified by the analytical method used. Therefore, all data points critical to the sampling program in terms of completeness will be 100% validated by the ERG contract in accordance with the ERG's generic Support For NMOO SNMOC, UATMP, and PAMS Networks, Contract No. 68-D-99-007, Quality Assurance Project Plan, Section 15. With 100% validation, the rationale for considering data points non-critical is not required.
10.0 Performance and Systems Audits
10.1 Assessments and Response Actions •
No performance audit of field operations is anticipated at this time. I f conducted, performance and systems audits will be in accordance with:
• U.S. EPA (Environmental Protection Agency) Region II . April 2000. SOP SCST-1, Standard Operating Procedure (S.O.P.) for Performing Oversight of CERCLA Field Operations. Revision 0. Division of Environmental Services and Assessment, Hazardous Waste Support Branch, Hazardous Waste Support Section, Edison, NJ.
11.0 PREVENTIVE MAINTENANCE
11.1 Instrument/Equipment Testing, Procedures & Scheduled Inspection and Maintenance Requirements
As previously stated, calibration and preventative maintenance of analytical laboratory equipment will follow procedures as specified in ERG's generic Support For NMOO
16
SNMOC, UA TMP, and PAMS Networks, Contract No. 68-D-99-007, Quality Assurance Project Plan, Section 15, which can be found as Appendix B.
11.2 Inspection/Acceptance Requirements for Supplies and Consumables
Due to the nature of air sampling rinsate and trip blanks are not applicable. SUMMA™ canister quality control includes calibration of the canister itself, method blanks performed by the laboratory and laboratory control samples, also performed by the laboratory.
12.0 SPECIFIC ROUTINE PROCEDURES/MEASUREMENT PARAMETERS INVOLVED
12.1 Reconciliation with Data Used to Assess PARCC for Quality Objectives Measurement
Sample collection precision will be evaluated by collecting and analyzing a field duplicate sample. The field duplicate samples will be used to evaluate errors associated with sample heterogeneity, sampling methodology and analytical procedures. The analytical results from the field duplicate will provide data on the overall measurement precision. Precision will be reported as the relative percent difference (RPD) for two measurements. The acceptance criteria for the field duplicate samples are located in Table 2 on page 17.
Data will be generated through the collection of air samples in residential basements in the area of the White Swan Laundry and Cleaners Site. This data will be used to determine the location and concentration of contamination in the residents, the extent of contamination, evaluate potential health threats, and determine environmental impacts while identifying clean-up criteria.
TABLE 2: PRECISION AND ACCURACY
Sample Parameter/Fraction
Sample Matrix
Analytical Method
Method Detection
Limit 1
Quantitation Limit
Estimated Accuracy1
Accuracy Protocol
Estimated Precision1
Precision Protocol
Title III Clean Air Amendment List
Volatile Organic Compounds (VOCs)
Air TO-15 0.04 -0.26 ppbv
ppbv <or= 30% Non-RAS % difference and absolute % difference
Non-RAS
' The method detection limits were provided by ERG as per their generic Support For NMOO SNMOC, UA TMP, and PAMS Networks, Contract No. 68-D-99-007, Quality Assurance Project Plan. ,
13.0 CORRECTIVE ACTION
13.1* Assessments and Response Actions
Procedures are provided for project personnel to make changes, take corrective actions and document the process through Corrective Action Request Forms. Corrective action can occur during field activities, laboratory analysis, data validation, and data assessment.
17
Corrective action in the field may be necessary when the monitoring network design is changed. A change in the field includes: increasing the number or type of samples or analyses; changing sampling locations; and/or modifying sampling protocol. When this occurs, the project officer or project QA officer will identify any suspected technical or QA deficiencies and note them in the field logbook. The project QA officer will be responsible for assessing the suspected deficiency and determining the impact on the quality of the data. Development of the appropriate corrective action will be the responsibility of the OSC.
Data validation and data assessment corrective action will be in accordance with the U.S. EPA Region II CERCLA Quality Assurance Manual.
14.0 QA REPORTS TO MANAGEMENT
14.1 Distribution List
The following project personnel will receive copies of the approved QAPP and any subsequent revisions.
Project Personnel Title
Tom Budroe On-Scene Coordinator ERRD/RAB
Diane Salkie Project Officer DESA/HWSB
Pat Sheridan Quality Assurance Officer DESA/HWSB
14.2 Reports to Management
The data collected as a result of sampling activities; will be organized, analyzed and summarized in a final project report that will be submitted to the OSC according to the Project Schedule. The report will be prepared by the project officer or project quality assurance officer and include appropriate data quality assessment.
APPENDIX A
SITE MAPS
I I_* ; ASBURY PARK, N.J. 40074-Bl-TF-024
Ai 1989 — A DMA6.64MNE-SERJ0SV822
Magnolia Avenue Ground Water Contamination Area MAP 2C
Outlined area depicts the extent of PCE, TCE and DCE contamination plume.
Coast Guard
1.6 Miles
Gulf Service Station Sun Cleaners White Swan L&C
Township of Wall Monmouth County. Tax Map 1969 Block 706 Lot 2
White Swan Laundry & Cleaners 1322 Sea Girt Avenue Wall Twp. Monmouth Co. New Jersey
MAP 2
S-1
GW-29
Parking S-2
GWl
GW-30 GW-2
GW-7
former location
of White Swan building
White Swan Launder & Cleaners
1322 Sea Girt Avenue
Wal Twp. Monmouth Co.
New Jersey
MAP 3
GW-1
C
Parking'
grass island 3
Of ass area
LEGEND • Ground Water Sample • Soil Sample A Ground Water and
Soil Sample
Gulf Service Station 1324 Sea Girt Ave. Wall Twp Monmouth County New Jersey .
MAP 3A
Sun Cleaners Site Map/Sample Location Map
MAP-4
Atlantic Ave
Sun Cleaners Building Sun Cleaners Property
200 200 400 600 800 Feet
APPENDIX B
Eastern Research Group (ERG)
Support for NMOC/SNMOC, UATMP and PAMS Networks, Contract No. 68-D-99-007. Quality Assurance Project Plan.
Morrisville, North Carolina
March 2000
SUPPORT FOR NMOC/SNMOC, UATMP, AND PAMS NETWORKS
Contract No. 68-D-99-007
2000
Quality Assurance Project Plan
Eastern Research Group, Inc. P.O. Box 2010
Morrisville, North Carolina 27560
Approved by:
ERG Program Manager:
ERG Deputy Program Manager: :
ERG Program QA Officer:
U.S. EPA Project Officer:
Project No. 0121.00 Element No. A2 Revision No. 1 Date March 2000 Page ii of viii
DISCLAIMER
This Quality Assurance Project Plan has been prepared specifically for the operation and management of the U.S. EPA National NMOC/SNMOC, UATMP, PAMS, and HAPS Programs. The contents have been prepared in accordance with Level III Specification of the EPA Guidance for Quality Assurance Project Plans, EPA QA/G-5.
Project No. Element No. Revision No Date Page
TABLE OF CONTENTS
Section
List of Tables : vi List of Figures vii Symbols and Abbreviations viii A PROJECT MANAGEMENT . . 1 of 6
1 Project/Task Organization 1 of 6 1.1 Assignment of Program Personnel 1 of 6
2 Problem Definition/Background 1 of 2 3 Project/Task Description and Schedule 1 of 15
3.1 NMOC and SNMOC . . l o f l 5 3.2 UATMP 6 of 15 3.3 PAMS . .' 10 of 15 3.4 HAPs 13 of 15
4 Data Quality Objectives and Criteria for Measurement Data l o f l 5 5 Special Training Requirements/Certification 1 of 2
5.1 Sampling Personnel •••• 1 of2 5.2 Analytical Laboratory Personnel 1 of 2
B MEASUREMENT DATA ACQUISITION 1 of 8 6 Sampling Process Design . 1 of 8
6.1 NMOC and SNMOC Sampling 1 of 8 6.2 UATMP Sampling . . . . 3 of 8 6.3 PAMS Sampling 8 of 8 6.4 HAPs Sampling 8 of 8
7 Sample Handling and Custody Requirements 1 of 17 7.1 NMOC, SNMOC, and UATMP Sample Custody 1 of 17 7.2 Carbonyl Sample Custody 12 of 17 7.3 HAPs Sample Custody ." 14 of 17 7.4 Sampling Monitoring Data 17 of 17
8 Analytical Methods Requirements 1 of 17 8.1 Canister Cleanup System l o f l 7 8.2 NMOC Analytical Systems 4 of 17 8.3 SNMOC Analytical Systems 6 of 17 8.4 UATMP and Concurrent Analytical System 6 of 17 8.5 PAMS Analytical Systems 9 of 17 8.6 Semivolatile Analytical Systems 11 of 17 8.7 Ethylene Oxide by Gas Chromatograph Analytical Systems . . . . 13 of 17 8.8 Dioxin/Furan by High Resolution Mass Spectroscopy
Analytical Systems 16 of 17 8.9 Metals Using an Inductively Coupled Argon Plasma Mass
Spectroscopy Analytical System 17 of 17
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Project No. 0121.00 Element No. A2 Revision No. 1 Date March 2000 Page iv of viii
TABLE OF CONTENTS (Continued)
9 Quality Control Requirements l o f l 6 9.1 Sample Canister Cleanup Studies l o f l 6 9.2 Standard Traceability , l o f l 6 9.3 Accuracy and Acceptance 2 of 16 9.4 Precision 9 of 16 9.5 Completeness • 9 of 16 9.6 Representativeness . . . . .. 11 of 16 9.7 Comparability 11 of 16 9.8 Lowest Quantitation Limits 11 of 16
10 Instrument/Equipment Testing, Inspection, and Maintenance Requirements 1 of 2 10.1 NMOC 1 of 2 10.2 SNMOC, UATMP, and PAMS 1 of 2 10.3 PAMS 2 of 2 10.4 HAPS 2 of 2
11 Instrument Calibration and Frequency 1 of 11 11.1 NMOC Calibration . . . l o f l l 11.2 SNMOC Calibration 3 of 11 11.3- UATMP Calibration 4 of 11 11.4 PAMS Calibration 7 of 11 11.5 HAPS Calibration 7 of 11
12 Data Management l o f l C ASSESSMENT/OVERSIGHT 1 of 3
13 Assessments and Response Actions 1 of 3 13.1 QA Performance Audits 1 of 3 13.2 Performance Evaluation and System Audits 1 of 3
. 13.3 QA Reports 1 of 3 14 Reports to Management : 1 of 2
14.1 QA and QC Functions 1 of 2 D DATA VALIDATION AND USABILITY 1 of 9
15 Data Review, Validation, and Verification Requirements 1 of 9 15.1 NMOC/SNMOC Data Reduction, Validation, and Reporting 2 of 9 15.2 UATMP Data Reduction, Validation, and Reporting 4 of 9 15.3 PAMS Data Reduction, Validation, and Reporting 6 of 9 15.4 HAPS Data Reduction, Validation, and Reporting 7 of 9 15.5 Aerometric Information Retrieval System Air Quality Subsystem
(AIRS AQS) . . : 8 of 9 16 Reconciliation with Data Quality Objectives l o f l 17 References 1 of 3
APPENDICES
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v of viii
TABLE OF CONTENTS (Continued)
The following methods are included by reference. These methods are available through the U.S. EPA Bulletin Board —www.epa.gov/:
ttn/amtic/airtox.htlm—
EPA Compendium Method TO-12, "Method for the Determination of Non-Methane Organic Compounds (NMOC) in Ambient air Using Cryogenic Preconcentration and Direct Flame Ionization Detection (PDFID)"
EPA Compendium Method TO-14A, "Determination of Volatile Organic Compounds (VOCs) in Ambient Air Using Specially Prepared Canisters with Subsequent Analysis by Gas Chromatography"
EPA Compendium Method TO-15, "Determination of Volatile Compounds (VOCs) in Air Collected in Specially Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS)"
EPA Compendium Method TO-11 A, "Determination of Formaldehyde in Ambient Air Using Adsorbent Cartridge Followed by High Performance Liquid Chromatography (HPLC) [Active Sampling Methodology]"
EPA Compendium Method TO-9A, "Determination of Polychlorinated, Polybrominated and Brominate/Chlorinated Dibenzo-p-Dioxins and Dibenzofurans in Ambient Air"
sw-846/sw-846.htm—
Method 8290, "Polychlorinated Dibenzodioxins (PCDDs) and Polychlorinated Dibenzofurans (PCDFs) High-Resolution Gas Chromatography/High-Resolution Mass Spectrometry (HRGC/HRMS)"
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Project No. 0121.00 Element No. A2 Revision No. 1 Date March 2000 Page vi of viii
LIST OF TABLES
Table
1-1 1999/2000 Program Organization 1 of 6 I - 2 QC Responsibilities and Review Functions 5 of 6
3-1 SNMOC Target Compounds 4 of 15 3-2 UATMP Target Compounds 8 of 15 3-3 PAMS VOC Target Compounds 12 of 15 3-4 Carbonyl Target Compounds 14 of 15 3- 5 Analysis of Hazardous Air Pollutants .' 15 of 15
4- 1 NMOC Data Quality Objectives 2 of 15 4-2 Summary of SNMOC Procedures 3 of 15 4-3 Air Toxics TO-15 QC Procedures . . 4 of 15 4-4 Carbonyl Data Quality Objectives 7 of 15 4-5 Quality Control Procedures for Analysis of Semivolatile Organic Samples
According to EPA Method 8270 9 of 15 4-6 Quality Control Parameters for Ethylene Oxide Analysis Performed According to
the Analytical Procedures of NIOSH Method 1614 12 of 15 4-7 Quality Control Parameters for Dioxin/Furan Analysis Performed According to
the Analytical Procedures of EPA Method 8290 13 of 15 4-8 Quality Control Parameters for Phosgene Performed According to the
Analytical Procedures of Compendium TO-6 14 of 15 4-9 Quality Control Measures for Metals Analysis According to Method 10-3.5 . . . . 15 of 15
8-1 UATMP GC/FID/MSD Operating Conditions 7 of 17 8- 2 Semivolatile Organic Compounds to be Analyzed by the Analytical Procedures of
Method 8270, with Estimated Method Detection Limits 14 of 17
9- 1 Decafluorotriphenylphosphine (DFTPP) Key Ions and Ion Abundance Criteria According to EPA Method 8270 5 of 16
9-2 Quality Control Measures for Metals Analysis 10 of 16 9-3 SNMOC Lowest Quantitation Limits 13 of 16 9-4 TO-15 Analyte Lowest Quantitation Limit (LQL) 15 of 16 9-5 Lowest Quantitation Limits, Underivatized Concentration (ppbv) ,.> 16 of 16
I I - i Analytical Equipment Calibration Requirements . . 9 of 11
14-1 QC Responsibilities and Review Functions . 2 of 2
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Project No. 0121.00 Element No. A2 Revision No. 1 Date ' March 2000 Page vii of viii
LIST OF FIGURES
Figure
I - 1 Program Organization Chart . . 2 of 6
6-1 NMOC, SNMOC, and 3-Hour Air Toxics Sampling System Components 2 of 8 6-2 Carbonyl Sampling System 4 of 8 6-3 Sampling Assembly for the UATMP .'. 6 of 8 6- 4 Cross-Sectional View of the Ozone Scrubber Assembly 7 of 8
7- 1 Canister Sample Data Sheet 2 of 17 7-2 Sample Receipt Login Information 3 of 17 7-3 Canister Tag 4 of 17 7-4 NMOC Invalid Sample Form 5 of 17 7-5 NMOC Daily HP 5880 Calibration Form 7 of 17 7-6 Canister Cleanup Log • 8 of 17 7-7 UATMP Analysis Log 10 of 17 7-8 Carbonyl Field Data Sheet 13 of 17 7-9 Label for Sample Identification 15 of 17 7- 10 Corrective Action Report 16 of 17
8- 1 Canister Cleaning Apparatus : 2 of 17 8-2 Schematic of Analytical Systems for NMOC 5 of 17 8-3 Gas Chromatograph/Mass Spectrometer/FID System 8 of 17 8-4 HPLCSystem 10ofl7
I I - 1 Dynamic Flow Dilution Apparatus 6 of 11
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Project No. Element No. Revision No Date Page
SYMBOLS AND ABBREVIATIONS
ug Micrograms
uL Microliters
AC Area Counts
AIRS AQS Aerometric Information Retrieval System Air Quality Subsystem
BFB 4-Bromofluorobenzene
cm Centimeter
DNPH 2,4-Dinitrophenylhydrazine
EPA EnvironmentalProtection Agency
ERG Eastern Research Group, Inc.
FID Flame Ionization Detector
GC Gas Chromatograph
GC/MSD Gas Chromatograph/Mass Selective Detector
Hg Mercury
HPLC High Performance Liquid Chromatography
ID Identification
KI Potassium Iodide
m Meter
MB Megabyte
MDL Method Detection Limit
min Minute
mL Milliliter
mm Millimeter
MS/MSD Method Spike/Method Spike Duplicate
NAAQS National Ambient Air Quality Standard
NERL National Exposure Research Laboratory
NIST National Institute of Standards and Technology
nm Nanometer
NMOC Nonmethane Organic Compound
OAQPS Office of Air Quality Planning and Standards
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PAMS
PDF ID
ppbC -
ppbv
ppmC
pprhv
psig
QA/QC
QAD
QAPP
RCA
RPD
RSD
RTP
SIP
SNMOC
TAD
UAM
UATMP
VOC
SYMBOLS AND ABBREVIATIONS (Continued)
Photochemical Assessment Monitoring Station
Preconcentration Direct Flame Ionization Detection
Parts per Billion as Carbon
Parts per Billion Volume
Parts per Million as Carbon
Parts per Million Volume
Pounds per Square Inch Gauge
Quality Assurance/Quality Control
Quality Assurance Division
Quality Assurance Project Plan
Recommendation for Corrective Action
Relative Percent Difference
Relative Standard Deviation
Research Triangle Park
State Implementation Plan
Speciated Nonmethane Organic Compound
Technical Assistance Document for Sampling and Analysis of Ozone Precursors
Urban Airshed Model
Urban Air Toxics Monitoring Program
Volatile Organic Compound
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Project No. 0121.00 Element No. A4 Revision No. 1 Date March 2000 Page 1 of 6
A—PROJECT MANAGEMENT
SECTION 1
PROJECT/TASK ORGANIZATION
1.1 Assignment of Program Personnel
Table 1-1 presents the 1999/2000 program organization listing the program assignment
and responsible person.
Table 1-1
1999/2000 Program Organization
Program Assignment Program Personnel Assigned
Program Manager Dave-Paul Dayton
Deputy Program Manager ; Julie Swift
Task Leader - Site Coordination/NMOC Analysis Peer Reviewer
Mitch Howell Julie Swift
Task Leader - SNMOC Analysis Peer Reviewer
Donna Tedder Julie Swift
Task Leader - Air Toxic Analysis Peer Reviewer
Mitch Howell Julie Swift
Task Leader - Carbonyl Analysis Peer Reviewer
Randy Bower Donna Tedder
Task Leader - PAMS Support Peer Reviewer
Dave-Paul Dayton Rob Martz
Task Leader - HAPS Support Peer Reviewer
Rob Martz Julie Swift
Task Leader - Reporting Peer Reviewer
Julie Swift Dave-Paul Dayton
Task Leader - AIRS Peer Reviewer
Randy Bower Dave-Paul Dayton
Program QA Officer Joan Bursey
Senior Technical Advisor Ray Merrill
Project Administrator Carol Hobson
Project Secretary Gail Pierce
The program organizational chart is presented in Figure 1-1.
glp/D:\SECT1.WPD
" D
o
o
o EPA Project Officer
Vickie Presnell
EPA Delivery Order Manager Sharon Nizich
SNMOC Analysis Task Leader
Donna Tedder
Peer Reviewer Julie Swift AirT
Task Mitch
oxics Leader Howell
Peer Reviewer Julie Swift
Program QA Officer Joan Bursey
Program Manager Dave-Paul Dayton
Senior Technical Advisor
Raymond Merrill Deputy Program Manager Julie Swift
Project Administrator Carol Hobson
Project Secretary Gail Pierce
1
Carbonyis Analysis Task Leader
Randy Bower
Peer Reviewer Donna Tedder
NMOC Analysis & Site Coordination
Task Leader Mitch Howell
PAMS Support Task Leader
Dave-Paul Dayton
Peer Reviewer Julie Swift
HAPS Support Task Leader Rob Martz
Peer Reviewer Rob Martz
AIRS Dz TaskL
Randy
tabase eader 3ower
Peer Reviewer Dave-Paul Dayton
Peer Reviewer Julie Swift Rep
TaskL Julie S
Drt =ader swift
Peer Reviewer Dave-Paul Dayton
y o 5* P m o °5 I < C/5
o '
o
CD " ,
CD' o
O 2. o
3 o
M to N> Figure 1-1. Program Organization Chart o ^ ^ 0\ O H o
Project No. Element No. Revision No. Date
0121.00 A4
1 March 2000
3 of 6 Page
1.1.1 Program Manager
ERG's program manager, Dave-Paul Dayton, a member of ERG's technical staff, has the
primary concern of understanding the state's and EPA's needs at the program level and ensuring
overall timely performance of high quality technical services. He coordinates with the technical
advisors, peer reviewers, coordinators, directors, and the task leaders to communicate technical
issues and needs and to ensure that these individuals are involved in management decisions
appropriate for their roles in this contract.
1.1.2 Deputy Program Manager
As the Deputy Program Manager, Julie Swift is responsible on a day-to-day basis for the
technical conduct of the program and for leading the analytical tasks and providing technical
direction and support. She assists with any technical problems that arise. She responds to the
task leaders regarding any project issues that affect their task(s). She assists with analytical
analysis, data reduction, review and reporting. She is responsible for ensuring that the
appropriate level of staffing, number of work shifts, and committed resources (automated
analytical equipment) exist to meet the required project deliverables and sample turnaround time.
She tracks budget performance for all tasks and reports this information to the Program Manager
and all Task Leaders. She also ensures that all management systems and tools required for this
program are implemented and tracked, and tracks deliverables and budget performance to present
project performance information to the EPA at monthly meetings and in monthly progress
reports.
1.1.3 Program QA Officer
The Program QA Officer, Joan Bursey, is responsible for ensuring the overall integrity
and quality of the project results. She reviews the QAPP and coordinates data and laboratory
audits that will provide information relative to data quality and determine whether procedures are
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Project No. 0121.00 • Element No. A4
Revision No. 1 Date March 2000 Page 4 of 6
in accordance with the QAPP. The lines of communication between management, the Program
QA Officer, and the technical staff are formally established and allow for discussion of real and
potential problems, preventive actions, and corrective procedures. The major QC responsibilities
and QC review functions are summarized in Table 1-2.
Anytime during the program, additional QA/QC measures may be initiated upon
consultation between the task leader, Program QA Officer and the senior technical advisor.
1.1.4 Senior Technical Advisor
The senior technical advisor, Dr. Raymond G. Merrill, is responsible for ensuring the
overall technical quality of ERG's approach to the program. Dr. Merrill's ultimate responsibility
is ensuring client satisfaction and that components of effective management are active at all
times during the contract performance period.
1.1.5 Task Leaders
The ERG task leaders are responsible for meeting the project objectives, meeting budgets
and schedules, and directing the technical staff in execution of the technical effort for their
respective task(s). The task leaders manage the day-to-day technical activities. They assess and
report on the project's progress and results (e.g., recordkeeping, data validation procedures,
sample turnaround time), and ensure timely, high-quality services and adherence to the project
QA plan.
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Project No. 0121.00 Element No. A4 Revision No. 1 Date March 2000 Page 5 of 6
Table 1-2
QC Responsibilities and Review Functions
Responsible Person Major Responsibilities
Program Manager • Ensure overall timely performance of high quality technical services • Communicate technical issues and needs • Track all management systems and tools • Track deliverables and budget performance • Review reports before reporting to the client
Deputy Program Manager
• Ensure data quality • Check information completeness • Assist with technical problems • Ensure appropriate leyel of staffing and committed resources exist to perform
work • Review data completeness and quality before reporting to client • Review all reports • Report project performance (budget and deliverables) to EPA at monthly
meetings and in monthly progress reports • Day-to-day management of task leaders
Program QA Officer Review QC reports • Make QA recommendations • Write and/or review test plan • Write and/or review QAPP • Audit laboratory(s) • Review documentation (reports, etc.)
Technical Advisor • Propose procedural change • Propose equipment change • Assist with technical problems.
Peer Reviewer • Ensure final data quality • Final data review • Assist with technical problems
Analytical Task Leader • Review documentation • Develop analytical procedures • Propose procedural changes .
Data review and validation • Analyst training and supervision • Meet task budgets and report schedules • Manage day-to-day technical activities • Check information completeness • Review instrument and maintenance log books • Review calibration factor drift • Perform preventive maintenance • Prepare monthly/quarterly reports
1.1.6 Peer Reviewers
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The ERG peer reviewers are responsible for ensuring the final data quality before
anything is reported to the client. They perform the final data review on the analytical reports.
The peer reviewers also assist in resolving any technical problems that occur in the laboratory or
at the sites.
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SECTION 2
PROBLEM DEFINITION/BACKGROUND
The Clean Air Act Amendments of 1990 required the Environmental Protection Agency's
(EPA's) Office of Air Quality Planning and Standards (OAQPS) to set National Ambient Air
Quality Standard (NAAQS) for the "criteria" pollutant, ozone. In areas of the country where the
NAAQS for ozone is being exceeded, additional measurements of the ambient nonmethane
organic compound (NMOC)(1) concentration are needed to assist the affected states in developing
revised ozone control strategies. Measurements of ambient NMOC are important to the control
of volatile organic compounds (VOCs) that are precursors to atmospheric ozone. Because of
previous difficulty in obtaining accurate NMOC concentration measurements, EPA and Radian
Corporation started a monitoring and analytical program in 1984 to provide support to the states.
Studies indicate that a potential for elevated cancer risk is associated with certain toxic
compounds often found in urban ambient air.(2) In 1987, EPA developed the Urban Air Toxics
Monitoring Program (UATMP) to help State arid local agencies characterize the nature and
extent of potentially toxic air pollution in urban areas. Since 1987, several State and local
agencies have participated in the UATMP by implementing ambient air monitoring programs.
These efforts have helped to identify the toxic compounds most prevalent in the ambient air and
indicate emissions sources that are likely to be contributing to elevated concentrations. As a
screening program the UATMP also provides data input for models used by EPA (and others) to
assess risks posed by the presence of toxic compounds in urban areas. The UATMP program is a
year-round sampling program, collecting 24-hour integrated ambient air samples at urban sites in
the contiguous United States every 12 days, and is also supported by ERG.
The speciated NMOC (SNMOC) program was initiated in 1991 in response to requests
by State agencies for more detailed speciated hydrocarbon data for use in ozone control strategies
and Urban Airshed Model (UAM) input. In 1996, Radian Corporation sold the EPA contracts
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and necessary resources to Eastern Research Group, Inc. (ERG), who now support EPA for the
NMOC and SNMOC programs.
Title I , section 182 of the Clean Air Act Amendments of 1990 requires states to establish
Photochemical Assessment Monitoring Stations (PAMS) as part of their state implementation
plan (SIP) for ozone nonattainment areas. The rule revises the ambient air quality surveillance
regulations to include enhanced monitoring of ozone and its precursors. The regulations
promulgated in 1993 require monitoring of ozone, oxides of nitrogen (NOx), selected carbonyl
compounds, and VOCs. The required monitoring is complicated and requires considerable lead
time for the agencies to acquire the equipment and expertise to implement their PAMS network.
Under the PAMS program, each site may require a different level of support with respect to
sampling frequency, sampling equipment, analyses, and report preparation. Presampling,
sampling, and analytical activities are performed according to the guidance provided in the
Technical Assistance Document for Sampling and Analysis of Ozone Precursors (TAD), 1998
revision/3' The specific methodology applicable to the PAMS program will be discussed in this
Quality Assurance Project Plan (QAPP).
In 1999, the EPA expanded this program to provide for the measurement of additional
Clean Air Act Hazardous Air Pollutants (HAPs) to support the Government Performance and
Results Act (GPRA). As required under the GPRA, the EPA developed a Strategic Plan that
includes a goal for Clean Air. Under this goal, there is an objective to improve air quality and
reduce air toxic emissions to levels 75 percent below 1993 levels by 2010 in order to reduce the
risk to Americans of cancer and other serious adverse health affects caused by airborne toxics.
This combined QAPP defines the presampling and sampling activities and laboratory
analyses conducted by ERG for the NMOC, SNMOC, UATMP, PAMS, and HAPs programs and
describes the quality assurance/quality control (QA/QC) procedures used to assess data quality.
Many of these procedures are based on previous NMOC studies.(4"'0,12"l6>
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SECTION 3
PROJECT/TASK DESCRIPTION AND SCHEDULE
This section describes the acti vities performed under each of the major program
components (NMOC, SNMOC, UATMP, PAMS, and HAPs). The SUMMA® canisters used by
this laboratory are dedicated to each separate program. Sampling and analysis schedules are
prepared in the project instructions when the delivery orders are provided by EPA.
3.1 NMOC and SNMOC
The NMOC and SNMOC programs require several activities for a successful monitoring
program. The monitoring program begins with presample collection activities. The NMOC and
SNMOC sample collection systems are designed to collect ambient air samples in
SUMMA®"treated stainless steel canisters over a 3-hour period. The sample collection period
occurs from 6:00 - 9:00 a.m. local time to capture mobile source pollutants during the morning
"rush hour" simultaneously with sunrise, which provides the energy necessary for many
photochemical reactions.
A selected number of canisters from state and EPA directed sites are analyzed for
additional air toxic compounds; the sites and canisters are identified at the beginning of the
program to ensure sample completeness. Some sites also collect carbonyl samples for analysis..
The analytical methods and procedures are discussed later in the UATMP and PAMS project
descriptions.
The SUMMA® canisters dedicated to the program are checked for leaks, repaired, and
cleaned using a vacuum and pressurization canister cleaning system. The canisters are certified
by ERG for cleanliness by analyzing the contents using EPA Compendium Method TO-12 for
determining total NMOC concentration.
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The State or local agency site personnel are contacted to coordinate site installation,
operator training, sample collection, and shipping. ERG provides installation of the sample
collection system, supporting documentation, training of the site operator for collection of
scheduled samples, and ongoing technical support and coordination for sample collection during
the entire monitoring program.
Samples are collected by State or local agency personnel every weekday starting on the
first Monday of June through the end of September at each of the designated sites. At least two
days before each sample collection episode, ERG ships the necessary clean, certified canisters to
the site along with the field sample collection form and chain of custody forms. The time
integrated ambient samples are then collected and shipped to ERG for analysis.
Samples are delivered to a dedicated loading dock area that is part of the laboratory space
used for the programs. Samples are received and logged into a sample receipt log and into a
computerized login database networked to be accessible to all analysts and task leaders. After
the sample identification number, date received, sample date, project name, canister pressure, and
storage location are documented, the field sample collection form is reviewed and any
discrepancies or invalidated samples are reported to the Deputy Program Manager. ERG
contacts the site operator for resolution of any sample issues. The samples are then taken to the
laboratory for analysis.
The analytical equipment used for the NMOC program consists of two modified
Preconcentration Direct Flame Ionization Detection (PDFID) Hewlett-Packard gas
chromatographs (GC) with cryogenic sample preconcentration systems and dual-channel Flame
Ionization Detectors (FIDs). EPA Compendium Method TO-12 is used for the analysis.
The PDFID systems used for analyses are calibrated and blanked daily before sample
analysis. Cleaned, humidified air from the canister cleaning system is analyzed to determine the
level of organic compounds present in the analytical system. Upon achievement of acceptable
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system blank results (< 10 ppbC), a daily QC check sample of propane is analyzed. The
QC check sample is used to check the calibration of the analytical system. Upon acceptable
calibration results (r2 2:0.995), sample analysis begins.. Ten percent of the total number of
samples received are collected in duplicate and analyzed twice to determine the precision and
analysis for the program.
The NMOC data are then processed to determine the total NMOC present in the sample.
The parts per million as carbon (ppmC) concentration of the NMOC is determined using the
daily propane calibration response factor. Preliminary data summaries are compiled monthly for
all sites and distributed to the site contacts and the EPA Project Officer.
During the 1997 season, ERG's laboratory implemented a system on the standard
UATMP instrumentation to analyze the SNMOC canisters. For the first time, all analyses -
SNMOC, UATMP and PAMS compounds. - can be obtained from one analysis. Because of this
analytical achievement, effort and costs for any combination of analyses are significantly
reduced. ,
Speciated NMOC analysis is performed to identify and quantify the VOC species present
in the ambient air. The analytical equipment used,for the SNMOC program consists of an
Entech 7100 Preconcentrator, a Hewlett-Packard GC/FID/MSD, and a data acquisition system.
ERG staff analyze the samples for SNMOC compounds (listed in Table 3-1) in accordance with
the methodology specified in the TAD ( 3 ) using a GC/MSD and an FID following EPA
Compendium Methods TO-14A and TO-15. The FID is used to perform quantitative analysis of
the SNMOC compounds of interest; the MSD is used for confirmation and identification of .
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Table 3-1
SNMOC Target Compounds
Compound
Ethylene 2,3-Dimethylpentane Acetylene 3-Methylhexane Ethane 1-Heptene Propylene 2,2,4-Trimethylpentane Propane «-Heptane Propyne : Methylcyclohexane Isobutane 2,2,3-Trimethylpentane Isobutene 2,3,4-Trimethylpentane 1 -Butene Toluene 1,3-Butadiene 2-Methylheptane «-Butane 3-Methylheptane /ra;«-2-Butene 1-Octene cw-2-Butene n-Octane 3-Methyl-l-Butene Ethylbenzene Isopentane p,w-Xylene 1-Pentene Styrene 2-Methyl-1 -Butene o-Xylene «-Pentane 1-Nonene Isoprene n-Nonane
. ;ra«.y-2-Pentene Isopropylbenzene c';i-2-Pentene «-Propylbenzene 2-Methyl-2-Butene • a-Pinene 2,2-Dimethylbutane (Neohexane) • m-Ethyltoluene Cyclopentene /7-Ethyltoluene 4-Methyl-l-Pentene 1,3,5 -Trime thylbenzene 2,3-Dimethylbutane o-Ethyltoluene Cyclopentane P-Pinene 2-Methylpentane (Isohexane) 1,2,4-Trimethylbenzene 3-Methylpentane 1-Decene 2-Methyl-1-Pentene «-Decane 1-Hexene 1,2,3 -Trime thylbenzene 2-Ethyl-l-Butene w-Diethylbenzene «-Hexane p-Diethylbenzene trans-2-Hexene 1 -Undecene cw-2-Hexene n-Undecane Methylcyclopentane Dodecene 2,4-Dimethylpentane n-Dodecane Benzene Tridecene Cyclohexane n-Tridecane 2-Methylhexane (Isoheptane) Total NMOC
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compounds of interest. The FID provides good sensitivity and uniform response based on the
number of carbon atoms per compound.
Moisture and carbon dioxide are removed from the analytical system using a microscale
purge and trap dehydration device located in the Entech 7100 Preconcentrator. Personnel
perform cryogenic concentration of the samples using a trap consisting of chromatographic-grade
stainless steel tubing packed with commercially available hybrid 60/80 mesh Tenax®/deactivated
glass beads maintained at -160°C during sample concentration. The concentrated VOCs are
thermally desorbed at room temperature to revolatilize them for transfer to the secondary trap.
The secondary trap is Tenax® at -60°C. The VOCs are then back-flushed while heating to be
further focused on an open-tubular focusing trap for rapid injection onto the analytical column.
The sample is injected onto the cold column to separate C2 through C1 3 hydrocarbons and to
obtain a total SNMOC concentration.
The SNMOC systems are calibrated monthly using propane and blanked daily prior to
sample analysis. A QC standard is analyzed daily prior to sample analysis to ensure the validity
of the current monthly response factor. Following the daily QC standard analysis, cleaned, dried
air that has been humidified from the canister cleaning system is analyzed to determine the level
of organic compounds present in the analytical system. Upon achieving acceptable system blank
results, sample analysis begins. Samples are analyzed for the target compounds listed in
Table 3-1. Ten percent of the total number of samples are analyzed twice to determine the
precision of analysis for the program.
The SNMOC raw data from the PE-Turbochrom® (Perkin Elmer) chromatography data
acquisition system are processed and reduced to determine peak identifications for any target
analytes present in the samples. The propane response factor from the calibration curve
determines the parts per billion as carbon (ppbC) concentration of the target analytes.
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At the end of the sample collection period, the postsampling activities begin. The sample
collection equipment is recovered from the sites and refurbished as necessary by ERG, who
collect and store the equipment in a dedicated area until the next monitoring program
presampling activities begin. ERG then prepares the final program report describing procedures,
results, discussion of results, compilation of statistics, and recommendations. Upon approval by
the EPA Project Officer and Delivery Order Manager, ERG distributes the final report to
designated persons. ERG provides the final data summaries to EPA in Excel® format on
magnetic floppy disk media, archives all project files, raw data, reports, correspondence, memos,
letters, and copies of the final report, and formats the finalized data for input into the AIRS AQS
3.2 UATMP
The UATMP requires several key activities for a successful monitoring program. The
program originates with presample collection activities. The UATMP sample collection system
is designed to collect whole-air 24-hour integrated ambient air samples in SUMMA®-treated
stainless steel canisters, resulting in a subatmospheric final pressure. Prior to field installation,
the sample collection systems are certified using a dual-manifold certification system, which
verifies cleanliness and determines the background level of target organic compounds introduced
by the sample collection system. The certification procedure also determines the percent
recovery of selected target analytes by challenging the system with a known concentration of
selected toxic organic compounds.
The SUMMA® canisters are checked for leaks, repaired i f necessary by ERG or the
canister vendor, cleaned using a vacuum and pressurization canister cleaning system, and then
certified for cleanliness. The cleanliness of a canister is determined by analyzing the contents
using EPA Compendium Method TO-15 for determining volatile compound concentration and
by analyzing one canister per cleaned set by Gas Chromatograph/Flame Ionization
Detector/Mass Selective Detector (GC/FID/MSD).
database.
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The analytical equipment used for the UATMP consists of a cryogenic sample
concentration system and a GC/FID/MSD with a FID detector for hydrocarbon analysis. The
FID is used concurrently with the MSD to quantitate the 59 target compounds present in the
sample. UATMP target compounds are listed in Table 3-2. This system provides the required
sensitivity and confirmation of target compound identification to determine the detection limits
needed for the assessment of potential risks associated with the toxic compounds measured for
this program. The EPA Compendium Method TO-14A is followed as well as TO-15 to illustrate
that analyses for all compounds requested can be achieved depending on EPA's preference for
method.
As with NMOC and SNMOC activities, the State or local agency site personnel are
contacted to coordinate installation, operator training, sample collection, and shipping activities.
ERG provides installation of the sample collection system, support documentation, training of
the site operator for collection of scheduled samples, and ongoing technical support and
coordination of sample collection.
Samples are collected by State or local agency personnel once every 12 days for a period
of 1 year at each of the designated sites. At least 2 days prior to the sample collection episode,
ERG ships the necessary cleaned and certified canisters to the site along with the chain of
custody form and field sample collection form. The ambient air samples are collected in
canisters over a 24-hour period from midnight to midnight local standard time. Ten percent of
the total number of samples are received in duplicate and analyzed in replicate to statistically
determine the precision of sampling and analysis for the program.
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Table 3-2
UATMP Target Compounds
UATMP Target Compounds
Acetylene Ethyl Acrylate
Propylene Bromodichloromethane
Dichlorodifluoromethane Trichloroethylene
Chloromethane Methyl Methacrylate
Dichlorotetrafluoroethane cis-1,3 - D ichloropropene
Vinyl Chloride Methyl Isobutyl Ketone
1,3-Butadiene ira^-l^-Dichloropropene
Bromomethane 1,1,2-Trichloroethane
Chloroethane Toluene
Acetonitrile Dibromochloromethane
Trichlorofluoromethane 1,2-Dibromoethane l
Acrylonitrile t
n-Octane 1,1-Dichloroethene Tetrachloroethylene
Methylene Chloride Chlorobenzene
Trichlorotrifluoroethane Ethylbenzene
trans-1,2-Dichloroethylene m-//?-Xylene
1,1-Dichloroethane Bromoform
Methyl te/Y-Butyl Ether Styrene
Methyl Ethyl Ketone 1,1,2,2-Tetrachloroethane
Chloroprene o-Xylene
cis-1,2-Dichloroethene 1,3,5-Trimethylbenzene
Bromochloromethane 1,2,4-Trimethylbenzene
Chloroform m-Dichlorobenzene
Ethyl te>7-Butyl Ether. Chloromethylbenzene
1,2-Dichloroethane /7-Dichlorobenzene
1,1,1 -Trichloroethane '• o-Dichlorobenzene
Benzene 1,2,4-Trichlorobenzene
Carbon Tetrachloride Hexachloro-1,3-Butadiene
fcrt-Amvl Methvl Etlier 1,2-DichloroDrorjane
Samples are shipped to ERG and received in a loading dock area that is part of the
dedicated laboratory space used for the program. ERG then logs the samples into the sample
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receipt log book and documents the sample identification number, date received, sample date,
project name, canister vacuum, and storage location. ERG also logs samples into the •
computerized login database. After comparing the above information with the field sample
collection form, ERG brings any discrepancies or invalidated samples to the attention of the
Deputy Program Manager. ERG contacts the site operator for resolution of any sample issues,
and the samples are then taken to the laboratory for analysis.
The GC/FID/MSD system is calibrated for the target compounds in Tables 3-1 and 3-2
and blanked daily prior to sample analysis. The validity of the tune of the MSD is verified daily
using 4-Bromofluorobenzene (BFB). A QC check sample is also analyzed daily using a
UATMP standard and PAMS standard to validate the response factors from the calibration of the
analytical system. Upon acceptable QC results, a daily blank sample is analyzed. Clean,
humidified air from the canister cleaning system is analyzed to determine the level of organic
compounds present in the analytical system; upon acceptable blank results, sample analysis
begins.
ERG uses Hewlett-Packard Chemstation® and Perkin Elmer Turbochrom® data systems to
acquire data. Personnel identify compounds by referring to a combination of the compound's
retention time, the MSD library, and the analyst's experience and judgment. All of the target
UATMP compounds are quantitated using the MSD; all target SNMOC compounds are
quantitated using the FID. Sample concentrations are calculated using the monthly calibration
curve response factor from the MSD and propane monthly calibration for the FID. Preliminary
data summary reports are compiled every quarter for all sites and distributed to the site contacts
and the EPA Project Officer. ERG staff also finalize and format data for input into the AIRS
AQS database.
ERG oversees recertification and refurbishment of the samplers once a year to enable
sampling to continue from season to season without interruption. Staff prepare the final program
report describing the procedures, results, discussion of results, compilation of statistics, and
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recommendations and, upon approval of the report by the EPA Project Officer, distribute the
final report to the sites and other persons as designated by the Project Officer. ERG staff also
provide the final data summaries to the EPA in Excel® format on magnetic floppy disk media.
All project files, raw data, reports, correspondence, memoranda, letters, and copies of the final
report are put in short-term file storage and archived.
3.3 PAMS
The program objective of PAMS is to provide data that are consistent with the proposed
rule for Ambient Air Quality Surveillance in accordance with 40 CFR Part 58. As a team, the
ERG staff can offer site support to any state that needs to set up a PAMS site or maintain it with
technical help.
After a PAMS program has been established by the State or local agency, ERG contacts
the EPA site personnel to coordinate sample collection and sample shipment. ERG maintains
coordination of the sample collection and sample shipments with the site contact and resolves
any issues that occur during the sampling season.
The State or local agency typically provides the program's SUMMA®-treated canisters.
ERG cleans the canisters using a vacuum and pressurization canister cleaning system, and then
certifies them for cleanliness by analyzing the contents using EPA Compendium Method TO-12
for determining total NMOC. Canisters are recycled through the canister cleaning and
verification process as needed to support the sample collection schedule for the program.
Sep-Pak® chromatographic-grade silica gel cartridges are used for carbonyl sample
collection. The vendor precoats the cartridges with 2,4-Dinitrophenylhydrazine (DNPH). A
potassium iodide (KI) ozone scrubber, actively maintained at about 65°C during sample
collection, is required to remove ozone from the sample stream.
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Following sample collection, the site contact ships the canisters, cartridges, and
documentation to the ERG laboratory. Project personnel receive samples in a loading dock area
that is part of the dedicated laboratory space used for the programs, log them into the sample
receipt log book and the computerized log, and document the information pertaining to the
sample identification number, the date received, sample date, project name, canister vacuum, and
storage location. Project personnel review the chain of custody and field sample collection forms
and any discrepancies or invalidated samples are brought to the attention of the PAMS Task
Leader. If necessary, the Site Preparation Task Leader contacts the site for resolution of issues
for subsequent samples. The canister samples are then taken to the laboratory for analysis and
the cartridges are stored under refrigeration.
ERG staff analyze samples for PAMS VOC (listed in Table 3-3) in accordance with the
methodology specified in the TAD ( 3 ) using a GC/MSD and a FID. The FID is used to perform
quantitative analysis of the compounds of interest; the MSD is used for confirmation and
identification of compounds of interest. The FID provides good sensitivity and uniform response
based on the number of carbon atoms per compound. Moisture is removed from the FID
analytical system using a microscale purge and trap dehydration device. Personnel perform
cryogenic concentration of the samples using a trap consisting of chromatographic-grade
stainless steel tubing packed with commercially available 60/80 mesh deactivated glass beads
maintained at -180°C during sample concentration. The concentrated VOCs are thermally
desorbed at room temperature to revolatilize them for transfer to the secondary trap. The second
trap is Tenax® at -60°C. The VOCs are then back-flushed while heating to be further focused on
an open-tubular focusing trap for rapid injection onto the analytical column.
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Table 3-3
PAMS VOC Target Compounds
, Compound
Acetylene 3-Methylhexane Ethylene 2,2,4-Tri methylpentane Ethane n-Heptane Propylene Methyl cycl ohexane Propane 2,3,4-Trimethylpentane
. Isobutane Toluene 1-Butene 2-Methylheptane n-Butane 3-Methylheptane trans-2-Buterie «-Octane m-2-Butene Ethylbenzene Isopentane m-Xylene 1-Pentene ^-Xylene rc-Pentane Styrene Isoprene o-Xylene ;ra«s-2-Pentene «-Nonane c/s-2-Pentene Isopropylbenzene 2,2-Dimethylbutane ^-Propylbenzene Cyclopentane m-Ethyltoluene 2,3-Dimethylbutane p-Ethyltoluene 2-Methylpentane 1,3,5-Trimethylbenzene 3-Methylpentane o-Ethyltoluene 1-Hexene 1,2,4-Trimethylbenzene n-Hexane «-Decane Methylcyclopentane 1,2,3-Tri methy lbenzene 2,4-Dimethylpentane m-Diethylbenzene Benzene /j-Diethylbenzene Cyclohexane «-Undecane 2-Methylhexane Total NMOC 2,3-Dimethylpentane
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The carbonyl samples are analyzed for the carbonyl compounds listed in Table 3-4 using
EPA Compendium Method TO-11 A. The analytical instrument consists of a Varian 5000 High
Performance Liquid Chromatograph (HPLC) with a multiwavelength UV detector operated at
360 nanometers (nra). The HPLC is configured with a 25 centimeter (cm), 4.6 millimeter (mm)
ID CI 8 silica analytical column with a 5-micron particle size. Typically, 25 microliter (uL)
aliquots are injected with an automatic sample injector.
A PE-Turbochrom® chromatography data acquisition system is used to retrieve data from
both the ozone precursor and carbonyl analytical instruments. The data are processed and peak
identifications are made using retention times and relative retention times. After peak
identifications are made, the concentration of each target analyte is determined using individual
response factors for carbonyl compounds or propane response factors for ozone precursor
compounds. Preliminary data summary reports are distributed to the sites and the EPA Project
Officer once per month. Final data summary and a letter report are provided to the sites and the
EPA at the program end. Final data summary information is formatted for inclusion into the
AIRS AQS database upon approval by the EPA Project Officer.
3.4 HAPs
The program objective of HAPs is to provide data that are needed to support the
Government Performance and Results Act (GPRA). As a team, and with assistance from
Contractors, the ERG staff can offer site support to any state that needs HAPs analysis. The
responsibility for the equipment for sample collection falls on the state or local agency. The
analytical services support for this line item is shown in Table 3-5.
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Table 3-4
Carbonyl Target Compounds
Compounds
Formaldehyde Isovaleraldehyde Acetaldehyde Valeraldehydes Propionaldehyde Tolualdehydes Crotonaldehyde Hexaldehyde Butyraldehyde 2,5-Dimethylbenzal dehyde Isobutyraldehyde Acetone Benzaldehyde
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Table 3-5
Analysis of Hazardous Air Pollutants
Analytical Analytical HAP Method HAP Method
Category I Category IV
Benzene TO-14A/TO-15 Acenaphthene TO-13A Carbon Tetrachloride TO-14A/TO-15 Acenaphthylene TO-13A Chloroform TO-14A/TO-15 Anthracene . TO-I3A Chloroprene TO-14A/TO-I5 Benzo(ghi)perylene TO-13A 1,4-Dichlorobenzene TO-14A/TO-15 Fluoranthene TO-13A Ethylene Dibromide TO-14A/TO-15 Fluorene TO-13A Ethylene Dichloride TO-14A/TO-15 Naphthalene TO-13A Hexachlorobenzene TO-14A/TO-15 Phenanthrene TO-13A Methyl Bromide TO-14A/TO-15 Pyrene TO-13A Methyl Chloride TO-14A/TO-15 Benz(a)anthracene TO-13A Styrene TO-14A/TO-15 Benzo(a)pyrene TO-13A Tetrachloroethylene TO-14A/TO-I5 Benzo(b)fluoranthene TO-13A Toluene TO-14A/TO-15 Benzo(k)fluoranthene TO-13A Trichloroethylene TO-14A/TO-15 Chrysene TO-13A Vinyl Chloride TO-14A/TO-15 Dibenz(a,h)anthracene TO-I3A Xylenes TO-14A/TO-I5 Indeno( 1,2,3-cd)pyrene TO-I3A 1,3-Butadiene TO-14A/TO-15 Acrylonitrile TO-14A/TO-15
Category II Category V
Acetaldehyde TO-11A Antimony & Compounds 10-3.5 Formaldehyde TO-11A Arsenic & Compounds 10-3.5
Beryllium & Compounds 10-3.5 Cadmium & Compounds 10-3.5 Chromium & Compounds* 10-3.5 Lead & Compounds 10-3.5 Manganese & Compounds 10-3.5 Mercury & Compo'unds IO-3.5 Nickel & Compounds 10-3.5
Category III
Phosgene TO-6 bis(2-Chloroethyl) Ether TO-13A bis(2-Ethylhexyl) Phthalate TO-13A 2,3,7,8-Tetrachlorodibenzo-p-Dioxin TO-9 Ethylene Oxide NIOSH 1614 ,.
*Chromium determined from a filter is total chromium, not chromium VI. Chromium VI oxidizes when sampled on a filter.
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Project No. Element No. Revision No Date Page
SECTION 4
DATA QUALITY OBJECTIVES AND CRITERIA FOR MEASUREMENT DATA
The data quality objectives for the four programs—NMOC, UATMP, PAMS, and
HAPs—are similar but are not identical. Therefore, the programs are discussed separately.
Data quality objectives are presented in Table 4-1. for the NMOC monitoring program
and in Table 4-2 for the SNMOC monitoring program. The major quality objectives of these
programs are to ensure that ambient air samples are collected in a prescribed manner and NMOC
and SNMOC concentrations are measured precisely and accurately. Because the SNMOC
samples are also analyzed by the UATMP system, the quality objectives presented in Table 4-3
are adhered to also when applicable to hydrocarbon analyses (flagged with an ®).
The quality objectives of the UATMP and the HAPs supported Category I Analytes listed
in Table 3-5 are to ensure that ambient air samples are collected in the prescribed manner and to
ensure that target compound qualitative and quantitative analyses are performed with known
precision and accuracy. Data quality objectives for the UATMP are presented in Table 4-3. The
data quality objectives for PAMS ambient air canister analyses are the same as those described
for the SNMOC and the UATMP (flagged with a @) and summarized in Tables 4-2 and 4-3,.
respectively.
The following canister pressure acceptance criteria have been adopted for the UATMP
program:
• . Based on previous experience,(4"10'12"16) no upper limits on the canister pressure are obtained from a UATMP sampling site. If the initial vacuum is less than 0.5 inches Hg, however, the sample is flagged on the data sheet, chromatogram, and log book.
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Table 4-1
m o NMOC Data Quality Objectives "a o
QC Check Frequency Acceptance Criteria Corrective Action
Calibration Check (midpoint of curve)
Daily Relative percent difference within 20% of average calibration response (avg-daily)/avg
1) Repeat analysis of the point
2) Repeat analysis at different level
3) Repeat calibration curve 4) Remake and reanalyze
standard
System blank - Wet Air <50% %RH
Daily (after a calibration check)
<10.0ppbC 1) Repeat analysis 2) Leak check system 3) Notify task leader
Multi-point Calibration; 5 point plus zero, 3 injections per point
At the beginning and end of the sampling season
Correlation criteria (r2) > 0.995. Each point must have an RSD <3% (except zero)
1) Repeat one or two individual points
2) Repeat entire curve 3) Remake and reanalyze
curve
Replicates All duplicates Within 100 area counts - RSD ±5%
1) Notify coordination director
Can Cleaning One can analyzed on the Air Toxics system per batch of eight-highest total NMOC
Less than 10.0 ppbC 1) Repeat analysis once 2) Reclean canister batch
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Summary of SNMOC Procedures
QC Check Frequency Acceptance Criteria Corrective Action
System Blank Analysis Daily, following calibration check
20 ppbC total 1) Repeat analysis 2) Check system for leaks 3) Clean system with wet air
Multiple point calibration (5 points minimum); propane bracketing the expected sample concentration.
Prior to analysis and monthly Correlation Coefficient (r)>0.995
1) Repeat individual sample analysis
2) Repeat linearity check 3) Prepare new calibration
standards and repeat
Calibration check using midpoint of calibration " curve spanning the carbon range (C,-C10)
Daily on the days of sample analysis
Response for selected hydrocarbons spanning the carbon range within ±30% difference of calibration curve slope
1) Repeat check 2) Repeat calibration curve
Replicate analysis All duplicate field samples Total NMOC within ±30% RSD
Repeat sample analysis
Canister cleaning certification
One can analyzed on the Air Toxics system per batch of eight-highest total NMOC
< 10 ppbC total Reclean canisters and reanalyze
Table 4-3
Air Toxics TO-15 QC Procedures
QC Check Frequency Acceptance Criteria Corrective Action
Bromofluorobenzene (BFB) Instrument Performance Check®
Daily* prior to calibration check and sample analysis
Analyst evaluates by HP Chemstation®; criteria can be found in software
1) Retune 2) Clean ion source and/or
quadrupoles
Five point calibration bracketing the expected sample concentration
Following any major change, repair or maintenance if daily QC is not acceptable. Recalibration not to exceed six weeks.
1) Relative Standard Deviation (RSD) of response factors <30%
2) Relative Retention Times (RRT) for target peaks ±0.06 units from mean
. relative retention time
1) Repeat individual sample analysis
2) Repeat linearity check 3) Prepare new calibration
standards and repeat analysis
Calibration check using mid-point of calibration . curve or one other point in curve®
Daily* on the days of sample analysis
Analyst verifies that the response factor <30% bias from calibration curve average response factor
1) Repeat calibration check 2) Repeat calibration curve
System Blank Analysis® Daily* following BFB and calibration check; prior to analysis
1) 0.2 ppbv per analyte or the MDL, whichever is greater
2) Internal Standard (IS) area response ±40% and IS Retention Time (RT) ±0.33 min. of most recent calibration check
1) Repeat analysis with new blank can
2) Check system for leaks, contamination
3) Reanalyze blank
Laboratory Control Standard (LCS)
Daily* 1) Recovery Limits 70% - 130% 2) IS RT ±0.33 min. of most recent
calibration
1) Repeat analysis 2) Repeat calibration curve
Replicate Analysis® All duplicate field samples
<30% Relative Percent Difference (RPD) for compounds greater than 5 times MDL
1) Repeat sample analysis
Table 4-3
(Continued)
QC Check Frequency Acceptance Criteria Corrective Action
Canister Cleaning Certification
One can analyzed on the Air Toxics system per batch of eight-highest total NMOC
<0.2 ppbv per VOC targeted compounds or MDL, whichever is greater
1) Reclean canisters and reanalyze
Sampler Certification Annual 1) Recovery 80% to 120% of targeted compounds for certification challenge
2) <0.2 ppbv or the MDL whichever is greater of targeted compounds for blank certifications
1) Repeat certification of canisters
Samples® All samples IS RT±0.33 min. of most recent calibration validation
1) Repeat analysis
*Every 24 hours frequency. ®QA criteria also needed for SNMOC and PAMS analysis.
Project No. Element No. Revision No. Date Page
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• If the elapsed time for sample collection is less than 20 hours or greater than 28 hours, the sample will be flagged on the data sheet, the chromatogram, and log book.
• Because the analytical system cannot extract a sample from a vacuum greater than 10 inches Hg, any canisters received with vacuum greater than 10 inches Hg will be ' voided.
• If the final canister vacuum is between ,7 and 10 inches Hg, the analysis is performed, but the sample is flagged on the data sheet, the chromatogram, and in the log book. If two successive samples from the same site result in canister vacuums greater than 11 inches Hg for each canister, the site operator is contacted and appropriate corrective action taken.
• For duplicate samples, if one or both canisters have a final vacuum between 7 and 10 inches Hg, only the canister with the higher vacuum will be analyzed, but the analysis cannot be replicated. If one of the duplicate canisters has a final vacuum higher than 15 inches Hg, neither is analyzed.
• If the duplicate samples have initial canister pressures that differ more than 0.5 inches Hg, only the canister with the higher vacuum will be analyzed and the occurrence recorded in the sample log book.
Quality objectives determined for the carbonyl analysis and the HAPs supported carbonyl
compounds listed in Category II analytes in Table 3-5 are to ensure that ambient air samples are
collected in the prescribed manner and to ensure that compound quantitative analyses are
performed with known accuracy and precision. The data quality objectives for carbonyl analysis
are presented in
Table 4-4.
Quality objectives determined for Semivolatile organic compounds (Category III) and
Polynuclear Aromatic Hydrocarbons (PAHs, Category IV) are-to ensure that ambient air samples
are collected in the prescribed manner and to ensure that target compound quantitative analyses
are performed with known precision and accuracy. The data quality objectives for these
compounds are presented in Table 4-5.
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Table 4-4
Carbonyl Data Quality Objectives
Parameter Quality Control
Check Frequency Acceptance Criteria Corrective Action
HPLC Column Efficiency
Analyze second source QC sample (SSQC)
At setup and 1 per sample batch
Resolution between acetone and propionaldehyde > 1.0 Column efficiency > 5,000 plate counts
Eliminate dead volume, back flush, or replace the column, repeat analysis
Linearity Check
Run a 5-point calibration curve and SSQC in triplicate
At setup or when calibration check is out of acceptance criteria
Correlation coefficient > 0.999, relative error for each level against calibration curve ± 20% or less Relative Error
Check integration, reintegrate or recalibrate
Linearity Check
Run a 5-point calibration curve and SSQC in triplicate
At setup or when calibration check is out of acceptance criteria
Intercept acceptance should be < 10,000 area counts per compound which correlates to 0.06 mg/mL
Check integration, reintegrate or recalibrate
Retention Time Analyze calibration midpoint
Once per 10 samples Acetaldehyde, Benzaldehyde, Hexanaldehyde within retention time window established by determining 3o or ±2% of the mean calibration and midpoint standards, whichever is greater
Check system for plug, regulate' column temperature, check gradient and solvents
Calibration Check
Analyze midpoint standard
Once per 10 samples 85-115% recovery Check integration, recalibrate or. remake standard, reanalyze samples not bracketed by acceptable standard
Calibration Accuracy
SSQC Once after calibration in triplicate
85-115% recovery Check integration, recalibrate or remake standard, reanalyze samples not bracketed by acceptable standard
Calibration Accuracy
Analyze O.lug/mL standard
Once after calibration in triplicate
±25% difference
Check integration, recalibrate or remake standard, reanalyze samples not bracketed by acceptable standard
System Blank Analyze acetonitrile Bracket sample batch, 1 at beginning and 1 at end of batch
Measured concentration < 5 times the MDL Locate contamination and document levels of contamination in file
Duplicate Analyses
Duplicate samples As collected ±20% difference Check integration, check instrument function, reanalyze duplicate samples
Replicate Analyses
Replicate injections Duplicate samples only <, 10% RPD for concentrations greater than 1.0 pg/mL.
Check integration, check instrument function, reanalyze duplicate samples
Table 4-4
(Continued)
Parameter Quality Control
Check Frequency Acceptance Criteria Corrective Action
Method Spike/Method Spike Duplicate (MS/MSD)
Analyze MS/MSD One MS/MSD per 20 samples
80-120% recovery for all compounds. Check calibration, check extraction procedures
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Quality Control Procedures for Analysis of Semivolatile Organic Samples According to EPA Method 8270
Quality Control Check Frequency Acceptance Criteria Corrective Action
Decafluorotripheny 1-phosphine (DFTPP) instrument tune check
Daily prior to calibration check and sample analysis; every 12 hours if instrument is operated 24 hours/day
Evaluation criteria in Table 3 of Method 8270
1. Re-tune instrument; re-analyze 2. Clean ion source; re-tune
instrument; re-analyze 3. Prepare new tune check standard;
analyze
Five-point calibration Following any major change, repair, or maintenance if daily quality control check is not acceptable. Minimum frequency every six weeks, more frequently if required
Average Relative standard deviation (RSD) of response factors for all compounds should be <30%;. average RSD for Calibration Check Compounds must be <30%
1. Repeat individual sample analyses 2. Check calculations 3. Perform maintenance on GC,
especially leak check 4. Clean ion source 5. Prepare new calibration standards
and repeat analysis
System Performance Check Compounds (SPCCs) •
Daily (or every 12 hours) Minimum response for SPCCs of0.050
1. Repeat individual sample analyses 2. Check calculations 3. Perform maintenance on GC,
especially leak check 4. Clean ion source 5. Prepare new calibration standards
and repeat analysis
Calibration Check Compounds (CCCs)
Daily (or every 12 hours) Percent difference for each compound must be less than 30% relative to the mean of the calibration curve
1. Repeat individual sample analyses 2. Check calculations 3. Perform maintenance on GC,
especially leak check 4. Clean ion source 5. Prepare new calibration standards
and repeat analysis
Reagent Blank Once per 20 samples (5%) All analytes <5 x Method Detection Limit
1. Repeat analysis 2. Flag data
Table 4-5
(Continued)
Quality Control Check Frequency Acceptance Criteria Corrective Action
Surrogate compound Every sample 1. Repeat analysis recoveries 2. Flag data nitrobenzene-d5 35-114% 2-fluorobiphenyl 43-116% /?-terphenyl-d14 33-141% phenol-d6 10-94% 2-fluorophenol 21-100% 2,4,6-tribromo- 10-123%
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Project No. Element No. Revision No. Date
0121.00 A7
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The data quality objectives for phosgene, 2,3,7,8-tetrachlorodibenzo-p-dioxin, and
ethylene oxide (Category III) from the HAPs Table 3-5 are to ensure that ambient air samples are
collected in the prescribed manner and to ensure that target compound qualitative and
quantitative analyses, are performed with known precision and accuracy. The data quality
objectives for phosgene, 2,3,7,8-tetrachlorodibenzo-p-dioxin, and ethylene oxide are listed in
Tables 4-6, 4-7, and 4-8, respectively.
Quality objectives determined for the Clean Air Act metals (Inorganic HAPs, Category V
from Table 3-5) are to ensure that ambient air samples are collected in the prescribed manner and
to ensure that compound quantitative analyses are performed with known accuracy and precision.
The data quality objectives for the metals analysis are presented in Table 4-9.
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Project No. Element No. Revision No. Date Page
Table 4-6
Quality Control Parameters for Ethylene Oxide Analysis Performed According to the Analytical Procedures of NIOSH Method 1614
Parameter Frequency Acceptance Criteria Corrective Action
Six-point calibration Initially - prepare with samples
Checked by blind spikes and analyst spikes
1. Re-analyze individual calibration standards
4. Re-prepare calibration standards; reanalyze
Calibration check I -(Analyst spikes)
Daily - analyze 3 Relative percent difference between compound and mean response factor from calibration curve <20%
1. Re-analyze calibration check I
2. Check calculations 3. Re-prepare analyst
spike 4. Re-calibrate
Calibration check I I -(Blind spikes)
Daily - analyze 3 Relative percent difference between compound and mean response factor from calibration curve 5; 20%
1. Re-analyze calibration check I I
2. Check calculations 3. Re-calibrate
Reagent blank, Laboratory,blank
One per batch of samples
No analyte present above method detection limit
1. Repeat analysis 2. Re-prepare reagent
blank; analyze 3. Flag data
Measure breakthrough for each sample
All samples If the sample back analysis is > one tenth of the sample front analysis. Wb>Wf/10
1. Report breakthrough and possible sample loss.
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Project No. 0121.00 Element No. A7 Revision No. 1 Date March 2000 Page 13 of 15
Table 4-7
Quality Control Parameters for Dioxin/Furan Analysis Performed According to the Analytical Procedures of EPA Method 8290
Parameter Frequency Acceptance Criteria Corrective Action
Five-point calibration Initially; repeat when • daily calibration check does not meet acceptance criteria
Relative standard deviation for response factors <20%, <30% for labeled reference compounds
1. Re-analyze individual calibration standards
2. Re-tune HRMS 3. Clean ion source 4. Re-prepare
calibration standards; reanalyze
Calibration check Daily (or every 12 hours if instrument is . operated 24 hrs/day)
Relative percent difference between compound and mean response factor from calibration curve <25%, <30% for labeled reference compounds
1. Re-analyze calibration check standard
2. Check calculations 3. Re-calibrate
Method spike/method spike duplicate
One per twenty samples (5%)
Accuracy: ± 30% Precision: ±50%
1. Repeat analysis 2. Flag data
Reagent blank, Laboratory blank
One per twenty samples (5%)
No analyte present above method detection limit
1. Repeat analysis 2. Re-prepare reagent
blank; analyze 3. Flag data
Field duplicate One per twenty samples (5%)
No analyte present above method
1. Repeat analysis 2. Re-prepare reagent
blank; analyze 3. Flag data
Trip blank One per twenty samples (5%)
No analyte present above method
1. Repeat analysis 2. Re-prepare reagent
blank; analyze 3. Flag data
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Project No. 0121.00 Element No. A7 Revision No. 1 Date March 2000 Page 14 of 15
Table 4-8
Quality Control Parameters for Phosgene Performed According to the Analytical Procedures of Compendium TO-6
Parameter Frequency Acceptance Criteria Corrective Action HPLC Column Efficiency
Analyze second source QC sample (SSQC)'
At setup and 1 per sample batch
Five-point calibration
Five-point calibration Initially; repeat when daily calibration :check does not meet acceptance criteria
Relative standard deviation for response factors <20%, <30% for labeled reference compounds
1. Re-analyze individual calibration standards
4. Re-prepare calibration standards; reanalyze
Calibration check -intermediate concentration standard near anticipated'levels -at least 10 times the detection limit
Daily Relative percent difference between compound and mean response factor from calibration curve zl0%
1. Re-analyze calibration check . standard
2. Check calculations 3. Re-prepare
calibration standard 4. Re-calibrate
Method spike/method spike duplicate
One per batch of samples (5%)
Accuracy: ± 30% Precision: ±50%
1. Repeat analysis 2. Flag data
Reagent blank, Laboratory blank
One per batch of samples (5%)
No analyte present above method detection limit
1. Repeat analysis 2. Re-prepare reagent
blank; analyze 3. Flag data
Replicate Analysis One per batch of samples
Relative standard deviation of ±15-20%
1. Repeat analysis 2. Flag data
Precision and Recovery Once per year Recovery and Precision comparable as listed: Cone, (ppbv) 0.034 63% 13 std 0.22 87% 14 std 3.0 99% 3 std 4.3 109% 12 std 20 99% 14 std 200 96% 7 std
1. Repeat analysis 2. Re-prepare reagent
blank; analyze 3. Flag data
glp/D:\SECT4.WPD
Table 4-9
Quality Control Measures for Metals Analysis According to Method 10-3.5
Parameter Frequency Acceptance Criteria Corrective Action
Multipoint calibration Daily Correlation coefficient > 0.995
1. Repeat analysis of calibration standards
2. Re-prepare calibration standards and re-analyze
Calibration check Daily Recovery 95-105% for all analytes
1. Repeat analysis of calibration check standard
2. Repeat analysis of calibration standards
3. Re-prepare calibration standards and re-analyze
Continuing calibration verification Every 10 samples Recovery 90-110% 1. Repeat analysis of continuing calibration verification sample
2. Reprepare continuing calibration -verification sample and re-analyze
3. Reanalyze samples since last acceptable continuing calibration verification
Method blanks Every 10 samples Analytes below method detection limit
1. Reanalyze 2. Reprepare blank and re-analyze 3. Correct contamination and reanalyze
blank 4. Repeat analyses of all samples since
last clean blank
Laboratory control sample One per sample batch Recovery 80-120% Reprepare sample batch; re-analyze
Method spike/method spike duplicate one per sample batch Recoveries 80-120% Flag data.
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1 of 2
0121.00 A8.
Page
SECTION 5
SPECIAL TRAINING REQUIREMENTS/CERTIFICATION
This program is an ambient monitoring program, performed using recognized EPA
sampling and analytical protocols and requiring the efforts of field sampling personnel and
analytical laboratory staff.
5.1 Sampling Personnel
Sampling personnel involved in this project have been trained in their tasks and have
from 1 to 25 years of experience in the duties they will be performing in the field. The field
testing staff will be subject to on-site surveillance by the EPA and ERG Task Leader with
appropriate corrective action enforced, if necessary. ERG personnel setting up the sampling
equipment will also be subject to on-site surveillance by the ERG Task Leader with appropriate
corrective action enforced, if necessary. ERG provides employee training, with specialized,
in-house training classes and on-the-job training by supervisors and co-workers. The monitoring
sites may be inside a sampling building or outside. There are no unusual hazards and no special
safety training or equipment required. All sampling staff will follow the ERG Health and Safety
Plan. The ERG Task Leader will pay special attention to potential heat or pollutant exposure on
a daily basis as conditions change at the site.
5.2 Analytical Laboratory Personnel
Analytical laboratory personnel involved in this project have been trained in their tasks
and have from 1 to 25 years of experience in the duties they will be performing in the analytical
laboratory. Laboratory staff will be subject to on-site surveillance by the Quality Assurance
staff. The samples involved in this program are being generated by monitoring of air emissions.
No unusual hazards are expected and no special safety training or equipment will be required to
perform the analyses. The laboratory will adhere to the ERG Health and Safety manual.
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B—MEASUREMENT DATA ACQUISITION
SECTION 6
SAMPLING PROCESS DESIGN
Sampling procedures for the NMOC and UATMP programs are discussed in this section.
ERG provides site-specific support for the PAMS and HAPs sampling.
6.1 NMOC and SNMOC Sampling
Sampling takes place each workday from the beginning of June to the end of September
at NMOC and SNMOC sites from 6:00 a.m. to 9:00 a.m., standard time. Sampling procedures
have been discussed in detail in other documents.0'10 Figure 6-1 is a diagram of the sampling
system used for collecting the ambient air samples. Evacuated stainless steel canisters are
shipped daily from ERG's Research Triangle Park (RTP) Laboratory to the NMOC and SNMOC
sites. Canisters are connected by local operators to the sampling system as shown. The timer
will automatically activate the pumps and solenoid valve to begin and complete the sampling.
The Metal Bellows®-pump will pressurize air samples during the sampling period to about
15 psig, and the critical orifice will operate at sonic velocity to ensure a constant sampling rate
over the 3-hour period (a 21 micron stainless steel filter is installed in the sampling line and
removes particulate from the ambient air that may damage or plug the critical orifice). The
sample intake point ranges from 3 to 10 meters above ground level.
ERG installs the site sampling systems and trains designated local operators on-site. It is
the responsibility of the local operators to operate the sampling apparatus and complete the field
sample data form that ERG supplies with each canister. ERG staff maintains telephone contact
throughout the project to provide whatever assistance is needed to solve technical problems that
occur during the course of the program.
glp/D:\SECT6.WPD
Filter O Timer
• Sample inlet is an Inverted glass funnel. Lines and fittings are stainless steel.
Out
Solenoid Latching Valve
Metal Bellows® Pump MB151
Pressure Gauge
9
Canister(s)
Figure 6-1. NMOC, SNMOC, and 3-Hour Air Toxics Sampling System Components
Project No. Element No. Revision No. Date
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1 March 2000
3 of 8 Page
ERG creates a sampling schedule, including the appropriate number of samples, when
sites are specified and site requirements are established.
All NMOC and SNMOC sites are usually scheduled to begin sampling at the beginning
of June and continue to the end of September. With a 3-hour ambient air sample, both PDFID,
SNMOC, and air toxics measurements may be performed on the same canister i f enough pressure
remains in the canister. It is recommended that any aliquots for analysis be taken from the
canister on successive days to allow equilibration between analyses.
6.1.1 Air Toxic Compounds Sampling
The 3-hour air toxics samples under the NMOC program are analyzed from the same
canisters as the NMOC and/or SNMOC samples. Refer to Section 6-2 for sampler certification.
6.1.2 Carbonyl Compounds Sampling
Carbonyl samples are collected using DNPH cartridges with an integrated sampling
system (e.g., stand-alone pumps, capillary critical orifices, ozone scrubbers ahead of the
DNPH cartridges), shown in Figure 6-2.
6.2 UATMP Sampling
Prior to installation of the UATMP sampler at a site, the sampler is tested at the ERG
RTP laboratory for performance capability and qualified for cleanliness. Cleaned, humidified air
is flushed through the sampler for at least 48 hours to remove organic contaminants in the
system. The cleaned, humidified air is then analyzed and the results placed in a permanent file to
record any contamination following EPA Compendium Methods TO-14A and TO-15. The
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Project No. Element No. Revision No. Date Page
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Power Line
Sample Inlet
Thermocouple Line
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Cartridge '
Calibrated Rotometer Duplicate ( V )
Orifice V
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Sample Cartridge
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Elapsed Timer
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Figure 6-2. Carbonyl Sampling System
Project No. 0121.00 Element No. Bl Revision No. 1 Date March 2000
. Page 5 of 8
samplers are then challenged with a mixture of known concentration to qualify the sampler.
These results are placed in a permanent file.
ERG will establish a schedule for the UATMP sites when the sites are identified. A total
of 30 sampling days will be scheduled per site program and will be identified in the schedule.
Days for duplicate sampling will be designated.
Integrated ambient air samples are taken in 6-liter stainless steel SUMMA®-treated
canisters for a 24-hour period beginning at midnight. Cleaned canisters are shipped to the site
under vacuum from the ERG RTP laboratory. After sampling, the final desired pressure in the
canister should be between 2 and 5 inches Hg vacuum.
The sampling assembly for the UATMP is shown in Figure 6-3. The driving force for
filling the canister is its initial vacuum. The single-head purge pump shown in Figure 6-3 is used
to purge the sample inlet lines and to draw ambient air through the carbonyl sampling probe and
cartridges.
6.2.1 Carbonyl Compounds Sampling
Carbonyl sampling occurs at UATMP sites at the same time the canister samples are
taken. DNPH sampling cartridges are connected to the UATMP sampler as shown in
Figure 6-3 when the 6-liter canisters are connected, and ambient air is drawn through the
cartridges through a separate heated sampling probe. Each DNPH cartridge has an ozone
scrubber (Figure 6-4) in the sample manifold to remove ozone before the ambient air sample
enters the DNPH cartridge. The ozone scrubbers are replaced before each season (yearly).
Purchased DNPH cartridges are shipped to each site for carbonyl sampling. A total of 34 tubes
will be analyzed per site, including ten percent duplicate samples and ten percent field blanks per
season.
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Sectional View
~ 3" Potassium Iodide Coated 1/4" O.D. Copper Tubing
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Figure 6-4. Cross-Sectional View of the Ozone Scrubber Assembly
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/ Project No. . 0121.00 Element No. Bl Revision No. 1 Date March 2000 Page 8 of 8
ERG ships DNPH sampling cartridges to each site in the shipping container with the
6-liter canister(s). The carbonyl samples are also collected for a 24-hour period. After sampling,
the cartridges are removed from the sampling apparatus, sealed, and returned to the ERG RTP
laboratory in the shipping container with the canister(s). Disposable polyethylene gloves are
used by the field operators when handling the cartridges to reduce background contamination
levels. Additional details of the carbonyl sampling and analysis procedures are presented in the
EPA Compendium Method TO-11 A.
6.3 PAMS Sampling
PAMS sampling is performed completely by the PAMS sites in accordance with the
TAD, ( 3 ) with ERG supplying only such support as requested (e.g., sampling system and training,
automated GC systems). ERG ships cleaned canisters and prepared carbonyl compounds
sampling cartridges to the PAMS sites on the appropriate schedule to support the sampling
program, and the samples are shipped to the ERG RTP laboratory for analysis. Exact provision
for support of automated GC systems is site specific; each site may work with Chromlan during
the sampling season.
6.4 HAPs Sampling
HAPs sampling is performed completely by the sites in accordance with the methods
listed in Table 3-5. ERG receives the samples from the sites for analysis only.
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0121.00 B2
Page
SECTION 7
SAMPLE HANDLING AND CUSTODY REQUIREMENTS
Similar canister sample custody procedures are followed for all monitoring programs;
however, program-specific differences exist because the canister cleanliness requirements and
the analytical requirements for the three programs vary.
7.1 NMOC, SNMOC, and UATMP Sample Custody
7.1.1 NMOC Sampling Field Data Forms
A color-coded, three-copy canister sample data sheet (Figure 7-1) is shipped with each
6-liter canister to an NMOC/SNMOC or UATMP site. If duplicate samples are to be taken, two
canisters and two data sheets are sent in the shipping container to the site. When a sample is
taken, the site operator fills out the field data form according to the instructions in the
NMOC/SNMOC or UATMP on-site notebook. The site operator detaches the pink copy, inserts
it in the on-site notebook, and sends the remaining copies with the canister in the shipping
container to ERG's laboratory.
Upon receipt, the sample canister vacuum/pressure is compared against the field
documented vacuum/pressure to ensure the canister remained airtight during transport. If any
leaks are detected, the sample is voided. The canister information is then entered electronically
into the computer login (login information is shown in Figure 7-2), given a unique ERG
identification (ID) number, and tagged (see Figure 7-3), noting the site location and the sample
collection date. The samples are also logged into the computerized login database. The
remaining copies of the canister sample data sheet are separated; the white copy is stored with
the
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Project No. Element No. Revision No. Date Page
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lERG t i "
Canister Sample Data Sheet LAB ID # EASTERN RESEARCH GROUP, INC;
Q _ l uu
o z > j j o 111
Location: City / State _ Sampling Period: Nox Analyzer Operating: Average PPM:
Elapsed Time:
Average Wind Speed: _ Average Wind Direction: Average Temperature: _ Average Barometric Pressure: Relative Humidity: Flow Controller Set at: Comments:
Site Code: Collection Date:
Canister Number: Operator:
Initial Vacuum: Final Field PressureA/acuum:
Duplicate (Y/N) Duplicate Can #:
Options: Flow Controller Zero Reading:
Received by: •_ Date Received: Carbonyl Tubes:
Carbonyl ID #:
Pressure @ Receipt: Void Acceptable Yes No
Stored:
o o
Analyst: Analysis Date: Analysis Time: NMOC Instrument:
Area Counts run 1: ppmC run 1:
Canister Number: Analysis Pressure: Sample Replicate:
Initial or Repeat:
Area Counts run 2: ppmC run 2:
Average AC: Standard Dev:
Entered into Database by:
Average ppmC: Standard Dev:
Area Counts run 3: ppmC run 3:
Date:
o O s z
Analyst: Analysis Pressure: Load Volume:
Date: Data File Name: Duplicate File Name:
Date:
V) o X o
Analyst: Analysis Pressure: Load Volume:
Date: Data File Name: Duplicate File Name: Replicate File Name:
White: Sample File Copy Yellow: Receiving Copy Pink: Field Copy
Figure 7-1. Canister Sample Data Sheet
glp/D:\SECT7.WPD
Sample Login
ERG Sample ID Date
Received Rec'd
By Date
Sampled Canister Number
coc Present
Tubes Present Project Name & Sample Description
Storage Location
ERG Sample ID Date
Received Rec'd
By Date
Sampled Canister Number
coc Present
Tubes Present Project Name & Sample Description Cans Tubes
* •
-
Figure 7-2. Sample Receipt Login Information *n o w I_d
™. CD O O 3 rt
^ 5 2
3 o tr
O to O
>— o - J o
o to
o o
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o
Site:
Date:
I.D. #
Channel PPMC
Figure 7-3. Canister Tag
canister until analysis is complete and the yellow copy is stored chronologically in the receiving
notebook. The sample ID number is written on the canister tag and on all ERG copies of the data
sheet.
7.1.2 NMOC Invalid Sample Forms
The canister sample data sheet may indicate that the sample sent from a site is invalid.
When a sample is designated as invalid, the assigned ERG ID number is voided and an NMOC
invalid sample form (Figure 7-4) is attached to the data sheet. The sites will be notified in the
analytical reports of any invalid samples. I f the site seems to have problems taking a valid
sample, normally two voids in a row, the site task leader will work with the site personnel to
eliminate the problem.
glp/D:\SECT7.WPD
Project No. Element No. Revision No Date Page
*ERG EASTERN RESEARCH GROUP. INC.
INVALID SAMPLE FORM Site Code: .__
City: ; State:
Sample Collection Date: ; Operator:
Sample Canister Number: •
Sample Duplicate for this Date: Yes • No •
If Yes, Duplicate Canister Number: .
Reason for Invalid or Missed Sample:
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Average NOx Analyzer Reading for this Collection Date:
Wind Speed: Wind Direction: •
Rotameter Numbers: . 'Rotameter Indicated Flow Rate:
Average Barometric Pressure (mm Hg or inches Hg):
Ambient Temperature (°F): Relative Humidity:
Sky/Weather Conditions:
Received By: Date: ._ Action Taken:
Resolution:.
Field Invalid or In-house Invalid
Figure 7-4. NMOC Invalid Sample Form
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Project No. 0121.00 Element No. B2 Revision No. 1 Date March 2000 Page 6 of 17
7.1.3 NMOC Sample Analysis Fonns
The ERG NMOC analyst completes the canister sample data sheet-NMOC section and
NMOC daily HP5880 calibration form (Figure 7-5), which must include the following items:
• Critical instrument parameters (check-list format)
• Sample canister number
• Analysis date
Sequential ERG ID
• The analyst's name
• Calibration cylinder used
• Analysis start time
• Results of the NMOC analysis (individual replicates and NMOC average)
The information from the daily calibration form is added to the computer data file.
NMOC daily HP5880 Calibration forms are filed consecutively by ERG Sample ID number in a
three-ring analysis notebook for permanent record.
7.1.4 NMOC Canister Log
All canisters are cleaned prior to reuse using ERG SOP-MOR-062. All canisters,
whether used for NMOC, UATMP, or PAMS, are cleaned by the same procedure and are entered
into the canister cleanup log, shown in Figure 7-6.
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*EKG E A S T E R N R E S E A R C H G R O U P . I N C .
Date:
FID Instrument (A-D):
'Hydrogen Pressure:
Air Pressure:
NMOC Daily HP5880 Calibration Form
. Analyst
Propane Calibration Cylinder No.:
Label Concentration:
Actual Concentration:
ppmC Propane
Initial Daily Calibration:
Time:(DST) ;
Zero Air AC
X =
Rropane AC
Calibration Factor ppmC Propane
(Propane AC - Zero Air AC)
ppmv
ppmv
Final Calibration:
Time:(DST) _
Zero Air AC
[(
Propane AC
) - ( )]
X = > X =
Calibration Factor = ppmC Propane fProDane AC - Zero Air A O
j : , : } ; [( ) - ( )]
Figure 7-5. NMOC Daily HP 5880 Calibration Form
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Project No. Element No. Revision No. Date Page
Canister Cleanup Log
Can #
Cyc. 1 Cyc. 2 Cyc. 3 Pre
ppmC Post AC
Post ppmC
Final V
Date/ Initials Can # V P V P V P
Pre ppmC
Post AC
Post ppmC
Final V
Date/ Initials
V
!
« >
•
1
AC = Area Counts Figure 7-6. Canister Cleanup Log
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7.1.5 Canister Analytical Routing Schedule
The canisters received from the monitoring sites are placed in the laboratory by ERG
staff. The canisters are analyzed daily in the ERG RTP laboratory.
For the sites at which 3-hour air toxics will be analyzed, ten 3-hour air toxics samples per
site are selected from the NMOC samples at random. After NMOC analyses (PDFID), the
samples are sent to the ERG Air Toxics Laboratory for UATMP and speciated NMOC/PAMS
(GC/FID/MSD) analysis.
7.1.6 SNMOC/UATMP/PAMS Analysis Log
The SNMOC/UATMP/PAMS analysis log is shown in Figure 7-7 (Parts 1 and 2). The'
log is generic and is bound into a book with hard covers. The column headings on the log sheet
are given below, followed by a description of the information contained in the various cells for
the SNMOC, UATMP, or PAMS analyses:
UATMP sample identification.
UATMP site code.
DATA FILE NAME The data file number used by the Perkin Elmer
Turbochrom®, Analytical Software and the Hewlett Packard Chemstation® Software programs.
SAMPLE DATE Date the sample was taken.
ANALYSIS DATE Date the analysis was performed.
SAMPLE ID
FIELD ID
glp/D:\SECT7.WPD
</> m o UATMP Analysis Log
o Sample ID Field ID
Data File Name
Sample Date
Analysis Date
Standard Ref. No. Method
EM Voltage
. _.. - - -,- ,. - •- •• • -•• — • - - --
ere CD J2. CD o
o 3
o
3
2; o o •
o
C3 o cr to o o o
o to
to o o
Figure 7-7. UATMP Analysis Log
UATMP Analysis Log
Load Volume Can No. Analyst Comments Inches Hg Liters Can No. Analyst Comments
. _
Figure 7-7. (Continued)
STANDARD REF. NO.
METHOD
EM VOLTAGE
LOAD VOLUME
CAN NO.
ANALYST
COMMENTS
Project No. 0121.00 Element No. B2 Revision No. 1 Date March 2000 Page 12 of 17
Standard reference number. For samples and system blanks the column is left blank or indicated by "NA."
Method used to acquire data in HP Chemstation.
The electron multiplier voltage of the instrument.
Inches Hg - Canister pressure in inches of mercury. This column is not used because the volume is given in liters.
Liters - The load volume is recorded in liters according to the autosampling system.
Canister reference number
Analyst initials.
Any appropriate comments relative to the analysis.
7.2 Carbonyl Sample Custody
Figure 7-8 shows the multipage field data and custody sheet used for all carbonyl
sampling documentation. A field data sheet is shipped to the site with blank carbonyl tubes if the
tubes are provided by ERG, or blank data sheets are provided to sites supplying their own tubes
for sampling. After sampling, the field data sheet is completed by the site operator and a copy
retained for site records. The carbonyl sample tubes and field data sheet are shipped to the
analytical laboratory.
When samples are received, they are recorded in the sample receipt logbook (see
Figure 7-2), given an ERG sample ID number, and logged into the computerized database. The
database records each carbonyl sample and the field data sheet are put into a bag labeled with the
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*£RS E A S T E R N R E S E A R C H G R O U P . I N C .
Shipped
Recv'd
CARBONYL DATA SHEET
City Site Operator
AIRS No.
PAMS
SAMPLE DATE/TIME
SAMPLE DURATION
SAMPLE VOLUME LOT NUMBER
SAMPLE ID NUMBER
NMOC/TOXICS
Date
Lab ID
Duration
Rotameter Reading: @ set up
Rotameter Number
Lot Number
@ recovery
Volume (calculated by Lab)
Comments:
V
White - Lab Canary -' Receiving Pink - Sampler/Local Program
Figure 7-8. Carbonyl Field Data Sheet
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ERG ID number, site code, sampling date, individual tube designations, and date of receipt and
initials of receiving personnel. This sample bag is stored in a refrigerator designated for carbonyl
samples.
7.3 HAPs Sample Custody
Documentation while in the field monitoring phase of the program will use preformatted
forms. Field testing personnel will record data on a "Field Data Sheet." The field data sheet
provides for documentation of time, date, location, meteorological parameters and possibly some
laboratory parameters. Other documentation that will be used in the field is the identification
label shown in Figure 7-9. If Corrective Action is required during the portion of field
monitoring activities, the reason for the correction and action taken will be documented on the
"Corrective Action Report" (Figure 7-10). All forms will be written in indelible ink. I f
correction is required on the form, a single line will be drawn through the erroneous entry and the
correction will be dated and initialed. Any blank spaces will have a line drawn through to ensure
that the space is not filled in later. AH corrections will be authorized by the Site Coordination
Task Leader.
All analytical laboratories will provide sample tracking forms, narratives describing any
anomalies and any modifications to analytical procedures, data and sampling handling records,
and laboratory notes for inclusion in the final report. All laboratory electronic records will be
recorded for archive on magnetic media, and all hardcopies of raw data will be included in the
project archive file. *
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Project No. 0121.00 Element No. B2 Revision No. 1 Date March 2000 Page 15 of 17
Site Name
Site Address
Sampler Identification
Sample Type
Sampling Period
Date Collected
Signature
Figure 7-9. Label for Sample Identification
All records generated by measurement activities are signed or initiated by the person
performing the work and reviewed by an appropriate supervisor. Measurement results become
part of a project report which is reviewed by a technical reviewer. All notebooks are kept in
black ink, dated and signed by the person making the entries, and routinely inspected by the
appropriate supervision, as evidenced by his/her initials and data of inspection. Laboratory
notebook maintenance procedures are regulated by Standard Operating Procedures.
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Project No. 0121.00 Element No. B2 Revision No. 1 Date March 2000 Page 16 of 17
Corrective Action Report
Originator: Date:
Project Number: Corrective Action Number:
Description of Problem: (Give Date and Time Identified)
State Cause of Problem:
State Corrective Action Planned: (Include Persons Involved in Action)
QA Officer Comments:
Signatures: Project Manager Comments:
QA Officer:
Project Manager Comments:
Project Manager:
Project Manager Comments:
Originator:
Project Manager Comments:
Figure 7-10. Corrective Action Report
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7.4 Sampling Monitoring Data
All data sheets from the monitoring sites will be collected at the end of each monitoring
episode by the Task Leader and maintained in his custody throughout the monitoring program.
The data sheets will be released to the report writer after a thorough debriefing. The original
field data will remain in ERG custody and eventually stored on file with the final report.
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SECTION 8
ANALYTICAL METHODS REQUIREMENTS
Analytical procedures are program-specific because the instrumentation and the target
compounds of the four programs differ. The primary analytical instrument is PDFID for NMOC;
GC/FID/MSD for SNMOC, UATMP, VOCs and PAMS hydrocarbons; HPLC for carbonyls for
UATMP and PAMS; GC/MS for Semi volatile? and Phosgene; GC/ECD for Ethylene Oxide;
.HRMS for Dioxin/Furan; and ICPMS for Metals. All samples taken for SNMOC, UATMP, or
PAMS hydrocarbons can be evaluated for any of these parameters because the instrumentation is
currently collecting the same data.
8.1 Canister Cleanup System
A canister cleanup system (Figure 8-1) has been developed and is used to prepare sample
canisters for use and reuse after analysis (Standard Operating Procedure, ERG-MOR-062). An
oil-free compressor with an 80-gallon reservoir provides source air for the system. The
compressor was chosen to minimize hydrocarbon contamination. A coalescing filter removes
water mist and particulate matter down to a particle size of 10 microns and permeation dryers
remove water vapor from the compressor source air. The permeation dryers are used with a
moisture indicator to show detectable moisture in the air leaving the dryer.
Next, air is passed through catalytic oxidizers to destroy residual hydrocarbons. The'
oxidizers are followed by in-line filters for secondary particulate matter removal, and by
cryogenic traps to condense any residual water and organic compounds not destroyed by the
catalytic oxidizers. A single-stage regulator controls the final air pressure in the canisters and a
metering valve is used to control the flow rate at which the canisters are filled during a cleanup
cycle. The flow direction is controlled by a separate rotameter, installed in the clean, dried air
glp/D:\SECT8.-WPD
5.ty Filter Assembly
Air Compressor
Air Flow Rotameters
Dry Rotameter
_ . Air Cryolrap Pressure _ . . . Regulator Purge Valves
LU—1> ,_, Flow
Controller
2£
Catalytic Oxidizers
Cryolrap Purge Valve
Air Bypass -
Roughing
Pump
8-Port Manifold
D O O D D D D D D D O D D O D D
8Port Manifold
To Cert if leal ion System
o/&'g/mor/33961099T7-1 .b'f
A. Manifold Air Pressure Valve B. Manifold Vacuum Valve
C. Manifold Pressure Release Valve
D. Manifold Port for Connecting Canisters to be Cleaned
Figure 8-1. Canister Cleaning Apparatus
Project No. Element No. Revision No. Date
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line. A shutoff valve exists between the clean dried air line and the humidifier system (which is
made up of a SUMMA® treated 6-liter canister partially filled with HPLC-grade water). One
flowmeter and flow-control valve route the cleaned, dried air into the 6-liter canisters, where it. is
bubbled through the HPLC-grade water; a second flow-control valve and flowmeter allow air to
bypass the canister/bubbler. By setting the flow-control valves separately, the downstream
relative humidity can be regulated. A setting of 100% relative humidity is used for canister
cleaning with the wet rotameter on and the dry rotameter off. Another shutoff valve is located
between the humidifier and each 8-port manifold where the canisters are connected for cleanup.
The vacuum system consists of a Precision Model DD-310 turbomolecular vacuum
pump, a cryogenic trap, an absolute pressure gauge, and a manifold vacuum valve connected as
shown in Figure 8-1. The cryogenic trap prevents the sample canisters from being contaminated
by back-diffusion of hydrocarbons from the vacuum pump into the cleanup system. The
manifold vacuum valves enable isolation of the vacuum pump from the system without shutting
off the vacuum pump. . . .
After sample analyses are completed, a bank of eight canisters is connected to each
manifold as shown in Figure 8-1, with each canister valve open and the air pressure, vacuum,
and bellows valves closed. The vacuum pump is started and one of the bellows valves is opened,
drawing a vacuum on the canisters connected to the corresponding manifold. After reaching
10 mm Hg absolute pressure, as indicated by the absolute pressure gauge, the vacuum is
maintained for 30 minutes. The bellows valves are then closed and the cleaned, dried air that has
been humidified is introduced into the evacuated canisters at a rate of 7.0 liters per minute until
the pressures reach approximately 20 psig. This flow rate has been recommended by the _
manufacturer as the highest flow rate at which the catalytic oxidizers can handle elimination of
.hydrocarbons with a minimum of 99.7% efficiency. The evacuation and pressurization of the
canisters constitutes one cleanup cycle.
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Project No. 0121.00 Element No. B3 Revision No. 1 Date March 2000 Page 4 of 17
The cleanup cycle is repeated twice more during the canister cleanup procedure.
Following the third pressurization, the canister valves are closed and the canister that had the
highest pre-cleanup concentration is selected for cleanliness verification. The cleanliness of the
canister is qualified by GC/MSD analysis (one canister per bank of cleaned canisters - one
canister per eight cleaned). Upon meeting the cleanliness criterion of the programs, the canister
is reconnected to the cleanup manifold. All canister valves are opened and the canisters are
evacuated to approximately 0.5 mm Hg absolute pressure a fourth time,-in preparation for
shipment to the site.
8.2 NMOC Analytical Systems
Two modified Hewlett-Packard Model 5880 dual-channel FID chromatographs are used
to determine the NMOC concentrations in the ambient air samples shipped daily to the ERG RTP
laboratory. Figure 8-2 shows a diagram of one NMOC system channel; four analytical channels
are designated as ERG Channels A, B, C, and D. A specific volume of sample is drawn from the
canister into a cryogenic trap and cooled with liquid argon. The NMOC fraction is condensed in
the sample trap. The 6-port valve is changed to the "Inject" position, the liquid argon is
removed, and the oven door of the chromatograph is closed. The oven is heated to 90°C at
30°C/min, and the NMOC is carried into the FID by the helium carrier gas. The results are
reported on the integrating recorder of the instrument. The analytical procedure described is the
PDFID method and is described in detail elsewhere.''•2'410)
Sites requesting 3-hour toxic analysis will have selected samples analyzed by
GC/FID/MSD. The analytical procedures for the GC/FID/MSD are described in Section 8.4. .
Sites requesting carbonyl analysis will have samples analyzed by the HPLC. The
analytical procedures for the HPLC are described in Section 8.5.
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Absolute Pressure Gauge
Pressure Regulator
Vacuum Valve
Vacuum Pump
Dewar Flask
Glass Beads
Vent (excess)
1
Canister \ / Valve Y (optional fine
A ™ Canister
-O
1 1
Rotameter i FID
i
Integrator Recorder
Gas Purifier
Pressure Regulator
o/s/g/mor/33961099Zf7-2.tif
Figure 8-2. Schematic of Analytical Systems for NMOC glp/D:\SECT8.WPD
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8.3 SNMOC Analytical Systems
The SNMOC and 3-hour toxic analysis'samples are analyzed by the same procedures
described for UATMP GC/FID/MSD in Section 8.4. The list of SNMOC target compounds is
shown in Table 3-1.
Sites requesting carbonyl analysis will have samples analyzed by the HPLC. The
analytical procedures for the HPLC are described in Section 8.5.
8.4 UATMP and Concurrent Analytical System
The UATMP GC/FID/MSD analyses are performed on a 400 mL sample from the
canister with a Hewlett Packard 5890 Series II GC and a Hewlett Packard 5971 Mass Selective
Detector using a 60 m by 0.32 mm ID and a 1pm film thickness J&W DB-1 capillary column
followed by a 2:1 splitter that sends the larger portion of the column effluent to the MSD and the
smaller fraction to the FID. Table 8-1 shows the GC/FID/MSD operating conditions. Figure 8-3
shows the GC/FID/MSD system arrangement. The list of UATMP target compounds is shown
in
The chromatograph oven, which contains the DB-1 capillary column, is cooled to -50°C
with liquid nitrogen at the beginning of the sample injection. This temperature is held for five
minutes and then increased at the rate of 15°C per minute to 0°C. The temperature is then
ramped at 6°C per minute to 150°C, then ramped at 20°C per minute to 225°C and held for
8 minutes. The gas eluting from the DB™-1 capillary column goes through the 2:1 fixed splitter,
which divides the flow to the MSD and FID.
The analytical procedure for UATMP carbonyl analysis performed by HPLC is described
in Section 8.5 for PAMS carbonyl analysis, '
Table 3-2.
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Table 8-1
UATMP GC/FID/MSD Operating Conditions
Parameter Operating Value
Sample Volume 400 mL
J&W DB-l Capillary Column: Length Inside diameter Film thickness Oven temperature
60 m 0.32 mm
1 (im
-50°C for five minutes, 15°C/min to 0°C
then 6°C/min to 150°C, then 20°C/min to 225°C for 8
minutes
Temperatures: FID Injector Oven Temperature Auxiliary Temperature
300°C 210°C 278°C
Gas Flow Rates: Helium Carrier Gas Helium Make-up H 2 to FID Air to FID
1.5 mL/min 30 mL/min 30 mL/min
300 mL/min
Entech Sample Interface Conditions
Module 1 - Glass Bead Trap Initial Temperature Module 2 - Tenax® Trap Initial Temperature Module 3 - Cryofocuser Temperature
-180°C -40°C
-180°C
glp/D:\SECT8.WPD
6L S a m p l e Canisters
En tech 7000
Preconcen t ra to i
16-port Entech Autosampler
HP 5971 Mass Spect rometer
Detector
0.53 m m Silica C o a t e d
Guard C o l u m n
HP 5890 Series II Gas C h r o m a i o g a p h
Persona) C o m p u t e r suppl ied with
PE Turbocarbon for FID Peak Ident i f icat ion a n d Entech Software
Personal C o m p u t e r Suppl ied with
HP Chemsto t lon - for Mass Spectra
Ident i f icat ion
Nell son Analyt ical
A/D Inter face
Co lumn : J&WDB- l * Capi l lary C o l u m n
1 u FPm Thickness 6 0 m x 0 . 3 2 m m
Low D e a d Volume Stainless Steel Union
3:1 sp l l t -0 .5mi to FID-1 ml to MS
CSQ CD
a as CD ^
O 2
z o
tji ^} 1-1
3 a>' rt Z-o •
o o OO £3* i—'
O K ) ^
— o w o - J O i—' U ) o Figure 8-3. Gas Chromatograph/Mass Spectrometer/FID System
Project No. Element No. Revision No Date Page
8.5 PAMS Analytical Systems
The following analyses are included in the PAMS program.
The PAMS hydrocarbon samples are analyzed by the same procedures described for the
Concurrent GC/FID/MSD in.Section 8.4, with the target list shown in Table 3-3.
The PAMS and UATMP carbonyl samples are stored in the refrigerator after they are
received from the field prior to analysis. Sample preparation is performed by removing the
DNPH cartridge from its shipping vial and attaching it to the end of a 5-mL Micro-Mate glass
syringe. Four mL of acetonitrile is added to the syringe and allowed to drain through the
cartridge into a graduated centrifuge tube. After drainage has stopped, the extract is diluted with
acetonitrile to the 4-mL mark and mixed. This solution is then transferred to a 4-mL sample vial
fitted with a Teflon®-lined, self-sealing septum'and stored in a refrigerator until analysis is
performed.
The analytical separation of carbonyls is performed using either a Varian® 9000 HPLC or
a Waters HPLC configured with a 25 cm by 4.6 mm C-18 silica analytical column with a
5 micron particle size. A typical HPLC system is shown in Figure 8-4. ERG's system uses a •
Nelson Analytical A/D interface as the data system. Typically, 20-uL samples are injected with
an automatic sample injector. A mobile phase gradient of water, acetonitrile, and methanol is
used to perform the analytical separation at a flow rate of 1.0 mL/min. A multiwavelength
UV detector is .used at 360 nm.
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glp/D:\SECT8.WPD
m o
a
Column
Mobile Phase
OQ D ^ W J
2 o
3 CD
o
o
o
Figure 8-4. HPLC System o
- J
l - t o cr O o o
o
o o
Project No. Element No. Revision No. Date
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8.6 Semivolatile Analytical Systems
Sampling modules containing XAD-2® and petri dishes containing filters, together with
Chain of Custody forms and all associated documentation, will be shipped to the ERG laboratory
from the field. Upon receipt at the laboratory, samples will be logged into the laboratory sample
tracking system and sent to the sample preparation laboratory. Sample preparation and analysis
procedures are based on SW-846 Method 3542 and SW-846 Method 8270.
To prepare the samples for analysis, a large Soxhlet extractor, containing approximately
500 mL of methylene chloride and several boiling chips is assembled. The sorbent from the
PS-1 sampling module is spiked with Method 8270 surrogate Compounds, and the XAD-2® is
placed in the Soxhlet extractor. Surrogate compounds are spiked into all of the samples,
including field sample and blanks. The filter from the associated petri dish is added to the top of
the XAD-2®. (If a field blank is to be prepared, clean XAD-2® and a clean filter from the same
batch as the filter and resin used for the field samples are used instead of the sampled resin and
filter.) The samples and blanks are extracted for 18 hours, and the round bottomed flask
containing the extracted sample is removed from the extractor.
A Kuderna-Danish apparatus with a 10 mL concentrator tube is assembled. A piece of •
pre-extracted glass wool is placed in a glass funnel and 20g of anhydrous Na2S04 is placed in the
inlet of the Kuderna-Danish apparatus. The round bottomed flask is rinsed three times into the
funnel with 10 mL aliquots of methylene chloride. A 3-bali macro Snyder column is pre-wetted
with methylene chloride and attached to the Kuderna-Danish inlet. The entire apparatus is placed
on a water bath at 85°C. The concentrator tube is half-immersed in the water bath, and the flask
is bathed in water vapor. The apparatus is removed from the water bath when an apparent'
volume of 5 mL is observed in the concentrator tube. The solvent is allowed to drain for
5 minutes. The Snyder column is rinsed with 1 mL of methylene chloride and allowed to drain
into the concentrator tube. The concentrator tube is removed from the evaporator, and a 2-ball
macro Snyder column is attached to the concentrator tube and pre-wetted with 2 mL of
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methylene chloride. The apparatus is placed on the water bath and the sample concentrated to
2 mL. The Snyder column is removed and the volume is brought up to 5 mL with methylene
chloride. The extract is placed in a vial with minimal headspace, the solvent level is carefully,
marked, the vial is labeled, and placed in storage at 4°C until analysis.
Sample extracts will be analyzed for semivolatile organic compounds using the analytical
procedures of SW-846 Method 8270. Instrument operating conditions are shown in
Method 8270 and the laboratory standard operating procedure. The mass spectrometer will be
tuned and mass calibrated as required using peffluorotributylamine (FC-43), as per the
manufacturer's instructions. The tune of the instrument is verified by injecting 50 ng of
decafluorotriphenylphosphine (DFTPP) and checking the ion abundance criteria against the ion
abundance criteria listed in Method 8270. If the DFTPP mass spectrum does not meet method
specifications, the DFTPP is re-analyzed or the mass spectrometer is re-tuned so that the
instrument will meet the tuning criteria. The DFTPP tune criteria must be met before analysis of
samples can begin. The acceptability of the instrument tune will be verified by analysis of the
DFTPP solution every twelve hours.
Method 8270 calibration procedures and criteria apply. Calibration check compounds
and system performance check compounds must meet the criteria outlined in Method 8270. A 9
multipoint calibration is performed initially to determine system response factors for the
compounds of interest; system calibration is verified daily (or every 12 hours) by analyzing a
mid-level calibration standard in accordance with Method 8270 specifications. All samples will
be spiked with Method 8270 internal standards immediately prior to analysis.
A solvent blank is analyzed prior to sample analysis to demonstrate that the analytical
system is free from contamination. Internal standard area counts for each sample analysis must
be between 50 and 150% of the last daily calibration standard, in accordance with Method 8270
specifications. Surrogate compound recoveries1 for each sample are checked against
Method 8270 surrogate spike recovery limits for soil/sediment samples. - Surrogate compound
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recoveries from the XAD-2® and the sample matrix used in this work have not been established
experimentally; recoveries of the listed compounds from XAD-2® will be determined
experimentally prior to the initiation of the monitoring program. Samples will be re-analyzed if
surrogate compound recoveries fall below the levels specified in Method 8270. In order to
evaluate recoveries of compounds of interest from XAD-2®, a method detection limit study will
be performed using spiked XAD-2® and the procedures of 40 CFR Part 136B.. The spiked
samples will be subjected to the same sample preparation procedures as the samples generated in
the field.
Criteria for identification of the mass spectra of the compounds of interest are positive
matching of the relative retention times and the mass spectra of the sample and the standard
components in accordance with the specifications of Method 8270. Quantitative analysis is
achieved by the use of automated procedures in'the Hewlett-Packard data system. Mass spectral
interpretation of tentatively identified compounds (if performed) will be verified manually by
experienced interpreters of mass spectral data using the NBS reference library, with automated
semi-quantitative analysis achieved by comparison of the peak area of the tentatively-identified
compound to that of the closest-eluting standard.
The compounds of interest and iexperimental method detection limits are shown in
Table. 8-2.
8.7 Ethylene Oxide by Gas Chromatograph Analytical Systems
Ethylene Oxide samples are stored in the refrigerator after they are received from the field
prior to analysis. Sample preparation is performed by scoring the sample tube with a file and
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Table 8-2
Semivolatile Organic Compounds to be Analyzed by the Analytical Procedures of Method 8270; with Method Detection Limits
Compound MDL
0*gj Compound MDL > g )
acenaphthene. 5.82 2-methylphenol 9.44
acenaphthylene 8.87 4-methylphenol 7.69
acetophenone 13.87 naphthalene 15.46
aniline 16.20 1-naphthylamine 5.42
anthracene 17.06 2-naphthylamine 10.22
4-aminobiphenyl 9.60 2-nitroaniline 12.30
benzidine 0.00 3-nitroaniline 8.70
benzoic acid 12.3d 4-nitroaniline 10.40
benzo(a)anthracene 8.33 nitrobenzene 24.86
benzo(b)fluoranthene 17.34 2-nitrophenol 10.07
benzo(k)fluoranthene 23.61 . 4-nitrophenol 7.36
benzo(g,h,i)perylene 15.05 N-nitroso-di-n-butylamine 22.42
benzo(a)pyrene 18.17 N-nitrosodiphenylamine 50
benzyl alcohol 8.15 N-nitrosodipropylamine 21.48
bis(2-chloroethoxy)methane 14.03 N-nitrosopiperidine 17.32
bis(2-chloroethyl)ether 11.66 pentachlorobenzene 9.74
bis(2-chloroisopropyl)ether 11.07 pentachloronitrobenzene 10.37
bis(2-ethylhexyl) phthalate 11.62 pentachlorophenol 14.74
4-bromophenyl phenyl ether 11.30 phenanthrene 10.29
butyl benzyl phthalate 11.66 phenol 22.48
4-chloroaniline 16.83 2-picoline 11.15
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Table 8-2
(Continued)
Compound MDL (Hg) Compound
MDL (^g)
1 -chloronaphthalene 30.03 pyrene 10.54
2-chloronaphthalene 18.48 1,2,4,5-tetrachlorobenzene 10.54
4-chloro-3-methylphenol 16.80 2,3,41,6-tetrachlorophenol 9.67
2-chlorophenol 9.99, 1,2,4-trichlorobenzene 13.62
4-chlorophenyl phenyl ether 6.79 2,4,5krichlorophenol 6.90
chrysene 10.57 2,4,6-trichlorophenol 8.35
dibenz(a,h)anthracene j 15.85 diphenylamine 25.39
dibenzofuran \ 9.28 1,2-diphenylhydrazine 50
di-/z-butyl phthalate 14.01 ' dir«-octyl phthalate 13.19
1,3-dichlorobenzene 12.05 fluoranthene 14.49
1,4-dichlorobenzene 10.86 fluorene 10.01
1,2-dichlorobenzene t 10.96 hexachlorobenzene 14,12
3,3'-dichlorobenzidine \ ' 8.95 hexachlorobutadi ene 13.23
2,4-dichloro phenol , 14.55 hexachlorocyclopentadiene 21.74
2,6-dichlorophenol 18.10 hexachloroethane 5.65
diethyl phthalate 7.20: inderio( 1,2,3 -cd)pyrene 14.56
p-dimethylaminoazobenzene 50 !: isophorone 22.61
7,12-dimethylbenz(a)anthracene ; 19.04 methyl methanes ulfonate 16.50
a-, a-dimethylphenethylamine 1 oov 2-methylnaphthalene 11.36
2,4-dimethylphenol 17.64 2,4-dinitrophenol 10.05
dimethyl phthalate 9.15 2,4-dinitrotoluene 9.71
4,6-dinitro-2-methylphenol 11.31 2,6-dinitro toluene 9.38
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Table 8-2
(Continued)
removing the front sorbent section and first glass wool plug to a 2 mL vial. The middle glass
wool plug and back sorbent section goes into another vial. One milliliter of
dimethylformamide(DMF) is added to each vial and they are capped. Each sample is shaken for
10 seconds and allowed to stand for 5 minutes. A 20 pL aliquot of the DMF solution is
transferred to another 5 mL vial containing 2.0 mL 2% N-heptafluorobutyrylimidazole (HFB1)
(v/v) in isooctane. Each sample is shaken for 1 minute to ensure complete hydrolysis of excess
HFB1 forming 2-bromoethylheptafluorobutyrate. One milliliter of this sample is transferred to a
2 mL vial and analyzed by GC/ECD.
The analysis of 2-bromoethylheptafluorobutyrate is performed using a Varian® 9000 GC
equipped with an ECD detector. This system is configured with a 3m by 4 mm glass column
with 10% SP-100 on 80/100 Chromosorb WHP; ERG's system uses a Nelson Analytical
A/D interface as the data system. Typically, 1-uL samples are injected with an automatic sample
injector. The carrier gas composition for the analysis is 5% methane in argon at 25 mL/minute.
The detection range for the ethylene oxide analysis is 2 to 42 pg ethylene oxide per sample.
8.8 DioxinVFuran by High Resolution Mass Spectroscopy Analytical Systems
After receipt of the sample shipment, the samples are checked against the Chain-of-
Custody forms and then assigned an analytical laboratory sample number. Each sample
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component is examined to determine if damage occurred during travel. Color, appearance, and
other particulars of the samples are noted. Samples are extracted within 21 days of collection
and processed through cleanup procedures before concentration and analysis.
The analytical procedure used to obtain PCDD/PCDF concentrations uses high resolution
gas chromatography (HRGC) coupled with high resolution mass spectrometry (HRMS), with a
resolution from 8000-10000. Dioxin 2,3,7,8-tetrachlorpdibenzo-p-dioxin is to be analyzed by
Columbia Laboratories, Inc., using Compendium Method TO-9A and Method 8290.
In case of a failure in the analytical system, Columbia Laboratories will be responsible
for corrective action.
8.9 Metals Using an Inductively Coupled Argon Plasma Mass Spectroscopy Analytical System
After receipt of the sample shipment, the samples are checked against the Chain-of-
Custody forms and then assigned an analytical laboratory sample number. Each sample
component is examined to determine if damage occurred during travel. Color, appearance, and
other particulars of the samples are noted. Samples are extracted within according to standard
procedures determined by First Analytical.
The analytical procedure used to obtain the metal concentrations uses inductively coupled
argon plasma mass spectrometry (ICPMS). The metals are to be analyzed by First Analytical,
using approved methods as published in 40 CFR Parts 50, 51, and 58.
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SECTION 9
QUALITY CONTROL REQUIREMENTS
This section describes the quality control requirements performed under each of the major
program components (NMOC, SNMOC, UATMP, Carbonyls, PAMS, and HAPS).
9.1 . Sample Canister Cleanup Studies
Before any samples are collected for a program, all stainless steel sample canisters are
checked for leaks. The canisters are filled to about 15 psig pressure with zero-grade air from a
cylinder and the valve.and fittings are checked for leaks. The canisters are then cleaned using the
procedure described in Section 9.
After cleanup, each canister is analyzed and the results are noted on the custody form for
the permanent record. In order for the canister to be used without further cleanup, the analysis
must show that it meets the quality objective for cleanliness.
9.2 Standard Traceability
The standards used for the NMOC/SNMOC and PAMS are vendor-supplied National
Institute of Standards and Technology (NIST) standards or referenced to a vendor-supplied NIST
standard. The standards used for UATMP are certified by comparison to external audit samples.
The SOP used to prepare standards is the SOP for Standard Preparation Using Dynamic Flow
Dilution, ERG-MOR-061.
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9.3 Accuracy and Acceptance
Because ambient air measurements encompass a range of mixtures of organic compounds
whose individual concentrations are unknown, defining absolute accuracy is not possible.
Instead, accuracy is determined relative to standards with internal and external audit samples.
9.3.1 NMOC Instrument Calibration
Accuracy is monitored throughout the program using in-hduse QC samples. On days
when ambient air samples are analyzed for NMOC content, an in-house QC sample of propane is
also analyzed. The QC samples are prepared by diluting dry propane with cleaned, dried air
using calibrated flowmeters. The concentration of the in-house QC samples will be set close to
the concentration levels seen in the ambient air samples.
9.3.2 SNMOC Instalment Calibration
Because all samples analyzed for volatile analyses utilize the same instrument and have
the potential to report all analytes possible, the hydrocarbon and TO-14A/TO-15 parameters
must pass the standard procedures' set; and listed in Tables 4-2 and 4-3.
Prior to sample analysis for SNMOC, a quality control standard, prepared using either a
Scott Specialty Gas or Spectra certified high pressure gas, is analyzed daily to ensure the
validity of the current monthly response factors. This standard will have an approximate range
from 15 ppbv to 40 ppbv.
For each detector, load volumes and the standard response area counts are entered into a
computer spreadsheet and the current monthly response factors are used to calculate propane
concentrations. The concentration is compared to the calculated theoretical concentrations of the
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QC standard. A percent bias less than or equal' to 30 percent for each compound is considered
acceptable.
If the QC standard does not meet the 30 percent criterion, a second QC standard is
analyzed. If the second QC standard meets the criterion, the analytical system is considered in
control. If the second QC check does not meet'acceptance criteria, a leak test and system
maintenance are performed. Following this, a third QC standard analysis can be performed. I f
the criterion is met by the third analysis, the analytical system is considered in control. I f
maintenance causes a change in system response, a new calibration curve is required.
A system blank of cleaned, humidified air is analyzed after the daily QC standard
analysis before the sample analysis. The system is considered in control i f the total NMOC
concentration for the system blank is less than or equal to 20 ppbC.
- 9.3.3 UATMP Instrument Calibration
The tune of the MSD is verified using 4-bromofluorobenzene (BFB) on a daily basis.
The tune is usually verified during the analysis of the QC sample. Before sample analyses, a
standard prepared at approximately 5 ppbv from a certified cylinder is used for a daily
calibration. The resulting response factors for each compound will be compared to the monthly
calibration curve response factors generated from the GC/MSD using the HP Chemstatioh®
Software. An absolute value of less than or equal to 30 percent is considered acceptable for the
quantitated compounds. If the first QC check does not meet this criterion, a second standard may
be analyzed. If the second QC standard is acceptable, sample analysis can continue. I f the
second check does not meet acceptance criteria, a leak check and system maintenance are •i
performed. If the system maintenance is completed and a third QC analysis meets the criterion,
then analysis may continue. If the maintenance causes a change in the system response, a new
calibration curve must be analyzed before sample analyses can continue.
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After acceptance of the daily standard, a system blank consisting of cleaned, humidified
air is analyzed. A total concentration of less than 0.2 ppbv (or the lowest quantitation limit,
whichever is smaller) per compound indicates that the system is in control. I f a concentration
greater than the acceptance criterion is detected, a second system blank is analyzed. If the second
system blank fails, system maintenance is performed. Another system blank can be analyzed and
if it is in control, ambient air samples are analyzed.
9.3.4 PAMS VOC Analysis
Daily QC checks for PAMS VOC analysis are the same as those described for SNMOC
in Section 9.3.2.
9.3.5 Carbonyl Compounds Analysis
Daily calibration checks are performed to ensure that the analytical procedures are in
control. Daily QC checks are performed after every 10 samples on the days that samples are
analyzed. Compound responses must be within 15% bias relative to the responses from the
current calibration curve. Compound retention time drifts are also measured from this analysis
and tracked to ensure that the HPLC instrument is operating within acceptable parameters.
If this daily QC check does not meet the criterion, a second injection of the QC standard
is performed. If the second QC check does notpass or i f more than one daily QC check does not
meet the criterion, a new calibration curve (5 concentration levels) is analyzed. All samples
analyzed with the unacceptable QC check will be reanalyzed.
An acetonitrile system blank is analyzed after the daily calibration check and before
sample analysis. The system is considered in control if target compound concentrations are less
than the current detection limits.
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9.3.6 Analysis of Semivolatile Organic Compounds Using EPA Method 8270
Prior to using Method 8270, the filter/sorbent samples are prepared for analysis using the
procedures of EPA Method 3542 (Appendix I). The extracts are analyzed by GC/MS, using a
fused silica capillary column and a mass spectrometer capable of scanning from 35 to 500 mass
units every 1 sec or less, using a nominal electron energy of 70 eV in the electron ionization
mode. The mass spectrometer must be capable of producing a mass spectrum for
decafluorotriphenylphosphine (DFTPP) that meets all of the acceptance criteria in Table 9-1
when 1 pL of the GC/MS tuning standard is injected through the GC.
Table 9-1
Decafluorotriphenylphosphine (DFTPP) Key Ions and Ion Abundance Criteria According to EPA Method 8270
Mass Ion Abundance Criteria
51 30-60% of mass 198
68 <2%ofmass69
70 <2%ofmass69
127 40-60% of mass 198
197 <1% of mass 198
198 Base peak, 100% relative abundance
199 5-9% of mass 198
275 ' 10-30% of mass 198
365 >1% of mass 198
441 Present but less than mass 443
442 >40%ofmass 198
443 .17-23% of mass 442 ' *
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The Method 8270 surrogate compounds will be used to spike the sorbent immediately
before extraction. These surrogate compounds are phenol-d6, 2-fluorophenol,
2,4,6-tribromophenol, nitrobenzene-d5, 2-fluorobiphenyl, and /?-terphenyl-d14. Surrogate
recovery ranges have not been established for XAD-2® extraction; surrogate recovery acceptance
ranges from Method 8270 will be used as a guideline.
A GC/MS system performance check must be performed to ensure that minimum average
response factors are met before the multipoint calibration is used. For semivolatile organic
compounds, the System Performance Check Compounds are N-nitroso-di-«-propylamine,
hexachlorocyclopentadiene, 2,4-dinitrophenol, and 4-nitrophenol. These System Performance
Check Compounds typically have very low response factors (0.1 - 0.2) and the response factors
tend to decrease as the chromatographic system begins to deteriorate or as the standard begins to
deteriorate. These compounds are usually the first to show poor performance, and these
compounds must, therefore, meet the minimum requirement when the system is calibrated.
After the analytical system performance check is met, the calibration check compounds
are used to check the validity of the initial multipoint calibration. These calibration check
compounds are acenaphthene, 1,4-dichlorobenzene, hexachlorobutadiene, N-nitroso-di-
phenylamine, di-«-octyl phthalate, fluoranthene, benzo(a)pyrene, 4-chloro-3-methylphenol,
2,4-dichlorophenol, 2-nitrophenol, phenol, pentachlorophenol, and 2,4,6-trichlorophenol. The
response factor for the calibration check compounds must be within ±30% of the mean response
factor from the initial calibration.
Internal standard responses and retention times must also be evaluated for stability. EPA
Method 8270 also presents detailed guidelines for qualitative analysis of mass spectra, as well as
a detailed analytical scheme to determine that all target analytes are quantitated relative to the
nearest-eluting internal standard.
9.3.7 Ethylene Oxide Analysis
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Daily calibrations with at least six working standards over the range of 1 to 42 pg
ethylene oxide per sample is performed to ensure that the analytical procedures are in control.
Daily QC checks are performed after every lO samples with response within 20% bias relative to
the responses from the calibration curve. Compound retention time drifts are also measured from
this analysis and tracked to ensure that the instrument is operating within acceptable parameters.
If this daily QC check does not meet the criterion, a second injection of the QC standard
is performed. If the second QC check does not pass or if more than one daily QC check does not
meet the criterion, a new calibration curve (6 concentration levels) is analyzed. All samples
analyzed with the unaccepted QC check will be reanalyzed. Three system blanks are prepared
and analyzed to ensure that the calibration graph is in control.
9.3.8 Analysis of Polychlorinated Dibenzodioxins Using EPA Compendium Method TO-9 and EPA Method 8290 .,
EPA Method 8290 provides procedures for the determination of polychlorinated dibenzo-
/7-dioxins (tetra- through octachlorinated dioxins) in a variety of environmental matrices at part-
per-trillion to part-per-quadrillion concentrations. The Method 8290 analytical methodology
requires the use of high resolution gas chromatography (HRGC) coupled with high resolution
mass spectrometry (HRMS). Method 8290 has been applied to water, soil, sediment, paper pulp,
fly ash, fish tissue, human adipose tissue, sludges, and still fuel oil but the sample preparation
and purification methodology of Method 8290 is not directly applicable to ambient air samples
collected on PUF according to EPA Compendium Method TO-9A. The analytical procedures of
EPA Method 8290, however, are directly applicable to the ambient samples generated by EPA
Method TO-9A.
A Soxhlet extraction using toluene is used to extract the dioxins/furans from the filter and
PUF sampling module. Ambient air samples do not generally require the extensive chemical
cleanup procedures described in Method 8290. Toluene extracts are concentrated and analyzed
by HRGC/HRMS.
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The HRGC/HRMS system is calibrated using isotopically labeled internal standards and
recovery standards, with a number of unlabeled analytes that are representative of the various
chlorine number congeners.
Prior to calibration, the HRMS is tuned to the manufacturer's specifications with a
minimum resolving power of 10,000 using perfluorokerosene. The lowest point of the
calibration is near but not at the method detection limit, and the upper point of the calibration is
adjusted to cover the anticipated concentration range of the samples. The calibration is
acceptable if the percent relative standard deviations for the mean response factors from the
17 unlabeled standards do not exceed ±20%, and those for the nine labeled reference compounds
do not exceed ±30%.
A'column performance check solution is used to verify that the performance of the
HRGC column meets method specifications. Because Method 8290 is based upon the
application of Selected Ion Monitoring techniques to identify and quantify the analytes, method
specifications for the required abundance ratios of chlorine isotopes at the different chlorine
numbers are presented. If at least two peaks of the chlorine isotope cluster at a given chlorine
number (i.e., pentachlorodibenzodioxin) are not present in the correct ratio relative to the
theoretical value, the compound cannot be identified as pentachlorodibenzodioxin.
Because additional air samples will not be available for preparation/analysis of a matrix
spike/matrix spike duplicate, a method spike/method spike duplicate will be prepared and
analyzed in the laboratory using clean sorbent media.
9.3.8 Quality Control Measures for Analysis of Airborne Metals Collected on a Filter
Analysis of the metals will be performed by inductively coupled argon plama mass
spectroscopy for antimony, arsenic, beryllium, cadmium, total chromium, lead, manganese and
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nickel, and by cold vapor atomic absorption spectrophotometry for mercury. Quality control
measures for the metals analysis are shown in Table 9-2.
9.4 Precision
Analytical precision is estimated by repeated analysis of samples. For all samples, the
second analysis is performed at least 24 hours after the first analysis. This procedure is followed
for the canister samples in particular to ensure that sufficient time has elapsed to allow the
canister contents to equilibrate with the solid surfaces and to allow any concentration gradients
within the canister to disperse.
Duplicate samples are reanalyzed once each to determine overall precision, including
sampling and analysis variability.
Precision estimates are calculated in terms of percent difference and absolute percent
difference. Because the true concentration of the ambient air sample is unknown, these
calculations are relative to the average sample concentration.
9.5 Completeness
Completeness, a quality measure, is calculated at the end of the program. Percent
completeness is calculated as the ratio of the number of valid samples received to the number of
scheduled samples (beginning with the first valid sample received through the last sample
received). This quality measure is presented in the final report.
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Table 9-2
Quality Control Measures for Metals Analysis
Parameter Frequency Acceptance Criteria Corrective Action
Multipoint calibration Daily Correlation coefficient > 0.995
1. Repeat analysis of calibration standards 2. Re-prepare calibration standards and re-analyze
Calibration check Daily Recovery 95-105% for all analytes
1. Repeat analysis of calibration check standard 2. Repeat analysis of calibration standards 3. Re-prepare calibration standards and re-analyze
Continuing calibration verification
Every 10 samples Recovery 90-110% 1. Repeat analysis of continuing calibration verification sample 2. Reprepare continuing calibration verification sample and re-analyze 3. Reanalyze samples since last acceptable continuing calibration verification
Method blanks Every 10 samples Analytes below method detection limit
1. Reanalyze 2. Reprepare blank and re-analyze 3. Correct contamination and reanalyze blank 4. Repeat analyses of all samples since last clean blank
Laboratory control sample One per sample batch Recovery 80-120% Reprepare sample batch; re-analyze
Method spike/method spike duplicate
one per sample batch Recoveries 80-120% Flag data.
001210 0003 TOW
T vu 9U<*01
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9.6 Representativeness
Representativeness measures how well the reported results reflect the actual ambient air
concentrations. This measure of quality can be enhanced by ensuring that a representative
sampling design is employed. This design includes proper integration over the desired sampling
period and following siting criteria established for each task. The experimental design for
sample collection should ensure samples are collected at proper times and intervals for their
designated purpose according to the data quality objectives. For example, NMOC/SNMOC
samples are collected to gain information about PAMS VOCs. Therefore, collection of 3-hour
samples from 6:00 a.m. to 9:00 a.m. each weekday is appropriate. Quality measures of duplicate
sample collection and replicate analyses are included.
9.7 Comparability
Comparability is a measure of how well the program data compare to like data. Sample
exchange is a means of determining comparability.
When EPA directs, an exchange of NMOC samples can be made with EPA-QAD and the
EPA's National Exposure Research Laboratory (NERL). SNMOC and PAMS samples can be
exchanged with EPA-NERL for concentration;comparisons and with GC/MSD for identification
confirmations. For sites choosing site support̂ an exchange of samples between the site's
analytical laboratory and ERG can be conducted. i
• t (
9.8 Lowest Quantitation Limits
For SNMOC, UATMP and carbonyls,"the lowest quantitation limits of the target
compounds are determined by performing seven replicate analyses of a standard that is at a
concentration within five times the expected quantitation limits. This procedure follows the
method listed in the Federal Register, Appendix B, Part 136.(17) The quantitation limits
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determined are verified by analyzing multiple injections of standards at the obtained limits to
confirm the reported lowest level concentration.:
The lowest quantitation limits for the SNMOC are listed in Table 9-3, for UATMP
compounds in Table 9-4, and for the carbonyl compounds in Table 9-5. All laboratories at
ERG's Morrisville location verify the lowest quantitation limits once a year by preparing and
analyzing the seven replicate standards. The semivolatile quantitation limits were presented
previously in Table 9-1. Dioxin and metal detection limits are summarized in the separate
subcontractor quality assurance plans.
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Project No. 0121.00 Element No. B4 Revision No. 1 Date March 2000 Page 13 of 16
Table 9-3
SNMOC Lowest Quantitation Limits
Compound Quantitation Limit (ppbC) Compound
Quantitation Limit (ppbC)
Acetylene/Ethane 0.62 . ; Meth'ylcyclohexane 3.72
Benzene 2.13 Methylcyclopentane 2.13
1,3-Butadiene 0.20 2-Methylheptane 4.73
«-Butane 0.20 3-Methylheptane 4.73
cz's-2-Butene 0.20 2-Methylhexane 3.72
/ra«5-2-Butene 0.20 3-Methylhexane 3.72 '
Cyclohexane 2.13 2-Methylpentane 2.13
Cyclopentane 0.37 3-Methylpentane 2.13
Cyclopentene 0.37 2-Methyl-1-Pentene 2.13
/7-Decane 4.60 4-Methyl-1-Pentene 2.13
1-Decene 4.60 /7-Nonane 4.60
m-Diethylbenzene 4.60 1-Nonene 4.60
/?-Diefhylbenzene 4.60 n-Octane 4.73
2,2 -Dimethy lbutane 2.13 1-Octene 4.73
2,3-Dimethylbutane 2.13 rc-Pentane 0.37
2,3-Dimethylpentane 3.72 1 -Peritene 0.37
2,4-Dimethylpentane 3.72 . cw-2-Pentene 0.37
n-Dodecane 4.60 trans-2-Venter\Q 0.37
1 -Dodecene 4.60 a-Pinene 4.60
2-Ethyl-l-Butene 2.13 P-Pinene 4.60
Ethylbenzene 4.73 Propane 0.31
Ethylene 0.62 «-Propylbenzene 4.60
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Project No. 0121.00 Element No. B4 Revision No. 1 Date March 2000 Page 14 of 16
Table 9-3
(Continued)
Compound Quantitation Limit (ppbC) , Compound
Quantitation Limit (ppbC)
m-Ethyltoluene 4.60 Propylene 0.31
o-Ethyltoluene 4.60 Propyne 0.31
p-Ethyltoluene 4.60 Styrene 4.73
//-Heptane 3.72 Toluene 3.72
1 -Heptene 3.72 «-Tridecane 4.60
«-Hexane 2.13 1 -Tridecene 4.60
1 -Hexene 2.13 "• 1,2,3-Trimethylbenzene 4.60
c/.s-2-Hexene 2.13 ' 1,2,4-Trimethylbenzene 4.60
trans-2-Hexene 2.13 1,3,5-Trimethylbenzene 4.60
Isobutane 0.20 2,2,3 -Trimethylpentane 4.73
Isobutene/1-Butene 0.20 . 2,2,4-Trimethylpentane 4.73
Isopentane 0.37 ; 2,3,4-Trimethylpentane 4.73
Isoprene 0.37 «-Undecane '4.60
Isopropylbenzene 4.60 1-Undecene 4.60
2-Methyl-1-Butene 0.37 . m.jC-Xylene 4.73
2-Methyl-2-Butene 0.37 o-Xylene 4.73
3-Methyl-1-Butene • 0.37
Project No. 0121.00 Element No. B4 Revision No. 1 Date March 2000 Page 15 of 16
Table 9-4
TO-15 Analyte Lowest Quantitation Limit (LQL)
Compound ppbv Compound ppbv
Acetylene 0.10 1 ;2-Dichloropropane 0.04 Propylene 0.10 Ethyl Acrylate 0.10 Chloromethane 0.13 Bromodichloromethane 0.05 Vinyl Chloride 0.06 : Trichloroethylene 0.04 1,3-Butadiene 0.09 "i
i
Methyl Methacrylate 0.07 Bromomethane . 0.1.4 c/.s-l,3-Dichloropropene 0.06 Chloroethane , 0.06 Methyl Isobutyl Ketone 0.07 Acetonitrile 0.57 ?ra«5-l,3-Dichloropropene 0.11 Acrylonitrile 0.21 1,1,2-Tri chloroethane 0.11 Methylene Chloride 0.09 Toluene 0.21 trans-1,2-Dichloroethylene 0.12 Dibromochloromethane 0.15 1,1 ,-Dichloroethane 0.10 ; «-Octane 0.21 Methyl tert-Butyl Ether 0.06 1 Tetrachloroethylene 0.22 Methyl Ethyl Ketone 0.17 Chlorobenzene 0.07 Chloroprene ; 0.10 Ethylbenzene 0.12 Bromochloromethane 0.09 m,p-Xy\ene 0.23 Chloroform 0.06 . ' Bromoform 0.15 Ethyl tert-Butyl Ether : 0.07 ! Styrene 0.10 1,2-Dichloroethane 0.06 1,1,2,2-Tetrachloroethane 0.17 1,1,1 -Trichloroethane 0.05 o-Xylene 0.10 Benzene 0.07 m-Dichlorobenzene 0.15 Carbon Tetrachloride 0.05 p-Dichlorobenzene 0.13 tert-Amyl Methyl Ether 0.07 o-Dichlorobenzene 0.16
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•
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Table 9-5
Carbonyl Lowest Quantitation Limits, Underivatized Concentration (ppbv)
COMPOUND SAMPLE VOLUME (L)
100 200 300 400 500 600 700 800 900 1000
Formaldehyde 0.03 0.02 0.011 0.008 0.006 0.005 0.005 0.004 0.004 0.003 Acetaldehyde 0.04 0.02 0.013 0.010 0.008 0.007 0.006 ' 0.005 0.004 . 0.004 Acrolein 0.05 0.02 0.016 0.012 0.010 0.008 0.007 0.006 0.005 0.005 Acetone 0.03 0.01 0.009 0.007 0.005 0.004 0.004 0.003 0.003 0.003 Propionaldehyde 0.02 0.01 0.006 0.005 0.004 0.003 0.003 0.002 0.002 0.002 Crotonaldehyde 0.04 0.02 0.013 0.010 0.008 0.006 0.005 0.005 0.004 0.004 Butyr/lsobntyraldehyde 0.05 0.02 0.015 0 011 0.009 0.008 0.006 0.006 0.005 0.005 Benzaldehyde 0.02 0.01 0.008 0.006 0.005 0.004 0.003 0.003 0.003 0.002 Isovaleraldehyde 0.10 0.05 0.034 0.025 0.020 0.017 0.014 0.013 0.011 0.010 Valeraldehyde 0.06 0.03 0.021 0.016 0.013 0.011 0.009 0.008 0.007 0.006 Tolualdehydes 0.09 0.05 0.031 0̂ 023 0.019 6.016 0.013 0.012 0.010 0.009 Hexaldehyde 0.04 0.02 0.013 0.010 0.008 0.006 0.006 0.005 0.004 0.004 2,5 -dimethy lbenzaldehy de 0.05 0.03 0.017 0.013 0.010 0.008 0.007 0.006 0.006 0.005
COMPOUND SAMPLE VOLUME (L)
1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
Formaldehyde 0.0029 0.0026 0.0024 0.0023 0.0021 0.0020 0.0019 0.0018 0.0017 0.0016 Acetaldehyde 0.0036 0.0033 0.0030 0.0028 0.0026 0.0025 0.0023 0.0022 0.0021 0.0020 Acrolein - 0.0044 0.0040 0.0037 0.0035 0.0032 0.0030 0.0029 0.0027 0.0026 0.0024 Acetone 0.0024 0.0022 0.0020 0.0019 0.0018 0.0017 0.0016 0.0015 0.0014 0.0013 Propionaldehyde 0.0017 0.0016 0.0015 0.0014 0.0013 0.0012 0.0011 0.0011 0.0010 0.0010 Crotonaldehyde 0.0035 0.0032 0.0029 0.0027 0.0025 0.0024 0.0022 0.0021 0.0020 0.0019 Butyr/Isobutyraldehyde 0.0041 0.0038 0.0035 0.0032 0.0030 0.0028 0.0027 0.0025 0.0024 0.0023 Benzaldehyde 0.0022 0.0020 0.0018 0.0017 0.0016 0.0015 0.0014 0.0013 0.0012 0.0012 Isovaleraldehyde 0.0092 0.0084 0.0078 0.0072 0.0067 0.0063 0.0059 0.0056 0.0053 0.0050 Valeraldehyde 0.0058 0.0054 0.0049 0.0046 0.0043 0.0040 0.0038 0.0036 0.0034 0.0032 Tolualdehydes 0.0085 0.0078 0.0072 0.0067 0.0063 0.0059 0.0055 0.0052 0.0049 0.0047 Hexaldehyde 0.0035 0.0032 0.0030 0.0028 0.0026 0.0024 0.0023 0.0021 0.0020 0.0019 2.5-dimethvlbenzaldehvde 0.0046 0.0042 0.0039 0.0036 0.0034 0.0032 0.0030 0.0028 0.0027 0.0025
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Project No. 0121.00 Element No. B5 Revision No. 1 Date March 2000 Page 1 ol"2
SECTION 10
INSTRUMENT/EQUIPMENT TESTING, INSPECTION, AND MAINTENANCE REQUIREMENTS
To ensure the quality of the sampling and analytical equipment, ERG conducts
performance checks for all equipment used in the programs. ERG personnel check, and if
needed, repair the sampling systems before the seasons begin each year. ERG tracks the
performance of the GCs to ensure proper operation. ERG also maintains a spare parts inventory
to prevent equipment downtime.
10.1 NMOC
The Hewlett-Packard (H-P) GCs used for NMOC measurements are maintained on an
as-needed basis. Before the beginning of the analytical season, an H-P technical service
representative performs preventive maintenance. Throughout the analytical season, minor
maintenance is performed by ERG personnel.
The SNMOC analytical system is maintained as described in Section 10.2.
10.2 SNMOC, UATMP, and PAMS
The GC/FID/MSD system is maintained under a service agreement. Twice a year,
preventive maintenance is performed by a technical representative. ERG personnel perform
minor maintenance, such as ferrule changes, carrier gas filter replacements, column maintenance,
and source cleaning. ,
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Project No. 0121.00 Element No. B5 Revision No. 1 Date March 2000 Page 2 of 2
10.3 PAMS
The VOC PAMS analytical system is maintained as described in Section 10.2.
The PAMS carbonyl HPLC analytical system receives preventive maintenance by a
technical service representative before the beginning of the analytical season. ERG personnel
perform other minor maintenance, such as column and detector maintenance, on an as-needed
basis.
10.4 HAPS
The GC/MSD system is maintained under a service agreement! Twice a year, preventive
maintenance is performed by a technical representative. ERG personnel perform minor
maintenance, such as ferrule changes, carrier gas filter replacements, column maintenance, and
source cleaning.
For the other HAPs sample analyses performed on the GC/ECD,' HRMSD, and ICPMS
analytical systems, preventive maintenance is performed by competent technical service
representatives as needed. ERG and subcontractor personnel perform minor maintenance, such
as column and detector maintenance, on an as-needed basis.
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Project No. Element No. Revision No. Date
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1 March 2000
1 of 11 Page
SECTION 11
INSTRUMENT CALIBRATION AND FREQUENCY
Because the requirements of the programs for analytical system calibrations differ, the
programs are discussed separately in this section.
11.1 NMOC Calibration
Before the analytical program begins, an NMOC calibration curve is generated at the
beginning and the end of the sampling season using five propane NIST certified standards and
zero air. Propane concentrations for the calibration curve are prepared at a concentration range
from zero to 10 ppmC. Zero concentration air is made from clean humidified air, The standards
are prepared from NIST certified cylinders. These standards are analyzed directly from an NIST
certified standard into the GC-PID.
Calibration curves are calculated by linear regression, assuming a linear relationship
between area counts and concentration. If the regression coefficient for any channel is less than
0.995, the entire curve is regenerated.̂ If a relative standard deviation of 3% for each point is not
met, the point is repeated.
Response factors for the NMOC calibration are verified every morning samples are
analyzed by making two injections of the mid-range QC calibration standard, an independently
prepared calibration standard with a concentration of approximately 3.0 ppmC. The relative
standard deviation (RSD) is computed and a third injection is analyzed i f the RSD is greater than
3%. After the third injection, the RSD is computed again.
RSD = SD
(Eq. 114) SamDle Averaee
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Project No. 0121.00 Element No. B6 Revision No. 1 Date March 2000 Page 2 of 11
where:
SD = Sample Standard Deviation calculated with the denominator of N- l . N = Number of injections. •
The relative error from the pair of QC injections should be within 20% of the theoretical
concentration.
TPC - DPC Relative Error = — * 100 (Eq. 11-2)
TPC
where:
TPC = Theoretical Propane Concentration. DPC = Daily Propane Concentration.
If the QC value does not meet the 20%'requirement, the QC check analysis is repeated. I f
the 20% requirement is again not met, the analysis is repeated using a lower level standard
(0.5 ppmC). If, after trying a second concentration level, the QC still does not meet acceptance
criteria, the task leader is contacted and the analyst and task leader discuss rerunning the
calibration curve.
After running and checking the QC, two zero air samples at 50% relative humidity are
injected to determine system cleanliness. The'average of the two area counts should be less than
10.0 ppbC. If the concentration is greater than 10.0 ppbC, an additional injection is analyzed and
the analyst averages all three. If the concentration is still greater than 10.0 ppbC, a leak check of
the analytical system is performed and the Task Leader is contacted.
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11.2 SNMOC Calibration
For the SNMOC instrument, a carbon response factor is obtained monthly based on the
analysis of humidified propane calibration standard. These standards are prepared by using the
Dynamic Flow Dilution System (SOP Number ERG-MOR-061) to dilute Scott Specialty or
Spectra Gas NIST certified standards into clean, evacuated stainless steel canisters. HPLC grade
water is injected to humidify the standard to approximately 75%. The standard is diluted with
nitrogen to achieve the desired concentrations for the calibration. The response factors generated
from the calibration are.used to determine concentrations in detected compounds, on the
assumption that FID response is linear with respect to the number of carbon atoms present in the
compound.
Calibration curve standards are made in ranges from 5 to 90 ppbC concentrations. The
calibration standards are analyzed in order of increasing concentration, and followed by the
system blank analysis to ensure no carryover after analysis of the high level standard. The
propane area count recorded by the FID is correlated to propane concentration by a least squares
linear regression and is used to quantitate the C2 through C,3 compounds. The calibration is
considered representative if the coefficient of correlation for the points from the curve and the
blank is greater than or equal to 0.995: for propane. The slopes of the regression lines are then
used to calculate monthly response factors.
Daily, before sample analysis, a QC standard, a certified PAMS standard prepared by
Scott Specialty or Spectra Gases is analyzed to ensure the validity of the current monthly
response factors. This standard has a midpoint concentration from the calibration for compounds
that span the carbon range. This level is considered representative of the majority of
concentrations expected in ambient air samples. The concentrations computed from the
QC standard are compared to the calculated theoretical concentrations. A concentration percent
bias of less than or equal to 30% is considered acceptable and the analytical system is in control.
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Project No. • 0121.00 Element No. B6 Revision No. 1 Date March 2000 Page 4 of 11
If the daily QC standard does not meet the 30% criterion, a second QC standard is
prepared and analyzed. If the second QC standard meets the criterion, the analytical system is
considered in control. If the second QC check does not pass, a leak test and system maintenance
is performed, and a third QC standard analysis is performed. I f the criterion is met by the third
analysis, the analytical system is considered in control. If the maintenance causes a change in
system response, a new calibration curve is required.
A system blank of cleaned, humidified air is analyzed after the daily QC standard
analysis and before sample analyses. The system is considered in control i f the total NMOC
concentration for the system blank is less than.or equal to 20 ppbC.
Retention time standards are used to gather information and set up a reference database
using relative retention times referenced to toluene. These relative retention times are used to
identify the target compounds in the ambient air samples.
For simplicity, each instrument is calibrated for all of the SNMOC, PAMS, and UATMP
compounds daily. All QC check standards have to pass each of the calibration procedures listed
in Sections 11.2, 11.3, and 11.4.
11.3 UATMP Calibration
Calibration of the GC/FID/MSD is accomplished by analyzing humidified calibration
standards generated from Scott Specialty or Spectra Gas certified standards. The certified
standards contain the UATMP target compounds at approximately 500 ppbv - polar compounds
at 1 ppm. Although the MSD is the primary quantitation tool, responses on the FID are recorded
and quantitated to detect and quantitate hydrocarbon peaks and can be used for SNMOC or
PAMS results. The calibration for these hydrocarbon peaks should be accomplished as explained
in Sections 11.2 and 11.4, respectively. >
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Project No. 0121.00 Element No. B6 Revision No. 1
; Date March 2000 Page 5 of 11
Calibration curves for the UATMP samples should include a five-point calibration and
daily calibration checks at a mid-level concentration for the target compounds (see Standard
Operating Procedure, ERG-MOR-061).
Calibration standards are generated with a dynamic flow dilution apparatus (Figure 11-1).
The gases are mixed in a SUMMA®-treated mixing sphere and bled into evacuated canisters.
One dilution air stream is routed through a SUMMA®- treated bubbler containing HPLC-grade
water to humidify; the other stream is not humidified. The dilution air streams are then brought
together for mixing with the streams from the certified cylinders. Flow rates from all streams are
gauged and controlled by mass flow controllers. The split air dilution streams are metered by
"wet" and "dry" rotameters from the humidified and unhumidified dilution air streams,-
respectively. Air is controlled from channel 4 where the mass flow controller ranges from
0-5 L/min, whereas all other channels range from 0-20 mL/min.
The system is evacuated with a vacuum pump while the closed canister is connected. The
lines leading to the canister and to the mixing sphere are flushed for at least 15 minutes with
standard gas before being connected to the canister for filling. A precision absolute pressure
gauge measures the canister pressure before and after filling.
Initial calibration curve standards are prepared at an average of 0.5, 1, 5, 10, and 15 ppbv
for each of the target compounds. All standards and samples are analyzed with the following
internal standards: «-hexane-d14, 1,4-difluorobenzene, and chlorobenzene-d5.
Bromofluorobenzene is also injected with the internal standards to verify mass spectrometer
tune. The calibration requires an average response factor, based on the internal standard, of
±30% relative standard deviation. The zero air used for canister cleaning and for standard
dilution is analyzed at the time of calibration, but the results are not included in the calibration
curve. Daily quality control verification is done with standards made from Scott certified gases
at an average concentration of 5 ppbv.
glp/D:\SECT11.WPD
CO m o
Absolute Pressure y ^ Gauge
Rotameter (exit)
Thermocouple
500-mL Summa® Treated Mixing Flask
All Tubing is Chromatographic Grade Stainless Steel All fittings are 316 Stainless Steel
Bellows Valve
Summa® Treated Canister
Mass Flow Controller
0:100 mUrn
Mass Flow Controller 0-20 mUm
Mass Flow Controller 0-20 mL/m
Mass Flow Controller 0-20 mL/m
Mass Flow Controller 0-20 mL/m
Mass Flow Controller 0-5 Urn
2.8-L Summa® Treated Humidifier
0,'s/g,'mO(,'33961099/15-1 .tif
O W tji <S ft ° ° « I 8
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Figure 11-1. Dynamic Flow Dilution Apparatus
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Project No. Element No. Revision No. Date
0121.00 B6
1 March 2000
7 of 11 Page
For simplicity, each instrument is calibrated for all of the SNMOC, PAMS, and UATMP
compounds daily. All QC check standards have to pass each of the calibration procedures listed
in Sections 11.2, 11.3 and 11.4.
11.4 PAMS Calibration
The PAMS hydrocarbon analysis system is calibrated using the same procedure described
for SNMOC in Section 11.2 on the GC/FID/MSD system.
For the PAMS carbonyl analyses, the HPLC instrument is calibrated using 0.2 to
20 micrograms per milliliter (ug/mL) nominal concentrations of the derivatized targeted
compounds contained in a solution of acetonitrile. The: calibration curve consists of six
concentration levels between 0.2 and 20 ug/mL, and each is analyzed in replicate. The standard
linear regression analysis performed on the data for each analyte must have a correlation
coefficient greater than or equal to 0.995.
As a QC procedure to check HPLC column efficiency, a second source QC (SSQC)
sample solution containing 11 target carbonyl compounds at a known concentration is analyzed
after every calibration curve. A calibration accuracy check ( a midpoint calibration standard) is
analyzed after every 10 samples (meeting the ±15% criteria), and a system blank brackets the
analytical batch, by analyzing one blank at the beginning and one at the end.
11.5 HAPS Calibration
Analytical instruments and equipment are calibrated prior to each use or on a scheduled
periodic basis. Analytical methods requiring calibration standards are governed by Standard
Operating Procedures (SOPs) for laboratory standards.,; Calibration standards must be National
Institute of standards and Technology (NIST) traceable. Appropriate standards are prepared by
serial dilutions of pure substances or accurately prepared concentrated solutions. Many
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8 of 11 Page
analytical instruments have high sensitivity, so calibration standards must be extremely dilute
solutions. In preparing stock solutions of calibration standards, great care is exercised in
measuring weights and volumes, since analyses following the calibration are based on the
accuracy of the calibration. Calibration requirements for the HAPS analytical methods are
shown in Table 11 -1.
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Project No. • 0121.00 Element No. • B6 Revision No. 1 Date March 2000 Page 9 of 11
Table 11-1
Analytical Equipment Calibration Requirements
Analytical Parameter
Quality Parameter Method of Determination
Frequency Acceptance Criteria
Particulate Matter Electronic Balance Calibrated against NIST Class S weights-
Post-test Within 2.0 mg
Metals - ICPMS ICAP Calibration-Quantitative
Initial analysis of 3 levels of standards bracketing sample concentrations
Twice per 3 runs Linear correlation coefficient >0.995
ICAP Calibration -Blanks
With calibration . standards
Every 10 samples Per manufacturer's specifications
ICAP Calibration -Interference Check
With calibration standards
Beginning and end of analyses
80-120% of expected value
ICAP Calibration -Continuing Check
Analysis of mid-range calibration standard
Once per 10 samples
90-110% of expected value
Ethylene Oxide -GC/ECD
GC/ECD Calibration -Quantitative
Analysis of 6 standards over the range of 1 to 42 u,g
Daily Nonlinear least squares fit in necessary to obtain the best fit.
GC/ECD Blanks With calibration standards
Every 10 samples Less than quantitative limit of 0.1 |ag
GC/ECD method spikes
Analysis of QC blind spikes
Per sample batch 80- 120% of expected value
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Project No. Element No. Revision No. Date Page
0121.00 B6
1 March 2000
lOof 11
Table 11-1
(Continued)
Analytical Quality Parameter Method of Frequency Acceptance Parameter Determination Criteria
PCDD/PCDF - Calibration - Initial analysis of Prior to sample Variability of mean HRGC/HRMS Quantitative standards at 5 levels analysis Response Factor
bracketing sample must be <25-20% concentrations Relative Standard
Deviation for each unlabeled analyte and internal standard and
; recovery standard. Signal/Noise ratio must be >2.5. Ion abundance ratios must be within control limits
Calibration - Analysis of column At start of each 12- Document Column Performance Check hr period resolution between Performance Check solution of 2,3,7,8-TCDD and
PCDD/PCDF other TCDDs (25% congeners valley)
Calibration - Analysis of mid- Every 12 hours Variability of mean continuing ' range calibration Response Factor
standard must be <25-20% Relative Standard Deviation for each unlabeled analyte and internal standard and
• recovery standards. Signal to Noise ratio must be > 2.5. Ion Abundance ratios must be within control limits.
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Project No. Element No. Revision No Date Page
Table 11-1
(Continued)
Analytical Parameter
Quality Parameter Method of Determination
Frequency Acceptance Criteria
Calibration Confirmation -Quantitative
Initial analysis of standards at 5 levels bracketing sample concentrations
Prior to sample analysis
Variability of mean Response Factor must be <25-20% Relative Standard Deviation for each unlabeled analyte and internal standard and recovery standards. Signal to Noise ratio must be > 2.5. Ion Abundance ratios must be within control limits.
Semivolatiles -GC/MS
Calibration -Quantitative
Initial analysis of standards at 5 levels bracketing sample concentrations
Prior to sample analysis
Variability of average Relative Response Factor < 30%
Calibration -Calibration Check Compounds
With calibration standards
Prior to sample analysis
Relative Response Factor MUST be <30%
Calibration -System Performance Check Compounds
With calibration standards
Prior to sample analysis
Minimum Relative Response Factor for Check Compounds > 0.050
Calibration - Daily calibration check
Every 12 hours Prior to sample analysis
Relative percent difference compared to mean of calibration curve <30%
Calibration - Blanks 20% of samples Concurrent with sample analysis
Analytes < Method Detection Limit
0121.00 B6
1 March 2000
11 of 11
Project No. 0121.00 Element No. B7 Revision No. 1 Date March 2000 Page 1 of 1
SECTION 12
DATA MANAGEMENT
All data generated in the ERG laboratory are collected on electronic tape or disk drives
and also paper copies. The printed copies of all reports are kept on file in the laboratory or in
storage. Final data are entered into Excel® and printed for the monthly or quarterly reports.
These reports are mailed to the EPA, State agencies, and participants. ERG will prepare a final
report containing all aspects of the program, including data summaries, QA, QC, and data
analysis results for the EPA, and distribute site-specific summaries of the final data to designated
State and local personnel.
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1 March 2000
1 of 3 Page
C—ASSESSMENT/OVERSIGHT
SECTION 13
ASSESSMENTS AND RESPONSE ACTIONS
13.1 QA Performance Audits
Quality assurance performance audit samples are provided by the EPA (or an EPA
contractor) as available. Percent accuracy (or bias) is calculated using the EPA-reported audit
sample concentration as the true value. For the NMOC program, audit samples of propane or
multicomponents in air are analyzed as received. Multi-component audit samples will be
analyzed for the 12-month UATMP by the GC/FID/MSD. For the SNMOC and PAMS
programs, multicomponent audit samples are also analyzed as received by the GC/FID/MSD
analytical system.
13.2 Performance Evaluation and System Audits
The Program Manager, Deputy Program Manager, Task Leader, and Program QA Officer
for ERG conduct performance and system audits on the laboratory procedures and the records
kept in the laboratory.
Program Manager, and Program Manager as needed. These reports are provided whenever a
QC problem that requires a change in the operating procedure occurs. These reports address
QC problems arising in the application of the work plan, an assessment of the probable
significance of the problems, and recommended corrective actions. QC problems to be addressed
may arise from:
13.3 QA Reports
The Program QA Officer provides written QA reports to the Task Leader, Deputy
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Project No. 0121.00 Element No. . CI Revision No. 1 Date March 2000 Page 2 of 3
• Poor compliance with sampling procedures reported by the project personnel;
• Invalid samples;
• In-process procedure changes required by the nature of the program; and
• Quality control waivers dictated by operating conditions.
The final report also addresses QA considerations of the whole project.
The assessment of the significance of the problems is based, in part, on the probable
effect on program completeness and validity of inferences made from the data.
Recommended actions include, as applicable:
• Tests that may clarify the problem;
• Corrective actions to alleviate the problem;
• Further documentation of the problem; and
• Acceptance of the anomalous condition with associated risk.
These reports will also include:
• Periodic assessment of measurement accuracy, precision, and completeness; and
• Results of performance and laboratory system audits.
In the final project report, a QA summary discusses all the QA activities and results for
the entire project.
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0121.00 C2
1 March 2000
1 of 2 Page
SECTION 14
REPORTS TO MANAGEMENT
14.1 QA and QC Functions
The lines of communication between management, the Program QA Officer, and the
technical staff are formally established and allow for discussion of real and potential problems,
preventive actions, and corrective procedures. The major QC responsibilities and QC review
functions are summarized in Table 14-1.
Anytime during the program, additional QA/QC measures may be initiated upon
consultation between the Task Leader, Program QA officer and the Senior Technical Advisor.
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Project No. 0121.00 Element No. C2 Revision No. 1 Date March 2000 Page 2 of2
Table 14-1
QC Responsibilities and Review Functions
Responsible Person Major Responsibilities
Program Manager • Ensure overall timely performance of high quality technical services • Communicate technical issues and needs • Track all management systems and tools • Track deliverables and budget performance • Review reports before reporting to the client
Deputy Program Manager
• Ensure data quality • Check information completeness • Assist with technical problems • Ensure appropriate level of staffing and committed resources exist to perform
work • Review data completeness and quality before reporting to client
Review all reports • Report project performance (budget and deliverables) to EPA at monthly
meetings and in monthly progress reports • ' Day-to-day management of task leaders
Program QA Officer Review QC reports • Make QA recommendations • Write and/or review test plan • Write and/or review QAPP • Audit laboratory(s) • Review documentation (reports, etc.)
Technical Advisor • Propose procedural change Propose equipment change
• Assist with technical problems
Peer Reviewer • Ensure final data quality • Final data review ' • Assist with technical problems
Analytical Task Leader • Review documentation • Develop analytical procedures
Propose procedural changes • Data review and validation • . Analyst training and supervision
Meet-task budgets and report schedules • Manage day-to-day technical activities • Check information completeness
Review instrument and maintenance log books • Review calibration factor drift • Perform preventive maintenance • Prepare monthly/quarterly reports
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D—DATA VALIDATION AND USABILITY
SECTION 15
DATA REVIEW, VALIDATION, AND VERIFICATION REQUIREMENTS
ERG uses several software programs maintained on microcomputers for data storage,
retrieval, analysis, and reporting. These programs include Microsoft Excel®; Access®; and SAS®.
Data summaries, QC charts, and other graphs, generated in a cost-effective manner, aid in
maintaining consistent data quality.
Each sample received at the ERG Laboratory is logged into the sample logbook and into
the computerized login. The accompanying field data forms are reviewed to verify that all forms
are complete.
The reliability and acceptability of environmental analytical information depends on the
rigorous completion of all the requirements outlined in. the QA/QC protocol. During data
analysis and validation, data are filtered and accepted or rejected based on the set of QC criteria.
The data are critically reviewed to locate and isolate spurious values. This review may involve
only a cursory scan to detect extreme values or a detailed evaluation requiring the use of a
computer. In either case, when a spurious value is located, it is not immediately rejected. All
questionable data, whether rejected or not, are maintained along with rejection criteria and any
possible explanation. A detailed approach such as this can be time-consuming but can also be
helpful in identifying sources of error and, in. the long run, save time by reducing the number of
outliers.
Prior to any statistical approach, the reported data are checked to ensure accurate
transcription. The value is double-checked and a comparison to previously recorded data is
made. Using conveniently formatted and bound prepared data recording forms is essential;
hardcopies of data can also be obtained directly from measuring devices that are equipped with
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the necessary digital recording peripheral. Usually, this method of recording data is sufficient if
the hardcopies are properly labeled and filed, although periodic checks should be performed to
ensure the proper operation of such a device.
The collected data are reviewed by the analyst and the task leader. The data are
scrutinized daily to eliminate the collection of invalid data. The analyst records any unusual
instances (no matter how minor) during analysis (e.g., power loss or fluctuations, temporaiy
leaks or adjustments, operator error) on the chain of custody forms and. notifies the analytical
task lead.
15.1 NMOC/SNMOC Data Reduction, Validation, and Reporting
Analytical data forms have been developed for samples receiving analysis. A copy of the
field data sheet is attached to the analytical form. The analytical data form includes site
collection information from the field data sheet, as well as analysis information and results; this
information is transferred to computer programs, including Excel®, for data storage, retrieval,
analysis,, and reporting. The analytical data forms (with attached field data sheet) are stored in
notebooks or folders in order of ID number.
15.1.1 NMOC Data Reduction. Validation, and Reporting
Monthly site-specific NMOC data update summaries are developed for the purpose of
distribution to the participating EPA technical,staff, administrators, and to the administrators of
the State agencies involved in the study. Each summary updates prior data listings. Cumulative
listings are periodically generated upon request. Even though these data summaries have not
passed through the final data validation steps, this timely turnaround of NMOC data assists in
planning, preliminary modeling, and program development for the participating State agencies.
Any changes made in the preliminary data as a result of subsequent data validation processes are
noted in the cumulative project data summaries for each specific sampling site.
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Ten percent of the NMOC database is checked to verify its validity. Items checked
include original data sheets, checks of all calculations (from calibration to sample analysis), and
data transfers. Corrections are made to the database as errors or omissions are encountered. The
analytical reviewer examines all data for overall data quality and completeness. The Deputy
Program Manager reviews all data before data are reported to the EPA or the states.
A final report containing all aspects of the NMOC program including data summaries,
QA results, QC results, and data analysis results is prepared for EPA. Site-specific data
summaries are prepared and distributed to designated State and local agencies. The final
NMOC data are submitted to the Aerometric Information Retrieval System (AIRS) Air Quality
Subsystem (AQS) as detailed in Section 15:4
15.1.2 SNMOC Data Reduction. Validation, and Reporting
A sample analysis logbook is maintained to detail pertinent sample information at the
time of analysis. Entries include site code, sample date, analysis date, and electronic file names.
A PE Nelson Turbochrom® Navigator Data System consisting of a 900 Series Intelligent
Interface and a PC system containing the Turbochrom® software is used to acquire, integrate, and
store the analytical data. A chromatograph and area count report from each detector are printed
for each analysis. Electronic copies of the data are stored on 1.44 MB flexible disk cartridges
and a compressed backup tape (250MB).
The data are processed using PE Nelson Turbochrom® version 4.1 software. The
software uses a database containing relative retention time information for all compounds of
interest and applicable response factors to process the data files. A preliminary report is
generated containing possible peak identifications and quantitations based on the carbon
response factors for propane in effect at the time of analysis.
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A data reviewer compares the Turbochrom raw data report to the chromatogram to
determine proper peak identifications. A second data review is performed to check for items that
may have been overlooked on the first pass. After the data are reviewed twice, a final report, in
Excel® format, is processed and reviewed for completeness. Final report versions containing
information on all quantitated peaks are printed and filed with the analysis chromatogram
printout and preliminary Excel® report. Electronic copies of all Excel® reports are kept on file.
The analytical reviewer examines all data for overall data quality and completeness. The Deputy
Program Manager reviews all data before it is reported to the EPA or the states. These
procedures are outlined in the laboratory SOP (ERG-MOR-005) for Sample Analysis and
Validation of Hydrocarbons on the UATMP system with a GC/FID detector.
A final report containing all aspects of the SNMOC program (including data summaries,
QA, QC, and data analysis results) is prepared for EPA. Site-specific data summaries are
prepared and distributed to designated State and local contacts. The final SNMOC data are
submitted to the AIRS AQS.
15.2 UATMP Data Reduction, Validation, and Reporting
A sample analysis logbook is maintained to detail pertinent sample information at the
time of analysis. Entries include site code, sample data, analysis date, and electronic file names.
A Hewlett Packard Chemstation® and PE Turbochrom® Data System consisting of a
900 Series Intelligent Interface and a PC system containing the software are used to acquire,
integrate, and store the analytical data. The MSD data are reported with the chromatograph and
detailed information. A chromatograph and area count report from each detector are printed for
each analysis. Electronic copies of the data are stored on tape or disk.
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The task leader reviews all of the generated analytical reports to verify peak
identifications. Printed copies of all reports are kept on file in the laboratory or in storage. Final
data are entered into Excel® and printed for the quarterly or monthly reports.
Quarterly GC/FID/MSD data summaries are developed for distribution to the
participating EPA technical staff, administrators, and administrators of the State agencies
involved in the study. The data summaries include:
'• Site code
• • Sample identifications >
• Sample dates
• Target compound list
• Concentrations (ppbv)
Quarterly preliminary data summaries are mailed to the State agencies and participants. These
data summaries are considered preliminary until the final report, at which time the data are
validated.
The analytical reviewer examines all data for overall data quality and completeness. The
Deputy Program Manager reviews all data before they are reported to the EPA or the states.
ERG prepares a final report containing all aspects of the UATMP including data summaries, QA,
QC, and data analysis results for EPA, and distribute site-specific summaries of the final data to
designated State and local personnel. ERG staff follow the SOP for the Concurrent
GC/FID/MSD Analysis of Canister Air Toxic Samples (ERG-MOR-005). ERG will submit the
final UATMP data to the AIRS AQS, as detailed in Section 15.4.
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15.3 PAMS Data Reduction, Validation, and Reporting
15.3.1 VOC Data
Data from PAMS VOC hydrocarbon analyses performed at ERG are processed using the
same procedures described for UATMP in Section 15.2. The final data are submitted to the
AIRS AQS as detailed in Section 15.4. For the PAMS sites, there is an option of statistically
validating the data generated using software generated by using Sonoma Technical Institute'
(VOCDat).
15.3.2 Carbonyl Compounds Data
All carbonyl samples received are given an ID number that corresponds to the
VOC canister sample. An extraction log is maintained to record pertinent information at the time
of extraction. A sample analysis log is also maintained to record peilinent information at the
time of analysis.
A PE Turbochrom® Data System is used to acquire, integrate, quantitate, and store the
analytical data. Preliminary peak identifications are determined based on elution times. A data
reviewer compares the chromatogram and the QC chromatogram to determine proper peak
identifications and determine i f reintegration is needed on any peak. Quantitations are based on
raw amounts of analyte in pg/mL calculated by the Turbochrom Data System from a 6-point,
least-squares regression. Results in ppbv are then calculated as described in Method TO-11A.
The analytical reviewer examines all data for overall data quality and completeness. The Deputy
Program Manager reviews all data before they are reported to the EPA or the states. Final report
versions containing information on all quantitated peaks are printed using spreadsheet software,
and the final data is submitted to the AIRS AQS as detailed in Section 15.4.
15.4 HAPS Data Reduction, Validation, and Reporting
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The HAPS analytical procedures performed during the monitoring program will be
checked against those described in the QAPP. Deviations from the QAPP will be classified as
acceptable or unacceptable, and critical or noncritical. Acceptance criteria are stated in each
method and in Section 8 of this document. The critical or noncritical nature of a deviation will
be determined in the DQA process.
Quality control samples and procedures performed during the monitoring program will be
checked against those described in Section 4 of the QAPP. Omissions will be discussed in the
final report. Quality control results (matrix/method spike recoveries, blank analysis, duplicate
analysis, etc.) will be reviewed. All results outside specified parameters will be discussed with
the EPA Delivery Order Manager for corrective action. In some cases, reference methods have
guidance on corrective action. Where available, the guidance in the reference methods will be
followed.
Documentation of equipment and instrument calibration (e.g., monitoring equipment and
analytical instalments) will be checked against' the values used in data collection. Errors and
omissions will be discussed in the final report. The documentation will be checked to ensure that
the calibration: •
• Was performed within an acceptable time prior to the sampling dates;
• Includes the proper number of calibration points;
• Was performed using appropriate standards for the reported measurements;
• Had acceptable checks to ensure that the measurement system or analytical system was stable when the calibration was performed.
The data processing systems will be checked by using raw data for which calculated
values are already known. The example data will be put into the system and the calculated
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results compared to the known values. Hand calculations will be used to check the data
processing system. Findings from these audits will be included in the final report.
15.5 Aerometric Information Retrieval System Air Quality Subsystem (AIRS AQS)
ERG submits all data collected for the NMOC, UATMP, and PAMS programs to the
AIRS AQS Subsystem.
Prior to ERG's submittal of data to AIRS, the State or local agency submits monitor
transactions (Type Fl) or ensures that monitor transactions (Type Fl) have been submitted.
ERG supplies the State or local agency with assistance concerning parameter coding for this
submittal. The Type Fl cards prepare the AIRS AQS for the raw data transactions (Type 1 or 2).
The AIRS submittal process involves the following six steps:
The raw data are formatted to comply with the requirements of AIRS AQS. The hourly data (sampling intervals of less than 24 hours) are formatted to comply with the hourly file (Type 1). The daily data (sampling intervals of 24 hours) are formatted to comply with the daily file (Type 2).
The Type 1 transaction files and Type 2 transaction files are reviewed to ensure that proper monitor ID (including state, county, site, parameter, and POC codes), interval, units, method, date, start hour, decimal point indicators, and sample value codes are correct.
The transaction files are loaded into the screening,file currently assigned to ERG.
The transaction files in the screening file are edited, the records examined in the screening file, and the data validated. The three edit checks ensure that proper codes have been used, that proper relationships exist (e.g., the reported compound and method agree), and that proper relationships exist with the data currently in the AIRS database.
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The transaction files in the screening file are corrected. Any records that do not pass the edit checks are corrected. Edit checks are then performed on the corrected data.
The AIRS Database Administrator is notified that the transactions in the screening are ready to be used in an update.
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SECTION 16
RECONCILIATION WITH DATA QUALITY OBJECTIVES
The project management team, quality assurance officer, and sampling and analytical
team members are responsible for ensuring that all measurement procedures are followed as
specified and that measurement data meet the prescribed acceptance criteria. Prompt action is
taken to correct any problem that may arise.
QC problems requiring major corrective action are documented. The Program
QA Officer or other project members initiate corrective action if QC results exceed control
limits, or i f another problem or potential problem is identified. Corrective action is immediately
reported in a corrective action report to appropriate project management and the Program
QA Officer. Corrective action is also initiated by the Program QA Officer based on QC data or
audit results.
' In addition to the corrective action reporting system for addressing problems identified
through the internal QC system, a system for issuing recommendations for corrective action
exists for addressing problems identified through QA review. Each recommendation addresses a
specific problem or deficiency.
Each of these written recommendations requires a written response from the responsible
party. Each also requires the Program QA Officer to respond and verify that the corrective action
has been implemented.
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SECTION 17
REFERENCES
1. McElroy, F.F., V.L. Thompson, and H.G. Richter. A Cryogenic Preconcentration-Direct FID (PDFID) Method for Measurement of NMOC in Ambient Air, EPA-600/4-85-063. Research Triangle Park, NC: U.S. Environmental Protection Agency, 1985.
2. McAllister, R. A., D-P. Dayton, and D. E. Wagoner. 1985 Nonmethane Organic Compounds Monitoring Assistance for Certain States in EPA Regions I , III , V, VI, and VII. Radian Corporation, DCN No. 85-203-024-35-01, prepared for Dr. Harold G. Richter, Research Triangle Park, NC: U. S. Environmental Protection Agency, 1986.
3. Purdue, L.J., D-P. Dayton, and J. Rice. Technical Assistance Document for Sampling and Analysis of Ozone Precursors. EPA 600/8-91-215. Research Triangle Park, NC: U.S. Environmental Protection Agency, 1991. Revised in 1994 and 1998.
4. McAllister, R. A., D-P. Dayton, and D. E. Wagoner. Nonmethane Organic Compounds Monitoring Assistance for Certain States in EPA Regions III. IV, V, VI, and VII. Phase I I . Radian Corporation, DCN No. 85-203-024-12-02, prepared for Dr. Harold G. Richter, Research Triangle Park, NC: U.S. Environmental Protection Agency, 1985.
5. McAllister, R. A., R. F. Jongleux, D-P. Dayton, P. L. O'Hara, and D. E. Wagoner. 1986 Nonmethane Organic Compounds Monitoring. Radian Corporation, DCN No. 87-203-024-93-11, prepared for Dr. Harold G. Richter, Research Triangle Park, NC: U. S. Environmental Protection Agency, 1987.
6. McAllister, R.A., P.L. O'Hara, D.E. Wagoner, D-P. Dayton, R.F. Jongleux. 1987 Nonmethane Organic Compound and Air Toxics Monitoring Program. Volumes I and II . Radian Corporation, DCN No. 87-203-024-93-11, prepared for Dr. Harold G. Richter, Research Triangle Park, NC: U. S. Environmental Protection Agency, 1988.
7. McAllister, R.A., W.H. Moore, D-P. Dayton, J. Rice, R.F. Jongleux, R.G. Merrill, Jr., J.T. Bursey, and P.L. O'Hara. 1989 Nonmethane Organic Compound and Urban Air Toxics Monitoring Programs. Final Report. Volume I . Nonmethane Organic Compound and Three-Hour Air Toxics Monitoring Programs. Radian Coiporation, DCN No. 88-262-045-25, prepared for Dr. Harold G. Richter, Research Triangle Park, NC: U. S. Environmental Protection Agency, 1988.
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9.
10.
11.
12.
13.
14.
McAllister, R.A., B.W. Nelson, W.H. Moore, D-P. Dayton, .1. Rice, R.F. Jongleux, R.G. Merrill, Jr., J.T. Bursey, and P.L. O'Hara. 1989 Nonmethane Organic Compound and Three-Hour Air Toxics Monitoring Program, Final Report. Radian Corporation, DCN No. 262-045-89, prepared for Neil J. Berg, Jr., Research Triangle Park, NC: U. S. Environmental Protection Agency, 1990.
O'Hara, P.L., R.A. McAllister, D-P. Dayton, J.E. Robbins, R.F. Jongleux, R.G. Merrill, Jr., J. Rice, J.E. McCartney, T.L. Sampson, and J.Y. Martin. 7997 Nonmethane Organic Compound, Speciated Nonmethane Organic Compound, and Three-Hour Air Toxics Monitoring Program, Final Report. Radian Corporation, DCN No. 92-262-045-90, prepared for Neil J. Berg, Jr., Research Triangle Park, NC: U. S. Environmental Protection Agency, 1992.
O'Hara, P.L.,.R.G. Merrill, Jr., T.L. Sampson, D-P. Dayton, J. Rice, J.E. McCartney, and J.Y. Martin. 1992 Nonmethane Organic Compounds and Speciated Nonmethane Organic Compounds Monitoring Programs, Final Report. Radian Corporation, DCN No. 93-298-017-70-13, prepared for Neil J. Berg, Jr., Research Triangle Park, NC: U. S. Environmental Protection Agency, 1993.
Dayton, D-P., R. A. McAllister, D. Wagoner, F. F. McElroy, V. L. Thompson, and H. G. Richter, U. S. Environmental Protection Agency, "An Air Sampling System for Measurement of Ambient Organic Compounds," Paper presented at the 1986 U.S. EPA/APCA Symposium: Measurement of Toxic Air Pollutants, Raleigh, NC, April 27-30, 1986.
1993 Nonmethane Organic Compounds and Speciated Nonmethane Organic Compounds Monitoring Programs, Final Report. Radian Corporation, DCN No. 93-298-130-12-10, prepared for Neil J. Berg, Jr., Research,Triangle Park, NC: U. S. Environmental Protection Agency, 1994.
1994 Urban Air Toxics Monitoring Program, Final Report. Radian Corporation. Prepared for Kathy Weant and Neil J. Berg, Jr., Research Triangle Park, NC: U..S. Environmental Protection Agency, 1996.
Steger, J., and J. Rice. 1995 Non-Methane Organic Compounds and Speciated Non-Methane Organic Compounds Monitoring Programs, Final Report. Eastern Research Group, Inc., prepared for Kathy Weant and Neil J. Berg, Jr., Research Triangle Park, NC: U. S. Environmental Protection Agency, 1996.
1995 Urban Air Toxics Monitoring Program, Final Report. Eastern Research Group, Inc., prepared for Kathy Weant and Neil J. Berg, Jr., Research Triangle Park, NC: U. S. Environmental Protection Agency, 1997.
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APPENDIX C
U.S. Environmental Protection Agency (EPA)
Compendium Method TO-15: Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specialty-Prepared
Canisters and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) from the
Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air Second Edition
Center for Environmental Research Information
Office of Research and Development. Cincinnati, OH January 1999 :
U'.-VOiD/K-vO/OlOb
Compendium of Methods for the Determination of
Toxic Organic Compounds in Ambient Air
i
l
Second Edition ; ! i i i i
Compendium Method TO-15
Determination Of Volatile Organic Compounds (VOCs) In Air Collected In
Specially-Prepared Canisters And Analyzed By Gas Chromatography/
Mass Spectrometry (GC/MS)
Center for Environmental Research Information Office of Research and Development
U.S. Environmental, Protection Agency Cincinnati, OH 45268
January 1999
METHOD TO-15
Determination of Volatile Organic Compounds (yOCs) In Air Collected In Specially-Prepared Canisters And Analyzed By Gas Chromatography/
Mass Spectrometry (GC/MS)
TABLE OF CONTENTS
Page
1. Scope
2. Summary of Method 1>2
. 3. Significance \ ' • 15-3
4. Applicable Documents 4.1 ASTM Standards ' . ' . . ' ' [[ ' [ [ [ " ' ] ' ' [ ' ' " " .' 4.2 EPA Documents , ~
15-4 5. Definitions
' ''. ; lD-4 6. Interferences and Contamination ... , c r
' ' '• I 5-6 7. Apparatus and Reagents ^ ^
7.1 Sampling Apparatus : J 5 6
7.2 Analytical Apparatus •. . j 5 §
7.3 Calibration System and Manifold Apparatus 15 10 7.4 Reagents..... \\\\\\\\\\\\\\[ [ [ [ [ [ [ [ ';' ^
8. - . Collection of Samples in Canisters 15 10 8.1 Introduction 15 10 8.2 Sampling System Description 1 5 1 1
8.3 Sampling Procedure 15 12 8.4 Cleaning and Certification Program 1' ' 15 14
9. GC/MS Analysis of Volatiles from Canisters j 5_, 6
9.1 Introduction . 15 16 9.2 Preparation of Standards ) 5 " ] 7
10. GC/MS Operating Conditions 1 5 9 ]
10.1 Preconcentrator . , " 10.2 GC/MS System I'"99 10.3 Analytical Sequence • [ 5
10.4 Instrument Performance Check . 1 5 ? ~ 10.5 Initial Calibration \S~2n
10.6 Daily Calibration 1 5 9 ^ 10.7 Blank Analyses : ) 5 9 7
10.8 Sample Analysis >cZ0
It!
J C . in
METHOD TO-15
Determination of Volatile Organic Compounds (VOCs) In Air Collected In Specially-Prepared Canisters And Analyzed By Gas Chromatography/
Mass Spectrometry (GC/MS)
1. Scope
1.1 Tins method documents sampling and analytical procedures for the measurement of subsets of the 97 volatile organic compounds (VOCs) that are included in the 189 hazardous air pollutants (HAPs) listed in Title HI of the Clean Air Act Amendments of 1990. VOCs are defined hereas organic compounds having a vapor press
• greater than 10;' Torr at 25'C and 760 mm Hg. Table 1 is the list of the target VOCs alone wit^heTcAS number, boiling point, vapor pressure and an indication of their membership in both the list of VOCs covered by Compendium Method TO-14A (I) and the list of .VOCs in EPA's Contract Laboratory Program (CLP) document entitled: Statement-of-Work (SOW) for the Analysis of Air Toxics from Superfund Sites (2).
Many of these compounds have been tested for stability in concentration when stored in specially-prepared canisters (see Section 8) under conditions typical of those encountered in routine ambient air analysis The stability of these compounds under all possible conditions is not known. However, a model to predict compound los.es due to physical adsorption of VOCs on canister walls and to dissolution of VOCs in water condensed in the canisters has been developed (3). Losses due to physical adsorption require oniv the S s h m e m of equihonum between the condensed and gas phases and are generally considered short term losses (i occurring over minutes to hours). Losses due to chemical reactions of the VOCs with collected ozone or other gas phase species also account for some short term losses. Chemical reactions between VOCs and substances ins.de the canister are generally assumed to cause the gradual decrease of concentration over time (i e Ion* term losses over days to weeks). Loss mechanisms such as aqueous hydrolysis and biological degradation (4) also exist. No models are currently known to be available to estimate and characterize all these potential losses although a number of experimental observations are referenced in Section 8. Some of the VOCs listed in Title III have short atmospheric lifetimes and may not be present except near sources.
1.2 This method applies to ambient concentrations of VOCs above 0.5 ppbv and tvpically requires VOC enrichment by concentrating up to one liter of a sample volume. The VOC concentration range for ambient air in many cases includes the concentration-at which continuous exposure over a lifetime is estimated to constitute a 10 or higher lifetime>nsk of developing cancer in humans. Under circumstances in which many hazardous VOCs are present at 10"6 risk concentrations, the total risk may be significantly greater.
13 This method applies under most conditions encountered in sampling of ambient air into canisters However the composition ot a gas mixture in a canister, under unique or unusual conditions, will change so that the sample is known not to be a true representation of the ambient air from which it was taken. For example, low humiditv condi ons in the sample may ead to losses of certain VOCs on the canister walls, losses that wo Id not happen if the humidity were higher: If the canister is pressurized, then condensation of water from high humidity sample may cause fractional losses of water-soluble compounds: Since the canister surface area is limited aliases are ..i competition for the available active sites. Hence an absolute storage stability cannot be assigned to a%ecitic gas. Fortunately, under conditions of normal usage for sampling ambient air. most VOCs can be recovered from canisters near their original concentrations after storage times of up to thirty days (see'Section 8).
1.4 Use of the Compendium Method TO-15 for many of the VOCs listed in Table 1 is likely to present two difficulties: (I) what calibration standard to use for establishing a basis for testing and quantitation, and (2) how
January 1999 Compendium of Methods tor Toxic Organic Air Pollutants P a g e 15-1
VOCs Method TO-15
reducing the sample size. For example, a small sample can be concentrated on a cold trap and released directly to the gas chromatographic column. The reduction in sample volume may require an enhancement of detector sensitivity.
Other water management approaches are also acceptable as long as their use does not compromise the attainment of the .performance criteria listed in Section II." A listing of some commercial water management systems is provided in Appendix A. One of the alternative ways to dry the sample is to separate VOCs from condensate on a low temperature trap by heating and purging the trap.
2.5 The analytical strategy for Compendium Method TO-15 involves using a high resolution gas chromatograph (GC) coupled to a mass spectrometer. If the mass spectrometer is a linear quadrupole system, ft is operated either by continuously scanning a wide range of mass to charge ratios (SCAN mode) or by monitoring select ion monitoring mode (SIM) of compounds on the target list. If the mass spectrometer is based on a standard ion trap design, only a scanning mode is used (note however, that the Selected Ion Storage (SIS) mode for the ion trap has features of the SIM mode). Mass spectra for individual peaks in the total ion chromatogram are examined with respect to the fragmentation pattern of ions corresponding to various VOCs including the intensity of primary and secondary ions. The fragmentation pattern is compared with stored spectra taken under similar conditions, in order to identify the compound. For any given compound, the intensity of the primary fragment is compared with the system response to the primary fragment for known amounts of the compound. This establishes the compound concentration that exists in the sample. . ' ,
Mass spectrometry is considered a more definitive identification technique than single specific detectors such as flame ionization detector (FID), electron capture detector (ECD), photoionization detector (PID), or a multidetector arrangement of these (see discussion in Compendium Method TO-14A). The use of both gas chromatographic retention time and the generally unique mass fragmentation patterns reduce the chances for misidentification. If the technique is supported by a comprehensive mass spectral database and a knowledgeable operator, then the correct identification and quantification of VOCs is further enhanced.
3. Significance
3.1 Compendium Method TO-15 is significant in that it extends the Compendium Method TO- 14A description for using canister-based sampling and gas chromatographic analysis in the following ways:
• Compendium Method TO-15 incorporates a multisorbent/dry purge technique or equivalent (see Appendix A) for water management thereby addressing a more extensive set of compounds (the VOCs mentioned in Title III of the CAAA of 1990) than addressed by Compendium Method TO-14A. Compendium Method TO-14A approach to water management alters the structure or reduces the sample stream concentration of some VOCs, especially water-soluble VOCs.
• Compendium Method TO-15 uses the GC/MS technique as the only means to identify and quantitate target compounds/The GC/MS approach provides a more scientifically-defensible detection scheme which is generally more desirable than the use of single or even multiple specific detectors.
• In addition, Compendium Method TO-15 establishes method performance criteria for acceptance of data, allowing the use of alternate but equivalent sampling and analytical equipment. There are several new and viable commercial approaches for water management as noted in Appendix A of this method on which to base a VOC monitoring technique as well as other approaches to sampling (i.e., autoGCs and solid
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 15-3
5.2 Absolute Pressure—pressure measured with reference to absolute zero pressure, usually expressed in units ofkPa,orpsi.
5.3 Cryogen—a refrigerant used to obtain sub-ambient temperatures in the VOC concentrator and/or on front of the analytical column. Typical cryogens are liquid nitrogen (bp -195.8°C), liquid argon (bp -185 7°C) and liquid CO: (bp-79.5°C).
5.4 Dynamic Calibration—calibration of an analytical system using calibration gas standard concentrations in a form identical or very similar to the samples to be analyzed and by introducing such standards into the inlet of the sampling or analytical system from a manifold through which the gas standards are flowing.
5.5 Dynamic Dilution—means of preparing calibration mixtures in which standard gas(es) from pressurized cylinders are continuously blended with humidified zero air in a manifold so that a flowing stream of calibration mixture is available at the inlet of the analytical system.
5.6 MS-SCAN—mass spectrometric mode of operation in which the gas chromatograph (GC) is coupled to a mass spectrometer (MS) programmed to SCAN all ions repeatedly over a specified mass range.
5.7 MS-SIM—mass spectrometric mode of operation in which the GC is coupled to a MS that is programmed to scan a selected number of ions repeatedly [i.e., selected ion monitoring (SIM) mode].
5.8 Qualitative Accuracy—the degree of measurement accuracy required to correctly identify compounds with an analytical system.
5.9 Quantitative Accuracy—the degree of measurement accuracy required to correctly measure the concentration of an identified compound with an analytical system with known uncertainty.
5.10 Replicate Precision—precision determined from two canisters filled from the same air mass over the same time period and determined as the absolute value of the difference between the analyses of canisters divided by their average value and expressed as a percentage (see Section 11 for performance criteria for replicate precision).
5.11 Duplicate Precision—precision determined from the analysis of two samples taken from the same canister. The duplicate precision is determined as the absolute value of the difference between the canister analyses divided by their average value and expressed as a percentage.
5.12 Audit Accuracy—the difference between the analysis of a sample provided in an audit canister and the nominal value as determined by the audit authority, divided by the audit value and expressed as a percentage (see Section 11 for performance criteria for audit accuracy).
6. Interferences and Contamination
6.1 Very.volatile compounds, such as chloromethane and vinyl chloride can display peak broadening and co-elution with other species if the compounds are not delivered to the GC column in a small volume of carrier gas. Refocusing of the sample after collection on the primary trap, either on a separate focusing trap or at the head of the gas chromatographic column, mitigates this problem.
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VOCs Method TO-15
7.1.1.6. Electronic Timer. For unattended sample collection. 7.1.1.7 Solenoid Valve. Electrically-operated, bi-stable solenoid valve with Viton® seat and O-rings. A
Skinner Magnelatch valve is used for purposes of illustration in the text (see Figure 2). 7.1.1.8 Chromatographic Grade Stainless Steel Tubing and Fittings. For interconnections. All such
materials in contact with sample, analyte, and support gases prior to analysis should be chromatographic grade stainless steel or equivalent. "
7.1.1.9 Thermostatically Controlled Heater. To maintain above ambient temperature inside insulated sampler enclosure.
. 7.1.1.10 Heater Thermostat. Automatically regulates heater temperature. 7.1.1.11 Fan. For cooling sampling system. 7.1.1.12 Fan Thermostat. Automatically regulates fan operation. 7.1.1.13 Maximum-Minimum Thermometer. Records highest and lowest temperatures during sampling
period. 7.1.1.14 Stainless Steel Shut-off Valve. Leak free, for vacuum/pressure gauge. 7.1.1.15 Auxiliary Vacuum Pump. Continuously draws air through the inlet manifold at 10 L/min. or
higher flow rate. Sample is extracted from the manifold at a lower rate, and excess air is exhausted.
[Note: The use of higher inlet flow rates dilutes any contamination present in the inlet and reduces the possibility of sample contamination as a result of contact with active adsorption sites on inlet walls.]
7.1.1.16 Elapsed Time Meter. Measures duration of sampling. 7.1.1.17 Optional Fixed Orifice, Capillary, or Adjustable Micrometering Valve. May be used in lieu
of the electronic flow controller for grab samples or short duration time-integrated samples. Usually appropriate only in situations where screening samples are taken to assess future sampling activity.
7.1.2 Pressurized (see Figure 1 with metal bellows type pump and Figure 3). 7.1.2.1 Sample Pump. Stainless steel, metal bellows type, capable of 2 atmospheres output pressure.
Pump must be free of leaks, clean, and uncontaminated by oil or organic compounds.
[Note: An alternative sampling system has been developed by Dr. R. Rasmussen, The Oregon Graduate Institute of Science and Technology, 20000 N.W. Walker Rd., Beaverton, Oregon 97006, 503-690-1077, and is illustrated in Figure 3. This flow system uses, in order, a pump, a mechanical flow regulator, and a mechanical compensation flow restrictive device. In this configuration the pump is purged with a large sample flow, thereby eliminating the need for an auxiliary vacuum pump to flush the sample inlet.]
7.1.2.2 Other Supporting Materials. All other components of the pressurized sampling system are similar to components discussed in Sections 7.1.1.1 through 7.1.1.17.
7.2 Analytical Apparatus
7.2.1 Sampling/Concentrator System (many commercial alternatives are available). 7.2.1.1 Electronic Mass Flow Controllers. Used to maintain constant-flow (for purge gas, carrier gas
and sample gas) and to provide an analog output to monitor flow anomalies. 7.2.1.2 Vacuum Pump. General purpose laboratory pump, capable of reducing the downstream pressure
of the flow controller to provide the pressure differential necessary to maintain controlled flow rates of sample air. !
7.2.1.3 Stainless Steel Tubing and Stainless Steel Fittings. Coated with fused silica to minimize active adsorption sites. • *
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VOCs Method TO-15
parallel array of rods under the influence of the generated field. Ions which are successfully transmitted through the quadrupole are said to possess stable trajectories and are subsequently recorded with the detection system. When the DC potential is zero, a wide band ofm/z values is' transmitted through the quadrupole. This "RF only" mode is referred to as the "total-ion" mode. In this mode, the quadrupole acts as a strong focusing lens analogous to a high pass filter. The amplitude of the RF determines the low mass cutoff. A mass~spectrum is generated by scanning the DC and RF voltages using a fixed DC/RF ratio and a.constant drive frequency or bv scanning the frequency and holding the DC and RF constant.. With the quadrupole system only 0.1 to 0.2 percent ofthelons formed in the ion source actually reach the detector.
7.2.2.3.2Ion Trap Technology. An ion-trap mass spectrometer consists of a chamber formed between two metal surfaces in the shape of a hyperboloid of one sheet (ring electrode) and a hyperboloid of two sheets (the two end-cap electrodes). Ions are created within the chamber by electron impact from an electron beam admitted through a small aperture in one of the end caps.' Radio frequency (RF) (and sometimes direct current voltage offsets) are applied between the ring electrode and the two end-cap electrodes establishing a quadrupole-electric field. This field is uncoupled in three directions so that ion motion can be considered independently in each direction; the force acting upon an ion increases with the displacement of the ion from the center of the field but the direction of the force depends on.the instantaneous voltage applied to the ring electrode. A restoring force along one coordinate (such as the distance, r, from the ion-trap's axis of radial symmetry) will exist concurrently with a repelling force along another coordinate (such as the distance, z, along the ion traps axis), and if the field were static the ions would eventually strike an electrode. However, in an RF field the force along each coordinate alternates direction so that a stable trajectory may be possible in which the ions do not strike a surface. In practice, ions of appropriate mass-to-charge ratios may be trapped within the device for periods of milliseconds to hours. A diagram of a typical ion trap is illustrated in Figure" 7. Analysis of stored ions is performed by increasing the RF voltage, which makes the ions successively unstable. The effect of the RF voltage on the ring electrode is to "squeeze" the ions in the xy plane so that they move along the z axis. Half the ions are lost to the top cap (held at ground potential); the remaining ions exit the lower end cap to be detected by the electron multiplier. As the energy applied to the ring electrode is, increased, the ions are collected in order of increasing mass to produce a conventional mass spectrum. With the ion trap, approximately 50 percent of the generated ions are detected. As a result, a significant increase in sensitivity can be achieved when compared to a full scan linear quadrupole system.
7.2.2.4 GC/MS Interface. Any gas chromatograph to mass spectrometer interface that gives acceptable calibration points for each of the analytes of interest and can be used to achieve all acceptable performance criteria may be used. Gas chromatograph to mass spectrometer interfaces constructed of all-glass, glass-lined, or fused silica-lined materials are recommended. Glass.and fused silica should be deactivated.
7.2.2.5 Data System. The computer system that is interfaced to the mass spectrometer must allow the continuous acquisition and storage, on machine readabje media, of all mass spectra obtained throughout the duration of the chromatographic program. The computer must have software that allows searching any GC/MS data file for ions of a specified mass and plotting such ion abundances versus time or scan number. This type of plot is defined as a Selected Ion Current Profile (SICP). Software must also be available that allows integrating the abundance in any SrCP between specified time or scan number limits. Also, software must be available that allows for the comparison of sample spectra with reference library spectra. The National Institute of Standards and Technology (NIST) or Wiley Libraries or equivalent are recommended as reference libraries.
7.2.2.6 Off-line Data Storage Device. Device must be capable of rapid recording and retrieval of data and must be suitable for long-term, off-line data storage.
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VOCs Method TO-15
8.2.2 Pressurized Sampling [see Figure 1 (with metal bellows type pump)]. 8.2.2.1 Pressurized sampling is used when longer-term integrated samples or higher volume samples are
required. The sample is collected in a canister using a pump and flow control arrangement to achieve a typical 101-202 kPa (15-30 psig) final canister pressure. For example, a 6-liter evacuated canister can be tilled at 10 mL/min for 24 hours to achieve a final pressure of 144 kPa (21 psig).
8.2.2.2 In pressurized canister sampling, a metal bellows type pump draws in air from the sampling manifold to till and pressurize the sample canister.
8.2.3 All Samplers. 8.2.3.1 A flow control device is chosen to maintain a constant flow into the canister over the desired
sample period. This flow rate is determined so the canister is filled (to about 88.1 kPa for subatmospheric pressure sampling or to about one atmosphere above ambient pressure for pressurized sampling) over the desired sample period. The flow rate can be calculated by:
F = P x V
T x 60
where:
F = flow rate, mL/min. P = final canister pressure, atmospheres absolute. P is approximately equal to
kPa aauae . is—:=_ + 1
101.2
V = volume of the canister, mL. T = sample period, hours.
For example, if a 6-L canister is to be filled to 202 kPa (2 atmospheres) absolute pressure in 24 hours, the flow rate-can be calculated by:
F = 2 * 6 0 0 0 = 8.3 mL/min 24 x 60
8.2.3.2 For automatic operation, the timer is designed to start and stop the pump at appropriate times for the desired sample period. The timer must also control the solenoid valve, to open the valve when starting the pump and to close the valve when stopping the pump.
8.2.3.3 The use of the Skinner Magnelatch val ve (see Figure 2) avoids any substantial temperature rise that would occur with a conventional, normally closed solenoid valve that would have to be energized during the entire sample period. The temperature rise in the valve could cause outgassing of organic compounds from the Viton® valve seat material. The Skinner Magnelatch valve requires only a brief electrical pulse to open or close at the appropriate start and stop times and therefore experiences no temperature increase. The pulses may be obtained either with an electronic timer that can be programmed for short (5 to 60 seconds) ON periods, or with a conventional mechanical timer and a special pulse circuit. A simple electrical pulse circuit for operating the Skinner Magnelatch solenoid valve with a conventional mechanical timer is illustrated in Figure 2(a). However, with this simple circuit, the valve may operate unreliably during brief power interruptions or if the timer is manually switched on and off too fast. A better circuit incorporating a time-delay relay to provide more reliable valve operation is shown in Figure 2(b).
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'. . Method TO-15
8.3.7 The "practice" canister and certified mass flow meter are disconnected and a clean certified (see Section 8.4.1) canister is attached to the system.
8.3.8 The canister valve and vacuum/pressure gauge valve are opened. 8.3.9 Pressure/vacuum in the canister is recorded on the canister FTDS (see Figure 9) as indicated by the
sampler vacuum/pressure gauge.
8.3.10 The vacuum/pressure gauge valve is closed and the maximum-minimum, thermometer is reset to current temperature. Time of day and elapsed time meter readings are recorded on the canister FTDS.
8.3.11 The electronic timer is set to start and stop the sampling period at the appropriate times. Sampling starts and stops by the programmed electronic timer.
8.3.12 After the desired sampling period, the maximum, minimum, current interior temperature and current ambient temperature are recorded on the FTDS. The current reading from the flow controller is recorded.
.8.3.13 At the end of the sampling period, the vacuum/pressure gauge valve on the sampler is briefly opened and closed and the pressure/vacuum is recorded on the FTDS. Pressure should be close to desired pressure.
[Note: For a subatmospheric sampling system, if the canister is at atmospheric pressure when the field final pressure check is performed, the sampling period may be suspect. This information should be noted on the sampling field data sheet.]
Time of day and elapsed time meter readings are also recorded. 8.3.14 The canister valve is closed. The sampling line is disconnected from the canister and the canister is
removed from the system. For a subatmospheric system, a certified mass flow meter is once again connected to the inlet manifold in front of the in-line filter and a "practice" canister is attached to the Magnelatch valve of the sampling system. The final flow rate is recorded on the canister FTDS (see Figure 9).
[Note: For a pressurized system, the final flow may be measured directly.]
The sampler is turned off.
8.3.15 An identification tag is attached to the canister. Canister serial number, sample number, location, and date, as a minimum, are recorded on the tag. The canister is routinely transported back to the analytical laboratory with other canisters in a canister shipping case.
8.4 Cleaning and Certification Program i
8.4.1 Canister Cleaning and Certification. 8.4.1.1 All canisters must be clean and free of any contaminants before samplecollection. 8.4.1.2 All canisters are leak tested by pressurizing them to approximately 206 kPa (30 psig) with zero
air. . *
[Note: The canister cleaning system in Figure 10 can be used for this task.]
The initial pressure is measured, the canister valve is closed, and the final pressure is checked after 24 hours. If acceptable, the pressure should not vary more than ± 13.8 kPa (± 2 psig) over the 24 hour period.
8.4.1.3 A canister cleaning system may be assembled as illustrated in Figure 10. Cryogen is added to both the vacuum pump and zero air supply traps. The canister(s) are connected to the manifold. The vent shut-off valve and the canister valve(s) are opened to release any remaining pressure in the canister(s). The vacuum pump is started and the vent shut-off valve is then closed and the vacuum shut-off valve is opened. The canister(s
. evacuated to O.05 mm Hg (see Appendix B) for at least I hour. are
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[Note: In the following sections,, "certification" is defined as evaluating the sampling system with humid zero air and humid calibration gases that pass through all active components of the sampling svstem. The svstem is "certified" if no significant additions or deletions'(less than 0.2 ppbv each of target compounds) have occurred when challenged with the test gas stream.]
8.4.3.1 The cleanliness of the sampling system is determined by testing the sampler with humid zero air without an evacuated gas sampling canister, as follows.
8.4.3.2 The calibration system and manifold are assembled, as illustrated in Figure 8. The sampler (without an evacuated gas canister) is connected to the manifold and the zero air.cylinder is~activated to generate a humid gas stream (2 L/min) to the calibration manifold [see Figure 8(b)].
8.4.3.3 The humid zero gas stream passes through the calibration manifold, through the sampling system (without an evacuated canister) to the water management system/VOC preconcentrator of an analyticafsystem.
[Afore; The exit of the sampling system (without the canister) replaces the canister in Figure 11.] •
After the sample volume (e.g., 500 mL) is preconcentrated on the trap, the trap is heated and the VOCs are thermally desorbed and refocussed on a cold trap. This trap is heated and the VOCs are thermally desorbed onto the head of the capillary column. The VOCs are refocussed prior to gas chromatographic separation. Then, the oven temperature (programmed) increases and the VOCs begin to elute and are detected by a GC/MS (see Section 10) system. The analytical system should not detect greater than 0.2 ppbv of any targeted VOCs in order for the sampling system to pass the humid zero air certification test. .Chromatograms (using an FID) of a certified sampler and contaminated sampler are illustrated in Figures 12(a) and 12(b), respectively^ If the sampler passes the humid zero air test, it is then tested with humid calibration gas standards containing selected VOCs at concentration levels expected in field sampling (e.g., 0.5 to 2 ppbv) as outlined in Section 8.4.4.
8.4.4 Sampler System Certification with Humid Calibration Gas Standards from a Dynamic Calibration System
8.4.4.1 Assemble the dynamic calibration system and manifold as illustrated in Figure 8. ' 8.4.4.2 Verify that the calibration system is clean (less than 0.2 ppbv of any target compounds) by
sampling a humidified gas stream, without gas calibration standards, with a previously certified clean canister (see Section 8.1).
8.4.4.3 The assembled dynamic calibration system is certified clean if less than 0.2 ppbv of any targeted compounds is found.
8.4.4.4 For generating the humidified calibration standards, the calibration gas cylinder(s) containing nominal concentrations of 10 ppmv in nitrogen of selected VOCs is attached to the calibration system as illustrated in Figure 8. The gas cylinders are opened and the gas mixtures are passed through 0 to 10 mL/min certified mass flow controllers to generate ppb levels of calibration standards.
8.4.4.5 After the appropriate equilibrium period, attach the sampling system (containing a certified evacuated canister) to the manifold, as illustrated in Figure 8(b).
8.4.4.6 Sample the dynamic calibration gas stream with the sampling system. 8.4.4.7 Concurrent with the sampling system operation, .realtime monitoring of the calibration gas stream
is accomplished by the on-line GC/MS analytical system [Figure 8(a)] to provide reference concentrations of generated VOCs.
8.4.4.8 At the end of the sampling period (normally the same time period used for experiments), the sampling system canister is analyzed and compared to the reference GC/MS analytical system to determine if the concentration of the targeted VOCs was increased or decreased by the sampl ing system.
8.4.4.9 A recovery of between 90% and 1 10% is expected for all targeted VOCs. 8.4.5 Sampler System Certification without Compressed Gas Cylinder Standards.
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VOCs Method TO-15
9.2 Preparation of Standards
9.2.1 Introduction. 9.2.1.1 When available, standard mixtures of target gases in high pressure cylinders must be certified
traceable to a NIST Standard Reference Material (SRM) or to a NIST/EPA approved Certified Reference Material (CRM). Manufacturer's certificates of analysis must be retained to track the expiration date.
9.2.1.2 The neat standards that are used for making trace gas standards must be of high purity; generally a purity of 98 percent or better is commercially available.
9.2.1.3 Cylinder(s) containing approximately 10 ppmv of each of the target compounds are typically used as primary stock standards. The components may be purchased in one cylinder or in separate cylinders depending on compatibility of the compounds and the pressure of the mixture in the cylinder. Refer to manufacturer's specifications for guidance on purchasing and mixing VOCs in gas cylinders.
9.2.2 Preparing Working Standards. 9.2.2.1 Instrument Performance Check Standard. Prepare a standard solution of BFB in humidified
zero air at a concentration which will allow collection of 50 ng of BFB or less under the optimized concentration parameters.
9.2.2.2 Calibration Standards. Prepare five working calibration standards in humidified zero air at a concentration which will allow collection at the 2, 5, 10, 20, and 50 ppbv level for each component.under the optimized concentration parameters.
9.2.2.3 Internal Standard Spiking Mixture. Prepare an internal spiking mixture containing bromo-chloromethane, chlorobenzene-d5, and 1,4-difluorobenzene at 10 ppmv each in humidified zero air to be added to the sample or calibration standard. 500 uL of this mixture, spiked into 500 mL of sample will result in a concentration of 10 ppbv. The internal standard is introduced into the trap during the collection time for all calibration, blank, and sample analyses using the apparatus shown in Figure 13 or by equivalent means. The volume of internal standard spiking mixture added for each analysis must be the same from run to run.
9.2.3 Standard Preparation by Dynamic Dilution Technique. 9.2.3.1 Standards may be prepared by dynamic dilution of the gaseous contents of a cylinder(s) containing
the gas calibration stock standards with humidified zero air using mass flow controllers and a calibration manifold. The working standard may be delivered from the manifold to a clean, evacuated canister using a pump and mass flow controller.
9.2.3.2 Alternatively, the analytical system may be calibrated by sampling directly from the manifold if the flow rates are optimized to provide the desired amount of calibration.standards. However, the use of the canister as a reservoir prior to introduction into the concentration system resembles the procedure normally used to collect samples and is preferred. Flow rates of the dilution air and cylinder standards (all expressed in the same units) are measured using a bubble meter or calibrated electronic flow measuring device, and the concentrations of target compounds in the manifold are then calculated using the dilution ratio and the original concentration of each compound.
9.2.3.3 Consider the example of 1 mL/min flow of 10 ppmv standard diluted with 1,000 mL/min of humid air provides a nominal 10 ppbv mixture, as calculated below:
Manifold Cone. = (Original >Conc.) (Std. Gas Flowrate) (Air Flowrate) + (Std. Gas Flowrate)
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VOCs Method TO-15
9.2.5.2 An aluminum cylinder is flushed with high-purity nitrogen gas and then evacuated to better than 25 in. Hg.
9.2.5.3 Predetermined amounts of each neat standard compound are measured using a microliter or gastight syringe and injected into the cylinder. The cylinder is equipped with a heated injection port and nitrogen flow to facilitate sample transfer.
9.2.5.4 The cylinder is pressurized to 1000 psig with zero nitrogen.
[Note: User should read all SOPs associated with generating standards in high pressure cylinders. Follow all safety requirements to minimize danger from high pressure cylinders.]
9.2.5.5 The contents of the cylinder are allowed to equilibrate (-24 hrs) prior to withdrawal of aliquots into the GC system.
9.2.5.6 If the neat standard is a gas, the cylinder concentration is determined using the following equation:
Volume , , Concentration, ppbv = s o n d a r d x 109
• V 0 l l I m e d i l u u o n gns
[Note: Both values must be expressed in the same units.]
9.2.5.7 If the neat standard is a liquid, the gaseous concentration can be determined using the following equations:
y - n R T
and:
n = (mL)(d) MW
where: V = Gaseous volume of injected compound at EPA standard temperature (25°C) and pressure (760 mm Hg), L.
n= Moles. R = Gas constant, 0.08206 L-atm/mole °K. T = 298 ° K (standard temperature). P = 1 standard pressure, 760 mm Hg (1 atm).
mL= Volume of liquid injected, mL. d = Density of the neat standard, g/mL.
MW = Molecular weight of the neat standard expressed, g/g-mole.
The gaseous volume of the injected compound is divided by the cylinder volume at STP and then multiplied by 10'J to obtain the component concentration in ppb units.
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VOCs Method TO-15
Set point Sample volume Carrier gas purge flow
-150°C -up to 100 mL - none •
Set point Sample volume Carrier gas purge flow
27°C - up to 1,000 mL - selectable
[Note: The analyst should optimize the flow rate, duration of sampling, and absolute sample volume to be used. Other preconcentration. systems may be used provided performance standards (see Section 11) are realized.]
10.1.2 Desorption Conditions
Cryogenic Trap
Desorb Temperature Desorb Flow Rate Desorb Time
120°C - 3 mL/min He <60 sec
Adsorbent Trap
Desorb Temperature Desorb Flow Rate Desorb Time
Variable ~3 mL/min He <60 sec
The adsorbent trap conditions depend on the specific solid adsorbents chosen (see manufacturers' specifications).
10.1.3 Trap Reconditioning Conditions.
Cryogenic Trap
Initial bakeout Variable (24 hrs) After each run
10.2 GC/MS System
120°C(24hrs)
120°C(5 min)
Adsorbent Trap
Initial bakeout
After each run Variable (5 min)
• 10.2.1 Optimize GC conditions for compound separation and sensitivity. Baseline separation of benzene and carbon tetrachloride on a 100% methyl pofysiloxane stationary phase is an indication of acceptable chromatographic performance.
10.2.2 The following are the recommended gas chromatographic analytical conditions when using a 50-meter by 0.3-mm I.D., 1 um film thickness fused silica column with refocusing on the column.
Item
Carrier Gas: Flow Rate: Temperature Program:
Condition
Helium Generally 1-3 mL/min as recommended by manufacturer Initial Temperature: -50 °C Initial Hold Time: 2 min Ramp Rate: 8° C/min Final Temperature: • 200°C Final Hold Time: Until all target compounds elute.
10.2.3 The following are the recommended mass spectrometer conditions:
Item Condition
I Is" I m I Ha ! IE
I m
-w - IE. i E . If)
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10.4.6 Documentation. Results of the BFB tuning are to be recorded and maintained as part of the instrumentation log.
10.5 Initial Calibration
.' 10.5.1 Summary. Prior to the analysis of samples and blanks but after the instrument performance check standard criteria have been met, each GC/MS system must be calibrated at five concentrations that span the monitonng range ot interest in an initial calibration sequence to determine instrument sensitivitv and the linearitv of GC/MS response for the target compounds. For example, the range of interest mav be 2 to 20 ppbv in- which case the five concentrations would be 1, 2, 5, 10 and 25 ppbv.
One of the calibration points from the initial calibration curve must be at the same concentration as the dailv calibration standard (e.g., 10 ppbv).
10.5.2 Frequency. Each GC/MS system must be recalibrated following corrective action (e a ion source cleaning or repair, column replacement, etc.) which may change or affect the initial calibration crite'ria or if the daily calibration acceptance criteria have not been met.
If time remains in the 24-hour time period after meeting the acceptance criteria for the initial calibration samples may be analyzed.
If time does not remain in the 24-hour period after meeting the acceptance criteria for the initial calibration a new analytical sequence shall commence with the analysis of the instrument performance check standard followed by analysis of a daily calibration standard.
10.5.3 Procedure. Verify that the GC/MS system meets the instrument performance criteria in Section 10.4.
The GC must be operated using temperature and flow rate parameters equivalent to those in Section 10 ? 2 Calibrate the preconcentration-GC/MS system by drawing the standard into the system.. Use one of the standards preparation techniques described under Section 9.2 or equivalent.
A minimum of five concentration levels are needed to determine the instrument sensitivity and linearity One of the calibration levels should be near the detection level for the compounds of interest. The calibration range should be chosen so that linear results are obtained as defined in Sections 10.5.1 and 10.5.5.
Quantitation ions for the target compounds are shown in Table 2. The primary ion should be used unless interferences are present, in which case a secondary ion is used.
10.5.4 Calculations.
[Note: In the following calculations, an internal standard approach is used to calculate response factors The area response used is that of the primary quantitation ion unless otherwise stated.]
10.5.4.1 Relative'Response Factor (RRF). Calculate the relative response factors for each target compound relative to the appropriate internal standard (i.e., standard with the nearest retention time) usin* the following equation: a
• A C RRF = x i s
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VOCs Method TO-15
RRT = £ H I i=i n
where: RRT - Mean relative retention time for the target compound for each initial calibration standard.
RRT = Relative retention time for the target compound at each calibration"leVel. 10.5.4.6 Tabulate Primary Ion Area Response (Y) for Internal Standard. Tabulate the area response
(Y) of the primary ions (see Table 2) and the corresponding concentration for each compound and internal standard.
10.5.4.7 Mean Area Response (Y) for Internal Standard. Calculate the mean area response (Y) for each internal standard compound over the initial calibration range using the following equation:
n v
Y = £ l i ; i=i n
where: Y = Mean area response. ,.
Y = Area response for the primary quantitation ion for the internal standard for each initial calibration standard.
10.5.4.8 Mean Retention Times (RT). Calculate the mean of the retention times (RT) for each internal standard over the initial calibration range using the following equation:
RT = J2 1
i=i n
where: RT = Mean retention time, seconds
RT = Retention time for the internal standard for each initial calibration standard, seconds: 10.5.5 Technical Acceptance Criteria for the Initial Calibration.
10.5.5.1 The calculated %RSD for the RRF for each compound in the calibration table must be less than 30% with at most two exceptions up to a limit of 40%,
[Note: This exception may not be acceptable for all projects. Many projects may have a specific target list of compounds which would require the lower limit for all compounds.]
10.5.5.2 The RRT for each target compound at each calibration level must be withiin 0.06 RRT units of the mean RRT for the compound.
10.5.5.3 The area response Y of at each calibration level must be within 40% of the mean area response Y over the initial calibration range for each internal standard.
10.5.5.4 The retention time shift for each of the internal standards at each calibration level must be within 20 s of the mean retention time over the initial calibration range for each internal standard.
10.5.6 Corrective Action. 10.5.6.1 Criteria. If the initial calibration technical acceptance criteria are not met, inspect the system
for problems. It may be necessary to clean the ion source, change the column, or take other corrective actions to meet the initial calibration technical acceptance criteria..
10.5.6.2. Schedule. Initial calibration acceptance criteria must be met before any field samples, performance evaluation (PE) samples, or blanks are analyzed.
*! It! IE
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 15-25
VOCs • '• : Method TO-15
usmg a,, reagents, standards, equipment, apparatus, glassware, and solvents that would be used for a sample
A laboratory method blank (LMB) is an unused, certified canister that has not left the laboratory Th, hi L canister is pressurized with humidified ultra-mire rem air ,„H • A , moratory. The blank
10.7.2 Frequency. The laboratory method blank must be analyzed after the calihnrinn « A A, s A before any samples are analyzed. • calibration standard(s) and
under Section 10.8.
apply equations in Section 10.5.4
The blank sample should be analyzed using the same procedure outlined U 1 I U C I o c l
10.7.4 Calculations. The blanks are analyzed similar to a field sample and the
10.7.5 Technical Acceptance Criteria. A blank canister should be analyzed daily.
The retention time for each of the internal standards must be within ±0 3 most recent valid calibration. 3 minutes between the blank and the
10.8 Sample Analysis
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 15-27
VOCs Method TO-15
A, = Area of the characteristic ion tor the compound to be measured, counts.
A i s = Area of the characteristic ion for the specific internal standard, counts.
Cis = Concentration of the internal standard spiking mixture, ppbv
RRF - Mean relative response factor from the initial calibration.
DF = Dilution factor calculated as described in section 2. If no dilution is performed. DF = 1.
[More: The equation above is valid under the condition that the volume (-500 pi) of internal standard spiking mixture added in all field and QC analyses is the same from run to run, and that the volume (~ 500 mL) of held and QC sample introduced into the trap is the same for each analysis.]
10.8.5 Technical Acceptance Criteria.
(Note: If the most recent valid calibration is an initial calibration, internal standard area responses and RTs in the sample are evaluated against the corresponding internal standard area responses and RTs in the mid level standard (10 ppbv) of the initial calibration.] •
10.8.5.1 The field sample must be analyzed on a GC/MS svstem meeting the BFB tuning initial calibration, and continuing calibration technical acceptance criteria at the frequency described in Sections 10 4 10.5 and 10.6. ' '
10.8.5.2 The field samples-must be analyzed along with,a laboratory method blank that met the blank technical acceptance criteria.
10.8.5.3 All of the target analyte peaks should be within the initial calibration range. 10.8.5.4 The retention time for each internal standard must be within ±0.33 minutes of the retention time
ot the internal standard in the most recent valid calibration. 10.8.6 Corrective Action. If the on-column concentration of any compound in any sample exceeds the
initial calibration range, an aliquot of the original sample must be diluted and reanalvzed. Guidance in performing dilutions and exceptions to this requirement are given below.
• Use the results of the original analysis to determine the approximate dilution factor required to *et the largest analyte peak within the initial calibration range. &
• The dilution factor chosen should keep the response of the largest analyte peak for a target compound in the upper half of the initial calibration range of the instrument.
[Note: Analysis involving dilution should be reported with a dilution factor and nature of the dilution gas.]
10.8.6.1 Internal standard responses and retention times must be evaluated during or immediately after data acquisition. If the retention time for any internal standard changes by more than 20 sec from the latest daily (24-hour) calibration standard (or mean retention time over the initial calibration range), the GC/MS system must be inspected tor malfunctions, and corrections made as required.
10.8.6.2 If the area response for any internal standard changes bv more than ±40 percent between the sample and the most recent valid calibration, the GC/MS system must be inspected tor malfunction and
Ho •ft! :ie IE
I It!
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 15-29
VOCs Method TO-15
11.3.2 There are several factors which may affect the precision of the measurement. The nature of the compound of interest itself such as molecular weight, water solubility, polarizability, etc., each have some effect on die precision, for a given sampling and analytical system. For example, styrene, which is classified as a polar VOC, generally shows slightly poorer precision than the bulk of nonpolar VOCs. A primary influence on precision is the concentration level of the compound of interest in the sample, i.e., the precision degrades as the concentration approaches the detection limit. A conservative measure was obtained from replicate analysis of "real world" canister samples from the TAMS and UATMP networks. These data are summarized in Table 5 and suggest that a replicate precision value of 25 percent can be achieved for each of the target compounds.
11.4 Audit Accuracy
11.4.1 A measure of analytical accuracy is the degree of agreement with audit standards. Audit accuracy is defined as the difference between the nominal concentration of the audit compound and the measured value divided by the.audit value and expressed as a percentage, as illustrated in the following equation:
A J V A 0 / Spiked Value - Observed Value Audit Accuracy, % = —!- x 100 Spiked Value
11.4.2 Audit accuracy results for TAMS and UATMP analyses are summarized in Table 6 and were used to form the basis for a selection of 30 percent as the performance criterion for audit accuracy.
i A
i -.
12. References
1. Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air: Method TO-14A, Second Edition, U. S. Environmental Protection Agency, Research Triangle Park, NC, EPA 600/625/R-96/010b, January 1997.
2. Winberry, W. T, Jr., et al., Statement-of-Work (SOW) for the Analysis of Air Toxics From Superfund Sites, U. S. Environmental Protection Agency, Office of Solid Waste, Contract Laboratory Program, Washington, D.C., Draft Report, June 1990.
3. Coutant, R.W., Theoretical Evaluation of Stability of Volatile Organic Chemicals and Polar Volatile Organic Chemicals in Canisters, U. S. Environmental Protection Agency, EPA Contract No. 68-DO-0007, Work Assignment No. 45, Subtask 2, Battelle, Columbus, OH, June 1993.
4. Kelly, T.J., Mukund, R., Gordon, S.M., and Hays, M.J., Ambient Measurement Methods and Properties of the 189 Tide I I I Hazardous Air Pollutants, U. S. Environmental Protection Agency, EPA Contract No. 68-DO-0007, Work Assignment 44, Battelle, Columbus, OH, March 1994.
5. Kelly T. J. and Holdren, M.W., "Applicability of Canisters for Sample Storage in the Determination of Hazardous Air Pollutants," Atmos. Environ., Vol. 29, 2595-2608, May 1995.
6. Kelly, T.J., Callahan, P.J., Pleil, J.K., and Evans, G.E., "Method Development and Field Measurements for Polar Volatile Organic Compounds in Ambient Air," Environ. Sci. Techno!., Vol. 27, 1146-1153, 1993. '
January 1999 Compendium of Methods for Toxic Organic Air Pollutants Page 15-31
7. McCIenny, W.A.. Oliver, K..D. and Daughtrey, E.H.., Jr. "Dry Purging of Solid Adsorbent Traps to Remove Water Vapor Before Thermal Desorption of,Trace Organic Gases," J. Air and Waste Manag. Assoc., Vol 45, 792-800, June 1995.
8. Whitaker, D.A., Fortmann, R.C. and Lindstrom, A.B. "Development and Testing of a Whole Air Sampler for Measurement of Personal Exposures to Volatile Organic Compounds," Journal of Exposure Analysis and Environmental Epidemiology, Vol. 5, No. 1, 89-100, January 19.95. '
9. Pleil. J.D. and Lindstrom, A.B., "Collection of a Single Alveolar Exhaled Breath for Volatile Organic Compound Analysis," American Journal of Industrial Medicine,,.Vol. 28, 109-121, 1995.
. 10. Pleil, J.D. and McCIenny, W.A., "Spatially Resolved Monitoring for.Volatile Organic Compounds Using Remote Sector Sampling," Atmos. Environ., Vol. 27A, No. 5, 739-747, August 1993.
11. Holdren, M.W., et al., Unpublished Final Report, EPA Contract 68-DO-0007, Battelle, Columbus, OH. Available from J.D. Pleil, MD-44, U. S. Environmental Protection Agency, Research Trianale Park. NC, 27711, 919-541-4680.
12. Morris, CM., Burkley, R.E. and Bumgarner, J.E., "Preparation of Multicomponent Volatile Organic Standards Using Dilution Bottles," Anal. Letts., Vol. 16 (A20), 1585-1593, 1983.
13. Pollack, A.J., Holdren, M.W., "Multi-Adsorbent Preconcentration and Gas Chromatographic Analysis of Air Toxics With an Automated Collection/Analytical System," in the Proceedings of the 1990 EPA/A&WMA International Symposium of Measurement of Toxic and Related Air Pollutants, U. S. Environmental Protection Agency, Research Triangle Park, NC, EPA/600/9-90-026, May 1990.
14. Stephenson, J.H.M., Allen, F., Slagle, T., "Analysis of Volatile Organics in Air via Water Methods" in Proceedings of the 1990 EPA/A&WMA International Symposium on Measurement of Toxic and Related Air Pollutants, U. S. Environmental Protection Agency, Research Triangle Park, NC, EPA 600/9-90-026, May 1990.
15. Oliver, K. D., Adams, J. R., Davehtrey, E. H., Jr.; McCIenny, W. A., Young, M. J., and Parade, M. A., "Techniques for Monitoring Toxices VOCs in Air: Sorbent Preconcentration Closed-Cycle Cooler Cryofocusing, and GC/MS Analysis," Environ. Sci. Techno!., Vol. 30, 1938-1945, 1996.
Page 15-32 Compendium of Methods for Toxic Organic Air Pollutants January 1999
APPENDIX B.
COMMENT ON CANISTER CLEANING PROCEDURES
The canister cleaning procedures given in Section 8.4 require that canister pressure be reduced to <0.05mm Hg before the cleaning process is complete. Depending on the vacuum system design (diameter of connecting tubing, valve restrictions, etc.) and the placement of the vacuum gauge, the achievement of this value'may take several hours. In any case, the pressure gauge should be placed near the canisters to determine pressure. The objective of requiring a low pressure evacuation during canister cleaning is to reduce contaminants. If canisters can be routinely certified (<0.2 ppbv for target compounds) while using a higher vacuum, then this criteria can be relaxed. However, the ultimate vacuum achieved during cleaning should always be <0.2mm Hg.
Canister cleaning as described in Section 8.4 and illustrated in Figure 10 requires components with special features. The vacuum gauge shown in Figure 10 must be capable of measuring 0.05mm Hg with less than a 20% error. The vacuum pump used for evacuating the canister must be noncontaminating while being capable of achieving the 0.05 mm Hg vacuum as monitored near the canisters. Thermoelectric vacuum gauges and turbomolecular drag pumps are typically being used for these two components.
An alternate to achieving the canister certification requirement of <0.2 ppbv for all target compounds is the criteria used in Compendium Method TO-12 that the total carbon count be <10ppbC. This check is less expensive and typically more exacting than the current certification requirement and can be used if proven to be equivalent to the original requirement. This equivalency must be established by comparing the total nonmethane organic carbon (TNMOC) expressed in ppbC to the requirement that individual target compounds be <0.2 ppbv for a series of analytical runs.
Page 15-34 Compendium of Methods for Toxic Organic Air Pollutants January 1999
Method TO-15 VOCs
APPENDIX D.
LISTING OF COMMERCIAL SUPPLIERS OF PERMEATION TUBES AND SYSTEMS
Kin-Tek 504 Laurel St. Lamarque. Texas 77568 (409) 938-3627 (800) 326-3627
Vici Metronics, Inc. 2991 Corvin Drive Santa Clara, C A 95051 (408)737-0550
Analytical Instrument Development. Inc. Rt. 41 and Newark Rd. Avondale, PA 19311 (215) 268-3181
Ecology Board, Inc. 9257 Independence Ave. Chatsworth, CA 91311 (213)882-6795
Tracor, Inc. . • . . -Jo. 6500 Tracor Land m Austin, TX • « (512) 926-2800 ' |S
Metronics Associates,.Inc. J ^ 3201 Porter Drive / Standford Industrial Park !,: Palo Alto, CA 94304 . p (415)493-5632
Page 15-36 Compendium of Methods for Toxic Organic Air Pollutants January 1999
TABLE 1. (continued)
Compound CAS No. BP (°C) y.p.
(mmllg)1 M W TO-I4A CLP-SOW Chloroprene (2-chloro-l ,3-butadiene); C4H5CI 126-99-8 59.4 226 88.5 Chloromelhyl methyl ether; C2H5CIO 107-30-2 59.0 224 805 Acrolein (2-propenal); C3H40 107-02-8 52.5 220 56 X 1,2-Epoxybutane (1,2-butylene oxide); C4H80 106-88-7 63.0 163 72 Chloroform; CHCI3 ! 67-66-3 61.2 160 119 X X Ethyleneimine (aziridine); C2H5N ' 151-56-4 56 160.0 43 .1,1-Dimethylhydrazine; C2H8N2 57-14-7 63 157.0 60.0 Hexane;C6HI4 110-54-3 69.0 120 86.2 X 1,2-Propyleneimine (2-methylaziridine); C3H7N 75-55-8 66.0 112 57.1 Acrylonitrile (2-propenenitrile); C3H3N 107-13-1. 77.3 100 53 X Methyl chloroform (1,1,1 -trichloroethane); C2H3CI3 71-55-6 74.1 100 133.4 X - X Methanol; CH40 67-56-1 65.0 92.0 32 X Carbon tetrachloride; CCI4 56-23-5 76.7 90.0 153.8 X X Vinyl acetate; C4H602 108-05-4 72.2 83.0 86 X Methyl ethyl ketone (2-butanone); C4H80 . - - 78-93-3 79.6 77.5 72 X Benzene; C6H6 71-43-2 80.1 76.0 78 X X Acetonitrile (cyanomethane); C2H3N 75-05-8 82 74.0 41.0 X Ethylene dichloride (1,2-dichloroethanc); C2I I4CI2 107-06-2 • 83.5 61.5 99 X X Triethylamine; C6H15N 121-44-8 89.5 54.0 101.2 Methylhydrazine; CH6N2 60-34-4 87. 8 49.6 46.1
Propylene dichloride (1,2-dichloropropane); C3H6CI2 • 78-87-5 97.0 42.0 113 X X 2,2,4-Ti imethyl pentane CSHI8 540-84-1 99.2 40.6 114 1,4-Dioxane (1,4-Diethylene oxide); C4H802 "' " 123-91-1 101 37.0 ' 88 Bis(chloromethyl) ether; C2H4CI20 542-88-1 104 30.0 115 Ethyl acrylate; C5H802 140-88-5 100 29.3 100
Methyl methacrylate; C5H802 80-62-6 101 28.0 100.1
Compound
Cumene (isopropylbenzene); C9H 12
Acrylic acid; C3H402
N.N-Dimethylformamide: C3H7NO
1,3-Piopane sultone; C3H6Q3S
Acetophenone; CSII80
Dimethyl sulfate; C2H604S
TABLE 1. (continued)
CAS No.
98-82-8
79-10-7
68-12-2
1120-71-4
98-86-2
77-78-
BP(°C)
153
153
180/30n
202
. v.p. (mmllg)'
3.2
3.2
2.7
2.0
1.0
1.0
M W
120
72
TO-I4A
73
122.1
120
126.1
CLP-SOW
Benzyl chloride (a-chlorotoluene); C7H7CI
,1,2-Dibrotno-3-chloropropane; C3H5Br2CI
Bis(2-Chloroethyl)ether; C4H8C120
Chloroacetic acid; C2H3CIQ2
Ariiline (aminobenzene); C6H7N
,4rDichlorobenzcne (p-); C6H4CI2
Ethyl carbamate (methane); C3H7NQ2
Aciylamide; C3H5NO
N,N-Dimethylaniline; C8HI IN
Hexachloroethane; C2CI6
lexachlotohutadicne; C4CI6
sophorone; C9HI4Q
N-Nitrosomorpholine; C4H8N2Q2
Stymie oxide; CSH80
Diethyl sulfate; C4H10O4S
Cresylic acid (cresol isomer mixture);C7H8Q
o-Cresol; C7H80
Catechol (o-hydroxyphenol); C6H6Q2
Phenol; C6H6Q
100-44-7 179 1.0 126.6
96-12-8 196 0.80 236.4
111-44-4 178 0.71 143
79-11-8 189 0.69 94.5
62-53-3 0.67
106-46-7 173 0.60
51-79-6 183
79-06-1 125/25 mm
0.54
0.53
93
147
89
71
121-69-7 192 0.50 121 67-72- Sublimes at 186 0.40 236.7
87-68-3 215 0.40 260.8
78-59-1 215 0.38 138.2
59-89-2 225 0.32 I 16.
96-09-3 194 0.30 120.2 64-67-5 208 0.29 154
1319-77-3 202 0.26 108
95-48-7 191 0.24 108
120-80-9 240
108-95-2 182
0.22
0.20 94
Method TO-15 VOCs
TABLE 2. CHARACTERISTIC MASSES (M/Z) USED FOR QUANTIFYING THE TITLE III CLEAN AIR ACT AMENDMENT COMPOUNDS
Compound CAS No. Primary Ion Secondary Ion Methyl chloride (chloromethane): CH3C1 74-87-3 50 52 Carbonvl sulfide: COS 463-S8-I 60 62 Vinvl chloride (ehloroethene): C2H3C! 7S-01-4 62 64 Diazomethane: CH2N2 334-88-3 42 41. Formaldehyde: CH20 50-00-0 29 30 1.3-Butadiene: C4H6 106-99-0 39 54 Methyl bromide (bromomethane): CH3Br 74-83-9 94 96 Phoscene: CC120 75-44-5 63 65 Vinyl bromide (bromoethene): C2H3Br 593-60-2 106 108 Ethvlene oxide: C2H40 75-21-8 29 44 Ethyl chloride (chloroethane): C2H5C1 75-00-3 64 66 Acetaldehyde (ethanal): C2H40 75-07-0 44 29. 43 Vinylidene chloride 1 1.1-dichloroethvlene): C2H2C12 75-35-4 61 ' 96 Propylene oxide: C3H60 ' 75-56-9 58 57 Methyl iodide (iodomethane): CH3I 74-88-4 142 127 Methylene chloride: CH2C12 75-09-2 49 84. 86 Methvl isocvanate: C2H3NO 624-83-9 .57 56 Allyl chloride (3-chloropropene): C3H5C1 107-05-1 76 41.78 Carbon disulfide: CS2 75-15-0 76 44. 78 Methyl tert-butyl ethen C5H120 1634-04-4 73 ' 41. 53 Propionaldehyde: C2H5CHO 123-38-6 58 29. 57 Ethylidene dichloride (1.1-dichloroethane): C2H4C12 . 75-34-3 63 65. 27
Chloroprene (2-chloro-1.3-butadiene): C4H5C1 126-99-8 . 88 53. 90 Chloromethvl methvl ether: C2H5C10 107-30-2 45 29. 49 Acrolein (2-propenal); C3H40 107-02-8 56 55
1.2-Epoxybutane (1.2-butvlene oxide); C4H80 106-88-7 42 41. 72 Chloroform: CHC13 67-66-3 83 85. 47 Ethyleneimine (aziridine): C2H5N 151-56-4 42 43 1.1-Dimethylhydrazine: C2H8N2 57-14-7 60 45. 59 Hexane:C6H14 110-54-3 57 41. 43 1.2-Propyleneimine (2-methvlazindine): C3H7N 75-55-8 56 ' 57:42 Acrylonitrile (2-propenenitrile): C3H3N 107-13-1 53 52 Methyl chloroform (1.1.1 trichloroethane): C2H3CI3 71-55-6 •97 • 99.61 Methanol: C1-140 67-56-1 31 29 Carbon tetrachloride: CC14 56-23-5 117 1 19 Vinvl acetate: C4H602 108-05-4 43 86 Methvl ethvl ketone (2-butanone): C4I-I80 78-93-3 43 72
Page 15-42 Compendium of Methods for Toxic Organic Air Pollutants January 1999
Method TO-15 VOCs
Compound CASNo. Primarv Ion Secondary Ion Aeetophenone: C8HSO 98-86-2 105 . 77.120 Dimethyl sulfate: C2H604S . 77-78-1 95 66.96 Benzyl chloride (a-chlorotoluene): C7H7CI 100-44-7 91 126 l.2-Dibromo-3-chloroDroDane: C3H5Br2CI 96-12-8 57 155. 157 Bis(2-Chloroethvl)ether: C4HSCI20 111-44-4 93 63. 95 Chloroacetic acid: C2H3CI02 79-11-8 50 45. 60 Aniline (aminobenzene): C6H7N 62-53-3 93 66 1.4-Dichlorobenzene (p-): C6H4CI2 106-46-7 146 148. i 1 1 Ethyl carbamate (urethane): C3H7N02 51-79-6 31 44. 62 Acrylamide: C3H5NO 79-06-1 .44 55. 71 N.N-Dimethvlaniline: C8H1 IN 121-69-7 120 77. 121 He.xachloroethane: C2CI6 67-72-1 201 199. 203 Hexachlorobutadiene: C4CI6 87-68-3 225 227. 223 Isophorone: C9HI40 7S-59-1 82 138 N-Nitrosomorpholine: C4H8N202 :
59-89-2 56 86. 1 16 Styrene oxide: C8H80 96-09-3 • 91 120 Diethyl sulfate: C4H10O4S 64-67-5 45 59. 139 Cresylic acid (cresol isomer mixture); C7H80 . 1319-77-3 o-Cresol: C7H80 95-48-7 108 107 Catechol (o-hydroxvphenol): C6H602 120-80-9 110 64 Phenol: C6H60 108-95-2 94 66 1.2.4-Trichlorobenzene: C6H3CI3 120-82-1 180 182. 184 Nitrobenzene: C6H5N02 ]; 98-95-3 77 ' 51. 123
Page 15-44 Compendium of Methods for Toxic Organic Air Pollutants Ja
Method TO-15 VOCs
TO-l4AList Lab#k SCAN Lab #2. SIM Benzene 0.34 0.29 Benzyl Chloride
Carbon tetrachloride 0.42 0.15 Chlorobenzene 0.34 ' 0.02 Chloroform ' 0.25 0.07 1.3-Dichlorobenzene • 0.36 0.07 1.2-Dibromoethane 0.05 1.4-Dichlorobenzene 0.70 0.12 1.2-Dichlorobenzene 0.44 1.1-Dichloroethane 0.27 0.05 1.2-Dichloroethane 0.24 l.l-Dichloroethene 0.22 cis-1.2-Dichloroethene 0.06 Methvlene chloride 1.38 0.84 1.2-DichloroDrooane 0.21 cis-1.3-DichloroDTODene : 0.36 trans-1.3-Dichloroprooene , 0.22 Ethvlbenzene 0.27 0.05 Chloroethane 0.19 Trichlorofluoromethane
1.1.2-Trichloro-1.2.2-trifluoroethane
1.2-Dichloro-1.1.2.2-tetrafluoroethane
Dichlorodifluoromethane
Hexachlorobutadiene
Bromomethane ' 0.53 Chloromethane 0.40 Stvrene 1.64 0.06 1.1 -2.2-Tetrachloroethane 0.28 0.09 Tetrachloroethene 0.75 0.10 Toluene 0.99 0.20 1.2.4-Trichlorobenzene
l.I.I-Trichloroethane 0.62 0.21 1.1.2-Trichloroethane . 0.50 Trichloroethene 0.45 0.07 1.2.4-Trimethvlbenzene
I.3.5-Trimethvlbenzene
Vinvl Chloride 0.33 0.48 m.p-Xvlene 0.76 0.08 o-Xylene 0.57 0.28
« •Ha IE IE
«n, IO me (JIUUUCI oi tne stanaarci deviation ot seven replicate analyses and the student's "t" test value for 99% confidence. For Lab #2, the MDLs represent an average over four studies MDLs are for MS/SCAN for Lab ft I and for MS/SIM for Lab W>
Page 15-46 Compendium of Methods for Toxic Organic Air Pollutants . January 1999
Method TO-15 VOCs
To AC
Inlet
Insulated Enclosure
Electronic Timer
Electronic Timer
Electronic Timer
Vocuum/Pressure Gouge
Valve
To AC
Figure 1. Sampler configuration for subatmospheric pressure or pressurized canister sampling. '
Page 15-48 Compendium of Methods for Toxic Organic Air Pollutants January 1999
Method TO-15 VOCs
Heated Enclosure
Inlet
A
~ 1 . 6 Meters (~5 f t )
Ground Level
7T
Inlet Manifold
Pump
Thermostat
Prsssura Gouge
T Vent
Electronic Timer
Heater
Tan
I ; _ _ _ _
I Vent
T
I Auxi l iary Vacuum
Pump
Vacuum/Pressure Gauge
Magnelatch Volve
Vent
r Valve)
Canister
1
To AC
Figure 3. Alternative sampler configuration for pressurized canister sampling.
Page 15-50 Compendium of Methods for Toxic Organic Air Pollutants January 1999
o
Z D O O
Si tr < LU W z o to uu rr z LU CD O CC Q > X
150
140
130
120
110 -
1 0 0 , r
100 200 300 400 500 600 700 800 900 1000 1100 PURGE VOLUME, ml
Figure 5. Residua! water vapor on VOC concentrator vs. dry He purge volume.
Colibrotion Gos Cylinder
Zero Air Cylinder
(o) Reol Time GC-FID-ECD-PID
or GC-MS
Moss Flow Control ler
( 0 - 5 0 m L / m i n )
Mass Flow Control ler
( 0 - 5 0 L / m i n )
(b) Evacuated or Pressurized Conister Sampling System
500 mL R o u n d - B o t t o m
Flask
Humidif ier
Vocuum/Pressure Gouge
Shut Off . Volve
(c) Canister Transfer Slandord
Figure 8. Schematic diagram of calibration system and manifold for (a) analytical system calibration, (b) testing canister sampling system and (c) preparing canister transfer standards
Pressure Regulator
Exhaust
Exhaust
Vocuum Pump Vent Shut. Off Valve Valve Check Valve
Exhaust <4 t / * \ J
Vent Shut Off
Valve
Cryogenic Trap Cooler
(Liquid Argon)
Humidifier
Zero Shut Off
Valve
Manifold
Optional Isothermol
Oven
Figure 10. Canister c lean ing system.
Page 15-56 Compendium of Methods for Toxic Organic Air Pollutants January 1999
Method TO-15 VOCs
! m i «!
TIME
(b). Contaminated Sampler
Figure 12. Example of humid zero air test results for a clean sample canister (a) and a contaminated sample canister (b).
Page 15-58 Compendium of Methods for Toxic Organic Air Pollutants January 1999
3-WAY VALVE
Figure 14. Water method of standard preparation in canisters.
Page 15-60 Compendium of Methods for Toxic Organic Air Pollutants January 1999
STATUS:
TRAP 1: Sampling TRAP 2: Desorbing
CLOSED A oreNift Mrc PUMP MT£T
SAMPLE PUMP
SAMPLE INLET
CAL/INT STD VENT
PURGE GAS
CALGAS
INTERNAL STD
| MFC |-
• t><3 SV-2I
f—C*r—<»
sv
•A—<> A—
PUgGE GAS SAMPLE___PUnGFi VENT
IILLIUM
SOLID SORDENT CONCENTRATOR
i '>:'>:'>:'>:'>:'>:'>:'>:\
iiiiiiiiiiiiiiiiii 1
TO GC/ ; »»
DETECTOR
STIRLING CYCLE COOLER
Figure 16r Sample flow diagram of a commercially-available concentrator showing the combination of multisorbent ti.be and cooler (Trap 1 sampling; Trap 2 desorbing).
APPENDIX D
U.S. EPA Environmental Response Team (ERT)
Standard Operating Procedure (SOP) #1704: SUMMA Canister Sampling
July 1995
m U. S. EPA ENVIRONMENTAL RESPONSE TEAM W •
STANDARD OPERATING PROCEDURES SOP:
PAGE: REV:
DATE:
1704 1 of 15
0.1 07/27/95
SUMMA CANISTER SAMPLING
CONTENTS
1.0 SCOPE AND APPLICATION
2.0 METHOD SUMMARY
3.0 SAMPLE PRESERVATION, CONTAINERS, HANDLING, AND STORAGE
4.0 INTERFERENCES AND POTENTIAL PROBLEMS
5.0 EQUIPMENT/APPARATUS
5.1 Subatmospheric Pressure Sampling Equipment
5.2 Pressurized Sampling Equipment
6.0 REAGENTS
7.0 PROCEDURES
7.1 Subatmospheric Pressure Sampling 7.1.1 Sampling Using a Fixed Orifice, Capillary, or Adjustable Micrometering Valve ' 7.1.2 Sampling Using a Mass Flow Controller/Vacuum Pump Arrangement (Andersen Sampl
87-100)
7.2.1 Sampling Using a Mass Flow Controller/V acuum Pump Arrangement (Andersen Sampler Model 87-100)
7.2 Pressurized Sampling
8.0 CALCULATIONS
9.0 QUALITY ASSURANCE/QUALITY CONTROL
10.0 DATA VALIDATION
11.0 HEALTH AND SAFETY
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1.0 SCOPE AND APPLICATION
The purpose ofthis standard operating procedure (SOP) is to describe a procedure for sampling of volatile organic compounds (VOCs) in ambient air. The method is based on samples collected as whole air samples in Summa passivated stainless steel canisters. The VOCs are subsequently separated by gas chromatography (GC) and measured by mass-selective detector or multidetector techniques. This method presents procedures for sampling into canisters at final pressures both above and below atmospheric pressure (respectively referred to as pressurized and subatmospheric pressure sampling).
This method is applicable to specific VOCs that have been tested and determined to be stable when stored in pressurized and subatmospheric pressure canisters. The organic compounds that have been successfully collected in pressurized canisters by this method are listed in the Volatile Organic Compound Data Sheet (Appendix A). These compounds have been measured at the parts per billion by volume (ppbv) level.
These are standard (i.e., typically applicable) operating procedures which may be varied or changed as required, dependent on site conditions, equipment limitations or limitations imposed by the procedure or other procedure limitations. In all instances, the ultimate procedures employed should be documented and associated with the final report.
Mention of trade names or commercial products does not constitute U.S. EPA endorsement or recommendation for use.
2.0 METHOD SUMMARY
Both subatmospheric pressure and pressurized sampling modes use an initially evacuated canister. Both modes may also use a mass flow controller/vacuum pump arrangement to regulate flow. With the above configuration, a sample of ambient air is drawn through a sampling train comprisedof components that regulate the rate and duration of sampling into a pre-evacuated Summa passivated canister. Alternatively, subatmospheric pressure sampling may be performed using a fixed orifice, capillary, or adjustable micrometering valve in lieu of the mass flow controller/vacuum pump arrangement for taking grab samples or short duration time-integrated samples. Usually, the alternative types of flow controllers are appropriate only in situations where screening samples are taken to assess for future sampling activities.
3.0 SAMPLE PRESERVATION, CONTAINERS, HANDLING, AND STORAGE
; After the air sample is collected, the canister valve is closed, an identification tag is attached to the canister, and the canister is transported to a laboratory for analysis. Upon receipt at the laboratory, the canister tag data is recorded. Sample holding times and expiration should be determined prior to initiating field activities.
4.0 INTERFERENCES AND POTENTIAL PROBLEMS
UBHBj U. S. EPA ENVIRONMENTAL RESPONSE TEAM
STANDARD OPERATING PROCEDURES SOP
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DATE SUMMA CANISTER SAMPLING
4. Particulate matter filter - 2- m sintered stainless steel in-line filter (Nupro Co., Model SS-2F-K4-2, or equivalent).
5. Cliromatographic grade stainless steel tubing and fittings - for interconnections (Alltech Associates, Cat. #8125, 'or equivalent). All materials in.contact with sample, analyte, and support gases should be chromatographic grade stainless steel.
6.0 REAGENTS
This section is not applicable to this SOP.
7.0 PROCEDURE
7.1 Subatmospheric Pressure Sampling
7.1.1 Sampling Using a Fixed Orifice, Capillary, or Adjustable Micrometering Valve
Prior to sample collection, the appropriate information is completed on the Canister Sampling Field Data Sheet (Appendix C).
A canister, which is evacuated to 0.05 mm Hg and fitted with a flow restricting device, is opened to the atmosphere containing the VOCs to be sampled.
The pressure differential causes the sample to flow into the canister.
This technique may be used to collect grab samples (duration of 10 to 30 seconds) or time-integrated samples (duration of 12 to 24 hours). The sampling duration depends on the degree to which the flow is restricted.
A critical orifice flow restrictor will have a decrease in the flow rate as the pressure approaches atmospheric.
Upon sample completion at the location, the appropriate information is recorded on the Canister Sampling Field Data Sheet.
7.1.2 Sampling Using a Mass Flow Controller/V acuum Pump Arrangement (Andersen Sampler Model 87-100)
1: Prior to sample collection the appropriate information is completed on the Canister Sampling Field Data Sheet (Appendix C).
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1.
2.
3.
4.
5.
6.
bRBM U. S. EPA ENVIRONMENTAL RESPONSE TEAM
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8.0 CALCULATIONS
1. A flow control device is chosen to maintain a constant flow into the canister over the desired sample period. This flow rate is determined so the canister is filled to about 88.1 kPa for subatmospheric pressure sampling or to about one atmosphere above ambient pressure for pressurized sampling over the desired sample period. The flow rate can be calculated by:
F WW (7X60)
where: •
flow rate (cmVmin) final canister pressure, atmospheres absolute volume of the canister (cm3) sample period (hours)
For example, if a 6-L canister is to be filled to 202 kPa (two atmospheres) absolute pressure in 24 hours, the flow rate can be calculated by:
F W 0 0 0 ) 8 3 c / n 3 / m i n
(24)(60)
F P V T
If the canister pressure is increased, a dilution factor (DF) is calculated and recorded on the sampling data sheet.
DF I* Xa
where:
U. S. EPA ENVIRONMENTAL RESPONSE TEAM
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3. J. F. Walling, "The Utility of Distributed Air Volume Sets When Sampling Ambient Air Using Solid Adsorbents," Atmospheric Environ., 18:855-859, 1984.
4. J. F. Walling, J. E. Bumgarner, J. D. Driscoll,C. M. Morris, A. E. Riley, and L. H. Wright, "Apparent Reaction Products Desorbed From Tenax Used to Sample Ambient Air," Atmospheric Environ., 20:51 -57, 1986.
5. Portable Instruments User's Manual for Monitoring VOC Sources, EPA-340/1 -88-015, U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards, Washington, D.C., June 1986.
6. R. A. Rasmussen and J. E. Lovelock, Atmospheric Measurements Using Canister Technology, J. Geophys. Res., 83: 8369-8378, 1983.
R. A. Rasmussen andM. A. K. Khalil, "Atmospheric Halocarbon: Measurements and Analysis of Selected Trace Gases," Proc. NATO ASI on Atmospheric Ozone, BO: 209-231.
EPA Method TO-14 "Detennination of Volatile Organic Compounds (VOCs) in Ambient Air Using Summa Passivated Canister Sampling and Gas Chromatographic Analysis", May 1988.
APPENDIX A Volatile Organic CompoundiData Sheet
SOP #1704 July 1995
U. S. EPA ENVIRONMENTAL RESPONSE TEAM
STANDARD OPERATING PROCEDURES SOP
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APPENDIX B Figure
SOP #1704 July 1995
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APPENDIX C Canister Sampling Field Data Sheet
SOP #1704 July 1995
APPENDIX E
U.S. EPA Environmental Response Team (ERT)
Standard Operating Procedure (SOP) #170: Sample Documentation
September 1994
| | | p U. S. EPA ENVIRONMENTAL RESPONSE TEAM
STANDARD OPERATING PROCEDURES . ' SOP: 1703
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:CONTENTS
I . 0 SCOPE AND APPLICATION ''
2.0 METHOD SUMMARY
3.0 SAMPLE PRESERVATION, CONTAINERS, HANDLING AND STORAGE
3.1 Canister Receipt
3.2 Canister Storage
4.0 INTERFERENCE AND POTENTIAL PROBLEMS '
5.0 EQUIPMENT/APPARATUS
5.1 Canister .; '
5.2 Canister Cleaning System
6.0 REAGENTS ' ,
7.0 PROCEDURE
7.1 System Set-Up 7.2 Cleaning
7.3 Leak-Testing . ' ;•• . [
8.0 CALCULATIONS
9.0 QUALITY ASSURANCE/QUALITY CONTROL ! .
10.0 DATA VALIDATION ' '
I I . 0 HEALTH AND SAFETY
12.0 REFERENCES : :
13.0 APPENDIX
A - Figures
SUPERCEDES: SOP #1703; Revision 2.1; 05/24/91; U.S. EPA Contract 68-03-3482.
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1.0 SCOPE AND APPLICATION
This standard operating procedure (SOP) is intended for use when cleaning Summa polished stainless steel canisters. Summa canisters provide a medium to sample gas-phase Volatile Organic Compounds (VOCs) on-site at concentrations of one part per billion by volume (ppbv) and greater. This procedure is to assure that canisters have been sufficiently cleaned prior to sampling, to the extent that no VOC contamination is present at concentrations greater than 0.2 ppbv.
These are standard (i.e., typically applicable) operating procedures which may be varied or changed as required, dependent on site conditions, equipment limitations or limitations imposed by the procedure or other procedure limitations. In all instances, the ultimate procedures employed should be documented and associated widi the final report.
Mention of trade names or commercial products does not constitute U.S. EPA endorsement or recommendation for
2.0 METHOD SUMMARY
After use, canisters are logged in and physically inspected. These canisters are vented to the outside air under an operating exhaust hood. Canisters are connected to a manifold which is attached to a vacuum pump via a cryogenic trap. The canisters and lines are evacuated and then the canisters are heated to an elevated temperature for a prescribed time period. During the heating period, the canisters are filled with humidified nitrogen and pressurized. The process is repeated. The filling and pressurizing functions are followed by evacuation and heating and are performed a total of three times.
Canisters are confirmed free of VOC contamination by pressurizing the canisters with ultra high purity nitrogen and analyzing on the GC/MS. If no VOC contamination is present at concentrations greater than 0.2 ppbv, the canister is determined clean. Clean canisters are leak-tested by pressurizing with nitrogen for 24 hours. Canisters that have
. been determined clean and without leaks are evacuated. These canisters are logged in as cleaned and certified and are stored in the evacuated state with brass cap fittings until needed for sampling.
3.0 SAMPLE PRESERVATION, CONTAINERS, HANDLING AND STORAGE
3.1 Canister Receipt
use.
The overall condition of each sample canister is observed. Any canister having physical defects requires corrective action.
2 Each canister should be observed for an attached sample identification number.
Each canister is recorded in the dedicated laboratory logbook by its Summa canister number.
3.2 Canister Storage
« g f | ) U. S. EPA ENVIRONMENTAL RESPONSE TEAM
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6.0 REAGENTS
Gas cylinders of nitrogen, ultra high purity grade.
Cryogen - liquid nitrogen (bp -195°C).
Distilled, deionized water, ultra high purity.
7.0 PROCEDURE •
7.1 System Set-Up
1. All connections in the vacuum system except the canisters and manifold are sealed. All connections, lines, and valves are checked for leaks by pressurizing the line to 30 psig and using a soap solution. The septum is checked for leaks by visual inspection.
2. The liquid nitrogen is added to the cryogenic trap and allowed to equilibrate.
3. Check the pump to assure proper working order by achieving a vacuum of 0.05 mm Hg in the line that normally attaches to the manifold but is now capped. Valve A is open and Valve B is closed. After the vacuum test is completed, turn the pump off and remove the cap to break the vacuum.
4. Check the oven to assure proper working order by heating the oven to 100°C and measuring the internal temperature with a thermometer.
5. Check reagents to assure proper purity.
6. Set the back pressure on the nitrogen to 30 psig.
7.2 Cleaning
1. All canisters are vented to the outside air under an operating exhaust hood.
2. Connect the canisters (with the valves closed on the canisters) to the manifold by the Swagelok fittings. Connect the manifold to the vacuum system by the Swagelok fitting.
3. Open Valve A, assure Valve B is closed, and start vacuum pump.
4. Once a vacuum (0.05 mmHg) is obtained in the line and the manifold, Valve A is closed. The system is then examined for leaks by comparing the initial vacuum reading and a second vacuum reading three minutes later. I f the vacuum deteriorates more than 5 mm Hg, a leak exists and corrective action, such as tightening all fittings, is necessary.
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5. If no leaks are observed, Valve A is opened and the Canister 1 valve is opened. Evacuate Canister 1 to 0.05 mm Hg, then close Canister 1 valve. By evacuating one canister at a time, cross contamination between canisters is minimized.
y U, S. EPA ENVIRONMENTAL RESPONSE TEAM A;
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7.3 Leak-Testing
Once the canister lot is determined as being clean, the canisters are pressurized to 30 psig with nitrogen..
2 The initial pressure is measured via the pressure gauge, die canister valve is closed, and die brass cap is replaced. Document the time and pressure.
After 24 hours, the final pressure is checked. Document the time and pressure.
4. If leak tight, the pressure should not vary more than ±13.8 kPa (±2 psig) over the 24-hour period. If this criterion is met, the canister is capped with a brass fitting and stored. If a leak is present, corrective action such as tightening all fittings, is required. Document the results.
8.0 CALCULATIONS
There are no calculations for this SOP.
9.0 QUALITY ASSURANCE/QUALITY CONTROL -
The following specific quality assurance/quality control procedures are applicable for Summa canister cleaning
1. • All connections, lines, and valves are checked to assure no leaks are present.
2. The septum is checked, to assure no leaks are present, by removing the septum and visually examining it.
3. The pump is checked to assure proper working order by achieving a vacuum of 0.05 mm Hg prior to cleaning.
4. The oven is checked to assure proper working order by comparing the oven setting at 100°C to the internal temperature with a thermometer.
5. The reagents are checked to assure sufficient purity.
6. All canisters are to be evacuated to 0.05 mmHg during each cycle of the cleaning process and the results are to be documented. '
7. All canisters are to be evacuated at 100°C for one hour during each cycle of the cleaning process. Results are to be documented.
8. All canisters are to be evacuated, heated, and pressurized three times during the cleaning process. Document each cycle.
9. The selected canister from the cleaning lot to be tested must be analyzed by GC/MS as shown to be sufficiently cleaned to the extent that no VOC contamination is present at concentrations greater than 0.2 ppbv for the canister lot to be considered cleaned. If the VOC contamination is greater than 0.2 ppbv, the canister lot must be cleaned again. In either case, the results will be documented.
(iKHRJ U. S. EPA ENVIRONMENTAL RESPONSE TEAM
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APPENDIX A Figures
SOP #1703 September 1994
APPENDIX F
ERG's Method Detection List
Compound ppbv | Compound ppbv [Ethyl Aery late 0.16 | Bromodichloromethane 0.06 jTrichloroethylene 0.07 | Methyl Methacrylate 0.18 \cis-1,3-Dichloropropene 0.1 |Methyl Isobutyl Ketone 0.15 \trans-1,3-Dichlordpropene 0.11 |1,1,2-Trichloroethane 0.06 |Toluene 0.06 |Dibromochloromethane 0.08 |1,2-Dibromoethane 0.08 ui-Octane 0.06 |Tetrachlproethylene 0.06 jChlorobenzene 0.06 jEthylbenzene 0.04 ]m,p-Xylene 0.05 |Bromoform 0.08 |Styrene 0.07 |1,1,2,2-Tetrachloroethane 0.06 |0-Xy/ene 0.05 j 1,3,5-Trimethylbenzene 0.07 11,2,4-Trimethylbenzene 0.07 | m-Dichlorobenzene 0.05 | Chloromethylbenzene 0.07 \p-Dichlorobenzene 0.09 \o-Dichlorobenzene 0.06 11,2,4-Trichlorobenzene 0.06 |Hexachloro-1,3-Butadiene 0.06
[Acetylene 0.13 [Propylene 0.05 jDichlorodifluoromethane 0.04 IChloromethane 0.06 iDichlorotetrafluoroethane 0.05 iVinyl Chloride 0.06 :1,3-Butadiene 0.07 iBromomethane 0.09 Chloroethane 0.08 Acetonitrile 0.25 [Acetone 0.26 iTrichlorofluoromethane 0.04 iAcrylonitrile 0.21 h,1-Dichloroethene 0.1 ! Methylene Chloride 0.06 jTrichlorotrifluoroethane 0.07 \ trans-1,2-Dichloroethylene 0.06 1,1,-Dichloroethane 0.08 Methyl tert-Butyl Ether 0.18 Methyl Ethyl Ketone 0.15 Chloroprene 0.1 cis-1,2-Dichloroethene 0.1 Bromochloromethane 0.12 Chloroform 0.05 Ethyl tert-Butyl Ether 0.15 1,2-Dichloroethane 0.06 1,1,1-Trichloroethane 0.06 Benzene 0.04 Carbon Tetrachloride 0.08 tert-Amyl Methyl Ether 0.12 1,2-Dichloropropane 0.07
APPENDIX G
Example Questionnaire
Example Canister Field Data Sheet
and
Example Chain of Custody
Project No. Element No. Revision No. Date Page
0121.00 B2
1 March 2000.
2 of 17
IBS EASTERN RESEARCH GROUP, INC
Canister Sample Data Sheet LAB ID#
UJ u.
CD z -> o LU DC.:
o O
Location: City / State Sampling Period: Nox Analyzer Operating: Average PPM:
. Elapsed Time:
Average Wind Speed: _ Average Wind Direction: Average Temperature: Average Barometric Pressure: Relative Humidity: Flow Controller Set at: Comments:
Site Code: Collection Date:
Canister Number: Operator:
Initial Vacuum: Final Field Pressure/Vacuum:
Duplicate (YIN) Duplicate Can #:
Options Flow Controller Zero Reading
Received by: Date Received: Carbonyl Tubes:
Carbonyl ID #: _
Pressure @ Receipt: Void Acceptable Yes No
Stored:
Analyst: Analysis Date: Analysis Time: NMOC Instrument:
Area Counts run 1: ppmC run 1:
Canister Number: Analysis Pressure: Sample Replicate:
Initial or Repeat:
Average AC: Standard Dev:
Entered into Database by:
Area Counts run 2: ppmC run 2: •
Average: ppmC: Standard Dev:
Area Counts run 3: ppmC run 3:
Date:
o o 5 z w
Analyst: _ _ _ _ _ Analysis Pressure: Load Volume:
Date: Data File Name: Duplicate File Name:
Date:
g " X "
o I V
Analyst: Analysis Pressure: Load Volume:
Date: Data File Name: Duplicate File Name: Replicate File Name:
White: Sample File Copy Yellow: Receiving Copy
Figure 7-1. Canister Sample Data Sheet
Pink: Field Copy
glp/D:\SECT7,WPD
Site:
Date:
I.D. #
Channel PPMC IB:
rata
Figure 7-3. Canister Tag
US EPA REGION 2
CHAIN OF CUSTODY/ FIELD DATA FORM Page of pages
SURVEY NAME & LOCALITY
PROGRAM: SF'("~
Permit #
SITE ID OPERABLE UNIT PROJECT LEADER
PROGRAM RESULTS CODE
RCRA • NPDES • SDWA • AM _ CAA • TSCA |~1 ENFORCEMENT: CRIMINAL O CIVIL •
LAB ID/ FIELD ID
o Z £ SPECIAL ni « =H REQUIRE-
DESCRIPTION & INSTRUCTIONS INCLUDING LOCATION, ESTIMATED CONCENTRATIONS, SPECIAL REPORTING LIMITS, SPECIAL TEST REQUIREMENTS & ALIQUOTING
Preservative
(circle)
Collection Time (24hr clock) //////////////
Collection Date
u 1 2 3 4 5 6 7 8 E
11 I I i i / u u / y y
• 1 2 34 5 6 7 8S
L I 1 2 3 4 5 6 7 89
• .1 2 3 4 5 6 7 8 9
• 1 2 3 4 5 6 7 8 9
• 12 3 4 5 6 7 8 9
I I • ' • 1 2 3 4 5 6 7 8 9
• • • 12 3 4 5 6 7 8 9
u 1 2 3 4 5 6 7 8 9
U 1 2 3 4 5 6 7 8 9
C O M M b N I S : •
Matrix: A=aqueous B=aqueous (chlorinated) C=soil D=sediment E=sludge
F=multiphasic G=solvent H=biota l=oil J=other
Survey Complete? Y • N •
Relinquished By:
Relinquished By:
Relinquished By:
1=ice 2=H2S04 pH<2 3=HN03 pH<2 4=HCI pH<2 5=Na2S203 6=NaOH pH>9 7=Ascorbic Acid
8 = FAS 9=ZnAc
Time
Person Assuming Responsibility for Sample(s):
Received By:
Received By:
Received By:
Date
INDOOR AIR QUALITY- BUILDING SURVEY
Occupant/Building Name: Date:
Address:
Completed by: Case #
Building type: residential/office/commercial/industrial
Basement size: ft3
Number of floors
below grade: - (full basement/crawl space/slab)
at or above grade:
Foundation type: poured concrete (over gravel) /cinder blocks/earthen/ other (specify)
Buildings occupants: Children under age 13 Children age 13-18 Adults
Contaminant Source Category Yes No Comments/Locations
OUTSIDE SOURCES
Garbage dumpsters
Heavy motor vehicle traffic
Construction activities
Nearby industries (identify)
UST/AST (gasoline, heating fuel)
BASEMENT SURVEY
Wall construction (cinder block, sheet rock, paneling, etc.)
type: condition:
Floor Construction (earthen, slab, floating, etc)
type: condition:
Number of windows present on each wall and size North: East: South: West:
Was basement painted recently? oil-base or latex paints
date: type of paint:
Sump present (PID/FID/CGI#s?)
YES NO
Location of sump
New flooring in basement?(list type - carpet, tile)
using glue
New furniture added to basement type: date:
Staining on floors/walls
Moisture visually present in the basement
Pipes running through walls, floor (conduits-describe, give FID/PID/CGS readings)
Odors detected by inspector
Basement used as living space
Time occupants spend in basement (hours/day/per person)
Items stored in basement: solvents
gasoline
paint/thinners
polishes/waxes
insecticides
kerosene
household cleaning products
mothballs
other items?
NOTES:
FIRST FLOOR SURVEY
Wall construction (cinder block, sheet rock, paneling, etc)
> type: condition:
Was painting done recently? oil-base or latex?
date: type of paint:
New flooring on 1 s t floor? (list type - carpet, tile)
using glue
YES NO
New furniture added to 1 s t floor? (list type - carpet, tile)
type: date:
Staining on floors/walls
Pipes running through walls, floor (describe)
Odors detected by inspector
Items stored on this floor
solvents
gasoline
paint/thinners
polishes/waxes
, insecticides
kerosene
household cleaning products
mothballs
other items?
NOTES:
PERSONAL ACTIVITIES
Does anyone in the building smoke?
approx. number of tobacco products per day, per person
Does anyone dry-clean their clothes?
List hobbies of Residents
Any house pets?
MISCELLANEOUS
Have the occupants ever noticed unusual odors in building ?
describe: location:
Known spill outside or inside building (Specify location)
Type of heating used in building oil
natural gas
kerosene
YES NO
electric
other (specify)
If heating oil, identify the location and age of the storage tank
Is the heating unit properly vented?
Water damage or standing water in building (historic or current)
Fire damage to building date:
Pest control applications date:
Septic system
FIELD SCREENING RESULTS FID pro CGI C02 Rel. Hum
Basement
First Floor
Additional Floors
Other (specify)
APPENDIX H
Resident Instructions
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
REGION II
The United States Environmental Protection Agency is conducting an investigation of air quality in residential homes in your area. Concerns over contamination allegedly linked to a former dry cleaning operation has sparked local and federal attention. As result, the US EPA will be corning to your home to discuss this matter with you, and collect air samples from your basement.
PUBLIC FACT SHEET r AIR SAMPLING
Why is the United States Environmental Protection Agency collecting air samples from my basement?
An agreement has been formulated by local, state, and federal environmental agencies that your home should be tested for indoor air quality. As a result, US EPA personnel will conduct the sampling of air from your basement, at no charge to you. The sampling of air is to deterrnine whether you and/or your family are at risk of breathing harmful contaminants that may be associated with local environmental issues.
How is the air being collectedfrom my basement?
A device, known as a SUMMA Canister, will be placed in your basement to draw in air for a period of 24 hours. Initially, pressure inside the canister is set at a lower pressure than that of the air in your basement. During the 24 hour time frame, air will flow into the SUMMA canister until the pressure of air inside equals the pressure outside the canister. Air will not flow out of the device. These canisters are completely safe and pose no danger to you or your children.
Who is doing the analysis of the samples?
While US EPA personnel are collecting the air samples, a private laboratory has been contracted to perform the analytical procedures. .
What should I NOT do so that I do not damage or disrupt the sampling device?
Air sampling devices are particularly sensitive, and can be damaged very easily. This is why it is important to practice the following precautions, starting 24 hours prior to sampling:
-do not smoke in the basement -minimize your movement around the device -do not bring dry-cleaning in the house -do not use solvents of any type -do not open your basement windows -do not utilize fans or vents in the basement -do not paint or clean paint brushes . -do not polish your shoes " -do not pour gasoline or liquid fuels inside your house or attached garage -do not move the canister(s) under any circumstances.
The US EPA apologizes for any inconveniences that may occur as part of this sampling event. However, your cooperation and understanding is greatly appreciated. Remember, we are doing this for the protection of your health, as well as the surrounding community's.
EPA Contact: Andrew Confortini 732/906-6827 [email protected]