v>EPA
           United States
           Environmental Protection
           Agency

           Air/Superfund
            Office of Air Quality        EPA-451/R-93-007 i-^
            Planning and Standards      (replaces EPA-450/1-89-004)
            Research Triangle Park NC 27711  May 1993
AIR/SUPERFUND
NATIONAL TECHNICAL
GUIDANCE STUDY SERIES
          Volume IV - Guidance  for
          Ambient Air Monitoring
          at Superfund Sites (Revised)

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^
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V,
                    AIR/SUPERFUND NATIONAL TECHNICAL
                          GUIDANCE STUDY SERIES
                                 Report ASF-4

                  GUIDANCE FOR AMBIENT AIR MONITORING
                             AT SUPERFUND SITES
                                 Prepared for:

                          Environmental Services Division
                               U.S. EPA Region I
                               60 Westview Street
                             Lexington, MA 02173
                                  April 1993
                                                 U.8. EnvironmentaU'rotection Agency
                                                                '
                                                                       12*
                                                   wllL  60604.3590 -

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                                       Preface

             This is one in a series of manuals dealing with air pathway assessments at
hazardous waste sites.  This document was developed for the Office of Air Quality Planning
and Standards in cooperation with the Office of Emergency and Remedial Response
(Superfund).  It has been reviewed by the National Technical Guidance Study Technical
Advisory Committee and an expanded review group consisting of State agencies, various
groups within the U.S. Environmental Protection Agency, and the private sector.  This
document is an interim final manual offering technical guidance for use by a diverse audience
including EPA Air and Superfund Regional and Headquarters staff, State Air and Superfund
program staff, Federal and State remedial and removal contractors,  and potentially
responsible parties in analyzing air pathways at hazardous waste sites.  This manual is
written to serve the needs of individuals having different levels of scientific training and
experience in designing, conducting, and reviewing air pathway analyses.  Because
assumptions and judgements are required in many parts of the analysis, the individuals
conducting air pathway analyses need a strong technical background in air emission
measurements, modeling, and monitoring.  Remedial Project Managers, On Scene
Coordinators, and the Regional Air program staff,  supported by the technical expertise of
their contractors, will use this guide when establishing data quality objectives and the
appropriate scientific approach to air pathway analysis.  This manual provides for flexibility
in tailoring the air pathway analysis  to the specific conditions of each site, the relative risk
posed by this and other pathways, and the program resource constraints.

             Air pathway assessments cannot be reduced to simple "cookbook" procedures.
Therefore, the manual is designed to be flexible, allowing use of professional judgment. The
procedures set out in this manual are not intended, nor can they be  relied upon, to create
rights substantive or procedural, enforceable by any party in litigation with the United States.

             It is envisioned that this manual will be periodically updated to incorporate
new data and information on air pathway analysis procedures.  The Agency reserves the right
to act at variance with these procedures and to change them as new information and technical
tools become available on air pathway  analyses without formal public notice. The Agency
will, however, attempt to make any  revised or updated manual available to those who
currently have a copy through the registration  form included with the manual.

             Copies of this report are  available, as supplies permit, through the Library
Services Office  (MD-35), U.S. Environmental Protection Agency, Research Triangle Park,
North Carolina 27711 or from the National Technical Information Services,  5285 Port Royal
Road, Springfield, Virginia 22161.
                                          11

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                                   Disclaimer
            Mention of trade names or commercial products does not constitute
endorsement or recommendation for use by the Air Management Division, U.S.
Environmental Protection Agency.
                                        in

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                            ACKNOWLEDGMENT
            This document was prepared for the U.S. Environmental Protection Agency
(EPA) under EPA Contract No. 68-DO-0125, Work Assignment 11-80. The project was
managed by Mr. Peter Kahn of EPA-Region I.  Several figures and tables appearing in
Section 3 were adapted from presentations given by W.  T. Winberry.
                                       IV

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                                TABLE OF CONTENTS
      PREFACE  	ii
      DISCLAIMER	iii
      ACKNOWLEDGEMENTS 	.  . iv
      SUPERFUND ABBREVIATIONS AND ACRONYMS	viii

      1.0         INTRODUCTION	1-1
                 1.1   Background  	1-1
                 1.2   Objectives and Scope  	1-2
                 1.3   Overview of Air Monitoring at Superfund Sites  	1-3

      2.0         PROGRAM DESIGN	2-1
                 2.1   Program Goals  	2-1
                 2.2   Target Compounds	2-5
                 2.3   Defining Data Quality Objectives	2-7
                 2.4   Sampling Periods and Frequencies  	2-9
                 2.5   Number and Locations of Sampling Sites  	2-11
                 2.6   Selecting Appropriate Monitoring Methods	2-14
                 2.7   Meteorological Monitoring	2-16

      3.0         SAMPLING AND ANALYTICAL METHODS	3-1
                 3.1   Sampling Methods  	3-2
                 3.2   Analytical Methods	3-38

      4.0         QUALITY ASSURANCE AND QUALITY CONTROL  	4-1
                 4.1   General Principles of Quality Assurance and Quality Control .... 4-1
                 4.2   Quality Assurance Project Plan 	4-4

      5.0         DATA MANAGEMENT  	5-1
                 5.1   Data Management Planning	5-2
                 5.2   Data Acquisition   	5-4
                 5.3   Data Reduction  	5-7
                 5.4   Data Validation	5-8
                 5.5   Data Reporting  	5-13
*                5.6   Data Usage	5-18

      6.0         ESTIMATION OF PROGRAM COSTS  	6-1

      7.0         REFERENCES	7-1

      APPENDIX A:     BIBLIOGRAPHY OF NTGS DOCUMENTS
      APPENDIX B:     USEFUL CONTACTS AND TELEPHONE NUMBERS
      APPENDIX C:     LIST OF VENDORS FOR ANALYTICAL AND SAMPLING EQUIPMENT
      APPENDIX D:     CASE EXAMPLE

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                                LIST OF FIGURES


1-1          Phases of the Superfund Process	1-4

2-1          Air Sampling Plan Checklist	2-3

2-2          Depiction of Maximum and Minimum Number of Recommended
             Monitoring Locations for a Typical Site	2-13

3-1          Compendium of EPA Toxic Organic Methods	3-8

3-2          Detection Limit and Applicable Range for TO Methods	3-9

3-3          Detection Limit and Applicable Range for Various Sampling
             and Analytical Methods  	3-10

3-4          Compendium of TO Analytical Methods  	3-42

5-1          Simplified Data Flow Diagram for A AM Programs at Superfund Sites .  . . 5-6

5-2          Sample Wind Rose Diagram	5-14

5-3          Regression Equation of Concentration Versus Percent Downwind
             Overlayed with 95% Confidence Intervals for the Mean - Acetaldehyde  .  5-16
                                         VI

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                                LIST OF TABLES


1-1         APA Activities During Various Superfund Actions	1-5

2-1         Eight Steps to Designing an Ambient Air Monitoring Project	2-2

2-2         Summary of AAM Design Elements for a Typical Superfund Site	2-2

2-3         Recommended Meteorological Data Quality Objectives:  Accuracies
            and Resolutions  	2-18

3-1         Characterization of Organic Compounds by Vapor Pressure  	3-7

3-2         Summary of VOC Sampling Methods	3-12

3-3         Summary of Information for Selected Classes of Real-Time Instruments .  3-18

3-4         Comparison of Conventional Point Monitoring and Open Path Monitors .  3-24

3-5         Methods for Monitoring Specific Compounds	3-25

3-6         Detection Limits for OPMs  	3-27

3-7         Summary of SVOC Sampling Methods  	3-28

3-8         Summary of Inorganic Compound Sampling Methods  	3-34

3-9         Summary of Analytical Methods  for the Various Compound Types ....  3-40

4-1         Types of QA/QC Samples	4-10

5-1         Database Development Issues	5-5

5-2         Suggested Meteorological Data Screening Criteria  	5-11

6-1         Estimated Costs for Implementing a VOC Air Monitoring Program	6-4

6-2         Estimated Costs for Implementing a SVOC Air Monitoring Program  .... 6-5

6-3         Estimated Costs for Implementing an Inorganic Compound
            Air Monitoring Program	6-6

6-4         Summary of Information for Selected Classes of Real-Time Instruments . . 6-7
                                       vn

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	SUPERFUND ABBREVIATIONS AND ACRONYMS	
AAL        Ambient air level
AAM        Ambient air monitoring
ACGIH      American Conference of Governmental Industrial Hygienists
AMTIC      Ambient Monitoring Technology Information Center
APA        Air pathway assessment (or analysis)
ARARs      Applicable or Relevant and Appropriate Requirements
ATSDR      Agency for Toxic Substances and Disease Registry
AWMA      Air & Waste Management Association
CAA        Clean Air Act of 1990
CAAA       Clean Air Act Amendments
CERCLA    Comprehensive Environmental Response, Compensation and Liability Act
CERI        Center for Environmental Research Information
CHIEF       Clearinghouse for Inventories and Emission Factors
CTC        Control Technology Center
DL          Detection Limit
DQO        Data quality objective
ECAO       Environmental Criteria and Assessment Office
EMTIC      Emission Measurement Technical Information Center
EPA        Environmental Protection Agency
ER          Emergency removal
FS          Feasibility study
FTIR        Fourier Transform Infrared
GFC        Gas filter correlation
GC          Gas chromatograph
HAP        Hazardous air pollutant
HRS        Hazard ranking system
HSL        Hazardous Substances List
IH          Industrial hygiene
IRIS         Integrated Risk Information System
ISC          Industrial source complex
IUR         Inhalation unit risk
MEI         Maximum  exposed individual
met          Meteorological
NAAQS      National Ambient Air Quality Standards
NATICH    National Air Toxics Information Clearing House
NCP        National Oil and Hazardous  Substances Pollution Contingency Plan
NESHAPS   National Emissions Standards for Hazardous Air Pollutants
NIOSH      National Institute for Occupational Health and Safety
NPL        National Priorities List
NSPS        New Source Performance Standards
                                         Vlll

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	SUPERFUND ABBREVIATIONS AND ACRONYMS
NTG        National technical guidance
NTGS       National technical guidance study
NTIS        National Technical Information Services
NWS        National Weather Service
O&M        Operation and maintenance
OAQPS      Office of Air Quality Planning and Standards
OEL        Occupational exposure limit
OPM        Open path monitor
OSC        On-Scene Coordinator
OSHA       Occupational Safety and Health Administration
OSWER     Office of Solid Waste and Emergency Removal
PA          Preliminary assessment
PAL        Point, Area, Line
PCBs        Polychlorinated biphenyls
PEL        Permissible exposure limit
PM         Paniculate matter
PM10        Paniculate matter of less than 10 microns in diameter
PNAs       Polynuclear aromatic compounds
ppb         Parts per billion
ppbv        Parts per billion on a volume basis
PPE        Personal protective equipment
PSD        Prevention of significant deterioration
PUF        Polyurethane foam
QA          Quality assurance
QC          Quality control
RA          Remedial action
RAGS        Risk Assessment Guidance for Superfund
RCRA        Resource Conservation and Recovery Act
RD          Remedial design
RfC         Reference concentration
RfD         Reference dose
RI           Remedial investigation
 RISC        Risk Information Support Center
 RI/FS        Remedial investigation/feasibility study
 ROD         Record of Decision
 RPM        Remedial Project Manager
 SACM       Superfund accelerated cleanup model
 SARA        Superfund Amendments and Reauthorization Act
 SCBA        Self-contained breathing apparatus
 SCRAM      Support Center for Regulatory Air Models
                                          IX

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	SUPERFUND ABBREVIATIONS AND ACRONYMS
SCREEN     (atmospheric dispersion model)
SI           Site inspection
SITE         Superfund Innovative Technology Evaluation
STEL        Short-term exposure limit
SVOC        Semi-volatile organic compound
TBC         To be considered
THC         Total hydrocarbons
TLV         Threshold limit value
TLV-C       Threshold limit value - ceiling
TLV-STEL   Threshold limit value - short term exposure limit
TLV-TWA   Threshold limit value - time weighted average
TNMHC     Total non-methane hydrocarbons
TO          Toxic organic
TRI          Toxic chemical Release Inventory
TSCREEN   (emission model/atmospheric dispersion model)
TSDF        Transfer, storage, and disposal facilities
TSP          Total suspended particulates
TTN         Technology Transfer Network
TWA        Time-weighted average
TWA-REL   Time-weighted average - recommended exposure limit
TWA-STEL   Time-weighted average - short-term exposure limit
UST         Underground storage tank
UV-DOAS   Ultraviolet - Differential Optical Absorbance Spectrometer
VOC         Volatile organic compound

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                                    SECTION 1
                                 INTRODUCTION

             This report presents the results of an EPA-sponsored study to develop
guidance for designing and conducting ambient air monitoring at Superfund sites.  By law,
all exposure pathways - including the air pathway - must be evaluated for every Superfund
site; therefore, some level of ambient air monitoring usually is necessary at each site.  This
introduction provides background information related to this study, identifies the objectives
and scope of the study, and contains an  overview of air monitoring at Superfund sites.

1.1          BACKGROUND

             The Office of Air Quality Planning and Standards (OAQPS) directs  a national
Air/Superfund Coordination Program to help EPA Headquarters and the Regional  Superfund
Offices evaluate Superfund sites and determine appropriate remedial actions to mitigate their
effects on air quality. Each Regional Air Program Office has an Air/Superfund Coordinator
who coordinates activities at the Regional level.  OAQPS has a number of responsibilities
related to the  Air/Superfund program, including preparation of national technical guidance
(NTG) documents.

             Among the documents that have been prepared are a four-volume series on air
pathway assessments (APA).M These have been widely distributed and used.  (A  list of all
Air/Superfund documents is given in Appendix A.)  This document is a revision of the
original  Volume IV (EPA-450/1-89-004) of this series which was titled, "Volume  IV -
Procedures  for Dispersion Modeling and Air Monitoring for Superfund Air Pathway
Analysis".  Because the APA  documents were originally published in 1989, they reflect
information available as of 1988.  Improved sampling and analytical techniques have been
developed since then and  this  revision of Volume IV was prepared to incorporate  this new
information.
                                        1-1

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             This document has a narrower focus than the original Volume IV; it addresses

air monitoring but not dispersion modeling.  The guidance for dispersion modeling at

Superfund sites will be updated at a later date and published as a stand-alone document. In

the interim, the guidance on atmospheric dispersion modeling given to the old  Volume IV is

still valid.


1.2           OBJECTIVES AND SCOPE


             The overall objectives of this  study were to review the  original Volume IV,
identify portions of the document that needed to be revised  or updated, and implement these

changes.  This was accomplished by:


             •       Performing a literature search to identify recent relevant  citations on
                    ambient air monitoring methods; and

             •       Conducting a telephone survey of selected EPA staff and EPA
                    contractors to  elicit suggestions for  improving the document.


             The recommendations for changes to the document included:


             •       Tables to help users select appropriate air monitoring and
                    sampling/analytical methods for specific compounds or classes  of
                    compounds;

             •      Guidance on designing networks for ambient air monitoring studies;

             •      More detailed information on  quality assurance  and quality control for
                    long-term and short-term  ambient air  monitoring efforts;

             •      Guidance for managing and using the large quantities of data generated
                    by ambient air monitoring networks;

             •      Guidance on how to compare data from open-path monitors with data
                    from more traditional  measurement techniques;  and

             •      Guidance on using ambient air monitoring data  to derive emission
                    source terms for use with dispersion models.
                                         1-2

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             This document is an interim final manual that offers technical guidance for use
by a diverse audience, including EPA Air and Superfund Regional and Headquarters staff,
State Air and Superfund staff, federal and state remedial and removal contractors, and
potentially responsible parties.  This manual is written to serve the needs of individuals with
various levels of scientific training and experience in selecting and using ambient air
monitoring (AAM) methods in support of air pathway assessments.  Assumptions and
judgements are needed to develop air monitoring approaches, so the individuals involved in
this activity would benefit from having a strong technical background in air emissions
measurements, instrumentation, dispersion modeling, monitoring, and risk assessment.
Remedial project managers, on-scene coordinators, and regional air program staff,  supported
by the technical expertise of their contractors, can use the information in this report when
developing ambient air monitoring programs.

             The development of an AAM program cannot be reduced to simple
"cookbook" procedures.   There is always a potential need for professional judgement and
flexibility when developing compliance monitoring programs for specific Superfund sites.
The  information set forth in this manual is intended solely for technical guidance.  This
information is not intended, nor can it be relied upon, to create rights substantive or
procedural, enforceable by any party in litigation with the United States.

1.3          OVERVIEW of AIR MONITORING at SUPERFUND SITES

             The U.S. Environmental Protection Agency (EPA) under the Comprehensive
Environmental Response, Compensation, and Liability Act (CERCLA) and the Superfund
Amendments and Reauthorization Act (SARA),  is required to develop and implement
measures to clean up hazardous or uncontrolled waste sites.  The Superfund process consists
of three phases:  pre-remedial,  remedial and post-remedial.  The cleanup of a contaminated
site under the Superfund program proceeds via a series of actions (see Figure 1-1)  designed
to remove or stabilize the contaminated material in a controlled way.  Activities  related to an
air pathway assessment for a Superfund site may be necessary during the Site Inspection (SI),
Emergency Removal  (ER), the Remedial Investigation (RI), the Feasibility Study (FS), the
                                          1-3

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      Site Discovery
 Preliminary Assessment
     Site Inspection
                     Ranking
  National Priorities List
  Remedial Investigation/
     Feasibility Study
    Record of Decision
     Remedial Design
     Remedial Action
Operation and Maintenance
                                     Pre-Remediation
                                 Emergency Removal
                                       Remediation
Post Remediation
        Figure 1-1.  Phases of the Superfund Process.
                         1-4

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Remedial Design (RD), the Remedial Action (RA) and the Post Remediation which is often
called Operation and Maintenance (O&M).  Typical air pathway assessment (APA) activities
associated with each action are summarized in Table 1-1.  An overview of air monitoring at
Superfund sites adapted from a recent EPA publication is given below.1

             The overall goal of an APA is to evaluate a given site's actual or potential
effects on air quality.  The specific goal of any  associated air monitoring work is typically to
evaluate the exposure of on-site workers or the  off-site populace and surrounding
environment. The air monitoring issues related to these goals are discussed below, followed
by a discussion of general air monitoring issues.

1.3.1        Evaluate Exposure of On-Site Workers

             On-site workers at Superfund sites may be exposed to significant amounts of
air pollutants in the course of performing their jobs.  Any source of emissions at a site will
result in an emissions plume.  Fugitive air emission releases at Superfund sites usually occur
at ground level and are not thermally buoyant; therefore, the maximum ambient air
concentrations for such sources occur immediately downwind of the source and at ground
level. Point sources such as  air strippers may have relatively short stacks and nonbuoyant
plumes; the maximum ambient air concentrations resulting from such sources often may
occur within the site boundaries.  It frequently is necessary for on-site workers to operate
equipment or otherwise work in contact with such emission plumes. As a consequence, on-
site workers must undergo training to recognize and respond to such potentially adverse
exposures as part of their OSHA-mandated safety training.

             On-site personnel may work close to emission sources and they also tend to
move around over time, which makes it very difficult to accurately predict worker exposure
using a modeling approach.  Instead, monitoring is usually performed to determine worker
exposure.  This monitoring may entail the use of both portable monitoring instruments (e.g.,
THC or TNMHC hand-held analyzers) to provide immediate feedback on  surrogate indicators
such as total hydrocarbons, and industrial hygiene (IH) sampling to provide information on
                                         1-5

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exposure to specific compounds. IH sampling involves placing dosimeters or low-volume
sampling pumps with sorbent tubes, filters, etc. on the workers and measuring the average
concentrations of selected contaminants in the breathing  zone over a given period (e.g., 8- to
10-hour worker shift).  The IH type of sampling yields more detailed information than
portable monitoring instruments do, but data turnaround time is usually at least 24 hours.
For either type of sampling,  the measured values can be compared with occupational
exposure limits to determine whether worker exposure is within safe levels.  In general,
short-term acute exposure is  more of a concern for on-site workers than is long-term chronic
exposure.  A series of action levels is  often established that relate the level of required
personal protective equipment (PPE) to specific ambient air concentrations. For  example,
workers may be required to put on respirators if the total hydrocarbon (THC) concentration
in the breathing zone at the work area  exceeds some level for a specified period  (e.g., if the
THC concentration exceeds 10 ppmv for 1 minute).

              In many cases, the site health & safety plan requires a conservative (i.e.,
restrictive)  approach.   At the start of  the project, on-site workers are required to wear
adequate PPE to safely work under assumed worst-case levels of emissions.  The PPE
requirements are gradually reduced if the air monitoring data collected in and near the work
zones indicate that no problems have been encountered,  i.e., that no action levels have been
exceeded.  Information regarding on-site worker exposure can  also be useful for  estimating
air impacts further downwind.

1.3.2         Evaluate Exposure of Off-Site Community/Environment

              A major concern at Superfund sites is the potential exposure via the air
pathway of residents and workers  in the areas surrounding the  site.  The  degree  of concern
varies from site to site, as discussed below, depending on the nature of the contamination,
the proposed remedy, and  the proximity of the off-site populace (receptors).   The exposure
of off-site receptors typically is evaluated at several steps of the Superfund process,  and both
modeling and monitoring approaches may be employed as part of the exposure assessment.
                                          1-7

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             The evaluation of human exposure (due to inhalation) using a monitoring
approach generally involves measuring the concentrations of target analytes at the fenceline
of the site for ground-level emission sources and at the areas of maximum estimated ground-
level impacts for elevated emission sources (e.g., thermal treatment unit smokestacks).            "  i
Additional AAM may be conducted at  selected receptor locations in  the surrounding
                                                                                           r
community (e.g., at nearby  schools) or on site, if there is public access. Data are collected       •  *'
at locations upwind and downwind of the  site. The data are compared with action levels to
determine if there is cause for concern at  downwind locations. If downwind concentrations
exceed levels of concern,  actions must be taken to  reduce pollutant emissions. The
difference in the concentrations measured downwind and upwind of the site yields an
adjusted concentration considered to represent the contribution of the site emissions to the
local air quality.

             The evaluation of off-site exposure generally requires that monitoring be
                                                                                            ซr
performed whenever significant air emissions may  be released from  the site.  At sites that
have the potential for adversely affecting the air, this is often addressed by performing a           *.
short baseline study, followed by continuous monitoring whenever active remediation is being
conducted at the site.  Usually, a fixed network of point samplers is located around the
perimeter of the site, samples are collected continuously during on-site activities, and all
samples are analyzed. Additional samplers may be located near the working areas.  The
number of sampling locations will depend on the size of the site, among other factors.  For
large sites surrounded by nearby residences,  a twelve-station network may be used to provide
nearly  complete coverage of the fenceline (i.e., a station every 30 degrees).  In  some cases,
only samples from stations located directly upwind or downwind of the site for a given
sampling period will be analyzed to save  time and money; samples collected at locations
perpendicular to the emission plume(s) are not analyzed. Alternatively, a smaller number of
AAM  stations  may be used, and  these stations may be moved from  day to day according to
predicted wind patterns.   If the predictions are wrong, however, the monitoring stations may        ;
not be in the emission plume as needed.
                                          1-8

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1.3.3        General Air Monitoring Issues

             Typical APA activities at Superfund sites can be divided into the following
four categories:

             1)     Screening evaluation of site emissions and their impacts on air quality
                    under baseline or undisturbed conditions;
             2)     Refined evaluation of site emissions and their effect on air quality
                    under baseline or undisturbed conditions;
             3)     Refined evaluation of emissions and their effect on air quality from
                    pilot-scale remediation activities;  and
             4)     Refined evaluation of the effects on air quality of full-scale remediation
                    activities.

Other APA activities may be appropriate for specific site applications.  Screening studies are
performed to better define the nature and extent of a problem (i.e., to limit the number of
questions to be considered for a site); refined studies are performed to find definitive answers
to one or more air-related questions.  While screening  studies are less time- and resource-
intensive than refined studies, they do not necessarily use different monitoring methods or
approaches.   Screening studies should not be thought of as  being necessarily inexpensive,
"quick-and-dirty," or qualitative in nature.  Screening studies have more uncertainty
associated with them than refined studies do, so their experimental design should be more
conservative. For example, if only a few days of monitoring data are to be collected,  it
should be collected during periods of worst-case conditions.

             Superfund sites often contain a complex  mixture of contaminants. The
potential adverse health effects vary from compound to compound, and the health-based
action levels  may vary by orders of magnitude  between compounds with relatively similar
structures and physical properties.  Therefore, the most significant compounds at the site
from a health risk standpoint may not necessarily be those compounds present in the highest
concentrations in the soil or water at the site.  The compounds addressed in the air
monitoring program will typically be a subset of the contaminants present at the site, since it
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is often prohibitively expensive to generate data for all the contaminants present. Risk
assessments for the air pathway usually indicate that a relatively few compounds account for
most of the risk.

             The proposed remedy will greatly influence the potential emissions from a site.
In general, in-situ remediation methods result in lower levels of air emissions than ex-situ
remediation methods.  Any activity that moves or disturbs the waste present at the site can
potentially result in emissions of VOCs and PM.  Public concern historically has focused on
point sources of air emissions such  as incinerator stacks, but fugitive sources of emissions
such as materials handling operations may result in greater air emissions at many sites.

             The appropriate monitoring methods used to check compliance with established
action levels will vary from target compound to target compound and from site  situation to
site situation.  Compliance monitoring for long-term action levels tends to involve the
continuous collection of time-integrated samples at fixed locations;  compliance monitoring for
short-term action levels tends to involve the periodic collection  of nearly instantaneous
samples at various locations of interest.  Long-term monitoring  is intended more to document
actual exposure than to provide feedback to on-site operations.  Short-term monitoring is
intended  to provide  information to on-site decision makers to help  them select operating rates
and decide whether  emission control measures are needed.

             In general, compliance with long-term action  levels  is based on daily samples
collected at each location within an AAM network. Broad-based collection methods such as
evacuated canisters, Tenax tubes, or charcoal tubes are usually  selected for VOCs so that all
the target analytes can be measured using only one or two sampling and analysis approaches.
Alternatively, dedicated gas chromatographs (GCs) or gas chromatographs/mass
spectrometers (GC/MSs) used as point samplers, or open path monitors (OPMs) may be used
in some cases to provide near real-time data and to minimize unit  analytical costs.  Fewer
options exist for standard PM10, metals, and some SVOCs, although standard methods are
available.
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             Selecting monitoring methods to document compliance with short-term action
levels often is more difficult than selecting methods to determine compliance with long-term
action levels. Dedicated GC, GC/MS, or OPM  systems are the only realistic options for the
cost-effective continuous or semi-continuous monitoring of individual volatile organic
compounds.  These methods require a relatively  large capital investment and they may not be
a viable option for certain compounds or mixtures of compounds. Several methods are
commonly used for periodic compliance monitoring for short-term action levels. Fixed or
portable broad-band analyzers for total hydrocarbons (THC) or total non-methane
hydrocarbons (TNMHC) can be used if it is assumed that the instrument response (or some
fixed fraction thereof) is wholly due to the most hazardous compound present.  Compound-
specific colorimetric tubes are available for many compounds, though usually only for
relatively high concentration ranges (e.g., ppm levels). Short-term monitoring  for SVOCs
and metals cannot be performed directly. Instead, portable monitors for paniculate matter
can be used to measure total suspended paniculate matter (TSP). An action level can be
established if the average fraction of SVOCs or metals associated with the TSP is assumed.

             The need to  determine compliance with short-term action levels requires a
timely turnaround of data.  The most critical need for timely information is to compare AAM
data with short-term action levels during remediation. As previously discussed, the most
common solution is to use broad-band THC or TNMHC analyzers or to use colorimetric
tubes.  For sites where the concentration of specific analytes must be measured, dedicated
gas chromatographs (GC) and GC/MS systems used as point samplers  have until recently
been the only realistic option.  They can provide updated values every 30 minutes or so.
The main drawbacks of the use of their instruments as short-term monitors have been the
cost of the equipment (e.g., $100,000 per station), the complexity of installing  and
controlling the monitoring network, maintenance requirements, and the labor required to
reduce and manage the data.
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             A promising monitoring approach for Superfund remedial actions is the use of
open path monitors (OPM).5 OPMs are spectroscopic instruments configured to monitor the
open air over extended paths of hundreds of meters or more.  They rely on the interaction of
light with matter to obtain information about that matter.  The potential advantages of OPMs
compared with more conventional air monitoring approaches include:   1) there is rapid,
essentially real-time data analysis; 2) no sample collection is required in the normal sense of
the term; 3) no additional analytical costs are associated with each additional sampling
episode; and 4) data are path-weighted concentrations rather than concentrations for specific
sampling points. The first advantage implies that information is available to site decision
makers within minutes and short-term fluctuations in ambient concentrations can be detected.
The last advantage listed implies that it is less likely that an emission  plume will evade the
monitoring network and that source terms can be directly determined.  Data management
software is available for handling the very large quantities of data generated. The main
disadvantages of OPMs at this time are the lack of standard operating procedures, the lack of
qualified equipment operators,  the lack of standardized  procedures for dealing with spectral
interferences, the lack of reference spectra for some compounds of interest,  and detection
limits that, for some compounds (e.g., benzene), are higher than those for conventional
methods.

             Detection limits are often a concern when selecting a monitoring device.
Compliance monitoring for action levels generally requires that the detection limit of the
sampling and analytical approach be lower than the action level  concentration.  Changes in
ambient concentration due to emissions from the site must be distinguished from  the sample-
to-sample variability that is always present.  Therefore, the precision  of the measurement
method is critical, but the precision of analytical methods tends  to deteriorate as the detection
limit is approached.  There often is a trade-off between analytical data turnaround time and
detection  limit.  Measurement  methods that provide rapid data turnaround often are screening
methods that provide rapid feedback for parts-per-million concentration levels rather than for
parts-per-billion or lower concentration levels.  The data accuracy and precision of such
screening methods also tend to be more variable that those  for non-screening methods.  For
example, portable THC analyzers may exhibit a large daily zero and  upscale drift, especially
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if they are exposed to very high concentration levels or if the internal batteries are allowed to
fully discharge.  As previously mentioned, dedicated GC, GC/MS, or OPM systems may be
the best options to meet data turnaround and detection limit requirements at sites where
potential adverse effects on air quality are a major concern.

             The uncertainty of the AAM data also is an issue.  The accuracy of the
monitoring data must be adequate to determine whether action levels are exceeded.  The
AAM data must be precise enough to determine differences from ambient or upwind
concentrations of the compounds of interest.  If the action levels selected are at or near
detection limits, the uncertainty of the analytical data usually will be greater than it would be
for measurements of those compounds at higher concentrations.
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                                     SECTION 2
                                PROGRAM DESIGN

             There is no universal approach to conducting an AAM program that would
satisfy the needs of every air pathway assessment.  Instead, each program should be designed
to match the specific program needs and available resources.  A framework for designing an
effective ambient air monitoring (AAM) program consists of the eight basic steps listed in
Table 2-1.  This framework parallels earlier EPA guidance on applying the Data Quality
Objectives Process for ambient air monitoring around Superfund sites.6-7 The first step to
designing an AAM program consists of defining the program goals.  Once these have been
established, specific  data needs in terms of target compounds, data quality, temporal
resolution, and spatial resolution can be defined. The selection  of appropriate monitoring
equipment will depend on these specific data needs and therefore selection should occur only
after an initial determination of the data requirements has been made.  Guidelines for
addressing five of the elements of program design are summarized in Table 2-2.  An
example checklist for developing an AAM plan is given as Figure 2-1. Detailed discussions
of specific measurement methods, elements of quality assurance/quality control, and data
management appear  in subsequent sections of this document.

2.1           PROGRAM GOALS

             Section 1.3 of this document gave examples of reasons to conduct air
monitoring around Superfund sites. In each example, air monitoring data were used for
comparison with certain risk-based action levels to determine the need for reducing the
exposures  of either on-site workers or the general public to pollutants.  For an AAM
program to be effective, goals should be defined in  terms of certain key questions whose
answers will depend on the outcome of the monitoring results.  For example, "Has remedial
activity  caused the ambient air concentrations to exceed  applicable risk-based concentration
levels?"6 If the answer to this question  is "yes," specific planned  actions must be taken to
reduce pollutant exposures.  Such actions might be to: (1) institute additional emission
controls, (2) temporarily halt remedial activities, or (3) evacuate the receptor population.
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                                     Table 2-1.
          Eight Steps to Designing an Ambient Air Monitoring Project
Step \
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
= :,; Description : f ' -^
Define program goals
Select target compounds
Establish data quality objectives
Select number and location of monitoring sites
Select duration and frequency of monitoring
Choose monitoring methods
Establish a quality assurance/quality control program
Establish a data management system
                                     Table 2-2.
       Summary  of AAM  Design Elements for a Typical1 Superfund Site
Design Element
Number of Target
Compounds
Data Quality
Objectives
Sampling: Period
Duration
Frequency
Number of Sampling
Locations
Required Monitoring
Method
Characteristics
Typical1 Goal or Range of Values :
Baseline Study
• Multiple compound classes
• Full analyte list
Identify compounds accurately;
semi -quantitatively
24-hour
5 days to 1 year
Daily to once every 6 days
4-12
• Low DLs
• Applicability to broad range of
compounds
Monitoring During
Remedial Activities
1-20
Quantify level of
specified compound(s).
8-24 hours
Duration of remediation
Daily
4-12
• Rapid Data-Turnaround
• Low DLs
Post-Remediation Study
<10
Quantify level of
specified compound(s).
24-hour
5 days to 1 year
Daily to Quarterly
4-12
• Low DLs
'Superfund sites vary greatly from one to another in a number of relevant areas. The information in this table is
intended to provide general guidance as to the design boundary conditions expected for most sites.
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The following checklist consists of a series of questions to consider when developing the sampling program.

   /.  Objectives of the Sampling Program and Implied Assumptions

	A.  Have clear, concise objectives for the sampling program been defined?

	B.  Have the assumptions of the sampling program been clearly defined (e.g., sampling under "worst-case"
          conditions, sampling under "typical" conditions, sampling under routine, periodic schedule, etc.)?

	 C.  What will the data be used for (e.g., risk assessment, compliance with action levels)?

	  D.  Other:	
   //.  Selection of Sampling and Analytical Methods

      A.  Selection of Target Compounds

      	 1. Has background site information been consulted?

      B.  Selection of Method  (Sampling and/or analytical)

      	 1. Can selected methods detect the probable target compounds?

      	 2. Do the selected analytical methods have detection limits low enough to meet the overall objectives of the
            sampling program?

      	 3. Would the selected methods be hampered by any interfering compounds?

  	C.  Will the selected methods, when applied to the projected sampling location(s), adequately isolate the relative
          downwind impact  of the site from that of other upwind sources?

  	 D.  Are the selected methods logistically  feasible at this site?

      E.  Other	
  ///.  Location(s) and Number of Sampling Points

 	 A.  Do the locations account for all the potential on-site emission sources that have been identified from the initial
          site background information and from walk-through inspections?
      B.  Will the sampling locations account for all the potential emission sources upwind from the site?

      C.  For short-term monitoring programs, was a forecast of the local winds for the day(s) of the program obtained7

      D.  For a long-term monitoring program, were long-term air quality dispersion models and historical meteorological
          data used to predict probable area of maximum impact (when applicable)?

      E.  Does the sampling plan account for the effects of local topography on overall wind directions and for potential
          shifts in direction during the day (e.g., valley effects, shoreline effects, hillside effects)7

      F.  Does the sampling location decisions account for the effects of topography on surface winds, especially under
          more stable wind directions  (e.g., channelization of surface winds due to buildings, stands of trees, adjacent hills,
          etc.)?

      G.  Can any sampling equipment left at these locations be  adequately secured?

      H.  Other	            	         	             	
                                  Figure 2-1.   Air Sampling Plan  Checklist8
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IV.  Time, Duration, and Frequency of Sampling Events

    A.  When the sampling time periods (the actual days, as well as the time span during specific days) were selected,
        were the effects of the following conditions on downwind transport of contaminants considered:

    	• Expected wind direction?

    	• Expected atmospheric stability classes and wind speeds?

    	 • Evening and early morning temperature inversions?

    	• Changes in atmospheric pressure and surface soil permeability on lateral, off-site migration of gases from
          methane-producing sources such as landfills?

    	• During indoor air investigations, gas infiltration rates into homes due to changes in atmospheric pressure and
          to the depressurization of homes caused by many home heating systems?
           Other
    B.  When the sampling time periods (the actual days, as well as the time span during specific days) were selected,
        were the effects on potential site emissions listed below considered:

    	•  Effect of site activities?

    	•  Effect of temperature and solar radiation on volatile compounds?

    	 •  Effect of wind speeds on particulate-bound contaminants and on volatiles from lagoons?

    	 •  Effect of changes in atmospheric pressure on landfills and other methane-producing emission sources?

    	 •  Effect of recent precipitation on emissions of both volatile and particulate-bound compounds?

    	•  Other	

    C.  Do the time periods selected, allow for contingencies, such as difficulties in properly securing the equipment, or
        public reaction to the noise of generators for high volume samplers running late at night?

    D.  When determining the length of time over which individual samples are to be taken, were the following questions
        considered (when applicable)?

    	•  Will sufficient sample volumes be taken to meet the desired analytical method detection limits?

    	 •  Will the sampling durations be adequate either to cover the full range of diurnal variations in emissions and
           downwind transport, or to isolate the effects of these variations?

    	 •  Are the sampling intervals consistent with the averaging period of the applicable action levels?

    	 •  When applicable, do the selected time intervals account for potential wind shifts that could occur due to local
           topography such as shorelines and valleys?
           Other
 V.  Meteorological Data Requirements

	 A. Has a source of meteorological data been identified to document actual conditions at the time the sampling event
        takes place?

	 B. Has the placement of an on-site meteorological station been considered in the sampling plan if no off-site station
        has been identified?

 VI.  QA/QC Requirements (see Chapter 5 for additional information on QA/QC requirements)

	A. What level of QA/QC will be required'
     B.   Have the necessary QA/QC samples been incorporated into the sample design to allow for the detection of
         potential sources of error?

     C.   Does the QA/QC plan account for verification of the sample design and the sample collection'
                                            Figure 2-1.   (Continued)
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             The Remedial Program Manager (RPM) or On-Scene Coordinator (OSC) will
usually take the lead role in defining program goals and determining what actions might be
necessary if pollutant concentrations exceed levels of concern.  During this initial stage of
program design, the RPM or OSC should also discuss the goals of the program with the
technical staff to make sure that these objectives can be reasonably accomplished within the
limitations of available technical and financial resources.  This will usually require a
preliminary assessment (in very general terms) of the types of data required, the uses of the
data, and any consequences of an incorrect decision, based on the measurement results. In
some cases, program goals may have to be revised if inadequate resources are available.

2.2          TARGET COMPOUNDS

             After the goals of the air pathway assessment have been defined, a list of
analytes should  be determined. Superfund sites often contain a complex mixture of
contaminants, and not every contaminant will pose a significant risk via the air pathway.
Factors that affect the magnitude of any risk posed by a particular contaminant include the
concentration of the compound in the buried waste or soil, the compound's volatility or the
rate at which the compound is emitted to the air, and the toxicity or unit risk factor of the
particular compound.

             Certain compounds typically are considered to "drive" the risk assessment at
Superfund sites, i.e., they pose the most significant risk.  Air pathway assessment studies,
therefore, will typically focus available resources on those compounds thought to pose  the
most significant risk at a site,  rather than include an evaluation of every compound  found at
the site. The selected analytes are sometimes referred to as target compounds or compounds
of potential concern.  Compounds  of frequent concern at Superfund sites include:

             •      Volatile organic compounds (VOCs), especially benzene and
                    chlorinated solvents such as vinyl chloride, methylene chloride,
                    chloroform, etc.;
             •      Semi-volatile organic compounds (SVOCs), such as  polychlorinated
                    biphenyls (PCBs), poly nuclear aromatic  compounds  (PNAs), and
                    pesticides;
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             •      Semi-volatile inorganic compounds such as those containing mercury;
                    and
             •      Nonvolatile compounds such as asbestos and cyanides; and heavy
                    metals, such as lead, chromium, cadmium, zinc, beryllium, copper,
                    and arsenic.

             Of course, not every compound listed above is present in significant quantities
at every Superfund site.  Site records must be reviewed to determine the nature of the buried
waste.  Wastes are typically classified according to RCRA codes that are defined with respect
to compound constituents in the Code of Federal Regulations (40 CFR, Part 261). If site
records are unavailable, soil sampling and analysis must be conducted to determine which
compounds are present in significant enough quantities to possibly warrant air monitoring.

             The rate at which soil contaminants are emitted to the air depends in part on
their volatilities (for gaseous contaminants only), which in turn depend on vapor pressures
and Henry's Law constants. Highly volatile compounds will typically be emitted at a higher
rate than compounds of similar concentration in the soil but lower volatility.  Computer
models that rely in part on  compound vapor pressure and Henry's Law data as input are
often used to estimate potential emissions to the air. Emission  rates can  then be used as
input to an atmospheric dispersion  model to gauge both short-term (e.g., one-hour) and long-
term (e.g., one-year) concentration levels at the facility fenceline and off-site receptors.
Semi-volatile and non-volatile  compounds may also be of concern  whenever they exist in
significant concentrations and there is the potential for the dispersion of wind-blown dust.

             It often is not practical to monitor for every compound present in the  soil or
ambient air, because of the limitations of available technical or financial resources.  In these
cases,  potential target compounds must be ranked in terms of predicted concentration levels
and applicable health-based action  levels.  Note that the potential adverse health effects vary
from compound to compound, and the health-based action levels may vary by orders of
magnitude between compounds with relatively  similar structures and physical properties.  For
example, 1,2-dichloroethane is considered to be a much more potent carcinogen than 1,1-
dichloroethane, and benzene is considered to pose a much more significant risk  than equal
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amounts of toluene or xylene.  Therefore, the most significant compounds at the site from a
health risk standpoint might not necessarily be those present in the highest concentrations in
the soil or water. To prepare a list of potential target compounds, the potential health risks
associated with each  compound can be ranked in terms of a hazard index (HI), where HI is
the ratio of the predicted concentration to the applicable action level.  Measurement resources
should be focused on those compounds with the highest hazard indices.

              Emission  and dispersion models can be limited in their ability to predict actual
environmental conditions because of inherent simplifications and assumptions in both the
model and the model's input.   Therefore, the most effective, albeit more costly,  way to
determine which compounds may or may not be of concern is to conduct a short-term
intensive monitoring  effort to screen for  a comprehensive list of potential high-risk
compounds.  Based on the results of this initial screen, a more realistic ranking of the
potential hazards associated with each compound can usually be made.

2.3           DEFINING DATA QUALITY OBJECTIVES

              Data quality objectives (DQOs) are statements of the level of uncertainty a
decision maker is willing to accept where making decisions based on the air monitoring
data.6  Note that DQOs  differ from data  quality indicators such as measurement precision and
accuracy  in that they express the limits of the overall uncertainty of a project's results in
terms of the probability  and consequences of making a wrong decision (rather than as the
limits of certainty about specific  measurements).  How data quality objectives relate to
accuracy  and precision is described in  the following paragraphs.

              Establishing DQOs must be one of the first steps in  the design of an AAM
program.  This must be done before sampling and analytical methods  are selected for
performing the measurements. EPA has adopted a three-stage process for establishing DQOs
for ambient air monitoring around superfund sites.6'7  Combined, the three  stages of the DQO
process take into account all of the eight elements of project design to ensure that sufficient,
valid data are collected to  achieve the goals of the program.  During the first stage of the
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DQO process, the goals of the APA are defined in terms of certain critical decisions that
require ambient measurement data,  and the feasibility of achieving those goals within the
constraints of the available technical and financial resources are determined.  During the
second stage, specific data requirements in terms of temporal resolution, spatial resolution,
and data quality are defined.  At the third stage of the DQO process, a viable data collection
program that meets the Stage I and  Stage II objectives is designed.  Guidelines for defining
the temporal and  spatial resolutions  of the measurement domain are addressed in Sections 2.4
and 2.5, respectively, and guidelines for selecting appropriate measurement methods are
given in Section 2.6.  The remainder  of Section 2.3 pertains to defining the limits of data
quality.

              Data quality objectives  are expressed in terms of acceptable probabilities that
the measurement  results will lead to incorrect decisions.  Two general types of incorrect
decisions can occur:  false positive  errors and false negative errors.  False positive  errors
result in decisions to take action to  reduce pollutant exposures when the true  concentrations
are actually below levels of concern.  False negative errors result in not taking action  when,
in fact,  concentration levels are above those thought to pose a serious risk. While false
negative errors are usually more detrimental because of the health risks that might
unknowingly be imposed on the public, false positive errors are also counterproductive
because of the money and  time wasted taking unnecessary  action.  Data quality objectives,
therefore, place limits on the acceptable probabilities  that either a false positive or false
negative error will be made.  The acceptable probability that a measurement  result  will lead
to an incorrect decision should depend on the seriousness of the consequences of the
incorrect decision. The following examples of APA data quality objectives demonstrate the
relationship between acceptable probability rates and  the seriousness of the incorrect
decision1:

              •      At a true concentration of 1A the level of concern, the probability of a
                     false positive finding should be less  than 10% (i.e., at  least 90% of the
                     time, the data would correctly indicate that there is no  problem).
              •      When the true concentration is  1 l/2 times the level of concern, the
                     probability  of a false negative finding should be less than 5% (i.e.,  at
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                    least 95 % of the time, the monitoring data would correctly indicate that
                    there is a problem).
             •      When the true concentration is 2 times the level of concern,  the
                    probability of a false negative finding should be less than 1% (i.e.,  at
                    least 99 % of the time, the monitoring data would correctly indicate that
                    there is a problem).

             The probability of a false finding is directly and quantitatively related to the
accuracy and precision of the measurement method.  For instance, in the examples above, a
measurement method with a precision of 20% (expressed as relative standard deviation) and
no systematic biases would be needed to satisfy each of the three conditions. More details
on applying the DQO process to AAM around  Superfund sites are given in References 6 and
7.

             In addition to quantitative limits  of data quality, data quality objectives must
also be defined  qualitatively in terms of representativeness and comparability.
Representativeness refers to the specific conditions of space and time to which  measurement
value is intended to relate.  For example, if data are to be compared with 30-minute
inhalation-based action levels,  the measurement values must be representative of conditions in
the typical breathing zone (i.e., approximately 5' to 6' above ground in an area with
unrestricted air  flow) and averaged  over 30-minute intervals.   Comparability refers to
assurances that  the measurement results are expressed in a manner and format  that enables
direct comparison with applicable action levels (i.e., standardized units) or, if necessary,
with other, similar types of data.

2.4          SAMPLING PERIODS AND FREQUENCIES

             The temporal resolution of the measurement domain is defined by the sampling
period and  frequency.  Sampling period refers to the length of time to which each
measurement value is  referenced (e.g., 30-minute,  one-hour, 24-hours, etc.). The sampling
frequency is the number of sampling periods conducted  within a given time interval (e.g.,
daily, one every third day,  etc.). For typical APA  monitoring programs, the sampling
period may range from a few seconds to 72-hours, depending on the specific goals and data
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requirements of the program.  Sampling periods of a few seconds are performed using real-
time or grab sampling techniques, whereas longer sampling periods are usually performed
using integrated methods.  For real-time monitoring, the sampling frequency is usually
continuous, although sampling may be limited to certain times of the day when remedial
activity is occurring. Integrated sampling may be performed continuously (i.e., back-to-back
sample collection), or at intermittent, discrete intervals.  Specific program goals and
available funding will normally dictate whether continuous or intermittent sampling intervals
are performed.  Grab sampling is only performed when an instantaneous, spot check of the
air constituents is required (e.g., as a pre-monitoring screen for constituent compounds).

             Sampling periods must be chosen for comparability with relevant action levels
or ARARs.  For example, if the measurement data are to be compared with a 30-minute
action level, a 30-minute sampling period is normally required (alternatively, continuous,
real-time monitoring can be performed and the resulting data averaged over 30-minute
intervals).  Compliance with long-term action levels usually is determined using a series of
24-hour sampling periods. In some cases, sampling periods also may  depend on  the amount
of sample volume needed to achieve acceptable detection limits.  For instance,  a one-hour
sampling period will yield a detection limit twice as low as the same technique operating with
the same flow rate for 30 minutes.

             The required frequency of sample collection depends primarily on:  (1) the
temporal variability of emission rates with respect  to the temporal scale of the action level,
(2) the variability  of meteorological and other factors that might affect pollutant dispersion,
(3) the level of confidence needed for determining mean or maximum  downwind
concentrations, and (4) the level of available funding.  When action levels are based on
short-term averages and the pollutant concentrations are expected to vary significantly over
time, continuous sample collection may be needed to achieve an acceptable level  of
confidence that action levels are not exceeded. Note that the level of  confidence required in
the measurement results may  depend on how close the measured ambient concentration levels
are to the action level concentrations (i.e., the higher the measured concentrations, the
greater the confidence required).  For determining compliance with long-term action levels,  a
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minimum sampling frequency of once every sixth day is normally required.  However, if the
measured concentration levels are near levels of concern, a greater frequency of collection,
perhaps daily, will be required (e.g., operating schedule for PMJO sampling given in 40 CFR,
Part 58.13).

2.5           NUMBER AND LOCATIONS OF SAMPLING SITES

              The spatial resolution of the measurement domain is defined by the number
and locations of the sampling sites.  Factors that influence the required number and locations
of monitoring sites are:  (1) the locations of potential on-site emission sources; (2) the
locations of topographic features that affect the dispersion and transport of site emissions;  (3)
the variability of local wind patterns; (4) the locations of sensitive receptors such as schools,
hospitals, and concerned citizens;  (5) the level of confidence needed to ensure that the
maximum concentration levels are observed; and (4) the level of available funding.

              Typically, programs designed for determining long-term concentration levels
(e.g., annual  or lifetime exposures) will require fewer monitoring locations than those
intended to monitor compliance with short-term action levels. This is because the long-term
prevailing wind directions are usually more predictable  than day-to-day wind patterns, and
sampling sites therefore can be more accurately  situated for measuring  significant long-term
effects. For  example, the dispersion modeling of source emissions, using climatological
wind data as  input, can be performed to  determine the most appropriate sampling locations
(i.e., areas of maximum or significant effects).

              For determining concentration levels with respect to short-term effects, a fixed
network of sampling sites ideally should be located around the perimeter of the waste site,
with additional samplers located near working areas and near sensitive receptors.  The
number of sampling sites will depend, in part, on the size of the  waste site.  For large sites
surrounded by nearby residences,  a 12-station network would provide nearly complete spatial
coverage of the fenceline (i.e., one sampling station every 15 degrees).  In some cases, only
samples from stations located directly upwind or downwind of the site for a given sampling
                                         2-11

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period will need to be analyzed.  Alternatively, a smaller number of stations may be used
and these stations moved from day to day according to predicted wind patterns.  If

predictions are wrong, however, the monitoring stations may not be in the emission plume as

needed.  The minimum and maximum number of recommended monitoring locations for a
typical site are shown in  Figure 2-2.


              In many cases, constraints on placing samplers can be encountered because of

wind flow obstructions caused by nearby buildings, trees, hills, or other obstacles.   Other

constraints might be related to security,  the accessibility of electrical power, as well as the

proximity to roadways or other pollution sources that might affect the representativeness of

the sample for measuring the waste site's effects on air quality.  Specific guidelines for
selecting sites to achieve representative conditions are9:


              •      The most desirable height for sampler inlets is near the breathing zone
                    (i.e., about 5' to 6' above ground).  Practical  factors  such as high
                    impermeable fences surrounding the waste site may sometimes require
                    that sampling inlets be placed slightly higher (at least 1 meter above the
                    top of the fence).

              •      Samplers should be located at least 20 meters  from the dripline of
                    nearby trees  and must be at least 10 meters from the dripline of trees
                    when the trees act as  an obstruction to airflow.

              •      Samplers must be  located away from obstacles and buildings  such that
                    the distance between the obstacles and  the sampler inlet is at  least twice
                    the height that the obstacle extends above the  sampler inlet.  Airflow
                    must be unrestricted in an arc of at least 270ฐ  around the sampler, and
                    the predominant wind direction for the season of greatest pollutant
                    concentration potential must be included in the 270ฐ arc.

              •      The sampler and nearby roadways must be sufficiently separated to
                    avoid the effects of dust reentrainment and vehicular  emissions on
                     measured air concentrations.

              •       Stations for measuring particulate matter should not be located in an
                     unpaved area unless there is vegetative ground cover year round so  that
                     the effect of locally reentrained or fugitive dusts will be  kept to a
                     minimum.
                                          2-12

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                  Maximum - One Station Every 30(
        Minimum - One Upwind and Three Downwind Stations
                                               Wind Direction
Figure 2-2.   Depiction of Maximum and Minimum Number of Recommended Monitoring
          Locations for a Typical Site
                              2-13

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2.6          SELECTING APPROPRIATE MONITORING METHODS

             Because of the wide variety of data needs that may be encountered when
designing an APA monitoring program, there is no single monitoring method that applies
equally to every situation.  Factors that might influence the selection of appropriate
monitoring  methods to suit particular data needs are:  (1) target compounds, (2) data
turnaround  time, (3) detection limits, (4) data quality, (5) temporal resolution, (6) spatial
resolution,  and (7) cost.  The merits and limitations of various conventional and novel
measurement methods are given in Section 3.0. The factors that should be considered when
selecting a  measurement method are discussed below.

             Data turnaround time is one of the most important factors to consider when
choosing appropriate measurement technology.  In contrast to typical non-Superfund
applications where data turnaround times may be several weeks, data turnaround during
remediation at Superfund sites typically must be within one or two days for comparison with
long-term action levels and within hours  for comparison with short-term action levels.  Data
turnaround  times are most stringent when the monitoring data are being compared with short-
term action levels during remediation.  In these cases, immediate or real-time feed back of
ambient concentration levels is usually required.  In these situations, the most appropriate
monitoring method will be a broad-band total hydrocarbon (THC) or total non-methane
hydrocarbon (TNMHC)  analyzer.  For sites where the concentration of specific analytes must
be measured, dedicated on-site GC, GC/MS, or OPM systems may be the only applicable
option.  For long-term monitoring programs, data turnaround time can be as  much as 48
hours. This may also require a dedicated on-site laboratory because of the large number of
samples likely to be analyzed during the course of the program.

             Detection limits are another factor that must strongly influence the selection of
appropriate monitoring methodology.   Compliance monitoring for action levels generally
requires that the detection limit be lower than the action level concentration.  Note that there
is often a tradeoff between detection limits and data turnaround times.  For instance,
measurement methods that provide real-time or near real-time results often are screening
                                         2-14

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methods that provide rapid feedback for parts-per-million concentration levels.  This might
be adequate for some programs designed for determining short-term risks; however, it would
usually not be adequate for long-term assessment programs for which levels of concern are
often on the order of parts-per-billion or less.

              When selecting appropriate measurement technology, one must first decide on
the necessary turnaround time and the required detection limits. Once these are defined,
other factors such as temporal resolution, spatial resolution, data quality and cost can be
considered.  Temporal resolution differs  from  data turnaround time in that it relates to the
time period during which a sample is collected (sample integration period) rather than how
fast the sample can be analyzed and reported.  Some methods may require a long integration
period in order to acquire sufficient volume of sample to achieve acceptable detection limits.
Other methods may achieve the same detection limits with a shorter sampling period.

              Spatial resolution must also be considered when determining the measurement
methodology.  A high degree of spatial resolution in ambient air concentrations may be
needed in some cases, such as when multiple emission sources are in close proximity to
receptors.  The higher the degree of spatial resolution required, the more sampling locations
are needed.  Increasing the number of sampling locations will increase the cost of the AAM
program, if the sampling methods and frequency are held constant. Obviously, OPM
systems provide the most complete coverage for monitoring emissions at a site boundary;
however, OPMs provide a path-integrated measurement  and might not be as accurate as other
techniques for determining the peak concentration of a narrow plume.

              Note that many interacting factors must be considered when selecting
appropriate measurement methods.  These factors must be ranked so  that those issues most
important to the particular needs of a specific  program are given the appropriate attention.
                                         2-15

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2.7          METEOROLOGICAL MONITORING

             Meteorological measurements will often be required along with ambient air
quality data when assessing the risks associated with waste site air pathway emissions. At a
minimum, wind direction and wind speed should be measured so that the direction of air
pathway migration from the site can be assessed during all times that ambient air quality data
are collected.  Other meteorological parameters that are relevant to the air pathway
assessment because of their effects on emission rates or dispersion of pollutants are:
temperature, precipitation, relative humidity, barometric pressure,  and sigma theta (standard
deviation of the wind direction).

             Meteorological measurements must be collected with similar concerns  for
quality assurance and quality control as the air pollutant measurements.  That is,
measurements must be: (1) representative of the atmospheric conditions that affect pollutant
emissions,  transport and dispersion; (2) comparable across the measurement network; and (3)
of sufficient quality to support meaningful interpretations of the air pollutant data.

             Meteorological measurements must be representative of the conditions at the
source and at the locations of the sampling stations. In areas of uniform terrain,  one
meteorological  monitoring station may be sufficient to represent the entire source and
sampling domain.  In some cases,  meteorological data from an existing, off-site monitoring
station (e.g., at a local airport) may serve this purpose. However, one should recognize that
off-site data from other sources  may not always be obtained with the same concerns  for
quality control  and data management as data collected specifically to support the APA.

              In regions of complex terrain or near large bodies of water where local
topographical features can influence air flow and temperature, more  meteorological
monitoring  stations are usually required to  represent the different local domains.  Assurances
must also be made that the meteorological  sensors are exposed to atmospheric conditions that
are indeed characteristic of the area that the data are intended to represent.  This requires
that sensors be mounted away from the immediate influence of trees, buildings, steep slopes,
                                          2-16

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ridges, cliffs, and hollows. Sensors located in the vicinity of any such obstructions should be
mounted at a horizontal distance at least 5 to 10 times the height of the obstruction9.

             Comparability of meteorological measurement data across the monitoring
network is achieved by adhering to a standard set of guidelines or criteria for monitoring site
selection and sensor exposure.  Detailed siting guidelines for meteorological instrumentation
are given in Volume IV of EPA's Quality Assurance Handbook for Air Pollution Monitoring
Systems.  Typically, a 10 meter sensor height is recommended for wind speed and wind
direction measurements, however, for short term screening studies when fixed monitoring
stations may not be practical, a 2-3 meter sensor height is usually adequate. Additional
guidelines for siting temperature, relative humidity, precipitation, and solar radiation sensors
are given in the QA handbook.

             Meteorological sensors must be capable of providing data of sufficient
accuracy and resolution to enable a meaningful interpretation of the monitoring results.
Recommended system accuracies for various measurement parameters are given in Table 2-3.
The accuracies  of meteorological sensors should be checked periodically during the course of
a long-term measurement program (e.g., every three  months or every six  months) as part of
the quality assurance audit program  (e.g., see Section 4.0).
                                         2-17

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                     Table 2-3.
Recommended Meteorological Data Quality Objectives:
             Accuracies and Resolutions9
Meteorological Variable
Wind Speed
Wind Direction
Ambient Temperature
Dew Point Temperature
Precipitation
Pressure
Time
System Accuracy'
ฑ(0.2 m/s -f 5% of observed)
ฑ5 degrees
ฑ0.5ฐC
ฑ1.5ฐC
ฑ10% of observed
ฑ3 mb (0.3 kPa)
ฑ5 minutes
Measurement Resolution ; : ;
0.1 m/s
1 degree
0.1 ฐC
0.1 ฐC
0.3 mm
0.5 mb
—
                        2-18

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                                    SECTION 3
                    SAMPLING AND ANALYTICAL METHODS

             In this section, appropriate sampling and analytical methods for monitoring air
emissions from Superfund sites under baseline conditions or during remediation are
discussed.  The sampling and analytical methods are divided into categories according to the
class of target chemical.  The four categories addressed are  volatile organic compounds,
semi-volatile organic compounds, paniculate matter, and inorganic compounds.

             Methods for volatile organic compounds (VOCs) are divided into categories
for aromatic, halogenated, and oxygenated organic compounds.  For semi-volatile organic
compounds (SVOCs), specific sampling and analytical methods are described for polynuclear
aromatic hydrocarbons (PAHs), pesticides, polychlorinated biphenyls (PCBs), and
polychlorinated dibenzo(p)dioxins/polychlorinated  dibenzo(p)furans (PCDDs/PCDFs).
Methods for total paniculate matter (PM) and for PM of less than 10 micron aerodynamic
diameter (PMi0) are also described.  The inorganic compounds addressed in this section are
heavy metals, including mercury, and soluble salts of cyanide.

             EPA has prepared a compendium of sampling and analytical procedures for
many toxic organic compounds.10 The "Compendium of Methods for the Determination of
Toxic Organic Compounds in Ambient Air" gives  general guidance for sampling and
analyzing of many compounds listed in this document; however, experience has shown that,
in some instances, the methods need to be modified to obtain the highest quality data.

             Sampling methods are described first, followed by a discussion of analytical
methods.  For each, a general overview is given, followed by a discussion of specific
methods.
                                        3-1

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3.1          SAMPLING METHODS

3.1.1        Overview of Sampling Methods

             A variety of sampling methods can be used to monitor for the types of
compounds found around Superfund sites.  The methods vary by sample type (i.e., volatile
compounds, semi-volatile compounds, and paniculate borne compounds).  Each method has
various advantages, disadvantages, and specific uses.  The greatest number of available
methods for any one type are for VOCs.  Semi-volatile organic compounds (SVOCs) may
exist in both the paniculate and vapor phases, so appropriate sampling methods are limited to
those that apply to both phases.  The concentration of particulate-borne contaminants can be
estimated from the data for total paniculate matter (PM) loadings; however, these values are
extremely conservative.

             Sampling techniques may be divided into two broad classes, regardless of the
analytes of interest - integrated sampling and grab sampling:

             •     Integrated Sampling — methods that involve the  collection of a sample
                   over a fixed time period (e.g., 8-hours or 24-hours) and provide a
                   single, integrated (i.e.,  time-averaged) value.  Included in this
                   classification are sorbent tube collection methods and most paniculate
                   matter and semi-volatile compound collection methods.
             •     Grab Sampling — methods that involve collection of an instantaneous
                   whole air sample or real-time analysis.

Each of these classes of methods has certain  advantages and disadvantages, depending on the
monitoring objectives,  the required detection  levels, and the duration of the monitoring
program.  These two classes of sampling methods are briefly described below.
                                         3-2

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             Integrated Sampling

             Integrated sampling methods are among the most commonly used procedures
for sampling air, since most contaminants are present in ambient air at relatively low levels,
and some type of sample concentration is therefore necessary to meet detection limit criteria.
Appropriate integrated sampling methods exist for collecting VOCs, SVOCs, and PM.

             Integrated sampling methods can be useful for determining time-integrated
pollutant concentrations, such as 8-hour OSHA PELs or other regulatory standards. When
performing any integrated sampling, the  sampling period must be long enough to collect
sufficient analyte to achieve the desired detection limits.  In general, the longer the sampling
duration, the more analyte is trapped and the lower the detection  limit.  Therefore, integrated
sampling methods may not be adequate for evaluating compliance with short-term (e.g., 15
minute, 1 hour) action levels.  For example,  even a high-volume particulate sampler
generally will not be capable of collecting enough sample to determine compliance with
short-term action limits for heavy metals. Similarly, most sorbent collection methods for
VOCs will  require sampling periods of several hours or more to  achieve typical required
detection limits.

             The objectives of ambient air monitoring (AAM) at Superfund sites are
different than those for compliance or PSD monitoring.  As discussed in Section 1.3, the
primary goal(s) usually is to evaluate the potential human health risk to on-site workers or
the surrounding populace. For some analytes such as dioxins, a sampling period of 48 or
even 72 hours  may be needed to obtain adequate sample for the desired detection limits.  Of
course, the exact duration of sampling is not  as important as achieving a compound detection
limit capable of meeting the preset action limits.

             One drawback of time-integrated sampling is the lack of immediate feedback,
compared with the data that provided by  real-time or automated continuous monitoring
methods. Integrated sampling methods typically do not give site  decision makers  timely data
so that they can determine worker and community exposure to pollutants or the need for
implementing emission controls.
                                        3-3

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             Grab Sampling

             Grab sampling consists of collecting a single point-in-time sample.  Among
these methods are the collection of whole air samples in SUMMAฎ polished stainless steel
canisters or Tedlarฎ bags and the collection of samples using colorimetric gas detection
tubes, such as those made by Drager or Gastek Corporations.  Samples are collected over a
period of a few seconds to a few  minutes. Real-time monitoring methods usually involve
grab sampling.

             Grab sampling is commonly used as a screening technique to identify
contaminants that might be present in an area of interest and to determine the approximate
concentrations of these contaminants.  For example, grab  samples may be collected during
the SI using SUMMAฎ canisters and analyzed by GC or GC/MS to aid the development of a
target analyte list for any long-term VOC monitoring.

             Frequency of Data Updates

             The categories of integrated sampling and grab sampling can be further
subdivided according to the frequency with which the data values are updated (or the rapidity
with which the data are reported): single value, real-time monitoring, and continuous or
semi-continuous monitoring.

             Single value methods involve the collection and analysis of a discrete sample.
Included in this category are all methods that involve collecting the sample in a container or
on a matrix and subsequently transporting the sample to an on-site or off-site laboratory for
analysis.

             Automatic continuous systems are methods that involve the semi-continuous,
automated collection of samples followed by one or more detection methods. This approach
usually is  used as part of a fixed  monitoring network to minimize the labor requirements
                                         3-4

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associated with sampling and analysis.  The sampling and analytical methods tend to be
similar to single value methods, except they are automated as far as possible.

             The samples may be analyzed directly at the collection point,  or the sample
may be transported up to several hundred feet to an analytical device.  In the latter case, a
single analytical device may be used to analyze samples from multiple monitoring stations.
The analyzer periodically cycles through the network.  Automated analytical systems may
involve gas chromatography (GC), gas chromatography/mass spectrometry (GC/MS), mass
spectrometry/mass spectrometry (MS/MS),  infra-red spectrometry (IR), Fourier Transform
Infrared (FTIR) spectrometry, or ultra-violet, differential absorbance spectrometry  (UV-
DOAS).

             Real-time monitoring refers to methods that provide (nearly) instantaneous
values, so multiple measurements can be made over a period of minutes.  A wide range of
methods fall under this classification, including such widely used  portable instruments as the
FoxBoro Organic Vapor Analyzer  (OVA) or the HNu Photoionization Detector (PID), and
similar instruments.  In addition, specialty gas monitors that measure specific compounds or
compound classes also fit into this category. These usually are process-type monitors
designed to continuously monitor for ppm or percent levels of specific analytes.  Another
real-time (or near real-time) monitoring approach is optical remote sensing using
spectroscopic methods such as FTIR and UV-DOAS.

             Real-time analyzers  usually are used to monitor at or near  areas of high
emissions such as areas of active remediation, to give site decision makers timely
information. Most of the portable real-time monitors react with entire classes of compounds
and tend to not be specific  for a given compound.  For example,  PIDs are very sensitive to
aromatic hydrocarbons but  significantly less sensitive to aliphatic  hydrocarbons.
Furthermore, they cannot differentiate between benzene and toluene if both compounds are
present. In many instances, an action  level  will be set, based on  a total response, as if the
instrument response were due solely to benzene and not other aromatic compounds.
                                         3-5

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             A guide has recently been published for selecting real-time ambient air
monitoring instruments for use at Superfund sites."  Users should consult that publication for
more detailed information about specific models of real-time instruments.

             Method Selection

             Information is given in the following subsections about specific methods for
VOCs, SVOCs, etc. that will aid in the selection of a specific sampling method once the
target analytes and their classification are known.  Organic compounds can be grouped as
VOCs, SVOCs, and non-volatiles as shown in Table 3-1.

             A number of toxic organic (TO) sampling methods exist for VOCs and
SVOCs, as shown in Figure 3-1. The  detection limits and applicable range for these
methods are given in Figure 3-2. Similar information for a wide range of sampling and
analytical methods is given in Figure 3-3.

3.1.2         Sampling Methods for Volatile Organic Compounds (VOCs)

             VOCs are among the most common type of contaminant of concern at
Superfund sites.  Three  classes of VOCs  generally are a concern at Superfund sites,  and  the
specific class  of VOCs present will dictate the appropriate sampling and analytical protocols.
The VOC  classes of most common interest  are:

             •     Aromatic compounds  such as benzene, toluene, ethylbenzene,  and
                   xylene(s) (BTEX);
             •     Halogenated hydrocarbons such as vinyl chloride, trichloroethylene,
                   and 1,1,1-trichloroethylene; and
             •     Oxygenated compounds such as formaldehyde or acetone.
                                        3-6

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                       Table 3-1.
Characterization of Organic Compounds by Vapor Pressure
Vapor
Pressure

-------
    n-Nitrosodimethylamine
    Volatile-10 C to 200 C
    Volatiles-15 to 120 C
    Volatiles 80 - 200 C
                                SPECIFIC
                                  SEMI-
                             VOLATCLES
                             VOLATILES
                                                               TO-8
      Cresols/Phenols
            TO-9
                                                                Dioxins
                                                               TO-10
                                                              Pesticides
           TO-11
                                                           Formaldehyde
                                                               TO-12
            NMOC
           TO-13
        Semi-Volatile
                                                          J    TO-14
Volatiles - 100 to 179 C
Figure 3-1.  Compendium of EPA Toxic Organic Methods (Temperature ranges refer to
           boiling points).
                                    3-8

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Compend.
Methods
TO-1
TO-2
TO-3
TO-4
TO-5
TO-6
TO-7
TO-8
TO-9
TO-10
TO-11
TO- 12
TO-1 3
TO-1 4
Compound
Class
Volatiles
Volatiles
Volatiles
Pesticides
Ald/Ketones
Phosgenes
Amines
Phenols
Dioxins
Pesticides
Ald/Ketones
NMOC
PAHs
Volatiles
Methodology
Sampling
Tenax
CMS
CRYO
PUF
Impinger
Impinger
Adsorb
Impinger
PUF
PUF
Sep-PAK
Canister
PUF
Canister
Analysis
GC/MS
GC/MS
GC/FID
GC/ECD
HPLC
HPLC
GC/MS
HPLC
HRGC/MS
GC/FID
HPLC
FID
GC/ECD
GC/MS
Compendium Methods for Sampling and Analysis
or Organic Air Toxics
••:••••' I
- : m : i

•: I I


%:

'" : I
3S ':j

: ':I4 - JM
••-:- ,,:!;"
1
                               0.01    0.10    1.0     10     100     1000
                                      Approachable Detection Limits, ppb
Figure 3-2.  Detection Limit and Applicable Range for TO Methods.
                              3-9

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Remote FTIR
Remote MS/MS
Total HC Analyzers
Portable GC/FID
Portable GC/FPD
Portable GC/ECD/PID
Portable Electrochemical
Continuous Colorimeters
Detector Tubes
Portable IR
Colorimetric Tape Monitor
Passive Dosimetry
Impingers
CEMs (Chemiluminescent)
-. . ' • • ••••• ••."•;:!







• ' •.... 1

1
I

1
                                    1       I          I         I       I          I
                                   0.10   1.0       10       100   1,000     10,000
                                                  Approachable Detection Limits, ppb
Figure 3-3.   Detection Limit and Applicable Range for Various Sampling and Analytical
             Methods.
                                         3-10

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The sampling and analytical methods chosen will depend on the number and type of
compounds of interest and on the required minimum detection limits.  Sampling methods for
a number of commonly encountered VOCs are described in Table 3-2. For guidance on
compounds or compound types not found in Table 3-1,  consult "Compendium of Methods
for the Determination of Toxic Organic Compounds in Ambient Air"10 or the NIOSH
Methods Manual.12

3.1.2.1      Whole Air Sample Collection

             Whole air samples can be collected in glass or steel sample bombs, Tedlar
bags,  or SUMMAฎ polished stainless steel canisters.  The collection and analysis of whole
air samples has several advantages over integrated samples collected using sorbent methods.
Since the sample is collected whole instead of being adsorbed onto a medium, concerns about
collection efficiency or breakthrough are eliminated,  as are concerns about desorption
efficiency.  In addition, there are fewer problems with artifact formation, which can be a
problem with sorbent methods.  The various whole air sample collection methods are
discussed in the following subsection.

             SUMMAฎ Polished Stainless Steel Canisters

             SUMMAฎ  polished stainless steel canisters are specially passivated containers
used to collect whole air samples.  The interior surfaces of the canisters are coated with pure
nickel-chromium oxide (SUMMAฎ polishing process), which renders them inert.  Because
the entire container is metallic, no photochemical reactions occur after sample collection, and
permeation of the compounds in or out of the container does not occur.  The  samples can
leak, however, if the inlet lines, valves, and seals are defective or not used properly. The
sample atmosphere can be kept at negative pressure to minimize the effects of water vapor
condensation and chemical reactions. Also, the canisters can be reused after a relatively
simple cleaning procedure.  This is the only suitable whole air collection method if samples
must be stored for more than 24 hours before analysis.
                                         3-11

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CO
 CD

1
                                            3-12

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             Most hydrocarbons and chlorinated hydrocarbons (including BTEX) are stable
in SUMMA* canisters for periods of at least 30 days.13-14-15  The holding times for some of
the light oxygenated compounds such as acetone or methanol, however,  are not well
documented, but are thought to be two weeks or more.

             Samples can be collected in evacuated canisters in one of two ways: under
positive pressure or negative pressure (subambient).  In subambient pressure sampling, a
mass flow controller or vacuum regulator is used to control the flow  of sample into the
evacuated canister.  The difference in pressure between the canister  and the ambient
environment provides the driving force for collecting the sample.  Sampling may continue
until the canister is slightly below atmospheric pressure.  It is best not to continue sampling
until the pressure is equalized, since this makes it difficult to ascertain exactly when sampling
ceased and  if leakage has occurred.  Also,  the sample flow rate will typically drop off as the
canister nears ambient pressure.

             Vacuum regulators are designed to maintain a constant flow as long as the
difference in vacuum between the source (in these cases, the canister) and  the ambient
environment is within a certain range.  Vacuum flow regulators usually provide a constant
flow until the vacuum inside the canister reaches approximately 8-10" Hg (approximately 5
psig) vacuum. At this point, the flow rate  will decrease at an almost linear rate until the
canister reaches ambient pressure.  Once the flow rate begins to decrease,  there is no longer
true integrated sampling.  A mass flow controller used  with a subambient sampling system,
on the other hand, can be used to within approximately  1" Hg  (0.5 psig) with no change in
the flow rate.  Therefore, when using subambient (non-pumped) sampling  systems, the
sampling run  should be stopped  with 8-10" Hg remaining in the canister when using vacuum
flow regulators for controlling the flow and with 1-2" Hg remaining in the canister when
using mass  flow to control the sampling systems.

             The second collection method involves using a pump to fill the canister to
above ambient pressure.  With this  system, canister leakage will not affect sample integrity
to the same extent as for subambient systems, since any leakage will  be  of sample out of the
                                         3-13

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canister rather than of ambient air into the canister.   When sampling with a pump in areas
with high humidity, however, water may condense inside the canisters if they are pressurized
above 5 psig.  This can cause compounds to adsorb into the water droplets and also
subsequently cause canister cleaning problems.  Another potential drawback of a pump-based
canister sampling system is that pumps are more difficult to keep clean because of the teflon
or other porus materials typically contained in pump diaphragms or parts.  In general, the
less material and void volume between the sample inlet and the canister, the better the
sample representativeness and integrity.

              Glass Sampling Bombs

              Glass sampling bombs are generally small (125-ml to 1000-ml) glass
containers with a stopcock on each end.  These are fairly inexpensive, easy to handle, and
are relatively inert. They generally make good containers for grab sampling if the contents
will be analyzed within 8 hours of sample collection.  They are, however, quite prone to
breakage and must be protected from light so photo-induced reactions won't occur.  They
also are not suitable for integrated  sampling.

              Stainless Steel Bombs

              Stainless steel bombs are  another option for collecting grab  samples.  They are
identical to the canisters discussed  above, but they are not SUMMAฎ passivated.  Since these
devices are not passivated,  they are not  as inert as the SUMMAฎ processed  canisters and are
therefore more prone to reactions (including corrosion of the interior surface).  Stainless steel
bombs are usually less than 1 liter in volume and have most of the same attributes as glass
bombs, but they are not prone to breakage.  They usually have valves on both ends and the
sample can be introduced by using the vacuum of an evacuated bomb to pull in ambient air,
or by using  a pump to force air into the bomb.  Samples should not be held for over 24
hours unless the stability of the compounds of interest in these containers  has  been
documented.  In general, these vessels should be considered only for grab sampling  and on-
site analysis.
                                          3-14

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             Gas Sampling Bags

             Gas sampling bags are used to collect and store air samples for short periods
(less than 8 hours). The sampling bags are known by various trade names such as Tedlarฎ,
Teflonฎ, Mylarฎ, and Saranฎ.  These bags are relatively inert but can be prone to leakage or
permeation of compounds into and out of the bag.  The materials from which these bags are
made are somewhat porous and therefore tend to adsorb organic compounds.  Consequently,
it is difficult to clean gas sampling bags to meet strict background (blank) standards.  As a
general rule, gas sampling bags are not suitable for collecting samples for the analysis of
sub-ppm levels of ambient organic compounds.

3.1.2.2      Sorbent Collection Methods

             Solid sorbents are a collection  medium used to adsorb and hold VOCs, which
are then desorbed from the medium using either thermal or chemical extraction before
analysis. Sorbent media are able to concentrate organic analytes from an air stream, thus
decreasing the detection limits (DLs) for those analytes over DLs for whole air collection
methods used with direct injection analytical methods (whole air samples can be
preconcentrated,  as with EPA Method TO-14). Sorbent methods have certain general
advantages and disadvantages that should be considered  before a sampling and analytical
method is selected for a given application.  In addition,  many different sorbents are
available, and each has its  own specific advantages and disadvantages.

             Sorbent sampling techniques tend to be relatively cost effective.  The medium
itself is inexpensive, readily available from several manufacturers, and available for many
specific compounds or compounds classes.  Since sample volumes can be adjusted (to a
certain extent) according to anticipated ambient levels of the target analyte(s), adequate
detection limits for many compounds can be attained.
                                         3-15

-------
             There is no "universal"  sorbent; consequently, sorbent selection should be
carefully tailored for the target analyte(s).  If the target analyte list contains a variety of
compound types, several different sorbents (e.g., multi-bed sorbent tubes) may be needed.
Factors to consider when selecting a specific sorbent include sample interferences, ambient
moisture (humidity), breakthrough characteristics of the compound(s), the desorption
characteristics of the analyte with the particular sorbent, and sample stability.

             There are two basic types of sorbent materials: those that adsorb the VOCs
onto the sorbent medium and those that chemically react with the target analyte(s) to form a
new compound. Chemically-reactive sorbents are typically used to collect compounds that
are very unstable or reactive. For example, HBr-coated charcoal tubes can be used to collect
ethylene oxide, and dinitrophenylhydrizine (DNPH)-coated silica gel can be used to collect
aldehydes and ketones (EPA Method TO-13).

             Although many types of sorbent materials are available for sampling VOCs,
each sorbent type has certain limitations that must be considered.  Many sorbents are affected
by high ambient humidity. For these  sorbents,  moisture coats the sorbent material,
effectively "blinding" the  medium by filling the active sites  with water instead of VOC.  The
other potential problem with sorbent tubes is breakthrough,  as discussed above.

             Many of the sorbent tube sampling methods were developed for industrial
hygiene (IH) applications.  The detection limits needed for work-place exposure estimates are
generally orders of magnitude higher than those needed to determine long-term health effects,
such as the 1 in 106 cancer risk.  Problems that can be encountered when attempts are made
to adapt IH methods to fence-line ambient monitoring; are:

              •      Moisture interference from longer sampling periods;
              •      Breakthrough  due to longer sampling periods;
              •      Sample or compound degradation due to larger air volumes; and
              •      Insufficient sample detection limits.
                                          3-16

-------
All of these considerations need to be evaluated before selecting a sampling method.  In
some instances, the site investigators should perform a methods development program to
determine whether a specific method is adaptable to a given application.  The review and
input of staff experienced in the sampling and analysis of VOCs is recommended as part of
the method selection process.

3.1.2.3       Automated Fixed-Location Continuous Analyzers

             The use of fixed-location continuous analyzers has increased in recent years.
These instruments are capable of the near real-time analysis of a range of organic
compounds, at detection limits in many cases equal to what can be achieved in the
laboratory.  A few of these techniques include a sample preconcentration system to increase
analyte detection limits.  A  common preconcentration approach is the use of a sorbent with
thermal desorption. Information about real-time instruments, including automated continuous
analyzers, is summarized in Table 3-3.

             These systems offer many advantages, particularly when site remediation is
expected  to last several years.  The systems can be configured many different ways using
detectors best suited for the given target analytes.  The near real-time (each analysis taking
approximately 30 minutes) data collection allows the investigator to  make decisions whether
ambient levels of pollutants are exceeding action levels and about what action to take, instead
of having to rely on less accurate methods (such as OVAs) to determine whether remediation
should continue or be curtailed.  Also, compliance with the action level(s) for a given
compound is known immediately instead of several days after the fact.

             The  main disadvantages of these methods are high detection limits,  expense,
maintenance, and siting.   Original equipment costs (including shelters) can run as  high as
$100,000 per site, depending on the sophistication of the instruments purchased  and siting
concerns. Also, a  network of this type will require highly  trained and knowledgeable
technicians to keep the equipment functioning properly and to ensure the that data collected
meet program objectives.  Since these units need a clean, climate-controlled shelter, siting
                                         3-17

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                                                      3-19

-------
can pose problems.  The shelters need electrical service (a minimum of 100 amps to support
the heating and cooling equipment), level-protected sites, and telephone lines if data are to be
retrieved electronically.  Given the cost and logistical constraints, this sampling option is best
suited for AAM studies expected to last over one year.

3.1.2.4      Portable Real-Time Analyzers

             Portable real-time analyzers are generally used to provide screening or
industrial hygiene applications. These analyzers are usually either the general-response type,
i.e., they respond to general classes of compounds, or specific-response analyzers which only
respond to a specific compound.  Most real-time instruments (excluding paniculate analyzers
and fixed location instruments such as GC, GC/MS, or FTIR) can be separated into three
broad categories according to their detection methodology:

             •      Electrochemical Systems;
             •      Total Hydrocarbon Systems; and
             •      Spectrophotometric Systems.

Information about portable real-time analyzers is included in Table 3-3.

             A wide selection of electrochemical systems is available for measuring toxic
gases.  These systems are commonly  used in industrial hygiene applications because of their
small size,  simple operation, and low cost.  Electrochemical sensors are designed to be
compound specific;  they respond to only one compound (i.e., oxygen,  carbon monoxide,
hydrogen sulfide,  hydrogen chloride,  sulfur dioxide, etc.) rather than to a broad family of
compounds.

             Total hydrocarbon monitors are capable of detecting a wide range of
hydrocarbons.   The most widely-used total hydrocarbon systems are those that use flame
ionization detectors  (FID) and photoionization detectors (PID).  Thermal detection monitors
and solid-state detectors are also available. The most commonly used total hydrocarbon
analyzers are the OVA,  which uses an FID to detect hydrocarbons, and the HNuฎ,  which
uses a PID to detect hydrocarbons. Both of these analyzers report a total instrument
                                         3-20

-------
response rather than data for individual species. The PID analyzer is less sensitive to
aliphatic hydrocarbons than the OVA, but is very sensitive to aromatic hydrocarbons, such as
benzene; however, it cannot differentiate one compound from another.

              Spectrophotometric analyzers encompass a broad range of widely-used
analyzer systems that determine airborne pollutant concentrations by  measuring their
absorption of radiant energy. In most instrument applications, radiant energy from the
ultraviolet, visible, or infrared regions of the electromagnetic spectrum is used.
Spectrophotometric systems most applicable to Superfund air monitoring applications include
Nondispersive infrared (NDIR) analyzers and Optical Remote Systems (see Section 3.1.2.6).

              A more complete discussion of real-time monitoring instruments and their
capabilities, along with a current list of the vendors, can be found in Reference 11.

3.1.2.5       Colorimetric  Gas Detection Tubes

              Colorimetric gas detection tubes produce a color change when exposed to the
target compound. These tubes were originally designed for industrial hygiene applications;
however, many are capable of measuring contaminants at ambient levels.  This technique
involves pulling  an air sample through the detection tube with either a hand- or battery-
operated pump.  The tubes are calibrated based on a preset sample volume specific to each
tube.

              Colorimetric gas detection tubes offer the advantage of being small, portable,
and inexpensive; in addition, they provide essentially instantaneous results. Gas detection
tubes are also  available for a wide array of compounds.   Their main  disadvantages include
lack of specificity (interferences from other compounds that may be present), lack of
adequate detection limits for some compounds, and inability to be used for automated
sampling. Also, sampling techniques relying on gas detection tubes cannot be readily
modified to meet special program demands.
                                         3-21

-------
             Another type of colorimetric detection system are portable tape instruments.
These instruments collect an air sample onto a chemically treated tape whose color changes if
the specific compound is present. The color intensity is proportional to the concentration of
the compound.  These monitors are available for only a small number of compounds.  They
generally offer good analytical detection limits for those compounds in ambient air.

             When considering a colorimetric gas detection tube or portable tape monitor,
the vendor literature should be consulted to determine if the particular technique will be
sensitive enough for its application, if it is free from interferences,  and if it will meet the
monitoring goals of the program. These techniques are generally best used for area or
personnel  monitoring, and  are not typically appropriate for fence-line or perimeter
monitoring or for evaluating community exposure downwind of the contaminated site.

3.1.2.6      Open Path Monitors

             An emerging set of technologies for monitoring ambient air are open path
monitors (OPMs).16 OPMs rely on the interaction of light with matter to yield qualitative
and quantitative information about that matter.  Since every molecule and atom exhibits a
unique spectral pattern as a function of wavelength, the identification of each molecule or
atom is possible  if enough  of the spectral pattern is  obtained.  Two types of OPM systems
are commercially available for  ambient air monitoring — the Ultraviolet-Differential Optical
Absorbance Spectrometer (UV-DOAS) and the Fourier Transform Infrared (FTIR)
spectrometer.  The UV-DOAS  is normally configured as an open path monitor (OPM); the
FTIR can be used as an OPM or a closed path monitor (CPM).  A third OPM system, gas
filter correlation (GFC), also is currently ready for  use at Superfund sites.

             The FTIR and UV-DOAS systems  direct a beam of light through the ambient
air (the sample), collect the transmitted light, and analyze the change in light intensity at
selected wavelengths.  The UV-DOAS is capable of path lengths on the order of 3
kilometers; the FTIR is capable of path lengths approaching 1 kilometer.  Since the light
beam is interacting with molecules along its entire beam path, its output is a path-weighted
                                         3-22

-------
concentration with units of concentration times distance such as ppm*meter.  The ppm*m
value can be converted to a direct concentration by dividing by the path length; however, this
will only yield an accurate concentration measurement at a specific point along the path if the
compound is homogeneously distributed along the path.

             Open path monitors are useful when long perimeter distances need to be
monitored, a fast time response is required, or continuous monitoring is required.  The OPM
output of ppm*m can be used with an inverted dispersion equation to calculate a source term,
which is then used in a dispersion model to predict downwind concentrations.5  Information
on the use of OPM data is given in Section 5.

             The FTIR also can be used as a CPM by allowing the sample to flow through
an optical cell.  The light is multi-passed through the cell; path lengths of 400 meters for
cells 3 meters in length are achievable.17  By design, the CPM is a point sampler. It retains
the advantage of fast time response and continuous monitoring but loses the wide area
monitoring capabilities.   The use of CPM systems versus OPM systems is compared in Table
3-4.

             OPM systems are capable of detecting a wide range of compounds as shown in
Table 3-5; the ability of canister methods (TO-14) to detect these  same compounds  is also
shown for comparison.  Detection limit information for OPM systems is shown in Table 3-6.

3.1.3        Semi-Volatile Compound Sampling Techniques

             Semi-volatile compounds (SVOCs) include polynuclear aromatic compounds
(PAHs), their halogenated derivatives such as PCBs, organopesticides, and polychlorinated
dibenzo(p)dioxins and furans.  Depending on the number of fused carbon rings and the vapor
pressure of the compound, these compounds will exist in both vapor phase and particulate-
bound forms.  Therefore, a collection system capable to  collecting both phases is needed to
collect representative  samples.  Table 3-7 summarizes the sampling methods used to collect
the SVOCs normally  encountered at Superfund sites.
                                        3-23

-------
                               Table 3-4.
    Comparison of Conventional Point Monitoring and Open Path Monitors

Detection Limits
Data Turn Around
Dispersion Model Inputs
Unknowns
Guidance
Site Layout
CPM
Lower detection limits than OPMs;
usually below the long-term action
levels.
For speciated data, at least 1-hour, but
generally 24-48 hours; may not be able
to warn if short-term action levels are
exceeded.
Must be extrapolated from a line of
point samplers.
More accurately identifies the presence
of compounds near the detection limit;
accuracy doesn't necessarily improve as
concentrations increase.
Well documented and accepted.
Sensitive to areas where sampler can
not be placed on the ground; insensitive
to hilly or broken site terrain.
OPM , /. r;^;-
Higher detection limits than CPMs on
most path lengths; may be above some
long-term action levels.
Speciated data for tens of compounds
available in minutes. Can warn of short-
term health exceedances.
Direct output in one or two dimensions.
Less accurate at lowest concentrations
observable, but gets better as
concentration increases over reasonable
range. Easier to identify unknowns at
reasonable concentrations.
Little documentation; still not well
understood.
Sensitive to Hne-of-sight obstruction;
insensitive to recessed obstacles such as
lagoons and pits.
CPM = Conventional Point Monitor
                                   3-24

-------
                Table 3-5.
Methods for Monitoring Specific Compounds
: Compounds
Canister
UV-DOAS
FTIR
GFC
ALKANES
Ethane
Propane
n-Butane
n-Hexane
Isopentane
Isooctane
Cyclopentane
X
X
X
X
X
X
X







X
X
X
a
a
a
X
X
X
X
a
a
a
X
ALKENES
Ethene
Propene
1-Butene
1-Hexene
Trans-2-butene
1,3-Butadiene
Isoprene
X
X
X
X
X
X
X







X
X
X
X
X
X
X
X
X
X
X
X
X
X
ALKYNES
Acetylene
X

X
X
AROMATICS
Benzene
Toluene
Ethyl benzene
o-Xylene
p-Xylene
m-Xylene
1,3,5-Trimethyl benzene
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
HALOGENATED
Trichloroethylene
Chloroform
Tetracholoroethylene
1,1,1 -Tricholorethane
Methylene chloride
t- 1 ,2-Dichloroethane
Vinyl chloride
1 , 2-Dichloroethane
Chlorobenzene
1,1-Dichloroethane
Carbon Tetrachloride
PCB's
X
X
X
X
X
X
X
X
X
X
X












b
X
X
X
X
X
X
X
X
X
X
X
b
X
X
X
X
X
X
X
X
X
X
X
b
                   3-25

-------
                             Table 3-5.  (Continued)
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METALS
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Cadmium
Chromium
Copper
Lead
Mercury
Zinc












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OXYGENATES
Methanol
Ethanol
n-Propyl alcohol
Dimethyl ether
Methyl t-butyl ether
Acetone
Formaldehyde
Acetaldehyde
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c
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c
c
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X

X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
OTHERS
Hydrogen chloride
Hydrogen fluoride
Hydrogen cyanide
Chlorine
Bromine
Fluorine
Carbon dioxide










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X
X

X
X
X



X
X
X
X



X
CRITERIA POLLUTANTS
Ozone
Nitrogen dioxide
Sulfur dioxide
Carbon monoxide




X
X
X

X
X
X
X
X
X
X
X
X         = A compound is detectable by this method.
a          = These compounds are generally reported as part of the hydrocarbon continuum
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b          = These techniques have the potential to measure this compound but no detection
             limit information is available.
c          = "Polar" compounds, specifically oxygenates, may not be measured accurately
             by canisters.
UVDOAS  = Ultraviolet-Differential Optical Absorbance Spectrometer
FTIR      = Fourier Transform Infrared Spectrometer
GFC       = Gas Filter Correlation Spectrometer
                                        3-26

-------
                                   Table 3-6.
                           Detection Limits for OPMs
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Chloroform
Tetrachloroethylene
1 , 1 1 1-Trichloroethane
Methylene chloride
t- 1 ,2-dichloroethylene
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1 ,2-dichloroethane
Chlorobenzene
1 , 1-dichloroethane
Carbon Tetrachloride
PCBs
Benzene
Toluene
m-Xylene
o-Xylene
p-Xylene
Ethylbenzene
Phenol
Cyanides
Arsenic Compound
Cadmium Compound
Chromium Compound
Copper Compound
Lead Compound
Mercury Compound
Zinc Compound
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       Sampling systems for SVOCs must employ a quartz fiber (or other low background)
filter followed by a suitable sorbent media. Also, these systems generally require large air
volumes (e.g., the use of a high-volume air sampler) to achieve the necessary detection limits
for evaluating health risk or action levels for SVOCs.

       Even though these samples are collected on combined filter and sorbent media, it
cannot be assumed that separate analyses of the two substrates will yield the relative
particulate-bome and vapor-phase constituent concentrations. Some SVOCs will be
transferred from the paniculate phase to the vapor phase because of the vacuum applied
during the sampling process.  The phase distribution  depends on the temperature and the
degree of volatility of the individual compound.  Techniques for phase distribution analysis
are still being developed.  Most of the phase distribution techniques require the use of low-
volume sampling techniques and therefore are not appropriate for many compounds that have
low health effects levels.

       Polvchlorinated Biphenvls (PCBs)

       PCBs usually are collected using a high-volume PS-1 sampler manufactured by
General Metal Works, Village of Cleves, Ohio.  Substrates consisting of a quartz fiber filter
(or similar low background filter) with a solid sorbent consisting of layers of polyurethane
foam (PUF) between  a  layer of Florisilฎ resin.  Foam plugs alone can be used; however,
when using PUF plugs  alone, the collection efficiency of mono- and di-chlorinated congeners
may decrease.

       Sampling duration should be approximately 24 hours, or 200 cubic meters (m3).
Sample volumes significantly less than 200 m3 may result in diminished detection limits,
while sample air volumes in excess  of 275 m3 may result in analyte breakthrough. These
sample volumes will generally be adequate for any Superfund site containing  PCB-
contaminated soils. If the  known contamination levels are extremely high,  lower sample
volumes and/or shorter  sampling durations may be used, however, it is probably best  to start
                                         3-29

-------
with the sampling times and volumes outlined and adjust them accordingly as data becomes
available.

       A NIOSH method using sorbent tubes for determining PCB concentrations also exists.
This method is similar to the high-volume methods described above in terms of sorbent
media type and analytical method, but it uses small sorbent tubes and low volumes.  This
technique was developed to monitor workplace exposure and consequently has detection
limits several orders of magnitude higher than those needed to determine action levels for
community exposure.  The techniques may be appropriate for monitoring worker exposure
during remediation, but it should not be used for fenceline monitoring or to determine
compliance with  health risk action levels.
       Polychlorinated Dibenzo(p)dioxins and Polychlorinated Dibenzo(p)furans
       (PCDDs/PCPFs)
       Polychlorinated dibenzo(p)dioxins and polychlorinated dibenzo(p)furans
(PCDDs/PCDFs) may be found at Superfund sites either due to their presence in soil from
contamination by organopesticides or their production during the on-site incineration of soil
or waste containing high levels of chlorinated compounds (such as chlorinated solvents).

       PCDDs/PCDFs are toxic to varying degrees, depending on the number of chlorine
molecules and the position of those molecules.  Generally, only the fifteen 2,3,7,8-substituted
isomers of PCDDs/PCDFs are a major health risk concern; 2,3,7,8-tetrachloro-
dibenzo(p)dioxin (TCDD) is the greatest risk.  Although the octa-chlorinated dioxins and
furans are ubiquitous in the environment, they pose little health risk and therefore are seldom
quantitated.

       Action levels for 2,3,7,8-TCDD may be on the order of 3.0 pg/m3 to 5.5 pg/m3.18
Action levels are not normally used for the other 2,3,7,8-substituted isomers.  To obtain such
low detection levels,  very large air sample volumes must be sampled (800-1200 m3).
Samples should be collected on quartz  fiber  filters (or equivalent) with a PUF plug solid
sorbent using a PS-1  high-volume air sampler.  Sample collection duration will be 48-72
                                         3-30

-------
hours, depending on the analytical technique used to analyze the samples.  Sample
breakthrough with PCDDs/PCDFs is not a problem; however, it is important that surrogate
compounds be added to each PUF plug before sampling to determine sampling and analytical
recoveries. The air volume needed will depend somewhat on the analytical technique used to
analyze the samples; the lower value (800 m3) is needed for high resolution gas
chromatography/mass spectroscopy (GC/MS), and larger volumes are required for medium
or low resolution GC/MS.

      Organochlorine Pesticides

      Organochlorine pesticides can be collected using a low-volume sampling technique,
adsorbing the pesticides on to polyurethane foam (EPA Method TO-10), or they can be
collected using a high-volume technique.  Care must be taken when using high volume
sampling techniques because many of these compounds have low breakthrough volumes with
PUF sorbent media. An additional sorbent medium, such as Florisilฎ resin, should be used
in addition to the PUF plugs. When using a high-volume approach, adequate surrogates
should be added to help determine the  potential for breakthrough.

       The advantage of high-volume sampling is the ability to concentrate more ambient air
and consequently lower the detection limits.  Using the PUF along with Florisilฎ resin allows
for the simultaneous collection of both PCBs and pesticides, with the Florisil resin helping to
prevent breakthrough of the lighter molecular weight pesticides.

      Polvnuclear Aromatic Hydrocarbons (PAHs)

      Polynuclear aromatic hydrocarbons (PAHs or PNAs), can be encountered at many
sites,  especially old "Town Gas" sites.  PAH compounds range from three to six aromatic
rings and will exist in both the vapor and particulate-borne phases.  The percentage of the
compound found in each form generally depends on the molecular weight of the compound
(i.e., the lower the molecular weight the greater the percentage of compound found in the
vapor phase).
                                        3-31

-------
      Like other semi-volatile compounds, PAHs also must be collected with both a
paniculate filter and back-up sorbent media.  Several sorbents have been used to collect the
PAHs, including Tenax GC, XAD-2, and PUF.  All these compounds have been found to
have a high collection efficiency for benzo(a)pyrene (B[a]P). EPA Method TO-13 specifies
the use of either XAD-2 resin or PUF.  Other variants include XAD-2 resin sandwiched
between two one-inch PUF plugs, or XAD-2 resin supported by a one-inch PUF plug.  For
the heavier PAHs, any of these techniques should prove satisfactory; however, if lower
molecular weight compounds, such as naphthalene, acenaphthylene, or acenaphthene are to
be quantitated, XAD-2 resin without any PUF should be used.  This is due to high
background levels in the PUF material. The XAD-2 resin also has  a high background level
of naphthalene; however, typical ambient levels should be well above the background level if
careful cleaning is performed.

      As with most of the semi-volatile compounds, samples usually are collected using PS-
1 high-volume samplers. Other low- and medium-volume samplers are also acceptable;
however, the lower the total sample volume,  the worse the analytical detection limits.  In
some cases, such as when reliable electrical power is not available,  battery-operated, low-
volume samplers may be necessary. Sampling periods may need to be extended if low-
volume samplers are used.

      A NIOSH method exists that uses  filter and sorbent tubes for determining PAH
concentrations.  This method is similar to the high-volume method described above in
sorbent media type and analytical method, but it uses small sorbent tubes and low volumes.
The technique was developed to monitor workplace  exposure; consequently, the detection
limits are several orders of magnitude higher than those needed to determine action levels for
community exposure.  The technique may be appropriate for monitoring worker exposure
during remediation  but it should not be used  for fenceline monitoring or determine
compliance with health risk action levels.
                                        3-32

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3.1.4  Particulate Matter

       Solid or liquid participates (aerosols) can be released from Superfund sites into the
ambient air.  These can include contaminated and noncontaminated soil particles, heavy
metal particulates, pesticide dusts, and droplets of organic or inorganic or organic liquids.
Particulate matter (PM) is collected to determine the total or size-fractionated paniculate
matter concentrations, heavy metals concentrations, and/or particulate-borne aerosols/organic
compound concentrations in the ambient environment surrounding a site.  Table 3-8
summarizes the advantages and disadvantages of certain paniculate sampling techniques.

       Several different sampling devices can be used to collect the samples including real-
time analyzers,  low- to high-volume paniculate samplers, and sampling systems that only
collect a certain size fraction of the paniculate matter. Manual collection methods are by far
the most commonly used  for measuring both total suspended paniculate (TSP) matter19 and
paniculate matter with  an aerodynamic diameter of less than 10 microns (PM10).20 Both
methods require the subsequent analysis  of collection filters, a process that can take, at the
very least, 24 hours.

       Two types of high-volume samplers are commonly used to collect paniculate matter.
The first collects all airborne paniculate matter and is referred to as a total suspended
paniculate (TSP) sampler, while the second collects only paniculate matter with an
aerodynamic diameter of  less than 10 microns (PM10). The PM10 paniculate matter is
important  from  a health risk perspective, since this  size fraction can enter the human
respiratory system because it is too small to be filtered out by the body's defense
mechanisms.  At most sites, PM10 will be measured because the results  from this analysis can
be directly correlated with potential health effects.  If environmental impacts being evaluated,
TSP samplers may be more appropriate.
                                         3-33

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                                   3-34

-------
       Direct reading instruments able to continuously monitor and display ambient air
particulate counts have been available for several years and are increasing in use.   They fall
into two classes:  optical devices and radiometric devices.

       Optical-based paniculate monitors include Transmissometers and Light Scattering
devices.  A  transmissometer consists of a light source and a detector.  By comparing the
obstruction of a light beam by paniculate matter in the  sample gas to an unobstructed light
path.  These types of monitors are also used for in-situ applications, such as across a stack.
Radiometric monitors measure paniculate matter by a radiation attenuation technique; low-
energy beta radiation is normally used. In the typical beta-gauge, a filter tape is slowly
moved past  a radioactive beta source, and the sample is drawn into the sample inlet of the
instrument,  where it passes through a tape filter mechanism.  The radiometric attenuation of
the filter is then measured before collection in  the clean state and after collection in the  dirty
state.

       Automated paniculate monitors (of either type described above) are able to provide
real or near-real time data of ambient air paniculate concentrations.   They are particularly
valuable, therefore, in emergency removal applications, where frequent updates  are required.
Automated particulate monitors are more expensive than more conventional paniculate
sampling techniques and, because of their increased complexity, require greater  technical
skills  by the operators responsible for maintaining them.  Also, they must be installed in an
environmentally controlled  shelter, making them less amenable to small or short-term
monitoring programs.  No information about heavy metal concentrations or other constituents
can be discerned from these monitors.

       At many sites where the pollutant of interest is particulate borne (e.g., heavy  metals),
portable analyzers can only be used to estimate the potential exposure from the pollutant by
using  the particulate value to extrapolate a heavy metal concentration. The action limits set
using  these analyzers are usually quite conservative and are generally based on historical data
from high-volume sampling techniques.  Portable real-time PM analyzers are available with
detection limits of 1 /zg/m3.11
                                         3-35

-------
3.1.5  Inorganic Compound Collection Methods

       Heavy metals, including lead, arsenic, chromium, cadmium, nickel, and zinc, are a
concern at many Superfund Sites.  Mercury and such inorganic compounds such as cyanide
are also encountered frequently. These elements may have vastly differing effects on human
health, depending on the form or compound in which the element exists.  An example is the
difference between hexavalent chrome  (chrome (VI)) and trivalent chrome (chrome (HI)).

       Methods for determining the different forms or valence states of an element or
compound can be labor and time intensive in relation to determining the existence of the base
compound.  In many instances, an action level will be based on the concentration of the base
compound (e.g., total chrome) as if it were all in the more toxic form (i.e., hexavalent
chrome).  This may hamper remediation efforts  if such efforts are curtailed when a  "true"
health concern does not actually exist.   In this instance, performing the more difficult and
expensive analysis could remove some undue restraints from the remediation effort.  Various
methods for collecting the inorganic compounds commonly found at Superfund sites are
discussed below.

       High-Volume Sampling For Heavy Metals

       As the name implies, high-volume collection methods collect large volumes of air.
Most metal samples are collected on either quartz or glass fiber filter.  While either of these
filters can be used, experience has shown that quartz fiber filters provide lower background
levels of compounds of interest and less chance of interferences.  Since heavy metals are
associated with paniculate matter in  the environment, a decision as to what particulate
fraction to collect must be made.

       There are two basic types of high volume samplers  — those that  filter out all
particulate matter in the air sample (TSP) and those that collect a certain size fraction,
normally 10 microns and less (PM10).   Particles with an aerodynamic diameter of more than
 10 microns aren't generally able to enter the human body because they are filtered out by the
                                          3-36

-------
body's defense mechanism.  Particles smaller than 10 microns are able to enter the body and
therefore pose a greater risk to human health.  If a health risk action level based  on
respiratory action is being applied, PM10 paniculate matter should be collected.  TSP
samplers are appropriate where the potential for land deposition and bio-accumulation is of
concern.

       Medium- and Low-Volume Sampling

       Medium- and low-volume paniculate sample collection methods are those  that collect
less than 10 cubic feet-per-minute; some samplers designed to collect only a few  liters-per-
minute. Samplers included in this class include the Dichotomous sampler, the Battelle-
Columbus medium-volume air sampler, and other portable paniculate samplers.

        These samplers are generally used for specialty applications (i.e., the Dichotomous
sampler is used to size  fractionate ambient paniculate matter) or where large masses of
paniculate matter are not needed for chemical speciation.  Also,  there are low-volume solar
or battery operated paniculate samplers for use in areas where electrical service is not
available.  As a general rule, if electrical service is available, high-volume methods are
generally preferable to low-volume methods when the paniculate matter needs to  be
analyzed.

       Mercury

       Almost all metals can be collected using a high-volume sampling technique. The one
notable exception is mercury. Mercury can exist in several forms, including vapor-phase
elemental mercury, which is the most common form in ambient air. Because  of  the volatility
of mercury, high-volume filtration techniques are not appropriate for sampling mercury.
From a health effects perspective, the elemental and methylmercury forms are the most
serious. Methylmercury forms when mercury is deposited in freshwater lakes and is
transformed into methylmercury at the water sediment interface.  Therefore, methylmercury
should not be of concern at most Superfund sites.  Elemental mercury will typically be the
                                         3-37

-------
primary form.  The best methods for collecting mercury involve amalgamating the mercury
with gold.  Several researchers, including Gary Glass with the U.S. EPA in Duluth,
Minnesota,20 have used the Jerome mercury analyzer with good results.  This analyzer can be
used to determine real-time mercury concentrations and, by using gold foil dosimeters, can
be used to measure time-integrated samples.

       Cyanide

       The commonly employed methods for determining cyanide involve collecting the
cyanide in basic (either NaOH or KOH) impingers. If both the paniculate cyanide and
gaseous cyanide are to be determined,  a teflon filter can be used before the impingers.
Potassium hydroxide (KOH) is the recommended impinger solution; however, sodium
hydroxide (NaOH) can also be used.

3.2    ANALYTICAL METHODS

       An overview of analytical methods is given below, followed by a discussion of
specific methods for analyzing VOCs,  SVOCs, and PM/Metals.

3.2.1  Overview of Analytical Methods

       To a certain extent, the sampling  method used to collect the samples will dictate what
analytical methods can be used. In some instances, however, several analytical methods will
be appropriate and a decision as to what method to use will have to be made.  Choosing an
analytical method will require a knowledge of the form of the analyte being determined as
well as other factors,  including:

       •     Level of quantitation required to meet action levels;
       •     The sample turnaround time;
       •     Anticipated form(s) of the analyte present in the sample; and
       •     Availability and capability of on-site or nearby laboratories.
                                        3-38

-------
       An example of the trade-offs in choosing among analytical methods is the availability
of GC and GC/MS techniques for analyzing both VOCs and SVOCs.  For most of the
organic compounds discussed in this section, both GC and GC/MS methods are given.  As a
general rule, GC methods coupled with appropriate detectors are more sensitive, in some
cases by several orders of magnitude, than the corresponding GC/MS method.  GC methods,
however, all suffer from the potential co-elution of peaks, although using multiple detectors
can help alleviate some of this problem.  GC/MS is much more accurate from a qualitative
standpoint, but often is unable to detect compound levels commensurate with pre-set action
levels. Determination of the most appropriate analytical method for each target analyte will
have to be based on site-specific objectives.

       This section briefly describes appropriate analytical methods for many compounds
typically encountered  at Superfund sites.  Real-time monitors, remote sensing
instrumentation, and fixed location continuous analyzers are not discussed in this section,
since their applications are a combination of simultaneous sampling and analytical functions.
A summary of the various analytical methods, along with the advantages and disadvantages
of each, is presented in Table 3-9.  The various analytical approaches used in the TO
methods are shown in Figure 3-4.

3.2.2   Volatile Organic Compound (VOC) Methods

       This section discusses VOC samples collected in SUMMAฎ polished stainless steel
canisters and those collected on sorbent media.  Because of the vast number of sorbents for
collecting VOCs, only general guidance for performing sorbent analysis is given.

       Canister Methods

       Canister sampling techniques are appropriate  for a wide range of volatile organic
compounds.  Likewise the two most commonly used analytical techniques for analyzing
canister samples are able to determine a wide range of compounds.  These methods are gas
chromatography with  multiple detectors (GC/MD) or gas chromatography with mass
spectroscopy (GC/MS).   These two analytical techniques are the basis of EPA Method TO-
14.
                                       3-39

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          GC
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Figure 3-4. Compendium of TO Analytical Methods
           3-42

-------
       GC/MD uses several analytical detectors either in series or in parallel.  Since
selection of the detectors can be based on the compounds present at the site, lower detection
limits or greater specificity for certain compounds can be achieved.  An example of this is
the use of a Hall Electroconductivity Detector (HECD) for detecting halogenated compounds.
This detector is capable of detecting many halogenated compounds at ambient concentrations
of 10-100 parts-per-trillion with good precision and accuracy.  With either method, some
type of sample preconcentration is required.  Normally cryogenic preconcentration is used;
however, sorbent preconcentration with thermal desorption can also  be used.

       Selecting GC/MD or GC/MS will depend on several factors, including:

       •      The physical characteristics of the compounds to be analyzed;
       •      The number of compounds quantitated; and
       •      The detection levels required (usually driven by health risk criteria).

There are  several types of GC/MS systems, and the specific operating mode will affect the
choice of analytical techniques.  All GC/MS  techniques involve separating a gas sample
using capillary chromatography  and  basing the identification of compounds on the compounds
mass fractionation.  In general,  however, all GC/MS techniques suffer for similar problems.
They include:

       •      Sensitivity to water vapor; the samples  must be thoroughly dry before analysis;
       •      Difficulty in determining low molecular weight compounds; and
       •      Generally less sensitivity than GC only methods.

GC/MS instruments are typically operated in either full scan mode or in selective ion
monitoring (SIM) mode. SIM is used  when a small target list (usually less than 15 target
compounds) of compounds are being quantitated. SIM has the advantage of being
significantly more sensitive than the full-scan mode for most compounds,  but cannot detect
ions from  other compounds that are  not on the target list.  Full-scan monitoring provides
more qualitative information, but may  not be sensitive enough to determine the  health risk
potential of many ambient compounds.
                                        3-43

-------
      Because of the number of different detectors available, GC/MD may be preferable in
some instances. GC/MD systems are not as sensitive to water vapor as GC/MS systems;
therefore, they can be used to analyze samples containing polar compounds, which would
typically be removed in the sample drying process.  A GC/MD will normally be capable of
detecting significantly lower ambient concentrations than a GC/MS, although SIM may
achieve  similar analytical detection limits.  When using SIM, however, the ability to detect a
large number of compounds will be jeopardized.  GC/MD relies primarily on
chromatographic retention time to determine compound identity. Co-elution of compounds
may cause interference; however, the compound identity can many times be confirmed by the
relative  responses for that compound from the different detectors.

      Both GC/MD and GC/MS are excellent analytical methods, and each has certain
advantages and disadvantages for specific applications; however, the overall differences
between the two methods are fairly  minor.  The choice of GC/MD or GC/MS should be
made by an experienced chemist, based on the compounds present at the site, the potential
uses of the data, the project needs, and the necessary detection limits required.

      Sorbent Methods

      Because of the number of sorbent methods for collecting and analyzing volatile
organic  compounds, this section will only deal with general cautions and concerns with
sorbent  sampling in general.  Sorbent media analysis  may involve many techniques, including
gas chromatography with a variety of different detectors and high-performance liquid
chromatography (HPLC). Regardless of the exact analytical technique, all sorbent sampling
has common steps involved in collecting and analyzing the samples.  They include:

      •     Drawing ambient air  through the medium and adsorbing the analyte(s) of
             interest onto the medium;
      •     Preservation of the collected species until analysis can be performed;
      •     Desorption of the analytes of interest from the medium; and
      •     Separation and detection of the target analytes.

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       Precautions that need to be taken while VOCs are being collected on the sorbent
medium are discussed in Section 3.1; therefore, sampling precautions are not discussed
further here. Once the sample is collected, two main factors affect the reliable quantitation
of the target species — media artifacts and the desorption characteristics of the  medium and
analytes.

       Media artifacts or background compound levels must be known to adequately
characterize the analytes being sampled.  If the background level is large in relation to
ambient concentrations of target compounds, adequately characterizing the target compounds
will be difficult.  Also, media artifacts can form during sampling that may co-elute with the
analytes, thereby masking the true analyte concentration.  For any sorbent tube sampling,
adequate media blanks must be analyzed to ensure that background levels of the analytes of
interest will not interfere with the method.

       Spiked media samples should also be analyzed to ensure that media artifact peaks are
not occurring during sampling. This is done by spiking one sorbent tube with  the analytes of
interest and collecting an ambient sample with this tube side-by-side with an unspiked tube.
The spike recovery  will be determined by the difference between the unspiked  sample
concentration and the spiked sample concentration minus the spike value. In addition to
helping to determine the  formation of possible interference compounds during sampling, this
technique also helps to evaluate overall sample collection, desorption, and analysis
procedures.

       The other test that must be done on all sorbent tubes is  a desorption study.
Regardless of the desorption technique (e.g., solvent extraction, or thermal desorption), the
efficiency of removing the target analytes from the sorbent media needs to be ascertained.
One potential drawback of some sorbents is that they "hang on" to the compounds too
tightly, and removing the targets from the media is difficult. Because of the generally rapid
turnaround required for Superfund monitoring this may not be a problem; however, if
samples are collected and archived, this may need to be considered.
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      Desorption studies should be performed by spiking the sorbent medium with the target
analytes and leaving the spike on the medium the same length of time that ambient samples
are on the medium.  Then the spikes are handled in the same way as the field samples.  If
the data indicate a consistent bias due to desorption efficiency, either internal standards can
be added before sampling to adjust the data, or a factor can be used to correct for the bias
caused by incomplete desorption.

3.2.3 Semi-Volatile Compounds  (SVOQ Methods

      This section discusses the general methods used to analyze ambient,air samples for
classes of semi-volatile compounds that may be encountered at Superfund sites.  The
sampling methods for these compounds have been discussed in Section 3.1.2.  In some
instances, only a single method is suited for the analysis of the compounds,  in others, two or
more methods may be appropriate.   In these instances, the differences in the methods will be
discussed, as will the relative advantages of each method.

      Polvchlorinated Biphenvls  (PCBs)

      There are two generally accepted methods for determining the quantity of PCBs
collected on PUF or on combined PUF/solid sorbent media, gas chromatography with
electron capture detection (GC/ECD) or gas chromatography/mass spectroscopy (GC/MS).
GC/ECD is the analytical method outlined in EPA Method TO-4.  This method detects PCBs
by their Aroclor pattern. An Aroclor is a mixture of compounds that make up a commonly
used product.  Since various PCBs have historically been  used for a variety of purposes, the
individual arochlor can be identified. GC/ECD analysis has the advantage of being fairly
simple and relatively inexpensive to perform.  The major drawback of this analysis is the
inability to detect the compounds when such things as incineration  or thermal destruction
have degraded the individual Aroclors.
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      If PCBs are being remediated at a site using incineration (or some other high-
temperature treatment) on-site, GC/MS must be used to determine if PCBs are present.  This
is necessary if the Aroclors are being incompletely combusted, the Aroclor pattern is
destroyed and the GC/ECD analysis would not be able to recognize the characteristic pattern.
      Polvchlorinated Dibenzo(p)dioxins/PolYchlorinated Dibenzo(p)furans
      (PCDDs/PCDFs)
      PCDDs/PCDFs or dioxins and furans have very low health risk action levels (NOEL
of 5.5 pg/m3 for 2,3,7,8-TCDD);18 therefore, the collection and analysis of these compounds
is quite difficult and expensive. It is generally accepted that at least 800 m3 of air sample be
collected for analysis.  Analyses should be performed using high resolution gas
chromatography/high resolution mass spectroscopy (HRGC/HRMS); however, if the air
volume is increased to approximately 1200 m3, medium resolution GC/MS may be used.

      Dioxins and furans are very heavy compounds and, depending on the molecular
structure of the congener, they can be quite difficult to remove from the PUF medium used
to collect them.  It is very important when monitoring for PCDDs/PCDFs that the laboratory
personnel be experienced in this analysis. Because of the very low levels found, laboratory
contamination is a serious problem,  especially if the same laboratory is also  handling high-
level samples such as  those found in contaminated soils.

      Because of the risk of losing or of not being able to remove these compounds from
the various media used to collect and clean the samples during the sample collection and
analysis processes, many surrogate compounds must be added at various steps along the
sample collection/sample analysis process.  Surrogate compounds are isotopically labeled
compounds that will act similarly to the native compounds but that can be differentiated from
the native compounds because of the mass difference of the isotope. It is not uncommon for
up to 13 surrogate compounds to be added to each sample.  The surrogates are used to
correct sample concentrations due to losses from incomplete desorption of the targets and
losses during sample "clean-up."
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      Because of the complexity of the sampling and analysis of PCDD/PCDF compounds
and the extremely high level of quality control needed, the sampling and analysis should only
be performed by individuals experienced in this area. Also, care must always be exercised
to prevent contamination or other bias in the sample collection and analysis.

      Organochloride Pesticides

      The two primary analytical methods for determining concentrations of organochlorine
pesticides in air samples, gas chromatography with electron capture detection (GC/ECD) and
gas chromatography/mass spectroscopy (GC/MS).  GC/ECD is by far the preferred method
because of its lower cost and greater sensitivity. GC/ECD has an order of magnitude, or
greater, sensitivity than GC/MS.  Compound identification by  GC/ECD is accomplished by
using characteristic retention  times,  compound standards, and second detector confirmation.
Therefore, GC/MS offers greater confidence in compound identification because of the mass
spectra produced during analysis; however, many sample concentrations will be below what
is detectable by GC/MS.

       Polvnuclear Aromatic Hydrocarbons (PAHs)

       Polynuclear Aromatic Hydrocarbons (PAHs)  are generally analyzed by either high-
performance liquid chromatography (HPLC) or gas chromatography/mass spectroscopy
(GC/MS).  HPLC methods involve  using high-pressure liquid  chromatography  coupled to
either a fluorescence detector or a combination of a  fluorescence and ultraviolet detectors.
Because of the second detector confirmation, this latter method renders highly accurate
results.  Also, many fluorescence detectors are capable of being  programmed to scan certain
wavelengths for additional confirmation and lower detection limits.

       Like the other method comparisons described above, GC/MS is capable of accurate
identification; however, its sensitivity is generally less  by an order of magnitude or more.
GC/MS is also more costly than HPLC.  Depending on what ambient levels are detected,
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identification of a few samples by GC/MS will help confirm identifications made by the
HPLC analysis.

3.2.4  Inorganic Compound Methods

       The inorganic compounds normally found at Superfund sites include heavy metals,
including mercury, and cyanide salts.  These analytical methods are discussed in this section.

       Heavy Metal Analytical Methods

       Filter samples from high-volume samplers are digested in acid and analyzed by one of
several methods.  The potential methods include atomic absorption spectroscopy (AAS),
inductively coupled argon plasma emission spectroscopy (1CAPES), and graphite furnace
atomic absorption spectroscopy (GFAAS). These three methods are similar in their
analytical theory, the differences being primarily in the exact technique.  The merits of these
methods are discussed below.

       Atomic absorption spectroscopy (AAS) involves aspirating an acid-digested filter
sample into a flame, which vaporizes the element of interest. Light of known intensity
characteristic of the element is directed through the metal vapor where it is absorbed.  The
absorption is proportional to the concentration over a certain range.  This technique is
relatively inexpensive, readily available, and quite sensitive for most heavy metals.  Its major
drawback is that only one element at a time can be determined.

       Inductively coupled plasma atomic emission spectroscopy (ICP-AES) uses a very
high-temperature argon plasma flame to excite the atoms.  1C APES can be used to detect up
to 40 elements simultaneously, which makes it very cost effective for analyzing samples of
several elements.  While these instruments are widely available in laboratories, they are
expensive and may not be suitable for an on-site laboratory because of their cost.
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      There are several commonly occurring metals found at Superfund sites that are not
amenable to either AAS or 1C APES. They include notably lead and arsenic.  For these
compounds, GFAAS should be used. Although they can be detected by the other two
methods, the sensitivity is significantly better on GFAAS. For instance, the typical
laboratory detection limit for lead by 1C APES is approximately  50 /*g/L, while for GFAAS,
the laboratory detection limit is approximately 5 /xg/L. If very high lead concentrations are
always found, the ICAPES could be used as a more cost effective way (since it could be
done simultaneously with other metals) to determine lead; however, if greater sensitivity is
desired, GFAAS should be used.

      Mercury was discussed in the metals sampling section. Although there are other
methods for collecting mercury,  the most accurate methods involve amalgamating the
mercury with gold.  As mentioned earlier, the Jerome analyzer  (which uses gold foil
techniques) can be used quite successfully for sampling and analyzing mercury.  Another
technique (which also involves collecting the mercury on gold) uses cold vapor atomic
absorption spectroscopy to quantitate the mercury concentration. This technique measures
the mercury concentration "cold" without using flame or a high-temperature furnace. The
Jerome analyzer flashes the mercury off the gold dosimeter and measures the difference in
conductance before and after flashing.

       Cyanide

       Cyanide generally refers to all the CN groups in a compound that can be determined
as the CN" ion. Cyanide compounds may be classified as being either simple, in which the
CN group is present as either CN" or HCN, or complex, where the CN group is complexed,
typically to a heavy metal.  Generally, simple cyanides are more toxic than the complex, due
to the greater availability of HCN.

       It is possible, by selective preparation methods, to differentiate between the simple
and complex forms of cyanide.  Simple  cyanides may usually be brought into solution by
aqueous dissolution, as in an impinger.  Complex cyanides require a more rigorous  digestion,
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such as in acid and with a catalyst, to liberate CN for analysis.  After the appropriate
preparation of a collected sample, all solutions may be analyzed for CN~ by the methods
described below.

       Three commonly used analytical techniques are used to measure cyanide
concentrations.  They include:

       •      Cyanide ion-specific electrodes;
       •      Colorimetric procedures using spectrophotometric techniques; and
       •      A titration technique using silver nitrate.

       The major drawbacks of the ion-specific electrode include potential interferences,
many of which could easily be present, along with cyanide contamination, at a site. The
interferences include sulfide, chloride, iodide, bromide, cadmium, zinc, silver, nickel,
cuprous iron, and mercury.

       The colorimetric method converts the cyanide to cyanogen chloride, complexing the
cyanogen chloride with a pyridine-barbituric acid reagent to form the color, and measuring
the absorbance.  This method is fairly sensitive, with a detection limit of approximately 0.02
mg/L. The major interferences include thiocyanates, sulfide,  and high concentrations of
cadmium.

       The third method involves titrating the impinger solutions with a solution of silver
nitrate in the presence of a silver-sensitive indicator. This method is best suited to higher
levels of cyanide (i.e., more than 1 mg/L in the solution). Sulfides are the major interferant.

       The analytical method chosen  for cyanide will depend  on what other compounds are
also present at the site, since all three analytical methods have interferences.  The various
analytical methods are  also sensitive to concentration.  To get the best mix of sampling time
or volume, along with  the appropriate analytical technique, may require some methods
development and trial and error.  Again, the review and input of staff experienced  in this
type of sampling is recommended as part of the method selection process.
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                                    SECTION 4
                QUALITY ASSURANCE AND QUALITY CONTROL

             EPA requires that a quality assurance project plan (QAPP) be prepared and
implemented for all environmental measurement programs mandated or supported by the
agency through regulations, grants, contracts, or other formalized means.  The main purpose
of the QAPP is to specify the minimum procedures that must be used to ensure that the
accuracy, precision, completeness, and representativeness of the resulting measurement data
are known, documented, and sufficient to achieve the overall goals of the measurement
program.  The information for ambient air monitoring (AAM) programs at Superfund sites
may be incorporated into other documents, such as the site Health & Safety Plan or Remedial
Design Documents, rather than as a stand-alone document.  For sites where AAM will be
conducted on a long-term basis, however, a separate QAPP for the AAM program is
recommended.
  •
             The general principles of quality assurance and quality control are described in
Section 4.1 of this document. Specific guidelines for preparing and implementing QAPPs for
Superfund Air Pathway Assessment Programs appear in Section 4.2.

4.1          GENERAL PRINCIPLES OF QUALITY ASSURANCE AND QUALITY
             CONTROL

             In the context of this document, as in other EPA reports, the term quality
assurance refers to the entire system of activities, planned  or taken, to ensure that the
measurement data are of sufficient quality to meet the overall goals of the program.   In this
context, quality assurance includes such things as:  quality planning, personnel  training,
standardization of procedures, documentation, data validation, and data quality evaluations.
The term quality control relates more specifically to  the operational techniques and activities
used to sustain acceptable levels of data quality. Such things as routine instrument checks,
flow rate checks, duplicate samples, blanks, calibration checks, etc., are part of quality
control.
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             Detailed guidelines and procedures for achieving quality assurance and quality
control in air pollution measurement systems are given in EPA's five-volume series, "Quality
Assurance Handbook for Air Pollution Measurement Systems".21'25 Although the series deals
primarily with routine air monitoring for criteria air pollutants (SO2, NO2, O3, CO, PM10 and
Pb), the principles of quality assurance given in Volume I of this QA Handbook form an
appropriate basis for designing a quality assurance program for air pathway assessment
activities.  Other useful references are EPA's "Technical Assistance Document for Sampling
and Analysis of Toxic Organic Compounds in Ambient Air"26 and "Preparing Perfect Project
Plans".27 Much of the information that follows is drawn from these documents.

             The QA handbook and TAD both describe several different elements of quality
assurance that together make up  a comprehensive QA program.   The individual QA
elements, listed in Table 4-1, are grouped  into separate functional units that relate to the
organizational level to which responsibility is normally assigned.  These functional units are:
(1) quality assurance management,  (2) sampling quality assurance, (3) analytical quality
assurance, and (4) data management quality assurance.  The Quality Assurance Project Plan
should address each specific feature of sampling, analytical, and data management quality
assurance.  Specific guidance for addressing  each of these topics in a QAPP is given in
Section 4.2.   QA management deals with  the underlying QA principles and structure used  to
design and implement the QAPP. A brief discussion of QA management is given below.

4.1.1         Quality Assurance Management

              To be effective, a quality assurance program must be thoroughly integrated
with the overall monitoring effort.  A prerequisite to achieving this goal is establishment of a
QA policy,  objectives, and organizational  structure to support the QA program.  All
members of the project  team must  be familiar with the goals and underlying principles on
which the QA program  is based. In the most general terms, the objectives of the QA
program should be to ensure that the measurement data are (1) technically sound and
defensible and (2) of sufficient quality to achieve the specific goals of the air pathway
assessment.  Whenever  practical, one person within the organization should be responsible
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for coordinating all of the quality assurance activities for the measurement program and for
determining whether the objectives of the QA program are being met. To maintain
objectivity, however, the QA coordinator should not be responsible for directly implementing
the specific QA activities associated with data collection and management (i.e., the specific
elements of sampling QA, analytical QA, or data management QA).  These responsibilities
should be assigned to other qualified personnel.

             After establishing the QA policy, objectives, and organizational structure, a
QA project plan should be developed.  The main purpose of the QA project plan is to specify
in advance the actions that will be taken to accomplish the QA objectives.  Specific
guidelines and specifications for preparing QA project plans were previously established by
EPA and are discussed with specific regard to the AAM program in Section 4.2.  The
structural format of the QAPP (as well as that of all other formal documentation of
procedures, plans, and specifications) should include a system of document control for
managing the organization and distribution of document revisions.

             In addition to the QA items described above, QA management also involves
such things as training personnel, evaluating data, conducting quality assurance audits,
preparing quality assurance reports, and taking corrective action. EPA offers an extensive
list of self instructional and other training courses pertaining to QA/QC through their Air
Pollution Training Institute (APTI).  For a list of courses or other related information, write
to:

                   Registrar
                   Air Pollution Training Institute (MD-20)
                   U.S. Environmental Protection Agency
                   Research Triangle Park, NC  27711
                   (919) 541-2401

The remaining aspects of QA management are the key elements of a QAPP, these are
discussed at length in Section 4.2.
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4.2          QUALITY ASSURANCE PROJECT PLAN

             Guidelines and specifications promulgated by EPA require that 16 essential QA
elements be addressed by the QAPP.28 The first two of these elements, title page and table
of contents, pertain only to the structure and format of the QAPP; others provide background
information, such as project objectives and measurement approaches, so that individuals not
already  familiar with the project can be appropriately informed. Most of the QAPP
elements, however, describe the specific actions that will be taken to ensure that the data are
of known, defensible, and sufficient quality. The 16 essential elements of a QAPP are
described below.  Wherever appropriate, guidance is given  on how to address these elements
with specific regard to an air pathway assessment (for some topics, specific guidance is given
in other sections of this document—e.g., site selection and measurement methods are
described in Sections 2.0 and 3.0, respectively).  The QA/QC elements of a long-term A AM
program are illustrated for a "typical" Superfund scenario in Appendix D.

4.2.1        Title Page

             In addition to the obvious information, the title page should indicate that the
QAPP has  been approved by the project manager, quality assurance coordinator, and either
the remedial project manager or on-site coordinator. Approvals should be  shown at the
bottom of the title page by the signatures of the appropriate personnel.

 4.2.2       Table of Contents

             As part of the system of document control, the QAPP Table of Contents
should specify the number of pages, revision number, and date of last revision for each of
the QAPP  sections.  A distribution list, indicating all official recipients of the QAPP should
be included at the end of the Table of Contents.
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4.2.3        Project Description

             A general description of the measurement program should be included to
provide background information for persons responsible for reviewing the QAPP. The
project description should include: (1) a description of the site and the status of any  remedial
activities, (2) the purpose of the measurement program, (3) target analytes and a brief
description of the measurement approach, (4) specific uses of the measurement data, and (5)
scheduled start-up and ending dates of the measurement program.

4.2.4        Project Organization and Responsibility

             The QAPP should include an organization chart identifying all of the  key
individuals involved in the technical, QA/QC, and managerial aspects of the measurement
program. The specific responsibilities and authorities assigned to each key individual and, in
some cases, their qualifications should also be described.  In  some cases, it might also be
desirable to indicate the telephone numbers  and office or lab  locations of key individuals.

4.2.5        Data Quality Objectives

             Data quality objectives, in terms of precision, accuracy, and completeness,
must be specified for each primary measurement parameter.  These objectives must  be
defined in terms of project requirements (not  based on the capabilities of the measurement
methods used) as discussed in Section 2.3 of this document.  Qualitative objectives pertaining
to the representativeness and comparability of the measurement data should also be
addressed. In addition, a discussion of the ramifications of not meeting the stated DQOs
should be included in the QAPP.
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4.2.6        Site Selection and Sampling Procedures

             The QAPP must document the proposed monitoring site locations, and the
rationale for their selection. Whenever practical, site maps and schematic diagrams  should
be used to identify specific locations and monitoring configurations.  Photographs taken from
each monitoring site showing the ground cover and fields of view in all directions from the
monitoring site, as well as a closeup view of the actual site location, are also recommended.

             The QAPP must also include a description of the sampling equipment and
procedures used for each primary measurement parameter.  Whenever practical, conventional
EPA sampling protocols such as those described in the various TO Methods should be
employed.  If standard methods are used, it is enough to simply reference the method.
However, if standard methods are  modified or if alternate methods are used, a description of
the method and the rationale for its selection should be given.  The description of sampling
procedures should include any specifications for:  (1) preparation, cleaning and certification
of sampling equipment; (2) sample preservation, transport, and storage; and (3) sample
holding times before extraction and analysis.

4.2.7        Sample Custody

             A description of all  sample custody procedures, forms,  documentation, and
personnel responsibilities pertaining to both field and laboratory operations must be  included
in the QAPP.  Specific items that  must be addressed in this regard are:  (1) documentation of
procedures for preparing of reagents or other supplies that become an integral part of the
sample (e.g., filters, sorbent  media, or reagents);  (2) procedures and forms for documenting
the dates, times, locations, and other relevant data pertaining to sample collection and
analysis; (3) documentation of sample custodians in the field and laboratory; (4)
documentation of sample preservation methods; (5) sample labels and custody seals; (6) field
and laboratory sample tracking mechanisms; and (7) procedures for  sample handling, storage,
and final disposition.
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             The level at which these items should be addressed depends on the specific
scope and objectives of the air pathway assessment.  If the results of the air pathway
assessment will be used in litigation, strict chain-of-custody measures, as defined by EPA's
Office of Enforcement, can be required.  In other cases,  the goals of sample custody can
simply be to maintain the scientific credibility and integrity of the measurement data.

             Detailed guidelines for establishing sample custody procedures are given in
Volume II of EPA's QA Handbook for Air Pollution Measurement Systems.22 Key points in
this regard are: (1) all samples must be uniquely identified to ensure positive identification
throughout the test and analysis procedures; (2) all samples must be handled in a manner
suitable to ensuring that there is  no contamination or other breach of sample integrity that
might otherwise be caused by leakage,  reactive decay, accidental destruction, or tampering;
(3) chain-of-custody  forms must  accompany all samples from the field to the laboratory or
intermediate storage  points, and  the chain-of-custody forms should be signed by  all persons
who handle the samples along the way; (4) samples should be shipped only by registered
mail or other forms of registered service, and they should be addressed  to the specific person
authorized to receive them; and  (5) all  field notes, laboratory notes, and original calculations
should be saved.

4.2.8        Calibration Procedures and Frequency

             The QAPP must include a description of the calibration procedures and the
recalibration frequencies for each measurement parameter and measurement system. If
standard, documented methods are used, simply referring to the method is sufficient.
Otherwise, a complete description of the calibration  approach  should be given.  The
description of calibration procedures should address:  (1) the maximum  allowable time
between calibrations and calibration checks, (2) the quality and source of calibration
standards  (as a general rule, calibration standards should be certified to  between four and ten
times the accuracy of the equipment being calibrated), (3) the traceability of standards to
NIST Standard  Reference Materials or  equivalent Commercial Certified Reference Materials,
(4) the documentation of calibration results, and (5)  a statement of the appropriate
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environmental conditions needed to ensure that the equipment is not adversely affected by its
surroundings (e.g., adverse temperatures, humidity, vibration, lighting, chemical emissions,
radio frequency interferences, or electrical voltage fluctuations).

              The frequency of calibration should be in accord with any applicable
regulatory requirements  or recommendations of the equipment manufacturer.  In the absence
any such guidance, an initial calibration interval should be determined, based on the inherent
stability, precision, bias, and degree of use of the equipment.  The time interval may then be
shortened or lengthened, depending on the consistency of results obtained from  successive
calibrations.

4.2.9         Analytical Equipment and Procedures

              Officially  approved EPA analytical procedures should be used whenever they
suit the particular scope  and objectives of the air pathway assessment.  In these situations,
the applicable method should be referenced in the QAPP. Section 3.0 contains  a list of
standard methods that might apply to the air pathway assessment.  If standard methods are
modified or alternative methods employed, the modifications or alternate methods must be
described and the rationales must be given for their selection.  Whenever modified or
nonstandard methods are used, they must first be validated to demonstrate their performance
characteristics in terms of accuracy, precision, detection  limit, and specificity.  Procedures
and acceptance terms for the method validation study should be described in the QAPP.

4.2.10        Data Reduction. Validation, and Reporting

              A description of the  data reduction, validation, and reporting procedures for
each primary measurement parameter must be included in the QAPP. These procedures
should specify:  (1) all equations and statistical approaches used  to reduce the measurement
data, (2) the method for treating blanks during data reduction, (3)  the method for treating
cases of undetected compounds in the statistical calculations, (4) the methods used to identify
and  treat outliers, (5) the criteria for flagging  and validating data,  and (6) the units for
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reporting results. A flow chart is sometimes helpful for depicting the series of specific steps
taken from initial data collection, on through data reduction, validation, reporting, and final
storage.  Specific guidance for reducing, validating and reporting measurement data is given
in Section 5.0.

4.2.11        Internal Quality Control

              Internal quality control checks should be performed on all sampling and
analytical systems to verify and document whether such systems are operating within control
limits or require corrective action.  The procedures, control limits, corrective actions, and
frequencies with which QC checks should be performed should be specified in the QAPP.
Items to  be considered as part of internal quality control for field sampling systems include:
flow rate checks; leak checks; timer checks; and visual inspections of sample lines and inlets
for cracks, moisture, or debris. Whenever practical, these checks should be conducted
immediately before and after each sample collection period. The procedures for conducting
QC checks are likely to be instrument-specific. Equipment manuals or EPA-approved
Standard Operating Procedures (e.g., TO Methods) should be consulted for specific guidance
on designing internal QC procedures.

              Examples  of items to be considered as part of analytical internal quality
control are:   system blanks, replicate analyses, surrogate samples, spiked samples, reagent
checks, and calibration checks.  A listing of QA/QC samples is given in Table 4-1.  These
checks can be used to provide immediate feedback for  identifying whether the analytical
systems are operating within pre-established control limits. If control limits are exceeded,
corrective actions should be implemented before additional samples are analyzed.  Analytical
control checks should be performed at least once a day, or after every  10 samples are
analyzed.
                                          4-9

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             In addition to sampling and analytical control checks, quality control samples
should also be collected and analyzed to evaluate the overall performance of the measurement
system.  Types of quality control samples include:  field blanks, field duplicates, and field
matrix spikes.  Note that these types of samples differ from the analytical control samples
described above in that they originate at the field site and therefore reflect the combined
performance of both sampling and analytical systems. Field QC samples therefore provide a
more representative way to evaluate overall data quality, but because of lag times between
collection and analysis they are not as effective as analytical control checks for identifying
the need for corrective action.  The recommended frequency for collecting each type of field
QC sample is one per sampling event. Less frequent sample collection is sometimes
acceptable, but the total number obtained during any given period should be at least 5 % of
the total number of ambient samples.

             Whenever appropriate,  control  charts should be used to depict trends in the
QC data, distinguish patterns of random variation from variations  of assignable causes, and
identify when the measurement system is out  of control.rcf Determinations of appropriate
control limits should be based on either the performance characteristics of the measurement
system or on the specified requirements of the measurement procedure.  Common practice
sets control limits at ฑ 3 standard deviations  (excluding outliers) from the mean of previous
measurements.  Appendix H  of The QA Handbook, Volume I, gives detailed guidelines for
control charting QC data.21

4.2.12       Performance and System Audits

             Performance and system audits are the primary method to determine if the  QA
goals and objectives have been met.  The  scope and schedule for auditing each primary
measurement system or parameter, as well as the personnel conducting the audits,  must be
specified in the QAPP.  Performance audits are used to quantitatively evaluate the accuracy
of the data being generated, typically  by evaluating the recovery of certified reference
materials through the sampling and analytical systems.  System audits address, in qualitative
                                         4-11

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terms, the capabilities of the measurement system for generating data that meet QA
objectives for representativeness and comparability.  Such things as adherence to established
sampling and analytical procedures, sample custody, and equipment maintenance should be
addressed in a system audit.

             To maintain objectivity, performance and system audits should be conducted
by the project's QA Coordinator or other individuals who are not responsible for the
operational aspects of the air pathway assessment.  All materials and  supplies used in the
audit should also be different from those used during routine operation and calibration of
equipment.  Performance audits should be conducted at least once every three months for
long-term AAM networks; however, a more frequent schedule is recommended if results are
highly variable from one audit to the next.  A system audit should be conducted before or
shortly after the system becomes operational and should be repeated regularly thereafter
(e.g., quarterly or semi-annually).

4.2.13       Preventive Maintenance

             The following types of preventive maintenance should  be considered part of
the quality assurance program and addressed in the QAPP: (1) a schedule of important
preventive maintenance tasks that must be carried out to minimize instrument downtime, and
(2) a list of any critical spare parts that should be on hand to minimize instrument downtime.
Preventive maintenance  tasks and spare parts are instrument-specific.  Equipment manuals
and EPA-approved SOPs should be consulted for guidance on establishing specific
procedures and schedules.

4.2.14        Procedures Used to Evaluate Data Precision. Accuracy and Completeness

              Specific procedures used to evaluate data quality in terms of the precision,
accuracy, and completeness of all primary measurement parameters must be described in the
QAPP.   These procedures should specify the methods used to gather data for evaluating the
precision and accuracy and all  equations used in subsequent calculations.  Specific
                                         4-12

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requirements for evaluating the quality of the data generated by criteria air pollutant
measurement systems are given in the Code of Federal Regulations and other EPA guidance
documents.9'30  These methods are not always adaptable to air toxics measurement systems,
but whenever practical they should be applied.  These and alternative procedures for
evaluating data quality are described below. Note that data quality must always be
determined in a manner compatible with established data quality objectives.

             Recommended procedures for determining precision and accuracy depend on
whether the measurement method involves automated on-site analysis or requires integrated
sampling subsequent analysis off site.  For  automated on-site analytical systems, precision
data should be obtained by periodically (e.g., daily or weekly) challenging the analyzer with
a gas standard of known concentration and  observing the analyzer's response.  Calculation
procedures given  in the Federal Register (Part 58, Appendix B) are used to express precision
in terms of the upper and lower probability limits of the percent differences between the
known and observed concentration values.  Although EPA requires these procedures for
certain types of criteria air pollutant monitoring systems, no specific requirements exist for
air pathway assessments.  An alternative expression for precision, in this case,  is the relative
standard deviation (i.e., standard deviation divided  by the mean, expressed as a percentage)
of successive precision check results.

             Procedures for determining the accuracy of automated on-site analytical
systems should be similar to those for determining precision, except that the assessment must
be performed by someone other than the operator or analyst who conducts the routine
monitoring and must be performed using gases made from different working standards.
Accuracy should be expressed as the percentage difference between the known and observed
concentration values.  Alternatively, accuracy can be expressed as the percent of the known
concentration recovered through the analytical system (i.e., the observed concentration
divided by the known concentration, expressed as a percentage).
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              For measurement methods that require integrated sampling and off-site analysis
(these methods are sometimes referred to as manual methods), duplicate (collocated) sample
results should be used for determining data precision.   To obtain precision data, collocated
samplers should be located at the site with the highest expected concentration levels of target
analytes.  Duplicate samples can be also obtained at alternating sites if portable or multi-
channel samplers are used. Equations for expressing precision in terms of the upper and
lower probability limits of the percent difference of duplicate sample results are given in the
Federal Register (Part 58, Appendix B). Alternatively, precision can be expressed as the
relative percent difference of duplicate sample results, or pooled standard deviation.1*

              Accuracy determinations for manual methods should be performed by spiking
sampling media with known quantities of target analytes and measuring their recovery
through the extraction and analytical systems.   Media spikes should be prepared by the QA
Coordinator or another individual not involved in the operational activities associated with
sample collection or analysis. The accuracy of the measurement data should be expressed as
the percentage of the spiked amount recovered in the analysis.

              Data completeness for both automated and manual methods should be
expressed as the percentage of valid data relative to the amount of data that was expected to
be obtained under correct normal conditions.

4.2.15        Corrective Action

              A plan for initiating and implementing corrective actions must be included in
the QAPP.  The plan should specify:  (1) conditions that will automatically require corrective
actions; (2) personnel responsible for initiating, approving, implementing, and evaluating the
resolution of corrective actions; and (3) specific corrective action procedures used when
predetermined control limits are exceeded.  Corrective actions are usually instrument-
specific.  Equipment manuals and EPA-approved standard operating procedures should be
consulted for guidance on establishing specific corrective action procedures.
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4.2.16       Quality Assurance Reports to Management

             The QAPP should define a mechanism for periodically reporting to
management on the performance of the measurement systems and data quality.  At a
minimum, QA reports should include:  (1) assessments of measurement data accuracy,
precision, and completeness; (2) performance and system audit results; and (3) significant
QA problems and recommended solutions.
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                                     SECTION 5
                               DATA MANAGEMENT

             The goal of ambient air monitoring (AAM) programs at Superfund sites is to
generate accurate, verifiable reports on ambient concentrations of air pollutants in the area of
concern. These data are usually applied to evaluations of the risk to on-site personnel and
the surrounding community. The data used in these evaluations must be defensible and must
meet the criteria established in the Quality Assurance Project Plan (QAPP) or AAM Plan for
accuracy, precision, completeness, and representativeness.  Therefore, establishing sound
data management procedures and objectives early in the program can be critical to its
success.

             Long-term AAM programs may generate tremendous amounts of data. In
most cases, AAM data are reviewed regularly (e.g., daily) and compared with action levels
to see if any exceedances have occurred.  The AAM data are then stored in hard-copy form,
entered  into databases, or summarized in word processing software.  Frequently, problems
arise when, at some future date, someone needs to review or use the data.  In too many
cases, the data record is incomplete, the data are stored in a variety of formats,  or they have
not been consistently validated.  It may then be expensive or impossible to reconstruct  a
complete set of validated data; therefore,  a data management program should be established
before any long-term AAM program begins.  Much of the information in this section also
applies to short-term AAM programs.

             The key elements of data management for AAM programs  include:  data
management planning, data acquisition, data reduction, data validation, and data reporting.
These elements  are discussed in the following sections.
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5.1          DATA MANAGEMENT PLANNING

             Collecting and maintaining unnecessary or redundant data can create needless
data management costs, while insufficient, improperly formatted, or poorly managed data can
prove equally costly to the program. To maximize the efficiency of the data management
process, data collection methods and standards should be developed early in the program
with the end use of the data in mind. Specific information management objectives may
require the comparison of data with chemical-specific health criteria, state or local air toxics
guidelines, ambient air standards, or other compliance requirements. Monitoring results may
be applied to health risk assessment models to calculate the individual or community health
risks associated with ambient air pollutants, or they  may be used to validate predictive
software models.

             The QAPP or the AAM plan should provide  a management framework to
coordinate and evaluate data management program activities.  Data management procedures
should be contained or referenced in these documents to ensure that sampling and analytical
data are captured,  stored, and maintained in an efficient and secure environment and that the
quality of the measurement data is high enough to meet the goals of the program.  Program-
specific information for documentation and recordkeeping requirements, data quality
objectives, and data storage, transfer, and manipulation should be specifically addressed.

             Documentation and Recordkeeping

             The sampling plan or the QAPP should specify the data recording procedures
for the AAM program.  Data must be collected and supporting documentation maintained
for:

              •     Periodic readings of meteorological conditions at appropriate  time
                    intervals;
              •     Temperature, flow rates, volumes and other measured parameters at
                    specified time intervals;
              •     Instrument operating variables;
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             •      Upset conditions, such as emergency releases;
             •      Calibration or maintenance procedures; and
             •      Sample tracking and analytical results.

             A logbook should be maintained for the entire sampling program to document
sampling descriptions, meteorological data and upset conditions. Logbooks should be
maintained for each instrument to record calibration and maintenance activities.  Data sheets
and forms should be designed to support raw data collection and chain-of-custody
information.  Documentation of analytical procedures and results must also be developed and
maintained throughout the life of the program. Responsibility for maintaining and  storing
program documents should be clearly specified to facilitate the rapid retrieval of information.

             Data Quality Objectives

             Data quality objectives (DQOs) and procedures for evaluating data quality are
specified in the QAPP to ensure the representativeness, completeness and comparability of
measurement data.  Acceptance criteria for accuracy, precision, and completeness must be
specified for each primary parameter.  Corrective action methods for addressing
measurements not meeting  stated DQOs should be addressed, as well as standard statistical
and analytical procedures for manipulating the measurement data.

             Data Transfer. Storage and Reporting

             Data management procedures for the typical AAM program are characterized
by the need to store and integrate large volumes of data derived from a variety of data
sources. Because these data may be collected over a long period of time by different parties,
developing an integrated data management system for the transfer,  storage, and manipulation
of data to create final reports is an essential program planning activity.
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             The integration and management of AAM program data are typically supported
by a central, integrated database system. The design and structure of the supporting software
should be compatible with program objectives and, at a minimum, should offer:

             •      Storage for all required data;
             •      Interfaces for accessing or entering field and laboratory information;
             •      The ability to retrieve data in the form of standard or user-specified
                    reports.

In most cases, the database system must be developed or modified from an existing system to
support  the unique needs of the program.  Table 5-1 summarizes the topics of concern when
developing databases for AAM programs.

5.2          DATA ACQUISITION

             Figure 5-1 depicts a data flow diagram for a typical AAM program.  Field-
based data acquisition systems and sampling methods are predefined in the QAPP or
sampling plan.  In a well-structured data acquisition environment, automatic interfaces with
the central database are present to reduce data handling costs. In current AAM programs,
monitoring systems may be linked to the central database via modem or another electronic
interface.  Sampling information and analytical results are often keyed into the system from
hard-copy data sheets.  In some cases, raw or analytical data may also be transferred via
diskette or other electronic medium, and the data are electronically imported into the central
database.

             The efficiency of the data acquisition process depends directly on the
compatibility of sample numbering schemes, data element  definitions,  data formats, and units
of measure for each priority  parameter. Standardization of these  items facilitates data
transfer, reduces data acquisition costs, simplifies data reduction and validation activities, and
ensures  the defensibility of the final reports.
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         Table 5-1.
Database Development Issues
lIC-iE^Pri^ii
Data Volume
Data Structures
Data Relationships/
Indexes
Data Redundancy
Data Formatting
Meaning of Fields
Documentation
;;%$$^e Results
Data volume
exceeds expectations
Incorrect design
Design not
optimized for
program data
Existence of
duplicate data
Data inconsistency
Fields incorrectly
defined or having
multiple definitions
Inadequate/poorly
maintained
Polsnfial-lH^iils
• unacceptable response times
• excessive resource utilization (update time, disk space)
• inflexibility
• poor performance
• increased storage
• update problems
• false interferences
• inefficient updates
• complex reporting
• poor interactive response
• inefficient data retrieval
• error-phone reports
• complex updates
• increased data volume
• increased maintenance costs
• impedes data transfer
• inefficient data comparison/manipulation
• error-phone reports
• loss of data integrity
• incorrect interferences
• programming errors
• poor program communication
• vulnerable to staff turnover
• miscommunication between staff
• programming errors
• expensive maintenance
            5-5

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Validation Steps
    Level I
    Level H
   Level m
             Data Flow
                            Data Acquisition
Reduction
Validation
                            Central Database
                  Reduction
                          Validation
                             Data Reporting
               QA/QC Procedures
                                        Calibration Maintenance
                                       Inspection Sampling Plan
                                                            Data Management
                                                                 QA/QC
    Figure 5-1.  Simplified Data Flow Diagram for AAM Programs at Superfund Sites.
                                      5-6

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5.3          DATA REDUCTION

             Data reduction is the manipulation of raw data, by averaging, integration, and
statistical methods, to create intermediate products for analytical applications and assessment
reporting. Each phase of data reduction is accompanied by a parallel data validation step to
ensure the early detection and resolution of data anomalies.

             In AAM programs, data reduction is an ongoing process that begins with the
field instrumentation and supporting data processors that automatically average measurement
parameters for specified  time intervals.  Laboratory methods for analyzing samples generate
individual sample data (e.g., the integration of a chromatographic peak) by manual analysis
or the use of supporting  software tools. These type of data reduction activities are validated
by QA/QC activities for instrument calibration and maintenance and program-specified
laboratory methodologies (see Figure 5-1).

              Loading field and laboratory data into the central database may require
additional data treatment to meet database requirements for units, data formats, etc.  Data
compatibility issues  can be resolved with preprogrammed conversion routines.  These
activities begin what is typically viewed as the 'data management' portion of the project and
are integrated with field  and lab QA/QC activities specified for the program, as shown in
Figure 5-1.

             Once  loaded into the central database, raw data should be stored for the life  of
the program. For long-term AAM programs,  raw data may be periodically archived for
database maintenance. In all cases, the maintenance of raw data files should be supported by
regular backup procedures.  These data,  once validated, are further reduced to create data
summaries (intermediate data) and final reports.
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             Data reduction procedures involve the application of standard statistical
methods for averaging, establishing minimum and maximum values, generating standard
deviations, etc.  Statistical calculations for determining ambient concentrations of air
pollutants are complicated by the limitations of existing measurement methods,  which operate
within detection limits above those of actual concentration values.  For samples characterized
as "not detected" the conventional practice is to substitute such value with a value one-half
the detection limit.  This may,  however, result in erroneous or unacceptably high estimates
of risk if a number of toxic or  carcinogenic compounds are among the target analytes. This
effect is exacerbated if the number of "not detected" values make up a significant portion of
the data set.

5.4          DATA VALIDATION

             Data validation is the systematic review of measurement data for outlier
identification or error detection.  Suspect values are deleted or flagged by manual or
automated data validation methods.  The term  "validation" typically  implies those activities
performed upon collected data.  Validation is distinguished  from the quality control activities
that prevent bad data from being collected.

             There are three general levels of validation in A AM programs:

             •      Level I validation — involves validity  checks of raw monitoring data;
             •      Level n validation ~ the independent  evaluation of analytical results by
                    a qualified person; and
             •      Level HI ~ a review to identify data outliers and anomalies.

             Level I validation activities involve reviewing chain-of-custody forms to detect
any problems with sampling equipment, canister leakage, etc. that might have contributed to
nonstandard sampling intervals, insufficient sample volume, or other problems that  may
negate the sampling event or create questionable results.  For monitoring systems, validation
of the raw data is inherent in quality control procedures for calibration and maintenance.
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              Level II validations verify preliminary compound identifications, confirm that
analytical systems are operating within acceptance criteria, and identify anomalies associated
with any analysis that might undermine compound results. These activities are performed by
a qualified chemist or air specialist and are designed to ensure that the data criteria for each
analyte are met. Suspect data are deleted or flagged for resolution; measurement bias,
system contamination,  or the lack of reproducibility of measurement data may be reasons to
judge the data invalid.

              In Level III validation, the data are screened for outliers, concentrations
inconsistent with historical measurement trends, or measurements that are incompatible with
prevailing wind conditions.  The validation activities should attempt to correlate any data
anomalies with treatment process conditions or on-site activities.  Level III validation
typically occurs with data stored and reduced in the central database system and is supported
by manual review or automated data validation routines.

              Acceptance Criteria

              The process of data validation ensures that the DQOs for each measured
parameter are met.  A key acceptance criterion is the data recovery rate, which expresses the
number of valid observations as a percentage of total possible observations.  Data recovery
rates are typically 80% for air quality data and 90%  for meteorological data, based on 1990
EPA recovery standards established for permitting purposes.

              Section  1.4.17.2.1 of Volume I of the Quality Assurance Handbook for Air
Pollution Measurement Systems,21 contains detailed  information on data validation and
screening procedures.  In this document, data validation procedures are subdivided into four
general categories:

              •     Routine check and review procedures;
              •     Tests for internal consistency of data;
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                    Tests of consistency of data sets with previously analyzed data sets
                    (historical or temporal comparisons);

                    Tests of consistency with data sets collected at the same time or under
                    similar conditions.
             Table 5-2 summarizes the specific criteria for screening meteorological data,

extracted from "On-Site Meteorological Program Guidance for Regulatory Modeling

Applications,".28


             Air monitoring data validation should include evaluating collocated station

results and audit results to determine data precision and accuracy, as described below.


             •      The percent difference between the air concentrations measured at
                    collocated samplers is:

                                 d  =  Yi-Xi  x 100
where:
d,
the percent difference between the concentration of air toxic
constituents Yj measured by the collocated monitoring station
and the concentration of air toxic constituent X;, measured by
the monitoring station reporting the air quality.
                    The average percent difference dj for the monitoring period is:


                                     d. = 1  E  d
                                      j   n  ,-=i   l
where:
             n
             percent difference defined above, and
             number of samples collected during the monitoring period.
                    The standard deviation S,- for the percent differences is:
1
n-1
n 2
S d f
1
n
n f
S dj
/ .
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                                           Table 5-2.
                  Suggested Meteorological Data Screening Criteria*
  Meteorological
    Variable
                                Screening Criteria1
 Wind Speed
• Is less than zero or greater than 25 m/s;
• Does not vary by more than 0.1 m/s for 3 consecutive hours; and
• Does not vary by more than 0.5 m/s for 12 consecutive hours.
 Wind Direction
  Is less than zero or greater than 360ฐ;
  Does not vary by more than 1 ฐ for more than three consecutive hours; and
  Does not vary by more than 10ฐ for 18 consecutive hours.
 Temperature
  Is greater than the local record high;
  Is less than the local record low; (The above limits could be applied on a monthly basis.)
  Is greater than a 5ฐ change from the previous hour,
  Does not vary by more than 0.5ฐC for 12 consecutive hours.
 Temperature
 Difference
• Is greater than 0.1 ฐC/m during the daytime;
• Is less than -0.1ฐC/m during the nighttime; and
• Is greater than 5.0ฐC/m or less than -3.0ฐC/m.
 Dew Point
 Temperature
• Is greater than the ambient temperature for the given time period;
• Is greater than a 5ฐC change for the previous hour;
• Does not vary by more than 0.5ฐC for 12 consecutive hours; and
• Equals the ambient temperature for 12 consecutive hours.
 Precipitation
• Is greater than 25 mm in one hour;
• Is greater than 100 mm in 24-hours; and
• Is less than 50 mm in three months.
  (The above values can be adjusted base on local climate.)
 Pressure
• Is greater than 1,060 mb (sea level);
• Is less than 940 mb (sea level); and
  (The above values can be adjusted for elevations other than sea level.)
• Change by more than 6 mb in three hours.
'Some criteria may have to be changed for a given location.

SOURCE:  Reference 28
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                    The 95-percent probability limits for precision are:
                                                              S,
                    Upper 95 % Probability Limit - ^ + 1.96
                                                             v/2
                                                             S,
                     Lower 95% Probability Limit - d - 1.96 -J-
                    The accuracy is calculated for the monitoring period by calculating the
                    percent difference dj between the indicated parameter from the audit
                    (concentration, flow rate, etc.) and the known parameter, as follows:
                                 d  -  i-li x 100
where:       Yt     =     monitor's indicated parameter from the i* audit check; and
             X;     =     known parameter used for the r* audit check.

             These results should then be compared with the QA/QC criteria stipulated in
the monitoring plan to determine the validity of the data.

             Resolution of Data Concerns

             To support the resolution of data anomalies, records should be maintained to
track raw data as it is reduced and validated to create intermediate data sets and reporting
summaries.  At any stage in this process, data flags may be appended to a measurement.
The specific methods for flagging data may be manual or automatic;  they depend on the
program design and the sophistication of supporting software tools. Flags appended to data
during validation may be reclassified or removed after the specific issues for that data point
have been resolved in accordance with the corrective action procedures established for the
program.
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5.5          DATA REPORTING

             Meteorological and air monitoring data summaries are prepared from validated
database files. These reports summarize data for airborne pollutant concentrations at sample
locations and facilitate the determination of exposure potentials.

             Meteorological Pafo Summaries

             Meteorological data summaries should contain at least the following
information:

             •     Hourly averages for all meteorological parameters for the sampling
                   period;
             •     Summary wind roses, including daytime and nighttime wind roses (for
                   coastal or complex terrains);
             •     Data recovery summaries for each measured parameter;
             •     Summary of dispersion conditions for the sampling period;
             •     Tabular summaries of means and extremes for temperature  and other
                   parameters.

             It is recommended that sequential hourly data be derived for the summary
reports to keep data volumes down and avoid undue complications in evaluating the data.  A
one-hour time frame is enough to account for temporal variabilities  in the measured
parameters.  For multistation sites, it may be useful to  format the data in adjacent columns to
facilitate manual comparisons. Data recovery target standards are 90% for meteorological
parameters and are an initial reflection of data completeness and representativeness.

             Statistical summaries by month, year, season, and for the monitoring period
can be derived from the meteorological data summaries. Figure 5-2 depicts a useful format
for representing wind rose summary data. For sites with diurnal wind patterns, separate wind
rose summaries for daytime and nightime conditions are recommended.
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                        WIND ROSE
N
        7.0
                                               Wind Speed
                                                 (mph)
0 PcL
         SJJPct
                  lOJJPct
                                           Pet Calms - 4.68
        December 1,  1991  -  November 30,  1992
              Figure 5-2.  Sample Wind Rose Diagram
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             Air Data Summaries

             Air data summaries list the concentrations of all monitored constituents
by station and monitoring/sampling period.  The summarized data should include method
detection limits, undetected compounds, and upwind/downwind exposure classifications.
Operational data for monitoring stations, such as sample flow rates, station numbers, and
sampling duration should also be reported.

             For each measured constituent at each monitoring station, the following  data
should be presented:

             •     Total number of samples;
             •     Data recoveries (target 80%);
             •     Mean, median, minimum, and maximum concentrations;
             •     Detection limits;
             •     Frequency above and below detection limits;
             •     Number of exceedances for QAPP-selected values; and
             •     Upwind and downwind exposure summaries.

             The standard unit of measure for reporting air concentrations is micrograms
per cubic meter, or parts per billion (ppb).  It is also useful to include raw data used to
derive concentration values, such as the duration of sampling event (unit time); the volume of
sampled air (cubic meters); the temperature (degrees Fahrenheit); the pressure (mm Hg); and
constituent content in the sample (micrograms).  Upwind and downwind summaries, such as
those shown in Figures 5-3 and 5-4, should be included for each monitoring station to
support data interpretation.  Upwind conditions are applied to background characterization,
and concentrations measured downwind are applied to source-specific exposure assessments.

             Further analyses  or statistical treatment of these basic data are carried out to
derive information for sample event and results summaries; relationships between sample
events, unit operating efficiencies and meteorological conditions; and comparisons with
background levels and other air emission sources.  The air monitoring data summary
typically includes a narrative discussion of sampling results and conclusions about the  quality
of the data set according to established data quality objectives.

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6H
                      i i  i  i i  i i  i  I i  i i  i
                                  Parent Downwind (%)
 Figure 5-3.   Regression Equation of Concentration versus Percent Downwind Overlayed
             with 95% Confidence intervals for the Mean
                                        5-16

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             Reports

             Data summaries are further reduced and validated to present statistical reports
for the monitoring period and for monthly, seasonal, and annual ambient conditions. The
information in final reports is used to support data interpretation and program decision-
making.  Concentration means and extremes, exceedances of health and safety criteria and
other selected compliance thresholds, and data quality summaries are typically included in
annual or final reports. These reports should be reviewed by knowledgeable individuals to
validate the summary conclusions and to ensure that the data are accurately represented to
avoid the possible misinterpretation of reported results

             Data from AAM reports are often used to augment and validate air dispersion
models, which aide in the  interpretation and extrapolation of ambient concentration  data to
unmonitored on and off site locations. These data can be applied to health risk assessment
models to determine the risk of exposure of site personnel and the surrounding community.

5.6          DATA USAGE

             Ambient air monitoring data may be generated from a variety of sampling
locations at Superfund sites, including personal (IH) samplers, and samplers situated at the
work zone, site perimeter  (fenceline), and off-site near sensitive receptors.   These  data may
have several uses.  The most common usage is to compare the measured air concentrations
with short- or long-term action levels. Comparisons with short-term action levels can be
done directly with individual data points. Any exceedance of short-term action levels may
indicate that adverse exposures have occurred.  Comparisons with long-term action  levels can
be done with individual data points,  but  more meaningful comparisons are made using data
averages developed from weeks or months of data. Any exceedances may not necessarily
indicate a problem, because long-term action levels typically are based on lifetime exposures.
If the data trends  show a consistent pattern of exceeding the long-term action levels, then
some remedial action may be warranted.
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             Ambient air monitoring data frequently are used in conjunction with dispersion
modeling results.  The AAM data can be used to validate the model outputs for the specific
site of interest.  This is done by comparing measured ambient air concentrations to the
concentrations predicted by an atmospheric dispersion model that uses the actual
meteorological conditions present during the monitoring. Dispersion  models are inherently
conservative, so the model output will usually overpredict ambient concentrations.  The
degree to which the model over (or under) predicts will depend on  site-specific factors.  The
degree of overprediction observed for the short-term dispersion modeling may be used, with
limitations, as a correction factor when  interpreting long-term dispersion modeling results.
All of the above discussion, of course, assumes that the source term (i.e., emission rate) for
the site is known.

             AAM data can, under ideal conditions, be used to generate a source term for a
site.  This is done by  modelling a unit emission rate (i.e.,  1 g/sec)  and ratioing the estimated
downwind concentrations to the actual measured concentrations (measured/estimated).  This
ratio can then multiplied by the unit emission rate to yield  a source term.  If multiple sets of
AAM data versus model output show a consistent ratio, then the estimated source term can
be assumed  to have less uncertainty than a ratio derived  from a single data set.  It may be
difficult or impossible to estimate a source term using AAM data if multiple emission  sources
exist  at the site, if the emission rate varies over timeframes that are shorter than the AAM
duration, or if there are upwind emission sources.

             AAM data obtained from OPM systems usually are in  path-weighted units of
ppm*meter or ug/m2 and, therefore, are not directly comparable to typical action levels or
health standards that are given in units of ug/m3 or ppm. This does not mean that the OPM
data are not usable, only that the OPM data may require further data reduction before
comparisons can be made.  The most common data treatment is to  divide the OPM data by
pathlength to yield a path-averaged concentration (in ppm or ug/m3) along the path that is
monitored.  This average concentration is  analogous to an  average  obtained from a line of
point samplers.  The  OPM data, however, can not be used directly to determine if the mass
of emissions was equally distributed along the beam path or if there were localized "hot
                                          5-18

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spots" of relatively high air concentrations.  Such information can be obtained only if
multiple OPM configurations are used; for example, different path lengths could be used and
the measured concentrations compared to identify when contributions from any hot spots are
observed.

             OPM data also can be used to back-calculate a source term using one of
several methods.  If the emission plume is fully contained within the beam path, one need
only determine the vertical dispersion to calculate the source term (see Reference 5).  The
vertical dispersion can be evaluated using a vertical array of point samplers, or it may be
extrapolated from measurement of the wind direction standard deviation (sigma  theta) by
using Pasquill-Gifford stability classes and the associated dispersion curves. A second
method is to use a tracer gas on the site. The tracer gas is released at a controlled rate.  The
path-weighted concentration of the tracer is measured at a downwind line.  The  simplest
method of calculating a source term using a tracer gas is to ratio the measured concentrations
of the tracer gas and the compound of interest and use this as a multiplier to the known
emission rate of the tracer gas to obtain the emission rate of the compound of interest. This
approach is limited by the degree to which the tracer release approximates the emission
source and, in some cases, by differences in atmospheric transport between the tracer gas and
the compound(s) of interest.
                                         5-19

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                                     SECTION 6
                       ESTIMATION OF PROGRAM COSTS

             The costs associated with conducting ambient air monitoring (AAM) at
Superfund sites will depend on a number of issues, including:

             •      Objectives of the monitoring program;
             •      Target analyte list;
             •      Frequency of monitoring; and
             •      Duration of the AAM program.

             The objectives of the AAM program will dictate the costs.  Usually,
monitoring objectives will involve some combination of documenting community exposure to
ensure the protection  of the surrounding community and documenting the exposure of on-site
workers (industrial hygiene).  Since these two primary objectives may involve significant
differences in the sampling approach taken and in the type of equipment,  as well as
differences in analytical methodology, the differences in costs can be substantial. The air
action levels (AALs)  set for community exposure are normally much lower than equivalent
AALs for on-site workers,  since on-site workers can use personal protective equipment.
Therefore, the evaluation of community exposure generally requires more sensitive
monitoring and analytical methods, thus increasing the costs of this type of monitoring.

             The number  and type of target analytes selected will influence the types of
analytical methods used and the detection limits that must be achieved; therefore, they may
have a significant impact on program costs. Depending on the analyte and associated
analytical method, analytical costs may run  from as little as $25  for the determination of lead
on a high-volume filter to over $2000 per PUF sample for dioxins and furans.  Savings in
analytical and data management costs can be achieved by selecting an appropriate subset of
the compounds present at the site  as target analytes, instead of monitoring for an extensive
list of compounds.

             The frequency  of sample collection will have a significant effect on program
costs.  For long-term programs, these costs may easily out-weigh all other monitoring costs,

                                        6-1

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including capital equipment and operation costs.  Depending on the estimated duration of the
program, it may be more cost-effective to use automated real-time monitoring or to set-up an
on-site laboratory  than to use a more traditional approach of sending discrete samples to an
off-site analytical laboratory. Data turnaround and laboratory responsiveness should also be
factors in such a decision.

             The duration of the monitoring program may influence the selection or
implementation of sampling and analytical methods. For example, a more labor-intensive
sampling approach might be considered for a three-week program than for a two-year
program.  In general, the longer the program the more cost-effective automated real-time
monitoring becomes.

             The cost estimates given in this section are based on the assumption that all
capital equipment  for a given application would be acquired for the program, regardless of
the sampling duration. Although some ambient equipment can be leased (especially portable
real-time monitors), many  monitors are not readily available or, if they are, they have short
recovery costs, such as 3-6 months.

             Tables 6-1 through 6-3 present the estimated costs  of an AAM program for
volatile, semi-volatile, and inorganic compounds. Whenever possible,  costs are provided on
a per-unit or per-sample basis, both for equipment and analytical work. Other expenses,
such as labor requirements for network operation and data management and reporting are
given as estimated number of hours.  The unit cost for labor and the actual labor hours
themselves may vary significantly, depending on the level of personnel involved and  the
charge rates of the individuals or organizations actually performing the work. Therefore,
these estimates are, at best, general guidelines.

             Program costs will of course vary considerably depending on the area  of the
country, the availability  of equipment manufacturers and suppliers, analytical laboratories and
contractors.  These estimates should  only be used to try to estimate "ballpark" costs  that may
be associated with the start-up and execution of an ambient monitoring program.  Of course,
                                         6-2

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RPMs/OSCs or their designates should get detailed price quotes to determine actual program
costs before initiating or committing to an ambient monitoring program.

              Site preparation costs also can vary considerably from site to site. These costs
will depend on the distances involved and  the complexity of providing electrical service to
the monitoring location, on whether, and to what extent, site security needs to be provided
for each monitoring location, and on what other types of preparation the site needs.
Normally, the acquisition of electrical power will be the most costly item associated with site
preparation; therefore, if utility service is readily available, site preparation costs should be
in the low range of the estimates given.

              The costs of real-time analyzers can vary over more than an order of
magnitude.  The typical costs of selected categories of real-time monitoring equipment are
given in Table 6-4.
                                          6-3

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                         Table 6-1
Estimated Costs for Implementing a VOC Air Monitoring Program
Cost Type
Capital Cost
Start-up Costs
Operational Costs
Data Management
and Reporting
Cost Elements
SJnit Costs ($)
Option 1 - Time-integrated whole-air canister sampling
Canister samplers
6-liter SUMMAฎ Canisters
Packing crates for shipping canisters
4000-12,000
500-800
100-300
Option 2 - Time-integrated sorbent tube sampling
Sorbent tube samplers
Sorbent tubes (per box)
500-10,000
50-250
Option 3 - Automated fixed-location continuous analyzers
Analytical equipment
Climate controlled shelters
Spare parts (per location/station)
2,000-150,000
8,000-15,000
2,000-5,000
Option 4 - Remote sensing systems (FI1R/UV-DOAS)
Analytical Equipment
Climate Controlled Shelter
Develop Monitoring Plan
Equipment set-up/installation - includes utilities,
site pad, manpower, etc. (per site)
Operator Training
Option 1 - SUMMAฎ canister analysis
Option 2 - Sorbent tube analysis
Option 3 - Calibration supplies/expendables
Quarterly field QA/QC audits (options 1, 2, & 3)
Laboratory audit (options 1 & 2)
Data validation (per site/month)
Database processing and maintenance (per
site/month)
Data interpretation and reporting (per site/month)
> 100,000
8,000-15,000
200-400 hours
2,000-15,000
80-160 hours
350-600
80-200
3,000-5,000
4,000-5,000
1,500-2,500
20-40 hours
20-40 hours
40-80 hours
                            6-4

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                         Table 6-2
Estimated Costs for Implementing a SVOC Air Monitoring Program
, Cbstl^pe ;
Capital Costs
Start-up Costs
Operational Costs
Data Management
and Reporting
	 f* \ Cost Elements
General Metal Works, PS-1 high-volume sampler
PS-1 calibration kit
Spare parts (per sampler)
Glass Sampling Cartridges (need approximately
6/sampler)
Monitoring Plan Development
Equipment set-up/installation - includes utilities,
site preparation (if required), and manpower (per
site)
Operator Training
Sampling media (including PUFs, sorbents, and
filters) per cartridge includes preparation
Analysis Costs (PCBs by GC/ECD)
Analysis Costs (PCBs by GC/MS)
Analysis costs (PCDDs/PCDFs by HRGC/HRMS)
Analysis costs (PCDDs/PCDFs by medium
resolution GC/MS)
Analysis costs (organochloride pesticides by BCD)
Analysis costs (organochloride pesticides by
GC/MS)
Analysis Costs (PAHs by HPLC)
Analysis Costs (PAHs by GC/MS)
Quarterly field QA/QC audit
Quarterly laboratory audit
Data validation (per site)
Database processing and maintenance (per
site/month)
Data interpretation and reporting (per site/month)
Unit Casts ($)
2000-2500
700-800
150-250
75-100
200-400 hours
1,000-5,000
40-80 hours
100-250
150-250
250-500
1,800-2,400
800-1,00
150-250
250-500
150-250
250-500
4,000-5,000
1,500-2,500
20-40 hours
20-40 hours
40-80 hours
                            6-5

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                     Table 6-3
Estimated Costs for Implementing an Inorganic Compound
               Air Monitoring Program
Costl^ype
Capital Costs
Start-up Costs
Operational Costs
Data Management
and Reporting
Cost Elements
High-volume air sampler (TSP)
High-volume PMj0 air sampler
Spare parts (per sampler)
Low/medium-volume air samplers
Hardware for impinger sampling (CN~)
Monitoring Plan Development
Equipment set-up/installation - includes utilities,
site preparation (if required), and manpower (per
site)
Operator Training
Sampling media - quartz or glass fiber filters
Filter preparation/weighing
Filter digestion/analysis preparation
Analysis Costs - ICP-AES analysis - depending on
number of elements per scan
Analysis Costs - AAS - per element
Analysis costs - GFAAS - per element
Analysis costs cyanide
Quarterly field QA/QC audit
Quarterly laboratory audit
Data validation (per site)
Database processing and maintenance (per
site/month)
Data interpretation and reporting (per site/month)
Unit Costs ($)
1,800-2,500
4,000-4,500
150-250
2,000-4,000
500-1000
200-400 hours
1,000-5,000
40-80 hours
1-5
0.25-0.50 hours
20-40
45-250
20-40
20-40
40-100
4,000-5,000
1,500-2,500
20-40 hours
20-40 hours
40-80 hours
                         6-6

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                                 Table 6-4.
    Summary of Information for Selected Classes of Real-Time Instruments
5 ••• •• Measurement System
Electrochemical
Total Hydrocarbon
Flame lonization Detector
Photoionization Detector
Thermal Detector
Solid State
Colorimetric
Solid
Paper Tape
Liquid
Spectrophotometric
Nondispersive Infrared
Optical Remote Systems
Gas Chromatograph
Gas Chromatograph/Mass Spectrometer
Particulate
Optical
Radiometric
Gases Measured
T, C, O2, THC, H2S, CO
THC, VOC, SVOC
VOC, SVOC
THC, H2
THC, T, C
VOC, SVOC, THC, T, C
02, T, C
T, Formaldehyde
VOC, SVOC, T, HC
VOC, SVOC, THC, T, C
VOC, SVOC, THC, T, C
VOC, SVOC, THC, T, C
TSP
PM10
Topical Cost
$1,500
$4,000 - $8,000
$5,000
$1,500
$2,000
$400
$5,000 - $10,000
$6,000
$7,500
>$100,000
$14,000
> $75, 000
$8,000
$14,000
KEY:
      C     = Combustibles                      SVOC
      CO   = Carbon Monoxide                  T
      HC   = Hydrocarbons                     THC
      H2S   = Hydrogen Sulfide                  TSP
      O2    = Oxygen                           VOC
      PM10  = Particles < 10 microns diameter
= Semi-Volatile Organic Carbon
= Toxic Compounds
= Total Hydrocarbons
= Total Suspended Particulates
= Volatile Organic Compounds
                                     6-7

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                                   SECTION 7
                                 REFERENCES

1.          Eklund, B.  Procedures for Conducting Air Pathway Analyses for Superfund
            Activities, Interim Final Document: Volume 1 - Overview of Air Pathway
            Assessments for Superfund Sites. EPA-450/1-89-00la. February 1993.

2.          Schmidt, C., et al.  Procedures for Conducting Air Pathway Analyses for
            Superfund Activities, Interim Final Document: Volume 2  - Estimation of
            Baseline Air Emissions at Superfund Sites (Revised). EPA-450/l-89-002a
            (NTIS PB90-270588). August 1990.

3.          Eklund, B., et al.  Procedures for Conducting Air Pathway Analyses for
            Superfund Activities, Interim Final Document: Volume 3  - Estimation of Air
            Emissions From Clean-up  Activities at Superfund Sites.  EPA-450/1-89-003
            (NTIS PB89-180061/AS).  January 1989.

4.          Stoner, R.,  et al. Procedures for Conducting Air Pathway Analyses for
            Superfund Activities, Interim Final Document: Volume 4  - Procedures for
            Dispersion Modeling and  Air Monitoring for Superfund Air Pathway Analyses.
            EPA-450/1-89-004 (NTIS PB90-113382/AS).  July 1989.

5.          Draves, J. and B. Eklund. Applicability of Open Path Monitors for Superfund
            Site Cleanup.  EPA-451/R-92-001 (NTIS PB93-138154).  May 1992.

6.          Salmons, C., F. Smith, and M. Messner.  Guidance on Applying the Data
            Quality Objectives For Ambient Air Monitoring Around Superfund Sites
            (Stages I & II). EPA-450/4-89-015 (NTIS PB90-204603/AS).  August 1989.

7.          Smith, F., C. Salmons, M. Messner, and R. Shores. Guidance on Applying
            the Data Quality Objectives For Ambient Air Monitoring  Around Superfund
            Sites (Stage III).  EPA-450/4-90-005 (NTIS PB90-20461 I/AS).  March 1990.

8.          U.S. EPA Removal Program Representative Sampling Guidance; Volume II -
            Air. Draft  Report.

9.          U.S. EPA.  Ambient Monitoring Guidelines for Prevention of Significant
            Deterioration (PSD).  EPA 450/4-97-007.  May 1987.

10.         U.S. EPA.  Compendium of Methods for Determination of Toxic Organic
            Compounds in Air. EPA/600/4-89-017.  June 1988.

11.         Ranum, D.  and B. Eklund. Compilation of Information on Real-Time Air
            Monitors For Use at Superfund Sites. Draft Report to Mark Hansen of EPA
            Region VI.  January 1993.
                                       7-1

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12.          NIOSH Manual of Analytical Methods, 3rd Edition, P.M. Eller, Editor.  U.S.
            Department of Health and Human Services, National Institute of Occupational
            Safety and Health, Cincinnati, Ohio.  February 1984.

13.          Oliver, K.D., J.D. Pleil, and W.A. McClenny.  "Sample Integrity of Trace
            Level Volatile Organic Compounds in Ambient Air Stored in SUMMAฎ
            Polished Canisters."  Atmospheric Environment, Vol. 20.  1986.

14.          Brymer, D.A., L.D. Ogle, W.L. Crow, M.J. Carlo, and L.A. Bendele.
            "Storage Stability of Ambient Level Volatile Organics in Stainless Steel
            Canisters." Proceedings of the 1988 APCA Conference.

15.          Cox,  R.D.  "Sample Collection and Analytical Techniques for Volatile
            Organics in Air."  Proceedings of the 1988 APCA Conference.

16.          Spellicy, R.L., W.L. Crow, J.A. Draves, W.H. Buchholtz, and W.H.  Herget.
            "Spectroscopic Remote Sensing:  Addressing Requirements of the Clean Air
            Act."  Spectroscopy  6, 24 (1991).

17.          Draves, J. (Radian).   Personal communication.  1993.

18.          Fairless, BJ. and J.L. Hudson.   "Monitoring Ambient Air for Dioxins."
            Proceedings of the 1988 EPA/APCA  International Symposium on the
            Measurement of Toxic and Related Air Pollutants.

19.          40 CFR, Part 50, Appendix  B.

20.          40 CFR, Part 50, Appendix  J.

21.          U.S.  EPA. Quality  Assurance Handbook for Air Pollution Measurement
            Systems; Volume I - Principles.  EPA-600/9-76-005.  March 1976.

22.          U.S.  EPA. Quality  Assurance Handbook for Air Pollution Measurement
            Systems; Volume II  - Ambient Air Specific Methods.  EPA-600/4-77-027a.
            May  1977.

23.          U.S.  EPA. Quality  Assurance Handbook for Air Pollution Measurement
            Systems; Volume III - Stationary Source Specific Methods.  EPA-600/4-77-
            027b. August 1977.

24.          U.S.  EPA.  Quality  Assurance Handbook for Air Pollution Measurement
            Systems; Volume IV - Meteorological Measurements.  EPA-600/4-82-060.
            February 1983.

25.          U.S.  EPA.  Quality  Assurance Handbook for Air Pollution Measurement
            Systems; Volume V - Precipitation Measurement Systems.  EPA-600/4-82-
            042a. March 1983.

                                        7-2

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26.          U.S. EPA. Technical Assistance Document for Sampling and Analysis of
             Toxic Organic Compounds in Ambient Air.  EPA-600/4-83-027. June 1983.

27.          U.S. EPA. Preparing Perfect Project Plans.  EPA-600/9-89-087. October
             1989.

28.          U.S. EPA. Interim Guidelines and Specifications for Preparing Quality
             Assurance Project Plans.  EPA-600/4-83-004. December 1980.

29.          Pritchett, T.  Personal Communication to Bart Eklund of Radian Corporation.
             February 1993.

30.          Code of Federal Regulations. Quality Assurance Requirements for Prevention
             of Significant Deterioration (PSD) Air Monitoring. Part 58, Appendix B.
                                        7-3

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          APPENDIX A




BIBLIOGRAPHY OF NTGS DOCUMENTS

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                                APPENDIX A
                 BIBLIOGRAPHY OF NTGS DOCUMENTS

ASF-1      Eklund, B.  Procedures for Conducting Air Pathway Analyses for Superfund
           Activities, Interim Final Document: Volume 1 - Overview of Air Pathway
           Assessments for Superfund Sites (Revised).  EPA-450/l-89-001a. February
           1993.
ASF-2      Schmidt, C., et al. Procedures for Conducting Air Pathway Analyses for
           Superfund Activities, Interim Final Document: Volume 2 - Estimation of
           Baseline Air Emissions at  Superfund Sites (Revised).  EPA-450/l-89-002a
           (NTIS PB90-270588).  August 1990.
ASF-3      Eklund, B., et al. Procedures for Conducting Air Pathway Analyses for
           Superfund Activities, Interim Final Document: Volume 3 - Estimation of Air
           Emissions From Clean-up Activities at Superfund Sites.  EPA-450/1-89-003
           (NTIS PB89-180061/AS).  January 1989.
ASF-4      Hendler, A., et al. Procedures for Conducting Air Pathway Analyses for
           Superfund Activities, Interim Final Document:  Volume 4 - Guidance for
           Ambient Air Monitoring at Superfund Sites. April 1993.
ASF-5      U.S. EPA.  Procedures for Conducting Air Pathway Assessments for Superfund
           Sites, Interim Final Document: Volume 5 - Dispersion Modeling. [Proposed
           document].
ASF-6      TRC Environmental Consultants.  A Workbook of Screening Techniques For
           Assessing Impacts of Toxic Air Pollutants.  EPA-450/4-88-009 (NTIS PB89-
           134340).  September 1988.
ASF-7      Salmons, C., F. Smith, and M. Messner.  Guidance on  Applying the Data
           Quality Objectives For Ambient Air Monitoring Around Superfund Sites (Stages
           I & II).  EPA-450/4-89-015 (NTIS PB90-204603/AS). August 1989.
ASF-8      Pacific Environmental  Services. Soil Vapor Extraction VOC Control
           Technology Assessment.   EPA-450/4-89-017 (NTIS PB90-216995).  September
           1989.
ASF-9      TRC Environmental Consultants.  Review and Evaluation of Area Source
           Dispersion Algorithms for Emission Sources at Superfund Sites. EPA-450/4-
           89-020 (NTIS  PB90-142753). November 1989.
ASF-10    Letkeman, J.  Superfund Air Pathway Analysis Review  Criteria Checklists.
           EPA-450/1-90-001 (NTIS  PB90-1825447AS). January 1990.
ASF-11    Smith, F., C.  Salmons, M. Messner, and R. Shores.  Guidance on Applying
           the Data Quality Objectives For Ambient Air Monitoring Around Superfund
           Sites (Stage III). EPA-450/4-90-005 (NTIS PB90-20461 I/AS).  March 1990.
ASF-12    Saunders, G.  Comparisons of Air Stripper Simulations  and Field Performance
           Data. EPA-450/1-90-002 (NTIS PB90-207317). March 1990.

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ASF-13     Damle, A.S., and T.N. Rogers.  Air/Superfund National Technical Guidance
           Study Series:  Air Stripper Design Manual. EPA-450/1-90-003 (NTIS PB91-
           125997).  May 1990.
ASF-14     Saunders, G.  Development of Example Procedures for Evaluating the Air
           Impacts of Soil Excavation Associated with Superfimd Remedial Actions.  EPA-
           450/4-90-014 (NTIS PB90-255662/AS). July 1990.
ASF-15     Paul, R.  Contingency Plans at Superfund Sites Using Air Monitoring.  EPA-
           450/1-90-005 (NTIS PB91-102129).  September 1990.
ASF-16     Stroupe, K., S. Boone, and C. Thames. User's Guide to TSCREEN - A  Model
           For Screening Toxic Air Pollutant Concentrations.  EPA-450/4-90-013 (NTIS
           PB91-141820). December 1990.
ASF-17     Winges, K.D.. User's Guide for the Fugitive Dust Model (FDM)(Revised),
           User's Instructions. EPA-910/9-88-202R (NTIS PB90-215203, PB90-502410).
           January 1991.
ASF-18     Thompson,  P., A.  Ingles, and B. Eklund.  Emission Factors For Superfund
           Remediation Technologies.  EPA-450/1-91-001 (NTIS PB91-190-975),  March
           1991.
ASF-19     Eklund, B., C. Petrinec, D. Ranum, and L. Hewlett.  Database of Emission
           Rate Measurement Projects -Draft Technical Note. EPA-450/1-91-003 (NTIS
           PB91-222059). June 1991.
ASF-20     Eklund, B., S. Smith, and M. Hunt. Estimation of Air Impacts For Air
           Stripping of Contaminated Water.  EPA-450/1-91-002 (NTIS PB91-211888),
           May 1991 (Revised August 1991).
ASF-21     Mann, C. and J. Carroll.  Guideline For Predictive Baseline Emissions
           Estimation Procedures For Superfund Sites. EPA-450/1-92-002 (NTIS PB92-
           171909).  January  1992.
ASF-22     Eklund, B., S. Smith, P. Thompson, and A. Malik.  Estimation of Air Impacts
           For Soil Vapor Extraction (SVE) Systems. EPA-450/1-92-001 (NTIS PB92-
           143676/AS), January 1992.
ASF-23     Carroll, J.  Screening Procedures For Estimating the Air Impacts of
           Incineration at Superfund Sites.  EPA-450/1-92-003 (NTIS PB92-171917).
           February 1992.
ASF-24     Eklund, B., S. Smith, and A. Hendler.  Estimation of Air Impacts For the
           Excavation  of Contaminated Soil.  EPA-450/1-92-004 (NTIS PB92-171925),
           March 1992.
ASF-25     Draves, J. and B.  Eklund.  Applicability of Open Path  Monitors for Superfund
           Site Cleanup. EPA-451/R-92-001 (NTIS PB93-138154). May 1992.
ASF-26    U.S. EPA.  Assessing  Potential Air Impacts for Superfund Sites.  EPA-451/R-
           92-002. September 1992.

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ASF-27     Hueske, K., B. Eklund, and J. Barnett.  Evaluation of Short-Term Air Action
           Levels for Superfund Sites, (in press).  April 1993.
ASF-28     Ranum, D. and B. Eklund. Compilation of Information on Real-Time Air
           Monitors for Use at Superfund Sites,  (in press). April 1993.
ASF-29     U.S. EPA. Air Emissions From Area Sources: Estimating Soil and Soil-Gas
           Sample Number Requirements.  EPA-451/R-93-002.  March 1993.
ASF-30     Eklund, B. and C. Albert.  Models For Estimating  Air Emission Rates From
           Superfund Remedial Actions.  EPA-451/R-93-001.  March 1993.
ASF-31     U.S. EPA. Contingency Analysis Modeling for Superfund Sites and Other
           Sources.  EPA-454/R-93-001.  1993.
ASF-32     Eklund, B., C. Thompson,  and S. Mischler. Estimation of Air Impacts From
           Area Sources of Paniculate Matter Emissions at Superfund Sites,  (in press).
           April 1993.
ASF-33     Dulaney, W., B. Eklund, C. Thompson, and S. Mischler.  Estimation of Air
           Impacts For Bioventing Systems Used at Superfund Sites,  (in press). April
           1993.
ASF-34     Eklund, B., C. Thompson,  and S. Mischler. Estimation of Air Impacts For
           Solidification and Stabilization Processes Used  at Superfund Sites,  (in press).
           April 1993.
ASF-35     Dulaney, W., B. Eklund, C. Thompson, and S. Mischler.  Estimation of Air
           Impacts For Thermal Desorption Systems Used at Superfund Sites,  (in press).
           April 1993.
Affiliated Reports
           Eklund, B., et al.  Control  of Air Emissions From  Superfund Sites.  Final
           Revised Report. EPA/625/R-92-012. U.S. EPA, Center  for Environmental
           Research Information.  November 1992.

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              APPENDIX B




USEFUL CONTACTS AND TELEPHONE NUMBERS

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                                 APPENDIX B

            USEFUL CONTACTS AND TELEPHONE NUMBERS

1.    EPA Regional Offices

      Each EPA regional office has the following staff positions:

      •     Air/Superfund Coordinator;
      •     ARARs Coordinator; and
      •     Air Toxics Coordinator.

      The Air/Superfund coordinator is the best single point of contact for air issues related
to Superfund Sites.  The individuals in the staff positions listed above can be reached through
the office switchboards at the following numbers:
l?;;;:RegWu:f:.
I
n
m
IV
V
VI
vn
vm
IX
X
".'$'.: iilxxaUon
Boston
New York
Philadelphia
Atlanta
Chicago
Dallas
Kansas City
Denver
San Francisco
Seattle
Telephone Number
(617) 565-3420
(212) 264-2657*
(215) 597-9800
(404) 347-3004
(312) 353-2000
(214) 655-6444
(913) 551-7000
(303) 293-1603
(415) 744-1305
(206) 442-1200
*Air Programs Branch x-2517
2.    Air/Superfund Program Contact

      The primary contact for the Air/Superfund program is Mr. Joseph Padgett of EPA's
Office of Air Quality Planning and Standards at (919) 541-5589.
3.    Document Ordering Information

      Documents can be obtained through the National Technical Information Service
(NTTS) at (703) 487-4650.  Information of Air/Superfund reports that are not yet in the NTIS
system can be obtained from Environmental Quality Management at (919) 489-5299.

-------
      Other sources of documents include:

      •     EPA's Control Technology Center (CTC) at (919) 541-0800;

      •     EPA's Center for Environmental Research Information (CERI) at (513) 569-
            7562; and

      •     U.S. Government Printing Office (USGPO) at (202) 783-3238.


4.    Other Useful Contacts

      Air and Waste Management Associates (412) 232-3444.


5.    Hotlines
      OAQPS TIN
Modem #
(919) 541-5742
      The OAQPS TTN consists of the following:
:! Bulletin | Board ^t
AMTIC
APTI
CHIEF
CTC
EMTIC
OAQPS
SCRAM
!;.,::% Contact- .. •; ='
JoeElkins
Betty Abramson
Michael Hamlin
Joe Steigerwald
Dan Bivins
Herschel Rorex
Russ Lee
; Phone^1SEtimbeฃ
(919) 541-5653
(919) 541-2371
(919) 541-5232
(919) 541-2736
(919) 541-5244
(919) 541-5637
(919) 541-5638
       AIRS Database
       BLIS Database
       (RACT/BACT/LAER)
       NATICH Database
       TOXNET
       IRIS
Andrea Kelsey
Joe Steigerwald

Vasu Kilaru
Information
User Support
(919) 541-5549
(919) 541-2736

(919) 541-0850
(301) 496-6531
(513) 569-7254

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                      APPENDIX C




LIST OF VENDORS FOR ANALYTICAL AND SAMPLING EQUIPMENT

-------
                            Electrochemical Systems
k ' V* A
^v...-,, ^ ;Yeaaor
AIM USA
AIM USA
Bacharach Inc.
Bacharach Inc.
Bacharach Inc.
Bacharach Inc.
Bacharach Inc.
Bacharach Inc.
Bacharach Inc.
Biosystems, Inc.
CEA Instruments Inc.
CEA Instruments Inc.
Capital Controls Co. Inc.
Gas Tech Inc.
Gas Tech Inc.
Gas Tech Inc.
Gas Tech Inc.
Industrial Scientific Corp.
Industrial Scientific Corp.
Industrial Scientific Corp.
Industrial Scientific Corp.
International Sensor Tech
Lumidor Safety Prod/ESP Inc.
Lumidor Safety Prod/ESP Inc.
Lumidor Safety Prod/ESP Inc.
Lumidor Safety Prod/ESP Inc.
Lumidor Safety Prod/ESP Inc.
Metrosonics Inc.
Sensidyne Inc.
Instrument
Model 1100
Model 2000
Sentinel 4
TLV Sniffer
Model 505
Gas Pointer H
Sentinel 44
Sniffer 302
Sniffer 303
Cannonball 2
TG-BA
TG-KA
Multipoint Gas Detector 1660
GX-86
GX-91
HS-91
HS-91
HS560
CL266
MX 251
TMX410
Remote Link System III
Model MPU-16
Model MPU-44
Gas Pro SGM-1000
MPU-220 (Pump)
MPU-220 (Remote)
PM-7000
SS-2000
Gases Measured Illlyl
THC



Yes





Yes











Yes







Toxtes
Yes
Yes


Yes

Yes


Yes
Yes
Yes
Yes
Yes
Yes

Yes
Yes
Yes

Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Combustibles
Yes

Yes

Yes
Yes
Yes
Yes
Yes
Yes



Yes
Yes
Yes
Yes


Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes


Abbreviations:
            THC   =
            02
Total Hydrocarbon
Oxygen

-------
             Total Hydrocarbon Systems:  Flame lonization Dectors
% s ; Vendor
CSI
CSI
Eagle Monitoring
Eagle Monitoring
Eagle Monitoring
Eagle Monitoring
Foxboro Company
Foxboro Company
GOW-MAC Instrument Company
GOW-MAC Instrument Company
GOW-MAC Instrument Company
GOW-MAC Instrument Company
Heath Consultants
Heath Consultants
Heath Consultants
MSA Instrument Division
MSA Instrument Division
MSA Instrument Division
MSA Instrument Division
MSA Instrument Division
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Pace Environmental
Rosemount Analytical
Rosemount Analytical
Rosemount Analytical
Rosemount Analytical
Rosemount Analytical
Rosemount Analytical
Sensidyne Inc.
Thermo Environmental
Thermo Environmental
<
Instrument
HC 5002C
HC5002C
EM7000
EM700
EM7000
EM700
OVA-108
OVA-88
Model 23-500
Model 23-500
23500 TH Analyzer
23500 TH Analyzer
DP-IH
DP-EM
PF-II
Model 10 ISA
Model 1015H
Gas Corder - FID
Model 1015H
Model 1015A
JUM 109A
JUM - VE7
JUM 3-100
JUM 3-100
JUM 3-300
JUM 5-100
JUM - VE7
JUM 5-100
JUM 3-300
JUM 109A
400A
404A
402
404A
400A
402
Portable FID
Model 51
Model 51
Gases Measured
'VOC


Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes


Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
















Yes


5-VOC


Yes
Yes
Yes
Yes
Yes
Yes































THC
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes

Yes
Yes
,n-CH4 '




















Yes








Yes









Abbreviations:
  VOC  = Volatile Organic Compounds
 S-VOC  = Semi-Volatile Organic Compounds
 THC  = Total Hydrocarbons
n-CH4  = Non-Methane Hydrocarbons

-------
             Total Hydrocarbon Systems: Photoionization Detectors
- Vendor
HNU Systems
HNU Systems
HNU Systems
HNU Systems
HNU Systems
HNU Systems
HNU Systems
HNU Systems
MSA Instrument Division
MSA Instrument Division
MSA Instrument Division
MSA Instrument Division
Photovac Inc.
Sentex Systems
Thermo Environmental
Thermo Environmental
Thermo Environmental
Thermo Environmental
Instrument
DL-101
HNU 201
HNU 201-250
HNU 201
HW-101
PI-101
HNU 201-250
IS-101
Model 1015C
R-Photon PID
Model 1015C
Gas Corder - PID
Microtip
Scentogun
Model 52
Model 580S
Model 52
Model 580 B
Gases Measured
VOC
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
S-VOC
Yes
Yes

Yes
Yes
Yes

Yes
Yes

Yes
Yes
Yes

Yes
Yes
Yes
Yes
THC
Yes
Yes

Yes





Yes

Yes
Yes
Yes

Yes


H-CH4









Yes

Yes



Yes


Abbreviations:
             VOC  =     Volatile Organic Compounds
             S-VOC =     Semi-Volatile Organic Compounds
             THC  =     Total Hydrocarbons

-------
                           Total Hydrocarbon Systems:   Others

*- ' Vendor
AIM USA
Bacharach Inc.
International Sensor Tech.
Matheson Gas Products
Matheson Gas Products
%
instrument
Model 1200
TLV Sniffer
Remote Link System III
Model 80SA
Custom Gas Del. Sys.

Detector
TD
EC, CB
EC, SS
SS, TC, Plat
SS

VOC



Yes
Yes

S-VOC



Yes
Yes

THJCJ:
Yes
Yes
Yes
Yes
Yes
leasureid ;-.:
•*&&8&tง


Yes
Yes
Yes
!.'•'!. t .: :': : V- '!-•!
•Combustibles


Yes
Yes
Yes
Abbreviations:
               VOC
               S-VOC
               THC
               TD
               EC
               SS
               TC
               Plat
Volatile Organic Compounds
Semi-Volatile Organic Compounds
Total Hydrocarbons
Tin Dioxide
Electrochemical
Solid State
Thermal Conductivity
Platinum

-------
                                 Spectrophotometric Systems
^ A •. y.\ : :: f
'-.' -^, , ^faSof
CEA Instruments Inc.
MSA Instrument Division
Milton Roy
Rosemount Analytical Inc.
Foxboro Company
Foxboro Company
ABB Environmental
ABB Environmental
AIM USA
Anarad Inc.
MDA Scientific Inc.
MIDAC Corporation
Mattson Instruments Inc.
Nicolet Instrument Corp.
Bruel & Kjaer
Instrument
RI-411A
LIRA-3000
Model 3300A
880A
MIRAN203
MIRAN 1B-X
ER130
ER110
0PM
AR9000
FTIR Remote
Sensor
FTIR
REA-FTIR
FTIR 0PM
Type 1302
Detector
NDIR
NDIR
NDIR
NDIR
IR
IR
UV
UV
GFC
FTIR
FTIR
FTIR
FTIR
FTIR
IPA
Gases Measured
VOC




Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
s-yoc




Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Tes
THC

Yes

Yes





Yes
Yes
Yes
Yes
Yes
Yes
Toxics

Yes
Yes
Yes


Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes

Combustibles


Yes



Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes

Others
Yes







Yes






Abbreviations:
               VOC
               S-VOC
               THC
               CO2
               NDIR
               IR
               UV
               GFC
               FTIR
               IPA
Volatile Organic Compounds
Semi-Volatile Organic Compounds
Total Hydrocarbon
Carbon Dioxide
Non-dispersive Infrared
Infrared
Ultraviolet
Gas Filter Correlation
Fourier-Transform Infrared
Infrared Photoacoustic Absorption

-------
                                 Colorimetric Systems
Vendo?
CEA Instruments Inc.
MDA Scientific Inc.
MDA Scientific Inc.
MSA Instrument Division
Matheson Gas Products
National Draeger Inc.
Sensidyne Inc.
Instrument ..
TGM-555
Portable 7100
TLD-1
Detector Tubes
Matheson-Kitagawa
Detector Tubes
Detector Tubes
Detector
Liquid
Tape
Tape
Solid
Solid
Solid
Solid
Gases Measured
'VOC



Yes
Yes
Yes
Yes
S-VOC



Yes
Yes
Yes
Yes
THC




Yes
Yes
Yes
Toxics
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Combustibles

Yes

Yes
Yes
Yes
Yes
Others
Yes
Yes





Abbreviations:
              VOC   =      Volatile Organic Compounds
              S-VOC  =      Semi-Volatile Organic Compounds
              THC   =      Total Hydrocarbon

-------
                        Gas  Chromatograph/Mass Spectrograph Systems
^Waiter
CMS Research Corporation
Foxboro Company
HNU Systems Inc.
HNU Systems Inc.
MSA Instrument Division
MSA Instrument Division
MTI Analytical Instruments
MTI Analytical Instruments
MTI Analytical Instruments
Microsensor Systems
Microsensor Systems
Microsensor Systems
Microsensor Systems
Photovac Inc.
Photovac Inc.
Photovac Inc.
SRI Instruments Inc.
Sentex Systems Inc.
ABB Process Analytics
Extreal Corporation
ELI Eco-Logic
Viking Instruments
Instrument
2000 Minicams Sys
OVA-128
HNU 301-DP
HNU Model 311 GC
Model 8550
Model 1030A
Quad 400 gas analyzer
P 200 Microgas Anlyzr.
M200 Microgas GC
MSI-301A
MSI-301E
MSI-301B
MSI-301
10-S Plus
10-S Plus
Snapshot
Model 8610 GC
Scentograph
EnviroSpec 3000
Questor II Process MS
Sims 500
2400-700
Detector(s)
FID.PID.FP
FID
FID.PID.UV.ECD
PID.UV.ECD
FID,PID,TCD,HID,ECD
FID
SS
SS
SS
TCD
TCD
TCD
TCD
PID
PID
PID
FID,PID,FP,ECD,ELCD
PID.TCD.AID.ECD
MS
MS
MS
MS
Gases Measured
VOC
Yes
Yes
Yes
Yes
Yes

Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
s-voc

Yes
Yes
Yes
Yes

Yes
Yes
Yes




Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
THC

Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes




Yes
Yes
Yes
Yes
Yes
Yes
Yes


Toxics




Yes

Yes
Yes
Yes







Yes

Yes


Yes
Combust2>ks






Yes
Yes
Yes







Yes

Yes


Yes
Abbreviations:
                   VOC
                   S-VOC
                   THC
                   FID
                   PID
                   FP
                   UV
                   ECD
                   TCD
                   HID
                   SS
                   ELCD
                   AID
                   MS
Volatile Organic Compounds
Semi-Volatile Organic Compounds
Total Hydrocarbons
Flame lonization Detector
Photoionization Detector
Flame Photometric
Ultraviolet
Electron Capture Detector
Thermal Conductivity Detector
Helium lonization Detector
Solid State
Electroytic Conductivity Detector
Argon lonization Detector
Mass Spectrograph

-------
Particulate Samplers
Vendor
Anderson Samplers Inc.
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Climet Instrument Company
Dasibi Environmental Corp.
Mffilnc.
Mffilnc.
Mffilnc.
Mffilnc.
Mffilnc.
Mffilnc.
Sensidyne Inc.
Wedding & Associates
Instrument .:..
FH 61 1-N Beta
CI-4224
CI-4120
CI-7350
CI-4124
CI-4220
CI-7300
CI-7400
CI-4100
CI-4200
CI-7600
CI-7200
PM-10 Beta Gauge
FM-7400
PDM-3
RAS-2
RASSEx
RAM-1
RAM-5
LD-1
PM-10 Beta Gauge
'•••• \- Detector
Radiation-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Radiation-based Particulate Monitor
Laser Fiber Detection
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Opacity-based Particulate Monitor
Laser Light Scattering
Radiation-based Particulate Monitor

-------
                                 APPENDIX D

                               CASE EXAMPLE
NOTE:      This case example is a slightly modified version of a case example originally
            published in "Guidance on Applying the Data Quality Objectives Process for
            Ambient Air Monitoring Around Superfund Sites (Stage III)".

-------
D.I          BACKGROUND

             This hypothetical Superfund site, located on the outskirts of an urban area,
consists of approximately 180 acres.  The fenced-in site property is mostly flat, covered by
weeds and brushes 1 to 2 meters in height.  Also, there is a continuous row of both
deciduous and nondeciduous trees ranging from 18 to 23 meters in height, just inside the
boundary fence.  Figure 1 is a scaled map of the site.

             Site records indicate that approximately 20,000 drums containing waste from
local industries were buried here from 1959 until 1980.  Most of the drums were buried in a
single layer at a depth of about 2 meters.  The 3-acre area marked "A" in Figure 1
designates where the drums were buried.  The drums contain  mainly spent solvents
representing RCRA waste codes F001 through F006.

             Some of the drums have leaked and contamination of soil and  ground water is
possible.  This potential problem led to a  Remedial Investigation/Feasibility Study (RI/FS)
for the site.  The remedial action selected following the RI/FS was to dig up the buried
drums, pack them into larger drums labeled as containing hazardous waste, and transport
them to a nearby hazardous waste facility. This remediation effort is expected to take 12
months of on-site activity based on  an 8-hour, 5-day-a-week work schedule.

             During the RI/FS, drums were disturbed and an unusual  odor  was detected at
the house identified as receptor Rl in Figure 1. A measurement made  with a total VOC
instrument indicated that VOCs had been released into the air; therefore,  monitoring will be
necessary to detect any subsequent releases to the ambient air which would pose a threat to
public health during remediation.

             A State-operated meteorological monitoring station has been operating  for a
number of years outside the fenceline of this site (see Figure 1).  Its location adjacent to the
site is coincidental, but historical meteorological data such as  wind speed, wind direction,
rainfall, and temperature will be useful in designing the monitoring network.  In addition,
data from the nearest National Weather Service station could be used to provide
supplementary information.

D.2          WASTE CHARACTERIZATION

             There are no compound-specific air monitoring data available  for this site.
Therefore, to gain an understanding of which VOCs  may be released to the atmosphere
during remediation, it was necessary to determine the composition of the  buried waste.   The
first step was to review  the site records, which showed that the site contained waste codes
F001 through F006.  A  list of VOCs contained within each waste code was obtained  from 40
CFR, Part 261 (subpart D, paragraph 261.31 of Table  1).  Physical  property data were  then
used to rank the compounds according to  their volatility (vapor pressure or Henry's Law
constant) and their toxicity (carcinogen or noncarcinogen) to select target  compounds.

-------
Trees and brush,
combination of
spruce, pine, oak,
and maple, 18-23 m
            Gravel road, fugitive
            emissions control
            with water spraying
                                             Site Boundary
           Open area
           -1-2 m weeds,
           brush, and grass.
           Bush-hogged annually.
                                    Designated route
                                    for excavation work
                                    and site visitors
                  agency air
                  monitoring
                  station
                         Elevation at 470 m;
                         grade is mostly flat ฑ 6m
0    60  120  180   240

1 cm  = 60 m
ฎ Canister Sampling Site
       N
      Figure 1.  Hypothetical Superfund Site with Location of Buried Drums.

-------
D.3          OVERVIEW OF AAM PROGRAM

             The measurement system design consists of three monitoring strategies.  First,
modeling data indicated that in the absence of open pools of liquid waste, the probability of
the residents at the receptor sites being exposed to VOC concentration levels of concern was
very small.  Thus, a single screening strategy was designed to provide the RPM/OSC with
real-time information on total VOC concentrations near and downwind of the work site to
allow timely initiation of emission control procedures when necessary.

             The second element selected for the monitoring system design was a refined
screening strategy. This strategy will be employed if the results from the screening work
show that a preset criterion has been exceeded.  The reason for implementing the refined
screening strategy is to provide the RPM/OSC with real-time or near real-time concentrations
of the six indicator compounds near and downwind of the work site.  Since the concentration
level of concern is different for each VOC, a knowledge of the individual VOC
concentrations provides the RPM/OSC with more information to assess the risk of not
initiating emission control actions than is available from the screening results.  Also, this
refined screening  strategy provides total VOC concentrations at the impacted receptor site in
real-time to allow for timely initiation of emission control actions and provide information on
short-term exposure levels.

             When on-site measurements from the screening and/or refined screening
strategies exceed preset criteria (i.e., action levels), a third element of the monitoring
system, a quantitative assessment strategy will be employed to provide the RPM/OSC with 8-
hour average concentrations of individual VOCs at the receptor sites for that work day. The
monitoring methods that are  selected should have detection levels equal to or lower than the
applicable action levels.

             Procedures for selecting monitoring instrumentation for each of the three
monitoring strategies  are discussed  separately by strategy in the following subsections. The
selection process starts with a description of the performance and operational requirements of
the monitoring instrument.  This is followed by an overview of the commercially available
instruments considered for this application. Finally, the instrument and associated apparatus
selected for this application are discussed.

D.4          INSTRUMENT SELECTION

             Instrument Selection for Screening Strategy

             The primary function of the monitoring  instrument for the screening  strategy is
to provide a continuous, real-time indication of VOC concentrations near and downwind of
the work site. There are several commercially available VOC  monitors that provide real-
time data for total VOC  concentrations.

             The operational requirements and performance capabilities of an instrument for
this application are as follows:

             •      Operate outside year-round.

-------
             •      Operate continuously over an 8-hour work day without external
                    electrical  power.

             •      Be portable, easily carried by one person.

             •      Respond to all six indicator compounds.

             •      Have a detection limit of better than 1 ppm for isobutylene (the
                    calibration gas).

             •      Be capable of recording the total VOC data over an 8-hour period.

             •      Not respond to interferences common  to Superfund sites including
                    methane,  water, carbon dioxide, nitrogen,  and oxygen.

             •      Be capable of visual or audible alarms at preset total VOC
                    concentration levels.

             There are a number of manufacturers marketing total VOC monitors. Each
manufacturer usually specializes in a monitor with one of two possible detectors:  a flame
ionization detector (FID) and a photoionization detector (PID). Thus, the first decision  in the
instrument selection process was to decide on the appropriate detection technique.  The  PID
responds to all six compounds with detection limits below the respective levels of concern
(0.1 of the OSHA Permissible Exposure Limit).  The FID does  not respond to carbon
disulfide.  Also, a total VOC monitor equipped with a PID  does not require a source of
hydrogen gas as does a monitor equipped with an FID.  The FID hydrogen-burning system
requires more controls and a more complicated pneumatic system.

             The instrument chosen for this task was a total VOC-PID monitor with the
following capabilities:

             •      Designed to operate outside in the extremes of weather.

             •      Designed to operate continuously throughout the 8-hour work day with
                    the use of an additional battery.

             •      Is  portable, easily carried by one person, and easy to operate and
                    maintain.

             •      Responds to all six indicator compounds at concentration below the
                    respective levels of concern.

             •      Shows a detection  limit of 0.1 ppm for the calibration gas, isobutylene.

             •      Incorporates advanced  microprocessor technology for real-time digital
                    or graphic data assessment and built-in data logging capability for
                    storing data, including concentration with  time and location.

-------
             •     Does not respond to methane, water, carbon dioxide, nitrogen, and
                   oxygen.

             •     Programmed to sound an alarm at predetermined total VOC
                   concentrations.

             Instrument Selection for Refined Screening Strategy

             The refined screening strategy provides the RPM/OSC with near real-time
concentrations of the six high-risk indicator compounds near the work site and total VOC
concentrations at the impacted receptor site.  Also, the refined screening strategy will
provide information on the appropriateness of the six high-risk compounds selected as
indicators.  This strategy will provide tentative identification of unknown compounds released
from the work site, serve to determine when to implement the quantitative assessment
strategy, and provide guidance on when to submit the quantitative assessment sample for
analysis by GC/MS to identify unknown compounds. This information is  used to assess the
seriousness of the emissions from the  work site.

             The instrument for providing total VOC concentrations at the receptor is a
total VOC-PID.  It was selected for the same reasons discussed in the screening strategy.

             The operational requirements and performance capabilities of an instrument for
providing near real-time concentrations of at least the six indicator compounds near the work
site are as follows:

             •     Operate outside  year-round.

             •     Operate continuously over an 8-hour work day without external
                   electrical power.

             •     Be portable, easily carried by one person.

             •     Respond to all six indicator compounds.

             •     Have a detection limit of better than  1 ppm for benzene.

             •     Be capable of recording the total VOC data over an  8-hour period.

             •     Have a precision, expressed as  a relative standard deviation, of 20% or
                   better for each of the six indicator compounds at their respective levels
                   of concern, and  have a negligible bias.

             There are a number of  manufacturing marketing portable GCs which are
equipped with one or more detectors.  The four available detection techniques are argon
ionization detector (AID), photoionization detector (PID), flame ionization detector (FID),
and electron capture detector (ECD).  The PID and AID respond to all six indicator
compounds with detection limits below the respective levels of concern (0.1 PEL). The AID
and PID provide similar responses for four of the six compounds with the AID having

-------
superior sensitivity for the two remaining compounds.  At least one of the six compounds
result in minimal or no response using the FID and ECD detection techniques.

             The detection technique chosen for this application is the AID because of its
ability to respond  to all six indicators. Once the detection technique was selected,
recommendations  were solicited from individuals with experience using the portable GC-AID
in the field.  One  GC-AID monitor possessing all the required capabilities was reviewed and
selected for this application.  The instrument chosen  was a portable GC-AID  monitor with
the following features:

             •      Designed to operate outside in  the extremes of weather.

             •      Designed to operate on batteries and continue throughout the 8-hour
                    work day.

             •      Is portable, easily carried by one person, and easy to operate and
                    maintain.

             •      Responds to all six indicator compounds at concentrations below  the
                    respective levels of concern.

             •      Shows a detection limit of better than  0.1 ppm for benzene.

             •      Incorporates advanced microprocessor technology for near real-time
                    data output.  Data can be retrieved by either reviewing  on a computer
                    screen or connecting the GC-AID to a printer. The computer program
                    provides peak identification of  up to at least 9 peaks, calibration
                    information, and concentrations of the 9 peaks.

             Instrument Selection for Quantitative Assessment Strategy

             The purpose of the quantitative assessment strategy is to document the ambient
air 8-hour average concentrations that occurred at the receptors  during the work day.  Note
that the total VOC-PID monitor described in the refined screening strategy provides real-time
total VOC concentrations at the receptor site.

             The operational requirements and performance capabilities of an instrument for
this application include the following:

             •      It must  collect a representative 8-hour sample year-round.

             •      It must  provide data of sufficient quality (precision and bias) for
                    meeting the DQOs.

             •      It must  provide concentration results within one week of sampling.

             •      It must  provide speciation of all VOC compounds identified in the
                    liquid waste.

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             Sample collection can be conducted using either a sorbent or a stainless steel
canister.  Summa canisters and adsorbent tubes have both been successfully used for ambient
air monitoring at Superfund sites.  Both methods have their strengths, their applications, and
their problems. Experienced users of both methods believe that they are capable of
producing data of sufficient quality to satisfy the DQOs.  For actual application, the selection
would probably be based on the personal preference of the user.  For this illustration,
canister samplers serve as the selected method of collection 8-hour VOC samples.

             To provide data of sufficient quality to satisfy the DQO, a laboratory GC is
required for analysis of the canister samples. A GC with one or more of three detectors or a
GC with mass spectrometry will provide the quality of data necessary.  The three detectors
generally available are PID, FID,  and ECD; many times, more than one detector would be
operated on the same GC (note the AID has lower detection limits but may not, at this time,
be available in most laboratories).   The PID responds to all six indicator compounds with
detection limits below the respective levels of concern. For this application,  the low
detection limits are important since most of the VOC concentrations will be below the levels
of concern.  At least one of the six compounds provide minimal or no response using the
FID or ECD detection techniques.

             Since both systems  GC/MS and GC-PID with confirmation by FID will
reportably produce data of sufficient quality to satisfy the DQOs and have similar costs the
selection is based on convenience.  Because of a local laboratory equipped with and
experienced in the  use of GC-PID/FID, this becomes the method of choice for this
application.

             The  selected  system will use evacuated canisters to collect an ambient air
sample and use GC-PID with confirmation by FID to analyze the ambient air sample.  Ten
percent of the samples  will be subjected to GC/MS for qualitative confirmation. The
primary criterion for subjecting  a  sample to analysis by GC/MS is an indication by the on-
site portable GC-AID monitor that unknown compounds were released from the work site
during that work day.  These GC/MS analyses will be performed by a laboratory that does
not use a perma-pure drier in the  GC/MS sampling line because of the potential sample
losses of methyl ethyl ketone and  carbon disulfide.  The canister will begin and end sampling
under a vacuum (not using a sample pump) to minimize the potential of contamination.  The
canister analysis will be conducted by a laboratory with demonstrated experience.
Demonstrated experience was documented by participating successfully in the EPA's audit
cylinder repository program.  Prior to initiating  the remediation activities, the laboratory
chose to analyze the canisters will demonstrate capabilities for analysis of at  least the six
indicator compounds.

             The  sampling system selected for this application will provide the following:

              •      A representative 8-hour sample;

              •      Detection  limits of sufficient sensitivity;

              •      A precision  of 20% RSD (relative standard deviation) with no overall
                    bias to satisfy the DQOs; and

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             •      Specification of all compounds expected to be emitted from the
                    Superfund site.

D.5          MONITORING SYSTEM DESIGN

             One function of this monitoring system is to provide the RPM and/or on-site
coordinator (OSC) with data of sufficient quantity and quality to allow for timely initiation of
emission control actions.  These emission control actions should preclude exposing the
subject population to VOC concentrations greater than the levels of concern.  This function
of the monitoring  system will be partially accomplished by a screening strategy that employs
a total VOC-PID monitor at the work site to provide real-time data on emissions from the
site.  In addition,  if the screening strategy results show that total VOC concentrations exceed
a preset level, a refined screening strategy is initiated.  The refined screening strategy
employs two instruments, a portable GC-AID near the work site to provide near real-time
concentration values for the six high risk indicator compounds and a total VOC-PID at the
receptor site to  provide real-time total VOC concentrations. This limited speciation by the
portable GC-AID  will reveal the presence or absence of the high risk compounds. The
presence of one or more of these compounds  at preset concentration levels will be reason to
alert the RPM/OSC  to initiate emission  control actions, and, under certain conditions, to shut
down the remediation activity.  The total VOC concentrations measured at the receptor site
will also be used to  alert the RPM/OSC if predetermined concentrations are exceeded.

             Another important function of the monitoring system is to generate data
necessary to preclude the RPM/OSC from unnecessarily slowing or stopping the remediation.
This function is also fulfilled by using the refined screening strategy.  As part of the refined
screening strategy, the portable GC-AID is deployed to provide compound-specific data on
the high risk compounds.  For example, if the total VOC-PID monitor at the work site
indicates a VOC concentration of 100 ppm, the RPM/OSC may be inclined to stop the
remediation activity if, for example, the portable GC-AID  indicates that the total 100 ppm is
benzene, which has  a PEL of 1  ppm. Conversely, the RPM/OSC would not be as concerned
if the total 100  ppm was, for example, methyl ethyl ketone (which has a PEL of 200 ppm).
Thus, this function of the monitoring system could be very important in the overall efficiency
of the remediation program.  Also, results  from the portable GC-AID can be used to provide
tentative identification of unknown  compounds by comparing  the observed relative retention
time of an unknown peak against relative retention times that had been obtained for the more
volatile, non-indicator compounds.  The other part of the refined screening strategy involves
deploying a total VOC-PID monitor at the nearest  impacted receptor site.  This total VOC-
PID monitor at the receptor site will be used  to inform the RPM/OSC that VOCs emitted at
the work site are  reaching the receptor site.

             A third function of the monitoring system is to provide information of
sufficient quantity and quality to assure the RPM/OSC, decision maker, and residents at the
receptor sites that the DQOs were met.  This function is fulfilled by the quantitative
assessment strategy  consisting of an evacuated canister that collects an 8-hour sample at the
subject  receptor site  for subsequent analysis by laboratory  GC-PID with FID confirmation.
The precision, bias, and speciation capabilities of this procedure indicate that the DQOs will
be satisfied for the compounds of interest for this Superfund site.  Since real-time will not be
available,  the action levels should  be reasonably conservative. There  is conflicting data on

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the stability of methyl ethyl ketone and carbon disulfide in canisters.  For this illustration it
is assumed that they are stable.  Recent evaluation tests indicate that at least methyl ethyl
ketone can be successfully collected in  canisters.

             A special characteristic of this site that has influenced the monitoring system
design is that the fenceline around the site is lined with a row of full-grown trees,
invalidating the customary procedure of monitoring at the fenceline. This factor, plus the
closeness of the receptor sites to the fenceline, means that the sample must be collected at or
adjacent to the receptor to be representative of the air at the receptor.

             Based on the modeling data and to fulfill the three functions described  above,
three different monitoring strategies are being employed for this project.

             •     Screening at the work site for total VOC concentrations in real-time.

             •     Refined screening at the work site for near real-time concentrations of
                    the six indicator compounds and at the receptor site for real-time
                    concentrations of total VOCs.

             •     Quantitative assessment at the receptor site for integrated 8-hour
                    averages of individual VOCs.

These monitoring strategies will be used together to guide the on-site personnel in applying
emission control actions and to  document off-site concentrations at the receptor sites.

             Design for Screening Measurements

             Screening is the least costly monitoring strategy, but provides the least amount
of information.  It does provide real-time data, however,  allowing for a quick response to a
problem should one occur.  Screening is to be employed at the beginning of the project
and/or work day and will continue until emissions from the work site result in a  measured
VOC concentration that exceeds a preset level.  The monitoring system selected for screening
is a total VOC-PID monitor.  This monitor will serve dual  roles.  It will provide health  and
safety data and screening data for the potential off-site  migration of VOCs emitted from the
work site.

             For the screening strategy, when not in conflict with health and safety
monitoring,  the total VOC-PID monitor will be positioned on a stable tripod 30 meters
downwind of the work site and operated for  the 8-hour work day.  The monitor will be
repositioned at  least once an hour if necessary  to remain in the plume center directly
downwind of the work site.  An on-site meteorological station will be used  to gauge  the
direction of  the emission plume from its source.  In addition, wind socks will be located near
major emission sources.  (As needed, or when operation in the refined screening level, the
total VOC-PID monitor can be  used to evaluate upwind concentrations and/or to help the on-
site personnel locate the exact emission source at the work  site.)

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             Based on modeling data, the probability of experiencing VOC concentration
levels of concern at any of the receptor sites is very low.  Thus, this simple screening
measurements may prove to be the only air monitoring required during the remediation
program.

             Screening results are available in real-time and are used to alert the on-site
personnel to potential problems. Specifically, results from the total  VOC-PID monitor based
on preset criteria are used to:

             •     Alert the RPM/OSC that there is an emission source, allowing the
                   source  to be  located and controlled if necessary;

             •     Alert the RPM/OSC to check the proper protective clothing is being
                   worn;

             •     Direct the monitoring crew to initiate refined screening; and

             •     Direct the RPM/OSC to initiate emission control actions.

             Design for Refined Screening Measurements

             Refined screening is employed when a potential problem is indicated by the
total VOC-PID response.  Refined screening is more costly than screening, but it provides
some compound-specific information, allowing the RPM/OSC to better evaluate the
seriousness of the problem.  The portable GC-AID monitor selected for refined  screening can
be programmed to identify and quantify at least nine compounds.  The nine programmed
compounds can be changed if unexpected compounds posing high  risk to the resident
population are identified during the clean-up process.  Initially, the portable GC-AID monitor
will be programmed to identify and quantify responses for the six indicator compounds.  The
total VOC-PID monitor for this strategy  is in addition to the one used in the screening
strategy. It provides the RPM/OSC real-time data on total VOC concentration at the
impacted receptor site.

             Refined screening is conducted with the portable GC-AID monitor positioned
30  meters downwind of the work site. The instrument must be calibrated and ready for
operation at any time during the 8-hour work day. It should be capable of being placed  on-
site and generating data within 15  minutes.  The portable GC-AID monitor will be
repositioned as necessary, but at least once an hour (while refined screening is in effect) to
stay in the plume center-line, directly downwind of the work site.  An alternative approach to
be  considered is to set-up  the portable GC-AID in the on-site laboratory and take syringe
samples in the field for analysis in the laboratory.

              The total VOC-PID will be located at the receptor site with the highest
probability of being affected should a spill occur.  This monitor will be used during the  work
day and after work hours  on evenings when meteorological conditions indicate that there
could be an atmospheric temperature inversion.

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             Concentration values for up to nine compounds are provided by the portable
GC-AID approximately once every 10 minutes.  These compound-specific data help the
RPM/OSC know when to take action and the proper action to take.

             Results  from the portable GC-AID monitor based on preset criteria are used
to:

             •      Notify the monitoring crew to go to the quantitative assessment
                    strategy, or

             •      Notify the RPM/OSC to initiate emission control actions.

             Design  for Quantitative Assessment Measurements

             Quantitative assessment strategy provides more compound-specific information
than does  refined screening. Results from the quantitative assessment strategy are directly
applicable to the receptor site.  The monitoring system selected  for this level of monitoring
includes the use of an evacuated canister to collect the sample and a laboratory GC-PID with
FID confirmation for analysis.  Also, at least 10% of the canister samples analyzed will be
subjected to GC/MS for qualitative confirmation. Specifically, the downwind canister
sample(s)  collected on days that the portable GC-AID results indicate that unknown
compounds were released from the work site will be subjected to GC/MS analysis to  identify
the unknown compounds.

             For quantitative assessment, one or two receptor areas identified as having the
greatest probability of being impacted (i.e., being downwind of the work site) will be
instrumented with an evacuated canister sampling system. Meteorological information will
be used to identify the site(s).  In  areas where two or more receptors are located, a sampling
site will be selected so as to be representative of all these clustered receptors  Also, an
upwind or parallel site will be selected and instrumented.  On a predetermined schedule a co-
located sampler will be placed at the receptor site most likely to be impacted as part of the
QA program.  The samplers must be in place and operating over the 8-hour work day.
Results from the portable GC-AID and/or total VOC-PID, combined with meteorological
data, will  be used to determine if  the collected sample will  be forwarded to the off-site
laboratory for analysis.

             Results from analysis of quantitative assessment samples  are not available until
about two days after sample collection.  Thus, the data will be used to develop a data base
documenting VOC concentration levels experienced at one or more of the receptor sites for
various work-site situations. For  example, values for the ratio of the concentrations of an
indicator compound at the work site and  the receptor site for known meteorological and work
site conditions (for example, multiple accidental spills) will be calculated.  This information
will assist the RPM/OSC in making decisions about  the need  for emission control actions
under similar future work site conditions.

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             Results of quantitative assessment strategy based on preset criteria will be used
to:

             •      Notify the RPM/OSC that remediation procedures must be changed to
                    reduce emissions if levels of concern are regularly approached or
                    frequently exceeded at one or more receptor sites.

             •      Notify the RPM/OSC that certain receptor  sites must be evacuated
                    before continuing remediation if the levels  of concern are regularly
                    exceeded in spite of attempted emission control procedures.

             •      Provide  the RPM/OSC with accurate measures of VOC concentration
                    levels experienced at receptor sites.

D.6         CRITERIA FOR EMPLOYING A MONITORING STRATEGY

             The criteria for moving from one strategy to another is based on measured
VOC concentrations. In the absence of VOC ambient air measurement data, the criteria are
purposely set to error on the side of safety. These criteria will be re-evaluated and changed
if necessary as monitoring data become available.  The criteria are discussed for each
strategy in the following subsections.

             The screening strategy is to be employed at the beginning of each work day,
unless experience has shown that the remedial activity will result in emission levels that
trigger the need for refined screening.  The criterion for moving up to the refined screening
strategy is any time the total VOC response exceeds 5 ppm for 10 consecutive minutes.  This
is also the safety criterion  for changing from Level C to Level B dress for on-site workers.

             Moving from the refined screening strategy back to the screening strategy is
accomplished by simply discontinuing the use of the portable GC-AID. The criterion for this
move is when the total  VOC-PID response has been below 5 ppm for two consecutive hours
after the incident that triggered the need for refined screening.

             The rationale for the criterion of 5 ppm VOC for  10 consecutive minutes (in
addition to it being  the safety  criterion) follows:  benzene, identified as posing the highest
risk form the list of compounds in the buried waste,  has a PEL  of 1 ppm.  If, for example,
the refined screening results showed the 5 ppm VOC measurement to be 5  ppm benzene,
then the RPM/OSC will be notified to initiate emission control actions. Likewise, if the 5
ppm VOC was shown to be 5 ppm methyl ethyl ketone, which has a PEL of 200 ppm, the
remediation activity could proceed unimpeded.

             The refined screening strategy  is employed whenever the total VOC-PID
response has exceeded 5 ppm for more than 10 consecutive minutes, or at the beginning of
the work day if experience indicates a high probability that initiation of remediation will
result in screening results  greater than 5 ppm.

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             The quantitative assessment strategy is implemented in the event that results
from either the on-site portable GC-AID or the total VOC-PID monitor located at the
receptor site exceed preset values. The quantitative assessment strategy  is then initiated (that
is, one or both of the downwind canister samples (plus the upwind, co-located and trip blank
samples)  is forwarded to the laboratory for analysis at the end of the 8-hour work day) if the
calculated Em is greater than 1 for 30 minutes or more during the work day.

             A second criterion, independent of the portable GC-AID result, is based on
total VOC measurements at the receptor site. The quantitative assessment strategy is
initiated if the refined  screening strategy results show total VOC concentrations  greater than
0.5 ppm  for 30 minutes or more during the work day.

             These criteria are subjective; however, compound concentrations giving an
equivalent exposure value greater than 1 occurring 30 meters downwind of the work site may
result in  measurable levels at the impacted receptor site(s). Also, a total VOC concentration
of 0.5 ppm, corrected for background levels, signal the need for application of emissions
control actions at the work site.

             The reason for having two criteria, one based on total VOC and one on
compound-specific results, is that the total VOC concentration may represent compounds
other than the six indicator compounds.  The quantitative assessment strategy  would identify
and quantify all VOCs present at or above detection limit  concentrations.at the receptor site.

              Criteria for taking actions based on screening strategy results follow:

              •      If the total VOC-PID response is 5 ppm or greater for 10  successive
                    minutes, alert the RPM/OSC that there is an emission source so  that the
                    source may be located and controlled as necessary.

              •      If the total VOC-PID response is 5 ppm or greater for 10  successive
                    minutes, alert the RPM/OSC to check that proper protective clothing is
                    being worn.

              •      If the total VOC-PID response is 200 ppm or greater for 10 successive
                    minutes, alert the RPM/OSC that emissions must be reduced within the
                    next 30 minutes or halt the remediation activity. (This applies only if
                    the monitoring staff for some reason has been unable to initiate the
                    refined screening  strategy in this time period.)

              The rationale for the criterion of 5 ppm total VOC is that benzene could
account for the major portion  of the  VOC measurement.   Benzene has a short-term  exposure
limit (STEL) of 5 ppm; thus, the on-site workers would be alerted to wear the proper
protective clothing.  Also, a potential 5 ppm  concentration of benzene 30 meters downwind
of the work site may result in a concentration near  the level of concern  (100 ppb) at one of
the receptor sites.

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             The rationale for the criterion of 200 ppm for 10 successive minutes is that on-
site VOC concentrations at this level will probably result in measurable VOC concentrations
off-site.

             The compound-specific information provided by the portable GC-AID monitor
is used to guard against allowing one or more of the high risk compounds to reach the
receptor site at concentration levels near one tenth of their respective PELs.

             There are two criteria for initiating emissions control actions based on refined
screening data.  The two should be evaluated separately, that is action must be taken should
either one be exceeded. The criterion for emission control actions  follows:

             •     The RPM/OSC is notified that emissions must be reduced within 30
                   minutes or remediation will have to be halted if the portable GC-ATD
                   monitor response results in a calculated Em greater than 1 for 10
                   successive minutes.

             •     The RPM/OSC is notified that emissions must be reduced within 30
                   minutes or remediation will have to be halted if the total VOC-PID
                   monitor at the  receptor site shows a concentration of 0.5 ppm or
                   greater for 10 successive minutes.

             The rationale for the criterion of ฃ,„ >  1 for 10 successive minutes is that one
or more of the six indicator compounds could be present at concentrations  near their
respective PEL which  could result in receptor site concentrations near the levels of concern.
A  total VOC concentration of 0.5 ppm at the receptor site is one tenth of the work site
criterion of 5 ppm for moving from  Level C to Level B protective  clothing.  This is the same
rationale used for establishing the level of concern at one tenth of the PEL.

             Quantitative assessment results directly  estimate the health risks experienced
by residents at the receptor sites.   Thus,  these  results  are used by the RPM/OSC to assess
when the remediation process being  used needs to be changed so that emissions are reduced.

             Criteria for taking action based on quantitative assessment strategy results
follow:

             •     The RPM/OSC is notified that remediation procedures must be changed
                   to reduce emissions if any compound identified routinely approaches  or
                   exceeds 0.1 PEL, or that the remediation activity must be halted.

             •     The RPM/OSC is notified that a certain receptor  site must be evacuated
                   during the 8-hour work day when meteorological information indicates
                    that it will be in the plume's path and if results have shown one or
                    more compounds to exceed 0.2 PEL under similar meteorological
                    conditions.   Otherwise, the remediation activity must be halted.

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             These above criteria of 0.1 PEL and 0.2 PEL are used here because they are
the concentration levels of concern (0.1 PEL) and the concentration level at which the
decision maker stated that the monitoring system  should be such that the probability of a
false negative is no greater than 1 percent.

D.7          ESTIMATED TOTAL LABOR AND COST

             In Stage I of the DQO, the following resources were made available for this
ambient air monitoring effort:

             •      A mobile laboratory to be placed on-site for the duration of the clean-
                    up operation.

             •      Equipment necessary for cleaning the SUMMAฎ canisters in the on-site
                    laboratory.

             •      Two monitoring technicians to be dedicated to this air monitoring effort
                    (i.e., 2 FTEs).

             The monitoring effort is estimated  to require a total work force of 3 FTEs.
Thus, one FTE will be required in addition to the two provided by the ESD.  It is important
to not over-commit the on-site workers because concentrated monitoring activities could
occur at any time and the monitoring staff needs  to be prepared. The three monitoring
personnel will probably have to stagger their shifts in order to fully service the three
monitoring systems before and after the work day. That is, the two total VOC-PID monitors
and the portable GC-AID must be calibrated before and after each work day.  Also the
canisters must be deployed and the samplers set to take a sample spanning the 8-hour work
day. Costs have been estimated  for each monitoring strategy and are based on the
assumption that the refined screening and quantitative assessment strategies will be required
infrequently.

             Individual costs estimates  listed below are only for illustrating the process.
The individual item costs are believed to be reasonable but they do not represent actual
quotes from manufacturers or contractors nor is the listing presented as a comprehensive list.

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Project Planning
    DQO Package
    -   Sampling and analysis plan
    -   Quality assurance project plan
    -   Summary work plan
                                                       Subtotal:
$75,000
 $75,000
Manpower
    One technician (1 FTE) (estimated at $2,500 per week for 52
    weeks this includes per diem, overtime, etc.)
                                                       Subtotal:
$130,000
$130,000
Screening Strategy Costs
    Purchase price of total VOC-PID monitor
    Supplementary field kit
    Supplementary battery
    Replacement battery
    Replacement lamp
    Inlet filters (5)
    Calibration standard
                                                        Subtotal:
 $4,500
     600
     300
     300
     215
      25
     500
  $ 6,440
Refined Screening Strategy Costs
    Purchase price of portable GC-AID monitor
    Spare parts and filters
    Calibration standard and carrier gas for portable GC-AID
    Purchase price of total VOC-PID monitor and needed supplies
                                                        Subtotal:
 $ 20,500
     525
    3,100
    6,440
 $30,565
Quantitative Assessment Strategy Costs
•   Purchase price of canister sampler (4)
•   Purchase price of 34 canisters
•   Canister analysis by GC-PID/FID at $500 per sample (130)
•   Canister analysis by GC/MS at $1,000 each (5 assumed)
                                                        Subtotal:
 $ 20,000
  25,000
  65,000
    5,000
$115,000
                                                          GRAND TOTAL:

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-451/R-93-007
                                                           3. RECIPIENT'S ACCESSION NO.
4..TirLE AND SUBTITLE .         ,.,ซ..,     ซ
Air/Superfund National Technical Guidance Study
Series - Volume IV - Guidance for Ambient Air
Monitoring at Superfund Sites
                                                           5. REPORT DATE
                                  May 1993
                            6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
                                                           8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
3501 Mo-Pac Boulevard
Austin, Texas  78159
                                                            10. PROGRAM ELEMENT NO.
                            11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Office of Air Quality Planning  and Standards
Research Triangle Park, North Carolina  27711
                            13. TYPE OF REPORT AND PERIOD COVERED
                                  Final
                            14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
      This  report presents the results of an  EPA-sponsored study to develop guidance for
designing and conducting ambient air monitoring at Superfund  sites.   By law, all exposure
pathways -  including the air  pathway - must be evaluated for every Superfund site; therefore,
some level of ambient air monitoring usually is necessary at each site.

      This document offers technical guidance for use by a diverse audience, including EPA Air
and Superfund Regional and  Headquarters staff, State Air and Superfund staff, federal and state
remedial and removal contractors, and potentially responsible parties.  This manual is written to
serve the needs of individuals with various levels of scientific training  and experience in selecting
and using ambient air monitoring methods in support of air pathway assessments.

      There is no universal  approach to conducting an  ambient air monitoring  program that
would satisfy the needs of every air pathway assessment.   Instead, each program should be
designed to match  the specific program  needs  and available resources.   A framework for
designing an  effective ambient  air  monitoring is  presented in the document.  The framework
parallels earlier EPA guidance on applying the Data Quality Objectives  Process for ambient air
monitoring around Superfund sites.
IT*
KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b-IDENTIFIERS/OPEN ENDED TERMS
                                         c.  COSATI Field/Group
      Air Pollution
      Superfund
      Air Monitoring
VS. DISTRIBUTION STATEMENT
                                              19. SECURITY CLASS (This Report)
                                                                         21. NO. OF PAGES
                                              20. SECURITY CLASS (Tins page!
                                                                         22. PRICE
EPA Form 2220-1 (Rev. 4-77)   PREVIOUS EDI TION i s OBSOLETE

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                                                         INSTRUCTIONS

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        number and include subtitle for the specific title.

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        approval, date of preparation, etc.}.

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   11.   CONTRACT/GRANT NUMBER
        Insert contract or grant number under which report was prepared.

   12.   SPONSORING AGENCY NAME AND ADDRESS
        Include ZIP code.

   13.   TYPE OF REPORT AND PERIOD COVERED
        Indicate interim final, etc., and if applicable, dates covered.

   14.   SPONSORING AGENCY CODE
        Insert appropriate  code.

   15.   SUPPLEMENTARY NpTES
        Enter information not included elsewhere but useful, such as:  Prepared in cooperation with. Translation of, Presented at conference of.
        To be published in, Supersedes, Supplements, etc.

   16.   ABSTRACT
        Include a brief (200 words or less) factual summary of the most significant information contained in (he report. If the report contains a
        significant bibliography or literature survey, mention it here.

   17.   KEY WORDS AND DOCUMENT ANALYSIS
        (a) DESCRIPTORS - Select from the Thesaurus of Engineering and Scientific Terms the proper authori/ed terms that identify the major
        concept of the research and are sufficiently specific and  precise to be used as index entries for cataloging.

        (b) IDENTIFIERS AND OPEN-ENDED TERMS - Use identifiers  for project names, code names, equipment designators, etc.  Use open-
        ended terms written in descriptor form for those  subjects for which no descriptor exists.

        (c) COSATI FIELD GROUP - Field and group assignments are to be taken from the 1965 COSAT1 Subject Category List.  Since the ma-
        jority of documents are multidisciplinary in nature, the Primary Field/Group assignmcnt(s) will be specific discipline, area of human
        endeavor, or type of physical object. The application(s) will be cross-referenced with secondary  I leld/Group assignments that will follow
        the primary postmg(s).

   18.   DISTRIBUTION STATEMENT
        Denote releasability to the public or limitation for reasons other than security for example "Release Unlimited." C'ite any availability to
        the public,  with address and  price.

   19. &20. SECURITY CLASSIFICATION
        DO NOT submit classified reports to the National Technical  Information service.

   21.   NUMBER OF PAGES
        Insert the total number of pages, including this one and  unnumbered pages, but exclude distribution list, if any.

   22.   PRICE
        Insert the price set by the National Technical Information Service or the Government Printing Office, if known.
EPA Form 2220-1 (Rev. 4-77) (Reverse)

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