Technical Design Proposal

                               Clean Air
                     Status and Trends Network
                             (CASTNET)
                     By The Environmental Protection Agency
                            In Cooperation With
                The National Oceanic And Atmospheric Administration
                          And Other Federal Agencies
EPA
450/
1992.1
February 1992

-------
              Technical Design  Proposal

            Clean Air Status and Trends Network
                          (CASTNET)
4
                        February 1992
                    Contributors Are Listed In Appendix A
     .
!' :§ '')

            Atmospheric Research and Exposure Assessment Laboratory
                    Office of Research and Development
               .    U.S. Environmental Protection Agency
                    Research Triangle Park, NC 27711
                           JEEA Headquarters library

-------

-------
                                           Notice
       The use of trade names or commercial products in this document does not constitute endorsement



or recommendation for use.
                                    Acknowledgements
       This document was prepared jointly by the U.S. Environmental Protection Agency; other federal



agencies; state and local agencies; universities; and the Canadian environmental community.  Specific



coordination was provided by the National Oceanic and Atmospheric Administration. A complete listing



of contributors in the planning and review of this document is presented in Appendix A.

-------
                                                                            February 1992
                                        Contents

 Section                                                                           Page

 List of Tables	vii

 List of Figures  	  viii

 List of Acronyms and Chemical Symbols	ix

 Executive Summary	  xiii

 Introduction	   1

    CASTNET Organization	   1

       Total Deposition	   3
       Aquatic and Terrestrial Effects	   3
       Visibility/Acid Aerosols	   4
       Air Toxics	   4
       Statistical Network Design for Status and Trends  	.. ..	   5
       Data Management	   5
       Instrumentation/Methods	   5
       Contract Acquisition	;	   5

    Drawing on Existing Resources	   6
    The "80% Network"	   8
    Reporting Results	   8
    Quality Assurance	   9
    This Report	   9

Total Deposition Monitoring	11

    Monitoring Objectives	11
    Technical Approach	,	12

       Description of Measurements—Wet Deposition	17
       Description of Measurements—Dry Deposition	 .  18
       Treatment of Confidence and Uncertainty	21

    Sites and Implementation	24
    Relationship with Existing Networks	 ...  30
    Report Formats	32
                                           HI

-------
                                                                            February 1992

    Future Research Needs	33

       Sample-Averaging Times  	33
       Wet Deposition	34
       Dry Deposition  	35
       Regional Deposition Model Evaluation	36

 Aquatic and Terrestrial Effects Monitoring  	39

    Monitoring Objectives	39
    Three Types of Monitoring Required  	40
    Technical Approach—Aquatics Effects and Stressor Monitoring	42

       Description of Measurements	51

    Additional Aquatics Research and Monitoring Programs  	52

       The Adirondacks Aquatics Effects Program	52
       The EPA EMAP—Wetlands Program	53

    Technical Approach—Terrestrial Effects and Stressor Monitoring	53

       Description of Measurements	60

    Deposition Sites and Implementation	61
    Relationship with Existing Networks	61
    Report Formats .	62
    Future Research Needs	63

Visibility/Add Aerosols Monitoring	65

    Monitoring Objectives	  65
    Technical Approach	66

       Description of Measurements	69
       Treatment of Confidence and Uncertainty	72

    Sites and Implementation	72
    Relationship with Existing Networks	76

    Report Formats	,	77
    Future Research Needs .	77

Air Toxics Monitoring	79

    Monitoring Objectives	79

                                           iv

-------
                                                                            February 1992

       Great Waters Program	79
       Area Source Program	80

    Technical Approach		82

       Great Waters Program	82
       Area Source Program  	84
       Identification of Affected Areas  	;	:  ... 86
       Description of Measurements	87
       Treatment of Confidence and Uncertainty	90

    Sites and Implementation	 .	91
    Relationship with Existing Networks	92
    Future Research Needs	93

Statistical Network Design for Status and Trends	97

    Air and Deposition Variables	 97
    Integration of Existing Monitoring Network Data	98
    Frequency of Field Sampling  	98
    Media Representation and Area! Coverage	99
    Design of Optimal Network .;	99
    Preliminary Findings	  101

       Wet Deposition	  101
       Dry Deposition  	..'•;				  104
       Ozone	  104

Data Management	  105

    Recommendation	'.	  105
    Data Collection and Storage	  106
    Initial System Concept  	  107
    Quality Assurance/Quality Control	  107
    AIRS Selection Rationale	  110

       Advantages		  110
       Disadvantages  .. . .	  110
       Implementation Schedule	  HI

Instrumentation/Methods	 .  113

    Current Projects		  113

       Developing Passive Sampling Devices (PSDs)  	  113
       Evaluating the Versatile Air Pollution Sampler (VAPS)	114

-------
                                                                            February 1992

       Real-Time Acid Aerosol Instrument Development	  115
       Initiating Experiments with Filterpacks	US
       Monitoring of Hazardous VOCs with Automated Gas Chromatographs (autoGCs)	116
       Sorbent-Based Sampling and Analysis of Hazardous Polar VOCs	116

    Projects for Future Work	  117

       EstablishING Comparability of SO2 PSD Results with Filterpack Results at Four
        Additional Geographically Diverse Locations  	117
       Deploying a Better Sample Collection Device	  117
       Deploying a Screening Device for Acid Sulfate	117
       Testing PSDs for Other Trace Gases	  118
       Developing a VOC Sampling System	  118

    General Recommendations	  118
    Specific Recommendations	  119

       Total Deposition	  119
       Aquatic and Terrestrial Effects	  119
       Visibility/Acid Aerosols	 .  119
       Air Toxics  	  119


Appendix A - CASTNET Work Group Members and Workshop Participants	A-l

Appendix B - CASTNET CAAA Mandate Summary and Reporting Requirements   	B-l

Appendix C - Selected References   	C-l
                                         i
Appendix D - Sample Instrumentation/Methods "White" Paper	D-l
                                           VI

-------
                                                                              February 1992
Table

   1

   2


   3

   4

   5
                                      List of Tables
Method and Spatial Interpolation Uncertainties	22

Precision, Accuracy, and Site-Specific Uncertainty Estimates for Major
  Species Measured  	•	23

Characteristics of Some Nonurban Monitoring Networks in North America	31

Summary of Visibility Equipment Types and Analyses	71

System Inputs, Processes, and Outputs	108
                                           vii

-------
                                                                             February 1992
                                     List of Figures

Figure                                                                               Page

   1       Acid Deposition and Ozone Regions Based on Topographical, Chemical
           Concentration, and Climatic Characteristics  	16

   2       Currently Operating Wet Deposition Monitors as of March 1991	25

   3       Currently Operating Dry Deposition Monitors as of March 1991  	26

   4       Possible CASTNET Deposition Monitoring Sites	  28

   5       Possible Site Types at Proposed CASTNET Monitoring Locations	29

   6       Map of High-Interest Areas  	46

   7       Sensitive Terrestrial Ecosystems With Defined or Likely Effects From Air
           Pollution Stress	57

   8       Trends in U.S. Haze Based on Extinction Coefficients From Airport
           Observations	68

   9       Priority Areas for Visibility Monitoring		73

  10       Combined Existing and Proposed Visibility Monitoring	74

  11       Wet Sulfate Regional Trend Assessment  	103

  12       CASTNET Data Flow	 109
                                           via

-------
                                                                          February 1992
                       List of Acronyms and Chemical Symbols
 Acronyms
 ADS — Acid Deposition System
 AIRMoN — Atmospheric Integrated Research Monitoring Network
 AIRS — Aerometric Information and Retrieval System
 ANC — Acid-neutralizing capacity
 ANL — Argonne National Laboratory
 AQS — AIRS Air Quality Subsystem
 AREAL — Atmospheric Research and Exposure Assessment Laboratory
 CAAA — Clean Air Act Amendments of 1990
 CASTNET — Clean Air Status and Trends Network
 DIC — Dissolved inorganic carbon
 DOC — Dissolved organic carbon
 DOE — Department of Energy
 DQOs — Data quality objectives
 EAM — Engineering Aerosol Model
 EC — Canada:  Environment Canada
 EMAP — Environmental Monitoring and Assessment Program
 EPA — Environmental Protection Agency
 FHMP — Forest Health Monitoring Program
 FTIR — Fourier transform infrared
 GCRP — Global Change Research Program
 CIS — Geographic Information System
 GLWQA — Great Lakes Water Quality Agreement
 HAPs — Hazardous air pollutants
 IAA — Infrared aerosol analyzer
 IADN — Integrated  Atmospheric Deposition Network
 IMPROVE — Interagency Monitoring of Protected Visual Environments
 LAI — Leaf area index
 LaMP — Lake-wide Management Plan
 LJDAR — Light Detection and Ranging
 LOD — Level of detection
 LOQ — Level of quantitation
 NAAQS — National Ambient Air Quality Standards
NADP/NTN — National Atmospheric Deposition Program/National Trends Network
NAPAP — National Acid Precipitation Assessment Program
NDDN — National Dry Deposition Network
NEP — National Estuary Program
 NERR — National Estuarine Research Reserves
NESCAUM — Northeast States for Coordinated Air Use Management
                                          IX

-------
                                                                          February 1992
 NOAA — National Oceanic and Atmospheric Administration
 NFS — National Park Service
 NSWS — National Surface Water Survey
 NWS — National Weather Service
 OAQPS — Office of Air Quality Planning and Standards
 OME — Canada: Ontario Ministry of the Environment
 PAHs — Polycyclic aromatic hydrocarbons
 PCBs — Polychlorinated biphenyls
 PICs — Products of incomplete combustion
 PSDs — Passive sampling devices
 QA — Quality assurance
 QC — Quality control
 RADM — Regional Acid Deposition Model
 RFP — Request for proposals
 RLTM — Regionalized Long-Term Monitoring
 SAMWG — Standing Air Monitoring Work Group
 SGCP — Southern Global Change Program
 SIP — State Implementation Plan
 SOPs — Standard operating procedures
 SVOCs — Semi-volatile organic compounds
 TAMS — Toxics Air Monitoring System
 TIME — Temporally Integrated Monitoring of Ecosystems
 TVA — Tennessee Valley Authority          :
 USFS — U.S. Forest Service
 USGS — U.S. Geological Survey
 VAPS — Versatile air pollution sampler
 VOCs — Volatile organic compounds
 XAD/PUF — Sorbent/polyurethane foam
Chemical Symbols

     — Aluminum ion
     — Calcium ion
      Chlorine ion
      Hydrogen ion
      - Hydrogen peroxide
      — Nitric acid
      Potassium ion
     — Magnesium ion
     - Sodium ion
     -Ammonia
     — Ammonium ion
      Nitrogen oxide
      Oxides of nitrogen
NO2 — Nitrogen dioxide
ci--
H*-
HA-
HNO3
Na*-
NH,-
NH/
NO-

-------
                                                                               February 1992
NO3' — Paniculate nitrate
Oj — Ozone
Pb-Lead
PO4*" — Phosphate ion
SO2 — Sulfur dioxide
S0«* — Paniculate sulfate
                                             XI

-------
                                      February 1992
xii

-------
                                                                                       February 1992
                                       Executive  Summary

        The Clean Air Act Amendments (CAAA) of 1990 will have profound and far-reaching
 effects on air pollution and public health

 during the next decade and beyond.  The

 CAAA incorporate significant new

 regulatory requirements designed to reduce

 risks to public health and welfare as well

 as broad new research provisions that can

 substantially improve our scientific  -

 understanding of the causes and effects of

 damage caused by air pollution.

        Among the most significant of the

 new research provisions are the

 requirements for enhanced environmental

 measurement and monitoring contained in

 Titles I, m, IV, vm, and K of the

 CAAA.  These provisions require

 measurement and monitoring of acid

 deposition, ozone, acid aerosols, and
 CAAA MONITORING AND RESEARCH
      PROVISIONS ADDRESSED BY
                 CASTNET

• Total Deposition
  - National network and reports every five yean
  - NAPAP (EPA and othera) monitoring and two year
    report*
  - Western high elevation monitoring and annual
    report!
  - National network and report* every five yean
  - Ecomtem research on came*, effects, and trends
    (forest* , crop*, toils; surface water, groundwater,
    estuaries, wetlands)
  - NAPAP (EPA) report every two yean on effects, and
    every four yean on preventive deposition level*
  . Annual report oa Western high elevation effect*
  - EPA report on SO, (or NO. trades; and feasibility of
    preventive standard in three yean
  - National Acid Late* Regirtrv
  - Adirondack* watershed research

• Vribifiry/Acid Aerasoh
  - National network, and report* every five yean
  - NAPAP (EPA) reports every two yean
  ~ da** I ana monitoniig ud research

• Air Toxics
  - EPA/NOAA assessment, and reports every two yean
 --Rve station* in Great Lakes, one per Great Lake
  - Regulations in five yean for air deposition to Great
    I,aktSi Chesapeake Bay, Lake Champlain, and coastal
    w»t*r* a* deemed neeeatary by the Report due to
    Congrea* in three yean
  • Urban toitics research and monitoring, with report in
    three yean and rational control strategy in five yean
hazardous air pollutants.

        Examined collectively, these requirements impose the need for a substantial expansion of the

existing national program for urban air measurements and monitoring; this current program has
                                                 xiu

-------
                                                                                February 1992

 provided the historical scientific basis for the establishment and subsequent revision of die National

 Ambient Air Quality Standards (NAAQS).  For the first tune, the CAAA also mandate a broad

 measurement and monitoring program beyond our populated urban areas that will advance our

 understanding of die effects of air pollutants in rural areas and in aquatic and terrestrial ecosystems.

        The CAAA provisions also impose a

 requirement to enhance and accelerate

 environmental research and determination of

 status and trends in crucial areas.  In general,

 the provisions also present two significant

 scientific challenges.  The initial challenge is

 to develop 3 research  and monitoring program

 that integrates as many measurements as

 possible into a single monitoring program that  *

 in turn integrates network design, trans-

jurisdictional operation, and data analysis.

The second challenge  is to establish an adequate number of sites in appropriate locations to ensure

mat the resulting measurements can be interpreted with confidence and accuracy.

        Neither of these scientific issues has been addressed explicitly and scientifically as our

national air pollutant monitoring networks have evolved over the past twenty years.  Resolutions must

be generated, however, if we are to advance our research on the effects of air pollution and the

impacts of the CAAA  of 1990 in reducing this pollution.

       This document presents the preliminary design for a comprehensive research monitoring and

measurement network that meets the objectives established in the CAAA. An important element of
           REPRESENTATIVE LIST
      OF WORK GROUP PARTICIPANTS

     •  Environmental Protection Agency (EPA)
     •  National Oceanic and Atmospheric
        Administration (NOAA)
     •  U.S. Forest Service (USFS)
     *  National Park Service (NPS)
     •  U.S. Geological Survey (USGS)
     •  Canada: Ontario Ministry of the
        Environment (OME)
     •  Canada: Environment Canada (EC)
     •  Colorado State University
     •  Rensselaer Polytechnic Institute
     •  Standing Air Monitoring Work Groin)
        (SAMWG)
     •  Northeast States for Coordinated Air Use
        Management (NESCAUM)
XIV

-------
                                                                                 February 1992



 this design is a rigorous analysis of alternative approaches that could be taken, with emphasis on



 deciding the appropriate number and distribution of sites required to provide interpretable



 measurements mat are both scientifically rigorous and suitable for policy and regulatory analysis.  The



 value of the air pollution related status and trends data of the kind to be collected and coordinated



 through CASTNET is expected to extend beyond state and federal regulators to resource managers,



 policy makers, and others.



        Because of the underlying continental scale and scientific complexity of the scientific issues



 that must be addressed in mis design, mis document necessarily is the product of extensive



 collaboration within the United States and Canadian community of environmental scientists and



 engineers. The workshops on which this document is based were attended by representatives of all



 major North American organizations currently involved in environmental monitoring, including the



 Environmental Protection Agency (EPA), the National Oceanic and Atmospheric Administration



 (NOAA), the U.S. Forest Service (USFS), the National Park Service (NFS), the U.S. Geological



 Survey (USGS), the Ontario Ministry of the Environment (OME), Environment Canada (EC),



 Colorado State University, Rensselaer Polytechnic Institute, the Standing Air Monitoring Work Group



 (SAMWG), and the Northeast States for Coordinated Air Use Management (NESCAUM). Appendix



 A identifies the individual scientists who have contributed in the preparation and review of this



 document.



        The design overview  on this page is a brief synopsis of the design of the environmental



 research network that would respond to the CAAA. It is essential mat mis overview be interpreted in



 the context of the detailed information contained in each of the subsequent chapters of this document.



 Briefly, the network design incorporates the following monitoring sites that are essential to achieving



the Clean Air Act's research goals during the next ten to fifteen years: 51 additional site locations to
                                              xv

-------
                                                                                  February 1992
 monitor wet deposition, dry deposition,

 ozone, or a combination thereof; 20

 aerosol-only and 12 "full" visibility

 monitoring sites; one air toxics site per

 Great Lake with piloting and eventual

 expansion to Great Waters and appropriate

 urban areas; and integration of several

 existing monitoring networks data.  While

 much of this network is regional or

 national in scope, it also includes a focus

 on specific regions and sensitive

 ecosystems which require more intensive

 research to elucidate the processes, rates,

 and effects that are active there. The

 network also includes a focus on urban

 areas which represent elements of the	

 expanded urban  air monitoring and  .

 research program mandated by the Amendments.

        A small  network of more intensive (daily sampling) measurement sites operated by NOAA is

 important to the development of CASTNET.  It is designed to test and evaluate new instruments and

monitoring techniques.  The shorter sampling period is also valuable in developing a better

understanding of atmospheric phenomena associated with deposition processes and model validation,

and may allow the rapid detection of emission reductions from specific source areas.
          DESIGN OVERVIEW

Total Deposition
  . 19 additional sites added to existing
     NADP/NTN
  - 31 additional sites added to existing
     NDDN
  - 45 ozone sites added

Aquatic and Terrestrial Effects
  - An application of EMAP's TIME and
     RLTM programs in the NE lakes and Mid-
     Appalachian streams
  - An application of the USFS FHMP in the
     NE, SE/S, and W
  - 10 to 15 Intensive Monitoring Sites

Visibility/Acid Aerosols
  - 12 "foil* and 20 aerosol-only sites
     complementing existing IMPROVE
     network

Air Toxics
  • 1 station per Great Lake by 12/31/91
  - Integrated pilot study on Lake Michigan
  - Preliminary monitoring in diverse locations
  - Expansion of piloted method to other Great
     Waters
  - Monitoring and source characterization in a
   . "representative* number of cities
                                              XVI

-------

                                                                                  February 1992



       All of these networks are designed to be extensions of current activities, necessitated to



answer the questions posed in the Clean Air Act Amendments in the tune that is available.
                                             xvn

-------
                                       February 1992
XVIll

-------
                                                                                February 1992




                                        Introduction



        On November 15, 1990, the President signed the Clean Air Act Amendments (CAAA) which



 were designed to address the problems of acid rain, ozone nonattainment, and air toxics.  The CAAA



 included a call for an unprecedented, extensive national monitoring program to assess improvements



 in the nation's air quality and overall environment.  The challenge was considerable, not only because



 of the sheer size of the effort but also because of the logistical, technical, and scientific requirements



 involved. In addition to air quality monitoring, the CAAA address a wide range of interrelated



 monitoring, assessment, and research efforts ranging from atmospheric pollutant monitoring, effects



 of air pollution on aquatic and terrestrial ecosystems,  and visibility and air toxics monitoring.



        To meet part of the challenge, an integrated program has been developed to reflect the



 interagency, intergovernmental, and international requirements of large-scale monitoring and



 assessment. The key component of this multi-agency activity is the Clean Air Status and Trends



 Network (CASTNET) developed by the Environmental Protection Agency (EPA) in specific



 coordination with the National Oceanic and Atmospheric Administration (NOAA).



        CASTNET's goal is to establish an effective monitoring and assessment network to:



        *   Determine the status and trends of air pollutant levels and their environmental effects.



        •   Develop a scientific database to better understand causality for policy considerations.



        These two goals are integral parts of the ultimate question that must be answered:



        •  How well are the Clean Ah* Act goals being met?



CASTNET Organization



        CASTNET has two separate and distinct functions:  that of creator of the proposed network



design,  capable of fulfilling the CAAA mandates, and  that of the entity that will

-------
   CASTNET WORK GROUPS

Program Work Groups:
   • Total Deposition
   • Aquatic and Terrestrial Effects
   • Visibility/Acid Aerosols
   • Air Toxics
Support Work Groups:
   • Statistical Network Design for
       Status and Trends
   • Data Management
   • Instrumentation/Methods
   • Contract Acquisition
   -                                                                             February 1992

 implement the proposed CASTNET monitoring

 sites and perform the integrated assessments for

 the reports to Congress. This document is a

 product of the first function. Its

 recommendations, however, are linked to the

 second function, which is responsible for the

 action items described.

        Eight work groups were created for

 CASTNET. Four program areas were defined to

 design monitoring networks in their respective

 areas:  Total Deposition, Aquatic and Terrestrial Effects, Visibility/Acid Aerosols, and Air Toxics;

 At the first of two all-hands workshops held in November 1990 (the second being hi February 1991),

 these program groups were charged with designing an optimum network with alternatives for their

program areas, with the following specifics to be identified:

       1. The Clean Air Act monitoring objectives being served.

       2. An approach that identifies affected areas.

       3. A description of measurements, to be made by:

          a.  location

          b.  type

          c.  frequency

          d.  instrumentation

       4-  Proposed  relationship with existing networks: state, local, and Canadian networks, and

          networks run by other federal agencies.

-------
                                                                                  February 1992



        S. Sites to satisfy the CAAA requirements and implementation schedule.



        6. Cost implications.



        7. Treatment of uncertainties and confidence limits associated with data.



        8. Formats for reports generated by the network.



        9. Future research needs.



        The other four work groups were created to provide the program groups the support



 necessary for their network design: Statistical Network Design for Status and Trends, Data



 Management, Instrumentation/Methods, and Contract Acquisition.  Each of the eight work groups is



 identified below, along with a summary of salient considerations affecting network design. The



 specific mandates for each program area will be described in the appropriate section. See Appendix



 A for a list of work group and workshop participants.



 Total Deposition



        The  work group was to design a monitoring network to determine how wet and dry



 deposition levels for acid deposition and rural ozone concentrations have changed on a regional,



 national, and critical ecosystem scale.  Spatial and temporal coverage were required to be adequate



 for annual and seasonal resolution both for direct evaluation of deposition changes and for relating



 ecosystem changes to this deposition.  The dry deposition component was presumed to involve



 monitoring concentrations in air rather than deposition levels, while techniques for this are being



 developed. Monitoring for terrestrial effects needed to include ozone.




Aquatic and Terrestrial Effects



        The work group was charged with designing  an aquatics and terrestrial effects monitoring



program and  an atmospheric monitoring network to allow for an assessment of effects of atmospheric



constituents on  surface water quality and forest condition.  The monitoring of effects of air pollution

-------
                                                                                 February 1992



 on surface water, (including wetlands and estuaries) and groundwater, as well as on forests, crops, and



 soils was to be provided for.  The proposed network also was to include determination of the



 occurrence and effects of acid deposition on Western and high-elevation ecosystems, including forests




 and surface waters.



 Visibility/Acid Aerosols



        The work group's initial task was to design a network to determine how visibility levels



 effected by acid aerosols have changed in those areas most affected and how they have changed over



 large regions. Because visibility can vary greatly within the season, appropriate resolution on a



 temporal scale was necessary. The network also had to supply information regarding the causes of



 visibility problems and improvements.  Ultimately, the group will consider the design of the network



 to monitor changes in atmospheric acid aerosol related both to environmental and human health



 effects.



 Air Toxics



        There are two separate mandates for this work group: the "Great Waters" program and the



 Area Source Program.  The "Great Waters" program (which includes the Great Lakes, Chesapeake



 Bay, Lake Cbamplain,  and approximately 40 to 50 estuarine systems) is concerned with monitoring



hazardous air pollutants (HAPs) deposition to these waters and with the hazards to water quality (and



indirectly to people) and the environment (aquatic life and terrestrial wildlife).  The CAAA mandate



one monitoring facility per Great Lake by December 31, 1991.  The Area Source Program focuses on



ambient air monitoring of HAPs from urban area sources and the resultant hazards to human health.



The list of potential HAPs that must be monitored  is long, and the task is complicated by the lack of



measurement technology for many of the pollutants.

-------
                                                                                February 1992




 Statistical Network Design for Status and Trends



        This work group will play an integral part in selecting areas for potential future monitoring



 sites and in evaluating the statistical contributions of existing monitoring sites. Its statistical



 evaluations of network design will help ensure that the generated data will allow adequate estimations



 of ecosystem exposure as well as adequate detection and quantification of trends to a desired level of



 precision within a specified period.



 Data Management



        In  large integration efforts, and CASTNET  is no exception, the importance of data



 management cannot be overstated.  Hits work group was charged with developing a comprehensive



 standardization program to ensure mat all CASTNET data, which will be provided by a myriad of



 entities, are of comparable quality and are available in the format required by the various user groups.



 Instrumentation/Methods



        This work group surveyed current instrumentation and methodologies and recommended



 specific methods to choose from for each of the monitoring networks being designed.



 Recommendations were arrived  at by analyses encompassing reliability, accuracy and precision, and



 cost/benefits for each option. Research projects considered most crucial to CASTNET needs were



 pursued.



 Contract Acquisition



        Creating the statement of work for the CASTNET contract was this work group's



 responsibility. The contract will be the instrument for conducting monitoring, not provided by other



agencies, at sites that CASTNET establishes. Considerable work was required to make the contract



flexible enough to encompass the .variety and scope  of monitoring that may be needed.  Contract



proposals are currently being evaluated, with final selection of a contractor pending.

-------
                              February 1992
      REPRESENTATIVE LIST
 OF WORK GROUP PARTICIPANTS

• Environmental Protection Agency (EPA)
• National Oceanic and Atmospheric
   Administration (NOAA)
• U.S. Forest Service (USFS)
• National Park Service (NFS)
• U.S. Geological Survey (USGS)
• Canada: Ontario Ministry of the
   Environment (OME)
• Canada: Environment Canada (EC)
• Colorado State University
• Rensselaer Polytechnic Institute
• Standing Air Monitoring Work Group
   (SAMWG)
• Northeast States for Coordinated Air Use
   Management (NESCAUM)
 Drawing on Existing Resources

        To meet the CAAA objectives in the

 most efficient, cost-effective manner,

 CASTNET will use the resources of other

 programs, agencies, and networks at the

 federal, state, local, and international levels.

 The importance of these existing programs and

 their integration with the CASTNET effort

 cannot be overstated.  This document, for ease

 of presentation, is structured to present each

 work group's recommendations as a separate

 entity.

       The details of implementing each proposed network design make it clear, however, that

 CASTNET itself will be involved only in air and deposition monitoring. In most cases, it will merely

 supplement and/or upgrade an existing monitoring site, while relying on other programs for the

 biological and chemical effects monitoring required.  Some of the organizations included in the

 CASTNET design, as well as their expected contributions, are described on the next page.  It should

be noted mat many of the people involved in CASTNET also are involved in one or more of the

listed organizations, which should facilitate coordination in these partnerships.

       State networks are not discussed extensively in this document, because of the number of such

networks and die variations among the different state programs.  These networks will be incorporated

into the CASTNET program as indicated by considerations of network siting and installation.

Preference will be given to existing sites and networks where the methods  and  data generated are

-------
                                                                              February 1992
   CASTNET Design Participant
   research
                        NADP/NTN
                        NDDN
                        NAPAP
                        EMAP/TIME
                        EMAP-Surface Waters
                        EMAP-Forests
                        FHMP
                        GCRP
                        NFS
                        USFS
                        IMPROVE/NFS
                        IADN
   CASTNET Supporting Networks

                        NOAA-CORE
                        NOAA-AIRMoN
                        State networks
Contribution

       Wet deposition data
       Dry deposition (concentration) data
       Data relating to acid deposition
       Aquatic chemical data
Aquatic biological data
Terrestrial biological data
Terrestrial chemical and biological data
       Terrestrial cause and effects research
       Terrestrial cause and effects research
       and some
        national air monitoring data
       Aquatic and terrestrial cause and effects

        and some national air monitoring data
       Visibility data
       Air toxics monitoring at Great Lakes

Contribution

Dry deposition reference data
       Short-term data for atmospheric effects
Air quality and deposition data
compatible with CASTNET requirements.                                          ....'.

       Identifying site locations during all phases of siting will involve making.a preliminary

assessment based on a particular need (that is, to improve spatial or temporal resolution, to reduce

interpolation errors, or to provide ecosystem specific and critical ecoregion monitoring).  After a

potential site location has been identified, maps of existing sites (wet, dry, ozone, visibility, air

toxics) will be overlaid to discover whether mere are existing sites that could be used with minimal

modification or whether any could be augmented or upgraded to fulfill the monitoring need in that

-------
                                                                                 February 1992



area. The appropriate site-operating authorities will be contacted and included in the site location



process from the outset.  In the interest of creating the most efficient and cost-effective national



monitoring network possible, sites will be collocated at every available opportunity.  This strategy is



the keystone of CASTNET.



The "80% Network"



        CASTNET participants are charged with establishing the most comprehensive national air



pollution effects environmental monitoring program to date. They generally agree that the current



planned levels of resources and the level of scientific and engineering knowledge will allow about 80



percent of the network to be established, operated, and maintained.  Future resource and research



needs, challenges in statistical design,  data gathering needs, and needed instrument and protocol



development in some areas preclude the ability to complete a 100 percent network in the short term.



CASTNET will be able to complete its mission of fully determining all related CAAA environmental



status and trends when the remaining 20 percent of the network is in place. This objective depends



on resource availability and will require improvements in methods, siting, statistics,  assessment



protocols, and quality assurance.  Best estimates are that the advances necessary to implement the full



network will be made over the next three to five years.



Reporting Results



        Although the more pressing aim of CASTNET is to add monitoring sites across the country



and to increase the assessment of environmental data, the results of these activities will only become



useful when they are reported.  Consequently, the CAAA require each program area to provide



regular reports of its findings. The frequency and description of these reports are provided in



Appendix B.

-------
                                                                               February 1992




 Quality Assurance



        EPA has stringent quality assurance (QA) requirements for all of its field monitoring



 programs that cover all aspects from sampling to analysis and reporting. QA/SOPs (Standard



 Operating Procedures) exist for most measurements. CASTNET will develop appropriate QA/SOPs



 for those measurements that currently lack them, as well as for any new procedure that is adopted.



 Most, if not all, of the large networks CASTNET will be incorporating operate under an approved



 plan (see Appendix C for selected QA, implementation, and field operation references).



        Before any monitoring data is incorporated into  CASTNET, there will have to be an approved



 QA plan as well as a review of existing data and their associated QA procedures. Comparability of



 data relating to the chemical composition of the air and  precipitation will be established in part by



 periodic analytical testing with known samples.  Comparability of data relating to the deposition of



 chemicals would involve additional tests of the flux-determining techniques.  This is done with



 intercomparisons and by deployment of research-grade methodologies at a subset of locations, and



 would include a periodic rotation among CASTNET sites. Such intercomparison programs are the



 raison d'etre of the existing research networks operated  by NOAA, with which the CASTNET



program will be tightly linked. By maintaining a well quality-assured federal network, establishment



of data comparability between states will be facilitated.



This Report



       This is a combined report of the CASTNET work groups, and consists of a series of



recommendations.  It is not meant as a scientific review or summary on network design and



operations. Familiarity of the reader with modern monitoring methods is assumed.

-------
                                    February 1992
THIS PAGE INTENTIONALLY



      LEFT BLANK
          10

-------
                                                                                  February 1992
                                Total Deposition  Monitoring




 Monitoring Objectives



        In the present context, the topic of "total deposition" is considered to include acid deposition,



 deposition of related air chemicals, and information on their concentrations in both air and



 precipitation.  The Clean Air Act Amendments (CAAA) require monitoring of acid deposition, which



 occurs when sulfur dioxide and nitrogen oxide emissions are transformed in the atmosphere and



 return to earth, and ozone, which occurs as a result of nitrogen oxide reactions with volatile organic



 compounds (VOCs) in the atmosphere.  Both of these components are suspected health hazards and



 are implicated in forest damage. In addition, acid rain  damages lakes and buildings and indirectly



 contributes to reduced visibility:



        Monitoring objectives addressed in Title IV (Section 404) of the CAAA include identification



of sensitive and critically sensitive aquatic and terrestrial resources, and a report on the feasibility and



effectiveness of an acid deposition standard or standards to protect them.



       Title DC of die CAAA [Sections 103(c), (e), Q)» and 901 (g)] requires the establishment of a



national network to assume eight responsibilities associated with total deposition:



        1. Monitor, collect, and compile data, quantifying certainty in the status and trends of air



          emissions, deposition, and air quality.



       2. Ensure comparable air quality data from different states and nations.



       3. Determine trends by region and effects on water quality, forests  and crops, sensitive



          ecosystems, and materials.



       4. Provide data for model maintenance and application and for estimating transboundary



          impacts.






                                              11

-------
                                                                               February 1992



        5.  Develop improved atmospheric dispersion models.



        6.  Develop monitoring systems and networks for evaluating and quantifying exposure to and



           effects of multiple environmental stresses associated with air pollution.



        7.  Conduct research on the occurrence and effects of acid deposition on surface waters in the



           United States west of the Mississippi River and on high-elevation ecosystems; conduct



           research on the occurrence and effects of episodic acidification, particularly for high-



           elevation watersheds.



        8.  Continue the National Acid Precipitation Assessment Program (NAPAP) and report



           information about acid deposition hi a format appropriate for policy makers and the



           public.



        The Total Deposition work group reviewed existing wet and dry deposition networks and



generally found mem inadequate to meet the objectives of the Clean Air Act Amendments.



particularly in regard to dry deposition. Although NAPAP ultimately received a mandate to continue



under the CAAA, several of the major networks that were designed and funded during the period of



the NAPAP program were reduced in size or terminated in 1990 (such as the  MAP3S and OEN



networks),  resulting in a reduced field of monitoring sites from which CASTNET could draw. The



group proposed die following approach to establishing wet and dry networks to allow the CAAA



objectives to be met hi the most efficient and cost-effective manner.



Technical  Approach



       The CAAA requires a total deposition monitoring network to determine spatial and temporal



trends of acid deposition and rural ozone and to address the effects of deposition and



ozone on aquatic and terrestrial ecosystems. Data on the concentration and deposition of acidic



materials and ozone will be collected to:
                                             12

-------
                                                                                  February 1992

        *   Support water-quality

            determinations.

        •   Perform aquatic and

            terrestrial effects

            research.

        •   Determine regions of

            the country at risk.

        *   Assess materials

            damage.

        •   Perform model

            maintenance and

            application.

        •   Assess the effectiveness

           of emissions reductions on air chemistry and deposition.

        *  Determine transboundary impacts.

        Pollutants are deposited to the earth's surface through wet processes (precipitation), and dry

processes associated with the atmosphere's interaction with the surface.  Characterizing wet deposition

patterns is much simpler than characterizing dry deposition patterns because of differences in available

measurement systems. Precipitation processes mat remove pollutants from the atmosphere are

comparatively easily studied by analyzing precipitation samples.

        Such samples have been analyzed at many sites in North America to characterize the spatial

patterns and temporal trends for wet deposition. Dry deposition patterns have not been similarly

characterized because cost-effective direct measurement systems are not available. Dry deposition is
      WET DEPOSITION MONITORING

Network Participation Proposed:
  •  NADP/NTN
  •  States
  •  fannHign networks
  •  Others

Proposed Number of Wet Deposition Sites:
  •  19 additional wet deposition sites

Proposed Wet Deposition Site Locations:
  •  Eastern high elevations (Appalachians)
  •  Western high elevations (Rockies and Cascades)
  •  East and West coasts
  •  Underrepresented low elevation areas in Northeast

Proposed Wet Deposition Variables:
  •  In rain or snow - SO4*. NO/, H+, NH/, O% K+,
     Na+, Mg2*, Ca3+, PO4*. pH, and conductance
  •  In clouds or fog - SO4*, NO/, H+, NH«\ CT,
     Mg*% and Ca1*
      13

-------
                                                                                 February 1992
 estimated using an inferential

 model approach tor the 50-station

 National Dry Deposition Network

 (NDDN) and for the nine-station

 National Oceanic and Atmospheric

 Administration (NOAA) CORE

 research network. Fifteen of the

 NDDN sites are collocated with

 NADP/NTN wet monitoring sites,

 and five of the NOAA CORE sites

 are collocated with NDDN sites.

       The inferential model

 approach determines deposition

 flux as the product of a measured

 concentration and a modeled

 deposition velocity based on

 measurements of meteorological

variables and physical/biological
       DRY DEPOSITION AND OZONE
                 MONITORING

Network Participation Proposed:
    NDDN
    NFS
    NOAA
    States
    Canadian networks
    Others

Proposed Number of Dry Deposition and Ozone Sites:
  •  An additional 31 dry deposition and 45 ozone
     monitoring sites

Proposed Dry Deposition and Ozone Site Locations:
    Eastern high elevations (Appalachians)
    Western high elevations (Rockies, Cascades, Sierra
     Nevadas, and San Bernardinos)
    Intennountain West
    Great Lakes
    East and West coasts
    Underrepresented low elevation areas in Northeast,
     South, Mississippi Delta, and Plains

Proposed Dry Deposition Variables:
  »  Air concentrations - SO4*, NO,*, HNOj, O,, and
     SO,
  •  Meteorological parameters - wind velocity,
     temperature, temperature lapse rate (delta T),
     relative humidity, solar radiation, precipitation,
     and surface wetness
  •  Vegetation parameters - vegetation status and leaf
     area index
surface conditions.  The Total

Deposition work group recommends this approach, which can provide relevant information to the

Clean Air Status and Trends Network (CASTNET) at a reasonable cost. Other approaches such as

eddy .correlation, throughfall, and gradient processes, are in an exploratory phase of development.
                                              14

-------
                                                                                February 1992



 Although these "direct" flux measurements have not been used in routine monitoring programs, they



 should nevertheless be used at selected sites for comparison to inferential measurements.



        For wet deposition monitoring, the principal goal of CASTNET relates to the need to assess



 deposition trends and inputs for effects studies. For this purpose, monthly or seasonal averages are



 adequate. The wet deposition monitoring community concerned with ecological-effects and trends in



 the United States has settled  on  a weekly sampling protocol. CASTNET will continue this practice,



 relying on the existing National Atmospheric Deposition Program/National Trends Network



 (NADP/NTN) led by the USGS.



        For studies of more localized atmospheric consequences and consequences more closely tied



 to individual source regions, shorter-period samples are beneficial.  The atmospheric deposition



 research community has settled on a daily sampling protocol for mis purpose.  CASTNET will rely



 on the NOAA AIRMoN (Atmospheric Integrated Research Monitoring Network) program for input of



 this kind.



        In discussions of the weekly-sampling network, the work group divided the 48 contiguous



 states into separate regions based on topographical, chemical concentration, and climatic



 characteristics for both acid deposition and ozone for the purpose of establishing reporting regions for



 statistical changes.  These regions are shown in Figure 1. The monitoring requirements for bom the



 wet deposition and dry deposition networks are addressed separately. CASTNET will provide



 estimates of total nitrogen and sulfur deposition and of ozone and sulfur dioxide concentrations.



       It should be noted here that the approach adopted is most readily applicable to the wet



deposition component.  Dry deposition varies from site to site within any given region, and so



regionalization as described above is more imprecise.  While this problem is widely appreciated,  the



scientific capability to fully address it and to take the corresponding complexity into proper account is






                                              15

-------

-------
                                                                                February 1992



 still under development.  It is, in part, for this reason that the integrated network that is anticipated



 will need different arrays of stations to address questions of wet and dry deposition.



 Description of Measurements—Wet Deposition



        Wet depositioD data are needed; (a) to contribute to the assessment of total deposition, as



 affects the terrestrial and aquatic environment, and (b) to indicate by simple measurement practice



 changes in air quality as may be related to changes hi emissions.



        The chemical species or variables proposed for monitoring at the wet deposition sites are



 SO,2", NOj', H+, NH4+, C1-, K+, Na+, Mg2*, Ca2+, PO4*. pH^ and conductance.  These are the



 species and variables currently being monitored by NADP/NTN.



        A wet/dry collector manufactured by Aerochem Metrics has been used exclusively hi



 NADP/NTN since the late 1970s to monitor wet deposition. Precipitation is measured with a Belfort



 recording rain gauge with event marker; pH and conductivity are measured with standard instruments.



 The major cations and anions are measured at a central analytical laboratory using proven ion



 chromatographic and atomic absorption techniques.



        For monitoring cloud/fog deposition (S04*. NO,% H4, NH/, Cl', Mga% and Ca*+) which is



 limited to areas above cloud base and along some coastal areas, an automated cloud collection system



 developed by the Environmental Protection Agency (EPA), Tennessee Valley Authority (TVA),



 ManTech, and North Carolina State University is recommended.  This system, chosen after careful



 revjew of several designs, provides a level of accuracy and precision comparable to manual methods,



but at lower cost. Manual methods entail collecting droplets on a series of fine strings and analyzing



the droplets for cations and anions.



       Field instrumentation and analytical methods are generally well  established and have proven



satisfactory for meeting the majority of wet deposition monitoring objectives given a stringent quality






                                              17

-------
                                                                                February 1992



 assurance (QA) program.  Some important technical issues, however, heed to be addressed that relate



 to data quality and the ability to obtain complete spatial coverage.  For example, rain and snow



 samples are more easily collected at low elevations than high elevations, particularly at sites receiving



 significant snow and cloud/fog water deposition and wind. High elevations often restrict site access,



 and severe whiter conditions frequently cause equipment to operate poorly, resulting hi inadequate



 sampling of rainfall, snowfall, and cloud/fog deposition.  To improve sample collection at high-



 elevation and remote sites, establishing alternate sampling protocols may be required.  Snow core



 sampling may provide the total deposition to an area over a specified time period, but would not be



 adequate should separate wet and dry determinations be required.  If snow core sampling results



 prove inadequate, then improved equipment and sampling methods will be required.



 Description of Measurements—Dry Deposition



       The chemical species and meteorological and vegetation parameters proposed to be



 measured/monitored at the dry deposition sites are:



       •  Chemical species: SO**, NO,% HNQ,, O,, and SO*



       •  Meteorological parameters: Wind speed, wind direction, standard deviation of wind



          direction, temperature, temperature lapse rate (delta T), relative humidity, solar radiation,



          precipitation, and surface wetness.



       •  Vegetation parameters: Vegetation status and leaf area index (LAI).



Currently, the NDDN and the National Park Service (NFS) monitor these species and variables, with



the exception of vegetation status and leaf area index at all NFS sites, and HNQ, at some of the NFS



sites.  The NOAA dry deposition CORE program makes all of these measurements, but also focusses



on improving the methodologies for inferring dry deposition rates from such information and on



testing the quality of the answers by comparison against research grade techniques.






                                              18

-------
                                                                                 February 1992



        The NDDN measures concentrations of SO,*, N0j% HN03, and SOa using a filterpack.



 Ozone is measured on a continuous basis using a UV photometric analyzer. Because ozone is one of



 the atmospheric constituents for which a National Ambient Air Quality Standard (NAAQS) has been



 set, the detection limits, measurement range, precision, and accuracy of ozone measurement methods



 are well defined.  Meteorological measurements use systems that meet established stringent



 requirements. Filterpack techniques based on initial developments at Brookhaven National Laboratory,



 and like the methods popularized in Canadian networks, have been used in several networks to



 measure sulfur dioxide and nitric acid and is the technique currently used by the NDDN.  Several



 variations on this general design have been developed, with slightly differing performance



 characteristics that are still being explored.  The critical uncertainty relates to the precision of



 measurement of HNO3 and SO2, bom of which are often present in sufficiently low concentrations mat



 simple filterpack methods do not always work well.  The accuracy of filterpack techniques has been



 estimated to be of the order of 25 percent for HNO,, and somewhat better for S02 - currently



 adequate for estimating deposition rates, but not sufficiently precise for applications such as the



 testing of regional models..



       A real-time UV fluorescence  technique for continuous measurement of low-level sulfur



 dioxide is commercially available.  Although this is the ideal measurement method for sulfur dioxide,



 it is expensive. Various types of filterpack or annular denuder integrated collection systems have



been used in some networks.  On a 24-hour collected sample, the minimum detection limit, precision,




 and accuracy of the integrated techniques compare favorably to real-time monitors. Samples collected



for periods of a week are subject to problems inherent in the system (such as compound interactions



and gas loss) and therefore tend to  yield greater uncertainties. Considering all of these factors, the



filterpack technique remains the recommended method for measuring SO2 at this time, as the






                                              19

-------
                                                                                  February 1992



 projected uncertainty is within required limits.  The work group also recommends placing low-level



 continuous S03 monitors at several sites with varying concentrations for comparison purposes.



        Although many techniques are available to measure ambient nitric acid, a major end product



 of nitrogen oxide emissions, few of those techniques are applicable to network use.  Concentrations of



 nitric acid are low in rural areas, but dry deposition of nitric acid can add to the total nitrogen



 deposition to forests. For. nitric acid vapor, annual denuder systems (integrated 24-hour) provide



 improved speciation, however, use in networks has been limited because the applicability to weekly



 sampling is not well defined and because additional evaluation is needed. While the filterpack



 technique does not provide an unambiguous measurement of nitric acid, it does provide a



 measurement of total nitrate.  Thus, the filterpack technique is also recommended for measuring nitric



 acid in the network at this tune.



        Adding to total deposition are coarse and  fine particles containing sulfate, calcium, nitrates,



 ammonium, aluminum,  and other metals. The particles usually are collected on a substrate or filter, a



 filter being the case in the filterpack technique, These samplers may or may not have devices to



 separate particles into size ranges before analysis. Chemical Con  chrpmatographic) or physical (X-ray



 fluorescence) techniques will be used for analysis.



       In general, recent developments in measurement methodology indicate a shift toward multi-



 constituent samplers  (such as annular denuders), especially for dry deposition. Multi-constituent



samplers, as well as  integrated sampling methods  (passive samplers) for ozone, could have a



significant effect on network design because of the cost savings potential. Research continues on such



measurement technology.  As  the methods become more suitable for large- scale implementation, they



will be considered for use in the network.
                                               20

-------
                                                                                February 1992



        Observations of vegetation status and leaf area index are made periodically at all dry



 deposition sites so that dry deposition loadings to vegetation can be calculated using the inferential



 approach.



        Weekly sampling is proposed for both of the wet and dry deposition routine networks, with



 the exception of ozone to be measured continuously and cloud/fog deposition to be measured on an



 episodic basis.  More frequent sampling, such as daily/event sampling, may be needed for special



 studies and is the focus of the NOAA/AIRMoN program.  Diurnal sampling (daytime vs. nighttime)



 integrated over a week may give better estimates of dry deposition than a single weekly sample.



        Instrument and sampling protocol development will be an integral part of CASTNET. New



 instruments such as denuders and new protocols  such as day/night sampling will be evaluated with



 regard to precision and accuracy, cost, comparability, and network suitability. Changes in network



 protocol will be made only after thorough evaluation and consultation with the work groups and



 concerned parties, including the states and other  federal  agencies.



 Treatment of Confidence and Uncertainty



        Table 1 shows method  and spatial interpolation uncertainty considerations for wet and dry



deposition; the numbers for dry deposition represent weekly integrated values for inferential as well



as measurement (eddy correlation) approaches.  Table 2 shows the precision,



accuracy, and site-specific uncertainty estimates for the major species measured.  The precision and



accuracy estimates for. site-specific measurements are acceptable in regional stressor monitoring for all



constituents measured by the NADP/NTN and the NDDN except HNQ, in  dry measurements and H*



in wet measurements, which are marginal.  The variability of sulfate wet deposition trend predictions



has been reduced by adjusting the data for the effects of precipitation (as measured by the



NADP/NTN). Future research will incorporate National Weather Service (NWS) precipitation data






                                             21

-------
                                                                              February 1992
     TABLE 1.  METHOD AND SPATIAL INTERPOLATION UNCERTAINTIES
     Species


     Wet

     Dry
           Gases


           Aerosols

           Deposition
           (Inferential)
Method


±5-15%


±5-20%


 ±5%


±30-50%
       }
           Deposition
           (Eddy Correlation/
           Gradient Approach)    ± 15-30%
              Spatial Interpolation
              (current vs. goal)

              ±20-200% vs.  ±25-40%
              ±25-200% vs. ±25-40%
                                              ±50-200% vs. ±25-40%
     Meteorology
±10-50%      N/A
(the NWS has a denser network of rain gauges than the NADP/NTN) to improve the accuracy and

precision of spatial interpolation estimates.             ...

       Statistical analyses conducted to date on the spatial interpolation of air concentration and wet

deposition data indicate that uncertainties in concentration estimates are lower than those of

deposition. It is difficult to determine empirically the accuracy of measurement and inferential

approaches to monitoring dry deposition because accuracy varies according to the species,

vegetation, terrain, and the nature of the major sources affecting the site. By all methods, the

uncertainty generally should decrease as integration time increases. In other words, monthly,

seasonal, and  annual values should yield decreased uncertainty compared to weekly values.
                                            22

-------
 Q
 CM
 CO
       a  g
       '-S3 '5
       fll
CO
I

-------
                                                                                 February 1992


        The gradient approach for HN03 is considered promising because of the large gradient often


 encountered.  Uncertainties in the eddy correlation approach are estimated to be 15 percent for O, and


 =20 percent for S02.  Uncertainties in the inferential approach are greater in all cases: approximately


 50 percent or greater for HNO,, NO,', and SO,2", and 30 percent for SO2 and O,,


        Hie numbers generally reflect the level of experience and accuracy in measuring


 concentrations.  For example, direct eddy correlation measurements of Q, flux have been made for at


 least 10 years, resulting in a refined technique, decreased uncertainty, and a good database for


 parameterizing the inferential method.


        Although eddy correlation flux measurements for S02 are becoming more  common, direct


 measurements for SO/ and HNO, are not,  which is reflected in the high uncertainty of the inferential


 approach.  The statistics for dry deposition uncertainty in Table 1 are for relatively uniform terrain of


 low and uniform vegetation cover.  Uncertainty is greater for tree-covered,  complicated terrain


 because few direct measurements  have been made in such environments and because some of the


 processes are poorly understood.  Extending the inferential approach to estimate deposition on a large
                         . .        .             «•

 area adds additional uncertainty because of the difficulty in characterizing the vegetation cover over a


 large area and because the meteorology and ambient concentrations are more likely to vary


 significantly. Uncertainty estimates for warm-region cloud deposition are based on the Modified

                                                          w'
 Cloud Deposition Model.  Estimates are for a site with a uniform forest canopy, with discrete cloud


 water collection periods in which  the physical input parameters for the model are well characterized.


 Sites and Implementation


       The Total Deposition work group's initial recommendation is that 51 additional site locations


(measuring wet deposition, dry deposition* ozone, or a combination thereof) will be required to fulfill


the mandates of the CAAA. Figures 2  and  3 show maps of existing wet deposition sites




                                              24

-------
r*
I

-------

-------
                                                                                  February 1992



 (NADP/NTN and some Canadian sites) and dry deposition sites (NDDN, NOAA, Wisconsin, Florida,



 and some Canadian sites).



        Figure 4 reflects potential locations of these 51 additional sites and is intended merely as a



 starting point for further analyses and deliberations on specific site selections.  Figure 5 shows the



 site types proposed based on preliminary analyses. The initial recommendation is that of the 51



 proposed sites, 6 would monitor dry deposition only; 14 would monitor dry deposition and ozone; 11



 would monitor dry deposition, wet deposition, and ozone; 8 would monitor wet deposition and ozone;



 and 12 would monitor ozone only.  This results in 31 dry deposition monitoring sites, 19 wet



 deposition monitoring sites, and 45  ozone monitoring sites.  To create the most efficient and cost-



 effective monitoring network possible, it is assumed that wet,  dry, and ozone sites will be collocated



 whenever possible. Although this discussion is focusing on acid deposition and ozone monitoring



 sites, it is not meant to preclude the possibility of collocation with either visibility or air toxics



 monitoring sites. Further,  during actual siting the proximity and availability of existing comparable



 sites will influence final site selection.



       Figure 4 was created from the integration of the monitoring needs for the Total Deposition,



 Aquatic and Terrestrial Effects, and Statistical Network Design work groups.  Implementation of the



 51 proposed monitoring sites is planned in two stages reflecting the likelihood of a multi-year build-



 up to fit within available resources.



       Stage I is composed of 13 sites whose immediate implementation is deemed most crucial to



CASTNET.  Stage n is composed of the remaining 38 key sites. The goal for the Statistical Network



Design group, was to systematically fill gaps in under-represented areas, whether for sensitive



ecosystems such as the Appalachians or for providing spatial coverage adequate to reduce



interpolation  errors to acceptable levels.  This latter goal requires placing some sites within 150 km of






                                               27

-------
                                                          •a
                                                          00
                                                         O
                                                        fe
                                             60
                                            S
                                            V)
jfi
£

-------
29

-------
                                                                               February 1992
        Total implementation of the needed sites will take from one to three years, depending on the

 number of sites in existing networks mat can be upgraded and incorporated into the NADP/NTN or

 NDDN.
STAGE I
3 EutemcoiM
S Northent AppthcbiaD Mwntriiv
4 Mid-Southern ApptUduan Mountain*
1 Uader-fcpneoud ireu in Nonhead
(MB
2 and in South (NC and G A)
TOTAL 13
Number of She*
3
2
2
1
4
3
4
4
1
1
2
2
3
C
TOTAL 31
STAGED
Location
Eotem (2) cod Weftrm (1) coach
Cascade Mountain
Siena Nevada Mountain*
g— f-t |fL _!>•«• |m
Rocky Mcmduai
Gre«tLike»
Untar-KpmHntod mat oi-
Noi1neut/Nof«teutemApi«iMhBBi
Mounlu»(VT. NH. CT, NY)
Mid-Api»bdkaa MMBHUDI (PA)
Midwen(OH)
Phum(MN«ndAR)
Mbnntnu Delta (LA. TX. MS)
South (1 tnek m SC ml PU 2 «ch it
ALadGA)
Relationship with Existing Networks

       In addition to the NADP/NTN wet deposition network and the NDDN dry deposition

network, other networks in the United States will be considered for integration into the CASTNET

program.  Some of these networks are listed in Table 3, "Characteristics of Nonurban Monitoring
                                                                         i
Networks in Norm America." Another potential rich source of sites not listed in Table 3 are those

belonging to state-operated networks.

       As noted in the previous section, specific locations of new sites cannot be identified precisely

at this time, nor can sites from other networks be identified that would be appropriate to include in
                                             30

-------
TABLE 3. CHARACTERISTICS OF SOME NONURBAN MONITORING NETWORKS IN
        NORTH AMERICA
NETWORK
NADP/NTN
MAP3S/PCN
UAPSP(OEN)
EPA-SON
TVA
CARB(CA)
NEW YORK
PADMN (PA)
CLAD (Gnat
Lakes)
NDDN
OEN(UAPSP)
NPS(GASES)
NFS/IMPROVE
NFS
FADMP(FL)
CAPMoN
APIOS-C
APIOS-D
QUEBEC
SITES
200
9
25
27
32
13
7
7
8
55
25
42
16
17
7
4
24
11
38
i
17
4
51
TYPE
Wet only
Wet only
Wet only
Wet only
Wet only
Wet only
We«/Diy
Wet
Wet
WeJ/Diy
Wet/Dry
Diy
Dry/Vis
Dry/Vis
Wet
Dry
Wet
Dry
Wet only
Wet
Dry
Wet only
VARIABLES
(1)
(1)
(3)
(2)
(2)
(1)
(")
(1)
(12)
(1).(5)
W)
O
(8)
(8) .
(«)
(5)
(2)
(10)
<<)
(2)
(5)
0)
FREQUENCY
Weekly
Dairy
Daily
Weekly
14 Day
Weekly
Weekly
Weekly
Weekly
Weekly(cont.Oj)
Daily(cont.NO2)
continuous
continuous
continuous
4-Daily
- 3-Dairy
2-3 Day
2-Daity
Daily
Daily
28 day
Dairy
Dairy
' Weekly
INITIATED
1978
1976
1981
1982
1978
1985
1987
1983
1981-82
1987
1988
1988
1980
1980
1982
1981
1983
1980
1980
1981
STOPPED
Continuing
1991
1988
Continuing
1987
1993
Continuing
Continuing
Continuing
Continuing
1990
Continuing
Continuing
Continuing
Continuing
Continuing
Continuing
Continuing
Continuing
Continuing
AGENCY
NADP/USGS
DOE/NOAA
EPR1
EPA
TVA
CA/ARB
NY/DEC
PA/DER
EPA
EPA
EPRI
NPS
NPS/EPA
NPS
FCG
(Florida Power
Companies)
AES (Canada)
OME (Ontario,
Canada)
Quebec.
Canada
(1) SO^ NOj, Q, PO4> H, NH* Ca, Mg, Na. K, spedfic conductance and precipitation depth.
(2) Same as (1) including SO3.
(3) Same as (1) except conductance not measured. '
(4) Same as (2) including strong acid, total acid, and total organic carton.
(5) Same as (1) except total P and N and including Zn. Fe, Ni, Cu, Pb, Cd, Mn, and V.
(6) 03 (continuous); Our pack SO2 and HNOj vapor, paniculate SO4 and NOj; met data includes windspeed, wind direction,
. temperature, relative humidity, solar radiation, precipitation, and delta temperature.
(7) Same as (1) including At (total), organic carbon, acidity.
(8) O3 (41 sites continuous); SOj (14 sites continuous. 17 sites 2-24 hr. samples/week); met data at 36 sites (see (6)).
(9) Fine Particles and Visibility - 33 sites (16-NPS/IMPROVE, 17 NFS) measuring mass, SO* NO,, H, C, N, O, Na through Pb,
total organic and elemental carbon, all with cameras and IS sites with transmissometers.
(10) Same as (6) plus Q, NH* Na, K. but no met data.
(11) Same as (1) plus NO* Br, F, HPO4 ions for wet samples.
(12) Same as (1) except total P and including Cd, Hg, Pb, Ni. Cr. As, Cu, PC, Al, B, Be, Ba, Co, U, Mn, Sr, Ti, V, Zn.
                                                                1A5/92
                                31

-------
                                                                                February 1992

 the future monitoring program.  Because of differences in siting and sampling criteria, many of the

 sites in existing networks are not suitable for inclusion in CASTNET. Identifying the exact location

 of new sites will require an analysis of the needs in under-represented areas and an analysis of current

 data to determine whether present site density is adequate to meet future data-quality objectives.  It is

 hoped that many new site needs will be met by matching CASTNET requirements with operating

 characteristics of some existing sites under one or more of die referenced networks. Subsequent to

 design, a matching process will be conducted with existing networks to discuss and arrange sites on a

 case-by-case basis.

        The Statistical Network Design work group will be involved in determining the areas and

 numbers of new sites needed for wet and dry deposition. Assessing data comparability of existing

 networks is essential before historical data sets can be merged.  Concerns focus on different levels of

 uncertainty within and among networks which could confound attempts to determine spatial patterns

 and  temporal trends.             	   ,     „  .' '
           . •      '„,../*                           -
 Report Formats               _  	   ...

        Existing protocols for data reporting will be followed. All concentration and meteorological

data will be provided in electronic format for incorporation into the Aerometric Information and

Retrieval System (AIRS). The AIRS system is administered by the  EPA's Office of Air Quality

Planning and Standards (OAQPS) and was put in production in July 1987 as the database management

system for the national database for ambient air quality, emissions, and compliance data. The wet

deposition program will be an enhancement of the existing NADP/NTN program.   NADP/NTN will

continue producing an annual report that lists weekly precipitation chemistry data and precipitation

amounts for each site.  NADP/NTN also produces annual and seasonal statistical summaries for each
                                              32

-------
                                                                                 February 1992



 site.  EPA will, combine these annual summaries with dry deposition data and summaries to produce



 national concentration and deposition isopleth maps.



        The inferential deposition values for dry deposition will be calculated for weekly periods and



 integrated to seasonal and yearly values for inclusion in the AIRS database.  When combined with wet



 deposition data, the air concentration and dry deposition data will be used to produce annual and



 seasonal summaries, spatial maps (when appropriate), and trend statistics for the CASTNET program.



 Future Research Needs



        There are several research needs for total deposition monitoring.  Investigations should focus



 on:



        •  Evaluating the benefit/cost for shorter sample-averaging times,



        •  Evaluating inferential deposition models at sites with different topographical and ecological



           structures.         >            .              .



        •  Improving wet deposition sampling methods at high-elevation sites.



        •  Incorporating hydrogen and ammonium ion stabilizing techniques into wet deposition



           samples.  :       ,:  ,



        •  Determining the applicability of integrated techniques for measuring ozone.



Sample-Averaging Times



        An evaluation of sample-averaging times is recommended to determine whether weekly



sampling is adequate. Research has indicated mat biases of up to 20 percent in the calculated dry



deposition may result when a weekly (168-hour) integrated concentration is used in the calculation



rather than two separate, 84-hour, day-and-night integrated periods. Methods have been developed  to'



adjust for such effects, but as yet the overall accuracy of the inferential method does not warrant such



fine tuning.  If the need for day/night (or some similarly more detailed) dry deposition sampling is






                                              33

-------
                                                                                 February 1992



 indicated, collocation with weekly samplers at a limited number of sites should be a first step.  Hie



 NOAA dry deposition CORE network was designed with the intent to provide side-by-side



 comparisons of routine weekly sampling protocols with weekly integrals of dry deposition



 determinations based on hourly data.  These stations provide an ongoing research basis for tests of



 different sampling protocols.



        For wet deposition sampling, weekly sampling is the U.S. continental norm, but other



 networks in the United States and especially in Canada use daily sampling. In practice, the two major



 goals for wet deposition sampling impose different sampling criteria: for annual and seasonal trends



 detection and for ecological  effects studies, weekly samples are adequate, but for relating deposition



 to specific atmospheric events and for detecting short-term trends from monitoring data, daily samples



 are preferable. The integrated national program of which CASTNET is the keystone must utilize both



 approaches, since a number  of different goals must be addressed. If the need for day/night dry



 deposition sampling or event/daily wet deposition monitoring is indicated,  collocation with weekly



 samplers at a limited number of sites will be a first step in determining the effect of sample-averaging



 times.  Further research underway now will help determine the optimum mix of weekly and daily



 samples in the network.                         ......




 Wet Deposit/on



       Improved sampling methods for high elevations are urgently needed; snow and cloud water



 might be me most significant routes for chemical deposition at high elevations.  Existing equipment



 makes  collection and measurement of these samples difficult, especially in remote areas. In areas



 where sampling on a weekly basis is impossible due to severe weather conditions and access



problems, development of alternative sampling methodologies may be the only viable option. Current



networks, with the exception of six NADP/NTN sites in  Colorado and Wyoming, do not measure wet






                                              34

-------
                                                                                 February 1992




 deposition in high-elevation areas of either the eastern or western United States, even though these



 areas represent some of the nation's most sensitive ecosystems and have the greatest amounts of



 precipitation.



        Currently, wet samples can undergo significant hydrogen and ammonium ton loss over very



 short time periods as a result of chemical reactions whose mechanisms are not fully understood.



 Most of the change in collected samples occurs in the first day.  The Global Precipitation Chemistry



 Program of NOAA has established a method, by the addition of a biocide, for preserving nitrogen and



 hydrogen ions in precipitation.  This methodology has been widely tested, and is available for



 exploitation if further analysis reveals  that the chemical change of deposited materials during storage,



 prior to chemical analysis, is an important factor.



 Dry Deposition        .



         The inferential approach currently used to assess dry deposition is a modeling technique



 through which surface deposition is calculated from ambient concentrations. Additional research  is



 needed to unprove the model's ability  to make accurate estimates.  Such research should focus on



developing unproved empirical and theoretical characterizations of the dry deposition processes and



on refining appropriate measurements  of the governing variables. Past cooperative efforts hi mis area



by EPA, NOAA, and the Department  of Energy (DOE) should be built upon.



       Concerns of die current inferential model are:



       •   Biological interaction of pollutants with vegetation species. .



       *   Impact of water stress on plants.



       •   Parameterization of surface turbulence processes.



       •   Observations and impact of surface wetness.



       •   Deposition to snow cover.






                                              35

-------
                                                                                  February 1992



 A viable research program to address these concerns would involve further analyses of existing



 databases of collocated inferential and eddy correlation measurements.  Additional measurements of



 dry deposition are therefore recommended by direct techniques, such as eddy correlation, and indirect



 methods such as throughfall, and gradient/Bowen approach.



        Research should also determine the most efficient and cost-effective method of collecting the



 concentration measurements on which the inferential approach is based. Currently, the filterpack



 method is used to determine pollutant concentrations, which are multiplied by the modeled deposition



 velocity based on measurements of physical and biological variables. Improving the accuracy of



 pollutant concentration measurements would increase (he confidence in the inferential approach.



 Measurements of nitric acid vapor appear especially vulnerable.



        Because of the potential acute effects  of ozone on biological systems, past development of



 measurement methodology has focused on measurement in real tune. Recent developmental efforts,



 on the other hand, focus on daily or weekly integrated techniques for measuring ozone.  If integrated



 techniques are determined to be applicable to effects monitoring, spatial coverages could be attained at



 reduced cost.                                    - "



 Regional Deposition Modal Evaluation .



       Mathematical models requiring a variety of physical and chemical measurements are used to



provide spatial estimates of dry deposition and cloud deposition.  Uncertainty estimates can be



assigned to model outputs only for specific sites at which chemical and physical parameters are very



well defined, or at which independent verification has been achieved.  Information is available on



model development,  sensitivity analysis of input variables, and evaluation of models at sites meeting



certain criteria.  Such sites generally have uncomplicated terrain and low and  uniform vegetation.



Additional research is needed to evaluate the models at sites with different topographical and






                                               36

-------
                                                                                  February 1992



ecological structures, such as forests in complex terrain for the dry deposition model and non-



homogenous forests for the cloud deposition model.
                                              37

-------
                                     February 1992
THIS PAGE INTENTIONALLY
      LEFT BLANK
          38

-------
                                                                                  February 1992
                        Aquatic and Terrestrial Effects Monitoring




Monitoring Objectives                                   •



       The Clean Air Act Amendments (CAAA) define two categories of aquatic and terrestrial



effects monitoring: effects on water quality, and biological effects on aquatic or terrestrial



ecosystems. Further, Title IV, Section 404 mandates identifying sensitive and critically sensitive



aquatic and terrestrial resources and evaluating the feasibility/effectiveness of an acid deposition



standard or standards to protect them.



       Title DC, Sections 103(c), (e), (j), and 901 (g), of the CAAA requires aquatic and terrestrial



effects monitoring and research and specifically mandates the following:



       1.  Establishing a national network to monitor status and trends of surface water quality and



           forest conditions and to develop monitoring to characterize regional ozone trends.



       2.  Evaluating risks to ecosystems exposed to air pollutants, including characterizing the



           causes and effects of chronic and episodic exposures and determining the reversibility of



           those effects.



       3.  Evaluating air pollution effects on water quality, including the short- and long-term



           ecological effects of acid deposition and other atmospherically derived pollutants on



           surface water (including wetlands and estuaries) and groundwater; and evaluating air



           pollution effects on forests, crops, and soil.



       4.  Continuing the National Acid Precipitation Assessment Program (NAPAP) and providing



           reports on the status of ecosystems (including forests and surface waters) affected by acid



           deposition, as well as reports on the causes and effects of such deposition, including



           changes hi surface water quality, and forest and soil conditions.






                                               39

-------
                                                                                   February 1992



        5. Researching the occurrence and effects of acid deposition on high-elevation ecosystems,



           including forests and surface waters.



        The work group has identified sensitive and critically sensitive aquatic and terrestrial



 ecosystems and also has outlined the appropriate biological and stressor measurements to relate to



 effects.



 Three Types of Monitoring Required



        NAPAP addressed the biological effects of acid deposition on lakes and streams and the



 biological effects of acid deposition and ozone on forests. The results of the aquatics biological



 effects research produced more  definitive answers than the forest research, allowing inferences of fish



 health when changes in water chemistry are known. Considerable research is continuing on the



 effects of ozone and acid deposition on forested ecosystems;  this research will be supplemented



 directly through CASTNET. The monitoring of effects refers in this context to indirect chemical



 measures, such  as acid neutralizing capacity (ANC) and pH,  and direct biological measures, such as



 fish species, for aquatics; and indirect chemical measures, such as soil chemistry, and direct measures



 such as visual damage, growth,  and nutrient uptake for forests.



       The Aquatic and Terrestrial Effects work group determined the need for three types of



monitoring. Two types are effects monitoring: Chemical indicators monitored will be used to



measure the acidity of surface waters and the chemical balance of forest soils, and biological



indicators monitored will be used to assess ecological health.  In addition, atmospheric monitoring



will be necessary to support effects research in sensitive ecosystems as well as to establish a sufficient



database to allow for the interpretive and integrative status and trends assessments required.



Regional-scale monitoring will be needed to address die many different ecosystem types and different



levels of atmospheric inputs.






                                               40

-------
                                       February 1992
              AQUATIC EFFECTS

Water chemical measurements    EMAP/TIME

Water biological measurements   EMAP-Surface Waters

Atmospheric chemistry          CASTNET (with others)
  monitoring

           TERRESTRIAL EFFECTS

                        FHMP (wi«fa USFS)
Biological and chemical
  measurements

Cause and effects research

Cause and effects research
  and some national
  atmospheric monitoring

Atmospheric chemistry
  monitoring
                            GCRP (through USFS)

                            NFS



                            CASTNET (with others)
        For aquatic effects

 monitoring, the Environmental

 Monitoring and Assessment

 Program (EMAPyTemporally

 Integrated Monitoring of

 Ecosystems (TIME) will conduct

 water chemical measurements,

 EMAP-Surface Waters will

 conduct water biological

 measurements, and CASTNET

 (with others as described

 previously, including the

 NADP/NTN and NDDN) will

 conduct atmospheric chemistry and deposition monitoring.  In addition, data on water chemical and

 water biological measurements from federal Class I areas will be available from the USFS's Air

 Resource Management Monitoring program.  For terrestrial effects monitoring, the joint USFS-EPA-

 EMAP-NPS Forest Health Monitoring Program (FHMP) will conduct biological and chemical

 measurements; the USFS Global Change Research Program (GCRP) will conduct cause and effects

research; the National Park Service (NPS) will conduct cause and effects research and some national

atmospheric monitoring; and CASTNET (and others) will conduct atmospheric chemistry and

deposition monitoring.

       Because the issues addressed by the Effects work group are complex and interrelated, some

aspects of aquatic and terrestrial.effects will be discussed separately.
     41

-------
                                                                                  February 1992

 Technical Approach—Aquatics Effects and Stressor Monitoring

        To meet the needs of Title DC for

 aquatics effects assessment, largely created

 for acid deposition control, the monitoring

 design under EPA's Environmental

 Monitoring and Assessment Program

 (EMAP) was enhanced in the form of the

 Temporally Integrated Monitoring of

 Ecosystems (TIME) project. TIME'S goal

 is to estimate, through long-term

 monitoring, the changes and trends in

 chemical conditions in acid-sensitive

 surface waters of die United States that

 result from changes in acidic deposition.

 The TIME project will achieve mis goal

 through a combination of annual,

probability-based surveys of lakes and streams in selected regions and intensive monitoring of a few

regionally representative lakes and streams.  Although TIME itself is a chemical monitoring project, it

has been designed in parallel with the surface waters component of EMAP, which has a broader

ecological focus. The goals of EMAP-Surtace Waters are to:

       •  Estimate the current extent (location, number, surface area or length) of the nation's lakes

           and streams on regional and national scales, with known confidence.
   ENVIRONMENTAL MONITORING
 AND ASSESSMENT PROGRAM (EMAP)

  EMAP (the Environmental Monitoring and
Assessment Program) was established by EPA as a
program aimed at monitoring for results; that is,
confirming that the nation's environmental
protection efforts are truly maintaining or
improving environmental quality. Planning is
being conducted in cooperation with other agencies
and organizations that share responsibilities for
renewable natural resources or environmental
quality.  Over the next five years, integrated
monitoring networks will be designed and
implemented with the following objectives:
  1. Estimate current status, extent, changes,
     and trends in indicators of the condition of
     the nation's ecological resources on a
     regional basis with known confidence.
  2. Monitor indicators of pollutant exposure
     and habitat condition and seek associations
     between human-induced stresses and
     ecological condition.
  3. Provide periodic statistical summaries and
     interpretative reports on status and trends
     to the EPA Administrator and the public.
                                               42

-------
                                                                                  February 1992



        •  Estimate the current status, changes, and trends in indicators of the ecological condition of



           the nation's lakes and streams, on regional and national scales, with known confidence.



        •  Monitor indicators of pollutant exposure and habitat condition within lakes and streams



           and seek associations  between human-induced stressors and ecological condition that



           identify possible causes of adverse effects.



        •  Publish annual statistical summaries on the extent and the status of indicators of ecological



           condition of lakes and streams, and publish periodic interpretative reports on the status



           and trends of indicators of ecological condition of lakes and  streams to die EPA



           Administrator and the public.



        EMAP draws on the success of the National Surface Water Survey (NSWS) in applying a



probability design to regional surveys.  With this design, sites (for example, lakes and streams) are



randomly chosen from a target population (for example, all lakes greater than one hectare in size and



greater than one meter in  depth) within a given region.  This subsample of sites is then sampled, and



results are extrapolated  to the target population that the subsample represents.  As an example, the



NSWS utilized a probability design to make estimates (with known confidence) of the number of



acidic lakes (acidic lakes are defined as those with acid neutralizing capacity, or ANC, <_ 0 jteqL'1)



in seven major regions of the United States. EMAP will extend this approach to monitor long-term



indicators of ecological  health for all major resources (surface waters, forests, wetlands, etc.) of the



United States, without focussing on any specific environmental stress (such as acid deposition or



habitat modification). Indicators  implemented as part of EMAP-Surface Waters will be primarily



biological (species composition of fish, diatoms, zooplankton, etc.), in keeping, with the EMAP goal



of monitoring ecological condition. Probability sites hi EMAP will be sampled on a 4-year rotation,



with one quarter of the sites being sampled each year during a summer  index period (July-August),
                                               43

-------
                                                                                              February 1992
 and returning to the same set of sites in the

 fifth year as in the first year.

         The objectives of the TIME project

 are a specific subset of the objectives of

 EMAP.  The first objective is that TIME

 must be able to make regional  estimates of

 changes (or trends) in acid/base status.

 Secondly, the project must be able to

 detect regional trends  in acid-sensitive

 systems in a policy-relevant time span

 (< 10 years). Thirdly, TIME must be able

 to relate changes in acidic deposition (of

 nitrogen and sulfur) to regional changes in

 the acid/base status of surface waters.

 And lastly, the network should be national

 in scale, but regional in implementation,

 allowing phased implementation in line

 with funding availability.

         In order to make regional estimates

of trends in the acid/base status of surface
    AQUATIC EFFECTS MONITORING
Network Participation Proposed:
 •  EMAP-TTMEandRLTM
 •  EMAP-Surface Waters
 •  CASTNET (with others)

Proposed Number of Deposition and Ozone Sites:
 •  A* described in the Total Deposition section, 51
    ute location* monitoring wet depoiiiion, dry deposition,
    ozone, or a combination thereof

Proposed Effects Monitoring Locations!
 •  TIME- Northeast lake* in 1991. Mid-Atlantic Highland
    ttieamt in 1992 and Upper Midwest streams in 1993.
    Episodic monitoring (RLTM sites) in the Sierra Nevada
    Mountain* and Colorado Rockiea. Northeastern
    dreams, Southern Blue Ridge stream*, Mid-Atlantic
    Coastal Plain streams, Florida streams, sad Florida and
    Northern Cascade lakes later
 •  Surface Waters - Northeast lakes in 1992 and Northeast
    streams in 1993
 •  USFS - Federal Class I areas
 •  CASTNET (MA others) - Highest-priority areas are
    identical to thaw of TIME.  Proposed site locations
    are detailed in the Total Deposition section

Proposed Effects Variables:
 •  TIME - Dissolved oxygen, temperature, site depth, and
    secchi depth in the field. Air-equilibrated pH, closed
    htadspace pH, ANC, specific conductance, SO,*'.
    NO,'. 0-, Ca*.*.- Nt*. Mg»*; K*. NH,*, silica, total  .
    mononieric aluminum, organic monomeric ^Iviriinyni,
    total dissolved aluminum, dissolved organic carbon
. -  (DOC), dissolved inorganic carbon (DIG), color,
    turbidity, total nitrogen, and total phosphorus in die
    laboratory
 •  KLTM - All major ions, pH, ANC, conductance,
    ahimiiMlm Mid DOC
 •  Surface Water* • Chlorophyll; fish, macroinvertebrate,
    •ijrf zooplankton SMTIM ••MJ fltvinrfflnff^i sediment
    diatoms; physical habitat; and possible sediment
    toxiciry, ^*K tiffut c.flntnp*"t«tifin- itwf shoreline bird
    species and abundance
 •  CASTNET fivlth other*) - Proposed wet and dry
    deposition variables to be monitored are detailed in
    the Total Deposition section
waters, TIME will use the same

probability design as EMAP uses.  This probability design, like that of the NSWS, allows results to

be expressed as estimates of population characteristics (such as the number or proportion of acidic
                                                      44

-------
                                                                                  February 1992



 lakes in a region, or the change in mean ANC of lakes within a region over time).  This regional



 focus is important, as effects of emissions reductions will be felt on a regional scale.  Regions for



 TIME will be identified on the basis of two important criteria: (1) the selected areas should exhibit a



 uniform response (change in acidic deposition) as a result of a change in emissions reductions (that is,



 the regions should be airsheds); and (2) the region should contain surface waters with similar gross



 characteristics that will make them sensitive (or insensitive) to acidic deposition. By the first



 criterion, for example, the Northeast is considered a region, but the Adirondack Mountains are not;



 the response to emissions reductions would be expected to be uniform across the entire northeastern



 United States because prevailing wind patterns expose the region to emissions from  the same source



 areas.  By the second criterion, the Northeast would be separated from, for example, the Southern



 Blue Ridge Province, even if the two areas were expected to undergo the same changes  in deposition,



 because the two regions have dissimilar surface water characteristics mat can be expected to make



 mem react very differently to changes in acidic deposition.  High-interest areas will be those where a



 large proportion of surface waters are known to be susceptible to acidic deposition and where



 acid/base conditions are expected to change. This change in acid/base status might  be a response to:



 (1) a future decrease in deposition (for example, as a result of the CAAA emissions reductions); (2)



high levels of deposition in die past (for example, in regions with delayed responses); or (3) future



 increases in deposition (for example, in areas like the mountainous West, unaffected by the CAAA).



High-interest regions for TIME are shown in Figure 6.



       A key factor in the design of TIME is the ability to detect trends in a policy-relevant time



span. The design of TIME, particularly the selection of a sample size (the number  of sites monitored



in a single region over a 4-year sampling rotation), is geared toward detecting trends in regional mean



values  of acid/base indicators (for example, ANC, pH, SO**, NO3~) in 10 years. The strategy for
                                               45

-------
o c
                             I

-------
                                                                                  February 1992


 trend detection in TIME requires that all sites in each region be assigned to a unique subpopulation or


 class.  The easiest way to conceptualize this process is to think in terms of a geographical


 classification. According to this scenario, all sites in one contiguous geographic area (for example,


 the Adirondack Mountains or the Maine coastal plain) would be grouped together in a single class.


 Trends would then be identified separately for each class or subpopulation of sites. .There are two


 objectives in the classification exercise: (1) to lower the site-to-site variability in each class, thereby


 improving the ability to detect significant trends; and (2) to group together sites that are likely to


 show the same response to a change in deposition.  Monitoring for trends in subpopulations has the


 added advantage that TIME can determine which groups of sites (for example, the most sensitive) are


 exhibiting improvements and which sites are not.  The actual method used to identify subpopulations


 for TIME will not be simply geographical, as in the example given here, but will include more


 explicit geochemical and biogeochemical information, and will be designed to make more refined


 distinctions between classes of sites man can be done simply with  geographical location.  The sum


 total of trend test results for each of the subpopulations may then give a more precise picture of


 improvement, or lack of improvement, for the entire region than if trends are examined only for the


 entire regional population. Initial results for the Northeast suggest that TIME will be able to detect


 (with 90 percent certainty and approximately 90 percent power) regional trends of ±5 /teqL"1 in
         t

 ANC,  SO/, and NO,' in 10 years (for example, trends of ±0.5 peqL*1).


        TIME must also relate observed changes in regional acid/base status to regional changes in


 deposition.  This suggests that TIME and CASTNET will need to be able to detect trends in at least


two key acidifying elements, sulfur and nitrogen, and in two separate media, deposition and surface


waters. For most  of the country, we can confidently expect to be able to measure changes in SO**


concentrations in surface waters by sampling regional probability sites on an annual basis.  This is




                                               47

-------
                                                                                 February 1992



 because the relationships between sulfur emissions, sulfur deposition, and surface water SO*



 concentrations are fairly straightforward and direct, and because S04* concentrations are well-



 characterized by sampling in a single index period (that is, SO*2" concentrations exhibit little seasonal



 variability). In some regions, however, ANC and NO3* undergo pronounced short-term changes



 during snow melt or seasons of heavy rainfall.



        The incidence and severity of short-term, or episodic, acidification of lakes and streams is one



 of the largest unanswered questions in the area of aquatic effects of acidic deposition, and one that is



 specifically addressed in the CAAA. Biological damage may result in systems that are not chronically



 acidified, but that do experience episodic acidification, and so the assessment of episodic acidification



 has been made a priority for TIME.  Long-term changes hi ions mat show high seasonal variability



 will not be adequately assessed by sampling probability sites during a summer index period, or during



 any other single index period. In order to monitor changes in the  occurrence of episodic events,



 TIME will utilize a second tier of sampling sites, where monitoring will be conducted on a monthly



 (during most of the year) to weekly (during snow melt) basis. These sites (known as Regionalized



Long-Term Monitoring, or RLTM,  sites), will be hand-chosen to be representative of each of the



subpopulations of sites identified for regional trend testing (described above). The TIME design  will



therefore consist of a number of large regions, each of which is broken up into  a number of coherent



subpopulations. Within each subpopulation, a large number of probability sites will be monitored



annually during a summer index period, and a small number of RLTM sites will be monitored more



frequently. Results from the probability sites will be used to estimate regional trends, while results



from RLTM sites will be used to estimate the occurrence of short-term events.  By explicitly .



associating RLTM sites with classes or subpopulations of sites hi the probability sample, TIME will



also be able to make strong inferences about the behavior of the probability sites (and therefore the
                                              48

-------
                                                                                 February 1992



 target population) outside of the sampled index period.  Examples of questions that could be answered



 with this design are: (1) What proportion of non-acidic lakes or streams in each subpopulation



 undergo episodic acidification during some seasons? (2) How much do spring NO,* concentrations



 differ from summer NO}* concentrations in each subpopulation? and (3) How much do organic acids



 contribute to acidification at different seasons in each subpopulation?



        The temporal changes mat TIME will detect in surface waters must also be related to regional



 changes in sulfur and nitrogen in deposition.  This can best be accomplished by testing whether trends



 in the two media (air and surface waters) are of the same direction and magnitude. Work with the



 TIME design is based on trends hi surface water condition expected to result from a 30-40 percent



 decline in emissions.  The success of the TIME project depends on a similar ability to detect regional



 trends in deposition.  Experience with current methods of deposition monitoring suggests mat changes



 on the order  of ±25 percent over a 10-year period are detectable in SO4* concentrations in deposition



 at single sites.  This level of precision should be adequate if the emissions reductions mandated by the



 CAAA  (30-40 percent) are as expected, but will need to be expanded to the detection of regional



 trends, rather man site-specific trends, and will need to include both sulfur and nitrogen species.  If



 CASTNET can detect regional changes in deposition of ±25 percent, then TIME should have the



 capability to make strong inferential statements about changes in surface water condition attributable



to changes hi deposition.



        The final key objective of TIME is to design a network mat is national in scale, but that is



regional in implementation.  The results of the NSWS put TIME  in a good position to identify those



regions  of the country where concerns for the effects of acidic deposition are warranted.  The ideal



monitoring network would include all of these regions of potential concern.  The financial resources



needed to  support a national network would be substantial, however, and reason dictates that TIME
                                              49

-------
                                                                                 February 1992



 will be implemented in the highest-priority regions.  Additional regions may be added as funding



 permits.  High-priority regions include those where a large proportion of chronically acidic lakes and



 streams currently exist, and where improvements in condition can be expected to result from



 emissions reductions (for example, the Northeast and Mid-Atlantic Highland regions). Chronic



 acidification is rare or absent in some regions, but surface waters have a high probability of



 experiencing episodic acidification; these regions are also of high priority.  Other regions may not



 exhibit chronic acidification at current levels of deposition, but might  be expected to acidify in the



 future despite emissions reductions. Hie setting of priorities for TIME has included all of these



 criteria, and does not focus only on those regions with high concentrations of chronically acidic



 surface waters.



        The TIME project was implemented in the highest-priority region (Northeast lakes) in 1991.



 TIME is scheduled to be extended to streams in the Mid-Atlantic Highlands in 1992, and to the Upper



 Midwest in 1993. In addition, some regions will be monitored using a modified TIME design, which



 includes only RLTM sites.  Regions included in this latter category are the  Sierra Nevada Mountains



 in California and the Colorado Rockies.  Regions mat are not currently funded, but would  rank as



 high priorities, include Northeastern streams, Southern Blue Ridge streams, Mid-Atlantic Coastal



 Plain streams, Florida streams, and lakes in Florida and the Northern  Cascades.  EMAP-Surface



 Waters is scheduled to be implemented in the Northeast lakes in 1992 and in the Northeast streams in



 1993.



       Although TIME has been  designed as a chemical monitoring project, its integration into



 EMAP allows for substantial inference of biological effects.  TIME and EMAP use the same method



 for selecting probability sites, with the result that many sites are common to both monitoring projects.



TIME does, however, have a higher density of sites than EMAP (where required to achieve sufficient






                                              50

-------
                                                                                February 1992



 sample sizes for trend detection), so that not all TIME sites within each region are also EMAP sites.



 In the Northeast, for example, TIME will sample approximately 350 sites over each 4-year cycle, of



 which 250 will also be EMAP sites.  At each EMAP site, there will be data available for fish,



 invertebrate, and algal communities, collected during the same summer index period as TIME data.



 The existence of biological data for a high proportion of TIME sites (for approximately 70 percent of



 the sites in this example) will create important opportunities to interpret TIME results in terms of both



 chemical and biological responses.



        The Ah- Resource Management Monitoring program is another aquatic effects monitoring



 effort operated by the USFS Regions primarily for the purpose of evaluating ah* pollution effects on



 resources in Class I areas. This effort is similar to those conducted by TIME and EMAP-Surface



 Waters, incorporating determinations of lake and stream chemistry with macroinvertebrate and flora



 and fauna surveys.  Their monitoring efforts will provide another potential source for  aquatic effects



 data.                          ...




 Description of Measurements



        At each TIME probability site, a single epilimnetic (m the case of lakes) or grab (hi the case



 of streams) sample is collected during the summer index period (July-August) by EMAP crews.   Field



 measurements  of dissolved oxygen, temperature, site depth, and Secchi depth are made at the same



 tune as samples are collected.  Water samples are shipped on ice to a central laboratory, where



 analyses are begun within 48 hours of sample collection. Laboratory analyses include air-equilibrated



pH, closed headspace pH, ANC, specific conductance, SO,*, N03% Cl', Ca2*, Na*, Mg2+,  K+,



NH4+, silica, total monomeric aluminum, organic monomeric aluminum, total dissolved aluminum,



dissolved organic carbon (DOC), dissolved inorganic carbon (DIG), color, turbidity, total nitrogen,
                                             51

-------
                                                                                February 1992



 and total phosphorus. Quality assurance guidelines have been developed to ensure that measurement



 precision is adequate for TIME'S trend detection goals.



        A modified list of variables is monitored at each RLTM site by individual cooperators in each



 region. Approximately 15 tunes per year, samples for all major ions, pH, ANC, conductance,



 aluminum, and DOC are collected at each RLTM site.  In addition, continuous measurements of



 stream discharge are made at stream sites.



        The EMAP-Surface Water sites will have additional information on chlorophyll, fish species



 and abundance, macroinvertebrate species and abundance, sediment diatoms, physical habitat,



 zooplankton species and abundance, and possible sediment toxicity, fish tissue contamination, and



 shoreline bird species and abundance.



        The Aquatic and Terrestrial Effects work group designed air chemistry monitoring



 specifications, based on the need to tie effects to causes, and passed on its requirements to the Total



 Deposition work group. (Refer to Total Deposition sections on Description of Measurements and



 Treatment of Confidence and Uncertainty for details.)



 Additional Aquatics Research and Monitoring  Programs



 The Adlrondacks Aquatics Effects Program



       The Clean Air Act Amendments require establishing a program to conduct research on acid



deposition effects on aquatic ecosystems in New York's Adirondack Mountains. The Adirondack



Aquatics Effects Program, a multi-year  effort, will  concentrate on the condition of biota in the lakes



and streams of the Adirondack and on determining how changes in deposition levels impact these




waters.
                                             52

-------
                                                                              February 1992




 The EPA EMAP-Wetlands Program



       Wetlands is one of seven broad ecological resource categories EMAP has identified for



 monitoring to determine the current status and long-term trends of conditions.  The objectives of the



 EMAP-Wetlands Program are to:



       •  Quantify the regional status of wetlands by measuring indicators of wetlands ecological



           condition and stressors on wetlands systems.



       •  Monitor changes of these indicators and stressors.



       •  Assess the effectiveness of mitigation of stressors on wetlands condition.



       *  Identify the causes of change in wetlands condition.



       •  Provide annual summaries and interpretive assessments of wetlands status and trends.



       These objectives are a combination of long-term, intermediate, and short-term goals. Over



 the short term, EMAP-Wetlands will provide standardized protocols for measuring wetlands



 condition, as well as estimates of wetlands condition in several regions. Trends detection is an



 intermediate goal. Over the long-term, EMAP-Wetlands will implement programs to identify or



 eliminate causes of change in  wetlands condition.  CASTNET has deferred the wetlands issue to



 EMAP as a future research objective and is relying on EMAP for planning wetlands monitoring to



 address this area.                           .   •    .



Technical Approach—Terrestrial Effects and Stressor Monitoring



       The seven main programs being relied upon for needed terrestrial effects monitoring and



research are the Forest Health Monitoring Program (FHMP), the EMAP-Forest program, CASTNET



Regional  Stressor Monitoring, the Global Change Research Program (GCRP), the NFS monitoring



and effects research programs, the USFS Air Resource Management Monitoring program, and



CASTNET Intensive Stressor Monitoring.  These programs conduct activities for biological,






                                            53

-------
                                                                                February 1992



 chemical, stressor monitoring, and cause and effects research.  Each of these programs will be



 discussed separately below.



        The U.S. Forest Service (USFS), EPA, EMAP-Forests, and the National Park Service (NFS)



 are combining efforts to develop and implement the FHMP to measure the long-term status and trends



 of the condition (health) of the nation's forests. Objectives of this program are to:



        •  Estimate the current status and determine the trends of forest health using a series of



           biological and physical/chemical indicators as a measure of condition.



        •  Monitor pollutant exposure to determine associations between stresses and forest



           condition.



        •  Provide statistical summaries of status and trends and interpretive reports assessing forest



           health.



        Hie FHMP relies on the permanent national sampling framework designed by EMAP,



 supplemented with a survey approach used  by the USFS.  The program will provide regional



 estimates of forest condition by sampling all of EMAP's forest plots every year over the next four



years, and 25 percent every year thereafter. Currently used indicators of forest health are crown



assessments, visual symptoms, growth, and soil characterization.  Indicators under evaluation for



possible implementation are soil chemistry, foliar nutrients, lichen biomonitoring, and vertical



vegetation structure. CASTNET's deposition monitoring (which incorporates the EMAP-Air and



Deposition program) will provide the pollutant air concentration/deposition information required by



the FHMP.



       The FHMP, like TIME for surface waters, is a national program being implemented on a



regional basis.  Data on crown assessments, visual symptoms, growth, and soil characterization will



become available for the Northeast in 1991, the Southeast/South in 1992, and the West in 1993. The






                                              54

-------
                                                                                           February 1992
 Midwest and Intennountain regions

 will be incorporated into this program

 in following years.

         EMAP-Forests, one of the

 major players in the FHMP, is the

 second  program being relied on for

 terrestrial effects  monitoring.  The

 overall  goal of EMAP-Forests is to

 develop and implement a program to

 monitor, evaluate, and report on the

 long-term status and trends of the

 nation's forest ecological resources as

 these resources relate to changes in

 and among  natural phenomena,

 resource management practices, and

 pollutants across the landscape.  .   .

 EMAP-Forests will assess the health
   TERRESTRIAL EFFECTS MONITORING

Network Participation Proposed:
 • USFS, EPA, EMAP-Forests, and NFS - FHMP
 • USFS (with EPA) - GCRP
 • NFS
 • CASTNET (with other.)

Proposed Number of Deposition and Ozone Sites:
 • As described in the Total Deposition lection, 51
    site location* monitoring wet deposition, dry depoiition,
    ozone, or a combination thereof; and 10-15 Intensive
    Monitoring Site*

Proposed Effects Monitoring Locations:
 • FHMP - Northeast in 1991, Southeast/South in 1992, and Wect
    in 1993. Mid-West and Intennounttin region* later
 • GCRP- South in 1991, North in 1992, and Interior West and
    Pacific Coast in 1993
 • NFS - National parks and wilderness areas
 • CASTNET (wUh others) - Priority region* are the Southeast,
    Northeast, Southern California. Pacific Cascades, and the
    Rockies. Sensitive ecosystems of priority for Intensive
    Monitoring Site* an the Appalachian Mountains; die San
    Bernardino, San Gabriel, and Santa Rosa Mountains; and the
    Siem Nevada Mountains
                             out - Crown assessments.
Proposed Effects Variables:
 • Biological and chemical meat
    visual symptoms, growth, and aoil characterization. Possibly
    soil chemistry,, foliar nutrients, lichen biomonhoring, and
    vertical vegetation structure
 • Came and ejffeeo research - Secondary streason being evaluated
    include fire occurrence sad severity, insects and disease, and
    climate cbanfie      ~
 • CASTNET 
-------
                                                                                  February 1992



 forested ecosystems.  Ozone is an important regional pollutant stressor; it is ubiquitous in the eastern



 United States and in parts of the West.  Acid deposition is the predominate regional stressor in the



 Northeast, Upper Midwest, and Mid-Atlantic regions. Figure 7 shows regions of the United States



 that are sensitive terrestrial ecosystems with defined or likely effects from air pollution stress.  The



 work group has compiled a list of prioritized regions for pollution monitoring to be conducted by



 CASTNET and other networks based on their likelihood to experience effects from acid deposition



 and ozone on their terrestrial ecosystems.  These regions also represent areas in which gaps exist in



 the spatial coverage required to meet the CAAA requirements for regional deposition monitoring.



 These regions, in order of priority, are:



        1. Northeast



        2. Southeast



        3. Southern California



        4. Pacific Cascades



        5. Rocky Mountains           ..             .



        The fourth program, initiated by the USFS, is the GCRP.  The GCRP is a nationally



coordinated research effort which will be managed on a regional basis, the four regions being the



North, South, Interior West, and Pacific Coast. In the southern United States, the GCRP conducts



research and monitoring to determine the interactive relationship among forest ecosystems,



atmospheric pollution, and climate change, and uses mis information to manage and protect forest



environments and their associated resources.  The four geographic programs have the following



common objectives:            :



       •   Perform integrated ecosystem-level research. ;



       •   Study the biotic and abiotic interactions that cause changes in natural ecosystems.






                                              56

-------
                                                     §
                                                    *s
                                                    I
                                                    •5
                                                    I
                                                    I
                                                    I
                                                     8

                                                    I
57

-------
                                                                                February 1992



        »  Understand how climate can enhance/mitigate air pollution impacts and bow climate and



           air pollution can combine to cause multiple stresses on vegetation.



        •  Understand how global change might influence the availability of water.



        Each regional program will be tailored to the specific resources at risk. Research topics for



 each region are discussed in the Global Change Research Program Plan published by the USFS in



 May 1990.  The first region, to be implemented in 1991, is the South.



        Through CASTNET, EPA and the USFS Southern Global Change Program (SGCP) are



 cooperating in research and in monitoring effects of potential changes in environmental conditions on



 forest ecosystems. The SGCP emphasizes research on the interaction of stressors and their effect on



 forests.  Highest priority is given to ozone, carbon dioxide, temperature, and moisture, whereas



 secondary stressors being evaluated include fire occurrence and severity and insects and diseases.



 Cooperative efforts between CASTNET and the SGCP include understanding the role of ozone as a



 stressor; determining/evaluating the link of acid deposition, soils, and forest health in the Southern



 Appalachian Mountains; supplying regional climate analyses and climate change scenarios; and



 identifying locations for new monitoring sites for the NDDN and rural ozone monitors.  EPA



 (through CASTNET) will provide regional monitoring and site-specific atmospheric data for cause



 and effect research. EPA (through CASTNET) will provide similar support to the Northeast GCRP



 region in 1992 and to the other GCRP regions starting in 1993.



       The fifth program comprises NPS efforts. The NFS conducts some national atmospheric



 monitoring as well as cause and effects research. CASTNET will incorporate these data into its



program and may supplement the NPS network by monitoring at their research sites. The NPS is



 currently expanding their research efforts on air pollution effects on national parks and wilderness



 areas on an individual park basis.  For example, the NPS is implementing a Great Smokies watershed






                                             58

-------
                                                                                  February 1992



 study, In which NFS will incorporate atmospheric monitoring being conducted by EPA (through



 CASTNET and others) to determine the total deposition on a throughput basis.



        The sixth program is the Air Resource Management Monitoring program mentioned in the



 Aquatic Effects section which is operated by the USFS Regions primarily for the purpose of



 evaluating air pollution effects on resources in Class I areas.  The USFS conducts both wet and dry



 deposition monitoring, but of specific interest to CASTNET, conducts research on the relationship



 and long-term effects of ambient ozone levels on vegetation.



        The final major monitoring effort recommended by CASTNET, Intensive Stressor



 Monitoring, will respond to specific concerns cited in the amended Clean Air Act regarding sensitive



 ecosystems, such as high elevation forests.  In the NAPAP State-of-Science 16 dealing with changes



 in forest health and productivity, concern was expressed about the contribution of cloud/fog



 deposition in addition to ozone and possibly acid deposition to the decline of forested ecosystems.



        Monitoring at these Intensive Sites will support research on the contribution of total (cloud,



 precipitation, and dry) acid deposition and/or ozone to effects observed  in these sensitive ecosystems.



 The aim is to address such issues as the long-term effects of acid deposition on forest element cycles



 and tree nutrition, including: the potential extent, magnitude, and time scale of accelerated



 acidification and nitrogen saturation; and the interaction of these atmospheric stressors with other



 biotic and abiotic stressors such as pests and climate.



        Monitoring  at these Intensive Sites for ozone, wet deposition, dry deposition, and cloud/fog



deposition will follow the same requirements as those planned for the regional stressor monitoring



sites for constituents measured, sample frequency, measurement methodology, and precision and



accuracy. Determining the effects of acid deposition on sensitive ecosystems such  as forests requires



characterizing the deposition profile through the forest canopy and through the tree root-soil structure.






                                              59

-------
                                                                                February 1992



 Consequently, in addition to the measurements to be conducted at Regional Stressor Monitoring Sites,



 stemflow, throughfall, and soil chemistry/nutrient cycling measurements also may be conducted at the



 Intensive Monitoring Sites. Actual CASTNET measurements and siting will depend on the efforts of



 others at any particular site to take advantage of USFS and NFS efforts wherever possible and to



 avoid duplication of efforts. Sensitive ecosystems under stress because of acid deposition and/or



 ozone and considered priorities for Intensive Monitoring Sites are:



        •  Appalachian Mountains



        •  San Bernardino, San Gabriel, and Santa Rosa Mountains



        *  Sierra Nevada Mountains



        *  Cascade Mountains



        •  Rocky Mountains



 All five of these regions are mountainous areas, where deposition is intensified, or near large urban



 centers, where ozone settles on the mountain slopes. Site locations for these areas will be coordinated



 with federal and state agencies conducting research.  Most, if not all, of these sites will be part of the



 CASTNET Regional Stressor Monitoring network and will serve multiple purposes.



 Description of Measurements



       The Aquatic and Terrestrial Effects work group designed air chemistry monitoring



 specifications, based on the need to tie effects to causes, and passed on its requirements to the Total



Deposition work group.  (Refer to Total Deposition sections on Description of Measurements  and



Treatment of Confidence and Uncertainty .for details.)
                                              60

-------
                                                                                 February 1992

 Deposition Sites and implementation

        To provide the coverage needed for a regional ecosystem assessment of conditions and causes,

 SI additional deposition monitoring site locations (monitoring dry deposition, wet deposition, ozone,

 or a combination thereof) are recommended, as detailed in the Total Deposition section.

        The Effects work group also recommends an additional 10 to 15 Intensive Monitoring Sites,

 to be collocated (if possible) with sites from among the proposed 51 regional deposition monitoring

 sites, to complete the requirements mandated by the CAAA. For Stage I in 1992, the following sites

 are recommended:

        •   1-3 sites in the Appalachian Mountains (priority ecosystem number 1).

 As funding allows, the proposed 10 to 15 Intensive Monitoring Sites will be distributed as follows:

                         Number of Sites           Location
                             5-6
                             1-2
                             1-2
                             1-2
                             2-3
Appalachian Mountains
San Bernardino, San Gabriel, and Santa Rosa Mountains
Sierra Nevada Mountains
Cascade Mountains
Rocky Mountains
Relationship with Existing Networks

       A thorough review of current monitoring in rural areas has been completed. Other agencies

and states are being contacted to determine whether mutual monitoring is possible at some of their

existing sites. Gaps exist, so additional air and deposition sites will be needed to provide spatial

coverage to meet regional stressor monitoring and intensive monitoring requirements. The Statistical


                                              61

-------
                                                                                 February 1992



 Network Design work group will provide consultation on the number and location of additional sites.
 Report Formats



        Two levels of reports will be generated by CASTNET; annual statistical summaries and



 biennial interpretative assessments.  Annual summaries of air concentration/deposition data from each



 site on a seasonal and yearly basis, summaries of ecological data, and interpolated data will be used to



 provide regional estimates.  Every two years, an assessment linking stressor and ecological effects



 will be produced.



        For reports on aquatic effects, TIME will provide statistical summaries of chemical data to



 CASTNET, and EMAP-Surface Waters will provide statistical summaries of biological data.



 Regional forest health monitoring data and reports will be provided under the joint USFS-EPA



 FHMP.  The FHMF annual statistical summaries will provide descriptions of regional status and



 trends of forest indicators.  Biennial interpretive reports will provide analysis and assessment of forest



 health. As part of these interpretive reports, various stresses on forested ecosystems will be assessed.



 Stresses to be included are natural, climatic, pests, and anthropogenic stresses such as acid deposition



 and ozone exposure.   CASTNET deposition monitoring will monitor deposition in high-priority



 regions and will provide regional data on the status and trends of acid deposition.  CASTNET also



 will be responsible for interpretative and integrated assessment reports — tying together the effects



 and atmospheric stressor data — produced biennially and used as the basis for required reports to



Congress.



       For reports on sensitive ecosystems, detailed analyses of atmospheric constituent exposure and



deposition will be provided annually for each site.  The analysis  will include time series plots,



monthly summaries, growing season summaries, and seasonal and yearly trends.  The organizations






                                              62

-------
                                                                                    February 1992



 jointly conducting the effects research and CASTNET will cooperate in producing reports and articles



 relating atmospheric exposure and deposition to observed effects.



 Future Research Needs



        A series of watershed studies are needed. These are high-priority projects for both aquatic



 (TIME) and terrestrial effects monitoring (CASTNET); they will provide information on the



 relationship of surface water, forest, and soils relating to nitrogen saturation, causes of episodic



 acidification, and  responses of forests to acid deposition. The studies will include verifying and



 improving existing models, establishing critical loads, and regionalizing site-specific information.



 Integrated surface water/forest/soils monitoring sites will provide maximum information  at greatest



 cost savings.



       Tracking deposition, nutrient flux, soil condition, and surface water chemistry will provide



the first quantifiable indication of ecosystem change from a change in acid deposition.  Priorities for



regional implementation of these studies are the Northeast, Mid-Appalachian Highlands,  and the



Southern Blue Ridge/Great Smoky Mountains.
                                               63

-------
                                     February 1992
THIS PAGE INTENTIONALLY
      LEFT BLANK
          64

-------
                                                                                  February 1992
                             Visibility/Acid Aerosols Monitoring




 Monitoring Objectives



        The legislative mandate for visibility protection began with the Clean Air Act Amendments of



 1977, which called for the prevention of any future and the remedying of any existing impairment



 from man-made air pollution of visibility in Class I federal areas. In Title IX, Section 103(c) of the



 1990 Amendments, the establishment of a national network to monitor (beyond Class I areas), collect,



 and compile data on visibility impairment and  air quality  is required.  The network will characterize



 trends in visibility and acid aerosol as indicators of changing air quality and will provide explanations



 of why these changes occur or, in some cases  where expected, why they do not occur.  Planned



 aerosol measurements at mis time are only for surrogate (optical) visibility measurements.  Research



 on methods and siting is needed before an acid aerosol network related to health effects can be



 designed. This research is ongoing with results expected in time for CASTNET 1993 network



 enhancement.                 ~



        In Title Vm, Section 169B was added to specifically address visibility research issues for



 Class I areas, giving EPA the lead role.  Sources of visibility impairment as well as regions with



predominantly clean air were to be studied, including expanding current visibility-related monitoring



 in largely western Class I areas;  assessing current sources of visibility-impairing pollution and clean



 air corridors; adapting regional air quality models for visibility assessment; and studying the



atmospheric chemistry and physics of visibility.



        The Visibility work group explored issues concerning visibility and acid aerosol, including



their significance, measurement methods, design considerations, regulatory requirements, and model



evaluations. The work group recommends a network design that will use existing air quality






                                               65

-------
                                                                                   February 1992



 monitoring programs to meet CASTNET objectives in the most comprehensive, efficient, and cost-



 effective manner, building largely upon the NFS and IMPROVE (Interagency Monitoring of Protected



 Visual Environments) programs developed for federal Class I areas and national parks (described



 below).



 Technical Approach



        Hie national monitoring network is required to track the trends of pollution resulting from



 emission reductions.  Two key elements expected from emissions reductions are improved visibility, a



 welfare effect, and acid aerosol reduction,  which has health effects.  Both health and welfare effects



 research issues are addressed in the Title DC mandate.



        Visibility responds readily to changes in air quality. In virtually every attempt to quantify



 economic effects or benefits of air pollution, visibility has been highly valued by the public and is



 perceived as an index of health risk (visibility is closely related to acid aerosols and organics). Acid



 aerosol is an emerging health effect issue, and although it is currently under consideration for



 designation as a criteria pollutant, virtually no data exist for status and trends analysis of acid aerosol.



       Visibility impairment in the United States, other than mat caused by precipitation events and



 fog, is primarily attributable to anthropogenic fine particles and gases, such as sulfur oxides, nitrogen



 oxides, and hydrocarbons, emitted from urban and industrial sources. Upon emission, many of the



gases convert to aerosols.  Haze is a mixture of gases and secondary aerosols which form within 100



km of a source such as  an urban center, power plant, or other industrial facility.  After pollutants are



transported hundreds of kilometers, the haze which is formed is composed mainly of fine primary and



secondary aerosols  such as sulfate and organic aerosols.  Forms of natural aerosols that also affect



visibility are condensed water vapor (water droplets), wind-blown dust, and their primary  and



secondary aerosols  (including natural organics).






                                               66

-------
                                                                                        February 1992

         The Visibility work group

 reviewed past trends in baze using

 airport data (Figure 8) and discussed

 model output scenarios from the

 Regional Acid Deposition Model

 (RADM) as well as other related

 sources of information. EPA

 regional offices polled their states

 for visibility or acid aerosol

 monitoring efforts and for

 recommended areas suitable for

 visibility monitoring sites.  These

 polls revealed that only a few states

 have acid aerosol or visibility

 monitoring programs.

        After this review, the

 Visibility work group established a design for visibility and acid aerosol monitoring intended to detect

a significant change within the seasonal or annual averages of visibility and its indicators.  The design

goal is to provide an estimate of selected visibility indicators for any region of the country with a

relative error of ±50 percent, with a 95-percent confidence level.
 VISIBILITY/ACID AEROSOLS MONITORING

 Network Participation Proposed:
    NFS
    IMPROVE
    NESCAUM
    Other States
    Others

 Proposed Number of Visibility Sites:
,  • 12 "full" and 20 aerosol-only sites

 Proposed Visibility Monitoring Locations:
  • Full sites will be located in: (1) Areas where significant
     change is expected (in sulfate concentrations in New
     York and the Ohio River Valley, and in mobile
     source concentrations in California); (2) Areas east
     of the 105th meridian (Rockies) and west of the
     Mississippi River where there is a dearth of data; and
     (3) The central states located along the east-west
     transition. corridor
  • Aerosol-only sites will provide more uniform spatial
     coverage and refinement in areas with complex
     pollution scenarios at substantial cost savings

 Proposed Visibility Variables:
  • Atmospheric optical properties (total light extinction),
     visual scene (photographs), and fine particle
     composition (to include elemental, organic, and total
     carbon; acidity; mass; sulfate; nitrate; and the trace
     dements sodium through lead)
                                                  67

-------

-------
                                                                                 February 1992



 Description of Measurements



        There are three types of visibility measurements:



        •  Optical — optical properties of the atmosphere (total light extinction) are monitored to



           provide a scene-independent measure of air quality.



        •  Scene — characteristics of .a scene, viewed at a distance, are monitored to document the



           scene-specific visibility.



        •  Aerosol — the aerosol characteristics are determined so that atmospheric optical properties



           can be associated with the responsible pollutants.



        Acid aerosols can be measured by adding denuders to the aerosol instrumentation used for



 visibility.  Supplemental data such as meteorology and continuous gaseous concentration data are



 important for correct interpretation.



        Optical Monitoring:  The best choice of optical equipment depends on the characteristics of



 each site.  Although several methods are used for monitoring optical properties of the atmosphere, the



 two methods most commonly employed are integrating nephelometry and transmissometry, each of



 which has advantages and disadvantages.  The atmospheric extinction coefficient is essential to



 understanding how atmospheric aerosols affect the visibility of targets.  The nephelometer measures



 the scattering coefficient of particles, which is the major portion of the total extinction coefficient.



 The nephelometer, however, may modify the particles by heating them, causing evaporation of



 associated moisture and resulting in an over-estimation of die visual range.  Nephelometers also suffer



 from the fact that they yield only point measurements. Calculations of atmospheric extinction using



the transmissometer are sensitive to both scattering  and absorption, and they measure effects of



different-size particles in the ambient aerosols. Methods do not yet exist to routinely account for light



scattered into the  sight path of the transmissometer, which hi remote locations without continuous






                                              69

-------
                                                                                February 1992



 visual observations, make it difficult to remove the effects of cloud and precipitation from the data



 base.  The major drawback to the transmissometer is that it has difficult siting requirements in that a



 long visual path is usually required. The ultimate choice between the two measurement options is



 therefore left to be decided by the characteristics of the site involved.



        Scene Monitoring:  Photos taken with an automated camera are recommended for scene or



 view monitoring.  This method allows for perception studies, trend evaluations, and sensitivity



 assessments of a view to changes in air quality. Additional information yielded from this method



 includes frequency and intensity of plumes and elevated haze levels associated with local sources.



 This approach, however, requires accurate recording of brightness, color,  and spatial detail of the



 scene.  Without these data, it is difficult to make meaningful  comparisons  among different scene-



 specific conditions. The work group recommends that photos be taken three times a day, every day



 at 9:00 a.m., 12:00 p.m., and 3:00 p.m.    .



        A erosoi Monitoring: The work group also  recommends that CASTNET measure fine



particle composition with the Modular Aerosol Monitoring Sampler currently used by the IMPROVE



Program to determine which atmospheric constituents are responsible for changes in visibility



impairment. The aerosols associated with visibility reduction are mainly fine particles, with light



scattering attributed primarily to particles of less man 2.5 /tm in diameter. The aerosol measurements



required are elemental, organic, and total carbon; acidity; mass; sulfate; nitrate; and the trace



elements sodium through lead. Of the four filter modules in  me IMPROVE sampler, three collect



fine particle samples (2.5 fan), whereas the fourth samples respirable particles (< 10 /tin).  A



summary of the equipment and analyses for the optical, scene, and aerosol measurements is presented



in Table 4.  Keep in mind that aerosol monitoring is being planned  as a visibility surrogate only, and



that an aerosol health network is not being proposed at this time.






                                             70

-------
                                                                           February 1992
     TABLE 4.  SUMMARY OF VISIBILITY EQUIPMENT TYPES AND ANALYSES
Device
Nephelometer
Transmissometer
35-mm camera
Fine particle
sampler:
Module A: fine
Module B:fiae
Module C:fine
Module D.-PMIO
Measurement
>
Fine particle
scattering
Atmospheric
extinction
Visual scene
25-mm teflon
47-mm nylasorb
25-mm quartz
25-mm teflon
Frequency
Hourly
Hourly
3 times daily
24-hour, every
third day
24-hour, every
third day
24-hour, every
mud day
24-hour, every
third day
Analyses



Mass, absorption
elements (H, Na-Pb)
Nitrate
Organic and elemental
carbon
Mass
       Research continues to enhance the IMPROVE aerosol sampler recommended by die work



group. It should be noted that some researchers have experienced problems in the field with critical



orifices clogging on some samplers. As well as continuing to study and document the current



IMPROVE system, the CASTNET Instrumentation/Methods work group recommends using a mass



flow controller-based flow system at a few sites, which will provide good



control and give a continuous flow output readable by a data logger.  After adequate data have been



collected for comparison of the two configurations, a benefit/cost analysis can be performed.



Additional modification to die IMPROVE sampler protocol, such as use of a larger-diameter filter,



will reduce potential filter clogging problems at more polluted sites. Using the IMPROVE sampler




                                           71

-------
                                                                                 February 1992



 will preclude die need for parallel sampling at a variety of sites to ensure data comparability with the



 National Park Service (NFS) sites, which, as discussed below, will be an integral part of this



 monitoring effort. National Weather Service (NWS) meteorological data (for example, relative



 humidity and temperature) will be used to help validate local instrumentation data that may be used in



 modeling efforts.



 Treatment of Confidence and Uncertainty



        The inherent uncertainty in optical measurements falls within 10 to 15 percent.  Uncertainty



 of aerosol data varies depending on the element.  Uncertainty cannot be quantified for camera data.



 In developing trends in extinction owing to different species, uncertainty levels are expected to be 10



 to 15 percent for sulfur, 20 to 30 percent for organics, and 20 to 30 percent for water/particle



 interactions.  No estimates exist for the uncertainty in regional acid aerosol trends, although the level



 of uncertainty is expected to emerge from the Summer 1991 Acid Aerosol Study.



 Sites and Implementation



        The Visibility work group designated high-priority areas for visibility monitoring (Figure 9)



 after reviewing siting of existing visibility networks, such as IMPROVE, reviewing model outputs



 from RADM and the Engineering Aerosol Model (EAM), exploring the consequences of expected



 shifts in urban sources and the possible trading of emissions, and defining the east-west transition area



 and other areas that are simply lacking available visibility data.



        The work group determined that augmenting the fully equipped IMPROVE and NFS networks



 ("full" sites) would yield the best and most cost-effective national  coverage.  Collocating sites with



 existing air quality monitoring sites, such as those for wet (NADP/NTN) and dry (NDDN)



deposition, would result hi substantial  cost savings. IMPROVE and NFS sites are located in national



parks and in federal Class I areas and  can provide only limited coverage between the 95th and 105th






                                              72

-------
                                                  •a
                                                  i
                                                 t
                                                 Ch
73

-------
                                        f
                                       £•

                                       I
                                       1
                                       I
                                      I
74

-------
                                                                                    February 1992



 meridians, but they leave few inadequately covered areas in the West.  The work group recommends



 that 12 "full" sites and 20 aerosol-only sites (see Figure 10) be added to provide complete national



 coverage in sufficient detail to conclusively delineate the relationship between visibility changes and



 air quality.



        An individual site that does not represent the surrounding area can bias spatial pattern and



 trend  estimates, leading to inappropriate inferences.  Sites in remote regions exert a disproportionate



 influence on spatial isopleth patterns.  Because many areas in the country do not have enough



 quantifiable visibility monitoring data for a statistical analysis of network design, the work group used



 expert opinion in designating areas for recommended site locations.  As the Statistical Network



 Design work group determines sulfate distributions, this information will be used to locate new sites



 and evaluate existing ones.



        Sites were chosen to complement, not duplicate, data collected by the IMPROVE and NFS



 networks.  Preference was given to nonurban sites; areas with little other monitoring coverage; areas



 with high current emissions levels or those predicted  to have the greatest change in emissions (by



 RADM); and areas in which spatial and statistical patterns are most complex. The 12 "full" sites



 were located in:                           , •     -



        1.  Areas in which a significant change is expected: in sulfate concentrations in New York



           and the Ohio River Valley; and in mobile source concentrations in California.



        2.  Areas east of the 105th meridian (Rockies) and west of the Mississippi River where there



           is a dearth of data.



        3.  The central states located along the east-west transition corridor.



The 20 aerosol.sites will provide more uniform spatial coverage and refinement in areas with complex



pollution scenarios at a substantial cost savings.
                                               75

-------
                                                                              February 1992



        An alternate design for siting is to implement sufficient coverage in some areas predicted to



 change most (by RADM, EAM, etc.), so that trends can be detected on a smaller regional scale, with



 large gaps between regions. This alternative design is not a viable option, however, because it



 provides insufficient spatial coverages to achieve the national goals of the CAAA mandate.



        The goal is to implement the visibility network during a two-year period, half being



 implemented each year.  If funding is not available for the complete network, the work group has



 assigned priorities to site locations so that expected changes can be tracked for specific regions.  To



 determine trends on a national scale, the full CASTNET network is required, as is continuation of the



 other networks on which CASTNET depends. An oversight committee will be formed to coordinate



 visibility monitoring efforts, such as IMPROVE and NFS hi federal Class I areas, to monitor other



 networks' program viability and  direction.



 Relationship with Existing Networks



        In 1980, EPA issued regulations requiring visibility monitoring, new source review, and long-



 term strategies for protecting visibility in Class I areas. EPA has implemented these monitoring



 requirements through a cooperative effort with Federal Land Managers and certain state



 organizations, called the Interagency Monitoring of Protected Visual Environments (IMPROVE),



 which is funded by EPA State Grants and the NFS.



        In addition to IMPROVE, other significant air quality monitoring efforts include the NFS,



 USFS, NDDN, NADP/NTN, and NESCAUM, all of which vary substantially in monitoring,



 analysis, and regional coverage.  The USFS sites are camera-only,  and the NESCAUM sites are



 aerosol-only. The IMPROVE  and NPS networks meet CASTNET recommendations because they



have complete visibility measurement equipment, including transmissometer or nephelometer, aerosol



sampler, and 35-mm camera.






                                             76

-------
                                                                               February 1992



        CASTNET's success depends on continued operation of current IMPROVE, NFS, and



 proposed Eastern IMPROVE sites for the next 10 years.  CASTNET coordination with IMPROVE,



 NFS, and NESCAUM sites will enhance each of these programs.  For example, establishing a



 CASTNET site in parallel with California's visibility network will result in operational savings and



 comparability with other California sites. It is anticipated that other state programs will contribute



 significantly. NESCAUM will continue to operate  its aerosol-only sites, for which CASTNET will



 conduct the filter analyses.  Moreover, EPA Health Studies and various Visibility Transport



 Commissions (as authorized hi the CAAA) will benefit from sulfate/nitrate and acid aerosol data



 collected at CASTNET sites.



 Report Formats



        CASTNET will follow existing protocols for data reporting. Reports will be issued annually,



 with quarterly breakouts,  following the current IMPROVE schedule.  All aerosol and optical data



 will be deposited in AIRS. For special research needs, (invalidated optical data will be available the



 next day, camera data will be available quarterly, and aerosol data will be available six months after



 the close of a quarter. The work group recommends annual reports to document and summarize



 available data for the science community. Biennial  interpretive reports, using graphics such as those



 in Figure 8, are also recommended to exhibit national trends.



       The network data will be used to indicate die average seasonal visibility for die nation, with a



 resolution of about one state area.  Data from the network will be used with other CASTNET data to



study the impact of specific source groups on air quality and visibility.



 Future Research Needs



       Because the CASTNET visibility network design depends on the continuation of other



networks, a contingency plan is needed to prepare for possible failure of one or more of these






                                             77

-------
                                                                                  February 1992



 networks.  The aforementioned oversight committee will coordinate with other visibility efforts to



 monitor other networks' program viability and direction.



        To ensure data quality and comparability, the work group recommends developing an external



 quality assurance program that works with all networks. A centralized database that includes



 mechanisms for data distribution will need to be established between the different networks and the



 scientific community.



        Acid aerosol methods and procedures research and site characterization studies must be



 initiated to provide complete pollutant characterization and size distribution profiles that will help



 determine the sources and sulfate species responsible for visibility impairment.  For example, it is



 known that the particles most efficient at scattering visible light (light scattering is usually going to



 dominate over light absorption in remote areas) are those with diameters between 0.1 and 0.9 /on.



 But additional instrumentation, with an on-site operator, is required to classify these fine particles,



 which makes routine network deployment prohibitively expensive at this time. Special studies to



 classify the distribution of particle sizes could provide important information on the causes of



visibility impairment at a greatly reduced cost.   Other studies to support needed research are the



EPA's Acid Aerosol Study at Union Town and the NFS Acid Aerosol Summer Study at Shenandoah



National Park. It is hoped that mis research will lead to an acid aerosol-health component within



CASTNET.
                                              78

-------
                                                                                February 1992
                                   Air Toxics Monitoring




Monitoring Objectives



       Hie Clean Air Act Amendments (CAAA) specify two monitoring requirements that are of



concern to the Air Toxics work group: the "Great Waters" program, which monitors deposition of



hazardous air pollutants (HAPs) to specified water bodies for assessing the resultant environmental



and human health effects, and the Area Source Program, which monitors ambient concentrations,



sources, transformation processes, and public health risks from HAPs.



Great Waters Program



       Title m, Section 112(m), of the CAAA requires that EPA, in cooperation with the National



Oceanic and Atmospheric Administration (NOAA), conduct a program to identify and assess the



extent of atmospheric deposition of hazardous air pollutants, and other pollutants at the



Administrator's discretion, to the Great Lakes, Chesapeake Bay, Lake Charaplain, and coastal waters.



Because the study covers many significant national  public trust waters, and to distinguish it from other



ongoing, related efforts, the study is referred to as  "the Great Waters Program."



       The Great Waters Program is required to include:



       •  Atmospheric deposition monitoring.



       •  Investigations of sources and deposition rates of air pollutants as well as their



          transformation precursors/products.



       •  Monitoring methodology research.



       •  Determination of relative contribution of ah* deposition to total loading in the waters.



       •  Evaluations of adverse effects from deposition, including indirect effects to health and to



          the environment.






                                             79

-------
                                                                                 Febniaiy 1992



        •  Assessments of contribution of such deposition to violations of water quality standards.



        »  Biological sampling to identify the presence of HAPs mat deposit from the air.



        Some water body-specific requirements also are listed, the most important being the



 requirement for one hazardous air pollutant sampling station per Great Lake by 12/31/91. The



 requirements of Section 112(m) either directly dictate the needs of the Great Waters Program or make



 them inherently necessary for a mandated report to Congress.  A report is due to Congress, in



 cooperation with NOAA, in 1993 and biennially thereafter and is required to include, at minimum:



        •  The relative contribution of HAPs to total loading of the listed waters.



        •  HAP-caused environmental and human health effects to listed waters.



        •  Sources of HAPs.



        •  Determination of whether HAP loadings cause or contribute to water quality violations or '



           violation of the Great Lakes Water  Quality  Agreement (GLWQA).



        •  Description of regulatory revisions  (to the Clean Air Act and other applicable federal



       .... . laws) necessary to ensure protection of the  waters.                 -  •



Based on mis report and within five years of enactment, the Administrator of EPA is required to



promulgate any further regulations deemed necessary and appropriate.



Area Source Program



       Title HI, Section 112(k), of the CAAA requires the EPA to conduct a research program, the



Area Source Program (also known as the Urban Area Source Program), to support a national strategy



to reduce risks from hazardous air pollutants from area sources in urban areas. The research program



must include:
                                              80

-------
                                                                                February 1992



        *  Ambient monitoring in a representative number of urban locations for a broad range of



           HAPs, including, but not limited to, volatile organic compounds (VOCs), metals,



           pesticides, and products of incomplete combustion (PICs).



        •  Characterizing the sources of the HAPs by focusing on area sources and their contribution



           to public health risks.     ,.      .



        •  Considering transformations and other factors that may elevate the risks to public health.



The legislation requires a preliminary research report to Congress in November 1993 and a



comprehensive national strategy by 1995.



       The national strategy must identify:



       *  At least 30 pollutants that pose the greatest threat to public health in the largest number of



           urban areas.



       *  Source categories that individually or together present a threat of adverse effects to human



           health or the environment.



       •   Source categories that together represent 90 percent of the area source emissions of the 30



         .  aforementioned HAPs.     .



       •   Schedule of actions to reduce urban cancer risk by at least 75 percent by controlling HAPs



           emissions from all stationary sources.                                          '



       •   Research needs in sampling and analysis methodology, modeling, or pollution control.



       •   Recommended regulatory changes to further the CAAA goals.



       •   Provision for ambient monitoring and emissions modeling to demonstrate progress toward



           strategy goals.
                                              81

-------
                                                                                February 1992



As a part of the strategy, ambient monitoring and emissions modeling also are required, as



appropriate, to demonstrate that the goals and objectives of the strategy are met.  Future CASTNET



monitoring and network refinements are the intended means of meeting these latter needs.



       The Air Toxics work group's goal is to construct a program to meet the mandated CAAA



deadlines on schedule and to provide the essential information for sound regulatory decisions.  To



design an efficient, cost-effective program, the work group recommends supplementing existing or



planned stations and expanding as possible to meet legislative deadlines.



Technical Approach



       To design a program for air toxics monitoring, the work group was required to address both



die Great Waters and Urban Area Source perspectives.  The following are specific objectives and



recommended approaches of each of these program areas:



Great Waters Program



       A national monitoring program should be implemented consisting of the following steps On



order of priority):                          .



       1.  Establish the initial network of comprehensive stations (Integrated Atmospheric Deposition



           Network (IADN) master sites), one per lake (two in Canada and three in the United



           States), which will measure nutrients, precipitation, pH, conductivity, particles, VOCs,



           semi-volatile organic compounds (SVOCs: pesticides, polychlorinated biphenyls (PCBs),



           etc., both in precipitation and in air),  polycyclic aromatic hydrocarbons (PAHs),



           meteorology (such as temperature, wind  speed, and relative humidity), and elemental



           compounds (in both precipitation and in air).



       2.  A Lake Michigan integrated, pilot, mass balance study should be established to answer



           questions on siting, network design, and  basic deposition processes.






                                              82

-------
       INTEGRATED ATMOSPHERIC
         DEPOSITION NETWORK

    The Integrated Atmospheric Deposition Network
  (IADN) is a joint effort between the U.S. and
  Canada and was created to fulfill Annex IS of the
  Great Lakes Water Quality Agreement (GLWQA).
  The objective is to acquire sufficient, quality-
  assured data to estimate with a specified degree of
  confidence the loading to the Great Lakes Basin of
  selected toxic substances. The network will consist
  of several master (research grade) stations
  augmented by a number of satellite (routine)
  stations.  •
                                                                                 February 1992

        3. Existing deposition monitoring

           sites on Lake Champlain and

           Chesapeake Bay should be

           expanded to measure particle

           mass, the ratio of coarse/fine

           particles, elemental

           composition, and other

           compounds of interest, using a

           dichotomous (or similar)

           sampler.

        4. New preliminary sites should be added for coastal estuaries measuring particle mass, the

           ratio of coarse/fine particles, and elemental composition.

        5. The program should be expanded to add more sites, or to add additional important

           pollutants, or altered to correct problems.

        The use of a dichotomous sampler for preliminary monitoring of Lake Champlain,

Chesapeake Bay, and the coastal estuaries allows for a relatively low-cost, reliable means of attaining

a broad geographic representation of elemental deposition to the Great Waters.

        The contribution of atmospheric pollutants relative to total loading can be determined by

calculating atmospheric loading through deposition monitoring (with adjustments for meteorological

variability), verified by periodic intensive studies, and by incorporating the atmospheric contribution

into mass balance modeling. The adverse effects of HAPs loading on human health and the

environment can be determined in three steps.  The first is to determine human exposure to HAPs

through the water, the second and third steps are to determine the atmospheric contribution to
83

-------
                                                                                February 1992

 exposure of aquatic life to HAPs, then

 determine bioaccumulation and subsequent

 health and environmental effects.

 Modeling and other techniques, with

 monitoring results for trace chemicals, can

 be used to identify sources of HAPs.  The

 approach recommended to determine

 departures from water quality criteria

 (established by the Federal Water Pollution

 Control Act, the Safe Drinking Water Act,

 or GLWQA) is to determine the

 atmospheric contribution to water column

 concentrations, using atmospheric loading

 information.  Hie final objective of the

 Great Waters air toxics monitoring is to supply the information needed so mat EPA can recommend

 regulatory revisions to prevent adverse effects.  This objective will be met by determining the

predicted improvement attributable to existing regulations and by identifying additional load

reductions needed.

Area Source Program

        A national monitoring network will be  developed by installing monitoring sites in populous

urban areas, as feasible. Recommended steps for establishing the monitoring network, in order of

priority, are:
      AIR TOXICS MONITORING
     GREAT WATERS PROGRAM

Network Participation Proposed:
  •  IADN

Proposed Number of Toxics Sites:
  •  Five IADN Master Stations, one site per
     Great Lake

Proposed Toxics Site Locations:
  •  One site in Canada on Lake Huron (Burnt
     Island), one on Lake Ontario (Pt. Petre),
     and, in the U.S., one each on Lake
     Michigan (Sleeping Bear Dunes), Lake
     Erie (Sturgeon Point) and Lake Superior
     (Keweenaw Peninsula).  Chesapeake Bay,
     Lake Champlain, and coastal estuaries later

Proposed Toxics Variables:
  •  Rain (pH, conductivity, nutrients); particle
     mass and size; trace elements (in particles);
     pesticides, PCBs, and PAHs (in air and
     precipitation)
                                             84

-------
           .    .                                                                 February 1992

        1. Identify and characterize the scope of existing urban toxics monitoring stations and

           programs.

        2. Establish an Urban Area Source monitoring network by augmenting selected enhanced

           ozone monitoring sites with sampling for hazardous VOCs, metals, pesticides, and PICs.

           Consideration will be given to sites that can also serve as part of the Great Waters

           network.               .

        3. Enhance measurements as needed to identify sources and human health risks, or to

           demonstrate progress toward goals of the national strategy.

        4. Expand the network as feasible.

        An EPA multi-office work group will assess existing urban monitoring data to identify the

 broad range of HAPs present in urban areas, and then to identify the 30 pollutants that pose the

 greatest threat to public health in the

 largest number of urban areas.. They will

 also identify the source categories that

 represent 90 percent of me aggregate

 emissions of those pollutants. Exposure  .

 and risk will be estimated from available

 data on emissions, concentrations,

populations, and the pollutants' adverse  .

 effects on human health. Sources of the

pollutants will be identified both by

emission inventories and by apportionment modeling.  As research provides more information, these

lists will be refined.
      AIR TOXICS MONITORING
  URBAN AREA SOURCE PROGRAM

 Network Participation Proposed:
. r • Enhanced Ozone Monitoring Network  .
[•ff> .  . _, ,

 Proposed Number of Toxics Sites:
   • Supplement selected "**&*****& Ozone sites
      for air toxics measurements
 -~-*  . ,*       .  '  •• *
 Proposed Toxics Site Locations:
  "• Selected serious, severe, and extreme ozone
         latiainmtvit cities
 Proposed Toxics Variables:
  • VOCs, metals, pesticides, and PICs
                                              85

-------
                                                                                February 1992



        The ultimate objective of the Area Source program and its ambient air toxics monitoring



 network is to supply the information needed to develop regulatory revisions to reduce adverse effects.



 Monitoring and modeling studies are also required to assess progress as the national strategy is



 implemented.



 Identification of Affected Areas



        The Great Waters program will address the significant public trust waters listed in the Act,



 including the Great Lakes, Chesapeake Bay, Lake Champlain, and coastal waters.  Coastal waters are



 defined as those areas designated as either EPA National Estuary Program (NEP) estuaries or as



 NOAA National Estuarine Research Reserves (NERR).  These coastal waters comprise 19 NEP



 estuaries and 27 NERR estuaries, geographically ranging from Maine to Washington, touching nearly



 every coastal state on the continent, and including sites in Hawaii and Puerto Rico.



        The limitless nature of the CAAA mandates and budget realities concerned preclude the initial



 study of all the designated waters and will force the work group to consider the minimum  needs of



 the toxics programs.  To meet the purposes of the CAAA in identifying problems and assessing



 regulatory needs, initial monitoring will emphasize methodology assessment and priority issues.



 Consequently, in defining a national atmospheric deposition network, monitoring will be focused on



 the better-studied waters and on existing (such as: the three New York and three Massachusetts



 Institute of Technology sites, one each on Lake Erie, Lake Ontario,  and Lake Champlain; the two




Vermont sites on Lake Champlain; and the five sites on the Chesapeake Bay operated by the



 University of Maryland (two), Virginia Institute of Marine Science (one), and the University of



Delaware (two)) or planned stations and will be expanded as budget allows to the other water bodies,



specifically the less-studied Great Lakes, Lake Champlain, Chesapeake Bay, and coastal waters.



Coastal stations not on Chesapeake Bay will be selected to represent the continental U.S. coastal






                                              86

-------
                                                                                 February 1992



 regions:  North Atlantic, Mid-Atlantic, South Atlantic, East Gulf of Mexico, Central Gulf, West Gulf,



 South Pacific, Mid-Pacific, and North Pacific.



        The Area Source program is concerned with human exposure.  As a result, the areas of



 interest are urban locations with large populations. The first step of the Area Source Program is to



 identify the broad range of HAPs (from which will be determined 30 or more) mat present the



 greatest human health threat. Urban areas to be studied will overlap those areas that are affected by



 the enhanced ozone monitoring regulations since ozone exceedences also tend to occur in the nation's



 most populous areas. Under the CAAA, VOC monitoring will be required for ozone nonattainment



 areas classified as serious, severe, or extreme. These 25 areas will present a ready opportunity for



 collocation of sites for toxics monitoring.



 Description of Measurements



       A program to measure toxic air pollutants must address their various forms, including volatile



 organic compounds,  semi-volatile organic compounds, metals, and particle-bound species.  Critical to



 the calculation of deposition estimates are the size distribution of particles, as well as the phase



 distribution, or the proportion of the toxic pollutant that is in the gas vs. particle phase.



       Great Waters Program: To support modeling calculations, several "non-target" tracer



 compounds must be measured.  For example, to separate the contribution of residential wood



 combustion from mobile source emissions, "non-target" tracers like potassium or isooctane may be



 measured.                                                      .    .     .



       Great Waters preliminary stations should provide information on rain (pH, conductivity,



 nutrients), particle mass, trace materials (in particles), and particle sizing.  The standard, low-volume



dichotomous sampler gives mass,  size distribution (coarse from 2.5 pm to 10 /un, and fines below 2.5



jim), and trace elements from analysis of 37-mm teflon filters.  Measuring trace elements determines






                                              87

-------
                                                                                 February 1992



 the concentration of some toxic compounds (for example, lead, cadmium, arsenic, and so forth) and



 provides tracers for source identification. A high-volume sampler also gives the total paniculate



 mass, a sample for determining total organic carbon, and elemental and volatilizable carbon



 measurements that are useful for source apportionment.



        Semi-volatile organic carbon compounds, which exist in gas and particle phase at ambient



 conditions, are collected using an XAD/PUF (sorbent/polyurethane foam) cartridge in line with a



 filter so that both gases and particles are available for later analysis. Hie number and size of samples



 required will depend directly on the number of pollutants of interest and their expected



 concentrations.



       Gases or VOCs are collected in 6-liter, summa-polished, stainless-steel canisters and analyzed



 at a central laboratory. Although mere are a number of otter equally acceptable methods for



 collecting VOC samples, this method is recommended for its reasonable cost and ease of use in



 remote sampling locations. Hie fewest number of different analytical laboratories should be used to



 assure quality assurance measures are met.



       Hie work group has established protocols for sampling. Integrated samples should be



 collected over 24 hours.  When some special study samples are being collected, two 12-hour samples



 are preferred over one 24-hour sample to allow determinations of significant differences in daytime



and nighttime conditions, especially with respect to particle concentration  and size distribution.



Weekly samples  are generally taken at random, one 12- or 24-hour sample every 6 days, to allow for



random sampling of different days of the week.



       Area Source Program: The sampling schedule for areas affected by the enhanced  ozone



monitoring regulations (The Enhanced  Ozone Monitoring Network) will be eight 3-hour samples for



VOCs and four 6-hour samples for aldehydes, either every day or every third day, depending on

-------
                                                                                February 1992



 population. The Air Toxics work group recommends supplementing this VOC monitoring with toxics



 sampling at several sites, with preference given to those sites located on or near water bodies of



 interest. The VOC sampling schedule may necessitate a different approach to air toxics monitoring



 than in the Great Waters program.  The VOC monitoring would be expanded to include more toxic



 VOCs. Monitoring for pesticides, toxic metals, and PICs would  be identical to methods under the



 Great Waters program.



        Meteorological Factors:  Integrated samples during periods of intensive field research



 should be collected daily for 12-hour periods (or less) for the reasons discussed above.  Because



 sampling across multiple meteorological conditions is undesirable, allowances should be made for



 changes in synoptic conditions.  Despite the difficulty hi coordinating all field programs to make use



 of meteorological data, sample protocols should be adjusted when it becomes obvious through the use



 of simple isobaric trajectory forecast models, National Weather Service products, or other field-tested



 techniques  that sampling is likely to occur across multiple air masses in a single sampling period.  If



 adjustments are not possible, such periods of record should be flagged in the final data  sets using post



 facto meteorological information so mat data users are aware of potential limitations.



        Station S'rtina:  Because the initial five stations in the Great Waters program also will be



 IADN sites, station siting will follow existing IADN protocols, which specify nonurban settings with



 no significant sources of particles, SVOCs, or VOCs near enough to the monitoring stations to have



 any measurable impact.  IADN also specifies location requirements including acceptable height above



ground, distance from trees and other obstructions, and location of roadways or sources of traffic.




Future Great Waters site locations should include urban and  nonurban settings.
                                              89

-------
                                                                                 February 1992



        Urban-influenced sampler siting protocols can be studied in the 1991 Lake Michigan Air



 Toxics Study and the Lake Michigan integrated pilot study. This information will be integrated into



 future site selection procedures.



 Treatment of Confidence and Uncertainty



        A number of factors complicate establishing precision and accuracy levels for toxic air



 pollutants:



        •  Data for these compounds have either been collected relatively recently, are not fully



           evaluated, or are non-existent.



        •  Analytical costs of collocated  sampling have prevented establishing a sufficient database.



        •  Reference samples for blind laboratory analysis do not exist for many of the toxic



           compounds.



        •  Accuracy determinations are more difficult for complex  mixtures of related compounds,



           such as PCBs and dioxins.



       Although precision and accuracy levels have not been determined for many of the toxic



compounds of interest, they can be estimated to establish Data Quality Objectives (DQOs) once



sufficient information on variability is established. The level of detection (LOD) or level of



quanthation (LOQ) of the analysis procedure is a reasonable starting point, particularly in the absence



of any other information on method variability.  Precision and accuracy levels will be established



when quality assurance blind reference  standards are available, when laboratory analysts gain



experience with the toxic compounds, and when sufficient information on method variability is



obtained. The data collected under the Area Source Program is to be used in conjunction with



modeling to evaluate progress toward reducing the cancer risk from area sources by 75 percent.
                                              90

-------
                                                                               February 1992



 DQOs must be established to permit this determination in the presence of significant meteorological



 variability.



 Sites and Implementation



        To meet the requirement of one site per Great Lake for measuring HAPs deposition by the



 end of 1991, IADN placed one site in Canada on Lake Huron (Burnt Island), one on Lake Ontario



 (Ft. Petre), and, in the United States, one each on Lake Michigan (Sleeping Bear Dunes), Lake Erie



 (Sturgeon Point), and Lake Superior (Keweenaw Peninsula). Additional sites are recommended in the



 Chesapeake Bay, Lake Champlain, and the coastal estuaries. .It is anticipated that the existing state



 and university operated sites previously described will be excellent candidates for monitoring of both



 the Chesapeake Bay and Lake Champlain.  The CAAA do not specify the number of sites or



 deadlines for these non-Great Lake monitors.



       The Air Toxics work group recommends that the initial Great Waters sites adopt a minimum-



 sampling approach as is in place for the IADN master stations, sufficient to meet the CAAA-required



 deadlines.  The work group determined that implementing a large network covering all potential toxic



pollutants would not be cost-effective, considering the complex nature of the research issues. In



 addition to meeting the deadlines mandated by the CAAA, the work group recommends a minimum



sampling approach in other sites for geographic representation coupled with a research program in the



form of a comprehensive mass-balance pilot study on Lake Michigan.  Lake Michigan was chosen for



the pilot study to support development of the Lake-wide Management Plan (LaMP), because a



significant preliminary urban air toxics study was conducted for 1991, and because additional



sampling is being planned for the first of the lake-wide mass balances. (Like IADN, LaMP was



spawned by the GLWQA.  The mass balance of each Great Lake is an important part of these



management plans.)






                                             91

-------
                                                                                 February 1992



        The Lake Michigan pilot study can provide critical information on siting, network design, and



 representativeness (urban vs. rural, land vs. water).  Intensive, daily sampling will be conducted



 during a three- to four-month period at multiple sites in and on the lake.  It would be highly desirable



 to monitor during different seasons of the year to clarify the pronounced seasonal concentration



 patterns of pollutants such as PCBs.



        Urban area source measurements of toxic air pollutants can overlap with VOC measurements



 to be made by the enhanced ozone monitoring network for State Implementation Plan (SIP)



 development as required by CAAA. Sites are to be located within the urban area of each of the 25



 serious, severe, and extreme ozone nonattainment areas.  To monitor urban area source pollution,



 CASTNET will use at least one enhanced ozone monitoring site in each urban area design. The



 measurements at the enhanced ozone site will be supplemented by other types of samplers (for PICs,



 metals, and pesticides) and  by increased  analysis of VOCs to include toxic compounds such as carbon



 tetrachloride and vinyl chloride as well as the VOCs needed for ozone modeling. Sites located near



 Great Waters areas would be given high priority, because they would serve dual purposes.



        In addition to technical considerations, the Air Toxics work group must coordinate both



 monitoring and research resources and activities.  For example, the Urban Area Source Program will



 require coordination with the Enhanced Ozone Network. Such a well-defined, designed, and



 integrated approach will allow a systematic examination of the complex research issues as well as an



 efficient utilization of resources.



 Relationship with Existing Networks



       The proposed CASTNET network will share resources to the maximum extent possible with



existing and planned networks of all federal, state, or local agencies. Samplers will be added as



necessary in each of the networks for a common sampling array at all locations, but this overlap will






                                              92

-------
                                                                                February 1992




                        Network                           Minimum Number of Sites




                        Great Lakes                                   15



                        Pilot Mass-Balance on Lake Michigan          8-10



                        Lake Champlain



                        Chesapeake Bay



                        Coastal Estuaries



                        Urban Air Toxics
                                             TOTAL
    2



    3



 8-10



 8-10



44-50
be allowed only when important common needs and quality concerns can be met.



        Plans call for using the data from the EPA Toxics Air Monitoring System (TAMS) sites in



Boston and Houston, which were recently terminated (8/91), as the base of the Urban Area Source



program.  These site locations also are being considered for inclusion in the enhanced ozone



monitoring network. The Air Toxics work group will incorporate planned enhanced ozone



monitoring sites into their efforts, if at all possible.



       The monitoring requirement for five sites in the Great Lakes by December 31, 1991, has been



met by accelerating the schedule for the U.S.-Canadian-funded IADN.  Existing state-operated sites



can be used as initial sites in the Chesapeake Bay and Lake Champlain areas if arrangements suitable



to all parties can be agreed upon.



Future Research Needs



       There are a number of early research needs associated with Great Waters monitoring to



ensure mat monitors are appropriately sited and models are based on realistic processes.




Investigations should focus on but are not limited to:
                                             93

-------
                                                                                  February 1992



        •  Determining the representativeness of data from land-based sites used to characterize



           deposition over water.



        •  Determining the representativeness of data from nonurban locales used to characterize the



           deposition to the entire lake surface.



        •  Collecting sufficient data to assess parameters and define physical and chemical processes,



           such as dry deposition rates (velocities), transmedia flux, particle sizing (including



           pollutant concentration by particle size), and phase distribution.



        •  Determining atmospheric reactivity and transformation of toxics.



        •  Determining transboundary and long-range transport.



        •  Evaluating natural source impacts, such as erosion.



        •  Assessing environmental and human health effects.
        Urban Area Source Program research needs which are to be addressed in part or in whole



tinder CASTNET include, but are not limited to:



        •   Determining initial broad range of HAPs to be monitored.



        •   Developing meteorological methodologies for determining mixing heights.



        •   Developing data analysis procedures for source strength attribution.



        •   Establishing human health risk assessment methods for the HAPs to be monitored.



        •   Compiling health assessment data for urban pollutants.



        •   Determining whether one sampling site per city is representative of the urban toxics



           mixture.



        *   Characterizing the effect of mixtures in urban exposure scenarios for non-cancer



           endpoints.






                                               94

-------
                                                                                 February 1992



        Key unresolved issues for network design are the total number of sites needed in the final



networks, the frequency of sampling necessary, and site locations. Data management issues include



formatting and archiving data, and establishing procedures for obtaining a good emissions inventory.



Consideration of these data management issues is necessary for modeling activities, for evaluating the



effectiveness of implementation measures taken for control of sources, and for predicting the impact



of future control measures.



        The aforementioned research issues are unresolved because of a dearth of information on the



spatial and temporal patterns of these pollutants and on the extent to which vegetation and bodies of



water remove or introduce pollutants from or into the atmosphere. In addition, technical issues need



to be addressed regarding sampling/analysis limitations, sampling media, procedures/protocols,



sampling time, sample handling, shipping, analysis, and data reporting.  Particular focus should be



directed at developing methods for sampling and analysis of toxic compounds of interest which cannot



currently be measured, and at standardizing and improving presently available methodologies.



        The work group recommends a mmmqim monitoring approach until these research issues are



resolved, enabling the work group to complete network design criteria.  At mat time, the network



should be expanded in order of the priority steps previously described.
                                              95

-------
THIS PAGE INTENTIONALLY
      LEFT BLANK
                                     February 1992
          96

-------
                                                                                  February 1992
                    Statistical Network Design for Status and Trends




        The process of air and deposition network siting and data collection will be the critical factor



 in obtaining valid statistical information on deposition status and trends.  Network design is difficult



 for air and deposition variables that vary in both time and space because these variations are usually



 neither random nor well behaved.  Examining the following aspects of network design will ensure the



 ultimate provision of data that allow estimates of ecosystem exposure and adequate assessment of



 trends to a desired level  of precision:



        •  Air and deposition variables of interest.



        •  Integration of existing network data.



        •  Frequency of field sampling.



        •  Media representation and area! coverage.



        Criteria in each of these areas form the basis for an optimal CASTNET network design. As



there is a threshold level of sites required to perform any sort of meaningful analysis, this



methodology has been applied only to wet deposition, dry deposition, and ozone. There are simply



too few toxics sites to allow for reliable statistical assessment of network design at mis time.  The



statistical design of the visibility network is underway with assessment of candidate variables and a



review of existing networks for possible inclusion in the design.



Air and  Deposition Variables



       Core variables represent those species that are considered to affect adversely or beneficially



the health of ecosystems  or to represent criteria air pollutants whose levels should respond to



emissions reductions. The Statistical Network Design work group has been advised by the Total



Deposition and Effects  work groups that the core wet deposition variables are SO/, NO,', H+, and






                                               97

-------
                                                                                 February 1992



 rural O3 for ecosystem exposure and temporal trends analysis. Proposed core air concentration



 variables are SO4*, Q,, HNQj, S02, and NO,'.  As tbe CASTNET program objectives evolve,



 variables may be added following a thorough evaluation of available monitoring and analytical



 methods for each new variable.



 Integration of Existing Monitoring Network Data



        Several factors justify focusing on information from existing networks for which established



 quality assurance and data comparability exist. First, such collaboration significantly reduces the



 effort required to implement an integrated monitoring network, and it reflects CASTNETs role to



 supplement and integrate, not replace, these networks. Second, the data can provide current status



 and trend information for most of the atmospheric variables.  All data will be evaluated for potential



 contribution to the final, long-term monitoring network.



        Determining which network sites to include is part of network design and requires considering



 the objectives and spatial coverage of each network, quality assurance/quality control (QA/QQ



 associated with the data, and compatibility of network monitoring and data validation protocols.  Site



 selection for spatial pattern and trend analyses may greatly affect the statistical results.  Expert



judgment will be used hi conjunction with quantitative assessment in designing the network.



 Frequency of Field Sampling



        To establish a valid monitoring network, the effect of averaging times requires careful study.



Monitoring must be conducted on time and distance scales of die same magnitude as the duration of



changes in variable deposition/concentration levels.  If possible, monitoring on a more refined time



scale is preferable to that intrinsic to the trend or spatial pattern under study. Even large-scale



changes can be misinterpreted when observations are averaged over long periods.
                                              98

-------
                                                                                February 1992



        Successive weekly sampling periods should provide the level of accuracy and precision



 required to satisfy the estimation goals for seasonal and annual trends for most of the core wet and



 dry variables. Rural ozone measurements will be computed according to the definition of the SUM06



 variable — the variable frequently used to characterize rural ozone, which is the sum of successive



 hourly ozone measurements above 0.06 ppm from April through October.



        For purposes of detecting changes in air quality and in deposition that can be directly related



 to changes occurring hi emissions from specific regions on a smaller scale, daily sampling appears



 optimal. The NOAA monitoring programs are constructed around this premise, and will be designed



 accordingly, in conjunction with the EPA CASTNET design.



 Media Representation and Areal Coverage



        Although atmospheric wet deposition variables should  be monitored over the continental



 United States, budget limitations may initially restrict complete implementation to high-priority



 regions or sensitive ecosystems.  The primary factors to be considered in network design are the



 spatial distribution of sensitive ecosystems and sources of pollutant emissions.  Because of scarcity of



 siting or sampling equipment limitations, current deposition networks have under-represented areas,



 such as high-elevation lakes and streams in the West and Eastern coastal areas.  Correcting these



 monitoring problems is the first priority for the Statistical Design Network work group.



 Desion ot Optimal Network



       Because the environment can never be sampled without error, determining the degree of



 sampling uncertainty mat can be tolerated is an immediate concern. The network design must satisfy



design goals and meet the estimation requirements of several user groups. CASTNET serves two



main user groups within the scientific community:  monitoring users who are interested primarily in



status and trends information; and ecosystem groups that require spatial estimates of






                                             99

-------
                                                                                  February 1992




 concentration/deposition for relating pollutant exposure to ecological health.  CASTNET has three



 broad monitoring goals hi meeting the needs of these user groups, and they are to:



        1.  Characterize in nonurban areas the status and trends of near-surface air concentrations and



           deposition for regional/ecosystem areas.



        2.  Confirm that predicted results of control programs are achieved for chemical pollutant air



           concentration and deposition.



        3.  Establish specialized concentration/deposition monitoring at ecosystem process study



           research sites.



        The ah- and deposition network should allow the detection of significant, long-term (seasonal



 and annual) temporal trends and spatial patterns for the core monitoring variables.  Determining the



 spatial distribution of the core variables will require interpolation of data among monitoring sites.



 Uncertainty for these estimates will depend on the natural variability, measurement precision, and



 network design—the latter depending primarily on site density and location. If the uncertainties of



 interpolated values provided by existing networks are too great, site density may need to be increased.



 In addition, CASTNET should determine the response of the core variables to changing emissions



 levels, a process mat requires assessing the sensitivity of existing networks hi detecting changes over



 time. Short-term trends caused by meteorological variations must be distinguished from long-term



 trends caused by changes in emissions. Long-term trends caused by changes hi climate will be



difficult to  separate from anthropogenic trends, but need to be studied.



       For the core monitoring variables, the  specific estimation and network design objectives are



to:



       1.  Estimate seasonal and annual spatial patterns over nonurban areas within a relative



           interpolation error of less than 50 percent at systematic grid locations.






                                               100

-------
                                                                                  February 1992



        2. Estimate average seasonal and annual deposition for die specified deposition areas with



           average relative errors of less than 40 percent.



        3. Estimate total change in deposition from data observed to date at existing monitoring sites



           and for average deposition within the regional areas.



        4. Assess the capabilities of deposition and air quality monitoring networks to detect



           hypothesized future reduction scenarios for the core variables. This analysis will



           determine the scope of monitoring needed to detect a trend of particular type and will



           provide guidance on the potential need for additional monitoring to reduce time to



           detection.                               .



        The final network design must reflect consideration of data collection economics and intended



 uses of the data by deposition trends and ecosystem groups.  The current location of sites may not



 prove sensitive to trends and may yield unacceptably large uncertainty levels associated with point or



 ecosystem/regional estimates. Either deficiency may dictate adding or relocating monitoring sites to



 improve CASTNETs ecosystem  estimation capabilities.        .



 Preliminary Findings



 Wet Deposition



        Soatial Interpolation: The work group recommends locating additional sites in under-



 represented high elevation and coastal ecosystem areas.  The analysis presented below necessarily



 excludes these  areas, and the interpolation results are valid for areas representative of the



 NADP/NTN siting criteria.  An analysis of NADP/NTN annual 1989 wet sulfate,  nitrate, and pH



data indicated that the relative errors of interpolation across most of the eastern United States were



less than SO percent and that the regional errors were below 40 percent, except in  the West. Kriging



predictions are based on the correlation  in measurements of neighboring sites (currently, mere are






                                              101

-------
                                                                                 February 1992



 very few sites within 150 km of one another, particularly in the West).  Consequently, it is



 anticipated that the error of interpolation could be reduced in regions characterized by high relative



 errors by locating sites within 150 km of existing ones. To provide critical information on non-



 monitored sensitive ecosystems, the work group recommends locating new sites at high-elevation



 remote areas and coastal areas. Future research will incorporate NWS precipitation data to improve



 the precision of spatial interpolation on annual  and seasonal time scales.



        Trend Detection: One of CASTNET's primary concerns is whether future deposition



 monitoring will be capable of detecting changes in annual sulfate deposition in an accurate, timely



 fashion.  Familiarity with existing networks' detection and quantification capabilities is required for



 evaluating current networks and for designing new or extended networks.  An analysis of existing wet



 deposition NADP/NTN sites in the eastern United States was conducted to determine whether this



 network  could detect and quantify the total RADM-projected sulfate deposition reduction (reduction of



 10 million tons with no trading) in seven steps  at 1994, 1995, 1996, 2000, 2001, 2002, and 2003 (see



 Figure 11).  The probability of correctly detecting a decreasing change in deposition is at least 80



percent by the end of the CAAA Phase I reductions in 1996 for the eastern half of me country.



These results do not apply to the Mississippi delta, where the probability is low («40 percent by



1996) due to the inadequate number of sites in  this region and the Appalachians where little



monitoring information exists at high elevation areas.  The probability of estimating the change in




sulfate (quantifying the trend) to within 20 percent of the projected change ranges from 40 to 65



percent by 1999.  Increasing this probability to 80 percent would require monitoring to 2001 for die



Midwest, South, Mid-Atlantic, and Northeast regions. The variability of annual sulfate wet



deposition has been reduced by adjusting the data for the effects of precipitation (as measured by the



NADP/NTN). The work group recommends an additional 19 wet deposition monitoring sites in high






                                              102

-------
                              Reliable
                             Detection

                                 y
                 93   94   95    96   97    98   99
   Reliable

Quantification

,      T
00    01    02   03
            5-
           10
Percent

Reduction
           15
           20
           25
           30
                                                  i     t
Figure 11. Wet sulfate regional trend assessment
                                     103

-------
                                                                                   February 1992



 elevation and coastal areas to provide the critical information required on these non-monitored



 sensitive ecosystems for adequate spatial resolution.



 Dry Deposition



        An extremely limited pool of data exists for dry deposition analyses.  Analyses similar to



 those for wet deposition are being attempted using air concentration variables (SO3, SO^, and HNO3)



 as surrogates for dry deposition. In the case of dry deposition, spatial fields are not as easily defined



 as for wet deposition, because dry deposition varies greatly from place to place even when air



 concentrations are the same.  With so few existing sites, there is very poor characterization of the



 spatial fields, resulting in large gaps. Because of the spatial irregularity of dry deposition (much like



 the temporal irregularity of wet deposition), interpolation among existing data is particularly



 vulnerable to error. Detection of trends in dry deposition can easiest be considered for each specific



 site at which appropriate air concentration measurements are made. For trends over large areas,



 detection relies on a modeled translation introducing additional error. This is complicated by the lack



 of a historical data set.  The work group recommends 31 additional dry deposition monitoring sites to



 enhance trend quantification.  At the same time, efforts will be ongoing to develop methods for



 constructing improved area! averages (through improved inferential modeling) on the basis of these



 data, on annual and seasonal scales.



 Ozone



       To increase the spatial resolution of ozone in sensitive ecosystems of interest and hi large



forested areas (terrestrial ecosystems) in the Southeast, the work group recommends an additional 45



ambient rural  ozone monitoring sites. The data from these sites will also provide the concurrent



ozone and deposition data needed to differentiate  if potentially adverse effects are due primarily to



ozone or to dry deposition.






                                               104

-------
                                                                               February 1992
                                    Data Management




 Recommendation



        The Data Management group's most important role is to develop a comprehensive program of



 standardization to ensure mat all CASTNET data, which will be provided by myriad entities, are of



 comparable quality. Comparable-quality data are relatively easy to achieve for NAAQS variables for



 which standard monitoring guidelines exist. For the other variables that will be monitored, collection



 and analytical methods are not standardized. Although similar hi concept, the methodologies diverge



 in important ways in bom the  collection and analytical phases.  A comprehensive data standardization



 program is the first step in building a uniform database.



        The Data Management group recommends EPA's Aerometric Information Retrieval System



 (AIRS) as the eventual archival and reporting system for atmospheric measurements.  AIRS is



 currently limited to the NAAQS, meteorological, some toxic, and visibility measurements, but  it can



 be expanded and modified to manage CASTNET data.



        Meanwhile, the existing NDDN and Acid Deposition System (ADS) database systems will be



 merged into a new system that will serve as die archival and retrieval system for acid deposition and



 acid aerosol measurements. The Atmospheric Research and Exposure Assessment Laboratory



 (AREAL) will oversee receipt and validation of contractor-supplied data during the AIRS transition.



Additional databases will be managed separately, such as dry deposition calculations and interpolated



 (kriged) area deposition grids. AIRS will be the source database for all acidic deposition calculations.



Databases external to AIRS will use common designs, architecture, and methodologies to the extent



possible to permit close integration with AIRS and other distributed systems, such as die



Environmental Monitoring  and Assessment Program (EMAP).






                                             105

-------
                                                                                  February 1992



        Initial users of CASTNET data will be EPA regional offices, program offices, and scientists



 interested in the extent of current deposition in particular regions. Congress has called for periodic



 updates on the status, trends, and potential impact on ecosystems of acid deposition, ozone, and air



 toxics through a series of mandated reports. Future regulatory actions may be based on the



 broadening database, necessitating provable data quality.  Generally, it is the intent of CASTNET



 managers to prepare biennial assessment reports based on this data, and release the data itself within



 one year  of its being quality controlled and entered into the AIRS system.



 Data Collection and Storage



        Data are collected and stored for ongoing projects and several special-purpose studies.



 Sampling intervals include hourly, weekly, bi-weekly, monthly, seasonal, yearly, and episodic, or by



 event.  Camera data are three 35-mm slides per day.  Sample averaging times include daily, weekly,



 monthly,  quarterly, seasonal, and yearly.  Both sampling  interval and sample averaging times are



 pollutant-specific and collection-method-specific.



        Scientists retrieve information from a number of databases, including AIRS/Air Quality



 Subsystem (AQS) and EMAP.  Because certain information is available only in hard copy, the group



 recommends*



        •  Developing a database "clearinghouse" of acid rain reference material.



        •  Developing an abstract bibliography of related materials with key word-search capability,



          especially for acid deposition, air toxics, and visibility.



        *  Providing on-line laboratory and field standard operating procedure manuals.



        Reporting criteria important to researchers include ad hoc, or customized, reporting format  •



capability; easy access; standardized reports for pollutants such as ozone and acid deposition,
                                              106

-------
                                                                                 February 1992



 including accepted statistical summaries for the data; and selection by monitoring network, site, and



 special study name.



        Frequency of existing database access varies from daily, weekly, quarterly, to yearly, and is



 expected to increase with the CAAA implementation efforts underway.



        The CASTNET data management system should include interactive and batch processing



 capabilities; help screens; menu-driven software; PC front-end, report-generator, graphics/Geographic



 Information System (GIS) capability; and a technical and user-support hotline. The work group



 indicated that such a system would store related data in a single database, which would provide quick



 access and better comparability of data as standards are defined.



 Initial System Concent



        The data management system will be a collection of databases, screening and acceptance



 criteria, retrieval options, reports and associated analyses, and graphics capabilities (see Table 5).



 The database consists of a catalog of metadata (descriptive and summary information) that facilitates



 access to information stored in the main data repository.



        Figure 12 shows the CASTNET information flow and basic system components required to  •



 satisfy the needs of the CASTNET user community. Acquisition equipment for air pollutants is used



 to obtain raw data, which will be converted to a format for input into the repository database. The



 converted data will be stored in a temporary hold file for quality assurance/quality control (QA/QC)



processing.



 Quality Assurance/Quality Control                                                        .   ;



        The two forms of QA/QC are data processing, which verifies the data integrity of the



 converted data, and scientific, which verifies the quality of raw data by flagging the values and



ensuring proper Standard Operating Procedures (SOPs) are followed. Reports will show the status of






                                              107

-------
TABLE 5. SYSTEM INPUTS, PROCESSES, AND OUTPUTS
            Inputs
      Processes
        Outputs
 Acid deposition data
   • APIOS-C
   • APIOS-D
   • APN
   • CAPMoN
   •NADP/NTN
   • MAP3S (historical)
   •TVA
   • UAPSP (historical)
   •GARB
   •FADS
   •GLAD
   •MGCP
   • NDDN

 Aquatic and terrestrial effects
   • NADP/NTN
   - NDDN
   • MAP3S (historical)
   • NPS
   • EMAP
   •NFHM
   •TIME

 Visibility impairment  • .   * •
   •NPS
   •TVA
   • IMPROVE

Acid aerosol data
   •NPS
   •NDDN
   • IMPROVE

Air toxics
   •TAMS
   • Extended TAMS
  •IADN

QA/QC indicators
User interface

QA/QC

Data entry
  •Add
  •Modify
  • Delete

Database extraction

Algorithms

Data conversion
  • Input
  • Output

Query construction

Report generation
Raw data

Detailed reports

Summary reports

Error reports (QA)

Study abstracts

Study guidelines

Monitoring information
  • Methods
  • Stations

QA/QC standards

Graphical reports
                                    108

-------
 ill
LULL:
EEC
ES

        CK--OH
         II

•*-•
o
Q.
0)
DC

V)
o
+•*
to
+5
CO
+"*
CO


CO
0

O — CO

f*t
           T3
           O
       e-
       0)
       4^
0)
LU
DC
O
CO
o
Q.
LU
CC


CO
CC







i«
£*<
^

- '


O
Q
O
• •
CO
fe
^^
6


p
CO
     08
     t
INPUTS
Q.
O
O
"CD
CO
o
CO
CO
O
Aerosols
Met
CO
o
X
£
o
o • - •
>
                  I
                      CO

                      3
                      ri
         109

-------
                                                                                 February 1992



 these QA/QC checks.  The raw data will then be input to the repository database along with die



 QA/QC flags and will be available to scientists. CASTNET users will require raw data reports,



 summary reports, and graphic output. Hie output function is the process by which data are extracted



 and transferred to an external repository (for example, magnetic tape or disk file) in a specified



 format.



 AIRS Selection Rationale



        The choice of AIRS to store measurement data was not preordained. The work group



 considered various options before making its recommendation, ultimately developing a list of relative



 advantages and disadvantages of using AIRS, which appears below:



 Advantages



        1. AIRS is accepted as the official national air quality database.



        2. AIRS has an established infrastructure, staff, and budget.



        3. User training is already established and easily accessible.



        4. Some CASTNET users have already used AIRS to retrieve data.



        5. Use of edit checking can improve overall data quality and reduce manual review of



           ambient data.



        6.  AIRS access is available in EPA Regional Offices and Research Laboratories within EPA



           and in a majority of state environmental offices. Extension to other agencies presents few



           problems.



       7.  AIRS already contains some visibility data.



Disadvantages



        1.  Modification of AIRS is complicated by the need to avoid changing the original function



           of the system.






                                              110

-------
                                                                              February 1992



       2. The AIRS User's Guide initially will need to be used frequently.  Planning is underway



          for on-line help so the user can be less dependent on manuals.



       3. Data submitted to AIRS that do not pass edit checks will be rejected and won't be loaded



          into the AIRS files.  The data manager will need to correct the data or override the AIRS



          edit checks.



       4. Graphic representation of data is not currently available but is being developed.



       S. Cost of modifying large systems can be more than creating a new system. In the long



          run, operating costs of a large system may be greater for a new system than for a



          modified system.



Implementation Schedule



       Assuming AIRS is used, the Data Management work group recommends the following



implementation schedule:



                                         Phase I



       1. Establish edit checks based on EPA-defined acceptance criteria.



       2. Establish QA/QC for data of suspect quality.



       3. Design separate CASTNET file (input routines and storage file).



       4. Enhance output routines to provide CASTNET standard reports, summary reports, and



          other EPA-desired outputs.



       5. Modify AIRS Geo-Common to contain CASTNET-specific codes.



                                         Phase n



       1. Provide additional enhancements to AIRS/AQS as CASTNET evolves.



..  .    2. Provide additional standard reports.  The ad hoc/custom report option may be included in



          Phase I if it is a priority for CASTNET users.






                                            Ill

-------
                                                                        February 1992



3. Enhance QA/QC flagging capability.



                                  Phase m




1. Design on-line help capability.



                                  Phase IV



1. Provide additional graphic outputs hi the form of standard SAS/GRAPH reports and



   customize graphic report capabilities.



2, Provide additional on-line help as user community expands.
                                     112

-------
                                                                               February 1992
                                 Instrumentation/Methods




        The Instrumentation/Methods work group is responsible for providing advice on



 instrumentation and monitoring methods when questions arise in the other CASTNET committees.



 Hie group has reviewed the status of instrumentation for the Total Deposition, Aquatic and Terrestrial



 Effects, Visibility/Acid Aerosols, and Air Toxics program work groups.  Written status reports have



 been provided in these areas during the instrumentation selection process, and several projects critical



 to CASTNET monitoring goals have been identified as methods development projects.  Some of these



 projects are being funded as part of other methods development programs, the results from which will



 become part of the CASTNET information base for methods.  Methods development activities for



 monitoring of hydrocarbons and hazardous VOCs, as required by Titles I and m of the CAAA, are



 examples (see Current Projects below).  Other projects have been or will be funded as part of the



 CASTNET program.  Proposed future projects, general recommendations, and specific



 recommendations by program work group are discussed in mis section.  -



 Current Projects



 Developing Passive Sampling Devices (PSDs)



        A set of passive sampling devices (PSDs) is needed for supplemental sampling sites around



the main CASTNET sites. These units require no electricity and may provide cost-effective



 alternatives to fully configured monitoring sites.  They appear especially well-suited to supplementing



spatial information on the ambient air concentrations of O,, NO,, and SO,. Field evaluation is



required to determine their ruggedness during week-long sampling intervals and to establish data



comparability with the real-time instruments that are the  currently accepted monitoring standards for



network stations.






                                            113

-------
                                                                                 February 1992



        CASTNET has provided funding for continuing field evaluations of PSDs at the NDDN site



 in Prince Edward, Virginia.  These tests were begun in the fall of 1990 and included PSD



 comparability tests for SO2, NO, NO2, and 0,.  Maintaining this evaluation during the summer



 months of 1991 was considered essential to monitor the effects of seasonal changes in atmospheric



 chemistry on the integrity of samples.  Atmospheric chemistry is also dependent on the part of the



 country in which the monitoring is done, for example, paniculate nitrate is significantly higher at



 west coast locations.  For this reason, the NFS has arranged to deploy Q, PSDs at several of then-



 sites across the country.  Similar deployment of PSDs for SOj, NO, and NOj must be carried out in



 the future.



        As a continuation of the work on PSDs, a cooperative agreement with Harvard University has



 been initiated to design a simplified network monitoring station to operate free of power utilities. He



 design will be similar to the prototype station used at the NDDN site in Prince Edward, Virginia.



 Evaluating the Versatile Air Pollution Sampler fVAPSJ



       The Versatile Air Pollution Sampler (VAPS) is being evaluated  as an alternative to the



 IMPROVE sampler in use at network stations for characterizing visibility-related atmospheric



 constituents. The VAPS  is a new type of sampler that combines the features of a dichotomous



 sampler and an annular denuder.  The fine particles are split into two equal fractions and collected on



 separate filterpacks, which allows different filter materials - such as teflon and quartz - to be used for



 collecting fine particles. Annular denuder sections are used to remove individual gas species.  An



additional feature of VAPS is mat die coarse fraction (containing coarse particles and a small fraction



of fine particles) can be used to determine the  chemical properties of individual particles by scanning



electron microscopy.            .       .
                                             114

-------
                                                                               February 1992



        The VAPS is being tested in the laboratory and in the field at a network monitoring station



 maintained by the NFS in the Shenandoah Valley, Virginia.  Comparisons between the VAPS and



 IMPROVE sampler will be noted and may lead to simplification of sampler design.  The ability of the



 two samplers to provide acid aerosol concentration values is a major criterion hi their evaluation.



 Real-Time Acid Aerosol Instrument Development



        The infrared aerosol analyzer (IAA) has been developed by the Argonne National Laboratory



 (ANL) to measure ammonium sulfate, ammonium bisulfate,  and ammonium nitrate in near real tune.



 The instrument provides the infrared absorption spectra of particulate matter collected by impaction



 onto special substrates. The instrument is unique in the nondestructive measurement of the frequency,



 temporal duration, and intensity of acid aerosol events.  EPA requires this information to develop the



 appropriate sampling strategy to relate health and ecological effects to acute and chronic exposure to



 acid aerosols.                                             .  -       •



       The IAA was used at a common monitoring site near State College, Pennsylvania, with other



 instruments for one month in 1991.  The study should yield  a comparison of die IAA with 12- to 24-



 hour tune-integrated sampling systems that require post-sampling analysis at a laboratory site. The



 project also included the use of an FTIR (Fourier transform  infrared) -based system for nondestructive



 analysis of particles collected on in-line filters over 24 hours.



 Initiating Experiments with Rherpacks



       The filter pack used in NDDN differs from mat used in some other networks; the NOAA



 filterpack, for example, exposes the incoming air to a small  amount of heating, so as to eliminate



problems associated with liquid water forming on the particulate (teflon) and HNOj  (nylon) filters.



The NDDN filterpack is similar to that used in Canada, which lacks heating of the inlet air (a nicety



that is likely unimportant at high latitudes but which could cause sampling differences in more humid






                                             115

-------
                                                                               February 1992



 environments - e.g. the U.S. southern states).  Hie NDDN sampler is known to read low for SO2



 because SO2 is lost to the in-line nylon filter placed just before the carbonate-impregnated filter that



 collects SO2. (This does not appear to be the case for the NOAA filterpack.)  Even though the



 NDDN nylon filter is extracted to retrieve captured S02, 10 to IS percent is not recoverable.  To the



 extent that the bias is constant, an average percent correction can be made. The bias is unknown,



 however, unless it is measured each time a sample is taken.  Special precautions must be taken to



 detect any changes in the retentive properties of the nylon filters, such as those associated with



 unannounced changes in die filter manufacturing process.  Without these precautions, filter pack



 analyses could indicate spurious trends.



        To address this issue, arrangements have been made to check the bias periodically by loading



 a second filter pack side-by-side, using a carbonate-impregnated filter in place of the nylon filter. •



 This procedure is currently in place at the five NDDN sites that operate duplicate filter packs.



 Monitoring of Hazardous VOCs with Automated Gas Chromatographs (autoGCsJ



        As mentioned in the Air Toxics section, automated gas chromatographs (autoOCs) will be



 deployed at state-maintained monitoring stations to measure gaseous hydrocarbons (ozone precursors)



 as required in Title I. At a subset of these stations, chromatograms from the autoGCs will be



 examined for evidence of hazardous VOCs as an initial attempt at complying with Title m



 requirements.  Three methods development tasks are being carried out to strengthen autoGC design to



 improve data capture, mlnipnigft use of consummables such as liquid cryogens, and to improve



 chromatographic resolution for target VOCs of interest.



 Sorbem-Based Sampling and Analysis of Hazardous Polar VOCs



       Two methods development tasks are in progress to develop sampling and analysis methods for



polar VOCs using carbon-based solid sorbents for sample collection.  This approach is receiving






                                             116

-------
                                                                               February 1992



 renewed attention due to the availability of new sorbents and the acceptance of multi-sorbent tubes for



 sample collection.  In multi-sorbent tubes, two or three sorbents are packed in series to increase



 retentive power. Heating the tube and backflushing with purge gas is one example of how adsorbed



 compounds are retrieved.  An alternative to thermal desorption of adsorbed compounds under



 consideration is supercritical fluid extraction. The advantage to this latter method is that it would



 avoid thermal decomposition of adsorbed compounds.



 Projects for Future Work



 Establishing Comparability of SO, PSD Resu/ts with Filterpack Results at Four Additional



 Geographically Diverse Locations



       Tests are needed to establish the comparability of data  obtained by SO2 PSDs with data



 obtained by filterpacks at different locations  and during different seasons.  Once such data are



 available, a simpler monitoring scheme can be deployed. That is, a filterpack with only two filters



 (for paniculate matter and  HNO3) and two PSDs (for O3 and SO^ can obtain the same data currently



 being collected at the NDDN stations, but without the question surrounding the SO2 values.



 Deploying a Better,Sample Collection Device



       A sampler design using a particle sizing inlet and annular denuder system sections could be



 adapted to preserve and measure aerosol acidity and additional trace gases.  The coarse particles are



 collected on an inlet impactor.  Annular denuder sections are added in front of the filterpack to collect



 acid gases and ammonia.  If fine particle acidity is required, then a minimum of a particle sizing inlet



 and an ammonia denuder are needed. It may be necessary in some parts of the country to include in-



line filters (downstream of the fine particle filter) for HNO3 and NH3 to account for decomposition of



 ammonium nitrate. This design option would be complemented by the use of PSDs for Q, and



possibly for NO and NO2.






                                             117

-------
                                                                               February 1992



 Deploying a Screening Device for A cid Sulfate



        Based on recent in-house experimental results at EPA, FTTR transmission spectroscopy can be



 used as a screening device for acid sulfate collected on teflon filters.  In-line filters, such as those



 used in filterpacks, can be nondestructively analyzed for acid sulfate with a simple, compact,



 commercially available FTIR system.  This system needs to be field-demonstrated to gain the



 credibility necessary for acceptance as a routine monitoring tool.



 Testing PSDs for Other Trace Oases



        The use of PSDs can be extended to other gases, such as NO, NOj, HNO3, and NH3.  This



 option depends  on the perceived need by other CASTNET committees.



 Developing a  VOC Sampling System



        Monitoring certain categories of VOCs may be desirable at CASTNET sites.  Either a



 sequential,  battery-operated sampler (for multiple 24-hour samples) or an event sampler can be



 considered. Designs which have incorporated specially prepared canisters for whole air collection or



 the new generation carbon-based solid adsorbents are available commercially. Adequate field testing,



however, has not been completed and QA/QC procedures must be developed.



 General Recommendations



       The Instrumentation/Methods work group recommends several guidelines for improved



instrumentation:



       •  Establish data comparability when changes in instrumentation are made so that information



          on concentration trends is preserved.



       •  Standardize instrumentation intended for gathering data of the same type in order to



          minimize efforts needed to substantiate data comparability.
                                            118

-------
                                                                               February 1992



        •  Design network instrumentation to facilitate internal quality assurance procedures and



           thereby ensure high-quality data.



        •  Compile and update the "white" papers developed by this work group for the program



           work groups on the status of monitoring methods. Appendix D contains an example of a



           "white" paper on methods for nitrogen containing compounds.



Specific Recommendations



        Specific recommendations for each of the program work groups are as follows:



Total Deposition



        •  Continue to establish data comparability between PSDs and samplers used for dry



           deposition purposes.



        •  Develop and test the throughfall method for dry deposition.



        •  Develop/choose sampler for cloud impact sampling at high elevation sites. If acceptable,



           deploy at high elevation sites hi the wet deposition network.



Aquatic and Terrestrial Effects



        •  Continue interference testing of PSDs for sampling of NO2, SO2, and O3.



        •  Consider the LEDAR (Light Detection and Ranging) fluorescence technique for airborne



           measurement and survey of algae formation in estuaries.



        *  Add daily wet deposition  sampling at selected sites to compare with longer-term sampling,



           particularly for H+ and NH/.



VisibiKt y/Acid Aerosols



        •   Finish characterization of the VAPS with respect to particle and acid gas transmission



           characteristics of the cyclone and virtual impactor.



        •  Run data comparability tests between the VAPS and IMPROVE samplers.






                                             119

-------
                                                                               February 1992



       *  Establish the frequency, duration, and intensity of acid aerosol events with the IAA at the



          Shenandoah IMPROVE site.




Air Toxics



       *  Continue efforts to improve the autoGC design.



       •  Continue efforts to improve sampling and analysis methods for polar VOCs using carbon-



          based solid sorbents for sample collection.



       •  Finish characterization of the UMASS sampler (the four channel, high volume sampler for



          organics) and establish data comparability with PS-1 samplers.



       •  Select and evaluate the most promising monitoring techniques for airborne mercury.
                                            120

-------
                   Appendix A:  CASTNET Work Group Members and Workshop Participants
lommittee Co-Chairs:
        Dale A. Pahl
        Atmospheric Research and Exposure Assessment Labontoiy
        U.S. Environmental Protection Agency
        MD-56
        Research Triangle Park, NC   27711
         Junes S. Vickecy
         Atmospheric Research and Exposure Assessment Labontoiy
         U.S. Environmental Protection Agency
         MD-75
         Research Triangle Park, NC  27711
    1 Deposition:

        Julian Chazin
        Wisconsin Department of Natural Reaoutcet
        Box 7921
        Madison, WI  53707

        loon F. Clarke
        Atmospheric Research and Exposure Assessment Laboratory
        U.S. Bnvironmenlal Protection Agency
        MD-80
        Research Triangle Park, NC  27711

        Miguel Flores
        National Park Service - Air
        P.O. Box 25287
        Denver, CO  80225

        Jim Gibson
        Colorado State University
        Natural Resources Ecology Labontoiy
        Fort Collins, CO  80525

        William F. Hunt
        OfBceof Air Quality Planning and Standards
        U.S. Environmental Protection Agency
        MD-14
        Research Triangle Park, NC  27711

        PaiUKapinos
        U.S. Geological Survey
        416 National Center
        Reaton, VA  22092
         Office of Atmospheric and Indoor Air Program*
         U.S. Environmental Protection Agency
         401 M Street, S.W.
         Washington, D.C.  20460

         Barry E. Martin
         Atmospheric Research and Exposure Assessment Laboratory
         U.S. Environmental Protection Agency
         MD-76
         Research Triangle Park, NC  27711

         Peter Summers
         Atmospheric Environmental Service
         4905 Dufferin Street
         Downsview
         Ontario, Canada  M3H5T4
Aquatic and Terrestrial Effects:

      *   Ralph E. Battfngardner
         Atmospheric Research and Exposure Assessment Laboratory
         U.S. Environmental Protection Agency
         MD-76
         Research Triangle Park, NC  27711
         Charles Boylea
         RcnMciiicr Polytechnic
        Dennis A. Leaf (ANR-445)
         Clean Water Institute
         Troy, NY  12181
         Robert Hannah
         Department of Environmental Quality
         11720 Airline Highway
         Baton Rouge, LA  70817

         Dennis A. Leaf (ANR-445)
         Office of Atmospheric and Indoor Air Programs
         U.S. Environmental Protection Agency
         401 M Street, S.W.
         Washington, D.C.  20460
                                                                A-l

-------
                                                                                                         February 1992
          PaulRingoId
          Office of Environmental Processes and Effects Research
          U.S. Environmental Protection Agency
          RD-682
          401M Street, S.W.
          Washington, D.C.  20460

          Rosaliaa Rodriguez
          Office of Air Quality Planning and Standard*
          U.S. Environmental Protection Agency
          MD-I2
          Research Triangle Park, NC  27711

          John Stoddard
          ManTech EnviroamenUl Technology, Inc.
          200 SW 35th Street
          Corvallit, OR 97333

          KenSiolte
          National Park Service - Air
          P.O. Box 25287
          Denver, CO  80225

          Rick Slrassznan
          Air Quality Division
          Acid Deposition Division
          Minneaota Pollution Control Agency
          520 Lafayette Avenue
          St. Paul, MN 55155

          Alan Van Arsdale
          NESCAUM
          85 Merrimsc Street
          Boston, MA  02114
Visibility/AcidAerosols;
         VicfciAtwell
         Office of Air Quality Planning and Standard*
         U.S. Environmental Protection Agency
         MD-11
         Research Triangle Park, NC  27711
         Neil J. Berg, Jr.
         Office of Air Quality Planning and Standards
         U.S. Eovironmental Protection Agency
         MD-14
         Reaeareh Triangle Park. NC  27711

         Robert M. Burton
         Atmospheric Reaeareh and Exposure Atariimmt Laboratory
         U.S. Environmental Protection Agency
         MD-56
         Research Triangle Park, NC  27711

         E. Gardner Evani
         Atmospheric Research and Exposure Aaaeeement Laboratory
         VS. Bnviromnental Protection Agency
 MD-56
 Reiearcn Triangle Park, NC  27711

 Rich Fisher
 Rocky Mountain Station
 USDA Forest Service
 240 West Prospect
 Fort Coliint, CO  80526

 Bill Malm
 National Park Service - Air
 CIRA - Foothills Campua
 Colorado State University
 Fort Collioi, CO  80523

 Jan H. Moneysmitb
 Environmental Services Division
 U.S. Environmental Protection Agency
 MD6E-SA
 First Interstate Bank Tower at Fountain Place
 1445 Ross Avenue 12th Floor, Suite 1200
 Dallas, TX  75202

 BillOshmd
 California Air Resources Board
 Monitoring Laboratory Division
 P.O. Box 2815
 Sacramento, CA  95812

 MarkPitchford
 Environmental Monitoring Systems Laboratory (EMSL)/ORD
 U.S. Environmental Protection Agency
 P.O. Box 15027
 Las Vegas, NV  89114

 Richard Potrot
 Vermont Air Program
 Building 3 South
 109 S. Main Street
 Weterbury.VT  05676

 Bruce V. Polkowafcy
 Office of Air Quafity Planning and Standards
 U.S. Environmental Protection Agency
 MD-12
Research Triangle Park, NC  27711

 Larry J. Purdue
 Atmospheric Research and Exposure Assessment Laboratory
 U.S. Environmental Protection Agency
 MD-77
Research Triangle Park. NC  27711

Mark Scruggs
 National Park Service - Air
P.O. Box 25287
 Denver, CO  80225

Riiuell W. Wiener
 Atmospheric Research and Exposure Assessment Laboratory
                                                                  A-2

-------
                                                                                               February 1992
 U.S. Environmental Protection Agency
 MD-77
 Reaearch Triangle Park, NC  27711
 RiekArtz
 NOAA-Air Resources Laboratory (R/B/AR)
 SSMCJl, Rm. 9358
 1325 Eait Wen Highway
 Silver Spring, MD 20910

 Terry L. Clait
 Atmospheric Research and Exposure Assessment Laboratory
 U.S. Environmental Protection Agency
 MD-80
 Research Triangle Park, NC  27711

 Larry T. Cupitt
 Atmospheric Reaearcb and Exposure Assessment Laboratory
 U.S. Environmenial Protection Agency
 MD-75
 Research Triangle Park, NC  27711

 Geraldine J. Dorosz
 Office of Air Quality FUnning and Standards
 U.S. Environmental Protection Agency
 MD-14
 Rewarch Triangle Park, NC  27711

 Robert B. Faoro
 Office of Air Quality Planning and Standards
 U.S. Environmental Protection Agency          ...
 MD-14
 Reaearch Triangle Park, NC  27711

 joanne Foy                                  * >•.
 Michigan Department of Natural Resources.,.       . .  -
 Air Quality Division                       ,   • - -
 Box 30028
 Laming, MI 48909

 Steve Hedtke    .                              .
 Environmental Reaearch Laboratory
 U.S. Eavironmental Protection Agency   '
 6201 Congdon Boulevard
 Duhrth, MN 55804

Dwight Hlustick
Office of Reaearch and Development
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, D.C. 20460

AlaoJ. Hoffiaan
Atmoapheric Reaearcb and Expomre Aueaiment Laboratory
U.S. Environmental Protection Agency
MD-76
Research Triangle Park, NC  27711
         Meluaa W. McCullough
         Office of Air Quality Planning and Standards
         U.S. Environmental Protection Agency
         MD-13
         Reaearcb Triangle Park, NC  27711

         Neville Reid
         Air Resource* Branch, OME
         880 Bay Street, 4th Floor
         Toronto, Canada  M5S 1Z8

         Wayne Wilford
         Great Lake* National Program Office
         U.S. Environmental Protection Agency
         230 South Dearborn Street
         Chicago, IL  60604
Statistical Network Design for Status and Trends;

      •   Thomas C. Cuma
         Office of Air Quality Planning and Standardi
         U.S. Environmental Protection Agency
         MD-14
         Research Triangle Park, NC   27711

         Robin L. Dennia
         Atmospheric Reaearch and Exposure Aaaeatroent Laboratory
         U.S. Environmental Protection Agency
         MD-80
         Reaearch Triangle Park, NC   27711

         Michele Ferland
         Director, Atmospheric Networks
         2360 Chemin Ste-Foy
         Sto-Foy, Quebec
                 OIV4H2
                                             ntalCo
Philip I. GaMn
New York State Department of Envir
30 Wold Road
Room 140
Albany, NY  12233
         David M. Holland
         Atmospheric Reaearch and Exposure Attewmeot Laboratory
         U.S. Environmental Protection Agency
         MD-56
         Reaearch Triangle Park, NC  27711

         Larry Lanen
         California Air Reaoureea Board
         Technical Support DivUion
         P.O. Box 2815
         1131 S. Street
         Sacramento, CA  95812
Tony Olsen
Environmental R
                        aearch Laboratory /ORD
         U.S. Environmental Protection Agency
                                                         A-3

-------
                                                                                                         February 1992
          200 SW 35ft Street
          CorvaIIii,OR  97333

          Bob Vet
          Atmospheric Environmental Service*
          4905 Duflerin Street
          Downsview
          Ontario, Canada  M3H5T4
 Data Management:
          John C. Bosch
          Office of Air Quality Panning and Standards
          U.S. Environmental Protection Agency
          MD-14
          Research Triangle Park, NC 27711

          Thomas C. Lawless
          Aunoipheric Research and Exposure Assessment Laboratory
          U.S. Environmental Protection Agency
          MD-56
          Research Triangle Park, NC 27711
         lameaA. Reagan
         Atmospheric Research and Exposure Aaaeanneat Laboratory
         U.S. Enviroiiniental Protection Agency
         MD-56
         Research Triangle Park, NC  27711

         IMC M. Sune
         Atmospheric Research and Exposure Aitfiismntt Laboratory
         U.S. Environmental Protection Agency
         MD-76
         Reaearch Triangle Park, NC  27711
Instrumentation/Methods:
                                                ^
         William F. Barnard
         Atmoapheric Research and Exposure Assessment Laboratory
         U.S. Eovironinental Protection Agency
         MD-77B
         Reaearch Triangle Park, NC  27711

         Harold M. Barnes
         Atmospheric Rewarch and Exposure Assessment Laboratory
         U.S. Environmental Protection Agency
         MD-46
         Reaearch Triangle Park, NC  27711
                                          Thomas C. BUeatad
                                          Atmospheric Rewarch and Expocure Assegsmeni Laboratory
                                          U.S. Environmental Protection Agency
                                          MD-S7
                                          Research Triangle Park, NC  27711

                                          Thomas A. Hanlage
                                          Atmospheric Research and Exposure Assessment Laboratory
                                          U.S. Environment^] Protection Agency
                                          MD-76
                                          Research Triangle Park, NC  27711

                                          William F. Hunt
                                          Office of Air Quality Planning and Standards
                                          U.S. Environmental Protection Agency
                                          MD-14
                                          Research Triangle Park, NC  27711
                                                                                 snt Laboratory
William A. McClenny
Atmospheric Reaearch aod Exposure Asses!
U.S. Environmental Protection Agency
MD-M
Research Triangle Park, NC  27711
                                          StuMcNair
                                          Atmospheric Enviroomental Services
                                          4905 Dufferin Street
                                          Downsview
                                          Ontario, Canada  M3H 5T4

                                          James D. Mulik
                                          Atmospheric Reaearch and Exposure Assessment Laboratory
                                          U.S. Environmental Protection Agency
                                          MD-44
                                          Reaearch Triangle Park, NC  27711

                                          AlanW.Oi
                                          Environmental Services Division
                                          U.S. Environmental Protection Agency
                                          60 Wearview Street
                                          Lexington, MA  02173

                                          Joseph B. Sickles, U.
                                          Atmospheric Research and Exposure Assessment Laboratory
                                          U.S. Envtronmental Protection Agency
                                          MD-7S
                                          Reaearch Triangle Park, NC  27711

                                          Robert K. Stevens
                                          Atmoapheric Reaearch and Exposure Assessment Laboratory
                                          U.S. EnvironmcDtal Protection Agency
                                          MD-47
                                          Reaearch Triangle Park, NC  27711
         Robert M. Burton
         Atmospheric Reaearch and Exposure
         U.S. Environmental Protection Agency
         MD-56
         Reaearch Triangle Park. NC  27711
                                 Contract Acquisition:
Assessment Laboratory
                                          Rudolph P. Bokaleitner
                                          Atmospheric Research and Exposure Assessment Laboratory
                                          VJS. Environmental Protection Agency
                                                                  A-4

-------
                                                                                                     February 1992
      MD-76
      Research Triangle Park, NC 27711

      Andrew E. Bond
      Atmospheric Research and Exposure Assessment Laboratory
      U.S. Environmental Protection Agency
      MD-76
      Research Triangle Park, NC 27711

      Steven M. Bromberg
      Atmospheric Research and Exposure Assessment Laboratory
      U.S. Environmental Protection Agency
      MD-75
      Research Triangle Park, NC 27711

      lohnB. Clioe
      Office of Administration and Resources Management
      U.S. Environmental Protection Agency
      MD-33
      Research Triangle Park, NC 27711

      William P. Hunt
      Office of Air Quality Planning and Standards
      U.S. Environmental Protection Agency
      MD-M
      Research Triangle Park, NC 27711
er Workshop Participants

     John D* Bachmann
     Office of Air Quality Planning and Standard!
     U.S. Environmental Protection Agency
     MD-11
     Research Triangle Park, NC  27711

     Joe Barnard
     USDA Forest Service
     Forestry Science Laboratory
     Box 12254
     Research Triangle Park, NC 27709

     Jack A. Bowen
     Atmospheric Research and Exposure Assessment Laboratory
     U.S. Eoviromncntal Protection Agency
     MD-77B
     Research Triangle Park, NC  27711

     Ronald L. Bndow
     Atmospheric Research and Exposure Assessment Laboratory
     U.S. Eavinuunental Protection Agency
     MD-56
     Research Triangle Park, NC  27711

     Robert S. Chapman
     Health Effects Research Laboratory
     U.S. Environmental Protection Agency
     MD-58
     Research Triangle Park, NC  27711
Nancy Cobb
NOAA/OAR
1335 East-West Highway
Silver Spring, MD  20910

William M. Cox
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
MD-14
Research Triangle Park. NC  27711

Ed deSteiguer
U.S. Forest Service
1509 Vanity Drive
Raleigh, NC 27606
Ronald J. Drago
Atmospheric Research and Exposure Assessment Laboratory
U.S. Environmental Protection Agency
MD-76
Research Triangle Park, NC  27711

Gary F.  Evans
Atmospheric Research and Exposure Assessment Laboratory
U.S. Environmental Protection Agency
MD-56
Research Triangle Park, NC  27711

Gary J. Foley
Atmospheric Research and Exposure Assessment Laboratory
VS. Environmental Protection Agency
MD-75
Research Triangle Park, NC  27711
William G.'
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
MD-14
Research Triangle Park, NC  27711

Robert G. Lewis
Atmospheric Research and Exposure Assessment Laboratory
U.S. Environmental Protection Agency
MEM4
Research Triangle Park, NC  27711

RickLii
Atmospheric Research and Exposure Assessment Laboratory
U.S. Environmental Protection Agency
MD-75
Research Triangle Park, NC  27711

Lester Machta
NOAA-Air Resources Laboratory (R/E/AR)
SSMCn. Rm. 9358
1325 East West Highway
Silver Spring, MD  20910

Frank McEiroy  (RD-680)
                                                               A-5

-------
                                                                                               February 1992
 Office of Reaearch and Development
 U.S. Environmental Protection Agency
 401 M Street, S.W.
 Washington, D.C.  20460

 Jay I. Metier
 Atmospheric Research and Exposure Assessment Laboratory
 U.S. Environmental Protection Agency
 MD-75
 Research Triangle Pa*, NC   27711
 William J. Mitchell
 Atmospheric Research and Exposure Assessment Laboratory
 U.S. Environmental Protection Agency
 MD-75
 Research Triangle Park, NC  27711

 Peter K. Mueller
 EPRI
 P.O. Box 10412
 Palo Alto, CA

 Tom Pheiffer
 Office of Program Management
 VS. Environmental Protection Agency
 OS-110
 401 M Street, S.W.
 Washington, D.C.  20460

 Linda P. Porter
 Atmospheric Research and Exposure Aneiiment Laboratory
 VS. Environmental Protection Agency
 MD-77B
 Research Triangle Park, NC  27711
                                Allen Wiebe
                                Atmoapheric Environmental Service
                                4905 Dufferin Street
                                Downjview
                                Ontario, Canada  M3H5T4
                               Nancy K. Wilson
                               Atmoapberie Research and Exposure Aaseaament Laboratory
                               U.S. Environmental Protection Agency
                               MD-44
                               Research Triangle Park, NC  27711
 Lisa I. Smith
 Atmospheric Research and Exposure
 U.S. Environmental Protection Agency
 MD-S6
 Rewarch Triangle Park. NC  27711
L&bonttny
Jack C.Sugg*
Atmoapheric Research and Exposure Asaeaameot Laboratory
U^. Environmental Protection Agency
MD-77B
Reaeareb Triangle Park, NC  27711

Hemy C. Thomas, Jr.
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
MD-12
Reaearch Triangle Park, NC  27711

Dan Vallero
Atmoapheric Research and Exposure Assessment Laboratory
U.S. Environmental Protection Agency
MD-75
Research Triangle Park, NC  27711
                                                         A-6

-------
                                                                                      February 1992
* Denotes work group co-chain.
'Retired.
' On •uignment to the Office of Air Quality Planning and Standard!.
                                                   A-7

-------

-------
                                                                                February 1992
   Appendix B: CASTNET CAAA Mandate Summary and Reporting Requirements
 Total Deposition and Aquatic and Terrestrial Effects

 Title IV:

 Section 404

        Report in 36 months on the identification of sensitive and critically sensitive aquatic and
        terrestrial resources, and the feasibility and effectiveness of an acid deposition standard or
        standards to protect them.

 Title IX:

 Section I03(c}

        Establishment of a national network to monitor, collect, and compile data with quantification
        of certainty in the status and trends of deposition, surface water quality, and forest condition.
        Develop improved methods and technologies to increase understanding of the sources of
        ozone precursors, and on ozone formation and transport.  Reports to Congress every 5 years
        which evaluate and assess the effectiveness of air pollution control regulations.

Section 203(e)

        EPA,  in cooperation with NOAA, shall  conduct a research program on the short-term and
        long-term causes, effects, and trends of ecosystems damage from air pollutants.  The program
        is to include:  an evaluation of the risks to ecosystems, with causes and effects of chronic and
        episodic exposures to air pollutants; an evaluation of air pollution effects on water quality,
        including ecological effects of air pollution on surface water (including wetlands and estuaries)
        and groundwater; and an evaluation of air pollution effects on forests, crops, biological
        diversity, soils, and other aquatic and terrestrial systems.

Section 1030)

        Continuation of the National Acid Precipitation Assessment Program (NAPAP).  Reports to
        Congress starting in 1992 and biennially thereafter on actual and projected emissions and acid
        deposition trends; ambient concentrations; status of ecosystems (including forests and surface
        waters), materials, and visibility; causes and effects of such deposition, including changes in
        surface water quality and forest and soil conditions; and the occurrence and effects of episodic
        acidification, particularly to high  elevation watersheds. In 1996, and every 4 years thereafter,
        the report shall include: deposition rates necessary to prevent adverse ecological effects; and
   •    the costs and benefits of the acid deposition control program.
                                              B-l

-------
                                                                                 February 1992
Section 901 (g)
        Report to Congress annually, with periodic assessment reports, on the occurrence and effects
        of: acid deposition on surface waters west of the Mississippi River; acid deposition on high
        elevation ecosystems (including forests and surface waters); and on episodic acidification.

Visibility/Acid Aerosols

We VIII

Section 169B

        EPA, in conjunction with the NFS, is to conduct research on sources and source regions of
        both visibility impairment and regions that provide predominately clean air in Class I areas.
        To include: expansion of current visibility monitoring in Class I areas; assessment of current
        sources of visibility impairing pollution; adaptation of regional air quality models; and studies
        of the atmospheric chemistry and physics of visibility. Report on interim findings in 3 years.
        In 24 months, assess likely improvement in visibility in Class I areas due to CAAA.  Every 5
        years thereafter, assess the actual progress and improvement in visibility in Class I areas.

Tide IX

Section 103(c)

        Establishment of a national network to monitor, collect, and compile data with quantification
        of certainty in the status and trends of visibility impairment.  Reports to Congress every 5
       years which evaluate and assess the effectiveness of air pollution control regulations.
                                              B-2

-------
                                                                                February 1992
Air Toxics
We III
Section 112(k)
       EPA to conduct research on the sources of HAPs in urban areas.  To include: ambient
       monitoring of VOCs, metals, pesticides, PICs, and other toxic pollutants; sources of
       pollution, focusing on area sources and their contribution to public health risks; consideration
       of atmospheric transformation and other factors which can elevate public health risks; and the
       role of such pollutants as precursors of ozone or acid aerosol formation. Preliminary results
       of such research is due in 3 years.  A comprehensive strategy to control emissions of HAPs
       from area sources in urban areas is due to Congress in 5 years.
Section 112(m)
       EPA, in cooperation with NOAA, to identify and assess the extent of atmospheric deposition
       of HAPs (and other pollutants) to the Great Lakes, Chesapeake Bay, Lake Champlain, and
       coastal waters. To include: monitoring; sources and deposition rates of air pollutants and
       precursors; relative contribution of HAPs to total pollution loadings;  the contribution of mis
       deposition to violations of water quality standards; and sampling for such pollutants hi biota,
       fish, and wildlife, with characterization of the sources of such pollutants. One monitoring
       site, for both wet and dry deposition, to be established in each of the Great Lakes by
       12/31/91.  Report in 3 years, then biennially, to include at a minimum: 1) relative pollutant
       loading from the atmosphere compared to total loading; 2) adverse effects on human health
       and the environment; 3) sources of those HAPs; 4) contribution to violations of water quality
       standards or criteria; and 5) recommended regulatory revisions to prevent adverse effects.  In
       5 years, promulgate any further  standards deemed necessary (per the report to Congress) to
       prevent adverse effects, including effects due to bioaccumulation and indirect exposure
       pathways.
                                              B-3

-------

-------
                                                                           February 1992
                           Appendix C:  Selected References
 Aubertin, G.M.; Bigelow, D.S.; Malo, B.A. (editors)  1990.  Quality Assurance Plan: NADP/NTN
       Deposition Monitoring.  National Atmospheric Deposition Program.  Natural Resources
       Ecology Laboratory, Colorado State University; Fort Collins, CO.

 Bigelow, D.S.  1984.  Instruction Manual: NADP/NTN Site Selection and Installation.  Natural
       Resources Ecology Laboratory, Colorado State University; Fort Collins, CO.

 Bigelow, D.S.; Dossett, S.R. 1988.  NADP/NTN Instruction Manual: Site  Operation. Natural
       Resources Ecology Laboratory, Colorado State University; Fort Collins, CO.

 Environmental Sciences and Engineering, Inc.  1990. National Dry Deposition Network.  Project
       Work Plan.  Gainesville, FL.

 Environmental Sciences and Engineering, Inc.  1990. National Dry Deposition Network.  Field
       Operations Manual.  Gainesville, FL.

 Environmental Sciences and Engineering, Inc.  1989. National Dry Deposition Network.  Project
       Quality Assurance Plan.  GainesvUle, FL.

 Morrison, M.; Newell, A.D.; Hjort, R.  1990.  Data User's Guide to the United States
       Environmental Protection Agency's Long-Term Monitoring Project:  Quality Assurance Plan
       and Data Dictionary.  EPA 600/_/_.  Office of Research and Development, Washington,
       D.C.

 Peck, D.  1991.  EMAP Integrated Quality Assurance Project Plan for the Surface Waters
       Resource Group - Fiscal Year 1991.  EPA 600/_/_. Office of Research and Development,
       Washington, D.C.

 U.S. Environmental Protection Agency. 1990.  IMPROVE Progress Report: Appendices A-H.
       EPA 4SO/4-90-008a and 008b.

U.S. Environmental Protection Agency. 1987.  Handbook of Methods for Acid Deposition
       Studies, Laboratory Analyses for Surface Water Chemistry.  EPA 600/4-87/026.  Office of
       Research and Development, Washington, D.C.

U.S. Environmental Protection Agency/Canada Ontario Coordinated Committee on Annex 15.
       IADN Implementation Plan.  1990.
                                           C-l

-------

-------
                                                                        February 1992
         Appendix D:  Sample Instrumentation/Methods "White" Paper
                Status of Measurement Methodology for Nitrogen Oxides
                                 by J.E. Sickles, II

     Oxides of nitrogen include many individual chemical species: NO. N02. HNO3, HN02,
 NO3 radical,  N2O5, PAN. other organic nitrates, and paniculate nitrates (NO3~). Table I
 summarizes selected  characteristics ol instruments and methods currently available for
 sampling and analyzing many of these compounds. N2OS is not included because tt has not
 been determined in the troposphere,  tt has, however, been observed in the stratosphere
 using spectroscopic methods.
     Measuring the chemiluminescence (CLM) following the reaction of NO and O3 is the
 method  of choice (or NO.  Commercially available instrumentation  can measure NO
 specifically with a nominal detection limit of 1 ppb. As noted in Table I, refinements of CLM
 as well as other technologies exist for the determination of NO.  These methods are generally
 research or laboratory tools and as a result must undergo refinement prior to deployment in
 routine monitoring networks.   •      *••'•.-•.-•-
    Nitrogen  dioxide  may be measured as NO by CLM following catalytic or photolytic
 conversion. Commercially available CLM instruments have detection Dmits in the range of 1
 to 10 ppb.  This type of device is not specific for N0? and other gaseous oxides of nitrogen
 may. act as direct interferents. The Luminox NO2 Analyzer is sensitive but has a nonlinear
response below 10  ppb  and is subject  to interferences  by  PAN, HNOj, and O3.
Spectroscopic methods (e.g. TOLAS and DOAS) are specific and sensitive, but their cost is
a major limitation to widespread deployment  Integratjve methods employing  a chemical
reaction with NO2 are available and range from bubbler (EPA equivalent) methods to passive
sampling devices (PSD). These methods are subject to interferences from other nitrogen
oxides, but with development may prove useful.
                                        D-l

-------
                                                                         February 1992
     It should be noted that in the case of integrative methods the sensitivity depends on the
 sampled air volume and the sensitivity of the analytical finish. As an example, for a sampler
 operating at 1 m3/h for 24-h, extracted in 10 ml, and analyzed by 1C with a sensitivity of
 0.05 pg/ml, the method sensitivity is 0.02 pg/m3 (0.01 ppb NO2).  This sensitivity would be
 0.3 ppb for a 1-h sample at the same flow rate and 0.2 ppb for a 24-h sample at 1 ipm.
     PAN and  other organic nitrates are most  commonly determined  using  integrative
 sampling with analysis by gas chromatography with electron capture detection  (GC-ECD).
 Other methods are in early stages of development.
     The simplest method for HN03 employs collection downstream of a paniculate filter on
 a nylon or chemically impregnated filter followed by extraction and analysis for NO3- by ion
 chromatography (1C). Although the method is appealing because of its simplicity, it is subject
 to artifacts/interferences (e.g., volatilizing NH^NO-j). The denuder avoids these problems, but
 Is more cumbersome and complex to use. Spectroscopic methods are available, but their
 expense is a major limitatioa
    The denuder approach (employing a NaCI-coaied denuder followed by two NdjCO^
 coated denuders) can provide sensitive determinations  of HNO^  but  is limited by its
 integrative approach. Other methods (i.e., differential optical absorption spectroscopy and
 laser induced fluorescence) are research tools and may not be well suited for widespread
 deployment.                                	
    The  nitrate radical may be determined sensitively using remote sensing (le..  OOAS). it
should be noted that the sensitivity of methods that rely on fight absorption increases with the
path length employed. Path lengths for the various absorption methods are given in Table I.
    Paniculate NO3- is easily collected on filters. Ambient aerosols including NH4NO3 have
significant vapor pressures at  ambient temperature and  pressure, and  as a result  may
volatilize during sampling. Ammonium nitrate may be in equilibrium with gaseous  HN03 and
NHg in ambient air. The use of denuders upstream to remove HNO9 and NHg before filter(s)
to collect paniculate N03~ permits reconciliation of ambient gaseous and paniculate N03~
    As an aside, pulsed fluorescence and flame photometric based instruments may be used
to monitor SOg.  Commercially available instruments have 10-20 ppb detection limits, with
                                         D-2

-------
                                                                             February 1992
 precision of 2-6  ppb,  response times of 2-5 min. and minor interferences from aromatic
 hydrocarbons.  Newer, more sensitive models have shown a detection limit of 0.1  ppb.
 precision of 0.03 ppb, response time of 4 min, and interferences of 2-3% for NO, 1% for
 xylene, and 0.1% for H2S.  Sulfur dioxide can also be collected using solutions of water,
 glycerine,  and alkaline salts (e.g.,  NagCOg)  as coatings for denuders or filters.  The
 performance of these methods for 24-h samples shows detection limits of 8 ppt and precision
 of Jess than 5%.
     Paniculate SO4*~ is easily collected on filters.  Suttates are not known to volatilize.  As a
 result denuders are not required to sample S042' unambiguously.  However, Teflon or quartz
 fitters are preferred since drawing S02-laden air through alkaline (i.e., glass fiber) filters can
 cause the formation of artifact SO4Z~ on the filters.  For 24-h  samples, filtration shows
 performance similar to that for the integrative methods for SO2 noted earlier: detection limit
 of 0.02 jtg/m3 and precision of less than 5%.
                                units = ppb
Lab
Lab
Field
                               NO,
                                   -S0.2—
                         LMA-3   CSI-1600  TECO 43s
LoD (ppb)
LoQ (ppb)
                         0.01
                         0.03
                        0.3
0.1
0:3
0.03
         Precision (ppb)   0.6
         Interferences
         PAN            65%
         HN02           50%
         HN03           0%
         NO              NA
         HjS             NA
         Xylene           NA
Response Time (min)     25         4
Reference WfigM. R.S., etal. (1989). Laboratory and Field Evaluations oJ ExtruensMve NO2 end SO, Analyze*.
Paper 89-65.1 AWMA 62nd Annual Meeting, Anaheim. CA.
NA
NA
100%
NA
NA
NA
NA
NA
NA
2-3%
0.1%
1%
                                           D-3

-------
                                                                    February 1992
TABLE I - Selected Instruments and Methods for Determining Ambient Oxides of Nitrogen
Species
NO





NOZ














PAN




Other Nitrates
HNO,
*



Method*
CLM(1)
CLM(1)
LIF
TOLAS
TTFMS
Passive
CLM(1)
CLM(1)
CLM(2)

Uf
TOLAS
TTFMS
OOAS
DIAL
Bubbler
TEA Fitter
Gualacol Denuder
DPACart

TEA PSD
GC-ECD

GC-CLM(f)
AlkaBne Hydrolysis
TTFMS
OC-ECD
FDtor

Denuder
TOLAS
TTFMS
Tree"
tAC
IAC
IAC
IAC
IAC
IP.I
IAC
IAC
IAC

IAC
IAC
IAC
RAC
RAC
IAI
IAI
UU
IAI

IP.I
IAI

IAt
IAI
IAC
IAI
IAI

IAI
IAC
IAC
Development Measure™
Stage0 Time
C
R
R
R.C
L
C
C
R
C

R
ac
L
ac
H
RM
L
L
L

L
aRM

L
L
L
R
aRM

aRM
ac
L
Srnhi
2-606
30s
60S
60S
24 hd .
5 mh>
<100S
1008

2ffiin
60s
60S
12rr*i
.
24 h"
24 h-
1h«
9hd

24 h*
IS min*

*
-
60S
24 h<
24 h-

24 h"
Snrin
60s
*nf .
Precision
0.3 ppb
20ppl
-
.
.
-
10%
20ppt
0.6 ppb
*
20ppt
.
*
.
,
6 ppb
15%
4%
e%

30%
~

-
'
»
•
10%

8%
.
- .
Performance
Accuracy
^
ZOppt
16%
-
.
-
20%
30%
.

16%
15%
.
10%
•
20%
10%
.
.

ippb
30%

•
•
•
-
20%

*
20%
-
MDL
ippb
Sppt
IDppt
0.5 ppb
4ppt
70 ppb-h
9 ppb
10-25 ppt
10ppt

12ppl
100 ppt
0.3 ppt
4 ppb
10 ppb <
eppb
0.2 ppb
0.1 ppb
0.1 ppb

30 ppb-h
10ppl

10 ppb
-
2ppt
1ppt
Sppt

eppt
too ppt
0.3 ppJ
Comments
f
-
Two-photon
40-m path length
100-rn path length
Uses oxidizer plus TEA
EPA reference method; many interferences
Uses thermal or phototytic converters
Interferences: PAN. HNO,. Oa:
Non linear response below 3 ppb
Two-photon
ISO-m path length
.
800-m path length
6-km path tength
EPA equivalent methods'
Interferences: PAN and HNOZ*
Stability of extract uncertain*
DPA may volatilize;
Interferences: KNO2 and PAN
SimBar lo Palmes Tube; interferences as above*
Sensitivity can be enhanced by using
cryogenic sampling and capillary columns
*
e
100-m path length
Sample collected on charcoal
May be nylon or Nad-Impregnated titter;
Subject lo artifacts*
Not subject lo above artifacts*
150-m path length
100-m path length
                               D-4

-------
                                          February 1992
ill  I
!•*

TO ^
 §V


-------