OSWER DIRECTIVE 9502.00-6C
RCRA FACILITY INVESTIGATION (RFI) GUIDANCE
VOLUME III OF IV
AIR AND SURFACE W
_^V NAILY19I
^ NX/
/ASTE MANAGEMENT DIVISION
OFFICE OF SOUD WASTE
U.S. ENVIRONMENTAL PROTECTION AGENCY
-------
ABSTRACT
On November 8, 1984, Congress enacted the Hazardous and Solid Waste
Amendments (HSWA) to RCRA. Among the most significant provisions of HSWA are
§3004(u), which requires corrective action for releases of hazardous waste or
constituents from solid waste management units at hazardous waste treatment,
storage and disposal facilities seeking final RCRA permits; and §3004(v), which
compels corrective action for releases that have migrated beyond the facility
property boundary. EPA will be promulgating rules to implement the corrective
action provisions of HSWA, including requirements for release investigations and
corrective measures.
This document, which is presented in four volumes, provides guidance to the
owner or operator of hazardous waste management facilities as to the conduct of
the second phase of the RCRA Corrective Action Program, the RCRA Facility
Investigation (RFI). Instruction is provided for the development and performance of
an investigation based on determinations made by the regulatory agency as
expressed in the schedule of a permit or in an enforcement order issued under
HSWA53008(h). The purpose of the RFI is to obtain information to fully characterize
the nature and extent of releases of hazardous waste or constituents. This
information will be used to determine whether interim corrective measures or a
Corrective Measures Study will be necessary.
-------
DISCLAIMER
This Draft Report was prepared for the U.S. Environmental Protection Agency
by the NUS Corporation, Waste Management Services Group, Gaithersburg, MD
20878, in fulfillment of Contract No. 68-01-7310, Work Assignment No. 5, and is
based on previous work performed by Alliance Technologies, Inc., under Contract
No. 68-01-6871. The opinions, findings, and conclusions expressed herein are those
of the authors and not necessarily those of the U.S. Environmental Protection
Agency or the cooperating agencies. Mention of company or product names is not
to be considered an endorsement by the U.S. Environmental Protection Agency.
This document is intended to assist Regional and State personnel in exercising
the discretion conferred by regulation in developing requirements for the conduct
of RCRA Facility Investigations (RFIs) pursuant to 40 CFR 264. Conformance with this
guidance is expected to result in the development of RFIs that meet the regulatory
standard of adequately detecting and characterizing the nature and extent of
releases. However, EPA will not necessarily limit acceptable RFIs to those that
comport with the guidance set forth herein. This document is not a regulation (i.e..
it does not establish a standard of conduct which has the force of law) and should
not be used as such. Regional and State personnel must exercise their discretion in
using this guidance document as well as other relevant information in determining
whether an RFI meets the regulatory standard.
-------
ACKNOWLEDGEMENTS
This document was developed by the Waste Management Division of the
Office of Solid Waste (05W).
Mr. George Dixon was the EPA Work Assignment
Manager and Mr; Art Day was the Section Chief. Additional assistance was provided
by Ms. Lauris Davies and Mr. Paul Cassidy.
Guidance was also provided by the EPA RFI Work Group, including:
George Furst, Region
Andrew Bellina, Region II
William Smith, Region II
Jack Potosnak, Region Ill
Douglas McCu try, Region IV
Francine Norling, Region V
Lydia BoadaClista, Region VI
Karen Flourney, Region VII
Larry Wapensky, Region VIII
Julia Bussey, Region IX
Melanie Field, Region IX
Jim Breitiow, Region IX
Paul Day, Region X
David Adler, OPPE
Joanne Bahura, WMD
Janette Hansen, PSPD
Lisa Fe ldt, HSCD
Stephen Botts, OECM
Chris DeRosa, OHEA
James Durham, OAQPS
Mark Guilbertson, OWPE
Nancy Hutzel, OGC
Steve Golian, OERR
Dave Eberly, PSPD
Jackie Krieger, OPPI
Lisa Lefferts, PSPD
Florence Richardson, CAD
Reva Rubenstein, CAD
Steve Sisk, NEIC
This document was prepared by the NUS Corporation, Tetra Tech, Inc., and
Labat Anderson, Inc., and was based on previous work performed by Alliance
Technologies, Inc. The principal authors included:
Todd Kimmell, NUS
Kurt Sichelstiel, NUS
William Murray, NUS
Ron Stoner, NUS
John George, NUS
Ray Diver, NUS
Dave Navecky, NUS
Tom Grieb, Tetra Tech
Kay Johnson, Tetra Tech
Bill Mills, Tetra Tech
Nick Pangaro, Alliance
Linda Marie ,, Alliance
Andrea Mysliki, Labat Anderson
I II
-------
RCRA FACILITY INVESTIATION (RFI) GUIDANCE
VOLUME III
AIR AND SURFACE WATER RELEASES
TABLE OF CONTENTS
SECTION PAGE
ABSTRACT I
DISCLAIMER
ACKNOWLEDGEMENTS
TABLE OF CONTENTS IV
TABLES Xi
FIGURES X i i i
LIST OF ACRONYMS x i v
Iv
-------
VOLUME III CONTENTS (Continued)
SECTiON PAGE
12.0 AIR 12-1
12.1 OVERVIEW 12-1
12.2 APPROACH FOR CHARACTERIZING RELEASES TO AIR 12-2
12.2.1 General Approach 12-2
12.2.1.1 Information Collection/Air Monitoring 12-2
12.2.1.2 Emission/Dispersion Modeling 12-15
12.2.2 Inter.medla Transport 12-20
12.3 CHARACTERIZATION OF THE CONTAMINANT 12-21
SOURCE AND THE ENVIRONMENTAL SETTING
12.3.1 WagteCha,acterjzai on 12-22
12.3.1.1 PresenceofConstjtuen 12-22
12.3.1.2 Physical/Chemical Properties 12-23
12.3.2 UnitCharacterization 12-28
12.3.2.1 Type of Unit 12-28
12.3.2.2 SizeoflJnit 12-35
12.3.2.3 Control Devices 12-36
12.3.2.4 Operational Schedules 12-36
12.3.2.5 Temperature of Operation 12-37
12.3.3 Characterization of the Environmental Setting 12-37
12.3.3.1 Climate 12-37
12.3.3.2 Soil Conditions 12-39
V
-------
VOLUME III CONTENTS (Continued)
SECTiON PAGE
12.3.3.3 Terrain 12-40
12.3.3.4 Receptors 12-40
12.3.4 Review of Existing Information 12-41
12.3.5 Determination of Reasonable Worst Case 12-43
Exposure Period
12.4 DESIGN OF A MONITORING PROGRAM TO 12-44
CHARACTERIZE RELEASES
12.4.1 Objectives of the Monitoring Program 12-45
12.4.2 Monitorin 9 Constituents and Sampling 12-45
Consideraflons
12.4.3 Meteorological Monitoring 12-46
12.4.3.1 Meteorological Monitoring Parameters 12-46
12.4.3.2 Meteorological Monitor Siting 12-48
12.4.4 Monitoring Schedule 12-50
12.4.4.1 Screening Sampling 12-50
12.4.4.2 Initial Monitoring 12-51
12.4.4.3 Subsequent Monitoring 12-54
12.4.5 Monitoring Approach 12-55
12.4.5.1 Ambient Air Monitoring 12-55
12.4.5.2 Source Emissions Monitoring 12-57
12.4.6 Monitoring Locations 12-58
12.4.6.1 Upwind/Downwind Monitoring Location 12-58
12.4.6.2 StackNent Emission Monitoring 12-62
12.4.6.3 Isolation Flux Chambers 12-63
vi
-------
VOLUME Ill CONTENTS (Continued)
SECTION PAGE
12.5 DATA PRESENTATION 12-63
12.5.1 Waste and Unit Characterization 12-63
12.5.2 Environmental Setting Characterization 12-64
12.5.3 Characterization of the Release 12-65
12.6 FIELD METHODS 12-70
12.6.1 Meteorological Monitoring 12-70
12.6.2 Ambient Air Monitoring 12-71
12.6.2.1 Screening Methods 12-73
12.6.2.2 Quantitative Methods 12-77
12.6.2.2.1 Monitoring Organic Compounds.in 12.78
Ambient Air
12.6.2.2.1.1 Vapor-Phase Organics 12-78
12.6.2.2.1.2 Particulate Organics 12-96
12.6.2.2.2 Monitoring Inorganic Compounds in 12-97
Ambient Air
12.6.2.2.2.1 Particulate Metals 12-97
12.6.2.2.2.2 Vapor-Phase Metals 12-99
12.6.2.2.2.3 Monitoring Acids and Other 12-105
Compounds in Ambient Air
12.6.3 Stack/Vent Emission Sampling 12-105
12.6.3.1 Vapor Phase and Particulate Associated 12-107
Organ ics
12.6.3.2 Metals 12-112
12.7 CHECKLIST 12-115
12.8 REFERENCES 12-118
vii
-------
VOLUME III CONTENTS (Continued)
SECTiON PAGE
13.0 SURFACE WATER 13-1
13.1 OVERVIEW 13-1
13.2 APPROACH FOR CHARACTERIZING RELEASES TO 13-2
SURFACE WATER
13.2.1 GeneralApproach 13-2
13.2.2 Inter-media Transport 13-7
13.3 CHARACTERIZATION OF THE CONTAMINANT 13-8
SOURCE AND THE ENVIRONMENTAL SETTING
13.3.1 Waste Characterization 13-8
13.3.2 UnitCharactenzatjon 13-15
13.3.2.1 UnitCharacteristics 13-17
13.3.2.2 Frequency of Release 13-17
13.3.2.3 Form of Release 13-18
13.3.3 Charactenzation of the Environmental Setting 13-19
13.3.3.1 Characterization of Surface Waters 13-19
13.3.3.1.1 Streamsand Rivers 13-20
13.3.3.1.2 Lakesand Impoundments 13-22
13.3.3.1.3 Wetlands 13-24
13.3.3.1.4 Marine Environments 13-25
13.3.3.2 Climatic and Geographic Conditions 13-26
13.3.4 Sources of Existing Information 13-27
13.4 DESIGN OF A MONITORING PROGRAM TO 13-28
CHARACTERIZING RELEASES
13.4.1 Objectives of the Monitoring Program 13-28
13.4.1.1 Phased Characterization 13-30
via I
-------
VOLUME Ill CONTENTS (Continued)
SECTION PAGE
13.4.1.2 Development of Conceptual Model 13-30
13.4.1.3 Contaminant Concentration vs 13-31
Contaminant Loading
13.4.1.4 Contaminant Dispersion Concepts 13-33
13.4.1.5 Conservative vs Non-Conservative Species 13-36
13.4.2 Monitoring Constituents and Indicator 13-36
Parameters
13.4.2.1 Hazardous Constituents 13-36
13.4.2.2 IndicatorParameters 13-36
13.4.3 Selection of Monitoring Locations 13-42
13.4.4 Monitoring Schedule 13-44
13.4.5 Hydrologic Monitoring 13-45
13.4.6 The Role of Biomonitoring 13-46
13.4.6.1 Community Ecology Studies 13-47
13.4.6.2 Evaluation of Food Chain/Sensitive Species 13-48
Impacts
13.4.6.3 Bioassay 1349
13.5 DATA MANAGEMENT AND PRESENTATION 13-50
13.5.1 Waste and Unit CharacterizatiOn 13-50
13.5.2 Environmental Setting CharacterizatiOn 13-51
13.5.3 Characterization of the Release 13-51
13.6 FIELDANDOTHER METHODS 13-52
13.6.1 Surface Water Hydrology 13-53
13.6.2 SamplIng of Surface Water. Runoff. Sediment 13-55
and Biota
13.6.2.1 SurfaceWater 13-55
ix
-------
VOLUME III CONTENTS (Continued)
SECTiON PAGE
13.6.2.1.1 Streams and Rivers 13-55
13.6.2.1.2 Lakes and Impoundments 13-56
13.6.2.1.3 Additional Information 13-57
13.6.2.2 Runoff Sampling 13-57
13.6.2.3 Sediment 13-59
13.6.2.4 Biota 13-62
13.6.3 Characterization of the Condition of the 13-63
Aquatic Community
13.6.4 Bioassay Methods 13-66
13.7 CHECKUST 13-68
13.8 REFERENCES 13-71
APPENDICES
Appendix E: Emmission Isolation Flux Chamber
x
-------
TABLES
NUMBER PAGE
12-1 Recommended Strategy for Characterizing Releases to Air 12-3
12-2 Release Characterization Tasks for Air 12-12
12-3 Parameters and Measures for Use in Evaluating Potential 12-24
Releases of Hazardous Waste Constituents to Air
12-4 Physical Parameters of Volatile Hazardous Constituents 12-26
12-S Physical Parameters of PCB Mixtures 12-27
12-6 Summary of Typical Unit Source Type and Air Release Type 12-30
12.7 Recommended Siting Criteria to Avoid Terrain Effects 1 2-49
12-8 Applicable Air Sampling Strategies by Source Types 12-56
12-9 Typical Commercially Available Screening Techniques 12-74
for Organics in Air
12-10 Summary of Selected Onsite Organic Screening 12-75
Methodologies
12-hA Summary of Candidate Methodologies for Quantification of 12-80
Vapor Phase Organics
12-11 B List of Compound Classes Referenced in Table 12-1 1A 12-82
12-12 Sampling and Analysis Techniques Applicable to Vapor 12-83
Phase Organics
12-13 Compounds Successfully Monitored Using EMSL-RTPTenax 12-87
Sampling Protocols
12-14 Summary Listing of Organic Compounds Suggested for 12-91
Collection With a Low Volume Polyurethane Foam Sampler
and Subsequent Analysis With an Electron Capture Detector
(GC/ECD)
12-15 Summary Listing of Additional Organic Compounds 12-92
Suggested for Collection With a Low Volume Polyurethane
Foam Sampler
x l
-------
TABLES (continued)
NUMBER PAGE
12-16 Sampling and Analysis Methods for Volatile Mercury 12-100
12.17 Sampling and Analysis of Vapor State Trace Metals 12-103
(Except Mercury)
12-18 Sampling Methods for Toxic and Hazardous Organic 12-108
Materials From Point Sources
12-19 RCRA Appendix VIII Hazardous Metals and Metal 12-113
Compounds
13-1 Recommended Strategy for Characterizing Releases to 133
Surface Water
13-2 Release Characterization Tasks for Surface Water 13-6
13-3 lmportantWaste and Constituent Properties Affecting 13-9
Fate and Transport in a Surface Water Environment
13-4 General Significance of Properties and Environmental 13-16
Processes for Classes of Organic Chemicals Under
Environmental Conditions
xii
-------
FIGURES
NUMBER PAGE
12-1 Release Characterization Strategy for Air - Overview 12-6
12-2 Develop Monitoring Procedures -Overview 12-7
12-3 Conduct Initial Monitoring Phase 12-8
12-4 Collect and Evaluate Results• Overview 12-9
12-5 Subsequent Monitoring - Overview 12-10
12-6 Example Air Monitoring Network 12-60
12-7 Example of Downwind Exposures at Air Monitoring Stations 12-69
13-1 Qualitative Relationship Between Various Partitioning 13-10
Parameters
13-2 Typical Lake Cross Section 13-23
xiii
-------
UST OF ACRONYMS
AA - - Atomic Absorption
Al - Soil Adsorption Isotherm Test
ASCS - Agricultural Stabilization and Conservation Service
ASTM - American Society for Testing and Materials
BCF - Bioconcentration Factor
BOO - Biological Oxygen Demand
CAG - EPA Carcinogen Assessment Group
CPF - Carcinogen Potency Factor
CBI - Confidential Business Information
CEC Cation Exchange Capacity
CERCLA - Comprehensive Environmental Response, Compensation, and
Lability Act
CFR - Code of Federal Regulations
CR - Color Infrared
CM - Corrective Measures
CMI - Corrective Measures Implementation
CMS - Corrective Measures Study
COD - Chemical Oxygen Demand
CO LI WASA - Composite Liquid Waste Sampler
DNPH - Dinitrophenyl Hydrazine
DO - Dissolved Oxygen
DOT - Department of Transportation
ECD - Electron Capture Detector
EM - Electromagnetic
EP - Extraction Procedure
EPA - Environmental Protection Agency
FEMA - Federal Emergency Management Agency
FID - Flame Ionization Detector
Foc - Fraction organic carbon in soil
FWS - U.S. Fish and Wildlife Service
CC - Gas Chromatography
CC/MS • Gas Chromatography/Mass Spectroscopy
GPR - Ground Penetrating Radar
HEA - Health and Environmental Assessment
HEEP Health and Environmental Effects Profile
HPLC - High Pressure Liquid Chromatography
HSWA - Hazardous and Solid Waste Amendments (to RCRA)
1 mM - Hazardous Waste Management
ICP • Inductively Coupled (Argon) Plasma
ID - Infrared Detector
Kd • Soil/Water Partition Coefficient
Koc - Organic Carbon Absorption Coefficient
Kow • OctanobWater Partition Coefficient
LEL - Lower Explosive Limit
MCL - Maximum Contaminant Level
MM S - Modified Method S
MS/MS - Mass Spectroscopy/Mass Spectroscopy
NFIP - National Flood Insurance Program
NIOSH - National Institute for Occupational Safety and Health
NPDES - National Pollutant Discharge Elimination System
OSHA - Occupational Safety and Health Administration
xiv
-------
UST OF ACRONYMS (Continued)
OVA Organic VaporAnalyzer
PID •— Photo Ionization Detector
pKa Acid Dissociation Constant
ppb partsperbillion
ppm - parts per million
PUF - Polyurethane Foam
PVC - Polyvinyl Chloride
QAIQC - Quality Assurance/Quality Control
RCRA • Resource Conservation and Recovery Act
RFA • RCRA Facility Assessment
RfD - Reference Dose
RFI - RCRA Facility Investigation
RMCL - Recommended Maximum Contaminant Level
RSD Risk Specific Dose
SASS Source Assessment Sampling System
SCBA Self Contained Breathing Apparatus
SCS Soil Conservation Service
SOP - Standard Operating Procedure
SWMU - Solid Waste Management Unit
TCLP - Toxicity Characteristic Leaching Procedure
TEGD - Technical Enforcement Guidance Document (EPA, 1986)
TOC Total Organic Carbon
TOT - Time of travel
TOX - Total Organic Halogen
USGS - United States Geologic Survey
USLE - Universal Soil Loss Equation
UV - Ultraviolet
VOST - Volatile Organic Sampling Train
VSP - Verticte Seismic Profiling
WQC - Water Quality Criteria
xv
-------
SECTION 12
AIR
12.1 OvervieW
The objective of an investigation of a release to air is to characterize the nature,
extent, and rate of migration of the release of hazardous waste or constituents to
that medium. This is done by characterizing long-term ambient air concentrations
(commensurate with the long-term exposures which are the basis for the health and
environmental criteria presented in Section 8) associated with unit releases of
hazardous wastes or constituents to air. This section provides:
• A recommended strategy for characterizing releases to air, which includes
characterization of the source and the environmental setting of the
release, and conducting a monitoring and/or modeling program which will
characterize the release itself;
• Recommendations for data organization and presentation;
• Field methods which may be used in the investigation; and
• A checklist of information that may be needed for release characterization.
The exact type and amount of information required for sufficient release
characterization will be site-specific and should be determined through interactions
between the regulatory agency and the facility owner or operator during the RFI
process. This guidance does not define the specific data needed in all instances; it
identifies possible information necessary to perform release characterizations and
methods for obtaining this information. The RFI Checklist, presented at the end of
this section, provides a tool for planning and tracking information for release
characterization. This list is not a list of requirements for all releases to air. Some
release investigations will involve the collection of only a subset of the items listed,
while other releases may involve the collection of additional data.
12-1
-------
Case studies 14 and 15 in Volume IV (Case Study Examples) illustrate several ofd
the air investigation concepts discussed in this section.
12.2 Approach for Characterizing Releases to Air
12.2.1 General Approach
The intent of the air release investigation is to determine actual or potential
effects on off-site receptors. This differs from the other media discussed in this
Guidance. During the health and environmental assessment process for the air
medium (see Section 8), the decision as to whether interim corrective measures or a
Corrective Measures Study will be necessary is based on actual or potential effects
on off-site receptors, and is not (as with the other media), based on potential effects
beyond the boundary of the waste management area. This general approach is
detailed in the sections below.
12.2.1.1 Information Collection/Air Monitoring
Characterization of releases from waste management units to air may b
approached in a tiered or phased fashion as described in Section 3. The key
elements to this approach are shown in Table 12-1. An overview of the release
characterization strategy for air is illustrated in Figures 12-1 through 12-5.
Two major elements can be derived from this strategy:
• Collection and review of data to be used for characterization of the source
of the air release and the environmental setting for this source. Source
characteristics will include obtaining information on the unit operating
conditions and configuration, and may entail a sampling and analytical
effort to characterize the waste material in the unit or the incoming waste
streams.
• Development and implementation of monitoring and/or modeling
procedures to be used for characterization of the release (from a unit or
contaminated soil) itself. Utilizing a phased approach, the air release
12-2
-------
Table 12-1
Recommended Strategy for Characterizing Releases to Air
INITIAL PHASE
Collect and review preliminary information for use in formulating monitoring
procedures:
- Characterization of the Contaminant Source
Waste Characterization
Unit Characterization
- Characterization of the Environmental Setting
Climate (especially wind patterns which may require an onsite -
meteorological monitoring survey)
Soil
Terrain
Receptors
- Review of Existing Air Monitoring Results
- Determination of Reasonable Worst Case exposure period over a 90 day
period at point of evaluation
2. Identify and collect additional information necessary to characterize release.
- Spatial extent of release
- Release constituents present and concentration levels
- Inter-media transport
- Conceptual model of release
3. Develop monitoring procedures:
- Conduct screening sampling
Verify existence of release
Emphasis on near-source sampling
Provide information to finalize monitoring program design
- Meteorological monitoring
- Determining constituents of concern/indicator parameters
- Sampling approach selection
- Sampling schedule
- Monitor placement
• Analytical Methods
- QA/QC protocols
4. Conduct initial monitoring phase:
- Evaluate upwind (background) and air quality levels downwind of the
source
12-3
-------
Table 12.1 (Continued)
Recommended Strategy for Characterizing Releases to Air
- If practical, conduct air monitoring at or near actual offsite receptor
location.s in order to characterize exposures at these points of evaluation
• Collect samples and complete field analyses
- Analyze samples for selected constituents and parameters
5. Collect, evaluate and report results:
- Account for source and meteorological data variability during monitoring
program
- EvaFuate long-term representativeness of air monitoring data
- Apply emission/dispersion models as appropriate to aid in data
interpretation and to estimate air constituent concentrations levels at
actual points of offsite exposure
- EPA as well as owner or operator to independently compare
monitoring/modeling results to health and environmental criteria and
identify and respond to emergency situations and identify priority
situations that may warrant interim corrective measures
- Determine completeness and adequacy of collected data
- Summarize and present data in appropriate format
- Determine if monitoring program objectives were met
• Determine if monitoring locations, constituents and frequency were
adequate to characterize release
SUBSEQUENT PHASES (If necessary)
Identify additional information necessary to characterize release:
- May be required if air concentration levels are of concern based on health
and environmental assessment and more refined concentration estimates
(e.g., larger monitoring data base or additional monitoring stations at
actual offsite receptor locations) are needed to characterize the release
• May be required after corrective measures have been identified and
implemented to evaluate air concentration trends
2. Expand initial monitoring as necessary:
• Expand air monitoring network as necessary (e.g., downwind monitoring
at locations further downwind may be warranted at complex terrain sites
for which modeling results would have a high degree of uncertainty or at
ctual offsite points of evaluation if practical)
3. Conduct subsequent monitoring phases:
• Perform expanded monitoring of area
- Analyze samples for selected constituents and parameters
12.4
-------
Table 12-i (Continued)
Recommended Strategy for Characterizing Releases to Air
4. Collect evaluate and report results/identify additional information necessary
to characterize release:
- Account for source and meteorological data variability during monitoring
program
- Evaluate long-term representativeness of air monitoring data
- Apply emission/dispersion models as appropriate to aid in data evaluation
and to provide concentration estimates at actual offsite receptor locations
as input to health and environmental assessment
- EPA as well as owner or operator to independently compare monitoring
results to health and environmental criteria and identify respond to
emergency situations and identify priority situations that may warrant
interim corrective measures
• Determine completeness and adequacy of collected data
• Summarize and present data in appropriate format
- Determine if monitoring program objectives were met
- Determine if monitoring locations, constituents, and frequency were
adequate to characterize release (nature, extent, and rate)
- Identify additional information needs, if necessary
- Determine need to expand monitoring system
- Evaluate potential role of inter-media transport
The potential for inter-media transport of contamination should be
evaluated continually throughout the investigation.
12-5
-------
IUN STRATEGY FOR AIR-OVERVIEW
COLLECTAND REVIEW
PRELIMINARY INFORMATION
Waste/Unit
Characteristics
Historical Air
Monitoring
Data
Environmental
Characterisitics
I
Develop Conceptual Model of Release
I
DEVELOP
MONITORING PROCEDURES
CONDUCT INITIAL
MONITORING PHASE
COLLECT. EVALUATE
AND REPORT RESULTS
RFI DECISION POINTS
(REFER TO SECTION 3)
I
ps•••..•..s.... ,...,s.....I.I
•
• SUBSEQUENT MONITORING
(IF REQUIRED)
$ • • ••u••••• a • a a.. a •ISIUSSI U U I
12-6
-------
FIGURE 12-2
DEVELOP MONITORING PROCEDURES- OVERVIEW
Waste/U nit Historical Environmental
Characteristics Air Monitoring Characteristics
Data
+ ‘1 ___
Candidate
IDENTIFY AIR
Screening -0 MONITORING CONSTITUENTS Air Emission List
AirSampls (s.sADP. idii9 L%t2)
SELECT AIR MONITORING
APPROACH/PROCEDURES
Site
I Meteorological
MONITOR [ aracter Izat Ion
PLACEMENT _________
Dispersion
Modeling
CONDUCT INITIAL
MONITORING PHASE
* I At facility to in crease potential for release detection
• At actual receptors beyond the facility property boundary to support health and
environmental assessment (if practical)
12-7
-------
FIGURE 12-3
CONDUCT INITIAL MONITORING PHASE - OVERVIEW
DEVELOP MONITORING PROCEDURES
$
IMPLEMENT 90-DAY
MONITORING PROGRAM
I I I
_ + + __t
24-Hour Sample S-Day Composite Emission
for Target or intermittent Meteorological Rate Samples
Constituents Monitoring Samples Monitoring for Selected
Every 6th Day• at Each Station Cases
i
COLLECT AND EVALUATE RESULTS
* To be implemented if ambient air contaminatión is susnected to be less than monitoring detection levels and
ste characterization data not sufficient for applic i of air emission release rate models
-------
FIGURE 12-4
COLLECT AND EVALUATE RESULTS- OVERVIEW
- CONDUCT INITIAL MONITORING PHASE
SUMMARIZE DATA
______________________________________ I _________________________________
Waste/Unit Meteorological Air
Characterization Monitoring Monitoring
Data Summaries Data Summaries
Supplemental
Modeling
Analyws
I
RFI DECISION POINTS
(REFER TO SECTION 3)
• To evaluate representatives of air monitoring data
• To estimate concentrations at actual receptor locations beyond the facility property
boundary (as necessary)
12-9
-------
FIGURE 12-S
SUBSEQUENT MONITORING - OVER VIEW
RFI DECISION POINTS
(REFER TO SECTION 3)
SUBSEQUENT MONITORING
(IF REQUIRED)
1
DEVELOP/EXPAND
MONITORING PROCEDURES
1
CONDUCT SUBSEQUENT
MONITORING PHASE(S)
4
COLLECT AND
EVALUATE RESULTS
RFI DECISION POINTS
(REFER TO SECTION 3)
a a a aaa.. UIad uuI 1•I
r a a
I ADDITIONAL MONITORiNG
(IF REQUIRED)
L _ e — a a — — — a — — a a a a a a
1*.u1
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
1
I
12-10
-------
characterized in terms of the types and amounts of hazardous constituents
being emitted, leading to a determination of actual or potential exposure to
offsite receptors. This may involve ambient monitoring (i.e., monitoring
concentrations at locations away from the source) and/or emission
monitoring (i.e.. monitoring at a source to determine emission rates), coupled
with dispersion modeling. A phased approach may not always be necessary
to achieve adequate release characterization.
This strategy provides an acceptable technical approach to characterize the
nature and extent of air releases from units. The collection and review of
information for characterization of the contaminant source and the environmental
setting is the primary basis for development of monitoring procedures used to
characterize air emissions. These input data should be compiled from available
sources. The air pathway data collection effort should also be coordinated, as
appropriate, with similar efforts for other media investigations. Tasks for
implementing the release characterization strategy for releases to air are
summarized in Table 12-2.
An important aspect of the environmental characterization process is the need
to identify site-specific wind patterns as a basis for specifying the station locations
for the air monitoring network. This will generally require an onsite meteorological
monitoring survey prior to completing the design of the air monitoring program.
The meteorological monitoring survey should be conducted for at least one
month, or longer if necessary (especially at complex terrain and coastal locations),
to define diurnal and seasonal wind patterns expected during the air monitoring
phase of the RFI. The limited onsite data should be compared to representative 1
long-term meteorological data to account for expected seasonal variations at the
site. Representativeness of the onsite monitors can be evaluated by comparing
short-term onsite versus long-term offsite wind distributions (wind roses), stability
frequency tables, and dispersion patterns based on modeling results (assuming an
arbitrary source emission rate). An onsite meteorological monitoring survey may
not be necessary for inland flat terrain site for which regional National Weather
Service station data representative of local site conditions are available.
12-11
-------
Table 12.2
Release Characterization Tasks for Air
e
[ Investigatory Tasks
Investigatory Techniques
1. Waste/Unit characterization
• Identification of waste
constituents
See Section 3, land Volume I,
Appendix B List 2
Listiri of potential release
constiluents -
• Pnoritjzationofair,mission
Constituents
Wastesamplingand
characterization
Listingoftargetair .mission
constituents for monitoring
• Identification of unit
characteristics which may
promote an air release
2. environmental 5ethreg
I Characterization
I - Definition of climate
See Section 7
climate summaries for regional
National Weather Service
stations (may require onsite
meteorological monitoring
survey)
. Description of the unit
. Wind roses and statistical
tabulations for parameters of
interest
• Definition of iite-specific
meteorological conditions
Orsite meteorological
monitoring concurrent with air
monitoring
Wind roses and tabulations for
parameters of interest
• Definition of soil conditions
to characterize emission
potential for particulate
emissions and for certain
units (e.g. landfills and land
treatment) for gaseous
emissions
See Section 9
Soil physical properties (e.g..
porosity, organic matter
content)
• Definition of site-specific
terrain
• Identification of potential
air.pathway receptors
3. Release Characterization
See Section 7 9 and Appendix A
(Volume 1)01 RFI and recent
aerial photographs and U.S.
Geolgoical Survey maps
Census data, area surveys, recent
aerial photographs and U.S.
Geological Survey topographic
maps
Topographic map of site area
Map with identification of
nearby populations and
buildings
- Identification of
- Reasonable Worst Cas.
conditions
Wind patterns and/or
emission/dispersion modeling
Monthly seasonal wind roses
and/or table of predicted
concentrations as a function of
downwind distances and
wind/stability conditions
- Screening evaluation of air
release to finalize air
monitoring program design
and select tarQet
constituents aT concern
Limited source/near-source
sampling
Listing of concentration levels
• Characterization of target
constituents
Upwind/downwind air
monitoring, or (for certain
situations) source emission rate
monitonna dispersion modeling
Tables of concentrations.
Detailed assessment of extent
and magnitude of air releases
12-12
-------
Development of monitoring procedures generally includes the collection of
meteorological data concurrent with air quality measurements. The meteorological
data are needed_ during the air monitoring program to characterize emission
potential and atmospheric dispersion conditions. This information is also used to
evaluate source/receptor relationships and to interpret the air monitoring data.
Development of monitoring procedures should address selection of target air
emission constituents. One acceptable approach is to monitor for all Appendix VIII
potential air emission constituents (See Appendix B, List 2) applicable to the unit or
release of concern. An alternative approach is to use unit- and waste-specific
information to identify constituents that aPe expected to be present, thus reducing
the list of target monitoring constituents (See Section 3.6).
Development of monitoring procedures should also include selection of
appropriate field and analytical methods for conducting the air monitoring
program. Candidate methods and criteria for monitoring program design (e.g..
relevant to sampling schedule and monitor placement) should be limited to
standard published protocols (such as those available from EPA. NIOSH. and ASTM).
Selection of appropriate methods will be dependent on site and unit-specific
conditions.
The air monitoring program will generally consist of several phases as follows:
• Screening sampling to verify the presence of a suspected release (in those
cases where release verification is appropriate), to prioritize sources (based
on emission potential asdetermined byobtaining airsamplesatorneafthe
source) at multiple-unit facilities, and to obtain information to aid in
design of the air monitoring program;
• Initial monitoring (air monitoring shou’d be conducted for a 90-day period)
to characterize air concentrations at actual offsite receptor locations as
input to the health and environmental assessment. This will generally
involve air monitoring stations at the facility (to maximize the potential for
detection of the release) and at actual offsite receptor locations (if
practical), or application of dispersion models to estimate offsite
concentration levels at receptor locations; and
12-13
-------
• Subsequent monitoring, if needed, to better define the magnitude and’
extent of the release to air or, in certain cases, to evaluate the air
concentration levels subsequent to the implementation of corrective
measures. Subsequent monitoring will be necessary if results of initial
monitoring and modeling do not provide an adequate basis for estimating
long term exposures at actual offsite receptor locations. For example,
subsequent monitoring would be necessary if the initial monitoring phase
was not representative of long-term exposure conditions
All phases may not be needed for each investigation depending on the site-
specific air monitoring data available and the nature and magnitude of the release.
A limited sampling program may be necessary for screening purposes to finalize
design of the air monitoring program. The objective of this screening sampling will
be to verify a suspected release, if appropriate, and to further assist in identificating
and quantifying of release constituents of concern. Screening sampling at each unit
for a multiple-unit facility can be used to prioritize release sources. Therefore, the
emphasis during this screening will be on obtaining air samples near the source, or
collecting a limited number of source emission samples. The availability of air
monitoring data or units with a limited set of air emission constituents may
preclude the need for screening sampling during the RFI process.
An initial air monitoring program should be conducted, as necessary, to
characterize the magnitude and distribution of air concentration levels for the
target constituents selected. Subsequent monitortng may also be necessary to more
thoroughly evaluate concentration levels at offsite receptors.
The basic approach for the initial air monitoring will consist of collection of
ambient air samples for four target zones: the first zone located upwind of the
source to define background contamination levels; the second zone located
downwind at the unit boundary; the third zone located downwind at the facility
property boundary to maximize the potential for release detection; and a fourth
zone offsite, as practical, to determine concentrations at actual offsite receptors for
input into the health and environmental assessment. Offsite air monitoring may
r ot always be practical due to various problems (e.g., vandalism, public tampering
12-14
-------
with equipment, public relations and legal access problems). Dispersion modeling
can be used to estimate offsite concentrations if monitoring data are not available
for the actual reeptor locations of interest. Multiple monitoring stations will
generally be required for each of the four target zones.
The location of air monitors within each zone should be based on site-specific
diurnal and seasonal wind patterns appropriate for the monitoring period. The
objective of the monitoring network should be to provide adequate coverage for
primary air flowpaths for each of the zones enumerated above.
As concentration measurements or estimates for offsite receptor locations
become available, both within and at the conclusion of discrete investigation
phases, they should be reported to the regulatory agency as directed. The
regulatory agency will compare the concentrations with applicable health and
environmental criteria to determine the need for (1) interim corrective measures;
and (2) a Corrective Measures Study. In addition, the regulatory agency will
evaluate the data with respect to adequacy and completeness to determine the
need for any additional characterization efforts. The health and environmental
criteria and a general discussion of how the regulatory agency will apply them are
supplied in Section 8. A flow diagram illustrating RFI Decision Points is provided in
Section 3 (See Figure 3-2).
Notwithstanding the above process, the owner or operator has a continuing
responsibility to identify and respond to emergency situations and to define priority
situations that may warrant interim corrective measures. For these situations, the
owner or operator is advised and follow the RCRA Contingency Plan requirements
under 40 CFR Part 264 Subpart D and Part 265, Subpart D.
12.2.1.2 Emission/Dispersion Modeling
Modeling can be an integral part of the release characterization for air. The
major modeling applications can be summarized as follows:
S Emission models can be used in conjunction with screening sampling results
to prioritize sources at a facility to support the design of an air monitoring
12-15
-------
program (e.g., to identify units that warrant placement of one or more air.
monitoring stations nearby);
• Dispersion models can be used to identify expected high concentration
areas relative to actual offsite receptor locations which can be considered
priority locations for air monitoring stations;
• Dispersion models, using available onsite or offsite historical
meteorological data, can be used to identify the “reasonable worst case”
90-day period for conducting the air monitoring program;
• Dispersion models with concurrent meteorological monitoring data as
input can be used to determine if the air monitoring was conducted during
a reasonable worst case” conditions;
• Monitoring and/or emission rate data are available within the facility
property boundary, dispersion models can be used to estimate
concentrations at actual offsite receptor locations if monitoring data arei
not available for these locations; and
• Both emission and dispersion models can be used to estimate
concentrations if analytical detection limits for ambient and emission rate
(source) monitoring are greater than expected constituent concentrations.
Emission rate models can provide a screening test to support the design of an air
monitoring program. These models can be used to identify potential major air
emission sources at a facility (especially multiple unit-facilities). For this type of
application, modeling results are used to compare routine long-term emissions from
various units to prioritize the need for air monitoring at each unit. (For example,
modeling results may indicate that 90 percent of the volatile organic compound
emissions at a facility are attributable to surface impoundment units and only 10
percent to other sources. Therefore, emphasis should be on characterizing releases
from the surface impoundments.) Emission rate modeling results are used on a
comparative basis; absolute emission rates are not a primary objective of the
assessment.
12-16
-------
Atmospheric dispersion models can also be used to assist in designing an air
monitoring program. Modeling results can be used to identify offsite areas of high
concentration relative to actual receptor locations. High concentration areas which
correspond to actual receptors are priority locations for air monitoring stations.
Dispersion models can also be used to provide seasonal dispersion “patterns
based on available representative historical meteorological data (either onsite or
offsite). Comparison of seasonal dispersion patterns can be used to identify
reasonable worst case N 90-day period for monitoring. Dispersion patterns based
on modeling results can similarly be used to evaluate the representativeness of the
data collection period. Representativeness is determined by comparing the
dispersion patterns for the air monitoring period with historic seasonal dispersion
patterns.
Frequently, it may not be practical to place air monitoring stations at actual
offsite receptor locations. However, it will be necessary to characterize
concentrations at these locations to conduct a health and environmental
assessment. In these cases, dispersion patterns based on modeling results can be
used to extrapolate concentrations monitored at the facility property boundary to
offsite receptor locations.
Modeling can also be used to estimate offsite concentrations if it is not feasible
to collect air monitoring data at the facility property boundary. Source emission
rate monitoring data may be collected for some situations if analytical detection
limits for ambient monitoring are expected to be less than constituent
concentrations. These emission rate monitoring data can be input into a dispersion
model that can be used to estimate offsite concentrations.
The objective of the modeling applications discussed above involves the
estimation of long-term (i.e., several months to years) concentration patterns.
These long-term patterns do not have the variability associated with short-term
(i.e., hours to days, such as a 24-hour event) emission rate and dispersion conditions.
Concentration patterns derived from models will primarily be used to estimate
relatively high concentration areas. For such an application, it will not be necessary
to calculate actual concentrations; instead, dispersion or dilution patterns are
12-17
-------
derived. Dispersion or dilution patterns illustrate the relative change in
concentration as a function of distance and direction from the release source. As aru
example, dilutior pattern results may indicate that the concentration at the nearest”
receptor is expected to be one half of the value at the facility property boundary.
Therefore, if a 10 ug/m 3 value was measured at the facility property boundary, a
concentration df S ug/m 3 would be expected at the nearest receptor.
Modeling applications are, however, limited by the amount, quality, and
representativeness of the input data. Meteorological data are the key input for
developing dispersion or dilution patterns. In addition, standard dispersion models
are not considered to be accurate for most complex terrain applications (results can
be off by greater than a factor of 10). Air emission release rate models require
waste constituent information as key input. However, the spatial variation of
wastes at some units may not be well known and, therefore, modeling may not be
appropriate if adequate input data are not available.
The use of the Industrial Source Complex (ISC) Model is recommended for
evaluating dispersion of hazardous air pollutants. Applicable ISC source types
include stack, area, and volume sources. Concentration estimates can be based or
times of as short as one hour and as long as annual average times. The model can b
used for both flat and rolling terrain. The ISC model can also account for
atmospheric deposition (i.e., inter-media transport to soil). The ISC Model, (see EPA
45014.79-030) as well as alternative EPA-approved models (e.g., the UNAMAP series)
is available through the NT iS.
Alternative dispersion models, including the use of simple screening models
(e.g., EPA-model Point Plume, PTPLU) or hand calculation approaches are available
for point sources located in flat terrains based on the following guidance:
Turner, DL 1969. Workbook of Atmospheric Dispersion Estimates . Public
Health Service. Cincinnati, OH.
Guidance on application of the SC model and other acceptable dispersion
models, as well as on modeling for complex terrain sites is provided in the following
documents:
12-18
-------
U.S. EPA. July, 1986. Guidelines on Air Quality Models (Revised) . EPA-45012-78-
027R. NTIS P886-245248. Office of Air Quality Planning and Standards. Research
Triangle Park,.N.C. 27711.
U.S. EPA. October 1977. Guidelines for Air Quality Maintenance Planning and
Analysis. Vol. 10 (Revised): Procedures for Evaluating Air Quality Impact of New
Stationary Sources . EPA-450/4-77-O01. NTIS PB274-087. Office of Air Quality
Planning and Standards. Research Triangle Park, NC. 27711.
Air emission release rate models, including models that are available for use on
personal computers, are presented in the following reference:
US. EPA. 1987. Hazardous Waste Treatment, Storage and Disposal Facilities
( TSDF) - Air Emission Models - Draft Report Office of Air Quality Planning and
Standards. Research Triangle Park, NC 27711.
Additional pertinent references include the following:
U.S. EPA. 1985. Compilation of Air Pollutant Emission Factors . EPA, AP-42.
Office of Air Quality P’anning and Standards. Research Triangle Park, NC 27711.
U.S. EPA. 1984. Evaluation and Selection of Models for Estimating Air Emissions
from Hazardous Waste Treatment, Storage and Disposal Facilities . EPA 450/3-84-
020. Office of Air Quality Planning and Standards. Research Triangle Park, NC
27711.
U.S. EPA. June, 1984. Evaluation of Air Emissions from Hazardous Waste
Treatment. Storaae and Disposal Facilities . EPA 600/2-85-1057. Office of
Research and Development. Cincinnati, OH 45268.
U.S. EPA. February, 1985. Rapid Assessment of Exposure to Particulate Emissions
from Surface Contamination Sites . EPA/600-18-85/002. Office of Health and
Environ mental Research. Washington, D.C. 20460.
For some applications, it can be assumed that all the volatile wastes handled
will eventually be emitted to the air. This assumption is generally appropriate for
12-19
-------
volatile organic compounds placed in a disposal unit such as a surface
impoundment. In these cases, the air emission rate can be assumed to be equivalent
to the disposal rate and a emission rate model may not be required. This
assumption is valid because of the long-term residence time for wastes in the
disposal units. Frequently 1 a substantial portion of the volatile constituents will be
released to the atmosphere within several days from open units such as surface
impoundments. However, for more complex situations (e.g., storage or treatment
units where total volatilization of the constituents is not expected), air emission
models can be used to obtain a more refined long-term release rate.
Before proposing any models, the owner or operator is advised to consult with
the regulatory agency.
12.2.2 lnter.media Tr*nsport
Subsurface gas migration, contaminated surface water and contaminated soil
can all result in inter-media transport of contaminants to air. Subsurface gas can
migrate to the land surface or be released to the atmosphere artificially from gas
vents or from gas collection systems. Volatilization is the primary mechanism for
release to air from contaminated surface water Release to air from contaminated
soil can be caused by the volatilization of organics or from wind erosion of
‘particulates (e.g., containing heavy metals). Therefore, information collected from
other media investigations can provide useful input data for characterizing releases
to air. It may also be efficient to concurrently investigate these media. However,
once releases become airborne, the characterization approach presented in this
section is applicable.
Releases to air also have the potential for contaminating other media. Releases
to air can contaminate soil and surface water via [ wet and dry] deposition. It is
generally difficult to directly monitor these deposition processes. In these cases,
removal rates can be estimated by use of specialized atmospheric dispersion models
or by direct measurements of soil and surface water contaminants. Information
from the investigation can provide useful input for assessing the significance of
atmospheric deposition.
12-20
-------
12.3 Characterization of the Contaminant Source and the Environmental
Setting
Release investigations can be conducted in an efficient, effective and
representative manner if certain information is obtained prior to implementation
of the effort. This information consists of both waste/unit characterization and
characterization of the environmental setting. Review of information from existing
sources can be used to identify data gaps and to initiate data collection activities to
fill these data gaps. Waste/unit characterization and characterization of the
environmental setting are discussed below:
Waste and unit specific information . Data on the specific constituents
present in the unit that are likely to be released to the air can be used to
design sampling efforts and identify candidate constituents to be
monitored. This information can be obtained from either a review of the
existing information on the waste or from new sampling and analysis. The
manner in which the wastes are treated, stored or disposed may have a
bearing on the magnitude of air emissions from a unit. In many cases, this
information may be obtained from facility records, contact with the
manufacturer of any control devices, or 1 in some cases, from the facility’s
RCRA permit application.
Environmental settinQ information . Environmental setting information,
particularly climatological data, is essential in characterizing an air release.
Climatological parameters such as wind speed and temperature will have a
significant impact on the distribution of a release and in determining
whether a particular constituent will be released. Climatological and
meteorological information for the area in which the facility is located can
be obtained either through an onsite monitoring effort or from the
National Climatic Data Center (Asheville, NC). The climatologial data
should be evaluated considering site topography and other local influences
that can affect the data representativeness.
Information pertaining to the waste, unit, and environmental setting can be
found in many readily available sources. General information concerning
12-21
-------
waste/unit characterization is discussed in Section 7. Air specific information is
provided in the following discussions.
12.3.1 Waste Characterization
Several waste characteristics contribute to the potential for a waste constituent
to be released via the air pathway. These characteristics, in conjunction with the
type of unit and its operation, will determine whether a release will be via
volatilization of the constituent or as particulate entrainment. Malor factors
include the types and number of hazardous constituents present, the
concentrations of these constituents in the waste(s), and the chemical and physical
characteristics of the waste and its constituents. AU of these factors should be
considered in the context of the specific unit operation involved. It is important to
recognize that the constituents of concern in a particulate release may involve
constituents that are either sorbed onto the particulate, or constituents which
actually comprise the particulate.
12.3.1.1 Presence of Constituents
The composition of the wastes managed in the unit of concern will influence the
nature of a release to air. Previous studies may indicate that the constituents are
present in the unit or that there is a potential for the presence of these constituents.
In determining the nature of a release, it may be necessary to determine the specific
waste constituents in the unit if this has not already been done. Guidance on
selecting monitoring constituents is presented in Section 3 (and Appendix 8); waste
characterization guidance is presented in Section 7.
12.3.1.2 Physical/Chemical Properties
The physical and chemical properties of the waste constituents will affect
whether they will be released, and if released, what form the release will take (i.e.,
vapor, particulate, or particulate-associated). These factors are identified in Table
12-3 as a function of emission and waste type. Important factors to consider when
assessing the volatilization of a constituent include the following:
12-22
-------
• Water solubility . The solubility in water indicates the maximum
concentration at which a constituent can dissolve in water at a given
temperature. This value can help the investigator estimate the distribution
of a constituent between the dissolved aqueous phase in the unit and the
undissolved solid or immiscible liquid phase. Considered in combination
with the constituent’s vapor pressure, solubility can provide a relative
assessment of the potential for volatilization of a constituent from an
aqueous environment.
• Vapor pressure . This property is a measure of the pressure of vapor in
equilibrium with a pure liquid. It is best used in a relative
sense;constituents with high vapor pressures are more likely to be
released than those with low vapor pressures, depending on other factors
such as relative solubility and concentration (e.g.. at high concentrations
releases can occur even though a constituent’s vapor pressure is relatively
low).
• Octanol/water partition coefficient . The octanol/water partition
coefficient indicates the tendency of an organic constituent to sorb to
organic components of soil or waste matrices. Constituents with high
octanoltwater partition coefficients tend to adsorb readily to organic
carbon, rather than volatilizing to the atmosphere. This is particularly
important in landfills and land treatment units, where high organic carbon
content in soils or cover material can significantly reduce the release
potential of volatile constituents.
• Partial pressure . For constituents in a mixture, particularly in a solid matrix,
the partial pressure of a constituent will be more significant than pure
vapor pressure. A partial pressure measures the pressure which each
component of a mixture of liquid or solid substances will exert in order to
enter the gaseous phase. The rate of volatilization of an organic chemical
when either dissolved in water or present in a solid mixture is charcterized
by the partial pressure of that chemical. In general, the greater the partial
pressure, the greater the potential for release. Partial pressure values are
unique for any given chemical in any given mixture and may be difficult to
12-23
-------
TABLE 12.3
PARAMETERS AND MEASURES FOR USE IN EVALUATING POTENTIAL
RELtASES OF HAZARDOUS WASTE CONSTITUENTS TO AIR
Emission and Waste TyDe Units of Concern IL Useful
A. Vapor Phase Emissions
• Dilute Aqueous Surface Impoundments, Tanks, Solubility, Vapor Pressure,
Solutuonl/ Containers Partial Pressure 31
• Conc. Aqueous Tanks, Containers, Surface Solubility, Vapor Pressure,
So lution 2 / Impoundments Partial Pressure, Raoults
Law
- Immiscible Liquid Containers, Tanks Vapor Pressure, Partial
Pressure
- Solid Landfills, Waste Piles, Land Vapor Pressure, Partial
Treatment Pressure, OctanolPWater
Partition Coefficient,
Porosity
B. Particulate Emissions
Solid Landfills, Waste Piles. Land Particle Size Distribution,
Treatment Unit Operations,
Management Methods
1/ Incinerators are not specifically listed on this table because of the unique issues concerning air emissions from
these units. Although Incinerators can burn many forms of waste, the potential for release from these units is
primarily a function of incinerator operating conditions and emission controls, rather than waste
characterisitics.
21 Although the octanoltwater partition coefficient of a constituent is usually not an important characteristic in
these waste streams, there are conditions where it can be cntical Specifically, in waste containing high
concentrations of organic particulates, constituents with high octanol/water partition coefficients will adsorb
to the particulates. They will become part of the sludge or sediment matrix, rather than volatilizing from the
unit.
3’ Applicable to mixtures of volatile components.
12-24
-------
obtain. However, when waste characterization data is avatlable, partial pressure
can be estimated using methods commonly found in engineering and
environmental science handbooks.
• Henry’s Law constant . Henry’s law constant is the ratio of the vapor
pressure of a constituent to its aqueous solubility (at equilibrium). This
constant can be used to assess the relative ease with which the compound
may vaporize from the aqueous phase. It is applicable onty for low
concentration (i.e., less than 10 percent) wastes in aqueous solution arid
will be most useful when the unit being assessed is a surface impoundment
or tank containing dilute wastewaters. The potential for significant
vaporization increases is the value for Henry’s Law Constant increases;
when it is greater than 1OE•3, rapid volatilization will generally occur.
• Raoult’s Law . Raoult’s Law accurately predicts the behavior of most
concentrated mixtures of water and organic solvents (i.e., solutions over
10% solute). According to Raoult’s Law, the rate of volatlization of each
chemical in a mixture is proportional to the product of its concentration in
the mixture and its vapor pressure. Therefore, Raoult’s Law can be used to
characterize volatilization potential. This will be expecially useful when
the unit of concern entails container storage, tank storage, or treatment of
concentrated waste streams.
A summary of some of these factors for several constituents is given in Tables 12-
4 and 12-5. The following document contains a compilation of chemical-physical
properties for several hundred constituents. Additional references for these data
are provided in Section 7.
U.S. EPA. 1987. Hazardous Waste Treatment Storage arid Disposal Facilities
( TSDF) • Air Emission Models . Office Air Quality Planning and Standards.
Research Triangle Park, N.C. 27711
For airborne particluates, the particle size distribution plays an important role in
both dispersion and actual inhalation exposure. Large particles tend to settle out of
the air more rapidly than small particles. Very small particles (i.e., those that are less
12-25
-------
TABLE 12.4
PHYSICAL PARAMETERS OF VOLATiLE HAZARDOUS CONSTITUENTS
Hazardous COnStTtuent
Molecular
P
at 25°C (rn /U
1
Acetald.hyd•
44
915
1 OOE + 06
9.5 0E• 05
Acrol*,n -
56
244
4 OOE + 05
4.07E-05
Acrylonitrile
53
114
7 90E • 04
B 80E-05
Allyichioridi
76.S
340
340E•01
Benaeni
78
95
1 78E +03
5 50E.03
8erizyl chloride
126 6
1 21
1 00
Carbon tetrachloride
154
109
8.OOE + 02
2.OOE02
ChlorobenZ,n.
112
12
SOOE. 02
200E• 03
Chloroform
119
192
8.OOE +03
3 OOE-03
Chloroprene
885
215
Cresols
108
0.4
2.OOE.04
4.60E- 07
Cumene (isopropylbenzerie)
120
4 6
SO 0
2. O OE-04
1,4-dichjorob er iz,ne
147
1.4
49 00
1,2-dichloroethan,
99
62
8.69E .03
1.OOE-04
Dichloromethane
85
360
2.OOE • 04
2.OOE-03
Dioxin
178
7 6E-7
3 17E-04
1.20E•03
pich lorohydrin
92.5
13
6.OOE.04
3.08E-05
thylbenzen.
106
10
152
7.OOE-03
thyleneoxid.
44
1,095
1.3SEi 05
Formaldehyde
30
3,500
3.OOE • 05
Hexich lorobutadien,
261
0.15
Hydrogen cyanide
27
726
Hydrogen flouride
20
900
Hydrogen sulfide
34
15.200
Hexachlorocyclop.ntadi.n,
273
0.03
Maliic anhydrid.
98
0.3
1 63E + 05
Methyl acetate
74
170
3.19E .05
1. O OE-04
N-Dimethylnitrosamine
81
3.4
Naphthl.n.
123
0.23
Nitrobenzene
Ilitrosomoipholine
Phenol
0.3
1.90E .03
1 30E•05
5.3
94
0.34
930E404
102E -05
Phosgeno
98
1,300
Phthalicarihydnde
148
0.03
6.17E +03
9.OOE-07
Propylene oxide
400
1,1,2,2-tetrachloroethan,
168
9
2.90E +03
2.OOE-04
T .trachloroethylene
166
15
200
Toluerie
92
30
534
5.OOE03
1,1 ,1 .tnchloroethan.
133
123
720
2.15E .02
Trichloroethyline
131
90
1.IOE +03
8.92E-03
Vinylchioride
62 5
2,600
6.OOE + 03
1.90E.01
Vinylidenechloride
97
500
Xyl enes
106
8 5
1 00
4.04E04
4i iC
-------
TABLE 12.5
PHYSICAL PARAMETERS OF PCB MIXTURES*
0 —
Arochior
(PCB)
Vapor pressure
at 25°C (atm)
Solubility
at 25°C (mg/i)
Henry’s Law
constant
(atm-m3/mol)
1242
2.19E-07
2400
238E-08
1248
1.02E-07
520
1.02E-08
1254
1.85E-08
120
1.40E-08
1260
5.17E-09
30
6.46E -08
* All values estimated based on calculations.
12-27
-------
than 2.5 to 10 microns in diameter) are considered to be respirable and thus present.
a greater health hazard than the larger particles. Therefore, the source of th
release should b examined to obtain information on particle size. Process
information may be sufficient to grossly characterize the potential for particulate
formation. For xample, the presence of ash materials and similar wastes would be
a case in which particulate emissions would be of concern.
12.3.2 Unit Characterization
Different types of units may have differing release potentials. The particular
type of unit, its configuration, and its operating conditions will have a great effect
on the nature, extent, and rate of the release. These practices or parameters should
be determined and reasonable worst-case operating practices or conditions should
also be identified prior to initial sampling.
12.3.2.1 Type of Unit
The type of unit will affect its release potential and the types of releases
expected. For the purpose of this guidance, units have been divided into three
general types with regard to investigating releases to air. These are:
• Area sources having solid surfaces, including land treatment facilities,
surfaces of landfills, and waste piles;
• Point sources, including vents, (e.g., breathing vents from tanks) and
ventilation outlets from enclosed units (e.g., container handling facilities or
stacks); and
• Area sources having liquid surfaces, including surface impoundments and
open-top tanks.
The following discussion provides examples for each of these unit types and
illustrates the kind of data that should be collected prior to establishing a sampling
plan. Table 12-6 indicates types of releases most likely to be observed from each of
these example unit types. It should also be recognized that releases to air can be4
continuous or intermittent in nature.
12-28
-------
TABLE 12.6
SUMMARY OF TYPICAL UNIT SOURCE TYPE AND AIR RELEASE TYPE
Typical
Unit Type
Source Ipe
Potential Phase
of Release
Area Sources
with Uquid
Surface
Aria Sources
with Solid
Surface
Point Sources
Vapor
Particulate
Waste Piles
X
X
X
Land Treatment
Units
X
X
X
Landfills
X
X
X
X
Drum Handling
Facilities
X
X
X
Tanks
X
X
X
Surface
Impoundments
X
x
lncinerators
X
X
X
Includes units (e.g., 9arbage incinerators) not covered by 40 CFR Part 264
SubpartO which pertains to hazardous waste incinerators.
12-29
-------
Waste piles--Waste piles are primarily Sources of particulate releases due to!
entrainment intothe air of solid particles from the pile. Waste piles are generally
comprised of dry materials which may be released into the air by wind or
operational activities. The major air contaminants of concern from waste piles will
be those compounds that are part of or have been adsorbed onto the particulates.
Additionally, volatilization of some constituents may occur. Important unit factors
include the waste pile dimensions (e.g., length, width, height, diameter and shape).
and the waste management practices (e.g., the frequency and manner in which the
wastes are applied to the pile and whether any dust suppression procedures are
employed). The pile dimensions determine the surface area available for wind
erosion. Disturbances to the pile can break down the surface crust and thus increase
the potential for particulate emissions. Dust suppression activities, however, can
help to reduce particulate emissions.
Land treatment units--Liquid or sludge wastes may be applied to tracts of soil in
various ways such as surface spreading of sludges, liquid spraying on the surface,
and subsurface liquid injection. These methods may also involve cultivation or,
tilling of the soil. Vapor phase and particulate contaminant releases are influenced
by the various application techniques. Particulate or volatile emission releases are
most likely to occur during initial application or during tilling, because tilling keeps
the soil unconsolidated and loose, and increases the air to waste surface area.
Important unit factors in assessing an air release from a land treatment unit include:
• Waste application method Liquid spraying applications tend to minimize
particulate releases while increasing potential volatile releases. Subsurface
applications generally reduce the potential for particulate and volatile
releases.
• Moisture content of the waste - Wastes with high moisture content will be
less likely to be released as particulates; however, a potential vapor phase
release will become more likely.
12-30
-------
• Soil characteristics - Certain constituents, such as hydrophobic organics, will
be more..likely to bound to highly organic soils than non-organic soils.
Therefore, releases of these types of constituents are most likely to be
associated with particulate emissions.
Landfills—Landfills can result in particulate and vapor phase releases. This process
generally involves placement of waste in subsurface disposal cells and subsequent
covering of the waste with uncontaminated soil. Landfill characteristics that can
affect contaminant release include:
• Porosity and moisture content of the soil or clay covering can influence the
rate at which vapor phase releases move through the soil towards the
surface. Finer.soils with lower porosities will generally slow movement of
vapors through the unit. The frequency of applying soil cover to the open
working face of a landfill will also affect the time of waste exposure to the
air.
• Co-disposal of hazardous and municipal wastes will often increase the
potential for vapor phase releases, because biodegradation of municipal
wastes results in the formation of methane gas as well as other volatile
organics. Methane gas may act as a driving force for release of other
volatile hazardous components that may be in the unit (See Section 11 -
Subsurface gas.)
• Landfill gas vents, if present, can act as sources of vapor phase emissions of
contaminated landfill gases.
• Leachate collection systems can be sites of increased vapor phase emissions
due to the concentrated nature of the leachate collected. Open trenches
are more likely to be emission sources than underground collection sumps
due to the increased exposure to the atmosphere.
• Waste mixing or consolidation areas where bulk wastes are mixed with soil
or other materials (e.g., fly ash) prior to landfilling can be contributors to
both particulate and vapor phase air releases. Practices such as spreading
12-31
-------
materials on the ground to release moisture prior to landfilling will also
increase exposure to the atmosphere.
.
Drum handling facilities--Emissions from drum or container handling areas can
result from several types of basic operations. Frequently, emissions from these
operations are vented to the air through ducts or ventilation systems. Air sampling
to assess emissions from these operations may include sampling of the control
device outlets, the workplace atmosphere at each operation, or the ambient air
downwind of the unit. Factors which effect emissions include:
• Filling operations can be a major source of either vapor or particulate
emissions due to agitation of the materials during the filling process.
Spillage which occurs during loading may also contribute to emissions.
Organic waste components with high volatility will readily vaporize into
the air. Similarly, particulate matter can be atmospherically entrained by
agitation and wind action. The emission potential of filling operations will
be affected by exposure to ambient air. Generally, fugitive emissions from
an enclosed building will be less than emissions created during loading in,
an open structure.
• Cleaning operations can have a high potential for emissions. These
emissions may be enhanced by the use of solvents or steam cleaning
equipment. The waste collection systems at these operations usually
provide for surface runoff to open or below ground sumps, which can also
contribute to air emissions.
• Volatilization of waste components can also occur at storage units. Since it
is common practice to segregate incompatible wastes during storage, the
potential for air releases may differ within a storage unit depending on the
nature of the wastes stored in any particular area. The most common
source of air emission releases from drum storage areas is spills from drums
ruptured during shipping and handling.
• For offsite facilities, storage areas frequently are located where drums are
sampled during the waste testing/acceptance process. This process involves
12-32
-------
drum opening for sampling and could also include spillage of waste
materials on the ground or floor.
Important release information includes emission rates, and data to estimate
release rise (e.g.. vent height and diameter as well as vent exit temperature and
velocity). Information pertaining to building dimensions/orientation of the unit
and nearby structures is needed to assess the potential for aerodynamic behavior of
the stack/vent release. These input data would be needed if atmospheric dispersion
modeling was necessary.
Tanks-.Tanks can emit volatile waste components under various circumstances. A
major determinant of any air emission will be the type of tank being studied. Closed
or fixed roof storage tanks will most likely exhibit less potential for air emissions
than open topped tanks. Some tanks are equipped with vapor recovery systems
that are designed to reduce emissions. Important process variables for
understanding air emissions from tanks can be classified as descriptive and
operational variables:
• Descriptive variables include - type, age, location, and configuration of the
tank.
• Operational variables include aeration, agitation, filling techniques,
surface area, throughput, operating pressure and temperature, sludge
removal technique and frequency, cleaning technique and frequency,
waste retention and vent pipe dimensions and flow rate.
Important release information includes emission rates, and data to estimate
plume rise (e.g. 1 height and diameter as well as exit temperature and velocity).
Information pertaining to building dimensions/orientation of the unit and nearby
structures is needed to assess the potential for aerodynamic behavior of the
stack/vent release. These input data would be needed if atmospheric dispersion
modeling was necessary.
Surface impoundments—Surface impoundments are similar in many ways to tanks in
the manner in which air emissions may be created. Surface impoundments are
generally larger, at least in terms of exposed surface area, and are generally open to
12-33
-------
the atmosphere. The process variables important for the evaluation of releases to
air from surface impoundments can also be classified as descriptive and operational.’
• Descnptive parameters include - dimensions, including length, width, and
depth, berm design, construction and liner materials used, and the location
of the unit on the site.
• Operational parameters include - freeboard filling techniques (in
particular, splash versus submerged inlet), depth of liquid and sludge
layers, presence of multiple liquid layers, operating temperature, sludge
removal techniques and frequency, cleaning technique and frequency,
presence of aerators or mixers, biological activity factors for biotreatment,
and the presence of baffles, oil layers, or other control measures on the
liquid surface. (These factors are relevant to some tanks as well.)
Some surface impoundments are equipped with leak collection systems that
collect leaking liquids, usually into a sump. Air emissions can also occur from these
sumps. Sump operational characteristics and dimensions should be documented
and, if leaks occur, the volume of material entering the sump should be
documented. (These factors are relevant to some tanks as well.)
Incinerators - Stack emissions from incinerators (i.e., incinerator units not addressed
by RCRA in Part 264, Subpart 0, e.g., municipal refuse incinerators) can contain both
particulates and volatile constituents. The high temperatures of the incineration
process can also cause volatilization of low vapor pressure organics and metals.
Additional volatile releases can occur from malfunctioning valves during incinerator
charging. The potential for air emissions from these units is primarily a function of
incinerator operating conditions and emission controls. Important unit release
information indudes emission rates, and data to estimate plume rise (e.g., height
and diameter as well as exit temperature and velocity), as well as building
dimensions/orientation of the unit and nearby structures. This information is
needed to assess the aerodynamic behavior of the stack/vent release and for input
to atmospheric dispersion models.
12-34
-------
12.3.2.2 Sizeof Unit
The size of tht unit(s) of concern will have an important impact on the potential
magnitude of a release to air. The release of hazardous constituents to the air from
an area source is often directly proportional to the surface area of the unit, whether
this surface areLa is a liquid (e.g., in a tank) or a solid surface (e.g., a land treatment
unit). The scope of the air investigation may be a function of the size of the unit.
Generally, more sampling locations will be required as the unit increases in size, due
primarily to increased surface area. Also, as the total amount of waste material
present in a particular unit increases, it will represent a larger potential reservoir or
source of constituents which may be released.
Scaling factors, such as surface area to volume ratios should also be evaluated.
One large waste pile, for instance, can exhibit a lower ratio of surface area to total
volume than the sum of two smaller piles in which the total volume equals that of
the larger pile. Other units such as tanks may exhibit a similar economy of surface
area, based on the compact geometry of the unit.
Because releases to air generally occur at the waste/atmosphere interface,
surface area is generally a more important factor than total waste volume.
Consequently, operations that increase the atmosphere/waste interface, such as
agitation or aeration, splash filling, dumping or filling operations. and spreading
operations will tend to increase the emission rate. Total emissions, however, will be
a function of the total mass of the waste constituent(s) and the duration of the
release.
For point sources, the process or waste throughput rate wiH be the most
important unit information needed to evaluate the potential for air emissions (i.e..
stack/vent rsliasss).
12.3.2.3 Control Devices
The presence of air pollution control devices on units can have a major influence
on the nature and extent of releases. Control devices can include wet or dry
3crubbers, electrostatic precipitators, baghouses. filter systems. wetting practices for
solid materials, oil layers on surface impoundments, charcoal or resin absorption
12-35
-------
systems, vapor flares, and vapor recovery systems. Many of these controls systems
can be installed on many of the unit types discussed in this section. Due to th
variety of types o devices and the range of operational differences, an in depth
discussion of individual control devices is not presented here. Additional
information on control technologies for hazardous air pollutants is available in the
following references:
U.S. EPA. 1986. Handbook - Control Technologies for Hazardous Air Pollutants .
EPAi62516-861 014. NTIS PB 86-167U20 and PB 86-167038. Office of Research and
Development. Research Triangle Park, N.C. 27711.
U.S. EPA. 1986. Evaluation of Control Technologies for Hazardous Air
Pollutants : Volume 1 - Technical Report. EPAJ600/7-86/009a. NTIS PB 86-167020.
Volume 2 - Appendices. EPA/600/7-86/OOgb. NTISPB 86-167038. Office of
Research and Development, Research Triangle Park, N.C. 27711.
If a control device is present on the unit of concern, descriptive and operational
characteristics of the unit/control device combination should be reviewed and4
documented. In many cases, performance testing of these devices has been’
conducted after their installation on the unit(s). Information from this testing may
help to quantify releases to air from the unit(s); however, this testing may not have
been performed under a reaso bl worst-cases situation. The conditions under
which the testing was performed should be documented.
12.3.2.4 Operational Schedules
Another characteristic which can affect the magnitude of a release to air from a
unit is the unit’s operational schedule. If the unit is operational on a part time or
batch basis, the emission or release rate should be measured during both
operational and non-operational periods. In contrast to batch operations, emission
or release rates from continuous waste management operations may be measured
at any time.
12-36
-------
12.3.2.5 Temperature of Operation
Phase change of liquids and solids to gases is directly related to temperature.
Therefore, vapor phase releases to air are directly proportional to process
temperature. Thus, it is important to document operational temperature (i.e.,
waste temperature) and fluctuations to enhance the understanding of releases to
air from units. Particular attention should be paid to this parameter in the review of
e,zisting data or information regarding the operation of the unit.
The release rate of volatile components also generally increases with
temperature. Frequently, the same effeet is observed for particulates. because
entrainment is enhanced as materials are dried. Thus, the evaporation of any water
from solids, which generally increases as temperature increases, will likely increase
the emissions of many particulates in the waste streams. Evaporation of water may
also serve to concentrate wastes, leading to conditions more conducive to vapor
phase releases to air. It should also be noted that the destruction efficiency of
incinerators is also a function of temperature (i.e., higher temperatures are
generally associated with greater destruction efficiency).
12.3.3 CharacterizatiOn of the Environmental Setting
Environmental factors can influence not only the rate of a release to air but also
the potential for exposure. Significant environmental factors include climate, soil
conditions, terrain and location of receptors. These factors are discussed below:
12.3.3.1 Climate
Wind, atmospheric stability and temperature conditions affect emission rates
from area sources as well as atmospheric dispersion conditions for both area and
point sources. Historical summaries of climatic factors can provide a basis to assess
the long-term potential for air emissions and to characterize long-term ambient
concentration patterns for the area. Short-term measurements of these conditions
during air monitoring will provide the meteorological data needed to interpret the
concurrent air quality data. Meteorological monitoring procedures are discussed in
Section 12.6. Available climatic information, on an annual and monthly or seasonal
basis, should be collected for the following parameters:
12-37
-------
• Wind direction and roses (which affects atmospheric transport, and can be
used to determine the direction and dispersion of release migration);
• Mean wind speeds (which affects the potential for dilution of releases to
air);
• Atmospheric stability distributions (which affects dispersion conditions);
• Temperature means and extremes (which affects the potential for
volatilization, release rise and wind erosion);
• Precipitation means (which affects the potential for wind erosion of
particulates);
• Atmospheric pressure means (which affects the potential for air emissions
from landfills); and
• Humidity means (which can affect the air collection efficiencies of some
adsorbents - see Section 12.6).
The primary source of climate information for the United States is the National
Climatic Data Center (Asheville, NC). The National Climatic Data Center can provide
climate summaries for the National Weather Service station nearest to the site of
interest. Standard references for climatic information include the following:
National Climatic Data Center. Local Climatological Data - Annual Summaries
with Comparative Data , published annually. Asheville, NC 28801.
National Climatic Data Center. Climates of the States . 1973. Asheville, NC
28801.
National Climatic Data Center. Weather Atlas of the United States . 1968.
Asheville, NC 28801.
12-38
-------
The climatological data should be evaluated considering the effects of
topography and other local influences that can affect data representativeness.
A meteorological monitoring survey should be conducted prior to ambient air
monitoring to establish the local wind flow patterns and for determining the
number and locations of sampling stations. The survey results will be used to
characterize local prevailing winds and diurnal wind flow patterns (e.g., daytime
upsiope winds, nighttime downslope winds, sea breeze conditions) at the site. The
survey should be conducted for a one-month period and possibly longer to
adequately characterize anticipated wind patterns during the air monitoring
program. Inland, flat terrain conditions may not necessitate an onsite
meteorological monitoring survey if representative data are available from previous
onsite studies or from National Weather Service stations.
The meteorological monitoring data collected during the initial air monitoring
phase can serve as a basis for the placement of air sampling stations during any
subsequent monitoring phases.
12.3.3.2 Soil Conditions
Soil conditions (e.g., soil porosity) can affect air emissions from landfills and the
particulate wind erosion potential of contaminated surface soils. Soil conditions
pertinent to characterizing the potential for air emissions include the following:
• Soil porosity (which affects the rate of potential gaseous emissions);
• Particle size distribution (which affects the potential for particulate
emissions from contaminated soils); and
• Contaminant concentrations in soil (i.e., potential to act as air emission
sources).
Soil information characterization information is presented in Section 9.
12-39
-------
12.3.3.3 Terrain
Terrain features can significantly influence the atmospheric transport of air
emissions. Terrain heights relative to release heights will affect groundlevel
concentration. lerrain obstacles such as hills and mountains can divert regional
winds. Likewise, valleys can channel wind flows and also limit horizontal dispersion.
In addition, complex terrain can result in the development of local diurnal wind
circulations and affect wind speed, atmospheric turbulence and stability conditions.
Topographic maps of the facility and adjacent areas are needed to assess local and
regional terrain. Guidance on the appropriate format and sources of topographic
and other maps is presented in Section 7 and Appendix A.
12.3.3.4 Receptors
Information concerning the locations of nearby buildings and the population
distribution in the vicinity of the site are needed to identify potential air-pathway
receptors. This receptor information provides a basis for specifying strategies for air
sampling locations. Environmental and human receptor information is needed to 1
assess potential air-pathway exposures and to determine air monitor placement.
Such information may include:
• A site boundary map;
• Location of nearest buildings and residences for each of the sixteen 22.5
degree sectors which correspond to major compass points (e.g., north,
north.northwest);
• Location of buildings and residences that correspond to the area of
maximum offsite groundlevel concentrations based on preliminary
modeling estimates (these locations may not necessarily be near the site
boundary for elevated releases); and
• Identification of nearby sensitive receptors (e.g., nursing homes, hospitals,
schools, crticial habitat of endangered or threatened species).
12-40
-------
The above information should be considered in the planning of an air
monitoring program. Additional guidance on receptor information is provided in
Section 2.
12.3.4 Review of Existing Information
The review of existing air monitoring data entails both summarizing the
reported air contaminant concentrations as well as evaluating the quality of these
data. Air data can be of many varieties and of varying utility to the RFI process. One
of the most basic parameters to review in any type of air data should be the validity
of the sampling locations used during the collection of the data. The results of
previous investigations should be assessed with respect to the upwind-downwind
pattern around the unit to determine the likelihood that the sampling devices
would have measured releases from the unit of concern. For relatively simple sites
(e.g.. flat terrain, constant wind speed and direction), this determination should be
fairly straight-forward; however, for complex sites (e.g.. complex terrain, variable
winds, multiple sources, etc.), assessing the appropriateness of past sampling
locations should consider such factors as potential interferences that may not have
been addressed by the sampling scheme.
The most useful monitoring data are compound-specific results which can be
associated with the unit being investigated, or, for point sources (such as vent stacks
or ventilation system outlets), direct measurements of the exhaust prior to its
release into the atmosphere. Because the hazardous properties and health and
environmental criteria are compound-specific, general compound category or class
data (e.g., hydrocarbon results) are less meaningful. Any existing air data should
also be described and documented as to the sampling and analysis methods utilized,
the associated detection limits, precision and accuracy, and the results of QAIQC
analyses conducted. Results reported as non-detected (i.e., not providing numerical
detection limits) are likely to be of no value.
In addition, available upwind and downwind ambient air data should be
evaluated to determine if the contamination is due to releases from the unit. If
background data are available for the unit of concern, the data will be of much
greater use in the planning of additional air monitoring tasks. Upwind data (to
characterize ambient air background levels) are important for evaluating if
12-41
-------
downwind contamination can be attributed to the unit of concern. If background.
data are not available, the existing downwind air concentration data will be of lesi
value in characterizing a release; however, the lack of background data does not
negate the utility of the available monitoring data.
Data may also be available from air monitoring studies that did not focus directly
on releases from a unit of concern. Many facilities conduct onsite health and safety
programs, including routine monitoring of air quality for purposes of evaluating
worker exposure. This type of data may include personnel hygiene monitoring
results from personal sampling systems worn by employees as they perform their
jobs, general area monitoring of zones at which hazardous operations are
conducted, or actual unit-emission monitoring. The detection limits of these
methods (generally in parts per million) are frequently higher than are needed for
RFI purposes. However, this type of industrial hygiene monitoring is frequently
compound-specific, and can be useful in qualitatively evaluating the air emissions
from particular sources.
Indoor air monitoring, generally only applicable to units that are enclosed in a
building (e.g., drum handling areas or tanks), often includes flow monitoring of the’
ventilation system. Monitoring of hoods and ductwork systems may have been
conducted to determine exchange time and air circulation rates. These flow
determinations could prove to be useful in the evaluation of air emissions
measurements during the RFI.
Another important aspect of the existing data review is to document any
changes in composition of the waste managed in the unit of concern since the air
data were collected. Also, changes in operating conditions or system configuration
for waste generation and/or unit functions could have major effects on the nature
or extent of releases to air. If such operational or waste changes have occurred,
they should be summarized and reviewed to determine their role in the evaluation
of existing data. This summary and review will not negate the need to take new
samples to characterize releases from the unit. However, such information can be
useful in the planning of the new air monitoring activities.
12-42
-------
12.3.5 Determination of “Reasonable Worst-Case” Exposure Period
A reasonable. worst-case” exposure period over a 90 day period should be
identified to aid in planning the air monitoring program. Determination of
reasonable worst-case exposure conditions is dependent on seasonal variations an
emission rates and dispersion conditions.
The selection of the “reasonable worst-case” 90-day exposure period for the
conduct of air monitoring should account for the following factors:
• For vapor phase releases, wind speed and temperature are the key factors
affecting releases from the unit. In general, the higher the temperature
and wind speed, the greater the rate of volatilization of constituentj of
concern from the waste. This process is tempered, however, by the fact
that at higher windspeeds, dispersion of the release is generally greater.
resulting in lower downwind concentrations at potential exposure point.
• For particulate releases, wind speed is the key meteorological factor. The
amount of local precipitation contributing to the degree of moisture of the
waste may also be important. In general, the higher the windspeed, and
the drier the waste, the greater will be the potential for particulate release.
As with vapor phase releases, higher wind speeds may also lead to greater
dispersion of the release, resulting in lower downwind concentrations.
• For point source releases, increased wind speeds and unstable atmospheric
conditions (e.g., during cloudless days) enhance dispersion but also tend to
reduce plume height and can lead to relatively high groundlevel
concentrations.
• Constituent concentrations at any downwind sector will also be
directly affected by the wind direction and frequency.
Air emission release rate models and atmospheric dispersion models can be used
to identify reasonable worst-case exposure conditions (i.e., to quantitatively
account for the above factors). For this application it is recommended that the
modeling effort be limited to a screening/sensitivity excercise with the objective of
12-43
-------
obtaining relative” results for a variety of source and meteorological scenarios. 8 ”
comparing results in a relative fashion, only those input meteorological parameter?
of greatest sigriifkance (e.g., temperature, wind speed and stability) need to be
considered. Case Study number 15 in Volume IV (Case Study Examples), illustrates
this approach.
In general, the summer season will be the reasonable worst-case exposure
period at most sites because of relatively high temperatures and low windspeeds.
Spring and fall are also candidate monitoring seasons that should be evaluated on a
site-specific basis. Winter is generally not a prime season for air monitoring due to
of the lower temperatures and higher wind speeds.
12.4 Design of a Monitoring Program to Characterize Releases
Based on gathering of the information previously described, including
determination of reasonable worst-case scenarios as discussed in the previous
section, monitoring procedures can b3 developed. This section discusses the
recommended monitoring approaches.
Primary elements in designing a monitoringsystem include:
• Establishing monitoring objectives;
• Determining monitoring constituents of concern;
• Monitoring heduIe;
• Monitoring approach; and
• Monitoring locations.
Each of these elements should be addressed to meet the objectives of the initial
monitoring phase, and any subsequent phases that may be necessary. These
elements are described in detail below.
12-44
-------
12.4.1 Objectives of the Monitoring Program
The overall goal of the air monitoring program is to determine concentrations at
actual offsite receptor locations as input to the health and environmental
assessment process. As discussed previously, the monitoring program may be
conducted in a phased approach, using the results of initial monitoring to
determine the need for and scope of subsequent monitoring.
Principal objectives of both the initial and subsequent monitoring phases are:
• Identification of constituents;
• Characterization of long-term ambient constituent concentrations (based
on a reasonable worst case”exposure period) at:
- the unit boundary to maximize the potential for release detection
• the facility property boundary
- actual offsite receptor locations
- areas upwind of the release source in order to characterize
background concentrations; and
• Collection of meteorological data during the monitoring period to aid in
evaluating the air monitoring data
Atmospheric dispersion modeling may be needed to estimate concentrations at
offsite receptor locations if monitoring at offsite locations is not practical, as
discussed previously.
Subsequent monitoring may be necessary if initial monitoring and modeling
data were not sufficient to characterize long-term ambient constituent
concentrations at actual offsite receptors. Subsequent monitoring may also be
required to determine the effectiveness of interim control measures, if applied.
12.4.2 Monitoring Constituents and Sampling Considerations
Sampling and analysis may be conducted for all appropriate Appendix VIII
constituents that have an air pathway potential (See Section 3 and Appendix B). An
12-45
-------
alternative approach is to use unit and waste-specific information to identify
constituents that are not expected to be present and thus, reduce the list of targetd
monitoring constituents. For example, the industry specific monitoring constituent’
lists presented in Appendix B, List 3 can be used to identify appropriate air
monitoring constituents for many applications (especially for units that serve only
one or a limited number of industrial categories).
Results from the screening sampling phase as defined later in Section 12.4.4.1),
may also be used as a basis for selection of monitoring constituents. These short-
term air sampling results may confirm/identify appropriate monitoring constituents
for the unit of concern.
12.4.3 Meteorological Monitoring
Monitoring of onsite meteorological conditions should be performed in concert
with other monitoring activities to aid in the interpretation of air-quality
monitoring data. Results of such monitoring can serve as input for dispersion
models, and can be used to assure that the monitoring effort is conducted during
the appropriate meteorological conditions (e.g., “reasonable worst case” period fo
initial monitoring).
12.4.3.1 Meteorological Monitoring Parameters
The following meteorological parameters should be routinely monitored while
collecting ambient air samples:
• Horizontal wind speed and direction;
• Ambient temperature;
• Atmospheric stability (e.g., based on the standard deviation of horizontal
wind direction or alternative standard methodologies);
• Precipitation measurements if representative National Weather Service
data are not available; and
12-46
-------
• Atmospheric pressure (e.g., for landfill sites or contaminated soils) if
representative National Weather Service data are not available.
It is recommended that horizontal wind speed and direction, and air
temperature be determined onsite with continuous recording equipment.
Estimates from offsite monitors are not likely to be representative for all of the
conditions at the site. Input parameters for dispersion models, if appropriate,
should be reviewed prior to conducting the meteorological data collection phase to
insure that all necessary parameters are included.
Field equipment used to collect meteorological data can range in sophistication
from small, portable, battery-operated units with wind speed and direction sensors,
to large, permanently mounted, multiple sensor units at varying heights. Individual
sensors available can collect data on horizontal wind speed and direction, three-
dimensional wind speed, air temperature, humidity, dew point, and mixing height.
From such data, variables for dispersion models such as wind variability and
atmospheric stability can be determined. Additional guidance on meteorological
measurements can be obtained from:
U.S. EPA. February 1983. Quality Assurance handbook for Air Pollution
Measurement Systems: Volume iv. Meteorological Measurements . EPA-
600/4-82-060. NTIS PB 254-658/8. Office of Research and Development.
Research Traingle Park, N.C 27711.
U.S. EPA. July 1986. Guidelines on Air Quality Models (Revised) . EPA-450/2-78-
027R. NTIS PB 86-245248.OffiCe of Air Quality Planning and Standards. Research
mangle Park, NC. 27711.
Appropriate performance specifications for monitoring equipment are given in the
following document:
U.S. EPA. November 1980. Ambient Monitoring Guidelines for Prevention of
Significant Deterioration (PSD) . EPA-45014-801012. NTIS PB 81.1 53231. Office of
Air Quality Planning and Standards. Research Triangle Park, N.C. 27711.
12-47
-------
12.4.3.2 Meteorological Monitor Siting
Careful place ient of meteorological monitoring equipment (e.g., sensors) is
important in gatherrng relevant data. The objective of monitoring tower
placement is to position sensors to obtain measurements representative of the
conditions that determine atmospheric dispersion in the area of interest. The
convention for placement of meteorological monitoring equipment is:
• At or abovea height of lOmetersabove ground; and
• At a horizontal distance of 10 times the obstruction height from any
upwind obstructions
In addition, the recommendations given in Table 127 should be followed to avoid
effects of terrain on meteorological monitors.
Depending on the complexity of the terrain in the area of interest and the
parameters being measured, more than one tower location may be necessary.
Complex terrain can greatly influence the transport and diffusion of a contaminant
release to air so that one tower may not be able to account for these influences.
The monitoring station height may also vary depending on source characteristics
and logistics. Heights should be selected to minimize nearground effects that are
not representative of conditions in the atmospheric layer into which a constituent
of concern is being released.
A tower designed specifically to mount meteorological instruments should be
used. Instruments should be mounted on booms projecting horizontally out from
the tower at a minimum distance of twice the tower diameter. Sound engineering
practice should be used to assure tower integrity during all meteorologic
conditions.
Further guidance on siting meteorological instruments and stations is available
in the following publications:
U.S. EPA. November 1980. Ambient Monitoring Guidelines for Prevention of
Significant Deterioration (PSD) . EPA.450/4-800 12 . NTIS PB 81-153231. Office of
Air Quality Planning and Standards. Research Triangle Park, NC. 27711.
12-48
-------
TABLE 12.7
RECOMMENDED SITING CRITERIA TO AVOID TERRAIN EFFECTS
Distance from Tower
(meters)
Maximum Acceptable Construction
or Vegetation Height
(meters)
0-15
0.3
15-30
0.5.1.0
30-100
3
100-300
10
12-49
-------
U.S. EPA. February 1983. Q iality Assurance Handbook for Air Pollutiol
Measurement Systems: Volume IV. Meteorological Measurements . EPA- 600/4-
82-060. NTIS PB 254-658/8. Office of Research and Development. Research
Triangle Park. N.C. 27711.
12.4.4 Monitoring Schedule
Establishment of a monitoring schedule is an important consideration in
developing a monitoring plan. When appropriate, air monitoring should coincide
with monitoring of other media (e.g., subsurface gas, soils, and surface water) that
have the potential for air emissions. As with all other aspects of the monitoring
program, the objectives of monitoring should be considered in establishing a
schedule. As indicated previously, monitoring generally consists of screening
sampling, initial monitoring, and subsequent monitoring. The monitoring schedule
during each of these phases is discussed below.
12.4.4.1 Screening Sampling
A limited screening sampling effort may be necessary to focus the design of
subsequent monitoring phases. This screening phase can also be used to verify the
existence of a release to air and prioritize the major release sources at the facility.
Screening sampling should be used to characterize air emissions (e.g., by using total
hydrocarbon measurements as an indicator), and to confirm/identify the presence
of candidate constituents. Screening samples should generally consist of source
emissions measurements or ambient air samples collected at or in close proximity to
the source. This approach will provide the best opportunity for detection of air
emission constituents. (A discussion of available screening methods is discussed in
Section 12.6.) An alternative screening approach involves collection of a limited
number of air samples to facilitate the analysis of a wide range of constituents (e.g.,
collection via Tenax adsorption tubes or whole air sampling with analysis by GC/MS -
see Section 12.6).
The screening study should generally involve collection of a limited number of
grab or time-integrated samples (several minutes to 24-hours) for a limited tim
period (e.g., one to five days). Sampling should be conducted during
12-50
-------
emission/dispersion conditions that are expected to result in relatively high
concentrations (as discussed in Section 12.3.5). Screening results should be
interpreted cons&dering the representativer eSS of the waste and unit operations
during the sampling, and the detection capabilities of the screening methodology
used.
12.4.4.2 Initial Monitoring
The primary objective of initial monitoring is to characterize long-term
exposures that may be associated with air emissions from the unit under reasonable
worst-case conditions. A schedule should be proposed that will provide an
adequate degree of confidence that those compounds that may be released will be
detected. A recommended sampling schedule for meeting this objective is given
below:
• Meteorological monitoring -90 days continuous monitoring.
• Air Monitoring (Alternative 1) -90 days:
- Analysis of 24-hour time integrated samples for target constituents
every day during the 90-day period (total of 90 samples)
• Air Monitoring (Alternative 2) -go days:
- Analysis of 24-hour integrated samples for target constituents every
sixth day (total of 15 samples per station resulting in a total of 15 days
of monitoring coverage); and
- Analysis of a five-day composite sample at each station (consisting of
five 24-hour integrated samples), or intermittent sampling (e.g.. a
continuing cycle of one minute of sampling and five minutes of off-
time), during a five-day period (total of 15 additional samples per
station, which results in 75 days of monitoring coverage).
• Emission rate monitoring - 1 to 3 days (for selected cases such as point
sources, or area sources (such as closed landfills) with variable spatial
distribution of waste, for which ambient monitoring detection limits are
expected to be less than constituent concentrations).
12-51
-------
The 90-day monitoring program (i.e., Alternatives i and 2) will facilitat
collecting samples over a wide range of emission and dispersion conditions. The 90 ’
day period should be selected, as previously discussed, to coincide with the expected
season of highest ambient concentrations. Meteorological monitoring should be
continuous and concurrent with this 90-day period to adequately characterize
dispersion conditions at the site and to provide meteorological data to support
interpretation of the air-quality monitoring data.
Alternative 2 air monitoring approach consists of analyzing 24-hour time-
integrated samples every sixth day, plus analyzing the equivalent of a five day time-
integrated sample for the remaining portions of each 6-day monitoring cycle
throughout the 90-day period. Analysis of the 24-hour time-integrated samples
provides the basis to detect high concentration short-term events. These high
concentration events may result in the mathematical calculation of an average long-
term concentration during the 90-day period that might otherwise not be possible
to quantify (i.e., would be less than the analytical detection limit). The five-day
time-integrated samples provide an efficient basis to achieve continuous air
monitoring during the “reasonable worst case” 90-day monitoring period.
The collection of a time-integrated sample based on continuous monitoring for
several days can result in technical difficulties (e.g., poor collection efficiencies for
volatile constituents or large sample volumes). The application of five-day
composite samples at each station, or intermittent sampling during the five days,
results in continuous monitoring coverage during the 90-day period and facilitates
the characterization of long-term exposure levels.
Although there are some limitations associated with composite/intermittent
sampling (e.g., the potential for sample degradation), the 24-hour samples
collected every sixth day will provide a second data set for characterizing ambient
concentrations. Although the results of the two data sets should not be directly
combined (because of the different sampling periods) they provide a
comprehensive technical basis by which to evaluate long-term exposure conditions.
Emission rate monitoring may be necessary to characterize a release if ambient
levels are expected to be less than analytical detection limits. This approac
involves stack or vent emission monitoring for point sources. Point source
12-52
-------
monitoring is not dependent on meteorological conditions. However, emission rate
monitoring for both point and area sources should be conducted during typical or
reasonable wont case” conditions. Emission rate monitoring for area sources
should not be conducted during or immediately following precipitation or if hourly
average wind speeds are greater than 15 miles per hour. It should also be noted
that soil or cover material (if present) should be allowed to dry prior to continuing
monitoring operations, as volatilization decreases under saturated soil conditions.
In these cases, the monitoring should be interrupted and resumed as soon as
possible after the unfavorable conditions pass. Similarly, operational interruptions
such as unit shutdown should also be factored into the source sampling schedule.
Point source emission sampling generally requires only a few hours of sampling
and occurs during a more limited time (e.g.. one to three days). Guidance on point-
source sampling schedules is presented in the following:
U.S. EPA. November 1985. Practical Guide - Trial Burns for Hazardous Waste
Incinerators . NTIS PB 86-190246. Office of Research and Development.
Cincinnati, OH 45268.
U.S. EPA. Code of Federal Regulations. 40 CFR Part 60: Appendix A: Reference
Methods . Office of the Federal Register. Washington, D.C. 20640.
U.S. EPA. 1978. Stack Sampling Technial Information. A Collection of
Monographs and Papers. Volumes I-Ill . EPA-450/2-78-042a,b,c. NTIS PB 80-
161672, 80-161680, 80-161698. Office of Air Quality Planning and Standards.
Research Triangle Park, N.C. 27711.
U.S. EPA. February 1985. Modified Method 5 Train and Source Assessment
Sampling System Operators Manual . EPA-600/8-85-003. NTIS PB 85-169878.
Office of Research and Development. Research Triangle Park, N.C. 27711.
U.S. EPA. March 1984. Protocol for the Collection and Analysis of Volatile POHCs
Using yOST . EPA-600/8-84-007. NTIS PB 84-170042. Office of Research and
Development. Research Triangle Park, N.C. 27711.
12-53
-------
U.S. EPA. February 1984. Sampling and Analysis Methods for Hazardous Waste
Combustion . EPA-600/8-84-002. NTIS P884-155845. Washington, D.C. 20460.
U.S. EPA. 1981. Source Sampling and Analysis of Gaseous Pollutants . EPA- APTI
Course Matnial 468. Air Pollution Control Institute. Research Triangle Park, N.C.
27711.
U.S. EPA. 1979. Source Sampling for Particulate Pollutants . EPA-APTI Course
Manual 450. NTIS PB 80-188840, 80-182439, 80-174360. Air Pollution Control
Institute. Research Triangle Park, N.C. 27711.
U.S. EPA. 1986. Test Methods for Evaluating Solid Waste . 3rd Edition. Office of
Solid Waste. EPAISW-846. GPO No.955-001-00000-i. Washington, D.C. 20460.
Guidance on area source emission rate monitoring is provided in the following:
U.S. EPA. 1986. Measurement of Gaseous Emission Rates from Land Surfaces
Using an Emission Isolation Flux Chamber: User’s Guide . EPAI600/8-86/OO8. NTIS
PB86-223161. Environmental Monitoring Systems Laboratory. Las Vegas, NV
89114.
12.4.4.3 SubsequentMonitoring
Subsequent monitoring may be necessary if initial monitoring data were not
sufficient to estimate “reasonable worst case long-term concentrations at actual
offsite receptors. Additional monitoring may also be necessary to evaluate air
concentration levels subsequent to the implementation of corrective measures.
The same schedule specified for the initial monitoring phase is also applicable to
subsequent monitoring. However, when evaluating the results of subsequent
monitoring and comparing them to previously collected data potential differences
in emission/dispersion conditions and other data representativeness factors should
be accounted for.
12-54
-------
12.4.5 Monitoring Approach
Use of an upw4nd/downwind network of monitors or sample collection devices is
the primary approach recommended to determine ambient and background
concentrations of the constituents of concern. Dispersion models may also be used
for many applications to extrapolate ambient data collected at the facility to actual
offsite receptor locations, if it is not feasible to collect offsite monitoring data.
Alternatively, for certain situations emission monitoring can be performed at the
source of the release to determine the rate of the release, with downwind
concentrations estimated using mathematical dispersion models.
Emission monitoring in conjunction with dispersion modeling may be an
effective alternative for the following cases:
• Meteorological conditions (e.g., constant high winds) or high background
concentrations of contaminants prevent viable measurement of the
release;
• The source can be localized sufficiently to a Iow representative collection of
emission samples (e.g., landfill vents, incinerator stacks, etc.); and
• Expected ambient constituent concentrations from an area source are
expected to be below analytical detection limits but may still be of concern.
In this case, isolation flux chamber sampling at the unit may be applied.
This device is discussed below and in Appendix E.
A summary of applicable air monitoring strategies related to source type is
presented in Table 12-8.
12.4.5.1 Ambient Air Monitoring
Upwind/downwind ambient air monitoring networks provide concentrations of
the constituents of concern at the point of monitoring, whether that be at the unit
boundary, facility property boundary, or at a receptor point. The
upwind/downwind approach involves the placement of monitors or sample
collection devices at various points around the unit of concern. Each air sample
12-55
-------
TABLE 12-8
APPUCABLE AIR SAMPLING STRATEGIES BY SOURCE TYPES
Unit Type/Expected Emission
Air Sampling Strategy
Ambient
Monitoring
Emissions Monitoring
Source
Sampling
Isolation
Flux
Chambers
AREA SOURCES WITH LIQUID SURFACES
Surface Impoundments
Vapor Phase
Particulates
Open Roof Storage/Treatment
Tanks
Vapor Phase
x
X
X
X
X
X
AREA SOURCES WITH SOLID SURFACES
Waste Piles
Vapor Phase
Particulates
Landfill Surface
Vapor Phase
Particulates
Land Treatment
Vapor Phase
Particulates
x
- X
x
X
x
X
X
X
X
POINT SOURCES
Vents from container Handling
Un its
Vapor Phase
Landfill Vents
Vapor Phase
Storage/Treatment Tank Vents
Vapor Phase
Incinerators
Vapor Phase
Particulates
X
X
X
x
X
X
X
X
X
X
X
12-56
-------
collected is classified as upwind or downwind based on the wind conditions for the
sampling period. Downwind concentrations are compared to those measured at
upwind points to determine the relative contribution of the unit to ambient
concentrations of toxic compounds. This is generally accomplished by subtracting
the upwind c•ncentration (which represents background conditions) from the
concurrent downwind concentrations. Applicable field methods for ambient air
monitoring are discussed in Sectson 12.6. Ambient downwind concentrations at the
facility can be extrapolated to actual offsite receptor locations by using dispersion
modeling results. As discussed previously, this may be necessary if practical
limitations (e.g., potential for vandalism, site access limitations) preclude the
collection of offsite air monitoring data.
12.4 5.2 Source Emissions Monitoring
Monitoring at the source to measure a rate of emission for the constituents of
concern may, in some cases, offer a more practical approach to characterizing air
emissions. Using this technique, the emission rate is then input into a mathematical
dispersion model for estimation of downwind concentrations. One distinct
disadvantage of this approach is that the value achieved for a concentration at a
downwind point is not a measurement, but an.estimation modeled from a series of
input parameters such as wind speed and emission rate. However, the approach
does have advantages in that interference from sources close to the unit are
eliminated because the source is isolated from the ambient atmosphere for
monitoring purposes, and in that source monitoring techniques do not require the
level of sensitivity required by ambient monitors. Concentrations of airborne
constituents at the source are generally higher than at downwind locations due to
the lack of dispersion of the constituent over a wide area. The concentrations
expected in ambient air (generally part-per-billion levels) may be at or near the limit
of detectability of the methods used. Methods for source emissions monitoring for
various constituent classes are discussed in Section 12.6.
Area sources (such as landfills, land treatment units, and surface impoundments)
can be monitored using the isolation flux chamber approach. This method involves
isolating a small area of contamination under a flux chamber, and passing a known
amount of a zero hydrocarbon carrier gas through the chamber, thereby picking up
any volatile emissions in the effluent gas stream from the flux chamber. Samples of
12-57
-------
this effluent stream are collected in inert sampling containers, usually stainless steel
canisters under vacuum, and removed to the laboratory for subsequent analysis.
The analytical rest Its of the identified analytes can be converted through a series of
calculations to direct emission rates from the source. These emission rates can be
used to evaluate downwind concentrations by application of dispersion models.
More information on use of the isolation flux chamber is provided in Appendix E
and in the following reference:
U.S. EPA. 1986. Measurement of Gaseous Emission Rates from Land Surfaces
Using an Emission Isolation Flux Chamber User’s Guide . EPA/600/8- 86/008. NTIS
PB 86-223161. Washington, D.C. 20460.
Some area source units may not be amenable to the source sampling approach,
however. A unit in which the source cannot be isolated and viable measurements
taken of the parameters of concern is one example. This includes active areas of
landfills and land-treatment areas, as well as aerated surface impoundments. Also,
area sources in which particulate emissions are of concern cannot be measured
using an isolation flux chamber due to technical limitations in the technique. For
these applications, only an upwind/downwind monitoring approach should be
used.
12.4.6 Monitoring Locations
As with other factors associated with air monitoring, siting of the monitors
should reflect the primary objective of the monitoring to characterize
concentrations at existing offsite receptors. This section discusses monitoring
locations for both upwind/downwind approaches and source monitoring
techniques in relation to the objectives of both initial and subsequent monitoring.
12.4.6.1 Upwind/Downwind Monitoring Locations
The ambient air monitoring network design should provide adequate coverage
to characterize both upwind (background) and downwind concentrations.
Therefore, four air monitoring zones are generally necessary for initial monitoring.
Multiple monitoring stations per zone will frequently be required to adequately
characterize the release. An upwind zone is used to define background
12-58
-------
concentration levels. Downwind zones at the unit boundary and at or beyond the
facility property boundary are used to define potential offsite receptor exposure.
The location of air monitoring stations should be based on local wind patterns.
Air monitoring statior s should be placed at the following strategic locations, as
illustrated in Figure 12-6:
• Upwind (based on the expected prevailing wind flow during the 90-day
monitoring period) of the unit and near the facility property boundary to
characterize background air concentration levels.
• Downwind (based on the expected prevailing wind flow during the 90-day
monitoring period) at the unit boundary plus stations at adjacent sectors
also at the unit boundary (the seperation distance of air monitoring
stations at the unit boundary should be 30° or 50 feet, whichever is
greater).
• Downwind (based art the expected prevailing wind flow during the 90-day
monitoring period) at the facility property boundary (this station may not
be required if the site perimeter is within 100 m of the unit boundary).
• Downwind (at the area expected to have the highest average
concentration levels during the 90-day monitoring period) just beyond the
facility property boundary.
• Downwind at actual offsite receptor locations (if practical) expected to
have the greatest impact from the release.
• Additional locations at complex terrain and coastal sites associated with
pronounced secondary air flow paths (e.g., downwind of the unit neat the
facility property boundary for both primary daytime and nighttime flow
paths).
The above locations should be selected prior to initial monitoring based on the
onsite meteorological survey and on evaluation of available representative offsite
meterological data. This analysis should provide an estimate of expected wind
12-59
-------
FIGURE 12-6. EXAMPLE AIR MONITORING NETWORK.
Expected Maximum
Long Term
Concentration Area
x
Actual Offsite
Receptor (with
expected maxirpum
release impact)
PREVAILING
F
WIND DIRECTION
I
— Upwind
Station
Unit boundary
X
X Downwind
Stations
--X.--
X
I
X
I
t
I
I
X
/
Facility property boundary
-------
conditions during the 90-day initial monitoring period. If sufficient representative
data are available, dispersion modeling can be used to identify the area of
maximum long term concentration levels at the facility property boundary and at
actual offsite receptors. If not, the facility property boundary sector nearest to the
unit of concern should be selected for initial monitoring.
The network design defined above will provide an adequate basis to define
long-term concentrations based on continuous monitoring during the 90-day initial
monitoring period. The monitoring stations at the unit boundary should increase
the potential for release detection. The facility property boundary air monitoring
stations should provide data (with the aid of dispersion modeling, if appropriate) to
characterize offsite concentrations.
Ambient monitoring at offsite receptors may be impractical in many cases,
because analytical detection limits may not be low enough at offsite receptor
locations to measure the release. Also, a 90-day offsite monitoring program can be
problematic. Factors such as vandalism, erroneous readings due to public
tampering with the equipment, public relations problems in setting up the
equipment. and legal access problems may preclude the use of offsite air
monitoring stations. For these cases, dispersion models may be used to extrapolate
monitoring data collected at the facility to actual offsite receptor locations.
If subsequent monitoring is required, a similar network design to that illustrated
in Figure 12-6 will generally be appropriate. Evaluation of the meteorological
monitoring data collected during the initial phase should provide an improved basis
to identify local prevailing and diurnal wind flow paths. Also, the site
meteorological data will provide dispersion modeling input. These modeling results
should provide dilution patterns that can be used to identify areas with expected
relatively high concentration levels. However, these results should account for
seasonal meteorological differences between initial and subsequent monitoring
periods.
Wind-directionally controlled air monitoring stations can also be used at sites
with highly variable wind directions. These wind-directionally controlled stations
should be collocated with the fixed mdnitoring stations. This approach facilitates
determination of the unit source contribution to total constituent levels in the local
12-61
-------
area. These automated stations will only sample for a user-defined range of wind
directions (e.g., dOwnwind stations would only sample if winds were blowing fror
the source towaras the station.) Interpretation of results from wind.directjona lly’
controlled air monitoring stations should account for the lower sampling volumes
(and therefore, the possibility that not enough sample would be collected for
analysis) generally associated with this approach.
The inlet exposure height of the air monitors should be 2 to 15 m to be
representative of potential inhalation exposure but not unduly biased by road dust
and natural wind erosion phenomena. Further guidance on air monitoring network
design and station exposure criteria (e.g., sampling height and proximity to
structures and air emission sources) is provided in the following reference:
U.S. EPA. September 1984. Network Design and Site Exposure Criteria for
Selected Non-criteria Air Pollutants . EPA-450/4-84 -022. Office of Air Quality
Planning and Standards. Research Triangle Park, N.C. 27711.
The above referenced document recommends the use of dispersion models to
identify potential relatively high concentration areas as a basis for network design.
This topic is also discussed in the following document:
U.S. EPA. July 1986. Guidelines on Air Qualilty Models (Revised) . EPA- 450/2-78-
027R. Office of Air Quality Planning and Standards. Research Triangle Park, N.C.
27711.
Uniformity among the sampling sites should be achieved to the greatest degree
possible. Descriptions should be prepared for all sampling sites. The description
should include the type of ground surface, and the direction, distance, and
approximate height with respect to the source of the release. Location should also
be described on a facility map.
12.4.6.2 StackNent Emission Monitoring
Point source measurements should be taken in the vent near the point of
release. If warranted, an upwind/downwind monitoring network can be used to
supplement the release rate data. Both the VOST and Modified Method S
12-62
-------
methodologies describe the exact placement in the stack for the sampler inlet. (See
Section 12.6.3).
12.4.6.3 Isolation Flux Chambers
Monitor placement using flux chambers (discussed earlier) is similar to
conducting a characterization of any area source. Section 3 of this guidance
discusses establishment of a grid network for sampling. Such a grid should be
established for an area source, with sampling points established within the grids, as
appropriate. It is suggested that a minimum of six points be chosen for each
monitoring effort. Once these areas are sampled, the results can be averaged to
provide an overall compound specific emission rate for the plot. Additional
guidance on the use of isolation flux chambers is presented in Appendix E.
12.S Data Presentation
As discussed in Section 5, progress reports will be required by the regulatory
agency at periodic intervals during the investigation. The followtng data
presentation formats are suggested for the various phases of the air investigation in
order to adequately characterize concentrations at actual offsite receptors.
12.5.1 Waste and Unit Characterization
Waste and unit characteristics should be presented as:
• Tables of waste constituents and concentrations;
• Tables of relevant physical/chemical properties for potential air emission
constituents;
• Tables and narratives describing unit dimensions and special operating
conditions and operating schedules concurrent with the air monitoring
program;
• Narrative description of unit operations; and
12-63
-------
• Identification of 0 reasonable worst case TM emissions conditions that
occurred during the monitoring period.
12.5.2 Environmental Setting Characterization
Environmental characteristics should be presented as follows:
• Climate (historical summaries from available onsite and offsite sources):
• Annual and monthly or seasonal wind roses;
• Annual and monthly or seasonal tabular summaries of mean wind
speeds and atmospheric stability distributions; and
- Annual and monthly or seasonal tabular summaries of temperature
and precipitation.
• Meteorological survey results:
- Hourly listing of all meteororogical parameters for the entire
monitoring period;
- Daytime wind rose (at coastal or complex terrain sites);
- Nightime wind rose (at coastal or complex terrain sites);
• Summary wind rose for all hours;
• Summary of dispersion conditions for the monitoring period (joint
frequency distiibutions of wind direction versus wind speed category
and stability class frequencies); and
- Tabular summaries of means and extremes for temperature and other
meteorological parameters.
• Definition of soil conditions (if appropriate):
12-64
-------
- Narrative of soil characteristics (e.g., temperature, porosity and
org nic matter content); and
- Characterization of soil contamination conditions (e.g., in land
treatment units, etc.).
S Definition of site-specific terrain and nearby receptors:
- Topographic map of the site area with identification of the units.
meteorological and air monitoring stations, and facility property
boundary;
• Topographic map of 10-kilometers radius from site (U.S. Geological
Survey 7.5 minute quandrangle sheets are acceptable); and
- Maps which indicate location of nearest residence for each of sixteen
22.5 degree sectors which correspond to major compass points (e.g..
north, north-northwest, etc.). nearest population centers and
sensitive receptors (e.g., schools, hospitals and nursing homes).
• Maps showing the topography of the area, location of the unit(s) of
concern, and the location of meteorological monitoring equipment.
• A narrative description of the meteorological conditions during the air
sampling periods, including qualitative descriptions of weather events and
precipitation which are needed for data interpretation.
12.5.3 Characterization of the Release
Characteristics of the release should be presented as follows:
• Screening sampling:
- Identification of sampling and analytical methodology;
12-65
-------
• Map which identifies sampling locations;
- Listing of measured concentrations indicating collection time period
and locations;
• Prioritization of units as air release sources which warrant monitoring
based on screening results;
• Discussion of QA/QC measures and results; and
- Listing and discussion of meteorological data during the sampling
period.
• Initial and subsequent monitoring results:
- Identification of monitoring constituents;
• Discussion of sampling and analytical methodology as well a
equipment and specifications;
• Identification of monitoring zones as defined in Section 12.4.6.1;
- Map which identifies monitoring locations relative to units;
- Discussion of QA/QC measures and results;
• Listing of concentrations measured by station and monitoring period
indicating concentrations of all constituents for which monitoring
was conducted. Listings should indicate detection limits if a
constituent is not detected;
• Summary tables of concentration measured indicating maximum and
mean concentration values for each monitoring station;
12-66
-------
- Discussion of meteorological station locations selection, sensor
height, local terrain, nearby obstructions and equipment
speZifications;
• Listing of all meteorological parameters concurrent with the air
sampling periods;
- Daytime wind rose (only for coastal or complex terrain areas);
• Nightime wind rose (only fo coastal or complex terrain areas);
- Summary wind rose based on all wind direction observations for the
sampling period;
- Summary of dispersion conditions for the sampling period (joint
frequency distributions of wind direction versus wind speed category
and stability class frequences based on guidance presented in
Guidelines on Air Quality Models , U.S. EPA, July 1986);
• Tabular summaries of means and extremes for temperature and other
meteorological parameters;
- A narrative discussion of sampling results, indicating problems
encountered, relationship of the sampling activity to unit operating
conditions and meteorological conditions, sampling periods and
times, background levels and identification of other air emission
sources and interferences which may complicate data interpretation;
• Presentation and discussion of models used (if any), modeling input
data arid modeling output data (e.g., dilution or dispersion patterns
based on modeling results); and
- Concentrations based on monitoring and/or modeling for actual
offsite receptor locations.
12-67
-------
Interpretation of air monitoring results should also account for additional
factors such as complex terrain, variable winds, multiple contaminant sources and
intermittent or irregular releases. The key to data interpretation for these cases as
to evaluate monitoring results as a function of wind direction.
Terrain factors can alter wind flow trajectories especially during stable nightime
conditions. Therefore, straightline wind trajectories may not occur during these
conditions if there is intervening terrain between the source and the air monitoring
station. For these cases wind flows will be directed around large obstacles (such as
hills) or channeled (for flows within valleys). Therefore, it is necessary to determine
the representativeness of the data from the meteorological stations as a function of
wind direction, wind speed and stability conditions. Based on this assessment, and
results from the meteorological survey, upwind and downwind sectors (i.e., a range
of wind direction as measured at the meteorological station) should be defined for
each air monitoring station to aid in data interpretation. Figure 12-7 illustrates an
example which classifies a range of wind directions during which the air monitoring
stations will be downwind of an air emission source. Therefore, concentrations
measured during upwind conditions can be used to characterize background
conditions and concentrations measured during downwind conditions can be used
to evaluate the air-quality impact of the release.
Complex terrain sites and coastal sites frequently have very pronounced diurnal
wind patterns. Therefore, as previously discussed, the air monitoring network at
these sites may involve coverage for multiple wind direction sectors and use of
wind-directionally controlled air samplers. This monitoring approach is also
appropriate for sites with highly variable wind conditions. Comparing results from
two collocated air monitoring stations (i.e., one station which samples continuously
and a second station at the same location which is wind-directionally controlled on
an automated basis), facilitates determination of source contributions to ambient
air concentrations.
Comparison of results from collocated (continuous versus wind-directionally
controlled) air monitoring stations can also be used to assist in data interpretation
at sites with multiple air emissions sources or with intermittenVirregular releases.
For some situations, the consistent appearance of certain air emission constituents
can be used to ufingerprintu the source. Therefore, the air monitoring results can
12-68
-------
Figure 12•7
EXAMPLE OF DOWNWIND EXPOSURES
AT AIR MONITORING STATIONS
DOWNWIND SECTOR
• MONITORING STATIONS
UNIT SOURCE
12-69
-------
be classified based on these fingerprint” patterns. These results can then b ”
summarized as two seperate data sets to assess background versus source’
contributions to ambient concentrations.
The use of collocated (continuous and wind-directionally controlled) air
monitoring stations is a preferred approach to data interpretation for complex
terrain, variable wind, multiple source and intermittent release sites. An alternative
data interpretation approach involves reviewing the hourly meteorological data for
each air sampling period. Based on this review, the results from each sampling
period (generally a 24-hour period) for each station are classified in terms of
downwind frequency. The downwind frequency is defined as the number of hours
winds were blowing from the source towards the air monitoring station divided by
the total number of hours in the sampling period. These data can then be processed
(by plotting scattergrams) to determine the relationship of downwind frequency to
measured concentrations.
Data interpretation should also take into account the potential for deposition,
degradation and transformation of the monitoring constituents. These mechanismi
can affect ambient concentrations as well as air sample chemistry (during storage).
Therefore, standard technical references on chemical properties, as well as the
monitoring guidance previously cited, should be consulted to determine the
importance of degradation and transformation for the monitoring constituents of
concern.
12.6 Field Methods
This section describes field methods which can be used during initial or
subsequent monitoring phases. Methods are classified according to source type and
area. Guidance on meteorological monitoring methods is also provided in this
section.
12.6.1 Meteorological Monitoring
Meteorological monitoring generally should employ a 10-meter tower equipped
with wind direction, wind speed, temperature and atmospheric stability
Instrumentation. Wind direction and wind speed monitors should exhibit a starting
12-70
-------
threshold of less than 0.5 meter per second (rn/s.). Wind speed monitors should be
accurate above the starting threshold to within 0.25 mIs at speeds less than or equal
to 5 rn/s. At higher speeds the error should not exceed 5 percent of the wind speed.
Wind direction monitors errors should not exeed 5 degrees. Errors in temperature
should not exceed 0.5°C during normal operating conditions.
The meteorological station should be installed at a location which is
representative of overall site terrain and wind conditions. Multiple meteorological
station locations may be required at coastal and complex terrain sites.
Additional guidance on equipment performance specifications, station location,
sensor exposure criteria, and field methods for meteorological monitoring are
provided in the following references:
U.S. EPA. February 1983. Quality Assurance Handbook for Air Pollution
Measurement Systems: Volume IV,, Meteorological Measurement .
EPA-600-4-82-060. NTIS PB 254-658/8. Office of Research and Development,
Research Triangle Park, N.C. 27711.
U.S. EPA. November 1980. Ambient Monitoring Guidelines for Prevention of
Significant Deterioration (PSD) . EPA-45014-80-012. NTiS PB 81-15323 1. Office of
Air Quality Planning and Standards. Research Triangle Park, NC 27711.
U.S. EPA. july 1986. Guidelines on Air Quality Models (Revised) .
EP-450/2-78-027R. NTIS PB 288-783. Office of Air Quality Planning and
Standards, Researth Triangle Park, NC 27711.
12.6.2 Ambient Air Monitoring
Selection of methods for monitoring ambient contaminants should consider a
number of factors, including the compounds to be detected, the purpose of the
method (e.g., screening or quantification), the detection limits, and sampling rates
and duration required for the investigation.
Organic and inorganic constituents require different analytical methods. Within
these two groups, different methods may also be required depending on the
12-7 1
-------
constituent and its physical/chemical properties. Another condition that affecti the
choice of monitoring technique is whether the compound is primarily in the gaseous
phase or is found dsorbed to solid particles or aerosols.
Screening for the presence of ambient air constituents involves techniques and
equipment that are rapid, portable, and can provide ‘real-time 0 monitoring data.
Air contamination screening will generally be used to confirm the presence of a
release, or to establish the extent of contamination during the screening phase of
the investigation. Quantification of individual components is not as important
during screening as during initial and subsequent monitoring, however the
technique must have sufficient specificity to account for the hazardous constituents
of concern from potential interferences, even when the latter are present in higher
concentrations. Detection limits for screening devices are often higher than for
quantitative methods.
Laboratory analytical techniques must provide positive identification of the
components, and accurate and precise measurement of concentrations. This
generally means that preconcentration and/or storage of air samples will be
required. Therefore, methods chosen for quantification usually involve a longer
analytical time-period, more sophisticated eqaipment, and more rigorous quality
assurance procedures.
The following list of references provides guidance on ambient air monitoring
methodologies:
U.S. EPA. June 1983. Technical Assistance Document for Sampling and Analysis
of Toxic Organic Compounds in Ambient Air . NTIS PB 83-239020.
EPA-60014-83-027. Office of Research and Development. Research Triangle Park,
NC 27711.
U.S. EPA. April 1984. Compendium of Methods for the Determination of Toxic
Organic Compounds in Ambient Air . EPA-60 0/444-041. Office of Research and
Development. Research Triangle Park, NC 27711.
NIOSH. February 1984. NIOSH Manual of Analytical Methods . NTIS PB 85-
179018. National Institute for Occupational Safety and Health. Cincinnati, OH.
12-72
-------
U.S. EPA. September 1983. Characterization of Hazardous Waste Sites A
Methods Manual: Volume I I, Available Sampling Methods . NTIS PB 84-126929.
EPA-600/4-83- 040. Office of Solid Waste. Washington, D.C. 20460.
U.S. EPA. September 1983. Characterization of Hazardous Waste Sites - A
Methods Manual: Volume III. Available Laboratory Analytical Methods . EPA-
600/4-83-040. NTIS PB 84-126929. Office of Solid Waste, Washington, D.C.
20460.
U.S. EPA. September, 1986. Test Methods for Evaluating Solid Waste . 3rd
Edition. EPA SW-846. GPO No 955-001-00000-1. Office of Solid Waste,
Washington, D.C. 20460.
ASTM. 1982. Toxic Materials In the Atmosphere . ASTM, STP 786. Philadelphia,
PA.
ASTM. 1980. Sampling and Analysis of Toxic Organics in the Atmosphere . ASTM,
STP 721. Philadelphia, PA.
ASTM. 1974. Instrumentation for Monitoring Air Quality . ASTM, STP 555.
Philadelphia, PA.
APHA. 1977. Methods of Air Sampling and Analysis . American Public Health
Association. Cincinnati, OH.
ACGIH. 1983. Air Sampling Instruments for Evaluation of Atmospheric
Contaminants . American Conference of Governmental Industrial Hygienists.
Washington, D.C.
12.6.2.1 Screening Methods
Screening techniques for vapor-phase constituents fall into two main categories.
(1) organic and non-organic compound-specific indicators, and (2) general organic
detectors. Table 12-9 presents a summary of commercially available screening
methods for these compounds.
12-73
-------
TABLE 129
TYPICAL COMMERCIALLY AVAILABLE SCREENING TECHNIQUES FOR ORGANICS IN AIR (FROM RIGGIN, 1983)
Technique
Manufacturers
Compounds Detected
Comments
Gas Detection Tubes
I asgar
atiw o n
Kitagawa
Various organics and
inorganics
0.1 to 1 ppmv
Sensitivity and selectivity highly dependent on
Component of interest.
Continuous Flow
Colorimeter
CEA Instruments.
Inc.
Acrylonitrile
Formaldehyde
Ptiosgene. and various
oi’ganics
005 to 0.5 ppmv
Sensitivity and selectivity similar to ddtector
tubes.
Colorimetric Tape Monitor
KHDA Scientific
Toluene. diisocyanate
dinitro toluene
phosgene and various
iflorganics
0.05-0 S ppmv
Same as above
Infrared Analysis
FoxbovalWilkes
Most organics
1-10 ppmv
Some inorganic gases (H 2 0 CD) will be detected
and therefore are potential interferences
FID (Total Hydrocarbon
Analyzer)
Beckman
HSA. Inc.
AID. Inc.
Most organics
05 ppmv
Responds uniformly to most organic compounds
on a carbon basis.
GCIFID (portable)
FoxborolCentury
AID Inc.
Same as above except
that polar compounds
may not elute from the
column.
05 ppmv
Qualitative as well as quantitative information
obtained
PID and GCIPID (portable)
HNU. Inc.
AID. Inc
Photovac Inc.
Most organic
compounds can be
detected with the
exception of methane
0.1 to 100 ppbv
Selectivity can be adjusted by selection of lamp
energy Aromatics most readily detected.
GCIICD (portable)
AID. Inc.
Halogenated and nitro-
substituted compounds
0 1 to 100 ppbv
Response varies widely from compound to
compound
GCIFPD (portable)
AID. Inc.
Sulfur or phosphorus-
containing compounds
10-100 ppbv Both inorganic and organic sulfur or phosphorus
compounds will be detected
Chemiluminescent
Nitrogen Detector
Antek lix
Nitrogen-containing
compounds -
0.1 ppmv (as N) Inorganic nitrogen compounds will interfere
-a
p*J
- .4
-------
Indicator tubes and other colorimetric methods--Indicator tubes, also known as
gas detector or raeger tubes, are small glass tubes filled with a reagent-coated
material which changes color when exposed to a particular chemical. Air is pulled
through the tube with a low-volume pump. Tubes are available for 4.0 organic
gases, and for 8 hour or 15 minute exposure periods. Indicator tubes were designed
for use in occupational settings, where high levels of relatively pure gases are likely
to occur. Therefore, they have only limited usefulness for ambient air sampling,
where part-per-billion levels are often of concern. However, because they are
covenient to use and available for a wide range of compounds, detector tubes may
be useful in some screening/sampling situations.
Other colorimetric methods, such as Continuous flow and tape monitor
techniques, were developed to provide real-time monitoring capability with
indicator methods. The disadvantages of these systems are similar to those of
indicator tubes.
Instrumental detection screening methods--More Commonly used for volatile
organic surveys, are portable instrumental detection methods including flame
ionization detectors (FID), photoionization detectors (PID), electron Capture
detectors (ECD) and infrared detectors (ID). Also in use are detectors that respond
to specific chemical classes such as sulfur- and nitrogen- containing orgarucs. These
instruments are used to indicate levels of total organic vapors and for identification
of ‘hot zones’ downwind of the release source(s). They can be used as real-time
non-specific monitors or, by adding a gas chromatograph, can provide
concentration estimates and tentative identification of pollutants.
Of the available detectors, those that are the most applicable to an RFI are the
FID and PID. Table 12-10 summarizes four instruments (two FID and two PID
versions) which are adequate for the purposes of the screening phase.
Flame Ionization Detectors—The Century OVA 100 series and AID Model 550
utilize a FID to determine the presence of vapor phase organics. The detector
responds to the total of all organics present in the air at any given moment. Flame
ionization detectors will respond to most organics, but are most sensitive to
hydrocarbons, (i.e., those chemicals which contain only carbon and hydrogen
12-75
-------
Table 12-10
Sumriary of Selected Onsite Organic Screening Methodologies
Instrument Measurable Low ran 9 e
or detector parameters of detection Comments
Century Series 100 or Volatile organic Low ppm Uses Flame Ionization
AID Model 550 species Detector (FID)
(survey mode)
HNU Model P1-10 1 Volatile organic Low ppm Photo-ionization (P1)
species detector-provides
especially good
sensitivity to low
molecular weight
aromatic compounds
(i.e., benzene, toluene)
Century Systems Volatile organic Low ppm Uses GC column for
OVA-128(GC mode) species possible specific
compound
identification
Photo Vac 1OA1O Volatile organic Low ppm Uses P1 detector.
species Especially sensitive to
aromatic species. May
be used for compound
identification if
interferences are not
present
12-76
-------
molecules such as benzene and propane). FIDs are somewhat less sensitive to
compounds containing chlorine, nitrogen, oxygen, and sulfur molecules. The
response is calibrated against a reference gas, usually methane. FID response is
often termed total hydrocarbons ; however, this is misleading because particulate
hydrocarbons are not detected. FID detection without gas chromatography is not
useful for quantification of individual compounds, but provides a useful tool for
general assessment purposes. Detection limits using a FID detector alone are about
1 ppm. Addition of a gas chromatograph (GC) lowers the detection limit to ppb
levels, but increases the analysis time significantly.
Photoionization Detectors--Portable photoionization detectors such as the HNU
Model P1-101 and the Photovac 1OA1O operate by applying UV ionizing radiation to
the contaminant molecules. Some selectivity over the types of organic compounds
detected can be obtair ed by varying energy of the ionizing beam. In the screening
mode this feature can be used to distinguish between aliphatic and aromatic
hydrocarbons and to exclude background gases from the instrument’s response.
The HNU and Photovac can be used either in the survey mode (PID only), or with GC.
Sensitivity with PID alone is about 1 ppm, but can go down to as low as 0.1 ppb
when a GC is used for preconcentration.
Pt and Fl detectors used in the GC mode can be used for semiquantitative analysis
of compounds in ambient air. However, in areas where numerous contaminants are
present, identification of peaks in a complex matrix may be tentative at best.
Another method which can be used as a survey technique is mobile mass
spectrometry. Ambient air is drawn through a probe directly into the instrument,
which is usually mounted in a van. Particularly in the MS/MS configuration this is a
powerful technique which can provide positive identification and semiquantitative
measurement of an extremely wide range of organic and inorganic gaseous
contaminants.
12.6.2.2 Quantiative Methods
Laboratory analysis of hazardous constituents in ambient air includes the
following standard steps:
12-77
-------
• Preconcentration of organics (as necessary to achieve detection limit
goals);
• Transfer to a gas chromatograph or HPLC (High Pressure Liquid
Chromatography); and
• Quantification and/or identification with a detector.
Broad-spectrum methods applicable to most common air contaminants are
discussed below.
12.6.2.2.1 Monitoring Organic Compounds in Ambient Air
Due to the large number of organic compounds that may be present in ambient
air, and their wide range in chemical and physical properties, no single monitoring
technique is applicable to all organic air contaminants. Numerous techniques have
been developed, and continue to be developed, to monitor for specific compound
classes, individual chemicals, or to address a wide range of hazardous contaminants.
This last approach may be the most efficient approach to monitoring at units where
a wide range of chemicals are likely to be present. Therefore, methods that apply to
a broad range of compounds are recommended. In cases where specific compounds
of concern are not adequately measured by broad-spectrum methods, compound-
specific techniques are described or referenced.
12.6.2.2.1.1 Vapor•Phase Organics
The majority of hazardous constituents of concern can be classified as gaseous or
(vapor-phase) organics. These constituents include most petroleum-related
hydrocarbons, organic solvents, and many pesticides, and other semivolatile organic
compounds. Methods to monitor these compounds generally include on-site
analysis (making use of onsite concentration techniques, where necessary), or
require storage in a tightly sealed non-reactive container.
12-78
-------
Techniques for volatile and semivolatile organics measurement include:
• Adsorptibn of the sample on a solid sorberit with subsequent desorption
(thermal or chemical), followed by gas chromatographic analysis using a
variety of detectors.
• Collection of whole air (grab) samples in an evacuated flask or in Tedlar or
Teflon bags, with direct injection of the sample into a GC using high
sensitivity and/or constituent-specific detectors. This analysis may or may
not be preceded by a preconcentr tion step.
• Cryogenic trapping of samples in the field with subsequent instrumental
analysis.
• Bubbling ambient air through a liquid-filled impinger, containing a
chemical that will absorb or react with specific compounds to form more
stable products for GC analysis.
• Direct introduction of the air into a MS/MS or other detector.
Tables 12.11 (A and B), 12-12, and 12-13 summarize sampling and analytical
techniques that are applicable to a wide range of vapor phase organics, have been
widely tested and validated in the literature, and make use of equipment that is
readily available. A discussion of general types of techniques is given below.
Sorbent techniques--A very common technique used to sample vapor-phase
organics involves sorption onto a solid medium. Methods of this type usually
employ a low- or high-volume pump to pull air through a glass tube containing the
sorberit material. Organic compounds are trapped (removed from the air) by
chemical attraction to the surface of the adsorbent material. After a predetermined
volume of air has been pulled through the trap, the tube is capped and returned to
the laboratory for analysis. Adsorbed organics are then thermally or chemically
desorbed from the trap prior to GC or GCIMS analysis.
12-79
-------
-‘
p*J
0
TABLE 12-1 1A. SUMMARY OF CANDIDATE METHODOLOGIES FOR QUANTIFICATION OF VAPOR PHASE ORGANICS
Collection Technique
:
Positive Aspects
Negative Aspects
I Sorption onto Tenax-
GC or carbon molecular
sieve packed cartridges
using low-volume
pump
Thermal
Dssorptlon into
GC or GCIMS
I
• adequate QAIQC data
base
S widely used on
investigations around
uncontrolled waste sites
• wide range of
applicability
• plm 3 detection limits
• practicality for field use
• possibility of contamination
S artifact formation problems
S rigorous cleanup needed
S no possibility of multiple analysis
S low breakthrough volumes for some
compounds
II Sorption onto charcoal
packed cartridges using
low-volume pump
Resorption with
solvent-analysis
by GC or GCIMS
II
S large data base for
various compounds
S wide use in industrial
applications
• practicality for field use
• problems with irreversible adsorption of
some compounds
• high (mglm 3 ) detection limits
S artifact formation problems
S high humidity reduces retention
efficiency
Ill. Sorption onto
polyurethane foam
(PUF) using low-volume
or high-volume pump
Solvent e*traction
of PUE; analysis by
GCIMS
I. II , Ill
S wide range of
applkability
• easy to p.-eclean and
extract
• very low blanks
• excellent collection and
retention efficiencies
• reusableuptolOtimes
• possibility of contamination
• losses of more volatile compounds may
occur during storage
IV Sorption on passive
dosimeters using Tenax
or charcoal as
adsorbing medium
Analysis by
chemical or
thermal
desorption
following by GC
or GCIMS
I or II
..
S samplers are small.
portable, require no
pumps
• makes use of analytical
procedures of known
precision and accuracy
for a broad range of
compounds
S pglm 3
• problems associated with sampling using
sorbents (see #1 and 11) are present
• uncertainly in volume of air sampled
makes concentration calculations difficult
• requires minimum external air (low rate
-------
TABLE 12-1 1A (Continued)
-a
p.J
- e
Analytical
Technique Technique
Applicability
Me ,
.
Positive Aspects
•
Negative Aspects
trapping of Desorption into
the field GC
II. Ill
• applicable to a wide
range of compounds
• artifact formation
minimized
• low blanks
• requires field use of liquid nitrogen or
oxygen
• sample is totally used in one analysis - no
reanalysis possible
• samplers easily clogged with w4ter vapor
S no large data base on precision or
recoveries
obtain samples
sample taken Cryogenic
stainless steel trapping or direct
injection into GC
or GCIMS (onsste
or laboratory
analysis)
II. Ill
• useful for grab sampling
• large data base
• excellent long-term
storage
• wide applicability
S allows multiple analyses
• to
S low sensitivity of preconcentratson is not
used -
uncertain
sample taken Cryogenic
Bag trapping or direct
injection into GC
or GCIMS (onsite
or laboratory)
II. Ill
• grab or integrated
sampling
• wide applicability
• allows multiple analyses
• long-term
• low sensitivity if preconcentration is not
used
• adequate cleaning of containers between
samples may be difficult
- HPLCIUV analysis
Liquid
Sampling
Low-Volume
introduction by Mobile MS/MS
IV
I. II. III. IV
• specific to aldehydes and
ketones
• good stability for
derivatszed compounds
S low deteciton limits
S immediate results
• field identification of air
contaminants
• allows real-time
monitoring
• widest applicability of
any analytical method
a fragile equipment
• sensitivity limited by reagent impurities
• problems with solvent evaporation when
long-term sampling is performed
• high instrument cost (S250K)
• requires highly trained oeprators
• grab samples only
• no large data base on precision or
accuracy
-------
TABLE 12-11 B. LIST OF COMPOUND CLASSES REFERENCED IN TABLE 12-1 3A
Category
Types of Compound
I
Volatile, nonpolar organics (e.g., aromatic
hydrocarbons, chlorinated hydrocarbons) having boiling
points in the range of 80 to 200°C.
II
Highly volatile, nonpolar organics (e.g., vinyl chloride,
vinylidene chloride, benzene, toluene) having boiling
pointsintherangeof-lSto + 120°C.
Ill
Semivolatile organic chemicals (e.g., organochlorine
pesticides and PCBs).
IV
Aldehydes and ketones.
12-82
-------
TABLE 12-12. SAMPLING AND ANALYSIS TECHNIQUES APPLICABLE TO
VAPOR PHASE ORGANICS
Compound
Name
Whole
Air
Tenax
Cartridge
TO-I
Carbon MS
Cartridge
TO-i
Cryogenic
Trapping
10-3
Hi-Vol
PUF
10-4
Liquid
Impinger
10-5
PI IOSH
Method
Number
CommenWOthers
Acetophenone
X
X
Acrolein
X
X
‘.
Acrylonitrile
X
X
X
‘
Aniline
X
K
2002
Arsenic and compounds
7900
Solid, use Std. Hi-Vol
Benzene
X
X
K
K
Bis(2-ethylhexy9phalate
5020
Broniomethane
K
NP
K
2520
Cadmium and compounds
7048
Solid, use Std Hi-Vol
Carbon disulfide
K
NP
X
1600
Carbon Tetrach loride
K
B
K
x
1003
Chlordane
K
K
X
Chloroaniline (p)
NP
NP
No validated Method
Ch lo robenzene
X
X
K
1003
Chloroform
K
B
K
K
1003
Chloomethane (methyl chloride)
K
B
NP
NP
Ch lorophenol
Needs XAD-2 Backup
Chloroprene (Neoprene)
X
X
NP
X
1002
Chromium and compounds
7024
Solid, use SW. Hi-Vol
Copper cyanide
7029
Solid, use Std Hi-Vol
-.
(U
-------
TABLE 12-12 (continued)
Compound
Name
Whole
Air
Tenax
Cartridge
TO-i
Carbon MS
Cartridge
70-2
Cryogenic
Trapping
70-3
Hi-Vol
P1W
TO-4
.
4 1 W
mpinger
NIOSH
Method
Number
Comments/Others
Cresol (0)
Cresol (p)
2001
2001
Syn: methyiphenol
Cyanide
X
Syn: methyiphenol
Dschloro-2-butene(i .4)
X
X
X
7904
•
Dichioro benzene (1,2)
X
X
X
1003
DIch lorobenz.ne(l,4)
X
X
X
Dichlorod,fluoromethar
X
NP
NP
NIOSH 1012 should
Dichloroethane(11)(ethylids n e
chloridej
X
X
NP
X
1003
work
Oschlorophenoxyaceljc acid (2,4)
X
NP
Dichloropropane(1 ,2)
X
X
X
1013
Syn: 2,4-0
Method l O O3maybe
Dlchlo ropropene(1 ,3)
X
NP
X
used
Diethyl phthalate
Dinotrotoluene (24)
No method identified
Yellow crystals, use Hi-
Dioxan.(14)
X
X
X
1602
Vol
Diphenylhydrazine(1 ,2)
No
Ethylene dibromide
X
B
X
1008
method identified
Ethylene dichioride
X
B
X
1003
Syn: l,2-dibrontoethane
Fluorides
7902
Syn: I.2-dIchloroeth n
Std Hi-Vol fOr
Heptachior
particulate fraction
Waxy solid, use Std Hi-
Vol
Hexachiorobutadien.
X
1 Blank spaces indicate that the method is inappropriate (or that compound
2 B = small breakthrough volume for adsorbent
3 NP = proven for this adsorbent, but may work
4 X ptable media for collection
-------
TABLE 12-1k. (continued)
Compound
Name
Whole
Air
Tenax
Cartridge
TO-i
Carbon MS
Cariridge
TO-i
Cryogenic
Trapping
10-3
Hi-Vol
PUF
T0-4
. d
iC lUi
mprnger
NIOSH
Method
Number
Commentsl0thers
Hexach loroethane
NP
X
1003
Syn: perchloroethane
Isobutanol
NP
X
1401
Syn. ssobutyl alcohol
Lead and compounds
7802
Mostly particulate, use
Hi-Vol
Mercury and compounds
7300
Mostly particulate, use
Hi-Vol
Methacrylonitrile
X
NP
X
Methyl ethyl ketone
X
X
2500
Syn. 2-butanone
Methyl methacrylate
X
NP
X
Methylene chloride
B
X
X
1005
Syn: dichloromethane
Naphthalene
X
X
5515
Method 10-4 needs
XAD-2
Nickel and compounds
.
7300
Mostly particulate, use
Hi-Vol
Nitrobenzene
X
X
X
2005
Nitrophenol
X
NP
X
Parathion
NP
5012
?entachlorobenzene
X
NP
X
Pentachloroethane
X
X
x
pentachloropheno$
X
NP
Perchloroethylene
X
X
X
Syn.
Tetraithloroethylene
Phenol
X
X
X
3502
Phorate
X
X
Pyr,dine
X
ResorcinOl
X
Styrene
— X
NP
X
1501
Syn Polystyrene
p . -,
Co
U’
-------
TABLE 12-12. (continued)
Compound
Name
Whole
Air
Tenax
Cartridge
TO-i
Carbon MS
Cartridge
TO-2
Cryogenic
Trapping
TO-3
Hi-Vol
PUF
TO-4
Li d
Im ( Ui
NIOSH
Method
Number
CommenWOthers
TCDD (2 3.7 8)
X
Toluene
X
X
X
X
Toxaphene
X
NP
1501
Syn: Chl rinated
Trichlorobenzene
X
NP
NP
camphene
Trichloroetha n e(i1.1)
X
a
X
X
1003
Trich loroethylene
X
X
X
X
Syn: Methyl Chloroform
Trichloropropane(12 3)
X
X
X
Vanadium pentoxide
Mostly particulate, use
Vinyl acetate
x
X
Hi-Vol
Vinyl chloride
X
X
X
1007
Vinylsdenech lo.jde(1 ,1
lichloroethylene)
X
X
X
Syn: l ,1-dschtoroeffiene
Xylene(m ,o ,p)
X
X
X
150 1
Zinc oxide
7530 and
Syn: dimethylbenzene
Solid, use Std Hi-Vol
p..J
a’
-------
Table 12-13
Campounds Successfully Monitored Using EMSL-RTP
Tenax Sampling Protocols
2-Ch loropropane 1 -Bromo-3-chloropropane
1,1-Dich loroethene Ethylbenzene
Bromoethane Bromoform
1-Chioropropane Ethenylbenzene
Bromochioromethane o-Xylene
Chloroform 1 ,122-Tetrachloroethane
Tetrahydrofuran Bromobenzene
1,2-Dichloroethane Berizaldehyde
1 ,11-Trichioroethane Pentachloroethane
Benzene 4-Chlorostyrerte
Carbon tetrachloride 3-Chloro-1-propene
Dibromomethane 1 ,4-Dichlorobutane
1 ,2-Dichloropropane 1 ,2,3.Trichloropropane
Trichloroethene 1,1 -Dichloroethane
11 ,2-Trichloroethane 2-Chiorobutane
2,3-Dichlorobutane 2-Chioroethyl vinly ether
Bromotrichloromethane 1.1,1 2-Tetrachloroethane
Toluene p-Dioxane
1,3-Dichloropropane Epichlorohydrin
1,2 .Dibromomethane 1,3-Dichiorobutane
Tetrachioroethene p-Dichlorobenzene
Chlorobenzene cis-1 4-Dichloro-2-butene
1,2-Dibromoproparie n-Butyl benzene
Nitrobenzene 3,4-Dichloro-1 -butene
Acetophenone 1,3,5-Trimethyl benzene
Benzonitrite
sop ropyl benzene
p.lsopropyltoluene
12-87
-------
Thermal desorption is accomplished by rapidly heating the sorbent tube while a
stream of inert gas flushes desorbed organics directly onto the GC column
Generally a secondary trap (either another sorbent or a cryogenically cooled loop) is
used to hold the organics until injection into the GC column, but this step precludes
multiple analyses of the sample.
Chemical desorptiori involves flushing the sorbent tube with an organic solvent,
and analysis of the desorbed organics by GC or GCIMS. Since only a portion of the
solvent is injected into the GC, sensitivity is lower than with thermal adsorption.
However, reanalysis of samples is possible. The most common application of
chemical desorption is for analysis of workplace air samplers, where relatively high
concentrations of organics are expected.
The primary advantages of sorbent techniques are their ease of use and ability to
sample large volumes of air. Sorbent cartridges are commercially available for many
applications, and can easily be adapted to portable monitoring pumps or personal
samplers. A wide variety of sorbent materials are available, and sorbent traps can
be used singly or in series for maximum retention of airborne pollutants. Sorbent
methods are especially applicable to integrated or long•term sampling, because
large volumes of air can be passed through the-sampling tube before breakthrough
occurs.
In choosing a sorbent method, the advantages and limitations of specific
methods should be considered along with general limitations of sorbents. Some
important considerations are discussed below.
• Sorbents can be easily contaminated during manufacturing, shipping or
storage. Extensive preparation (cleaning) procedures are generally needed
to insure that the sorbent is free from interfering compounds prior to
sampling. Tenax, for example, is often contaminated with benzene and
toluene from the manufacturing process, requiring extensive solvent
extraction and thermal conditioning before it is used. Once prepared,
sampling cartridges must be protected from contamination before and
after sampling.
12-88
-------
• No single adsorbent exists that will retain all vapor phase organics. The
efficiency of retention of a compound on a sorbent depends on the
chemicatpropertieS of both compound and sorbent. Generally, a sorbent
that works well for nonpolar organics such as benzene will perform poorly
with polar organics such as methanol, and vice versa. Highly volatile
compounds such as vinyl chloride will not be retained on weakly adsorbing
materials such as Tenax, while less volatile compounds will be irreversibly
retained on strong adsorbents such as charcoal. The optimal approach
involves use of a sorbent that will retain a wide range of compounds with
good efficiency, supplemented by techniques specifically directed towards
problem TM compounds.
• Tenax -GC is a synthetic polymeric resin which is highly effective for volatile
nonpolar organics such as aliphatic and aromatic hydrocarbons, and
chlorinated organic solvents. Table 12-13 lists compounds that have been
successfully monitored using a Tenax sorption protocol. Tenax has the
important advantage that it does not retain water. Large amounts of
water vapor condensing on a sorbent reduces collection efficiency and
interferes with GC and GCIMS analysis. Another advantage of this material
is the ease of thermal or chemical desorption.
The major limitation of Tenax is that certain highly volatile or polar
compounds are poorly retained (e.g., vinyl chloride, methanol). Formation
of artifacts (i.e., degradation products from the air contaminant sample
collected due to hydrolysis, oxidation, photolysis or other processes) on
Tenax has also been noted, especially the oxidation of amines to form
nitrosamines, yielding false positive results for the latter compounds.
Carbon sorbents include activated carbon, carbon molecular sieves, and
carbonaceous polymeric resins. The major advantage of these materials is
their strong affinity for volatile organ’cs , making them useful for highly
volatile compounds such as vinyl chloride. The strength of their sorptive
properties is also the major disadvantage of carbon sorbents because some
organic compounds may become irreversibly adsorbed on the carbon.
Thermal desorptiofl of compounds with boiling points above
approximately 80°C is not feasible due to the high temperature (400°C)
12-89
-------
required. Carbon adsorbents will retain some water, and therefore may
not be useful in high humidity conditions.
In addition to the Tenax and carbon tube sampling methods shown above,
passive sorption devices for ambient monitoring can be used. These passive
samplers consist of a portion of Tenax or carbon held within a stainless steel
mesh holder. Organics diffuse into the sampler and are retained on the
sorbent material. The sampling device is designed to fit within a specially
constructed oven for thermal desorption. Results from these passive
samplers were reported to compare favorably with pump-based sorbent
techniques. Because of the difficulty of determining the volume of air
sampled via passive sampling, these devices would appear to be mainly
applicable for screening purposes.
• Polyurethane foam (P1W) has been used extensively and effectively for
collection of semivolatile organics from ambient air. Semivolatiles include
PCBs and pesticides. Such compounds are often of concern even at very low
concentrations. A significant advantage of PUF is its ability to perform ati
high flow rates, typically in excess of 500 liters per minute (I/rn). Thu
minimizes sampling times.
PUF has been shown to be effective for collection of a wide range of
semivolatile compounds. Tables 12-14 and 1215 list compounds that have
been successfully quantified in ambient air with PUF. Compounds that have
shown poor retention or storage behavior with PUF include
hexachlorocyclohexane, dimethyl and diethylphthalates, mono- and
dichiorophenols, and trichioro- and tetrachlorobenzenes. These
compounds have higher vapor pressures, and may be collected more
effectively with Tenax or with resin sorbents such as XAD-2.
PUF is easy to handle, pre-treat, and extract. Blanks with very low
contamination concentations can be obtained, as long as precautions are
taken against contamination after pretreatment. Samples have been
shown to remain stable on PUF during holding times of up to 30 days. PUF
12-90
-------
(ABLE 12-14. SUMMARY LISTING OF ORGANIC COivPOUNDS SUGGESTED FOR COLLECTION WITH A LOW
VOLUME POLYURETHANE FOAM SAMPLER AND SUBSEQUENT ANALYSIS WITH AN
ELECTRON CAPTURE DETECTOR (GC/ECD)a
Polvchlonnated Biohertvls fPCBs ) p, p’DDT Chlorinated Phenols
Endosulfan a
Aroclor 1221’ Heptachlord 2,3-Dichlorophenolb
Arodor 1232d AldriM 2,4 Dsch1orophenolb
Arodor 1242k 2,5Dichlo rophen ofb
Aroclor 1016’ 2,6 DKhlorophenolb
Aroclor 1248d Polychiorinated Napthplenes ( PCN ) 3,4 Dichlorophenolb
Aroclor 12S4a 3.5 Dich1orophenolb
Aroclor 1260. Halowax 1001’ 2.3,4 Trichlorophenold
Halowax 1013C 2 ,3,5 Trichlorophenoli
2,36 Trichlorophenold
Chlorinated Pesticides 2 ,45-Trichlorophenol
Chlorinated Benzene 2 ,4,6.Trichlorophenold
a-chlordane 3 ,4,5TrichlOrophenOld
Y-chlordane 1 ,2,3-Trichlorobenzene 2 ,3.4 ,S Tetrachlorophenold
Chlordane ( technical)a 1,2,4.Trschlo .obenzened 2,3.4.6.Tetrachlofophenold
Mirex* 1 .3 ,5Trichtorobenzened 2.35.6- Tetrachlorophenold
a BHCa I ,2 ,3,4-Tetrachlorobenzene Pentachiorophenol’
B.BHCd 1 ,2.3,5 Tetrachtorobenzened
-BHC (Lindane) 1 ,2,4,S.Tetrachlorobenzened
BHCd Pentachlorobenaenea
p,p’ DDDd Hexach1orobenzene
p,p’-DDEa Pentachto,onitrobenzeflea
a Method validation data for all components, unless otherwise noted, are available in the literature. This includes collection efficiency
data andlor retention efficiency data, method recovery data, and in some cases, storage stability data on selected isomers from this
compound class.
b Method validation data not presently available in the literature for either a low or high volume sampling procedure Dichiorophenols,
however, are amenable to the same analytical protocols suggested for the higher molecular weight clorophenol isomers (trichloro,
tetrachloro, and pentachioro)- Users are cautioned that sample collection efficiencies may not be as high for dschlorophenols as for the
higher molecular weight chlorophenols. Collectionlretention efficiency data should be generated for each specific program
C Validation data employing low volume sampling conditions not presently available in literature Component has, however, been
evaluated using high volume PUF sampler
d Actual validation data for isomer(s) employing low volume PUF sampler not available in literature Behavior under low volume sampler
conilitions should be similar to other sirwiural isomers listed Component is amenable to analyiual scheme employing G JFCD
-------
TABLE 12-15. SUMMARY LISTING OF ADDITIONAL ORGANIC COMPOUNDS SUGGESTED FOR COLLECTION WITH A
LOW VOLUME POLYURETHANE FOAM SAMPLER
Polynudear Aromatic Hydrocarbons Herbicide Esters j Q sticides
Napthalene 2.4-D Esters, isopropyic Monuronc
Biphenyl 2,4-D Esters. butylc Diuronc
Fluorene 2 ,4-D Esters, isobulylc Linuronc
Dsbenzothioph.ne 2,4-D Esters, isoocty lc Terbuthiuronc
Phenanthrene Fluometuronc
Anthracene urganopnosphorous Pesticides Chloroto luronc
Carbazole
2-Methy lanthracene Mevinphosb Trsazine Pesticides
1 -Methyl phenanthrene Dichloivo s c
Fluoranthene Ronneic Simazinec
Pyrene Chlorpyriposc Atrazine’
Benzo(a)fluorene Diazinonc Propazinec
Benzo(b)f luorene Methyl parathion’
Benzo(a)anthracene Ethyl parathion’ Pyrethrin Pesticides
Chryseneltriphenylene
Benzo(b)fluoranthene Carbpmaie Pesticides Pyrethrin IC
Benzo(e)pyrene Pyrelhrin II ’
Benzo(a)pyrene Propoxur Allethrin ’
Perylene Carbofu ran’ d -trans-Al lethrinc
0 Phenytenepyrene Bendiocarbc D.crotophosc
Dibenzo(ac)l(ah)anthracene Me*acarbatec Resmethrinc
Benzo(g .hi)perylene Carbarylc Fenvalerate ’
Coronene
a These components have been reported in the literature using polyurethane foam samplers Users are cautioned that this listing is
provided solely as a working reference Method validation studies including collection efficiencies, retention efficiencies etc
employing the sampling procedutes cited in this document have not been conduned Procedures other than those noted in this
document may be more applicable in routine use
b Validation data employing low volume sampling conditions not presently available in literature Component, however, has been
evaluated using high volume PUF sampler
c sampler evaluation data for these compound classes using a low voiume (PUF) sampler contained in the literature
-------
concentration methods have shown excellent collection efficiency and
recovery of sorbed compounds from the material.
Most PUF methods specify the use of a filter ahead of the PUF cartridge, to
retain particulates. The filter prevents plugging of the PUF which would
reduce air flow through the sorbent. Some methods recommend
extracting the filter separately to obtain a value for particulate organics.
However, because most semivolatile compounds have sufficient vapor
pressure to volatilize from the filter during the collection period,
particulate measurements may not be representative of true particulate
concentrations. Therefore, results from the PUF analyses may overestimate
gaseous concentrations of semi-volatile compounds due to volatilization of
semi-volatiles originally collected on the sampler inlet filter and
subsequently collected by the PUF cartridge.
• Cryogenic methods for capturing and collecting volatile organics involve
pulling air through a stainless steel or nickle U-tube immersed in liquid
oxygen or liquid argon. After sampling, the tube is sealed, stored in a
coolant, and returned to the laboratory for anlaysis. The trap is connected
to a GC, rapidly heated, and flushed into a GC or GCIMS for analysis.
The major advantage of cryogenic concentration is that all vapor phase organics,
except the most volatile, are concentrated. This is a distinct advantage over sorbent
concentration, which is especially selective for particular chemical classes.
Contamination problems are minimal with cryogenic methods because a collection
media is not required.
Several disadvantages limit the current usefulness of cryogenic methods,
including:
• Samplers rapidly become plugged with ice in high humidity conditions. This
limits the volume of air that can be sampled.
• The entire sample is analyzed at once, enhancing sensitivity but making
multiple analyses of a sample impossible.
12-93
-------
• The necessity of handling and transporting cryogenic liquids makes thu
method cumbersome for many sampling applications.
• There is a possibility of chemical reactions between compounds in the
cryogenic trap.
Whole air sampling--Air may be collected without preconcentration for later use
in direct GC analysis or for other treatment. Samples may be collected in glass or
stainless steel containers, or in inert flexible containers such as Tedlar bags. Rigid
containers are generally used for collection of grab samples, while flexible
containers or rigid containers may be used to obtain integrated samples. Using a
flexible container to collect whole air samples requires the use of a sampling pump
with flow rate controls. Sampling with rigid containers is performed either by
evacuating the contaitler and allowing ambient air to enter, or by having both inlet
and outlet valves remain open while pumping air through the container until
equilibrium is achieved.
Whole air sampling is generally simple and efficient. Multiple analyses ar 1
possible on samples, allowing for good quality control. This method also has the’
ability to be used for widely differing analyses on a single sample. The method has
been widely used, and a substantial data base has been developed.
Problems may occur using this method due to decomposition of compounds
during storage and loss of some organics by adsorption to the container walls.
Sample stability is generally much greater in stainless steel containers than in
glass or plastic. Whole-air sampling is limited to relatively small volumes of air
(generally up to 20 liters due to the impracticality of handling larger sample
collection containers), and has higher detection limits than some sorbent
techniques.
Impinger collection—lmpinger collection involves passing the air stream through
an organic solvent. Organ ics in the air are dissolved in the solvent, which can then
be analyzed by GC/MS. Large volumes of air sampled cause the collection solvent to
evaporate. In addition, collection efficiency is dependent on flow rate of the gas,
and on the gas-liquid partition coefficier ts of the individual compounds. However
there are certain specialized applications of impinger sampling that have been
12-94
-------
found to be preferable to alternate collection techniques (e.g., sampling for
aldehydes and ketones).
Certain compounds of interest are highly unstable or reactive, and will
decompose during collection or storage. To concentrate and analyze these
compounds, they must be chemically altered (derivatized) to more stable forms.
Another common reason for derivatization is to improve the chromatographic
behavior of certain classes of compounds (e.g., phenols). Addition of the
derivatization reagent to impinger solvent is a convenient way to accomplish the
necessary reaction.
A widely used method for analysis of aldehydes and ketones is a DNPH
(dinitrophenylhydrazine) impinger technique. Easily oxidized aldehydes and
ketones react with DNPH to form more stable hydrazone derivatives, which are
analyzed by high performance liquid chromatography (HPLC) with a UV detector.
This method is applicable to formaldehyde as well as less volatile aldehydes and
ketones.
Direct analysis--A method not requiring preconcentration or separation of air
components is highly desirable, because it avoids component degradation or loss
during storage. Air is drawn through an inert tube or probe directly into the
instrument detector. Several portable instruments exist that can provide direct air
analysis, including infrared spectrophotometers, mobile MS instruments, and
portable FID detectors. Some of these instruments have been discussed in the
section on screening methods.
Mobile mass spectrometry has been used to compare upwind and downwind
concentrations of organic pollutants at hazardous waste management facilities.
The advantage of the multiple mass spectrometer configuration (MS/MS or triple
MS) over a single MS system is that multiple systems can identify compounds in
complex mixtures without pre-separation by gas chromatography. Major
limitations of MS/MS methods are low sensitivity and high instrument cost.
12-95
-------
In summary, of the methods described in this subsection, the majority of vapor-
phase organics can be monitored by use of the following sampling methods:
• Concentration on Tenax or carbon adsorbents, followed by chemical or
thermal desorption onto GC or GC/MS.
• Sorption on polyurethane foam (PUF) cartridges, followed by solvent
extraction.
• Cryogenic trapping in the field.
• Whole-air sampling.
12.6.2.2.1.2 Particulate Organics
Certain hazardous organic compounds of concern in ambient air are primarily
associated with airborne particles, rather than in the vapor phase. Such compounds
include dioxins, organochlorine pesticides, and polyaromatic hydrocarbons.
Therefore, to measure these compounds accurately, it is necessary to monitor
particulate emissions from units of concern.
Measurements of particulate organics is complicated because even relatively
nonvolatile organics exhibit some vapor pressure, and will volatilize to a certain
extent during sampling. The partitioning of a compound between solid and
gaseous phases is highly dependent on the sampling conditions (e.g., sampling flow
rate, temperature). Particulate sampling methods generally include a gas phase
collection device after the particulate collector to trap those organics that become
desorbed during sampling.
The most common methods used for collection of particles from ambient air are:
• Filtration
• Cellulose Fiber
• Glass or Quartz Fiber
- Teflon Coated Glass Fiber
12-96
-------
Membranes
• Centrifugal Collection (e g., cyclones)
• Impaction
• Electrostatic Precipitation
The standard sampling method for particulates, is filtration. Teflon-coated glass
membranes generally give the best retention without problems with separating the
particulates sampled from the filter. Problems, however, may be caused by
desorption of organics from the filter, by chemical transformation of organics
collected on the filter, and with chemical transformation of organics due to reaction
with atmospheric gases such as oxides of nitrogen and ozone. These problems are
worsened by the large volumes of air that must be sampled to obtain sufficient
particulate material to meet analytical requirements. For example, to obtain 50
milligrams of particulates from a typical air sample, 1000 cubic meters of air must be
sampled, involving about 20 hours of sampling time with a high-volume sampling
pump.
Despite the drawbacks mentioned above, filtration is currently the simplest and
most thoroughly tested method of collecting particulates for organic analysis.
Other methods, such as electrostatic precipitation, make use of electrical charge or
mechanical acceleration of the particles. The effect of these procedures on
compound stability is poorly understood.
12.6.2.2.2 Monitoring Inorganic Compounds in Ambient Air
12.6.2.2.2.1 Particulate Metals
Metals in ambient air can occur as particulates or can be adsorbed on other
particulate material. Metals associated with particulate releases are effectively
collected by use of filter media allowing for the collection of adequate samples for
analysis of a number of particulate contaminants.
12-97
-------
Collection on filter media--Sampling methods for particulate metals are
generally based on capture of the particulate on filter media. For the most part,
glass fiber filters are used; however, organic and membrane filters such as cellulose
ester and Teflon can also be used. These membrane filters demonstrate greater
uniformity of pore size and, in many cases, lower contamination levels of trace
metals than are found in glass fiber filters. Analytical procedures described in the
following reference can be utilized to analyze particulate samples.
U.S. EPA. 1986. Test Methods for Evaluating Solid Waste . 3rd Edition. EPA SW-
846. GPO No. 955-001-00000-1. Office of Solid Waste, Washington, D.C. 20460.
Hi-Vol collection devices--The basic ambient air sampler is the high volume
sampler which can collect a 2000 cubic meter sample over a 24-hour period and
capture particulates on an 8 x 10 inch filter (glass fiber) as described in 40 CFR Part
50. It has a nominal cut point of lOOum for the maximum diameter particle size
captured. A recent modification involves the addition of a cyclone ahead of the
filter to separate respirable and non-respirable particulate matter. Health criteria
for particulate air contaminants are based on respirable particulate matter.
Personnel samplers--Another particulate sampling method involves the use of
personnel samplers according to NIOSH methods (NIOSH, 1984). The NIOSH
methods are intended to measure worker exposure to particulate metals for
comparison to OSHA standards. A 500-liter air volume is sampled at approximately
2 liters per minute. This method is most efficient when less than 2 mg total
particulate weight are captured. Capture of more than 22 mg may lead to sample
losses during handling of the sample. The preferred filter medium is cellulose ester
(47 mm diameter) which will dissolve during the standard acid digestion.
The NIOSH method, however, is not recommended for the RFI for several
reasons. The NIOSH analytical methods (and good QA/QC practices) require several
aliquots of the sample to be prepared for best analytical results. The 47 mm filter is
too small for aliquoting; therefore, use of the NIOSH method would require the
simultaneous operation of several sampling systems. More importantly, the 500
liter sample volume generaly does not provide sufficient particulate matter for the
analytical methods to detect trace ambient levels of metals. The method is best
suited for industrial hygiene applications.
12.98
-------
Dichotomous Samplers--Dichotomous samplers (virtual impactors) have been
developed for particle sizing with various limit cutpoints for use in EPA ambient
monitoring programs. These samplers collect two particulate fractions on separate
37 mm diameter filters from a total air volume of about 20 cubic meters. The
standard sampling period is 24 hours. Teflon filters are generally recommended by
sampler manufacturers because they exhibit negligible particle penetration and
result in a low pressure drop during the sampling period. However, glass fiber and
cellulose filters are also acceptable.
The need for multiple extractions would require multiple sampling trains. If the
two filters are combined to form one aliquot and extracted together, they will
provide sufficient sensitivity for some but not all analytical procedures and defeat
the purpose of fractioning the sample. The use of the dichotomous sampler is,
therefore, limited.
12.6.2.2.2.2 Vapor Phase Metals
Most metallic elements and compounds have very low volatilites at ambient
temperatures. Those that are relatively volatile, however, require a different
sampling method than used for collection of particulate forms, although analytical
techniques may be similar. For the purpose of ambient monitoring, vapor-phase
metals are defined as all elements or compounds that are not effectively captured
by standard filter sampling procedures. Available methods for the measurement of
vapor phase metals are presented in Tables 12-16 and 12-17. These available
methods are generally developed for industrial hygiene applications by NIOSH.
The methods for measuring vapor-phase metals presented in Tables 12-16 and
12-17 have undergone limited testing for precision and accuracy and have had
matrix interferences documented. Therefore, they should be used in lieu of any
methods which have no supporting data.
Several methods are suitable for quantification of vapor-phase mercury. If
elemental mercury is to be measured, the silver amalgamation technique with
12-99
-------
TABLE 12-16. SAMPLING AND ANALYSIS METHODS FOR VOLATILE MERCURY
Method/Reference
Species measured
Procedures summary
Advantages
Disadvantages
NIOSH P&CAM 6000
Particulat. organic and
elemental mercury
Sampling (rain consists of
membrane filter to capture
particulate Hg. followed by
Carbosieve B to trap organic Hg.
and then silver coated Chromosorb
P (CP) to collect elemental Hg.
Each section is analyzed separately
by thermal desorption into a
flameless AA. Filters are acid
digested, reduced to Hg and
amalgamated on Ag CP prior to the
AA analysis step.
- Standard method
• Permits
measurement of all
three types of
mercury
- Method selective to
mercury
,
- Requires use of complex
desorption unit
Cl 2 interferes with sampling
- Separation of organic and
metallic mercury is uncertain
at 0.001 HbJtotal Hg
- Requires pIepar .on of
special sorbents
NIOSH SCP-S342
Organic mercury
Filter to Separate particulate;
adsorb organic Hg on Carbosseve
B; thermally desorb into flameless
AA unit
- Standard method
- Option to P&CAM
175 if organic
mercury is only
concern
- Range is 20-80
tig/m with a 3 liter
sample volume
- Requires complex thermal
desorption unit
EPA Method 101
Particulate and
vaporous mercury
Collection in acidified 0.1 NHCS
impinger solution; analysis by ftIAA
or optionally by cold vapor AA
- Standard method
- Detection limit of I
pg/m i
- Fairly stable reagent
- Same reagent has
been used for
volatile Pb (Ref 572)
- NAA expensive ($1 25/sample)
and not routinely available
- Ice interferes with cold vapor
AA method at low
concentrations of Hg
- Instability of collected Hg
compounds in solution has
been reported
Canadian EPS
Standard Method
Particulate and
vaporous mercury
Collection in impinger solution of
10% H 2 S0 4 12% KMnO 4 ; analysis by
cold vapor AA
- Standard method
- Collection efficiency
90%
- KMnO 4 and AA
compatible
- AA costs
S3Wsample
• Reagent gives low
- kMnO 4 reagent must be
prepared within 12 hours of
use
Short sample holding time
Reagent can be easily
expended in oxidizing and
organic matrices
-------
TABLE 12-16. (continued)
Method/Reference
Species measured
Procedures summary
Advantages
Standard method
Disadvantages
- Compte!
Environment Canada
Vaporous mercury or
particulate mercury
Vaporous mercury is collected by
amalgamation on silver
Particulate is collected on
mscroquartz filters Both are
analyzed by thermal desorption
and/or pyrolysis with re-
amalgamation. then thermal
desorption for determination by
UV absorption at 253 7
-
for ambient air
Used in range of 4•
22 mg/rn)
- Claimed to be
inexpensive
desorptionlamalgamatson
unit
interferes with
3M Badge
Elemental Hg vapor
Passive device-diffusion of Hg
through membrane,
amalgamation on gold, analysis of
badges performed by 3M
- Very simple and
mercury specific
method
- Requires no analysis
to be performed by
users
Gives 8-hour time
weighted average
and concentrations
of up to 20 p g /rn 3
- Cl 2
sampling
efficiency
- High H 2 S and SO also
interfere
- Temperature variations affect
diffusion rates and must be
corrected for
- Large coefficient of variation
MSA Method
Elemental and organic
mercury
Adsorb mercury on iodine
impregnated charcoal; place in
tantalum boat and volatilize
- Simple equipment
requirements
- Range of 50-200
pg/rn 3 tested
equipment
- Quality of results are very
much operator dependent
- Only works well at 200 pg/m i
- Does not provide (or analysis
Hopcalite Method
Elemental and organic
mercury
Adsorb on hopcal.te; dissolve
sorbent and mercury in HNO 3 •
HO; analyze by cold vapor PA
- Simple
requirement
- Evaluated in range
of 50-200 Iignn 3
of particulate mercury
- Insufficient performance data
in available literature
p.J
-e
a
-------
TABLE 12-16 (continued)
Method/Reference
Species measured
Procedures summary
Advantages
Disadvantages
Silver
amalgamation and
APHA
Vaporous elemental
mercury
Amalgamation on silver wool or
silver gauge; thermal desorption
with analysis by flameless AA or UV
absorption
.
- Substantial
information on the
method,
interferences
provided in the
references
- Ag wool- 24 hour
sample can be used
with lSng-lOpglm)
levels
- Ag gauge 2 hour
sample can give
concentrations of 5
ng-IOO saglm 3
- Collection efficiency for
organic mercury is in question
- Oxidants could interfere with
sampling procedure unless
removed before reaching
silver
lmpiriger/Dithizone
Organic, particulate and
vaporous mercury
Collect in impinger solution of 0 I
NiCI and OS m HCI; analyze by the
dithizone colorimetruc method
- Efficient capture of
all three types of
volatile mercury
Dithizone method suffers
from high blanks,
interference from SO 2 and
interference from several
other metals
- Mercury compounds collected
in HCI are unstable
Jerome Instrument
Corp . Model 411.
Gold Film Hg Vapor
Analyzer
Elemental mercury
Onsite monitor-amalgamation of
Hg on gold, measure concentration
by change in gold foil resistance
- Selective for
mercury
- Direct reading
eliminates sample
transport and
analysis
- Concentration
range from ag /rn 3
to mWm 3
- Monitor costs $3500-$4000
- May suffer interference from
oxidants as noted for 3M
badges
* Recommended methods
-------
TABLE 12-17.
SAMPLING AND ANALYSIS OF VAPOR STATE TRACE METALS (EXCEPT MERCURY)
Element
Reference(s)
measured
Procedures summary
mercuric chloride
Advantages
- Standard method
Disadvantages
- Range only 0.1-1 0 ng/m 3
Antimony
NIOSH 5243
Stibine (SbH 3 )
on
impregnated silica gel; extract with
concentration HCI. oxidize Sb(1 11)
to Sb(V) with ceric sulfate;
colorimetric analysis by Rhodamsne
charcoal; desorb with
- Standard method
using a 20-liter sample
- Analytical interferences
by Pb(Ill), 11(1). and Sb(lI)
.
- Possible brea(through at
Arsenic
NIOSH P&CAM
6001
Arsin (A5H)
on
HNO 3 . analyze by furnace AA
265
that
- Standard method
high concentrations
- Possible breakthrough at
NIOSH 5229
NIOSH 1900
Arsin. (AsH 3 )
Same as
except
HP40 3 desorption is performed with
10 ml rather than 1 ml
NaOH solution;
- Working range 0 09-
0 1 mglm 3
- Only method
high concentrations
- Earlier version of P8ICAM
265
- No supporting data
As 1 Oj and
others
Absorb
analytical procedure not specified
but it may be suitable to use arsine
generation or furnace AA
proposed for AS 1 0 3
in available
literature
- Relatively simple
available
NIOSH S383 and
S384
Tetraethyl lead
and tetramethyl
lead
Adsorb on XAD-2; desorb with
pentane; analysis by GC
Standard method
- Permits separation
of the various alkyl
lead compounds
- Range 0045-0 20
nglm 3 (as Pb)
• Can alter GC
conditions to
remove
interferences with
analysis
Compound identification
only by GC retention
times; must verify
Alkyl lead
Collect in HCIINiCI impinger
solution; analyze by dithizone
collection efficiency
literature
compounds
colorimetriC method when 8-hour
sampling period or by AA for 24
hour sample
-
-
Dithizone detection
limit - 10 gIm 3
AA detection limit -
0.2 - 10 Ii lm 3
-
Dithizone method may
have same problems
noted elsewhere for
other elements
r.J
—a
a
Lead
-------
TABLE 12-17. (continued)
Element
Reference(s)
Species
Procedures summary
Advantages
Disadvantages
Alkyl lead
compounds
Adsorb on activated carbon, digest
with HNO 3 • HCIO 4 ; analyze by
dithizone method
- Good collection
efficiency
Low detection limits
passable
- No data available
- Dithizone method may
have interferences as
noted above
Nickel
NIOSH P1CM
344
NiCkel
t.trac.rbonyl
(Ni(CO) 4 )
Adsorb on charcoal; desorb with
dilute HNO 3 ; analyze by furnace AA
- Standard method
- AA specific for
Nickel
- Range 2-60 igIm 3
- Sorbeat capacity limits
upper concentration
Ref 120. 142
Nickel
tetracarbonyl
(Ni(CO) 1 )
Absorb in 3% HCI impinger solution;
analyze by colorimetric method in
which color development in
chloroform phase is measured
- Detection limit -
0001 ppm
- Not a standard method
- Interference may occur
from other Nickel
compounds, Cu. Pb. Cr.
Se and V
Selenium
Se0 1 , H 2 Se0 3
Collect in impanger with aqueous
solution of Na 2 SO 3 , Na 1 S. or NaOH,
analyze by NAA, AA. GC.
colorimetry. fluorimetry. ring oven
techniques, or catalytic methods
Only method
suggested in
literature for
volatile S.
No data to support this
method
-------
thermal desorption and flameless AA (atomic absorption) analysis is recommended.
This technique is presented in American Public Health Association (APHA) Method
317. which can a hieve nanogram per cubic meter detection limits. If organic and/or
particulate mercury are also to be determined, NIOSH methods (NIOSH, 1984) are
recommended. These methods can measure all three airborne mercury species, but
require a complex two stage thermal desorption apparatus.
12.6.2.2.2.3 Monitoring Acids and Other Compounds in Ambient Air
Monitoring for acids and other inorganic/non-metal compounds (e.g., hydrogen
sulfide) in the ambient air will generally require application of industrial hygiene
technologies. Applicable methods have been compiled in the following references:
NIOSH. February 1984. NIOSH Manual of Analytical Methods . NTIS PB 85-
179 108. National Institute for Occupational Safety and Health. Cincinnati. OH.
ASTM. 1981. Toxic Materials in the Atmosphere . ASTM, STP 786. Philadelphia.
PA.
APHA. 1977. Methods of Air Sampling arid Analysis . American Public Health
Association.
ACGIH. 1983. Air Sampling Instruments for Evaluation of Atmospheric
Contamination . American Conference of Governmental Industrial Hygienists.
Cincinnati, OH.
12.6.3 StackiVent Emission Sampling
EPA methods for source-sampling and analysis are documented in the following
reference:
Code of Federal Regulations. 40 CFR Part 60, Appendix A: Reference Methods.
Office of the Federal Register, Washington. D.C. 20460.
12-105
-------
Additional guidance is available in the following references:
U.S. EPA. 19 8. Stack Sampling Technical Information, A Collection of
Monographs and Papers. Volumes I-Ill . EPA-450/2-78-042 a, b, c. NTIS PB 80-
161672, 80-1616680, 80-161698. Office of Air Quality Planning and Standards.
Research Triangle Park, NC 27711.
U.S. EPA. February 1985. Modified Method 5 Train and Source Assessment
Sampling System Operators Manual . EPA-600/8-85-003. NTIS PB 85-169878.
Office of Research and Development. Research Triangle Park, NC 27711.
U.S. EPA. March 1984. Protocol for the Collection and Analysis of Volatile
POHC’s Using yOST . EPA-600/8-84.007. NTIS PB 84-177799. Office of Research
and Development. Research Triangle Park, NC 27711.
U.S. EPA. February 1984. Sampling and Analysis Methods for Hazardous Waste
Combustion . EPA-600/8-84.NTIS PB 84-145580. Washington, D.C. 20460.
U.S. EPA. November 1985. Practical Guide - Trial Burns for Hazardous Waste
Incinerators . NTIS PB 86-190246. Office of Research and Development.
Cincinnati, OH 45268.
U.S. EPA. 1981. Source Sampling and Analysis of Gaseous Pollutants . EPA- APTI
Course Manual 468. Air Pollution Control Institute. Research Triangle Park, NC
27711.
U.S. EPA. 1979. Source Sampling for Particulate Pollutants . EPA-APTI Course
Manual 450. PB 80-188840, 80-174360. 80-182439. Air Pollution Control
Institute. Resarch Triangle Park, NC 27711.
U.S. EPA. 1986. Test Methods for Evaluating Solid Waste . 3rd Edition. EPA/SW-
846. GPO No. 955-001-00000-1. Office of Solid Waste, Washington, D.C. 20460.
12-106
-------
12.6.3.1. Vapor-Phase and Particulate Associated Organics
Generally, poi t source vapor-phase samples are obtained from the process vents
and effluent streams either by a grab sample technique or by an integrated
sampling train: Careful planning is necessary to insure that sampling and analytical
techniqes provide accurate quantitative and qualitative data for measurements of
vapor-phase organics. Considerations such as need for real-time (continuous) versus
instantaneous or short-term data, compatibility with other compounds/parameters
to be measured, and the need for onsite versus offsite analysis may all be important
in the selection process.
Monitoring for complex organic compounds generally requires detailed
methods and procedures for the collection, recovery, identification, and
quantification of thesE compounds. The selection of appropriate sampling and
analytical methods depends on a number of important considerations, including
source type and the compounds/parameters of interest. Table 12-18 lists several
sampling methods for various applications and compound classes (applicable to
combustion sources). The first three methods listed are fixed-volume, grab-
sampling methods. Grab sampling is generally the simplest technique to obtain
organic emission samples.
Sample collection by the bag and canister sampling methods can be used to
collect time-integrated samples. These methods also allow for a choice of sample
volumes due to a range of available bag sizes (6, 12, and 20 liter capacities are
typical). Bags of various materials are available, including relatively inert and
noncontaminating materials such as Teflon, Tedlar, and Mylar. All sample collection
bags types may have some sample loss due to adsorption of the contaminants
collected to container walls. The bag sample is collected by inserting the bag into
an airtight, rigid container (lung) and evacuating the container. The sample is
drawn into the bag because reduced pressure in the container provides adequate
suction to fill the bag. This procedure is presented in detail in 40 CFR, Part 60
Appendix A (Method 3).
12-107
-------
TABLE 12-18. SAMPLING METHODS FOR TOXIC AND HAZARDOUS ORGANIC MATERIALS FROM POINT SOURCES
Sampling
Method
De Cii
p
Applicable
Source Type
Applicable
Compound Type
Method(s)
Sampling Method
m t 10n 5
Syringe
flow-through
bottle
Evacuated
canister
Tedlar bag
(EPA Method 3)
Instantaneous grab
Non-combustion
(storage tanks
spray booths
paint bake
ovens, etc)
Low moisture
content
combustion
emissions
(boilersdry
control
incinerators,
etc).
Volatiles. Ci-
CiO
Volatiles. C 1 -
C to
Volatiles, C-
C 1
Volatiles. C1-
C 10
GC FlDa
GC MSb or
GC-PID’
Sample size and therefore detectable
concentration are limited by container
size; 1 ppm
‘
Bag samples are subject to absorptive
losses ol sample components
instantaneous grab
Integrated grab
Integrated grab
EPA method 25
Two stage integrated grab train
consisting of cold trap followed
by evacuated S S. tank.
Non-combustion
and low
moisture
content
combustion
emissions as
above.
Volatiles and
semi-volatiles,
C,-C 16
Oxidationl
reduction
followed by
GCIFID.
Sample size is limited by tank volume
CO 2 and II0 can produce significant
interferences System is
compleit/cumbersome
.VOSTd
Water-cooled sample gas.
including condensate, is passed
throughdual in-seriessorbent
traps. Teriax GC in first tube
followed by Tenax GC backed-up
by charcoal in second tube
Combustion
emissions
(boilers.
hazardous
waste
incinerators,
etc )
Volatiles and
smi volatiles,
C 1 -C 16 .Ci-Ci
GC-MS
GC-ECD
GC-PID
Sample size is limited to 20 liters per
pair of sorbent tubes. Sorbent tubes
aresusceptable tocontamination
from organics in ambient air during
installation and removal from train
-------
TABLE 12-lb continued)
GC-FlD - gas chromatography with flame ionization detector.
b GC-MS - gas chromatography-mass spectrometry.
GC-P ID - gas chromatograPhy-PhOtOlOflh1at10 detector.
d VOST - volatile organic sampling train.
e Sorbents include Florisil . XAD-2 resin, and Tenax-GC among the most commonly used
-‘
p . .,
a
0
Sampling
Method
escri
p
Applicable
Source Type
Applicable
Compound Type
Meth s)
Sampling Method
Limitations
Modified
Method 5
Water-coiled sample gas. with
condensate is passed through
single sorbent trap Sorbent type
dependent on compound(s) of
interest.’
Combustion
emission as for
yOST
Semi-volatiles.
PCB’s, other
halogenated
organics. c-c, .
ci••-(i
GC-ECD.
GC-HECD.
GC-MS
Single trap system does not provide
check for breakthrough. Flow rate
limited to approiümately I cpm
High Volume
Modified
Method 5
Sample gas is passed through
condensers where moisture is
removed before passing through
two sorbent traps, primary
followed by back-up Flow rates
of up to 5 cpm are achievable
Sorbent type dependent on
compounds of interest
Combustion
emissions
Semi-volatiles.
PCBs, other
halogenated
organics. C,-C 16 .
C 1 -C 0
GC-ECD,
GC-H(CD.
GC-MS
High flow rate results in high
sampling train pressure drop
requiring large pump capacity
compleit. large and
SASS Train
Sample gas passes through a cold
trap followed by an XAD-2
sorbent trap. Train is all stainless
steel construction,
Combustion
emissions
(boilers. .
hazardous
waste
incinerators)
Semi-volatiles.
and other, non-
halogenated
organics. c 7 -c- 6
GC-ECD.
GC-H(CD.
GC-MS
ystem is
cumbersome Recovery of organics
from cold trap can be difficult S S
construction makes train components
highly susceptable to corrosion from
acid gases especially HCI
Source: Hazardous Waste Management. Vol 35. No 1, January 1985
-------
Evacuated canisters are conventionally constructed of high grade polished
stainless steel. There are many versions available ranging from units with torque
limiting needle 7alves, purge free assemblies, internal electropolished surfaces and
versions utilizing stainless steel beakers with custom designed tops and fittings.
Also, differenj container materials may react differently with the sample.
Therefore, sample storage time or sample recovery studies to determine or verify
inertness of the sampling canister should be considered.
Canisters are generally used to collect samples by slowly opening the sample
valve, allowing the vacuum to draw in the sample gas. In less than a minute, the
container should equilibrate with the ambient atmospheric pressure. At that time,
the sample valve is closed to retain the sample. To collect composite samples over
longer intervals, small calibrated orifices can be inserted before the inlet valve to
extend the time required for equilibration of pressures once the sample valve is
opened.
The sample collection procedure for EPA Method 25 (U.S. EPA, 1981) is similar in
principle to that for the evacuated canister. The train consists of a polished
stainless steel canister with a cold condensate trap in series and prior to the caniste
to collect a higher boiling point organic fraction. This two fraction apparatu
provides for separate collection of two concentration ranges of volatile organic
compounds based on boiling point.
The following four sampling methods utilize sample concentration techniques
using one or more sorbent traps. The advantages of these methods is an enhanced
limit of detection for many toxic and hazardous organic compounds. These
techniques are preferred due to their lower detection limit. The Modified Method 5
(MM5) sampling train (U.S. EPA, 1981) is used to sample gaseous effluents for vapor-
phase organic compounds that exhibit vapor pressures of less than 2 mm Hg (at
20’C). This system is a modification of the conventional EPA Method 5 particulate
sampling train. The modified system consists of a probe, a high efficiency glass or
quartz fiber filter, a sorbent module, impirigers, and related control hardware. The
sample gas is passed through a single sorbent trap, containing XAD -2. The MM5
train is limited due to the single sorbent trap design that does not provide a backup
for breakthrough. This is especially important when large volumes of sample are
collected.
12-110
-------
To minimize the potential for breakthrough, the MM5 train can be modified to
provide a backup trap. l owever. this dual trap modification increases the pressure
drop across the train, reducing the range of flow rates possible for sample
collection. To overcome this pressure drop and maintain the desired flow rate, the
high-volume MMS train utilizes a much larger capacity pump.
The Source Assessment Sampling System (SASS) train is another comprehensive
sampling train, consisting of a probe that connects to three cyclones and a filter in a
heated oven module, a gas treatment section, and a series of impingers to provide
large collection capacities for particulate matter, semivolatiles, and other lower
volatility organics. The materials of construction are all stainless stee’ making the
system very heavy and cumbersome. The stainless steel construction is also very
susceptible to corrosion. This system can, however, be used to collect and
concentrate large sample volumes providing for a much lower detection limit.
Because of the sorbents used (generally XAD-2), its use is limited to the same class o
lower volatility organics and metals as the MM5 train.
The Volatile Organic Sampling Train (yOST) has proven to be a reliable and
accurate method for collection of the broad range of organic compounds. By using
a dual sorbent and dual n-series trap design, the VOST train can supplement either
the MMS or SASS methods allowing for collection of more volatile species. However,
yOST has several limitations, including a maximum sample flow rate of 1.0
liter/minute, and a total sample volume of 20 liters per trap pair. Therefore,
frequent changes of the trap pairs are required for test periods that exceed 20
minutes. The frequent change of traps makes the samples more susceptible to
contamination.
Any of the point source monitoring techniques described above can be adapted
for use with the isolation flux chamber techniques described in Appendix D. For
point sources where particulate emissions are of concern, the Modified Method S or
SASS train (originally designed to measure particle emissions from combustion
effluents) are also applicable and proven technologies.
Analytical methodologies for the techniques discussed above will vary with the
technique used. While certain techniques will offer advantages over others in the
12-111
-------
measurement of specific contamu,ants, the investigator is advised to utilize
standard methodologies whenever possible in performing the RFI. For example, use
of the VOST and/Or the MM5 train, and their associated analytical methodologies is
recommended for point source monitoring of the applicable compounds.
Descriptions for both of these methods are included in the 3rd Edition of uTest
Methods for Evaluating Solid Waste (EPA SW-846), 1986 (GPO No. 955-001-00000-
1). Although these methods are designed for the evaluation of incinerator
efficiencies, they are essentially point-source monitoring methods which can be
adapted to most any point sources.
12.6.3.2 Metals
Although the emission of metallic contaminants is primarily associated with
particulate emission from area sources caused by the transfer of material to and
from different locations, wind erosion, or general maintenance and traffic activities
at the unit, point source emission of particulate or vapor-phase metals can exist.
Metallic constituents may exist in the atmosphere as solid particulate matter, as
dissolved or suspended constituents of liquid droplets (mists), and as vapors.
Metals specified as hazardous constituents fri 40 CFR Part 261, Appendix VIII are
generally noted as the element and compounds not otherwise specified (NOS)”, as
shown in Table 12-19, indicating that measurement of the total content of that
element in the sample is required.
Vapor phase metals—For the purpose of point-source monitoring, vapor-phase
metals will be defined as all elements or compounds thereof, that are not
quantitatively captured by standard filter sampling procedures. These include
volatile forms of metals such as elemental and alkyl mercury, arsine, antimony, alkyl
lead compounds, and nickel carybonyl.
The sampling of point sources for vapor phase metals has not been a common or
frequent activity for the investigation of air releases from solid waste management
units. If a point source of vapor-phase metals is identified, the sampling approach
12-112
-------
Table 12-19.
RCRA Appendix VIII Hazardous Metals and Metal Compounds
Antimony and compounds NOSa
Arsenic and compounds NOSb
Barium and compounds NOSb
Beryllium and compounds NOS
Cadmium and compounds NOS
Chromium and compounds NOS
Lead and compounds NOS
Mercury and compounds NOSb
Nickel and compounds NOSb
Selenium and compounds NOSb
Silver and compounds NOSb
Thallium and compounds NOSb
aNOS not otherwise specified.
bAdditional specific compound(s) listed for this element.
12-113
-------
identify the best available monitoring techniques, considering that many have been
developed which are specific to single species rather than multiple species of many
different metal ëlements. The primary references for identifying available
techniques include National Institute of Occupational Safety and Health (NIOSH,
1984) methods, EPA methods such as those presented in SW-846 and in the Federal
Register under the National Emissions Standards for Hazardous Air Pollutants
(NESHAPs), and American Public Health Association (APHA, 1977) methods. The
basic monitoring techniques include collection on sorbents and in impinger
solutions. The particular sorbent or impinger solution utilized should be selected
based on the specific metal species under investigation.
Particulate Metals Point-source releases to air could also require investigation of
particulate metals. Source sampling particulate procedures such as the Modified
Method 5 or SASS methods previously discussed are appropriate for this activity.
EPA Modified Method 5 is the recommended approach. Modifications of this basic
technique involving the collection of particulate material on a filter with
subsequent analysis of the collected particulate for the metals of concern, could
include higher or lower flow rates and the use of alternate filter media. Such
modifications may be proposed when standard techniques prove to be inadequate.
Several important particulate metal sampling methods are available in the NIOSH
methods manuals (NIOSH, 1984); however, these methods were designed for
ambient or indoor applications and may require modification if used on point
sources.
12-114
-------
1 2.7 Checklist
RFI Checklist- AIR
Site NameILoc atson ________________________________________________
Type of Unit _____________________________________________
1. Does waste characterization include the following information? (YIN)
• Physical form of the waste __________
• Identification of waste components _________
• Concentrations of constituents of concern _________
• Chemical and physical properties of constituents
of concern
2. Does unit characterization include the following i f rrnation (YIN)
• Type of unit
• Types and efficiencies of controldevices ________
• Operational schedules ________
• Operating logs
• Dimensions of the unit ________
• Quantities of waste managed
• Locations and spatial distribution/
variation of waste in the unit _______
• Past odor complaints from neighbors
• Existing air monitoring data _______
• Flow rates from vents
3. Does environmental setting characterization include
the following information? (YIN)
• Definition of regional climate
• Definition of site-specific meteorological conditions
• Definition of soil conditions
12-115
-------
• Definition of site-specific terrain
• Identification of potential release receptors
4. Have the following data on the initial phase of the release
characterization been collected’ (V/N)
• Identification of reasonable worst case”
conditions
• Meteorological conditions during monitoring _______
• Release source conditions during monitoring _______
• Basis for selection of monitoring constituents
• Concentrations of released constituents at unit,
facility and nearby actual offsite receptors based
on monitoring or modeling and “reasonable
worst case” conditions
5. Have the following data on the subsequent phase(s) of the
release characterization been collected (V/N)
• Identification of “reasonable worst case”
conditions
• Meteorological conditions during monitoring
• Release source conditions during monitoring
• Basis for selection of monitoring constituents
• Concentrations of released constituents at unit,
facility and nearby actual offsite receptors
based on monitoring or modeling and
representative of reasonable “worst case”
conditions
12-116
-------
12.8 References
ACGIH. 1983. AipSampling Instruments for Evaluation of Atmospheric
Contamination . American Conference of Governmental Industrial Hygienists.
Washington, D.C.
APHA. 1977. Methods of Air Sampling and Analysis . American Public Health
Associations. Cincinnati, OH.
ASTM. 1982. Toxic Materials In The Atmosphere . ASTM, SIP 786.
Philadelphia, PA.
ASTM. 1981. Toxic Materials in the Atmosphere . ASTM, SIP 786.
Philadelphia, PA.
ASIM. 1980. Sampling and Analysis of Toxic Organics in the Atmosphere . ASTM,
SIP 721. Philadelphia, PA.
ASTM. 1974. Instrumentation for Monitoring Air Quality . ASTM, SIP 555.
Philadelphia, PA.
National Climatic Data Center. Climates of the United States . Asheville, NC 28801.
National Climatic Data Center. Local Cljmatological Data -Annual Summaries
with Comparative Data , published annually. Asheville, NC 28801.
National Climatic Data Center. Weather Atlas of the United States .
Asheville, NC 28801.
National Institute for Occupational Safety and Health. NTIS PB 85-179018. (NIOSH).
1985. NIOSH Manual of Analytical Methods .
Turner, D I. 1969. Workbook of Atmospheric Dispersion Estimates . Public Health
Service. Cincinnati, OH.
12-117
-------
U.S. EPA. 1987. Hazardous Waste Treatment Storage and Disposal Facilities ( TS9fj
Air Emission Models . Draft Report. Office of Air Quality Planning and Standards
Research Truanble Park, NC 27711.
U.S. EPA. 1986.-Evaluation of Control Technologies for Hazardous Air Pollutants :
Volume 1 -Technical Report. EPA/60017-86/009a. NTIS PB 86-167020. Volume 2-
Appendices. EPAI600I7-86/009b. NTIS PB 86-167038. Office of Research and
Development. Research Triangle Park, NC 27711.
U.S. EPA. Septmber 1986. Handbook Control Technologies for Hazardous Air
Pollutants . EPA/625 16-86/014. NTIS PB 86-167020, 86-167038. Office of Research
and Development. Research Triangle Park, NC 27711.
U.S. EPA. 1986. Measutement of Gaseous Emission Ratesfrom Land Surfaces
Using an Emission Isolation Flux Chamber: User’s Guide . 1986. EPAJ600/8-
86/008. NTIS PB 86-223161. Environmental Monitoring Systems Laboratory. Las
Vegas, NV 89114.
U.S. EPA. 1986. Test Methods for Evaluating Solid Waste . 3rd Edition.
EPA SW-846. GPO No.955-001-00000-i. Washington, DC 20460.
U.S. EPA. July 1986. Guideline on AirQuality Models ( Revised) . EPA 450/2.78-027R.
NTIS PB 86-288783. Office of Air Quality Planning and Standards. Research
Triangle Park, NC 27711.
U.S. EPA. November 1985. Practical Guide - Trial Burns for Hazardous Waste
Incinerators . NTIS PB 86-190246. Office of Research and Development. Research
Triangle Park, NC 27711.
U.S. EPA. February 1985. Rapid Assessment of Exposure to Particulate Emissions
from Surface Contamination Sites . EPAI600/8-85/002. NTIS PB 85-1922 19. Office
of Health and Environmental Assessment. Washington, D.C. 20460.
U.S. EPA. February 1985. Modified Method STrain and Source Assessment
Sampling System Operators Manual . EPA.600/8-85-003. NTIS PB 85-169878.
Office of Research and Development. Research Triangle Park, NC 27711.
12-118
-------
U.S. EPA. 1985. Compilation of Air Pollutant Emissions Factors . EPA AP-42. NTIS PB
86-124906. Office of Air Quality Planning and Standards. Research Triangle
Park, NC 27711.
U.S. EPA. 1984: Evaluation and Selection of Models for Estimating Air Emissions
from Hazardous Waste Treatment 1 Storage 1 and Disposal Facilities . EPA- 450/3.
84-020. NTIS PB 85-156115. Office of Air Quality Planning and Standards.
Research Triangle Park, NC 27711.
U.S. EPA. September 1984. Network Design and Site Exposure Criteria
for Selected Noncriteria Air Pollutants . EPA-450/4-84-022. Office of Air Quality
Planning and Standards. Research Triangle Park, NC 27711.
U.S. EPA. June 1984. Evaluation of Air Emissionsfrom HazardousWaste
Treatment 1 Storage and Disposal Facilities . EPA 600/2-85/057. NTIS PB 85-
203792. Office of Research and Development. Cincinnati, OH 45268.
U.S. EPA. April 1984. Compendium of Methods forthe Determination of Toxic
Organic Compounds in Ambient Air . EPA-600/4-84-041. Office of Research and
Development. Research Triangle Park, NC 27711.
U.S. EPA. March 1984. Protocol for the Collection and Analysis of Volatile
POHCs Using yOST . EPA-600/8-84-007. NTIS PB 84-170042. Office of Research
and Development. Research Triangle Park, NC 27711.
U.S. EPA. February 1984. Sampling and Analysis Methods for Hazardous Waste
Combustion . EPA-60018•84-002. NTIS PB 84-155845. Washington. D.C. 20460.
U.S. EPA. September 1983. Characterization of Hazardous Waste Sites-
A Methods Manual: Volume II. Available Sampling Methods . EPA-600/4-83- 040.
NTIS PB 83-014799. Office of Solid Waste . Washington, D.C. 20460.
U.S. EPA. July 1983. Guidance Manual for Hazardous Waste Incinerator Permits .
EPA-OSW. NTIS PB84-100577. Office of Solid Waste. Washington. D.C. 20460.
12-1 19
-------
U.S. EPA. June 1983. Technical Assistance Document for Sampling and Analysis
of Toxic Organic Compounds in Ambient Air . EPA-600/4.83..027 NTIS PB
239020. Office of Research and Development. Research Triangle Park, NC
27711.
U.S. EPA. February 1983. Quality Assurance Handbook for Air Pollution
Measurement Systems: Volume IV, Meteorological Measurement . NTIS PB
25465818. February 1983. EPA-600-4 .82-060. Office of Research and
Development. Research Triangle Park, NC 27711.
U.S. EPA. November 1980. Ambient Monitoring Guidelines for Prevention of
Significant Deterioration (PSD) . EPA45014 -80•012. NTIS PB 81-153231. Office of
Air Quality Planning and Standards, Research Triangle Park, NC 27711.
U.S. EPA. 1978. Stack Sampling Technical Information. A Collection of
Monographs and Papers, Volumes I-Ill . EPA-450/2-78-042a,b,c. NTIS PB 80-
161672, 80-161680, 80-161698.
U.S. EPA. October 1977. Guidelines for Air Quality Maintenance Planning and
Analysis. Volume 10 (Revised): Procedures•for Evaluating Air Quality Impact of
New Stationary Sources . EPA 450/4-77.001. NTIS PB 274087/661. Office of Air
Quality Planning and Standards. Research Triangle Park, NC 27711.
U.S. EPA. Code of Federal ReQulations. 40 CFR Part 60: Appendix A:
Reference Methods . Office of the Federal Register. Washington, D.C. 20410.
U.S. EPA. 1981. Source Sampling and Analysis of Gaseous Pollutants .
EPA-APTI Course Manual 468. Air Pollution Control Institute. Research Triangle
Parlc,NC 27711.
U.S. EPA. 1979. Source Sampling for Particulate Pollutants . EPA-APTI Course
Manual 450. NTIS PB 80-182439, 80•174360. Air Pollution Control Institute.
Research Triangle Park, NC 27711.
12-120
-------
SECTiON 13
SURFACE WATER
13.1 Overview
The objective of an investigation of a release to surface water is to characterize
the nature, extent, and rate of migration of the release to this medium. This section
provides the following:
I An overall strategy for characterizing releases to the surface water system
(e.g., water column, bottom sediments, and biota), which includes
characterization of the source and the environmental setting of the
release, and conducting a monitoring program that will characterize the
release;
o A discussion of waste and unit source characteristics and operative release
mechanisms;
o A strategy for the design and conduct of monitoring programs considering
specific requirements of different wastes, release characteristics, and
receiving water bodies;
o Recommendations for data organization and presentation;
o Appropriate field and other methods that may be used in the
investigation; and
o A checklist of information that may be needed for release characterization.
The exact type and amount of information required for sufficient release
characterization will be facility and site-specific and should be determined through
interactions between the regulatory agency and the facility owner or operator
during the RFI process. This guidance does not define the specific data needed in all
13-1
-------
instances; however, it identifies the information that is likely to be needed tn
perform release characterizations and identifies methods for obtaining this’
information. The’RFI Checklist, presented at the end of this section, provides a tool
for planning and tracking information collection for release characterization. This
list is not a list of requirements for all releases to surface water. Some releases will
involve the collection of only a subset of the items listed, while others will involve
the collection of additional data.
Case Study Numbers 10, 11, 12 and 29 in Volume IV (Case Study Examples)
illustrate various aspects of surface water investigations which are described below.
13.2 Approach for Characterizing Releases to Surface Water
13.2.1 General Approach
The general approach recommended for characterization of releases to surface
waters consists of a series of steps summarized in Table 13-1. These steps outline a
phased approach, beginning with evaluation of existing data and proceeding to
design and implementation of a monitoring program, revised over time, as
necessary, based on findings of the previous phase. Each of these steps is discussed
briefly below.
The first step in the general approach is the collection and review of available
information on the contaminant source and the environmental setting. Some
information on the contaminant source will be available from several reports and
other documents. The RCRA Permit, Compliance Order, or RFA report will provide a
summary of information regarding actual or suspected releases from the various
units. The facility owner or operator should be familiar with this information as a
basis for further characterization of the release(s) in the RFI. In addition, thorough
understanding of the environmental setting is essential to an adequate
determination of the nature and extent of releases to surface waters. Monitoring
data should also be reviewed focusing on the quality of the data. If the quality
is determined to be acceptable, then the data may be used in the design of
the monitoring program. Guidance on obtaining and evaluating the necessary
13-2
-------
Table 13-1
Recommended Strategy for Characterizing Releases to Surface Water
INITIAL PHASE
Collect and review preliminary information for use in formulating monitoring
procedures.
- Waste and unit characteristics
- Surface water characteristics
- Actual or suspected release characteristics
2. Identify additional information necessary to characterize release
- Release location, frequency and form
- Surface water characteristics (e.g., stream discharge, lake stratification)
- Inter-media transport
- Conceptual model of release
3. Develop monitoring procedures
- Determine monitoring program objectives
- Select monitoring constituents and indicator parameters
- Select monitoring locations
- Determine monitoring frequency
- Incorporate hydrologic monitoring as necessary
- Determine role of biomonitoring and sediment monitoring
4. Conduct initial monitoring phase
- Collect samples under initial monitoring phase procedures and complete
field analyses
- Analyze samples for selected parameters and constituents
5. Collect, evaluate, and report results
- Compare analytical and other monitoring procedure results to health and
environmental criteria and identify and respond to emergency situations
and identify priority situations that may warrant interim corrective
measures- Notify regulatory agency
- Determine completeness and adequacy of collected data
• Summarize and present data in appropriate format
- Determine if monitoring program objectives were met
• Determine if monitoring locations, constituents and frequency were
adequate to characterize release (nature, extent, and rate)
• Report results to regulatory agency
13-3
-------
Table 13-1 (continued)
Recommended Strategy for Characterizing Releases to Surface Water
SUBSEQUENT PHASES (If necessary)
Identify additional information necessary to characterize release
- Identify additional information needs
- Determine need to include or expand hydrologic, and sediment and bio-
mon itonng
- Evaluate potential role of inter-media transport
2. Expand initial monitoring as necessary
- Relocate, decrease or increase number of monitoring locations
- Add or delete constituents and parameters of concern
• Increase or decrease monitoring frequency
• Delete, expand, or include hydrologic, sedimentor bio-monitoring
3. Conduct subsequent monitoring phases
• Collect samples under revised monitoring procedures and complete field
analyses
- Analyze samples for selected parameters and constituents
4. Collect, evaluate and report results/identify additional information necessary
to characterize release
• Compare analytical and other monitoring procedure results to health and
environmental criteria and identify and respond to emergency situations
and identify priority situations that may warrant interim corrective
measures- Notify regulatory agency
- Determine if monitoring program objectives were met
- Determine if monitoring locations, constituents, and frequency were
adequate to characterize release (nature, extent, and rate)
- Identify additional information needs
- Determine need to include or expand hydrologic, sediment, or bio-
monitoring
- Evaluate potential role of inter-media transport
- Report results to regulatory agency
* Surface water system is subject to inter-media transport. Monitoring program
should incorporate the necessary procedures to characterize the relationship, if
any, with ground water, sediment deposition, fugitive dust and other potential
release migration pathways.
13-4
-------
information on the contaminant source and the environmental setting is given in
Section 13.3.
During the initial investigation particular attention should be given to sampling
run-off from contaminated areas, leachate seeps and other similar sources of
surface water contamination, as these are the primary release pathways for surface
water.
Based on the collection and review of existing information, the design of the
monitoring program is the next major step in the general approach. The
monitoring program should include clear objectives, monitoring constituents and
indicator parameters, monitoring locations, frequency of monitoring, and
provisions for hydrologic monitoring. In addition to conventional water quality and
hydrologic monitoring, sediment monitoring and biomonitoring may also have a
role in the surface water evaluation for a given RFI. Guidance on the design of the
monitoring program is given in Section 13.4.
Implementation of the monitoring program is the next major step in the general
strategy for characterizing releases to surface water. The program should be
implemented in a phased manner that allows ‘for modifications to the program in
subsequent phases. For example, initial monitoring results may indicate that
downstream monitoring locations have been placed either too close to or too far
from the contaminant source to accurately define the complete extent of
downstream contamination. In this case, the program should be modified to
relocate monitoring stations for subsequent monitoring phases. Similarly, initial
monitoring may indicate that biomonitoring of aquatic organisms is needed in the
next phase. Guidance on methods that can be used in the implementation of the
program is given in Section 13.6.
Finally, the results of the characterization of releases to surface waters must be
evaluated and presented in conformance with the requirements of the RFI. Section
13.5 provides guidance on data presentation. Table 13-2 summarizes the
techniques and data-presentation methods for the key characterization tasks.
13-5
-------
3. Release Characterization
• Delineate Areal Extent
of Contamination
• Define Distribution
Between Sediment.
Biota and Water
Column
- Tables of Results, Contour
Maps, Maps of Sampling
Locations
• Graphs and Tables
• Determine Rate of
Migration
- Flow Monitoring
Graphs and Tables
- Describe Seasonal
Effects
- Repetitive Monitoring
- Graphs and Tables
TABLE 13-2
RELEASE CHARACTERIZATION TASKS FOR SURFACE WATER
Investigatory Tasks
Investigatory Techniques
1.
Waste/Unit
Characterization
- Waste Composition and
Analysis
•
See Section 13.3.1
-
Data Tables
• Unit or Facility
Operations
•
Review waste handling and
disposal practices and
schedules
-
Schematic diagrams of flow
paths, narrative
•
Review environmental
control strategies
- Release Mechanisms
.___________________________
•
See Section 13.3.1 Review
operational information
-
Site-specific diagrams,
maps, narrative
2.
Environmental Setting
Characterization
- Geographic Description
- Classification of Surface
Water and Receptors
-
-
Review topographic, soil
and geologic setting
information
See Section 13.3.3.1
•
-
Maps, Tables, Narrati
Maps, Cross Sections,
Narrative
- Define Hydrologic
Factors
-
See Section 13.3.3.1
•
Tables, Graphs, Map
• Sampling and Analysis
• Sampling and Analysis
13-6
-------
As monitoring data become ava able, both within and at the conclusion of
discrete investigation phases, they should be reported to the regulatory agency as
directed. The regulatory agency will compare the monitoring data to applicable
health and environmental criteria to determine the need for (1) interim corrective
measures; and (2) a Corrective Measures Study. In addition, the regulatory agency
will evaluate the monitoring data with respect to adequacy and completeness to
determine the need for any additional monitoring efforts. The health and
environmental c.nteria and a general discussion of how the regulatory agency will
apply them are supplied in Section 8. A flow diagram illustrating RFI decision points
is provided in Section 3 (See Figure 3-2).
Notwithstanding the above process, the owner or opeiator has a continuing
responsibility to identify and respond to emergency situations and to define priority
situations that may warrant interim corrective measures. For these situations, the
owner or operator is directed to obtain and follow the RCRA Contingency Plan
requirements under 40 CFR Part 264, Subpart D and Part 265, Subpart D.
13.2.2 Inter-media Transport
Surface waters are subject to inter-media transport, both as a receptor of
contamination and as a migration pathway. For example, surface waters are
generally engaged in a continual dynamic relationship with ground water. Ground
water may discharge to a surface water body that may, in turn, recharge an aquifer.
Hence, contamination may be transported from ground water to surface water and
from surface water to ground water. Release of contaminants from a receiving
water body to soil can also occur through deposition of the contaminants in
floodplain sediments. These sediments may be exposed to wind erosion and
become distributed through fugitive dust. Sediments may be exposed to air during
periods of low flow of water in streams and lakes and when sediments are
deposited by overland flow during rainfall-runoff events. Contaminants may also
enter the air from surface water through volatilization.
13-7
-------
13.3 Characterization of the Contaminant Source and Environmental Setting
The initial step in developing an effective monitoring program for a release to
surface waters is to investigate the unit(s) that is the subject of the RFI, the waste
within the unit(s), the constituents within the waste, the operative release
mechanisms and migration pathways to surface water bodies, and the surface water
receptors. From this information, a conceptual model of the release can be
developed for use in designing a monitoring program to characterize the release.
13.3.1 Waste Characterization
Knowledge of the general types of wastes involved is an important
consideration in the development of an effective monitoring program. The
chemical and physical properties of a waste and the waste constituents are major
factors in determining the likelihood that a substance will be released. These waste
properties may also be important initially in selecting monitoring constituents and
indicator parameters. Furthermore, once the wastes are released, these properties
play a major role in controlling the constituent’s migration through the
environment and its fate. Table 13-3 lists some of the significant properties in
evaluating environmental fate and transport In a surface water system. Without
data on the wastes, the investigator may have to implement a sampling program
involving many constituents to ensure that all potential constituents have been
addressed. General guidance on defining physical and chemical properties and
identifying possible monitoring constituents and indicator parameters is provided
in Sections 3 and 7.
Below are brief synopses of several of the key release, mobility, and fate
parameters summarized in Table 13-3. Figure 13.1 shows the qualitative
relationship between various environmental partitioning parameters. Neely and
Blau (1985) provide a good description of environmental partitioning effects of
constituents and application of partition coefficients.
13-8
-------
Table 13.3
— Important Waste and Constituent Properties
Affecting Fate and Transport in a Surface Water Environment
Bulk waste properties affecting mobilitya
‘ Physical state (solid, liquid, gas) of waste
o Chemical nature (e.g., aqueous vs non-aqueous) of waste
O Density (liquid)
o Viscosity (liquid)
o lnterfacial tension (with water and minerals) (liquid)
Properties to assess mobility of constituentsb
° Solubility
• Vapor pressure
• Henry’s law constant (or vapor pressure and water solubility)
• Bioconcentration factor
• Soil adsorption coefficient
• Diffusion coefficient (in air and water)
• Acid dissociation constant
• Octanol-water partition coefficient
• Activity coefficient
• Mass transfer coefficients (and/or rate constants) for intermedia transfer
• Boiling point
• Melting point
Properties to assess persistencec
• Rate of biodegradation (aerobic and anaerobic)
• Rate of hydrolysis
• Rate of oxidation or reduction
• Rate of photolysis
a These waste properties will be important when it is known or suspected that the
waste itself has migrated into the environment, e.g., due to a spill.
b These properties are important in assessing the mobility of constituents present
in low concentrations in the environ ment.
c For these properties, it is generally important to know (1) the effects of key
parameters on the rate constants (e g., temperature, concentration, pH) and (2)
the identity of the reaction products.
Sources of values for these and other parameters include Mabey. Smith, and Podall,
(1982), and Callahan, et al. (1979). Parameter estimation methods are described by
Lyman, Riehl , and Rosenblatt, (1982), and Neely and Blau (1985).
13-9
-------
S
Kow
FIGURE 13-1
QUAUTAUVE RELATIONSHIP SE1WEEN VARIOUS PARTITIONING PARAMETERS
uaanosiwater partition coefficient
Sioconcentration factor
SoiI!sediment adsorption coefficient
S
BCF Koc
Kow
Koc Koc
S
Kow
Kow
BCF
Solubilhty
S:
Kow:
S d:
Koc:
-------
• Physical State:
Solid wastes would appear to be less susceptible to release and migration
than liquids. However, processes such as dissolution (i.e., as a result of
leaching or runoff), and physical transport of waste particulates can act as
significant release mechanisms.
• Water Solubility:
Solubility is an important factor affecting a constituent’s release and
subsequent migration and fate in the surface water environment. Highly
soluble contaminants (e.g., methanol at 4.4 x 106 mg/L. at 77°F) are easily
and quickly distributed within the hydrologic cycle. These contaminants
tend to have relatively low adsorption coefficients for soils and sediments
and relatively low bioconcentration factors in aquatic life. An example of a
less soluble constituent is tetrachloroethylene at 100 mg/L at 77°F.
• Henry’s Law Constant:
Henry’s Law Constant indicates the relative tendency of a constituent to
volatilize from aqueous solution to the atmosphere based on the
competition between its vapor pressure and water solubility. Contaminants
with low Henry’s Law Constant values (e.g., methanol, 1.10 x 10-6 atm-
m 3 /mole at 77°F) will tend to favor the aqueous phase and volatilize to the
atmosphere more slowly than constituents with high values (e.g., carbon
tetrachloride, 2.3 x 102 atm-m 3 /mole at 77°F). This parameter is important
in determining the potential for intermedia transport to the air media.
• Octanol’Water Partition Coefficient (Kow):
The octanol/water partition coefficient (K ,) is defined as the ratio of an
organic constituent’s concentration in the octanol phase (organic) to its
concentration in the aqueous phase in a two-phase octanol/water system.
Values of K carry no units. K can be used to predict the magnitude of
an organic constituent’s tendency to partition between the aqueous and
organic phases of a two phase system such as surface water and aquatic
13-11
-------
organisms. The higher the value of Kow, the greater the tendency of a
organic constituent to adsorb to soil or waste matrices containing
appreciible organic carbon or to accumulate in biota. Generally,
constituents with K , values greater than or equal to 2.3 are considered
potentially bioaccumulative (Veith et al, 1980).
• Soil-Water Partition Coefficient (Kd):
The mobility of contaminants in soil depends not only on properties related
to the physical structure of the soil, but also on the extent to which the soil
material will retain, or adsorb, the hazardous constituents. The extent to
which a constituent is adsorbed depends on chemical properties of the
constituent and of the soil. Therefore, the sorptive capacity must be
determined with reference to a particular constituent and soil pair. The
soil-water partition coefficient (Kd) is generally used to quantify soil
sorption. Kd is the ratio of the adsorbed contaminant concentration to the
dissolved concentration, at equilibrium.
• Bioconcentratjor, Factor (BCF):
The bioconcentration factor is the ratio of the concentration of the
constituent in an organism or whole body (e.g., a fish) or specific tissue
(e.g., fat) to the concentration in water. Ranges of BCFs for various
constituents and organisms are reported in the literature (Callahan, et al. ,
1979) and these values can be used to predict the potential for
bioaccumulation, and therefore to determine whether sampling of the
biota may be necessary. Constituents exhibiting a BCF greater than 1.0 are
potentially bioaccumulative. Generally, constituents exhibiting a BCF
greater than 100 cause the greatest concern.
• The Organic Carbon Adsorption Coefficient (Ku):
The extent to which an organic constituent partitions between the solid
and solution phases of a saturated or unsaturated soil, or between runoff
water and sediment, is determined by the physical and chemical properties
of both the constituent and the soil (or sediment). The tendency of a
constituent to be adsorbed to soil is dependent on its properties and on the.
organic carbon content of the soil or sediment. Koc is the ratio of th
13-12
-------
amount of constituent adsorbed per unit weight of organic carbon in the
soil or sediment to the concentration of the constituent in aqueous
solution-at equilibrium. K 0 c can be used to determine the partitioning of a
constituent between the water column and the sediment. When
constituents have a high K , they have a tendency to partition to the soil
or sediment. In such cases, sediment sampling would be appropriate.
• Other Equilibrium Constants:
Equilibrium constants are important predictors of a compound’s chemical
state in solution. In general, a copstituent which is dissociated (ionized) in
solution will be more soluble and therefore more likely to be released to
the environment and more likely to migrate in a surface water body. Many
inorganic constituents, such as heavy metals and mineral acids, can occur as
different ionized species depending on pH. Organic acids, such as the
phenolic compounds, exhibit similar behavior. It should also be noted that
ionic metallic species present in the release may have a tendency to bind to
particulate matter, if present in a surface water body, and settle Out to the
sediment over time and distance. Metallic species also generally exhibit
bioaccumulative properties. When metallic species are present in a release.
both sediment and biota sampling would be appropriate.
• Biodegradation:
Biodegradation results from the enzyme-catalyzed transformation of
organic constituents, primarily from microorganisms. The ultimate fate of
a constituent introduced into a surface water or other environmental
system (e.g.. soil), could be a constituent or compound other than the
species originally released. Biodegradation potential should therefore be
considered in designing monitoring programs. Section 9.3 (Soils) presents
additional information on biodegradation.
• Photolysis:
Photodegradation or photolysis of constituents dissolved in aquatic systems
can also occur. Similar to biodegradation. photolysis may cause the
ultimate fate of a constituent introduced into a surface water or other
environmental system (e.g., soil) to be different from the constituent
13-13
-------
originally released. Hence, photodegradatian potential should also be
considered in designing sampling and analysis programs.
• Chemical Degradation (Hydrolysis and Oxidation/Reduction):
Similar to photodegradation and biodegradation, chemical degradation,
primarily through hydrolysis and oxidation/reduction (REDOX) reactions,
can also act to change constituent species once they are introduced to the
environment. Hydrolysis of organic compounds usually results in the
introduction of a hydroxyl group (-OH) into a constituent structure.
Hydrated metal ions, particularly those with a valence of 3 or more, tend to
form ions in aqueous solution, thereby enhancing species solubility. Mabey
and Mill (1978) provide a critical review of the hydrolysis of organic
compounds in water under environmental conditions. Stumm and Morgan
(1982) discuss the hydrolysis of metals in aqueous systems. Oxidation may
occur as a result of oxidants being formed during photochemical processes
in natural waters. Similarly, in some surface water environments (primarily
those with low oxygen levels) reduction of constituents may take place.
Degradation, whether biological, physical or chemical, is often reported in the
literature as a half-life, which is usually measured in days. It is usually expressed as
the time it takes for one half of a given quantity of a compound to be degraded.
Long half-lives (e.g., greater than a month or a year) are characteristic of persistent
constituents. It should be noted that actual half-life can vary significantly over
reported values based on site-specific conditions. For example, the absence of
certain microorganisms at a site, or the number of microorganisms 1 can influence
the rate of biodegradation, and therefore, half-life. As such, half-life values should
be used only as general indications of a chemical’s persistence.
In addition to the above, reactions between constituents present in a release
may also occur. The owner or operator should be aware of potential
transformation processes, based on the constituents’ physical, chemical and
biological properties, and account for such transformations in the design of
monitoring procedures and in the selection of analytical methods.
13-14
-------
Table 13.4 provides an application of the concepts discussed above in assessing
the behavior of waste material with respect to release, migration, and fate. The
table gives gener.al qualitative descriptors of the significance of some of the more
important properties and environmental processes for the major classes of organic
compounds likely to be encountered.
Table 13-4 can be used to illustrate several important relationships.
• Generally, water solubility varies inversely with sorption, bioconcentration,
and to a lesser extent, volatilization.
• Oxidation is a significant fate process for some classes of constituents which
can volatilize from the aqueous phase.
• Variations in properties and environmental processes occur within classes
as indicated by the pesticides, monocyclic aromatics, polycyclic aromatics,
and the nitrosamines and other nitrogen-containing compounds.
Characterizing the environmental processes and properties of inorganic waste
constituents takes a similar approach to that.shown on Table 13-4 for organics.
However, characterizing the metals on a class-by-class basis is not advisable because
of the complex nature of each metal and the many species in which the metals
generally occur. The interaction of each metal species with the surface water
environment is generally a function of many parameters including pH, REDOX
potential, and ionic strength. See Stumm and Morgan (1982) for additional
discussions on this subject. Generally, however, when metal species are present in a
release, it is advisable to monitor the sediment and biota, in addition to the water
column. This is due to likely deposition of metals as particulate matter, and to
potential bioaccumulation.
13.3.2 Unit Characterization
The relationship between unit characteristics and migration pathways provides
the framework in this section for a general discussion of release mechanisms from
units of concern to surface waters.
13-15
-------
TABLE 13-4
GENERAL SIGNIFICANCE OF PROPERTIES AND ENVIRONMENTAL PROCESSES FOR
CLASSES OF ORGANIC CHEMICALS UNDER ENVIRONMENTAL CONDITIONS
ChmacslCl
Soiubditp
Sorption
Biocon.ntration
Volatshzatson
Photolyiii
Oaidation
Hrdrol),sn
Pest iudes
Organochlonns
Oganoiospliot. s
Carbamat.s
Low
Moderate
Moderat.
High
Moderate
Moderate
High
Low
Moderate
High
Low
Low
Moder a le
High
Moderate
Low
High
Moderate
Low
Moderate-High
Moderate
Polychkw.nal.d B.pl*nyls
Low
High
High
Moderate
Low
Low
Halogenated Aliphatits
Moderate
Low
Low
High
Low
Haioqenatcd £thrs
High
Low
Low
Low
Low
H.gh
High
Low
Monocycig A104fljti($
To luene
Phenol
Moderate
High
Moderate
Low
Low
-Low
High
Low-Moderate
Low
Moderate
Hiyh
Moderate
Low
Low
Phthaiat.fs(en
Low
High
High
tow
Low
Low
Low
Polycydic Aroinotics
Naphthalene
Benzo(K)fluo, anthene
Moderate
Low
High
High
Low
tow
Moderate
Low
High •
H igh
Low
tow
Low
Low
Nit rosamines and other Nitrogen -
Containing Compounds
Benzeduie
Dl-n-piopylnitrosam,n .
Moderate-High
High
High
Low
Low
Low
Low
Low
High
High
High
Low
Low
Atmospheric oxidation (volatile organic chemicals).
‘ Dissolved portion only
Table entries are qualitative only and based on a typical chemical within the class
Variations are observed within each class
-------
13.3.2.1 UnitCharacteristics
Information on design and operating characteristics of a unit can be helpful in
characterizing a release. Unsound unit design and operating practices can allow
waste to mugr te from a unit and possibly mix with runoff. Examples include
surface impoundments with insufficient freeboard, allowing for periodic
overtopping; leaking tanks or containers; or land-based units above shallow, low-
permeability materials which, if not properly designed and operated, can fill with
water and spill over. In addition, precipitation falling on exposed wastes can
dissolve and thereby mobilize hazardous constituents. For example, at uncapped
active or inactive waste piles and landfills, precipitation and leachate are likely to
mix at the toe of the active face or the low point of the trench floor. Runoff may
then flow into surface water through drainage pathways.
13.3.2.2 Frequency of Release
Releases to surface waters may be intermittent, continuous, or a past occurrence.
It is important to consider the anticipated frequency of a release to establish an
effective monitoring program.
Most of direct releases to surface waters are intermittent. Intermittent
discharges may be periodic, but may occur more often in a non-periodic manner, for
example, in response to rainfall runoff. Other common factors affecting
intermittent releases include fluctuations in water levels and flow rates, seasonal
conditions (e.g., snow melt), factors affecting mass stability (e.g., waste pile mass
migration), basin configuration, quantity/quality of vegetation, engineering control
practices, integrity of the unit, and process activities.
Erosion of contaminated materials from a unit (e.g., a landfill) is generally
intermittent, and is generally associated with rainfall-runoff events. Similarly.
breaches in a dike are generally short-term occurrences when they are quickly
corrected following discovery. Leaks, while still predominantly intermittent in
nature, may occur over longer spans of time and are dependent on the rate of
release and the quantity of material available.
13-17
-------
Direct placement of wastes within surface waters (e.g., due to movement of an
unstable waste pi e) has the potential to continuously contribute waste constituent!
until the wastes have been removed or the waste constituents exhausted. Direct
placement is usually easily documented by physical presence of wastes within the
surface water body.
The frequency of sample collection should be considered in the design of the
monitoring program. For example, intermittent releases not associated with
rainfall runoff may require more frequent or even Continuous sample collection to
obtain representative data on the receiving water body. Continuous monitoring is
generally feasible only for the limited number of constituents and indicator
parameters for which reliable automatic sampling/recording equipment is available.
Intermittent releases that are associated with rainfall runoff may requite event
sample collection. With event sampling, water level or flow-activated automatic
sampling/recording equipment can be used. For Continuous releases, less frequent
sample collection is generally adequate to obtain representative data on the
receiving water body.
Previous intermittent releases may be identified through the analysis of bottom
sediments, and whole body or tissue analyses of relatively sessile and long-lived
macroanvertebrates (e.g., clams), or other species, such as fish. These analyses may
identify constituents that may have adsorbed onto particulates and settled to the
sediment, as well as bioaccumulative contaminants. In addition, intermittent
releases may be detected through the use of bioassays. Using these
procedures, the test specie(s) is held within the effluent or stream flow and
periodically checked for survival and condition.
13.3.2.3 Form of Release
Releases to surface waters may be generally categorized as point sources or non-
point sources. Point sources are those that enter the receiving water at a definable
location, such as piped discharges. Non-point source discharges are all other
discharges, and generally cover large areas.
13-18
-------
In general, most unit releases to surface waters are likely to be of a point source
nature. Most spills, leaks, seeps, overtopping episodes, and breaches occur within
an area which cen be easily defined. Even erosion of contaminated soil and
subsequent deposition to surface water can usually be identified in terms of point
of introduction to the surface water body, through the use of information on
drainage patterns, for example. However, the owner or operator should be aware
of the potential for both point and non-point sources, as monitoring programs
designed to characterize these types of releases can be different. For example, the
generally larger and sometimes unknown areal extent of non-point source
discharges may require an increase in the number of monitoring locations from that
routinely required for point source discharges. The number of monitoring locations
must be carefully chosen to ensure representative monitoring results.
13.3.3 Characterization of the Environmental Setting
The environmental setting includes the surface water bodies and the physical
and biological environment. This section provides a general classification scheme
for surface waters and discusses collection of hydrologic data that may be important
in their characterization. Collection of specific geographical and climatological
data are also discussed. Characterization of the biotic environment is treated in
Section 13.4.
Note that some States have classified surface waters under investigations
pursuant to Clean Water Act goals (e.g., Class A, B, etc.). These classifications deal
primarily with the present quality of the surface water and use(s) of the surface
water (e.g., drinking, recreation). If applicable, the owner or operator should
report such ciassifications.
13.3.3.1 Characterization of Surface Waters
Surface waters can be classified into one of the following categories. These are
obviously not pure classifications; intergrades are common.
I Streams and Rivers;
13-19
-------
• Lakes and Impoundments;
• Wetlan&; and
• Marine Environments.
13.3.3.1.1 Streams and Rivers
Streams and rivers are conduits of surface water flow having defined beds and
banks. The physical characteristics of streams and rivers greatly influence their
reaction to contaminant releases and natural purification (i.e., assimilative
capacity). An understanding of the nature of these influences is important to
effective planning and execution of a monitoring program. Important
characteristics include depth, velocity, turbulence, slope, changes in direction and in
cross sections, and the nature of the bottom.
The effects of some of these factors are so interrelated that it is difficult to assign
greater or lesser importance to them. For example, slope and roughness of the
channel influence depth and velocity of flow, which together control turbulence.
Turbulence, in turn, affects rates of contaminant dispersion, reaeration.
sedimentation, and rates of natural purification. The nature of contaminant
dispersion is especially critical in the location of monitoring stations. All these
factors may be of greater or lesser importance for specific sites. It should also be
noted that these factors may differ at the same site depending on when the release
occurred. For example, differences between winter and summer flow may greatly
influence the nature of contaminant dispersion.
Of further relevance to a surface water investigation are the distinctions
between ephemeral, intermittent, and perennial streams, defined as follows:
• Ephemeral streams are those that flow only in response to precipitation in
the immediate watershed orin response to snow melt. The channel bottom
of an ephemeral stream is always above the local water table.
13-20
-------
• Intermittent streams are those that usually drain watersheds of at least one
square mile and/or receive some of their flow from baseflow recharge from
ground water during at least part of the year, but do not flow continually.
• Perennial streams flow throughout the year in response to ground water
discharge and/or surface water runoff.
The distinction between ephemeral, intermittent and perennial streams will also
influence the selection of monitoring frequency, monitoring locations and possibly
other monitoring program design factors. For example, the frequency of
monitoring for ephemeral streams, and to a lesser extent intermittent streams, will
depend on rainfall runoff. For perennial-stream monitoring, the role of rainfall
runoff in monitoring frequency may be of less importance under similar release
situations.
The location of ephemeral and intermittent streams may not be apparent to the
owner or operator during periods of little or no precipitation. Generally,
intermittent and ephemeral streams may be associated with topographic
depressions in which surface water runoff is conveyed to receiving waters. In
addition to topography, a high density of vegetation in such areas may be an
indicator of the presence of ephemeral or intermittent drainage.
Perennial streams and rivers are continually engaged in a dynamic relationship
with ground water, either receiving ground water discharge (gaining stream) or
recharging the ground water (losing stream) over any given stream reach. These
characteristics should be considered in the evaluation of contaminant transport and
fate.
The Ecoloav of RunninQ Waters (Hynes 1970) and Introduction to Hydrology
(Viessman it al., 1977) may be reviewed for basic discussions of surface water
hydrology.
13-2 1
-------
13.3.3.1.2 Lakes and Impoundments
Lakes are typically considered natural, while impoundments may be man-made.
The source for lakes and impoundments may be either surface water or ground
water, or both. Impoundments may be either incised into the ground surface or
may be created via the placement of a dam or embankment. As with streams and
rivers, the physical characteristics of lakes and impoundments influence the
transport and fate of contaminant releases and therefore the design of the
monitoring program. The physical characteristics that should be evaluated include
dimensions (e.g., length, width, shoreline, and depth), temperature distribution,
and flow pathways.
Especially in the case of larger lakes and impoundments, flow paths are not
clearcut from inlet to outlet. Not only is the horizontal component of flow in
question, but as depth of the water body increases in the open water zone, chemical
and more commonly physical (i.e., temperature) phenomena create a vertical
stratification or zonation. Figure 13-2 provides a typical lake cross section, showing
the various zones of a stratified lake.
Because of stratification, deeper water bodies can be considered to be comprised
of three lakes. The upper lake, or epilimnion, is characterized by good light
penetration, higher levels of dissolved oxygen, greater overall mixing due to wave
action, and elevated biological activity. The lower lake, or hypolimnion, is the
opposite of the epilimnion. Lying between these is what has been termed the
middle lake or mesolimnion, characterized by a rapid decrease in temperature with
depth. Were it not for the phenomenon of lake overturn, or mixing, contaminants
with specific gravities greater than water might be confined to the lowermost lake
strata, where they might remain for some time. Due to the potential importance of
lake mixing to contaminant transport, it is discussed below.
Temperatures within the epilimnion are relatively uniform because of the mixing
that occurs there. Water is most dense at 40 Centigrade (C); above and below 4°C
its density decreases. In temperate climates, lake mixing is a seasonal occurrence.
As the surface of the epilimnion cools rapidly in the fall, it becomes denser than the
13-22
-------
‘I
ii
1• / .a
.c T;u . : i I g
j: •
-
• I • i • / •
..s-, /•• . —
/ .;_•‘ , ,1 / /
‘ ‘. / /
.e” P’;•-
I. S
FIgure 13.2. Typical Lake Cross Section (Source: Adapted From Cole. 1975).
13•23
. 1 )4 ’- ;‘l .. •, 4’.
.v e
• i-:- • ‘.
• .
• -
Epilimnion f: f’
Umnion F
HypoLiaflic
-------
underlying strata. At some point, the underlying strata can no longer support the
denser water and an overturn” occurs, resulting in lake mixing. A similar
phenomenon occjirs in the spring as the surface waters warm to 4°C and once again
become denser than the underlying waters.
Because of the influence of stratification on the transport of contaminants
within a lake or reservoir, the location of monitoring points will largely depend on
temperature stratification. The monitoring points on water bodies that are not
stratified will be more strongly influenced by horizontal flowpaths, shoreline
configuration and other factors. The presence of temperature stratification can be
determined by establishing temperature-depth profiles of the water body.
More information on lakes and impoundments may be found in the following
references:
A Treatise on LimnoloQy. Volumes I and II (Hutchinson, 1957, 1967) or
Textbook of Limnolopy (Cole, 1975)
13.3.3.1.3 Wetlands
Wetlands are those areas that are inundated or saturated by surface or ground
water at a frequency and duration sufficient to support, and that under normal
circumstances do support, a prevalence of vegetation typically adapted for life in
saturated soil conditions. Wetlands include, but are not limited to, swamps,
marshes, bogs, and similar areas.
Wetlands are generally recognized as one of the most productive and sensitive
of biological habitats, often associated with critical habitat for State or Federally
listed special-status species of plants or wildlife. Wetlands also may play a
significant role in basin hydrology, moderating peak surface water flows and
providing recharge to the ground water system. The definition of the extent and
sensitivity of wetlands that may be affected by a release is essential to release
characterization.
13-24
-------
High organic content, fine-grained sediments, slow surface water movement
and lush vegetative growth and biological activity contribute to a high potential for
wetlands to contentrate contaminants from releases. This is especially true for
bioaccumulative contaminants, such as heavy metals. Seasonal die-off of the
vegetation and flooding conditions within the basin may result in the wetlands
serving as a s3gnificant secondary source of contaminants to downstream surface
water receptors.
13.3.3.1.4 Marine Environments
For the purpose of this guidance, marine environments are restricted to
estuaries, intermediate between freshwater and saline, and ocean environments.
Industrial development near the mouths of rivers and near bays outletting directly
into the ocean is relatively widespread, and the estuarine environment may be a
common receptor of releases from industrial facilities.
Estuaries are influenced by both fresh water and the open ocean. They have
been functionally defined as tidal habitats that are partially enclosed by land but
have some access to the open sea, if only sporadically, and in which ocean water is
partially diluted by fresh water. Estuaries may also experience conditions where
salinities are temporarily driven above the ocean levels due to evaporative losses.
Because of the protection afforded by encircling land areas, estuaries are termed
“low-energy environments, indicating that wave energy and associated erosive
and mixing processes are reduced.
The physical characteristics of an estuary that will influence the design of a
monitoring program are similar to those considered for lakes and impoundments
(i.e., length, width, shoreline, depth, and flow pathways). However, the increased
probability for chemical stratification due to varying salinities may be most
pronounced in areas where freshwater streams and rivers discharge into the
estuary. The monitoring program design should also consider tidal influences on
stratification and contaminant dispersion.
In addition, estuaries, or some portions of estuaries, can be areas of intergrained
sediment deposition. These sediments may contain a significant organic fraction.
13-2 5
-------
which enhances the opportunity for metal/organic adsorption, and subsequen
bioaccumulatiori. Hence, biomonitoring within an estuary may also be appropriat ..
13.3.3.2 Climatic and Geographic Conditions
A release to the surface water system will be influenced by local
climatological/meteorological and geographic conditions. The release may be
associated only with specific seasonal conditions like spring thaws or meteorological
events such as storms. If the release is intermittent, the environmental conditions at
the time of the release may help identify the cause of and evaluate the extent of the
release. If the release is continuous seasonal variationsshould also be evaluated.
The local climatic conditions should be reviewed to determine:
• The annual precipitation distribution (monthly averages);
• Monthly temperature variations;
• Diurnal temperature range (daytime/nighttime difference);
• Storm frequency and severity;
• Wind direction and speed; and
• Snowfall and snow pack ranges (if applicable).
This information will be useful in developing a sampling schedule and in
selecting sampling methods. From these data, it should be possible to anticipate
the range of dimatic conditions at the site. These conditions may be far more
complex than simple cold/hot or wet/dry seasons. Some areas have two or more
TM wet seasons, one characterized by prolonged showers, another by brief intense
storms, and perhaps a third as a result of snowmelt. Cold/hot seasons may overlap
these wet/dry seasons to create several climatologically identifiable seasons. Each
season may affect the release differently and may require a separate
characterization. The unique climatological seasons that influence the site shoulc
13-26
-------
be identified. Typical winter. spring, su mer and fall seasonal descriptions may not
be appropriate or representative of the factors influencing the release. Sources of
climatological data are given in Section 12 (Air).
In additionto the climatologicallmeteorological factors, local geographic
conditions will influence the design of the sampling program. Topographic
conditions and soil structure may make some areas prone to flash floods and stream
velocities that are potentially damaging to sampling equipment. In other areas
(e.g., the coastal dune areas of the southeastern states), virtually no runoff occurs.
Soil porosity and vegetation are such that all precipitation either enters the ground
water or is lost to evapotranspiration. (See Section 9 (Soil) for more information).
A description of the geographic setting will aid in developing a sampling
program that is responsive to the particular conditions at the facility. When
combined with a detailed understanding of the climatological/meteorological
conditions in the area, a workable monitoring framework can be created.
13.3.4 Sources of Existing Information
Considerable information may already be available to assist in characterizing a
release. Existing information should be reviewed to avoid duplication of previous
efforts and to aid in focusing the RFI. Any information relating to releases from the
unit, and to hydrogeological, meteorological, and environmental factors that could
influence the persistence, transport or location of contaminants should be
reviewed. This information may aid in:
• Delineating the boundaries of the sampling area;
• Choosing sampling and analytical techniques; and
• Identifying information needs for later phases of the investigation.
Information may be obtained from readily available sources of geological and
meteorological data, waste characteristics, and facility operations records. (See also
Sections 2, 3,7 and Appendix A).
13-27
-------
13.4 Design of a Monitoring Program
Following characterization of the contaminant source and environmental
setting, a monitoring program is developed. This section outlines and describes
factors that should be considered in design of an effective surface water monitoring
program. The characterization of contaminant releases may take place in multiple
phases. While the factors discussed in this section should be carefully considered in
program design, each of these genetic approaches may require modification for
specific situations.
The primary considerations in designing a surface water monitoring program
are:
• Establishing the objectives of the monitoring program;
• Determining the constituents of concern;
• Establishing the hydrologic characteristics of the receiving water and
characteristics of the sediment and biota, if appropriate;
• Selecting constituents and/or indicators for monitoring;
• Selecting monitoring locations and monitoring frequency; and
• Determining the need for sediment monitoring and, hydrologic and
biomonitoring.
13.4.1 Objictlves of the Monitoring Program
The principal objectives of a monitoring program are to:
• Identify the characteristics of releases (e.g., continuous vs intermittent);
• Identify the fate of constituents
13-28
-------
• Identify the nature, rate, and extent of the release and actual or potential
effects o water quality and biota; and
• Identify the effect of temporal variation on constituent fate and identify
impacts on water quality and biota.
Periodic monitoring of the surface water system is often the only effective means
of identifying the occurrence of releases and their specific effects. Releases can be
continuous or intermittent, point source, or non-point source. The concept of
monitoring is the same, regardless of the frequency or form of the release. A series
of measurements, taken over time, better approximate the actual release to surface
waters than a one-time grab sample.
The functional difference between monitoring the various types of discharges is
the point of measurement. Point source discharges may be monitored at and/or
near the discharge point to surface waters. The fate and potential effects of non-
point source discharges should be inferred through measurement of the presence of
constituents of concern or suitable indicators of water quality within the receiving
water body.
The monitoring program should also establish the background condition against
which to measure variations in a continuous release or the occurrence of an
intermittent release. Such information will enable the facility owner or operator to
compile data that will establish trends in releases from a given unit(s) as well as to
identify releases from other sources.
Monitoring programs should characterize contaminant releases as a function of
time. Clim.tologic factors such as frequency of intense rainfall, added effects of
snowmelt, temperature extremes, and mixing in lakes and estuaries should be
evaluated and quantified as causative agents for intermittent contaminant release.
Important concepts to consider in designing the monitoring program for surface
water to help meet the above-stated objectives are described below.
13-29
-------
13.4.1.1 Phased Characterization
The initial ph’ese of a surface water release characterization program may be
directed toward verification of the occurrence of a release identified as ususpectedu
by the regulatory agency. It may also serve as the first step for characterizing
surface water systems and releases to those systems in cases where a release has
already been verified.
The initial characterization will typically be a short-duration activity, done in
concert with evaluation of other media that may either transport contaminants to
surface waters, or may themselves be affected by discharges from surface waters
(i.e., inter-media transport). It may be particularly difficult to define intermittent
discharges in the initial characterization effort, especially if the contaminants from
these releases are transient in the surface water body.
If the waste characterization is adequate, the initial characterization phase may
rely upon monitoring constituents and suitable indicator parameters to aid in
defining the nature, rate, and extent of a release. Subsequent phases of release
characterization will normally take the form of an expanded environmental
monitoring program and hydrologic evaluation, sensitive to seasonal variations in
contaminant release and loading to the receiving water bodies, as well as to natural
variation in hydrologic characteristic (e.g., flow velocity and volume, stream cross
section).
13.4.1.2 Development of Conceptual Model
To effectively design a monitoring program, it is important to develop a
conceptual model or understanding of the fate of constituents of the release in the
receiving watir body. This conceptual understanding will assist in answering the
following questions.
I What portion of the receiving water body will be affected by the release
and what conditions (e.g., low flow, immediate stormwatet runoff)
represent reasonable worst case conditions under which sampling should
occur
13-30
-------
• What should the relative concentrations of contaminants be at specific
receptor-points within the water body (e.g., public water supply intakes
downstream of a site)?
• How does the release of concern relate to background contamination in
the receiving water body as a result of other discharges?
• How might the monitoring program be optimized, based on contaminant
dispersion and relative concentrations within the receiving water body?
The fate of waste constituents entering surface waters is highly dependent on
the hydrologic characteristics of the various classifications of water bodies, (i.e.,
streams and rivers, lakes and impoundments, wetlands, and estuaries, as discussed
earlier). Because of their complexity, methods for characterization of contaminant
fate in wetlands and estuaries is not presented in detail in this guidance. The reader
is referred to Mills (1985) for further detail on characterizing contaminant fate in
wetlands and estuaries.
13.4.1.3 Contaminant Concentration vs Contaminant Loading
Concentration and loading are different means of expressing contaminant levels
in a release or receiving water body. The concept is important in the selection of
constituents for monitoring. Both concentration and loading should be evaluated
with respect to the release and the receiving waters. Basing an evaluation solely on
concentration may obscure the actual events. In addition, it is essential to quantify
individual sources of contaminants and the relationships between media, as well as
the loading found in the receiving water body, to effectively define the nature and
extent of th. contaminant release.
Contaminant concentrations in receiving waters have specific value in
interpreting the level of health or environmental effects anticipated from the
release. Contaminant loading provides a common denominator for comparison of
contaminant inputs between monitoring points. In addition, especially in the case
of contaminants that are persistent in sediments (e.g., heavy metals), loadings are a
13-31
-------
convenient means of expressing ongoing contributions from a Specific discharge.
The distinction between concentration and loading is best drawn through th,
following example.
A sample cpllected from a stream just upgradient of a site boundary (Station A)
has a concentration of 50 micrograms per liter (ugh) of chromium. A second sample
collected just downstream of the site (Station B) has a chromium concentration of
45 ugh. From these data it appears that the site is not releasing additional
chromium to the stream. If, however, the stream flow is increasing between these
two sampling locations, a different interpretation is apparent. If the stream flow at
the upstream location is 1,000 gallons per minute (gpm) and the downstream
location is 1,300 gpm, the actual loading of chromium to the stream at the two
locations is as follows:
Station A
Chromium (50.0 ug/l)(1 ,000 gal/min)(1o.9 kg/ug)(6o min/hr)(3.785 I/gal) s 0.0114
kgTh r
Station B
Chromium = (45.0 ugil)(1300 gal/min)(1o-9 kg/ug)(60 minThr)(3.785 I/gal) • 0.0133
kg/hr
It is now apparent that somewhere between the two sampling stations is a
source(s) contributing o.ooig kg/hr of chromium. If all of the flow difference (i.e.,
300 gpm) is from a single source, then this source would have a chromium
concentration of 27.9 ugh:
Chromium • [ (0.0019 kg/hr)(109 ug/kg)(lhr/6omin)(1 min/300 gal)(1 ga l/3.785 l)J
27.9 ugh
If, however, 90 percent of this flow difference (i.e., 270 gpm) was due to
groundwater discharge with a chromium concentration below detectable limits and
the remaining 10 percent (i.e., 30 gpm) was the result of a direct discharge from the
facility, this discharge could have a chromium concentration of 279 ugh.
13-32
-------
13.4.1.4 Contaminant Dispersion Concepts
Contaminant ispersiofl concepts and models of Constituent fate can be used to
define constituents to be monitored and the location and frequency of monitoring.
Dispersion may occur in streams, stratified lakes or reservoirs, and in estuaries.
Dispersion may be continuous, seasonal, daily, or a combination of these.
The discussion below is based on information in the Draft Superfund Exposure
Assessment Manual (EPA, 1986) relative to simplified models useful in surface water
fate analyses. The reader is directed to that document for a more in.depth
discussion of models. The equations presented below are based on the mixing zone
concept originally developed for EPA’s National Pollutant.Discharge Elimination
System (NPDES) under the Clean Water Act. To avoid confusion over regulatory
application of these cancepts in the NPDES program, and the approach presented
below (basically to aid in the development of a monitoring program), the following
discussion refers to use of the Dispersion Zone.
The following equation provides an approximate estimate of the concentration
of a substance downstream from a point source release, after dilution in the water
body:
Cr + C Q
where:
C • downstream concentration of substance following complete
dispersion (mass/volume)
C • upstream concentration of substance before effluent release point
(mass/volume)
• concentration of substance in effluent (mass/volume)
= effluent flow rate (volume/time)
Qu upstream flow rate before effluent release point (volume/time)
13•33
-------
The following equation may be used to estimate instream concentrations after
dilution in situations where waste constituents are introduced via inter-media
transfer or from a non-point source, or where the release rate is known in terms of
mass per unit time, rather than per unit effluent volume:
C a Tr+Mu
where:
a inter-media transfer rate (mass/time)
M a upstream mass discharge rate (mass/time)
Qt a stream flow rate after inter-media transfer or non-point source release
(volume/time)
The above equations assume the following:
• Dispersion is instantaneous and complete;
• The waste constituent is conserved (i.e., all decay or removal processes are
disregarded); and
• Streamflow and rate of contaminant release to the stream are constant
(i.e., steady-state conditions).
For a certain area downstream of the point, of release the assumption of
complete dispersion may not be valid. Under certain situations, the dispersion zone
can extend downstream for a considerable distance, and concentrations can be
considerably higher within the dispersion zone than those estimated by the
equation. The length of this zone can be approximated by the following equation:
DZ • 0.4 w 2 u
13-34
-------
where:
DZ — dispersion zone length (length units)
w a width of the water body (length units)
u stream velocity (length/time)
d stream depth (length units)
S a slope (gradient) of the stream channel (length/length)
g a acceleration due to gravity (32 ft/sec2)
Within the dispersion zone, contaminant concentrations will show spatial
variation. Near the release point the contaminant will be restricted (for a discharge
along one shoreline) to the nearshore area and (depending on the way the
discharge is introduced and its density) can be vertically confined. As the water
moves downstream, the contaminant will disperse within surrounding ambient
water and the plume will widen and deepen. Concentrations will generally
decrease along the plume centerline and the concentration gradients away from
the centerline will decrease. Eventually, as described above, the contaminant will
become fully dispersed within the stream; downstream from this point
concentration will be constant throughout the stream cross-section, assuming that
the stream flew rate remains constant.
It is important to understand this concentration variability within the dispersion
zone if measurements are to be made near the release. Relatively straightforward
analytical expressions (See Neely, 1982) are available to calculate the spatial
variation of concentration as a function of such parameters as stream width, depth,
velocity, and dispersion coefficients. Dispersion coefficients characterize the
dispersion between the stream water and contaminated influx; they can, in turn, be
estimated from stream characteristics such as depth, gradient, and path (i.e..
straight or bends).
The above considerations are for instream concentrations resulting from the
releases of concern. If total instream concentrations are required, the
concentrations determined from background water samples should also be
considered. In addition, if introduction of the contaminant occurs over a fixed
13-3 5
-------
stream reach, as might be the case with a non-point discharge, it should be assumed
that the dispersion zone begins at the furthest downstream point within this reach.
13.4.1.5 Conservative vs Non-Conservative Species
The expressions presented thus far have assumed that the contaminant(s) of
concern is conservative (i.e., that the mass loading of the contaminant is affected
only by the mechanical process of dilution). For contaminants that are non-
conservative. the above equations would provide a conservative estimate of
contaminant loading at the point of interest within the receiv ng water body.
In cases where the concentration after dilution of a non -conservative substance
is still expected to be above a level of concern, it may be useful to estimate the
distance downstream where the concentration will remain above this level and at
selected points in between. The reader is referred to the Draft SuDerfund Exposure
Assessment Manual (EPA, 1986. Section 4.3.2), for details regarding this estimation
procedure.
13.4.2 Monitoring Constituents and Indicator Parameters
13.4.2.1 Hazardous Constituents
The facility owner or operator should propose a list of constituents and indicator
parameters, if appropriate, to be included in the Surface Water investigation. This
list should be based on a site-specific understanding of the composition of the
release source(s) and the operative release mechanisms, as well as the physical and
chemical characteristics of the venous classes of contaminants. These factors, as well
as potential release mechanisms and migration pathways, have been discussed in
Sections 13.3 and 13.4.1. Also refer to Sections 3 and 7 of this guidance 1 and to the
lists of constituents provided in Appendix B.
13.4.2.2 Indicator Parameters
Indicator parameters (e.g., chemical and biochemical oxygen demand, pH, total
suspended solids, etc.) may also play a useful role in release characterization.
13-36
-------
Though indicators can provide useful data for release verification and
charactenzatiofl, specific hazardous Constituent concentrations should always be
monitored.
Following are brief synopses of some common indicator parameters and field
tests that can be used in investigations of surface water contamination. The use of
biomonitoring as an indicator of contamination is discussed in Section 13.4.5.
Biochemical Oxygen Demand (BOO) and Chemical Oxygen Demand (COD)—BOD is
an estimate of the amount of oxygen required for the biochemical degradation of
organic material (carbonaceous demand) and the oxygen used to oxidize inorganic
material such as sulfides and ferrous iron. It may also measure the oxygen used to
oxidize reduced forms of nitrogen (nitrogenous demand) unless their oxidation is
prevented by an inhibitor. Because the complete stabilization of a BOD sample may
require an extended period. 5 days has been accepted as the standard incubation
period. While BOO measures only biodegradable organics, non-biodegradable
materials can exert a demand on the available oxygen in an aquatic environment.
COD measures the total oxygen demand produced by biological and chemical
oxidation of waste constituents. Availability of results for the COD in approximately
4 hours, versus 5 days for the BOD, may be an important advantage of its use in
characterizing releases of a transient nature.
COD values are essentially equivalent to BOD when the oxidizable materials
present consist exclusively of organic matter. COD values exceed BOD values when
non-biodegradable materials that are susceptible to oxidation are present. The
reverse is not often the case; however, refinery wastes provide a notable exception.
There are some organic compounds, such as pulp and paper mill cellulose, that are
non-biodegradable, yet oxidizable. Nitrogenous compounds, which may place a
significant drain on available oxygen in aquatic environments, are not measured in
the COD test. In addition, chlorides interfere with the COD test, leading to
overestimates of the actual COD. BOO/COD ratios, as an indicator of
biodegradability, are discussed in Section 9 (Soil). BOO and COD may be useful
indicator parameters if the release is due primarily to degradable organic wastes.
13-37
-------
Total Organic Carbon (TOC)--Total organic carbon is valuable as a rapid estimator of
organic contamination in a receiving water. TOC, however, is not specific to a given
contaminant or eVen to specific classes of organics. In addition, TOC measurements
have little use if the release is primarily due to inorganic wastes.
Dissolved Oxygen (DO)--Measurements of DO may be readily made in the field with
an electronic DO meter, which has virtually replaced laboratory titrations.
Especially in lake environments, it is valuable to know the DO profile with depth.
The bottoms of lakes are often associated with anoxic conditions (absence of
oxygen) because of the lack of mixing with the surface and reduced or non-existent
photosynthesis. Influx of a contaminant load with a high oxygen demand can
further exacerbate oxygen deficiencies under such conditions. In addition, low DO
levels favor reduction, rather than oxidation reactions, thus altering products of
chemical degradation of contaminants. DO levels less than 3 mg/titer (ppm) are
considered stressful to most aquatic vertebrates (e.g., fish and amphibians).
—pH is probably one of the most common field measurements made of surface
waters. It is defined as the inverse log of the hydrogen ion concentration of an
aqueous medium. pH is generally measured in the field with analog or digital
electronic pH meters.
As an indicator of water pollution, pH is important for two reasons:
• The range within which most aquatic life forms are tolerant is usually quite
narrow. Thus, this factor has significant implications in terms of impact to
aquatic communities; and
• The pH of a solution may be a determining factor in moderating other
constituent reactions.
Temperature—Along with pH, temperature is a fundamental parameter that should
always be recorded in the field when a water sample is collected. Temperature is
most often measured by electronic meters that can simultaneously record pH and/or
specific conductance. Temperature isa significant parameter because:
13.38
-------
• Most aquatic species are sensitive to elevated temperatures;
• Elevatedtemperatures can be an indication of a contaminant plume;
• Most c.hemical reactions are temperature-dependent; and
• Temperature defines strata in thermally-stratified lakes.
Alkalinity—Alkalinity is the capacity of water to resist a depression in pH. It is,
therefore, a measure of the ability of the water to accept hydrogen ions without
resulting in creation of an acid medium. Most natural waters have substantial
buffering capacity (a resistance to any alteration in pH, toward either the alkaline
or acid side) through dissolution of carbonate-bearing minerals, creating a
carbonate/bicarbonate buffer system.
Alkalinity is usually expressed in calcium carbonate (CaCO3) equivalents and is
the sum of alkalinities provided by the carbonate, bicarbonate, and hydroxide ions
present in solution. Alkalinities in the natural environment usually range from 45 to
200 milligrams per liter (mg/I). Some limestone streams have extremely high
buffering capacities, while other natural streams are very lightly buffered and are
extremely sensitive to acid (or alkaline) loadings.
Hardness--The sum of carbonate and bicarbonate alkalinities is also termed
carbonate hardness. Hardness is generally considered a measure of the total
concentration of calcium and magnesium ions present in solution, expressed as
CaCO3 equivalents.
Calcium and magnesium ions play a role in plant and animal uptake of
contaminanb; knowledge of the hardness of a surface water is necessary for
evaluation of the site-specific bioaccumulative potential of certain contaminants
(e.g., heavy metals).
Total Solids—Analytically , the total solids (TS) content of a water is that remaining
after evaporation at 103-115° C or 180°C, depending on the method. The residue
remaining represents a sum of the suspended, colloidal, and dissolved solids.
13-39
-------
Hazardous constituents with high vapor pressures (i.e., volatiles, semi-volatiles) will 1
not remain after evaporation, and will not contribute to the IS determination.
SusDended Solids--Suspended solids are those materials that wiH not pass a glass-
fiber filter. Suspended solids contain both organic and inorganic compounds. For
the purpose of comparison to water samples, the average domestic wastewater
contains about 200 ppm (mg/I) of suspended solids.
Volatile SusDended Solids--Volatile suspended solids are the volatile organic portion
of the suspended solids. Volatile suspended solids are the components of
suspended solids that volatilize at a temperature of 6000 C. The residue or ash is
termed fixed suspended solids and is a measure of the inorganic fraction (i.e.,
mineral content). The only inorganic salt that will degrade below 600° C is
magnesium carbonate.
Total Dissolved Solids--Total dissolved solids context is obtained by subtracting
suspended solids from total solids. Its significance lies in the fact that it cannot be
removed from a surface water or effluent stream through physical means or simple
constituent processes, such as coagulation.
Salinity--The major salts contributing to salinity are sodium chloride (NaCI) and
sulfates of magnesium and calcium (MgSO 4 , CaSO 4 ). The following represents an
example of classification of saline waters on the basis of salt content.
T e of Water Total Dissolved Solids ( As Salts )
brackish i,ooo to 35,000 mg/I
seawater 35,000 mg/I
brine >3 5,000 mg/i
Specific Conductance _ conductivity measures the capacity to conduct current. Its
counterpart is, of course, resistance, measured in ohms. The unit of conductivity has
been defined as the mho. Specific conductance is conductivity/unit length. The most
common units for specific conductance are mho/cm. Specific conductance can be
measured instantaneously with electronic conductivity meters to comparatively
high levels of accuracy and precision in the field and is an excellent real-time
indicator parameter.
13-40
-------
Conductivity generally rises with increased concentration of dissolved (ionic)
species. Therefore, waters with high salinities, or high total dissolved solids, can be
expected to exhibit high conductivitieS. Variations in specific conductance within a
stream reach at a portion of an impoundment may indicate the presence of
contaminant release points.
Maior Ion Chemistry--The nature and prevalence of ionic species may serve as
indicators of pollution from waste sources containing inorganics. Ions result from
the dissociation of metal salts. The cation (e.g.. Na•, Ca•, Mg +) is typically a
metallic species and the anion (e.g., Cl - , S04—) a non-metallic species.
A common approach to use of ion chemistry as an indicator of waste
contamination in surface waters is to analyze for anions. Standard Methods
(American Public Health Association, 1985). protocol no. 429 includes the following
common anions as analytes:
Chloride (Ci ’)
Fluoride (F-)
Bromide (Br-)
Nitrate (N03-)
Nitrite (N02)
Phosphate (P04—)
Sulfate (S04)
While elevated concentrations of these anions may indicate the presence of
inorganic constituents or other contaminants, no information will be provided
regarding the identity of specific constituents or contaminants. In addition,
elevated levels of anions may be associated with effluent from domestic refuse
and/or runoff from fertilized agricultural fields.
The nature and concentrations of naturally-occurring ions in surface waters are a
function of the geologic setting of the area, and may be temporarily affected by
stormwater runoff, which may cause resuspension of streambed sediments.
13-41
-------
In reference to their inertness with respect to constituent and bioIogica
degradation, ionic species are termed TM conservative.” The fact that their mass is no
altered (i.e.. is conserved) in surface waters permits them to be used in simple
dilution modeling.
13.4.3 Selection of Monitoring Locations
The selection of monitoring locations should be addressed prior to simple
acquisition because it may affect the selection of monitoring equipment and
because monitoring locations will affect the representativeness of samples taken
during the monitoring program. Samples must be taken at locations representative
of the water body or positions of the water body with specific physical or chemical
characteristics. As discussed in Section 13.4.1.2 (Development of Conceptual
Model), one of the most important preliminary steps in defining monitoring
locations in a surface water monitoring program is developing a conceptual model
of the manner in which the release is distributed within the receiving water body.
This is dependent on the physical and chemical characteristics of the receiving
water, the point source or non•point source nature of the discharge, and the1
characteristics of the constituents themselves.
As a practical example, if a release contains contaminants whose specific
gravities exceed that of water, it may behave almost as a separate phase within the
receiving water body, traveling along the bottom of the water body. As another
example, certain contaminants may be found in comparatively low concentrations
in sediments or within the water column, yet may accumulate in aquatic biota via
bioaccumulation. In this case monitoring of the biota would be advised. If the
facility owner or operator is unaware of these phenomena, it would be possible for
the monitoring program to show no evidence of contamination.
In general, it will be desirable to locate monitoring stations in three areas
relative to the discharge in question.
• Background monitoring stations;
13-42
-------
Background monitoring should be performed in an area known not to be
influenced by the release of concern (e.g., upstream of a release).
• Monitoring stations at the release point(s) or area:
If the release is a point source or area source, periodic monitoring should
be performed at monitoring stations near the discharge origin to
determine the range of contaminant concentrations. The contaminant
stream (e.g., leachate seep, runoff) should also be subjected to
monitoring.
• Monitoring of the receiving water body within the area of influence:
One means af evaluating the water quality effects of a discharge is to
monitor the discharge point and model its dispersion (for example using
dispersion zone concepts discussed previously) within the receiving water
body. The results of this modeling may be used to determine appropriate
sampling locations. Actual sampling of the area thought to be influenced
by the release is required. The area of infiuence may be defined as that
portion of the receiving water withirr which the discharge would show a
measurable effect. As described prev ously, the area to be sampled is
generally defined in a phased fashion, based on a growing base of
monitoring data. It is usually prudent to start with a conservatively large
area and continually refine its boundaries. This is particularly true where
sensitive receptors (e.g., public water supply intakes, sensitive wetlands,
recreation areas) lie downstream of the release. In addition, in order to
determine the full extent of the release (and its effects), samples should
be taken at locations beyond the perceived area of influence.
The majority of the effort of the monitoring program will take place within the
area of influence, as defined above. Many factors are involved in selecting
monitoring stations within this area, the most critical being:
• The homogeneity of the water body in terms of temperature, flow, salinity.
and other physical and chemical characteristics;
13-43
-------
• The representatuveness of the monitoring point, in terms of both’
contamil’ ant characteristics and use factors;
• The presence of areas of pronounced water quality degradation; and
• Defensible monitoring design, including the choice of the monitoring
scheme (random, stratified random, systematic, etc.). the experimental
design, and adequate sample size determination.
Estuarine areas are particularly difficult in terms of selecting monitoring
locations that will allow an adequate evaluation of constituent distribution,
because detailed knowledge of the hydrologic characteristics of the estuary is
required to accurately locate representative monitoring points. Freshwater. salt
water stratification is a particularly important consideration, If stratification is
known to occur or is suspected, sampling should be conducted at a range of depths
within the estuary as well as at surface locations.
The selection of sampling locations is described in much greater detail in EPA
(1973. 1982).
13.4.4 Monitoring Schedule
The monitoring schedule or frequency should be a function of the type of
release (i.e., intermittent vs Continuous), variability in water quality of the receiving
water body (possibly as a result of other sources), and other factors causing the
release (e.g., meteorological or process design factors). Therefore, frequency of
monitoring should be determined by the facility owner or operator on a site-
specific basis. All sampling points should be sampled as close to simultaneously as
possible, regardless of the monitoring frequency established.
Factors important in determining the required frequency of monitoring include:
13-44
-------
• The homogeneity of the receiving water in terms of factors that may
affect the fate of constituents. The most important of these are flow and
seasonal or diurnal stratification.
• The characteristics of the releases. Releases may be continuous or event-
associated.
As an example, continuous, point source releases of low variability subject to
few, if any, additional releases may require relatively infrequent monitoring. On
the other hand, releases known to be related to recurrent causes, such as rainfall
and runoff, may require monitoring associated with the event. Such monitoring is
termed event sampling. To evaluate the threshold event required to trigger
sampling, as well as the required duration of the monitoring following the event, it
is necessary that the rele of the event in creating a release from the unit be well
understood. In what is probably the most common example, if stormwater runoff is
the event of concern, a hydrograph for various storm return intervals and durations
should be estimated for the point or area of interest and the magnitude and
duration of its effects evaluated.
Continuous monitoring can be accomplished through j probes that provide
frequent input to field data storage units. However, continuous monitoring is
feasible only for the limited number of constituents and indicator parameters foe
which reliable automatic sampling/recording equipment is available.
In estuaries, samples are generally required through a tidal cycle. Two sets of
samples are taken from an area on a given day, one at ebb or flood slack water and
another at three hours earlier or later at half tide interval. Sampling is scheduled
such that th. mid-sampling time of each run coincides with the calculated
occurrence of the tidal condition.
13.4.5 Hydrologic Monitoring
The monitoring program should also include provisions for hydrologic
monitoring. Specifically, the program should provide for collection of data on the
hydrologic condition of the surface water body at the time of sampling.
13-45
-------
For example, some indication of the stage and discharge of a stream beii,
monitored need, to be recorded at the time and location each water sample is
collected. Similarly, for sampling that occurs during storms, a record of rainfall
intensity overthe duration of the storm needs to be obtained. Without this
complementary hydrologic data, misinterpretation of the water quality data in
terms of contaminant sources and the extent of contamination is possible.
The techniques for hydrologic monitoring that could be included in a monitoring
program range in complexity from use of simple qualitative descriptions of
streamflow to permanent installation of continuously-recording stream gages. The
techniques appropriate in a given case will depend on the characteristics of the unit
and of the surface waters being investigated. Guidance on hydrologic monitoring
techniques can be found in the references cited in Section 13.6.1.
13.4.6 The Role of Biomonitoring
The effects of contaminants may be reflected in the population density, speciel
composition and diversity, physiological condition, and metabolic rates of aquati
organisms and communities. Biomonitoring techniques can provide an effective
complement to detailed chemical analyses for identifying chemical contamination
of water bodies. They may be especially useful in those cases where releases involve
constituents with a high propensity to bioaccumulate. This includes most metal
species and organics with a high bioconcentration factor (e.g., >10) or a high
octanol/water partition coefficient (e.g., >2.3). These properties were discussed in
Section 13.3.
Biomonitoring techniques may include:
• Community ecology studies;
• Evaluation of food chain/sensitive species impacts; and
• Bioassays.
These techniques are discussed below.
13-46
-------
13.4.6.1 Community Ecology Studies
Indicator species are useful for evaluating the well-being of an aquatic
community that may be stressed by the release of contaminants. For example, the
condition of the benthic macroinvertebrate community is commonly used as an
indicator of the presence of contaminants. The objective of studying the naturally-
occurring biological community is to determine community structure thatwould be
expected, in an undisturbed habitat. If significant changes occur, perturbations in
the community ecology may be linked to the disturbance associated with release of
contaminants to the water body.
EPA is engaged in research to develop rapid bioassessment techniques using
benthic macroinvertebrates. Although protocols are being considered, in general
these techniques suffer. from lack of data on undisturbed aquatic communities and
associated water quality information. For some areas (e.g., fisheries), however.
indices to community health based on benthic invertebrate communities are
available (Hilsenhoff 1982, Cummins and Wilgbach, 1985).
Because spec’es diversity is a commonly-used indicator of the overall health of a
community, depressed community diversity may be considered an indicator of
contamination. For example, if a release to surface waters has a high chemical
oxygen demand (COD) and, therefore, depresses oxygen levels in the receiving
water body, the number of different species of organisms that can colonize the
water body may be reduced. In this case the oxygen-sensitive species (e.g..the
mayfly), is lost from the community and is replaced by more tolerant species. The
number of tolerant species is small, but the number of individuals within these
species that can colonize the oxygen-deficient waters may be quite large. Therefore.
the overall species diversity could be low, even though the numbers of organisms.
may be high.
Evaluations of community ecology should however, be sensitive to the role that
habitat variability may play in altering community structure. Diversity of habitat
may be altered by natural physical conditions (e.g., a rapid increase in stream
gradient), substrate characteristics (e.g., silty versus rocky substrate), and so forth. It
may also be difficult to directly link contaminant levels with the presence or absence
13-47
-------
of aquatic organisms, unless there is a secondary impact that is more self ..eviden
such as high oxygen demand, turbidity, or salinity.
13.4.6.2 Evaluation of Food Chain Sensitive/Species Impacts
At this level of biomonitoring, the emphasis is actually on the threat to specific
fish or wildlife species, or man, as a result of bioaccumulation of constituents from
the release being carried through the food web. Bioaccumulative contaminants are
not rapidly eliminated by biological processes and accumulate in certain organs or
body tissues. Their effect may not be felt by individual organisms that initially
consume the contaminated substrate or take up the contaminants from the water.
However, organisms at higher trophic levels consume the organisms of the lower
trophic levels. Consequently, contaminants may become bioaccumulated in
organisms and biomagnified through the food web.
Examination of the potential for bioaccumulation and biomagnification of
contaminants requires at least a cursory characterization of the community to
define its trophic structure, that is, which organisms occupy which relative position
within the community. Based on this definition, organisms representative of the
various trophic levels may be collected, sacrificed, and analyzed to determine the
levels of the contaminants of interest present.
If a specific trophic level is of concern, it may be possible to short-cut the process
by selectively collecting and analyzing organisms from that level for the
contaminants of concern. This may be the case, for instance, if certain organisms
are taken by man either commercially or through recreational fishing, for
consumption. It may also be necessary to focus on the prey of specialitatus fish or
wildlife (e.g., eagles and other birds of prey) to establish their potential for
exposure. This type of biomonitoring may be especially useful if constituents
released have a relatively high potential to bioaccumulate. A discussion of
indicators that are generally predictive of constituents which have a significant
potential for bioaccumulation was presented in Section 13.3.
In addition, in the selection of organisms it is important to consider the ability of
a given organism to accumulate a class of contaminants and the residential vsl
13-48
-------
migratory nature of the organisms. For example, bullfrogs are superior for
accumulating metals but poor for organics; spawning (thus migratory) salmon
would be much less useful for characterizing a release from a local facility than
would resident fish.
13.4.6.3 Bioassay
Bioassay may be defined as the study of specially selected representative species
to determine their response to the release of concern, or to specific constituents of
the release. The organisms are monitored for a period of time established by the
bioassay method. The objective of bioassay testing is to establish a concentration-
response relationship between the contaminants of concern and representative
biota that can be used to evaluate the effects of the release. Bioassay testing may
involve the use of indigenous organisms (U.S. EPA, 1973) or organisms available
commercially for this purpose. Bioassays have an advantage over strict constituent
analyses of surface waters and effluents in that they measure the total effect of all
constituents within the release on aquatic organisms (within the limits of the test).
Such results, therefore, are not as tightly constrained by assumptions of
contaminant interactions. Discussions of bioassay procedures are provided by
Peltier and Weber (1985) and Horning and Weber (1985).
The criterion commonly used to establish the endpoint for a bioassay is mortality
of the test organisms, although other factors such as depressed growth rate,
reproductive success, behavior alteration, and flesh tainting (in fish and shellfish)
can be used. Results are commonly reported as the LC5O (i.e., the lethal
concentration that resulted in 50 percent mortality of the test organisms within the
time frame of the test) or the ECSO (i.e., the effective concentration that resulted in
50 percent of the test organisms having an effect other than death within the time
frame of the test).
One potential use of bioassays during the RFI is to predict the effect of a release
on sensitive species residing in the affected surface water(s). Bioassay may be
especially useful if the release is intermittent. In this case, samples of the waste may
be taken from the unit of concern and used to conduct bioassay tests. The bioassay
may be conducted using the waste at 100 percent strength, and in diluted form, to
13-49
-------
obtain a concentration response relationship. The results of this testing may then,
be used to predict the effects of a release on the surface water biota.
Bioassays can serve as important complements to the overall monitoring
program. In considering the role and design of bioassays in a monitoring program,
however, the facility owner or operator should be aware of problems involved in
toxicity testing. Some bioassay problems include the following considerations:
toxicity meaurements are difficult to interpret in terms of actual instream impacts;
toxicity test-method precision is low and difficult to quantitate; actual exposure and
species sensitivity is variable; and antagonistic and synergistic effects are likely. A
review of these issues is provided by Brandes et at. (1985).
13.5 Data Management and Presentation
The owner or operator will be required to report on the progress of the RFI at
appropriate intervals during the investigation. The data should be reported in a
dear and concise manner, and interpretations should be supported by the data. The
following data presentation methods are suggested for the various phases of the
surface water investigation. Further information on the various procedures is given
in Section 5. Section 5 also provides guidance on various reports that may be
required.
13.5.1 Waste and Unit Characterization
Waste and unit characterigjc should be presented as:
• Tables of waste constituents, concentrations, effluent flow and mass
loadings;
• Tables of relevant physical and chemical properties of potential
contaminants (e.g., solubility);
• Narrative description of unit operations;
• Surface map and plan drawings of facility, unit(s), and surface waters; and
13-50
-------
• Identification of reasonable worst case contaminant release to surface
wate rs.
13.5.2 Environmental Setting Characterization
The environment of the waste unit(s) and surface waters should be described in
terms of physical and biological environments in the vicinity. This description
should include:
• A map of the area portraying the location of the waste unit in relation to
potential receiving waters;
• A map or narrative classification of surface waters (e.g.. type of surface
water, uses of the surface water, and State classification, if any);
• A description of the climatological setting as it may affect the surface
hydrology or release of contaminants; and
• A narrative description of the hydrologic conditions during sampling
periods.
13.5.3 Characterization of the Release
The complex nature of the data involving multiple monitoring events,
monitoring locations, matrices (water, sediment, biota), and analytes lends itself to
graphic presentation. The most basic presentation is a site map or series of maps
that locate th. monitoring stations for each monitoring event. These maps may
also be adapted to include isopleths for specific analytes; however, since the
isopleths imply a continuity within their borders, they may not be appropriate
unless they are based on an adequate number of monitoring points and
representative data. The contours should be based on unit intervals whose accuracy
ranges do not overlap. In most situations, two separate reporting formats are
appropriate. First, the data should be included as tables. These tables should
generally be used to present the analytical results for a given sample. Each table
13-5 1
-------
could include samples from several locations for a given matrix, or could include
samples from each location for all sample matrices. Data from these tables can then
be summarized fdr Comparison purposes using graphs.
Graphs are most useful for displaying spatial and temporal variations. Spatial
variability for a given analyte can be displayed using bar graphs where the vertical
axis represents concentration and the horizontal axis represents downstream
distance from the discharge. The results from each monitoring station can then be
presented as a concentration bar. Stacked bar graphs can be used to display these
data from each matrix at a given location or for more than one analyte from each
sample.
Similarly, these types of graphs can be used to demonstrate temporal variability
if the horizontal axis represents time rather than distance. In this configuration,
each graph will present the results of one analyte from a single monitoring location.
Stacked bars can then display multiple analytes or locations. Line graphs, like
isopleths. should be used cautiously because the line implies a continuity, either
spatial or temporal, that may not be accurately supported by the data.
Scatter plots are useful for displaying correlations between variables. They can
be used to support the validity of indicator parameters by plotting the indicator
results against the results for a specific constituent.
Graphs are used to display trends and correlations. They should not be used to
replace data tables, but rather to enhance the meaning of the data.
13.6 FIeld and Other Methods
The purpose of this section is to provide an overview of methods that can be
used to characterize the nature, rate, and extent of contaminant releases to surface
water. Detailed descriptions of specific methods can be found in the indicated
references.
The methods presented in this section relate to four specific areas, as follows:
13-52
-------
• Surface Water Hydrology;
• SampIin and Constituent Analysis of Surface Water, Sediments, and
Biota;
• Characterization of the Condition of the Aquatic Community; and
• Bioassay Methods.
13.6.1 Surface Water Hydrology
The physical attributes of the potentially affected water body should be
characterized to effectively develop a monitoring program and to interpret results.
Depending on the characteristics of the release and the environmental setting, any
or all of the following hydrologic measurements may need to be undertaken.
• Overland flow:
- Hydraulic measurement;
• Rainfall/runoff measurement;
• Infiltration measurement; and
• Drainage basin characterization (including topographic characteristics.
soils and geology, and land use).
• Open channel flow:
• Measurement of stage (gaging activities);
• Measurement of width, depth, and cross-sectional area;
• Measurement of velocity;
- Measurement of channel discharge;
- Measurement of channel discharge at controls (e.g.. dams and weirs);
and
• Definition of flow pathways - solute dispersion studies.
• Closed conduit flow:
- Measurement of discharge.
13-5 3
-------
• Lakes and impoundments:
• Morphometric mapping;
- Bathymetric mapping;
- Temperature distributions; and
• Flow pathways.
The following references provide descriptions of the measurements described
above.
National Oceanic and Atmospheric Administration. Rainfall Atlas of the U.S .
Viessman, et al., 1977. Introduction to Hydrology .
USGS. 1977. National Handbook of Recommended Methods for Water-Data
Acquisition Chapter 1 (Surface Water) and Chapter 7 (Physical Basin
Characteristics for Hydrologic Analyses).
US 1 Department of Interior. 1981. Water Measurement Manual . Bureau of
Reclamation. GPO No. 024.003-00158-9. Washington, D.C.
Chow. 1964. Open Channel Hydraulics . McGraw-Hill. New York, N.Y.
In addition, the following monographs in the Techniques of Water Resources
Investigations series of the USGS (USGS-WSP-1822 , 1982) give the reader more
detailed information on techniques for measuring discharge and other
characteristics of various water bodies and hydrologic conditions:
Benson and Dalrymple. 1967. General Field and Office Procedures for Indirect
OiSChb?OL* Measurement .
Bodhaine, 1968. Measurement of Peak Discharge at Culverts by Indirect
Methods . USGS-TWI-03-AS.
Buchanan and Somers. 1968. Staae Measurements at Gaging Stations .
13-54
-------
Carter and David ian. 1968. General Procedure for Gaping Streams . USGS-1WI-
03-AL.
13.6.2 Sampling of Surface Water. Runoff, Sediment, and Biota
13.6.2.1 SurfaceWater
The means of collecting water samples is a function of the classification of the
water body, as discussed in Section 13.3.3.1. The following discussion treats lakes
and impoundments separately from streams and rivers although, as indicated
below, the actual sampling methods are similar in some cases. Wetlands are
considered intergrade between these waters. Stormwater and snowmelt runoff is
also treated as a separate category (Section 13.6.2.2). Although estuaries also
represent somewhat of an intergrade , estuary sampling methods are similar to
those for large rivers and lakes.
13.6.2.1.1 Streams and Rivers
These waters represent a continuum from ephemeral to intermittent to
perennial. Streams and rivers may exhibit some of the same characteristics as lakes
and impoundments. The degree to which they are similar is normally a function of
channel configuration (e.g., depth, cross sectional area and discharge rate). Larger
rivers are probably more similar to most lakes and impoundments, with respect to
sampling methods, than to free-flowing headwater streams. In general, however,
streams and rivers exhibit a greater degree of mixing due to their free-flowing
characteristics than can be achieved in lakes and impoundments. Mixing and
dilution of inflow can be slow to fast, depending on the point of discharge to the
stream or river and the flow conditions.
Stream and river sampling methods do not differ appreciably from those
outlined in the following section (Lakes and Impoundments). However, the
selection of monitoring stations must consider additional factors created by
differential flow velocities within the stream cross section. Strong currents and
turbulence as a result of channel configuration may affect the amount of mixing
and the distribution of contaminants in the stream. The reader may wish to refer to
13-55
-------
the references provided in Section 13.3.1 for a discussion of the manner in which
differential velocities are handled in stream gaging studies to obtain representative
discharge measu ments.
13.6.2.1.2 Lakes and Impoundments
These waters are, by definition, areas where flow velocity is reduced, limiting the
circulation of waters from sources such as discharging streams or ground water.
They often include a shoreline wetland where water circulation is slow dilution of
inflowrng contaminants is minimal, and sediments and plant life become significant
factors in sampling strategies. The deeper zones of open water may be vertically
stratified and subject to periodic turnover, especially in temperate climates.
Sampling programs should be designed to obtain depth-specific information as well
as to characterize seasc nal variations.
Access to necessary monitoring stations may be impeded by both water depth
and lush emergent or floating aquatic vegetation, requiring the use of a floating
sampling platform or other means to appropriately place the sampling apparatus. It
is common to employ rigid extensions of monitoring equipment to collect surface
samples at distances of up to 30 or 40 feet from the shoreline. However, a boat is
usually the preferred alternative for distances over about six feet. A peristaltic
pump may also be used to withdraw water samples, and has the added advantage
of being able to extract samples to a depth of 20 to 30 feet below the surface.
Many sampling devices are available in several materials. Samples for trace
metals should not be collected in metal bottles, and samples for organics should not
be collected in plastic bottles. Teflon or Teflon-coated sampling equipment.
including bottles, is generally acceptable for both types of constituents. EPA (1982)
and EPA (1986) provide an analysis of the advantages and disadvantages of many
sampling bottles for specific sampling situations. Detailed descriptions of the use of
dippers/transfer devices pond samplers, peristaltic pumps. and Kemmerer bottles
are provided by EPA (1984).
Depthspecific samples in lake environments are usually collected with
equipment such as Kemmerer bottles (commonly constructed of brass), Van Dorn
13-56
-------
samplers (typically of polyvinyl chloride Or PVC construction), or Nansen tubes. The
depth-specific sample closure mechanism on these devices is tripped by dropping a
weight (messenger) down the line. Kemmerer bottles and Nansen tubes may also
be outfitted with a thermometer that records the temperature of the water at the
time of collection.
13.6.2.1.3 Additional Information
Additional information regarding specific surface water sampling methods may
be found in the following general references:
U.S. EPA. 1986. Methods for Evaluating Solid Wastes . EPA/SW-846. GPO No.
955-001.00000-1. Office of Solid Waste. Washington, D.C. 20460.
U.S. EPA. 1984. Characterization of Hazardous Waste Sites -- A Methods Manual:
Volume II. Available Sampling Methods . EPA-600/4-84076. NTIS P8-168771.
Washington, D.C. 20460.
U.S. EPA. 1986. Handbook of Stream Sampling for Wasteload Allocation
p lications . EPAJ62S/6 .83/013.
U.S. EPA. 1982. Handbook for Sampling and Sample Preservation of Water and
Wastewater . NTIS P883-124503.
USGS. 1977. National Handbook of Recommended Methods for Water-Data
Acgu ,sitiOn .
13.6.2.2 Runoff Sampling
Runoff resulting from precipitation or snowmelt creates an intermittent release
situation that requires special treatment for effective sampling. The contaminant
release mechanism in runoff situations may be overflow of ponds containing
contaminants or erosion of contaminated soils. Based on an evaluation of the waste
characteristics and the environmental setting, the facility owner or operator can
13-57
-------
determine whether waste constituents will be susceptible to this release mechanism
and migration pathway.
Once it has been determined that erosion of contaminated soils is of concern,
the quantity of sail transported to any point of interest, such as the receiving water
body, can be determined through application of an appropriate modification of the
Universal Soil Loss Equation (USLE). The LiSLE was developed by the U.S.
Department of Agriculture, Agricultural Stabilization and Conservation Service
(ASCS) to assist in the prediction of soil loss from agrscultural areas. The formula is
reproduced below:
A RKLSCP
where:
A Estimated annual average soil loss (tons/acre)
R Rainfall intensity factor
K Soil erodibility factor
I Slope-length factor
S Slope-gradient factor
C Cropping management factor
P Erosion control practice factor
*C and P factors can be assumed to equal unity in the equation if no specific crop
or erosion management practices are currently being employed. Otherwise, these
factors can be significantly less than unity, depending on crop or erosion control
practices.
Section 3.7 (Soil Contamination) of the Draft Superfund Exposure Assessment
Manual (EPA, 1986) provides a discussion of the application of the USLE to
characterization of releases through soil erosion.
If the potential for significant contaminant release exists, based on analysis of
the hydrologic situation and waste site characteristics, event samples should be
taken during high runoff periods. In situations where high runoff is predictable,
13-58
-------
such as spring runoff or the summer thundershower season, automatic samplers
may be set to sample during these periods. Perhaps the most effectiv, way to
ensure sampling during significant events is to have personnel available to collect
samples at intervals throughout and following the storm. Flow data should be
collected coincident with sample collection to permit calculation of contaminant
loading in the runoff at various flows during the period. Automated sampling
equipment is available that will collect individual samples and composite them
either over time or with flow amount, with the latter being preferred. Flow-
proportional samplers are usually installed with a flow-measuring device, such as a
weir with a continuous head recorder. Such devices are readily available from
commercial manufacturers and can be rented or leased. Many facilities with an
NPDES discharge permit routinely use this equipment in compliance monitoring.
Automated samplers are discussed in Section 8 of Handbook for Sam linp and
Sample Preservation of Water and Wastewater (EPA, 1982) (NTIS P8 83-124503); this
publication also includes other references to automated samplers and a table of
devices available from various manufacturers.
13.6.2.3 Sediment
Sediment is traditionally defined as the deposited material underlying a body of
water. Sediment is formed as waterborne solids (particulates) settle out of the
water column and build up as bottom deposits.
Sedimentation is greatest in areas where the stream velocity decreases, such as
behind dams and flow control structures, and at the inner edge of bends in stream
channels. Sediments also build up where smaller, fast-flowing streams and runoff
discharge into larger streams and lakes. These areas can be important investigative
areas. Some sections of a streambed may be virtually without sediments. In some
streams or some areas of streams, water velocity may be too fast for sediments to
deposit and actually may scour the bottom, transporting material and depositing it
further downstream. The stream bed in such an area will be primarily rocks and
debris.
13-59
-------
In some situations, such as low.flow conditions, the overlying water temporarily
recedes, exposing sediments to the air. Runoff channels, small lakes, and small
streams and rivers using may on occasion dry completely. In these cases, samples
can be collected using the same procedures described in the Soils section (Section 9)
of this document.
For this discussion, the definition of sediment will be expanded to include any
material that may be overlain by water at any time during the year. This definition
then includes what may otherwise be considered submerged soils and sludges.
Submerged soils are found in wetlands and marshes. They may be located on the
margins of lakes, ponds, and streams, or may be isolated features resulting from
collected runoff, or may appear in areas where the ground.water table exists at or
very near the land surface. In any instance they are important investigative areas.
Sludges are included for discussion here because many RCRA facilities use
impoundments for treatment or storage and these impoundments generally have a
sludge layer on the bottom. Sampling these sludges involves much the same
equipment and techniques as would be used for sediments.
There are essentially two ways to collect sediment samples, either by coring or
with grab/dredges. Corers are metal tubes with sharpened lower edges. The corer
is forced vertically into the sediment. Sediments are held in the core tube by friction
as the corer is carefully withdrawn; they can then be transferred to a sample
container. There are many types and modifications of corers available. Some units
are designed to be forced into the sediments by hand or hydraulic pressure; others
are outfitted with weights and fins and are designed to free fall through the water
column and are driven into the sediment by their fall.force.
Corers sample a greater thickness of sediments than do grab/dredges and can
provide a profile of the sediment layers. However, they sample a relatively small
surface area. Most corers are less than four inches in diameter and are more
commonly two inches in diameter.
Grab/dredges are basically clamshell-type scoops that sample a larger surface
area but offer less depth of penetration. Typical grab/dredge designs are the Ponar,
13-60
-------
Eckman, and Peterson versions; each has a somewhat different operating
mechanism and slightly different advantages. Some use spring force to close the
jaws while othernre counter-levered like ice tongs.
In sediment sampling, vertical profiling is not normally required since deposition
of hazardous material is often a recent activity in terms of sedimentary processes.
Grab/dredges that sample a greater surface area may be more appropriate than
corers. Similarly, shallow sludge layers contained in surface impoundments should
.be sampled with grab/dredges because corer penetration could damage the
impoundment liner, if present. Thicker sludge layers which may be present in
surface impoundments. may be sampled using coring equipment if it is important to
obtain vertical profile information.
Submerged soils are generally easier to sample with a corer, than with a
grab/dredge because vegetation and roots can prevent the grab/dredges from
sealing completely. Under these conditions, most of the sample may wash out of
the device as it is recovered. Corers can often be forced through the vegetation and
roots to provide a sample. In shallow water, which may overlie submerged soils,
sampling personnel can wade through the water (using proper equipment and
precautions) and choose sample locations m the small, clear areas between
vegetative stems and roots.
A wide variety of sampling devices are available for collection of sediment
samples. Each has advantages and disadvantages in a given situation, and a variety
of manufacturers produce different versions of the same device. As with water
sampling, it is important to remember that metal samplers should not be used when
collecting samples for trace metal analysis, and sampling devices with plastic
components should not be used when collecting samples for analysis of organics.
The following references describe the availability and field use of sediment
samplers:
U.S. EPA. 1982. Handbook for Sampling and Sample Preservation of Water and
Wastewater . Environmental Monitoring and Support Laboratory.
EPA-600/4-82-029. NTIS PB 83-124503.
13-6 1
-------
U.S. EPA. 1985. Methods Manual for Bottom Sediment Sample Collection . NTIS’
P986-1O7414.
USGS. 1977-update June 1983. National Handbook of Recommended Methods
for Water-Data ACQUISitIOn .
U.S. EPA. 1984. Characterization of Hazardous Waste Sites - . A Methods Manual:
Volume II. Available Sampling Methods . EPA-600/444-076. NTIS PB 85-168771.
13.6.2.4 Biota
Collection of biota for constituent analysis (whole body or tissue) may be
necessary to evaluate Exposure of aquatic organisms or man to bioaccumulative
contaminants. For the most part, collection should be restricted to representative
fish species and sessile macroinvertebrates, such as mollusks. Mollusks are filter.
feeders; bioaccumulative contaminants in the water column will be extracted and
concentrated in their tissues. Fish species may be selected on the basis of their
commercial or recreational value, and their resultant probability of being consumea
by man or by special status-species of fish or wildlife.
The literature on sampling aquatic organisms is large. Most sampling methods
include capture techniques that be collected using sampling bottles (as for water
samples) or nets of appropriate mesh sizes. Periphyton may be most easily collected
by scraping off the substrate to which the organisms are attached. Other techniques
using artificial substrates are available if a quantitative approach is required.
Aquatic macroinvertebrates may be collected using a wide variety of methods,
depending on the area being sampled; collection by hand or using forceps may be
efficient. Grab sampling, sieving devices, artificial substrates and drift nets may also
be used effectively. EPA (1973) provides a discussion of these techniques, as well as
a method comparison and description of data analysis techniques.
Fish collection techniques may be characterized generally as follows (USGS,
1977):
13-62
-------
• Entangling gear:
Gill nets and trammel nets.
Entt ’ pping gear:
Hoop nets, basket traps, trap nets, and fyke and wing nets.
• Encircling gear:
Haul seine, purse seine, bay seine, and Danish seine.
Electroshocking gear:
Boat shockers, backpack shockers, and electric seines.
Selection of sampling equipment is dependent on the characteristics of the water
body, such as size and conditions, the size of the fish to be collected, and the overall
objectives of the study. Fisheries Techniques (Nielsen and Johnson, 1983) and
Guidelines for Sam linq Fish in Inland Waters (Backiel and Welcomme, 1980)
provide basic descriptions of sampling methods and data interpretation from
fisheries studies.
13.6.3 Characterization of the Condition of the Aquatic Community
Evaluation of the condition of aquatic communities may proceed from two
directions. The first consists of examining the structure of the lower trophic levels as
an indication of the overall health of the aquatic ecosystem. With respect to RFI
studies, a healthy water body would be one whose trophic structure indicates that t
is not impacted by contaminants. The second approach focuses on a particular
group or species, possibly because of its commercial or recreational importance or
because a substantial historic data base already exists.
The first approach emphasizes the base of the aquatic food chain, and may
involve studies of plankton (microscopic flora and fauna), periphyton (including
bacteria, yeast, molds, algae, and protozoa). macrophytori (aquatic plants), and
benthic macroinvertebrates (e.g., insects, annelid worms, mollusks, flatworms,
roundworms, and crustaceans). These lower levels of the aquatic community are
studied to determine whether they exhibit any evidence of stress. If the community
appears to have been disturbed, the objective is to characterize the source(s) of the
stress and, specifically, to focus on the degree to which the release of waste
constituents has caused the disturbance or possibly exacerbated an existing
13•63
-------
problem. An example of the latter would be the further depletion of already 10w1
dissolved oxygen levels in the hypolimnion of a lake or impoundment through the!
introduction of waste with a high COD and specific gravity.
The samplir g methods referenced in Section 13.6.2.4 may be adapted (by using
them in a quantitative sampling scheme) to collect the data necessary to
characterize aquatic communities. Hynes (1970) and Hutchinson (1967) provide an
overview of the ecological structure of aquatic communities.
Benthic macroinvertebrates are commonly used in studies of aquatic
communities. These organisms usually occupy a position near the base of the food
chain. Just as importantly, however, their range within the aquatic environment is
restricted, so that their community structure may be referenced to a particular
stream reach or portion of lake substrate. By comparison, fish are generally mobile
within the aquatic environment, and evidence of stress or contaminant load may
not be amenable to interpretation with reference to specific releases.
The presence or absence of particular benthic macroinvertebrate species,
sometimes referred to as indicator species, may provide evidence of a response to
environmental stress. Several references are available in this regard. For more
information, the reader may consult Selected BibliograDhy on the Toxicology of the
Benthic Invertebrates and PeriDhyton (EPA, 1984).
A species diversity index provides a quantitative measure of the degree of
stress within the aquatic community, and is an example of a common basis for
interpretation of the results of studies of aquatic biological communities. The
following equation (the Sannon-W,ener Index) demonstrates the concept of the
diversity index:
H • (P1) (logs Pi)
‘SI
where:
H = species diversity index
13-64
-------
s = number of species
p 1 proportion of total sample belonging to the ith species
Measures of species diversity are most useful for comparison of streams with similar
hydrologic characteristics or for the analysis of trends over time within a single
stream. Additional detail regarding the application of other measures of
community structure may be found in the following references:
U.S. EPA. 1973. Biological Field and Laboratory Methods for Measuring the
Quality of Surface Water and Effluents .
USGS. 1977, Update May, 1983. National Handbook of Recommended Methods
of Water-Data Acquisition .
Curns, J. Jr., and K.L. Dickson, ads. 1973. ASTM STP 528: Biological Methods for
the Assessment of Water quality . American Society for Testing and Materials.
STPS28. Philadelphia, PA.
The second approach to evaluating the condition of an aquatic community is
through selective sampling of specific organisms, most commonly fish, and
evaluation of standard condition factors (e.g., length, weight, girth). In many
cases, receiving water bodies are recreational fisheries, monitored by state or
federal agencies. In such cases, it is common to find some historical record of the
condition of the fish population, and it may be possible to correlate operational
records at the waste management facility with alterations in the status of the fish
population.
Sampling of fish populations to evaluate condition factors employs the same
methodologies referenced in Section 13.6.2.4. Because of the intensity of the effort
usually associated with obtaining a representative sample of fish, it is common to
coordinate tissue sampling for constituent analysis with fishery surveys.
13-65
-------
13.6.4 Bioassay Methods
The purpose af a bioassay, as discussed is more detail in Section 13.4.6.3. is to
predict the response of aquatic organisms to specific changes within the
environment. jn the RFI context, a bioassay may be used to predict the potential
adverse environmental effects of releases to surface water. Thus, bioassay is not
generally considered to be an environmental characterization or monitoring
technique. As indicated below, bioassay may be required for Federal water quality
programs or state programs, especially where stream classification (i.e., warm-water
fishery, cold water fishery) is involved.
Bioassays may be conducted on any aquatic organism including algae,
periphyton, macroinvertebrates, or fish. Bioassay includes two main techniques,
acute toxicity tests and chronic toxicity tests. Each of these may be done in a
laboratory setting or using a mobile field laboratory. Following is a brief discussion
of acute and chronic bioassay tests.
Acute Toxicity Tests--Acute toxicity tests are used in the NPDES Permit Program t
identify effluents containing toxic wastes discharged in toxic amounts. The data are
used to predict potential acute and chronic toxicity in the receiving water, based on
the LC5O and appropriate dilution, and application of persistence factors. Two types
of tests are used; static and flow-through. The selection of the test type will depend
on the objectives of the test, the available resources, the requirements of the test
organisms, and effluent characteristics. Special environmental requirements of
some organisms may preclude static testing.
It should be noted that a negative result from an acute toxicity test with a given
effluent sample does not preclude the presence of chronic toxicity, nor does it
negate the possibility that the effluent may be acutely toxic under different
conditions, such as variations in temperature or contaminant loadings.
There are many sources of information relative to the performance of acute
bioassays. Methods for Measuring the Acute Toxicity of Effluents to Freshwater and
Marine Organisms (Peltier and Weber, 1985) provides a comprehensive treatment
of the subject.
13-66
-------
Chronic Toxicity Tests ..ChroniC toxicity tests may include measurement of effluent
effects on growth and reproductive success. These tests usually require long periods
of time, depending on the life cycles of the test organisms. Chronic bioassays are
generally relatively sophisticated procedures and are more intensive in terms of
manpower, time and expense than are acute toxicity tests. The inherent complexity
of these tests dictate careful planning with the regulatory agency prior to initiation
of the work. Methods for Measuring the Chronic Toxicity of Effluents to Aquatic
Organisms (Horning and Weber, 1985) is a companion volume to the methods
document noted above, and contains method references for chronic toxicity tests. A
discussion of bioassay procedures is also provided in Protocol for Bioassessment of
Hazardous Waste Sites . NTIS PB 83.241737. (Tetra Tech, 1983).
13-67
-------
13.7 Checklist
RFI Checklist - Surface Water
Site Name/Location _____________________________
Type of Unit _____________________________
1. Does waste characterization include thefl following information? (V/N)
• Constituents of concern
• Concentrations of const tuefltS
• Mass of the constituent
• Physical state of waste (e.g., solid, liquid, gas)
• Water solubitity
• Henry’s Law Constant
• OctanollWater Partition Coefficient (K )
• Bioconcentration Factor (BCF)
• Adsorption Coefficient (KOC)
• Physical, biological, and chemical degradation
2. Does unit characterization include the following information’ (V/N)
• Ageofunit
• Typeof unit
• Operating practices
• Quantities of waste handled
• Presence of cover or other surface covering
• Dimensions of unit
• Presence of natural or engineered barriers near unit
• Release frequency
• Release volume and rate
• Non-point or point source release
• Intermittent or continuous release
13-68
-------
RFI Checklist Surface Water (Continued)
3. Does environmental setting information include the following?
(YIN)
• Areal extent of drainage basin
• Location and interconnection of all streams, lakes
and other features
• Flow identification as ephemeral, intermittent or perennial
• Channel alignment, gradient and discharge rate
• Flood and channel control structures
• Source of lake and impoundment water
• Lake and impoundment depths and surface area
• Vertical temperature stratification of lakes and impoundments
• Wetland presence and role in basin hydrology
• NPDES and other discharges
(‘ USGS gaging stations or other existing flow monitoring systems
• Surface water quality characteristics
o Average monthly and annual precipitation values
o Average monthly temperature
O Average monthly evaporation potential estimates
• Storm frequency and severity
0 Snowfall and snow pack ranges
4. Have the following data on the initial phase of the release characterization
been collected? (YIN)
• Monitoring locations
• Monitoring constituents and indicator parameters
• Monitoring frequency
• Monitoring equipment and procedures
• Concentrations of constituents and locations
at which they were detected
• Background monitoring results
13-69
-------
RFI Checklist - Surface Water (Continued)
• Hydrologic and biomonitoring results
• Inter-media transfer data
• Analyses of rate and extent of contamination
5. Have the following data on the subsequent phase(s) of the release
characterization been collected? (V/N)
• New or relocated monitoring locations
• Constituents and indicators added or deleted for monitoring
• Modifications to monitoring frequency, equipment
or procedures
• Concentratior s of constituents and locations at which
they were detected
• Background monitoring results
• Hydrologic and biomonitonng results
• Inter-media transfer data
• Analyses of rate and extent of contamination
13-70
-------
13.8 References
American Public Wealth Association, (APHA). 1985. Standard Methods for the
Examination of Water arid Wastewater . 16th Edition. American Public Health
Association, Washington, DC.
Backiel,T., and R. Welcomme. 1980. Guidelines for Sampling Fish in Inland
Waters . EIFAC Technical Paper No. 33. Food and Agriculture Organization of the
United Nations, Rome, Italy.
Benson, M.A., and T. Dalrymple. 1967. General Field and Office Procedures for
Indirect Discharge Measurement . Techniques of Water Resources Investigations
series. U.S. Geological Survey, Reston, VA.
Bodhaine, G. L. 1968. Measurement of Peak Discharge atCulverts by Indirect
Methods . Techniques of Water Resources Investigations Series. U.S. Geological
Survey, Reston, VA.
Brandes, R., B. Newton, M. Owens, and E. Southertand. 1985. The Technical Support
Document for Water quality-Based Toxics Control . EPA-44014-85-032. Office of
Water Enforcement and Permits. Washington, D.C. 20460.
Buchanan, T. J., and W. P. Somers. 1968. Stage Measurement at Gaging Stations .
Techniques of Water Resources Investigations Series. U.S. Geological Survey,
Reston, VA.
Cairns, J. Jr., and K. L Dickson, eds. 1973. Biological Methods for the Assessment of
Water quality (SIP 528) . American Society for Testing and Materials,
Philadelphia, PA.
Callahan, M., M. Slimak, N. Gabel, I. May, et al. Water-Related Environmental
Fate of 129 Priority Pollutants. Volumes I & II . EPA 440/4.79-029a/b. Monitoring
and Data Support Division. NTIS 029A/80-204373 and 0298/80-
204381 .Washington, DC 20460.
13-71
-------
Carter, R. W., and J. Davidian. 1968. General Procedure for Gaging Streams .
Techniques of Water Resources Investigations Series. U.S. Geological Survey,
Reston, VA.
Chow, V. T. 1964. Open-Channel Hydraulics . McGraw-Hill. New York, NY.
Cole, G. A. 1975. Textbook of Limnology . The C. V. Mosby Company, St. Louis, MO.
Cowardin, L. M., V. Carter, F. C. Golet, and E. T. LaRoe. 1979. Classification of
Wetlands and Deepwater Habitats of the United States . U.S. Fish & Wildlife
Service. NTIS PB 80-168784. Washington, D.C.
Cummins, K. W. and N. A. Wilgbach. 1985. Field Procedures for Analysis of
Functional Feeding Groups of Stream Macroinvertebrates . Contribution 1611.
Appalachian Environmental Laboratory, University of Maryland.
Hilsenhoff,W. 1.. 1982. Using a Biotic Index to
Technical Bulletin No. 132. Department of Natural Resources. Madison, WI.
Homing, W., and C. I. Weber. 1985. Methods for Measuring the Chronic Toxicity of
Effluents to Aquatic Organisms . U.S. EPA, Office of Research and Development.
Cincinnati, OH.
Hutchinson, G. E. 1957. A Treatise on Limnology: Volume I , Geography. Physics.
and Chemistry . John Wiley & Sons, Inc. New York, NY.
Hutchinson, G. E. 1967. A Treatise on Limnology: Volume II. Introduction to Lake
Biology and Limnoplankton . John Wiley & Sons, Inc. New York, NY.
Hynes, H. B. N. 1970. The Ecology of Running Waters . University of Toronto
Press. Toronto, Ontario.
Lyman, W. J., W. F. Riehi, and D. H. Rosenbaltt. 1982. Handbook of Chemical
Property Estimation Methods . McGraw-Hill. New York, NY.
13-72
-------
Mabey, W., and T. Mill. 1978. CritiCal Review of Hydrolysis of Organic Compounds
in Water Under Environmental ConditiOflS.N Journal of Environmental
ChemiSt . VoL.7, No.2.
Mabey, W. R., J. H Smith, R. T. Podall, et al. 1982. Aquatic Fate Process Data for
9 aanic Priority Pollutafi . EPA 440/4-81-014. Washington 9 D.C. 20460.
Mills, W. B.. 1985. Water Quality Assessment: A Screening Procedure for Toxic
and Conventional Pollutants Ifl Surface and Ground Water: Parts 1, 2 andJ . EPA
600/6.85-002. a.b.c. NTIS PB 83.153122 and NTIS PB 83-153130. U.S. EPA. Office
of Research and Development. Athens, GA.
National Oceanic and Atmospheric Administration. Rainfall Atlas of the U.S .
Neely,W. B. 1982. The Definition and 5 fMixiflgZot e5 ”. Environ. Sci.TechflQi .
16(9):520A -521A.
Neely, W. G., and G. E. Blau, eds. 1985. Environmental Exposure from Chemicals 1
Volumel . CRC Press. Boca Raton, FL
Nielsen, L. A., and 0. L. Johnson, eds. 1983. FisherieS TechnQue . The American
Fisheries Society. 3lacksburg, VA, 468 pp.
Peltier, W. H., and C. i.Weber. 1985. MethodS for Measurifla the Acute TOXiCitYQ !
Effluents to Freshwater and Marine OraaniS!!1S . EPA 600/4.85/0 13. NTIS PB 85-
205383. U.S.EPA. Environmental Monitoring and Support LaboratOfY. Office of
Research and Development Cincinnati, OH.
Stumm, W. and i. J. Morgan. 1982. guatic Chemist!Y . 2nd Edition. Wiley
Interscieflce. New York, NY.
Tetra Tech. 1983. Protocol for BioassesSmeflt of Hazardous Waste Sites . U.S.
EPA. NTIS PB 83-241737. Washington 9 D.C. 20460.
13-73
-------
U.S. Department Of Interior. 1981. Water Measurement Manual .
Bureau of Reclamation. GPO No.024-003-00158.9. Washington, DC.
U.S. EPA. 1973. Biological Field and Laboratory Methods for Measuring the Quality
of Surface Water and Effluents . EPA-67014-73.OO1. Office of Research and
Development. Washington, D.C. 20460.
U.S. EPA. 1982. Handbook for Sampling and Sample Preservation of Water and
Wastewater . Environmental Monitoring and Support Laboratory. EPA-600/4-82-
029. NTIS PB 83-124503. Washington, D.C.
U.S. EPA. 1984. Characterization of Hazardous Waste Sites- A Wetlands Manual-
Volume II -Available Sampling Methods . EPA-600/4-84-076. NTIS PB 85-168771.
Washington, D.C. 20460.
U.S. EPA. 1984. Selected Bibliography on the Toxicology of the Benthic
Invertebrates and Periphyton . Environmental Monitoring and Support
Laboratory. NTIS PB 84-130459.
U.S. EPA. 1985. Methods Manual for Bottom Sediment Sample Collection .
NTIS P8107414. Washington, D.C. 20460.
U.S. EPA. 1986. Draft Superfund Exposure Assessment Manual . Office of
Emergency and Remedial Response. Washington, D.C. 20460.
U.S. EPA. 1986. Methods for Evaluating Solid Waste . EPA/SW-846. GPO No.
955-001-00000-1. Office of Solid Waste. Washington, D.C. 20460.
U.S. EPA. 1986. Handbook of Stream Sampling for Wasteload
Allocation ApDlications . EPAi625/6-83/O 13.
USGS. 1977. National Handbook of Recommended Methods for Water-Data
Acguisitjon . U.S. Geological Survey. Office of Water Data Coordination. U.S.
Government Printing Office. Washington, D.C.
13-74
-------
‘Veith, G., Macey, Petrocelli and CarrolL 1980. An Evaluation of Using Partition
Coefficients and Water Solubility to Estimate Biological Concentration Factors
for Organic Chemicals in Fish . Proceedings, ASTM 3rd Symposium on Aquatic
Toxicity. ASTM SIP 707.
Viessman, W., ii ’., W. Knapp. G. L. Lewis, and I. E. Harbaugh. 1977. Introduction
to Hydrology . 2nd Edition. Harper and Row, Publishers, New York, NY.
13-75
-------
APPENDIX E
THE EMISSION ISOLATION FLUX CHAMBER
E- 1
-------
APPENDIX E
THE EMISSION ISOLATION FLUX CHAMBER
GENERAL DESCRIPTION
The Emission Isolation Flux Chamber technique is a direct approach that uses an
enclosure device (flux chamber) to sample gaseous emissions from a defined surface
area. Clean, dry sweep air is added to the chamber at a fixed controlled rate. The
volumetric flow rate of sweep air through the chamber is recorded and the
concentration of the species of interest is measured at the exit of the chamber. The
emission rate is expressed as:
CR/A (Equation 1)
where, E 1 emission rate of component i, lb/ft2.sec
C concentration of component i in the air flowing from the chamber,
I bift3
R flow rate of air through the chamber, ft 3 /sec
A surface area enclosed by the chamber, ft2
All parameters in Equation 1 are measured directly. The general reference for use
of this device is:
U.S. EPA, 1986. Measurement of Gaseous Emissions Rates from Land Surfaces
Using an Emissions Isolation Flux Chamber: Users Guide . EPA 600/8-86-008. NTIS
PB 86-223161. Washington, D.C. 20460.
A diagram of the flux chamber apparatus is shown in Figure E-1. The sampling
equipment consists of a stainless steel/acrylic chamber with impeller, ultra-high
purity sweep air and rotameter for measuring flow into the chamber, and a
sampling manifold for monitoring and/or collection of the specie(s) of interest.
E2
-------
I EMPIEI AIIIIIL
IILAI OUI
SAUPI L COIl tCIION
ANDSOII ANALYSIS
flC MO1OR
ONIOFI 110W
CON 11 101
GRAD SAMI’LE
Poll,
GAS
FXIC.S ASS
$6•
‘ :3
I
U
Figure E-1. Surface Flux Chamber and Peripheral Equipment
-------
Concentrations of total hydrocarbons are monitored Continuously in the
chamber outlet gas stream using portable FID- and/or PID-based analyzers. Samples
are collected for subsequent GC analysis once a steady-state emission rate is
obtained. Air and soil/liquid temperatures are measured using a thermocouple. The
system pressureis monitored using a Magnahelic pressure gauge.
ANALYTICAL METHODS
The analytical systems generally used during surface flux chamber sampling are
real-time monitors, portable gas chromatographs, and off-site gas chromatographs.
Each is described below.
• Real-time monitors - These are used to determine when steady-state
conditions have been reached and when syringe sampling can be initiated.
The instruments used are a PID with a range of 0.1-2000 ppmv and an FID
with a range of 1-10,000 ppmv. Generally speaking, the PlO shows a better
response to aromatic species and the FID to aliphatic species. Based upon
the real-time monitor data, the sweep air flow rate is adjusted to achieve
the desired concentration range for GC analysis.
• Portable Gas Chromatograph - Once steady state had been reached and
verified in the flux chambers, a grab sample is collected in a glass gas- tight
syringe from the chamber exit line. The samples are shielded from light
and analyzed generally within 30 mm. The GC used is equipped with a PlO
or FID. A packed capillary column is operated isothermally.
• Off-Site Gas Chromatograph - Gas samples are collected in evacuated
stainless steel canisters and shipped to the laboratory for detailed analysis.
Th. canisters are then pressurized with ultra high purity nitrogen to
provide positive pressure for removing the sample for analysis and to dilute
oxygen and moisture in the sample to minimize component reactions. The
analytical system used is the same GCIFIO, PID system. If necessary, aliquots
of the gas canister samples can be analyzed by gas chromatography/mass
spectrometry (GCIMS) to verifythe species identifications.
E -4
-------
METHOD EVALUATiON
Some of the advantages of the flux chamber technique include:
• The soil and any associated emission processes are undisturbed;
• Sampling is rapid, normally requiring 1/2 hr per sampling point;
• The technique is suited to most soil types;
• The sampling equipment used is fairly simple and widely available; and
• The sampling technique’s accuracy and precision iswell documented.
Disadvantages of the flux chamber technique include:
• The sweep air dilutes the gas sample and therefore decreases the method’s
sensitivity;
• The flux chamber sampling technique has a measurable effect on the
emission rate being measured;
• Gas concentrations at the surface are normally lower than at subsurface
sampling locations;
• The technique functions poorly when the soil being sampled is saturated
with water and gas transport pathways are blocked; and
• Sites with caliche or other semi-impermeable soil strata may be unsuited
for sampling by this method.
E-5
------- |