&EPA
United States Industrial Environmental Research EPA-600/7-79-029a
Environmental Protection Laboratory January 1979
Agency Research Triangle Park NC 27711
Emissions Assessment
of Conventional Stationary
Combustion Systems:
Methods and Procedures
Manual for Sampling
and Analysis
Interagency
Energy/Environment
R&D Program Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy /Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-79-029a
January 1979
Emissions Assessment of Conventional
Stationary Combustion Systems:
Methods and Procedures Manual
for Sampling and Analysis
by
J.W. Hamersma, D.G. Acker man, M.M. Yamada, C.A. Zee,
C.Y. Ung, K.T. McGregor, J.F. Clausen,
M.L Kraft, J.S. Shipiro, and E.L Moon
TRW Systems Group
One Space Park
Redondo Beach, California 90278
Contract No. 68-02-2197
Program Element No. EHB525
EPA Project Officer: Ronald A. Venezia
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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ABSTRACT
This manual describes a detailed and integrated set of sampling
and analytical procedures for conventional combustion sources which are
compatible with the information requirements of a comprehensive Level 1
environmental assessment. The purpose of the data to be generated by
these tests is to ultimately provide emission factors for conventional
stationary combustion sources.
This is the first detailed application of Level 1 procedures to all
phases (sampling, sample handling, disbursement, and analysis) of a
specific program. Although this manual has been designed to meet the
exact data needs of this program, the procedures have general appli-
cability to most environmental assessment activities. Specific chapters
are included for quality assurance, sample and data management, field
sampling, field analysis, organic analysis, and inorganic analysis.
11
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PREFACE
This procedures manual has been prepared for the Industrial and Environ-
mental Research Laboratory, Chemical Processes Branch, Research Triangle Park,
North Carolina, as required by EPA Contract 68-02-2179 for Emissions Assess-
ment of Conventional Combustion Systems. Dr. Ron Venezia is the Project
Officer at CPB and Mr. Birch Matthews is Program Manager at TRW.
The manual was originally designed to be an internal working document
for TRW and its subcontractors. However, because 1t is the first detailed
application of Level 1 procedures on a specific program requiring the sampl-
ing of a large number of sites and analysis of a large number of samples,
it was decided to publish it as an official EPA document. This process
required the interpretation of sometimes conflicting requirements and the
addition of procedural details not supplied in the Level 1 manual. In some
cases, development work was performed to reduce the procedures to practice.
Some of this work has been Incorporated Into the revised Level 1 manual and
some remains specific to this program. These changes are documented 1n
detail 1n the latter part of this section.
The objective of this project is to assess air and water pollutants
generated by conventional stationary combustion systems including those
pollutants generated from related solid waste disposal. The final assess-
ment will be based upon appropriate existing emissions data as well as new
data acquired through source sampling and analysis. To accomplish this
objective, the project scope of work Includes the following activities:
1) Define criteria for determining the adequacy of existing emission
data.
2) Identify emission source categories or category portions which
have been adequately assessed based upon the developed criteria.
3) Specify those source categories that require additional Investiga-
tion.
4) Develop a test program to complete the emissions assessment.
5) Implement the test program and complete the emissions assessment.
The procedures are designed to be an integral part of the phased
environmental assessment approach and apply primarily to Level 1. The
purpose of the initial phase is to obtain preliminary environmental assess-
ment information, identify problem areas and provide the basis for the
prioritlzatlon of streams, components and classes of materials for further
111
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testing by more stringent techniques and procedures. As such, the results
of the sampling and of the corresponding analysis procedures are quantita-
tive within a factor of +_ 2 to 3. A detailed discussion of the approach
along with the criteria used for method selection is given in the IERL-RTP
Document # EPA-600/2-76-160a, IERL Procedures Manual; Level 1, Environ-
mental Assessment, which has been the guideline for preparation of this
document and by reference, is made an integral part of it.
Level 2 sampling and analysis has not been systematically addressed in
the manual because it 1s impossible to predict how the Level 1 results of
this program will affect the need for Level 2 analysis. Consequently, Level
2 sampling and analysis plans will be submitted as these requirements are
made known. In the cases of polynuclear aromatic hydrocarbons (POM), and
sulfate compound determinations, Level 2 needs are presently delineated
and consequently procedures are included for sampling and analysis of these
materials.
The manual has been designed to fit the specific sampling and analysis
requirements for this program although it 1s recognized that the procedures
are general enough to be modified easily for EPA activities relating to
other emission sources. In order to avoid confusion, project related
deviations are listed 1n Table 1. In addition to these, revisions have
been made during the course of the program to reflect experience, changing
data needs and EPA directed Level 1 changes. These are listed in Table ii.
1v
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Table i. Program Related Additions and/or Deletions to Level 1 Procedures
Parameter/Analysis
of Interest
Polynuclear Organic
Material
Polychlorinated
Biphenyls
Controlled Condensation
System (CCS)
Bacharach Smoke Spot
Test
Cyclone Deletion
Guidelines
Duty Cycle Testing
Chloride and Fluoride
BOD and COD
Fugitive Emission
Studies
Speciation in
Bulk TCO Analysis
Parr Bomb Combustion
Hg, As, Sb Wet Chemical
Analysis
Mater Sampling and
Analysis
Ash Sampling and
Analysis
Computation of Inor-
ganic Emissions from
Oil and Gas Fired Units
Deletion of SASS
Inorganic Analysis on
Gas and 011 Fired Sites
Combination of all
Organic Samples for a
Change and Reason Section Number
Added as program requirement.
Added as program requirement, deleted from this revision because of uniformly negative
results on other programs.
Added to obtain particulate sulfate, aerosol H.SO-, and SO- information unavailable from
Level 1 procedures.
Added as program requirement.
Added to save leak check and clean-up time in field when previous data indicates a cyclone
catch will be nil. Updated to increase capability with EPA's fine particulate data
bank In September, 1978.
Added to answer questions on the effect of the duty cycle and emissions level in residential
sources.
Added - these elements are often difficult to analyze by SSMS, A set of analysis was
developed to check SSMS data in selected cases.
Dropped for cooling and ash quenching stream because of known promlems in interpreting results.
Reduced because sufficient data input is being generated by other EPA programs.
Added to provide data concerning individual C7-C1g species for OAQPS
Modified by addition of a quartz liner to reduce blanks. Accepted as official Level 1 change.
Modified or method changed when reduced to practice. All changes accepted as official Level 1
changes.
Reduced to fit actual data needs of program. Directed change June, 1978.
Reduced to fit actual data needs of program. Directed Change June, 1978.
Modified to assume that inorganic emissions are nil from gas fired sites and to assume that all
inorganics in fuel are emitted from the stack. Directed change June, 1978.
Deleted because very low particulate loadings did not give technically acceptable results.
Directed change June, 1978.
Modified so that the XAD-2 extract and all rinses are combined into a single sample because of
very low levels of organics in all samples except XAD-2 extract. Directed chance
3.4.2
7.10
3.4.1
3.3.3
5.6
8.8
6.7
3.3.1
5.2.8
3.3.2
3.4.3
8.9
8.10
3.4.6
7.7
8.2.1
8.4
8.5
8.6
3.8
3.9
7.1
8.1
3.9
7.1
8.1
3.9
7.1
Single Analysis for Oil
and Gas Fired Site
Inorganic (Field) Gas
Analysis
June, 1978.
Modified to a two column Molecular Sieve 13X and Chromosorb 102 system so that all species of
interest can be analyzed properly.
6.2
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Table ii. Modification and EPA Directed Changes to Level 1 Procedures.
Parameter/ Ana lys i s
of Interest
Field Analysis for
Gaseous Species
Impingers
Probe, Cyclone, and
XAD-2 Module Rinses
SASS Train Passivation
Procedure
First H-O- Impinger
NOX Analysis
As and Sb Analysis
SSMS Analysis
Slurry Sampling
Total Chroma tographable
Organics (TCO)
Liquid Chromatography (LC)
Liquid Chromatography
XAD-2 Nodule Condensate
Batch LRMS on LC
Fractions
Change and Reason
Original Level 1 procedures still in use.
The use of isopropyl alcohol to wash out impinger bottles was dropped because excessive
amounts sometimes interfered with AA analysis.
Acetone was substituted for methanol because water could not be removed from methanol
easily and TCO loss during concentration.
Changed to a 15Z HMO, soak for 30 minutes to reduce SASS train corrosion.
Official Level 1 change.
H,02 content reduced for sites using low sulfur fuel to save reagent and reduce analysis
pfool em
Changed to EPA Method 7 because NO deteriorates in bag used to take and transport sample
for analysis.
Wet methods deleted, SSMS method of choice.
Completely revised to reflect program experience.
Procedure modified to reflect EPA Level 1 change. No samples taken by old method
Dropped for all SASS train samples except XAD-2 resin extract and condensate extract.
EPA Level 1 change.
Dropped Fraction 8. EPA Level 1 change.
Original Level 1 procedure retained when TCO is less than 102 of total organics.
Sample not analyzed if it is less than 10* of the organics in the XAD-2 extract. Only
acid extraction performed.
Official EPA change not implemented becasue of cost impact and the procedure was not in
original scope of work. Original Level 1 criteria retained.
Date
8/77
9/77
6/77
6/77
8/78
6/78
9/78
6/78
8/78
7/77
7/77
7/77
7/77
Section
Number
6.2
5.2.11
5.2.11
5.2.6
5.9
5.3.4
6.4
8.11
8.1
8.3
5.4
3.7.1
7.2
7.7
7.8
7.2
7.8
3.7.1
7.2
3.6
7.2
3.6
7.2
7.9
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CONTENTS
Page
1.0 INTRODUCTION 1-1
1.1 General Information 1-1
1.2 Multimedia Sampling Procedures 1-3
1.2.1 Classification of Streams for
Sampling Purposes 1-3
1.3 Analysis of Samples 1-7
2.0 QUALITY ASSURANCE 2-1
2.1 Purpose 2-1
2.2 Quality Policies 2-1
2.3 Quality Objectives 2-2
2.4 Organization 2-2
2.5 QA Tasks 2-4
2.5.1 Indoctrination and Training 2-4
2.5.2 Procedure Review and Approval 2-4
2.5.3 Sample Identification and Traceability 2-6
2.5.4 Quality Control 2-7
2.5.5 Computation and Data Reporting 2-9
2.5.6 Auditing 2-10
2.5.7 Discrepancies 2-14
2.5.8 Quality Assurance Reporting and Documentation. . . . 2-14
2.6 Guidelines for Implementation of QA 2-16
2.6.1 Applicability 2-16
2.6.2 Level 1 Quality Assurance Activities 2-16
2.6.3 Minimum Number of "Blank" Tests Acceptable
for Level 1 Tests 2-17
2.6.4 Minimum Number of Replicate Tests for Level 1. . . .2-18
2.6.5 Decision Plan for Number of Replicate Tests 2-20
3.0 SAMPLING AND ANALYSIS DECISION CRITERIA 3-1
3.1 Introduction 3-1
3.2 Requirement of Planning and Assessment Task 3-1
3.3 Field Sampling and Analysis Decision Criteria 3-2
3.3.1 SASS Train Cyclone Deletion Guidelines 3-2
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CONTENTS - Continued
3.3.2 Special Procedures for Home Heating Units 3-7
3.3.3 S03/S02 Measurements 3-7
3.4 Special Case Analysis Plan 3-7
3.4.1 Polychlorinated Biphenyls (PCB) 3-10
3.4.2 Polynuclear Organic Material (POM) 3-10
3.4.3 Chloride and Fluoride Analysis 3-10
3.4.4 Water Quality Tests 3-11
3.4.5 Special Inorganic Compound Identification Studies. . 3-11
3.4.6 Fugitive Emission Studies 3-12
3.4.7 Fuel Feed Analysis 3-12
3.5 Analysis Criteria for Limited Quantities of
Particulate Samples 3-12
3.6 Analysis Criteria for XAD-2 Module Samples 3-15
3.7 Planning and Analysis Criteria for Organic Components . . . 3-15
3.7.1 General Organic Decision Criteria 3-15
3.7.2 Prediction of Quantity of Organic Material in
Particulate Catches 3-20
3.8 Water Sampling and Analysis Protocol 3-20
3.8.1 Sampling Wastewater Emissions 3-20
3.8.2 Analysis 3-23
3.9 Special Analysis Criteria for Gas, Distillate Oil and
Residual Oil Combustion Sources 3-25
3.10 References 3-26
4.0 SAMPLE AND DATA MANAGEMENT 4-1
4.1 Sample Management 4-1
4.1.1 Sample Receiving 4-1
4.1.2 Sample Bank and Storage 4-3
4.1.3 Sample Disbursement 4-5
4.1.4 Sample Coding 4-11
4.1.5 Sample Tracking 4-11
4.1.6 Sample Retainment 4-13
4.2 Data Management 4-19
4.2.1 Data Recording 4-19
4.2.2 Data Reduction 4-19
viii
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CONTENTS - Continued
Page
4.2.3 Data Review 4-19
5.0 FIELD SAMPLING 5-1
5.1 Introduction 5-1
5,2 Sampling in Particulate Laden Streams 5-2
5.2.1 Scope and Application 5-2
5.2.2 Summary of Method 5-2
5.2.3 Definitions 5-2
5.2.4 Apparatus: The SASS Train 5-2
5.2.5 Reagents: ACS Reagent Grade or Better Quality. . . 5-4
5.2.6 Sample Collection 5-5
5.2.7 Pre-Test Checkout Operations 5-8
5.2.8 SASS Train Cyclone Deletion Guidelines 5-10
5.2.9 Sample Acquisition 5-13
5.2.10 Filter Changing and Transfer 5-29
5.2.11 Sample Handling and Transfer 5-29
5.2.12 Plume Opacity Tests 5-34
5.3 Gas Sampling 5-35
5.3.1 Method 1 5-35
5.3.2 Method II 5-36
5.3.3 Reagents 5-36
5.3.4 Sampling Procedure 5-36
5.4 Liquid and Slurry Sampling 5-40
5.4.1 Scope and Application 5-40
5.4.2 Summary of Methods and General Considerations . . . 5-40
5.4.3 Apparatus 5-41
5.4.4 Reagents 5-42
5.4.5 Equipment Preparation 5-42
5.4.6 Sampling Procedures 5-43
5.4.7 Sample Handling and Shipment. . 5-46
5.5 Solids Sampling 5-50
5.5.1 Scope and Application 5-50
5.5.2 Summary of Methodologies 5-50
ix
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CONTENTS - Continued
5.5,3 Apparatus 5-50
5.5.4 Reagents 5-50
5.5.5 Procedures 5-50
5.6 Controlled Condensation System (CCS) 5-52
5.6.1 Scope and Application 5-52
5.6.2 Reagents 5-52
5.6.3 System Design 5-52
5.6.4 Preparation 5-52
5.6.5 Sampling 5-52
5.6.6 Sample Recovery 5-55
6.0 FIELD ANALYSIS
6.1 Introduction 6-1
6.2 Field Gas Chromatographlc Analyses 6-1
6.2.1 Scope and Application 6-1
6.2.2 Summary of Method 6-2
6.2.3 Definitions 6-2
6.2.4 Sample Handling and Preservation 6-2
6.2.5 Apparatus 6-2
6.2.6 Reagents. 6-4
6.2.7 Procedure - Cl to Cs Analysis 6-4
6.2.8 Calculations - Cl to Cs Hydrocarbons 6-6
6.2,9 Procedure - Inorganic Gases 6-7
6.2.10 Calculations - Inorganic Gases 6-8
6.2.11 Checking the Gas Sample Valve for Cleanliness ... 6-9
6.2.12 Precision and Accuracy 6-9
6.3 NOX Analysis - Chemlluminescence Measurement
on Gas Bag Sample 6-10
6.3.1 Scope and Applications 6-10
6.3.2 Summary of Method 6-10
6.3.3 Interferences 6-10
6.3.4 Apparatus 6-10
6.3.5 Reagents 6-10
6.3.6 Procedure 6-10
x
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CONTENTS - Continued
Page
6.3.7 Accuracy and Precision 6-10
6.4 NOX Analysis - EPA Method 7 6-11
6.4.1 Scope and Application 6-11
6.4.2 Summary of Method 6-11
6.4.3 Interferences 6-11
6.4.4 Apparatus, Reagents, and Procedures 6-11
6.5 Water Analysis 6-12
6.5.1 Acidity 6-12
6.5.2 Alkalinity 6-15
6.5.3 Specific Conductance 6-19
6.5.4 Total Suspended Solids (TSS) 6-22
6.5.5 Hardness 6-23
6.5.6 pH 6-26
6.5.7 Nitrate Nitrogen 6-27
6.5.8 Phosphate, Total Organic and Inorganic 6-29
6.5.9 Sulfite Analysis 6-34
6.5.10 Sulfate 6-36
6.5.11 Cyanide, Free 6-39
6.5.12 Ammonia Nitrogen 6-42
6.6 Opacity Measurements (Modified by EPA Method 9) 6-49
6.6.1 Scope and Application 6-49
6.6.2 Procedure 6-49
6.6.3 Calculations 6-52
6.6.4 Accuracy and Precision 6-52
6.7 Bacharach Smoke Spot Test 6-52
6.7.1 Procedure 6-53
6.7,2 Comments 6-53
6.7.3 Precision and Accuracy 6-56
7.0 ORGANIC ANALYSIS PROCEDURES 7-1
7.1 Introduction 7-1
7.2 Level 1 Organic Analysis Methodology. . 7-1
7.3 Extraction of Samples for Organlcs 7-6
7.3.1 Extraction of Aqueous Samples for Organlcs 7-6
x1
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CONTENTS - Continued
Page
7.3.2 Extraction of Solid Samples for Organics 7-8
7.3.3 Combination of SASS Train Samples 7_n
7.4 Concentration of Organic Extracts 7-11
7.4.1 Scope and Application 7_11
7.4.2 Summary of Method 7_TI
7.4.3 Definitions 7_12
7.4.4 Sample Handling 7_12
7.4.5 Apparatus 7_12
7.4.6 Reagents 7_-]2
7.4.7 Procedure 7_12
7.5 Gravimetric Determinations for Organics 7-14
7.5.1 Scope and Application 7.14
7.5.2 Summary of Method 7_14
7.5.3 Sample Handling 7_14
7.5.4 Apparatus 7_14
7.5.5 Reagents 7_14
7.5.6 Procedure 7_15
7.5.7 Calculations 7_15
7.6 Infrared Analysis 7_15
7.6.1 Scope and Application 7.16
7.6.2 Summary of Method 7_16
7.6.3 Definitions 7_17
7.6.4 Sample Handling and Preservation 7-17
7.6.5 Apparatus 7_13
7.6.6 Reagents 7_lg
7.6.7 Procedure 7_13
7.6.8 Calculations 7_22
7.6.9 Accuracy and Precision 7_22
7.7 C7-C16 Total Chromatographable Organic
Material Analysis 7_22
7.7.1 Scope and Application 7_22
7.7.2 Summary of Method 7_24
7.7.3 Definitions 7.24
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CONTENTS - Continued
7.7.4 Sample Handling and Preservation 7-24
7.7.5 Apparatus 7-25
7.7.6 Reagents 7-26
7.7.7 Procedures 7-26
7.7.8 Sample Analysis Decision Criterion 7-30
7.7.9 Calculations 7-30
7.8 Liquid Chromatographic Separations 7-36
7.8.1 Scope and Application 7-36
7.8.2 Summary of Method 7-37
7.8.3 Definitions 7-37
7.8.4 Sample Handling and Preservation 7-37
7.8.5 Apparatus 7-37
7.8.6 Reagents 7-38
7.8.7 Decision Criteria for Technique to be Used in
Performing LC Separations 7-38
7.8.8 Procedure 7-39
7.8.9 Calculations 7-43
7.9 Low Resolution Mass Spectrometric Analysis 7-44
7.9.1 Scope and Application 7-44
7.9.2 Summary of Method 7-44
7.9.3 Definitions 7-45
7.9.4 Sample Handling and Preservation 7-45
7.9.5 Apparatus 7-45
7.9.6 Reagents 7-46
7.9.7 Procedure 7-46
7.9.8 Data Interruption 7-48
7.9.9 Quantisation of Results 7-50
7.10 Polynuclear Organic Compound Analysis by Gas
Chromatography/Mass Spectrometry 7-50
7.10.1 Scope and Application 7-50
7.10.2 Summary of Method 7-51
7.10.3 Definitions 7-51
7.10.4 Sample Handling and Preservation 7-52
/
xlii
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CONTENTS - Continued
Page
7.10.5 Apparatus 7-52
7.10.6 Reagents 7-53
7.10.7 Procedure 7-54
7.10.8 Data Processing and POM Quantification 7-57
8.0 INORGANIC ANALYSIS PROCEDURES 8-1
8.1 Introduction 8-1
8.2 Sample Preparation 8-5
8.2.1 Parr Bomb Combustion 8-5
8.2.2 Aqua Regia Digestion 8-7
8.2.3 XAD-2 Resin Acid Extraction 8-8
8.2.4 Condensate, XAD-2 Module Wash, XAD-2 Resin
Extract, and \\2$2 Impinger Composite (Pending). . . 8-11
8.3 Spark Source Mass Spectrographic Analysis 8-11
8.3.1 Scope and Application 8-11
8.3.2 Summary of Method 8-11
8.3.3 Apparatus 8-14
8.3.4 Reagents 8-17
8.3.5 Procedures 8-18
8.3.6 Calculations 8-24
8.3.7 Precision and Accuracy 8-26
8.3.8 References 8-27
8.4 Mercury Analysis 8-28
8.4.1 Scope and Application 8-28
8.4.2 Summary of Method 8-28
8.4.3 Apparatus 8-28
8.4.4 Reagents 8-29
8.4.5 Procedure 8-30
8.4.6 Calculation 8-31
8.4.7 Precision and Accuracy 8-32
8.5 Arsenic Analysis 8-32
8.5.1 Scope and Application 8-32
8.5.2 Summary of Method 8-32
8.5.3 Apparatus 8-32
xiv
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CONTENTS - Continued
8.5.4 Reagents 8-33
8.5.5 Procedures 8-34
8.5.6 Calculations 8-35
8.5.7 Precision and Accuracy 8-35
8.6 Antimony Analysis 8-36
8.6.1 Scope and Application 8-36
8.6.2 Summary of Method 8-36
8.6.3 Apparatus 8-36
8.6.4 Reagents 8-37
8.6.5 Procedure 8-37
8.6.6 Calculations 8-39
8.7 Sulfate Analysis 8-40
8.7.1 Scope and Application 8-40
8.7.2 Summary of Method. 8-40
8.7.3 Apparatus 8-40
8.7.4 Reagents 8-41
8.7.5 Procedure 8-41
8.7.6 Calculation 8-42
8.8 Controlled Condensation Sampling Train (CCS) - Sample
Preparation and Analysis 8-43
8.8.1 Hot Water Extraction 8-43
8.8.2 Hot HC1 Extraction 8-45
8.8.3 Sulfurlc Add Analysis - Level 2 Analysis of
CCS Coil Sample 8-45
8.9 Fluoride Analysis 8-50
8.9.1 Scope and Application 8-50
8.9.2 Summary of Method 8-51
8.9.3 Apparatus 8-51
8,9.4 Reagents 8-52
8.9.5 Procedure 8-52
8.9.6 Calculations 8-54
8.10 Chloride Analysis 8-57
8.10.1 Scope and Application 8-57
8.10.2 Summary of Method 8-57
xv
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CONTENTS - Continued
Page
8.10.3 Apparatus 8-57
8.10,4 Reagents 8-58
8.10.5 Procedure 8-58
8.10.6 Calculations 8-59
8.11 Phenodisulfonic Acid Procedure for Determination
of Nitrogen Oxides (EPA Method 7) 8-62
8.11.1 Scope 8-62
8.11.2 Apparatus 8-63
8.11.3 Reagents 8-64
8.11.4 Procedure 8-65
8.11.5 Calibration 8-66
8.11.6 Calculations 8-66
APPENDIX A - Criteria for a Cost-Effective Level 1 Quality
Assurance Program A-l
APPENDIX B - Analytical Traveler Worksheets B-l
APPENDIX C - Standard EPA Gas Sampling Methods C-l
APPENDIX D - Procedure for Coning and Quartering Samples D-l
APPENDIX E - XAD-2 Resin Cleaning Procedure E-l
APPENDIX F - Schematic of TRW Sampling Van F-l
xv i
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LIST OF FIGURES
Figure Page
1-1 Multimedia Sampling Approach Overview 1-4
1-2 Basic Level 1 Sampling and Analytical Scheme
for Particulates and Gases 1-5
1-3 Basic Level 1 Sampling and Analytical Scheme
for Solids, Slurries and Liquids 1-6
2-1 Function Diagram for Quality Assurance 2-3
2-2 Training Activity Associated with Each Procedure 2-4
2-3 QA Function Relative to Procedures 2-5
2-4 QA Activities for the Sample Bank 2-6
2-5 Quality Control Operations to be Emphasized in
this Program 2-7
2-6 Activities in the Quality Data Validation
and Assessment Program 2-10
2-7 QA Audit Approach 2-12
2-8 Activities of QA Relative to Discrepancies 2-15
2-9 Decision Plan Describes the Action Needed
to Identify the Need for Replication 2-20
2-10 Decision Criterion for Application of
Laboratory Tests . . 2-23
3-1 Particulate Analysis Prediction Nomograph 3-4
3-2 Source Type and Complexity Classification to
Level 1 Sampling and Analysis 3-8
3-3 Special Case Analysis Plan 3-9
3-4 Particulate Analysis Decision Criteria
for Coal Fired Systems 3-13
3-5 XAD-2 Module Analysis Decision Criteria
for Oil Fired Systems , 3-14
3-6 XAD-2 Module Organic Analysis Decision
Criteria 3-16
3-7 XAD-2 Module Inorganic Analysis Decision
Criteria 3-17
3-8 XAD-2 Module Inorganic Analysis Decision
Criteria Pending EPA Approval 3-18
xvil
-------
LIST OF FIGURES
(Continued)
Figure Page
4-1 Sample Receiving Check List 4-2
4-2 Sample Receiving QC 4-4
4-3 Disbursement 4-6
4-4 EACCS Sample Control Numbers 4-12
4-5 Weekly, Status Report 4-14
4-6 Summary: Weekly Status Report 4-15
4-7 Analytical Schedule Flow Control Chart 4-16
4-8 Analytical Schedule Flow Control Chart
Organic Analysis 4-17
4-9 Analytical Schedule Flow Control Chart
Inorganic Analysis 4-18
5-1 SASS Schematic 5-3
5-2 SASS Cleaning Procedures 5-6
5-3 Particulate Analysis Prediction Nomograph 5-11
5-4 Minimum Number of Traverse Points 5-17
5-5 Example Showing Circular Stack Cross Section
Divided Into 12 Equal Areas, with Location of
Traverse Points at Controld of Each Area 5-19
5-6 Example Showing Rectangular Stack Cross Section
Divided Into 12 Equal Areas, with Traverse
Points at Centrold of Each Area 5-20
5-7 P1tot Tube - Manometer Assembly 5-21
5-8 Standard P1tot Tube 5-23
5-9 Velocity Traverse Data 5-25
5-10 Sample Handling and Transfer-Nozzle,
Probe, Cyclones and Filter 5-31
5-11 Sample Handling and Transfer-XAD-2 Module . . . 5-32
5-12 Sample Handling and Transfer-Implngers 5-33
xvlii
-------
LIST OF FIGURES
(Continued)
Figure Page
5-13 Integrated Gas Sampling Train-Method I 5-35
5-14 Integrated Gas Sampling Train-Method II 5-37
5-15 Method II Steel Drum Top View 5-37
5-16 Decision Matrix for Liquid/Slurry Sampling .... 5-40
5-17 Assembly for Tap Sampling 5-44
5-18 Heat Exchange Sampler 5-45
5-19 Field Handling Scheme for Liquid/Slurry Samples 5-47
5-20 Controlled Condensation System Setup 5-53
5-21 Controlled Condensation Field Data Sheet .... 5-56
5-22 Controlled Condensation Coil Rinsing Apparatus 5-58
6-1 Data Sheet - Acidity 6-44
6-2 Data Sheet - Alkalinity 6-45
6-3 Data Sheet - Conductivity 6-46
6-4 Data Sheet - Hardness 6-47
6-5 Data Sheet - pH 6-48
6-6 Record of Visual Determination of Opacity 6-50
6-7 Observation Record 6-51
6-8 Insertion of Filter Paper Strip into Bacharach
Test Plunger Strip 6-54
6-9 Procedure for Obtaining a Sample Using the
Bacharach Smoke Spot Test Plunger Pump 6-54
6-10 Procedure for Analysis of Smoke Spot on
Bacharach Scale 6-55
7-1 Level 1 Organic Analysis Flow Chart 7-3
7-2 Level 1 Organic Analysis Methodology 7-4
7-3 Standard Polystyrene Film Spectra Showing
Acceptable Resolution 7-21
xlx
-------
LIST OF FIGURES
(Continued)
Figure Page
7-4 Retention Times Versus Normal Boiling
Points for C7-C16 Hydrocarbons 7-31
7-5 Calibration of FID-GC with n-Decane 7-32
7-6 Sample Chromatogram with Retention Times
and Peak Areas Noted 7-34
7-7 Example of a Computer Generated Total
Ion Chromatogram 7-57
8-1 Level 1 Inorganic Analysis Plan (Prior to June 1978). . . . 8-2
8-2 Level 1 Inorganic Analysis Plan (After June 1978) 8-3
8-3 Hydride Evolution Apparatus ,.,.., ... 8-38
8-4 Analysis Scheme for Controlled
Condensation Train Samples 8-44
xx
-------
LIST OF TABLES
Table Page
1-1 Recommended Sample Sizes and Detection Limits 1-8
1-2 List of Analysis Procedures in the Combustion Source
Assessment Methods and Procedures Manual 1-9
3-1 SASS Train Cyclone Use Criteria (Before 1 September 1979) . 3-5
3-2 Expected Application of SASS Train Cyclone Use
Criteria as a Function of Fuel Type (Before 1
September 1979) 3-5
3-3 SASS Train Cyclone Use Criteria (After 1 September 1979). . 3-6
3-4 Expected Application of SASS Train Cyclone Use
Criteria as a Function of Fuel Type (After 1
September 1979) 3-6
3-5 Organic Analysis Decision Points 3-19
3-6 Wastewater Emissions from Stationary Combustion
Sources 3-21
3-7 Liquid Stream Sampling and Analysis Protocol 3-24
5-1 SASS Train Cyclone Use Criteria 5-12
5-2 Expected Application of SASS Train Cyclone as a
Function of Fuel Type 5-12
5-3 SASS Train Impinger System Reagents 5-14
5-4 Location of Traverse Points in Circular Stacks 5-18
5-5 List of Analyses to be Performed on Liquid/
Slurry Samples 5-49
5-6 Cleaning Procedures 5-54
5-7 Sampling Recovery 5-57
6-1 Alkalinity Relationship ..... 6-16
7-1 Instrument Scanning Parameters 7-20
7-2 Specific Ions Used in PAH Data Search 7-58
7-3 Minimum List of POM's Monitored 7-59
xx1
-------
LIST OF TABLES
("Continued)
Table
8-1 Suggested Instrument Conditions for Obtaining
Mass Spectral Data as a Graded Series of Exposures 8-21
8-2 Fluoride Analysis: "Addition Procedure" Table for
Q versus A.E (millivolts) at 25°C for 10% Volume Change . . . 8-55
8-3 Chloride Analysis: "Addition Procedure" Table for
Q versus AE (millivolts) at 25°C for 10% Volume Change . . . 8-60
XX11
-------
ACKNOWLEDGMENTS
This procedure manual has been prepared for the Industrial and
Environmental Research Laboratory, Chemical Processes Branch, Research
Triangle Park, North Carolina, as required by EPA Contract 68-02-2197 for
Emissions Assessment of Conventional Combustion Systems. Dr. Ron Venezia
is the Project Officer at CPB and Mr. Birch Matthews is Program Manager
at TRW.
The Chemistry Department of the Chemistry and Chemical Engineering
Laboratory, Applied Technology Division was responsible for the work
performed on this task,
This manual was prepared under the technical direction of Dr. J.W.
Hamersma of the Chemistry Department. Major technical contributions were
provided by the following individuals from TRW:
D.G. Ackerman M.O'.Rell
R.B. Beimer S. Reynolds
T. Eggleston L.E. Ryan
B. Eisenberg J.S. Shapiro
A. Grant R. Sung
M.L. Kraft C..Y. Ung
D.J. Luciani M.M, Yamada
R.F. Maddalone C.L. Yu
E. Moon C.A. Zee
Acknowledgment is also made to those individuals at GCA under the
direction of Dr. A. Werner who provided technical input:
P. Fennelly L. Oliverio
K. McGregor M. Chillingworth
B. Myatt
Ms. M.M. Yamada and Ms. M. Jennings supervised the preparation and
publication of this report.
xxiii
-------
1.0 INTRODUCTION
1.1 GENERAL INFORMATION
This procedures manual has been prepared for the Industrial and
Environmental Research Laboratory, Chemical Processes Branch, Research
Triangle Park, North Carolina, as required by EPA Contract 68-02-2197 for
Emissions Assessment of Conventional Combustion Systems. Dr. Ron Venezla
is the Project Officer at CPB and Mr. Birch Matthews is Program Manager
at TRW.
The objective of this project is to assess air and water pollutants
generated by conventional stationary combustion systems Including those pol-
lutants generated from related solid waste disposal. The final assessment
will be based upon appropriate existing emissions data as well as new data
acquired through source sampling and analysis. To accomplish this objective,
the project scope of work will Include the following activities:
1) Define criteria for determining the adequacy of existing
emissions data.
2) Identify emission source categories or category portions which
have been adequately assessed based upon the developed criteria.
3) Specify those source categories that require additional
Investigation.
4) Develop a test program to complete the emissions assessment.
5) Implement the test program and complete the emissions
assessment.
The manual describes an Integrated set of sampling and analytical
procedures for conventional combustion sources which are compatible with
the information requirements of a comprehensive Level 1 environmental
assessment. The purpose of the data to be generated by these tests is to
ultimately provide emission factors for conventional stationary combustion
sources.
1-1
-------
The procedures are designed to be an integral part of the phased
environmental assessment approach and apply primarily to Level 1. The
purpose of the initial phase is to obtain preliminary environmental assess-
ment information, identify problem areas and provide the basis for the
prioritization of streams, components and classes of materials for further
testing by more stringent techniques and procedures. As such, the results
of the sampling and of the corresponding analysis procedures are quantita-
tive within a factor of t 2 to 3. A detailed discussion of the approach
along with the criteria used for method selection is given in the IERL-RTP
Document # EPA-600/2-76-160a, IERL Procedures Manual: Level 1. Environmental
Assessment, which has been the guideline for preparation of this document
and by reference, is made an integral part of it.
The manual has been designed to fit the specific sampling and analysis
requirements for this program although it is recognized that the procedures
are general enough to be modified easily for EPA activities relating to
other emission sources. Recognizing that the document is being issued after
the initial phase of the program, minor to substantive revisions will be
necessary to some procedures as data and experience are gained and as program
needs change which would require adapting methods. Thus, it is anticipated
that a review and revision process will take place continually during the
remainder of the program. Revisions will be documented and controlled 1n
accordance with a standard TRW document control system described 1n the
QA section.
Level 2 sampling and analysis has not been systematically addressed
in the manual because it is impossible to predict how the Level 1 results
of this program will affect the need for Level 2 analysis. Consequently,
Level 2 sampling and analysis plans will be submitted as these requirements
are made known. In the case of polynuclear aromatic hydrocarbons (PAH),
and sulfur compound determinations, Level 2 needs are presently delineated
and consequently procedures are included for sampling and analysis of these
materials.
1-2
-------
1.2 MULTIMEDIA SAMPLING PROCEDURES
The Level 1 procedure described in this manual can be utilized to
acquire process samples, effluent samples, and feed stock samples. The
Level 1 environmental assessment program must, at a minimum, acquire a
sample from each process feed stock stream, and from each process effluent
stream. The feed streams data are necessary to establish a baseline for
comparison. The effluent stream sampling program is required to determine
the mass emissions rate and the corresponding environmental insult. Con-
sequently, all samples will be taken downstream of any control devices.
Sampling and analytical procedures which are required to support compre-
hensive environmental source assessments must be multimedia in nature.
1.2.1 Classification of Streams for Sampling Purposes
The basic multimedia sampling strategy shown in overview form in
Figure 1-1 has been organized around the three general types of samples
found in industrial and energy producing processes. This facilitates the
complex and difficult tasks of organizing the manpower and equipment
necessary for successful field sampling and establishing meaningful units
of cost.
The three sample types are:
• Gas/Vapor - These include samples from input and output
process streams, process vents, ducts, stacks and ambient air.
The samples will be examined for light hydrocarbons and
inorganic gases as well as entrained particulates.
• Li quid/Slurry Streams - Liquid streams are defined as those
containing less than 5 percent solids. Slurries are defined
as those containing greater than 5 percent solids. Non-
slowing pastes are considered solids.
• Solids - These include a broad range of material sizes from
large lumps to powders and dusts, as well as non-flowing
wet pastes.
Flow diagrams which show the overall relationship of the samples to
the analysis scheme are shown in Figures 1-2 and 1-3.
1-3
-------
MULTIMEDIA SAMPLING
APPROACH OVBtVIEW
GASES
LIQUIDS
SOLIDS
FLUE
GASES
COOLING
TOWER
WATERS
SLOWDOWNS
FUGITIVE
EMISSIONS
SLURRIES
EVAPORATION
PONDS
COAL PILES
AND/OR
RAW
MATERIALS
ASH PILES
AND/OR
REFUSE
SLUDGES AND
SEDIMENTS
GASEOUS
SPECIES
SASS
TRAINS
PARTICULATES
CONDENSIBLES
Figure 1-1. Multimedia Sampling Approach Overview
-------
I
01
PARTICULATE 1
MATTER I
I
C^^ f£/^\ 1
^\J*W wX^M 1
1
SOURCE — fc
1
1 OPACITY 1 1
| (STACKS) |
|
•WEIGH
INDIVIDUAL
CATCHES
PROBE AND J,,,rt^AK,,« ELEMENTS (SSMS) ANU
CYCLONE • ' 1 >|INORGANICS SELECTED ANIONS**
J ORGANICS
SASS TRAIN GAS 1 CAIIW-' 1
CONDITIONER
CONDENSATE J|NORGAN1CS
SASS TRAIN IINORGANICS
IMPINGERS 2ND jAs, Sb, Hg
» "-*lftll * 1 fc.
hi i-in»i* 1 — »•
— M FILTER 1 *
EXTRACTION | ^INORGANICS
INTO FRACTIONS, J nBrANIir<; SEPARATION
LC/IR/MS H ORGANICS |NTO FRACT|ONS,
ELEMENTS (SSMS) AND
SELECTED ANIONS
ELEMENTS AND
SELECTED ANIONS
ELEMENTS (SSMS) AND
SELECTED ANIONS
EXTRACTION | H ORGANICS
SAME AS ABOVE
^NOV CHEMILUMINESCENCEI
* OR METHOD 7 I
H INORGANIC
(GRAB)
INTO FRACTIONS
LC/IR/MS
rtuc ci-re <~A« iiii<->D/~,iKii/~c 1 cixwicnia \Mmj;«i-«w
THROMATO«^i»»V r . , „ J JtLCCTCD ANIONj
H ORGANIC
MATERIAL >C&
XAO-2
MOPMIFWKKF
ORGANICS MUWUV.M rv^R w«^-»
..^^ f /- CHROMATOGRAPHIC
*•?" ^16 ANALYSIS
PHYSICAL SEPARATION § i A „* ,„ l(J
^ ORGANIC
* MATERIAL Cj -C^
ON-SITEGAS •NTO/CiAS*
CHROMATOGRAPHY
> OBfiAMir*; rnT3i«-«u jtrfMv-mvi-.
^ UW»AINH_S INTO FRACTIONS
"IF INORGANICS
ARE GREATER THAN
10% Of TOTAL CATCH.
Figure 1-2. Basic Level 1 Sampling and Analytical Scheme
for Particulates and Gases
-------
SOLIDS
SOURCE
LEACHABLE
MATERIALS
ORGANIC*
UKOANIC5
INORGANICS
PHYSICAL SEPARATION
INTO FRACTIONS LC/IR/MS
ELEMENTS (SSMS) AND
SELECTED ANIONS
INORGANICS ELEMENTS (SSMS) AND
llNUK^AiNH-i I SELECTED ANIONS
ORGANICS
SLURRIES
I
LIQUIDS
PHYSICAL SEPARATION
INTO FRACTIONS,
LC/IR/MS
SUSPENDED
SOLIDS
INORGANICS ELEMENTS (SSMS) AND
iiNUK^ANi^bi ANIONS
ORGANICS
PHYSICAL SEPARATION
INTO FRACTIONS
LC/IR/MS
INORGANICS I ELEMENTS (SSMS) AND
INORGANICS I $ELECTED XN| QMS
SELECTED
WATER
TESTS
ORGANIC
EXTRACTION
OR DIRECT
ANALYSIS
ORGANICS
>C
16
ORGANICS
-------
1.3 ANALYSIS OF SAMPLES
Chapters 6 through 8 specify recommended analysis schemes and
procedures that will provide data that can be related both to existing
EPA standards and those additional data requirements specified in this
chapter for Level 1 environmental assessment. Because quality assurance
is an important part of data acquisition, this area is treated separately
in Chapter 2. Also, quality control parameters have been integrated into
all the procedures. The decision criteria for sampling and analysis is
covered in Chapter 3. Chapter 4 describes sample handling and disbursement
procedures while Chapter 5 details the acquisition of ducted air and water
emissions, liquids, slurries, solids and fugitive air and water emissions,
as well as the sample recovery and handling procedures necessary to ready
the samples for analysis.
There are five categories of analysis:
• Organic Analysis - Qualitative and quantitative techniques are
used to Identify compound classes by functional group and
boiling point range.
• Inorganic Analysis - Based primarily on spark source mass
spectroscopy (SSMS) which can perform a general survey of
all effluent streams for possible inorganic elements and
atomic absorption spectrophotometry (AAS) for specific elements.
• Water Analysis - Reagent test kits will be used as a supple-
ment for those analyses that are not covered by SSMS or
organic analysis.
• Field GC Analysis - Consists of on-site analysis of gaseous
and/or low boiling organic and inorganic species.
• Opacity - This test will be performed using a simple
Ringelmann Chart and the Bacharach test.
Table 1-1 shows the recommended sample volumes that must be collected
in order to obtain the listed sensitivities when the recommended analysis
method is used. These sensitivities have been selected by PMB-IERL-RTP
for both inorganic and organic compounds so that all species of current
interest can be analyzed at levels which at present are the lower limits
of environmental concern. Table 1-2 provides a complete list of the
analysis procedures, a brief description of the procedures and the section
number where each can be found in the manual.
1-7
-------
Table 1-1. Recommended Sample Sizes and Detection Limits
Sample Source Sample Type Inorganic Organic
Stack 30m3 ~ Participate Matter .. (hOlng/m? 2ug/m?
(1,060ft3) Sorbent Trap, >Ci6 £ O.Olug/nf5 2ug/m^
Sorbent Trap, C7-Clfic; - 2yg/rrf
/ID i j» \
d) ie) T'
Gas 3 liters General Components, 1 mg/m lOOrig/m
Sulfur Compounds ^' lug/nr lwg/nr
Liquid ^15 liters 10 Ion-site extraction 10pg/l n)
(4 gal) 1 J pH<2 with HNO,. lug/] 0
1 a neutral j) d
Solid 1 kg — 1 mg/g 100 ng/g
(2.2 Ib)
a) At STP
b) The analysis is terminated for organic material if less than 15 mg
(0.5 mg/m3) of organic components are extracted from the total sample.
c) Assumes that the XAD extract is concentrated to 10 ml and a 1 jil sample
is injected into a G.C. with a flame ionization detector with a 0.1 ng
detection limit.
d) A maximum sample size of 10 ml is assigned for all cases.
e) Detection limit is approximately 1 ppm.
f) Detection limit is approximately 0.1 ppm.
g) Detection limit is approximately 1 ppb.
h) Detection limit of 100 ug/class.
i) Assuming a 1.0 ml sample for SSMS electrode formation and a 10"9g
instrument sensitivity.
j) Reserve sample.
1-8
-------
Table 1-2. List of Analysis Procedures in the
Combustion Source Assessment Methods
and Procedures Manual
PARAMETER OF INTEREST
METHOD DESCRIPTION
SECTION NUMBER
IN MANUAL
FIELD GAS ANALYSIS
C]-Cg Hydrocarbons
C02, 02, N2 and CO
NOX
FIELD WATER ANALYSES
Acidity
Alkalinity
Conductivity
Total Suspended Solids
(TSS)
Hardness
PH
Nitrate Nitrogen
Phosphate, Total
Organic and Inorganic
Sulfite
Sulfate
Cyanide
Ammonia Nitrogen
Opaci ty
Gas Chroma to graphy
Gas Chromatography
Chemi luminescence or Method
7 (laboratory analysis)
Titration with NaOH to
pH 4 and pH 8
H;?S04 titration to pH 4.5
with two indicators
Self-contained conductivity
meter
Spectrophotometry
(turbidimetry)
EDTA titration
Direct reading electrode
Diazotization followed by
Spectrophotometry
Oxidation with potassium per-
sulfate and Spectrophotometry
lodide-iodate titration
Precipitation with BaCl2 and
turbidimetry using SulfaVer
IV Test Kit
Colorimetry using Hach
Cyanide Test Kit '
Nessler (mercuric and
potassium iodide)
Ringelmann and Bacharach tests
6.2
6.2
6.3
6.4
6.5-1
6.5.2
6.5.3
6.5.4
6.5.5
6.5.6
6.5.7
6.5.8
6.5.9
6.5.10
6.5.11
6.5.12
6.6 and 6.7
1-9
-------
Table 1-2. List of Analysis Procedures in the
Combustion Source Assessment Methods
and Procedures Manual (Continued)
PARAMETER OF INTEREST
METHOD DESCRIPTION
SECTION NUMBER
IN MANUAL
LABORATORY ANALYSES
Organic Analyses
Extraction of samples
Concentration
Gravimetric
determinations
Infrared spectrometry
C/-C16 hydrocarbons
Liquid chromatography
Low resolution mass
spectrometry
PAHs
Inorganic Analyses
Sample preparation
Spark source mass
spectrometry
Mercury
Arsenic
Antimony
Sulfate
Sulfur species
Fluoride
Chloride
Liquid-liquid and Soxhlet
solvent extractions
Kuderna-Danish exaporative
concentrations
Analytical balance weighing
of organic residues
Salt window smears and KBr
pellets
Gas chromatography
Seven fraction separation on
silica gel
Solids probe, temperature
programmed analysis
Combined gas chromatography/
mass spectrometry
Parr bomb combustion, Soxhlet
aqua regia extraction, hot
water digestion
Graphite electrodes with visual
photographic plate data
interpretation
SnCl2 reduction and measurement
by AAS: cold vapor method
Hydride generation and AAS
detection
Hydride generation and AAS
detection
Turbidimetric measurement of
barium sulfate precipitate
in suspension
Controlled Condensation
System (CCS) for deter-
mination of S02, S03 and
oarticulate sulfate
Selective ion electrode
Selective ion electrode
7.3
7.4
7.5
7.6
7.7
7.8
7.9
7.10
8.2
8.3
8.4
8.5
8.6
8.7
8.8
8.9
8.10
1-10
-------
2.0 QUALITY ASSURANCE
2.1 PURPOSE
The primary objective of the Quality Assurance function is to ensure
that all data collected and reported are meaningful, precise and accurate
within the stated acceptance criteria. In designing the Quality Assurance
procedure described in this chapter, both the EPA* and TRW quality assur-
ance and guidelines were adapted to the specific requirements of this pro-
gram. This goal will be accomplished by:
• A continuing evaluation of the adequacy and effectiveness of
the overall quality control program,
• Verifying strict adherence to equipment, specification, and
procedural requirements
• Requiring correction of weaknesses in the quality program.
2.2 QUALITY POLICIES
The data quality program will verify that the data generated by
project personnel meet all the established criteria. The data quality
program will have the following characteristics:
t It will be complete in nature. Not only in-house activities,
but also the activities of associate contractors and subcon-
tractors will be included. This QA proaram will cover
sampling, analysis, data processing and handling, and all
supporting activities in these areas.
• It will be integrated. All procedures will include quality
control provisions delineating the practices, requirements
and procedures which are to be implemented at each phase of
the program.
The quality program will be implemented at two levels:
• Quality control level. To ensure that data quality is
sufficient to meet project requirements, all procedures are
to be approved by the QA Manager prior to implementation.
* Franklin Smith and James Buchanan, "IERL-RTP Data Quality Manual", EPA
600/2-76-159, U.S. Government Printing Office, Washington, D.C. 1976
2-1
-------
• Quality assurance level. Quality assurance procedures for
independently monitoring and assessing the efficiency and
adequacy of individual quality control programs will be
administered by the QA office with full power to enforce
changes in procedures as needed. Such procedures are subject
to periodic review and audit by the EPA Quality Contractor RTI.
The primary objectives of this data quality program are to determine,
ensure, and document that the quality (i.e., precision, accuracy, and
completeness) of measurements made on this program is commensurate with
the end use of the data. Management, administrative, statistical,
investigative, preventive, and corrective techniques will be employed for
this purpose.
2.3 QUALITY OBJECTIVES
Specific quality objectives for this program are:
• To require that approved procedures are used between various
sites and laboratories.
• To review quality among various sites and laboratories and
account for disparities to the extent possible.
• To identify the need for and contribute to the selection of
procedures and methods necessary to secure the collection of
data of acceptable quality (i.e., of acceptable precision,
accuracy and completeness).
• To verify that quality control programs are developed for use
on each specific sampling and analysis task.
• To develop and implement a quality assurance process which will
independently monitor the effectiveness of these individual
quality control programs.
2.4 ORGANIZATION
The Quality Assurance Manager will report directly to the Program
Manager. He will have complete freedom to inspect, audit, and otherwise
review each parameter, process, etc., throughout the program. Quality
recommendations will be reviewed and implementation enabled by the Program
Office. The QA manager will interface with EPA and other contractors regard-
ing the QA Program to aid in incorporation of optimum controls.
2-2
-------
PROGRAM MANAGER
QUALITY ASSURANCE
MANAGER
QA
INDOCTRINATION
SEMINARS
PROCEDURE
REVIEW AND
APPROVAL
rv>
i
SAMPLE
IDENTIFICATION
AND
TRACEABIUTY
INTERFACES
n
QUALITY
CONTROL
DATA
ASSESSMENTS
SAMPLE
BANK
PERSONNEL
INTERFACES
QA
AUDITS
FEEDBACK
AND
CORRECTIVE
ACTION
INTERFACES
INTERFACES
INTERFACES
Figure 2-1. Function Diagram for Quality Assurance
-------
2.5 QA TASKS
Figure 2-1 shows the QA organizational structure, the QA tasks, and
the required interfacing with other groups on the program.
Each category of Figure 2-1 is discussed below.
2.5.1 Indoctrination and Training
The activities of the QA indoctrination and training program are
outlined in Figure 2-2 and include:
• Personnel indoctrination to QA program
• Identification of training elements
• Preparation and training of supervisory and test personnel
• Refresher QC training meetings, as needed
REVIEW
APPROVED
PROCEDURE
IDENTIFY
TRAINING
ELEMENTS
IN
PROCEDURE
REFRESHER
MEETINGS
REVIEW
TRAINEE
VS. PROCEDURE
CRITERIA
PREPARE
TRAINING
PLAN
IMPLEMENT
TRAINING
SESSION
Figure 2-2. Training Activity Associated with Each Procedure
2.5.2 Procedure Review and Approval
Quality control steps will be reviewed and approved for all proce-
dures, instructions, specifications, equipment, etc. The QA approval
cycle is shown in Figure 2-3. Because of the cycle time between QA and
the authors, a concentrated effort in procedure approval will be
necessary.
2-4
-------
FIRST DRAFT
PROCEDURES
SUBMITTED
QA
PROCEDURE
REVIEW
QA
APPROVAL
INCORPORATE
QA COMMENTS
IN PROCEDURES
CONFIGURATION
CONTROL
Figure 2-3. QA Function Relative to Procedures
2-5
-------
QA will also ensure that the documentation system will maintain a
current configuration (latest revision) of procedures being used in
testing. There is a requirement that whenever it is evident that
data being obtained are not sufficiently accurate or appropriate for the
intent of this program, the sampling and/or analytical procedure shall be
modified after coordination with other groups. Thus, revisions are to be
expected. A list of the latest revisions shall be issued by QA for posting
by appropriate field and laboratory supervisors.
2.5.3 Sample Identification and Traceability
The size and complexity of this program, which includes thousands of
data points coming from several laboratories, requires a firm system of
data processing and accountability. Since this system provides a vital
link in the quality of the emission source assessment system, Quality
Assurance personnel will contribute in both its initial development and
in the continuous monitoring of its effectiveness. The tasks as shown in
Figure 2-4 are:
• Sample Bank Development Assistance - Sample bank development
will be monitored by QA to assist in introducing proper QC
steps and to increase dependability of the system.
t Review Sample Bank System and Implementation Forms - The
completed sample bank system will be reviewed in detail,
including all procedures and forms required in the system.
• Monitor Sample Bank Function - The sample bank function will
be periodically inspected to ensure up-to-date, proper label-
ing of samples, proper control and traceability maintained on
samples, proper disbursement of samples for analyses, and that
all data books are accompanying each sample. Complete
traceability of samples shall be verified.
ANALYSIS OF
SAMPLE BANK
QUALITY
ASSURANCE
ASPECTS
REVIEW
SAMPLE BANK
SYSTEM AND
FORMS
PARTICIPATE IN
SAMPLE BANK
DEVELOPMENT
MONITOR
SAMPLE BANK
FUNCTION
Figure 2-4. QA Activities for the Sample Bank
2-6
-------
• Analysis and Reports of Sample Bank - An assessment of the
sample bank system will be made, including traceability,
based on the results of this inspection. Criteria for this
assessment will be based on the requirement that the sample
bank should be able to show the exact treatment sequence and
the dates of the various critical types of treatment (i.e.,
stabilization, digestion and titration, etc.) for each sample.
2.5.4 Quality Control
The following key aspects of the QA effort in this program for
reviewing the adequacy of the QC Program are shown in Figure 2-5 and
discussed below.
METROLOGY
COMPUTATION
AND DATA
REPORTING
STANDARD -
CENTRAL
STORAGE BANK
SAMPLING
AND
ANALYSIS
PROCEDURES
MATERIAL AND
EQUIPMENT
PROCUREMENT
CONTROLS
QUALITY
ASSURANCE
ACCEPTABLE
DATA
IDENTIFICATION
QUESTIONABLE
DATA
IDENTIFICATION
DISCREPANCIES
IN DATA
IDENTIFICATION
Figure 2-5. Quality Control Operations to be Emphasized in this Program
2-7
-------
2.5.4.1 Procurement Quality Control
t All procured materials must conform to the appropriate
procedure specification.
• Reagents and chemicals that have limited shelf life will be
identified and used within the specified expiration date.
t All acceptance tested materials and equipment procured for
this program will be inventoried. Traceability of all
acceptance testing, including all data and test methods, will
be maintained. Discrepant procurement, fabrication, cleanli-
ness, metrology, standardization, materials and processes,
etc., will be subjected to discrepancy analysis (see
Section 2.5.7).
2.5.4.2 Cleanliness Controls
All equipment and glassware in contact with samples will be cleaned
in accordance to a detailed cleaning procedure designated to prevent
contamination. Any special cleaning required in a specific test will be
added to the test procedure.
Cleaned equipment and glassware will be identified and dated, or
stored in dated storage areas to ensure traceability.
2.5.4.3 Metrology and Standardization
Equipment shall be certified, as required, by the TRW or GCA
Metrology Departments in accordance with EPA Document 600/2-76-159 or
DOD Documents MIL-Q-9858A and MIL-C-45662A or acceptable alternative pro-
cedures prior to being used on the program.
Metrology Department will routinely inspect, calibrate, and certify
designated equipment at specific intervals. Metrology personnel will
routinely examine designated analytical equipment on a monthly basis. It
is expected that contractors will implement a similar regular inspection
program, or justify its absence. Metrology and calibration will be docu-
mented against an inventory list of equipment showing scheduled equipment
verification.
Results of metrology activities will be reported to the QA Manager
of this program.
2-8
-------
2.5.4.4 Central Storage Bank Quality Control
The data bank and sample identification system for this program (see
Chapter 4) will include controls on the overall quality of the system.
Some of the QC factors to be considered in these controls are:
• Legibility,
• Permanence of record.
• Standardization of notation.
• Completeness check list at each significant data transfer
step.
• Systematic storage of in-process data forms, sample location,
etc.
2.5.5 Computation and Data Reporting
The QA functions in the data assessment area are shown in Figure 2-6
and consist of the following:
t Verification of the acceptability of the computation steps and
calculation checks used in the analytical procedures. This
will include any computer programs for processing raw data.
• Statistical evaluation of comparisons between standards,
replicates, spiked samples and the routine analyses.
• Records and trend analyses to identify potential QA problem
areas in the assessment scheme.
t Data validation procedures shall be defined for all measure-
ment systems.
• Provision for clear definition of various parameters, such as
flow rates and calibration data.
• Use of minimum detectable limits to evaluate trace data for
appropriateness.
• Examination of negative data points immediately for possible
cause, error, interferences.
• Concern with all rejected data and the cause or reason for
rejection.
• Relation between data and standards, replicates, spikes, etc.,
and Level 1 requirements.
2-9
-------
2.5.6 Auditing
Quality audits will be made of all the critical functions in the
emission study program. The audits will include:
• Verification that standards, procedures, records, drawings,
specifications, requirements, etc., are maintained in the
most current approved version.
t Verification that actual practice in tests, data storage,
sampling, etc., agrees with approved written instructions.
REVIEW
RAW DATA,
ANALYSES, AND
CALCULATIONS
RECORDS
AND
TRENDS
STATISTICAL
ANALYSES
QA
REVIEW
QUESTIONABLE
RESULTS
ACCEPTABLE
RESULTS
Figure 2-6. Activities 1n the Quality Data Validation and
Assessment Program
2-10
-------
• Assessment of adequate Quality Control of program by use of
replicate samples, independent analyses, spiked samples,
"dry runs," traceability studies, etc.
• Providing substantiative evidence that failure risk is con-
trolled by the use of precautionary measures, such as
cleanliness, orderliness, environmental control, and by the
use of industry-accepted techniques for common technical
operations.
Auditing will be done as shown in Figure 2-7, by apportioning a
percentage of the total auditing effort to: (a) purely random selection
of audit material; (b) a percentage to areas either totally new or
suspected to be "weak links" in the quality control system; (c) and the
remaining to areas which are found to be "trouble spots" due to high
frequency of repair, schedule delay, replacements, spoilage, or poor
performance in the most recent audit.
2.5.6.1 Audit Items
A review will be made of all functions required for this program
through existing documentation such as processing flow diagrams, data flow
diagrams, procedures, procurement practices, etc. Two kinds of audits
will be performed: quantitative and qualitative. The quantitative audit
will utilize check methods such as standard analytical samples, and spiked
samples. The qualitative audit will assess and document (1) facilities;
(2) equipment; (3) systems; (4) record keeping; (5) data validation;
(6) operation, maintenance, and calibration procedures; and (7) reporting
aspects of the total quality control program.
2.5.6.2 Audit Apportionment
Audit apportioning will consist of allocation of audit effort among
random audits, suspect item audits and problem audits within the con-
straints of the program. The auditing effort may be qualitative, quanti-
tative, or both, and either a complete audit or a partial audit may be
allocated.
2.5.6.3 Audit Frequency and Schedule
Auditing frequency will be determined by the nature of the audit
effort, its cost, risk factors in not auditing, and priority.
2-11
-------
REVIEW
PROCEDURES,
RECORDS,
SPECIFICATIONS, ETC.
IN STATIONARY
SOURCE
PROGRAM
APPORTION
FUNCTIONS
TO BE AUDITED
PROBLEM
AUDIT
SUSPECT
ITEM AUDIT
RANDOM
AUDIT
SUSPECT AREA
AUDIT
PROBLEM AREA
ALL FUNCTIONS
IDENTIFIED
ASSOCIATED
VMATERIAL/
Figure 2-7. QA Audit Approach
2-12
-------
Functions in which problems have been identified will generally be of
highest priority. Areas suspected of being "weak links" in the data
chain, for example, a process having marginal reproducibility character-
istics, will be of next concern. Of lowest priority, yet of importance,
is the random auditing of any process to sample for continued process
acceptability. For this program, random audits will be held on at least
two sites during the first year. Using constraints of schedule, cost,
and availability of the audit function, random audits must be considered
along with the problem and suspect area audits. To do this, an integrated
approach will be used in which audit activities are combined in an audit
visit as much as possible. Excessive problem demand or similar demands
requiring unplanned QA audit effort will necessarily affect the audit
frequency or planning.
2.5.6.4 Audit Procedures
Some general considerations in the audit procedures are:
• Audits will be conducted on all phases of each test via a
random selection process without prior notice. Thus,true
representative audits will be attained.
• Audits will be conducted in the field, in the laboratory, in
the data handling center and in the data assessment areas.
• Subcontractors will also be audited.
• All violations or infractions will be noted and immediate
notification of appropriate personnel at all levels will be
made. Corrective action must be immediately implemented or
the testing will be labeled "Potentially Erroneous Data."
• All unreliable data will be noted and replacement samples or
analysis will be performed wherever possible.
• All auditing will consist of observations and notation as to
whether approved procedures are used and as to the level of
proficiency. Any deviation will immediately be noted.
• When subcontractors are employed to perform certain analytical
tasks, a program is established whereby known reference
samples are sent to them interspersed with actual samples.
The quality of the subcontracting laboratory's work can then
be readily determined. Their methods and QA functions are
also fully examined so that TRW will have confidence 1n
their data.
2-13
-------
• Quality audits shall be coordinated with Data Assessment groups
in terms of notification of results. No advance warning will
be given to personnel of any impending QA audit in order to
assure a valid and representative audit.
2.5.6.5 Audit Performance and Reports
The actual audit and the reporting of the audit findings will be
thoroughly documented.
2.5.7 Discrepancies
The efficient and thorough identification of discrepancies in the
methodology of emission assessment is essential to maintain effective
quality assurance. A discrepancy, for purposes of QA.is considered to be
any deviation from accepted procedures, requirements, or processes, or
defects in a material part or result compared to a requirement. Dis-
crepancies may arise from QA audits, from any of the quality functions in
the program, as well as from other program sources such as procurement,
testing, sampling, data handling, etc. Systematic and thorough treatment
of discrepancies will follow the plan shown in Figure 2-8. This systematic
approach provides a basis for maintaining the quality audit at a minimum
sampling level.
The three major activities in which QA must participate are:
• Discrepancy review board participation
• Review of failure analysis and recommendations
• Approval of final closeout activities of problems and
discrepancies
2.5.8 Quality Assurance Reporting and Documentation
Quality Assurance will issue special reports of audits in field
and/or audits in laboratory. When indications that quality may be com-
promised exist, depending on the severity of the infraction, meetings of
all appropriate personnel would also be instituted.
The final or annual reports will include a section on Quality
Assurance. A summarization of all data quality can be given as it
relates to:
2-14
-------
LABORATORY
OR FIELD
DISCREPANCY
REPORT
DISCREPANCY
REVIEW BOARD
CLOSE OUT
DISCREPANCY
AND ISSUE
REPORT
PROBLEMS
IDENTIFICATION
FAILURE
ANALYSIS AND
RECOMMEND-
ATIONS
CLOSE OUT
ACTIVITIES,
AND ISSUE
FAILURE
REPORTS
Figure 2-8. Activities Relative to Discrepancies
2-15
-------
• Quality and percentage of replicate samples and replicate
analysis.
• Percentage of questionable data as discovered by audits.
• On-site audit inspection and its results.
0 Discrepancies.
• Review of performance audit including precision, accuracy,
and completeness of data, as well as how representative the
data are.
• Discussion of precision and/or accuracy of subcontractors
data.
• Any quality assurance problems occurring during the performance
of this task and how they were solved.
The report shall go to all levels of personnel in order that they
may fully comprehend any problems and the criticality of strict QA/QC.
2.6 GUIDELINES FOR IMPLEMENTATION OF QA
2.6.1 Applicability
The principles and procedures discussed in Sections 2.2 thru 2.5 are
applicable to Levels 1, 2 and 3 testing. While many Level 1 tests will
be performed optionally with quality control at intensified levels, it is
possible to define certain minimum criteria to insure adequate quality for
Level 1 testing. The basis for the minimum criteria is the recognition
that Level 1 sampling and analyses will be acceptable within an accuracy
factor of two to three.
2.6.2 Level 1 Quality Assurance Activities
For Level 1, it can be assumed that normal day-to-day sampling,
material control testing, standardization, and metrology are adequately corn
trolled by personnel selection, training programs, equipment controls and
supervision. In other words, existing practices, equipment and personnel
are "state-of-the-art", and controlled by adequate guidelines and procedures
to Level 1 accuracy. If this is so, the Level 1 quality program should
aim to reduce the occurrence of excursions from procedures. Excursions
would cause gross undetected variation, while procedures, as expected
from development work, are ad'equate to produce Level 1 accuracy.
2-16
-------
To do this, the quality program must identify and emphasize the
sources of error which are most likely to cause extreme variation.
Examples of such gross sources of error are:
• contamination
• cumulative buildup in sampling equipment
• sample loss or concentration
• transposed data numerals
• erroneously marked sample identity
t incorrect physical units or loss of digit in recorded
parameter.
In addition, particular procedures may have specific key process
steps which,if violated,could cause serious errors where Level 1 accuracy
is required. It is therefore assumed that Level 1 accuracy will most
probably be exceeded by human error in following actual procedural steps.
A method for auditing procedural adherence can be developed by observing
procedural adherence a given number of times. One method is described
in detail in Appendix A, Section A.
2.6.3 Minimum Number of "Blank" Tests Acceptable for Level 1 Tests
A minimum number of reagent "blank" tests from a container can be found
which will indicate further testing is not needed to indicate good quality
control practices are being used. The technique can be applied to any pro-
cedure in the program which requires blank testing, and will indicate that
emission factors are not unduly influenced by unexpected variability among
the blanks.
The approach is as follows:
• Identify the desired accuracy requirement for the procedure.
• Estimate the parameter mean, the average change between blanks
and its standard deviation obtained from repeated testing of
the container for its "blank" value.
• Determine the level of risk to be afforded in assuming blank
testing may be stopped.
• Determine the number of tests to show the parameter will not
exceed the accuracy requirement with the selected risk of
being Incorrect, using Equation (A.7) of Appendix A.
2-17
-------
More testing is automatically required when the emission values are
nearer the detection limit, when the variability is higher, or when a low
risk is desired. The procedure is discussed in detail in Appendix A,
Section B. It is found, for example, that the repeated testing of "blank"
solvent samples could be terminated when 1/4 of the solvent container has
been used while maintaining Level 1 accuracy, if the unaccounted variation
of the blanks is not more than about - 0.6% of the emission value. This
work indicates that in the Level 1 testing, when the blank is not higher
than 10% of the observed value, and is relatively reproducible, repeated
testing of the solvent is relatively unproductive. A possible quality
assurance test of this assumption can be made by subsequently running a
blank on the last of the container to verify the correctness.
2.6.4 Minimum Number of Replicate Tests for Level 1
The decision criteria in this section will determine the minimum
extent of analytical test replication needed to support the concept of
Level 1 accuracy in the data base. The approach is based on the observa-
tion that repeated replication of data after the test has demonstrated
an adequate accuracy 1s useful mainly as a form of Insurance against
outliers and sudden changes in the reproducibility. For Level 1 accuracy
requirements, the need for this insurance is less than with ordinary
analytical testing, and an adequate control is provided by strict adherence
•
to procedural details and a QA monitoring program. Thus, the use of
replicate testing can be curtailed as soon as it has been demonstrated
either that the method is sufficiently accurate for Level 1 purposes, or
that the method is not as accurate as desired but further testing adds
little to its characterization.
The decision criteria do not apply to replications required because
of a suspected error in handling or testing which may occur in a given
test. These replications are part of a problem-solving process and are
generally not applicable as estimates of normal operation.
2-18
-------
Further, if the decision criteria have been applied and replication of
a test has ceased, replication should be reinitiated whenever the assump-
tion of test method stability is suspect. For example, if new technicians
are introduced, procedures modified or equipment changed, replication should
be applied until the decision criteria have evaluated the new conditions.
The decision to cease replication is based simply on having obtained
an adequate representation of the variability of the test method.
Knowledge of the variability (obtained through replicate analysis) is
adequate when there is little risk (less than 10%) that the Level 1 accep-
tability of the results will be proven wrong by further testing, or for
methods having unavoidably high inaccuracy, that further testing will reveal
an inaccuracy grossly larger than suspected. In this latter case,
"grossly larger" is taken to mean that the method reproducibility estimate
Itself is within Level 1 accuracy. The development of the approach is given
in Appendix A, Section C.
The decision criteria are based on several assumptions:
(1) The reproducibility of the test is not affected by the type
of site sampled.
(2) The reproducibility of the test will not change during the
course of the program, given one set of procedures and
personnel.
(3) The inaccuracy of a pollutant determination is predominately
due to random sampling and test variation, i.e., bias, if
present, is either relatively small or known and therefore
correctable.
(4) The Level 1 accuracy factor for sampling and analysis for each
site is 3, and for analysis alone, is 2.
Assumptions (1) and (2) can be checked by quality assurance testing
during the program.
2-19
-------
2.6.5 Decision Plan for Number of Replicate Tests
The following decision plan, shown schematically in Figure 2-9,
defines the actions to be taken to identify the need for replication,
COMPLEXITY A
1
SITE 1
COMPUTE
S* AND A,
(d-D
SA/A FIG. 1
DISCONTINUE
REPLICATES
ALL POLLUTANT
ANALYSES TO DATE
COMPLEXITY B COMPLE)
If
(INDIVIDUAL
POLLUTANT TEST)
(ECT.) (ETC.)
1
SITE 2 SITE
1
COMPUTE COMP
1
COMPUTE
=
FIGURE 1
(4-2)
SA/^ FIG. 1 AT
VA FIG< ] AT " 17
CONTINUE REPLICATES 1
UP TO MAXIMUM OF 17 >
KITY C COMPLEXITY D
3 SITE 4
UTE COMPUTE
DAT S^ANDA,
SA/A»FIG. IAT^-17
OR
SVA>0.567AT,-6
DISCONTINUE REPLICATION
\FTER v "6
Figure 2-9. Decision plan describes the action
needed to identify the need
for replication
2-20
-------
In this plan:
if
c
_
A n.| + n^ + ...nv - v
2
where each s Is the variance of the test results for
the pollutant at a given site, and each n 1s the
number of tests for that pollutant at that site.
A is computed as the average value of the pollutant determination
of each of the four complexities shown in Figure 3-2. Compute A as:
nK 4* n A 4* in S
_ 1 1 llpr\o • • • II n
V II £ £ V V
A =
n1 + n + n
I ~ \\n ' • « • II
where A, etc., are the Individual site average values.
If only duplicates are taken at each site,
A, + A + . . .A
- 1) + n - 1 + ...(n - 1)
v
where n, 1s the number of repeated tests for
pollutant A at site 1 of the complexity group.
2-21
-------
For Application of the Criteria
d-1 Discontinue replicate testing when the value of SA/^ at the level of
v used is less than that required by Figure 2-10.
d-2 When SA/^ is greater than that required by Figure 2-10 at the level of
v used, but less than the curve at v = 17, (i.e., 0.310), continue
testing until d-1 is met or 17 replicates have accrued (v = 17).
d-3 When S./x will clearly not meet the criterion at v = 17 (i.e., the
valu6 of SA/£ is sufficiently larger than the curve criterion, that
it is highly unlikely that added testing will improve SA or A
sufficiently to meet the criterion), stop replication at v « 6.
2-22
-------
IQ
G
re
ro
n> n>
-o n
' o ->'
ro o» o
Q) O
cr 3
o
-S -h
QJ o
(D
•_"•
rt
1/1
STOP REPU GATES
AT »* 6 IF
SA/A >.567
NO REPLICATES
BEYOND v - 17
NO FURTHER
REPU CAT! ON
REQUIRED
-------
3.0 SAMPLING AND ANALYSIS DECISION CRITERIA
3.1 INTRODUCTION
This chapter presents the basic decision and planning criteria that
will be used in the design and execution of the entire sampling and
analysis program. These decision criteria also outline the approach for
acquiring special samples and/or data not normally collected for a Level 1
environmental assessment. A set of criteria are given for cases in which
either sample availability or data availability may limit the number of
analyses that may be performed. Samples such as fuel, water, ash, and
slurries are available in large quantities and will not require analytical
prioritization. Samples from the SASS train will often require a priori ti-
zation matrix in order to make effective use of the available sample.
Because planning and analysis decisions concerning the analysis of SASS
train samples for organics can not be made solely on the basis of sample
weight, a nomograph has been developed to predict the amount of extractable
organics and allow decisions to be made concerning those cases which
warrant solvent extraction and a full range of organic analysis. In
addition, an approach to effluent water sampling and analysis is presented.
3.2 REQUIREMENTS OF PLANNING AND ASSESSMENT TASK
As part of every environmental assessment, a planning and assessment (P&A)
task is necessary to give overall focus to the sampling and analysis tasks.
The initial work for this program will center on the review and evaluation
of the existing emissions inventory as it relates to the combustion sources
identified for study. This assessment and prioritization effort will be
part of the early phases of the program. This will result in the generation
of an overall field testing and laboratory analysis plan designed to acquire
additional emissions data for those sources and emissions species which are
determined to be presently inadequate. Because the data to be generated
by the analysis task is based on the assumption that no prior data exist,
the actual needs of data for assessment purposes will override all sub-
sequent decision criteria.
3-1
-------
Planning and assessment activities continue throughout this project
to evaluate the data from the sampling and analysis effort and from other
sources as it becomes available. In other words, an iterative process will
continue in the area of emissions assessment, source prioritization, field
sampling, and laboratory analysis as new data are generated or become
available and as the project emphasis shifts.
3.3 FIELD SAMPLING AND ANALYSIS DECISION CRITERIA
A set of guidelines must be developed for the field sampling crews
in order to 1) gather samples for analysis in a cost-effective manner,
2) meet the requirements of the planning and assessment task, and
3) meet the needs of laboratory operations to generate the proper data.
The basic input will be provided by the P&A effort which will define the
number of sites and general samples to be taken. This selection process
has been treated in other program documents. However, as described in
this section, an additional set of criteria has been developed so that
the field samples will be taken in a manner that will result in meaningful
laboratory analyses. These are described in the following sections, and
detailed application of these concepts is given in Chapters 5 and 6.
3.3.1 SASS Train Cyclone Deletion Guidelines
The combustion sources that will be sampled for this program include
a significant number of categories burning fuels such as distillate oil,
diesel fuel, natural gas, and to a certain extent residual oil that will
result in grain loadings below 0.1 grains/SCF. The resulting catches are
less than 7 g. As the grain loading is lowered, the >3y catch in partic-
ular drops off rapidly to the point where the 3 and 10y cyclone catches
are too small to be recovered. As the grain loadings are lowered further,
the ly cyclone catch also approaches zero. The use of cyclones where
very small (<10 mg) catches occur will result in high sample loss and con-
tamination. In addition, large amounts of labor are expended precleaning,
leak checking and post-cleaning the cyclones in order to obtain non-
existent or very small samples that will result in no useful data being
generated. Therefore, for both technical and economic reasons, a set of
decision criteria has been developed for removal of the cyclones at lower
grain loadings so that a maximum amount of useful data will be generated.
3-2
-------
The basis for these criteria is the nomograph shown in Figure 3-1
which displays the estimated >3y and <3y catches as a function of grain
loading. The data used for this nomograph were obtained from real case
12 3
sampling efforts using the SASS train ' and comprehensive studies by 6CA
and MRI . These studies include coal, oil, and gas fired units under a wide
range of grain loadings. Because the >3y fraction drops off to zero as the
grain loading goes down and because this is the primary trend that affects
the decision criteria displayed below, these data were always interpreted
with a conservative positive bias for the weight of the >3y fraction.
This was especially true when two different types of boilers or fuels gave
differing particulate distributions. This nomograph has been verified by
results obtained on this program.
Based on Figure 3-1, the set of decision criteria for cyclone use
shown in Table 3-1 was developed. In general, a projected catch of 5-10
mg in a given cyclone results in that cyclone being eliminated. This
cut-off point was chosen because samples of this size represent the lower
limit of recovery and are marginal in terms of analysis (only SSMS can be
performed). Table 3-2 shows how the decision criteria are expected to
apply to the combustion source categories to be tested in this program.
In all cases, the conservative approach will be taken, and an additional
cyclone will be used for the first one or two sites tested using each
type of fuel. In general, these guidelines were found to be adequate.
However, in order to make the data output of this program more nearly
compatible with the EPA's fine particulate data base, it was agreed that
after 1 September 1979 the 3y cyclone would always be used. In this way,
an absolute statement can be made that no particulate greater than 3y
was collected. The revised guidelines are shown in Figures 3-3 and 3-4.
Tables 3-1 and 3-3 are used subject to the following criteria:
• The maximum expected grain loading will be determined using pre-
vious test data or estimates provided by site personnel, actual
TRW/GCA field experience, and existing data concerning similar
sites. When in doubt, the next higher grain loading will be used.
3-3
-------
% CAT
A FUN
OF GR
LOADI
— - — •.
CHAS
CTION
AIN
NG
- — -~.— -
=100.0
8=1 99.8
— 99
— 98
— 97
— 96
— 95
— 94
— 93
— 92
— 91
— 90
— 80
— 70
— 60
— 50
— 40
— 30
— 20
— 10
— .5
t 2
^
TOTAL W
CATCH '
GRAMS
" — "" — ^
GRAIN
LOADING
EIGHT OF TOTAL WE
>3* IN CATCH <
GRAMS
CATCH GRAIN
WEIGHT LOADING
rBAIKl CATCH P0-1 ""
LoJffilNO ™ (
EXPANDED
1.0 —
0.9 —
0.8 —
0.7—
0.6 —
0.5—
0.4-
0.3—
0.2—
0.1 —
0.04 —
.9 SCALE
.01- -.ov . Q 2
) '
.02 - -1.4 *^_s
.03- -2.1
0.3 —
•04J-2.8
— 55.1 0.4 —
— 43.3 0.5— ,
— 33.0 ^°«6 —
— 24.1 / 0.7—
S
— 16.5X 0.8 —
X
^•10.3 0.9—
—5.5 1.0 —
— 2.1
— 0.7
—0.06
_ 0.003
IGHT OF
3 \i IN
CATCH
WEIGHT
=.2.8
6.9
—13.1
— 18.5
— 22.0
4i.i
— 24.8
-24.1
— 22.0
— 18.6
— 13.8
Figure 3-1. Participate Analysis Prediction Nomograph
3-4
-------
Table 3-1, SASS Train Cyclone Use Criteria*
(Before 1 September 1979)
Grain Loading
>o.n
0.051-0.10
0.021-0,050
0.0001-0.020
<0.0001
Projected Catch(g)
>3y <3y
>0.006 >6.9
0.004-0.006 3.1-6,9
nil 1.4-3,1
nil 0.007-1.4
nil <.007
Cyclones Required
ly 3y lOy
Yes Yes Yes
Yes Yes No
Yes No No
No No No
Use filter, XAD-2
module and
1mp1ngers only
*A filter 1s used In all cases.
Table 3-2. Expected Application of SASS Train Cyclone Use
Criteria as a Function of Fuel Type*
(Before 1 September 1979)
Fuel Type
Coal
Residual 011
Distillate Oil
Diesel Fuel
Projected Grain Loading
>0.1
0.051-0.10
0.021-0.05
<0.020
<0.02
<0.02
Cyclones Required
ly 3y lOy
Yes Yes Yes
Yes Yes No
Yes Not No
No No* No
No Not NO
Not No No
A filter 1s to be used in all cases.
"h"his cyclone will be used until field tests show that
1t is not necessary.
3-5
-------
Table 3-3. SASS Train Cyclone Use Criteria*
(After 1 September 1979)
Grain Loading
>0.11
0.051-0.10
Q. 021-0. 050
0.0001-0.020
<0.0001
Projected Catch (g)
>3y <3y
>0.006 >6.9
0.004-0.006 3.1-6.9
nil 1.4-3.1
nil 0.007-1.4
nil <.007
Cyclones Required
ly 3y lOy
Yes Yes Yes
Yes Yes No
No Yes No
No Yes No
Use filter, XAD-2
module and
impingers only
*A filter is used in all cases.
Table 3-4. Expected Application of SASS Train Cyclone Use
Criteria as a Function of Fuel Type*
(After 1 September 1979)
Fuel Type
Coal
Residual Oil
Distillate Oil
Diesel Fuel
Projected Grain Loading
>0.1
0.051-0.10
0.021-0.05
<0.020
<0.02
<0.02
Cyclones Required
ly 3y 10y
Yes Yes Yes
Yes Yes No
Yes Yes No
No Yes No
No Yes No
Not Yes No
*A filter is to be used in all cases.
'This cyclone will be used until field tests show that
it is not necessary.
3-6
-------
t All catches will be photomicrographed, checked for significant
oversize participate, and a rough particle size distribution will
be determined.
• If the field test produces results that indicate the use of
additional cyclones, the test will be repeated.
t If special conditions indicate their need, additional cyclones
will be used.
3.3.2 Special Procedures for Home Heating Units
In the case of the home heating units which are not run continuously,
the units will be run continuously until the required 30 m (STP) is
collected. However, concern over the variation of organic emissions as
a function of duty cycles resulted in additional testing of these units
with a 20 min. on, 10 min. off and 50 min. on, 10 min. off duty cycles.
For both oil and gas fired units, no significant differences were found.
3.3.3 S03/S02 Measurements
It is the objective of this program to determine S03/S02 ratios for a
selection of large utility combustion sources. These measurements have
been the subject of investigation on TRW's EPA Contract 68-02-2165 in which
it was found that the most effective method of making these measurements is
by a modified Goksoyr-Ross technique as delineated by EPA Document "Guidelines
for Combustion Source Sulfuric Acid Emission Measurements." This technique
will be used on at least 10 category C and D (Fig. 3-2) sites as stipulated
by the Planning and Assessment Task.
3.4 SPECIAL CASE ANALYSIS PLAN
In order to gather data in a cost-effective manner for species of
current environmental interest and requiring specialized techniques for
sampling and/or analysis and also for samples where considerable data is
available, a "Special Case Analysis Plan" has been developed and the
major components are shown in Figure 3-3. This plan is designed to show
the rationale that will be developed in detail during the program in
order to analyze a statistically significant cross-section of samples that
will satisfy the needs of the program. The following sections briefly
explain the criteria in Figure 3-3. Complexity categories, discussed
below, are defined in Figure 3-2.
3-7
-------
COMPLEXITY
ASSUMPTIONS FOR GENERALIZED COMPLEXITY CATEGORIES
GASEOUS EMISSIONS
ONLY - GAS AND OIL
FIRED COMBUSTION
SOURCES
ALL OIL OR GAS INTERNAL OR EXTERNAL COMBUSTION
SOURCES IN THE RESIDENTIAL AND COMMERCIAL/
INSTITUTIONAL CLASSES
ALL OIL OR GAS INTERNAL COMBUSTION SOURCES IN
THE INDUSTRIAL OR ELECTRICAL GENERATION CLASSES
ASSUMPTIONS:
1. NO SIGNIFICANT PARTICULAR >3p WILL BE
COLLECTED
2. NO SIGNIFICANT FUGITIVE EMISSIONS ARE PRESENT
3. NO SOLID STREAMS ARE PRESENT
4. NO WATER STREAMS ARE PRESENT
B
GASEOUS/ASH
EMISSIONS ONLY -
COAL FIRED
COMBUSTION
SOURCES
ALL COAL-FIRED COMBUSTION SOURCES IN THE
RESIDENTIAL AND COMMERCIAL/INSTITUTIONAL
CLASSES
ASSUMPTIONS:
1. FULL RANGE OF PARTICULATE WILL BE COLLECTED
2. NO SIGNIFICANT FUGITIVE EMISSIONS ARE PRESENT
3. NO WATER STREAMS ARE PRESENT
COMPLEX OIL AND
GAS FIRED
COMBUSTION
SOURCES
ALL EXTERNAL OIL AND GAS FIRED COMBUSTION
SOURCES IN INDUSTRIAL AND ELECTRICAL GENERATION
CLASSES
ASSUMPTIONS!
1.
WILL BE
NO SIGNIFICANT PARTICULATE
COLLECTED
2. NO SIGNIFICANT FUGITIVE EMISSIONS ARE PRESENT
FUGITIVE SURVEY WILL BE PERFORMED AT OIL FIRED
SITES IF OBVIOUS PROBLEMS EXIST
3. NO BOTTOM ASH SAMPLES WILL BE TAKEN
4. THREE WATER STREAMS WILL ALL BE SINGLE PHASE
COMPLEX COAL AND
REFUSE FIRED
COMBUSTION
SOURCES
ALL COAL AND REFUSE FIRED COMBUSTION SOURCES IN
INDUSTRIAL AND ELECTRICAL GENERATION CLASSES
ASSUMPTIONS:
1. FULL RANGE OF PARTICULATE WILL BE COLLECTED
2. FUGITIVE EMISSIONS SURVEY WILL BE PERFORMED
IF OBVIOUS PROBLEMS EXIST
3. SEVEN WATER STREAMS INCLUDING THREE TWO PHASE
STREAMS WILL BE SAMPLED
4. TWO ASH STREAMS INCLUDING BOTTOM ASH AND
PARTICULATE CLEAN-UP ASH WILL BE SAMPLED
Figure 3-2. Source Type and Complexity Classification
for Level 1 Sampling and Analysis
3-8
-------
SPECIAL CASE
ANALYSES
d'ANDF"
ANALYSES CHECK
ON SELECTED
SAMPLES
CO
I
vo
WATER QUALITY- PERIODIC
TESTS
NEGATIVE RESULTS:
PERIOD SPOT CHECKS
ON CATEGORIES B
ANDD
POSITIVE RESULTS:
REPORT RECOMMENDA-
TIONS FOR MORE
DETAILED STUDY
COMPOUND IDENTI-
FICATION STUDIES
ESCA, X-RAY DIFF-
RACTION AND
OTHER TECHNIQUES
FORSULFATEAND
OTHER COMPONENT
STUDIES
FUGITIVE EMISSIONS
NOTE SPECIAL CON-
DITIONS. TAKE
SAMPLES WHERE
APPROPRIATE OR USE
INDICATOR TUBE
TESTS
TEST PLAN
PRODUCES THE
DESIRED
INFORMATION
COMPOUNDS
IDENTIFIED ARE OF
SPECIAL OR UNUSUAL
ENVIRONMENTAL
INTEREST-
RECOMMENDATIONS
FOR MORE DETAILED
STUDY
NEGATIVE RESULTS FOR A
SPECIFIC PARAMETER OR
COMPONENT WILL EXCLUDE
THAT PARAMETER OR
COMPONENT
POSITIVE RESULTS FOR A
SPECIFIC PARAMETER OR
COMPONENT WILL REQUIRE
RECOMMENDATIONS FOR
MORE DETAILED STUDY
FUEL ANALYSIS
COMPLETE INORGANIC
CHARACTERIZATION
IF ANALYSIS DEVIATIONS
ARE STATISTICALLY INSIG-
NIFICANT, THEN OBTAINED
DATA MAY BE USED FOR
MASS BALANCE FOR
REMAINING TESTS
IF DEVIATIONS ARE
STATISTICALLY
SIGNIFICANT, THEN
ALL FUELS MUST BE
ANALYZED FOR THE
DURATION OF THE
PROJECT.
DEVELOP SPECIAL
TEST PLAN WHERE
NECESSARY
Figure 3-3. Special Case Analysis Plan
-------
3.4.1 Polychlorinated Biphenyls (PCB)
The various polychlorinated biphenyl species are of current
environmental interest. While it is unlikely that these species will be
found in any appreciable quantity, those samples in which they are the
most likely to occur have been identified for detailed study. Complexity
category B and D systems are coal fired and, based on current data, are
likely sources for PCB analysis. For this reason, it was planned to
select three sites from category B and two sites from category D for initial
PCB sampling and analysis. However, from the inception of this program to
date, no PCBs have been found on any concurrent EPA program. Thus, the PCB
analysis requirement was dropped.
3.4.2 Polynuclear Organic Material (POM)
POMs are known to exist as by-products of coal combustion. These
combustion systems have been studied but the exact extent and range of
their emissions are for the most part unknown. For this reason, all
sample extracts are identified for GC/MS analysis. If results are positive
for POM, GC/MS will continue to be performed for particulate and XAD-2
module samples. If no POMs are found by GC/MS in the first five samples
studied for each type of fuel (gas, oil and coal) or source category, the
analysis intensity will be reduced to periodic spot checks.
3.4.3 Chloride and Fluoride Analysis
Chloride and fluoride analysis are difficult to obtain by SSMS
methods because the volatility of these elements. The special analysis
techniques for these elements, as described in Sections 8.9 and 8.10, re-
present an additional cost over SSMS analysis and considering the available
data on chloride and fluoride distributions in fuels and ash, it will not
be cost effective to perform these.analyses on all samples from all sites.
A selection of samples will be chosen for complete Cl" and F" analysis.
If the results are as expected, periodic spot checks will be continued.
If the results are unique, recommendations will be made for more detailed
study.
3-10
-------
3.4.4 Water Quality Tests
Complexity category C and D sites are the only sources that are
expected to generate aqueous samples requiring both traditional and the
more complex Level 1 water quality testing. However, at present most of
these sites are monitored for compliance to water quality standards by
various federal, state, and local agencies. Thus, it is expected that the
water quality data base will be sufficient to preclude extensive water
testing. Thus, these tests will be limited to the following:
• All sites where water quality standards are not enforced.
t Three sites from each complexity category where standards
are enforced.
Specific problem areas identified as a result of the water quality
analyses will be isolated for additional study at the conclusion of the
three site analyses. Periodic spot checks will then be performed on
incoming samples to increase reliability of preliminary observations.
This topic is treated in detail in Section 3.8.
3.4.5 Special Inorganic Compound Identification Studies
X-ray diffraction, scanning electron microscopy - electron dispersive
X-ray spectrometry, electron spectroscopy for chemical analysis and other
sophisticated instrumental techniques are used for inorganic compound
characterization studies on particulate and solids. Although these are
Level 2 techniques, present evidence indicates that the identification of
the various species (especially sulfate) may be required on sites from each
complexity category. Selected samples will be used for more detailed com-
pound identification testing based on the Level 1 results and program data
needs.
Because much of this technology is state of the art and also the sub-
ject of special investigation under another contract at TRW (EPA Contract
68-02-2165), a separate test plan will be prepared at a later date
utilizing the results of this program and/or integrating the two programs
subject to the approval of the respective project officers.
3-11
-------
3.4.6 Fugitive Emissions Studies
It is expected that fugitive emission data will be required mainly
for those coal fired source categories assigned to complexity categories
B and D and to a lesser extent to those large scale oil fired sources
assigned to complexity category C. Because complex and detailed fugitive
emission studies are presently being carried out by IERL for those types
of combustion sources, it is anticipated that these studies will supply
the data necessary for this program.
Each field test crew will be supplied with a set of indicator tubes
to measure gaseous species where known problems exist or are expected to
exist, (e.g., tests for SOX, NOX, and C02 in the furnace rooms of
boilers with positive pressure.)
3.4.7 Fuel Feed Analysis
In order to obtain mass emission data, a reliable analysis of the
fuel feed stock is required. It is expected that feed stocks will differ
enough from site to site that individual analyses will be required on a
per site basis. In the event that component differences between like
fuel feeds are not significant enough to negatively impact mass emission
determinations, a sufficient number of fuels will be analyzed to provide
a reliable data base. If this data base can be established, fuel feed
analysis will be terminated.
3.5 ANALYSIS CRITERIA FOR LIMITED QUANTITIES OF PARTICULATE SAMPLES
Figures 3-4 and 3-5 illustrate the analysis planning criteria for those
flue gas samples which are limited in quantity due to a low grain loading
of the flue gas. In this scheme, inorganic analysis always has first
priority. In those samples where quantity is extremely limited, SSMS
only will be performed. Particulate samples from sources with a grain
loading of less than 0.01 grain/SCF will not normally be analyzed. In
systems where grain loading is high enough to produce a sufficient quantity
of particulate to warrant solvent extraction for organic material, the
removal of 5% of the catch for inorganics will not significantly impact
the analysis results.
3-12
-------
COAL
FIRED SYSTEMS
>0.9 GR/SCF -
>3»i >43 GRAMS;
<3»» >19 GRAMS
< 0.9 GR/SCF-
>3>t < 43 GRAMS;
<3lt < 19 GRAMS
COMPLETE ORGANIC
AND POM ANALYSIS
ON >3H SIZE FRACTION;
LIMITED NUMBER PCB'S
5% OF BOTH CATCHES
FOR INORGANIC
COMBUSTION OR
DIGESTION
FROM 0.2 GR/SCF TO
0.89 GR/SCF COM-
BUST! ON, DIGESTION,
AND INORGANICS.
LIMITED ORGANIC
ANALYSES.
FROM 0.04 GR/SCF TO
0.89 GR/SCF COMBUS-
TION, DIGESTION, AND
INORGANICS. LIMITED
ORGANIC ANALYSES.
NO ORGANIC AND
POM ANALYSIS ON
THE <3H CATCH
AS NECESSARY
<0.2 GR/SCF -
SSMS ONLY ON THE
CATCH.
CI'ANDF"
ON A LIMITED NUMBER
OF SAMPLES.
Figure 3-4. Partlculate Analysis Decision Criteria
for Coal Fired Systems
3-13
-------
OIL
FIRED SYSTEMS
>0.02 GR/SCF
CATCH = 100% <3j.
>1.4 GRAMS
< 0.02 GR/SCF
CATCH = 100%
<1.4 GRAMS
COMPLETE PAH AND
ORGANIC ANALYSIS •
PAHS LIMITED
IN NUMBER
COMBUSTION,
DIGESTION, AND
INORGANICS ON
5% OF THE CATCH
ORGANIC ANALYSIS
LIMITED IN NUMBER
COMBUSTION,
DIGESTION, AND
INORGANICS
Cl AND F
ON A LIMITED NUMBER
OF SAMPLES
Figure 3-5. XAD-2 Module Analysis Decision Criteria
for Oil Fired Systems
3-14
-------
3.6 ANALYSIS CRITERIA FOR XAD-2 MODULE SAMPLES
The XAD-2 module produces several samples that must be analyzed both
for inorganic and organic components. Because individual analysis of
samples is neither necessary nor cost effective, these samples are combined
and analyzed once for inorganic and organic components as shown in Fig-
ures 3-6 and 3-7. Figure 3-8 shows the inorganic analysis scheme effective
after EPA approval (after September, 1978).
3.7 PLANNING AND ANALYSIS CRITERIA FOR ORGANIC COMPONENTS
The analysis of samples for organic components is a very complex
and cost sensitive area and for this reason a high degree of effort will
be expended in the planning and tracking of samples for organic analysis.
Generally speaking, all SASS train rinses and extractable samples such as
particulates, XAD-2 resin and condensate, water, bottom ash, and slurries
will be extracted and analyzed for organics unless experience or the
organic analysis decision criteria indicates termination of the analysis
procedure. Because fuels have been extensively analyzed for organic com-
ponents, no analysis of these components will be performed unless a direct
link between fuel composition and fuel gas emission is suspected.
3.7.1 General Organic Decision Criteria
The area of organic analysis is unique in that several decision
points are an integral part of the procedure and must be applied by the
analyst as an integral part of the procedure. In this revision, the
detailed application of these criteria is included in Chapter 7. A
summary of these decision points/criteria is given in Table 3-5.
3-15
-------
XAD-2
MODULE
SAMPLES
ORGANIC
MODULE SOLVENT
RINSE COMBINED
WITH XAD-2
RESIN EXTRACT
XAD-2 MODULE
CONDENSATE
EXTRACT
KUDERNA-DANISH
CONCENTRATION
AND GRAVIMETRIC,
|R, C7-C,6 GC
SEPARATE
ANALYSIS
ANALYZE SEPARATELY
IF ORGAN!CS ARE
GREATER THAN 10%
OF MODULE RINSE AND
RESIN EXTRACT
f
1
1
TCO AND GRAV
<0.5MG/M3STOP
AT THIS POINT
TCO AND GRAV
*0.5MG/M3LC
SEPARATION AND
FURTHER ANALYSIS
SEE FIGURE 7-2
i
POMS AS
SPECIFIED
LRMS ON EVERY
FRACTION »15MG;
SPOT CHECKS ON
OTHER FRACTIONS
Figure 3-6, XAD-2 Module Organic Analysis
Decision Criteria
3-16
-------
XAD-2
MODULE
SAMPLES
CO
I
INORGANIC
MODULE 15% HNOgACID
RINSE COMBINED WITH
CONDENSATE AND
H O IMPINGER
PARR BOMB
COMBUSTION
OF 2 GRAMS
OF RESIN
PRIORITY NO. 1
TRACE ELEMENT
ANALYSIS
PRIORITY NO. 2
Cl" AND F" LIMITED
IN NUMBER
PRIORITY NO. 1
TRACE ELEMENT
ANALYSIS
PRIORITY NO. 2
Cl "AND F" LIMITED
IN NUMBER
Figure 3-7. XAD-2 Module Inorganic Analysis Decision Criteria
-------
XAD-2
MODULE
SAMPLES
CO
00
1
H2°2
IMP1NGER
INORGANIC
i
t
MODULE 15% HNO,
ACID RINSE J
i
' 1
XAD-2
MODULE
CONDENSATE
t
ACID EXTRACTION
OF 15 GRAMS OF
RESIN
COMPOSITE FOR
PRIORITY NO. 1
TRACE ELEMENT
ANALYSIS
COMPOSITE FOR
PRIORITY NO. 2
Cl" AND F" LIMITED
IN NUMBER
Figure 3-8.
XAD-2 Module Inorganic Analysis Decision Criteria
Pending EPA Approval
-------
Table 3-5. Organic Analysis Decision Points
Decision Point
Description
Section
Initial Extraction
Gravimetric Analysis
Total Chromatographable
Organics, C7-Ci6 (TCO)
Infrared Analysis
Low Resolution Mass
Spectroscopy
POM Analysis
Organic analysis omitted if 3.5
quantity of particulate catch is
limited and/or meets certain
criteria (see below).
a) Analysis terminated if organics 7.5
concentration is <0.5 mg/m3
b) Analysis on the XAD-2 conden-
sate is discontinued if
nonvolatile matter <10% of
total organics or <0.5 mg/m3.
Simplified liquid chromatographic 7.7, 7.8
(LC) separation used if TCO <10%
total organics.
Analysis not run on less than 7.6
0.5 mg for basic gravimetric
residues and for LC fractions.
Run only on total residues of LC 7.6, 7.9
fractions, if present in concentra-
tions of >0.5 mg/n)3.
Performed only on all fractions. 7.10
3-19
-------
3.7.2 Prediction of Quantity of Organic Material In Participate Catches
The organic analysis planning and decision criteria is being
emphasized for participate samples because these samples represent a large
proportion of the total sample collected. Significant cost savings with
no loss in technical quality can be realized if samples that will not meet
the Level 1 organic analysis criteria (i.e., <0.5 mg/m3) can be eliminated
without the expenditure of significant quantities of labor. However, pro-
gram requirements to analyze all extracts for ROMs, the lack of >3y
particulate in all cases where the source was controlled, and the gener-
ally very low amounts of <3y particulate has resulted in little need for
the prediction criteria presented in earlier draft version of the manual.
Thus, the nomograph and the remaining parts of the section have been
deleted.
3.8 WATER SAMPLING AND ANALYSIS PROTOCOL
3.8.1 Sampling Wastewater Emissions
The major wastewater emissions from stationary combustion sources are
described in Table 3-6. These wastewater emissions are similar in character-
istics for the utility and industrial sectors, and insignificant or non-
existent in terms of total quantities discharged for the commercial/
institutional and residential sectors. An adequate characterization of the
wastewater emissions from the utility sector is therefore considered
adequate for all combustion source types.
3-20
-------
Table 3-6. Wastewater Emissions from Stationary
Combustion Sources
Unit Operation
Fly ash pond discharge
Bottom ash pond discharge
Coal pile drainage
Cooling system waste
Boiler blowdown
Water treatment
Equipment cleaning
Desulfurization Wastewater
Fuel
Coal
S
S
S
IS
IS
IS
IS
S
Res id
Oil
MS
MS
NA
IS
IS
IS
IS
S
Distillate
Oil
MS
MS
NA
IS
IS
IS
IS
S
Gas
NA
NA
NA
IS
IS
IS
IS
NA
S = source
MS = minor source
IS = sources for which wastewater characteristics are Independent
of type of fuel burned.
NA = not applicable
3-21
-------
As discussed in Reference 5, review of recent and current combustion
system studies indicates that there are a number of parallel projects that
are directed towards the characterization of wastewater emissions from
power plants, Specifically, these projects include:
1) A current TVA study (EPA-IAG-D5-E721, TV-41967A) to
characterize coal pile drainage, ash pond discharges,
chlorinated once-through cooling water discharge, and
chemical cleaning wastes from periodic boiling-tube
cleaning to remove scales. The TVA program samples
and analyzes the waste water emissions from TVA owned
coal burning power plants. The TVA power plants are
either of the pulverized dry bottom or the cyclone
variety.
2) A current study conducted by Hittman Associates to
characterize ash handling and material storage wastes
from four coal burning power plants (lignite, subbit-
uminous, and bituminous coal), cooling system wastes
from eight power plants (once through and recircula-
tive system, fresh and saline water), copper boiler
wastes from two power plants, and low volume wastes
(such as equipment cleaning wastes) from two power
plants.
3) Current and recent studies conducted by the Aerospace
Corporation to provide data on the characteristics of
wastewater emissions from flue gas desulfurization
systems. The four systems from which scrubber liquors
were analyzed included the EPA/TVA Shawnee steam plant
venturi and spray tower, the EPA/TVA Shawnee steam
plant turbulent contact absorber, the Arizona Public
Service Cholla Station flooded disc scrubber and
absorption tower, and the Duquesne Light Phillips
Station single and dual stage venturi.
Our analysis of currently available information, however, shows,
a number of areas where there are significant data gaps. In summary,
the following conclusions have been reached:
3-22
-------
• Adequate emissions data for coal pile drainage will be
available from the TVA program.
• Emissions data for water treatment wastes are considered
adequate because both the quantity and the characteristics
of the water treatment wastes can be estimated with
reasonable accuracy from mass balance calculations.
• Emissions data for cooling system wastewater, equip-
ment cleaning wastewater, desulfurization wastewater
and boiler blowdown are limited.
• Emissions data for ash pond discharges are adequate
for bituminous pulverized dry bottom boilers and
inadequate for other types of coal-fired boilers,
and.also inadequate for resid oil fired boilers.
Based on the above conclusions, the present sampling plan for
wastewater emissions are as follows: ^Q ^
Unit Operations Test Sites
Ash Pond Discharge
Bituminous Wet Bottom 5
Bituminous Cyclone 2
Bituminous Stoker 1
Lignite Pulv. Dry Bottom 2
Lignite Cyclone 2
Lignite Stoker 1
Resid Oil 5
Cooling Tower Blowdown 2-5
Once through Cooling System 2-5
Boiler Blowdown 3-5
Equipment Cleanup 2-5
Desulfurlzation Wastewater 2-5
3.8.2 Analysis
Due to the large number and quantity of samples required for analysis
and the potential for sample degradation during shipment, most of the
standard waste water analyses will be performed in the fields by the Hach
analysis methods as described in Chapter 6. BOD and COD analysis were
thoroughly investigated, and it was found out that these results were not
necessary. A summary of the water analyses to be performed is given in
Table 3-7. 3.23
-------
Table 3-7. Liquid Stream Sampling and Analysis Protocol
General Information
Parameters to
be Analyzed
Flow
PH
Cond
TSS
Hardness
Alk. or Acid
NHyN
Cyanide
NO,-N
P04-P
so3
SO.
4
Cl
F
Ca
Mg
K
Ma
Other Trace
Elements
Total
Organics
PAH
PCB
Other Organics
Analysis
Location
Field
F
F
F
F
F
F
F
F
F
F
F
F
Lab
L
L
L
L
L
L
L
L
L
Volume
Sample Required
1 liter
1
200
i
i
il
i
800 ml
It Organic
L CHoCU Extract
L
l I
Method
of Analysis
Plant
Meter
or
tucket/Stopwatch
Portable Meter
Hach Kit
Hach Kit
Hach Kit
Hach Kit
Hach Kit
Hach Kit
Hach Kit
Hach Kit
Hach Kit
Hach Kit
i Specific ion
) Electrode
\
SSMS
GC-TCO and
Gravimetric
GC/MS
GC/MS
i
Sampl e
Preservation
Required
;
Non
i
0.1N
|
a
t
HN03
to pH 2
!
|
CH2C12
r
i
Ext
Amber Bottle
with Teflon
Seal
i K
Sampling Locations and Analysis Requirements
Type A
Ash Ponds
X
X
X
X
x.
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Type B
Cooling H»0
B1 owdown
X
X
X
X
X
X
Cr (Total)
X
X
X
Type C
Cleaning
Waste
X
X
X
X
X
X
X
X
X
X
X
X
X
,
Comments
May be discontinued later on
May be discontinued later on
May be discontinued later on
CO
ro
-------
3.9 SPECIAL ANALYSIS CRITERIA FOR GAS, DISTILLATE OIL AND RESIDUAL OIL
COMBUSTION SOURCES
The available literature and program experience had indicated that a
complete Level 1 analysis of gas, distillate oil, and residual oil com-
bustion sources was not providing meaningful data due to the very low
levels of particulate and organic material present. Specifically, the
various Level 1 analysis for the different samples from the SASS train
were either giving negative results or results with high variance due to
low levels present. Thus, for these sources a series of analysis deletions,
and sample combinations were proposed in order to reduce analysis costs
and increase data precision and accuracy for these sites. These were
implemented as a directed contract change after June 7, 1978. They are
listed below.
• Natural Gas Fired Sites
a) Eliminate all inorganic analysis on SASS train samples.
b) Combine all SASS train organic extracts and rinses into
a single sample before analysis.
• Distillate and Residual Oil Fired Sites
a) Compute inorganic emissions from fuel analysis assuming
100% emissions.
b) Eliminate all inorganic analysis on SASS train samples.
c) Combine all SASS train organic extracts and rinses into
a single sample before analysis.
3-25
-------
3.10 REFERENCES
1) C. A. Zee, et al, "Evaluation of the SASS Train and Level 1 Sampling
and Analysis Procedures Manual", TRW Contract No. 68-02-2165 Task 5,
Redondo Beach, Ca.
2) S. L. Reynolds, et al, "SASS Train and Level 1 Procedures Evaluation"
TRW Contract No. 68-02-2165 Task 14, Redondo Beach, Ca.
3) Norman Surprenant, et al, "Preliminary Emissions Assessment of
Conventional Stationary Combustion Systems, Volume II", Contract
No. 68-02-1316 Task 2, GCA Corporation, Bedford, Mass.
4) A. E. Vandegrift, et al, "Particulate Pollutant System Study",
Vol. 1, 2 and 3, Contract No. 22-69-104, Midwest Research
Institute, Kansas City, Mo.
5) C. C. Shih to B. J. Matthews. Emissions Data Needed from Field
Sampling and Analysis Efforts. IOC 4342.5-77-009. 1 February 1977.
3-26
-------
4.0 SAMPLE AND DATA MANAGEMENT
The sample and data management function will involve the Sample Bank
Manager along with the Laboratory Operations Manager and will provide
interfacing and support in several key areas:
• Receiving field samples
• Maintaining a sample bank
• Relating field results to laboratory decisions
t Disbursing samples to analysts
• Tracking and controlling sample flow
• Collecting and reducing analytical data
• Preparing reports of analytical data
4.1 SAMPLE MANAGEMENT
4.1.1 Sample Receiving
The inspection and logging of samples as they are received is, in
essence,a quality control measure. The shipment of field data forms
and samples are checked for procedural correctness and completeness,
field measurements of volumes and weight are remeasured for QC, and solid
samples are photographed for documentation.
4.1.1.1 Unpacking and Inventory
An area of the laboratory is dedicated and maintained for sample
receiving. As the samples are unpacked, the exterior of the sample
containers is wiped with a damp paper towel. The samples are logged
in using the form shown in Figure 4-1. Notes and comments written on
the sample container labels are recorded and solid samples that are
subject to oxidative changes are purged with dry nitrogen and sealed
with Teflon tape. There is also space allowed on this form to note
samples which have been photographed (see Section 4.1.1.3).
4-1
-------
SAMPLE RECEIVING CHECK LIST
iAMn-CillC
rrs in MO
DATF SH|PPFD DATE RFrFJVFD
TEST NO
DATF UNPACKFD
SAMPLE
CONTROL NO.
-
SAMPLE
DESCRIPTION
DAMP
WIPE
PHOTO
N2
PURGE
TEFLON
SEAL
COMMENTS
_
__
-
4-1. Sample Receiving Check List
4-2
-------
4.1.1.2 Quality Control Check
To verify the quality of the recorded field data, selected samples
from each shipment will be checked for the following critical parameters:
• Sample collection weight
• Sample volume
• pH value from a field fixing operation
• Type of container used *
For this check, the form shown in Figure 4-2 will be used. Collection
weights will be checked on cyclone catch samples. Volumes will be checked
on all solvent samples (hardware rinses and liquid extractions), acid
XAD-2 module rinses, and impinger liquids. Samples that have had acidic
splits prepared (bulk liquids and XAD-2 module condensates) will be
checked for pH. This work is to be done in the Cleanroom area at TRW
(01/2031) and in an equivalent facility at GCA .
4.1.1.3 Photography
Photographs of the SASS train filters will be taken to document the
"as received" condition of the samples and general gross characteristics.
Photomicrography will then be conducted on filter samples or solid samples
designated by the Laboratory Operations Manager to observe and record finer
structural characteristics. Magnifications from 30X to 600X will be used
to examine the samples. The microscopic work will also be conducted in the
Cleanroom area at TRW (01/2031) and 1n an equivalent facility at GCA.
4.1.2 Sample Bank and Storage
The sample barik consists of a centralized locked storage area to which
only the Sample Bank Manager and his designees have access. Cabinets for
active storage will be located at TRW and at GCA. Long term storage for
both TRW and GCA samples will be maintained at TRW. These facilities
assure that the temperature, humidity and light exposure will be maintained
within a constant range. (Temperature 65-75°F, relative humidity 20-4035 and
storage 1n the dark). Organic samples resulting from solvent rinses and
extractions will be stored 1n explosion-proof refrigerators to preserve
sample Integrity and minimize solvent loses.
4-3
-------
SAMPLE RECEIVING OC
SAMPLE SITE
CCS ID NO.
QC CHECK PERFORMED ON (DATE):
TEST N0._
., BY (SIGNATURE):.
SAMPLE
CONTROL NO.
TYPE OF
CONTAINER
WEIGHT (g)
FIELD
LAB
VOLUME (ml)
FIELD
LAB
PH
FIELD
LAB
COMMENTS
Figure 4-2. Sample Receiving QC
4-4
-------
4.1.3 Sample Disbursement
The samples remain in active storage until the Laboratory Operations
Manager directs the Sample Bank Manager to disburse the samples and a
disbursement plan .is agreed upon. The basic plan, as shown in Figure 4-3,
will be followed for all facilities with adjustments and allocations
determined by the decision criteria discussed in Chapter 3.
The actual manipulation which reduces the gross samples to repre-
sentative aliquots .for analysis must be conducted in the Cleanroom to
prevent contamination. The issuing of aliquots will be done at one time
as much as possible for ease of handling the divided samples and also
to maintain consistency and integrity. The homogenizing and disbursement
of each bulk sample and SASS train catch are discussed separately in
the following paragraphs.
4.1.3.1 Bulk Liquid Samples
Bulk liquid samples are received in gallon (4-liter) containers and
represent collected waste water, reservoir water, cooling water, evapora-
tion pond water, the liquid portion of a slurry, or bulk fuel oil samples.
The aqueous samples will have been extracted for organics with methylene
chloride in the field. These solvent extracts proceed directly to the
organic analysis scheme. The aqueous phase from the field extraction
will have been split into acidic and neutral portions for trace metal,
suIfate and anion analyses. Aliquots are taken by agitating
the containers for 30 seconds and then pipeting the sample volume specified
by the disbursement plan into a suitably cleaned container.
Aliquots of the bulk fuel oil samples for ultimate analysis, and Parr
bomb combustion, and Inorganic analyses are taken by simply pouring an un-
measured portion into a small, clean container and allowing the analyst to
weigh out the precise sample amount needed.
4-5
-------
ANALYTICAL TESTS
DISBURSEMENT
TRAVELERS ISSUED
WEIGHTS/VOLUMES
INDICATED
BULK LIQUID
1
SLURRY
BULK SOLIDS -
TATE
CONE AND
QUARTER
FILTER
1 TO 3^ CYCLONE »
SECTION
COMBINE
CONE AND
QUARTER
3 TO lOd CYCLONE
>10M CYCLONE
SOLVENT
PROBE/CYCLONE
RINSE
XAD-2
SOLVENT MODULE
RINSE
CONDENSATE
SOLVENT EXTRACT
CONDENSATE
HN03 MODULE ]
RINSE |
IMPINGER
CONE AND
QUARTER
COW
BINE
CONE AND
QUARTER
AGITATE
FILTER
SOLIDS
CONE AND
QUARTER
-
APS
IMPINGERS
PROPOR1
COMBIN
IONAL
ATION
f
AGITATE
AGIT
ATE
._ VOLUMETRIC
ALIQUOT
t
SOLVENT
EXTRACT
_ WEIGHSD
ALIQUOT
_ SOLVENT
EXTRACT
__ PARR BOMB
COMBUST
_-. AQUA R£GIA
P DIGEST
H
\_ SOLVENT
EXTRACT
__. AQUA REGIA
P WGEST
L SOLVENT
EXTRACT
H VOLUMETRIC
ALIQUOT
J WEIGHED
" ALIQUOTS
1 '
"*1 SOLVENT
EXTRACT
^PARR BOMB
COMBUST
A JP
«/i x
*
*
sf
*
•o
1
J*
*
IK/WT.AKMS 1
IC/\VT.A*MS
*
j
PROXIMATE
& ULTIMATE t 1
Figure 4-3. Disbursement
* Ai AND Sb PERMOHWED BY SSMS
WHERE POSSIBLt AFTER 6/1/78
t FUEL SAMPLE ONLY
4-6
-------
4-1.3.2 Bulk Solid Samples
Bulk solid samples are received 1n large jars, bags or cans and Include
ashes and fuels. They will be prepared for analysis by the ASTM coning and
quartering procedure (Appendix D). This procedure shows in detail how to
systematically divide a large sample into representative parts. Coning
and quartering of all samples 1s to be conducted in the Cleanroom's laminar
flow bench on a piece of precleaned Teflon sheet. The Sample Bank Manager
Is responsible for calculating from the reported bulk sample weight how
many dividing steps must be performed to obtain the sample weight specified
by the disbursement plan. In some cases, it may be necessary to obtain a
fairly large portion, grind this to a finer mesh, and then proceed with
the coning and quartering to obtain analytical size samples.
Bulk fuel samples will require disbursement of about 150 g for proxi-
"»te and ultimate analysis and about 5 g for Parr bomb combustion and in-
organic analysis. Other process solid samples (bottom ash, flyash, pre-
cipitate dusts, etc.) will be allquoted for both organic and inorganic
routine analyses. Special testing requested by the Laboratory Operations
Manager, e.g., XRD or ESCA, will require disbursing additional aliquots.
4.1.3.3 Particulate Filters
Partlculates, whether collected on a filter or in bulk, contain varying
amounts of moisture. Before any sample is disbursed for analysis, it must
be desiccated adequately to produce a constant sample weight. Each sample,
"In its open container, is placed in a desiccator containing Drierite for
seven days. At the end of this period, the sample is weighed on an analy-
tical balance to the nearest 0.1 mg. All samples are returned to the
desiccator for an additional minimum of 24 hours. A series of at least
four weighings is needed as a check of the accuracy and reproducibillty of
the original weight, although more may be needed. A standard deviation, s,
of less than 10 mg 1s one criterion for deciding whether the average weight
Is stable. Applying a statistical test to the results to detect a gradual
change 1n the average weight, or constant weight, 1s often required. The
average variance between successive pairs of weighings, q2, Is compared
with the overall variance of all weighings, s . The calculated ratio
22
°. /s a r can be compared with values in statistics tables. Weighings are
4-7
-------
continued and outlying value discarded until an acceptably low r value 1s
obtained. Then the average weight Is accepted as valid.
The quantity q 1s given by
2 n-1
(n-1)2
where
D1 = difference between consecutive weighings
n = number of weighings
The filter collected sample typically cannot be representatively
removed by mechanical methods. It is, therefore, sectioned using a pre-
cleaned knife. Sections are wedges produced by cutting along the diameter
of the filter. The number of sections to be cut and their disbursement
will depend on the type of source sampled and the weight of collected
material as discussed in Chapter 3, Decision Criteria, and thus will be
specified as part of each site's disbursement plan.
4.1.3.4 1 to 3 Micron Cyclone
The l-3y cyclone sample handling and disbursement parallels that of
the filter, because these two samples are generally combined for analysis.
For example, assume that the filter from a site test is disbursed 1/2 for
organic solvent extraction and 1/4 for aqua regia extraction (with 1/4
held 1n reserve in the sample bank) and that the 100 ml aqua regia extract Is
In turn disbursed 80 ml for Hg and SO. and 20 ml for SSMS. To proportion-
ally combine the l-3y cyclone catch, that sample would be disbursed 50%
for organic solvent extraction, 20% for aqua regia extraction, and 5% for
SSMS. After desiccation to constant weight, the cyclone catch Is coned
and quartered in the same manner as the bulk solid samples.
4.1.3.5 3-10 and >10 Micron Cyclones
After having been desiccated for a sufficient time to attain a con-
stant weight (Section 4.1.3.3), these two cyclone samples are separately
coned and quartered and then combined by a weight which represents an
equal percentage of each. Portions are then disbursed for organic solvent
extraction, aqua regia extraction, SSMS, and other special tests as
necessary and as the quantity of sample available permits.
4-8
-------
4.1.3.6 Solvent Probe/Cyclone Rinse
The solvent rinse of the probe and cyclones Is filtered through a pre-
cleaned and tared Teflon MllUpore filter, and the solvent filtrate 1s then
disbursed for organic analysis. The filtered sol Ids are desiccated and
weighed; and if they are found to represent > 10% of the total partlculate
catch, they are disbursed for inorganic analyses by direct SSMS and aqua
regla extraction for Hg and S04.
4-1.3.7 XAD-2 Resin
Resin samples are also coned and quartered, with the bulk of each
sample going for solvent extraction. The only other aliquot taken is
approximately 10 g, from which the sample for Parr bomb combustion is
weighed, with the remainder being kept in the bank as a reserve. The
solvent extract of the resin 1s subsequently combined with the solvent
rinse of the XAD-2 module for organic analysis. The Parr bomb solution
Proceeds through the inorganic analysis as an Integral sample without
being combined with any other SASS samples.
This Procedure will be changed along with Figure 4.3, if the proposed
procedure in Section 8.2 is approved by EPA. In order to provide adequate
sample representation in the inorganic, organic and reserve sample aliquots,
the following steps will have to be performed when the new procedure is
adopted.
1. Keep the wet or dry XAD-2 resin in the original bottle as received
from the field.
2. Stir the resin with a glass stirring rod. It is important that
the resin is thoroughly mixed. Stir constantly for at least two
minutes.
After mixing, place the following aliquots in the indicated
containers:
a. 10 grams of resin in a 50 ml amber glass jar for Parr Bomb
combustion and sample reserve.
b. 15 grams of resin in a 50 ml amber glass jar for the proposed
inorganic analysis.
c. The remaining resin, * 125 grams, in the original container
received from the field for organic analysis.
4-9
-------
4.1.3.8 XAD-2 Module Condensate
In the field, 90$ of the condensate is extracted with methylene
chloride. The unextracted portion of the aqueous phase from the extractior
is then acidified. When these samples are received in the lab, they are
disbursed as follows:
• Neat Extracted Condensate - no routine disbursement, this sample
is held in the bank until a special analytical need is identified
by the Laboratory Operations Manager.
• Methylene Chloride Extract - this sample 1s disbursed for organic
analysis as an integral sample.
• Acidic Split - an aliquot proportional to the percentage of resin
used for inorganic extraction, is combined with portions of the
acid module rinse and the first impinger, and the resulting
solution is disbursed for SSMS and Hg analyses.
4.1.3.9 XAD-2 Module Solvent Rinse
The solvent module rinse is proportionally combined with the extract
of the XAD-2 resin and is then disbursed for organic analysis.
4.1.3.10 XAD-2 Module Acid Rinse
An acid module rinse aliquot proportional to the percentage of resin
used for inorganic extraction, is combined with portions of the acidic
condensate split and the first impinger solution, and inorganic extraction.*
The resulting solution is disbursed for inorganic analyses as specified
1n each site's disbursement plan. The aliquot volume of each sample to be
combined will also be specified in the disbursement plan.
4.1.3.11 First Impinger
A peroxide Impinger volume proportional to the percentage of resin
used for Inorganic extraction 1s combined with portions of the acidic
condensate split, the acid module rinse and inorganic extract.* The
resulting solution is disbursed for Inorganic analyses as specified 1n
each site's disbursement plan. The aliquot volume of each sample to be
combined will also be specified 1n the disbursement plan.
4.1.3.12 Second and Third Impingers
An aliquot of the combined second and third (ammonium persulfate)
Impinger solutions 1s disbursed for Hg, As, and Sb analyses.
This presumes approval of the procedure in Section 8,2.
4-10
-------
4>1-4 Sample Coding
The sample coding system to be used In this program 1s outlined 1n
Figure 4-4. This system will be used to label and Identify samples from
the time they are taken in the field through all laboratory analyses.
The sample control numbers derived through this coding system will appear
on all container labels, analytical travelers, and analytical schedule
flow control charts. Key aspects of the coding system worth noting are:
• The assigned numbers shown 1n the attached figure cover only
the samples and procedures that are currently expected to be
part of most, 1f not all, Level 1 tests. Additional numbers
can be assigned to Identify optional and Level 2 samples and
procedures.
• Sample types 1, 2, 7, and 8 do not necessarily have to be
separated slurries, but 1f slurries are encountered these
are the code numbers that should be used for them.
• If more than one partlculate filter 1s used in a test, the
letters, a, b, c, etc. can be added to the sample type code
to Identify the multiple samples.
• Samples disbursed from the sample bank will be labeled with
the sample control number identifying the next procedure to
be performed. For example, an XAD-2 sample (from the first
site sampled by the TRW east coast team) for Parr bomb com-
bustion will have the sample control number 200-XR-PB. After
the combustion, an aliquot of that sample for sulfate analysis
will be labeled 200-XR-PB-S04.
• Samples that are combined for certain analyses will acquire
a new sample type code 1n their subsequent sample control
numbers. For example, when the XAD-2 resin extract and the
solvent module rinse (from the second site sampled by the
TRW west coast team) are combined for Kuderna-Danish concen-
tration, the sample control number that will be on the sample
container and analytical traveler will be 101-XM-SE-KD.
4tl*5 Sample Tracking
Samples are tracked by using a combination of analytical traveler
worksheets, weekly and monthly summary reports, and analytical schedule
flow control charts. The traveler worksheets are issued by the Sample
ank Manager along with the samples and they contain all pertinent
"formation needed by the analyst (volume, matrix, etc.) as well as
space for the analyst to record his data. A copy of the Issued traveler
4-1-1
-------
xxx-xx-xx-xxx-xx-x
* ^*— ' " >^ ^^^V — ^SECOND LEVEL I
SITE IDENTIFICATION SAMPLE TYPE SAMPLE PREPARATION FIRST LEVEL ANALYSIS ANALYSIS THIRD LEVEL ANALYSIS
Consecutively numbered
by sampling team:
100-199, TRW West Coast
200-299, TRW East Coast
300-399, GCA
Numbers and corresponding
sample types are as
follows:
1-bulk. liquid
(separated from a
slurry)
2-bulk liquid
(separated from a
slurry)
3-bulk liauid
4-bulk liquid
FF-liquid fuel feed
CD-condensate from
XAD-2 module
PR-solvent probe/
cyclone rinse
MR-solvent XAD-2
module rinse
HM-HN03 XAD-2 module
rinse
HI-H202 impinger
AI-APS impingers
XR-XAD-2 resin
PF-filter(s)
IC-l-Sn cyclone
3C-3-10H cyclone
10C->10n cyclone
XM-XR extract plus MR
CH-HM plus CD plus HI
FC-PF plus 1C
CC-3C plus IDC
CF-solid fuel feed (coal)
5-bulk solids
6-bulk solids
7-bulk solids (separated
from a slurry)
8-bulk solids (separated
from a slurry)
Numbers and corresponding
preparation steps are
as follows:
0-no preparation
LE-liquid-liquid extraction
SE-Soxhlet extraction
A-acidified aliquot
B-basified aliquot
PB-Parr bomb combustion
HH-hot water extraction
AR-aqua regia extraction
Numbers and corresponding
procedures are as
f ol 1 ows :
Organic
0-no cone
requ i red
GC-C7-C17 GC
KO-K-0 Cone
Inorganic
SS-SSMS
AAS-Hq,As,Sb
S04-S04
N03-N03
CF-C1.F
Organic analyses on
cone samples will
be coded as
follows:
GM-GC/MS for PAHs
GI-Grav.JR
MS-LRMS
LC-LC separation
Resulting LC fractions
for grav./IR/LRMS
analyses will be
numbered in order,
1-7
Figure 4-4. EACCS Sample Control Numbers
-------
worksheets is kept by the bank manager as a record of samples in process
and the completed forms are also returned to the bank manager. Examples
of the analytical traveler worksheets to be used are shown in Appendix B.
At the end of each week, the analysts will report to the Sample
Bank Manager on the status of their areas of responsibility using the
form shown in Figure 4-5. These individual reports will then be summarized
by the bank manager and reported to the Laboratory Operations Manager
on the form shown in Figure 4-6. Similar forms to be used at month end
will include cost as well as schedule information.
The schedule data provided on the weekly summary reports will then
be used to update the analytical schedule flow control charts. These
charts, shown in Figures 4-7 to 4-9, constitute a visual system for
tracking the status of all on-going analyses. They are to be posted in
the laboratories so that the analysts and technicians can monitor their
sample workload.
4.1.6 Sample Retainment
In-process samples will be retained in the active storage areas
until completion and submittal of the analytical report. At that time,
the sample containers will be purged with dry nitrogen, sealed with tape,
and transferred to long-term storage. There they will be retained until
EPA's acceptance of the reports pertaining to them, but generally not
longer than six months.
4-13
-------
WEEKLY STATUS REPORT
ANALYTICAL SCHEDULE
WEEK ENDING: WSR NO.
ANALYSES REPORTED/JN::
ACTIVE SITES:
TOTAL NUMBER OF ANALYTICAL SCHEDULE ITEMS THIS WEEK:.
NO. COMPLETED AHEAD OF SCHEDULE:
NO. COMPLETED ON SCHEDULE:
NO. COMPLETED BEHIND SCHEDULE:
NO. STILL BEHIND SCHEDULE:
COMMENTS:.
RESPONSIBLE ANALYST:
Figure 4-5. Weekly Status Report
4-14
-------
SUMMARY
WEEKLY STATUS REPORT
ANALYTICAL SCHEDULE
WEEKENDING: WSR NO.
ACTIVE SITES:
TOTAL NUMBER OF ANALYTICAL SCHEDULE ITEMS THIS WEEK:
NO. COMPLETED AHEAD OF SCHEDULE:
NO. COMPLETED ON SCHEDULE:
NO. COMPLETED BEHIND SCHEDULE: .
NO. STILL BEHIND SCHEDULE:
COMMENTS:
Figure 4-6. Summary: Weekly Status Report
4-15
-------
Figure 4-7. Analytical Schedule Flow Control Chart (Sht 1 of 2—Organic)
4-16
-------
-
—
—
mill HANK
KN|
1
HOT WAtll
EXTIACItON
$CN|
1
AQUA KCIA
1XTIACT1ON
SCN|
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SCN|
[
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SCN|
|
Cl
JCN|
ISMS
SCN|
|
HI
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Al
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1
Sk
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1
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KNl .
r
SCN|
_L
' O™XililMl**• *• C' ***'AN*l¥S"*" ""*
t fiorouD. ui HcnoN 1.1
Figure 4-7. Analytical Schedule Flow Control Chart (Sht 2 of 2—Inorganic)
4-17
-------
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Figure 4-8. Analytical Schedule Flow Control Chart (Sht 2 of 2)
(Solid/Organic Analysis)
4-19
-------
ANALYTICAL KMDUU PlOW CONTROL CHWt
INOtOANK ANALVKS •
AU*t, », Cl, ANOr*NUYMtAMON*NOniONUIUISONiV
Figure 4-9. Analytical Schedule Flow Control Chart (Sht 1 of 2)
(Liquid/Inorganic Analysis)
4-20
-------
*NWVIKM KMDUU HOK CONIKX CHMI
INOUAMC«NUV1H •
Figure 4-9. Analytical Schedule Flow Control Chart (Sht 2 of
(Solid/Inorganic Analysis)
4-21
-------
4.2 DATA MANAGEMENT
4.2.1 Data Recording
All primary data generated by the analysts and technicians will be
recorded on the analytical traveler worksheets shown in Appendix B. If it
should be necessary to use other papers such as lab notebooks or calibra-
tion curve graphs, copies of these are to be attached to the traveler
worksheet when it is turned in to the Sampler Bank Manager.
4.2.2 Data Reduction
The first step in data reduction will be to convert the quantities
measured in the analyses to total sample concentrations. This will be
done by the responsible analysts who will obtain from the Sample Bank
Manager all of the gross volume and disbursement aliquoting information
with which to perform the required calculations. Bulk liquid and solid
data will be reduced to mg/liter and mg/kg values, respectively. All
SASS samples will be reduced to mg/m .
4.2.3 Data Review
Data calculated by the Sample Bank Manager will be reviewed for
reasonableness and consistency by the Laboratory Operations
Manager and the Quality Assurance Manager. Procedures for the handling
of discrepant data are discussed in Chapter 2 of this manual. The final
tabulated data will also be subject to review at any point during its
use or interpretation during the program.
4-22
-------
5.0 FIELD SAMPLING
5.1 INTRODUCTION
This chapter covers the sampling methodology to be used during
the field effort to collect the required samples for analysis. The
methods are as detailed as possible, but it should be realized that every
detail for every source cannot be covered. It is important therefore* that
the personnel involved in the field effort be well trained and experienced.
Accurate records and notes must be maintained to document specific opera-
tions carried out at each location. Sound engineering judgment must be
exercised. In those unusual circumstances that warrant, the field team
will contact the project manager to resolve a specific problem, thus rely-
ing on a single source for these decisions throughout the program. This
will help to provide continuity and uniformity.
5-1
-------
5.2 SAMPLING IN PARTICULATE LADEN STREAMS
5.2.1 Scope and Application
This method will be used on those sources having a ducted
effluent from combustion sources.
5.2.2 Summary of Method
The method extracts a sample from the gas stream through a
sample nozzle at a rate approximately equal to the flue gas velocity. The
particulate matter is collected by a series of cyclones and a filter, and
then the gaseous constituents are collected by an adsorbent module and
absorbing solutions. Provisions are made to monitor all the required
parameters such as temperatures, pressures, and volumes. The sample
fractions are then recovered and shipped to the laboratory for analysis.
5.2.3 Definitions
SASS - Source Assessment Sampling System
SSMS - Spark Source Mass Spectometry
V/V - Volume to Volume
5.2.4 Apparatus; The SASS Train
The sampling train to be used for gaseous streams containing
particulate matter consists of a stainless steel probe which enters an
oven module containing 3 cyclones and a filter. Size fractionation is
accomplished in the series cyclone portion of the SASS train, which
incorporates the cyclones in series to provide large quantities of
particulate matter size-classified into three ranges: a) >10 urn,
b) 3 Him to 10 \j.m, and c) 1 \j.m to 3 ^m. Together with a 142 mm filter a
fourth cut, <1 jim, is obtained. Volatile organic material is collected
in a XAD-2 sorbent trap. The XAD-2 trap is an integral part of the gas
treatment system which follows the oven containing the cyclone system
(See Figure 5-1). The gas treatment system is composed of four primary
components: the gas conditioner, the XAD-2 adsorbent trap, the aqueous
5-2
-------
Ol
1
to
STACK T.C.
HEATER
CON-
TROLLER
GAS COOLER
\ / W
*—' CONVECTION A
Sa___oyEj^ II
It
GAS
TEMPERATURE
T.C.
XAD-2
CARTRIDGE
/
OVEN
T.C.
AWA
IMP/COOLER
TRACE ELEMENT
COLLECTOR
DRY GAS METER ORIFICE METER
CENTRALIZED TEMPERATURE
AND PRESSURE READOUT
CONTROL MODULE
CONDENSATE
COLLECTOR
10 CFM VACUUM PUMPS
Figure 5-1. SASS Schematic
IMPINGER
T.C.
-------
condensate collector, and a temperature controller. The XAD-2 sorbent 1s
a porous polymer resin with the capability of adsorbing a broad range of
organic species. The resin cleaning procedure is given in Appendix E. Some
trapping of volatile inorganic species is also anticipated as a result of
simple impaction. Volatile inorganic elements are collected in a series of
impingers. The pumping capacity is supplied by two 10-cfm high volume
vacuum pumps. Required pressure, temperature, power and flow conditions are
obtained from a main controller.
Apparatus Quantity
3
Sufficient to allow for
rotational mailings to
home base for cleaning
Assume 3 per SASS
run
One roll
Assume 10 per SASS
run
Assume 5 per SASS
run
Assume 5 per SASS
run
Assume 2 per SASS
run
Item
Five-gallon glass or high density poly-
ethylene containers to be used 1n cleaning
operations.
Nylon brushes - TRW Material Cat.
Nos. SB-941, BS-942, and BS-943.
150 x 15 mm polystyrene petri dishes,
SP Cat. No. Dl 990-25
Clean-room grade nylon 1 yard x 20 yards
High density polyethylene wide mouth con-
tainers for parti cul ate, Thomas
No. 1720-Q33 (6 oz.)
Amber glass containers for organic solutions
500 ml capacity
High density polyethylene containers for
1mp1nger solutions, 1 liter capacity,
Thomas No, 1706-K73
High density polyethylene containers
0.5 liter capacity.
5.2.5 Reagents: ACS Reagent Grade or Better Quality
• Nitric add (concentrated)
• Distilled water
• Methylene chloride
• Acetone
5-4
-------
• Silica gel desiccant - (3-8 mesh)
t Hydrogen peroxide - 30%
i Silver nitrate
t Ammonium persulfate
5.2.6 Sample Collection
The following sections discuss the equipment preparation
required for the SASS train, Including cleaning procedures of the train
components and sample containers, and apparatus checkout. The SASS train
schematic and other parts of the train are shown 1n Figure 5-1.
Precleanlng Procedures for the SASS Train and Sample Containers
The SASS train Is the most complex sampling unit discussed 1n
this manual, and an overall generalized cleaning procedure cannot be
established. Two primary cleaning methodologies are required. The first
methodology described 1n this section concerns the technique Involved 1n
producing biologically Inert surfaces throughout the SASS train. The
second methodology presents the techniques required for cleaning or
removing sample from various parts of the train after the run (Section
5.2.11), All cleaning procedures are shown diagrammatically 1n
Figure 5-2.
The first stage in preparing the sampling train and sample
containers for sample collection 1s prepasslvatlon with a nitric add
solution. All surfaces in the sampling train which come in contact with
sample, as well as all sample containers and containers for the implngers,
will be prepasslvated by a 60-minute standing contact with 15% (V/V)
aqueous nitric add. Agitate the parts initially to remove trapped air
bubbles. Rinse 1n a second solution of 15 percent (V/V) HN03 by dipping
and agitating the part in the solution for approximately 10 seconds.
Remove HN03 by rinsing with distilled water. Re-rinse by spraying thorough-
ly with acetone, covering all surfaces of the part, or dip 1n acetone and
agitate for 10 seconds. Blow dry with purified air.
Note that acetone has been substituted for Isopropyl alcohol.
5-5
-------
CLEANING
PROCEDURES
* t
SASS TRAIN PARTS
AND ALL SAMPLE
RECEPTACLES
NYLON BRUSHES TRW MATERIAL CATALOG
NUMBERS: SB-741, SB-942. 5B-943
IMPiNGERS
PREPASSIVATION BY ONE
HOUR STANDING CONTACT
WITH 15% HNO0
CLEAN ALL WORK AREAS WITH
AN I5OPROPYL ALCOHOL WIPE
PREPASSIVATION BY ONE
HOUR STANDING CON-
TACT WITH 15% HNO,
tn
i
DISTILLED WATER
RINSE
DUST LEVEL CHECK THROUGH VISUAL
OBSERVATION OF ONE HOUR SETTLING
ON BLACK PAPER DISC. SECTION
DISTILLED WATER
RINSE
ACETONE RINSE
ACETONE RINSE
METHYLENE CHLORIDE
RINSE
DRY WITH A FILTERED
STREAM OF AIR OR
DRY NITROGEN
YES
DRY WITH A FILTERED
STREAM OF AIR
(NITROGEN PERMISSIBLE)
INSPECT VISUALLY
FOR CONTAMINATION
INSPECT VISUALLY
FOR CONTAMINATION
REASSEMBLE AND
CAP OFF ORIFICES
USED PARTS
RINSE ONLY
NO
REASSEMBLE AND
CAP OFF ORIFICES
Figure 5-2. SASS Cleaning Procedures
-------
Passivation should be carried out every six months when the
frequency of tests is one per month or less, every three months when the
frequency of tests is between one per week and one per month, and monthly
for testing in excess of one per week. If the tests are more frequent or
of longer duration, passivation should be conducted more frequently. If
corrosion has occurred, the corrosion should be removed and the passivation
repeated.
The passivation and rinse solutions should be replaced after
every fourth use and should be discarded weekly.
Two separate approaches are used for subsequent cleanings, one
for SASS train components and organic sample receptacles, and the other for
bottles holding impinger solutions. The first group is cleaned in three
successive stages using a different solvent in each stage. The solvents
used are distilled water, acetone, and methylene chloride, in the order
listed. ACS reagent grade shall be used. Two washings with each solvent
will be accomplished. This procedure removes all extraneous particulate
matter and produces a clean, dry surface. As each part is treated with the
final solvent (methylene chloride), it is purged dry in a filtered stream
of air or dry nitrogen and visually inspected thoroughly for any sign
of contaminating residue, scale, rust, etc. A contaminated train com-
ponent may not be used in a sampling run. All equipment treated in the
above fashion must be placed in a clean area to await the next test.
The bottles holding the impinger solution are cleaned in two
successive stages, involving distilled water, followed by acetone.
The field area in which these cleaning operations are per-
formed must be as clean as possible under existing field conditions. An
enclosed space is required in which reasonable precaution has been taken
to remove spurious dust, dirt or particulate contaminants. Reasonable
precaution is intended to mean that the area has been swept clean; doors
or significant draft inducing sources have been closed and; an isopropyl
alcohol wipe has been performed over the work bench area. A laminar flow
bench will be used for handling the various fractions of the sample
during recovery.
5-7
-------
To ensure work area cleanliness, dust level checks are run
using the following procedure. A disc of black glazed weighing paper
(Sargent Welch #S-65225-A) is placed in an open petri dish and allowed to
stand on a bench in the work area. Wipe a finger across the paper. If no
dust appears to have been brushed off the paper, the area is clean enough
to proceed with sample transfer and/or cleaning operations. If a dust
trace is visible on the paper, the area must be cleaned and appropriate
measures must be1taken to lower the dust levels. This'may involve
dusting and sweeping the area, performing counter wipes, etc. A second
paper disc is then placed in the work area and the dust level check pro-
cedure is repeated until no visible dust trace is observed.
5.2.7 Pre-Test Checkout Operations
Prior to test-site arrival a number of checkpoints are required
to ensure a smooth field operation.
1) Sufficient quantity of solvents are required to maintain
adequate reserves during the elapsed time in the field.
2) A tank of purified dry nitrogen or a clean compressed air
source must be available in the van.
3) Swagelok fittings for each SASS train must be on inventory
in triplicate.
4) All SASS train parts must be closely examined for defects
which might induce down time problems in the field.
5) The entire system must be leak checked.
5-8
-------
The SASS train leak checking procedure 1s described 1n detail 1n the
operator's manual. Briefly, the procedure Involves assembling the entire
train, sealing off the probe tip, bringing the oven and probe to operating
temperatures, turning on the pump and observing flow meter gauges for the
existence of any appreciable flow. The allowable SASS train leak rate for
a Level 1 test 1s'0.05 cfm at 20 Inches of Hg. If an unacceptable leak
rate 1s found, move 1n the direction of the probe starting at the pump
and tighten each fitting 1n order to ensure that a loose fitting 1s not
responsible for the problem. If this action does not solve the leak
problem, the train must be disassembled on a modular basis starting at the
pump and progressing towards the probe while leak-checking each Individual
module until the problem area 1s pinpointed. Once discovered, 1f the
problem 1s one which cannot be solved with the materials at hand, 1t 1s
to be designated as the manufacturer's responsibility and substitute
spare parts should be obtained. Under no condition may a sampling test be
conducted with a leak rate 1n excess of 0.05 cfm at 20 Inches of Hg.
5-9
-------
5.2.8 SASS Train Cyclone Deletion Guidelines
Due to the lower grain loadings encountered in many oil and gas
fired boilers, a set of decision criteria has been developed for cyclone
deletion in order to maximize the amount of useful data obtained. The
nomograph presented in Figure 5-3 illustrates the estimated >3n and <3n
catches as a function of grain loading. (Use of Figure 5-3 is described in
Chapter 3.) Based on this figure decisions may be madefto retain or
remove the 1, 3, and/or 10 micron cyclones as indicated in Table 5-1.
In general, a projected catch of 5-10 mg in a given cyclone results in
that cyclone being eliminated. This cutoff point was chosen because
samples of this size represent the lower limit of recovery and are only
marginal in terms of analysis (i.e., only SSMS can be performed).
Table 5-1 will be used, subject to the following criteria:
• The maximum expected grain loading will be determined
using previous test data or estimates provided by site
personnel, actual TRW field experience, and existing data
concerning similar sites. When in doubt, the next higher
grain loading will be used.
• All catches will be photomicrographed, examined visually
for significant quantities of oversize particulate, and
a rough particle size distribution will be determined.
• If the field test produces results that indicate the use
of additional cyclones, the test will be repeated.
t Additional cyclones will be used if special conditions
indicate.
Table 5-2 shows how the decision criteria are expected to
apply to the combustion source categories to be tested in this program.
In all cases, the conservative approach will be taken and an additional
cyclone will be used for the first 1 or 2 sites tested using each type of
fuel.
5-10
-------
%CAT(
AFUN(
OFGfc
LOADI
— — — ••
—
_
^ ^
CHAS
CTION
MN
NG
• — «•
JOO.t
™99.J
— 99
— 98
— 97
— 96
-95
— 94
— 93
— 92
— 91
— 90
• f^t
— 80
— 70
— 60
— 50
— 40
— 30
— 20
— 10
—.5
2
TOTAL W
CATCH :
GRAMS
_- -- — •
GRAIN
LOADING
GRAIh
LOAD
1.0 —
0.9 —
0.8-
0.7—
0.6 —
0.5—
X
X
0.4-
0.3—
0.2—
0.1—
0.04 —
EIGHT OF
>3K IN
"~^* -
CATCH
WEIGHT
TOTAL WE
CATCH <
GRAMS
GRAIN
LOADING
. CATCH MOll **B
JNG ^'g0"1 (
.01- -.69
.02- -1.4
.03- -2.1
.041 2.8
— 55.1
— 43.3
— 33.0
-24.1
X
— 16.5X
X
X
£10.3
—5.5
— 2.1
— 0.7
— 0 *06
_ 0.003
EXPANDED
SCALE
JO,-
0.3—
0.4 —
0.5 -,
X
/
X0l6 —
X
x
X 0.7—
X
0.8—
0.9—
1.0 —
IGHT OF
3 H IN
CATCH
WEIGHT
—2.8
6.9
—13.1
—18.5
—22.0
^21.1
— 24.8
-24.1
— 22.0
— 18.6
— 13.8
Figure 5-3. Participate Analysis Prediction Nomograph
5-11
-------
Table 5-1. SASS Train Cyclone Use Criteria*
Grain Loading
>0.11
0.051-0.10
0.021-0.050
0.0001-0.020
<0.0001
Projected
Catch g
>3jj <3y
>.006
.004-. 006
nil
nil 0
nil
>6.9
3.1-6.9
1.4-3.1
.007-1.4
<.007
Cyclones Required*
ly 3y 10y
Yes Yes Yes
Yes Yes No
No Yes No
No Yes No
Run XAD-2 module
and Implngers only
*A filter 1s used 1n all cases.
Table 5-2. Expected Application of SASS
Train Cyclone as a Function
of Fuel Type*
Fuel Type
Coal
Residual 011
Distillate 011
Natural Gas
Gasoline
Diesel Fuel
Projected Grain Loading
>0.1
0.051-0.10
0.021-0.05
<0.020
<0.02
<0.02
<0.02
<0.02
Cyclones Required*
ly 3y
Yes Yes
Yes Yes
Yes Yes
No Yes
No Yes
No* Yes
Not yes
No* Yes
10y
Yes
No
No
No
No
No
No
No
*A filter 1s to,be used 1n all cases. The 3\i cyclone will be used 1n all
tests In order to provide data for the EPA Fine Partlculate Emissions
Information System.
fTh1s cyclone will be used until field tests show that 1t 1s not necessary,
5-12
-------
5.2.9 Sample Acquisition
This section is divided into two predominant parts: the first
part lists briefly the specific steps required to obtain a sample, while
the second part describes in detail the procedures required in performing
each step. In this way, personnel familiar with the functional require-
ments of each step are not hindered by unnecessary narrative, while those
who are not familiar with certain aspects of the operation may refer to
the second part of this section.
Assuming that all SASS train components and sample receptacles
have been treated and cleaned in accordance with the foregoing procedures,
a Level 1 sample will be taken as follows.
5.2.9.1 Sample Acquisition Steps
1) Fill the impinger bottles with the reagents and volumes
specified in Table 5-3.
2) Assemble sampling apparatus in accordance with the
manufacturer's specifications.
3) Preheat the probe and the oven. Under most conditions,
15 to 30 minutes are required for these components to reach operating
temperature. The oven and probe shall be maintained at 205°C (400°F).
For gas fired units the oven and probe temperature shall be maintained
at 150°C (300°F).
4) Measure the stack temperature, moisture content, and
velocity.profile. Determine the position in the stack which corresponds
to the average stack velocity (See Section 5.2.9.2).
5) Leak test the system. The allowable leak rate for a
Level 1 test is 0.05 cfm at 20 Inches of mercury. Leak rates in excess
of this value must be corrected.
6) Using the procedures and calibration curves supplied by
the manufacturer, compute the appropriate sampler flow rate and the
proper nozzle size.
7) Install the nozzle on the probe, and then insert the
probe into the stack or duct. The nozzle should be 1n the proper position
1n the duct, as determined in step 4.
5-13
-------
Table 5-3. SASS Train Impinger System Reagents
Impinger
#1
#2
#3
#4
Reagent
30% H202(a»b)
0.2 M (NH4)2S2Og(b)
+0.02 M AgN03
0.2 M (NH4)2S208
-------
8) To initiate the sampling run, turn on the vacuum pump and
throttle the intake valve to achieve the flow rate determined (in step 6).
9) During the course of the run, minimum of 20-minute checks and
adjustment of flow rates and temperatures will be made and recorded on a
standard data sheet.
5.2.9.2 Procedural Details for Individual Steps
The nine previously listed sample acquisition steps are self-
explanatory for step numbers 1, 3, 7, 8 and 9. Numbers 2, 4, 5 and 6
require additional elaboration for indivuduals unfamiliar with these
applications.
• Step 2, Apparatus Assembly
The appropriate procedures to be used are detailed in the
Aerotherm operating manuals.
§ Step 4, Temperature, Moisture and Velocity Profile
The general framework from standard EPA methods ^1 through 4
will be used to determine the stack gas velocity profile.
Since EPA standard methods 1 through 4 are compliance
methods they require degrees of accuracy in excess of those
needed for Level 1. In Level 1 , for example, sophisticated
moisture determinations (Method 4) are unnecessary since
plant data or stoichiometric calculations will suffice.
Also, Orsat analysis (Method 3) to determine stack gas
composition is unnecessary since GC data will exist for this
purpose. The mathematics used in determining the velocity
profile are independent of the data acquisition technique
and will therefore be used as stipulated in the standard
methods. Modified versions of Methods 1 and 2
which are appropriate for Level 1 sampling are
explained in detail in sections 5.2.9.3 and 5.2.9.4.
0 step 5r Leak Test
The appropriate procedures to be used are detailed in
the Aerotherm operating manuals.
5-15
-------
• Step 6, Nozzle and Flow Rate Selection
The appropriate procedures to be used are detailed in
the Aerotherm operating manuals.
5.2.9.3 Method 1 - Sample and Velocity Traverses for Stationary Sources
1) Principle and applicability
A sampling site and the number of traverse points are selected
to aid in the extraction of a representative sample. This method is
applicable to sampling of gas streams contained in ducts, stacks, or flues.
It is intended that all new sources consider the requirements
of this method before construction of the affected facility. Should they
be overlooked, some sites may not lend themselves to this method and
temporary alterations to the stack or deviation from the standard proce-
dure may be required.
This method is not applicable to stacks containing cyclonic or
swirling flow or stacks smaller than about 0.3 m (1 ft) in diameter or
? 2
0.07 m (0.8 ft ) in cross sectional area.
2) Procedure
a) Sampling Site,
Select a sampling site that is at least 8 stack or duct dia-
meters downstream and 2 diameters upstream from any flow disturbance such
as a bend, expansion, contraction or visible flame. If impractical,
select an alternate site that is at least 2 stack or duct diameters down-
stream and 0.5 diameter upstream from the flow disturbances. For a
rectangular cross section, use an equivalent diameter calculated from the
following equation to determine the respective distances:
2LW
D> = L + W Equation 5-1
where:
D. = equivalent diameter
L = length
W = width
5-16
-------
b) Minimum Number of Traverse Points
When the 8 and 2 diameter criterion can be met, the
minimum number of traverse points shall be 12 for stack diameters greater
than 0.6 m (24 in.) and 8 for stack diameters equal to or less than
0.6 m (24 in.).
When the 8 and 2 diameter criterion cannot be met use
Figure 5-4 to determine the minimum number of traverse points. To use
this figure, first determine the distances from the chosen sampling
location to the nearest upstream and downstream disturbances. Divide
each distance by the diameter or equivalent diameter to determine the
distance in terms of the number of duct diameters. Then, determine from
Table 5-4 the minimum number of traverse points that corresponds: 1) to
the number of duct diameters upstream, and 2) to the number of diameters
downstream. Select the higher of the two minimum numbers of traverse
points, or a greater value, such that for circular stacks the number is a
multiple of four, and for rectangular stacks, the number follows the
criteria in section c.
NUMBER OF DUCT DIAMETERS UPSTREAM*
( DISTANCE A)
1.0 1.5 2.0 Z.5
IO
^
A
i
1
e
1,
i
(
DISTURBANCE
SAMPLING
SITE
^DISTURBANCE
1FROM POINT OF ANY TYPE OF DISTURBANCE
(BEND, EXPANSION. CONTRACTION, ETC.)
10
NUMBER OF DUCT DIAMETERS DOWNSTREAM*
( DISTANCE B )
Figure 5-4. Minimum Number of Traverse Points
5-17
-------
Table 5-4. Location of Traverse Points in Circular Stacks
(Percent of stack diameter from inside wall to traverse point)
Traverse
point
number
diameter 2 4
1 14.6 6.7
2 85.4 25.0
3 75.0
4 93.3
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Number of
6 8 10
4.4 3.3 2.
14.7 10.5 8.
29.5 19.4 14.
70.5 32.3 22.
85.3 67.7 34.
95.6 80.6 65.
89.5 77.
96.7 85.
91.
97.
traverse points on a diameter
5
2
6
6
2
8
4
4
8
5
12
2.
6.
11.
17.
25.
35.
64.
1
7
8
7
0
5
5
75.0
82.
88.
93.
97.
3
2
3
9
14
1.8
5.7
9.9
14.6
20.1
26.9
36.6
63.4
73.1
79.9
85.4
90.1
94.3
98.2
16
1.6
4.9
8.5
12.5
16.9
22.0
28.3
37.5
62.5
71.7
78.0
83.1
87.5
91.5
95.1
98.4
18
1.
4.
7.
10.
14.
18.
23.
29.
38.
61.
70.
76.
81.
85.
89.
92.
95.
98.
4
4
5
9
6
8
6
6
2
8
4
4
2
4
1
5
6
6
20
1.3
3.9
6-7
9.7
12.9
16.5
20.4
25.0
30.6
38.8
61.2
69.4
75.0
79.6
83.5
87.1
90.3
93.3
96.1
98.7
22
1.1
3.5
6.0
8.7
11.6
14.6
18.0
21.8
26.1
31.5
39.3
60.7
68.5
73.9
78.2
82.0
85.4
88.4
91.3
94.0
96.5
98.9
24
1.1
3.2
5.5
7.9
10.5
13.2
16.1
19.4
23.0
27.2
32.3
39.8
60.2
67.7
72.8
77.0
80.6
83.9
86.8
89.5
92.1
94.5
96.8
98.9
c) Cross Sectional Layout and Location of Traverse Points.
Circular stacks. Locate the traverse points on two per-
pendicular diameters according to Table 5-4 and the example shown in
Figure 5-5.
One of the diameters shall be in a plane containing the
greatest expected concentration variation, e.g., after bends one diameter
shall be in the plane of the bend. This latter requirement becomes less
critical as the distance from the disturbance increases. Therefore, other
diameter locations may be used.
5-18
-------
TRAVERSE
POINT
2
3
4
5
6
DISTANCE,
% OF DIAMETER
4.4
14.7
29.5
70.5
85.3
95.6
Figure 5-5. Example Showing Circular Stack Cross Section Divided into
12 Equal Areas, with Location of Traverse Points at
Centroid of Each Area
In addition, for stacks greater than 0.6 m (24 in.) no sampl-
ing points shall be selected within 2.54 cm (1 in.) of the stack walls,
and for stacks equal to or less than 0.6 m (24 in.) no sampling points
within 1.27 cm (1/2 in.) of the stack walls. To meet these criteria, do
the following:
• Stacks greater than 0.6 m (24 in.): When any of the
traverse points, as located above, fall within 2.54 cm
(1 in.) of the stack walls, relocate them away from the
stack walls to a distance of 1) 2.54 cm (1 in.), or 2) a
distance equal to the nozzle inside diameter, whichever is
larger. These relocated traverse points (on each end of
a diameter) shall be the "adjusted" traverse points. In
some cases, two successive traverse points may need to be
relocated to a single adjusted traverse point at each end
of the traverse diameters.
• Stacks equal to or less than 0.6 m (24 in.): Follow the
procedure above noting only that the "adjusted" points
should be relocated at 1.27 cm (0.5 in.) from the wall
Instead of 2.54 cm (1 in.).
5-19
-------
Rectangular stacks. Divide the cross section into as many
equal rectangular areas as traverse points, such that the ratio of the
length to the width of the elemental areas is between one and two.
Locate the traverse points at the centroid of each equal area according
to the example in Figure 5-6.
d) Verification of Non-Cyclonic or Non-Swirling Flow
Generally, cyclonic or swirling flow can be expected after
such devices as cyclones and inertial demisters that follow venturi
scrubbers or in stacks that have tangential inlets or two inlets that are
opposite each other. At times, cyclonic flow can be detected by visual
observations of the effluent plume. However, a Type S pi tot tube as
described in Method 2 can be used as a tool to verify the presence of
cyclonic or swirling flow by doing the following:
Level and zero the manometer. Position the Type S pi tot tube
at each of the traverse points such that the face openings are perpendicu-
lar to the stack cross-sectional plane. A null (zero) reading at "0°
reference" denotes the absence of cyclonic flow. If the reading is not
zero, then rotate the pitot tube about +10°. A null reading within the
limits of +10 rotation from 0° reference indicates an acceptable flow
condition.
Conduct a velocity traverse according to Method 2. If there
are negative velocity pressure readings, ensure that the pitot lines are
not reversed.
Figure 5-6. Example Showing Rectangular Stack Cross Section
Divided into 12 Equal Areas, with Traverse
Points at Centroid of Each Area
5-20
-------
5.2.9.4 Method 2 - Determination of Stack Gas Velocity and Volumetric
Flow Rate (Type S Pi tot Tube)
1) Principle and applicability
Stack gas velocity is determined from the gas density and from
measurement of the velocity head using a Type S (Stausscheibe or reverse
type) pitot tube. This method is applicable for measurement of the average
velocity of a gas stream and for quantifying gas flow. This procedure is
not applicable for direct measurement in cyclonic or swirling gas streams.
(Method 1, section 2, d, shows how to determine unacceptable flow con-
ditions.)
2) Apparatus
a) Pitot Tube
Type S (Figure 5-7), or equivalent, calibrated according to
the procedure in section 4.
1.90-2.54 CM
(0.75-1.0 IN.)
TYPE-S PITOT TUBE
Figure 5-7. Pitot Tube-Manometer Assembly
5-21
-------
b) Differential Pressure Gauge_
Inclined manometer, or equivalent device, capable of
measuring velocity head to within 10 percent of the minimum measured
value or +0.013 mm (0.005 in.), whichever is greater. Below a differential
pressure of 1.3 mm (0.5 in.) water gauge, micromanometers with sensi-
tivities of 0.013 mm (0.0005 in*) should be used. However, micromano-
meters may not easily be adaptable to the existing field conditions and
are not easy to use with pulsating flow.
The calibration of magnehelics, if used, must be checked
after each test series against an oil manometer to agree within 5 percent as
specified in the Federal Register.
c) Temperature Gauge
Thermocouple, liquid-filled bulb thermometer, bimetallic
thermometer, mercury-in-glass thermometer, or other gauges that are
capable of measuring temperature to within 1.5 percent of the minimum
absolute stack temperature. The temperature gauge shall be attached to
the pi tot tube such that the sensor does not touch any metal and its
position is adjacent and about 1.90 to 2.54 cm (0.75 to 1 in.) from the
pi tot tube openings (see Figure 5-7). Alternate positions may be used if
the pi tot tube-temperature gauge system is calibrated according to the
procedure of section 4. If it can be shown to the satisfaction of the
Test Leader that a difference of not more than 1 percent in the velocity
measurement will be introduced, the temperature gauge need not be attached
to the pi tot tube.
d) Pressure Probe and Gauge
Piezometer tube and mercury or water-filled U-tube mano-
meter capable of measuring stack pressure to within 2.5 mm Hg (0.1 in. Hg).
The static tap of a standard type pi tot tube or one leg of a Type S
pi tot tube with the face openings positioned parallel to the gas flow
may also be used as the pressure probe.
5-22
-------
e) Barometer
Mercury, aneroid or other barometers capable of measuring
atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg). In many cases, the
barometric reading may be obtained from a nearby weather bureau station,
in which case the station value (which is the absolute barometric pressure)
shall be requested and an adjustment of elevation differences between the
weather station and the sampling point shall be applied at a rate of minus
2.5 mm Hg (0.1 in. Hg) per 30 m (100 ft.) elevation increase or vice versa
for elevation decrease.
f) Gas Analyzer
Shimadzu GC-3BT chromatograph with dual thermal conduc-
tivity detectors as described in section 6.2.5 under field analysis.
g) Calibration Pi tot Tube, Standard Type
The standard type pi tot tube shall have a known coef-
ficient obtained from the National Bureau of Standards, Route 70 S,
Quince Orchard Road, Gaithersburg, Maryland. An alternative is to use a
Prandtl type pi tot tube designed according to the criteria given below and
illustrated in Figure 5-8; which ensure that its coefficient will be
0.99 +0.01.
• Hemispherical or ellipsoidal tip (inlet end of the impact
tube). I
STATIC HOLES>
HEMISPHERICAL TIP-
Figure 5-8. Standard Pi tot Tube
5-23
8D
-------
• Eight diameters of straight run (based on the diameter of
the external tube) between the tip and the static pressure
holes.
• Sixteen diameters between the static pressure holes and the
centerllne of the external tube, following the 90° bend.
• Eight static pressure holes of equal size (approximately
0.71 mm or 1/32 1n. diameter), equally spaced in a
piezometer ring configuration.
• Ninety-degree bend of relatively large radius (approxi-
mately three diameters).
h) Calibration Differential Pressure Gauge
For calibration purposes, inclined manometer, or equivalent
device capable of measuring velocity head to within 0.13 mm HgO (0.005 in.
H20).
3) Procedure
a) Set up the apparatus as shown in Figure 5-7, Make sure
all connections are tight and leak free. Level and zero the manometer.
Because the manometer level and zero may drift due to vibration and
temperature changes, make periodic checks during the sample run. Record
all necessary data as shown 1n the example data sheet (Figure 5-9).
b) Measure the velocity head and temperature at the
traverse points specified by Method 1.
c) Measure the static pressure 1n the stack. One reading
1s usually adequate for all measuring points during the test; however,
this must be confirmed by randomly moving the pressure probe over the
cross section to see 1f there are any significant variations, I.e.,
greater than about 100 mm HgO (4 1n. HgO). If there are significant
variations, measure and record the static pressure at each traverse point.
5-24
-------
PLANT.
DATE.
.AUK NO.,
STACK DIAMETER OP. Otr.'.EWtO.'.'S.ntin.)
BAROYETRIC PRESSURE, mm Hj (in. Hj)
C*OSSSECTIONAL AREA,m2{l:2)
OPERATORS
PITOTTU3EI.D.r;C.
AVG. COEFFICIENT,Cp".
LAST DATE CALIBRATED.
SCHEMATIC OF STACK
MOSS SECTION
Avcrejt
iff pnltmimry Invtitfjittsit rioiw thit Pj vwlsi no mart thin 100 mm HjO
(4 in. HjO), record flni reiJinj.
Figure 5-9. Velocity Traverse Data
5-25
-------
d) Determine the atmospheric pressure.
e) Determine the dry stack gas molecular weight. This
may be done either by plant run data or by GC data as derived in
section 6.2.
f) Determine the moisture content by either plant run
data or by stoichiometric calculation.
g) Determine the cross sectional area of the stack or duct
at the sampling location. Whenever possible, it is better to physically
measure the stack dimensions rather than using blueprints.
4) Calculations
Carry out calculations, retaining at least one extra decimal
figure beyond that of the acquired data. Round off figures after final
calculation.
2 2
A = Cross sectional area of stack, m (ft )
Bwa = Water vapor 1n the gas stream« Proportion by volume
C = Pitot tube coefficient, dimensionless
K = Pitot tube constant,
34.97
m
sec
(g/g-mole)(mm Hg)
(OK).(mm H20)
for the metric system and
85.48
ft (lb/lb-mole)(1n. Hg)
sec L (ORTTin. H20)
1/2
for the English system
MJ - Molecular weight of stack gas, dry basis, g/g-mole
d (Ib/lb-mole)
M_ • Molecular weight of stack gas, wet basis, g/q-mole
s (Ib/lb-mole) y G
• Md (1 - Bwa) + 18 Bwa
5-26
-------
Pbar = AtmosPnen'c Pressure, mm Hg (in. Hg)
P = Stack static pressure, mm Hg (in. Hg)
P = Absolute stack gas pressure, mm Hg (in. Hg)
= P. + P
bar rg
Pstd = standard absolute pressure, 760 mm Hg (29.92 in. Hg)
Q . = Dry, volumetric stack gas flow rate corrected to standard
conditions, dscm/hr (dscf/hr)
t = Stack temperature, °C (°F)
Ol/ /Or
T = Absolute stack temperature, K ( R)
= 273 + t for metric
- 460 + tg for English
Tstd = standard absolute temperature, 293°K (528°R)
v = Average stack gas velocity, m/sec (ft/sec)
Ap = Velocity head of stack gas, mm H20 (in. H20)
3600 = Conversion factor, sec/hr
18 = Molecular weight of water, g/g-mole (Ib/lb-mole)
Average stack gas velocity.
Average stack gas dry volumetric flow rate
Q . = 3600 (1 - R ) V A
Ls(avg)
5-27
-------
The quantities of sample needed in order to perform the
required analyses are presented earlier. Naturally, the knowledge of
whether or not these quantities have been acquired during the run cannot be
obtained until subsequent gravimetric analyses have been performed. For
this reason the PMB has developed a series of sampling guidelines criteria
for acquiring the required quantity of sample during each run. These
criteria are:
o
• At least one combustion process cycle and 30 standard m
(1060 scf) of the process effluent are to be sampled
during each run,
• In the event that the combustion process is not cyclic in
o
nature, the 30 standard m figure must still be satisfied
over a period of time conducive to obtaining a sample
representative of process conditions. A sampling duration
of five hours has satisfied this requirement in the past.
To fulfill the above conditions it may be necessary on several
occasions (due to high grain loading conditions) to interrupt the progress
of the run to change the filter or nozzle due to clogging problems.
Indicate start and stop times on run sheets and extend run time to main-
tain a total of 30 m of gas collection. This is an acceptable procedure,
however, care must be taken to avoid contamination in the process of
transfer. A detailed log should be kept to record any relevant conditions
pertaining to the change.
5-28
-------
5.2.10 Filter Changing and Transfer
To fulfill the sampling requirements 1t may be necessary on
several occasions (depending on grain loading conditions) to interrupt the
sampling run to change the filter as a result of clogging problems. This
will be required whenever it is no longer possible to maintain flow by
throttling the pump. Filter transfer tends to be a time-consuming process
which may require as much as 1.5 to 2 hours depending on sampler location
as well as possible difficulties which may be encountered 1n removing the
housing. Once removed, the housing must be carried intact to the clean
area of the van for transfer. Care must be taken to avoid contamination
1n the process of the transfer. The filter 1s to be transferred to a
clean, tared, 150 x 15 mm plastic petri dish. In each case the clean filter
and petri dish are tared together so that a final weight may be obtained
in the laboratory. The non-sampling time lapse is to be added to the
overall sampling duration and is to be duly recorded on the run sheet.
5.2.11 Sample Handling and Transfer
The procedures used in transfering acquired sample from various
portions of the SASS train are extremely Involved. To expedite the
explanation of the procedures involved in sample transfer and handling,
the subject is discussed in terms of a modular approach. For this reason,
the SASS train 1s considered in terms of the following sections:
1) Nozzle and probe
2) Cyclone system interconnect tubing
3) Cyclones and filter
4) XAD-2 module
5) Impingers
5-29
-------
At the conclusion of the sampling run, the train is dis-
assembled and transported to the mobile lab unit or prepared work area
as follows:
1) Open the cyclone oven to expedite cooling, disconnect
the probe and cap off both ends.
2) Disconnect the line joining the cyclone oven to the
XAD-2 module at the exit side of the filter and cap off:
a) The entrance to the 10u cyclone,
b) The filter holder exit, and
c) The entrance to the join line which was disconnected
from the filter holder exit point.
3) Disconnect the line joining the XAD-2 module to the
impinger system at the point where it exits and XAD-2 module. Cap off
the exit of the XAD-2 module and the entrance line to the impinger
system.
4) Disconnect the line exiting the silica gel impinger at
the point where it leaves the impinger and cap off the impinger box to
facilitate carrying.
The solvent system to be used for line rinse and final clean-
out of adhered sample consists of a 51%/49% mixture of methylene chloride
and acetone.
Since step-by-step procedural instruction in narrative form
would be voluminous, time-consuming to follow, and might be confusing to
the reader, each step is presented in the following series of flow
diagrams (Figures 5-10 to 5-12). These diagrams will be placed in an
easily visible location near the cleaning area in the van as an aid to
the sample transfer activity.
5-30
-------
CH2d2: ACETONE RINSE
ADD TO 10»i CYCLONE RINSE
STEP1: TAP AND BRUSH
CONTENTS FROM WALLS
AND VANE INTO LOWER
CUP RECEPTACLE
REMOVE LOWBR CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
A TARED NALGENE CONTAINER
STEP 2: RECONNECT LOWER CUP
RECEPTACLE AND RINSE ADHERED
MATERIAL ON WALLS AND VANE
INTO CUP (CH2CI2: ACETONE)
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER, USING
CH2CI2: ACETONE
STEP 1: TAP AND BRUSH
CONTENTS FROM WALLS
INTO LOWER CUP RECEPTACLE
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
A TARED NALGENE CONTAINER
STEP 2: RECONNECT LOWER CUP
RECEPTACLE AND RINSE ADHERED
MATERIAL WITH CH,CI,: ACETONE
INTO CUP * l
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS
USING CH2CI2: ACETONE
STEPS: RINSE WITH CH2CI2:
ACETONE INTERCONNECT TUBING
JOINING 10 M TO3^ INTO ABOVE
CONTAINER
'COMBINE
ALL RINSES
IN AMBER
GLASS BOTTLE
FOR SHIPPING
AND
vANALYSIS
STEP1: TAP AND BRUSH
CONTENTS FROM WALLS
INTO LOWER CUP RECEPTACLE
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
A TARED NALGENE CONTAINER
STEP 2: RECONNECT LOWER CUP
RECEPTACLE AND RINSE ADHERED
MATERIAL WITH CH-CI,: ACETONE
INTO CUP
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTANTS
USI NO CH2CI2i ACETONE
STEP 3: RINSE WITH CHjClj: ACETONE
INTERCONNECT TUBING JOINING
3 it TO 1 it INTO ABOVE CONTAINER
STEP 1: REMOVE FILTER AND
PLACE IN TARED PETRI DISH
STEP 2: BRUSH PARTI CULATE FROM
BOTH HOUSING HALVES ONTO
FILTER IN PETRI DISH
NOTES: ALL CHjClj: ACETONE
MIXTURES ARE 51%/49%
ALL BRUSHES MUST HAVE
NYLON BRISTLES
ALL NALGENE CONTAINERS
MUST BE HIGH DENSITY
POLYETHYLENE
STEP 3: WITH CH2CI2:ACETONE
RINSE ADHERED PARTI CULATE
INTO AMBER GLASS CONTAINER
STEP 4: WITH CHjCljt ACETONE
RINSE INTERCONNECT TUBE
JOINING 1M TO HOUSING
INTO ABOVE CONTAINER
Figure 5-10.
Sample Handling and Transfer
Cyclones and Filter
- Nozzle, Probe,
5-31
-------
COMPLETE XAD-2
MODULE AFTER
SAMPLING RUN
RELEASE CLAMP JOINING
XAD-2 CARTRIDGE SECTION
TO THE UPPER GAS CON-
DITIONING SECTION
REMOVE CONDENSATE
RESERVOIR AND DRAIN
CONDENSATE THRU VALVE
INTO THE CONDENSATE
DRAIN CONTAINER USED
TO COLLECT CONDENSATE
DURING THE SASS RUN
MEASURE VOLUME AND PH
1
MEASURE 20%
OF TOTAL
CONDENSATE
PLACE IN
NALGENE
CONTAINER.
ADJUST'PH
TO < 2.0
WITH CONC.
HN03
1
REMAINDER
EXTRACTED
THREE TIMES
WITH CH2CI2,
USING 10% OF
TOTAL LIQUID
VOLUME, IN
1 / SEPARATORY
FUNNEL
1
ORGANIC
PORTION
MEASURED
AND PLACED
IN AMBER
CONTAINER
AQUEOUS
PORTION
DISCARDED
CLOSE CONDENSATE
VALVE AND REASSEMBLE
TO MODULE TO
COLLECT WASHINGS
RELEASE UPPER CLAMP
AND LIFT OUT INNER
WELL
RINSE WITH TFE WASH BOTTLE
(CH2CI2-ACETONE 51%/49%)
ALONG INNER WELL SURFACE
AND CONDENSER WALL
PLACE INNER WELL
ASIDE IN CLEAN AREA
RINSE ENTRANCE TUBE
AND BACK HALF OF
FILTER HOUSING INTO
MODULE. RINSE DOWN
CONDENSER WALL
RELEASE CENTRAL CLAMP TO
SEPARATE CLEAN CONDENSER
SECTION FROM LOWER SEC-
TION. RINSE LOWER SECTION
INTO CONDENSATE CUP.
RELEASE THE BOTTOM CLAMP
AND RINSE INTO CONDEN-
SATE CUP. DRAIN INTO
AMBER BOTTLE VIA DRAIN
VALVE***
REASSEMBLE THE 3 SECTIONS
(WITHOUT RESIN CUP) AND
REPEAT WASHING STEPS USED
WITH THE ORGANIC SOLVENT,
BUT USING 13% HNOg.**
WASH INNER WALL OF
RESIN CUP
CLEAN ALL MODULE
METAL PARTS BY
CLEANING PROCEDURE
REMOVE XAD CARTRIDGE
FROM HOLDER. REMOVE
SCREEN FROM TOP OF
CARTRIDGE. EMPTY RESIN
INTO A WIDE MOUTH
AMBER JAR USING CLEAN
FUNNEL
RINSE SCREEN AND
CARTRIDGE INTO RESIN
CONTAINER WITH CH.CI
ACETONE 51%/49% *
LABEL RESIN
CONTAINER
AND RINSINGS
MEASURE VOLUME AND
SAMPLE FOR ALL
ORGANIC SOLVE NT
PORTIONS
MEASURE VOLUME OF
AQUEOUS AND ACID
WASHES AND ADJUST
TO pH LESS THAN 2 IF
NECESSARY*
CAN USE pH PAPER FOR THIS STEP
"15%" HNOg IS MADE BY COMBINING
ONE VOLUME 70% HNOj AND FOUR
VOLUMES H2O.
THIS PROCEDURE ENSURES MATING LIPS
OF EQUIPMENT ARE PROPERLY CLEANED.
Figure 5-11. Sample Handling and Transfer - XAD-2 Module
5-32
-------
ADD RINSE FROM
CONNECTING LINE
LEADING FROM XAD-2
MODTOFIRSTIMPINGER
IMPINGERNO. 1
MEASURE VOLUME
TRANSFER TO NALGENE CONTAINER
AND MEASURE TOTAL VOLUME
RINSE WITH A KNOWN AMOUNT OF
DIST.
IMPINGERNO. 2
MEASURE VOLUME
IS)
2
JE
RINSE WITH A KNOWN AMOUNT OF
1ST.
IMPINGERNO. 3
MEASURE VOLUMF
RINSE WITH A KNOWN AMOUNT OF
COMBINE AND
MEASURE TOTAL
VOLUME FOR
SINGLE ANALYSIS
DIST.
IMPINGERNO. 4
DISCARD /REGENERATE
Figure 5-12. Sample Handling and Transfer-Implngers,
5-33
-------
Samples will be shipped by the most expeditious manner and will
not be delayed unnecessarily.
At the completion of all sample transfer activities, all SASS
train components must be completely re-cleaned in preparation for the
next sampling run. This may be accomplished by following the steps out-
lined in Figure 5-2.
5.2.12 Plume Opacity Tests
Plume opacity determinations shall be conducted for all
sources using both the Ringelmann and the Bacharach tests.
The Ringelmann test utilizes a chart which consists of a
series of graduated shades of grey, varying in five equal steps from
white (Ringelmann Number 0) to black (Ringelmann Number 5). The shades
in between are represented by standard grids. In the field, a comparison
is made between the stack plume and Ringelmann grids and the grid number
most closely resembling the plume shade is chosen and recorded. The
Ringelmann technique usually requires a person who has been certified to
take the reading; however, for Level 1 purposes, this requirement has
been waived. The exact procedure is given in section 6.6.
The Bacharach test is used in the field to supplement the
Ringelmann test. The Bacharach test uses a small plunger pump to pull a
sample of the duct effluent through an inserted filter, thus causing a
gray color spot on the filter. This color spot is then compared to a
standard scale and the appropriate density reading is chosen which
corresponds to the filter shade. The step by step procedure for a
Bacharach test is presented in Section 6.7.
5-34
-------
5.3
GAS SAMPLING
Gas samples are taken using an integrated gas sampling train.
The gas sample is drawn through a stainless steel probe and an ice bath
condenser. Two methods are used. See Figure 5-13 for Method I and Figures
5-14 and 5-15 for Method II.
5.3.1
Method I
a. Apparatus:
• Probe - Stainless steel probe containing a glass wool
filter to remove particulate matter.
§ Condenser - Water cooled condenser to remove excess
moisture.
• Valve - Needle valve to adjust sample gas flow.
• Pump - Leak-free, diaphragm-type or equivalent, to
transport sample gas to Tedlar bag.
• Bag - Tedlar sample bag.
• Flow meter - Capable of measuring 0.5 £/min.
PROBE
ICE BATH
GLASS
WOOL
FILTER
SAMPLE BAG
VALVE F/M
Figure 5-13. Integrated Gas-Sampling Train . Method I
5-35
-------
5.3.2 Method II
a. Apparatus:
• Probe - Same as Method I w/fliter.
• Condenser - Same as Method I.
• Valve - Same as Method I.
• Pump - High volume vacuum pump.
• Bag - Same as Method I.
• Flow meter - Same as Method I.
• Steel drum - Drum equipped with Swagelok quick dis-
connect female connectors.
5.3.3 Reagents
None
5.3.4 Sampling Procedure
Prior to field use, all Polymer sandwiched aluminum bags are
to be leak checked. The bags are leak checked by inflating them to a
pressure of 5 to 10 cm H^O (2-4 in. FLO) as determined by an in-line
manometer. Any displacement in the manometer after a 10-minute time
interval indicates a leak. In the field prior to the sampling operation,
the train is also leak checked. This is done by placing a vacuum gauge
at the condenser inlet, pulling a vacuum of at least 250 mm Kg (10 in. Hg),
plugging the outlet at the quick disconnect, and then turning off the
pump. The vacuum should remain stable for at least one minute.
The sampling point in the duct should be approximately at
the centroid of the cross section at a point no closer to the walls than
one meter (3.28 ft). This is only a general rule, however, which may
vary considerably depending on duct diameter. A sample 1s taken as
follows:
• Place the probe in the stack at the sampling point and
then purge the sampling line up to the bag.
t Connect the bag and make sure that all connections are
tight and leak free.
• Flush sample bag three times with sample.
5-36
-------
PROBE
QUICK DISCONNECT
FOR DRUM
EVACUATION
GLASS VALVE
WOOL
FILTER
ICE BATH
QUICK
DISCONNECT
EVACUATED DRUM
Figure 5-14, Integrated Gas Sampling Train - Method II.
QUICK DISCONNECT FITTING
QUICK DISCONNECT FITTING
PLEXIGLASS WINDOW W/"O" RING SEAL
STEEL DRUM TOP
Figure 5-15, Method II Steel Drum Top View
5-37
-------
• Sample at a rate of 0.5 liter per minute.
• At the conclusion of the sampling interval, disconnect the
bag and transport as rapidly as possible to the van for
analysis. The analysis procedure is given in Chapter 6.
5.3.4.T NO Sampling and Analysis*
' A
The Level 1 determination of NO/NOg concentrations is per-
formed using chemiluminescence analyzers. The sample for analysis
consists of an increment taken from the same bag which is used for field GC
analysis. The sample bag is connected to the inlet of the instrument
so that the required sample volume can be pumped at a known rate into a
properly calibrated analyzer. The instrument response is then recorded.
Depending upon the instrument, the readout can be directly in concentration
units. The primary consideration for chemiluminescence instruments involves
the calibration procedure which must be carried out on a daily basis while
in the field. This procedure is to be done in accordance with the manu-
facturer's specifications. The manufacturer's manual should be consulted
to avoid interference from water and ammonia.
5.3.4.2 NO Sampling and Analysis
J\
EPA Method 7 will be employed after 27 July 1978 for NOX sampling
and analysis. The full Federal Register text for NOX is given in Appendix C.
*This procedure was utilized prior to July 27, 1978 and discontinued be-
cause of NOX loss in gas bag gives low and unreliable results.
5-38
-------
5.4 LIQUID AND SLURRY SAMPLING
5.4.1 Scope and Application
The methods presented in this section are applicable to
obtaining representative samples of the following:
• Cooling tower water - sample to be taken from the input
and output stream to the tower.
• Cooling water (no cooling towers present) - sample to be
taken from input and output streams.
• Boiler blowdown streams — sample to be taken after
condensation.
t Slurries - from wet ash sluicing or bottom ash handling;
sample from sluice or scrubber outlet.
t Evaporation pond — samples taken away from the shore
boundary.
• Settling pond - overflows, if present.
The need, application, and analysis for each type of sample
is given in Chapter 3, Section 3.8.
5.4.2 Summary of Methods and General Considerations
Any of the above four groups may be sampled by one or more
of the following three methods depending on sample consistency: 1) tap
sampling, 2) heat exchange sampling, and 3) dipper sampling. Detailed
procedures for each of these three methods are presented in this section.
For the purposes of this assessment effort, liquids will be
distinguished from slurries by a solids content value of <5%. This value
is intended only to be used as a decision guideline for sampling procedure
selection and consequently must be chosen subjectively. The same is true
for the temperature value of 50°C which is chosen primarily for safety
reasons. A decision matrix relating stream condition to sampling pro-
r
cedures for liquids and slurries is presented in Figure 5-16.
5-39
-------
I
J5»
O
LIQUID AND
SLURRY SAMPLES
t
LIQUID SAMPLES
< 5% SOLIDS
t
1 PIPES
|
t 1
>50»C
(HOT)
<50
t 1
HEAT EX-
CHANGE
SAMPLE
r i
PC
1
*
TANKS
|
1
>50"C
(HOT)
1
TAP
SAMPLE
<50
1
HEAT EX-
CHANGE
SAMPLE
TAP
SAM
'
PC
f
PI
E
SLURRY SAMPU
>5% SOLIDS
t
* t
IpoHirv: 5% TO 10% SOLIDS
ruMU* |N PIPES
OPTION B t OPTION A
t t
DIPPFR TAP SAMPLE ONLY IF ...ppp. ,.. ..-. F
10% SOLIDS
IN SLUICES
1
DIPPER SAMPLE
MUST BE TAKEN
FIND OPENING
Figure 5-16. Decision Matrix for Liquid/Slurry Sampling
-------
Prior to sampling any liquid stream, plant data concerning the
stream must be recorded on a sample log sheet. Many streams exist under
pressure or elevated temperature or both; attempts to sample such a stream
without prior knowledge of its condition could result in severe injury.
The following data points are required from the plant engineer:
• temperature,
0 pressure,
• flow rate,
• stream identification (blowdown, cooling tower, etc.), and
• solids content.
The data points required from the sampler are:
• temperature,
• sample volume,
• sampling methods used, and
9. observations (sample is cloudy, has odor, etc.).
All samples are to be drawn from a point or area which will
provide as nearly a representative sample as possible. A flowing stream
containing particulate or insoluble phases will be stratified, The optimum
sampling location will, therefore, be located after a bend where turbulent
mixing will induce homogeneity. In all cases the main pipe or stream flow
must be sampled, Because sol Ids can accumulate in seldom used vent or
slipstreams, these lines are not recommended for sample acquisition.
5.4.3 Apparatus
• Tap sampler: A supply of thin wall 6.4 mm Teflon tubing
with a complete range of Teflon or stainless steel adapters
to fit successively larger tap outlet fittings. Poly-
ethylene bottle, A.M. Thomas Catalog No. 1732-B10, or
equivalent.
• Dipper sampler: High-density polyethylene beaker or con-
tainers which may be attached to rod extensions to reach
ponds and sluices.
5-41
-------
0 Heat exchange sampler: Same as tap sampler with the
addition of a coiled length of Teflon tubing and a container
to use as a condenser.
• Sample bottles: A supply of 1-and 2-liter high-density
polyethylene bottles for inorganics, and a supply of
2-liter amber glass bottles with Teflon lined lids for
organic samples.
• Filter paper: Acid washed, ashless, hard-finish paper
sufficiently retentive for fine particulates.
0 Separatory funnel: Glass, Teflon stopcock, 1-liter
capacity.
• Buchner funnel: 1-liter capacity
• Vacuum flask: 10-liter capacity
• Water aspirator.
5.4.4 Reagents
All reagents are reagent grade.
• Nitric acid
• Sodium hydroxide (0.1 N)
• Distilled water
0 Sulfuric acid
0 Strong soap solution
0 Acetone
0 Methylene chloride
5.4.5 Equipment Preparation
Containers intended for sampling industrial water streams must
be made of a high-density polyethylene or polypropylene. Plastic bottles
for aqueous stream samples should be cleaned by:
a) Detergent wash,
b) Distilled water rinse,
c) Nitric acid, 15% v/v.
5-42
-------
d) Distilled water rinse,
e) Acetone rinse, and
f) Blow dry with clean filtered air.
Organic samples, including CH2C12 extractions, must be placed
in amber glass bottles to inhibit sample degradation. These amber glass
bottles are cleaned by:
a) Strong soap solution,
b) Liberal tap water rinse,
c) Nitric acid, 15% v/v,
d) Distilled water rinse,
e) Acetone rinse,
f) Methylene chloride rinse, and
g) Drying a clean, hot air stream or placing in an oven at
40°C (140°F).
After the containers have been cleaned, dried and capped, they
should be stored in boxes to prevent spurious contamination.
5.4.6 Sampling Procedures
5.4.6.1 Tap Sampling
Tap sampling is generally applicable to contained liquids in
motion or static liquids in tanks or drums. Slurries are occasionally
sampled using the technique but sample representativeness is unreliable if
solids content exceeds 10%.
To acquire a tap sample the valve or stopcock used for sample
removal must be fitted with a length of pre-cleaned Teflon tubing long
enough to reach the bottomvof the sample container. Because of the wide
diversity 1n valve and stopcock nozzle sizes, a full range of male to
female and female to male Teflon or stainless steel tube adapters are
required. A piece of Teflon tubing sufficient in length to reach to
bottom of the sample container is coupled to the appropriate male or female
adapter. The adapter is then coupled to the valve or stopcock.
5-43
-------
The sample is removed by a stopcock or valve by inserting
a clean Teflon line into the sampling bottle so that it touches the
bottom. The clean sample bottle should be flushed with sample prior
to filling. The sample line flow must be regulated so it does not exceed
500 ml/min after the sample line has been flushed at a rate high enough
to remove all sediment and gas pockets. The apparatus used for tap
sampling is illustrated in Figure 5-17. If sampling valves or stopcocks
are not available, samples may be taken from water-level or gauge-glass
drain lines or petcocks.
As indicated previously, caution must be exercised while sampling
with this technique. The valve must be cracked slowly to allow for
escaping air pockets, and to prevent injury due to toxic or heated streams.
LINE
OR
TANK
WALL
6.4 mm
(1/4 In.)
Figure 5-17. Assembly for Tap Sampling
5-44
-------
5.4.6,2 Heat Exchange Sampling
No difference exists between this sampling technique and the
previous sampling technique except that it applies to streams >50°C and
therefore requires a condenser coil. The coll is to be constructed from
6.4 mm O.D. Teflon tubing and may be connected directly to the valve or
tap or by a coupling. The coil is cooled by Immersion into a water circu-
latlve or ice condenser. One possible construction of this device is
illustrated 1n Figure 5-18. As 1n the case of the tap sample, a heat
exchange sample is removed from a stopcock or valve by Inserting the exit
tube of the condenser coll Into the sampling bottle so that it touches the
bottom. The sample bottle must be thoroughly rinsed with sample prior to
filling and sample line flow must be regulated so as not to exceed
500 ml/min after the sample line has been flushed to remove all sediment
and gas pockets. This technique is applicable to any liquid stream >50°C
(122°F).
5.4..6.3 Dipper Sampling
The dipper sampling procedure is applicable to sampling sluices,
ponds, or open discharge streams of thick slurry or stratified composition.
The dipper 1s made with a flared bowl and attached handle, long enough to
,>,-.
Somplt Outlet
Tanacnttal Cooltnj
Water Outltt
-Jtamttli Mi 14
Steel
or Scam/ess
Siftl Httical
Coil
Figure 5-18. Heat Exchange Sampler
5-45
-------
reach sluice or discharge areas. The apparatus is constructed of high
density polyethylene. The sample is pre-cleaned in accordance with the
specifications presented in Section 5.4. 5.
A dipper sample is obtained by inserting the dipper into the
free flowing stream so that a portion is collected from the full cross-
section of the stream. The optimum position for obtaining this sample
will be located directly after a bend where mixing will promote sample
homogeneity. If the stream exists in an enclosed or inaccessible sluice,
the sample may be taken from the outfall.
Whenever ponds are being sampled, shore and outfall areas are
to be avoided since neither of these positions will yield a representative
pond sample. The dipper is to be extended as far as possible toward the
pond center and the sample is to be removed from this area.
5.4.7 Sample Handling and Shipment
Sample handling where liquids are concerned is an extremely
involved operation due to the many possible combinations and analysis con-
siderations applicable to each sample. A liquid or slurry sample may exist
in any one of the following six categories:
1) Aqueous,
2) Aqueous/Organic,
3) Organic,
4) Aqueous/Solid,
5) Organic/Solid, or
6) Aqueous/Organic/Solid.
In order to accommodate the various chemical and physical states
which may potentially exist in any given sample,a field handling scheme for
liquid and slurry samples is presented in Figure 5-19. All samples will be
subjected to this handling scheme.
Also, due to the inherent instability of environmentally signi-
ficant species in acqueous media, stringent field sample preservation
steps are required. All sample preservation techniques and handling
5-46
-------
AQUEOUS/SLURRY SAMPLES
~ 15 LITER SAMPLE
1 LITER SAMPLE
STORE IN
NALGENE
FILTER
IF NEEDED
-------
procedures are Itemized in Table 5-5, The on-s1te analysis scheme 1s
shown in Chapter 6 and in Table 3-7. Samples which must be cooled
to 4°C prior to shipment are to be packed in ice in a leak-proof styro-
foam container and sent air freight. Recent changes 1n airline policy
allow for this type of freight; however, TRW will be held liable for any
property damage due to leakage. For this reason the packaging activity must
be carefully supervised. The field analysis procedures for these samples
are presented in Chapter 6.
5-48
-------
Table 5-5. List of Analyses to be Performed on Liquid/Slurry Samples
Analysis
Acidity
Alkalinity
Conductivity
Suspended Solids
Total Dissolved Solids
Hardness
Water and HC1 teachable
Anions
Cations and Elemental Anions
PH
Organic Material in Methylene
Chloride Extracts
Cyanides
Ammonia Nitrogen
Nitrate
Phosphate
Sulfite.
Sulfate
Field
Analysis
X
X
X
X
X
X
X
X
X
X
X
X
Lab
Analysis
X
X
X
X
X
Fraction
Untreated
Untreated
Untreated
Untreated
Untreated
Untreated
Basify
Acidify
Untreated
Untreated
Untreated
Untreated
Untreated
Untreated
Untreated
Untreated
Field
Preservation
Requirements*
None Required
None Required
None Required
None Required
None Required
Cool to 4°C
NaOH to pH 12
HN03 to pH <2
None Required
None Required
NaOH to pHof 12
H2S04 to pH <2
H2S04 to pH <2
None Required
None Required
None Required
Maximum
Holding
24 hours
24 hours
24 hours
24 hours
24 hours
7 days
Depends on
An ion
38 days
No holding
7 days
24 hours
24 hours
24 hours
7 days
*Preservation and holding requirements applicable only if analysis is not done immediately
in field.
-------
5.5 SOLIDS SAMPLING
5.5.1 Scope and Application
This methodology is intended for use in the collection of
solid samples associated with combustion sources, such as fly ash, bottom
ash, scrubber input materials, and coal feed.
5.5.2 Summary of Methodology
The solid sampling procedure used will be shovel grab samples
unless the plant has an automatic sampling system. These techniques are
presented in the following sections.
5.5.3 Apparatus
• Square edged shovel, 12 inches wide,
• 1-gallon wide mouth polypropylene (high-density); Thomas
Catalog No. 1717 K-22 bottles, or equivalent.
5.5.4 Reagents
None
5.5.5 Procedures
5.5.5.1 Fractional Shovel Grab Samples
The concept of fractional shoveling involves the acquisition
of a time integrated grab sample representative of overall process input
or output during a given run time period. This procedure uses a standard
square edged shovel, 12 inches wide. For streams In motion, either
entering or exiting a process operation, a sample is taken from the belt
on an hourly basis. A full cross-stream cut should be taken. Each
hourly shovel sample is added to a pile to eventually form a run time period
composite. At the conclusion of the run this pile will be coned and
quartered (as described below in Section 5.5.5.3) to form a final repre-
sentative sample weighing from 2,3 to 4.5 kilograms (5 to 10 pounds).
It 1s always preferable to sample a moving stream rather than
a stationary storage access. This is particularly true if a large particle
or lump size distribution exists 1n the material. Stored containers or
heaped beds of material tend to settle, creating segregation of particles
5-50
-------
according to size and density, and it is more difficult to account for
this bias in the sampling. If it becomes necessary to sample a stationary
pile, every attempt should be made to a fully representative sample by
taking a number of grab samples from a variety of different areas in
the pile.
5.5.5.2 Automatic Samplers
Many plants are equipped with automatic samplers on process
input streams. The units are calibrated to remove representative cross
sections of a stream while automatically forming a homogeneous composite.
Whenever these units are available the sampling team should make use of
them in preference to the shovel technique.
5.5.5.3 Coning and Quartering
After a suitable composite has been formed a representative
sample for laboratory analysis must be removed. The usual method of
accomplishing this task involves the coning and quartering technique.
The coning and quartering procedure involves the following
6 steps:
1) The material is first mixed and formed into a neat cone.
2) The cone is flattened by pressing the top without further
mixing.
3) The flat circular pile is then divided into four quarters.
4) The two opposing quarters are discarded.
5) The two remaining quarters are mixed and steps 1-5 are
repeated until a 5-10 pound laboratory sample is obtained.
6) The 5-10 pound laboratory sample is to be placed in a
1-gallon wide-mouthed polypropylene bottle, or other suitable containers.
5-51
-------
5.6 CONTROLLED CONDENSATION SYSTEM (CCS)
5.6.1 Scope and Application
The Controlled Condensation System (CCS) is designed to measure
the vapor phase concentration of SOg as HUSO, in controlled or uncontrolled
flue gas streams. This method is specifically designed to operate at
temperatures up to 250°C (500°F) with 3000 ppm S02, 8-16 percent H20, and
up to 9 g/m (.4 gr/cf) of particulate matter.
By using a modified Graham condenser, the gas is cooled to the
acid dew point at which the SQ^ (HgSO^., vapor) condenses. The temperature
of the gas is kept above the water dew point to prevent an interference
from S02 while a heated quartz filter system removes particulate matter.
The condensed acid is then titrated with 0.02 N NaOH using Bromphenol Blue
as the indicator.
5.6.2 Reagents
• 30% H202
• 8% Na(.C03)2
• Acetone
• Deionized water
• 15% HN03
5.6.3 System Design
The S03 (H2.S04 vapor) Controlled Condensation System (CCS) con-
sists of a heated Vycor probe, a modified Graham condenser (condensation
coil), impingers, a pump and a dry test meter (see Figure 5-20)
5.6.4 Preparation
The cleaning procedures for the entire sampling train are
systematically listed 1n Table 5-6.
5.6.5 Sampling
Since a gas, or a small aerosol is being sampled, no traverse
will be performed in the stack. It can be shown that the average degree
of stratification in the duct is £15 percent of the mean concentration.
Because of the large fluctuation in source emission rates (^50 percent),
elimination of the error due to stratification will not significantly
5-52
-------
RUBBER VACUUM
HOSE
STACK
ADAPTER FOR CONNECTING HOSE
TC WELL
GLASS-COL
HEATING
MANTLE
X
ASBESTOS CLOTH
INSULATION
MY TEST
METE*
en
i
en
CO
WEE WAY
VALVE
STYROFOAM
ICE CHEST
Figure 5-20. Controlled Condensation System Setup
-------
Table 5-6. Cleaning Procedures
— — — •^•••^^•^•i^™
COMPONENT
Nylon Brush
Probe Liner
Cyclone
Filter Housing
Impingers
Connecting
Glassware
Controlled
Condensation
Coil
Filter
Tissuequartz
Plastic Storage
Bottles
CLEANING PROCEDURES (ORDER APPLIED LEFT TO RIGHT)
MUFFLE
(288°C)
4 hr.
BRUSH
X
X
Optional
Optional
15% HN03
3 hr.
Rinse/Brush
Rinse/Brush
Rinse
Rinse
Rinse
3 hr. /Rinse
3 hr.
H20
Rinse
Rinse
Rinse
Rinse
Rinse
Rinse
Rinse
Rinse
ACETONE
•K^^HBBW
Rinse
Rinse
Rinse
Rinse
Rinse
Rinse
Rinse
AIR
DRY
m^^^^m
X
X
X
X
X
X
X
X
REMARKS
Inspect for corrosion, 1
degradation and bristle 1
shredding; discard if 1
any found.
All material must be removed
via brushing and rinsing.
All material must be removed
via brush and rinsing.
Back flush to remove any
impacted material in the
front/ side.
1
HN03 soak not necessary if
no particulate in coil,
simply rinse.
Field blank samples will be
analyzed in parallel with
actual samples.
Linear polyethylene or 1
polypropylene.
-------
improve the sampling accuracy. Thus, the sample probe will be positioned
at the center of the duct or stack. Assemble the sampling train, so all
fittings and connections are as leak free as possible. An acceptable
leak rate is .03 CFM. The flowrate should be maintained at 8 liters per
minute. Sample for a period of one hour or until the coils are frosted
to 2/3 of their length. Temperature at the probe and filter holder must
be maintained at a minimum of 288°C. Figure 5-21 is an example of an
appropriate field data sheet listing the required test data.
5.6.6 Sample Recovery
Table 5-7 lists the step-by-step recovery procedure. Care
must be taken to avoid introducing any dust or grease into the rinse
solutions. Figure 5-22 illustrates the rinsing apparatus for the controlled
condensation coil. Multiple rinses are recommended to ensure a quanti-
tative wash of the coil. Place all solutions into properly labeled
storage containers, noting liquid levels and rinse volumes. Package and
ship recovered samples as to standard operating procedure.
5-55
-------
Sample Location^
Run frf
Run Date/Time.
Operator
Flowrate (cfm)
Ambient Pressure (P)
AEROSOL S03
(CONTROLLED CONDENSATION)
FIELD DATA SHEET
Reheater A1r Flow Rate, acfm_
Inlet Gas Rate, acfir
Sample Location $02 (ppm].
Boiler Load (mw)
Leak Rate
Time (Min)
•
AVG.
Temperature (°F)
Stack
Probe
Filter
Skin
Out
Reci re.
Water
Exit
Coil
Dry Gas
Meter
In
Out
Gas Meter
Reading,
cu. ft.
Figure 5-21. Controlled Condensation Field Data Sheet
5-56
-------
Table 5-7. Sample Recovery
Recovery Procedure
Storage
Probe
Probe shaken or tapped to remove
loose particles then brushed.
Nalgene
bottle.
20 ml
Probe Rinse
Remaining particulate matter rinsed
Into a separate container with
acetone.
Nalgene
bottle,
500 ml
Filter
Controlled
Condensation
Coil CCC
Remove and place in petri dish.
Remove coil from train, invert
over container and rinse
repeatedly with high purity H20.
Plastic
Nalgene
bottle,
250 ml
H202 Implngers
Using known amounts of high purity
H20, rinse all condensate from
preceding lines into the implnger.
Remove solution, record rinse
volume and total solution volume.
Nalgene
bottle,
500 ml
Na2C03
Implngers
Using known amounts of high purity
H20, rinse all condensate from
preceding lines into the impinger.
Remove solution, record rinse
volume and total solution volume.
Nalgene
bottle,
500 ml
Empty Implngers
Using known amounts of high purity
H20, rinse all condensate from
preceding lines into the implnger.
Remove solution, record rinse
volume and total solution volume.
Nalgene
bottle,
250 ml
Blanks
Place samples of high purity H20,
H202 and Na2COo solutions 1n
separate containers. Return to
laboratory for analysis.
Nalgene
bottle,
250 ml
5-57
-------
D.I.
FROM COIL
PIPET BULB
ADAPTER
D.I. H20
SOLUTION
POSITIONING
DRAIN
STOPCOCK VALVE
125 ML ERLENMEYER FLASK
Figure 5-22. Controlled Condensation Coil Rinsing Apparatus
5-58
-------
6.0 FIELD ANALYSES
6.1 INTRODUCTION
Field analyses are limited to those analyses that either: 1) are
required due to significant sample degradation if delayed, or 2) simplicity
dictates analysis over handling and shipping. These will include the
following:
• Gas chromatographic analyses for:
1) C1-C6 hydrocarbons
2) Inorganic species such as COg, 02» N2» and CO
• NO analysis - chemiluminescence (prior to July 27, 1978)
/\
• Water analyses
1) Acidity 7) Nitrate
2) Alkalinity 8) Phosphate
3) Conductivity 9) Sulfite
4) TSS 10) Sulfate
5) Hardness 11) Cyanide
6) pH 12) Ammonia
Nitrogen
t Opacity measurements by Ringelmann and Bacharach tests
6.2 FIELD GAS CHROMATOGRAPHIC ANALYSES
6.2.1 Scope and Application
This procedure defines the Level 1 field analyses of environmental
samples for:
• C1-C6 hydrocarbons, organic compounds boiling in the range
160° to 90°C.
• Inorganic compounds - COg, CO, 02» N2
Reporting Limitations. This is a survey procedure. For organic compounds,
species elutlng 1n the specified boiling point ranges are quantified as
n-alkanes. This procedure 1s Intended to give quantitative accuracy within
a factor of 3.
6-1
-------
Calibration Limitations. Quantisation based upon calibration with a gas
standard is limited to the accuracy of the gas standard. Certified mixtures
will be used.
Detection Limitations. The sensitivity of the flame ionization detector
varies from compound to compound. However, n-alkanes as a class have a
greater response than other classes. Consequently, using a n-alkane as
a calibrant and assuming equal responses of all other compounds tends to
give low reported values. Nominal detection limits were 1 ppm prior to
March 1978 and 0.1 to 0.2 ppm after this date.
6.2.2 Summary of Method
A gas sample is analyzed in the field by gas chromatography. The
instrument is set up with the column and conditions appropriate for the
specific analysis to be performed. Retention time and quantisation
calibrations are made with the proper standard gas mixture. Species
are identified by retention times or retention time ranges and then are
quantitated.
6.2.3 Definitions
• GC - Gas Chromatograph or Gas Chromatography
0 NBP - Normal Boiling Point
0 FID - Flame ionization detector
0 TCD - Thermal conductivity detector
0 RSD - Relative standard deviation
6.2.4 Sample Handling and Preservation
The samples of this analysis are contained in Tedlar bags or glass
gas sampling containers. They should be analyzed as soon after acquisition
as possible, preferably within two hours. Exposure to extremes of light and
temperature should be avoided.
6.2.5 Apparatus
0 Gas Chromatographs
This procedure is written for use on a Shimadzu GC-Mini 1
gas Chromatograph with dual flame ionization detectors and
linear temperature programmer and a Shimadzu GC-3BT Chroma-
tograph with dual thermal conductivity detectors. Both GCs
are also equipped with gas sampling valves. Any other equi-
valent instruments can be used, provided that instrument
operating parameters be changed appropriately.
6-2
-------
• Recorder
A recorder 1s required. Appropriate parameters are 1
1nch/m1n chart speed, 1 mV full scale, 1 sec full scale
response time.
• Gases
1. He Hum-minimum quantity is reactor grade. A 4A or 13X
molecular sieve drying tube is required. A filter
should be placed between the drying tube and the
instrument. The tube should be recharged after
every third tank of helium.
2. Air - "Zero" grade air is satisfactory. Air supplied
by a compressor and purification train is acceptable.
3. Hydrogen - Instrument grade is satisfactory. Hydrogen
supplied by a generator is also acceptable.
Gas Sampling Valve
Gas samples are injected by valves. The valves may have
single or dual matched loops. Dual loops should have
volumes matching within 1%, Various sized loops (e.g.,
1, 3, and 5 ml) should be available.
Integrator
An integrator is required. Peak area measurement by hand
is satisfactory but too time-consuming. If manual integra-
tion is performed, the height times width at half-height
method 1s used.
The Instrument settings made by the operator of an integrator
vary with each instrument make and model and will need to
be determined for the Shimadzu Instruments. Typical
parameters which need to be considered are the following.
These should be adjusted until acceptable performance is
achieved (operator judgement) and then should not be
changed. These parameters should be recorded in the instru-
ment log book.
Noise Supression - As required
Up-Slope Sensitivity - As required, mV/min
Down-Slope Sensitivity - As required, mV/min
Baseline Reset Delay - As required, min
6-3
-------
Area Threshold - As required, Vsec
Front Shoulder Control - As required
Rear Shoulder Control - As required
Date Sampling Frequency - As required, per sec
• Columns
1) For the inorganic gases (CO, C02, N2> 02), the following
columns are needed: (a) 5 ft x 1/8 in., stainless steel,
packed with Chromosorb 102, (b) 8 ft x 1/8 in., stainless
steel, packed with 13X molecular sieve, and (c) 5 ft x
1/8 in., steel, empty.
2) For the C1-C6 hydrocarbons, a 6 ft x 1/8 in., stainless
steel column packed with Poropak Q is required. If
temperature programming is required, dual and matched
columns are necessary.
6.2.6 Reagents
0 Gas standard - Cl to C6 n-alkanes in nitrogen. Concentrations
may range from 5-100 ppm. The standard must be certified.
• Gas standard - inorganic gases CO, C02, 02 in N2> This
standard must be certified.
6.2.7 Procedure - Cl to C6 Analysis
During van set-up at each new test site, the GCs will be fully
calibrated as described below. Partial calibrations will be performed
as required, specified, or directed by the test director.
Setup and Checkup. Each day the operator will verify the following:
1. All gas supplies are adequate and at the proper pressures.
2. Verify carrier gas flow rate is 30 + 2 ml/min. Flow rate is
checked at analytical column outlet after disconnection from
the instrument. The instrument must be at room temperature.
3. Verify hydrogen flow rate is 30 ^ 2 ml/min. Flow rate is
checked at the gas control panel on the GC. This flow rate
may change with other instruments.
4. Verify air flow is 300 +_ 20 ml/min. Air flow rate is
checked at the gas control panel on the GC.
5. Verify the electrometer is functioning properly. The
electrometer will be balanced and the bucking controls
will be set as required.
6-4
-------
6. Verify integrator and recorder are functioning properly,
7. Obtain a list of samples to be analyzed.
Calibration. To obtain the temperature ranges for reporting the
results of the C1-C6 GC analyses, the chromatograph is given a normal
boiling point-retention time calibration. The n-alkanes, their normal
boiling points (NBP), and data reporting ranges are given below.
NBP.°C Reporting Range. °C Report As
Methane -161 -160 to -100 Cl
Ethane -88 -100 to -50 C2
Propane -42 -50 to 0 C3
Butane 0 0 to 30 C4
Pentane 36 30 to 60 C5
Hexane 69 60 to 90 C6
• Apparatus
The required apparatus is specified below.
1. GC-Mini 1, recorder, and integrator set up according
to manufacturer's manual and performance-checked.
2. Standard mixture as specified in Section 6.2.6.
3. Conditions: Injector temperature ; detector
temperature ; oven temperature, isothermal
at °C or programmed from °C to °C
at °C/min.
• Initial Calibration Procedure
Connect the C-j-Cg standard gas bottle to the sampling
valve, and flow the gas through the valve at a constant,
low and reproducible flow rate of 20 std. ml/min measured
at the sample valve outlet using a soap bubble flowmeter.
When the sample valve is sufficiently purged, actuate the
valve and inject the contents of the sample loop into the
chromatograph. Simultaneously, start the integrator
and temperature programmer (if it is used). Obtain the
chromatograms and the integrator output. Retention times
and responses shall agree to within 5% relative standard
deviation. If any doubt exists concerning the relation-
6-5
-------
ship between the real sample GC peaks and those obtained
from calibration, a small aliquot of the calibration gas
should be spiked with the sample 1n order to verify
retention times.
• Dally Calibration Check
The C,-Cg standard gas mixture will be Injected and
analyzed at the start of each day. The retention times
and responses for each component should agree with the
Initial calibration data to within +10% relative. The
full calibration need not be repeated.
• Analysis of Samples
1. Chromatograph, recorder, and integrator set up
according to the manufacturer's manuals, calibrated,
and confirmed operating parameters. Parameters are to
be listed on each chromatogram.
2. Conditions: Column temperature, 100°C, electrometer,
1 x 10"10 A/mV; recorder, 1 inch/min and 1 mV full
scale.
3. Label recorder chart: sample number, date, etc.
4. Connect sample bag to gas sample valve, purge the
sample loop with the sample and then inject the con-
tents of the loop.
5. Start integrator and recorder.
6. When analysis is finished, give chromatogram and
integrator output to data analyst.
6.2.8 Calculations - Cl to C6 Hydrocarbons
Boiling Point - Retention Time Calibration
The calibration curve is constructed in the following manner:
1. For each alkane, calculate the average retention time
and relative standard deviation.
2. Plot the normal boiling points of the alkanes versus the
average retention times (1n seconds).
3. Draw in the curve.
4. On the curve, locate and record the retention times
corresponding to the reporting ranges: -160° to -100? -100°
to -50°, -50° to 0°, 0° to 30°, 30° to 60°, and 60° to
-------
Quantitation Calibration
The required data for this calibration are on the data sheet. The
calibration and quantisation are effected in the following manner:
1. Calculate the average area responses and relative standard
deviations for the propane calibrant.
2. Plot response (/jV-sec) as ordinates versus the concentra-
3
tion of the standard in mg/m injected, as abscissae. Draw
in curve. Perform least squares linear regression and
o
obtain the slope (nV-sec-m /mg).
Quantisation - Analyses
The required data are on the data sheet. The quantisation is
effected in the following manner:
1. In each retention time range, sum up the peak areas.
o
2. Convert peak areas (/LtV-sec) to mg/m by dividing by the
proper response (slope factor).
3. Record the total concentration of material in each
retention time range on the data sheet.
6.2.9 Procedure - Inorganic Gases
During van setup at each new test site, the GCs will be fully
calibrated as described below. Partial calibrations will be performed
as specified below and/or as directed by the Test Director.
Setup and Checkout. Each day the operator will verify that:
1. The carrier gas supply is adequate and at the proper
pressure.
2. The carrier gas flow rate (nitrogen) is 30 +_ 2 ml/min.
The flow rate is checked at the column outlet. The
column must be at room temperature.
3. The detector is set and working properly.
4. The recorder and integrator are working properly.
5. Obtain a list of samples to be analyzed.
Calibration. Connect the inorganic standard gas bottle to the gas
sampling valve, and flow the gas through the valve at a constant and
reproducible flow rate of 20 std. ml/min, measured at the sample valve
outlet with a soap bubble flow meter. When the valve is sufficiently
purged, actuate the valve, and inject the contents of the sample loop
into the chromograph. Simultaneously, start the integrator. When the CO,
6-7
-------
peak has eluted, switch the detector polarity and obtain the remaining
peaks. The retention times and peak areas will agree to within 5% re-
lative standard deviation.
The inorganic standard gas mixture will be injected and analyzed at
the start of each day. The retention times and responses of each com-
ponent will agree with the initial site calibration data to within +10%.
Analysis of Samples
1. Chromatograph, recorder, and integrator setup according
to manufacturer's manuals, calibrated, and confirmed
operating parameters. Parameters are to be listed on
each chromatogram.
2. Conditions
- Carrier flow rate: 30 +_ 2 ml/mv
- Bridge current: 100 mA
-Detector temperature: 100°C
-Oven temperature: 45°C
-Attentuator: as required
-Recorder: ImV full scale, 1 inch/min
-Integrator: as required
3. Label the recorder chart with sample number, date, and
operating parameters.
4. Connect the gas sampling container to the gas sampling
valve. Purge the sample loop with the sample. Inject
the sample.
5. Simultaneously, start the integrator and recorder.
6. When the analysis is finished, give the chromatogram
and integrator output to the data analyst.
6.2.10 Calculations - Inorganic Gases
The required data for these analyses are on the data sheet.
Calibration
1. Calculate average and standard deviation of the retention
time and response for each component in the chromatograms
of the standard.
2. Plot response (piV-sec) as ordinates versus the concentra-
tion of each component (mg/m3) injected as abscissae.
Draw in the curves. Perform least squares linear
6-8
-------
regressions for each component, and obtain the slopes
o
(jiV-sec-m /mg).
Analyses
The* required data are on the data sheet. Data reduction is effected
as follows:
1. Components (CO, C02, 02, N2) are identified by retention
time comparison with the standard chromatograms. (Flow
rate reproducibility is critical.)
2. Divide the areas found in the sample chromatogram by
the appropriate slope and obtain the concentration of
3
each component in mg/m .
6.2.11 Checking the Gas Sample Valve for Cleanliness
Periodically, the gas sampling valve should be checked to determine
if it is contributing contamination to the analysis of samples. Pass the
helium carrier through the sample loops then inject their contents and
analyze as if it were a sample. If significant peaks are noted, the
valve should be cleaned per the manufacturer's instructions.
6.2.12 Precision and Accuracy
An error propagation analysis is beyond the scope of this procedure.
With reasonable care, peak area reproducibility of a standard should be
of the order of 1% relative standard deviation (RSD). The RSD of the sum of
all peaks in a fairly complex sample might be of the order of 5%-10%.
Accuracy is more difficult to assess. With good analytical technique,
accuracy and precision should be of the order of 10%-20/L
Since both standards and samples are injected at ambient pressure,
calibration curves will vary from site-to-site with variations in
ambient pressure. If ambient pressure is noted at the start of each
analysis, data can be corrected to a common pressure for better
comparison.
6-9
-------
6.3 NOY ANALYSIS - CHEMILUMINESCENCE MEASUREMENT ON GAS BAG SAMPLE
A.
6.3.1 Scope and Applications*
Method is applicable to the determination of N0/N02 in all gas
samples, including samples collected in the integrated gas sampling
train using Tedlar bags. The method is suitable for detection of
NO/NO in the 0-2,500 ppm range. Sensitivity is approximately 1 ppb.
X
6.3.2 Summary of Method
NO and 03 react (NO + 0^ N02 + 02 + hv) and emit light at 0.6 - 3y.
A high sensitivity photomultiplier monitors the light emitted in the
reaction chamber of the chemiluminescence instrument. NO is determined
A
in the same fashion after N02 is reduced to NO in a catalytic converter.
6.3.3 Interferences
Water and ammonia may interfere with the analyses. The manufacturer's
manual should be consulted for recommendations on avoiding these inter-
ferences.
6.3.4 Apparatus
Chemiluminescence instrument.
6.3.5 Reagents
No reagents are required for this analysis.
6.3.6 Procedure
The analysis procedure using the chemiluminescence instrument is
straightforward and simply requires the introduction of the sample into
the sampling port. The primary consideration for chemiluminescence analysis
involves calibration of the instrument, which must be performed on a
daily basis. This procedure can be conducted using manufacturer specifications-
6.3.7 Accuracy and Precision
Data are unavailable on the precision and accuracy attainable with
the procedure.
*This method was utilized prior to July 27, 1978.
6-10
-------
6.4 NOV ANALYSIS - EPA METHOD 7
A
This method was adopted for use after July 27, 1978 because 1t was
found that there was significant deterioration of NOV 1n the gas bag which
/\
caused results to be low, Although these results were usually within a
factor of 2, much higher accuracy 1s required 1n order that the data for this
criteria pollutant be useful,
6.4.1 Scope and Application
This method 1s applicable to the determination of N0/N02 1n all stack
gas samples in most concentrations expected in the program up to 3000 ppm.
Method 7 may not provide accurate results at NOX concentrations below 200 ppm.
6.4.2 Summary of Method
A special sample of stack gas 1s drawn Into a specially designed glass
vessel which contains an oxidizing solution. NO 1s absorbed Into the
A
solution and converted Into nitrate which 1s determined.
6.4.3 Interferences
S02 will Interfere with this analysis 1f care 1s not taken to absorb
all of the gas Into the oxidizing solution as soon as possible. This 1s
done by vigorously shaking the sample vessel immediately after the sample
1s taken.
6.4.4 Apparatus. Reagents, and Procedure
The detailed Method 7 procedure is reproduced from the Federal Register
1n Appendix C.
6-11
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6.5 WATER ANALYSIS
To facilitate the analysis of simple water quality parameters and to
provide for a most cost effective method to acquire appropriate source
data, the Hach analysis kit DR-EL/2 model will be utilized in the field
for a Level 1 water analysis effort. Parameters to be analyzed by the
Hach Kit include pH, acidity or alkalinity, conductivity, hardness,
TSS, N03; P04H, S03r, S04=, CN~and NH3-N. The following is a discussion
of the methodologies utilized for these analyses. For a complete water
analysis sampling and analysis plan, see Section 3.8, Sample data sheets,
Figures 6-1 to 6-5,are at the end of this Section.
6.5.1 Acidity
6.5.1.1 Scope and Application
This method is applicable to surface waters, sewage and industrial
wastes, particularly mine drainage and receiving streams, and other waters
containing slowly hydrolyzable materials 1n sufficient concentration
to significantly delay attainment of equilibrium at the titration end
point. The method covers the range.from approximately 10 mg/liter
acidity to approximately 1000 nig/liter as CaC03, using a 50 ml sample.
6.5.1.2 Summary of Method
Two titrations are performed on each sample with standard alkali
to designated pH levels, with the end points determined by the color
change of added indicators. To measure the acidity resulting from
oxidation, hydrolysis or similar reactions of species in the water, one
sample aliquot is boiled to accelerate and complete these reactions prior
to the titration.
6.5.1.3 Definitions
This method measures the mineral acidity of a sample plus the
acidity resulting from oxidation and hydrolysis of polyvalent cations,
including salts of iron and aluminum.
6.5.1.4 Interferences
Natural color on the formation of a precipitate while titrating the
sample may mask the color change of the indicators. Oxidizing and reducing
species and some industrial waste water components may also interfere
with the color change producing reactions of the indicators. Volatile
components contributing to the sample acidity may be lost when the
sample is boiled, thus introducing some degree of error.
6-12
-------
6.5.1.5 Apparatus
a Erlenmeyer flasks, 50 ml, well rinsed with deionized water
• Pipets, graduated with capacity greater than 12 ml
• Hot plate
6.5.1.6 Reagents
0 Sodium hydroxide standard solution 0.02N
0 Brom Cresol Green-Methyl Red Indicator Solution (Hach catalog
number 451-36)
0 Phenolphthalein indicator solution, 1 g/1
6.5.1.7 Procedure for Methyl Orange Acidity
1) Pipet 11.4 ml of the water sample into the 50-ml Erlenmeyer
flask.
2) Add 2 drops of brom cresol green-methyl red indicator solution
and swirl to mix. If the sample turns green, the methyl
orange acidity is zero. If the sample turns pink, proceed
with Step 3.
3) Titrate the sample with sodium hydroxide standard solution,
0.0227N, while constantly swirling the flask, until the color
changes from pink to the first shade of blue-gray.
6.5.1.8 Procedure for Phenolphthalein Acidity
1) Pipet 11.4 ml of the water sample into the 50-ml erlenmeyer
flask.
2) Add 2 drops of phenolphthalein indicator solution and swirl
to mix.
3) Boil the sample for 2 minutes.
4) If the sample turns pink with the addition of the Phenolphthalein
and remains pink after boiling, the phenolphthalein acidity
is zero. If the sample remains colorless with the addition of
the Phenolphthalein or turns pink initially and the color
fades during boiling, proceed with Step 5.
5) Titrate the hot sample with sodium hydroxide standard solution,
0.0227N, while continuously swirling the flask, until a pink
color appears.
6-13
-------
6.5.1.9 Calculations
Methyl orange acidity, as mg/1 CaCOg = TOO x V, x N
where Vj = volume of standard alkali used 1n tltratlon to brom
cresol green-methyl red end point
N = normality of standard alkali
Phenolphtaleln acidity, as mg/1 CaC03 = 100 x V2 x N
where Vg = volume of standard alkali used 1n tltratlon to
phenolphthaleln end point
N = normality of standard alkali
6.5.1.10 Precision
On a round robin conducted by ASTM on 4 acid mine waters, including
concentrations up to 2000 mg/Hter, the precision was found to +10
mg/Hter.
6-14
-------
6.5.2 Alkalinity
6.5.2.1 Scope and Application
This method is applicable to drinking, surface, and saline waters,
domestic and industrial wastes. The method is suitable for all concentration
ranges of alkalinity; however, appropriate aliquots should be used to avoid
a titration volume greater than 50 ml. Automated titrimetric analysis is
equivalent. The sample must be analyzed as soon as practical; preferably,
within a few hours. Do not open sample bottle before analyses. Substances,
such as salts of weak organic and inorganic acids present in large amounts,
may cause interference in the electrometric pH measurements. Oil and grease,
by coating the pH electrode, may also interfere, causing sluggish response.
6.5.2.2 Summary of Method
An unaltered sample is titrated to an electrometrically determined
end point of pH 4.5. The sample must not be filtered, diluted, concentrated,
or altered in any way.
6.5.2.3 Reagents
The following reagents are obtained from HACH.
Cat. No. Description
• 203-14 Sulfuric Acid Standard Solution, 0.020N.
• 451-36 Brom Cresol Green-Methyl Red Indicator
Solution
§ 1897-36 Phenolphthalein Indicator Solution,
Ig/liter
6.5.2.4 Procedure
1) Pipet 10.0 ml of the water sample into the 50-ml Erlenmeyer
flask. See Note A.
2) Add one drop Phenolphthalein Indicator Solution and swirl
to mix.
3) If the sample turns pink, titrate with Sulfuric Acid
Standard Solution, Q.Q2QN_, to a colorless end point. Record
volume. If the pink color does not develop, proceed with
Step 5.
4) Multiply the number of ml of Sulfuric Acid Standard Solution
0.020NU used in Step 3 by 100 to obtain the mg/liter
pheonolphthalein alkalinity (as CaCOg). See Note B.
5) Add 2 drops of Brom Cresol Green-Methyl Red Indicator
Solution and swirl to mix.
6-15
-------
6) Continue the titration with Sulfuric Acid Standard Solution
0.020N., until the color changes from green or blue-green to
pink. Record volume.
7) Multiply the number of ml of Sulfuric Acid Standard Solution
0.020N., used in both tests by 100 to obtain the mg/liter total
alkalinity (as CaC03). See Note B.
TABLE 6-1. Alkalinity Relationship
Result of Titration
Hydroxide
Alkalinity
Carbonate
Alkalinity
Bicarbonate
Alkalinity
Phenolphthalein
Alkalinity. = 0
Equal to total
Phenolphthalein
Alkalinity less than
half of Total Alka-
T1n1ty
2 times the
Phenolphthalein
Alkalinity
Total Alkalinity
minus two times
Phenolphthalein
Alkalinity
Phenolphthalein
Alkalinity equal to
half of Total Alka-
linity
2 times the
Phenolphthalein
Alkalinity
Phenolphthalein
Alkalinity greater
than one half of Total
Alkalinity
2 times the
Phenolphthalein
minus Total
Alkalinity
2 times the
difference between
Total and Phenol-
phthalein
Alkalinity
Phenolphthalein
Alkalinity equal to
Total Alkalinity
Equal to the
Total Alkalinity
Notes
A. The 50 ml Erlenmeyer flask should be rinsed with demineralized
water three or more times before each test.
B. The mg/liter hydroxide, carbonate, and bicarbonate alkalinities
(as CaC03) can be calculated from the Table 6-1, Alkalinity
Relationship.
6-16
-------
6.5.2.5 Precision and Accuracy
Forty analysts in seventeen laboratories analyzed synthetic water
samples containing increments of bicarbonate, with the following results:
Increment as
Alkalinity
mg/ liter,
CaCO,
•3
8
9
113
119
Precision as
Standard Deviation
mg/ liter, CaC03
1.27
1.14
5.28
5.36
Bias,
%
+10.61
+22.29
- 8.19
- 7.42
Accuracy as
Bias
mg/llter CaC03
+0.85
+2.0
-9.3
-8.8
In a single laboratory using surface water samples at an average concentra-
tion of 122 mg CaCOo/Hter the standard deviation was +3.
™™
6-17
-------
FIGURE 6-2. Data Sheet - Alkalinity
SAMPLE LOCATION DATE SAMPLE REC'D
SAMPLE MEDIUM DATE SAMPLE ANALYZED
LOG NUMBER ANALYZED BY
VERIFIED BY
I STANDARD REAGENTS USED REFERENCE METHOD DATE REAGENT STANDARDIZED
1. __ _ __ _
2. __ _ __
3. _ __ _ __
4. _____ _ __
II CALCULATIONS
TOTAL ALKALINITY
As mg/liter CaC03 = ^A^ff X 5°?00° - 20* Vacld
* Valid when Nacid = 0.02 N, and Vsample » 50 ml
III SPECIFIC COMMENTS ON SAMPLE CHARACTERISTICS
VISUAL
ODOR
COLOR
SPECIFIC COMMENTS ON SAMPLE ANALYSIS
VISUAL
ODOR
ERRORS OBSERVED
6-18
-------
6.5.3 Specific Conductance
6.5.3.1 Scope and Application
The method 1s applicable to drinking, surface, and saline waters,
domestic and Industrial wastes.
6.5.3.2 Summary of Method
The specific conductance of a sample 1s measured by use of a self-
contained conductivity meter, Wheatstone bridge-type, or equivalent.
Samples are preferably analyzed at 25°C. If not, temperature cor-
rections are made and results reported at 25°C.
6.5.3.3 Definition
Conductivity measures the ability of a water sample to carry an
electric current. This depends on the total concentration of ionizable
species dissolved 1n the water and the temperature at which the measurement
1s made.
6.5.3.4 Sample Hand!1ng and Preservation
Representative samples shall be taken in distilled water rinsed
glassware.
Since delayed analysis of sample may cause C02 absorption and
subsequently change the conductivity value, determination will be made
as soon as possible.
6.5.3.5 Apparatus
Self-contained conductance Instrument; a thermometer capable of
reading to the nearest 0.1°C, conductivity cell.
6.5.3.6 Reagents
• Distilled water with conductivity less than Ipmhos/cm
• Standard potassium chloride 0.0100 M
6.5.3.7 Procedure
1. Insert the Conductivity Meter Scale in the meter and set
the RANGE switch to 5.
2. Connect the probe assembly to the five-pin receptacle on the
spectrophotometer panel.
3. Immerse the probe in a beaker containing the sample or
standard solution. The depth of the solution must be
sufficient to allow the probe to be immersed to the vent
holes.
6-19
-------
4. Select the appropriate range, beginning with the highest
range and working down. Each range on the meter scale is
numbered to correspond with the switch position numbers.
If the reading is in the lowest 10 percent of the range,
switch to the next lower range. Take the reading and
record. See Notes A and B.
Notes:
A. Additional conductivity meter scales have been included
as part of the conductivity option to provide equivalent
readings in ohms/cm, mg/liter sodium chloride and gr/gal
sodium chloride. Keep in mind that the sodium chloride
calibrations are based on pure NaCl solutions. Readings
taken from these scales should only be considered as
representing the concentration of sodium chloride which
is a conductivity equivalent to the conductivity of the
sample solution and does not necessarily represent the
actual concentration of sodium chloride in the sample.
B. Water samples containing oils, greases, or fats will
coat the electrodes and affect the accuracy of the
readings. Should this occur, the probe should be
cleaned with a strong detergent solution or dipped
in a one-to-one mixture of hydrochloric acid and
distilled water and then thoroughly rinsed with
distilled water.
6.5.3.8 Comments
Instrument must be standarized with KC1 solution before daily use.
Conductivity cell must be kept clean.
6.5.3.9 Precision and Accuracy
Forty-one analysts in 17 laboratories analyzed six synthetic water
samples containing increments of inorganic salts, with the follwoing
results:
6-20
-------
Increment as
Specific Conductance
H mhos/cm
100
106
808
848
1640
1710
Precision as
Standard Deviation
IJL mhos/cm
7.55
8.14
66.1
79.6
106
119
Accuracy as
Bias,
%
-2.02
-0.76
-3.63
-4.54
-5.36
-5.08
Bias,
M mhos/cm
-2.0
-0.8
-29.3
-38.5
-87.9
-86.9
In a single laboratory (MDQARL), using surface water samples with an
average conductivity of 536 ymhos/cm at 25°C, the standard deviation
was +6.
6-21
-------
6.5.4 Total Suspended Solids (TSS)
6.5.4.1 Scope and Application
Method 1s applicable to drinking, surface, and saline waters, domestic
and industrial wastes. The practical range of determinations is 0-500 mg/1;
this range can be extended by sample dilution.
6.5.4.2 Summary of Method
The sample is prepared by homogenizing it in a high speed blender,
and the turbidity is determined using the Hach Test Kit spectrophotometer.
6.5.4.3 Interferences
Gas bubbles in the sample must be removed by swirling or by addition
of tap water.
6.5.4.4 Apparatus
• Graduated Cylinder, 500 ml
• Glass Stirring Rod
• Blank Meter Scale for Hach Test Kit
• Serological Pipet
• Pipet Filter
• Blender
6.5.4.5 Reagents
0 Tap water
6.5.4.6 Procedure*
1. Fill a sample cell to the 25 mark with tap water and place it
in the cell holder. Insert the Suspended Solids Meter Scale
in the meter and adjust the Wavelength Dial to the end of travel
at the infrared (IR) end of the scale. Adjust the LIGHT CONTROL
for a meter reading of zero mg/1.
2. Take a water sample by filling a clean 500-ml graduated cylinder
to the 500-ml mark. Pour the sample into the container of
a blender. See Note A.
3. Blend at high speed for exactly two minutes.
4. Pipet 25 ml of the sample from the center of the blender container
into a clean sample cell.
Adapted from Hach Direct Reading Engineers Laboratory Methods Manual
(DR-EL/2).
6-22
-------
5. Check the meter reading to be sure the zero mg/1 setting has
not varied.
6. Swirl the sample cell containing the prepared sample, place it
in the cell holder, and read the mg/1 suspended solids. See
Note B.
Notes;
A. A Waring blender or equivalent is suggested for use in
this step. Equipment of this type is generally available
from hardware stores or applicance centers.
B. The meter scale has been calibrated using samples from two
municipal sewage treatment plants, one a trickling filter
and the other an activiated sludge unit. Simultaneous
samples were run using the photometric method and the
membrane filter technique. For greater accuracy, a blank
meter scale can be calibrated to a specific sample by
simultaneous comparison with the membrane filter method.
6.5.4.7 Calculations
Mg/1 of suspended solids are read directly from the spectrophotometer.
6.5.4.8 Precision and Accuracy
Data are unavailable on the precision and accuracy of the method,
6.5.5 Hardness
6-5.5.1 Scope and Application
This method is applicable to drinking, surface, and saline waters,
domestic and Industrial wastes. The method is suitable for all concentra-
tion ranges of hardness; however, in order to avoid large titration volumes,
use a sample aliquot containing not more than 25 mg CaCOv
O
Excessive amounts of heavy metals can interfere. This is usually
overcome by complexing the metals with cyanide.
Routine addition of sodium cyanide solution (Caution: deadly
poison) to prevent potential metallic interference is recommended.
6.5.5.2 Summary of Method
Calcium and magnesium ions in the sample are sequestered upon the
addition of disodium ethylenediamine tetraacetate (Na2EDTA). The end
point of the reaction is detected by means of Calmagite Indicator, which
has a red color in the presence of calcium and magnesium and a blue color
when the cations are sequestered.
6-23
-------
6.5.5.3 Reagents ^
The following reagents are obtained from Hach.
Cat. No. Description
• 205-14 Titra Ver Hardness Titrant
• 424-13 Buffer Solution
• 928-99 Man Ver II Hardness Indicator Powder Pillow
6.5.5.4 Procedure
1. Pipet 10.0 ml of the water sample into a 50-ml Erlenmeyer
flask.
2. Add 3 drops of Buffer Solution and swirl to mix.
3. Add the contents of one ManVer II Hardness Indicator Powder
Pillow and swirl to mix.
4. While constantly swirling the flask, titrate the sample
with Titra Ver Hardness Titrant until the color changes from
red to pure blue. See Note A.
5. Multiply the number of ml of TitraVer Hardness Titrant used
by 100 to obtain the rug/liter total hardness (as CaCOg).
See Note B.
Notes:
A. Titrate slowly towards the end point to allow time for
the reaction and color change to take place.
B. The presence of copper and/or iron may cause the end
point to be masked or delayed. These interferences
can be overcome by adding a 0.2-gram scoop of Potassium
Cyanide after Step 2.
6.5.5.5 Precision and Accuracy
Forty-three analysts in nineteen laboratories analyzed six synthetic
water samples containing exact increments of calcium and magnesium salts,
with the following results:
6-24
-------
Increment as
Total Hardness
"9/liter, CaC03
31
33
182
194
417
444
Precision as
Accuracy as
Standard Deviation Bias Bias
mg/ liter, CaCo- % mg/ liter, CaCCL
0 3
2:87
2.52
4.87
2.98
9.65
8.73
-0.87
-0.73
-0.19
-1.04
-3.35
-3.23
-0.003
-0.24
-0.4
-2.0
-13.0
-14.3
!n a single laboratory (MDQARL), using surface water samples at an average
concentration of 194 mg CaC03/liter the standard deviation was +3.
6-25
-------
6.5.6
6.5.6.1 Scope and Application
This method is applicable to drinking, surface, and saline waters,
domestic and industrial wastes.
6.5.6.2 Summary of Method
The pH of a sample is an electrometric measurement, using either a
glass electrode in combination with a reference potential (saturated
calomel electrode) or a combination electrode (glass and reference).
6.5.6.3 Comments
• The sample must be analyzed as soon as practical;
preferably within a few hours. Do not open sample
bottle before analysis.
• Oils and greases, by coating the pH electrode, may
interfere by causing sluggish response.
• At least three buffer solutions must be used to
initially standardize the instrument. They should
cover the pH range of the samples to be measured.
6.5.6.4 Precision and Accuracy
Forty-four analysts in twenty laboratories analyzed six synthetic
water samples containing exact increments of hydrogen-hydroxyl ions, with
the following results:
Increment as
pH Units
3.5
3.5
7.1
7.2
8.0
8.0
Precision as
Standard Deviation
pH Units
0.10
0.11
0.20
0.18
0.13
0.12
Accuracy as
Bias,
%
-0.29
-0.00
-i-l.Ol
-0.03
-0.12
+0.16
Bias
pH Units
-0.01
+0.07
-0.002
-0.01
+0.01
In a single laboratory (MDQARL), using surface water samples at an
average pH of 7.7, the standard deviation was +0.1.
6-26
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6.5.7 Nitrate Nitrogen
6.5.7.1 Scope and Application
Method is applicable to drinking, surface and saline waters, domestic
and industrial wastes. Modification can be made to remove or correct for
turbidity, color, salinity, or dissolved organic compounds in the sample.
The applicable range is 0-30 mg/1, although this range can be extended
with suitable dilution.
6-5.7.2 Summary of Method
The sample is reacted with Hach NitraVer V Nitrate Reagent which
consists of a reducing agent, such as granulated copper-cadmium, plus a
diazotization agent (sulfan 11 amide) and a coupling agent N-(l-naphthyl)
• ethylenediamine dihydrochloride. This forms a highly colored azo dye
which is measured spectrophotometrically at 500 nm. The method is also
known as the cadmium reduction method.
6.5.7.3 Interferences
Interferences from nitrite ion can be eliminated by adding bromine
water dropwise to the sample until the yellow color of bromine persists,
followed by addition of one drop of phenol solution to destroy the color
(see Reagents, Section 6.5.7.5). Strong oxidizing and reducing substances
will also interfere. Ferric iron causes high results and must not be
Present. Large amounts of chloride cause low results.
6.5.7.4 Apparatus
Hach Portable Test Kit Spectrophotometer for use at 500 nm, providing
a light path of 1 cm or longer. Standard laboratory glassware, including
an eye dropper.
6.5.7.5 Reagents
• Hach NitraVer V Nitrate Reagent Powder Pillows
• Nitrate Nitrogen Standard Solution, 10 mg/Hter as N
• Phenol Solution, 3 percent
• Bromine Water
6-5.7.6 Procedure*
1. Fill a clean sample cell with sample to the 25 mark. See
Notes A and B.
* Abstracted from Hach Direct Reading Engineers Laboratory Methods
Manual (DR-EL/2)
6-27
-------
Add the contents of one NitraVer V Nitrate Reagent Powder Pillow
to the sample cell, stopper, and shake vigorously for exactly one
minute. See Notes C and D. An amber color will develop if
nitrate nitrogen is present. To allow time for proper color
development, wait at least 5 minutes but not more than 15
minutes before completing Steps 3 and 4.
Fill another sample cell to the 25 mark with some of the
original water sample and place it in the cell holder. Insert
the Nitrogen, Nitrate (NitraVer V Method) Meter Scale in the
meter and adjust the Wavelength Dial to 500 nm. Adjust the
LIGHT CONTROL for a meter reading of zero mg/1.
Place the prepared sample in the cell holder and read the mg/1
nitrate nitrogen (N). See Notes E and F.
Notes:
A. The sample cells and stoppers should be rinsed by shaking
with portions of demineralized water several times before
each test.
B. NitraVer V Nitrate Reagent is slightly temperature sensitive.
For best results, the test should be performed with a sample
temperature of 20° to 24^(68° to 75°F).
C. A deposit of unoxidized metal and drying agent will remain
after the NitraVer V Nitrate Reagent Powder has dissolved.
This will have no effect on test results.
D. The extent of color development in the nitrate nitrogen
test using NitraVer V Nitrate Reagent Powder is partially
affected by the shaking time and technique of the analyst.
For most accurate results, the analyst should make successive
tests on a solution containing a known amount of nitrate
and adjust his or her shaking time to obtain the most accurate
results.
E. The results can be expressed as mg/1 nitrate (N03) by
multiplying the mg/1 nitrate nitrogen (N) and 4.4.
F. The reagent blank must be determined on each new lot of
NitraVer V Nitrate Reagent by running the test using
demineralized water in Steps 1 and 3. The value of the
6-28
-------
blank must then be subtracted from the final reading for
each sample tested with that reagent lot. An occasional
check should also be made between purchases to determine
the condition of the NitraVer V Nitrate Reagent.
6.5.7.7 Calculations
The concentration of nitrate nitrogen in mg/1 is read directly from
the instrument. As indicated in Note E above, this concentration can be
converted to mg/liter (N03) by multiplying the mg/liter nitrate nitrogen
(N) concentration by 4.4.
6.5.7.8 Precision and Accuracy
Three laboratories analyzed four natural water samples containing
exact increments of inorganic nitrate, with the following results:
Increment as Precision as Accuracy As
Nitrate Nitrogen Standard Deviation R. .,
mg N/liter mg N/liter bias' 7a B™?»
mg N/liter
0.29 0.012 + 5.75 +0.017
0.35 0.092 +18.10 +0.063
2.31 0.318 + 4.47 +0.103
2.48 0.176 - 2.69 -0.067
6-5.8 Phosphate. Total Organic and Inorganic
6-5.8.1 Scope and Application
Method is applicable to drinking, surface and saline waters, domestic
and industrial wastes. It may also be applicable to sediment-type samples,
sludges,1algal blooms, etc. The range of application is 0-2 mg/liter.
6'5-8.2 Summary of Method
Total organic and inorganic phosphate are determined by oxidation of
the Phosphorous forms present in the sample to orthophosphate using potas-
sium persulfate. The orthophosphate present is then treated with Hach
PhosVer in Phosphate Reagent Powder Pillow (ammonium molybdate and antimony
Potassium tartrate in an acidic medium) to form an antimony-phospho-
molybdate complex, which is subsequently reduced to an intensely blue-
colored complex (by ascorbic acid) and measured spectrophotometrically at
700 nm.
6-29
-------
6.5.8,3 Interferences
The following Interfere above the concentrations listed: copper,
10 mg/lj Iron, 50 mg/1j silica, 50 mg/1; and silicate, 10 mg/1. Arsenate
and hydrogen sulflde also Interfere.
6.5.8.4 Apparatus
Hach Portable Test Kit Spectrophotometer for use at 700 nm. Standard
laboratory glassware.
6.5.8.5 Reagents
• Sulfuric add solution, 5.25N
• Hach Potassium Persulfate Powder Pillow
• Soli urn hydroxide, 5.ON
• Hach PhosVer III Phosphate Reagent Powder Pillow
t Sterno, 2-5/8 oz cans.
• Demineralized Water
• Filtration Aid Solution
6.5.8.6 Procedure*
1. Fill a clean 25-ml graduated cylinder with sample to the
25-ml mark. Pour the sample into a clean 50-ml Erlenmeyer
flask. See Note A.
2. Add the contents of one Potassium Persulfate Powder Pillow and
swirl to mix.
3. Add 2 ml of 5.25N Sulfuric Acid Standard Solution using the 1.0
ml calibrated dropper and swirl to mix.
4. Place the flask on a hot plate or over a flame (Sterno provided)
and boil gently for 30 minutes, maintaining the sample volume
near the 20-ml mark with demineralized water. See Note B.
Do not allow the volume to exceed 20 ml toward the end of the
30-minute period and do not boil to dryness. Allow the sample
to cool before proceeding.
5. Add 2 ml of 5.ON Sodium Hydroxide Standard Solution using the
1.0 ml calibrated dropper and swirl to mix.
* Abstracted from Hach Direct Reading Engineers Laboratory Methods
Manual (DR-EL/2)
6-30
-------
6. Return the sample to the graduated cylinder. Bring the volume
to 25 ml by rinsing the flask with small portions of demineralized
water and using the rinse water to correct the volume.
7. Take sample from (6) by filling a clean sample cell to the 25
mark. See Note C.
8. Add the contents of one PhosVer III Phosphate Reagent Powder
Pillow and swirl to mix. See Note D. A Blue-violet color
will develop if phosphate is present. Allow at least 2 minutes,
but not more than 10 minutes, for the color to fully develop
before completing Steps 3 and 4.
9. Fill another sample cell to the 25 mark with some of the
original water sample and place it in the cell holder.
Insert the Phosphate (PhosVer III Method) Meter Scale in
the meter and adjust the Wavelength Dial to 700 nm. Adjust
the LIGHT CONTROL for a meter reading of zero mg/1.
10. Place the prepared sample in the cell holder and read the
mg/1 total phosphate (P04). See Note E.
11. To determine inorganic phosphate only, repeat Steps 1 through
10 above, but omit Step 2. Read the results as mg/1 total
inorganic phosphate.
12. The mg/1 of organic phosphate can be determined by subtracting
the amount of total inorganic phosphate (Step 11) from the
results of the total phosphate test (Step 10).
Notes:
A. If the sample is turbid or colored the procedure must be
run using a 50-ml sample, 2 Potassium Persulfate Pillows
and 4 ml each of Sulfuric Acid and Sodium Hydroxide Standard
Solutions with a 50-ml graduated cylinder and a 125-ml
Erlenmeyer flask. Use 25 ml of the oxidized sample to
zero the instrument in Step 9. This will compensate for
any turbidity'or color which is destroyed during the
oxidation. If the sample is highly turbid it may be
necessary to carry out the filtration procedure described
in Note C before the hydrolysis of a 25 ml sample of
the filtrate.
6-31
-------
B. The 30-minute digestion procedure can be more easily
accomplished by using a "double boiler" technique. Place
the flask containing the sample in a small pan or beaker
filled with enough water to bring its level above the level
of the sample in the flask. Heat the water to boiling and
continue heating until the sample in the flask has boiled
for 30 minutes. This technique assures even heating of
the sample and helps prevent boiling to dryness.
C. Large amounts of turbidity may cause inconsistent results
in the phosphate tests because the acid present in the powder
pillow nay dissolve some of the suspended particles and
because of variable desorption of orthophosphate from the
particles. The following pretreatment is recommended for
highly turbid samples although it will result in the loss
of any suspended orthophosphate which may be present.
1. Take a water sample by filling a clean 100-ml graduated
cylinder to the 100-ml mark. Pour the sample into a
clean 125-ml Erlenmeyer flask.
2. Add 5 drops of Filtration Aid Solution and swirl to
mix. Allow the sample to stand for 10 minutes.
3. Filter the solution and proceed with the test using
the filtrate in Steps 7 and 9 above. The result will
be the mg/1 of soluble orthophosphate.
D. The PhosVer III Phosphate Reagent Powder may cause some
turbidity depending on a large number of factors. It is
highly recommended that a reagent blank of PhosVer III
Phosphate Reagent Powder in about 25 ml demineralized
water be used to zero the instrument in Step 9.
E. The results may be expressed as mg/1 phosphorus (P) by
dividing the final scale reading by 3. To obtain the
mg/1 phosphorus pentoxide (P205), multiply the final
reading by 0.75.
6.5.8.7 Calculations
The concentration of phosphate (total inorganic and organic) is read
directly from the instrument. As indicated in Steps 11 and 12 (Section
6.5.8.6), the concentration of Inorganic phosphate is measured directly
6-32
-------
from the instrument, and the concentration of total organic phosphate
is determined by subtracting the amount of total inorganic phosphate from
the results of the total phosphate concentration.
6.5.8.8 Precision and Accuracy
Thirty-three analysts in nineteen laboratories analyzed natural
water samples containing exact increments of organic phosphate, with the
following results:
Increment as
Total Phosphorus
mg P/liter
0.110
0.132
0.772
0.882
Precision as Accuracy as
Standard Deviation Bias, Bias
mg P/Hter - mg/P
* liter
0.033
0.051
0.130
0.128
+ 3.09
+11.99
+ 2.96
- 0.92
+0.003
+0.016
+0.023
-0.008
6-33
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6.5.9 Sulfite Analysis
6.5.9.1 Scope and Application
This method is applicable to aqueous samples of low turbidity and
color or where filtration will not result in loss of sulfite. Silica
in excess of 500 mg/1 and large amounts of organic matter will interfere
with precipitation yielding low results. Nitrite should be absent.
6.5.9.2 Summary of Method
This method makes use of the colloidal precipitate formed by sulfate
(SO*") and barium chloride under strongly acidic conditions. One sample
aliquot is precipitated with BaClp reagent and its turbidity 1s measured.
30% hydrogen peroxide is added to a second aliquot to oxidize the sulfite
to sulfate. This second aliquot is then precipitated with BaCl2 reagent.
The difference in turbidity can then be related to the sulfite
concentration.
6.5.9.3 Definitions
No unique terminology is used in this method.
6.5.9.4 Apparatus
• Portable Test Kit Spectrophotometer for use at 445 nm.
• Standard laboratory glassware.
6.5.9.5 Reagents
t SulfaVer IV powder pillows, Hach No. 12065.
• 30% H202, J.T. Baker No. 2186
6.5.9.6 Procedure
1) The sample cannot be preserved. It must be analyzed as soon
as possible after collection.
2) Add 25.0 ml of sample (less if high in sulfate) to each of two
sample cells, A and B. If the sample is turbid, filter through
Whatman No. 2 paper. Add 25 ml H20 to a third sample cell
to act as a blank.
3) To cell A, add 0.5 ml of 30% H202 and mix. Allow this mixture
to stand at least three minutes. To cell B add 0.5 ml of H20
and mix.
6-34
-------
4} Add a package of SulfaVer IV to each of the three samples and
mix until dissolved. Malt about ten minutes to allow turbidity
to develop.
5) Set wavelength dial to 450 ml. Place cell C In sample holder
and use light control knob to set meter at zero mil1 grams per
liter. Record readings for cells A and B.
6.5.9.7 Calculations
Sulflte concentration = |^- (A-B)
A = Reading for Cell A
B = Reading for Cell B
If sample size 1s other than 25 ml multiply the above result by
y
-s£- where
X = ml of sample used (should be same for A and B)
6.5.9.8 Accuracy and Precision
This method 1s accurate to 1 mg/1. A synthetic unknown containing
259 mg/1 sulfate was analyzed 1n 19 laboratories by the turb1d1metr1c
method, with a relative standard deviation of 9.1% and a relative error
of 1.2%.
6-35
-------
6.5.10 Sulfate
6.5.10.1 Scope and Application
Method is applicable to drinking and surface waters, domestic and
industrial wastes. The method is suitable for all ranges of sulfate;
however, for reliable readings, sample aliquots containing not more than
40 mg/1 SO^ should be used.
6.5.10.2 Summary of Method
Sulfate ion Is converted to a barium sulfate suspension under control-
led conditions, using Hach SulfaVer IV Sulfate Reagent (barium chloride).
The resulting turbidity is determined spectrophotometrically at 450 nm.
6.5.10.3 Interferences
Silica in excess of 500 mg/1 will interfere. The test is not
temperature dependent.
6.5.10.4 Apparatus
Hach Portable Test Kit spectrophotometer for use at 450 nm. Standard
laboratory glassware.
6.5.10.5 Reagents
• Hach SulfaVer IV Sulfate Reagent Powder Pillow.
• Sulfate standard solution, 50 mg/1 S04.
6.5.10.6 Procedure*
1. Fill a clean sample cell with sample to the 25 mark. See
Note A.
2. Add the contents of one SulfaVer IV Sulfate Reagent Powder
Pillow and swirl to mix. A white turbidity will form if
sulfate is present. Allow at least 5 minutes but not more
than 15 minutes for the turbidity to fully develop before
completing Steps 2 and 4. See Note B.
* Abstracted from Hach Direct Reading Engineers Laboratory Methods
Manual (DR-EL/2).
6-36
-------
3. Fill another sample cell to the 25 mark with some of the
original water sample and place it in the cell holder. Insert
the Sulfate (SulfaVer IV Method) Meter Scale in the meter and
adjust the Wavelength Dial to 450 nm. Adjust the LIGHT CONTROL
for a meter reading of zero mg/1.
4. Place the prepared sample in the cell holder and read the
mg/1 sulfate (S04).
Notes;
A. Filtering is recommended for highly colored and/or turbid
water samples. Large amounts of color and/or tubidity will
interfere and cause high readings. The filtered sample is
then used in Steps 1 and 3.
B. The sample should not be disturbed during the 5-minute
turbidity development period. Results will not be affected
if the SulfaVer IV Sulfate Reagent Powder does not completely
dissolve.
6.5.10.7 Calculation
As indicated above, the concentration of sulfate is read directly from
the instrument.
6.5.10.8 Comment
After each test the sample cells should be cleaned using a brush and
soap, if this is not done soon after each test, a white film will develop
on the inside of the cells and lead to errors in future tests.
6.5.10.9 Precision and Accuracy
Thirty-four analysts in sixteen laboratories analyzed six synthetic
water samples containing exact increments of inorganic sulfate with the
following results:
6-37
-------
Increment as
Sulfate
mg/11ter
8.6
9.2
no
122
188
199
Precision as
Standard Deviation
mg/Hter
2.30
1.78
7.86
7.50
9.58
11.8
Accuracy
Bias
%
-3.72
-8.26
-3.01
-3.37
+0.04
-1.70
as
Bias
mg/
liter
-0.3
-0.8
-3.3
-4.1
+0.1
-3.4
6.38
-------
6.5.11 Cyanide. Free
6.5.11.1 Scope and Application
This method is applicable to the determination of free cyanide in
saline and non-saline waters, domestic and industrial wastes. If a total
cyanide concentration value is required, i.e., a value for both free
and complex cyanides, a distillation must be performed prior to analysis-^
6.5.11.2 Summary of Method
Free cyanide is determined colorimetrically using the prepackaged
Hach Model CYN-2 Cyanide Test Kit. Although the contents of the "Powder
Pillows" used in the reaction are not stated, it is quite probable that
as in the standard colorimetric measurement procedure the cyanide is con-
verted to cyanogen chloride, CNC1, by reaction with chloramine -T at a pH
less than 8. When this reaction is complete, color is formed on the
addition of pyridine-pyrazolone or pyridine-barbituric acid reagent.
The color intensity is then compared with standard colors to determine
the free cyanide content of the sample.
6.5.11.3 Interferences
Although the Hach procedure does not discuss interferences, it is
most probable that sulfides would adversely affect this procedure,as
well as the standard colorimetric technique.
If a drop of sample on lead acetate test paper indicates the presence
of sulfides, treat 25 ml more of the stabilized sample (pH>12) than that
required for the cyanide determination with powdered cadmium carbonate.
Yellow cadmium sulfide precipitates if the sample contains sulfide.
Repeat this operation until a drop of the treated sample solution does
not darken the lead acetate test paper. Filter the solution through a
dry filter paper into a dry beaker, and from the filtrate, measure the
sample to be used for analysis. Avoid a large excess of cadmium and
a long contact time in order to minimize a loss by complexatlon or
occlusion of cyanide on the precipitated material.
Distillation procedure may be found in ASTM Standards, Part 23, Water:
Atmospheric Analyses, p. 498, Method D2036-72 Reference Method A(p 173).
2Hach Direct Reading Engineers Laboratory Methods Manual (DR-EL/2).
6-39
-------
6.5.11.4 Sample Handling and Preservation
Samples should be analyzed as rapidly as possible after collection.
If storage is required, the samples should be stored in a refrigerator
or in an ice chest filled with water and ice to maintain temperature at
4°C.
If a sample were to be returned to the laboratory for subsequent
distillation and total cyanide analysis, the sample should be collected
in plastic bottles of 1 liter or larger size. (All bottles must be
throughly cleansed and thoroughly rinsed to remove soluble material
from containers.) The sample must also be preserved with 2 ml of 10 N
sodium hydroxide per liter of sample (pH£12) at the time of collection.
6.5.11.5 Apparatus
• Hach Portable Test Kit Spectrophotometer
• Standard laboratory glassware.
6.5.11.6 Reagents
Reagents for the Hach Model C4N-2 Cyanide Test Kit include the
following:
1) Metal Inhibitor Powder Pillow
2) CyanlVer I Powder Pillow
3) CyanfVer II Powder Pillow
6.5.11.7 Procedure
1) If the water sample is turbid, filter a sample for testing.
To do this, place the funnel on one of the square mixing
bottles. Place a piece of folded filter paper in the funnel.
Pour the water sample into the filter paper and allow it
to pass through. Filter enough sample to fill the square
mixing bottle up to the shoulder.
2) Add the contents of one Metal Inhibitor Powder Pillow to the
filtered sample. Swirl to mix.
3) Add the contents of one CyaniVer I Powder Pillow. Swirl to
mix and dissolve.
4) Add the contents of one CyaniVer II Powder Pillow. Swirl to
mix and dissolve. If cyanide is present, a pink color will
develop in a short time. Allow 15 minutes for color develop-
ment, during which the color becomes progressively more purple,
6-40
-------
and will then become a true blue. Swirl the sample bottle
from time to time to aid in dissolving the powders.
(See Note A).
5) Fill a color viewing tube to the 5 ml mark with the prepared
sample, and place it in the right opening in the comparator.
6) Fill the other color viewing tube to the 5 ml mark with clear
water and place it in the left opening in the comparator.
7) Rotate the color disc until a color match is obtained. Read
the ppm Cyanide (CN) from the scale window.
NOTES:
A. Fifteen minutes is the time usually required at 25°C. If
the sample is colder, a longer time will be required, and
if wanner, a shorter time. In all cases, wait until the
color changes to a true blue, with no trace of red remaining.
If the sample stands too long, the color will eventually
turn a greenish-blue. If over-development occurs, repeat
the test.
6.5.11.8 Calculations
The free cyanide concentration of the sample is read directly from
the scale window on the colorimeter in this test kit.
6.5.11.9 Precision and Accuracy
There are no data available at this time on the precision or
accuracy of this method.
6-41
-------
6.5.12 Ammonia Nitrogen
6.5.12.1 Scope and Application
The method covers the determination of ammonia in drinking, surface
and saline waters, domestic and industrial wastes in the range of 0-2 mg/1.
6.5.12.2 Summary of Method
The sample is reacted with Nessler Reagent (a solution of mercuric
iodide in the presence of potassium iodide). The yellow color which
develops is proportional to the concentration of ammonia present, which
is determined spectrophotometrically at 425 nm.
6.5.12.3 Interferences
If the hardness of the water sample is above 100 mg/1 (about 6 grains)
a precipitate of magnesium hydroxide may form a slight turbidity and cause
high readings. One drop of Rochelle Salt Reagent added to each sample will
eliminate this interference.
Iron and sulfide will interfere by causing a turbidity with the Nessler
Reagent. Less common interferences such as hydrazlne, glycine, aliphatic
and aromatic amines, organic chloramines, acetone, aldehydes, and alcohols
may cause greenish or other off-colors, or turbidity. These Interferences
can be overcome by distilling the sample before making the test.
6.5.12.4 Apparatus
Hach Portable Test Kit spectrophotometer for use at 425 nm. Standard
laboratory glassware.
6.5.12.5 Reagents
• Nessler reagent
t Rochelle salt reagent
• Ammonia Nitrogen Standard Solution, 1.0 mg/1
6.5.12.6 Procedure*
1. Fill a clean 25 ml graduated cylinder with sample to the
25 ml mark. Pour Into a clean sample cell.'
2. Measure 25 ml of deminerallzed water by filling another clean
25 ml graduated cylinder to the 25 ml mark. Pour the
demlneralized water into another clean sample cell. See Note A.
3. Using the 1 ml calibrated dropper, add 1 ml of Nessler Reagent
to each sample cell and swirl to mix. See Note B. A yellow
color will develop if ammonia nitrogen 1s present. Allow at
least 10 minutes, but not more than 25 minutes for the color
6-42
-------
to fully develop before performing Steps 4 and 5.
4. Place the sample cell containing the prepared demlnerallzed
water solution 1n the cell holder. Insert the Nitrogen, Ammonia
(Nessler Method) Meter Scale 1n the meter and adjust the
Wavelength Dial to 425 nm. Adjust the LIGHT CONTROL for a
meter reading of zero mg/1.
5. Place the prepared sample 1n the cell holder and read the mg/1
ammonia nitrogen (N). See Note C.
Notes;
A. The temperature of the demlnerallzed water and the water
sample should be 20° + 1°C (68° + 2°F) for best results.
Higher temperatures will cause high readings and lower
temperatures will cause low results.
B. A slight precipitate 1n the Nessler Reagent is normal.
These solids should not be disturbed when transferring the
reagent. If the Nessler Reagent turns a dark brown, 1t
should be discarded and a fresh supply ordered.
C. The results may be expressed as mg/1 ammonia (NHJ or
mg/1 ammonium (NH4) by multiplying the final scale reading
by 1.22 or by 1.29, respectively.
6.5.12.7 Calculation
As Indicated above, the concentration of ammonia 1s read directly from
the spectrophotometer.
6.5.12.8 Precision and Accuracy
Data are unavailable on the precision and accuracy of the method.
Abstracted from Hach Direct Reading Engineers Laboratory Methods
Manual (DR-EL/2).
6-43
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Figure 6-1. Data Sheet - Acidity
SAMPLE LOCATION DATE SAMPLE REC'D
SAMPLE MEDIUM DATE SAMPLE ANALYZED
LOG NUMBER ANALYZED BY
VERIFIED BY
I STANDARD REAGENTS USED REFERENCE METHOD DATE REAGENT STANDARDIZED
1.
2.
3.
4.
II CALIBRATION CURVE RUN DATE CALIBRATION RUN
1.
2.
3.
4.
Ill CALCULATIONS
Methyl orange acidity mg/1 Phenolphthalein acidity, mg/1
CaC03 = 100 x V] x N CaC03 = 100 x V2 x N
V-j = volume of titrant V2 = volume of titrant
= ml = ml
N = normality of titrant N = normality of titrant
Acidity = mg/1 CaC03 Acidity = mg/1 CaC03
IV SPECIFIC COMMENTS ON SAMPLE CHARACTERISTICS
VISUAL
ODOR
COLOR
SPECIFIC COMMENTS ON SAMPLE ANALYSIS.
VISU AU.
ODOR
ERROR OBSERVATIONS.
6-44
-------
Figure 6-2. Data Sheet - Alkalinity
SAMPLE LOCATION . DATE SAMPLE REC'D
SAMPLE MEDIUM DATE SAMPLE ANALYZED
LOG NUMBER ANALYZED BY
VERIFIED BY
I STANDARD REAGENTS USED REFERENCE METHOD DATE REAGENT STANDARDIZED
1. __
2. _____
3.
4.
II CALCULATIONS
TOTAL ALKALINITY
A /i._ o on vacid x Nacid x 50,000 _ 9n* .. ..
As mg/liter CaC03 = Vsample = 20* Vacid
* Valid when Nacid - 0.02 N, and Vsample = 50 ml
III SPECIFIC COMMENTS ON SAMPLE CHARACTERISTICS
VISUAL
ODOR
COLOR
SPECIFIC COMMENTS ON SAMPLE ANALYSIS
VISUAL
ODOR
ERRORS OBSERVED
6-45
-------
Figure 6-3. Data Sheet - Conductivity
SAMPLE LOCATION DATE SAMPLE REC'D
SAMPLE MEDIUM DATE SAMPLE ANALYZED
LOG NUMBER ANALYZED BY
VERIFIED BY
I CALCULATIONS
r 1 x 10 C where R = Resistance of Sample
b = R(l+0.0200 (t-25) C = Cell Constant
t = temp, C
- (Meter Reading*x Scale Factor x C)
Applicable for field meter with temp compensation
II SPECIFIC COMMENTS ON SAMPLE CHARACTERISTICS
VISUAL
ODOR
COLOR
SPECIFIC COMMENTS ON SAMPLE ANALYSIS
VISUAL_
ODOR
ERRORS OBSERVED
6-46
-------
Figure 6-4. Data Sheet - Hardness
SAMPLE LOCATION DATE SAMPLE REC'D
SAMPLE MEDIUM DATE SAMPLE ANALYZED
LOG NUMBER ANALYZED BY
VERIFIED BY
I CALCULATIONS
ing/liter Total Hardness • Number of ml Titrant x 20
(as CaCOj
O
II SPECIFIC COMMENTS ON SAMPLE CHARACTERISTICS
VISUAL
ODOR
COLOR
SPECIFIC COMMENTS ON SAMPLE ANALYSIS
VISUAL
ODOR
ERRORS OBSERVED
6-47
-------
Figure 6-5. Data Sheet - pH
SAMPLE LOCATION DATE SAMPLE REC'D
SAMPLE MEDIUM DATE SAMPLE ANALYZED
LOG NUMBER ANALYZED BY
VERIFIED BY
I CALIBRATION CURVE RUN ON BUFFER SOLN: DATE CALIBRATION RUN
1. pH 4 BUFFER
2. pH 7 BUFFER
3. pH 10 BUFFER
4.
II CALCULATIONS
pH units = Direct Reading from Meter
III SPECIFIC COMMENTS ON SAMPLE CHARACTERISTICS
VISUAL
ODOR
COLOR
SPECIFIC COMMENTS ON SAMPLE ANALYSIS
VISUAL
ODOR
ERRORS OBSERVED
6-48
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6.6 OPACITY MEASUREMENTS (MODIFIED EPA METHOD 9)
6.6.1 Scope and Application
The opacity of emissions from stationary sources is determined
visually. This method is applicable for the determination of the opacity
of emissions from stationary sources. Also see Section 5.2.11.
6.6.2 Procedure
The observer shall use the following procedures for visually deter-
mining the opacity of emissions:
Position. The observer shall stand at a distance sufficient to provide
a clear view of the emissions with the sun oriented in the 140° sector
to his back. Consistent with maintaining the above requirement, the
observer shall, as much as-possible, make his observations from a position
such that his line of vision is approximately perpendicular to the plume
direction, and when observing opacity of emissions from rectangular
outlets (e.g., roof monitors, open baghouses, noncircular stacks), approx-
imately perpendicular to the longer axis of the outlet. The observer's
Une of sight should not include more than one plume at a time when
multiple stacks are involved, and in any case, the observer should make
his observations with his line of sight perpendicular to the longer axis
of such a set of multiple stacks (e.g. stub stacks on bag-houses).
field Records. The observer shall record the name of the plant, emission
location, type facility, observer's name and affiliation and the date on
a field data sheet (Figure 6-6 and 6-7). The time, estimated distance to the
emission location, approximate wind direction, estimated wind speed, descrip-
tion of the sky condition (presence and color of clouds), and the plume
background are recorded on a field data sheet at the time opacity readings
are initiated and completed.
Observations. Opacity observations shall be made at the point of greatest
opacity In that portion of the plume where condensed water vapor is not
present. The observer shall not look continuously at the plume, but instead
shall observe the plume momentarily at 15-second intervals.
Attached Steam Plumes. When condensed water vapor is present within the
Plume as It emerges from the emission outlet, opacity observations shall
be made beyond the point in the plume at which condensed water vapor Is
no longer visible. The observer shall record the approximate distance
from the emission outlet to the point 1n the plume at which the observa-
tions are made. 6-49
-------
RECORD OF VISUAL DETERMINATION OF OPACITY
PAGE
of
o»
i
(71
O
PHMPAMY
LOCATION
TFCT UIMRFR
DATE
TYPF FACILITY
rniiTRni DEVICE
CLOCK TIME
OBSERVED LOCATION
Distance to Discharge
Direction from Discharge
Height of Observation
Point
BACKGROUND DESCRIPTION
WEATHER CONDITIONS
Mind Direction
Wind Speed
Ambient Temperature
SKY CONDITIONS (clear,
overcast, % clouds, etc
PLUME DESCRIPTION
Color
Distance Visible
OTHER INFORMATION
HOURS OF OBSERVATION
Initial
i
Final
OBSERVE
OBSERVE
OBSERVE
POINT 0
HEIGHT
H
R CERTIFICATION DATE
R AFFILIATION
F FMT^TONS
OF DISCHARGE POINT
SUMMARY OF AVERAGE OPACITY
Set
Number
Readings r
The source
the time e
Time
Start— End
Opacity
Sum
Average
anqed from to * opacity
was/was not in compliance with at
•valuation was made.
Figure 6-6. Record of Visual Determination of Opacity
-------
COMPANY
LOCATIOK
TEST HUHBER_
DATE
OBSERVATION RECORD
OBSERVER
PAGE OF
TYPE FACILITY
POINT OF EMISSIONS
Ok
I
Hr.
Min.
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
IS
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Seconds
0
Ib
M
45
Steam Plume
(Check if applicable)
Attached
Detached
Comments
COMPANY
LOCATION
TEST NUMBER_
DATE
OBSERVATION RECORD
(Continued)
OBSERVER
PAGE OF
TYPE FACILITY
POINT OF EMISSIONS
Hr.
Min.
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
Seconds
0
15
w
45
Steam Plume
(Check If Applicable)
Attached
Detached
Comments
Figure 6-7. Observation Record
-------
Detached Steam Plume. When water vapor in the plume condenses and becomes
visible at a distinct distance from the emission outlet, the opacity of
emissions should be evaluated at the emission outlet prior to the con-
densation of water vapor and the formation of the steam plume.
Recording Observations. Opacity observations shall be recorded to the
nearest 5 percent at 15-second intervals on an observational record sheet.
(See Figure 6-7 for an example.) A minimum of 24 observations shall be
recorded. Each momentary observation recorded shall be deemed to represent
the average opacity of emissions for a 15-second period.
6.6.3 Calculations
Opacity shall be determined as an average of 24 consecutive obser-
vations recorded at 15-second intervals. Divide the observations recorded
on the record sheet into sets of 24 consecutive observations. A set is
composed of any 24 consecutive observations. Sets need not be consecutive
in time and in no case shall two sets overlap. For each set of 24
observations, calculate the average by summing the opacity of the 24
observations and dividing this sum by 24. If an applicable standard
specifies an averaging time requiring more than 24 observations, calculate
the average for all observations made during the specified time period.
Record the average opacity on a record sheet. (See Figures 6-6 and 6-7
for an example).
6.6.4 Accuracy and Precision
The use of a qualified observer has been waived for this program.
Therefore previously determined accuracy and precision cannot be relied
on. The results should be expected to fall well within the established
limits for this program.
6.7 BACHARACH SMOKE SPOT TEST
The Bacharach test is used in the field to supplement the Ringelmann
test. The Bacharach test uses a small plunger pump to pull a sample of the
duct effluent through an inserted filter, thus causing a gray color spot on
the filter. This color spot is then compared to a standard scale and the
appropriate density reading is chosen which corresponds to the filter shade.
The step-by-step procedure for a Bacharach test is presented below.
6-52
-------
6.7.1 Procedure
The following procedure has been abstracted from the instruction manual
for the "True-Spot" Model RCC-B Bacharach test kit.
1. Tear a strip from the perforated filter paper sheet (supplied
in the test kit "smoke scale" envelope). Loosen the clamp
screw in the plunger pump and insert the end of the paper strip
into the slot (see Figure 6-8). Tighten the clamp screw and
release the sampling tube from the rubber barrel clip.
2. Insert the sampling tube at least 2-1/2 inches into the flue
through a 1/4-inch diameter hole located between the furnace/
boiler flue outlet and draft regulator.
3. Pull the pump handle through ten full pump strokes (Figure
6-9).
4. Remove the sampling tube from the flue, loosen the clamp
screw and remove the filter paper.
5. Match the color of the smoke spot on the filter paper strip
to the closest spot on the smoke scale provided. In comparing
the color of the smoke spot to the chart, slide the filter
paper strip between the back of the smoke scale and the white
plastic slide viewing the smoke spot on the filter paper
through the window in the center of the color spots on the
smoke scale with the smoke spot backed by the white plastic
slide (see Figure 6-10).'
6. Take additional samples as required by clamping the filter
paper strip in the slot so that the previous spot is the
visible outside spot.
^•7.2 Comments
The True-Spot Model RCC-B test kit plunger pump should be warmed
to room temperature before sampling begins. This will retard moisture
build-up in condensate traps.
After every 10th sample, the sampling tube should be tapped to
^oosen soot and rust. The pump should also be purged with several rapid pump
strokes to draw in room air (without filter paper in the slot).
When obtaining a sample, a steady pull motion should be used so that
a full stroke is obtained in 3 or 4 seconds.
6-53
-------
Figure 6-8. Insertion of Filter Paper Strip Into
Bacharach Test Plunger Pump
Figure 6-9. Procedure for Obtaining a Sample Using the
Bacharach Smoke Spot Test Plunger Pump
6=54
-------
u
10
(O
o
•p
o
Q.
•o
o
I
3
cn
6-55
-------
For maximum accuracy, the smoke scale should be held at arm's length
when comparing the smoke spot on the filter paper. The smoke scale should
be kept clean and stored in an envelope when not in use.
The test kit apparatus should be subjected to periodic inspection and
maintenance. This includes emptying condensate traps, checking for leakage,
periodic cleaning and lubrication, and replacement of worn and damaged
parts as required, (Additional instructions on general maintenance and
operation of Bacharach test kits, such as the True Spot Model RCC-B, are
provided with each kit).
6.7.3 Precision and Accuracy
Data are unavailable on the precision and accuracy of the Bacharach
test.
fr-56
-------
7.0 ORGANIC ANALYSIS PROCEDURES
7-l INTRODUCTION
The analytical procedures presented in this chapter are designed for
use in Level 1 surveys where it is important both to evaluate the overall
Missions from a large number of sources in a cost effective manner and
to ascertain that relevant information about actual or potential emissions
Problems is properly obtained and utilized. The objective of the pro-
cedures given here is to provide an estimate of the predominant classes
of organic compounds present in a given sample. Thus, the procedures
comprising this total methodology are intended to determine the presence
Or absence of all major classes of organic compounds within the prescribed
'evel of accuracy for a Level 1 analysis.
In addition to the information generated by the Level 1 procedures,
the EPA has additional specific needs for data on the nature and quantity
of all polynuclear aromatic hydrocarbons (PAH) present in samples and
anv unique materials identified 1n specific LC fractions. For thts
reason, "Level 2" analytical gas chromatography/mass spectrometry
(GC/Ms) procedures for these materials are provided in the Level!
analysis scheme.
The samples obtained 1n accordance with the procedures outlined in
Chapter 5 will be liquids or solids. Chapter 3 discusses procedures for
the apportionment of samples between inorganic and organic analyses.
7'2 LEVEL 1 ORGANIC ANALYSIS METHODOLOGY
An overview of the sources of the samples and the appropriate
Co"ib1nations of the samples for analysis is shown in Figure 7-1. The
6Xact handling procedures for disbursing these samples Is described In
Chapter 4.0 and Figures 4-3 and 4-4. The overview of the methodology
u*ed for the Level 1 organic analysis 1s shown in Figure 7-2 and Includes
sample preparation for analysis, decision criteria, and the appropriate
Action for each procedure. It is assumed that the Initial samples have
already been combined and apportioned for the organic and Inorganic
analyses (see Chapter 4). The XAD-2 module samples will have to be com-
for analysis after preliminary workup.
7-1
-------
As of 1 August, 1978, a directed program change requires that all SASS
train organic rinses and extracts from gas and oil (distillate and residual
fired sites be combined Into a single sample (Section 7.3.3). Treatment of
condensate extract samples from these sites is not affected; they are
treated 1n the usual manner.
As indicated in Figures 7-1 and 7-2, the extent of sample preparation
required varies with sample type. The low molecular weight hydrocarbons
(boiling at s90°C) are determined by gas chromatography on-site as
described in Section 6.2 and require negligible preparation. Organic
liquids will not need pretreatment. The majority of the samples, however,
such as SASS train components, aqueous solutions, bottom ashes, and other
solids require an initial solvent extraction (Section 7.3) to separate
the organic and Inorganic portions of the samples before the analyses
can proceed.
Both the extracts and the neat organic liquids are then concentrated
in a Kuderna-Danlsh evaporator to a 10 ml volume (Section 7.4). Two 1 ml
aliquots are then taken from each concentrate for the following analyses:
1) total chromatographable organic material (6C-TCO, Section 7.7) and
GC/MS analysis, should Level 2 efforts be required (.Section- 7,10); and
2) gravimetric determination of non-volatile organic material (Section 7.5)
and an Infrared analysis on the residue from the gravimetric determination
(Section 7.6)
The data provided by performing the TCO and the gravimetric analyses
are now used to make the decision as to the analysis path to be followed
for all other determinations. The TCO analysis provides quantitative
information on the bulk amount of semi-volatile organic material in the
boiling range of the C7 to C16 alkanes--90° to 300°C. The gravimetric
analysis provides quantitative results on the amount of nonvolatile
organics in the sample. These two values combine to give an estimate of
the total organic content of the sample. If the total organic content
of the sample is equivalent to a stack concentration of 500 ^g/m3 or less,
the organic analysis is terminated. If the value is greater than 500 fig/m3
stack concentration, the direction of the analyses will depend on the
TCO, which is the volatile content of the sample.
7-2
-------
-a
i
CO
Figure 7-1. Level 1 Organic Analysis Flow Chart
-------
SAMPLE
APPORTIONATION
SECTION 3.0
1
LIQUID SAMPLES
*
'
SASS TRAIN
SOLVENT RINSES
i
1
AQUEOUS
SOLUTIONS
+
1 ML ALIQUOT
FOR GC-TCO,
SECTION 7. 7 AND
GC/MS SECTION
7.10
TCO II
V
CONCENTRATE
SECTION 7.4
1PUT A
SOLID SAMPLES
V 1
SOLID
MATERIALS
F
PARTI CULATE
OR ASH
+
GRAV INPUT
1
p
r
EXTRACTION
SECTION 7.3
1
'
^
XAD-2
RESIN
^
1 ML
ALIQUOT FOR
GRAVIMETRIC, SECTION 7.5
AND IR SECTION
7.*
METHOD 1
QUANTITY
OF TOTAL
ORGANICS AND
TOTAL ORGANIC
>SOO ^(/M3
TCO >IO% TOTAL
METHOD 2
ALIQUOT FOR LC
9 MG TO 100 MG
UP TO 8 ML
TOTAL ORGANICS
>SOO no/M3;
TCO
GRAVT*IR
FRACTION
>500ng/M3 OR OF
SPECIAL INTEREST,
SECTION
0
LOW RESOLUTION
MASS SPECUOSCOPY,
SEQION 7.9
Figure 7-2. Level 1 Organic Analysis Methodology
7-4
-------
If the TCO is less than 1Q% of the total organic material, the
analytical pathway labeled "Method 2" in Figure 7.2 is followed. A suitably
sized sample aliquot is taken for liquid chromatographic fractionation,
evaporated to dryness and transferred to the LC column (Section 7.8). Each
separated fraction is subsequently subjected to gravimetric and infrared
analyses (Section 7.5 and 7.6, respectively). Whenever the TCO is greater
than 10% of the total organics, an aliquot for LC is prepared by solvent
exchange (Section 7.8) to preserve the volatile species. In this "Method 1"
procedure, each fraction separated still undergoes gravimetric and infrared
analyses; however, the LC fractions are also analyzed for TCO (Section
7.7).
The GC-TCO analysis is used to obtain information on the quantity of
material boiling within discrete ranges which are defined by the n-alkanes,
C7 through CIS, in addition to data on the total amount of'material in
the n-alkane boiling range. It should be noted that all compounds con-
taining oxygen, nitrogen, sulfur or halogens will also be reported as
alkanes. Materials are classified solely on the basis of their retention
time relative to the n-alkane, and are quantitated as n-decane.
The infrared analyses provides information on the major functional
groups, (i.e., chemical compound classes) present in a sample. Data
obtained by the GC-TCO and IR analyses are complementary: many compounds
detected in the GC analysis are too volatile to remain for IR analysis,
and many compounds detected in the IR analysis have too low a volatility
to be detected by the GC-TCO procedure. In a similar manner, the results
of GC analyses of the LC fractions complement the IR analyses of these
samples.
The remaining sections of this chapter contain procedures for sample
handling, preparation, and analysis using the above-mentioned techniques.
All classes of compounds and specific individual species identified in
the total sample must be accounted for in succeeding determinations.
7-5
-------
7.3 EXTRACTION OF SAMPLES FOR ORGANICS
7.3.1 Extraction of Aqueous Samples for Organics
7.3.1.1 Scope and Application
The purpose of this procedure is to prepare liquid samples in the
field for subsequent Level 1 and Level 2 analyses for organics. Typical
liquid samples that may be generated in this program are aqueous conden-
sates, settling pond samples, and ambient water samples. These liquid
extractions are performed with standard separatory funnels. Various
sizes of separatory funnels are used depending upon the size of the sample
and the estimated level of organics in the sample. Thus, before this
procedure is initiated, a decision must be made concerning the appropriate
size separatory funnel which must be used.
7.3.1.2 Summary of Method
The sample volume is measured and the sample is transferred to the
separatory funnel. If necessary, the pH of the sample is adjusted to
neutral with either a saturated solution of sodium bicarbonate or
ammonium chloride. The sample is extracted three times with a volume of
high-purity methylene chloride that is approximately 5 percent of the
sample volume. The resulting extract is measured, dried, and then con-
centrated, as described in Section 7.4, in preparation for analysis.
7.3.1.3 Definitions
0 Sep. funnel - separatory funnel
• MC - methylene chloride
7.3.1.4 Sample Handling
All apparatus (i.e., sample containers, pi pets, graduated cylinders,
etc.) that contact either the liquid samples or the solvent extracts are
to be glass, Teflon, or stainless steel. No grease or lubricant of any
kind is to be used on the ground glass joints of the extraction apparatus.
All glassware is to be rinsed with high-purity MC.
7-6
-------
7.3.1.5 Apparatus
• pHydrlon paper 1n a range of pH 1 to pH 11.
• Separatory funnels with Teflon stopcocks in a range of sizes
from 250 ml to 2000 ml.
t Filter tubes, 150 x 24 mm, Corning 9480 or equivalent.
7.3.1.6 Reagents
• Methylene chloride, high purity - suppliers of high purity
material are:
1) Burdick and Jackson, Distilled-in-Glass.®
2) E. Merck, LiChrosolv.®
3) Fisher Scientific, HPLC.®
• Acetone, only B&J Dist1lled-1n-6lass is acceptable.
• Ammonium chloride - J. T. Baker, "Baker Analyzed" reagent grade.
• Sodium bicarbonate - J. T. Baker, "Baker Analyzed" reagent grade.
• Anhydrous sodium sulfate, granular, reagent grade - eliminate
any organlcs by heating for 3 hours at 450°C.
7.3.1.7 Procedure
a) Select a separatory funnel approximately twice the volume of
the sample to be extracted.
b) Measure the volume of the sample with a graduated cylinder
and transfer It to the separatory funnel. Record this volume.
Label the funnel with the appropriate sample code
identification.
c) Measure the pH of the sample with pH sensitive paper and
adjust the pH, 1f necessary, to neutral. If the pH 1s less
than 6, adjust with NaHC03 solution. If the pH is greater
than 8, adjust with NH4ClJsolut1on.
d) Pour a volume of MC that Is approximately 5 percent of the
sample volume (e.g., for a 1000 ml sample, 50 ml of CHJHJ
Into the graduated cylinder used to measure the sampleSofume.
Rotate the cylinder to rinse the sides and then transfer the
solvent to the separatory funnel.
7-7
-------
e) Extract by shaking vigorously for 2 minutes. Allow the layers
to separate and draw off the MC layer. Repeat two times and
combine the extracts. If an emulsion forms, take appropriate
steps (stir, let stand, etc.) to break it before separating
the layers.
f) Dry the MC extracts by adding anhydrous Na2S04 and filtering
through a glass wool plug.(which has previously been extracted
with MC).
g) Measure the volume of the extract with a graduated cylinder.
h) Transfer the total amount of organic extract to an appropri-
ately sized Kuderna-Danish evaporating apparatus and proceed
with concentration to 10 ml volume according to Section 7.4.
i) After any change in reagents and with changes in sample type
(i.e., requiring pH adjustment), prepare a blank by extract-
ing 1000 ml of deionized water using steps a) through h).
7.3.2 Extraction of Solid Samples for Organic^
7.3.2.1 Scope and Application
The purpose of this procedure is to prepare solid samples for subse-
quent organic analyses. Typical solid samples that may be generated in
this program are cyclone catches, particulate filters, XAD-2 resin
samples, coal, bottom ashes, and electrostatic precipitator dusts.
Various sizes of Soxhlet extractors will be used for this procedure
depending upon the size of the sample and the estimated concentration of
organics in the sample. Thus, before this procedure is begun, the
appropriate size of Soxhlet extractor to be used must be selected.
7.3.2.2 Summary Of Method
The sample is placed or weighed into glass thimbles and extracted for
24 hours with high purity methylene chloride. The resulting extracts are
concentrated according to the procedure described 1n Section 7.4, to a
final volume of 10 ml.
7.3.2.3 Definitions
MC - Methylene chloride
7-8
-------
7.3.2.4 Sample Handling
All equipment (i.e., sample containers, spatulas, tweezers, etc.)
that contacts either the solid samples or the solvent extracts is to
be glass, Teflon, or stainless steel. No grease or lubricant of any
kind is to be used on the ground glass joints of the extraction
apparatus.
All glassware is to be rinsed with the same high purity MC used for
the sample extraction.
7.3.2.5 Apparatus
• Soxhlet extractors in a range of sizes (Ace Glass sizes A to 6)
with glass thimbles and condensers.
• Boiling flasks in a range of sizes from 125 ml to 3000 ml with
stoppers.
• Heating mantles to fit boiling flasks and variable trans-
formers or steam baths.
• Filter paper, Whatman No. 40.
7.3.2.6 Reagents
• Methylene chloride, Distilled-in-Glass^or equivalent.
7-3.2.7 Procedure
a) Place the sample to be extracted in the glass thimble.
• XAD-2 resin; weight directly into thimble if the resin is
dry. If the resin is wet, follow the procedure in Section
7.3.2.8.
t Particulate filters; place pre-weighed filter (or portions
of filter) in thimble.
• Afehes, dusts, etc.; weight onto pre-extracted Whatman filter
discs, fold Into cone shape and place in thimble.
b) Fill the boiling flask 1/2 full with MC.
c) Fit the extractor onto the flask and insert the thimble Into
extractor and add more solvent to fill the extractor. Label
the extractor with the sample code Identification. Complete
assembly by attaching condenser and clamping entire apparatus
In position in heating mantle.
7-9
-------
d) Heat the flask sufficiently to produce one discharge cycle
about every ten to fifteen minutes. Extract each sample for
24 hours. During the first cycle, check the seating of the
ground glass joints by rotating the joints while pushing the
condenser/extractor and extractor/flask together. Check for
solvent loss periodically throughout the extraction and add
solvent as necessary. Record the volume of solvent added.
e) At the completion of the extraction, allow the extractor to
cool. Remove the condenser. Pull out the thimble allowing
any remaining solvent to drain into the extractor. Transfer
the extracted sample to a glass bottle, label with the sample
code identification, and return to the sample bank.
f) Siphon off any solvent in the extractor into the boiling flask.
Remove the extractor. Measure the volume of the solution with
a graduated cylinder. If the Kuderna-Danish concentration
cannot be performed immediately, stopper the boiling flask
until ready. If the evaporation 1s to be performed immediately,
transfer the extract and rinsings to K-D evaporation apparatus
and proceed according to Section 7.4.
g) With every set of samples extracted, prepare a blank by follow-
ing steps b) through g). Leave the glass thimble empty. If
Whatman No. 41 filters are used in the extraction of a set of
samples, then the blank is prepared by adding a pre-extracted
Whatman No. 41 to the glass thimble.
7.3.2.8 Special Procedure for Preparing XAD-2 Resin for Extraction
XAD-2 resin blanks returned from the field may still be packed in
water. All water must be separated from the resin before the Soxhlet ex-
traction with methylene chloride can be performed because the immiscibility
of these two solvents hinders extractor operation.
a) Set a tared size F glass Soxhlet thimble in a large glass
beaker (greater than 500 ml).
b) Drain as much water from the resin as possible, discarding
the water
c) Transfer the resin slurry into the thimble and allow
water to drain into the beaker. Discard the water.
d) Wash the resin with 50 ml Distilled-in-Glass acetone.
Add the acetone slowly, so it can mix with the water in
the resin. The resin will visibly compact as the acetone
passes through the thimble. If the resin still seems to
contain water, more acetone may be passed through the thimble.
Record the total acetone volume used.
e) Retain the acetone for K-D concentration and combination
with the methylene chloride extract of the resin as
described in Section 7.4.7.
7-10
-------
f) Proceed with the extraction of the resin.
g) After completing the extraction, reweigh the thimble and the
dry resin to determine the quantity of resin extracted,
7.3.3 Combination of SASS Train Samples
A directed program change (1 August 1978) requires that all SASS train
organic rinses and extracts from gas and oil (distillate and residual) fired
sites be combined into a single sample. Treatment of condensate from these
sites is not affected by this change. This Section describes how these
samples are to be combined.
The SASS train samples will be combined on the basis of equal volume
percent. The amount of XAD-2'resin taken for organic extraction will de-
termine the percentage of other rinses and extracts to take for combining.
Typically, when the XAD-2 sample weighs 150 g, 10 g is taken as a reserve,
and 140 g is extracted for organics. Thus, 93.3% of the resin is extracted.
Therefore, 93.3% of all other SASS train rinses and extracts are combined
with the resin sample extract. The exact percentage is determined by
actual weights of resin. Blanks are handled in the same way.
XAD-2 resin samples and blanks, and other SASS train solids, are
extracted by Procedure 7.3.2. The combined sample is concentrated by
Procedure 7.4. Because the combined sample contains acetone (from probe
and module rinses and resin blanks), be sure to use Procedure 7.4.7.f.
7.4 CONCENTRATION OF ORGANIC EXTRACTS
7.4.1 Scope and Application
The purpose of this procedure is to concentrate samples for organic
analysis. These samples will be in the form of solvent extracts of solid
and liquid samples and of solvent rinses of sampling hardware. The con-
centrations will be performed with Kuderna-Danlsh evaporators. Various
sizes of evaporators may be used depending upon the size of the sample to
be concentrated.
7.4.2 Summary of Method
The solvent extract or Hnse sample is transferred to a Kuderna-
Danlsh evaporator. The evaporator apparatus 1s heated on a steam bath
to drive off the solvent. When the sample 1s sufficiently concentrated,
7-11
-------
the evaporator is removed from the steam bath and allowed to cool. The
sample is then transferred to a 10 ml volumetric flask.
7.4.3 Definitions
K-D - Kuderna-Danish evaporator
MC - Methylene chloride
7.4.4 Sample Handling
All apparatus (i.e., sample containers, flasks, etc.) that contact
either the solvent extracts and rinses or the concentrates are to be
glass, Teflon, aluminum, or stainless steel. No grease or lubricant of
any kind is to be used on the ground glass joints of the concentration
apparatus.
All glassware is to be rinsed with high-purity methylene chloride.
7.4.5 Apparatus
a) Steam bath.
b) Kuderna-Danish concentrators consisting of flask (125, 250,
and 500 ml), Snyder columns, steel springs, concentrator
tubes (10 ml) and adapters as needed.
c) Disposable Pasteur pipets.
d) Class A pipets, 1 mt.
e) Liquid scintillation vials, aluminum-lined caps.
V
7.4.6 Reagents
a) Methylene chloride, Distilled-in-Glass or equivalent grade
b) Pentane, Distilled-in-Glass
7.4.7 Procedure
a) Select an appropriate size K-D flask and attach a con-
centrator tube with the steel springs. Place one 3 mm glass
bead in the bottom of the tube. Label the K-D flask with
the sample code identification.
7-12
-------
b) The sample must be dried before it is concentrated. Add 5g of
high purity anhydrous Na^SC., which has previously been treated
for three hours at 450°C. Shake thoroughly and observe any
changes in the solution. If necessary, add more Na?SOd and
repeat until the sample appears dry. Filter the solution through
a Whatman 41 filter containing glass wool, both of which have
previously been extracted with methylene chloride.
c) Transfer the sample to the K-D flask. Rinse the sample container
with three 10 ml portions of the same high purity solvent used
when the sample was taken. Add the rinsings to the K-D flask.
d) Attach a Snyder column to the K-D flask and clamp the flask in
position over the steam bath. The solvent should boil at such
a rate that the top ball of the Snyder column bounces lightly.
e) Concentrate the sample to~5 ml. Should there be sufficient
water in the system to form a two-phase system at any time during
the evaporation, stop the concentration and remove the water.
To avoid losing any organics which might be dissolved in the
water, extract it three times with methylene chloride (Section
7.3.1). Combine all the organic extracts and the partially
completed organic concentrate in the K-D apparatus as before
and resume the evaporation.
f) This step applies only to those samples in which the solvent is
an acetone-MC mixture, i.e., probe and module rinses and resin
blank extracts. Concentrate these samples to 10 ml. Add 60 ml
high purity pentane to ensure the formation of a pentane-acetone
(80:20) azeotrope. Reconcentrate to 10 ml. This step occurs
very rapidly because the azeotrope boils at 32°C. If instruc-
tions have been given to add the XAD-2 extract to the module
rinse and/or the probe rinse, this is the time to combine them
in the K-D apparatus. Reconcentrate once again to 10 ml.
g) Remove the K-D assembly from the bath and allow to cool. With
a disposable pipet, add ~1 ml of methylene chloride to the top
of the Snyder column. Allow to drain into K-D flask and then
remove the column.
h) Rinse the sides of the K-D flask with another 1-2 ml of solvent.
Remove the flask, stopper the concentrator tube and mix the tube
contents by shaking vigorously.
i) Transfer the contents of the concentrator tube to a 10 ml volu-
metric flask. Rinse the tube and stopper with 1-2 ml more of
solvent; add these rinsings to the flask and make the flask to
standard volume. Label the flask with the sample code identi-
fication.
j) With a 1 ml Class A pipet, transfer 1 ml of the concentrate to
an ampoule or liquid scintillation vial for TCO analysis and
possible subsequent^GC/MS analysis. Label the container with the
sample code Identification.
7-13
-------
k) With the same plpet as 1n step h, transfer a 1 ml aliquot to a
liquid scintillation vial for gravimetric and IR analysis.
Label the container with the appropriate sample code Identifi-
cation.
7.5 GRAVIMETRIC DETERMINATIONS FOR OR6ANICS
7.5.1 Scope and Application
The purpose of this procedure is to determine the weight of non-
volatile organic species in samples for Level 1 organic analyses. The
procedure 1s performed on the concentrates obtained from the Kuderna-
Danlsh concentrations of solvent extract and rinse samples. Weights of
organic residues as small as 0.1 mg can be measured.
7.5.2 Summary of Method
The samples are transferred to either small glass beakers (for LC
fractions) or tared aluminum weighing dishes. The samples are then
evaporated at ambient temperature to a constant weight. The dry samples
are always stored in a desiccator.
7.5.3 Sample Handling
All apparatus that contact either the concentrate or evaporated
residue samples are to be glass, Teflon, aluminum, or stainless steel.
Evaporation of the samples is to be carried out in an area clean of
airborne dust and organic vapors that could contaminate the samples.
7.5.4 Apparatus
• Analytical balance capable of weighing 0.1 mg with an accuracy
of ±,0.03 mg.
t Stainless steel desiccating cabinet with gasket-sealed closure.
• Volumetric plpet, 1 ml, class A.
• Aluminum weighing dishes.
• Glass beakers, 10 to 50 ml.
7.5.5 Reagents
0 Methylene chloride, D1stilled-1n-Glass^or LiChrosolv
(EN
• Pentane, Distil led-1n-Glass'
or
• Methanol, Distilled-in-Glass^57or LIChrosolV '
7-14
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7.5.6 Procedure
a) Rinse the weighing dishes, or beakers with the high purity
methylene chloride. Oven dry them at 110°C, then cool in a
desiccator. Label with the appropriate sample code
identification, weigh to the nearest 0.1 nig, and record the
tare weights.
b) For organic concentrate samples, transfer 1 ml of the
material from the volumetric flask to the labeled weighing
dish with a 1 ml pi pet, which has been rinsed with methylene
chloride and dried with nitrogen.
c) For LC column fractions, transfer the contents of each
volumetric flask to a pre-cleaned, tared, and labeled
beaker. Rinse each flask with a small amount of the appro-
priate solvent and add the rinsings to the beaker.
Rinsing solvents are as follows:
Fraction 1 - Pentane
Fractions 2-4 - Methylene Chloride
Fractions 5-8 - Methanol
d) Allow the samples in the weighing dishes to evaporate at
ambient conditions in a clean fume hood until visually dry.
Store overnight in the desiccator and then weigh on an
analytical balance. Record this weight to the nearest
0.1 mg. If a concentrate is found to weigh less than 10 mg,
reweigh the pan plus the sample on a micro-balance. Record
this weight to the nearest 0.001 mg.
e) If it was necessary to weigh the sample on a micro-balance,
a more accurate tare weight of the pan will be needed. After
constant weight has been reached and recorded, rinse the
contents from the pan with three successive portions of
methylene chloride into another container and allow the pan to
7-15
-------
air dry in a clean fume hood until visually dry. Store over-
night in the desiccator and reweigh the pan on the micro-
balance. Record this weight to the nearest 0.001 mg.
Calculate the sample weight to 3 significant figures.
7.5.7 Calculations
Subtract the tare weight from the final sample weight for each sample.
This gives the weight of the organic residue. Multiply the residue weight
by the aliquot factor to obtain the total organic residue in the concen-
trate sample.
(Final weight- Total concentrate volume, _ Total organic
tare weight) Aliquot volume ~ residue (mg)
7.6 INFRARED ANALYSIS
7.6.1 Scope and Application
This procedure 1s used to determine the functional groups present in
an organic sample or LC fraction of a partitioned sample. The IR spectra,
when Interpreted, provide Information on functionality (e.g., carbonyl,
aromatic hydrocarbon, alcohol, amine, aliphatic hydrocarbon, halogenated
organic, etc.). Compound identification is possible only whan a compound
1s known to be present as a dominant constituent 1n the sample, which
foreknowledge 1s not likely.
Sample amounts required for this analysis are in the milligram (mg)
range with a lower limit of approximately 0.5 mg. A compound must be
present in the sample at about 5%-10% (w/w) or more in order for the
stronger functional groups of the compound to become apparent for inter-
pretive purposes. Organic solvents, water and some inorganic materials
cause interferences. Water and other substances may also cause a decrease
in the quality (e.g., resolution of a spectrum, sensitivity) of the
analysis.
7.6.2 Summary of Method
The initial organic sample or 1C fraction, after evaporation, is
either (1) taken up in a small amount of carbon tetrachloride or methylene
chloride and transferred to a NaCl window, or (2) mixed with powdered KBr,
7-16
-------
ground to a fine consistency, and then pressed into a pellet. Whenever
LRMS will also be run on the sample, because the criterion weight has been
met, the residue Is mixed and only a portion taken for the IR scan. A
grating IR spectrophotometer 1s used to scan the sample in the IR region
from 2.5 to 15 microns. The spectrum is then interpreted to determine
functional group types 1n the sample.
7.6.3 Definitions
Sample cell - Two NaCl plates with the sample sandwiched in between.
7.6.4 Sample Handling and Preservation
These samples will have been prepared in aluminum weighing dishes
or in glass beakers (LC fractions) (Sections 7.5 or 7.8) from which
solvent, water and other volatile matter have been removed by evaporation
and subsequent desiccation. The samples, when not being used, should be
covered and stored in a desiccator containing a drying agent such as
silica gel, drierite or an ascarite/silica gel mixture. Samples being
stored should also be protected from light in order to avoid deterior-
ation of light sensitive materials.
All glassware and implements must be carefully cleaned, solvent
rinsed and dried before use in the analysis of any sample by this procedure.
Contact of the sample with hands, unprepared surfaces Or any other possible
source of contamination must be avoided.
Low resolution mass spectrometry (LRMS) will be performed on the LC
fractions which exceed specific quantity criteria (Section 3.0)*. The
samples for these analyses will be from the same material on which IR
spectra are determined. Therefore, the analyst performing the IR must take
care to provide the analyst to be performing the LRMS with a sufficient
quantity of homogeneous, uncontaminated sample.
*LRMS are obtained if a sample residue, when referenced to the source,
contains more than the following amounts of material:
Gases - SASS train samples 0.5 mg/m flmiomicS?iinHnnc n i
- Ambient air-part1culates lyg/m3 Aqueous Solutions 0.1
- Ambient a1r-sorbent trap 0.5 mg/m-5
7-17
-------
A sample aliquot for LRMS will be taken, when required, in the follow-
ing manner.
a) Dissolve the dried sample in 1 ml spectrograde carbon tetra-
chloride or methylene chloride. Mix well to ensure homo-
geneity.
b) Pi pet 0.5 ml of the well mixed solution to a clean, labeled,
tight sealing container.
c) Refrigerate the LRMS sample.
d) Proceed with the IR analysis on the remaining sample portion.
7.6.5 Apparatus
• Infrared (IR) spectrophotometer, grating dispersion. Perkin-
Elmer 283 or equivalent.
t NaCl windows - Configured to fit sample holder of spectro-
photometer. Transparent to the IR in the 2.5 to 15 micron
region.
• KBr pellet press - Hydraulic type is preferred (Carver Model C
or equivalent) but hand-held devices are acceptable, e.g.,
Perkin-Elmer 186-0436 or equivalent.
• KBr pellet die - To prepare 13 mm diameter or equivalent pellet
to contain approximately 1 mg of sample. Perkin-Elmer 186-00250
or equivalent.
• Pipet, Pasteur, disposable - Sargent S-69647-30 or equivalent.
t Standard polystyrene film sample - Normally supplied by
instrument manufacturer.
7.6.6 Reagents
• Methylene chloride - D1st1lled-1n-Glass and/or
• Carbon tetrachloride - Distilled-in-61ass
• KBr powder - Spectrograde, dried at 105°C
7.6.7 Procedure
It is possible that two sample forms will occur: (1) an amorphous
mass (expected to be the typical sample), and (2) a crystalline or
powdery mass. Separate procedures are desirable for these two forms in
order to obtain the best available spectra.
7-18
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7.6.7.1 Procedure for Amorphous Material
Add a few drops of carbon tetrachloride or methylene chloride to
solubilize the sample slightly and mix with the tip of a disposable
Pasteur pipet. Then using the pipet, take a few drops of this material and
transfer to a clean NaCl window. Allow the solvent to evaporate at ambient
temperature and then press the two NaCl windows together to spread the
sample throughout the area where the IR beam impinges on the plate. Mount
the sample cell in the sample compartment of the spectrophotmeter pre-
viously set up according to the manufacturer's manual and check for
resolution (see Note on Resolution). Scan the region from 2.5 to 15
microns using the parameters in Table 7-1. The sample size should be
adjusted so that the most intense peak in the spectrum has a percent
transmittance of between 5 to 15 percent. If the spectrum is too weak,
more sample must be added, the solvent evaporated, the plates reassembled,
and the spectrum rerun as above. If the spectrum is too strong, i.e.,
peaks with less than 5 percent transmittance, excess sample must be
removed by wiping the plates and rerun as above.
7.6.7.2 Procedure for Crystalline Material
The preferable IR sample preparation for crystalline or powdery
materials is a KBr pellet. Mix the sample thoroughly to ensure homo-
geneity. Take about 1 mg of sample and mix with typically 300 mg of
KBr powder (amounts can be adjusted to meet specifications of the KBr
pellet die used). A small mortar and pestle can be used to mix the
sample, but the use of a sample amalgamator or motorized grinder is
probably preferable. Add the mixture to the pellet die, assemble and press
the pellet according to the manufacturer's instructions, and check for
resolution (see Note below). The resulting pellet is placed in the
instrument's sample stage, and it is scanned using the parameters in
Table 7-1. Normally, the ratio of 1 mg sample to 300 mg KBr powder
yields a spectrum of the proper intensity. However, more sample can be
added, or the pellet diluted with more KBr, reground, and rerun as
required. Excessively thick samples, as evidenced by an opaqueness of
7-19
-------
the sample pellet or by an extremely low level of transmittance when the
sample is placed in the instrument's sample beam, are to be reground,
diluted with KBr and re-pelletized. These thick samples will not produce
a spectrum with resolution suitable for interpretation and identification
of chemical groups.
Table 7-1. Instrument Scanning Parameters
Scan time for 2.5 - 15 microns 1Q-12 minutes
Scale expansion 1X-10X, as required
Transmittance/absorbance mode switch Transmittance
Note on Resolution
The instrument settings affecting resolution will vary somewhat
with different instrument manufacturers and models. The instrument pre-
paration shall include a test scan using a standard polystyrene film.
Comparison of the obtained spectra with an acceptably resolved standard
spectra will demonstrate that the instrument is performing acceptably.
This resolution check shall be performed at least once each day that
samples are analyzed. Figure 7-3 (a) and (b) shows typically acceptable
resolutions.
The resulting spectra are interpreted by one with training and
experience in this field. Access to the several general and special
literature sources on IR interpretation are assumed.
Note on Moisture in Sample
A very broad peak over the area 2.9 to S.Otiand a moderately strong
peak at 6.0jji are generally indicative of water in the sample or in the
KBr in the case of a pellet. The pellet should be reground, dried
further and then remade before a spectrum is recorded for analysis pur-
poses. A sample on a salt window may need to be dried under a heat lamp
before .a satisfactory scan can be made. The water spectrum can obscure
bands produced by particular functional groups, and can thereby result
in an inaccurate spectral interpretation.
7-20
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Wavelength, ion
5.0 6.0
7.0 ao 9.0 10 12 14 16
4000
3000
3000
2500
2000 1800 1600 1400 1200 1000 800 62$
Wavenumbei, cm"1
Wavenumber, cm-1
4000 3000
2000
1500
100
FIGURE 7-3.
Standard Polystyrene Film Spectra Showing Acceptable
Resolution, (a) Linear 1n Wave Number (cm-l), (b) Linear
in Wave Length
7-21
-------
7.6.8 Calculations
Calculations are not required in this qualitative technique.
7,6.9 Accuracy and Precision
Values cannot be given owing to (1) the variable nature of the
sample and (2) the qualitative, not quantitative, nature of the analyses.
7.7 C7 - C16 TOTAL CHROMATOGRAPHABLE ORGANIC MATERIAL ANALYSIS*
7.7.1 Scope and Application
7.7.1.1 Scope
In tMs procedure, gas chromatography is used to determine the quan-
tity of lower boiling hydrocarbons (boiling points between 90° and 300°C)
in the concentrates of all organic solvent rinses, XAD-2 resin and LC
fractions-when Method 1 is used (Figure 7-2 and Section 7.8)-encountered
in Level 1 environmental sample analyses. Data obtained using this
procedure serve a twofold purpose. First the total quantity of the
lower boiling hydrocarbons in the sample is determined. Then whenever
the hydrocarbon concentrations 1n the original concentrates exceed 75
g
ug/m , the chromatography results are reexamined to determine the amounts
of individual species.
The extent of compound identification is limited to representing all
materials as normal alkanes based upon comparison of boiling points. Thus,
the method is not qualitative. In a similar manner, the analysis 1s
sem1quant1tat1ve: calibrations are prepared using only one hydrocarbon.
They are replicated but samples routinely are not.
7.7.1.2 Application
This procedure applies solely to the Level 1 C7-C16 gas chromato-
graphic analysis of concentrates of organic extracts, neat liquids, and
of LC fractions. Throughout the procedure, it is assumed the analyst has
been given a properly prepared sample.
*TCO analyses of particulate extracts and probe and cyclone rinses were
eliminated after March, 1978, 'by an official U.S. EPA change to Level 1.
7-22
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7.7.1.3 Sensitivity
The sensitivity of this procedure, defined as the slope of a plot of
response versus concentration is dependent on the instrument and must be
verified regularly. TRW experience indicates the nominal range is of the
order of 77 yV-sec-yl/ng of n-heptane and 79 yV-sec'yl/ng of n-hexadecane.
The instrument is capable of perhaps one hundredfold greater sensitivity.
The level specified here is sufficient for Level 1 analysis.
7.7,1.4 Detection Limit
The detection limit of this procedure as written is 1.3 ng/p.1 for a
1 nl injection of n-decane. This limit is arbitrarily based on defining
the minimum detectable response as 100 yV-sec. This 1s an easier operational
definition than defining the minimum detection limit to be that amount of
material which yields a signal twice the noise level.
7.7.1.5 Range
The range of the procedure will be concentrations of 1.3 ng/yl and
greater.
7.7.1.6 Limitations
Reporting Limitations. It should be noted that a typical environ-
mental sample will contain compounds which: (a) will not elute in the
specified boiling ranges and thus will not be reported and/or (b) will not
elute from the column at all and thus will not be reported. Consequently,
the organic content of the sample as reported is a lower bound and should
be regarded as such.
Calibration Limitations. Quantltation is based on calibration with
n-decane. Data should therefore be reported as, e.g., mg C8/m3 as n-decane.
Since response varies linearly with carbon number (over a wide range the
assumption may Involve a 20% error), it is clear that heptane (C7) detected
In a sample and quantltated as decane will be overestimated. Likewise,
nexadecane (C16) quantltated as decane will be underestimated. From pre-
vious data, 1t is estimated the error involved is on the order of 6-7£.
7-23
-------
Detection Limitations. The sensitivity of the flame ionization
detector varies from compound to compound. However, n-alkanes as a class
have a greater response than other classes. Consequently, using an n-alkane
as a calibrant and assuming equal responses of all other compounds tends
to give low reported values.
7.7.2 Summary of Method
A 1 ml aliquot of all 10 ml concentrates is disbursed for gas
chromatography analysis. When Method 1 is followed (see Section 7.2),
LC fractions are also disbursed for GC-TCO analysis. With boiling point-
retention time and response-amount calibration curves, the data (peak
retention times and peak areas) are interpreted by first summing peak
areas in the ranges obtained from the boiling point-retention time
calibration. Then, with the response-amount calibration curve, the area
sums are converted to amounts of material in the reported boiling point
ranges.
After the instrument is set up, the boiling point-retention time
calibration is effected by injecting a mixture of n-C7 through n-C16
hydrocarbons and operating the standard temperature program. Response-
quantity calibrations are accomplished by injecting n-decane in, n-pentane
standards and performing the standard temperature program.
7.7.3 Definitions
0 GC - Gas chromatography or gas chromatograph
0 C7-C16 n-alkanes: heptane through hexadecane
0 GCA temperature program: 4 minutes isothermal at 60°C,
10°C/min from 60° to 220°C
• TRW temperature program: 5 minutes isothermal at room
temperature, then program from 30°C to 250°C at 15°C/min.
7.7.4 Sample Handling and Preservation
After concentration of organic extracts and rinses to 10 ml (Sec-
tion 7.4), a 1 ml aliquot is taken for both this analysis and possible
subsequent GC/MS analysis (Section 7.10) and set aside in the sample bank.
7-24
-------
For each GC-TCO analysis, obtain the sample sufficiently in advance to
allow it to warm to room temperature. For example, after one analysis is
started, return that sample to the sample bank and take the next sample.
7.7.5 Apparatus
7.7.5.1 Gas Chromatograph
This procedure is intended for use on a Varian 1860 gas chromatograph,
equipped with dual flame ionization detectors and a linear temperature
programmer. Any equivalent instrument can be used provided that electrom-
eter settings, etc., be changed appropriately.
7.7.5.2 Gases
• Helium - minimum quality is reactor grade. A 4A or 13X
molecular sieve drying tube is required. A filter must
be placed between the trap and the instrument. The trap
should be recharged after every third tank of helium.
• Air - zero grade air is satisfactory.
• Hydrogen - zero grade.
7.7.5.3 Syringe
Syringes are Hamilton 701N, 10 ul, or equivalent.
7.7.5.4 Septa
Septa will be of such quality as to produce very low bleed during the
temperature program. An appropriate septum 1s Supelco Mlcrosep 138, which
Is Teflon backed. If septum bleed cannot be reduced to a negligible level,
It will be necessary to Install septum swingers on the Instrument.
7.7.5.5 Recorder
The recorder for this procedure must be capable of no less than 1 mV
full-scale display, a 1 second time constant, and 0.5 Inch per minute chart
rate.
7.7.5.6 Integrator
An integrator is required. Peak area measurement by hand 1s satis-
factory but too time-consuming. If manual Integration Is required, the
height times width at half height method 1s used.
7-25
-------
7.7.5.7 Columns
• Preferred column - 6 ft x 1/8 in. O.D. stainless steel
column of 10% OV-101 on 100/120 mesh Supelcoport.
• Alternate column - 6 ft x 1/8 in. O.D. stainless steel
column of 10% OV-1 (or other silicon phase) on 100/120
mesh Supelcoport.
7.7.5.8 Syringe Cleaner
Hamilton syringe cleaner or equivalent connected to a suitable vacuum
source.
7.7.6 Reagents
• Pentane - "D1stnied-1n-Glass"®or "Nanograde"® for standards
and for syringe cleaning.
• Methylene chloride - "Distilled-in-Glass"®or "Nanograde"®
for syringe cleaning.
7.7.7 Procedures
7.7.7.1 Setup and Checkout
Each day, the operator will verify the following:
1. Supplies of carrier gas, air and hydrogen are sufficient,
I.e., each tank contains > 100 psig.
2. After replacing any gas cylinder, all connections leading
to the chromatograph will.,be leak checked.
3. The carrier gas flow rate 1s 30 +2 ml/m1n; the hydrogen
flow rate 1s 30 +2 ml/m1n; and tFe air flow rate 1s
300 +20 ml/m1n. ~~
4. Verify the electrometer 1s functioning properly.
5. Verify recorder and Integrator are functioning properly.
6. Leak check the septa. Leak checking 1s effected by placing
the soap bubble flow meter Inlet tube over the Injection
port adaptors. Septa are replaced after no more than 20
Injections.
7. Obtain 11st of samples to be run.
7-26
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7.7.7.2 Retention Time Calibration
To obtain the temperature ranges for reporting the results of the
analyses, the chromatograph is given a normal boiling point-retention
time calibration. The n-alkanes, their boiling points, and data reporting
ranges are given in the table below.
NBP. °C Reporting Range, °C Report As
98
126
151
174
194
214
234
252
270
288
90-110
110-140
140-160
160-180
180-200
200-220
220-240
240-260
260-280
280-300
C7
C8
C9
CIO
cn
C12
C13
C14
C15
C16
n-heptane
n-octane
n-nonane
n-decane
n-undecane
n-dodecane
n-tridecane
n-tetradecane
n-pentadecane
n-hexadecane
Preparation of Standards. Preparing a mixture of the C7-C16 alkanes
1s required. There are two ways: (1) there are standards kits
(Polysdence Kit) 1n which there are bottles of mixtures of selected
n-alkanes which may be combined to produce a C7-C16 standard; and (2)
there are bottles of the Individual C7-C16 alkanes from which accurately
known volumes may be taken and be combined to give a C7-C16 mixture.
Procedure (Depends on Instrument Used)
1. The programmer upper limit 1s set at 250°C. If this setting
does not produce a column temperature of 250°C, find the
correct setting.
7-27
-------
2. The programmer lower limit is set at 30°C.
3. Verify the instrument and samples are at room temperature.
4. Inject 1 yl of the n-alkane mixture.
5. Start the integrator and recorder.
6. Allow the instrument to run isothermally at room temperature
five minutes.
7. Shut the oven door.
8. Change mode to Automatic and start the temperature
program.
9. Repeat steps 1-9 a sufficient number of times so that the
relative standard deviation of the retention times for
each peak is <5%.
To attain the required retention time precision, both the carrier gas
flow rate and temperature program specifications must be observed.
This calibration is performed at the start of an analytical program.
The mixture is chromatographed at the start of each day.
7.7.7.3 Response Calibration
For the purposes of a Level 1 analysis, response-quantity calibration
with n-decane is adequate. A 10 yl volume of n-decane is injected into a
tared 10 ml volumetric flask. The weight injected is obtained and the
flask is diluted to the mark witn n-pentane. This standard contains about
730 ng n-decane per yl n-pentane. The exact concentration depends on
temperature, so that a weight is required. Two serial tenfold dilutions are
made from this standard, giving standards at about 730, 73, and 7.3 ng n-
decane per yl n-pentane, respectively.
Procedure
1. Verify instrument is set up properly.
2. Set electrometer at 1 x 10"10 A/mV.
3. Inject 1 yl of the highest concentration standard.
7-28
-------
4. Run standard temperature program as specified above.
5. Clean syringe.
6. Make repeated injections of all three standards until the
relative standard deviations of the areas of each standard
is $5%.
7. This calibration is performed at the start of an analytical
program and monthly thereafter. The most concentrated
standard is injected once each day. Any change in calibra-
tion necessitates a full recalibration with new standards.
Standards are stored in the refrigerator locker and are
made up monthly.
7.7.7.4 Sample Analysis Procedure
Apparatus
• Gas chromatograph set up and working.
• Recorder, integrator working.
• Syringe and syringe cleaning apparatus.
• Parameters: Electrometer setting is 1 x 10 A/mV; recorder
is set at 0.5-in/min and 1 mV full-scale.
1. Label chromatogram with the date, sample number, etc.
2. Inject sample.
3. Start integrator and recorder.
4. After isothermal operation for 5 minutes, begin
temperature program.
5. Clean syringe.
6. Return sample;obtain new sample.
7. When analysis is finished allow instrument to cool. Turn'
chromatogram and integrator output and data sheet over to
data analyst.
7.7.7.5 Syringe Cleaning Procedure
1. Remove plunger from syringe.
2. Insert syringe into cleaner; turn on aspirator.
7-29
-------
3. Fill pi pet with pentane; run pentane through syringe.
4. Repeat with methylene chloride from a separate pi pet.
5. Flush plunger with pentane followed by methylene chloride.
6. Repeat with methy!ene chloride.
7.7.8 Sample Analysis Decision Criterion
The data from the TCO analyses of organic extract and rinse
concentrates are first used to calculate the total concentration of
C7-C16 hydrocarbon-equivalents (Section 7.7.9) in the sample with respect
to the volume of air actually sampled, i.e., yg/m3. On this basis, a
decision is made both on whether to calculate the quantity of each
n-alkane equivalent present and on which analytical procedural pathway
will be followed. (See Figure 7-2). If the total organic content is
great enough to warrant continuing the analysis -- >500 yg/m3 — a TCO of
o
less than 75 yg/m will require only LC fractionation and gravimetric
determinations and IR spectra to be obtained on each fraction. If the
o
TCO is greater than 75 yg/m, then the first seven LC fractions of each
sample will be reanalyzed using this same gas chromatographic technique.
7.7.9 Calculations
7.7.9.1 Boiling Point - Retention Time Calibration
The required data for this calibration are on the chromatogram and on
the data sheet. The data reduction is performed as follows:
1. Average the retention times and calculate relative
standard deviations for each n-hydrocarbon.
2. Plot average retention times as abscissae versus normal
boiling points as ordinates.
3, Draw 1n calibration curve.
4. Locate and record retention times corresponding to boiling
ranges 90-110, 110-140, 140-160, 160-180, 180-200, 200-220,
220-240, 240-260, 260-280, 280-300°C (See example 1n
Figure 7-4),
7.7.9.2 Response-Amount Calibration
The required data for this calibration are on the chromatogram and on
the data sheet. The data reduction is performed as follows:
7-30
-------
o
I
4->
o
1J
.
Q
fO
O
II»O
I»QO
Retention time, sec.
Figure 7-4. Retention Times Versus Normal Boiling
Points For C7-C16 Hydrocarbons
1. Average the area responses of each standard and calculate
relative standard deviations.
Plot response (yV.sec) as ordinate versus ng/yl as
abscissa. (See example in Figure 7-5.)
Draw in the curve. Perform last squares regression and
obtain slope (yV.sec.yl/ng).
7-7-9.3 Total C7-C16 Hydrocarbons Analysis
The required data for this calculation are on the chroma tog ram and on
the data sheet. The data reduction is performed as follows:
1. Sum the areas of all peaks within the retention time range
of interest.
2. Convert this area (yV.sec) to ng/yl by dividing by the
weight response for n-decane (yV.sec.yl/ng).
3. Multiply this weight by the total concentrate volume
(10 ml) to get the weight of the C7-C16 hydrocarbons
in the sample.
7-31
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...^—...-f _, -T-T-——-•• —p— —
Jntericepjt :?.:7C
10
n-Decane concentration, ng/yl
Figure 7-5. Calibration of FID-GC
With n-Decane
4. Using the volume of gas sampled or the total weight of
sample acquired, convert the result of step 3 above to
yg/m3.
5. If the value of total C7-C16 hydrocarbons from step 4
above exceeds 75 yg/m3, calculate individual hydrocarbon
concentration in accordance with the instructions in
Section 7.7.10.4 below.
7-32
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7-7.9.4 Individual C7-C16 n-Alkane Equivalent Analysis
The required data from the analyses are on the chromatogram and on
the data sheet. The data reduction is performed as follows:
1. Sum the areas of peaks in the proper retention time
ranges.
2. Convert areas (uV.sec) to ng/yl by dividing the proper
weight response (yV.sec.yl/ng),
3. Multiply each weight by total concentrate volume (10 ml)
to get weight of species in each range in the sample.
4. Using the volume of gas sampled on the total weight of
sample acquired, convert the result of step 3 above to
yg/m3.
A sample chromatogram is quantitated in Figure 7-6.
7-'.10 Precision and Accuracy
Even relatively comprehensive error propagation analysis is beyond
the scope of this procedure. With reasonable care, peak area reproduci-
bility of a standard should be of the order of 1% RSD. The relative
standard deviation of the sum of all peaks in a fairly complex waste might
be of the order of 5-10%. Accuracy is more difficult to assess. With
9ood analytical technique, accuracy and precision should be of the order
°f 10-20%.
7-33
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iwgRrlg
!ffc1
-LII.J*,
-••
.._).
y&F-a***. ~(ty
; I
Figure 7-6. Sample Chromatogram With Retention
Times and Peak Areas Noted
Example Calculations
1. Sum the peak areas:
Total Area = 320 + 119 +595 + 716 + 24025
= 25775 HV.sec
2. Convert area to concentration by dividing by weight response
of n-decane
ng_ 25775 yV.sec
ul ' 78.21 yV.sec.yl/ng
ng
= 329.6 -r
|Al
3. Calculate weight of species in concentrated sample
Weight = 329.6 Hi x 10 ml x ^ y1 *
ng
3.30 x 10 yg
7-34
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4. Calculate concentration of species in original sample
TCO
- 3<3° x IQ2 ug
30 m3
= 1,10 x 102 Htg/m3
3
Since this sample contains more than 75 pg/m , the individual
n-alkane equivalents will need to be calculated.
1. Sum the peak areas in the proper retention time ranges:
C7 = 320 yV.sec
C12 = 119 yV.sec
C14 = 595 + 716 + 24025 = 25336 fiV.sec
2. Convert area to concentration by dividing by weight
response of proper n-alkane
/ i P-T 320 uV.sec _ . •,
ng/yl C7 = 7?t74 yV.sec.yl/ng " *§l
/ i no 119 yV.sec , c
ng/^1 cl2 = 78.40 yV.sec.yl/ng " ]'5
/ -, o-i/i 25336 uV.sec
ng/yl C14 = 78f53 yV.sec.yl/ng
3. Calculate weight of each species in concentrated sample
C7 = 4.1-gf-x 10ml x
C12= 1.5
C14 v 323-gf x 10 ml x 103-^fx 10"3-^-= 3.2 x 103 ng
4. Calculate concentration of each species 1n original sample
41 |xg 3
30 m3
C12 = I5 K9- = 0.5 fjig/m3
30 m3
CM'- 3'2 x if M .
30 mj
7-35
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7.8 LIQUID CHROMATOGRAPHIC SEPARATIONS
7.8.1 Scope and Application
7.8.1.1 Scope
This procedure is designed to give a separation of a sample into
seven reasonably distinct classes of compounds.
7.8.1.2 Application
This procedure applies to Level 1 analyses and to SASS train samples
which contain a minimum of 12 mg of nonvolatile organics. Sample weights
from bulk liquids and solids will need to be evaluated on a case-by-case
basis.
7.8.1.3 Sensitivity
As defined, this procedure will permit the analyst to measure as low
as 1 H9 of residue.
7.8.1.4 Detection Limit
The detection limit is 0.1 mg of residue.
7.8.1.5 Range
Samples may range from 9 to 300 mg. The optimum size is considered
to be 100 mg.
7.8.1.6 Limitations
Compounds of too high polarity or molecular weight will not be eluted
from the column since this procedure 1s a compromise between cost and data
acquisition. Also, compounds of too low molecular weight may be evapor-
ated along with the sample solvent during sample preparation.
Classes of compounds may be observed in more than one fraction as a
result of the limited fractionating capacity of this chromatographlc pro-
cedure.
7-36
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7.8.2 Summary of Method
A sample weighing from 9 to 100 mg is placed on a silica gel liquid
chromatographic column. A series of seven eluents are employed to sepa-
rate the sample into nominally eight distinct classes of compounds for
further analyses.
Depending on the TCO level in the concentrated sample, the fractions
may be analyzed by the TCO procedure (Section 7.7) for information on the
mass of material present in each fraction. These data supplement the
gravimetric and infrared analyses which are performed on all fractions
(Sections 7.5 and 7.6).
7.8.3 Definitions
7.8.4 Sample Handling and Preservation
The traveler for this analysis will specify the volume of concen-
trated extract to be taken to give an appropriate weight of material for
the separation. This specific volume is withdrawn with a graduated pipet.
Then the sample is returned to storage.
7.8.5 Apparatus
~' " ii.' i '• iiiiii i i ^
t Column: Water jacketed 200 mm x 10.5 mm i.d. glass column
with Teflon stopcock.
• Absorbent: Davison Silica Gel, 60-200 mesh, Grade 950.
• Graduated cylinders: 25 ml and 10 ml.
t Volumetric Flasks: One 25 ml and six 10 ml, precleaned.
• Beakers: 10 and 50 ml.
t Miscrospatula.
• Pipet: 1 ml, Class A.
t Liquid scintillation vials.
t Disposable pipets.
• Glass Wool: Extracted 24 hours with methylene chloride in
Soxhlet apparatus.
• Funnel.
7-37
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7.8.6 Reagents
Solvents are all D1stilled-1n-Glas£-< quality.
t Cyclopentane
• E1uents Amounts Collected
1) pentane 25 ml
2) 20% CH2C12/pentane 10 ml
3) 50% CH2Cl2/pentane 10 mi
4> CH2CV 10ml
5) 5% CH3OH/CH2C12 10 ml
6) 20% CH3OH/CH2C12 10 ml
7) 50% CH3OH/CH2C12 10 ml
7.8.7 Decision Criteria for Technique to be Used In Performing 1C
. Separations
As indicated in Figure 7.2, two distinct analytical procedures may be
used in the performance of LC fractionations and subsequent analyses.
The selection of the pathway "Method 1" or "Method 2" will be based on
the results of gravimetric and TOO determinations on the concentrated
organic sample (Sections 7.5 and 7.7 ). For a LC separation to be required,
the total organic content of the total, original sample must exceed 500 wg/m .
Method 2 is used whenever the volatile hydrocarbon content determined by the
TCO analysis is low -- less than 10% of the total. Method 1 is used whenever
the volatile materials content is in excess of 10% of the total.
The first difference between Method 1 and Method 2 is in the method
of preparing the sample for introduction onto the LC column. In Method 2,
where there are few volatile substances, a simple, direct solvent evapora-
tion step is sufficient. In Method 1, however, care must be taken to pre-
serve all the lower boiling components for the LC separation and subsequent
analyses. Therefore, a solvent exchange step has been incorporated to
transfer the sample from methylene chloride to the non-polar solvent
7-38
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cyclopentane. In addition, when Method 1 1s used, a TCO analysis will be
performed on the seven fractions. Since the TCO of the original sample
1s a significant portion of .the total organic content, 1t 1s Important to
know more about the types of volatile compounds present.
7.8.8 Procedure
The volume of samples expected during the Source Assessment program
means that a reasonable number of LC separations will be performed. Six
columns are the maximum that will be operated by any single analyst. Of
these six columns, one will be a blank, unless experience shows the blank
Is reproducible. Then the blank may be run with every second or third set
of columns.
The data to be obtained and recorded are:
• Weight of sample added to column.
• Weights of all fractions as determined 1n the TCO procedure.
• Weights of fractions after they have been evaporated 1n glass
beakers to constant weight.
7.8.8.1 Sample Preparation by Solvent Exchange (Method 1)
1. Obtain volume of sample extract calculated to contain 9 to 100
mg of solute: 9 mg 1s the minimum usable quantity, and 100 mg
1s the optimum weight.
2. P1pet the extract Into a K-D receiver graduated centrifuge tube.
3. Add 200 mg of cleaned, freshly activated silica gel (Section
7.8.8.3} to the sample and mix thoroughly using a mlcrospatula.
4. Protecting the container opening with a small ribbed watch glass
or cleaned aluminum foil, set 1t In a hood and allow the solvent
to evaporate at room temperature to a 1 ml volume.
5. Add 1 ml cyclopentane and mix by gentle agitation.
6. Again allow the solvent to evaporate to a 1 ml volume.
7. Repeat steps 5 and 6.
8. The cyclopentane and silica gel are now ready for transfer to
the top of a previously prepared LC column. A Pasteur plpet
is suggested to handle this material.
9. Rinse the sample container used with another 0.5 ml of cyclo-
petane, then transfer this solvent to the top of the LC column.
7-39
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7.8.8.2 Method 2 Sample Preparation, Evaporation to Dryness
1. P1pet or accurately measure a volume of sample extract calculated
to give either the optimum weight, 100 mg, or a weight not less
than 9 mg. Calculate the exact weight from the gravimetric
determination (Section 7.5).
2. Obtain a precleaned and labeled beaker of at least 30% greater
capacity than the required volume of sample. Pi pet the sample
into the beaker, cover loosely with a watch glass, place in a
fume hood and evaporate the solvent nearly to dryness.
3. Add 0.5-1.0 g of freshly activated silica gel (Section 7.8.8.3)
to the sample container and mix thoroughly with sample using a
microspatula.
4. Add 5 ml cyclopentane and allow the sample to evaporate again to
about 1 ml.
5. Transfer the 1 ml mixture of cyclopentane and silica gel via a
Pasteur pi pet to the top of the prepared LC column.
6. Rinse the receiver with another 0.5 ml cyclopentane and transfer
this volume of solvent to the top of the LC column.
7.8.8.3 Cleaning and Activation of Silica Gel
The silica gel is cleaned by extracting it in a Soxhlet apparatus for
24 hours using the sequence of solvents methanol, methylene chloride, and
finally pentane. The apparatus and procedure are as follows:
Apparatus
t Soxhlet extractor with glass thimble and condenser.
• Boiling flask with stopper of a size to match the Soxhlet
extractor.
• Heating mantle to fit boiling flask and variable transformer or
steam bath.
Reagents
§ Methanol, Distllled-in-Glass®
• Methylene chloride, Distilled-in-Glass®
• n-Pentane, Distilled-in-Glass^
7-40
-------
Procedure
a) Place the silica gel to be extracted in the glass thimble.
b) Fill the boiling flask half-full with methanol.
c) Fit extractor onto flask and insert thimble into extractor
and add more solvent to fill the extractor. Complete
assembly by attaching condenser and clamping entire
apparatus in position in heating mantle.
d) Heat the flask sufficiently to produce one discharge cycle
about every ten to fifteen minutes. Extract each sample
for 24 hours. During the first cycle, check the seating
of the ground glass joints by rotating the joints while
pushing the condenser/extractor and extractor/flask together.
Check for solvent loss periodically throughout the extraction
and add solvent as necessary.
e) At the completion of the extraction, allow the extractor to
cool. Remove the condenser. Pull out the thimble allowing
any remaining solvent to drain into the extractor.and siphon
off any solvent in the extractor into the boiling flask.
Remove the extractor.
f) Discard the solvent.
g) Repeat the process with methylene chloride and then with
n-pentane.
h) When the extraction is completed, transfer the silica gel
to either a large shallow pan or a rotary evaporator to dry.
Activate the solvent free silica gel by heating at 110°C for two
hours in a suitable oven. Then cool and store in a desiccator.
7.8.8.4 Column Preparation
1. Plug the outlet of the precleaned column with glass wool.
Dry pack the column with 6.5 grams of freshly activated
silica gel. For freshly activated silica gel, this weight
occupies 9 ml in a 10-ml graduated cylinder. Tap the
column briefly with the microspatula to compact the bed.
7-41
-------
2. Take a 50 ml volume of pentane and pour it through the
column until the bed is homogeneous, free of any cracks,
and free of any air bubbles. Continue pentane flow until
the 50 ml volume is used. The pentane level should be at
the top of the bed.
NEVER ALLOW THE TOP OF THE BED TO GO DRY.
3. Keep the column cool to prevent air bubbles and gel cracks.
Inlet water temperature to the water jacket should be
18-22°C. If water jackets are not available, wrap the
column with acetone moistened towels. (Do not allow any
acetone to drip into sample receivers.)
7.8.8.5 Elution of Sample
1. Position a 25-ml volumetric flask as a receiver under the
column. Transfer the prepared sample onto the column.
Rinse the sample container into the column three times with
1 ml of pentane each time. Begin adding 22 ml of pentane,
and start elution at a flow rate not greater than 1 ml/min.
Collect 22 ml of pentane, adding more to the column if
necessary. Do not allow pentane level to go below the top
of the bed.
2. When 22 ml of pentane are collected, the pentane level is
at the top of the bed. Take 10 ml of Eluent No. 2 in a
graduated cylinder. Use 2 ml to rinse the sample container
into the column. Add the remaining 8 ml of Eluent No. 2
to the column and start eluting. Collect 3 ml more of eluent
in the 25 ml receiver, then stop elution. This is the first
fraction. Label this and succeeding fractions as they are
col 1ected.
3. After the first fraction has been collected, place
a 10 ml volumetric flask under the column as receiver.
Start elution and collect 10 ml of Fraction 2, adding
small amounts of Eluent No. 2, 20$ CH2C12 in pentane,
as necessary, At the end of collection, the solvent
level must be at the top of the bed. This is fraction
No. 2.
4. Replace the receiver with another 10-ml volumetric
flask. Take 10 ml of Eluent No, 3, 50% CH2C12/
pentane in a graduated cylinder. Rinse sample container into
the column with 2 ml of solvent. Start elution and add
remaining solvent. Collect 10 ml of Fraction No. 3, adding
small amounts of the solvent if necessary. Again, at the
end of collection, the solvent level must be at the top of
the bed.
7-42
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5. Repeat step 4 with the remaining eluents:
t CH2C12, 10 ml
• 5% CH3OH/CH2CL2, 10 ml
• 20% CH3OH/CH2C12, 10 ml
• 50% CH3OH/CH2CL2, 10 ml
6. Reserve 1 ml allquots of each fraction for TCO analyses by
transferring 1 ml with a plpet to a liquid scintillation vial
Label these vials with the sample number.
7. In the.area specified for solvent evaporation, quantitatively
transfer sample Fractions 1-7 Into precleaned, tared, and
labeled glass beakers. Final quantitative transfer 1s achieved
by rinsing each sample fraction receiver two times with 2-ml
volumes of methylene chloride.
8. The solvents are allowed to evaporate. When all fractions appear
dry, weigh twice dally until weights stabilize to within +0.002 mg.
9. After final weights are obtained, store the beakers 1n a dlslccator
and return to sample controller.
7.8.9 Calculations
Data collected are:
t Weights of sample when constant weight was achieved.
• Weights of the fractions when constant weights were achieved'.
t Weights of the blank fractions when constant weights were
achieved.
0 Weights of volatile materials 1n the fractions from TCO
analyses.
The weights of the sample fractions are corrected for the weights
of corresponding blank fractions before being transmitted to program manage-
ment. For Internal use, the percentage distribution 1n the fractions will
also be calculated.
7-43
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7.9 LOW RESOLUTION MASS SPECTROMETRIC ANALYSIS
7.9.1 Scope and Application
7.9.1.1 Scope
This procedure is a survey analysis used to determine compound types
in an organic sample or in an LC fraction of a sample. The analyst is
specifically searching for hazardous compounds or compounds which may be
generally considered toxic. Examples are aromatic hydrocarbons and
chlorinated organics. Analysis using different sample ionizing parameters
results in molecular weight data, which, combined with IR and sample source
data, can provide specific compound identifications on a "most probable"
basis.
The mass spectrometer (MS) used in this procedure should have sufficient
sensitivity such that 1 nanogram or less presented to the ionizing chamber
will result in a full spectrum with a signal ratio of 10:1. A dynamic
range of 250,000 or better should be achievable.
7.9.1.2 Detection Limit
The detection limit for a specific compound related to the size of
an air sample or liquid sample will vary widely depending on the types
and quantities of the species in the mixture. This is because of inter-
fering effects in the spectrum caused by multiple compounds. The impact
of this interference may be reduced by lowering the ionization
voltage to produce spectra containing relatively more intense molecular
ions.
7.9.2 Summary of Method
Solid samples are placed in a sample cup or capillary for introduc-
tion via the direct insertion probe. More volatile samples are weighed
into a cuvette for introduction through a batch or liquid Inlet system. The
probe or cuvette is temperature programmed from ambient temperature to
300°C. Periodic MS scans are taken with a 70 eV ionizing voltage as the
sample is volatilized during the program. A lower ionizing voltage range
(10-15eV) may be used at the discretion of the operator if the 70eV data are
complex. Spectra are interpreted using reference compound spectral
7-44
-------
libraries, IR data, and other chemical information available on the sample.
The results of LRMS analysis give qualitative information on compound
types, homologous series and, in some cases, identification of
specific compounds. This information is then used to assess the hazardous
nature of the sample.
7.9.3 Definitions
• LRMS - Low resolution mass spectrometry. Low resolution
means that only unit mass data are typically obtained,
i.e., instrument resolution is sufficient to separate
and identify peaks differing by one atomic mass unit
(AMU).
e LC - Liquid Chromatography
t MS - Mass Spectrometer
0 Molecular ion - The unfragmented ionized molecule. This
ion provides the molecular weight of the molecule when
detected.
• "Most probable" - This term refers to the confidence in
a compound identification based upon all chemical and
spectroscopic information known about the sample.
7.9.4 Sample Handling and Preservation
Samples are usually residues in aluminum dishes or glass beakers, from
which solvents have been removed by evaporation and desiccation. Occasionally,
the residue will be somewhat fluid due to the presence of a rather nonvolatile
liquid. Samples should be stored in a refrigerator when not in use. All
dishes and implements must be carefully washed in warm soapy water, rinsed
several times with water followed by pure organic solvents such as hexane,
acetone, or methylene chloride and finally dried. Contacting the sample
with hands, fingers and other sources of outside contamination must be
avoided.
7.9.5 Apparatus
Finnigan - Model 4023 Automated GC/MS
Several other quadrupole or magnetic sector MS instruments, automated
or manual, can be used to perform this analysis. Minimum requirements are:
• Resolution sufficient to separate nominal mass peaks
from 40 to 1000 AMU
7-45
-------
• A solid inlet system (probe)
• A batch Inlet system for liquid samples. (This can be
the gas chromatograph).
• Variable ionization voltages from 4 eV to at least 70 eV
t Electron multiplier detection system
7.9,6 Reagents
Supplies of the following, pesticide grade, Distilled-in-Glass®,
solvents or their equivalents should be kept in 1 or 2 liter quantities.
These solvents are used to dissolve and homogenize the sample residues
prior to placement in the solid probe capillary. Solvent selection is at
the discretion of the operator and is based on knowledge of the sample
(e.g., which LC fraction, IR data, solubilities, etc.). The solvents are:
• Pentane
• Methylene Chloride
• Methanol
• Petroleum ether
• D1-ethyl ether
7.9.7 Procedure
7.9.7.1 Instrument Preparation
The procedure assumes that the MS has been activated in accordance
with the .instrument instruction manual and has been prepared to gather and
record data. Briefly, summarized this procedure includes:
t Monitoring all applicable pressures and confirming that
proper vacuum levels are being achieved.
• Checking all applicable temperatures and making adjust-
ments as necessary.
• Checking performance of Ionizer.
t Optimizing resolution/sensitivity
• .Confirming that all electronics associated with data
collection are functioning properly.
When all the necessary checks have been performed, proceed with the analysis,
7-46
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7.9.7.2 Analysis of the Sample
1. Place 1 microgram or less of the sample in a solid probe
glass capillary. The sample may be loaded as a solid,
however, it is preferable to dissolve the sample in a
solvent and load it as a solution. Both techniques,
described in steps (a) and (b) below, ensure controlled
evaporation of the sample into the ion source. Avoid
touching or otherwise contaminating the solid probe tip
or the glass capillary. Always wear clean nylon gloves
or equivalent when handling the solid probe tip, and
use forceps to handle the glass capillaries.
a. If the sample is in solution, the solvent must be
evaporated prior to inserting the sample into the
mass spectrometer. Do this by gently heating the
glass capillary under a heat lamp or with an
appliance such as a hair dryer.
b. If the sample is inserted as a solid, it may occa-
sionally blow out of the capillary if it is heated
too quickly. To prevent this, place the sample
at the bottom of the glass capillary and insert a
small quantity of silanized glass wool (pyrex)
over it.
CAUTION: Sample size should be 1 ug or less to minimize
contamination of the ion source.
2. Place the capillary tube into the end of the solid probe
by pushing the retaining spring aside and then releasing
it to hold the capillary tube in place.
3. Insert the solid probe tip into the slip vacuum seal at
the entrance of the solid inlet and push the solid probe
in until the index pin in the guide rod snaps into the
hole in the tube.
4. Tighten the slip vacuum seal by turning the black knob
clockwise.
5. Evacuate the solid inlet and monitor the inlet pressure.
When it has reached 0.04 torr stop the evacuation.
6. Open the solid probe valve by rotating the crank counter-
clockwise.
7. Depress the locking button on the guide rod, and slowly
push in the solid probe to the full length of travel.
8. Connect one end of the solid probe heating cable to the
socket 1n the handle of the probe. Connect the other
end of the cable to the connector labeled Program.
7-47
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9. Prepare the mass spectrometer for acquiring data.
Parameters which must be entered into the MS controller
include:
Solid probe temperature - Program rate to be
determined
Mass range - 40-600
Scan time for mass range — 2 sec
Scan interval - 50°C
Record this data in the instrument log book.
10. Set the temperature program controls for a heating
interval of ambient to 300°C at the temperature increase
rate desired. The rate may be adjusted by the operator
at his discretion to control sample sputtering, etc.
Depress the Solid Probe Selector push button under the
temperature readout to monitor the probe temperature.
11. Start data collection and depress the Solid Probe
pushbutton to start the heating cycle.The probe will
now heat at the selected rate while MS data is acquired,
processed, and stored in the computer.
12. When the probe temperature reaches 300°C, stop data
acquisition by pressing the appropriate computer stops.
Turn the solid probe heater off and allow the probe to
cool. Then disconnect the cable from the probe handle
and pull the probe out to the stop. Close the solid
inlet valve by turning the handle clockwise. Loosen
the slip vacuum seal knob. Push down on the stop pin
in the guide rod, and withdraw the probe. Remove the
capillary and visually estimate if possible, the amount
of sample that has volatilized. Record this estimate
as either 0, 25, 50, 75, or 100 percent volatilized.
7.9.8 Data Interruption
The raw data from an LRMS analysis consist of mass spectra recorded
on oscillograph recorder paper or computer output from a printer plotter.
The data are equivalent and consist of atomic mass units (AMU) on the
bottom of the chart (abscissa) and the relative ion intensity on the sides
(ordinate). Interpretation of a spectrum is accomplished by utilizing
several sources of information. All inputs are considered in making a
determination and in estimating the degree of confidence in the spectral
7-48
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assignments. Assistance with interpreting data is available from several
sources, including the following:
1. The nature of the sample, e.g., water extract, fuel
extract, which of the several liquid chromatography frac-
tions, etc.
2. Results of infrared spectrophotometric analysis on same
sample and other chemical information.
3. Published compilations of MS data for standard compounds.
4. Operator experience and skills using correlations between
molecular structure and mass spectra as well as the
simple ability to recognize spectral features critical
to the identification of compound classes or compound
group types.
No standardized spectral interpretation procedure is believed to be
used by a majority of operators. However, the basic elements of data inter-
pretation are presented below.
.. 1. Study all available information about the sample.
2. Verify that the mass counter is accurate.
3. Study the general appearance of the spectrum, e.g.,
molecular ion intensities, isotopic abundances as an
indication of certain heteroatoms, rings plus double
bonds,based on the molecular ion and characteristic
ions.
4. Identify neutral species accompanying high mass fragment
ion formation.
5. Postulate classes of compounds, and test against refer-
ence spectra for the same or similar compounds. If
these are not available, spectra predicted from 1on
decomposition mechanisms may be used. Examine the data
from analyses run with the low ionization potentials
to check molecular ions.
In the analysis mode where low ionization voltages are used (10-15 eV)
the intensity of the peaks caused by molecular ions of "most probable"
identified compounds can be examined to provide an estimate of the abun-
dances of identified species. Only an estimate can be given because the
production and stability of molecular ions is not equal for all compounds.
This type of estimation is significantly more error prone when 70 eV
7-49
-------
ionization energies are used. The estimation procedure is carried out by
normalizing all of the molecular ion peaks and reporting each species as
a fraction of the total.
7.9.9 Quantisation of Results
The relative quantity of each compound category identified should be
estimated on a scale ranging from 100 (major) to 10 (minor) to 1 (trace).
It should be possible to account for nearly all observed species by using
a relatively small list of compound categories.
7.10 POLYNUCLEAR ORGANIC COMPOUND ANALYSIS BY GAS CHROMATOGRAPHY/MASS
SPECTROMETRY (POM's by GC/MS)
7.10.1 Scope and Application
7.10.1.1 Scope
This is an analysis method for polynuclear organic materials, partic-
ularly the polynuclear aromatic hydrocarbons (PAH) 1n various environmental
samples. Aromatic compounds containing heteroatoms 1n the condensed rings
may also be Included in the scope of this analysis. The manner 1n which
the GC/MS data are gathered and stored will enable the operator to search
for a list of compounds of Interest 1n a routine manner. The 11st of
compounds can be changed as required.
7.10.1.2 Sensitivity
The GC/MS sensitivity varies with several parameters, Including the
type of compound, Instrument Internal cleanliness, resolution of closely
eluting peaks, etc. Under "everyday" operating conditions 5 nanograms (ng)
elutlng 1n a peak about 5 seconds wide will yield a MS signal with a usable
signal-to-no1se ratio. A dynamic range of greater than 100,000 1s achiev-
able.
7.10.1.3 Detection Limit
There will typically have to be at least 10 yg of any single PAH com-
pound extracted from a sample and concentrated to 10 ml of solution for
detection limit of 0.3 vg/m3. This presumes a 2:1 dilution for addition
of the Internal standard, a 10 yl sample Injection volume, the typical
Instrument sensitivity specified above, and the sample preparations described
below.
7-50
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7.10.1.4 Interferences
This analysis 1s performed using the MS In the Total Ion Monitoring
(TIM) mode. In this mode, all 1on fragments 1n a specified mass range are
monitored and as a result, all compounds elutlng from the GC 1n detectable
quantities can be Identified. During the search of the data for POM
compounds, non-POM compounds jnay..Interfere, especially 1f they co-elute
with a POM. Computerized data reduction techniques, such as 1on mapping
and selected 1on chromatograms, keep these Interferences to a minimum. If
a discrete list of POMs exists for which to search, then a spectral library
of these compounds can be stored 1n the computer data bank as standards
against which sample spectra are compared.
7.10.2 Summary of Method
This 1s a combined gas chromatography/mass spectrometry (GC/MS) method
for qualitative and quantitative POM determinations, M1crol1ter quantities
of concentrated sample extracts derived from various samples obtained from
the sampling activity are used for this analysis. The extraction and con-
centration procedures are described 1n Sections 7.3 and 7.4.
Micro!1ter sized (5-10 yl) samples are Injected onto a gas chromato-
graphlc column and are separated by the differences 1n the retention
characteristics between the sample components and the column material. As
the components elute from the GC column, they are transported via an
Interface to the 1on source of the mass spectrometer (MS). The components
are Ionized 1n the MS and the 1on fragments mass analyzed 1n the 40-400
AMU range. The resulting mass spectra are stored by the computerized
data system. The computer 1s used to search the stored spectra for mass
fragments common to the POMs of Interest. Spectra from the GC peaks
suspected to be POMs are examined. If a POM 1s confirmed, the peak 1s
quantltated using an Internal standardization method.
7.10.3 Definitions
GC/MS - gas chromatograph/mass spectrometer
POM - polynuclear organic materials
PAH - polynuclear aromatic hydrocarbons
PCB - polychlorlnated blphenyl compounds
7-51
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AMU - atomic mass unit
IS - internal standard
SIM - selected ion monitoring
TIM - total ion monitoring
7.10.4 Sample Handling and Preservation
These samples are organic solutions resulting from extraction and con-
centration of envirnomental samples. They are contained in capped or
sealed ampoules or vials typically containing 1 to 2 ml. These samples
may contain toxic materials and due care shall be used in handling all
samples and standards. Gloves and fume hoods are appropriate consider-
ations.
7.10.5 Apparatus
This section specifies the major pieces of apparatus required. A
normal complement of glassware and implements is assumed.
7.10.5.1 Automated GC/MS - Finnigan Corporation, Model 4023 or Dupont
Dimaspec, Model 321
Other quadrupole or magnetic sector instruments coupled with appropri-
ate computer data systems are available to perform this analysis. Basic
required capabilities include:
• Resolution sufficient to obtain unit mass peaks in'the
range from 40 to at least 400 AMU
t Capability for 2 mm ID packed columns and a sample enrichment
device to achieve yields and efficiencies such that the 5 ng
total instrument sensitivity is achieved
• Electron multiplier detection system
• Total ion monitoring capability in the 40-400 AMU range
7.10.5.2 Interactive Data System
Capable of gathering and storing TIM data, generating total ion and
selected ion chromatograms, library searching, and quantitation.
7.10.5.3 GC Column
Six foot X 2 mm ID glass column containing 3% Dexsil 300 on 100-120
mesh Gas Ghrom Q, Chromosorb WHP, or equivalent.
7-52
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7.10.5.4 GC Injection Syringes
Ten ul syringes with 0.2 yl graduations.
7.10.5.5 Analytical Balance
Capable of weighing +0.05 mg.
7.10.6 Reagents
7.10.6.1 Solvents
Supplies of the following solvents, Pesticide Grade, Distilled-in-
Glass? or equivalent should be kept at hand in 1 or 2 liter quantities.
These solvents will be used to prepare analytical standards, make dilutions,
do solvent exchange or other similar activities as required.
• Toluene
• Pentane
• Methylene chloride
0 Methanol
• Acetone
• Hexane
7.10.6.2 Standard Compounds
The following compounds are used for retention time and detection limit
determination. This list can be expanded or changed as POMs of interest
are added or deleted.
Compound Molecular Weight
Naphthalene 128
Acenaphthene 159
5,6-Benzoquinilene 179
Dibenzothiophene 184
Fluoranthene 202
Pyrene 202
1,2-Benzanthracene 228
l,2-Benzo[a]pryene 252
1,2,5,6-D1benzanthracene 2?8
Coronene 30°
7-53
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7.10.6.3 Internal Standard for Working Standard Mixtures
Weigh out 0.01 g +0.01 mg of a-chloronaphthalene (making corrections «,
for purity 1f 1t 1s less than 99 percent) and dissolve 1n toluene contained
1n a Class A 100 ml volumetric flask. This yields a 100 yg/ml solution.
7.10.6.4 Internal Standard for Unknown Samples
Take 20 ml of the above stock solution by plpet and transfer to a
100 ml volumetric flask. Fill to the mark with toluene and mix well.
This yields a 20 ug/ml solution.
Note: Different Internal standard stock solution concentrations
are required depending on whether the sample 1s a POM
standard or an unknown sample. Care must be taken to
use the correct stock solution.
7.10.7 Procedure
The GC/MS sample solutions will be prepared 1n such a way that the
solutions will: 1) be concentrated as much as 1t practical and 2) contain
an Internal standard for quantification and checking Instrument response.
The procedures for these preparations are discussed below.
7.10.7.1 Preparation of the Sample Solutions
The 1 ml aliquot of the 10 ml sample resulting from the Kuderna-Danlsh
concentration of the sample extracts should be contained 1n a clean Teflon
capped vial large enough to hold at least 2 ml. Plpet 1.0 ml of the Internal
standard solution (7.10.6.4) Into the vial and shake well to mix. In practice
1t 1s probable that samples will be assigned that do not contain 1 ml. These
solutions can be prepared as received without further allquoting but the
volume of Internal standard solution to be added to the sample must be equal
to the volume of the received sample aliquot.
7.10.7.2 Preparation of POM Standard Solutions
Concentrated stock solutions of the POM compounds of Interest shall be
made. Ten milligrams of a POM in 50 mill inters of toluene produces a
suitable concentration of 200 nanograms per nrlcroHter (ng/yl). Portions
of these stock solutions can be serially diluted or combined with one
another to produce working standard mixtures. The working standard
solutions will be made up 1n 10 ml volumetric flasks. When making the
7-54
-------
working standard mixtures up to 10 ml volume, 1.00 ml of the internal
standard stock solution for working standard mixtures (7.10.6.3) will be
added as part of the diluent. This will yield solutions that always con-
tain 10 ng of internal standard per yl solution. These POM standard
solutions are subjected to the same instrumental analysis given the unknown
samples. Data are collected in the same manner as the unknown samples.
The responses of individual POM compounds relative to the internal
standard are then calculated as shown 1n Section 7.10.8.
The stock solutions described above will be stored in a refrigerator
or preferably a freezer. The volumetric flasks should be wrapped 1n
plastic to minimize exposure to moisture. Storage life times for these
solutions have not been specifically measured but they should remain
stable for 6 months. All working mixtures and standards should also be
stored 1n the refrigerator when not in use and should be protected from
sunlight and fluorescent lighting. These working solutions should be
prepared on a monthly basis.
7.10.7.3 Preparation of the GC/MS Instrument
The gas chromatograph shall be prepared according to the manufac-
turer's operating manual. Key operating parameters to be used are as
follows:
Column - 6 ft. X 2 mm ID glass packed with 3$ Dexsll 300 on
100-120 Chromosorb WHP or 100-120 Gas Chrom Q.
Carrier Gas - Helium, zero grade at 30 ml/m1n.
Oven Temperature - 100° - 295°C programmed at I0°/m1n (the program
may be varied to suit a specific situation).
Injector Temperature - 300°C.
Transfer Lines and Separator - oven 260 *C - 280eC.
The mass spectrometer shall be prepared according to the manufac-
turer's operating manual. Briefly summarized, this procedure Includes:
t Monitoring all applicable pressures and confirming that proper
vacuum levels are being achieved. Proper levels are specified
1n the manual
7-55
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t Checking all applicable temperatures and making adjustments
as necessary:
Ion source block - 200°C
Manifold containing source,
electron multiplier etc. - 40°C to 60°C
0 Checking performance of ionizer
• Optimizing resolution, sensitivity and proper spectral pattern
using a call brant such as FC-43 and/or Ultramark 443
• Confirming that all electronics associated with data collection
are functioning properly.
Important MS parameters to be set are as follows:
Electron energy 70 eV
Ionizing energy 0.2 milHamp
Electron multiplier Adjusted for optimum signal
to noise ratio (1.5 to 2.5 KV)
Sensitivity 10" amps/volt
Analyzer pressure 5 X 10 torr or less
Optimum MS parameters can be varied for different instrument systems.
Record parameters in Instrument log book.
7.10.7.4 Preparation of Computerized Data Acquisition System
Use the Operating Manual for the data system to select the operating
parameters for data collection, storage, and processing time.
Mass range 40 - 400 AMU
Scan function Up 1.9 seconds
Down 0.0 seconds
Hold at top 0.0 seconds
Hold at bottom 0.1 seconds
Ion abundance threshold Set to minimize "random ion" noise
7.10.7.5 Starting the Analysis
When all preparations have been completed, inject the sample into the
gas chromatograph while 1t 1s 1n the solvent divert mode. At a set time
after Injection, adjust the solvent divert valve as as to direct the GC
7-56
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effluent into the MS. Start data acquisition according to the preselected
parameters. The instrument will then gather and store data over the time
interval during which the components of the sample mixture will elute.
Analysis will continue for a pre-set time or until the operator intervenes.
The system shall be programmed to stop the analysis after enough time has
elapsed in order for coronene MW 300 to elute.
7.10.8 Data Processing and POM Quantification
7.10.8.1 Computer Generated Total Ion Chromatogram (TIC)
Direct the data system to reconstruct a total ion chromatogram using the
acquired data. The peak heights on the chromatogram shall be standardized so
that all are relative to the strongest peak which is maximized at 100% of chart.
The purpose of the RGC is to provide the analyst with an overview of the relative
number and concentration of compounds in the sample. An example of such a chrom-
atogram is shown in Figure 7-7.
§.
1.
IL,
t
H.
X.
9.
0 tO -iff
to a v
» its ua ta i»
Figure 7-7
Example of a Computer Generated
Total Ion Chromatogram
7.10.8.2 Processing Sample Data and Search for POHs
This section summarizes the manner in which stored data are searched
for POMs. A reconstructed total ion gas chromatogram is prepared-by the
computer over the 40 - 400 AMU range. Selected ion mass chromatograms are
then prepared using pre-selected m/e values corresponding to the molecular
Ions of many polynuclear aromatic hydrocarbons. A list of these ions is
found in Table 7-2. Table 7-3 is a minimum list of POMs monitored by selected
7-57
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mass chromatograms using the masses 1n Table 7-2. Many more ROMs of similar
molecular weights probably exist and will also be detected. Additional POM
isomers not listed in Table 7-3, also exist and will be detected. A peak
in any of these selected mass chromatograms indicates the potential presence
of p POM and must be investigated further by examining the full mass spectra.
If a spectrum has an intense molecular ion at one of the m/e values listed
in Table 7.2 and if the spectrum is consistent with other POM type compounds,
it is assigned to the POM class of compounds. For example, if the mass
chromatogram for m/e 128 in the specific ion chromatogram displays peaks, the
presence of naphthalene, or azulene, or a similar compound is suspected. The
full mass spectrum is taken from an appropriate portion of the chromatogram
peak. The spectrum is then examined to confirm the identification.
Table 7-2. Specific Ions Used in PAH Data Search
128
154
162
166
178
179
180
184
192
202
216
228
242
252
256
278
300
302
7.10.8.3 The Use and Calculation of Relative Response Factors
Prior to quantification of unknown POMs, it is necessary to determine the
relative response factors of known POMs to the internal standard. To do this,
analyze the standard mixtures prepared 1n 7.10.7.2 with the 6C/MS operating
under the same conditions used for the unknowns. Calculate the Relative
Response Factor (RRF) for each POM in the standard as follows:
(1)
"15 "POM
Where
RRFPOM = Relative response factor for a POM relative to an Internal
ru standard
ApQ» * Total 1on peak area for a POM
AIS • Total 1on peak area for the Internal standard
7-58
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Table 7-3. Minimum List of ROMs Monitored
Compound Name
Naphthalene
Blphenyl
Benzlndene
Fluorene
9,10-D1hydro-phenanthrene
9,10-D1hydro-anthracene
2-Methyl-fluorene
1-Methyl-fluorene
9-Methyl-fluorene
Phenanthrene
Anthracene
Benzoqu1nol1ne
Acr1d1ne
3-Methyl-phenanthrene
2-Methyl-phenanthrene
2-Methyl-anthracene
Fluoranthene
Pyrene
Benzo[a]fluorerie or 1,2-benzofluorene
Benzo[b]fluorene or 2,3-benzofluorene
Benzo[c]fluorene or 3,4-benzofluorene
2-Methyl-f1uoranthene
4-Methyl-pyrene
3-Methyl-pyrene
1-Methyl-pyrene
Benzp[c]phenanthrene
Benzo[gh1]f1uoranthene
Benzo[a]anthracene
Chrysene
Trlphenylene (9,10 Benzo phenanthrene)
4-Methyl-benzo[aJ anthracene
IrMethyl-chrysene
6-Methyl-chrysene
MW
128
154
166
166
180
180
180
180
180
178
178
179
179
192
192
192
202
202
216
216
216
216
216
216
216
228
228
228
228
228
242
242
242
(Continued)
7-59
-------
Table 7-3. (Continued)
Compound Name MW
7,12-Dimethyl-benzo[a]anthracene 256
9,10-Dimethyl-benzo[a]anthracene 256
Benzo[f]fluoranthene 252
Benzo[k]fluoranthene 252
Benzo[b]fluoranthene 252
Benzo[a]pyrene 252
Benzo[e]pyrene 252
Perylene 252
1,2,3,4-Dibenzanthracene 278
2,3,6,7-Dibenzanthracene 278
Benzo[b]chrysene 278
Plcene 278
Benzo[c]tetraphene 256
Benzo[ghi]perylene 302
Coronene 300
1,2,3,4-Dibenzpyrene 302
1,2,4,5-Dibenzpyrene 302
Cnnu = Concentration of the POM in the standard mixture.
POM
CIS = Concentration of the internal standard in the standard
mixture
7.10.8.4 Quantifying POM Peaks in Sample
Calculate the quantity of each POM in the mass chromatogram as
follows:
CD™ * APOM x CTC x _J X Vfinal (2)
POM -T IS "KWp Tl V '
MIS K POM vas received
7-60
-------
Where
= Concentration (yg/ml) of the POM in the GC/MS prepared
sample diluted with IS solution.
= Area of unknown peak.
AIS = Area of internal standard peak.
CIS = Concentration (yg/ml) of internal standard in the sample
solution.
RRFDAM = Relative response factor of the POM as calculated from
POM Equation 1.
V,. •, = Volume of sample (ml) after addition of internal standard
f1nal solution.
Vas received = Volume of sample as received.. (Normally an aliquot
of the 10 ml total sample after Kuderna-Danish
concentration).
7.10.8.5 Automated GC/MS Data Reduction and Quantification
Most of the computer software supplied with state-of-the-art com-
puterized GC/MS systems have automated quantification routines which
utilize the internal standardization and the quantification techniques
described above. The application of these techniques to routine POM
analysis is recommended for qualitative and quantitative accuracy as well
as reduced labor requirements.
7-61
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8.0 INORGANIC ANALYSIS PROCEDURES
8.1 INTRODUCTION
Level 1 inorganic analyses will consist of a Spark Source Mass
Spectrometric (SSMS) elemental survey along with specific analyses for mer-
cury and sulfate on all samples, ultimate analysis on fuel oil samples, and
ultimate and proximate analyses on all coal samples. Additional analyses
for arsenic and antimony will be performed on the APS impinger samples.
Fluoride and chloride analyses will also be performed on selected Level 1
sites as directed by the Laboratory Operations Manager. The plan for sam-
ple preparation and analysis, as shown in Figure 8-1 and 8-2, includes all
possible sample types and procedures. However, all of these samples may
not exist for a site, or as a result of applying the decision criteria in
Chapter 3, not all analyses will always be performed.
The plan given in Figure 8-1 is applicable to all analyses done before
June 1978 and that in Figure 8-2 is applicable after this date. The
changes incorporated into Figure 8-2 are the result of either EPA mandated
Level 1 changes or directed changes by the project officer based on TRW
recommendation. Th'ese latter changes are based on initial results of the
program and were made to effect cost savings without affecting the quality
of the technical output of the program. These changes include:
• Performing all As, Sb, Cl, and F analysis by SSMS where possible.
t Deleting all elemental analysis on all gas fired sites.
• Using fuel analysis to compute elemental emissions 1n all oil
and residual oil fired sites.
t Performing ultimate analyses on fuel oils and ultimate and
proximate analyses on all coal.
• Replacing the Parr bomb combustion procedure for XAD-2 resin
with an acid extraction procedure. (This procedure is pending)
8-1
-------
SAMPIf
APPOmONATlON
SECTIONS
1 INORGANIC
ANALYSIS
• — —
LIQUID
SAMPIES
MJUC
UQUDS
T
ICONDENSATE
AND HN03 MNSE
HjC,
IMPINGER
APS
IMP1NGER
oo
i
ro
AQUEOUS
ORGANIC
PARR BOMB
COMMJSHON
SECTION 8.2.1.2
SOj
SECTION 8.2.1.3
HB. SECTION 8.3.2
As, SECTION S.3.3
Sb, SECT! ON 8.3.4
SSMS, SECTI ON 8.3.1
Hg. SECTION 8.3.2
At. SECTION 8.3.3
Sb, SECTION 8.X4
SO4, SECTION 8.4.1
AQUA REGIA
EXTRACTION
SECTION 8.2.1.1
PARR BOMB
COMBUSTION
SECTION 8. 2.1.2
SSMS
SECTI ON 8.3.1
AQUA REGIA
EXTRACTION
SECTI ON 8.2.1.1
Hg,
A*
Sb.
so4.
SECTI ON 8. 3.2
SECTI ON 8.3.3
SECTION 8.3.4
SECTI ON 8. 4.1
Figure 8-1. Level 1 Inorganic Analysis Plan (Prior to June 1978)
-------
SAMHf
AmonunoN
SECTION)
00
CO
CT~[
&.
XAO-1MOOUU
KS.*10!
INCMQANC
ANALVHS
auo
IMfU
1
. 1
H,P
wn
I
i
NOB
AK
uvu
,
jqas
*
XA
•3
D-2
IN
1
m
iti
i
souo
SAMIUS
,,
—
J
J
FU
cc
u>
a
ELS
ML
D
L
I 1
AO4MKGIA
EXTMCHON
HCKIMATC
AND
ULTIMATE
ANALYSIS
Figure 8-2. Level 1 Inorganic Analysis Plan (After June 1978)
-------
• Combining all samples after the filter into a single sample.
This includes the condensate, XAD-2 module rinse, ^2 impinger,
and XAD-2 resin acid extract into a single sample for SSMS ana-
lysis. (This procedure is pending).
• Elimination of the nitrate analysis because of the lack of any
definitive interest by EPA.
• The application of a set of decision criteria based on results
of fuel and XAD-2 module composite analyses in order to eliminate
unnecessary Hg, As, and Sb analyses.
A discussion of these changes and the rationale that goes into these
applications is given in Chapter 3.
Samples for laboratory analysis will be either liquid or solid. Aque-
ous liquids require only minor preparation which is described in each ana-
lytical procedure. Organic materials, both liquid and solid, must be com-
busted in a Parr oxygen bomb to destroy the organic matrix. An alternative
procedure to Parr Bomb combustion for preparation of XAD-2 resin for ana-
lysis is included. Approval of this procedure is pending, therefore its
use is not yet authorized. Solids that are primarily inorganic (with the
exception of glass fiber particulate filters) can be analyzed directly by
SSMS, but must be digested with aqua regia for the individual analyses.
Particulate filters generally are acid digested for SSMS analysis because
of the cohesion and sparking problems that are associated with having glass
fibers in the graphite electrodes. It is still preferable, however, to run
all particulate samples for SSMS neat, and this will be done whenever pos-
sible. Samples for chloride analysis will be prepared by extraction with
hot water. When available, these hot water extract solutions will also be
the preferred sample for sulfate analysis. Mercury is analyzed by the cold
vapor technique, and both arsenic and antimony are determined by hydride
generation and AAS detection. The sulfate determination is a- turbidimetric
procedure, and specific ion electrodes are used to analyze both chloride
and fluoride.
In addition to the information generated by the Level 1 procedures,
the EPA has additional specific needs for data on the amount of ^$04 (S03)
emissions on many of the combustion sources that will be studied. For this
reason, a series of procedures for the analysis of samples from the con-
trolled condensation system (CCS) for the collection of F^SCty aerosols are
included.
8-4
-------
8.2 SAMPLE PREPARATION
The following procedures will be used to prepare all Level 1 samples
for inorganic analyses. The procedures apply to-sol id and organic liquid
materials since aqueous liquids do not require any preparation. Parr bomb
combustion is used to prepare organic solids and liquids (i.e., XAD-2 resin,
coal and fuel oil) for SSMS, Hg, 804, F, and Cl analyses. Aqua regia
digestions are used to dissolve solid samples such as particulates, fly
ash, bottom ash, etc. for Hg, $04, and F analyses. Whenever possible, SSMS
will be performed on neat solid samples. However, particulate catches on
glass fiber filters will generally be embedded in the pores of the filter
and will require an aqua regia digestion for the SSMS analysis as well.
Hot water extractions are used to dissolve Cl in solid samples, since this
anion can not be analyzed in aqua regia solutions. Hot water extract solu-
tions are also preferred the SCty analysis.
An Improved procedure pending EPA approval for extracting Inorganic
species from XAD-2 resin with acid is given in Section 8.2.3. Reference
to this procedure is shown in dotted lines on Figure 8-2.
8.2.1 Parr Bomb Combustion
8.2.1.1 Scope and Application
Parr oxygen combustion is applicable for the preparation of all com-
bustible materials for inorganic analysis. For Level 1 samples, the mate-
rials to be combusted are fuel oil, coal, and XAD-2 resin. Significant
background quantities of Cr, Fe, Ni, and Mn can be encountered as a result
of attack on and leaching of the stainless steel bomb components during
combustion. To eliminate this background, samples for SSMS analysis are
combusted by a more rigorous method using platinum electrodes and a quartz
cup and lid to line the bomb.
8.2.1.2 Apparatus
• Parr oxygen bomb - 342 ml capacity, equipped with platinum
electrodes
• Oxygen supply and regulator
• Parr pellet press and die
• Vycor sample cups
8-5
-------
• Platinum firing wire
• Glass beakers, 250 ml and 100 ml
• Natch glasses
• Whatman filters, #41
• Nalgene volumetric flasks, 100 ml
• Nalgene funnels
• Quartz cup and lid
• Mortar and pestle, ceramic
8.2.1.3 Reagents
• 4 percent collodion in amyl acetate or equivalent
• 1:1 HN03, H20
• Benzoic acid
8.2.1.4 Sample Preparation
Three types of samples will be run: fuel oil, coal and XAD-2 resin.
No sample preparation is necessary for fuel oil samples; however, the other
two sample types will require steps to ensure complete combustion.
a Coal - Weigh 1 g coal into Vycor sample cup, add 0.25 g
benzoic acid and mix. Transfer contents to pellet die and
press coal sample into pellet.
• XAD-2 Resin - Weigh 1 g of resin into Vycor sample cup. Add
~3 ml of collodion solution, mix and flatten the sample into
a cake. Place sample in oven at 110°C for -20 minutes.
8.2.1.5 Combustion Procedure
a For SSMS Analysis Samples
Place 1 ml of 1:1 HN03 in quartz cup and place in Parr bomb.
Place Vycor cup with sample in Pt holder and attach platinum
firing wire being certain contact is made with sample. The
quartz cup and lid fit the bomb snugly. Care must be taken
when placing the quartz lid down onto the cup to assure that
the quartz lid forms a seal with the cup. Assemble the bomb
and pressurize to 30 atm with 03. Insert bomb in calorimeter,
attach electrical leads and ignite. Allow to cool for ~15 min-
utes and slowly release the pressure. Disassemble bomb and
8-6
-------
wash bottom of quartz lid and contents of Vycor cup into quartz
cup. Remove the quartz cup and wash the contents into a
Nalgene bottle and make up to -50 ml. Label the sample and
turn it in to the Sample Bank Manager.
• For Other Samples (not sensitive to Parr Bomb contamination)
Place 1 ml of 1:1 HN03 in bottom of Parr bomb. Place sample cup
in holder and attach platinum firing wire, being certain contact
is made with sample. Assemble bomb and pressurize to 30 atm with
02. Insert bomb in calorimeter, attach electrical leads and
ignite.
Allow to cool for ^15 minutes and slowly relieve pressure.
Disassemble bomb and wash contents into 250 ml beaker, cover with
a watch glass and digest on hot plate for 30 minutes; do not allow
to boil. Cool and filter through a number 41 Whatman filter, sup-
ported in a Nalgene funnel, into a 100 ml Nalgene volumetric.
Dilute to volume, label, and turn in to Sample Bank Manager.
8.2.2 Aqua Regia Digestion
8.2.2.1 Scope and Application
Aqua regia digestion is used for the preparation of loose particulate,
particulate collected on glass fiber filters, and bulk solids (e.g., fly
ash and bottom ash) for inorganic analysis. This method is appropriate
for species, such as Hg, As, Sb, $04, and F, which are soluble in aqua
regia.
8.2.2.2 Apparatus
t Distillation flasks, flat-bottom, 200 ml
• Condenser, Liebig or Allihn type
• Hot plate
t Volumetrics, Nalgene, 100 ml
• Filter funnels, Nalgene
• Filter paper, Whatman number 41
8.2.2.3 Reagents
Constant boiling aqua regia - 4 parts cone. HN03 + I part cone. HC1,
mix fresh daily.
8-7
-------
8.2.2.4 Procedure
The weighed sample aliquot is placed in the distillation flask. Sixty
ml of constant boiling aqua regia solution are added, the condenser attached,
and the apparatus secured over a hot plate. The acid is refluxed for
^6 hours at which time the apparatus is removed from the hot plate and
allowed to cool. Rinse the contents of the condenser into the distillation
flask using 10 ml of deionized water and disconnect the condenser. Filter
the contents of the distillation flask through a through a Whatman 41 filter
supported by a Nalgene funnel. Collect the filtrate in a Nalgene volumetric
and wash the filter with two-10 ml volumes of deionized water. Make the
volumetrics to volume, label, and turn the digested samples In to the Sample
Bank Manager.
8.2.3 XAD-2 Resin Acid Extraction
8.2.3.1 Scope and Application
The following procecure was developed to replace the Parr Bomb proce-
dure currently used for inorganic analysis of XAD-2 resin. All equipment
cleanup procedures, sample disbursement activities, and sample proportioning
methodologies are listed. Implementation of this procedure is pending.
8.2.3.2 Apparatus
• Condenser - Pyrex, any type with J 34/45 bottom fitting
t Extraction tube, Soxhlet, Pyrex, top joint T 34/45, bottom joint
T 24/40,
• Extraction thimble, Pyrex, with fritted disc, pore size: 40 microns,
diameter: 25 mm., height: 85 mm.
• Heating tape — grounded, minimum 6' length
• Asbestos — Cloth tape or sheet minimum 100 square Inches
• Jars, amber glass 50 ml., 11ds with Teflon liners
t Glass wool, Pyrex
0 Flask, round bottom, Pyrex, ml. with T 24/40 joint
• Stirring rod, glass diameter: 3/16", length: 10"
• Variac transformer, 117 VAC.
8-8
-------
8.2.3.3 Reagents
• Aqua regia - constant boiling - 80% nitric acid plus 20%
hydrochloric acid
• Deionized water
t Acetone — reagent grade
• Methylene chloride, Distilled-in-Glass
8.2.3.4 Equipment Cleanup Procedures
Before any activity is undertaken, the following equipment procedure
is necessary for all glass apparatus.
1. Wash and soak for 2 hours all glassware in aqua regia.
2. Rinse equipment thoroughly at least six times. Extreme caution
and care must be taken to ensure the glass frit in the thimble
is thoroughly rinsed.
3. Rinse all equipment once in acetone.
4. Rinse all equipment twice in methylene chloride.
5. Thoroughly dry all equipment.
6. NOTE: Glass wool should also be acid cleaned, solvent rinsed,
and dried.
8.2.3.5 Procedure
1. Equipment Setup
a. Place XAD-2 resin inorganic aliquot in thimble with tightly-
packed glass wool on top of the resin in the thimble. This
will prevent the resin from floating. Place thimble in the
extraction tube.
b. Place 100 ml. of aqua regia in the round bottom flask.
c. Assemble the condenser, extraction tube, and flask. Do not
use any stopcock grease.
d. Place assembly on top of a hot plate (if self-standing flask)
or use round bottom flask heating mantle. Use appropriate
clamps for support.
e. Carefully wrap the heating tape around the Soxhlet extraction
tube section which transmits the heated vapors from the round
bottom flask to the condenser. Do not wrap the entire Soxhlet
extraction tube assembly with the heating tape.
8-9
-------
f. Carefully wrap the entire Soxhlet extraction tube with
asbestos tape or cloth. Keep in place with heat resistant
tape.
g. Plug the heating tape into the Variac.
2. Extraction Procedure
It is mandatory that the extraction must begin 6 hours before the
end of the working day.
a. Turn on the hot plate or heating mantle and adjust the heat
until the aqua regia is boiling vigorously.
b. Turn on the heating tape and adjust the heat until aqua regia
vapors reach the condenser. At least two turnovers per hour
should be achieved.
c. Carefully observe the extraction over the next 6 hours. If
the total acid level noticeably drops (33 percent or more),
add more aqua regia and check for leaks. Since the Soxhlet
will be running overnight, no more than 25 percent of the acid
can be lost over a period of 6 hours. There must be at least
25 ml of aqua regia in the round bottom flask at all times.
d. After ensuring all glass joints and seals are properly secured,
allow the apparatus to run over night. The entire extraction
should run for at least 18 hours.
e. Before disconnecting the system, allow the aqua regia to accu-
mulate in the thimble. Just before the liquid starts to
siphon back into the round bottom flask, turn off the heating
tape and remove the asbestos cloth. Turn off the hot plate
or heating mantle.
f. If the aqua regia siphons into the round bottom flask as the
system is cooling, turn on the heat again and allow liquid to
accumulate in the thimble. Repeat step (e) above.
g. If there is 30 ml or less of aqua regia remaining in the entire
extraction system, turn off all heat and allow the system to
cool.
h. After the system cools, save the aqua regia in the round bottom
flask for inorganic analyses. Store the aqua regia in an acid
cleaned plastic bottle (Nalgene, high density linear
polyethylene).
8-10
-------
8.2.4 Condensate, XAD-2 Module Hash, XAD-2 Resin Extract, and H202 Impinger
Composite (Pending)
In order to make a single sample from the four discrete samples that
may contain inorganic material passing the filter, a proportional composite
is made based on the fraction of XAD-2 resin extracted. For example, if
15 percent of the XAD-2 is extracted, 15 percent of each of the other samples
is taken and composited with the acid extract samples. Blanks should be
determined on the original components and applied to the sample using the
appropriate correction factors. In this way, one set of blanks can be
used for several sites using the same reagent lots.
8.3 SPARK SOURCE MASS SPECTROGRAPHIC ANALYSIS
8.3.1 Scope and Application
Spark Source Mass Spectrography (SSMS) is used to perform a semi-
quantitative elemental survey analysis on all types of Level 1 samples.
The procedures described here refer specifically to use of JEOL Analytical
Instruments Inc., Model JMS-01BM-2 Mass Spectrograph, but they are also
applicable in principle to any other type of spark source instrument. The
JMS-01BM-2 is a high resolution, double focusing mass spectrometer with
Mattauch-Herzog ion optics and ion sensitive photoplate detection. The
instrument is specially designed to carry out high sensitivity trace ele-
ment analysis of metals, powders, or semiconductor type materials using an
RF spark ion source.
8.3.2 Summary of Method
Elemental analysis by SSMS involves the incorporation of a sample ali-
quot into two conducting electrodes which are decomposed and subsequently
analyzed by a mass determination using a double focusing mass spectrometer.
Decomposition of the sample electrodes is accomplished by the application
of a radio frequency (~1 MHz) potential of about 4 kV. This induces an
electrical discharge in the form of a spark plasma. Because of the high
energy associated with the discharge, the spark plasma created is composed
primarily of elemental species. The positively charged ions contained in
the plasma are accelerated and formed into an ion beam by a high potential
electric field (
-------
Spark Source Mass Spectrography can be used to detect elemental species
contained in the sample electrodes at levels down to 10~9 grams. Although
the sensitivity varies somewhat, depending on the element of interest and
the sample type, practically all elements in the periodic table can be
detected. Using photoplate detection, all elements having masses in the
range 6 to 240 can be detected simultaneously. Concentration data are
derived from the intensities (optical density) of the mass spectral lines.
There are several methods for determining concentration data from photoplate
spectral line densities. The methods vary widely in terms of their com-
plexity and corresponding precision and accuracy of the results. The
photoplate interpretation procedures followed for this program and for
Level 1 survey work in general are designed to yield concentration data
accurate to within a factor of 2 for some 70 elements. A further discussion
of precision and accuracy of the technique is given later in this section.
The procedures described here address three major aspects of the ana-
lysis: operation of the instrument, electrode preparation, and interpre-
tation of spectral plates. The highlights of each of these activities are
described below, with more detail provided in subsequent sections of the
manual.
8.3.2.1 Operation of the Instrument
The instrument can be operated conveniently by one person for limited
numbers of samples. For analyzing large numbers of samples it is more
efficient to use two operators - one to generate the mass spectra and one
to analyze the spectral plates. In operating the instrument, the electrode
samples are first mounted in the ion source, and the photoplates are mounted
in the detection chamber. The system is then evacuated and readied for the
generation of mass spectra. Evacuation to typical operating pressures
(10~8 torr) usually takes 10 to 30 minutes assuming the analyzer and mag-
netic field sections are maintained in a tiigh vacuum state. The data are
acquired by photographing many spectra in successive stages on a single
photoplate while the amount of exposure is changed sequentially. A single
photoplate can accommodate 16 exposures. The amount of exposure refers to
the number of ions deposited on the photoplate in terms of the total ion
charge reaching the photoplate. For higher sensitivities, correspondingly
longer exposure times are required. For example, 2 to 3 hours (including
8-12
-------
the pumpdown time) is usually required to detect elements at 1 ppb levels
whereas detection at the 3 ppm level usually requires about 1 hour (including
the pumpdown time).
The extent of exposure is determined by measuring the total ion charge
entering the detection region on a coulomb meter. Typically an exposure
range of 10~7 to 10"13 coulombs is used. Once the spectra have been
acquired, the system is vented, and the spectral plates are removed for
development and subsequent analysis. The sample electrodes are removed and
the ion source prepared for another analysis.
8.3.2.2 Electrode Preparation
In spark source mass spectrometry, conducting materials such as metals
are simple pressed or shaped into the desired electrodes. The electrodes
are usually cylindrical or rectangularly shaped and are typically 2 x 2 x
15-mm. Nonconducting materials must be ground to a fine powder, mixed with
a conducting material (e.g., graphite), and pressed into the desired elec-
trode shape. Electrodes are usually formed with a hydraulic press system.
Sample homogeneity is especially important, and care must be taken to
ensure the sample and the electrode material are well mixed. In preparing
electrodes, there are five major features to be considered:1 (1) the elec-
trodes must be electrically conducting, (2) the physical strength must be
sufficient to tolerate being clamped into the electrode holders, (3) there
must be minimum interference from the mass spectrum of the support material,
(4) any materials in the support material must be present at low and known
concentrations, and (5) for quantitative analysis, the contribution of the
support material (and the sample) to the spark and therefore to the total
1on current should be constant and consistent.. Spectral grade graphite
generally meets all of the above requirements as a support matrix for elec-
trode preparation.
8.3.2.3 Plate Reading
In reading the spectral plates, one must first identify the various
masses and then establish the relative intensities of the various peaks.
Identifying the mass peaks is relatively straightforward; a mass scale 1s
developed using various elements which are known to be present, as well as
isotopes and multiply charged ions of these same elements as marker ions.
The known elements are introduced into the mass spectrometer in the form
8-13
-------
of a standard mixture which is sparked under the same conditions as the
sample will be run. Once the reference spectrum has been analyzed, a mass
scale is developed and marked at convenient mass intervals, usually 5 to
10 atomic mass units. The unknown spectrum is then compared with the
reference sample in order to identify the components present.
Establishing the intensities of the various lines is less straight-
forward. Quantitative intensity data are best obtained with microdensito-
meters which measure photographic darkening in terms of percent transmittance.
Transmittance data are then converted to units of intensity or ion density,
which are proportional to the number of ions that cause the darkening. This
conversion can be performed in a number of ways: manually, using digital
or analog computers^; with experimental calibration data^» 10» H; or
with theoretical relationships,^ which include some experimentally deter-
mined parameters. All of the above techniques suffer to a large degree
from at least one of the following: inflexibility, imprecision, insuffi-
cient allowance for corrections, large time requirements, and high cost.
The simplest method for evaluating spectra is done manually and is usually
referred to as the disappearing line technique. Here, the aim is to deter-
mine the ratio of the minimum exposures (in coulombs) at which the low
level impurity element and a major element in the electrode matrix or an
internal standard (spike) are just detectable on the photoplate. To per-
form the analysis, a series of spectra are taken using the total beam
monitor to control the exposure. After the series of spectra are recorded,
the exposures at which the impurity line and matrix line "disappear" are
determined visually by examining the spectra under magnification (or magni-
fied projection). The exposure ratio thus determined may then be used to
obtain concentration data as described in detail later in this section.
8.3.3 The Apparatus
The JMS-01BM-2 is a high resolution, double focusing mass spectrometer
with Mattauch-Herzog ion optics. The instrument is specially designed to
carry out high sensitivity trace element analysis of metals, semiconductors
and miscellaneous powders with the aid of an RF spark ion source and photo-
plate detection. The instrument may also be fitted with an electrical
detection system which can be used as desired. The instrument has a
resolution (M/AM) of 10.000 using photoplate detection and can detect ele-
8-14
-------
ments as low as 10"9 atomic fraction. All elements are detected simulta-
neously with a single exposure covering a mass range of mass ratio 1:36
(e.g., Li to U in a single exposure). The instrument maintains a very
high vacuum; typically, pressures on the order of 10~8 torr are necessary
for adequate performance. Brief descriptions of the major components and
the operating parameters used for this program are given below.
• Ion Source - An RF spark ion source is used. The sample (in the
form of rod electrodes) is placed in a pair of sample holders.
A radio frequency high voltage is then applied to the sample.
The ion source parameters used for all analyses are as follows:
- RF pulse oscillator:
Oscillating frequency: approx. 1 MHz
Anode potential: approx. 4 kV
Pulse width: 20 or 40 ysec
Pulse repetition frequency: 300 or 100 Hz
-Accelerating voltage power supply unit:
Accelerating Voltage: approx. 27.8 kV
The source is fitted with a cryosorption pumping attachment that
absorbs residual gases in the source region which increases the
vacuum and reduces background spectra. It is also equipped with
a sample cooling unit which can be used to maintain a sample tem-
perature of 77°K (using liquid nitrogen). This permits the
effective analysis of low melting point materials, as well as
further increasing the degree of vacuum.
• Automatic Spark Gap Controller - The JMS-01BM-2 is equipped with
an automatic spark gap controller which considerably enhances the
reproducibility of the analysis. This unit continuously monitors
the electrode gap potential and, via a servo-mechanism, maintains
a constant spark gap and uniform sparking conditions. For the
present program, all analyses are carried out with an electrode
gap of 180 urn.
• Monitors — The ion beam current is monitored by an ammeter with
full-scale outputs in the range 1 y-amp to 30 pi co-amps selectable
in twelve increments.. The total ion charge reaching the photo-
plate is monitored by a vibrating reed electrometer and is used
to control the photoplate exposure. The electrometer can auto-
matically control total ion exposures in the range 1000 y-coulombs
to 1 pi co-coulomb.
8-15
-------
Detector - The JMS-01BM-2 can be equipped with either electrical
or ion sensitive photoplates detection. For this program, the
Ilford Q2 (15 x 2 x 0.040 inch) ion sensitive photoplate is used
for spectral data collection.
Synchronous Passer - A Synchronous Passer is placed between the
ion source and the electrostatic analyzer to control the ion beam
so that mass spectra with differing exposures (from long to short
exposure times) are photographed under constant sparking conditions.
The pulse applied to the deflection gate is synchronized with the
spark pulse from the ion source, thus improving the accuracy of
quantitative determinations. The specifications of the synchronous
passer are as follows:
Pulse width: 60 ysec
Pulse repetition frequency: 1, 3, 10, 30, 100, 300,
Ik, 3k, 10 kHz
Voltage: DC 400V
Electrostatic Field Unit -A spherical lens with the following
specifications is Incorporated to Improve the ion current density
and sensitivity:
Rotation angle (e): 30°
Mean radius (re): 200 mm
Voltage: approx. 2.8 kV
Stability: 40 ppm/40 min
Magnetic Field Unit - The magnetic field unit parameters are listed
below:
Rotation angle Um): 90°
Mean radius (rm)
Photoplate detection: max 315 mm
min 52 mm
Field current supply: 4.0 amps (approx. 7,500 gauss)
Field current stability: 2 x 10~5 amps/40 min
8-16
-------
• Vacuum System — The vacuum system is comprised of the following
elements:
Rotary Pumps: 150
80 A/min
Oil diffusion pumps: 6 inches
(with liquid nitrogen 4 inches
cold traps) 2.5 inches
Ion getter pump: 160 Jl/sec
The ultimate degrees of vacuum (and the vacuum required for sample
analysis) for the system components are:
Ion Source: 2 x 10"8 (5 x 10"7) torr
-9 8
Electrostatic Field: 5 x 10 (3 x 10 ) torr
Magnetic Field: 1 x 10~8 (1 x 10"7) torr
8.3.4 Reagents
• Graphite - High purity, spectrographic grade graphite is needed
for preparation of electrodes, e.g., ultrasuperior purity gra-
phite powder, Ultra- 1-N-USP, from Ultracarbon Corp., Bay City,
Michigan or National Spectrographic Grade SP-1 from Union Carbide
Corp., New York, N.Y.
• Spex Mix Standard Mixtures - For routine calibrations, standard
mixtures of elements are required. These are conveniently pro-
vided in: Spex Mix - a mixture of 40 elements as salts or oxides
in which each element is present at 1.27 percent by weight; Spex
Rare Earth Mix - a mixture of 16 rare earth elements at concen-
trations of 5.28 percent each; Spex Noble Metal Mix - a mixture
of 10 noble metals at concentrations of 9.32 percent each (Spex
Industries, Inc., Metuchen, New Jersey). Individual elements in
a variety of compound forms at very high purity (4-9's to 6-9's)
may also be obtained from Spex Industries.
• National Bureau of Standards, Standard Reference Material - As
primary standards, the following NBS standard reference materials
(SRM) are required: SRM 1632 trace elements in coal, SRM 1633
trace elements in coal fly ash, and SRM 1634 trace elements in oil.
• Internal Standard - All samples analyzed will be "spiked" with
Indium. The internal standard will be added as a solution pre-
pared from high purity InNOa, deionized-distilled water, and
Ultrex HNOa as required.
• Photoplates - Ilford Q2 ion sensitive photoplates are used for
obtaining spectra .
8-17
-------
• Developer - Ilford ID-13 developer is used for developing plates.
0 Ethanol - High Purity (Gold Seal) ethanol is used as wetting
agent to facilitate electrode preparation.
8.3.5 Procedures
The Individual procedures to be followed in performing SSMS analysis
are described below. In general, the details of instrument operation have
been omitted; the manufacture's instruction manual should be consulted for
these details. Quality Control functions peculiar to the SSMS analysis are
indicated where appropriate.
8.3.5.1 Electrode Preparation
Sample aliquots for SSMS electrode preparation are obtained from the
Sample Bank either as prepared liquids or as neat solids.
Solid samples must be of a particle size fine enough to pass through
a 100-mesh sieve (a powder the consistency of flour). If solid samples of
large particle size are received, they must be ground with an agate mortar
and pestle before an aliquot is removed for electrode preparation. The
optimum aliquot size for solid samples is 50-150 mg. While somewhat smaller
samples can be effectively analyzed, samples sizes of less than 10 mg should
not be used.
For liquid samples, the volume used for electrode preparation should
be that which produces the desired detection limits. As for solid samples,
the resulting solids content of the electrode set should not exceed ISO-
ZOO mg. Preparing electrodes with the desired properties from liquid
samples may be predicted from knowledge of the sample type and/or deter-
mined by trial and error, Generally, when preparing impinger-composite or
water samples, 20 ml of solution is sufficient. For extract and Parr-
bombed aliquots, the initial amount of sample prepared should be taken into
consideration prior to electrode preparation.
The steps necessary for adequate electrode preparation for both solid
and liquid samples are detailed below. l
• Solid Samples
1) Accurately weigh the sample aliquot and transfer to a Vycor
evaporating dish.
8-18
-------
2) Wet the sample aliquot with about 1 ml of DDI water, add the
appropriate amount of graphite (the graphite added should
yield a total solids weight of approximately 250 mg which is
sufficient to prepare a set of 3 electrodes), the internal
standard (usually ^10 yg of In), and 3 drops of Gold Seal
Ethanol.
3) Slurry the electrode mixture with a Nylon rod, place under an
IR lamp, and heat to near dryness. Before the mixture is com-
pletely dry, extinguish the lamp and allow to cool. (The
remaining liquid will evaporate from the heat of the dish.)
Repeat the slurrying process with 1 ml of water and 3 drops
of ethanol at least 3 times.
4) Transfer the electrode mixture to an agate mixing vial and
further homogenize the sample by mixing in a mixer mill (Spex
Industries) for 30 minutes.
5) Pack the electrode mixture into a polyethylene electrode slug
with a Teflon funnel and Nylon rod. Place the slug in a suit-
able metal die, and apply 12 tons/in2 of pressure for 30 seconds,
6) Allow the die to stand for 15 minutes and remove the slug.
The electrodes may be stored in the slug until analysis.
• Liquid Samples
1) Pipette the appropriate volume of liquid into a Vycor evapora-
ting dish and pre-concentrate to a few ml under an IR lamp.
Wash down the sides of the dish with about 2 ml of DDI water.
2) Spike the concentrate with the internal standard (as above),
add an appropriate amount of graphite, and 3 drops of ethanol.
3) Continue the electrode preparation from step a.3 above.
8.3.5.2 Spectral Data Collection
Prior to data collection, the instrument should be prepared for analysis
(consult the Manufacturer's Instruction Manual as necessary) by setting the
instrumental parameters and evacuating the various system components to the
values specified in Section 8.3.3. In addition, the ion sensitive photo-
plates should be pre-evacuated under diffusion pumping for at least 6 hours
before being placed in the detection chamber. They should be allowed to
condition for at least 30 minutes in the detection chamber before spectra
are accumulated. The following list enumerates the discrete operations
associated with spectral data collection.
8-19
-------
1) Secure the sample electrodes in the tantulum holders so that about
5 mm of the electrodes protrude, and mount on the source flange
(the electrodes should be handled with clean stainless steel for-
ceps, and care should be taken to prevent contamination from over-
handling). Adjust the electrodes in the X-, Y-, and Z- directions
for a horizontal electrode - gap to accelerating slit distance of
5-6 mm. Restore the source flange in its housing and evacuate to
^ 10"7 torr.
2) Apply the anode potential and accelerating voltages and spark the
electrodes. If transmission is not up to specification, refer to
alignment procedures.
3) Pre-spark the electrodes in order to remove any loose particles and
possible surface contamination. The pre-sparking period should be
sufficient to collect about 50 nC of charge. After loose particles
are removed and the electrodes are out-gased, a source pressure
less than 5 x 10"7 should be obtainable. If proper source vacuum
is not achieved, activate the source and sample cryopumping units
as necessary.
4) Adjust the inter-electrode distance (gap) while monitoring the
automatic spark gap controller. First, short the electrodes and
zero the controller. Second, separate the electrodes (cease spark-
ing) and adjust the controller gain to 15 volts. Finally, close
the gap until the gap voltage drop is 7.5 volts; for graphite elec-
trodes this corresponds to a gap width of 180 ym. Place the con-
troller unit in automatic operation for the duration of the data
collection phase. If subsequent tuning of the instrument becomes
necessary, repeat the above steps and establish stable sparking
conditions before collecting spectral data.
5) Obtain a graded series of exposures on the photoplate by collecting
spectra with the total charge accumulations and beam control con-
ditions given in Table 8.1. The ion beam control parameters given
in Table 8.1 are typical and serve as a guide to proper spectral
data collection. In general, the ion current passed to the photo-
plate should not exceed 1 X10~9 amps. Ion currents exceeding this
value tend to increase the system vacuum and therefore ion colli-
sions (produce charge exchange spectra) and increase secondary ion
images in the form of excessive photoplate fogging. In this event,
implement synchronous passing and beam chopping as appropriate to
limit the ion current. In general, the beam chopping should be
scaled according to the scheme shown in Table 8.1.
6) Remove the exposed photoplate from the detection chamber and the
analyzed electrodes from the source, and ready the instrument for
subsequent analyses.
7) Develop exposed photoplates using Ilford ID-13 developer prepared
at one half the recommended strength for 5 minutes (twice the recom-
mended development time.1-3 Stop the plate development in standard
photographic stop-bath for 15 seconds, and fix the plate for 3 min-
utes 1n standard photographic fix solution with hardener. Wash the
developed plates for 30 minutes in running water.
8-20
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Table 8.1. Suggested Instrument Conditions for Obtaining Mass
Spectra] Data as a Graded Series of Exposures.
CO
Photoplate
Level
0
2
4
6
8
10
12
14
16
18
20
22
24
26
28
30
32
Stage
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Relative
exposure
Prespark
12.000
6,000
3,000
1,500
800
400
200
100
50
25
12
6
3
1.5
0.75
0.40
Couloab
exposure
5 x IO-8
1.2 x IO-7
6 x IO-8
3 xlO-8
1.5 x 10"8
8 x 10"9
4 x «f9
2 xlO-9
1 x Hf9
5 xlO-10
2.5 xlO-10
1.2 x ID'10
6 x 10
3 x 10'11
1.5 x 10"11
7.5 x ID'12
4.0 x 10"1Z
Beam*
chopping
frequency
(Hz)
_
_
.
_
_
.
_
-
-
100
30
30
10
3
30
3
10
10
10
1
1
1
Count
50
120
60
30
15
8
4
2
1
1
2
2
1
2
1
2
2
1
0.5
1.5
1
1
Coulo*
•eter Synchronous
full scale passer
1 x
3 x
1 X
1 x
3x
1 x
1 x
1 x
3 x
3 x
3 x
3 x
3 x
1 x
IO-9 Pass
IO-10 Chop
io-10
io-10
io-11
io-11
UT10
ID'11
10"11
io-11
10-"
ID'12
ID'12
io-12*
These settings are typical for a spark repetition rate of 300 Hz and a resulting ion current less than 1 nC. Depending on the ion current
and charge accusation rate, it Bay be necessary to reduce the beam chopping frequency and spark repetition rate.
-------
8.3.5.3 Photoplate Interpretation
The interpretation of spectral data collected on a photoplate consists
of two discrete operations. The first, and obviously the most critical, is
the qualitative interpretation; i.e., the assignment of a mass spectral line
to a particular element. The second involves a determination of the relative
number of ions which produced the spectral line (the relative concentration
of the element). The steps to be carried out in order to make these deter-
minations are given below.
1) Develop the mass/charge (m/e) scale using the 12cn (e=l)
spectral lines and the spectral lines of elements known to be pre-
sent (multiple isotopes and multiply charged ions are also useful).
Mark the photoplate according to the nominal mass scale so devel-
oped. A numbering every 5-10 mass units is sufficient.
2) Determine the probable presence or absence of each element of
interest. For an unambiguous determination, at least one of the
following criteria (sn order in decreasing importance) must be
met:
a. The isotopic abundance ratios agree with the naturally occur-
ing fractional abundances.
b. Multiply charged ions (e = 2,3,. . .) of the element of interest
can be identified.
c. A mass measurement of sufficient accuracy to confirm the pre-
sence of the element in question can be made.
3) Confirm the presence of each element deemed probable in Step 2 by
ruling out all interferences likely to be present. Possible inter-
ferences are dimers, trimers, oxides, and carbides of elements
present in high concentrations and hydrocarbon molecules. Hydro-
carbon molecules are easily recognized since they form "runs" con-
sisting of CnHn+x (where x = 1,2,3,...), and the distribution of
intensity about x = 2 is symmetrical. Hydrocarbon runs occur
only in samples of high organic content. If these interferences
are too severe for effective photoplate interpretation, the sample
should be combusted according to Section 8.2 and reanalyzed.
If photoplate interpretation is straightforward, all elements
whose presence can not be ruled out nor confirmed should be quan-
tified according to the methods described below and identified
with "less than" values.
8-22
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4) Determine the relative exposures of the spectral line of each
element of interest which is "just detectable" as a line on the
photoplate. For spectral lines which are more'than "just detect-
able" on a given stage but are completely absent on the following
stage, a logarithmic interpolation of the exposure should be made
(the interpolation is logarithmic owing to the characteristic
response of ion sensitive photoplates).
5) For all spectral lines for which a "just detectable" exposure can
not be determined, measure the percent transmittance (percent T)
of one or more exposure levels. The lines chosen for percent T
measurement should be free from line-broadening, i.e., fall within
the limits of the typical linewidth versus mass characteristic
curve (see below), and have optical densities in the range 0.2 to
0.5; i.e., percent T's in the range 63 to 30 percent. Elements
which have no spectral lines which met the above criterion are
denoted as major components (MC) of the sample. It should be
noted that MC concentrations can indicate actual concentrations
in the range 0.5 to 100 percent depending on the particular ele-
ment under analysis.
6) Determine the "just detectable" exposure of the internal standard.
If percent T measurements were required for elements of interest,
measure the percent T of all standard lines which meet the above
criteria.
8.3.5.4 Calibration Parameters
As with all analytical methods, a SSMS analysis relies on a calibra-
tion via the determination of several instrumental parameters. These deter-
minations need not be made prior to each sample analysis but as an initial
calibration procedure and should be repeated on a periodic basis as part
of the quality assurance program. The principal calibration requirements,
and the suggested frequency of determination are given below.
1) The mass resolution should be known prior to interpretation of
spectral data. wTvfle the resolution is of prime importance to
the qualitative determination of the presence of an element, it
is the ultimate consideration in ruling out an interfering species.
Hence the instrumental resolution can both confirm elemental com-
position and lend credit to the quantitative determination. The
resolution is primarily a function of the main slit (first slit
at ground potential) width. Theoretically, the resolving power
is given by R0 = re/S0» where re is the rotation radius of the
electrostatic field, and S0 is the main slit_width. In jDractice,
the resolution is measured according to R = M/AM, where M is the
mean mass of the M/e lines of interest, and AM is the mass sepa-
ration. For typical environmental samples, a resolution of greater
than 3,000 is desirable.
8-23
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2) The photoplate response to an ion is primarily a function of its
mass and energy (for emulsion based photoplates). For constant
charge(e), the response of Ilford Q2 photoplates varies approxi-
mately as nrl/2; e.g., Li is the most sensitive and U the least.
Also, the greater the charge (the more energetic), the greater the
response. The in'1/2 variation in response of the Ilford Q2 photo-
plate is well documented in the literature and can be verified
most easily by recording.the response produced by elemental species
with multiple isotopes [Li and W are suitable choices).
3) The spectral line width is primarily a function of ion-optics
employed in the spectrometer; i.e., a function of the ion beam
focusing. An instrument with Mattauch-Herzog ion optics in
"perfect" focus should yield a spectral line whose relative width
is proportional to the square root of the mass, M. In practice,
mass spectrometers are not capable of perfect focus, and in many
cases it is desirable to use other focal arrangements. Therefore,
the spectral line widths should be determined experimentally for
each focal setting and after any change in focal setting.
4) The relative sensitivity of the SSMS analysis to a particular ele-
mental species depends on a number of factors including ioniza-
tion potentials, bond or dissociation energies, boiling points,
heats of sublimation, etc., as well as instrumental parameters.
Since many of these variables are compound-specific, the use of
well characterized standards whose matrices closely resemble
sample matrices is highly desirable.
For the present program, sample types analyzed by SSMS can be
grouped into two basic categories: 1) particulate or fly ash,
and 2) extracts or solutions which contain excess nitric acid.
Therefore, the sensitivity factors used for this program are deter-
mined from 1) NBS SRM 1633 Fly Ash Standard, and 2) a laboratory
prepared standard containing the nitrate salts (or nitric acid
dissolution of the oxides) of all elements of interest. Sensi-
tivity factors are determined relative to an indium value of
unity in all cases.
In general, the relative sensitivity factors (RSFs) are determined
by running the standard materials under experimental conditions
Identical to the conditions used when running samples. Calcula-
tions of RSF data using the "just detectable" line technique for
exposure measurements should be carried out using a minimum of six
determinations so that statistically meaningful data result.
8.3.6 Calculations
As indicated 1n the above procedures, the elemental concentration data
are obtained by the "just detectable" line technique when possible and from
percent T data, otherwise. In either case, variables to be determined are
8-24
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the exposures necessary to produce identical responses for the unknown and
internal standard mass spectral lines. Concentration data may then be cal-
culated according to
r - r • F -A • w • M /s
cu " Lk LR AR WR VbR
where Cu — is the unknown concentration;
Ck - is the known concentration (internal standard);
ED - is the ratio of the exposure (E|
-------
Photoplate data for the standard materials are collected and inter-
preted according to the procedures described above. Mass responses, MR,
should be verified and spectral line widths measured according to 8.3.5.
Relative sensitivity data can be determined by rearranging the concentra-
tion equation given above and calculating SR for each element using the
known standard concentrations.
8.3.7 Precision and Accuracy
Spark Source Mass Spectrometry in general is a semiquantitative tool.
Although precisions of ±5 to 10 percent can be achieved,^ the methodology
for such analyses are very time-consuming when comprehensive elemental
surveys are being performed. Typical factors which affect the precision
and accuracy of SSMS analyses include sample homogeneity, preparation of
electrodes which adequately represent the sample, photoplate irregularities,
spark discharge characteristics, and the general lack of well-characterized
standards. In addition, the methods used for spectral line intensity deter-
minations can limit the precision and accuracy a priori. The methodology
employed for the present program was designed to yield precision on the
order of 50 to 100 percent. While absolute accuracies depend on the quality
of the standards used, typical accuracies of 100 to 200 percent are obtained.
8-26
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8.3.8 References
1. Guthrie, J.W. Analysis of Special Samples in Mass Spectrometric
Measurements of Solids. A.J. Ahearn, ed. Elsevier Publishing
Co., Amsterdam, p. 124 (1966).
2. Owens, E.B. and N.A. Giardino. Anal. Chem., 35_, 1172 (1963).
3'. Bey, P.P. and J.G. Allard. NRL Report 6655, Naval Research
Laboratories, Washington, D.C. ' (1968).
4. Conzemius, R.J., D.H. Erbeck, S.T. Elbert. USAEC R&D Report
IS-1693. October 1967.
5. Desjardin M. and J.A. Moore. Appl. Spectrosc., 22_, 713 (1968).
6. Franzen, J., K.D. Shuy, Z. Naturforsh. 21a. 1479 (1966).
7. Woodston, J.R. 13th Annual Conference on Mass Spectrometry.
St. Louis, p. 79, May 1965.
8. Bonham, R.W. and J.O. Humphries. 16th Annual Conference on Mass
Spectrometry, Pittsburgh, May 1968.
9. Paulson, P.J. and P.E. Branch. 14th Conference of Mass Spectro-
metry, Dallas, May 1966.
10. J. Mattauch and H. Ewald. Naturwissenschaften, 41, 487 (1943).
11. Dornenburg, E., H. Hintenburger, Z. Naturforsch. 16a, 676 (1961).
12. Hull, C.W. 10th Annual Conference on Mass Spectrometry.
New Orleans, June 1962.
13. Paulson, P.J. National Bureau of Standards, Washington, D.C.,
Private Communication.
14. Nicholls, G.D., A.I.. Grahm, E. Williams, and M. Wood. Anal. Chem.
39, 584 (1967).
8-27
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8.4 MERCURY ANALYSIS
8.4.1 Scope and Application
The cold vapor mercury analysis described here is applicable for the
Level 1 and Level 2 determination of Hg in hydrogen peroxide and ammonium
persulfate impinger solutions, bulk liquids, dilute HN03 solutions re-
sulting from the Parr Bomb combustion of fuels and XAD-2 resin samples, and
aqua regia solutions from the digestion of particulates. Sensitivity and
detection limits are 0.004 and 0.001 yg, respectively, with an upper limit
of 0.25 yg.
8.4.2 Summary of Method
The cold vapor mercury analysis is based on the reduction of mercury
species in acid solution with stannous chloride and the subsequent sparg-
ing of elemental mercury, with nitrogen, through a quartz cell where its
absorption at 253.7 nm is monitored.
8.4.3 Apparatus
• Mercury reduction apparatus. The usual design, consisting of
a jar incorporating a two-hole rubber stopper through which a
gas bubbler tube and a short gas outlet tube pass, can be used.
The TRW design is essentially a U tube with a glass frit on one
side. The frit serves as a mixing device as well as the gas
bubbler, thus eliminating the need for a separate magnetic
stirrer and a stirring bar to mix the reductor contents.
• Atomic absorption spectrophotometer. Use a mercury hollow
cathode lamp at a wavelength .of 253.7 nm. (or equivalent)
• Absorption cell. A cylindrical tube approximately 25 mm I.D.
x 125 mm long, with quartz windows, and incorporating inlet
and outlet side arms to permit introduction and discharge of
carrier gas. This type of cell is available commercially from
several manufacturers of atomic absorption equipment, or it may
be constructed from readily available materials. In the latter
case, the cell should be tested carefully for possible leakage
after.assembly. The cell is mounted in the optical path of
the AAS.
t Flowmeter. Capable of measuring a gas flow on the order of
1.9 liters/min (4 ft3/hr).
8-28
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Scavenging tube. This tube is filled with soda lime and is
connected between the gas outlet tube of the reduction vessel
and the inlet side arm of the absorption cell with Tygon tubing.
The soda lime is replaced every 25 determinations; otherwise,
a loss in sensitivity occurs.
• Erlenmeyer flasks, 125 ml
• Beakers, 150 ml
• Pellet press
• Funnels
0 Filter paper, Whatman #41
8.4.4 Reagents
Stock Mercury solution, approximately 1 gram/liter (1000 ppm).
Weigh one gram of pure, elemental mercury to the nearest 0.1 mg
and dissolve in a solution consisting of 150 ml deionized water
and 50 ml concentrated HN03 (sp. gr. of 1.42). Dilute this
solution to 1000 ml with deionized water. The final solution
contains approximately 1000 ppm mercury (record exact concen-
tration) in a matrix of 5 percent (v/v) nitric acid. A com-
mercially obtained 1000 ppm Hg solution can also be used.
Standard mercury solutions. Prepare working standard solutions
of mercury down to 1 ppm by serial dilutions of the 1000 ppm Hg
stock solution with 5 percent (v/v) HNOs. Such solutions can be
assumed to be stable for up to one week. Below 1 ppm Hg.
standard solutions should be prepared daily and diluted with
5 percent (v/v) HNOs and/or deionized water as appropriate so
the final sblution matrix is approximate 1 percent (v/v)
• 1:1 Nitric acid solution. Dilute 500 ml cone, nitric acid to
1000ml.
t Stannous chloride solution. Dissolve 20 g of SnCl2.H20 in 20 ml
cone. HC1 (warm the solution to accelerate the dissolution
process) and dilute to 100 ml.
• Potassium permanganate solution . Dissolve 5.0 g KMnO. 1n
deionized water and dilute to 1 liter.
• Nitrogen carrier gas.
t Nitric acid, cone.
0 Hydrochloric acid, cone.
• Benzoic acid.
8-29
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8.4.5 Procedure
8.4.5.1 Standardization
Standards in the range of 1-10 ppb are made. To the reduction vessel,
transfer 10 ml 1:1 nitric acid solution, 3 ml cone. HgSO,, 5 ml of a
standard solution, and deionized water to bring the volume to a total of
50 ml. Add 5 ml of stannous chloride solution. Close the system and
immediately initiate the nitrogen flow. The optimum flow rate will vary
from system to system, therefore, several flow rates should be tried until
maximum sensitivity is obtained. Repeat the procedure for varying concen-
trations of mercury throughout the specified range. The glass frit is
cleansed in between analyses by flushing with 1:1 nitric acid'followed by
deionized water. Blanks should be run using deionized water. Plot
absorption (peak height) against standard concentration to obtain a
calibration curve.
8.4.5.2 Analysis
In the determination of mercury by the cold vapor technique, certain
volatile organic materials may absorb at 253.7 nm. If this is expected,
the sample should be analyzed by the regular procedure and again under
oxidizing conditions, i.e., without the addition of stannous chloride. The
true mercury concentration can be obtained by taking the difference of the
two values.
• Aqueous samples are analyzed by the same procedure as that used
for standardization. If a larger sample size is used resulting
in a total volume greater than 50 ml, a new calibration curve
must be constructed using the new total volume.
• 3M H202 has shown an interference by consuming the stannous
chloride reducing agent. This problem is circumvented by
decomposing the excess H202 with permanganate prior to stannous
chloride addition. Pipet an aliquot into a 125 ml Erlymeyer and
add 10 ml cone. HN03. Add KMn04 solution with stirring until
the MnO? precipitate that forms will not redissolve. At this
point add 2 ml cone. H2S04 and 1 drop 30 percent H?02. After
precipitate has redissolved continue adding KMn04 dropwise
until a permanent reddish color is obtained. Transfer contents
to reduction apparatus and adjust volume to approximately
50 ml. Proceed as per the standardization procedure.
8-30
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• The presence of the silver nitrate catalyst in the ammonium
persulfate solution has been shown to yield low Hg recoveries.
Removal of Ag+ by addition of Cl" followed by filtration has
been found to be an effective procedure for the removal of
this interference. Pipet an aliquot into a 150 ml beaker.
Add 10 ml cone. HNOs and 2 ml HC1. Filter through #41 What-
man filter. Wash several times with deionized water and
dilute filtrate to approximately 50 ml. Transfer filtrate
to reduction vessel and proceed as per standardization
procedure.
• In analyzing organic solids, aliquots from Parr bomb decom-
position over acid are used. If there is doubt as to whether
the sample has undergone complete oxidation during combustion,
add 5 percent potassium permanganate solution dropwise until a
pink color persists. Proceed with the determination as
described under standardization. As the bomb ages, there may
be a tendency for mercury to become trapped in the bomb wall
fissures during combustion. In addition, if the same bomb is
used for normal calorimetry work, there may be a tendency for
mercury to accumulate in the bomb with time. Consequently,
before a series of mercury determinations is undertaken, several
blank determinations should be made by firing benzoic acid
pellets (approximately 1 gram) in place of the sample. Benzoic
acid firings should be repeated until a stable, consistently low
blank value is obtained. This final blank value is then used to
correct the mercury values obtained for subsequent samples. The
condition of the interior of the bomb should be inspected at
frequent intervals. If evidence of significant pitting or
corrosion is observed (usually indicated by erratic mercury
values for samples or benzoic acid blanks), the bomb should be
returned to the manufacturer for reconditioning.
• To analyze particulates, aliquots from the aqua regia digestion
are used. Proceed with the determination as described under
standardization.
8«4.6 Calculation
Compare the absorption of the samples to the calibration curve and
calculate the amount of mercury content as follows:
W
Hg content (ppm) = y
Where
W - weight of mercury, ^9
V • volume of aliquot, ml
8-31
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8.4.7 Precision and Accuracy
Mercury at a concentration of 0.4 fig/liter yields a precision of
+21.2 percent RSD with a relative error of 2.4 percent.
8.5 ARSENIC ANALYSIS
8.5.1 Scope and Application
Arsenic analysis by hydride generation and atomic absorption
spectrometric detection is applicable for Level 1 analysis of impinger
solutions, coal, fly ash and XAD-2 resin samples. Detection limit for the
procedure is 0.1 i^g with a calculated sensitivity of 0.8 p.g. Either of two
arsine evolution methods can be used: gas can be generated in a reaction
with stannous chloride and zinc slurry, or in a reaction with sodium
borohydride. Some interferences have been reported for this arsenic pro-
cedure. In particular, it has been found that excess HpOp and HNO, must be
removed prior to the addition of either the Zn slurry or NaBH^.
8.5.2 Summary of Method
The procedure entails the reduction and conversion of .arsenic to its
hydride in acid solution with either SnClp and metallic Zn or NaBH^. The
volatile hydride is swept from the reaction vessel, in a stream of argon,
into an argon-hydrogen flame in an atomic absorption spectrophotometer.
There, the hydride is decomposed and its concentration monitored at the
resonance wavelength 193.7 nm. Arsenic reaction stoichiometry is 1:1.
8.5.3 Apparatus
§ Flow meter, capable of measuring 1 liter of gas/min.
• Medicine dropper, capable of delivering 1.5 ml, fitted into
a size "0" rubber stopper.
• Reaction flask, 50 ml capacity pear-shaped vessel with side
arm having 5 14/20 joints on both the neck and side arm.
• Special gas inlet-outlet tube, constructed from a micro
cold finger condenser by cutting off the portion below the $
14/20 ground glass joint.
• Magnetic stirrer, strong enough to homogenize the zinc slurry.
• Drying tube, 10-cm long polyethylene tube filled with glass
wool to keep particulate matter out of the burner,
8-32
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Apparatus setup involves: 1) connecting the outlet of the
reaction vessel to the auxiliary oxidant input of the spec-
trophotometer burner with Tygon tubing and 2) connecting the
inlet of the reaction vessel to the outlet side of the
auxiliary oxidant (argon supply) control valve of the
instrument.
8.5.4 Reagents
• Potassium iodide solution; Dissolve 20 g KI in 100 ml
delon1zed water.
• Stannous chloride solution: Dissolve 100 g SnCl2 1n 100 ml
cone. HC1.
• Z1nc slurry: Add 50 g zinc metal dust (200 mesh) to 100 ml
deionlzed water.
• Diluent: Add 100 ml 18 N H2S04 and 400 ml cone. HC1 to
400 ml deionized water in a 1 liter volumetric flask and
bring to volume with delonized water,
• Sodium borohydrlde solution: Dissolve 5 g NaBH4-H?0 1n
100 ml deionlzed water. Make fresh prior to eaSh use.
• Arsenic solutions:
1) Stock arsenic solution: Dissolve 1,3209 g arsenic
trloxide, AS203, 1n 100 ml deionlzed water containing
4 g NaOH and dilute to 1000 ml with deionlzed water,
1.00 ml solution contains 1.00 mg As,
2) Intermediate arsenic solution: Pipet 1 ml stock arsenic
solution Into a 100 ml volumetric flask and bring to
volume with deionlzed water containing 1.5 ml cone.
HN03/Hter. 1.00 ml solution contains 10ng As.
3) Standard arsenic solution: Pipet 10 ml Intermediate
arsenic solution Into a 100 ml volumetric flask and bring
to volume with deionlzed water containing 1.5 ml cone,
HN03/Hter. 1.00 ml solution contains 1 Mg As,
8-33
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8.5.5 Procedures
8.5.5.1 Instrument Operation
Because of differences between makes and models of satisfactory
atomic absorption spectrophotometers, it is not possible to formulate
instructions applicable to every instrument. In general, proceed as follows:
1) Install an arsenic hollow cathode lamp in the instrument,
and align the lamp in accordance with the manufacturer's
instructions.
2) Set the wavelength selector at 193.7 nm.
3) Set the slit width according to the manufacturer's
suggested instructions for analyzing As.
4) Turn on the instrument and apply the amount of current to the
hollow cathode lamp suggested by the manufacturer.
5) Allow the instrument to warm up until the energy source
stabilizes. This process usually requires 10 to 20 min.
6) Install a Boling burner head.
7) Turn on the argon and adjust to a flow rate of about 8 liters/
m1n, with the auxiliary argon flow at 1 Uter/min.
8) Turn on the hydrogen, adjust to a flow rate of about 7 liters/
min and ignite the flame. The flame is essentially colorless.
To determine whether the flame is ingited, pass the hand
about 30 cm (1 ft) above the burner to detect the heat
emitted.
9) Atomize the standard solution (1.00 ml = 1.00 M.g of
arsenic) and adjust the burner both sideways and
vertically in the light path until maximum response is
obtained.
10) The instrument 1s now ready to run standards and samples.
8.5.5.2 Sample Preparation
a) Condensate sample - Add 25 ml sample, 20 ml cone. HC1 and
5 ml 18 N H2S04 to a 50 ml volumetric flask.
b) Peroxide samples, aqua regia and nitric acid solutions - To
a 25 ml aliquot in a 150 ml beaker, add 5 ml cone. HNOs and
6 ml 18 N HgSOa. Evaporate to $03 fumes. To avoid the loss
of arsenic, maintain oxidizing conditions at all times by
adding small amounts of nitric acid whenever the red brown
N0£ fumes disappear. Cool, transfer to a 50 ml volumetric,
add 20 ml cone. HC1, and dilute to volume.
8-34
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c) Ammonium persulfate samples - Add 5 ml cone. HNO, and treat as
WbY.
d) Coal and XAD-2 resin samples - Treat Parr bomb solutions as in
_y_
8.5.5.3 Preparation of Standards
Transfer 0.5, 1.0, 1.5, and 2.0 ml of standard arsenic solution to
100 ml volumetric flasks and bring to volume with diluent to obtain
concentrations of 5, 10, 15, and 20 |j.g/liter arsenic.
8.5.5.4 Treatment of Samples and Standards
Transfer a 25 ml portion of sample prepared as in Section 8.5,5.2 or
standard prepared as in Section 8.5.5.3 to the reaction vessel and add
1 ml potassium iodide solution to arsenic samples and standards. If the
Zn slurry addition method is to be followed, add 0.5 ml SnCl2 solution.
'Allow at least 10 minutes for the metal to be reduced to its lowest oxida-
tion state. Attach the reaction vessel to the special gas inlet-outlet
jlassware. Fill the medicine dropper either with 1.50 ml zinc slurry that
has been kept in suspension with the magnetic stirrer, or with 1.50 ml
NaBH4 solution. Firmly insert the stopper containing the medicine dropper
into the side neck of the reaction vessel. Squeeze the bulb to introduce
either the zinc slurry or the NaBfy solution into the sample or standard.
The metal hydride will produce a peak almost immediately. When the
recorder pen returns to the baseline, remove the reaction vessel, empty,
and proceed with the next sample..
8.5.6 Calculations
Draw a standard curve by plotting peak heights of standards versus
concentration of standards. Measure the peak heights of the samples and
read the concentration from the curve. Multiply these concentrations by the
appropriate dilution factor.
8.5.7 Precision and Accuracy
Replicate lOng/liter samples exhibit a relative standard deviation
°f +6% and a relative error of +1.0%.
8-35
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8.6 ANTIMONY ANALYSIS
8.6.1 Scope and Application
This method is applicable for the analysis of ammonium persulfate,
hydrogen peroxide and dilute nitric acid and aqua regia solutions
obtained from Level 1 samples,
8.6.2 Summary of Method
Organic antimony-containing compounds are decomposed by adding
sulfuric and nitric acids and repeatedly evaporating the sample to fumes
of sulfur trioxide. The antimony liberated, together with the inorganic
antimony originally present, is subsequently reacted with potassium iodide
and stannous chloride, and finally with sodium borohydride to form stibine.
The stibine is removed from solution by aeration and swept by a flow of
nitrogen into a hydrogen diffusion flame in an atomic absorption spec-
trometer. The gas sample absorption is measured at 217.6 nm. Since the
stibine is freed from the original sample matrix, interferences in the
flame are minimized.
8.6.3 Apparatus
t Atomic absorption spectrometer and recorder
Refer to the manufacturers' manuals or procedures to optimize
output of the instruments for the following parameters:
Grating Ultraviolet
Wavelength 217.6 nm
Source (Electrodeless
discharge or hollow
cathode lamp) Antimony
Burner Three-slot burner or equivalent
Fuel Hydrogen
Diluent Nitrogen
Carrier Nitrogen
8-36
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Stibine vapor analyzer (Figure 8-3) consisting of: 1) a 100 ml
capacity three-neck round-bottom flask; 2) gas dispersion tube,
coarse frit (Scientific Glass Apparatus Co. No. JG-8500 has been
found satisfactory); and 3) 2 ml capacity medicine dropper, or
5 ml capacity automatic pipetter.
8.6.4 Reagents
• Antimony standard solution I, 1.00, ml = 100 M? Sb. Dissolve
274.3 mg antimony potassium tartrate, (SbOjKCJLOc'l^HeO, in
deionized water and dilute to 1 liter with deionTzed water,
• Antimony standard solution II. 1,00 ml • 10 pig Sb. Dilute 50,0
ml antimony solution I to 500.0 ml with deionized water.
t Antimony standard solution III. 1.0 ml = 0.10 ng Sb. Dilute
5.0 ml antimony standard solution II to 500.0 ml with deionized
water. Prepare fresh before each use.
• Hydrochloric acid, cone, (sp gr 1,19).
• Nitric acid, cone, (spgrl.41).
• Potassium iodide solution. 15 g/100 ml. Dissolve 15 g KI in
100 ml deionized water. This solution is stable when stored
in an amber bottle.
• Sodium boronvdride solution. 4 g/100 ml. Dissolve 4 g NaBH4
pellets in 100 ml deionized water (Alfa Products No, 14122
has been found satisfactory). Prepare fresh just before
each use.
• Stannous chloride solution. 4,6 g per 100 ml cone. HC1.
Dissolve 5 g SnC^'HgO in 100 ml cone. HC1 (sp gr 1.19), This
solution is stable if a few pieces of mossy tin are added to
prevent oxidation.
• Sulfuric acid 9M. Cautiously, and with constant stirring and
cooling, add 250 ml cone. H2S04 (sp gr 1,84) to 250 ml
deionized water.
8.6.5 Procedure
1) Prepare, in 150 ml beakers, a blank and sufficient standards
containing from 0.0 to 1.5 n-g Sb by diluting 0.0 to 15.0 ml
portions of antimony standard solution III to 100 ml with
deionized water.
2) To each beaker, add 7 ml 9M H?S04 and 5 ml cone. HNOa, Add
a small boiling chip and carefully evaporate to fumes of 503.
Maintain an excess of HNOs until all organic matter is
destroyed as evidenced by a clear solution. This prevents
8-37
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N2 INLET
EYE DROPPER FOR
No BH4 ADDITION
*- TOAA
GAS DISPERSION TUBE
100 ML THREE NECK
ROUND BOTTOM FLASK
Figure 8-3. Hydride Evolution Apparatus
darkening of the solution and possible reduction and loss
of antimony. Cool, add 25 ml deionized water, and again
evaporate to fumes of $03 to expel oxides of nitrogen.
3) Cool, and adjust the volume of each beaker to approximately
50 ml with deionized water.
4) To each beaker, add successively, with thorough mixing after
each addition, 4 ml cone, HC1, 1 ml KI solution, and 0.5 ml
SnCl2 solution. Allow about 15 minutes for reaction *
5) To set the N2 carrier gas flow rate, place 55 ml of deionized
water in the round-bottomed flask and put a rubber stopper in
place of the medicine dropper. Increase the N2 flow slowly
until a maximum is reached which still avoids carrying liquid
into the tubing leading to the AA instrument. Empty the flask
and begin analyzing the samples by transferring the contents
of each beaker, one at a time, to the flask and proceeding
with the NaBH4 reaction.
8-38
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6) Fill the medicine dropper with-1 ml NaBfy solution and insert
into a one-hole rubber stopper that has been tightly fitted
into the center neck of the three-neck round-bottom flask.
Press the dropper and rubber stopper both in tightly.
7) Add the NaBH* solution all at once quickly to the sample
solution. After the absorbance has reached a maximum and
has returned to the baseline as measured by the AAS instru-
ment, remove the flask. Rinse the gas dispersion tube in
deionized water before proceeding to the next sample. Treat
each succeeding sample, blank, and standard in a like manner.
8.6.6 Calculations
The fig of Sb in each sample aliquot is determined by comparison to a
standard curve that plots absorbance vs. concentration. Exact reproduce
bility is not obtained; therefore, a standard must be prepared with each
set of samples, compared with the standard curve and an appropriate
correction made.
Determine the concentration of Sb as follows:
Sb, ppm = A x (T
Where:
A = nig Sb in sample, taken from calibration curve
B = Standard, known concentration |j.g Sb
C = Standard, ng Sb taken from calibration curve
D = Sample volume, ml
8-39
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8.7 SULFATE ANALYSIS
8.7.1 Scope and Application
The turb1d1metric procedure 1s designed to be used for Parr bomb
combusted XAD-2 resins or fuels and for hot water and add extracted particu-
late samples. For those cases 1n which both a hot water and an add
extraction is performed on allquots of the same partlculate sample, the
sulfate analysis is to be performed on the hot water extract. The turbldl-
metric procedure may be performed on the add extract of partlculate samples.
However, the values may be low because of Incomplete formation of barium
sulfate as a result of the high acid content 1n the sample. Color or sus-
pended matter 1n large amounts will Interfere with this method. Correc-
tions for color can be made using appropriate blanks and suspended matter
may be removed by filtration. Silica in excess of 500 mg/llter will Inter-
fere, and in waters containing large quantities of organic material 1t may
not be possible to precipitate barium sulfate satisfactorily.
There are no Ions other than sulfate in normal solutions that will form
Insoluble compounds with barium under strongly add conditions. Determina-
tions should be made at room temperature, which may vary over a range of
10°C without causing appreciable error.
The minimum detectable concentration is approximately 1 mg sulfate/
liter.
8.7.2 Summary of Method
Sulfate ion is precipitated In a hydrochloric add medium with barium
chloride 1n such manner as to form barium sulfate crystals of uniform size.
The absorbance of the barium sulfate suspension 1s measured by a transmis-
sion photometer and the sulfate ion concentration 1s determined by compari-
son of the reading with a standard curve.
8.7.3 Apparatus
0 Magnetic stlrrer. It is convenient to Incorporate a timing
device to permit the magnetic stlrrer to operate for exactly
1 minute. The stirring speed should not vary appreciably. It
1s also convenient to Incorporate a fixed resistance 1n series
with the motor operating the magnetic stlrrer to regulate the
speed of stirring. If more than one magnet 1s used, they should
8-40
-------
be of identical shape and size. The exact speed of stirring
is not critical, but it should be constant for each run of
samples and standards and should be adjusted to about the
maximum at which no splashing occurs.
• Photometer. One of the following is required with preference
in the order given: nephelometer, such as Coleman Model #9;
spectrophotometer, for use at 420 nm and providing a light path
of 4-5 cm; filter photometer, equipped with a violet filter
having maximum transmittance near 420 nm and providing a light
path of 4-5 cm.
• Stopwatch, if the magnetic stirrer is not equipped with an
accurate timer.
t Measuring spoon, capacity 0.2-0.3 ml.
8.7.4 Reagents
• Conditioning reagent. Mix 50 ml glycerol with a solution
containing 30 ml concentrated HC1, 300 ml deionized water,
100 ml 95 percent ethyl or isopropyl alcohol, and 75 g sodium
chloride.
• Barium chloride, crystals, 20-30 mesh.
• Standard sulfate solution. Prepare a standard sulfate
solution by diluting 10.41 ml of standard 0.0200 N H2S04
titrant to 100 ml with deionized water. Dissolve 147.9 mg
anhydrous'sodium sulfate, NagS04, in deionized water and
dilute to 1000 ml.
8.7.5 Procedure
8.7.5.1 Formation of Barium Sulfate Turbidity
Measure 100 ml sample, or a suitable aliquot (record volumes) made
up to 100 ml, into a 250 ml Erlenmeyer flask. Add exactly 5.00 ml con-
ditioning reagent and mix in the stirring apparatus. While the solution
is being stirred, add a spoonful of barium chloride crystals and begin
the timing immediately. Stir for exactly 1 minute at a constant speed.
8.7.5.2 Measurement of Barium Sulfate Turbidity
Allow sample to set for 10 minutes prior to measurement. To measure
the turbidity, pour some of the solution into the absorption cell of the
photometer and record the absorbance.
8-41
-------
8.7.5.3 Preparation of Calibration Curve
Estimate the sulfate concentration in the sample by comparing the
turbidity reading with a calibration curve secured by carrying sulfate
standards through the entire procedure. Space the standards at 5 mg/liter
increments in the 0-40 mg/liter sulfate range. Above 40 mg/liter the
accuracy of the method decreases and the suspensions of barium sulfate
lose stability. Check reliability of the calibration curve by running a
standard with every three or four unknown samples. Record results on
analytical traveler.
8.7.5.4 Correction for Sample Color and Turbidity
Correct for the color and turbidity present in the original sample
by running blanks from which the barium chloride is withheld. Obtain
blank from diluted sample prior to addition of BaCl2. Record blanks
equivalent absorbance vs. deionized water.
8.7.6 Calculation
Sulfate content (mg/liter) = sample Aliquot Volume, ml
where:
A = SO^" content of sample interpolated from calibration curve,
mg/liter (ppm)
B = S04~ equivalent of blank interpolated from calibration curve,
mg/liter (ppm)
8-42
-------
8.8 CONTROLLED CONDENSATION SAMPLING TRAIN (CCS) - SAMPLE
PREPARATION AND ANALYSIS
This section describes sample preparation and analysis procedures for
CCS train samples. These procedures, summarized in Figure 8-4, include
optional analyses for chloride and fluorides, along with the usual $03, SOg,
and particulate sulfate analyses.
8.8.1 Hot Water Extraction
8.8.1.1 Scope and Application
This procedure is to be used to prepare particulate samples for the
determination of water soluble Cl, $04, and F am'ons. It is very similar
to the aqua regia digestion procedure. However, it is necessary to main-
tain separate sets of glassware and Nalgene in order to avoid contamination
of these samples with aqua regia.
8.8.1.2 Apparatus
• Distillation flasks, flat-bottom, 100 ml
• Condensers, Liebig or Allihn type
• Hot plate
• Volumetrics, 50 ml
• Filter funnels,
• Filter paper, Whatman No. 41
8.8.1.3 Reagent
Deionized water
8.8.1.4 Procedure
The weighed sample aliquot is placed in the distillation flask, 30 ml
of delonized water are added, the condenser is attached, and the apparatus
is secured over a hot plate. The water is refluxed for ^1/2 hour at which
time the apparatus is removed from the hot plate. While still hot, the
solution in the distillation flask is filtered through a Whatman No. 41
filter into a volumetric. Wash several times with hot water, cool and
dilute to volume. Label the volumetric and turn the sample in to the
Sample Bank Manager.
8-43
-------
TRAIN COMPONENT
PPr^RP PAPTI(*III ATF
MATTER
FILTER
(AND BLANK)
CONTROLLED
CONDENSATION
COIL RINSE
H7O. IMPINGER
Kin rr\ iMPiwrtFB
PREPARATION
HOT H2O
EXTRACTIO
\
SI
I
WEIGH
Jr,ITrc| EXTRAa
POLIOS ^
HOT 10%
HCI EXTRACTION
AND
RECORD
JDESI
^OVE
AIR
Aa
(SAM
(MAT
CCATE I
ANIGHT!
PORATE -*
TONE
<
V
f
A
E
DESICCATE
OVERNIGHT
I
WEIGH
AND
RECORD
i
IOMBINE
VI TH PROBE
ARTICULATE
AATTER AND
XTRAa
|ri* 1 EXTRAa
^SOLIDS^V
DISCARD |
EAS
BE PARTI CULATE
TER
ADD
HIG
.* NC«
MAK
PH(
ENOUGH
H PURITY
COgTO
E ALKALINE
J-9)
H
2°
RINSE
BOIL TO
_» DESTRO^
^0,
f
^ DILUTE TO
* 100 ML
RE-WEIGH
RECORD
ANALYSIS
^ ri~ F~ SO.=I
_fc Crt r c™
-> su^ , h
ACID/BASE
» TITRATION,
so4-
k SO/. Ci.
F
„ S0/f CI"."
, so/,
* C!-,F-
SPECIES FOUND
-» SOLUBLE SO47
CI", F-
WATER
^ INSOLUBLE
- SQT,r
J H,SO,
»| 2 4
fc SO,, H CI,
* Hr
. SO,, HCt
^ HF
SO,, H CI,
* HF
¥ HjO CALC.
Figure 8-4. Analysis Scheme for Controlled Condensation Train Samples
8-44
-------
8.8.2 Hot HC1 Extraction
8.8.2.1 Scope and Application
This procedure 1s to be used to prepare particulate samples for the
determination of water Insoluble 864 and F. This procedure 1s nearly
Identical to Section 8.2.2. This glassware must not be Interchanged with
that used 1n Section 8.8.1.
8.8.2.2 Apparatus
• Distillation flasks, flat-bottom, 100 ml
• Condensers, L1eb1g or AlUhn type
• Hot plate
t Volumetrlcs, 50 ml
• Filter funnels
• Filter paper, Whatman #41
8.8.2.3 Reagent
10 percent Hydrochloric add solution
8.8.2.4 Procedure
The weighed sample aliquot 1s placed 1n the distillation flask, 30 ml
of the hydrochloric add solution 1s added, the condenser 1s attached, and
the apparatus 1s secured over a hot plate. The solution 1s refluxed for
1/2 hour after which time the apparatus 1s removed from the hot plate.
While still hot, filter the solution 1n the distillation flask through a
Whatman #41 filter Into a volumetric. Wash several times with 10 percent
HC1 solution, cool and dilute to volume. Label the volumetric and turn
the sample 1n to the Sample Bank Manager.
8.8.3 SulfuHc Add Analysis - Level 2 Analysis of CCS Coll Sample.
8.8.3.1 Scope and Application
SulfuMc add 1n the CCS train coll condensate sample 1s determined
by acid-base tltratlon. All other CCS train samples are analyzed for
sulfate by the turbldlmetrlc method given 1n Section 8.7.
8-45
-------
8.8.3.2 Summary of Method
The preferred method of analysis is the acid/base titration using
Bromphenol Blue indicator. Carefully handle and store the samples in clean
glassware and analyze them as soon as possible. Record all results on the
laboratory data sheet.
Each acid/base indicator in this procedure will change color over a
different pH range. For example:
Indicator pH range Color Change
Bromphenol Blue 3.0-4.6 yellow to blue
Phenolphthalein 8.2-10.0 colorless to pink
The point measured by the indicator is simply the point at which the
color change occurs. The actual end point where exactly the right amount
of acid and base have reacted (equivalence point) can be close to or far
away from the indicator end point. Thus Bromphenol Blue is chosen for the
NaOH + H2S04 titration, since the equivalence point occurs at about pH 3.
Phenolphthalein is used for the KHP + NaOH standardization titration
because the equivalence point is near pH 7.
Even though the indicators have been selected to be as close as possible
to the actual end point, a small difference still exists and is called the
indicator blank. The indicator blank for phenolphtalein is the amount of
NaOH required to change a specific amount of water containing a known number
of drops of phenolphtalein pink. This value is subtracted from the milli-
liters used to titrate the sample.
The indicator blank from Bromphenol Blue is determined in the same
way (known volume and number of drops) except that a standard acid (HgSO^
is used to backtitrate the indicator in distilled water to a yellow color.
The number of milliequivalents used is added to the amount found titrating
the sample.
NOTE
Blanks can vary with sample size and number of drops
of Indicator; therefore, determine the indicator blank
under the same conditions in which the sample is
titrated.
8-46
-------
8.8.3.3 Apparatus
• Ten milliliter micro-buret, Kimble 17132F (A.M. Thomas,
No. 1993-M-30 or equivalent)
• Four Erlenmeyer flasks with 28/15 ball-and-socket joint, 125 ml
(Ace Glass Co., Louisville, Ky., No. 6975 or equivalent).
8.8.3.4 Reagents H?S04 Titration
• Carbon dioxide-free distilled water - Prepare all stock and
standard solutions, and dilution water for standardization
procedure, using distilled water which has a pH of not less
than 6.0. If the water has a lower pH, it should be freshly
boiled for 15 minutes and cooled to room temperature.
NOTE
Deionized water may be substituted for
distilled water provided that it has a
conductance of less than 2 micro-ohms/cm
and a pH greater than 6.0.
• NaOH pellets - Reagent grade.
• Stock 1.0 N NaOH - Dissolve 40 g of reagent grade NaOH in 1 liter
of C02 free distilled water. Stored in a pyrex glass container
with a tight-fitting rubber stopper.
• 0.0200 N NaOH - Dilute 20 ml of•1 N NaOH with C0£ free
distilled,water to 1 liter. Store in a tightly rubber-
stoppered pyrex glass bottle protected from atmospheric
C02 by a soda lime tube. For best results, prepare
daily. This solution will be standardized against potas-
sium biphthalate.
• Potassium biphthalate (KHCsH404)-Anhydrous - Reagent grade.
a 0.0200 N potassium biphthalate (KHP) solution - Dissolve
4.085 g of dry (110°C for 1 hour) KHP into 1 liter of C02
free distilled water.
NOTE
The normality of the KHP solution equals
(wt. KHP)/204.2.
• Anhydrous ethyl alcohol - U.S.P. or equivalent.
8-47
-------
• Phenolphthaleln Indicator solution - Dissolve 0.05 g of reagent
grade phenolphthaleln 1n 50 ml ethyl alcohol and dilute to 100 ml
with C02 free water,
• Bromphenol Blue Indicator solution - Dissolve 0.1 g in 7.5 ml
of 0.02 N NaOH. Dilute to 250 ml with C02 free distilled water.
8.8.3.5 Procedures
Technique Since the end points for tltrations are very color depen-
dent, the end point will probably vary slightly for each operator's sense
of color. To obtain the most accurate data, the following techniques
should be employed in all titrations:
• Always add the same number of drops of indicator.
• Have the same operator do blank and sample.
0 Always titrate to the same color intensity.
• Avoid parallax errors — keep eyes at the same level as the
liquid meniscus and hold a white piece of paper behind it
with a dark line horizontal to the table top.
• Remove air bubbles from buret tip prior to use.
• Never store reagent 1n buret. Always rinse out buret with a
slight amount of titrant.
• Always record titrant type and volume used.
Standardization and Analysis
1) Pipet 10 ml of the 0.0200 N KHP solution into a 125 ml
wide-mouth Erlenmeyer flask.
2) Add 3 drops of the Phenolphthlein Indicator. With a
swirling action the flask, titrate with 0.02 N NaOH
solution until the first pink color stays. Record
the volume and repeat from (1) 1n triplicate. Repeat
this procedure using D.I. H20 (blank).
3} Average the volume used to titrate the KHP solution.
The true normality of the standard NaOH solution equals:
[(0.0200)]
10 ml
(ml titrant -ml tTank)
8-48
-------
4) To titrate the H2S04 in the condensation coil, probe,
and filter rinses, pi pet 10 ml of these solutions into
a 125-ml Erlenmeyer flask. Add three drops of the
Bromphenol Blue indicator to the solution and titrate
to the blue end point. Triplicate analyses should be
performed as well as an indicative blank. Be sure to
use the same size aliquot and number of drops during
the blank test titration. (See Paragraph 8.8.3.2).
Remember this Bromophenol Blue sample blank is added
to the sample value.
Calculations Using either the sulfate of acid/base titration, the
concentration (ppm, V/V) of $03 as H2S04 in the flue gas stream can be
calculated.
1) From the Field Data Sheet obtain the average dry test
meter temperature, volume of gas sampled and atmospheric
pressure. Record these values on the Laboratory Data
Sheet (Appendix B).
2) Using the Laboratory Data Sheet, insert the correct
numbers into the following formula:
ppm H2S04 -1202.52
The result is ppm (v/v) H2S04 at STP.
NOTE
This value can be 12 percent low due to fly ash
present on the filter
Accuracy Check. In order to check the accuracy of the titrations
performed on these samples, an Independent check of the NaOH solution
and titration method is required. An unknown standard sample of H2S04
approximately 0.01 N should be analyzed by the lab personnel every couple
of weeks. Analysis of the sample should be in triplicate and reported to
3 places (O.X Y Z). Analysis of this sample will provide information on
the precision of the CCS titrations and accuracy of the results.
8-49
-------
The procedure follows:
1) Take a 10 ml aliquot of the unknown standard.
2) Titrate in triplicate with Bromphenol Blue to the blue
end point and record the number of millilHers used.
3) Determine the normality of the solution from:
NB VB
where
N. = Normality of the acid
V- = Volume acid aliquot taken (ml)
ND = Normality of the base
D
VD = Volume of the base used to titrate the sample (ml)
b
The results of the determination should not differ by more than
±10 percent within the triplicate numbers nor should the determined normality
be off by more than ±10 percent.
If the values differ by more than 10 percent:
• Check the calculations and be sure the correct values have
been used.
• Repeat the analysis.
• If the value is still off, restandardize the NaOH with KHP.
0 Repeat the test.
8.9 FLUORIDE ANALYSIS
8.9.1 Scope and Application
This method is applicable to the measurement of fluoride in aqueous
bulk liquids, solutions from H202 containing impinger samples, aqua regia
extractions and Parr bomb combustions of SASS train samples.
Concentrations of fluoride from 0.1 up to 1000 ppm may be measured.
Concentrations as low as 0.02 ppm can also be measured but a substantial
8-50
-------
length of time (on the order of several minutes) may be necessary for the
electrode to stabilize and respond to the sample.
8.9.2 Summary of Method
Fluoride is determined potentiometrically using a selective ion
fluoride electrode in conjunction with a standard single junction sleeve-
type reference electrode and a pH meter having an expanded millivolt scale
or a selective ion meter having a direct concentration scale for fluoride.
Sample pH should be between 5 and 9. Polyvalent cations of Si+4,
Fe+3 and Al+3 interfere by forming complexes with fluoride. The addition
of a pH 5 total ionic strength adjuster buffer (TISAB II) containing a
strong, chelating agent preferentially complexes aluminum (the most common
interference), silicon, and iron and eliminates the pH problem.
The addition of TISAB II also provides a high total ionic strength
background to help mask the difference in total ionic strengths between
samples and standards. However, the TISAB II can not entirely compensate
for this difference due to the very high and variable level of ionic
strength in the Level 1 SASS samples. Thus a known addition technique is
employed to eliminate the necessity of drawing different calibration curves
for different types of samples.
8.9.3 Apparatus
t Electrometer (pH meter), with expanded mv scale, or a selective
ion meter.
• Fluoride Ion Activity Electrode
t Reference electrode, single junction sleeve-type. Because
all the SASS samples for fluoride measurement have an ionic
strength above 0.2 M, the filling solution used is 4 M KC1
(saturated with respect to silver ion by adding a dilute
silver nitrate solution dropwise, until a milky silver
chloride precipitate froms.)
• pH electrode
• Magnetic mixer, Teflon-coated stirring bar.
8-51
-------
• Plastic lab ware - glassware cannot be used because of its
reaction with fluoride.
Beakers, 150 ml
Volumetric flasks, 50 ml
Pi pets, 100 ml
• Graph paper - 4 cycle, semi log.
8.9.4 Reagents
• Total ionic strength adjuster buffer (TISAB II) -This
solution can be obtained commercially (Orion # 94-09-09)
or prepared in laboratory by adding 57 ml of glacial
acetic acid, 58 g of sodium chloride and 2g of CDTA to
approximately 500 ml deionized water in a 1 liter beaker^1/.
Stir to dissolve and cool to room temperature. Adjust
pH of solution to between 5.0 and 5.5 with 5 N sodium
hydroxide (about 150 ml will be required). Transfer
solution to a 1 liter volumetric flask and dilute to the
mark with deionized water.
• Sodium fluoride solution: 1.0 ml =0.1 mg F. Dissolve
0.2210 g of sodium fluoride in deionized water and dilute
to 1 liter in a volumetric flask. Store in chemical-
resistant glass or polyethylene.
• NaOH, 5 N - Dissolve 20 g of NaOH in 100 ml of deionized
water.
0 HMOs* 1:1 - Dilute 500 ml cone. HN03 to 1 liter with deionized
water.
8.9.5 Procedure
8,9.5.1 Sample Preparation
Take a 5 ml aliquot of the sample and dilute it to ^0 ml with
deionized water in a 150 ml plastic beaker. Add 50 ml of TISAB II, mixing
~[T] CDTA is known as either cyclohexylene dinitrilo tetraacetic acid or
1,2 diaminocyclohexane N, N, N1, N1, —tetraacetic acid.
8-52
-------
well. Measure the pH by pH electrode. Adjust the pH to 5.0 - 5.5 with
5 N NaOH. Bring the final total volume to 100 ml with deionlzed water.
8.9.5.2 Calibration of the Electrode and the Meter
1) Read the manufacturer's Instruction manual for the
electrode and the meter to understand their operating
procedures.
2) To measure the fluoride concentration using the known
addition technique, the fluoride concentration of the
sample must be known to within an order of magnitude,
and a calibration curve must be prepared for that
concentration range.
3) Prepare a series of standards 1n the range of 0.02 to 10 ppm
by plpetlng the appropriate volumes of stock fluoride solution
Into 50 ml volumetric flasks. Add 0.5 ml of 1:1 HN03 to
simulate the sample matrix of most SASS samples. Add deionlzed
water to bring the volume to 50 ml.
4) Measure the potential of these standards as described
1n Section 8.9.5.3.
5) Using semllog graph paper, plot the concentration of
fluoride 1n mg/Hter on the log axis vs. the electrode
potential developed 1n the standard on the linear axis,
starting with the lowest concentration at the bottom of
the scale.
6) From the calibration curve, read the value of the slope
(the change 1n potential observed when the concentration
changes by a factor of ten). Correct electrode and
meter operation 1s Indicated by a slope of 58 ± 1 mV,
at a temp of 20° - 25°C. If the change 1n potential
1s not within this range, refer back to the manufacturer's
manual for suggested corrective actions.
8.9.5.3 Measurement of Potential
1) Place 50.0 ml of sample or standard solution and 50.0 ml
of buffer 1n a beaker.
2) Place on a magnetic stlrrer and mix at medium speed. Use
the nominal values of the standards 1n calibrating the
electrodes, e.g.. If a 10 ppm standard 1s diluted with
TISAB, the reading obtained 1s still designated "10 ppm".
8-53
-------
3) Immerse the electrodes in the solution and observe the
meter reading while mixing. The electrodes must remain
in the solution for at least three minutes or until the
reading has stabilized. At concentrations under 0.5 ppm
F, it may require as long as five minutes to reach a
stable meter reading: higher concentrations stabilize
more quickly.
4) Record the potential measurement for each unknown sample
and convert the potential reading to the fluoride ion
concentration of the unknown using the standard curve.
8.9.5.4 Known Addition Procedure
1) Measure the potential of the sample solution at 25°C as
described above. Leave the electrode in the solution.
2) Prepare a 50 ml standard solution containing about 10
times as much fluoride as the sample. Add 50 ml TISAB II.
(Use the nominal value of the standard in calculating
results; e.g., if a 10 ppm standard is dilute with
TISAB, the standard is still designated "10 ppm".
3) Pipet 10 ml of this standard into the sample solution
and stir well.
4) Record this potential measurement also.
8.9.6 Calculations
Calculate the difference in potential,AE, after the addition of the
fluoride standard.
From Table 8.2, find the concentration ratio, Q, that corresponds to
the change in potential,AE. To determine the original total sample
concentration, multiply Q by the concentration of the added standard:
C0 = fQCs
where:
C = total sample concentration
Q = reading from known addition table
C = concentration of added standard
f = dilution factor, e.e., if a 5 ml sample aliquot is taken and
diluted to 50 ml, then f = 10.
8-54
-------
Table 8-2.
Fluoride Analysis: "Addition Procedure" Table for Q
AE traillivolts) at 25°C for 10% Volume Change
vs
AE
-5.0
5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8
8.9
Q
0.297
0.293
0.288
0.284
0.280
0.276
0.272
0.268
0.264
0.260
0.257
0.253
0.250
0.247
0.243
0.240
0.237
0.234
0.231
0.228
0.225
0.222
0.219
0.217
0.214
0.212
0.209
0.207
0.204
0.202
0.199
0.197
0.195
0.193
0.190
0.188
0.186
0.184
0.182
0.180
AE
10.0
10.2
10.4
10.6
10.8
11.0
11.2
11.4
11.6
11.8
12.0
12.2
12.4
12.6
12.8
13.0
13.2
13.4
13.6
13.8
14.0
14.2
14.4
14.6
14.8
15.0
15.2
15.4
15.6
15.8
16.0
16.2
16.4
16.6
16.8
17.0
17.2
17.4
17.6
17.8
Q
0.160
0.157
0.154
0.151
0.148
0.145
0.143
0.140
0.137
0.135
0.133
0.130
0.128
0.126
0.123
0.121
0.119
0.117
0.115
0.113
0.112
0.110
0.108
0.106
0.105
0.103
0.1013
0.0997
0.0982
0.0967
0.0952
0.0938
0.0924
0.0910
0.0897
0.0884
0.0871
0.0858
0.0846
0.0834
AE
-20.0
20.2
20.4
20.6
20.8
21.0
21.2
21.4
21.6
21.8
22.0
22.2
22.4
22.6
22.8
23.0
23.2
23.4
23.6
23.8
24.0
24.2
24.4
24.6
24.8
25.0
25.2
25.4
25.6
25.8
26.0
26.2
26.4
26.6
26.8
27.0
27.2
27.4
27.6
27.8
Q
0.0716
0.0707
0.0698
0.0689
0.0680
0.0671
0.0662
0.0654
0.0645
0.0637
0.0629
0.0621
0.0613
0.0606
0.0598
0.0591
0.0584
0.0576
0.0569
0.0563
0.0556
0.0549
0.0543
0.0536
0.0530
0.0523
0.0517
0.0511
0.0505
0.0499
0.0494
0.0488
0.0482
0.0477
0.0471
0.0466
0.0461
0.0456
0.0450
0.0445
AE
30.0
30.2
30.4
30.6
30.8
31.0
31.2
31.4
31.6
31.8
32.0
32.2
32.4
32.6
32.8
33.0
33.2
33.4
33.6
33.8
34.0
34.2
34.4
34.6
34.8
35.0
36.0
37.0
38.0
39.0
40.0
41.0
42.0
43.0
44.0
45.0
46.0
47.0
48.0
49.0
Q
0.0394
0.0390
0.0386
0.0382
0.0378
0.0374
0.0370
0.0366
0.0362
0.0358
0.0354
0.0351
0.0347
0.0343
0.0340
0.0336
0.0333
0.0329
0.0326
0.0323
0.0319
0.0316
0.0313
0.0310
0.0307
0.0304
0.0289
0.0275
0.0261
0.0249
0.0237
0.0226
0.0216
0.0206
0.0196
0.0187
0.0179
0.0171
0.0163
0.0156
8-55
-------
Table 8-2. Fluoride Analysis: "Addition Procedure" Table for Q
vs.. A€ (millivolts} at 25°C for 10% Volume Change (Continued)
AE
9.0
9.1
9.2
9.3
9.4
9.5
9.6
9.7
9.8
9.9
Q
0.178
0.176
0.174
0.173
0.171
0.169
0.167
0.165
0.164
0.162
AE
18.0
18.2
18.4
18.6
,18.8
19.0
19.2
19.4
19.6
19.8
Q
0.0822
0.0811
0.0799
0.0788
0.0777
0.0767
0.0756
0.0746
0.0736
0.0726
AE
28.0
28.2
28.4
28.6
28.8
29.0
29.2
29.4
29.6
29.8
Q
0.0440
0.0435
0.0431
0.0426
0.0421
0.0417
0.0412
0.0408
0.0403
0.0399
AE
50.0
51.0
52.0
53.0
54.0
55.0
56.0
57.0
58.0
59.0
Q
0.0149
0.0143
0.0137
0.0131
0.0125
0.0120
0.0115
0.0110
0.0105
0.0101
8-56
-------
8.10 CHLORIDE ANALYSIS
8.10.1 Scope and Application
This method is applicable to the measurement of chloride in aqueous
bulk liquids, solutions from H202 impingers, module condensates and rinses,
hot water extractions of particulates and Parr bomb combustions of Level 1
samples. Chloride concentrations from 0.05 to 1000 ppm may be measured.
8.10.2 Summary of Method
Chloride is determined potentiometrically using a solid state selective
ion chloride electrode in conjunction with a double junction reference
electrode and a pH meter having an expanded millivolt scale or a selective
ion meter having a direct concentration scale for chloride. The solid
state electrode is used because it is not sensitive to the higher levels
of nitrate, sulfate or bicarbonate which could be present in several of
the Level 1 samples. This method does require that the sample and standards
have the same total ionic strength. Because Level 1 samples can have a
very high and variable level total ionic strength, a known addition technique
is employed to eliminate the necessity of drawing different calibration
curves for different types of samples.
8.10.3 Apparatus
t Electrometer (pH meter), with expanded mv scale, or a selective
ion meter.
• Chloride ion activity electrode, solid state
• Reference electrode, double junction
• Magnetic mixer, Teflon coated stirring bar
• Beakers, 150 ml
• Pi pets
• Volumetric flasks, 100 ml
• Graph paper, 4 cycle, semilog.
8-57
-------
8.10.4 Reagents
t Sodium chloride stock solution: 1.0 ml = 1.0 mg Cl" Dissolve
2.037 g of sodium chloride in deionized water and dilute to
1 liter in a volumetric flask.
• HN03, 1:1 - Dilute 500 ml cone. HN03 to 1 liter with deionized
water.
8.10.5 Procedure
8.10.5.1 Calibration of the Electrode and the Meter
1) Read the manufacturer's instruction manual for the electrode
and the meter to understand their operating procedures.
2) To measure the chloride concentration using the known addi-
tion technique, the chloride concentration of the sample
must be known to within an order of magnitude. A calibra-
tion curve has to be drawn.
3) Prepare a series of standards in the range of 0.05 to
100 ppm by pipeting the appropriate volumes of stock
chloride solution into 100 ml volumetric flasks. Add
0.5 ml of 1:1 HNOs to simulate the sample matrix of most
SASS samples. Add deionized water to bring the volume
to 100 ml.
4) Measure the potential of these standards as described in
Section 8.10.5.2.
5) Using semi log graph paper, plot the concentration of
chloride in mg/liter on the log axis versus the electrode
potential developed in the standard on the linear axis,
starting with the lowest concentration at the bottom of
the scale.
6) From the calibration curve, read the value of the slope
(the change in potential observed when the concentration
changes by a factor of ten). Correct electrode and meter
operation is indicated by a slope of 58 ± 1 mV, at a temp
of 20°-25°C. If the change in potential is not within
this range, refer back to the manufacturer's manual for
suggested corrective actions.
8.10.5.2 Measurement of Potential
1) Put 50 ml of sample or an aliquot diluted to 100 ml into a
150 ml beaker.
2) Place on magnetic stirrer and stir at medium speed.
8-58
-------
3) Immerse the electrodes in the solution and observe the
meter reading while mixing. The electrodes must remain
in the solution for at least three minutes or until the
reading has stabilized. At concentrations under 0.5 ppm
Cl, it may require as long as five minutes to reach a
stable meter reading: higher concentrations stabilize
more quickly.
4) Record the potential measurement for each unknown sample
and convert the potential reading to .the chloride ion
concentration of the unknown using the calibration curve.
8.10.5.3 Known Addition Procedure
1) Measure the potential of the sample solution at 25°C as
described above. Leave the electrode in the solution.
2) Prepare a standard solution containing about 10 times as
much chloride as the sample.
3) Pi pet 5 ml of this standard into the sample solution and
stir well.
4) Record this potential measurement also.
5) Perform this procedure with a blank of 50 ml deionized
water also.
8.10.6 Calculations
Calculate the difference in potential,AE, after the addition of the
chloride standard.
From Table 8.3, find the concentration ratio , Q, that corresponds to
the change in potential, AE. To determine the original total sample con-
centration, multiply Q by the concentration of the added standard:
50 (QSCS - QbCb)
Co V
where:
C = total sample concentration
Q = reading from known addition table for the sample
C = concentration of added standard
V = volume of sample aliquot, ml
8-59
-------
Table 8-3. Chloride Analysis: "Addition Procedure" Table for Q
vs. AE (millivolts) at 25°C for 10% Volume Change
AE
+2.4
+2.3
+2.2
+2.1
+2.0
+1.9
+1.8
+1.7
+1.6
+1.5
+1.4
+1.3
+1.2
+1.1
+1.0
+0.9
+0.8
+0.7
+0.6
+0.5
+0.4
+0.3
+0.2
+0.1
0.0
-0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
Q
52.6
17.2
10.3
7.32
5.68
4.63
3.91
3.38
2.98
2.66
2.40
2.19
2.01
1.86
1.72
1.61
1.51
1.42
1.34
1.27
1.21
1.15
1.09
1.05
1.00
0.959
0.921
0.886
0.853
0.822
0.794
0.767
0.742
0.718
0.696
0.675
0.655
0.637
0.619
AE
4.5
4.6
4.7
4.8
4.9
5.0
5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
Q
0.322
0.319
0.312
0.307
0.302
0.297
0.293
0.288
0.284
0.280
0.276
0.272
0.268
0.264
0.260
0.257
0.253
0.250
0.247
0.243
0.240
0.237
0.234
0.231
0.228
0.225
0.222
0.219
0.217
0.214
0.212
0.209
0.207
0.204
0.202
0,199
0.197
0.195
0.193
AE
13.0
13.2
13.4
13.6
13.8
14.0
14.2
14.4
14.6
14.8
15.0
15.2
15.4
15.6
15.8
16.0
16.2
16.4
16.6
16.8
17.0
17.2
17.4
17.6
17.8
-18.0
18.2
18.4
18.6
18.8
19.0
19.2
19.4
19.6
19.8
20.0
20.2
20.4
20.6
Q
0.121
0.119
0.117
0.115
0.113
0.112
0.110
0.108
0.106
0.105
0.103
0.1013
0.0997
0.0982
0.0967
0.0952
0.0938
0.0924
0.0910
0.0897
0.0884
0.0871
0.0858
0.0846
0.0834
0.0822
0.0811
0.0799
0.0788
0.0777
0.0767
0,0756
0.0746
0.0736
0.0726
0.0716
0.0707
0.0698
0.0689
AE
27.0
27.2
27.4
27.6
27.8
28.0
28.2
28.4
28.6
28.8
29.0
29.2
29.4
29.6
29.8
30.0
30.2
30.4
30.6
30.8
31.0
31.2
31.4
31.6
31.8
32.0
32.2
32.4
32.6
32.8
33»0
33.2
33.4
33.6
33.8
34.0
34.2
34.4
34.6
Q
0.0466
0.0461
0.0456
0.0450
0.0445
0.0440
0.0435
0.0431
0.0426
0.0421
0.0417
0.0412
0.0408
0.0403
0.0399
0.0394
0.0390
0.0386
0.0382
0.0378
0.0374
0.0370
0.0366
0.0362
0.0358
0.0354
0.0351
0.0347
0.0343
0.0340
0.0336
0.0333
0.0329
0.0326
0.0323
0.0319
0.0316
0.0313
0.0310
8-60
-------
Table 8-3. Chloride Analysis: "Addition Procedure" Table for 0
vs. AE (millivolts) at 25°C for 10% Volume Change (Continued)
AE
1.5
1.6
1.7
1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
-3.0
3.1
3.2
3.3
3.4
v • T^
3.5
w • v
3.6
*/ • v
3.7
v • /
3.8
v • W
3.9
4.0
• 4.1
r • A
4.2
4.3
4.4
Q
0.602
0.586
0.571
0.556
0.542
0.529
0.516
0.504
0.493
0.482
0.471
0.461
0.451
0.441
0.432
0.423
0.415
0.407
0.399
0.391
0.384
0.377
0.370
0.363
0.357
0.351
0.345
0.339
0.333
0.327
AE
8.4
-8.5
8.6
8.7
8.8
8.9
9.0
9.1
9.2
9.3
9.4
9.5
9.6
9.7
9.8
9.9
10.0
10.2
10.4
10.6
10.8
11.0
11.2
11.4
11.6
11.8
12.0
12.2
12.4
12.6
12.8
Q
0.190
0.188
0.186
0.184
0.182
0.180
0.178
0.176
0.174
0.173
0.171
0.169
0.167
0.165
0.164
0,162
0.160
0.157
0.154
0.151
0.148
0.145
0.143
0.140
0.137
0.135
0.133
0.130
0.128
0.126
0.123
AE
20.8
21.0
21.2
21.4
21.6
21.8
22.0
22.2
22.4
22.6
22.8
23.0
23.2
23.4
23.6
23.8
24.0
24.2
24.4
24.6
24.8
25.0
25.2
25.4
25.6
25.8
26.0
26.2
26.4
26.6
26.8
Q
0.0680
0.0671
0.0662
0.0654
0.0645
0.0637
0.0629
0.0621
0.0613
0.0606
0.0598
0.0591
0.0584
0.0576
0.0569
0.0563
0.0556
0.0549
0.0543
0.0536
0.0530
0.0523
0.0517
0.0511
0.0505
0.0499
0.0494
0.0488
0.0482
0.0477
0.0471
AE
34.8
35.0
36.0
37.0
38.0
39.0
40.0
41.0
42.0
43.0
44.0
45.0
46.0
47.0
48.0
49.0
50.0
51.0
52.0
53.0
54.0
55.0
56.0
57.0
58.0
59.0
Q
0.0307
0.0304
0.0289
0.0275
0.0261
0.0249
0.0237
0.0226
0.0216
0.0206
0.0196
0.0187
0.0179
0.0171
0.0163
0.0156
0.0149
0.0143
0.0137
0.0131
0.0125
0.0120
0.0115
0.0110
0.0105
0.0101
8-61
-------
Q. = reading from known addition table for the blank
C. = concentration of standard added to the blank
8.11 PHENOLDISULFONIC ACID PROCEDURE FOR DETERMINATION OF NITROGEN OXIDES
(EPA Method 7)
8.11.1 Scope
8.11.1.1 Application
This procedure is dictated for the analysis of nitrogen oxides (NOx)
from stationary sources by the Environmental Protection Agency.* The sam-
ples received by the laboratory have been obtained by rapidly pulling the
sample gas into an evacuated 2 liter borosilicate vessel which contains 25 ml
of an absorbing solution. The sample gas will have been in contact with the
0.003 percent ^2 in 0.1 NH2S04 absorbing solution for a minimum of 16 hours
to ensure complete conversion of NOX to the nitrate ion.
The laboratory analysis requires first quantitatively transferring the
sample solution to an appropriate container, neutralizing it with NaOH and
evaporating it to dryness. The residue is then reacted with phenol-
disulfonic acid (PDSA), diluted and made alkaline with NltyOH. This results
in the formation of a yellow nitro chromogen which can be measured spectro-
photometrically at 405 nm.
8.11.1.2 Range
The range of the method is stated to be 2 to 400 mg NOX as N02 per dry
standard cubic meter, although 16 hours reaction time may not be adequate for
o
a complete reaction to occur whenever the NOx concentration is below 200 ppm.
8.11.1.3 Interferences
HC1, which will be present in stack gases from coal burning facilities,
will interfere with this determination due to the formation of NOC1. Method
7 does not offer any means of eliminating this interference. Martens, et al.»
have described procedural modifications which can be used to minimize this
2
problem.
^'Method 7 - Determination of Nitrogen Oxide Emissions from Stationary Sources."
Federal Register, Vol. 41, No. Ill, June 8, 1976. pp. 23085-23087.
2Martens, H.H., Dee, L.A., Nakamura, J.T., and Jaye, F.C., Environ. Sci.
Tech., Vol 7., December, 1973. pp. 1152-1154.
8-62
-------
Unacceptable variability in absorbance readings can also result from
solution turbidity, C02 evolution and the loss of nitro-PDSA by adsorption
onto the glass evaporating dish.
Filtering will remove turbidity. C02 evolution can be minimized by
slow, careful neutralization of the absorbing solution with NaOH. Also,
avoiding the addition of excess NaOH enhances the recovery and makes the
evaporation easier. Using new smooth evaporating dishes reduces the possi-
bility of nitro-PDSA absorbing or reacting with the silicates in the glass.
8.11.2 Apparatus
• Graduated cylinder-50 ml with 1-ml divisions
• Storage container-Leak-free polyethylene bottles
• Wash bottle- Teflon
• Glass stirring rod
0 pH test paper-Litmus paper is sufficient
• Volumetric pipets-Two 1-ml, two 2-ml, one 3-ml, one 4-ml and
two 10-ml, and one 25-ml for each sample and standard.
• Borosilicate Evaporating dishes - 175 to 250 ml capacity with
lip for pouring, one for each sample and each standard. N.B.
Use only new borosilicate glass dishes. Old dishes may be
etched and provide sites for nitro-PDSA to be absorbed and
lost.
• Steam bath. (A hot plate is not acceptable.)
• Dropping pi pet or dropper-Three required
• Teflon policeman-One for each sample and each standard
• Graduated cylinder-100-ml with 1-ml divisions
8-63
-------
• Volumetric flasks-50-ml (one for each sample). 100-ml (one
for each sample, each standard and one for the working standard
KN03 solution), and one 1000-mA.
t Spectrophotometer-To measure absorbance at 405 nm.
• Graduated pipet-10-ml, with 0.1-ml divisions.
t Analytical balance-To measure to 0.1 mg.
8.11,3 Reagents
Unless otherwise indicated, it is intended that all reagents conform
to the specifications established by the Committee on Analytical Reagents
of the American Chemical Society, where such specifications are available;
otherwise, use best available grade.
• Absorbing solution-Cautiously add 2.8 ml concentrated
H2S04 to 1 liter of deionized, distilled water. Mix
well and add 6 ml of 3 percent hydrogen peroxide, freshly
prepared from 30 percent hydrogen peroxide solution. The
solution should be used within one week of its preparation.
Do not expose to extreme heat or direct sunlight.
• Fuming sulfuric acid-15 to 18 percent by weight free sulfur
trioxlde. Handle with caution.
0 Phenol-White solid.
• Sulfuric acid-Concentrated, 95 percent minimum assay. Handle
with caution.
• Potassium nitrate-Dried at 105-110°C for minimum of two hours
just prior to preparation of standard solution.
• Standard solution-Dissolve exactly 2.1980 of dried potassium
nitrate (KNOa) 1n deionized, distilled water and dilute to 1
liter with deionized, distilled water 1n a 1000-ml volumetric
flask. For the working standard solution, dilute 10 ml of the
standard solution to 100 ml deionized distilled water. One
ml of the working standard solution is equivalent to 100 ug
nitrogen dioxide (NOg).
• Water-Deionized and distilled.
• Phenoldlsulfonic acid solution-Dissolve 25 g of pure white
phenol 1n 150 ml concentrated sulfuric add on a steam bath.
Cool, add 75 ml fuming sulfuric acid, and heat at 100°C
(212°F) for 2 hours. Store 1n a dark, stoppered bottle.
8-64
-------
8.11.4 Procedure
a) Note Level of liquid in container and confirm whether or
not any sample was lost during shipment by noting this on
analytical data sheet.
b) Transfer the contents of the shipping container to a 50-ml
volumetric flask, rinse the container twice with 5-ml portions
of deionized, distilled water, add the rinse water to the
flask and dilute to the mark with deionized, distilled water.
c) Mix thoroughly and pipet a 25 ml aliquot into the evaporating
dish.
d) Evaporate the solution to dryness on a steam bath (use only
a steam bath - a hot plate 1s unacceptable).
e) Add 2 ml phenoldisulfonic acid to the dried residue and
triturate thoroughly with a Teflon policeman. Be sure the
solution contacts all the residue.
f) Add 1 ml deionized, distilled water and 4 drops of concentrated
H2S04.
y) Heat the solution on a steam bath for 3 minutes with occasional
stirring.
h) Cool, add 20 ml deionized, distilled water and mix well.
i) Add 15 ml concentrated ammonium hydroxide slowly, preferably
dropwise, with constant stirring.
j) If the sample contains solids, filter through Whatman No. 41
filter paper into a 100-ml volumetric flask; rinse the
evaporating dish with three 5-ml portions of deionized,
distilled water and add these to the filter. Wash the filter
with at least three 15-ml portions of deionized, distilled
water. Add the filter washings to the contents of the
volumetric flask and dilute to the mark with deionized, dis-
tilled water. If solids are absent, transfer the solution
directly to the 100-ml volumetric flask, dilute to the mark
with deionized distilled water and mix thoroughly.
h) Measure the absorbance of the solution at 405 nm using the
blank solution as a zero reference. Dilute the sample and
the blank with a suitable amount of deionized, distilled
water if absorbance exceeds the absorbance of the 400 yg N02
standard.
8-65
-------
8.11.5 Calibration
a) Add 0.0 ml, 1.0 ml, 2.0 ml, 3.0 ml and 4.0 ml of the KN03
working standard solution (1 ml ± 100 yg NOg) to a series
of evaporating dishes.
b) To each, add 25 ml of absorbing solution, 10 ml deionized,
distilled water and N NaOH dropwise until the solution is
basic to litmus. (Avoid adding excess base.)
c) Follow the analysis procedure given in the preceding section,
beginning with step (d) to determine the spectrophotometer
calibration factor.
d) Calculate the spectrophotometer calibration factor Kc as
follows.
AH-2A0+3A04A.
K - 100 234
c xwu . 2,» 2.n 2.fl 2
where:
K = Calibration factor
A, = Absorbance of the lOOyg N0£ standard
A2 = Absorbance of the 200yg N02 standard
A3 = Absorbance of the 300yg N02 standard
A, = Absorbance of the 400yg N0£ standard
e) Repeat this calibration on every day samples are analyzed.
8.11.6 Calculations
Carry out the calculations, retaining at lease one extra decimal
figure beyond that of the acquired data. Round off figures after final
calculations,
Total yg N02 per sample.
m = 2KC AF
8-66
-------
where:
A = Absorbance of sample
F = Dilution factor (i.e., 25/5, 25/10, etc., required only if
sample dilution was needed to reduce the absorbance into
range of calibration)
K = Spectrophotometer calibration factor
m = Mass of NOX as N02 in gas sample, yg
NOTE
If other than a 25-ml aliquot is used for analyses, the
factor 2 must be substituted by a corresponding factor.
8-67
-------
APPENDIX A
CRITERIA FOR A COST-EFFECTIVE
LEVEL 1 QUALITY ASSURANCE PROGRAM
A-l
-------
APPENDIX A
This appendix discusses a cost-effective quality assurance proqram
for the EACCS Level 1 testing. The approach presumes that currently-
maintained test procedures and consistently trained personnel are available,
The quality assurance activities consist of monitoring compliance with
the established procedures and verifying the reproducibility of the data
produced from application of these procedures. The program is made cost-
effective by formulating Q.A. limits and emphases which are consistent
with the Level 1 accuracy requirement. Basically, this approach differs
from the approach used in Level 2 or Level 3 in that the emphasis is
centered on maintaining reasonable confidence that most data will fall
within the relatively broad limits of Level 1 testing, as opposed to
tightening controls so that maximum accuracy is obtained from a test.
For example, a Level 1 quality audit will verify that precautions are
effective against repeated occurrence of gross errors (i.e., errors much
beyond the desired accuracy factor of 3). An appropriate Level 2 or Level
3 quality audit would, in addition, verify that testing was within accept-
able limits of standard materials or carefully performed reference tests.
Early reduction in the quality testing needed to verify the quality limits
are being met 1s also possible because the requirements are less strin-
gent than for Level 2 or Level 3 tests. This technique is discussed 1n
this appendix for the program replicate testing and repeated testing of
"blank" reagents.
A. AUDITING LEVEL 1 TESTS
The Level 1 EACCS program is primarily intended as a screening mech-
anism for potential problem sources of pollutants, and an accuracy factor
of 3 has been used to express acceptability of sampling and analysis for
the Level 1 testing. An accuracy factor of three is liberal for many
accepted analytical test procedures and methods of sampling. For example,
2/3 of the analytical tests in Reference (a)* are precise (2 x coefficient
*Reference (a): Guidelines for Environmental Assessment Quality Assurance
Program, R.T.I. (Rough Draft), September 1976.
-------
of variation) to better than ± 30 percent, and biases, if present, are
corrected by various means such as calibration curves, etc. Thus the
analytical accuracy factor for these tests would be approximately 1.4.
Sampling error, i.e., the taking of a non-representative sample because of
non-representative conditions by poor identification of isokinetic points
in stacks, insufficiently flushed water lines, etc., is probably less than
a factor of 2 because of the probability that severely atypical conditions
will be noted by experienced personnel and because inherent random mixing
tends to reduce the effects of stratification, a major cause of non-repre-
sentative samples. Thus, except for specific tests or methods which may
be inadequately characterized at this time, the procedures and methods to
be used for Level 1 testing can be assumed to be inherently capable of
factor of 3 accuracy.
This is an important assumption. It means that normal day-to-day
sampling, material control testing, and standardization metrology are
adequately controlled by personnel selection, training programs, equipment
controls and supervision. In other words, existing practices, equioment
and personnel are "state-of-the-art" and controlled by adequate guidelines
and procedures to Level 1 accuracy. If this is so, the Level 1 quality
program should aim to reduce the occurrence of excursions from procedures
in factors which will cause undetected variation rather than verify the
adequacy of the procedures to produce Level 1 accuracy.
To do this, the quality program must identify and emphasize the
sources of error which are most likely to cause extreme variation. Examples
of such gross sources of error are:
• contamination
• cumulative buildup in sampling equipment
t sample loss or concentration
• transposed data numerals
t erroneously marked sample identity
0 incorrect physical units or loss of digits 1n recorded parameters.
In addition, particular procedures may have specific key items. Examination
of this 11st shows cleanup, mathematical procedures, and spillage to be
the features of each procedure needing quality assurance, rather than
traceabillty of reagents, routine instrument settings, etc.
A-3
-------
It 1s therefore assumed that Level 1 accuracy will be most probably
exceeded by human error In following procedural steps Involving potential
error sources similar to those above, which can be Identified from the
procedures.
If 1t 1s assumed further* that procedures are about equal.1n quality
control sophistication, the frequency of deviation from procedures will be
more related to an Individual than to the procedure Itself. Thus, if we
then audit a given total number of critical procedural steps for an Indi-
vidual (to be anonymous), we have a sample from which to estimate the
probable number of "failures" (critical procedure deviations) associated
with the testing by that individual. For example, using the binomial
population assumption for "successes" and "failures", the reliability of
the audited individual could be estimated to be 0.98 with 90 percent con-
fidence with no deviation in 114 points of audit, or with one deviation,
1n 193 points of audit. It must be noted that, hopefully, not all critical
procedural excursions will exceed Level 1 accuracy, consequently, a minimum
reliability of 0.98 may 1n fact represent a much higher actual reliability
in terms of the data reported being within Level 1 accuracy.
For some procedures, the assumption of Inherent Level 1 accuracy may
not be valid. Thus, in addition to the above audit, some characterization
of accuracy and precision will be needed. These procedures will then be
evaluated by using "spiked" samples, blind samples, standards, etc. If
Level 1 accuracy 1s not demonstrated, 1t will be necessary to study pro-
cedural detail to devise a tightened control for that procedure. Subs'e*
quent audits will then Include auditing the application of these tightened
controls.
B. SELECTION OF NUMBER OF BLANKS FOR A REAGENT USED REPEATEDLY FROM
THE SAME CONTAINER
B.I Nature of the Problem
Repeated blanks on the same container protect against probable gradual
contamination of the container during usage. This protection may be
excessive 1n terms of Level 1 accuracy when adequate chemical precautions
are taken. A more serious problem 1s the possible accidental gross
contaminations which could affect Level 1 results. However, gross
A-4
-------
contamination is a problem associated with compliance by personnel with
procedures and accepted techniques. The Q.A. technique discussed in
Section A provides a method for limiting the risk of gross contamination
on this basis.
To verify that continuous sampling of the same container is conserv-
ative, repeated sampling within containers is required. When it is demon-
strated that the value of the blank remains sufficiently stable during the
usage of the container that Level 1 accuracy will not be affected, sampling
of that type of container can be limited.
B.2 Limiting Accuracy Required for Blank
Assume the Level 1 accuracy to be within a factor of 3 for sampling
and analysis, and that the analysis alone is desired within a factor of 2.
For a factor of 2, the ratio of the highest allowable value to the lowest
is 4, i.e. » -~r> = 4» where 2y is the highest emission factor result and
y/2 is the lowest, and y is the true value. If the observed emission
factor average (an estimate of y) is A, then:
- 4 (A.I)
where a is the coefficient of variation divided by 100 times the multiple
of the "t" distribution selected to express the expected variation.
When Equation (A.I) is solved, a = 0.6, hence the emission factor
limiting accuracy is A ± 0.6A.
A second consideration is that normal chemical practice does not permit
values of blanks which constitute more than P percent of the total value,
i.e., the blank X 1s not permitted if X/(X + A) x 100 > P, where X is in
emission factor units. Hence, the maximum error allowed for the blank
(assuming no error in the uncorrected value) is:
|X - Xt| l(P/100)(0.6A) = 0.006PA (A. 2)
where Xt 1s the true value for the blank.
A-5
-------
B.3 Cumulative Contamination of Solvent Blanks
Suppose a solvent container contains sufficient volume for JTI_ tests,
and that a blank is always run on a new container. The first blank result
in terms of emission factor units is X , and its error is X - Xt. The
second blank error is then X, - Xt, and an estimate of the progressive
contamination expected is (X, - X.) - (X - Xt) = X, - X = A, .
Additional extimates of this progressive contamination are given by
(X2 - Xj) = A2, (X3 - X2) = A3, etc.
As long as the blanks are tested, the progressive error is accounted
for, since the most recent blank is used in the computation and the
residual error, (X^ - Xt), becomes part of the overall reproducibility of
the test, to be discussed in Section C. However, if blanks are no longer
tested, the subsequent values for blanks must be approximated. One method
for doing this is to determine the average change between consecutive
blanks, A, and add one A to each successive use, starting with the last
measured value for the blank. A is calculated from:
- V =T= 1/(n-]) s Ai (A'3)
If, for example, after n tests, no more blanks are run,. the last
result, X , will be used by adding to it A for each succeeding use. Tbere
will be (m - n) times that the value for the blank will be used without
further confirmation. The estimate to be used will be X , and X . ,
= Xn + A", Xn+2 = Xn + 2A, and the last usage will be:
Xm = Xn + (m - n>s- (A'4)
If the last usage still meets the criteria of Level 1 accuracy, all earlier
usages are also acceptable. The added variability of Xm is due to the
uncertainty in knowing the value of A to be used. This uncertainty 1s
calculated from the standard deviation of "A, which is:
A-6
-------
The expected limit of variation of A is taken as tS^, where t is
selected at a selected confidence level, and n - 2 degrees of freedom.
Then, the estimated error of cumulated, but untested contamination of
the blank is for X , (m - n) tSp and this is limited by Equation {A. 2)
to:
0.006PA > (m - n) tS (A.6)
or
If Sy /A 1s less than this limit, additional blank testing is not
required. For example, suppose that we do not wish to make an excessively
large blank correction more than one time 1n eight (12.5%). "Excessively
large" 1s taken to mean that the blank Is more than 10% of the emission
factor (P = 10%), and the observed variation of the average blank already
run 1s about + 0.01A. 0.01A, expressed as the standard deviation, S^,
[Equation (A. 5)]. Assume the container holds 10 usages, or m = 10. Then,
from Equation (A. 7):
0.006 x 10 > 0.01A
(10 - n)t " A
6 > (10 - n)t
6/t S 10 - n.
By examination of the t table at n - 2 degrees of freedom (since
we are using the variance of A\ one degree of freedom is used to com-
pute "A) .
A-7
-------
n
3
4
5
6
7
t
2.41
1.60
1.42
1.34
1.30
10 - n
7
6
5
4
3
6/t
2.5
3.75
4.23
4.46
4.60
When 6 blanks have been tested, the blank correction can be
calculated for the next 4.
Equation (A.7) was used to plot the cases where blanks are proposed
to be tested for 1/3, 1/4, and 1/5 of the total usage of the reagent
(n/m) for various sized containers. To do this, Equation (A.7) was
modified to express the ratio n/m:
SA _ 0.006P
(m - n)t
(A. 8)
0.006P
n(m/n - l)t
In the figure, the ratio S^/A, the repeatability of the average
difference between blanks to the emission factor value for a test (the
ordinate) is a measure of the allowed lack of reproducibility of blanks
for a given level of emission factor. Thus, when one-third of the total
solvent usage times are tested for blanks, m/n = 3, only about half as
accurate blanks are required than if only one-fifth of the total solvent
usage times are tested, m/n = 5. Figure 1 shows:
• SA/A is initially stringent because the variability of the
blank is not well-known.
t SA/A tends to become more stringent with containers which
contain more total usages (increase in m) , which is in the
direction one would intuitively desire.
• An optimum reagent container size selection is possible.
C. SELECTION OF NUMBER OF REPLICATES FOR LEVEL 1 TESTING
In Section B, the accuracy factor, X, of 2 was used 1n finding
the criteria for the repeating of a blank sample analysis. Since the
-------
Figure 1. Minimum Repeatability Requirement for Discontinuance of Blank Tests
to
.004
.003
.002
.001
STOP TESTIHG AFTER
1/5 OF REAGENT USED
O
STOP TESTING AFTER
1/3 OF REA6EIT •USED
STOP TESTING;AFTER.
1/4 OF REA6EBT USED
HIMBER OF BLANKS TESTED
7 8
10 11
-------
resulting blank sample testing limitations use up a part of the accuracy
factor of 2 allowed for an analysis, we must determine the remaining
allowable accuracy limits. If P, the percentage allowable allocation to
the blank is 10 percent, then, for a total factor of 2, where A is the
emission factor, the fraction, a, allowable variation in A is found from
the emission factor data ratio, or:
A + (0.9 + 0.1 )aA 2A .
A - (0.9 + 0.1 )aA " 1/2 A ~ *
a = 0.6
0.9a = 0.54
xA
Then, if x is the new emission factor data ratio for analysis =
0.46
the accuracy factor for analysis is, thus, 1.83.
If replicate analyses should have a 90 percent confidence limit
that the test results will fall within ±0.54A, a Student "t" value at
this level can be used and,
tS ^ ±0.54A
(A.9)
S. < ±0.54
A " t
S is to be estimated from pairs of tests, with each pair giving one
degree of freedom for S. Such a pair is called a duplicate analysis,
and the numbers of such pairs, n, is to be found by solving Equation
(A.9) with values from the t table (two-sided), e = 0.10. The value of
n which meets Equation (A.9). 1s then selected. For tests In which S/A
clearly meets the criteria by being very small, when n = 1 , no further
replication is needed. For tests in which the criteria for Equation (A.9)
can probably be met by replication between n = 1 and n = 17, n should
be selected from Equation (A.9) (n = 17 is a budget constraint that
A-10
-------
about 10 percent of the samples may be retested during the duration of
the program). For tests which clearly will not meet the coefficient of
variation, S/A, requirement [Equation (A.9)], the following method
should be used.
The Level 1 accuracy requirement for these tests is 1.83 (see above),
Even though a, the true variation in the method, is too large to meet
the accuracy requirement, it will be useful to limit the extent to which
our test sample, S, can wander about the true value a. If we know this,
then we can at least identify the best accuracy factor that can be
expected at a level of confidence.
We assume that the true value of the standard deviation, a, should
not be less than S/1.83, nor greater than 1.83S which is the accuracy
factor ratio of 3.348 used before. This implies the only inaccuracy in
the emission factor over a is that due to our imperfect knowledge of a,
and hence is the best accuracy we could have.
Then, if we choose a 5 percent risk level for 0.547S < a < 1.83S,
the sample size can be derived from an F table with («>, n) degrees of
freedom or directly from the table given in Dixon and Massey, Introduc-
tion to Statistical Analysis, 3rd Ed., McGraw-Hill, 1969, Pg. 469.
The lower limit, with only 5 percent chance of a being smaller,
can be established with n = 2. The upper limit with 95 percent chance
that a is not larger, can be established with n = 6.
Hence 6 replicates will adequately characterize a at Level 1
accuracy under the assumptions made.
Equation (A.9) and the limit for S discussed above were used in
Figure 2-10 as the decision criteria to discontinue replicate testing.
The decision plan of 2.6.5 was developed, however, as an extension
of this approach to cover testing in more than one site, in which the
same analytical method and technicians were used, and the general site
complexities were the same. It is assumed that the sampling and
analysis reproducibility is the same among these similar sites, and thus
the variability obtained from the replicate analyses among the sites
A-ll
-------
can be pooled and used to reduce the need for added replication. In this
case, S, as used above becomes SA (a pooled estimate of variability
among the sites for analyses "A"), and the criteria uses A, which is the
weighted average value of analyses ''A" among the similar sites.
A-12
-------
APPENDIX B
ANALYTICAL TRAVELER WORKSHEETS
B-l
-------
Requestor.
JN
Assigned to __
Date Assigned
WORKSHEET FOR SOXHLET EXTRACTIONS - PROCEDURE 7.3.2
Summary: Samples are extracted for 24 hours with meth/lene chloride. At the end of the
extraction, sol vent sample is dried with sodium sulfate and concentrated with the Kuderna-
Danish apparatus.
Sample
Control
Number
(SCN)
Soxhlet
Size
Sample
Weight
(0)
Aliquot
Factor
Initial
Solvent
Volume
(ml)
B-2
Completion
Date /Initials
Comments
and
Observations
-------
Requestor,
JN
Assigned to_
Date Assigned,
WORKSHEET FOR KUDERNA-DANISH CONCENTRATIONS - PROCEDURE 7.4
Summary: The volume of each sample is measured and then each sample is dried and concentrated
to ~ 5 ml. The concentrate is transferred to a 10 ml volumetric flask and brought to volume with
the' same solvent as the sample. Two 1 ml aliauots are taken for the GC and grav. analyses and
[he remaining 8 ml are transferred to a vial. All samples are labeled and placed in the refrigerator
For storage.
Sample
Control
Number
(SCN)
Sample
Solvent
Sample
Volume
M)
Completion
Date/Initials
B-3
Comments
and
Observations
Disbursement
-------
Requestor.
JN
Assigned to_
Date Assigned
WORKSHEET FOR GRAVIMETRY - PROCEDURE 7.5
Summary: Each sample Is received in a small glass bottle. The entire contents of each bottle
are transferred to a fared aluminum weighing dish. The sample is allowed to evaporate to
dryness at ambient conditions and is weighed back. IR scans are then conducted with the
evaporated residues.
Sample
Control
Number
(SCN)
Sample
Solvent
Sample
Aliquot
Factor
Gravimehy, (g)
Rsd&dish
Di>h
Residue
Rsd & dish
Dish
Residue
Rsd & dish
Dl.h
Residue
Rid & dish
Dl.h
Residue
Rsd & dish
Dl.h
Residue
Rsd & dish
ni.h
Residue
Rsd & dish
Dt.h
Residue
Rsd & dish
Dish
Residue
Rsd & dish
Dish
Residue
Grav.
Comple-
tion
Date/
Initials
IR
Comple-
tion
Date/
Initials
Comments
and
Observations
B-9
-------
Requestor
JN
Assigned to«_
Date Assigned
WORKSHEET FOR GRAV/IR ON LC FRACTIONS - PROCEDURES 7.5 AND 7.6
Summary: Samples will usually be received In 10 or 25 ml volumetric flasks. The entire volume of
each sample fraction is evaporated and weighed. Fractions 1 - 7 are done in aluminum pans and
Fraction 8 In « small glass dish. If the grav. result is >15 mg, be careful to use no more than half
the residue for the IR scan.
Sample
Control
Number
(SCN)
Fraction 1
Fraction 2
Fraction 3
Fraction 4
Fractions
Fraction 6
Fraction 7
Fraction 8
Sample
Volume
(ml)
Sample
Aliquot
Factor
Gravimetry, (g)
Rsd & dish
D1«h
Residue
Rsd & dish
nt.h
Residue
Rsd & dish
Dlth
Residue
Rsd & dish
nuk
Resjdue
Rsd & dish
nt«K
Residue
Rsd & dish
Dt.k
Residue
Rsd & dish
ni.k
Residue
Rsd & dish
ni.k
Residue
Grav.
Comple-
tion
Date/
Initials
IR
Comple
rlon
Date/
Initials
Comments
and
Observations
B-5
-------
Requestor.
JN
Assigned to
Date Assigned.
WORKSHEET FOR TCO (C7-C16) GC - PROCEDURE 7.7
Cfl
Summary: Samples are received in small glass vials and are analyzed by the conditions and
parameters set forth in the procedures manual. These parameters should also be recorded on
the chromatogram. After analysis, the samples are stored in the refrigerator for subsequent
POM GC/MS analysis.
Sample
Control
Number
(SCN)
Comple-
tion
Date
/Initials
Injection
Volume,
Ml
Total
Sample
Volume,
ml
Quantitation, jtig
a
O3
C9
CIO
Cll
CI2
CIS
CH
CIS
C16
Total
-------
Requestor
JN
Assigned to _
Dote Assigned.
WORKSHEET FOR LC SEPARATIONS - PROCEDURE 7.8
Summary: The indicated volume of sample is evaporated to a residue unless a solvent exchange
is called for. The sample 5s then placed on the prepared column and eluted using 8 solvent frac-
tions. The fractions are collected in volumentrtc flasks and 1 ml aliquots are taken if TCOs are
to be done on the fractions, (i.e., those samples that go through the solvent exchange procedure).
Sample
Control
Number
(SCN)
Solvent
Exchange
Needed
Sample
Solvent
Aliquot
To Be
Taken
(ml)
Organic
Loading
inLC
Aliquot
Comments
and
Observations
Comple-
tion
Date/
Initials
B-7
-------
Requestor
JN
Assigned to
Dote Assigned _
Required Completion Dote _
WORKSHEET FOR ROMs BY GC/MS - PROCEDURE 7.10
Summary: Generally 1 ml sample aliquot* are received after their analysis for
C7-17. The samples are then evaporated under a stream of high-purity inert
gas and made up to 2 ml with the internal standard and benzene* Procedures
for performing the GC/MS analysis are given in the EACCS manual and
instrument operating manuals. Attach tabulation of reduced data to this
worksheet.
Sample
Control No.
(SCN)
Sample
Description
Type of
Source
/B-8
Initial
Sample
Volume
(ml)
Volume
Before
Injection
(ml)
Injection
Volume
foo
Date
Complete/
Initials
-------
GC/MS PACKING SHEET
Complete, sign, and return to Indicate receipt of samples.
Sample
Control No.
(SCN)
Volume
Sample
Description
Requestor __
Date Shipped.
Date Received.
Received By—
Condition
After
Shipment
B-9
-------
DESICCATION OF SOLID SAMPLES TO CONSTANT WEIGHT
\Mtnp
1.
3.
lerion uares
2.
4.
Indicate by numbers in box
under Sample column.
1.
2.
3.
4.
5.
7.
8.
1.
2.
3.
4.
5.
6.
7.
8.
1.
2.
3.
4.
5.
6.
7.
8.
1.
2.
3.
4.
5.
6.
7.
8.
TARE WEIGHT
9.
IP.
11.
12.
13.
14.
15.
16.
9.
10.
11.
12.
13.
14.
15.
16.
9.
10.
11.
12.
13.
14.
15.
16.
9.
10.
11.
12.
13.
14.
15.
16.
ALL WEIGHTS IN GRAMS
Requestor
JN
Assigned to
Dare Assigned
TARE + SAMPLE WEIGHT 1
1. 9.
SAMPLE FILTER OR
NUMBER CONTAINER*
NUtK OK CONTAINER
PLUS SAMPLE
FILTER OR
CONTAINER TARF
SAMPLE
SAMPLE FILTER OR
NUMBER CONTAINER*
rlLIcK OK CONTAINER
PLUS SAMPLE
FILTER OR
CONTAINER TARE
SAMPLE
SAMPLE FILTER OR
NUMBER CONTAINER*
FILTER OR CONTAINER
PLUS SAMPLE
_ FILTER OR
CONTAINER TARE
SAMPLE
SAMPLE FILTER OR
— klllilBCB — — . _.
NUMBER CONTAINER*
FILTER OR CONTAINER
_ PLUSSAMPlF
- FILTER OR
CONTAINER TARE
SAMPLE
2.
3.
4.
5.
6.
7.
8.
1.
2.
3.
4.
5.
6.
7.
8.
1.
2.
3.
4.
5.
6.
7.
8.
1.
2.
3.
4.
5.
6.
7.
8.
10.
11.
12.
13.
14
15.
16.
9.
10.
11.
12.
13.
14
15.
16.
9.
10.
11.
12
13.
14
15.
16.
9
10.
11.
12.
13.
14
15.
16. *
B-10
-------
INORGANIC SAMPLE DISBURSEMENT WORKSHEET
FOR SAMPLE COMBINATION
Requestor _
JN
Assigned to
Date Assigned.
Indicate by number In box
under Sample column.
SAMPLE COMBINATION DISBURSEMENT
1. Combine the indicated aliquots for each COMPOSITE sample into one plastic (liquids) or glass (solids) container.
See Sec. 4.1.3.
2. Label the combined aliquots with the COMPOSITE SAMPLE NAME.
Quantities in grams or milliliters
COMPOSITE
SAMPLE
NAME
J
J
J
J
J
J
J
J
u
11
n
IF
J
H
U
COMPOSITE
TOTAL
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
SAMPLE #
AMOUNT
COMBINE THESE SAMPLE ALIQUOTS TO MAKE COMPOSITE SAMPLE
"
B-ll
-------
INORGANIC SAMPLE DISBURSEMENT WORKSHEET
FOR SAMPLE PREPARATION
Requestor
JN
Indicate by number in box
under Sample column.
Assigned to
Date Assigned
SAMPLE PREPARATION DISBURSEMENT
1. Place the indicated (IND.) aliquot amounts for each sample into separate plastic (liquids) or glass (solids)
containers.
A. Liquids - Use volumetric pipets or pipettors.
B. Solids - Cone and quarter to desired amount. Use microbalance. See Sec. 4.1.3.2 and Appendix D.
C. Filters - All filter weights are gross weights (filter + particulate). Use a pre-cleaned knife. See Sec. 4.1.3.3.
D. Slurries — Separate solids and liquids with Whatman #41 filter and Buchner funnel. Apportion solids and
liquids as above.
2. Label these aliquot containers with: A. The sample name and B. The sample preparation, e.g., AR, etc.
3. Write the actual (ACT.) amount disbursed. Notify the requestor if IND. and ACT. differ by more than 5%.
Quantities in grams or milliliters
SAMPLE
CONTROL NUMBER
(SCN)
ORIGINAL
AMOUNT
ALIQUOT FOR
IND
ACT
ALIQUOT FOR
IND
ACT
ALIQUOT FOR
INO
ACT
ALIQUOT FORn
IND
ACT
ALIQUOT FOR
IND
ACT
B-12
-------
Indicate by number in box
under Sample column.
INORGANIC SAMPLE DISBURSEMENT WORKSHEET
FOR SAMPLE ANALYSIS
SAMPLE ANALYSIS DISBURSEMENT
Requestor.
JN
Assigned to
Date Assigned.
1. Place the indicated (IND.) aliquot amounts for each sample into separate plastic (liquids) or glass (solids) containers.
A. Liquids — Use volumetric pipets or pipettors
B. Solids — Weighed on microbalance
C. Filters — Use a pre-cleaned knife
2. Label these aliquot containers with: A, The sample name and B, The sample analysis, e.g.. Hg, AA. ICP, SSMS, etc.
3. Write the actual (ACT.) amount disbursed. Notify the requestor if IND. and ACT. differ by more than 5%.
Quantities in grams or milliliters
SAMPLE
CONTROL
NUMBER
(SCNJ
ORIG
AMT
ALIQUOT
FOR
IND
ACT
ALIQUOT
FOR
IND
ACT
ALIQUOT
FOR
IND
ACT
ALIQUOT
FOR
IND
ACT
ALIQUOT
FOR
IND
ACT
ALIQUOT
FOR
IND
ACT
ALIQUOT
FOR
IND
ACT
ALIQUOT
FOR
IND
ACT
ALIQUOT
FOR
IND
ACT
ALIQUOT
FOR
IND
ACT
ALIQUOT
FOR
IND
ACT
w
-------
Requestor,
JN
Assigned to „__
Date Assigned
WORKSHEET FOR PARR BOMB COMBUSTIONS - PROCEDURE 8.2.1
Summary: Samples for SSMS analysis are prepared by combusting a one gram sample
using the quartz cup and lid arrangement. Tne combustion solution is rinsed direct!
into a Nalgene bottle made up to 50 ml, and labeled. Samples for Hg, As, Sb,
Cl, and/or F are prepared by a standard combustion of 1 to 2 grams of sample
followed by digestion on a hot plate and filtration of the solids. The filtrate is then
made up to 100 ml and labeled.
Sample
Control No.
(SCN)
Amount to
be Taken/
Forfe)
Sample Weighings
Final
Volume
(ml)
Date
Complete
/Initials
Disbursement
B-14
-------
Requestor,
JN
Assigned to _
Date Assigned.
WORKSHEET FOR AQUA REGIA DIGESTIONS - PROCEDURE 8.2.2
Summary: The weighed sample Is placed in a boiling flask and is refluxed with
constant boiling agua regia for six hours on a hot plate. The solution is filtered
into a Nalgene volumetric and made to a 100 ml volume when cool.
Volume
of Acid
Used
(ml)
Date
Complete
/Initials
Sample
Control No.
(SCN)
Final
Volume
(ml)
Weight of
Sample
(mg)
Sample
Aliquot
Factor
Disbursement
B-15
-------
Requestor.
JN
Asiignad to
Dott Assigned _
WORKSHEET FOR HOT WATER EXTRACTIONS - PROCEDURE 8.2.3
Summary: The weighed sample it placed In a boiling flask and Is refluxed with
delonlzed water for 1/2 hour. The solution Is then filtered and made up to
50 ml volume for analysis.
Sample
Control No.
(SCN)
Weight of
Sample
(mS)
Sample
Aliquot
Factor
Volume
of Water
Used
(ml)
Final
Volume
W)
Date
Complete
/Initials
Disbursement
9-16
-------
Assigned to _______
Dote Assigned
WORKSHEET FOR SSMS ANALYSIS - PROCEDURE 8.3
Summary: Typically, either 100 ml of an aqueous solution on 100 mg of a solid
are used to prepare the graphite sample electrodes. These electrodes are Ionized
and the resulting mass spectra are recorded on photoplates. Procedures for per-
forming the SSMS analysis are given in the EACCS manual and Instrument
operating manuals. Attach tabulation of reduced data to this worksheet.
Amounts used in this worksheet may be either volume or weight, so units must
be given for each sample.
Sample
Control No.
(SCN)
„
un
Amount
of
Prepared
Sample
Received
Amount
of
Prepared
Sample
Used
___•—
Initial
Amount
of
Prepared
Sample
Ratio of
Prepared
to Total
Sample
Appropriate
Blank to be
Subtracted
Factor
to be
Applied
to Blank
Sample
Gas
Volume
(DSCM)
•M^MHHMWB
Date
Complete
B.17
-------
SSMS PACKING SHEET
Complete, sign, and return to indicate receipt of samples.
Sample
Control No.
(SCN)
Volume or
Weight
Sample
Description
rv* ttitpp~i
B.«.iu~< Ry
Condition
After
Shipment
B-18
-------
Requestor
JN
Assigned to
Date Assigned
WORKSHEET FOR COLD VAPOR MERCURY - PROCEDURE 8.4
Summary: The indicated volume of sample is reduced with stannous chloride and
the elemental mercury formed is sparged into a quartz cell where its absorbance at
253.7 nm is measured. Special procedures must be followed for different types
of samples in order to get good results. The amount of Mercury in the sample
aliquot is read from a calibration curve.
Sample
Control No.
(SCN)
Type
of
Sample
Maximum
Volume
to be
Taken
(ml)
Actual
Volume
Taken
(ml)
Sample
Reading
Blank
Reading
Mercury
Amount in
Aliquot
to)
Concen-
tration
(fig/m\)
Date
Complete/
Initials
B-19
-------
Requestor,
JN
Assigned to.
Date Assigned
WORKSHEET FOR ARSENIC HYDRIDE GENERATION - PROCEDURE 8.5
Summary: The indicated volume of sample is diluted, if necessary, to 25 ml and is
reacted with zinc slurry and stannous chloride. The arsenic hydride formed is sparged
into an argon-hydrogen flame in the AA with a stream of argon, and its concentration
is measured at 193.7 nm. Special procedures must be followed for different types of
samples in order to get good results. The amount of Arsenic Is read from a calibration
curve.
Sample
Control No.
(SCN)
Type
of
Sample
Maximum
Volume
to be
Taken
(ml)
•
Actual
Volume
Taken
(ml)
Sample
Reading
Blank
Reading
Arsenic
Amount in
Aliquot
0/g)
Concen-
tration
G/g/ml)
Date
Complete/
Initials
B-20
-------
Requestor.
JN
Assigned to ___
Date Assigned,
WORKSHEET FOR ANTIMONY HYDRIDE GENERATION - PROCEDURE 8.6
Summary: The Indicated volume of sample is oxidized with H9SO^ and HNO,, and
then reacted with HCl, Kl, and SnCL reagents. The final * J
hydride evolution is done with NaBrL and the antimony is sparged with nitrogen into
a hydrogen diffusion flame in the AA. Its concentration is measured at 217.6 nm, and
the amount of Antimony is read from a calibration curve.
Sample
Control No.
(SCN)
TiT
Sample
Maximum
Volume
to be
Taken
(ml)
Actual
Volume
Taken
(ml)
B-2
Sample
Reading
Blank
Reading
Antimony
Amount
in
Aliquot
Concen-
tration
(ug/ml)
,
Date
Complete/
Initials
••MHBMH^M
-------
Requestor
JN
Assigned to
Date Assigned
WORKSHEET FOR TURBIDIMETRIC SULFUR - PROCEDURE 8.7
Summary: The indicated volume of sample is diluted, if necessary, to 100 ml,
reacted with barium chloride, and its turbidity measured after 10 minutes.
Colored and naturally turbid samples must also be measured before the addition
of BaCl2 reagent to obtain a blank reading.
Sample
Control No.
(SCN)
•
Maximum
Volume
to be
Taken
(ml)
Actual
Volume
Taken
(ml)
Blank
Reading
For Color
Reacted
Sample
Reading
Sample
Reading
Minus
Blank
SC
Amount
In Aliquot
(mg)
34
Concen-
tration
(mg/ml)
Date
Complete/
Initials
/
B-22
-------
Requestor
JN
Assigned to
D*to Assigned
WORKSHEET FOR BRUCINE NITRATE - PROCEDURE 8.8
Summary: The indicated volume of sample is mixed with rUSO^ and brucine reagents
under carefully temperature-controlled conditions. The developed color is measured
at 410 my. Measurements are also made before the brucine reagent addition to
correct for color already present in the sample by obtaining a blank reading.
Sample
Control No.
(SCN)
Maximum
Volume
to be
Taken
(ml)
Actual
Volume
Taken
(ml)
Blank
Reading
For Color
Reacted
Sample
Reading
,
Sample
Reading
Minus
Blank
,
NC
Amount
in Aliquot
frig)
>3
Concen-
tration
(mg/ml)
Date
Complete/
Initials
B-23
-------
Requestor.
JN
Assigned to
Date Assigned.
WORKSHEET FOR FLUORIDE ELECTRODE - PROCEDURE 8.9
Summary: The Indicated volume of sample is diluted, if necessary, to 50 ml and the
fluoride concentration is measured by specific ion electrode using a known additions
technique.
Sample
Control No.
(SCN)
Type of
Sample
Maximum
Volume
to be
Taken
(ml)
Actual
Volume
Taken
(nl)
Dilution
Factor
Initial
Reading
Reading
with Std.
Addition
Fluoride
Concen-
tration
in Undiluted
Sample
Date
Complete
Initials
B-24
-------
Requestor.
JN
Assigned to
Dote Assigned
WORKSHEET FOR CHLORIDE ELECTRODE - PROCEDURE 8.10
Summary: The indicated volume of sample is diluted, if
chloride concentration is measured by specific ion electi
technique.
necessary, to 100 ml and the
ecrrode using a known additions
Sample
Control No.
(SCN)
Type of
Sample
Maximum
Volume
to be
Taken
(ml)
Actual
Volume
Taken
(ml)
Dilution
Factor
Initial
Reading
Reading
with Std.
Addition
Chloride
Concentratior
in Undiluted
Sample
Date
Complete/
Initials
B-25
-------
WORKSHEET FOR
BY ATOMIC ABSORPTION SPECTROSCOPY
Method (M): A = Flame AAS; B • Graphite Furnace AAS
.DETERMINATION
Requestor.
JN
Assigned To
Date Assigned
A - FLAME PARAMETERS: Instrument
Abs Line _______ nm Energy .
Non Abs Line ______ nm Energy
.Slit.
Slit.
. Recorder
.Lamp Curr.
. Lamp Curr. .
.ma
ma
Fuel
Oxidant .
Flow.
Flow
B - GRAPHITE FURNACE PARAMETERS:
Abs Line ________ nm E
Non Abs Line nm I
Complexing Reagents (CR): (
Empty Tube Readings (Noise)
fERS; ln«ti-iim*nh , Amen Flow Rnmn
rmrgy _ Slit
1' *
. I.Cfnp Olrr,
_ lamp Curr. _____
mn DRY «.^
mn ASH soe.
,.l ATOM ,«r,
nmp
°C
•r
«r
Sample Control
Number (SCN)
M
CR
STD
ADD
Maximum
Volume
Allowed
Dilution
of Aliquot
Chart
Reading
Minus
Empty
Tube
Concentration
Aliquot
Slope
Correlation
Coefficient
B-26
-------
APPENDIX C
STANDARD EPA GAS SAMPLING METHODS
C-l
-------
23060
PROPOSED RULES
ENVIRONMENTAL PROTECTION
AGENCY
[40CFRPart60]
[FRL 636-4]
STANDARDS OF PERFORMANCE FOR
NEW STATIONARY SOURCES
Proposed Amendments to Reference
Methods
On December 23, 1071, the Environ-
mental Protection Agency promulgated
standards of performance for five cate-
gories of stationary sources under sec-
tion 111 of the Clean Air Act, as
amended. An appendix to the regulation
contained Reference Methods 1-9, which
detailed requirements for performance
testing of stationary sources. Since
promulgation of these reference methods
EPA has continued to evaluate them. As
a result, the need lor a number of
changes which would clarify the methods
and/or improve their accuracy and
reliability has become apparent. The
following proposed amendment* Incor-
porate these changes to Reference Meth-
ods 1-9. Revisions to Reference Method
9 were promulgated on November 12,
1974 (39 FR 39872).
Changes common to all eight of the
reference methods are: (1) the clarifica-
tion of procedures and equipment spec-
ifications, and (2) the addition of metric
units along with English units. Specific
changes to the methods are:
METHOD 1
A statement was added to clarify that
the method does not apply to stacks con-
taining cyclonic or swirling flow or stacks
smaller than 0.3 m (1 ft) in diameter or
0.07 m' (0.8 ff > in cross sectional area.
A procedure for verifying the existence
of non-cyclonic or non-swirling flow was
added. For cases where large cross sec-
tional variation of the pollutant concen-
tration is suspected or for unusually large
diameter stacks, the method was revised
to provide that more than two traverse
diameters may be specified by the
Administrator.
METHOD 2
The use of the method has been limited
to non-cyclonic or non-swirling gas
streams. Greater details for calibration
of the Type 8 pltot tube have been added
including: criteria for standard type
pltot tubes; specification of calibration
at 915 m/mln (3000 ft/min); details of.
acceptable wind tunnel systems; and
additional details for calibrating iso-
lated pltot tubes and pltobe assemblies.
' METHOD 3
For determining the molecular weight
of a stack gas sample, it is now acceptable
to use either an Orsat analyzer or a
Fyrite * type combustion analyzer. Previ-
ously, only the Orsat analyzer was
specified. The Integrated gas-sampling
train for. this method was altered to in-
clude a surge tank before the rate meter
in order to eliminate pulsation effects
.caused by the diaphragm pump. Also,
because this method requires propor-
tional sampling, an Inclined manometer
was added to the train to measure veloc-
ity head.
Where low CO. (less than 4%) or high
Oi (greater than 15%) concentrations
exist, the procedure has been revised to
require an Orsat having at least 0.1%
subdivisions. The revised method also
provides sampling site selection criteria
and criteria for determining the num-
ber of sample points. More detail has
been added to the analytical procedure.
Finally, the former criteria for three
consecutive measurements have been
changed to require three measurements
within 0.3% for greater than 3%'CO,
and 0.2% for less than 3% CO*
METHOD 4
This method now contains two sepa-
rate methods for moisture determina-
tion: (1) a reference method for cases
where the Method 5 train is not used, and
(2) an approximation method for mois-
ture content to be used for'setting isoki-
netic sampling rates. In the moisture
sampling'train by the approximation
method, the rate meter is now located
before the dry gas meter.
METHOD ft
The specification for temperatures
around the filter holder was revised to
read "no greater than 120 ±14* C
(248±28* F), or such other temperature
as specified by an applicable subpart of
the standards." The revised wording of
the temperature specification does not
change the procedure contained in the
original method; It only clarifies the In-
tended procedure by providing more
specific instruction. The revised language
also provides flexibility for the Adminis-
trator to specify other temperature limits
in applicable subparts of the standards.
Method 5 employs an but-of stack filter
to facilitate temperature control. This
usage is not changed by these proposed
amendments.' Specifications for weight
and volume measurements were changed
to reflect the capabilities of most widely
used apparatus. To further insure the
validity of the sample, leak checks of the
sampling train are now required after
i Mention of trada name* U not Intended
to constitute endowment by XPA.
sampling runs as well as before. Finally.
the gas-sampling train was altered to
include a stack gas temperature sensor.
^METHOD 0
In the sampling train, 4he flow control
valve is now located before the pump In-
stead of after to allow bettor leak checks.
Samples collected by the train are to be
diluted to 100 ml instead of 50 ml to al-
low the number of rinses of the Imping-
ers necessary for adequate sample recov-
ery. The average flow rate through the
sampling train was reduced to 1 liter/
min to prevent reagent carry-over from
one taplnger to the next
METHOD 7
A provision was added to require the
potassium nitrate used for preparation
of the standard solution to be dried at
105-110* C for a minimum of two hours.
Currently, during sample recovery,
sodium hydroxide is added to the sample
solution. These revisions require that
only enough sodium hydroxide be added
to adjust the pH to 9-12. This will pre-
vent a large excess of sodium hydroxide.
Similarly, during the analysis procedure,
only enough ammonium hydroxide may
be added to the sample to raise the pH
to 10. This requirement prevents possible
differences in color intensity due to an
excess of ammonium hydroxide. Also
during sample analysis, only one-half of
the sample is to be analyzed to avoid loss
of the sample due to analytical error.
Finally, two changes concerning the
spectrophotometor were made: (1) for
spectrophotometer calibration, an equa-
tion is provided to determine ft factor
that insures the best fit through the
calibration points, and (2) the absorb-
ftnce measurement is now to be made at
410 nm instead of 420 nm.
METHOD 8
During sample analysis a 10 ml ali-
quot of SO* sample is specified instead of
25 ml to reduce the amount of titrant re-
quired. A stack gas temperature sensor
was added to the integrated gas-sam-
pling train.
Finally, EPA is presently In the process
of converting the units in its standards to
the International System of Units (SI).
In keeping with this policy, we will soon
convert the equipment specifications and
procedures of the reference methods to
BL We anticipate that in some situa-
tions it wffl be necessary, for practical
application, to use a mixture of 81 and
metric units. We solicit any commento
that win expedite and facilitate tills
transition.
RDItAl UOISTIK, VOL 41, NO. Ill—TUM0AY, JUNI I, W*
C-2
-------
PROPOSED RULES
23061
By this notice, the Administrator Is In-
viting comments on the proposed revi-
sions. Submittals should, wherever pos-
sible, be supported with data and/
calculations.
Comments on the proposed revisions
should be submitted, In triplicate, to the
Emission Standards and Engineering
Division, U.S. Environmental Protection
Agency, Research Triangle Park, North
Carolina 27711, Attention: Mr. Don R.
Goodwin. All comments post-marked no
later than July 23, 1976 will be
considered.
Copies of comments received will be
available for public • inspection during
normal business hours at the Public In-
formation Reference Unit (EPA Li-
brary), Room 2922, 401 M Street, 8W.,
Washington, D.C.
nils amendment is proposed under the
authority of section 111 of the Clean Air
Act, as amended (42 U.S.C. 18S7c6).
Dated: May 27,1976.
JOHN QTJAHLBS,
Acting Administrator.
It Is proposed to amend Part 60 of
Chapter I of Title 40 of the Code of Fed-
eral Regulations by revising Methods 1
through 8 of Appendix A—Reference
Methods as follows:
APPENDIX A—RETEBENCE METHODS
METHOD 1—SAMPLE AND VELOCITY TBAVZBSES
FOB STATIONARY SOURCES
1. Principle and AppHeablUty,
1.1 Principle. A sampling site and the
number of traverse points are selected to old
in the extraction of a representative sample.
12 Applicability. This method la appli-
cable to sampling of gas streams contained
In ducts, stacks, or flues.
It la intended that all new sources con-
sider the requirements of this method before
construction of the affected facility. Should
they be overlooked, some sites may not lend
themselves to this method and temporary
alterations to the stack or deviation from the
standard procedure may be required. Such
cases are subject to approval by the Admin-
istrator.
This method Is not applicable to stacks
containing cyclonic or swirling flow (see
13.4) or stacks smaller than about 0.3 m
(1 ft) In diameter or 0.07 m* (0.8 ff) In cross
sectional area. When these eases are so-
countered, an alternate procedure, subject to
approval of the Administrator, is required.
2. Procedure.
2.1 Sampling site. Select a sampling site
that is at least 8 stack or duct diameters
downstream and 2 diameters upstream from
any flow disturbance such as a bend, ex-
pansion, contraction, or visible flame. If Im-
practical, select an alternate site that is at
least 2 stack or duct diameters downstream
and 0.8 diameter upstream from the flow
disturbances. For a rectangular cross section.
use an equivalent diameter calculated from
the following equation to determine the
respective distances:
D..
aLW
Equation 1-1
where:
D.=cquivalent diameter
L=Length
W=Width
2.3 Minimum number of traverse points.
When the 8 and 2 diameter criterion can be
met, the minimum number of traverse points
shall be 12 for stack diameters greater than
0.6m (M In.) and 8 for stack diameter* equal
to or less than 0.6 m (34 in.).
When the 8 and 3 diameter criterion can-
not be met, use Figure 1-1 to determine the
minimum number of traverse points. To
use this figure, first determine the dis-
tances from the chosen sampling location
to the nearest upstream and downstream dis-
turbances. Divide each distance by the diam-
eter or' equivalent diameter to determine the
distance In terms of the number of duct
diameters. Then, determine from Figure 1-1
the minimum number of traverse points that
corresponds (1) to the number of duct diam-
eters upstream and (8) to the number of
diameters downstream. Select the higher of
the two minimum numbers of traverse points.
or a greater value, such that for circular
stacks the number is a multiple of four, and
for rectangular stacks, the number follows
the criteria In section 2.3.2.
• NUMBER OF DUCT DIAMETERS UPSTREAM-
DISTANCE A
1.0 1.8
• FROM POINT OF ANY TYPE OF
DISTURBANCE (BEND. EXPANSION. CONTRACTION, ETC.]
4 C 6 7
•NUMBER OF DUCT DIAMETERS DOWNSTREAM •
DISTANCE 8
Figure M, Minimum number of traverse points.
23 Cross sectional layout and location of
traverse points.
24.1 Circular stacks. Locate ttte traverse
points on two perpendicular diameters ac-
cording to Table 1-1 and the example shown
In Figure 1-2.
When large cross sectional variation of the
pollutant concentration la suspected, the Ad-
ministrator may specify that more than two
diameters which divide the stack cross sec-
tion Into equal parts shall be used. More than
two diameters may also be used with ap^
proval from the Administrator for unusually
large diameter stacks.
One of the diameters shall be In a plan*
containing the greatest expected concentra-
tion variation, e.g., after bends one diameter
shall be in the plane of the bend. This latter
requirement becomes less critical as the dis-
tance from the disturbance increases. There-
lore, other diameter locations may be used,
subject to approval from the Administrator.
la addition, for stacks greater than 0.6 m
(24 in.) no sampling points shall be selected
within 3,64 cm (1 In.) of the stock walls, and
for stacks equal to or less than 0.6 m (24 In.),
no sampling points within 1.27 cm (V4 m.)
of the stock walls. To meet this criterion, do
the following:
2.8.1.1 Stacks greater than 0.6 m (24 In.).
When any of the traverse points, as located
in section 2.8.1. rail within 2.64 cm (1 in.) of
the stack walls, relocate them away from the
stack walls to a distance of (1) 3.64 cm (1
In.) or (2) a distance equal to the nozzle
inside diameter, whichever is larger. These re-
located traverse points (on eaoh end of a
diameter) shall be the "adjusted" traverse
points.
RDBIAl IMISnt, VOL 41, NO. Ill—TUBSDAY, JUNE 8, 1976
C-3
-------
23062
PROPOSED RULES
1
0 | 0
1
1
0 .} 0
— — p— -
1
0 | 0
t
t
1
l__
1
1
1
1
1
1
1
0 1 0
— -f — • — —
. 1 .
TrTjT ^^Jt ^m JTUI,, am *
o i o
Figure 1-3. Example showing rectangular slack cross section divided Into
12 equal areas, with traverse points at centroid of each area.
Table 1-1. Location of traverse points in circular stacks
JPercent_of ttack diameter fron^lnsjde^waiU to traverse point)
Traverse
point
number
on a
diameter
1
1
2
3
4
S
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Hur
2
14 6
1 ~ » V
85.4
4 1 6
6.7
W» *
25.0
7S.O
93.3
i
4.4
14.7
29.5
70.5
85.3
S5.6
ibcr of traverse p<
"ii nn a diamete
1 6
4.9
8.5
12.5
16.9
22.0
28,3
37.5
62.5
71.7
78.0
83.1
87.5
91.5
95.1
98,4
1.4
4.4
7.5
10.9
14.6
\8.8f
23.6
29.6
33.2
61.8
70.4
76.4
81.2
85.4
89.1
92.5
95.6
98.6
r
"20~
1.3
3.9
6.7
9.7
12.9
16.5
20.4
1.1
3.5
.6.0
8.7
11,6
14.6
18.0
1
25.0 21.8
30.5
33.8
61.2
69.4
75.0
79.6
83.5
26.1
31.5
39.3
60.7
68.5
73.9
78.2
87.1 J82.0
90.3 I«5.4
93.3 ICB.A
96,1
98,7
191.3
94,0
36.5
98,9
'24
1 1
3.2
S.S
7.9
10.5
13.2
16.1
19.4
23.0
27.2
32.3
39.8
60.2-
67.7
72.8
77.0
80.6
83.9
86.8
89-5
92.1
94.S
96.8
98.9
KDfRAL UOISm, VOL. 41, NO. Ill—TUKDAY, JUNI I,
C-4
-------
nOPOSED HOLES
29063
TRAVERSE
POINT
1
2
3
4
5
DISTANCE.
% el diameter
4.4
14.7
29.B
70.5
86.3
»c.e
Figure 1-2, Example Showing circular stack cross section (CvMod into
12 equal areas, with location of traverso points at controid or each area.
In some eases, two successive traverse
points may need to be relocated to a single
adjusted traverse point at each end of the
traverse diameters. Hie sampling time at
each of these "adjusted" traverse points shall
be twice as long as at a "non-adjusted"
campling point as determined by the respec-
tive pollutant sampling method, e«.. Meth-
od 6. ' '
9,3.1.9 Stacks equal to or less than 0.8 m
(It In.). *Wlow the procedure in section
94.1.1. noting only that the "adjusted"
points should be relocated at 147 em (03
in.) from the wall Instead of 344 cm (1 In.) .
3.8.3 Rectangular stacks. Divide the cross
section Into as many equal rectangular areas
as traverse points aa determined In sections
2.1 and 34 of this method, such that the
ratio of the length to the width of the ele-
mental areas Is between one and two. Locate
the traverse points at the otntroid of each
equal area according to the example in
Figure 1-3.'
The situation of section 34.1 concerning
eampllng pointa too close to the stack walla
to not expected to arise with rectangular
•tacks. On the remote possibility that It does
occur, consult with the Administrator.
3.4 Verification of non-cyclonic or non-
awlrllng flow. Generally, cyclonic or, swirling
How can be expected after such devices aa
cyokmea and Inertia! demiaters that follow
venturl scrubbers or In stacks that have tan-
gential inlets or two inlets that are opposite
each other. At times, cyclonic flow can be
detected by visual observations of the effluent
plume. However, a Type S pltot tube aa de-
scribed to Method 3 can be used aa a tool
to verify the presence of cyclonic or swirling
flow by doing the following:
9.4.1 Level and sero the manometer. Posi-
tion the Type 8 pltot tube at each of the
traverse points such that the face openings
•re perpendicular to the stack eross-eeotlonal
ptoneV A null (aero) reading at "0* refer-
once" denotes the absence of cyclonic flow.
Xf the reading la not aero, then rotate the
pltot tube about ±10*. A nun reading with-
in the limits of ±10* rotation from 0* refer-
ence indicates an acceptable flow condition.
244 conduct a velocity traverse accord-
ing to Method a. If there are negative velocity
pressure readings, unacceptable flow condi-
tions exist.
• 944 When unacceptable flow conditions
•re encountered, alternate procedures, sub-
ject to approval of the Administrator,, are
required.
I. XC/W
S.1 Determining Dust Concentration to
• oas Stream, A8MB Peerformance Test Code
«37, Hew TO*. K.T,1«B7.
84 Devorkln, Howard, et al.. Air Pollu.
tion Source Testing Manual. Air Pollution
Control District, Los Angeles, Calif.. Novem-
ber 1908.
.84 Methods for Determination at Velo-
city. Volume, Dust and Mist Content of
Oases. Western .Precipitation Division of Joy
Manufacturing Oo., Los Angeles, Calif. Bul-
letin WP-M. IMS.
84 Standard Method for Sampling Stacks
for Parttoulato Matter, to: »71 Book of
A8TM Standards, Part 98, Philadelphia, Pa.
1071. A8TM Designation D-9038-71.
MCTHOO 9—DSTKUWXHATION OF STACK OAK
VB&OCRT am Voiuurnuc PLOW RAW (Tn>»
SPrror Toast)
1. Principle and Applicability.
1.1 Principle, stack gas velocity to de-
termined from the gaa density and from
measurement of the velocity head using a
Type S (Stausschelbe or reverse type) pltot
tube.
14 Applicability. This method to appli-
cable for measurement of the average
velocity of a gas stream and for quantifying
gas flow.
This procedure la not applicable for direct
measurement to cyclonic or swirling gaa
streams. (Method l, section 9.4 shows how to
determine unacceptable flow conditions.)
When these conditions exist, procedures such
aa the use of flow straightening devices must
be employed subject to approval by the Ad-
ministrator, to make accurate flow rate de-
terminations.
2. Apparatus.
Specifications for the apparatus are given
below. Any apparatus which has been dem-
onstrated subject to approval of the Ad-
ministrator, to be capable of'meeting the
specifications will be considered acceptable
for the purposes of thla method.
9.1 Pttot tube. Type a (Pigure 9-1). or
equivalent, calibrated according to the pro-
cedure to section 4. Other devices may be
used when approved by the Administrator.
24 Differential pressure -guage. Inclined
manometer, or equivalent device, capable of
measuring velocity head to within 10% of
the mhiHiMmi measured value <* ±0.018 mm
(0.000 to.), whichever to greater. Below a dif-
ferential pressure of 14 mm (0.09 in.) water
gauge, mloromanometera with sensitivities of
0.018 mm (OAOM to.) should be need. Bow-
ever, micromanometers may not easny be
adaptable to y*^ yrf^tfog field conditliyM
and are not easy to use with pulsating flow.
Thus, alternative methods or other devices
acceptable to the Administrator may be used
when conditions warrant.
MOMTH, VOL 41, NO. Ill—TUWDAY, JUNt I, 1W
C-5
-------
28064
PROPOSED RULIS
f.80'lS4cffi
fOJS-lJBiaJ
rm-SPITOTTUSE
MANOMETER
Figure 2-1. Pitot tube-manometer assembly.
Tao calibration of mqg&ehellaa, U used,
must be checked on-slte before and after
each test run.
2.3 Temperature gauge. Thermocouple,
liquid filled bulb thermometer, bimetallic
thermometer, mereury-ln-gloss thermometer,
or other gauges that ore capable of measur-
ing temperature to within 1 J% of the mini-
mum absolute stock temperature. The ten*
perature gauge shall be attached to the pltot
tube such that the ee&aor doee not touch my
metal ud Its position la adjacent and about
ISO to 3.H cm (0.78 to 1 In.) from the pltot
tube openings (see Figure 3-1). Alternate
positions may be ueed If the pltot tube-tem-
perature gauge system IB calibrated accord-
ing to the procedure of section 4. If tt can be
shown to the satisfaction of the Administra-
tor that a difference of not more than 1%
In the Telocity measurement will be In-
troduced, the temperature gauge need not be
attached to the pltot tube,
9.4 Pressure probe and gauge. Piezometer
tube and mercury- or water-filled XT-tube
manometer capable of measuring stack pres-
sure to within 3.6 nun Hg (0.1 In. Hg). TIM
static tap of • standard type pltot tube or
one teg of « Type 8 pltot tube with the face
openings positioned parallel-to the gas flow
may also be used a* the pressure probe.
a* Barometer. Mercury, aneroid, or other
barometers capable of measuring atmos-
pheric pressure to within 3.8 mm Hg (0.1 In.
Hg). In many oases, the barometric reading
may be obtained from » nearby weather bu-
reau station, In which ease the station value
(which to the absolute barometric pressure)
shall be requested and an adjustment for
elevation differences between the weather
station and the sampling point shall bo
applied at a rate of minus 3.8 mm Rg (0.1 in.
Hg) per 80 m (100 ft) elevation Increase or
vice vena for elevation decrease.
3.9 Oaa analyser. To analyze gas com-
position for determining molecular weight.
Use Method 8 or other methods specified *y
the Administrator for dry molecular weight
and use Method 8 or Reference Method 4 for
moisture content Other methods may be
used when approved by the Administrator. .
3.T calibration pltot tube. Standard type,
to calibrate the Type 8 pltot tube. The stand-
ard type pltot tube shall have a known co-
efficient obtained from the National Bureau
of Standards, Route, 70 8, Quince. Orchard
Road, Oalthersburg, Maryland. An altama*
tire Is to .use a Prandtl type pltot tube de-
signed according to the criteria (given below
and illustrated la Figure fl-ft see also Refer-
ence 6.7 or 63 tot greater detail) which en-
sure that its eoefflotent will tea O.TO±0.01.
9.74 Hemispherical or eUtpsodlal tip (la-
tot end of the Impact tube).
HOMAL ttOllTR, VOL 41, NO. Ill—1UBSDAY, JUNB •,
C-8
-------
o
I
HBntntEMCtt,
Bttndntf ntrt tube.
9.7J Hgh« dtaateten of rtwJght FOB
(based on the diameter of the external tube)
between the tip and toe static pressure holes.
9.7.8 Sixteen diameters between the static
pressure holes and the «enterllna of the ex-
ternal tube, following the 90* bend.
9.7.4 Eight status pressure holes of equal
sn» (approximately 0.71 mm or I/a m.
diameter), equally opaeed In a piezometer
ring configuration.
9.73 Ninety-degree bend of relatively
large radius (approximately three dtametera).
9A Calibration differential pressure
gauge—To? calibration purposes, inclined
manometer, or equivalent device, capable of
meararlng Telocity head to within 0.18 mm
H.O (0.005 In. H,O).
8* PFOC60UIT0B
SJ Bet up the apparatus as abown in
Figure 3-1. Make anre all connections are
tight aad leak free. Level and zero the ma-
nometer. Because the manometer level and
BOO may drift due to vibrations and tem-
perature changes, make periodic checks dur-
ing the sample run. Record all necessary data
ae shown In the example data sheet (Figure
a-8).
8.2 Measure the velocity head and tem-
perature at the traverse points apedfled by
Method I.
8.8 Measure the static pressure in the
ateok. One reading to usually adequate for
all measuring points during the test; how-
ever, this must be confirmed by randomly
moving the piesauie probe over the cross sec-
tion to aee if there are any significant varia-
tions. La, greater tban about 100 mm H,O
(4 in. H.O). If there are significant varia-
tions, check the location for disturbances. If
none are found, measure and record the
etatle pressure at each traverse point.
1
1
;
I
I
1
1
mTf HUM «n
STACK OlAMt
JAROVETRICI
tSSSSSECTIO
)PCRATORS
>rrOTTUBEI.(
AV6. COEFI
LAST DATE
Trmnt
Pt.Ne.
rERORDfc:EKSio"!
'RESSURE.mmHgOl
r^Al ARFA f"2;i!2)
: «,rin )
, P,»
i »-n
ripirrrr r_«
£fl! IRRATFD
reft
Suck Tmiptniun
t*. 'C (®F)
Amiga
TtOKCR)
SCHEMATIC OF STACK
CROSS SECTION
V
iBmHglinJtjJ
/IT
•W prdlmlnrT towrtipfloii Aew thrt Pj wrtM no wow thw 108 mm Hj8
(4 to. HjO). neord en* taadiog.
Figure 2-3. Velocity traverse data.
FEDERAL REGISTER. VOL 41, NO. 111—TUESDAY. JUNE 8, 1976
-------
23066
PROPOSED RULES
3.4 Determine the atmospberlo pressure.
8 JJ Determine the dry stack gM moleoulmr
weight. For combtutloa processes, UM Method
3. For processes emitting essentially sir, an
analysis need not be conducted: UM * molec-
ular weight of 30. For other processes, con-
sult the Administrator.
3.8 Obtain the moisture- content from
Method 6 or by using Preference Method 4.
3.7 Determine the croM aeotlonal are* of
the atack or duct at the sampling location.
Whenever possible. It Is better to physically
measure the stack dlmenaloni rather than
•using blueprints.
4. Calibration.
4.1 Pitot tube.
4.1.1 Calibration aet-up—Calibration shall
be don* in a flow system having the follow-
ing essential design features:
4.1.1.1 The flowing gas stream must be
confined to a definite cross-secttonal area.
either circular or rectangular. For circular
cross-eecttons. the minimum duct diameter
•hall be 30.6 cm (13 inches); for rectangular
cross-sections, the width (shorter side) shall
be at least 38.4 cm (10 inches).
4.1.1.2 The cross sectional area must be
constant over a distance of 10 or more duct
diameters. For a rectangular cross section,
use an equivalent'diameter calculated from
he following equation to determine the num-
ber of duct diameters:
D.=
2LW
"(L+W) Equation2-1
where:
D.= Equivalent diameter
L=Length
W=Width
To ensure the presence of stable, fully
developed flow patterns at the calibration
site, or "test section," the site must be lo-
cated at least 8 diameters downstream and
two diameters upstream from the nearest
disturbances.
Hon.—Wind tunnels with well-developed
flow patterns (I.e., flow parallel to the duct
axis) may also be used.
4.1.1.3 The flow system shall have the ca-
pacity to generate a test-section velocity
around 016 m/m*n. (8000 ft/mln.). which Is
the approximate midpoint of the "normal
working range" SOB to 1635 m/mln. or
~1000 to 6000 ft/mln. This velocity must be
constant with time, to guarantee steady
flow during calibration.
Mote that Type-S pitot tube coefficients
obtained by single-velocity calibration at the
midpoint of the normal working range will
generally be valid to within ±8 percent over
the entire range. If a more precise correla-
tion between C, and velocity is desired, the
flow system shall have the capacity to gen-
erate a number of distinct, time-invariant
test-section velocities, covering the normal
working range, and calibration data shall be
taken at regular velocity intervals between
SOB and 1628 m/mln. (1000 and 8000 ft/
mln.). (See Reference 6.9 for details.)
4.1.1.4 Two entry ports, one each for the
standard and Type 8 pitot tubes, shall be
cut in the test section; the standard pitot
entry port shall be located slightly down-
stream of the Type 8 port, so that the
standard and Type 8 Impact openings will
lie in the same eroes-section-1 plane during
calibration. To facilitate alignment of the
pitot tubes during calibration, it is advisable
that the test section be constructed-of plexl-
glas or some other transparent material.
4.1.3 Calibration procedure. Note that
this procedure is a .general one, and must not
to* used without first referring to the specific
•OnsMerattoM presented in sections 4.1.4-
4.1.8. Note also that this procedure applies
only to single-velocity calibration: see Pref-
erence 6.9 for more details. It is recom-
mended that an identification number be
assigned to the pitot tube, and that this
number be permanently marked or engraved
on the body of the tube; also, one leg of the
tube should be marked "A", and the other,
"B". To obtain calibration data for both the
"A" and "B" sides, proceed as follows:
4.1.3.1 Make sure that the manometer is
properly filled cad that the on Is free from
contamination. Inspect and leak-check all
pitot lines; repair or replace if necessary.
4.1.3.3 Level and MTO the manometer.
Turn on the fan and allow the flow to
stabllis*. Seal the Type S entry port.
4.1.3.8 Ensure that the manometer is level
and Mroed. Position the standard pitot tube
at the calibration point (determined as out-
lined In sections 4.1.4 and 4.1.6), and align it
so that its tip Is pointed directly into the
flow. Particular care should be taken In
aligning the tube, to avoid yaw and pitch
angles. Make sure that the entry port sur-
rounding the tube is properly sealed.
4.1.2.4 Pead AP«i and record its value In
a data table, similar to the one shown in
Figure 3-4. Bemove the standard pitot tube
from the duet and disconnect it from the
manometer. Seal the standard entry port.
4.1.3.6 Connect the Type 8 pitot tube to
the manometer. Open the Type 8 entry port.
Check the manometer level and zero. Insert
and align the Type 8 pitot tube so that its
"A" side Impact opening is at the same point
as was the standard pitot tube, and Is pointed
directly into the flow. Make sure that the
entry port surrounding the tube Is properly
sealed.
4.1.3.6 Pead APi and enter its value In the
data table. Bemove the Type 8 pitot tube
from the duct and disconnect It from the
manometer.
4.12.7 Repeat steps 4.1.3.3 through 4.1.3,6
above, until three sets of velocity head read-
ings have been obtained.
4.1.3.8 Repeat steps 4.1.3A through 4.1.2.7
above for the B-side of the Type 8 pitot tube.
PITOT TUBE IDENTIFICATION NUMBER:.
. DATE:.
CALIBRATED BY:.
RUN NO.
1
2
3
"A" SIDE CALIBRATION
AP$td
ctnHjO
(in.H20)
*P«
cmH?0
-------
PROPOSED RULES
23067
where:
'Equation 2-3
C,<»—Typ« 8 pi tot tube coefficient
O,(,td>™Standard pitot tube coefficient; use 0.89 If the coefficient ia unknown and the
tuele ia designed according to the guidelines in aeotion 2.7
Ap.u"»Velocity head measured by the standard pitot tube, em H»0 (in. HiO)
Apt—Velocity head measured by the Type 8 pitot tube, cm H»0 (in. H|O)
4.1.3.S Calculate O, (side A), tba mean A-slde opefflolent, and O, (side B). the mean
B-slde coefficient; calculate the dlfferenee between these two average vataes.
4.1»» Calculate the deviation of each of the three A-slde values of O»<«• aerodynamic interactions
between the pltot tube and sampling nonle
there must be a separation distance (free-
space) of at least 1.90 em (K in.) between
the noBsle and pltot tube, with the largest
alee nozzle (usually 1.8 cm or % In., l.d.) in
place. (See Figure 3-6.)
(b) To minimise aerodynamic interactions
between the thermocouple and pltot tube,
the thermocouple wire must be mounted on
the pltot tube In such a way that the tip of
the wire is In line with, but at least l.flO
cm (% in.) from the center of the pltot tube
Impact openings. (See Figure 9-4.)
(c) To eliminate pltot tube-probe sheath
Interference, there must be at least 7.63 em
(8 In.) between the leading edge of the probe
and the center of the pltot tube impact open-
Ings. (Bee Figure 3-7.)
For those assemblies which either (1)
meet requirements (a) through (c) above
but have unknown isolated coefficients, or
(3) fail to meet these (equipments, use the
procedures «e calibrate fee pttet vube-noa-
He-ttMnnoeoupIo assembles outlined In sec-
tions 4.1.3 and 4.1^, in oon^unetlan with
the following special considerations, to
determine the A and B-slde coefficients of
the Type 8 pltot tube:
Tm-imOTTUBEt
X>UOe»(Mia)fsrD.-UM (1/2la)
SASIPUNC MOau
Figure 3-5. Minimum pitet-nents npratlcn nMded to prtvmt fnttrftnn
>7J2csi(ll
TMcnMoeoune
J.C
jw>uzMObj|
^^ tl>tJ
roE-SPITOTTUBI (£1
i
ilil.
SAMPLE PROBE
Ml
i
Figure 2-6. Proper thermocouple placement to prevent Interference.
RDIRAL UOIini. VOL. 41. NO. Ill—TUUDAY, JUM 8. We
C-9
-------
23068
PROPOSED RULES
TYPE-S PITOT TUBE
SAMPLE PROBE
Figure 2-7. Minimum phot-sample probe eeparatfon needed to prevent Interference,
Figure 2-8. Projected-vet models for typIctJpltobeanemWIei.
(1) Although It is preferable that the cali-
bration point be located at or near the cen-
ter of the duct, Insertion of a probe *h*ath
Into a small duct may cause significant cross-
seotlonal area blockade, and yield Incorrect
coefficient Talue*. Therefore, to mlnlmlne
the blockage effect, the calibration point may
be a few Inches off-oenter If necessary. To
keep the actual reduction In O» due to
blockage below 1 percent, It I* necessary that
the theoretical blockage, as determined by
a projected-area model of the probe sheath.
be 3 percent or less of the duct cross-
•eettonal area for assemblies without ex-
ternal sheaths (see Figure Ma) and 8 par-
cent or leas for assemblies with external
sheaths (Figure »-8b).
(U) For pitob* assemblies In which pltot
~ Interference Is a factor (U,
If the tub* ha* been algnlnoantty damaged
by neld UM (for example, If the Impact
opening* art bent out of •hape, out, nicked,
or noticeably misaligned), It thall be repaired
If possible and recalibrated, or replaced, If
those in which the pltot-nonle separation
distance U leu than 1*0 em (K In.) with a
14 cm (K In.) noszle in place) the value of
O» will depend somewhat on the amount of
free space between the tube and noaHe; la
these H"*""««. separate calibrations shall
be performed with each of the-commonly
used nflq^i+ sfswsj In place* Note that single"
vetocttf calibration technique will be ac-
ceptable for this purpose, eren though the
larger nosxie stcee (>«A30 cm or 14 in.) an
not ordUHwOf used for laoklnetle sampling
at velocities around 915 m/mln, (8000 fV
mln,), which is the calibration Telocity.
4,1.8 Beoallbrattoa and Field Use.
4.1.6M the Type B pltot tube shall b*
calibrated before Its Initial use. Thereafter.
4.1.9J When the Type 8 pltot tube Is used
in the neld. the appropriate A or B-slde co-
efficient shall be used to perform Telocity
calculations, depending upon which side/ of
the pltot tub* to pointed toward the now.
4,1.6.8 When sampling a small duct
(-13-80 Inch** In diameter) with a pltobe
assembly, the probe sheath can block a sig-
nificant part of the duct cross-section, oaus-
(Ing a reduction In the Talue of O». There-
fore. In certain Instance* It may be necewary,
prior to sampling, to pittfr^ adjustments I1*
^li^ coefficient Tallies obtained by calibra-
tion, Oonndt Beferenoo 9A for details.
4£ Temperature gauges. Calibrate dial
and liquid filled bulb thermometers and
thermocouple-potentiometer lystoms against
meroury-ln-glaas thermometers. Ice bath and
boiling water (corrected for barometric pres-
sure) are acceptable reference points. For
other dertoes. check with the Admlnistator.
44 Barometers. Calibrate against a mer-
cury barometer.
B. OoloulaNon*.
Carry out calculations, retaining at least
one extra decimal figure beyond that of the
acquired data. Bound off figures after final
8.1 Nomenclature.
HDMAL UOlim, VOL 41. Ma 111—TUISDAr, JUNI 8, 1*74
C-10
-------
PROPOSED RULES
23069
X— Cross sectional area of stack, m* fff)
B.,- Water vapor In the gas stream (from Method 5 or Reference Method 4), pro-
portion ay volume
C,— Pi tot tube coefficient, dimenslonless
IT,— Pitot tube constant,
94 07 J2. r(g/g-mol«) (mm HgnV
eeci (*K)(mm H»O) J
for the metric system and
ft rOb/lb-moleWn.Hgny,
iec L (*R)1%) with cross Motion and with time. If they do, consult with the A
determine an acceptable procedure.
•A Average ste^ gas dry volumeWo flow rate.
(I.e.
trator to
., M^anlcal ^neer,
' - Wtl8ht terminations,
, Obemlcal Znglneers' »>u.tlon ga. analynr.
Pwry J.
Bandbook, MoOrsw-HUl Book Co., Inc., New
1 A Applicability. This method !• appll-
Bamplto« Mearanmeota. Paper presented at
toe Annual Meeting of tbe Air Pollution
AiMflUtlon' ^ ^^ M°- **• "-
«.* tandard Method for Sampling Btacta
for Partloulate Matter. In: 1B71 Book of
A8TU Standards. Part 93. Phlladelpola. Pa.,
9. Apparattu.
Aay «PP*ratu. wbleh has been demon-
itr*t*<1 *° W* "*&* acceptable to the Ad-
mlnutrator win be considered acceptable for
tbe purpose* of this method.
obanies, John Wiley ft Boos, Inc., New York.
K>T"
and A
fl.7 ASBRAB Handbook of rundamentali.
1979, p. 908. ..--.,« ^
0 j A8TM Annual Book of A8TM Stand-
aids. Part 96, 1874. p. 848.
8.9 Vollaro, B»-F. Guidelines for Type-8
Pitol Tube CW»br»tlon. '«'Pr»»*»d •*
91.1 Probe— Stainless steel or boroslllcate
gUM •«u>PI»«"'»»th a flltw (either ln-rtaek
- •*— « * — - P-*— "tter.
9.1J Pump— One-way squeeze bulb, or
equlTaUnt, to transport gas sample to
92 Integrated sample (Figure 8-3).
93.1 Probe-etalnlsse rteel or boroalllcate '
8— OA» AnALTsa ro« OAUOM Di-
ozm*, OzToar, XXCSH A», urn D«T Mouto-
uua WBOHT
1. PrtnetpU end ^ppltooWHty.
IJl Principle. An Integrated or grab gas
•ample Is extracted from a stack and analysed
«* out-stack) to remove partleulate matter
> Mention of trade names or specific prod-
nets daee not ooastltnte endorsement by the
Bnvlronmental Protection Agency.
HDIIAI HOISTIR, VOL. 41, NO. 1 1 1— IUIJOAY, JUNI I, If 76
C-ll
-------
23070
-PROPOSED RULES
•ROBE
FLEXIBLE TUBING
FILTER (OL ASS WOOL)
70 ANALYZER
SQUEEZE BULB
Figure 3-1. Grab-sampling train.
F1TOTTUBE
Utm(0.7Sinj
•ROBE-WOT TUBE
Figure 3-2. Integrated gas-sampling train.
3.2.2 Condenser—Air-cooled condenser, or
equivalent, to remove excess moisture.
3.2.3 Valve—Needle valve, to adjust sam-
ple gas Bow rate.
2.2.4. Pump—Leak-tree, diaphragm type,
or equivalent, to transport sample gas to the
flexible bag. Install a small surge tank be-
tween the pump and rate meter to eliminate
pulsation effect of diaphragm pump on the
rotameter.
2.3.8 Bate meter—Potameter, capable of
measuring a flow range from 0 to 1.0 litre per
minute.
2.2.8 Flexible bag—Tedlar.i or equivalent,
with a capacity in the range of 88 to 00
liters. Before each field test run make sure
the bag is leak-iree by checking it for teaks.
To leak cheok, connect a water manometer
and pressurize the bag to fl-10 om H,O (9-4
in. H,O). Allow stand for 10 minutes. Any
displacement In the water manometer indi-
cates a leak.
NOTE.—An alternative leak check method
is to pressurize the bag to 6-10 cm H,O or
fl-t in, H.O and Know to stand overnight.
A deflated bag Indicates a leak.
3.2.7 Pltot tube-Type 8, or equivalent,
attached to the probe to allow constant moni-
toring of the stack gas velocity so that the
sampling flow rate can be regulated propor-
tional to the stack gas velocity. The tips of
the probe and pltot tube shall be adjacent to
each other and the free space between them
shall be about IS em (0.75 in.). When used
with this method, the pltot tube need not
be calibrated.
2.2.8 Differential pressure gauge—Inclined
manometer capable of measuring velocity
head to within 10% of the minimum meas-
ured value or ±0.013 mm (0.0008 In.), which-
ever Is greater. Below a differential pressure
of 1.8 mm (O.OB in.) water gauge, mlcroma-
nometers with sensitivities of 0.018 mm
(0.0006 In.) should be used. However, micro-
manometers may not easily be adaptable to
the existing field conditions and are not easy
to use with pulsating Jlow. Thus, alternative
methods or other devices acceptable to the
Administrator may be used when conditions
warrant.
2.2.9 Manometer—About 28 cm (12 in.)
water-filled U-tube manometer, or equiva-
lent, to be used for the flexible bag leak
check.
2.2.10 Vacuum gauge—At least TOO mm
Eg (80 in. Hg) gauge, to be used for the sam-
pling train leak check.
2.8 Analysts.
2J.I Orsat analyzer or'Fyrlte type com-
bustion gas analyzer. The latter is used only
for molecular weight determination. For low
CO, (lees than 4 percent) or high O,
(greater than 16 percent) concentrations, the
measuring burette of the Orsat must have at
least 0.01% subdivisions.
3. Sampling Procedure.
3.1 Grab sampling. This procedure is pri-
marily used for. but not limited to, deter-
mining molecular weight. Other uses must
first be approved by the Administrator.
3.1.1 The sampling point in the duct
shall be at the centrotd of the cross section
or at a point no closer to the walls than 1 m
(3.28 ft), unless otherwise specified by the
Administrator.
8.1.2 Set up the equipment as shown in
Figure 3-1, making sure all connections are-
tight and leak-free by following the proce-
dure In Section 4.
3.15 Place the probe In the stack at th»
sampling point and then purge the sampling
line. Draw a sample into the analyzer and
analyze according to Section 4.
8.2 Integrated sampling (required when
the analytical results will be used to calculate-
a pollutant emission rate correction factor).
8.3.1 Select the sampling location accord-
ing to Method 1. In addition to the criteria
of Method 1, the sampling location shall be
at least 3 diameters downstream from any
point of air In-leakage. The downstream dis-
tance shall be calculated using the linear
distance from the point of air In-leakage,
and the diameter of the stack at the sam-
pling location.
332 A minimum of 8 traverse points,
selected according to Method 1, shall be used
for circular stacks with diameters less than
0.6 m (3 ft.), A minimum of 12 traverse
points, selected according to Method 1, shall
be used for all other cases, unless otherwise
specified in an applicable subpart, or unless
specifically approved by the Administrator.
333 Leak check the flexible bag as in
Section 23.6. Set up the equipment as shown
in Figure 3-2. Just prior to sampling, leak
check the train by placing a vacuum gauge
at the condenser inlet pulling a vacuum of
at least 350 mm Hg (10 in. Hg), plugging the
outlet at the quick disconnect, and then
turning off the pump. The vacuum shall
remain stable for at least one minute. Evacu-
ate the flexible bag. Connect the probe and
place it in the stack and then purge the
sampling line. Now, connect the bag and
make sure that all connections are tight and
leak free.
83.4 Sample at a rate proportional (with-
in 20% of constant proportionality, or as
specified by the Administrator) to the stack
velocity, traversing all sampling points. Re-
cord proportional sampling data as shown in
Figure 8-3. When analytical results will be
used to calculate a pollutant emission rate
correction factor, the sampling Must span
the length of time'the pollutant emission
rate is being determined, sampling at each
traverse point for an equal length of time.
Collect at least 30 liters (1 ft") of sample
gas-
3.3.5 Obtain and analyze at least one- In-
tegrated flue gas sample during each polhi-
tant emission rate determination.
4. Analytical Procedure.
4.1 Leak check for Orsat analyzer. Mov-
ing an Orsat analyzer frequently causes it to
leak. Therefore, an Orsat analyzer should be
thoroughly leak-checked on-slte before the
flue gas sample la Introduced into it. The
suggested procedure tor leak-checking an'
Orsat analyzer is:
4.1.1 Bring the liquid level In each pipette
up to the reference mark on the capillary
tubing and then close the pipette stopcock.
FBMRAl MOISTER, VOL, 41, NO. Ill—TUISDAY, JUNE B, Wo
C-12
-------
PROPOSED RULES
23071
TWE
IMVERSI
-£•»
a
1pm
AVERAGE
•XDEV" (^J3)iOfl (MUST BE 5 2W
";&
J
KDEV."
Figure 3-3. Proportional sampling data.
4.1.3 Balse the leveling bulb sufflclently
to bring the eonflnlng liquid meniscus onto
the graduated portion of the burette and
then eloee tbe manifold stopcock. •
4.1.3 Beeord tbe meniscus position.
4.1.4 Observe the mentaoua la tbe burette
and the liquid level In the pipette for move-
ment over the next four minutes.
4.1.6 For the Orsat analyzer to paea the
leak-check, two conditions must be met:
4.1.8.1 Tbe Uquld level In each pipette
must not fall below the bottom of the capil-
lary tubing during this four-minute Interval.
4.1.6.2 Hie meniscus In the burette must
not change by more than 04 ml during this
four-minute Interval. For the results to be1
valid the Great analyzer must pass this leak
test before and after tbe analysis.
4.1.8 If the analyzer falls the leak-check
procedure, ail rubber connections and stop-
cocks should be checked until the cause of
the leak Is Identified. leaking stopcocks
must be disassembled, cleaned and regreaeed.
rubber connections. must be re-
plaeed. After the analyzer is reassembled, the
leak-check procedure must be repeated.
4.3 Determination of stack gas molecular
weight. (Drsat leak check described above is
optional). Within eight hours after the
•ample Is taken, analyze tt for percent carbon
dioxide and percent oxygen using either an
Orsat analyzer or a Fyrtte type combustion
gas analyzer. Determine the percent of the
gas that I* nitrogen and carbon monoxide by
subtracting the sum of the percent carbon
dioxide and percent oxygen from 100 percent.
45.1 Orab samples— Bepeat the sampling
and analysis until the molecular weight from
each of three consecutive grab samples dif-
fers from their means by BO more than 04
grams/gram mole (04 pounds/pound mole) .
444 Integrated Bamnlee — Bepeat -the
analysis until the molecular weight for three
consecutive analyses differs from their mean
by no more than 04 gram/gram mole (04
pound/pound mole).
44 Determination of Ov CO,, o* excess air
for calculating pollutant emission rate cor-
rection factors.
NOT*.—The Fyrite type combustion gas
analyzers are not acceptable for this pur-
pose, unless otherwise approved by the Ad-
ministrator. The results may also be used for
determining stack gas molecular weight.
44.1 Leak check the Orsat analyzer as
described in section 4.1. This procedure is
mandatory.
444 Within four hours after the in-
tegrated sample is taken, analyze it for per-
cent carbon dioxide and percent oxygen us-
ing an Orsat analyzer. To ensure complete
absorption of these gases make repeated
passes through the absorbing solution until
two consecutive readings are the same.
Several passes (*-«) should be made between
readings. (If constant readings cannot be ob-
tained after three consecutive .readings, re-
place the absorbing solution.) Determine the
percent of the gas that Is nitrogen and
carbon monoxide by subtracting the sum of
the percent carbon dioxide and percent
oxygen from 100 percent.
This procedure assumes that carbon
nwnoxlde concentration is negligible. If ap-
preciable quantities are expected, alternate
procedures subject to approval of the Ad-
ministrator, must be used.
444 Bepeat the analysis on the Inte-
grated sample until each of three oonaecuttve
analyses for percent carbon dioxide and per-
cent oxygen differ by no more than 04 per-
cent by volume when carbon dioxide to
greater than 3% and 04 percent by volume
when carbon dioxide to Mat than* or equal to
8%.
6. CohwteMoiu.
B.l Nomenclature;
Dry molecular weight (gram/gram mole)
Percent exoees air
iCOi—Percent carbon dioxide by volume (dry basis)
~ ~,» Percent oxygen by volume (dry basis)
i« Percent nitrogen by volume (dry bada)
"Ratio of oxygen to nitrogen in air, v/v
0.28—Molecular weight of both nitrogen and CO divided by 100
0.82- Molecular weight of oxygen divided by 100
0.44-Molecular weight of carbon dioxide divided by 100
•4 Excess air. Use equation a-t to calculate the percent simse air wlrtr the three
consecutive analyses that meet the requirements of section 444. nun calculate the
average percent excess air.
0.204 %N,-%0« Equation 8-1
i.—The equation above assumes that carbon monoxide concentration to negligible.
notable carbon monoxide concentrations an expected, consult witn the
—*•— *• —
RDKAL UOUTn, VOL 41, NO. HI—TUISOAV, JUKI •, 197*
C-13
-------
23072
PROPOSED RULES
8.3 Dry molecular weight. TJse equation 8-9 to calculate the dry molecular weight*
using dat*. obtained from Motions 4.3.1, 4.9.2, or 4.3.3 and 4JJ, average Hi* results and
report to the nearest 04 g/g-mol* (0.1 Ib/lb-mole).
Md-0.44(%CO,)+0.32(%Oi)+0.28(%N,+ %CO) Equation 3-2
5.4 Carbon dioxide concentration calcu-
lation. Using the three consecutive carbon
dioxide analyses that meet the requirements
of section 4.3.8, calculate the average carbon
dioxide concentration.
6. Referenoei.
6.1 Altshuller, A. P. Storage of dase* and
Vapors In Plastic Bags, International Journal
of Air and Water Pollution, 5, 75-81 (1983).
6.3 Connor, William D. and J. 8. Nader,
Air Sampling with Plastic Bags, Journal of
the American Industrial Hygiene Association,
2o', 291-297 (1964).
6.3 "Burrell Manual for Gas Analysts,"
Seventh edition (1051), Available from Bur-
rell Corporation, 2293 fifth Avenue, Pitts-
burgh, Penna. 15218.
METHOD 4—DETERMINATION or MOISTURE IN
STACK OASES
1. Principle and ApptcablUt]/.
1.1 Principle. A gas sample ti extracted
proportionally from the source and moisture
is removed from the gas stream, condensed,
and determined either volumetrloally or
gravlmetrleally.
1.2 Applicability. This method is ap-
plicable for the determination of moisture
In stack gas.
Two method* are given. One is a reference
method for the accurate determination of
moisture content as needed to calculate
emission data. The other is an approximation
method for moisture content to be subse-
quently used for setting isoklnetlc sampling
rates, For this latter purpose, the tester may
use any alternate means for approximating
the moisture content, e.g. drying tubes, wet
bulb-dry bulb technique condensation tech-
niques, stoichlometrlc calculations, previous
experience, etc, However, the actual iso-
klnetlc rate maintained during a pollutant
sampling run and the moisture content used
to calculate emission data will not be based
on the results of the approximation method
(aee exception in. note below), but will be
determined from the data of the reference*
method, which Is normally conducted
simultaneously with a pollutant measure-
ment run.
NOTE.—Any of the approximation methods
which are shown to the satisfaction of the
Administration of yielding results to
within 1% H>O of the reference method re*
sulta may be used in Jleu of the reference
method.
These methods are not applicable to gas
streams that contain liquid droplets. For
these cases, assume that the gas stream is
saturated. Determine the average stack gas
temperature using gauges described in
Method 2 and by traversing according to
Method 1. Then obtain the moisture per-
centage by (1) using a psychometric chart
and making appropriate corrections, if stack
pressure is different from that of the chart,
for absolute preesurt or (•) by using satura-
tion vapor pressure tables.
3. Reference iiethod.
The procedure for determining moisture
content described in Method 5 la acceptable
aa a reference method.
3.1 Apparatus. A schematic of the sam-
pling train used In this reference method is
shown in Figure 4-1. All components shall
be maintained and calibrated according to
the procedure outlined in Method 5.
3.1.1 Probe—Stainless steel or glass tub-
ing, sufficiently heated to prevent water con-
densation and equipped with a filter (either
in-slack or heated out-stack) to remove
participate matter.
3.1.2 Condenser—Any system that cools
the sample gas stream and allows measure-
ment of the water condensed and moisture
leaving the condenser,-each to within 1 ml
or 1 g. Acceptable means are to measure the
condensed water either gravlmetrleally or
volumetrtcfttly and to measure the moisture
leaving the condenser by (1) monitoring the
temperature and pressure at the exit of the
condenser and using Dalton's law or (3) by
passing the sample gas stream through a
tared silica 'gel trap with exit gases kept
below 90' C (88* F) and determining the
weight gain.
3.1.3 Cooling system—Ice bath container
and crushed ice, or equivalent, .to aid in con-
densing moisture.
3.1.4 Drying tube—Tube packed with 6-16
mesh indicating-type silica gel, or equivalent,
to dry the sample gas and protect the pump
and dry gas meter. This may be an Integral
part of the condenser system, in which case
the tlibe shall be immersed in the ice bath
and a thermometer placed at the outlet for
monitoring purposes. If approach (1) * of
section 9.1.3 is used to measure the moisture
leaving the condenser, the temperature and
pressure must be monitored before the silica
gel tubs.
3.1.5 Metering system—Vacuum gauge,
leak-free pump, thermometers capable of
measuring temperature to within 3* C (5.4*
F), dry gas meter with ±3 percent accuracy,
and related equipment, or other metering
systems approved by the Administrator, as
required to maintain a proportional sampling
rate and to determine sample gas volume.
2.1.6 Barometer—Mercury, aneroid, or
other barometers capable of measuring
atmospheric pressure to within 3.5 mm Hg
(0.1 In. Hg). In many cases, the barometric
reading may be obtained from a nearby
weather bureau station. In which cose the
station value (which Is the absolute baro-
metric pressure) shall be requested and an
adjustment for elevation differences between
the weather station and the sampling point
shall be applied at a rate of minus 3.5 mm
Hg (0.1 in. Hg) per 80 m (100 ft) elevation
Increase or vice versa for elevation decrease.
HDIRAL MGISTtR, VOL. 41, NO. 111—TUISDAY, JUKI I, 1776
C-14
-------
PROPOSED RULES
23073
Uwlt.H!iO
moit
CONMMEMCt1MH WtTW WttUDWO
Flgur* 4-1. MoUluri wmptlng trilnT«fer«nct mtthod.
IMATKM.
Mil
•MMX
IMVOHMWr
IMMHS
MM
u*.
OWKi MOB
UM.
•AllAMKinMWMTUM
At MR «M MTU
&%
CMMIIM
IM1WMU.
HOHMi IMISTH, VOL 41, NO, Ml-TUUOAt, AIM t. 1*74
C-15
-------
J3074
PIOPOSED ftULES
FINAL
INITIAL
DIFFERENCE
IMPINGER
VOLUME,
ml
SILICA GEL
WEIGHT.
8
Figure 4-3. Analytical data-reference method.
3.1.7 Pltot tube—Type B, or equivalent,
attached to probe to allow constant monitor-
lag of the stack gas Telocity so that tbe
sampling flow rate can b» regulated pro-
portional to the eteck gas Telocity. The tip*
of the probe «nd pltot tube shall be adjacent
to e»oh other and the fr*» space between
them •hall be about IS) em (0.78 In.). When
wed with this method, tbe pltot tube need
not be calibrated.
9.1.8 Differential pressure guage—In-
cllaed manometer capable of measuring
Telocity head to within 10 percent of the
•nnnmnm measured value or ±0.013 mm
(0.0006 In.), in whtoherer to greater. Below a
differential pnavur* of 14 mm (0.08 In.)
water gauge, mleromanometen with sensi-
tivities of 0.018 mm (0.0006 In.) abould be
used. BoweTer, mleromanometen are not
easily adaptable to field conditions and are
not easy to use with the pulsating flow. Thus,
methods or other donees acceptable to the
Administrator may be used when conditions
warrant.
3.1.0 Temperature gauge—Thermocouple,
liquid filled bulb thermometer, bimetallic
thermometer, mercury-ln-glass thermometer.
or other gauges that are capable of measur-
ing temperature to within 1.8 percent of the
minimum absolute stack temperature.
a.1.10 Graduated cylinder and/or bal-
ance—To measure condensed water and
moisture caught in tbe suloa gel to within 1
ml or 1 f. Graduated cylinders shall have
subdivisions no greater than a ml. Most lab-
oratory balances are capable of weighing to
the nearest 0.8 g or less. These balances are
suitable for use here.
a.l.ll Temperature and pressure gauge*—
If Dalton's law to used to monitor tempera*
ture and pressure at condenser outlet. The
temperature gauge shall have an accuracy of
1* O (3* F).The pressure gauge tnaQ be capa-
ble of measuring pressure to within 3.8 mm
Eg (0.1 in.Eg).
9.1.13 Silica gel—If used to measure
moisture leaving condenser, Indicating type.
8-16 mesh. If previously used, dry at 178* O
(880* F) for 3 hours. New silica gel may be
used as received.
3.3 Procedure. The procedure below is
written for a condenser system Incorporating
allloa gel and gravimetric analysis to measure
the moisture leaving tbe condenser and volu-
metric analysis to measure the condensed
moisture.
3,34 Select the campling site and ratal-
mum number of sampling points according
to Method 1 or as specified by tbe Admin-
totrator. Determine the rang* of Telocity
head using Method a for the purpose of mak-
ing proportional sampling rat* calculations.
Select a suitable Telocity bead to correspond
to about 0.014 mvmm (OJJ efm). Select *
suitable probe and probe length such that all
traverse points- can be sampled. Consider
sampling from opposite aide* (four total
sampling ports) for Urge stacks to enable
use of shorter probe length*. Mark probe with
he** resistant tape or by some other method
to denote the proper distance into the stack
or duet for each sampling point. Weigh and
record weight of allloa gel to the nearest 0.6 g.
322 Select a suitable total sampling time
of notes* than 1 hour such that a mlnli
total gas sample volume of 04 m> (90 tv) at
standard condition* wlB be collected and the
sampling time per traverse point to not less
than 3 mln, or some greater time Interval
as specified by the Administrator. '
32.8 Set up the sampling train as shown
In Figure 4-1. Turn on the probe heating sys-
tem to about 130' O (348* F) so as to prevent
water condensation and allow time for tem-
perature to stabilise. Place crushed ice in
tbe lee bath container. Leak check the train
by plugging the probe inlet and pulling a 880
mm Hg (18 tn. Eg) vacuum. A leakage rat*
In excess of 4 percent of the average sampling
rate or 0.00067 mvmra. (0.03 efm), which
ever to lea*, to unacceptable.
32.4 During tbe sampling run. "^n^n
a sampling rat* within 30 percent, or as speo-
ifled by the Administrator, of constant
proportionality. For each run. record the
data required on the example datt_»QMt
shown in Figure 4-3. Be sure to record the
Initial dry gas meter reading. Record the dry
gas meter reading at tbe beginning and end
of each sampling time increment, when
change* in flow rates are made, and when
sampling to halted. Take other data point
readings at each sample point at least one*
during each time increment.
32.8 To begin sampling position the probe
tip at the first traverse point. Immediately
•tart the pump and adjust the flow to pro-
portional conditions. Traverse the cross sec-
tion. Add more lee and, if necessary, salt to
maintain a temperature of less than 30* O
(68* F) at the silica gel outlet to avoid exces-
sive moisture losses.
32.6 After collecting the sample, measure
the volume increase of tbe liquid to the near-
est 1 ml. Determine the Increase in weight
of the silica gel tube to tbe nearest 0,9 t.
Record the information (see example data
sheet. Figure 4-3) and calculate the moisture
percentage.
32 Calculations. Carry out calculations.
retaining at least one extra decimal flgur*
beyond that of th* acquired data. Bound off
figures after final calculation,
3.8.1 Nomenclature.
MDUAL MOISTn, VOL 41, NO. HI—TUISDAY, JUNI 8, 1*74
C-16
-------
. by volume
weight of water, 18 g/g-mfle (18 Ib/Ib-m«Je)
P.—Absolute pressure (for this method, same as barometric pnsrare) at tbt dry
gas meter, mm Hg (in. Hg)
P*j—8tandard absolute pressure, 760 mm Hg (29.92 in. Hg)
R—Ideal gas constant, 0.06236 (mm hg)(m1)/(g-mole)(*K) for metrio unite End
21Jt3Qn. Hg)(f«q/ab-mole)/(lb-mole)(*R) for English unite
T.—Absolute temperature at meter, °K ("R)
T-4-Absolute temperature, 293° K (528* R)
V»—Dry gas volume measured by meter, dem (def)
V«<^«—Dry gas volume measured by the dry gas meter, corrected to standard condi-
tions, dscm (dscf)
j—Volume of water vapor condensed corrected to standard conditions, m* (ft1)
»—Volume of water vapor collected In silica gel corrected to standard conditions,
V|—Final volume of condenser contents, ml
V i—Initial volume, if any, of condenser contents, ml
Wj—Final weight of condenser contents, g
W|—Initial weight of condenser contents, g
p.-Density of water, 1 g/ml (0.00220 Ib/ml)
Volume of water vapor
-K(V,-Vi) Equation 4-1
Where:
_
T» Equation 4-3
where:
K—0.3855 •E/mm Hg for metric unite
-17.65 "B/in. Hg for EngUsh units
2.3.5 Moisture Content:
o
9JJ
H-> silica get.
K-* 0.00134 m*/ml for metric unite
-0.0472 ft'/ml for English unite
Volume of water vapor ooUeoted In
Equation 4*4
Proportional sampling constant—
For each tim* Incmment, calculate
where:
K— 0.00134 m'/g for metric unite
-0.0472 ft«/g for English units
3J.4 oas votnme.
Calculate the average. XT the value for any
tune increment falls beyond 30 percent of the
average, reject the results and do run over.
Equation 4-2 *• A.pprothnaUo» Method.
The approximation method described be-
low U presented only u a suggested method.
3.1 Apparatus.
8J.1 Probe—Stainless steel or glass tub-
ing sufficiently heated to prevent water con-
densation and equipped with a filter (either
tn-etack or heated out-stack) to remove par-
tlculat* matter.
3.1.3 implngers—Two midget bnplngers,
each with 30 ml capacity, or equivalent.
HttftDI
StUCA GEL TUBE UTtBCTtt,
WHF
Molttttrs-MRVlIngtrain.
LOCATION..
TOT
toot
OPBMIM.
tAROUEmCPBESSUKL
CLOCK TMB
GAS VOLU9IE THROUGH
METER. (Vm).
«»Cft-1
RATE METEB SETTlMa
mVmiB, («t3/mla.|
UnERTEWtMTUK.
•C«"R
Figure 4-8. Fisld moisture aeitrolrauian.
FEDEIAL RfOISffit, VOL 41, NO. Ill—TUISDAT, JUNE I, 197ft
-------
23076
8.14 Ice bath— Container and l«e, to aid
In condensing moisture In Impingers.
8.1.4 Drylngtuba— Tub* packed with «-lfl
mesh indicating-type silica gel, or equivalent,
to dry the sample KM and to protect the
natter and pump.
8.1.5 Valve— Needle valve, to regulate
•ample gas flow rate.
8.1* Pump— Leak-free, diaphragm type,
or equivalent, to pull gas through the train.
8.1.7 Volume meter— Dry gat meter, suf-
ficiently accurate to meamire the sample vol-
ume within 3 percent, and calibrated over the
range of flow rates and conditions actually
used during sampling.
8.14 Bate meter— Botameter, to measure
the flow range from 0 to 8 1pm (0 to 0.11
efm).
3.1.9 Graduated cylinder— 35 ml.
3.1.10 Barometer— Mercury, aneroid, or
other barometers capable of measuring
atmospheric pressure to within 34 mm Hg
(0.1 in. Bg). In many eases, the barometric
reading may be obtained from a nearby
weather bureau station, in which case the
station value (which to the absolute baro-
metric pressure) shall be requested and an
adjustment for elevation differences between
the weather station and sampling point shall
be applied at a rate of minus 34 mm Bg
(0.1 in. Hg) per 80 m (100 ft) elevation In-
crease or vice versa for elevation decreases.
8.1.11 Vacuum gauge-^At least 700 mm
Bg (80 In. Bg) gauge, to be used for the
sampling leak check.
84 Procedure.
84.1 Place exactly 5 ml distilled water la
each Implnger. Assemble the apparatus
without the probe as shown in Figure 4-4.
Leak check by placing a vacuum gauge at the
Inlet to the first Implnger and drawing a
vacuum of at least 350 mm Bg (10 In. Bg).
plugging the outlet of the rotemeter, and
then turning off the pump. The vacuum shall
.remain constant for a least one minute.
Carefully release the vacuum gauge before
releasing the rotemeter end.
844 Connect the probe and sample at a
constant rate of 3 1pm (0.071 cfm) . Continue
Hunpllng until the dry gas meter registers
•bout 80 liters (1.1 ftf) or until visible liquid
droplets are carried over from the first Im-
plnger to the second. Record temperature.
pressure, and dry gas meter readings M re-
quired by Figure 4-0.
844 After collecting the sample, combine
the contents of the two implngers and meas-
ure volume to the nearest 04 mL
84 Calculations. The calculation method
•resented Is designed to estimate the moto-
ture in the stack gas aad therefore other
data, which are only necessary for accurate
moisture determinations, an not eoUeoted.
The following equations adequately estimate
the moisture content for the purpose of de-
termining isokinetle sampling rate settings.
84.1 Homenclature.
— Approximate water vapor In the
gas stream leaving the 1m-
pinger, 0.025 proportion by
volume
- Water vapor in the gas stream, .
proportion by volume
Molecular weight of water, 18
g/g-mole (18 Ib/llwnole)
Absolute pressure (for this
method, same as barometric
pressure) at the dry gas meter
P^-Standard absolute pressure, 760
mm Hg (29.02 in. Hg)
P-Ideal gas constant, 0.06236 (mm
Hg)V)/(g-moleS(DK) for met-
riounita and 21.83 (to, Hg) (tV)l
. (lb-mole)(°R) for English unite
T.-Abaolute temperature at meter,
•KfR)
M.
P.
PROPOSED RULES
•Standard absolute temperature,
293° K (628° R)
•Final volume of implnger con-
tents, ml
•Initial volume of implnger eon-
tents, ml
' Dry gas volume measured by dry
gas meter, dcm (dcf)
• Dry gas volume measured by dry
gas meter, corrected to stand-
ard conditions, dscm (dscf)
.Volume of water vapor con-
densed, corrected to standard
. conditions, m1 (ff)
>.-= Density of water, 1 g/ml (0.00220
Ib/mt)
844 Volume of water vapor collected.
T,i«
V,
Vi
V.
V»(.id)
=K(V,-Vi) Equation 4-8
Where:
K— 0.00134 m'/ml for metric unite
-0.0472 ft'/ml for English unite
844 CMS volume.
V-P-
where:
K= 0.3855 °K/mm Hg for metric unite
=17.66 °R/in. Hg for English units
84.4 Approximate moisture content.
Vw»
Equation 4-7
4. Calibration.
4.1 O*» mrthodit and equipment as spec-
iflled in Methods 3 and 5 and AFTD-0676 to
calibrate dry gas meter, barometer, and ther-
mometers.
0.1 Air Pollution Engineering Manual,
Danlelson, J. A. (ed.). TJB. DHBW. PBS, Na-
tional Center for Air Pollution Control, Cin-
cinnati, Ohio, PBB Publication Mb. 999-AP-
40,1967.
64 Devorkln, Howard, et al., Air Pollution
Source Testing **»«•"*'. Air Pollution Control
District, Los Angeles, Calif., November 1963.
64 Method* for Determination of Velocity.
Volume, Dust and Mist Content of Gases,
Western Precipitation Division of Joy Manu-
facturing Co., Loe Angeles, Calif., Bulletin
WP-ftO. 1968.
METHOD 6—DITEBKINATION OF
BiassioK FBOK STATIOHABT BOWKS*
1. Principle and AppHoaXHUtv.
1.1 Principle. Particulate matter is with-
drawn boklnettcally from the source and cd-
14TO Mm
.TEMPERATURE SENSOR*
PROSE
leoted on glass fiber filter matrvtnln»a at tem-
peratures in the range of 120±14> O
-------
PROPOSED RULES
23077
9.1.1 Probe noBBle—Stainless Bteel (316)
with sharp, tapered leading edge. The angle
of taper shall bes£30« and the taper shall
be on the outride to preserve a constant
Internal diameter. The probe nozzle shall
be of the button-hook or elbow design, tin-
lew otherwlM approved by tee Administra-
tor. The nozzle ahall be constructed from
Beamiest stainless steel tubing. Other con-
figurations and construction material may
be used subject to approval from the Admin-
istrator. ,
A range of sizes suitable for isoklnetlo
sampling should be available*, e.g., 0.83 em
(H In.) up to 1.37 em (V4 In.) (or larger
If higher volume sampling trains are used)
Inside diameter (ID) nozzles In Increments
of 0.18 em (M« in.). Bach nozzle shall be
calibrated according to the procedures out-
lined in the calibration section.
3.1.a Probe liner—Boroslllcate or quartz
glass tubing with a heating system capable
of maintaining a gas temperature at the'
exit end during sampling of no greater than
I30±14* O (248±25a F) or no greater than
such other temperature at specified by an
applicable subpart of the standards. Since
the actual temperature at the outlet of the
probe Is not monitored during sampling,
probes constructed according to APTD-0581
and utilizing the calibration curves of
APTD-0578 or calibrated according to the
procedure outlined in APTD-OB76 will be
considered as acceptable.
Borosilicate or quarto glass probe liners
ahall be used for temperatures up to about
480* O (900* F) and quartz liners for tem-
peratures up to about BOO* O (I860* F). Both
may be used at higher temperatures for
abort periods of time, but must be approved
by the Administrator. The softening tem-
perature for borostllcate Is 820' 0 (1608* F)
and for quartz it is 1800* 0 (3783* F).
When length limitations, i.e. greater than
about 3.B m (8.3 ft), are encountered at
temperatures less than 830* O (60S' F),
stainless steel (318) of Inooloy 838 > (both
of seamless tubing), or other materials M
approved by the Administrator, may be used.
Metal probes for sampling gas streams at
temperatures in excess of 930* O (80S* F)
must be approved by the Administrator.
3.1.3 Pltot tube—Type S, or other device
approved by the Administrator, attached to
probe to allow constant monitoring of the
stack gas velocity. The face openings of the
pltot tube and the probe nozzle shall be
adjacent and parallel to each other, not
necessarily on the same plane, during sam-
pling. The free space between the nozzle
and pltot tube shall be at least 1.9 cm
(0.75 in.). The free space shall be set based
on a 1.3 cm (0.6 In.) ID nozzle. If the sam-
pling train is designed for sampling at higher
*ow rates than that described In APTD-
0581, thus necessitating the use of larger
sized nozzles, the largest sized nozzle shall
be used to set the free epace.
The pltot tube must also meet the criteria
specified in Method 3 and calibrated ac-
cording to the procedure in the calibration
section of that method.
3.1.4 Differential pressure gauge—Inclined
manometer capable of measuring velocity
head to within 10 percent of the minimum
measured value or ±0.018 mm (0.008 In.),
whichever Is greater. Below a differential
pressure of 1.8 mm (0.08 in.) water gauge,
mlcromanometers with sensitivities of 0.013
mm (0.0008 in.) should be used. However,
mleromanometers are not easily adpatable
to field conditions and are not easy to use
with pulsating flow. Thus, methods or other
'Mention of trade names or specific prod-
ucts does not constitute endorsement by the
Environmental Protection Agency.
devices acceptable to the Administrator may
be used when conditions warrant.
3.1.8 Filter holder—Borosilicate glass
frit filter support and a sillcone rubber gas-
ket. Other materials of construction may be
used with approval from the Administrator,
e.g., if probe liner to stainless steel, then the
filter holder may be stainless steel. The holder
design shall provide a positive seal against
leakage from the outside or around the
filter.
9.1.6 Filter heating system—Any beating
system capable of maintaining a tempera-
ture around the filter holder during sam-
pling of no greater than 130 ±14* O (248
±35* F), or such other temperature as spec-
ified by an apppllcable subpart of the stand-
ards. A temperature gauge capable of
measuring temperature to within 30* O (8.4'
F) shall be Installed such that temperature
around the filter holder can be regulated
and monitored during sampling. Heating
systems other than shown In APTD-0581
may be used.
3.1.7 Condenser—Any system that cools
the sample gas stream and allows meas-
urement of the water condenser and mois-
ture leaving the condenser, each to within
1 ml or 1 g. Acceptable means are to meas-
ure the condensed water either gravlmetrl-
cally or volumetrlcally and to measure the
moisture leaving the condenser by (1) mon-
itoring the temperature and pressure at the
exit of the condenser and using Dalton's
law or (3) by passing the sample gas stream
through a tared silica gel trap with exit
gases kept below 90* O (88* F) and deter-
mining the'weight gain.
Norr.—If "condenslble participate mat-
ter" is desired, in addition to moisture eon-
tent, the following system shall be vised—
four Implngers connected in series with
ground glass, leak free fittings or any simi-
larly leak free noncontamlnatlng fittings.
The first, third, and fourth Implngers shall
be of the Oreenburg-Smith design, modified
by replacing the tip with a 1.3 cm (H in.)
ID glass tube extending to about 1.3 cm (V,
In.) from the bottom of the flask. The sec-
ond Implnger shall be of the Greenburg-
Smith design with the standard tip. Indi-
vidual States or control agencies requiring
this information shall be contacted as to
the -sample recovery and analysis of the Im-
plnger contents.
For purposes ot writing the procedure of
this method, the system described in the
note above will be used for determining the
moisture content of the stack gas. Modifi-
cations (e.g. using flexible connections be-
tween the impingers or using material* other
than glass) may be used with approval from
the Administrator.
If means other than silica gel are used to
determine the amount of moisture leaving
the condenser, it is recommended that silica
gel still be used between the condenser
system and pump to prevent moisture con-
densa^on In the pump and metering devices.
Unless otherwise specified by the Admin-
istrator, flexible vacuum lines may be used
to connect the filter holder to the condenser.
Xl.ft Metering system—Vacuum gauge,
leak-free pump, thermometers capable of
measuring temperature within 3* O (6.4* F),
dry gas meter with 9 percent accuracy, and
related equipment, or equivalent, as required
to maintain an laokinetic sampling rate and
to determine sample volume. Sampling trains
utilizing metering systems designed tor
higher flow rates than that described la
APTD-0581 or APTD-OB76 may be used pro-
vided that the specifications In section 9
of this method are met. When the metering
system is used in conjunction with a pilot
tjube, the system shall enable checks of
uoklnetic rates.
9.1.9 Barometer—Mercury, aneroid, or
' other barometers capable of measuring at-
moepherlo pressure to within 3.8 mm Hg
(0.1 in. Hg). In many cases, the barometric
reading may be obtained from a nearby
weather bureau station, in which case the
station value (which la the absolute baro-
metric pressure) shall be requested and an
adjustment for elevation differences between
the weather station and sampling point shall
be applied at a rate of minus 3.8 mm Hg (0,1
in. Hg) per 30 m (100 ft) elevation increase
or vice vena for elevation decrease,
3.1.10 Oas density determination equip-
ment—Temperature and pressure gauges and
gas analyzer as described in Methods 3 and
3.
2a.ll Temperature and pressure gauges—
If Dalton's law U used to monitor tempera-
ture and pressure at condenser outlet. The
temperature gauge shall have an accuracy
of r O (2« F). The pressure gauge shall be
capable of measuring pressure to within 3.6
mm Hg (0.1 in. Hg). If silica gel Is used In
the condenser system the temperature and
pressure must be measured before the silica
gel component.
2.2 Sample recovery.
3.3.1 Probe liner and probe nozzle
brushes—Nylon bristles with stainless steel
wire handles. The probe brush shall have
extensions, at least as long as the probe, of
stainless steel, nylon, teflon, or similarly
Inert material. Both brushes shall be properly
Bleed and shaped to brush out the probe
liner and nozzle.
9.3.3 Glass wash bottles—Two.
3.3.3 Glass sample storage containers—
Chemically, resistant, borosilieate glass hot-
tlea, for acetone washes, 500 ml 'or 1,000 ml.
Screw cap closures shall be teflon rubber-
backed liners or of such construction so
as to be leak free and prevent chemical at-
tack from the acetone. (Narrow mouth glass
bottles have been found to be leu prone to
leakage.) Other types of containers must be
approved by the Administrator.
3.2.4 Petrl dishes—For filter samples,
glass or polyethylene, unless otherwise
specified by the Administrator.
3.3.8 Graduated cylinder and/or bal-
ance—To measure condensed water to within
1 ml or 1 g. Graduated cylinders shall have
subdivisions no greater than 3 ml. Moat
laboratory balances are capable of weighing
to the nearest 0.5 g or less. Any of these
balances are suitable for use here and In
section 9.3.4.
2.2.0 Plastlo storage containers—Air
tight containers to store silica gel.
2.2.7 Funnel and rubber policeman—To
aid in transfer of silica gel to container; not
necessary if silica gel is weighed In the field.
2.3 Analysis,
2.3.1 Glass weighing dishes.
9.3.9 Desiccator.
3.33 Analytical balance—To measure to
within 0.1 mg.
3.3.4 Balance—To measure to within O.S
'3.3.8 Beakers—250,ml.
9.8 ,fl Hygrometer—To measure the rela-
tive humidity of the laboratory environment.
3.3.7 Temperature gauge—To measure
the temperature of the laboratory
environment.
3. Reagents.
3.1 Sampling.
8.1.1 Filters—Glaas fiber filters, without
organic binder exhibiting at least 99.95 per-
cent efficiency («£0.05 percent penetration)
oa 0.3 micron dloetyl phthalate smoke par-
ticles. The filter efficiency test shall be con-
ducted In accordance with ASTM standard
method D 9988-71. Test data from the sup-
plier's quality control program Is suffleteat
for this purpose.
riDIRAL UOISTtt, VOL. 41, NO. Ill—TUMDAY, JUNI I, 1976
C-19
-------
23078
PROPOSED RULES
3.14 Silica gel—Indicating type, «-!«
mesh. If previously used, dry at 178* O (800*
F) for 3 noun. New silica gel may be used
•a received.
8.1.3 Water—When analysis of the mate-
rial caught In the impinger* is required, dis-
tilled water shall be wed. Bun blanks prior
to field-use to eliminate a high blank on test
samples.
8.14 Crushed toe.
8.1.5 Stopcock grease Acetone insoluble.
beat stable silicon* grease. This Is not neces-
sary >t screw-on connectors with teflon
sleeves, or similar, are used.
3.2. Sample recovery.
33.1 Acetone—Reagent grade. ^0.001 per-
cent residue, In glass bottles. Acetone from
metal containers generally has a high residue
blank and should not be used. Sometimes.
suppliers transfer acetone to glass bottles
from metal containers. Thus, acetone blanks
shall be run prior to field use and only ace-
tone with low blank values (=£0.001 percent)
shall be used.
3.3 Analysis.
3.3.1 Acetone—Same as 3.3.1.
333 Desiocant—Anbyrdous calcium sul-
fate, indicating type.
4. Procedure.
4.1 Sampling. The sampling shall be con-
ducted by competent personnel experienced
with this test procedure.
4.1.1 Pretest preparation. All the com-
ponents shall be maintained and calibrated
according to the procedure described in
AFTD-0576. unless otherwise specified herein.
Weigh approximately 300-300 g of allloa
gel In air tight containers to the nearest
0.0 g. Record the total weight, both silica gel
and container, on the container. More silica
gel may be used but care should be taken
during sampling that It Is not entrained and
carried out from the tmplnger. As an alter-
native, the silica gel may be weighed directly
In the impinger or Its sampling .holder Just
prior to the train assembly.
Check niters visually against light for
irregularities and flaws or plnhole leaks. Label
a filter of proper diameter on the back side
near the edge using numbering mac.hlnn
Ink. As an alternative, label the shipping
container (glass or plastic petrl dishes) and
keep the filter in this container at all times
except during sampling and weighing.
Desiccate «be filters at ao±6.o' C (68±10*
*) and ambient pressure for at least 34 hours
and weigh at 0 or more hour intervals to a
constant weight, l.e.. ^0.8 mg change from
previous weighing, and record results to the
nearest 0.1 mg. During each weighing the
filter must not be exposed to the laboratory
atmosphere for a period greater than 3 min-
utes and a relative humidity above BO per-
cent.
4.13 Preliminary determinations. Select
the sampling site and the minimum number
of sampling points according to Method 1 or
as specified by the Administrator. Determine
the stack pressure, temperature, and the
range of velocity heads using Method 3 and
moisture content using Approximation
Method 4 or its alternatives for the purpose
of making isoklnetle sampling rate calcula-
tions, estimates may be used. However, final
result* will be based on actual measurements
made during the test.
Select a nozzle stee based on the range of
velocity heads such that it Is not necessary
to change the notale SUM In order to main-
tain Isoklnetic sampling rates. During the
ran, do not change the norale suse. Insure
that the differential pressure gauge is capable
of measuring the f^n*™™™ velocity head
value to within 10 percent, or as specified by
the Administrator.
Select a suitable probe liner and probe
length such that all traverse points can be
sampled. Consider sampling from opposite
sides for large stacks to reduce the length of
probes.
Select a total sampling time greater than
or equal to the minimum total sampling tin
in the' test procedures for the spe-
cific Industry such that the sampling time
per point Is not toss than a mln. or some
greater time Interval as specified by the Ad-
ministrator and the sample volume that win
be taken will exceed the required minimum
total gas sample volume specified in the test
procedures for the specific industry. The lat-
ter Is based on an approximate •average
sampling rate. Note also that the minimum
total sample volume Is corrected to standard
conditions.
It is recommended that >/4 or an Integral
number of minutes be sampled at each point-
in order to avoid timekeeping errors.
In some circumstances, e.g. batch cycles,
it may be necessary to sample for shorter
times at the traverse, points and to obtain
smaller gas sample volumes. In these cases,
the Administrator's approval must first be
obtained.
4.1.8 Preparation of collection train. Dur-
ing preparation and assembly of the sampling
train, keep all openings where contamination
can occur covered until Just prior to as-
sembly or until sampling is about to begin.
Place 100 ml of water in each of the first
two implngers, leave the third impinger
empty, and place approximately 300-300 g
or more, if necessary, of prewelghed silica gel
In the fourth Impinger. Record the weight
of the silica •gel and container to the nearest
0.6 g. Place the container In a clean place
for later use in the sample recovery.
Using a tweezer or clean disposable surgi-
cal gloves, place the labeled (identified) and
weighed filter in the filter bolder. Be sure
that the filter Is properly centered and the
gasket properly placed so as not to allow the
sample gas stream to circumvent the filter.
Check filter for tears after assembly is
completed.
When glass liners are used, install selected
nozele using a Viton A1 O-ring when stack
temperatures are toes than 360* O (COO* F) •
or an asbestos string gasket when tempera-
tures are higher. The Viton A O-rlng and
asbestos string gasket are Installed as a seal
where the noale is connected to a glass
liner. See AFTD-OBTo for details. When metal
.liners are need, Install the nozzle as above
or by a leak free direct mechanical connec-
tion. Mark probe with heat resistant tape or
by some other method to denote the proper
distance into the stack or duct for each
sampling point.
tTnless otherwise specified by the Adminis-
trator, attach a temperature probe to the
metal sheath of the sampling probe so that
the sensor extends beyond the probe tip and
does not touch any metal. Its position should
be about li to 3.64 cm (0.76 to 1 in.) from
both the pltot tube and probe nozzle to
avoid Interference with the gas flow.
Set up the train as In Figure 6-1. using, if
necessary, a very light coat of sillcone grease
on all ground glass Joints, greasing only the
eater portion (see APTD-0676) to avoid pos-
sibility of contamination by the sillcone
grease. With approval from the Administra-
tor, a glass cyclone may be used between the
probe and filter bolder.
Place crushed toe around the implngers.
4.1.4 Leak check procedure—After the
sampling train has Been assembled, turn on
and set the filter and probe heating system
to the power required to reach a temperature
of iao±14' C (348±96* V} or such other
'Mention of trade names Is not intended
to constitute endorsement by KPA,
IfORAL ttOMTH, VOL 41, NO. Ill—TUtSDAY, JUNI I, 1W6
C-20
-------
PROPOSED RULES
23079
temperature M specified by an applicable
eubpart of the standard* for the leak check.
(If water condensation to not a problem the
probe and/or filter heating system need not
be used.) Allow time tot the temperature to
stabilize. If • Vlton A O-rtag or other leak
free connection is used In assembling the
probe nozzle to the probe liner, leak check
KANT
LOCATIOI*
orcnATOd
DATE
RUN NO _
SAMPLE BOX NO..
METER BOX N0._
UHERAH0
CFACTOR
the train at the lampllng site by.plugging
the nocEle and pulling a 380 mm Hg (16 In.
Bg) vacuum.
Won.—A lower vacuum may be need pro-
Tided that It to not exceeded during the test.
'If an asbestos string is used, do not con-
nect the probe to the train during the leak
check. Instead, leak check the train as above
by first plugging the Inlet to the filter
holder. Then connect the probe to the train
and leak check at about 38 nun Hg (1 in.
Kg) vacuum. A leakage rate In excess of 4
percent of the average sampling rate or
0.00067 m'/mln. (0.03 cfm). whichever is lew.
to unacceptable In either <
MOT TUBE COEFFICIENT. C,.
SCHEMATIC OF STACK CBOSS SECTION
AMOtr.Nl UUPCnATURE
BAnnurrmc PRESSURE
ASSUMED MOISTURE. %
PROBE LENGTH, m (111 _
NOZZLE IDENTIFICATION N0.__
AVERAGE CALIBRATED NOZZLE DIAMETER, twIW-
PROBE HEATER SETTING
LEAK RATE.mVmla Mm)
PROBE LINIR MATERIAL
TRAVERSE POINT
NIWKR
TOTAL
AVERAGE
SAMPLING
TIME
(01, ml*
-
STATIC
PRESSURE
HM MQ
(i« MB)
-
STACK
TEMPERATURE
|T$I
•C (»Ft
VELOCITf
HEAD
(APj).
wwflHtjHjO
PRESSURE
DIFFERENTIAL
ACROSS
ORIFICE
METER
miH20
(In. H20)
GAS SAMPLE
VOIUUE
n3 (lljl
CAS SAMPLE TE1VEHA1URE
AT ORT GAS METER
INIET
»C »»FI
A«g.
OUTLET
•C (»F|
Avg.
Avg.
FILTER HOLDER
TFWERATURE.
•c i*«.
TEMPERATURE
OF CAS
UAVINO
CONDENSER OR
LAST IUPINGER.
•CI«FI
The following leak check Instructions for
the sampling train described In AFTD-0576
and APTD-0681 may be helpful. Start the
pump with by-paw valve fully open and
coarse adjust valve completely closed. Par-
tially open the coarse adjust valve and "lowly
close the by-pass valve until 880 mm Bg (IB
In. Hg) vacuum to reached. Do not reverse
direction of by-pass valve. This wffl cause
water to back up into the niter holder. If
880 mm Hg (IB In. Hg) Is exceeded, either
leak check at this higher vacuum or end
the leak check as shown below and start
When the leak cheek Is completed, first
slowly remove the plug from the inlet to
the probe or filter holder and Immediately
turn off the vacuum pump. This prevents
the water in the Implngers from being forced
backward into the filter holder and silica
gel from being entrained backward Into the
third Implnger.
Leak checks shall be conducted as de-
scribed whenever the train to disengaged, e.g.
for silica gel or filter changes during the
test, prior to each test run, and at the com-
pletion of each test run. If leaks are found
to be In excess of the acceptable rate, the test
Figure 5-2. Paniculate field data.
win be considered Invalid. To reduce lost
time due to leakage occurrences. It Is recom-
mended that leak cheeks be conducted be-
tween port changes at the highest vacuum
reading drawn during that sampling traverse.
4.1.6 Partloulate train operation—Dur-
ing the sampling run, tooklnetlo sampling
rate to within 10 percent, or as specified by
the Administrator, of true Isoklnetie and the
temperature around the filter of no greater
than iaO±14* O (248±96* P), or as speci-
fied by an applicable subpart of the stand-
ards, thftll be maintained.
For each run, record tne data required on
the example data sheet shown in Figure 5-3.
Be .sure to record the Initial dry gas meter
reading. Record the dry gas meter readings
at the beginning and end of each sampling
time Increment, when changes in flow rates
are made, and when sampling Is halted. Take
other d*ta point readings at least once at
each sample point during each time Incre-
ment and additional readings when signifi-
cant changes (30 percent variation In veloc-
ity head readings) necessitate additional
adjustments In flow rate. Level and eero the
manometer.
Clean the portholes prior to the test run
to uninfiMtMi the chance of sampling the de-
posited material. To begin sampling, remove
the nozzle can, verify that the filter and
probe are up to temperature, and that the
pilot tube and probe are properly positioned.
Position the nozzle at the first traverse point
with the tip pointing directly into the gas
stream. Immediate start the pump and ad-
Just the flow to Isoklnetie conditions. Nomo-
graphs are available for sampling trains us-
ing type B pltot tubes with 0.85±0.02 co-
efficient and when sampling In air or a stack
gas with equivalent density (molecular
weight equal to 38±4). which aid in the
rapid adjustment of the Isoklnetie sampling
rate without excessive computation*. AFTD-
0676 details the procedure for using these
nomographs. If O, and M* are outside the
above stated ranges, do not use the nomo-
graph unless appropriate steps (see Infer-
ence 7.7) are taken to compensate for th»
deviations.
When the stack is under significant nega-
tive stack pressure '(height of Implnger
stem), take care to close the coarse adjust
valve before inserting the probe into the
stack to avoid water backing into the filter
RDEIAL MOISTIR, VOl. 41, NO. til—TUiSDAY, JUNE 8,
C-21
-------
23080
PROPOSED RULES
bolder. If necessary, the pump may be turned
on with the coarse adjust valve closed.
When the prob« it In position, block on
the openings around the probe and port-
bole to prevent unrepresentative dilution of
the gas stream.
Traverse the stack cross section, as re-
quired by Method 1 or as specified by the
Administrator, being careful not to bump
the probe nozzle into the stack walls when
sampling near the walls or when removing
or inserting the probe through the portholes,
to minimize chance of extracting deposited
material.
During the test run, make periodic ad-
justments to keep the temperature around
the alter holder at the proper temperature
and add more ice and, if necessary, salt to
maintain a temperature of less than 20'O
(88'P) at the condenser/silica gel outlet to
avoid excessive moisture losses. Also, periodi-
cally check the level and zero of the mano-
meter.
If the pressure drop across the filter be-
comes too high making Isoklnetlo sampling
difficult to maintain, the filter may be re-
placed In the midst of a sample run. It Is
recommended that another complete filter
Assembly be used rather than attempting
to change the filter Itself. After the new
niter or filter assembly Is Installed conduct
a leak check. The participate weight shall
Include the summation of all filter as-
sembly catches.
A single train shall be used for the entire
•ample run, except for filter and silica gel
changes. However, If approved by the Admin-
istrator, two or more trains may be used for
a single test run when there are two or
more ducts or sampling ports. The results
•hall be the total of all sampling train
catches,
'At the end of the sample run, turn off
the pump, remove the probe and nozzle from
the stack, and record the final dry gas meter
reading. Perform a leak check at a vacuum
equal to or greater than the maximum
reached during sampling. Calculate percent
Jsoklnetlo (see calculation section) to de-
termine whether another test run should be
made. If there Is difficulty in maintaining
Isoklnetlo rates due to source conditions,
consult with the Administrator for possible
variance on the isoklnetic rates.
4.3 Sample recovery- Proper cleanup pro-
cedure begins as soon as the probe Is re-
moved from the stack at the end of the
sampling period. Allow the probe to cool.
When the probe can be safely bandied,
wipe off all external "partlculate matter near
the tip of the probe nozzle and place a cap
over It to prevent losing or gaining par-
tlculate matter. Do not cap off the probe
tip tightly while the sampling train is cool-
ing down as this would create a vacuum in
the filter holder, thus drawing water from
the Impingers Into the filter.
Before moving the sample train to the
cleanup site, remove the probe from the
•ample train, wipe off the sUlcone grease,
and cap the open outlet of the probe. Be
careful not to lose any condensate, if present.
Wipe off the slilcone grease from the filter
Inlet where the probe was fastened and- cap
It. Remove the umbilical cord from the last
Implnger and cap the Implnger. If a flexible
line I* used between the first Implnger or
condenser and the niter holder, disconnect
the line at the Alter holder and let any
condensed water or liquid drain Into the
implngers or condenser. After wiping off the
sllicone grease, cap off the filter holder out-
let and Implnger Inlet. Either ground glass
stoppers or plastic caps or serum caps may
be used to close these openings.
Transfer the probe and filter-implngor as-
sembly to the cleanup area. This area should
be clean and protected from the wind so that
the chances of contaminating or losing the
sample will be minimized.
Save a portion of the acetone used for
cleanup as a blank. Place about 300 ml of
this acetone taken directly from the wash
bottle being used In a glass sample container
labeled "acetone blank."
Inspect the train prior to and during dis-
assembly and note any abnormal conditions.
Treat the samples as follows:
Container No. 1, Carefully remove the filter
from the filter holder and place In it* Iden-
tified petrl dish container. Use a pair of
tweezers and/or clean disposable surgical
gloves to handle the filter. If it is necessary
to fold the filter, do so such that the par-
tlculate cake Is Inside the fold. Quantita-
tively remove any paniculate matter anci/.or
filter which adheres to the filter holder gas-
ket by carefully using a dry nylon bristle
brush and/or a sharp-edged blade and place
Into this container. Seal the container.
Container No. 2. Taking care to see that
dust on the outside of the probe or other
exterior surfaces does not get Into the sample,
quantitatively recover participate matter or
any condensate from the probe nozzle, probe
fitting, probe liner, and front half of the
filter holder by washing these component*
witb acetone and placing the wash Into a
glass container in the following manner:
Distnied water may be used instead of
acetone when approved by the Administrator
or shall be used when specified by the Ad-
ministrator. In these cases, save a water
blank and follow Administrator's directions
on analysis.
Carefully remove the probe nozzle and
dean the inside surface by rinsing with ace-
tone from a wash bottle and brushing with
a nylon bristle brush. Brush until acetone
rinse shows no visible particles, after which
make a final rinse of the inside surface with
acetone.
Brush and rinse with acetone the inside
parts of the Swagelok fitting in a similar way
until no visible particles remain.
Rinse the probe liner with acetone by tilt-
Ing the probe and squirting acetone into its
upper end, while rotating the probe BO that
all inside surfaces will be rinsed with ace-
tone. Let the acetone drain from the lower
end into the sample container. A funnel may
be used to aid in transferring liquid washes
to the container. Follow the acetone rinse
with a probe brush. Hold the probe in an
Inclined position, squirt acetone into the
upper end as the probe brush Is being pushed
with a twisting action through the probe,
hold a sample container underneath the low-
er end of the probe, and catch any acetone
and participate matter which is brushed
from the probe. Run the brush through the
probe three times or more until no visible
partlculate matter is carried out with the
acetone or remains in the probe liner on
visual inspection. With stainless steel or
other metal probes, run the brush through
in the above prescribed manner at least six
times since metal probes have small crevices
in which paniculate matter can be en-
trapped. Rinse the brush with acetone and
quantitatively collect these washings in the
•ample container. After the brushing make
a final acetone rinse of the probe f. de-
scribed above.
It Is recommended that two people be used
to clean the probe to minimise losing the
•ample. Between sampling runs, keep brushes
clean and protected from contamination.
After ensuring that all Joints are wiped
clean of sllicone grease, clean the Inside of
the front half of the filter holder by nibbing
the surfaces with a nylon bristle brush and
rinsing with acetone. Rinse each surface
three times or more • if needed to remove
visible paniculate. Make a final rinse of
the brush and filter holder. After all acetone
washings and paniculate matter are collected
In the sample container, tighten the lid on
the sample container so that acetone will
not leak out when it Is shipped to the labora-
tory. Mark the height of the fluid level to
determine whether or not leakage occurred
during transport. Label container to clearly
Identify its eontents.
Container No. 4.-Note color of indicating
silica gel to determine If it has been com-1
pletely spent and make a notation of its
condition. Transfer the silica gel from the
fourth Implnger to the original container
and seal. A funnel may make it easier to
pour the silica gel without •pilling. A rubber
policeman may be used as an aid in removing
the silica gel from the Implnger. It is not
necessary to remove the small amount of
dust particles that may adhere to the wall*
and are difficult to remove. Since the gain
in weight Is to be used for moisture calcula-
tions, do not use any water or other liquids
to transfer the silica gel. If a balance U
available in the field, follow the procedure
under analysis.
Impinger water. Treat the Implnger* or
condenser as follows: Make a notation of
any color or film in the liquid catch. Measure
the liquid which Is in the first three Implng-
ers to within ±1 ml by using a graduated
cylinder or, if available, to within ±0.6 g by
using a balance. Record the volume or weight
of liquid present. This Information it re-
quired to calculate the moisture content of
the effluent gas.
If analysis of the Implnger catch is not
required, discard the liquid after measuring
and recording the volume or weight. If anal-
ysis of the Implnger catch Is required, leave
the Implngers intact to transfer the liquid,
cap off the inlet, and pour the liquid through.
the outlet into the graduated cylinder or into
a sample container after it* weight .has been.
determined.
If a different type of condenser is used,
measure the amount of moisture condensed
either volumetrlcally or gravtmetrlcally.
4.3 Analysis. Record the data required on
the example sheet shown in Figure 8-3. Han-
dle each sample container a* follows:
Container No. l. Leave In ahipplng con*
talner or transfer the filter and any loose
paniculate from the sample container to a
tared glass weighing dish and desiccate for
94 hours in a desiccator containing anby-.
drous calcium sulfate. Weigh to a constant
weight and report the results to- the nearest
0.1 mg. for purposes of this section 4.S, the
term "constant weight" mean* a difference
of no more-than 0.8 mg or 1 percent of total
weight less tare weight, whichever U greater,
between two consecutive weighing*, with no
lee* than 0 hours of desiccation time between
weighing* and no more than 3 minute* ex-
posure to the laboratory atmosphere (must
be lees than 60 percent relative humidity)
during weighing.
FEDERAL IMISTER, VOL. 41, NO. Ill—TUUDAY, JUNI t, 1W
C-22
-------
PROPOSED RULES
29061
Plant.
Date.
Run No..
Relative Humidity
Amount liquid lost during transport
Acetone blank voNime.ml
Acetone wash volume, ml
Acetone blank concentration, mg/mg (equation 5-4).
Acetone wash blank, mg (equation 5-5)
CONTAINER
NUMBER
WEIGHT OF PARTICIPATE COLLECTED,
mg
FINAL WEIGHT
TARE WEIGHT
WEIGHT GAIN
2
Let* acetone blank
Weight of paniculate matter
FINAL
INITIAL
LIQUID COLLECTED
TOTAL VOLUME COLLECTED
VOLUME OF LIQUID
WATER COLLECTED
IMPINGER
VOLUME.
ml.
SILICA GEL
WEIGHT.
9
fl'l ml
CONVERT WEIGHT OF WATER TO VOLUME BY DIVIDING TOTAL WEIGHT
INCREASE BY DENSITY OF WATER (Ig/ml).
INCREASE. 8 >VOLlny|EWATeRtm|
Ig/ml
Figure 5-3. Analytical data.
MMfiu, VOL 41. NO. in—TutsoAr. JUM a, me
C-23
-------
29082 MOPOSED RULES
Container No. 2. Not* level of liquid In When nozzles become nicked, dented, or
container and confirm on analysis sheet corroded, they shall be reshaped, sharpened.
whether or not leakage occurred during and recalibrated before use.
transport. Measure the liquid In this eon- Bach neavle shall be permanently and
tamer either volumetrlcally to ±1 ml or uniquely Identified.
gravlmetrlcally to ±0.6 g. Transfer the con- 5.2 Pitot tube. The pltot tube •hall be
tents to a tared 260 ml beaker, and evaporate calibrated according to the procedure out-
to dryness at ambient temperature and pres- lined in Method 2.
sure. Desiccate for 34 hours and weigh to a 6.8 Dry gat meter and orifice meter. Both
constant weight. Report the result* to the meters shall be calibrated according to the
nearest 0.1 mg. procedure outlined in APTD-0678. When ft
Container No. 3. Weigh the spent silica gel diaphragm pump Is used, assure that there
to the nearest 0.5 g using a balance. This is no leak.
step may be conducted in the field. 6.4 Probe heater calibration. The probe
"Aettoiu Blank" Oonttriner. Measure aos- heating system shall be calibrated according
tone in this container either TolumetrlcaUy to the procedure innrtalnnd in APTD-0876.
or gravlmetrloally. Transfer the acetone to a Probes constructed •'"""Ulry to APTO-OB81
tared 380 ml beaker and evaporate to dryness need not be calibrated U the calibration
at ambient temperature and pressure. Deslc- curves la AFTD-0678 are used.
cate for 34 hours and weigh to a constant 5.6 Temperature gauges. 'Calibrate
weight. Report the results to the nearest and liquid filled bulb thermometers
0.1 mg. thermocouple-potentiometer systems against
0. Calibration. mercury-ln-glaee thermometers. Ice bath and
Maintain a laboratory log of all callbra- boiling water (corrected for barometric pres-
ttona. sure) are acceptable reference points. Per
8.1 Probe nozzle. Using a micrometer, other devices, check with the Administrator.
measure the inside diameter of the noole fl. Calculations,
to the nearest 0.095 mm (0.001 In.). Make 8 carry out calculations, retaining at least
of the measuremente. The difference between «o««l»« «•*•• *ound off figures after final
the high and low numbers shall not exceed calculation.
0.1 mm (0404 In.). 6.1 nomenclature
A.— Cross sectional area of noule, m*
Bw.— Water vapor in the gas stream, proportion by volume
C.— Acetone blank residue concentration,' mg/g
e. — Concentration of partieulate matter in stack gas, dry basis, corrected to standard
conditions, g/daom (g/dscf)
I «• Percent of laokinetlo sampling
m»— Total amount of particulate matter collected, mg
M.» Molecular weight of water, 18 g/g-mole (18 lb/lb-mole)
m»>»Mass of residue of acetone after evaporation, mg
!**»•• Barometric preasure at the sampling site, mm Hg On. Hg)
P.— Absolute staek gas pressure, mm Hg (in. Hg)
P,jd«" Standard absolute pressure, 760 mm Hg (29.02 in. Hg)
S- Ideal gas constant, 0.06236 mm Hg-m»rK-g-moleJ2f;83 In. Hg-ff/fP-lb-mole)
TB— Absolute average dry gas meter temperature see (Figure 6-3), *K (*R)
T.« Absolute average stack gas temperature (see Figure &-2), *K (*R)
T..d— Standard absolute temperature, 293° K'(«
V,™ Volume of acetone blank, ml
V..— Volume of acetone used in wash, ml
Vi.— Total volume of liquid collected in impingers and silica gel (M* Figure 6-3), ml
V.— Volume of gas sample as measured by dry gas meter, dcm (dcf)
V.dM)— Volume of gas sample measured by the dry gas meter corrected to standard
conditions, dsem (dsef)
V, <,«]—• Volume of water vapor in the gas sample corrected to standard conditions,
som (scf)
v.-SUck gas velocity, calculated by Method 3, Equation 3-7 using data obtained
from Method &Y in/see (ft/tee)
W»™ Weight of residue in acetone wash, mg
AH— Average pressure differential across the orifice meter (pee Figure 5-2), mm H|0
(in. HiO)
ft •- Density of acetone, mg/ml (see label on bottle)
p.- Density of water. 1 g/ml (0.00220 Ib/ml)
6— Total sampling time, min
13.8 -Specific gravity of mercury
60-Sec/min
100— Conversion to percent
6 J Average dry gas meter temperature and average orifice pressure drop. Bee data sheet
(Figure 6-9).
9* Dry gas volume. Correct the sample volume measured by the dry gas meter to
standard conditions (to* O, T80 mm Hg or 6T P. MM in. Eg) by using Bquatton 6-1*
where:
K-0.3865 eK/mm Hg for metric units
• 17.65 •R/m. Hg for English nniti
RDIIM UOISIU. VOL 41, MO, 111—TUUOAY, MNI 6,
C-24
-------
PROPOSED RULES
29083
6.4 Volume of water vapor.
Vw
{»td>«
Equation 6-2
mVml for metric unite
—0.0472 ftf/ml for English unite
content
— -!-= -
Equation 5-3
64 Acetone blank concentration.
Equation 5-5
9* Total partlaulato weight. Determine
the total partieulate catch from the sum
of tli* weights obtained from containers 1
and 3 less the acetone blank r ~
»-»).
09 Parttculate concentration.
o.- (0.001 g/mg) (m/V.
Equation 5-0
' 6.10 Conversion factors:
To- MnWply by-
KL ............... m* ----------------
f/W
Equation 5-4 i/ft«III"I"""II
0,0281
14.4
U.I1
•6.7 Acetone wash blank.
0.11 ttoklnetle variation.
6.11.1 Calculations from raw data.
when:
100TJKV,«+ (VJT.)P,«,+AH/13.«)1
6WV.P.A.
K=0.00346 mm Hg-m'/ml-'K for metric units
-0.00267 In. Hg-ft'/ml-'R for English unite
Equation 5-7
6.1UJ
values.
Calculation! from tntermediate
I-
where:
Equation 5-8
E « 4.323 for metric unite
-0.0944 for English unite
6.U Acceptable result*. If 90 percent
£3 f£110 percent, the results are acceptable.
It the results are low in comparison to the
•taadards and I Is beyond toe acceptable
range, the Administrator may option to ac-
cept the results. Use reference 7.4 to mak»
judgments. Otherwise, reject the results and
repeat tbe test.
7. JtS/STtfflCS*
71 Addendum to Specifications for Incin-
erator Testing at Federal Facilities,. FOB,
MOAPO. Deo. 6,1967.
7J Martin, Robert M, Construction De-
tails of isoklnetto Source Sampling equip-
ment. Environmental Protection Agency,
AFTD-OUl, April 1971.
7.3 Bom, Jerome J., Maintenance, Calibra-
tion, and Operation of Isokinetlc Source flanv
pnng Bqulpment, Bnvlronmental Protection
Agency. APTD-0576, March 1973.
7.4 Smith. W. S., B. T. Bhlgehara. and W.
P. Todd. A MetiMd of Interpreting Stack
Sampling Data, Paper presented at the 684
f~™,^ Meeting of the Air Pollution Control
>latton, St. Louis, Ibx, June 14-19,1970.
7 J Smith, W. S, «i «!., Stack Oas Sam-
pling Improved and Simplified with New
Equipment, APOA*paper Ko. 67-119,1967.
7.6 Specifications for Incinerator Testing
a* Federal Faculties, PH8. KOAPO, 1967.
7.7 anlgebars, B. T. Adjustments la the
EPA Nomograph for Different Pltot Tube Co-
efficients and Dry Molecular Weigh**, Stack
Sampling Mews 9:4-11, Oct. 1974.
MBTHOB 6—D*nuoirAnow or Bmrm Di-
oznus JbuanoKa r»oit STATIONAET Somew
1. Principle and AppHeabCtty.
1.1 Principle. A gas sample Is extracted
from the sampling point In the stack. The
add mist (Including sulfur trtozlde) and
the sulfur dioxide an separated. The sulfur
dioxide fraction Is measured by the barlum-
tborln titratlon "TtthfMl,
la AppucabUltf. This method is applica-
ble for the determination of sulfur dioxide
emissions from stationary sources. The mint-
mum detectable limit of the method has been
determined to be 3.4 mg of BOi/m* (9.1XUK
U>/ff). Ho upper limit has been established.
a. Apparatus.
9.1 Sampling. See Figure 6-1.
a.1.1 Probe—Borosllloate glass, approxi-
mately 6 to 6 mm m. with a heating system
to prevent water condensation aad equipped
with a alter (either In-stack or heated out-
stack) to remove particulate matter includ-
ing sulfurio add mlsti
2.1 J Bubbler and Implngers One midget
bubbler, with medium coarse glass frit and
borosilicato or quarts glass wool packed la
top (see Figure 6-1) to prevent sulfurtc add
mist carryover; and three midget Implngers,
each with 80 ml capacity, or equivalent. The
bubbler and midget Implngers shall be con-
nected in series with leak free glass connec-
tors. Silicons grease may be used, If oeeai
sary, to prevent leakage.
2.1.3 Glass wbol-BorosUlcate or quarts.
HONAL UOISTU, VOL 41, NO. Ill—TUIWAY, JUNI I, We
C-25
-------
23084
PIOPOSED RULES
HJCAaa
MrwaiuM
1VI4fflOriUK
NOW* H. $92 Mmpllnj train. Mm TAW
3.14 Stopcock gn
-Aoeteone insoluble,
may b» USed, U
necessary.
3.14 Drying tube-Tube packed with 6 to
16 mesh indicating-type silica gel, or equiv-
alent, to dry the gM sample and to protect
the motor Ml*1
pl* gM flow rate.
9.1.7 Pump— Leak free diaphragm pump,
or equivalent, to pull KM through the train.
9.14 Volume mater— Dry gM meter, sum-
dently •count* to measure th* sample
volume within a percent, calibrated over the
rang* of flow ratee and condition* actually
used during eampUng and equipped with a
temperature gauge (dial thermometer, or
ottuivslont) •
9.14 Flow Meter— Rotameter, or equiv-
alent. to measure flow range from 0-a ipm
(OtoBefh).
S.1.10 Fltot tube— Type B, or equivalent
attached to probe to allow constant monitor-
lag of the etaok CM velocity eo that the
sampling flow rate can be regulated propor-
tkmal to the etaok gM velocity. The tip* of
the probe and pltot tube ehall be adjacent
to each other and the free space between
them ahaU be about 14 cm (0.78 in.). When
wed with this method, the pltot tube need
BO* be calibrated.
The pltot tube ehall be equipped with am
Inclined manometer, or equivalent device,
capable of mcMurtng velocity head to within
10 percent of the minimum measured value
«*> $0418 mm (0.0006 in.), whichever is
greater.
a.1.11 Temperature gauge— Dial ther-
mometer. or equivalent, to measure tempera-
ture of gM leaving Implnger train to within
i« o (a* r>.
2.1.13 Barometer— Mercury, aneroid, or
other barometers capable of measuring
atmospheric pressure to within 94 mm Hg
(04 in. Hg). In many cases, the barometric
reading may be obtained from a nearby wea-
ther bureau station. In which case the station
value (which Is the absolute barometric pres-
sure) shall be requested and an adjustment
for elevation differences between the weather
station and sampling point ahaU be applied at
a rate of minus 34 mm Hg (0.1 in. Kg) per
SO m (100 ft) elevation increase or vice vena
for elevation decrease.
9.1.1* Vacuum gauge— At least 700 mm Hg
(30 m. Rg) gauge, to be used for the sam-
pling tram leak check.
94 Sample recovery.
84.1 Wash bottles—Polyethylene or glass.
WO ml, two,
844 Storage bottles—Polyethylene, 100
ml. to store Implnger samples (one per
sample).
34 Analysis.
94.1 Pipettes—Volumetric type. 8 ml eke,
30 ml sis* (one per sample), and 38 ml dae.
344 Volumetric flasks—100 ml sue (one
per sample) and 1000 ml suses.
343 Burettes—B ml and BO ml SUMS.
94.4 Brlenmeyer flasks—060 ml sis* (one
for each sample, blank, and standard).
344 Dropping bottle—126 ml sloe, to add
indicator.
34.0—Graduated cylinder—100 ml suse.
3. Reagtntt.
Unless otherwise indicated, it to intended
that all reagents conform to the specifica-
tion* established by VP+ Committee on Ana*
lyttoal Reagents of the American Chemical
Society, where such specifications are avail-
able; otherwise use best available grade.
3.1 Sampling.
3.1.1 Water—DeionlMd. distilled to eon-
form to ABTIC spedfleaaon Dl 103-73, Type 3.
8.14 Isopropanol, 80 pcroent-aox go ml
of laopropanol with 90 ml of ddonlsod, dis-
tilled water.
3.14 Hydrogen peroxide, 8 percent-
Dilute 30 percent hydrogen peroxide 1:3
(v/v) with ddonlssd. distilled water (80 ml
is needed per sample). Prepare fresh dally.
84 Sample recovery.
84.1 Water—DeionlMd, distilled, M in
8,1.1.
844 Zsopropanot, 80 percent—im 80 ml
of isopropanol with 30 ml of delonuwd. dis-
tilled water.
84 Analysis.
84.1 Water—Delcnlzed,* distilled, M in
8.1.1.
844 Isopropanol, 100 percent.
844 Thorin indicator—l-(o-anonophen-
ylaBO)-a-naphtol-3. a-disulfonlo add. di-
aodlum salt, or equivalent. Dissolve 040 g in
100 ml of detonmed, distilled water.
84.4 Barium perchlorate solution, 0.01 It—
Dissolve 146 g of barium perchlorate trlhy-
drate |B»(O1O4), • 8H.OJ in 300 ml distilled
water and dilute to 1 liter with laopropanol.
Bad, • 2H.O (142 g) may also be used.
Standardize M in section 84.
844 Bulfurio sold standard, 0.01 K—
Purchase or standardise to ±04002 N against
041 H NaOH which has previously been
standardized against potassium acid phtha-
late (primary standard grade).
4. Procedure.
4.1 Sampling.
4.1.1 Preparation of collection train.
Measure 16 ml of BO percent Isopropanol into
the midget bubbler and IB ml of 8 percent
hydrogen peroxide into each of the first two
midget Implngen. Leave the final midget Im-
plnger dry. Assemble the train M shown in
Figure 0-1. Adjust probe heater to operating
temperature. Place crushed Ice and water
around the implngers. Leak check the sam-
pling train Just prior to use at toe sampling
alt* by placing a vacuum gauge at the inlet
to the first Implnger and pulling a vacuum
of at least 360 mm Hg (10 In. Hg), plugging
or pinching off the outlet of the flowmeter.
and then turning off the pump. The vacuum
shall remain stable for at toast one minute.
Carefully release the vacuum gauge before
releasing the flowmeter end. Connect the
probe.
4.14 Sample collection. Record the initial
dry gM meter reading and barometric pres-
sure. To begin sampling, position the tip of
the probe at the sampling point and start
the pump. Adjust the sample flow to a rate of
approximately 1 1pm M indicated by the
rotameter. Sample at a rate that is propor-
tional (within 20 percent of the average
V./V5F)
to the stack gM velocity throughout the
run. Take readings (dry gM meter, tempera-
tures at dry gM meter and at Implnger out-
let, rate meter, and velocity head) at toMt
•very five minutee and when significant
ehanges (20 percent variation In velocity
head readings) in stack conditions neces-
sitate additional adjustments In sample flow
rate. Add more too during the run to keep
the temperature of the gases leaving the iMt
Implnger at 90* C <«• F) or less. At the
conclusion of each run, turn off the pump,
remove probe from the stack, and record the
final readings. Conduct a teak check M be-
fore. If excessive leakage rate is found void
the test run. Remove the probe from the
stack and disconnect it from the train.
Drain the ice bath and purge the remain-
ing part of the train by drawing clean
ambient air through the system for IB min-
utes at the «M«pii«g rate.
Nora.—Clean ambient air oan be provided
by nesting air through a charcoal filter or
through an extra midget implnger with 18
ml 8 percent H,OP The tester may option
to simply use the ambient air.
44 Sample recovery. Disconnect the Im-
plngers after purging. Discard the contents
at the midget bubbler. Pour the contents of
the midget Implngen into a leak-free poly-
ethylene bottle for shipment. Rinse the three
midget implngers and the connecting tubes
with drtotittiert, distilled water and add the
washings to the same storage container.
Mark the fluid level. Seal and Identify the
sample container.
44 Sample analysis. Note level of liquid
In fwtntalner and confirm whether or not any
sample WM lost during shipment by noting
this on analytical data sheet.
Hois. Protect the 0.01 H barium perchlo-
rate solution from evaporation at an times.
Transfer the contents of the storage con-
tainer to a 100 ml volumetric flask and
dilute to exactly 100 ml with delonused. dis-
tilled water. Pipette a 90 ml allquo of this
solution into a 360 ml Brlenmeyer flask, add
80 ml of isopropanol, two to four drops of
thorln Indicator and titrate to a pink end-
point using 0.01 I? barium perchlorate. Re-
peat and average the tttratton volumes. Run
a blank with each series of samples. Repli-
cate titrations shan agree within l percent.
B. Calibration.
6.1 XJte method* and equipment M spec-
ified in Methods 8 and B and APTD-087B to
KDtftAL UOISTH, VOL 41, NO. Ill—TUISDAV, JUNI B, 1976
C-26
-------
PROPOSED RULES
23085
calibrate the roUm»ter, pltot tube, dry gas
mater, barometer, and thermometers.
6.3 Standardize the barium perchlorate
solution against 25 ml of standard sulfurlc
acid to which 100 ml of laopropanol has been
added.
6. Calculations. .
Carry out calculations, retaining at least
one extra decimal figure beyond that of the
acquired data. Round off figures after final
calculation,
0.1 Nomenclature.
Csoi" Concentration of sulfur dioxide.
dry basis corrected to standard
conditions, mg/dscm (Ib/dscf)
N= Normality of barium perchlorate
tltrant, milllequivalents/ml
Ph., -Barometric pressure at the exit
orifice of the dry gas meter,
mm He (in. Hg)
P.UI- Standard absolute pressure, 780
mmHg(29.92in.Hg)
Tm=» Average dry gaa meter absolute
temperature? 8K (8R)
I.*- Standard absolute temperature,
293° K (528° R)
V.— Volume of sample aliquot titrated,
ml
Vm=Dry gas volume as measured by
the dry gas meter, dcm (dcf)
Vmt.hD — Dry gas volume measured by the
dry gas meter, corrected to
standard conditions, dscm (dscf)
V,,i»— Total volume of solution in which
the sulfur dioxide sample is
contained, 100 ml
V,-Volume of barium perchlorate
titrant used for the sample, ml
(average of replicate titrations)
V,b-Volume of barium perchlorate
titrant used for the blank, ml
32.03 -Equivalent weight of snlfur
dioxide
8.3 Dry sample gaa volume, corrected to
standard conditions.
Equation 6-1
where:
*\*™ UiOww *»/•*•••* *"B ""• «"•-----
= 17.85 °R/in. Hg for English units
6.3 Sulfur dioxide concentration.
Hg for metric units
Equation 6-2
where:
K— 32.03 mg/meq. for metric units
-7.05X lO-' for Engllsh UnltS
7. Reference*.
7.1 Atmospheric Emissions from Sulfurlo
Acid Manufacturing Processes, U.S. DHEW,
PH8, Division of Air Pollution, Public Health
Service Publication No. 999-AP-13, Cincin-
nati, Ohio, 1966,
7.3 Oorbett, P. F.. The Determination of
SO, «nd SO, in Flue Oaies, Journal of the
Institute Of Fuel, 34, 337-343, 1901.
7.3 Matty. B. E. and E. K. Dlehl, Measur-
ing Flue-Qas SO, and SO., Power 101 :94-97,
November 1SB7.
7.4 Patton, W. F. and J. A. Brink, Jr.,
New Equipment and Techniques for Sam-
pling Chemical Process Oases, J. Air Pollu-
tion Control Association, 13, 182 (1963) .
7.S Bom, J. J., Maintenance, Calibration,
and Operation of Isoklnetlc Source-Sampling
Equipment. Office of Air Programs, Environ-
mental Protection Agency, Research Triangle
Park, N.O.. March 1972. APTD-OB76.
7.6 Hamll, H. F. and Camann, D. B., Col-
laborative Study of Method for the Deter-
mination of Sulfur Dioxide Emissions From
Stationary Sources. Prepared for Methods
Standardization Branch, Quality Assurance
and Environmental Monitoring Laboratory,
National Environmental Research Center,
Environmental Protection Agency, Research
Triangle Park, N.0.37711.
7.7 Annual Book of A8TM Standards. Part
23; Water, Atmospheric Analysis, pp. 303-208.
American Society for Testing and Materials,
Philadelphia, Penna. (1972).
METHOD 7—DETERMINATION or Nrrnoorn
Oxioc EMISSIONS FROM STATIONARY Bounces
1. Principle ant Applicability.
1.1 Principle. A grab sample Is collected In
an evacuated flask containing a dilute sul-
furlc acid-hydrogen peroxide absorbing solu-
tion, and the nitrogen oxides, except nitrous
oxide, are measured colormetrlcally using the
phenoldisuifonlc acid (PDS) procedure.
1.3 Applicability. This method Is appli-
cable to the measurement of nitrogen oxides
emitted from stationary sources. The range
of the method has been determined to be 3
to 400 milligrams NO. as No, per dry stand-
ard cubic meter without having to dilute
the sample.
3. Apparatus.
3.1 Sampling (See' Figure 7-1).
3.1.1 Probe—Boroslllcate glass tubing
sufficiently heated to prevent water conden-
sation and equipped with a filter (either In-
slack or heated out of stack) to remove
paniculate matter. Heating is unnecessary
if the probe remains dry during the purging
period.
3.1.2 Collection flask—Two-liter borosill-
cate, round bottom with short neck and
34/40 standard taper opening, protected
against implosion or breakage,
3.1.3 Flask valve—T-bore stopcock con-
nected to a 24/40 standard taper Joint.
3.1.4 Temperature gauge—Dial-type ther-
mometer, or equivalent, capable of measur-
ing 1* C (2- F) intervals from -5 to
50'C (28 to 135'F).
PROM
N.ASK VAL'
FILTH
GROUND-CUSS SOCI
} NO. 12/5
•Nd"
110 mm
J-HAY STOPCOCK:
T-BOM. ! firm.
i-mmBOM. t-i
aHOUNO-GUS:
STANDARD TAPER.
| StHVf NO. 21/40
FLASK
FLASK IHiaOL..',
(-.BOUND-GLASS
SOCHT. 3 NO.
me*
Flgurt 7-1. Sampling train, flltk vilvt. tnd Haiti.
FOAM INCAStMENT
BOILING FLASK.
MITCH, HOUND-BOTTOM. 1HORT NICK.
WITH {SLEEVt NO. 24/40
3.1,8 Vacuum line—Tubing capable of
withstanding a vacuum of 78 mm Hg (3 In.
Hg) absolute pressure, with "T" connection,
and T-bore stopcock.
2.1.6 Pressure gauge—U-tube monometer,
1-meter, with 1-mm (38-ln., with 0,1-ln.)
divisions, or equivalent.
2.1.7 Pump—Capable of evacuating the
collection flask to a pressure equal to or less
than 76 mm Hg (3 In. Hgf absolute.
3.1.8 Squeeze bulb—One-way
2.1.9 Volumetric pipette—28-ml.
2.1.10 Stopcock and ground joint grease—
A high vacuum, high temperature chloro-
fluorocarbon grease Is required. Halocar-
bon1 20-68 has been found to be effective.
3.1.11 Barometer—Mercury, aneroid, or
other barometers capable of measuring at-
mospheric pressure to within 2.6 mm Hg
(0.1 in. Hg). In many cases, the barometric
1 Mention of trade names or specific prod-
ucts does not constitute endorsement by the
Environmental Protection Agency.
reading may be obtained from a nearby
weather bureau station, in which case the
station value (which is the absolute baro-
metric pressure) shall be requested and an
adjustment for elevation differences between
the weather station and sampling point shall
'be applied .at a rate of minus 3.6 mm Hg (0.1
In. Hg) per 30 m (100 ft) elevation Increase
or vice versa for elevation decrease.
3.2 Sample recovery.
2.2.1 Graduated cylinder—60-ml with 1-
ml divisions.
2.3.2 Storage container—Leak-free poly-
ethylene bottles,
3.3.3 Wash bottle—polyethylene- or glass.
2.3.4 Glass stirring rod.
3.3.6 pH indicating teat paper—To cover
the pH range of 7-14.
2.a Analysis.
3.3.1 Volumetric pipettes—Two l-ml, two
3-ml, one 3-ml, one 4-ml and two 10-ml. and
one 28-ml for each sample and standard.
3.3.2 Porcelain evaporating dishes. 176 to
360-ml capacity with Up for pouring, one for
FiDERAL RiOISTH», VOL. 41, NO. Ill—TUESDAY, JUNI B, 1976
C-27
-------
23086
PROPOSED RULES
each sample and each standard. The Coon*
#40006 (shallow-form, 196 ml) has been
found'to be satisfactory.
2.8.3 steam bath. (A hot plate la not ac-
ceptable.)
3.3.4 Dropping pipette or dropper—Three
required.
2.3.5 Polyethylene policeman—One for
each sample and each standard.
23.6 Graduated cylinder—100-ml with 1-
ml divisions.
3.3.7 Volumetric flasks—50-ml (one for
each sample), 100-ml (one for each sample.
each standard and one for the working stand-
ard KNO, solution), and one 1000-ml.
2.3.8 Spectrophotometer—To measure ab-
sorbance at 410 nm.
3.3.9 Graduated pipette—10-ml, with 0.1-
ml divisions.
3.8.10 pH Indicating test paper—To cover
the pH range of 7-14. ;
3.3.11 Analytical balance—To measure to
0.1 mg.
8. Reagents.
Unless otherwise Indicated, It is Intended
that an reagents conform to the specifica-
tions established by the Commute* on Ana-
lytical Reagents of the American Chemical
Society, where such specifications are avail-
able; otherwise, use best available grade.
8.1 Sampling.
3.1.1 Absorbing solution—Cautiously add
2.8 ml concentrated H£O4 to 1 liter of de-
Ionized, distilled water. Mix well and add
6 ml of 3 percent hydrogen peroxide, freshly
prepared from 30 percent hydrogen peroxide
solution. The solution should be used within
one week of Ito preparation. Do not expose to
extreme beat or direct sunlight.
3.2 Sample recovery.
3,2.1 Sodium hydroxide (IN)—Dissolve
40 g NaOH in delonized, distilled water and
dilute to 1 liter.
8.2.2 Water—Delonized, distilled to con-
form to ASTM specifications DH93-72, Type
3.
8.3 Analysis.
8.3.1 Fuming sulfurlc acid—IB to 18 per-
cent by weight free sulfur trloxlde. Handle
with caution.
8.3.3 Phenol—White solid.
85.3 Bulfurio acid—Concentrated, 65 per-
cent minimum assay. Handle with caution.
8.8.4 Potassium nitrate—Dried at 108-
110* O for a minimum of two hours Just prior
to preparation of standard solution.
8&A Standard solution—Dissolve exactly
3.1980 a of dried potassium nitrate (KNO.)
In deionized. distilled water and dilute to 1
liter with delonized, distilled water in a
1000-ml volumetric flask. POr the working
standard solution, dilute 10 ml of the stand-
ard solution to 100 ml with deionized dis-
tilled water. One ml of the working standard
solution is equivalent to 100 *g nitrogen
dioxide (NO,).
8.3.6 Water—Delonleed, distilled as In
section 3.3.3.
8.3.7 Fhenoldisulfonle acid solutiop—Dis-
solve 38 g of pure white phenol la 150 ml
concentrated sulf uric add on a steam bath.
Oool. add 76 ml fuming sulfurto acid, and
beat at 100* O (313* P) for 3 hours. Store
In a dark, stoppered bottle.
4. Procedure.
4.1 Sampling.
4.1.1 Pipette 39 ml of absorbing solution
into a sample flask, retaining a sufficient
» Mention of trade names or specific prod-
nets does not constitute endorsement by the
Xnvtronmental Protection Afeney.
quantity for use in preparing the calibration
standards..Insert the flask valve stopper into
the flask with the valve in the "purge" posi-
tion. Assemble the sampling train as shown
In figure 7-1 and. place the probe at the
sampling point. Make sure that all fittings
are tight and leak free, and that all ground
glass joints have been properly greased with
a high vacuum, high temperature chloro-
fluorocarbon-based stopcock grease. Turn the
flask valve and the pump valve to their
"evacuate" positions. Evacuate the fiask to
76 mm Hg (3 in. Hg) absolute pressure, or
less. Evacuation to a lower pressure (ap-
proaching the vapor pressure of water at .the
existing temperature) is even more desirable.
Turn the pump valve to Its "vent" position
and turn off the pump. Check for leakage by
observing the manometer for any pressure
fluctuation. (Any variation, greater than 10
mm Hg (0.4 In. Hg) over a period of 1
minute is not acceptable, and the flask is not
to be used until the leakage problem is cor-
rected. Pressure in the flask is not to exceed
76 mm Hg (3 in. Hg) absolute at the time
sampling is commenced.) Record the volume
of the flask and valve (V<), the flask tem-
perature (Ti), and the barometric pressure.
Turn the flask valve counterclockwise to its
"purge" position and do the same with the
pump valve. Purge the probe and the vacuum
tube using the squeeze bulb. If condensation
occurs in the probe and the flask valve area,
heat the probe and purge until the conden-
sation disappears. Then turn the pump valve
' to Its "vent" position. Turn the flask valve
clockwise to its "evacuate" position and re-
cord the difference in the mercury levels in
the manometer. The absolute internal pres-
sure in the flask (Pi) is equal to the
barometric pressure less the manometer read-
Ing. Immediately turn the flash valve to the
"sample" position and permit the gas .to
enter the fiask until pressures In the flask
and sample line (i.e., duct, stack) are vir-
tually equal. This will usually require about
16 seconds. A longer period indicates a "plug"
in the probe which must be corrected before
sampling is continued. After collecting the
sample, turn the flask valve to its "purge"
position and disconnect the flask from the
sampling team. Shake the flask for at least
8 minutes.'
4,12 If the gas being sampled contains
Insufficient oxygen for the conversion to
NO to NO*, e«. an applicable subpart of
the standard may require taking a sample
of a calibration gas mixture of NO in Nf,
then oxygen shall be Introduced Into the
flask to permit this conversion. Oxygen may
be introduced into the flask by one of three
methods: (1) Before evacuating the sam-
pling flask flush with pure cylinder oxygen
(then evacuate flash to 75 mm Hg ( 8 in.
Hg) absolute pressure or less); or (3) inject
oxygen into the flask after sampling; or (8)
sampling may be terminated with a mini-
mum of 80 mm Hg (3 In. Hg) vacuum re-
maining in the flask, recording this final
pressure and then venting the flask to the
atmosphere until the flask pressure is al-
most equal to atmospheric pressure.
4.2 Sample recovery.
4.3.1 Let the flask set for a minimum
of 16 boors and then shake the contents
for 3 minutes. Connect the fiask to a mer-
cury filled XT-tubs manometer, open the
Valve from the flask to the manometer, and
record the flash temperature (Tt). the baro-
metric pressure and the difference between
the mercury levels in the manometer. The
absolute Internal pressure in the flask (Pi)
It the barometric pressure less the manom-
eter reading. Transfer the contents of the
flask to a leak-free polyethylene bottle. Rinse
the flask twice with 6-ml portions of de-
ionized, distilled water and add the rinse
water to the bottle. Adjust the pH to 9-12
by adding sodium hydroxide (IN) dropwise
(about 25 to 35 drops). Check the pH by
dipping a stirring 'rod into the solution and
then touching it to the pH test paper.
Remove as little material as possible during
this step. Mark the height of the liquid level
to determine whether or not leakage oc-
curred during transport. Label container to
clearly identify its contents. Seal the con-
tainer for shipping.
4.3 Analysis.
4.3.1 Note level of liquid in 'container
and confirm whether or not any sample was
lost during shipment by noting this on
analytical data sheet. Transfer the contents
of the shipping container to a 50-ml volume-
tric flask, rinse the container twice with
6-ml portions of delonized, distilled water.
add the rinse water to the flask and dilute
to the mark with deionized, distilled water.
Mix thoroughly and pipette a 25-ml aliquot
into the porcelain evaporating dish. Evapo-
rate the solution to dryness on a steam bath
and allow to cool. (Use only a steam bath—
a hot plate is not acceptable.) Add 2 ml
phenoldisulfonlc acid solution to the dried
residue and triturate thoroughly with
a polyethylene policeman. Make sure the
solution contacts all the residue. Add 1 ml-
delonized, distilled water and four drops of
concentrated sulfurlc acid. Heat the solu-
tion on a steam bath for 8 minutes with
occasional stirring. Cool, add 20 ml deionized,
distilled water, mix well by stirring and add
concentrated ammonium hydroxide dropwlse
with constant stirring until pH is 10 (as
determined by pH paper). If the sample con-
tains solids, filter through Whatman No. 41
filter paper into a 100-ml volumetric flask;
rinse the evaporating dish with three 6-ml
portions of delonized, distilled water and add
these to the filter. Wash the niter with at
least three 15-ml portions of deionized, dis-
tilled water. Add the filter washings to the
contents of the volumetric flask and dilute
to the mark with delonized. distilled water.
If solids are absent, transfer the solution
directly to the 100-ml volumetric flask and
dilute to the mark with deionized, distilled
water. Mix thoroughly and measure the ab-
sorbance at 410 nm using the blank solution
as a zero reference. Dilute the sample and
the blank with a suitable amount of de-
ionized, distilled water if absorbance exceeds
Ai, the absorbance of the 400 iig NOa stand-
ard (See section 6.3).
6. Calibration.
5.1 Flask volume. Assemble the flask and
flask valve and fill with water to the stop-
cock. Measure the volume of water to±lO
ml. Number, and record the volume on the
flask.
5.2 Spectrophotometer calibration. Add
0.0 ml, 1.0 ml, 3.0 ml, 8.0 ml and 4.0 ml
of the KNO* Working standard solution (1
ml=lOO *g NO») to a series of five porcelain
evaporating dishes. To each, add 38 ml of
absorbing solution, 10 ml delonized, distilled
water and sodium hydroxide (1 N) drop-
wise until the pH is 9-12 (about 26 to 85
drops each). Beginning with the evaporation
step, follow the analysis procedure of Sec-
tion 4.3 to collect the data necessary to cal-
culate the calibration factor (Section 6.8).
This calibration procedure must be repeated
on each day that samples are analyzed.
6J Determination of Spectrophotometer
calibration factor K4.
HDOAHttOWH, VOL 41. WO. Ill—TUIJOAY, JUNI », 1*7*
C-28
-------
PROPOSED RULES
23087
K.= 100
A,+2A<+3A»+4A<
0.4 Sample concentration, dry basis, cor-
rected to standard conditions.
Equation 7-1
where:
KO=Calibration factor
AI = Absorbance of the 100 Mg NOj stand-
ard
Aa=Absorbance of the 200 UK NO> stand-
ard
Aj=Absorbance of the 300 ^p NO, stand-
ard
A<=Absorbnrici- of the 400 ^g NO8 stand-
ard
5.4 Barometer. Calibrate against a mer-
cury barometer.
6.6 Temperature gauge. Calibrate dial
thermometers against mercury-in-glass ther-
mometers.
'6. Calculations,
Carry out the calculations, retaining at
lease one extra decimal figure beyond that
of the acquired data. Bound off figures after
final calculations.
6.1 Nomenclature.
A=Absorbance of sample
C = Concentration of NO. as NOa, dry
basis, corrected to standard condi-
tions, mg/dscm (Ib/dscf)
F» Dilution factor (i.e., 25/5, 25/10, etc,
required only if sample dilution
was needed to reduce the absorb-
ance into the range of calibration)
K. = Spectrophotometer calibration factor
in = Mass of NO, as NO» in gas sample,
(LIg
P; = Final absolute pressure of flask, mm
Hg(in. Hg)
P, = Initial absolute pressure of flask, mm
Hg (in. Hg)
Standard absolute pressure, 760 mm
P.,a=
T,=
Ti=
T.,d=
V,.=
vf.
v.=
2*
Hg (28.92 in. Hg)
inal absolute temperature of flask,
= Fin
orf
= Initial absolute temperature of flask,
°K (°R)
= Standard absolute temperature, 293°
K (528° R)
= Sample volume at standard condi-
tions (dry basis), ml
= Volume of flask and valve, ml
= Volume of absorbing solution. 25 ml
= 50/25, the aliquot factor. (If other
than a 25-ml aliquot was used for
analysis, the corresponding factor
must be substituted.)
6.2 Sample volume, dry basis, corrected
to standard conditions.
'--
as <*-"•
=K(V,-25ml)|jjj-iyj]
Equation 7-2
for metric units
, for English units
in. Hg
6.3 Total/tg NO, per sample.
m=2K. AF Equation 7-3
NOTE.—If other than a 25-ml aliquot ia
used for analyses, the factor 2 must be sub-
stituted by a corresponding factor.
Where:
K=0.3855
-17.65 r
C=Kn-
Kqufition 7-4
where:
=6.243X10-'for English unite
Mg/ml
7. References.
7.1 Standard Methods of Chemical Analy-
sis. 6th ed. New York, D. Van Nostrand Co.,
Inc., 1062, YOl. 1, p. 329-330.
13 Standard Moht* dofteTst:uaE*Ni
7.2 Standard Method of Test Tor Oxides
of Nitrogen in Gaseous Combustion Products
(Phenoldlsulfonlc Acid Procedure), In: 1968
Book of ASTM Standards, Part 33, Philadel-
phia, Pa., 1968, ATSM Designation D-1608-
60, p. 725-729.
7.3 Jacob, M. B., The Chemical Analysis
of Air Pollutants, New York, N.Y., Inter-
scienee Publishers, Inc., 1960. vol. 10, p. 361-
356.
7.4 Beatty, B. L., Berger, L. B. and
Schrenk, H. H., Determination of Oxides of
Nitrogen by the Phenoldisulfonic Acid
Method. B. I. 3687, Bureau of Mines, U.S.
Dept. Interior, February (1943).
7.5 Hamil, H. F., and Camann, D. E., Col-
laborative Study of Method for the Deter-
mination of Nitrogen Oxide Emissions from
Stationary Sources (Fossil Fuel-Fired Steam
Generators), Southwest Research Institute
report for Environmental Protection Agency,
October 5,1973.
7.6 Hamil, H. F., and Thomas, B. E., Col-
laborative Study of Method for the Deter-
mination of Nitrogen Oxide Emissions from
Stationary Sources (Nitric Acid Plants),
Southwest Research Institute report for En-
vironmental Protection Agency, May 8, 1974
METHOD 8—DETERMINATION OF SULFUHIC ACID
MIST AND Strum DIOXIDE EMISSIONS FROM
STATIONARY SOURCES
1. Principle and Applicability.
1.1 Principle. A gas sample Is extracted
isokinetlcally from the stack. The acid mist
(including sulfur trioxlde) and the sulfur
dioxide are separated and both fractions are
measured separately by the barlum-thorin
tltratlon method.
1.2 Applicability. This method Is appli-
cable for the determination of sulfuric acid
mist (Including sulfur trioxlde) In the ab-
sence of other parttculate matter and for
sulfur dioxide from stationary sources. Col-
laborative teats nave shown that the mini-
mum detectable limits of the method are
0.05 mg/m» (0.03X10-' lb/ft') for sulfur tri-
oxlde and 1.2 mg/m» (0.74X10-* lb/ft3) for
sulfur dioxide. No upper limits have been
established.
2. Apparatus
3.1 Sampling. A schematic of the sam-
pling train used In this method is shown In
Figure 8-1; It Is similar to the Method 8 train
except that the filter position Is different and
beating of the filter holder is not required.
Commercial models of this train are available!.
However, If one desires to build his own, com-
plete construction details are described in
APTD-0881; for changes from the APTD-
0581 document and for allowable modifica-
tions to Figure 8-1, see the following sub-
section*.
KDERAUJEOISTE*, VOL 41, NO. HI-
C-29
-TUESDAY. JUNE t, 1976
-------
23088
PROPOSED RULES
(t»T01toJ TEMPERATURE SENSOR
. PROBE
=£ PITOTTUBE
1.9 cm (3.75 in.) W^^TACK WALL
WOCE LJ
FILTtR HOLDER
THKRVOVEUB
MVERSt-TVPE
riTOT TUBE
•VACUUM
LINE
PUMP
DRY nST METER
Figure 8 1. Sulfurle tcid mist sampling train.
The operating and maintenance procedures
for the campling train are described In APTD-
0678. Since correct usage is Important In ob-
taining valid results, all user* should read
the AFTD-0576 document and adopt the
operating and maintenance procedures
outlined In it, unless otherwise specified
herein. Further details and guidelines on op-
eration and maintenance are given in Method
A and should be read and followed whenever
they are applicable.
9.1.1 Probe nozzle—Stainless steel (316)
with sharp, tapered leading edge. The angle
of taper shall be £ 30* and the taper shall
be on the outside to preserve a constant
internal diameter. The probe nozzle shall be
of the button-hook or elbow design, unless
otherwise specified by the Administrator. The
nozzle shall be constructed from seamless
stainless steel tubing, pther configurations
and construction material may be used with
approval from the Administrator.
A range of sizes suitable for isoklnetlc
sampling should be available, e.g., 0.32 cm
(% in.) up to 157 cm (V4 !»»•) (or larger if
higher volume sampling trains are used)' In-
side diameter (ID) nozzles In increments of
0.18 cm (1/16 in.). Each nozzle shall be cali-
brated according to the procedures outlined
in the calibration section.
2.1.3. Probe liner—Boroslllcate or quartz
glass, with a beating system to prevent visi-
ble condensation during sampling.
8.1,8 Pltot tube—Type 8, or other device
approved by the Administrator, attached to
probe to allow constant monitoring of the
•tack gas velocity. The face openings of the
pltot tube and the probe nozzle shall be ad-
jacent and parallel to each other, not neces-
sarily on the same plane, during sampling.
The free space between the nozzle and pltot
tube shall be at least 1.0 cm (0.75 to.). The
free space shall be set baaed on" a 15 cm
(0.5 In.) ID nozzle. If the sampling train ts
designed for sampling at higher flow rates
than that described in APTD-0581. thus
necessitating the use of larger, sized nozzles.
the largest sized nozzle shall be used to set
the free space.
The pltot tube must also meet the criteria
specified in Method 2 and be calibrated ac-
cording to the procedure in the calibration
section of that method.
2.1.4 Differential pressure gauge—In-
clined manometer capable of measuring
velocity head to within 10 percent of the
minimum measured value or ±0.013 mm
(0.0005 in.), whichever is greater. Below a
differential pressure of 1.3 mm (0.05 In.)
water gauge, mlcromanometers with sensi-
tivities of 0.013 mm (0.0005 In.) should be
used. However, mlcromanometers are not
easily adaptable to field condition* and are
not easy to use with pulsating flow. Thus,
methods or other devices acceptable to the
Administrator may be used when conditions
warrant.
2.1.5 Filter bolder—Borosillcate glass
with a glass frit filter support and a sillcone
rubber gasket. Other materials of construc-
tion may be used with approval from the Ad-
ministrator. The holder design shall provide
a positive seal against leakage from the out-
side or around the filter.
2.1.6 Implngers—Four as shown in. Figure
8-1. The first and third shall be of the
Oreenburg-Smith design with standard tips.
The second and fourth shall be of the Oreen-
burg-Smith design, modified by replacing the
.insert with an approximately 13 mm (0.5
in.) ID- glass tube, having an unconstrlcted
.tip located 13 mm (0.5 in.) from the bottom
of the flask. Similar collection systems, which
have been approved by the Administrator
may be used.
3.1.7 Metering system—Vacuum gauge,
leak-free 'pump, thermometers capable of
measuring temperature, to within 3* C
(6.4* F), dry gas metef with 2 percent ac-
curacy, and related equipment, or equivalent,
aa required to maintain an isokinetic sam-
pling rate and to determine sample volume.
When the metering system is used in con-
junction with a pltot tube, the system shall
enable cheek* of IsokUieUo rates.
2.1.8 Barometer—Mercury, aneroid, or
other barometers capable of measuring
atmospheric pressure to within 2.5 mm Hg
(0.1 In. Hg). In many cases, the barometric
reading may be obtained from a nearby
weather bureau station, In which the station
value (which Is the absolute barometric pres-
sure) shall be requested and an adjustment
for elevation differences between the weather
station and sampling point shall be applied
at a rate of minus 2.5 mm Hg (O.I in. Hg)
per 30 m (100 ft) elevation Increase or vice
versa for elevation decrease.
2.1.0 Temperature gauge—Thermometer,
or equivalent, to measure temperature of gas
leaving Implnger train to within 3*C(5*F).
2.2 Sample recovery.
2.2.1 Wash bottles—Polyethylene or glass.
600 ml. (two).
2.2.2 Graduated cylinders—250 ml, 1 liter.
(Volumetric flasks may also be used.)
2.2.3 Storage bottles—Leak-free polyeth-
ylene bottles, 1000 ml size. (Two for each
sampling run.)
2.3 Analysis.
2.3.1 Pipette—Volumetric 25 ml. 100 ml.
3.8.3 Burette—BO ml.
2.3.3 Brlenmeyer flask—250 ml. (One for
each sample blank and standard.)
2.3.4 Graduated cylinder—100 ml.
2.3.5 Trip balance—300 g capacity, to
measure to ±0.8 g.
3.3.0 Dropping bottle—to add Indicator
solution, 125 ml size.
8. Reagentt.
Unless otherwise indicated, it Is Intended
that all reagents conform to the specifica-
tions established by the Committee on Ana-
lytical Reagents of the American Chemical
Society, where such specifications are avail-
able; otherwise use best available grade.
3.1 Sampling.
3.1.1 Filters—Glass fiber filters, without
organic binder exhibiting at least 99.99 per-
cent efficiency (£0.05 percent penetration)
on 0.3 micron dloctyl phthalate smoke par-
ticles. The filter efficiency test shall be con-
ducted In accordane with ASTM standard
method D 2986-71. Test data from the sup-
plier's quality control program Is sufficient
for this purpose.
3.1.2. Silica gel—Indicating type. 6-16
mesh. If previously used, dry at 176* C (350*
F) for 2 hours. New silica gel may be used
as received.
3.13 Water—DeIonized, distilled, to con-
form to ASTM specifications D1193-72,
Type 3.
3.1.4 Isopropanol, 80 percent—Mix 800 ml
of Isopropanol with 200 ml of delonfzed dis-
tilled water.
NOTE.—Experience has shown that only
A.C.8. grade Isopropanol Is satisfactory.
3.1.5 Hydrogen peroxide, 3 percent—Di-
lute 100 ml of 30 percent hydrogen peroxide
to 1 liter with deionlzed, distilled witer. Pre-
pare fresh dally.
3.1.6 Crushed Iced.
35 Sample recovery.
3.2.1 Water—Deionlzed, distilled, to con-
form-to ASTM specifications Dl 193-72, Type
8.
3.25 Isopropanol, 80 percent—Mix 800 ml
of isopropanol with 200 ml of deionlzed dis-
tilled water.
NOT*.—Experience baa shown that only
A.C.S. grade Isopropanol Is satisfactory.
33 Analysis.
3.3.1 Water—Deionlzed. distilled, to con-
form to ASTM specifications DU93-72, Type
8.
8.85 Isopropanol, 100 percent.
3.3.3 Thorin indicator—l-(o-arsonophen-
yUzo)-2-naphthol-3. 6-dlsulfonlo acid, dl-
sodlum salt, or-equivalent. Dissolve 050 g
in 100 ml of deionlzed distilled water.
FEDERAL REGISTER, VOL 41, NO. HI—TUESDAY, JUNE I, 1976
C-30
-------
PROPOSED RULES
23089
3.8.4 Barium perchlorate (0.01 N)—DIs-
. solve LOT g of barium perehlorate trlhydrate
(Ba(ClO.),-3H1O) In aOO.nl delontaed dis-
tilled water and dilute to 1 liter with isopro-
p*nol. Standardize with aulfurle acid aa la
Section 8.2. This solution must be protected
against evaporation at all times. (Bad, may
also be used.)
3.3.8 Sulfurto acid standard (0.01 N)—
Purchase or standardize to ±0.0009 N against
0.01 N NaOH which has previously been
standardized against primary standard po-
tassium acid phthalate.
4. Procedure.
4.1 Sampling.
4.1.1 Pretest preparation—Follow the
procedure outlined in Method 8, Section 4.1.1,
except that the filter need not be weighed or
Identified. If the effluent gas is considered
to be dry. I.e.. moisture free, the silica gel
need not be weighed.
4.1.8 Preliminary determinations—Follow
the procedure outlined in Method 6, Section
4.1 JJ.
4.13 Preparation of collection train—Fol-
low the procedure outlined In Method 5,
Section 4.1.2.
4.13 Preparation of collection train—Pol-
low the procedure outlined in Method 5, Sec-
HANT ., -
LOCATION
PPEHflTtlR
DATE
BUN NO
SAMPLE BOX NO.
METER BOX ""
METER A H«
C FACTOR^
tlon 4.1.3, except for the second paragraph
and use Figure 8-1 instead of Figure 8-1. Re-
place the second paragraph with: Place 100
ml of 80 percent isopropanol In the first 1m-
pinger, 100 ml of 8 percent hydrogen per-
oxide in both the second and third Imping-
ers, and about 200 g of silica gel In the fourth
Implnger. Retain a portion of the reagents
for use as blank solutions.
4.1.4 Leak-check procedure—Follow the
procedure outlined In Method 8, Section
4.1.4, except that the probe heater shall be
adjusted to the minimum temperature re-
quired to prevent condensation.
4.1.6 Train operation—Follow the proce-
dure outlined In Method 8, Section 4.1.5,
except record the data required on the ex-
ample sheet shown In Figure 8-9. During the
sampling period, observe the line between
the probe and the first Implnger for signs of
condensation. If it occurs, adjust the probe
heater setting upward to the minimum tem-
perature required to prevent condensation.
After turning off the pump and recording the
final readings at the conclusion of each run,
remove the probe from the stack and dis-
connect It from the train. Drain the ice bath
and purge the remaining part of the train by
drawing clean ambient air through the sys-
tem for 18 minutes at the average flow rate
used for sampling.
NOTE.—Clean ambient air can be provided
by passing air through a charcoal filter.
4.2 Sample recovery.
4.2.1 Container No. 1—Transfer the con-
tents of the first Implnger to a 960 ml gradu-
ated cylinder. Rinse the probe, first Implnger,
and all connecting glassware before the filter
with 80 percent isopropanol. Add the rinse
solution to the cylinder. Dilute to 960 ml
with 30 percent isopropanol. Add the filter to
•the solution, mix, and transfer to the storage
container. Protect the solution against evap-
oration. Mark the .level of liquid on con-
tainer and Identify the sample container.
4.2.2 container No. 9—Transfer the solu-
tions from the-second and third Implngem
to a 1000 ml graduated cylinder. Rinse all
glassware between the filter and silica gel
Implnger with delonlzed, distilled water and.
add this rinse water to the cylinder. Dilute
to a volume of 1000 ml with delonlzed, dis-
tilled water. Transfer the solution to a stor-
age container. Mark the level of liquid on
container. Seal and identify the sample con-
tainer.
WOT TUflE COEFFICIENT, Cp.
AMBIENT TEMPERATURE.
BAROMETRIC PRESSURE .
ASSUMED MOISTURE. S_
PROBE LENGTH.m (ft)
NOZZLE IDENTIFICATION NO
AVERAGE CALIBRATED NOZZLE DIAMETER,em W.
PROBE HEATER SETTING
LEAK RATE. m3/mln (cfm)
PROBE LINER MATERIAL
SCHEMATIC OF STACK CROSS SECTION
TRAVERSE POINT
NUMBER
T01AL
AVERAGE
SAMPLING
TIME
(91. mln.
STATIC
PRESSURE
(Ps).irniHg
imHa)
STACK
TEMPERATURE
-------
23090'
4.3 Analyili.
Not* Itvel of liquid In containers 1 and
2 and confirm whether or not any sample
was loat during ihipment by noting this
on analytical data iheet.
4.9.1 Container No. 1—Shake the con-
tainer holding the laopropanol solution and
the filter. If the filter breaks up, allow
the fragments to settle for a few minutes
before removing a sample. Pipette a 100 ml
aliquot of this solution Into a 260 ml Erlen-
meyer flask, add 2 to 4 drops of thorln Indi-
cator, and titrate to a pink endpolnt using
0.01 H barium penhlorate. Repeat the tltra-
tlon with a second aliquot of sample and av-
erage the tltratlon values. Replicate tltra-
tlons should agree within 1 percent.
4.3.3 Container No. a—Throughly mix the
solution In the container holding the con-
tents of the second and third Implngers.
Pipette a 10 ml aliquot of sample Into a 280
ml Erlenmeyer flask. Add 40 ml of Isopro-
panol, 2 to 4 drops of thorln Indicator, and
titrate to a pink endpolnt using 0.01 N barium
perohlorate. Repeat the tltratlon with a
second aliquot of sample and average the
tltratlon values. Replicate tltrattons should
agree wjthln 1 percent.
4.3.8 Blanks—Prepare blanks by adding
9 to 4 drops of throln indicator to 100 ml of
80 percent isopropanol. Titrate the blanks
In the same manner as the samples.
8. Calibration.
5.1 Us* methods and equipment as speci-
fied In Methods 2 and 8 and APTD-0576 to
calibrate the orifice meter, pltot tube, dry gas
meter, thermometers, and barometer.
9.2 standardize the barium perchlorate
solution with 28 ml of standard sulfurlo acid,
to which 100 ml of Isopropanol have been
added,
6. Oaleulationi,
Now.—Carry out calculations retaining at
least one extra decimal figure beyond that of
the acquired data. Round off figures after
final calculation.
0.1 Nomenclature.
PROPOSED RULES
Vm(.i,n-» Volume of gan sample measured
by the dry Ban motor corrected
to standard conditions, dscm
(dscf)
v,- Stack gas velocity, calculated by
Method 2. Equation 2-7 using
data obtained from Method 8,
in/see (ft/see)
V.-i.—Totnl volume of solution in which
the sulfurlo add or sulfur
dloxldo sample Is contained,
260 ml or 1000 ml, respectively
Vt- Volume of barium pcrehlorato
titrant used for the sample, ml
Vib- Volume of barium perchlorate
titrant unod for tho blank, ml
9- Total sampling time, min
13.6 -Specific gravity of mercury
60-8eo/mln
100- Conversion to percent
0.2 Average dry gn meter ' temoenture
and average orifice pressure drop. Set data
sheet (Figure 8-2).
8.8 Dry gas volume. Correct the sample
volume measured by the dry gas meter to
standard conditions (20* 0 and 780 mm Hg
or 68* V and 26.03 In. Hg) by using Equation
8-1.
Vm(.ul)
A.
B.,
Cn,so4
Cso,
p
-Bull
N-
p.-
Pi*1
T»-
T.-
AH
where:
r+ AH/13.6.
Equation 8-1
i Cross sectional area of nonle, m1
(ft»)
Water vapor in the gas stream,
roportlon by volume
furlo acid (Including SOi) con-
centration, g/dscm (Ib/dscf)
Sulfur dioxide concentration, g/
dscm (Ib/draO
Percent of Isoklnctlc sampling
Normality of barium perchlorato
titrant, g. equiv/llter
•Baromotrlo pressure at the sam-
pling site, mm Hg (In. Hg)
•Absolute stack gas pressure, mm
Hgfln, Hg)
•Standard absolute pressure, 760
mm Hg (20.02 in. Hg)
•Absolute average dry gas meter
temperature (see Figure 8-2),
°K fa)
Absolute average stack Baa tem-
ture (sea Figure 8-2), °K
K-0.3855 °K/mm Hg for metric unite
-17.65 °R/in. Hg for English unite
8.4 Volume of water vapor and moisture
content. Use Equation 8-2 and 8-3 of
Method 8. If the effluent gas Is considered to
be dry, these calculations need not be carried
out.
8.8 Sulfurlo acid (Including SO,) concen-
tration.
N(V,-V,b) V'
where:
Equation 8-2
K-0.04804 g/mUllequtvalent for metric
unite •
-1.08X10-4 Pyfah tor English units
8.8 Sulfur tlioxlde concentration:
Equation 8-3
—Standard absolute temperature,
293* K (528° R)
V.-Volume of sample aliquot titrated. .
100 ml for H|804 and 10 ml whwe-
V,.-ToftSv?UeofUquldcollectedln K-0,03203 g/milUequlyalent for metric
impingew and silica gel (see unite
Figure 8-2), ml nwm
V- - Volume of gas sample as measured _ 7.05x 10-* , v, i for English unite
by dry gas meter, dcm (dcf) (gJvW)
8.7 Iioklnetlo variation.
8.7.1 Calculations from raw data.
. 100T,[KVi.+ (V../TJ (Pb.,+ AH/13.6)]
*"
where:
Equation 8-4
K- 0.00346 mm Hg-m'/ml-°K for metric
unite
-0.00267 in. Hg-ft'/ml-°R for English
unite
8.7.2 Calculations from intermediate
values.
T T.VB,(.ld)P.nlOO
™T,wv.9A.P.60( 1-
Tf
"JX
F^r.A.«(l-B«)
Equation 8-5
where:
K—4.323 for metric units
-0.0044 for English unite
6.8 Acceptable results. If BO percent^ I
sSUO percent, the resulte art acceptable. If
the results are low In comparison to the
standards and I Is beyond the acceptable
range, the Administrator may option to ac-
cept the results. Use reference 7.4 of Method
6 to make judgments. Otherwise, reject the
results and repeat the test.
7. Reference!.
7.1 Atmospheric Emissions from Butfurlo
Acid Manufacturing Processes, UJS. DHEW,
PH8, Division of Air Pollution, Public Health
Service Publication No. B99-AP-18, Cincin-
nati, Ohio, 1085.
73 Corbett, D. F., The Determination of
SO. and SO, In Flue Oases, Journal of the
Institute of Fuel, 24:337-243, 1081.
7.3 Martin, Robert M.. construction De-
tails of Isoklnetle Source Sampling Equip-
ment, Environmental Protection Agency, Air
Pollution Control Office Publication No.
APTD-OS81.
7.4 Patton, W. if., and Brink, Jr., J. A..
New Equipment and Techniques for Sam-
pling Chemical Process Oases, J. Air Pollu-
tion Control Assoo. 13, 182 (1883).
7.8 Rom, J. J., Maintenance, Calibration.
and Operation of Isoklnetle Source-Sampling
Equipment. Office of Air Programs, Environ-
mental Protection Agency. Research Trian-
gle Park, N.O., March 1072. APTD-0676.
7.8 Hamll, H. F., and Oamann, D. E., Col-
laborative Study of Method for the Determi-
nation of Sulfur Dioxide Emissions from Sta-
tionary Sources. Prepared for Methods Stand-
ardization Branch, Quality Assurance and
Environmental Monitoring Laboratory, Na-
tional Environmental Research Center, En-
vironmental Protection Agency, Research Tri-
angle Park. N.O. 27711.
7.7 Annual Book of ASTM standards.
Part 23; Water, Atmospheric Analysis, pp.
203-208. American Society for Testing and
Materials, Phlla., Pa. (1973).
• » • ' • .•
|FR Doo.76-16008 Filed 8-7-78:8:48 am]
FIDIKAl MOISTIR, VOL 41, NO. 1II-TUHDAY, JUNI 8, W*
C-32
-------
APPENDIX D
PROCEDURE FOR CONING
AND QUARTERING SOLID SAMPLES
D-1
-------
D.I INTRODUCTION
This procedure 1s an adaptation of ANSI/ASTM procedure 346-78, Standard
Method of Sampling Coke for Analysis, which Is hereby included as a reference.
D.2 SCOPE AND APPLICATION
This procedure applies to the acquisition of solid samples in the field,
preparing field samples for shipment by coning and quartering, and any
subsequent treatment in the laboratory prior to analysis. Typical solid
samples requiring use of this procedure are fly ash, bottom ash, scrubber
Input materials, and coal feed.
The most preferable method of sample acquisition is by use of a plant's
automic sampling system. If there is no automatic system for a required
sample, time-Integrated grab samples will be taken by shovel. Coning
and quartering will be used to produce a representative sample for ship-
ment to the laboratory and for reducing the size of samples in the labora-
tory.
D.3 APPARATUS
o Standard shovel, square edged, 12-inches wide
o Specified sample containers
o Clean Teflon sheet (for laboratory)
o Lamifiar flow bench (for laboratory)
D.4 REAGENTS
None
D.5 PROCEDURES
D.5.1 Automatic Sampling
Many plants are equipped with automatic samplers on process Input
streams. The units are calibrated to remove representative cross sections
of a stream while automatically forming a homogeneous composite. Whenever
D-2
-------
these units are available, the sampling team should make use of them 1n
preference to the shovel technique 1n Section D.5.2.
D.5.2 Fractional Shovel Grab Sampling
Fractional shoveling Involves the acquisition of a time-Integrated
grab sample representative of overall process "Input or output during a
given run time period. This procedure uses a standard square edged
shovel, 12 Inches wide. For streams 1n motion, either entering or exiting
a process operation, a sample 1s taken from the belt on an hourly basis.
A full cross-stream cut should be taken. Each hourly shovel sample is
added to a pile to form eventually a composite for the entire test period.
At the conclusion of the run, this pile will be coned and quartered (as
described below 1n Section D.5.4) to form a final representative sample
weighing from 2.3 to 4.5 kilograms (5 to 10 pounds).
It 1s always preferable to sample a moving stream rather than a
stationary storage pile. This 1s particularly true If a large particle
or lump size distribution exists 1n the material. Stored containers or
heaped beds of material tend to settle, creating segregation of particles
according to size and density, and it 1s more difficult to account for this
bias In the sampling. If It becomes necessary to sample a stationary
pile, every attempt should be made to acquire a fully representative sample
by taking a number of grab samples from a variety of different areas and
depths 1n the pile. A scheme for sampling stationary piles is given in
the referenced ANSI/ASTM procedure.
D.5.3 Coning and Quartering
After a suitable composite sample has been acquired, a reparesentative
sample for laboratory analysis must be removed. The usual method of accom-
plishing this task Involves the coning and quartering technique.
The coning and quartering procedure Involves the following 6 steps:
1) The material 1s first mixed and formed into a neat cone.
2) The cone 1s flattened by pressing the top without further mixing.
3) The flat circular pile is then divided Into four quarters.
4) The two opposing quarters are discarded.
5) The two remaining quarters are mixed and steps 1-5 are repeated
until a 5-10 pound laboratory sample 1s obtained.
D-3
-------
6) The 5-10 pound laboratory sample 1s to be placed In a 1-gallon
wide-mouthed polypropylene bottle, or other suitable containers.
D.6 REFERENCES
ANSI/ASTM 346-78. Standard Method of Sampling Coke for Analysis.
Annual ASTM standards, Part 26, p. 213, 1978.
D-4
-------
APPENDIX E
XAD-2 RESIN CLEANING PROCEDURE
E-l
-------
E. CLEANING PROCEDURE FOR THE XAD-2 RESIN
The resin as supplied by the manufacturer is impregnated with a bi-
carbonate solution to inhibit microbial growth during storage. The salt
solution as well as extractable organic species must be removed by the
cleaning procedure prior to use as a sorbent agent. Purification of
the resin is accomplished by a series of extractions employing three
different solvents.
E.I EXTRACTION APPARATUS
The continuous extractor fabricated for the extraction process is
shown in Figure E-l. The resin container is constructed from a 3-liter
resin kettle and accommodates ^800 g of resin. All materials of con-
struction are glass, Teflon or stainless steel to maintain as low a level
of contamination as possible. A coarse glass frit is placed at the bottom
of the extractor to support the resin and at the same time allow for
even distribution of the freshly distilled solvent. The distillation
pot is a 5-liter flask and is equipped with a column, distillation head
and condenser. During the extraction process, solvent is distilled and
continuously cycled up through the XAD-2 resin for extraction and returned
to the distillation flask through the Teflon line as shown in the diagram.
Flow is from the bottom to the top in the extractor to allow maximum
solvent contact and prevent channeling. Washing with water is performed
employing a reversed flow. Water is added to the top of the extractor and
allowed to drain out the bottom. The reversed flow is necessary because
of the wetting characteristics of the resin. After extraction of the resin
with the organic solvents (methanol and methylene chloride), the resin is
dried using a stream of nitrogen. No heat is employed in the drying
process.
E.2 OPERATING PROCEDURES
E.2.1 Mater Mash
Add sufficient XAD-2 resin to fill the extractor to within -vl/2 inch
of the top of the main body. Attach the resin kettle top to extractor body
and evenly tighten clamps. Attach water line from reservoir (5 gal.) so that
water enters the extractor at the top and flows out the bottom (Figure E-l ).
E-2
-------
THERMOMETER
GLASS WOOL
1/4"
TEFLON
TUBING
5-GAL
WATER
RESERVOIR
3-1 RESIN
KETTLE
GLASS FRIT
GLASS WOOL
WATER DRAIN
Figure E-l.
Schematic of Continuous Extractor
for Cleaning Resin
E-3
-------
Fill the reservoir with 5 gallons of deionized water, then start addition
of water to the extractor. Adjust water flow out of extractor using the
stopcock so that the resin Is thoroughly wetted. The flow rate should be
MOO ml/m1n. Continue washing until a total of 10 gallons of water has
passed through the extractor. Allow the water to drain from the extractor
for about 10 minutes. Then wash the resin with 1-liter of methanol by
adding the solvent to the top of the extractor and allowing it to perco-
late through the resin and drain out the bottom. This step removes the
bulk of the remaining water. After the methanol rinse, proceed to the methanol
extraction.
E.2.2 Methanol Extraction
Set up the extraction apparatus as shown in Figure E-l so that the
freshly distilled solvent will enter the resin bed at the bottom of the
canister. Add ^3 liters of methanol (DIstilled-in-Glass grade) to the
distillation flask and fill the extractor to the body/top joint with the
same solvent. Heat the distillation flask until solvent is refluxlng.
Adjust heat input so that boil-up rate, the amount of methanol condensed
and passed through the extractor, is 20 ml/min. As the extractor 1s
filled, check for any leaks 1n the system. Continue the methanol extraction
for at least 16 hours. This time period will allow a sixfold change-
over In solvent. Turn off the heat on the distillation flask, allow reflux
to stop, then drain the methanol from the extractor using the 3-way
stopcock at the bottom of the extractor. Remove methanol from the dis-
tillation flask and replace with methylene chloride (~3 liters, Dlstilled-
in-Glass grade). Proceed with the methylene chloride extraction.
E.2.3 Methylene Chloride Extraction
The same apparatus setup used for the methanol extraction 1s employed
for the methylene chloride extraction. Fill the extractor with DlstHled-
1n-Glass methylene chloride and heat the distillation flask until the
solvent refluxes. Adjust boil-up rate to provide a flow of 15 ml/m1n Into
the extractor. Extract the resin for 24 hours. Periodically check the
apparatus for leaks and replace methylene chloride to maintain ^2.5 liters
of solvent in the distillation flask. After 24 hours turn off the heat for
E-4
-------
the distillation flask and drain the solvent from the extractor through the
3-way stopcock.
E.2.4 Drying XAD-2 Resin
Connect a gas line (Teflon 1s preferred) from a nitrogen cylinder to
the bottom of the extractor. This line 1s to be equipped with a tube
containing clean XAD-2 resin to trap any organic components present 1n
the nitrogen stream to prevent contamination of the purified resin, Re-
move two stoppers from the resin kettle top and start a slow flow of
nitrogen through the resin. Periodically adjust the rate of gas flow so
that the extractor and resin bed do not become supercooled during the
drying step. Complete drying requires 24 to 48 hours and consumes a full
cylinder of nitrogen. The dried resin 1s transferred to a clean bottle
and sealed. Four batches are mixed together 1n the holding vessel to
provide a lot of resin. Mixing 1s best accomplished by rolling the con-
tainer of resin on a roller for ^30 minutes. Each lot of resin must pass
quality control tests for volatile and nonvolatile organic content before
being bottled for use 1n the field. After quality control testing, cleaned
restn 1s packed Into the bottles; the bottles are filled with distilled,
delontzed water; and the bottles are sealed. Each bottle contains sufficient
resin to fill one SASS train resin canister.
E-5
-------
APPEND!* F
SCHEMATIC OF TRW SAMPLING VAN
F-l
-------
RUE
EXTINGUISHES
AIR COMPRESSOR/PURIFIER
ISOLATION
TRANSFORMER F,DANOTC
INTEGRATING / GAS CHROMATOGRAPHS
RECORDER
I
ro
VENT
HOOD
REFRIGERATOR UNDER COUNTER
Figure F-l. Schematic of TRW Sampling Van
-------
TECHNICAL REPORT DATA
(Please read fauruttiont on the reverse before completing)
1. REPORT NO.
EPA-600/7-79-029a
2.
4. TITLE AND SUBTITLE Emissions Assessment of Conventional
Stationary Combustion Systems: Methods and Proce-
dures Manual for Sampling and Analysis
3. RECIPIENT'S ACCESSION-NO.
B. REPORT DATE
January 1979
B, PERFORMING ORGANIZATION CODE
7. AUTHOR(s)JtWgHamersma ^ Dt G> Acker man, M. M. Ya-
mada.C. AJZee, C. Y.ync ,K. T. McGregor, J. F. Clau-
sen .M.L/Kraft. J.S.ShipTro. and E.LrMoon
8. PERFORMING ORGANIZATION REPORT NO
B. PERFORMING ORGANIZATION NAME AND ADDRESS
TRW Systems Group
One Space Park
Redondo Beach, California 90278
10. PROGRAM ELEMENT NO.
EHB525
11, CONTRACT/GRANT NOT
68-02-2197
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
RIOD COVERED
14. SPONSORING AGENCY CODE
EPA/600/13
iB.SUPPLEMENTARY NOTESTERL_RTP project officer is Ronald A. Venezia, MD-62, 919/541^
2547.
. ABSTRACT The manuai describes a detailed and integrated set of sampling and analy-
tical procedures for conventional combustion sources which are compatible with the
information requirements of a comprehensive Level 1 environmental assessment.
The purpose of the data to be generated by these tests is to ultimately provide emis-
sion factors for conventional stationary combustion sources. This is the first de-
tailed application of Level 1 procedures to all phases (sampling, sample handling,
disbursement, and analysis) of a specified program. Although the manual has been
designed to meet the exact data needs of this program, the procedures have general
applicability to most environmental assessment activities. Chapters include quality
assurance, sample and data management, field sampling, field analysis, organic
analysis, and inorganic analysis.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
). IDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
Pollution
Sampling
Analyzing
Industrial Processes
Energy Conversion
Gas Sampling
8. DISTRIBUTION STATEMENT
Unlimited
Aerosols
Liquids
Slurries
Solids
Inorganic Com-
pounds
Organic Compounds
Pollution Control
Stationary Sources
Environmental Assess
ment
Energy Processes
13B
14B
13H
10A,10B
19. SECURITY CLASS (TMtRtport)
Unclassified
07D
11G
07B
07C
34. NO. 6F PAGES
428
20. SECURITY CLASS (Thltpugt)
Unclassified
22. PRICE
F-3
*U.S. GOVERNMENT PRINTING OFFICE; 1979-6^0-01^ 4209 REGION NO.
------- |