EPA-600/2-77-024
January 1977
Environmental Protection Technology Series
TECHNICAL MANUAL FOR INORGANIC
SAMPLING AND ANALYSIS
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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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 five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecblogical Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental
Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the
views and policy of the Agency, 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/&-77-024
January 1977
TECHNICAL MANUAL
FOR INORGANIC SAMPJLING
AND ANALYSIS
by
R. F. Maddalone and S. C. Quinlivan
TRW—Defense and Space Systems
One Space Park
Redondo Beach, California 90278
Contract No. 68-02-1412, Task 16
ROAPNo. 21AZZ-015
Program Element No. 1AB013
EPA Task Officer: Robert M. Statnick
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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CONTENTS
Page
Acknowledgment xiii
Introduction 1
01-Sampling
01-01 Table of Contents for Sampling Gas/Vapor in Flue Gas ... 5
01-01 Application Matrix for Sampling Gas/Vapor in Flue Gas ... 6
01-01 Sampling Gases or Vapors in Flue Gas (see 02-05-01 for
probes and filters) 7
01-01-01 Adsorption in Liquids
01-01-01-01 Determination of Sulfur Dioxide Emissions
Stationary Sources 12
01-01-01-02 Oxides of Nitrogen in Gaseous Combustion
Products by the Phenol"Disulfonic Acid Procedure .... 13
01-01-01-03 High Pressure Gas Sampling Train (Gasifier
Output Sampling) 14
01-01-01-04 Collection of Mercury in Gaseous Emissions
from Stationary Sources 16
01-01-01'05 Sampling Vaporous Trace Elements in Flue Gas . 17
01-01-01-06 Determination of Sulfuric Acid Mist and
Sulfur Dioxide Emissions from Stationary Sources .... 18
01-01-01-07 Determination of Hydrogen Sulfide Emissions
from Stationary Sources 19
01-01-01-08 Sample and Velocity Traverses for Stationary
Sources 20
01-01-01-09 Stack Gas Velocity and Volumetric Flow Rate
(Type S Pitot Tube) . . . . 23
01-01-02 Adsorption on Solids
01-01-02-01 Sampling Flue Gases Using Direct Reading Gas
Detection Tubes 25
01-01-02-02 S02 Adsorption on Solids (Silica Gel) 28
01-01-03 Condensation Techniques
01-01-03-01 Sulfur Oxides in Flue Gas by Controlled
Condensation (Goksoyr-Ross Method) 30
01-01-04 Gas Grab Sampling
01-01-04-01 General Gas Grab Sampling Techniques 31
01-01-04-02 Flue Gas Grab Sampling Using Plastic Bags ... 33
01-01-04-03 High Pressure Gas Grab Sampling (Natural Gas
Containing Hydrocarbons and Nitrogen, Sulfur) 35
ill
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CONTENTS (Continued)
Pa^e
01-02 Table of Contents for Sampling Liquid/Slurry 37
01-02 Application Matrix for Liquid/Slurry Sampling 38
01-02 Sampling Liquid and Slurry 39
01-02-01 Automatic Liquid/Slurry Sampling
01-02-01-01 Sampling Liquid Streams with a CVE Composite
Sampler 43
01-02-01-02 Model 1680 Sequential Liquid Slurry Sampler . . 45
01-02-01-03 Liquid Sampling of Lines or Tanks Using
Model L Sampler 46
01-02-02 Liquid/Slurry Grab Sampling
01-02-02-01 Grab Sampling of Water 48
01-02-02-02 Liquid/Slurry Grab Sampling (Dipper Sampling,
Thief Sampling) 51
01-03 Table of Contents for Sampling Solids 53
01-03 Application Matrix for Solid Sampling 54
01-03 Sampling Solids 55
01-03-01 Automatic Solid Sampling
01-03-01-01 Sampling Solid Materials With a Pneumatic
Sampler 61
01-03-01-02 Sampling of Solids (Coal) Using Standard
Mechanical Methods 63
01-03-02 Solid Grab Sampling
01-03-02-01 Solids Grab Sampling (Long-Pile, Alternate
Shovel Method) 65
01-04 Table of Contents for Sampling for Particulate or Aerosol
in Flue Gas 69
01-04 Application Matrix for Particulate or Aerosol Sampling
in Flue Gas 7Q
01-04 Sampling for Particulate or Aerosol in Flue Gas 7]
01-04-01 Mass Loading Techniques
01-04-01-01 Sampling Flue Gas for Trace Inorganic
Materials 74
01-04-01-02 Particulate Sampling in Flue Gas Streams for
Non-Trace Element Constituents 7g
01-04-02 Particle Sizing Techniques
01-04-02-01 Particulate Size Sampling in Flue Gas Streams . 78
01-04-02-02 Level 1 Environmental Assessment Flue Gas
Sampling Train 80
iv
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CONTENTS (Continued)
Page
01-05 Table of Contents for Sampling for Fugitive Gas Emissions . 83
01-05 Application Matrix for Sampling for Fugitive Gas Emissions 84
01-05 Sampling for Fugitive Gas Emissions 85
01-05-01 Absorption in Liquids
01-05-01-01 Nitrogen Dioxide Content of the Atmosphere
Using the Griess-Saltzman Reaction 89
01-05-01-02 Oxidant (Ozone) Content of the Atmosphere ... 90
01-05-01-03 Sulfur Dioxide Content of the Atmosphere
(West-Gaeke Method) 91
01-05-02 Adsorption on Solids
01-05-02-01 Fugitive Gas Sampling with Direct Reading
Colorimetric Detection Tubes 92
01-05-02-02 Sampling for Lead in the Atmosphere 93
01-05-02-03 Impregnated Paper Tape Methods for Determina-
tion of Hydrogen Sulfide in Air 94
01-05-02-04 Fugitive Gas Sampling by Adsorption on Solids
(Carbon, Silica) 95
01-05-03 Condensation Techniques
01-05-03-01 Fugitive Gas Sampling by Condensation
Techniques 97
01-05-04 Fugitive Gas Grab Sampling
01-05-04-01 General Fugitive Gas Grab Sampling Techniques . 99
01-05-04-02 Fugitive Gas Grab Sampling Using Plastic Bags . 101
01-06 Table of Contents for Sampling for Fugitive Particulate
Emissions 103
01-06 Application Matrix for Fugitive Particulate Emissions . . . 104
01-06 Sampling for Fugitive Particulate Emissions 105
01-06-01 Mass Loading Techniques
01-06-01-01 Collection and Analysis of Dust Fall (Settleable
Particulates) 108
01-06-01-02 Continuous Monitoring of Mass Loadings Using
Beta Attenuation 109
01-06-01-03 Piezo-Electric Aerosol Mass Concentration
Monitor Ill
01-06-01-04 Sampling Fugitive Emissions by High Volume
Samplers 112
01-06-01-05 Fugitive Emissions Sampling With an Electro-
static Precipitator 114
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CONTENTS (Continued)
01-06-01-06 Combined Sampling Analysis Method for Deter-
mination of Trace Elements Atmospheric Parti culates
(Graphite Cup) ..................... Mt>
01-06-01-07 Sampling Fugitive Emissions With Sequential
Tape Samplers ........ . ............ '
01-06-02 Particle Sizing Techniques
01-06-02-01 Particle Sizing of Fugitive Emissions ..... 118
02-Analysis
02-01 Table of Contents for Laboratory Preparation ....... ^*
02-01 Application Matrix for Laboratory Preparation ....... 12°
02-01 Laboratory Preparation .................. 121
02-01-01 Reagent/Equipment Preparation
02-01-01-01 Reagent Quality Water (for Preparation, Cleaning
of Sample Containers) ................. 128
02-01-01-02 NBS Certified Standards for Elements in Lubri-
cating Oils ...................... 13°
02-01-01-03 Storage of Reagents Used in Chemical Analyses . 132
02-01-01-04 NBS Standard Reference Materials for Coal and
Fly Ash ........................ 133
02-01-01-05 Cleaning Procedures for Laboratory Glassware
and Plastic Containers ................. 134
02-01-01-06 Preparation of High Purity Reagents for Trace
Analysis ........................ 135
02-01-01-07 Gas Sampling Container Cleaning Procedure ... 137
02-01-02 Sample Separation
02-01-02-01 Ion Exchange Method for the Isolation of
Fluoride from Environmental Samples .......... 138
02-01-02-02 Willard Winter Distillation for the Isolation
of Fluoride from Atmospheric Samples .......... 139
02-01-02-03 Separation of Liquid/Slurry Samples ...... 140
02-01-03 Sample Handling/Preservations
02-01-03-01 Recommendations for Preservation of Samples
According to Measurement ................ 142
02-01-03-02 Preparing Coal Samples for Ultimate and/or
Proximate Analysis (Mechanical and Manual Reduction
and Division) .................. 145
02-01-03-03 Sample Recovery from Impingers ........ 149
02-01-03-04 Removal of Filters from Filter Holder ..... 150
vi
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CONTENTS (Continued)
Page
02-01-03-05 Removal of Particulate from Cyclones 152
02-01-03-.06 Handling of Probe Liner Samples 153
02-01-04 Sample Dissolution
02-01-04-01 Total Chlorine in Coal (Eschka Analysis) ... 154
02-01-04-02 Coal Dissolution Scheme for Various Elements . 156
02-01-04-03 Low Temperature Plasma Ashing and Dissolution
of Collected Particulate 158
02-01-04-04 Mixed Ligand Extraction of Ag, Cd, Co, Cu, Fe,
Ni, Pb, Zn and Be from Tape Sampler Dust Spots 159
02-02 Table of Contents for Elemental Analysis 161
02-02 Application Matrix for Elemental Analysis 162
02-02 Elemental Analysis 163
02-02-01 Single Element/Cation Analysis
02-02-01-01 Lead Analysis by Dithizone Colorimetric
Procedure 169
02-02-01^02 Determination of Hg in Iodine Monochloride
Impinger Solutions 170
02-02-01-03 Ultimate Analysis of Coal (for Carbon and
Hydrogen, Nitrogen and Oxygen) 172
02-02-01-04 Analysis of Coal and Coke Ash for Al, Si, Fe,
Ti, P, Ca, Na by Photometry and/or Chelatometric
Titration 173
02-02-01-05 Atomic Absorption Techniques for Ba, Be, Cd,
Ca, Cr, Cu, Pb, Mn, Hg, Ni, V, Zn, Al, Sb, As, Co, Fe,
Mg, Mn, Mo, K, Ag, Na, Th, Sn, Ti 175
02-02-OU06 Determination of Acidity by Electrometric
Titration 178
02-02-01-07 Determination of Arsenic by Silver Diethyl
Dithiocarbamate Method 179
02-02-01-08 Determination of Biochemical Oxygen Demand
Using Bioassay Procedures 180
02-02-01-09 Determination of Dissolved Oxygen (Modified
Winkler With Full Bottle Technique) 181
02-02-01-10 Determination of Dissolved Oxygen (DO) by
Electrode (Probe) Method ... 182
02-02-01-11 Determination of Boron by Curcumin Method ... 183
02-02-01-12 Determination of Calcium by Titrimetry .... 184
02-02-01-13 Determination of Total Residual Chlorine by
Amperometric Titration or lodometric Titration 185
vi i
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CONTENTS (Continued)
02-02-01-14 Determination of Silica (Dissolved) ...... 186
02-02-01-15 Spectrophotometric Determination of Antimony . 187
02-02-01-16 Determination of Selenium by Di ami nobenzi dine
Method ......................... 188
02-02-01-17 Determination of Selenium by Distillation-
Diaminobenzidine Method ................
02-02-01-18 Determination of Cations Using Specific Ion
Electrodes (SIE) .................... 19°
02-02-01-19 Determination of Ammonia by Colorimeric-
Phenate Method ..................... 193
02-02-01 -.20 Determination of Total Nitrogen by Kjeldahl
Method ......................... 194
02-02-01-21 Determination of Heavy Metals by Dithizone
Method ......................... 196
02-02-01-22 Determination of Hexavalent Chromium by
Diphenyl Carbazide Method ............... 198
02-02-01-23 Determination of Iron (Total, Filterable, or
Ferrous) by Phenanthroline Method ........... 199
02^02-01-24 Determination of Chemical Oxygen Demand .... 200
02-02-01-25 Determination of Ammonia by Distillation
Procedure ....................... 201
02-02-01-26 Determination of Beryllium by Aluminon Method . 202
02-02-01-27 Determination of Total Chromium by Diphenyl
Carbazide Method .................... 203
02-02-01-28 Determination of Total Copper by Neocuproine
Method . ........................ 204
02-02-01-29 Determination of Calcium by Gravimetric Method 205
02-02-01-30 Determination of Total Magnesium by Gravimetric
Method ........ ................. 206
02-02-01-31 Determination of Nickel by Heptoxime Method . . 207
02-02-01-32 Determination of Potassium by Cobalti nitrite
Method ......................... 208
02-02-01-33 Determination of Vanadium by Gallic Acid
Method ......................... 2og
02-02-01-34 Method for Determination of Total Alpha
Radioactivity Using Proportional or Scintillation
Counters ........................ 210
02-02-01-35 Method for Determination of Total Beta
Radioactivity Using Proportional or Geiger-Muller
Counters ........................ 211
viii
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CONTENTS (Continued)
Page
02-02-01-36 Method for Determination of Alpha and Beta
Radioactivity Counting Error 212
02-02-01-37 Method for Determination of Radium in Water . . 213
02-02-02 Multielement Analysis
02-02-02-01 Inductively Coupled Plasma Optical Emission
Spectroscopy 214
02-02-02-02 X-Ray Fluorescence of Environmental Samples . .
02-02-02-03 Optical Emission Spectroscopy (DC Arc/AC Spark) 219
02-02-02-04 Differential Pulse Anodic Stripping of Trace
Metals 222
02-02-02-05 Instrumental Neutron Activation Analysis ... 224
02-02-02-06 Spark Source Mass Spectrometry (SSMS) with
Photographic Plate Detection 226
02-02-02-07 Multielement Analysis Using Spark Source
Mass Spectrometry (SSMS) with Electrical Detection ... 228
02-03 Table of Contents for Species Analysis 231
02-03 Application Matrix for Species Analysis 232
02-03 Species Analysis 233
02-03-01 Laboratory Gas Analysis
02-03-01-01 GC Analysis of Flue Gas Samples (Instrumental
Orsat Analysis) 237
02-03-01-02 Laboratory Analysis of Sulfur-Containing Gases
by GC 238
02-03-02 Anion Analysis
02-03-02-01 Anion Analysis Using Specific Ion Electrodes
(SIE) 239
02-03-02-02 Spectrophotometric Determination of Fluoride
With Alizarin Complexone Reagent 242
02-03-02-03 Barium Chioranilate Colorimetric Sulfate
Method 243
02-03-02-04 Gravimetric and Titrimetric of Sulfate, Pyritic
Sulfur and Organic Sulfur in Coal 244
02-03-02-05 Determination of Sulfate by the Thorin Method . 246
02-03-02-06 Determination of Sulfate in Scrubber Liquors
(Sulfonazo III Titration) 247
02-03-02-07 Determination of Alkalinity by Electrometric
Titration 248
02-03-02-08 Determination of Bromide by Titrimetry .... 249
ix
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CONTENTS (Continued)
Page
02-03-02-09 Determination of Chloride by Titrimetry .... 250
02-03-02-10 Determination of Total Cyanide by Volumetric
Titration or Spectrophotometry
02-03-02-11 Determination of Iodide by Titrimetry 252
02-03.02-12 Determination of Nitrate Nitrogen by Brucine
Method 253
02-03-02-13 Determination of Nitrate-Nitrite Nitrogen by
Cadmium Reduction Method 254
02-03--02-14 Determination of Nitrite Nitrogen by
Spectrometry 256
02-03-02-15 Determination of Phosphorous (All Forms) by
Single Reagent Method 257
02-03-02-16 Turbidimetric Detection of Sulfate 259
02-03-02-17 Determination of Total and Dissolved Sulfite
Using Titrimetric Iodine Method 260
02-03-02-18 Determination of Sulfite Using Titrimetric
lodide-Iodate Method 261
02-03-02-19 Determination of Chloride by Colorimetry ... 262
02-03-02-20 Determination of Nitrate Nitrogen by Phenol
Disulfonic Acid Method 263
02-03-02-21 Determination of Total Solids 264
02-03-02-22 Determination of Total Dissolved (filterable)
Solids 265
02-03-02-23 Determination of Total Suspended (nonfilterable)
Solids 266
02-03-02-24 Determination of Total Volatile Solids .... 267
02-03-02-25 Determination of Total Hardness 268
02-03-02-26 Determination of Color by Spectrophotometric
Method 260
02-03-02-27 Determination of Color by Platinum Cobalt
Method 270
02-03-02-28 Determination of Specific Conductance 271
02-03-02-29 Determination of Turbidity by the Nephelometric
Method 273
02-03-02-30 Visual Determination of the Opacity of
Emissions from Stationary Sources 274
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CONTENTS (Continued)
Page
02-04 Table of Contents for Particulate Compound Analysis .... 275
02-04 Application Matrix for Solid and Particulate Compound
Analysis 276
02-04 Solid and Particulate Compound Analysis 277
02-04-01 Microscopic Analysis
02-04-01-01 Polarized Light Microscope Identification of
Air Particulate 282
02-04-01-02 Quantitative Analysis Using Transmission
Electron Microscopy (TEM) 284
02-04-01-03 Electron Probe Microanalysis (EPMA) for
Particulate Analysis 285
02-04-01-04 Scanning Electron Microscope (SEM) for
Qualitative Particulate Analysis 287
02-04-02 Chemical Analysis
02-04-02-01 Quantitative Compound Chemical Analysis by
X-Ray Powder Diffraction (XRD) 288
02-04-^02-02 Compound Identification by Electron Spectro-
scopy for Chemical Analysis (ESCA) 290
02-04-02-03 Chemical (Elemental) Analysis Using Scanning
Electron Microscope (SEM), Electron Probe Microanalysis
(EPMA) with an Energy Dispersive X-Ray Spectrometer
(EDX) 291
02-05 Table of Contents for On-Line Continuous Analysis 293
02-05 Application Matrix for On-Line Continuous Analysis .... 294
02-05 On-Line Continuous Analysis 295
02-05-01 On-Line Gas Analysis/Sampling
02-05-01-01 Probe and Filters for On-Line Measurement of
Fugitive Emissions on Flue Gas 298
02-05-01-02 Membrane Conditioning System for On-Line
Continuous Monitoring of Atmospheres and Flue Gases . . 299
02-05-01-03 Gas Conditioning by Controlled Condensation . . 301
02-05-01-04 Continuous On-Line Gas Monitoring Systems
Design 303
02-05-01-05 Multiport Probe for Continuous Gas Monitoring . 304
02-05-02 On-Line Continuous Gas Analysis
02-05-02-01 Continuous Monitoring of NO/N02 308
02-05-02-02 Continuous Monitoring of Ozone 311
02-05-02-03 Continuous Monitoring of Sulfur Dioxide .... 314
xi
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CONTENTS (Continued)
Page
02-05-02-04 Continuous Monitoring of C0/C02 377
02-05-02-05 Continuous Monitoring of H2S 320
02-05-02-06 Determination of Hydrocarbons Corrected for
Methane 322
02-05-03 On-Line Continuous Liquid Analysis
02-05-03-01 Continuous On-Line Liquid Analysis With a
Technicon Monitor IV System 323
02-05-03-02 Continuous On-Line Monitoring of Liquid Streams
With Orion Specific Ion Electrons 324
xli
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ACKNOWLEDGMENT
This document constitutes the draft report for the work
accomplished on Task 16, Technical Manual for Inorganic Sampling
and Analysis on EPA Contract No. 68-02-1412, Quick Reaction
Technical Services in Air Pollution Sampling Acquisition and
Analysis, Process Instrumentation, Process Research and Process
Evaluation.
TRW's Applied Chemistry and Materials Laboratory Applied
Technology Division was responsible for the work performed on
this task. The work was conducted under the technical direction
of Dr. R. M. Statnick, EPA Task Order Manager, and administrative
direction of Dr. L. D. Johnson, National Environmental Research
Center, Research Triangle Park, North Carolina. Dr. E. A. Burns,
Manager of the Applied Chemistry Department, was Program Manager,
and Task Order Manager was Dr. C. A. Flegal. Major technical
contributions were provided by Dr. R. F. Maddalone and Ms. S. C.
Quinlivan. Acknowledgment is made to Dr. J. W. Hamersma and
Mr. S. R. Reynolds for technical review provided during the program.
The authors wish to thank Mr. Chuck Weekley, Ms. Mary McKay and
Ms. Carmen de la Fuente for their efforts in the preparation and
publication of this report.
xiii
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ixv
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INTRODUCTION
This technical manual has been prepared for the Industrial and
Environmental Research Laboratory of the Environmental Protection Agency,
Research Triangle Park, North Carolina, in partial fulfillment of Task 16
of Contract #68-02-1412. The manual is written for personnel who are
experienced in collecting and analyzing samples from industrial and energy
producing processes. This manual includes general introductions to a
variety of sampling and analysis procedure categories as well as abstracts
on each specific method.
A. DESIGN OF MANUAL
This technical manual presents the state of the art of Inorganic
Sampling and Analysis (ISA) procedures in a standardized format that makes
methodology readily available to the professionals in the field. Because
of the breadth of ISA, a system was developed to avoid burying specific
methods in an avalanche of narrative. This design concept makes the
techniques of sampling and analysis easily accessible, while providing a
comprehensive, cross-referenced index of process stream and chemical test
situations, and procedures.
The sampling and analysis procedures in this manual are compatible with
either environmental assessment or process measurement activities. The
intent of this manual is to provide a compilation of methods applicable
to these activities. The methods included in this manual generally are
proven procedures from standard sources. In many cases, where gaps in
sampling or analysis procedures existed, the open literature and government
reports were combed for appropriate methods.
B. ORGANIZATIONAL OUTLINE
An eight-digit identification number is assigned to each sampling and
analysis method. The eight-digit identification (ID) number is designed to
cross-reference particular methods with the procedures associated with the
sampling phase and the analysis phase. The identification number functions
as follows. The first pair of digits of the ID number represents either
the sampling phase (designated 01) or the analysis phase (designated 02).
The phases are subdivided into process stream and chemical test categories
1
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(represented by the second pair of digits in the ID number) which have
procedures associated with them (represented by the third pair of digits
of the ID numbers). For each type of procedure there are specific examples
of implemented methods (designated by the fourth pair of digits in the ID
number), presented as abstracts. The abstract will provide enough informa-
tion to allow the measurement professional to decide whether or not the
method meets his needs. The abstract sheets contain a primary reference
that provides the reader with all the information required to implement
the procedure.
Each abstract contains the following information:
1) TITLE. The title is either a description of the technique, or the
specific name of the technique if it is from a standard source.
2) IDENTIFICATION CODE. This can be up to an eight-digit number which
signifies the procedural category grouping of the specific technique.
3) ABSTRACT OF METHODOLOGY. This section describes the key steps of
the laboratory preparation or procedure involved in a particular
sampling analysis. References to other pertinent abstracts are
included.
4) APPLICATION (HEADING). These headings are the possible use cate-
gories and will be arranged in descending order of applicability.
The categories are: Compliance, Engineering Evaluation R&D and
Environmental Assessment.
The compliance category contains most of the EPA approved methods
for water [Federal Register, 41 (232), 52780 (1976)] and air
[Federal Register, 41 (111), 23061 (1976)]. The environmental
assessment methods are those approved methods found in J.W. Hamersma,
S. L. Reynolds and R. F. Maddalone "IERL-RTP Procedures Manual:
Level 1 Environmental Assessment", TRW Systems Group, EPA
600/2-76-160a, June 1976. The Engineering Evaluation R&D methods
are taken from a variety of sources and provide sampling and analysis
alternatives to meet specific measurement problems. These
categories are not meant to restrict the use of the methods to the
specific applications, but are meant to be a guide to their source
and primary use.
a) Operational Scope: Describes the possible process streams to
which these specific techniques or methods can be applied.
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b) Interferences/Limitations: Describes the chemical or physical
interferences or limitations of the abstracted procedure.
c) Recommended Use Area: Specifies the intended use of the method.
5) OPERATIONAL PARAMETERS.
a) Range: Lists the working range and sensitivity (2
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C. BENEFITS OF THIS APPROACH
This system fulfills the need for general concepts while allowing:
t Easy review and update—Rather than rewriting extensive narrative,
each abstract is readily corrected or updated separately.
• Multidimensional expansion—Because the format is designed as a
four-level branching network, major categories and specific
examples can be added as appropriate. Furthermore, the exact
instructions can be printed on a continuation sheet and inserted
behind the abstract sheet.
• Cross-reference access to procedures—Since each abstract is key-
worded, a thesaurus of keyword ID numbers can be developed.
• Recommended methods can be clearly identified—Since each procedure
is in abstract form, either a list of ID numbers or color-coded
pages can be used to specify recommended procedures.
• Readily used as source for procedure manuals —Individual abstracts
for specific process sampling and analysis needs can be rapidly
assembled as a "rough draft" to form a procedures manual. From
this assemblage of abstracts, a smooth narrative can be written
using the information and figures provided in the abstracts. The
abstracts are then kept in an appendix as a source of reference.
Thus, this technical manual is designed to be a living document, one that
can be continually updated, revised and expanded simply by changing or adding
abstract sheets.
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Table of Contents for 01-01 Sampling Gas/Vapor in Flue Gas
01-01-01 Adsorption in Liquids
01-01-01-01 Determination of Sulfur Dioxide Emissions
Stationary Sources
01-01-01-02 Oxides of Nitrogen in Gaseous Combustion
Products by the Phenol Disulfonic Acid Procedure . .
,01-01-01-03 High Pressure Gas Sampling Train (Gasifier
Output Sampling) .
01-01-01-04 Collection of Mercury in Gaseous Emissions
from Stationary Sources
01-01-01-05 Sampling Vaporous Trace Elements in Flue Gas .
01-01-01-06 Determination of Sulfuric Acid Mist and
Sulfur Dioxide Emissions from Stationary Sources . . . .
01-01-01-07 Determination of Hydrogen Sulfide Emissions
from Stationary Sources
01-01-01-08 Sample and Velocity Traverses for Stationary
Sources . .
01-01-01-09 Stack Gas Velocity and Volumetric Flow Rate
(Type S Pi tot Tube)
01-01-02 Adsorption on Solids
01-01-02-01 Sampling Flue Gases Using Direct Reading Gas
Detection Tubes
01-01-02-02 S02 Adsorption on Solids (Silica Gel) .
01-01-03 Condensation Techniques
01-01-03-01 Sulfur Oxides in Flue Gas by Controlled
Condensation (Goksoyr-Ross Method)
01-01-04 Gas Grab Sampling
01-01-04-01 General Gas Grab Sampling Techniques
01-01-04-02 Flue Gas Grab Sampling Using Plastic Bags . . .
;01-01-04-03 High Pressure Gas Grab Sampling (Natural Gas
Containing Hydrocarbons and Nitrogen, Sulfur)
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APPLICATION MATRIX FOR 01-01 SAMPLING GAS/VAPOR IN FLUE GAS
METHOD
01-01-01-01
01-01-01-02
01-01-01-03
01-01-01-04
01-01-01-05
01-01-01-06
01-01-01-07
01-01-01-08
01-01-01-09
01-01-02-01
01-01-02-02
01-01-03-01
01-01-04-01
01-01-04-02
01-01-04-03
LEVEL I
ENVIRONMENTAL
ASSESSMENT
i' . -
•
•
•
•
•
•
COMPLIANCE
•
' •
•
1
•
•
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SAMPLING GASES OR VAPORS IN FLUE GAS - ID No. 01-01
This section will discuss the sampling of gases or vapors in flue gas
streams. The techniques employed are absorption in liquids, adsorption on
solids, condensation and grab sampling. No one specific technique is
best for all situations, but on the basis of use, absorption in liquids is
the most popular, followed by grab sampling.
Recent studies (reference 001) have shown that a high degree
(10-20%) of stratification of gases occurs in flue gas ducts. Consequently,
gas sampling requires techniques similar to particulate sampling. The
exception to this comparison is that gas sampling does not require
isokinetic flow rates to obtain a representative sample, but standard
procedures (reference 002) should be used to choose a representative
sampling point.
The point of this discussion is that each method has its limitations.
No one method will fulfill all sampling needs. The analyst, by under-
standing the benefits and drawbacks of each procedure, will make the right
choice for a given sampling task.
01-01-01 Absorption in Liquids (Abstracts 01-01-01-01 Through
01-01-01-057 • ' ——
Absorption of gases in a liquid bath retains and concentrates the
contaminant for subsequent analysis. The flow rate will depend on the
equipment used. Typical flow rate values for various liquid absorbing
systems are: 2 1pm for fritted bubblers, 2.8 1pm for midget impingers,
28 1pm for Greenburg-Smith impingers, arid 140 1pm for impingers found in
high volume stack samplers (see 01-04-01-02).
The efficiencies of these collection devices typically run between
95 to 99% for reactive collection media (for example 3% hUjOp for S02,
see 01-01-01-01). These efficiencies are influenced by several factors:
1) Solubility of contaminant in collection medium - Normally,
reactive media are chosen to prevent escape of absorbed
gases.
2) Rate of diffusion into the medium - This is partially influenced
by temperature and bubble size which depends on flow rate and
choice of impinger.
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3) Vapor pressure of contaminant at sampling temperature - Normally
ice baths are used to cool gases and reduce volatility.
4) Chemical reactivity of contaminant with sampling medium -
Reaction rate is the most important variable. The contaminant
must react faster than it can be revolatilized (01-01-01-02).
5) Flow rate - The flow rate will affect contact time in the bubbler
and because of the above considerations will directly affect
efficiency.
Finally, the prime consideration when using liquid absorbers is to
select a medium which does not interfere with any subsequent analysis.
In all cases, the analyst must be aware of the ultimate goal of the
sampling task so that the choice of sampling system does not complicate
or invalidate the final analysis of the collected sample. For example, if
compound identification is the ultimate goal of the sampling task, collection
cf Hg and (CH3)2 Hg in an oxidative scrubber (01-01-01-02, 01-01-01-05) will
destroy the compounds and yield the total Hg content of the stream. Either
grab sampling or selective adsorption would be a better choice.
01-01-02 Adsorption on Solids (Abstracts 01-01-02-01 Through
01-01-02-03)
Adsorption on solid media and in particular silica gel for inorganic
compounds provides a viable alterative to liquid absorption. Silica gel
or molecular sieve packing materials adsorb inorganic gases readily while
allowing quantitative removal back in the laboratory. Silica gel has
found extensive use (see 01-01-02-01) as a support medium for direct
reading colorimetric sampling tubes (reference 003). As with liquid
absorption, several factors (reference 004) can affect the efficiency of
solid adsorbents:
1) Previous history of the gel - The silica gel is usually cleaned
by heating in a nitrogen atmosphere at 350 to 400°C.
2) Size of gel particles - The smaller the particle size, the
greater the surface area for adsorption, but the higher the
pressure drop. Normally, a gel size range of 6 to 28 mesh is
satisfactory, provided a narrow (6-16 or 14-28) range of
particles is actually used.
8
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3) Amount of gel particles - The bed depth and mass of silica gel
used ultimately affects the capacity and efficiency of the
adsorbing system. The minimum diameter of the adsorbing column
should be several times larger than the diameter of the gel to
prevent channeling.
4) Flow rate - This is a difficult variable to assess and probably
will depend on the species being adsorbed as well as the chemical
reaction (if impregnated silica gel is used). Nominal linear flow
rates are from 50 to 1000 cm/min.
5) Temperature - In most cases, this variable should be kept as
low as possible. Normally, room temperature is sufficient.
Direct reading colorimetric tubes are useful up to 50°C.
6) Chemical reactions - One must always guard against unwarranted
side reactions once the gas is adsorbed. In particular,
oxidation of adsorbed S02 must be prevented by rapid analysis
or storage under nitrogen.
Desorption of gases (S02, NHg) adsorbed on silica gel (01-01-02-02,
01-01-02-03) is normally done by heating the adsorption tube in the
presence of an inert gas flow. The gas can then be analyzed by liquid
absorption or by instrumental techniques. Solid adsorption effectively
concentrates the gas sample so the analyst has a much easier analysis
task.
01-01-03 Gas Condensation Techniques (Abstract 01-01-03-01)
Condensation or freeze-out techniques are more useful for organic vapor
sampling. Inorganic gases normally require too low of a temperature to
make freeze-out techniques practical. Controlled condensation of a gas
like SO, can be accomplished because of its affinity for water. This
procedure is described in 01-01-03-01 and is recommended over Method 8
as the method of choice for SO, measurements. Recent studies (reference
005) have shown that 80% isopropanol picks up significant quantities of
S02 which oxidizes in solution causing a positive error.
01-01-04 Flue Gas Grab Sampling (Abstracts 01-01-04-01 Through
01-01-04-037
Grab sampling is the use of rigid or nonrigid containers for collect-
ing a single point/single sample or multipoint/composite sample of gas
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for subsequent laboratory analysis. For flue gas sampling plastic
bags are not recommended, though they can be used under a narrow set cf
temperature and gas component conditions (see 01-01-04-02). For the
most part, flue gas grab sampling will be accomplished using rigid con-
tainers made of glass or stainless steel (01-01-04-01, 01-01-04-03).
The key problem with grab sampling is the possibility of chemical
changes occurring in or catalyzed by the sample container. Gas phase
reactions do not stop once the gases are removed from the gas stream.
In fact, removal from the gas stream probably will initiate reactions.
For example, once the gas container is filled, the temperature will fall
causing any excess moisture to condense. The condensation process can
change the gas phase concentration of S02» COp or HpS. If glass containers
are used, photochemical reactions must be guarded against by keeping the
container in a dark place prior to analysis.
The biggest problem with grab samples is the adsorption of gases onto
the walls of the container. To a certain extent, the containers can be
warmed prior to analysis or flushed with inert gas to remove any adsorbed
gases. The preferred approach to this problem is to analyze the gas in
the container as soon as possible after sampling.
Since the rigid containers will be reused, caution must be exercised
to remove any last traces of the previous sample. Since the last gas
sampled could conceivably activate the container walls to subsequent
chemical reactions by the next gas sample, each container should be
passivated by the appropriate technique prior to reuse (see 02-01-01-07).
10
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REFERENCES
001 Brooks, E.F., C.A. Flegal, L.N. Harriett, M.A. Kolpin, D.L. Luciani
and R.L. Williams, "Continuous Measurement of Gas Composition from
Stationary Sources," EPA-600/2-75-012, TRW Systems, Redondo Beach,
CA., July 1975.
002 Federal Register, "Method 1 - Sample and Velocity Traverses for
Stationary Source," 36_(247), 24882 (December 23, 1971).
003 Leichnity, K., "Detector Tube Handbook," 2nd ed., Dragerwerk-A-G-
Lubeck, October 1973 (obtained from National Mine Service Co.,
Pittsburgh, PA.).
004 Ind. Hyg. Assoc., "AIHA Analytical Guides," 1965, p. 8-16.
005 Grant, A., D.L. Luciani and R.F. Maddalone, "Final Report for Process
Measurements Development: Particulate Sulfate Emissions," TRW Systems,
Redondo Beach, CA., EPA Contract No. 68-02-14-12, March 1975.
11
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1. TITLE DETERMINATION OF SULFUR DIOXIDE EMISSIONS FROM STATIONARY SOURCES
2. IDENTIFICATION CODE
01-01-01-01
1 ABSTRACT OF METHODOLOGY
A gas sample is removed from the gas stream and the acid mist, including sulfur trioxide, is separated from the sulfur dioxide using a
midget bubbler filled with 80 percent isopropyl alcohol. The resultant gas stream is passed through two midget impingers containing a
3 percent solution of H.,0,, to remove the sulfur dioxide. The peroxide solution is titrated with barium perchlorate using thorin as the
indicator (see 02-03-02-05).
4. APPLICATION^ Compliance, engineering evaluation R&D.
A) OPE RATIONAL SCOPE
This procedure is designed to sample S02 from flue gas streams to determine compliance with New Source Performance Standards of the
EPA.
B) INTERFERENCES/LIMITATIONS
Varying amounts of SO, can be collected in the isopropyl alcohol trap and cause negative results. The 80 percent IPA impinger should
be purged with nitrogen into the 5 percent H202 impingers to remove any S02 absorbed in the IPA.
C) RECOMMENDED USE AREA
Compliance testing of stationary sources.
5. OPERATIONAL PARAMETERS
A) RANGE N/Q (10 ppm lower limit estimated).
B) ACCURACY *5%
C) PRECISION ±3X or better.
6. REAGENTS REQUIRED
Water (D.I.), isopropanol (80%), hydrogen peroxide (3%), thorin,
barium perchlorate, sulfuric acid.
7. EQUIPMENT REQUIRED
Glass probe, midget bubbler, glass wool, midget impinger, drying
tube, needle valve, vacuum pump, rate meter, dry gas meter,
laboratory glassware.
8. KEYWORD INDEX: Flue gas sampling, S02 sampling, compliance, sampling.
9. CROSS REFERENCE ID NUMBERS 02-03-02-05,-06; 02-01-01, 03.
10. REFERENCES
A) PRIMARY SOURCE
006 Federal Register, "Determination of Sulfur Dioxide Emissions from Stationary Sources," 36J247), 24890 (1971).
B) BACKGROUND INFORMATION
007 NoS'999-AP-l>3!'cincinnItf!rOhio1n965)."AtlI'0$PheriC Eln1SSi0nS fr™ SulfuHc Acid Manufacturing Processes," PHS Publication
008 Patton, W.F.,and J.A. Brink, Jr., "New Equipment and Techniques for Sampling Chemical Process Gases," J.A.P C A 13 162(1963)
C) FIELD APPLICATIONS •—••—• Vi»<";
009 Corbett, P.P., "The Determination of S02 and S03 in Flue Gases," J. Inst. Fuel. 24, 237 (1961).
010 Matty, R.E.,and E.K. Diehl, "Measuring Flue Gas S02 and S03>" Power, 101. 94 (1957).
Oil Driscoll, J..J. Becker, R. Hebert K. Horbal, and M. Young, "Validation of Improved Chemical Methods for Sulfur Oxides
ments from Stationary Sources," Walden Res. Corp., Cambridge, Mass., PB215-887, November 1972.
012 Driscoll, J.,and AW. Berger, "Improved Chemical Methods for Sample and Analysis of Gaseous Pollutants from the Combustion of
Fossil Fuels, Ualden Res. Corp., Cambridge, Mass.. PBZ09-267. June 1971. '""stion of
J2
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1 TiTLc OXIDES OF NITROGEN IN GASEOUS COMBUSTION PRODUCTS BY THE
l. lliuc PHENOL D|SULFON|C AC!D PROCEDURE
IDENTIFICATION CODE
01-01-01-02
3. ABSTRACT OF METHODOLOGY
The gas sample is admitted into an evacuated flask containing an oxidizing absorbent consisting of hydrogen peroxide in dilute sulfuric
acid. The oxides of nitrogen are converted to nitric acid by the solution. The NOX as nitrate ion is reacted with phenol disulfonic
acid to produce a. yellow compound which is measured colorimetrically at 400 ran (see 02-03-02-20).
4. APPLICATION- Compliance, engineering evaluation R&D.
A) OPERATIONAL SCOPE
This method can be used to measure the total oxides of nitrogen (N-0 excepted) in gaseous effluents from combustion and other
nitrogen oxidation processes.
B) INTERFERENCES/LIMITATIONS
Inorganic nitrates, nitrites or organic nitrogen compounds that are easily oxidized to nitrates interfere with the method and give
erroneous high results. Under conditions of high sulfur dioxide concentrations, care must be taken to ensure that there is enough
hydrogen peroxide solution to absorb both the S02 and the oxides of nitrogen. NOTE: ASTM admits that the role of some of the
constituents of combustion effluents as possible interferences has not been thoroughly investigated as of 1974.
C) RECOMMENDED USE AREA
Compliance testing.
5. OPERATIONAL PARAMETERS
A) RANGE This method is applicable to a concentration range of oxides of nitrogen as nitrogen dioxide from 5 to several
thousand parts per million.
B) ACCURACY N/Q
C) PRECISION
for synthetic samples.
6. REAGENTS REQUIRED
Hydrogen peroxide, sulfuric acid, ammonium hydroxide,
phenol disulfonic acid, potassium nitrate, sodium
hydroxi de.
7. EQUIPMENT REQUIRED
Calibrated sampling flask, spectrophotometer
glassware, mercury manometer, pump (vacuum),
, laboratory
water bath.
8. KEYWORD INDEX: Sampling, gas sampling, NOX analysis.
9. CROSS REFERENCE ID NUMBERS 02-03-02-20; 01-01-04.
10. REFERENCES
A) PRIMARY SOURCE
590 U. S. Environmental Protection Agency, FED. Reg., 41 (111), 23085 (1976).
B) BACKGROUND INFORMATION
013 ASTM Standards, Part 26, "Standard Method of Tests for Oxides of Nitrogen in Gaseous Combustion Products (Phenol
Disulfonic Acid Procedure)," 1974, p. 323.
C) FIELD APPLICATIONS
13
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PAGE 1 OF 2 FOR
1. TITLE HIGH PRESSURE GAS SAMPLING TRAIN (GASIFIER OUTPUT SAMPLING)
2. IDENTIFICATION CODE
01-01-01-03
3. ABSTRACT OF METHODOLOGY
The sampling train (Figure 01-01-01-03A) consists of a modified ASTM liquid sampling probe, an impinger for condensing product water and
oils in an ice bath under pressure, followed by pressure reduction and a second impinger series. The second set of impingers is designed
for oxidative scrubbing of the sample to remove acid gases (Impinger No. 1, 3 H H.,0,,), trace metals absorption (Impinger No. 1, as above,
and Impingers No. 2 and 3, consisting of 3 M hydrogen peroxide, 0.2 M (NH4)2 SjOg and 0.02 M silver nitrate), and drying of the sampled
gases (Impinger No. 4, containing Drierite). Gas sampling ports are included to obtain gaseous samples for analysis before and after
trace metals scrubbing. Table 01-01-01-03A lists analyses which can be performed on collected samples.
4. APPLICATION- Engineering evaluation R&D.
A) OPE RAT I ON A L SCOPE
The sampling train is applicable to gasifier output sampling involving temperatures up to and greater than 500°C, pressures up to
and greater than 300 psig for acid gases, mists, and trace metals.
B) INTERFERENCES/LIMITATIONS
The test should be conducted under isokinetic conditions as far as possible, although this parameter is difficult to determine.
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D method for high pressure gas sampling.
5. OPERATIONAL PARAMETERS
A) RANGE Method requires a sampling rate of 2 to 10 m3 of gas over a 1-to 4-hour period, in order to detect 60 yg/m3 of a given
volatile trace element in the gas stream.
B) ACCURACY 10-202; relative error.
C) PRECISION ±10X or better.
6. REAGENTS REQUIRED
Impinger reagents (3 M hydrogen peroxide, 0.2 M hydrogen peroxide,
0.2 M nitric acid, 0.02 M silver nitrate, Drierite drying agent),
ice.
7. EQUIPMENT REQUIRED
ASTM sampling probe, all metal condenser module fabricated from
low carbon steel, standard impinger module; pressure gauges;
sampling vessels; dry test meter; 20-40 meter exhaust hose.
& KEYWORD INDEX: Gas sampling, impingers, ASTM liquid probe.
9. CROSS REFERENCE ID NUMBERS 02-02; 02-03; 02-04.
10. REFERENCES
A) PRIMARY SOURCE
014 ""Group;'™
°f Coal Gasification Processes," TRW
B) BACKGROUND INFORMATION
015 ASTM Committee D-2 and F-7, "Petroleum Products-LPS, Aerospace Materials, Sulfonates, Petrolatum, Wax," 1971 Annual Book of
ASTM Standards, Part 18, D270-65, "Sampling Petroleum and Petroleum Products," American Society for Testing and Materials,
Philadelphia, PA., 1971, p. 47-71.
016 Personal Communication, S. Gasior, U.S. Bureau of Mines to J.W. Hamersma, TRW Systems Group, February 24, 1975.
017 Personal Communication, D. Olsen, IGT-Hygas to O.W. Hamersma, TRW Systems Group, February 24, 1975.
C) FIELD APPLICATIONS
018 Flegal, C.A., M.L. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Technical Manual for Process Measurements: Trace
Inorganic Materials," TRW Systems Group, EPA Contract No. 68-02-1393, July 1975.
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PAGE 2 OF 2 FOR
TITLE HIGH PRESSURE GAS SAMPLING TRAIN (GASIFIER OUTPUT SAMPLING) (CONTINUED) ID NO. 01-01-01-03
Table 01-01-03-03A. Analysis of Gasifier Output (Reference 014).
i
i
Sample
Gases
Organic Liquids
Water
Class
Inorganic gases
Sulfur-containing gases
Organic compounds
Class analysis
Trace elements
Trace elements
Anions
Ammon i a
Analysis or Components
H2, CO, C02, 02, N2
H2S, S02> COS, CS2> inercaptans, thiophenes
CH4, C2Hg, C^H4, C3H6 through higher boil-
ing homologues.
A. Low boiling paraffins, aromatics,
phenols, basic nitrogen compounds,
and organosulfur compounds.
B. High boiling paraffins, and organic
material including PAH, neutral and
basic nitrogen compounds, oxygen, and
sulfur compounds.
Ba, Be, Ca, Cd, Cr, Cu, F", Hg, Mn, Ni ,
Pd, Sb, Se, Sr, Zn
Ba, Be, Ca, Cd, Cr, Cu, F", Hg, Mn, Hi,
Pb, Sb, Se, Sr, Zn.
ClT, Cr, F', S, NOj, 50^
NH,
3
Principal Position In Sampling
Train
First Impinger Series; Gas
Sampling Vessels
First Impinger Series; Gas
Sampling Vessels
First Impinger Series; Gas
Sampling Vessels
First Impinger Series
First Impinger Series
Second Impinger Series
Second Impinger Series
Second Impinger Series
First Impinger Series; Gas
Sampling Vessels
IMPINGER NO. 1
IMPINGER NO. 2
IMPINGER NO. 3
IMPINGER NO. 4
FLOW METER
GAS SAMPLING
PORT
Figure 01-01-01-03A. Suggested Gasifier Sampling Train (Reference 014).
15
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1. TITLE COLLECTION OF MERCURY IN GASEOUS EMISSIONS FROM STATIONARY SOURCES
2. IDENTIFICATION CODE
01-01-01-04
3. ABSTRACT OF METHODOLOGY
Gaseous samples from a stationary source are removed from the gas stream using a heated (121°C or higher depending on stream conditions)
glass probe. The gas is then passed through a heated line to the impinger system (see Figure 01-01-01-04A). Three of the midget
impingers are filled with 15 ml of IC1 and the fourth with silica gel. The IC1 oxidizes any Hg present in the gas stream to Hg ,
effectively scrubbing the Hg vapor. The gas stream is sampled for a minimum of 1.5 hours and 0.1 m . The Hg content of the impingers
is measured by flameless AAS back in the laboratory (see 02-02-01-02).
PROBE
MIDGET IMPINGI
,ERS
DRY GAS METER
ACID ABSORBING TUBE
ICE BATH
VALVE
PUMP
/ ' ' £T~O.
ROTAMETER
Figure 01-01-01-04A. Hg Sampling Train.
4. APPLICATION^ Compliance, engineering evaluation R&D.
A) OPERATIONAL SCOPE
This method is applicable for the determination of mercury gaseous emissions from stationary sources. These test procedures are
primarily used for determining compliance with clean air acts.
B) INTERFERENCES/LIMITATIONS
IC1 has a large molecular background and can interfere with the AAS analysis. Method cannot be used in presence of easily
oxidized background, e.g., SOj.
C) RECOMMENDED USE AREA
Compliance Testing.
5. OPERATIONAL PARAMETERS
Al RANGE 0.1 ppm mercury can be found in the impingers.
B) ACCURACY N/Q (±10%).
C) PRECISION N/Q (±10%).
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Potassium iodide, hydrochloric acid, potassium iodate,
distilled water, iodine chloride, nitric acid, sodium
hydroxide, zero grade air, mercuric chloride.
Sampling train (see Figure 01-01-01-04) barometer, anemometer,
thermometer, laboratory glassware.
& KEYWORD INDEX^ Sampling, mercury sampling, compliance testing.
9. CROSS REFERENCE ID NUMBERS 02-02-01-02.
10. REFERENCES
A) PRIMARY SOURCE
019 Federal Register, Vol. 36, No. 234, p. 23248, 1971.
B) BACKGROUND INFORMATION
020 Martin, R.M., "Construction Details of Isokinetic Source Sampling Equipment," Environmental Protection Aqencv, APT-0581
021 Smith, W.S., et al, "Stack Gas Sampling Improved and Simplified with New Equipment," APCA paper No. fi7-119, 1967.
022 Hatch, W.R., and W.L. Ott, "Determination of Submicrogram Quantities of Mercury by Atomic Absorption Spectrophotometrv "
Anal. Chem., 40, 2085 (1968). ' V>
023 Rome, J.J., "Maintenance Calibration and Operation of Isokinetic Source Sampling Equipment," EPA, APTD E-05-76.
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Book of ASTM Standards, Part 23, 02928-71, "Standard
Method for Sampling Stacks for Particulate Matter," American Society for Testing and Materials, Philadelphia, PA., I97i_
Ci FIELD APPLICATIONS
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1. TITLE SAMPLING VAPOROUS TRACE ELEMENTS IN FLUE GAS
2. IDENTIFICATION CODE
01-01-01-05
1 ABSTRACT OF METHODOLOGY
A system of four impingers commonly found In a Method 5 train is filled with 3H H202 in the first inoinqer, 0.2 M (NH.)2 5,0-
plus 0.02 M AgNO, in the next two impingers, and Drierite in the last impinger. For the most accurate results, the Trace
Material Sampling Train (01-04-01-01) is recommended.
The 3M H.O- passes Hg vapor but removes the S02 to prevent depletion of the Ag catalyzed (NH^),, SjOg solution. The oersulfate
solution is specifically designed to remove Hg, but will collect any Se, Sb, As or Pb that passes through the peroxideimpinger.
In all cases, the volatile species are oxidized in the H^O., or (NH^),, S,,0g and are effectively scrubbed from the gas stream.
4. APPLICATION: Engineering evaluation RRD.
A) OPE RATION A L SCOPE
This oxidative system was designed to operate in the modified Aerotherm HVSS, but can be used in any commercially available system
employing glass or plastic impingers. The system is 100% efficient for Hg scrubbing at flowrates up to 5 cfm.
B) INTERFERENCES/LIMITATIONS
(NH.)2 SoOj, is not stable in solution, so the solution must be made up just prior to use. Because of its strong oxidative nature,
metal parts in contact with the solution will contaminate the sample with Ni, Cr, and Fe. Glass or plastic impingers are
recommended.
C) RECOMMENDED USE AREA
Engineering evaluation of the gas streams for volatile trace metals.
5. OPERATIONAL PARAMETERS
A) RANGE Designed to sample trace quantities of Hg, Se, Sb, As and Pb in flue gas.
B) ACCURACY System is 100* effective for Hg removal up to 5 cfm.
C) PRECISION (tlO* estimated)
6. REAGENTS REQUIRED
(NH4)2 S20g, H202, high purity H20.
7. EQUIPMENT REQUIRED
Glass or plastic impingers
(see 01-04-01-01).
(Greenberg-Smith) , pump, flowmeter
KEYWORD INDEX-' Sampling, vapors, Hg, Se, Sb, As, Pb.
9. CROSS REFERENCE ID NUMBERS 01-04-01-01; 02-01-03-03.
10. REFERENCES
A) PRIMARY SOURCE
018 Flegal, C.A., M.L. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Procedures for Process Measurements of Trace
Inorganic Materials," TRW Systems Group, EPA Contract No. 68-02-1393, July 1975.
B) BACKGROUND INFORMATION
C) FIELD APPLICATIONS
025 Flegal, C.A., M.L. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Final Report for Measurements Techniques for
Inorganic Trace Materials in Control System Streams," TRW Defense and Space Systems, EPA Contract Number 68-02-1393, in press.
17
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DETERMINATION OF SULFURIC ACID MIST AND SULFUR DIOXIDE EMISSIONS FROM
1. TITLE STATIONARY SOURCES
2. IDENTIFICATION CODE
01-01-O1-06
3. ABSTRACT OF METHODOLOGY
A gas sample is removed from a sampling point in the stack and collected in a series of impingers, as shown in Figure 01-01-01-06A.
The sulfuric acid mist, including S03> is collected both in the first impinger containing 8Q% isopropanol, and on the filter. The
SO, is collected in the second and third impingers, which contain 3% hydrogen peroxide solution. The four impingers are Greenburg-Smith
impingers. The first and third impingers have standard tips; the second and fourth impingers are modified by replacing the standard
tip with a 1/2-inch ID glass tube extending to one-half inch from the bottom of the impinger flask. Analysis on the sampled gases are
performed using the barium-thorin titration method (see 02-03-02-05).
Figure 01-01-01-06A. Sulfuric Acid Mist Sampling Train
4. APPLICATION'- Compliance.
A) OPERATIONAL SCOPE
Method is applicable to determination of sulfuric acid mist (including SOj) and SO, from stationary sources when specified by test
procedures for new source performance standards.
B) INTERFERENCES/LIMITATIONS
SOj may be trapped in the isopropyl alcohol solution, causing low results. The alcohol solution should be purged with nitrogen
into the hydrogen peroxide impingers to remove any S02 trapped in the IPA. At recommended temperatures H2S04 will condense in
the probe and tubing leading to the first impinger.
C) RECOMMENDED USE AREA
5. OPERATIONAL PARAMETERS
A) RANGE N/Q
B) ACCURACY N/A
C) PRECISION N/A
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Glass fiber filters, silica gel, 80% isopropanol, 3% hydrogen
peroxide, crushed ice.
Sampling probe, nozzle, pitot tube, filter holder, metering
system, barometer, impingers, standard laboratory glassware.
& KEYWORD INDEX: Flue gas sampling, sulfuric acid mist, sulfur dioxide, compliance.
9. CROSS REFERENCE ID NUMBERS 01-01-01-01; 02-03-02-05.
10. REFERENCES
A) PRIMARY SOURCE
006
"'
*** '""
D''°Xide Qrissions f™ Stationary Sources,"
B) BACKGROUND INFORMATION
007 U.S. DHEW, PHS Division of Air Polution, "Atmospheric Emissions from Sulfuric Arid Mannfart „• »
PHS Publication NO. 999-AP-13, Cincinnati, Ohio, 1965 suiwic Acid Manufacturing Processes,"
008 Patton, W.F., and
565
, Jr., "New Equipment and Techniques for Sampling Chemical Process Gases,"
*"" *"" Dete™inat1on of H2S04 M1st ™* ™2 Emissions from Stationary Sources,"
Cl FIELD APPLICATIONS
009 Corbett, D.F., "The Determination of S02 and S03 in Flue Gasses," J. Inst. Fuel. 24, W7-243 (1961)
482 Rom, J.J., "Maintenance, Calibration, and Operation of Isokinetic Source SamplinaTauiompnt " Fm,i..n™,=n»>i „
Agency, Air Pollution Control Office Publication No. APTD-0576. «'"M'ing Equipment, Environmental Protection
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1. TITLE DETERMINATION OF HYDROGEN SULFIDE EMISSIONS FROM STATIONARY SOURCES
2. IDENTIFICATION CODE
01-01-01-07
1 ABSTRACT OF METHODOLOGY
A sample of gas is removed from the gas stream and hydrogen sulfide is collected in a series of midget impingers containing alkaline
cadmium hydroxide (see Figure 01-01-01-07A). The cadmium sulfide which precipitates is then dissolved in hydrochloric acid solution
and absorbed in iodine, then is titrated with standard thiosulfate solution (see 02-03-02-17).
TEFLON SAMPLING LINE (HEATED)
MIDGET IMPINGERS
SILICA CEl TUBE
DRY GAS METER
RATE METER'
Figure 01-01-01-07A. Field Data
PUMP (NOT REQUIRED
IF LINES PRESSURIZED)
4. APPLICATION: Compliance.
A) OPERATIONAL SCOPE
Method is applicable to measurement of rS to determine compliance with New Source Performance Standards.
B) INTERFERENCES/LIMITATIONS
The analysis titration should be conducted at the sampling location in order to prevent iodine loss from the sample. The sample
should not be exposed to direct sunlight during titration.
C) RECOMMENDED USE AREA
OPERATIONAL PARAMETERS
A) RANGE N/Q
B) ACCURACY N/Q
C) PRECISION N/Q
6. REAGENTS REQUIRED
Cadmium sulfate hydrate, sodium hydroxide, 3% hydrogen
peroxide, hydrochloric acid solution, ice.
a KEYWORD INDEX: Flue gas sampling, H2S, compliance, sampling.
7. EQUIPMENT REQUIRED
Sampling probe, impingers, silica gel drying tube, standard
laboratory glassware.
9. CROSS REFERENCE ID NUMBERS 02-03-02-17; 01-02-01; 01-02-02
10. REFERENCES
AI PRIMARY SOURCE
481 U.S. Environmental Protection Agency, "Determination of Hydrogen Sulfide Emissions from Stationary Sources," Title 40,
Part 60, Chapter 1, Appendix A, Washington, O.C., 1971, p. 792.
B) BACKGROUND INFORMATION „, r, . „ , ,
483 "Determination of Hydrogen Sulfide, Aiimoniacal Cadmium Chloride Method," API Method 772-54, in Manual on Disposal
of Refinery Wastes," Volume 5, American Petroleum Institute, Washington, B.C., 1954.
484 "Tentative Method for Determination of Hydrogen Sulfide and Mercaptan Sulfur in Natural Gas," Natural Gas Processors
Association, Tulsa, Oklahoma, NGPA Publication No. 2265-65, 1965.
C) FIELD APPLICATIONS
19
-------
1. TITLE SAMPLE AND VELOCITY TRAVERSES FOR STATIONARY SOURCES
PAGE 1 OF 3 FOR
•••••^•^^•^••^^^•••^^^^M
2. IDENTIFICATION CODE
01-01-01-08
3. ABSTRACT OF METHODOLOGY
Method Involves the measurement of the distance from the chosen sampling location to the nearest upstream and downstream disturbances.
The sampling site should be at least eight stack- or duct-diameters downstream and two diameters upstream from any flow disturbance
such as a bend, expansion, contraction, or flame. The minimum number of traverse points is then 12. The equivalent diameter of a
rectangular cross section is determined using Equation (1):
equivalent diameter 2
'(length) (width) \
length + width I
(1)
When the above criteria cannot be met, the number of sampling points for each distance is selected from Figure 01-01-01-08A. Next,
the cross-sectional layout and location of traverse points are determined. Traverse points for circular stacks are located using
Figure 01-01-01-08B and Table 01-01-01-08A. Traverse points for rectangular stacks are located using Figure 01-01-01-08C.
4. APPLICATION'- Compliance.
A) OPERATIONAL SCOPE
Method is applicable to the measurement of gas streams emitted to the atmosphere without further processing, to determine
compliance with New Source Performance Standards.
B) INTERFERENCES/LIMITATIONS
N/Q
C) RECOMMENDED USE AREA
This is the compliance method for the positioning of velocity and sampling traverses.
5. OPERATIONAL PARAMETERS
A) RANGE Method can be used to sample all gaseous streams.
B) ACCURACY N/Q
C| PRECISION N/Q
6. REAGENTS REQUIRED
None.
7. EQUIPMENT REQUIRED
Linear measurement equipment.
8. KEYWORD INDEX: Sample traverse, velocity traverse, flue gas, compliance.
9. CROSS REFERENCE ID NUMBERS 02-02; 02-03; 01-01-01-09
10. REFERENCES
A) PRIMARY SOURCE
481 U.S. Environmental Protection Agency, "Sample and Velocity Traverse for Stationary Sources," Title 40, Part 60, Chapter 1,
B) BACKGROUND INFORMATION
485
486
487
024
tunuunu mrimMA i IUIN
"Determining Dust Concentration in a Gas Stream," ASME Performance Test Code #27, New York N Y 1957
Devorkin, H., et al, "Air Pollution Source Testing Manual," Air Pollution Control District', Los'tageles, California
Nov. 1963. ' "
"Methods for Determination of Velocity, Volume, Dust and Mist Content of Gases," Western Precioitation nii/ici™ «r i
Manufacturing Co., Los Angeles California, Bulletin WP-50, 1968. precipitation Division of Joy
ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards Part 23 02928 71
"Standard Method for Sampling Stacks for Particulate Matter," American Society for Testing and Materials! Philadelphia PA
C) FIELD APPLICATIONS
20
-------
PAGE 2 OF 3 FOR
TITLE SAMPLE AND VELOCITY TRAVERSES FOR STATIONARY SOURCES (CONTINUED)
10 NO. 01-01-01.08
50
40
30
20
i 10
0.5
NUMBER OF DUCT DIAMETERS UPSTREAM
(DISTANCE A)
I.O 1.5 2.0
I
I
I
T
T
*FROM POINT OF ANY TYPE OF
DISTURBANCE (BEND, EXPANSION, CONTRACTION, ETC.)
2.5
A
f
3
1
-
t
i
7 DISTURBANCE
SAMPLING
r SITE
^DISTURBANCE
NUMBER OF DUCT DIAMETERS DOWNSTREAM
(DISTANCE B)
Figure 01-01-01-08A. Minimum Number of Traverse Points
Figure 01-01-01-08B. Cross Section of Circular Stack Divided
into 12 Equal Areas, Showing Location
of Traverse Points at Centroid of each
Area
O
0
o
o
r
o
o
o
!..-_
O
o
o
o
o
Figure 01-01-01-08C. Cross Section of Rectangular Stack
Divided into 12 Equal Areas, with
Traverse Points at Centroid of Each
Area
21
-------
PAGE 3 OF 3 FOR
TITLE SAMPLE AND VELOCITY TRAVERSES FOR STATIONARY SOURCES (CONTINUED)
ID NO. 01-01-01-08
Traverse
point
number
on a
di ameter
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
FIGURE 01-01-01-08C.
LOCATION OF TRAVERSE POINTS IN CIRCULAR STACKS
(Percent of stack diameter from inside wall to traverse point)
Number of traverse points on a diameter
14.6
35.4
6.7
25.0
75.0
93.3
4.4
14.7
29.5
70.5
85.3
95.6
3.3
10.5
19.4
32.3
67.7
80.6
89.5
96.7
10
2.5
8.2
14.6
22.6
34.2
65.8
77.4
85.4
91.8
97.5
12
2.1
6.7
11.8
17.7
25.0
35.5
64.5
75.0
82.3
88.2
93.3
97.9
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
4.4
7.5
10.9
14.6
18.8
23.6
29.6
38.2
61.8
70.4
76.4
81.2
85.4
89.1
92.5
95.6
98.6
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
92.3
95.1
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
63.5
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
22
-------
PAGE 1 OF 2 FOR
1. TITLE STACK GAS VELOCITY AND VOLUMETRIC FLOW RATE (TYPE S PITOT TUBE)
2. IDENTIFICATION CODE
01-01-014)9
3. ABSTRACT OF METHODOLOGY
Method involves determination of stack gas velocity using gas density and velocity head measurement using a Type S (Stauscheibe or
reverse type) pitot tube. Figure 01-01-01-09 shows the pitot tube-monometer assembly. The stack veloci y h La d el e
measured at traverse points specified in 01-01-OL08. Next, static pressure is measured. Finally, stack ^1 1 ' ,
deterged by gas analysis and calculations (see Method 02-03-01-01). Excess air is calculated using Equation 1-
(% 02) - 0.5(% CO)
0.264(!S N2) - (% 02) + 0.5(X CO) x
and dry molecular weight is calculated using Equation 2:
Mo - 0.44(5! C02) + 0.32U 02) + 0.28(2 N2 + % CO)
(1)
(2)
4. APPLICATION: Compliance
A) OPERATIONAL SCOPE
Method is applicable to the measurement of stack gas streams to determine compliance with new Source Performance Standards.
B) INTERFERENCES/LIMITATIONS
S-pitot tubes are very susceptible to misalignment in the gas flow for accurate measurements, be sure to align s-pitot parallel
to gas flow.
C) RECOMMENDED USE AREA
This is the compliance method for performing velocity traverses.
& OPERATIONAL PARAMETERS
A) RANGE Method can be used to measure all gaseous streams.
B) ACCURACY N/Q
C) PRECISION N/Q
6. REAGENTS REQUIRED
None.
7. EQUIPMENT REQUIRED
Pitot tube - Type S, differential pressure gauge,
gauge, pressure gauge, barometer, gas analyzer.
temperature
& KEYWORD INDEX: stack gas velocity, volumetric flow rate, compliance
9. CROSS REFERENCE ID NUMBERS 02-02; 02-03; 01-01-01-08
10. REFERENCES
481 U.S. Environmental Protection Agency, "Determination of Stack Gas Velocity and Volumetric Flow Rate (Type S Pitot Tube),"
Title 40, Part 60, Chapter 1, Appendix A, Washington, D. C., 1971, p. 763.
B) BACKGROUND INFORMATION
488 Mark, L.S., "Mechanical Engineers' Handbook," McGraw-Hill Book Co., Inc., New York, N.Y., 1951.
489 Perry, J.H., "Chemical Engineers' Handbook," McGraw-Hill Book Co., Inc., New York, N.Y , 1960.
490 Shigihara, R.T., W.S. Smith, and W.F. Todd, "Significance of Errors in Stack Sampling Measurements, paper presented at the
annual meeting of the Air Pollution Control Association, St. Louis, MO., June 14-19, 1970.
491 Vennard, J.K., "Elementary Fluid Mechanics," John Wiley and Sons, Inc., New York, N.Y., 1947.
C) FIELD APPLICATIONS
23
-------
TITLE
STACK GAS VELOCITY AND VOLUMETRIC FLOW RATE
(TYPE S PITOT TUBE) (CONTINUED)
PAGE 2 OF 2 FOR
ID NO. 01-01-01-09
PIPE COUPLING.
/TUBING ADAPTER
MANOMETER
Figure 01-01-01-09. Pitot Tubemanometer Assembly
2'!
-------
PAGE 1 OF 3 FOR
1. TITLE SAMPLING FLUE GASES USING DIRECT READING GAS DETECTION TUBES
2. IDENTIFICATION CODE
01-01-02-01
3. ABSTRACT OF METHODOLOGY
Gas detection tubes are based on the principle that if a known volume of gas containing a species of interest is pulled through a tube
that contains a solid adsorbent impregnated with an indicating reagent, that the length of the stain on the indicating gel will be pro-
portional to the amount of gas species in the sampled air. The use of detecting tubes is extremely simple. After their two sealed ends
are broken open, the glass tubes are placed in the manufacturer's holder which is fitted with a calibrated squeeze bulb or piston pump.
The recommended air volume is then drawn through the tube by the operator. When sampling hot gases, such as from a furnace stack or an
exhaust, cooling of the sample gas is essential, otherwise the calibration would be inaccurate and the volume of gas sampled uncertain. A
probe of glass or metal may be attached to the inlet end of the detector tube with a short piece of flexible tubing. If this tube is
cold initially, a length of as little as 10.2 cm (4 inches) outside of the furnace is sufficient to cool the gas sample from 250°C to
about 30°C. Note: One must be careful in employing this type of probe since in some cases serious adsorption (for example SO,,) errors
can occur either on the tube or in condensed moisture.
4. APPLICATION^ Environmental assessment.
A) OPERATIONAL SCOPE
By using a probe to cool the gas prior to sampling with the detection tube, the temperature range under which the detection tube
can be used can be extended to as high as 572°C. Since precleansing layers are present in the detection tube, the interferences to
the specific measurement are minimized. These tubes can be used to sample most flue gases as long as the pressure in the stack is
close to ambient. Instructions are provided with the tube to correct for temperature and pressure changes.
B) INTERFERENCES/LIMITATIONS
Even with the precleansing layers there are interferences to the gases being measured (see Table 01-01-02-01A). One must always
be aware of possibility of spurious results because of these interferences. Experience in sampling a known concentration is of
great value in training the operator to know whether to measure the length of the beginning or end of the stained front or what
portion of the original shaped stain to use as the limit. Care must be taken to see that the pump valves and connections are leak-
proof. The color in the indicating tube can fade with time, so the measurement of the stain length should be accomplished as
soon as possible. If the tube is to be kept as evidence, then both ends should be sealed with wax.
C) RECOMMENDED USE AREA
Level 1 environmental assessment.
5. OPERATIONAL PARAMETERS See Table 01-01-02-01A.
A) RANGE N/Q
B) ACCURACY The tube reading deviates from the true value by ±25% at most. For many tubes, the deviation is less than ±102!.
C) PRECISION Precision will primarily depend upon the technique of the operator in measuring the length of the stain.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Detector tubes can be obtained from several sources. (National
Mines Service Co., Pittsburgh, Pa., and Unico Environmental
Instruments, Fall River, Mass.)
A gas detection kit normally includes detection tubes of interest
and necessary pumps and attachments needed to perform the test.
a KEYWORD INDEX: Sampling, detection tubes.
9. CROSS REFERENCE ID NUMBERS 01-01-02-01.
10. REFERENCES
A) PRIMARY SOURCE
026 American Conference of Governmental Industrial Hygienists, "Air Sampling Instruments," ACGIH, Cincinnati, Ohio, 4th ed.,
1972, p. S-l to S-50.
B) BACKGROUND INFORMATION
See Table 01-01-02-01B.
C) FIELD APPLICATIONS
See Table 01-01-02-01C.
25
-------
PAGE 2 OF 3 FOR
TITLE SAMPLING FLUE GASES USING DIRECT READING GAS DETECTION
TUBES (CONTINUED)
ID NO. 01-01-02-01
Table 01-01-02-01A. UNICO (KITAGAMA) Gas Detector Tubes (Reference 026).
Detector Tube
Ammonia-high range
Ammonia— low range
Arsine
Bromine
Carbon Dioxide-high
range
Carbon Dioxide-low
range
Carbon Disulfide
Carbon Monoxide
Carbon Monoxide— in the
the presence of
ethyl ene
Carbon Monoxide- in the
presence of hydro-
carbons and nitrous
gases
Carbon Tetrachloride
Chlorine
Chlorine Dioxide
Hydrogen Cyanide-high
range
Hydrogen Cyanide— low
range
Hydrogen Selenide
Hydrogen Sul fide-high
range
Hydrogen Sul fide— low
range
Hydrogen Sul fide— in the
presence of sulfur
dioxide
Hydrogen Sul fide
Mercury (inorganic)
Methyl Mercaptan
Nickel Carbonyl
Nitrogen Dioxide
Oxygen
Phosgene
Measurable
Concentration
1-25%
20-700 PPM
5-160 PPM
10-300 PPM
0.1-2.6%
300-7,000 PPM
10-200 PPM
25-6,000 PPM
25-6,000 PPM
25-6,000 PPM
5-300 PPM
1-40 PPM
10-500 PPM
0.01-3.0%
10-100 PPM
1-600 PPM
0.01-0.17%
5-160 PPM
0.005-0.16%
1000-3000 PPM
0.1-2.0 mg/m3
1-20 PPM
5-120 PPM
20-700 PPM
1-1,000 PPM
2-30%
5-50 PPM
T.L.V.
0.005%
50 PPM
0.05 PPM
0.1 PPM
0.5%
5,000 PPM
20 PPM
50 PPM
50 PPM
50 PPM
10 PPM
**
1 PPM
0.1 PPM
0.00 IX
10 PPM
0.05 PPM
0.001%
10 PPM
0.001X
10 PPM
0.1 mg/m3
10 PPM
0.001 PPM
5 PPM
0.1 PPM**
Lower
Explosive
Limit
15%
160,000 PPM
-
-
-
-
12,500 PPM
125,000 PPM
125,000 PPM
125,000 PPM
-
-
-
6%
-
-
4.3%
43,000 PPM
4.3%
-
_
-
-
-
Shelf
Life
unlimited
1 yeart
3 years
1 yeart
3 years
3 years
1 yeart
3 years
3 years
1 yeart
6 monthst
1 yeart
1 yeart
1 yeart
1 yeart
1 yeart
3 years
1 yeart
3 years
3 years
1 yeart
1 yeart
6 mos.t
1 yeart
1 yeart
1 yeart
Discoloring of Reagent
Original Change
pink
pink
white
white
blue
purple
blue
purple
blue
purple
pale
yel 1 ow
pale
yel 1 ow
pale
yell ow
yellow
white
white
yellow
yel 1 ow
pale
yellow
white
white
pale
yellow
white
yellowish
gray
white
pale
yellow
grayish
white
white
white
purplish
blue
pale yellow
brownish
black
greenish
orange
pale pink
pale pink
white
green and
blue
green and
blue
green and
blue
blue
pale
orange
orange
reddish
brown
red
dark
brown
black
brown
blackish
blue
black
pale
orange
orange
blackish
purple
pale
orange
brown
reddish
brown
Interferences
Hydrogen sulfide
Amines
Hydrogen sulfide, phosphine
Chlorine, iodine, nitrogen
dioxide
Acid gases at high
concentration
Acid gases at high
concentration
Hydrogen sulfide above
50 PPM, sulfur dioxide
above 150 PPM
Hydrocarbons, hydrogen
sulfide, nitrogen dioxide,
ammonia
Nitrogen dioxide
none
Phosgene
Other halogens, ozone,
nitrous gases, bromine,
iodine
Chlorine, ozone, nitrous
gases, iodine
Cyanogen, hydrogen
sulfide, sulfur dioxide
Hydrogen chloride,
sulfur dioxide
Arsine, hydrogen sulfide
Sulfur dioxide
Sulfur dioxide
Hydrocarbons , carbon
monoxide, nitrous gases,
hydrogen cyanide
Sulfur dioxide
Chlorine, hydrogen sulfide
Methyl sulfide, chlorine,
acetylene, nitrogen dioxide,
carbon monoxide, ethylene,
ethyl mercaptan
Hydrogen sulfide,
sulfur dioxide
Chlorine, ozone, iodine,
bromine, chlorine dioxide
none
Chlorine, nitrogen dioxide,
hydrogen chloride
Tentative - 1967 Revision tAll short shelf life tubes can be extended by refrigeration.
26
-------
PAGE 3 OF 3 FOR
TITLE
GASES USING DIRECT READING GAS DETECTION
ID NO. 01-01-02-01
Table 01-01-02-01A.UNICO (KITAGAWA) Gas Detector Tubes (Continued)
Detector Tube
Measurable
Concentration
T.L.V.
Lower
Explosive I Shelf
Limit I Life
Discoloring of Reagent
Original Change
Interferences
Phosphine-high range
20-800 PPM
0.3 PPM
| unlimited pale blue reddish
purple
Hydrogen sulfide
Phosphine-low range
5-90 PPM
0.3 PPM
' unlimited
pale blue yellowish
brown
Hydrogen sulfide
Sulfur Dioxide-tiigh
range
0.1-0.4?,
unlimited
yellow
light blue
Hydrogen sulfide
Sulfur Dioxide-middle
range
0.02-0.3'f.
o.ooos:;
3 years
wh i te
orange
Hydrogen sulfide
Sulfur Dioxide—low
range
5-300 PPM
5 PPM
1 yeart
I
blue
purple
white
Hydrogen sulfide
Sulfur Dioxide-0 type
1-80 PPM
5 PPM
1 yeart
bl ue
purple
whi te
Hydrogen sulfide,
nitrogen dioxide
Sulfur Dioxide-
determinations in
flue gases
0.02-0.30*
5 PPM
3 years
white
orange
tAll short shelf life tubes can be extended by refrigeration.
Table 01-01-02-Q1B Background Information
027 Kitagawa, Tetsuzo, "Rapid Analysis of Phosphine and
Hydrogen Sulfide in Acetylene," J. Japan Chem. Ind. Soc.,
No. 33, (Feb. 1951).
028 Hubbard, B.R., and L. Silverman, Arch. Ind. Hyg. and
Oce. Med., 2_, 49 (1950).
029 Grosskopf, Karl, Agnew, Chem., 53_, 306 (1951).
030 Grosskopf, Karl, "Detector Tubes as Detectors in Gas
Chromatography," (German) Erdohl und Kohle, 11,
304-6 (1958). '
031 Ingram, W.T., "Personal Air-Pollution Monitoring
Devices," Am. Ind. Hyg. Assoc. J., 25_, 298-303 (1964).
032 Kinosian, J.R., and B.R. Hubbard, "Nitrogen Dioxide
Indicator," Amer. Ind. Hyg. Assoc. J.. 19. 453 (1958).
033 Kitagawa, Tetsuzo, "Rapid Method of Quantitative Gas-
Analysis by Means of Detector Tubes," Kagaku no
Ruoiki, j6_, 386 (1952).
034 Sacks, Volkmar, "Carbon Monoxide Detection by
Means of the Colorimetric Gas Analyzer," (German)
Deutsche Zeitschrift Fur Gerichtliche Medizin, 45_,
68-71 (1956).
035 Silverman, Leslie, and G.R. Gardner, "Potassium
Pall ado Sulfite Method for Carbon Monoxide Detection,"
Am. Ind. Hyg. Assoc. J.. 26, 97-105 (1965).
036 Kusnetz, H.L., "Air Flow Calibration of Direct Reading
Colorimetric Gas Detecting Devices," Amer. Ind. Hyg.
Assoc. J.. 21. 340-1 (1960).
037 Saltzman, Bernard E., "Basic Theory of Gas Indicator
Tube Calibrations," Am. Ind. Hyg. Assoc. J., 23,
112-26 (1962).
038 Scherberger, R.F., D.W. Fassett, G.P. Hapo and
F.A. Miller, "A Dynamic Apparatus for Preparing
Air-Vapor Mixtures of Known Concentrations," Am.
Ind. Hyg. Assoc. J., 19., 494-8 (1958).
039 Saltzman, Bernard E., "Preparation and Analysis of
Calibrated Low Concentrations of Sixteen Toxic
Gases," Anal. Chem., 33, 1100-12 (1961).
040 Cotabish, H.N., P.M. McConnaughey and H.C. Messer,
"Making Known Concentrations for Instrument Calibration,"
Am. Ind. Hyq. Assoc. J., 22, 392-402 (1961).
041 Hersch, P.A., "Controlled Addition of Experimental Pollu-
tants to Air," J. Air Poll. Control Assoc., 19, 164-72
(1969).
042 Kusnetz, H.L., M.E. Lanier and B.E. Saltzman,
"Calibration and Evaluation of Gas Detecting Tubes,"
Am. Ind. Hyq. Assoc. J.. 21, 361-73 (1960).
Table 01-01-02-01C Field Applications
043 Ketcham, N.H., "Practical Experiences with Routine Use of
Field Indicators," Am. Ind. Hyg. Assoc. J.. 23, 127-31 (1962).
044 Kitagawa, Tetsuzo, "Detection of Underground Spontaneous
Combustion in Its Early Stage With Detector," Tenth
International Conference of Directors of Safety in Mines
Research, Pittsburgh, Pennsylvania, 1959.
045 Kitagawa, Tetsuzo, "The Rapid Measurement of Toxic Gases
and Vapors," The 13th International Congress on Occupational
Health, New York, N.Y., July 25-9, 1960.
046 Silverman, L., "Panel Discussion of Field Indicators in
Industrial Hygiene," Am. Ind. Hyg. Assoc. J., 23_, 108-11
(1962).
047 Silverman, Leslie, "Techniques to Improve the Accuracy of
Detector Tubes," Am. Ind. Hyg. Assoc., Cincinnati, Ohio,
May 1963.
048 Banks, O.H., and D.R. Nelson, "Evaluation of Commercial
Detector Tubes," presented at 22nd Annual Meeting, Am. Ind.
Hyg. Assoc.. Detroit, Michigan, April 13, 1961.
049 Hay III, E.B., "Exposure to Aromatic Hydrocarbons in a Coke
Oven By-Product Plant," Am. Ind. Hyg. Assoc. J.. 25_, 386-91
(1964).
050 LaNier, M.B., and H.L. Kusnetz, "Practices in the Field Use
of Detector Tubes," Arch. Environmental Health. 6_, 418-21 (1963).
051 Kitagawa, Tetsuzo, "Detector Tube Method for Rapid Determina-
tion of Minute Amounts of Nitrogen Dioxide in the Atmosphere,"
Yokohama National Univ. (July 1965).
27
-------
PAGE 1 OF 2 FOR
1. TITLE S02 ADSORPTION ON SOLIDS (SILICA GEL)
2. IDENTIFICATION CODE
01-01-02-02
3. ABSTRACT OF METHODOLOGY
Figure 01-01-02-02A shows a typical sampling apparatus for S0? adsorption. The tube is placed in an appropriate sample port. A
known volume of flue gas is drawn through the tube using an evacuated cylinder of known volume or a metered pump. The adsorbed
SO. is desorbed at 500°C, then reduced in a hydrogen stream to H.,S, which is then determined spectrophotometrically as molybdenum
blue. A typical desorption apparatus consists of a hydrogen source (steel cylinder and laboratory gas meter), a furnace, a quartz
contact tube (26 cm x 8 mm I.D.) containing 3 x 6 cm2 platinum wire grid of 3600 mesh/cm2, connected to a reagent scrubber containing
5 ml reagent solution. Desorption consists in heating the silica gel tube in the presence of the hydrogen gas to 500°C; the desorbed
gas is then passed over the platinum catalyst and heated in the presence of hydrogen to 600°C by the contact burner. The H2S which
is formed is then allowed to pass through a tube containing 5 ml of reacient solution (see Section 6 below for reagent composition).
The resulting solution is analyzed spectrophotoraetrically, as indicated above.
Other general methods for desorbing gases and vapors from silica gel include blowing with contaminant-free air at temperatures up to
350°C, extraction with polar solvents such as water or alcohols, and distillation with saturated steam at ambient pressures
(see 01-05-02-04).
Silica gel can also be used as an adsorbent for HjS, NH3 and AsH3, if impregnated with suitable reagents prior to sampling. Impregnants
include solutions of lead acetate or silver cyanide for hydrogen sulfide, sulfuric acid for NHj, and copper and silver oxidation
catalysts for arsine.
4. APPLICATION: Environmental assessment, engineering evaluation R&D
A) OPERATIONAL SCOPE
The method is applicable to sampling most flue gas streams containing SO,, involving temperatures of 200 C, and pressures of
1 atmosphere.
B) INTERFERENCES/LIMITATIONS
Trace sulfur-containing contaminants must be removed from the silica prior to use as an adsorbent by heating several hours in
nitric acid in a water bath under a reflux condenser.
C) RECOMMENDED USE AREA
This is the recommended level 1 environmental assessment method for sampling flue gases containing SO..
5. OPERATIONAL PARAMETERS
A) RANGE Sampling rate of 2 to 10 m3 of stack gas over period of 1 to 4 hours (See 01-01-01-04) is possible. The range sensi-
tivity of the method can be increased by impregnation with suitable solutions, as described above
B) ACCURACY 10% or better.
C) PRECISION +10* or better.
6. REAGENTS REQUIRED
Purified silica gel; reagent solution, consisting of 2 volumes of A + 3
volumes of B (A = 0.5g urea in 1000 ml 1 N HjSO^; B 33. 3g ammonium
lolybdate in 1000 ml water); solutions for impregnating silica gel
lead acetate, silver cyanide, sulfuric acid).
7. EQUIPMENT REQUIRED
Adsorption tube; desorption apparatus including quartz contact tube
(length, 26 cm; 8 mm I.D.) containing tightly coiled 3 x 6 cm2
platinum wire grid of 3600 mesh/cm2; furnace, steel cylinder of
hydrogen and laboratory gas meter.
KEYWORD INDEX: Adsorption on solids, S02, silica gel, desorption.
9. CROSS REFERENCE ID NUMBERS 01-05-02-04, 01-05-04-01; 01-01-04-01, 01-01-02-03; 02-03-01; 01-01-01-04.
10. REFERENCES
A) PRIMARY SOURCE
052 Leithe, W., "The Analysis of Air Pollution," London, Ann Arbor-Humphrey Science Publishers, 1970, p. 158-60.
B) BACKGROUND INFORMATION
026
C) FIELD APPLICATIONS
28
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PAGE 2 OF 2 FOR
TITLE SO2 ADSORPTION ON SOLIDS (SILICA GEL) (CONTINUED)
ID NO. 01-01-02-02
Figure 01-01-02-02A. Evacuated Grab Sampling Apparatus (3 liters).
29
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SULFUR OXIDES IN FLUE GAS BY CONTROLLED CONDENSATION
1. TITLE (QOKSOYR-ROSS METHOD) __
2. IDENTIFICATION CODE
01-01-03-01
3. ABSTRACT OF METHODOLOGY
Using a borosilicate glass probe of suitable length, gas samples are removed from the stack. Particulates are removed from the gas stream
by a quartz wool plug placed at the end of the heated (250°C) probe. The sulfur trioxide is condensed as sulfuric acid by controlled
cooling of the flue gas as it passes through a water jacketed (62°C) condenser. The resulting sulfuric acid aerosol is collected on a
filter which is maintained above the water dewpoint by the water jacket to prevent SO,, from being washed out of the gas stream. Sulfur
dioxide is collected in midget impingers in a series with the SO,, collector and oxidized to sulfuric acid by aqueous 3 percent hydrogen
peroxide solution. The sulfate concentration of each solution is then determined separately (see 02-03-02-03 for details of a sulfate
procedure recommended for this sampling method).
THERMOCOUPLE
WELL
60 MM MEDIUM
FRIT
7 MM O.D. COILS 28/15
•4.0 CM-
=?
/
mmmm^
>
E
•>J g r~M
=«
|
3
D
i
5.2
CM
ii A
("M
-3.8CM
Figure 01-01-03-01A. Soksoyr/Ross Coil (Reference 053).
4. APPLICATION- Engineering evaluation R&D, environmental assessment.
A) OPERATIONAL SCOPE
This method covers the high precision determination of sulfur oxide emissions in flue gases.
B) INTERFERENCES/LIMITATIONS
It is also possible that S02 can be oxidized by the quartz wool or by the particulates collected on the quartz wool. The
temperature of the particulate filter should be kept >225°C.
C) RECOMMENDED USE AREA
Engineering evaluation R&D of flue gas streams for
5. OPERATIONAL PARAMETERS
A) RANGE This method is applicable to the determination of SO, from 10 3000 ppm and SO, from 10 - 300 ppm.
B) ACCURACY 5% (estimated).
C) PRECISION For S02>±2.62 at 1500 ppra. For S03, ±5% at 10 ppm (estimated).
6. REAGENTS REQUIRED
Ethyl alcohol, hydrogen peroxide, high purity water.
7. EQUIPMENT REQUIRED
Borosilicate glass, probe with heating attachment, $03 condenser
coil (see Figure 01-01-03-01A), midget impingers, critical orifice
meter, powerstats, stop watch, thermometer, plastic bottles,
laboratory glassware, constant water bath.
& KEYWORD INDEX.' Sampling, sulfur trioxide, sampling.
9. CROSS REFERENCE ID NUMBERS 02-03-02-03.
0. REFERENCES
A) PRIMARY SOURCE
. 1" F1Ue GaS6S (BaHm c"lor.nn.te Controlled Condensation
B) BACKGROUND INFORMATION
054 Goksoyr, H.,and K. Ross, Journal of Institute of Fuel (London), 35_, 177 (1962).
055 Lisle, E.S., and J.D. Sensenbaugh, Combustion. 36_, 12 (1965).
056 Burger, A.W., J.N. Driscoll, and P. Morgenstem, Ind. Hyg. Assoc. J.. 33_, 3397 (1972).
C) FIELD APPLICATIONS
012 Driscoll, J.N., and A.M. Berger, "Improved Chemical Methods for Sampling & Analysis of Gaseous Pollutants from Combustion
of Fossil Fuels," Final Report, Vol. 1, Sulfur Oxide, Contract No. CPA22-69-95 (June 1971), APD No. 1106, p. 209.
30
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PAGE 1 OF 2 FOR
1. TITLE GENERAL GAS GRAB SAMPLING TECHNIQUES
2. IDENTIFICATION CODE
01-01-04-01
3. ABSTRACT OF METHODOLOGY
When there is an abundant supply of gas, an air displacement procedure may be used to obtain a sample. The procedure involves purging
the sample container (which is connected to an appropriate probe and line, and which precedes any impingers located in the sampling train)
with a volume of gas equivalent to 10 times the sample container volume prior to collection of the sample. Typical glass and metal sample
containers are shown in Figure 01-01-04-01A. If the gas is under low pressure, an aspirator or suction device is first connected to the
end of the sample container for purging purposes. A liquid displacement method is used when the gas supply is limited. Composite con-
tinuous samples of several cubic feet or larger can also be taken using liquid displacement techniques. Figure 01-01-04-01B shows a gas
grab purge sampling apparatus, including a simple open-end sampling probe.
4. APPLICATION- Environmental assessment, engineering evaluation R&D.
A) OPERATIONAL SCOPE
Method is applicable to sampling flue gases and other streams involving temperatures of 200°C, and pressures slightly greater
than 1 atm.
B) INTERFERENCES/LIMITATIONS
Gases containing corrosive constituents must be avoided, in order to prevent damage to lines, containers and auxiliary equipment.
Interferences to sampling by air contamination, leakage, absorption/chemical reaction must be avoided. The successful application
of the sampling method must reflect consideration of purpose for which sample is collected, in terms of volume of sample required,
size and length of sampling line, and size and design of containers.
C) RECOMMENDED USE AREA
This is the recommended level 1 environmental assessment procedure for sampling inorganic gases, acid gases, and sulfur compounds.
5. OPERATIONAL PARAMETERS
A) RANGE
Range is primarily governed by size and design of sample containers, and to a lesser extent, the other components
of sampling equipment. Typical sampling rate is 2 to 10 m3 of gas over 1-to 4-hour period.
B)
C)
ACCURACY N/Q
PRECISION ±10%
6. REAGENTS REQUIRED
Mercury, or other liquid, for liquid
displacement method.
7. EQUIPMENT REQUIRED
Sampling probes, preferably metal sampling lines (iron pipe, copper, monel metal, brass tubing;
glass or quartz tubing for sulfur compounds sampling at low pressures, aluminum tubing for sulfur
compound sampling at high pressures). Sample containers (glass, steel, metal, or metal alloys)
(see Figure 01-01-04-01A and B); aspirators and pumps; stopcock lubricant.
8. KEYWORD INDEX^ Gas sampling, grab, composite continuous sampling, air displacement, liquid displacement.
9. CROSS REFERENCE ID NUMBERS 01-05-04-01; 01-01-01-04; 02-02-01; 02-03-01.
10. REFERENCES
058
A) PRIMARY SOURCE
057 ASTM Committee 0-3 and D-5, "Gaseous Fuels, Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, D1247-54,
"Standard Method of Sampling Manufactured Gas," American Society for Testing and Materials, Philadelphia, PA., 1971, p. 222-231.
Hamersma, O.W.,and S.R. Reynolds, "Tentative Procedures for Process Measurements, Lurgi Coal Gasification Process,"
TRW Systems Group, EPA Contract No. 68-02-1412, March 1975, p. 5-4.
B) BACKGROUND INFORMATION
024 ASTM Committee D-19 and 0-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, 01605-60, "
Atmospheres for Analysis of Gases and Vapors," American Society for Testing and Materials, Philadelphia, PA., 1971, p.
052 Leithe, W., "The Analysis of Air Pollutants," Ann Arbor-Humphrey Science Publishers, Ann-Arbor, Michigan, 1970.
C) FIELD APPLICATIONS
058 Cropper, F.R., and S. Kaminsky, "Determination of Toxic Organic Compounds in Admixture in the Atmosphere by Gas
Chromatoqraphy." Anal. Chem., 35(6). 735 (1963). .
059 Novak, 0., J. Janak and V. Vasaic, "Chromatographic Method for the Concentration of Trace Impurities in the Atmosphere
and Other Gases," Anal. Chem.. 37(6), 660-666 (1965).
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PAGE 2 OF 2 FOR
TITLE GENERAL GAS GRAB SAMPLING TECHNIQUES (CONTINUED)
ID NO. 01-01-04-01
Type C
D 1247
Type F
Figure 01-01-04-01A. Glass and Metal Sample Containers (Reference 057).
Figure 01-01-04-01B. Grab Purge Sampling Apparatus (3 liters) (Reference 058).
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PAGE 1 OF 2 FOR
1. TITLE FLUE GAS GRAB SAMPLING USING PLASTIC BAGS
2. IDENTIFICATION CODE
01-01-04-02
3. ABSTRACT OF METHODOLOGY
Plastic bags of various compositions are suitable for the collection of flue gas grab samples. Typical apparatus includes a standard
probe which is connected to an air movement device, followed by the sampling line leading to the inflatable plastic sample bag
(usually Mylar, Tedlar, etc.) See Table 01-01-04-02A for some storage properties of gases in plastic bags.
4. APPLICATION- Environmental assessment, engineering evaluation R&D.
A) OPERATIONAL SCOPE '
The method is applicable to wide range of samples, sample volumes, etc. (see Table 01-Q1-Q4-02A); temperature range is dependent
upon individual plastic used, with maximum temperatures up to a 100°C.
B) INTERFERENCES/LIMITATIONS
Method cannot be used for sulfur gases, or organics which may chemically interact. Sample loss/contamination is dependent upon
type of plastic used, type and concentration of sample, etc.; temperature, pressure, and likelihood of chemical interactions
among the compounds of the trapped samples (particularly organic samples).
C) RECOMMENDED USE AREA
This is the recommended environmental assessment procedure for flue gas sampling.
5. OPERATIONAL PARAMETERS
A) RANGE Collected gases can be contained for periods of several days, with 9051 or better retention. Up to several cubic-feet
of sample can be collected. The flue gas sampling rate of 2 x 10 m3 over a 1-to 4-hour period is acceptable.
B) ACCURACY 10% or better.
C) PRECISION
N/Q
& REAGENTS REQUIRED
See Table 01-01-04-01A for plastic bag compositions.
7. EQUIPMENT REQUIRED
Plastic bag, plastic box for housing the bag (optional), probe,
air movement device and sampling lines.
KEYWORD INDEX: Flue gas sampling.grab sampling, plastic bags, Tedlar, Mylar.
9. CROSS REFERENCE ID NUMBERS 01-05-04-02; 02-02-01; 02-03-01.
10. REFERENCES
A) PRIMARY SOURCE
026 American Conference of Governmental Industrial Hygienists, "Air Sampling Instruments for Evaluation of Atmospheric
Contaminants," Cincinnati, "Amer. Conf. of Governmental Industrial Hygienists," 4th ed., 1972, p. R-5 to R-7.
B) BACKGROUND INFORMATION
024
ASTM Committee D-19 and D-23, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, D1605-60, "Sampling
Atmospheres for Analysis of Gases and Vapors," American Society for Testing and Materials, Philadelphia, PA., 1971, p. 351-2.
060 Altshuller, A. P., I,R. Cohen, S.F. Selva and A.F. Wartburg, "Storage of Vapors and Gases in Plastic Bags,"
Int. J. Air Hat. Poll.. 6_, 75-81 (1962).
061 Conner. W.D., and J.S. Nader, "Air Sampling with Plastic Bags," Amer. Indust. H.yg. Assoc. J..25, 291-297 (1964).
062 Baker, R.A., and R.C. Doerr, "Methods of Sampling and Storage of Air Containing Vapors and Gases," Int. J. Air
Poll., 2, 142-158 (1959).
063 Ringold, A., R. Finn, J.R. Goldsmith, H.L. Helwig and F. Schuetts, "Estimating Recent Carbon Monoxide Exposures,"
Arch. Environ. Health. 5_, 38-48 (1962).
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PAGE 2 OF 2 FOR
TITLE FLUE GAS GRAB SAMPLING USING PLASTIC BAGS (CONTINUED)
ID NO. 01-01-04-02
B) BACKGROUND INFORMATION
064 Tamplin, B., Unpublished data, Air and Industrial Hygiene Laboratory, California State Department of Public
Health (1963).
065 Schuette, F.J., Unpublished data, Air and Industrial Hygiene Laboratory, California State Department of Public
Health (1962).
066 Schuette, F.J., "Plastic Bags for Collection of Gas Samples," A.I.H.L. Report No. 19, California Department
of Public Health (December 1965).
C) FIELD APPLICATIONS
067 "Tentative Method for Analysis of Ci through C5 Atmospheric Hydrocarbons," Review Draft (1965) Method SDPH:
1-50, Air and Industrial Hygiene Laboratory, California State Department of Public Health.
068 Steward, R.D., D.S. Erley, H.H. Gay, C.L. Hake, and J.E. Peterson, "Observations on the Concentrations of
Trichloroethylene in Blood and Expired Air Following Exposure of Human," Amer. Indust. Hyg. Assoc. J., 23,
167-170 (1962).
069 O'Keefe, A.E., 1965, Private communication, Laboratory of Engineering and Physical Sciences, Division of Air
Pollution, U.S. Public Health Service, Cincinnati, Ohio.
070 Wilson, K.W., and H. Buchberg, "Evaluation of Materials for Controlled Air Reaction Chambers," Indust. Eng.
Chem, 50, 1705-1708 (1958).
Table 01-01-04-02A. Some Storage Properties of Vapors and Gases in Plastic Bags (Reference 026).
Plastic
Film
Mylar
Poly vinyl
Scotch Pak
Kel-F
Reference
060, 061
060, 061
060, 061
063
064
062
Gas or Vapor
Stored
Ozone
N02
S02
co2
co2
N02
Concentration
70 ppm
0.2 to 0.5 ppm
0.5 ppm
1 to 100 ppm
1 to 100 ppm
1 ppm
Remarks
10% loss in 5 hrs in synthetic air
5% in 8 hrs in synthetic air
Stable for 4 hrs in synthetic air
Storage variable with source of supply
Stable several days in expired air
Stable for 120 hrs
-------
PAGE 1 OF 2 FOR
1. TITLE
(NATURAL GAS CONTAINING HYDROCARBONS
2. IDENTIFICATION CODE
01-01-04-03
3. ABSTRACT OF METHODOLOGY
For collecting relatively large samples in high pressure containers, the apparatus depicted in Figures 01-01-04-03A and 01-01-04-03B
are used; for the collection of very large samples, several containers of sample may be simultaneously collected using a manifold
system. The valves leading from the gas mains (flues) shown in the figures can be substituted with probes and lines (Teflon or 316 SS).
An average sample can be obtained by taking a series of consecutive grab samples, using air or liquid displacement techniques.
Alternatively, a continuous sampling method having direct connection to analytical instrumentation can be used.
4. APPLICATION- Environmental assessment, engineering evaluation RSD
A) OPE RATIONAL SCOPE
Method is applicable to gasifier streams, having gas under pressure as high as 9,000 10,000 psi. Inorganic gases, acid gases
and sulfur compounds can be sampled (see Table 01-05-04-01A).
B) INTERFERENCES/LIMITATIONS
Proper sampling will reflect consideration of constituents present in the gas. For sampling sulfur-containing gases, air dis-
placement methods and aluminum tanks should be used. For gases containing greater than 0.5* C0_, an air displacement method
must be used.
C) RECOMMENDED USE AREA
This is the recommended level 1 environmental assessment high pressure gas grab sampling procedure.
5. OPERATIONAL PARAMETERS
A) RANGE Range is governed by size and design of sample containers, and of other components of sampling equipment. Typical
flue gas sampling rate of 2 to 10 ir? over a 1- to 4-hour period is applicable.
B) ACCURACY N/Q
C) PRECISION
+10%
6. REAGENTS REQUIRED
Mercury or other liquid for liquid displacement methods.
7. EQUIPMENT REQUIRED
Sampling connections (threaded or welded pipe), sampling lines (iron
pipe, copper, brass or aluminum tubing, high pressure hose; glass,
quartz or porcelain tubing for low gas pressures), sample containers
(iron, steel or glass - see Figure 01-01-04-01A).
& KEYWORD INDEX: Sas grab sampling, air displacement, liquid displacement, high pressure.
9. CROSS REFERENCE ID NUMBERS 01-05-04-01; 01-01-04-01; 02-02-01; 02-03-01.
10. REFERENCES
A) PRIMARY SOURCE
057 ASTM Committee 0-3 and D-5, "Gaseous Fuels; Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, 01145-53,
"Standard Method of Sampling Natural Gas," American Society for Testing and Materials, Philadelphia, PA., 1971, p. 208-221.
B) BACKGROUND INFORMATION
071 Altieri, V.J., "Gas Analysis and Testing of Gaseous Materials," American Gas Association, p. 76-79.
C) F IE LD APPLICATIONS
35
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PAGE 2 OF 2 FOR
TITLE HIGH PRESSURE GAS GRAB SAMPLING (NATURAL GAS CONTAINING HYDROCARBONS
AND NITROGEN; SULFUR; C02) (CONTINUED)
ID NO. 01-01-04-03
WELDERS RUBBER HOSE
GAS MAIN
HAND PUMP
STEEL CYLINDER
Figure 01-01-04-03A. Apparatus for Collecting a Sample in a Steel Container Under Pressure, Either
Direct from Gas Main or Using a Hand Pump (057).
VALVE OPEN
COPPER OR IRON PIPE
SAMPLING LINE
VALVE OPEN
GAS LINE
VALVE OPEN SUFFICIENTLY
TO PERMIT CHANGE OF
CYLINDER CONTENT
DURING DESIRED PERIOD
OF SAMPLING
ORIFICE OF PROPER
SIZE MAY BE USED
IN THIS LINE
CYLINDER FILLED
WITH GAS FROM
GAS LINE AT LINE
PRESSURE
O 1145
Figure 01-01-04-03B. Arrangement of Apparatus for Collecting an Average Sample, Dry, Under Pressure (057).
36
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Table of Contents for 01-02 Sampling Liquid/Slurry
01-02-01 Automatic Liquid/Slurry Sampling
01-02-01-01 Sampling Liquid Streams with a CVE Composite
Sampler
01-02-01-02 Model 1680 Sequential Liquid Slurry Sampler ,
01-02-01-03 Liquid Sampling of Lines or Tanks Using
Model L Sampler
01-02-02 Liquid/Slurry Grab Sampling
01-02-02-01 Grab Sampling of Water
01-02-02-02 Liquid/Slurry Grab Sampling (Dipper Sampling,
Thief Sampling) , . . ,
37
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APPLICATION MATRIX FOR 01-02 LIQUID/SLURRY SAMPLING
METHOD
01-02-01-01
01-02-01-02
01-02-01-03
01-02-02-01
01-02-02-02
LEVEL .1
ENVIRONMENTAL
ASSESSMENT
• . ,
•
: - • ,
•
•
COMPLIANCE
,
ENGINEERING
EVALUATION
,R/D
•
•
•
38
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SAMPLING LIQUID AND SLURRY ID No. 01-02
Wastewater from plants consists of both contaminated and relatively
clean effluent streams. In general, the contaminated wastewaters are
those taken from processes while the clean wastewaters are those used for
indirect heat exchange, general washing, etc. Sources of contaminated
wastewaters include:
• Brines from electrolysis and crystallization
• Filter cake washings (mining operations)
• Waste acid and alkaline streams (wet scrubber equipment)
t Washing streams containing substantial amounts of suspended
particulate matter (coal gasifiers).
In general, these waters are characterized by suspended solids ranging
from tenths to tens of percent of the total weight.
Clean wastewaters are primarily composed of steam condensate and
cooling water. Normally, these are released into the environment with
little or no treatment. Due to process leaks, makeup water, boiler blow-
down, etc., these streams can become polluted and would be sources for
sampling.
An important factor which must be considered in sampling liquid/slurry
streams is the size of sample required. There are two principal require-
ments which determine how much sample must be collected. The first require-
ment is that the amount of sample collected must be sufficient for the
testing and analysis procedures to furnish an accurate and precise result.
The second requirement, which determines the amount of sample to be col-
lected, is the statistical sampling error that can be tolerated. The mini-
mum sample required for analysis varies considerably for the trace analysis.
The minimum element concentration level varies between 1 and 1000 pg for
most analysis procedures. For the lower ppm concentration levels of
interest, this translates into minimum sample volumes ranging between
one ml and one liter. This range of sample volumes is easily within the
operating limits of presently available liquid sampling equipment and
presents no special difficulties.
39
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Determining the minimum size liquid sample that must be collected to
reduce statistical sampling error to acceptable limits is considerably more
difficult. The total error of sampling and analysis is equal to:
Where E, = the total error of the combined sampling and analysis
S = error in sampling
A = error in analysis
For example, to meet a goal of a combined relative sampling and analy-
sis error of +25 percent, the allowable error between sampling and analysis
must be budgeted. Allowing a maximum 15 percent error for analysis, the
sampling error can be as high as 20 percent and meet the 25 percent over-
all error (25 = V2Q2 + 152).
The equipment discussed in this section is capable of handling the
wide variety of process streams found in most industrial applications. In
streams with highly corrosive materials present, the Teflon coating all
metal parts to prevent contamination of the samples and destruction of the
sampling system should be considered. However, for most applications, the
built-in flexibility of the off-the-shelf samplers is adequate.
01-02-01 Automatic Liquid/Slurry Sampling
(Abstracts 01-02-01-01 through 01-02-01-03)
The factors which must be considered in accurately sampling a liquid/
slurry stream include:
• Stream homogeneity
• Stream flow rate and variations
• Prevention of sample loss
• Sources of contamination
• Sample size required.
Of these, stream homogeneity is perhaps the most important factor.
Unlike stack effluent streams which are mixed fairly evenly due to higher
thermal agitation and lower fluid viscosities, liquid streams tend to be
40
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more stratified and require more careful sampling. A flow-proportional
composite sampling technique is required for sampling liquid and slurry
streams for trace materials. In obtaining a composite representative
sample from a stack, a traverse of the pipe or duct is made. This is
usually impractical in sampling liquid streams. In liquid streams, a
composite sample (01-02-01-01, 02) can be taken by using several differ-
ently positioned probes, a single multi-ported probe, or a combination of
these. While any of these approaches is suitable, the single multi-ported
sampler is usually more convenient.
In the case of slurry sampling, it is also important to avoid segrega-
tion of liquid and solid phases. This is similar to the requirement for
isokinetic sampling in particulate-laden gas streams. Sampling velocity
is the most critical factor in sampling sewage slurries. The EPA (Refer-
ence 072) has shown that suction line velocity is only one of many varia-
bles, and that line velocity differences within a reasonable range (approxi-
mately 0.6-1.5 m/sec or 2 to 5 ft/sec) do not have a consistent effect on
sample composition. Outside of this range, certain low velocity piston or
peristaltic pumps and high velocity vacuum samplers often preclude large
composition deviations. In other cases such as storage tanks or pipes
under high pressure, pumps are not necessary. Special samplers (01-02-02-03)
are available for this specialized purpose.
01-02-02 Liquid/Slurry Grab Sampling
(Abstracts 01-02-02-01 through 01-02-02-02)
Grab sampling of tap water (01-02-02-01) requires that the tap and
any associated lines are purged completely. A sample can then be taken
or composited over a period of time. Free flowing streams (01-02-02-02)
simply require that the sample container be positioned so that a portion
is collected from the full cross-section of the stream. Because composi-
tion can vary with depth in storage tanks or tank cars, samples should
be taken at depths representing the midpoint of the upper, middle, and
lower parts of the tank (01-02-02-02).
Trace materials in liquid phases may be lost from a sample through
adsorption on sampling line or reservoir surfaces. Borosi1i cate glass
41
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(Pyrex) surfaces appear to be particularly effective in removing trace
heavy metals, especially under alkaline conditions. Plastics such as
polyethylene, polypropylene, and Teflon show little or no tendency .to
adsorb inorganic materials. It is essential, therefore, that the sampling
lines and collection reservoirs (01-02-02-01) used for sampling liquid
streams be made of plastic, preferably Teflon because of its superior
chemical inertness toward strong acids and alkalis and other chemical
reagents.
Just as material may be lost from a sample due to surface effects,
so may a sample be contaminated with elements from those surfaces. Sur-
face wall material can be deposited in a sample either by a chemical
extraction of the wall materials by reagents in the sample or by physical
abrasion or erosion of the wall by a sample. The latter case can be a
significant problem for slurry systems because of the chemical interaction
of the sample with wall materials and the possibility that a sample could
become contaminated with elements from a sample probe or a sample line.
The proper cleaning procedures must be followed (see 02-01).
REFERENCES
072 Shelley, P.E.,and G. A. Kirkpatrick, "An Assessment of Automatic
Flow Samples," EPA Report R2-73-261 (1973).
42
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PAGE 1 OF 2 FOR
1. TITLE SAMPLING LIQUID STREAMS WITH A CVE COMPOSITE SAMPLER
2. IDENTIFICATION CODE
01-02-01-01
3. ABSTRACT OF METHODOLOGY
The vacuum system lifts liquid through a suction line into the sampling chamber. When filled, the chanuer is automatically closed to
the vacuum. The pump then shuts off and the sample is forcibly drawn into the sample container. A secondary float check prevents any
liquid from reaching the pump, should the primary shutoff pass any material. The suction line drains by gravity back into the source.
No pockets of fluid remain to contaminate subsequent samples. Automatic blowdown of suction lines and the entire liquid system assures
that no material remains to contaminate the current sample (see Figure 01-02-01-01A).
4. APPLICATION: Engineering evaluation R&D, environmental assessment
A) OPE RATIONAL SCOPE
This sampler can be used in flowing streams with dissolved salts, in open channels, partially full pipe flows with sampling port
greater than 0.64 cm (1/4 inch) ID, full pipe flows at atmospheric pressure, flowing streams (open channel and flows with sus-
pended solids of 0.32 cm (1/8 Inch) particle size or less). This instrument also can sample to a maximum depth of 6.96 m (20 feet).
B) INTERFERENCES/LIMITATIONS
This instrument is designed t
up to a total of the gallon storage capacity.
This instrument is designed to operate at temperatures less than 200°C. Between 20 to 50 mi-sized samples per cycle can be taken,
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D liquid/slurry sampler.
5. OPERATIONAL PARAMETERS
A) RANGE N/A
B) ACCURACY This instrument was evaluated by the EPA as the best liquid/slurry automatic sampler (see Table 01-02-01-01A).
C) PRECISION N/A
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
None
Model CVE liquid slurry sampler (Quality Control Equipment Corp.,
Des Moines, Iowa).
a KEYWORD INDEX: Sampling, liquid slurry sampling, CVE sampler.
9. CROSS REFERENCE ID NUMBERS 02-01-02, 02-01-03.
10. REFERENCES
A) PRIMARY SOURCE
072 Shelley, P.E., and G.A. Kirkpatrick, "An Assessment of Automatic Flow Samplers," EPA R2-73-261 (1973).
B) BACKGROUND INFORMATION
C) FIELD APPLICATIONS
073 Harris, J., and W.J. Keefer, "Wastewater Sampling Methodologies and Flow Measurement Technioues," EPA-907/9-74-005,
June 1974.
-------
PAGE 2 OF 2 FOR
,
TITLE SAMPLING LIQUID STREAMS WITH A CVE COMPOSITE SAMPLER (CONTINUED) ID NO. 01-02-01-01
L.in.i— —i- — i, „_„„.„.„ — .___ _ , — — — — . 1
Table 01-02-01-01A. Incidence of Sampler Malfunction*
Influent Sampling Stations Effluent Sampling Stations
Ovprn 1 1
Automatic Total Total Failure
Wastewater Times Times Rate
Sampler Used Failed Percent Used
Sigmamotor WA-2 24 6 25 8
Sigmamotor WD-2 31 4 13 15
Brailsford DU-1 45 15 33 40
Brailsford EV-1 29 5 17 26
Brailsford EP-1 63 6 10 55
QCEC CVE 90 4 4 77
Pro-Tech C6-125P 10 4 40
ISCO 1391-X 16 4 25 16
ISCO 1392 17 1 5 15
N-Con Scout 14 2 14 14
N-Con Surveyor 7 3 43 5
Total and Mean
Failure Rates 346 54 16 271
Failure Failure
Rate Rate
Failure Percent Used Failure Percent
4 50 16 2 13
2 13 16 2 13
13 33 52 40
5 19 3 0 0
6 11 8 0 0
4 5 13 0 0
,-iOT BROKEN DOWN
4 25 0 0 j 0
17200
2 14 0 0 0
3 60 2 0 0
44 16 65 6 9
*
From Harris and Keefer (see Field Applications Reference 073}
VACUUM SYSTEM
I BLOW-DOWN
1 SOLENOID
V VALVk
VACUUM )= a——
PUMP ^ r~]|
XV
FLOAT -T
CHECK | |
BLEED AND \ /
DRAIN ] L
VALVE ~~"~^i-J5 —
^^ ~/* >
,~ ^ " INTERVAL
V , y TIMER
. f~L ~\
115V INPUT
SAMPLE
=^ a CHAMBER
/V* -CHECK
D1 —
/Y ^
SAMPLE I
JAR %a /
t
LIQUID SYSTEM
Figure 01-02-01-01A. Schematic of CVE Composite Sampler.
-------
1. TITLE MODEL 1680 SEQUENTIAL LIQUID/SLURRY SAMPLER
2. IDENTIFICATION CODE
01-02-01-02
3. ABSTRACT OF METHODOLOGY
Samples can be collected at intervals of 1 to 999 minutes with a maximum sample size of 500 ml, While 28 bottles (see 02-01-01-05)
are provided, 1 to 4 samples may be added to each bottle to provide a limited compositing capability with the sequential sampling. An
ice compartment has adequate capacity to keep the samples 4.4°C below ambient temperature for 12 hours (-1.1°C for 24 hours). The samples
are collected using a peristaltic pump with valves on metering chambers, which minimizes equipment failure and sample contact.
4. APPLICATION- Engineering evaluation R&D, environmental assessment
A) OPE RATIONAL SCOPE
This instrument can be used in flowing streams, dissolved salts and open channel flows, partially-filled pipe fills with sampling
ports greater than 1.27-cra (1/2 inch) ID, full pipe flows at atmospheric pressure, flowing streams (open channels and closed) with
suspended solids (0.32-cm or 1/8-inch particle size). The maximum depth of sampling is 6.96 m (20 ft).
B) INTERFERENCES/LIMITATIONS
This unit is designed to sample streams at temperatures less than 200°C. Each sample bottle contains up to 500 ml with a
total of 28 bottles. Because of the arrangement of the bottles, the ice cooling capability is less effective.
C) RECOMMENDED USE AREA
This unit is second choice as an engineering evaluation R&D liquid/slurry sampler.
5. OPERATIONAL PARAMETERS
A) RANGE N/A
B| ACCURACY The Model 1680 was also highly recommended in an EPA assessment study. It is currently being used in the Los Angeles
County district.
C) PRECISION N/A
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
None
Model 1680 sequential liquid/slurry sampler (Instrumentation
Specialities, Co., Lincoln, Nebr.).
a KEYWORD INDEX: Sampling, liquid sampling, sequential sampling.
9. CROSS REFERENCE ID NUMBERS 02-01-01-05, 02-01-02, 02-01-03.
10. REFERENCES
A) PRIMARY SOURCE
072 Shelley, P.E.,and G.A. Kirkpatrick, "An Assessment of Automatic Flow Sampler," EPA Report Number R2-73-261 (1973).
B) BACKGROUND INFORMATION
C) FIELD APPLICATIONS
073 Harris, D.J.,and W.J. Keefer, "Wastewater Sampling Methodologies and Flow Measurement Techniques,"'EPA 907/9-74-005,
June 1974.
-------
PAGE 1 OF 2 FOR
1. TITLE LIQUID SAMPLING OF LINESOR TANKS USING MODEL L SAMPLER
2. IDENTIFICATION CODE
01-02-01-03
3. ABSTRACT OF METHODOLOGY
The Model L sampling probe (see Figure 01-02-01-03A) is moved by an air cyclinder in and out of the liquid line or tank. Machined to a
fine tolerance, this air liquid sampler has long-life Teflon seals that will keep it leakproof. Samples are gravity expelled into
receptacles under the unit. No residual is left behind to foul succeeding samples. Quantity of the sample ranges from 2 ml to 30 ml.
It is constructed of 316 SS and can be mounted through a side wall or a pipe or tank or at an elbow. This type of sampler is extremely
useful if sampling lines have access ports already available.
4. APPLICATION: Environmental assessment, engineering evaluation R&D.
A) OPERATIONAL SCOPE
This sampler is designed to sample liquids in a pipe or in a tank containing liquids that are compatible with 316 SS. This system
is particularly useful if the liquid is under pressure at the sampling point.
B) INTERFERENCES/LIMITATIONS
Since the sampler is constructed of 316 SS, contamination through corrosion of the SS by corrosive liquids is possible. Contami-
nation of the collected sample by the corrosion products of 316 SS (Ni, Cr and Fe) should be considered prior to using this sampler.
C) RECOMMENDED USE AREA
Environmental assessment of pressurized lines.
5. OPERATIONAL PARAMETERS
A) RANGE N/A
B) ACCURACY N/A
C) PRECISION N/A
6. REAGENTS REQUIRED
Sampling bottles (see 02-01-01).
7. EQUIPMENT REQUIRED
Type L liquid sampler (Quality Control Liquid Company,
Des Moines, Iowa).
KEYWORD INDEX: Liquid sampling, Type L sampler.
9. CROSS REFERENCE ID NUMBERS 02-01-01, 02-01-02.
10. REFERENCES
A) PRIMARY SOURCE
074 Manufacturer's Bulletin on Type L Sampler from Quality Control Equipment Co., 2505 McKinlev Avenue, Des Moines, Iowa 50315.
B) BACKGROUND INFORMATION
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, D510-68, "Standard
Methods of Sampling Drilled Water," American Society for Testing and Materials, Philadelphia, PA., 1971, p. 2.
025 Brown, E., M.J. Fishman and N.W. Skougstad, "Methods for Collection and Analysis of Water Samples for Dissolved Minerals
and Gases, U.S. Geological Survey, Technical Water Resources Inventory, 5, Chapter Al, 1970.
C) FIELD APPLICATIONS
072 Shelley, E.E.,and G.A. Kirkpatrick, "An Assessment of Automatic Flow Samplers," EPA Report Number R2-73-261 (1973).
-------
PAGE 2 OF 2 FOR
TITLE LIQUID SAMPLING OF LINES OR TANKS USING MODEL L SAMPLER (CONTINUED)
ID NO. 01-02-01-03
Figure 01-02-01-03A. Model L Sampling Probe (Quality Equipment Co.).
-------
PAGE 1 OF 3 FOR
1. TITLE GRAB SAMPLING OF WATER
2. IDENTIFICATION CODE
01-02-02-01
3. ABSTRACT OF METHODOLOGY
A tap sampling assembly is shown in Figure 01-02-02-01A. Before sampling, the tap and associated lines must be thoroughly flushed to
avoid contamination. A clean delivery tube is then connected to the tap, and a sample of 0.25 liters or more per hour can be collected.
When sampling from cocks or valves, the flow is conducted through a sampling line or a polyethylene tube extension of the sampling
line to the sample bottle until it reaches the bottom. A volume of 10 times the volume of the sample container is then allowed to
flow before a sample is taken.
Depth samples are obtained using the standard depth sampling rigs (e.g., Sirco Uniscoop). The sampler is typically lowered into the
sample using nylon rope or plastic-coated wire to a desired depth, after which a messenger weight can be lowered to trip a valve-
closing mechanism.
Samples at low or subatmospheric pressures can be obtained by inserting a water-cooled condenser, and a pump or aspirator between
the flue and the sample container. The volumes of sample required for some typical analyses are shown in Table 01-02-02-01A.
4. APPLICATION^ Environmental assessment
A) OPERATIONAL SCOPE
Method is applicable to sampling most industrial aqueous streams. The tap sampling procedure is applicable to sampling liquids
of 11.8 kg (1.83 kgf/cm2) Reid vapor pressure or less.
B) INTERFERENCES/LIMITATIONS
Special precautions may be required for handling of water containing unstable constituents, including those marked with an
asterisk in Table 01-02-02-01A.
C) RECOMMENDED USE AREA
This is the recommended level 1 environmental assessment procedure for aqueous grab sampling.
5. OPERATIONAL PARAMETERS
A) RANGE Range depends on size and/or type of apparatus used; see Table 01-02-02-01A for partial listing of volume require-
ments. Sampling rates will conform to flow rate of the sampled stream. Depth samples may be obtained from any desired depth.
B) ACCURACY N/Q
C| PRECISION ±10%, if proper sampling procedures for obtaining representative samples are followed.
& REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Cleaning solutions (solvents, soap, etc.); reagent water for
rinsing sample containers.
Sampling apparatus as shown in Figures 01-02-02-01A,
delivery tubes; sample containers.
8. KEYWORD INDEX: Grab sampling, water, tap sampling, depth sampling (Kemmerer type), reduced pressure samples.
9. CROSS REFERENCE ID NUMBERS 02-02; 02-03.
10. REFERENCES
A) PRIMARY SOURCE
024 ASTM Committee D-19 and 0-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, D510-68, "Standard
Methods of Sampling Industrial Water," American Society for Testing and Materials, Philadelphia, PA., 1971 p 2-17
015 Af^c™TJ"ee 5"2 2nd FTl7'J™t!21T Products - LPG> Aerospace Materials, Sulfonates, Petrolatum, Wax," 1971 Annual Book
nf flvTM Q-f anrt-xv+Af D*v>+ 1 Q f!97n C.C (lmn«J --._ C —-i _i... j: -r A.J i u~ j _• i _ m . •. .. .. _. ' „" ' '
058
of ASTM Standards, Part 18, D270-65, American Society for Testing and Materials,"ph11adelphTa"-PA7|''l97?! pi'47-71.'"
Hamersma, J.W.,and S.R. Reynolds, "Tentative Procedures for Process Measurements, Lurgi Coal Gasification Process " TRW Svsteras
Group, EPA Contract No. 68-02-1412, March 1975, p. 8-7. '
B) BACKGROUND INFORMATION
024 SoMifiS^88*0"1? a"d D"22i "Water; AtmosPher1c Analysis," 1971 Annual Book of ASTM Standards, Part 23, D1192-70, "Standard
pi 190-195 E<'u1Pment for Sampling Water and Steam," American Society for Testing and Materials, Philadelphia, PA., 1971,
024 £iI^«™l*!8%D~1;! and ?',2,2' "Watf; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, D1193-70 "Standard
O FIELD^APPLICATIONS'" " S°dety for Test1"9 and Materia1s> philade'P"". PA., 1971, P! 195-7.
48
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PAGE 2 OF 3 FOR
TITLE GRAB SAMPLING OF WATER (CONTINUED) ID NO. 01-02-02-01
Table 01-02-02-01A. Volume of Sample Required for Determination of the Various Constituents of Industrial Water {Reference 024).
Specific Determination
Physical Tests
*Color and odor
*Corrosivity
*Electrical conductivity
*pH, electrornetric
Radioactivity
*Specific gravity
*Temperature
*Toxicity
Turbidity
Chemical Tests
Dissolved Gases:
tAmmonia, NH,
tCarbon dioxide, free CO.,
tChlorine, free Cl,
tHydrogen, H,
£
tHydrogen sulfide, H,S
tOxygen, 0.,
C.
tSulfur dioxide, free S02
Miscellaneous:
Acidity and alkalinity
Bacteria, iron
Bacteria, sulfate-reducing
Biochemical oxygen demand
Carbon dioxide, total CO? (including
C03", HC03- and free)
Chemical oxygen demand
(dichromate)
Chlorine requirement
Chlorine, total residual Cl2 including
OC, HOC1, NH2 Cl, NHC12, 12 and free
Hardness
Microorganisms
Volatile and filming amines
pH, colorimetric
Polyphosphates
Silica
Solids, dissolved
Solids, suspended
Volume of
Sample,3 ml
100 to 500
flowing sample
100
100
100 to 1000
100
flowing sample
100 to 20 000
100 to 1000
500
200
200
1000
500
500 to 1000
100
100
500
100
100 to 500
200
50 to 100
2000 to 4000
200
50 to 100
100 to 200
500 to 1000
10 to 20
100 to 200
50 to 1000
100 to 20 000
50 to 1000
Specific Determination
Cations :
Aluminum, Al
tAmmonium,-NH.
Antimony, Sb to Sb
Arsenic, As to As+++++
Barium, Ba
Cadmium, Cd
Calcium, Ca+t
Chromium, Cr+++ to Cr++++t+
Copper, Cu
tlron, Fe and Fe
Lead, Pb++
•H.
Magnesium, Mg
Manganese, Mn to Mn
+
Mercury, Hg and Hg
Potassium, K
ii
Nickel, Ni
i
Silver, Ag
Sodi urn , Na
++
Strontium, Sr
Tin , Sn and Sn
Zinc, Zn
Anions :
Bicarbonate, HCO^
Bromide, Br"
Carbonate, CO,"
•J
Chloride, Cl"
Cyanide, CN"
Fluoride, FT
Hydroxide, OH~
lodide, I "
Nitrate, N03"
Nitrite, N02'
Phosphate, ortho, P04~", HP04"",
2 4
Sulfate, S04~", HS04"
Sulfide, S~~, HS"
Sulfite, S03"~, HS03"
Volume of
Sample,3 ml
100 to 1000
500
100 to 1000
100 to 1000
100 to 1000
100 to 1000
100 to 1000
100 to 1000
200 to 4000
100 to 1000
100 to 4000
100 to 1000
100 to 1000
100 to 1000
100 to 1000
100 to 1000
100 to 1000
100 to 1000
100 to 1000
100 to 1000
100 to 1000
100 to 200
100
100 to 200
25 to 100
25 to 100
200
50 to 100
100
10 to 100
50 to 100
50 to 100
100 to 1000
100 to 500
50 to 100
aVo1umes specified in this table should be considered as a guide for approximate quantity of sample necessary for the particular analysis
The exact quantity used should be consistent with the volume prescribed in the standard method of analysis, whenever the volume is
specified.
Aliquot may be used for other determination.
Samples for unstable constituents must be obtained in separate containers, preserved as prescribed, completely filled and sealed
against all exposure.
-------
TITLE GRAB SAMPLING OF WATER (CONTINUED)
PAGE 3 OF 3 FOR
ID NO. 01-02-02-01
LINE
OR
TANK
WALL
7 MM
(1/4 IN.)
Figure 01-02-02-01A. Assembly for Tap Sampling (Reference 058).
50
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PAGE 1 OF 2 FOR
1. TITLE LIQUID/SLURRY GRAB SAMPLING (DIPPER SAMPLING, THIEF SAMPLING)
2. IDENTIFICATION CODE
01-02-02-02
3. ABSTRACT OF METHODOLOGY
Dipper sampling can be conducted by using a dipper having a flared bowl and adequate capacity for the sample to be collected. The
dipper is inserted into a free-flowing stream so that a portion is collected from a full cross-section of the stream. Sampling is
conducted at time intervals such that a representative sample is collected (see 01-02).
Thief samplers (shown in Figures 01-02-02-02A, B) should be lowered into the dome of a tank car or hatch at depths representing the
midpoint of the upper, middle and lower parts of the tank. When full, the thief is removed and the contents are transferred to a
sample container.
Continuous sampling methods (discussed in 01-02-01) can also be used to obtain grab samples, except that only a single 1-liter
sample is needed.
4. APPLICATION'- Environmental assessment
A) OPERATIONAL SCOPE
Method is applicable to sampling most noncorrosive liquids. The dipper method is applicable for sampling liquids of 0.91 kg
(0.4 kgf/cm ) Reid vapor pressure or less, and for semi-liquids where an open discharge stream exists; the thief procedure is
applicable to obtaining bottom samples or semi-liquids in storage tanks.
B) INTERFERENCES/LIMITATIONS
Some limitations on obtaining representative samples include cleanliness of the sample container and use of proper sampling
procedure.
C)
RECOMMENDED USE AREA
This is the recommended level 1 environmental assessment method for liquid/slurry grab sampling of process effluent.
5. OPERATIONAL PARAMETERS
A) RANGE Range is dependent upon size and type of sampling equipment used. Sampling rate, governed by stream rate, is
virtually limitless. Apparatus should be designed such that proper depth is sampled.
B) ACCURACY N/Q
C) PRECISION ±10-20%
& REAGENTS REQUIRED
Cleaning solutions (solvents, such as naphtha soap solutions).
7. EQUIPMENT REQUIRED
Sampling apparatus as shown in Figures 01-02-02-02A and B;
delivery tubes; sample containers.
8. KEYWORD INDEX: Grab sampling, liquid sampling, slurry sampler, dipper sampler, thief sampler.
9. CROSS REFERENCE ID NUMBERS 01-02; 02-02; 02-03.
10. REFERENCES
015 ASTM Committee D-2 and F-7, "Petroleum Products LP6, Aerospace Materials, Sulfonates, Petrolatum, Wax," 1971 Annual Book
of ASTM Standards, Part 18, D270-65, American Society for Testing and Materials, Philadelphia, PA., 1971, P. 47-71.
B) BACKGROUND INFORMATION
015 ASTM Committee D-2 and F-7, "Petroleum Products-LPG, Aerospace Materials, Sulfonates, Petrolatum, Wax," 1971 Annual Book
of ASTM Standards, Part 18, 01265, American Society for Testing and Materials, Philadelphia, PA., 1971, p. 256-258.
018 Fleqal C A , M.I. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Procedures for Process Measurements, Trace
Inorganic Materials," TRW Systems Group, EPA No. 68-02-1412, July 1975, p. 8-9.
C) FIELD APPLICATIONS
51
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PAGE 2 OF 2 FOR
TITLE LIQUID/SLURRY GRAB SAMPLING (DIPPER SAMPLING, THIEF SAMPLING)
(CONTINUED)
ID NO. 01-02-02-02
3/8 IN.
I 1/4 IN. DIA.
3/8 IN.-»-
K-T
METRIC EQUIVALENTS
IN. 1/8 3/8 1 1/4 40
MM 3 10 32 1016
Figure 01-02-02-02A. Sampling Thief or Tube (Reference 018).
IN.
I
rf
N.
SIN
21/2
^
4
> ii (
_i-
L
-d_
J
-*-3 1/2 IN:-»-
DIA.
- 4 LUGS
1/4 IN.
HIGH
(A) BOMB-TYPE SAMPLING THIEF
(B) CORE THIEF. TRAP TYPE
METRIC EQUIVALENTS
IN. 1/4 | 21/23 1/2 8 10 1/2 15 3/4
MM 7 25 64 89 203 267 400
Figure 01-02-02-02'D. Sampling Thiets (Reference 018).
52
-------
Table of Contents for 01-03 Sampling Solids
01-03-01 Automatic Solid Sampling
01-03-01-01 Sampling Solid Materials With a Pneumatic
Sampler
01-03-01-02 Sampling of Solids (Coal) Using Standard
Mechanical Methods
01-03-02 Solid Grab Sampling
01-03-02-01 Solids Grab Sampling (Long-Pile, Alternate
Shovel Method)
53
-------
APPLICATION MATRIX FOR 01-03 SOLID SAMPLING
METHOD
01-03-01-01
01-03-01-02
01-03-02-01
LEVEL I
ENVIRONMENTAL
ASSESSMENT
•
•
•
COMPLIANCE
t
ENGINEERING
EVALUATION
R/D
•
•
54
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SAMPLING SOLIDS ID No. 01-03
Solid sampling covers a broad spectrum of material sizes from large
lumps down to powders and dusts. There is an equally diverse assortment
of potential sample sites including railroad cars, large heaps, plant
hoppers, conveyor belts, and process stream pipes. Obviously no one method
or piece of equipment can cover all of the situations that could be
encountered. One needs to be aware of the advantages and disadvantages
of all the procedures and then select whichever is most appropriate for
each field test. The discussion presented in this section is a brief over-
view of common solid sampling situations and of some of the alternatives
available to a field test team.
The chief consideration of solid sampling methodology is the problem
of acquiring representative samples. There are several procedures for
shovel sampling which attempt to make the sampling as representative as
possible. A statistical means of determining the sample size needed to
yield results having a prescribed level of precision based on the above
factors has been derived theoretically (Reference 076).
The general form of this equation is:
n =
where:
n = number of units to be taken for sample
a = advance estimate of the standard deviation
E = maximum allowable difference between the result to be obtained
from the sample and the result of testing the entire bulk of
material
t = a factor corresponding to the acceptable risk of exceeding E
The terms "E" and "t" are relatively easy to assign as they are the
parameters of the desired precision. The t is a statistical factor
55
-------
expressing the probability that, by chance, E will be exceeded. The
following lists values of t for a few approximate probability values:
t Probability that E will be exceeded
3 3 in 1000
2.58 1 in 100
2 45 in 1000
1.96 1 in 20
1.64 1 in 10
Generally, a factor of 3 is used to minimize the possibility of the
sampling error exceeding E. Any degree of precision can be chosen for E,
bearing in mind that the sample size increases as the square of the entire
precision term. E can be expressed as percent or in units of measurement;
however, a must be expressed in the same way so that the resultant, n, is
unitless.
The answer then comes out as n units of sample. These units (e.g.,
shovelfuls, pounds, or whatever) must be the same as those used to deter-
mine the standard deviation, a, in order to relate the two sides of the
equation. This means one of two things must be done. Either a preliminary
test must be run on at least 10 units of sample to calculate the standard
deviation between units, or a can be estimated, a somewhat larger number
of units taken for the sample than the estimated necessary, and the sample
size readjusted after the actual a has been determined.
The following is an example of this statistical equation. Using some
type of pipe sampler, a flowing stream of pulverized coal is being sampled
for percent ash. A preliminary test showed the average deviation between
samples taken by the pipe sampler to be 25 percent and a maximum sampling
error of 10 percent is required: Then:
n =
(3) (25)
10
2 2
= (7.5r = 56.25
= 57 samples
must be taken to determine percent ash in the coal with a maximum error
of 10 percent.
56
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01-03-01 Automatic Solid Sampling
(Abstracts 01-03-01-01 through 01-03-01-02)
Sampling solids as they move through pipes is the method of choice if
it is possible. There are a variety of pipe samplers commercially avail-
able. The best type of sampler of this variety is the pneumatic sampler
(01-03-01-01). This sampler eliminates the screw type or scraping action
of other types of samplers which grind the sample and abrade the sampler,
thereby introducing considerable contamination.
Mechanical samplers (01-03-01-02) require that the sample material be
in motion to present it to the cutters as a thin ribbon or stream. Design
considerations for feeding these samplers and catching the sample and
rejected material generally necessitate the installation of the sampler in
a permanent manner into the flow stream of the sample material. Numerous
mechanical samplers have been designed and the most popular designs have
been variously modified to satisfy specific applications. Nevertheless,
all mechanical samplers fall into two general types: those that take part
of the stream all of the time (stationary samplers), and those that take
all of the stream part of the time (moving samplers).
In stationary mechanical samplers, the entire sample stream is fed
continuously through the device and the stationary cutting edges remove
or divide out specific fractions. The two best known designs of this type
are rifflers and whistle-pipes.
Rifflers take several slices of the stream by means of parallel chutes
alternately placed at 90° angles to each other, thereby cutting the stream
in half. Successive rifflers can be arranged in banks to cut the stream
into any desired fraction. The smaller the chute width, the greater the
number of increments in the sample. Therefore, the accuracy of riffler
sampling increases as the ratio of chute width to particle size decreases,
to the limiting condition where the chutes tend to clog. In general, chutes
should be at least three times the diameter of the largest size particle to
avoid clogging. Care must be taken to feed the riffler with a well-mixed,
uniform sheet of material as any compositional variations due to cross-
sectional segregation are multiplied by a bank of rifflers.
57
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A whistle-pipe sampler consists of a vertical pipe with notched
openings cut halfway through the pipe, each spaced 90° horizontally from
the one above. Rectangular steel plates are placed in the notches at a
45° angle to the vertical so that the top edges coincide with a diameter of
the pipe. Thus each notch halves the sample and, with a series of five
openings, the sample obtained as 1/32 of the original volume. The same
fraction with improved accuracy can be obtained by using a cutter arrange-
ment that quarters the stream, rejecting opposite quarters, and spacing
each cutter at 45° horizontally from the one above. In either design, a
hopper-shaped liner is placed above each notch to re-center the stream
before it reaches the next cutter.
Both these stationary samplers have irresolvable design problems that
reduce their reliability. Worn or bent cutting edges distort both the
volume and the particle size distribution of the sample. The housing
necessary for these samplers prevents examining them for clogged openings
while in operation. Material streams whose composition varies along the
transverse section will be further segregated by either of these samplers.
Moving samplers consist of cutters that move through the free-falling
sample stream taking all the stream for the duration of time they are
moving through it. There are two ways of effecting this. One is with
rotating or oscillating samplers whose cutters are set on radii of an arc,
and the other is with straight-line samplers whose cutting edges are set
parallel to each other and perpendicular to the line of their path.
Among the well-known designs of rotating arc-path samplers are Vezins,
Synders, and Chas. Synders. They all consist generally of scoops with
vertical sides, set on an axis parallel to the stream flow. The best
oscillating samplers are known as Bruntons. The scoop travels back and
forth acfross the stream in a pendulum-type motion. The travel path must
be sufficiently long to minimize the bias created by taking more sample
from the sides of the stream than from the middle. All the arc-path
samplers have the advantage over stationary samplers in that they take an
accurate cut, are simply constructed, and are accessible for observation
while in operation. Damp sample material may tend to clog the scoops and
care must be taken to maintain the cutting edges in good condition and to
keep them completely radial.
58
-------
The straight-line samplers are generally considered to be the most
reliable and accurate of all available types of samplers. The design of
their cutters is such that the sampling scoop spends an equal amount of
time in every portion of the stream. Generally the travel is at right
angles to the stream. Though they provide increased reliability, these
samplers require more maintenance and attention because of their increased
mechanical complexity.
Thus automatic sampling will normally consist of using in-house equip-
ment. If these types of equipment are not available, standard solid grab
sampling techniques must be used.
01-03-02 Solid Grab Sampling
(Abstracts 01-03-02-01)
Grab sampling in its simplest form consists of taking small, equal
portions at random or regular intervals from the mass, typically from rail-
road cars, large heaps, or hoppers. The method is quick and inexpensive.
However, it makes no allowance for segregation due to particle size and
tends to give consistently high or consistently low results depending on
the person sampling. As such, grab sampling should only be used for no
more than rough checking.
Coning and quartering (01-03-02-01) consists of carefully piling the
material into a conical heap, then flattening the cone into a circular cake.
The cake is then marked into quadrants with opposite quadrants being taken
for sample and the other two discarded. The entire process can be repeated
until the desired sample size is obtained. This method is time-consuming
and the symmetry of the intended vertical size segregation is difficult to
achieve in practice.
In fractional shoveling, (01-03-02-01) every third, fourth, fifth, or
tenth shovelful is taken for sample and is applicable to materials being
loaded, unloaded, or moved from one place to another by shoveling. This
method is inexpensive and relatively fast. If performed conscientiously,
fractional shoveling can be more reliable than coning and quartering. How-
ever, its applicability is limited and errors are easily introduced by
carelessness.
59
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Pipe borers represent another class of solid sampling methodology.
The usual method for pipe borers is to insert the pipe into the material to
be sampled at regular intervals. Provided that the pipe is long enough to
reach the bottom of the material, the method is fairly reliable. However,
it is only applicable to fine or powdered dry materials, because lumps or
any stickiness will jam or plug the pipe. Small pipe borers can be used
to sample sacks or cans of material. There are primarily two designs that
give best results. One is a simple pipe that is tapered so the end first
inserted is smaller in diameter than the handle end. A more sophisticated
design, known as a thief, makes the sample more representative vertically.
It consists of two close-fitting concentric pipes sealed at the base in a
conical point. Longitudinal slots are cut along the side of each pipe.
The thief is inserted with the slots turned away from each other and then,
when the sampler is in position, the outer pipe is rotated, lining up the
slots and allowing the inner pipe to fill the sample. For proper results
with any design of pipe borer, whatever opening the sample material passes
through (slots or circular pipe ends) must be large relative to the maximum
particle size.
Auger samplers, a form of drill, pack the sample in the helical
groove of the auger and can be enclosed in a casing if the nature of the
sample is such that it will spill when the auger is removed from the hole.
They are simple to use, like the pipe borers, and have the further advantage
of being applicable to a greater variety of materials. For materials that
are packed too hard for a pipe sampler to be forced in, augers work well.
For very packed materials, machine-driven augers are available. However,
if spill is a serious problem a thief type pipe sampler would be the better
choice. Both pipe samplers and augers will yield poor results if the
material being sampled is poorly mixed.
REFERENCES
076 Weicher, et a]I, "Standard Methods of Chemical Analysis," Vol. II A,
otn ed. (1963).
60
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PAGE 1 OF 2 FOR
1.
3.
TITLE SAMPLING SOLID MATERIALS WITH A PNEUMATIC SAMPLER
ABSTRACT OF METHODOLOGY
The most suitable type of sampler for trace element sampling is a pneumatic sampler. This
scrapping action of the other types of samplers which can grind the
2. IDENTIFICATION CODE
01-03-01-01
type of sampler eliminates the screwed or
sample and abrase the sampler at the same time. This scrapping
or
grinding action introduces considerable contamination to the solid sampler. The best sampler currently available is the Model RTA of
the Quality Control Equipment Corp. All parts in contact with the sample can be made of Teflon or nylon. The sampling tube is extended
into the air line where it dwells for a short adjustment period (see Figure 01-03-01-01A).
The sample is trapped in a suitably sized
cavity in the sampling tube which is then automatically retracted and the sample rejected by an air blast. The sample is completely
discharged and no carry-over occurs. Samples collected by this device should be stored in a prewashed and predried plastic bottle or
plastic-lined drums. If plant personnel are to take the sample, they should be provided with appropriate bottles or containers.
4.
APPLICATION'- Engineering evaluation R&D, environmental assessment.
A) OPE RATIONAL SCOPE
This unit can be used to sample solids with particle size less
from pipes fitted with at least 5.08-cm (2-in.) diameters of
is 250°C. Stainless steel can be used at higher temperatures,
B) INTERFERENCES/LIMITATIONS
Under high temperature conditions where nylon or Teflon cannot
sample.
C) RECOMMENDED USE AREA
than 0.64 cm (1/4 in.
i in diameter, as well as slurries and liquids
inports. If a Teflon sampler is used, the maximum temperature range
but contamination (Ni,
Cr, Fe) is added to the sample.
be used, the SS collection area can be corroded and contaminate
the
Trace Material sampling (if Teflon parts are used) for engineering evaluation RSD.
5.
6.
OPERATIONAL PARAMETERS
A) RANGE N/A
B) ACCURACY N/A
C) PRECISION N/A
REAGENTS REQUIRED
Sample bottles (see 02-01-01).
a
9.
10.
KEYWORD INDEX: Sampling, solid sampling, pneumatic sampler.
CROSS REFERENCE ID NUMBERS 02-01-01, 02-01-02.
REFERENCES
7. EQUIPMENT REQUIRED
Model RTA Pneumatic Sampler (Quality Control Equipment Corp.
Des Moines, Iowa).
t
A) PRIMARY SOURCE
018 Flegal, C.A., M.L. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Procedures for Process Measurement: Trace
Inorganic Materials," TRW Systems Group, EPA Contract Number 68-02-1398, July 19, 1975.
B) BACKGROUND INFORMATION
077 Perry, J.H. (ed.). Chemical Engineers Handbook, 4th ed., McGraw-Hill, New York,
C) FIELD APPLICATIONS
1969.
61
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PAGE 2 OF 2 FOR
TITLE SAMPLING SOLID MATERIALS WITH A PNEUMATIC SAMPLER (CONTINUED)
ID NO. 01-03-01-01
SAMPLE INLET
SAMPLING TUBE
MOUNTING FLANGE TO SAMPLE PORT
25 1/2 IN.
SAMPLE OUTLET
AIR FITTINGS
Figure 01-03-01-01A. Pneumatic Sampler Schematic.
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PAGE 1 OF 2 FOR
1. TITLE SAMPLING OF SOLIDS (COAL) USING STANDARD MECHANICAL METHODS
2. IDENTIFICATION CODE
01-03-01-02
3. ABSTRACT OF METHODOLOGY
When the top size range of the coal and condition of coal preparation are known, a gross sample is obtained; the minimum number of
sample increments and their minimum specified weight are shown in Table 01-03-01-02A.
There are two general types of mechanical samples which can be employed for increment-taking: (a) moving samplers, which take a sample
of all the stream part of the time; and (b) stationary samplers, which take part of the stream all of the time. In stationary mechanical
samplers, the entire stream is continuously fed through the device and stationary cutting edges remove specific fractions. The most
common stationary devices are rifflers and whistle-pipes. (See 02-01-03-02 for riffle description.)
Moving samplers use cutters which move through the stream for continuous sampling for a given time period. Moving samplers use either
cutters which are set on radii of an arc, or cutters with edges parallel to each other and perpendicular to the stream. When sampling
characteristics or variances other than top size range and coal preparation are known, the number and weight of increments which need to
be taken for each gross sample are calculated using standard formulae. The collected samples are then subsampled by riffling or by
manual subdivision. (See 02-01-03-02.)
4. APPLICATION- Environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to sampling (coal) from plant hoppers, conveyor belts, process stream pipes, etc., and stationary
sources such as storage piles, rail cars, or barges. Both mechanically cleaned coals and raw coals can be sampled. See
Table 01-03-01-02A for top size ranges.
B) INTERFERENCES/LIMITATIONS
Proper use of methods must reflect a consideration of the physical character of the coal, the number and weight of increments,
and the overall precision required.
The system as a whole, including sample cutter, chutes, conveyors, crushers and other devices, should be self-cleaning and non-
clogging. One must be aware that sampling devices not designed for trace material sampling can contaminate the sample (does not
include teflon or polyethylene).
C) RECOMMENDED USE AREA
This is the recommended environmental assessment procedure for mechanical solid (coal) sampling.
5. OPERATIONAL PARAMETERS
A) RANGE Sampling rates are governed by the specifications and/or limitations of the manual or automatic methods used.
(See Table 01-03-01-02A.)
B) ACCURACY The sampling accuracy of < ±1/10 of the ash content of the sample can be attained, based on calculations for general
and specific sampling procedures for known sampling characteristics. The accuracy of riffle sampling increases as the ratio of
chute width to particle size decreases. Arc-path moving samplers are generally more accurate than straight-line samplers.
C) PRECISION The precision for general and specific sampling procedures based on known sampling characteristics can be
-------
PAGE 2 OF 2 FOR
TITLE SAMPLING OF SOLIDS (COAL) USING STANDARD
MECHANICAL METHODS (CONTINUED)
ID NO. 01-03-01-02
Table 01-03-01-02A. Number and Weight of Increments for General Purpose Sampling Procedure3
{FromASTM, Part 19, D2234-68, 1971, p. 357).
Top Size Range
16 mm (5/8 in. ) and under
Over 16 to 50 mm
(5/8 to 2 in. 1
incl.
Over 50 to 150 mm
(2 to 6 in. )
incl.
Mechanically Cleaned Coal
Minimum number of increments ( 1)
Minimum weight of increments, kg
15
2
- 1
15
6
3
15
15
7
Raw (Uncleaned Coal)
Minimum number of increments t1'
Minimum weight of increments, Ib
Minimum weight of increments, kg
35
2
1
35
6
3
35
15
7
For coals above 150 mm (6 inches top size, the sampling procedure should be mutually agreed up>m in
For quantities up to 1, 000 tons (900, 000 kg), it is recommended that one gross sample represent
the lot. For samples of 1,000 tons or over, several alternative methods are available (see
Reference 057).
-------
PAGE 1 OF 3 FOR
1. TITLE SOLIDS GRAB SAMPLING (LONG-PILE ALTERNATE SHOVEL METHOD)
i IDENTIFICATION CODE
01-03-02-01
3. ABSTRACT OF METHODOLOGY
Grab sampling of solids consists in taking small, equal portions at random or regular intervals from heaps or piles, or during loading/
unloading or discharge from storage bins. Gross samples are taken for each 250 tons of sample, in quantities shown in
Table 01-03-02-01A, in 25-50 equal increments, using a shovel or other similar mechanical means. The entire gross sample is then
crushed using jaw crushers, rollers, etc., with crushing sizes indicated in Table 01-03-02-01B. The sample is then mixed and
reduced by the long-pile, alternate shovel method, followed by coning and quartering, (e.g., piling the sample into a conical heap,
then flattening the cone into a circular cake, followed by marking of the cake into quadrants and taking two opposite quadrants
while discarding the remaining two quadrants) as illustrated in Figure 01-03-02-01A. The sample is then ready for shipment to the
laboratory.
Further subdivision of the sample for analyses can be performed in the laboratory by similar manual methods or by use of riffle
samplers (see 02-01-03-02 for details).
4. APPLICATION- Environmental assessment, engineering evaluation R&D.
A) OPE RATIONAL SCOPE
Methods are applicable to any gross load of solid, whether stationary or during loading/unloading operations.
B) INTERFERENCES/LIMITATIONS
N/Q
C) RECOMMENDED USE AREA
This is the recommended level 1 environmental assessment procedure for the grab sampling of solids (coal, coke, etc.).
5. OPERATIONAL PARAMETERS
A) RANGE A gross sample can be taken for each 909,000 kg (1000 tons) or less, according to quantities shown in Table 01-03-02-01B;
larger tonnages can also be sampled with pre-determined quantities.
8) ACCURACY w% or better
C) PRECISION ±0.5%
6. REAGENTS REQUIRED
N/A
7. EQUIPMENT REQUIRED
Shovel, crushing equipment; sample containers (Polyethylene
bags).
a KEYWORD INDEX: Solids, grab sampling, shovel method.
9. CROSS REFERENCE ID NUMBERS 02-01-03-02; 02-02-02-02, 02-02-02-07, 02-02-02-08.
10. REFERENCES
A) PRIMARY SOURCE
057 ASTM Committee D-3 and D-5, "Gaseous Fuels; Coal and Coke," 1971 Annual Book of ASTM Standards, 0346-35, Part 19, "Standard
Method of Sampling Coke for Analysis," p. 50-56, American Society for Testing and Materials, Philadelphia, PA., 1971, p. 50-56
018 Flegal, C.A., M.L. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Procedures for Process Measurements: Trace
Inorganic Materials," EPA Contract No. 68-02-1393, TRW Systems Group, July 1975, p. 5-1.
B) BACKGROUND INFORMATION . , „ L
nlK ASTM Committee D-2 and F-7, "Petroleum Products LPG, Aerospace Materials, Sulfonates, Petrolatum Wax 1971 Annual BOOK
015 of ASTM Standards, Part'18, 0270-65, "Sampling Petroleum and Petroleum Products," American Society for Testing and Materials,
Philadelphia, PA., 1971, p. 47-71.
C) FIELD APPLICATIONS
079 Fieldner, A.C., and W.A. Selvig, "The Determination of Moisture in Coke," U.S. Bureau of Mines Technical Paper
No. 148 (1971).
-------
TITLE SOLIDS GRAB SAMPLING (LONG-PILE ALTERNATE SHOVEL METHOD)
(CONTINUED)
PAGE 2OF3 FOR
ID NO. 01-03-02-01
Table 01-03-02-01A. Sample Types and Minimum Weights of Gross Samples (Reference 057).
Sample Type
Minimum
Weight of
Gross Samples,
kg (1b)
Run-of-oven, blast-furnace, foundry, water-gas, and any coke containing a range of size of pieces made
from uncrushed or coarsely crushed coal**, except coke breeze.
Run-of-oven, blast-furnace, foundry, water-gas, and any coke containing a range of size of pieces made
from crushed coals***, except coke breeze.
Closely-sized coke made from uncrushed or coarsely crushed coal** free of coke breeze.
Closely-sized coke made from crushed coal*** free of coke breeze.
Coke breeze (all passing a 1.27- or 1.90-cm (1/2- or 3/4-in.) square-hole sieve).
228 (500)*
111 (250)*
114 (250)*
57 (125)*
57 (125)*
*In case the pulverization of the coal is not known, take quantities designated for coke made from uncrushed or coarsely crushed
coal.
**More than 10 percent on a 0.635 cm (1/4-in.) square-hole sieve.
***Not less than 90 percent passing through a 0.635 cm (1/4-in.) square-hole sieve.
Table 01-03-02-01B Weights of Coke Samples with Corresponding Crushing Sizes (Reference 057).
Weight of Sample to be Divided, kg (Ib.)
Largest Size of Coke and Impurities
Allowable in SampleBefore Division,
cm. (in.)
114 (250) or over
57 (125)
27 (60)
14 (30)
2.54 (1)
1.90 (3/4)
1.27 (1/2)
0.635 (1/4)
66
-------
CRUSH 1,000-POUND SAMPLE 1,000-POUND SAMPLE
ON HARD, CLEAN SURFACE CRUSHED TO 1" AND
TO 1" SIZE CONED
CRUSH 500-POUND SAMPLE
(FIG. 5, A) TO 3/4" SIZE
500 POUNDS CRUSHED TO
3/4" AND CONED
MIX BY FORMING LONG PILE.HALVING BY ALTERNATE LONG PILE DIVIDED INTO
A - SPREADING OUT FIRST SHOVEL METHOD. SHOVELFULS TWO PARTS:
1,3,5, ETC. .RESERVED AS 5,A; A RFSFRVF- R Be IFfT
COMPLETED 2,4,6, ETC., REJECTED AS 5,B A RE5ERVE' B - REJECT
SHOVELFUL
B-LONG PILE i
10
MIX BY FORMING LONG PILE. HALVING BY ALTERNATE LONG PILE DIVIDED INTO
A-SPREADING OUT FIRST SHOVEL METHOD. SHOVELFULS TWO PARTS-
SHOVELFUL. 1,3,5,ETC, RESERVED AS 10,A; A . RESERVE'; B - REJECT
B -LONG PILE COMPLETED. 2.4,6, ETC'., REJECTED AS 10,6.
NOTE
SELECT A HARD, CLEAN
SURFACE, FREE OF
CRACKS AND PROTECTED
FROM RAIN, SNOW,
WIND, AND BEATING
SUN. DO NOT LET
CINDERS, SAND, CHIP-
PINGS FROM FLOOR, OR
ANY OTHER FOREIGN
MATTER GET INTO THE
SAMPLE. PROTECT
SAMPLE FROM LOSS OR
GAIN IN MOISTURE.
13
15
CRUSH 250-POUND SAMPLE 250 POUNDS CRUSHED TO MIX BY FORMING NEW CONE QUARTER AFTER FLATTENING SAMPLE DIVIDED INTO RETAIN OPPOSITE QUARTERS
(FIG. 10,A) TO 1/2" SIZE 1/2" AND CONED CONE QUARTERS A,A. REJECT QUARTERS B,B.
FIRST STAGE
IN THE
PREPARATION
OF A 1,000-LB
SAMPLE
SECOND STAGE
THIRD STAGE
H
m
8
o
3)
e
o
<
CRUSH 125-POUND SAMPLE MIX BY ROLLING ON
(FIG. 16: A, A) TO 3/8" SIZE BLANKET
FORM CONE AFTER MIXING QUARTER AFTER FLATTENING SAMPLE DIVIDED INTO
CONE QUARTERS
FOURTH STAGE
RETAIN OPPOSITE QUARTERS
A, A. REJECT QUARTERS B,B.
o
o
c
m
O
23
»--."*3»..
CRUSH 60-POUND SAMPLE MIX BY ROLLING ON
(FIG. 22: A,A) TO 1/4" SIZE BLANKET
27
FORM CONE AFTER MIXING QUARTER AFTER FLATTENING SAMPLE DIVIDED INTO
CONE QUARTERS
FIFTH STAGE
RETAIN OPPOSITE QUARTERS
A, A. REJECT QUARTERS fl,B.
CRUSH 30-POUND SAMPLE MIX BY ROLLING ON
(FIG. 28: A,A)TO3/16" OR BLANKET
TO PASS A 4760-MICRON
(NO. 4) SIEVE
33
FORM CONE AFTER MIXING QUARTER AFTER FLATTENING SAMPLE DIVIDED INTO
CONE QUARTERS
THE LABORATORY SAMPLE TO
BETAKEN FROM A, A.
SIXTH STAGE
Figure 01-03-02-01A. Standard Method of Sampling Coal for Analysis (Reference 057).
s
6
PO
6
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Table of Contents for 01-04 Sampling for Particulate or
Aerosol in Flue Gas
01-04-01 Mass Loading Techniques
01-04-01-01 Sampling Flue Gas for Trace Inorganic
Materials
01-04-01-02 Particulate Sampling in Flue Gas Streams for
Non-Trace Element Constituents
01-04-02 Particle Sizing Techniques
01-04-02-01 Particulate Size Sampling in Flue Gas Streams
01-04-02-02 Level 1 Environmental Assessment Flue Gas
Sampling Train
69
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APPLICATION MATRIX FOR 01-04 PARTICULATE OR AEROSOL SAMPLING IN FLUE GAS
METHOD
01-04-01-01
01-04-01-02
01-04-02-01
01-04-02-02
LEVEL I
ENVIRONMENTAL
ASSESSMENT
•
COMPLIANCE
•
ENGINEERING
EVALUATION
R/D
•
•
•
70
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SAMPLING FOR PARTICULATE OR AEROSOL IN FLUE GAS - ID No. 01-04
To obtain a representative particulate sample, general flue gas
sampling concepts must be followed. When sampling particles in a flue gas
stream, the prime consideration is to sample the gas isokinetically
(reference 084). If the sample velocity is below isokinetic conditions,
too many large particles will be collected. On the other hand, too many
small particles will be collected if the sampling rate is faster than
isokinetic conditions. Also, the long axis of the sampling head must be
parallel to the direction of the gas flow. In this case, too few large
particles will be collected at the sampling head. It is extremely impor-
tant to avoid collecting size-weighted samples, since it has been shown
(references 081, 082, 083) that trace elements show a definite trend
in concentration with particle size- Any size weighting of the collected
material would affect the concentration of trace elements in a nonrepre-
sentative manner.
The sampling probe itself should be capable of resisting corrosion in
the environment of the gas stream. Furthermore, the probe and sampling
lines should be heated to 25°C over the stack temperature to prevent con-
densation of water vapor or other borderline vaporous compounds.
01-04-01 Mass Loading Techniques
(Abstracts 01-04-01-01 through 01-04-01-02)
When sampling flue gas for particulates, a decision must be made before
the probe is inserted in the stack as to whether trace material or non-
trace material is going to be sampled. Furthermore, if trace materials are
to be sampled, the specific elements of interest must be known. This
decision will have an impact on quality control, equipment design, and
laboratory procedures. Obviously, if nontrace materials are to be sampled,
the degree of quality control and analytical sensitivity is reduced and
thus reagent quality chemicals (02-01-01-01) and acids can be used rather
than high purity reagents (02-01-01-06). By the same token if the analyst
knows what elements he wishes to collect, even nontrace element trains can
be used. For example, if the analyst is interested in As, Se, or Pb, an
unlined 316 SS probe could be used rather than the recommended probe
71
-------
(01-04-01-01), since the common contaminates (Fe, Cr, Ni) will not be
measured. However, each case must be decided individually by asking these
questions:
1) Will the train contribute contamination to the collected sample?
2) Will the train modify or irreversibly retain the species or element
of interest?
3) What precision and accuracy is acceptable?
The size of the sample to be collected is determined by the sensitivity
and detection limit of the analytical procedures to be employed and the
background levels of the materials of interest. For trace analysis methods,
the required element sample sizes range from 10 to 1,000 pg. For a stream
3 3
containing 60 ug of an element of interest per m, between 0.2 and 15 m
(7-420 ft3) will need to be sampled in order to furnish an adequate sample
size. It is clear that in order to acquire this sample in a reasonable
3
period of time (two hours or less) a sampling rate of the order of 0.2 m /
o
min (5 ft /min) is required.
If one is interested in factor-of-two survey methods (Level 1
environmental assessment) the high volume cyclone train (01-04-02-02) is
recommended. If nontrace elements or trace elements other than Fe, Cr, Ni,
Mo, Mn, Cu, and V are to be sampled, then the unmodified HVSS train can
be used (01-04-01-02). If there is any doubt about compatibility, then
the recommended trace material sampling train must be used (01-04-01-01).
01-04-02 Particle Sizing Techniques
(Abstracts 01-04-02-01 through 01-04-02-02)
Both in-stack and out-of-stack particle sizing equipment is available.
The utility of each approach is mainly dictated by the mass loading and
particle size distribution in the gas stream. Out-of-stack sizing methods
work where low mass loadings and smaller particle sizes (<3p) are
found. Typically these conditions occur after process control equipment
such as electrostatic precipitators or wet scrubbers. Since the particles
are small, the chance of collecting particles in the probe and sampling lines
is minimized. The Source Assessment Stack Sampler (SASS) (01-04-02-01) uses a
series of cyclones (<10y, <3y, < lu) to fractionate the particulates out-
side of the stack.
72
-------
The SASS train utilizes a flowrate of 4 cfm so that sampling periods
are kept to a minimum. This train is designed to be a survey tool for
environmental assessment of pollution sources and is the recommended Level 1
environmental assessment train.
In-stack particle sizing employs cascade impactors. By eliminating
the probe and sampling lines, particle loss is essentially eliminated.
Many units are on the market, but the MRI unit (01-04-02-01) has the best
design and field utility of the commercial units. The MRI impactor is made
of aluminum (or 316 SS) and is designed to be placed in the stack (7.62 cm
or 3 in. diameter part required). Its high flowrate (up to 1 cfm) and
simple design aids in the collection and removal of samples particle.
REFERENCES
080 Faith, W.L., and A.A. Atkisson, "Air Pollution," John Wiley, 1972,
p. 110.
081 Davison, R.L., et al, "Trace Elements in Fly Ash: Dependence of
Concentration on Particle Size," Environ. Sci. Tech.. 8(13), 1107
(1974).
082 Lee, R.E., H. Christ, K. MacLeod and A. Riley, "Concentration and
Size of Trace Metal Emissions from a Power Plant, a Steel Plant and
a Cotton Gin," Environ. Sci. Tech.. 9_(7), 643 (1975).
083 Lee, R.E., R. Enrione, S. Goranson and G. Morgan, "National Air
Surveillance Cascade Impactor Network: II. Size Distribution
Measurements of Trace Metal Components," Environ. Sci. Tech.. 6_(12),
1025 (1972).
084 "Methods of Air Sampling and Analysis," American Public Health
Association, Washington, D. C., 1972.
73
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PAGE 1 OF 2 FOR
1. TITLE SAMPLING FLUE GAS FOR TRACE INORGANIC MATERIALS
2. IDENTIFICATION CODE
01-04-01-01
3. ABSTRACT OF METHODOLOGY
This procedure is designed to sample flue gas streams for trace inorganic materials. A standard Aerotherm high volume
stack sampler (HVSS) was modified in 3 areas: 1) the probe was lined with an inner removable liner made of Kapton
polyimide film to prevent nickel, chromium and other stainless steel elements from contaminating the participate catch;
2) Gelman Spectrograde type A glass fiber filter was used as the filtering medium and 3) a special oxidative impinger
system was developed to sample vaporous elements such as arsenic, mercury, selenium and antimony. The oxidative system
consisted of four impingers: one impinger with 3M H202, two impingers with 0.2 M (NH4)2 S20g plus 0.02 M ftgN03 and a fourth
impinger with Drierite. The impinger nozzles were coated with Teflon to prevent corrosion of the SS components due to the
oxidative solutions. Figure 01-04-01-01A shows the Aerotherm high volume stack sampler and Figure 01-04-01-01B is a schematic
diagram of a Kapton liner inside the probe tube.
4. APPLICATION: Engineering evaluation R&D
A) OPE RATIONAL SCOPE
This system is designed to operate in a flue gas stream at temperatures up to 450°C. The sampling rate reaches
90 1pm (3 cfm). This system is primarily designed for trace material sampling, but can also be used to collect
information on mass loadings.
8) INTERFERENCES/LIMITATIONS
While the Kapton lined probe can operate up to 450°C, Teflon gaskets and coated hardware are not compatible with temperatures
much above 270°C. The Aerotherm system is also heavier and larger than low volume Method 5 type samplers. Cleaning the
cooling coils can be difficult and time-consuming, and they also show potential for corrosion or impinger sample contamination.
While manufacturer specifications indicate that a sampling rate of 180 1pm (6 cfm) is possible, present field sampling has
demonstrated that a sampling rate of 90 1pm (3 cfm) is possible with the present configuration.
C) RECOMMENDED USE AREA
This train is recommended as an engineering evaluation R&D trace element sampling train for flue gas streams.
5. OPERATIONAL PARAMETERS
A) RANGE The flow rate of the trace material sampling train approaches 90 1pm.
B) ACCURACY The oxidative impinger system was to be a hundred percent efficient for sampling gaseous mercury.
C| PRECISION The original Aerotherm HVSS was designed as a Method 5 sampling train; consequently, the built-in precision
was better than ±10%.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
High purity water, ammonium persulfate, silver nitrate,
Drierite, nitric acid, hydrochloric acid.
Aerotherm high volume stack sampler, Kapton film, bushing
inserts, (for a complete list of equipment to perform a 2-point,
20-run gas test, see Ref. 018).
& KEYWORD INDEX: Flue gas sampling, trace material sampling.
9. CROSS REFERENCE ID NUMBERS 01-01-01-05; 02-02-01-05.
10. REFERENCES
A) PRIMARY SOURCE
018 Flegal, C.A., M.L. Kraft, C. Lin, R F. Maddalone, J.A. Starkovich and C. Zee, "Procedures for Process Measurements
of Trace Inorganic Materials," TRW Systems Inc., EPA Contract 168-02-1393, July 1975. Access Measurements
B) BACKGROUND INFORMATION
Cl FIELD APPLICATIONS
025 rl^l* C'V ";L' Kraf.t\C- u"> R-f.' Maddalone, J.A. STarkovich and C. Zee, "Final Report for Measurement
in press65 Inor9anlc Trace Materials in Control Systems, Streams," TRW Systems Group, EPA Contract *68-02-1393,
-------
PAGE 2 OF 2 FOR
TITLE SAMPLING FLUE GAS FOR TRACE INORGANIC MATERIALS (CONTINUED)
10 NO. 01-04-01-01
OVEN
STACK TEMPERATURE T.C.
< g
PROBE TEMPERATURE T.C.
CYCLONE I
FILTER
PITOT A?
MAGNEHELIC
OVEN! 1
T.C.
IMPINGER IMPINGER
PAS MFTFP ADJUSTMENT .- •
GAS METER BY PASS VALVE ICE BATH
T.C. /
COARSE
ADJUSTMENT
VALVE
VACUUM
GAUGE
AIR TIGHT
VACUUM
PUMP
DRY TEST METER
ORIFICE 4P
MAGNEHELIC GAUGE
Figure 01-04-01-01A. Aerotherm High Volume Stack Sampler Schematic.
UNION
FITTING KAPTON LINING
STAINLESS STEEL PROBE
STAINLESS STEEL BUSHING
Figure 01-04-01-018. Schematic Diagram of Kapton Liner Inside Probe Tube.
VACUUM
LINE
75
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PAGE 1 OF 2 FOR
_._. e PARTICULATE SAMPLING IN FLUE GAS STREAMS FOR NON-TRACE
1. TITLL ELEMENT CONSTITUENTS
2. IDENTIFICATION CODE
01-04-01-02
3. ABSTRACT OF METHODOLOGY
Table 01-04-01-02A shows representative equipment for non-trace material sampling. Table 01-04-01-02A lists several isokinetic sampling
trains. Depending on the grain loading in the gas stream, either high volume (Aerotherm HVSS) or low volume (Joy EPA) sampling trains
can be used. The final choice will ultimately depend on the analytical method.
4. APPLICATION^ Compliance, engineering evaluation R&D
A) OPERATIONAL SCOPE
These systems can be used in most flue gas streams at temperatures up to 250°C. Glass-lined probes are available for extremely
corrosive streams and for compliance testing.
B) INTERFERENCES/LIMITATIONS
One must realize that the sampling train can contaminate the collected samples. This awareness will dictate the choice of chemical
tests that can be performed so that meaningful data will be generated. For example, the stainless steel components will add Ni, Cr,
Fe to the particulate catch, so chemical analyses for these elements would be worthless due to contamination (see 01-04-01-01).
C) RECOMMENDED USE AREA
These sampling trains are recommended for non-trace material sampling for engineering evaluation. When a low volume train (1-2 cfti)
is used, then this method conforms to compliance testing for mass loading.
5. OPERATIONAL PARAMETERS
A) RANGE
Up to 250°C and most flue gas environments. Special probes (Quartz and Inconel) are available from manufacturer.
B) ACCURACY
±10%
C) PRECISION
±10%
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
The exact reagents required will be dictated by the goal of
the sampling task. See 01-01-01-05 for specific examples.
See Table 01-04-01-02A.
a KEYWORD INDEX: Sampling, particulate sampling.
9. CROSS REFERENCE ID NUMBERS 01-04-01-011 01-01-01-01, 02, 03, 04, 05.
10. REFERENCES
A) PRIMARY SOURCE
085 Stern, A.C. (ed), "Air Pollution," Academic Press, New York, 2:, 1968.
019 U. S. Environmental Protection Agency, Federal Register 36, No. 234, 24838, December 23 1971
B) BACKGROUND INFORMATION
026 "Air Sampling," Am. Conf. Gov. Ind. Hyg., 4th ed., Cincinnati, Ohio (1972).
•085 "Collaborative Study of Method for the Determination of Particulate Matter Emissions from Stationary Sources (Fossil Fuel-Find
Steam generators)," EPA 650/4-74-021, June 1974.
086 "Collaborative Study of Method for Determination of Particulate Matter Emissions from Stationary Sources (Municipal Incinerators),
EPA 650/4-74-022, April 1974.
087 "Collaborative Study of Method for Determination of Particulate Hatter Emissions from Stationary Sources (Portland Cement
Plants)," EPA 650/4-74-029, May 1974.
C) FIELD APPLICATIONS
025 Flegal, C.A., M.L. (Craft, C. Lin, R. F. Maddalone, J.A. Starkovich and C. Zee, "Final Report; Measurement Techniques for Inorgani
Trace Materials in Control System Streams ," EPA Contract No. 68-02-1393, TRW Defense and Space Systems, Redondo Beach, Ca.,
76
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PAGE 2 OF 2 FOR
TITLE PARTICULATE SAMPLING IN FLUE GAS STREAMS FOR NON-TRACE ID NO.
ELEMENT CONSTITUENTS (CONTINUED)
01-04-01-02
Table 01-04-01-02A.
Operating Principle
Construction
Size Cut-offs
Air Flowrates
Weight (complete)
Aerotherm HVSS
Gas sampled isokinetically
and passed through a
cyclone, filter and
impinger system
Stainless steel, teflon,
line hose, viton seals,
Lexan impingers
> 3p cyclone on filter
remainder
Up to 5 cfm
•»80 kg (175 Ib)
JOY EPA
Same as Aerotherm
HVSS
Stainless steel,
ball joints,
glass lines and
glass impingers
> 3y cyclone
(optional)
remainder on
filter
Up to 3 cfm
«• 50 kg (110 Ib)
Lear-Siegler PM-100
Same as Aerotherm
HVSS
Stainless steel, ball
joints, glass lines
and glass impingers
> 1.5u remainder
on filter
Up to 3.5 cfm
MS kg (105 Ib)
Rader Pneumatics
Gas sampled isokinetically
and parti cul ate collected
in filter
All aluminum with silicone
gaskets
None available
Up to 65 cfm
12.3 kg (27 Ib)
77
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PAGE 1 OF 2 FOR
1. TITLE PARTICULATE SIZE SAMPLING IN FLUE GAS STREAMS
2. IDENTIFICATION CODE
01-04-02-01
3. ABSTRACT OF METHODOLOGY
Inertial impactors separate particles on the basis of their aerodynamic size. The sample is drained isokinetically from the source. The
sample gas then passes through a series of jet stages. The sample velocity is increased by each stage, thereby imparting an increased
inertia to the entrained aerosol. Particles achieving a sufficient inertia to escape the flow stream are impacted on the collection
disc located below each jet stage, as shown in Figure 01-04-02-01A. In practice, Mylar liners coated with a grease (typically Apiezon L)
are added to prevent particle bounce or re-entrainment of the particles. These liners reduce the weighing problems by eliminating the
need to weigh the particles on aluminum or stainless steel collection plates. Table 01-04-02-01A summarizes the characteristics of
several commercially available impactors.
4. APPLICATION' Engineering evaluation R&D
A) OPERATIONAL SCOPE
This technique can be used in all flue gas streams and is only limited by the corrosive nature of stream. The MRI unit can be made
out of 316 stainless steel. The maximum normal operating temperature is 225°C. The MRI unit does not require a probe, since it is
inserted directly into the stack.
B) INTERFERENCES/LIMITATIONS
Except when the Brink unit is used, liquid aerosol streams cannot be sampled. The maximum weight per stage is 10 mg, which makes
the chemical analysis difficult.
C) RECOMMENDED USE AREA
The MRI unit is recommended for engineering evaluation R&D for particles in flue gas at low gas loadings. The Brink unit is
recommended for liquid aerosol collection and for particles in flue gas at high grain loadings.
5. OPERATIONAL PARAMETERS
A) RANGE
Up to 225°C
B) ACCURACY
N/Q (±10% estimated)
C) PRECISION
N/Q (±10% estimated)
6. REAGENTS REQUIRED
Apiezon L, Mylar, high purity water, acetone.
7. EQUIPMENT REQUIRED
MRI Model 1502 (MRI, Altadena, California) or the Brink BMS-11
with deep cups (Monsanto Envirochem, St. Louis, Mo.), pumps
(1 cfm flowrate), metering system, probe (only for Brink).
KEYWORD INDEX: Sampling, particle sizing, MRI, Brink.
9. CROSS REFERENCE ID NUMBERS See appropriate analytical method.
10. REFERENCES
A) PRIMARY SOURCE
026 'American Conference of Governmental Industrial Hygienists, "Air Sampling Instruments," Cincinnati, Ohio, 4th ed., 1972.;
B) BACKGROUND INFORMATION
Meeting'of Wl.^.^ \t«&^* Cas«de **»<*>**.• P-per delivered at 65th
088
C) FIELD APPLICATIONS
089 Brink, I.A., "Cascade Impactor for Adiabatic Measurements," Ind. Eng. Chem.. SOUK 645 (1958)
090 Ensor, D.S., et al , J. Colloid Interface Sci.. 38, 242 (1972).
78
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PAGE 2 OF 2 FOR
TITLE PARTICULATE SIZE SAMPLING IN FLUE GAS STREAMS (CONTINUED)
ID NO. 01-044)2-01
Table 01-04-02-01A.
Model Specifications
Operating Principle
Construct! on
Collection Stages
Range (Microns)
Air Flow Rate (cfm)
Backup Filter
Nozzle Sizes (mm)
Collection Efficiency
Dimensions
Height
Features
Opti ons
Brink Deep Cup
Impactor
Multijet out of stack
Stainless steel
5 stage
0.25 to 2.5
0.01 to 0.1
Not included
1.5. 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, and
15
Practically \00%
3.8 cm x 38 cm
(1.5 inch x 15 inches)
2.3 kg (5 Ibs)
Deep cups to collect
up to 3 ml of liquid
BMS-11 is complete
sampling kit
^
V
|*F
r
[jjes
Pollution Control Systems Cascade
Impactor, Mark V
Multijet
in stack
Stainless steel
12 stage
0.2 to 20
0.10 to ]
.00
Not included
1/4, 3/16, 3/3, 1/2
Practically 100%
7.6 cm OD 35.6 cm
(3 inch OD - 14 inch)
4.6 kg (10 Ibs)
Minimal blowoff and handling
losses
Cyclone attachment available
2
VUVfeA
(
P
ill
J(
ir
T
r
: f
I' 1 jj
X j
-J^-J
""ipS
Meteorology Research
Impactor Model 1503
Multijet in stack
Aluminum
7 stage
0.3 to 30
0.1 to 1.0
47 mm glass fiber
filter
1/8, 3/16, 1/4, 5/16,
3/8, 7/16, 1/2
Practically 100%
6.99 cm OD 29.2 cm L
(2 3/4 inch OD -
11 1/2 inch L)
1.6 kg (3.5 Ibs) (Al)
Minimal blowoff and
handling losses
Heating mantel , Miin-
less steel body (11502)
Figure 01-04-02-01A. Schematic of Inertial Impactor.
79
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PAGE 1 Of 2 FOR
1. TITLE LEVEL 1 ENVIRONMENTAL ASSESSMENT FLUE GAS SAMPLING TRAIN
Z IDENTIFICATION CODE
01-04-02-02
ABSTRACT OF METHODOLOGY
In order to sample a flue or duct in such a way that particulate size is measured during the sampling process, a sampling train was
designed to collect large quantities of particulate matter, size classified in the ranges of: (a) 10u , (b) 3^-lOp and (c) In to 3u,
with a final filter to provide a sub-micron size cut (Figure 01-04-02-02A). The sampling train consists of a stainless steel probe
which enters an oven module containing three cyclones and a filter designed to give the particulate delineation mentioned above. The
oven module 1s followed by an impinger system designed to entrap volatile trace elements (based on 01-01-01-05) with the pumping
capacity supplied by one or more high volume vacuum pumps. Necessary pressure, temperature, flow and power conditions are obtained
from a main controller. The entire system is represented schematically in Figure 01-04-02-02B.
For level 1 environmental assessment, a pseudo isokinetic (single initial isokinetic calculation at start of sampling) sampling will
be used to provide survey data on a qualitative, semi-quantitative basis.
4. APPLICATION^ Level 1 environmental assessment.
A) OPERATIONAL SCOPE
This system is designed to operate up to 205°C in flje gas streams.
B) INTERFERENCES/LIMITATIONS
This system is designed to operate unattended and unsequentially if the degree of non-isokinetic sampling varies widely.
Probe, cyclones and tubing are made out of Inconel or 316 SS and will contaminate the sample with Fe, Cu, and Ni.
C) RECOMMENDED USE AREA
Level 1 environmental assessment.
OPERATIONAL PARAMETERS
A) RANGE Up to 700°C
B) ACCURACY Factor of 2
C) PRECISION Variable
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
(W4)2S208, AgN03, High purity H20,
Environmental Assessment Train (Aerotherm Corp.,
Mountainview, Ca.).
KEYWORD INDEX: Sampling, environmental assessment train.
9. CROSS REFERENCE ID NUMBERS 01-01-01-05| 02-01-03-03, 04, 05, 06.
10. REFERENCES
A) PRIMARY SOURCE
091 Sales Literature,
(Private
B) BACKGROUND INFORMATION
092
corp-Hountalnview-
Cal1bration of series cycione
C) FIELD APPLICATIONS
093 Clausen, J., A. Grant, 0. Moore and S. Reynolds, "Interim Report: Field Sampling for Cvtotoxicitv Test Samoles Usino a
Cyclone Sampling Train," TRW Systems Group, Redondo Beach, California, EPA tontract #68-02-1412;October 1975! 9
Series
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PAGE 2 OF 2 FOR
TITLE LEVEL 1 ENVIRONMENTAL ASSESSMENT FLUE GAS SAMPLING TRAIN (CONTINUED)
Figure 01-04-02-02A. Photograph of Probe, Cyclones and Filter.
, CONVECTION
OVEN
FILTER
GAS COOLER
GAS X X
TEMPERATURE -// \
T.C.
CONDENSATE
COLLECTOR
IMP/COOLER
TRACE ELEMENT7
COLLECTOR
10 CFM VACUUM PUMP
Figure 01-04-02-02 B. System Schematic.
81
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Table of Contents for 01-05 Sampling for Fugitive Gas Emissions
01-05-01 Absorption in Liquids
01-05-01-01 Nitrogen Dioxide Content of the Atmosphere
Using the Griess-Saltzman Reaction ,
01-05-01-02 Oxidant (Ozone) Content of the Atmosphere
01-05-01-03 Sulfur Dioxide Content of the Atmosphere
(West-Gaeke Method)
01-05-02 Adsorption on. Solids
01-05-02-01 Fugitive Gas Sampling with Direct Reading
Colon metric Detection Tubes
01-05-02-02 Sampling for Lead in the Atmosphere
01-05-02-03 Impregnated Paper Tape Methods for Determina-
tion of Hydrogen Sulfide in Air
01-05-02-04 Fugitive Gas Sampling by Adsorption on Solids
(Carbon, Silica)
01-05-03 Condensation Techniques
01-05-03-01 Fugitive Gas Sampling by Condensation
Techniques
01-05-04 Fugitive Gas Grab Sampling
01-05-04-01 General Fugitive Gas Grab Sampling Techniques
01-05-04-02 Fugitive Gas Grab Sampling Using Plastic Bags
83
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APPLICATION MATRIX FOR 01-05 SAMPLING FOR FUGITIVE GAS EMISSIONS
METHOD
01-05-01-01
01-05-01-02
01-05-01-03
01-05-02-01
01-05-02-02
01-05-02-03
01-05-02-04
01-05-03-01
01-05-04-01
01-05-04-02
LEVEL I
ENVIRONMENTAL
ASSESSMENT
•
•
•
•
•
•
•
COMPLIANCE
•
•
•
ENGINEERING
EVALUATION
R/D
e
n
9
•
•
•
84
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SAMPLING FOR FUGITIVE GAS EMISSION- ID No. 01-05
The differences between flue gas and fugitive gas sampling are more
a matter of degree rather than kind. All of the procedure categories
for flue gas sampling are applicable to fugitive gas emission sampling, and
the reader is directed to 01-01 for a detailed discussion of the problems
associated with the different procedure categories. This introduction
will discuss the problems associated with fugitive gas sampling, and
briefly review the compiled methods.
Sampling for fugitive emissions around a plant will involve sampling
vents (atmospheric and high pressure) as well as closed areas surround-
ing a pollution source (for example, the building housing an open
hearth) and boundaries of the plant parameter. All vents to the atmosphere
require a means of access as well as a suitable working space for personnel
involved in the sampling process. Vent systems generally consist of relief
tubes or exit ducts regulated by in-line pressure release valves. Vents
of this type are found in holding tanks and storage tanks and are usually
released into the air when the tank pressure exceeds the pressure setting
of the in-line valve. The velocity of the gases being emitted from vent
systems, as well as the time duration of the vent cycle, is directly
proportional to: 1) the diameter of the vent tube, 2) the headspace volume
of the system being vented, and 3) the pressure setting of the in-line
relief valve.
Important considerations in obtaining a representative sample from
these sources are:
• The sample must be taken while the vent cycle is in progress.
(Cycle periods for individual processes should be known as a
result of the pre-test survey).
t The entrance nozzle of the sampling unit should be situated in
such a way that a representative sample of the vent effluent is
obtained without contamination by ambient air.
85
-------
Manufacturing, process, or transfer areas either enclosed or open are
major sources of fugitive emissions. Depending on the control devices
present, the emissions can range from slightly above ambient to near flue
gas levels. In all cases, the duration of the sampling period should be
integrated with the cyclic nature of the processes.
In obtaining fugitive boundary samples, the perspective is considerably
altered with respect to the methods which apply to enclosed structure
sampling. Depending on the size of the plant in question, there can be a
multitude of isolated sources,each of which contributes to the overall
particulate population from different locations in the plant. Naturally,
atmospheric mixing will play a role in homogenizing individual emission
sources, but certainly not to a reliable degree.
It is recommended that at least four sample points be established at
equal distances apart in such a way that if the process under investigation
were quartered, each quarter would be represented by one sampler. If
the plant is larger, it can be divided into sixths with one sampler for
each sixth, and etc., depending on the. size of the installation to be
sampled. Consequently, in order to obtain reliable data the decision as
to the position and number of samplers and the sampling time should be
based on:
1) The analytical objectives for the acquired samples - If a
factor of 2 (level 1) analyses are to be performed, then
sampling accuracy can be of the same order (see 01-02 for
statistical explanation).
2) The total land area of the process in question - Larger plants
will require a greater number of sampling points to provide the
proper coverage. Too few sampling points in a large plant
could conceivably miss sampling point sources (stacks, vents,
etc.) due to meteorological conditions.
3) The number of emission sources within the system - In order to
avoid a biased sample when many emission sources exist in the
plant boundaries, the number of sample points should be in-
creased.
86
-------
4) The estimated average fugitive emission concentration - Many
situations will require long sampling periods to obtain
enough sample for analysis. Thus, the time required to sample
will vary inversely with emission concentrations.
5) The number of enclosed structures in which particulate levels
are expected to be high - Obviously, when more sources of
different emissions exist, the network of samplers must also
be increased to obtain representative samples.
6) Cyclic nature of emissions - All plants will have operations that
vary with time. The sample team has the choice to sample for
a period of time to overlap the cycles or to time the sampling
period to the cycle.
By noting the above considerations, a representative sample of fugitive
emissions can be obtained using the methods in this section.
01-05-01 Absorption in Liquids (Abstracts 01-05-01-01 through
01_05:01_03y
The principal inorganic gases that are monitored in fugitive
emissions are N02, S02 and 03 (total oxidant). Standard methods for these
gases employ trapping the gas in a reactive solution, and reacting the
trapped species with a suitable reagent producing a color change.
The Griess-Saltzman reaction (01-05-01-01) is both a sensitive
and accurate method of ambient N02 monitoring. On the other hand, the
current compliance test (KI) for 03 (01-05-01-02) has been under study
(094) to correct the conflicting results sometimes encountered. Included
in these recommendations were:
1. Use of constant voltage transformer as part of the ozone
generation system.
2. Use of midget impingers rather than Saltzman bubblers.
3. Use of higher purity KI.
4. Use of air free of H20, 03, NO, N02, and hydrocarbons.
87
-------
The West-Gaeke test for S02 (01-05-01-03) is widely used for low
level S02 measurements. Recent tests (094) have shown that temperature
control during sampling and storage is necessary to prevent S02 loss.
Temperature control at 20°C or less is adequate to reduce the daily loss
to >1.0%
01-05-02 Adsorption on Solids (Abstracts 01-05-02-01 through
01-05-02-037
The main use of solid adsorbents for fugitive emission sampling is
for direct reading colorimetric detection tubes (01-05-02-01). Activated
charcoal (01-05-02-02) has been used to sample vaporous lead (volatile
inorganic and organic lead). Impregnated filter tapes (01-05-02-03) have
been used to sample H2S.
01-05-03 Condensation Techniques
As in flue gas sampling, however, most inorganic gases of interest
have too low of a boiling point to use condensation as a routine sampling
procedure. The use of condensation- techniques for fugitive gas sampling
is described in 01-05-03-01.
01-05-04 Fugitive Gas Grab Sampling (Abstracts 01-05-04-01 through
01-Q5-04-02T
The same gas containers (01-05-04-01) used for stack gas sampling
(01-01-04) can be used for fugitive emissions. Where temperature and
pressure allow, plastic bags (01-05-04-02) may be used. Plastic bags
are especially useful when low concentrations and large samples are
required.
REFERENCES
094 Personal communication to Ray Maddalone, TRW Systems, from John
Clements, Chief of Methods Standardization and Performance Evaluation
Branch.
-------
1. TITLE NjTROQEM DIOXIDE CONTENT OF THE ATMOSPHERE USING THE GR.ESS-SALTZMAN
3. ABSTRACT OF METHODOLOGY
i IDENTIFICATION CODE
01-05-01-01
The gas sample Is passed through dfi absorbing/color-forming reagent of sulfanllic acid, glacial acetic acid and K-(l-naphthyl)-
ethylenediamine dihydrochloride (NAD-C1). This reagent solution scrubs the N02 from the gas stream ard the MO reacts with the
NAD-C1 to form a red-violet color. The absorbance of this solution is read at 550 nni.
4. APPLICATION- Compliance, level 1 environmental assessment, engineering evaluation R&D.
A) OPERATIONAL SCOPE
This method covers the manual determination of nitrogen dioxide in the atmosphere using fritted bubblers. The method is preferred
when high sensitivity is needed. For higher concentrations, for automotive exhaust, or for samples relatively high in sulfur
dioxide content, other methods should be used (see 01-01-01-02).
B) INTERFERENCES/LIMITATIONS The tenfold ratio of sulfur dioxide to nitrogen dioxide produces no effect. A thirtyfold ratio
bleaches the color to a slight extent. The addition of 1 percent acetone to the reagent before use retards the fading by forming
a temporary addition product with sulfur oxide. Pre-acetone addition permits reading within 4-5 hours without appreciable inter-
ferences. A fivefold ratio of ozone to N02 will cause a small interference. Peroxyacylnitrate (PAN) can give a response of approx-
imately 15-35X of an equivalent molar concentration of N02. Normal PAN ambient air concentrations are too low to cause any signi-
ficant error if an evacuated bottle or syringe method is used to sample concentrations above 5 ppm. (Interference from NO due to
oxidation is possible.) Note: If strong or oxidizing agents are present, the color should be measured in 1 hour if possible to
minimize any loss.
C) RECOMMENDED USE AREA
Compliance testing of fugitive emissions.
& OPERATIONAL PARAMETERS
A) RANGE
B) ACCURACY
C) PRECISION
0.005 ppm to about 5 ppm
N/Q
±1%
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Sulfanilic acid, glacial acetic acid, N-(l-naphthyl)-
ethylenediamine dihydrochloride, nitrate-free water,
sodium nitrate.
Glass manometer, fritted lubber (max. pore size of 60u) flowmeter
pump.
& KEYWORD INDEX: Sampling, N02 sampling.
9. CROSS REFERENCE ID NUMBERS
01-01-01-02.
10. REFERENCES
ffU ASTjf^Standar^Method for Tests for Hltrogen Dioxide Content of the Atmosphere (Griess-Saltzman Reaction)," 1974 Annual Book
of ASTH Standards, Part 26, p. 317.
480 U.S. Environmental Protection Agency, Title 40, Part 50, Chapter 1, Appendix F, Washington, n. L.
B) BACKGROUND INFORMATION (1054)
095 Saltzman, B.E., "Colorimetric Micro Determination of Nitrogen Dioxide in the Atmosphere," Anal. Chem... 26, 1949 U» >•
C) FIELD APPLICATIONS
096
097
n, B.E., "Preparation and Analysis of Calibrated Low Concentrations of 15 Toxic Gases," Anal. Chem.. 33, 1103 (1961).
E., "The Measurement of Nitrogen Oxide in the Air," Atm. Environ.. 81 (1967).
-------
1. TITLE OXIDANT (OZONE) CONTENT OF THE ATMOSPHERE
2. IDENTIFICATION CODE
01-05-01-02
ABSTRACT OF METHODOLOGY
Micro amounts of oxidant (ozone) are collected by absorption in a solution of alkaline potassium iodine. After acidification, the iodine
equivalent to the concentration of the oxidant present in the air is determined precisely and rapidly by spectrophotometric measurement
of the absorption of the tri-iodide ion at 352 nm.
4. APPLICATION- Compliance, level 1 environmental assessment, engineering evaluation R&D.
A) OPE RATIONAL SCOPE
This method covers the determination of low concentrations of oxidant (ozone) in the atmosphere. The method is not specific for
ozone since other oxidants and reducing substances interfere. The interference of sulfur dioxide and nitrogen dioxide can be
eliminated during the analysis of the sample.
B) INTERFERENCES/LIMITATIONS
Oxidizing and reducing substances may interfere with the oxidation of potassium iodide. Sulfur dioxide will not interfere if the
absorbed gas is oxidized with hydrogen peroxide and the excess peroxide boiled off before the acid is added. The oxygen of the
atmosphere does not oxidize the absorbing solution appreciably.
C) RECOMMENDED USE AREA
Compliance.
5. OPERATIONAL PARAMETERS
A) RANGE The limit for detection of ozone collected by the method described is 1 to 16 ug. For higher concentrations,
appropriate dilutions with absorbing solutions must be made.
B) ACCURACY N/Q (According to the primary source, no absolute tests using ozone have been completed).
C) PRECISION Samples collected in parallel and in the same atmosphere give values that are in good agreement with each other.
& REAGENTS REQUIRED
Potassium iodide, sodium hydroxide, glacial acetic acid,
hydrogen peroxide, iodine, DI water.
7. EQUIPMENT REQUIRED
PVC tubing, impinger, air flow meter, air pump,
spectrophotometer.
a KEYWORD INDEX: Sampling, ozone sampling.
9. CROSS REFERENCE ID NUMBERS 02-05-02-02.
10. REFERENCES
A) PRIMARY SOURCE
053 '3*^ Mnth?d,?f TesH,for Ox1dant <°z<"ie) Content of the Atmosphere," 1974 Annual Book of ASTM Standards,
9-oQ» Part 26, p. 327.
B) eGRbuNDINFORMATIONeCt10n A9en°y' TU1e 4°> Pdrt 5°' Chapter ]' A>»>endix D- **h1ngton. D. C.
098 Smith, R.G.,and P. Diamond, "The Micro Determination of Ozone (Preliminary Studies)," Amer.Ind.Hyg Assoc Quart.,
H, 235 (1952).
C) FIELD APPLICATIONS
90
-------
1. TITLE SULFUR DIOXIDE CONTENT OF THE ATMOSPHERE (WEST-GAEKE METHOD)
3. ABSTRACT OF METHODOLOGY
Z IDENTIFICATION CODE
01-05-01-03
A measured air sample containing sulfur dioxide is absorbed in 10 ml 0.4 M sodium or potassium tetrachloromercurate (TCM) using a
midget impinger. This procedure stabilizes the S02 as a dichlorosulfitomercurate complex which resists air oxidation. Ethylene-
diaminetetraacetic acid disodium salt is added to the 0.4 M TCM to prevent heavy metals from oxidizing the S02 prior to stabilization
as the dichlorosulfitomercurate complex. After absorption, any ozone in solution is allowed to decay. The TCM solution is first
treated with sulfamic acid to oxidize any nitrite formed from the absorption of oxides of nitrogen. Formaldehyde and acid-bleached
pararosaniline (containing phosphoric acid to control pH) are added next to the TCM. These reagents react with the sulfite in the
dichlorodisulfitomercurate complex to form an intensely colored compound, pararosaniline methyl sulfonic acid, whose color at a pH
of 1.6 and 548 nm is directly related to the S02 (SOJ) in the TCM.
4. APPLICATION: Compliance, engineering evaluation R&D.
A) OPERATIONAL SCOPE
This method is applicable to collecting and measuring SO- at low levels from fugitive emissions.
B) INTERFERENCES/LIMITATIONS
The interference by oxides of nitrogen are eliminated by sulfamic acid, the ozone by time delay, and the heavy metals by EDTA and
phosphoric acid. At least 60 yg of Fe (III), 10 ng of Mn (II), and 10 iig of Cr (III) in 10 ml of absorbing reagent can be tolerated
in the procedure. No significant interference was found with 10 ug of Cu (II) and 22 ug of V (¥).
C) RECOMMENDED USE AREA
This is the recommended compliance method for sulfur dioxide in fugitive emissions.
5. OPERATIONAL PARAMETERS
A) RANGE 0.003 to 5 ppm S02-
B) ACCURACY N/Q (±15 percent estimated).
C) PRECISION ±4.6 percent.
6. REAGENTS REQUIRED
Potassium chloride, mercury (II) chloride, sulfamic acid,
1-butanol, sodium acetate, EDTA, hydrochloric acid, phosphoric
acid, pararosaniline hydrochloride, formaldehyde, iodine, starch,
sodium sulfite (or SO? permeation tube for calibration purposes).
7. EQUIPMENT REQUIRED
Midget impingers (or liquid absorption systems), flowmeter,
manometer, UV/VIS spectrometer, teflon tubing.
a KEYWORD INDEX: Air sampling, S02 absorption.
9. CROSS REFERENCE ID NUMBERS 02-05-02-03,- 01-01-01-01.
10. REFERENCES
A) PRIMARY SOURCE
053 ASTM, "Tentative Method of Test for Sulfur Dioxide Content of the Atmosphere (West-Gaeke Method)," 1974 Annual
Book of ASTM Standards, Part 26, Method D2914-70T, p. 579.
480 U. S. Environmental Protection Agency, Title 40, Part 50, Chapter 1, Appendix A, Washington, D. C.
B) 099ACKWest>,Up.Dw!?Fa(ndMGAc!0GNaeke, "Fixation of Sulfur Dioxide as Sulfito Mercurate (II) and Subsequent Colonmetric Determination,"
100 Pate; J^i'sffl A™onsl9J6p'. Lodge and G.A. Swanson, I "Nitrite Interference in Spectrophotometric Determination of Atmospheric
101
, "Evaluation of Teflon Permeation Tubes for Use with Sulfur Dioxide," Am^nd-
Hyg. Assoc. J.,_28, 260 (1967).
C) FIELD APPLICATIONS
102 Scaringelll, F.P., B.E. Saltzman and S.A. Frey, "Spectrophotometric Determination of Atmospheric Sulfur Dioxide," Anal. Chem.
39, 1709 (1967).
91
-------
1. TITLE FUGITIVE GAS SAMPLING WITH DIRECT READING COLORIMETRIC DETECTION TUBES
2. IDENTIFICATION CODE
01-05-02-01
3. ABSTRACT OF METHODOLOGY
Gas detection tubes are narrow glass cylinders containing a solid absorbent impregnated with a chemical reagent. This reagent turns
color as a. known volume of the gas is pulled through the tube by means of a small hand pump. The length of the stain on the
absorbing material is directly related to the concentration of the species in the gas sample. The scale corresponding to the concen-
tration may be printed either directly on the tube or on a chart which is provided with the detection tubes. In some cases, the
stains change with time, and thus a reading should be made immediately after sampling. If the detector tubes are to be kept as
evidence, it is recommended that the open ends be sealed.
4. APPLICATION:
Environmental assessment.
A) OPERATIONAL SCOPE
These tubes can be used to sample fugitive emissions for many varieties of gases. Table 01-01 -02-01A lists typical gases that can
be sampled by the Kitagawa gas detection tubes. Detection tubes are also available for many organic gases. Normally, the tubes are
designed to sample gases in a temperature range from 0 to 50°C. It is also assumed that the sampling pressure is 760 millimeters
of mercury. If the conditions deviate widely from these conditions, the appropriate correction factors derived from the gas law
are available for a particular pressure. (See 01-01-02-01 for information on using detection tubes to sample flue gas
streams.)
B) INTERFERENCES/LIMITATIONS ' "
Experience in sampling known concentrations of gas is of great value in training the operator to know whether to measure the length
up to the beginning or the end of the stained front or what portion of an irregular shaped stain to use as a limit. Care must be
taken to see that pump valves and connections are maintained and that all connections are leak-proof. In all cases, one must be com-
pletely aware of possible interferences to the measurement of the gas of interest. These interferences are listed in
Table 01-01-02-01A.
C) RECOMMENDED USE AREA
This is the recommended level 1 environmental assessment fugitive emission survey gas analysis technique.
5. OPERATIONAL PARAMETERS
A) RANGE
See Table 01-01-02-01A for the gas of interest.
B) ACCURACY
The tube reading deviates from the true value by ±25% at most. For many tubes with scales, the deviation is less than ±103!.
C| PRECISION
Precision will depend on the operator. Experience is needed to obtain accurate and precise measurements.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Detector tubes (several possible sources are available: National
Mine Service Co., Pittsburgh, Pa.; Unico Environmental Instruments
Corp., Fall River, Mass.).
Hand pump (Note: The detector tubes normally come in a complete
kit containing hand pump and any equipment necessary to sample
gas using the tubes.}.
KEYWORD INDEX: sampling, detector tubes.
9. CROSS REFERENCE ID NUMBERS 01-01-02-01.
10. REFERENCES
A) PRIMARY SOURCE
026 American Conference of Governmental Industrial Hygienists, "Air Sampling Instruments," Cincinnati, Ohio, 1972, p. S-l
through S-50.
Bl BACKGROUND INFORMATION
Table 01-01-02-01A
C) FIELD APPLICATIONS
Table 01-01-02-01A
92
-------
1. TITLE SAMPLING FOR LEAD IN THE ATMOSPHERE
i IDENTIFICATION CODE
01-05-02-02
3. ABSTRACT OF METHODOLOGY
The sample is drawn through a sampling train consisting of a 0.45 u membrane filter or its equivalent and then through a sampling
tube containing activated carbon. A sample of 150-200 ms is collected. (See 02-01-01-01 for analysis techniques.) This sampling
train separates particulate lead and vaporous lead. Paniculate lead is that sample collected or an 0.4b u filter. Vaporous lead
is that which passes through the 0.45 u membrane filter, and includes various tetraethyllead compounds or their partially decomposed
products or both.
4. APPLICATION'- Engineering evaluation R&D.
A) OPERATIONAL SCOPE
This mathod is primarily intended for measuring weekly averages of: a) vaporous lead in fugitive emissions at concentrations below
0.5 ug/m3 and b) the particulate lead in fugitive emissions at concentrations of 0.01 ug of lead per m of air.
B) INTERFERENCES/LIMITATIONS Particulate lead is an ever-present interference when measuring vaporous lead in ambient air. It
must be excluded from the activated carbon absorber by use of highly efficient filter and filter holder. Leak-proof gas tubing
connections and proper sealing of the filter in the filter holder are necessary to prevent leaks of nonfiltered air. The
particulate lead in air entering the carbon absorber must be reduced to less than 0.01 ug of lead per m3 of air to avoid a positive
interference in measuring vaporous lead.
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D sampling method for vaporous lead in the atmosphere.
5. OPERATIONAL PARAMETERS
A) RANGE Less than 0.5 ug/m3 vaporous lead and between 0.01 to 10 ug/m particulate lead.
B) ACCURACY ±10% (estimated).
C) PRECISION ±102 (estimated).
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Activated charcoal.
Filters (millipore membrane filter, Type HA or equivalent),
filter holder, gas meter, vacuum pump.
& KEYWORD INDEX: Sampling, particulate lead, vaporous lead.
9. CROSS REFERENCE ID NUMBERS 02-02-01-01.
10. REFERENCES
** ' the Atmosphere by C0lorimetric Dithizone Procedure," 1974 Annual Book of ASTH Standards, Part 26, D3112-72-T,
American Society for Testing and Materials, Philadelphia, PA., 1971, p. 633.
B) BACKGROUND INFORMATION
103 Snyder, L.J.. Anal. Chem.. 39. 591 (1967).
104 Snyder, L.J., Anal. Chem., 19, 684 (1947).
105 Henderson, F.R., and L.J. Snyder, Anal. Chem.. 3J, 2113 (1959).
C) FIELD APPLICATIONS
93
-------
, _._. _ IMPREGNATED PAPER TAPE METHODS FOR DETERMINATION OF HYDROGEN
I. IIILC SULF)DE |N AIR
2. IDENTIFICATION CODE
01-05-02-03
3. ABSTRACT OF METHODOLOGY
on nunupt rnllpction of H?S on impregnated paper tapes under controlled conditions (see Table 01-05-02-03A). Tape reagents include
silver nitrate s°vlr cyanide mercuric chloride and lead acetate. The hydrogen sulfide reacts with the tape reagent to form a precipi-
tatefeilveTulfId mercur fiuTflde and lead sulfide) which produces a visible coloration on the paper tape. The optical densities of
the metal sulf de spots are then used as measures of the H2S concentration, using the equation: cone. H2S (PP™ KAD/V, where K is a
constant which depends on the optical design of the densitotter, A is the area of the sulfide spot, D is the diffuse optical density,
and V is the sample volume.
Table 01-05-02-03A. Experimental Conditions Required for Hydrogen Sulfide
Determinations Using Impregnated Tapes (Reference 106).
—
Chemical Impregnant
AgN03
HgCl2
Ag(CN)'
Pb(OAc)2
Optimal Flow Rate
(liters/min/in2)
<60
<15
<10
<5
'^Relative Humidity (RH)
Exposure to Light
Exclude light
-
-
Exclude light
Other Requirements
Avoid temperatures > 40°C; avoid high flow rates
at < }Q% RHH); hold tape by edges only.
Redevelop spots with NH3 when necessary; avoid
high flow rates at < 10'. RH.
RH > 20%; avoid storage > 3 months.
RH > 20%; exclude 502 levels equal to HjS levels;
maintain acidic impregnating solutions. Least
useful .
4. APPLICATION^ Environmental assessment.
A) OPERATIONAL SCOPE . , ,„„(. ,0..ocl
Method is applicable to gas grab sampling of flue gas, fugitive gas emissions, etc., up to approximately 100 C IZ1Z F).
B) INTERFERENCES/LIMITATIONS . , • .„
Moisture must be maintained in order to achieve quantitative collection of H?S. Impregnation of the tapes with glycerol will
eliminate this interference. Other precautions necessary for good quantitative analysis are shown in Table 01-05-02-03A. Silver
nitrate is the most sensitive and specific determination; lead acetate tapes are the least desirable, but are suitable for semi-
quantitative determinations.
C) RECOMMENDED USE AREA
This is the recommended level 1 environmental assessment method for determination of hydrogen sulfide in gaseous effluents.
5. OPERATIONAL PARAMETERS
A) RANGE 0.001 to 50 ppm using silver nitrate tapes.
B) ACCURACY 85% or better.
Cl PRECISION Reproducibility achieved for air containing 0.008 ppm H?S at flow rates and sampling times giving optical densities of
_. ._ft *
=0.005 were ±&%, ±6%, ±12%, ±15% for AgNOa, HgCl2, Ag(CN>2, and Pb(OAc)2 tapes, respectively.
& REAGENTS REQUIRED
Silver nitrate, potassium cyani
acetate, nitric acid, glycerol.
7. EQUIPMENT REQUIRED
Glass fiber tapes (Gelman Type A) or Whatman No. 1,4 or 41 paper
tapes; automatic paper tape sampler (Gelman, Bendlx); densitometer,
& KEYWORD INDEX: Hydrogen sulfide, gas grab sampling, impregnated paper tapes.
9. CROSS REFERENCE ID NUMBERS 01-01-04-01; 01-05-04-01; 02-03; 01-01-01-07
10. REFERENCES
A) PRIMARY SOURCE
106 Natusch,. D.F.S.,, JR. Sewell and R.L. Tanner, "Determination of Hydrogen Sulfide in Air - An Assessment of Impregnated Paper
Tape Methods," Anal. Chem. 46(3). 411, March 1974.
B) BACKGROUND INFORMATION
015 ff™ sCnorteHvHrDnina1,nFfLTf ,^i^^!!;0^^!1C:9^^^L!0ae0adf ^llll^^ -< 18' D242°-66> "SUndard Meth°d
C,
.h.PA
107 ASTM Committee D-l D- 16 and D-17 "Paint Varnish, Lacquer and Related Products," Part 20, D353-47, "Standard Method of
0' Industriai Aromatic
?no U'r' ;ial?deTson' M' Katz and R- Thomas' J. Air Pollut. Control. Assoc.. 16, 328 (1966)
109 A.F. Smith, D.E. Cunningworth and D.A. Jenkins. J. Appl. Chem.'. TTT7l7Tl96n
111 Hi5' Natusch- Clean Air. 4, 69 (1970). --
in Wohlers, H.C., and M. Feldstein, J. Air Poll ut. Control Assoc.. 16, 19 (1966).
-------
PAGE 1 OF 2 FOR
1. TITLE FUGITIVE GAS SAMPLING BY ADSORPTION ON SOLIDS (CARBON, SILICA)
~— •— " •
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
01-05-02-04
Table 01-05-02-04A gives retentivities (practical sorption capacities) of activated carbon for some commonly encountered gases. To
collect samples of vapors having retentivity of over 5«, a metered air stream must be passed through a carbon bed of 3/4 inch (19 mm)
thickness, with contact time of 1/3 seconds or more [1 1/2 in. thickness (3.81 cm) and 2/3 seconds for 5i or less retentivity].
Table 01-05-02-04B gives minimum specifications for activated carbon for sampling heavy gases boiling above 0°C.
Adsorbed gases and vapors may be desorbed from activated carbon by: 1) displacement by superheated steam, and 2) heating under vacuum,
with distilling into cold traps. (See 01-01-02-02)
The adsorbent can also be impregnated with suitable reagents (e.g., lead acetate for H2S, sulfuric acid for NH3) in order to
facilitate sorption of low boiling vapors. (See 01-05-02-03)
4. APPLICATION^ Engineering Evaluation R&D, environmental assessment.
A) OPERATIONAL SCOPE
Method 1s applicable to low boiling vapors (-100 to 0°C) with critical temperatures between 0 and 150°C and to heavier vapors
(boiling above 0°C); applicable streams include product gas, process vents, and ambient air. See Table 01-05-02-04A for list of
applicable samples.
B) INTERFERENCES/LIMITATIONS
Gases having boiling points below -150°C and critical temperature below -50°C (-58°F) (e.g., H2, l<2, 02, CO, CH4) are nonadsorbable
at ordinary temperatures.
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D method for fugitive gas sampling by adsorption on solids, such as carbon or
silica.
5. OPERATIONAL PARAMETERS
A| RANGE Range is generally dependent upon size and design of adsorbers, desorption apparatus, etc. Sensitivity of carbon or silica
for hydrogen sulfide can be improved by using lead acetate or silver cyanide impregnants; for ammonia, sulfuric acid; for arsine,
B) ACCURACY copper and silver oxidation catalysts. (See 01-05-02-01)
N/Q
C) PRECISION
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Activated carbon (see Table 01-05-02-04B for specifications)
or silica; reagents for impregnation of adsorbent.
Adsorber; blower apparatus, superheated steam or vacuum desorption
apparatus, consisting of ice-salt, dry ice and liquid nitrogen traps
connected in series.
& KEYWORD INDEX: Fugitive gas sampling, adsorption on solids, activated carbon, silica gel.
9. CROSS REFERENCE ID NUMBERS 01-05-02-03, 01-05-04-01; 01-01-02-02; 02-03-02; 01-05-02-01
10. REFERENCES
AJ PRIMARY VJl iRf*F
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, J1505-60,
"Standard Recommended Practices for Sampling Atmospheres for Analysis of Gases and Vapors, American iociety tor
Testing and Materials, Philadelphia, PA., 1971, p. 349-370.
B) BACKGROUND INFORMATION
026 American Conference of Governmental Industrial Hygienists, "Air Sampling Instruments for Evaluation of Atmospheric Contaminants,"
Cincinnati, 4th ed., 1972, p. R-4 through R-6.
C) FIELD APPLICATIONS
112 White, L.D., R. Kupel, P. Mauer and D. Taylor, Industrial Hygiene News Report. 12J7), July 1969.
95
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PAGE 2 OF 2 FOB
TITLE FUGITIVE GAS SAMPLING BY ADSORPTION ON SOLIDS (CARBON, SILICA) (CONTINUED)
10 N0- 01-05-02-04
Table 01-05-02-04A. Retentivity of Vapors by Activated Carbon (Reference 024) (Percentage by Weight
Retained in a Dry Air Stream at 20°C, 760 torr).
Substance
Ammonia
Bromine
Chlorine
Hydrogen
Hydrogen
Hydrogen
Hydrogen
Hydrogen
Iodine
bromide
chloride
fluoride
iodide
sulfide
Nitric acid
Nitrogen
Ozone
dioxide
Sulfur dioxide
Sulfur trioxide
Sulfuric
Water
acid
Formula
NH,
•3
Br2
C12
HBr
HC1
HF
HI
H?S
h
HNOj
N02
°3
so2
so3
H2S04
H20
Molecular
Weight
17.0
159.8
70.9
80.9
36.5
20.0
127.9
34.1
253.8
63.0
46.0
48.0
64.1
80.1
98.1
18.0
Normal
Boiling
Point,
Deg C at
760 torr
-33
59
-34
-67
-84
19
-35.4
(4 atm)
-62
183
86
21
-112
-10
45
330
100
Approximate
Retentivity,
Percent at
20°C and
760 torr
negligible
40 (dry)
15 (dry)
8
4
8
15
3 (dry)
40
20
10
decomposes
to oxygen
10 (dry)
15 (dry)
30
none
Characteristics
refrigerant
organic synthesis,
I
I
strong acid
strong acid
strong acid
strong acid
oxidizes to increase retentivity
antiseptic
oxidizing acid
hydrolyzes to increase retentivity
generated by electrical discharge
oxidizes to sulfur trioxide; common in
city atmospheres
hydrolyzes to sulfuric acid
Table 01-05-02-04B. Specifications for Air-Purification Activated Carbon (Reference 024).
Property
Activity for CCl4a
Retentivity for CCl4b
Apparent density
Hardness (ball abrasion)0
Particle size
Specification
at least 50 percent
at least 30 percent
at least 0.42 g/ml
at least 80 percent
passing on No. 6 (3.35-mm) sieve
retained on No. 14 (1.40-mm) sieve
aHaximum saturation of carbon at 20°C and 760 mm, in an air stream equilibrated with
CC14 at 0°C.
Maximum weight of adsorbed CC1. retained by carbon on exposure to pure air at 20°C
and 760 mm.
Percentage of carbon passing a No. 6 (3.35-mm) sieve and largely retained on a No. 8
(2.36-mm) sieve, that remains on a No. 14 (1.40-mm) sieve after vibrating with 30 steel balls
of 0.25 to 0.37 in. in diameter/50 g of carbon, for 30 min.
96
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PAGE 1 OF 2 FOR
1. TITUE FUGITIVE GAS SAMPLING BY CONDENSATION TECHNIQUES
— • '•' "" - ' i .in ,.__
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
01-05-03-01
Sample collection by condensation involves drawing the sample through condensers or U-tube traps which have been cooled below the
boiling point of the gas or vapor.
A representative list of refrigerants is given in Table 01-05-03-01A. Table 01-05-03-01B gives vapor pressure data for several
co»on gases. The vapor pressure of the trapped gases should be 1 torr or lower at trap temperatures. The proper refrigerant is thus
selected accordingly.
A typical condensation trap is a glass sampling tube having inlet and outlet ports. The trap may be used as a flask for isothermal
distillation at progressively higher temperatures. A U-shaped trap which can be set in a Dewar flask can also be used for collection
of gas by condensation.
Table 01-05-03-01A. Refrigerant Temperatures (Reference 024!.
Refrigerant System
02 (liquid) = 02 (gas)
CS2 (solid) CS2 (liquid)
C02 (solid) C02 (gas)
NH3 (liquid) NH3 (gas)
H20 (solid) H20 (liquid)
Temperature,
deg C
-183.0
-118.5
78.5
33.4
0
4. APPLICATION- Engineering evaluation R&D.
A) OPE RATIONAL SCOPE
The method is applicable to all gases having vapor pressures of i 1 nrn at liquid oxygen or higher temperatures. Sampleable
streams include product gas, process vents and ambient air.
B) INTERFERENCES/LIMITATIONS
The formation of condensation mists can reduce the equipment collection efficiency; these can be removed by a simple filter
(glass wool plug).
The main disadvantage of the condensation technique is the cumbersome nature of the equipment, which also requires frequent
attention. The collected sample must be maintained at low temperatures prior to analysis.
C) RECOMMENDED USE AREA
This method is applicable as an engineering evaluation R&D fugitive gas sampling method.
5. OPERATIONAL PARAMETERS
A) RANGE Collection range depends on availability of suitable refrigerants for the sampled vapors; sampling rate depends on
capability of aspirator, pump, etc.
B) ACCURACY 10X or better.
C) PRECISION +10%
6. REAGENTS REQUIRED
See Table 01-05-03-01A for listing of suitable refrigerants.
7. EQUIPMENT REQUIRED
Condensation apparatus (Figure 01-05-03-01A); glass wool plug
aspirators or pumps to facilitate drawing the sample through
the apparatus (see 01-05-04-01).
8. KEYWORD INDEX: Fugitive gas sampling, condensation.
9. CROSS REFERENCE ID NUMBERS 01-01-03-03, 01-05-04-01; 02-02; 02-03.
10. REFERENCES
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTtl Standards, 01605-60, Part 23,
"Standard Recommended Practices for Sampling Atmospheres for Analysis of Gases and Vapors," American Society for
Testing and Materials, Philadelphia, PA., 1971, p. 349-370.
B) BACKGROUND INFORMATION
026 American Conference of Governmental Industrial Hygienists, "Air Sampling Instruments for Evaluation of Atmospheric
Contaminants," 4th ed., 1972, p. R-3 through R-4, R-12 and R-13.
C) FIELD APPLICATIONS
113 Sanderson, T.T., "Vacuum Manipulation of Volatile Compounds," Appendix, Table XVII, Hew York, J. Wiley and Sons,
Inc., 1948.
114 Shepherd, M., et al, Anal. Chem. ANCHA. Vol. 23, p. 1431, 1951.
97
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PAGE 2 OF 2 FOR
TITLE FUGITIVE GAS SAMPLING BY CONDENSATION TECHNIQUES (CONTINUED)
ID NO. 01-05-03-01
Table 01-05-03-01B. Properties of Some Gaseous Atmospheric Contaminants (Reference 024).
Substance
Ammonia
Arsine
Carbon disulfide
Chlorine
Hydrogen chloride
Hydrogen sulfide
Ozone
Sulfur dioxide
Molecular
Wt
17.0
77.9
76.1
70.9
36.5
34.1
48
64.1
Boiling
Point,
deg C
-33.4
-55
46.3
-33.8
-84
-61.8
-112
-10.0
Freezing
Point,
deg C
-77.7
-113.5
-111.8
-102
-112
-82.9
-251
-72.7
Ordinary
State
vapor
vapor
liquid
vapor
vapor
vapor
gas
vapor
Vapor Pressure, torra
20°C
8.46 atm
15.0 atm
295.0
6.6 atm
41.6 atm
17.7 atm
3.2 atm
Ice
4.2 atm
8.4 atm
127.0
3.7 atm
25.5 atm
10.2 atm
. . .
1.5 atm
NH3
-33.4°C
1 atm
2.8 atm
21.0
1 atm
9 atm
3.6 atm
. . .
225
co2
-78.5°C
44.0 (solid)
338.0
0.6
62.0
1.3 atin
259.0
. . .
cs2
-111.8°C
0.6 (solid)
36.0
. . .
2.5 (solid)
120.0
16.0 (solid)
1 atm
8.4 (solid); . . .
°2
-183°C _|
. . .
0.2
. . .
. . .
0.8
0.1 (solid)
0.17
In torr, unless otherwise stated. Vapor pressues are referred to refrigerant temperatures of Table 01-05-03-01A.
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PAGE 1 OF 2 FOR
1. TITLE GENERAL FUGITIVE GAS GRAB SAMPLING TECHNIQUES
2. IDENTIFICATION CODE
01-05-04-01
3. ABSTRACT OF METHODOLOGY
Fugitive gas emissions may be collected by gas or liquid displacement techniques using evacuated containers, as illustrated in
Figures 01-05-04-01A and 01-05-04-01B.
Figure 01-05-04-01A consists of a glass bulb from which air has been removed using a vacuum pump, and the neck of which is sub-
sequently sealed by heating and drawing to & tip. Figure 01-05-04-01B shows an evacuated 3-liter sampling bomb with valve inlet and
styrofoam protector. Both types of sample containers above are suitable for trapping carbon dioxide, methane and other nonreactive
gases. For the sampling of H2S, S02 or NOX an in-line silica gel adsorption tube must be used in order to trap the reactive acid
gases as well as particulate, as illustrated in Figure 01-05-04-01D. To fill the pre-evacuated sample containers, the sealed neck of the
container or the container valve must be opened to admit the surrounding atmosphere.
Figure 01-05-04-01C shows a grab purge apparatus for the collection of sample by gas displacement. The glass vessel is connected
to an aspirator or hand pump at inlet B. A sample container similar to the glass bomb in construction (e.g., having inlet and exit
valves) can be connected to inlet B between the glass vessel and aspirator. The glass vessel is then purged with 10-15 volumes of gas
by aspiration prior to collection of the sample in order to avoid sample contamination by the original contents. The in-line con-
tainer acts as a trap for any air leaks in the aspirator.
4. APPLICATION' Environmental assessment.
A) OPE RATIONAL SCOPE
Method can be used on gaseous process streams, product gas, and ambient air samples for sampling inorganic gases and organics
(CO-, 0,, CH., CO, Ho, N£, C,Hg, etc.) and gases containing sulfur compounds, nitrogen oxides, etc., when suitable adsorption
tubes are included in the sampling train.
B) INTERFERENCES/LIMITATIONS
Acid gases (HjS, S02> nitrogen oxides) and particulates interfere, but may be removed by silica gel absorption tubes positioned
at the inlet end of the sample container (See Figures 01-05-04-01B and C).
C) RECOMMENDED USE AREA
This is applicable to the environmental assessment of fugitive gas emissions.
& OPERATIONAL PARAMETERS
A) RANGE N/A
B) ACCURACY IM or better
C) PRECISION N/Q
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Sealing wax.
Sample containers, gas pumps (aspirators, hand pumps, siphons),
gas metering devices, adsorption tubes.
& KEYWORD INDEX: Gas grab sampling, gas displacement, fugitive emissions.
9. CROSS REFERENCE ID NUMBERS 01-01-04-01, 01-01-04-02; 02-02; 02-03; 02-01-01-07.
10. REFERENCES
* 024R'MARASTMUfo"ttee D-19 and 0-22, "Water; Atmospheric Analysis " 1971 Annual Book of f™ Standards Part 23 01605-60,
"Standard Recommended Practices for Sampling Atmospheres for Analysis of Gases and Vapors, American bociety tor
Testing and Materials, Philadelphia, PA., 1971, p. 349-370. Gasification Process,"
058 Hamersma, J.W.,and S.R. Reynolds, "Tentative Procedures for Process easurements, Lurgi Coal Gasification
TRW Systems Group, EPA Contract No. 68-02-1412, March 1975, Chapter V.
B) BACKGROUND INFORMATION
052 .Leithe, «.. "The Analysis of Air Pollutants," Ann-Arbor Humphrey Science Publishers, Ann Arbor, Michigan, 1970.
C) FIELD APPLICATIONS
99
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PAGE 2 OF 2 FOR
TITLE GENERAL FUGITIVE GAS GRAB SAMPLING TECHNIQUES (CONTINUED)
ID NO. 01-05-04-01
SCALED WITH
CAHTMIDW
-FILLED
WAX- FILLED
CARTRIDGE
290 to 900 e.c
CAPACITY
Figure 01-05-04-01A. Evacuated Sample Container,
ADSORBTION TUBE
Figure 01-05-04-01B. Evacuated Grab Sampling Apparatus (3 liters).
FLOW
ADSORBTION TUBE
Figure 01-05-04-01C. Grab Purge Sampling Apparatus (500 ml).
100
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PAGE 1 OF 2 FOR
1. TITLE FUGITIVE GAS GRAB SAMPLING USING PLASTIC DAGS
3. ABSTRACT OF METHODOLOGY
IDENTIFICATION CODE
01-05-04-02
Plastic bags of various compositions are suitable for the collection of gas samples. Some storage properties of gases in plastic
bags are shown in Table 01-05-04-02A. Figure 01-05-04-02A shows a typical integrated air sampling apparatus using a plastic sampling
bag. The bag can be evacuated prior to arrival at the test site. The rigid box which houses the sample bag must be airtight and must
have two openings - one for the sample inlet and the other for the pump tube. Alternatively, the bag can be filled by use of a small
electric blower, or if wind velocity is sufficient, by simply pointing the bag in the direction of the wind.
4. APPLICATION^ Environmental assessment
A) OPERATIONAL SCOPE
The method is applicable to sampling of product gas, process streams, ambient air, etc. (See Table 01-05-04-02A) Plastic bags
have temperature stability of several hundred degrees Celsius.
B) INTERFERENCES/LIMITATIONS
Method cannot be used for sulfur gases, or organics which may chemically interact. The rate of loss or contamination of sample
from plastic bags, (not including direct leakage) is dependent upon type of plastic used, adsorption/diffusion characteristics
for the plastic used, type and concentration of sample, temperature, pressure, and likelihood of intrasample interactions.
C) RECOMMENDED USE AREA
This is the recommended level 1 environmental assessment method for fugitive gas grab sampling using plastic bags.
5. OPERATIONAL PARAMETERS
A) RANGE Collected gases may be contained for periods of several days, with 90% or better retention. Up to several
cubic feet can be collected.
B) ACCURACY 10X or better.
C) PRECISION
N/Q
REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
See Table 01-05-04-02A for plastic bag compositions.
Plastic box for housing the bag; flowmeter, valve; pump
(see Figure 01-OB-04-02A).
& KEYWORD INDEX: Fugitive gas grab sampling, plastic bags, Tedlar, Mylar.
9. CROSS REFERENCE ID NUMBERS 01-01-04-02; 02-02-Oli 02-03-01; 02-02-02; 02-03-02
10. REFERENCES
A) PRIMARY SOURCE
026 American Conference of Governmental Industrial Hygienists, "Air Sampling Instruments for Evaluation of Atmospheric Contaminants,"
Cincinnati, American Conference of Industrial Hygienists, 4th ed., 1972, p. R-5 to R-7.
024 ASTM Committee D-17 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Dl605-60, Part 23,
"Standard Recommended Practices for Sampling Atmospheres for Analysis of Gases and Vapors," American Society tor
Testing and Materials, Philadelphia, PA., 1971, p. 351-2.
B) INTERFERENCES/LIMITATIONS
115 Schuette, F.J., "Plastic Bags for Collection of Gas Samples," A.I.H.L. Report No. 19, California Dept. of Public Health, December 1965.
116 Smith, B.S., and J.O. Prince, "The Use of Plastic Bags for Industrial Air Sampling," Amer. Indus*- Hyg. Assoc- J" 31' 343-348-
117 Altshuller, A.P., I.R. Cohen, S.F. Selva and A.F. Wartburg, "Storage of Vapors and Gases in Plastic Bags," Int. J. Air Hat. Poll..
6, 75-81 (1962).
118 Conner, W.D., and J.S. Nader, "Air Sampling with Plastic Bags," Amer. Indust. Hyg. Assoc. J..2J. 291-297 (1964).
101
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PAGE 2 OF 2 FOR
TITLE FUGITIVE GAS GRAB SAMPLING USING PLASTIC BAGS (CONTINUED)
ID NO. 01-0&04-02
B)
C)
BACKGROUND INFORMATION (Continued)
119 Baker, R.A.,and R.C. Doerr, "Method of Sampling and Storage of Air Containing Vapors and Gases," Int. J. Afr.Pol]..
2, 142-158 (1959).
120 Tamplin, B.,Unpublished data, Air and Industrial Hygiene Laboratory, California State Department of Public Health (1963).
121 Schuette, F.J.,Unpublished data, Air and Industrial Hygiene Laboratory, California State Department of Public Health (1962).
122 Ringold, A., R. Finn, J.R. Goldsmith, H.L. Helwig and F. Schuette, "Estimating Recent Carbon Monoxide Exposures,"
Arch. Environ. Health.j, 30-48 (1962).
058 Hamersma, J.W.,and S.R. Reynolds, "Tentative Procedures for Process Measurements, Lurgi Coal Gasification Processes,"
EPA Contract No. 68-02-1412, TRW Systems Group,.March 1975, p. 5-6.
FIELD AP»',ICATIONS
123 "Tentative Method for Analysis of C-j Through C5 Atmospheric Hydrocarbons," Review Draft (1965) Method SOPH: 1-50,
Air and Industrial Hygiene Laboratory, California State Department of Public Health.
124 Stewart, R.D., D.S. Erley, H.H. Gay, C.L. Hake and J.E. Peterson, "Observations on the Concentrations of Trichloroethylene
in Blood and Expired Air Following Exposure of Human," Amer. Indust. Hyg. Assoc. J.. 2:3, 167-170 (1962).
125 O'Keefe, A.E.,Private Communications, Laboratory of Engineering and Physical Sciences, Division of Air Pollution,
U.S. Public Health Service, Cincinnati, Ohio, 1965.
126 Wilson, K.W., and H. Buchberg, "Evaluation of Materials for Controlled Air Reaction Chambers," Indust. Eng. Chem..
50, 1705-1708 (1958).
Table 01-05-04-02A. Some Storage Properties of Vapors and Gases in Plastic Bags (Reference 115).
Plastic
Film
Mylar
Polyvinyl
Scotch Pak
Kel-F
Ref.
117, 118
117, 118
117, 118
122
120
126
Gas or Vapor
Stored
Ozone
N02
so2
Carbon monoxide
Carbon monoxide
N02
Concentration
70 pphms
0.2 to 0.5 ppm
0.5 ppm
1 to 100 ppm
1 to 100 ppm
1 ppm
Remarks
10% loss in 5 hrs in synthetic air
5% in 8 hrs in synthetic air
Stable for 4 hrs in synthetic air
Storage variable with source of supply
Stable several days in expired air
Stable for 120 hrs
AMBIENT AIR
PLASTIC BOX
MYLAR OR
TEDLAR BAG
Figure 01-05-04-02A. Integrated Air Sampling Apparatus Schematic.
102
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Table of Contents for 01-06 Sampling for Fugitive Particulate Emissions
Ql'06-01 Mass Loading Techniques
01-06-01-01 Collection and Analysis of Dust Fall (Settleable
Particulates) . . . .'
01-06-01-02 Continuous Monitoring of Mass Loadings Using
Beta Attenuation
01-06-01-03 Piezo-Electric Aerosol Mass Concentration
Monitor
01-06-01-04 Sampling Fugitive Emissions by High Volume
Samplers
01-06-01-05 Fugitive Emissions Sampling With an Electro-
static Precipitator
01-06-01-06 Combined Sampling Analysis Method for Deter-
mination of Trace Elements Atmospheric Particulates
(Graphite Cup)
01-06-01-07 Sampling Fugitive Emissions With Sequential
Tape Samplers
01-06-02 Particle Sizing Techniques
01-06-02-01 Particle Sizing of Fugitive Emissions . . .
103
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APPLICATION MATRIX FOR 01-06 FUGITIVE PARTICULATE EMISSIONS
METHOD
01-06-01-01
01-06-01-02
01-06-01-03
01-06-01-04
01-06-01-05
01-06-01-06
01-06-01-07
01-06-02-01
LEVEL I
ENVIRONMENTAL
ASSESSMENT
Q
•
•
COMPLIANCE
•
ENGINEERING
EVALUATION
R/D
•
•
•
•
•
104
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SAMPLING FOR FUGITIVE PARTICULATE EMISSIONS - ID No. 01-06
Particulates can be chemical elements or compounds in either solid
or condensed liquid droplet form. Solid particulates can be grouped into
several categories, based on particle size and method of evolution.
Dusts, which can range in size from visible to mm diameter particles,
are formed from solids by mechanical processes such as grinding, crushing,
and pulverizing. Fumes, which range in size from 1 to 0.0001 y, are
formed from solids by evaporation, condensation, and various gas phase
molecular reactions. The third type of particulate matter, smokes, are pro-
ducts of incomplete combustion of organic materials and are characterized by
optical density; the size of smoke particles is approximately 0.5 p. if
vents are sampled, then the conditions for isokinetic sampling (01-04) must
be met. Ambient or enclosed areas do not need to follow those rules.
Principal process areas which are sampled for fugitive particulate
emissions include coal pile storage areas, including grinding and
sifting areas, gasifier input areas (lock-hoppers) and miscellaneous
process vents. The general rule for particulate collection requires that
enough sample be pulled through the sampler to establish a net particulate
weight of 50 to 250 mg. Air flow through the filter can be adjusted so
that the sample weight falls within this range over a 24-hour period.
The graphs shown in Figure 01-06-A can be used as aids in obtaining the
proper flow rate.
For details on the placement of sampling units and the problems
collecting fugitive emissions, the reader is directed to 01-05.
01-06-01 Mass Loading Techniques (Abstracts 01-06-01-01 through
01-06-01-08)~
Sampling fugitive particulate emissions requires either high flow
rates or high analysis sensitivity to overcome the low mass loading
normally encountered. The standard piece of equipment for particulate
sampling is the high volume sampler (01-06-01-05). Because of changes
in the pressure drop across the filter, it is recommended that the
commercial equipment selected have an automatic constant flow rate
control to insure accurate flow rate measurement. An electrostatic
precipitator (01-06-01-06) is another high volume sampler. An ESP has
105
-------
130
120
§110
u.
o
o 'oo
-
o 8U
o
Q 7C
i~l
O
UJ
Z 60
O
Z
s; so
u. 40
O
y*
2 30
20
10
.13M3/MINFLOW
(40 CFWO
.566 M3/MIN FLOW
(20 CFM!
10 15 20 25 35 0
100
200 300 200
300
400 500 700 9001100
FLOW RATE CURVE TO BE USED
WHEN DUST CONCENTRATIONS
ARE NOT VISIBLE
CLEAR-
VERY LIGHT HAZE
PARTICULATE/M0 IN AMBIENT AIR
FLOW RATE CURVE TO BE USED
UNDER HAZE CONDITIONS
LIGHT HAZE-
HEAVY HAZE
FLOW RATE CURVE TO BE USED
WHEN DUST CONCENTRATIONS
ARE VISIBLE
HEAVY HAZE -
->• THICK DUST
Figure 01-06-A. Sampler Flow Rate Settings for Dust (References 024 and 127)
-------
the dual advantages of a low pressure drop and particulate collection in
a small area. If semi-continuous or sequential sampling of the fugitive
emissions is desired, tape samplers (01-06-01-08) can be used. Because
of their lower flow rate, sampling times and analytical methods (02-01-04-04
and 02-02-01-05) must be selected carefully. An integrated sampling and
analysis approach is described in 01-05-01-07 where a spectrographic graphite
electrode is used to sample the air, and then analyzed by Optical Emission
Spectroscopy (02-02-02-03). If mass loading information only is required,
then a piezo-electric (01-06-01-03) or 3 attenuation (01-06-01-04)
monitor can perform this task in a continuous manner. Many of the
commercial instruments using these approaches collect the particulate
sample for later chemical analysis. Finally, settlable particulates
(01-06-01-01) are measured with standard techniques.
01-06-02 Particle Sizing Techniques (Abstract 01-06-02-01)
Analysis of fugitive emission for particle size distribution is
becoming increasingly important. Concern about the distribution of the
respirable portion (1-10 y) of particulate has dictated an increase in
the use of cascade impactors (01-06-02-01). Commercially available units
have reasonably high flow rates (20-40 cfm) and large collection capacities.
REFERENCES
024 "Planning the Sampling of the Atmosphere", ASTM 1974 Annual Book of
Standards, Part 23, Dl357-57.
127 Danielson, J.A., "Air Pollution Engineering Manual", Air Pollution
Control District County of Los Angeles, 2nd ed., May 1973.
107
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1. TITLE COLLECTION AND ANALYSIS OF DUST FALL (SETTLEABLE PARTICULATES)
2. IDENTIFICATION CODE
01-06-01-01
3. ABSTRACT OF METHODOLOGY
Open-top collectors of specific size and shape are located at carefully positioned sites outdoors to collect settleable participates.
The collected material can be taken to the laboratory in a closed container for further analysis. Settleable particulates for this
method are described as any particle, liquid, or solid small enough to pass through a 1 millimeter screen and large enough to settle
in the collector.
4, APPLICATION: Engineering evaluation R&D.
A) OPERATIONAL SCOPE
This method covers the procedure for the field collection of settleable particulates, and can be used in areas where windblown dust
from the ground or storage areas is not a problem.
B) INTERFERENCES/LIMITATIONS . , ,, c . .
Care must be taken to avoid matter from trees, bird droppings.and other such deposits. Also, material collected by action of wind
must be prevented. Care must be taken in selecting the sampling site to prevent undue influence from a particular source, thus
biasing the composition of the particulates collected.
C) RECOMMENDED USE AREA
Engineering evaluation R&D fugitive emissions survey technique.
OPERATIONAL PARAMETERS
A) RANGE N/A
B) ACCURACY N/Q; care must be taken in using this method because of its simple and unsophisticated approach to collection.
C) PRECISION N/Q
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Reagent grade water; isopropyl alcohol, reagent grade.
Collector (an open-top cycl.inder with vertical sides, flat bottom),
No. 18 sieve.
& KEYWORD INDEX: Sampling, mass loading techniques, settleable particulates.
9. CROSS REFERENCE ID NUMBERS 01-06-01-04, 05, 07.
10. REFERENCES
A) PRIMARY SOURCE
013 Part'26Stpnd340 Meth°d f°r Collect1on and Analys1s Thus Far>" 1974 Annual Book of ASTM Standards, Method D1739-70,
B) BACKGROUND INFORMATION
128 Meethan, A.R., "Atmospheric Pollution; Its Origin and Prevention," Pergaraon Press, London, 3rd ed., 1964,
Chapter 11, "Measurements of Air Pollution."
129 Air Pollution Control System Association, "Recommended Standard Method for Continuous Dust Fall Survey
(APM-1, Revision 1)," J.A.P.C.A.. ]6_, 372 (1966).
C) FIELD APPLICATIONS
130 Nader, J.S., "Dust Retention Efficiencies of Dust Fall Collectors," J.A.P.C.A., 8, 35 (1958).
108
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PAGE 1 OF 2 FOR
1. TITLE CONTINUOUS MONITORING OF MASS LOADINGS USING BETA ATTENUATION
_______—^^^^^^——_______^_^__^^_^___
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
01-06-01-02
Beta attenuation instruments consist of a beta radiation source (usually 14c), a detector, and a tape sampler Particles from
known volume of air are collected on a filter tape and then placed between the radiation source and detector The difference
in the detector count before and after the particles are collected is a measure of the mass of the particles.
4. APPLICATION: Engineering evaluation R&D.
A) OPERATIONAL SCOPE
These units are designed for semi continuous analysis to atmosphere. By using sampling lines and a switching system,
a series of sampling points can be monitored. These systems provide a continuous measure of mass loading while at
the same time collecting a sample for chemical analysis.
B) INTERFERENCES/LIMITATIONS
One must always be aware of the collection efficiency of the filter tape. In many cases, Whatman filter paper is used
in the tape sampler; this filter ranges from 50 to 80% as efficient as glass fiber filters for smaller particles.
C) RECOMMENDED USE AREA
This method is used for engineering evaluation R&D.
5. OPERATIONAL PARAMETERS
A) RANGE jne un-jts are completely automated and the amount of sample taken can be adjusted to compensate for high and low
mass loadings.
Bl ACCURACY ±15%
C) PRECISION
N/Q
R REAGENTS REQUIRED
None
7. EQUIPMENT REQUIRED
A typical automatic beta continuous attenuation sampling
device can be obtained from the Research Appliance Co.,
Allison Park, Penn. A high volume unit can be obtained
from the 6CA Technology Division, Bedford, Mass.
8, KEYWORD INDEX: Sampling, beta continuous.
9. CROSS REFERENCE ID NUMBERS
02-01-02-04.
10. REFERENCES
A) PRIMARY SOURCE . T , .
131 Nader, J.S., and D.R. Allen, "A Mass Loading and Radioactivity Analyzer for Atmospheric Particulates, «". indust.
Hyg. Assoc. J., 1, 300 (1960).
B) BACKGROUND INFORMATION
132 Lilienfeld, P., and J. Dulchinos, "Vehicle Particulate Exhaust Mass Monitor," Final Report for EPA on Contract
No. 68-02-0209 (1972).
134 Dresia, H.,and F. Spohr, "Experience with the Radiometric Dust Measuring Unit." Staub-Reinhalf Luft (English
translation), 31, 6 (1971).
1C35 FIEL^TkelTR°,Nand Y.C. Boong, "Development of a Nucleonic Particulate Emission Gauge," Industrial Nucleonic Corp., Columbus,
Ohio, NTIS, DB 209954, 1972.
136 Hering, R., "Beta Gauge and Filter Collection System for Determination of Automobile Particulate Ehrissions, preprint,
Joint Conference on Sensing of Environmental Pollution, Palo Alto, Ca., Nov. 8, ia/i.
109
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PAGE 2 OF 2 FOR
TITLE CONTINUOUS MONITORING OF MASS LOADINGS USING BETA
ATTENUATION (CONTINUED)
ID NO. 01-06-01-02
10. REFERENCES (Continued)
137
Huser, R.B., and S.C. Heiseler, "Proceedings from the Conference on Methods in Air Pollution Industrial Hygiene Study,"
State of California Dept. of Public Health, Berkeley, California,October 1972.
110
-------
2. IDENTIFICATION CODE
3. ABSTRACT OF METHODOLOGY
This instrument continuously monitors the aerosol mass concentration by monitoring the change in the residence frequency of a piezo
electric quartz crystal accompanying the precipitation of the particulate on the face of the crystal. Aerosol is run through the
system by a vacuum pump at 1 1pm. The sampling crystal is the collecting surface of an electrostatic precipitator, which collects
particles from 0.01 through 10 microns in diameter. A second crystal, not exposed to the aerosol, balances out frequency changes due
to temperature, pressure and humidity changes. Recent advances have used several crystals stacked in a cascade impaction device to
monitor the mass loading versus particle size on a continuous basis. The rate of change of the output frequency is directly proportional
to the mass concentration of the airborne particles. Thus, mass concentration equals the change in frequency during a given time
period divided by a sensitivity constant. The sensitivity constant is supplied with each unit. Direct monitoring of the output is
easily accomplished by means of an electronic counter.
4. APPLICATION' Engineering evaluation R&D.
A) OPERATIONAL SCOPE
This instrument has sufficient sensitivity to measure ambient particulate mass concentration and has also been used to
measure particulate concentrations in flue gas (see Ref. 141 in Field Applications).
8) INTERFERENCES/LIMITATIONS
Since the piezo-electric device depends upon efficient sampling of the electrostatic precipitator, the same problems
that occur with electrostatic precipitators (changes in efficiency with particle size and humidity) will affect the ultimate
efficiency of the piezo-electric mass concentration monitor.
C) RECOMMENDED USE AREA
This method can be used for ambient engineering evaluation R&D.
5. OPERATIONAL PARAMETERS
A) RANGE A determination of particle mass concentration in the range of 100 pg/m3 is possible.
B) ACCURACY ±10% with a sampling time of 1 minute.
Cl PRECISION N/Q
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
None
Piezo-electric Aerosol Mass Concentration Monitor (a typical
piezo-electric aerosol mass concentration monitor can be
obtained from Thermal Systems, Inc., St. Paul, Minn.).
& KEYWORD INDEX: Sampling, mass loading, Piezo-electric sampler.
9. CROSS REFERENCE ID NUMBERS 01-06-01-02.
10. REFERENCES
A) PRIMARY SOURCE ,
138 Brenchley, L.D., C.D. Turley and R.G. Yaime, "Industrial Source Sampling," Ann Arbor Science Publishers, Ann Arbor, Mich.
1973.
B) BACKGROUND INFORMATION
139 Olin, J.G., Adv. Instr., 26, 1 (1971).
HO Olin, J.G., L. Christeson and G.J. Sem, Am. Ind. Hyg. Assoc._J.. J2, 209 (1971).
C) FIELD APPLICATIONS
141 Chuan, R.L., "Application of an Oscillating Quartz Crystal to Measure the Mass of Suspende d
Chapter 9 in "Anal. Methods Applied to Air Pollution Measurement," edited by R.K. Stevens ana
Science, Ann Arbor, Mich., 1974.
142 Carpenter, T.E., and L.D. Brenchley, Am. Ind. Hyg. Assoc. J., 33, 503 (1972).
Arbor
Ill
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PAGE 1 OF 2 FOR
1. TITLE SAMPLING FUGITIVE EMISSIONS BY HIGH VOLUME SAMPLERS
2. IDENTIFICATION CODE
01-06-01-04
3. ABSTRACT OF METHODOLOGY
A measured and representative sample of the atmosphere under investigation is drawn through a filter media which has been specifically
selected to collect the suspended participate. Because of the low grain loadings normally found in ambient atmospheres, high volume
(3 m3/min) samplers are employed. These compact and portable collectors consist of a large area filter holder, a high capacity blower,
and a built-in flow indicator. In order to measure the mass concentration, a pre-conditioned (constant weight) tared filter is used to
collect the sample. After the sample has been collected, the filter is then reconditioned in the same manner and reweighed. It is
recommended that a Gelman Type A Spectrograde glass fiber filter be used to collect a particulate sample if chemical analysis is to be
performed. As a second choice, acid-washed Whatman 41 can be used to collect the sample. If chemical analysis is to be conducted on
the filter, care must be taken to avoid contamination by dust or handling methods, and at all times the filter should be transported in
a container which has been suitably cleaned for trace analysis work (see 02-01-01, 03, -04).
4. APPLICATION' Compliance, environmental assessment.
A) OPERATIONAL SCOPE
This procedure covers the collection of particulate matter from an atmosphere by filtration and for the measurement of either
mass loading or chemical analysis of the particulates collected. Although especially applicable to collection of solid particles,
the filter method may be also used to collect liquid particles if droplet size need not be determined.
8) INTERFERENCES/LIMITATIONS
Large samples must be taken over a period of time and,consequently, the daily fluctuations in particle concentrations cannot be
determined (for semi-continuous methods, see 01-06-01-02, -03). During the sampling period, the filter will tend to become loaded
and the flow rate will decrease as filter resistance increases. Therefore, it may be necessary to adjust the flow rate frequently
or provide for essentially constant flow automatically by means of a critical orifice.
C) RECOMMENDED USE AREA
Environmental assessment.
5. OPERATIONAL PARAMETERS
A) RANGE
N/A
B) ACCURACY The accuracy of the method will depend upon how accurately the filter is weighed and how accurately the flow rate
is measured.
C) PRECISION N/A
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Analytical balance, desiccator, petri dishes, high volumesamplingunit
(typical suppliers are: Gel man Instrument Co., Chelsea, Mich.; Mine Safety
Appliances, Pittsburg, Penn.; Staplex Co. .Brooklyn, N.Y.;Union Indust-
rial Equipment, Portchester, N.Y.; Production Equipment Co., Detroit
Hir.hA -
None
KEYWORD INDEX: 02-01-01, 03, 04; 01-06-01-02, and 03.
9. CROSS REFERENCE ID NUMBERS
10. REFERENCES
A)
B)
C)
PRIMARY SOURCE
053 ASTM, "Collection by Filtration and Determination of Mass, Number and Optical Sizing of Atmosphere Particulates,"
1974 Annual Book of ASTM Standards, Part 26, Method D2009-65, p. 422
BAfKGROUN^NFORMATION Pr0tect1°" A9enc*' Tit1e 40- ^ BO, Chapter 1, Appendix B, Washington, D.C.
143 Smith Walter J., and N.F. Surerenat, "Properties of Various Filter Media for Atmospheric Dust Sampling," Proceeding.
Ao I n « 03 $ lz?DQ.
144 Silver-man, L., and F.J. Biles, "A High Volume Air Sampling Filter Weighing Method for Certain Aerosols," J. of Ind. Hyg.
HjX • y 3\J \ L. } 9 I CH .
FIELD APPLICATIONS
145 J^ofT an'R'11a'''' ApPardt"S f°r SamPlin9 of Lar9e Air Volumes for Industrial Air Analysis,"
146
gTox282i(l946
147
Dams, R.N., and R. Heindryckx, Atm. Environ, 7(3). 319 (1973).
Determination of Air
112
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PAGE 2 OF 2 FOR
TITLE SAMPLING FUGITIVE EMISSIONS BY HIGH VOLUME SAMPLERS (CONTINUED)
ID NO. 01-06-01-04
C) FIELD APPLICATIONS
148 Pluss, T.H., and W. Strauss, Atm. Environ.. 7_(6), 657 (1973).
149 Rahn, K.A., G. Beke and G. Wlndels, Atm. Environ.. 8, 635 (1974).
150 "Calibrative Study of Reference Method for Determination of Suspended Particulates in the Atmosphere," Quality
Assurance and Environmental Laboratory, Environmental Protection Agency, Research Trianeile, N.C. , PB 205-891,
June 1971.
-------
1. TITLE FUGITIVE EMISSIONS SAMPLING WITH AN ELECTROSTATIC PRECIPITATOR
Z IDENTIFICATION CODE
01-06-01-05
3. ABSTRACT OF METHODOLOGY
In the electrostatic precipltator (ESP), dust-laden air is passed between two surfaces carrying a high electric potential. This high
electric potential causes the ionization of air molecules. These charged molecules can interact with the particles in the gas stream
and cause them to attain a charge. Under the force of the electric field, the charged particles are then driven to a collecting
electrode where they are precipitated. Normally, the collection plate is small and hence the collected particles can be weighed
accurately. The precipitation is highly efficient, air flows are high, and pressure drops are low. In general, electrostatic pre-
cipitators have two important advantages over filters: 1) the sampling rate is not affected by the amount of sample collected, and
2) the sample is usually in a readily recoverable form.
4. APPLICATION' Environmental assessment.
A) OPERATIONAL SCOPE
This method can be used to sample fugitive emissions under ambient conditions.
B) INTERFERENCES/LIMITATIONS
Electrostatic precipitators are higher in initial cost than other high volume sampling units. Because of the electrical discharge
in the sampling area, they cannot be used in explosive atmospheres. This electric field also generates small amounts of ozone and
oxides of nitrogen. Some units employ a positive corona discharge which lowers the amount of ozone produced. One must realize
that gases such as 502 Passing through the corona can be oxidized to sulfuric acid and coat the particles. Subsequent chemical
analysis will be jeopardized, especially if surface techniques such as ESCA are employed. Under most conditions, however, the oxi-
dation of 502 should be minimal.
C) RECOMMENDED USE AREA
This device can be used as an alternate fugitive emission sampling system.
OPERATIONAL PARAMETERS
A) RANGE Typical flowrates are from 500 to 10,000 1pm.
B) ACCURACY At 5000 1pm, a typical unit collected 90% of O.lu particles.
C) PRECISION N/Q
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
None
Typical ESP samplers can be obtained from Environmental
Research Corp., St. Paul, Minn., and Del Electronic Corp.,
Mt. Vernon, N.Y.
& KEYWORD INDEX: Sampling, electrostatic precipltator, ESP.
9. CROSS REFERENCE ID NUMBERS 02-04-01, 02-04-02.
10. REFERENCES
A) PRIMARY SOURCE
026 "Air Sampling Instruments," American Conference of Governmental Industrial Hygienists, Cincinnati, Ohio, 1972.
B) BACKGROUND INFORMATION
151 Lipmann, M , S. Cravaugh, H.J DiGiovanni and P. Lilienfeld, "Lightweight High Volume Electrostatic Precipitator Survey
Sampler," AIHA Journal, 26, 485 (Sept.-Oct. 1965).
1« f-?we>.Vu ^ y'";,,,-^35' "Ihe PhriCS Of E!ectrostatic Precipitation," Brit. J. Appl. Pnys.. 24, Sup. 2, 40 (1953).
Rev' Sci Instr 38 100 0967) "Electrostatic Aerosol Sampler for Light and Electron Microscopy/
C) FIELD APPLICATIONS
114
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PAGE 1 OF 2 FOR
ffgHgp^^
1. TITLE
^^^••••l^—v^—•
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
01-06-01^)6
Porous cup spectrographic graphite electrodes are used as filters to collect atmospheric particulates and then are analyzed for
elements directly by an emission spectrographic method. Each graphite collection filter is solution-doped with 0 25 micrograms
of indium as an internal standard and dried in a vacuum oven at atmospheric pressure prior to field use. Using the sampling device
shown in Figure 01-06-01-06A, a sample is taken using a flowmeter and vacuum pump. The spectrographic analysis is carried out
using a Jarrell-Ash Custom Varisource (Model 40-750). Concentrations are determined from analytical curves developed by means of
appropriate standard solutions.
4. APPLICATION: Engineering evaluation R&D.
A) OPE RATIONAL SCOPE
This method is designed to be used for sampling atmospheric particulates. Because of its high
sensitivity, it is extremely useful in sampling atmospheres using a short sampling time.
B) INTERFERENCES/LIMITATIONS
While the equipment in this particular technique is readily available, the techniques
employed are not applicable to most laboratories.
C) RECOMMENDED USE AREA
This method is applicable to engineering evaluation R&D programs for ambient measurements.
OPERATIONAL PARAMETERS
A) RANGE Several elements, such as lead, which are distributed in the atmosphere as particulates at concentrations less
m .~,,,D,™ tnan O-1 ug/m3 per cubic meter, are determined using a 30-min. collection cycle.
B) ACCURACY — —
Ct PRECISION ±10-20%
a REAGENTS REQUIRED
Spectrographic electrode (Ultra carbon, No. 202), high purity
nitric acid (standard solutions that were used in this technique
for calibration purposes were prepared from analytical grade
reagent or spectrographic metals or metal oxides).
7. EQUIPMENT REQUIRED
Jarrell-Ash Custom Varisource (Model 40-750), spectrograph
(Baird-Atomic 3-metef Model 169).
& KEYWORD INDEX: Sampling, graphite cup method.
9. CROSS REFERENCE ID NUMBERS 02-02-02-03.
10. REFERENCES
AJ PRIMARY SflIIRf*F
154 Seeley, J.L.,and R.K. Skogerboe, "Combined Sampling Analysis 'Method for the Determination of Trace Elements in
Atmospheric Particulates," Anal. Chem., 46, 415 (1974).
B) BACKGROUND INFORMATION
155 Katz, M., "Measurement of Air Pollutants," World Health Organization, Geneva, 1969.
Cl FIELD APPLICATIONS
156 Wbodriff, R., and J.F. Leach, Anal. Chem., 34, 1323 (1972).
157 Skogerboe, R.K., A.T. Kashuba and G.H. Morrison, Appl. Spectr., 23, 169 (1969).
158 Bedrosian, A.J., G.H. Morrrison and R.K. Skogerboe, Anal. Chem., 40, 854 (1968).
115
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PAGE 2 OF 2 FOR
TITLE COMBINED SAMPLING ANALYSIS METHOD FOR DETERMINATION OF TRACE ELEMENTS
ATMOSPHERIC PARTICULATES (GRAPHITE CUP) (CONTINUED)
ID NO. 01-06-01-06
• 0-RW6 SEALS
D TEFLON
V. GRAPHITE
TO VACUUM
g
c
Figure 01-06-01-06A. Porous Cup Spectrographic Graphite Electrode Sampler
(from Anal. Chem., 46, 415 (1974).
116
-------
1. TITLE SAMPLING FUGITIVE EMISSIONS WITH SEQUENTIAL TAPE SAMPLERS
2. IDENTIFICATION CODE
01-06-01-07
3. ABSTRACT OF METHODOLOGY
A tape sampler uses a strip of filter paper (Whatman 41) or sor.e related material (glass fiber) as a sampling medium. Typically
this tape is about 2.54 cm (one in.) wide, 304.3 n, (1000 ft.) long and is supplied in a roll form. The tape is threaded from
a supply spool through an advancing n.echanisn and sappling head onto a take-up spool. On the sampling head the tape is supported
so that an area is sealed within the sampling train. Particulates are collected by filtration (typically 1C to 20 1pm' into a
narrowly defined "dust spot" on the paper. Host instruments can be automatically sequenced to intermittently advance a fresh col-
lection surface. The individual dust spots can be returned to the laboratory for chemical analysis (see 02-01-04-04i 02-02-01-05).
4. APPLICATION- Engineering evaluation R&D.
A) OPERATIONAL SCOPE
These units are designed to sample fugitive emissions, in a sequential time-oriented mode.
B) INTERFERENCES/LIMITATIONS
Filtration efficiency of paper falls off with smaller particles, while the chemical Hank of glass fiber is much higher than acid-
washed filter paper. Under heavy dust build-up, flowrate can vary and lead to inaccuracies in mass loading calculations.
C) RECOMMENDED USE AREA
Collection of fugitive emission particulates for engineering evaluation R&D.
5. OPERATIONAL PARAMETERS
A) RANGE
Normal ambient temperatures.
B) ACCURACY
N/Q (collection efficiency varies with particle size).
C) PRECISION
N/Q
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
None
Tape samplers can be obtained from Gilman Instr. Co.,
Precision Scientific, Research Appliance Co., or National
Environmental Instruments.
8. KEYWORD INDEX: sampling, tape sampler.
9. CROSS REFERENCE ID NUMBERS 02-02-01-05i 02-01-04-04.
10. REFERENCES
A) PRIMARY SOURCE
159 "Air Quality Cri
Washington, D.C.
B) BACKGROUND INFORMATION ,.„,.• • nan nhin 1972
026 American Conference of Governmental Hygienists, "Air Sampling Instruments," Cincinnati, Ohio,
A) PRIMARY SOURCE
159 "Air Quality Criteria for Particulate Matter,11 National Air Pollution Control Administration Publication No. AF-49,
Washington, D.C., 1969.
C) FIELD APPLICATIONS „ _ . . ,nn ,10(-7v
160 Chatfield, E.J., "A Battery Operated Sequential Air Concentration and Deposition Sampler, Atm. Envirn.. I. 509 (1967).
161 Parker, W.V, and M.A. Huey, "Multipurpose Sequential Samplers," J...A1r Pol. Cont. Assgc.. 17, 388 <1967>-
117
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1. TITLE PARTICLE SIZING OF FUGITIVE EMISSIONS
2. IDENTIFICATION CODE
01-06-02-01
3. ABSTRACT OF METHODOLOGY
An Anderson Sampler is used to collect and size fugitive emissions. Air is drawn through the sampler, producing a jet of air from
each of the 400 holes in each stage, directed at the collection plate below. The size of the holes is constant for each stage,
but is smaller in each successive stage. Consequently, the jet velocity is uniform in each stage, but increases in each succeeding
stage. When the velocity imparted to a particle is sufficiently great, its inertia will overcome the aerodynamic drag^and the
particle will impact on the surface. Thus, each stage collects smaller particles than the preceding one. Since the unit can sample
up to 1 cfm of air and because of the number of the collection points, sufficient quantities of sized particulate matter can be
collected for chemical or microscopic analysis.
Care must be taken in site selection so that a representative sample can be obtained. (See 01-06.)
4. APPLICATION'. Environmental assessment.
A) OPERATIONAL SCOPE
This unit is designed to operate under ambient conditions to collect airborne particulate matter.
B) INTERFERENCES/LIMITATIONS
In many cases the collection area must be coated with a sticky material to ensure particles will not be reentrained.
This procedure can interfere with chemical analysis. An additional filter is required for <0.5i. collection.
C) RECOMMENDED USE AREA
Particle size information for level 1 environmental assessment of fugitive emissions.
OPERATIONAL PARAMETERS
Al RANGE Ambient conditions. Six stages from 0.5 to In, 1 to 2y, 2 to 3.5y, 3.0 to 6.Op, 5 to 11.Sv, and >8.5|i.
B) ACCURACY N/Q (±25%).
C) PRECISION N/Q (±25!!).
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
N/A
Anderson Sampler (Anderson 2000, Inc., Salt Lake City, Utah).
a KEYWORD INDEX: Sampling, particle sizing.
9. CROSS REFERENCE ID NUMBERS 02-01-03-04, (Also, appropriate chemical analyses), 01-06.
10. REFERENCES
A) PRIMARY SOURCE
026 "Air Sampling Instruments," Am. Conf. Gov. Ind. Hyg.. Cincinnati, Ohio, p. 0-23.
B) BACKGROUND INFORMATION
162 Anderson, A.A., "A New Sampler for the Collection, Sizing and Enumeration of Viable Airborne Bacteria,"
J. Bact.. 76_(11), 471 (1958).
163 Anderson, A.A., "A Sampler for Respiratory Health Hazard Assessment," Amer. Ind. Hyg. Assoc. J.. 27, 160 (March-April
1966). —
C) FIELD APPLICATIONS
164 Burton, R.M., et al, "Field Evaluation of the High Volume Particle Fractionating Cascade Impactor -A Technique for
Respirable Sampling," presented at 65th Annual Meeting of the Air Pollution Control Association, June 1972.
118
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Table of Contents for 02-01 Laboratory Preparation
02-01-01 Reagent/Equipment Preparation
02-01-01-01 Reagent Quality Water (for Preparation, Cleaning
of Sample Containers)
02-01-01-02 NBS Certified Standards for Elements in Lubri-
cating Oils
02-01-01-03 Storage of Reagents Used in Chemical Analyses
02-01-.01-04 NBS Standard Reference Materials for Coal and
Fly Ash
02-01-01-05 Cleaning Procedures for Laboratory Glassware
and Plastic Containers
02-01-01-06 Preparation of High Purity Reagents for Trace
Analysis
02-01-01-07 Gas Sampling Container Cleaning Procedure . .
02-01-02 Sample Separation
02-01-02-01 Ion Exchange Method for the Isolation of
Fluoride from Environmental Samples
02-01-02-02 Willard Winter Distillation for the Isolation
of Fluoride from Atmospheric Samples
02-01-02-03' Separation of Liquid/Slurry Samples
02-01-03 Sample Handling/Preservations
02-01-03-01 Recommendations for Preservation of Samples
According to Measurement
02-01-03-02 Preparing Coal Samples for Ultimate and/or
Proximate Analysis (Mechanical and Manual Reduction
and Division)
02-01-03-03 Sample Recovery from Impingers
02-01-03-04 Remova.l of Filters from Filter Holder
02-01-03-05 Removal of Particulate from Cyclones
02-01-03-06 Handling of Probe Liner Samples
02-01-04 Sample Dissolution
02-01-04-01 Total Chlorine in Coal (Eschka Analysis) . . .
02-01-04-02 Coal Dissolution Scheme for Various Elements ,
02-01-04-03 Low Temperature Plasma Ashing and Dissolution
of Collected Particulate •
02-01-04-04 Mixed Ligand Extraction of Ag, Cd, Co, Cu, Fe,
Ni, Pb, Zn and Be from Tape Sampler Dust Spots . . . .
119
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APPLICATION MATRIX FOR 02-01 LABORATORY PREPARATION
METHOD
02-01-01-01
02-01-01-02
02-01-01-03
02-01-01-04
02-01-01-05
^•BMW_>BlllH-M~m^^^^^^^M«IB^_«alM_
02-01-01-06
02-01-01-07
02-01-02-01
02-01-02-02
02-01-02-03
02-01-03-01
02-01-03-02
02-01-03-03
02-01-03-04
02-01-03-05
02-01-03-06
02-01-04-01
02-01-04-02
02-01-04-03
02-01-04-04
LEVEL I
ENVIRONMENTAL
ASSESSMENT
•
•
•
•
•
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•
•
•
•
•
•
•
•
COMPLIANCE
•
•^ ^^— ^^^••••M
•
ENGINEERING
EVALUATION
R/D
•
•
•
•
•^^^^^••^^^^^••^^•^^•^^••^••^••••^wvai^MMii
•
•
•
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120
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LABORATORY PREPARATION - ID No. 02-01
Proper sampling and analysis of inorganic samples must take into account
the problems of contamination by: a) container material, b) improper
cleanliness, and c) impure reagents. Standard laboratory procedures relating
to cleanliness and equipment are generally acceptable for most sampling and
analysis methods. However, more rigorous techniques must be used when
dealing with trace level elements.
02-01-01 Reagents/Equipment Preparation (Abstracts 02-01-01-01
Through 02-01-01-07)
Sample loss and contamination due to apparatus may result if the
surface of the apparatus is attacked, dissolved or etched by the sampled
material. The history of the apparatus must also be considered, due to
the possibility of sample contamination by previous samples which remain
in the container. High temperatures, high pressures and long contact times
may accelerate corrosion of the apparatus and adhesion of the sample on the
container surface. Materials used in labware construction must be thermally
resistant, chemically resistant, chemically inert, and also economical.
Generally, the following materials are preferred: borosilicate glass,
polyethylene, Teflon, platinum and fused silica. However, even these
materials may contain impurities at ppm levels. Plastic labware is
preferred to glassware because of its lower metal content. Table 02-01-A
lists the trace elements content of some common laboratory materials
compared to sea water.
Materials used in the construction of grinders, crushers, mortars
and pestles, etc., must be characterized by greater hardness. Vitreous
alumina, tungsten carbide and boron carbide are preferred to agate,
mullite (3 Al203'2Si02) and hardened steel.
Cleanliness of laboratory glassware (02-01-01-05) is a major require-
ment in order to prevent contamination and to avoid material losses.
Chromic acid cleaning solution is widely used in cleaning of laboratory
glassware; chromium usually remains on the surface of the apparatus even
after rinsing. However, for trace element analysis, the use of a 1:1
concentrated sulfuric acid and concentrated nitric acid is preferred.
Plastic ware can also be cleaned with mixed acids, but prolonged contact
121
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Table 02-01-A. Trace Element Content of Sea Water and Common
Laboratory Materials: PPB (165).
Sea Water
Pyrex
Quartz
Polyethylene
Teflon
Rubber
PVC
Plexiglas
Mi 111 pore
Kimwipe
Zn
10
730
25
25
9
4.1X107
7.1X103
<10
2.4X103
4.9X104
Fe
10
2.8X105
—
1.1X104
35
<100
2.7X105
<140
330
1X103
Sb
0.3
2.9X103
40
0.8
0.4
360
2.7X103
<0.01
39
16
Cr
0.5
--
200
19
<30
4.2X105
2
<10
1.8X104
500
122
-------
with the cleaning solution must be avoided in order to prevent deterioration
of the polymer. After cleaning, labware must be carefully dried and stored
ready for use in a manner which will preclude the possibility of in-
advertent contamination.
Sample contamination by use of reagents which contain various
impurities must also be avoided. Very pure reagent quality solutions
(02-01-01-06) are commercially available, but these reagents may still
contain ppb levels of impurities. Sample contamination may be minimized,
however, by limiting the use of reagents which contain particularly
undesirable contaminants.
High purity reagents (02-01-01-06) may be prepared in the laboratory
when they are not commercially available, or when the purity requirements
of commercial reagents are less than acceptable. A list of some common
laboratory methods of high purity reagent purification and preparation are
listed in 02-01-01-06. Distillations, extractions and ion exchange
columns are the most commonly used methods for reagent purification.
Recrystallization and zone-melting techniques may also be used.
Additional precautions which can be taken in order to minimize
contamination include proper storage of reagents (02-01-01-03), the
avoidance of prolonged storage of reagents, and use of minimum amounts
of reagents. Reagents should be stored in clean suitable containers in
clean storage spaces (drawers or cabinets). Prolonged storage of reagents
must be avoided in order to prevent deterioration of reagents and to
minimize risks of interaction with container walls.
The use of standards (02-01-01-02, 04) in the analysis of samples by
instrumental methods is often required for accurate determinations. Since
the same concentration of a species typically gives different signal
strengths in different matrices, a standard is required in order to
duplicate the chemical and physical nature of the sample as closely as
possible. Standards must be prepared using extremely pure materials.
For example, solutions of metal standards should be prepared from the
pure metals using high purity acids. In order to match the matrix,
special compounds in matrices are available as standards. For example,
stable oil-soluble compounds are available from the National Bureau of
Standards as certified standards for 24 elements in petroleum products
123
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(02-01-01-02). Extra precautions, such as storage of the standards in
desiccators, may be required in order to maximize accuracy in analysis.
Certified gas standards, such as permeation devices, dilution systems,
cylinders of externally calibrated gas mixtures are commercially avail-
able and are being improved. It is recommended that the new aluminum
(AIRCO) cylinders be used to store calibration gases. These containers
have been shown to have +U stability over periods as long as two years
(170, 171). Reliably certified zero air standards (containing 0.1 ppm
maximum hydrocarbons) are currently being developed. Other standards
include gaseous air pollution standards, which will permit determinations
of collection efficiencies for a given particle size, range, and dust
standards of known size distribution.
02-01-02 Sample Separation (Abstracts 02-01-02-01 Through 02-01-02-03)
Sample loss and contamination may arise from improper techniques
(02-01-02-03) in sample separation. Sample separation may be necessary
in order to isolate a specific element or species from the sample, to
remove constituents which interfere with the determination, and to increase
the sensitivity of the subsequent analysis by increasing the weight or
volume concentration of the species of interest. Methods of sample
separation include distillation (02-01-02-02), filtration (02-01-02-03),
precipitation, solubilization, ion exchange (02-01-02-01), and extraction.
Modern complexation methods are based on the formation of organometallic
complexes, which are then separated by precipitation or solvent extractions.
The major source of error in chelation and other techniques stems from
incomplete separation. Other minor sources of error, which may arise
from the use of inpure reagents or partial decomposition of reagents due
to prolonged storage, can and must be avoided.
02-01-03 Sample Handling/Preservation (Abstracts 02-01-03-01 Through
-
Sample handling and preservation procedures are designed to prevent
sample loss prior to analysis. Specific preservation techniques are
employed for each species to be determined (02-01-03-01). In general,
samples must be received, stored and handled in a clean work area.
Laboratory surfaces and ventilation systems should minimize airborne
124
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contaminants. All laboratory reagents and substances which have any
possibility of contaminating the sample should be removed. After samples
are received and removed from their shipping boxes, they must be wiped
clean, arranged in a series, and logged on a master list. Table 02-01-B
shows a sample analytical log and checklist. A preliminary examination
of the sample is then conducted; all particulate samples are weighed
(02-01-03-04, 05, 06), all liquid volumes are measured (02-01-03-03) and
the appearance of any precipitates, organic films or scums and discolorations
are noted. After the preliminary sample preparation has been completed, the
appropriate separation and dissolution procedures can be followed.
02-01-04 Sample Dissolution (Abstracts 02-01-04-01 Through 02-01-04-04)
Standard procedures may involve dry or wet ashing procedures (02-01-04-
01, 02). Sample losses in dry ashing procedures may result from volatiliza-
tion of As, B, Cd, Cr, Cu, Fe, Pb, Hg, Ni, P and V as metals, chlorides and
organometallic compounds; from adsorption of trace elements on walls of
vessels and foaming of the sample during heating; from incomplete sample
oxidation. Wet ashing procedures, in which the sample is oxidized with
liquid reagents and which generally use lower temperatures, are preferred
to dry ashing procedures due to ease in sample recovery. However, there is
still a danger of loss of Sb, As, B, Cr, Ge, Hg, Se, Sn, P, Os, Re, Ru and
Au by volatilization. In some cases, dissolution by organic chelate
extraction of solid materials is possible (02-01-04-04). However, in all
wet methods, sample contamination due to the physical manipulations are
disadvantages. For trace element analysis, the use of the low temperature
oxygen plasma asher is recommended (02-01-04-03). This method has been
shown to be most effective in minimizing loss of trace elements due to
volatilization.
Other forms of sample loss or contamination, can be anticipated and
avoided. Personnel working with trace elements should minimize use of
cosmetics, tobacco, etc., which could disperse through the air. The paint
and coatings of walls and ceilings may act as sources of contamination, since
they contain Ba, Pb, Sb, Ti and Zn. Paints based on epoxy amide resins
are generally recommended. At all times a thorough system of reagent
and system blanks should be run to quantify and identify possible problem
areas.
125
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ro
Sample
Identification
(Cross ref-
erence to
sample
number)
Date
Rec'vd
Prelim.
Wt./Vol.
Physical
Examination
©
Sample Work Up
Drying
Grinding
Blending
Oxygen
PI asma
Ashing
Dissolu-
tion
©
Pre-
Concen-
tration
®
Analysis
®
NOTES: 1. Insert dates at completion of each increment and the analyst's initials.
2. Describe any anamalous behavior, i.e., formation of precipitates, discoloration, films, scums,
ejifervescence, etc.
3. (JN) denotes data and procedure review points.
Table 02-01-B. Sample of Analytical Test Checklist.
-------
REFERENCES
165 Aheya, S. (ed.), "Chemical Analysis of the Environment and Other
Modern Techniques," Plenum Press, New York, 1973, p. 12.
166 Morrison, 6.H., "Trace Analysis; Physical Methods," Interscience
Publishers, New York, 1965.
167 Pinta, M., "Detection and Determination of Trace Elements," Ann
Arbor Science Publishers, London, 1962.
168 Meinke, W. Wayne, and B.F. Scribner (eds.), "Trace Characterization;
Chemical and Physical," NBS Monograph 100, Washington, 1967.
169 McAdie, H.G., and F.J. Hapton, "The Need for Practical Standards in
Air Pollution Measurement," American Laboratory, p. 13-20, December
1975.
018 Flegal, C.A., M.L. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and
C. Zee, "Procedures for Process Measurements; Trace Inorganic Materials,"
EPA Contract No. 68-02-1393, July 1975.
014 Hamersma, J.W., and S.L. Reynolds, "Tentative Procedures for Sampling
and Analysis of Coal Gasification Processes," EPA Contract No. 68-02-
1412, March 1975.
170 Grieco, H.A., and S.G. Wechter, "The Trouble with Reactive Calibration
Gas Blends and What to Do About It," presented at Gulf Coast
Instrumental Analysis Conference at Houston, Texas, November 1, 1974.
171 Wechter, S.G., "Preparation of Stable Pollution Gas Standards Using
Treated Aluminum Cylinders," presented at ASTM Calibration Symposium
at Boulder, Colorado, August 5, 1975.
127
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PAGE 1 OF 2 FOR
1. TITLE REAGENT QUALITY WATER (FOR PREPARATION, CLEANING OF SAMPLE CONTAINERS)
2. IDENTIFICATION CODE
02-01-01-01
3. ABSTRACT OF METHODOLOGY
Type I reagent water, which is used with trace analysis methods is prepared by distillating water having a maximum electrical
conductivity of 20 micromhos/cm at 25°C (77°F) from glass or Teflon apparatus, followed by further purification with a mixed bed of
ion exchange materials. Type II reagent water, which is used for general laboratory testing, is prepared by single distillation from
a glass or Teflon apparatus. Reagent water must conform to specifications shown in Table 02-01-01-01A.
4. APPLICATION^ Engineering evaluation R&D, environmental assessment.
A) OPERATIONAL SCOPE
This is the recommended procedure for the preparation of all reagent quality waters. Reagent waters are suitable for use in
all standard methods of chemical analyses of all collected samples, where appropriate. (See 02-02-01-01 through 02-02-01-18;
02-03-02-01 through 02-03-02-21)
B) INTERFERENCES/LIMITATIONS
The ion-exchange process used in preparing Type I water may add organic contaminants.
C) RECOMMENDED USE AREA
This is the recommended method for preparation of reagent quality water for all engineering evaluation R&D.
5. OPERATIONAL PARAMETERS
A) RANGE See Table 02-01-01-01 for reagent water specifications.
B) ACCURACY N/A
C) PRECISION N/A
6. REAGENTS REQUIRED
Potassium permanganate solution (ACS reagent grade), concentrated
sulfuric acid (ACS reagent grade), Type I water.
7. EQUIPMENT REQUIRED
Apparatus for determining particulate matter, including sample
reservoir, evaporation apparatus (i.e., dust shield, evaporator
assembly, electronic control circuit, etc.).
8. KEYWORD INDEX: Reagent water specification; water for analysis; reagent preparation; equipment cleaning.
9. CROSS REFERENCE ID NUMBERS01"02"02"011 02-02-01-01 through 02-02-01-18; 02-03-02-01 through 02-03-02-21
10. REFERENCES
A) PRIMARY SOURCE
024 ASTM Committees D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23 D-1193-70,
"Standard Specification for Reagent Water," American Society for Testing and Materials, Philadelphia, PA.,'1971, p. 196-7.
B) BACKGROUND INFORMATION
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, D-1888,
Standard Method of Test for Particulate and Dissolved Matter in Industrial Water," p. 448-457.
024 ASTM Comittee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part ?! n nw
p. 156-161. u "» u-iizo,
024 AST868°885ttee °"19 and °~22' "Wat6r; AtmosPnen'c Analysis," 1971 Annual Book of ASTM Standards, Part 23, E-200,
C) FIELD APPLICATIONS
128
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PAGE 2 OF 2 FOR
ITLE
REAGENT QUALITY WATER (FOR PREPARATION, CLEANING OF SAMPLE
CONTAINERS) (CONTINUED)
10 NO. 02-01-01-01
Table 02-01-01-01A. Requirements for Type I and
Type II Reagent Water (Reference 024).
Reagent water shall conform to the following requirements:
Type I
Type II
Total matter, max, mg/liter (ppm)
Electrical conductivity, max, /„,
micromhos/cm at 25°C (77°F)1 '
Consumption of potassium
permanganate(3)
(1)
0.1
0.1
pass
test
2.0
5.0
pass
test
(1)
(2)
(3)
Total matter is determined in accordance with Method A of
ASTM D-1888, Test for Particulates and Dissolved Matter in
Industrial Water (Reference 024).
Electrical conductivity is determined in accordance with
ASTM Method D-1125, Test for Electrical Conductivity of
Water (Reference No. 024).
Consumption of potassium permanganate is determined by
adding 0.20 ml of KMnCty solution (0.316 g/liter) to a
mixture of 500 ml of reagent water and 1 ml of ^504 in a
stoppered bottle of chemically resistant glass.
129
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PAGE 1 OF 2 FOR
1. TITLE MBS CERTIFIED STANDARDS FOR ELEMENTS IN LUBRICATING OILS
2. IDENTIFICATION CODE
02-01-01-02
3. ABSTRACT OF METHODOLOGY
Table 02-01-01-02A lists stable, oil-soluble compounds which are certified standards for 11 elements commonly found in petroleum products.
A solution of one or more elements can be prepared by placing 5 ml of 2-ethylhexanoic acid, 4 ml of 6-methyl-2,4-heptanedione, and 2 ml
of xylene in a flask, followed by addition of the required weight of certified standard (see Table 02-01-01-02A). The solution is then
heated until the salt dissolves; this procedure is repeated for each standard added.
Two ml of bis (2-ethylhexyl) amine is added, followed by the addition of cool lubricating oil. The solution is reheated to 85°C,
allowed to cool and stored until use.
4. APPLICATION! Environmental assessment, engineering evaluation R&D.
A) OPERATIONAL SCOPE
Method is applicable to the identification of trace metals in organic liquids including Ba, Cd, Ca, Cr, Cu, Pb, Mn, Ni, Sr, V, and Zn.
B) INTERFERENCES/LIMITATIONS
Minimal, if proper precautions are taken in the preparation of the certified stock solutions.
C) RECOMMENDED USE AREA
These standards are applicable to all use areas as trace analysis standards for fuels.
& OPERATIONAL PARAMETERS
A) RANGE N/Q
B) ACCURACY ±10% or better relative area.
C) PRECISION ±102 or better.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
See Table 02-01-01-02A.
Standard atomic absorption spectrometer.
8. KEYWORD INDEX! Trace element analysis, atomic absorption spectrometry, certified organic standards.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02; 02-02-01-05.
10. REFERENCES
A) PRIMARY SOURCE
014 Hamersma, J.W., and S.R. Reynolds, "Tentative Procedures for Sampling and Analysis of Coal Gasification Processes," TRW Systems
Group, EPA Contract No. 68-02-1412, March 1975.
B) BACKGROUND INFORMATION
172 Dean, J.A., and T.C. Rains, "Flame Emission and Atomic Absorption Spectrometry," New York, Marcel Dekker, Inc., 1971.
018 FTegal, C.A., M.L. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Procedures for Process Measurements: Trace
Materials," TRW Systems Group, EPA Contract No. 68-02-1393, February 1975.
C) FIELD APPLICATIONS
130
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PAGE 2 OF 2 FOR
TITLE NBS CERTIFIED STANDARDS FOR ELEMENTS IN LUBRICATING OILS (CONTINUED) ID NO. 02-01-01-02
Table 02-01-01-02A. Standard Reference Materials in Lubricating Oil
(Element of Interest, 500 ug/g) (Reference 014).
NBS No.a
105 Ib
1053
1074a
1078
1080
1059b
1062a
1065b
1070a
1052b
1073b
Element of Interest
Ba
Cd
Ca
Cr
Cu
Pb
Mn
Ni
Sr
V
Zn
Compound
Cyclohexanebutyrate
Cyclohexanebutyrate
2-Ethylhexanoate
Tris (l-phenyl-l,3-butanediono)-chromium (III)
Bis (l-phenyl-l,3-butanediono)-copper (II)
Cycl ohexanebutyrate
Manganese (II) Cyclohexanebutyrate
Cyclohexanebutyrate
Cyclohexanebutyrate
Bis (l-phenyl-l,3-butanediono)-oxovanadium (IV)
Cyclohexanebutyrate
Drying
time, hrb
24
48
48
1
0.5
48
48
48
24
2
48
Weight
used, gc
0.174
0.202
0.373
0.515
0.303
0.136
0.362
0.360
0.242
0.348
0.299
National Bureau of Standards (U.S.) standard reference material.
Dried over P-O,- in desiccator.
Sleight of dried material which contains 50 mg of element of interest.
dDried in oven at 110°C.
eWeight of element, 20 mg, and gives a final concentration of 200 ug/g.
-------
1. TITLE STORAGE OF REAGENTS USED IN CHEMICAL ANALYSES
2. IDENTIFICATION CODE
02-01-01-03
3. ABSTRACT OF METHODOLOGY
Glass containers are suitable for the storage of most standard acidic or neutral reagent solutions; polyolefin containers (e.g., high
density polyethylene, polypropylene are preferred) are recommended for the storage of alkaline solutions. (See 02-01-01-05 for
suitable cleaning procedures of polyolefin containers.)
When large quantities of solutions are prepared, care must be taken to avoid changes in normality due to the absorption of gases
or water vapor from the ambient air. As volumes of solution are withdrawn from the original container, the incoming air should be
passed through a drying tube filled with sections of 8-to 20-mesh soda lime, oxalic acid and 4-to 8-mesh anhydrous calcium chloride,
with each separate section separated by a glass wool plug.
Once prepared, most standard solutions (1,000 ppm) should be periodically restandardized as a precautionary measure. Dilute solutions
(<1,000 ppm) should be prepared fresh from stock solutions prior to use.
4. APPLICATION'- Environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to the storage of reagent solutions for use in the recommended analytical procedures {see 02-02, 02-03)
for samples obtained from all types of effluent streams.
B) INTERFERENCES/LIMITATIONS
See (3) above for discussion of interferences by absorption of gases or water vapor during container transfers. Hg could cause
interference if not present in the ionic state.
C) RECOMMENDED USE AREA
This is the recommended method for storage of chemical reagents used in all the analytical procedures.
5. OPERATIONAL PARAMETERS
A) RANGE N/A
B) ACCURACY N/A
C) PRECISION N/A
6. REAGENTS REQUIRED
8- to 20-mesh soda lime; oxalic acid; 4- to 8-mesh anhydrous
calcium chloride for drying tube.
7. EQUIPMENT REQUIRED
Glass containers of appropriate size for storage of acidic and
neutral solutions; polyolefin containers (polyethylene or
polypropylene) containers of appropriate size for storage of
alkaline solutions; drying tube; tubing for solution transfer.
KEYWORD INDEX: Reagent storage, polyolefin containers.
9. CROSS REFERENCE IDNUMBERS See Sections 02-02 and 02-03; 02-01-01-01, 02-01-01-05.
10. REFERENCES
A) PRIMARY SOURCE
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, E200-67, "Preparation,
Philadelphia!0™!" 1971?p! °8f70"arldard Solutions for Chemical Analysis," American Society for Testing and Materials,
B) BACKGROUND INFORMATION '
173 ASTM Comittee E-2, E-3 and E-16, "Chemical Analysis of Metals; Sampling and Analysis of Metal Bearing Ores," 1971 Annual
Book of ASTH Standards, Part 32, "Apparatus, Reagents and Safety Precautions for Chemical Analysis of Metals " American
Society for Testing and Materials, Philadelphia, PA., 1971, p. 282-328.
C) FIELD APPLICATIONS
132
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1, TITLE NBS STANDARD REFERENCE MATERIALS FOR COAL AND FLY ASH
2. IDENTIFICATION CODE
02-01-01-04
3. ABSTRACT OF METHODOLOGY
It is recommended that prior to an actual sampling and analysis task, all the selected analytical techniques be tested in the
laboratory with NBS standards. This dry run of sample preparation, dissolution and analysis using Standard Reference Materials (SRMs)
will uncover any flaws in methodology, as well as acting as a check of the accuracy of the actual analysis. For environmental inorganic
samples, NBS SRM 1632 (coal) and SRH 1633 (coal fly ash) offer a rigorous test of the precision and accuracy of an environmental analysis
laboratory. They also can act as a blind test of commercial laboratories that are contracted to perform selected analyses.
4. APPLICATION: AH levels.
A) OPE RATIONAL SCOPE
This recommended methodology is designed to act as a check of the accuracy and precision of the personnel, equipment and
laboratory involved in the chemical analysis.
B) INTERFERENCES/LIMITATIONS
There are a limited number of elements certified in each SRM. Other researchers have determined other elements in the samples
and their results can be used as a guide for comparison (see references, background information).
C) RECOMMENDED USE AREA
These standards are applicable to all areas when standards for trace element analysis of fuels are required.
OPERATIONAL PARAMETERS
A) RANGE Trace element content.
B) ACCURACY NBS certified.
C) PRECISION NBS certified.
6. REAGENTS REQUIRED
Reagents required will be dictated by the choice of method and
preparation procedures.
7. EQUIPMENT REQUIRED
Depends on analytical methods of choice.
8. KEYWORD INDEX: SRM, analysis, NBS standards.
9. CROSS REFERENCE ID NUMBERS 02-02; 02-03; 02-04.
10. REFERENCES
a ..: NBS Standard Reference Materials," NBS Special Publication #260, U.S. Dept of Commerce, National Bureau of
Standards, June 1975.
Concentrations in NBS Environmental Coal and Flyash Standard Reference Materials," ML.
Chem., 47_, 1102 (1975).
FIELD APPLICATIONS
133
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1. TITLE CLEANING PROCEDURES FOR LABORATORY GLASSWARE AND PLASTIC LABWARE
2. IDENTIFICATION CODE
02-01-01-05
3. ABSTRACT OF METHODOLOGY
The stepwise procedure for preparation of labware for analytical use can be stated as follows:
(1) Remove old labels or markings with acetone or dry abrasive cleaners (Ajax, Dutch cleanser, etc.).
(2) Wash with 2:1 solution of Alconox or dry abrasive cleaner; rinse with tap water. Thoroughly rinse pipets and volumetric flasks.
(3) Rinse with the appropriate acid wash. Aqua regia (3:1 HCl-HNOj) is used on all labware used in Hg analysis. H2$04-HN03 in a
1:1 ratio is used on all other glassware, except volumetric flasks, for which concentrated warm (60°C) sulfuric acid is used.
Twenty percent nitric acid is used for plastic labware. A 24-hour soaking in chromic acid (100 g K2Cr20? per 3.5 liter H2SO.)
is required for pipets.
(4) Rinse once with tap water; flush 3 times with high purity water (see 02-01-01-01).
(5) Dry and store for use. Flasks with glass stoppers should be capped immediately after rinsing and stored. Open-mouth glassware
should be turned upside down on a rack and allowed to dry in an area free from contaminating drafts. One to 5 ml high purity
water should be poured into volumetric flasks, the glass stoppers inserted, and the flask inverted several times to see that the
water flows smoothly and no beading occurs in the neck (all the water to remain while storing). All labware should be stored in
clean, closed cabinets or drawers.
4. APPLICATION^ Engineering evaluation R&D, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to preparation of labware for analysis, including trace element analysis of liquids and slurries,
impinger solutions, bulk solids, particulate, matter, etc.
B) INTERFERENCES/LIMITATIONS
N/A
C) RECOMMENDED USE AREA
These are recommended procedures for preparation of all laboratory glassware and containers for analytical use in trace analysis.
5. OPERATIONAL PARAMETERS
A) RANGE N/A
B) ACCURACY N/A
C) PRECISION N/A
6. REAGENTS REQUIRED
Alconox, dry abrasive cleaners (Ajax, Dutch cleanser, etc.),
acetone, concentrated acids (hydrochloric, nitric, sulfuric),
potassium dichromate.
7. EQUIPMENT REQUIRED
N/A
R KEYWORD INDEX." Cleaning, labware, glassware, analysis.
9. CROSS REFERENCE ID NUMBERS 02-01-01-01, 02-01-01-07.
10. REFERENCES
A) PRIMARY SOURCE
018 Flegal, C.A., M.L. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Procedure for Process Measurements: Trace
Inorganic Materials," TRW Systems Group, EPA Contract No. 68-02-1393, July 1975, p. 7-1 and 7-2
B) BACKGROUND INFORMATION
024 ASTM Committee D-l9 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, D1193-70
Standard Specification for Reagent Water," American Society for Testing and Materials, Philadelphia, PA., 1971, p. 196-7.
C) FIELD APPLICATIONS
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PAGE 1 OF 2 FOR
1, TITLE PREPARATION OF HIGH PURITY REAGENTS FOR TRACE ANALYSIS
— ' "-
1 ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-01-01-06
Laboratory methods of purification and preparation of some common reagents used for separations in trace analysis are shown in
Table 02-01-01-06A. Although distillations are most widely used for volatile reagents, various other separation methods are also
useful for purifying reagents. For example, heavy metal impurities are satisfactorily removed from neutral aqueous solutions of
various salts by extraction with a carbon tetrachloride solution of dithizone or with a chloroform solution of oxine, and from
hydrochloric acid by passing through an anion exchange resin column. Table 02-01-01-06A summarizes the recommended procedures
for purification.
4. APPLICATION: Engineering evaluation R&D.
AJ OPERATIONAL SCOPE
These procedures are designed to remove trace impurities from laboratory reagents.
B) INTERFERENCES/LIMITATIONS
These methods require scrupulous cleaning of all glassware involved in the purification procedure. Because of the time and
cost involved in batch purifications, commercial high purity reagents are recommended.
C) RECOMMENDED USE AREA
This method is useful when high purity materials are required and not commercially available.
5. OPERATIONAL PARAMETERS
A) RANGE N/A
B) ACCURACY N/A
C) PRECISION N/A
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
See Table 02-01-01-06A.
Glass/teflon distillation apparatus, laboratory glassware.
& KEYWORD INDEX-' Analysis, high purity reagents.
9. CROSS REFERENCE ID NUMBERS 02-01-01-03, 05.
10. REFERENCES
A) PRIMARY SOURCE
166 Morrison, 6.H. (ed.), "Trace Analysis Physical Methods," Interscience Publishers, New York, N. V., 1965.
B) BACKGROUND INFORMATION „ ul • u w J VA..V 1017 n 273
176 Thiers, R.E., in "Methods of Biochemical Analysis," D. Glick (ed.), Vol. 5, Interscience Publishers, New York, 1957, p. 273.
177 Irving, H., and J.J. Cox, Analyst, 83, 526 (1958).
178 Wickbold, R., Z. Anal. Chern., Vn, 81 (1959).
179 Rees. H.T., Analyst, 87, 202 (1962).
180 Stegemann, H.. Z. AhaTT Chem.. 154. 267 (1957).
C) FIELD APPLICATIONS
235
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PAGE 2 OF 2 FOR
TITLE PREPARATION OF HIGH PURITY REAGENTS FOn TRACE ANALYSIS (CONTINUED)
ID NO. 02-01-01-06
Table 02-01-01-06A. (From Morrison, "Trace Analysis," Ref. 166).
Recommended Laboratory Methods of Purification and Preparation of High Purity Reagents
1
i Reagent
Water
HC1
HN03
H2S04
HC104
HF
NH^OH
NaOH
KOH
Method
Ion exchange followed by distillation
Dissolution of anhydrous HC1 gas in pure water
Repeated distillation of 65% HN03
Repeated distillation
Repeated distillation
Distillation
Dissolution of HF gas in pure water
Dissolution of anhydrous NH, gas in pure water
Conversion of NaCl (purified by extraction with oxine and dithizone) with an OH-form anion
exchange resin
Conversion of KC1 (purified by extraction with oxine and dithizone) with an OH-form anion exchange
resin
Background Information
Reference
176
I
178, 179 |
180 i
176
176
136
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1. TITLE GAS SAMPLING CONTAINER CLEANING PROCEDURE
•i " —
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-01-01-07
Sample containers used in gas sampling procedures should be constructed of chemically resistant glass in order to avoid sample
contamination. New containers should be conditioned prior to use by allowing them to stand full of distilled water for several days.
Conditioning may be accelerated by treatment with dilute hydrochloric acid. Prior to use, the containers should be thoroughly
cleaned in order to remove extraneous dirt. A 2:1 mix of Alconox or abrasive cleaner and water may be used on the exterior and
interior of the container, followed by rinsing with tap water. The container is then rinsed with an acid wash; an aqua regia
(3:1 HC1-HN03) acid cleaning solution is used on all labware involved in Hg analysis, while a 1:1 H2S04-HNO is used on all remain-
ing glassware (see 02-01-01-05). After tap water rinsing of the acid, the sample container is immediately flushed with 3 volumes of
high purity water. The container is then filled with deionized water prior to storage.
4. APPLICATION- Engineering evaluation R&D, environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to preparation of all glass sampling containers used in gas sampling.
B) INTERFERENCES/LIMITATIONS
N/A
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D and environmental assessment procedure for the preparation of glass
containers for sampling gases.
5. OPERATIONAL PARAMETERS
A) RANGE
B)
C)
N/A
ACCURACY
N/A
PRECISION
N/A
6. REAGENTS REQUIRED
Alconox or abrasive cleaner (Ajax, Dutch cleanser, etc.),
deionized water; aqua regia (3:1 HC1-HN03), concentrated sulfuric
acid, concentrated nitric acid.
7. EQUIPMENT REQUIRED
N/A
8L KEYWORD INDEX: Container cleaning procedure, gas sampling.
9. CROSS REFERENCE ID NUMBERS 02-01-01-01, 02-01-01-05; 01-05-04-01; 01-01-04-01.
10. REFERENCES
A) PRIMARY SOURCE Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, Dl192, "Standard
Sp™1fi™tion for Equipment for Sampling Water and Steam," American Society for Testing and Materials, Philadelphia, PA.,
1971, p. 190-194.
B) BACKGROUND INFORMATION „ „ --_-_*«• Trace
—
C) FIELD APPLICATIONS
137
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_ , ION EXCHANGE METHOD FOR THE ISOLATION OF FLUORIDE FROM
1. TITLE ENVIRONMENTAL SAMPLES
Z IDENTIFICATION CODE
02-01-02-01
3. ABSTRACT OF METHODOLOGY
Fluoride is removed from solution by preferential absorption on an ion exchange resin followed by desorption of fluoride
in a small volume of eluting solution. Concentration of fluoride from an impinger or bubbler collection medium may be
achieved without danger of contamination from prolonged exposure of solutions, such as occurs with steam distillation.
4. APPLICATION'- Engineering evaluation R&D, environmental assessment.
A) OPERATIONAL SCOPE
This method is applicable to any environmental sample which requires isolation handling of small quantities of fluoride.
B) INTERFERENCES/LIMITATIONS
This method removes interfering cations by absorbing the fluoride on the anion exchange resin, allowing the cations to pass
through. The fluoride is then eluted with sodium hydroxide solution. Aluminum or Si will interfere by forming
complexes with F .
C) RECOMMENDED USE AREA
Recommended for any sample at any level where less severe interferences to fluoride measurement exist. The Nillard/Winter
distillation is the recommended procedure where Al and Si are present (see 02-01-02-02).
5. OPERATIONAL PARAMETERS
A) RANGE
Hicrogram to low milligram quantities.
B) ACCURACY +_5% Note: Low recovery indicates incomplete preconditioning of a new column, while high recovery may be due
to contamination or failure to elute the previous sample.
C. PRECISION N/Q (±M estimflted)_
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Anion exchange resin [Duolite A-41, A-43; lonac A302;
PERMUTIT A; REXYN 205(OH)],hydrochloric acid, sodium hydroxide,
quartz sand.
Chromatography column, lab glassware.
8. KEYWORD INDEX. Analysis, fluoride analysis, ion exchange, fluoride.
9. CROSS REFERENCE ID NUMBERS 02-03-02-01, 02-03-02-02(02-01-02-02.
10. REFERENCES
A) PRIMARY SOURCE
103 ASTM, "Tentative Methods for Analysis for Fluoride Content of Atmosphere and Plant Tissue (Manual Procedures),"
1974,3Annual Book of ASTM Standards, Part 26, D3269-73T, American Society for Testing and Materials, Philadelphia, PA., 1971,
B) BACKGROUND INFORMATION
181 Newman, A.C.D., "Separation of Fluoride Ions from Interfering Ions and Cations by Anion Cation Exchanne Chromatrophotorcetry,"
Anal. Chim. Acta. 19_, 471 (1958).
C) FIELD APPLICATIONS
182 Nielson, A.P., and A.D. Dangerfield, "Use of Ion Exchange Resin for Determination of Atmospheric Fluorides," A.M.A.
Archives of Industrial Health, JJ_, 61 (1955).
138
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1. TITLE WILLARD WINTER DISTILLATION FOR THE ISOLATION OF FLUORIDE FROM
ATMOSPHERIC SAMPLES
Z IDENTIFICATION CODE
02-01-02-02
3. ABSTRACT OF METHODOLOGY
The prepared sample is distilled from a strong acid such as sulfuric or perchloric in the presence of a source of silicate. Fluoride
is steam distilled as the fluorosilicic acid under conditions permitting a minimum of volatilization and an entrapment of liberating acid.
Samples relatively free of interfering materials and containing easily liberated fluoride forms can be subjected to a single dissolution
from perchloric acid at a 135 C. Samples containing aluminum, boron or silicon may require a higher temperature and a larger volume
of distillate for quantitative recovery. In this case, a preliminary displacement from sulfuric acid at 165°C is commonly used. Chlorides
are separated by precipitation with silver perchlorate.
4. APPLICATION: Engineering evaluation R&D
A) OPERATIONAL SCOPE
This distillation procedure can be used for any environmental sample provided that major interferences such as aluminum, silicon and
boron are not present. In the event that these three are present, the double dissolution procedure is the recommended mode of
operation.
B) INTERFERENCES/LIMITATIONS
Not useful for low level fluoride.
C) RECOMMENDED USE AREA
Engineering evaluation R&D.
5. OPERATIONAL PARAMETERS
A) RANGE From 1 mg to 100 mg.
B) ACCURACY In general, recoveries will be ±10% of the fluoride present.
C) PRECISION Standard deviations under favorable circumstances have been as low as 0.5*.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Perchloric acid, silver perchlorate and sulfuric acid.
Steam generator,distillation flask, Liebig condenser, steam
release tube, thermometer, support plate, receiver, safety
tube, rubber tubing, soft glass beads, boiling chips, pinch cock.
8. KEYWORD INDEX: Analysis, fluoride analysis, fluoride dissolution.
9. CROSS REFERENCE ID NUMBERS 02-01-02-01; 02-03-02-01, 02-03-02-02.
10. REFERENCES
M native Methods for Analysis for Fluoride Content of the Atmosphere and Plant Tissues (Manual Procedures),
1974 Annual Book of ASTM Standards, Part 26, Method D3269-731, p. 735.
B] BACKGROUND INFORMATION ^ „ ., „ . . c ..„„, .„,,
183 Willard, H.H., and O.B. Winter, "Volumetric Method for Determination of Fluoride, Ind. Eng. t-hem. flnai.,
5th ed., 5_, 7 (1933).
O.E. Gardner, "The Drten.1n.t1on of Fluoride in Urine," Am. Ind. Hyg. Assoc.. 16, 215 (1955).
139
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PAGE 1 OF 2 FOR
1. TITLE SEPARATION OF LIQUID/SLURRY SAMPLES
2. IDENTIFICATION CODE
02-01-02-03
3. ABSTRACT OF METHODOLOGY
Once a liquid or liquid/slurry sample is collected, it must be properly stored prior to return to the laboratory. In many
cases, it is desirable to separate the filterable and nonfilterable solids from the liquid and store them in separate
containers for analysis in the laboratory. Filterable (dissolved) solids are those which pass through a standard glass
fiber filter; they are determined by evaporation of the filtrate to constant weight at 180°C (356°F). Nonfilterable (suspended)
solids are those which are retained by a standard glass fiber filter; retained residues are then determined by
drying to constant weight at 103-105 C.
Total solids (suspended solids and dissolved materials) are quantitatively determined by evaporation to dryness in
an evaporation dish and weighing. Figure 02-01-02-03A outlines the separation techniques required to separate water-
solid, water-organic liquid, and water or organic liquid-solid streams into their component parts. Addition of nitric
acid to one-half of the filtrate is designed to keep most cations in solution and to prevent them from absorbing on the
polyethylene container walls. On the other hand, sodium hydroxide is added to stabilize anions such as cyanide during
shipment. (For specific additives to samples for preservation see 02-01-03-01.)
4. APPLICATION: Environmental assessment.
A) OPERATIONAL SCOPE
These methods are designed to be used on any stream containing solids, liquids, and organic liquids in any combination.
B) INTERFERENCES/LIMITATIONS
In general, the addition of nitric acid or sodium hydroxide should not interfere with any analytical procedures to be
performed on the sample. The analyst must always remember the ultimate analysis goal of the collected samples, and prevent
separations or reagent additions from interfering with his analysis scheme.
C) RECOMMENDED USE AREA
Preservation of samples for environmental assessment.
5. OPERATIONAL PARAMETERS
A) RANGE 10 to 20,000 ing/liter of dissolved solids; 20 to 20,000 mg/liter suspended solids; 10 to 30,000 mg/liter
total solids; N/Q for volatile solids.
B) ACCURACY N/A
C) PRECISION Standard deviation of ±11 mg/liter at 170 mg/liter volatile solids concentration was determined for 4 samples
in 3 laboratories.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
High purity nitric acid, high purity sodium hydroxide, high
purity methanol, high purity distilled water.
Teflon filters, Nalgene separatory funnel, Nalgene filter flask,
Nalgene vacuum pump; Gelman Spectrograde glass fiber filters (or
equivalent), Nalgene Buchner funnel, laboratory oven (103-105°C,
8. KEYWORD INDEX: Analysis, sample storage, liquid/slurry separation.
9. CROSS REFERENCE ID NUMBERS 02-01-03-01,02-01-01-06.
10. REFERENCES
A) PRIMARY SOURCE
018 Flegal, C.A., M.L. Kraft, C. Lin, R.F. Haddalone, J.A. Starkovich and C. Zee, "Procedures for Process Measurements: Trace
Inorganic Materials, TRW Systems Group, EPA Contract #68-02-1392, July 1975.
185 "Methods for Chemical Analysis of Water and Wastes," National Environmental Research Center, EPA-625/6-74-003.
Washington, 1974.
B) BACKGROUND INFORMATION
186 AgencyC°PB-228-425 "
C) FIELD APPLICATIONS
And1yt1cal Methods' Vo1- "• Method Summaries," U.S. Environmental Protection
140
-------
TITLE
SEPARATION OF LIQUID/SLURRY SAMPLES (CONTINUED)
PAGE 2 OF 2 FOR
ID NO. 02-01-02-03
WATER
\
HNO,
NaOH
WATER-SOLID
FILTER H20 WASH
FILTRATE
\
SOLIDS - STORE
IN CLEAN BOTTLE
WITH FILTER
HNO-
NaOH
WATER-ORGANIC LIQUID
SEPARATORY
FUNNEL
WATER
/ \
HNO,
NaOH
ORGANICS-
REFRIGERATE
AND SHIP IN
DRY ICE
WATER-ORGANIC LIQUID-SOLIDS
FILTER-WASH WITH FILTRATE
SOLIDS - STORE
IN CLEAN BOTTLE
WITH FILTER
WATFR
y v* ORGANICS - REFRIGERATE
f ^™, AND SHIP IN DRY ICE
DO NaOH
Figure 02-01-02-03A. Typical Separation Schemes for Process Liquids.
M
-------
PAGE 1 OF 4 FOR
1. TITLE RECOMMENDATIONS FOR PRESERVATION OF SAMPLES ACCORDING TO MEASUREMENT
Z IDENTIFICATION CODE
02-01-03-01
3. ABSTRACT OF METHODOLOGY
Table 02-01-03-01A is a general summary of the preservation methods that are employed to retard change in the samples.
Table 02-01-03-01B details methods of preservation that are intended to retard biological action, hydrolyses of chemical
compounds and complexes, and to reduce volatility of constituents. This table also contains information concerning the
normal volume required for a standard AIHA analytical analysis, as well as the type of storage container and the longest
holding time possible in that container.
4. APPLICATION: A11 ieveis.
A) OPERATIONAL SCOPE
These preservation techniques are designed to be used on samples of domestic sewage, industrial waste or
natural waters.
B) INTERFERENCES/LIMITATIONS
Regardless of the nature of the sample, complete stability for every constituent can never be achieved. At best,
preservation techniques can only retard the chemical and biological changes that inadvertently continue after the
sample is removed from the parent source. The only solution to this problem is speedy analysis of the sample once it
has been removed from the source.
C) RECOMMENDED USE AREA
These practices are recommended for all use areas.
5. OPERATIONAL PARAMETERS
A) RANGE These preservation techniques can be used to preserve trace to major components of the sample.
B) ACCURACY N/A
C] PRECISION N/A
6. REAGENTS REQUIRED
(See Table 02-01-03-01A and B)
7. EQUIPMENT REQUIRED
(See Table 02-01-03-01A and 8)
8. KEYWORD INDEX: Analysis, sample preservation.
9. CROSS REFERENCE ID NUMBERS
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Waste," National Environmental Research Center, EPA 625/6-74-003, Washington, 1974.
B) BACKGROUND INFORMATION
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, "Standard Methods
ot Sampling Industrial Water," American Society for Tasting and Materials, Philadelphia, PA., 1971, p. 2.
C) FIELD APPLICATIONS
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PAGE 2 OF 4 FOR
1
TITLE RECOMMENDATIONS FOR PRESERVATION OF SAMPLES ACCORDING ID NO. 02-01-03-01 I
TO MEASUREMENT (CONTINUED)
Table
Preservative
HgCl2
Acid (HN03)
Acid (H2S04)
Alkali (NaOH)
Refrigeration
02-01-03-01A. General Preservation Techniques (185).
Action
i
Bacterial Inhibitor
Metals solvent, prevents
precipitation
Bacterial Inhibitor
Salt formation with
organic bases
Salt formation with
volatile compounds
Bacterial Inhibitor
Applicable to:
Nitrogen forms,
phosphorus forms
Metals
Organic samples
(COD, oil and grease,
organic carbon)
Ammonia, amines
Cyanides, organic
acids
Acidity-alkalinity,
organic materials,
BOD, color, odor,
organic P, organic N,
carbon, etc. , biologi-
cal organism
(coliform, etc. )
I
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PAGE 3 OF 4 FOR
TITLE
RECOMMENDATIONS FOR PRESERVATION OF SAMPLES ACCORDING.
TO MEASUREMENT (CONTINUED)
ID NO. 02-01-03-01
Table 02-01-03-018. Recommendation for Sampling
Preservation of Samples According to Measurement
and
(185).
Measurement
Acidity
Alkalinity
Arsenic
BOD
Bromide
COD
Chloride
Chlorine Req.
Color
Cyanides
Dissolved Oxygen
Probe
Kinkier
Fluoride
Hardness
Iodide
MBAS
Metals
Dissolved
Suspended
Total
Mercury
Dissolved
Total
Nitrogen
Ammoni a
Kjeldahl
Nitrate
Nitrite
NTA
Vol.
Req.
(ml)
100
100
100
1000
100
50
50
50
50
500
300
300
300
100
100
250
200
100
100
100
400
500
100
50
50
Container
P, G<2'
P, G
P, G
P, G
P. G
P, G
P, G
P, G
P, G
P, G
G only
G only
P. G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
Preservative
Cool, 4°C
Cool, 4°C
HN03 to pH <2
Cool, 4°C
Cool, 4°C
HjS04 to pH <2
None Req.
Cool, 4°C
Cool, 4°C
Cool, 4°C
NaOH to pH 12
Det. on site
Fix on site
Cool, 4°C
Cool, 4°C
Cool, 4°C
Cool , 4°C
Filter on site
HN03 to pH <2
Filter on site
HN03 to pH <2
Filter
HN03 to pH <2
HN03 to pH <2
Cool, 4°C
H2S04 to pH <2
Cool, 4°C
H2S04 to pH <2
Cool, 4°C
H2S04 to pH <2
Cool, 4°C
Cool, 4°C
Holding
Time(6)
24 Mrs.
24 Hrs.
6 Mos.
6Hrs.<3'
24 Hrs.
7 Days
7 Days
24 Hrs.
24 Hrs.
24 Hrs.
No Holding
Ho Holding
7 Days
7 Days
24 Hrs.
24 Hrs.
6 Mos.
6 Mos.
6 Mos.
38 Days
(Glass)
13 Days
(Hard
Plastic)
38 Days
(Glass)
13 Days
(Hard
Plastic)
24 Hrs.'4'
24 Hrs.(4)
24 Hrs.'4'
24 Hrs.'4'
24 Hrs.
-------
TITLE
PAGE 4 OF 4 FOR
—-
ID NO. 02-01-03-01
'Table 02-01-03-01B. (Continued)
Measurement
i- ,.
Oil & Grease
Organic Carbon
pH
Phenol ics
Phosphorus
Ortho-
phosphate,
Dissolved
Hydrolyzable
Total
Total ,
Dissolved
Residue
Filterable
Non-
Filterable
Total
Volatile
Settleable Matter
Selenium
Silica '
Specific
Conductance
Sulfate
Sulfide
Sulfite
Temperature
Threshold
Odor
Turbidity
Vol.
Req.
(ml)
'1000
25
25
500
50
50
50
50
100
100
100
100
1000
50
50
100
50
50
50
1000
200
100
Container
G only
P, G
P, G
G only
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P only
P, G
P, G
P. G
P, G
P. G
G only
P, G
Preservative
Cool, 4°C
H2S04 to pH <2
Cool, 4°C
H2S04 to pH <2
Cool, 4°C
Det. on site
Coo], 4°C
HrfOn to pH <4
1.0 g CuS04/l
Filter on site
Cool , 4°C
Cool, 4°c
H2S04 to pH <2
Cool, 4°C
Filter on site
Cool, 4°C
Cool, 4°C
Cool, 4°C
Cool, 4°C
Cool, 4°C
None Req.
HN03 to pH <2
Cool, 4°C
Cool, 4°C
Cool, 4°C
2 ml zinc
acetate
Cool , 4°C
Det. on site
Cool, 4°C
Cool, 4°C
Holding
Time(6)
24 Hrs.
24 Hrs.
6Hrs.<3>
24 Hrs.
24 Hrs.(4)
24 Hrs.(4)
24 Hrs. <4'
24 Hrs.(4)
7 Days
7 Days
7 Days
7 Days
24 Hrs.
6 Mos.
7 Days
24 Hrs.'5'
7 Days
24 Hrs.
24 Hrs.
No Holding
24 Hrs.
7 Days
1. More specific instructions for preservation and sampling are found with
each procedure as detailed in this manual. A general discussion on
sampling water and industrial wastewater may be found in ASTM, Part 23,
p. 72-91 (1973).
2. Plastic or Glass
3. If samples ca.njiot be returned to the laboratory in less than 6 hours and
holding time exceeds this limit, the final reported data should indicate
the actual holding time.
4. Mercuric chloride may be used as an alternate preservative at a concen-
tration of 40 mg/1, especially if a longer holding time is required.
However, the use of mercuric chloride is discouraged whenever possible.
5. If the sample is stabilized by cooling, it should be warmed to 25°C for
reading, or,temperature correction made and results reported at 25°C.
6. It has been shaw/i that samples properly preserved may be held for
extended periods beyond the recommended holding time.
145
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PAGE 1 OF 3 FOR
, _._. _ PREPARING COAL SAMPLES FOR ULTIMATE AND/OR PROXIMATE ANALYSIS
1. IIILt (MECHANICAL AND MANUAL REDUCTION AND DIVISION)
2. IDENTIFICATION CODE
02-01-03-02
3. ABSTRACT OF METHODOLOGY
Figure 02-01-03-02A presents a flow diagram which sunmarizes the procedure of sample preparation for analysis. The recommended minimum
sizes for initial reduction of the gross sample (collected using procedure of 01-03-01) are shown in Table 02-01-03-02A. The sample
is then ground to pass a No. 4 mesh sieve (4.75 x 0 mm) as indicated in Table 02-01-03-02B. The sample is then divided using a large
riffle (see Figure 02-01-03-02B for diagram of acceptable riffle sampler) to a quantity not less than shown in Table 02-01-03-02B,
followed by further reduction to No. 8 mesh sieve with suitable pulverizing equipment. The subsample is then divided by riffling to not
less than the quantity shown in Table 02-01-03-02B. Successive reductions and divisions are carried out until No. 60 mesh sieve is
achieved. Mechanical dividers other than rifflers, such as reciprocating or rotating cutters, rotating hoppers, etc., can also be
used.
When rifflers or other mechanical devices are unavailable, samples can be reduced by manual coning and quartering methods, as illustrated
in Figure 01-03-02-01A.
4. APPLICATION- Environmental assessment.
A) OPE RATIONAL SCOPE
The methods are applicable to all coal samples collected under 01-03-01, at ambient temperatures and pressures.
B) INTERFERENCES/LIMITATIONS
Proper use of the methods reflect consideration of the gas sample itself and of number and weight of increments required. Results
are influenced by skill of the personnel involved and the care taken in the procedures employed.
C) RECOMMENDED USE AREA
This is the recommended procedure for the preparation of coal samples for all levels of analysis. Methods apply
to all coals sampled by procedures cited in 01-03-01. See 02-02-01-03, 02-03-04, and 02-02-01-04.
5. OPERATIONAL PARAMETERS
A) RANGE Sample reduction and division depends on the range of the equipment (manual and automatic) used.
Bl ACCURACY 10% or better.
C) PRECISION ±10* or better.
a REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
N/A
Air drying oven (optional), gross sample scale, laboratory balance; crushers or
grinders (jaw, cone, or rotary crusher or hammer mill); pulverizer or mill
(porcelain-jar ball mill); mixing wheel; sieves; mortar and pestle; mechanical
sample dividers, riffles, feed scoop, feed trough; laboratory sample containers.
& KEYWORD INDEX: Sample preparation, solids, reduction/division, air drying, moisture.
9. CROSS REFERENCE ID NUMBERS 01-03-01-02« 02-02-01-03, 02-02-01-04; 01-03-02-01; 02-03-04.
10. REFERENCES
A) PRIMARY SOURCE
057 ASTM Committee D-3 and D-5, "Gaseous Fuels; Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, D2013-68,
"Preparing Coal Samples for Analysis," American Society for Testing and Materials, Philadelphia, PA., 1971, p. 323-336.
058 Hamersma, J.W.,and S.R. Reynolds, "Tentative Procedures for Process Measurements, Lurgi Coal Gasification Process,"
EPA Contract No. 68-02-1412, March 1975.
B) BACKGROUND INFORMATION
057 ASTM Committee D-3 and D-5, "Gaseous Fuels; Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, 02234, "Standard
Methods for Sampling of Coal," American Society for Testing and Materials, Philadelphia, PA., 1971, p. 357-375.
057 ASTM Committee D-3 and D-5, "Gaseous Fuels; Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, Ell, "Wire
Cloth Sieves for Testing Purposes," American Society for Testing and Materials, Philadelphia, PA., 1971, p. 431-435.
057 ASTM Committee D-3 and D-5, "Gaseous Fuels; Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, 0197-30. "Samplm
and Fineness Test of Pulverized Coal," American Society for Testing and Materials, Philadelphia, PA., 1971, p. 10-12.
057 ASTM Committee D-3 and D-5, "Gaseous Fuels; Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, D410-38,
Qt^^,.4 Hethod of Test for Sieve Ana]ysjs Qf C(ja]>,, A(nen.can Society for Testing and Materials, Philadelphia, PA., 1971
146
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PAGE 2 OF 3 FOR
TITLE PREPARING COAL SAMPLES FOR ULTIMATE AND/OR PROXIMATE ANALYSIS
(MECHANICAL AND MANUAL REDUCTION AND DIVISION) (CONTINUED)
ID NO.
02-01-03-02
C) FIELD APPLICATIONS
186 Silverman, L., et al, "Particla Size Analysis in Industrial Hygiene," New York, Academic Press, 1971, p. 71.
SAMPLE COLLECTED
PER ASTH METHOD
D2234
(SEE 01-03-01-02)
1
WEIGH, AIR DRY,
REWEIGH
REDUCE TO INTERMEDIATE
SIZE (2.4 MM X 0) BY
GRINDING
WEIGH, AIR DRY (OPTIONAL
IF SAMPLE IS ALREADY DRY),
REWEISH
DIVIDE INTO SHIPPING
(1 KG) SAMPLE
FINAL REDUCTION
FOR LAB ANALYSIS
ANALYZE
Figure 02-01-03-01A. Scheme for Preparation of Coal Samples for Analysis (From Reference 057).
FEED CHUTE
AT LEAST FOURTEEN
13 MM (1/2 IN.) TO
25 MM (1 IN.)
OPENINGS
RIFFLE SAMPLER
RIFFLE BUCKET AND
SEPARATE FEED CHUTE STAND
Figure 02
-01-03-02B. Riffle Samplers (From Reference 057).
147
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PAGE 3 OF 3 FOR
TITLE PREPARING COAL SAMPLES FOR ULTIMATE AND/OR PROXIMATE ANALYSIS
(MECHANICAL AND MANUAL REDUCTION AND DIVISION) (CONTINUED)
ID NO.
02-01-03-02
Table 02-01-03-02A. Size Reduction of Gross Sample* (Reference 057).
Material passing 100% through screen
5 15 cm (2 - 6 in.)
1.6 - 15 cm (5/8 - 2 in.)
1.6 cm (5/8 in.) and under
Divide to a minimum weight of kg ~~~
Group A**
105 kg
45 kg
15 kg
Group B***
245 kg
100 kg
35 kg
*Based on the data from Table 01-03-01-02A
Mechanically cleaned coal
***
All other coal
Table 02-01-03-02B. Preparation of Laboratory Samples (Reference 057).
Divide to a minimum weight of g*
Crush to pass at least 95% through sieve
Group A**
Group B*
No. 4 (4.74 mm)
No. 8 (2.36 mm)
No. 20 (850 urn)
No. 60 (250 urn) (100% through)
2000
500
250
50
4000
1000
500
50
If a moisture sample is required,increase the quantity of No. 4 (4.75 mm) or No. 8 (2.36 mm) sieve subsample
by 500 g
Mechanically cleaned coal
*
All other coals
-------
1. TITLE SAMPLE RECOVERY FROM IMPINGERS
_- •"• — "•• —__„___
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-01-03-03
Upon completion of sampling by absorption in liquids contained in impingers, the contents of each impinger are returned quantitati 1
to individually labelled original solution bottles. Each liquid impinger is rinsed with 50 ml portions of high purity water- the
rinsings are then combined with the catch. Concentrated nitric acid may be added to reduce the pH to between 1 and 2 in order to
stabilize metal ions and to prevent formation of precipitates (hydroxides) and/or absorption of sample trace elements'on container
surfaces. Alternatively, sodium hydroxide can be added to stabilize anions. Following shipment to and receipt of the samples in the
laboratory, the volumes of each of the solutions are measured using a clean graduated cylinder, and the solutions are then returned
to the original containers. It is desirable to begin with the last impinger solution in the sampling train and to work toward the
first solution which has the greatest concentration of trapped species. The graduated cylinder is rinsed between each solution
measurement, and cleaned with nitric acid between series of solutions.
4. APPLICATION- Environmental assessment, engineering evaluation R&D
A) OPERATIONAL SCOPE
Method is applicable to sample recovery of liquid impingers and pre-cooler trap, from flue gas and fugitive gas sampling.
B) INTERFERENCES/LIMITATIONS
Precipitate formation and trace element absorption on container walls may occur if low pH is not maintained in solutions.
C) RECOMMENDED USE AREA
This is the recommended procedure for sample recovery from impingers, including pre-cooler traps for environmental assessment
and engineering evaluation R&D.
5. OPERATIONAL PARAMETERS
A) RANGE N/A
B) ACCURACY N/A
C) PRECISION N/A
a REAGENTS REQUIRED
Concentrated nitric acid, reagent quality water.
7. EQUIPMENT REQUIRED
Graduated cylinder, labeled solution bottles.
8. KEYWORD INDEX: Sample recovery, impingers.
9. CROSS REFERENCE ID NUMBERS 01-05; 02-01-01-01, 02-01-01-05, 02-01-03-01.
10. REFERENCES
1CAE, M.L. Kraft, C. Lin, R.F. Maddalone 0 A Starch and C. Zee .'Procedures for Process Measurements:
Trace Inorganic Materials," TRW Systems Group, EPA Contract #68-02-1393, July ia/5.
B) BACKGROUND INFORMATION
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis " 1971 Annual Book:o£ AST* "andards Part 23 D1 93-70,
"Standard Specification for Reagent Water," American Society for Testing and Materials, laaeipma,
C) FIELD APPLICATIONS
-------
PAGE 1 OF 2 FOR
1. TITLE REMOVAL OF FILTERS FROM FILTER HOLDERS
2. IDENTIFICATION CODE
02-01-03-04
3. ABSTRACT OF METHODOLOGY
The filter must be carefully removed from the sampler in a clean, dust-free area using the following procedure. First, the filter holder is
loosened, and the clamp frame is carefully removed from the surface of the filter. Using duct-bill tweezers, filter material adhering to
the clamp frame is scraped onto the filter surface. Next, the tweezers are inserted under the filter (between the filter and filter support)
and one inch (2.54 cm) of the outer boundary is folded toward the center. The filter is then folded in half, then in quarters (see Figure
02-01-03-01A). The folded filter is then placed in a labeled petri particulate-bearing filter and is dried at 105°C .for three hours, cooled
in a desiccator and weighed. Any paniculate matter collected from liners, cyclone and cyclone wash are then transferred to the filter pad
after they are individually weighed (see 02-01-03-05).
The composite sample is ready for subsequent analysis by oxygen plasma ashing (see 02-01-04-02). The filter used in the high volume stack
sampler (see 01-01-01-03) is removed from the housing using polyethylene gloves in a clean, dust-free environment and is then transferred
to a polyethylene envelope for subsequent morphological analysis (see 02-04-01-03, 02-04-01-04, 02-04-02-03) or chemical analysis (02-02).
4. APPLICATION- Environmental assessment, engineering evaluation R&D.
A) OPERATIONAL SCOPE
Method is applicable to all standard filters used in flue gas and fugitive gas sampling equipment.
B) INTERFERENCES/LIMITATIONS
Care must be taken to avoid loss of sample due to spillage, or sample contamination by dust, dirt, or equipment.
C) RECOMMENDED USE AREA
This procedure is used for environmental assessment and engineering evaluation R&D.
5. OPERATIONAL PARAMETERS
A) RANGE N/A
B) ACCURACY N/A
Cl PRECISION N/A
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
N/A
Drying oven (to 105°C); desiccator; analytical balance.
a KEYWORD INDEX: Filter, particulate, handling.
CROSS REFERENCE ID NUMBERS 01-01-01-03; 02-01-04-02, 02-01-03-05, 02-01-03-06; 02-04-01-04, 02-04-01-03, 02-04-02-03.
10. REFERENCES
A) PRIMARY SOURCE
058 Hamersma, J.W., and S. Reynolds, "Tentative Procedures for Process Measurements; Lurgi Coal Gasification Process," EPA
Contract No. 68-02-1412, TRW Systems, Inc., March 1975, p. 4-6.
B) BACKGROUND INFORMATION
018 T^Lv'S'; M'-L; K™™', Cc' tin> P- Melons, J-A- Starkovich and C. Zee, "Procedures for Process Measurements: Trace
Inorganic Materials," TRW Systems Group, EPA Contract #68-02-1393, July 1975.
187 uMctmbd $23 D?Hrmnat1on of Particulate Emissions from Stationary Sources," Federal Register 36, No. 247. 24888-9,
C) FIELD APPLICATIONS
ISO
-------
TITLE REMOVAL OF FILTERS FROM FILTER HOLDERS (CONTINUED)
PAGE 2 OF 2 FOR
-—
ID NO. 02-01-03-04
Figure 02-01-03-04-A. Folding Procedure for Particulate-Laden Filter
from High Volume Air Sampler (Ref. 058).
151
-------
1. TITLE REMOVAL OF PARTICULATE FROM CYCLONES
2. IDENTIFICATION CODE
02-01-03-05
3. ABSTRACT OF METHODOLOGY
At the conclusion of sampling, sampled participates are removed from cyclones using the following procedure. First, the heaters are
turned off and the oven door is opened to cool the filter housing and cyclone parts. These components are then removed and the
sample is quantitatively transferred to a labeled, preweighed nalgene bottle using antistatic nylon brushes or by tapping the
sides of the cyclone. The contents of all the remaining connectors and transformers are then brushed and flushed with solvent
(acetone) into separate labeled containers. In preparation for analysis, the dry particulate sample is dried for three hours at
105°C, cooled in a desiccator and weighed. The acetone rinse samples are evaporated to dryness on a steam bath, then cooled in a
desiccator and weighed. All samples must be retained in their respective beakers. The samples are then combined with particulates
collected on the high volume air sampler filter pad (see 02-01-03-04) and analyzed by suitable methods (e.g., microscopy, etc.).
(See 02-01-04-02, 02-04-01-03, 02-04-01-04, 02-04-02-03.)
4. APPLICATION^ Environmental assessment, engineering evaluation R&D.
A) OPERATIONAL SCOPE
Method is applicable to all cyclones used in flue gas sampling.
B) INTERFERENCES/LIMITATIONS
Care must be taken to avoid sample loss due to spillage, or sample contamination by dust, dirt, etc.
C) RECOMMENDED USE AREA
This method is recommended for engineering evaluation R&D and environmental assessment.
5. OPERATIONAL PARAMETERS
A) RANGE N/A
B| ACCURACY N/A
C) PRECISION N/A
& REAGENTS REQUIRED
Acetone (reagent grade or better).
7. EQUIPMENT REQUIRED
Drying oven (to 105°C); desiccator; analytical balance.
a KEYWORD INDEX: Cyclone, particulates, sample handling.
9. CROSS REFERENCE ID NUMBERS 01-01-01-03; 02-01-03-04, 02-01-04-02; 02-04-01-03, 02-04-01-04, 02-04-02-03.
10. REFERENCES
A) PRIMARY SOURCE
018 Flegal, C.A M.L Kraft C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Procedures for Process Measurements: Trace
Inorganic Materials," TRW Systems Group, EPA Contract No. 68-02-1393, July 1975
093 Clausen, J., A Grant, D. Moore and S. Reynolds, "Field Sampling for Cytotoxicity Test Samples Using a Series Cyclone
Sampling Train, Interim Report, 17 March 1975 to 26 September 1975, EPA Contract No. 68-02-1412, TRW Systems, Inc.,
Appsnoix A.
B) BACKGROUND INFORMATION
188 "Meth°d 5= Determination of Particulate Emissions from Stationary Sources," Federal Register 36, No. 247, 24888-9,
UGCGfflDGr to, 1971,
CJ FIELD APPLICATIONS
152
-------
1. TITLE HANDLING OF PROBE LINER SAMPLES
Z IDENTIFICATION CODE
02-01-03-06
3. ABSTRACT OF METHODOLOGY
The probe liner (Kapton) is removed from the probe, first using plastic tweezers to pull it out far enough to get a firm ha
Using polyethylene disposable gloves, the liner is pulled from the probe and gently rolled as it is removed- the roll is the 1 "'d
in a pre-tared polyethylene bottle for weighing. Upon receipt in the laboratory, the liner is cut into sniler sections- each secti
is then rinsed with acetone into a pre-tared 250-ml beaker. The acetone and water are then evaporated on a steam bath; the beaker
is then cooled in a desiccator, and the particulate weight is subsequently determined.
The probe liner particulates are then combined with particulates collected on the HVSS filter pad (see 02-01-03-04) for subsequent
preparation by plasma ashing (see 02-01-04-03) or other suitable techniques.
4. APPLICATION: Engineering evaluation R&D.
A) OPE RATIONAL SCOPE
Method is applicable to all probe liner samples collected in flue gas sampling.
B) INTERFERENCES/LIMITATIONS
Samples must be protected from contamination by dust, dirt, etc., and loss due to spillage must be avoided.
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D procedure for the removal of particulates from probe liner samples.
5. OPERATIONAL PARAMETERS
A) RANGE N/A
B) ACCURACY N/A
C) PRECISION N/A
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Acetone
Steam bath; desiccator; 250-ml beaker; analytical balance.
KEYWORD INDEX: Probe liner sample, particulates, sample handling.
— .
9. CROSS REFERENCE ID NUMBERS 01-01-01-03; 02-01-03-04, 02-01-04-03.
^^•~-^m^—<^^^^^^^^^^^^^^^«
10. REFERENCES
A) PRIMARY SOURCE
018 Regal, C. A., H.L. Kraft, C. Lin, R.F. Maddalone J.A Starkovich and C Zee "Procedures for Process Measurers:
Trace Inorganic Materials," TRW Systems Group, EPA Contract No. 68-02-1393, July 1975, r>. / J.
Bl BACKGROUND INFORMATION
188 "Method 5: Determination of Particulate Emissions from Stationary Sources," Federal Register 36, No. 247, 24888-9,
December 23, 1971.
C) FIELD APPLICATIONS
-------
PAGE 1 OF 2 FOR
1. TITLE TOTAL CHLORINE IN COAL (ESCHKA ANALYSIS)
Z IDENTIFICATION CODE
024)1-04-01
3. ABSTRACT OF METHODOLOGY
A weighed sample of coal, which is ground to pass a No. 60 mesh sieve, is mixed with Eschka mixture and burned in a bomb containing
oxygen under pressure and a small amount of ammonium carbonate solution. Alternatively, a similar sample of coal is mixed with Eschka
mixture and heated at 675 ±25°C in an oxidizing atmosphere in a muffle furnace.
The chlorides contained in the resultant ammonium carbonate solution or incinerated Eschka mixture are subsequently determined by
potentiometric titration or a modified Volhard procedure (see 02-03-02-01).
4. APPLICATION^ Engineering evaluation R&D.
A) OPERATIONAL SCOPE
The method is applicable to all sampled coals, coke and related materials (ground to pass a No. 60 mesh sieve) and is best
performed by commercial analytical laboratories.
B) INTERFERENCES/LIMITATIONS
N/Q
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D procedure for the determination of total chlorine in coal and coke.
OPERATIONAL PARAMETERS
A) RANGE Methods have sensitivities of ±10X or less.
B) ACCURACY 10* or better.
C)
PRECISION 0.03? chlorine for duplicate determinations performed in the same laboratory.
minations performed in different laboratories.
0.06", chlorine for duplicate deter-
& REAGENTS REQUIRED
Reagent water, ammonium carbonate, Eschka mixture (light calcined
magnesium oxide with one part of anhydrous sodium carbonate),
ferric ammonium sulfate indicator solution, nitric acid solution,
nitrobenzene, oxygen, potassium thiocyanate (standard solution),
silver nitrate (standard solution).
7. EQUIPMENT REQUIRED
Laboratory balance, apparatus for bomb combustion or the sample,
including oxygen bomb, capsule, firing wire, firing circuit, and
metal vessel for bomb immersion in 2 liters of water; apparatus
for Eschka combustion, including crucibles and muffle furnace;
potentiometric titration assembly (see 02-03-02-01).
& KEYWORD INDEX: Total chlorine analysis, coal, combustion, potentiometric titration.
9. CROSS REFERENCE ID NUMBERS
02-03-02-01.
10. REFERENCES
AJ
057
B)
057
024
024
PRIMARY SOURCE
ASTM Committee D-3 and D-5, "Gaseous Fuels, Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, D2361-66, "Standard
Method for Test for Chlorine in Coal," American Society for Testing and Materials, Philadelphia, PA., 1971, p. 376-78.
BACKGROUND INFORMATION
ASTM Committee D-3 and D-5, "Gaseous Fuels, Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, 02015-66 "Standard
Method of Test for Chlorine in Coal," American Society for Testing and Materials, Philadelphia, PA., 1971, pp. 343-350.
ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, E200-67, "Standard
Methods for Preparation, Standardization and Storage of Standard Solutions for Chemical Analysis " American Society for Testing
and Materials, Philadelphia, PA., 1971.
ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, D1193, American Society
for Testing and Materials, Philadelphia, PA., 1971.
154
-------
TITLE TOTAL CHLORINE IN COAL (ESCHKA ANALYSIS)
PAGE 2 OF 2 FOR
.
ID NO. 02-01-0*01
B) BACKGROUND INFORMATION
189 ASTM Committee E-l, et al , "General Test Methods," 1971 Annual Book of ASTH Standards, Part 30, E144-64
for Safe Use of Oxygen Combustion Bombs," pp. 287-288. '
Cl FIELD APPLICATIONS
D *<
Practice
155
-------
PAGE 1 OF 2 FOR
1. TITLE COAL DISSOLUTION SCHEME FOR VARIOUS ELEMENTS
2. IDENTIFICATION CODE
02-01-04-02
3. ABSTRACT OF METHODOLOGY
Figure 02-01-04-02A shows the recommended ashing and dissolution techniques for coal samples. Specific methods for individual elements
and groups of elements are given. Recommended methods are also given for the final analysis. Prior to decomposition, the coal is around
to a minimum of 100 mesh in a ball mill. Particle size is verified using a nylon 100-mesh screen. Any particles which are not ground to
the correct size in the ball mill are broken up with an agate mortar and pestle. Finally, the sample is dried at 50°C overnight.
4. APPLICATION^ Engineering evaluation R&D.
A) OPERATIONAL SCOPE
These procedures are designed to be used on any coal sample for the purpose of trace metal analysis. Low temperature plasma
ashing is recommended because of its proven ability to prevent loss of volatile elements through vaporization.
B) INTERFERENCES/LIMITATIONS
Drying to constant weight may not be possible for a coal sample. Care must be taken to maintain cleanliness and the use
of high purity reagents is important to limit blank values.
C) RECOMMENDED USE AREA
Engineering evaluation R&D.
5. OPERATIONAL PARAMETERS
Al RANGE N/A
B) ACCURACY N/q (Normal retention values for these ashing techniques are better than 90«).
C) PRECISION N/A
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
High purity nitric ana hydrochloric acids, high purity sodium
hydroxide, high purity sodium carbonate, high purity hydro-
fluoric acid.
Low temperature plasma asher (International Plasma
Corporation Model 1001B or equivalent), muffle furnace.
KEYWORD INDEX: Coal, coal dissolution, ashing.
9. CROSS REFERENCE ID NUMBERS 02-01-03-02; 02-02-01-05; 02-01-01. 02-01-04-03.
10. REFERENCES
A) PRIMARY SOURCE
018 Flegal, C.A., M.L. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Procedures for Process Measurements: Trace
Inorganic Materials," TRW Systems Group, EPA Contract No. 68-02-1393, July 1975.
B) BACKGROUND INFORMATION
C) FIELD APPLICATIONS
025 Flegal, C., M.L. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Final Report of Measurement Techniques for
Inorganic Trace Materials in Control Systems Streams," TRW Defense and Space Systems, Redondo Beach California, EPA
Contract No. 68-02-1393, in press.
156
-------
COAL
Ba, Be, Ca, Cd, Cr,
Cu, Mn, Ni, Pb, Sb,
Se, Sr, V, Zn
1. PARR COMBUSTION OVER DILUTE HNO,
2. DILUTE TO 100 ml J
3. TAKE ALIQUOT FOR SnClj REDUCTION,
COLD TO VAPOR AAS METHOD
1. PARR COMBUSTION OVER IN NaOH
2. TRANSFER TO PLASTIC BEAKER
3. DETERMINE BY SPECIFIC ION
ELECTRODE METHOD
As
1. MUFFLE ASH AT 550°C
2. FUSE WITH N^CO.,
3. DISSOLVE IN HCI AND EXTRACT B
WITH 2-ETHYL-l, 3-HEXANEDIOL
4. DETERMINE BY CURCUMIN
COLORIMETRIC METHOD
1. ADD MgO AND MUFFLE ASH AT 550°C
2. ADD HCI, Kl, SnCI2 AND Zn
3. DETERMINE BY Ag-DIETHYLDiTHIOCARBAMATE
COLORIMETRIC METHOD
1. PLASMA ASH
2. DIGEST WITH HNO,
AND HF 3
3. FILTER
FILTRATE
RESIDUE
DILUTE TO 100 ml
FOR ANALYSIS
1. MUFFLE ASH AT 550°C
2. FUSE WITH Na2CO3
3. DISSOLVE WITH HCI
Ba, Be, Ca, Cd, Cr, Cu,
Mn, Ni, Pb, V, Zn
Sr
ATOMIC ABSORPTION
SPECTROSCOPY
ATOMIC EMISSION
SPECTROSCOPY
Sb
5 ml ALIQUOT
DETERMINE BY
DIAMINOBENZIDENE
COLORIMETRIC METHOD
5 ml ALIQUOT,
DETERMINE BY RHODAMINE I
COLORIMETRIC METHOD
Figure 02-01-04-02A. Specialized Coal Dissolution and Analysis Scheme.
-------
1. TITLE LOW TEMPERATURE PLASMA
ASHING AND DISSOLUTION OF COLLECTED PARTICULATE
Z IDENTIFICATION CODE
02-01-04-03
1 ABSTRACT OF METHODOLOGY
The co^oslte particulate samples on the filter are placed In a Urge petri dish and oxygen plasma ashed for hours. The samples are
thin Zved. Transferred to pre-c,eaned. covered 250-*, beakers, and digested for 2 hours in 40 .1 constant tolling ao.ua regia solution
?.lT. HC1 02 .1 40% HN03). The solutions are filtered through No. 4! Whatman filter paper into 10CH.1 Nalgene volumetnc flasks. If
appreciable residue remains, it can be recombined with the original filtrates by ashing at 550°C and fusing with a small amount of
N.2CO, (* 10 parts Na2C03 to 1 part residue), followed by re-dissolution with 1:1 HC1. In all cases when trace elements are to be
determined high purity reagents, such as J.T. Baker Ultrex Brand, are to be used (see 02-01-01-06).
4. APPLICATION: Engineering evaluation R&D.
A) OPERATIONAL SCOPE
This procedure is applicable to all particulates collected from probe liner, filter or cyclones. This procedure can also be
used on solid samples that are ground to less than 100 mesh.
B) INTERFERENCES/LIMITATIONS
This method is primarily designed to dissolve flyash or other particulates from process sources. Geological samples might
require more strenuous wet ashing.
C) RECOMMENDED USE AREA
Engineering evaluation R&D.
& OPERATIONAL PARAMETERS
Trace quantities.
A) RANGE
B) ACCURACY Better than 95% recovery for most elements.
Cl PRECISION N/Q (±10%).
& REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
High purity HC1, HNOj, Na2C03.
Plasma Asher (International Plasma Corp. Model 1001 IB or
equivalent), Nalgene labware, muffle furnace.
a KEYWORD INDEX: Analysis, plasma ashing, particulate dissolution.
91 CROSS REFERENCE ID NUMBERS 02-01-04-03, 02-01-01-06.
10. REFERENCES
A) PRIMARY SOURCE
018
81 BACKGROUND INFORMATION
C) FIELD APPLICATIONS
for process
: Trace
to
in pres
"f""4'?"8' J'A- Starkovich, and C. Zee, "Final Report for Measurement Techniques for
'"" DefenSe """ Space S*steras- Redondo Beach- California, m
-------
i TITI f MIXED LIGAND EXTRACTION OF Ag. Cd, Co, Cu. Fe, Ni. Pb. Zn AND Be FROM TAPE
1. III« SAMPLER DUST SPOTS
i IDENTIFICATION CODE
02-01-04-04
ABSTRACT OF METHODOLOGY
Oust spots collected on filter tape (see 01-06-01-07) or high volume (see 01-06-01-05) samplers are extracted with a mixed ligand system
to remove the metals. An aliquot of the filter or the entire dust spot [normally 2.54 cm (1 inch) in diameter] is placed in a beaker and 2 m
of 15* aimonium acetate is added to adjust the pH (5-7). The NH4C2H302 is followed by 20 ml of an ethyl propionate solution of mixed
ligands (0.1 g diphenylthiocarbazone, 0.75 g 8-quinolinol and 20 ml acetyl acetone made up to 100 ml with ethyl propionate). The
solution is allowed to equilibrate and then directly aspirated into an atomic absorption spectrophotometer or ICPOES for analysis (see
02-02-01-05 or 02-03-02-01). Standards are added to unused filters and extracted in the same manner.
4. APPLICATION: Engineering evaluation R&D.
A) OPERATIONAL SCOPE
This method of extracting Ag, Cd, Co, Cu, Fe, Ni, Db, In and Be can be used on samples of ambient particulates collected on
glass fiber or acid-washed filter paper. The best results are obtained with acid washed filter paper. If metal sulfides are
present,the sample is exposed to bromine vapors for 10 minutes (S -S04').
B) INTERFERENCES/LIMITATIONS
This procedure reduces interferences and sample blanks by direct extraction. Under nonstandard conditions (other than common
salts, sulfides) the efficiency of the extraction can vary. Also,this method is limited to the 9 metals discussed.
C) RECOMMENDED USE AREA
This method is applicable for fugitive emission analysis for engineering RSD.
5. OPERATIONAL PARAMETERS
A) RANGE Depending on the metal, between 2 to 120 ug of the element can be present without the need for dilution.
B) ACCURACY +10 to 20%.
Cl PRECISION N/Q (+10% estimated).
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Aimonium acetate, ethyl propionate, diphenylthiocarbazone,
8-quinolinol, acetyl acetone, bromine.
Tape sampler, lab glassware, atomic absorption
spectrophotometer.
& KEYWORD INDEX: Analysis, separation, mixed ligand.
9. CROSS REFERENCE ID NUMBERS 01-06-01-05, 07; 02-02-01-05, 02-03-02-01.
0. REFERENCES
A) PRIMARY SOURCE
190 West, P.M., "The Determination of Trace Metals in Air," in "Determination of Air Quality," edited by Gleb Mamantov ana
W.D. Shults, New York, Plenum Publishing Corporation.
B) BACKGROUND INFORMATION
191 Sachdev, S.L.,and P.W. West, Environ. Sci. Tech.. 4, 749 (1970).
Cl FIELD APPLICATIONS
159
-------
Table of Contents for 02-02 Elemental Analysis
02-02-01 Single Element/Cation Analysis
02-02-01-01 Lead Analysis by Dithizone Colorimetric Procedure
02-02-01-02 Determination of Hg in Iodine Monochloride Impinger Solutions
02-02-01-03 Ultimate Analysis of Coal (for Carbon and Hydrogen, Nitrogen
and Oxygen)
02-02-01-04 Analysis of Coal and Coke Ash for Al, Si, Fe, Ti, P, Ca, Na
by Photometry and/or Chelatometric Titration
02-02-01-05 Atomic Absorption Techniques for Ba, Be, Cd, Ca, Cr, Cu, Pb,
Mn, Hg, Ni, V, Zn, Al, Sb, As, Co, Fe, Mg, Mn, Mo, K, Ag, Na, Th, Sn, Ti
02-02-01-06 Determination of Acidity by Electrometric Titration
02-02-01-07 Determination of Arsenic by Silver Diethyl Dithiocarbamate
Method
02-02-01-08 Determination of Biochemical Oxygen Demand Using Bioassay
Procedures
02-02-01-09 Determination of Dissolved Oxygen (Modified Winkler With Full
Bottle Technique)
02-02-01-10 Determination of Dissolved Oxygen (DO) by Electrode (Probe)
Method
02-02-01-11 Determination of Boron by Curcumin Method
02-02-01-12 Determination of Calcium by Titrimetry
02-02-01-13 Determination of Total Residual Chlorine by Amperometric
Titration or lodometric Titration
02-02-01-14 Determination of Silica (Dissolved)
02-02-01-15 Spectrophotometric Determination of Antimony
02-02-01-16 Determination of Selenium by Diaminobenzidine Method
02-02-01-17 Determination of Selenium by Distillation-Diaminobenzidine
Method
02-02-01-18 Determination of Cations Using Specific Ion Electrodes (SIE)
02-02-01-19 Determination of Ammonia by Colorimetric Phenate Method
02-02-01-20 Determination of Total Nitrogen by Kjeldahl Method
02-02-01-21 Determination of Heavy Metals by Dithizone Method
02-02-01-22 Determination of Hexavalent Chromium by Diphenyl Carbazide
Method
02-02-01-23 Determination of Iron (Total, Filterable, or Ferrous) by
Phenanthroline Method
02-02-01-24 Determination of Chemical Oxygen Demand
02-02-01-25 Determination of Ammonia by Distillation Procedure
02-02-01-26 Determination of Beryllium by Aluminon Method
02-02-01-27 Determination of Total Chromium by Diphenyl Carbazide Method
02-02-01-28 Determination of Total Copper by Neocuproine Method
02-02-01-29 Determination of Calcium by Gravimetric Method
02-02-01-30 Determination of Total Magnesium by Gravimetric Method
02-02-01-31 Determination of Nickel by Heptoxime Method
02-02-01-32 Determination of Potassium by Cobaltinitrite Method
02-02-01-33 Determination of Vanadium by Gallic Acid Method
02-02-01-34 Method for Determination of Total Alpha Radioactivity Using
Proportional or Scintillation Counters
02-02-01-35 Method for Determination of Total Beta Radioactivity Using
Proportional or Geiger-Muller Counters
02-02-01-36 Method for Determination of Alpha and Beta Radioactivity
Counting Error
02-02-01-37 Method for Determination of Radium in Water
02-02-02 Multielement Analysis
02-02-02-01 Inductively Coupled Plasma Optical Emission Spectroscopy
02-02-02-02 X-Ray Fluorescence of Environmental Samples
02-02-02-03 Optical Emission Spectroscopy (DC Arc/AC Spark)
02-02-02-04 Differential Pulse Anodic Stripping of Trace Metals
02-02-02-05 Instrumental Neutron Activation Analysis
02-02-02-06 Spark Source Mass Spectrometry (SSMS) With Photographic Plate
Detection
02-02-02-07 Multielement Analysis Using Spark Source Mass Spectrometry
(SSMS) with Electrical Detection
161
-------
APPLICATION MATRIX FOR 02-02 ELEMENTAL ANALYSIS
METHOD
02-02-01-01
02-02-01-02
02-02-01-03
02-02-01-04
02-02-01-05
02-02-01-06
02-02-01-07
02-02-01-08
02-02-01-09
02-02-01-10
02-02-01 -11
02-02-01-12
02-02-01-13
02-02-01-14
02-02-01-15
02-02-01-16
02-02-01-17
02-02-01-18
02-02-01-19
02-02-01-20
02-02-01-21
02-02-01-22
02-02-01-23
02-02-01-24
02-02-01-25
02-02-01-26
02-02-01-27
02-02-01-28
02-02-01-29
02-02-01-30
02-02-01-31
02-02-01-32
02-02-01-33
02-02-01-34
02-02-01-35
02-02-01-36
02-02-01-37
02-02-02-01
02-02-02-02
02-02-02-03
02-02-02-04
02-02-02-05
02-02-02-06
02-02-02-07
LEVEL I
ENVIRONMENTAL
ASSESSMENT
•
•
•
•
•
•
•
*
•
•
•
•
_
•
•
•
•
•
•
•
•
•
COMPLIANCE
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
ENGINEERING
EVALUATION
R/D
•
•
•
•
•
•
" - • • • •!• imf~^^^—^^^^^**^H***~~i
•
•
•
•
•
•
•
162
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ELEMENTAL ANALYSIS- ID No. 02-02
The abstracts presented in this section discuss the procedure categories
of (02-02-01) single element/cation analysis and (02-02-02) multielement
analysis. The methods employed for single element and cation analysis are
spectrophotometry, atomic absorption spectroscopy, bioassay, specific ion
electrodes, and volumetric, chelatometric, and electrometric (ampero-
rnetric and potentiometric) titration methods. Specific procedures are
recommended for each element or cation discussed. The techniques employed
for multielement analysis include optical emission spectroscopy (inductively
coupled plasma, DC arc, AC graphite spark), x-ray fluorescence, differential
pulse anodic stripping, instrumental neutron activation analysis, and spark
source mass spectrometry.
02-02-01 Single Element/Cation Analysis (Abstracts 02-02-01-01
through 02-02-01-23)~~
Spectrophotometric methods (02-02-01-01, 02, 03, 04, 07, 11, 14, 15, 16,
17, 19, 21, 22, 23), specific ion electrodes (02-02-01-18) electrode probes
(02-02-01-10), potentiometric, chelatometric and volumetric titrations (02-
02-01-04, 06, 09, 12, 13, 20) are commonly used in the analysis of single
elements and cations. Some important factors which must be considered in
the proper application of most of these methods are discussed in the intro-
duction to Section 02-03 of this manual.
In addition to volumetric, potentiometric, and chelatometric titrations,
amperometric (02-02-01-13) titrations can also be used. This technique is
primarily used in precipitation reactions, although redox and chelatometric
reactions may also be determined by amperometric titrations. In order to
obtain a sharp endpoint in precipitation titration curves, however, the
solubility of the precipitate cannot be high. This can be avoided by
adjustment of the solvent used in order to limit the solubility of the
product.
Atomic absorption spectroscopy (AAS) is one of the more sensitive
methods for quantitative identification of a wide range of elements and
cations. Some important considerations to the proper use of atomic absorp-
tion spectroscopy include the type or source of lamp to be used, the use of
suitable fuel and oxidant, and optimum concentrations for standard solutions.
163
-------
A variety of technical and commercial literature is currently available
which gives specific procedures and optimum operating conditions for cations
and elements (reference 193). The scope of AAS has recently been extended
by the use of microprocessor-based computer instruments, which make high
precision analyses on both major and minor constituents in the same sample
possible. Two major advantages which are characteristic of the microprocessor
technique are a signal integration capability, which significantly improves
analytical precision, and an automatic calibration capability, using multiple
standards for the handling of wide ranges of concentration in the same sample
with good precision (reference 193).
The BOD procedure (02-02-01-08) which is used in the determination
of biochemical oxygen demand (BOD) is an empirical method which measures the
dissolved oxygen consumed by microbial life while oxidizing the organic matter
present. Although high precision can be achieved using this technique,
there is no acceptable method for determining accuracy. Additional informa-
tion relating to the oxygen demand characteristics of samples may be obtained
by applying specific samples (usually liquids or slurries).
Actual determinations of the dissolved oxygen present in the sample
involves use of probe methods (membrane or thallium probes). Some important
factors in the performance of membrane probes include concentration of dis-
solved inorganic salts and reactive species, and temperature. Broad varia-
tions in the kinds and concentrations of salts in the sample can impair the
accuracy obtained, particularly when membrane probes are used. Certain
gases (chlorine, hydrogen sulfide) which can pass through the membrane may
also interfere. Chlorine may depolarize the cathode and cause a high probe
output. Long-term exposures to chlorine will coat the anode with the chloride
of the anode metal and eventually desensitize the probe. Hydrogen sulfide
will interfere with membrane probes if the applied potential is greater than
the half-wave potential of the sulfate ion. If the applied potential is
less than the half-wave potential, an interfering reaction will not occur,
but coating of the anode with the sulfide of the anode metal can take place.
The performance of membranes is generally not affected by pH changes, but
membrane probes are temperature sensitive.
164
-------
02-02-02 Multielement Analyses (Abstracts 02-Q2-Q2-m throuah
Q2-02-02-07T ouq"
Methods used in multielement analysis include optical emission spectros-
copy, including inductively coupled plasma OES (02-02-02-01), and DC arc/AC
spark OES (02-02-02-03), X-ray fluorescence (02-02-02-02), anodic stripping
voltamnetry (02-02-02-04), instrumental neutron activation analysis (02-02-
02-06) and spark source mass spectrometry (02-02-02-07 and -08).
Table 02-02-A lists some performance characteristics of most of these
methods as applied to trace metal analysis, including the range of elements
which can be examined, and selection criteria which can be applied to their
usage. Table 02-02-B compares the screening capability of several multi-
element methods.
The methods generally function in either of two ways: by analyzing a
given sample for a number of elements simultaneously (e.g., OES, SSMS, INAA)
or by analyzing a sample for a number of elements consecutively, without
manual adjustment (e.g., XRF). One determining factor in the choice of
techniques is the availability of the instrument to the user, since the
equipment is generally complex and not readily available. In many cases,
extensive preparation of the sample will be required prior to actual analysis.
Interferences are generally encountered in applying the techniques to
specific matrices. Special handling procedures such as plasma ashing, stan-
dard addition, dilution, or concentration steps are often required. Because
the techniques are sensitive to very low or trace levels of elements, high
purity reagents should be used in laboratory sample preparations.
Spark source mass spectrometry (02-02-02-06 and -07) is perhaps one
of the most sensitive and universal techniques which is available for
inorganic analysis. Matrix effects are important to accurate determinations.
Samples high in organic content require ashing prior to analysis.
OES (02-02-02-01, -03) is an acceptable alternative to SSMS. Although
the sensitivity of the method is less than SSMS, OES is more widely avail-
able. XRF (02-02-02-02) is less sensitive than either SSMS or OES. However,
little or no pretreatment is required for samples when XRF is used. More-
over, the technique is nondestructive. The sensitivity of the INAA technique
165
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Analytical Technique
Emission Spectroscopy
DC Arc/ AC Spark
Inductively Coupled
Plasma O.E.S.
X-Ray Fluorescence
Electrochemical Methods
Anodic Stripping Voltammetry
Nuclear Methods
INAA*
Mass Spectroscopic
Spark Source
Analytically Useful
Elemental Range
Li to U
Be to U
Na to U
Pb, Cd, As, Cr, Se, Mn,
Sn, Zn, Tl, Co, Cu, Fe,
Hg, Sb, Al, Ni, Ag
H to U
H to U
Availability
High
Low
Intermediate
High
Low
Low
Accuracy
Capability
Acceptable
Good
Acceptable
Good
Good
Poor-
Acceptable
Sampl e
Pre-
paration
Moderate
Minimal
Moderate
Minimal
Minimal
Moderate
Cost
Effective-
ness
Excellent
Excellent
Good
Good
Excellent
Excellent
Analysis
Time
Medium
Short
Medium
Medium
Protracted
Medium
"Instrumental Neutron Activation Analysis
Table 02-02-A. Summary of Multielement Analytical Technique Performance
for Trace Material Sample Analysis.
-------
TECHNIQUE
EMISSION SPECTROSCOPY
DC ARC/AC SPARK (OES)
APOES *
X-RAY FLUORESCENCE (XRF)
INSTRUMENTAL NEUTRON
ACTIVATION (INAA)
SPARK SOURCE MASS
SPEC (SSMS)
MULT I
ELEMENT
CAPABILITY
UNABLE TO RUN
lig, Se, Sb, F
ANY ELEMENTS
TO A MAX. OF
50 PRESET AT
FACTORY TO
USERS SPECS
UNABLE TO RUN
Li, Be, B
Be CANNOT BE
DONE
ALL ELEMENTS
CAN BE DETER-
MINED
ACCURACY
±30-50% SEMiqUANT.
±105; QUANT.
+40% SEMIQUANT
±10% QUANT.
QUALITATIVE TO
±10% DEPENDING
ON ELEMENT AND
MATRIX
±30% SEMIQUANT.
2-3% QUANT.
100-300% "QUICK
AND DIRTY"
+30% SEMIQUANT.
SENSITIVITY
GENERALLY
ACCEPTABLE,
VARIES WITH
MATRIX
BETTER THAN
AAS FOR ALL
ELEMENTS
VARIABLE,
DEPENDS ON
ELEMENT AND
MATRIX
ACCEPTABLE,
VARIES WITH
MATRIX
ACCEPTABLE
MATRIX
COAL FLY ASH HATER
REMOVAL BY NONE EVAPORATION
ASHING OF NECESSARY
ORGANIC
MATRIX
ASH, ACID NONE
FOLLOWED DISSOLUTION NECESSARY
BY ACID
DISSOLUTION
CAN BE RUN GRIND AND RUN DIRECT
DIRECT AFTER BRICKET
GRINDING AND
BRICKETING
NONE NONE NONE
NECESSARY NECESSARY NECESSARY
REMOVE NONE EVAPORATION
ORGANIC NECESSARY
BY ASHING
COST
135.00/SAMPLE
SEMIQUANT.
$14.00/SAMPLE
S50.00/SAMPLE
QUALIFICATION
SAMPLE
$325.00/SEMIQUANT.
$35.00/ELEMENT/
SAMPLE QUANT.
145.00/SAMPLE
±100-300%
S225.00/SAMPLE
SEMIQUANT.
INDUCTIVELY COUPLED ARGON PLASHA OPTICAL EMISSION SPECTROSCOPY
Table 02-02-B. Screening capability of Several Multielement Techniques.
-------
varies for different elements. The sensitivity depends upon the intensity
of the activating source and the capacity of a specific element to absorb
neutrons. For some elements (In, Re, Ir, Sm, Eu, Dy, Ho, Lu, V, As, Sb)
activation analysis has greater sensitivity than chemical methods; for
others (Fe, Ca, Pb, Bi, Zn, Cd, Na, K) INAA is less than or equal to
chemical methods.
REFERENCES
192 Ewing, G.W., "Instrumental Methods of Chemical Analysis," New York,
McGraw-Hill Book Co., 1960.
193 Perkin-Elmer Corporation, "Analytical Methods for Atomic Absorption
Spectrophotometry," Perkin-Elmer Corporation, May 1966.
194 Fernandez, F.J., and J.D. Kerber, "High-precision Analyses by Atomic
Absorption," Am. Lab., 49, March 1976.
195 Barnett, W.B., and J.D. Kerber, Am. Lab.. 7.(8), 43 (1975).
196 Orion Research, "Analytical Methods Guide," Orion Research, Inc., 7th
ed., Cambridge, Mass., May 1975.
197 Radian Corporation, "Sampling and Analytical Strategy for Potentially
Hazardous Compounds in Petroleum Refinery Streams," Radian Corporation,
Austin, Texas.
198 Harrison, W.W., G.G. Clemenas and C.W. Magee, J. Assoc. Offie. Anal.
Chem.. 54, 929 (1971).
199 Brown, R., M.L. Jacobs and H.E. Tayler, Am. Lab.. 4.(11), 29 (1972).
168
-------
1. TITLE LEAD ANALYSIS BY DITHIZONE COLORIMETRIC PROCEDURE
Z IDENTIFICATION CODE
02-02-01 -01
1 ABSTRACT OF METHODOLOGY
Paniculate lead is digested with nitric and perchloric acids. Vaporous lead collected on activated charcoal is extracted
with aqua regia for 16 hrs at a temperature of 90 to 100°C. The carbon is removed by filtration prior to analysis. To these
solutions a reducing/buffer (citrate-cyanide hydroxylamine-ammonium hydroxide), and dithizone in carbon tetrachloride are
added. The lead is extracted into the carbon tetrachloride phase and the absorbance of the CCl4/dithizone is read at 510 nm.
4. APPLICATION^ Engineering evaluation R&D, level 1 environmental assessment.
A) OPERATIONAL SCOPE
This method covers the determination of low levels of atmospheric lead. This method is primarily used for samples collected
as particulate lead on filters or vaporous lead on activated charcoal and is not meant to be used directly for wastewater
streams or process waters.
B) INTERFERENCES/LIMITATIONS
Dithizone gives colored complexes with bismuth, stannous tin, monovalent thallium, and indium; the procedures stated in this
method reduce the interferences due to those four metals. Only in cases where the analyst suspects large quantities of these
interfering ions should extra precautions be taken. Glassware used in this method must be of borosilicate glass and deleaded
by soaking in warm nitric acid followed by rinsing with several portions of distilled water.
C) RECOMMENDED USE AREA
Engineering evaluation R&D testing for lead fugitive emissions.
5. OPERATIONAL PARAMETERS
A) RANGE 0.001 to 1 ppm (estimated).
B) ACCURACY £10% (estimated).
C) PRECISION +10X (estimated).
6. REAGENTS REQUIRED
High purity water, buffer solution (dibasic ammonium citrate, hydrox-
ylamlne hydrochloride, potassium cyanide, and ammonium hydroxide), ED-
TA, dithizone, hydrochloric acid, lead nitrate, nitric acid, perchloric
acid. (Note: All acids should be of high purity, see 02-01-01-06.)
7. EQUIPMENT REQUIRED
Absorbance cell (200 ml capacity modified),
spectrophotometer, automatic dispensing burets.
8. KEYWORD INDEX: Analysis, lead analysis, dithizone.
9. CROSS REFERENCE ID NUMBERS 01-05-02-02; 02-01-01-06.
10. REFERENCES
053
A) PRIMARY SOURCE „.„ ,„
ASTH, "Lead in the Atmosphere by Co^rimetric Dithizone Procedure/ 1974 Book of ASTM Standards, Part 26, D3112-72T,
American Society for Testing and Materials, Philadelphia, PA., 1974, p. btt.
B) BACKGROUND INFORMATION
200 Synder, L.J., Anal. Chem., 39, 591 (1967).
201 Synder, L.J., Anal. Chem., 19., 684 (1947).
202 Henderson, F.R., and L.J. Synder, Anal. Chem., 3]_, 2113 (1959).
C) FIELD APPLICATIONS
-------
PAGE 1 OF 2 FOR
1. TITLE DETERMINATION OF Hg IN IODINE MONOCHLORIDE IMPINGER SOLUTIONS
2. IDENTIFICATION CODE
02-02-01-02
3. ABSTRACT OF METHODOLOGY
Gaseous emissions are sampled from the stationary sources and collected in an iodine monochloride solution. The mercury collected
(in the mercuric state) is reduced to elemental mercury in basic solution by the addition of hydroxylamine sulfate. Mercury is
vaporized from the solution using a zero grade air stream and passed through a cylindrical gas cell (approximately 3.8 cm OD x 18 cm,
see Figure 02-02-01-02A) with quartz windows. This gas cell is mounted in the burner area (without the flame) of the AAS. The internal
optics of the AAS are used to monitor the absorption of the 253.7 nm line of the AAS hollow cathode lamp. Both blanks (any unused Id
solution) and standards are run in solutions containing IC1.
3.8 CM
-18 CH-
QUARTZ
WINDOW
7 MM OD TUBING
7 MM OD TUBING
INLET OUTLET
Figure 02-02-01-02A. Gas Cell Schematic (019).
QUARTZ
WINDOW
4. APPLICATION: compliance, engineering evaluation R&D, environmental assessment.
A) OPERATIONAL SCOPE
This method is specifically used for the determination of mercury in the IC1 impinger solutions (see 01-01-01-02). This chemical
system can also be used for other solutions containing mercuric salts.
B) INTERFERENCES/LIMITATIONS
Iodine monochloride is a very caustic and messy solution to handle in the field. Typically, iodine vapor escapes from the impingers
and is passed through the train. While iodine monochloride tm/st be used for compliance testing, a silver catalyzed persulfate
solution provides an efficient and easily handled solution for trapping volatile metals and mercury in particular (see 01-01-01-02).
Furthermore, the ammonium persulfate solution does not give a large background signal to the AAS analysis.
C) RECOMMENDED USE AREA
Compliance testing for Hg in flue gas stream.
5. OPERATIONAL PARAMETERS
A) RANGE 0.1 ppm of mercury can be determined in the impinger solutions.
B) ACCURACY N/Q (£155! estimated).
C) PRECISION N/Q (±10% estimated).
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Potassium iodine, hydrochloric acid, potassium hydroxide, distilled
water, iodine monochloride, glass fiber filter (MSA-1106BH or equiv-
alent), nitric acid, silica gel, soda lime, sodium hydroxide, mercuric
chloride, hydroxylamine sulfate, sodium chloride.
Atomic absorption spectrophotometry (Perkin-Elmer Model 303 or
equivalent), balance, gas cell (see Figure 02-02-01-02A).
a KEYWORD INDEX: Sampling, mercury sampling.
9. CROSS REFERENCE ID NUMBERS 01-01-01-02; 01-04-01-01.
10. REFERENCES
A) PRIMARY SOURCE
019 u. S. Environmental Protection Agency, Federal Register 36, No. 234, p. 23243, 1971
B) BACKGROUND INFORMATION
020 Martin, R.M.."Construction Details of Isokinetic Source Sampling Equipment," Environmental Protection Agency, APT-0581.
021 Smith, M.S., et al, "Stack Gas Sampling Improved and Simplified with New Equipment", APCA Paper No. 67-119, 1967.
022 Hatch, W.R., and W.L. Ott, "Determination of Submicrogram Quantities of Mercury by Atomic Absorption Spectrophotometry,"
C)
Anal. Chem., 40, 2085 (1968).
FIELD APPLICATIONS
170
-------
PAGE 2 OF 2 FOR
TITLE DETERMINATION OF Hg IN IODINE MONOCHLORIDE IMPINGER SOLUTIONS (CONTINUED)
ID NO. 02-02-01-02
10. REFERENCES (Continued)
b) BACKGROUND INFORMATION (Continued)
023 Rome, J.J., "Maintenance Calibration and Operation of Isokinetic Source Sampling Equipment," EPA,
APTD E-05-76.
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Book of ASTM Standards, Part 23,
D~2928-71 "Standard Method for Sampling Stacks for Participate Matter," American Society for Testing
and Materials, Philadelphia, PA., 1971.
171
-------
1. TITLE ULTIMATE ANALYSIS OF COAL (FOR CARBON AND HYDROGEN. NITROGEN AND OXYGEN)
i IDENTIFICATION CODE
02-02-01-03
1 ABSTRACT OF METHODOLOGY
The determination of carbon and hydrogen is made by complete oxidation of sample (see 01-03-01-02 and 02-01-03-02 for samp1e collection
and preparation procedures) in a closed combustion tube which is packed with materials for the removal of interfering species. A typical
tube is packed with sections of cupric oxide and lead chromate. The products of the combustion are then fixed in an absorption train
consisting of a water absorber (solid dehydrating agent), a solid carbon dioxide absorber, and a guard tube which is packed with equal
volumes of water absorbent and solid carbon dioxide absorbent. The percent carbor, and hydrogen is then calculated from an increase in
weight of the tubes.
The determination of nitrogen is performed by the Kjeldahl-Gunning method, involving conversion of nitrogen into ammonium salts followed
by decomposition of the salts and subsequent distillation of liberated ammonia into a sulfuric acid solution and back-titration of
excess add.
An alternative method for nitrogen determination involving distillation of the ammonia into a solution of boric acid rather than
sulfuric acid can be used.
The percent oxygen in the sample is not measured directly but is calculated by subtracting the percent of H, C, N, S, moisture and
ash from the sample.
4. APPLICATION: Engineering evaluation R&D.
A) OPE RATIONAL SCOPE
Method is applicable to analysis of solid samples (coal, coke) collected from process streams.
B) INTERFERENCES/LIMITATIONS
Oxides of sulfur can interfere with C and H analyses, unless adequate combustion tube packings are used (cupric oxide, and lead
chromate or silver). Also, oxides of nitrogen formed during the combustion procedures may lead to high results for carbon.
There are no known interferences to nitrogen or oxygen determinations.
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D procedure for the ultimate analysis of coal and coke for carbon and
hydrogen, nitrogen and oxygen.
5. OPERATIONAL PARAMETERS
A) RANGE Method gives the total percentages of carbon and hydrogen in the coal, including carbonate carbon, and hydrogen in
moisture and in water of hydration of silicates. Method also gives total oxygen and nitrogen.
B) ACCURACY N/Q
Cl PRECISION Permissible percentage differences in results obtained by the same laboratory include: Carbon - 0.3;Hydrogen - 0.07;
Nitrogen 0.05.
6. REAGENTS REQUIRED
For carbon and hydrogen determination: oxygen, cupric oxide,
lead chromate, silver gauze, copper gauze, water absorbent
(anhydrous magnesium perchlorate), carbon dioxide absorbent
(sodium or potassium hydroxide in an inert carrier).
For nitrogen determination: alkali solution (potassium sulfide/
sodium hydroxide), ethyl alcohol, mercury, potassium permanganate,
potassium sulfate, sucrose, sulfuric acid, zinc and for Kjeldahl-
Gunning Method, methyl red indicator; for alternate method,
boric acid solution.
7. EQUIPMENT REQUIRED
For carbon and hydrogen determination: oxygen purifying train,
consisting of first water absorber, carbon dioxide absorber,
and guard tube; flow meter, combustion unit consisting of
3 furnace sections, combustion tube, combustion boat. For
nitrogen determination: digestion unit, distillation unit,
condenser, Kjeldahl digestion flask, Kjeldahl connecting bulb,
Erlenmeyer flasks, glass connecting tubes, rubber tubing.
8. KEYWORD INDEX: Ultimate analysis; carbon, hydrogen, nitrogen, oxygen; absorption tube, Kjeldahl-Gunning.
9. CROSS REFERENCE ID NUMBERS 01-03-01-02; 02-01-03-02.
10. REFERENCES
A) PRIMARY SOURCE
057 ASTM Committee D-3 and D-5, "Gaseous Fuels; Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, D271-70, "Standard
Methods of Laboratory Sampling and Analysis of Coal and Coke," American Society for Testing and Materials, Philadelphia, PA.,
B) BACKGROUND INFORMATION
057 ASTM Committee 0-3 and D-5, "Gaseous Fuels; Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, D271-70, "Standard
Methods (^Laboratory Sampling and Analysis of Coal and Coke," American Society for Testing and Materials, Philadelphia, PA.,
C) FIELD APPLICATIONS
014 Hamersma, J.W., and S.L. Reynolds, "Tentative Procedures for Sampling and Analysis of Coal Gasification Processes," TRH
Systems Group, EPA Contract No. 68-02-1412, March 1975.
172
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PAGE 1 OF 2 FOR
ANALYSIS OF COAL AND COKE ASH FOR ALUMINUM. SILICON IRON TITANIUM
1. TITLE ft$?$(0lNOUS- CALCIUM AND SO0101* BY PHOTOMETRY AND/OR CHELATOMETRIC
2. IDENTIFICATION CODE
02-02-01-04
3. ABSTRACT OF METHODOLOGY
The sample to be analyzed (see 01-03-01 and 02-04-03-02 for sample collection and preparation procedures) is ashed under standard condi
tions and ignited to constant weight. Two solutions are then prepared from the ash: Solution A, (for SiO and Al 0 analyses) b
the ash with sodium hydroxide followed by final dissolution of the melt in dilute hydrochloric acid; Solution B, (for the remaining
elements), by decomposition of the ash with sulfuric, hydrofluoric and nitric acids.
The two solutions are subsequently analyzed by a combination of methods: a) spectrophotometric procedures for SiO , Al 0 , Fe 0 TiO
and P205; b) chelatometric titration for CaO and MgO; and c) flame photometry for Na20 and K20. Figure 02-02-01-04A summarizes$the ?
methods and procedures for each determination.
APPLICATION^ Engineering evaluation R&D.
Al OPERATIONAL SCOPE
The methods are applicable to all solid samples (coal, coke, etc) which have been collected from process streams. Analyses a
best performed by commercial analytical laboratories.
B) INTERFERENCES/LIMITATIONS
Insoluble barium sulfate may precipitate out in the sample diluted for chelatometric determination of calcium. However, the
precipitate may be removed by filtration.
C) RECOMMENDED USE AREA
Engineering evaluation R&D.
OPERATIONAL PARAMETERS
A) RANGE Methods have ppm sensitivities.
B| ACCURACY 5% or better.
C) PRECISION ±103!
6. REAGENTS REQUIRED
See Table 02-02-01-04A for summary of specific required reagents.
Reagents for general analysis solutions include: hydrochloric acid,
hydrofluoric acid, NBS No. 99a Soda Feldspar (SiOj + AlgOa), nitric
acid, sodium hydroxide, and sulfuric acid.
7. EQUIPMENT REQUIRED
Laboratory balance, crucibles, muffle furnace,
photometer, absorption spectrophotometer (380
emission flame
to 780 ran).
a KEYWORD INDEX: Elemental analysis; coal ash; coke ash; silicon, aluminum, iron, titanium, phosphorous, calcium and sodium.
9. CROSS REFERENCE ID NUMBERS 01-03-01-02; 02-04-03-02; see also 02-02-01-12 and 02-02-01-14.
10. REFERENCES
A) PRIMARY SOURCE x ,„ rmoc co
057 ASTM Committee 0-3 and D-5, "Gaseous Fuels; Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, 02795-69,
"Standard Methods of Analysis of Coal and Coke Ash," American Society for Testing and Materials, Phi ladeipma, m.,
-. 1971. p. 407-414.
Bl BACKGROUND INFORMATION
024 ASTM Conrcittee D-19 and D-22, "Water; Atarcspheric Analysis," 1971 Annual Book of «™ Standards, Part 23 200-67,
"Standard Methods for Preparation, Standardization and Storage of Standard Solutions for Chemical snaiysi:,,
American Society for Testing and Materials, Philadelphia, PA., 1971, p. 868-885.
C) FIELD APPLICATIONS
203 Novitskii, N.V.,and N.I. Ivanova, Khim. Tverd. Topi., £, 64-8, 1973 (Russ); Chen. Abstr.. 80, 5586.
173
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PAGE 2 OF 2 FOR
r
ANALYSISOF COAL AND COKE ASH FOR ALUMINUM. SILICON, IRON. TITANIUM, 1 |Q NO. 02-02-01-04
TITLE PHOSPHOROUS, CALCIUM AND SODIUM BY PHOTOMETRY AND/OR CHELATOMETRIC |
TITRATION (CONTINUED)
Solution A
Fuse 005 g osh with
NoOH. Dissolve in
water and HCL.
Dilute to 1,000 ml
| 1
10 ml 10ml
I 1
Molybdenum
blue
650 nm
Calcium
alizarin
red S
complex
475 nm
1 1
i
10ml
1
Dilute
to 50 ml.
UselOml.
o( dilute
sample
o-phen-
onthroline
510 nm
1
i
Solution B
Digest 04 g ash with
HFand
H2SQ4, evaporate to SO;
fumes. Dissolve m water
and
dilute to 250 ml.
25ml 25ml 25ml 25ml
Hydrogen
peroxide
in
5 percent
H.SO,
C.
410 nm
Ammonium
molybdo-
vanadate
430 nm
1
EDTA
titrotion.
Screened
calcein
indicator
EOTA Flame
titrotion spectra-
Screened photometer
phthalein
purple
indicator
!
1
SiO.,
AI203
TiO,
P2°5
CoO
MgO
No20
K20
Figure 02-02-01-04A. Outline of Rapid Methods for Analysis of Coal Ash (Reference 057).
Table 02-02-01-04A. Summary of Reagents Required for Analysis.
Species
Reagents Required
SiO,
A1203
Ti02
P2°5
CaO
MgO
Na20, K20
Ammonium molybdate solution, sodium sulfite, l-amino-2-naphthol-4-sulfonic acid,
sodium metabisulfite, tartaric acid solution.
Glacial acetic acid, Alizarin Red-S solution, calcium chloride solution, sodium
acetate-acetic acid buffer, hydroxylamine, hydrochloride solution, thioglycollic
acid.
Hydroxylamine hydrochloride solution, orthophenanthroline, sodium citrate, ferrous
ammonium sulfate.
3% hydrogen peroxide, NBS Sample No. 154a (99.6f, TiO?), potassium pyrosulfate,
potassium bisulfate.
Ammonium molybdovanadate, potassium dihydrogen phosphate.
Ammonium hydroxide, calcein indicator (thymolphthalein and potassium chloride),
EDTA, potassium hydroxide, calcium carbonate, triethanolamine.
Ammonium hydroxide, phthalein purple indicator (phthalein purple, methyl red,
Naphthol Green 15, potassium chloride), triethanolamine, EDTA.
Potassium sulfate solution; sodium sulfate solution, synthetic ash solution
(aluminum, calcium carbonate, magnesium sulfate, sulfuric acid).
-------
PAGE 1 OF 3 FOR
1, TITLE
ATOMIC ABSORPTION TECHNIQUES FOR Ba, Be, Cd, Ca, Cr, Cu, Pb, Mn, Hg. Ni; V, Zn
MI Sbi A& co Fe Mg Mg Mo K ^ M,, T,, s,, Tj
Z IDENTIFICATION CODE
02-02-01-05
3. ABSTRACT OF METHODOLOGY
MS (atomic absorption spectrometry) as a general analytical tool is normally considered free of interelement interferences, and because
of the large dilutions employed, is usually unresponsive to matrix changes. High solids concentrations after typical dissolution procedures
as well as complicated matrices make it mandatory for the analyst to be aware of and to investigate the presence of interferences. The
interference types encountered, are classified into the following three categories:
, Interelement or chemical interferences. For .the most part, these interferences when present can be eliminated by usinq a high
temperature NeO-acetylene flame, or by adding suppressants. y 9 a nlgn
I Matrix effects. These effects are compensated for by specially preparing the standards to match the expected acid and salt content
of the sample, or by applying standard addition techniques. content
I Molecular absorptions. Molecular absorptions occur from species such as CaOH or SrO or from organic materials. The end result is a
positive error in the absorption measurement. A double beam AAS is required to both monitor this molecular absorption and aoolv
the appropriate correction electronically.
The solutions prepared as described in 02-01-02, 03, 04 can be analyzed directly by AAS for Mn, Cu, Cr, Ni, Sn, V, Pb, Cd, Zn, Ba, Cd,
Ca, and Be using the operating conditions specified in Table 02-02-01-05A. If no chemical or matrix interferences are found after perform-
ing accuracy checks, it is possible to use distilled water standards. The implementation of either the factor method short curve or
standard addition technique for obtaining the required accuracy is sample dependent and also depends on the skill of the analyst.
4. APPLICATION: Engineering evaluation R&D, compliance
A) OPERATIONAL SCOPE
These procedures can be used on all samples generated from 02-01-02, 03, 04.
B) INTERFERENCES/LIMITATIONS
It is possible that matrix problems will reduce the sensitivities reported in Table 02-02-01-05A
C) RECOMMENDED USE AREA
These methods are especially useful for engineering evaluation R&D but at the same time they are the recommended compliance
procedures.
5. OPERATIONAL PARAMETERS
A) RANGE See Table 02-02-01-05A.
B) ACCURACY ±15%
C) PRECISION ±10%
6. REAGENTS REQUIRED
None
7. EQUIPMENT REQUIRED
Double beam AAS (Jarrel-Ash 810 or equivalent).
8. KEYWORD INDEX'. Analysis, atomic absorption spectrometry.
9. CROSS REFERENCE ID NUMBERS 02-01-02, 03, 04; 02-01-01-02.
10. REFERENCES
tofor Chemtca! Analysts of Hater and «aStes'., Methods Develop and Quality Assurance Research Laboratory,
National Environmental Research Center, EPA No. 625/6-74-003, Washington, D.C., 1974.
BACKGROUND INFORMATION
See Table 02-02-01-05A.
FIELD APPLICATIONS
See Table 02-02-01-05A.
-------
PAGE 2 OF 3 FOR
TITLE ATOMIC ABSORPTION TECHNIQUES FOR Ba, Be, Ca.Cr,Cu,Pb. Mn,Hg,Ni, V.Zn ID NO.
Al, Sb, As, Co, Fe, Mg, Mn, K, Mo, Ag, Na, Th, Sn, Ti (CONTINUED)
Table 02-02-01-05A. Typical Atomic Absorption Operating Parameters
Element
Ba
Be
Cd
Ca
Cr
Cu
Pb
Mn
Hg
Ni
V
Zn
Al
Sb
As
Co
Fe
Mg
Mn
Mo
K
Ag
Na
Th
Sn
Ti
Slit
Width (mn)
0.4
1.0
0.4
1.0
0.2
1.0
0.4
0.4
1.0
0.2
1.0
1.0
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
Wavelengths, nm
Analytical
553.6
234.9
228.8
422.7
357.9
324.7
283.3
279.5
253.7
232.0
318.4
318.4
309.2
217.6
193.7
240.7
248.3
285.2
279.5
313.3
766.5
328.1
589.6
276.8
286.3
365.3
Background
Ni-231.6 Non-
Absorbing
226.5
351.9
323.4
282.0
Pb 282.0 Non-
Absorbing
Si 252.5
231.6
312.5
210.0
Gas Mixture •
N,0 acetylene
N,0 acetylene
Air acetylene
N.,0 acetylene
N20 acetylene
Air acetylene
Air acetylene
Air acetylene
Flameless
Air acetylene
N20 acetylene
Air acetylene
N-0 acetylene
Ai r acetylene
Avgon hydrogen
Air acetylene
Air acetylene
Air acetylene
Air acetylene
N?0 acetylene
Air acetylene
Air acetylene
Air acetylene
Air acetylene
Air acetylene
N20 acetylene
Detection
Limit (ppm)
0.03
0.005
0.003
0.005
0.005
0.003
0.03
0.003
0.1 pg
0.01
0.01
0.003
0.1 mg/i.
0.2 mg/i
2-20
ug/«.
0.03 mg/i
0.02 mg/i
0.0005
mg/l
0.01 mg/i
0.1 mg/i
0.005
mg/i
0.01 mg/i
0.002
mg/i
0.1 mg/i
0.8 mg/i
0.3 mg/i
Comments
Add 0.1XK as an ioni-
zation suppressant
Add 1%K as an ioniza-
tion suppressant
Reduction using
SnCl2
Add 1 ,000 pg/mi as
ionization
suppressant
Interference due to
Pb may occur; use
231.1 line
Interference due to Al
at cmc greater than
2 mg/i is masked by
addition of lanthanum
Sodium may interfere if
present at levels
significantly higher
( than potassium
References
084, 205, 209, 185
084, 205, 209, 218, 185
084, 024, 205, 207, 209,
210, 213, 216, 185
084, 024, 205, 207, 209,
210, 213, 216, 185
084, 024, 205, 207, 213, 185
084, 204, 205, 209, 210,
213, 216, 217, 185
084, 024, 205, 209, 213,
216, 217, 185
084, 204, 024, 209, 211,
213, 216, 217, 185
205, 206, 209, 212, 219
024, 205, 209, 213, 217
205, 208, 209, 214
084, 204, 024, 205, 209,
210, 213, 216, 217
204, 185
185
185
185
185
185
185
185
185
185
185
185
185
185
176
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PAGE 3 OF 3 FOR
TITLE ATOMIC ABSORPTION TECHNIQUES FOR Ba, Be, CA, CR, Cu, Pb, Mn. Hg. Ni, V, Zn
Al, S(,. As, Co. Fe. Mg. Mn, Mo, K, Ag. Na. Th, Sn, Ti (CONTINUED)
ID NO. 02-02-01-05
American Public Health Association (APHA), American Water Works Association, and Water Pollution Control P.*, ,f »« A A
Methods for the Examination of Water and Waste Water," 135th ed., Washington, DC ,1971, 174 pp. Deration, "Standard
" of the Association of Official Analytical Chemists," 11th ed., Association of
084
204
024
205 Angino, E.E., and G.K. Billings, "Atomic Absorption Spectrometry," in "Methods in Geochemistry and Geophysics," Elsevier
Publishing, New York USD/).
206 Rains, T.C., and 0. Menis, "Accurate Determination of Sufamicrogram Amounts of Mercury in Standard Reference Materials by
Flameless Atomic Absorption Spectrometry," Analytical Chemistry Division, National Bureau of Standards, Washington, D.C., 1972.
207 Wilson, L., "The Determination of Cadmium in Stainless Steel by Atomic Absorption Spectroscopy," Anal. Chim. Acta.. 35_, 123-126 (1966).
208 Delgado, L.C., and D.C. Manning, "Determination of Vanadium in Steels and Gas Oils," Atomic Absorption Newsletter. 5_, 1, (1966).
209 Slavin, W., "Atomic Absorption Spectrometry," Wiley Interscience Publishers, New York, N.Y., 1968, 307 pp.
210 Ramakushna, T.V., et al, "Determination of Copper, Cadmium and Zinc by Atomic Absorption Spectroscopy," Anal Chim Acta 37
20-26 (1967). —
211 Delgado, L.C., and D.C. Manning, "The Determination by Atomic Absorption Spectroscopy of Several Elements Including Silicon
Aluminum and Titanium in Cement," Analyst, 92, 553-557, Sept. 1967.
212 Hatch, R.R., and W.L. Ott, "Determination of Sub-Microgram Quantities of Mercury by Atomic Absorption Spectrophotometry,"
Anal. Chem., 40 (14), 2085-2087, Dec. 1968.
213 Perhac, R.M., and C.J. Whelan, "A Comparison of Water-Suspended Solid and Bottom Sediment Analysis for Geochemical Prospecting
in a Northeast Tennessee Zinc District," Journal of Geochemical Exploration, 1_, 47-53 (1973).
214 S. Ahuja, et al (ed.), "Chemical Analysis of the Environment and Other Medium Techniques," Progress in Analytical Chemistry,
Vol. 5, New York, Plenum Press, 1973.
215 Kneip, J.J., et al, "Tentative Method of Analysis for Chromium Content of Atmospheric Particulate Matter by Atomic Absorption
Spectroscopy," Health Lab. Sci., 10 (4), 357-361 (Oct. 1973).
216 "Instrumental Analysis of Chemical Pollutants, Training Manual," PB 214-504, Environmental Protection Agency Water Quality Office,
Washington, D.C., April 1971, 294 pp.
217 Hedley, W.H., S.M. Metha and P.L. Sherman, "Determination of Hazardous Elements in Smelter-Produced Sulfuric Acid," EPA 650.2-74-131,
Monsanto Research Corporation, Dayton, Ohio, Dec. 1974, 49 pp.
218 Tucker, G.H., and H.E. Malone, "Atmospheric Diffusion of Beryllium," Final Report A/F Sys. Command AFRLP-TR-70-65, Vol. No. 1,
113 (July 1971).
219 Baldeck, C., and G.W. Kalb, "The Determination of Mercury in Stack Gases of High SOj Content by the Gold Amalgamation Technique,"
EPA-R2-73-153, (PB 220-323), TraDet Inc., Columbus, Ohio, Jan. 1973, 111 pp.
177
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1. TITLE DETERMINATION OF ACIDITY BY ELECTROMETRIC TITRATION
2. IDENTIFICATION CODE
02-02-01-06
3. ABSTRACT OF METHODOLOGY
The method Involves the determination of total acidity, due to strong and weak acids, plus acidity resultirm from the formation of stable
hydroxy complexes by metal ions. The initial PH of the sample is measured with a pH meter. If the pH is above 4.0, standard sulfuric acid
is added to lower pH to 4 or less. Hydrogen peroxide is then added for the oxidation and hydrolysis of polyvalent cations, such as iron and
aluminum salts. After boiling and cooling to room temperature, the sample is titrated electrometrically with standard alkali to oH 8.2.
Acidity is then reported as equivalent concentration of hydrogen ions in milligrams per liter, or alternatively, as equivalents of calcium
carbonate.
4. APPLICATION- Compliance, environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to all aqueous streams (liquid and slurry discharges) including surface waters, sewages, and other industrial
wastes.
B) INTERFERENCES/LIMITATIONS
A sluggish electrode response may be observed due to presence of suspended matter or precipitates formed during the titration.
This is offset by slow, dropwise addition of titrant near the endpoint, or by 15-20 second pauses between titrant additions.
C) RECOMMENDED USE AREA
This is the recommended level 1 environmental assessment procedure for the measurement of mineral acidity of aqueous effluents,
plus acidity from oxidation and/or hydrolysis of polyvalent cations (iron and aluminum salts) and is applicable to all liquid/
slurry streams.
5. OPERATIONAL PARAMETERS
A) RANGE 10 to 1,000 mg/liter acidity as CaCO,, using samples having volumes of 50 ml.
B) ACCURACY 10% relative error or less.
C) PRECISION +10 mg/liter.
6. REAGENTS REQUIRED
Hydrogen peroxide, 0.02N standard sodium hydroxide, 0.02N standard
sulfuric acid, indicators (Bromcresol Green, Methyl Orange,
Methyl Purple, Methyl Red, Phenolphthalein).
7. EQUIPMENT REQUIRED
Pipet, Erlenmeyer flask, electrometric titration apparatus.
8. KEYWORD INDEX: Acidity, aqueous effluents, liquid/slurry, electrometric titration.
9. CROSS REFERENCE ID NUMBERS 01-02-02-02, 01-02-02-01.
10. REFERENCES
A)
B)
C)
PR (MARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory, Natl.
Environmental Research Center, EPA No. 625/6-74-003, Washington, 1974, p. 1-2.
BACKGROUND INFORMATION
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," Part 23, ASTM Method D-1067, "Standard Methods of Test for
Acidity or Alkalinity of Water," American Society for Testing and Materials, Philadelphia, PA., 1971, Method B, p. 138.
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," Part 23, ASTM D1293-65, "Standard Method of Test for pH of
240r241 Watel" and Irdustl"ial Wastewater," American Society for Testing and Materials, PHiladelphia, PA., 1971,
084 American Public Health Association (APHA), American Water Works Association and Water Pollution Control Federation,
"Standard Methods for the Examination of Water and Wastewater," 13th ed., Washinqton, D C 1971 Method 201, p. 370.
FIELD APPLICATIONS ' '
178
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1. TITLE DETERMINATION OF ARSENIC BY SILVER DIETHYL DITHIOCARBAMATE METHOD
•
ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-02-01-07
Inorganic arsenic compounds are reduced to arsine by zinc in an acid medium. The resulting gas mixture is passed through a scrubber
packed with glass wool which has been impregnated with a lead acetate solution, and into an absorbing tube for subsequent digestion in
a pyridine (or 1-ephedrine in chloroform) solution of silver diethyl dithiocarbamate. The red complex formed is measured spectrophoto-
metrically at 535 nm, and arsenic is determined by reference to an analytical curve prepared from standards.
4. APPLICATION- Engineering evaluation R&D, environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to all aqueous streams (liquids and slurries) including surface, ground and saline water, domestic and
industrial effluents.
B) INTERFERENCES/LIMITATIONS
High concentrations of chromium, cobalt, copper, mercury, molybdenum, nickel and silver may provide interference. Industrial
effluents having high concentrations of organic matter may be oxidized prior to digestion (see Ref. 204).
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D procedure for the determination of total inorganic arsenic. Industrial wastes
having low arsenic concentrations may be concentrated prior to digestion, or spiked with a known concentration of arsenic in order
to improve accuracy. Streams having high trace metal concentrations may provide interference.
5. OPERATIONAL PARAMETERS
A) RANGE Inorganic arsenic is determined at concentrations of 10 pg/liter or greater.
B) ACCURACY Relative error of 0% has been achieved in analyses performed on synthetic unknown samples having 40 ^g/liter arsenic.
Cl PRECISION Relative standard deviation of 13.8% has been achieved in analyses performed on synthetic unknown samples having
40 vg/liter arsenic.
6. REAGENTS REQUIRED
Lead acetate; silver diethyl dithiocarbamate solution in pyridine
(or 1-ephedrine in chloroform).
7. EQUIPMENT REQUIRED
Beakers; spectrophotometer;
absorber, glass wool.
arsine generator, scrubber and
8. KEYWORD INDEX: Arsenic, aqueous effluents, silver diethyl dithiocarbamate method, spectrophotometry.
9, CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02.
W. REFERENCES
A) PRIMARY SOURCE „ f. -,
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory, National
Environmental Research Center EPA No. 625/6-74-003, Washington, 1974, p. 9-10.
« BACKGROUND INFORMATION
204 American Public Health Association (APHA), American Water Works Association and Water Pollution ^tro1 Federation
"Standard Methods for the Examination of Water and Wastewater," 13th ed., Washington, D. C., 1971, Method 104(A . p.
204 African Public Health Association (APHA), American Water Works Association and Water Pollution Contro Fe erat on,
"Standard Methods for the Examination of Water and Wastewater," 13th ed., Washington, D. (.., is/i.
Procedure 4a, p. 65.
0 FIELD APPLICATIONS t- of
205 Liederman, D, J.E. Bowen and O.I. Milner, "Determination of Arsenic in Petroleum Stocks and Catalysts by Evo u ion
Arsine, Anal. Chem.. 31. 2052 (1959).
:?:
'eg-,' ^inTtotef^tandards,'' Public Health Service Pub., 956, p. 7 (1962).
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1. TITLE DETERMINATION OF BIOCHEMICAL OXYGEN DEMAND USING BIOASSAY PROCEDURES
Z IDENTIFICATION CODE
02-02-01-08
3. ABSTRACT OF METHODOLOGY
Method involves use of empirical bioassay-type procedure to measure the dissolved oxygen consumed by microbial life in the digestion of
organic matter present in a sample. A sample is incubated in the dark at 2p°C for 5 days. Dissolved oxygen is measured both before and
after incubation using either the Modified Winkler with Full Bottle Technique (see 02-02-01-09) or the probe method (02-02-01-10).
4. APPLICATION' Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to all aqueous streams (liquids and slurries) including industrial effluents.
B) INTERFERENCES/LIMITATIONS
None
C) RECOMMENDED USE AREA
This is the recommended compliance method for BOD for all aqueous effluents.
OPERATIONAL PARAMETERS
A) RANGE N/Q; typical BOD range from one to several hundred rag/liter.
B) ACCURACY No acceptable procedure exists for measurement of accuracy of BOD test.
C) PRECISION Standard deviations of +0.7 and +26 mg/liter BOD were observed for mean values of 2.1 and 175 nig/liter BOD.
6. REAGENTS REQUIRED
See 02-02-01-09 and 02-02-01-10.
7. EQUIPMENT REQUIRED
Incubator
8. KEYWORD INDEX: Biochemical oxygen demand (BOD), aqueous effluents, oxygen requirements.
9. CROSS REFERENCE ID NUMBERS 01-02-02-02, 01-02-02-01; 02-02-01-09, 02-02-01-10.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Reserach Laboratory, National
Environmental Research Center, EPA No. 525/6-74-003, Washington, 1974, p. 11-12.
B) BACKGROUND INFORMATION
204 American Public Health Association (APHA), American Water Works Association and Water Pollution Control Federation,
Standard Methods for the Examination of Water and Wastewater," 13th ed., Washington, D. C., 1971, Method 219, p. 489.
C) FIELD APPLICATIONS
180
-------
1 TITLE ?!JS^Mc7ION °F D|SSOLVED OXYGEN (MODIFIED WINKIER WITH FULL-BOTTLE
'* TECHNIQUE:/
^^•»— l""^" !••! **•— • — ...
3. ABSTRACT OF METHODOLOGY
I IDENTIFICATION CODE
02-02-01-09
Method involves treatment of sample with manganous sulfate, a solution of potassium hydroxide, potassium iodide (and sodium azide
optional) and sulfuric acid. The manganous hydroxide precipitate combines with the dissolved oxygen to form a new brown precipitate of
manganic hydroxide, which is converted to manganic sulfate upon acidification. The manganic sulfate reduces the potassium iodide and
releases free iodine, which is then titrated with sodium thiosulfate or phenylarsine oxide (PAO) using starch as the indicator
4. APPLICATION' Compliance, environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to liquid/slurry effluents (drinking, surface and saline waters, domestic and industrial wastes) containing
not more than one mg/liter of ferric iron (up to 200 mg/liter, if 1 ml of fluoride solution is added before sample modification).
B) INTERFERENCES/LIMITATIONS
Other interferences include nitrite nitrogen (eliminated by the Alsterberg azide modification) and high organic content (compensated
for by the Theriault procedure). Samples containing sulfite, thiosulfate, polythionate, chlorine or hypochlorite, high suspended
solids, organics which are oxidized by alkali and iodine, untreated domestic sewage, biological floes, and highly colored samples
interfere with the azide modification.
C) RECOMMENDED USE AREA
This is the recommended compliance procedure for the determination of DO in aqueous effluents not high in organic content (ash
dewatering effluent, product gas dehydration units, etc.).
5. OPERATIONAL PARAMETERS
A] RANGE N/Q
B) ACCURACY 10% relative error or less.
C) PRECISION Reproducibility of 0.2 ppm DO at the 7.5 ppm level has been reported.
6. REAGENTS REQUIRED
Manganous sulfate; potassium hydroxide; potassium iodide; cone.
sulfuric acid; sodium thiosulfate, (sodium and potassium
azide-optional , starch suspension).
7. EQUIPMENT REQUIRED
BOD sample bottle; laboratory glassware; titration
assembly.
& KEYWORD INDEX: Dissolved oxygen (DO), aqueous effluents, Modified Kinkier.
9, CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02; 02-02-01-08.
10. REFERENCES
A) PRIMARY SOURCE
.185' "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory,
National Environmental Research Center, EPA No. 625/6-74-003, Washington, 1974. p. bi-w.
B> BACKGROUND INFORMATION
209 Kroner, R.C., R. Gorman and J. Longbottom, "A Comparison of Various Reagents PropoMdforUse In the Winker Quality1"6
Dissolved Oxygen," PUS Water Pollution Surveillance System Applications and Development, Report No. U, V
Section, Basic Data Branch, July 1964.
0 FIELD APPLICATIONS
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1. TITLE DETERMINATION OF DISSOLVED OXYGEN (DO) BY ELECTRODE (PROBE") METHOD
2. IDENTIFICATION CODE
02-02-01-10
3. ABSTRACT OF METHODOLOGY
The electrode (probe) method uses commercially available probes for the determination of dissolved oxygen (DO). These include membrane
probes and thallium probes. Membrane probes measure partial pressure of oxygen, which is a function of dissolved organic salts; the
current or potential is then correlated with DO concentrations. The thallium probe requires salt concentrations which provide a minimum
conductivity of 200 micromhos.
4. APPLICATION^ Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to all aqueous (liquid and slurry) streams, including those excluded from the Modified Winkler procedure
(see 02-02-01-09).
B) INTERFERENCES/LIMITATIONS
When membrane probes are used, reactive gases (chlorine, hydrogen sulfide) may interfere. For thallium probes, sulfur compounds
such as hydrogen sulfide, sulfur dioxide and mercaptans, may cause interference. Dissolved organics do not cause interference.
Membrane performance is not affected by pH changes.
C) RECOMMENDED USE AREA
This is the recommended compliance procedure for DO determination for all aqueous streams (ash dewatering effluent, condensate
recycle water, product dehydration effluent) which are low in sulfur compounds.
OPERATIONAL PARAMETERS
A) RANGE Standard probes have sensitivity of 0.05 mg/liter.
B) ACCURACY ±1% accuracy.
C) PRECISION 0.1 mg/liter repeatability.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
N/A
Probe, such as: Weston and Stack DO Analyzer Model 30; Yellow
Springs Instrument(YSI) Model 54; Beckman Fieldlab Oxygen Analyzer
8. KEYWORD INDEX: Dissolved oxygen (DO), aqueous effluent, probe method.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02; 02-02-01-08, 02-02-01-09.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory,
National Environmental Research Center, EPA No. 625/6-74-003, Washington, 1974, p. 56-58.
B) BACKGROUND INFORMATION
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory,
National Environmental Research Center, EPA No. 625/6-74-003, Washington, 1974, p. 51-55.
C) FIELD APPLICATIONS
182
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1. TITLE DETERMINATION OF BORON BY CURCUMIN METHOD
_ •
3, ABSTRACT OF METHODOLOGY
IDENTIFICATION CODE
02-02-01-11
Method involves sample acidification and evaporation in the presence of curcumin to form the red-colored rosocyanine. The rosocyanine
is then extracted into a suitable solvent (ether, alcohol) and determined spectrophotometrically at 530 nm.
4. APPLICATION' Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to all aqueous (liquid and slurry streams) having 0.1-1.0 mg/liter boron (optimum range).
8) INTERFERENCES/LIMITATIONS
Interferences are nitrate nitrogen concentrations above 20 mg/liter, and total calcium and magnesium hardness above 100 mg/liter
as CaCO,. This is eliminated by use of a cation exchange resin.
C) RECOMMENDED USE AREA
This is anaalternate compliance procedure for the determination of boron in most industrial aqueous effluents, (i.e., ash
dewatering effluent, condensate recycle water, dehydration and cooling water, etc.) (see 02-02-01-05).
5. OPERATIONAL PARAMETERS
A) RANGE l mg/liter or below.
B) ACCURACY 0% relative error on the synthetic sample determinations described below (5c).
0 PRECISION Relative standard deviation of 22.8% measured on synthetic samples prepared by Analytical Reference Service, PHS,
containing 240 pg/liter Be, 20 ug/liter Se, and 6 pg/liter V, in 30 laboratories.
6. REAGENTS REQUIRED
Concentrated standard acid, curcumin.
7. EQUIPMENT REQUIRED
Standard laboratory glassware; spectrophotometer.
& KEYWORD INDEX: Boron, aqueous effluents, curcumin method, spectrophotometry.
9- CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02-02, 02-02-01-05.
10. REFERENCES
A) PRIMARY SOURCE
"Methods for unemicai nnaiysis or water ana wastes, i
National Environmental Research Center, EPA No. 625/6
B» BACKGROUND INFORMATION
185 »Mttodsr Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory,
No. 625/6-74-003, Washington, 1974, p. 13.
GROUND INFORMATION
American Public Health Association (APHA), American Water Works Association and Water Pollution Control Federation,
"Standard Methods for the Examination of Water and Wastewater," 13th ed., Washington, u.
FIELD APPLICATIONS
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1. TITLE DETERMINATION OF CALCIUM BY TITRIMETRY
2. IDENTIFICATION CODE
02-02-01-12
3. ABSTRACT OF METHODOLOGY
Method involves titration of calcium with EDTA (disodium dihydrogen ethylenediamine tetraacetate). EDTA forms a colorless stable
complex with calcium. The murexide indicator is dark purple in the absence of calcium, but forms a light salmon-colored complex with
calcium. The endpoint of the titration is determined visually.
4. APPLICATION: Compliance.
A) OPERATIONAL SCOPE
Method is applicable to all aqueous (liquid/slurry) streams containing dissolved calcium, including domestic and industrial
effluents and drinking and surface waters.
B) INTERFERENCES/LIMITATIONS
Strontium and barium interfere; alkalinity of 30 mg/liter interferes. Magnesium interference is eliminated by raising pH between
12-13 to precipitate magnesium hydroxide. The heavy metal interferences can be eliminated using alkaline hydroxide and sulfide
treatments.
C) RECOMMENDED USE AREA
This is an alternative compliance procedure for the determination of calcium in most aqueous effluents with low
alkalinity (see 02-02-01-05).
5. OPERATIONAL PARAMETERS
A) RANGE Lower detection limit is 0.5 mg/liter as CaC03; the upper detection limit can be extended to all concentrations by
sample dilution, to 25 mg as CaC03, or less.
B) ACCURACY 1.9% in 44 laboratories using synthetic unknown samples containing 108 mg/liter Ca, S3 nig/liter Mg, 3.1 mg/liter K,
19.9 mg/liter Na, 241 mg/liter chloride, 1.1 mg/liter nitrate, 250 ug liter/nitrite nitrogen, 259 mg/liter sulfate and
42.5 mg/liter (total alkalinity).
C) PRECISION Relative standard deviation of 9.2% on samples described above.
6. REAGENTS REQUIRED
EDTA, murexide indicator, standard base for pH adjustment
(optional).
7. EQUIPMENT REQUIRED
Standard laboratory glassware; visual titration assembly.
a KEYWORD INDEX: Calcium, aqueous effluents, titrimetric method.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02, 02-02-01-05.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory,
( National Environmental Research Center, EPA No. 625/6-74-003, Washington, 1974, p. 19.
B) BACKGROUND INFORMATION
204 American Public Health Association (APHA), American Water Works Association, and Water Pollution Control Federation,
"Standard Methods for the Examination of Water and Wastewater," 13th ed.. Washington, 0. C., 1971, Method HOC, p. 84.
210 Banks, J., "The Volumetric Determination of Calcium and Magnesium by the Ethylenediamine Tetraacetate Method," Analyst,;
77, 484 (1952).
O FIELD APPLICATIONS
211 Brown, E., et al, "Methods for Collection and Analyses of Water Samples for Dissolved Minerals and Gases," Chapter A-l
"Techniques of Water-Resources Investigations of the United States Geological Survey," Washington, 1970, p. 64-67.
210 Banks, J., "The Volumetric Determination of Calcium and Magnesium by the Ethylenediamine Tetraacetate Method,"
Analyst._77. 484 (1952).,
of
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1 TITI E DETERMINATION OF TOTAL RESIDUAL CHLORINE BY AMPEROMETRIC TITRATION
1. TITLE OR ,ODOMETR|C TITRATION
_
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-02-01-13
Method Involves titration of a buffered sample contained In an amperometric titration cell with phenyl arsine oxide (PAD). Endpoint
is reached when the generation of current ceases (working electrode vs sat. Ag/AgCl set at +1.13 v).
When chlorine is present as the chloraraine, potassium iodide is added and an iodometric titration is performed. The chlorine
liberates free iodine from potassium iodide solutions when the pH is 8 or below. The liberated iodine is then titrated with a
standard solution of sodium thiosulfate or phenylarsine oxide (PAD) with starch as an indicator.
4. APPLICATION' Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to all aqueous streams (liquids and slurries) which do not contain large quantities of organic matter.
B) INTERFERENCES/LIMITATIONS
Organic material interferes; color, turbidity, iron, manganese and nitrate nitrogen do not interfere.
C) RECOMMENDED USE AREA
This is the recommended compliance procedure for determination of total residual chlorine for aqueous streams low in organic matter
(i.e., ash dewatering effluents, cooling tower waters, etc.).
5. OPERATIONAL PARAMETERS
A) RANGE Method is applicable to samples containing 5 mg/liter or below.
B| ACCURACY N/Q
Cl PRECISION N/Q
6. REAGENTS REQUIRED
Phenylarsine oxide; buffer solution;
thiosulfate; starch.
8. KEYWORD INDEX: Chlorine, total
9. CROSS REFERENCE ID NUMBERS
potassium iodide; sodium
7. EQUIPMENT REQUIRED
Amperometric titration cell, or standard manual
assembly.
residual; aqueous effluents; amperometric titration; iodometric titration.
01-02-02-01, 01-02-02-02.
ti trati on
W. REFERENCES
A) PRIMARY SOURCE
',185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance
National Environmental Research Center, EPA No. 625/6-74-003, Washington, 1974, p. *.
81 S
Research Laboratory,
Association (APHA), American Water Works Association and Water Pollution , Control ;ederati on, g^
"Standard Methods for the Examination of Water and Wastewater," 13th ed. , Washington, u i,.. '
024 ASTM CoMrittees D-19 and D-22, "Water; Atmospheric, Analysis," Part 23, Method D 12 -68 , Delphi a^PA. , 197!,
of Test for Residual Chlorine in Industrial Water," American Society for Testing and naterid,
p. 214.
0 FIELD APPLICATIONS
212 California State Water Quality Control Board, "Water Quality Criteria," Pub. 3-A, p. 162 (
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1. TITLE DETERMINATION OF SILICA (DISSOLVED)
2. IDENTIFICATION CODE
02-02-01-14
3. ABSTRACT OF METHODOLOGY
Method involves filtration of sample through a membrane filter, followed by addition of molybdate ion in acidic solution to the
filtrate. The resultant greenish-yellow silico-molybdate complex is then measured spectrophotometrically at 700 nm. The silico-
molybdate complex may form as alpha and beta polymorphs, which have absorbance maxima at different wavelengths. The addition of
acid (to pH 2.5) favors the development of the preferred beta form.
4. APPLICATION. Compliance, environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to all aqueous (liquid and slurry) streams, including drinking, surface and saline waters, domestic and
industrial wastes.
8) INTERFERENCES/LIMITATIONS
Excessive color and turbidity interfere but may be corrected by blank determinations using uncomplexed sample. Phosphate inter-
feres, but is suppressed by addition of tartaric acid. Hydrogen sulfide may be removed by boiling. Addition of EDTA prevents
interference by high iron concentrations, and also complexes calcium.
C) RECOMMENDED USE AREA
This is the recommended compliance procedure for determination of dissolved silica in aqueous effluents.
5. OPERATIONAL PARAMETERS
A) RANGE 2 to 25 mg silica/liter. The upper range may be extended by taking sample aliquots; the lower range, by treatment
of the sample with amino-naphthol-sulfonic acid, with subsequent spectrophotometric measurement.
B) ACCURACY N/Q
C) PRECISION 4% of the quantity of silica measured, using samples with 2 to 50 mg/liter. Precisions of +0.10 mg/liter are
obtained in the range from 0 to 2 mg/liter.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Ammonium molybdate solution; amino-naphthol-sulfonic acid
(optional); hydrochloric acid; standard silica solution, EDTA;
tartaric acid.
Spectrophotometer; 0.45u membrane filter, standard laboratory
glassware.
8. KEYWORD INDEX: Silica, dissolved; aqueous effluents; spectrophotometry; ammonium molybdate.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02.
10. REFERENCES
AJ PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory,
National Environmental Research Center, EPA No. 625/6-74-003, Washington, 1974. p. 274.
213 Brown, E., "Techniques of Water-Resources Investigations of the U.S. Geological Survey," Washington, 1970, p. 139.
B) BACKGROUND INFORMATION
024 ASTM Committee D-19 and D-23, "Water; Atmospheric Analysis," Part 23, D859-68, "Standard Methods of Test for Silica in
Industrial Water and Industrial Waste Water," American Society for Testing and Materials, Philadelphia, PA., 1973, p. 401
204 Standard Methods for the Examination of Water and Wastewater, 13th ed., Method 151B, 1971, p 303.
214 Strickland, J.D.H., "The Preparation and Properties of Silicomolybdic Acid; I. The Properties of Alpha Silicomolybdic
215 Govett,~B7j.S., "Critical Factors in the Colorimetric Determination of Silica," Anal. Chem. Acta. 25, 69 (1961).
C) FIELD APPLICATIONS
216 Minhoff, C.E., "Boiler Water Conditioning to Prevent Turbine Deposits," Petroleum Refiner. 27., 438 (1948).
186
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1. TITLE SPECTROPHOTOMETRIC DETERMINATION OF ANTIMONY
3. ABSTRACT OF METHODOLOGY
^ IDENTIFICATION CODE
02-02-01-15
In preparation for spectrophotometric determination, the sample is digested using H2S04 - HN03. Oxidizing conditions must be maintained
The digest or aliquot is then transferred to a 125 ml Erlenmeyer. Sulfuric acid is added to make a total of 5 ml of the acid and the
sample is evaporated to fumes of S03. The flask is cooled, perchloric acid is added and the digest is again evaporated to white fumes
The digest is cooled in an ice bath 30 minutes, and 5 ml precooled 3N H3P04 is added. Then 5 ml of precooled Rhodainine B solution
is added, and the flask is stoppered and shaken vigorously. The sample 1s transferred to a precooled 125 ml separator. Next, 10 ml
of precooled benzene are pipetted into the separator, which is then shaken vigorously. The benzene layer (red if Sb is present) is
then transferred to a test tube in order to let the water settle. The sample is then measured spectrophotometrically at 565 mm
against a benzene blank. Concentration of Sb is determined by comparison to a standard curve.
4. APPLICATION: Environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to aqueous (liquid and slurry) effluents, including surface and saline water, domestic and industrial
effluents.
B) INTERFERENCES/LIMITATIONS
The individual operations in the procedure should be performed as quickly as possible, particularly up until
the color is extracted into benzene. The color is stable in benzene for several hours.
C) RECOMMENDED USE AREA
This is an alternative engineering R&D procedure for the determination of antimony in aqueous effluents where the MS
procedure is inoperable.
5. OPERATIONAL PARAMETERS
A) RANGE All concentrations of antimony can be determined, using suitable aliquots.
B) ACCURACY N/Q
C) PRECISION N/Q
6. REAGENTS REQUIRED
Hydrochloric acid, dilute phosphoric acid, Rhodamine B solution,
antimony standard solutions, sulfuric acid, benzene.
7. EQUIPMENT REQUIRED
Spectrophotometer; standard laboratory glassware,
stoppered Erlenmeyer flasks.
including
KEYWORD INDEX: Antimony, aqueous effluents, spectrophotometry.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02.
W. REFERENCES
cl, M.L. Kraft, C. Lin, R.F. Maddalone, ..A. Starkovich and C Zee ^Procedures for Process Measurements: Trace
Inorganic Materials," TRW Systems Group, EPA Contract No. 68-02-1393, July IB/b.
BACKGROUND INFORMATION . „ ,. 1971 Annuai
173 ASTM Cowittee E-2, E-3 and E-16, "Chemical Analysis of Metal.! Sampling an<| Analysis of ^al-Beanng ^ .^ ^^
Book of ASTM Standards, Part 32 E87, "Photometric Methods for Chemical ^s^ OT ueaa>
American Society for Testing and Materials, Philadelphia, PA., 19/1, P- *<"•
FIELD APPLICATIONS
187
-------
1. TITLE DETERMINATION OF SELENIUM BY DIAMINOBENZIDUME METHOD
2. IDENTIFICATION CODE
02-02-01-16
3. ABSTRACT OF METHODOLOGY
Method involves oxidation of all selenium compounds found in the sample to selenate using potassium permanganate. The selenate is
then reduced to selenite in warm dilute hydrochloric acid. Diaminobenzidine is then added, and the resultant species (piazselenol)
is determined spectrophotometrically at 420 nm.
4. APPLICATION: Environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to aqueous (liquid and slurry) streams, including natural waters and industrial effluents, not containing
high concentrations of iodide and bromide.
B) INTERFERENCES/LIMITATIONS
Iodide and bromide interfere. Compounds which oxidize the diaminobenzidine reagent interfere, although EDTA removes this
interference.
C) RECOMMENDED USE AREA
This is the recommended environmental assessment method for the determination of selenium in aqueous samples.
5. OPERATIONAL PARAMETERS
A) RANGE Method is applicable to all ranges of selenium, using suitable aliquots.
B) ACCURACY N/Q
C) PRECISION Analysis of 3 test samples by 7 laboratories resulted in means of 49, 84 and lOug/liter, with standard deviations of
6, 8 and Bug/liter, respectively.
6. REAGENTS REQUIRED
Ammonium chloride, ammonium hydroxide, calcium chloride,
diaminobenzidine solution, EDTA-sulfate reagent, hydrochloric
acid, methyl orange indicator (optional), standard selenium
solutions.
7. EQUIPMENT REQUIRED
Spectrophotometer for use at 420 nm; standard laboratory glass-
ware; standard titration assembly (optional, for interference
removal).
8. KEYWORD INDEX: Selenium, aqueous effluents, diaminobenzidine method, spectrophotometry.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02.
10. REFERENCES
A) PRIMARY SQURCE
217 "Techniques of Water-Resources Investigations of the U.S. Geological Survey," Chapter Al,"Methods for Collection and Analysis
of Water Samples for Dissolved Minerals and Gases," Washington, 1970, p. 135-7.
B) BACKGROUND INFORMATION
218 California State Water Quality Control Board, "Water Quality Criteria," Pub. 3-A, p. 253 (1963).,
219 Rossum, J.R., and P.A. Villarruz, "Suggested Methods for Determining Selenium in Water," Am. Water Works Assoc. Jour.,
V. 54, p. 746 (1962).,
C) FIELD APPLICATIONS
220 Scott, R.C., and P.T. Voegeli, "Radiochemical Analyses of Ground and Surface Water in Colorado, 1954-1961 " Colorado
Water Conserv. Board Basic-Data Rept. 7, 1961 .i
221 Maag, D.D., and M.W. Gleen, "Toxicity of Selenium: Farm Animals," Sec. Ill in "Selenium in Biomedicine-A Symposium,"<
The Avi Publishing Co., Westport, Conn., p. 127-140, 1967.
222 Muth, O.H.(ed.), "Selenium in Biomedicine," The Avi Publishing Co., Westport, Conn., p. 445, 1967.,
-------
1. TITLE DETERMINATION OF SELENIUM BY DISTILLATION - DIAMINOBENZIDINE METHOD
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-02-01-17
Sample is treated with bromine to form the volatile tetrabromide. The tetrabromide is distilled, along with a minimum of exce
bromine, and condensed and absorbed into a beaker of water. The excess bromine is removed by precipitation with a phenol solution
as tribromophenol, and the tetravalent selenium is subsequently treated with diaminobenzidine (see 02-02-01-16) and determi° d ^
spectrophotometrically at 420 nm.
4. APPLICATION^ Environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to aqueous (liquid and slurry) streams, including natural waters and industrial effluents, and including
waters containing high concentrations of iodide and bromide.
B) INTERFERENCES/LIMITATIONS
No known interferences.
0 RECOMMENDED USE AREA
This is the alternate recommended environmental assessment method for the determination of selenium, particularly for samples
containing bromide and iodide, (see 02-02-01-16)
5. OPERATIONAL PARAMETERS
A) RANGE Method is applicable to all ranges of selenium, using suitable aliquots.
B) ACCURACY N/Q
C) PRECISION No precision data are available; see 02-02-01-16 for results of diaminobenzidine method.
6. REAGENTS REQUIRED
Calcium chloride, diaminobenzidine solution, hydrochloric acid,
methyl orange indicator, potassium permanganate, standard
selenium solutions, sodium hydroxide, ammonium hydroxide, hydrogen
_. peroxide, phenol solution; potassium bromide-acid reagent.
7. EQUIPMENT REQUIRED
Distillation assembly; standard laboratory glassware, standard
titration assembly (optional, for interference removal),
spectrophotometer for use at 420 nm.
8. KEYWORD INDEX: Selenium, aqueous effluents, distillation-diaminobenzidine method, spectrophotometry
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02s 02-02-01-16.
10. REFERENCES
"
217VS°^eCcEhniques of Water Resources Investigations of the U.S. Geological Survey," Chapter Al "Methods for Collection
and Analysis of Water Samples for Dissolved Minerals and Gases," Washington, 1970, p. u/-».
B> BACKGROUND INFORMATION „„, ,. „ ,„ (1963)
218 California State Water Quality Control Board, "Water Quality Criteria Puti. 3-A,, p. "J ^ '445
222 Muth, O.H., ed., "Selenium in Biomedicine," Westport, Conn., The Avi Publish ng Co., 1967, P;^r Unrk, flssoc. Jour.,
219 Rossum, J.R.,and P.A. Villarruz,"Suggested Methods for Determining Selenium m Water, Mi. Mate _
54. P- 746, 1962,
~. ,— ..... and P.T. Voegeli, "Radiochemical Analyses of Ground and Surface Water in Colorado, 1954-1961," ^
Colorado Water Conserv. Board-Basic Data Rept. 7, 1961. "selenium in Biomedicine-A Symposium,
221 Maag, D.D., and M.W. Glenn, "Toxicity of Selenium: Farm Animals, Sec. in in
Westport, Conn., The Avi Publishing Co., p. 127-140.
189
-------
PAGE 1 OF 3 FOR
1.
3.
TITLE DETERMINATION OF CATIONS USING SPECIFIC ION ELECTRODES
ABSTRACT OF METHODOLOGY
(SIE)
2. IDENTIFICATION CODE
02-02-01-18
Specific Ion electrodes can be used to determine the cations and species shown in Table 02-02-01-18A. Samples can be
determined by direct reading measurements, in which the electrode is inserted into the sample and a reading is taken,
or by electrode titrations. There are 3 basic types of electrode titrations: R, S, and T. In R titrations, the
electrode senses the reagent (R) species (usually an indicator) that is added to the sample prior to titration. In
S titrations, the electrode senses the sample (S) species. In T titrations, the electrode senses the level of
titrant (T) during the course of addition to the sample. The titration method allows determination of a number of
4.
species not directly sensed by the electrode; e.g., aluminum can be
in a T type titration. R titrations can be used to measure nickel,
are shown in Table 02-02-01-18A.
APPLICATION: Environmental assessment.
A) OPERATIONAL SCOPE
titrated with fluoride, using the fluoride electrode
zinc, manganese and strontium. Other applications
Method is applicable to samples (aqueous samples, species absorbed in liquids) containing cations and
species shown in Table 02-02-01-18A.
B) INTERFERENCES/LIMITATIONS
Extremes of pH may interfere. Anions which complex with specific cations may interfere in the analysis
of the cation.
C) RECOMMENDED USE AREA
This is the applicable to level 1 environmental assessment procedure for determination of cations
5.
having concentration ranges listed in Table 02-02-01-18A.
OPERATIONAL PARAMETERS
A) RANGE See Table 02-02-01-18A for detectable concentrations of specific cations and species. Electrodes are capable of
measuring ion activities well below concentration limits for cadmium, lead, cupric ion, and other cations.
8) ACCURACY N/Q
6.
C) PRECISION +0.i or ]ess -jn many cases.
REAGENTS REQUIRED
Suitable precipitation or complexing agents, when required for
specific analyses; e.g., EDTA for analysis of copper; pH adjusters
and titrants (Table 02-02-01-01B).
a
9.
10.
7. EQUIPMENT REQUIRED
Specific ion electrodes, specific ion meter or standard pH meter
having an expanded millivolt scale standard laboratory glassware
(beakers, pipettes, volumetric flasks).
KEYWORD INDEX' Specific ion electrodes, aqueous effluents, aqueous absorbed samples,
cations.
CROSS REFERENCE ID NUMBERS 02-03-02-01; 01-02-01-02, 01-02-02-01, 01-02-02-02.
REFERENCES
A) PRIMARY SOURCE
223 Orion Research, "Analytical Methods Guide," Orion Research
B) BACKGROUND INFORMATION
(See reverse side)
C) FIELD APPLICATIONS
(See reverse side)
, Inc., 7th ed., May 1975.
190
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PAGE 2 OF 3 FOR
— . . 1 —
TITLE DETERMINATION OF CATIONS USING SPECIFIC ION ELECTRODES (SIE) (CONTINUED) ID NO. 02-02-01-18
. 1 _ ____
Table 02-02-01-18A. Cation and Species Analysis Using SIE (Reference 223).
Electrode
i ammonia
( aiiimoni urn)
i cadmium
i calcium
• carbon dioxide
• divalent cation
(water hardness)
• t'luoroborate
i hydrogen sulfide
i lead
< nitrogen oxide
(nitrite)
«pH
i potassium
• redox
i silver/sulfide
• sodium
• sulfur dioxide
(sulfite)
*For 10 percent
Type
gas sensing
solid-state
liquid
gas sensing
liquid
liquid
gas sensing
solid-state
gas sensing
glass
liquid
combination
solid-state
solid-state
combination
gas sensing
error
Concentration
Range (M)
10° to 10~6
10° to 10 7
10° to 10 5
W~d x 10 *
10° x 6 x 10"6
saturated to
3 x 10"6
10"2 to 10"6
10° to 10"7
10~2 to
5 x 10"7
pH 0-14
10° to 10"5
not applicable
10° to 10"7
Ag+ or S=
saturated to
ID'6
saturated to
10"6
10~2 to
3 x 10"6
Temperature
Range (°C)
0-50
0-80
0-50
0-50
0-50
0-50
0-50
0-80
0-50
0-100
0-50
0-80
0-80
0-80
0-80
0-50
Interferences
volatile amines
max level: Ag , Hg , Cu++< 10 7 H; high
levels of lead and ferric ion
i nterf ere
0.3 Na+; 2 x 10~6 Zn"H';
5 x 10"6 Pb++;
max level * (M) 7 x 10"5 Fe^, Cu++;
at 10"3 M Ca++ ' 8 x 10~3 Sr"", Mg4+;
3 x 10"2 Bat+;
^5 x 10~2 Nit+
volatile weak acids
3 x 10~2 Na+;
max level * M at 3 x 10"5 ^' l\'
ID'3 M Ca++/Hg++ 6 * "'* Fe ' ' '°~4 Ni +;
4 x 10"4 Sr ;
6 x 10'4 Ba++
!2 x 10"2 NO, ; 0.2 Br",
OAC-, HCO,-. F-. cr.
OH-, S04
none
max level: Ag+, HgH"f, Cu++slO"7 M; high
levels of cadmium and ferric
ion interfere
max level * (H) in 10"3 M NOx: CO,,
2 ^
3 x 10 M; volatile weak acids
i nterf ere
sodium interferes at pH 14
max level * (M)llO'4 Cs+; 3 x 10"3 N«4+;
at 10-3M K+ llO'2 H+, Tl+; 0.1 Ag+: 0.5 Na+
not applicable
max level: Hg++ <10"7 M
(3 x 10"7 Ag+; 10"6 H+;
5 x 10"5 Li+;
6 x ID'2 Cs+; 0.1 K+|
0.2 N(C2H5)+; 0.5 Tl+
same as solid state
max level * in 10"3 M S02 solution: HF,
3 x 10'3 M; acetic acid, 5 x 10" M;
HC1 > 1 M
Notes
measures organic N after
Kjeldahl digestion NO, after
reduction to NH^
can be used for chelometric
indicator titrations for metal
ions, e.g., Zn", Ni+'f
can also be used to measure
sulfate by titration with lead
measures NO and N02 in air
after scrubbing
not to be used in acid
fluoride solutions
10"8 lower limit possible with
proper pH adjustment
for measuring S02 in stack
gases
i—1"
191
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PAGE 3 OF 3 FOR
TITLE DETERMINATION OF CATIONS USING SPECIFIC ION ELECTRODES (SIE) (CONTINUED)
ID NO. 02-02-01-18
B) BACKGROUND INFORMATION
185 "Methods for Chemical Analysis of Water and Wastes," National Environmental Research Center, EPA 625/6-74-003
Cincinnati, 1974, p. 65-67. '
223 Crosby, N.T., A.L. Dennis and J.G. Stevens, "An Evaluation of Some Methods for the Determination of Fluoride
in Potable Waters and Other Aqueous Solutions," Analyst. 93J10), 643 (1968).
224 Tackett, S.L., "Automatic Titration of Calcium with EDTA Using a Calcium Selective Electrode," Anal. .Chem..
41(12), 1703 (1969).
225 Muller, D.C., R.H. Muller and P.W. West, "Determination of Silver Ion in Parts per Billion Range /nth a Selective
Ion Electrode," Anal. Chem., 41(14), 2038 (1969).
226 Baumann, E.W., "Determination of Aluminum by Potentiometric Titration with Fluoride," Anal. Chem., 420),
110 (1970).
227 Hadjiioannou, T.P., and D.S. Papastathopoulos, "EDTA Titration of Calcium and Magnesium with a Calcium-Selective
Electrode," Talanta. V7, 399 (1970).
C) FIELD APPLICATIONS
228 Lee, T.G., "A System for Continously Monitoring Hydrogen Chloride Concentrations in Gaseous Mixtures Using
a Chloride Ion Selective Electrode," Anal. Chem.. jlUz). 391 (1969).
,,Q Hicks, J.E., J.E. Fleenor and H.R. Smith, "The Rapid Determination of Sulfur in Coal," Anal. Chim. Acta..
"* 68, 480 (1974).
192
-------
1. TITLE DETERMINATION OF AMMONIA BY COLORIMETRIC PHENATE METHOD
3. ABSTRACT OF METHODOLOGY
I IDENTIFICATION CODE
02-02-01-19
The sample is treated with sodium phenolate and sodium hypochlorite solutions. The ammonia which is present reacts to
form indophenol blue. The color formed is then intensified by the addition of sodium nitroprusside. The indophenol
blue is determined spectrophotometrically at 630 nm; concentration is determined by comparison to standard curves.
Sample pretreatments Include the masking of calcium and magnesium ions with a 5% EDTA solution and/or filtration to
minimize turbidity.
4. APPLICATION: compliance
A) OPE RATIONAL SCOPE
Method is applicable to determination of ammonia in drinking, surface and saline waters, domestic and
industrial wastes.
B) INTERFERENCES/LIMITATIONS
Calcium and magnesium ions interfere, but are removed with EDTA. Mercury chloride, used as preservative,
gives negative interference by complexing with ammonia; this is overcome by addition of HgClj to ammonia
standards used in preparation of the standard curve. Turbidity and excessive color may also interfere.
C) RECOMMENDED USE AREA
This is the recommended compliance method for inorganic ammonia.
5. OPERATIONAL PARAMETERS
A) RANGE
0.01 to 2.0 mg/liter ammonia as nitrogen.
B| ACCURACY In a single laboratory with surface water samples of 0.16 and 1.44 mg NH3 as nitrogen per liter,
recoveries were 107% and 99%, respectively.
C) PRECISION Standard deviation of ±0.005 was obtained in a single laboratory with 1.41, 0.77, 0.59 and 0.43 mg
ammonia as nitrogen.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
High purity water, 5N sulfuric acid, sodium phenolate
solution, sodium hypochlorite solution, disodium ethylenediamine
tetraacetate (5X), sodium nitroprusside solution (0.05X), stock
'••- chloride solution.
Spectrophotometer for use at 630 nm with path length
of 1 cm.'
aimion
8. KEYWORD INDEX: Ammonia, spectrophotometry, phenate method.
J). CROSS REFERENCE ID NUMBERS 01-02; 02-02-01-20.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," National Environmental Research Center, EPA-625/6-74-003,
Washington, 1974, p. 168. n .,. u ...
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater" 13th ed.. *"jn«n Public Hea th
Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washington, u. t.,
1971, p. 232.
Bl BACKGROUND INFORMATION
186 Mitre Corporation, Compendium of Analytical Methods, Vol. II, Method Summaries, U.S. Environmental Protection
Agency, PB 228-425, April 1973. , w N-A 55, 657 (1963).
219 Rossum, J.R., and P.A. Villaruz, "Determination of An»nia by the Indophenol Method, 4jb!L__ ~ ^^
230 Weatherburn, M.W., "Phenol-Hypochlorite Reaction for Determination of Ammonia," Anal. Chern^. 39,
C> FIELD APPLICATIONS
193
-------
PAGE 1 OF 2 FOR
1. TITLE DETERMINATION OF TOTAL NITROGEN BY KJELDAHL METHOD
2. IDENTIFICATION CODE
02-02-01-20
3. ABSTRACT OF METHODOLOGY
Total Kjeldahl nitrogen is the sum of free ammonia and organic nitrogen compounds (amino acids, proteins, possibly amines,
nitro compounds, and hydrazones) which are converted to ammonium sulfate under the prescribed digestion conditions. The
sample is heated in the presence of concentrated sulfuric acid, potassium sulfate and mercurous sulfate and evaporated
until sulfur trioxide fumes evolve and the solution becomes colorless or pale yellow. The residue is cooled, diluted,
and treated with a hydroxide-thiosulfate solution. The ammonia is then distilled into U boric acid solution. Then
NH3 is determined by titration with standard sulfurfc acid to a pH endpoint of 6.8 (see 02-02-01-19 for colorimetric
finish, 02-02-01-18 for specific ion electrode finish) using methyl red/methylene blue mixed indicator.
4. APPLICATION: Compliance
A) OPERATIONAL SCOPE
Method is applicable to determination of total Kjeldahl nitrogen in drinking, surface and saline waters,
domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Samples which are preserved by addition of concentrated sulfuric acid or mercuric chloride should be
analyzed as soon as possible.
C) RECOMMENDED USE AREA
This is the recommended compliance method for total nitrogen.
OPERATIONAL PARAMETERS
A) RANGE 1 mg nitrogen/liter or above if titrimetric determination is performed; below 1 mg/liter if
colorimetry is used.
B) ACCURACY Accuracy as mg N/liter of +0.03, +0.02, +0.04 and -0.08 was obtained on samples containing
0.20; 0.31, 4.10 and 4.61 mg N/liter, respectively.
Cl PRECISION Precision as standard deviation of 0.197, 0.247, 1.056 and 1.191 was obtained on samples
cited above.
6. REAGENTS REQUIRED
High purity water, sulfuric acid-mercuric sul fate-potassium
sulfate solution; standard sulfuric acid solution,
methyl red-methylene blue indicator.
7. EQUIPMENT REQUIRED
Kjeldahl distillation apparatus, consisting of Kjeldahl
flask, bulb or trap, and vertical condenser titration assembly,
spectrophotometer for use at 425 nm.
& KEYWORD INDEX: Nitrogen (total), Kjeldahl, titrimetry, colorimetry.
9. CROSS REFERENCE ID NUMBERS 01-02; 02-02-01-19, 02-02-01-18.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," National Environmental Research Center
EPA-625/6-74-003, Washington, 1974, p. 175.
204 Taras, M.J. (ed ) "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D. C.,
! 3 / I , p. 232,
B) BACKGROUND INFORMATION
186 Mitre Corporation, "Compendium of Analytical Methods, Volume II, Method Summaries," U S Environmental
Protection Agency, PB-228-425, April 1973, p. B-36.
231
" "A NSW Method for the Determination of Nitrogen in Organic Matter," I. Anal. Chem. . 22,
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PAGE 2 OF 2 FOR
TITLE DETERMINATION OF TOTAL NITROGEN BY KJELDAHL METHOD (CONTINUED)
ID NO. 02-02-01-20
B| BACKGROUND INFORMATION (Continued)
232 Mackenzie, H.A.,and H.S. Wallace, "The Kjeldahl Determination of Nitrogen: A Critical Study of
Digestion Conditions," Austral. 0. of Chem., ]_, 55 (1954).
233 Boltz, D.F. (ed.), "Colorimetric Determination of Itonmetals," Interscience Publishers, New York,
p. 75-97, 1958.
C) FIELD APPLICATIONS
195
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PAGE 1 OF 2 FOR
1. TITLE DETERMINATION OF HEAVY METALS BY DITHIZONE METHOD
2. IDENTIFICATION CODE
02-02-01-21
3. ABSTRACT OF METHODOLOGY
Diphenylthiocarbazone (dithizone) reacts to form colored coordination compounds with silver, cadlura, lead, zinc and other heavy metals.
Under the proper conditions and with removal of interferences, the reaction can be made selective for a desired metal. Table 02-02-01-21A
lists specific procedures for removal of interferences for Ag, Cd, Pb and In. The colored metal-dithizone complexes are then measured
spectrophotometrically and specific concentrations are obtained from calibration curves prepared from standard solutions. Dithizone
solutions must be purified by filtration and extraction with aqueous ammonium hydroxide in order to remove oxidation contaminants
(di phenylthi ocarbondiazone).
4. APPLICATION: Engineering evaluation R&D.
A) OPE RATIONAL SCOPE
Method is applicable to heavy metal determinations in drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
See Table 02-02-01-21A for complete list of interferences. Oithizone solutions are decomposed by sunlight and in the light beam of
the spectrophotometer. Because of the extreme sensitivity of the method, all glassware used in the determinations should be thoroughly
cleaned with high purity water and segregated from other glassware prior to use.
C) RECOMMENDED USE AREA
This is an engineering evaluation R&D procedure for the determination of heavy metals in aqueous effluents.
5. OPERATIONAL PARAMETERS
A) RANGE see Tabie 02-02-01-21A.
B) ACCURACY The following relative errors have been determined: For Ag, 66.6*; for In, 25.9'?.; for Pb, 8.5 .
C) PRECISION The following relative standard deviations have been obtained: For Ag, 61.OX; for Zn, 18.2.'; for Pb, 42.U.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
See Table 02-02-01-21A.
Spectrophotometer; standard laboratory glassware for filtrations,
extractions.
& KEYWORD INDEX: Heavy metals, dithizone, spectrophotometry.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 02; 02-02-01-01.
10. REFERENCES
A) PRIMARY SOURCE
204 American Public Health Association (APHA), American Water Works Association, and Water Pollution Control Federation,
"Standard Methods for the Examination of Waste and Wastewater," 13th ed., Washington, D. C., 1971, 174 pp.
B) BACKGROUND INFORMATION
186 Mitre Corporation, "Compendium of Analytical Methods, Vol. II. Method Summaries,"EPA PB 228-425, April 1973.
C| FIELD APPLICATIONS
196
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PAGE 2 OF 2 FOR
TITLE DETERMINATION OF HEAVY METALS BY OITHIZONE METHOD (CONTINUED)
ID NO. 02-02-01-21
Table 02-02-01-21A. (Reference 204).
Metal
Ag
Cd
In
Pb
Minimum Detectable
Concentration
(vg)
0.2
0.5
1.0
2.0
Interferences
Ferric Ions, residual
chlorine, other oxidiz-
ing agents
Ag, Hg, Cu, Ni, Co inter-
fere in basic solutions;
organic material
interferes
Heavy metals
Heavy metals, particu-
larly tin; organic
material
Procedures for Removal
of Interferences
Ferric ion is removed by extraction with aqueous
ammonium thiocyanate reagent; sample is digested
with sulfuric add, urea, hydroxylamine sulfate.
)rganics are decomposed by digestion with HN03-
H2S04; Cl is precipitated with AgNOs. Cu, Ag
and Hg are extracted with dithizone in CHC13,
pH 2. After adjustment to pH 9, Ni and Co are
removed by dimethyl glyoxime. At pH 14, Zn and Cd
are extracted with dithizone in CHC13; Zn is then
removed by NaOH wash.
Sample is adjusted to pH 4-5.5; sodium thiosulfate
is added, with acetate buffer.
Organics are removed by acid digestion or ignition.
Sn is removed by volatilization as SnBr4. For
removal of other metals, sample is extracted with
ammonium citrate - hydroxylamine hydrochloride; then
is made alkaline; KCN is added and pH is adjusted
to 8.5 to 9. Then ammoniacal cyanide-citrate
reagent is added to complex remaining heavy metal
interferences.
Analytical x
(nm)
620
515
535
or 620
c-in
D1U
197
-------
1. TITLE DETERMINATION
OF HEXAVALENT CHROMIUM BY DIPHENYL CARBAZIDE METHOD
2. IDENTIFICATION CODE
02-02-01-22
3. ABSTRACT OF METHODOLOGY
Hexavalent chromium can be determined by treatment with an acidic solution of s-diphenyl carbazide reagent. A reddish purple complex is
formed, which can be measured spectrophotometrically at 540 rim. The concentration of the sample is obtained using calibration curves
prepared from standard solutions.
4. APPLICATION'. Environmental assessment, engineering evaluation R&D.
A) OPE RATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Mercury interferes by producing a blue-purple color, but the reaction is not extensive at the acidity level used. Iron at concentra-
tions greater than 1 mg/liter interferes by producing a yellow color. Vanadium also interferes, but the color produced fades rapidly
(10 minutes). Sample must be analyzed rapidly once the reagent is added, or low chromium values will be obtained.
C) RECOMMENDED USE AREA
This method is applicable to environmental assessment if specific valence state information about Cr is required.
5. OPERATIONAL PARAMETERS
A) RANGE Minimum detectable concentration is 5 ug/liter when a 5 cm light path is used for photometric measurement.
8) ACCURACY Accuracy is dependent upon the promptness of analysis.
C) PRECISION Photometric measurements in the range below 400 ug/liter can be made with a precision of 10 wg/liter Cr.
6. REAGENTS REQUIRED
High purity water; s-diphenyl carbazide in ethyl or isopropyl alcohol
with sulfuric acid; standard chromium solutions.
7. EQUIPMENT REQUIRED
Spectrophotometer for use at 540 nm; standard laboratory glassware.
KEYWORD INDEX: chromium, diphenyl carbazide; spectrophotometry.
9. CROSS REFERENCE ID NUMBERS 01_02-02, oi-02-Ol.
10. REFERENCES
AJ PRIMARY SOURCE
204 Taras, M.J. fed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D. C.,
iy/i, p. 156.
B) BACKGROUND INFORMATION
186 Mitre Corporation, "Compendium of Analytical Methods, Vol. II. Method Summaries," EPA, PB 228-425, April 1973, p. C-
C) FIELD APPLICATIONS
198
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1 TITtE DETERMINATION OF IRON (TOTAL, FILTERABLE OR FERROUS) BY PHENANTHROLINE
2. IDENTIFICATION CODE
02-02-01-23
3. ABSTRACT OF METHODOLOGY
For a determination of total iron, the sample iron is solubilized, then is reduced to the ferrous state by boiling with hydrochloric a id
and hydroxylamine solution. The solution is then treated with ammonium acetate buffer and 2 ml phenanthroline. Three molecules 17 helan
throline chelate each atom of ferrous iron to form an orange-red complex. Total iron is then determined spectrophotometrically at 510 nT~
after the solution is allowed to stand 10-15 minutes. For a determination of filterable iron, the sample is filtered immediately after
collection through a 0.45p membrane filter into a vacuum flask containing dilute HC1. Total filterable iron is analyzed as described
above. Filterable ferrous iron is determined by adding concentrated hydrochloric acid to the sample immediately after collection, fol-
lowed by addition of phenanthroline and ammonium acetate solutions. The spectrophotometric measurements are then performed within 5 to
10 minutes after addition of reagents. Concentrations are determined by comparison to calibration curves prepared using standard
reagents.
4. APPLICATION: Environmental assessment, engineering evaluation R&D.
A) OPE RATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Strong oxidizing agents interfere (cyanide, nitrite and phosphates; chromium and zinc in concentrations greater than 10 times iron;
cobalt and copper in excess of 5 mg/liter and nickel in excess of 2 mg/liter). Initial boiling with acid and hydroxylamine solution
eliminates these interferences. Excessive concentrations of metal ions or anions that complex iron, such as citrate, tartrate,
oxalate and phosphate, can be eliminated by a preliminary extraction procedure or using tripyridine.
RECOMMENDED USE AREA
C)
This method is applicable to environmental assessment when valence state information about Fe is required.
5. OPERATIONAL PARAMETERS
A) RANGE Minimum detectable concentration is 3yg spectrophotometrically using a 10-cm cell path length. Total, dissolved or ferrous
iron concentrations between 0.02 and 4.0 mg/liter can be determined directly, and higher concentrations can be determined by the use
B) ACCURACY of aliquots.
Relative error of 13.3% was obtained in 44 laboratories on synthetic unknown samples containing 300ug/liter Fe.
C) PRECISION
A relative standard deviation of 25.5Z was obtained using the sample described above.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
High purity water; concentrated hydrochloric acid; hydroxylamine
solution; ammonium acetate buffer.solution; 1, 10 - phenanthroline
monohydrate, standard iron (ferric ammonium sulfate) solutions.
Spectrophotometer for use at 510 ran; standard laboratory glassware,
including extraction funnels.
KEYWORD INDEX-'Iron, phenanthroline, spectrophotometry.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02, 02-02-01-05
10. REFERENCES
204 Taras, H.J5 (ed.), "Standard Methods for the Examination of Water and Vlastewater," 13th ed., American Public Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D. (..,
1971, p. 189.
O FIELD APPLICATIONS
of Analytical Methods, Vol. ,.. Method Summaries," EPA PB 228 425, April 1973, p. C-20.
199
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1. TITLE DETERMINATION OF CHEMICAL OXYGEN DEMAND
Z IDENTIFICATION CODE
02-02-01-24
3. ABSTRACT OF METHODOLOGY
Organic substances in the sample are oxidized by 0.250N potassium dichromate in 50% sulfuric acid solution at reflux temperature using
silver sulfate as catalyst and mercuric sulfate to remove interferences by chloride. The excess dichromate is titrated with standard
of 0.10N ferrous ammonium sulfate using orthophenanthroline ferrous complex as an indicator.
For samples having an organic carbon concentration of less than 15 mg/liter, the Low Level Modification should be used.in which
0.025N potassium dichromate is used to oxidize the sample, and 0.01N ferrous ammonium sulfate is used in the back-titration.
When the sample has a chloride concentration greater than 2,000 mg/liter, the Saline Water Modification should be used, in which a
standard curve of COD versus mg/liter of chloride is prepared using sodium chloride solutions of varying concentrations, using the
same procedure applied to the sample. A chloride range of 4,000 mg/liter to 20,000 mg/liter should be determined.
4. APPLICATION: Compliance, environmental assessment
A) OPE RATIONAL SCOPE
Method is applicable to domestic and industrial waste samples having an organic carbon concentration greater than 15 mg/liter.
B) INTERFERENCES/LIMITATIONS
Chloride interferes, but is removed by addition of mercuric sulfate. There is a risk of loss of volatile organics, which is
minimized by cooling the flask during the sulfuric acid addition.
C) RECOMMENDED USE AREA
This is the COD compliance test.
OPERATIONAL PARAMETERS
A) RANGE Method is applicable to waste samples having an organic carbon concentration greater than 15 mg/1. For lower concentrations
of carbon (as in surface waters), or for very high concentrations of chloride (>2,000 mg/1), procedural modifications are required
(see Abstract of Methodology).
B) ACCURACY Accuracy as percent relative error (bias) of -4.7% has been reported.
C) PRECISION Standard deviation of +17.76 mg/1 COD reported for analyses conducted in over 50 laboratories.
6. REAGENTS REQUIRED
Potassium dichromate solution, sulfuric acid, standard ferrous
ammonium sulfate titrant.
7. EQUIPMENT REQUIRED
Reflux apparatus.
a KEYWORD INDEX: Chemical oxygen demand (COD), aqueous effluents, dichromate oxidation
9. CROSS REFERENCE ID NUMBERS 01-02-02; 01-02-01
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory, National
Environmental Research Center, EPA 625/6-74-003, Washington, 1974, p. 20.
204 !?„?.!; M;J- !ed''', "standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health Association
(APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D.C., 1971, Method 220, p. 495.
B) BACKGROUND INFORMATION
492 Moore, W.A., F.J. Ludzack and C.C. Ruchhoft, "Dichromate Reflux Method for Determining Oxygen Consumed," Anal. Chem., 21_,
493 Medalia, A.I., "Test for Traces of Organic Matter in Water," Anal. Chem.. 23_, 1318 (1951).
494 Symons, J.M., H.H. Hassis and R.E. McKinney, "A Procedure for Determination of Biological Treatability of Industrial Wastes,"
J.H.P.C.F.. 32, 841 (1960).
C) FIELD APPLICATIONS
495 Muers, M.M., "Biological Purification of Whey Solutions," J. Soc. Chem. Ind.. 55, 711 (1936).
200
-------
1. TITLE DETERMINATION OF AMMONIA BY DISTILLATION PROCEDURE
_—.
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-02-01-25
The sample is buffered at pH 9.5 with a borate buffer to minimize hydrolysis of cyanates and organic nitrogen compounds. The sample
is then distilled into a boric acid solution. The ammonia present in the distillate is then determined by Nesslerization, or potentio-
metrically using an ammonia electrode, or by titration with sulfuric acid with a mixed indicator (see 02-02-01-19). Prior to analysis,
the samples may be preserved with 2 ml cone. H2S04 or 40 mg/1 HgCl2 and stored at 4°C.
4. APPLICATION' Compliance, environmental assessment
A) OPERATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
INTERFERENCES/LIMITATIONS
Residual chlorine interferes but can be removed by addition of sodium thiosulfate prior to distillation. Volatile alkaline
compounds (formaldehyde, certain ketones, and alcohols) may interfere with Nesslerization; these may be boiled off at pH 2-3
prior to distillation. If necessary, mercury salts are used to preserve the sample; these must be removed prior to distilla-
tion by addition of sodium thiosulfate.
RECOMMENDED USE AREA
This is an NH3 compliance test.
5. OPERATIONAL PARAMETERS
A) RANGE 0.05-1.0 mg/1 NH3 nitrogen for the colorimetric procedure; 1.0-25 mg/1 for the titritnetric procedure; 0.05-1400 mg/1
for the electrode method.
B) ACCURACY A study conducted by 24 analysts in 16 laboratories resulted in accuracies (as bias, mg N/liter) of -0.05 to +0.01
for samples having 0.21 to 1.92 mg N/liter.
C) PRECISION In the study described above, precisions ranging from 0.070 to 0.279 rag N/liter were achieved.
6. REAGENTS REQUIRED
Anrnonium chloride, borate buffer, mixed indicator (methyl red,
methylene blue); Nessler reagent (mercuric iodide, potassium
iodide), sulfuric acid, sodium hydroxide.
7. EQUIPMENT REQUIRED
Kjeldahl flask, Erlenmeyer flasks, Nessler tubes,
spectrophotometer.
KEYWORD INDEX: Ammonia, distillation, Nesslerization, titrimetry, potentiometry
9. CROSS REFERENCE ID NUMBERS 02-02-01-19; 02-02-01-20; 01-02-01; 01-02-02
K>. REFERENCES
185
PRIMARY SOURCE
-Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory, National
Environmental Research Center, EPA 625/6-74-003, Washington, 1974, p. 159.
Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., *"*<** *>» 'j
(APHA), American Water Works Association, and Water Pollution Control Federate, Washington, D.C., 1971, Me
497
219
BACKGROUND INFORMATION
Jackson, D.D., "Permanent Standards for Use in the Analysis of Water," Hassachusetts_JnsJJ_TechJ3oL_a!!ail- • ]-3-' 314
Nichols, M.S., and M.E. Fotte, "Distillation of Free Ammonia from Buffered Solutions," Ind.. En
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1. TITLE DETERMINATION OF BERYLLIUM BY ALUMINON METHOD
2. IDENTIFICATION CODE
02-02-01-26
3. ABSTRACT OF METHODOLOGY
Method involved pre-addition of ethylenediamine titraacetic acid (EDTA) to eliminate interference of aluminum, cobalt, copper, iron,
manganese, nickel, titanium, zinc, and zirconium. The sample is then treated with aluminon buffer reagent and the colored beryllium
complex formed is determined spectrophotometrically at 515 nm.
4. APPLICATION: Engineering evaluation R&D.
A) OPERATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
As indicated above, interferences due to aluminum, cobalt, copper, iron, manganese, nickel, titanium, zinc, and zirconium are
removed with addition of EDTA.
C) RECOMMENDED USE AREA
This colorimetric method is useful as an alternate to the AAS procedure (see 02-02-01-05).
5. OPERATIONAL PARAMETERS
A) RANGE Minimum detectable concentration is 5 wg/liter.
B) ACCURACY N/Q
C) PRECISION N/q
6. REAGENTS REQUIRED
EDTA reagent, aluminon buffer reagent, beryllium stock solution.
7. EQUIPMENT REQUIRED
Spectrophotometer for use at 515 nm,
glassware.
standard laboratory
& KEYWORD INDEX: Beryllium, aqueous effluents, aluminon, spectrophotometry
9. CROSS REFERENCE ID NUMBERS 01-02-01; 01-02-02, 02-02-01-05.
10. REFERENCES
A) PRIMARY SOURCE
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health Association
(APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D.C., 1971, Method 106B, p. 67.
B) BACKGROUND INFORMATION
499 Luke, C.L., and M.E. Campbell, "Photometric Determination of Beryllium in Beryllium-Copper Alloys," Anal. Chem., 24,
1056 (1952). "•
500 Luke, C.L., and K.C. Brown, "Photometric Determination of Aluminum in Manganese, Bronze, Zinc Die Casting Alloys, and
Magnesium Alloys," Anal. Chem., 24, 1120 (1952).
C) FIELD APPLICATIONS
202
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1. TITLE DETERMINATION OF TOTAL CHROMIUM BY DIPHENYL CARBAZIDE METHOD
.
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-02-01-27
The determination of total chromium involves the oxidation of chromium to the hexavalent state, followed by complexation with
diphenyl carbazide and spectrophotometric measurement at 540 nm (see 02-02-01-22). The sample is first digested with an
H2S04-HN03 or HN03-HC104 mixture in order tc decompose organic manner, then is adjusted to 0.5N acidity. Potassium permanganate
is next added to oxidize the chromium to Cr . Sodium oxide is added to reduce excess permanganate. Finally, the diphenyl
carbazide reagent is added and the red-violet complex is determined spectrophotometrically.
4, APPLICATION: Compliance.
A) OPERATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Vanadium interferes at concentrations greater than ten times the chromium concentration. Vanadium, molybdenum, iron and copper can
be removed by extraction into chloroform. Hexavalent Hg will also form a colored complex with the reagent, but its intensity is
lower than that for chromium at the specified pH.
0 RECOMMENDED USE AREA
This Is an alternate compliance test for total chromium.
5, OPERATIONAL PARAMETERS
A) RANGE 10 pg/liter using 100 ml aliquotes of sample.
B) ACCURACY N/Q
C) PRECISION N/Q
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Sodium azide, diphenyl carbazide, potassium permanganate,
sulfuric acid, nitric acid.
Spectrophotometer for use at 540 nm standard laboratory
glassware.
8. KEYWORD INDEX: Total chromium, aqueous effluents, diphenyl carbazide, permanganate oxidation
9. CROSS REFERENCE ID NUMBERS 02-02-01-22; 01-02-01; 01-02-02, 02-02-01-05
W. REFERENCES
A) PRIMARY SOURCE
2»" Taras, M.J., ed., "Standard Methods for the Examination of Water and Wastewater," American Public Health Association.
Edition, Method 211C, 1971, p. 426.
lrteTrSoT^endium of Analytical Methods, Vol. II.. Method Summaries," EPA PB 228-425 .April ,1973 - P^8
501 Rowland, G.P., Jr., "Photo Electric Colorimetry-Optical Study of Permanganate Ion and of Chromium uipnenyica
502 ^'-^ Permananate Oxidation," AjiaK. Ch«,. 24,
'016 (1952).
c> FIELD APPLICATIONS
of Chromium with Diphenylcarbazide by Permanganate Oxidation," AjiaK. Ch«,. 24,
203
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1. TITLE DETERMINATION OF TOTAL COPPER BY NEOCUPROINE METHOD
2. IDENTIFICATION CODE
02-02-01-28
3. ABSTRACT OF METHODOLOGY
The determination of total copper involves preliminary sample digestion to remove organics and interfering anions, followed by
+?
treatment of the sample with hydroxy1 amine hydrochloride to reduce copper to Cu and with sodium citrate for prevention of
complexation by interfering metal ions. Following pH adjustment (to pH 3-9) by addition of ammonia, the neocuproine reagent
is added and the resultant complex is extracted with chloroform-methanol solution, and determined spectrophotometrically at 457 rim.
4. APPLICATION: Compliance.
A) OPERATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Interference from chromium can be reduced by the addition of sulfurous acid. Cyanide, sulfide and organics interfere, but are
removed during digestion.
C) RECOMMENDED USE AREA
This is an alternative compliance method for Cu (see 02-02-01-05).
OPERATIONAL PARAMETERS
A) RANGE 30 pg/liter using a 100 ml sample aliquot and 1 cm cell; 6 ug/liter using a 100 ml sample aliquot and 5 cm cell.
B) ACCURACY N/Q
C) PRECISION N/Q
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Redistilled water, cone, sulfuric acid, 602 perchloric acid,
hydroxylamine hydrochloride solution, sodium citrate solution,
ammonium hydroxide, 2,9-dimethyl-l,10-phenanthroline hemihydrate.
Spectrophotometer for use at 457 my, standard laboratory
glassware, separatory funnels.
& KEYWORD INDEX: Total copper, aqueous effluents, phenanthroline, spectrophotometry.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02; 02-02-01-23, 02-02-01-05
10. REFERENCES
A) PRIMARY SOURCE
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Health Association (APHA),
American Water Works Association, and Water Pollution Control Federation, Washington, D.C., 1971, Method 211E, p. 430.
B) BACKGROUND INFORMATION
503 Smith, G.F., and W.H. McCurdy, "2,9-Dimethyl-l,10-Phenanthroline; New Specific Reagent in Spectrophotometric Determination of
Copper," Anal. Chem.,24. 371 (1952).
504 Gahler, A.R., "Colorimetric Determination of Copper with Neocuproine," Anal. Chem.. 26^, 577 (1954).
505 Fulton, J.W., and J. Hastings, "Photometric Determinations of Copper in Aluminum and Lead-Tin Solder with Neocuproine,"
Anal. Chem., 28, 174 (1956).
506 Frank, A.J., A.A. Deacutis and A.B. Goulston, "Spectrophotometric Determination of Copper in Titanium," Anal. Chem.. 29, 750
(1957).
C) FIELD APPLICATIONS
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1. TITLE DETERMINATION OF CALCIUM BY GRAVIMETRIC METHOD
__ _
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-02-01-29
Method involves the precipitation of calcium in the sample with ammonium oxalate to form calcium oxalate. The precipitatio '
accomplished in several stages with PH adjustments in order to maximize the amount of precipitate formed. The precipitate°formed
is ignited and weighed as calcium oxide.
The filtrate from the determination is used for the determination of total magnesium (see 02-02-01-30).
4. APPLICATION- Engineering evaluation R&D.
A) OPERATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
Bl INTERFERENCES/LIMITATIONS
Silica interferes, and can be removed by treatment with HC1. Aluminum iron and manganese interfere, but can be precipitated with
ammonium hydroxide. Suspended matter should also be removed by centrifuging or filtration.
0 RECOMMENDED USE AREA
This is an alternative engineering evaluation R&D procedure for Ca+2 when large quantities of Ca+2 are expected (see 02-02-01-05)
OPERATIONAL PARAMETERS
A| RANGE Samples or sample aliquots containing up to 250 mg Ca per 200 ml solution can be analyzed using this method.
Bl ACCURACY A synthetic sample containing 108 mg/1 Ca was determined in four laboratories, with a relative error of 1.9i.
C) PRECISION The determination on the sample described above gave a relative standard deviation of 3.7;.
REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Amoniurn oxalate, ammonium hydroxide, ammonium persulfate, and
amnonium chloride, hydrochloric acid for interference removals.
Standard laboratory glassware, platinum crucible, desiccator,
analytical balance.
KEYWORD INDEX: Calcium aqueous effluents, gravimetry, ammonium oxalate.
9. CROSS REFERENCE ID NUMBERS 02-02-01-30s 01-02-01, 01-02-02; 02-02-01-12, 02-02-01-05.
• REFERENCES
Al PRIMARY SOURCE
204 I™35! HJ- (ed->- "Standard Methods for the Examination of Water and Wastewater," 13th ed.. toerican K?bl£ "^^"'"gj1""
(APHA), American Water Works Association, and Water Pollution Control Federation, Washington. D.C., 1971, Method IIUA, p. ou.
B> BACKGROUND INFORMATION , N ,
507 195^"' H'H" C'E- Bricker and N-H' Furman' "El^nts of Quantitative Analysis," 4th ed.. D. Van Nostrand Co., Princeton, N.J.
508 Nei'Jo1?' LM" S' Bruckenste1n' E'J- Meenan and E'B- Sandell, "Quantitative Chemical Analyses," 4th ed., Macnrillan Co.,
509 Ingals. R.S., and P.E. Murray, "Urea Hydrolyses for Precipitating Calcium Oxalate," Ana.!_.. Chem.., 21, 525 (1949).
c> FIELD APPLICATIONS
205
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1. TITLE DETERMINATION OF TOTAL MAGNESIUM BY GRAVIMETRIC METHOD
2. IDENTIFICATION CODE
02-02-01-30
3. ABSTRACT OF METHODOLOGY
Using the filtrate from 02-02-01-30, magnesium is determined by precipitation with diamraonium hydrogen phosphate to give magnesium
ammonium phosphate. The precipitate is then ignited and determined as magnesium pyrophosphate. Prior to the actual precipitation,
the sample is treated with concentrated nitric acid for the removal of ammonium salts and oxalate. If this pretreatment is not
performed, the sample can be double-precipitated to ensure complete removal of magnesium.
Magnesium can be determined by the gravimetric method only after prior removal of calcium salts; this method is usually performed
on the filtrate and washings from the gravimetric calcium determination (see 02-02-01-29).
4. APPLICATION: Compliance.
A) OPE RATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Aluminum, calcium, iron, manganese, silica, strontium, and suspended matter interfere. The solution should contain less than
3.5-g NH4C1.
C) RECOMMENDED USE AREA
This is an alternative compliance test for Mg (see 02-02-01-05 for primary method).
5. OPERATIONAL PARAMETERS
A) RANGE To several hundred mg/1.
B) ACCURACY A synthetic sample containing 82 mg/1 magnesium was determined in eight separate laboratories with a relative error
of 4.9*.
C) PRECISION The determinations on the sample described above gave a relative standard deviation of 6.35,.
6. REAGENTS REQUIRED
Nitric acid, hydrochloric acid, methyl red indicator solution,
di ammonium hydrogen phosphate solution, ammonium hydroxide.
7. EQUIPMENT REQUIRED
Standard laboratory glassware, crucible.
& KEYWORD INDEX: Total magnesium, aqueous effluents, gravimetry, di ammonium hydrogen phosphate.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02; 02-02-01-29, 02-02-01-05.
10. REFERENCES
A) PRIMARY SOURCE
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," I3th ed., American Public Health Association
(APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D.C., 1971, Method 127A, p. 201.
B) BACKGROUND INFORMATION
510 Epperson, A.W., "The Pyrophosphate Method for the Determination of Magnesium and Phosphoric Anhydride," J. Amer. Chem..Soc^, 50,
321 (1928).
508 Kolthoff, I.M. and E.B. Sandell, "Textbook of Quantitative Inorganic Analysis," 3rd ed., Macmillan Co., New York, Chapter 22.
511 Hillebrand, W.F., et al, "Applied Inorganic Analysis," 2nd ed., John Wiley & Sons, Inc., New York. Chapter 41, p. 133-134.
C) FIELD APPLICATIONS
206
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TITLE DETERMINATION OF NICKEL BY HEPTOXIME METHOD
2. IDENTIFICATION CODE
02-02-01-31
i ABSTRACT OF METHODOLOGY
Method Involves preliminary digestion of the sample with a HN03-H,,S04 mixture, then treatment with cupferron reagent The iron and
copper cupferrates formed are then removed from the sample by extraction with chloroform. The sample is then treated with 1 2-
cycloheptanedionedioxime, and the nickel heptoxime complex formed is extracted with chloroform, reextracted into the aqueous'phase
with hydrochloric acid and is determined spectrophotometrically at 445 nm.
4. APPLICATION^ Compliance
A) OPERATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Iron and copper interfere, but are removed by preliminary treatment of the sample with cupferron reagent.
C) RECOMMENDED USE AREA
This is an alternate Ni compliance test (see 02-02-01-05).
5. OPERATIONAL PARAMETERS
A) RANGE To several hundred mg/1.
B| ACCURACY N/Q
C) PRECISION No precision data are available.
& REAGENTS REQUIRED
1,2-cycloheptanedionedioxime (heptoxime reaaent); cupferron
solution, nitric acid, sulfuric acid, hydroxylamine hydro-
chloride solution.
7. EQUIPMENT REQUIRED
Spectrophotometer for use at 445 nm, separating funnels,
standard laboratory glassware.
1 KEYWORD INDEX: Nickel, aqueous effluents, heptoxime method, colorimetry.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02, 02-02-01-05.
REFERENCES
a.), "Standard Methods for the Examination of Water and Was tewa ter . " 13th ed "
(APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D.C., is/I,
P 443
,erN and M.G. Mellon, "Colorimetric Determination of Metals in Sewa.e and .ndustrial Wastes,' Sew
"3 RrHonfR.C5!3and9cl Banks, "Spectrophotometric Determination of Nickel Using 1 ,2.Cyc,oheptanedionedioxime(heptoxi,ne),
«« ^l'^ocedures for Analyzing Meta, Finishing Wastes," Ohio Kiver Valley Water Sanitation
°' 1954-
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1. TITLE DETERMINATION OF POTASSIUM BY COBALTINITRITE METHOD
I IDENTIFICATION CODE
02-02-01-32
3. ABSTRACT OF METHODOLOGY
Method involves precipitation of potassium with trisodium cobaltinitrite, followed by oxidation of the dipotassiura sodium cobalti-
nitrite formed with potassium dichromate and sulfuric acid. The excess dichromate is then determined colorimetrically at 425 nm.
Since temperature and precipitation time affect the results, a series of standards containing known potassium concentrations should
be run simultaneously with the samples.
4. APPLICATION'. Engineering evaluation R&D.
A) OPERATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Ammonium ion interferes. Silica may interfere if silica gel forms during the evaporation and addition of the reagent. The gel
can be removed by filtration. No other common ions interfere.
C) RECOMMENDED USE AREA
This is an alternate colorimetric engineering evaluation R&D procedure for cobalt (see 02-02-01-05).
5. OPERATIONAL PARAMETERS
A) RANGE Samples of 100 to 700 mg/liter potassium can be determined, using 10 ml aliquots.
B) ACCURACY +0.5 mg potassium.
C) PRECISION N/Q
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Trisodium cobaltinitrite, potassium dichromate, nitric acid,
sulfuric acid, standard potassium stock solution.
Spectrophotometer for use at 425 nm, centrifuge, standard
laboratory glassware.
& KEYWORD INDEX: Potassium aqueous effluents, spectrophotometry, sodium cobaltinitrite.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02, 02-02-01-05.
10. REFERENCES
A) PRIMARY SOURCE
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health Association
(APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D.C.. 1971, Method 147B, p. 285.
B) BACKGROUND INFORMATION
515 Wander, I.W., "Photometric Determination of Potassium," Ind. Eng. Chem., Anal. Ed., 14, 471 (1942).
508 Kolthoff, I.M., S. Bruckenstein, E.J. Heehan and E.B. Sandell, "Quantitative Chemical Analysis," 4th ed., Macmillan Co.,
New York, 1969.
C) FIELD APPLICATIONS
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1. TITLE DETERMINATION OF VANADIUM BY GALLIC ACID METHOD
_ •—
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-02-01-33
Method involves treatment of the sample with gallic acid and ammonium persulfate-phosphoric acid reagent The vanadium Cat.lv,«
the oxidation of the gallic acid by persulfate; the extent of oxidation is proportional to the vanadi™ concentr^ r * 'the
sample. The vanadium is deterged by spectrophotometric measurement of the sample at 415 m and comparison to a calibration curve
plotted using standards prepared in the same way as the sample but having known concentrations of vanadium.
4. APPLICATION: Compliance.
A) OPE RATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
Bl INTERFERENCES/LIMITATIONS
The following ions interfere: Cr+6 (1.0 rag/1); Co+2 (1.0 mg/1); Cu*2 (0.05 mg/1); Fe+2 (0.3 mg/1); Fe+3 (0.5 mg/1); !"lo+6 (0.1 mg/1);
Ni+2 (3.0 rag/1); Ag (2.0 mg/1); U+6 (3.0 mg/1); Br" (0.1 mg/1); Cl" (100.10 mg/1); I" (0.001 mg/1). Addition of mercuric ion
eliminates interferences due to Cl", Br", and I~.
C) RECOMMENDED USE AREA
This is an alternate compliance test for vanadium (see 02-02-01-05).
5, OPERATIONAL PARAMETERS
A) RANGE Minimum detectable concentration is 0.025 ug.
8| ACCURACY A synthetic sample containing 6 yq/1 of vanadium was determined in 22 laboratories with no relative error.
C) PRECISION The determination on the sample described above gave a relative standard deviation of 20'.',.
6, REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Gallic acid solution, ammonium persulfate-phosphoric acid
reagent, mercuric nitrate solution, standard vanadium solution.
Spectrophotometer for use at 415 mm, water bath (25 + 0.5 C),
standard laboratory glassware.
8. KEYWORD INDEX: Vanadium, aqueous effluents, spectrophotometry, gallic acid.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02, 02-02-01-05.
10. REFERENCES
m 'Ta^Tfed.), "Standard Methods for the Examination of Water and Wastewater » 13th ed America,, Pub, 1c Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation, a
516 Fishman, M-J^and iTskougstad, "Catalytic Determination of Vanadium in Water," Anal... Che.,, 36. 1643 (1964).
FIELD APPLICATIONS
209
-------
, _._. , METHOD FOR DETERMINATION OF TOTAL ALPHA RADIOACTIVITY USING PROPORTIONAL
1. 1IILC OR SCINTILLATION COUNTERS
2. IDENTIFICATION CODE
02-02-01-34
3. ABSTRACT OF METHODOLOGY
Method involves determination of alpha radioactivity by means of proportional or scintillation counters, which consist of detecting
devices, amplifiers, power supplies, and sealers. Alpha particles which enter the proportional detector ionize the counting gas;
the negative ions produced are accelerated toward the anode and ionize additional counting gas, resulting in a voltage pulse. In
the scintillation detector, the alpha particles excite atoms of a phosphor material; the release of light quanta by these excited
atoms are detected and transformed into voltage impulses in a photomultiplier tube. The number of pulses per unit time in both
methods is related to the disintegration rate of the test sample.
Samples are prepared for counting by evaporation of a suitable volume of sample solution and several m. of concentrated nitric
acid in a beaker on a hot plate or steam bath, followed by further drying in an oven or with a Bunsen burner. Alternatively, the
sample may be precipitated in order to concentrate the radioactivity present into smaller amounts of material.
4. APPLICATION- Compliance, environmental assessment.
AJ OPERATIONAL SCOPE
Method is applicable to all aqueous effluents which emit alpha-emitting radioelements; method does nnt measure those radioelements
that are volatile under the conditions of analysis. It is sensitive to alpha emissions above 3.9 MeV in energy and at activity
levels above 0.5 pfM/mz. of aqueous water. Method is useful for both absolute and relative determinations.
B) INTERFERENCES/LIMITATIONS
Solids interfere with detection; the solids content should remain constant among related test samples. A 10-15''.' loss in counting
rate may be experienced due to 1 mg/cm solids content on the sample dish.
C) RECOMMENDED USE AREA
Compliance testing.
& OPERATIONAL PARAMETERS
A| RANGE Maximum radioactivity determinable is 100,000 com; the limit of sensitivity is dependent on the background counting rate,
which should be as low as possible.
B) ACCURACY Not available at this time.
C) PRECISION +5%
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Reagent grade water, concentrated nitric acid.
Sample mounting discs or dishes, scintillation or proportional
detector and sealer, Bunsen burner or oven (103 to 105°C),
standard laboratory glassware.
& KEYWORD INDEX: Radioactivity, aqueous effluents, proportional counter, scintillation counter, alpha radiation.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02; 02-02-01-35, 02-02-01-36.
10. REFERENCES
A) PRIMARY SOURCE
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, 01443-66,
"Standard Method for Measurement of Alpha Particle Radioar.tivitv of WatPr," American Societv for Testinq and Materials,
Philadelpha, PA., 1971, pp. 501-505.
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washington. D.C., 1971,
Method 302, p. 598.
B) BACKGROUND INFORMATION
517 Goldin, A.S., J.S. Nader and L.R. Setter, "The Detectability of Low-Level Radioactivity in Watpr," J Am Waterworks Assoc.
45, 73(1953). " -' "
518 Setter, L.R., A.S. Goldin and J.S. Nader, "Radioactivity Assay of Water and Industrial Waste-; with Internal Proportional
Counter," Anal. Chem., 26, 1304 (1954).
519 National Center for Radiological Health, "Radioassay Procedures for Environmental Samples," PHS Pun Nn 999-RII-27,
U.S. Dent, of Health, Education and Welfarp, Washington, D.C., Jan. 1967.
210
-------
,. TITLE
3. ABSTRACT OF METHODOLOGY
.ONAL OR
2. IDENTIFICATION CODE
02-02-01-35
Method involves determination of beta radioactivity by means of proportional or Geiger-Muller counters which con«i«t f „
(internal or external proportional gas-flow chambers or Geiger-Muller tubes) and combined an,P,ifier power sup 7 ',
proportional counter is preferred for samples having wide ranges of beta radioactivity (10 to 80,000 cpn) Beta Darti^ ['• J**
the detector ionize the counting gas; the resultant negative ions are accelerated toward the anode and ionize add 0 t
resulting in a voltage pulse. The number of pulses per unit of time is related to the disintegration rate of III Jest san^e
Sables are prepared for measurement by precipitation, ion exchange or evaporation methods. Measurement efficiency can be dete • „
by comparison of the use of standards having the sane radioelements and solids content as the test samples.
4. APPLICATION- Compliance, environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to all aqueous effluents, and can be used for either absolute or relative determination-;. It is sensitive to
beta emissions above 0.1 MeV in energy and activity levels above 0.5 pCi/mz of liquid sample. Method does not measure those
radioelements which are volatile under conditions of analysis.
B) INTERFERENCES/LIMITATIONS
High solids content in the sample as well as solids which are present between the test sample and the detector interfere.
Excessive alpha, gamma, and X-ray emissions interfere, since most beta radiation rounters can be used to measure these types
of radiation as well.
C) RECOMMENDED USE AREA
Compliance testing.
5. OPERATIONAL PARAMETERS
A) RANGE The limit of sensitivity of both proportional and Geiger-Muller counters is related to background radioactivity.
Both massive shielding and anti-coincidence detectors and circuitry can be used to minimize background detection.
B) ACCURACY Not available at this time; accuracy is dependent upon the accuracy of the standard (data furnished by supplier),
the measurement method, the number of nucleids present as well as the number of types of radiation energies present.
Cl PRECISION See reference of G. Friedlander and J.W. Kennedy (Ref. 521) for precision data.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Reagent grade water, concentrated nitric acid.
Beta particle counter, sample dishes. Bunsen burner or oven
(103 to 105°C), standard laboratory glassware.
& KEYWORD INDEX: Radioactivity, aqueous effluents, proportional counter, Geiger-Muller counter, beta radiation
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02; 02-02-01-34, 02-02-01-36.
'0. REFERENCES
A) PRIMARY SOURCE
°24 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, 0 1890-66,
"Standard Method of Test for Beta Particle Radioactivity of Water," American Society for Testing and Materials,
Philadelphia, PA., 1971, pp. 465-472.
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washington, u.u, is/i,
Method 302, p. 598.
B) BACKGROUND INFORMATION
Friedlander, G., and J.W. Kennedy, "Nuclear and Radiochemistry," John Wiley and Sons, Inc., New York, N.Y., 1955.
Goldin, A.S., J.S. Nader and L.R. Setter. "The Detectability of Low-Level Radioactivity in Water," J.. Am.. Water Works Assp_c.,
«. 73 (1953).
Heath, R.L., "Scintillation Spectrometry, Gamma Ray Spectrum IDO 16880," Technical Information Division, U.S. Atomic Energy
Commission, Washington, D.C., Vols. 1 and 2, 1964.
National Center for Radiological Health, "Radioassy Procedures for Environmental Samples," PHS I'ubl. No. 999-RH-2 ,
U-S. Dept. of Health, Education and Welfare, Washington, D.C., Jan. 1967.
521
517
520
519
211
-------
2. IDENTIFICATION CODE
1. TITLE METHOD FOR DETERMINATION OF ALPHA AND BETA RADIOACTIVITY COUNTING ERROR 02-02-01-36
3. ABSTRACT OF METHODOLOGY
Counting error, E (in picocuries/sample), at the 95% confidence level is calculated using Eq. 1:
„ 1.96o (R)
E ——-ftf-1- (])
where o(R) is the standard deviation of the counting rate, and i is counter efficiency.
The term c(R) can be calculated using Eq. 2:
o(R) t2*?- 12)
rl r2 ,
where R is the counting rate of the sample plus background, B is the background counting rate, and tp t,, are the times in min-
utes in which the gross sample and the background counting rates were measured.
Counter efficiency, I, is determined as the result of plots of measurements of different weights of a known standard as a calibra-
tion curve. Counting error in picocuries/liter should be divided by sample volume in liters to give error in pCi/liter.
4. APPLICATION- Compliance, engineering evaluation R&D.
A) OPERATIONAL SCOPE
Method is applicable to samples analyzed for total alpha radioactivity using proportional or scintillation counters (sec 02-02-01-39)
and for total beta, radioactivity using proportional or Geiger-Muller counters (see 02-02-01-40).
B) INTERFERENCES/LIMITATIONS
N/A
C) RECOMMENDED USE AREA
Compliance testing.
5. OPERATIONAL PARAMETERS
At RANGE See 02-02-01-39 and 40.
B) ACCURACY N/A
C) PRECISION N/A
6. REAGENTS REQUIRED
N/A
7. EQUIPMENT REQUIRED
N/A
a KEYWORD INDEX: Counting error, aqueous effluents, radioactivity, scintillation counter, proportional counter, alpha
radiation, beta radiation.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02; 02-02-01-34, 02-02-01-35.
10. REFERENCES
A) PRIMARY SOURCE
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation. Washington, D.C., 1971,
B, BAcMt&WtomfiM.-
522 Jarrett, A.A., "Statistical Methods Used in the Measurement of Radioactivity (Some Useful Graphs)," U.S. Atomic Energy
Commission Document No. AECU-262, Atomic Energy Commission, Washington, D.C., June 17, 1946.
523 Nader, J.S., G.R. Hagel and L.R. Setter, "Evaluating the Performance of the Internal Counter," Nucleonics, 12., 6, 29 (1954).
C) FIELD APPLICATIONS
212
-------
TITLE METHOD FOR DETERMINATION OF RADIUM IN WATER
.
ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-02.01-37
Method involves coprecipitation of total radium (radium-223, -224, and -226) with barium and
dissolved in ammoniacal EDTA, and the barium and radium sulfates are reprecioitat su'«tes. The precipitate is
--— — - «* «" -P— count deterged using a
is
with
4. APPLICATION: Compliance.
A) OPERATIONAL SCOPE
Method is applicable to all aqueous effluents.
B) INTERFERENCES/LIMITATIONS
Excessive barium content (>0.2 mg) interferes in the determination of chemical yield.
C) RECOMMENDED USE AREA
Compliance testing.
5. OPERATIONAL PARAMETERS
Al RANGE Method is applicable to all sample sizes by making suitable reductions in sample size; the lower limit of sensitivity
is one p Ci/liter.
B) ACCURACY N/A
C) PRECISION N/A
6. REAGENTS REQUIRED
Reagent water, barium nitrate, lead nitrate, citric acid,
ammonium hydroxide, disodium ethylenediamine tetra- acetate,
methyl orange indicator, sulfuric acid.
7. EQUIPMENT REQUIRED
Sample mounting discs or dishes, scintillation or proportional
detector and sealer, Bunsen burner or oven (103 to 105 C),
standard laboratory glassware.
8. KEYWORD INDEX: Radium, aqueous effluents, proportional counter, scintillation counter.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02; 02-02-01-34, 02-02-01-36.
W. REFERENCES
204 Taras, M.Tfed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health
Association (APHA), American Water Works, Association and Water Pollution Control Federation, Washington, U.C., is/i,
Method 304, p. 611.
024 ASTM Committee 0-19 and D-22, "Water; Atmospheric Analyses," 1971 Annual Book of ASTM Standards Part 23 02460-70,
"Standard Method of Test for Radionuclides of Radium in Water," American Society for Testing and Materials,
Philadelphia, PA., 1971, pp. 659-663.
B) BACKGROUND INFORMATION
517 Goldin, A.S., "Determination of Dissolved Radium," Anal. Chem. ANCHA, 33, 406 (1961).
524 Halb.dc. P.P. (ed.), "Radionuclide Analyses of Environmental Samples, Method RC-88A," U.S. Public Health Service Report
R59-6, 1959.
525
526
• *w.* v 5 g ^t*jy •
Hallden, N.A., and J.H. Harley, "An Improved Alphacounting Technique," Anal. Chem., 32, 1961 (1960)
Petrow, H.G., and R.J. Allen, "Estimation of the Isotopic Composition of Separated Radium Samples," AnaLJ^hem, . _.
13ns Mac-it
1303 (1961)!
-------
PAGE 1 OF 2 FOR
1. TITLE INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROSCOPY
2. IDENTIFICATION CODE
02-02-02-01
3. ABSTRACT OF METHODOLOGY
Inductively Coupled Plasma Optical Emission Spectroscopy (ICPOES) is based on the observation of atomic emission spectra when
samples in the form of an aerosol are injected into an inductively coupled plasma atomerization and excitation source. The
apparatus employed is essentially a flame emission technique, except that the flame is a plasma torch whose temperature is on the
order of 7000°K. Figure 02-02-02-01A is a generalized schematic of the ICPOES system. In practice, the solutions to be analyzed
are sprayed from a glass and Teflon nebulizer which aspirates approximately 3 ml per minute of solution with an argon flow rate of
about 1 ml per minute. The plasma torch sits on a Rowland circle and the emitted light is dispersed by a curved grating along
the curvature of the circle at specific points, depending on the emitted wavelength. Current commercial instrumentation employs
up to 40 collection points (photomultipliers), so that 40 elements can be measured simultaneously.
4. APPLICATION^ Engineering evaluation R&D.
A) OPERATIONAL SCOPE
ICPOES normally analyzes a sample after it has been placed in solution. Recent advances, however, make analysis of solid samples
and gases possible. For routine analyses, the manufacturers recomnend that the solutions contain less than 0.5% solids, but up to
19! solids can be tolerated. All elements can be analyzed using ICPOES, but the commercial instruments today are capable of measur-
ing only 40 elements simultaneously. Since the collection points for the individual elements must be physically placed on the
Rowland circle, they cannot be changed very readily. Consequently, it is important to either find an instrument employed by a
commercial testing laboratory that has the elements of interest, or when purchasing an instrument, to select the elements care-
fully to provide the needed coverage for specific analysis needs.
B) INTERFERENCES/LIMITATIONS
While the high temperature of the plasma eliminates most matrix problems, there still exists a small degree of chemical inter-
ferences. Solids still must be reduced to solutions and the solids content of the solutions must be below 1%. This can cause
problems when sodium carbonate fusion or sodium borate fusion is used as the dissolution technique.
C) RECOMMENDED USE AREA
This method is the recommended engineering evaluation R&D multi-element technique.
5. OPERATIONAL PARAMETERS
A) RANGE Powers of detection range from nanogram to fractions of micrograms per ml up through 4-5 orders of magnitude
sensitivity. Table 02-02-02-01A gives the sensitivity for representative elements.
B) ACCURACY For the major components of a sample, the accuracy ranges from 1-258. For the lower limits of detection (ppm
range) the accuracy is typically ±15%.
C) PRECISION The overall precision of the technique ranges from 5-10%.
& REAGENTS REQUIRED
High purity water, argon gas.
7. EQUIPMENT REQUIRED
Currently 2 companies are manufacturing ICPOES equipments:
ARL in Sunland, California, and Jarrell Ash in Pittsburgh,
Pennsylvania.
& KEYWORD INDEX: Analyses, multi-element analyses, ICPOES.
9. CROSS REFERENCE ID NUMBERS 02-02-01.
10. REFERENCES
A) PRIMARY SOURCE
234 Fassel, V.A.,and R.N. Kniseley, "Inductively Coupled Plasma Optical Emissions Spectroscopy", Anal. Chem., 46, 1110A (1974).
B) BACKGROUND INFORMATION
235
Jones, J.L., R.L. Dahlquist, R.E. Hagt and J.W. Knoll, "Liquids Analysis with the Inductively Coupled Plasma Torch -
a Multi-Channel Optical Emission System," Pittsburgh Conference, Cleveland, Ohio, 1974.
C) FIELD APPLICATIONS
236 Dahlquist, R.L., R.E. Hoyt and J.W. Knoll, "Application of the Inductively Coupled Plasma Using Thermal and Direct
Aerosol Generation, presented at the 21st Canadian Spectroscopic Symposium, Ottawa, Ontario, Canada, October 7-9, 197*.
214
-------
TITLE INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROSCOPY
PAGE 2 OF 2 FOR
10 NO- 02-02-02-01
Element A
Ag 3280
As 1937
B 2498
Cd 2265
Cr 2835
Cr 2677
Cu 3247
Fe 2599
Mg 2795
Mn 2576
Mo 3170
Na 3302
Ni 2316
Pb 2203
Sb 2068
Se 1960
Sn 1899
Ta 2400
V 3110
Zn 2138
! Height of
Observation
Above Coil
(mm)
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
16.5
2n- Limit of
Detection
(ug/ml)
0.01
0.04
0.03
0.02
0.006
0.007
0.003
0.003
0.0002
0.003
0.06
1.3
0.04
0.05
0.07
0.08
0.05
0.02
0.005
0.009
From Reference 234
POLYCHROMATOR
Figure 02-02-02-01A. Block Diagram of Plasma Torch and Spectrometer.
215
-------
PAGE 1 OF 3 FOR
1. TITLE X-RAY FLUORESCENCE OF ENVIRONMENTAL SAMPLES
2. IDENTIFICATION CODE
02-02-02-02
3. ABSTRACT OF METHODOLOGY
X-ray fluorescence (XRF) is based on the measurement of secondary X-rays that are produced when a sample Is irradiated with a beam of
X-rays.
In order to perform the most accurate analysis, the analyst must be aware of several factors:
1. Sample preparation: XRF can be used to directly measure particulates .collected on filter material, but other environmental samples
(solids and liquids) can be analyzed by XRF. Figure 02-n?-02-02A (from Gould) summarizes sample preparation techniques. Birks or
Morrison can provide more specific information. (See References below.)
2. Standards: In general, standards should match as closely as possible the sample to be analyzed, otherwise correction factors for matrix
effects will be required. Typical standard preparation consists of evaporating a solution of salts on filter paper or addition of
internal standards to solutions or to a borate glass fusion. Recently, standard metal particulates were generated and collected on a
filter media to provide standards (Dharmajan).
3. Filter Material: To obtain accurate and sensitive analyses of particulates collected on filter media, the background impurities must
be low. Birks (EPA-R2-72-063) has shown Millipore or Whatman filter paper to be the best choices for XRF analysis. Glassfiber
can be used if one of comparable purity can be found.
4. Particle Size Effects: The larger the particle, the greater the decrease in sensitivity for the same ug/cm2 concentration. For particles
above a few microns the X-ray intensity falls off dramatically. Empirical or theoretical calculations to correct for this problem can be
difficult or impossible on environmental samples. Use of fractionating impactor reduces this problem by providing standard-sized
samples which can be corrected on an individual basis.
5. Matrix Effects: Problems are encountered especially with the light elements due to absorption of low energy secondary X-rays by
the filter material or aerosol particles. In particular, one must be aware that variations in the elemental compositions within a
particle will affect the observed intensity by changing the degree of absorption.
6. Resolution: XRF energy dispersive instruments (XRF-ED) are relatively inexpensive and faster than crystal spectrophotometers (XRF-CS)
However, XRF-ED cannot separate the K line of one element from the K. line of the next lower atomic number in the region of S to
Ni. For this reason (and sensitivityaconsiderations) it is necessary to use XRF-CS to separate the lines of interest and retain
reasonable counting times for low concentrations.
4. APPLICATION^ Engineering evaluation R&D
A) OPERATIONAL SCOPE
This method can be used on liquid or solid samples from any industrial stream.
particulates collected on filters or impactor stages.
B) INTERFERENCES/LIMITATIONS
See Abstract of Methodology.
C) RECOMMENDED USE AREA
Analysis of collected particulates on filters for engineering evaluation R&D.
This method is particularly useful for
5. OPERATIONAL PARAMETERS
A) RANGE
See Table 02-02-02-02A for sensitivities. Ppm to percentage composition.
B) ACCURACY Variable, depends on sample, element and standards. Estimated at ±25? for environmental samples, (see Abstract
of Methodology)
C) PRECISION ±5%
6. REAGENTS REQUIRED
Reagents required will depend on preparation technique employed,
but in theory and practice samples can be run directly.
7. EQUIPMENT REQUIRED
XRF either with a crystal spectrometer for high resolution at Ion
sensitivities or with energy dispersive detector for less complex,
higher concentration samples.
a KEYWORD INDEX: Analysis, XRF.
9. CROSS REFERENCE ID NUMBERS 02-01-02,02-01-03.
10. REFERENCES
A) PRIMARY SOURCE
237 Birks, L.S., "X-ray Spectrochemical Analysis," Interscience Publishers, New York, 1969.
B) BACKGROUND INFORMATION
Refer to Continuation Sheet.
C) FIELD APPLICATIONS
Refer to Continuation Sheet.
216
-------
TITLE X-RAY FLUORESCENCE OF ENVIRONMENTAL SAMPLES (CONTINUED)
). REFERENCES (Cont)
PAGE 2 OF 3 FOR
ID NO. 02-02-02-02
B) BACKGROUND INFORMATION
:166 Morrison, G.H. (ed.), "Trace Analysis Physical Needs," Interscience Publishers, New York, N. Y., 1965.
238 Gould, R.W., "Recent Developments in Wavelength Dispersive X-ray Spectrometric Analysis," Am. Lab.. ]2_ (July 1974).
239 Gelfrich, J.V., L S. Birks and P.GBurkhalter "X-ray Spectrometry for Particulate Air Pollution A Quantitative
240 "Dharmarjan, V.,and P.M. West, "A Precise Method for the Generation of Standard Metal Salt Particules " Anal Chim
Acta, 69, 43 (1974). ' : '
241 Birks, L.S., P.G. Burkhalter and J.V. Gelfrich, "Development of X-ray Fluorescence Spectroscopy for Elemental Analysis
of Particulate Matter in the Atmosphere and in Source Emissions," Naval Research Laboratory Washinqton DC
EPA Report No. R2-72-063, November 1972. ' ' "
242 Birks, L.S., and J.V. Gilfrich, "Development of X-ray Fluorescence Spectroscopy for Elemental Analysis of Particulate
Matter in the Atmosphere and in Source Emissions," Phase II: Evaluation of Commercial Multiple Crystal Spectrometer
Instruments," Naval Research Laboratory, Washington, D. C., NRL Report 7617, June 1973.
243 Jakleric, J.M., et al ."Application of X-ray Fluorescence Techniques to Measure Elemental Composition of Particles in
the Atmosphere" in "Analytical Methods Applied to Air Pollution Measurement;1 edited by R.K. Stevens and W.F. Harget,
Ann Arbor Science, Ann Arbor, Michigan, 1974.
C) FIELD APPLICATIONS
244 Bowman, H.R., F. Asaro and J.G. Conway, Environ. Sci. Tech.. 6. 558 (1972).
245 Gianque, R.D., N.E. Brown and L.Y. Goda, "Characterization of Aerosols in California by X-ray Induced Xrray
Fluorescence Analysis," Environ. Sci. Tech., 8.(5), 436 (1974).
METALS
BULK SOLIDS
T-
POWDERS
/~
LOOSE POWDERS
POLISHING
NO PRETREATMENT
(DIRECT FUSION)
ORGANIC SOLIDS (PLASTIC, WOOD)
-v--
DISSOLUTION ASHING
GRINDING
BINDERS
MIXING
ADDED STANDARDS
CONCENTRATION
UNITED
LIQUID SOLUTION
METHODS
CHEMICAL SEPARATION'
SULPHIDE CONVERSION
OXIDATION
CONCENTRATION METHODS
SEPARATION EVAPORATION ION EXCHANGE
*
CHROMATOGRAPHY
ITY SPECIMENS (POLLUTION PARTICLES, THIN FILMS, CORROSION PRODUCTS)
FUsoN- DIRECT ANALYSIS (THIN FILM APPROXIMATION)
SELECTIVE
PRECIPITATION
THIN SUPPORT FILMS
(MYLAR, FORMVAR)
FILTER PAPER
ION EXCHANGE
MEMBRANE
ADHESIVE STRIPPING
(OXIDES)
Figure 02-02-02-02A. From Am. Lab., 12 (July 1974).
217
-------
PAGE 3 OF 3 FOR
TITLE X-RAY FLUORESCENCE OF ENVIRONMENTAL SAMPLES (CONTINUED)
ID NO. 02-02-02-02
Table 02-02-02-02A. From Anal. Chem.. 45, 2002 (1973).
100-Second Detection Limits a' for Various X-Ray Techniques, ng/cm
WAVELENGTH DISPERSION
X-Ray tube excitation
As measured
(900 watts)
Cr tube
Rh tube
W tube
ENERGY DISPERSION
X-Ray tube excitation
As measured
(150 wattsb)
Mo tube
W tube
W tube-Nifoil
Al
360
85
S
52
13
52
570
K
3
18
220
Ca
10
29
350
33
140
V
53
33
29
160
34
90
Fe
150
30
36
120
39
120
Cu
160
49
40
Zn
180
51
100
160
no
Se
820
150
100
48
110
81
Br
390
210
160
Zr
Au
Pb
1000
Z60
110
190
110
a) Detection limit defined as 3 o of background for given time.
b) 0.002 steradian aperture between X-ray tube and sample.
218
-------
TITLE OPTICAL EMISSION SPECTROSCOPY (DC ARC/AC SPARK)
ABSTRACT OF METHODOLOGY
Optical Emission Spectroscopy (OES) pertains to emission spectra in the near UV, visible,
02-02-02-03
or near IR wavelength regions of the
electromagnetic spectrum. Host direct trace element analysis by OES involves the use of the DC arc. The sample in
electrode is first made positive; then, a current of up to 30 amps (depending on the electrode diameter) i< „«! T.!
T1__ „,,! 4.^ .,4. i fnht- nm-5(- r- innf. .*-« -.i 4,_.-j-J._- /... , ci/is passed through the
improvement to the DC arc method
and increases signal.
since the intense heat generated
sample. The resultant light emissions are characteristic of the elements present. A recent
is the Stallwood Jet. This device stabilizes the arc, reduces background and selective volatilization,
The DC arc is employed both for trace and microanalysis, but is less suited for the latter,
frequently results in erratic sample vaporization. The AC spark method, in which two graphite electrodes bearing the sam e
are sparked together at a small (2 mm) gap with low capacitance and high inductance for cool excitation, is more suitable'Pfor
microanalysis. Liquid samples can be determined by means of a liquid sample injection system. In one method (porous cup
method), the sample is contained in a "cup" made of nonporous carbon. When arcing commences, the cup is broken and the sample
then comes in contact with the carbon counter electrode positioned beneath it. In a second (direct) method, the liquid sample
is placed on a solid matrix and loaded into a cup. Suitable matrix solids include Si02, MgO and carbon. The sample-bearing
matrix must be packed tightly in the cup to ensure that it will remain positioned during arcing.
OES is somewhat less costly than SSMS techniques, although sensitivities on the order of tens of nanograms rather than tenths of
nanograms can only be achieved.
4, APPLICATION- Engineering evaluation R&D.
A) OPERATIONAL SCOPE
OES is applicable to bulk solids, powders and liquids; OES is not suited to the determination of gases, halogens, carbon,
sulfur, phosphorous, and selenium. DC arc is useful for trace element analysis; AC spark is suitable for microanalysis.
B) INTERFERENCES/LIMITATIONS
Organic materials tend to ignite in the DC arc and must be removed prior to analysis (see 02-01-04-03). Arc wandering
causes wild fluctuations in radiation emitted; these effects of arc wandering are mitigated by using narrow (1/8 in. or 0.32 cm)
diameter electrodes and current adjustment.
0 RECOMMENDED USE AREA
This is the alternate recommended to engineering evaluation R&D procedure for trace element analysis and microanalysis
using OES for solids (bulk, ash), and liquids.
5, OPERATIONAL PARAMETERS (See reverse side)
A) RANGE
B) ACCURACY
C) PRECISION
6. REAGENTS REQUIRED
N/A
7. EQUIPMENT REQUIRED
DC arc or AC spark unit (Pacific Spectrochemical Co., Los Angeles),
including prisms and/or diffraction gratings, mirrors, slits;
and detection apparatus (e.g., photographic plate); development
equipment.
I & KEYWORD INDEX: Optical emission spectrometry, DC arc/AC spark, solid samples, liquids, multi-element analysis.
CROSS REFERENCE ID NUMBERS 01-02-02-01; 01-03; 01-04; 01-06.
1". REFERENCES (See reverse side)
*> PRIMARY SOURCE
B) BACKGROUND INFORMATION
FIELD APPLICATIONS
-------
TITLE OPTICAL EMISSION SPECTROSCOPY (DC ARC/AC SPARK) (CONTINUED)
PAGE 2 OF 3 FOR
ID NO. 02-02-02-03
OPERATIONAL PARAMETERS
A) RANGE With a range of 1650-9000 A, OES can be used to determine over 70 elements simultaneously; sample sizes of over Ig to
to 10"9g can be determined. See Table 02-02-02-03A for persistent lines and sensitivities of the elements using DC arc method
(with and without Stallwood jet).
B) ACCURACY ~30 - 50% accuracy.
C) PRECISION Precision varies, depending on instrumentation used. DC arc technique has lower reproducibility (higher
sensitivity) than AC spark method. The Stallwood jet improves the precision and accuracy achieved using the open arc
approach.
10. REFERENCES
A) PRIMARY SOURCE
166 Morrison, G.H. (ed.), "Trace Analysis Physical Methods," Interscience Publishers, New York, N. Y., 1965, Chapter 6.
?46 ASTH Committees A-6, B-4 and F-l, "Magnetic Properties," 1971 Annual Book of ASTM Standards, Part 8, "Standard
Method for Spectrochemical Analysis of Emissive Carbonates by the Powder DC Arc Technique," American Society for
Testing and Materials, Philadelphia, PA., 1971, p. 748.
B) BACKGROUND INFORMATION
247 "Sampling and Analytical Strategy for Potentially Hazardous Compounds in Petroleum Refinery Streams,"
Radian Corporation, Austin, Texas, p. 50.
248 Brown, R.M., et al, Amer. Lab.. 4(11), 29 (1972).
249 Fred, M., W.H. Nachtrieb and F.S. Tompkins, j^ Opt. Soc. Am.. 37, 279 (1947).
250 Morris, J.M., and F.X. Pink, ASTM Spec. Tech. Pub.. No. 221, 1957.
C) FIELD APPLICATIONS
251 Augey, H., J. Opt. Soc. Am.. 39_, 292 (1949).
252 Churchill, W.L.,and A.H.C.P. Gillieson, Spectrochim. Acta.. 5_, 238 (1952).
154 Seeley, J.L., and R.K. Skogerboe, "Combined Sampling and Analysis Method for the Determination of Trace
Elements in Atmospheric Particles," Anal. Chem., 46_(3), 415, 1974.
220
-------
TITLE OPTICAL EMISSION SPECTROSCOPY (DC ARC/AC SPARK) (CONTINUED)
(1)
PAGE 3 OF 3 FOR
1
ID NO. 02-02-02-03
Table 02-02-02-03A.U' Persistent Lines and Sensitivities
of the Elements3
Element
Ag
Al
As
Au
B
Ba
Be
Bi
Ca
Cd
Ce
Cea
Co
Cr
Cs
Cu
Dy
Er
Eu
Fe
Ga
Ga
Gd
Ge
Hf
Hg
Ho
In
In
Ir
K
La
Li
Lu
Mg
Line,
A.
3280.7
3092.7
2349.8
2428.0
2497.7
4554.0
2348.6
3130.4
3067.7
4226.7
3261.1
4186.6
4186.6
3453.5
2835.6
4555.4
3247.5
4046.0
3692.6
4594.0
3020.6
4172.1
2943.6
3422.5
2651.2
3194.2
2536.5
3891.0
4101.8
3256.1
3220.8
4044.1
3949.1
3232.6
2615.4
2795.5
Limit of
detection, ppm
Open
Arc
1
10
100
<5
2
5
0.1
0.5
5
1
20
1000
10
20
10
500
1
5
5
5
5
20
5
10
5
50
500
5
20
10
50
>1000
5
500
5
0.2
Stallwood
Jet
0.5
5
50
<5
2
2
0.5
0.02
2
0.2
10
500
5
5
5
500
0.5
2
2
2
2
5
5
2
5
10
50
2
5
<5
10
1000
2
500
2
0.2
Element
Mn
Na
Nb
Nd
Ni
P
Pb
Pd
Pr
Pt
Rb
Re '
Rh
Ru
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Tb
Te
Th
Ti
Tl
Tm
U
V
W
Y
Yb
Zn
Zr
Line,
A.
2576.1
3302.3
3094.2
4303.6
3414.8
2535.7
2833.0
3242.7
4225.3
3064.7
4201.8
3460.5
3434.9
3436.7
2598.0
4023.7
2062.8
2881.6
4424.3
3175.0
4077.7
3311.2
3509.2
2385.8
4019.1
3349.0
3775.7
3462.2
4241.7
3093.1
4302.1
3242.3
3289.4
3302.6
3496.2
Limit of
detection, ppm
Open
Arc
5
500
10
20
20
100
20
10
20
<5
>1000
50
10
100
50
1
1000
1
20
20
50
-
50
500
500
10
50
5
500
20
100
5
1
50
50
Stallwood
Jet
1
500
5
5
5
50
5
5
5
<5
1000
10
<5
10
50
0.5
500
0.5
5
5
5
-
10
100
500
1
20
2
500
5
100
2
0.5
10
10
(^Cited in Morrison, G. H., "Trace Analysis: Physical Methods,"
New York, Interscience Publishers, 1965, p. 197.
aThe data in Table 1 were obtained with a graphite matrix for
all of the elements save the rare earths for which the matrix
was lithium carbonate (Spex semiquantitative G and L
Standards). A 3.4 m spectrograph with a 600 L/mm grating set
for the first order was used.
221
-------
PAGE 1 OF 2 FOR
1. TITLE DIFFERENTAL PULSE ANODIC STRIPPING OF TRACE METALS
Z IDENTIFICATION CODE
02-02-02-04
3. ABSTRACT OF METHODOLOGY
Anodic Stripping Voltamraetry (ASV) is similar to classical polarographic analysis, but performs the analysis in two
steps. Using a hanging mercury drop electrode (HMDE) or a thin film mercury electrode, a portion of the metals in the
solution is preconcentrated by electrolytic deposition on the HMDE. The metals in the alamgam are reoxidized to the
component ions by applying a differential pulse voltammetry waveform. This DC pulse waveform consists of a slow
linear potential ramp upon which are superimposed fixed height voltage pulses. By sampling the current before and
after the pulse, a second derivative of the classical polarographic waveform is measured, generating a sharp peak
for each element.
Solids or particulates are dissolved prior to analysis (see 02-01-04) and placed into a suitable electrolyte. By
varying deposition potential, electrolyte and complexing agents, interelement effects and background current can be
minimized while peak separation and height are maximized.
4. APPLICATION'-- Engineering evaluation RSD.
A) OPE RATIONAL SCOPE
The main benefit of DPASV (differential pulsed ASV) is its extreme sensitivity to trace metals such as Cu, In, Cd,
As, Sn, Se, and Pb. These metals have been determined in waste effluent, tap water, cooling water, and in solid
matrices after a dissolution step.
Note: Because of DPASV's sensitivity, high purity reagents (see 02-01-01) must be used for the best results.
B) INTERFERENCES/LIMITATIONS
Formation of Zn-Cu or Ni-Zn intermetallics at the HMDE can be troublesome when they are present in high concentrations.
Organics present in the sample matrix should be removed prior to analysis to avoid large background or spurious results.
C) RECOMMENDED USE AREA
Trace metal analysis of Pb, As, Se, Cd, Sn, Zn, and Cu for engineering evaluation R&D.
5. OPERATIONAL PARAMETERS
A) RANGE 5 ppb to 10 ppm for Cd, Pb, Cu, Sn, Zn, 0.6 ppb to 60 ppb for As,
8 ppb to 400 ppb for Se.
B) ACCURACY N/Q (±20« estimated).
C) PRECISION ±53;
6. REAGENTS REQUIRED
Depends on element determined.
7. EQUIPMENT REQUIRED
A typical DPASV unit is made by Princeton Applied Research,
Princeton, New Jersey. Model 374 is completely automated
for continuous operation.
a KEYWORD INDEX: Analysis, differential pulsed ASV.
9. CROSS REFERENCE ID NUMBERS 02-01-04, 02-01-01.
10. REFERENCES
A) PRIMARY SOURCE
253 Siegerman, H., and G. O'Dunn, "Differential Pulse Anodic Stripping of Trace Metals," Am. Lab., June 1972.
B) BACKGROUND INFORMATION
254 Barker, G.C., and A.W. Gardner, Z. Anal. Chem.. 173_, 79 (1960).
255 Christian, G.D., "Anodic Stripping Pulse Voltammetry," J. Electroanal. Chem.. 23, 1 (1969).
256 Newnjerse°" Februar^ 1976 ""^ "* t0 M°de1 374>" Pn'nceton APPlied Research Corp., Princeton,
222
-------
PAGE 2 OF 2 FOR
-_ oiFFERENTIAL PULSE ANODIC STRIPPING OF TRACE METALS (CONTINUED)
ID NO. 02-02-02-04
C| FIELD APPLICATIONS
257 Colovas, G., J. Moyers and A.S. Wilson, Anal. Chem. Acta, 64_(3), 457 (1973).
KZ Mvers D J., and J. Osteryoung, "Determination of Arsenic (III) at PPB Level by Differential Pulse
Polarography," Anal. Chem., 45(2). 267 (1973).
259 Princeton Applied Research, "Selenium as Se-DAB Complex," Application Brief S-l, PAR, Princeton,
New Jersey.
260 Griffin, D.A., Anal. Chem., _4JU 462 (1969).
261 Princeton Applied Research, "Differential Pulse Stripping Analysis of Tap Water," Application Note 107,
PAR, Princeton, New Jersey.
223
-------
PAGE 1 OF 2 FOR
1. TITLE INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS (INAA)
2. IDENTIFICATION CODE
02-02-02-05
3. ABSTRACT OF METHODOLOGY
A sample of liquid, solid or particulates on a filter is exposed to a source of neutrons. The radioactive isotopes formed emit
characteristic gamma rays which are monitored using a thallium activated sodium iodide or lithium drifted germanium detector. The
gamma rays are absorbed by the Tl-Nal crystal and readmitted as light in the visible region. A photorcultiplier monitors these flashes
of light, while a multichannel analyzer converts this signal into an intensity versus energy spectrum. Calibration can be done directly
from counting data using the appropriate correction factors in the literature, but in practice known quantities of the elements are also
activated and compared to the sample values. Because of the extreme sensitivity of the method, care in collection and handling of the
samples is important (see 02-01-02, 03).
4. APPLICATION^ Engineering evaluation R&D.
A) OPE RATIONAL SCOPE
This method can measure elements from Na to Hg in any sample with minimal sample preparation.
B) INTERFERENCES/LIMITATIONS
An important environmental element, Pb,cannot be measured by this method. Long periods of time for decay and chemical separations
are sometimes necessary to remove interfering radioisotopes from complex matrices. This method is not readily available
commercially.
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D survey method for multi-element analysis.
5. OPERATIONAL PARAMETERS
A) RANGE Elements from Na through Hg at ppb sensitivities (see Table 02-02-02-05A for exact values).
B) ACCURACY ±5 to +25%.
Cl PRECISION ±5 to +25%.
& REAGENTS REQUIRED
N/A
7. EQUIPMENT REQUIRED
Commercial laboratories normally are employed to perform
this analysis. For example: General Activation Analysis,
11575 Dorrento Rd. No. 214, San Diego, Ca. 92121.
KEYWORD INDEX: Analysis, INAA.
9. CROSS REFERENCE ID NUMBERS 02-01-02, 03.
10. REFERENCES
A) PRIMARY SOURCE
252 Desoete, D., R. Gijbels and J. Hoste, "Neutron Activation Analysis," Wiley-Interscience Publishers, New York, 1972.
B) BACKGROUND INFORMATION
263 Kay, M.A., M. Eichor, 0. Gray, U. McKnown and J. Vogt, "Neutron Activation Analysis in Environmental Chemistry,"
Am. Lab.. 39_ (July 1973).
C) FIELD APPLICATIONS
264 D<>ms> "•» A. Rahn and J.W. Winchester, Environ. Sci. Tech, £, 441 (1972).
265 Das. H-fl-> J.P.M. Dyong and J.E. Evendijk, J. Radioanal. them.. V3(2), 413 (1973).
266 Matousek, J.P., and K.G. Brodie, Anal. Chan., 45, 160 (1973).
224
-------
TITLE INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS (INAAI (CONTINUED
10. REFERENCES (Cont)
267 Iddings, F.A., Environ. Sci. Tech., _3_, 132 (1969).
268 Zoller, W.H.,and G.E. Gordon, Anal. Chem., 42_, 256 (1970).
PAGE 2 OF 2 FOR
10 NO. 02-02-02-os
Table 02-02-02-05A.
Neutron Activation Analysis Detection Limits3
(based on a 1-hr irradiation at
4.5 X lO1^ n cm-2 sec'1^
Atomi c
number
11
12
13
14
16
17
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
37
38
39
40
42
44
45
46
Element
Na
Mg
Al
Si
S
Cl
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
Ge
As
Se
Br
Rb
Sr
Y
Zr
Mo
Ru
Rh
Pd
Detection0
limit, ug
0.0003
0.01
0.0005
3.0
7.0
0.003
0.01
0.1
0.001
0.004
0.00004
0.05
0.000004
10.0
0.0003
0.02
0.0001
0.008
0.0001
0.003
0.0002
0.002
0.0001
0.02
0.0001
0.02
0.1
0.005
0.001
0.0001
0.002
Atomi c
number
47
48
49
50
51
52
53
55
56
57
58
59
60
62
63
64
65
66
67
68
69
70
71
72
73
74
75
77
78
79
80
Element
Ag
Cd
In
Sn
Sb
Te
I
Cs
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Ir
Pt
Au
Hg
Detection^
limit, ,;g
0.0003
0.0004
0.000003
0.001
0.0002
0.002
0.00001
0.00005
0.0003
0.0004
0.01
0.002
0.0006
0.00003
0.000003
0.0006
0.003
0.000002
0.00007
0.0001
0.03
0.0005
0.00002
0.001
0.05
0.0002
0.00006
0.00002
0.01
0.00001
0.01
aFrom Kay, et al , Am. Lab,, 39 (July 1973).
bOther experimental parameters: zero decay time, 7.5-cm-diam
X 7.5-cm solid Nal (Tl) detector with 31 X counting geometry,
and 1.27-cm polystyrene beta absorber. Minimum detectable
photopeak count rate taken as 100 cpm for t1/2 < 1 hr and
10 cpm for ti/2 > 1 hr.
cThe detection limits for many of these elements can be
increased by increasing the irradiation time. On the other
hand, some of these detection limits may be limited by blank
values for the collection and irradiation containers.
225
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PAGE 1 OF 2 FOR
1. TITLE SPARK SOURCE MASS SPECTROMETRY (SSMS) WITH PHOTOGRAPHIC PLATE
DETECTION
2. IDENTIFICATION CODE
02-02-02-06
ABSTRACT OF METHODOLOGY
SSMS involves the breakdown of sample, which is present in the form of two electrodes, by an RF potential. The resultant ions are
accelerated out of the source through electrostatic and electromagnetic analyzers, similar to organic mass spectrometry. The method
of detection of the resultant ion beam determines the sensitivity and precision of the determination. Table 02-02-02-06A lists the
absolute elemental detection limits of SSMS. There are two general types of SSMS detection systems: (a) photographic plate, and
(b) electrical detection (02-02-02-07). The most widely used photoplate for SSMS ion detection is the IIford Q2 photoplate. To
achieve highest sensitivity, the attenuating plate exposure technique is used, whereby a series of exposure of the photoplate made
using the sample are followed by a series of exposures on a reference sample. Doubly charged ions give approximately a factor-of-2
greater response than singly charged counterparts, which must be taken into account in final calculations. Precision and accuracy
are highly dependent on spectral line widths and shapes. These parameters define optical densities, which are converted to ion
densities by means of calibration curves. A number of computer-oriented systems for the derivation and integration of ion intensity
profiles have been developed for use in accurate and precise determinations.
The photographic plate method is useful for the total characterization of a sample, since the entire periodic table is examined and
possible interfering ions are resolved.
4. APPLICATION^ Environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to the analysis of solid samples (coal, ash, particulates).
B) INTERFERENCES/LIMITATIONS
Emulsion variations may introduce significant error in measurement of line width. Highly reproducible plate development
techniques must be employed in order to minimize errors.
C) RECOMMENDED USE AREA
This is the recommended environmental assessment procedure for multi-element analysis.
OPERATIONAL PARAMETERS
A) RANGE Trace elements in quantities as small as 0.01 ppm can be determined. Particle sizes (coal) of 3y or less can be analyzed.
B) ACCURACY Accuracy varies with method of data interpretation; accuracy typically ranges from 100-500". Analytical accuracies ±15'i
have been reported using computer-oriented methods for development of ion intensity profiles.
C) PRECISION Precision varies with method of data acquisition. Precisions in the order of 10-20'* have been reported using computer-
assisted ion intensity profile methods.
6. REAGENTS REQUIRED
N/A
7. EQUIPMENT REQUIRED
Spark source mass spectrometer, such as Associated Electrical
Industries Limited MS702R, with Q2 photographic plate.
a KEYWORD INDEX: Spark source mass spectrometry (SSMS), photographic plate detection, solids, quantitative analysis.
9. CROSS REFERENCE ID NUMBERS 01-03-01-02, 01-03-02-01; 01-04-01-01; 01-06-01-01; 02-02-02-07.
10. REFERENCES
A) PRIMARY SOURCE
269 Ahearn, A.J., "Trace Analysis by Mass Spectrometry," New York, Academic Press, 1972, p. 9, 256, 484.
274 Nicholls, G.D., A. Graham, E. Williams and M. Wood, "Precision and Accuracy in Trace Element Analysis of Geological
Materials Using Solid Source Spark Mass Spectrography," Anal. Chem.. 39(6). 584 (1967).
B) BACKGROUND INFORMATION
270 Tranzen, J.,and K.O. Schery, Anal. Chem.. 225_, 295 (1967).
271 Owens, E.B.,and N.A. Giardino, Anal. Chem., 35. 1172 (1963).
272 Kennicott, P.R., ASTM-E14 Conf. Mass Spectrom., p. 278 (1966).
276 Honig, R., in "Advances in Mass Spectrometry" (W.L. Mead, editor), Vol. 3, p. 101-129, Institute of Petroleum, London.
277 Cavard, A., R. Bourgillot and R. Stefoni, C.R. Acad. Sci. Paris, B263, 928 (1966).
278 Jarvorski, J.F., "Sensitivity Calibration in Spark Source Mass Spectrometry," Anal_._Chem., 46(14), 2080 (1974).
279 Jharkey, A.G.,et al, "Advances in Coal Spectrometry; Mass Spectrometry," Bureau of Mines Report of Investigations #6318,
196o, 32 p.
226
-------
TITLE
'SSMS>«"™PHOTOGRAPH,CPLATE
PAGE 2 OF 2 FOR
ID NO. 02-02-02-06
"7i BACKGROUND INFORMATION (Continued) _
ASTM Committee E-l and E-2, et al , "General Test Methods," 1971 Annual Book of ASTM *t*^ j n
189 Practice for Use and Evaluation of Mass Spectrometers for Mass Spectrochemical Anal«£ «? ?,>-?1 ?' E304-68' "R«o»ended
Testing and Materials, Philadelphia, PA., 1971, p. 916. apectrocneimcal Analysis of Solids," American Society for
0 FIELD APPLICATIONS (continued)
^Source
°f
ElB"mts 1n PUt1"»
Dilution and
"Analysis of Trace Elements in Coal by Spark Source Mass Spectrometry," Bureau of Mines Report of Investigations S7714,
285
Kessler, T.,
Rept._, 42_, 1
Ahearn, A.J., "Mass Spectrographic Detection of Impurities in Liquids," Appl. Physics. 32_(7), 1197 (1961).
Schmidt, F.A., 0. Carlson, R. Conzemius and H Syec, "Diff
Mass Spectrometry as the Method of Analysis," Anal. Chem..
Hannay, N.B., and A.O. Ahearn, Anal. Chem., 26, 1056 (1954).
Kessler, T.,et al, "Spark Source Mass Spectrometer Investigation of Coal Particles and Coal Ash," Bu Mines Tech Proa
Rept._, 42_, 1971, 15 p. - :
Ahearn, A.J., "Mass Sp
Schmidt, F.A., 0. Carlson, R. Conzemius and H Syec, "Diffusion of Metallic Solutes in Vanadium Using Spark Source
Mass Spectrometry as the Method of Analysis," Anal. Chem.. 46J71. 810 (1974).
Table 02-02-02-06A. Absolute Detection Limits of Spark Source Mass Spectrometry'1', Ref. 269
Element
Ar
Ag
Al
As
Au
B
Ba
Be
Bi
Br
C
Ca
Cd
Ce
Cl
Co
Cr
Cs
Cu
Dy
Er
Eu
f
fe
Ga
Gd
Ge
H
He
Detection Limit
(nanograms)
0.03
0.2
0.02
0.06
0.2
0.01
0.2
0.008
0.2
0.1
0.01
0.03
0.3
0.1
0.04
0.05
0.05
0.1
0.08
0.5
0.5
0.2
0.02
0.05
0.09
0.5
0.2
0.0008
0.003
Element
Hf
Hg
Ho
I
In
Ir
K
Kr
La
Li
Lu
Mg
Mn
Mo
N
Na
Ne
Nb
Nd
Ni
Np
0
OS
P
Pa
Pb
Pd
Pr
Pt
Detection Limit
(nanograms)
0.4
0.6
0.1
0.1
0.1
0.3
0.03
0.1
0.1
0.006
0.1
0.03
0.05
0.3
0.01
0.02
0.02
0.08
0.4
0.07
0.01
0.4
0.03
-
0.3
0.3
0.1
0.5
Element
Pu
Rb
Re
Rh
Ru
S
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Tb
Te
Th
Ti
Tl
Tm
II
U
V
III
Xe
Y
I
Yb
Zn
Zr
Detection Limit
(nanograms)
-
0.1
0.2
0.09
0.03
0.03
0.02
0.04
0.1
0.03
0.5
0.3
0.09
0.2
0.1
0.3
0.2
0.05
0.2
0.1
0.2
0.04
0.5
0.4
0.07
0.5
0.1
0.1
'The absolute detection limits shown were calculated on the basis of experimental observations
of Hannay and Ahearn, Ref. 285; detection limits from SSMS are usually listed pa
per million atomic.
227
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PAGE 1 OF 2 FOR
. .,.,•. .- MULTIELEMENT ANALYSIS USING SPARK SOURCE MASS SPECTROIMETRV (SSMS)
1. TITLE ,.,ITH f, ECTRICAL DETECTION
2. IDENTIFICATION CODE
02-02-02-07
3. ABSTRACT OF METHODOLOGY
The SSMS technique involves the ionization of the sample, which is mixed with graphite to form two electrodes, by applying an rf potential
The ions which are produced by the high voltage rf discharge (spark) are accelerated out of the source through electrostatic and electro-
magnetic analyzers similar to organic mass spectrometry. The method of detection of the resultant ion beam determines the precision
and sensitivity of the determination. Electrical detection methods are more sensitive than photographic plate detectors.
Problems in quantitative spectral interpretation due to line-width variations, which are present in photographic plate detection
systems, are eliminated using electrical detection systems. Analyses are also considerably more rapid using electrical detection.
Two types of electrical detection systems are available: Log ratio exponential scanning can be used in a rapid (9-10 minute)
all-element survey analysis in which only moderate precision is required. Although slower, peak switching (electrostatic and
magnetic) techniques allow greater statistical precision for up to 10 selected elements with very high sensitivity. Automatic
spark discharge control has been developed for peak switching techniques, permitting unattended operation for long periods,
as well as giving improved reproducibility. (See Table 02-02-02-06-A for the absolute detection limits of SSMS.)
4. APPLICATION' Environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to the analysis of solid samples (coal, ash, particulates), and to detection of trace impurities in
I liquids with proper sample preparation (see reference 283).
B) INTERFERENCES/LIMITATIONS
Singly and doubly charged ions cannot be simultaneously determined, as with photoplate detection methods. Organic material
must be removed prior to analysis.
C) RECOMMENDED USE AREA
This method can be used for environmental assessment.
5. OPERATIONAL PARAMETERS
A) RANGE Sensitivity of log ratio exponential scanning is 0.1 to 100 ppm, and is dependent upon multiplier gain. Sensitivity
in the 1 to 5-nanogram range is attainable with electrostatic peak switching.
B) ACCURACY Accuracy of the peak switching method is dependent upon the availability of standards. The absolute accuracy has been
thee500-2?5001ppmSrangerd St6el Samples: mean aif^^^e between observed and quoted values was 4.2%for impurities in
C) PRECISION (See reverse side)
& REAGENTS REQUIRED
N/A
a KEYWORD INDEX:
7. EQUIPMENT REQUIRED
Spark source mass spectrometer, such as the Associated Electrical
Industries United MS207 R, with high gain electron multiplier
(e.g., Allen Type 20-Stage) , UV oscilloscope recorders, amplifiers,
for log ratio exponential scanning; with integrator for peak
Spark source mass spectrometry; Log ratio exponential scanning; Electrostatic and magnetic peak switching;
Electrical detection; Solids; Multielement analysis.
9. CROSS REFERENCE ID NUMBERS 01-03-01-02; 01-04-02-01; 01-06-01-01; 02-02-02-06,
10. REFERENCES
A) PRIMARY SOURCE
(See reverse side)
B) BACKGROUND INFORMATION
(See reverse side)
C) FIELD APPLICATIONS
(See reverse side)
228
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I!,., c MULTIELEMENT ANALYSIS USING SPARK SOURCE MASS SPECTROMETRY (SSMSi u,,-^
TITLE ELECTR|CAL DETECTION (CONTINUED) «.imjwt I HY (SSMS) WITH
PAGE 2 OF 2 FOR
•
3. 02-02-02-07
5. OPERATIONAL PARAMETERS (Continued)
C) PRECISION
Log ratio exponential scanning provides ±20-30% precision for concentrations in the 1 onm atnm- i
for peak switching precisions based on data for impurities in copper; precision is tvo? Si i J^M S See F1gure 02-02-02-07A
electrostatic peak switching; ±2X for chosen elements at 1 ppm concentrations Wlca11> *5% at the submicrogram level for
0. REFERENCES
A) PRIMARY SOURCE
286 BlnjjtajjjR.A.. and R.M. Elliott, "Accuracy of Analysis by Electrical Detection in Spark Source Mass Spectrometry," Anal. Chen,.. 43(1),
287 Guldoboni, R'J" "Determination of Trace Elements in Coal and Coal Ash by Spark Source Mass Spectrometry," Anal. Chem.. 45(7).
B) BACKGROUND INFORMATION
288 Franzen, J., and K.D. Schery, Z. Anal. Chem., 225, 295 (1967).
289 Evans, C.A., et al., Appl. Spectrosc., 24, 85 (1970).
283 Ahearn, A.J., "Mass Spectrographic Detection of Impurities in Liquids," J. Appl. Physics, 32, 1197 (1961).
290 Jaworski, J.F., "Sensitivity Calibration in Spark Source Mass Spectrometry," Anal. Chem., 46(14), 2080, 1974.
269 Ahearn, A.J. (ed), "Trace Analysis by Mass Spectrometry," New York, Academic Press, 1972, Chapter 8.
189 ASTM Committee E-l and E-2, "General Test Methods," 1971 Annual Book of ASTM Standards, Part 30, "Recomnended Practice for Use and
Evaluation of Mass Spectrometers for Mass Spectrochemical Analysis of Solids," American Society for Testing and Materials
Philadelphia, PA., 1971, p. 916.
C) FIELD APPLICATIONS
273 Brown, R., M. Jacobs and H. Taylor, "A Survey of the Most Recent Applications of Spark Source Mass Spectrometry," American
Laboratory, Nov. 1972, 15 pp.
291 Kessler, T., et al, "Analysis of Trace Elements in Coal by Spark-Source Mass Spectrometry," Bureau of Mines Report of Investigations
17714, 1973.
282 Kessler, T., et al, "Spark Source Mass Spectrometer Investigation of Coal Particles and Coal Ash," Bureau of Mines Technical
Progress Report, 42, 1971, 15 pp.
292 Sharkey, A.G., Jr., et al, "Advances in Coal Spectrometry, Mass Spectrometry," Bureau of Mines Report of Investigation J6318,
1963, 32 pp.
274 Brown, R., and H.E. Taylor, "The Application of Spark Source Mass Spectrometry to the Analysis of Water Samples," American Hater
Resources Association, Proc. No. 18, June 1974, p. 72.
293 Evans, C.A., Jr., "Spark Source Mass Spectrographic Method for the Survey Analysis of Trace Elements in Biological Materials,"
Cornell University, PhD Thesis, Ann Arbor, Michigan, 1968.
284 Schmidt, F.A., 0. Carlson, R. Conzemius and H. Svec, "Diffusion of Metallic Solutes in Vanadium Using Spark Source Mass
Spectrometry as the Method of Analysis," Anal. Chem.. 46(7), 810, 1974.
229
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Table of Contents for 02-03 Species Analysis
02-03-01 Laboratory Gas Analysis
02-03-01-01 GC Analysis of Flue Gas Samples (Instrumental Orsat Analysis)
02-03-01-02 Laboratory Analysis of Sulfur-Containing Gases by GC
02-03-02 Anion Analysis
02-03-02-01 Anion Analysis Using Specific Ion Electrodes (SIE)
02-03-02-02 Spectrophotometric Determination of Fluoride With Alizarin
Complexone Reagent
02-03-02-03 Barium Chloranilate Colorimetric Sulfate Method
02-03-02-04 Gravimetric and Titrimetric of Sulfate, Pyritic Sulfur and
Organic Sulfur in Coal
02-03-02-05 Determination of Sulfate by the Thorin Method
02-03-02-06 Determination of Sulfate in Scrubber Liquors (Sulfonazo III
Titration)
02-03-02-07 Determination of Alkalinity by Electrometric Titration
02-03-02-08 Determination of Bromide by Titrimetry
02-03-02-09 Determination of Chloride by Titrimetry
02-03-02-10 Determination of Total Cyanide by Volumetric Titration or
Spectrophotometry
02-03-02-11 Determination of Iodide by Titrimetry
02-03-02-12 Determination of Nitrate Nitrogen by Brucine Method
02-03-02-13 Determination of Nitrate-Nitrite Nitrogen by Cadmium Reduction
Method
02-03-02-14 Determination of Nitrite Nitrogen by Spectrometry
02-03-02-15 Determination of Phosphorous (All Forms) by Single Reagent
Method
02-03-02-16 Turbidimetric Detection of Sulfate
02-03-02-17 Determination of Total and Dissolved Sulfite Using Titrimetric
Iodine Method
02-03-02-18 Determination of Sulfite Using Titrimetric lodide-Iodate Method
02-03-02-19 Determination of Chloride by Colorimetry
02-03-02-20 Determination of Nitrate Nitrogen by Phenol Disulfonic Acid
Method
02-03-02-21 Determination of Total Solids
02-03-02-22 Determination of Total Dissolved (Filterable) Solids
02-03-02-23 Determination of Total Suspended (Nonfilterable) Solids
02-03-02-24 Determination of Total Volatile Solids
02-03-02-25 Determination of Total Hardness
02-03-02-26 Determination of Color by Spectrophotometric Method
02-03-02-27 Determination of Color by Platinum Cobalt Method
02-03-02-28 Determination of Specific Conductance
02-03-02-29 Determination of Turbidity by the Nephelometric Method
02-03-02-30 Visual Determination of the Opacity of Emissions From Stationary
Sources
231
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APPLICATION MATRIX FOR 02-03 SPECIES ANALYSIS
METHOD
02-03-01-01
02-03-01-02
02-03-02-01
02-03-02-02
02-03-02-03
02-03-02-04
02-03-02-05
02-03-02-06
02-03-02-07
02-03-02-08
02-03-02-09
02-03-02-10
02-03-02-11
02-03-02-12
02-03-02-13
02-03-02-14
02-03-02-15
02-03-02-16
02-03-02-17
02-03-02-18
02-03-02-19
02-03-02-20
02-03-02-21
02-03-02-22
02-03-02-23
02-03-02-24
02-03-02-25
02-03-02-26
02-03-02-27
02-03-02-28
02-03-02-29
02-03-02-30
LEVEL I
ENVIRONMENTAL
ASSESSMENT
•
•
•
•
•
•
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•••— -—I •'• ••••^•••••••••••^
COMPLIANCE
•
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-------
SPECIES ANALYSIS ID No. 02-03
The abstracts in this section discuss two major categories:
(02-03-01) laboratory gas analysis, and (02-03-02) anion analysis. The
methods employed are gas chromatography, specific ion electrode, spectro-
photometry, turbidimetry, gravimetric and titrimetric methods.
02-03-01 - Laboratory Gas Analysis - (Abstracts 02-03-01-01 to
02-03-01-02] •-
Laboratory analysis of gases, such as flue gases (02-03-01-01) and
sulfur-containing gases (02-03-01-02), involves the use of gas chromatography
(GC). Although GC is routinely used for qualitative and semi-quantitative
analysis, with careful calibration quantitative measurements can be made.
Syringe, ampoule and valve techniques are the most widely used methods
of introducing gaseous samples into the chromatogram. The use of pressure
lock syringes is desirable in the analysis of gases since this method assures
rapid injection of a precise quantity of pressurized sample. For the
analysis of samples trapped in metal bombs, the bomb valve may be connected
directly to the GC or to a sample reservoir by means of a simple valve
connection. When the reservoir method is used, a supply of carrier gas is
also connected to the reservoir by means of a separate valve. After the
sample reservoir is initially filled with sample gas from the bomb, the
bomb valve is closed off and the sample flushed into the chromatograph
by opening the carrier gas valve.
Another important factor in the use of GC is the possibility of corrosion
of the metal components of the GC lines and detection equipment by the
reactive species (acid gases) in the trapped samples. This can be minimized
by performing analyses on samples which are as small as possible, by flushing
of the system after use with suitable inert gases, and by proper cleaning
of exposed surfaces using standard cleaning techniques.
02-03-02 Anion Analysis (Abstracts 02-03-02-01 to 02-03-02-20)
Regarding the analysis of anions, modern methods involve use of specific
ion electrodes, (02-03-02-01) spectrophotometry, gravimetric (02-03-02-04) and
titrimetric methods (02-03-02-04, 06, 07-11, 17, 18). Ion concentrations
233
-------
can be determined using specific ion electrodes in several different ways.
When the direct measurement method is used, the concentration of the desired
species is read directly from the scale of a specific ion meter or from a
calibration curve. Matrix effects are an important consideration in direct
determinations. In general, matrix interferences can be eliminated by the
addition of small quantities of ionic strength or pH adjusters (acids,
bases, buffers) to both standard and sample solutions prior to measurement.
When the approximate concentration of the sample is known, but a
specific ion meter is not available, the preparation of a calibration curve
can be eliminated by using the standard addition technique. This method
involves original zeroing of the detecting meter with the electrodes immersed
in the sample, followed by addition of a known volume of standardizing
solution to the sample at a concentration approximately equal to the sample
itself. The resulting change in potential is then measured, and the original
sample concentration is determined by multiplying a Q value obtained from a
"standard addition table" times the concentration of the standard solution.
Electrode titrations (02-03-02-01) greatly increase the number of
species that can be measured. For example, T-type titrations, in which the
electrode senses the level of titrant as it is added to the sample, have been
applied to the determination of sulfate (lead titrant and electrode),
aluminum (fluoride titrant and electrode) and EDTA (copper titrant and
electrode). R-titrations, in which the electrode senses the reagent species
that has been added to the sample before titration, extends the number of
species that can be measured by electrode to include Ni, Zn, Mn and Sr.
Sample concentrations can be determined by incremental methods,
which involve determination of the change in electrode potential when a
standard solution is added to the sample (standard known addition) or
when the sample is added to the standard solution (sample addition). The
sample concentration can be determined using a reagent solution which
precipitates, complexes, or reacts with the species being measured. Gram's
plots, which are plots of series of incremental measurements, can be used
to increase the sensitivity for many titrations.
234
-------
Prior to sample measurement by SIE, some forms of sample preparation
may be required. This may involve dissolution of the sample in appropriate
solvent (or acid, base, buffer), adjustment of pH with standard buffer
solutions, adjustment of ionic strength, or other methods to eliminate
interferences. Many standard and commercial references are available which
list recommended specific procedures for sample preparation (Reference 223).
Spectrophotometry is routinely used in quantitative determination of
many anionic species (02-03-02, 02, 03, 05, 10, 12 through 16, 19, 20).
The determinations are based on Beers' law, which states that successive
increments in the number of identical absorbing molecules in the path of a
beam of monochromatic radiation absorb equal fractions of radiant energy
which traverses them. This law also indicates that the absorptivity of a
species is a constant which is independent of concentration, path length
and intensity of incident radiation. Since in many practical applications
Beers' law is not rigorously obeyed, quantitative analyses are usually
performed by means of calibration curves (plots of absorbance vs. concen-
tration) using standard solutions.
Because of the extreme sensitivity of spectrophotometric measurements,
care must be taken to prevent sample contamination by trace impurities.
High purity water should be used in the preparation of reagents and samples.
Excessive color due to species other than that being determined generally
interfere with spectrophotometric analyses. Turbid solutions may require
filtration in order to remove suspended solids.
Gravimetric and titrimetric procedures are routinely used in the
analysis of anions such as Group VII elements, sulfate, and alkalinity
(02-03-02-04, 06, 07-11, 17, 18). In order to obtain good accuracy and
precision in gravimetric determinations, the actual precipitation should be
carried out under controlled conditions. Factors such as temperature,
period of digestion, number and type of washings prior to drying, etc., must
be considered. Cleanliness of equipment and use of impurity-free water are
important factors in gravimetric and titrimetric procedures. For high
precision, titrations should be performed as far as possible under the
same conditions, using the same equipment and personnel. For accurate
results, blank determinations should accompany all sample determinations.
235
-------
REFERENCES
294 Ewing, G.W., "Instrumental Methods of Chemical Analysis," 3rd ed.,
McGraw-Hill Book Co., New York, 1969, p. 450-473.
295 Brody, S.S., and J.E. Chaney, J. Gas Chroma tog.. 4, 42 (1966).
223 Orion Research, "Analytical Methods Guide," 7th ed., Orion Research
Incorporated, Cambridge, Mass., May 1975.
236
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TITLE GC ANALYSIS OF FLUE GAS SAMPLES (INSTRUMENTAL ORSAT ANALYSIS)
Z IDENTIFICATION CODE
02-03-01-01
3. ABSTRACT OF METHODOLOGY
Samples returned to the laboratory are analyzed on a GC employing a dual column (Porapak N and Molecular Sieve 5A), a gas
sampling valve and a column switching valve to separate the components of a sulfur rich flue gas sample. While the switching
operations can be manual, automatic valve switching is recommended. This system utilizes the "Series/Bypass" technique in
which at selected times one column is bypassed by carrier gas flow, permitting certain components to be stored there while
separations are made on the other column.
4. APPLICATION- Engineering evaluation R&D, environmental assessment.
A) OPERATIONAL SCOPE
This method can be used to analyze sulfur rich flue gas stream for C02, ethylene, ethane, H2S, 02, N2, CH4, CO, H20, SOj.
B) INTERFERENCES/LIMITATIONS
If a sample is obtained using grab sampling techniques (01-01-04), one must be aware that changes can occur in the sample.
Analysis should be performed as soon as possible. On-line analysis requires a filtered paniculate sample (02-05-01-01).
C) RECOMMENDED USE AREA
Engineering evaluation R&D at any combustion process.
5. OPERATIONAL PARAMETERS
A) RANGE 7h-js system will analyze flue gas components at their nominal concentration range.
B) ACCURACY N/Q (+10% estimated).
C) PRECISION N/Q (±10% estimated).
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
N/A
Dual column GC with FID & TC detector (Carle Instruments,
Fullerton, California.makes a GC specifically for this
application).
& KEYWORD INDEX:
9. CROSS REFERENCE ID NUMBERS Ol-01-04s 02-05-01-01.
10. REFERENCES
A) PRIMARY SOURCE
296 "Sulfur Rich Flue Gas Analysis," Application No. 153-C, Carle Instrument Co., Fullerton, California.
B) BACKGROUND INFORMATION
297 Adams, D.F., et al, J.A.P.C.A.. 15(1), 31 (1965).
298 Juvet, R.S., "Advances in Chromatography," Vol. 1, Marcel Dekker Inc., New York, 1966, p. «».
FIELD APPLICATIONS
-------
1. TITLE LABORATORY ANALYSIS OF SULFUR-CONTAINING GASES BY GC
2. IDENTIFICATION CODE
02-03-01-02
3. ABSTRACT OF METHODOLOGY
The verification of sulfur-containing components from gas bomb and trap samples-can be made by GC analysis with flame photometric
detection having >30,000:1 specificity for sulfur and a reliable sensitivity of 1-10 PPb. Special columns are used, which contain
deactivated silica gel, Tracer silica and/or Triton X.
The chronograph should be equipped with gas valve injection, dual columns, and temperature programming. Sample loop volumes may be
determined based on anticipated concentrations of individual sample components. Generally, sample volumes of 0.25 to 0.5 ml are
sufficient.
4. APPLICATION- Environmental assessment, engineering evaluation R&D.
A) OPE RATIONAL SCOPE
Method is applicable to flue gas, fugitive gas, etc., contained in bombs and other grab sample containers.
{See 01-01-04-01, 01-01-01-02, 01-05-04-01, 01-05-04-02). Gases such as H2S, SOj and C$2 can be separated.
B) INTERFERENCES/LIMITATIONS
N/A
C) RECOMMENDED USE AREA
This is the recommended level 1 environmental assessment procedure for analysis of sulfur-containing gases by GC.
5. OPERATIONAL PARAMETERS
A) RANGE GC method has a sensitivity of up to 1-10 ppb for sulfur.
B) ACCURACY ±5« or better.
C) PRECISION ±10%
6. REAGENTS REQUIRED
Column packings cited above.
7. EQUIPMENT REQUIRED
Standard GC apparatus, with flame photometer detector.
KEYWORD INDEX: Sulfur gas analysis, gas chromatography, flame photometric detection, silica gel (Tracer), Triton X.
9. CROSS REFERENCE ID NUMBERS 01-01-04-01, 01-01-04-02; 01-05-04-01, 01-05-04-02.
10. REFERENCES
A) PRIMARY SOURCE
014 Hamersma, J.W.,and S.R. Reynolds, "Tentative Procedures for Sampling and Analysis of Coal Gasification Processes," TRW Systems
Group, EPA Contract No. 68-02-1412, March 1975, p. 5.11.
B) BACKGROUND INFORMATION
299 "Operation Manual for MT150 Series Gas Chromatograph, Flame Photometric Detector and Nickel-63 High Temperature Electron
Capture Detector," Tracor, Inc., Operations Manuals, 1968.
C) FIELD APPLICATIONS
300 Adams, D.F., and R.K. Koppe, "Gas Chromatographic Analysis of Hydrogen Sulfide, Sulfur Dioxide, Mercaptans, and Alkyl
Sulfide. and nisulfidp*." Tanni &.'>(~1\ .inlw IQKQ n cm cnc
..__ f . ,r _.._ .,_.._ .«wf*^wy ww wir r VIII w W^ I U^fll I \» fll I {t I V 3 I ^ \J | flj
Sulfide, and Disulfides," Tappi, 42(7), July 1959, p. 601-605.
238
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PAGE 1 OF 3 FOR
1. TITLE ANION ANALYSIS USING SPECIFIC ION ELECTRODE (SIE)
Mil, III III I _
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-03-02-01
Specific anion electrodes can be used to determine a wide variety of anions, including bromide chloride, cyanide, fluoride iodide
nitrate, perchlorate, thiocyanate, etc. (See Table 02-02-01-18A.) For example, fluoride is determined pctentiometrically'using a'
selective ion fluoride electrode in conjunction with a standard junction sleeve-type reference electrode and a PH meter having an
expanded millivolt scale, or a selective ion electrode having a direct concentration scale for fluoride. (See 02-02-01-18 for
titration procedures using SIE's.)
4. APPLICATION- Environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to samples (aqueous samples, species absorbed in liquids) containing species such as bromide, chloride, etc.
(See Table 02-02-01-018A.)
B) INTERFERENCES/LIMITATIONS
Extremes of pH may interfere. Cations which complex with specific anions may interfere in the analysis of the anion.
C) RECOMMENDED USE AREA
This is the recommended environmental assessment procedure for the determination of anions listed in Table 02-02-01-18A.
5. OPERATIONAL PARAMETERS
A) RANGE See Table 02-02-01-18A for detectable concentration ranges of specific anions.
B) ACCURACY See continuation sheet.
C) PRECISION See continuation sheet.
6. REAGENTS REQUIRED
pH adjusters and titrants; precipitation or complexing agents,
when required.
7. EQUIPMENT REQUIRED
Specific ion electrodes; specific ion meter or standard pH meter
having an expanded millivolt scale; standard laboratory glassware
(beakers, pipettes, volumetric flasks).
& KEYWORD INDEX: specific ion electrodes, aqueous effluents, anions.
9. CROSS REFERENCE ID NUMBERS 02-02-01-18; 01-02-02-01, 01-02-02-01; 01-05-01-02.
10. REFERENCES
A) PRIMARY SOURCE
223 Orion Research, "Analytical Methods Guide," Anion Research, Inc., 7th ed., May 1975.
B) BACKGROUND INFORMATION
See continuation sheet.
C) FIELD APPLICATIONS
See continuation sheet.
239
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PAGE 2 OF 3 FOR
TITLE ANION ANALYSIS USING SPECIFIC ION ELECTRODE (SIE) (CONTINUED)
ID NO. 02-03-02-01
5. OPERATIONAL PARAMETERS
B) ACCURACY
Accuracy varies with the species being determined. For fluoride determination, a mean of 0.84 mg 1 liter fluoride with a standard
deviation of 0.03 was obtained using synthetic samples containing 0.85 mg 1 liter fluoride by Analytical Reference Service, PHS.
C) PRECISION
+0.03 for fluoride determination; see (b) above.
10. REFERENCES
B) BACKGROUND INFORMATION
185 "Methods for Chemical Analysis of Waster and Wastes," National Environmental Research Center, EPA 625/6-74-003,
Cincinnati, 1974, p. 65-7.
301 Ross, J.W.,and M.S. Frant, "Fotentiometric Titrations of Sulfate Using an Ion Selective Lead Electrode," Anal. Chem., 41(7),
967 (1969).
302 Paletta, B., "The Direct Electrometric Measurement of Iodide and lodate Ions," Mikrochim Acta.6, 1210 (1969).
303 Florence, T.M., "Differential Potentiometric Titration of Parts per Billion Chloride with Ion-Selective Electrodes,"
J. Electro.Anal. Chem.. 31., 77 (1971).
C) FIELD APPLICATIONS
304 Elfter.L.A., and C.E Decker, "Determination of Fluoride in Air and Stack Gas Samples by Use of an Ion Specific Electrode,"
Ana 1. Lnem. » *HJ\ 11), IfaDo \ I?bo),
305 Ungmuir, D., and R. Jacobson, "Specific-Ion Electrode Determination of Nitrate in Some Freshwater and Sewage Effluents "
Envir. Sci. and Tech.. 4J10), 834 (1970).
306 Buck, H., and 6. Ruesmann, "A New Semi-Automatic Method for Fluoride Determination in Plant and Air Samples," Fluoride.
_i(U» 5 (1971), *
307 DHscoll, J.N J H. Becker, A.W. Berger, J.T. Funkhouser and J.R. Valentine, "Determination of Oxides of Nitrogen in Combustion
Atlintlc Cily^ N. J?7SSne°1971 * Electt"°de'" paper Presented at ^ «h Annual Meeting of the Air PollutionControl Assn,
210
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PAGE 3 OF 3 FOR
TITLE ANION ANALYSIS USING SPECIFIC ION ELECTRODE (SIE) (CONTINUED) ID NO. 02-03-02-01
Table 02-03-02-01A. Anion Analysis Using SIE.
Electrode
bromide
chloride
cupric
cyanide
fluoride
iodide
nitrate
perchlorate
silver/
sulfide
thiocyanate
•"^^•^^•^^^^^^
Type
solid-state
liquid
solid-state
solid-state
solid-state
solid-state
combination
solid-state
solid-state
liquid
solid-state
solid-state
Concentration
Range (M)
10° to 5 x 10"6
10° to 8 x 10"5
10° to 5 x 10"5
saturated to 10"8
10"2 to 10"6
saturated to 10
saturated to 10
10° to 2 x 10"7
10° to 6 x 10"6
10° to 2 x 10"6
10° to 10"7
Ag+ or S-
10° to 5 X 10"6
Hi^ ^ —
Temperature
Range
(°C)
0-80
0-50
0-80
0-80
0-80
0-80
0-80
0-80
0-50
0-50
0-80
0-80
______^^— «— •,
Interferences
max level: S"
-------
i TITI c SPECTROPHC'."
1. TITLE COMPLEXONE REAGENT
iTOMETRIC DETERMINATION OF FLUORIDE WITH ALIZARIN
2. IDENTIFICATION CODE
02-03-02-02
3. ABSTRACT OF METHODOLOGY
Three ml of an acidic solution of lanthanum-alizarin buffered to 4.50 ±0.02 is added to a 10 ml volumetric flask containing an
aliquot of the sample, and diluted to the mark. The mixture is allowed to stand for 30 minutes and then the absorbance is
measured at 622 nm in a 1 cm cell using a reagent blank as the reference. A calibration curve (prepared at the same temperature)
is used to quantify the amount of F in the sample.
Because of the possible interference from ions such as aluminum, iron, and phosphate, techniques such as distillation, diffusion
or ion exchange must be employed to remove these interferences (see 02-01-01-01, 02).
4. APPLICATIONS Engineering evaluation R&D, environmental assessment.
A) OPERATIONAL SCOPE
This method can be used to analyze impingers, bubblers, and particulate matter (once it has been dissolved) for the fluoride
content. By using a suitable separation procedure such as the WilHard-Winter distillation technique, more complex
solutions can be analyzed with this technique.
B) INTERFERENCES/LIMITATIONS
The lanthanum-alizarin complexone reagent has a pH sensitivity, so the solutions must not exceed the capacity of buffer system
'to maintain the apparent pH of 4.50 ±0.02. Aluminum and iron interfere with the fluoride reagent, and must be removed
or the fluoride separated by distillation, diffusion or ion exchange.
C) RECOMMENDED USE AREA
This is the recommended environmental evaluation R&D procedure for F after the appropriate separation is used.
OPERATIONAL PARAMETERS
A) RANGE 0.002 to 1.40 p.g of fluoride per ml. A lower detection range is available from 0.00 to O.B
of fluoride per ml.
B) ACCURACY N/Q
C) PRECISION +0.015 to 0.025 micrograms of fluoride per ml.
6. REAGENTS REQUIRED
Acetic acid, acetone, alizarin complexone, ammonium acetate
ammonium hydroxide, lanthanum chloride, sodium fluoride.
7. EQUIPMENT REQUIRED
Spectrophotometer, sample cells.
& KEYWORD INDEX-' Analysis, anion analysis, fluoride analysis.
9. CROSS REFERENCE ID NUMBERS 02-01-01-01, 02.
10. REFERENCES
A) PRIMARY SOURCE
084 NoHA12202-01-68T "washln"^^^1 * fl°972F1 U°ri* Content of the Atmosphere and Plant Tissues (Manual Methods),"
B) BACKGROUND INFORMATION
308 Belcher, R.', and T. S. West, "A Comparative Study of Some Lanthanum Chelates of Alizarin Complexone as Reagents for Fluoride,
C) FIELD APPLICATIONS
242
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1. TITLE BARIUM CHLORANILATE COLORIMETRIC SULFATE METHOD
— i.— ..-
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-03-02-03
The sulfate concentration in a liquid sample is determined by reaction with barium chloranilate in a pH controlled, 50% alcohol
solution to yield the highly colored acid chloranilate. The concentration of the product colored species is determined
spectrophotometrically at 530 nm. Since the barium chloranilate reacts 1 to 1 with sulfate in solution, the absorption is
directly related to the sulfate concentration.
4. APPLICATION^ Engineering evaluation R&D, environmental assessment.
A) OPERATIONAL SCOPE
This method is primarily designed to provide an analytical finish for sampling method 01-01-03-01. This sulfate method can be
applied to other liquid samples, but extreme precautions must be exercised because many cations and anions interfere with this
method. (See Ref. 053 under background information for a detailed listing of interferences.)
Bl INTERFERENCES/LIMITATIONS
Cations such as Al+3, 'Ca+2, Fe+3, Pb+2, Ca+2, and Zn+2 cause interference through precipitation of the acid chloranilate ion.
Anionic interferences such as oxalate and phosphate can interfere quite dramatically. Chloride and bicarbonate interfere, but
to a much smaller extent. When this procedure is used in conjunction with 01-01-03-01, the glass wool filter will remove most
of the particulates. Consequently, the possibility of interferences passing into the condenser or impinger system is low.
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D H,SO. analytical finish (see 01-01-03-01).
5. OPERATIONAL PARAMETERS
A) RANGE 0 to 500 ppm sulfate
B) ACCURACY N/Q
C) PRECISION ±0.4*
6. REAGENTS REQUIRED
Sodium carbonate, barium chloranilate, pH 5.6 buffer solution
(acetic acid and sodium acetate), ethyl alcohol, hydrochloric
acid, sulfuric acid.
7. EQUIPMENT REQUIRED
Centrifuge, balance (mg.), spectrophotometer.
& KEYWORD INDEX: Analysis, sulfate analysis, barium chloranilate.
9, CROSS REFERENCE ID NUMBERS 01-01-03-01.
10. REFERENCES
A) PRIMARY SOURCE
053 ASTM "Tentative Method of Tests for Sulfur Oxides in Flue Gases (Barium Chloranilate Controlled Condensation Method),
1974 Annual Book of ASTM Standards, Part 26, Method D3226-73T, ASTM Standards, p. 700.
B) BACKGROUND INFORMATION
309 Bertolacini, R.J.,and J.E. Barney, Anal. Chem.,29. 281 (1957).
310 Carlson, R.M., R.A. Rosell and W. Vallejos, Anal. Chem.., 39_, 689 (1967).
O FIELD APPLICATIONS
311 Bertolacini, R.J., and J.E. Barney, Anal. Chern^. 30, 202 (1958).
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PAGE 1 OF 2 FOR
GRAVIMETRIC AND TITRIMETRIC DETERMINATION OF SULFATE SULFUR, PYRITIC
1. TITLE SULFUR AND ORGANIC SULFUR IN COAL
2. IDENTIFICATION CODE
02-03-02-04
3. ABSTRACT OF METHODOLOGY
Sulfate sulfur is determined by extracting a weighed sample of air-dried coal (ground to pass a No. 60 mesh sieve) with dilute
hydrochloric acid, followed by precipitation with ammonium hydroxide, with subsequent precipitation with barium chloride and
weighing as barium sulfate. (See 01-03-01-02 and 02-01-03-02 for sample collection and preparation procedures.)
Pyritic sulfur is determined by extracting a weighed sample of coal with dilute nitric acid, followed by titrimetric determination
of iron in the extract as a measure of pyritic sulfur. Pyritic sulfur is thus determined indirectly by measuring the amount of
pyritic iron in the nitric acid extract. The pyritic iron in the extract is precipitated as the ferric hydroxide by adding ammonium
hydroxide. The amount of iron present, which is equivalent to the amount of pyritic sulfur, is then determined by titration with
potassium dichromate or permanganate.
Organic sulfur is determined by subtracting the sum of the sulfate sulfur and pyritic sulfur from the total sulfur (See Reference 057).
4. APPLICATION:
Engineering evaluation R&D.
A) OPERATIONAL SCOPE
The method is applicable to all sampled coals (ground to pass a No. 60 mesh sieve).
B) INTERFERENCES/LIMITATIONS
N/Q
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D procedure for the determination of sulfate sulfur, pyritic sulfur,
and organic sulfur in coal.
OPERATIONAL PARAMETERS
A) RANGE
Methods have sensitivities of ±0.10 percent or less.
B) ACCURACY
10? or better.
C) PRECISION Permissible differences in results obtained in the same (different) laboratory include: Sulfate sulfur: 0.02 (0.04);
pyritic sulfur, under 2 percent: 0.05 (0.03); pyritic sulfur, 2 percent or more: 0.10 (0.40).
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Reagent water; ammonium chloride, ammonium hydroxide, barium chloride, diphenylamine
sulfonate indicator solution, hydrochloric acid solutions, hydrogen peroxide, mercuric
chloride solution, methyl orange indicator solution, nitric acid, potassium dichromate
or potassium permanganate, stannous chloride solution, sulfuric-phosphoric acid
mixture, sulfuric-phosphoric acid-manganous sulfate mixture.
Laboratory balance, cold-finger condenser,
crucibles, hot plate, muffle furnace,
titration apparatus.
KEYWORD INDEX: Sulfur, sulfate, pyritic, coal, precipitation, titration, analysis.
9. CROSS REFERENCE ID NUMBERS 02-01-03-02; 01-03-01-02, 01-03-02-01.
10. REFERENCES
A) PRIMARY SOURCE
057
057
o D"3 and D"5' "Gaseous Fue1s; Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19,
Philadelphia PA 197lth°d 3R7T^St f<"" F°rms °f Su1fur 1n c°a>." American Society for Testing and Materials,
B) BACKGROUND INFORMATION' ' P' 387"388'
S5IJ! ^T^u6 °"3 and D"5> "Gaseous Fuels; Coal and Coke," 1971 Annual Book of ASTM Standards, Part 19, D271 , "Standard
D? ?0?i ubo!'at°pf Sampling and Analysis of Coal and Coke," American Society for Testing and Materials, Philadelphia,
rn. , I 3 / I t p. [ J-31 .
312 Powell, Alfred R., "The Analysis of Sulfur Forms in Coal," Technical Paper No. 254, U.S. Bureau of Mines, 1921.
313 rhlnHnpPi^er »i'"TSS In*eriaborat°ry Study of Methods for the Determination of Total Sulfur, Forms of Sulfur and
Chlorine in Coal, Report of Investigate, OESRA, Ohio State University Engineering Experiment Station, 1960.
(Continued on reverse side)
C) FIELD APPLICATIONS
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PAGE 2 OF 2 FOR
_. . GRAVIMETRIC AND TITRIMETRIC DETERMINATION OF SULFATE SULFUR. PYRITIC
II" LC SULFUR AND ORGANIC SULFUR IN COAL (CONTINUED)
ID NO. 02-03-02-04
B) BACKGROUND INFORMATION
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTH Standards, Part 23, E200-67, "Standard
Methods for Preparation, Standardization and Storage of Standard Solutions for Chemical Analysis," American Society for
Testing and Materials, Philadelphia, PA., p. 868-885.
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, D1193 "Standard
Specification for Reagent Water," American Society for Testing and Materials, Philadelphia, PA., 1971, p. 196-197.
215
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1. TITLE DETERMINATION OF SULFATE BY THE THORIN METHOD
2. IDENTIFICATION CODE
02-03-02-05
3. ABSTRACT OF METHODOLOGY
Method involves titration of the sample with barium perchlorate solution using thorin as indicator. Thorin and barium react to fom
a deep red-colored complex when the endpoint is reached. The color varies in intensity with different solvents, and an organic
solvent is the preferred medium for the analysis. The endpoint may be determined either spectrophotometrically or visually. When
the spectrophotometric method is used, the preferred titration medium is 80 percent alcohol maintained at pH 5 with sodium acetate
buffer. The endpoint may also be detected visually by viewing the solution through a didymium glass filter.
4. APPLICATION: Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to all samples (aqueous samples, acid gases absorbed in liquids) having sulfate content of less than
200 mg/liter.
B) INTERFERENCES/LIMITATIONS
Metal ions interfere, and can be removed by cation exchange. Phosphate interferes; with 100 mg/liter of sulfate, 10 and
20 mg/liter of phosphate give 2-3 percent positive error.
C) RECOMMENDED USE AREA
This is the recommended compliance procedure for determination of sulfur dioxide adsorbed in H.,0,, impinger solutions.
OPERATIONAL PARAMETERS
A) RANGE
Sulfate content must not exceed 200 mg/liter.
B) ACCURACY
N/Q
C) PRECISION Analysis of 2 test samples by 17 laboratories resulted in mean values of 394 and 21 mg/liter with standard deviations
of 10 and 1.1 mg/liter, respectively.
6. REAGENTS REQUIRED
Isopropanol, hydrogen peroxide, thorin indicator
(l-(arsonophenylazo)-2-naphthol-3, 6-disulfonic acid), barium
perchlorate, sulfuric acid standard.
7. EQUIPMENT REQUIRED
Pi pets, standard titration apparatus, standard laboratory
glassware, cation exchange column (optional); spectrophotorneter-
titration assembly, didymium glass filter (optional).
& KEYWORD INDEX: Sulfate, sulfur dioxide,aqueous effluents, titrimetry, spectrophotometry, thorin.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02.
10. REFERENCES
FPA
ProteCt1°n
"**""*
A) PRIMARY SOURCE
314 Federal '
185 National
B) BACKGROUND INFORMATION
315 California State Water Quality Control Board, "Water Quality Criteria," Pub. 3-A, 1963, p. 275.
316 U.S. Public Health Service, "Drinking Water Standards," Public Health Service Pub. 956, 1962, p. 7.
C) FIELD APPLICATIONS
317 Atmospheric Emissions from Sulfuric Acid Manufacturing Processes, U.S. DHEW, PHS, Division of Air Pollution, Public
r "* Pub1lcatlon N°- 999-AP-13, Cincinnati, Ohio, 1965.
11Q Stto Pc'f"j'?v ^termination of SO? and S03 in Flue Gases," Journal of the Institute of Kuel , 24, 237-243, 1961.
320 Patty> li P'' /', ; 1S V Measu,Hn9 Flue-Gas S02 and S03," PoweTT ioTT^-177 NoVeibe>~' 1957." '
Control Asso'ciatJ 13ni62 (1963 ^ EqUlf""ent and T^hniqueFToT Soling Chemical Process Gases," J. Air Pollution
216
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1. TITLE DETERMINATION OF SULFATE IN SCRUBBER LIQUORS (SULFONAZO III TITRATION)
Z IDENTIFICATION CODE
02-03-02-06
3. ABSTRACT OF METHODOLOGY
The total sulfur content of a scrubber liquor is determined by first passing the liquor through a cationic exchange resin. Next,
H202 is added to the treated liquor to oxidize sulfides and sulfites to sulfate. The excess H202 is decomposed by boiling, and then
acetone and the Sulfonazo III indicator are added to an aliquot of the treated liquor. The sulfate content is titrated with barium
perchlorate with Sulfonazo III as the indicator. The endpoint is reached when the color changes from purple to blue.
4. APPLICATION- Engineering evaluation R&D.
A) OPERATIONAL SCOPE
This procedure is applicable to the measurement of sulfate in aqueous wet scrubber process control liquors. The indicator,
Sulfonazo III, is applicable to any sulfate titrations and is especially recommended for any procedure currently using thorin.
B) INTERFERENCES/LIMITATIONS
Cu , Ni , Co , Zn , Fe and Pb must be removed by ion exchange prior to titration. pH should be adjusted to <4.
Treated solutions from the ion exchange column normally have a low enough pH.
C) RECOMMENDED USE AREA
Engineering evaluation R&D.
5. OPERATIONAL PARAMETERS
A) RANGE
B) ACCURACY
C) PRECISION
100 ppm sensitivity.
Better than ±5%.
Better than ±5%.
6. REAGENTS REQUIRED
Dowex 50W-X8 (or equivalent) cation exchange column,
Sulfonazo III, hydrogen peroxide, barium perchlorate.
7. EQUIPMENT REQUIRED
Laboratory glassware, titration assembly.
8, KEYWORD INDEX: Analysis, sulfate titration, Sulfonazo III.
9. CROSS REFERENCE ID NUMBERS 02-01-01, 02-01-02.
10. REFERENCES
Madda1on?.CR.F.. A. Grant and C. Zee, "Final Report, Task 6; Development: of Sulfonazc,111 Procedures for Sulfate,"
TRW Defense & Space Systems, Redondo Beach, California, February 1975 (EPA 68-02-I4U).
, "Determination of Sulfur & Sulfate by Titration with Barium Perchlorate," Anal. Chim.
Acta.. 39, 375 (1967).
Cl FIELD APPLICATIONS
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1. TITLE DETERMINATION OF ALKALINITY BY ELECTROMETRIC TITRATION
2. IDENTIFICATION CODE
02-03-02-07
3. ABSTRACT OF METHODOLOGY
The method involves the electrometric titration of the sample with a standard solution of strong acid. The endpoints of the titration
are determined with a pH meter and are selected as the inflection points in the titration of sodium carbonate with sulfuric acid,
(e.g., a bicarbonate endpoint at pH 4.5, and a carbonate endpoint at pH 8.3).
4. APPLICATION- Compliance, environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to all aqueous streams (liquid and slurry discharges) including drinking, surface and saline watei , and
industrial wastes. Samples having high concentrations of mineral acids should be titrated to pH 3.9 (see Ref. 024).
8) INTERFERENCES/LIMITATIONS
Interferences include large quantities of salts of weak organic and inorganic acids (e.g., silicic acid) and oil and grease which may
coat the pH electrode.
C) RECOMMENDED USE AREA
This is the recommended compliance procedure for determination of total alkalinity of all aqueous samples, including saline
samples.
5. OPERATIONAL PARAMETERS
A) RANGE
Method measures all concentration ranges of alkalinity, using samples having volumes of 50 ml.
B) ACCURACY The accuracy (bias) of 40 analysts in 17 laboratories analyzing synthetic water samples having 8, 9, 113 and 119
mg/liter alkalinity as CaC03 was reported as +0.85, +2.0, -9.3, -8.8 mg/liter CaC03, respectively.
C) PRECISION In a single laboratory (MDQARL) using surface water samples at an average concentration of 122 mg CaCOg/liter, a
standard deviation of +3 was obtained.
6. REAGENTS REQUIRED
0.02N standard hydrochloric acid; indicators (bromcresol green,
methyl orange, methyl purple, methyl red, phenolphthalein).
7. EQUIPMENT REQUIRED
Pipets, electrometric titration apparatus, Erlenmeyer flasks.
& KEYWORD INDEX: Alkalinity, aqueous effluents (liquid/slurry), electrometric titration.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01; 01-02-02-02.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory, Nationa'
Environmental Research Center, EPA No. 625/6-74-003, Washington, 1974, p. 3-4.
B) BACKGROUND INFORMATION
024 1ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, D-1067,
"Standard Methods for Test for Acidity or Alkalinity of Water," American Society for Testing and Materials, Philadelphia,
PA.,,1971, Method B., p. 138.
C) FIELD APPLICATIONS
323 Barnes, Ivan, "Field Measurement of Alkalinity and pH," U.S. Geol. Survey Water-Supply Paper 1535-H, 17 p. (1964).
324
325
Eaton, P.M. ."Formulas for Estimating the Drainage and Gypsum Requirements of Irrigation Waters," Texas Agr. Expt.
Sta. Misc. Pub. Ill, 1954.
A'ricSdHandbo k
i
Diagnos1s and ImP™>vement of Saline and Alkali Salts," U.S. Dept. Agriculture,
-------
1. TITLE DETERMINATION OF BROMIDE BY TITRIMETRY
2. IDENTIFICATION CODE
02-03-02-08
3. ABSTRACT OF METHODOLOGY
After pretreatment with calcium oxide for removal of interferences (iron, managanese and organic matter), the sample is divided into
2 aliquots. The first sample is treated with bromine water for conversion of iodide to iodate, then is titrated with phenyl arsine
oxide (PAD) or sodium thiosulfate using starch as the indicator for the determination of iodide. The endpoint is determined by means
of a pH meter rather than a pH indicator.
The second aliquot is analyzed for iodide plus bromide by conversion of these species to iodate and bromate with calcium hypochlorite.
Excess hypochlorite is decomposed with sodium formate. The sample is then titrated with PAD or thiosulfate, as above.
Bromide is then calculated by difference.
4. APPLICATION:
Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to all aqueous (liquid and slurry) streams, including drinking, surface and saline waters, domestic and
industrial wastes.
B) INTERFERENCES/LIMITATIONS
Interferences caused by iron, manganese and organic matter are removed by calcium oxide pretreatment. Color interferences are
eliminated by use of pH meter.
C) RECOMMENDED USE AREA
This is the recommended compliance procedure for bromide determinations of all aqueous industrial effluents.
5. OPERATIONAL PARAMETERS
A! RANGE Concentration range is 2 to 20 mg/liter of bromide.
B) ACCURACY 96, 83, 97, 99% recoveries on mixed domestic and industrial waste effluent having concentrations of 2.8, 5.3, 10.3
and 20.3 mg/liter of bromide.
Cl PRECISION Standard deviations of +0.13, ±0.37, ±0.38, ±0.44 and ±0.42 mg/liter on samples above having concentrations of 0.3,
2.8, 5.3,10.3 and 20.3 mg/liter, respectively.
6. REAGENTS REQUIRED
Acetic acid, bromine water, calcium carbonate, calcium
hypochlorite, calcium oxide, hydrochloric acid, potassium iodide,
phenylarsine oxide, sodium thiosulfate, starch solution, amylose
indicator.
7. EQUIPMENT REQUIRED
Standard laboratory glassware,
titration apparatus, pH meter.
8. KEYWORD INDEX: Bromide! aqueous effluents, titrimetric method.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01; 01-02-02-02.
10, REFERENCES
** ?85MASdsR
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1. TITLE DETERMINATION OF CHLORIDE BY TITRIMETRY
2. IDENTIFICATION CODE
02-03-02-09
3. ABSTRACT OF METHODOLOGY
Method involves acidification of sample, followed by tit ration with dilute mercuric nitrate solution, in the presence of a small
amount of mixed diphenylcarbazone-bromophenol blue indicator. The optimum pH range for the titration is pH 3.0-3.6. The proper pH
for the titration is easily obtained by adding bromphenol blue indicator and slowly adding dilute nitric acid or sodium hydroxide
to adjust the pH of the sample. The formation of the stable blue-violet mercury diphenylcarbazone complex indicates the endpoint
of the titration, which can be determined visually by observing the persistent blue-violet color, or spectrophotometrically, at
530 nm.
4. APPLICATION: Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to all aqueous (liquid and slurry) streams, including drinking, surface and saline waters, domestic and
industrial effluents.
B) INTERFERENCES/LIMITATIONS
Aniorts and cations at concentrations normally found in surface waters do not interfere (approximately 1 to 100 ppm range).
Sulfites interfere, but are removed by treatment with hydrogen peroxide.
C) RECOMMENDED USE AREA
This is the recommended compliance procedure for determination of chloride in all aqueous effluents with moderate
anion and cation levels (see above).
OPERATIONAL PARAMETERS
A) RANGE
Method is suitable for all ranges of chloride; sample aliquots of 10 to 20 mg Cl per 50 ml should be used.
B| ACCURACY Accuracy results (bias) of 42 analysts in 18 laboratories on samples having chloride increments as 17, 18, 91,
97, 382, 398 mg/liter were +0.4, +0.6, +0.1, -0.5, -2.3, and -4.7 respectively, in mg/liter.
Cl PRECISION In a single (MDQARL) laboratory, using surface water samples at an average concentration of 34 mg/liter Cl, the
standard deviation was ±1.0.
a REAGENTS REQUIRED
Mercuric nitrate solution; diphenylcarbazone-bromophenol blue
indicator.
7. EQUIPMENT REQUIRED
Standard laboratory equipment; titration assembly.
KEYWORD INDEX: Chloride, aqueous effluents, titrimetric method.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01; 01-02-02-02.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," National Environmental Research Center, EPA No. 625/6-74-003,
Washington, 1974, p. 29-30.
B) BACKGROUND INFORMATION
024 ASTM Comittee D-19 and D-22, "Water; Atmospheric Analysis," Part 23, D512-67, "Standard Methods of Test for
Chloride Ion in Industrial Water and Industrial Wastewater," Referee Method A, American Society for Testing and
Materials, Philadelphia, PA., 1973, p. 273.
Dubsky, J.V., and J. Trtilik, "Microvolumetric Analysis Using Diphenylcarbazide and Diphenylcarbazone as Indicators
(Mercunmetry)," Mikrochemle. V. 12, 315 (1933).
C) FIELD APPLICATIONS
328 Clarke, F.E., "Determination of Chloride in Water," Anal. Chem.. 22. 553, 1458 (1950).
Hi Eaton, P.M., "Formulas for Estimating the Drainage and Gypsum Requirements of Irrigation Waters," Texas Agr. Expt.
Sta. Misc. Rept., Ill, 1954.
327
330
Taylor, E.W., "The Examination of Waters and Water Supplies," 7th ed., Boston, Little, Brown & Co., 1958
U.S. Public Health Service, "Drinking Water Standards," Public Health Service Pub. 956, p. 7 (1956).
, 841 p.
250
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1. TITLE
-- •
3. ABSTRACT OF METHODOLOGY
VOLUMETRIC TITRATION
^ IDENTIFICATION CODE
02-03-02-10
The sample to be analyzed, which contains complexed cyanide, is subjected to reflux-distillation; the cyanide is released and absorbed
as HCN in a sodium hydroxide scrubber. The cyanide ion in the absorbing solution is then determined by volumetric titration or by
colorimetry. The titrimetric measurement uses silver nitrate as the titrant and p-dimethylaminobenzalrhodanine indicator The first
change in color from yellow to brownish-pink signals the endpoint of the titration. In the colorimetric measurement the cyanide is
converted to cyanogen chloride by reaction with chloramine-T at pH less than 8. A solution of pyridine-pyrazolone or pyridine-
barbituric acid is then added, and absorbance is measured at 620 nm or 578 nm, respectively.
4. APPLICATION^ Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to aqueous (liquid and slurry) streams, including drinking, surface, and saline waters, domestic and
industrial wastes.
Bl INTERFERENCES/LIMITATIONS
Oxidizing agents (chlorine) interfere, but can be removed by adding ascorbic acid until Kl-starch test paper remains colorless.
Sulfides interfere, but may be removed by treatment with cadmium carbonate. Fatty acids also interfere, but may be removed
by acidification and solvent extraction.
Cl RECOMMENDED USE AREA
This is the recommended compliance method for the determination of total cyanide in aqueous effluents, especially complexed
cyanide, which cannot be determined by S.I.E. method (see 02-03-02-01).
5. OPERATIONAL PARAMETERS
A| RANGE Volumetric titration measures cyanide concentrations greater than 1 mg/liter in 0.2 mg/200 ml of absorbing liquid.
Colorimetric procedure measures concentrations below 1 mg/liter of cyanide and is sensitive to 0.02 mg/liter.
Bl ACCURACY Recoveries of 85% and 102% were obtained in a single laboratory (MDQARL) using mixed industrial and domestic waste
waste samples having cyanide concentrations of 0.28 and 0.62 mg/liter cyanide.
C) PRECISION Standard deviations of ±0.005, ±0.007, ±0.031 and ±0.094 were obtained in a single laboratory (MDQARL) using mixed
industrial and domestic waste samples with concentrations of 0.06, 0.13, 0.28, and 0.62 mg/liter cyanide.
6. REAGENTS REQUIRED
Sodium hydroxide, cadmium carbonate, ascorbic acid, cuprous
chloride, sulfuric acid, sodium dihydrogen phosphate, standard
cyanide solution, silver nitrate solution, rhodanine indicator,
Chloranrine T, color reagents (pyridine-barbituric acid; pyridine-
7. EQUIPMENT REQUIRED
Reflux distillation apparatus microburet;
spectrophotomete r.
8. KEYWORD INDEX: Cyanide, aqueous effluents, volumetric titration, spectrophotometry.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02; 02-03-02-01.
10. REFERENCES
^J PRIMARY SOURCE
185 "Methods for Chemical Ana'ysis of Water and Wastes," National Environmental Research Center, EPA No. 625/6-74-003,
Washington, 1974, p. 40-48.
Bl BACKGROUND INFORMATION
024 ASTM Conmittee D-19 and D-22, "Water; Atmospheric Analysis," Part 23 IB-OK-H, "Standard Methods of Test for Cyanides
in Water," Referee Method A, American Society for Testing and Materials, Philadelphia, PA., ia/J, p. «»u.
332 Bark, L S , and H.G. Higson, "Investigation of Reagents for the Colorimetric Determination of Small Amounts of Cyanide,
Talanta. 2, 471-9 (1964).
0 ^D APPLICATIONS^ .^^ of ^.^ fay ^.^ ^^ Distjl lation>» ^ 40, 848-56 (1968).
331 U.S. Public Health Service, "Drinking Water Standards," Public Health Service Pub. 956, p. 6 (1952).
251
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1. TITLE DETERMINATION OF IODIDE BY TITRIMETRY
2. IDENTIFICATION CODE
02-03-02-11
3. ABSTRACT OF METHODOLOGY
The sample is first pretreated with calcium oxide in order to reduce interferences caused by iron, manganese and organic matter.
The sodium acetate-buffered sample is then oxidized with bromine to iodate, and the excess bromine is removed with sodium formate.
Iodine, which is equivalent to the iodide present in the sample, is then liberated by the addition of potassium iodide to an acidic
solution. The iodine is then titrated using standard thiosulfate solution, using starch as the indicator. The endpoint may be
determined with a pH meter, or by visual observation of the light yellow color.
4. APPLICATION' Compliance, environmental assessment.
••••••••••^^^^^^••^•^•1 Illl"! •
A) OPE RATIONAL SCOPE
Method is applicable to all aqueous (liquid and slurry) streams, including drinking, surface and saline waters, sewage and
industrial waste effluents.
B) INTERFERENCES/LIMITATIONS
Iron, manganese and organic material interfere, but these can be removed by pretreatment with calcium oxide.
C) RECOMMENDED USE AREA
This is the recommended compliance method for determination of iodide in all aqueous effluents.
5. OPERATIONAL PARAMETERS
A) RANGE
2 to 20 mg/liter iodide.
B) ACCURACY Recoveries of 80, 97, 97 and 92% were obtained in a single laboratory (MDQARL) using mixed domestic and industrial
waste effluent, at concentrations of 1.6, 4.1, 6.6, 11.6 and 21.6 mg/liter iodide.
C) PRECISION Standard deviations of ±0.23, ±0.17, ±0.10, ±0.06 and ±0.50 mg/liter were obtained for the samples described
in 5 (b) above.
6. REAGENTS REQUIRED
Acetic acid, bromine water, calcium oxide, potassium iodide,
sodium acetate, sodium formate, sulfuric acid, phenylarsine
oxide, amylose indicator, sodium thiosulfate.
7. EQUIPMENT REQUIRED
Standard laboratory glassware; titration assembly, pH meter
(optional).
a KEYWORD INDEX: iodide, aqueous effluents, titrimetry.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," National Environmental Research Center, EPA No. 625/6-74-003,
Washington, 1974, p. 74-7.
B) BACKGROUND INFORMATION
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," Part 23, D1246C, "Standard Methods of Test for Iodide and
Bromide in Industrial Water and Industrial Wastewater," American Society for Testing and Materials, Philadelphia, PA.,
197j, p. -j-jI~j.
333 Kolthoff, I.M., and E.B. Sandell, "Textbook of Quantitative Inorganic Analysis," New York, Macmillan Co., 3rd ed.,
I ybZ^ p. oo5.
C) FIELD APPLICATIONS
252
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TITLE DETERMINATION OF NITRATE NITROGEN BY BRUCINE METHOD
1 IDENTIFICATION CODE
02-03-02-12
ABSTRACT OF METHODOLOGY
Method is based on a spectrophotometrlc determination of the yellow-colored reaction product of the alkaloid brucine with nitrate in
an acid medium. The sample is prepared by adjustment of the PH to 7.0 with acetic acid or sodium hydroxide, and filtration to remove
turbidity. After treatment to remove interference (see 4(b) below), the sample is acidified with concentrated sulfuric acid Brucine-
sulfanilic acid reagent is then added, and the sample is heated in a boiling water bath. After cooling, the colored complex is
determined spectrophotometrically at 410 nm.
4, APPLICATION- Compliance, environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to most aqueous streams including drinking, surface and saline water, domestic and industrial effluents.
This method is especially useful on samples of high salinity.
8) INTERFERENCES/LIMITATIONS
Dissolved organic matter interferes, but can be removed by addition of suitable reagents. Addition of Nad to blanks, standard
and samples compensates for interfering chloride. Sodium arsenite eliminates interference due to residual chlorine {up to
5 mg/liter). Interference up to 1 mg/liter nitrite is eliminated by use of sulfanilic acid. Other strong redox agents inter-
fere. Iron and manganese interfere at concentrations greater than 1 mg/liter.
C) RECOMMENDED USE AREA
This is the recommended compliance procedure for determination of all nitrate nitrogen in aqueous effluents not exceeding
limitations cited above.
5. OPERATIONAL PARAMETERS
A) RANGE
0.1 to 2 mg nitrate nitrogen/liter.
B) ACCURACY Accuracy results (as bias in mg N/liter) obtained by 27 analysts in 15 laboratories on samples containing 0.16, n.19,
1.08 and 1.24 mg N/liter were -0.01, +0.2, +0.04 and +0.04 mg N/liter respectively.
C) PRECISION Precision (as standard deviations in mg N/liter) obtained by 27 analysts in 15 laboratories on samples containing
0.16, 0.19, 1.08 and 1.24 mg N/liter were'0.092, 0.083, 0.245, and 0.214 mg N/liter, respectively.
6. REAGENTS REQUIRED
Sodium chloride, sulfuric acid,
potassium nitrate, acetic acid,
brucine-sulfanilic acid,
sodium hydroxide.
7. EQUIPMENT REQUIRED
Spectrophotometer or filter photometer for optical density
measurement at 410 nm; glass sample tubes; neoprene-coated
wire racks to hold sample tubes; water bath (100°C), water
hath fin tn ISOP.). __
8. KEYWORD INDEX: Nitrate nitrogen, brucine, liquid/slurry, spectrophotometry. filter photometry.
9. CROSS REFERENCE ID NUMBERS 01-02, 01-02-02-01
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," National Environmental Research Center, EPA No. 625/6-74-003,
Washington, 1974, p. 197-200.
, ,
B, BACKGROUND ,NFORMAT,ONi9 ^ ^ ^^
in Water," American Society for Testing and Materials, pl"l»lJelP !?A
2M Sa^n fS&J.WSS E2TW
Method 213-C, p. 461.
0
*** "
""
335
336
" 13th ed American Public Health
Fede-ratlon, Washington, 0. C, 1971,
j r the Detem1natjon of Nitrate ,„ Ocean, Estuarine and Fresh Waters,"
FlSS?^.ft.F610si1^-«- -- Skougstad, .iazotization Method for «,tr.f. and NUrite,
. -
M.G. Mellon, "Colorimetric Determination of Nitrites, Ind. En,. Ch».. Anal. Ed, 18, 76 (1945).
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PAGE 1 OF 2 FOR
1. TITLE DETERMINATION OF NITRATE-NITRITE NITROGEN BY CADMIUM REDUCTION METHOD
2. IDENTIFICATION CODE
02-03-02-13
3. ABSTRACT OF METHODOLOGY
Method involves reduction of nitrate to nitrite by passage of a filtered sample through a column containing granulated copper-cadmium.
(The sample may be prefiltered through a glass filter or a 0.45 u membrane filter to eliminate interference due to turbidity.) A
typical reduction column is shown in Figure 02-03-02-13A. The column may be constructed from 2 pieces of tubing joined end to end,
or from a 100-ml pipet. The cadmium granules (new or used) are cleaned with dilute HC1 and copperized with a 2 solution of copper
sulfate. The column effluent is then used to diazotize sulfanil amide, which is then treated with N(l-naphthyl) ethylenediamine
dihydrochloride to form an azo dye. The dye is then determined spectrophotometrically at 540 nm.
A simple nitrite nitrogen value can be obtained by omitting the copper-cadmium reduction step. (See 02-03-02-14.) A simple nitrate
nitrogen value can be obtained from the difference between the nitrate-nitrite and simple nitrite determinations.
4. APPLICATION' Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to most aqueous streams including drinking, surface and saline water, domestic and industrial effluents.
B) INTERFERENCES/LIMITATIONS
Suspended particle can be removed by filtration; turbidity can be removed by treatment with zinc sulfate. Addition of EDTA
eliminates interferences due to high concentrations of trace metals (iron, copper, etc.). Oil and grease can interfere by coat-
ing the surface of the cadmium; this is eliminated by extraction with an organic solvent.
C) RECOMMENDED USE AREA
This is the recommended compliance method for determination of total nitrate-nitrite nitrogen and/or nitrite and nitrate nitrogen
alone, in aqueous effluents (liquids and slurries).
5, OPERATIONAL PARAMETERS
A) RANGE
0.01 to 10 mg/liter nitrate-nitrite nitrogen; range may be extended with sample dilution.
B) ACCURACY Recoveries of 100%, 102% and 100% were obtained in a single laboratory (MDQARL) using sewage samples at concentra-
tions of 0.04, 0.24, 0.55 and 1.04 mg nitrate-nitrite nitrogen/liter.
C) PRECISION The standard deviations of ±0.005, ±0.004, ±0.005 and ±0.01 were determined on samples cited above.
6. REAGENTS REQUIRED
Granulated cadmium; copper-cadmium; ammonium chloride-EDTA,
sulfanilamide and N(l-naphthyl)-ethylenediamine dihydrochloride,
zinc sulfate, sodium hydroxide, ammonium hydroxide, copper
sulfate, stock nitrite and nitrate solutions.
7. EQUIPMENT REQUIRED
Reduction column (see Figure 02-03-02- 13A);
for use at 540 nm, with path length of 1 cm
spectrophotometer
or longer.
KEYWORD INDEX: Nitrate-nitrite nitrogen, aqueous effluents, cadmium reduction method, spectrophotometry.
9. CROSS REFERENCE ID NUMBERS 01-02-02-02, 01-02-02-01; 02-03-02-14.
10. REFERENCES
A) PRIMARY SOURCE
185
'^Methods for Chemical Analysis of Water and Wastes," National Environmental Research Center, EPA No. 625/6-74-003,
B) BACKGROUND INFORMATION
204 Taras, M.J. (ed.J, "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public
Health Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washington,
D. C., 1971, Method 213-C, p. 458.
C) FIELD APPLICATIONS
337 Henrikson, A.,and Selmer-Olsen, "Automatic Methods for Determining Nitrate and Nitrite in Water and Soil Extracts,"
338 Grasshoff, K., "A Simultaneous Multiple Channel System for Nutrient Analysis in Sea Water With Analog and Digital
Data Record," Advances in Automated, Analyses. Technicon International Congress, Vol. 11, 133-45, 1969.
339 Brewer, P., and J.P. Riley, "The Automatic Determination of Nitrate in Sea Water," Deep Sea Research, Jl, 765-72, 1965.
29)
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PAGE 2 OF 2 FOR
TTLE DETERMINATION OF NITRATE-NITRITE NITROGEN BY CADMIUM REDUCTION
METHOD (CONTINUED)
ID NO. 02-03-02-13
3cm I.D.
Figure 02-03-02-13A. Reduction Column (Reference 185).
255
-------
1. TITLE DETERMINATION OF NITRITE NITROGEN BY SPECTROPHOTOMETRY
2. IDENTIFICATION CODE
02-03-02-14
3. ABSTRACT OF METHODOLOGY
The pH of the sample is first adjusted to pH 6 with 1:3 hydrochloric acid. The sample is then treated with sulfanilamide and
N-(l-naphthyl) ethylenediamine dihydrochloride. The nitrite diazotizes the sulfanilamide, and subsequent coupling of the species to
the diamine salt results in the formation of a red-colored azo dye. The dye is then determined spectrophotometrically at 540 nm.
4. APPLICATION^ Compliance, environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to most aqueous streams (liquids and slurries) including drinking, surface and saline waters, domestic
and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Strong oxidants or reductants interfere; high alkalinity (>600 mg/liter) gives low results due to shift in pH.
C) RECOMMENDED USE AREA
This is the recommended compliance procedure for determination of nitrite nitrogen.
5. OPERATIONAL PARAMETERS
A) RANGE 0.01 to 1.0 mg nitrite nitrogen per liter.
B) ACCURACY N/Q
C) PRECISION N/Q
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Distilled water; buffer-color reagent, (hydrochloric acid
sulfanilamide, N-(l-naphthyl) ethylenediamine dihydrochloride,
sodium acetate); nitrite solutions.
Spectrophotometer for use at 540 nm with 1 cm or greater cells;
50 ml Nessler tubes or 50 ml volumetric flasks.
& KEYWORD INDEX: Nitrite nitrogen, aqueous effluents, spectrophotometry.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02; 02-03-02-13.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," National Environmental Research Center, EPA No. 625/6-74-003,
Washington, 1974, p. 215-16.
8) BACKGROUND INFORMATION
204 "Standard Methods for the Examination of Water and Wastewater," 13th ed., Washington, D. C., 1971, p. 458.
C) FIELD APPLICATIONS
340 Henrikson, A., and Selmer-Olsen, "Automatic Methods for Determining Nitrate and Nitrite in Water and Soil Extracts,"
Analyst. 95_, 514-18 (1970).
256
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PAGE 1 OF 2 FOR
1. TITLE DETERMINATION OF PHOSPHOROUS (ALL FORMS) BY SINGLE REAGENT METHOD
2. IDENTIFICATION CODE
02-03-02-15
3. ABSTRACT OF METHODOLOGY
Figure 02-03-02-15A (from Reference A) shows the analytical scheme for differentiation of the various phosphorous (P) forms, which
is based on specific sample pretreatments. Total P is determined using the total sample with no prior filtration. Total orthophosphate
is measured by colorimetric detection of a blue-colored complex formed by reaction of the sample with ammonium molybdate and antimony
potassium tartrate. Total hydrolyzable P is determined by sulfuric acid hydrolysis procedure and colorimstry, minus predetermined
orthophosphates. Finally, total organic P is measured by persulfate digestion and colorimetry, and minus hydrolyzafale P and
orthophosphate.
Dissolved P includes all P present in the filtrate of the sample which has passed a membrane filter. Dissolved orthophosphate is
determined by colorimetry, as above. Dissolved hydrolyzable P is measured by sulfuric acid hydrolysis and colorimetry, minus pre-
determined dissolved orthophosphates. Dissolved organic P is measured by persulfate digestion and colorimetry, minus dissolved
hydrolyzable P and orthophosphate.
The colorimetric finish consists of adjusting the pH to 7 ± 0.2 and adding 8 ml of a combination reagent. The combination reagent
consists of: 50 ml 5N H2$04, 5 ml antimony potassium tartrate solution (1.3715 g/500 ml), 15 ml ammonium raolybdate solution
(20 g/500 ml), and ascorbic acid solution (0.1 M). The resultant color is measured at 650 or 880 nm with a spectrophotometer.
4. APPLICATION- Compliance, environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to aqueous (liquid and slurry) streams, including drinking, surface and saline waters, domestic and industrial
effluents; it may also be applicable to sediment-type samples, sludges, etc.
B) INTERFERENCES/LIMITATIONS
High iron concentrations can cause precipitation of phosphorous. Copper, iron and silicate may interfere at very high concen-
trations (much greater than sea level concentrations). Arsenate, at concentrations greater than sea water, may interfere.
Mercury chloride (used as sample preservative) interferes when the chloride level of the sample is low; this is overcome by addi-
tion of a minimum of 50 mg/liter of sodium chloride.
0 RECOMMENDED USE AREA
This is the recommended compliance procedure for determination of phosphores (all forms) in aqueous effluents.
5. OPERATIONAL PARAMETERS
A) RANGE
0.01 to 0.5 mg phosphorous/liter.
B) ACCURACY The accuracy (bias) obtained by 33 analysts in 19 laboratories using samples containing 0.110, 0.132, 0.772 and
0.882 mg P/liter were +0.003, +0.016, +0.023, -0.008 mg P/liter.
0 PRECISION The precisions obtained on the above samples were 0.033, 0.051, 0.130 and 0.128 mg P/liter, respectively.
6. REAGENTS REQUIRED
Sulfuric acid, antimony potassium tartrate, ammonium
molybdate, ascorbic acid, ammonium persulfate, standard
Phosphorous solution, sodium hydroxide, phenolphthalein.
7. EQUIPMENT REQUIRED
Spectrophotometer or filter photometer; acid-washed glassware;
0.45w membrane filter; standard laboratory equipment.
a KEYWORD INDEX: Phosphorous, aqueous effluents, spectrophotometry, ammonium molybdate, antimony potassium tartrate.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01; 01-02-02-02.
10. REFERENCES
A) PRIMARY SOURCE
103 PIS bFlOuS t VI l*J idii I i* a I nnw ij ^ •
Washington, 1974, p. 249-55.
Bl BACKGROUND INFORMATION
024
341
National Environmental Research center, EPA No. 625/6-74-003,
515-72 "Standard Methods of Test for Phosphate
. . 1973. p. 388.
Gales, M., Jr., E. Julian and R. Kroner, "Hethoc I for Quantitative Determination of Total Phosphorus in Water,'
J. Am. Mater works Assoc._, 58, No. 10, 1363 (1966).
c> FIELD APPLICATIONS
342 Murphy, J., and J. Riley, "A Modified Single Solution for the Determination of Phosphate in Natural Waters," AnaK
Chem. Acta.. 27^ 31 (1962).
-------
TITLE
DETERMINATION OF PHOSPHOROUS (ALL FORMS) BY SINGLE REAGENT
METHOD (CONTINUED)
PACE 2 OF 2 FOR
ID NO. 02-03-02-15
SAMPLE
TOTAL SAMPLE (NO FILTRATION)
DIRECT
COLORIMETRY
ORTHOPHOSPHATE
H2S04
HYDROLYSIS AND
COLORIMETRY
PERSULFATE
DIGESTION
COLORIMETRY
HYDROLYZABLE AND
ORTHOPHOSPHATE
PHOSPHORUS
FILTER (THROUGH 0.45 » MEMBRANE FILTER)
DIRECT
COLORIMETRY
HYDROLYSIS AND
COLORIMETRY
PERSULFATE
DIGESTION AND
COLORIMETRY
DISSOLVED
ORTHOPHOSPHATE
DISS. HYDROLYZABLE
AND ORTHOPHOSPHATE
DISSOLVED
PHOSPHORUS
Figure 02-03-02-15A. Analytical Scheme for Differentiation of Phosphorus Forms (Ref. 185).
258
-------
1. TITLE TURBIDIMETRIC DETERMINATION OF SULFATE
,-. • •—
3. ABSTRACT OF METHODOLOGY
I IDENTIFICATION CODE
02-03-02-16
Method involves precipitation of sulfate as barium sulfate using barium chloride and a suspending agent (gelatin in some cases)
The resultant turbidity is determined using a colorimeter, nephelometer, or transmission spectrophotometer and is compared to a
curve obtained using standard sulfate solutions.
4. APPLICATION- Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to aqueous (liquid and slurry) streams, including drinking and surface waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Excessive color and suspended matter interfere; this is overcome by blank determinations using samples not treated with barium
chloride. Silica in excess of 500 mg/liter will interfere.
C) RECOMMENDED USE AREA
This is the recommendeo level 1 environmental assessment procedure for determination of sulfate in aqueous samples.
5. OPERATIONAL PARAMETERS
A) RANGE
Method can be used for all concentration ranges of sulfate; aliquots of 40 mg sulfate/liter are recommended.
81 ACCURACY Accuracy results (bias) obtained by 34 analysts in 16 laboratories on samples containing 8.6, 9.2, 110, 122,
IBS and 199 mg/liter sulfate were -0.3, -0.8, -3.3, -4.1, +0.1, and -3.4 mg/liter, respectively.
C) PRECISION Precisions (as standard deviation) obtained on samples described above were 2.30, 1.78, 7.86, 7.50, 9.58 and
11.8 mg/liter, respectively.
6. REAGENTS REQUIRED
Barium chloride; proprietary reagents, such as Hach Sulfaver,
may be used.
7. EQUIPMENT REQUIRED
Colorimeter, spectrophotometer or nephelometer.
KEYWORD INDEX: Sulfate, aqueous effluents, turbidimetry.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02.
REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," National Environmental Research Center, EPA No. 625/6-74-003,
Washington, 1974, p. 277.
8) BACKGROUND INFORMATION
024 ASTM Cortttee D-19 and D-22, "Water; Atmospheric Analysis," Part 23, 0516-68. "Standard Methods of Test for Su fate
Ion in Industrial Water and Industrial Wastewater," American Society for Testing and Materials, nniiaae^r. a,
024 Taras,Tj°d(Bed.)', ^Standard Methods for the Examination of Water and Wastewater » 13th ed American Public Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D. C.,
., 1971, Method 213-C, p. 461.
c' f IELD APPLICATIONS
259
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1 TITI f DETERMINATION OF TOTAL AND DISSOLVED SULFIDE USING TITRIMETRIC
I. III 1C |OD)NE METHOD
Z IDENTIFICATION CODE
02-03-02-17
3. ABSTRACT OF METHODOLOGY
Method involves stripping of sulfides from an acidified sample by means of inert gas, followed by collection of the sulfide in a
zinc acetate solution with formation of zinc sulfide suspension. The suspension is treated with excess iodine; the iodine reacts
with the sulfide under acidic conditions. Unreacted iodine is titrated with thiosulfate solution, and the quantity of iodine
consumed by sulfide is determined by difference using starch as the indicator.
4. APPLICATION- Compliance, environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to aqueous (liquid and slurry) streams, including drinking, surface and saline waters, domestic and
industrial effluents.
B) INTERFERENCES/LIMITATIONS
Sulfite, thiosulfate, hydrosulfite, and other reduced sulfur compounds which are unstable in acid, interfere. Volatile iodine-
consuming substances give high results. Acid insoluble sulfides (e.g., CuS) are not determined by this method.
C) RECOMMENDED USE AREA
This is the recommended compliance procedure for determination of total and dissolved sulfides.
5. OPERATIONAL PARAMETERS
A) RANGE Sulfide concentrations above 1 mg/liter can be measured.
B) ACCURACY Accuracy of the method has not been determined.
C) PRECISION Precision of the method has not been determined.
6. REAGENTS REQUIRED
Zinc acetate solution, iodine, sodium thiosulfate solution,
inert gas, starch indicator.
7. EQUIPMENT REQUIRED
Standard laboratory equipment,
standard titration apparatus.
ft KEYWORD INDEX: Sulfide (total and dissolved), aqueous effluents, titrimetric iodine method.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," National Environmental Research Center, EPA No. 625/6-74-003,
Washington, 1974, p. 284.
B) BACKGROUND INFORMATION
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D. C., 1971,
Method 228A, p. 551-5. 3
C) FIELD APPLICATIONS
260
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1. TITLE DETERMINATION OF SULFITE USING TITRIMETRIC IODIDE-IODATE METHOD
2. IDENTIFICATION CODE
02-03-02-18
3. ABSTRACT OF METHODOLOGY
Method involves tltration of an acidified sample containing starch indicator with standard potassium iodide-iodate tltrant t
faint permanent blue end point, which is determined visually. The temperature of the sample should be maintained below 50°r TK
sample should be analyzed as quickly as possible, and care shou!d be taken to allow as little contact with air as possible (e
sample should not be filtered; the buret tip should be kept below the surface of the sample; dosed containers should be us d etc
to avoid oxidation of sulfite to sulfate. ;
4. APPLICATION- Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to aqueous (liquid and slurry) streams, including drinking and surface waters, sewage and industrial
wastes.
B) INTERFERENCES/LIMITATIONS
Organic compounds, ferrous iron and sulfide, and other oxidizable substances are positive interferences. Nitrite gives negative
interference; this can be eliminated by addition of sulfamic acid. Copper and other heavy metals interfere; these are
removed with EDTA.
C) RECOMMENDED USE AREA
This is the recommended compliance procedure for the determination of sulfite for aqueous samples such as ash dewatering
effluents, and dehydration waters.
5. OPERATIONAL PARAMETERS
A! RANGE 2 to 3 mg/liter sulfite.
B| ACCURACY Accuracy of the method has not been determined.
C) PRECISION Precision of the method has not been determined.
6. REAGENTS REQUIRED
Standard potassium iodide-iodate solutions, starch solution,
EDTA (optional), sulfamic acid (optional).
7. EQUIPMENT REQUIRED
Standard titration assembly; standard laboratory equipment.
8. KEYWORD INDEX: Sulfite, aqueous effluent, titrimetry, iodine-iodate.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02.
W. REFERENCES
*) PRIMARY SOURCE
'85 "Methods for Chemical Analysis of Water and Wastes," National Environmental Research Center, EPA No. 625/6-74-003,
Washington, 1974, p. 285.
81 BACKGROUND INFORMATION
ffi« ASTM Conwittee D-19 and D-22, "Water; Atmospheric Analysis," Part 23 Method D1339C 'Standard Methods of Test for
Sulfite Ion in Industrial Water," American Society for Testing and Materials, Phi adelphia, PJ- "". p. 436.
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater ' 13th ed American Public Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D. C.,
1971, Method 158, p. 337-8.
c) FIELD APPLICATIONS
261
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1. TITLE DETERMINATION OF CHLORIDE BY COLORIMETRY
2. IDENTIFICATION CODE
02-03-02-19
3. ABSTRACT OF METHODOLOGY
Method involves treatment of the sample with ferric ammonium sulfate (57% w/v) and mercuric thiocyanate (0.3% w/v). The chloride
ion reacts with the mercuric thiocyanate producing thiocyanate ion, which in turn combines with ferric ion to form red-colored
ferric thiocyanate.
The intensity of the color is then measured spectrophotometrically at a wavelength of 463 nm. The concentration of chloride is
then determined by comparison of the absorbance of the sample to a calibration curve prepared from reference standards containing
chloride ion.
4. APPLICATION^ Engineering evaluation R&D.
A) OPERATIONAL SCOPE
Method is applicable to aqueous (liquid and slurry) streams, including surface waters, domestic and industrial effluents.
B) INTERFERENCES/LIMITATIONS
Excessive color interferes. Bromides, iodides, cyanides, thiosulfates and nitrites interfere.
C) RECOMMENDED USE AREA
This is an alternative recommended engineering evaluation R&D procedure for determination of chloride in aqueous
effluents (see 02-03-02-09).
5. OPERATIONAL PARAMETERS
A) RANGE Method is applicable to all ranges of chloride, if suitable aliquots are used.
B) ACCURACY N/Q
C) PRECISION N/Q
& REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Ferric ammonium sulfate; mercuric thiocyanate solution in
methanol, sodium chloride.
Nessler tubes; filter photometer; spectrophotometer.
& KEYWORD INDEX: Chloride, aqueous effluents, ferric thiocyanate, colorimetry, spectrophotometry.
9. CROSS REFERENCE ID NUMBERS 01-02-02-01, 01-02-02-02; 02-03-02-09.
10. REFERENCES
A) PRIMARY SOURCE
018 Flegal, C.A., M.L. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Procedures for Process
Measurements: Trace Inorganic Materials," TRW Systems Group, EPA Contract #68-02-1393, July 1975.
B) BACKGROUND INFORMATION
343 Horowitz, W.(ed.), "Official Methods for Analysis of the Association of Official Analytical Chemists," llth ed., 1970.
C) FIELD APPLICATIONS
262
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TITLE DETERMINATION OF NITRATE NITROGEN BY PHENOL DISULFONIC ACID METHOD
Z IDENTIFICATION CODE
02-03-02-20
3, ABSTRACT OF METHODOLOGY
The sample is pretreated for the removal of interferences with: (1) aluminum hydroxide suspension to decolorize the sample, and (2)
silver sulfate solution for the removal of chloride. Nitrite is then converted -to nitrate with sulfuric acid, followed by potassium
permanganate or hydrogen peroxide. The pretreated sample is then neutralized to pH 7, then is treated with phenol disulfonic acid
reagent to form the characteristic yellow product. A standard hydroxide solution is then added until maximum yellow color is achieved
Flocculent hydroxides are then removed by passage through a filter, or addition of EDTA, until all turbidity redissolves. The yellow '
color is then determined spectrophotometrically at 410 ran.
4. APPLICATION- Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is primarily used to measure the nitrate content of impingers used to sample flue gas for NO,,.
B) INTERFERENCES/LIMITATIONS
Chloride interferes, but can be eliminated using silver sulfate. Nitrite interferes, but can be oxidized to nitrate with
permanganate or hydrogen peroxide. Excessive color interferes, but can be decreased using an aluminum hydroxide suspension.
C) RECOMMENDED USE AREA
This method is used in compliance testing of stacks for N02 content (see 01-01-01-02).
5. OPERATIONAL PARAMETERS
A) RANGE Method is sensitive to 1 ug nitrate (10 ppm in 100-ml sample).
B) ACCURACY N/Q
C) PRECISION N/Q
6. REAGENTS REQUIRED
Silver sulfate, phenol disulfonic acid, standard and stock nitrate
solutions; aluminum hydroxide suspension, sulfuric acid, potassium
permanganate, sodium hydroxide, hydrogen peroxide, EDTA.
7. EQUIPMENT REQUIRED
Spectrophotometer for use at 410 nm.
8. KEYWORD INDEX: Nitrate nitrogen, nitrogen dioxide, impingers, liquid/slurry, phenol disulfonic acid, spectrophotometry.
9. CROSS REFERENCE ID NUMBERS 01-01-01-02; 01-02-02-01, 01-02-02-02; 02-03-02-12.
W. REFERENCES
A) PRIMARY SOURCE
02" ASTM Committee D-19 and D-22, "Mater; Atmospheric Analysis," 1971 Annual Book of Standards, Part 23, D1608,
American Society for Testing and Materials, Philadelphia, PA., 1971, p. J»/-
B) BACKGROUND INFORMATION . ,_,n
343 Horowitz, W.(ed.), "Official Methods for Analysis of the Association of Official Analytical Chemists, llth ed., 1970.
FIELD APPLICATIONS
263
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1. TITLE DETERMINATION OF TOTAL SOLIDS
2. IDENTIFICATION CODE
02-03-02-21
3. ABSTRACT OF METHODOLOGY
Total solids is defined as the sum of homogeneous suspended and dissolved materials in a sample. An aliquot of the sample to be
determined is quantitatively transferred to a pre-weighed evaporating dish and evaporated to dryness (and constant weight) at
103-105 C on a steam bath.
4. APPLICATION- Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, as well as domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Large floating particles or submerged agglomerates should be removed from the test sample. Floating grease and oil should be
dispersed with a blender before aliquoting.
C) RECOMMENDED USE AREA
Compliance testing.
5. OPERATIONAL PARAMETERS
A) RANGE 10-20,000 rag/liter solids.
B) ACCURACY N/Q
C) PRECISION A standard deviation of 0.9 was found on samples of settled effluents.
6. REAGENTS REQUIRED
N/A
7. EQUIPMENT REQUIRED
Evaporating dishes (porcelain preferred; vycor or platinum),
desiccator, analytical balance.
& KEYWORD INDEX- Total solids, aqueous effluents, gravimetric method.
9. CROSS REFERENCE ID NUMBERS 01-02-02, 01-02-01; 02-03-02-22, 02-03-02-23, 02-03-02-24.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory, NERC,
EPA 625/6-74-003, Washington, 1974, p. 270.
204 Taras, M.J., "Standard Methods for the Examination of Water and Wastewater," American Public Health Association, 13th ed.,
Method 224A, 1971, p. 535.
B) BACKGROUND INFORMATION
532 Howard, C.S., "Determination of Total Dissolved Solids in Water Analysis," I_ndL_Eng. Chem., Anal. Ed., 5, 4 (1933).
533 Sokoloff, V.P., "Water of Crystallization in Total Solids of Water Analysis," In_d_,.Jng. Chem., Anal. Ed., 5, 336 (1933).
C) FIELD APPLICATIONS
-------
1. TITLE DETERMINATION OF TOTAL DISSOLVED (FILTERABLE) SOLIDS
_ . _
3, ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-03-02-22
To determine total dissolved (filterable) solids, the sample is filtered through a standard glass fiber filter The filtrate is
evaporated to dryness (and constant weight) in a pre-weighed dish at 180°C in an oven. The increase in weight represents total
dissolved or filterable solids and includes all materials (liquids and solids) which pass through the filter and are not volatilized
during the drying process.
4. APPLICATION' Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Samples containing high concentrations of calcium, magnesium, chloride, sulfate, and bicarbonate will require prolonged drying,
desiccation and rapid weighing. Maximum total residue should be less than 200 mg to prevent encrustation and water entrapment.
0 RECOMMENDED USE AREA
Compliance testing.
5. OPERATIONAL PARAMETERS
A) RANGE 10-20,000 mg/1 filterable solids.
B) ACCURACY N/Q
Cl PRECISION A synthetic sample containing 134 mg/1 filterable residue was determined with a standard deviation of +13 mg/1 in
18 laboratories (using a drying temperature of 103-105°C).
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
N/A
Glass fiber filter discs, filter holder, suction flash, Gooch
crucibles, evaporating dishes, steam bath, drying oven,
desiccator, analytical balance.
8. KEYWORD INDEX: Total dissolved solids, total filterable solids, aqueous effluents, glass fiber filtration.
9. CROSS REFERENCE ID NUMBERS 01-02-02, 01-02-01; 02-03-02-21, 02-03-02-23, 02-03-02-24.
«>. REFERENCES
A) PRIMARY SOURCE
!85 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory,
National Environmental Research Center, EPA 625/6-74-003, Washington, 1974, p. 266.
204 Taras, M.J. (ed.J, "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D.C., 1971,
Method 224E, p. 539.
B) BACKGROUND INFORMATION
534 Chanin, G., R.B. Alexander, E.H. Chow and J. Powers, "Use of Glass Fiber Filter Medium in the Suspended Solids Determination,
Sewage and Ind. Wastes, 30, 1062 (1958).
535 Wychoff, B.M., "Rapid Solids Determination Using Glass Fiber Filters," Water and Sewage Works, 1.1.1. 277 (1964).
ci FIELD APPLICATIONS
265
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1. TITLE DETERMINATION OF TOTAL SUSPENDED (NON FILTERABLE) SOLIDS
2. IDENTIFICATION CODE
02-03-02-23
3. ABSTRACT OF METHODOLOGY
The sample is filtered through a pre-weighed standard glass fiber filter. The filter and residue are dried to constant weight in
an oven at 103-105°C. The increase in weight of the filter represents the total suspended (nonfilterable) residue. The filtrate
from this method may be used in a determination of total dissolved (filterable) solids (see 02-06-01-02).
4. APPLICATION: Compliance, environmental assessment.
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
The quantity of residue on the filter should be minimized in order to prevent encrustation and entrapment of water.
C) RECOMMENDED USE AREA
Compliance testing.
5. OPERATIONAL PARAMETERS
A) RANGE 10-20,000 mg/1 suspended solids.
B) ACCURACY N/Q
C) PRECISION N/Q
6. REAGENTS REQUIRED
N/A
7. EQUIPMENT REQUIRED
Glass fiber filter discs, filter holders, suction flask, Gooch
crucibles, drying oven, desiccator, analytical balance.
8. KEYWORD INDEX: Total suspended solids, total nonfilterable solids, aqueous effluent, glass fiber filtration.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02; 02-03-02-21, 02-03-02-22, 02-03-02-24.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory, National
Environmental Research Center. EPA 625/6-74-003, Washington, 1974, p. 268.
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D.C., 1971,
Method 224C, p. 537.
B) BACKGROUND INFORMATION
536 Degen, J., and F.F. Nussberger, "Notes on the Determination of Suspended Solids," Sewage and Ind. Wastes, 28, 237 (1956).
537 Nusbaum, I., "New Method for Determination of Suspended Solids," Sew_a£e_and___I_nd..Wastes,, 30, 1066 (1958).
538 Smith, A.L., and A.E. Greenberg, "Evaluation of Methods for Determining Suspended Solids in Wastewater," J. Water Pollut.
Control Fed.. 35, 940 (1963).
C) FIELD APPLICATIONS
265
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1, TITLE DETERMINATION OF TOTAL VOLATILE SOLIDS
__
3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-0302-24
To det.nrin.tot.lvol.tn. solids, the residue obtained fro, the determination of total dissolved (filterable) solids (02 03 02 21)
or fro, the etermination of total suspended (nonfilterable) solids (02-03-02-23) is ignited at 550°C in a 1 a h"
loss in weight is then reported as rug/liter volatile residue. ™rnace. The
This procedure also gives an estimate of the amount of organic matter which is present in the solid fraction of the sample.
4. APPLICATION- Compliance, environmental assessment.
A) OPE RATIONAL SCOPE
Method is applicable to sewage, activated sludge, industrial wastes and bottom sediments.
Bl INTERFERENCES/LIMITATIONS
The method is subject to errors from the following sources: loss of water of crystallization; loss of volatile organic matter
prior to combustion; incomplete oxidation of complex organic substances; and decomposition of mineral salts during combustion.
C) RECOMMENDED USE AREA
Compliance testing.
S. OPERATIONAL PARAMETERS
A) RANGE 10-20,000 mg/1 solids.
B) ACCURACY N/Q
C) PRECISION A study of four samples using ten replicates in three laboratories gave a standard deviation of +11 mg/1 at 170 mg/1
volatile residue concentration.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
N/A
Muffle furnace (to 550°C), analytical balance.
8. KEYWORD INDEX-' Total volatile solids, aqueous effluents, muffle furnace ashing.
9. CROSS REFERENCE ID NUMBERS 02-03-02-21, 02-03-02-23; 01-02-01, 01-02-02.
10. REFERENCES
A) PRIMARY SOURCE
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory, National
Environmental Research Center, EPA 625/6-74-003, Washington, 1974, p. 272.
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater" 13th ed ^'"J^"^"^?!
Association (APHA), American Water Works Association, and Water Pollution Control Federate, Washington, B.C., is/1,
Method 224B, p. 536.
Bl BACKGROUND INFORMATION
539 Symons, G.E., and B. Morey, "The Effect of Drying Time on the Determination of Solids in Sewage and Sewage Sludges,"
Sewage Works J., 13, 936 (1941).
540 Howard, C.S., "Determination of Total Dissolved Solids in Water Analysis," I.nd, Eng, Chem,, Anal. Ed., 5, 4 (1933).
533 Sokoloff, V.P., "Water of Crystallization in Total Solids of Water Analysis," Ind,..En.a, Chem., Anal. Ed., 5, 336 (1933).
C) FIELD APPLICATIONS
267
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1. TITLE DETERMINATION OF TOTAL HARDNESS
2. IDENTIFICATION CODE
02-03-02-25
3. ABSTRACT OF METHODOLOGY
Total hardness is determined by titrating the sample with ethylenediamine tetra-acetic acid in the presence of an indicator buffered
at pH 10. Calcium and magnesium ions in the sample are sequestered upon the addition of disodium ethylenediamine tetra-acetate
(Na?EDTA). 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.
4. APPLICATION^ Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Certain metal ions (Al+3, Ba+2, Cd , Pb ) interfere but can be removed by the addition of various masking agents such as Clf
Suspended or colloidal organic matter may interfere, but can be removed by evaporation of a sample aliquot on a steam bath
followed by heating in a muffle furnace to 550°C.
C) RECOMMENDED USE AREA
Compliance testing.
5. OPERATIONAL PARAMETERS
A) RANGE Method is suitable for all hardness concentrations. To avoid large titration volumes, sample aliquots of <25 rag
CaC03 should be used.
B) ACCURACY The analysis of six samples in 19 laboratories gave accuracies (as mg/liter CaCOj) ranging from -0.003 to--14.3 for
samples having 31 to 444 mg/liter hardness as CaC03_
C) PRECISION Precisions obtained on the above analyses ranged from 2.52 to 9.65 mg/liter as CaCO,.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Ammonia buffer, inhibitor solutions, Eriochrome Black T, sodium
salt of EDTA.
Standard titration apparatus, evaporating dish, muffle furnace
(optional).
& KEYWORD INDEX- Total hardness, calcium and magnesium, aqueous effluents, titrimetry.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02; 02-02-01-12.
10. REFERENCES
A) PRIMARY SOURCE
185
"Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory, National
Environmental Research Center, EPA 625/6-74-003, Washington, 1974, p. 68.
204 Taras, H.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health
Association (APHA), American Water Works Association, and Water Pollution Control Federation, Washinqton, D C , 1971,
Method 122B, p. 179.
B) BACKGROUND INFORMATION
541 Barnard, A.J., Jr., W.C. Broad, and H. Flaschka, "The EDTA Titration," Chemist Analyst. 45, 86 (1956) and 46, 46 (1957).
542 Connors, J.J., "Advances in Chemical and Colorimetric Methods," i-_JiU_Water__Work.Assoc., 42, 33 (1950).
543 Schwarzenbach, G., and H. Flaschka, "Complexometric Titrations," 2nd ed., Barnes and Noble, Inc., New York, 1969.
C) FIELD APPLICATIONS
268
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TITLE DETERMINATION OF COLOR BY SPECTROPHOTOMETRIC METHOD
2. IDENTIFICATION CODE
02-03-02-26
ABSTRACT OF METHODOLOGY
Method involves measurement of the visible absorption spectrum (percent transmittance) of the sample on a spectrophotometer. The
transmittance values corresponding to the wavelengths shown in Columns X, V and Z of Table are then tabulated and the
totals are multiplied by the appropriate factors to obtain tristimulus values, X, Y and Z. The tristimulus value V is the percent
luminance of the waste. Next, the trichromatic coefficients X and Y are calculated using the equations:
X + Y + Z
Then, the pdiint (X, Y) is located on one of the chromativity diagrams in Figure and the dominant wavelength (in HIM) and
purity (in percent) are determined. The hue is determined from the dominant wavelength as indicated in Table
Since the method is pH dependent, two samples are determined simultaneously, one at the original pH, and one having pH of 7.6 from
the addition of sulfuric acid and sodium hydroxide.
4. APPLICATION- Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
B) INTERFERENCES/LIMITATIONS
Turbidity interferes; this can be eliminated by sample centrifuging and filtration. The determination should be performed as soon
as possible on the collected sample, which should be refrigerated at 4°C to retard biological activity.
C) RECOMMENDED USE AREA
Compliance testing.
5. OPERATIONAL PARAMETERS
Al RANGE Method is applicable to all colored wastes, including highly colored industrial wastes which cannot be determined by
the platinum-cobalt method (02-02-01-35).
B) ACCURACY Not available.
Cl PRECISION Not available.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Concentrated sulfuric acid, sodium hydroxide.
Spectrophotometer, pH meter, centrifuge, filter funnel, standard
laboratory glassware.
8, KEYWORD INDEX: Color, aqueous effluents, spectrophotometry.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02; 02-03-02-27.
W. REFERENCES
185 »MethodsYfo°rUChCemical Analysis of Water and Wastes", Methods Development and Quality Assurance Research Laboratory, National
Environmental Research Center, EPA 625/6-74-003, Washington, 1974, p. 39.
204 Jaras, H.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health Association
(APHA), American Water Works Association, and Water Pollution Control Federation, Washington, O.C., 1971, Method 206A, p. 392.
W BACKGROUND INFORMATION
44 Hardy, A.C., "Handbook of Colorimetry," Technology Press, Boston, Mass., 1936.
545 Rudolphs, W., and W.D. Hanlon, "Color in Industrial Wastes I. Determination by Spectrophotometric Method," Sewage and Ind.
>!«test23, 1125 (1951).
cl FIELD APPLICATIONS
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1. TITLE DETERMINATION OF COLOR BY PLATINUM-COBALT METHOD
Z IDENTIFICATION CODE
02-03-02-27
3. ABSTRACT OF METHODOLOGY
Method involves visual comparison of the sample with platinum-cobalt standards. The color of the solution is measured in units;
one unit of color is the color produced by 1 mg/1 platinum as chloroplatinate ion. The stock standard solution, which has a
color of 500 units, is prepared by dissolving 1.246 g potassium chloroplatinate and 1.00 g cobaltous chloride in 100 ml HC1 and
diluting to 1000 ml. Standards having color units of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, and 70 are then prepared from
the stock solution. The color of the sample (or sample aliquot) is then matched to that of the standards.
4. APPLICATION: Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to all aqueous streams except highly colored industrial wastes.
B) INTERFERENCES/LIMITATIONS
Visible turbidity interferes; this can be removed by centrifugation. Since the method is pH dependent, the pH of the sample should
be recorded.
C) RECOMMENDED USE AREA
Compliance testing.
5. OPERATIONAL PARAMETERS
A) RANGE Method is applicable to all samples except highly colored industrial wastes; the sample can be diluted until its
color is within the range of the standards.
B) ACCURACY Not available at this time.
Cl PRECISION Not available at this time.
6. REAGENTS REQUIRED
Potassium chloroplatinate, cobaltous chloride, concentrated
hydrochloric acid.
7. EQUIPMENT REQUIRED
Matched Nessler tubes, pH meter,
standard laboratory glassware.
8. KEYWORD INDEX: Color, aqueous effluents, colorimetry, platinum-cobalt method.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02; 02-03-02-26.
10. REFERENCES
A) PRIMARY SOURCE
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health Association
(APHAJ, American Water Works Association, and Water Pollution Control Federation, Washington, D.C., 1971, Method 118, p. 160.
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory, National
Environmental Research Center, EPA 625/6-74-003, Washington, 1974, p. 36.
B) BACKGROUND INFORMATION
546 Knight, A.6., "The Photometric Estimation of Color in Turbid Waters," J. Inst. Water Enq.. 5, 623 (1951).
547 Jullander, I., and K. Brune, "Light Absorption Measurements on Turbid Solutions," Acta. Chem. Scandinav.. 4, 870 (1950).
548 Lamar, W.L., "Determination of Color of Turbid Waters," Anal. Chem., 21, 726 (1949).
549 Block,.A.P., and R.F. Chrestman, "Characteristics of Colored Surface Waters," J. Am. Water Works Assoc.. 55_, 753 (1963)'.
550 Rudolphs, W., and W.D. Hanlon, "Color in Industrial Wastes," Sewage and Ind. Wastes, 23_, 1125 (1951).
C) FIELD APPLICATIONS
270
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1. TITLE DETERMINATION OF SPECIFIC CONDUCTANCE
^____ -....-.... .
3. ABSTRACT OF METHODOLOGY
Z IDENTIFICATION CODE
02-03-02-28
The specific conductance of a sample is determined by measurement of electrical resistance or its inverse, conductance, between
two electrodes one centimeter apart. A specific conductance cell, a Wheatstone bridge and a source of electric current, or a self-
contained conductance cell, are used to measure the electrical resistances of a sample and a potassium chloride solution of known
specific conductance. Since the method is temperature dependent, a water bath is used to maintain the samples at 25°c
4. APPLICATION- Compliance, environmental assessment.
A| OPERATIONAL SCOPE
Method is applicable to drinking, surface and saline waters, domestic and industrial wastes.
8) INTERFERENCES/LIMITATIONS
Samples should be protected from exposure to ammonia or acidic gases before measurement; also, samples should be protected from
absorption or desorption of dissolved gases.
C) RECOMMENDED USE AREA
Compliance testing.
& OPERATIONAL PARAMETERS
A) RANGE
Suitable for use on all aqueous samples
B) ACCURACY Analyses in 17 laboratories of six synthetic samples containing increments (as specific conductance) of 100 to
1710 umho/cm gave accuracies as percent bias from -0.76 to -5.36.
C) PRECISION The determinations on the samples described above gave precisions ranging from 7.55 to 119 umho/cm. In a single
laboratory using samples with an average conductivity of 536 umho/cm, a standard deviation of ±6 was obtained.
6, REAGENTS REQUIRED
Potassium chloride, reagent grade water, platinizing solution
(chloroplatinic acid, lead acetate) hydrochloric acid.
7. EQUIPMENT REQUIRED
Specific conductance cell, Wheatstone bridge, source of electric
current, water bath (25°C), standard laboratory glassware.
8. KEYWORD INDEX: Specific conductance, aqueous effluents, conductivity meter
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02.
10.
REFERENCES
A) PRIMARY SOURCE
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Public Health Association
(APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D.C., 1971, Method Ibt, p. ui.
185 "Methods for Chemical Analysis of Water and Wastes," Methods Development and Quality Assurance Research Laboratory, National
Environmental Research Center, EPA 625/6-74-003, Washington, 1974, p. 275.
024 ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 Annual Book of ASTM Standards, Part 23, D1125-64, "Standard
Methods of Test for Electrical Conductivity of Water," American Society for Testing and Materials, Philadelphia, HA., is/i,
PP. 156-161.
B> BACKGROUND INFORMATION
551 Robinson, R.A., and R.H. Stokes, "Electrolyte Solutions," 2nd ed., Academic Press, New York, N.Y., 1959, p. 466.
552 Lind, J.E., R.M. Fuoss and J.J. Zwolenik, "Calibration of Conductance Cells at 25°C with Aqueous Solutions of Potassium
Chloride," J. Am. Chem. Soc., 81., 1557 (1959).
271
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PAGE 2 OF 2 FOR
TITLE DETERMINATION OF SPECIFIC CONDUCTANCE (CONTINUED)
ID NO.
02-03-02-28
C) FIELD APPLICATIONS
553 Jones, G., and B.C. Bradshaw, "The Measurement of the Conductance of Electrolytes. V. A Redetermination of the Conductance of
Standard Potassium Chloride Solutions in Absolute Units," J. Amer. Chem. Soc., 55_, 1780 (1933).
554 Rossum, J.R., "Conductance Method for Checking Accuracy of Water Analyses," Anal. Chem.. 21_, 631 (1949).
555 Wilcox, L.V., "Electrical Conductivity," J. Am. Hater Works Assoc.. 42, 775 (1950).
272
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]. TITLE DETERMINATION OF TURBIDITY BY THE NEPHELOMETRIC METHOD
2. IDENTIFICATION CODE
02-03-02-29
3. ABSTRACT OF METHODOLOGY
A turbidimeter is used to measure the intensity of light scattered by a sample, compared to that scattered by a standard reference
suspension The turbidimeter consists of a nePhe10meter having a light source, one or more photoelectric detectors, and a readout
device winch indica es the light intensity scattered at right angles to the incident beam. Readings are recorded in nephelometric
turbidity unm (NTU's). A standard polymer solution (hydrazine sulfate or hexa.ethylenetetran.ine) is used as a reference
for instrument calibration.
4. APPLICATION- Compliance, environmental assessment.
A) OPERATIONAL SCOPE
Method is applicable to domestic, surface and saline waters.
B) INTERFERENCES/LIMITATIONS
Samples should be determined as soon as possible, since sediment will settle out and give low readings. Air or gas bubbles will
give high results. Excessive solution color will result in low values.
0 RECOMMENDED USE AREA
Compliance testing.
5. OPERATIONAL PARAMETERS
A) RANGE Suitable for use on all aqueous samples in the range of 0 to 40 nephelometric turbidity units.
B) ACCURACY Not available at this time.
C) PRECISION Standard deviations of ±0.60, ±0.94, ±1.2 and ±4.7 units were obtained in a single laboratory using surface water
samples at levels of 26, 41, 75 and 180 NTU.
6. REAGENTS REQUIRED
Turbidity-free water, standard turbidity suspension (hydrazine
sulfate or hexamethylenetetramine).
7. EQUIPMENT REQUIRED
Turbidimeter (such as Hach
pore size membrane filter,
analytical balance.
Model 2100 turbidimeter), 0.45p
standard laboratory glassware,
8. KEYWORD INDEX: Turbidity, aqueous effluents, nephelometry.
9. CROSS REFERENCE ID NUMBERS 01-02-01, 01-02-02.
10. REFERENCES
A) PRIMARY SOURCE
204 Taras, M.J. (ed.), "Standard Methods for the Examination of Water and Wastewater," 13th ed., American Publie Health Association
(APHA), American Water Works Association, and Water Pollution Control Federation, Washington, D.C., 1971, Method 163A, p. 349.
185 "Methods for Chemical Analysis of Water and Wastes." Methods Development and Quality Assurance Research Laboratory, National
Environmental Research-Center, EPA 625/6-74-003, Washington, 1974, Page 295.
B) BACKGROUND INFORMATION
556 Knight, H.G., "The Measurement of Turbidity in Water," J. Inst. Water Eng., 5_, 633 (1951).
557 Packham, R.F., "The Preparation of Turbidity Standards," Pmr. Snc. Hater Treatment and Exam.. U, 64 (1962).
558 Eden, G.E., "The Measurement of Turbidity in Water. A Progress Report on the Work of the Analytical Panel," P.roc. Soc. Water
Treatment and Exam.. 14, 27 (1965).
°1 FIELD APPLICATIONS
559 Black, A.P., and S.A. Hannah, "Measurement of Low Turbidities," ^ Am. water Works Assoc,, .57. 901 (1965).
273
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1. TITLE VISUAL DETERMINATION OF THE OPACITY OF EMISSIONS FROM STATIONARY SOURCES
2. IDENTIFICATION CODE
02-03-02-30
3. ABSTRACT OF METHODOLOGY
Method Involves the visual determination of the relative opacity of an emission (usually a plume) by a qualified observer using a
Ringelman smoke card. The determination of plume opacity involves the minimization of certain variables which may influence the
appearance of the plume but which may be controlled. These include: (1) angle of the observer with respect to the plume; (2) point
of observation of attached and detached steam plume; and (3) angle of the observer with respect to the plume emitted from a rectangular
stack with a large length-to-width ratio. Other variables which may not be controllable are luminescence and color contrast between
the plume and the background against which the plume is viewed.
4. APPLICATION: Compliance.
A) OPERATIONAL SCOPE
Method is applicable to the determination of the relative opacity of visible emissions from stationary sources.
B) INTERFERENCES/LIMITATIONS
Positive bias may result when the plume is viewed under maximum contrasting conditions. Negative bias can be obtained when the
plume is viewed under less contrasting conditions.
C) RECOMMENDED USE AREA
Compliance testing.
5. OPERATIONAL PARAMETERS
A) RANGE Method can be used to measure any range of plume opacity.
B) ACCURACY N/Q
C) PRECISION ±5% or better.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Not applicable.
Smoke miter, including light source and photo cell.
a KEYWORD INDEX: Opacity,'-Stationary' Sources, Compliancy. '
9. CROSS REFERENCE ID NUMBERS 01-01; 01-05.
10. REFERENCES
A) PRIMARY SOURCE
560 U.S. Environmental Protection Agency, "Visual Determination of the Opacity of Emissions from Stationary Sources," Federal Register 36
No. 247, 24895, Dec. 23, 1971.
Bl BACKGROUND INFORMATION
561 Air Pollution Control District Rules and Regulations, Los Angeles County, Air Pollution Control District, Chapter 2, Schedule 6,
Regulation 4, Prohibitions, Rule 50, 17pp."
562 Kudluk, R., "Ringelmann Smoke Chart," U.S. Dept. of Interior, Bureau of Mines, Information Circular No. 8333, May 1967.
563 Weisburd, M.I., Field Operations and Enforcement Manual for Air, U.S. Environmental Protection Agency, Research Triangle Park, N.C.
APTD-1100, Aug. 1972, p. 4.1-4.36.
C) FIELD APPLICATIONS
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Table of Contents for 02-04 Solid and Particulate Compound Analysis
02-04-01 Microscopic Analysis
02-04-01-01 Polarized Light Microscope Identification of
Air Particulate
02-^04-01-02 Quantitative Analysis Using Transmission
Electron Microscopy (TEM) ,
02-04-01-03 Electron Probe Microanalysis (EPMA) for
Particulate Analysis
02-04-01-04 Scanning Electron Microscope (SEM) for
Qualitative Particulate Analysis
02-04-02 Chemical Analysis
02-04-02-01 Quantitative Compound Chemical Analysis by
X-Ray Powder Diffraction (XRD)
02-04-^2-02 Compound Identification by Electron Spectro-
scopy for Chemical Analysis (ESCA)
02-04-02--03 Chemical (Elemental) Analysis Using Scanning
Electron Microscope (SEM), Electron Probe Microanalysis
(EPMA) with an Energy Dispersive X-Ray Spectrometer
(EDX)
275
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APPLICATION MATRIX FOR 02-04 SOLID AND PARTICIPATE COMPOUND ANALYSIS
METHOD
02-04-01-01
02-04-01-02
02-04-01-03
02-04-01-04
02-04-02-01
02-04-02-02
02-04-02-03
LEVEL I
ENVIRONMENTAL
ASSESSMENT
•
COMPLIANCE
ENGINEERING
EVALUATION
R/D
•
•
•
•
•
•
276
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SOLID AND PARTICULATE COMPOUND ANALYSIS- ID No. 02-04
A variety of instruments are available for the analysis of solids and
parti cul ate matter for morphological characteristics and compound analysis.
Analyses are routinely performed by scanning electron microscopy, electron
probe microanalysis, transmission electron microscopy, X-ray diffraction,
electron spectroscopy, and polarized light microscopy. They can be used to
determine a wide range of morphological characteristics, such as size,
shape, and size frequencies of the particles. These instruments are non-
destructive, allow multiple studies on single specimens, and are generally
characterized by high spatial resolution. A summary of these techniques,
the detectable particle sizes and principal information derived are
shown in Table 02-04A.
02-04-01 Microscopic Analysis (Abstracts 02-04-01-01 Through
Light microscopy (02-04-01-01) is routinely used for physical
inspection of samples, particularly as a means of quality control for
verification of the physical integrity of the sample. Light micro-
scope techniques measure incident and transmitted light and employ
bright field, dark field, polarized light and phase contrast techniques
to identify specimens. Most common minerals (or compounds) as small as
lOy can be identified.
One of the principal tools for analytical and morphological deter-
minations is the Scanning Electron Microscope (SEM) (02-04-01-04).
Quantitative (references 344, 345, 347, 355) analysis of particles as
small as O.ly for morphological and elemental composition is possible
when an energy-dispersive detector is used. Characteristic X-ray
emissions can be obtained from elements of atomic number 11, while
elemental content of 1% by weight can be routinely determined.
In the identification of fiber-like particles such as asbestos,
Transmission Electron Microscopy (TEM) (02-04-01-02) is preferred to
SEM and EPMA techniques. This is because: 1) smaller fibers can be
observed and identified by TEM, and 2) TEM using selected area electron
diffraction is more dependable for elemental analysis of particles. TEM
277
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Technique
Detectable
Particle Size
Principal Information
Derived
Method of Identification
00
Polarized Light Microscopy
Transmission Electron
Microscopy
Scanning Electron Microscopy
Electron Probe Microanalysis
Scanning Electron Microscope-
Energy Dispersive X-Ray
X-Ray Diffraction
Electron Spectroscopy for
Chemical Analysis
(TEM)
(SEM)
(EPMA)
(SEM-EDX)
(XRD)
(ESCA)
5 to
0.01-lp.
0.1 to 100(1
Ifi and larger
Structural parameters; general
sample integrity
Particle size distributions
Surface microstructure
Morphological parameters;
elemental distribution
Elemental ratios for
individual particles
Direct determination of
crystalline compounds present
Direct compound analysis
Imaging techniques using incident
and transmitted light
Detection of transmitted electron beam
Detection of secondary electron beam
Detection of emitted X-rays; compound
identification by ratio of elements
Compound identification by ratio of
known elements
By diffraction pattern of crystalline
material
By characteristic chemical shift of
photoelectron spectra
Table 02-04-A. Morphological and Compound Characterization Techniques.
-------
(reference 346) analyses are generally reliable even when the collected
particles are small in number compared to background particles because
a unique system of blank determination. TEM has been used to examine
particles ranging from 0.01 to 1 micron in size.
Electron Probe Microanalysis (EPMA) (02-04-01-03) is particularly
useful for obtaining compositional information, and a spatial resolution
of lym can be obtained for a sample. EPMA (reference 350) which is
equipped with an Energy Dispersive Spectrometer (reference 350) can
rapidly determine all elements with an atomic number greater than 11.
X-ray imaging systems are particularly useful by providing a visual map
of elemental distributions. Wavelength dispersive crystal spectrometers
are also available for quantitative analyses, and can determine characteristic
X-ray emissions from elements with atomic numbers of 6 or greater. Routine
precisions of ±1% can be attained; even more precise results are obtained
when standards are available which closely match the specimen being analyzed.
02-04-02 Chemical Analysis (Abstracts 02-04-02-01 Through 02-04-02-03)
Qualitative and quantitative chemical analyses are routinely performed
using SEM and EPMA (02-04-02-03) techniques, particularly when they are
coupled to energy dispersive spectrometers. These techniques have been
used to measure the distributions of Zn, Cu and Fe in mud samples; the Ag,
S, and Si distribution in ores, and the Cu and Zn content of brass samples.
The composition of fly ash also is routinely determined. Quantitative chemical
analysis is based on one or more computational schemes which convert the
x-ray intensity ratios to the chemical composition of the sample.
X-ray Diffraction (XRD) (02-04-02-01) provides a rapid method for
qualitative and semiquantitative determination of solids and particulates,
and yields compound information to compliment the morphological and
elemental information supplied by SEM, EPMA and TEM. Materials such as
lime, calcium carbonate, road salt, coke dust and aerosol from sinter
emissions as well as particulate samples obtained from dustfall or high
volume filter media are easily determined (references 351, 352, 353, 354).
The components of a sample may be identified by matching the diffraction
pattern obtained from a particle with known ASTM patterns. Internal
standards, such as calcium carbonate, kaolin or powdered amorphous glass
are also used.
279
-------
Unlike SEM, EPMA and TEM, Electron Spectroscopy for Chemical Analysis
(ESCA) (02-04-02-02) performs direct compound identification. ESCA
techniques can be used to qualitatively identify all elements present in
a sample, with the exception of hydrogen, and is also used in compound
identification (references 349, 356). ESCA measures the energy of the
photoelectrons ejected from a sample under bombardment by monoenergetic
X-rays. Minute shifts in the energy of the photoelectrons from the same
element but in different compounds identify the element's origin (compound).
Since peak areas are proportional to the concentrations of the correspond-
ing elements in a sample, calibration curves are used in quantitative compound
analysis. ESCA techniques have been used in the determination of small
molecules, such as carbon monoxide, nitrogen, methane, and in the identi-
fication of larger organic compounds (organophosphorous compounds, mercury-
containing compounds, fluoromethane gases). Recently (reference 356) ESCA
was used to measure the kind and quantity of sulfur and nitrogen compounds
present in an atmospheric aerosol.
REFERENCES
344 Goldstein, J.I., and H. Yakowitz, "Practical Scanning Electron
Microscopy," Plenum Press, New York, 1975.
345 Woldseth, R., "X-Ray Energy Spectrometry," Kevex Corporation,
Burlingame, CA., 1st ed., June 1973.
346 Blanchard, M.B., N.H. Farlow and G.V. Ferry, "Methods of Analyzing
Microsize Particulate Aerosols and Contaminants," AIAA paper No.
71-1104, Joint Conference on Sensing of Environmental Pollutants,
Nov. 8-10, 1971, p. 3.
347 Griffiths, B.W., "Analytical Scanning Electron Microscopy,"
Am. Lab.. April 1974, p. 83.
348 Brundle, C.R., "Some Recent Advances in Photoelectron Spectroscopy,"
Appl. Spect., 25(1), 8, 1971.
349 Betteridge, D., "Analytical Aspects of Photoelectron Spectroscopy,"
Intern. J. Envir. Anal. Chem.. 1_, 243-57 (1972).
350 Performance Evaluation of an Ion Microprobe, Applied Research
Laboratories brochure, P.O. Box 129, Sunland, CA., September 1971.
351 Richards, A.L., "Estimation of Trace Amounts of Chrysotile Asbestos
by X-Ray Diffraction," Anal. Chem.. 44(11), 1872, September 1972.
352 Oberg, M., "Evaluation of Quartz in Airborne Dust in the 0.5-2-
Micron Size Range," Environ. Sd. Tech.. 2.(10), 795, October 1968.
280
-------
353 Warner, P.O., J.O. Jackson and L. Saod, "Identification and
Quantitative Analysis of Participate Air Contaminants by X-Ray
Diffraction Spectrometry," Air Pollution Control Association,
64th Annual Meeting, Atlantic City, N. J., June 27-July 2, 1971.
354 Baldock, P.J., and A. Parker, "X-Ray Powder Diffractometry of Small
(20 u9 to 1 yg) Samples Using Standard Equipment," J. Appl. Cryst.,
6,, 153 (1973).
355 Waller, R.E., A.G.F. Brooks and J. Cartwright, "An Electron
Microscopy Study of Particles in Town Air," Int. J. Air Water Poll..
I, 779-786.
356 Novakov, T., et al, "Aerosols and Atmospheric Chemistry," G.M. Hidy
(ed.), Academic Press, N. Y., 1972, p. 285.
281
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PAGE 1 OF 2 FOR
1. TITLE POLARIZED LIGHT MICROSCOPE IDENTIFICATION OF AIR PARTICULATE
2. IDENTIFICATION CODE
02-04-01-01
3. ABSTRACT OF METHODOLOGY
Polarized light is used to view particles collected from various sources. Particles are first crushed to 0.05 ram and then
examined with the microscope. Figure 02-Q4-01-01A, which is taken from the primary reference, describes the steps leading to
particle identification. Of special importance are the observations of refractive index, (relief), isotropy or anisotropy, bire-
fringence, pleochroism, fracture, color, and crystal habit.
4. APPLICATION:
Environmental assessment.
A) OPE RATIONAL SCOPE
This method can be used to identify collected particulates from filters, cyclones, or impactors. Crystalline materials
are best suited for study, though many substances can be identified by observation of morphological properties
(see Ref. 359).
B) INTERFERENCES/LIMITATIONS
Polarized light microscopy is limited to single particle analysis. Trace constituents absorbed on particles or extremely
small particles (<0.5 p) must be measured by another technique (SEM EDX). Homogeneity is important for correct
identification.
C) RECOMMENDED USE AREA
Level 1 environmental assessment quality control and preliminary screening.
5. OPERATIONAL PARAMETERS
A) RANGE Particles > 0.5 y, major components.
B) ACCURACY N/Q (if particles are homogeneous, ±5:.' estimated).
C) PRECISION
N/Q
6. REAGENTS REQUIRED
Shellaber's Oil.
7. EQUIPMENT REQUIRED
Petrographic microscope, microscope slides, cover glasses.
& KEYWORD INDEX: Analysis, polarized light microscopy.
9. CROSS REFERENCE ID NUMBERS 01-06-01, 02; 01-04-01, 02.
10. REFERENCES
A) PRIMARY SOURCE
357 West, P.W., The Chemist Analyst, 34, 76 (1945).
358 West, P.W., The Chemist Analyst, 35, 28 (1946).
B) BACKGROUND INFORMATION
359 McCrone, W.C. (ed.), "The Particle Atlas," Ann Arbor Science Publishers, Inc., Ann Arbor, Michigan, 1967.
360 Chamot, E.M., and C.W. Mason, "Handbook of Chemical Microscopy," New York, John Wiley and Sons Inc., 2nd ed.,
1939, 2 volumes,
C) FIELD APPLICATIONS
282
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TITLE
PAGE 2 OF 2 FOR
ID NO.
02-04-01-01
CRUSH AND SCREEN SAMPLE
I
USING MEDIUM POWER, NOTE CRYSTAL SHAPE,
CLEAVAGE, INCLUSIONS, COLOR, PLEOCHROISM.
NOTE DEGREE AND CHARACTER OF RELIEF; DETER-
MINE APPROX. REFRACTIVE INDEX. FROM THESE
OBSERVATIONS, IDENTIFY FROM MEMORY OR BY
DIRECT COMPARISON.
ISOTROPIC
(CRYSTALS DARK)
I
OBSERVE BETWEEN CROSSED
PRISMS AND ROTATE STAGE
—^ ANISOTROPIC
(CRYSTALS FLASH COLOR)
I
DETERMINE EXTINCTION
DETERMINE INDEX OF REFRACTION
NOTE INTERFERENCE
OPTIC
POSITIVE ^ '
DETERMINE INDEX
OF REFRACTION
UNIA
FIGURE
UAL
hi MrrflTTvr
4 4 4
DETERMINE INDEX DETERMINE INDEX DETERMINE INDEX
OF REFRACTION OF REFRACTION OF REFRACTION
I
IDENTIFY FROM TABLES IDENTIFY FROM TABLES
\
IDENTIFY FROM TABLES IDENTIFY FROM TABLES
Figure 02-04-01-01A. From West, P.M., The Chemist Analyst, 34, 76 (1945).
283
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1. TITLE QUANTITATIVE ANALYSIS USING TRANSMISSION ELECTRON MICROSCOPY (TEM)
Z IDENTIFICATION CODE
02-04-01-02
3. ABSTRACT OF METHODOLOGY
TEM Involves the impingement of an electron beam on a thin film of sample. The resultant transmitted electron beam is observed and
recorded. Quantitative analysis using TEM is superior to SEN (02-04-01-04) because: a) smaller samples can be observed and identified
using TEM, and b) the selected area electron diffraction (SAED) is generally more dependable for identification of chemical species
such as asbestos than the elemental analysis capabilities of SEM. Sample preparation involves collection of sample on a membrane
filter; a section of the filter is then placed on a carbon-coated electron microscope grid, and the filter is then dissolved using
acetone in a Soxhlet extractor. Subsequent mass, density and size distribution can be achieved. Combinations of TEM and EPtW
(see 02-04-01-04) allow even greater resolution, with subsequent identification by diffraction pattern and elemental analysis.
4, APPLICATION: Engineering evaluation R&D.
A) OPE RATIONAL SCOPE
Method is applicable to analysis of particulates collected from flue gas and fugitive emissions.
B) INTERFERENCES/LIMITATIONS
N/Q
C) RECOMMENDED USE AREA
TEM is ona of the approaches usable for compound analysis..
OPERATIONAL PARAMETERS
A) RANGE Measurement range of angstroms can be attained.
B) ACCURACY N/Q
C) PRECISION N/A
6. REAGENTS REQUIRED
N/A
7. EQUIPMENT REQUIRED
Transmission electron microscope; EPMA apparatus (optional).
& KEYWORD INDEX: Transmission electron microscope, particulates, quantitative analysis, asbestos.
9. CROSS REFERENCE ID NUMBERS 01-04; 01-06; 02-04-01-04, 02-04-01-04.
10. REFERENCES
A) PRIMARY SOURCE
361 McCrone, W.C., and I.M. Stewart, "Asbestos," American Laboratory, p. 13-18, April 1974.
B) BACKGROUND INFORMATION
362 Goldstein, J.I., and H. Yakowitz, "Practical Scanning Electron Microscopy," New York, Plenum Press, 1975, p. 44.
Ct FIELD APPLICATIONS
363 Yakowitz, H.,et al, "Analysis of Urban Particulates bv Means of Combined Electron Microscopy am; X-Rav Microanalvsis."
Micron, 3, 506-525 (1972).
284
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PAGE 1 OF 2 FOR
1. TITLE ELECTRON PROBE MICROANALYSIS (EPMAI FOR PARTICULATE ANALYSIS
Z IDENTIFICATION CODE
02-04-01-03
3. ABSTRACT OF METHODOLOGY
EPMA (or electron microprobe) can be used in qualitative and quantitative determination of elements above atomic number 6.
A small energetic electron beam impinges the surface of the specimen and causes characteristic X-ray emissions which are
subsequently analyzed by wavelength dispersion techniques (see 02-04-02-03). The X-ray output consists of spectral probes
at characteristic wavelengths; the positions of the wavelengths are used for qualitative analysis. For quantitative
analysis, the peak heights (intensity ratios) are measured on both the unknown and a standard of known composition.
Chemical species in urban particulates mounted on carbon films or copper grids have been semi-quantitatively analyzed
using EPMA techniques (See Reference 368). Trace elements (Ti, V, Cr, Mn, Co, Cu, Ni and Zn) in silicates have also
been determined (See Reference 362).
4, APPLICATION^ Engineering evaluation R&D.
A) OPE RATIONAL SCOPE
Method is applicable to analysis of particulates collected from flue gas samples, fugitive emissions. This method is
intended for single particle chemical analysis.
B) INTERFERENCES/LIMITATIONS
Interferences may arise from the excitation of small surface contaminant particles lying atop larger particles. The use of
standards whose composition closely matches the specimen being analyzed gives better results than analyses performed without
standards.
C) RECOMMENDED USE AREA
This method is applicable to compound identification of single particles on homogeneous bulk samples.
5. OPERATIONAL PARAMETERS
A) RANGE For 15 kV operation, minimum detectability limits are 200+100 ppm for Ti; «0 ±200 ppm for Zn; particles of
<0.5Mm in diameter can be analyzed; sensitivities of 1/10SS to 1/1000X can be attained.
B) ACCURACY ggj; confidence levels can be achieved.
C) PRECISION values obtained by EPMA can fall within one standard deviation of the calibration curves for elemental NBS
standards.
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
N/A
EPMA microprobe, typically operated at 15 to 20 kV and
specimen currents of 2 x 10"8 amperes.
KEYWORD INDEX:
: Electron probe, microanalyses, particulates, quantitative analysis, silicates.
9. CROSS REFERENCE ID NUMBERS 01-04; 01-06; 02-04-01-04; 02-04-02-03.
10. REFERENCES
A) PRIMARY SOURCE
(See Continuation Sheet)
B) BACKGROUND INFORMATION
(See Continuation Sheet)
C) FIELD APPLICATIONS
(See Continuation Sheet)
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PAGE 2 OF 2 FOR
TITLE ELECTRON PROBE MICROANALYSIS (EPMA) FOR PARTICULATE
ANALYSIS (CONTINUED)
ID NO. 02-04-01-03
A) PRIMARY SOURCE
364 Heidel, R.H., and G.A. Desborough, "Precision and Detection Limits of Certain Minor and Trace Elements in
Silicates by Electron Microprobe Analysis," in "Proceedings of the 6th National Conference on Electron
Probe Analysis," Pittsburgh, PA., (July 27-30, 1971), p. 25 A-B.
365 "Advances in X-Ray Analysis," Volume 15, K.F.J. Heinrich (ed.), New York, Plenum Press, 1972. p. 150.
B) BACKGROUND INFORMATION
362 Goldstein, J.I., and H. Yakowitz, "Practical Scanning Electron Microscopy," New York, Plenum Press, 1975,
p. 1 and p". 230.
366 "Quantitative Electron Probe Microanalysis," National Bureau of Standards Special Publication 298, Washington,
October 1968.
367 DeHoff, R.T., and F.N. Rhines, "Quantitative Microscopy," New York, McGraw-Hill, 1968.
C) FIELD APPLICATIONS
237 Birks, L.S., "X-Ray Spectrochemical Analysis," Interscience Publishers, Inc., New York, 1959.
368 Yakowitz, H., et al, "Analysis of Urban Particulates by Means of Combined Electron Microscopy and
X-ray Microanalysis," Micron, 3., 506-525 (1972).
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1. TITLE SCANNING ELECTRON MICROSCOPY (SEM) FOR QUALITATIVE PARTICULATE ANALYSIS
2. IDENTIFICATION CODE
02-04-01-04
3. ABSTRACT OF METHODOLOGY
In scanning electron microscopy (SEM), the specimen is swept by an electron beam, and the variation of the secondary electron
emission intensity is recorded by a secondary electron detector. The signal simultaneously modulates the brightness of an
oscilloscope beam, producing an image on the surface of the oscilloscope screen. Since the secondary electron beam is localized
in the beam impact area, images of relatively high resolution are achieved. Morphological characteristics of the specimen are
then determined from the generated images. Some applications of SEM include analysis of small particles from ball bearings for
Fe, Si, K, Zn, the determination of percentage of oxides and sulfides in steel, silicates in wrought iron, and carbides in steel.
(See 02-04-02-03 and Reference 362.)
Combinations of SEM and EPMA techniques (see 02-04-02-03} yield qualitative and semi quantitative data. The SEM-EPMA approach
involves dispersal of sample (participates) on a suitable substrate (germanium) with subsequent scanning in raster form. When a
monitor on the secondary electron signal indicates that the electron beam has encountered a particle, the beam is stopped, and a
scan is also measured, and is related to the mass thickness of the sample. The accumulated data yield detailed information on
particle size, shape,mass distribution and tentative composition. (See Reference 372.)
4. APPLICATION: Engineering evaluation R&D.
A) OPE RATIONAL SCOPE
Method is applicable to analysis of particulates from flue gas sampling, fugitive emissions, and solid samples.
B) INTERFERENCES/LIMITATIONS
Interferences may arise from excitation of small surface contaminant particles lying atop larger particles.
This is essentially a surface technique.
C) RECOMMENDED USE AREA
This method can be used to identify a particle by its morphological characteristics.
5. OPERATIONAL PARAMETERS
A) RANGE Measurement range of several angstroms can be achieved, depending upon the resolution of the
imaging system.
B) ACCURACY N/fl
C) PRECISION
N/A
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
N/A
SEM apparatus is comprised of lens system, electron gun,
electron collector, visual and recording cathode ray tubes
and associated electronic hardware.
KEYWORD INDEX: scanning electron microscopy, electron microprobe analysis, particulates.
9. CROSS REFERENCE ID NUMBERS 01-04; 01-06; 02-04-01-03; 02-04-02-03.
10. REFERENCES
36oldsUte J.I. . and H. Yakowitz, "Practical Scanning Electron Microscopy " New York Plenum Press 1975, p. 236.
369 Griffiths, B.M.. "Analytical Scanning Electron Microscope," American Laboratory. 83-9, April 1974.
B) BACKGROUND INFORMATION . „ . „„„,,, ,,,, ,„,,
370 "Qualitative Metallurgical Systems (QMS)," Bausch » Lomb, Scientific Instrument D1ViS1on Brochure, Cat. No. 42-2337, 1071,
371 Griffiths, B., A.V. Jones and I. Kartell, "Scanning Electron Microscopv; f^^W}"*10"^ ^l^' ^ "' "2
372 "SEM/1973 Proceedings of the 6th Annual SEM Symposium," (0. Johan, ed.), IITRI, Chicago, in., an, P.
. I.. E. "enderson and H. Yakowit, "Proceedings of the Apollo 11 Lunar Science Conference," 1970, Vol. 1. p. 499.
374 Bayard, M. , "Microprobe Analysis," (C.A. Andersen, ed.), New York, Wiley, ltli, p.
375 Ruff, Jr., A.W. , NBSIR 74-474, 1974, p. 15.
287
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PAGE 1 OF 2 FOR
1. TITLE
QUANTITATIVE COMPOUND CHEMICAL ANALYSIS BY X-RAY POWDER
DIFFRACTION (XRD)
2. IDENTIFICATION CODE
02-04-02-01
3. ABSTRACT OF METHODOLOGY
X-Ray powder diffraction involves a powder sample diffracting a primary x-ray beam into a series of diffraction lines which are charac-
teristic of a given crystalline substance. Mineral determinations commonly employ 5 percent internal standard (CaCt^, kaolin) with
subsequent quantification by comparison to standard curves. Microgram quantities of Si02 and NaO, dispersed with a diamond grinding
paste of appropriate particle size, can be determined using fluorite windows cut parallel to 100 and 410 planes. Quantitative deter-
mination of Si02 on sized airborne particulates in conducted using CaF2 of the same size range as.the collected sample as the internal
standard; the results of the determinations are compared to calibration plots of the intensity of the CaF2/Si02 line versus weight of
CaF2/Si02.
A new technique which eliminates interferences caused by interal standards involves dispersal of the sample (mineral or particulates)
in a matrix of finely powdered amorphous glass. (Reference 376)
4. APPLICATION: Engineering evaluation R&D.
A) OPERATIONAL SCOPE
Method is applicable to analysis of crystalline components of particulates from flue gases and fugitive emissions. Solid material
can be crushed to less than 2 p. and then analyzed by this method.
B) INTERFERENCES/LIMITATIONS
Major spectral interferences due to use of kaolin, calcium carbonate, etc., are eliminated using amorphous glass as internal
standard. Method is not applicable to determination of S02 adsorbed on solid such as Pb02. Amorphous materials are not recorded.
C) RECOMMENDED USE AREA
This is the recommended engineering evaluation R&D method for the determination of crystalline compounds iniparticulate matter.
5. OPERATIONAL PARAMETERS
A) RANGE Samples of ng to microgram quantities can be determined, depending on the technique employed.
B) ACCURACY ±5% using the amorphous glass internal standard -±10? using microgram samples and parallel-cut fluorite windows.
C) PRECISION ±10% or better.
6. REAGENTS REQUIRED
Reagents are dependent upon technique used, e.g., powdered
amorphous glass, kaolin, calcium carbonate, etc.
7. EQUIPMENT REQUIRED
X-ray diffraction spectrometer with strip chart recorder; sample
preparation equipment (powder mixers, stainless steel balls).
a KEYWORD INDEX: X-ray diffraction, particulates, quantitative analysis.
9. CROSS REFERENCE ID NUMBERS 01-04-01-02, 01-04-02-01; 01-06-01-01, 01-06-02-01; 01-05-02-01.
10. REFERENCES
A) PRIMARY SOURCE
(See reverse side)
B) BACKGROUND INFORMATION
(See reverse side)
C) FIELD APPLICATIONS
(See reverse side)
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PAGE 2 OF 2 FOR
ITLE QUANTITATIVE COMPOUND CHEMICAL ANALYSIS BY X-RAY POWDER DIFFRACTION
(XRD) (CONTINUED)
ID NO. 02-0442-01
A) PRIMARY SOURCE
376 Warner, P.O., et al, "Identification and Quantitative Analysis of Particulate Air Contaminants by x-Ray Diffraction Spectrometry,"
presented at 64th Annual Meeting of the Air Pollution Control Association, Atlantic City, N.J., June 27 July 2, 1971, 15 pp.
378 Oberg, M., "Evaluation of Quartz in Airborne Dust In the 0.5- to 2-micron Size Range," Environ. Sci. Tech 2 (10) 795
(October 1968). -' l
379 Baldock, P.J., and A. Parker, "X-Ray Diffractometry of Small (20 ug to 1 yg) Samples Using Standard Equipment, J. Appl. Cryst, 6_,
B) BACKGROUND INFORMATION
361 McCrone, W.C., and I.M. Stewart, "Asbestos," Amer. Lab., pp. 13-18, April 1974.
362 Ewing, G.W., "Instrumental Methods of Chemical Analysis," New York, McGraw-Hill Book Company, Third Edition, 1960, p. 195.
C) FIELD APPLICATIONS
381 Waller, R.E., et al, "An Electron Microscope Study of Particles in Town Air," Int. J. of Air Hater Pollut. Pergamon Press,
1963, Vol. 7, pp. 787-97.
382 Johns, W.D., and R.E. Grim, "Quantitative Estimates of Clay Minerals by Diffraction Methods," Journal of Sedimentary Petrology,
24,(4), 242-51 (1954). '
383 Window, R.L., "Atmospheric Dust Records in Permanent Snowfields: Implications to Marine Sedimentation," Biological Society
of America Bulletin, 80, 761-82 (1969). ~ "'
384 Carl, H.F., "Quantitative Mineral Analysis with a Recording X-Ray Diffraction Spectrometer,11 Am Minerajpjist, 32, 508 (1947).
385 M. Feldstein, et al, "The Collection and Analysis of Inorganic Dust Downwind of Source Effluents," presented at 61st Annual
Meeting of the Air Pollution Control Association, 1968.
386 Leroux, J., and C.A. Powers, "Direct X-Ray Diffraction Analysis Quartz in Industrial Films Deposited on Silver Membrane Filters,"
Staub-Reinholt, 29, 26 (1969).
387 Talvetie, N.A., and H.W. Brewer, "X-Ray Diffraction Analysis of Industrial Dust," A_._I_.jy\.S.., 23, 214 (1962).
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COMPOUND IDENTIFICATION BY ELECTRON SPECTROSCOPY FOR CHEMICAL
1. TITLE ANALYSIS (ESCA)
2. IDENTIFICATION CODE
02-04-02-02
3. ABSTRACT METHODOLOGY
Electron Spectroscopy for Chemical Analysis (ESCA) accurately measures the binding energy of an electron both for elemental characterization
and for the measurement of chemical shifts resulting from the atomic environment of each element. The sample is irradiated with X-rays
causing inner orbital electroncs to be ejected. The energy of these photo-electrons is a measure of the binding energy of the electrons as
modified by the chemical surroundings of the emitting atom. Thus energy shifts in the binding energy of electrons emitted from the same
element indicate different chemical environments (i.e., compounds). ESCA is extremely surface limited as the electrons have a shallow
(3-20 A) escape depth. This feature makes ESCA an extremely useful tool to study adsorption phenomena such as SO,, or soot or fly ash. Most
commercial instruments have ion beam sputtering for sequential removal of atomic layers. Quantization of ESCA data is difficult and
normally requires comparison to standards in a similar matrix. Also assumptions about depth profile and homogeneity of the sample can
affect the ultimate accuracy of the quantification. One approach (Novakov) was to scan the sample with XRF to quantify the Pb present in
the sample and then measure the S to Pb for each oxidation state of sulfur with ESCA. The S/Pb ratio multiplied by the Pb content in
vg/m allowed calculations for atmospheric concentrations of S compounds.
4. APPLICATION'- Engineering evaluation R&D.
A) OPERATIONAL SCOPE
ESCA can be used on any gases, liquids and solids, depending on the accessory equipment available for the ESCA system.
Elements from Li to V can be studied.
B) INTERFERENCES/LIMITATIONS
As in any direct compound identification, the equipment is costly ($100 K), complicated and not readily available. Samples must
be sent to commercial laboratories specializing in ESCA analysis. This instrument is extremely useful for qualitative work, but
further work is needed on methods to quantify the results.
C) RECOMMENDED USE AREA
Valence state analysis of solid samples.
5. OPERATIONAL PARAMETERS
A) RANGE Elements from Li to V, sensitivity 10"2 to 10"3 atomic fraction.
B) ACCURACY p|/g
C) PRECISION N/Q
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
N/A
ESCA System - Commercial suppliers: Hewlett-Packard Corp.,
Palo Alto, Ca.; McPherson Instr., Acton, Mass.; E.I. duPont,
Monrovia, Ca.
& KEYWORD INDEX: Analysis, compound identification, ESCA.
9. CROSS REFERENCE ID NUMBERS 02-01-02.
10. REFERENCES
A) PRIMARY SOURCE
388 Siegbahn, K., et al, "Electron Spectroscopy for Chemical Analysis," Nova Acta Regiae Soc. Sci. Upsaliensis, Ser. IV,
Vol. 20 (1967), NTIS No. AD 844-315. ~
B) BACKGROUND INFORMATION
389 Evans, C.A., "Surface & Thin Film Compositional Analysis: Description & Comparison of Techniques," Anal. Chem.,
47, 819A (1975).
390 Evans, C.A., "Surface & Thin Film Analysis: Instrumentation," Anal. Chem., 47, 855A (1975).
C) FIELD APPLICATIONS
391 Novakov, T., A. Alcocer, P. Mueller and J. Otvos, "Chemical Composition of Pasadena Aerosol by Particle Size and
"Time of Day," J. Coll. Interface Sci., 39(7), 225 (1972).
392 Hulett, L.O., "Studies of Sulfur Compounds Adsorbed on Smoke Particles and Other Solids by Photoelectron Spectroscopy,"
Proceedings of the Symposium on Air Quality, 161st National Meeting of ACS, April 1-2, 1971, Los Angeles, California
(Plenum Publishing, Washington, D. C.).
393 Craig, N.L., "Determination of the Chemical States of Sulfur in Ambient Pollution Aerosols by X-Ray Photoelectron
Spectroscopy."Atm. Environ.. 8, 15 (1974).
290
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CHEMICAL (ELEMENTAL) ANALYSIS USING SCANNING ELECTRON MICROSCOPE ISEM),
1. TITLE ELECTRON PROBE MICROANALVSIS (EPMA) WITH AN ENERGY DISPERSIVE X-RAY
SPECTROMETER (EDX)
Z IDENTIFICATION CODE
02-04-02-03
3. ABSTRACT OF METHODOLOGY
Energy dispersive X-ray spectrometry (EDX) has replaced the more conventional wavelength dispersive spectrometry (WDS) in most
SEN (02-04-01-04) and EPMA (02-04-01-03) systems. The WDS system uses a dispersive crystal through which the X-rays which are
emitted from the sample are diffracted. The various X-ray wavelengths are dispersed to different angles. The X-ray spectrum
is then obtained by plotting intensity versus diffraction angle. In the EDX techniques, however, the emitted X-rays are
detected directly without the use of a crystal. The energy of the X-rays is measured by means of balance filters, selective
excitation or pulse height analysis. The appropriate atomic numbers can then be assigned to the spectral peaks once their
energies are determined. Elemental ratios are calculated and the compounds present are identified. EDX has several advantages:
1) it requires only a small X-ray source for sample excitation, 2) it provides direct observation, 3) the intensity of the
signal is high, and 4) data acquisition time is short. However. WDS must be used to resolve elements from S to Ni.
4. APPLICATION: Engineering evaluation RSD.
A) OPERATIONAL SCOPE
Method is applicable to the elemental analysis of partlculates from flue, fugitive emissions, and solid samples.
B) INTERFERENCES/LIMITATIONS
Although relatively long counting times are required for elements present in trace amounts, EDX instrument stability
limits counting time to 10 or 15 minutes, in practice. At high count rates, peaks may broaden. Particles in close
proximity may interfere and preclude unambiguous analysis.
C) RECOMMENDED USE AREA
This method can be used to identify single particles through morphology and elemental analysis.
5. OPERATIONAL PARAMETERS
A) RANGE Elements present in less than 100 ppm concentrations can be identified, if background intensity is subtracted.
B) ACCURACY 10% or less relative error.
C) PRECISION Dependent upon peak resolution; values not quoted.
6. REAGENTS REQUIRED
N/A
a KEYWORD INDEX: Ener9y dJsP?rs1,
"UCA microanalysis (
9. CROSS REFERENCE ID NUMBERS
7. EQUIPMENT REQUIRED
SEM or EPMA equipment with energy dispersive spectrometer.
ve spectrometry (EDX), Scanning electron microscopy (SEM), electron probe
EPMA), particulates, quantitative analysis.
01-04-01-01, 01-04-02-01; 01-06-01-01, 01-06-02-01; 02-04-01-03; 02-04-01-04.
W. REFERENCES
AJ PRIMARY SOURCE
3|>f Goldstein, J.I., and H. Yakowitz, "Practical Scanning Electron Microscopy," New York, Plenum Press, 1975, p. 402-3.
394 "Advances in X-ray Analysis," Vol. 15, (K.F.J. Heinrich, ed.), New York, Plenum Press, 1972, p. 197.
B) BACKGROUND INFORMATION
395 DeHoff, R.T., and F.N. Rhines, "Quantitative Microscopy," New York, McGraw-Hill, 1968.
FIELD APPLICATIONS
Ruff, A.W. , Jr., "National Bureau of Standards Report, NBSIR," 74-474, 1974, p. 15.
Baynard, M. , in "Microprobe Analysis," (C.A. Anderson, ed.), New York, Wiley, 1973, p. 323.
291
-------
Table of Contents for 02-05 On-Line Continuous Analysis
02-05-01 On-Line Gas Analysis/Sampling
02-05-01-01 Probe and Filters for On-Line Measurement of
Fugitive Emissions on Flue Gas
02-05-01-02 Membrane Conditioning System for On-Line
Continuous Monitoring of Atmospheres and Flue Gases . .
02-05-01-03 Gas Conditioning by Controlled Condensation . .
02-05-01-04 Continuous On-Line Gas Monitoring Systems
Design
02-05-01-05 Multiport Probe for Continuous Gas Monitoring .
02-05-02 On-Line Continuous Gas Analysis
02-05-02-01 Continuous Monitoring of N0/N02
02-05-02-02 Continuous Monitoring of Ozone
02-05-02-03 Continuous Monitoring of Sulfur Dioxide ....
02-05-02-04 Continuous Monitoring of CO/COg
02--05-02-05 Continuous Monitoring of HgS
02-05-02-06 Determination of Hydrocarbons Corrected for
Methane
02-05-03 On-Line Continuous Liquid Analysis
02-05-03-01 Continuous On-Line Liquid Analysis With a
Technicon Monitor IV System
02-05-03-02 Continuous On-Line Monitoring of Liquid Streams
With Orion Specific Ion Electrons
293
-------
APPLICATION MATRIX FOR 02-05 ON-LINE CONTINUOUS ANALYSIS
METHOD
02-05-01-01
02-05-01-02
02-05-01-03
02-05-01-04
02-05-01-05
02-05-02-01
02-05-02-02
02-05-02-03
02-05-02-04
02-05-02-05
02-05-02-06
02-05-03-01
02-05-03-02
LEVEL I
ENVIRONMENTAL
ASSESSMENT
•
•
•
O
•
•
•
COMPLIANCE
•
•
•
•
ENGINEERING
EVALUATION
R/D
•
•
•
•
•
•
•
•
•
•
•
•
294
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ON-LINE CONTINUOUS ANALYSIS- ID No. 02-05
This section contains methods for continuous analysis of gases and
liquids under flue gas, fugitive (ambient), or process stream conditions.
The measurement methods discussed in this section are designed for contin-
uous automated operation. While a compilation of methods has been given
for each gas discussed, specific instruments have been recommended as
the best choice for flue gas and fugitive monitoring.
02-05-01 On-Line Gas Analysis/Sampling (Abstracts 02-05-01-01
through 02-05-01-04}~~~
Analysis of the gases by a specific instrumental technique is only
part of the problem of on-line analysis. Sampling is an integral part of
on-line continuous analysis, especially for gases. Section 02-05-01 con-
tains specific procedures for gas sampling system design. Each particular
source will have its own unique problems but,in general, the following
concepts can be applied to all systems.
1. Sampling location and frequency - Sampling site and number of
sampling points should be selected to obtain representative samples.
Attention should be directed to local meterological conditions, unintentioned
proximity to sources, and possible anomalies in the parent air, especially
when sampling for fugitive emissions (01-05). The cyclic nature of many
processes should be considered in establishing the sampling times and lengths.
2. Gas flow characteristics - The sample should flow readily despite
changes in temperature or pressure. Sample lines should be protected from
clogging by particulates and/or condensation (02-05-01-01).
3. Removal of interferences - Converters or filters are employed to
remove species that can affect the system accuracy or operation (02-05-01-01).
These systems must be chosen with care to avoid removing or changing the
species of interest.
4. Sample conditioning - The collection device or analyzer may require
the sample to be within specified limits of temperature, pressure or humidity
(02-05-01-02, -03). Is is recommended that for S02 and C02 monitoring,the
membrane system of gas conditioning be used (02-05-01-02).
295
-------
5. Sampling train materials - Absorption, adsorption, condensation
and other chemical reactions can occur in the sampling system. When
temperature conditions allow, heat-traced Teflon tubing should be used
(02-05-01-04). For higher temperatures, borosilicate glass or 316
stainless steel lines can be used.
6. Calibration - Whenever possible, dynamic calibration under simu-
lated conditions is the desired approach. The concentrations of the
calibration gases should test the dynamic range of the instrument
(02-05-02-01, 02, 03, 04, 05). Recent studies (reference 170, 171) have
shown that aluminum cylinders provide the best stability for storing
certified gases.
02-05-02 On-Line Continuous Gas Analysis (Abstracts 02-05-02-01
through 02-05-02-05)
In abstracts 02-04-01-01 through 02-04-01-05, currently available
commercial approaches to on-line continuous monitoring of carbon dioxide,
carbon monoxide, ozone, NO , sulfur dioxide, and hydrogen sulfide are
-A
presented. The methods employed include colorimetric (NO , Og, H2S) and
coulometric (NO, 0,, CO, H2S) techniques, GC (C02, H2$), NDIR (NO, S02, CO,
C02),NDUV (NOX, S02), Dispersive Spectroscopy (03, CO, C02), electrochemical
methods (NOX, D02, CO, H2S), second derivative spectroscopy (NO, S02, 03),
correlation spectroscopy (S02, NO), chemilumenscence (NO, 0_, S02).
fluorescence (S02, CO) and catalytic oxidation (CO). For each gas, the
different methods are outlined and describe operating principles, the
species measured, sensitivity, range, and interferences. It is also noted
whether the particular instrument can be used to sample fugitive emissions,
flue gas emissions, or both. For each gas a specific instrument is
recommended for fugitive and flue gas monitoring.
02-05-03 On-line Continuous Liquid Analysis (Abstracts 02-05-03-01
to 02-05-03::02l
On-line continuous liquid analysis is not as developed as on-line gas
analysis. While many instruments are available for pH and temperature
monitoring, there are far fewer instruments capable of monitoring specific-
anions or cations. Abstracts 02-05-03-01 and -02 discuss the procedures for
using the Technicon and Orion continuous monitor systems. These systems
take the colorimetric and specific ion electrode approaches, respectively.
296
-------
While these systems require only small (ml) amounts of the process
stream to pass through their flowthrough systems, the same problems that
are involved with liquid/slurry (01-02) sampling must be considered. The
reader is directed to 01-02 to review the problems involved in obtaining
a representative liquid sample.
REFERENCES
171 Wechter, S.G., "Preparation of Stable Pollution Gas Standards Using
Treated Aluminum Cylinders," ASTM Calibration Symposium, Boulder,
Colorado, August 5, 1975.
170 Grieco, H.A., and S.G. Wechter, "The Trouble with Reactive Calibration-
Gas Blends and What To Do About It," Gulf Coast Instrumental Analysis
Conference, Houston, Texas, November 1, 1974.
297
-------
1. TITLE PROBE AND FILTERS FOR ON-LINE MEASUREMENT OF FUGITIVE EMISSIONS OR FLUE GAS
2. IDENTIFICATION CODE
02-05-01-01
3. ABSTRACT OF METHODOLOGY
In order to analyze a gas stream by continuous on-line instruments, a gas sample must be continuously extracted from the gas stream and
the particulates removed. For fugitive emissions a Teflon line (probe) and Teflon or glass filter will suffice. In flue gas streams,
a more elaborate system must be devised because of the higher temperatures and mass readings. The probe is kept at stack temperatures
by the gas stream or by a heating jacket, but never below 110°C. The recommended materials are 316 SS or Inconel. Figure 02-05-01-01A
shows a probe developed for high dust loadings. The large filter area allows long time intervals between changes. An equally usable
approach is to install a filter plug of ceramic or stainless steel mesh and periodically backflush with line air to clean the filter.
For high temperature applications (>500°C), water cooled probes are recommended. A typical high temperature probe consists of a water
or steam jacket with a quartz liner. This probe has been used up to 1000°C.
CERAMIC
FILTERS
MOUNTING
PROBE FLANGE •
STACK GAS
Figure 02-05-01-01A. (From Pol. Enq.. 26 (July, 1975)).
4. APPLICATION- Engineering evaluation R&D.
A) OPERATIONAL SCOPE
The equipment described can be used in flue gas streams at temperatures up to 1000°C.
B) INTERFERENCES/LIMITATIONS
The particulate loading in the filter should be kept low to prevent gases adsorbing on particulates. Chemical reactions on the
particulates might affect the concentration or composition of gas sampled.
C) RECOMMENDED USE AREA
Engineering evaluation R&D; proposed compliance method for aluminum refinery.
5. OPERATIONAL PARAMETERS
A) RANGE Up to 1000°C.
B) ACCURACY N/A
C) PRECISION N/A
6. REAGENTS REQUIRED
None
7. EQUIPMENT REQUIRED
Teflon tubing, 316 SS tubing, quartz tubes, SS water jacket.
a KEYWORD INDEX: Analysis, probes.
9. CROSS REFERENCE ID NUMBERS 02-05-02.
10. REFERENCES
A) PRIMARY SOURCE
398 Wolf, P.C.,. "Continuous Stack Gas Monitoring: Gas Handling Components and Accessories," Pol. Eng., 26 (July 1975).
B) BACKGROUND INFORMATION
018 Flegal, C.A., M.L. Kraft, C. Lin, R.F. Maddalone, J.A. Starkovich and C. Zee, "Procedures for Process Measurements:
Trace Inorganic Materials," TRW Systems Group, EPA Contract #68-02-1393, July 1975.
C) FIELD APPLICATIONS
-------
PAGE 1 OF 2 FOR
1 TITI F MEMBRANE CONDITIONING SYSTEM FOR ON-LINE CONTINUOUS MONITORING OF
I. IllLC ATMOSPHERIC AND FLUE GASES
2. IDENTIFICATION CODE
02-05-01:0.2
3. ABSTRACT OF METHODOLOGY
Many of the atmospheric or flue gas instrumental measurement methods require that the gas stream be conditioned prior to the actual
analysis of the gas. The particulates are first removed (see 02-05-01-01) and then the moisture content of the stream is reduced. At
all times, the gases are conveyed in either SS or Teflon heat traced lines to prevent condensation prior to the gas conditioning.
Figure 02-05-01-01A is a drawing of the membrane system for moisture separation. This unit operates by passing the wet sample flow
into the sample inlet which wets the inside wall of the tube. Water in the sample is continuously removed as water vapor on the shell
side at the purge outlet, by dry gas flowing countercurrent to the sample flow. This type of system is highly recommended for the analysis
of gases which have a high solubility in water (carbon dioxide, sulfur dioxide) and thus could be entrained in the condensate of a refri-
geration type unit. The upper temperature range of the unit is approximately 150°C.
4. APPLICATION'- Engineering evaluation R&D.
A) OPERATIONAL SCOPE
The sample conditioning methods in this abstract can be used for atmospheric or flue gas monitoring.
B) INTERFERENCES/LIMITATIONS
This gas conditioning system is only useful to 150°C. For higher temperature applications, use 02-05-01-03.
C) RECOMMENDED USE AREA
This unit is recommended for all levels to remove moisture from flue gas streams, especially when S02 or C02 is to be measured.
5. OPERATIONAL PARAMETERS
A) RANGE Up to 150 C.
B) ACCURACY NA
C) PRECISION NA
6. REAGENTS REQUIRED
None
7. EQUIPMENT REQUIRED
Membrane dryer (Perma Pure Products, Oceanport, N.J., is a
possible source).
8> KEYWORD INDEX: Analysis, sample conditioning.
_ __„ . — ' ~~
9. CROSS REFERENCE ID NUMBERS 02-05-01-01, 02-05-01-03, 02-05-01-04.
•
10. REFERENCES
"-
A) PRIMARY SOURCE
390 Perma Pure Products, Oceanport, N.J., Engineering Brochure.
B) BACKGROUND INFORMATION
391 Chapman, R.L., PoL-En^, 4(6) 38 (1972). Eng1neer1ng and Maintenance Conference, Chicago, 111.,
392 Lierop, B.V., Preprint, presented at 24th National a
March 9, 1973.
393 Morrow, N.L., R.R. Bertrand and R.S. Brief, Chen^Jn^, 79(2). 84 (1972).
C) FIELD APPLICATIONS
-------
PAGE 2 OF 2 FOR
TITLE MEMBRANE CONDITIONING SYSTEM FOR ON-LINE CONTINUOUS MONITORING OF
ATMOSPHERIC AND FLUE GASES (CONTINUED)
ID NO.
02-05-01-02
(ADD FLOW METER
FOR PRESSURE PURGE)
GAS
SAMPLE
30-100
PSIG
FILTER
t
VACUUM
GAUGE
TO
VACUUM PUMP
PERMA PURE DRYER
PERMEABLE TUBE
DRYER
INLET
PURGE INLET
FLOW METER FLOW
CON-I
FILTERED DRY
ATMOSPHERIC
PRESSURE AIR -»•
(FOR VACUUM PURGE)
FILTERED DRY GAS _*
PURGE (1-5 PSIG) ^
1
TROLLEI
"SELF PURGE
Figure 02-05-01-02A. (From Reference 390).
300
-------
PAGE 1 OF 2 FOR
1. TITLE GAS CONDITIONING BY CONTROLLED CONDENSATION
2. IDENTIFICATION CODE
02-05-01-03
3. ABSTRACT OF METHODOLOGY
Flue gases can be cooled to lower the moisture content of the gas stream. Figure 02-05-01-03A shows a typical design for a
condenser system. An electromechanical refrigerator is the most satisfactory device for condensate separation, but conditions
(limited electrical power) or complexity can dictate the use of ice/water or dry ice cooling.
The condensing section is designed so that the sample gas will have short residence times in the cooling coil. Also, the cooling coil-
condensate collector is such that the gas does not flow over the collected condensate surface. Both of these conditions will minimize
the amount of gas (especially C02 and S02) that will go into solution.
4. APPLICATION- Environmental assessment, engineering evaluation R&D.
A) OPERATIONAL SCOPE
Moisture removal in flue gas streams is particularly important. This condensation method of moisture removal can be used in all
areas, but it is primarily intended to be used in high temperature (>150°C) and survey (level 1 environmental assessment) work.
Depending on material design (Pyrex, quartz or stainless steel) the temperature range of the condenser system is limited only by its
ability to cool the gas stream to a constant temperature.
B) INTERFERENCES/LIMITATIONS
Whenever a condenser system is used to remove excess moisture from a gas stream, it is possible that gas concentrations could be
changed by the scrubbing action of the condensation mechanism (S02 and C02) or that a chemical change in the gas composition can be
induced (SOe MtHgSIH). Precautions as noted in Abstract of Methodology must be followed to limit these two possibilities.
C) RECOMMENDED USE AREA
Environmental assessment.
5. OPERATIONAL PARAMETERS
A) RANGE
UP to loocrc.
B) ACCURACY N/Q (±10% of actual gas concentrations estimated).
C) PRECISION N/Q (±10% estimated).
6. REAGENTS REQUIRED
Ice/water or antifreeze recirculating fluid.
7. EQUIPMENT REQUIRED
Commercial condenser unit (Beckman
Joy Manufacturing Co., Los Angeles
shown in Figure 02-05-01 -03A.
Instr., Fullerton.Ca. ;
, Ca.) or constructed as
KEYWORD INDEX: Analysis, gas conditioning, moisture condensation.
—. . — • '
9. CROSS REFERENCE ID NUMBERS 02-05-01-01, 02-05-01-02.
_.
—
10. REFERENCES
lTpCEC., "Continuous Stac* Gas Monitoring: Gas Handling Components and Accessories," PoKJnSL,
B) BACKGROUND INFORMATION
A) PRIMARY SOURCE
398
»75).
C) FIELD APPLICATIONS
301
-------
TITLE GAS CONDITIONING BY CONTROLLED CONDENSATION (CONTINUED)
PAGE 2 OF 2 FOR
ID NO. 02-05-01-03
V, = SAMPLE GAS IN
V2 = SAMPLE GAS OUT
Figure 02-05-01-03A. Schematic of Condenser Coil (from Reference 398).
302
-------
PAGE 1 OF 3 FOR
1. TITLE CONTINUOUS ON-LINE GAS MONITORING SYSTEMS DESIGN
^ IDENTIFICATION CODE
02-05-01-04
3. ABSTRACT OF METHODOLOGY
The ultimate performance of an analyzer will depend on how the sampling system (probe, lines, conditioning equipment, analyzer
and pumps) is designed. In all system designs, the calibration gas must be conditioned in the same fashion as the sample gas.
These calibration gases should be stored in aluminum-lined bottles (AIRCO) which have demonstrated improved reliability over
conventional steel containers. In general, the distance between the analyzer and the sampling point should be minimized. If
this is not possible, a bypass system is employed using high flow rate for gas sampling and line purge while a small quantity is
drawn off for analysis. In all cases, heat traced (^125°C) stainless steel or Teflon lines are to be used to conduct the gas to
the analyzer. Figure 02-05-01-04A shows a simple approach to single gas analysis system; Figure 02-05-01-048 shows a semi-
automated multigas sampling system specifically designed to use a membrane gas conditioning unit. Figure 02-05-01-04C shows
the schematic of a double pass fast-responding bypass system designed to monitor S02 inlet and outlet to FGD unit. This design
assures that H2SO^ and H2S03 aerosols will not precipitate in the sample lines.
4. APPLICATION'- Engineering evaluation R&D.
A) OPERATIONAL SCOPE
These systems are designed to operate at high or low mass loadings and up to temperatures of 1000°C (when refrigeration is
used to condition the gas). Membrane conditioning equipment'requires that the gas be cooled to temperatures less than 150°C.
See 02-05-01-01, 02, 03 for information about individual components.
B) INTERFERENCES/LIMITATIONS
The system must be adjusted to individual situations and problems such as high mass loading, corrosive gases and gases
measured. These factors all affect the ultimate reliability of the gas sampling system.
C) RECOMMENDED USE AREA
Engineering evaluation R&D for flue gas sampling.
5. OPERATIONAL PARAMETERS
A) RANGE Up to 10oo°C.
B) ACCURACY N/Q (+IQ% estimated).
Cl PRECISION N/Q (+10% estimated).
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
N/A
See Figures 02-05-01-04A through C for equipment needs.
* I nil
KEYWORD INDEX: Analysis, gas analysis, system design.
9. CROSS REFERENCE ID NUMBERS 02-05-01-01, 02, 03.
10. REFERENCES
—• „
A) PRIMARY SOURCE „ , ,g75)
399 Wolf., P.C., "Continuous Stack Gas Monitoring: Systems Design, Pol^n^, 36 (Aug. 1975).
B) BACKGROUND INFORMATION Analvzer Procedures," 1974 Annual Book of ASTM
ASTM, "Tentative Recommended Practice for General^^^ffi.i,. Philadelphia, PA., 1971, p. 708.
rs::::~OT^
- S^^^^-^a*wa^iSriIS!^r^'*™
C) FIELD APPLICATIONS
053
053
-------
TITLE CONTINUOUS ON-LINE GAS MONITORING SYSTEMS DESIGN (CONTINUED)
PAGE 2 OF 3 FOR
ID NO. 02-0501-04
HEATED LINE
STACK WALL
t
J
ANALYZER
OUTPUT
REGULATORS
SYSTEM OUTPUT
TO
RECORDER
INDICATOR
ALARM CONTACTS
COMPUTER. ETC
Figure 02-05-01-04A. Schematic of SCU Monitoring System With Second Passthrough Condenser (Reference 398).
2B,
3B
, .
'-*
HCF
R, ,
'-°
R.A.—O- -
•VENT
2 WAY BALL VALVE
WHITEY SS-4234
3 WAY BALL VALVE
WHITEY SS-43X54
SS-45X38
5 WAY BALL VALVE
WHITEY SS-432
FLOWMETER WITH INTEGRAL
CONTROL/SHUTOFF VALVE
HYDROCARBON REMOVAL
FILTER
PRESSURE REGULATOR WITH
GAGE (2 STAGE)
DRYER/FILTER
CONDENSATE TRAP
1/4 IN. TUBE
1/2 IN. TUBE
Figure 02-05-01-04B. Semi-automatic Multigas Sampling System with Membrane Gas Conditioning Unit.
304
-------
PAGE 3 OF 3 FOR
TITLE CONTINUOUS ON-LINE GAS MONITORING SYSTEMS DESIGN (CONTINUED)
ID NO.
02-05-01-04
SAMPLE BYPASS . EXHAUST
INSTRUMENT
AIR
PROBE HEATED LINE
PROBE TEMPERATURE
CONTROLLER
FILTER
REGULATOR
WITH GAGE
S?Al!| ZCTO I RECORDER |CONTROLLERl
GAS GAS
Figure 02-05-01-04C. Schematic of Automatic SO- Monitoring System (Reference 399).
-------
PAGE 1 OF 2 FOR
1. TITLE MULTIPORT PROBE FOR CONTINUOUS GAS MONITORING
2. IDENTIFICATION CODE
02-05-01-05
3. ABSTRACT OF METHODOLOGY
Because of gas stratification in flue gas ducts, it is recommended that a multiport probe be designed and built for continuous gas
sampling in a duct. The fabric design considerations are quite simple: 1) the probe should draw samples at a number of evenly spaced
points along a line across the duct, 2) the same sample rate should be maintained at each sampling point, and 3) the samples from each
point should be mixed and drawn through a single sampling line. Figure 02-05-01-05A is a schematic of the basic multiport design.
Eight holes are drilled at evenly spaced distances along the sampling tube. For a 0.5 1pm flowrate.a 1.295 am hole (or approximately a
#55 drill) is drilled (see primary source for calculations at other flowrates). The tube should also be equipped with backflushing
capability to periodically purge the holes of particulates. An internal filter should also be used to prevent fine particles from
reaching the sample lines (see 02-05-01-01).
4. APPLICATION'- Engineering evaluation R&D.
A) OPERATIONAL SCOPE
This probe is designed to obtain representative gas samples under stratified gas conditions. The probe is designed to operate
under moderate grain loading at temperatures and conditions acceptable to 316 SS or Inconel.
B) INTERFERENCES/LIMITATIONS
Particulates can enter probe, so an internal filter is required. Ports must face into the flow. (See primary source for advanced
design considerations.)
C) RECOMMENDED USE AREA
This is the recommended probe for continuous gas analysis by on-line instrumentation for all levels.
5. OPERATIONAL PARAMETERS
A) RANGE Moderate grain loading and temperatures and conditions suitable to 316 SS or Inconel.
B) ACCURACY +68!
Cl PRECISION ±5%
6. REAGENTS REQUIRED
N/A
7. EQUIPMENT REQUIRED
See Figure 02-05-01 -05A.
& KEYWORD INDEX' Sampling, gases, multiport sampling probe.
9. CROSS REFERENCE ID NUMBERS 02-05-01-01, 02, 03, 04.
10. REFERENCES
A) PRIMARY SOURCE
400 Brooks, E.F., C.A. Flegal, L.N. Harnett, M.A. Kolpin, O.J. Luciani and R.L. Williams, "Continuous Measurement of Gas Com-
position from Stationary Sources," EPA-600/2-75-012, TRW Defense and Space Systems, Redondo Beach, Ca., July 1975.
B) BACKGROUND INFORMATION
401 Zakak, et al, "Procedures for Measurement in Stratified Gases," EPA-650/2-74-086-a and -b, September 1974.
C) FIELD APPLICATIONS
-------
TITLE MULTIPORT PROBE FOR CONTINUOUS GAS MONITORING (CONTINUED)
PAGE 2 OF 2 FOR
ID NO. 02-05-01-05
HEAT TRACED
SAMPLE TUBE
COARSE
PARTICULATE poORF
FILTER BODY
— -
XV* ^\ ^^ XV XV XV j".
I ' UJJJ
II
DUCT
WALL
APPROXIMATE
LOCATION OF
FILTER
HEAT TRACED
SAMPLE TUBE
SAMPLE
PORT
PURGE
PLUG
DUCT
WALL
Figure 02-05-01-05A. Multi-hole Sampling Probe.
-------
PAGE 1 OF 3 FOR
1. TITLE CONTINUOUS MONITORING OF NO/NO2
2 IDENTIFICATION CODE
02-05-02-01
3. ABSTRACT OF METHODOLOGY
Table 02-05-02-01A summarizes representative equipment for NO/NOX analysis. The recommended method for fugitive emissions is either
chemiluminescent NO/NOX or coulometric analyzer. The chemiluminescent approach is favored for its higher sensitivity and specificity.
For flue gas analysis the NDIR unit or the chemiluminescent unit are recommended. The NDIR unit is favored for continuous process
monitoring, while chemiluminescent unit is better for engineering evaluation or level 2 environmental assessment.
While no instrument is recommended for remote sensing, the Barringer Cospec unit has proven its utility in the field.
4. APPLICATION- Engineering Evaluation R&D, Environmental Assessment.
A) OPE RATIONAL SCOPE
See Table 02-05-02-01A.
B) INTERFERENCES/LIMITATIONS
See Table 02-05-02-01A.
C) RECOMMENDED USE AREA
See Abstract of Methodology.
5. OPERATIONAL PARAMETERS
A) RANGE See Table 01-05-02-01A.
B) ACCURACY See Table 01-05-02-01A.
C) PRECISION See Table 01-05-02-01A.
6. REAGENTS REQUIRED
Calibration gases.
a KEYWORD INDEX:
9. CROSS REFERENCE
10. REFERENCES See
7. EQUIPMENT REQUIRED
See Table 01-05-02-01A.
Analysis, continuous monitoring, NOj, NO.
ID NUMBERS 01-05-01-01, 02, 03, 04.
Table 01-05-02-01A.
PRIMARY SOURCE
B) BACKGROUND INFORMATION
C) FIELD APPLICATIONS
308
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PAGE 2 OF 3 FOR
TITLE CONTINUOUS MONITORING OF N0/N02 (CONTINUED) ID NO 02-05-02-01
— L
Tab]e 02-05-02-01A. Representative Instruments for On-Line Continuous Monitoring of NO/NO .
Representative
Manufacturer/
Model
Barringer
Cospec IV
Beckman Model
909
Model 910
Beckman Model
865
DuPont Model
461
Dynascience
P100D
Lear Siegler
Spectrometrlcs
I
,
Technicon
Air Monitor
IV
^"^^^""•"^^•l !!•••! .
Therm Electron
Principle of Operation
• — — — — — - — •
Correlation Spectroscopy.
Instrument consists of 2 tele-
scopes, a 2-grating spectrom-
eter for dispersion, a disc
shaped multiple slit mask, and
electronics. Disc mask is a
high contrast ref. spectrum for
correlation against incoming
absorption spectra. Photo-
multiplier tubes detect light
modulations produced by rotation
of the disc. Unit continuously
measures optical depth in ppm-
meters of gas cloud under obser-
vation and uses sky light as
source of radiation.
! Coulometric. Inlet gas passes
thru selective scrubber to remove
S02, 02, N02, mercaptans and HpS
from sample. The NO is reacted
with ozone and the N02 formed
reacts with 13 in electrolyte
producing I2. The I2 is reduced
at the cathode and the current
required is proportional to the
NO.
Coulometric. Selective scrubber
removes 03, SO,, H2S from sample.
The N02 reacts with I" in elec-
trolyte producing I2. The I2 is
reduced at the cathode and the
current required is proportional
to the N02.
NDIR. Differential absorption of
infrared energy measured by a
selective gas microphase detector
in a dual beam optical system.
NDUV. A beam of light is passed
thru the sample, then split and
monitored.
Electrochemical cell. Instrument
includes sampling and condition-
ing equip, to monitor source
gases. Sample acquired thru use
of heateJ sintered SS filter and
heated sample lines. Principle
of operation is based on the com-
bined use of a semi -permeable
membrane and liquid state con-
trolled oxidation-reduction.
Second Derivation Spectroscopy and
Ultraviolet region from 190 nm-400
nm is automatically scanned and a
second derivative spectra is pro-
duced whose peak location and
intensity identifies the pollutant
and its concentration.
—
Colorimetric. N02 is monitored
directly using a modified Saltzman
reaction (diazotization and cou-
pling). NOX is found by oxidizing
10 with chromium trioxide and sub-
sequent measurement of N02 using a
modified Saltzman method.
_^ — - — ~ ~ ~~~
— — _— — ^
Cheroiluminescent. NO and 03 react
rNO+03 = N02+02+hv) and emit light
at 0.6-3n. A high sensitivity
photomultiplier monitors the light
emitted in the reaction chamber.
NO is determined in the same
fashion after N02 is reduced to
NO in a catalytic converter.
. —
Species
Monitored Range
_
H02 1-700 ppm
meters
NO 0-1.0 ppm
(3 ranges)
N02 0-1.0 ppm
(3 ranges)
NO 0-100%
(0-500 ppm)
NO 0-100 ppm
* 0-100%
NO /NO, 0-2000
x c (3 ranges)
NO/ HO, 0-10 ppm
(4 ranges)
-. — '
N02/NOX 0-0.15 ppm
_ .
NO/NO, 0-2500 ppm
x (9 ranges)
_ . — •*•
Sensitivity
1 ppm-meter
4 to 100 ppb
(depending
on range)
4 to 100 ppb
(depending
on range)
0.5S full
scale
5 ppm
2% of full
scale
.006 ppm NO
.040 ppm N02
__ — — — — —
.0015 ppm
—
ppb
—
Fugitive
Emissions
— -
Yes
-j f — — —
Flue Gas Interferences/
Emissions Remarks
Ref.
. — 1
Yes' 'Normal source anal- [ 402, |
ysis consists of
monitoring stack
plume. Monitors NO.
Yes
Yes
No
No
No
Yes
ii i
Yes
Yes
_
1
No
No
Yes
Yes
Yes
No
No
•~
Yes
03, S02, H2S, N02
and RS must be
removed prior to
analysis .
03, S02, H2S and RS
i;tust be removed
prior to analysis.
Can operate in rela-
tive humidities up
to 100:;.
Water interference
<2.8'» of HOX signal.
SO? interference
< 0.455) of NOX
signal.
Interferences
removed via internal
sample conditioning.
Interferences must
be detected thru
lanual scan.
403
«
405,
411
405 1
414, 1
411
405, 1
406 1
406
407,
408
409,
410
1
A 5x ozone concen-
tration to N02 will
cause slight inter-
'erence. A 30x sul-
ur dioxide cone, to
N02 might bleach the
404,
405
nnk azo dye to a 1 1
light extent. 1
, iBiM*»iiiimii~^»^^^^^^^B^^l__^^^^_^^^^^
nterferences com-
nonly found in
mbient air amount
0-^0.5 on most
ensitive range
0-0.01 ppni).
405,
412,
413
|_ \
1
. _
309
-------
TITLE CONTINUOUS MONITORING OF NO/NO2 (CONTINUED)
PAGE 3 OF 3 FOR
ID NO. 02-05-02-01
Table 02-05-02-01A (Continued)
402 Newcoinb, T.S., and H.M. Millan, IEEE Trans. Geo. Elect., GE-8, 149 (1970).
403 McCreight, C.R., and C.I. Tien, "Interpretation Problems In the Correlation Map Sensing Techniques," presented at the Joint
Conference on Sensing of Environmental Pollutants, Palo Alto, Calif. (Nov. 8-10, 1971); Available from AIAA Library, 750 Third
Avenue, New York, N.Y.
404 Harman, J.N., "Continuous Colorimetric Analysis of Ambient Oxides of Nitrogen (NO and N02)," Adv. Instr., 26, Part 1, Oct. 1971.
406 Decker, C.E., T. Royal and J. Tommerdahl, "Field Evaluation of New Air Pollution Monitoring Systems," Final Report of Research
Triangle Institute, Research Triangle Park, N.C., EPA Contract #CPA70-101, May 1972.
406 Saltzman, R.S., and J.A. Williamson, "Monitoring Stationary Source Emissions for Air Pollutants with Photometric Analyzer Systems,"
Air Quality Instrumentation, Vol. 1, Instrument Society of America, Pittsburgh, Pennsylvania.
407 Shen, T.T., and W.N. Stasivk, "Performance Characteristics of Stack Testing Instruments for Oxides of Nitrogen," APCA paper number
73-116, Presented at the 66th Annual Meeting of the Air Pollution Control Association, Chicago, 111., June 1973.
408 Snyder, A.D., E. Eimutis, M. Konicek, L. Parts and P. Sherman, "Instrumentation for the Determination of Nitrogen Oxides Content
of Stationary Source Emissions," Vol. 2, Report of Monsanto Research Corp., Dayton, Ohio, EPA Contract =EHSD71-30, EPA Publication
APTD-0942, Jan. 1972.
409 Hager, R.N., and R.C. Anderson, J. Opt. Soc. Amer., 60, 1444 (1970).
410 Williams, D.T., and C.S. Palmer, Field Applications of the Multicomponent D2 Spectrometer," Final Report on Project AP01294-01
for the EPA (Oct. 1, 1972).
411 Stevens, R.K., et al, "Field Performance of Advanced Monitors for All Sorts of Nitrogen, Ozone, Sulfur Dioxide, Carbon Monoxide,
Methane, and Non-Methane Hydrocarbons," APCA Paper #72-13, Presented at the 65th Annual Meeting of the Air Pollution Control
Assoc., Miami, Florida (June 18-22, 1972).
412 Winer, A.M., J.W. Peters, J.N. Pitts and J.P. Smith, Environ. Sci. Tech., 8(13), 1118 (1974).
413 Stedman, D.H., E. Daby, H. Niki and F. Stuhly, "Analysis of Ozone and Nitric Oxide by a Chemiluminescent Method in Laboratory
and Atmospheric Studies of Photochemical Smog," J.A.P.C.A.. 2£, 260 (1972).
310
-------
PAGE 1 OF 3 FOR
1. TITLE CONTINUOUS MONITORING OF OZONE
i IDENTIFICATION CODE
02-05-02-02
3. ABSTRACT OF METHODOLOGY
Table 02-05-02-02A summarizes representative equipment for continuous monitoring of 03. The measurement of ozone is primarily devoted
to fugitive emissions. The recommended unit for fugitive emissions is a chemiluminescent detector. If total oxidant is to be measured
or greater sensitivity is required, an amperometric total oxidant unit can be used. The Meloy instrument has been selected by the
EPA as a reference method for ambient ozone measurements.
4. APPLICATION: All areas.
A) OPERATIONAL SCOPE
These instruments are designed to operate in ambient conditions, but can be applied to flue gas monitoring.
B) INTERFERENCES/LIMITATIONS
The chemiluminescent detector is specific for ozone, while the amperometric detector responds to all oxidants.
C) RECOMMENDED USE AREA
The instruments discussed in the Abstract of Methodology can be used for all areas for fugitive emissions.
5. OPERATIONAL PARAMETERS See Table 02-05-02-02A.
A) RANGE
B) ACCURACY
C) PRECISION
"•" —^^^» ^^^»
6. REAGENTS REQUIRED
Calibration gases.
8L KEYWORD INDEX: Analysis, continuous monitoring, NO, N0r
—. •
9. CROSS REFERENCE ID NUMBERS 02-05-01-01, 02, 03, 04,.
—•
10. REFERENCES See Table 02-05-02-02B.
A) PRIMARY SOURCE
B) BACKGROUND INFORMATION
C) FIELD APPLICATIONS
7. EQUIPMENT REQUIRED
See Table 02-05-02-02A.
311
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PAGE 2 OF 3 FOR
TITLE CONTINUOUS MONITORING OF OZONE (CONTINUED) ID NO. 02-05-02-02
Table 02-05-02-02A. Representative Continuous On-Line 03 Monitors.
Representativ
Manufacturer/
Model
Beckman
Model 908
Dasibi
Model 1003-AH
Lear Siegler
Model III d2
Technicon
Air Monitor IV
Thermo
Electron
Model 10A
Meloy
Model
OA 350-2R
Principle of Operation
Araperoinetric. An air sample is
drawn through a detector cell
containing buffered KI. Oxidant
in the air sample oxidizes the
iodide to iodine which is
sensed by the electrode system.
The iodine produced is reduced
at the cathode yielding a cur-
rent proportional to the oxidant
present in the air sample.
Ultraviolet Absorption. The UV
absorbance of reference gas
stream (03 reduced catalytically
and a sample stream are taken at
253.7 nm. The absorbance of the
sample stream minus the referenc
absorbance is displayed on the
instrument as ppm Oj.
Second derivative Spectroscopy.
Ultraviolet region at 263^ is
automatically scanned and a sec-
ond derivative spectra is pro-
duced whose peak location and
intensity identifies the pollu-
tant and its concentration.
Colorimetric. Neutral KI is
reduced by 03 releasing Ij. The
quantity of 1 2 produced is
monitored spectrophotometrically
at 352 nm.
Chemi 1 umi nescence.
N03 + 03 — N02 + 02 + hv
(0.6-3f). In practice an
unknown stream of 03 is com-
bined in the reaction chamber
with NO and the reaction is
monitored with a photo-
mul tip! ier.
Chemi luminescence.
N03 + OT N02 + 0? + hv
(0.6-3p). In practice an
unknown stream of 03 is com-
bined in the reaction chamber
with NO and the reaction is
monitored with a photo-
multiplier.
Species
Moni torec
Total
Oxidant
°3
J
°3
3
Total
Oxidant
°3
°3
Range
0-1 ppm
(3 ranges)
0.003-
20 ppm
0-10 ppm
(4 ranges)
0-0.2 ppm
0-10,000 ppm
(8 ranges)
0-0.5 ppm
Sensitivity
4 ppb
3 ppb
0.025 ppm
0.0015 ppm
0.1 ppra
0.1 ppm
Fugitive
Emissions
Yes
Yes
Yes
Yes
Yes
Yes
Flue Gas
Emissions
No
Yes
No
Yes
Yes
No
Interferences/
Remarks
This type of
instrument does not
monitor ozone con-
centration directly.
Instead the total
oxidant level is
found.
No interference
from 1.0 ppm N02-
Interferences noted
by manually scan-
ning region of
interest.
Since this instru-
ment is not specific
to 63, one must be
aware that other
oxidants in the air
wi 11 also be meas-
ured. Nitrogen
dioxide at 0.100 ppm
will be read as
0.009 ppm 03. A
negative error from
SO? is reduced by
using an oxidizing
col umn to remove
the S02.
No known inter-
ferences. This
instrument can also
measure NO by
reversing the roles
of the gases.
No known inter-
ferences. This
instrument can also
measure NO by
reversing the roles
of the gases.
Ref.
405,414,
411,423,
424,427,
423,430,
436,438
405,415,
416,431,
432,433
417,418,
434,435
405,414,
425,426,
430
419,420,
421,422,
423,437,
439
564
312
-------
PAGE 3 OF 3 FOR
TITLE
CONTINUOUS MONITORING OF OZONE (CONTINUED)
ID NO. 02-0&02-02
Table 02-05-02-02B
References for Ozone Continuous Monitors
414
405
419
420
428
429
430
431
432
433
434
435
436
437
Royal and J Tommerdahl, "Field Evaluation of New Pollution Monitoring System: St Louis
:h Triangle Institute, Research Triangle Park, N.C., EPA Contract ICPA70-101, Aug 1971.
J. Tommerdahl, "Field Evaluation of New Air Pollution Monitoring Systems," Final Reoort Dent of
, Research Triangle Park, N.C., EPA Contract ICPA70-101, May 1972. P ' P
411 Stevens, R.K et al, "Field Performance Characteristics of Advanced Monitors for Oxides of Nitrogen, Ozone, Sulfur Dioxide
Control Assoc !'M*mi!nFl. June^l972 OCarb0"S'" ^ ^^ m'"' presented at the Annual Meeti"9 °f ^e Air Pollution'
415 Shikiya, J.M., et al, California Air Resources Board, Los Angeles, Rept. IIE-6, 1972.
416 Bowman, L.D., and R.F. Horak, "A Continuous Ultraviolet Absorption Ozone Photometer," presented at the 1972 ISA Conference in
Ssn Fr3ncisco t Msy 1972.
417 Hager, R.N., and R.C. Henderson, J. Opt. Soc. Am.. 60_, 144 (1970).
418 Williams, D.T., and C.S. Palmer, "Field Applications of the Multi-Component D4 Spectrometer," Final Report of Project AP01293-01
for the EPA (Oct. 1, 1972).
Reger, B.H., "Measurement of Atmospheric Ozone with the Chemiluminescence Method," J. of Geophy. Res.. 69, 3795 (1964).
Tommerdahl, J.B., "Ozone Chemi luminescence Study," Final Report of Research Triangle Instruments, Research Triangle Park, N.C.,
prepared for National Air Pollution Control Admin., USDHEW-PHS, Contract ICPA-22-69-7 (1969), NTIS Report fPB-194-116.
421
422
Hodgeson, J.A., K. Krost, A. O'Keefe and R. Stevens, "Chemiluminescence Measurement of Atmospheric Ozone," Anal. Chem., 42,
1795 (1970). —
Key to National Problems," National Bureau of Standards
Altshuller, A.P., "Analytical Problems in Air Pollution Control:
Special Publication 351 (Aug. 1972).
423 Stevens, R.K., L. Ballard, C. Decker and J. Hodgesen, "Ratio of Sulfur Oxide to Total Gaseous Sulfur Compounds in Ozone to Total
Oxidants in the Los Angeles Atmosphere," in "Determination of Air Quality," New York Plenum Press, 1970, p. 83.
424 Clark, T.A., R. Baumgardner, R. Stevens, and K. Krost, "Evaluation of New Ozone Monitoring Instruments by Measuring in Nonurban
Atmospheres," presented at the Conference on Instrumental Monitoring for Ambient Air, Boulder, Colorado (Aug. 14-16, 1973).
425 Tokiwa, Y., and P.K, Mueller, "Status of Measuring Air Quality," J. Environ. Sci., 14_, 10 (1971).
426 "Standard Method of Tests for Continuous Analysis and Automatic Recording of the Oxidant Content of the Atmosphere," in 1972
Annual Book of ASTM Standards, Part 23, American Society for Testing and Materials, Philadelphia, PA., p. 526.
427 "Tentative Method for Continuous Monitoring of Atmospheric Oxidant with Amperometric Instruments," Methods of Air Sampling and
Analysis, American Public Health Assoc., Washington, D.C., 1972, p. 341.
Wartburg, A.F., A.W. Brewer and J.P. Lodge, "Evaluation of Coulometric Oxidant Sensor, J. Air Water Pollut., 8, 21 (1964).
Potter, L., and S. Duckworth, "Field Experience with the Mass Ozone Recorder," J.A.P.C.A., 15, 207 (1965).
Siu, W., M.R. Alhlstrom and M. Feltein, "Comparison of Coulometric and Colorimetric Analyzer Data," presented at the 20th
Conference on Methods in Air Pollution and Industrial Hygiene Studies, California Dept. of Public Health, Berkeley, California,
(Feb. 19-21, 1969).
Renzetti, N.A., "Ozone in the Los Angeles Atmosphere," J. Chem. Phy., 24_, 909, (1956).
Coloff, S.G., M. Cooke, R.J. Drago and S.F. Sleva, "Ambient Air Monitoring of Gaseous Pollutants," Amer. Lab.. 5, 10 (1973).
P.L. Hanst and W.A. McClenny, "Air Pollution Monitoring by Advanced Spectrographic Techniques," Science, 182,
Hodgeson, J.A.
248 (1973).
Anal. Chem., 13, 1131A (1973).
Hager, R N , "Derivative Spectroscopy with Emphasis on Trace Gas Analysis,
Grunn, F., D. Paine and L. Solar, "Derivative Absorption and Emission Spectrophotometry," Appl. Opt., 11, 93 (1972).
Lindquist, F., Analyst, 97_, 549 (1972).
D H H Nici and D.F. Stuhl, J.A.P.C.A., 22, 260 (1972).
7felho"d for the Measurement of Photochemical Oxidants Corrected for Interferences
438 "tnterim Report of Collaborative Study-Ref. Method for the easuremen o
Due to Nitrogen Oxides and Sulfur Dioxides," EPA Report 1650/4-74-031, Feb. 1973. Pnlllltant, »
439 Stevens, R.K , and J.A. Hodgeson, "Applications of Chemiluminescence Reactions to the Measurement of Air Pollutants,
Anal. Chem., 45_, 443A (1973).
564 fed._ §§£._ 40 , 54856 (1975)
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PAGE 1 OF 3 FOR
1. TITLE CONTINUOUS MONITORING OF SULFUR DIOXIDE
2. IDENTIFICATION CODE
02-05-02-03
3. ABSTRACT OF METHODOLOGY
Table 02-05-02-03A summarizes the representative equipment for S02 continuous monitoring. The recommended method for fugitive
emission monitoring is the pulsed fluorescent instrument because of its sensitivity and specificity. For flue gas monitoring, either
the NDIR or electrochemical instrument is recommended. The NDIR unit is more useful for continuous process monitoring, while the
electrochemical unit's portability makes it more useful for environmental assessment. The Meloy (SA-185-2A) and the Thermo Electron
units are designated as equivalent compliance methods for ambient measurements.
4. APPLICATION: An areas.
A) OPE RATIONAL SCOPE
The equipment listed in Table 02-Q5-02-03A can be used for fugitive emission or flue gas monitoring.
B) INTERFERENCES/LIMITATIONS
See Table 02-05-02-03A.
C) RECOMMENDED USE AREA
See Abstract of Methodology.
5. OPERATIONAL PARAMETERS See Table 02-05-02-03A.
A) RANGE
B) ACCURACY
C) PRECISION
6. REAGENTS REQUIRED
Calibration gases.
7. EQUIPMENT REQUIRED
See Table 02-05-02-03A.
a KEYWORD INDEX: Analysis, continuous monitoring, SO,.
9. CROSS REFERENCE ID NUMBERS 02-05-01-01, 02-05-01-02, 02-05-01-03, 02-05-01-04.
10. REFERENCES See Table 02-05-02-03B.
A) PRIMARY SOURCE
B) BACKGROUND INFORMATION
C) FIELD APPLICATIONS
314
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PAGE 2 OF 2 FOR
TITLE CONTINUOUS MONITORING OF SULFUR DIOXIDE (CONTINUED)
• — ' : •, — — „ ,
ID NO. 02-05-02-03
• .
Table 02-05-02-03A. Continuous Monitoring Methods for Sulfur Dioxide.
Representative
Manufacturer/
Model
MELOY
Laboratory
Model 185-2A
Model FSA 190
Tracer 270HA
Thermo
Electron
Corporation
Model 43
Theta Sensors,
Inc.
Series 7100
Phillips
Electronics
PW 9700
Lear Siegler
SM 1000
Hi Iks
MIRAN-II
Beckman
Model 864 S
DuPont
Model 460
H^ ^^ ^^ _^__
Barringer
Res. Ltd.
Cosper II
Principle of Operation
Flame Photometric:
Hydrogen rich flame chem-
i luminescent reaction.
Photomultiplier pickup of
emitted light.
GC separation and then
analysis by F.P. Detector.
Pulsed Fluorescent:
Excitation of SOg mole-
cules by UV source.
Fluorescence measured.
Electrochemical :
Chemical reaction occurs
between a gas and a
charged electrode to
produce a current flow.
Coulometric: Based
on coulometric titration
of S02 with internal
regenerated bromine
Second derivative
spectroscopy: Second
derivative spectra
generated whose inten-
sity is proportional
to the gas concentration.
IR Spectroscopy:
Narrow band pass filters
used to remove all but
analytical wavelength
in IR region.
Nondispersive IR:
Differential absorption
of IR energy measured
by a selective gas
microphone detector in
a dual beam optical
Nondispersive UV:
A beam flight is passed
through the sample,
then split and moni-
tored by two photo-
tubes, one monitoring
a reference wavelength
and the other a non-
absorbing wavelength.
—
Correlation Spectro-
scopy: Instrument con-
sists of two telescopes,
a two-grating spec-
trometer for dispersion,
a disc shaped multiple-
slit mask, and elec-
tronics. Disk mask is a
high contrast reference
spectrum for correlation
against incoming absorp-
tion spectra and is com-
prised of arrays of
circular slits photo-
etched in aluminum on
quartz. Photomultiplier
tubes detect light modu-
lations produced by
rotation of disc. Unit
continuously measures
optical depth in ppm-
meters of gas cloud
under observation and
uses diffused sunlight
as a source of
radiation.
_
'
Species
Monitored
Sulfur
compounds
S02, H2S
so2
so2
c.
so?
c.
so2
£.
so2
so2
so2
!••
so2
t
Range
0.01 to 10 ppm
25 to
10,000 ppm
0 to 100 ppb
0 to 1 ppm
0 to 0.5 ppm
0 to 1 ppm
0 to 50 ppm
(0 to 5000 ppm]
0 to 5000 ppm
0 to 3 ppm
0 to 0.5 ppm
0 to 2.0 ppm
0 to M,
(variable)
0 to 100%
0 to 100 ppm
(0 to 100%)
— ""
1 to 1000 ppm
meters
Sensitivity
0.01 ppm
'5 ppm
1 ppb
5 ppb
0.01 ppm
4 ppb
0.010 ppm
0.14 ppm
0.57, full
scale
5 ppm
~— — — ^ — ~—
6 ppm meters
• L
_
Ambient
Analysis
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
_ M M
No
Source
Analysi
Hn
Yes
No
Yes
Yes
No
No
Yes
Yes
Yes
-^^—•M •— i
Yes
i
s Interferences/Remarks
Must be aware that all
sulfur compounds are
registered. Optional
scrubbers available to
remove interferents.
Because of the GC, this
instrument is specific
for S02.
Instrument is specific
for SOj.
Some sample condi-
tioning registered for
source monitoring.
Full-scale concentra-
tion set with calibra-
tion gas.
Specificity increased
due to pre-filters to
remove H^S, ozone, etc.
Second derivative
spectroscopy elim-
inates most wavelength
interferences .
Source analysis can be
complicated by
presence of water
vapor.
Sample must be condi-
tioned to lower water
vapor .
"
II 1 II 1 •! • ""•"""•
There are slight
interferences due to
changes in sky spec-
tral distribution.
Light scatter from
particulates might
cause interpretation
problems.
•
References
405,411,
443,444,
446,451
565
•
446,
451
445
566
447
405,440,
441,443
448
449
411,
441
441,
442
450
— — " '
— —
315
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PAGE 3 OF 3 FOR
TITLE CONTINUOUS MONITORING OF SULFUR DIOXIDE (CONTINUED)
ID NO, 02-0542-03
Table 02-05-02-03B. Reference for S02 Continuous Monitors
440 Kabot, F., "So Goes S02>" Ind. Res., Sept. 1970.
441 Saltzman, R.A., and J.A. Williamson, "Monitoring Stationary Source Emissions for Air Pollutants With Photometric Analyzer Systems,"
Air Quality Instrumentation, Vol. 1, Instrument Society of America, Pittsburgh, Pennsylvania.
442 Jaye, F.J., "Monitoring Instrumentation for the Measurement of Sulfur Dioxide in Stationary Source Emissions," EPA-R2-73-163,
Feb. 1973.
443 Stevens, R.K., L.F. Ballard and C.E. Decker, "Field Evaluation of Sulfur Dioxide Monitoring Instruments," U.S. Environmental
Protection Agency, Air Pollution Control Office, Raleigh, N.C.
444 Stevens, R.K., and E.O. O'Keefe, "Modern Aspects of Air Pollution Monitoring," Anal. Chem., 42, 143A (1970).
445 Zolner, W., E. Cieplinski and Dennis Helm, "Source Level 502 Analysis via Pulsed Fluorescence," Thermal Electron Corporation,
Waltham, Mass.
446 Brody, S.S., and J.E. Chaney, "Flame Photometric Detector," J. Gas Chrom., 1, 42 (1966).
447 "Plug-in Sensors and Membranes Put Finger on Air Pollutants," Prod. Eng., 41_, 40 (1970).
411 Stevens, R.K., et al, "Field Performance Characteristics of Advanced Monitors for Oxides of Nitrogen, Ozone, Sulfur Dioxide,
Carbon Monoxide, Methane, and Non-Methane Hydrocarbons," APCA Paper No. 72-13, presented at the 63rd Annual Meeting of the Air
Pollution Control Assoc., Miami, Florida (June 18-22, 1972).
405 Decker, C.E., T. Royal, and J. Tommerdahl, "Field Evaluation of New Pollution Monitoring Systems," Final Report of Research
Triangle Institute, Research Triangle Park, N.C., EPA Contract No. CP A70-101, May 1972 (Maloy).
448 Williams, D.T., and C.S. Palmer, "Field Applications of the Multicomponent 02 Spectrophotometer," Final Report on Project
APO 1293-01, for the EPA (Oct. 1, 1972).
449 Wilks, "Practical Approach to Internal Reflection Spectroscopy," Amer. lab. 4, 42 (1972).
450 Moffat, A.J., and M.N. Millan, "The Applications of Optical Relation Techniques to the Remote Sensing SO, Flumes Using
Skylight," Atm. Environ, Pergamon Press, 1971, Vol. 5, p. 677.
451 Barynin, J.A.M., and M.J.G. Wilson, Atm. Environ., 6, 197 (1972).
565 Fed. Reg. 41_, 3893 (1976).
566 Fed. Reg. 41_, 8531 (1976).
316
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PAGE 1 OF 3 FOR
1. TITLE CONTINUOUS MONITORING OF C0/C02
3. ABSTRACT OF METHODOLOGY
i IDENTIFICATION CODE
02-05-02-04
Table 02-05-02-04A suMnarizes representative CO/CO, instructs. The recorded method for furtive emission and f,ue gas
monitoring ,s NDIR WHh the proper conditioning,the ND.R unit „,„ provide accurate and rapid response. The Be^an Mode, 866
has been designated a reference method for ambient CO measurements.
4. APPLICATION: An areas.
A) OPE RATIONAL SCOPE
See Table 02-05-02-04A.
B) INTERFERENCES/LIMITATIONS
See Table 02-05-02-04A.
C) RECOMMENDED USE AREA
See Abstract of Methodology.
5. OPERATIONAL PARAMETERS See Table 02-05-02-04A.
A) RANGE
B) ACCURACY
C) PRECISION
6. REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Calibration gases.
See Table 02-05-02-04A.
& KEYWORD INDEX: Analysis, continuous monitoring, CO, C02.
- •—
9. CROSS REFERENCE ID NUMBERS 02-05-01-01, 02, 03,
— ————
10. REFERENCES See Table 02-05-02-04B.
• •
A) PRIMARY SOURCE
B) BACKGROUND INFORMATION
C) FIELD APPLICATIONS
-------
TITLE CONTINUOUS MONITORING OF CO/CO2 (CONTINUED)
ID NO. 02-05-02-04
Table 02-05-02-04A;. Summary of Representative Instruments for Continuous On-Line Monitoring of C0/C02.
Manufacturer
Model
Principle of Operation
Species
Monitored
Range
Sensi tivity
Fugitive
Emissions
Flue Gas
Emissions
Interferences/
Remarks
Ref.
Bacharack
Model US 400
Mercury Substitution - Ultraviolet
Absorption: The heterogenous
reaction between carbon monoxide
and mercuric oxide is utilized to
generate mercury vapor in the sam-
ple gas stream at a concentration
proportional to the original CO
concentration. Ultraviolet
photometry is used to measure the
Hg vapor specifically and with
great sensitivity.
CO
0-500 ppm
0.05 ppm
No
Other gases can
release the Hg and
must be scrubbed
from the sample
gas before contact
with the HgO.
453,
466
Beckinan
Model 866
NDIR: Differential absorption of
infrared energy measured by a
selective gas microphone detector
in a dual beam optical system.
CO
0-50 ppm
0.4 ppm,
Yes
No
Solid, rugged method
of CO monitoring.
HjO vapor should be
removed for most
accurate results.
568,
052,
452,
454,
466,
467
Enviro-
Metrics
Model C-328
Electrochemical cell: Some of
the sample gas molecules diffuse
through a membrane and dissolve in
a thin film covering a sensing
electrode. Electrooxidation or
reduction occur at this electrode.
The current is monitored versus a
reference electrode and related
to the gas of interest.
CO
0-10,000 ppm
(Range
variable)
1* full
scale
Yes
Yes
Sample conditioning
is essential to
operation of instru-
ment. Water, SO,
and NO? must be
removed.
455,
466
Environmenta
Data 1
Diga Series
Absorption Spectroscopy: Long
path in stack absorption of IR
radiation at 4.7(i for CO and
4.25jj. for C02-
CO/CO,
0-1000 ppm
(2 ranges)
N/Q
No
Yes
Sulfur dioxide, NO,
C02 and opacity can
also be measured.
456,
457,
466
Mine Safety
Appliances
Model D
Catalytic Oxidation: A sample of
air is drawn through two beds of
active and inactive Hopcalite.
Thermistors in each bed monitor
the heat of oxidation of CO to
CO
0-500 ppm
N/Q
Yes
CO
Interferences (SO?,
NO, and water) must
be removed before
sample is introduced
into the cell.
459,
460,
461,
466
2-
Philips
Amperometric: Dust and inter-
fering gases are removed from the
sample gas stream. The CO reacts
with an active element (iodine
Dentoxide) in an electrolytic
cell. The change in concentration
of the active element generates
a current which varies directly as
the concentration of the gas
component being measured.
CO
0-200
(4 ranges)
0.1 ppm
Yes
No
By proper choice
of prefilters this
unit can also mea-
sure S02, NOx, 03
and H2S. Inter-
ferences from
these gases are
less than 1%, but
require careful
conditioning of
interference
absorbant column.
458,
462
Wilks
Model 5630
Dispersive IR: This instrument
consists of a variable IR range
"rom 2.5 to 14.5^ and variable
iath gas cell from 3/4 to 20
meters. The CO absorbance at
.7u. or the C02 absorbance at
.25^ is monitored.
CO/CO,
0-8.3*
1.2 ppm
Yes
Yes
Water should be
eliminated by the
use of drying
agents. Contribu-
tions by other
interferents (N20,
H2S, olefins,
cyanogens, etc.) can
be subtracted from
the CO/C02 absorb-
ance by scanning the
2 to 14n spectrum.
458,
463,
464,
465,
467
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PAGE 3 OF 3 FOR
TITLE
CONTINUOUS MONITORING OF CO/CO2 (CONTINUED)
ID NO. 02-05-02-04
Table 02-05-02-04B
Continuous On-Line Instruments for C0/C02 Monitoring
452 Chapman, R.L., Pollut. Enq.. 4(6), 38 (1972).
453 Robbins, R.C., K.M. Bong and E. Robinson, "Carbon Monoxide in the Atmosphere," J^P.^A,. 18, 106 ( 1968).
052 Leithe, W., "The Analysis of Air Pollutants," Ann Arbor-Humphrey Science Publishers, London, 1970, p. 63-68.
454 Source Emission1"" VolT'Re""'°f S|!yder' "Instrumentation for the Determination of Nitrogen Oxide Control of Stationary
455 "Plug-In Sensors In Membranes Put Finger on Inter Pollutants," Prod. Eng., 41, 40 (1970).
456 Lord, H.C., et al, "Instantaneous, Continuous, Directly On-Stream Boiler Flue Gas Analysis," presented at the Instruments
Society of America, 24th Annual Power Industry Symposium, New York City, N.Y. (May 17, 1971).
457 Rosenthal, K., and R.J. Ambeck, "Continuous Monitoring of Stack Gases," presented at the Instrument Society of America, 18th Annual
Analytical Instrument Division Symposium, San Francisco, California (May 3, 1972).
458 Lord, H.C., "Absorption Spectrometry Applied to Monitoring Emissions from Stationary Sources," presented at the 1973 Spring
American Chemical Society Meeting, Dallas, Texas (April 8-13, 1973).
459 Christian, J.E., and J.E. Johnson, "Catalytical Combustion of Atmospheric Contaminants Over Hopcalite," Inter. J. of Air Hater
Pollut.. j, 1 (1965).
460 Salzberry, J.M., J.W. Cole and J.H. Yoe, "Determination of Carbon Monoxide," Anal. Chem.. 19_, 66 (1947).
461 Lindsley, C.H., and J.H. Yoe, "Simple Thermometric Apparatus for Estimation of Carbon Monoxide in Air," Anal. Chem. Acta, 2,
127 (1948).
462 Lysyj, I., A. Hanley and J.F. Zarembo, "Rapid Method for Determination of Small Amounts of Carbon Monoxide in Gaseous Mixtures,"
Anal. Chem., 31., 902 (1959).
463 Dubois, L:, J.R. Monkman and A. Zdrojewsky, "The Analysis of Carbon Monoxide in Urban Air at the PPM Level and the Normal Carbon
Monoxide Value," J.A.P.C.A., 15, 135 (1966).
464 Wilkes, P.A., "The Practical Approach to Internal Reflections Spectrography," Amer. Lab., 4, 42 (1972).
465 Pierson, R.H., N.F. Aaron and E. St Clair Cantz, "Catalog of Infrared Spectra for Qualitative Analysis of Gases," Anal. Chem., 28,
1218 (1956).
466 Mage, D.T., R.I. Allen, W.F. Dabberdt, W.B. Johnson and F.L. Ludwis, J.A.P.C.A., 23 970 (1973).
467 "Collaborate Reference Method for Continuous Measurement of Carbon Monoxide in the Atmosphere (Non-dispersable Infrared
Spectrometry)," NTIS #PB-211-265, May 1972.
568 Fed. Reg. 41, 3624 (1976).
319
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PAGE 1 OF 2 FOR
1. TITLE CONTINUOUS MONITORING OF HjS
1 IDENTIFICATION CODE
02-05-02-05
1 ABSTRACT OF METHODOLOGY
Table 02-05-02-05A summarizes the representative equipment for H_S nonitorinn. The recommended method for fugitive emissions is a GC
with a FP detector because of the high sensitivity normally required. For flue gas measurements,the electrochemical instrument is
recommended.
4. APPLICATION^ Engineering evaluation RSD, environmental assessment.
A) OPERATIONAL SCOPE
See Table 02-05-02-05A.
B) INTERFERENCES/LIMITATIONS
See Table 02-05-02-05A.
C) RECOMMENDED USE AREA
See Abstract of Methodology.
5. OPERATIONAL PARAMETERS See Table 02-05-02 05A.
A) RANGE
B) ACCURACY
C) PRECISION
& REAGENTS REQUIRED
7. EQUIPMENT REQUIRED
Calibration gases
bai I uiaci un vja=>e:>*
(Note: AIRCO's aluminum containers are recommended for storage)
See Table 02-05-02-05A.
& KEYWORD INDEX: Analysis, continuous monitoring, H,S.
9. CROSS REFERENCE ID NUMBERS 02-05-01-01, 02-05-01-02, 02-05-01-03, 02-05-01-04; 01-01; 01-05.
10. REFERENCES See Table 02-05-02-05B.
PRIMARY SOURCE
B) BACKGROUND INFORMATION
C) FIELD APPLICATIONS
320
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PAGE 2 OF 2 FOR
TITLE CONTINOUS MONITORING OF H2S (CONTINUED)
ID NO. 02-05-02-05
Table 02-05-02-05A.
Manufacturer/
Model
Environ-
metries
Model S-390
Representative HjS Continuous Monitors.
Principle of Operation
-^ —
Electrochemical cell:
Some of the sample gas
molecules diffuse through
a membrane and dissolve
in a thin film covering a
sensing electrode. Elec-
trooxidation or reduction
occurs at this electrode.
The current is monitored
versus a reference elec-
trode and related to the
gas concentration.
Species
Monitored
Range
D-5000 ppm
'3 ranges)
ensitivi ty
1% full
scale
'ugitive
missions
Yes
Flue
Gas
Emissions
Yes
Interferences/Remarks I References
Source sampling
requires sample con-
ditioning to remove
water and paniculate
447,
468
Philips
Coulometric: The sample,
cleaned of particulate
and conditioned via
selective filters, is
introduced into a meas-
uring cell. The H2S
reacts with the active
element in the electro-
lyte changing the con-
centration of the active
element. This generates
a current which varies
directly with the H£S
concentration.
0-10,000 ppb
[3 ranges)
10
Yes
No Care must be taken in
ensuring that inter-
fering gases such as
S02 or NOX are
removed or compen-
sated for in the final
analysis.
Techni con
Air
Monitor IV
Coloumetric: HjS in
the gas stream is reacted
in a flowthrough cell
with p-aminodimethyl-
aniline and Fed 3 to pro-
duce a colored product
whose absorbance is
monitored at 660 nm.
0-200 ppb
2 ppb
Yes
Yes
469,
470
Selective removal of
S02, N0x,03 required
for specific results
471,
472
Tracer
270H
Analyzer
GC - Flame Photometric
Detector: The sample
is eluted from the gas
chromatographic column,
mixed with air and
burned in an H2 rich
flame. The decomposi-
tion of the sample
in this flame gives a
characteristic optical
emission at 394 nm.
H?S,
Sf RSH
0-1 ppm
(variable)
5 ppb
Yes
Yes
Not truly continuous,
but sample injected
automatically on
column at pre-
selected times
allows analysis of
all sulfur compounds
465,
473,
474
Table 02-05-02-05B.
List of References Concerning Continuous Monitors for Hydrogen Sulfide Emissions.
447
468
469
470
472
472
473
405
474
"Plug-in Sensors in Membranes Put Finger on Air Pollutants," Prod. Eng., 41(26), 40 (1970).
Chand, R., and R.V. Marcote, "Evaluation of Portable Electrochemical Monitors and Associated Stack Sampling for Stationary Source
Monitoring," presented at the 68th National Meeting of the American Institute of Chemical Engineers, Houston, Texas.
Washburn, H.W., and R.R. Austin, "The Continuous Measurement of Sulfur Dioxide and Hydro Sulfide Emissions by Automatic Titration,"
Chapter 72 in Air Pollution Proceedings of the U.S. Technical Conference on Air Pollution, L.C. McCabe (chairman), McGraw-Hill,
New York, 1952.
R.R. Austin, 6.H. Dehaas, and G.N. Thoen, "Instrumentation for Quantitative Measurement of Sulfur Compounds in Flue Gases,"
(Journal of the Technical Assoc. of Pulp and Paper Industry), 5JU 246 (1968).
Rodes, C.E., et al , J.A.P.C.A., 19, 575 (1969).
Palmer, H.F., et al, J.A.P.C.A., 19, 778 (1969).
Stevens, R.K., and A.E. O'Keefe, Anal . Chem. , 42_, 143A (1970).
Decker, C.E., T. Royal and J. Tommerdahl , "Field Evaluation of New Air Pollution Monitoring Systems," Final Report of Research
, .., . . ,
Triangle Institute, Research Triangle Park, N.C., EPA Contract No. EPA-70-101, May 1972.
Ballard, L.F., et al , "Field Evaluation of New Air Pollution Monitoring Systems: The Los Angeles Study,"
Research Triangle Institute, Research Triangle Park, N.C., EPA Contract No. 70-101, EPA Publication APED-
r,
April
321
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1. TITLE DETERMINATION OF HYDROCARBONS CORRECTED FOR METHENE
Z IDENTIFICATION CODE
02-05-02-06
3. ABSTRACT OF METHODOLOGY
Method involves use of hydrogen flame detector to measure total hydrocarbon content, and a gas chromatograph to measure methane.
Figure 02-05-02-06 shows a typical apparatus flow diagram. An aliquot of collected sample gas is treated for the removal of water,
C02, and nonmethane hydrocarbons in a stripper column. Methane and CO are allowed to pass through a GC column for separation. The
eluted methane is then passed through a catalytic reduction tube into a flame ionization detector. The CO is then eluted into the
tube and reduced to methane, then is passed into the flame ionization detector.
The hydrocarbon content is corrected for methane by subtracting the methane value from the total hydrocarbon value.
to ElfOHOMUM
Figure 02-05-02-06. Schematic of GC operation
4. APPLICATION: Compliance.
A) OPE RATIONAL SCOPE
Method is applicable to semi-continuous measurement of hydrocarbons corrected for methane in ambient air.
B) INTERFERENCES/LIMITATIONS.
No interferences have been observed for methane measurement. Air peak interferences can be minimized by mechanical methods or
can be electronically negated.
C) RECOMMENDED USE AREA
5. OPERATIONAL PARAMETERS
A) RANGE
The range is 0-13.1 mg/m (0 to 2Q ppm) carbon as CH. and 0.655 rog/m methane for atmospheric analysis. Lower ranges
e available for special applications.
of full scale in lower special analysis ranges.
•1 o
(0-1.31 mg/m or 0 to 2 ppm carbon as CH,, and 0 to 1.31 rog/m methane) are available for special applications.
B) ACCURACY 1% of full scale in higher atmospheric analysis range, and
C) PRECISION ±0.5%.
6. REAGENTS REQUIRED
Combustion gas, fuel, carrier gas, zero gas, calibration gas,
span gas.
7. EQUIPMENT REQUIRED
Commercially available total hydrocarbon analyzer, sample intro-
duction system, filter, stripper or pre-column, oven.
& KEYWORD INDEX: Hydrocarbons, ambient air, compliance.
9. CROSS REFERENCE ID NUMBERS 02-05-01, 02-05-02-04.
10. REFERENCES
A) PRIMARY SOURCE
480 U.S. Environmental Protection Agency, "Reference Method for Determination of Hydrocarbons Corrected for Methane " Title 40
Part 50, Chapter 1, Subchapter C, Appendix E, Washington, 1971, p. 21. ,<.«=•».
B) BACKGROUND INFORMATION
527 Fee, G., "Multi-Parameter Air Quality Analyzer," ISA Proceedings, A10/CHEMPID Symposium, Houston, Texas, April 19-21, 1971.
528 Stevens, R.K., and A.E. O'Keeffe, Anal. Chem., 42, 143 A (1970).
529 Stevens, R.K., A.E. O'Keeffe and G.E. Ortman, "A Gas Chromatographic Approach to the Semi-Continuous Monitoring of
Atmospheric Carbon Monoxide and Methane," Proceedings of llth Conference on Methanes of Air Pollution on Industrial
Hygiene Studies, Berkeley, California, March 30-April 1, 1970.
530 Instruction Manual for Air Quality Chromatograph Model 6800, Beckman Instrument Co., Fullerton, California.
531 Instruction Manual, Bendix Corp., Ponceverte, W. VA.
C) FIELD APPLICATIONS
322
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3. ABSTRACT OF METHODOLOGY
2. IDENTIFICATION CODE
02-05-03-01
The Monitor IV system is a continuous on-line system for wet chemical analysis of water. The system operates on the principle
of continuous flow analysis, where air segmented streams of sample and reagents are brought together and reacted under carefully
controlled conditions. The resulting color, or color reduction, is measured by a beam of light as the analytical stream passes
through a colorimeter.
4. APPLICATION" Engineering evaluation R&D.
A) OPERATIONAL SCOPE
This equipment is designed to monitor industrial streams before and after water treatment. Instruments are available for:
Ortho Phosphate, Silicates, Cyanide, Ammonia, Nitrate and Nitrite, Copper, Cr (VI), Chloride, Hardness, Total Iron,
Hydrazine, Total Inorganic Phosphate.
B) INTERFERENCES/LIMITATIONS
Water clarity and color can affect instrument response. Preventive maintenance should be performed at seven-day intervals.
Wet analysis should be verified manually prior to automatic analysis.
C) RECOMMENDED USE AREA
This instrument is the recommended instrument for continuous on-line liquid analysis for engineering evaluation R&U.
5. OPERATIONAL PARAMETERS
A) RANGE Depends on analysis performed (ppb to ppm).
B) ACCURACY Depends on analysis performed (+10 to ^25% estimated).
C) PRECISION +2%.
a REAGENTS REQUIRED
Depends on analysis performed.
7. EQUIPMENT REQUIRED
Technicon Monitor IV system (Technicon Instruments Corp.,
Tarrytown, New York).
& KEYWORD INDEX: Analysis, continuous, liquid on-line analysis.
9. CROSS REFERENCE ID NUMBERS 02-03-02- (see specific wet chemical tests).
10. REFERENCES
A) PRIMARY SOURCE
im«nT ouunifC
475 Technicon Industrial Systems, "Specifications and Engineering Standards: M-IV," February 19, 1973
476 Technicon Industrial Systems, "Specifications and Engineering Standards
215, 255, 251, 305 and 147," January through May 1975
B) BACKGROUND INFORMATION
: M-IV/A-172, 171. 301, 212, 177, 207.
C) FIELD APPLICATIONS
323
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1 TITLE CONTINUOUS ON-LINE MONITORING OF LIQUID STREAMS WITH ORION SPECIFIC ION
I. IIIUC ELECTRODES
2 IDENTIFICATION CODE
02-05-03-02
3. ABSTRACT OF METHODOLOGY
The Orion series 1000 process stream monitor employs & specific ion electrode system to continuously monitor a process stream. The
instrument uses reagents which eliminate both electrode and method interferences. The monitor consists of a sensing electrode and
tag ion electrode (TIE) in a thermostatic flowthrough cell. The TIE is a second specific ion electrode which is responsive to a tag ion
(for example Na+) present in the reagent in sufficient quantities to swamp out the effect of any tag ion in the process stream. Propor-
tioning pumps supply filtered sample and reagent to a flowthrough cell where the measurement is made. The output is displayed on a
meter or strip recorder. Reagent supplies and automatic re-standardization allow unattended operation up to 60 days.
4. APPLICATION^ Engineering evaluation R&D, environmental assessment.
A) OPERATIONAL SCOPE
Present units are designed to monitor CN~, NH^ , halide ions, metal ions, water hardness, residual chelant, total acid and total
base. These units are designed to operate in industrial plant environments to control process streams or monitor pollution levels
in industrial waste streams.
B| INTERFERENCES/LIMITATIONS
Suspended solids can foul electrodes, but the bypass filter system is designed to reduce that problem. Reagents are designed
to eliminate interferences, but each electrode/stream combination should be studied to ensure accurate readings.
C) RECOMMENDED USE AREA
Process or pollution monitoring for engineering evaluation R&D.
5. OPERATIONAL PARAMETERS
A) RANGE Logarithmic response 4 decades of concentration (detection limits depend on electrode).
B) ACCURACY N/Q (±10*).
C) PRECISION ±5% over 4 decades.
6. REAGENTS REQUIRED
Depends on species monitored.
7. EQUIPMENT REQUIRED
Orion Series 1000 continuous chemical monitor (Orion Research,
Cambridge, Mass.).
& KEYWORD INDEX: Analysis, continuous liquid analysis.
9. CROSS REFERENCE ID NUMBERS 02-03-02-01.
10. REFERENCES
A) PRIMARY SOURCE
477 Orion Research, Newsletter, 5(1), 1973.
B) BACKGROUND INFORMATION
C) FIELD APPLICATIONS
478 Riseman, J.H., "Electrode Techniques for Measuring Cyanide in Waste Waters," Am. Lab.. £(12), 63 (1972).
479 Thomas, R.H.,and R.L. Booth, "Selective Electrode Measurement of Ammonia in Water and Wastes," Environ. Sc1. Tech..
7(6), 523 (1973) (see 02-03-02-01 for further references). ~~
-------
1. REPORT N0~
EPAz600A-77-024
4. TITLE AND SUBTITLE '
Technical Manual tor Inorganic Sampling and Analysis
7. AUTHOR(S)
R.F. MaddaloneandS.C. Quinlivan
9. PERFORMING URQAN.ZAT.ON NAMb AND ADDRESS
TRW--Defense and Space Systems
One Space Park
Redondo Beach, California 90278
3. RECIPIENT'S ACCESSION NO.
REPORT DATE
January 1977
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORG^>-: IATION REPORT NO
10. PROGRAM ELEMENT NO.
1AB013: 21AAZ-015
NO.
11. CONTRACT/GRANT
38-02-1412, Task 16
AME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 2-12/76
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES' IERL-RTP task officer for this manual is R.M. Statnick, Mail
Drop 82, 919/549-8411 Ext 2557.
The manual presents the state-of-the-art of inorganic sampling and analysis
(ISA) procedures in a standardized format that makes the methodology readily avail-
able to professionals in the field. Because of the breadth of ISA, a system was
developed to avoid burying specific methods in narrative. This design concept makes
the techniques of sampling and analysis easily accessible, while providing a compre-
hensive cross-referenced indexed of process stream and chemical test situations and
procedures. The sampling and analysis procedures in this manual are compatible
with environmental assessment and process measurement activities. The intent of
this manual is to provide a compilation of methods applicable to these activities. The
methods included in this manual are generally proven procedures from standard
reference sources which include ASTM procedures, reports in open literature, and
government reports.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
. COSATl I ield/Group
Air Pollution
Sampling
Analyzing
Inorganic Compounds
13. DISTRIBUTION STATEMENT
Unlimited
MMMMM»«^««B«a
EPA Form 2220-1 (9-73)
Air Pollution Control
Stationary Sources
19. SECURITY CLASS (This Re port)~
Unclassified
13B
14B
07B
21. NO. OF PAGES
336
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
325
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