EPA R4-73-027
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Volume II: method Summaries
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OFFICE OF MONITORING
THE U.S. ENVIRONMENTAL
PROTECTION AGENCY
flPRIL 1913
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This report has been reviewed by the
Office of Research and Monitoring, EPA,
and approved for publication. Approval
does not signify that the contents neces-
sarily reflect the views and policies of
the Environmental Protection Agency, nor
does mention of trade names or commercial
products constitute endorsement or
recommendation for use.
ii
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ABSTRACT
Host of the methods currently used, or in recent use, for the
analysis of pollutants in various media and categories were identified
by selected EPA laboratories. Important characteristics of each method
were abstracted for presentation in the form of a one-page summary of
that method. Methods are further summarized in a matrix that presents
(1) pollutant analyzed (2) medium in which it occurs, and (3) non-
quantitative descriptions of the measurement/detection method. Some
400 methods are included in the compendium.
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ACKNOWLEDGMENT
The Office of Monitoring acknowledges with gratitude the assist-
ance and guidance provided by the following persons in identifying or
suggesting analytical methods to be included in this compendium,
providing descriptions of methods, or reviewing and commenting upon
drafts of the method summaries:
Paul Altschuller
Dwight Ballinger
Daniel Bender
Fran Brezenski
Howard Crist
John Clements
Geneva Douglas
Henry Enos
Michael Gruenfeld
Seymour Hochheiser
Richard Jaquish
Bernd Kahn
Fred Kawahara
Kenneth Knapp
Herman Kreiger
Robert Lieberman
Earl McFarren
Donald Oakley
Andrew O'Keeffe
P. D. Lederman
Gordon Robeck
Frank Scaringelli
Ann Strong
James Symons
John Thompson
Richard Thompson
Darryl VonLehmden
Cornelius Weber
NERC/RTP
NERC/Cincinnati
NERC/Cincinnati
Region II Laboratory, Edison
NERC/RTP
NERC/RTP
NERC/Las Vegas
Primate Laboratory, Perrine
NERC/Edison
NERC/RTP
NERC/Las Vegas
NERC/Cincinnati
NERC/Cincinnati
NERC/RTP
NERC/Cincinnati
EERL, Montgomery
NERC/Cincinnati
Office of Radiation, Rockville
NERC/RTP
NERC/Edison
NERC/Cincinnati
NERC/RTP
EERL, Montgomery
NERC/Cincinnati
Primate Laboratory, Perrine
NERC/RTP
NERC/RTP
NERC/Cincinnati
iv
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TABLE OF CONTENTS
Page
PURPOSES 1
CONTENTS: FORM OF PRESENTATION 2
Matrix of Methods 2
Method Summaries 4
Definition of Headings 6
Organization of Matrix and Summaries 9
HOW THE COMPENDIUM WAS GENERATED 10
STATE OF COMPLETION OF THE COMPENDIUM 11
CORRECTIONS 12
SUMMARY OF ANALYTICAL METHODS A- 1
A. AIR METHODS A- 1
B. WATER AND WASTEWATER METHODS B- 1
C. DRINKING WATER SUPPLY METHODS C- 1
D. SOLID WASTE METHODS D- 1
E. RADIOACTIVITY METHODS E- 1
F. PESTICIDE METHODS F- 1
G. OIL AND GREASE METHODS G- 1
H. BIOLOGICAL METHODS H- 1
LIST OF REFERENCE SOURCES H-27
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PURPOSES
The primary purpose of this compendium is to draw together summary
descriptions of analytical methods in recent or current use in EPA
laboratories, to serve as a data base to assist the further develop-
ment of a program of standarization of EPA analytical methodology.
Secondarily, the document provides EPA management personnel with
easily accessible information on methods available for measuring
specific pollutants, and the more important characteristics of
these methods.
Methods included in the compendium cover a variety of applications,
ranging from research and routine monitoring through procedures that
have been officially selected or recommended by EPA for specific
applications (for example, those methods promulgated in the Federal
Register). The inclusion of a method in this compendium, however,
does not necessarily imply EPA endorsement. Certain of the methods are,
in fact, contraindicated for specific applications; such cases
are clearly identified.
For some pollutants, several methods are cited for measurement
or detection within a single medium. No attempt has been made in this
compendium to differentiate methods into groups that would classify
them according to uses (such as monitoring, research, enforcement, etc.)
or to preference. (Exceptions: (1) methods promulgated in the Federal
Register are identified in both the matrix and in the Method Summary,
and (2) when EPA laboratory personnel, in reviewing the Method Summaries
identified shortcomings of a method or expressed preference for one
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method over others for a specific application, their comments are reported
in the "User Comments" section of the Method Summaries.)
CONTENTS: FORM OF PRESENTATION
Each method summarized in the compendium is presented in two
levels of detail:
• A "matrix" form that relates the pollutant (or
other parameter of interest), the medium in which
it occurs, and skeletal, checklist information about
the measurement method.
• A "Method Summary" that includes a brief narrative
description of the analytical method applied to a
specific parameter in a given medium, plus a state-
ment of purpose of the analysis and quantitative
characteristics of the method.
Additional information about the methods can be found in the source
documents from which the summarized information was abstracted. Both
the matrix and the Method Summaries identify the reference sources.
The matrix of methods together with the list of source documents is
included in Volume I of the compendium. The compilation of Method
Summaries constitutes Volume II.
Matrix of Methods
This less detailed form of presentation is an alphabetical listing
of pollutants (or other parameters), segregated according to (1) the
medium in which the pollutant occurs (air, water, solid wastes),
(2) recognized categories of pollutants (pesticides, radioactivity,
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oils and greases, etc.), or (3) specialized categories of measurement
techniques (biological methods).
Each horizontal line of the matrix represents a combination of
9 a specific pollutant
• the medium, substrate, or category in which it occurs
• a specific procedure for obtaining the desired measure-
ment or analytical determination.
Checklist information relative to the procedure includes (where appli-
cable) the following categories of information:
• Type of source
• Type of sample
• Sample preservation and handling requirements
• Sample treatment prior to measurement or detection
• Detection or measurement technique
•Form of data output (visual reading, analog electric
signal, etc.)
•Form of record (manual entry, automatic graph, etc.).
In addition, each line on the matrix includes a reference number that
indicates the primary source of information listed in the "List of
Primary Reference Sources" included in Volume I. It also includes a
Method Summary Number that relates the matrix entry to one or more of
the Method Summaries presented in Volume II.
The same matrix headings and subheadings were used for all media
and special categories except biological measurements. Because of the
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nature of many biological measurement methods, a different set of matrix
headings was used.
The matrix of methods serves both as a source of highly abbrevi-
ated, non-quantitative information about a specific analytical pro-
cedure applied to a given pollutant in a given medium, and as an
index to the compilation of method summaries appearing in Volume II.
Method Summaries
The Summaries of Analytical Methods in Volume II of this compendium
present on a single page a brief description of an analytical method
applied to a specific pollutant (or other parameter) in a given medium.
Most of these methods yield quantitative results, although some are
used for identification, taxonomic classification, or other non-
quantitative purposes.
The information presented in the Method Summary expands upon the
highly abbreviated information given in the matrix. It is intended
primarily to provide a general description of the method—its
characteristics, applicability, and limitations, and is in no sense
given as a laboratory procedure.
Each Method Summary is intended to provide information in the
following categories:
• Identification of pollutant or parameter
• Medium in which parameter occurs (for which this
specific analytical method is applied)
• Purpose of measurement or qualitative determination
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• Brief description of analytical procedure
• Limitations of method
In particular, its
- range of applicability
- interferences
- pitfalls
• Statistical characteristics
- accuracy
- precision
- time required to perform measurement
• Calibration requirements
• Form of data output
*
• Comments by users of the method
•Sampling procedures or special requirements
• Reference source(s).
A primary reference, that is, the document from
which the content of the Method Summary was
abstracted, is given for each Method Summary. In
some cases, additional references are given by the
Method Summary. These secondary references are
usually identified in the primary reference. In
no case was the attempt made to relate specific
portions of the information presented in the
Summary to specific secondary references, since
essentially all information in the Summary was
drawn from the primary reference.
*
This category of information is included only in those summaries
for which EPA reviewers provided specific comments.
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Information was entered into each of these categories when avail-
able from the primary reference source identified in the summary, or
when provided by EPA reviewers. When information was not available
from the primary reference source or was not provided by the reviewer,
an entry of "Not stated" or equivalent was made for the corresponding
heading. This should not be taken to imply that the information is
not available from other sources, including secondary references
cited in some Method Summaries.
In addition, each Method Summary is numbered to permit ready
correlation with entries in the matrix. The reader should note that
several matrix entries may refer to a single summary, and conversly,
that a single matrix entry may refer to more than one summary. He
should also note that the Method Summary numbers are not necessarily
consecutive, since some methods were deleted after the Method Summaries
were numbered.
Definition of Headings in Method Summaries
Most of the information categories or headings used in the Method
Summaries are considered self explanatory. Others, listed below, require
definition or explanation of their use in this compendium.
Range of Applicability: This is intended to state the
upper and lower concentration (or other appropriate
characteristics of the parameter) for which the method
is applicable. When only an upper or lower limit is given
in the reference source, that information is entered. When
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non-quantitative information is given in the reference source,
that information may also be entered under this heading.
Sensitivity: In general, sensitivity is used synonymously with
"Detection Limit", to indicate the lowest concentration of a
pollutant (or lowest value of some other parameters) that
a given method can consistently measure. In a very few cases,
the source reference or reviewer distinguishes between "Detection
Limit" (as the lowest measurable value) and "Sensitivity" (as
the magnitude of signal needed to obtain a reliable measurement,
taking into account the noise level of the measurement system).
When this distinction is made in the reference source, it is
reflected in the Method Summary.
Sensitivity, in either of the senses discussed above,
may be considered to be either a statistical characteristic
or a limitation of the method. Sensitivity information was
available for a relatively small proportion of the methods
summarized. The "sensitivity" heading is not included on the
Method Summaries when data are not available. When sensitivity
information is reported, it is usually under the category of
"Limitations".
Accuracy and Precision: There is considerable diversity in the
use of these terms among the several reference sources from
which the Method Summaries were derived. Rather than impose
rigorous statistical definitions of these and related terms,
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the compilers of this compendium chose to accept the statistical
characteristics of the method as stated in the reference source,
and to fit this information as well as possible under the headings
Accuracy and Precision, as these terms were used more or less
consistently in most of the EPA source documents. In these
sources, the implied approximate definitions are as follows:
"Accuracy" — the average of the deviations of a set of
replicate measurements of a given variable from the "known"
value of that variable.
"Relative accuracy" (or "relative error", or "bias")
— the difference between average value of a set of
replicate measurements and the "known" value of the
variable expressed as a proportion or percentage of
the known value.
"Precision" — either the standard deviation
or the standard error of the mean I
L\ n(n - 1)
a set of n replicate measurements (XI) of a given variable.
"Relative precision" (or "relative standard deviation",
or "coefficient of variation") — the standard deviation
of a set of replicate measurements, expressed as a pro-
portion or percent of the average value of the set.
In cases where a significant divergence existed between the
statistical information in the source document and the above
definitions, the information was repeated as given in the source
document and the discrepancy noted by a footnote.
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Organization of the Mftrix and Summaries
When the format of the compendium was being developed, several
arrangements were considered. One attractive scheme was a strictly
alphabetical listing of pollutants/parameters, irrespective of medium.
This would permit easy comparison of the methods applicable to each
pollutant in various media, and would also make the method for a given
pollutant easier to locate.
The scheme selected for organizing the matrix in this document was
considered preferable primarily because it reflects existing organiza-
tional responsibilities and activities within EAP laboratories, and
because it facilitates production of a document of this nature. The
present arrangement necessarily involves considerable redundancy,
especially in the matrix.
The segregation of methods by special measurement category does
not imply that every method included in a given category belongs
exclusively in that category. For example, all methods grouped under
the heading "Radioactivity" do not involve radionuclides, but may be
used to determine stable Isotopes commonly investigated in conjunction
with radioactive isotopes.
EPA's Office of Monitoring is considering alternative arrangements
of the matrix and the compilation of method summaries for future issues
of the compendium, and will welcome suggestions by users of the document.
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HOW THE COMPENDIUM WAS GENERATED
The analytical methods in this compendium were selected for inclu-
sion at the suggestion of personnel in EPA NERC's and laboratories,
following contact by representatives of EPA Headquarters' Office of
Monitoring. Method descriptions suggested or provided by the laboratories
were summarized in a form similar to that presented in Volume II (and
described above). Rough drafts of the summaries were returned to the
laboratories for review and comment. The Method Summaries in Volume II
reflect the substantive comments resulting from this review.
There are certain exceptions to this review procedure, primarily
in the category of radiation measurements. Some older methods are
included that apparently are not in current use by EPA but nevertheless
are considered acceptable. Summaries are also included for certain
other radiochemical procedures which had been received too late to
permit review by EPA laboratory personnel. These special cases are
clearly indicated by asterisked footnotes.
Certain of the methods in the air and drinking water categories
were also indicated by the reviewer to be obsolete or not recommended.
Summaries of such methods are included in the compendium with the
reviewers' comments or caveat clearly flagged. These "not recommended"
method summaries were retained to indicate that they had been considered
and to emphasize that they were not used and not recommended for use
by EPA.
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STATE OF COMPLETION OF THE COMPENDIUM
This initial issue of the compendium contains methods suggested
by about twelve component organizations of EPA's National Environmental
Research Centers or other EPA laboratories. The compendium does not,
however, include all analytical methods in current use by EPA. Such
important categories as biological methods for drinking water analyses
and methods for air pollution from mobile sources were not included
because of time and budgetary limitations of the initial effort.
Expansion of the compendium to include additional methods is under
consideration by the Office of Monitoring.
The present compendium is incomplete in certain other respects.
Many of the Method Summaries contain a large number of "Not stated"
or "Information not available" entries for many of the headings,
especially those requiring quantitative data. As discussed earlier,
the "Not stated" entries imply only that the information was not avail-
able from the primary reference source from which the summary was
abstracted. In many cases, needed information was supplied by
reviewers in EPA Laboratories. It was, however, outside the scope
of the present effort to search secondary references for such data.
The process of abstracting information from a detailed analytical
procedure to develop a summary of the method necessarily involves
selection of certain material. The required degree of selection is
even greater in determining which elements should be included in the
highly condensed matrix format, to give even a key-word-type indication
of what the method involves. While the one page summaries give only
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a partial description of the analytical procedure, the matrix should
be considered to provide only a suggestion of the steps involved.
CORRECTIONS
In the first issue of a compilation of this size and nature, it is
possible that errors of various types (typographical, transposition,
technical, etc.) may escape detection during proofreading and other
checking procedures. The Office of Monitoring requests that readers
notify the Chief of Standardization Branch, Office of Research and
Monitoring, EPA Headquarters, of any significant errors they may
detect, in order that corrections may be made in subsequent issues.
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A. AIR METHODS
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No. A-2
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Aldehydes in Flue Gases.
Medium; Air (point source)
Name of Measurement Method: Not Stated
Principal Detection Techniques; Iodine Titration
Purpose of Measurement (Important Applications); Not Stated
Summary of Method: Aldehydes are collected in midget impingers con-
taining bisulfate absorbing media. Stable bisulfite addition compounds
are formed. Excess bisulfite is destroyed with iodine and the additional
complexes are then decomposed by shifting the pH of the sample. The
freed bisulfite, determined by iodine titration.is equivalent to the
aldehydes in the sample.
Limitations;
Range of Applicability: Lower limit of 1 ppm.
Interferences: Sulfur dioxide from bisulfite decomposition should
be removed, since it may affect end point. Methyl ketones if present
in gases would be included in the results.
Pitfalls; Special Precautions: None Stated
Statistical Characteristics:
Accuracy and Precision: No data available from Reference cited.
Time of Measurement (Maximum Frequency. Recovery Period, etc.);
None Stated
Calibration Requirements; No special requirements.
Data Outputs; Not stated. Assumed to be visual observation, manually recorded.
Special Sampling Requirements (Collection. Storage, Handling): Sampling
apparatus as shown reference cited below.
References; "Determination of Carbonyls (Aldehydes) in Flue Gases. D-ll,"
from an informal compilation of analytical methods provided by John B. Clements,
EPA, National Environmental Research Center, Research Triangle Park, N. C.
Letter dated October 5, 1972.
A-l
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No. A-3
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Ammonia '
Medium: Ambient Air
Name of Measurement Method: Automated
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications): Applicable to the analysis of
ammonia and ammonium ions.
Summary of Method: Ammonia reacts with alkaline Nessler's reagent to produce an
orange colored complex that absorbs at 400 to 425 nm. The intensity of color of
this complex is determined colorimetricallv. (A Tuclv.-ilcon AutoAnalyzcr is used.)
Limitations:
Range of Applicability: Concentrations up to 20 ug/ml
Interferences: Ca, Mg - Rochelle salt used to avoid precipitation.
Pitfalls; Special Precautions: (1) At higher concentrations, i.e., greater than
20 ug/ml, the complex may agglutinate. (2) Ammonia-free distilled water should
be used throughout for dilutions. (3) At the end of each day system should, be
flushed with 0.1N HgSO^ to clean, and finally rinsed with distilled water.
Statistical Characteristics:
Accuracy: Not stated.
Precision; Relative standard deviation is 1 + 0.08 pgNHj/ml.*
Time of Measurement: 60 samples analyzed per hour.
Calibration Requirements: Not «stflteH.
***Comments by Users: This method i£ considered obsolete and i.s_ not recommended.
Data Outputs: Strip chart recorder.
Special Sampling Requirements (Collection, Storage, Handling): High volume sampler.
Refluxing and extraction from 8% aliquot of the filter.
References:
(1) Morgan, G. B., Tabor, E. C.., Golden, C., and Clements, H., "Automated Laboratory
Procedures for the Analysis of Air Pollutants," presented at the Technicon
Symposium, Automation in Analytical Chemistry, New York, N.Y., Oct. 19, 1966.
(2) Morgan, G. B., Golden, C., and Tabor, E. C., "New and Improved Procedures for
Gas Sampling and Analysis in the National Air Sampling Network", presented at
the Technicon Symposium, Automation in Analytical Chemistry, New York, N. Y.,
Oct. 19, 1966.
*As stated in Reference (2)above
A-2
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No. A-4
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Ammonia
Medium: Air (Ambient)
Name of Measurement Method: Manual and Automated
Principal Detection Technique: Colorimetric
Purpose of Measurement (Important Applications): Allows field sampling and
return for laboratory analysis.
Summary of Method: The ammonium ion produced during sampling is reacted
with sodium phenolate and sodium hypochlorite to produce a blue colored
complex, which is measured colorimetrically.
Limitations:
Range of Applicability: 0.02 to 5.0 jig NHj/ml (equivalent to 3.8
to 950 (ig/mj for average volume air sample if 100 percent efficiency
and straightforward stoichiometry are assumed).
Interferences: Ferrous, chromous, manganous, and copper ions
cause errors.
Sensitivity: 0.02 fig NH-j/ml = 3.8 (ig NH-j/m3.
Statistical Characteristics:
Accuracy: Not available
Precision: Standard deviation is 0.11 fig NH./ml.
Stability: Color of complex is stable for at least 1 hour after
development.
Time of Measurement: Not stated
Calibration Requirements: No unusual requirements.
Data Outputs; Electrical signal displayed on meter or chart.
Special Sampling Requirements (Collection. Storage. Handling): Ammonia
extracted from air by dilute sulfuric acid. Efficiency (sampling) of
100 percent is assumed.
References: "Determination of Ammonia: Manual and Automated. M-2",
from an informal compilation of analytical methods provided by
John B. Clements, EPA, National Environmental Research Center,
Research Triangle Park, N.C. Letter dated October 5, 1972.
A-3
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No.A-5
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Ammonia
Medium: Air (Ambient)
Name of Measurement Method: Nessler's
Principal Detection Technique: Colorimetric
Purpose of Measurement (Important Applications): The method allows field
collection and subsequent laboratory analysis.
Summary of Method: Ammonia in the air is absorbed in 0.1 N sulfuric acid,
forming ammonium sulfate, which is retained in the acid medium. Neutralization
of the acid solution followed by the addition of Nessler's reagent, produces
a characteristic yellow color which is determined spectrophotometrically.
Limitations:
Range and Sensitivity: Concentration of 0.03 to 0.6 ppm. For
higher ammonia concentrations, a sampling period of less than 2 hours
or a lower sampling rate can extend the range to 5 ppm. The system
gives a straight-line plot of absorbance vs. concentration for
quantities up to about 100 Mg NH./25 ml of solution.
Interferences: Calcium, magnesium, iron, and sulfides, aliphatic and
aromatic amines, acetone, aldehydes, alcohol, ammonium ion.
Pitfalls; Special Precautions: Not Stated.
Statistical Characteristics:
Accuracy; No data are available from reference cited below.
Precision: The estimated standard error for the combined sampling and
analytical technique is + 10% in concentration range 0.03-5 ppm.
Time of Measurement: Not Stated
Calibration Requirements: Run a new calibration curve with each new batch of
Nessler's reagent prepared. The temperature of the calibration solution should
be the same as that of samples.
Data Outputs: Electrical signal on meter.
Special Sampling Requirements (Collection, Storage, Handling): All-glass midget
impingers are used for collection.
References! "Determination of Ammonia in Ambient Air: Nessler Method. H-2",
from an informal compilation of analytical methods provided by John B. Clements.
EPA, National Environmental Research Center, Research Triangle Park, «. C. ,
Letter dated October 5, 1972.
A-A
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No. A-6
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Ammonia in Stack Gas
Medium: Air (Stacks)
Name of Measurement Method; Kjeldahl
Principal Detection Techniques; Acid Titrimetric
Purpose of Measurement (Important Applications):
Summary of Method: Ammonia is collected from source effluents by passing
the gas through three midget impingers connected in series and containing
IS ml of 1 N sulfuric acid. Free ammonia is quantitatively recovered by
u modified Kjeldahl distillation at pH of 7.4. The distillate is collected
in boric acid and a mixed indicator. The color changes from purple to
green as the ammonia is distillea into boric acid and ammonium borate is
formed. Titration with a standard sulfuric acid yields the acid equivalent
to the isolated ammonia.
Limitations:
Range of Applicability: 0.3 to 10 mg/100 ml of indicator-boric acid
solution.
Interferences: Certain amines; calcium in excess of 250 mg/1 lowers
PH.
Pitfalls; Special Precautions: None stated
Statistical Characteristics:
Precision: Approximately + 2 percent.
End Point Stability: To ensure distinct end-point the indicator
solution should be added to the boric acid solution immediately
prior to use.
Time of Measurement: Not stated
Calibration Requirements: None stated
Data Outputs: Assumed to be visual observation.
Special Sampling Requirements (Collection, Storage, Handling): Schematic
presentation of sampling train is shown in referenced literature.
References: "Ammonia in Stack Gas: Kjeldahl Method", from an informal
compilation of analytical methods provided by John B. Clements, EPA,
National Environmental Research Center, Research Triangle Park, N.C.
Letter dated October 5, 1972.
A-5
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No. A--7
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Ammonium
Medium: Air (Ambient)
Name of Mesurement Method: Manual and Automated.
Principal Detection Technique: Colorimetric
Purpose_of Measurement (Important Applications): Applicable to ambient air
obta'ined'at "field stations for return to a central laboratory. Manual or
automated (Technicon AutoAnalyzer). Automated preferred because of greater
reproducibility.
Summary of Method: Ammonium ion is extracted from glass fiber filter and
reacted with sodium phenolate and sodium hypochlorite to produce a blue
colored complex. The intensity of the color is determined coloriretrIcalJy.
Limitations:
Jtange: 3.0 tc .V.O -jg T 3/111^ eT
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No. A-8
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Beryllium
Medium: Stationary Sources in Air
Name of Measurement Method: None stated
Principal Detection Technique: Atomic Absorption
Purpose of Measurement (Important Applications): Applicable for the determi-
nation of beryllium emissions only when specified by test procedures for
determining compliance with the Clean Air Act. (Public Law 91-604)
Summary of Method: Beryllium laden gases are withdrawn isokinetically from
the source, and the collected sample is digested in an acid solution and
analyzed by atomic absorption.
Limitations:
Range and Sensitivity: Not stated
Interferences: None stated
Statistical Characteristics:
Precision! Not stated
Accuracy: Not stated
Time of Measurement: Not stated
Calibration Requirements: Methods and equipment in APTD-0576 for calibration.
Data Outputs; Analog signal displayed on meter, digital display, etc.
Special Sampling Requirements (Collection, Storage, Handling): Sampling train.
Design specs used by EPA and described in APTD-0581. Commercial models are
available.
References: Fed. Register, Vol. 36, #235, Tues. Dec. 7, 1971.
A-7
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No. A-9
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Carbon liloxide
Medium; Air (Ambient)
Name of Measurement Method: Nondispersive Infrared
Principal Detection Technique: Infrared spectroscopy
Purpose of Measurement (Important Applications): Applicable to gases with
infrared absorption characteristics that can be determined in presence of
other gases.
Summary of Method: Sampling is performed on a continuous basis with a constant
flow of air drawn through the sample cell by a vacuum pump. The nondispersive
infrared analyzer operates on the principle of selective absorption of infrared
energy by carbon dioxide. This indicates a change in electrical capacitance,
which is picked up by an amplifier and transformed into an electrical signal
used to drive the recorder.
Limitations;
Range of Applicability; Range of instrument depends on sample cell volume
and can vary from ppm to 100% concentrations. Should include ranges of
300 to 500 ppm.
Interferences; Water vapor; changes in barometric pressure
Pitfalls; Special Precautions; None cited
Statistical Characteristics:
Accuracy: No data available; manufacturer stated accuracy is + 1%
full scale.
Precision: No data available ; manufacturer stated precision is + 12
full scale.
Stability; Sampling stability excellent—instrument precision and accuracy
are independent of flow rate or fluctuations. Manufacturer stated maximum
zero drift + 1% full scale each 8-hour period and maximum span drift
tl percent full scale each 24 hours.
Time of Measurement (Maximum Frequency, Recovery Period, etc.); Not stated,
but assumed to be rapid (several determinations per hour).
Calibration Requirements: Should be carried out under same barometric conditions
as those of measurement.
Data Outputs; Electric signal displayed on chart.
Special Sampling Requirements (Collection, Storage, Handling): Sampling performed
on a continuous basis.
References: "Continuous Measurement of Atmospheric Carbon Dioxide by Non-Dispersive
Infrared Instruments," from an informal compilation of analytical methods provided
by John B. Clements, EPA, National Environmental Research Center, Research Triangle
Park, N.C. Letter dated October 5, 1972.
A-8
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No. A-10
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Carbon Dioxide, Excess Air, and Dry Molecular Weight
Medium: Air (Stack Gases)
Name of Measurement Method: Gas Analysis
Principal Detection Technique: Orsat analyzer
Purpose of Measurement (Important Applications): Applicable only when specified
by the test procedures for determining compliance with the New Source Performance
Standards. (See Reference below)
Summary of Method: An integrated or grab gas sample is extracted from a sampling
point and analyzed for its components using Orsat analyzer.
Limitations:
Range of Applicability: Not stated
Interferences; Particulates removed by stainless steel or Pyrex probe.
Pitfalls; Special Precautions: None Cited
Statistical Characteristics:
Accuracy: Not stated
Precision: Not stated
Time of Measurement (Maximum Frequency, Recovery Period, etc.): Not stated
Calibration Requirements: Not stated
Data Outputs: Not stated
Special Sampling Requirements (Collection. Storage, Handling): Grab or Integrated
References! Federal Register, Vol. 36, #247, Thurs. Dec. 23, 1971.
A-9
-------
No. A-ll
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Carbon Monoxide
Medium: Air (Ambient)
Name of Measurement Method: Nondispersive IR Spectrometry
Principal Detection Technique. Infrared Spectrometry
Purpose of Measurement (Important Applications): Applicable to the determination
of carbon monoxide in ambient air, and to the analysis of gases under pressure.
Summary of Method: Method is based on the absorption of IR radiation by carbon
monoxide. Energy from an IR source is split into parallel beams and directed
through reference and sample cells. With a nonabsorbing gas in the reference
cell, and with no CO in sample cell, the signals from detectors are balanced
electronically. Any CO introduced in the sample cell will absorb radiation,
which reduces the temperature and pressure in the detector cell and displaces
a diaphragm. This displacement is detected electronically and amplified to
produce an output signal
Limitations:
Range and Sensitivity: 0-58 mg/m or 0-50 ppm, (the range most commonly
used in urban sampling). Sensitivity is 1% fullscale response/0.6 mg
CO/m3 (0.5 ppm).
Interferences: CO. minimal. Water vapor may cause error as high as
12 mg CO/m3.
Pitfalls; Special Precautions: None cited
Statistical Characterstics:
Accuracy: Depends on instrument linearity and absolute concentrations
of the calibrated gases. Accuracy of + 1% full scale in 0 - 58 mg/m
range obtainable.
Precision: Determined with calibrated gases precision is + 0.5% fullscale in
the 0-58 mg/m3 range.
Stability: Variations in ambient room temperature can cause Changes
equivalent to as much as 0.5 mg CO/m3°C. Pressure variations can cause
changes in instrument response.
Time of Measurement (Maximum Frequency, Recovery Period, etc.): None Stated
Calibration Requirements: Gases corresponding to 10, 20, 40, 80% full scale
used. Gases must be certified.
Data Outputs: Readout on data processing devices. Expressed as millivolts or
milliamps fullscale at a given impedance.
References: (1) Federal Register, Vol. 36, #84, April 30, 1971.
A-10
-------
No. A-12
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Chloride from participates
Medium: Ambient Air
Name of Measurement Method: Technicon AutoAnalyzer.
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications);
Summary of Method: Chlorides react with mercuric thiocyanate to form mercuric
chloride and to liberate thiocyanate. The liberated thiocyanate reacts with the
ferric ion to form a highly colored complex that obeys Beer's lau in concentrations
greater than 50 vigof fU/ml •
Limitations:
Range of Applicability: Not stated.
Interferences: None stated.
Pitfalls; Special Precautions: None stated.
Statistical Characteristics:
Accuracy: Not stated.
Precision; Relative standard deviation is 1.0 +0.1 ug of Cl/ral.
Time of Measurement: 60 analyses/hour.
Calibration Requirements: None stated.
Data Outputs: Stripchart recorder (electrical signal)
Special Sampling Requirements (Collection. Storage, Handling); High volume
sampler refluxing and extracting from 8% aliquot of filter.
References:
Morgan, G. B., Tabor, E. C., Golden, C., and Clements, H., "Automated Laboratory
Procedures for the Analysis of Air Pollutants," presented at the Technicon
Symposium, Automation in Analytical Chemistry, New York, N. Y., Oct. 19, 1966.
A-ll
-------
No.A-13
SUMMARY OF ANALYTICAL METHOD
Parameter (s) Measures: Chlorine
Medium: Air (Ambient)
Name of Measurement Method: Mercuric Thiocyanate.
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications); Applicable where the presence of
chlorine is suspected, e.g., in areas near the preparation of calcium chloride and
where chlorine gas is used.
Summary of Method (Short Paragraph): Chlorine in the air sample is absorbed in
0.02N sodium arsenite solution and reduced to chloride ion. Addition of ferric
alum and mercuric thiocyanate to the sample produces red ferric thiocyanate which
is determined spectrophotoraetrically.
Limitations:
Range of Applicability: 0 to 0.35 parts/million Cl~. For higher chlorine
concentrations a shorter sampling interval or a lower sampling rate can
extend the range to 5 ppm.
Interferences: Bromides, iodides, cyanides, thiosulfates, nitrites and
chlorides.
Pitfalls; Special Precautions: Since chloride is a common contaminant, extreme
care should be taken with cleanliness of glassware. Glassware should be
washed and rinsed thoroughly with deionlzed-distilled water.
Statistical Characteristics:
Accuracy: No data are available from reference cited below.
Precision; Estimated standard error for the combined sampling and analytical
procedure is + 10% in the concentration range of 0.01 to 5 ppm.
Stability: The color produced is stable for at least 1 hour.
Time of Measurement (Max. Freq., Recovery Period, etc.): Not stated.
Calibration Requirements: No unusual requirements.
Data Outputs: Electrical signal displayed on meter or graph.
Special Sampling Requirements (Collection. Storage. Handling): Sampling train
consisting of absorber, glasswool filter,critical orifice, and air pumps. All
probes and tubing upstream from the absorber should be Pyrex glass, stainless steel
or Teflon.
Reference: "DeternJnation of Chlorine in Ambient Air: Mercuric Thiocyanate Method. H-4",
from an informal compilation of analytical methods provided by John B. Clements,
EPA, National Environmental Research Center, Research Triangle Park N C Letter
dated October 5, 1972.
A-12
-------
No. A-U
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Ferric Ion
Medium: Air (Ambient)
Name of Measurement Method: Thiocyanate
Principal Detection Technique: Coloriraetric
Purpose of Measurement (Important Applications): Applicable to animal exposure
chambers and to ambient air if sufficient sample is collected.
Summary of Method: Ferric oxide aerosol is collected on glass filters
by pulling air through a calibrated orifice. The ferric ion reacts with
ammonium thiocyanate to give a color which is determined colorimecrically.
Limitations:
Range of Applicability: 10-200 ug/ml of Fe.O- in 100 ml. Best results
between 20 and 150 ug/ml.
Interferences: High humidity; large samples; cations in 3-700 ppm—Ag
Co , Cu , Hg +, Sr +, and MoO^. pH must be 1.2 to 1.5 for best results.
Pitfalls; Special Precautions: None Stated
Statistical Characteristics:
Accuracy: No data available
Precision: For precise results amount of reagents and standing
time must be kept constant (less than 5 minutes).
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Completed
samples can be placed in glassine envelopes for later analysis.
Calibration Requirements: Calibrated orifices are available commercially.
Data Outputs: None Stated
Special Sampling Requirements (Collection. Storage, Handling): Samples
with over 200 ug/ml Fe.O- should be avoided.
References: "Determination of Ferric Ion, C-l", Informal compilation by
John B. Clements, EPA, National Environmental Research Center, Research
Triangle Park, N. C. Letter dated October 5, 1972.
A-13
-------
No. A-15
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Fluoride
Medium: Air (Ambient)
Name of Measurement Method: Impregnated Filter
Principal Detection Technique: Specific ion electrode
Purpose of Measurement (Important Applications): Water soluble fluorides from
ambient air.
Summary of Method: Caseous and particulate fluorides in ambient air are collected
by filtration anH chemisorption on filter paper impregnated with sodium formate.
Water soluble fluorides art; extracted and buffered with O.JM sodium citrate.
The fluoride ion concentration is then measured with a specific ion electrode.
Limitations:
Range of Applicability: 0.05 to 1000 ug F~/m3 air. Calibration is for
0.05 to JO ng/m "at the given sampling rate.
Interferences: [OH-] > [F-]; A13+; Fe3+
Pitfalls; Special Precautions: None cited
Statistical Characteristics:
Accuracy: Not stated.
Precision: Relative standard deviation is +_ 2% as determined on standard
solutions.
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Not stated.
Calibration Requirements: No unusual requirements.
Data Outputs: Not stated. Assumed to be an electrical signal displayed on
meter or graph.
Special Sampling Requirements (Collection, Storage, Handling): Hi-volume
sequential sampler of 100 liters/rain air flow.
References: "Determination of Fluoride in Ambient Air—Impregnated Filter",
from an informal compilation of analytical methods provided by John B. Clements,
EPA, National Environmental Research Center, Research Triangle Park, N.C.
Letter dated October 5, 1972.
A-14
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No. A-16
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Fluorides (Water Soluble)
Medium: Ambient Air - atmospheric particulates
Name of Measurement Method: Not stated
Principal Detection Techniques: Specific Ion Electrode
Purpose of Measurement (Important Applications); Water soluble fluorides.
Not reliable for low fluoride concentrations.
Summary of Method: An aliquot of the glass fiber filter collected by a
high volume sampler is extracted with distilled water. The water soluble
fluorides are measured with a specific ion electrode of the kind developed
by Frant and Ross.
Limitations:
Range and Sensitivity: Sensitivity is 0.16 ng F /ml. Range is
0.16 to 5.00 (j.g F~/ml.
Interferences: Ionic strength affects activity of F~; pH dependent -
working pH range 5-8; iron, aluminum.
Pitfalls; Special Precautions: Interferences can be eliminated
by use of 0.2 M sodium citrate buffer.
Statistical Characteristics:
Accuracy: Not given in reference below.
Precision: The standard deviation is 0.017 ug F~/ml for the analytical
portion of the method.
Time of Measurement: Not stated
Calibration Requirements: Specific ion meter should be restandardized after
every 28 samples.
Data Outputs: Not stated. Assumed to be electrical signal displayed on
meter or graph.
Special Sampling Requirements (Collection, Storage, Handling): Hi-volume
sampler, as described in Fed. Register, Vol. 36 // 84, April 30, 1971.
Appendix B.
References: "Determination of Water Soluble Fluoride in Atmospheric
Particulates," from an informal compilation of analytical methods provided
by John B. Clements, EPA, National Environmental Research Center, Research
Triangle Park, N.C. Letter dated October 5, 1972.
A-15
-------
No. A-17
SUMMARY OF ANALYTICAL METHOD
Parameter (s) Measured; Fluorides in Stack Gas
Medium: Air (Point sonrre)
Name of Measurement Method: SPADNS
Principal Detection Techniques: Spectrophotcmetric
Purpose of Measurement (Important Applications) : Applicable for fluoride
determination in stack gas.
Summary of Method; Particulate and gaseous fluorides are collected from
the same stack gas sample using a combination particulate - gas sampling
train. Particulate fluorides are collected isokinetically while gaseous
fluorides are converted to soluble fluosilicic acid and slightly soluble
orthosilicic acid. Water soluble particulate fluorides, total particulate
fluorides, and soluble gaseous fluorides are determined separately. The
collected fluorides are distilled from sulfuric acid and analyzed spectro-
photometrically using the b>aching reaction of fluoride in a zirconium-dye
lake .
Limitations;
Range of Applicability: Beer's law is obeyed in F range of 0-1.4 iig/ml.
Detection limit is of the order of 0.02 ug/ml.
1-4- 2+ — ^+ (X^+ 24- 1 2
Interferences: Al ; Ca ; Cl ; Fe _; Mn^ ' j Mg ; PO^ ; SO^ j
Most are removed by distillation; Cl removed by adding silver sulfate.
Pitfalls; Special Precautions: Determination should be carried out with
standards and samples at the identical temperature. Error of 0.01 ml/liter
F occurs with each degree difference in temperature.
Statistical Charateristics:
Accuracy: No data aval J able.
Precision: Error +_ 15% Cor sampling and analytical procedure, and
4% for analytical.
Stability: Color stable for about 2 hours after Initial 15 minutes.
Time of Measurement; Not stated
Calibration RequlrGinc-nts: [to run new calibration curve each time new b.il.-li
o*~SPANDS reagent is pre'parod. Occasional recovery check with standard fluoride
will indicate when sulfurtc acid is to be replaced.
Data Outputs: Not stated. Assumed to be electric signal displayed on meter or
graph.
Special Sampling Requirements (Collection. Storage. Handling): Sampling train
is illustrated in reference below.
References; "Determination of Fluorides in Stack Gas", from an informal
compilation of analytical nethods provided by Tohn B. Clements, EPA, National
Environmental Research Center, Research Triangle Park, N.C. Letter dated
October 5, 1972.
A- 16
-------
No. A--16
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Fluoride in Stack Cases.
Medium: Air (Point source)
Name of Measurement Method:
Principal Detection Techniques; Specific Ion Electrode.
Purpose of Measurement (Important Applications) : Applicable to fluoride
emitted from stacks in plants of various industrial processes(aluminum
reduction, metal smelting, etc.)
Summary of Method:
Gaseous fluorides are collected and reacted to form water soluble fluosilicic
acid which is absorbed in distilled water. The collected solution is
buffered with sodium citrate to control the total ionic strength of the
solution, The fluoride ion concentration is determined with a specific ion
electrode.
Limitations:
Range of Applicability: 1 to 3000 ppra.
-3+3+
Interferences: OH If >F ; Al , Fe . Interference can be removed by
citrate buffer.
Pitfalls; Special Precautions: Care should be taken in selection
purification, and testing of reagents and apparatus so that samples
are exposed a minimum amount of time.
Statistical Characteristics:
Accuracy; Hot stated.
Precisions: The relative standard deviation of the analysis is
about 2% as determined on standard solutions.
Time of Measurement (Maximum Frequency.Recovery Period, etc.); wot stated.
Calibration Requirements: No unusual requirements.
Data Outputs: Not stated. Assumed to be electrical signal displayed on
graph or meter.
Special Sampling Requirements (Collection. Storage. Handling); Combination
particulate-gas sampling train as illustrated in the reference cited in the
Summary Method for determination of fluorides in stack gases by SPADNS Method.
References: "Determination of Fluorides in Stack Gas: Specific Ion Electrode,
H-8", from an informal compilation of analytical methods provided by John B.
Clements, EPA, National Environmental Research Center, Research Triangle Park,
N.C. Letter dated October 5, 1972.
A-17
-------
No. A-19
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Fluoride, Caseous and Particulate
Medium: Air (Point source)
Name of Measurement Method: Not stated
Principal Detection Techniques: Spectrophotometric
Purpose of Measurement (Important Applications): Applicable to industrial
sources that emit compounds containing fluorides, in which hydrogen fluoride
occurs in association with particulate fluoride (e.g., production of phosphate
fertilizers, glass and ceramics, processing of aluminum ore, iron and steel.)
Summary of Method: Particulate and gaseous fluorides arc collected Irom
stack gas by a combination particulate.i;as sampling train. Hyrirocon fluoride
is converted to loss reactive silicon tetrafluoriue beCorc the particulate is
collected by reaction with a glass sampling system held at. elevated tempera-
tures. The silicon tetrafluoride is collected in an alkaline solution. The
fluoride ion is reacted with the lanthanum saJt of alizarin complcxonc which
forms a soluble, blue ternary complex that is measured spectrophotometrically
at 662 nn.
l.initaLLons:
Range .,, rt.-pl I..ub •' 1 Itj '. TroT. 2 erv "p™ »• i-lv->ii«!anris of pom fluoride
and ds 111 Lie , - 0.1 , g f luor Lilt*.
Interferences: Chlorides and other halogens; cations such as Al and Fe
(These cations can be precipitated by the addition of a sodium acetate
buffer.)
Pitt'al Is, jji'cial rocaiit i_ons: l.'one ''.L.Hi'J
Statistical Characteristics:
Accuracy and ''rccision: No data available from reference cited below.
Sensitivity: Abcut 0.1 ug fluoride.
Time of Measurement; None indicated.
I'-alibration Requirements: Make new calibration curve with each new batch of
Belcher reagent.
Data Outputs: Mot stated. Assumed to be electrical signal displayed on meter
or graph.
Special Sampling Hequireaicnts (Collection Storage. Handling): Combination
particulate - p,as sar-.pii.nn train used.
References: "Determination of Gaseous and Particulate Fluorine in Industrial
Stack Cases", from an informal compilation of analytical methods provided by
.lolm B. Clements, Hi'A, National Environmental Research Center, Research Triangle
Park, N.C. Letter dated October 5, 1972.
A-18
-------
No. A-20
SUMMARY OF ANALYTICAL.METHOD
Parameter (s) Measured: Hydrocarbons (i\-rr .::.;•! Xi Motiune)
Medium; Air (Ambientl
Name of Measurement Method:
Frincinal Detection Technique: Cas Clirop>,il.i>i>r,ii.ln'. Carrier gas (He, N, Air, or
M.) contains less than 0.065 mp/m3 hlldrminrtni':J a« methane.
Purpose of Measurement (Important Appl i. .11 ions.). Applicable to the semicont inui'U'-
measurement of hydrocarbons corrected ;'IM methnni- in ambient air.
Summary of Method: Measured volumes of air arc delivered semicontinuously (4-12
times/hour) to a hydrogen flame ionization detector to measure its total hydro-
carbon (THC) content. The methane content of a sample of the same air is deter-
mined and subtracted from the THC to correct for the methane content.
Limitations;
Range and Sensitivity: THC range 0 to 13.1 ng'm (0 to 20 ppm) Carbon
(as CH,). CH, range 0 to 6.55 mg/m3. Lower ranges—THC 0-1.31 mg/m3 carbon
(as CH^) and CH, range to 1.31 mg/m3.
Sensitivity - (Higher Levels) for THC -s 0.065 mg/m carbon(as CH.)and
methane is 0.033 mg/m3. Lower: ScnsitivUy is O.Olb mg/m3.
Interferences: Air peak interference can bo negated electronically.
Statistical Characteristics:
Accuracy - Depends on linearity of instnimcnt and absolute concentration
of the calibration gases. Accuracy of 1% of full scale in higher and 2%
in lower concentration ranges.
"reclsion: U'ith calibration pases +0.5% of full scale in higher ranges.
Stability: Variations in ambient room temnerature can affect adverselv
performance characteristics. Instrument should meet performance specs.
with room temperature changes of ^3°C.
Time of Measurement: Hot stated.
Calibration Requirements: Gases for range 10,20,40,80% needed.
Data Outputs: Electrical signal disnlaved on meter or graoh, or entered into
data acquisition svstem.
Special Sanpling. Requirements (Collection, Storage, Handling): None stated.
References: Federal Register, "ol. 36, #84, Anril 30, 1971.
A-19
-------
No. A-21
SUMMARY OF ANALYTICAL METHOD
Parameter (s) Measured: Hydrogen Chloride and Chlorine in Stack Gas
Medium: Air(point source)
Name of Measurement Method; Volhard
Principal Detection Method: Titrimetric
Purpose of Measurement (Important Applications): Sources emitting both hydrogen
chloride and chlorine; O.K., hydrochloric acid manufacture.
Summary of Method: Hydrogen chloride and chlorine are collected from the
gas stream in a known quantity of alkaline arsenite absorbing reagent. The
chlorine is reduced to chloride by arsenite and measured by titrating the
unconsumed arsenite with standard iodine solution. Total chloride concen-
tration is determined by Volhard titration. Hydrogen chloride concentration
is calculated by subtraction of the chlorine concentration from total chloride
concentration.
Limitations:
R.ingc rf Applicability: Two procedures are given, with different: ranges
of applicability. Procedure A: 10 to JOOO ppm; Procedure B: 1000 ppr.
to perrenlacc; nuantities.
Interferences: Silver salts or substances that form them;
Hg2+; S02; I2; N02; and 0-j .
Pitfalls; Special Precautions: Temperature should be below 25°C
for titrations.
Statistical Characteristics:
Accuracy : Error + 10% (combined sampline and analytical errors).
Precision; Precision is + 2% on standard samples containing
NaCl and NaAs02<
Time of Measurement; Not stated
Calibration Requirements: No unusual requirements.
Data Outputs: Not stated; assumed to be visual observations, manually recorded.
Special Sampling Requirements (Collection, Storage. Handling): Midget
impingers, or grab sample flasks.
References: "Determination of Hydrogen Chloride and Chlorine in Stack Gas,"
from an informal compilation of analytical methods provided by John B. Clements,
EPA, National Environmental Research Center, Research Triangle Park, N.C.
Letter dated October 5. 1972.
A-20
-------
No. A-22
SUMMARY OF ANALYTICAL METHOD
***
Parameter(s) Measured: Hydrogen Sulfide - ^S
Medium: Ambient Air
Name of Measurement Method: Not stated.
Principal Detection Techniques; Colorimetric
Purpose of Measurement (Important Applications);
Summary of Method; Hydrogen sulfide is collected by drawing ambient air through
a suspension of cadmium hydroxide. The H.S is determined by reacting with para-
arainodimethylaniline and ferric chloride. This reaction results in the formation
of methylene blue. The excess ferric chloride is removed and the absorbance of
the resulting color determined photometrically.
Limitations:
Range of Applicability: Not stated.
Interferences: Sulfur dioxide - removed by doubling amount of ferric
chloride. Strong reducing agents also interfere.
Pitfalls; Special Precautions: At concentrations of 120 ug/ral, H.S acts
as a strong reducing agent and will inhibit the reaction. In this case
dilution would be necessary.
Statistical Characteristics:
Accuracy: :;ot stated.
Precision;;j0t stated.
Stability: The collected sample is stable for 3 to 5 days in stabilized
absorbing agent. Decrease of 10 to 20% of concentration occurs by end of
8 days.
Time of Measurement: Not stated
Calibration Requirements: Not given.
**«Corrments by Users; Very rarely used; lacks sensitivity
Data Outputs: Not stated. Assumed to be electrical signal displayed on stripchart.
Special Sampling Requirements (Collection, Storage. Handling); Collection efficiency
is more than 97% when collected in a restricted opening bubbler in 50 ml collecting
solution with the orifice submerged 3 1/2 in.
References:
Morgan, G. B., Golden, C., and Tabor, E. C., "New and Improved Procedures for
Gas Sampling and Analysis in the National Air Sampling Network", presented at the
Technicon Symposium, Automation in Analytical Chemistry, New York.N. Y., Oct. 19, 1966.
A-21
-------
No. A-23
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Hydrogen Sulfide
Medium: Air (Ambient)
Name or Measurement Method: Mercuric Chioride-Tape.
Principal Detection Techniques: Optical Transmittance
Purpose of Measurement (Important Applications): None stated.
Summary of Method: liydroecn sulfide in the atmosphere is chemically adsorbed
on filter paper tapes impregnated with mercuric chloride. Samples are taken
sequenti.il Iv with an AISI tape sampler. The collected hydrogen sulfide-
mercuric chloride complex reacts with ammonium hydroxide and produces a
darkened area on which optical transmittance measurements are made.
Limitations:
Range of Applicability: 0.5 to 15 ppb range and 0.5 ppb sensitivity—
with 2 hour sampling period and 7 liter/minute flow rate.
Interferences: None
Pitfalls: Special Precautions: None stated.
Statisiic.il Characteristics:
Ace1 uracy. Not stated.
Precision: Average standard deviation of + 0.5 ppb (in the range of
0 to L5 nub).
Time of Measurement; Sampling interval 10 to 210 minutes
Calibration Requirements: No special requirements.
Comments by Users: None
Data Outputs: Not stated; assumed to be visual observations, manually recorded.
Special Sampling Requirements (Collection, Storage, Handling) : AISI tape sampler
needed.
References: "Determination of Hydrogen Sulfide in Ambient Air. H-21",
from an informal compilation of analytical methods provided by John B. Clemen lb..
EPA, National Environmental Research Center, Research Triangle Park, N.C.
Letter dated October 5, 1972.
A-22
-------
No. A-24
SUMMARY OF ANALYTICAL METHOD
*•**
Parameter(s) Measured: Mercury
Medium: Air -(Stationary Sources)
Name of Measurement Method: None Stated
Principal Detection Technique: Atomic Absorption
Purpose of Measurement (Important Applications): Applicable to gaseous
emissions from stationary sources.
Summary of Method: Gaseous samples are collected in impingers containing
acidic iodine monochloride solutions. Collected mercury is reduced to the
elemental form in basic hydroxylamine sulfate. Mercury is vaporized by
zero grade air stream and determined on the atomic absorption spectrophotometer.
Limitations:
Range of Applicability: Not Stated
Interferences: Sulfur Dioxide
Pitfalls; Special Precautions: None Stated
Statistical Characteristics:
Accuracy or Precision: Mot Stated
Time of Measurement: Not Stated
Calibration Requirements: Use standard methods and equipment as detailed in
APTD-0576 to calibrate rate meter, and dry gas meter.
***CommenCs by Users; SO,, Interferes seriously; not aatlgfpcror" method
Data Outputs: Not stated, assumed to be analog signal displayed on graph.
Special Sampling Requirements (Collection. Storage. Handling): Sampling train
described in APTD-0581 used by EPA. Commercial models available.
References: Federal Register, Vol. 36, 0235, Dec. 7, 1971.
A-23
-------
Ho. A-25
SUMMARY OF ANALYTICAL METHOD
***
Parameter(s) Measured: Mercury
Medium; Air (Stationary Sources)
Name of Measurement Method: None Stated
Principal Detection Technique: Atomic Absorption - flameless mode.
Purpose of Measurement (Important Applications): Applicable to determination
of mercury in particulate and gaseous emissions from stationary sources.only when
specified by test procedures for determining compliance with the Clean Air Act
as amended (Public Law 91-604).
Summary of Method: Particulate and gaseous emissions are isokinetically
sampled from source and collected in acidic iodine monochloride solutions.
Mercury collected (in mercuric state) is reduced to elemental mercury in
basic solution of hydroxylamina sulfate. The mercury is vaporized using
zero grade air stream and then analyzed.
Limitations:
Range and Sensitivity: Not Stated
Interferences; Sulfur Dioxide
Pitfalls; Special Precautions: None cited
Statistical Characteristics:
Accuracy: Not Stated
Precision: Not Stated
Stability; Not Stated
Time of Measurement: Not Stated
Calibration Requirements: Use standard method as per APTD 0576 to calibrate
rate meter, pitot tube, dry gas meter and probe heater. Recalibrate after
each test.
***Comnients by Users; SO,, interferes seriously; not satisfactory method
Data Outputs: None stated i assumed to be electrical signal displayed on meter.
Special Sampling Requirements (Collection, Storage. Handling): Particulate
sample train used are described in Reference.
References: Federal Register, Vol. 36 0235, Tuesday, Dec. 7, 1971.
A-24
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No. A-26
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Metals from Airborne Participates
Antimony Chromium Nickel
Beryllium Copper Tin
Bismuth Iron Titanium
Cadmium Lead Vanadium
Cobalt Manganese Zinc
Medium: Air (Ambient)
Name of Measurement Method: Not stated.
Principal Detection Techniques: Emission Spectrometry or Atomic Absorption.
Purpose of Measurement (Important Applications): Potentially applicable to many
metals. Used to analyze Be, Bi, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sb, Sn, Ti, V
and Zn in atmosphere. Most applicable to extraction of large numbers of samples.
Summary of Method (Short Paragraph): Particulate is collected on high volume glass
fiber filters and ashed to remove organic matter. The metals are then extracted
with a mixture of hydrochloric and nitric acids. The concentration of the metals
is determined by emission spectrometry or atomic absorption Spectrometry.
Limitations:
Range of Applicability: The limits of range are determined by the sensitivity
limits of particular metals being analyzed. Ranges for these metalb by both
emission and alomi< adsorption spccLroscopy are given in the Reference below.
Interferences: The glass-fiber filter contributes a matrix effect and a metal
background, which must be taken into account.
Statistical Characteristics:
Accuracy and Precision: No data are available from reference.
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Not stated.
Calibration Requirements: No unusual requirements.
Comments by Users: None stated.
Data Outputs: Not stated. Assumed to be electrical signal displayed on meter.
Special Sampling Requirements (Collection, Storage. Handling); Hi-Vol sampler
as described in Federal Register, Vol. 36 #84, April 30, 1971, Appendix B.
References:
(1) "Acid Extraction of Metals from Airborne Particulate", from an
informal compilation of analytical methods provided by John B.
Clements, EPA, National Environmental Research Center, Research
Triangle Park, N.C. Letter dated October 5, 1972.
(2) "Atomic Absorption ol Selected Metals Ootained oy high Volume
Sampler", from an informal compilation of analytical methods
provided b> Jciin £. Clements, EPA, National Environmental
Resoarcn Center, Research Triangle Park, N.C. Letter dated
October 5, 1972.
~
-------
No. A-27
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Moisture
Medium; Air (Stack gases)
Name of Measurement Method: Not Stated
Principal Detection Technique: Volumetric
Purpose of Measurement (Important Applications): Applicable when specified by
new Source Performance Standards as indicated in Reference below. Notapplicable
when liquid droplets are present in gas stream.
Summary of Method: Moisture is removed from the gas stream, condensed, and
determined volumetrically.
Limitations:
Range of Applicability: Not Stated
Interferences! Liquid droplets, particulates
Pitfalls; Special Precautions: Use stainless steel or Pyrex probe.
Heat to prevent condensation.
Statistical Characteristics:
Accuracy: Not Stated
Revision: Not Stated
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Not Stated
Calibration Requirements: None
Comments by Users: None cited
Data Outputs: Visual observation and manual recording.
Special Sampling Requirements (Collection. Storage, Handling): Sample at rate ot
0.075 cfm.
References; Federal Register, Vol. 36, ff247, Thurs. Dec. 23, 1971.
A-26
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No. A-28
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Nicraces and Mrrite-3
Medium; Air (Ambient)
Name of Measurement Method: Diazotiation
Principal Detection Techniques: Colorimetric - Manual or automated
(Technicon AutoAnalyzer ).
Purpose of Measurement (Important Applications): For nitrate ions
in particulate matter collected by high volume sampling apparatus.
Summary of Method: An aliquot of the filter from high volume sample is extracted
with distilled water to remove water soluble nitrate. The nitrate is reduced to
nitrite by alkaline hydrazine and the nitrite is converted to nitrous acid which
diazotizes sulfanilamide. The resulting complex is coupled with N(l-napthyl)-
ethylenediamine dihydrochloride to give an intensely colored azo dye which is
determined colorimetrically.
Limitations:
Range of Applicability; Range is 0.1 to 50.0 (ig N0~ per ml, or
approximately 0.03 to 15 u,g nitrate per cubic meter of air.
Interferences: Corrections can be made for turbidiLy and the
presence of nitrites in sample.
Pitfalls; Special Precautions; Color developed must be measured
within 30 minutes of addition of the diazotiation coupling reagent
Statistical Characteristics:
Accuracy; Not stated
Precision: Standard deviation for analytical portions of the method is
4- 0.02 ug NO"/ml for samples containing 1.0 ng NO^/ml.
Sensitivity: 0.1 ug NO 3 per ml.
Time of Measurement (Maximum Frequency, Recovery Period, etc.): Virtually
100% of nitrate is reduced to nitrite 10 to 15 mins. at 52°C.
Calibration Requirements: No unusual requirements.
Comments by Users: None
Data Outputs: Not stated. Assumed to be electrical signal displayed on meter
Special Sampling Requirements (Collection, Storage, Handling):
High volume sampler as described in Federal Register, Vol. 36, #84,
April 30, 1971.
References:
(1) "Determination of Nitrate: Manual and Automated Analysis. M-23,"
from an informal compilation of analytical methods provided by
John 3. Clements, EPA, National Environmental Research Center,
Research Triangle Park, N.C. Letter dated October 5, 1972.
(2) Morgan G.ii., Tabor, E.C., Golden, C., and Clements, h.,
"Automated Laboratory Procedures for the Analysis of Air Pollu-
tants," presented at the Tecnnicon Symposium, Automation in
Analytical Chemistry, iiew York, N.Y., October 19, 1966.
A-27
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No. A-29
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Nitrogen Dioxide
Medium: Ambient Air
Name of Measurement Method: Automated
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications): Suitable for photometric
measurement.
Summary of Method: Nitrite diazotizes sulfanilamide quantitatively in aqueous
solution. A reddish-purple azo dye is produced by coupling the diazotized sulfanilamide
with N-napthyl-ethylene diamine dihydrochloride at pH 2.0 to 2.5. This is determined
colorimetrically. A Technicon AutoAnalyzer is used.
Limitations:
Range of Applicability: 0.1 to 2.0 ug N02/ml.
Interferences; None stated.
Pitfalls; Special Precautions: None stated.
Statistical Characteristics;
Accuracy; None stated.
Precision; Relative standard deviation is + 0.04 ugNO./ml.
Sensitivity; Approximately 0.02 UR/ml
Time of Measurement; 60 samples analyzed/hour. Hold up time for
manifold is 8 minutes.
Calibration Requirements: None stated.
Comments by Users: None
Data Outputs; Stripchart recorder.
Special Sampling Requirements (Collection. Storage. Handling): Collection in sulfa-
nilamide solution at rate of approx. 0.2 to 0.25 liter/rain, for total volume of about
0.27m3/day.
References:
(1) Morgan, G. B., Tabor, E. C., Golden, C., and Clements, H., "Automated Labora-
tory Procedures for the Analysis of Air Pollutants," presented at the Technicon
Symposium, Automation in Analytical Chemistry. New York, N. Y., Oct. 19, 1966.
(2) Morgan, G. B., Golden, C., and Tabor, E. C., "New and Improved Procedures for
Gas Sampling and Analysis in the National Air Sampling Network", presented at
the Technicon Symposium, Automation in Analytical Chemistry, New York, N.Y.,
Oct. 19, 1966.
A-28
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No. A- 30
SUMMARY OF ANALYTICAL METHOD
***
Parameter (s) Measured; Nitrogen Dioxide, Nitric Oxide, and Oxides of Nitrogen.
Medium: Air (Ambient)
Name of Measurement Method: Automated
Principal Detection Techniques: Clicmiluminescent reaction.
Purpose of Measurement (Important Applications) : Applicable to the measurement
of nitric oxide and nitrogen dioxide at concentrations found in the atmosphere
(0.005-1 ppm).
Sumnary of Method: Atmospheric concentrations of nitric oxide (NO) can be
measured by the chemiluminescent reaction of ozone with nitric oxide at reduced
or atmospheric pressure. Nitrogen dioxide (NO^) can be measured as nitric oxide
in the system after conversion of the nitrogen dioxide to nitric oxide. Air
samples are drawn directly into ths analyzer to establish a nitric oxide response;
then a switching valve directs the sample air through the converter where the NO 2
is converted quantitatively to NO. The detector then measures total oxides of
nitrogen (NOX) signal. By subtracting the NO signal from the NOX, the amount of
NO 2 present can be determined. The subtractive process is accomplished elec-
tronically in most commercial instruments.
Limitations:
•j
Range of Applicability: Different insLruiur.-.ts have rar.res from 0-12.3 t/'m
and 0-1226 x 10~3 g/mJ (0-1000 ppm).
Interferences: NH, at temperatures greater than 250°C. Also unstable nitrogen
compounds as PAN.
Pitfalls; Special Precautions: NOne stated
Statistical Characteristics:
Accuracy: + 2% is possible.
Precision: Precision determined with standard calibration gases is +_ 1.0% for
all measurement ranges.
Stability: Instrument stability dependent on proper pressure being maintained
in reaction chamber, and cooling of phototube to proper constant cooling
temperature.
Time of Measurement : Less than 1 minute
Calibration Requirements: Standard calibrated cylinder of NO (122,600 -g/m )
[(100 ppm)] in nitrogen used for calibration of system.
"**Comments bv Users: This is not now a reference method and is not
currently recommended for compliance use. It is currently in use as
a special study or research method.
n-iiii Outputs: Not stated. Assumed to be analog signal recorded on stripchart.
Special Sampling Requirements (Collection, Storage, Handling): Continuous as
outlined in reference below.
References: "Nitrogen Dioxide, Nitric Oxide, and Oxides of Nitrogen" from an informal
compilation of analytical methods provided by Andrew O'Keefe. EPA, National Environ-
mental Research Center, Research Triangle Park, N.C. (Received by MITRE,
November 1972.)
A- 29
-------
l!o. A-31
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Nitrogen Oxides
Medium; Air - stationary sources
Name of Measurement Method; Phenoldisulfonic acid (PDS)
Principal Detection Technique: Colorimetric
Purpose of Measurement (Important Applications); As specified for
determining compliance with New Source Performance Standards. (See P.ef. below)
Summary of Method: Grab sample is collected Jn an evacuated flask
containing a dilute sulfuric acid-hydrogen peroxide absorbing solution.
The nitrogen oxides, except nitrous oxide, are measured colorimetrically
using the phenoldisulfonic acid procedure.
Limitations:
Range of Applicability: Not Stated
Interferences; Particulate matter, moisture.
Pitfalls; Special Precautions: None Cited
Statistical Characteristics:
Accuracy and Reproducibility; Not Stated
Time of Measurement (Maximum Frequency, Recovery Period, etc.):
16 hours recovery time.
Calibration Requirements; None Stated
Comments by Users: None
Data Outputs: Not stated; assumed to be analog voltage displayed on meter.
Special Sampling Requirements (Collection. Storage, Handling):
Equipment as described on p. 24892, Federal Register 12/23/71
References; Federal Register, Vol. 36, #247, Thurs., Dec. 23, 1971.
A-30
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Ho. A-32
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Odor
Medium: Air (Ambient)
Name of Measurement Method: Scentomeier
Principal Detection Technique: Threshold value detection.
Purpose of Measurement (Important Appi i_--ai ions) : To determine order of
magnitude of the concentrjtion ot jn nciorous vapor detectable an free air
relative to the minimum detectable threshold concentration.
Summary of Method: Contaminated air is diluted with air that has been
carbon filtered to remove odor, to produce various dilutions of odor.
The size of odorous air inlet used to produce the highest detectable
dilution indicates the dilution factor, and correspondingly the approxi-
mate concentration of the odor in the atmosphere relative to the threshold
concentration in number of thresholds.
Limitations:
Range of Applicability: Graduated inlets OP. Scentometer give dilutions
that indicate odors in concentrations approximately 2, 7, 31 and 120 times
threshold concentration. This geometric progression of dilutions indicate
the magnitude of the odor concentration.
Interferences: Smoking, colds, etc.; factors that affect observer's
olefactory sense.
Pitfalls; Special Precautions: None stated.
StatisticaJ Characteristics:
Accuracy dnd Precision:
Averages and standard deviations based on measurements of air flow
with six different instruments were the following:
Threshhold Values
Diameter of Odorous-Air Inlet Theoretical Measured Standard Deviation
1/2 inch 3 2.3 0.2
1/4 inch 9 7.0 0.2
1/8 inch 33 31.0 1.3
1/16 inch 129 170. 12.
Time of Measurement; Not stated.
Calibration Requirements; None.
Comments by Users: None
Data Outputs: Not stated.
Special Sampling Requirements (Collection. Storage, Handling): Not stated.
References: "Determination of Relative Odor Concentration Scentometer," from
an informal compilation of analytical methods provided by John B. Clements,
EPA, National Environmental Research Center, Research Triangle Park, N.C.
Letter dated October 5, L972.
A-31
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No. A-33
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Opacity
Medium: Air (stationary sources)
Name of Measurement Method;
Principal Detection Technique; Visual
Purpose of Measurement (Important Applications): Applicable when
specified for determination of compliance with New Source Performance
Standards .(see Reference as cited below)
Summary of Method:
The relative opacity of an emission from a stationary source is
determined visually by a qualified observer certified to have completed
a smoke reading course conducted by EPA, or equivalent.
Limitations:
Range of Applicability;
Interferences: Not Stated
Pitfalls; Special Precautions; None Cited
Statistical Characteristics:
Accuracy and Reproducibility: None Cited
Time of Measurement (Maximum Frequency, Recovery Period, etc.);
Readings taken every 15 to 30 seconds to nearest 5% opacity,
and minimum of 25 readings.
Calibration Requirements: Certification renewable every 6 months.
Comments by Users: None
Data Outputs: Visual observation recorded manually.
Special Sampling Requirments (Collection. Storage, Handling):
None Cited
References; Federal Register, Vol. 36, 0247, Thurs., Dec. 23, 1971
A-32
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No. A-34
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Organic Acids (Total)
Medium: Air (point source)
Name of Measurement Method; None Stated
Principal Detection Techniques: Titrimetric
Purpose of Measurement (Important Applications); Applicable to sampling
from flue gases.
Summary of Method: Organic acids are collected by absorption in dilute sodium
hydroxide. The absorbing solutions are acidified and extracted with ether to
separate mineral from organic acids. A continuous reflux extractor provides
multiple contact to ensure efficient extraction. The organic acids are titrated
with standardized based using phenolphthalein Indicator.
Limitations;
Range of Applicability: Lower limit is 5 ppm. No upper limit, so long
as organic acids do not exhaust the sodium hydroxide scrubbers.
Interferences: S02 only known interference: this can be removed.
Pitfalls; Special Precautions: Lower molecular weight organic acids
are not extracted quantitatively.
Statistical Characteristics:
Accuracy; and Precision: No data available from reference cited.
T-lme of Measurement: Not stated
Calibration Requirements: No special requirements.
Comments by Users: None Cited
Data Outputs: None Cited
Special Sampling Requirements (Collection. Storage, Handling); Sampling
apparatus shown in reference cited.
References: "Determination of Total Organic Acids in Flue Gases, D-18,"
from an informal compilation of analytical methods provided by John B.
Clements, EPA, National Environmental Research Center, Research Triangle
Park, N.C. Letter dated October 5, 1972.
A-33
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No. A-35
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Particle Sizing
Medium : Air (Ambient)
Name of Measurement Method: BAHCO microparticle classifier.
Principal Detection Techniques; Gravimetric.
Purpose of Measurement (Important Applications): Laboratory use for
approximate size classification.
Summary of Method: Sample dust is fed into the center of a centrifuge
with a throttled air supply directed to oppose the outward movement of
the particles. Larger particles are retarded by the air stream and drop
into a chamber while the smaller particles proceed to the rim of the
centrifuge. The sample in the drop chamber is weighed and recorded as
% of loss of weight. The procedure is repeated with several throttles
to provide various size groupings.
Limitations:
Range of Applicability: 8 size groupings can be obtained with data
expressed as weight %. For particles with specific gravity of 2.75,
sizes from 0.95 to 26.8u diameter can be measured.
Interferences: Agglomeration during feed operation. Density of
material can limit number of cuts obtainable.
Pitfalls; Special Precautions: None Stated
Statistical Characteristics;
Accuracy: ;,-o data are in reference cited below.
Precision: Because of wide size range within each sample, the
instrument is useful only for approximate weight % distribution.
Time of Measurement (Maxjmum Frequency, Recovery Period, etc.):
None -.tated.
Calibration Requirements: Each total sample is the basis for 100% weight.
Comments by Users; None Cited
Data Outputs; None stated. Assumed to be visual observation and manual recording.
Special Sampling Requirements ^Collection. Storage. Handling); None stated.
References: "Particle Sizing BAHCO Microparticle Classifier, D-8-B", from an
informal compilation of analytical methods provided by John B. Clements, EPA,
National Environmental Research Center, Research Triangle Park, N.C. Letter
dated October 5, 1972.
A-3
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No. A-36
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Particle Sizing
Medium: Air (Ambient)
Name of Measurement Method; Coulter Counter
Principal Detection Techniques: Electronic Scaling
Purpose of Measurement (Important Applications): Limited to the labora-
tory, and to particles not soluble in an electrolyte.
Summary of Method: The size distribution of particulate material is analyzed
by electronically scaling and counting individual particles. The sample is
dispersed in an electrolyte into which dips a glass tube carrying a small
orifice in its wall. The electrolyte flows through the orifice, and if the
suspension is sufficiently dilute, the particles pass through the orifice
one at a time. As each particle passes through the orifice, it displaces
its own volume of electrolyte, changing the electrical resistance across
the orifice. This resistance change is detected by measuring the electric
current between electrodes in the electrolyte on either side of the orifice, •
and is converted into a voltage pulse whose amplitude for a given current
and electrolyte is proportional to the volume of the particle.
Limitations:
Range of Applicability: Aperture size should be selected such that largest
particle diameter in sample system is between 30 and 40% of orifice
diameter. Through the use of several apertures ranging in size from
lOu. to A00(j, particle size from 0.2^ to 250ji may be analyzed.
Interferences: (1) Electrical—motor brushes, welding equipment,
electrical typewriters, etc. (2) Coagulation of particles after
suspension in conducting fluid.
Statistical Characteristics;
Accuracy: Not stated.
Precision: Determinations usually give a vague size distri-
bution in comparison with other methods with a higher degree of
reproducibility.
Time of Measurement; Not stated.
Calibration Requirements: Each aperture must be calibrated. Follow
instructions furnished by manual.
Comments by Users: None
Data Outputs: Electrical signal displayed on chart or meter.
Special Sampling Requirements (Collection, Storage, Handling): Not stated.
References: "Particle Sizing—Coulter Counter, D-8-A," from an informal
compilation of analytical methods provided by John B. Clements, EPA,
National Environmental Research Center, Research Triangle Park, N.C.
Letter dated October 5, 1972.
A-35
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No. A-37
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Particulace Acids
Medium: Air (Ambient)
Name of Measurement Method:
Principal Detection Techniques: Titrimetric
Purpose of Measurement (Important Applications);
Summary of Method: The acid aerosol collected on a filter during high-volume
sampling is dissolved in distilled water by maceration of the filter. A
known quantity of sodium hydroxiJe is added, and the solution is back-
titrated with sulfuric acid to pH 7.
Limitations:
Range of Applicability: Particulates calculated as sulfuric acid
over range of 0.5 to 50 Pg/m3, with sensitivity of 0.5 ug/m3
Interferences: Presence of bases in particulates causes neutrali-
zation of the acids.
Pitfalls; Special Precautions: None stated.
Statistical Characteristics:
Accuracy and Precision; Have not been established
Sensitivity: 0.5 ug/m-*, expressed as sulfuric acid
Time of Measurement (Maximum Frequency, Recovery Period, etc.):
Calibration Requirements: No unusual requirements.
Comments by Users: None
Data Outputs: Not stated. Assumed to be visual observation, manually recorded.
Special Sampling Requirements (Collection, Storage, Handling):
Hi-Vol sampler, as described in Federal Register, Volume 36 #84, April 30, 1971.
References; "Determination of Particulatc Acids", from an informal compilation
of analytical methods provided by John B. Clements, EPA, National Environ-
mental Research Center, Research Triangle Park, N.C. Letter dated October
5, 1972.
A-36
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No. A-38
SUMMARY OF ANALYTICAL METHOD
ParameterCs) Measured: Particulates, Airborne (Fine)
Mcdiun: Air (AnbLent)
Kame of Measure-ient Method: Benzene Soluble "raction.
Principal Detection Technique: Gravimetric and Volumetric
Purpose of Measurement (Important Applications): Applicable to any particulate
collecteu on glass fiber filter from ambient air per Federal Register, Vol. 36,
084, April 30'," 1971.
Summary of "ethod: 'articulate collected on glass filters is extracted with
benzene, and the benzene is evaporated to leave the benzene soluble fraction
as a residue. The residue weight and volume are used to determine the concen-
tration of benzene soluble fractions of airborne particulate. (Other solvents
e.g. cyclohexane, acetone, chloroform, and dichloromethane have been used, but
yield different results.)
Limitations:
Range: Lower limits are 0.4 ug/nr* per 8000 mj air sample to 1.5 (Jig/or* per
2000 nr* air sample. Practically no upper limit—depends only on sampling
accurately.
Sensitivity; At least 3 mg of residue must be generated.
Interferences: (Nonvolatile) impurities in the benzene.
ritfalls; Special Precautions: Benzene is toxic and flammable and can
form explosive mixtures with air. Well functioning hood is essential.
Statistical Characteristics:
Precision, Accuracy and Stabllity: No data available from reference cited.
Time of Measurement: Not stated
Data Output: Not stated; assumed visual observation
Special Sampling Requirements (Collection, Storage, Handling): None stated
References: "Extraction of Airborne Particulates with Benzene, Ca-1," from
an informal compilation of analytical methods provided by John £. Clements,
EPA, National Environmental Research Center, Research Triangle Park, N.C.
Letter dated October 5, 1972.
A-37
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No. A-39
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Participates, Windblown (Coarse)
Medium: Air (Ambient)
Name of Measurement Method: Sticky Paper
Principal Detection Techniques: Visual
Purpose of Measurement (Important Applications): Suitable for airborne
particles in the size range 20 to 100 p (an indication of soiling potential
in atmosphere.) Data arc directional; aid in locating particle sources.
Summary of Method: Particulates carried by wind from a source of pollution
are captured by adhesive coated paper mounted on a cylinder that is positioned
perpendicular to the wind direction. The number of particles per square
millimeter (p/mm ) is estimated by visual comparison with reference standards.
The particulates may be examined microscopically to determine whether material
is predominantly erosion products, incineration products, vegetable matter, etc.
Analyses are made for the eight major directions. Data are directional and thus
helpful in locating source of particles.
Limitations:
Range of Applicability: Exposed sample compared with reference
standards ranging from 2 to 100 p/mm .
Interferences: Colored particulates interfere with visual comparison.
Pitfalls; Special Precautions: None Stated
Statistical Characteristics:
Accuracy: Not stated (see Precision)
Precision: Precision represented by geometric standard deviation
of + 1.5, i.e., any single measurement will approximate the mean
value within a factor of 3 with a 68% probability.
Sensitivity: 1 to 15 p/mm2
Stability: After treatment with clear enamel, samples are stable for
at least three months.
Time of Measurement (Maximum Frequency, Recovery Period, etc.); -'. oV- . •'
Calibration Requirements; Requires one-time preparation of comparison standards.
Comments by Users: None
Data Outputs: Not stated. Assumed to be visual comparison.
Special Sampling Requirements (Collection, Storage. Handling); No unusual
requirements.
References: "Windblown ('articulates: Sticky Paper", from an informal compilation
of analytical methods provided by John B. Clements, EPA. National Environmental
Research Center, Research Triangle Park, N.C. Letter dated October 5, 1972.
A-38
-------
No. A-40
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Particulate Emissions.
Medium: Air (Stationary sources)
Name of Measurement Method; Not stated
Principal Detection Technique; Gravimetric.
Purpose of Measurement (Important Applications); Applicable only when speci-
fied by procedures to determine compliance with New Source Performance
Standards (per Reference below).
Summary of Method; Particulate matter is withdrawn isokinetically from the
source and its weight is determined gravimetrically after removal of uncombined
water.
Limitations;
Range of Applicability: Not Stated
Interferences: Moisture
Pitfalls; Special Precautions: Pyrex probe. Heating system capable of
maintaining minimum gas temperature of 250°F to prevent condenstation
Statistical Characteristics;
Accuracy; Not Stated
Reproducibility; Not Stated
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Not Stated
Calibration Requirements; Recalibrate after each test.
Comments by Users: None Cited
Data Outputs; Not stated, assumed to be visual reading of scale.
Special Sampling Requirements (Collection. Storage. Handling); Sampling train
used by EPA as described in APTD-0581. Commercial models available.
References; Fed. Register Vol. 36, 0247, Thurs. Dec. 23, 1971.
A-39
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No. A-41
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Respirable Participate Fraction of Total Suspended
Particulate Mass.
Medium: Air (Ambient)
Name of Measurement Method: Cyclone separation
Principal Detection Techniques: Gravimetric and volumetric
Purpose of Measurement (Important Applications): Designed primarily for use in
industrial hygiene surveys, but has been adopted for sampling mass concentrations
of suspended particulates in ambient air.
Summary of Method: A cyclone separator is utilized to separate the respirable
particulate (RSP) fraction of suspended airborne particulates from the larger
particles found in ambient air. The smaller particles are captured on a filter
media. Mass concentration of both the respirable fraction and total particulate
matter found in ambient air is determined from the weight of samples collected
and the volume of air passing through the train during each sampling period.
Limitations:
Range of Applicability: If sampler is operated continuously for 2k hrs. at a
flow rate of 9 liters/min., a meaningful sample will^be obtained provided the
concentration of the ambient air is at least 30 iig/m . Weights are made to
nearest 0.1 mg. Flow rates measured to nearest 0.1 liter/minute. Real sampling
time recorded to nearest minute.
Interferences: High humidity or rainfall may affect sampling. Introduction
of moisture could cause errors in weights.
Pitfalls; Special Precautions: If chemical analysis is done for trace elements
and other constituents, care should be exercised to ascertain constituents of
filter media before use.
Statistical Characteristics:
Accuracy: Depends on degree of constant air flow rate maintained in RSP and
TSP samplers.
Precision: At average mass concentration of 115 mg/m of particulate ma^tei,
the standard deviation is 4.9 (corresponding to a relative standard deviation of
4.32); at an average of 39 mg/m^, Llie standard deviation is 5.1 (corresponding
to relative standard deviation of 13%) .Deviations apply to both RSP and TSP --impiing.
Time of Measurement: Not stated (See Sampling below)
Calibration Requirements; Critical orifices' flow rate must be calibrated before
field use and rocameter must be calibrated periodically.
Comments by Users:
Data Outputs: Not stated. Assumed to be visual and manually recorded.
Special Sampling Requirements (Collection. Storage. Handling): 24-hour sampling
periods - composite samples. Concentration of ambient air must be at least
30 mg/m at flow rate of 9 liters per minute.
References: "Tentative Procedure for Determination of the Respirable Particulatc
Fraction of Total Suspended Particulate Mass in the Atmosphere (Cyclone
Separation Method),'' informal compilation of analytical methods provided by
John B. Clements, EPA, Environmental Research Center, Research Triangle Park,
N.C. Letter dated October 5, 1972.
A-40
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No. A-42
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Suspended Particulates
Medium: Air (Ambient)
Name of Measurement Method: High Volume
Principal Detection Technique: Gravimetric and Volumetric
Purpose of Measurement (Important Applications): Applicable to measurement
of mass concentration of suspended particulates in ambient air.
Summary of Method: Air is drawn by means of a high-flow-rate blower into
a covered housing and through a filter that allows particles of less than
100 |^m to pass. These are collected on glass fibre filters. The mass con-
centration of particles is determined through measurement of mass of particles
collected and the volume of air sample.
Limitations:
Range and Sensitivity: At average flow rate of 170 m /min. for 24
hours adequate sample will be obtained, even at low concentrations
of 1 fjg/m particulates. At high particulate levels 6 to 8 hours are
satisfactory.
Sensitivity: Weights determined to nearest milligram; air flow
rates to measure 0.03 m3/min., time to nearest 8 mins.; and mass
concentrations to nearest mg/m .
interferences: Oily particulates - photochemical smog or wood
smoke may block filter and cause drop in air flow. Dense fog or
high humidity may severely reduce air flow. Glass filter can
introduce errors.
Pitfalls; Special Precautions; None Stated
Statistical Characteristics;
Accuracy; Error in measured average concentration may be greater
than + 50% of the average concentration.
Precision: The relative standard deviation for single analyst
variation is 3.0 percent. For multilaboratory variation it is
3.7 percent.
Time of Measurement; Not Stated
Calibration Requirements; Necessary for rotometer and orifice calibration
unit.
Comments by Users; None Stated
Data Outputs: None Stated- Assumed to be visual reading.
Special Sampling Requirements (Collection, Storage, Handling): High
volume sampling.
References: Federal Register, Vol. 36, 084, April 30, 1971.
A-41
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No. A-43
SUMMARY OF .ANALYTICAL^ METHOD
Parameter(s) Measured: Photochemical Oxidants (Ozone)
Medium: Air (Ambient)
Name of Measurement Method:
Principal Detection Technique: Chemilumine'scence; photometry.
Purpose of Measurement (Important Applications): Applicable to continuous
measurement of ozone in ambient air. Corrections made for nitrogen oxides
and sulfur dioxide.
Summary of Method: Ambient air and ethylene are delivered simultaneously to
a mixing zone, where the ozone in the air reacts with the ethylene to emit
light which is detected by a photomultiplier tube. The photocurrent is
amplified and read directly or displayed on recorder.
Limitations:
Range: 9.8 jig O./m to more than 1960 Ng O./m
Sensitivity: 9.8 ug 0-/m (0.005 ppm ozone)
Interferences: Other oxidizing and reducing species in ambient air
do not. interfere.
Statistical Characteristics.
Accuracy; Accurate within + 7 percent
Precision: Average deviation from mean of repeated single measurements
does not exceed 5% of the mean of mpasurements.
Time of Measurement: Not Stated
Calibration Requirements: KI calibration curve for standard solutions is
required: instrument not set must also be calibrated.
Comments by Users: None Stated
Data Outputs: Electrical signal recorded graphically.
Special Sampling Requirements (Collection. Storage. Handling):
Sampling train shown in Reference cited below.
References: Fed. Register, Vol. 36 084, April 30, 1971.
A-42
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No. A-44
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Sulfate
Medium: Air (Ambient)
Name of Measurement Method: Automated
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications): This method is applicable
only to an enclosed automated system such as AutoAnalyzer because the color
complex formed is oxidized by air.
Summary of Method: Air to be tested is drawn through a filter (per sampling
procedure cited below). An aliquot of the residue on the filter is extracted
with distilled water. The water soluble sulfate is reacted with a reagent
that contains equivalent amounts of barium chloride and methylthymol blue
while pH is maintained at 2.8. Subsequently pH is raised to 12.4 with
potassium hydroxide and the unreacted barium forms a chelate with the dye.
The excess dye, which is equivalent to the sulfate, becomes yellow and is
determined colorimetrically.
Limitations:
Range of Applicability: 1.0 to 150 pg SO^/ml or 0.3 to 45 ug SO^/m3
of air.
Sensitivity: + 1.0 yg SO^/ml.
Interferences: Heavy metals, particulates, oxidizing substances
Pitfalls; Special Precautions: Use nitrogen instead of air to segment stream
between AutoAnalyzer turntable and pump, in order to avoid oxidation.
Statistical Characteristics:
Precision: Standard deviation is 0.3 ug SO^/ml for samples containing
5.0 ug SOg/ml.
Stability: The standards are stable over an extended period. The
dye should be made fresh every day.
Time of Measurement (Maximum Frequency. Recovery Period, etc.):
Not stated.
Calibration Requirements; None stated.
Comments by Users: None Stated.
Data Outputs: None stated; assumed to be electrical signal recorded
on stripchart.
Special Sampling Requirements (Collection. Storage. Handling): High volume
sampling as described in the Federal Register, Vol. 36, 084, April 30, 1971,
Appendix B.
References:
(1) "Determination of Sulfate: Automated Method, M-15," from an informal
compilation of analytical methods provided by John B. Clements, EPA,
National Environmental Research Center, Research Triangle Park, N.C.
Letter dated October 5, 1972.
(2) Morgan, G.B., Tabor, E.C., Golden, C. and Clements, H., "Automated
Laboratory Procedures for the Analysis of Air Pollutants," presented
at the Technicon Symposium, Automation in Analytical Chemistry, New
York, N.Y.; October 19, 1966.
A-43
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No. A-45
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Sulfate
Medium: Air (Ambient)
Name of Measurement Method: Sulfa Ver
Principal Detection Techniques: Spectrophotometric or filter photometric.
Purpose of Measurement (Important Applications); Suitable to determine
sulfates that may exist in ambient air in the form of acid aerosols or
as combined salts.
Summary of Method: Sulfate is extracted from the glass fiber filter by
refluxing with water, followed by dilution or concentration. An aqueous
extract of the sample is treated with barium chloride in the presence
of Sulfa Ver, a stabilizing agent. Barium sulfate crystals of uniform
size are formed. The absorbance of the barium sulfate suspension is
measured by a spectrophotometer or a filter photometer.
Limitations:
Range or Applicability; 0.1 to 1.0 ug/m
Sensitivity: May be increased by concentrating sample or decreased
by diluting it.
Interferences: Ionic strength of other ions: changes in pH and
temperature; concentrations of the reagent.
Pitfalls; Special Precautions: None stated
Statistical Characteristics:
Accuracy: Based on recovery of standards is + 11.2%
Precision: Not stated
Stability: For maximum stability the following conditions should
be maintained. Temperature should not vary more than +5°C;
Sulfer Ver added should be 0.25 + O.lg; pH should not vary by
more than one unit; and specific conductance of the aqueous extract
should not vary by more than +300 p ohms/cm.
Time of Measurement: None stated
Calibration Requirements: Not stated.
Comments by Users: None Stated
Data Outputs: None stated; assumed to be an electric signal displaved on meter
or granh.
Special Sampling Requirements (Collection, Storage, Handling): High volume
sampling as described in Federal Register, Vol. 36, //84, April 30, 1971.
Appendix B.
References: "Determination of Sulfate - Sulfa Ver Method, M-18",from an Informal
compilation of analvtical methods provided by John B. Clements, EPA, National
Environmental Research Center, Research Triangle Park, N.C. Letter dated October
5, 1972.
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No. A-46
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Sulfate
Medium; Air (Ambient)
Name of Measurement Method; Turbidimetric Barium Sulfate
Principal Detection Techniques; Photometric, filter-photometric,
or, nephelometric.
Purpose of Measurement(Important Applications); Applicable for determination
of sulfate in particulate matter.
Summary of Method: Extracts of sulfate in particulate matter are treated
with barium chloride to form barium sulfate. The turbidity of the barium
sulfate is a measure of the sulfate content. The absorbance of the sulfate
suspension is measured by spectrophotmeter or filter photometer, or in the
case of very low concentration a nephelometer may be used.
Limitations:
Range of Applicability; 0.6 to 18 ug SO^/m of air. Can be expanded
by concentrating or diluting sulfate solution.
Interferences: Size of sulfate particles, concentration of the sulfate,
pH, ionic strength, or large temperature variation can affect the measurement.
Statistical Characteristics:
Accuracy and Precision: The coefficient of variation is 11%.
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Not
given.
Calibration Requirements: Not stated.
Comments by Users: None
Data Outputs: Electric signal displayed on meter or graph.
Special Sampling Requirements (Collection. Storage. Handling): High volume
sampling as described in Federal Register, Vol. 36, #84, April 30, 1971,
Appendix B.
References: "Determination of Sulfate—Turbidimetric Barium Sulfate Method",
from an informal compilation of analytical methods provided by John B. Clements,
EPA, National Environmental Research Center, Research Triangle Park, N.C. Letter
dated October S, 1972.
A-45
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No. A-47
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Sulfation Race
Medium: Ambient air
Name of Measurement Method: Lead Candle
Principal Detection Techniques: Colorimetry (Automated).
Purpose of Measurement (Important Applications):
Summary of Method: The lead peroxide of the exposed candle is quantitatively transferred
to a beaker. The sulfate is then solubilized and extracted and further treated to expel
carbon dioxide. A solution that is subsequently prepared is suitable for use in the
automated procedure. A Technicon AutoAnalyzer is used.
Limitations:
Range of Applicability: Not stated in reference bnlow.
Interferences: None stated.
Pitfalls; Special Precautions: None stated.
Statistical Characteristics:
Accuracy and Precision: Not stated.
Tjina of Mpaciiromont! Nor
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No. A-48
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Sulfur Dioxide
Medium: Ambient Air
Name of Measurement Method: Automated
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications):
Summary of Method: Sulfur dioxide in samnle reacts with tetrachloromercurate. Acid
bleached cararosaniline and formaldehvde react with the dichlorosulfito-mercurate
formed to give a red-ourple complex of intensitv orooorational to the original concen-
tration of sulfur dioxide. A Technicon AutoAnalyzer is used.
Limitations;
Range of Applicability: Concentrations up to 2.6 yg of S0_/ml
Interferences: Nitrogen dioxide is prevented from interfering by adding
sulfamic acid Just prior to adding pararosaniline.
Pitfalls; Special Precautions: None stated.
Statistical Characteristics:
Accuracy; Not stated.
Precision; The relative standard deviation is 1.0 + 0.05 pg of S02/ml.*
Time of Measurement; Retention time in flow system is approximately 12 minutes.
Rate of 60 samples/hour.
Calibration Requirements: None stated.
Comments by Users: None
Data Outputs: Strip chart recorder
Special Sampling Requirements (Collection. Storage, Handling): Air aspirated
through tetrachloromercurate at a rate of approximately 0.2 to 0.25 llter/min.
for total volume of about 0.27 m'/day.
References:
(1) Morgan, G. B., Tabor, E. C., Golden, C. and Clements, H., "Automated Laboratory
Procedures for the Analysis of Air Pollutants presented at the Technicon
Symposium, Automation in Analytical Chemistry, New York, N. Y., Oct. 19, 1966.
(2) Morgan, G. B., Golden, C., and Tabor, E. C., "New and Improved Procedures for
Gas Sampling and Analysis in the National Air Sampling Network", presented
at the Technicon Symposium, Automation in Analytical Chemistry, New York, N.Y.,
Oct. 19, 1966.
*As stated in Reference (1)above
A-47
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No. A-49
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Sulfur Dioxide
JMii!2>: Air (Ambient)
Name of Measurement Method: Automated.
Principal Detection Techniques: CouJometric - titrimetric
Purpose of Measurement; Applicable to continuous measurement of sulfur dioxide
in ambient atmosphere.
Summary of Method: Ambient air is drawn through a coulombic titration cell which
contains a solution of a buffered halide. Sulfur dioxide present in the air sample
reacts with the halide causing a decrease in current flow through the cell. The
current from the reference electrode needed to return the cell to a steady state
is directly related to the concentration of sulfur dioxide present
Limitations:
Range of Applicability: 0-5 ppm full scale. Lowest full scale range is
0-0.50 ppm full scale. Minimum detectable sensitivity is 0.020 ppm.
Interferences; Nitrogen dioxide, hydrogen sulfide, methyl mercaptan, ethylene,
ozone. These substances can be removed by scrubbers.
Pitfalls; Special Precautions; None stated
Statistical Characteristics:
Accuracy: Accuracy of 5% of full scale. Dependent on interference
equivalent, accuracy of calibration gases, linearily of instrument response.
Precision: Precision is +4% of full scale using standard gases.
Time of Measurement! Not stated, but assumed rapid.
Calibration Requirements: As outlined in instruction manual for instrument.
***Comments by Users: This is not now a reference method and is not currently
recommended for compliance use. It is currently in use as a special study
or research method.
Data Outputs: Read directly or displayed on recorder
Special Sampling Requirements (Collection, Storage, Handling): Continuous.
Filtration by gauze to remove interferences.
References;
"Sulfur Dioxide by Coulometry". From an informal compilation of analytical
methods provided by Andrew O'Keefe, EPA, National Environmental Research Center,
Research Triangle Park, N.C. (Received by MITRE, November 1972.)
A-48
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No. A-50
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Sulfur Dioxide
Medium: Air (Ambient)
Name of Measurement Method: Automated
Principal Detection Techniques: Flame Emission Spectrophotometric.
Purpose of Measurement (Important Applications): Applicable to determination
of total sulfur in most chemical components or in sulfur dioxide, which is
usually the primary sulfur pollutant of ambient air.
Summary of Method: The monitoring Instrument is based on the use of the
intensity of chemiluminescent light emitted by sulfur compounds in a hydrogen-
rich, hydrogen-air flame as a measure of the concentration of sulfur dioxide
in the air samples. The 384 nm emission band of sulfur is the most intense,
so when light from the luminescing sulfur passes through a narrow-band optical
filter only the 384 nm light is permitted to strike the photomultlplier tube.
The magnitude of the current produced is recorded.
Limitations;
Range of Applicability: Calibrated range is 0.1 to 1.5 ppm (V/V).
Minimum detectable concentration is 0.05 ppm at a signal-to-noise
ratio of 2.
Interferences; Appreciable presence of H.S and mercaptans removed
with selective scrubbers. However, interference from sulfur compounds
is usually small.
Pitfalls; Special Precautions: Drift in electronic circuitry and
deposits on optical surfaces in the burner housing also affect
accuracy, precision and stability of flame photometer. Both can
be corrected by adjusting the sensitivity of detecting circuitry.
Statistical Characteristics:
Accuracy: Instrument accuracy is within + 5% as determined by the
modified West and Gaeke colorimetric method.
Precision is within + 2 1/2% over range of 0.1 to 1.5 ppm. Response
of the instrument is within 95% within a maximum of 2 minutes.
Time of Measurement; Assumed to be rapid.
Calibration Requirements; Calibration may be accurate for several weeks
or months, depending on extent of contamination of air samples. Frequent
adjustment of sensitivity ensures reliable calibration curve.
Comments by Users; None stated
Data Outputs: Electrical signal entering automatic Data Acquisition System
with printing recorder.
Special Sampling Requirements (Collection. Storage. Handling); Important to
pump a constant air supply to burner when several sources are sampled. This
constancy of air flow affects accuracy, precision and stability critically.
References; "Determination of Sulfur Dioxide with an Automated Flame Emission
Photometric Instrument, C-5," from an informal compilation provided by
John B. Clements, EPA, National Environmental Research Center, Research
Triangle Park, N.C. Letter dated October 5, 1972.
A-49
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No. A-51
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Sulfur Dioxide
Medium: Air(stationary sources)
Name of Measurement Method: Barium Thorin
Principal Detection Technique; Titrimetric
Purpose of Measurement (Important Applications): Applicable when
specified for determination in compliance with New Source Standards
(per reference cited below).
Summary of Method; A gas sample is extracted from the sampling point
in the stack. The acid mist, including sulfur trioxicle is separated
from the sulfur dioxide. The sulfur dioxide fraction is measured by
the barium-thorin titration method.
Limitations:
Range of Applicability: Not stated in reference below.
Interferences: Particulate matter, sulfuric acid mist.
Pitfalls; Special Precautions: Pyrex glass probes must be used
to prevent condensation.
Statistical Characteristics:
Accuracy and Precision: No data cited.
Time of Measurement (Maximum Frequency. Recovery Period) Hot Stated
Calibration Requirements; Use standard methods and equipment approved
by administrator to calibrate rotameter, pi tot tube, dry gas meter, and
probe heater.
Comments by Users; None Stated
Data Outputs; Not Stated. Assumed to be visual observation.
Special Sampling Requirements (Collection, Storage, Handling);
Sampling train in Figure 6-1 p 24891, Federal Register 12/23/71
References; Federal Register, Vol. 36, //247, Thurs., Dec. 23 , 1971.
A-50
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No. A-52
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Sulfur Dioxide
Medium; Air (Ambient)
Name of Measurement Method; Hydrogen peroxide.
Principal Detection Techniques: Titrimetric.
Purpose of Measurement (Important Applications): Applicable to determine
SC>2 in ppm range in ambient air, where SO- is principal acid or basic
gaseous pollutant, or if long storage of samples is necessary prior to
analysis.
Summary of Method; Sulfur dioxide in ambient air is absorbed in hydrogen
peroxide at pH 5.0. This results in the formation of stable sulfuric
acid which is subsequently titrated with standard alkali.
Limitations:
Range of Applicability: 0.01 to 10.0 ppm
Interferences; Strong acid gases; reactive acid solids; sulfuric
acid if relative humidity >85%;< alkaline gases and basic solids;
sulfur trioxide; large amounts of solid material.
Pitfalls; Special Precautions: None cited
Statistical Characteristics:
Accuracy and Precision:
Error for the combined sampling and analytical technique
is + 10% in range <0.1 ppm. Accuracy incrases in range 0.1 to 1.0
ppm. Measurements should be reported to nearest 0.01 ppm.
Stability: The solutions after sample collection are stable for
at least one month and can be titrated long after collection.
Time of Measurement (Maximum Frequency, Recovery Period, etc.)
None stated
Calibration Requirements: Not stated
Comments by Users: None cited
Data Outputs: None Cited
Special Sampling Requirements Air metering and flow control
devices should be capable of controlling and measuring flows
with accuracy of + 2%.
References: "Determination of Sulfur Dioxide: Hydrogen Peroxide Method,
H-23", from an informal compilation of analytical methods provided by
John B. Clements, EPA, National Environmental Research Center, Research
Triangle Park, N.C. Letter dated Octover 5, 1972.
A-51
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No. A-53
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Sul fur Dioxide
Medium: Air (Ambient)
Name of Measurement Method: Pararosaniline
Principal Detection Techniques: Spectrophotometric
Purpose of Measurement (Important Applications); Applicable to the measurement
of sulfur dioxide in ambient air using sampling periods of 24 hours.
Summary of Method: Sulfur dioxide is absorbed from air in a solution of
potassium tetrachloramercurate (TCM). A dichlorosulfitomercurate complex, which
resists oxidation by air, is formed. The complex is then reacted with pararosaniline
and formaldehyde to form intensely colored pararosaniline methyl sulfonic acid. The
absorbance of the solution is measured spectrophotometrically.
Limitations:
Range of Applicability: 25 to 1050 ug/m (0.01 to 0.40 ppm> Concentration
3
below 25 Mg/m can be measured by sampling larger volumes of air, and higher
concentrations can be measured by using smaller gas samples.
Interferences: Oxides of nitrogen, ozone, heavy metals (all can be eliminated
by pretreatment.)
Pitfalls; Special Precautions: None Stated
Statistical Characteristics:
Accuracy: Not Stated
Precision; Relative standard deviation at 95% confidence level is 4.6% using
standard samples.
Stability; At 22°C. losses of S02 occur at the rate of 1% per day. At 5°C. no
detectable loss occurs. EDTA enhances stability of SO. in solution.
Time of Measurement: Not Stated
Calibration Requirements: As set out in method.
Comments by Users: None
Data Outputs: Not Stated. Assumed to be electrical signal displayed on
meter, graph, etc.
Special Sampling Requirements; 24-hour sampling; refrigerate at 5°C., keep from
direct sunlight.
References: Federal Register, Vol. 36, //84, Friday, Arril 30, 1971.
A-52
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No. A-54
SUMMARY OF ANALYTICAL METHODS
Parameter(s) Measured: Sulfur Dioxide, Hyd^tjgen Sulfide, Methyl Mercaptan and
Higher Molecular Weight Gaseous Compounds.
Medium: Air (Ambient)
***
Name of Measurement Method; Automated
Principal Detection Techniques: Gas Chromatographic, Flame photometric.
Purpose of Measurement (Important Applications): Applicable to measure ambient
concentrations of hydrogen sulfide, carbonyl sulfide, sulfur dioxide, methyl
mercaptan, ethyl mercaptan, dimethyl sulfide and propyl mercaptan, in both
urban and non-urban atmospheres.
Summary of Method; Air stream containing sulfur compounds is injected on an
analytical column, where the sulfur compounds are separated prior to entering the
flame detector. Hydrogen sulfide and carbonyl sulfide are eluted first, followed
by sulfur dioxide, methyl mercaptan, ethyl mercaptan, dimethyl sulfide and propyl
mercaptan. After each analysis cycle, a stripper column is backflushed to insure
that heavier sulfur compounds do not reach the chromatographic column.
Limitations;
Ranee of Applicability: Normal operating range of instrument is 0-2618 ug/m
(0-1.0 ppm). Minimum detectable sensitivity for most important sulfur compounds
is H,S 6.95 ng/n.3, SO 13.09 gg/m3, CH SH 9.81 ug/m3; (CH^S 38.01 ug/m^ and
CH3(CH2)2SH 46.59 yg/rn3.
Interferences: Carbonyl sulfide could interfere in t^S analysis. Use of
silver wool and scrubbers has overcome the difficulty.
Statistical Characteristics:
Accuracy; 1 percent to 2 percent of any full scale range.
Precision: Precision as determined with standard calibration gases is
within one percent of any full scale range.
Time of Measurement: Not stated
Calibration Requirements; A series of standard concentrations are needed for
each pollutant to be measured. Calibration curve is used to determine linearity
of response for each sulfur compound measured.
Comments by Users: This is not now a reference method and is not currently
recommended for compliance use. It is currently in use as a special study
or research method.
Data Outputs: Analog signal displayed on stripchart.
Special Sampling Requirements (Collection, Storage, Handling): Semi-continuous
(5-12 analyses per hour).
References: "Sulfur Dixoide, Hydrogen Sulfide, Methyl Mercaptan and Higher
Molecular Weight Gases Sulfur Compounds", from an informal compilation of
analytical methods provided by Andrew O'Keefe, EPA, National Environmental
Research Center, Research Triangle Park, N.C. (Received by MITRE, November 1972).
A-53
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No. A-55
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measures; Sulfuric Acid Aerosols
Medium: Air (Ambient)
Name of Measurement Method: None stated.
Principal Detection Techniques; Spectrophotometric , coulometric or
flame photometric.
Purpose of Measurement (Important Applications): Applicable to all ranges
in which sulfuric acid is found in the atmosphere. Sufficiently sensitive
to measure size distribution of the aerosols separated by multi-stage
impacters.
Summary of Method: Sulfuric acid is collected on glass-fiber filter or
by sonic impaction on copper discs. The sulfuric acid in the filter is
thermally decomposed at 400°C. to separate it from other sulfates. The
sulfur trioxide liberated from the sulfuric acid is reduced to sulfur
dioxide under an inert atmosphere. The resulting sulfur dioxide is
measured by spectrophotometry, by coulometry or by flame photometry.
Limitations:
Range of Applicability: For optimum precision, the method should be
limited to the collection and analyses of 0.4 to 40 |ig l^SO^ (spectrophoto-
metric); 0.6 to 15 \ig J^SCfy (flame photometric), and 0.1 to 20 jig H2SO^
(coulometric).
Sensitivity: Limits of the Spectrophotometric, coulometric and flame
photometric procedures are 0.8 ug, 0.03 ug and 0.0003 ug, respectively.
(Equivalent to parts per billion for 1-liter air samples.)
Interferences; Residual alkali in glass-fiber filters should be acid
washed. Filters made of organic materials should be avoided. Also
ammonium sulfate responds quantitatively as sulfuric acid.
Statistical Characteristics:
Accuracy; Not stated.
Precision; Glass fiber filters have a collection precision
within 1% for aerosols of 0.3p diameter or larger. Precision
for Spectrophotometric, coulometric and flame photometric pro-
cedures are 4.8%, 4.5% and 2.1% respectively.
Time of Measurement (Maximum Frequency. Recovery Period, etc.):
Not Stated.
Calibration Requirements: Calibration with working standards and the control
samples ensure the accuracy of the determination.
Comments by Users: None given.
Data Outputs: Not stated; assumed to be electric signal disolays on meter or
chart.
Special Sampling Requirements (Collection. Storage. Handling): Sulfuric acid
aerosols decav on the filter. Average rate of decav for a period of several
weens is about 2%. Probably higher for shorter intervals.
References: "Determination of Atmospheric Sulfuric Acid Aerosol", from an
informal compilation of analytical methods orovided by John B. Clemeni.-, EPA,
National Environmental Research Center, Research Triangle Park, N.C. Letter
dated October 5, 1972.
A-54
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No. A-56
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Sulfuric Acid Mist and Sulfur Dioxide
Medium: Air (Stationary sources)
Name of Measurement Method: Barium-thorin
Principal Detection Technique: Titrimetric
Purpose of Measurement (Important Applications): Only when specified for
test to determine compliance with New Source Performance Standards, as
outlined in reference below.
Summary of Method: Gas sample is extracted from a sampling point in a stack,
and the acid mist including sulfur trioxide is separated from sulfur dioxide.
Both fractions are measured separately by barium-thorin titration.
Limitations;
Range of Applicability; None stated.
Interferences: Moisture
Pitfalls; Special Precautions: None stated.
Statistical Characteristics:
Accuracy and Precision: None stated.
Time of Measurement (Maximum Frequency. Recovery Period, etc.) None stated.
Calibration Requirements: Use standard method and equipment approved by the EPA
Administrator to calibrate orifice meter, pitot tube, dry gas meter and probe heater.
Comments by Users: None Stated.
Data Outputs: Visual observations. Manually recorded.
Special Sampling Requirements (Collection. Storage. Handling): Sampling train Figure 8-1,
Federal Register 12/23/71 p 24893
Reference: Federal Register, Vol. 36., #247, Thurs., Dec. 23, 1971.
A-55
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No. A-57
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Stack Gas Velocity and Volumetric Flow Rate
Medium; Air (Point Source)
Name of Measurement Method; Type S Pitot tube
Principal Detection Techniques: Gravimetric and Volumetric
Purpose of Measurement (Important Applications): Should be applied only
when specified by the test procedures for determining compliance with the
New Source Performance Standards as set out in reference below.
Summary of Method: Stack gas velocity is determined from the gas density
and from measurement of the velocity head using a Type S pitot Tube. Involves
use of gas analyzer to determine average molecular weight of stack gases as
needed for computing gas velocity.
Limitations:
Range of Applicability: Not Stated
Interferences: Not Stated
Pitfalls; Special Precautions: None sited
Statistical Characteristics:
Accuracy and Precision; No data given in reference below.
Time of Measurement; Not Stated, but assumed to be very rapid or
semi-continuous.
Calibration Requirements; Pitot tube should be calibrated as outlined in
reference below after use at each field site.
Comments by Users: None stated
Data Outputs: Not stated. Assumed to be visual observations manually
recorded.
Special Sampling Requirements (Collection, Storage, Handling): Type S
(Stauscheibe or reverse) pitot tube.
Reference: Federal Register, Volume 36, #247, December 23, 1971.
A-56
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B. WATER AND WASTEWATER METHODS
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No. B-l
SUMMARY OF ANALYTICAL METHODS
Parameter(s) Measured; Acidity
Medium: Water
Name of Measurement Method: Not Stated
Principal Detection Technique: Titration
Purpose of Measurement (Important Applications);
Summary of Method: Sample is titrated to a final pH of 8.3. Results
reported as mg of CaCOj per liter.
Limitations;
Range of Applicability; (not stated in primary reference)
Interferences; Not applicable to acid samples from mine drainage
Pitfalls; Special Precautions;
Statistical Characteristics; Over Observed Range of:
By 40 analysts in 17 laboratories
Accuracy; Bias Acidity, as mg/1 CaCO-
+ 2.77% 20
+0.52% 21
Precision; Standard Dev.
1.79 mg/1 CaCO, 20
1.73 21
Time of Measurement (Max. Frequency, recovery period, etc.); Not stated,
but fast.
Calibration Requirements; Not Stated
Data Outputs; Analog signal displayed on meter.
Special Sampling Requirements (collection, storage, handling):
Refrigerate sample at A C. Maximum holding time is 24 hours
References: (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center,
Cincinnati, Ohio (1971).
(2) Annual Book of ASTM Standards, Part 23 (Method Designation
D1067), Society for Testing and Materials, Philadelphia,
Pennsylvania, (1970).
B-l
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No. B-2
SUMMARY OF ANALYTICAL METHODS
Parameter(s) Measured; Alkalinity
Med ium: Water
Name of Measurement Method: Electronetric Titration
Principal Detection Technique; Electrometric
Purpose of Measurement (Important Applications); Drinking waters,
ambient surface waters, domestic and industrial wastes, and saline waters.
Summary of Method; Unaltered sample is titrated to an electrometrically
determined end point of pH 4.5. Sample must not be filtered, diluted,
concentrated, or otherwise altered.
Limitations;
Range of Applicability; All concentrations
Interferences; Salts of weak acids, oils and greases
Pitfalls; Special Precautions; Analyze sample as soon as possible
after collection preferably within
a few hours.
Statistical Characteristics; Over Observed Range of:
Accuracy; Bias. % Alkalinity in mg/1 CaCO-
+ 22.29 9
- 8.19 113
Precision: Std. Dev.. mg/1 CaCOj
1.14 9
5.28 113
Time of Measurement (Max, frequency, recovery period, etc.); Not stated,
but rapid.
Calibration Requirements; None stated.
Data Outputs: Meter (analog voltage)
Special Sampling Requirements (collection, storage, handling);
Refrigerate at 4 C, Max. holding time 24 hours.
References; (1)" Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center,
Cincinnati, Ohio (1971).
(2) Annual Book of ASTM Standards, Part 23 (Method Designation
D1067), Society for Testing and Materials, Philadelphia
Pennsylvania, (1970).
B-2
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No. J-3
SUMMARY OF ANALYTICAL METHODS
Parameter(s) Measured: Total Alkalinity
Medium; Water
Name of Measurement Method: Automated Methyl Orange Method
Principal Detection Technique; Titration, with coloriir.etric detection
of end point.
Purpose of Measurement (Important Applications): Surface waters, saline
waters
Summary of Method; A Technicon Autoanalyzer is used, employing methyl
orange as indicator. This is dissolved in a weak buffer at pH of 3.1,
just below the equivalence point. Addition of alkalinity causes loss
of color proportional. Color measurement made by colorimeter at
approximately 550 nm.
Limitations;
Range of Applicability; 10 to 200 mg/1 expressed as CaCO,
Interferences; None
Pitfalls; Special Precautions; None Stated
Statistical Characteristics:
Precision; Std dev'n was±0.5 mg/1 CaCOj (in one lab) using
concentrations of 15, 57, 154, and 193 mg/1
CaC03
Time of Measurement (Max. Frequency, recovery period, etc.);
30 Min. warm-up, about 2 min per determination
Calibration Requirements; Requires preparation of standard curve of peak
heights vs. concentration
Data Outputs; Strip recorder (analog voltage)
Special Sampling Requirements (collection. Storage. Handling);
Refrigerated at AC; sample analyzed as soon as possible
References: (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center,
Cincinnati, Ohio (1971).
(2) Technicon Autoanalvzer Methodology: Bulletin 1261
(1961).
B-3
-------
No. B-5
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Arsenic
Medium; Water
Name of Measurement Method; Diethyldithiocarbamate method
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications); Most fresh water and
saline water.
Summary of Method; Arsenic in sample is reduced to arsine, AsU3, in
acid solution. The arsine is scrubbed to remove sulfide, and is absorbed
in a solution of diethyldithicarbamate dissolved in pyridine. The red
complex thus formed is measured in a spectrophotometer at 535 nm.
Limitations;
Range of Applicability; At or above 10 pg/1 As. (If arsenic
is organically bound, consult Standard
Methods, (13th Edition)).
Interferences; High concentrations of chromium, cobalt, copper,
mercury, molybdenum, nickel, or silver
Pitfalls; Special Precautions; Difficulties may be encountered
with certain industrial wastes containing volatile substances.
High sulfur content of wastes may exceed removal capacity of
FbAc scrubber.
Statistical Characteristics; In 46 laboratories:
Over Observed Range of;
Accuracy': Relative error = 0% 40 pg/1
Precision; Relative Std Dev = 13.8% 40 yg/1 as As
Time of Measurement; Not stated
Calibration Requirements; Not stated
Data Outputs: Chart or meter (analog voltage)
Special Sampling Requirements (collection, storage, handling); None stated
References: (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center,
Cincinnati, Ohio (1971).
(2) Standard Methods for Examination of Water and Waste-
water, 13th Edition, American Public Health Association
et al^, Washington, D.C. (1971).
B-4
-------
No. E- 6
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Biochemical Oxygen Demand (BOD)*
Medium; Water
Name of Measurement Method: 5-day BOD determination (using modified
Winkler with Full Bottle Technique).
Principal Detection Technique; Titration
Purpose of Measurement (Important Applications): Ambient surface water,
domestic and industrial waste waters (especially sewage treatment plant
effluent).
Summary of Method: Sample of waste, diluted as appropriate, is
incubated for 5 days in darkness at 20°C. The reduction in
dissolved oxygen concentration during this period yields a
measure of the biochemical oxygen demand.
Limitations: See summary for Dissolved Oxygen (Modified Winkler Method).
Range of Applicability: None Stated
Interferences: None Stated
Pitfalls; Special Precautions: None Stated
Statistical Characteristics:
Accuracy: None Stated
Precision; Over Observed Range of;
Seventy-seven analysts in fifty-three An unspecified range with
labs analyzed samples of natural water mean value of 194 mg/1 BOD
plus an exact increment of biodegradable
compounds. At a mean of 194 mg/1 BOD,
the standard deviation was±40 mg/1.
Time of Measurement (Maximum Frequency, Recovery Period, etc.);
Five to six days per determination.
Calibration Requirements; None Stated
^Comments by Users; Because of local conditions, types of samples to be
tested, and variabilities of the bioassay procedures, no specific standard
test for BOD has been selected by EPA.
Data Outputs: None Stated
Special Sampling Requirements (Collection, Storage, Handling): None Stated
References; (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center,
Cincinnati, Ohio (1971).
(2) Standard Methods for Examination of Water and Waste-
water, 13th Edition, American Public Health Association
et al., Washington, D.C. (1971).
B-5
-------
No. B-7
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Biochemical Oxygen Demand*(BOD)
Medium; Water
Name of Measurement Method; 5-Day BOD Determination (Using DO Probe)
Principal Detection Technique; Electrometric method.
Purpose of Measurement (Important Applications); See Summary of BOD Determination
using Modified Winkler Method.
Summary of Method; See BOD Determination using Modified Winkler Method.
Limitations; (See Summary for Dissolved Oxygen (Probe Method)).
Range of Applicability; Not stated
Interferences: See Summary No B-19
Pitfalls; Special Precautions: None stated
Statistical Characteristics; See DO Determination using Modified Winkler Method.
Accuracy: None stated
Precision; None stated
Time of Measurement; Not stated
Calibration Requirements; Not stated
*Comments by Users: Because of local conditions, types of samples to be
tested, and variabilities of the bioassay procedures, no specific standard
test for BOD has been selected by EPA.
Data Outputs: Electrical signal displayed on meter
Special Sampling Requirements (Collection. Storage. Handling); Refrigerate
at A C. Maximum storage time - 6 hours.
References; (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center,
Cincinnati, Ohio (1971).
(2) Standard Methods for Examination of Water and Waste-
water, 13th Edition, American Public Health Association
et al^, Washington, D.C. (1971).
B-6
-------
No. B-8
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Organic Carbon (Total and Dissolved)
Medium; Water
Name of Measurement Method: Not Stated
Principal Detection Technique; Infrared spectroscopy
Purpose of Measurement (Important Applications): Ambient surface waters,
domestic and industrial wastes, saline waters; used for assessing potential
oxygen-demanding load of organic matter.
Summary of Method: A micro sample of the wastewater to be analyzed is injected
into a catalytic combustion tube which is enclosed by an electric furnace
thermostated at 950°C. The water is vaporized and the carbonaceous material
is oxidized to carbon dioxide (CO.) and steam in a carrier stream of pure
oxygen or air. The oxygen flow carries the steam and CO. out of the furnace
where the steam is condensed and the condensate removed. The CO., oxygen,
and remaining water vapor enter an infrared analyzer sensitized to provide a
measure of CO.. The amount of CO. present is directly proportional to the
concentration of carbonaceous material in the injected sample.
Limitations;
Range of Applicability; 1 to 140 mg/1 total carbon.
Interferences: Carbonates, bicarbonates
Pitfalls; Special Precautions: Since sample is injected into apparatus
by syringe, the needle opening limits the size of particles reaching
combustor/detector.
Statistical Characteristics:
Twenty-eight analysts in twenty-one laboratories analyzed distilled water
solutions containing exact concentrations of oxidizable organic compounds, with
the following results:
Known Carbon
Conc'n. as TOC,
mg/liter
4.9
107
Precision as
Standard Deviation
TOC, mg/liter
3.93
8.32
Accuracy as
Bias, Bias,
% mg/liter
+15.27 + .75
+ 1.01 +1.08
Time of Measurement; Not stated; assumed to be rapid (several samples per hour).
Calibration Requirements: Requires preparation of calibration curve using
samples of known constituency. Described in detail in Ref. (1) below.
Data Outputs: Analog voltage recorded on strip chart.
Special Sampling Requirements (Collection, Storage, Handling); Minimize time
between sample collection and analysis. Store sample at 4°C. Protect from
sunlight and air. If stored for more than 2 hours, acidify to pH of 2.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati, Ohio (1971).
B-7
-------
No. B-9
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Chloride
Medium: Water
Name of Measurement Method: None stated
Principal Detection Technique; Iteration
Purpose of Measurement (Important Applications); Drinking waters, ambient surface
waters. Domestic and industrial wastes, saline waters.
Summary of Method; Dilute mercuric nitrate solution is added to an acidified
sample in the presence of mixed diphenylcarbazone - bromophenol blue indicator.
The end point of the titration is the formation of the blue-violet diphenylcarbazone
complex.
Limitations:
Range of Applicability: All concentrations ranges of chloride.
Interferences: Sulfites. If presence is suspected, oxidize with
hydrogen peroxide.
Pitfalls; Special Precautions; None cited
Statistical Characteristics: By 42 analysts in 18 laboratories:
Accuracy; Percent bias ranged from Over Observed Range of;
+3.50 (at 18 mg/1) to -1.19 (at 17, 18, 91, 97, 382, 398 mg/1 Cl"
398 mg/1).
Precision; Standard Deviations ranged Same
from 1.32 mg/1 (at 18 mg/1 Cl") to
11.8 mg/1 (at 398 mg/1 Cl~ )
Time of Measurement: Not stated
Calibration Requirements; Not stated
Data Outputs: Visual observation and manual recording (or may use automated
titration, yielding an analog voltage recorded on chart).
Special Sampling Requirements (Collection, Storage, Handling); None indicated.
Maximum holding time - 7 days.
References; (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al..
Washington, D.C. (1971).
(3) ASTM Standards, part 23, Water, Atmospheric Analysis (1970).
B-8
-------
No. B-10
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Chloride
Medium: Water
Name of Measurement Method: Automated Ferricyanide Method
Principal Detection Technique; Titration, using colorimeter
Purpose of Measurement (Important Applications); Ambient surface waters, domestic
and industrial wastes, saline waters.
Summary of Method ; Thiocyanate ion (SCN) is liberated from mercuric thiocyanate
through sequestration of mercury by chloride ion to form un-ionized mercuric
chloride ion. In the presence of ferric ion the thiocyanate SCN forms highly
colored ferric thiocyanate in concentration proportional to the original chloride
concentration.
The determination may be performed automatically using a Technicon AutoAnalyzer
employing a colorimeter with 480 nm filter for endpoint detection.
Limitations;
Range of Applicability: 1 to 250 mg/1 chloride
Interferences; None given
Pitfalls; Special Precautions: None stated
Statistical Characteristics: Over Observed Range of:
In a single laboratory:
Accuracy; Not Stated
Precision; Standard deviation of 1; 100; and 250 mg/1 chloride
±0.3 mg/1 chloride
Time of Measurement: About 2 minutes
per sample, with 30 min warm-up.
Calibration Requirements: Not Stated
Data Outputs; Analog voltage, recorded on strip chart
Special Sampling Requirements (Collection, Storage, Handling); None. Maximum
holding time - 7 days.
References; (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center,
Cincinnati, Ohio (1971).
(2) J.E. O'Brien, "Automatic Analysis of Chlorides in Sewage,"
Waste Engineering. _33_ 670-672 (December 1962).
B-9
-------
No. B-ll
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Chlorine Requirement
Medium; Water
Name of Measurement Method; None Stated
Principal Detection Technique; Colorimetry or Electrometric Determination
Purpose of Measurement (Important Applications); To determine the amount of
chlorine to be added to sample to achieve certain desired results, such as
control of coliform densities, destruction of certain chemical compounds,
or establishment of specified chlorine residuals.
The method given here is applicable to drinking water, surface waters, domestic
and industrial wastes, and saline water.
Summary of Method; A solution of known chlorine content is added incrementally
to a series of sample aliquots. At the end of the stipulated contact time or
when the desired result has been achieved the residual chlorine is measured by
the appropriate method.
Limitations;
Range of Applicability: Not a single, specific procedure, but varies with
purpose or result to be achieved.
Interferences: Not Specified.
Pitfalls; Special Precautions; When the purpose is to obtain a specified
chlorine residual, the same method of chlorine measurement should be
used for operational control and laboratory testing.
All pertinent information should be included in report of results, such as :
conditions of chlorination (pH, temperature, contact time); method used for
determining the desired result; and the chlorine required to produce result
Statistical Characteristics;
Accuracy and Precision; Nature of this test precludes the use of
accuracy and precision statements.
Time of Measurement (Maximum Frequency, Recovery Period, etc.); Not Stated
Calibration Requirements; Not Given
Data Outputs; Not given, but assumed to be analog voltage displayed on meter or chart.
Special Sampling Requirements (Collection. Storage. Handling): Not Given
References: (1) Methods for Chemical Analysis of Water and Wadtoa,
EPA National Environmental Research Center, Cincinnati*,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
B-10
-------
No. B-12
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Chemical Oxygen Demand (COD) (High Concentration)
Medium; Water
Name of Measurement Method: Not Stated
Principal Detection Technique: Titration
Purpose of Measurement (Important Applications); To determine quantity of oxygen
required to oxidize all organic matter in a wastewater sample under specified
conditions.
Summary of Method; Organic substances in the sample are oxidized by potassium
dichromate in 50% sulfuric acid solution at reflux temperature. Silver sulfate
is used as a catalyst and mercuric sulfate is added to remove chloride inter-
ference. The excess dichromate is titrated with standard ferrous ammonium
sulfate, using orthophenanthroline ferrous complex as an indicator.
Limitations;
Range of Applicability; Organic carbon concentration of 15 mg/1
or higher.
Interferences: Chloride concentration over 2000 mg/1
Pitfalls; Special Precautions; None Cited
Statistical Characteristics;
Accuracy; None Stated
Precision; Eighty-nine Analysts: Standard deviation of±27.5 mg/1 COD at
known value 270 mg/1 COD
Time of Measurement; Not Stated
Calibration Requirements; Not Stated
Data Outputs; Not Stated
Special Sampling Requirements (Collection, Storage. Handling): Add 2 ml H^O^ per
liter of sample- Maximum storage time - 7 days
References: (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al...
Washington, D. C. (1971).
B-ll
-------
No. B-13
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Chemical Oxygen Demand (COD) (Low Concentration)
Medium: Water
Name of Measurement Method; COD - Low Level
Principal Detection Technique; Titration
Purpose of Measurement (Important Applications); Ambient surface water, domestic
and industrial wastes with low oxygen demand characteristics).
Summary of Method; Similar to that for COD-High Level, except (1) that extreme
care is exercised during sample acquisition and handling and during analysis to
insure that no organic contaminants are introduced from glassware, atmosphere,
etc., (2) that highly pure reagents are used, and (3) that chlorides are
removed by complexing with mercuric sulfate.
Limitations;
Range of Applicability; 5 to 50 mg/1 COD
Interferences; Organic contaminants; chlorides
Pitfalls; Special Precuations; Volatile materials may be lost during
sulfuric acid addition step.
Statistical Characteristics;
Accuracy; Not yet determined (1971)
Precision; Not yet determined (1971)
Time of Measurement; Not Stated
Calibration Requirements; Standardize reagents dally
Data Outputs; Not Stated
Special Sampling Requirements (Collection, Storage, Handling); Use glass sample
bottles. Preserve with H.SO,. Test biologically active samples soon after
acquisiton.
References: (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
B-12
-------
No. B-14
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Chemical Oxygen Demand (COD) (In Highly Saline Waters)
Medium; Water
Name of Measurement Method; Saline Water COD Determination
Principal Detection Technique; Titration
Purpose of Measurement (Important Applications); COD Determination in Saline Waters
Summary of Method; Organic and oxidizable inorganic substances in an aqueous
sample are oxidized by potassium dichromate solution in 50 percent (by volume)
sulfuric acid solution. The excess dichromate is titrated with standard
ferrous ammonium sulfate using orthophenanthroline ferrous complex (ferroin)
as an indicator. Mercuric sulfate is added to complex the chlorides during digestion.
Limitations!
Range of Applicability; Minimum of 250 mg/1 COD when chloride concentration
exceeds 1000 mg/1. (The removal of chlorides by MgSO, may not be complete
in the case of strong brines.)
Interferences; Extraneous organic matter
Pitfalls; Special Precautions; None stated
Statistical Characteristics;
Accuracy; Not yet available (1971)
Precision; Not yet available (1971)
Time of Measurement: Not Stated
Calibration of Requirements; Not Stated
Data Outputs; Not Stated
Special Sampling Requirements (Collection, Storage. Handling); Use glass bottles
if possible; preserve with H.SO,.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-13
-------
No. B-15
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Color
Medium; Water
Name of Measurement Method; Not Stated
Principal Detection Technique; Visual Sensing
Purpose of Measurement (Important Applications); Measures color of
water derived from naturally occurring materials, e.g., vegetable residues
such as leaves, bark, humus, etc.
Summary of Method; Color is measured by visual comparison of the sample with
platinum-cobalt standards. One unit of color is that produced by 1 mg/1 platinum
in the form of the chloroplatinate ion.
The Spectrophotometric and Tristimulus methods are useful for detecting
specific color problems. The use of these methods, however, is laborious and
unless determination of the hue, purity, and luminance is desired, they are of
limited value.
Limitations;
Range of Applicability; Not Stated
Interferences; Turbidity; highly colored industrial wastes
Pitfalls; Special Precautions; Biological activity may change color
characteristics after sample is acquired.
Statistical Characteristics;
Accuracy; Not available (1971)
Precision: Not available (1971)
Time of Measurement: Not stated
Calibration Requirements: See Reference.
Data Outputs; Usually a visual observation, manually recorded
Special Sampling Requirements (Collection. Storage. Handling);
Store sample at 4 C. Maximum holding time - 24 hours.
References: (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater, .
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
B-14
-------
No. B-16
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Cyanide
Medium: Water
Name of Measurement Method; Not Stated
Principal Detection Technique; Colorimetric
Purpose of Measurement (Important Applications); Ambient surface water, domestic
and indsutrial wastes, saline waters.
Summary of Method: The cyanide as hydrocyanic acid (HCN) is released from
metallic cyanide complex ions by means of a reflux-distillation operation
and absorbed in a scrubber containing sodium hydroxide solution. The
cyanide ion in the absorbing solution is then determined by volumetric titration
or colorimetrically. The colorimetric measurement employs the pyridine-pyrazolone
reaction in which the cyanide is coupled with free chlorine to form cyanogen
chloride and then with pyridine to a glutaconic aldehyde. The aldehyde then
reacts with l-phenyl-3methyl-S-pyrazolone to form a highly colored blue dye.
Limitations!
Range of Applicability: Cyanide concentrations below 1 mg/1(sensitive to
about 0.5 Kg/1).
Interferences; Sulfides, oxidizing substances.
Pitfalls; Special Precautions: Material tested may be highly toxic and
should be treated accordingly. Sample should be maintained at a highly
basic pH.
Statistical Characteristics:
Determination by 47 analysts yielded:
Accuracy: Not Stated
Precision: Standard Deviation Known CN Concentration of:
0.020 mg/.l 0.02 mg/1
0.306 mg/1 1.10 mg/1
Time of Measurement; Not Stated
Calibration Requirements: Not Stated
Data Outputs; Analog signal (meter)
Special Sampling Requirements (Collection. Storage. Handling):
- minimum sample size - 1 liter
- adjust pH to 11 at time of sample collection (using soldium hydroxide)
- analyze as soon as possible after collection (maximum holding time - 24 hours)
- store at 4 C.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-15
-------
No. B-17
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Cyanide
Medium; Water
Name of Measurement Method; Not Stated
Principal Detection Technique: Titration
Purpose of Measurement (Important Applications): Ambient surface water,
domestic and industrial wastes, saline waters.
Summary of Method; The cyanide as hydrocyanic acid (HCN) is released from
metallic cyanide complex ions by means of a reflux-distillation operation
and absorbed in a scrubber containing sodium hydroxide solution. The
cyanide ion in the absorbing solution is then determined by volumetric titration
or colorimetrically. The titrimetric measurement uses a standard solution of
silver nitrate to titrate cyanide in the presence of a silver sensitive indicator.
Limitations;
Range of Applicability: Concentrations of cyanide exceeding 1 mg/1
Interferences: Sulfides, oxidizing substances
Pitfalls; Special Precautions; See summary for Cyanide, Colorimetric
Statistical Characteristics;
Results by 47 Analysts:
Accuracy; None Stated At Known
Precision; Standard Deviation CN Concentration of
0.035 mg/1 0.02 mg/1
0.333 mg/1 1.10 mg/1
Time of Measurement? Not Stated
Calibration Requirements; Not Stated
Data Outputs; Not stated. (Probably visual reading, recorded manually.)
Special Sampling Requirements (Collection. Storage. Handling): See summary
for Cyanide, Colorimetric.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-16
-------
Nc. B-18
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Dissolved Oxygen (DO)
Medium; Water
Name of Measurement Method: Modified Winkler with Full-Bottle Technique
Principal Detection Technique: Titration
Purpose of Measurement (Important Applications); Most ambient surface waters,
most waste waters (but not domestic sewage).
Summary of method: The sample is treated with manganous sulfate, potassium
hydroxide and potassium iodide and finally sulfuric acid. The initial
precipitate of manganous hydroxide combines with the dissolved oxygen in the
sample to form a brown precipitate, manganic hydroxide. Upon acidification, the
manganic hydroxide forms manganic sulfate which acts as an oxidizing agent to
release free iodine from the potassium iodine. The iodine, which is stoichio-
metrically equivalent to the dissolved oxygen in the sample is then titrated.
Limitations:
Range of Applicability: Not Stated
Interferences: Oxidizing or reducing materials (especially sulfites,
thiosulphates, polythionates, chlorine, hypochlorite) nitrate ions, ferrous
ions, organic matter, high concentrations of suspended solids.
Pitfalls; Special Precautions: Sample may contain low concentrations of
ferrous iron (less than 1 mg/1) and nitrates. High concentration of
either interfere.
Statistical Characteristics;
Exact data not available, the following are approximate.
Accuracy: Not Stated
Precision: Reproducibility of 0.2 ppm of
DO when known concentration is 7.5 ppm DO.
Time of Measurement: Not stated, but a complex proceeding.
Calibration Requirements: Not Stated
Comments by Users: Most common interferences overcome by use of 00 probe (See Mo.fi-19),
Data outputs; Visual observation or analog signal.
Special Sampling Requirements (Collection, Storage. Handling); Grab Sampling
acquisiton procedures are specified; also preservative reagents to be added.
Analysis should be completed within 4-8 hours after acquisition of sample.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-17
-------
No. B-19
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Dissolved Oxygen (DO)
Medium; Water
Name of Measurement Method; Probe Method
Principal Detection Technique: Electrometric
Purpose of Measurement (Important Applications): Ambient surface water, domestic
and industrial wastes.
Summary of Method; The most common instrumental probes for determination
of dissolved oxygen in water are dependent upon electrochemical reactions.
Under steady-state conditions, the current or potential can be correlated
with DO concentrations. Interfacial dynamics at the probe-sample interface
are a factor in probe response and a significant degree of interfacial
turbulence is necessary. For precision performance, turbulence should be
constant. The probe method may be used under any circumstances as a sub-
stitute for the modified Winkler procedure provided that the probe itself is
standardized against the Winkler method on samples free of interfering materials.
The electronic readout meter for the output from dissolved oxygen probes is
normally calibrated in convenient scale (0 to 10, 0 to 15, 0 to 20 mg/1 for
example) with a sensitivity of approximately 0.05 mg/14
Limitations:
Range of Applicability; Not stated
Interferences; Sulfur compounds and certain reactive gases (e.g., chlorine)
may interfere. Dissolved inorganic salts affect performance, but usually
can be compensated for. pH variation interferes with some probes.
Pitfalls; Special Precautions: Probes may be sensitive to temperature, and
may require temperature compensation.
Statistical Characteristics; Manufacturers' Claims:
Accuracy; + 1% of true DO value
Precision: 0.1 mg/1 repeatability
Time of Measurement;
Not stated, but rapid.
Calibration Requirements; Not Stated. (Should be calibrated against standards
with approximately the same concentration of suspended solids as the sample.)
Data Outputs; Electrical signal displayed on meter
Special Sampling Requirements (Collection. Storage. Handling); Not Stated.
Can provide continuous, in situ measurements.
References: Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-18
-------
No. B-20
SUMMARY OF ANALYTICAL METHODS
Parameter(s) Measured; Fluoride
Medium; Water
Name of Measurement Method: Automated Complexone Method
Principal Detection Technique; Photometric, automated (Technicon AutoAnalyzer)
Purpose of Measurement (Important Applications): Ambient surface water,
domestic and industrial wastes, saline water.
Summary of Method: Fluoride reacts with red cerous chelate of alizarin
complexone. A positive color is developed and intensity is measured by
a colorimeter at about 650 nm. Technicon AutoAnalyzer is used.
Limitations:
Range of Applicability; 0.05 to 1.5 mg/1 fluoride
Interferences: Aluminum
Pitfalls; Special Precautions: None cited
Statistical Characteristics;
Accuracy:
Precision: At one lab, standard deviation of measurement was
0.018 mg/1 F~ when actual concentrations were 0.06, 0.15, 0.55,
and 1.08 mg/1.
Time of Measurement; 12 samples per hour after 30 minutes warming
Calibration Requirements; Not cited
Data Outputs; Analog electrical signal recorded on stripchart.
Special Sampling Requirements (Collection, Storage, Handling); None cited.
Reference; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-19
-------
No. B-21
SUMMARY OF ANALYTICAL METHODS
Parameter(s) Measured: Fluoride
Medium: Water
Name of Measurement Method: SPADNS Method with Bellack Distillation.
Principal Detection Technique: Colorimetric
Purpose of Measurement (Important Applications): Drinking water, ambient
streams, industrial wastes, saline water; for use when probe unavailable.
Summary of Method: Sample distilled to remove most interferences. SPADNS
reagent added. Loss of color resulting from reaction of fluoride ion
with SPADNS dye is measured colorimetrically by use of photometer operating
near 570 my.
Limitations;
Range of Applicability; 0.1 to 2.5 mg/1 fluoride
Interferences; Among the more tolerant methods—no specific interferants
identified in primary reference.
Pitfalls; Special Precautions: Care needed in addition of reagent
Statistical Characteristics;
Accuracy; None given
Precision; Results from Std. Dev. Known Values
53 analysts: 0.09 mg/1 @ 0.83 mg/lF~
0.10 0.57 mg/1
0.09 0.68 mg/1
Time of Measurement; Not given
Calibration Requirements: Not given
Data Outputs; Meter (Analog voltage)
Special Sampling Requirements (Collection, Storage, Handling); None identified
References; (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
B-20
-------
No. B-22
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Fluoride
Medium: Water
Name of Measurement Method: Specific Ion Electrode Method
Principal Detection Technique; Electrometric
Purpose of Measurement (Important Applications); Drinking water, ambient surface
waters, brines, industrial wastes.
Summary of Method; The fluoride is determined potentiometrically using
a specific ion fluoride electrode in conjunction with a standard single
junction sleeve-type reference electrode and a pH meter having an expanded
millivolt scale or a specific ion meter having a direct concentration
scale for fluoride.
Limitations;
Range of Applicability; 0.1 to 1000 mg/1 fluoride
Interferences; Extreme pH's. (Should be between pH 5 and 9)
Also, some complexing cations (Si , Fe+3, Al+^.
Pitfalls; Special Precautions; None states
Statistical Characteristics;
Results by 111 Analysts Over Observed Range of:
Mean: 0.84 mg/1 F~ Known concentration
0.85 mg/1 F
Mean: 0.75 0.75 mg/1 F~/with
other materials
Precision; Std Dev:±0.030 n;g/l F" 0.85 mg/1 F~
±0.036 0.75 mg/1 F" (with
other materials)
Time of Measurement: Not Stated
Calibration Requirements: Requires preparation ana calibration curves by
measuring standard solutions.
Data Outputs; Analog electrical signal displayed on meter.
Special Sampling Requirements (collection, storage, handling): None
stated. Max holding time - 7 days
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-21
-------
No. B-23
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Hardness
Medium; Water
Name of Measurement Method: None stated
Principal Detection Technique; Titration
Purpose of Measurement (Important Applications); Drinking waters,
ambient surface waters, domestic and industrial wastes
Summary of Method; Calcium and magnesium ions in the sample are
sequestered upon the addition of disodium dihydrogen ethylenediamine
tetraacetate (Na2EDTA). The end point of the reaction is detected by
means of Chrome Black T or Calmagite, which has a red color in the
presence of calcium and magnesium and a blue color when the cations
are sequestered.
Limitations;
Range of Applicability; All concentrations of hardness.
Interferences; Excess concentrations of heavy metals (may be
removed by complexlng with cyanide)
Pitfalls; Special Precautions;
Statistical Characteristics; 43 analysts in 17 labs obtained the
following results Precision Over Known Range of
Accuracy (Bias) (Std. Dev.) Hardness as CaCOi
-0.003 mg/1 (as 2.87 mg/1 31 mg/1
-0.24 CaC03) 2.52 33
0.4 4.87 182
-2.0 2.98 194
-13.0 9.65 417
-14.3 8.73 444
Time of Measurement: Not Stated
Calibration Requirements; Not stated
Data Outputs; Not stated. Assume visual observation, manual recording
Special Sampling Requirements (collection, storage, handling); None.
Max. holding time 7 days
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-22
-------
No. B-24
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Total Hardness
Medium; Water
Name of Measurement Method; Automated Method
Principal Detection Technique! Colorimetry
Purpose of Measurement (Important Applications); Surface waters and
saline waters
Summary of Method; The disodium magnesium EDTA exchanges magnesium on
an equivalent basis for any calcium and/or other cations to form a more
stable EDTA chelate than magnesium. The free magnesium reacts with
calmagite at a pH of 10 to give a red-violet complex. Thus, by measuring
only magnesium concentration in the final reaction stream, an accurate
measurement of total hardness is possible.
Method assumes the use of a Technicon AutoAnalyzer, Colorimeter
is equipped with 520 nm filter.
Limitations:
Range of Applicability; 10 to 400 mg/1 expressed as CaCOj
Interferences! None
Pitfalls; Special Precautions; None stated
Statistical Characteristics;
Accuracy; Not stated
Precision: Results from a single lab:
Std. Dev. ' Known Concentration
+1.5 mg/1 19 mg/1 CaCO,
+1.5 120
+ 4.5 385
+ 5.0 366
Time of Measurement:
12 determinations per hour. 30 minutes warm up.
Calibration Requirements: Apparatus must be calibrated against stock
solutions of known concentration.
Data Outputs; Analog electrical signal, recorded on stripchart.
Special Sampling Requirements (Collection, Storage, Handling); None.
References; (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Technicon AutoAnalyzer Methodology, Bulletin No. 2
Channcey, New York (July 1960)
B-23
-------
No. B-25
SUMMARY OF ANALYTICAL METHOD
Parametcr(s) Measured: Metals
Aluminum Copper Potassium
Arsenic Iron Silver
Cadmium Lead Sodium
Calcium Magnesium Zinc
Chromium Manganese
Medium: Water
Name of Measurement Method: Atomic Absorption
Principal Detection Technique: Atomic Absorption Spectroscopy.
Purpose of Measurement (Important Applications^): Rapid determination of certain
metals In ambient surface water, domestic and Industrial water, and saline water.
Summary of Method: Atomic absorption spectroscopy is similar to flame emission
photometry in that a sample Is atomized and aspirated into a flame. Flame
photometry, however, measures the amount of light emitted, whereas, in atomic
absorption spectrophotometry, a light beam is directed through the flame into a
monochromator, and onto a detector that measures the amount of light absorbed.
In many Instances absorption is more sensitive because it depends upon the
presence of free, unexclted atoms and generally the ratio of unexcitcd to excited
atoms at a given moment is very high. Since the wavelength of the light beam is
characteristic of only the metal being determined, the light energy absorbed by
the flame is a measure of the concentration of that metal In the sample. This
principle is the basis of atomic absorption spectroscopy.
Analytical procedures specific to each of the metals listed above arc given in
the Reference cited.
Limitations:
Range of Applicability; Detection limits, sensitivities, and optimum ranges
of concentrations, vary with make and model of atomic absorption spectro-
meter. The following table provides some indication of ranges of measure-
ment. In many cases the range can be extended higher or lower by instrument
adjustment, use of a different wavelength, or sample pretreatment.
Metal
Aluminum
Arsenic
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Potassium
Silver
Sodium
Zinc
Detection
Limit
(mg/1)
0.1
0.5
0.001
0.003
0.01
0.005
0.004
0.01
0.0005
0.005
0.005
0.01
0.001
0.005
Sensitivity
(mg/1)
0.6
1.0
0.004
0.07
0.02
0.04
0.006
0.06
0.005
0.04
0.01
0.05
0.003
0.02
Optimum Concentration
Range
(mg/1)
10
10
0.1 -
1
1
0.1 -
0.1 -
1
0.01 -
0.1 -
0.01 -
0.1 -
1
0.1 -
1000
100
2
200
200
10
20
10
2
20
2
20
200
2
Accuracy and Precision Data:
Metal
Metal Concentration
fog/1)
Direct determination
Cadmium
Chromium
Copper
Iron
Magnesium
Manganese
Silver
Zinc
Extracted samples
Cadmium
Lead
50
50
1000
300
200
50
50
500
10
50
Relative
Error
(Percent)
8.15
2.29
3.42
0.64
6.30
6.00
10.57
0.41
3.03
19.00
Relative
Standard Deviation
(Percent)
21.62
26.44
11.23
16.53
10.49
13.50
17.47
8.15
72.77
23.46
Time of Measurement: Rapid
Calibration Requirements: See Reference
Data Outputs; Electrical signals.
Special Sampling Requirements (Collection, Storage. Handling): See Reference
References! Methods for Chemical Analysis of Water and Wastes, U.S. Environmental
Protection Agency, National Environmental Research Center, Analytical
Quality Control Laboratory, Cincinnati, Ohio 45268 (1971).
B-24
-------
No. B-26
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Mercury
Medium; Water
Name of Measurement Method: Flameless AA Procedure
Principal Detection Technique: Atomic Absorption Spectroscopy
Purpose of Measurement (Important Applications); Ambient surface water,
saline waters, wastewaters, and effluents. May also be used for fish
tissue, mud, sediments, and other materials following proper digestion.
Summary of Method; The flameless AA procedure is a physical method based
on the absorption of radiation at 253.7 nm by mercury vapor. The mercury
is reduced to the elemental state and aerated from solution in a closed
system. The mercury vapor passes through a cell positioned in the
light path of an atomic absorption spectrophotometer. Absorbance (peak
height) is measured as a function of mercury concentration and recorded
on a stripchart.
Limitations:
Range of Applicability; Detection limit is 0.2 (ig/J- mercury
Interferences; Sulfides, copper, high concentrations of chlorides,
and certain volatile organics
Pitfalls: Special Precautions; None stated
Statistical Characteristics; Using an Ohio River composite sample with
a background mercury concentration of 0.35 Ug/1, spiked with concentrations
of 1, 3 and 4 Mg/1, the standard deviations were ±0.14,±0.10 and ±0.08 ug/1,
respectively. Standard deviation at the 0.35 level was 0.16. Percent
recoveries at the three levels were 89, 87, and 87%, respectively.
Time of Measurement: Not Stated
Calibration Requirements; Detailed calibration instructions included
in Ref. (1) below.
Data Outputs; Analog electrical signal, displayed on stripchart.
Special Sampling Requirements (collection, storage, handling); Acidify
sample to pH of 2 or lower.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati
Ohio (1971).
B-25
-------
No. B-27
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Mercury
Medium: Water
Name of Measurement Method: Cold Vapor Technique
Principal Detection Technique: Atomic absorption spectroscopy
Purpose of Measurement (Important Applications): This method Is applicable
to surface waters, saline waters, wastewaters, effluents, and domestic
sewage.
Summary of Method; The atonic absorption procedure Is a physical method
based on the absorption of radiation at 253.7 nm by mercury vapor. The
mercury Is reduced to the elemental state and aerated from solution In
a closed system. The mercury vapor passes through a cell positioned in
the light path of an atomic absorption spectrophotometer. (Instruments
designed specifically for the measurement of mercury using the cold vapor
technique are commercially available and may be substituted for the atomic
absorption spectrophotometer.) Absorbance (peak height) is measured as
a function of mercury concentration and recorded In the usual manner.
In addition to Inorganic forms of mercury, organic mercurials may
also be present in an effluent or surface water sample. These orgonomercury
compounds will not respond to the flomeless atomic absorption technique
unless they are first broken down and converted to mercuric Ions. Potassium
permanganate oxidizes many of these compounds but recent studies have shown
that a number of organic mercurials, including phenyl mercuric acetate and
methyl mercuric chloride, are only partially oxidized by this reagent.
Potassium persulfate has been found to give approximately 100 percent
recovery when used as the oxidant with these compounds. Therefore, a
persulfate oxidation step following the addition of the permanganate has
been included to Insure that organomercury compounds, if present, will be
oxidized to the mercuric ion before measurement. A heat step is required
for methyl mercuric chloride when present In or spiked to a natural system.
For distilled water the heat step is not necessary.
Limitations;
Range of Applicability: The range of the method may be varied
through instrument and/or recorder expansion. Using a 100 ml sample,
a detection limit of 0.2 ug Hg/1 can be achieved; concentrations
below this level should be reported as <0.2.
Interferences; Sulfldes (Interference can be eliminated by addition
of potassium permanganate), high concentrations of copper and
chlorides. (Certain volatile organic materials may also interfere.)
Pitfalls; Special Precautions: None stated
Statistical Characteristics:
Accuracy and Precision: Using an Ohio River composite sample with
a background mercury concentration of 0.3S ug/1, spiked with concen-
trations of 1, 3 and 4 ug/1, the standard deviations were ±0.14, +0.10
and + 0.08 ug/1, respectively. Standard deviation at the 0?35 level
was +0.16. Percent recoveries at the three levels were 89, 87, and
87 percent, respectively.
Time of Measurement: Several hours.
Calibration Requirements: No unusual requirements. See Reference for
detailed procedure.
Special Sampling Requirements (Collection. Storage. Handling); Acidify
sample with nitric acid to pH of 2 or lower immediately upon collection.
(If only dissolved mercury is to be determined, sample should be filtered
before acidification.)
References: "Mercury in Water," (April 1972). Modification of procedure
appearing in the 1971 Issue of Methods for Chemical Analysis
of Water and Wastes. Analytical Quality Control Laboratory,
Cincinnati, Ohio (1971).
B-26
-------
No. B-28
SUMMARY OF ANALYTICAL METHOD
Paraneter(s) Measured; Mercury
Medium; Water
Sane of Measurement Method: Automated Cold Vapor Technique
Principal Detection Technique: Atonic Abaorptlon Spectroscopy
Purpose of Measurement (Important Applications): This method Is applicable
to surface waters. It nay be applicable to saline waters, wastewaters, effluents,
and domestic sewages provided potential Interferences are not present.
Summary of Method:
The flameless AA procedure is a physical method based on the absorption of
radiation at 253.7 nm by mercury vapor. The mercury Is reduced to the elemental
state and aerated from solution. The mercury vapor passes through a cell positioned
in the light path of an atomic absorption spectrophotometer. (Instruments designed
specifically for the measurement of mercury using the cold vapor technique are
commercially available and may be substituted for the atomic absorption spectro-
photometer).
In addition to Inorganic forms of mercury, organic mercurials may also be
present. These organomercury compounds will not respond to the flameless atomic
absorption technique unless they are first broken down and converted to mercuric
ions. Potassium permanganate oxidizes many of these compounds but recent studies
have shown that a number of organic mercurials. Including phenyl mercuric acetate
and methyl mercuric chloride, are only partially oxidized by this reagent. Potassium
persulfate has been found to give approximately 100 percent recovery when used as
the oxldant with these compounds. Therefore, an automated persulfate oxidation
step following the automated addition of the permanganate has been included to
Insure that organomercury compounds, if present, will be oxidized to the mercuric
ion before measurement.
A Technlcon AutoAnalyzer is used In this method.
Limitations:
Range of Applicability: 0.2 to 20 ug/1 of mercury
Interferences: Free chlorine may be formed from samples high in chlorides,
causing a positive interference. Certain volatile organics may also interfere.
Pitfalls; Specie! Precautions: Formation of a heavy precipitate in some
wastevaters and effluents has been reported upon addition of concentrated
sulfurlc acid for the oxidation step. If this is encountered, the problem
sample cannot be analyzed by this method.
Statistical Characteristics:
Accuracy and Precision; In a single laboratory (EPA Southeastern Water Laboratory,
Athens, Georgia), using distilled water standards at concentrations of 0.5,
1.0, 2.0, 5.0, 10.0, and 20 ug Hg/1, the standard deviations were +0.04, ±0.07,
+0.09, +0.20, +0.40, and +0.84 ug/1, respectively.
In a single laboratory (SEML), using surface water samples spiked with
ten organic mercurials at the 10 pg/1 level, recoveries ranged from 87 to 117
percent. Recoveries of the same ten organic mercurials in distilled water
at the 10ug/l level, ranged from 92 to 125 percent.
Time of Measurement: Not stated
Calibration Requirements: See Reference for procedure
Data Outputs: Electrical signals displayed or recorded.
Special Sampling Requirements (Collection. Storage. Handling); Acidify to pH 2 or
lower with nitric acid Immediately upon collection. If only dissolved mercury
is to be determined, filter before acidification. Samples containing solids must
be blended and then mixed while being sampled if total mercury values are to be
reported.
References: "Mercury in Water (Automated Cold Vapor Technique)" (April 1972)
Method description received from Analytical Quality Control
Laboratory, EPA National Enclronmental Research Laboratory,
Cincinnati, Ohio.
B-27
-------
No. B-29
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Mercury (Total)
Medium; Fish tissue (and other biological materials)
Name of Measurement Method: Cold Vapor Technique
Principal Detection Technique: Atomic absorption spectroscopy
Purpose of Measurement (Important Applications): To measure total mercury (organic
and inorganic) in fish and in other biological materials.
Summary of Method; Weighed portion of sample is digested with sulfuric and nitric
acid and oxidized overnight with potassium permanganate. Mercury content is
measured by the conventional cold vapor (Flameless AA) technique summarized in
Method Summary for Mercury in Water (this compendium) and described in References
(1) and (2) of that Summary.
Limitations:
Range of Applicability; 0.2 to 5 Pg/g. (May be extended by varying
sample size or through instrument control.)
Interferences; Most interferences are destroyed during digestion and
oxidation steps.
Pitfalls; Special Precautions; See "Sampling Requirements" below
Statistical Characteristics;
Accuracy; Not stated
Precision; The following standard deviations on replicate fish samples were
recorded at the indicated levels: 0.19 Mg/g + 0.02; 0.74 pg/g + 0.05; and
2.1 jjg/g + 0.07. The coefficients of variation at these levels~were
11.9 percent, 7 percent, and 3.6 percent respectively.
Time of Measurement: Several hours.
Calibration Requirements; No unusual requirements
Data Outputs; Electrical signals displayed or recorded.
Special Sampling Requirements (Collection, Storage. Handling); Mercury is not uniformly
distributed throughout the whole fish and it is therefore necessary to decide in advance
which part of the fish is to be analyzed. In the case of a large specimen, only a
selected part of the fish may be examined. (Ordinarily, only the edible flesh is
analyzed.) In any event, the portion analyzed should be reported.
If it becomes necessary to freeze the fish before analysis, the sample should
not be allowed to thaw before weighing as higher results may be observed.
References:
(1) "Mercury in Fish," (April 1972). Method description received from
Analytical Quality Control Laboratory, EPA National Environmental Research
Center, Cincinnati, Ohio.
(2) Uthe, J.F., Armstrong, F.A.J. and Stainton, M.P., "Mercury Determination
in Fish Samples by Wet Digestion and Flameless Atomic Absorption Spectrophotometry",
Jour. Fisheries Research Board of Canada. 27.> 805 (1970).
B-28
-------
No. B-30
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Mercury (Total) in Sediment
Medium: Sediments
Name of Measurement Method: Cold Vapor Technique
Principal Detection Technique; Atomic absorption spectroscopy
Purpose of Measurement (Important Applications): This procedure measures total
mercury (organic + inorganic) in soils, sediments, bottom deposits and sludge type
materials.
Summary of Method; A weighed portion of the sample is digested in aqua regia for
2 minutes at 95"C, followed by oxidation with potassium permanganate. Mercury in
the digested sample is then measured by the conventional cold vapor technique
(Flameless AA) summarized in the Method Summary for mercury in water (this compendium)
and described in the References cited in that Summary.
An alternate digestion involving use of an autoclave is also described in the
reference cited below.
Limitations:
Range of Applicability: 0.2 to 5 Ug/g. (Range may be extended by varying
sample size or through instrument control.)
Interferences; Sulfides, high copper or chloride concentrations, and other
materials cited in the Summary for Mercury in Water.
Pitfalls; Special Precautions; Care must be exercised to avoid contamination
of sample or apparatus by mercury in air or other extraneous sources.
Statistical Characteristics:
Accuracy and Precision: The following standard deviations on replicate
sediment samples were recorded at the indicated levels; 0.29 ug/g + 0.02 and
0.82 ug/g + 0.03. Recovery of mercury at these levels, added as methyl
mercuric chloride, was 97 and 94 percent, respectively.
Time of Measurement; Several hours.
Calibration Requirements: Given in Reference cited below
Data Outputs: Electrical signals displayed or recorded.
Special Sampling Requirements (Collection, Storage, Handling); Because of the extreme
sensitivity of the analytical procedure and the omnipresence of mercury, care must be
taken to avoid extraneous contamination. Sampling devices and sample containers
should be ascertained to be free of mercury; the sample should not be exposed to any
condition in the laboratory that may result in contact or air-borne mercury con-
tamination.
References: "Mercury in Sediment — Cold Vapor Technique," (April 1972). Provisional
Method. Description received from Analytical Quality Control Laboratory,
EPA National Environmental Research Center, Cincinnati, Ohio.
B-29
-------
No. 3-31
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Methylmercury in Fish
Medium: Fish tissue
Name of Measurement Method; Gas Chromatography Method
Principal Detection Technique: Electron-capture gas chromatography
Purpose of Measurement (Important Applications): To determine concentration
of methyl mercury in fish samples of all types.
Summary of Method; A measured weight of fish is treated with acid and bromide
salt. Methyl mercury is extracted as methyl mercury bromide with toluene. A
cleanup operation is performed by first extracting the toluene layer with aqueous
solution of sodium thiosulfate. The methyl mercury thiosulfate complex formed
in the aqueous layer is then reacted with an excess of potassium iodide. Benzene
is used to extract any methyl mercury as the iodide salt. A portion of the
benzene extract is chromatographed directly and response is compared to standard
responses. The iodide is detected using gas chromatography with an electron
capture detector.
Limitations:
Range of Applicability: Not stated
fensitivity; 0.01 ug/g
Interferences; Materials in sample will generally not cause a problem.
Toluene from extraction not removed by cleanup step may interfere.
Pitfalls; Special Precautions; Potassium iodide solution decomposes
readily. Any free iodine formed may cause interfering peaks on chromatogram.
Statistical Characteristics;
Accuracy and Precision: When seven portions of a filet of a large white
perch were analyzed by this method, a mean value of 0.37 yg/g was obtained,
with a standard deviation of 0.034 pg/g.
Recoveries of methyl mercury chloride injected into this same fish at the
0.20 yg/g level averaged 95.5 percent.
Time of Measurement: Approximately one hour
Calibration Requirements; No unusual requirements. Calibration procedure given in
Reference.
Data Outputs: Analog electrical signal recorded as chromatogram
Special Sampling Requirements (Collection, Storage. Handling):
Analysis should be performed on the fish before decay has begun. Fresh or
frozen fish can be analyzed with confidence; results on partially decomposed samples
must be viewed with caution and reported as such.
Fish samples can dehydrate rapidly unless protected during handling. Defrosting
and refreezing a frozen sample before analysis, and permitting a sample to stand open
at room temperature before weighing, must be avoided.
Selection of portions of the fish must be of a consistent nature and prooerlv
identified as to location on the specimen.
References: "Methyl Mercury in Fish", (April 1972). Provision Method. Descriotion
received from Analytical Quality Control Laboratory, EPA National
Environmental Research Center, Cincinnati, Ohio.
B-30
-------
No. B-32
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Methylmercury in Sediment
Medium: Sediment
Name of Measurement Method; Gas Chromatography Method
Principal Detection Technique; Electron capture gas Chromatography
Purpose of Measurement (Important Applications); This method is applicable to
bottom samples such as mud, sludge, silt and gravel.
Summary of Method; A measured weight of sediment is treated with acid and bromide
salt. Methyl mercury is extracted with toluene as methyl mercury bromide. A
cleanup operation is performed by first extracting the toluene layer with an
aqueous solution of sodium thiosulfate. The methyl mercury thiosulfate complex
formed in the aqueous layer is then reacted with an excess of potassium iodide.
Benzene is used to extract any methyl mercury as the iodide salt. A portion
of the benzene extract is chromatographed directly and response is compared to
standard responses. The iodide is detected using gas Chromatography with an
electron capture detector.
Limitations:
Range of Applicability; Not stated
Sensitivity; 0.001 ug/g
Interferences: Materials in sample generally will not cause a problem
Pitfalls; Special Precautions; Potassium iodide solution may decompose to
free iodine, which may cause interfering peaks on the chromatogram.
Statistical Characteristics:
Accuracy and Precision; Ten different sediment samples with a background
level of less than 0.0005 pg/g were spiked with 0.010 ug/g and measured with
this test. The average result was 0.00963 ug/g and the standard deviation
was 0.00087 yg/g.
Time of Measurement; Not stated
Calibration Requirements; Given in Reference below
Data Outputs; Analog electrical signal recorded as chromatogram.
Special Sampling Requirements (Collection, Storage. Handling); It should be under-
stood that methyl mercury is generated from inorganic mercury by biological methy-
lation. Since this can occur at widely varying rates in samples stored in a
laboratory, analyses intended to determine the methyl mercury concentration existing
at the sampling site at the time of sampling should be performed as quickly as
possible. Storing samples frozen or refrigerated before analysis is acceptable
but is a less desirable alternative.
References: "Methyl Mercury in Sediment" (April 1972). Provisional Method.
Description received from Analytical Quality Control Laboratory,
EPA National Encironmental Research Center, Cincinnati, Ohio.
B-31
-------
No. B-33
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Methylene Blue Active Substances (MBAS)
(Synthetic Detergents and Other Surfactants)
Medium; Water
Name of Measurement Method; Methylene Blue Method
Principal Detection Technique: Colorimetry
Purpose of Measurement (Important Applications); Determination of
concentration of detergents, phosphates, surfactants in drinking water,
ambient surface waters, domestic and industrial wastes.
Summary of Method; The dye, methylene blue, in aqueous solution reacts
with anionic-type surface active materials to form a blue colored salt.
The salt is extractable with chloroform anil the intensity of color pro-
duced is proportional to the concentration of MBAS.
Limitations;
Range of Applicability; 0.025 to 100 mg/1 of MBAS (expressed
as linear alkyl sulfonate — LAS)
Interferences; Chloride at concentrations over 1000 mg/1
sulfonates, carboxylates, phosphates, phenol, cyanates, and
thiocyanates (at concentrations higher than normally en-
countered in water or wastewater).
Pitfalls; Special Precautions;
Statistical Characteristics:
Accuracy; +1.2% to -11% bias (conditions as given for Precision).
Precision: Determinations by 110 analysts exhibited relative
standard deviations of 10 to 15 percent for known
concentrations of MBAS ranging from 0.27 to 2.94
mg/1 of LAS
Time of Measurement; Not Stated
Calibration Requirements; None stated
Data Outputs; Analog electrical signal, displayed on meter.
Special Sampling Requirements (collection, storage, handling): Not Stated
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-32
-------
No. B-34
SUMMARY OF ANALYTICAL METHOD
Parameter(s) measured: Nitrogen-Ammonia
Medium; Water
Name of Measurement Method; Distillation Procedure
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications); Ambient surface waters,
domestic and industrial wastewater, and saline water
Summary of Method; The sample is buffered at pH of 9.5 with a borate
buffer in order to decrease hydrolysis of cyanates and organic nitrogen
compounds, and is then distilled into a solution of boric acid. The
ammonia in the distillate can be determined either colorimetrically by
nesslerization,or titrimetrically with standard sulfuric acid with the
use of a mixed indicator, the choice between these two procedures
depending on the concentration of the ammonia.
Limitations;
Range of Applicability; 0.05 to 1.0 mg/1 ammoniacal nitrogen
Interferences; Cyanates, certain alcohols, aldehydes, and ketones
may interfere. (Certain amines would interfere if distillation
step were not included).
Pitfalls; Special Precautions; Residual chlorine must be removed.
If sample is preserved by a mercury salt, the mercury must be
complexed.
Statistical Characteristics; 24 analysts in 16 laboratories obtained:
Known Concentration Accuracy (Bias) Precision
in mg/1 Nitrogen mg/1 N (Std. Dev.) mg/l N
0.21 -0.01 0.122
0.26 -0.05 0.070
1.71 +0.01 0.244
1.92 -0.04 0.279
Time of Measurement: Not Stated
Calibration Requirements; Set up a series of standards in Nessler tubes.
Care needed in calibrating for saline water tests.
Data Outputs; Meter reading (analog electrical signal)
Special Sampling Requirements (collection, storage, handling);
Preserve with mercuric chloride and store at 4 C.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-33
-------
No. B-35
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Nitrogen-Ammonia
Medium; Water
Name of Measurement Method; Distillation Procedure — Titrimetric
Principal Detection Technique: Titration
Purpose of Measurement (Important Applications): Surface waters, domestic
and industrial wastewater, and saline water.
Summary of Method; The sample is buffered at pH of 9.5 with a borate
buffer in order to decrease hydrolysis of cyanates and organic nitrogen
compounds, and is then distilled into a solution of boric acid. The
ammonia in the distillate can be determined either colorimetrically by
nesslerization or titrimetrically with standard sulfuric acid and the
use of a mixed indicator, the choice between these two procedures
depending on the concentration of the ammonia.
Limitations;
Ranee of Applicability; i.o to 25 mg/1 ammoniacal nitrogen
Interferences; Cyanates, hydrozine and similar compounds
Pitfalls; Special Precautions; Residual chlorine and mercury must be
removed.
St-tistical .Characteristics;
Accuracy and Precision! Not stated
Time of Measurement; Not stated
Calibration Requirements; Not stated
Data Outputs: Not stated. Assumed to be visual observation and manual
recording.
Special Sampling Requirements (collection, storage, handling);
Preserve with mercuric chloride and store at 4 C.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-34
-------
No. B-36
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Nitrogen, Ammonia
Medium; Water
Name of Measurement Method; Automated Method
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications); Surface Waters,
saline waters
Summary of Method; The intensity of the indophenol blue color, formed
by the reaction of ammonia with alkaline phenol hypochlorite, is measured.
Sodium nitroprusside is used to intensify the blue color.
Uses Technicon AutoAnalyzer. Colorimeter is equipped with 630
or 650 run filters.
Limitations:
Range of Applicability; .01 to 2.0 mg/1 nitrogen as NH_
Interferences; Calcium and magnesium ions in higher concentrations,
also mercuric chloride (if used as a preservative).
Pitfalls; Special Precautions; Marked variations in pH among
samples should be eliminated.
Statistical Characteristics;
Precision; In a single laboratory using surface water at
concentrations of 1.41, 0.77, 0.59, 0.43 mg/1 of
N1U-N, the standard deviation was±0.005 mg/1-
Time of Measurement; Not stated
Calibration Requirements; Requires calibration against samples, both
for fresh water and subscitute ocean water of specified constituency.
Data Outputs; Analog electrical signal displayed on stripchart
Special Sampling Requirements (collection. Storage, Handling); Preserve
with mercuric chloride and refrigerate at 4 C. Max. holding time - 7 days
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-35
-------
No. B-37
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Nitrogen, Kjeldahl, Total (Titrimetric)
Medium; Water
Name of Measurement Method; Kjeldahl
Principal Detection Technique; Titriinecric
Purpose of Measurement (Important Applications): Surface waters,
domestic and industrial wastes, saline waters
Summary of Method; Total Kjeldahl nitrogen is defined as the sum of the
free ammonia and organic nitrogen compounds which are converted to
ammonium sulfate under defined conditions of digestion. The procedure
converts nitrogen components of biological origin such as amino
acids, peptides, and proteins to ammonia, but may not convert
the nitrogenous compounds of certain industrial wastes such as amines,
hydrazones, nitro compounds, and others.
The sample is heated in the presence of concentrated sulfuric acid,
K-SO^ and HgSO^ and evaporated until SO-j fumes are obtained and the
solution becomes colorless or pale yellow. The residue is cooled,
diluted, and is treated and made alkaline with a hydroxide-thiosulf&te
solution. The ammonia is distilled and determined after distillation
either by nesslerization or titrimetrically.
Limitations:
Range of Applicability; Concentrations above 1 mg/1 of nitrogen.
Interferences: None cited.
Statistical Characteristics; Results obtained by 31 analysts in 20
laboratories
Known Conc'n. of Precision as Accuracy as
Nitrogen, Kjeldahl Standard Deviation Bias, Bias,
mg N/liter mg N/liter _% mg N/liter
0.20 0.197 +15.54 +.03
0.31 0.247 + 5.45 +.02
4.10 1.056 + 1.03 +.04
4.61 1.191 - 1.67 -.08
Time of Measurement; Not stated, but fairly protracted
Calibration Requirements; Not stated
Data Outputs; Not stated, but assumed to be visual observations
recorded manually
Special Sampling Requirements (collection, storage, handling);
Unstable. Analyze soon after sample is acquired
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-36
-------
No. B-38
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Nitrogen, Kjeldahl, Total (Colorimetric)
Medium; Water
Name of Measurement Method; Kjeldahl
Principal Detection Technique; Colorimetric
Purpose of Measurement (Important Applications); Ambient surface waters, saline
waters, domestic and industrial wastes.
Summary of Method; See Summary for Nitrogen, Kjeldahl, Total, Colorimetric. For
Nesslerization, a spectrophotometer or colorimeter is used, filtered at 400 to
425 nm.
Limitations;
Range of Applicability; Concentrations of nitrogen below 1 mg/1
Interferences: None stated
Pitfalls; Special Precautions; None stated
Statistical Characteristics; See Method Summary for Nitrogen, Kjeldahl, Total
(Titrimetric)
Time of Measurement: Not stated, but long.
Calibration Requirements; Not stated
Data Outputs; Meter reading (analog electrical signal), recorded manually.
Special Sampling Requirements (Collection. Storage. Handling); Unstable—
analyze 'immediately after sample is acquired.
References: Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-37
-------
No. B-39
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Nitrogen, Kjeldahl, Total (Automated)
Medium: Water
Name of Measurement Method; Automated Phenolate
Principal Detection Technique: Colorimetry
Purpose of Measurement (Important Applicantions): Ambient surface waters,
saline waters, domestic and industrial wastes.
Summary of Method; The sample is automatically digested with a sulfuric acid
solution containing potassium sulfate and mercuric sulfate as a catalyst to con-
vert organic nitrogen to ammonium sulfate. The solution is then automatically
neutralized with sodium hydroxide solution and treated with alkaline phenol
reagent and sodium hypochlorite reagent. This treatment forms a blue color
designated as indophenol. Sodium nitroprusside, which increases the intensity
of the color, is added to obtain necessary sensitivity for measurement of low
level nitrogen.
Utilizes Technicon AutoAnalyzer. A colorimeter with 630 nm filter Is used.
Limitations;
Range of Applicability; Nitrogen concentrations from 0.05 to 2.0 mg/1
Interferences; Iron, chromium, or copper ions may interfere
Pitfalls; Special Precuations; None stated
Statistical Characteristics; Results from six laboratories analyzing natural
waters with known concentrations of Kjeldahl nitrogen:
Known Conc'n. of
Kjeldahl-Nitrogen
mg N/liter
1.89
2.18
5.09
5.81
Precision as
Standard Deviation
Kjeldahl-N, mg N/liter
0.54
0.61
1.25
1.85
Accuracy
Bias
% mg
-24.6
-28.3
-23.8
-21.9
as
Bias
N/liter
- .46
- .62
-1.21
-1.27
Time of Measurement; About 20 samples per hour
Calibration Requirements: Requires preparation of standardizations
Data Outputs: Analog electrical signal recorded on stripchart
Special Sampling Requirements (Collection, Storage, Handling); Preserve with
mercuric chloride; refrigerate at 4°C. Analyze immediately after acquisition.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-38
-------
No. B-40
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Nitrogen, Nitrate
Medium: Water
Name of Measurement Method;
Principal Detection Technique: Colorimetric
Purpose of Measurement (Important Applications); Ambient surface water, saline
water, domestic and industrial wastes.
Summary of Method;
This method is based upon the reaction of the nitrate ion with brucine sulfate
in a 13 N H.SO, solution at a temperature of 100°C. The color of the resulting
complex is measured at 410 nm. Temperature control of the color reaction is
extremely critical.
Limitations:
Range of Applicability; Nitrate nitrogen concentrations of 0.1 to 2.0 mg/1
Interferences; Ferric and ferrous iron and manganese give positive inter-
ference, but are negligible in concentrations of less than 1 mg/1
The following substances produce interference, but can be compensated for:
dissolved organic matter, salinity, strong oxidizing or reducing agents,
and residual chlorine.
Pitfalls; Special Precautions; Uneven heating of samples during reaction
time will produce erratic results. Absoute control of temperature is a
necessity.
Statistical Characteristics: 27 analysts in fifteen laboratories analyzed
natural waters containing known concentrations of nitrate nitrogen, obtaining
the following results:
Known Conc'n. of
Nitrogen, Nitrate
mg N/liter
0.16
0.19
1.08
1.24
Precision as
Standard Deviation
me N/liter
.092
.083
.245
.214
Bias,
%
-6.79
+8.30
+4.12
+2.82
Accuracy as
Bias,
mg N/liter
-.01
+.02
+.04
+.04
Time of Measurement; not stated
Calibration Requirements; Not stated separately from basic procedure
Data Outputs: Meter (analog electrical signal).
Special Sampling Requirements (Collection, Storage. Handling): Preserve with
mercuric chloride, refrigerate at 4C maximum storage time: 7 days
References: Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-39
-------
No. B-41
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Nitrogen, Nitrite
Medium; Water
Name of Measurement Method: None Stated
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications): Ambient surface waters, saline
waters, domestic and industrial wastes.
Summary of Method; The diazonium compound formed by diazotation of sulfanilamide
by nitrite in water under acid conditions is coupled with N-(l-naphtyl)-ethylene-
diamine to produce a reddish-purple color which is read in a spectrophotometer
at SAO nm against a blank. Concentration of NO_-N is plotted against optical
density.
Limitations:
Range of Applicability: 0.05 to 1.0 mg/1 nitrite nitrogen
Interferences; Strong oxidizing or reducing agents or high alkalinity
Pitfalls; Special Precautions; None cited
Statistical Characteristics; Precision and accuracy data not available from
Reference (1) below.
Time of Measurement; Not stated
Calibration Requirements; Requires use of standard solutions
Data Outputs; Meter reading (analog voltage).
Special Sampling Requirements (Collection, Storage. Handling); Preserve with
mercuric chloride; refrigerate at A°C. Maximum storage time - 7 days.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-AO
-------
No. B-42
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Nitrogen, Nitrate-Nitrite
Medium; Water
Name of Measurement Method; Automated Cadmium Reduction Method
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications); Determines nitrates and nitrites,
singly or combined, in surface and saline waters.
Summary of Method; The initial step is to reduce the nitrates to nitrites by using
a cadmium-copper catalyst. The nitrites (those originally present plus reduced
nitrates) are then reacted with sulfanilamide to form the diazo compound which is
then coupled in an acid solution (pH 2.0-2.5) with N-l naphtyl-ethylenediamine
hydrochloride to form the azo dye. The azo dye intensity, which is proportional
to the nitrite concentration, is then measured. Separate rather than combined
nitrate-nitrite values are readily obtainable by carrying out the procedure—
first with, and then without, the initial Cd-Cu reduction step.
A Technicon Autoanalyzer is used.
filters.
Limitations:
The colorimeter is equipped with 540 nm
Range of Applicability: 0.05 to 10.0 mg/1 nitrogen present as nitrate.
Interferences; Ammonia and primary amines; some metal ions (mercury and
copper) may produce interfering color complexes.
Pitfalls; Special Precautions: None Stated
Statistical Characteristics; Three laboratories analyzed four natural water
samples containing exact concentrations of inorganic nitrate, with the following
results:
Known Conc'n. of
Nitrate Nitrogen
mg N/Liter
0.29
0.35
2.31
2.48
Precision as
Standard Deviation
mg N/liter
0.012
0.092
0.318
0.176
Accuracy
Bias
I
+5.75
+18.10
+4.47
-2.69
as
Bias
mg N/liter
+.017
+.063
+.103
-.067
Time of Measurement; Not stated, but assumed to be rapid (i.e., several
samples per hour.
Calibration Requirements; Calibration against standard solutions is necessary.
Analysis of saline waters requires calibration against substitute ocean water.
Data Outputs; Analog electrical signal displayed on strip chart.
Special Sampling Requirements (Collection, Storage, Handling): Sample is not
stable since amines in natural waters may react with nitrites. Sample should be
analyzed as soon as possible after acquisition.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-41
-------
No. B-43
SUMMARY OF ANALYTICAL METHOD
Parametr(s) Measured: Nitrogen, Mtrate and Nitrice
Medium: Water
Name of Measurement Method; Automated Hydrazine Reduction Method
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications); Ambient surface waters and
domestic or industrial wastes.
Summary of Method; This method, using the Technicon AutoAnylyzer, determines
N02~N by the conventional diazotization-coupling reaction. The NO--N is
reduced with hydrazine sulfate in another portion of the sample and the nitrite
thus formed is determined in the usual manner.
Subtraction of the NO--N originally present in the sample from the total
N02-N found will give the original NO--N concentration in terms of NO.-N.
Utilizes Technicon AutoAnalyzer.
Limitations;
Range of Applicabilty; Nitrate or nitrite nitrogen in concentrations of
0.05 to 10.0 mg/lit.
Interferences; The following substances may interfere (concentrations
below which interference will not occur are listed in Reference):
chlorides, phosphates, sulfides, ammoniacal nitrogen, manganeses,
calcium, and ferric ions, and ABS.
Pitfalls; Special Precautions; Toxic reagents.
Statistical Characteristics: Nine laboratories analyzed four natural water samples
containing exact concentrations of inorganic nitrate,with the following results:
Known Conc'n. of
Nitrate Nitrogen
rag N/liter
0.29
0.35
2.31
2.48
Precision as
Standard Deviation
mg N/liter
0.053
0.058
0.258
0.217
Accuracy
Bias,
%
-0.8
+1.9
+3.0
-1.2
as
Bias,
mg N/liter
.002
.007
.07
.03
In a single laboratory, using surface water samples at concentrations of
0.1, 0.2, 0.8, and 2.1 mg-N/1, the standard deviations were 0.0, +0.04, +0.05,
and + 0.05, respectively.
Time of Measurement; About 20 samples per hour
Calibration Requirements; See Reference.
Data Outputs: Analog electrical signal displayed on strip chart.
Special Sampling Requirements (Collection. Storage, Handling); Preserve sample
with mercuric chloride. Refrigerate at 4°C. Maximum holding time—7 days.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-42
-------
No. B-44
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Nitrogen, Organic plus Ammonia
Medium; 'Water
Name of Measurement Method; Automated Phenolate Method
Principal Detection Technique: Colorimetry
Purpose of Measurement (Important Applications): Ambient Surface Waters and
Saline waters
Summary of Method: Organic nitrogen is determined by manually digesting the
sample with potassium persulfate and sulfuric acid to convert the organic nitrogen,
and any ammonia present, to ammonium sulfate. Subsequently, the automated phenol-
hypochlorite procedure is used to measure the ammonia nitrogen.- Nitrate-nitrite
nitrogen is not measured by this procedure.
Utilizes Technicon AutoAnalyzer with colorimeter equipped with 650 nm filter.
Limitations:
Range of Applicability; Nitrogen concentrations of 1.0 to 10.0 mg/1
Interferences; None
Pitfalls; Special Precautions; None cited
Statistical Characteristics; Accuracy and precision data not available from
Reference (1) below.
Time of Measurement; Not stable. Estimated to be between one and two hours
per determination.
Calibration Requirements; Calibrate against standard solutions
Data Outputs: Analog electrical signal recorded on stripchart.
Special Sampling Requirements (Collection. Storage. Handling); Preserve
with mercuric chloride. Refrigerate at 4°C. Maximum storage time - 7 days.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-43
-------
No. B-45
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; NTA (Trisodium-nitrilotriacetic Acid)
Medium; Water
Name of Measurement Method; Zinc-Zincon Method
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications): Ambient surface
waters (non-saline).
Summary of Method; Zinc forms a blue-colored complex with 2 carboxy-21-
hydroxy-5'-sulfoformazylbenzene (Zincon) in a solution buffered to pH
9.2. When NTA is added, the Zn-Zincon complex is broken which
reduces the optical density in proportion to the amount of NTA present.
A photometer equipped with 620 nm filter is used.
Limitations:
Range of Applicability; 0.5 to 10.0 mg/1 NTA
Interferences; Cations of common metals (calcium, magnesium,
zinc, copper, iron, manganese, et al).
Pitfalls;Special Precautions; Most interfering cations can be
removed by ion-exchange resin.
Statistical Characteristics;
Precision: In a single laboratory, using spiked
surface water samples at concentrations of 0.5, 2, 6, and 10
mg/1 NTA, standard deviations were +0.17, +0.14, +0.1, and
+0.16, respectively.
Time of Measurement; Not stated
Calibration Requirements; Requires stock solution
Data Outputs; Analog electrical signal displayed on meter.
Special Sampling Requirements (Collection, Storage, Handling); Sample
should be analyzed as soon as possible after acquisition, since NTA is
biodegradable.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-44
-------
No. B-46
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; NTA
Medium: Water
Name of Measurement Method: Automated Zlnc-Zincon Method
Principal Detection Technique: Colorimetry
Purpose of Measurement (Important Applications); Ambient surface
water (non-saline).
Summary of Method; Zinc forms a blue-colored complex with 2-carboxy-2'-
hydroxy-5'-sulfoformazylbenzene (Zincon) in a solution buffered to pU 9.2.
When NTA is added, the Zn-Zincon complex is broken which reduces the
optical density in proportion to the amount of NTA present.
A Technicon AutoAnalyzer is used. The colorimeter is equipped with
600 or 625 nm filter.
Limitations;
Ranee of Applicability; 0.04 to 1.0 mg/1 or 0.5 to 10.0 mg/1 NTA,
depending on type of manifold system.
Interferences; Common cations (calcium, magnesium, copper, iron.
mangagnese). Constituents of sewage cause come interference also.
Pitfalls; Special Precautions; Not applicable to saline water
Statistical Characteristics;
Reproducibility; In a single laboratory, using surface water samples
at concentrations of 0.1, 0.18, 0.27, and 0.44 mg/1, the standard deviations
were +0.01, +0.004, +0.004, +0.005, respectively. At concentrations of 1.3,
4.0, 5.8, and 7.4 mg/1, the standard deviations were +0.05, +0.05, +0.07,
and +0.1, respectively.
Time of Measurement; About 13 samples per hour
Calibration Requirements; Requires standard solutions
Data Outputs; Analog electric signal, recorded automatically.
Special Sampling Requirements (Collection. Storage. Handling);
Analyze soon after sample collection because of biodegradability of NTA
Reference; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-45
-------
No. B-47
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; OH and Grease*
Medium; Water
Name of Measurement Method; Extraction/Gravimetric
Principal Detection Technique:
Purpose of Measurement (Important Applications): Measures hexane-extractable
matter (animal fats, non-volatile hydrocarbons, waxes, greases) in surface
water, industrial wastes, and domestic sewage.
Summary of Method; The sample is acidified to a low pH (<3) and extracted
with hexane using a Soxhlet extraction. The solvent is evaporated from the
separated extract and the residue weighed.
Limitations;
Range of Applicability; 5 to 1000 mg/1 of extractable matter
Interferences; None Cited
Pitfalls; Special Precautions; None stated
Statistical Characteris tics; Precision and accuracy data not available
from Reference below.
Time of Measurement; Not stated, but several hours
Calibration Requirements; Not stated
Comments by Users;
Data Outputs; Read from analytical balance.
Special Sampling Requirements (Collection. Storage. Handling); None Stated
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
^Summaries of other specific analytical methods for detection, identifi-
cation, and quantitation of oils and greases are given in the section of
this compendium headed "Oils and Greases".
B-46
-------
No. B-48
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; pH
Medium; Water
Name of Measurement Method; Electrometric
Principal Detection Tehcnlque: Electrometric
Purpose of Measurement (Important Applications); Drinking water, ambient
surface waters, domestic and industrial wates, saline water.
Summary of Method; The pH of a sample is an electrometric measurement,
using either a glass electrode in combination with a reference potential
(saturated calomel electrode) or a combination electrode (glass and reference).
Limitations;
Range of Applicability; Not stated, but assumed broad
Interferences: Oil and grease
Pitfalls; Special Precautions; None stated
Statistical Characteristics; Forty-four analysts in twenty laboratories
analyzed six synthetic water samples containing exact concentrations of hydrogen-
hydroxyl ions, with the following results:
Known Conc'n. as
pH Units
3.5
3.5
7.1
7.2
8.0
8.0
Precision as
Standard Deviation
oH Units
0.10
0.11
0.20
0.18
0.13
0.12
Accuracy As
Bias, Bias,
% pH Units
-0.29 -0.01
-0.00
+1.01 +0.07
-0.03 -0.002
-0.12 -0.01
+0.16 +0.01
Time of Measurement; Not stated, but rapid (several per hour)
Calibratation Requirements; Instrument must be initially standardized
Comments by Users; Field pH measurements made with comparable instruments
are reliable.
Data Outputs; Analog signal displayed on meter.
Special Sampling Requirements (Collection, Storage, Handling); Analyze as
soon as possible after collection. No holding.
References; (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al..
Washington, D. C. (1971).
B-47
-------
No. B-49
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Phenolics
Medium; Water
Name of Measurement Method: 4-AAP Method with Distillation
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications): Drinking water, ambient
surface waters, domestic and industrial wastes, saline waters.
Summary of Method: Phenolic materials react with 4-aminoantipyrine in the
presence of potassium ferricyanide at a pH of 10 to form a stable reddish-
brown colored antipyrine dye. The amount of color produced is a function
of the concentration of phenolic material.
Limitations;
Range of Applicability; 5 to 1000 jig/1 phenol (with solvent extraction)
50 to 5000 p.g/1 phenol (without solvent extraction1)
Interferences; None stated. pH must be controlled
Pitfalls; Special Precautions: Method does not differentiate different
types of phenolic materials.
Statistical Characteristics; The following results were obtained by analysts
at six laboratories:
Known
Concentration
of Phenol
(PB/D
9.6
48.3
93.5
Time of Measurement:
Standard Deviation
(pg/1) with
Solvent
Extraction
0.99
3.1
4.2
Not Stated
Calibration Requirements; Color response varies with type of phenolic
material. Phenol is used as standard.
Data Outputs: Meter reading (analog electrical signal).
Special Sampling Requirements (Collection. Storage. Handling); None Stated
References: (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
B-48
-------
No. B-50
SUMMARY OF ANALYTICAL METHOD
Parameter(a) Measured: Phosphorus
Medium: Water
Name ot Measurement Method: Single Reagent Method
Principal Detection Technique; Colorlmetry
Purpose ot Measurement (Important Applications): Ambient surface waters,
drinking water, domestic and industrial wastes, saline waters (may also be
applicable to sediments, sludges, and algal blooms).
Summary of Method: Ammonium molybdate and potassium antimonyl tartrate react
in an acid medium with dilute solutions of phosphorus to form an antimony-phospho-
molybdate complex. This complex is reduced to an intensely blue-colored complex
by ascorbic acid. The color is proportional to the phosphorus concentration.
Only orthophosphate forms a blue color in this test. Polyphosphates (and some
organic phosphorus compounds) may be converted to the orthophosphate form by
sulfuric-acid-hydrolysis. Organic phosphorus compounds may be converted to the
orthophosphate form by sulfuric acid hydrolysis. Organic phosphorus compounds
may be converted to the orthophosphate form by persulfate digestion.
A spectrophotometer or filter photometer suitable for measurements at 880 nm
is used.
Limitations:
Range of Applicability; 0.01 to 0.5 mg/1 phosphorus
Interferences: High concentrations of Iron. Also, mercuric chloride
(when used as a preservative).
Pitfalls; Special Precautions: Avoid use of commercial detergents for
cleaning analytical apparatus. Avoid collection of benthic deposits with
sample.
Statistical Characteristics: Thirty-three analysts in nineteen laboratories
analyzed natural water samples containing exact concentrations of organic phosphate.
with the following results:
Known Conc'n. of
Total Phosphorus
mg P/liter
0.110
0.132
0.772
0.882
Precision as
Standard Deviation
me P/liter
0.033
0.051
0.130
0.128
Accuracy as
Bias,
X
+ 3.09
+11.99
+ 2.96
- 0.92
Bias,
mg P/liter
+.003
+.016
+.023
-.008
Twenty-six analysts in sixteen laboratories analyzed natural water samples con-
taining exact concentrations of orthophosphate, with the following results:
Known Conc'n. of
Orthophosphate
me P/liter
0.029
0.038
0.335
0.383
Precision as
Standard Deviation
mg P/liter
0.010
0.008
0.018
0.023
Accuracy as
Bias,
Z
-4.95
-6.00
-2.75
-1.76
Bias,
mg P/liter
-.001
-.002
-.009
-.007
Time of Measurement: Not Stated
Calibration Requirements: Requires ntandard solutions
Data Outputs: Meter (analog voltage), manually recorded
Special Sampling Requirements (Collection. Storage. Handling): If stored tore
than 8-10 hours. Add mercuric chloride or preservative and refrigerate at 4"C.
References: Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-49
-------
No. B-51
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Phosphorus
Medium: Water
Name of Measurement Method; Automated Single Reagent Method
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications): Ambient surface waters,
domestic and industrial wastes, saline waters. (May also prove applicable to
sediments, sludges.)
Summary of Method: Ammonium molybdate and potassium antimonyl tartrate react in
an acid medium with dilute solutions of phosphorus to form an antimony-phospho-
molybdate complex. This complex is reduced to an intensely blue-colored complex
by ascorbic acid. The color is proportional to the phosphorus concentration.
A Technicon AutoAnalyzer is used with a colorimeter equipped with 650 nm filter.
Limitations;
Range of Applicability; 0.01 to 1.0 mg/1 phosphorus
Interferences; Iron in high concentrations; mercuric chloride, when
used as a preservative, must be compensated for.
Pitfalls; Special Precautions; Benthic deposits must be avoided when
sample is collected; glassware must not be cleaned with commercial
detergents.
Statistical Characteristics; Six laboratories analyzed four natural water samples
containing exact concentrations of orthophosphate, with the following results:
Known Conc'n. of
Orthophosphate
mg P/liter
0.04
0.04
0.29
0.30
Precision as
Standard Deviation
mg P/liter
0.019
0.014
0.087
0.066
Accuracy as
Bias,
+16.7
- 8.3
-15.5
-12.8
Bias,
mg P/liter
+.007
-.003
-.05
-.04
Time of Measurement; About 20 samples per hour.
Calibration Requirements; Requires standard solutions, and standardized
substitute ocean water when analyzing saline water. See Ref. for
calibration details.
Data Outputs; Analog electrical signal recorded on strip chart.
Special Sampling Requirements (Collection. Storage. Handling); Avoid benthic
deposits during collection. If not analyzed same day as collected, preserve
with mercuric chloride and refrigerate at 4°C.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-50
-------
No. B-52
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Phosphorus
Medium; Water
Name of Measurement Method; Automated Stannous Chloride Method
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications); Ambient surface waters,
domestic and industrial wastes. (May prove applicable to sediment, sludge and
algae blooms).
Summary of Method; Phosphorus is determined by manually digesting the samples
with ammonium persulfate and sulfuric acid to convert the various forms of
phosphorus to the orthophosphate form.;and measurement of this orthophosphate
on a Technicon AutoAnalyzer, using (NH^^MoO, with SnCl2 reduction tp form
color complex.
Limitations;
Range of Applicability; 0.01 to 1.0 mg/1 phosphorus
Interferences; None Cited
Pitfalls; Special Precautions; Avoid benthic deposits when acquiring
sample. Do not use commercial detergents for cleansing apparatus.
Statistical Characteristics; In a single laboratory, using surface water
samples at concentrations of 0.06, 0.11, 0.48, and 0.62 mg P/l, the standard
deviation was +0.004 (AQC Laboratory).
Time of Measurement; About IS samples per hour
Calibration Requirements: Requires standard solutions. See Ref. (1) for details
Data Outputs; Analog electrical signal recorded on strip chart.
Special Sampling Requirements (Collection. Storage. Handling); Avoid benthic
deposits when sampling. If sample is not analyzed on day of acquisition,
preserve with mercuric chloride and refrigerate at 4°C.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-51
-------
No. B-53
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Selenium
Medium: Water
Name of Measurement Method: Diaminobenzidine Method
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications); Drinking waters, ambient
surface waters, saline waters, domestic and industrial wastes.
Summary of Method; All selenium compounds present in the sample are first
oxidized to selenate by acid permanganate. The selenate is then reduced to
selenite. Addition of diaminobenzidine reagent forms the piazselenol complex
which is subsequently extracted into toluene and the absorbance measured at
420 nm. The piazselenol color is stable, but evaporation of toluene
concentrates the color to a marked degree in a few hours.
Limitations:
Range of Applicability; 0.003-0.05 mg/1 selenium.
Interferences; Ferric ions, iodine, bromide.
Pitfalls; Special Precautions: Requires tight control of time, temperature,
and acid concentration.
Statistical Characteristics; A synthetic unknown sample containing 20 Mg/1
Se, 40 ng/1 As, 250 jig/1 Be, 240 pg/1 B, and 6 ng/1 V in distilled water
was determined by the diaminobenzidine method, with a relative standard de-
viation of 21.2 percent and a relative error of 5.0 percent in 35 laboratories.
Time of Measurement; Not Stated
Calibration Requirements; Not Stated
Data Outputs: Meter reading (analog voltage).
Special Sampling Requirements (Collection, Storage. Handling); Not Stated
References: (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Uastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
B-52
-------
No. B-54
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Silica, Dissolved
Medium; Water
Name of Measurement Method: Not given
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications); Drinking water, ambient
surface waters, domestic and industrial wastes, saline water.
Summary of Method: A well-mixed sample is filtered through a O.ASu
membrane filter. The filtrate, upon the addition of molybdate ion in
acidic solution, forms a greenish-yellow color complex proportional to
the dissolved silica in the sample. The color complex is then measured
spectrophotometrically.
Limitations;
Range of Applicability: 2 to 25 mg/1 silica
Interferences: Excessive color or turbidity
Pitfalls; Special Precautions; None Cited
Statistical Characteristics; Photometric evaluations by the amino-
naphthol-sulfonic acid procedure have an estimated precision of +0.10
mg/1 in the range from 0 to 2 mg/1 (ASTM). Photometric evaluation
of the silico-molybdate color in the range from 2 to 50 mg/1 have an
estimated precision of approximately 4 percent of the quantity of silica
measured (ASTM).
Time of Measurement; Not Stated
Calibration Requirements: Not Stated
Data Outputs; Analog electrical signal.
Special Sampling Requirements (Collection. Storage. Handling); None stated
References; (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) ASTM Standards, Part 23, Atmospheric Analysis,
Method D859-68 (1970).
B-53
-------
No. B-55
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Solids, filterable (Dissolved)
Medium; Water
Name of Measurement Method: Not Stated
Principal Detection Technique; Filtration/Gravimetric
Purpose of Measurement (Important Apllications); Ambient surface waters,
domestic and industrial wastes, saline waters
Summary of Method; A well-mixed sample is filtered through a standard glass
fiber filter. The filtrate is evaporated and dried to constant weight at
180°C. The filtered residue is then weighed.
Filterable solids are defined as those solids capable of passing through a
standard glass fiber filter and dried to constant weight at 180°C.
Limitations;
Range of Applicability: 10 to 20,000 mg/1 solids
Interferences; None Cited
Pitfalls; Special Precautions; Mineralized waters containing calcium, magnesium,
chloride and/or sulfate may be hygroscopic and will require prolonged drying and
quick weighing. Samples containing bicarbonates require careful drying at 1BO°C
to insure conversion to the carbonate.
Statistical Characteristics; Precision data not available at this time
(Ref. below). Accuracy data on actual sample cannot be obtained.
Time of Measurement; Not Stated
Calibration Requirements: Not Stated
Data Outputs; Read from analytical balance.
Special Sampling Requirements (Collection. Storage, Handling); Sample should be
analyzed as soon as possible after acquisition.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-54
-------
No. 3-56
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Solids, Non-Filterable (Suspended)
Medium; Water
Name of Measurement Method: Not Stated
Principal Detection Technique; Filtration/Gravimetric
Purpose of Measurement (Important Applications): Ambient surface waters,
domestic and industrial wastes, saline waters.
Summary of Method; A well-mixed sample is filtered through a standard glass
fiber filter, and the residue retained on the filter is dried to constant
weight at 103-105°C. Non-filterable solids are defined as those solids which
are retained by a standard glass fiber filter and dried to constant weight at
103-105°C.
Limitations:
Range of Applicability: 20 to 20,000 mg/1 solids
Interference: None cited
Pitfalls; Special Precautions; Too much residue on the filter will
entrap water and require prolonged drying.
Statistical Characteristics: Reproducibility data not available at this
time. Accuracy data on actual samples cannot be obtained.
Time of Measurement; Not stated
Calibration Requirements; Not stated
Data Outputs; Analytical balance reading.
Special Sampling Requirements (Collection, Storage, Handling); Preservation
of sample is not practical; analysis should begin as soon as practical. Non-
homogeneous particulates (sticks, fish, etc.) should be excluded from sample.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-55
-------
No. B-57
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Solids, Total
Medium; Water
Name of Measurement Method: Not given
Principal Detection Technique: Gravimetric
Purpose of Measurement (Important Applications): Ambient surface waters,
domestic and industrial wastes, saline waters.
Summary of Method: A well mixed aliquot of the test sample is quantitatively
transferred to a pre-weighed evaporating dish and evaporated to dryness at
103-105°C. (Total Solids are defined as the sum of the homogenous suspended
and dissolved materials in a sample).
Limitations;
Range of Applicability: 10 to 30,000 mg/1 solids
Interferences; None cited
Pitfalls; Special Precautions; Floating oils and greases, if present,
should be dispersed with a blender. Large floating particles should
be excluded.
Statistical Characteristics; Precision and accuracy data not availabe at
this time (Ref. (1)).
Time of Measurement; Not Stated
Calibration Requirements: Not Stated
Data Outputs; Read from analytical balance.
Special Sampling Requirements (Collection. Storage. Handling): None Cited
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-56
-------
No. B-58
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Solids, volatile
Medium; Water
Name of Measurement Method; Not Stated
Principal Detection Technique; Ignition/Filtration
Purpose of Measurement (Important Applications); The test is useful in
obtaining a rough approximation of the amount of organic matter present in the
solid fraction of sewage, activated sludge, industrial wastes, or bottom
sediments.
Summary of Method; The residue obtained from the determination of total,
suspended, or dissolved solids is ignited at 550°C in a muffle furnace. The
loss of weight on ignition is reported as mg/1 volatile solids.
Limitations:
Range of Applicability: Not Stated
Interferences; None Cited
Pitfalls; Special Precautions; The test is subject to many errors due
to loss of water of crystallization, loss of volatile organic matter
prior to combustion, incomplete oxidation of certain complex organics,
and decomposition of mineral salts during combustion.
Statistical Characteristics;
Reproducibility; A collaborative study involving three laboratories
examining four samples by means of ten replicates showed a standard
deviation of + 11 mg/1 at 170 mg/1 volatile solids concentration.
Time of Measurement; Not Stated
Calibration Requirements; Not Stated
Data Outputs; Read from analytical balance.
Special Sampling Requirements (Collection, Storage, Handling): No specific
requirements cited.
References; (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
B-57
-------
No. B-59
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Specific Conductance
Medium; Water
Name of Measurement Method: Not stated
Principal Detection Technique; Electrometric
Purpose of Measurement (Important Applications); Drinking water, ambient
surface waters, domestic and industrial wastes, saline waters.
Summary of Method: The specific conductance of a sample is measured by use
of a self-contained conductivity meter, Wheatstone bridge-type, or equivalent.
Samples are preferably analyzed at 25°C. If not, temperature corrections are
made and results reported at 2S°C.
Limitations;
Range of Applicability; Not stated
Interferences; None cited
Pitfalls; Special Precautions; None cited
Statistical Characteristics; Forty-one analysts in 17 laboratories analyzed
six synthetic water samples containing known concentrations of inorganic salts,
with known values of specific conductance. The following results were obtained:
Known Conc'n. of
Specific Conductance
p mhos/cm
100
106
808
848
1640
1710
Precision as
Standard Deviation
ymhos/cm
7.55
8.14
66.1
79.6
106
119
Accuracy as
Bias,
%
-2.02
-0.76
-3.63
-4.54
-5.36
-5.08
Bias,
M mhos/cm
-2.0
-0.8
-29.3
-38.5
-87.9
-86.9
In a single laboratory (AQC), using surface water samples with an average
conductivity of 536 pmhos/cm at 25°C, the standard deviation was'jjjS.
Time of Measurement: Not stated, but rapid (several per hour)
Calibration Requirements: Instrument must be standardized with potassium
chloride solution daily.
Data Outputs; Meter reading (analog electrical signal, manually recorded
Special Sampling Requirements (Collection, Storage. Handling); None stated
References; (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
B-58
-------
No. B-60
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Sulfate
Medium; Water
Name of Measurement Method: Automated Chloranilate Method
Principal Detection Technique: Colorimetry
Purpose of Measurement (Important Applications): Ambient surface
waters, domestic and industrial wastes, saline waters
Summary of Method; When solid barium chloranilate is added to a solution
containing sulfate, barium sulfate is precipitated, releasing the highly
colored acid chloranilate ion. The color intensity in the resulting
chloranilic acid is proportional to the amount of sulfate present.
Method employs Technicon AutoAnalyzer with colorimeter equipped with
520 nm filters.
Limitations:
Range of Applicability: 10 to 400 mg/1 sulfate
Interferences; Calcium, aluminum, iron interfere, but may be
removed by ion exchange.
Pitfalls; Special Precautions; None cited
Statistical Characteristics; In a single laboratory (AQC), using surface
water samples at concentrations of 39, 111, 188, and 294 mg SO,/I, the
standard deviations were ±0.6, +1.0, ±2.2, and ± 0.8, respectively.
Time of Measurement; About 15 samples per hour.
Calibration Requirements; Requires preparation of standard solutions and
calibration curve.
Data Outputs; Analog electrical signal, recorded on stripchart.
Special Sampling Requirements (Collection, Storage, Handling): Refrigerate
at 4C.
References: Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-59
-------
No. B-61
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Sulfate
Medium; Water
Name of Measurement Method: None Stated
Principal Detection Technique; Colorimetry
Purpose of Measurement (Important Applications): Drinking water, ambient surface
waters, domestic and industrial wastes.
Summary of Method; Sulfate ion is converted to a barium sulfate suspension
under controlled conditions. The resulting turbidity is determined by a
photoelectric colorimeter or spectrophotometer and compared to a curve prepared
from standard sulfate solutions.
Limitations;
Range of Applicability; All concentrations of sulfate ion. Higher
concentrations must be diluted such that sample aliquot contain less
than 40 mg/1 sulfate.
Interferences;
Suspended matter and color interfere. Correct by running blanks from
which the barium chloride has been omitted.
Pitfalls; Special Precautions; None cited
Statistical Characteristics; Thirty-four analysts in 16 laboratories analyzed
six synthetic water samples containing exact concentrations of inorganic sulfate
with the following results:
Known Conc'n. of
Sulfate
mg/liter
8.6
9.2
110
122
188
199
Time of Measurement:
Calibration Requirements:
Precision as
Standard Deviation
mg/liter
2.30
1.78
7.86
7.50
9.58
11.8
Rapid
Not stated
Accuracy as
Bias,
-3.72
-8.26
-3.01
-3.37
+0.04
-1.70
Bias,
mg/liter
-.3
-.8
-3.3
-4.1
+.1
-3.4
Data Outputs; Meter output (analog electrical signal), manually recorded.
Special Sampling Requirements (Collection. Storage. Handling); None Stated
References: (1) Methods for Chemical Analysis of Water and Wasces,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
B-60
-------
No. B-62
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Sulfide
Medium: Water
Name of Measurement Method; Titrimetric (Iodine) Method
Principal Detection Technique: Titration
Purpose of Measurement (Important Applications); Drinking waters,
ambient surface waters, domestic and industrial wastes, saline water.
Summary of Method; Sulfides are stripped from the acidified sample
with an inert gas and collected in a zinc acetate solution. Excess
iodine added to the zinc sulfide suspension reacts with the sulfide
under acidic conditions. Thiosulfate is used to measure unreacted
iodine to indicate the quantity of iodine consumed by sulfide.
Limitations;
Range of Applicability; Concentrations of sulfide above one mg/1.
Interferences; Sulfites, thiosulfates, hydrosulfates, and other
reduced sulfur compounds may interfere.
Pitfalls; Special Precautions; Sample should have minimal contact with
air or oxygen.
Statistical Characteristics; Precision and accuracy for this method
have not been determined, but it is claimed that the iodimetric titration
of the zinc sulfide is quite accurate.
Time of Measurement: Not stated
Calibration Requirements; Not given
Data Outputs; Not stated. Assumed to be visual observations manually
recorded.
Special Sampling Requirements (Collection, Storage, Handling); Minimize
contact with air. Preserve with zinc acetate unless analysis is performed
immediately.
References: (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
B-61
-------
No. B-63
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Temperature
Medium; Water
Name of Measurement Method: Not Stated
Principal Detection Technique: Thermoraetry
Purpose of Measurement (Important Applications); Drinking waters, ambient
surface waters, domestic and industrial wastes, saline waters.
Summary of Method; Temperature measurements may be made with any good grade
of mercury-filled or dial type centigrade thermometer, or a thermistor.
Limitations;
Range of Applicability; Thermometers or thermistors can be obtained to
give valid results over almost any range of ambient temperatures.
Interferences; None
Pitfalls; Special Recautions: Measurement device should be checked
against a precision thermometer certified by the National Bureau of
Standards.
Statistical Characteristics; There is no acceptable procedure for determining
the precision and accuracy of this test.
Time of Measurement; Rapid
Calibration Requirements; Not stated
Data Outputs; Usually a visual reading manually recorded. Instruments
producing analog voltages automatically recorded are readily available.
Special Sampling Requirements (Collection, Storage, Handling); None
References; (1) Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
(2) Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
B-62
-------
No. B-64
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Threshold Odor
Medium: Water
Name of Measurement Method: Consistent Series Method
Principal Detection Technique: Personal sensing
Purpose of Measurement (Important Applications): This method is applicable
to the determination of threshold odor of finished waters, surface waters,
domestic and industrial wastes, and saline waters.
Summary of Method; The sample of water is diluted with odor-free water until
a dilution that is of the least definitely perceptible odor to each tester is
found. The resulting ratio by which the sample has been diluted is called
the "threshold odor number" (T.O.).
People vary widely as to odor sensitivity, and even the same person will
not be consistent in the concentrations he can detect from day to day. There-
fore, panels of not less than five persons, and preferably 10 or more, are
recommended to overcome the variability of using one observer.
As an absolute minimum, two persons are necessary: one to make the sample
dilutions and one to determine the threshold odor.
Limitations:
Range of Applicability: Highly odorous samples are reduced in concentration
proportionately before being tested. Thus, the method is applicable to
samples ranging from nearly odorless natural waters to industrial wastes
with threshold odor numbers in the thousands.
Interferences; Chlorine in tap water and some wastewaters may affect
results. It is sometimes desirable to determine the odor of the
chlorinated sample and the same sample after removal of the chlorine.
Removal can be accomplished by use of sodium thiosulfate in stoichiometric
proportions.
Pitfalls; Special Precautions; It is important to check a blank to which
a similar amount of dechlorinating agent has been added to determine if
any odor has been imparted. Such odor usually disappears upon standing
if excess reagent has not been added.
Statistical Characteristics:
Accuracy and Precision: Data not available at the time of publication of
Reference cited below.
Time of Measurement; Several hours.
Calibration Requirements; See Reference
Data Outputs; Personal detection of odor
Special Sampling Requirements (Collection. Storage, Handling); Water samples
must be collected in glass bottles with glass or Teflon-lined closures. Plastic
containers are not reliable for odor samples and must not be used. Complete test
as soon as possible after sample collection. If storage is necessary, fill
container to the top and refrigerate.
Reference; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-63
-------
No. B-65
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Turbidity
Medium: Water
Name of Measurement Method: Nephelometric
Principal Detection Technique; Photometric (Nephelometer)
Purpose of Measurement (Important Applications): This method is applicable
to surface and saline waters in the range of turbidity from 0 to 40 Jackson units.
Summary of Method: The method is based upon a comparison of the intensity of
light scattered by the sample under defined conditions with the intensity of
light scattered by a standard reference suspension. The higher the intensity
of scattered light, the higher the turbidity. Readings, in Jackson units, are
made in a nephelometer designed according to specifications outlined in Reference
cited below. A standard suspension of Formazin, also prepared under closely
defined conditions, is used to calibrate the instrument. Formazin polymer is
used as the turbidity reference suspension for water because it is more
reproducible than other types of standards previously used for turbidity
standards. Design criteria for instrument are given in Reference.
Limitations:
Range of Applicability: 0 to 40 Jackson units. Sensitivity should be
0.02 units or less in waters having turbidity of less than one unit.
Interferences: Floating debris, coarse sediments, air bubbles, or
colored material in solution may interfere.
Pitfalls; Special Precautions; Care should be exercised in selection of
instrument that meets criteria given in Reference.
Statistical Characteristics:
Accuracy and Precision; Data not available at time of publication of
Reference-
Time of Measurement; Not stated. Assumed rapid but not instantaneous, because
sufficient time must be allowed after shaking sample for air bubbles to dis-
appear but not for all suspended particles to settle. (Five minutes or less)
Calibration Requirements: Follow instrument manufacturer's recommendations,
but reliance on manufacturer's solid scattering standard is not always acceptable.
See Reference below.
Data Outputs; Photoelectric detector (analog signal) with ammeter readout.
Special Sampling Requirements (Collection, Storage, Handling): Samples taken fo:
turbidity measurements should be analyzed as soon as possible. Preservation of
samples is not recommended.
References; Methods for Chemical Analysis of Water and Wastes,
EPA National Environmental Research Center, Cincinnati,
Ohio (1971).
B-64
-------
B. WATER AND WASTEWATER METHODS
-------
SUMMARY OF ANALYTICAL METHOD
C-l
PARAMETER(S) MEASURED: Arsenic *
MEDIUM: Drinking Water
NAME OF MEASUREMENT METHOD:
Mercuric Bromide Stain Method *
PRINCIPAL DETECTION TECHNIQUES:
Thin Layer ChromatoeraDhy
PURPOSE OF MEASUREMENT: Arsenic may occur in water as a result of mineral dissolution
industrial discharges, or the application of pesticides.
SUMMARY OF METHOD:
After concentration of the sample arsenic is liberated as arsine, AsHj, by
zinc in acid solution in a Gutzeit generator. The generated arsine is then
passed through a column containing a roll of cotton moistened with lead acetate
solution. The generated arsine is allowed to produce a yellow-brown stain on
test paper strips impregnated with mercuric bromide. The length of the stain
is roughly proportional to the amount of arsenic present.
LIMITATIONS:
Range of Applicability! Not stated.
Sensitivity: Minimum detectable concentration is 1 microgram As (as stated
in Reference cited below), but should be used only for qualitative or semi-quali-
tative determinations (±5//g).
Interferences: Antimony, if present in quantities greater than 0.10 rag.
Pitfalls; Special Precautions: During the oxidation of organic matter, the
sample should not be allowed to darken because arsenic is likely to be reduced and
lost.
STATISTICAL CHARACTERISTICS:
Accuracy: A synthetic unknown sample containing 50 H-g/1 As, 400 ug/1 Be, 180
u.g/1 B, and 50 u.g/1 Se in distilled water was determined by the mercuric
bromide stain method with a relative error of 60.0 percent.
Precision; A synthetic unknown sample containing 50 u.g/1 As, 400 Jig/1 Be,
180 u.g/1 B, and 50 Ug/1 Se in distilled water was determined by the mercuric
bromide stain metnod, with a relative standard deviation of 75.0 percent in five
laboratories.
Time of Measurement: Not stated.
CALIBRATION REQUIREMENTS: A calibration curve is prepared by measuring the average
length of stains produced by a standard solution.
COMMENTS BY USERS: Not recommended for water because of poor accuracy and precision.
DATA OUTPUTS: Visual observation"
SPECIAL SAMPLING REQUIREMENTS: Not Stated
REFERENCES Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al..
Washington, D. C. (1971).
C-l
-------
C-2
SUMMARY OF ANALYTICAL METHOD
PARAMETER(S) MEASURED:
Arsenic
MEDIUM:
Drinking Water
NAME OF MEASUREMENT METHOD;
Silver Diethyldithiocarbamate Method
PRINCIPAL DETECTION TECHNIQUES:
Photometric
PURPOSE OF MEASUREMENT;
Arsenic may occur in water as a result of mineral dissolution, industrial
discharges, or the application of pesticides.
SUMMARY OF METHOD:
Inorganic arsenic is reduced to arsine, AsH^, by zinc in acid solution in a
Gutzeit generator. The arsine is then passed through a scrubber containing glass
wool impregnated with lead acetate solution and into an adsorber tube containing
silver diethyldithiocarbamate dissolved in pyridine. In the absorber, arsenic
reacts with the silver salt, forming a soluble red complex suitable for photometric
measurement.
LIMITATIONS;
Range of Applicability! Not stated.
Sensitivity; Minimum detectable concentration is 1 micrograra As (as stated in
Reference cited below)
Interferences; Antimony salts
Pitfalls; Special Precautions: Not stated.
STATISTICAL CHARACTERISTICS;
Precision; A synthetic unknown sample containing 40 Kg/1 As, 250 ug/1 Be,
240 jig/1 B, 20 jig/1 Se, and 6 ug/1 V in distilled water was determined by
the silver diethyldithiocarbamate method, with a relative standard deviation
of 13.8 percent in 46 laboratories.
Accuracy; A synthetic unknown sample containing 40 u.g/1 As, 240 (ig/1 B,
250 ug/1 Be, 20 jig/1 Se, and 6 ug/1 V in distilled water was determined by
this method, with a relative error of 0 percent in 46 labs.
CALIBRATION REQUIREMENTS: Not stated
DATA OUTPUTS: Analog instrumental reading
SPECIAL SAMPLING REQUIREMENTS: Not stated
REFERENCE: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
C-2
-------
C 3
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Cadmium
Medium: Drinking Water
Name of Measurement Method: Dithizone Method
Principal Detection Technique: Colorimetric
Purpose of Measurement (Important Applications): The maximum concen-
tration permitted by the U.S. Public Health Service Drinking Water
Standards is 0.01 mg/1.
Summary of Method: Under suitable conditions, cadmium ions react with
dithizone to form a pink to red color which can be extracted with chlo-
roform. The chloroform extracts are measured photometrically and the
cadmium concentration is obtained from a calibration curve prepared from
a standard cadmium solution treated in the same manner as the sample.
Limitations:
Range of Applicability: Not stated.
Sensitivity: Minimum detectable concentration: 0.5 fig
Cd with a 2-cm light path (as stated in reference cited below).
Interferences: Under the conditions of this method, concentrations
of metal ions normally found in water do not interfere. Lead
concentrations up to 6 mg, zinc up to 3 mg, and copper up to 1 mg in
the aliquot taken for analysis do not interfere. Ordinary room
lighting does not affect the cadmium dithizonate color.
Statistical Characteristics:
Accuracy and Precision: A synthetic unknown sample containing
50 pg/1 Cd, 500 pg/1 Al, 110 pg/1 Cr, WO ug/1 Cu, 300 pg/1 Fe,
70 ug/1 Pb, 120 pg/1 Mn, 150 pg/1 Ag, and 650 pg/1 Zn was determined
by the dithizone method with a relative standard deviation of
24.6 percent and a relative error of 6.0 percent in 44 laboratories.
Time of Measurement: Not stated
Calibration Requirements; Standard curve
Data Outputs: Analog electrical signal; instrumental output
Special Sampling Requirements (Collection, Storage, Handling): Not Stated
Reference; standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
C-3
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C-4
SUMMARY OF ANALYTICAL METHOD
PARAMETER(S) MEASURED: Chloride*
MEDIUM: Drinking Water
NAME OF MESUREMENT METHOD: Argentometric Method*
PRINCIPAL DETECTION TECHNIQUES: Titrimetric
PURPOSE OF MEASUREMENT:
Chloride is one of the major anions in water and sewage. A high chloride
content exerts a deleterious effect on metallic pipes and structures, as well
as on agricultural plants.
SUMMARY OF METHOD:
In a neutral or slightly alkaline solution, potassium chromate can indicate
the end point of the silver nitrate titration of chloride. Silver chloride
is quantitatively precipitated before red silver chromate is formed.
LIMITATIONS:
Range of Applicability: Not skated
Interferences: Sulfide, thiosulfate, and sulfite ions, orthophosphate in
excess of 25 mg/1, and ion in excess of 10 mg/1 interfere.
Pitfalls; Special Precautions: If sample is highly colored the
suspension should be coagulated, allowed to settle, filtered, washed,
and the filtrate and washings combined.
STATISTICAL CHARACTERISTICS:
Accuracy: A synthetic unknown sample containing 241 mg/1 chloride, 108 mg/1
Ca, 82 mg/1 Mg, 3.1 mg/1 K, 19.9 mg/1 Na, 1.1 mg/1 nitrate N, 250 ug/1 nitrite
N, 259 mg/1 sulfate, and 42.5 mg/1 total alkalinity (contributed by NaHC03) in
distilled water was determined by the argentometric method, with a relative error
of 1.7Z.
Precision: A synthetic unknown sample continaing 241 mg/1 chloride,
108 mg/1 Ca, 82 mg/1 Mg, 3.1 mg/1 K, 19.9 mg/1 Na, 1.1 mg/1 nitrate N, 250 ug/1
nitrite N, 259 mg/1 sulfate, and 42.5 mg/1 total alkalinity in distilled water
was determined by the argentometric method, with a relative standard deviation of
4.2% in 41 laboratories.
Time of Measurement; Not stated
CALIBRATION REQUIREMENTS: The silver nitrate titrant should be established.
* COMMENTS BY USERS: The means of a consistent endpoint should be established by
the analyst. Note: The potentlometric method given on page 377 of reference cited is
recommended instead of this method. (See Method Summary C-6.)
DATA OUTPUTS: Manual reading and recording.
SPECIAL SAMPLING REQUIREMENTS: Not stated
REFERENCE: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
C-4
-------
SUMMARY OF ANALYTICAL METHOD - ,
.... ____ ^. ^
PARAMETER(S) MEASURED: Chloride
MEDIUM: Drinking Water
NAME OF MEASUREMENT METHOD: Mercuric Nitrate Method
PRINCIPAL DETECTION TECHNIQUES: Titrimetric
PRUPOSE OF MEASUREMENT:
Chloride is one of the major anions in water and sewage. A high chloride
content exerts a deleterious effect on metallic pipes and structures, as well as
on agricultural plants.
SUMMARY OF METHOD:
Chloride can be titrated with mercuric nitrate because of the formation
of soluble, slightly dissociated mercuric chloride. In the pH range 2.3-2.8,
diphenylcarbazone indicates the end point of this titration by formation of
a purple complex with the excess mercuric ions.
LIMITATIONS:
Range of Applicability: Increasing the strength of the titrant and modi-
fying the indicator mixture enables determination of the higher chloride
concentrations common In wastewater.
Interferences: Bromide, iodide, and chromate, ferric, and sulfite ions in
excess of 10 mg/1.
Pitfalls; Special Precautions: A 0.1 pH unit change will produce an error
SSSd15e°fuShStv?iT50l uh!.tltrant used in PH range 2-1-2-8- Test
Statistical Characteristics:
Accuracy: A synthetic unknown sample containing 241 mg/1 chloride, 108 mg/1
Ca, 82 mg/1 Mg, 3.1 mg/1 K, 19.9 mg/1 Na, 1.1 mg/1 nitrate N, 250 Ug/1 nitrite N,
259 mg/1 sulfate, and 42.5 mg/1 total alkalinity (contributed by NaHC03) in
distilled water was determined by the mercurimetric method, with a relative error
of 2.9%.
A synthetic unknown sample containing 241 mg/1 chloride,
108 mg/1 Ca, 82'mg/i Hg, J.I mg/1 K, 19.9 mg/1 Na, 1.1 mg/1 nitrate N, 250
ug/1 nitrite N, 259 mg/1 sulfate, and 42.5 rag/1 total alkalinity (Contributed
by NaHCOj) in distilled water was determined by the mercurimetric method with a
relative standard deviation of 3.3% in 10 laboratories.
iluie of Measurement: Not stated
CALIBRATION REQUIREMENTS: Not stated
DATA OUTPUTS: Manually read and recorded.
SAMPLING REQUIREMENTS: Not stated
REFERENCE; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al..
Washington, D. C. (1971).
C-5
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C-6
SUI-MARY OF ANALYTICAL METHOD
Paraneter(s) Measured: Cliloride
Medium: Drinking Water
Name of Measurement Method: Potentiometric Method
Principal Detection Technique: Potentiometric Titratton
Purpose of Measurement (Important Applications): To determine the concentration
of chloride ion in unter; useful in colored or turbid solutions.
Summary of Method: Potentiometric titration of chloride with silver nitrate is
performed bv use of a glass and silver-silver chloride electrode system. An
electronic voltmeter detects changes in potential between the electrodes. The
endpoint is determined bv the rate of voltage change relative to increments of
silver nitrate added.
Limitations:
Range of Applicability: Not stated
Interferences: Iodide, bromide, ferricyanide, chromate, dichromate, and
ferric ions. Certain of these interferences can be easily removed.
Pitfalls; Special Precautions: None identified
Statistical Characteristics:
Accuracy and Precision: About 2.5 percent in the absence of interferences,
or 5 percent where interferences are present.
Time of Measurement: Not stated, but rapid
Calibration Requirements: See Reference
Data Outputs: Electrical voltage
Special Sampling Requirements (Collection. Storage, Handling): None stated
References: Standard Methods for the Examination of Water and Waste
Uater, 13th Edition, American Public Health Association,
et al.. Washington, D. C. (1971)
C-6
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C-7
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Chlorinaced Hydrocarbon Pesticides
Medium: Drinking Water
Name of Measurement Method: Gas Chromatographic Method
Principal Detection Technique: Electron Capture Gas Chromatography
Purpose of Measurement (Important Applications): To determine concentrations of
chlorinated hydrocarbon and certain related pesticides in drinking water supply.
Summary of Method: Pesticides are extracted from the aqueous sample with hexane,
which is then separated frost the aqueous layer, drieii over anhydrous sodium sulfate,
nnH concentrate^ hv evsnoratlnn («»«>re necessary, interfering substances are'femoved
from the pesticides by eluting through a Florisil column). The concentrate is
injected into the gas chromatograph system, vaporized in the carrier gas, and moved
into the appropriately packed GC column. The pesticides travel through the column
at different rates. As each pesticide goes through the detector, a quantitatively
proportional electrical signal is recorded as a peak on a stripchart. The elution
time indicates a particular pesticide, and the height of the peak on the chart is
proportional to the quantity injected. Confirmatory identification can be made
from retention times by two or more columns with different packings.
Limitations;
Range of Applicability and Detection Limits; Depends upon clean-up efficiency,
instrument parameters, specific pesticides being determined, and other factors.
Llndane, for example, can usually be determined at 0.01 pg/1 In relatively
unpolluted water.
Interferences: Certain oxygenated and unsaturated compounds.
Pitfalls; Special Precautions: None specifically identified. Extreme care
must be exercised throughout the procedures in this method.
Statistical Characteristics:
Accuracy and Precision; Results are tabulated for three synthetic samples
containing known amounts of six pesticides (p, p-DDT, Dieldrln, Endrin, Heptachlor,
Heptachlor Epoxide, and Lindane) when analyzed in 29 to 37 laboratories. The
results for Dieldrin are as follows:
Concentration No. o
Ug/1 Labs
0.25 32
5.0 37
15. 29
Time of Measurement:
Relative
Error (12)
14.0
7.2
10.9
Not stated
See Reference
Relative
Std. Dev. (2)
35.7
42.2
20.2
Calibration Requirements:
Data Outputs: Analog electrical signals recorded on stripchart.
Special Sampling Requirements (Collection, Storage, Handling): Use glass sample
bottles with teflon-lined screw cap.
References; standard Methods for the Examination of Water and Waste
Water, 13th Edition, American Public Health Association,
et al., Washington, D. C. (1971).
C-7
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C-9
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Color
Medium: Drinking Water
Name of Measurement Method: Platinum-Cobalt method
Principal Detection Techniques: Visual Comparison
Purpose of Measurement (Important Applications): Determination of color is
applicable to nearly all samples of potable water.
Summary of Method: Color is determined by visual comparison of the sample with
known concentrations of colored solutions. Comparison may also be made with special
glass color discs if they have been properly calibrated. The platinum-cobalt method
of measuring color is given as the standard method, a unit of color being that
produced by 1 mg/1 platinum in the form of the chloroplatinate ion.
Limitations:
Range of Applicability: Not stated
Interferences: Slight turbidity causes apparent color to be higher than
true color. The recommended method for removal of turbidity is centrifugation.
Pitfalls; Special Precautions: The color value is pH dependent; the pH at
which the color is determined should be reported.
Statistical Characteristics!
Accuracy: Not stated
Precision: Not stated
Time of Measurement: Not stated
Calibration Requirements: Ratio of cobalt to platinum may be varied to match the
hue in special cases.
Data Outputs: Visual comparison
Special Sampling Requirements (Collection, Storage, Handling): Color determination
should be made within a reasonable period, as biologic and physical changes occurring
in storage may affect color.
References; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
•..-8
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C-8
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: HexavalenC Chromium
Medium; Drinking Water
Name of Measurement Method:
Principal Detection Technique: Colorimetric
Purpose of Measurement: The maximum hexavalent chromium concentration
allowed by the Public Health Service Drinking Water Standards is 0.05 mg/1.
Summary of Method: Hexavalent chromium reacts with diphenylcarbazide to
produce a reddish purple color in lightly acid solutions. The color pro-
duced is proportional to the concentration of chromium present.
Limitations:
Range of Applicability: Not stated
Sensitivity: Minimum detectable concentration is S ug/1 when a 5-cm
light bath Is used for photometric measurements, and 3 ug/1 when
detection is made using 50 ml nessler tubes.
Interferences: Mercury, iron in concentration >1 mg/1 and vanadium.
Pitfalls; Special Precautions: Not stated
Statistical Characteristics:
Accuracy: Accuracy depends on the promptness with which the
determination for hexavalent chromium is undertaken.
Precision: Photometric measurements in the range below 400 u.g/1
can be made with a precision of 10 ug/1 Cr.
Time of Measurement: Not stated
Calibration Requirements: Standard Curve
Data Outputs: Visual observation or analog electrical readout.
Special Sampling Requirements (Collection, Storage. Handling); New glass
bottles rather than old etched containers should be used for sample collection.
The sample should be tested during the day of collections.
Reference; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D.C. (1971).
C-9
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C-10
SUMMARY OF ANALYTICAL METHOD
FARAMETER(S) MEASURED: Copper
MEDIUM: Drinking Water
NAME OF MEASUREMENT METHOD: Bathocuproine Method
PRINCIPAL DETECTION TECHNIQUES: Colorimetric
PURPOSE OF MEASUREMENT:
Copper is an element essential to the human body and the adult dally require-
ment has been estimated at 2.0 mg. Large oral doses may, however produce ernesis
which, if prolonged, may result in liver damage. In amounts above 1.0 mg/1 copper
can impart a bitter taste to the water.
SUMMARY OF METHOD:
Cuprous ions form a water-soluble orange-colored chelate with bathocuproine
disulfonate. Although the color forms over the pH range of 3.5 to 11.0,
the recomended pH range is between 4 and 5. Hydrochloric acid and citrate buffer
the system at a pH of about 4.3, while hydroxylamine hydrochloride serves as a
reducing agent. The absorbance is measured at 484 mp. The method can be
applied to copper concentrations up to at least 5 mg/1 with a sensitivity of
20 ug/1.
LIMITATIONS:
Range of Applicability: Up to 5 mg/1.
Sensitivity: Minimum detectable concentration is 20 /^g/1.
Interferences: A list of ions and substances and their tolerable concentra-
tions to produce an error of less than + 2 percent is given in the refp.rp.nc>>..
STATISTICAL CHARACTERISTICS:
Accuracy and Precision: A synthetic unknown sample containing 1.00 mg/1 Cu,
500 ug/1 Al, 50 yg/1 Cd, 110 pg/1 Cr, 300 ug/1 Fe, 70 pg/1 Pb, 50 ug/1 Mn,
150 ug/1 Ag and 650 pg/1 Zn was determined by the bathocuproine method, with
a relative standard deviation of 4.1% and a relative error of 0.3% in
33 laboratories.
Time of Measurement! Not stated
CALIBRATION REQUIREMENTS: A calibration curve is prepared from a standard copper solution.
DATA OUTPUTS: Analog electrical signal; instrumental output.
SPECIAL SAMPLING REQUIREMENTS: Samples should be analyzed as soon as possible after
collection.If storage is necessary,acidification is used.
REFERENCES; standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al,,
Washington, D. C. (1971).
C-10
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SUMMARY OF ANALYTICAL METHOD c-11
PARAMETER(S) MEASURED: Copper
HSDIUM: Drinking Water.
NAME OF MEASUREMENT METHOD; Cuprethol Method
PRINCIPAL DETECTION TECHNIQUES: Colorimetric
PURPOSE OF MEASUREMENT:
Copper is an element essential to the human body and the adult daily require-
ment has been estimated at 2.0 mg. Large oral doses may, however, produce emesis
which, if prolonged, may result in liver damage. In amounts above 1.0 mg/1 copper
can impart a bitter taste to the water.
SUMMARY OF METHOD:
Cupric ions form a yellow-colored chelate with the reagent bis(2-hydroxyethyl)
dithiocarbamate, the popular name of which is cuprethol. The colored compound is
soluble and is formed quantitatively. Hydrochloric acid and sodium acetate buffer
the solution at a favorable pH, between 5 and 6. Pyrophosphate overcomes the
interference of iron up to 20 mg/1 as ferric ion and up to 50 mg/1 as ferrous ion.
LIMITATIONS:
Range of Applicability: This method is intended for the determination of
traces of copper in relatively unpolluted water.
Sensitivity: A copper concentration of 20 ftg/1 can be detected by visual
comparison in 100-ml nessler tubes.
Interferences; Bismuth, cobalt, mercurous, nickel, and silver ions interfere
seriously and must be absent. Other ions which Interfere must be limited to
the concentration shown in Reference.
Pitfalls; Special Precautions: Turbidity or color must be corrected by
photometric compensation techniques or by extraction of the copper chelate
with isoamyl alcohol.
STATISTICAL CHARACTERISTICS:
Accuracy and Precision: A synthetic unknown sample containing 470 ug/1
Cu, 500 ug/1 Al, 50 ug/1 Cd, 110 ug/1 Cr, 300 ug/1 Fe, 70 pg/1 Pb, 120 pg/1 Mn,
150 pg/1 Ag, and 650 pg/1 Zn in distilled water was determined by the cuprethol
method with a relative standard deviation of 17.5% and a relative error of 8.5Z
in 25 laboratories.
An unknown sample containing 1.00 mg/1 Cu, 500 u.g/1 Al, 50 u.g/1 Cd,
110 pg/1 Cr, 300 pg/l'Fe, 70 ug/1 Pb, 50 pg/1 Mn, 150 gg/1 Ag and 650 ug/1 Zn
was determined by the cuprethol method, with a relative standard deviation of
2.7Z and a relative error of l.OZ in 17 laboratories.
Time of Measurement: Not stated.
CALIBRATION REQUIREMENTS: A calibration curve is prepared from a standard copper solution.
DATA OUTPUTS; Analog electrical signal or visual comparison.
SPECIAL SAMPLING REQUIREMENTS; Samples should be analyzed as soon as possible
after collection. If storage is necessary acidification is used.
REFERENCES: Standard Methods for Examination of Water and Wastewatar,
13th Edition, American Public Health Association, e^a.^.,
Washington, D. C. (1971).
C-11
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C-12
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Cyanide
Medium; Drinking water
Name of Measurement Method: Colorimetric Method
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications): "Cyanide" refers to all of the CN
groups in the cyanide compounds present that can be determined as the cyanide ion,
CN_, by the methods used. The cyanide compounds in which cyanide can be obtained as
CN are classed as simple and complex cyanides. The cyanide ion, CN~, is very toxic.
Because the simple alkali cyanides form CN~ when dissolved in aqueous solution, they,
too, normally display intense toxicity.
Summary of Method: The CN~ in the alkaline distillate from a preliminary screening
procedure is converted to cyanogen chloride, CNC1, by reaction with chloramine-T at a
pH less than 8 without hydrolyzing to the cyanate. After the reaction is complete,
the CNC1 forms a blue dye on the addition of a pyridlne-pyrazolone reagent. The
dye is kept in an aqueous solution, and the absorbance is read at 620 mil.
Limitations:
Range of Applicability: Samples with less than 1 mg/1 CN
Interferences: All interferences are eliminated or reduced to a minimum by
using only a distillate from the preliminary screening procedure (see reference).
Pitfalls; Special Precautions: Not stated
Statistical Characteristics:
Accuracy and Precision: For aqueous color readings the coefficient of variation
was 1.72, the sensitivity 0.5 vg, and the effective range 1-5 ug. For extracted
color readings, the respective figures were 3.9%, 0.1 yg, and 0.2-2.0 yg. (Sensi-
tivity is defined here as the amount of CN required to produce an absorbance
of 0.05 or above with a precision not more than twice the coefficient of
variation given.)
Time of Measurement: Not stated
Calibration Requirements; To obtain colors of comparable intensity (for the
calibration curve), it is essential to have the same salt content in both the sample
and the standards.
Data Outputs; Analog electrical signal; instrumental output
Special Sampling Requirements (Collection, Storage, Handling): Analyze
immediately or raise pH.
Reference: Standard Methods for Examination of Water and Wasteuater,
13th Edition, American Public Health Association, et_al.,
Washington, D. C. (1971).
Described in Reference.
C-12
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C-14
SUMMARY OF ANALYTICAL METHOD
Paramecer(s) Measured: Flltrable Residue
Medium; Drinking Water
Name of Measurement Method: Filtrable Residue
Principal Detection Techniques; Gravimetric
Purpose of Measurement (Important Applications): Waters yielding considerable
residue are generally inferior with respect to palatability, or they may induce
an unfavorable physiological reaction in the transient consumer.
Summary of Method: The sample is filtered and the filtrate evaporated in a weighed
dish on a steam bath. The residue left after evaporation is dried to constant weight
in an oven. The increase In weight over that of the empty dish represents filterable
residue and includes all materials, liquid or solid, in solution or otherwise, which
pass through the filter and are not volatilized during the drying process.
Limitations;
Range of Applicability; All ranges
Interferences: None
Pitfalls; Special Precautions: None
Statistical Characteristics:
Accuracy; Not stated
Precision; A synthetic unknown sample containing 134 mg/1
filterable residue was determined gravimetrlcally, with a standard
deviation of + 13 mg/1 in laboratories, using a drying temperature
of 103-105 C.
Time of Measurement: Not stated
Calibration Requirements; None
Data Outputs: Mechanical scale reading
Special Sampling Requirements (Collection. Storage. Handling): None
References: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington. D. C. (1971).
C-13
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c-i:
SUMMARY OF ANALYTICAL METHOD
PARAHLTCiKS) .-lEASURED: Fluoride*
MEDIUM: drinking Water.
NAME OF MEASUREMENT METHOD: Alizarin Visual Method*
PRINCIPAL DETECTION TKCll.-iTljULS : Color Lmetric
The accurate determination of flu-.-ride in water supplies has
L.iiriMscd in iinmri im i- uiili t IK gruwUi ot the practice ot f I nor idatlon of supplies as
.1 uiiblu hf.ilil; nc.isui Tim m.iintu.i.ince of a constant :luo.-jdc concentration is
..sseiuial in iii.iii-i4ini.ii- ill" >•('! cct i veness and safely ol Llic f I nor idat ion procedure.
SUMMAKS OF
Tlie acid zi rcon> 1-jlizarin reagent and fluoride combine to form a color
Intensity proportional to the concentration of fluoride present.
LiMfT.vrio:;s:
Itange of Applicability 0.05 - 1.4 mg/1 F
Interferences: Aluminum, hexamctaphosphate, iron, chlorine, and orthophos-
phate adversely affect the colorimctric methods and necessitate recourse to
preliminary distillation (see reference).
Pitfalls; Special Precautions: The temperature of the samples should be same
as I lie standard solution used to develop the standard curve.
s.:. V L'iTj LAi. CMARAn CIUST K.b :
and Precision: Resnli:« ohtal"'"' •"• ">n ]p«-f.rai-prin^ •
Relative
Relative Error Std. Deviation
Without With Without With
Distillation Distillation Distillation Distillation
Svnthetic sample
with 830 jg/1
fluoride in
distilled water 3.6% 2.4% 4.9% 6.4%
T\;o svntlietic samples
with 570 and 680 :.g/l
fluoride plus inter-
ferences 29.8% 0-1.5% 5J.8% 10. 6-11. 1Z
Time of Measurement: Hot stated
CALIBRATION REQUIREMENTS: A standard curve is prepared using a fluoride standard
in the range 0 - 1.40 mg/1.
*COMMENTS iJY USERS: Method is no£ recommended without distillation.
DATA OUTPUTS: Analog electrical signal (instrumental output).
SPECIAL SAMPLING REQUIREMENTS (COLLECTION. STORAGE. HANDLING) : None stated
REFERENCES : Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al. .
Washington, D.C. (1971).
C-14
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C-16
SUMMARY OF ANALYTICAL METHOD
PARAMETER(S) MEASURED: Fluoride.
MEDIUM: Drinking Water
NAME OF MEASUREMENT METHOD: Electrode Method
PRINCIPAL DETECTION TECHNIQUES; Electrometric
PURPOSE OF MEASUREMENT:
The accurate decermination of fluoride in water supplies has increased in
importance with the growth of the practice of fluoridation of supplies as a public
health measure. The maintenance of a constant fluoride concentration is essential
in maintaining the effectiveness and safety of the fluoridation procedure.
SUMMARY OF METHOD:
The fluoride ion-activity electrode is a specific ion sensor. The key
element in the fluoride ion-activity electrode is the laser-type doped single
lanthanum fluoride crystal across which a current is established by the presence
of fluoride ions.
The fluoride ion-activity electrode can be used to measure the activity or
the concentration of fluoride in aqueous samples by use of an appropriate cali-
bration curve. The fluoride activity is dependent upon the total ionic strength
of the sample, and the electrode does not respond to fluoride which is bound
or complexed. These difficulties are largely overcome by the addition of citrate
ion to preferentially complex aluminum and by the addition of a buffer solution of
high total ionic strength to mask out variations in sample ionic strength.
LIMITATIONS:
Range of Applicability: The electrode method can be applied to fluoride
concentrations between 0.1 to 5 mg/1.
Interferences; Polyvalent cations such as Al(III), Fe(III), and Si(IV) will
complex fluoride ion. The extent to which complexing takes place depends, upon
the pH and the relative levels of the fluoride and the compounding species.
Pitfalls; Special Precautions: pH of the solution must be between 5-8.
STATISTICAL CHARACTERISTICS:
Accuracy: The relative error on three samples ranged from 0.2-4.9 percent
over observed range of 750 - 900 R/l.
Precision: The relative standard deviation on three samples ranged
from 2.9 - 4.8 percent.
Time of Measurement: Not stated
CALIBRATION REQUIREMENTS: The calibration of the electrode should be confirmed
after analyzing each unknown and after reading each standard when preparing the
standard curve?
DATA OUTPUTS: Analog electrical signal; instrumental reading
SPECIAL SAMPLING REQUIREMENTS: Not stated.
REFERENCE: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al. ,
Washington, D. C. (1971).
C-15
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C-17
SUMMARY OF ANALYTICAL METHOD
PARAMETER(S) MEASURED: Fluoride*
MEDIUM: Drinking Water
NAME OF MEASUREMENT MET
PRINCIPAL DETECTION TECHNIQUES: Colorimetric
PURPOSE OF MEASUREMENT:
The accurate determination of fluoride in water supplies has increased
in importance with the growth of the practice of fluoridation of supplies as
a public health measure. The maintenance of a constant fluoride concentration
is essential in maintaining the effectiveness and safety of the fluoridation
procedure.
SUMMARY OF. METHOD;. Zirconium combines with fluoride to produce a color intensity
proportional to the concentration of fluoride present. The reaction rate between
fluoride and zirconium ions is influenced greatly by the acidity of the reaction
mixture. By increasing the proportion of acid in the reagent, Che reaction can
be made practically instantaneous.
LIMITATIONS:
Range of Applicability: 0.05 - 1.4 mg/1 F
Interferences: Aluminum, hexaraetaphosphate, iron,chlorine,and orthophos-
phate adversely affect the colorimetric methods and necessitate recourse to
preliminary distillation (see reference).
Pitfalls; Special Precautions: The temperature of the samples should be the
same as the standard solution used to develop the standard curve.
STATISTICAL CHARACTERISTICS:
Accuracy and Precision: Results obtained at 53 laboratories using samples
ranging from 570 to 830 pg/1 fluoride:
Relative Error Relative Std. Deviation
Without With Without With
Distill'n. Distill'n. Distill'n. Distill'n.
Sample with
no Interferences 1.2% 2.4% 8.0% 11.0%
Samples containing
interferences 7.0 5.3-5.9 16.2 12.8-17.2
Time of Measurement: Not stated
CALIBRATION REQUIREMENTS: A standard curve is prepared using a fluoride standard
in the range 0 - 1.40 mg/1.
*COMMENTS BY USERS: Method is not recommended without distillation.
DATA OUTPUTS: Analog electrical signal, (instrumental output).
SPECIAL SAMPLING REQUIREMENTS (COLLECTION. STORAGE. HANDLING): None stated
REFERENCES: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D.C. (1971).
C-16
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C-18
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Gross Alpha and Gross Beta Radioactivity
Medium: Water (Drinking)
Name of Measurement Method:
Principal Detection Technique: Counting
Purpose of Measurement (Important Applications): The 1962 Public Health Service
Drinking Water Standards recommend limits for the concentration of radium 226
(3 pCi/1) and strontium 90 (10 pCi/1). If alpha emitters and strontium 90 are
known to be negligible fraction of the above specified limits, the water supply
would usually be regarded as radiologically acceptable, provided that the gross
beta concentration does not exceed 1,000 pCi/1.
Summary of Method: A sample containing not more than 200 mg of residue for
beta examination and not more than 100 mg of residue for alpha examination is
evaporated, dried in an oven at 103-105 C, and cooled in a desiccator. The
alpha and beta activity is then counted at the alpha and beta plateaus,
respectively. The sample is stored in a dessicator and counted for decay, if
necessary. The pretreatment steps vary for dissolved matter, suspended matter
or semi-solid samples.
Limitations:
Range of Applicability: Not stated
Interferences: Organic matter in samples must be oxidized
Pitfalls; Special Precautions: When assaying gross beta activity in
samples containing mixtures of naturally radioactive elements and
fission products, the choice of a calibration standard may signifi-
cantly influence the beta results because self-absorption factors and
counting chamber characteristics are beta energy dependent. For low-
level counting it is imperative to evaporate all moisture and
preferable to destroy organic matter before depositing a thin film
of sample solids from which radiation may readily enter the counter.
Statistical Characteristics:
Accuracy: The average recoveries of added gross alpha activity
from 15 laboratories was 86, 87, 84 and 82 percent for four samples.
The average recoveries of added gross beta activity from 16 labora-
tories was 99, 100, 100, and 100 percent for four samples.
Precision; The precision at 95 percent confidence level for the gross
alpha activity sample from the 15 laboratories was 20 and 24 percent
for two sets of paired samples. The precision at the 95 percent
confidence level was 12 and 18 percent for two sets of paired gross
beta activity samples.
Time of Measurement: Method requires only minutes to perform
following the pretreatment steps.
Calibration Requirements: When an internal proportional counter is used,
the system of assay is calibrated by adding standard nuclide portions to media
comparable to the samples and preparing, mounting and counting the standards
identical to that of the samples.
Data Outputs: Digital output
Special Sampling Requirements (Collection. Storage. Handling): None stated
References: Standard Methods for Examination of Water and Wastewater.
13th Edition, American Public Health Association, et al..
Washing;.-... *.C. (1971).
C-17
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C-19
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Iron
Medium: Drinking Water
Name of Measurement Method: Extraction Method
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications): Iron's importance in water derives
from the stains imparted to laundry and porcelain, and also the bittersweet astringent
taste which may be detectable by some persons at levels above 1 or 2 mg/1.
Summary of Method: This is a modification of the phenanthroline method.* If inter-
ference caused by the presence of metal ions or of anions that may complex iron is
suspected, iron can be separated by extraction from 7N-8N HC1 solution with diisopropyl
ether. The colorimetrie determination is made on a subsequent aqueous extract of the
iron from the ether by the phenanthroline method.
Limitations:
Range of Applicability: 0.1 - 20 mg/1.
Interferences: Cyanide, nitrite, phosphorous, and turbidity.
Statistical Characteristics:
Accuracy and Precision: A synthetic unknown sample containing 300 ug/1 Fe,
500 ug/1 Al, 50 ug/1 Cd, 110 ug/1 Cr, 470 ug/1 Cu, 70 ug/1 Pb, 120 ug/1 Mn,
150 ug/1 Ag and 650 ug/1 Zn in distilled water was determined by the phenana-
throline method, with a relative standard deviation of 25.5% and a relative
error of 13.3% in 44 laboratories.
Time of Measurement: Not stated
Calibration Requirements; Calibration curve is prepared using an electrolytic iron
wire or iron wire.
Data Outputs; Analog instrumental or visual comparison
Special Sampling Requirements (Collection. Storage, Handling): The sample should be
treated with acid at the time of collection or prior to analysis to prevent deposition of
iron on the container wall.
References; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Piblic Health Association, et_aj_. i
Washington, D. C. (1971).
* See Method Summary in this comptidium.
C-18
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C-20
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Iron (total, filterable, or ferrous)
Medium: Drinking water
Name of Measurement Method: Phenanthroline method
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications): Iron's importantance in water derives
from the stains imparted to laundry and porcelain, and also the bittersweet astringent
taste which may be detectable by some persons at levels above 1 or 2 mg/1.
Summary of Method: Iron is brought into solution, reduced to the ferrous state
by boiling with acid and hydroxylamine.and treated with 1,10-phenanthroline at pH 3.2-
3.3. The colored solution obeys Beer's law; its intensity is independent of pH from
3 to 9 and is stable for at least 6 months. Color intensity is determined colorlmetrically.
Limitations:
Ranee of Applicability: Direct application of method 0.02-4 mg/1.
Interferences: Strong oxidizing agents, cyanide, nitrite, and phosphates;
chromium; zinc in concentrations exceeding ten times that of iron; cobalt and
copper in excess of 5 mg/1, and nickel in excess of 2 mg/1. Bismuth, cadmium,
mercury, molybdate, silver and turbidity.
Statistical Characteristics:
Accuracy and Precision: A synthetic unknown sample containing 300 ug/1 Fe,
500 pg/1 Al, 50 ug/1 Cd, 110 ug/1 Cr, 470 ug/1 Cu, 70 ug/1 Pb, 120 ug/1 Mn,
150 ug/1 Ag and 650 ug/1 Zn in distilled water was determined by the phenanthroline
method, with a relative standard deviation of 25.5% and a relative error of 13.32
in 44 laboratories.
Time of Measurement: Not stated
Calibration Requirements: Electrolytic iron wire or iron wire is used to prepare the
standard iron solution.
Data Outputs: Analog instrumental or visual comparison
Special Sampling Requirements (Collection. Storage, Handling): The sample should be
treated with acid at the time of collection or prior to analysis to prevent deposit of iron
on the container wall.
Reference; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al..
Washington. D. C. (1971).
C-19
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C-21
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Iron
Medium: Drinking Water
Name of Measurement Method: Tripyridine Method
Principal Detection Techniques: Colorimecric
Purpose of Hesurement (Important Applications):
Iron's importance in water derives from the stains Imparted to laundry and
porcelain, and also the bittersweet astringent taste which may be detectable by
some persons at levels above 1 or 2 mg/1.
Summary of Method:
Iron is brought into solution by boiling with acid, is reduced to the ferrous
state by hydroxylamine, and is then treated with 2,2',2"-tripridine. The color complex
formed obeys Beer's law, Is independent of pti over the range 1.5 to 12, and is stable
for at least 3 months. Ethylendiamine is used to buffer the mixture at pH 9.6 and
to complex heavy metals which might otherwise interfere. Color intensity can be
determined visually or colorimetrically.
Limitations:
Range of Applicability: Direct application of method 0.02 - 4.0 mg/1.
Interferences: Strong oxidizing agents, color, turbidity, cyanide and nitrite
Statistical Characteristics:
Accuracy and Reproducibility: A synthetic unknown sample containing 300
Pg/1 Fe, 500 lig/1 Al, 50 Mg/1 Cd. 110 Mg/1 Cr, 470 Mg/1 Cu, 70 Mg/1 Pb, 120 ng/1
Mn, 150 Mg/1 Ag and 650 Mg/1 Zn in distilled water was determined by the tripyridine
method, with a relative standard deviation of 62.4% and a relative error of 13.32
In six laboratories.
Time of Measurement: Not stated
Calibration Requirements: A set of standards are prepared using electrolytic
iron wire or iron wire.
Data Outputs: Analog Instrumental reading or visual comparison
Special Sampling Requirements:
The sample should be treated with acid at the time of collection or prior to
analysis to prevent deposition of iron on the container wall.
Reference: Standard Methods for Examination of Water and Wastewater,
'13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
C-20
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C-22
SUMMARY OF ANALYTICAL METHOD
PARAMETER(S) MEASURED: Lead
MEDIUM: Drinking Water
NAME OF MEASUREMENT METHOD: Dithizone Method.
PRINCIPLE DETECTION TECHNIQUES: Colorimetric
PURPOSE OF MEASUREMENT:
The presence of lead in a water supply may arise from Industrial mine and
smelter discharges, or from the dissolution of old lead plumbing. Tap waters
which are soft, acid, and not suitably treated may contain lead resulting from an
attack on the lead service pipes.
SUMMARY OF METHOD:
Dlc'iu'zone dissolved in carbon tetrachloride will extract lead from a slightly
basic solution. Lead and dithizone form a metal complex, lead dlthizonate, which
is soluble in carbon tetrachloride, with the formation of a red color. Measurement
of the intensity of the color complex yields an estimation of the lead present.
LIMITATIONS:
Range of Applicability: Minimum detectable concentration 2 ug Pb.*
Interferences: All interferences can be removed.
Pitfalls, Special Precautions: The procedure is extremely sensitive, and
measurable amounts of lead may be picked up from glassware and reagents.
STATISTICAL CHARACTERISTICS:
Accuracy and Precision: A synthetic unknown sample containing 70 ug/1 Pb,
500 Pg/1 Al, 50 ug/1 Cd, 110 Pg/1 Cr, 470 ug/1 Cu, 300 Ug/1 Fe, 120 ug/1 Mn,
150 Pg/1 Ag and 650 Pg/1 Zn in distilled water was determined by the dithizone
method, with a relative standard deviation of 42.IX and a relative error of 8.53!
in 43 laboratories.
Time of Measurement: Not stated
CALIBRATION REQUIREMENTS: A calibration curve is prepared using dilutions
of a stock standard solution.
DATA OUTPUTS: Analog instrumental reading
SPECIAL SAMPLING REQUIREMENTS: Not stated
REFERENCES: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
As stated in Reference cited.
C-21
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C-23
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Manganese
Medium: Drinking Water
Name of Measurement Method: Periodate Method
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications): Manganese imparts objectionable
and tenacious stains to laundry and plumbing fixtures.
Summary of Method: With periodate as the oxidizing agent acting upon soluble
manganous compounds to form permanganate, Beer's law holds closely up to 15 mg.
The intensity of the color is not affected by variation in acid or periodate
concentration and the color is stable for many months.
Limitations:
Range of Applicability: 5 ug - 15 mg Mn*
Interferences: Oxidizable substances, chloride, and reducing agents
Pitfalls; Special Precautions: Not stated
Statistical Characteristics:
Accuracy and Precision: A synthetic unknown sample containing 120 pg/1 Mn, 500
7'g/l All 50 ug/1 Cd, 110 pg/1 Cr, 470 ug/1 Cu, 30 ug/1 Fe, 70 ug/1 Pb, 150 pg/1 Ag,
and 650 ug/1 Zn in distilled water was determined by the periodate method, with a
relative standard deviation of 36.0% and a relative error of 25.0% in 14 laboratories.
Time of Measurement: Not stated
Calibration Requirements: Calibration curve is generated using dilution of a
standard solution.
Data Outputs; Analog instrument reading or visual comparison.
Special Sampling Requirements: Manganese should be determined very soon after sample
collection. When delay is unavoidable, a total manganese can be determined if the
sample is acidified at the time of collection
Reference; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al..
Washington, D. C. (1971).
*
Units as given in Reference cited.
C-22
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C-24
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Manganese
Medium: Drinking Water
Name of Measurement Method: Persulfate Method
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications): Manganese imparts objectionable and
tenacious stains to laundry and plumbing fixtures.
Summary of Method: Fersulfate oxidation of soluble manganous compounds to form
permanganate is carried out in the presence of silver nitrate. The resulting color
is stable for at lease 2k hrs. if excess persulfate is present and organic matter is
absent. The color produced is proportional to the concentration of manganese present.
Limitations:
Range of Applicability: Minimum detectable concentration: 5 ug Mn
Interferences: Sodium cnloride >0.1 gram
Excessive amounts of bromide and iodine
Pitfalls; Special Precautions: Not stated
Statistical Characceriscics:
Accuracy and Precision: A synthetic unknown sample containing 120 pg/1 Mn,
500 ug/1 Al, 50 ug/1 Cd, 110 ug/1 Cr, 470 ug/1 Cu, 300 pg/1 Fe, 70 pg/1 Pb,
150 ug/1 Ag and 650 ug/1 Zn in distilled water had a relative standard
deviation of 26.3% and a relative error of 0% in 33 laboratories. A second
synthetic unknown sample, similar in all respects except for 50 ug/1 Mn and
1,000 pg/1 Cu, had a relative standard deviation of 50.3% and a relative
error of 7.2% in 17 laboratories.
Time of Measurement: Not stated
Calibration Requirements: Calibration curve is generated using dilution of a
standard solution.
Data Outputs: Analog instrumental reading or visual comparison.
Special Sampling Requirements (Collection. Storage, Handling): Manganese should be
determined very soon after sample collection. When delay is unavoidable, a total
manganese can be determined if the sample is acidified at the time of collection.
Reference: Standard Methods for Examination of Water and Uastewatcr,
13th Edition, American Public Health Association, et al..
Washington, D. C. (1971).
Units as stated in cited Reference.
C-23
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C-25
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Mercury
Medium: Drinking Water
Name of Measurement Method: Cold Vapor Method
Principal Detection Technique: Atomic Absorption Spectroscopy
Purpose of Measurement (Important Applications): To determine total mercury
(organic and inorganic) in potable water. Also applicable to surface waters
and various industrial effluents. May be adapted to apply to fish tissue.
Summary of Method: This is a physical procedure based on the absorption of
radiation at 253.7 nm by mercury vapor. Mercury in solution is reduced to
the elemental state then aerated from solution and the vapor passed through
a cell positioned in the light path of an atomic absorption spectrometer.
Absorbance (peak height) is a function of mercury concentration.
Mercury from organic compounds must be converted to ionic form before
being reduced to the elemental state. This is accomplished by oxidizing the sample
with potassium permanganate and potassium persulfate in an acidic medium.
Excess permanganate Is reduced by sodium chloride hydroxylamine. Mercury ions
then are reduced to elemental mercury by stannous sulfate. The processed sample
is aerated in a closed system such that the mercury vapor passes through the
absorption cell in the AA speccrophotometer.
Limitations:
Range of Applicability: Range is adjusted to about 0.02 - 0.5 ug Hg per
sample aliquot. For 100 ml aliquot, this corresponds to 0.2 - 5.0 ug/1.
Range can be varied by instrument adjustment and/or recorder expansion.
Interferences: Sulfides (interference eliminated by potassium permanganate);
high concentrations of copper or chloride; certain volatile organic compounds.
Pitfalls; Special Precautions: Absorption of radiation by water vapor.
Loss of mercury in sample handling and storage.
Statistical Characteristics:
Accuracy and Precision: Analyses of a composite sample of river water
containing background mercury concentration of 0.35 ug/1 and spiked with
concentrations of 1.0, 3.0, and 4.0 ug/1 yielded recoveries of 89, 87, and
87 percent, respectively, and exhibited standard deviations of +0.14, + 0.10,
and + 0.08, respectively.
Time of Measurement; Not stated, but not instantaneous, since the oxidation
step requires over 2 hours.
Calibration Requirements: See Reference
Data Outputs: Analog electrical signals displayed on stripchart.
Special Sampling Requirements (Collection, Storage, Handling): Acidify sample
to pH of 2 or less upon collection.
References: Kopp, John F., et al "'Cold Vapor' Method for Determining Mercury",
Journal of the American Water Works Association (January, 1972).
C-24
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C-26
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Metals
Aluminum Chromium Magnesium
Barium Copper Manganese
Beryllium Iron Silver
Cadmium Lead Zinc
Medium; Drinking Water
Hame of Measurement Method: Atomic Absorption Spectrometry
Purpose of Measurement (Important Applications): For rapid determination of
certain metals in aqueous solution.
Summary of Method; Atomic absorption spectroscopy is similar to flame emission
photometry in that a sample is atomized and aspirated into a flame. Flame
photometry measures the amount of light emitted, whole atomic absorption spectro-
photometry measures the amount of light absorbed. Absorption is usually more
sensitive because It depends upon the presence of free, unexclted atoms and
generally the ratio of unexclted to excited atoms at a given moment is very
high. Since the wavelength of the light beam is characteristic of only the
metal being determined, the light energy absorbed by the flame Is a measure
of the concentration of that netal in the sample.
Analytical procedures specific to each of the metals listed above are
given in the Reference cited.
Limitations;
Range of Applicability and Sensitivity; Detection limits and sensitivities
may vary with make and model of atomic absorption spectrometer. The
following table provides some indication of certain parameters of measurement.
Metal
Aluminum
Barium
Beryllium
Cadmium
Chromium
Copper
Iron
Lead
Magnesium*
Manganese*
Silver
Zinc
Statistical Characteristics:
Wavelength
nu
309.3
553. 6
234.8
228.8
357.9
324.7
248.3
283.3
285.2
279.4
328.1
213.8
Sensitivity*
ug/1 per 1 Percent
l.OOOpg/l*
200
100
40
150
200
300
500
15
ISO
100
40
Accuracy and Precision Data: Results of determinations made at several
laboratories (the number varies from 10 to 59 for the various metals
determined) are summarized In the following table:
Metal
Extracted Samples:
Aluminum
Beryllium
Cadmium
Lead
Direct Determination;
Barium
Cadmium
Chromium
Copper
Iron
Magnesium
Manganese
Silver
Zinc
Metal
Concentration
UK/1
50
300
750
5
50
100
10
50
500
1,000
5,000
50
50
1,000
300
200
50
50
500
Relative Relative Standard
Error Deviation
Percent Percent
26.0
0.7
7.9
20.0
2.0
3.0
3.0
19.0
8.6
2.7
1.4
8.2
2.3
3.4
0.6
6.3
6.0
10.6
0.4
76.2
22.2
16.5
34.0
39.2
35.0
72.8
23.5
10.0
8.9
3.7
21.6
26.4
11.2
16.5
10.5
13.5
17.5
8.2
Time of Measurement; Rapid
Calibration Requirements; See Reference
Data Outputs: Electrical signals
Special Sampling Requirements (Collection. Storage. Handling):
See Reference.
Reference; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al..
Washington, D.C. (1971).
C-25
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C 28
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Nitrate**
Medium; Drinking Water
Name of Measurement Method; Ultraviolet Spectrophotometric Method**
Principal Detection Techniques; Colorimetric
Purpose of Measurement (Important Applications); Nitrate in excessive amounts,
contributes to the illness known as infant methemoglobinemia. A limit of 45 mg/1
nitrate has accordingly been imposed on drinking waters as a means of averting
this condition.
Summary of Method; Measurement of the ultraviolet absorption at 220 mu enables
a rapid means of determining nitrate. The nitrate calibration curve follows
Beer's law up to 11 mg/1 N. Because dissolved organic matter may also absorb
at 220 mv and nitrate does not absorb at 275 mp, a second measurement is made at
275 mv for the purpose of correcting the nitrate value.
Limitations;
Ranee of Applicability; Near 40 Ug/1 up to 11 mg/1 nitrate nitrogen.
Sensitivity; Minimum detectable cone. - 40 gg/1 N
Interferences; Dissolved organic matter, nitrite, hexavalent chromium, and
surfactants interfere. The latter three substances may be compensated for
by the preparation of individual correction curves. Organic matter causes
a positive but variable interference.
Statistical Characteristics;
Accuracy and Precision; Not stated
Time of Measurement: Not stated
Calibration Requirements: Calibration curves are prepared using a standard solution
and correction curves are prepared using each expected interference.
**Comments by Users; This method is seldom used; instead, the Brucine. cadium
reduction, or chromoitropic acid methods described in Section 213 of cited Reference
are recommended..
Data Outputs: Analog instrument reading
Special Sampling Requirements (Collection. Storage. Handling); None stated
Reference; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al. .
Washington, D.C. (1971).
C-26
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C-29
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Odor
Medium: Drinking Water
Name of Measurement Method: Threshold Odor Number
Principal Detection Techniques: Odor
Purpose of Measurement (Important Applications): Taste and odor tests are useful as
a check on the quality of raw and finished water; for control of odor through the plant
and the determination of treatment dosages; as a test of the effectiveness of different
kinds of treatment; and as a means of tracing the source of contamination.
Summary of Method; The sample of water is diluted with odor-free water until a
dilution that is of the least definitely perceptible odor to each tester is found.
Panels of not less than five persons, and preferably 10 or more, are recommended to
overcome the variability of using one observer.
Limitations;
Range of Applicability: This threshold method is applicable to samples ranging
from nearly odorless natural waters to industrial wastes with threshold numbers
in the thousands.
Interferences; Not stated
Pitfalls; Special Precautions: Threshold values will vary with temperature; the
temperature at which observations are made should always be reported. All glass-
ware should be odor free.
Statistical Characteristics:
Accuracy and Precision: A threshold number is not a precise value. In the case
of the single observer, it represents a judgement at the time of testing. Panel
results are more meaningful because individual differences have less influence
on the result. Comparisons of data from time to time or place to place should
not be attempted unless all test conditions have been carefully standardized
and some basis for comparison of observer intensities exists.
Time of Measurement: Not stated
Calibration Requirements: None
Data Outputs:
Special Sampling Requirements (Collection. Storage, Handling); Samples should be
collected in glass bottles with glass or teflon-lines closures. If storage is
necessary the sample should be refrigerated.
References: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al..
Washington, D. C. (1971).
C-27
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C-30
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Organic Contaminants
Medium: Drinking Water
Name of Measurement Method: High-flow carbon adsorption method
Principal Detection Techniques: Gravimetric
Purpose of Measurement (Important Applications): According to the 1962 USPHS
Drinking Water Standards, a concentration of 200 pg/1 of CCE should not be exceeded.
Contaminants, both natural and man-made, can conceivably have undesirable effects on
health. Some of these materials interfere with water quality and kill fish.
Summary of Method: Activated carbon is an effective adsorption medium for many types
of organic materials. As used in a carbon adsorption unit (see diagram shown in reference),
it aids in the detection of low but significant quantities or organic contaminants
in large volumes of water. When a sufficient quantity of water has been run through
the unit, the carbon containing the adsorbed sample is removed, dried, and extracted
with chloroform. The removal of the chloroform by distillation leaves a weighable
residue of contaminants. Other solvents, such as ethyl alcohol, will remove additional
organics, but for monitoring and control purposes the chloroform extraction is
considered adquate.
Limitations:
Range of Applicability: This method is applicable to drinking waters but is
not limited to them.
Interferences: Not stated
Pitfalls; Special Precautions: Carbon does not adsorb all organics.
Statistical Characteristics:
Accuracy: Not given
Precision: Replicate samples agree within + 10 percent.
Recovery: Using known amounts of easily adsorbed materials, recoveries
may range from 50 to 90 percent.
Calibration Requirements: See Reference
Data Outputs: Mechanical scale
Special Sampling Requirements (Collection. Storage. Handling): See Reference
Reference; Standard Methods for Examination of Water and Wastewater, 13th Edition,
American Public Health Association, et al.. Washington, D.C. (1971).
C-28
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C-32
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Organic Contaminants
Medium: Drinking Water
Name of Measurement Method: Carbon Adsorption/Solvent Extraction MpthnH
Principal Detection Techniques: Gravimetric
Purpose of Measurement (Important Applications): According to the USPHS
Drinking Water Standards, a concentration of .70 mg/1 of CCE (carbon chloroform
extract) and 3.0 mg/1 of CAE (carbon alcohol extract) should not be exceeded.
Contaminants, both natural and man-made, can conceivably have undesirable
effects on health. Some of these materials interfere with water quality and
kill fish.
Summary of Method: tnis is a gravimetric adsorption/extraction method.
Organic materials adsorbed on a sample of activated carbon are removed by
sequential extraction with two organic solvents. The extracts are processed
by volume reduction through distillation and drying. The quantities of
organic materials are then determined gravimetrically. This method employs
a flow rate of 20 ml/min. and utilizes a miniature sampling apparatus.
Limitations:
Range of Applicability: Surface or treated waters, or groundwater.
Interferences: None specifically identified
Pitfalls; Special Precautions: Some organic compounds cannot be adsorbed
on activated carbon or recovered from the activated carbon by the solvents
used in this method. In organics substances may contribute to the weight
of the extract (positive error).
Statistical Characteristics:
Accuracy and Precision: The coefficient of variation of CCE-m and CAE-m
extracts using 70 gm of activated carbon exposed to same water in separated
mini-samplers ranged from 2.6-3.0% and 7.4-9.1%, respectively.
Time of Measurement: Sampling time is two days, total time of analysis is
8-9 days, actual manhour requirement.is less than six.
Calibration Requirements: See reference.
Comments by Users: Method is primarily for monitoring the general organic
content of water.
Data Outputs: Scale reading. Visual observation, manually recorded.
Special Sampling Requirements (Collection. Storage. Handling): If storage is
necessary, the dried, exposed activated carbon sample can be stored in sealed
glass containers at 4°C. (Uses special mini-sampler).
References: Buelow, R. W., Carswell, J. K., Symons, J. M., "An Improved
Method for Determining Organics in Water by Activated Carbon Adsorption and
Solvent Extraction", U.S. Environmental Protection Agency, Water Supply Research
Laboratory, National Environmental Research Center, Cincinnati, Ohio,
July, 1972 (Prepublication copy).
C-29
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C-33
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: ?H
Medium: Water (Drinking)
Name of Measurenent Method: Glass Electrode
Principal Detection Technique: Electrometric
Purpose of Measurement (Important Applications): Adjustment of the pH of
treatment plant effluent is practiced to control corrosion in the distribution
system.
Summary of Method: Several types of electrodes have been suggested for the
electrometric determination of pH. Although the hydrogen gas electrode is
recognized as the primary standard, the glass electrode in combination with
the reference potential provided by a saturated calomel electrode is most
generally used. The glass electrode system is based on the fact that a change
of 1 pH unit produces an electrical change of 59.1 mV at 25 C.
Limitations:
Range of Applicability: All ranges
Interferences: All interferences can be corrected except the variation
in the ionization of the sample with temperature.
Pitfalls; Special Precautions: Not stated
Statistical Characteristics:
Accuracy: +0.1 ph unit represents the limit of accuracy under
normal conditions.
Precision: A synthetic unknown sample was determined in 30 laboratories
with a standard deviation of +_ 0.13 pH unit.
Time of Measurement: Not stated
Calibration Requirements: No unusual requirements.
Data Outputs: Analog output
Special Sampling Requirements (Collection, Storage, Handling): None stated
References: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D.C. (1971).
C-30
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C-34
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Phenol
Medium! Drinking water
Name of Measurement Method: Colorimetric Determination
Principal Detection Technique; Colorimetric
Purpose of Measurement (Important Applications): Phenols appear in waste products of
oil refineries, coke plants and some chemical-producing facilities. Concentrations of
the order of 10 to 100 ug/1 are detectable by the taste and odor test. Trace amounts
approaching 1 ug/1 can impart an objectionable taste to a water following marginal
chlorination.
Summary of Method: Steam-distillable phenols react with 4-aminoantipyrlne at a
pH of 10.0 + 0.2 in the presence of potassium ferricyanide to form a colored anti-
pyrlne dye. This dye is extracted from aqueous solution with chloroform and the
absorbance is measured at 460 mp. (The concentration of phenolic compounds is
expressed as ug/1 of phenol.)
Limitations:
Range of Applicability: 0.0 to 1,000 ug/1 Phenol. The minimum detectable
quantity is 0.5 ug/1 Phenol in a 500 ml distillate.
Interferences: Phenol-decomposing bacteria, oxidizing and reducing agents,
and high alkalinity. Some of the treatment procedures used for the removal of
interferences prior to analysis may result in an unavoidable loss of certain
types of phenolic substances.
Pitfalls; Special Precautions: The percentage composition of the various
phenolic compounds present in a given sample is unpredictable. It is obvious,
therefore, that a standard containing a mixture of phenolics cannot be made
applicable to all samples. For this reason, phenol itself has been selected
as a standard, and any color produced by the reaction of other phenolic
compounds Is reported as phenol. This value will represent the minimum
concentration of phenolic compounds present In the sample.
Statistical Characteristics:
Accuracy and Precision; A synthetic unknown sample containing 2.0 ug/1
phenol in distilled water was determined by the distillation and chloroform-
extraction methods, with a relative standard deviation of 81.3Z and a relative
error of 45.2% in 65 laboratories. A second synthetic unknown sample containing
50 ug/1 phenol in distilled water was determined by the distillation and
chloroform-extraction methods, with a relative standard deviation of 20. BZ and
a relative error of 7.2% In 69 laboratories.
Time of Measurement: Not stated
Calibration Requirements: See reference
Comments by Users: Method provides extreme sensitivity and is adaptable for use in
water containing less than 1 mg/1 phenol.
Data Outputs: Analog electrical signal.
Special Sampling Requirements (Collection. Storage. Handling): Phenols in concentrations
found in wastewater are subject to biochemical and chemical oxidation. Samples should be
preserved by pH adjustment and addition of reagents unless they will be analyzed within
4 hours after collection.
Reference: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D.C. (1971).
C-31
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C-35
SUMMARY QF ANALYTICAL METHOD
Parameter(s) Measured: Phenol
Medium; Drinking Wacer
Name of Measurement Method: Direct Photometric
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications): Phenols are found in waste products
of oil refineries, coke plants and some chemical-producing facilities. Concentrations of
the order of 10 to 100 pg/1 are detectable by the taste and odor test. Trace amounts
approaching 1 ug/1 can impart an objectionable taste to a water following marginal
chlorinaLlon.
Summary of Method: The steam-distillable phenols react with 4-aminoantipyrine at a
pH of 10.0 ±0.2 in the presence of potassium ferricyanide to form a colored antl-
pyrlne dye. This dye is kept in an aqueous solution and the absorbance is measured
at 510 my.
Limitations:
Range of Applicability: 0.0 to 50 mg/1 phenol. The minimum detectable
quantity is 0.1 mg phenol when a 5-cm cell is used in the photometric
measurement and 100 ml distillate are used in the determination.
Interferences: All interferences are eliminated or reduced to a minimum
by using only the distillate from the preliminary distillation procedure.
Pitfalls; Special Precautions; The percentage composition of the various
phenolic compounds present in a given sample is unpredictable. It is obvious,
therefore, that a standard containing a mixture of phenols cannot be made
applicable to all samples. For this reason, phenol itself has been selected
as a standard, and any color produced by the reaction of other phenolic
compounds is reported as phenol. This value will represent the minimum
concentration of phenolic compounds present in the sample.
Statistical Characteristics:
Accuracy and Precision: The precision of this method is dependent on the skill
of the analyst and on the interferences present after the distillation procedure.
Because the "phenol" value is based on C.H^OH, this method can be regarded only
as an approximation and as representing the minimum amount of phenols present.
Time of Measurement: Not stated
Calibration Requirements: See Reference
Data Outputs: Analog electrical signal; instrumental output.
Special Sampling Requirements (Collection. Storage. Handling); Phenols in concen-
trations found in washwater are subject to biochemical and chemical oxidation.
Samples should be preserved by pH adjustment and reagents unless they will be
analyzed within 4 hours after collection.
Reference; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al..
Washington, D.C. (1971).
C-32
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C-36
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radium 226
Medium: Water (Drinking)
Name of Measurement Method:
Principal Detection Technique: Counting
Purpose of Measurement (Important Applications):
Summary of Method; The radium in water is concentrated and separated from sample
solids by coprecipitation with a relatively large amount of barium as the sulfate.
The precipitate is treated to remove silicates, if present, and to decompose
insoluble radium compounds; fumed with phosphoric acid to remove 803;and dissolved in
HC1. The completely dissolved radium is placed in a bubbler, which is then closed
and stored for a period of several days to four weeks for ingrowth of radon. The
bubbler is connected to an evacuated system and the radon gas is removed from the
liquid by aeration, dried with a desiccant, and collected in a counting chamber.
About four hours after radon collection, the alpha-counting rate of radon and
decay products is at equilibrium, and a count is obtained and related to radium 226
standards similarly treated.
Limitations:
Range of Applicability: Minimum detectable amount under routine conditions
is between 0.03 and 0.05 pCi.
Interferences: Radon 219, Radon 220.
Pitfalls; Special Precautions; Since some radium 226 is present in barium
salts, reagent tests are necessary in order to account for radium 226 intro-
duced in this way.
Statistical Characteristics:
Accuracy: The average recoveries of added radium 226 from four samples by
seven laboratories were 97.1, 97.3, 97.6 and 98.0 percent.
Precision; At the 95 percent confidence level, the precision was 6 percent
and 8 percent for two sets of paired samples (one simulated moderately hard
water and the other sample simulated hard water).
Time of Measurement! Not stated, but 4 weeks required for daughter ingrowth.
Calibration Requirements: When an Internal proportional counter is used the
system is calibrated by adding standard nuclide portions to media comparable
to the samples and preparing, mounting, and counting the standards identical
to that of the samples.
Data Outputs: Digital output.
Special Sampling Requirements (Collection. Storage. Handling): None stated
References; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D.C. (1971).
C-33
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C-37
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Selenium
Medium: Drinking Water
Name of Measurement Method: Diaminobenzidine Method
Principal Detection Technique; Colorimecric
Purpose of Measurement (Important Applications): Selenium has a toxic
effect upon man and animals comparable to that of arsenic. The maximum
allowable concentration permitted by the Public Health Service Drinking
Water Standards is 0.01 mg/1.
Summary of Method: Selenium compounds are oxidized to selenate by acid
permanganate. Selenate is then reduced to selenite in warm 4N HC1.
Selenite and the diaminobenzidine solution are reacted in the presence
of heat to form piazselnol. Piazselnol is extracted using toluene and
the absorbance is determined. Extraction of piazselenol is not quanti-
tative, but an equilibrium is attained rapidly.
Limitations:
Range of Applicability; Not given by Reference cited.
Sensitivity: Minimum detectable limit with 4 cm light path
is 1 iig Se (as stated in Reference cited)
Interferences: Iodide, Bromide
Pitfalls; Special Precautions: None cited
Statistical Characteristics:
Accuracy and Precision: A synthetic unknown sample containing 20 ug/1
Se, 40 ug/1 As, 250 Mg/1 Be, 240 ug/1 B, and 6 ug/1 V in distilled
water was determined with a relative standard deviation of 21.2 percent
and a relative error of 5.0 percent in 35 laboratories.
Time of Measurement: Not stated.
Calibration Requirements: Standard Curve
Data Outputs: Analog electrical signal readout
Special Sampling Requirements (Collection. Storage, Handling): Not stated.
Reference : Standard Methods for Examination of Hater and Waslewater,
13th Edition, American Public Health Association, et al. ,
Washington, D. C. (1971).
C-34
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C-38
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Selenium
Medium: Drinking Water
Name of Measurement Method: Distillation and Diaminobenzidine Method
Principal Detection Technique: Colorimetric
Purpose of Measurement (Important Applications): Selenium has a toxic
effect upon man and animals comparable with that of arsenic. The maximum
allowable concentration permitted by the Public Health Service Drinking
Water Standards is 0.01 mg/1.
Summary of Method: Selenium is quantitatively separated from most other
elements by distillation of the volatile tecrabromide from an acid solution
containing bromine. Selenium tetrabromide, along with a minimum of excess
bromine is absorbed in water, and the excess bromine is removed by precipitation
as tribromophenol. The quadrivalent selenium remaining in solucion is
determined with diaminobenzidine as described in the Method Summary for
Selenium using the Diaminobenzidine Method.
Limitations:
Range of Applicability: Not stated.
Sensitivity: Minimum detectable concentration with 4 cm
light path is 1 pg Se.
Interferences: None
Pitfalls; Special Precautions: Not stated
Statistical Characteristics:
Accuracy and Precision: A synthetic unknown sample containing 20 ug/1
Se, 40 ug/1 As, 250 ug/1 Be, 240 ug/1 B, and 6 ug/1 V in distilled
water was determined with a relative standard deviation of 21.2 percent
and a relative error of 5.0 percent in 35 laboratories.
Time of Measurement; Not stated
Calibration Requirements: Standard Curve
Data Outputs: Analog readout
Special Sampling Requirements (Collection, Storage, Handling):
References: Standard Methods for Examination of Water and Wastewatcr,
13th Edition, American Public Health Association, et al. .
Washington, D. C. (1971).
C-35
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C-39
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Silver
Medium: Water (Drinking)
Name of Measurement Method: Dithizone Method
Principal Detection Technique: Colorimetric
Purpose of Measurement (Important Applications): Silver can cause argyria, a per-
manent, blue-gray discoloration of the skin and eyes which presents a ghostly
appearance. This method is useful when atomic absorption is not available.
Summary of Method: Twenty metals are capable of reacting with dithizone to
produce colored coordination compounds. Under Che proper conditions or upon
the removal of all interferences, the reaction can be made selective for a
desired substance. The determination is then made by colorimctry.
Limitations:
Range of Applicability: Minimum detectable concentration: 0.2 ug Ag.*
Interferences: Extraction of the silver along with other metals
overcomes oxidation interferences from contaminants.
Pitfalls; Special Precautions: The extreme sensitivity, as well
as silver's affinity for being adsorbed, makes it desirable to
prepare and segregate glassware especially for this determination,
and to take unusual precautions at every step in the procedure.
Dithizone and the silver dithozonate both decompose rapidly in
strong light; therefore, they should not be left in the light beam
of the photometer for a longer period than is necessary.
Statistical Characteristics:
Precision and Accuracy: A synthetic unknown sample containing
150 ug/1 Ag, 500 fig/1 Al, 50 ug/1 Cd, 110 ug/1 Cr, 470 ug/1 Cu,
300 ug/1 Fe, 70 ug/1 Pb, 120 ug/1 Mn and 650 ug/1 Zn in distilled
water was determined by the dithizone method, with a relative
standard deviation of 61.0 percent and a relative error of 66.6
percent in 14 laboratories.
Time of Measurement: Not stated
Calibration Requirements: No unusual requirements
Comments by Users: In view of the sensitivity of the reaction and the
numerous Interferences among the common metals, the method is somewhat
empirical and demands careful adherence to the procedure.
Data Outputs: Analog reading
Special Sampling Requirements (Collection, Storage, Handling): Samples should
be examined as soon as possible after collection because of the silver loss
which may occur through adsorption on the container walls. The addition of a
small volume of nitric acid of known purity is advisable when sample storage
time is excessive. Sample containers should be washed with nitric acid
and rinsed with silver-free water before use.
References; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D.C. (1971).
*As stated in Reference
C-36
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C-40
SUMMARY OF ANALYTICAL METHOD
Paraiiieteris) Measured: Sodium
Medium: .Viilcr (Drinking)
Name of Measurement Method: Flame Photometric Method
Principal Detection Technique: Flame Photometry
Purpose of Measurement (Important Application): The ratio of sodium to total
cations is important in agriculture and human pathology. Soil permeability
has been found to be detrimentally affected by a high sodium ratio, while
certain diseases require water with a low sodium concentration.
Summary of Method; The sample is sprayed into a gas flame and excitation
is carried out under carefully controlled and reproducible conditions. The
desired spectral line is isolated and the intensity of light is then measured
by a phototube potentiometer or other appropriate circuit. The intensity
of light at 589 m|i is approximately proportional to the concentration of the
element.
Limitations:
Range of Applicability: With proper modifications in technique
the sodium level can be extended to 10 ug/1 or lower.
Interferences; Burner-clogging particulate matter should be
removed from the sample by filtration through a quantitative
filter paper of medium retentiveness. The problems of interference
can be minimized by procedures cited in Reference.
Pitfalls: Special Precautions: Locate the flame photometer in
an area away from direct sunlight or the constant light emitted
by an overhead fixture, and free of drafts, dust and tobacco
smoke. Guard against contamination arising from corks, filter
paper, perspiration, soap, cleansers, cleaning mixtures and
inadequately rinsed apparatus.
Statistical Characteristics;
Precision and Accuracy: A synthetic unknown sample containing
19.9 mg/1 Na, 108 mg/1 Ca, 82 mg/1 Mg, 3.1 mg/1 K, 241 mg/1 chloride,
250 ug/1 nitrite N, 1.1 mg/1 nitrate N, 259 mg/1 sulfate, and 42.5 mg/1
total alkalinity (contributed by NaHCC>3) was determined by the flame
photometric method, with a relative standard deviation of 17.3 percent
and a relative error of 4.0 percent in 35 laboratories.
Time of Measurement: Not stated
Calibration Requirements: No unusual requirement
Comments by Users: The flame photometric method is more rapid and
sensitive and generally more accurate than the gravimetric method, especially
for sodium concentrations below 10 mg/1.
Data Output: Analog reading
Special Sampling Requirements (Collection, Storage, Handling): Alkaline samples
or samples containing low sodium concentrations should be stored in polyethylene
bottles in order to eliminate the possibility of contamination of the sample
due to leaching of the glass container.
References: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al. '
Washington, D.C. (1971).
C-37
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C-41
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Specific Conductance
Medium: Water (Drinking)
Name of Measurement Method:
Principal Detection Technique: Electrometric
Purpose of Measurement (Important Applications): Specific conductance measure-
ments make possible the determination of the amount of ionic reagent needed in
certain precipitation and neutralization reactions.
Summary of Method: Specific conductance yields a measure of a water's capacity
to convey an electric current. This property is related to the total concen-
tration of the ionized substances in a water and the temperature at which the
measurement is made. A conductance cell and a Wheatscone bridge are essential
for measuring the electrical resistances of the sample and of a potassium
chloride solution of known specific conductance at the same temperature.
Limitations:
Range of Applicability: All ranges
Interferences: Not stated
Pitfalls; Special Precautions; Conductivity varies with temperature,
therefore all results are reported at 25°C.
Statistical Characteristics:
Accuracy and Precision: The precision and accuracy with which the
conductance of water can be determined depends on the equipment being
used. A precision and accuracy of about + 5% are possible with the
better commercial instruments.
Time of Measurement: Not stated
Calibration Requirements; Factor for converting specific conductance
measurements to 25°C are based upon a standard potassium chloride solution.
Data Outputs: Analog voltage
Special Sampling Requirements (Collection, Storage, Handling); None
References: Standard Methods for Examination of Water and Wastewator,
13th Edition, American Public Health Association, et al.,
Washington, D.C. (1971).
C-38
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C-42
SUMMARY OF ANALYTICAL METHOD
Parameter(3) Measured: Strontium 90
Medium: Water (Drinking)
Name of Measurement Metnod:
Principal Detection Technique: Counter
Purpose of Measurement (Important Applications): The 1962 Public Health Service
Drinking Water Standards limit the concentration of 90Sr in water to 10 pCi/1
when other sources of intake are not considered.
Summary of Method: A known amount of inactive strontium ions, in the form of
strontium nitrate, is added as a carrier. The carrier is precipitated as the
carbonate to concentrate the radlostrontium. The carrier, along with the radio-
nuclides of strontium, is separated from other radioactive elements and in-
active sample solids by precipitation as strontium nitrate from fuming nitric
acid solution. The strontium carrier, together with the radlonuclides of
strontium, is finally precipitated as strontium carbonate, which is dried,
weighed to determine recovery of carrier, and then measured for radioactivity.
Limitations:
Range of Applicability:
Interferences: All can be eliminated through separation techniques.
Pitfalls; Special Precautions: The final count must be corrected for
the carrier efficiency.
Statistical Characteristics:
90
Accuracy: The average recoveries of added Sr from four samples of
moderately hard water were 90, 96, 80 and 94 percent.
Precision; The precision at the 95 percent confidence level was 14
and 28 percent for the two sets of paired samples.
Time of Measurement: Not stated
Calibration Requirements: When an internal proportional counter is used
the system is calibrated by adding standard nucllde portions to media comparable
to the samples and preparing, mounting, and counting the standards identical
to that of the samples.
Data Outputs: Digital output
Special Sampling Requirements (Collection. Storage, Handling): None stated
References: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al..
Washington, D.C. (1971).
C-39
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SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Sulfate
Medium; Drinking water
Name of Measurement Method: Gravimetric method with drying of residue
Principal Detection Techniques: Gravimetric
Purpose of Measurement (Important Applications): Sulfate is widely distributed
in nature and may be present in natural waters in concentrations ranging from a
few to several thousand mg/1. Sodium sulfate exerts a cathartic action. The
recommended sulfate concentration in potable supplies is limited to 250 mg/1.
This method is relatively rapid and is useful when highest accuracies are not
required.
Summary of Method: Sulfate is precipitated in a hydrochloric acid medium as
barium sulfate by the addition of barium chloride. The precipitation is carried
out near the boiling temperature,and after a period of digestion the precipitate
is filtered, washed with water until free of chlorides, dried, and weighed as
BaS04.
Limitations:
Range of Applicability; Not stated.
Interferences: Suspended matter, silica,barium chloride precipitant, nitrate,
sulfite, water, and alkali metals.
Statistical Characteristics:
Accuracy and Precision: Method it, acceptable In routine work where the greatest
attainable accuracy is not required. Specific data not given in Reference cited.
Time of Measurement: Not stated
Calibration Requirements; Standard Curve
Data Outputs: Mechanical scale reading.
Special Sampling Requirements(Collection. Storage. Handling): Samples should be
stored at low temperatures or treated with formaldehyde.
Reference: standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
C-40
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C-44
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measures; Sulfate
Medium; Drinking Hater
Name of Measurement Method: Gravimetric Method with Ignition of Residue
Principle Detection Techniques: Gravimetric
Purpose of Measurement (Important Applications): This method Is relatively time
consuming, but is considered to provide high accuracy.
Sulfate is widely distributed in nature and may be present In natural waters
in concentrations ranging from a few to several thousand mg/1. Sodium sulfate exerts
a cathartic action. The recommended sulfate concentration in potable supplies is
limited to 250 mg/1.
Summary of Method: Sulfate is precipitated in a hydrochloric acid medium as
barium sulfate by the addition of barium chloride. The precipitation is carried
out near the boiling temperature, and after a period of digestion the preci-
pitate is filtered, washed with water until free of chlorides, Ignited or dried
at about 800 C, and weighed as barium sulfate.
Limitations:
Range of Applicability; Not stated.
Interferences; Suspended matter, silica, barium chloride precipitant, nitrate,
sulfite, water and alkali metals.
Statistical Characteristics:
Accuracy and Precision: A synthetic unknown sample containing 259 mg/1 sulfate,
108 mg/1 Ca, 82 mg/1 Mg, 3.1 mg/1 K, 19.9 mg/1 Na, 241 mg/1 chloride, 250 g/1
nitrite N, 1.1 mg/1 nitrate N, and 42.5 rag/1 total alkalinity (contributed
by NaHC03) was determined by the gravimetric method, with a relative standard
deviation of 4.72 and a relative error of 1.9% in 32 laboratories. Most
accurate method for sulfate concentrations above 10 mg/1.
Time of Measurement: Not stated
Calibration Requirements: No unusual requirement
Data Outputs: Mechanical scale reading.
Special Sampling Requirements (Collection. Storage. Handling): Sample should be
stored at low temperatures or treated with formaldehyde.
Reference: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
C-41
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C-45
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measures: Sulfate
Medium: Drinking Water
Name of Measurement Method: Turbidimetric Method
Principle Detection Techniques; Nephelometry
Purpose of Measurement (Important Applications): This method is quite rapid, but
its accuracy is sensitive to several factors, including skill of the analyst.
Sulfate is widely distributed in nature and may be present in natural waters in
concentrations ranging from a few to several thousand mg/1. Sodium sulfate exerts
a cathartic action. The recommended sulfate concentration in potable supplies is
limited to 250 mg/1.
Summary of Method: Sulfate ion is precipitated in a hydrochloric acid
medium with barium chloride in such manner as to form barium sulfate crystals of
uniform size. The absorbance of the barium sulfate suspension is measured by
a nephelometer or transmission photometer and the sulfate ion concentration is
determined by comparison of the reading with a standard curve.
Limitations:
Range of Applicability: 1-60 mg/1 sulfate
Interferences: Color or suspended matter
Statistical Characteristics:
Accuracy and Precision: A synthetic unknown sample containing 259 mg/1 sulfate,
108 mg/1 Ca, 82 mg/1 Mg, 3.1 mg/1 K, 19.9 mg/1 Na, 241 mg/1 chloride, 250 g/1
nitrite N, 1.1 mg/1 nitrate N, and 42.5 mg/1 total alkalinity (contributed by
NaHCO,) was determined by the turbidimetric method, with a relative standard
deviation of 9.1Z and a relative error 1.2% in 19 laboratories.
Time of Measurement: Not stated
Calibration Requirements: Calibration curve is prepared from a standard sulfate
solution.
Data Outputs: Analog instrumental output, manually recorded.
Special Sampling Requirements: Sample should be stored at low temperature or
treated with formaldehyde.
References: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al..
Washington, D. C. (1971).
C-42
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C-46
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measures: Surfactants (Anionlc)
Medium: Drinking Water
Name of Measurement Method: Carbon Adsorption Method
Principal Detection Techniques: Infrared spectrophotometric, or colorimetrlc
Purpose of Measurement (Important Applications; The permissible concentration
of surfactants is limited by the U.S. Public Health Service Drinking Water
Standards. This method is useful to determine the concentration of LAS (linear
alkyl sulfonate) in a sample shown by the methylene blue method to contain
high concentrations of methylene-blue active substances (which include both
LAS and ABS).
Summary of Method: This method involves the collection and Isolation of a
few milligrams of LAS and its quantitative determination based on infrared
absorption of an amine complex of LAS. When an infrared spectrophotometer
is not available a colorimetrlc determination can be substituted by recovering the
purified LAS and applying the methylene blue method (See Summary for that method).
Limitations;
Range of Applicability; Low LAS concentrations
Interferences: Not stated.
Pitfalls; Special Precautions: Most samples contain both solid and liquid
phases, and LAS is highly concentrated in the solid phase. For accurate
analysis, it is essential that the solids be representatively sampled or
excluded.
Statistical Characteristics:
Accuracy and Precision: This method is specific and accurate for low LAS
concentrations in water. Specific data not given in Reference.
Time of Measurement: Method is lengthy
Calibration Requirements: Not stated.
Data Outputs; Analog electrical slgnal/stripchart.
Special Sampling Requirements (Collection. Storage. Handling); Not stated.
Reference; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D.C. (1971).
C-43
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C-47
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measures: Surfactants (Anionic)
Medium: Drinking Water
Name of Measurement Method; Methylene Blue Method for Methylene Blue-Active
Substances (MBAS)
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications): The permissible concentration
of surfactants is limited by the U-.S. Public Health Service Drinking Water
Standards.
Summary of Method: This method depends on the formation of a blue-colored
salt when methylene blue reacts with anionic surfactants, which include
linear alkylate and alkyl benzene sulfonates. The salt is soluble in
chloroform and the intensity of color is proportional to the concentration. The
intensity is measured by making spectrophotometric readings in this solvent at
a wavelength of 652 my.
Limitations:
Range of Applicability: 0.025 - 100 mg/1 (LAS)
Interferences: Certain organic and inorganic compounds interfere. See Reference
for listing.
Pitfalls; Special Precautions: Analysis only provides an estimate of the
surfactants present because of the numerous interferences.
Statistical Characteristics:
Accuracy and Precision: A synthetic unknown sample containing 270 yg/1 LAS
in distilled water was determined, with a relative standard deviation of
14.8% and a relative error of 10.6% in 110 laboratories. (see reference
for additional data).
Time of Measurement: Not stated
Calibration Requirements: No unusual requirements
Data Outputs: Analog electrical signal readout
Special Sampling Requirements (Collection. Storage. Handling): Not stated.
Reference: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et a].,
Washington. D. C. (1971).
C-44
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C-48
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Turbidity
Medium: Drinking Water
Name of Measurement Method; Nephelometric Mechod
Principal Detection Techniques: Nephelometry
Purpose of Measurement (Important Applications): Turbidity is used as a
control parameter for the clarity of beverages, food, and water treatment
plants.
Summary of Method: This method is based upon a comparison of the intensity
of light scattered by the sample under defined conditions, with the intensity
of light scattered by a standard reference suspension under the same con-
ditions. The higher the intensity of scattered light, the higher the turbidity.
Formazin polymer is the turbidity standard reference suspension for water.
Limitations:
Range of Applicability: The determination of turbidity is applicable
to any water sample that is free of debris and coarse sediments which
settle out rapidly.
Interferences: Dirty glassware, the presence of air bubbles, and
the effects of vibrations which disturb the surface visibility of
the sample will lead to false results.
Pitfalls; Special Precautions: Not stated.
Statistical Characteristics:
Accuracy and Precision; The turbidity of a particular concen-
tration of formazin suspension is defined as 40 units. This same
suspension of formazin has an approximate turbidity of 40 units when
measured on the candle turbidimeter; therefore, turbidity units
based on the formazin preparation will approximate those derived
from the candle turbidimeter but will not be identical to them.
Reproducibillty statistical information is not stated in Reference.
Tiae of Measurement; Not statot"
Calibration Requirements: The accuracy of any supplied calibrated scales
should be checked.
Comments by Users: Greater precision, sensitivity and applicability
over a wide turbidity range make the nephelometric method preferable
to the visual methods.
Data Outputs: Scale reading
Special Sampling Requirements (Collection, Storage. Handling): Turbidity
should preferably be determined on the same day the sample is taken. If
longer storage is unavoidable, however, samples may be stored in the dark
up to 24 hours. For even longer storage, treat each 1 liter of sample
with 1 gm mercuric chloride. Prolonged storage before measurement is not
recommended. All samples should be vigorously shaken before examination.
References: Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al.,
Washington, D. C. (1971).
C-45
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C-50
SUMMARY OF ANALYTICAL METHOD
Parametr(s) Measured: Zinc
Medium: Drinking Water
Name of Measurement Method: Dithizone Method
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications): Zinc is an essential and
beneficial element in body growth. However, concentrations above 5 mg/1 can cause
a bitter astringent taste and an opalescence in alkaline waters.
Summary of Method: Zinc reacts with diphenylthiocarbazone to produce a colored
coordination compound. Zinc also forms a weak thiosulfate complex that tends to
retard the reaction between zinc and dithizone, a reaction which is demonstrably
slow and incomplete. For this reason the determination is empirical and demands
the use of an Identical technic in both standardization and actual sample analysis.
Limitations:
Range of Applicability; Minimum detectable concentration lug/1
Interferences: Ferric iron, residual chlorine, and other oxidizing agents
Pitfalls; Special Precautions: Glassware should be segregated especially
for this determination.
Statistical Characteristics:
Accuracy and Precision: A synthetic unknown sample containing 650 Mg/1 Zn,
500 ug/1 Al, 50 ug/1 Cd, 110 pg/1 Cr, 470 pg/1 Cu, 300 pg/1 Fe, 70 pg/1 Pb,
120 pg/1 Mn and 150 pg/1 Ag in distilled water was determined by the
dithizone method with a relative standard deviation of 18.2% and a relative
error of 25.9% in 46 laboratories.
Time of Measurement: Not stated
Calibration Requirements; A calibration curve is prepared using a standard zinc
solution.
Data Outputs: Analog instrumental reading or visual comparison, manual recording
Special Sampling Requirements (Collection, Storage. Handling): Sample should
preferably be analyzed within 6 hours after collection. The addition of hydro-
chloric acid will preserve the metallic ion content.
References; Standard Methods for Examination of Water and Wastewater,
13th Edition, American Public Health Association, et al..
Washington, D.C. (1971).
C-46
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D. SOLID WASTE METHODS
-------
No. D-l
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Percent Ash and Percent Weight Loss on Heating (WLOH)
at 600T.
Medium: Solid Waste
Name of Measurement Method: Weight loss on heating
Principal Detection Techniques: Gravimetric
Purpose of Measurement: The amounts of volatiles and solids in solid waste
materials is one parameter used to evaluate the efficiency of incinerators.
Summary of Method: This technique involves the gradual increase of the
temperature of a furnace containing the sample to 600°C for A hours. The
samples are uncovered to allow sufficient circulation of air over the sample,
which permits oxidation of elemental carbon in addition to volatilization of
hydrocarbons.
Limitations:
Range of Applicability: Not stated
Interferences: None
Pitfalls; Special Precautions: None cited
Statistical Characteristics:
Accuracy: Within 1 percent of theoretical value
Precision; Coefficients of variations of replicate sample
determination: about 0.05.
Time of Measurement: Not stated
Calibration Requirements: Not stated
Comments by Users: It is sometimes desirable to use WLOH at 960°C to evaluate
reduction efficiency of incinerators when large carbonate content is present.
Data Outputs: Manual readout
Special Sampling Requirements (Collection. Storage. Handling): Sample preparation
includes drying, pulverizing, homogenity, and redrying.
References: D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-l
-------
No. D-2
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: BOD
Medium: Solid Waste (Incinerator Quench Water and Landfill Leachate)
Name of Measurement Method: Azide Modification of the Winkler Method
Principal Detection Techniques: Titrimetric
Purpose of Measurement (Important Applications); BOD of leachate is measured
to determine the amount of oxidizable wastes that will be discharged into a
sewage system, a water course, or the ground water. It is also used to cali-
brate the dissolved oxygen probe which then must be used to determine BOD in
quenchwater.
Summary of Method: The analysis of an aerated, diluted sample for its BOD
involves the determination of its dissolved oxygen content before and after an
incubation period. The Azide Modification of the Winkler Method utilizes sodium
azide to reduce oxidizing agents which would otherwise give a positive interference.
Limitations:
Range of Applicability: The Azide Modification of the Winkler Method
is not applicable to samples with a dilution factor of 40, having a
5-day BOD value 54.1 ppm or less.
Interferences: Results obtained from the Azide Modification are
invalid if the final diluted sample contains more than four mg/1
nitrite, one mg/1 ferrous iron, or 200 mg/1 ferric iron; any sulfite
or thisulfate; or large amounts of chloride which may evolve as
chlorine during the analysis. As a result quenchwater is determined
by the dissolved oxygen probe, for which this serves to calibrate.
Pitfalls; Special Precautions; Because the test is qualitative and
involves a distinct color change, the analyst should have knowledge
of the desired color intensity and hue; on the other hand, the con-
centration of the reagents may be approximate. Samples which are
more than 24 hours old should not be analyzed.
Statistical Characteristics:
Accuracy; Not stated
Precision: The standard deviations for dilution water, quench
water, and dilution and quench water BODs are 0.27, 0.69, and 0.61
respectively.
Time of Measurement: Not stated
Calibration Requirements: Not stated
Data Outputs; Visual observation
Special Sampling Requirements (Collection, Storage. Handling); Samples in which
the first D.O. reading will be taken more than four hours after collection should
be cooled to 5°C and maintained in the dark. The initial D.O. must be read within
24 hours of sampling.
References: D. ?• Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-2
-------
No. D-3
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: BOD, (Dissolved Oxygen)
Medium: Solid Waste (Incinerator Quench Water and Landfill Leachate)
Njme ol Mo.-isnremenf Method: Dissolved Oxygen Analyzer Method*
rrincin.il Ui'U'i:i inn 'IVc.liniques: Electrical measuremetiL
Pu_rp_ose nl' Measurement: BOD of quench water and leachnte is measured to determine the
amount of oxiil i z.ih lu water that will discharge into a sewage system or a water course.
Summary of MoLhod: Tho analysis ol an aerated, diluted sample for its BOD involves
the dercrnun«ition of its dissolved oxygon content before and after an incubation period.
Li_mi tal ions:
Range of Applicability: Dissolved oxygen analyzer method is not applicable to
samples with a dilution factor of 40, having a 5-day BOD value of 23.5 mg/1 or less.
InterTerences:Although a probable output can be obtained from any element or
compound which diffuses through the semipermeable membrane and is reduced at a
potential of -0.578 volts or less, interferences of this nature are infrequent.
Hydrogen sulfide and chlorine,although not detected by the probe, will react with
Che lead anode and cause a decline in sensitivity. Greases and oils will coat
the semipermeable membrane, increase the diffusion resistance and decrease the
probe output.
The effect of variable temperatures is limited to + 2% over the temperature
range of 0° to 50°C when suitable turbulence is provided. A secondary resistance
to oxygen diffusion exists at the membrane; however, it is of minor significance
when the sample is vigorously agitated to produce a high degree of turbulence.
Statistical Characteristics;
Accuracy: (D.O. Analyzer) 1% of the reading and better than +0.1 mg/1.
Precision: The standard deviation of the BOD analysis is 0.30.
Time of Measurement: None Stated
Calibration Requirements: Probe must be calibrated using a liquid similar to the sample
to be analyzed whose D.O. value has been determined by the Winkler Method.
Data Outputs: Dial reading
Special Sampling Requirements (Collection. Storage. Handling); Samples in which the
first D.O. reading will be taken more than four hours after collection should be
cooled to 5°C and maintained in the dark. The initial D.O. must be read within
24 hours of sampling.
References; D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
* Summary is specific for the Weston and Stack D.O. Analyzer.
D-3
-------
No. D-4
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Carbon and Hydrogen
Medium; Solid Waste
Name of Measurement Method; Not stated
Principal Detection Techniques: Gravimetric
Purpose of Measurement (Important Applications): Not stated
Summary of Method: The sample is combusted in an atmosphere of oxygen within
a closed system and the combustion products are fixed in an absorption train. The
water is absorbed by magnesium perchlorate, and carbon dioxide is absorbed by
Indicarb or Ascarite and activated alumina.
Limitations:
Range of Applicability; Method is applicable to raw garbage, raw
refuse, compost, incinerator residue, etc. which have a carbon content of
0.5-83.0% and a hydrogen content of 0.01 to 7.80%. Since hydrogen is
analyzed as 1^0 all samples must be redried no more than a few days before
the analyses are performed. Sample weight must exceed one gram.
Pitfalls; Special Precautions; None Stated
Statistical Characteristics;
Accuracy: Within one actual percent of the true value.
Reproducibility: Pooled standard deviation of standard samples
ranged from 0.17-0.15 for carbon and 0.15-0.10 for hydrogen on
triplicate samples.
Time of Measurement: Not stated
Calibration Requirements: A blank analyses should be run to determine the
increase in weight of the absorption bulbs.
Data Outputs; Digital scale readings
Special Sampling Requirements (Collection. Storage. Handling); Samples must
be dried, ground to less than 2 mm and redried.
References; D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-4
-------
No. D-5
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Carbonate Carbon
Medium: Solid Waste
Name of Measurement Method:
Principal Detection Technique; Gravimetric
Purpose of Measurement (Important Applications): Serves as a criterion for
evaluating incinerator efficiency to dispose of organic carbon matter, and
affects the analysis of other constituents. The results are necessary
for the calculation of organic elemental carbon and elemental oxygen.
Summary of Method; Carbonate carbon is determined gravimetrlcally after
reacting a weighed, dry, uniform sample with dilute hydrochloric acid inside
a close system and fixing the evolved gases in an absorption train.
Limitations;
Range of Applicability; Should not be employed to analyze samples
which contain less than 0.01 percent carbonate carbon.
Interferences; None stated
Pitfalls; Special Precautions; Sample weights below 1 gram are
inadequate.
Statistical Characteristics:
Accuracy: Average percent carbon found in a standard sample and
analyzed eight times was 11.97 when actual percent was 12.01.
Precision: The standard deviation of the eight standard sample
analyses was 0.18.
Time of Measurement; 30 minutes per determination
Calibration Requirements; The carbonate carbon train should be checked
periodically by analyzing a standard.
Data Outputs;
Special Sampling Requirements (Collection, Storage, Handling); Sample must
be dried, ground to less than 2 mm and thoroughly mixed.
References: D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-5
-------
No. D-6
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Cellulose
Medium: Solid Waste (compost)
Name of Measurement Method; Anthrone Colorimetric Method
Principal Detection Technique; Colorimetric
Purpose of Measurement (Important Applications):
Summary of Method: A compost sample is extracted eight hours with benzene
followed by eight hours of extraction with hot water. The extracted
cellulose is then dissolved, reacted with anthrone in 100°C bath for
15 minutes, cooled to room temperature and analyzed on a colorimeter at 650
millimicrons.
Limitations:
Range of Applicability; Not stated
Interferences; None stated
Pitfalls; Special Precautions: None stated
Statistical Characteristics:
Accuracy: No data given. See "Comments" below.
Precision: No data given. See "Comments" below.
Time of Measurement: At least 16 hours.
Calibration Requirements; Not stated
Comments by Users; The method is accurate and reproducible for all analysis
performed on compost.
Data Outputs: Analog electric signal
Special Sampling Requirements (Collection. Storage. Handling); Sample
preparation: Sample should be finely ground and dried.
References: D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-6
-------
No. D-7
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Cellulose
Medium: Solid Waste (Compost)
Name of Measurement Method:
Principal Detection Techniques: Gravimetric
Purpose of Measurement (Important Applications):
Summary of Method; A compost sample is washed using four solvents (benzene,
ether, acetone, and methanol) and passed through an abestos filter on a suction
flask. The filter cake is ignited at 625 C for one hour and the loss of weight
after ignition of the sample is the amount of cellulose present.
Limitations:
Range of Applicability: Not stated
Interferences: Not stated
Pitfalls; Special Precautions; Benzene must be added while the sample
is hot in order to dissolve a tan-like material found in compost.
Statistical Characteristics;
Accuracy; The difference between the theoretical and found percent
cellulose for nine samples was less than one percent. Theoretical
cellulose values ranged from 28.2 to 65.4 percent.
Precision; Duplicate samples should be run to ensure precision.
(No data given.)
Time of Measurement:
Calibration Requirements:
Comments by Users: The gravimetric method is sometimes recommended over the
colorimetrie method because it is more rapid and easier to perform.
Data Outputs: Visual ovservation; manually recording
Special Sampling Requirements (Collection, Storage. Handling); Sample
Preparation: The sample should be finely ground and dried.
References; D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-7
-------
No. D-8
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Chemical Oxygen Demand
Medium: Solid Waste Compost
Name of Measurement Method:
Principal Detection Technique: Titrimetric
Purpose of Measurement (Important Applications): COD is a measure of the
stability of compost as a function of organic content.
Summary of Method; A sample is boiled with known amounts of potassium dichro-
mate and sulfuric acid, and the excess dichromate is titrated with ferrous
ammonium sulfate. The amount of oxidizable organic matter, measured as
oxygen equivalent, is proportional to the potassium dichromate consumed.
Limitations:
Range of Applicability; Not stated
Interferences: None stated
Pitfalls; Special Precautions; Short-straight-chain alcohols and
acids are oxidized 85 to 95 percent or more only when a silver
catalyst is used. Benzene, toluene, and pyridine are not oxidized
by the procedure.
Statistical Characteristics; For most organic compounds the oxidation is
95 to 100 percent of the theoretical value.
Accuracy; Not stated
Precision; No data given. (See "Comments by Users.")
Time of Measurement: Not stated
Calibration Requirements; Not stated
Comments by Users; Analysis provides good precision in duplicate assays.
Data Outputs: Visual observation; manual recording
Special Sampling Requirements (Collection. Storage, Handling); Sample Preparation:
Sample should be finely ground (2mm mesh).
References: D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-8
-------
No. D-9
SUMMARY OF ANALYTICAL METHOD
ParamcLor(&J Measured: Degree of Decomposition of Compost (Qualitative)
Medium: S.iliil W.istc
Name of Measurement Method: Starch - Iodine Method
Principal Detection Techniques: Colorimetric
Purpose of Measurement (Important Applications): Simple and rapid test to
determine the extent of decomposition of compost.
Summary of Method: Certain polysaccharides form characteristic color complexes when
combined with molecular iodine. The hydrolysis of starch may be followed by the
gradual change of the iodine complex color (blue-black to light blue to purple
to red to yellow to neon).
The rationale of the test rests on the hypothesis that all refuse contains
a measurable quantity of starch and that the starch must be degraded before the
compost can be considered acceptable.
Limitations:
Range of Applicability: All
Interferences: High turbidity
Pitfalls; Special Precautions; None stated
Statistical Characteristics:
Accuracy: Not stated
Precision; Not stated
Time of Measurement: Not stated
Calibration Requirements: Not stated
Data Outputs: Visual observation, manually recorded
Special Sampling Requirements (Collection, Storage, Handling); Not stated
References: D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical, and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-9
-------
Wo. D-10
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Total Heat of Combustion.
Medium: Solid Waste
Principal Detection Techniques; Calorimetric
Purpose of Measurement: The heat contents of solid waste materials are important to
determine the operating efficiency of an incinerator and the stability of compost
used for landfilling.
Summary of Method: A reaction chamber is immersed in a container filled with water.
Heat generated as the sample is burned in the presence of a catalyst (to ensure com-
plete combustion) is transferred to the water, and the conseauent temperature rise
of the water is recorded. From a knowledge of the quantity of water present, its
specific heat, and the change in temperature, the amount of heat involved In the
reaction can be determined.
Limitations;
Range of Applicability; Method should not be employed to analyze samples which
contain less heat content than the pooled standard deviation for that type of
sample.
Interferences: Corrections can be applied for all interferences which include
radiation, temperature rise of the vessels, etc.
Pitfalls; Special Precautions; None Stated
Statistical Characteristics;
Accuracy: The average of three determinations of a known sample was 1.2% from
the true value. The method can analyze solid waste materials to within 40 BTU/lb.
Precision; The standard deviation on an array of triplicate samples ranged from
40 to 110 BTU/lb. The BTU/lb range of the samples was from about 4,000 to 10,000.
Time of Measurement: Not stated
Calibration Requirements; The energy equivalent of the calorimeter should be
calculated using benzoic acid as a primary standard.
Data Outputs; Thermometer readings, scale readings (presumed to be visual
observations, manually recorded).
Special Sampling Requirements (Collection, Storage, Handling); Sample preparation:
Samples must be ground to a particle size less than 2 mm, thoroughly dried, and
homogenized. Fluffy materials must be pallatized.
References; D. F. Bender, H. Stierli and M.L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-10
-------
No. D-ll
SUMMARY OF ANALYTICAL METHOD
Parameter(«) Measured: Total Heat of Combustion
Medium; Solid waste
Name of Measurement Method: Modified Dulong Formula
Principal Detection Technique: None. Uses results of other analytical methods
Purpose of Measurement (Important Applications): The heat contents of solid
waste samples may be determined mathematically by a modified Dulong formula with
data from ultimate analysis.
BTU/// = 14,096 (decimal percentage of organic carbon) + 60,214 (total
decimal percentage of hydrogen) + 10,401 (total decimal percentage of nitrogen)
+ 3,982 (decimal percentage of total sulfur) + 8,929 (decimal percentage of
available hydrogen) + 4,274 (decimal percentage of organically bound oxygen)
- 6,382 (decimal percentage of inorganically bound carbon).
Limitations: See methods for analysis of specific constituents
Statistical Characteristics;
Accuracy and Precision dependent on analytical methods used for
determining specific constituents.
Time of Measurement: Not stated
Calibration Requirements: See the specific analyses
Comments by Users: Calculated BTU/// values are well within limits of require-
ments for an estimated BTU/// value of solid waste samples.
Data Outputs; A mathematical procedure. No measured data output.
Special Sampling Requirements (Collection. Storage, Handling); Not stated
References; D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-ll
-------
No. D-12
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Nitrogen (Organic and Ammoniacal)
Medium: Solid Waste
Name of Measurement Method: Kjeldahl - Wilfarth - Gunning - Winkler Method
Principal Detection Techniques; Titrimetric
Purpose of Measurement (Important Applications): To monitor the degrees and rate of
biological decomposition of organic matter and to determine the suitability of compost
for use in agricultural soils by using as part of determination of C/N ratio.
Summary of Method; Sample is digested with sulfuric acid, mercuric oxide, and
potassion sulfate. After the digestion is completed, the mixture is then heated with
alkaline sodium thiosulfate which destroys the mercuro-ammonium complex and permits
the distillation of ammonia into boric acid. Ammonium borate is then titrated with
sulfuric acid to a methyl blue-light violet end point.
Limitations:
Range of Applicability: Limited to the analysis of municipal refuse,unfortified
compost, incinerator residue, and other samples with little nitrate content.
Interferences; None Stated
Pitfalls; Special Precautions;
Statistical Characteristics;
Accuracy; Not stated
Precision; Standard deviation on standard samples ranged from 0.03 to 0.07
percent, where observed nitrogen content of samples ranged from 7.4 to
10.2 percent.
Recovery: 98.5 percent or more recovery on standard samples containing
50 mg or less N.
Time of Measurement; Not stated
Calibration Requirements; Not stated
Data Outputs; Visual observation, manually recorded
Special Sampling Requirements (Collection. Storage. Handling); Sample should be
dried, ground (2 mm or less), homogenized and redried before initiation of the
analysis.
References; D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-12
-------
No. D-13
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Total Nitrogen
Medium: Solid Waste
Name ol Measurement Method: Automated Dumas Method
Principal Detection Technique: Gas Absorption - Volume Displacement
Purpose of Measurement (Important Applications); To monitor the degree and
rate of biological decomposition of organic matter and to determine the
suitability of compost for use in agriculture soils by using as part of
determination of C/N ratio.
Summary of Method: A 100 mg (or less) solid sample is packed in a combustion tube,
and high purity carbon dioxide is employed to purge the system of entrapped air.
The sample is decomposed at 850-900°C in the presence of oxidizing agents, e.g.,
copper oxide and cobalt oxide. Nitrogen oxides are reduced to gaseous nitrogen
in the post-heater tube in the presence.of Cuprin. The gaseous mixture is
scrubbed thoroughly in a caustic solution to remove the carbon dioxide carrier
gas and the remaining nitrogen gas is collected and measured in a stainless
steel syringe linked to a digital counter.
Limitations:
Range of Applicability; Up to 100 mg of organic matter and up to 40 mg
of nitrogen
Interferences: None stated
Pitfalls; Special Precautions; The temperature of the combustion
furnace should always be maintained below 1020°C to prevent sintering of
the Cuprin tube packing. All fresh reagents should be employed.
Statistical Characteristics:
Recovery; Standard samples containing less than 20 mg nitrogen
yielded 99 or more percent nitrogen recovery.
Precision: Standard deviation on standard samples ranged from
0.02 - 0.06, where observed mean percent nitrogen ranged from 7.5 to
13.7.
Time of Measurement: Not stated
Calibration Requirements; Not stated
Data Outputs: Digital counts
Special Sampling Requirements (Collection, Storage, Handling); Sample preparation
sample should be dried, ground (0.5 mm or less) and redried before initiation of
the analysis.
References; D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-13
-------
No. D-14
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Total Nitrogen
Medium; Solid Waste
Name of Measurement Method: Comprehensive Nitrogen Method
Principal Detection Technique: Titrimetric
Purpose of Measurement (Important Applications); To monitor the degree and
rate of biological decomposition of organic matter and to determine the
suitability of compost for use in agriculture soils by using as part of
determination of C/N ratio.
Summary of Method: A sample is heated with metallic chromium in an acid
medium to reduce the nitrates. The mixture is digested with sulfuric acid
in the presence of mercuric oxide and potassium sulfate. The mixture is
treated with alkaline sodium thiosulfate which destroys the mercuro-
ammonium complex and permits the distillation of ammonia into boric acid.
Ammonium borate is then titrated with sulfuric acid.
Limitations:
Range of Applicability; Up to 60 mg of nitrogen
Interferences: None stated
Pitfalls; Special Precautions; None stated
Statistical Characteristics;
Accuracy; Not stated
Precision; Standard deviation on standard samples ranged from
0.04 - 0.09 (expressed as percent nitrogen) where observed mean
percent nitrogen ranged from 7.4 to 13.6.
Recovery; Analysis of standard samples containing less than 60 mg
nitrogen yielded 98.2 or more percent nitrogen recovery.
Time of Measurement; Not stated
Calibration Requirements; Not stated
Data Outputs;
Special Sampling Requirements (Collection, Storage. Handling); Sample preparation
sample should be dried, ground (2 mm or less), homogenized, and redried before
initiation of the analysis.
References: D. F. Bender, H. Stierli and M. L. Peterson (Editors),
Physical, Chemical and Microbiological Methods of Solid Waste
Testing, U.S. Environmental Protection Agency, National Environ-
mental Research Center, Cincinnati, Ohio (1973). (In process of
printing.)
D-14
-------
No. D-15
SUMMARY OF ANALYTICAL METHOD
Paramoi i-r(s)- MI-JKUI i-il; Total Oxygen
Mud iuiii: So I nl W i,LV
Namu ol Mea.siiii.-iii"iiL Melhod: Mathematical Determination
Princip.il Detection Techniques: See the specific analysis.
Purpose i'F Mo.iMircment: The oxygen analysis of solid wastes is necessary to determine
the efficiency of operation of an incinerator, the design of furnaces for incineration,
and a complete materials balance of incoming and outgoing materials.
Summary of Method: Two formulas* are used to calculate the total oxygen content which
correlates data from as many as eight different analysis. The eight components are
total carbon, carbonate carbon in total sample, carbonate carbon in ash from volatile
at 600°C, total hydrogen, total nitrogen, total sulfur, total chlorine, and volatiles
at 6()0°C or 950°C.
LimiuiLi cms:
Range of Applicability: See the specific analysis
Interferences: See the specific analysis
Pitfalls; Special Precuations: See the specific analysis
SL.IL i-,Lical Characteristics:
A.-i. uracy: Not Stated
Precision: The largest deviation from the average value exist usually in the
volatile an;ilysis, therefore, reproducibility of the volatile data mostly
determines the precision of the oxygen data. Past data indicates the total
oxygen value could vary one or two percent from the average. This is well
within acceptable limits.
Time of Measurement: Not stated
Calibration Requirements: See specific analysis
Special Sampling Requirements: See specific analysis
References: D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical
Chemical and .Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center. Cincinnati, Ohio (1973). (In process of printing.)
* Given in Reference cited.
D-15
-------
No. D-16
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Potential Heat Determination
Medium; Solid Waste
Principal Detection Technique: Calorimetric
Purpose of Measurement: The potential heat of a sample can be an important criterion
for evaluating the efficiency of an incinerator or for measuring the usefulness of
incinerator residue.
Summary of Method: A reaction chamber is immersed in a container filled with water.
Heat generated as the sample in the reaction chamber is burned is transferred to the
water, and the consequent temperature rise of the water is read from the thermometer.
From a knowledge of the quantity of water present, its specific heat, and the change
in temperature, the amount of heat involved in the reaction can be calculated.*
Limitations;
Range of Applicability: None Stated
Interferences: Corrections can be applied for all interferences.
Pitfalls; Special Precautions; The analyst must be certain that samples do
not partly ignite.
Statistical Characteristics;
Accuracy; Duplicate observations upon the same sample agree 95% of the time
within the range 25-244 BTU/lb when full combustion of the sample takes place.
Precision; The absolute value of the difference between duplicated observa-
tions should not exceed 1.96 (^/2 )(s), confidence interval, or 144 BTU/lb
more than 5% of the time. The pooled standard deviation of the three types of
samples tested ranged from 9.3 to 52.0 BTU/lb (minimum of 8 samples tested,
maximum of 13 samples tested).
Calibration Requirements: The energy equivalent of the calorimeter should be
calculated using benzoic acid as a primary standard.
Data Outputs; Digital output
Special Sampling Requirements: Sample Preparations: Samples must be ground to a
particle size less than 2mm, thoroughly dried, and homogenized. Fluffy materials
must be pelletized.
References; 0. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
^Description relates to the Parr Adiabatic Calorimeter.
D-16
-------
No. D-17
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Protein (Sample Preparation)
Medium; Solid Waste
Name of Measurement Method; Vacuum-Acid Hydrolysis Method
Principal Detection Technique; Column Chromatography, Photometry
Purpose of Measurement (Important Applications): Determination of protein
content.
Summary of Method: The sample is hydrolyzed under vacuum conditions in an
acid solution to liberate the amino acid groups prior to analysis on an
automatic amino acid analyzer.
Limitations:
Range of Applicability; Not stated
Interferences: Metal ions, undigested starchy and celluosic material
Pitfalls; Special Precautions; None stated
Statistical Characteristics:
Accuracy and Precision: Not stated
Recovery: The percent recovery for the standard mixture ranged from
95 to 101.
Time of Measurement; 48 hours required for complete hydrolysis procedure.
Calibration Requirements: Not stated
Data Outputs: Analog electrical signal, displayed on meter or graph.
Special Sampling Requirements (Collection, Storage. Handling): If an analysis
of the protein hydrolyzate is not made immediately, sample should be stored
in a freezer.
References! D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical, and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-17
-------
No. D-18
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Selenium
Medium: Solid waste, air, water
Name of Measurement Method: DAN procedure
Principal Detection Technique; Spectrophotoflurometer
Purpose of Measurement (Important Applications): Exposure to high concentrations
of selenium produces toxic effects. It is therefore of great importance to de-
termine the extent to which solid wastes handling, processing, and disposal are
contributing selenium to the environment.
Summary of Method: Selenium is isolated with toluene 3, 4-dithiol. Under acid
conditions, freshly prepared Dan (2, 3-diaminonaphthalene) is added and the
solution placed in a water bath at 50°C for 20 minutes and then tap cooled. The
solution is extracted in 125 ml separatory funnel containing cyclohexane and
the organic phase collected in a centrifuge tube. The tube is centrifuged at
2000 rpm for 2 minutes, and then read in a spectrophotofluorometer at emission
wavelength of 517 millimicrons with the excitation wavelength set at 370 milli-
microns.
Limitations:
Range of Applicability; Lower limit O.Olpg of selenium
Interferences; None stated
Pitfalls; Special Precautions; None stated
Statistical Characteristics;
Accuracy; Not stated
Precision; Not stated
Time of Measurement; Not stated
Calibration Requirements: Not stated
Data Outputs: Analog electrical signal
Special Sampling Requirements (Collection. Storage, Handling); Solid waste samples
must be ground, dried, pelletized and ashed using water as an absorbing solution.
References: D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-18
-------
No. D-19
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Volatiles or Percent Weight Loss on Ignition at 950"C
Medium: Solid Waste
Name of Measurement Method; Extension of Carbon-hydrogen gravimetric method.
Principal Detection Techniques; Gravimetric
Purpose of Measurement (Important Applications); One of the parameters used
to evaluate the efficiency of incinerators.
Summary of Method; The sample is oxidized in an atmosphere of oxygen with a
combustion aid (iron chips) and the combustion products are fixed in an
absorption train. The weight of the sample before and after combustion is
used to calculate the volatile content. This can also be done using a muffle furnace.
Limitations;
Range of Applicability: None Stated
Interferences: Metals
Pitfalls; Special Precautions; Only clay weighing boats can be
used during the test. (See summary for r.rrbon-Hydrogen Method)
Statistical Characteristics:
Accuracy; None Stated
Precision; Replicate sample show better agreement with this method
than that obtained using the muffle furnace method. Quantitative data
not cited.
Time of Measurement; Method adds 5 to 10 minutes extra time
to each carbon-hydrogen test.
Calibration Requirements; None Stated
Data Outputs; Digital
Special Sampling Requirements (Collection, Storage, Handling): Sample must
be dried, ground to less than 2 mm and redried.
References; D. F. Bender, H. Stierli and M. L. Peterson (Editors), Physical,
Chemical and Microbiological Methods of Solid Waste Testing,
U.S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio (1973). (In process of printing.)
D-19
-------
E. RADIOACTIVITY METHODS
-------
E-l
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Antimony
Medium; Water
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma ray spectroacopy to identify Sb isotopes.
Beta count to measure decay and confirm 60.2 d half-life.
Purpose of Measurement (Important Applications):
To evaluate potential, nealth nazard from radionucllde discharge: it nuclear
power stations during routine operations, the amount of the rarf-f on,-elide presc.u
Is determined.
Summary of Method: Antimony carrier and appropriate scavenging carriers are
added to the aqueous sample and impurities are removed by a basic sulfide pre-
cipitation. The antimony is collected as the sulfide in acid solution, and
reduced to the metal for counting.
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
Gamma Ray Beta Particle
I24Sb 0.04 0.02
The minimum detectable limits were calculated for 100 ml allquots for each
analysis and a 100 minute counting time. Although not always practical, lower
limits can be obtained with larger sample volumes and longer counting time.
For nuclides discharged from light-water moderated nuclear power reactors, the
composition of the test solutions has ranged from mixtures of many radio-
nuclides at microcuries per milliliter concentrations to barely detectable levels
at picocuries per liter concentrations. The substrate quality has ranged from
highly deionized coolant water to waste solutions of high salt contents plus
detergents.
Interferences: Decontamination Factors
131T 58/60- 110m,
1 Co Ag
103 103 103
Pitfalls; Special Precautions: If the aqueous sample has significant I
activity, it will be necessary to modify the procedure to assure complete
decontamination. With the multitude of reactor and waste solutions generated,
radlonuclide and chemical compositions will vary and therefore require
auxiliary treatment to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not Given
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Procedure
time: 4 samples - 3 hours. Iteta count at 3 - 4 week intervals.
Calibration Requirements: Counter background. Calibrate gamma spectrometer and
beta counter.
Data Outputs: Counts and time and energy.
Special Samplirie Requirements (Collection. Storage. Handling): The sample must be
strongly basic to ensure that antimony will stay in solution through the basic sulfide
precipitation.
References:
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environ-
mental Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Barnes, J. W., Collected Radiochemical Procedures, LA-1721 2nd Ed.,
156-162, LASL, U of Calif., 1958.
(3) Pocze, L., e£ al^, "Testing of Silver, Antimony, Zinc, Tin and
Selenium Content in High Purity Cappers by Activation Analysis",
Proc. Conf. Appl. Phys.-Chem. Methods Chem. Anal. Budapest 2, 270-5,
1966 (Chem. Abstr. 69, 8107 k, p. 8116, 1968). ~
E-l
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E-2
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Arsenic
Medium; Water
Name of Measurement Method; Not Given
Principal Detection Technique: Gamma ray spectroscopy.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method; Arsenic carrier and appropriate holdback carriers are added
to the acidified aqueous sample. The arsenic is collected as the sulfide in
acid solution and reduced to the metal for counting.
Limitations:
Range of Applicability: Minimum Detectable Limit (pCi/ml)
Gamma Ray Beta Particle
76As 0.1 0.02
The minimum detectable limits were calculated for 100 ml aliquots for each
analysis and a 100 minute counting time. Although not always practical, lower
limits can be obtained with larger sample volumes and longer counting time.
For nuclides discharged from light-water moderated nuclear power reactors, the
composition of the test solutions has ranged from mixtures of many radio-
nuclides at microcurles per milliliter concentrations to barely detectable levels
at picocuries per liter concentrations. The substrate quality has ranged from
highly deionized coolant water to waste solutions of high salt contents plus
detergents.
Interferences: Decontamination Factor
131T 58/60. 110m.
1 Co Ag
211
10* 10J 10J
He rails; Special Precautions:
With the multitude of reactor and waste solutions generated, radionuclide and
chemical compositions will vary and therefore require auxiliary treatment to
effect desired decontamination.
Plot garaa ray spectrum immediately to note presence of photo peaks indicative
of incomplete decontamination.
Statistical Characteristics:
Accuracy of Precision: Not Given
Time of Measurement (Maximum Frequency. Recovery t'eri.od, etc.); Procedure _-
time: 4 samples - 2 hours. Plot gamma ray spectrum immediately to identify As.
Repeat gamma measurements at 6, 12, and 24-hour intervals to corroborate
half-life.
Calibration Requirements: Counter background. Calibrate gamma spectrometer.
Comments by Users: It is essential that all IINO-j be removed to eliminate inter-
ference with the conversion of arsenic to the metal. However, do not let the
sample go to dryness.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage, Handling): Not Given
References:
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Lingane, J. J., Analytical Chemistry of Selected Metallic Elements,
pp. 27 and 28, Reinhold, 1966.
(3) Mas;e.r Analytical Manual, ORNL, TID-7015, Method 5-110600, 1957.
E-2
-------
E-3
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Barium
Medium: Water
Name of Measurement Method: ASTM D2038-68
Principal Detection Technique: Gamma spectroscopy; beta count to
substantiate half-life.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations,the amount of the radionuclide present is determined.
Summary of Method: Radioactive barium and added barium carrier are first
precipitated from water to reduce sample volume and then purified. The main
purification step is the repeated precipitation of barium chloride from a cold
hydrochloric acid-ether mixture and scavenging with ferric hydroxide. A final
precipitation of barium sulfate is made and the chemical yield is computed by
comparing the weight of the precipitate to the amount of carrier added originally.
Limitations;
Range of Applicability: Minimum detectable limits (pCi/ml)
140.. Gamma Ray Beta Particle
Ba 0.1 0.01
The minimum detectable limits were calculated for 100 ml allquots for
each analysis and a 100 minute counting time. Although not always
practical, lower limits can be obtained with larger sample volumes and
longer counting time. The composition of the test solutions has ranged
from mixtures of many radionuclides at microcuries per milliliter
concentrations to barely detectable levels at picocuries per liter
concentrations. The substrate quality has ranged from highly deionlzed
coolant water to waste solutions of high salt contents plus detergents.
Interferences: Decontamination Factors
131T 58/60., 110m.
I Co Ag
10* 103 10*
Lanthanum 140 is an interference
Pitfalls; Special Precautions: With the multitude of reactor and waste
solutions generated,radionuclide and chemical compositions will vary
and therefore require auxiliary treatment to effect desired decontamination.
140
Have to correct for the ingrowth of La. Make count as soon as possible
at end of method. If the count-is made within 30 minutes of the hydroxide
scavenge, there should be no La present.
Statistical Characteristics:
Accuracy and Precision: Not Given
Time of Measurement (Maximum Frequency, Recovery Period, etc.): Count
at 3-day intervals to measure ingrowth of •li|ULa. Beta count weekly over
a 30-day period to substantiate the 12.8 half-life of !^°Ba.
Special Sampling Requirements (Collection, Storage. Handling): Not Given
Calibration Requirements: Beta counter; gamma spectrometer; background
Data Outputs: Counts and time.
Reference :
Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
E-3
-------
E-4
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Barium
Medium: Water
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma ray spectroscopy ; beta counter
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations,the amount of the radionuclide present is determined.
Summary of Method: The strontium and barium carriers are added to the aqueous
sample collected as insoluble carbonates, and separated from most of the calcium
as nitrates. Impurities are removed by an hydroxide scavenge. The barium is
precipitated as the chromate and purified as BaSO, for counting; the strontium
is purified as SrCO., for counting. This method also precipitates strontium.
Limitations:
Range of Applicability: Same as Radioactive Barium by ASTM D2038-68.
Interferences: This method also precipitates strontium and calcium;
same as Radioactive Barium by ASTM D2038-68.
Pitfalls; Special Precautions: Make sure all calcium is removed. Plot
gamma ray spectrum to identify contaminating gamma emitters. With the
multitude of reactor and waste solutions generated,radionuclide and
chemical compositions will vary and therefore require auxiliary treatment
to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not Given
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Procedure
time: 4 samples - 6 hours. Immediately plot gamma ray spectrum. Repeat
gamma measurement over a period of a week to observe the ingrowth of the
"40La daughters. Beta count the planchet over a 2-week interval to check
the ingrowth of 140Ba - l*°La.
Calibration Requirements: Same as radioactive barium by ASTM D2038-68.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection, Storage. Handling): Not Given
Reference:
Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
-------
E-5
SUMMARY;-OF-ANALYTICAL METHOD
Parameter(s) Measured: Barium 140*
Medium; Milk
Name of Measurement Method: 'Gamma Spec'troscopy*
Principal Detection Technique; Gamma Spectroscopy
Purpose of-Measurement'dmportant Applications).:, Prevention and. control, of radio-
logical: hazards by,.defining rthe; transport of the radioactive contaminant "from" its
source•, to.its, ultimate .deposition in man.
Summary of Methodf i?our 'a measured (3'.5 liter')1 aliquot into 'the inverte'd^-well type
sample container which fits over the right-cylindrical sodium iodine crystal detector
and count.
Limitations:
Range of Applicability: Not Given
Interferences! Not-Given
Pitfalls.; Special-Precautions; -•-'Not Given
Statistical Characteristics:
Accuracy and Precision: +10 percent over the range 10-100 pCi/1
Time of Measurement: 40-60 minutes
Calibration Requirements: Counter background - gamma counter - counter efficiency
Data Outputs; Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling)': • Immediately after
collection of milk sample, a preservative is added' to the sample, and, if possible,
the sample Is refrigerated for ease of -handling.
References:
(1) Douglas, Geneva S. (Editor), Radioassay Procedures for Environmental Samples,
National Center for Radiological Health, .11. S. Public Health Service,
Rockville, Maryland",' January 1967.
(2) Kahn, B., G. K. Murphy, C. Porter, G. R. Hagee,' G. J.'Karches, and A. S. Goldin,
Rapid Methods for Estimating Fission Product Concentrations in Milk. Public
Health Service Publication No. 999-R-2, Environmental Health Series, Radio-
logical Health (1963).
(3) Ibid, p. 17.
*
This method Is considered acceptable by EPA, but Is not necessarily used in EPA
laboratories.
E-5
-------
E-6
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Cadmium
Medium: Water
Name of Measurement Method: Not Given
Principal Detection Technique: . Catania' ray sjSectrostppy to identity isotopes
Beta count to measure decay and confirm half-life
Purpose of Measurement (Important Applications):
To evaluate potential health hazard from radionucli.de discharges at nuclear power
stations during routine operations, the amount of the radionuclid- present i-s
determined.
Summary 'b£'Methba: Cobalt and cadmium carriers arfe added to the aqueous sample
and collected a"s 'insoluble 'hydroxides. The -cobalt is .p'recipi-tat'ed and purified -as
K_Co(NO_)6 for counting; cadmium is precipitated as the aulfide in acid sollition
and. piijr-tf JIM ..as C4.(pH)2 fo*. co,unti,ng,. _This method, precipitates, bot,h cobalt and
Limi cations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
Gamma Ray Beta Particle
115mCd 0.1 0.01
Interferences: Cobalt is also precipitated by this method:
Decontamination Factors
ISlj 58/60Co 110n,Ag
115m.. 105 102 10*
l«d
Pitfalls; Special Precautions: With the multitude of reactor and waste
solutions generated, radionuclide and chemical compositions will vary and
therefore require auxiliary treatment to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not Given
Time of Measurement 'flfettilmia frequency ,' Recovery Period.' 'etc.) '. Procedure
time: 4 samples - 8 hours. Plot gamma ray spectrum to identify 109Cd and
HSniCdv Beta, .count at two-week intervals to measure decay and confirm the
43-day half-life of 1.15raCd and/or the 453-day half-life of 109cd.
Calibration "Requirements: ' Counter background. Calibrate gamma spectrometer and
beta counter.
Comments by Users: 4 K beta in K.jCo(N02)6 will add approximately 10 dpm per
20 mg separated precipitate, and this background must be taken into consideration
during the beta-decay counting.
Data Outputs:' Counts, and tirte and .energy
Special Sampling Requirements (Collection, Storage. Handling): Not Given
Reference:
Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
E-6
-------
i -7
SUMMARY OF ANALYTICAL METHOD
Parameter(3) Measured; Calcium *
Medium: Milk
Name of Measurement Method: Flame photometric method *
Principal Detection Technique; Flame Photometry
Purpose of Measurement (Important Applications): Calcium plays an important
role in the biological uptake of strontium.
Summary of Method: Milk, to which acetic acid has been added, is heated in a
water bath until the casein separates. The mixture is centrifuged, filtered,
and the fitrate passed through a column of cation-exchange resin. The calcium
is eluted and its concentration is determined by flame photometry.
Limitations:
Range of Applicability: Any liquid milk sample
Interferences: Sodium, potassium, and magnesium also produced
Pitfalls. Special Precautions: Not Given
Statistical Characteristics:
Accuracy: Not Given
Precision; Duplicate sample analyses have a standard deviation of +0.05 g/liter
Time of Measurement; Not Given
Calibration Requirements: Flame photometer calibration curve; Background response
Data Outputs; Analog voltage
Special Sampling Requirements (Collection, Storage. Handling): Immediately after
collection of milk sample, a preservative is added to the sample, and, if possible,
the sample is refrigerated.
References;
(1) Douglas, Geneva S. (Editor), Radloassay Procedures for Environ-
mental Samples, National Center for Radiological Health, I). S.
Public Health Service, Rockville, Maryland, January 1967.
/2i Porter, C. R., R. J. Augustine, J. M. Matusek, Jr., and M. W. Carter.
v ' Procedures for Determination of Stable Elements and Radionuclies in Environ-
mental Samples. Public Health Service Publication No. 999-RH-10, Environmental
Health Series, Radiological Health (1965).
(3) Wenner, V. R. "Rapid Determination of Milk Salts and Ions. I. Determination
of Sodium, Potassium, Magnesium, and Calcium by Flame Spectrophotometry".
J. Dairy Sci 41:761-768 (1958)
This method is considered acceptable by EPA, but is not necessarily used in EPA
laboratories.
E-7
-------
E-8
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Calcium
Medium: Milk
Name of Measurement Method: Not given
Principal Detection Technique: Titration
Purpose of Measurement (Important Applications): To determine calcium content
of milk.
Summary of Method; An aliquot is diluted with water, hydroxylamine hydro-
chloride and potassium hydroxide are added, and the resulting solution is titrated
with disodium ethylenediaminetetraacetate, using Cal-Red as an Indicator.
Limitations:
Range of Applicability: Not given
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy: Not given
Precision: Not Riven
Time of Measurement: Not given
Calibration Requirements: Not given
Data Outputs: Visual
Special Sampling Requirements (Collection. Storage, Handling): Not given
References: Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972), U.S. Environmental Protection Agencv.
Las Vegas, Nevada.
E-8
-------
E-9
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Carbon-14
Medium: Water
Name of Measurement Method: Not Given
2
Principal Detection Technique: Thin-window (< 2 tag/cm ) beta counter
Purpose of Measurement (Important Applications); To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operation,the amount of the radionuclide present is determined.
Summary of Method: Carbon carrier in the form of sodium oxalate is added to an
unacidified aqueous sample in a closed distillation apparatus. An oxidizing agent
and acid are added to the sample to convert carbon compounds to CO.. Air is slowly
bubbled through the sample and heat is applied to transfer CO. into a flask that
contains a basic CaC]. solution. The collected CaOO. is centrifuged, washed,
transferred to a stainless steel planchet, weighed, and counted.
Limitations:
Range of Applicability: Minimum Detectable Limit (pCi/ml)
Beta Particle
UC 0.03
The minimum detectable limits were calculated for 100 ml aliquots for each
analysis and a 100-minute counting time. Although not always practical,
lower limits can be obtained with larger sample volumes and longer counting
time. For nuclides discharged from light-water moderated nuclear power
reactors, the composition of the test solutions has ranged from mixtures
of many radionuclides at microcuries per mllllliter concentrations to
barely detectable levels at picocuries per liter concentrations. The sub-
strate quality has ranged from highly deionlzed coolant water to waste
solutions of high salt contents plus detergents.
Interferences; Decontamination Factor
131t 58/60^ 110mAg
102 103 104
Pitfalls; Special Precautions: With the multitude of reactor and waste
solutions generated, radionuclide and chemical compositions will vary and
therefore require auxiliary treatment to effect desired decontamination.
A 3-month decay count will demonstrate absence of short-lived radioactive
impurities.
Statistical Characteristics:
Accuracy and Precision: Not Given
Time of Measurement: Procedure time: 1 sample - 1 hour. A 3-month decay
count will demonstrate the absence of short-lived radioactive impurities.
Calibration Requirements: Standard C absorption curve - Background count -
Beta Counter
14
Comments by Users; Decay counting for half life is not practical ( C£ ^.^ •
5730 years). The Na.C-0, should be frequently standardized by
replicate determinations. An alternate method for counting carbon -14 is by
liquid scintillation.
Data Outputs; Counts and time
Special Sampling Requirements (Collection, Storage. Handling): None Stated
Reference;
Procedures for Radlochemlcal Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
E-9
-------
E-10
SUMMARY OF ANALYTICAL METHOD
Paramecer(s) Measured: Radioactive Cerium
Medium; Water
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma ray spectroscopy - Beta count to measure
decay and confirm half-life.
Purpose of Measurement: To evaluate potential health hazard from radionuclide
discharges at nuclear power stations during routine operations, the amount
of the radionuclide present is determined.
Summary of Method: Cerium carrier is added to the aqueous sample, which is evapor-
ated to dryness, taken up in concentrated HC1 and passed through a mixed anlon
resin column. Manganese is scavenged from the effluent, and the cerium is pre-
cipitated as Ce(IO-), for counting.
Limitations;
Range of Applicability: Minimum Detectable Limits (pCi/ml)
mma Ray Beta Part
0.05 0.03
0.2
Interferences; Decontamination Factors
Nuclide Gamma Ray Beta Particle
141Ce
U4Ce 0.2 0.03
131T 58/60. 110m.
I Co Ag
10* 103 103
Pitfalls; Special Precautions: With the multitude of reactor and waste
solutions generated,radionuclide and chemical compositions will vary and
therefore require auxiliary treatment to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not ijtvea
Time of Measurement: Procedure Time: 2 samples - 6 hours.
Beta count at two week intervals.
Calibration Requirements; Counter background. Calibrate gamma spectrometer and
beta counter.
Data Outputs; Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling: Not given
Reference.
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Albu-Yaron, Ana, Mueller, D. W. and Settle, A.D., Jr., "Chemical
Separation of Cerium Fission Products from Microgram Quantities of
Uranium", Anal. Chem. 41, 1351, August 1969.
E-10
-------
E-ll
SUMMARY OF ANALYTICAL METHOD
Parameter (s) Measured; Cesium 137
Medium; Food
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma Spectrometrv
Purpose of Measurement (Important Applications) : Prevention and control of radio-
logical hazards by defining the transport of the radioactive contaminant from its
source to its ultimate deposition in man.
Summary of Method: Measure undissolved homogenate by gamma spectrometry.
Limitations:
Range of Applicability: Minimum detectable concentration is 10 pCl/kg
Interferences: Not Given
Pitfalls; Special Precautions; Not Given
Statistical Characteristics:
Accuracy and Precision: 10 pCi/Kg over the range 10-100 pCi/Kg; 10% when over 100
pCi/Kg.
Time of M»
Calibration Requirements: Counter background - Gamma spectrometer - counter efficiency
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling); The sample must
represent the edible portion or the portion actually consumed, should be prepared
and "served" in reasonable portions, must be made homogeneous and must be put in
solution. This can be done by ashing, digesting in acid , fusing, or a combination
of these. Food samples should be packaged in waterproof containers, frozen during
storage, and thawed prior to analysis. Preservatives may be needed.
Reference ; Douglas, Geneva S. (Editor), Radloassay Procedures for Environmental
Samples, National Center for Radiological Health, U. S. Public Health
Service, Rockville, Maryland, January 1967.
*
Thin method is considered acceptable by EPA, but is not necessarily used in EPA
laboratories.
E-ll
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E-12
SUMMARY OF ANALYTICAL METHOD
*
Parameter(s) Measured; Cesium 137
Medium: Milk
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma Spectroscopy
Purpose of Measurement (Important Applications); Prevention and control of radio-
logical hazards by defining the transport of the radioactive contaminant from its
source to its ultimate deposition in man.
Summary of Method: Pour a measured (3.5 liter) aliquot into the inverted-well
type sample container which fits over the right-cylindrical sodium iodine crystal
detector and count.
Limitations:
Range of Applicability: Not Given
Interferences: Not Given
Pitfalls; Special Precautions: Not Given
Statistical Characteristics;
Accuracy: Not Given
Precision; Not Given
Time of Measurement: Not Given
Calibration Requirements: Counter Background - Gamma spectrometer - counter efficiency.
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage. Handling); Immediately after
collection of milk sample, a preservative is added to the sample and, if possible,
the sample is refrigerated.
References:
(1) Douglas, Geneva S. (Editor), Radloassay Procedures for Environ-
mental Samples, National Center for Radiological Health, U. S.
Public Health Service, Rockvilie, Maryland, January 1967.
(2) Kahn, B., G. K. Hurthy, C. Porter, G. R. Hagee, G. J. Karches, and A. S. Goldin.
Rapid Methods for Estimating Fissions Product Concentrations in Milk. Public
Health Service Publication No. 999-R-2, Environmental Health Series, Radio-
logical Health (1963).
(3) Ibid., p. 17
*
Thit: method is considered acceptable by EPA, but is not necessarily used in EPA
laboratories
E-12
-------
E-13
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Cesium
Medium: Water
Name of Measurement Method: Not Given
Principal Detection Technique; Gamma ray spectroscopy. Beta count to measure
HPCSV and confirm half-ltfp.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stantions during routine
operations, the amount of the radionuclide present is determined.
Summary of Method; Cesium carrier is added to the aqueous sample. The cesium is
collected as the phosphomolybdate and purified as Cs^tCl^ for counting.
Limitations;
Range of Applicabilityi Minimum Detectable Limits
Gamma Ray Beta Particle
1JOCs 0.07 0.02
The minimum detectable limits were calculated for 100 ml aliquots for each
analysis and a 100 minute counting time. Although not always practical, lower
limits can be obtained with larger sample volumes and longer counting time.
For nuclides discharged from light-water moderated nuclear power reactors, the
composition of the test solutions has ranged from mixtures of many radio-
nuclides at microcuries per milliliter concentrations to barely detectable levels
at picocuries per liter concentrations. The substrate quality has ranged from
highly deionized coolant water to waste solutions of high salt contents plus
detergents.
Interferences: Decontamination Factors
131I 58/60Co 110mAg
10* 103 103
Pitfalls: Special Precautions: With the multitude of reactor and waste
solutions generated, radionucide and chemical corpositions will vary and
therefore require auxiliary treatment to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not Given
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Procedure
time: 4 samples - 5 hours. Repeat gamma spectral measurements at 1-week
intervals to measure decay of Cs . Beta count at 1-month intervals.
Calibration Requirements: Counter background. Calibrate gamma spectrometer and
beta counter.
Data Outputs:. Counts and time and energy.
Special Sampling Requirements (Collection. Storage, Handling): Not Given
Reference :
Procedures for Radlochemical Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
E-13
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E-14
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Chromium
Medium: Water
Name of Measurement Method: Chromium (Ion Exchange)
Principal Detection Technique: Gamma ray spectroscopy
Purpose of Measurement (Important Applications); To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method; Chromium carrier (Cr 7 and appropriate holdback carriers are+6
added to the acidified aqueous sample. Chromium is oxidized to the Chromate (Cr ),
and impurities are removed by nitric acid evaporations (to volatilize radioiodine)
and cation exchange. The chromium is precipitated as BaCrO, for counting.
Limitations:
Range of Applicability; Minimum Detectable Limits (pCl/ml)
Gamma Ray
51Cr 0.5
The minimum detectable limits were calculated for 100 ml aliquots for each
analysis and a 100 minute counting time. Although not always practical, lower
limits can be obtained with larger sample volumes and longer counting time.
For nuclides discharged from light-water moderated nuclear power reactors, the
composition of the test solutions has ranged from mixtures of many radio-
nuclides at microcuries per milliliter concentrations to barely detectable levels
at picocurles per liter concentrations. The substrate quality has ranged from
highly deionized coolant water to waste solutions of high salt contents plus
detergents.
Interferences; Decontamination Factors
131I 58/60Co 110mAg
103 103 102
Pitfalls; Special Precautions: With the multitude of reactor and waste
solutions generated, radionuclide and chemical compositions will vary
and therefore require auxiliary treatment to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not Given
Time of Measurement (Maximum Frequency. Recovery Period, etc.); Procedure
time: 2- samples - 5 hours. Repeat gamma spectral measurement at 1-month
Intervals to measure decay and confirm purity.
Calibration Requirements: Counter background - Gamma spectrometer.
Data Output; Counts and time and energy
Special Sampling Requirements (Collection. Storage, Handling): Not given
Rpfprenpp;
Procedures for Radiochemlcal Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-6A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
E-14
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E-15
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Cobalt 60
Medium: Soil and silt
*
Name of Measurement Method: Gamma spectrometry
Principal Detection Technique: Gamma spectrometry
Purpose of Measurement (Important Applications): Determine content of cobalt 60 in
soil and silt.
Summary of Method: Fuse sample. Place in container for gamma spectrometry.
Limitations:
Range of Applicability: Not Given
Interfences: Not Given
Pitfalls; Special Precautions: Not Given
Statistical Characteristics;
Accuracy: Not Given
Precision; Not Given
Time of Measurement: Not Given
Calibration Requirements: Background; gamma spectrometer; counter efficiency
Data Outputs: Counts, time, and energy
Special Sampling Requirements (Collection, Storage, Handling): Fuse sample
Reference:
Douglas, Geneva S. (Editor), Radioassay Procedures for Environmental Samples,
National Center for Radiological Health, U. S. Public Health Service,
Rockville, Maryland,January 1967.
*
This method Is considered acceptable by EPA, but is not necessarily used in EPA
laboratories.
E-15
-------
E-16
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Cobalt
Medium; Water
Name of Measurement Method: Cobalt-Nickel
Principal Detection Technique: Gamma spectroscopy to identify isotopes. Beta
count to measure decay and confirm half-life.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine opera-
tions, the amount of the radionuclide present is determined.
Summary of Method; Cobalt and nickel carriers added and precipitated as insoluble
hydroxides. Cobalt is separated and purified as K,CO(NO-)6 for counting. This
method also precipitates nickel.
Limitations;
Range of Applicability: See Cobalt-Cadmium Method for Cobalt (E-17).
Interferences: Nickel also precipitated. See Cobalt-Cadmium Method for
decontamination factors.
Pitfalls; Special Precautions; See Cobalt-Cadmium Method.
Statistical Characteristics;
Accuracy and Precision; Not Given
Time of Measurement: 2 samples - 8 hrs. (Includes time for preparation of nickel).
Repeat gamma measure after 2 and 4 weeks. Beta count at one month Intervals.
Calibration Requirements: Counter background - Calibrate gamma spectrometer and beta
counter.
Comments by Users: See Cobalt-Cadmium Method
Data Outputs; Counts and time and energy.
Special Sampling Requirements (Collection, Storage. Handling): Not Given
Reference.:
Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
E-16
-------
E-17
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured! Radioactive Cobalt
Medium: Water
Name of Measurement: Cobalt-Cadmium
Principal Detection Technique: Gamma ray spectroscopy co Identify Isotopes -
Beta count to measure decay and confirm half-life.
Purpose of Measurement (Important Applications); To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routlnte
operations,the amount of the radlonucllde present Is determined.
Summary of Method! Cobalt and cadmium carriers are added to the aqueous sample
and collected as Insoluble hydroxides. The cobalt Is precipitated and purified
as K.Co(NO-)g for counting; cadmium is precipitated as Che sulfide In acid solution
and purified as Cd(OH). for counting.
Limitations:
Range of Applicability: Minimum Detectable Limits (pCl/ml)
Gamma Ray Beta Particle Special Cases*
58Co 0.05 - 0.03
60Co 0.05 0.02 0.03
•based on 400 ml plastic container counted for 300 minutes
The minimum detectable limits were calculated for 100 ml allquots for each
analysis and a 100 minute counting time. Although not always practical, lower
limits can be obtained with larger sample volumes and longer counting time.
For nuclldes discharged from light-water moderated nuclear power reactors, the
composition of the test solutions has ranged from mixtures of many radlo-
nuclldes at microcuries per mllliliter concentrations to barely detectable levels
at plcocurles per liter concentrations. The substrate quality has ranged from
highly deionized coolant water to waste solutions of high salt contents plus
detergents.
Interferences: Cadmium Is also precipitated by this method.
Decontamination Factors
131X 110mAg
58Co 103 103
60Co 103 103
Pitfalls; Special Precautions: With the multitude of reactor and waste
solutions generated, radlonucllde and chemical compositions will vary
and therefore require auxiliary treatment to effect desired decontamination.
Beta count Immediately to corroborate Cobalt half-lives. Plot gamma ray
spectrum Immediately to identify 57 , 58 , and 60. .
Statistical Characteristics;
Accuracy and Precision: Not given
Time of Measurement: Procedure time: 4 samples - 8 hours; plot gamma
ray spectrum immediately. Repeat gamma measure after 2 weeks and after
It weeks to observe decav of shorter-lived cobalt Isotopes. Beta count
immedlatelv and at 1-month Intervals to corroborate half-lives of
57Co, 58Co, and 60Co.
Calibration Requirements: Counter background. Calibrate gamma spectrometer
and beta counter.
Comments by Users: The *°K beta in K]Co(NO2). will add approximately 10 dpm
per 20 mg separated precipitate, and chis background must be taken into consi-
deration during the beta decay counting.
Data Outputs: Counts and time and energy.
Special Sampling Requirements (Collection. Storage. Handling): Not given
References:
(1) Procedures for Radlochemlcal Analysis of Nuclear Reactor Aqueous
Solutions, Report Mo. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Llngane, J. J., Llngane, P. J., and Morris, M. D., Anal. Chlm. Acta,
29, 10 (1963).
(3) Lingane, J. J., ibid, 31, 315 (1964).
E-17
-------
E-18
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Copper
Medium; Hater
Name of Measurement Method: Not Given
Principal Detection Technique; Gamma ray spectroscopy to identify Cu and verify
purity of separation and to follow decay. Beta count to corroborate the half-life.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: Copper carrier and appropriate holdback carriers are added to
an acidified aqueous sample and both copper and technetium are precipitated as
sulfides. After dissolving the precipitate, the technetium is separated from the
copper by cation exchange purification and coprecipicated with copper carrier as
CuS for counting. The copper is eluted from the resin column, reduced to Cu+ with
ria.SO., and precipitated as CuCNS for counting.
Limitations; Range of Applicability! Minimum Detectable Limits (pCi/ml)
Gamma Ray Beta Particle
"Cu 0.1
The minimum detectable limits were calculated for 100 ml aliquots for each
analysis and a 100 minute counting time. Although not always practical, lower
limits can be obtained with larger sample volumes and longer counting time.
For nuclldes discharged from light-water moderated nuclear power reactors, the
composition of the test solutions has ranged from mixtures of many radlo-
nuclides at raicrocuries per milliliter concentrations to barely detectable levels
at picocuries per liter concentrations. The substrate quality has ranged from
highly deionized coolant water to waste solutions of high salt contents plus
detergents.
Interferences: Decontamination Factors
131T 58/60. 110m.
1 Co Ag
103 103 103
Techneclum is also precipitated by this method.
Pitfalls; Special Precautions; Gamma ray spectrum used to verify purity
of separation. Plot gamma ray spectrum immediately after separation. With
the multitude of reactor and waste solutions generated, radionuclide and
chemical compositions will vary and therefore require auxiliary treatment
to effect desired decontamination.
Statistical Characteristics;
Accuracy and Precision: Not given
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Procedure
time: 2 samples - 6 hours. Plot gamma ray spectrum immediately and repeat
daily for a week to follow decay. Beta count the planchet at 2, 6, 12, 24
and 48-hour intervals to corroborate half-life.
Calibration Requirements: Counter background. Calibrate gamma ray spectrometer
and beta counter.
Data Outputs; Counts and time and energy.
Special Sampling Requirements (Collection. Storage. Handling); Not given
Reference;
(1) Procedures for Radlochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA. Cincinnati, Ohio, 1972.
(2) Master Analytical Manual, ORNL, TID-7015, Method 5-11230, 1957.
(3) Kolthoff, I.M., and Sandell. K.B., Textbook of Quantitative Inorganic
Analysis, p. 701, The - n Co., 1946.
E-18
-------
E-19
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Gross beta activity and gross gamma activity*
Medium: Air
Name of Measurement Method: Gross beta counting; gamma pulse height analysis
Principal Detection Technique: Beta counter; gamma spectrometry
Purpose of Measurement (Important Applications): Determine which radionuclides to
analyze air sample for.
Summary of Method: Three to five days after collection, the gross beta activity Is
counted for one minute. If the count is less than 2000 cpm, the sample is stored and
the gross beta activity computed. If the count is greater than or equal to 2000 cpm,
the sample is counted again for gross beta activity seven days later and an estimate
of the age of the fission products is made and beta activity is extrapolated to time
of collection. Samples with more than 2000 cpm are analyzed by gamma spectrometry to
Identify and measure gamma emitters.
Limitations:
Range of Applicability: Continuous collection over 24 hours
Interferences: Radon daughter activity
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy; No attempt is made to evaluate the overall accuracy of the gross beta
activity measure. A confidence level would be of questionable value since there
are so many variables in the collection.
Precision: Reproducibility of the beta counting result Is very good.
Time of Measurement: Three to ten days for beta counting; at least two weeks
for gamma spectrometry.
Calibration Requirements:
90 90
Beta counter; gamma spectrometer; background strontium 90 count; Sr - Y
performance standard.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling): The air sample is a
filter on which partlculate or adsorbable airborne material is collected continuously
over a 24-hour period. If the field estimate of the filter shows at least SO pCi/M^
of gross beta activity (excluding radon daughter activity), a charcoal cartridge is
inserted behind the filter. Immediately after removal from the sampler, the filter
is placed in a glassine envelope. Five hours after collection, the beta-gamma activity
is estimated. Starting three to five days later, the gross beta activity, and if
applicable, the gross gamma activity is measured. The samples are then prepared for
radiochemical analysis according to the type of filter used.
References:
(1) Douglas, Geneva S. (Editor), Radioassay Procedures for Environ-
mental Samples, National Center for Radiological Health, U. S.
Public Health Service, Rockvllle, Maryland, January 1967.
(2) Way. K. and E. P. Wigner. "The Rate of Decay of Fission Products". Phys. Rev.
23:1318-1330 (1948)
(3) Covell, D.F. "Determination of Gamma-Ray Abundance Directly from Total Absorption
Peak". Anal Chem 31:1785-1790 (1959)
(4) Burrus, W. R. "Unscrambling Scintillation Spectrometer Data". IRE Trans on Nucl
Sci. NS-7. 20:102-111 (1960).
* This method Is considered acceptable by EPA, but Is not necessarily used in
EPA laboratories.
E-19
-------
E-20
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Gross Alpha and Beta Activity
Medium; Water
Name of Measurement Method: Not given
Principal Detection Technique; Alpha counter
Beta counter
Purpose of Measurement (Important Applications): To provide an index to the
radioactive contamination of the sample.
Summary of Method; Filter the sample. Place filter paper in a tared planchet
and ignite. Flame the planchet, weigh for self-absorption correction, and
alpha and beta count.
Add HNO. to the filtrate and evaporate to near dryness. Transfer to a tared
planchet. Flame the planchet, weigh for self-absorption correction and alpha
and beta count.
Limitations:
Range of Applicability: Total, or suspended and dissolved solids
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics;
Accuracy; Not given
Precision; Not given
Time of Measurement; Not given
Calibration Requirements: Alpha counter
Beta counter
Self-absorption factors
Background
Comments by Users; For drinking water, if the total alpha activity is greater
than 3 pCi/liter, radium 226 content must be determined. And, if the total beta
activity is greater than 10 pCi/liter, strontium 90 must be determined.
Data Outputs: Counts and time
Special Sampling Requirements (Collection, Storage. Handling): Not given
Reference;
Johns, ^rederick B., Southwestern Radiological i'ealth Laboratory,
Handbook of Tadlochemlcal Analytical Methods, March 1970 (reprint
January 1972).
E-20
-------
E-21
SUMMARY OF ANALYTICAL METHOD
*
Parameter(a) Measured: Gross alpha and gross beta activity
Medium; Hater
Name of Measurement Method: Gross alpha and gross beta activity in total residue
Principal Detection Technique; Internal proportional alpha counter; low background
beta counter.
Purpose of Measurement (Important Applications): To determine whether further tests of
radionuclides are necessary.
Summary of Method: A sample of water is evaporated and the residue is transferred
to a planchet for counting gross alpha and gross beta or beta-gamma activities.
Limitations;
Range of Applicability: Clear water
Interferences; Not given
Pitfalls; Special Precautions: Water polluted with industrial or domestic
wastes is subject to rapid chemical and biological changes. These should be
considered in relation to the objectives of studies on radionuclide content.
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement: Not given
Calibration Requirements: Counter backgrounds; alpha counter; beta counter
2 90 90
Comments by Users; If sample thickness exceeds 20 mg/cm , and Sr- Y self-
absorption factors are used, report beta-gamma activity rather than gross beta
activity.
Data Outputs: Counts and time (pCi/liter)
Special Sampling Requirements (Collection. Storage. Handling); Extreme caution should
be taken to assure proper sampling of water containing suspended matter. The
examination of suspended and filtrate activities precludes the addition of carrier or
preservatives. There should be no undue delay in processing such samples after
collection, wnen there is little or no suspended matter, add appropriate carriers
and hydrochloric or nitric acid. Turbid water requires stringent treatment.
Reference-.
(1) Douglas, Geneva S. (Editor), Radioassay Procedures for Environ-
mental Samples, National Center for Radiological Health, U. S.
Public Health Service, Rockvllle, Maryland, January 1967.
(2) Public Health Service Drinking Water Standards - 1962. Public Health Service
Publication No. 956, Washington, U. S. Government Printing Office (1962).
(3) Porter, C. E., R. J. Augustine, J. M. Matusek, Jr., and M. W. Carter. Procedures
for Determination of Stable Elements and Radionuclides in Environmental Samples.
Public Health Service Publication No. 999-RH-10, Environmental Health Series,
Radiological Health (1965).
*This mefhod is considered acceptable by EPA, but is not necessarily used in EPA
laboratories.
E-21
-------
E-22
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Iodine 131
Medium; Food
Name of Measurement Method: Not given
Principal Detection Technique; Gamma Spectrometry *
Purpose of Measurement (Important Applications): Prevention and control of radio-
logical hazards by defining the transport of the radioactive contaminant from its
source to its ultimate deposition in man.
Summary of Method: Measure undissolved homogenate by gamma spectrometry.
Limitations:
Range of Applicability; Minimum detectable concentration is 10 pCi/kg
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy and Precision; Not given
Time of Measurement: Not given
Calibration Requirements; Counter background; gamma spectrometer; counter efficiency.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection, Storage. Handling): The sample must
represent the edible portion or the portion actually consumed, should be prepared and
"served" in reasonable portions, must be made homogeneous and must be put in solution.
This can be done by ashing, digesting In acid, fusing, or a combination of these.
Food samples should be packaged in waterproof containers, frozen during storage, and
thawed prior to analysis. Preservatives may be needed.
Reference:
Douglas, Geneva S. (Editor), Radioassay Procedures for Environmental Samples,
National Center for Radiological Health, U. S. Public Health Service,
Rockville, Maryland, January 1967.
* ThJi method is considered acceptable by EPA, but is not necessarily used in EPA
laboratories.
E-22
-------
E-23
SUMMARY OF ANALYTICAL METHOD
Parameter (s) Measured: Iodine 131*
Medium: Milk
Name of Measurement Method: Not given
Principal Detection Technique: Gamma spectrometry *
Purpose of Measurement (Important Applications) : Prevention and control of radio-
logical hazards by defining the transport of the radioactive contaminant from its
source to its ultimate deposition in man.
Summary of Method: Pour a measured (3.5 liter) aliquot into the inverted-well
type sample container which fits over the right-cylindrical sodium iodine crystal
detector and count.
Limitations:
Range of Applicability: Not given
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement; Not given
Calibration Requirements: Counter background; gamma spectrometer; counter efficiency.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling); Immediately after
collection of milk sample, a preservative is added to the sample, and, if possible,
the sample is refrigerated.
Reference ;
(1) Douglas, Geneva S. (Editor), Radioassay Procedures for Environ-
mental Samples, National Center for Radiological Health, U. S.
Public Health Service, Rockville, Maryland, January 1967.
RH Mu ' ' ' e- G' J- Karches, and A. S. Goldin.
Rapid Methods for Estimating Fission Product Concentrations in Milk Public
Health SQ963) .P"bliCati°n »°' 9"-R~2' Environmental Health Series. Radiological
(3) Ibid., p. 17
This method is considered acceptable by EPA, but not necessarily used in EPA
laboratories.
E-23
-------
E-24
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Iodine
Medium: Water
Name of Measurement Method: ASTM D2334-68
131
Principal Detection Techniques: Gamma ray spectroscopy to identify I,
133j, and 135j. Beta count to measure decay and half-life.
Purpose of Measurement (Important Applications); To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: To assure chemical interchange with the iodine carrier,
an oxidation-reduction cycle is made. The iodide is oxidized with permangenate
to remove chlorine and bromine. Distillation of elemental iodine into cold
carbon tetrachloride is accomplished. After washing the carbon tetrachloride
with nitric acid, the iodine is reduced with bisulfate and back-extracted Into
water. Acidified silver nitrate solution is added to precipitate silver iodide.
The chemical recovery is used as a measure of radiochemical recovery. The
silver iodide precipitate is mounted for gamma counting.
Limitations:
Range of Applicability: Minimum Detectable Limits
Gamma Ray Beta Particle Special Case*
131j. 0.05 0.01 0.02
133 0.07 0.02
*Based on 400 mi-plastic container counted
for 300 minutes.
The minimum detectable limits were calculated for 100 ml aliquots for each
analysis and a 100-minute counting time. Although not always practical,
lower limits can be obtained with larger sample volumes and longer counting
time. For nuclides discharged from light-water moderated nuclear power
reactors, the composition of the test solutions has ranged from mixtures
of many radionuclides at microcuries per milliliter concentrations to
barely detectable levels at picocuries per liter concentrations. The sub-
strate quality has ranged from highly deionized coolant water to waste
solutions of high salt contents plus detergents.
Interferences: Bromine. Decontamination Factors
58/60Co 110 MAg
103 102
Pitfalls; Special Precautions: The permanganate oxidation step gives
added decontamination from bromine activation product. Plot gamma ray
spectrum immediately.
With the multitude of reactor and waste solutions generated,radionuclide
and chemical compositions will vary and therefore require auxiliary treat-
ment to effect desired decontamination.
Statistical Characteristics;
Accuracy and Precision; Not given
Time of Measurement (Maximum Frequency. Recovery Period, etc.); Plot
gamma ray spectrum immediately and after 6 hours, 24 hours, 2 days,,
5 days, 1 week and 3 weeks. Beta-count Agl daily to measure decay and
confirm half-line.
Calibration Requirements; Counter background. Calibrate gamma spectrometer
and beta counter.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling): Not given
Reference:
Procedure for Radiochemical Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research
Center, EPA, Cincinnati, Ohio, 1972.
E-24
-------
E-25
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radioactive Iodine
Medium; Water
Name of Measurement Method: Distillation
Principal Detection Technique; Gamma Ray Spectroscopy to identify isotopes.
Beta count to measure decay and confirm half-life.
Purpose of Measurement (Important Applications):
To evaluate potential health hazard from radionuclide discharges at nuclear
power stations during routine operations, the amount of the radionuclide present
is determined.
Summary of Method: Iodide carrier and appropriate holdback carriers are added
to the aqueous sample. After acidifying the sample, iodine is distilled into
caustic solution. The distillate is acidified and the iodine is extracted into
CC1,. After back extraction, the iodine is purified as Agl for counting.
Limitations;
Ranee of Applicability: Same as Radioactive Iodine by ASTM D2334-68.
Interferences: Same as Radioactive Iodine
Pitfalls; Special Precautions:
With the multitude of reactor and waste solutions generated,radionuclide and .
chemical compositions will vary and therefore require auxiliary treatment to
effect desired decontamination.
Statistical Characteristics: Accuracy and Precision: Not given.
Time of Measurement (Maximum Frequency. Recovery Period, etc.); Procedure
time: 2 samples - 6 hours; same as radioactive iodine.
Calibration Requirements; Same as Radioactive Iodine
Data Outputs; Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling): Not given.
Reference :
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
(2) Kleinberg, J. and Cowan, G.A., "The Radiochemistry of Fluorine, Chlorine,
Bromine, and Iodine," Nuclear Science Series, NAS-NS-3005, National Academy
of Science, National Res. Council, USAEC, 1960.
E-25
-------
-•-26
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radioactive Iron
Medium: Water
Name of Measurement Method: ASTM D2461-69
Principal Detection Technique; Gamma ray counter or spectrometer or beta particle
eg 55
detector to identify 45-d Fe . X-ray proportional counter to identify 2.7 yr. Fe
Purpose of Measurement'(Important Applications); To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: Radioactive iron and added iron carrier are separated from other
activities by hydroxide precipitation, liquid-liquid extraction, and ion exchange.
The separated iron is counted with a gamma counter or spectrometer, or a beta
particle detector.
Limitations;
Range of Applicability: Minimum Detectable Limits (pCi/ml)
Gamma Ray Beta Particle Special Case*
55Fe - - 0.02
39Fe 0.1
*value derived from 1000 minute count on the X-ray
proportional counter.
The minimum detectable limits were calculated for 100 ml aliquots for each
analysis and a 100-minute counting time. Although not always practical,
lower limits can be obtained with larger sample volumes and longer counting
time. For nuclides discharged from light-water moderated nuclear power
reactors, the composition of the test solutions has ranged from mixtures
of many radionuclides at microcuries per milliliter concentrations to
barely detectable levels at plcocuries per liter concentrations. The
substrate quality has ranged from highly deionized coolant water to waste
solutions of high salt contents plus detergents.
Interferences: Decontamination Factors
131T 58/60. 110m.
I Co Ag
55 104 102 10*
3 24
59^ 10J 10Z 10*
Pitfalls; Special Precautions: With the multitude of reactor and waste
solutions generated,radionuclide and chemical compositions will vary and
therefore require auxiliary treatment to effect desired decontamination.
Repeated countings with the X-ray proportional counter may be necessary•
to detect 58Co if present.
Special Characteristics;
Accuracy and Precision: Not given
Time of Measurement (Maximum Frequency, Recovery Period, etc.); Hot given
Calibration Requirements: Counter background. 'Caliorate gamma spectrometer
and beta counter.
Data Outputs: Counts and time and energy.
Special Sampling Requirements (Collection. Storage. Handling): Not given
Reference:
Procedures for Radlochemlcal Analysis of Nuclear Reactor Aqueous
Solutions, Report Ho. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
E-26
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27
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Iron
Medium! Water
Name of Measurement Method: Not given
59
Principal Detection Technique: Gamma ray spectroscopy to identify 45-d Fe.
X-ray proportional counter to identify 2.7 year Fe.
Purpose of Measurement (Important Applications);Same as radioactive iron by ASTM D2461-69.
Summary of Method: Iron carrier and the appropriate holdback carrier are added to the
acidified aqueous sample. Iron is extracted into trioctylphosphine oxide and back
extracted into dilute perchloric acid. After double precipitation of the hydrous
oxide to separate it from impurities, the iron is precipitated as the alcohol-washed
Fe(OH)3.?H20 for counting.
Limitations:
Range of Applicability: Same as radioactive iron
Interferences! Same as radioactive iron.
Pitfalls; Special Precuatlons; Same as radioactive iron.
For a sample containing significant cobalt activity, modification of the
procedure is necessary.
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement (Maximum Frequency, Recovery Period, etc.): Procedure
time: 2 samples - 4 hours
Calibration Requirements: Not given
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection, Storage. Handling): Not given
Reference;
Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
E-27
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E-28
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Krypton-85
Medium: Krypton Gas (derived from atmosphere)
Name of Measurement Method: Liquid scintillation counting
Principal Detection Technique: Liquid scintillation counting
Purpose of Measurement (Important Applications): Krypton 85 in air originates
primarily from nuclear reactors.
Summary of Method: Commercially available krypton gas is introduced into the
scintillation vials to the desired pressure by means of a manifold and the
deaerated scintillation solution introduced by means of a syringe. The vials are
capped and counted in a liquid scintillation counter.
Limitations:
Range of Applicability: Not given
Interferences: Not given
Pitfalls; Special Precautions: Do not exceed solubility of krypton in
scintillation mix.
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement: Not given
Calibration Requirements: Liquid scintillation counter
Comments by Users: Method can be used for any gas as long as the solubility of that
gas in the scintillation mix is not exceeded.
Data Outputs: Electromechanical Sealer
Special Sampling Requirements (Collection. Storage. Handling): Not given
References:
(1) Strong, Ann (Editor), Procedures for Radiochemical Analysis at the Eastern
Environmental Radiation Laboratory, EERL Report No. 7X-XXXX (Draft),
Eastern Environmental Research Laboratory, EPA, Montgomery, Alabama (Undated).
(2) Shuping, R.E., C.R. Phillips, and A.A. Moghissi, "Lou Level Counting of
Environmental Krypton-85 by Liquid Scintillation," Analyt. Chem. 41,
2082 (1969). ~
E-28
-------
E-29
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radiokrypton
Medium: Ambient air
Name of Measurement Method; Not given
Principal Detection Technique: Scintillation counter
Purpose of Measurement (Important Applications); To determine the radiokrypton con-
tent of ambient air.
Summary of Method: The sample is transferred to the gas analysis apparatus.
Water is removed by freezing and distillation. The radiokrypton, radioxenon,
radon 222, and carbon dioxide are separated by elution through a molecular
sieve column at various temperatures. The volumes of the separated gases are
measured for yield determination and transferred to appropriate counting
chambers.
Limitations;
Range of Applicability; Not given
Interferences; Not given
Pitfalls; Special Precautions; Not given
Statistical Characteristics;
Accuracy; Not given
Precision: Not given
Time of Measurement; Not given
Calibration Requirements;
Counter efficiency
Background
Data Outputs; Counts and time
Special Sampling Requirements (Collection. Storage. Handling); Samples may
be either grab or cryogenic.
Reference;
Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radtochemlcal Analytical Methods, March 1970 (reprint
January 1972).
E-29
-------
E-30
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radiokrypton
Medium; Natural gas
Name of Measurement Method; Not given
Principal Detection Technique; Scintillation counter
Purpose of Measurement (Important Applications); To determine radiokrypton
content of natural gas.
Summary of Method; Convert the sample to carbon dioxide and water by
combustion. Separate the water by freezing. The gases are then adsorbed
on charcoal at liquid nitrogen temperature and separated from carbon
dioxide and each other by a series of low temperature chromographlc steps.
The radiokrypton is then analyzed using the method listed in this compendium,
referenced under Frederick B. Johns, for radiokrypton in ambient air.
Limitations:
Range of Applicability; Not given
Interferences; Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics;
Accuracy; Not given
Precision! Not given
Time of Measurement: Not given
Calibration Requirements;
Counter efficiency
Background.
Data Outputs; Counts and time
Special Sampling Requirements (Collection. Storage. Handling); Not given
Reference;
Johns, Frederick S., Southwestern Radiological Health Laboratory
Handbook of Padlochemical Analytical Methods, March 1970 (reprint
January 1972).
E-30
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E-31
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Lanthanum (plus trlvalent rare earths and yttr^uc)
Medium: Water
Name of Measurement Method: Not given
Principal Detection Technique: Gamma ray spectroscopy for identification. Beta count
140 147
to corroborate La half-life and to ascertain if Pm is present.
Purpose of Measurement (Important Applications): To evaluate potential health hazard
from radionuclide discharges at nuclear power stations during routine operations,the
amount of the radionuclide present is determined.
Summary of Method; Lanthanum carrier and appropriate scavenging carriers are added
to the acidified aqueous sample and impurities are removed by cobaltinitrite and
iodate precipitations. The lanthanum is collected as the hydroxide and purified
as La2(C204)3.8H20 for counting.
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
Nuclide Gamma Ray Beta Particle
140La 0.1 0.01
The minimum detectable limits were calculated for 100 ml aliquots for each
analysis and a 100 minute counting time. Although not always practical, lower
limits can be obtained with larger sample volumes and longer counting time.
For nuclides discharged from light-water moderated nuclear power reactors, the
composition of the test solutions has ranged from mixtures of many radio-
nuclides at microcuries per mlllllitet concentrations co barely detectable levels
at picocuries per liter concentrations. The substrate quality has ranged from
highly deionized coolant water to waste solutions of high salt contents plus
detergents.
Interferences: Decontamination Factors for La
131, 58/60Co 110mAg
103 103 1C3
Pitfalls; Special Precautions: Plot gamma ray spectrum immediately. With
the multitude of reactor and waste solutions generated, radionuclide and
chemical compositions will vary and therefore require auxiliary treatment
to effect desired decontamination. If yttrium isotopes '°Y, '^-Y, or 93Y
are believed to be present, the yttrium procedure (see yttrium) should be
performed on an acidified aliquot for verification.
Statistical Characteristics:
Accuracy and Precision; Not given
Time of Measurement; Procedure Time: 4 samples..- 6 hours. Plot gamma ray
spectrum immediately and at daily intervals if r appears to be present:
continue at £^jeek intervals to confirm. Beta count at 2-dav intervals tg_
corroborate La half-life. After 1 month, beta count to ascertain if Pm
is present.
Calibration Requirements: Counter background. Calibrate gamma spectrometer and
beta counter.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage, Handling): Not given
Reference:
Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
E-31
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E-32
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Manganese 55*
Medium: Soil and Silt
Name of Measurement Method: Gamma spectrometry*
Principal Detection Technique: Gamma Spectrometry
Purpose of Measurement (Important Applications); Determine content of manganese 55 in
soil and silt.
Summary of Method: Fuse sample. Place in container for gamma spectrometry.
Limitations:
Range of Applicability! Not given
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement; Not given
Calibration Requirements: Background; gamma spectrometer
Data Outputs; Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling); Fuse Sample
Reference:
Douglas, Geneva S. (Editor), Radioassay Procedures for Environmental
Samples, National Center for Radiological Health, U. S. Public Health
Service, Rockville, Maryland, January 1967.
* This method is considered acceptable by EPA, but not necessarily used in EPA
laboratories.
E-32
-------
E-33
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Manganese
Medium: Water
Name of Measurement Method; ASTM D2039-70
Principal Detection Technique: Gamma ray spectroscopy
Purpose of Measurement (Important Applications): To evaluate potential health hazard
from radionuclide discharges at nuclear power stations during routine operations, the
amount of the radionuclide present is determined.
Summary of Method: Radioactive manganese and the added carrier are first precipitated
as manganese dioxide. A final gravimetric precipitation of manganese ammonium phos-
phate is used to compute the chemical yield of the process.
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
Gamma Ray Beta Particles Special Case*
54Mn 0.06 - 0.02
*For the special case the limits are based on a 100 ml
plastic container A" diameter by 2.5" high counted
for 300 minutes.
Interferences; Cobalt.
Decontamination Factor
»ll 58/6°Co 110%
103 103 10*
Pitfalls; Special Precautions; If cobalt contamination persists, the decon-
tamination procedure for cobalt should be repeated. With the multitude of
reactor and waste solutions generated,radionuclide and chemical compositions
will vary and therefore require auxiliary treatment to effect desired decon-
tamination.
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Plot gamma
ray spectrum immediately and after 4 hours to identify and quantify 2.58 hr
56Mn and 313d 5*Mn. Gamma scan again in 1 week to substantiate 313d *Mn.
Calibration Requirements: Counter background - Gamma ray spectrometer.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage, Handling): Not given
Reference:
Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
E-33
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E-34
SUMMARY OF ANALYTICAL METHOD
Parametcr(s) Measured: Radioactive Manganese
Medium: Hater
Name of Measurement Method; Not Given
Principal Detection Technique: Same as radioactive manganese (ASTM D2039-70).
Purpose of Measurement (Important Applications); Same as radioactive manganese.
Summary of Method: Manganese carrier and appropriate scavenging carriers are added
to the acidified aqueous sample and impurities are removed by cobaltinltrite and
hydroxide precipitations. The manganese is purified as MnNH.PO,.H_0 for counting.
Limitations:
Range of Applicability: Same as radioactive manganese
Interferences; Same as radioactive manganese
Pitfalls; Special Precautions: With the multitude of reactor and waste
solutions generated,radionuclide and chemical compositions will vary and
therefore require auxiliary treatment to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement (Maximum Frequency. Recovery Period, etc.); Procedure
time: 4 samples - 3 hrs; same as radioactive manganese
Calibration Requirements: Same as radioactive manganese
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling); Not given
Reference;
Procedures for Radiochemlcal Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
E-34
-------
E-35
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Molybdenum
Medium: Water
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma ray spectroscopy to identify Mo and
observe decay. Beta scan to corroborate half-life.
Purpose of Measurement (Important Applications) : To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: Molybdenum carriers and appropriate scavenging carriers are
added to the aqueous sample. Impurities are removed by a double hydroxide scavenge
followed by sample evaporation. The molybdenum is extracted into diethyl ether,
back extracted into water, precipitated with a-benzoinoxime and ashed to MoO, for
counting. •*
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
Gamma Ray Beta Particle
99Mo 0.3 0.01
Interferences : Decontamination Factors
131X 58/60Co 110mAg
102 103 103
Pitfalls; Special Precautions: With the multitude of reactor and waste
solutions generated, radionuclide and chemical compositions will vary and
therefore require auxiliary treatment to effect desired decontamination.
Plot gamma ray spectrum soon after separation to identify any contaminating
gamma emitters.
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Procedure
time: 2 samples - 6 hours. Plot gamma ray spectrum soon after separation
and gamma scan at 2 or 3-day intervals to observe decay. Starting two
days after separactlon, beta count at 3-day intervals to confirm half-life.
Calibration Requirements: Counter background. Calibrate gamma spectrometer
and beta counter.
Comments by Users; The presence of Ho can also be corroborated by following
the ingrowth of the 6.0 hr. '"Tc daughter. Two days after separation, "MO-
°9mTc equilibrium is nearly complete.
Data Outputs: Counts and time and energy
Special Sampling -Requirements (Collection. Storage, Handling): Not given
Reference:
Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
E-35
-------
E-36
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Neptunium
Medium: Water
Name of Measurement Method; Not given.
239
Principal Detection Technique: Gamma ray spectroscopy to identify Np.
Beta count to record decay and corroborate half-life.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: Cerium carrier is added to the acidified aqueous sample, and
is scavenged along with rare earth fission products by a fluoride precipitation
in an oxidized solution while neptunium remains in solution; Lanthanum carrier
and appropriate holdback carriers are added, and neptunium Is collected on the
lanthanum fluoride precipitate under reduced conditions. The neptunium is
purified by a double hydroxide precipitation and is carried on La(OH), for
counting.
Limitations;
Range of Applicability: Minimum Detectable Limits (pCi/ml)
Gamma Ray Beta Particle
2V>
Np 0.15 0.01
Interferences: Decontamination Factors
131Z 58/60Co llOm^
10* 10* 10*
Pitfalls; Special Precautions: Plot gamma ray spectrum Immediately after
separation to identify any contaminating gamma emitters. Further decon-
tamination can be accomplished by adding one drop each of the holdback
carriers and reprecipltating lanthanum fluoride under reducing conditions
after dissolving the first lanthanum fluoride precipitate. With the
multitude of reactor and waste solutions generated, radionuclide and
chemical compositions will vary and therefore require auxiliary treatment
to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement: Procedure time: 2 samples - 3 hours. Plot gamma
ray spectrum Immediately. Gamma scan at one-day intervals to observe
decay. Beta count daily.
Calibration Requirements: Counter background. Calibrate gamma spectrometer
ana oeta counter.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling): Not given
Reference:
Procedures for Radiochemlcal Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
E-36
-------
:<-37
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radioactive Nickel
Medium: Water
Name of Measurement Method: Cobalt-Nickel
Principal Detection Technique: Liquid scintillation spectrometer
Purpose of Measurement (Important Applications); To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: Cobalt and nickel carriers added and precipitated as
insoluble hydroxides. Cobalt is separated. The nickel is reprecipitated,
purified, and collected as the hydroxide in caproic acid. The solution is
mixed with scintillation solution and counted.
Limitations;
Range of Applicability: Minimum Detectable Limits (pCi/ml)
,, Beta particle
N 0.06
The minimum detectable limits were calculated for 100 ml aliquots for each analysis
and a 100 minute counting time. Although not always practical, lower limits can be
obtained with larger sample volumes and longer counting time. For nuclides dis-
charged from light-water moderated nuclear power reactors the composition of the
test solutions has ranged from mixtures of many radionuclides at microcuries per
millimeter concentrations to barely detectable levels at picocuries per liter con-
centrations. The substrate quality has ranged from highly deionized coolant water
to waste solutions of high salt contents plus detergents.
Interferences: Cobalt also precipitated.
Decontamination Factors
131 58/60. 110mA
1 Co Ag
104 103 103
Pitfalls; Special Precautions; Dark adapt prior to counting. Samples are
counted alternately with standard 63N1 and background samples to nullify
errors of aging of scintillation medium or instrument drift. With the
multitude of reactor and waste solutions generated, radionuclide and
chemical compositions will vary and therefore require auxiliary treatment
to effect desired decontamination.
Statistical Characteristics:
Accuracy: Count at two selected window settings.
Precision: Count at least three times until successive results are
within +2
-------
E-38
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Niobium
Medium: Water
Name of Measurement Method; 1. Zirconium-Niobium; 2. Tantalum-Niobium.
Principal Detection Technique: Gamma spectroscopy to identify; Beta count to
measure decay and confirm half-life.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: Zirconium and/or Tantalum carriers are added to acidified
aqueous sample and collected as phosphates. The zirconium is precipitated.
(Tantalum is extracted if being measured). Niobium is converted to a fluoride
complex and purified. After precipitation as the hydrous oxide, the niobium is
ashed to Nb_0_ for counting.
Limitations:
Range of Applicability; Minimum detectable limits (pCi/ml)
Beta Particle
0.06
The minimum detectable limits were calculated for 100 ml allquots for each
analysis and a 100-minute counting time. Although not always practical,
lower limits can be obtained with larger sample volumes and longer count-
ing time. For nuclides discharged from light-water moderated nuclear
power reactors, the composition of the test solutions has ranged from
mixtures of many radlonuclides at microcuries per millimeter concentra-
tions to barely detectable levels at picocurles per liter concentrations.
The substrate quality has ranged from highly deionized coolant water to
waste solutions of high salt contents plus detergents.
Interferences: Zirconium and/or Tantulum produced.
Decontamination Factors
131T 58/60Co 110mAg
10* 103 103
Pitfalls; Special Precautions: With the multitude of reactor and waste
solutions generated, radionuclide and chemical compositions will vary
and therefore require auxiliary treatment to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision; Not given
Time of Measurement; 2 samples - 8 hours (time for prepiration of
Zirconium and Niobium); (Ta-Ni preparation time) + 2 hours when
methods combined to measure all three. Beta count at one month Invervals.
Calibration Requirements: Gamma spectrometer - Beta counter - Background.
Comments by Users; Combining the two methods allows all three from one sample
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling); Not given
Reference:
Procedures for Radlochemical Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
E-38
-------
E-39
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radioactive Phosphorus
Medium; Water
Name of Measurement Method; Not given.
Principal Detection Technique: Beta count to corroborate half-life.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations,the amount of the radionuclide present is determined.
Summary of Method: Phosphorus carrier and appropriate scavenging carriers are
added to the acidified aqueous sample and impurities are removed by a double hydroxide
precipitation. The phosphorus is precipitated as MgNH.PO, for counting.
Limitations:
Range of Applicability; Minimum Detectable Limits (pCi/ml)
Gamma Ray Beta Particle
32P - 0.01
Interferences: Decontamination factors
131X 58/60Co 110mAg
102 103 103
Pitfalls; Special Precautions; With the multitude of reactor and waste
solutions generated,radionuclide and chemical compositions will vary and
therefore require auxiliary treatment to effect desired decontamination.
Plot gamma ray spectrum to ascertain whether any gamma photopeaks from
impurities are present.
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Procedure
time: 4 samples - 4 hours. Beta count at 1-week intervals to corroborate
half-life.
Calibration Requirements: Counter background. Calibrate gamma spectrometer
and beta counter.
Data Outputs: Counts and time
Special Sampling Requirements (Collection, Storage. Handling): Not given
Reference:
Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
E-39
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E-40
SUMMARV OF ANALYTICAL METHOD
Parameter(s) Measured: Plutonium (238 and 239)
Medium: Air
Name of Measurement Method: Liquid Ion Exchange, Co-Precipitation.
Principal Detection Technique: Alpha spectroscopy
Purpose of Measurement (Important Applications): Determine content of plutonium
238 and 239 in air.
Summary of Method; Add plutonium 236 tracer. Ash the air filter and then wet ash
with nitric acid and peroxide. The sample in an HC1 medium is extracted into TIOA
and plutonium stripped with 4t) HC1/0.5 tJ HF and coprecipltated with lanthanum fluoride
and counted.
Limitations;
Range of Applicability: Not given
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement: Not given
Calibration Requirements: Alpha spectrometer; counting efficiency;
background.
Data Outputs; Counts and time.
Special Sampling Requirements (Collection. Storage. Handling); Not given
Reference;
Strong, Ann (Editor), Procedures for Radiochemical Analysis at the
Eastern Environmental Radiation Laboratory, EERL Report No. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, EPA, Montgomery,
Alabama (Undated).
E-40
-------
E-41
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Plutonium (238 and 239)
Medium; Sea water
Name of Measurement Method; Liquid Ion Exchange, Co-Precipitation
Principal Detection Technique: Alpha spectroscopy
Purpose of Measurement (Important Applications); Determine content of Plutonium
238 and 239 in sea water.
Summary of Method; Add plutonium 236 tracer. Sea water is made 6 N. in HC1 and
peroxide added to convert all of Che plutonium to Pu (IV). The solution is extracted
into tri-isoctylamine (TIOA). The plutonium is converted to Pu (III) and stripped.
After wet ashing, the sample is coprecipitated with lanthanum fluoride and counted.
Limitations:
Range of Applicability: Not given
Interferences; Not given
Pitfalls; Special Precautions; Not given
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement: Not given
Calibration Requirements; Alpha spectrometer; counting efficiency;
background.
Data Outputs; Counts and time
Special Sampling Requirements (Collection. Storage. Handling); Not given
Reference:
Strong, Ann (Editor), Procedures for Radiochemlcal Analysis at the
Eastern Environmental Radiation Laboratory, EERL Report No. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, EPA, Montgomery,
Alabama (Undated).
E-41
-------
E-42
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Polonium 210 *
Medium; Biological materials
Name of Measurement Method: Plating on Silver
Principal Detection Tedhnique: Internal proportional alpha counter.
Purpose of Measurement (Important Applications): Determine Polonium 210 content of
biological materials such as tobacco, urine, and soft tissue.
Summary of Method: The dissolved sample is neutralized and then made 0.5 N^ in HC1.
Ascorbic acid added to immobilize iron. The acid solution is placed In a plating
cell, vanned to 95'C and stirred for several hours to induce plating onto a silver
disk. The silver disk is washed, dried and counted.
Limitations:
Range of Applicability: Not given
Interferences: Not given
Pitfalls; Special Precuations; Do not dry ash the sample. Cannot be adapted
to routine mass production since more or less constant analyst attention required.
Statistical Characteristics:
Accuracy; Plating efficiency is 95%.
Precision: Not given
Time of Measurement; Four to eight hours to complete the method
Calibration Requirements: Internal proportional alpha counter.
Data Outputs; Counts and time
Special Sampling Requirements (Collection. Storage. Handling); Wet ash the sample.
References:
(1) Douglas, Geneva S. (Editor), Radioassay Procedures for Environ-
mental Samples, National Center for Radiological Health, U. S.
Public Health Service, Rockvllle, Maryland, January 1967.
(2) Black, S. C. "Low Level Polonium Determination of Tissue and Urine".
University of Rochester Report No. UR-463, Rochester (1956).
(3) Ranford, E. P., Jr., V. R. Hunt, and D. Sherry. "Analysis of Teeth and Bones
for Alpha-Emitting Elements". Radiation Research 19:298-315 (1963).
*
Thl* method is considered acceptable by EPA, but not necessarily used in EPA
laboratories.
E-42
-------
E-43
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Potassium*
Medium: Environmental sample
Name of Measurement Method: Gamma spectrometry*
Principal Detection Technique: Gamma spectrometry
Purpose of Measurement (Important Applications); Determine content of stable
potassium In environmental samples other than air, food, water, or milk.
Summary of Method: Measure potassium 40 by gamma spectrometry. From measured
amount of potassium 40, stable potassium can be determined since potassium 40
occurs as a constant proportion of stable potassium.
Limitations:
Range of Applicability; Not given
Interferences; Not given
Pitfalls, Special Precautions: Not given
Statistical Characteristics:
Accuracy; Sot given
Precision; Not given
Time of Measurement: Mot given
Calibration Requirements; Background; gamma spectrometer; counter efficiency
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling): Not given
Reference : Douglas, Geneva S. (Editor), Radioassay Procedures Cor
Environmental Samples, National Center for Radiological Health, U. S.
Public Health Service, Rockville, Maryland, January 1967.
This mo'fcod is considered acceptable by EPA, but is not necessarily used in EPA
laboratories.
E-43
-------
E-44
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Potassium *
Medium: Food
Name of Measurement Method: Gamma Spectrometry
Principal Dececcion Technique: Gamma spectrometry
Purpose of Measurement (Important Applications): Prevention and control of radio-
logical hazards by defining the transport of the radioactive contaminant from its
source to its ultimate deposition in man.
Summary of Method: A 3.5 liter portion of the blended food sample is placed in a
Marinelli-type beakeruhich fits over a 4 x 4 thallium-activated sodium iodide crystal
detector. Potassium 40 is measured and the concentration of natural potassium is
computed.
Limitations:
Range of Applicability: Not given
Interferences; Not given
Pitfalls; Special Precautions: Immediately after collection of milk
sample, a preservative is added to the sample and, if possible, the sample
Is refrigerated.
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement: Not given
Calibration Requirements: Background count; gamma spectrometer; counter efficiency.
Comments by Users; The method is non-destructive and the sample may be ashed and
used for other analyses.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling): The sample must
represent the edible portion or the portion actually consumed, should be prepared and
"served" in reasonable portions, must be made homogeneous and must be put in solution.
This can be done by ashing, digesting in acid, fusing, or a combination of these. Food
samples should be packaged In waterproof containers, frozen during storage, and thawed
prior to analysis. Preservatives may be needed.
Reference; Douglas, Geneva S. (Editor), Radioassay Procedures for
Environmental Samples, National Center for Radiological Health, U. S.
Public Health Service, Rockville, Maryland, January 1967.
This method Is considered acceptable by EPA, but not necessarily used in EPA
laboratories.
E-44
-------
E-45
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Potassium*
Medium; Milk
Name of Measurement Method: Flame Photometric Method*
Principal Detection Technique: Flame Photometry
Summary of Method: Milk, to which acetic acid has been added, is heated in a water
bath until the casein separates. The mixture is centrifuged, filtered, and the
filtrate is passed through a column of cation-exchange resin. The potassium is eluted
and its concentration is determined by flame spectrometry.
Limitations:
Range of Applicability: Any liquid milk sample
Interferences; Calcium, sodium, and magnesium also produced.
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy; The precision! compares favorably with that of the determination of
potassium by gamma spectrometry.
Precision; Duplicate sample analyses have a standard deviation of + 0.05 g/liter.
Time of Measurement: Not given
Calibration Requirements; Flame photometer calibration curve; background response
Data Outputs: Analog Voltage
Special Sampling Requirements (Collection, Storage, Handling); Immediately after
collection of milk sample, a preservative is added to the sample, and if possible,
the sample is refrigerated.
References;
(1) Douglas, Geneva S. (Editor), Radioassay Procedures for Environ-
mental Samples, National Center for Radiological Health, U. S.
Public Health Service. Rockvllle, Maryland, January 1967.
(2) Porter, C.R., R.J. Augustine, J. M. Matusek, Jr., and M. W. Carter. Procedures
for Determination of Stable Elements and Radionuclldes in Environmental Samples
Public Health Service Publication No. 999-RH-10, Environmental Health Series,—
Radiological Health (1965).
(3) Wenner, V. R. "Rapid Determination of Milk Salts and Ions. I. Determination of
Sodium, Potassium, Magnesium, and Calcium by Flame Spectrophotometry". J. Dairy
Sci 41: 761-768 (1958). JL
* This method is considered acceptable by EPA, but is not necessarily used in EPA
laboratories.
E-45
-------
E-47
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Prometheum 147
Medium: Environmental samples
Name of Measurement Method: Slow Method
Principal Detection Technique: Liquid scintillation counter
Purpose of Measurement (Important Applications): Measure prometheum 147 in feces,
food, soil, etc.
Summary of Method: Process the same as the Slow Method for prometheum in urine (E-79)
except before passing through ion exchange column: ash the sample; add neodymlum
carrier; evaporate with UNO.; dissolve residue in nitric acid; and add hydrofluoric
acid.
Limitations:
Range of Applicability; Not given
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics;
Accuracy and Precision; Not given
Time of Measurement: Not given
Calibration Requirements: Liquid scintillation counter
Data Outputs; Electromechanical Sealer
Special Sampling Requirements; (Collection. Storage. Handling): Ash the sample
Reference ; Strong, Ann (Editor), Procedures for Radiochemical Analysis
at the Eastern Environmental Radiation Laboratory, EERL Report No. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, EPA, Montgomery, Alabama
(Undated).
E-46
-------
E-48
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Prometheum 147
Medium: Urine
Name of Measurement Method: Rapid MeLhud
Principal Detection Technique: Liquid scintillation counter
Purpose of Measurement (Important Applications): Determine prometheum 147 content
in urine and other aqueous solutions.
Summary of Method:
Add neodymium carrier to the sample. Add oxalic acid to form a precipitate, purify,
and reprccipitate with oxalic acid. Weigh the precipitate. Dissolve it in disodium
EDTA. Transfer to liquid scintillation counter for counting.
Limitations:
Range of Applicability: Not given
Interferences: Cerium
Pitfalls; Special Precautions: Use this method only if prometheum is the only
radionuclide present. Use the other, longer method if other radionuclidcs are
suspected.
Statistical Characteristics:
Accuracy and Precision: Soc given
Time of Measurement: Not given
Calibration Requirements: >;ot given
1)3La Outputs: I'lcrtrnn«.vh.inital Staler
Special Sampling Requirements (Collection, Storage, Handling): Not given
Reference : Strong. Ann (Editor), Procedures for Radiochemical Analysis
at the Eastern Environmental Radiation Laboratory, EERL Report No. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, EPA, Montgomery, Alabama
(Undated).
E-47
-------
E-49
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Pronetheun 147
Medium: Urine and aqueous solutions
Name of Measurement Method; Slow method
Principal Detection Technique! Liquid scintillation counter
Purpose of Measurement (Important Applications); Determination of Prometheum in
aqueous solutions, Including urine.
Summary of Method; Add neodymium carrier to sample. Pass sample, citric acid and
HC1 through Ion-exchange column. Add oxalic acid to the effluent and remove precipitate.
Dissolve in distilled water and evaporate to dryness. Add HC1 and oxalic acid to pre-
cipitate neodymium oxalate. Weigh and then add dlsodlun EOTA. Transfer to liquid
scintillation counter for counting.
Limitations;
Range of Applicability: Not given
Interferences; Not given
Pitfalls. Special Precautions: Use this method if other radionuclldes are
suspected in the sample; otherwise use the rapid method.
Statistical Characteristics!
Accuracy: Not given
Precision; Not given
Time of Measurement! not given
Calibration Requirements; Liquid scintillation counter
Comments by Users; Can also be counted by beta counter
Data Outputs; Electromechanical Sealer
Special Sampling Requirements (Collection. Storage. Handling); Not given
Reference' Strong, Ann (Editor), Procedures for Radiochemlcal Analysis
at the Eastern Environmental Radiation Laboratory. EERL Report No. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, EPA, Montgomery, Alabama
(Undated).
E-48
-------
E-50
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radium 226
Medium: Environmental samples
Name of Measurement Method: Ion-Exchange and Emanation Procedure.
Principal Detection Technique: Alpha scintillation counter
Purpose of Measurement (Important Applications): Measure radium 226 in environmental
samples.
Summary of Method: The sample with barium and strontium carriers is fused, complexed
with EDTA, passed over a cation-exchange resin column. Strontium is eluted with HC1.
Barium-radium fraction is eluted with NaCl and precipitated with additional strontium
carrier as Che carbonate. Tne precipitate is dissolved and barium-radium chromate is
precipitated. The precipitate is dissolved in acid and sealed in an emanation tube
for Ingrowth of Radon 222. When secular equilibrium Is reached, the gas is purged into
an alpha scintillation cell and counted. Barium 133 is used to determine chemical yield.
Limitations;
Range of Applicability: Not given
Interferences! Not given
Pitfalls; Special Precautions: Dark adapt at least four hours before counting.
Long counting time required.
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement: Secular equilibrium has to be attained.
Calibration Requirements: Background; counter efficiency.
Comments by Users: Use the same sample to measure radiostrontium in environmental
samples by Ion-Exchange - EDTA.
Data Outputs; Electromechanical sealer
Special Sampling Requirements (Collection. Storage. Handling): Not given
Reference; Strong, Ann (Editor), Procedures for Radlochemlcal Analysis
at the Eastern Environmental Radiation Laboratory, EERL Report No. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, EPA, Montgomery, Alabama
(Undated).
E-49
-------
E-51
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radium 226
Medium: Environmental samples
Name of Measurement Method: Radon Emanation
Principal Detection Technique: Alpha scintillation counter
Purpose of Measurement (Important Applications); To determine radium 226
content of environmental samples.
Summary of Method; The ashed sample is digested with nitric acid and hydrogen
peroxide. Barium carrier is added and ammonium carborate is added to precipi-
tate the carbonate. The precipitate is dissolved in nitric acid and precipitated
as a chromate. The precipitate is dissolved in hydrochloric acid and
reprecipltated as a chloride with hydrochloric acid-ether solution. The precip-
itate is readily soluble in less than 10 ml water. The solution is transferred
to an emanation tube for radon 222 ingrowth. When equilibrium is reached, the
gas is purged into an alpha scintillation cell and counted.
Limitations;
Range of Applicability; Not given
Interferences: Not given
Pitfalls; Special Precautions; Not given
Statistical Characteristics:
Accuracy: Not given
Precision; Not given
Time of Measurement; 28 days required for radon 222 ingrowth
Calibration Requirements: Background
Counter efficiency
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage. Handling): Ash the sample
Reference: Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-50
-------
E-52
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radium 226*
Medium: Food
Name of Measurement Method: Combination of KDEHP extraction method and radon 222
emanation method.
Principal Detection Technique: Same as either Radon 222 emanation method for Radium 226
(E-53 or E-54).
Purpose of Measurement (Important Applications): Prevention and control of radi-
ological hazards by defining the transport of the radioactive contaminant from its
source to its ultimate deposition in man.
Summary of Method: The aqueous solution from the HDEHP extraction method for
Strontium 90 is evaporated, dissolved in nitric acid and evaporated again.
The residue is analyzed by either Radon 222 emanation method.
Limitations;
Range of Applicability: Any sample which has been reduced to ash.
Interferences; Same as Radon 222 emanation method
Pitfalls; Special Precautions: Cannot be performed rapidly or by
untrained technicians.
Statistical Characteristics:
Accuracy: Not Given
Precision: High level of precision
Time of Measurement: Requires about 38 days to complete.
Calibration Requirements: Same as radon 222 emanation method
Data Outputs: See either Radon 222 Emanatron Method.
Special Sampling Requirements (Collection. Storage. Handling): The sample must
represent the edible portion or the portion actually consumed, should be prepared
and "served" in reasonable portions, must be made homogeneous and must be put in
solution. This can be done by ashing, digesting in acid, fusing, or a combination
of these. Food samples should be packages in waterproof containers, frozen during
storage, and thawed prior to analysis. Preservatives may be needed.
Reference; Douglas, Geneva S. (Editor), Radioassay Procedures for Environmental
Samples, National Center for Radiological Health, U.S. Public Health Service,
Rockville, Maryland, January 1967.
*
This method is considered acceptable by EPA, but is not necessarily used in EPA
laboratories.
E-51
-------
E-53
SUMMARY OF ANALYTICAL METHOD
Paramoter(s) Measured: Radium 226*
Medium; Food
Name of Measurement Method; Radon 222 emanation method - Procedure A
Principal Detection Technique: Count of alpha activity of a scintillation cell in a
radon counter.
Purpose of Measurement (Important Applications); Prevention and control of radio-
logical hazards by defining the transport of the radioactive contaminant from its
source Lo its ultimate dcoosltion in man.
Summary of Method: A weighed portion of an ashed sample is dissolved with nitric acid
and hydrogen peroxide. Barium carrier is added and carbonates precipitated. The
carbonate precipitate is dissolved In nitric acid, buffered and radium-barium chromate
precipitated. The chromates are dissolved in HC1 and barium chloride precipitated.
The radium-barium chloride precipitate is dissolved in water and the solution stored
in an emanation tube (radon bubbler) for 28 days. After secular equilibrium is
attained the radon 222 is removed to a scintillation cell by de-emanating the bubbler.
The cell is stored until the radon 219 and radon 220 daughters, If present, have
decayed out and radon 220 has come into equilibrium. After a suitable storage period,
the alpha activity is counted.
Limitations;
Range of Applicability; Bone, vegetable, or any sample which has been reduced
to an ash. Minimum detectable concentration is 1 pCi/kg.
Interferences; Specific for radium 226 as long as the alpha activity of the
scintillation cell is not counted until the thoron ( Rn) and actinon(219Rn)
daughters of any radium 224 and radium 223 present have had tine to decay out.
Pitfalls; Special Precautions: Cannot be performed rapidly or by untrained
technician. Extensive laboratory facilities and experienced technicians are
required.
Statistical Characteristics:
Accuracy: Not Given
Precision: High degree of precision
Time of Measurement: Requires approximately 30 days to complete (continuous
processing allows analysis of a large number of samples).
Calibration Requirements: Radon counter is plateaued and calibrated by preparing a
standard solution of radium 226 and processing it like the samples. Background count.
Efficiency of scintillation cell and counter.
Data Outputs: Electromechlcal sealer.
Special Sampling Requirements (Collection, Storage,Handling): The sample must represent
the edible portion or the portion actually consumed, should be prepared and "served"
In reasonable portions, must be made homogeneous and must be put in solution. This can
be done by ashing, digesting in acid, fusing, or a combination of these. Food samples
should be packaged in waterproof containers, frozen during storage, and thawed prior to
analysis. Preservatives may be needed
Reference.*;:
(1) Douglas, Geneva S. (Editor), Radloassay Procedures for Environ-
mental Samples, National Center for Radiological Health, U. 5.
Public Health Service, Rockvllle, Maryland, January i'J6T.
(2) Johns, F. B., E. Halker, and D. Moden. Analyses for Radlum-226. U. S.
Department of Health, Education, and Welfare, Public Health Service,
Southwestern Radiological Health Laboratory, Las Vegas (1965) Internal report.
(3> Rushing, D. C. Radlum-226 in Water (Total. Suspended, and Dissolved) by Radon
De-emanation. U. S. Department of Health, Education, and Welfare, Public
Health Service, Division of Water Supply and Pollution Control, Colorado River
Basin Water Quality Control Project Laboratory, Salt Lake City.
(4) Shearer, S. D., Jr. The Leachabllltv of Radium 226 from Uranium Mill Waste
Solids and River Sediments. Ph.D. dissertation. Department of Civil Engineering,
No. 603, University of Wisconsin, Madison (1962) 162 pp(Available through
Dissertation Abstracts, University of Michigan, Ann Arbor).
* This method is considered acceptable by EPA, but Is not necessarily used in EPA
laboratories.
E—52
-------
E-54
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radium 226*
Medium: Food
Name of Measurement Method: Radon 222 emanation method - Procedure B
Principal Detection Technique: Same as Procedure A (E-53).
Purpose of Measurement (Important Applications): Same as Procedure A. Gamma counting
to determine barium carrier recovery.
Summary of Method; The ashed food sample is dissolved in nitric acid. Barium carrier
and barium 133 tracer are added and radium is co-precipitated with barium sulfate. The
sulfate precipitate is converted to the carbonate and dissolved in nitric acid. Barium
carrier recovery is determined by gamma counting of barium 133 tracer in the solution.
The solution is de-emanated and aged to allow radon 222 to grow in. After sufficient
storage, it is again de-emanated and the radon collected in a scintillation cell and
alpha activity is measured in a radon counter.
Limitations:
Range of Applicability; Same as Procedure A
Interferences: Same as Procedure A
Pitfalls; Special Precautions; Same as Procedure A
Statistical Characteristics:
Accuracy: Not Given
Precision: Same as Procedure A
Time of Measurement: Same as Procedure A
Calibration Requirements; Same as Procedure A
Data Outputs: Same as Procedure A
Special Sampling Requirements (Collection. Storage. Handling): Same as Procedure A.
References:
(1) Douglas, Geneva S. (Editor), Radioassay Procedures Cor Environ-
mental Samples, National Center for Radiological Health, U. S.
Public Health Service, Rockville, Maryland, January 1967.
(2) Holaday, D. A., D. E. Rushing, R. D. Coleman, P. F. Woolrich, H. L.Kusnetz,
and W. F. Bale. Control of Radon and Daughters in Uranium Mines and Calcu-
lations on Biologic Effects. U. S. Department of Health, Education, and
Welfare, Public Health Service, Public Health Service Publication No. 494 (1957).
(3) Magno, P. J., E. J. Baratta, and E. Ferri. Procedures for the Chemical and
Radiochemical Analysis of Environmental Samples. Winchester, U.S. Department
of Health, Education, and Welfare, Public Health Service, Northeastern Radio-
logical Health Laboratory Report No. NERHL-64-1 (1964).
*
This method is considered acceptable by EPA, but is not necessarily used in EPA
laboratories.
E-53
-------
E-55
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radium 226
Medium; Soil
Name of Measurement Method; Leach Method
Principal Detection Technique; Alpha scintillation counter
Purpose of Measurement (Important Applications); To determine radium 226
content of soil.
Summary of Method; The sample is leached with hydrochloric acid, filtered
and diluted to a known volume; about 10 grams of soil leached to 10 ml of solution.
Ten ml of the solution are transferred to a radon bubbler for radon 222 ingrowth.
When equilibrium is reached, the gas is purged into an alpha scintillation cell.
Limitations;
Range of Applicability; Not given
Interferences; Not given
Pitfalls; Special Precautions; Not given
Statistical Characteristics;
Accuracy: Not given
Precision; Not given
Time of Measurement! 28 days required for radon 222 ingrowth.
Calibration Requirements;
• Counter efficiency
Background
Data Outputs; Counts and time
Special Sampling Requirements (Collection. Storage, Handling); Not given
References ; Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-54
-------
E-56
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radium 226
Medium: Soil, sludge, air filters, feces, and urine
Name of Measurement Method: Not given
Principal Detection Technique; Alpha scintillation counter
Purpose of Measurement (Important Applications): To determine radium 226
content of soil.
Summary of Method; Sample is transferred to a platinum crucible, mixed with
Nicholson's flux and fused. The fused cake Is dissolved in sulfurlc acid and
barium carrier is added. The barium sulfate is heated with phosphoric acid
to form the soluble phosphate. The cooled barium precipitate is dissolved
in HC1 and transferred to an emanation tube for radon 222 ingrowth. When
equilibrium is reached, the gas is purged into an alpha scintillation cell
and counted.
Limitations:
Range of Applicability: Not given
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics;
Accuracy: Not given
Precision! Not given
Time of Measurement! 28 days required for radon 222 ingrowth
Calibration Requirements: Background
Counter efficiency
Comments'by Users: 1. If organic matter is present, ignite overnight at
500° C. 2. Moisten air filter with 10Z ammonium sulfate. 3. If more
than a trace of heavy metals is present, a porcelain crucible should be used.
Data Outputs: Counts and time
Special Sampling Requirements (Collection, Storage, Handling): Not given
Reference: Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-55
-------
E-57
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radium 226
Medium; Urine
Name of Measurement Method: Emanation
Principal Detection Technique: Alpha scintillation counter.
Purpose of Measurement (Important Applications): Determine content of radium 226
in urine.
Summary of Method: Add sodium carbonate to the sample to precipitate barium and
radium. Treat the precipitate with nitric acid. Store in an emanation tube for the
ingrowth of radon 222. Count when secular equilibrium is reached. Barium 133 is used
to determine chemical yield.
Limitations;
Range of Applicability: Not given
Interferences; Not given
Pitfalls; Special Precautions; Not given
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement: 2 to 3 weeks required for radon 222 ingrowth.
Calibration Requirements: Background; counter efficiency.
Data Outputs: Electromechanical sealer
Special Sampling Requirements (Collection. Storage, Handling); Preserve with 1:1000
merthiolate and store at 4°C.
Reference : Strong, Ann (Editor), Procedures for Radiochemical Analysis
at the Eastern Environmental Radiation Laboratory, EERL Report No. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, EPA, Montgomery, Alabama
(Undated).
E-S6
-------
E-58
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radium 226
Medium; Water
Name of Measurement Method: Radon Emanation
Principal Detection Technique: Alpha scintillation counter
Purpose of Measurement (Important Applications): Determine radium 226
content of water
Summary of Method! Use lead carrier to co-precipitate radium an a sulfntp.
The lead-radium sulfate is reprecipltated as a carbonate. The precipitate
is dissolved in nitric acid and transferred to a radon bubbler for Ingrowth
of radon 222. When equilibrium is reached, the gas is purged into an alpha
scintillation cell and counted.
Limitations:
Range of Applicability: Not given
Interferences: Not given
Pitfalls; Special Precautions; Not given
Statistical Characteristics:
Accuracy! Not given
Precision: Not given
Time of Measurement: 28 days required for ingrowth of radon 222
Calibration Requirements; Counter efficiency
Background
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage. Handling): Not given
Reference = Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-57
-------
E-59
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radium 226
Medium: Water
Name of Measurement Method: Ion-Exchange and Emanation Procedure
Principal Detection Technique: Alpha scintillation counter
Purpose of Measurement (Important Applications); Measure radium 226 in fresh and
sea water.
Summary of Method; The method is the same as the Ion-Exchange and Emanation
Procedure for Radium 226 in environmental samples (E-SO) except that the sample is
not fused.
Limitations:
Range of Applicability: Fresh and sea water
Interferences: Sot given
Pitfalls; Special Precautions: Dark adapt at least four hours before
counting. Long counting time required.
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement: Secular equilibrium has to be attained.
Calibration Requirements; Background; counter efficiency.
Comments by Users; Use the same sample to measure radiostrontium by lon-Exchange-
EDTA (E-67).
Data Outputs; Electromechanical sealer
Special Sampling Requirements (Collection, Storage. Handling): Not given
Reference; Strong, Ann (Editor), Procedures for Radiochemical Analysis
at the Eastern Environmental Radiation Laboratory, EERL Report No. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, EPA, Montgomery, Alabama
(Undated).
E-58
-------
E-60
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radon 222
Medium! Ambient air
Same of Measurement Method; Not given
Principal Detection Technique; Scintillation counter
Purpose of Measurement (Important Applications); To determine radon content
of the ambient air.
Summary of Method; The sample is transferred to the gas separation apparatus. It is
then passed through a carbon dioxide removal trap (Ascarite), a water removal trap,
and two charcoal traps at ice water temperature. The radon is deeraanated with
helium and collected in scintillation cells.
Limitations;
Range of Applicability; Not given
Interferences; Not given
Pitfalls; Special Precautions; Not given
Statistical Characteristics;
Accuracy; Not given
Precision! Not given
Time of Measurement; Not given
Calibration Requirements;
Counter efficiency
Background
Data Outputs; Counts and time
Special Sampling Requirements (Collection. Storage. Handling); Can use either grab
or continuous samples.
Reference; Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemlcal Analytical Methods, March 1970
(reprint January 1972).
E-59
-------
E-61
SUMMARY 07 ANALYTICAL METHOD
ParameEer(s) Measured: Radon 222
Medium: Natural gas
Name of Measurement Method: Concentration
Principal Detection Technique; Alpha scintillation counter
Purpose of Measurement (Important Applications); To determine radon 222
content of natural gas.
Summary of Method: A large sample is passed through a room temperature
molecular sieve to remove heavy boilers (C. and higher), a steel ball trap
at liquid nitrogen temperature (to collect G£ - 05*3) and a charcoal trap
at liquid nitrogen temperature (to collect methane, radon and any other
low boilers). Any methane or radon collected in the steel ball trap is
transferred to the charcoal trap by wanning to dry ice-acetone temperatures.
Methane is removed from the charcoal trap by elution with helium. The
radon is transferred into two smaller charcoal traps by elution and heat.
The radon in each of the two small traps is transferred to the scintillation
cells.
Limitations:
Range of Applicability: Crude or processed natural gas.
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics;
Accuracy; Not given
Precision: Not given
Time of Measurement: Not given.
Calibration Requirements:
Counter efficiency
Background.
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage, Handling); Not given
Reference: Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-60
-------
E-62
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radon 222
Medium; Natural gas
Name of Measurement Method; Direct Transfer.
Principal Detection Technique; Alpha scintillation counting.
Purpose of Measurement (Important Applications); To determine radon 222
content of natural gas.
Summary of Method; Water and carbon dioxide are removed from the sample.
The sample is then transferred to an alpha scintillation cell for counting.
Limitations;
Range of Applicability; Samples that are 1 to 2 half-lives old.
Interferences; Not given.
Pitfalls; Special Precautions; Not given
S tatis tical Characteris tics;
Accuracy: Not given
Precision; Not given
Time of Measurement; Not given
Calibration Requirements;
Counter efficiency
Background.
Data Outputs; Counts and tine
Special Sampling Requirements (Collection. Storage. Handling); Not given
Reference; Johns, Frederick B.. Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-61
-------
E-63
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Ruthenium
Medium: Water
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma ray spectroscopy to identify 103Ru and 106Ru.
Beta count to measure decay and confirm half-life.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations,the amount of the radionuclide present is determined.
Summary of Method: Ruthenium carrier and the appropriate holdback carrier are
added to a sample in a special distillation flask. In acid solution, in the presence
of a strong oxidant.the ruthenium is converted to the tetroxide, distilled into
caustic, and reduced to the metal for counting.
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
Nuclide Gamma Ray Beta Particle
103Ru 0.05 0.01
106Ru 0.2 0.01
Interferences: Decontamination Factors
131I 58/60Co 110mAg
103RU 103 103 103
l06Ru 103 LO3 103
Pitfalls; Special Precautions: With the multitude of reactor and waste solutions
generated, radionuclide and chercical compositions will vary and therefore require
auxiliary treatment to effect desired decontamination.
Statistical Characteristics;
Accuracy and Precision: Not Given.
Time of Measurement (Maximum Frequency, Recovery Period, etc.): Procedure time:
4 samples - 3 hours. Plot gamma ray spectrum. Beta count at one month intervals
to measure decay and confirm half-life.
Calibration Requirements: Gamma ray Intensities of Ru and Ru at 500 and 600
KeV previously determined with standardized tracer solutions. Counter background.
Calibrate gamma spectrometer and beta counter.
Data Outputs; Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling): Not Given
Reference ;
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Wyatt, E. I. and Rickard, R. R., "The Radlochemistry of Ruthenium",
Nuclear Science Series, NAS-NS-3029, 48-50, Nat'l Acad. Sci.,
Nat'l. Res. Council, USAEC, 1961.
E-62
-------
E-64
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Silver
Medium: Water
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma ray spectroscopy to identify and
beta count to confirm half-life.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine opera-
tions, the amount of the radionuclide present Is determined.
Summary of Method: Silver carrier and the appropriate scavenging carrier are
added to the aqueous sample. After silver is collected as the hydrous oxide, impuri-
ties are removed by a cobaltinitrate precipitation. The silver is precipitated as
AgCl for counting.
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
110m Gamma Ray Beta Particle
A8 0.04 0.02
Interferences: Decontamination Factors
131T 58/60ro
I Co
io3 m3
Pitfalls; Special Precautions: The aqueous sample must not contain chlorides.
If cobalt activity is still present in the AgCl precipitate, further decon-
tamination is required. Plot summary spectrum to identify any contaminating
gamma emitters. With the multitude of reactor and waste solutions generated,
radionuclide and chemical compositions will vary and therefore require auxiliary
treatment to effect desired decontamination. Gamma spectrum will Identify
contaminating gamma emitters.
Statistical Characteristics:
Accuracy and Precision; Not Given
Time of Measurement (Maximum Frequency. Recovery Periodj^etc.) : Procedure time:
4 samples - 3 hours, plot gamma-ray spectrum to verify Ag. Beta count after
2 months and 6 months to confirm half-life.
Calibration Requirements: Counter background. Calibrate gamma spectrometer and beta
counter.
Data Outputs: Counts and time and energy.
Special Sampling Requirements (Collection. Storage. Handling): Not Given
Reference:
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Lingane, J. J., Analytical Chemistry of Selected Metallic Elements,
pp. AS and 99, Relnhold, 1966.
E-63
-------
E-65
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radiostrontium
Medium: Environmental samples
Name of Measurement Method: Ion-Exchange -EDTA
Principal Detection Technique: Low background beta counter.
Purpose of Measurement (Important Applications): Determine radiostrontium content of
environmental samples and food.
Summary of Method: The sample with added carriers is fused with a sodium-hydroxide-
sodium carbonate fusion. The method is then identical to Ion-Exchange - EDTA for
radiostrontium in water (see Method E-67 in this compendium).
Limitations:
Range of Applicability: Sensitivity of 0.1 pCi/gm of ash for strontium 90.
Interferences: None stated
Pitfalls; Special Precautions: None stated
Statistical Characteristics:
Accuracy and Precision: Procedure adapted to multivariate analysis.
Time of Measurement: One technician can analyze 40 samples per week. Count
again after 6-7 days.
Calibration Requirements: Beta counter; background; Counter efficiency;
self-absorption correction factors.
Comments by Users: Use the same sample to measure radium 226 by the ion-exchange and
emanation procedure.
Data Outputs: Counts and time
Special Sampling Requirements (Collection, Storage, Handling); Not given
References:
(1) Strong, Ann (Editor), Procedures for Radiochemical Analysis
at the Eastern Environmental Radiation Laboratory, EERL Report No.
7X-XXXX (Draft), Eastern Environmental Research Laboratory, EPA,
Montgomery, Alabama (Undated).
(2) Porter, C.R., B. Kahn, M. W. Carter, G. L. Rehnberg and E. W. Pepper,
"Determination of Radiostrontium in Food and Other Environmental Samples,"
Environmental Science & Technology 1, 745 (1967).
E-64
-------
E-66
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Strontium
Medium: Water
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma Ray Spectroscopy - Beta Counter
Purpose of Measurement (Important Applications) ; To evaluate potential
health hazard from radionuclide discharges at nuclear power stations during
routine operations, the amount of the radionuclide present is determined.
Summary of Method: The strontium and barium carriers are added to the
aqueous sample collected as insoluble carbonates, and separated from most
of the calcium as nitrates. Impurities are removed by an hydroxide scavenge.
The barium Is precipitated as the chromate and purified as BaSO, for counting;
the strontium is purified as SrCO, for counting.
Limitations:
Range of Applicability: Minimum Detectable Limits
Nuclide Gamma Ray Beta Particle
89Sr " 0.05
9°Sr - 0.01
Interferences: Calcium. This method also precipitates barium.
Decontamination Factors
131Z 58/60Co U0%
89Sr 10* 104 10*
*°Sr 104 10* 10*
Pitfalls; Special Precautions: Make sure all calcium is removed. The count-
ing result, immediately ascertained, represents the strontium activity
( Sr + Sr) plus an insignificant fraction of the Y that has grown in
90 fiQ QO
from the separated Sr. To determine the Sr and Sr with a greater
precision, the planchet should be stored at least two weeks so that
90 90
Sr - Y activity will be in equilibrium. At this point, further steps are
performed on the planchet. Plot gamma ray spectrum to identify contaminating
gamma ray emitters. With the multitude of reactor and waste solutions generated,
radicnuclide and chemical compositions will vary and therefore require auxiliary
treatment to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not Given
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Procedure Time-
* samples - 6 hours. Inmedlately plot gamma ray spectrum to identify 91Sr. Beta
! 90?? °V6r S 2~Week lnterVal t0 Chcck 9°Y decay and ehe ingrowth
Calibration Requirements: Counter background. Calibrate gairana spectrometer and beta
counters.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection. Storage. Handling): Not Given
Reference ;
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Hahn, R.B., and Straub, C. P. "Determination of Radioactive Strontium
and Barium in Water, J. Am. Water Works Assn. £7, 335 (April 1, 1955).
E-65
-------
E-67
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radiostrontium
Medium: Water
Name of Measurement Method: lon-Exchange-EDTA
Principal Detection Technique: Low background beta counter.
Purpose of Measurement (Important Applications): Measure radiostrontium content
of fresh and sea water.
Summary of Method: Strontium, barium and calcium carriers added co sample and
complexed with EDTA. Magnesium is precipitated and the solution passed over a
cation-resin exchange column. Stronium is eluted with HC1 and radium-barium is
eluted with sodium chloride. Strontium is precipitated as the carbonate, scavenged,
weighed, and counted.
Limitations:
Range of Applicability: Fresh and sea water
Sensitivity; 1.0 pCi/1
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement: Not given
Calibration Requirements: Beta Counter; background; counter efficiency; self-absorption
correction factors.
Comments by Users: Use the same sample to measure radium 226 by the ion-exchange and
emanation procedure (E-59).
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage, Handling): Samples containing
high brine content are pretreated to remove sodium chloride.
Reference: Strong, Ann (Editor), Procedures for Radiochemical Analysis
at the Eastern Environmental Radiation Laboratory, EERL Report No. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, EPA, Montgomery, Alabama
(Undated).
E-66
-------
E-68
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Strontium 89 and 90
Medium: Food and biological samples
Name oE Measurement Method; Not given
Principal Detection Technique: Beta counter
Purpose of Measurement (Important Applications): To determine the strontium 89
and 90 content of food and biological samples.
Summary of Method! The sample is ashed and then fused as a carbonate. The
strontium-calcium carbonates are dissolved in HC1, complexed with EDTA and passed
through an Ion exchange column on which the strontium is absorbed. The complexed
calcium passes through. The strontium is eluted, precipitated as the carbonate,
and mounted on a planchet for beta counting. Chemical yield is determined
gravimetrically.
Limitations:
Range of Applicability: Not given
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy: Not given
Precision; Not given
Time of Measurement; Not given
Calibration Requirements: Beta counter
Self-absorption factor
Background
Comments by Users; If insoluble residue (silica) is present, filter, wash residue
twice with 100-ml portions of distilled water and add to filtered solution; discard
residue.
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage, Handling): Ash the sample
Reference: Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-67
-------
E-69
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radiostrontium 89 and 90
Medium: Milk
Name of Measurement Method: Batch Ion Exchange
Principal Detection Technique; Low background beta counter
Purpose of Measurement (Important Applications): To determine radiostrontiun
content of milk.
Summary of Method: Carriers and EDTA are added to milk. Then cation resin Is
added, allowed to settle, and the milk decanted into more cation resin. The
milk is discarded and the resin is passed through an ion exchange column.
The alkaline earth metals are removed from the cation reain by elution with
sodium chloride and precipitated as the carbonates. Barium is removed by chromate
precipitation. Strontium 89 and 90 are determined by counting twice, once after
separation and again after yttrium 90 Ingrowth, and strontium 89 decay. Chemical
yield is determined gravimetrically.
Limitations:
Range of Applicability: Sour milk
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement: Seven days required for yttrium 90 ingrowth
Calibration Requirements; Beta counter
Self-absorption factor
Background
Comments by Users: An occasional sample will not precipitate. Warming the
solution with stirring will usually bring down the precipitate.
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage. Handling): Not given
Reference : Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-68
-------
E-70
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radiostrontium 89 and 90
Medium: Milk
Name of Measurement Method: Rapid Ion Exchange
Principal Detection Technique: Low background beta counter
Purpose of Measurement (Important Applications): To determine radiostrontium
content of milk.
Summary of Method: Milk with added carriers and EDTA is passed through ion
exchange columns; the radioiodine being adsorbed on the anlon resin, the alkali
metals and most alkaline earths being adsorbed on the cation resin and the
complexed calcium passing through.
The alkaline earth metals are removed from the cation resin by elution with
sodium chloride and precipitated as the carbonates. Barium is removed bv chroma to.
precipitation. Strontium 89 and 90 are determined by counting twice, once after
separation and again after yttrium 90 ingrowth, and strontium 89 decay. Chemical
yield is determined gravimetrically.
Limitations:
Range of Applicability: Non-sour milk
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement: Seven days required for yttrium 90 ingrowth
Calibration Requirements: Beta counter
Self-absorption factor
Background
Comments by Users: An occasional sample will not precipitate. Warming the
solution with stirring will usually bring down the precipitate.
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage, Handling): Not given
Reference; Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-69
-------
E-71
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Strontium 89 and 90
Medium: Milk
Name of Measurement Method: EDTA Batch Process
Principal Detection Technique: Low background beta counter
Purpose of Measurement (Important Applications): Determine strontium (89 and 90)
content of nonhomogeneous milk.
Summary of Method: Cation resin is added to milk containing EDTA complexing solution.
The resin is stirred and transferred to an 85-ml polyethylene column attached to the
top of a 45-ml column and washed with EDTA. Strontium and barium are eluted with NaCl
and precipitated as carbonates. Barium is separated as the chromate. Strontium is
reprecipitated as the carbonate, washed, weighed and counted. Count again after
6-7 days.
Limitations:
Range of Applicability: Nonhomogeneous milk
Sensitivity: 1.0 pCi/1
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement; 6-7 days between first and second count
Calibration Requirements: Beta counter; background; self-adsorption correction factors;
counting efficiency.
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage. Handling): Not given
Reference ; Strong, Ann (Editor), Procedures for Radiochemical Analysis
at the Eastern Environmental Radiation Laboratory, EERL Report No. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, EPA, Montgomery, Alabama
(Undated).
E-70
-------
E-72
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Strontium 89 and 90
Medium: Milk
Name of Measurement Method: Routine Ion Exchange
Principal Detection Technique: Low background beta counter
Purpose of Measurement (Important Applications): To measure the stronium 89
and 90 content of milk.
Summary of Method: Milk with added carriers is passed through ion exchange colums.
Strontium, barium, and calcium are adsorbed on the cation resin and the yttrium
is retained on the anion resin. Yttrium is eluted with HC1 and precipitated as
the oxalate. ' Lanthanum 140 contaminant is removed by dissolving in nitric acid
and the yttrium is extracted and reprecitated as the oxalate. The precipitate
is weighed to determine recovery.
Calcium, strontium and barium are eluted with sodium chloride solution. The
alkaline earth metals are precipitated as carbonates and nitrates. Barium is
removed by chrornate precipitation and the strontium nitrate is counted for total
radiostrontium; the yield is determined by flame spectrophotometry.
Limitations:
Range of Applicability; The milk must be reasonably homogeneous
Interferences: Lanthanum 140
Pitfalls; Special Precautions; Time from collection of sample to passage
through ion exchange colum must be recorded.
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement: Not given
Calibration Requirements; Beta counter
Self-absorption factor
Background
User Comments: This method, while a very good method, is obsolete, and is
not heln" u=«>H at "JF.RC/Las Vegas.
Data Outputs; Counts and time
Special Sampling Requirements (Collection, Storage, Handling): The sample must
be preserved with formaldehyde and refrigerated (approximately 0°C) for two weeks
to allow the yttrium 90 to come to equilibrium with the strontium 90.
Reference; Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-71
-------
E-73
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Strontium 89 and 90
Medium: Milk
Name of Measurement Method; Nitric Acid Procedure
Principal Detection Technique; Beta counter
Purpose of Measurement (Important Applications): To determine the strontium
89 and 90 content of milk.
Summary of Method: Strontium carrier is added and the milk proteins are
precipitated with trichloroacetic acid. Following filtration, excess oxalic
acid is added and the alkaline earths are precipitated as the oxalates and
then converted to the nitrates. Calcium and strontium are separated by
differences in solubility. The strontium is then scavenged. After a nitric
acid extraction of yttrium 90, the strontium precipitate is stored for a minimum
of one week for yttrium ingrowth. After this period, the strontium is reprecip-
itated and yttrium is recovered in the supernatant. Both fractions are counted
for beta activity.
Lioitations;
Range of Applicability: Whole milk
Interferences; Not given
Pitfalls; Special Precautions; Planchet must be absolutely dry
before beta counting.
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement: One week required for yttrium 90 ingrowth
Calibration Requirements: Beta counter
Background
Self-absorption factor
User Comments; This method, while a good method, is obsolete and is not
•>eii.
-------
E-74
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Strontium 90
Medium; Urine
Name of Measurement Method: Ion Exchange
Principal Detection Technique; Low background beta-counter
Purpose of Measurement (Import Applications): Determine strontium 90 in urine.
Summary of Method; Yttrium carrier added to sample and pH adjusted. The sample
is passed over an anion-exchange resin. Yttrium is eluted with HC1 and precipitated
as yttrium oxalate.
Limitations;
Range of Applicability: Not given
Interferences: Lanthanum 140; cerium 141-144; praseodymium
Pitfalls; Special Precautions: Count after three days to confirm absence
of contamination.
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement: Not given
Calibration Requirements; Beta counter; background; counter efficiency; self-
absorption correction factors.
Data Outputs; Counts and time
Special Sampling Requirements (Collection, Storage. Handling); Preserve with
1:1000 merthlolate and store at 4°C.
References;
(1) Strong, Ann (Editor), Procedures for Radiochemical Analysis at the Eastern
Environmental Radiation Laboratory, EERL Report No. 7X-XXXX (Draft),
Eastern Environmental Research Laboratory, EPA, Montgomery, Alabama (Undated).
(2) Cahill, D.F. , and G. J. Llndsey, "Determination of Strontium-90 in Urine by
Anion Exchange", Anal. Chem. 38, 639 (1966).
E-73
-------
E-75
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Sulfur
Medium: Water
Name of Measurement Method; Not Given
Principal Detection Technique; Gamma ray spectroscopy for purity - Beta
count to confirm half-life.
Purpose of Measurement (Important Applications); To evaluate potential
health hazard from radionuclide discharges at nuclear power stations during
routine operations, the amount of the radionuclide present is determined.
Summary of Method; Sulfur carrier and appropriate holdback carriers are
added to the aqueous sample. After sulfides are oxidized to sulfates,
impurities are removed by an hydroxide scavenge. The sulfur is purified as
NH,C,H.C,H.NH, . H,SO. for counting.
£ O 4 O 4 £ *•»
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
Gamma Ray Beta Particle
35S - 0.05
Interferences: Decontamination Factors
"4 58/60Co 110mAg
103 102 103
Pitfalls; Special Precautions: It is imperative that the carriers not be
prepared in the sulfate form to assure accurate calculation of chemical
yield. Plot gamma ray spectrum of separated sample to assure decontamina-
tion. If contaminated, repeat with appropriate scavenging steps and hold-
back carriers.
Statistical Characteristics;
Accuracy and Precision: Not Given
Time of Measurement (Maximum Frequency. Recovery Period, etc.); Procedure
time: 2 samples - 5 hours. Plot gamma ray spectrum. Beta count the planchet
several times over a 30-day period to confirm half-life.
Calibration by Users: Counter background. Calibrate gamma spectrometer and beta
counter.
Data Outputs; Counts and time and energy.
Special Sampling Requirements (Collection, Storage. Handling): Not Given
Reference;
Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX(Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
E-74
-------
--76
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Tantalum
Medium; Water
Name of Measurement Method: Tantalum-Niobium
Principal Detection Technique: Gamma spectroscopy to identify; Beta counting to
follow decay and corroborate half-life.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: Tantalum, niobium, and zirconium carriers added to acidified
samples and collected phosphates. Zirconium precipitated. The tantalum is
extracted into MIBK, back extracted into water and purified as Ta2°5 for counting.
Niobium can then be precipitated.
Limitations:
Ranee of Applicability: Minimum Detectable Limits (pCi/ml)
182_ Gamma Ray Beta Particle
Ta 0.08 0.02
Interferences:. Niobium and Zirconium also produced.
Decontamination Factors
131I 58/60Co 110mAg
103 103 103
Pitfalls; Special Precautions: Verify purity with gamma ray spectroscopy.
With the multitude of reactor and waste solutions generated, radionuclide and
chemical compositions will vary and therefore require auxiliary treatment to
effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not Given
Time of Measurement: 2 samples - 8 hours (time for preparation of tantalum and
niobium); (Zr-Nb preparation time) + 2 hours when methods combined to produce
all three (Tantalum, Niobium, and Zirconium).
Calibration Requirements; Background, eamroa soectrometer, beta counter.
Comments by Users; Combining this procedure with zirconium-niobium procedure
makes it possible to analyze all three from one sample.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection, Storage, Handling): Not Given
References:
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Faye, G. M. and Inman, W. R., Res. Rept. MD-210, Canadian Dept. of Mines and
Tech. Surveys, Aug. 1957.
E-75
-------
2-77
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Technecium
Medium: Water
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma ray spectroscopy to identify, follow decay and
corroborate half-life.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine opera-
tions, the amount of the radionuclide present is determined.
Summary of Method: Copper carrier and appropriate holdback carriers are added to
an acidified aqueous sample and both copper and technetium are precipitated as
sulfides. After dissolving the precipitate, the technetium is separated from the
copper by cation exchange purification and coprecipitated with copper carrie^ as
CuS for counting. The copper is eluted from the resin column, reduced to Cu with
Na^SO., and precipitated as CuCNS for counting. This method also precipitates copper.
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
Gamma Ray Beta Particle
99mTc 0.04 0.02
Interferences: This method also precipitates copper
Decontamination Factors
131I 58/60Co 110mAg
"V 102 103 103
Pitfalls; Special Precautions: Plot gamma ray spectrum Immediately. The
chemical yield for 99mTc does not account for any losses that may occur in
the first seven steps of the method. Studies with long-lived 99Tc have
indicated that 95% of the technetium activity was present in the resin
effluent. Analysts should determine their own average tracer loss and
incorporate it in the calculations. With the multitude of reactor and
waste solutions generated,radionuclide and chemical compositions will
vary and therefore require auxiliary treatment to effect desired decontam-
ination.
Statistical Characteristics;
Accuracy and Precision: Not Given
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Procedure
time: 2 samples - 6 hours. Plot gamma ray spectrum immediately and in 4
hours. Gamma scan after 24 hours to verify half-life.
Calibration Requirements: Counter Background - Gamma spectrometer.
Data Outputs: Counts and time and energy.
Special Sampling Requirements (Collection, Storage. Handling); Not Given
Reference;
(1) Procedures for Radlochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Master Analytical Manual, ORNL, TID-7015, Method 5-11230, 1957.
(3) Anders, E., "The Radiochemistry of Technetium", Nuclear Science
Series NAS-NS-3021, Nat'l. Acad. Sci., Nat'l. Res. Council, USAEC,
1960.
(4) Kolthoff, I.M. and Sandell, E.B., Textbook of Quantitative Inorganic
Analysis, p. 701, The Macmillan company, 1946.
E-76
-------
E-78
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Tellurium
Medium: Water
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma ray spectroscopy to identify isotopes
and observe decay. Beta count to corroborate half-life.
Purpose of Measurement(Important Applications); To evaluate potential health
hazard from radlonuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method; Tellurium carrier is added to the acidified aqueous sample.
Impurities are removed by a double hydroxide scavenge. The tellurium salts are
collected in acid solution and reduced to metal for counting.
Limitations:
Range of Applicability: Minimum Detectable Limit (pCi/ml)
132 Gamma Ray Beta Particle
Te 0.06 0.02
132
Interferences: Decontamination Factors for Te
131T 58/60,, 110m.
I Co Ag
102 102 103
Pitfalls; Special Precuations: Beta count immediately after separation.
With the multitude of reactor and waste solutions generated radionuclide
and chemical compositions will vary and therefore require auxiliary
treatment to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not given
Time of Measurement (Maximum Frequency. Recovery Period, etc.): Procedure
time: 4 samples - 8 hours. Plot gamma ray spectrum and repeat after
2 days. Beta,count immediately and at 2-dav intervals to corroborate
half-life of 13ZTe and 1Z9Te.
Calibration Requirements: Counter background. Calibrate gamma spectrometer and beta
counter.
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection, Storage, Handling): Not given
Reference;
Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous Solutions,
Report No. EPA-4A-72-XXXX (Draft), National Environmental Research Center,
EPA, Cincinnati, Ohio, 1972.
E-77
-------
E-79
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Thorium 230
Medium; Air
Name of Measurement Method: Not given
Principal Detection Technique: Alpha counter
Purpose of Measurement (Important Applications): To determine the throium 230
content of airborne dust particles.
Summary of Method; Depending on the weight of the airborne dust sample collected
on the membrane filter, either ignite the dust or wet ash the filter. Then concen-
trate the sample and dissolve in nitric acid. Add iron carrier.
Thorium is separated from calcium and sodium by co-precipitation with ferric
hydroxide. Separation from iron, titanium, and zirconium is accomplished by co-
precipitation with lanthanum or yttrium fluoride. The thorium is separated from
the lanthanum or yttrium by solvent extraction of the thenoyltrifluoroacetone
complex. The thorium is then counted.
Limitations:
Range of Applicability: Airborne dust
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement; Not given
Calibration Requirements: Alpha counter
Background
Calibration factors
Data Outputs: Counts and time
Special Sampling Requirements (Collection, Storage. Handling): Not given
Reference : Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-78
-------
E-80
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Thorium 230
Medium: Sediment and soil
Name of Measurement Method: Not given
Principal Detection Technique: Alpha counter
Purpose of Measurement (Important Applications): To determine thorium 230
content of sediment and soil.
Summary of Method: Concentrate the ashed sample, solubilize with nitric acid,
and add iron carriers.
Thorium is separated from calcium and sodium by co-precipitation with
ferric hydroxide. Separation from iron, titanium, and zirconium is accomplished
by co-precipitation with lanthanum or yttrium fluoride. The thorium Is separated
from the lanthanum or yttrium by solvent extraction of the thenoyltrifluoracetone
complex. The thorium is then counted.
Limitations:
Range of Applicability: Not given
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement: Not given
Calibration Requirements: Alpha counter
Background
Calibration factor
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage. Handling): Ash the sample
Reference ; Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-79
-------
E-81
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Thorium 230
Medium: Water (Suspended Solids)
Name of Measurement Method: Not given
Principal Detection Technique: Alpha counter.
Purpose of Measurement (Important Applications): To determine the thorium 230
content of water.
Summary of Method: Filter the sample and add concentrated hydrochloric acid.
Add nitric acid and appropriate carriers. Evaporate to drynees and then
dissolve in nitric acid.
Thorium is separated from calcium and sodium by co-precipitation with
ferric hydroxide. Separation from iron, titanium, and zirconium is accomplished
by co-precipitation with lanthanum or yttrium fluoride. The thorium is
separated from the lanthanum or yttrium by solvent extraction of the
thenoyltrifluoroacetone complex. The thorium is then counted.
Limitations:
Range of Applicability; Not given
Interferences; Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics;
Accuracy; Not given
Precision; Not given
Time of Measurement; Not given
Calibration Requirements:
Alpha counter
Background
Calibration factors.
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage. Handling); Not given
Reference: Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-80
-------
E-82
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Thorium 230
Medium: Water
Name of Measurement Method: Not given
Principal Detection Technique: Alpha counter
Purpose of Measurement (Important Applications): To determine thorium 230
content of suspended solids in water.
Summary of Method: Filter the sample. Depending on the weight of the suspended
solids, either ignite them or wet ash the filter. Then concentrate the sample,
solubilize with nitric acid and add iron carrier.
Thorium is separated from calcium and sodium by co-precipitation with ferric
hydroxide. Separation from iron, titanium, and zirconium is accomplished by co-
precipitation with lanthanum or yttrium fluoride. The thorium is separated from
the lanthanum or yttrium by solvent extraction of the thenoyltrifluoroacetone
complex. The thorium is then counted.
Limitations:
Range of Applicability: Suspended solids
Interferences: Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement: Not given
Calibration Requirements: Alpha counter
Background
Calibration factor
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage. Handling): Not given
Reference: Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-81
-------
E-83
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Thorium 232
Medium: Environmental samples
Name of Measurement Method: Ion-exchange separation and coprecipitatlon.
Principal Detection Technique: Alpha spectroscopy to measure activity; beta
count to determine recovery.
Purpose of Measurement (Important Applications): Determination of content of thorium
232 in environmental samples.
Summary of Method: This method can also be used to analyze uranium. Add uranium and
thorium carriers. Fuse the sample and remove silica with hydrofluoric acid. Dissolve
in HC1. Pass the sample over an anion-exchange resin. Uranium is adsorbed and thorium
passes through in the effluent. Elute the uranium. The thorium is purified by
adsorption on anion resin equilibrated with nitric acid and then coprecipitated with
lanthanam fluoride and counted.
Limitations:
Range of Applicability; Not given
Interferences; Not given
Pitfalls. Special Precautions; Not given
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement: Not given
Calibration Requirements; Alpha spectrometer; beta counter; background.
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage, Handling): Fuse sample
Reference; Strong, Ann (Editor), Procedures for Radiochemical Analysis
at the Eastern Environmental Radiation Laboratory, EERL Report Ho. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, EPA, Montgomery, Alabama
(Undated).
E-82
-------
r 84
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radioactive Tin
Medium: Water
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma spectroscopy to identify. Beta count to
substantiate half-life.
Purpose of Measurement (Important Applications); To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: Tin carrier and appropriate scavenging carriers added to
acidified sample and collected as mixed sulfides. Impurities removed by hydroxide
scavenging. Tin is precipitated with cupferron and ignited to SnO. for counting.
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
H3 Gamma Ray
Sn 0.01
Interferences: Decontamination Factors
131T 58/60. 110m.
I Co Ag
103 103 103
Pitfalls; Special Precautions: Gamma spectroscopy used to verify purity.
With the multitude of reactor and waste solutions generated,radionuclide and
chemical compositions will vary and therefore require auxiliary treatment to
effect desired decontamination.
Statistical Characteristics;
Accuracy and Precision: Not Given
Time of Measurement: 2 samples - 5 hours
Calibration Requirements: Counter background - calibrate gamma spectrometer and beta
counter.
Data Outputs: Comics anu time aiiu energy.
Special Sampling Requirements (Collection. Storage. Handling): Not Given.'
References
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Chemical Procedures Used in Bombardment Work at Berkeley, UCRL-432,
W. Wayne Meinke, ed., October 15, 1949.
(3) H.J.M. Bowen and D. Gibbons, Radioactivation Analysis, p. 250, Oxford
University Press, 1963.
(3) Lingane, J. J., Analytical Chemistry of Selected Metallic Elements, p. 105,
Reinhold, 1966.
E-83
-------
E-85
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Tritium
Medium: Water
Name of Measurement Method; Not Given
Principal Detection Technique: Liquid scintillation spectrometer.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: Distill - aqueous sample to dryness. Mix portion of
distillate with scintillation solution and count.
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
Special Cases*
0.17
*Based on a 4 ml aliquot counted 300 minutes
Interferences; Decontamination Factors
131I 58/60Co 110mAg
103 103 10A
Pitfalls; Special Precautions: Dark adapt prior to counting. Standard tritium
and background samples are prepared and counted alternately to nullify aging
errors in scintillation medium or instrument drift. With the multitude of
reactor and waste solutions generated, radionuclide and chemical compositions
will vary and therefore require auxiliary treatment to effect desired
decontamination.
Statistical Characteristics;
Accuracy: Count at two selected window settings.
Precision: Count at least three times until successive results are within
+ 2o of each other.
Time of Measurement; 1 sample - 2 hours.
Calibration Requirements: Tritium H standard
Comments by Users: Proceduxes similar to ASTM standard method (E-87), but employs
different scintillation solution which gives better Figure of Merit.
Data Outputs: Counts and time
Special Sampling Requirements (Collection, Storage. Handling): Not Given.
References:
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Butler, F. E., "Determination of Tritium in Water and Urine", Anal.
Chem. 23, 409, 1961.
E-84
-------
:-87
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Tritium
Medium: Water
Name of Measurement Method: ASTM D2476-70
Principal Detection Technique: Scintillation Detection
Purpose of Measurement (Important Applications):
To evaluate potential health hazard from radionuclide discharges at nuclear
power stations during routine operations,the amount of the radionuclide present
is determined.
Summary of Method: Filter sample through a membrane filter if turbid. Distill
the sample if ionizing radiation other than tritium is present. Mix the radioactive
sample with a standardized scintillation solution. Scintillation detection is used
to count.
Limitations:
Range of Applicability: Minimum detectable limits (pCi/ml)
Special Case*
0.17
*Based on a A-ml aliquot counted 300 minutes in a
liquid scintillation system.
Although not always practical, lower limits can be obtained with larger
sample volumes and longer counting time. For nuclides discharged from
light-water moderated nuclear power reactors, the composition of the test
solutions has ranged from mixtures of many radionuclides at microcuries
per millimeter concentrations to barely detectable levels at picocuries
per liter concentrations. The substrate quality has ranged from highly
deionized coolant water to waste solutions of high salt contents plus
detergents.
Interferences: Ionizing radiation other than tritium.
Decontamination Factors
131T 58/60Co 110mAg
1C3 103 10*
Pitfalls; Special Precautions: With the multitude of reactor and waste
solutions generated, radionuclide and chemical compositions will vary and
therefore require auxiliary treatment to effect desired decontamination.
To make certain that the samples have been dark adapted, count at least
three times until successive results are within 2
-------
E-88
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Tritium
Medium: Ambient air
Name of Measurement Method; Not given
Principal Detection Technique; Liquid scintillation counter.
Purpose of Measurement (Important Applications); To separate water from
the ambient air.
Summary of Method: The sample is transferred to a gas analysis apparatus.
Water is removed by freezing and distillation. The radlokrypton, radioxenon,
radon 222, and carbon dioxide are separated by elution through a molecular
sieve column at various temperatures. The volumes of the separated gases
are measured for yield determination and transferred to appropriate
counting chambers.
The water sample may then be analyzed for tritium using method E-89 listed in
this compendium.
Limitations:
Range of Applicability; Not given
Interferences; Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics;
Accuracy: Not given
Precision: Not given
Time of Measurement: Not given
Calibration Requirements:
Counter efficiency
Background.
Data Outputs; Counts and time
Special Sampling Requirements (Collection. Storage. Handling): Sample may be
either grab or continuous.
Reference ; Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-86
-------
E-89
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Tritium
Medium; Water
Name of Measurement Method; Not given
Principal Detection Technique; Liquid scintillation spectrometer
Purpose of Measurement (Important Applications): To determine tritium content
of water.
Summary of Method; The sample is distilled to remove any suspended or dissolved
solids. Aliquots of the distillate are pipetted into counting vials along with
a liquid scintillation solution. The sample is then counted in a liquid
scintillation spectrometer.
Limitations:
Range of Applicability; Not given
Interferences: Radioiodine interferes: must be removed by distillation
over AgNO,.
Pitfalls: Special Precautions : T'ot given
Statistical Characteristics;
Accuracy: No t given
Precision; Not given
Time of Measurement; Not given
Calibration Requirements:
Counter efficiency
Background
Data Outputs: Counts and time
Special Sampling Requirements (Collection. Storage. Handling); Not given
Reference: Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-87
-------
E-90
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Radioactive Tungsten
Medium: Water
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma spectroscopy to identify.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: Tungsten carriers added to basic sample and collected as
tungsten acid. Impurities removed by hydroxide and basic sulfide scavengers.
Tungsten reprecipitated as tungsten acid and purified as WO,(CgH,ON)..
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
187 Beta Particle
w 0.03
Interferences: Decontamination Factors
131, 58/60Co 110mAg
10J 10J 10J
Pitfalls; Special Precautions: Gamma count immediately for identification of
W and determination of impurities. With the multitude of reactor and waste
solutions generated radionuclide and chemical compositions will vary and there-
fore require auxiliary treatment to effect desired decontamination.
Statistical Characteristics;
Accuracy and Precision; Not Given
Time of Measurement: 2 samples - 4 hours. Gamma spectroscopy immediately and
daily to identify and to corroborate half-life. Beta count to follow decay.
Data Outputs: Counts and time and energy.
Special Sampling Requirements (Collection. Storage. Handling): Not Given
Scferences:
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Prestwood, R. J., Collected Radiochemical Procedures, LA-1721, 2nd Ed.,
191-196, LASL, U. of Calif., 1958.
E-88
-------
E-91
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Uranium
Medium: Air
Name of Measurement Method: Fluororaetry
Principal Detection Technique: Fluorometry
Purpose of Measurement (Important Applications): To determine uranium content
of air.
Summary of Method: Digest the air filter and evaporate to dryness. Dissolve in
nitric acid. Then proceed either as for uranium in water (E-94) or uranium in soil and
sediment (E-93), depending on the residue which remains.
Limitations:
Range of Applicability: Not given
Interferences: Iron with chloride and perhaps sulfate and chlorate.
Pitfalls; Special Precautions: Depending on the residue on the air filter,
the sample may subsequently need treatment as a sediment sample with extraction
of uranium.
Where high quenching effects are taking place, consideration of background
quenching might have to be made to avoid low results.
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement: Not given
Calibration Requirements: Background fluorescence
Uranium standard
Data Outputs: Analoq sionsl
Special Sampling Requirements (Collection, Storage, Handling): See Uranium in
water or soil and sediment.
Reference : Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-89
-------
E-92
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Uranium
Medium; Environmental Samples
Name of Measurement Method: Ion-exchange separation and coprecipitation.
Principal Detection Technique: Alpha spectroscopy.
Purpose of Measurement (Important Applications): Determine content of uranium in
environmental samples.
Summary of Method: This method can also be used to analyze thorium 232. Add uranium
and thorium carriers and then fuse the sample and remove silica with hydrofluoric
acid. Dissolve in HC1. Pass the sample over an anion-exchange resin. Uranium is
adsorbed and thorium passes through in the effluent. Uranium is eluted with very
dilute HC1 and coprecipitated with lanthanum fluoride and then counted.
Limitations:
Range of Applicability: Not given
Interferences; Not given
Pitfalls; Special Precautions: Not given
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement; Not given
Calibration Requirements: Self-absorption curve; alpha spectrometer.
Data Outputs; Counts and time
Special Sampling Requirements (Collection. Storage. Handling); Not given
Reference : Strong, Ann (Editor), Procedures for Radiochemical Analysis
at the Eastern Environmental Radiation Laboratory, EERL Report No. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, EPA, Montgomery, Alabama
(Undated).
E-90
-------
E-93
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Uranium
Medium: Soil and Sediment
Name of Measurement Method: Fluorometry
Principal Detection Technique: Fluorometry
Purpose of Measurement (Important Applications): To determine uranium content
of soil and sediment.
Summary of Method; Concentrate the ashed sample and solubilize with nitric acid.
A uranium-uranium fluoride complex Is then formed. A sample pellet is prepared
for analysis by fluorometry.
Limitations:
Range of Applicability; Not given
Interferences: Iron with chloride and perhaps sulfate and chlorate
Pitfalls; Special Precautions; Total dissolution of the sample is sometimes
a rather difficult and lengthy process.
Where high quenching effects are taking place, consideration of background
quenching might have to be made to avoid low results.
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement; Not given
Calibration Requirements: Background fluorescence
Uranium standard
Data Outputs: Analog signal
Special Sampling Requirements (Collection, Storage. Handling): Ash the sample.
Reference: Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-91
-------
E-94
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Uranium
Medium: Water
Name of Measurement Method: Fluorometry
Principal Detection Technique: Fluorometry
Purpose of Measurement (Important Applications): To determine uranium content
of water.
Summary of Method: Filter the sample, evaporate into a platinum dish, and
analyze by fluorometry. If there is too large a suppression of fluorescence,
form a uranium-uranium fluoride complex. Then a sample pellet is prepared and
analyzed by fluorometry.
Limitations:
Range of Applicability: Not given
Interferences: Iron with chloride and perhaps sulfate and chlorate.
Pitfalls; Special Precautions: Where high quenching effects are taking
place, consideration of background quenching might have to be made to
avoid Ifr-' results.
Statistical Characteristics:
Accuracy: Not given
Precision: Not given
Time of Measurement: Not given
Calibration Requirements: Background fluorescence
Uranium standard
Data Outputs: Analog signal
Special Sampling Requirements (Collection, Storage, Handling): Not given
Reference? Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-92
-------
E-95
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured! Radioxenon
Medium; Ambient air
Name of Measurement Method: Not given
Principal Detection Technique: Scintillation counter
Purpose of Measurement (Important Applications): To determine the radioxenon
content of ambient air.
Summary of Method: The sample is transferred to a gas analysis apparatus.
Water is removed by freezing and distillation. The radiofcrypton, radioxenon,
radon 222, and carbon dioxide are separated by elution through a molecular
sieve column at various temperatures. The volumes of the separated gases
are measured for yield determination and transferred to appropriate counting
chambers.
Limitations:
Range of Applicability; Not given
Interferences; Not given
Pitfalls; Special Precautions; Not given
Statistical Characteristics;
Accuracy: Not given
Precision; Not given
Time of Measurement: Not given
Calibration Requirements:
Counter efficiency
Background.
Data Outputs; Counts and time
Special Sampling Requirements (Collection. Storage. Handling); Sample may be
either grab or cryogenic.
Reference: Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-93
-------
E-96
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioxenon
Medium; Natural gas
Name of Measurement Method; Not given
Principal Detection Technique; Scintillation counter
Purpose of Measurement (Important Applications); To determine radioxenon
content of natural gas.
Summary of Method; Convert the sample to carbon dioxide and water by
combustion. Separate the water by freezing. The gases are then adsorbed
on charcoal at liquid nitrogen temperature and separated from carbon
dioxide and each other by a series of low temperature chromographic steps.
The radioxenon is then analyzed using the method for radioxenon in ambient
air.
Limitations:
Range of Applicability; Not given
Interferences; Not given
Pitfalls; Special Precautions; Not given
Statistical Characteristics;
Accuracy; Not given
Precision; Not given
Time of Measurement; Not given
Calibration Requirements:
Counter efficiency
Background.
Data Outputs; Counts and time
Special Sampling Requirements (Collection. Storage. Handling); Not given
Reference: Johns, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods, March 1970
(reprint January 1972).
E-94
-------
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Yttrium
Medium; Water
Name of Measurement Method: Not Given
93 91
Principal Detection Technique: Gamma spectroscopy to identify Y and Y.
Beta count to confirm presence of 90y and corroborate Y half-life.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: Yttrium carrier and appropriate holdback carriers are
added to acidified sample. Yttrium collected as the fluoride. After purification
by hydroxide precipitation and extraction into trlbutyl phosphate, the yttrium is
precipitated as Y2(C204)3.7 H20 for counting.
Limitations;
Range of Applicability: Not Given
Interferences:, Not Given
Pitfalls; Special Precautions: Gamma spectroscopy to determine impurities.
With the multitude of reactor and waste solutions generated, radionuclide and
chemical compositions will vary and therefore require auxiliary treatment to
effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not Given
Time of Measurement: 2 samples - 4 hours; gamma scan again after 5 days;
beta count daily.
Calibration Requirements: Counter background - calibrate gamma spectrometer and beta
counter.
Data Outputs: Counts and time ana energy.
Special Sampling Requirements (Collection, Storage, Handling): Not Given.
Reference :
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Stanley, C. W., Collected Radiochemical Procedures, LA-1721, 2nd Ed.,
104-107, LASL, U. of Calif., 1958.
E-95
-------
E-98
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Zinc 65
Medium: Soil and Silt
Name of Measurement Method: Gamma spectrometry
Principal Detection Technique: Gamma spectrometry
Purpose of Measurement (Important Applications): Determine content of zinc 65 in
soil and silt.
Summary of Method: Fuse sample. Place in container for gamma spectometry.
Limitations:
Range of Applicability: Not Given
Interferences: Not Given
Pitfalls; Special Precautions: Not Given
Statistical Characteristics:
Accuracy: Not Given
Precision: Not Given
Time of Measurement: Not Given
Calibration Requirements: Background; Gamma spectrometer
Data Outputs: Counts and time and energy
Special Sampling Requirements (Collection, Storage, Handling): Fuse sample.
Reference : Douglas, Geneva S. (Editor), Radloassay Procedures for Environmental
Samples, National Center for Radiological Health, U.S. Public Health Service,
Rockville, Maryland, January, 1967.
*This method is considered acceptable by EPA, but is not necessarily used in EPA
laboratories.
E-96
-------
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Zinc
Medium: Water
Name of Measurement Method: Not Given
Principal Detection Technique: Gamma Spectroscopy
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine opera-
tions, the amount of the radionuclide present is determined.
Summary of Method: Zinc carrier and appropriate scavenging carriers are added
to acidified sample and impurities removed by basic hydroxide and acid sulfide
precipitations. The zinc is collected as zinc mercuric thiocyanate and purified
as ZnCC.-HgNO^.H-O for counting.
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
fir Gamma Ray
Zn 0.15
Interferences: Decontamination factors
131T 58/60., 110m.
1 Co Ag
103 103 10*
Pitfalls; Special Precautions: Gamma spectrometry to note presence of
contaminants. With the multitude of reactor and waste solutions generated,
radionuclide and chemical compositions will vary and therefore require
auxiliary treatment to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not Given
Time of Measurement: 2 samples - 4 hours
Calibration Requirements: Background - Gamma spectrometer
Data Outputs; Counts and time and energy.
Special Sampling Requirements (Collection. Storage. Handling): Not Given
Reference:
(1) Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Lingane, J. J., Analytical Chemistry of Selected Metallic Elements, pp. 48
and 131, Reinhold, 1966.
(3) Bowen, H. J. M. and Gibbons, D., Radioactivation Analysis, p. 233,
Oxford University Press, 1963.
(4) Kolthoff, 1. M. and Sandell, E. B., Textbook of Quantitative Inorganic
Analysis, p. 85, The Macmillan Company, 1946.
E-97
-------
E-100
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Radioactive Zirconium
Medium! Water
Name of Measurement Method: Zirconium-Niobium
Principal Detection Technique: Gamma spectroscopy to identify; beta count to
measure decay and confirm half-life.
Purpose of Measurement (Important Applications): To evaluate potential health
hazard from radionuclide discharges at nuclear power stations during routine
operations, the amount of the radionuclide present is determined.
Summary of Method: Zirconium and niobium carriers added to acidified sample
and collected as phosphates. The zirconium is precipitated as the fluorozirconate,
reprecipitated and ashed to ZrO. for counting. Niobium can then be precipitated.
Limitations:
Range of Applicability: Minimum Detectable Limits (pCi/ml)
__ Gamma Ray Beta Particle
Zr 0.05 0.03
Interferences: Niobium also produced. Decontamination Factors
131T 58/60,, 110m,
I Co Ag
10A 102 103
Pitfalls; Special Precautions: With the multitude of reactor and waste
solutions generated, radionuclide and chemical compositions will vary and
therefore require auxiliary treatment to effect desired decontamination.
Statistical Characteristics:
Accuracy and Precision: Not Given
Time of Measurement; 2 samples - 8 hours (time to prepare zirconium and niobium).
(Ta-Ni preparation time) + 2 hours when methods combined to produce all three
(.zirconium, niobium and tantalum). Beta count at one month intervals.
Calibration Requirements: Gamma spectrometer; Beta Counter; background.
Comments by Users: Combining this procedure with tantalum-niobium method allows
all three to be analyzed from one sample.
Data Outputs: Counts and time and energy.
Special Sampling Requirements (Collection, Storage. Handling): Not given.
Reference:
(1) Procedures for Radlochemical Analysis of Nuclear Reactor Aqueous
Solutions, Report No. EPA-4A-72-XXXX (Draft), National Environmental
Research Center, EPA, Cincinnati, Ohio, 1972.
(2) Rodden, C. J., ed., Analysis of Essential Nuclear Reactor Materials,
Div. Tech. Inf., USAEC, 1964, p. 680 and 685.
(3) Steinberg, E. P., The Radiochemistry of Niobium and Tantalum, Nuclear
Science Series, NAS-NS-3039, 24-26, Nat'l Acad. Sci., Nat'l Red. Council,
USAEC, 1961.
E-98
-------
F. PESTICIDE METHODS
-------
No. F-l
SUMMARY OF ANALYTICAL METHOD
Paramcter(s) Measured: Bis(p-chlorophenyl) Acecic Acid (DDA)
HccHim: Human Urine
Name of Measurement Method: Cranmer, Carroll and Copeland Method.
1'rinripal Detection Technique; Microcoulometric and/or electron capture detection.
Purpose of Measurement (Important Applications): Applicable to the detection cf the
above named parameter in human urine.
Summary of Method: Urine sample is thoroughly mixed with an equal voli.mo of 2% acetic
add in hexane. Three such extractions are performed and the combined extracts are uvap-
orated to near dryness to remove all residual traces of water or acetic acid. The dry
extract is treated with boron trifluoridemethanol reagent to convert free p,p'-D'JA to
the methyl ester. After heating, the reaction is quenched with water and the reaction
mixture is then extracted three times with hexane. The combined hexane extracts ace
volume adjusted and the p,p'-DDA methyl ester is determined by microcoulo:netric and/or
electron capture detection. Cleanup of the hexane extract with a Florisil column is
necessary when detection is by electron capture.
Limitations:
Range of Applicability: Urine of humans or animals exposed to DDT wherein the
metabolic levels of DDA are 0.04 ppm or greater.
Sensitivity:
Detection Limit; 0.05 ppm
Interferences; None stated
Pitfalls; Special Precautions: None stated
Statistical Characteristics;
Accuracy; 90-102% range of recovery
Precision; No data
Recovery; Not stated
Time of Measurement; No data
Calibration Requirements; Operation within linear range of detector. Reference standard
must be of high purity.
Data Outputs; Electron capture or microcoulometric detection with strip chart recorder
readout.
Special Sampling Requirements (Collection, StorjRc, Handling): No special cor.siJer^ti^as.
Reference: Thompson, J. F. (Editor), Analysis of Pesticide Residues in Human and
Environmental Samples, EPA, "miniate & Pesticides Effects Laboratory,
Perrinc, Florida, January 19X1.
F-l
-------
No. F-2
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Chlorinated Hydrocarbon Pesticides such as Aldrin, (3-BHC, p.p'-DDD,
p,p'-DDE, o,p*-DDT, p,p'-DDT, Dieldrin, Endrin, Heptachlor, Heptachlor epoxide, Lindane.
Medium! Human Tissue (Liver, Kidney, Bone Marrow, Adrenal, Gonads, Brain)
Name of Measurement Method; Micro
Principal Detection Technique; Electron-Capture Gas Liquid Chromatography
Purpose of Measurement (Important Applications); To determine concentrations of the
above-listed pesticides in human tissue.
Summary of Method: A 500 mg sample is processed in a tissue grinder and extracted with
acetonitrile. (Twenty ng aldrin is added to 0.1 ml hexane in tissue grinder to act as
recovery check.) Sample is centrifuged and extracted twice more with aqueous acetonitrile
which is subsequently extracted with hexane. Combined extracts are concentrated by evap-
oration and eluted through a Florisil-packed micro column pre-wetted with hexane. Two
fractions are obtained: Fraction I, which is eluted by a measured quality of hexane
followed by 1% nethanol in hexane, contains heptachlor, aldrin, p,p'-DDE, o,p'-DDT and
p.p'-DDT. Fraction II, eluted with 1% methanol in hexane only, contains dieldrin, hepta-
chlor epoxide, endrin, B-BHC, lindane and p.p'-DDD. The volumes of the two fractions arc
adjusted and samples injected into electron-capture gas chromatography for analysis. Brain
extract must be treated with acetic anhydride and pyridine prior to chromatography.
Limitations:
Range of Applicability; Any human or animal tissue
Sensitivity; Gas chromatographic system must be capable of producing a peak of not
less than 50% f.s. recorder deflection resulting from injection of 100 picograms
of alclrin.
Detection Limit: .01 ppm
Interferences; Any electron capturing contaminants surviving the cleanup, and with
retention characteristics similar to specific pesticidal compounds.
Pitfalls; Special Precautions; Must take extreme pains with glassware cleaning.
Statistical Characteristics;
Accuracy; 80% mininum recovery
Precision; *2 standard deviations
Time of Measurement; 4 hours per sample in multiples of 6 or more samples.
Calibration Requirements; Operation within linear range of detector. Reference standards
must be of high purity.
Data Outputs; Gas-liquid chromatography, electron capture detection, strip chart recorder
or digital integrator readout.
Special Sampling Requirements (Collection, Storage. Handling): Refrigerate in freezer until
ready for analysis. Use only glass containers for samples.
Reference: Thompson, J. F. (Editor), Analysis of Pesticide Residues in Human and
Environmental Samples, EPA, Primate & Pesticides Effects Laboratory,
Perrine, Florida, January 1971.
F-2
-------
No. F-3
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured:
Chlorinated Hydrocarbon Pesticide and Metabolites (and certain other Pestlcidea—Aldrin;
a-BHC; B-BHC; Chlordane; Chlorobenslde; Chlorobenzllate; Diazinon; Dleldrln; Dilan; o,p'-DDD:
prp'-DDD; O,P'-DDE; p,p'-DDE; o.p'-DDT; p.p'-DDT; Endosulfan I; Endosulfan II; Endtin;
Ethion; Ethyl Parachion; y-BHC; Hcptachlor; Kept. Epoxlde; Isobut. ester,2,4,D; Isoctyl
cscer 2,4-D; Isopropyl ester 2,4-D; Isooctyl ester 2,4,5-T; Isopropyl ester 2,4,5-T:
Mai athlor; Methyl Parathion; Methoxychlor; n-Bufyl ester 2,4,5-T; Perthane; Ronncl; Tedion;
Trithion
Medium; Hunan or Animal Adipose Tissue
Name of Measurement Method: Modified Mills, Onley Gal (.her Procedure
Principal Detection Technique: Gas Chromatography
Purpose of Measurement (Important Applications): For determination of chlorinated hydro-
carbon pesticides in fatty tissue.
Summary of Method; A 3-gm sample of minced fat is mixed with clean sand and anhydrous
sodium sulfate. 200 nanograms of aldrin in hexane is added as a recovery check and to
aid in peak identification in later chromatogrnphy step (assuming that nldrin is not
suspected in the sample). The mixture is extracted three times with petroleum ether, the
extract is filtered, the solvent carefully evaporated, and then weighed to determine per-
cent fat in sample. A sample of the extracted fat Is dissolved in petroleum ether then
is extracted 4 times with acetonitrilc. Chlorinated hydrocarbons (if present in the sample)
are partitioned from the diluted acetonitrile by petroleum ether, with use of a sodium
chloride aqueous solution to improve recovery. The solution of pesticides in petroleum
ether is dried over anhydrous sodium sulfate and concentrated by careful evaporation. Thp.
concentrate is separated into fractions by a chromatographic column packed with Florisil.
After the concentrate is placed on the column, it is eluted with a solution of six percent
diethyl ether in petroleum ether to produce Fraction I, then with 15 percent dlethyl ether
in petroleum ether to produce Fraction II. The second fraction is spiked with 0.022 aldrin
in hexane for reasons given above. (If malathion is suspected in the sample, a third
fraction is obtained by eluting with 50% diethyl ether in petroleum ethsr). The pesticides,
which if present in the original sample would appear in each of the three fractions, are
identified in the reference cited below. The fractions are then concentrated, and each
is analyzed separately by gas chromatography.
Limitations:
Range of Applicability: Suitable for analysis of most tissue samples, human or
animal when sample size is 3 grams or greater.
Detection Limit; 0.01 to 0.10 ppm (depending on specific compound response)
Interferences: Any electron capturing contaminants with retention characteristics
similar to specific pesticldal compounds.
Pitfalls; Special Precautions; Florisil elution patterns and recovery potential must
be previously established by individual analyst under prevailing conditions.
Statistical Characteristics:
Accuracy: 855! recovery for chlorinated pesticides
Precision: ±2 standard deviations
Time of Measurement; 5 hours based on multiple analyses of 26 samples per month
per person.
Calibration Requirements: Operation within linear range of detector.
Data Outputs; Gas-liquid chromatography, electron capture detection, recorder or digital
integrator readout.
Special Sampling Requirements: Sample container restricted to glass vessels with lids
or plugs of glass, Teflon or foil. Avoid all plastic matciials.
Reference: Thompson, J. F. (Editor), Analysis of Pesticide Residues in Human
and Environmental Samples, EPA, Primate & Pesticides Effects
Laboratory, Perrine, Florida, January 1971.
F-3
-------
r.o. F-4
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Multiple Chlorinated Hydrocarbon Pesticides
Medium: Human Blood or Serum
Namp. of Measurement Method: Thompson, Walker, Enos - Manuscript in review
Principal Detection Technique: Electron capture, gas chromatography
Purpose of Measurement (Important Applications): A general and convenient survey method
to measure the level of chlorinated hydrocarbon pesticide in human blood.
Summary of Method: A 2 ml aliquot of serum is extracted with hexane. The extraction
is conducted Cor two hours on a slow speed rotating mixer. An aliquot of the hexane
layer is quantitatively transferred to an evaporative concentrator tube to whir.h is
affixed a modified micro-Snyder column. The extract is concentrated in a water or steam
bath and the final volume is adjusted to correspond to the expected concentration of the
pesticide residue. A suitable aliquot is analyzed by electron capture gas chromatography.
Limitations:
Range of Applicability: Suitable for blood or serum
Sensitivity: Not stated
Detection Limit: 1-2 ppb
Interferences: Not stated
Pitfalls; Special Precautions: Certain samples may produce heavy emulsions during
the extraction step. It is mandatory that centrifugation be conducted so that clear
extract is obtained for pipet transfer to evaporator tube.
Statistical Characteristics:
Accuracy: 85% recovery for many common organochlorine compounds.
Precision; ±2 standard deviations for p,p'-DDE and p,p'-DDT and 3 standard deviations
for lower level compounds such as dieldrin, o,p'-DDT, etc.
Sensitivity: Gas chromatographic system must be capable of producing a peak of not
less than 50% f.s. recorder deflection resulting from injection of 100 picograms
of aldrin.
Time of Measurement: 2 hours per sample in multiples of 6 or more samples.
Calibration Requirements: Operation within linear range of detector. Reference standards
must be high purity.
Data Outputs: Gas-liquid chromatography, electron capture detection, strip chart
recorder readout.
Special Sampling Requirements (Collection. Storage. Handling); Refrigerate in freezer
until ready for analysis. Samples should be in glass containers with glass, Teflon or
foil-lined caps.
Reference; Thompson, J. F. (Editor), Analysis of Pesticide Residues in Human and
Environmental Samples, EPA, Primate & Pesticides Effects Laboratory, Perrine, Florida,
January 1971.
F-4
-------
No. F-5
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Cholinesterase Activity
Medium; Blood
Name of Measurement Method; Continuous (Titration)
Principal Detection Technique; Titrimetric (Automatic)
Purpose of Measurement (Important Applications): To establish possible
exposure to organophosphates.
Summary of Method; The whole blood sample is separated into the plasma and
red blood cells.Each fraction is placed in the reaction vessel of a pH-Stat
and mixed with an excess of acetylcholine iodide (AChI). The Cholinesterase
present in the blood fraction reacts with the AChI releasing acetic acid.
A standardized solution of dilute sodium hydroxide is used as the titrant
for the released acid.
Limitations;
Range of Applicability! Lower limits of normal Cholinesterase
activity for human blood is 2.0 p.M/min/ml (plasma) and 8.0 ^M/min/ml
(red cells).
Sensitivity; Not stated
Detection Limit: Not stated
Interferences; None specified
Pitfalls; Special Precautions; Weighing of acetylcholine iodide
should be rapid, as it is hygroscopic hence the weight will
fluctuate with delay.
Statistical Characteristics;
Accuracy; Not stated
Precision: Not stated
Recovery; Not stated
Time of Measurement; Assumed to be rapid.
Calibration Requirements; No unusual requirements were indicated. Standard
solutions should be restandardized each time that a series of samples are run.
Data Outputs; Not stated; assumed to be electrical signals displayed on
meter or chart.
Special Sampling Requirements (Collection. Storage. Handling); Sample
preparation and analysis of blood should be carried out as soon as
possible after withdrawal of sample.
Reference; Thompson, J. F. (Editor), Analysis of Pesticide Residues in Human
and Environmental Samples, EPA, Primate & Pesticides Effects
Laboratory, Perrine, Florida, January 1971.
F-5
-------
SUMMARY OF ANALYTICAL METHOD No- F~6
Parameter(s) Measured: Methylmercury (CH.HG)
Modiuin: Fish, B]ood and Brain
III!
Nama of Measurement Method: Modified Westoo Method
Principal DotcctJon Technique: Gas Liquid Chromatography
Purpose of Measurement (Important Applications; Applicable for analysis of fish, red
blood cells, plasma and brain of hamsters.
Summary of Method; Methylmercuric chloride is formed by the addition of hydrochloric add
to homogenized tissue, and the organic salt is then extracted into benzene. The methyl
mercury is extracted from the benzene solution by partitioning it with aqueous cysteine
solution. The aqueous layer is acidified and the salt is re-extracted back into benzene.
The final benzene layer is analyzed by gas-liquid chromatography.
Limitations:
Range of Applicability: Not stated
Sensitivity: Not stated
Interferences: Not stated
Pitfalls; Special Precautions: Glassware used should be thoroughly
washed and rinsed successively with ammonium hydroxide, distilled
water and ethanol. Gas chromatographic column conditioning is very
critical. An improperly conditioned column will result in very
poor response.
Statistical Characteristics:
Accuracy; 75-85% range of recoveries
Precision: + 3 percent
Time of Measurement: Not stated
Calibration Requirements: See Reference
Data Outputs: Analog electrical signal displayed as chromatogram.
Special Sampling Requirements (Collection, Storage. Handling): Not stated
Reference; Thompson, J.F. (Editor), Analysis of Pesticide Residue in Human and
Environmental Samples, EPA, Primate & Pesticides Effects Laboratory,
Perrine, Florida, January 1971.
F-6
-------
SUMMARY OF ANALYTICAL METHOD
No' F~7
Paramcter(s) Measured; 1-Nsphthol
Medium: Urine (Human)
Name of Measurement Method; Shafik, Sullivan & Enos Method
Principal Detection Technique; Electron Capture Gas Chroma tography
Purpose of Measurement (Important Applications) ; Used as an indirect measure of the
residual level of the parent insecticide (carbaryl) on a variety of agricultural crops.
Summary ot Method; A small sample of urine is acidified with HC1 and refluxed on a steam
£S rhi-r±n8 M°Ut 2? ?iy8±S; *• 1-M*htho1 Present is extracted in benzene and reacted
with chloroacetic anhydride solution. After silica gel cleanup the resulting 1-naphthol
chloroacetate a quantitatively determined by electron-capture gas liquid chroma tography.
dwivatized" arC C°mpared a*alnst Peaks obtained from pure 1-naphthol standard, similarly
Limitations;
Range of Applicability; Not stated
Sensitivity; Not stated
Detection Limit; .02 ppm
Interferences; Not stated
Pitfalls; Special Precautions; Not stated
Statistical Characteristics;
Accuracy; No data are given in the reference cited below.
Precision; No data
Time of Measurement; Recovery checks should be done on known quantities of standards
added to urine sample and carried through the identical procedure.
Calibration Requirements; No unusual requirements
Data Outputs; Not stated; assumed to be electrical signals displayed graphically.
Special Sampling Requirements (Collection. Storage. Handling); Not stated
Reference; Thompson, J.F. (Editor), Analysis of Pesticide Residues in Human and
Environmental Samples, EPA, Primate & Pesticides Effects Laboratory,
Perrine, Florida, January 1971.
F-7
-------
No. F-8
SUMMARY OF ANALYTICAL METHOD
Parameter(a) Measured; Organochlorine Pesticides
Under some
Aldrln DDT Heptachlor Epoxide circumstances;
BCH Dieldrin Llndane Chlorodane (tech)
Chlordane (Y) Endosulfan Methoxychlor Kelthane
ODD EndrlD Perchane Scrobane
DDE. Heptachlor Sulphenone Toxaphene
Medium; Water
Name of Measurement Method! Gas-liquid chromatography (GLC)
Principal Detection Technique(s); Electron Capture (EC)
Mlcrocoulometrlc Tltratlon (MC)
Electrolytic Conductivity (BCD)
Purpose of Measurement (Important Applications); For identification and quantl-
tation of various organochlorine pesticides, certain degradations products, and
related compounds.
Summary of Method; The method offers several analytical alternatives, dependent on
the complexity of pesticides In the sample and the nature and amounts of Interferences.
In general, the pesticides in the aqueous sample are extracted by organic solvents
(e.g., hexane or hexane/ethyl ether mixtures), and the extract concentrated by
careful evaporation of the solvent. Removal of Interferences (when necessary) and
pre-separation of pesticide mixtures are accomplished by column chromatography, thin-
layer chromatography, or liquid-liquid partitioning. Identification of pesticides in
the mixture is made by selective gas chromatographic separations through the use of
two or more unlike columns. Detection and measurement of pesticides in the sample
are accomplished by electron capture, mlcrocoulometrlc, or electrolytic conductivity
techniques. Quantitative results are obtained by measurement of areas under peaks
In the resulting chromatogran.
The reference cited describes the use of an effective solvent for
extraction of pesticides from aqueous samples. It provides information on the
selection of appropriate clean-up procedures and detectors for various types of
pesticide mixtures, and suggests techniques for confirming qualitative identifications.
Limitations;
Range of Applicability: Specific concentration ranges for various
pesticides in environmental samples are not cited, but the detection
capabilities of four types of detectors are indicated below.
Sensitivity and Detection Limits;
Electron Capture Detector plcogran (10~ gram) quantities of
many organochlorine pesticides
Mlcrocoulometrlc Titratlon 5-20 ng of organochlorine pesticides
Electrolytic Conductivity Sensitivity 2 to 3 times as great as
Detector nlcrocoulometric procedure
Flame Photometric Detector Sub-nanogram quantities of sulfur
and phosphorus
Sample responses less than two times the detector noise level (N)
should be reported aa negative; responses greater than 2 N should be
quantified if possible.
Interferences: Folychlorinated biphenyls, phthalate esters, organo-
phoaphorua pesticides. The presences of the latter two clasaes of
compounds are Implicated in samples that respond to certain detection
techniques but not to others.
Pitfalls; Special Precautions; Contaminants in solvents, reagents,
glassware, and other equipment may yield results that cause misinter-
pretation of chromatograms.
Statistical Characteristics!
Accuracy! Not stated as Z relative error, but given as Z recovery in Ref.
Precision; Results are given for four specific pesticides. Those for
aldrin are as follows:
Mean recovery, Precision fan/liter)
No cleanup
Florlsll cleanup
Time of Measurement! Not stated
Calibration Requirements: Procedures are detailed in Reference.
Comments by Users; Recommended for use only by, or under close supervision
of, experienced residue analysts.
Data Outputs: Analog electrical signals recorded on strlpcharts.
Special Sampling Requirements (Collection. Storage. Handling); Wide-
mouth bottles with Teflon-lined screw capa are used for sample
collection. Size of sample depends on nature of pesticide mixture and
type of detector.
References; Methods for Organic Pesticides in Wster and Wastevater, U. S.
Environmental Protection Agency, National Environmental Research
Center, Analytical Quality Control Laboratory, Cincinnati, Ohio (1971).
F-B
(ng/llter)
10.42
79.00
17.00
64.34
Overall
4.86
32.06
9.13
27.16
Single-Operation
2.59
20.19
3.48
8.02
-------
No F—Q
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Metabolites or Hydrolysis Products of Organophosphorus Pesticides
Medium: Human Urine
Name of Measurement Method; Shafik el al., Primate & Pesticides Effects Laboratory
Principal Detection Technique; Gas Chromatography with Flame Photometric Detection
Purpose of Measurement (Important Applications): Permits the determination of six major
metabolites and hydrolysis products of Organophosphorus pesticides.
Summary of Method: Organophosphate metabolites in urine are extracted with 1:1 (v/v)
mixture of acetonitrile and diethyl ether after acidification with 6N HC1. An aliquot
of the extraction solvent containing the dialkyl phosphates is treated with diazopentane
to convert the dialkyl phosphates to the more volatile trialkyl phosphates which are also
more amenable to gas chromatography. Trialkyl phosphates are determined by gas chromaco-
graphy using flame photometric detection with a phosphorus filter (526 imi). The presence
of sulfur-containing trialkyl phosphates may be confirmed by use of the flame photometric
detector with a sulfur filter (394 mu).
Limitations:
Range of Applicability; No special considerations
Sensitivity Requirements; Injection of 2.5 nanograms ethyl parathion should result
in peak of not less than 503! f.s.d. with baseline noise not exceeding 2.5%.
Detection Limit; .01 ppm
Interferences: Tnorganic phosphate interferences are eliminated.
Pitfalls; Special Precautions; Necessary to clean up the alkyl phosphate derivatives
using silica gel chromotography to eliminate interferences and obtain separations
of compounds producing closely adjacent peaks.
Statistical Characteristics;
Accuracy; 85% minimum recovery
Precision; No data
Sensitivity: Stated to be very high. 0.01 ppm for various compounds in this
category (signal/noise ratio of 4:1).
Time of Measurement; 2.5 hours per sample
Calibration Requirements: Reference standards must be high purity
Data Outputs; Gas-liquid chromatography, flame photometric detection, strip chart
recorder output.
Special Sampling Requirements (Collection, Storage, Handling): Refrigerate in freezer
until ready for analysis.
Reference: Thompson, J. F. (Editor), Analysis of Pesticide Residues in Human and
Environmental Samples, EPA, Primate & Pesticides Effects Laboratory,
Perrine, Florida, January 1971.
F-9
-------
No. F-10
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Ha.isurod; Para-Nitrophenol (PNP)
Medium; Urine
Name of Measurement Method: Modified Elliott's method.
Principal Detection Technique: Gas Chromatography
Purpose of Measurement (Tpportanc Applications); To determine the level of PNP (the
phenolic metabolite of paraihJou, methyl parathion,and ENP) in urine.
Summary of Mccliod; A small volume of urine is hydroiyzert with hydrochloric acid to free
the PHP from the bound or adsorbed state. The hydrolyzed urine is raade alkaline and
extracted with benzene-other to minimize co-extraction of interferences in the subsequent
determinative extraction. The urine is then reacidified and extracted with benzene-ether.
The extract is dried, and a suitable aliquot is removed with the PNP being converted on
the column to the less polar and more volatile triinethylsHyl ether during the gas chro:aa-
tographic determinative steo.
Limitations!
Range; of Applicability: Acceptable analytical results at 50 ppb level.
Sensitivity; Not stated
Detection Limiti 0.05 ppm
Interferences! Not stated
Pitfalls; Special Precautions; Not stated
Statistical Characteristics;
Accuracy; 92-100% range of recoveries
Precision; No data
Time of Measurement; Less than 2 hours.
Calibration Requirements; See Reference
Data Outputs;Analog electrical signal displayed as chromatogram.
Special Sampling Requirements (Collection. Storage. Handling); Not stated
Reference; Thompson, J.F. (Editor), Analysis of Pesticide Residues in Human and
Environmental Samples, EPA, Primate & Pesticides Effects Laboratory,
Perrine, Florida, January 1971.
F-10
-------
Ho. F-ll
SUMMARY OF ANALYTICAL METHOD
Parnmel:cir(b) Measured: Pentachlorophenol (PCP)
Medium; Blood
of Measurement Method: Modified methods of Rivers
Principal Detection Technique; Electron-Capture Gas Liquid Chroma tography
Purpose of Measurement (Important Applications): To detect and measure PCP in human blood.
Summary of Method: This is a surveillance procedure involving no cleanup or partitioning
and is based upon the conversion of pentachlorophenol (PCP) to a methyl ether after a
2-hour extraction of the acidified sample in benzene. Electron-capture gas liquid chroma-
tography is utilized for quantitation, comparing sample peak against peaks from known
standards, similarly methylated.
Limitations:
Range of Applicability: Blood with PCP levels above 10 ppb
Sensitivity: Not stated
Detection Limit: 10 ppb
Interferences; All reagents including distilled water should be extracted with
hexane to eliminate contaminating PCP. Glassware should be washed with NaOH solution
and rinsed with deionizcd water and acetone.
Pitfalls; Special Precautions: Great care should be used in handling dlazoalkane
as it is toxic, carcinogenic and explosive.
Statistical Characteristics:
Accuracy; No data
Precision: No data
Sensitivity: Not stated
Time of Measurement; 1 hour per sample in multiples of 6 or more samples
Calibration Requirements; Operation within linear range of detector. Reference standards
must be high purity.
Data Outputs: Gas-liquid chroma tography , electron capture detection with strip chart
recorder readout.
Special Sampling Requirements (Collection, Storage, Handling): Samples or equipment nust
not be allowed to come in contact with wood or paper as PCP is very prevalent in these
materials in certain parts of tha country.
Reference: Thompson, J. F. (Editor), Analysis of Pesticide Residues in I'umpn and
Environmental Samples, EPA, Priume & Pesticides Effects Laboratory,
Perrine, Florida, January 1971.
F-ll
-------
SUMMARY OF ANALYTICAL METHOD No> F~12
Paramcter(s) Measured: Pentachlorophenol (PCP)
Medium: Human Urine
Name of Measurement Method; Cranmer and Freal Method
Principal Detection Technique: Gas Chromatography - Electron Capture
Purpose of Measurement (Important Applications); To indicate presence of PCP in human
sys ten.
Summary of Method; A sample of human urine is made alkaline and extracted with hexane
to remove basic and neutral interfering compounds. The alkaline urine is then acidified
and re-extracted with hexane. The PCP residue contained in a portion of the hexane
extract is derivatized with diazomethane. The aIkylated PCP is determined by gas
chromatography with electron capture detection.
Limitations;
Range of Applicability; Suitable for urine or water samples with
PCP levels down to 2 ppb.
Sensitivity; Not stated
Detection Limit; 2 ppb
Interferences! All reagents including distilled water should be extracted
with hexane to eliminate contaminating PCP. Glassware should be washed
with NaOH sol. and rinsed with deionized water and acetone.
Pitfalls; Special Precautions; Use extreme care in handling dialzoalkane
reagent as it is toxic, carcinogenic and explosive.
Statistical Characteristics;
Accuracy; No data
Precision; *5% from mean
Time of Measurement; 1-5 hours per sample In multiples of 6 or more samples.
Calibration Requirements: Operation within linear range of detector. Reference standard
must be high purity.
Para Outputs: Gas-liquid chromatography, electron capture detection, strip chart recorder
readout.
Special Sampling Requirements (Collection, Storage, Handling); Samples or equipment must
not be allowed to come in contact with, wood or paper as PCP is very prevalent in these
materials.
Reference; Thompson, J. F. (Editor), Analysis of Pesticide Residues in Human and
Environmental Samples, EPA, Primate & Pesticides Effects Laboratory,
Perrine, Florida, January 1971.
F-12
-------
SUMMARY OF ANALYTICAL METHOD No_ F_13
Parameter(s) Measured; Pesticides - Aidrin, Chlordane, Chlorobenside, a-BHC, 8-BHC,
Y-BHC, o,p'-DDE, p,p'-DDE, o,p'-DDD, p,p'-DDD, o,p'-DDT, p,p'-DDT, Diazinon, Dieldrin,
Endrin, Ethion, Ethyl Parathion, Heptachlor, Heptachlor Epoxide, Lindane, Malathion,
Methyl Parathion, Perthan, Tedion, Ronnel, Thiodan I, Thiodan II
Medium! Air
Mane of Measurement Method: Modification of Stanley et al., Midwest Research Institute
Principal Detection Technique; Electron Capture Detection and Flame Photometric Detection
Purpose of Measurement (Important Applications): To detect the presence of pesticides in
the atmosphere.
Summary of Method: A composite sample (e.g., all samples obtained over a day's operation
at a sampling site) is extracted repeatedly with hexane, dried over sodium sulfate, and
concentrated by evaporation. The hexane concentrate is placed on a Florisil column and
separated into three fractions by eluting three times with mixed ethers (diethyl ether and •
petroleum ether) of different proportions. Two of the fractions are diluted with hexane
and analyzed for chlorinated pesticides by electron capture gas chromotography. The third
fraction and a reconcentrate of the second fraction are analyze'd for brganophosphate
pesticides by flame photometry.
Limitations;
Range of Applicabilityt Samples collected in trapping medium of ethylene glycol.
Detection Limit: 0.2 to 3.0 ng/m. for common chlorinated pesticides,
0.4 to 3.0 ng/m for organuphosphorous pesticides listed in method.
Interferences: Organic pollutants
Pitfalls; Special Precautions; All glassware to be used must be scrupulously cleaned
and given a hexane rinse prior to use. Do not evaporate fractions to dryness.
Statistical Characteristics;
Accuracy; 85% minimum recovery
Precision: -2 standard deviations
Time of Measurement: 5 to 6 hours per sample (based on multiple analyses of 100
samples per month by three chemists)
Calibration Requirements: Operation within linear range of detector.. Reference standards
must be high purity.
Data Outputs; Gas-liquid chromatography, electron capture and flame photometric detection,
recorder or digital integrator readout.
Special Sampling Requirements (Collection, Storage. Handling): Air sampling unit developed
by Midwest Research Institute is used to collect samples. Store samples in glass.
RegriEeration required for periods exceeding 24 hours.
Reference; Thompson, J. F. (Editor), Analysis of Pesticide Residues in Human
and Environmental Samples, EPA, Primate & Pesticides Effects
Laboratory, Perrine, Florida, January 1971.
F-13
-------
No. F-14
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Pesticides
Medium; Water
Name of Measurement Method; Modified methods from Federal Water Quality
Administration.
Principal Detection Technique; Electron Capture, Gas Liquid Chromatography
Purpose of Measurement (Important Applications); To determine presence and
identification of pesticides in water.
Summary of Method; The water sample is subjected to multiple extraction by
ethyl ether/hexane. The combined extracts are dried with anhydrous sodium
sulfate, evaporated under a stream of nitrogen, and further concentrated by
heating. Aliquots of about 5 jil are used for the initial electron capture
gas liquid chromatography. Further identification may be necessary through
microcoulometry or thin layer Chromatography.
Limitations:
Range of Applicability; Not stated
Sensitivity! Not stated
Detection Limit; Not stated
Interferences: If interferences are indicated in initial
chromatograms, it may be necessary to conduct a Florisil
cleanup on the extract.
Pitfalls; Special Precautions: Not stated
Statistical Characteristics;
Accuracy; Not stated
Precision: Not stated
Time of Measurement: Not stated
Calibration Requirements; See Reference
Data Outputs: Analog electrical signal displayed as chromatogram.
Special Sampling Requirements (Collection. Storage. Handling); Sampling collection
glassware should be scrupulously cleaned. If storage is necessary, samples should
be kept in cool, dark place or preferably in a refrigerator.
Reference; Thompson, J. F. (Editor), Analysis of Pesticide Residues in Human
and Environmental Samples, EPA, Primate & Pesticides Effects
Laboratory, Perrine, Florida, January 1971.
F-14
-------
No. F-15
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Pesticides
Medium; Soils and House Dusts
Principal Detection Technique; Electron Capture Gas Chromatography and/or
Flame Photometric Detection.
Purpose of Measurement (Important Applications); Applicable to pesticide
detection in soil and dust from vacuum cleaner.
Summary of Method! Organochlorine pesticides, together with other lipid-soluble
substances, are extracted from homogenized samples of continuous Soxhlet extraction
with acetone-hexane. The solvent is evaporated and concentrated for determinative
analysis by electron capture or flame photometric detection. Confirmation as
needed can be done by microcoulometry and/or thin layer Chromatography.
Limitations:
Range of Applicability; Not stated
Sensitivity; Not stated
Detection Limits; Not stated
Interferences; Lipid-soluble materials are partially removed
by successive cleanup on aluminum oxide and Florisil columns.
Pitfalls; Special Precautions: None stated
Statistical Characteristics:
Accuracy; Not stated
Precision; Not stated
Time of Measurement; Not stated
Calibration Requirements; See Reference.
Data Outputs; Assumed to be electrical signals which are graphically displayed.
Special Sampling Requirements (Collection. Storage. Handling); Not stated
Reference: Thompson, J.F. (Editor), Analysis of Pesticide Residues in Human
and Environmental Samples, EPA, Primate & Pesticides Effects
Laboratory, Perrine, Florida, January 1971.
F-15
-------
No. F-16
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Polychlorinated Biphenyls (PCB's)
Medium: Adipose tissue
Name of Measurement Method; Modified Mulhorn, Chromartle, Relchel and
Bellsle Method.
Principal Detection Technique; Thin Layer Chromatography
Purpose of Measurement (Important Applications); Provides convenient means
of separating Aroclor 1254 and 1260 from common chlorinating pesticides;
confirms identification, and approximates concentration (semi-quantitative).
Summary of Method; Adipose tissue is subjected to extraction by petroleum
ether, acetonitrile partitioning, and Florlsll cleanup. A portion of the
resulting six percent ethyl-ether/petroleum-ether eluate in concentrated form,
is treated with KOH for dehydrochlorination of DDT and DDD to their olefins.
Oxidatlve treatment is applied and the polychlorinated biphenyls are then
determined by thin-layer chromatography.
Limitations;
Range of Applicability: Not stated
Sensitivity; Not stated
Detection Limit; Not stated
Interferences; DDT and its analogs are potential interferences
in the Chromatography step. Interference from DDE eliminated
by use of oxidative treatment; interference from DDD and DDT is
eliminated by the dechlorination.
Statistical Characteristics;
Accuracy: Not stated
Precision; Not stated
Recovery; Recovery studies have indicated 50 percent precision
for this procedure using Aroclor 1260 as reference standard.
Time of Measurement; Not stated
Calibration Requirements; See Reference.
Data Outputs; Analog electrical signal displayed as chromatogram.
Special Sampling Requirements (Collection. Storage, Handling); Not stated
Reference; Thompson, J. F. (Editor), Analysis of Pesticide
Residue in Human and Environmental Samples, EPA,
Primate & Pesticides Effects Laboratory, Perrlne,
Florida, January 1971.
F-16
-------
No. F-17
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: 2,4-D and 2,4,5-T
Medium; Urine
Name of Measurement Method: Shafik, Sullivan and Enos Method
Principal Detection Technique; Electron Capture - Gas Liquid Chromatography
Purpose of Measurement (Important Applications); Provides a rapid, sensitive
procedure for the detection of derivatives of 2,4-dichlorophenoxyacetic acid (2,4-D)
and 2,4,5-trichlorophenoxyacetlc acids (2,4,5-T) in human and animal urine.
Summary of Method; The phenolic conjugates are subjected to acid hydrolysis,
the free phenols and acids are extracted and ethylated with diazoethane.
Cleanup of the derivatized products is carried out on a silica gel column,
and the resulting eluate is concentrated to an appropriate extent and
subjected to analysis by electron capture gas liquid chromatography.
Limitations:
Range of Applicability; Suitable for urine or water samples.
Detection Limit; 0.02 to 0.05 ppm
Interferences; To avoid interferences all distilled water used
throughout the procedure must be benzene extracted.
Pitfalls; Special Precautions; Extreme caution should be
observed in the handling of reagents such as nitrosoguanidlne and
diazoethane. These chemicals have been demonstrated to be
carcinogenic and toxic.
Statistical Characteristics;
Accuracy; 84-107 percent recovery range
Precision! No data
Sensitivity; Gas chromatographic system must be capable of producing
a peak of not less than 50 percent f.s. recorder deflection resulting
from injection of 100 pgs of aldrin.
Time of Measurement; 1.5 hours per sample in multiples of 6
or more samples.
Calibration Requirements; Operation within linear range of detector. Reference
standards must be high purity.
Data Outputs; Electron capture detection, strip chart recorder readout.
Special Sampling Requirements (Collection. Storage. Handling); No special
considerations.
Reference: Thompson, J. F. (Editor), Analysis of Pesticide Residues in
Human and Environmental Samples, EPA, Primate & Pesticides
Effects Laboratory, Perrlne, Florida, January 1971.
F-17
-------
G. OIL AND GREASE METHODS
-------
No. G-l
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: API Gravity (Density)
Medium: Petroleum products
Name of Measurement Method: API Rravity of Crude Petroleum and Petroleum
Products (ASTM D 287)
Principal Detection Technique: Hydrometer (API gravity (degrees) is
141 5
'
defined as
sp. gr.60/60F
Purpose of Measurement (Important Applications) : For measuring API gravity
of petroleum products in the liquid state and having a Reid vapor pressure of
26 Ib. or less.
Summary of Method: A hvdrometer graduated in API gravity units is allowed to
float freely in the sample that has reached equilibrium temperature. The
temperature of the sample is measured and the API gravity read from the
hydrometer graduation nearest the horizontal surface of the liquid. Liquid
temperature may be between 0 and 195 F, but method is most nearly accurate
near 60 F. For samples at other temperatures, the observed reading is con-
verted to API gravity at 60Fbv standard tables.
Limitations:
Range of Applicability: Not stated, although hydrometers scaled
in API gravity units (degrees), from -1 to 101 degrees, are available.
Interferences: None identified
Sensitivity: 0.1 degree (API gravity)
Pitfalls; Special Precautions; Temperature conversion tables are not
applicable to non-hydrocarbons or essentially pure hydrocarbons (e.g.,
aromatics) . Temperature of sample must be maintained essentially constant
(within 0.2F) during determination.
Statistical Characteristics:
Accuracy and Precision: Results should be repeatable within 0.2 degrees
by the same analyst, and should be reproducible within 0.5 degrees from
one laboratory to another.
Time of Measurement: 30 minutes
Calibration Requirements; See Reference (1)
Comments by Users: Results may be useful in assessing the degree of weathering
undergone by the petroleum product in water.
Data Outputs: Visual observation (scale readings) , manually recorded
Special Sampling Requirements (Collection, Storage. Handling): None stated
References:
(1) "Standard Method for Test for API Gravity of Crude Petroleum and
Petroleum Products (Hydrometer Method)," ASTM Designation 287-67,
Book of ASTM Standards, (fart 18), American Society for Testing and
Materials, Philadelphia, Pennsylvania (1968).
(2) Kawahara, Fred K., Laboratory Guide for the Identification of
Petroleum Products, Federal Water Pollution Control Administration,
Division of Water Quality Research, Cincinnati, Ohio, January 1969.
G-l
-------
No. G-2
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Crude or Semirefined Oil or Oil Residual
Medium: Water (as per primary reference).
Name of Measurement Method:
Principal Detection Techniques: Fluorescence Spectroscopy
Purpose of Measurement (Important Applications): Passive tagging, i.e. comparing
crude and residual type oils for identification of the source of the residual oil.
Summary of Method: All crude and semirefined oils fluoresce when excited at 340 nm
by ultraviolet light. When the oil is excited at its excitation maximum, there is a
maximum in the emission spectrum at 386 nm, with two slight shoulders around 405 and
440 nm. The ratio of the maximum intensity at 386 nm with the shoulder intensity at
440 nm is an identification parameter for each oil.
Limitations:
Range of Applicability: Not stated
Interferences: None stated
Pitfalls; Special Precautions: Cyclohexane solvent produces a maximum emission
spectrum at 340 nm which may cause serious distortion difficulties at high
dilutions.
Statistical Characteristics:
Accuracy: Method, when used with six other analytical methods, provided
identification of an oil spill sample source.
Precision; See report
Time of Measurement: Not stated
Calibration Requirements: Not stated
Comments by Users: Method has also been used for sediments and biological tissue.
Data Outputs: Analog Instrumental reading
Special Sampling Requirements (Collection, Storage, Handling): Immediate sampling
of an oil spill is very important because prolonged exposure to sunlight can affect
fluorescence properties of oil.
References:
(1) Thurston, Jr., A. D., and Knight, R. W., "Characterization of Crude and
Residual-Type Oils by Fluorescence Spectroscopy." Environmental Science and
Technology. 5, 64-49 (1971).
(2) AQCL Newsletter, #15, October 1972.
G-2
-------
No. G-3
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Density and Specific Gravity
Medium: Petroleum Products
Name of Measurement Method: Bingham Pycnometric Method (ASTM D1217)
Principal Detection Technique:
Purpose of Measurement (Important Applications):
For liquids of limited sample life.
Summary of Method:
The liquid sample is injected from a hypodermic syringe into the pycnometer made
of borosilicate glass according to specifications given in Reference (1). The sample
and the instrument are brought to constant temperature and weighed. The density or
specific gravity of the sample is then calculated from this weight and the weight
of water required to fill the pycnometer at the same temperature (as determined
previously). A correction for air bouyancy is made.
Limitations:
Range of Applicability: Not stated in ranges of density units, but generally
applicable to pure hydrocarbons or petroleum distillates that boil between
194 F and 230 F, and that can be handled as liquids at 68 F and 77 F.
Interferences: None identified
Pitfalls; Special Precautions:
Effects of humidity and of electrostatic charges on the instrument and sample
must be compensated for or neutralized.
Statistical Characteristics:
Accuracy; Results should not differ from the theoretical value by more than
0.00003.
Precision: An analyst using the same apparatus and sample should be able to
duplicate his results within + 0.00002. Results by different analysts and
apparatus should be reproducible within + 0.00003.
Time of Measurement (Max. Freq., Recovery Period, etc.);
30 to 60 minutes.
Calibration Requirements: See Reference (1)
Comments by Users: 1 ml or 2 ml pycnometers have been used. Special aluminum
containers are used for No. 6 fuel oils and asphalts.
Data Outputs: Visual scale readings, manually recorded.
Special Sampling Requirements (Collection. Storage, Handling):
References;
(1) "Standard Method and Testing for Density and Specific Gravity of Liquids by
Bingham Pycnometer", ASTM Designation D1217-54, Book of ASTM Standards,
(Part 17), American Society for Testing and Materials, Philadelphia, Pennsylvania,
(Procedure reapproved in 1968).
(2) Kawahara, F.K., Laboratory Guide for the Identification of Petroleum Products,
Federal Water Pollution Control Administration, Division of Water Quality
Research, Cincinnati, Ohio, January 1969.
G-3
-------
No. C-4
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Density and Specific Gravity
Medium: Petroleum Products
Name of Measurement Method: Lipkin pycnometric bicapillary method (ASTM D 941)
Principal Detection Technique: Gravimetric and volumetric determination
Purpose of Measurement (Important Applications): For liquids of limited
sample size.
Summary of Method: The liquid sample is introduced into a weighed Pyrex
glass instrument constructed according to specifications given in Reference (1).
This instrument, the pycnometer, permits accurate determination of the liquid
volume. The instrument with sample is weighed, then brought to constant
temperature and the volume of sample is read. From the weight and volume,
the density is determined for the specific temperature at which the volume
measurement was taken. In reporting specific gravity, both the test
temperature and reference temperature are given.
Limitations:
Ranee of Applicability: Hydrocarbon materials that are normally in the
liquid state at temperatures of 20 and 25 C, and that have vapor pressures
below 600 mm Hg and viscosities less than 15 centistokes at 20 C.
Interferences: None cited
Statistical Characteristics:
Accuracy and Precision: Duplicate results by the same analyst should
not differ by more than 0.0001, and results between laboratories should
not differ by more than 0.0002 (based on 95 percent confidence interval).
Time of Measurement: Not stated
Calibration Requirements: See Reference (1)
Data Outputs: Visual observations, recorded manually
Special Sampling Requirements (Collection, Storage. Handling) : None stated
References:
(1) "Specific Method to Test for Density and Specific Gravity of Liquids
by Lipkin Bicapillary Pycnometer". ASTM Designation D 941-55,
Book of ASTM Standards (Fart 17), American Society for Testing and
Materials, Philadelphia, Pennsylvania (Method Re-approved 1968).
(2) Kawahara, Fred K., Laboratory Guide for the Identification of
Petroleum Products, Federal Water Pollution Control Administration,
Division of Water Quality Research, Cincinnati, Ohio, January 1969.
(3) Kawahara, Fred K. , Journal of Chromatographic Science. Vol.10, 629, 1972).
G-4
-------
No. G-5
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Distillation Ranges
Medium: Petroleum Products
Name of Measurement Method: Distillation of Petroleum Products (ASTM D86-67)
(Basically a manual method, although an automated procedure is also indicated).
Principal Detection Technique: Thermometry
Purpose of Measurement (Important Applications):
For gasoline, naphtha, kerosene, and similar petroleum products.
Summary of Method:
A 100 ml sample is distilled with distillation equipment as specified in ASTM
Designation E 133. During the distillation, observations are systematically
made of the vapor temperature in the distillation vessel and the volumes of
condensate. Observations are converted by means of graphical or arithmetic
procedures to a format that interrelates: (1) prescribed percent evaporated,
(2) corresponding percent recovered, and (3) corresponding temperature.
Limitations:
Range of Applicability: Overall range of boiling points not explicitly
stated, but inferred to be from about 50 F to 770 F.
Interferences: Water. Samples containing water must be dried prior to
test.
Pitfalls; Special Precautions:
Evaporation and contamination of the test material in surface waters will
affect the results.
Statistical Characteristics:
Accuracy and Precision; Repeatability and reproducibility data are indicated
in nomagraphic form for values of various distillation parameters (initials
final boiling point, percent evaporated or recovered at prescribed thermometer
readings, etc.).
Time of Measurement (Max. Freq.. Recovery Period, etc.): Not stated
Calibration Requirements: Not stated
Data Outputs: Visual observations, manually recorded
Special Sampling Requirements (Collection, Storage. Handling): See Reference (1)
References:
(1) "Standard Method to Test for Distillation of Petroleum Products" ASTM
Designation D86-67, ASTM Book of Standards (Part 17, American Society
for Testing and Material, Philadelphia, Pennsylvania (1968).
(2) Kawahara, F.K., Laboratory Guide for the Identification of Petroleum Products,
Federal Water Pollution Control Administration, Division of Water Quality
Research, Cincinnati, Ohio, January 1969.
(3) Worman, J.C. and Green, L.E. Anal. Chem. 37. 1620 (1965).
G-5
-------
No. G-6
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Distillation Ranges
Medium: Petroleum Products
Name of Measurement Method: Distillation of Industrial Aromatic Hydrocarbons
and Related Materials (ASTM D 850-70)
Principal Detection Technique: Thermometry
Purpose of Measurement (Important Applications): For aromatics hydrocarbons
and related material.
Summary of Method: A 100-ml sample of the material to be tested is distilled
with an apparatus configured as described in Reference (1). Temperatures of the
vapor in the distillation flask are systematically recorded when pre-selected
volumes of distillate are collected in the graduated receiving flask.
Limitations:
Range of Applicability: Applicable to aromatic hydrocarbons that boil
in the range 40 to 350 C.
Interferences: Water in sample
Pitfalls; Special Precautions; Evaporation and contamination in surface
waters will affect the results
Statistical Characteristics:
Accuracy: Not stated
Precision: Not stated
Time of Measurement: Not stated
Calibration Requirements: See Reference (1)
Comments by Users: When uncontaminated and unweathered, boiling points of fuel
oils are determined with excellent accuracy via the simulated gas chromatographic
method of Uorman and Green.
Data Outputs: Visual observations, manually recorded
Special Sampling Requirements (Collection. Storage, Handling) : No unusual
requirements.
References:
(1) "Standard Method of Test for Distillation of Industrial Aromatic
Hydrocarbons and Related Materials," ASTM Designation D 850-70 Book
of ASTM Standards (Part 17), American Society for Testing and
Materials, Philadelphia, Pennsylvania (1970).
(2) Kawahara, Fred K., Laboratory Guide for the Identification of
Petroleum Products, Federal Water Pollution Control Administration,
Division of Water Quality Research, Cincinnati, Ohio, January, 1969.
(3) Worman, J.C. and Green, L.E. Anal. Chem. 37, 1620 (1965).
G-6
-------
No. G-7
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Distillation Ranges (gasoline)
Medium: Petroleum Products
Name of Measurement Method: Distillation of Natural Gasoline (ASTM D216-54)
Principal Detection Technique: Thermometry
Purpose of Measurement (Important Applications):
To determine the distillation characteristics of natural gasolines.
Summary of Method: A 100 ml sample is distilled by use of an apparatus
specified in ASTM Designation E133 without fractionation at atmospheric
pressure. Readings are taken of the vapor temperatures corresponding to the
specified amounts of distillate.
Limitations:
Range of Applicability: Not specifically stated.
Interferences: None Identified
Pitfalls; Special Precautions: Evaporation and contamination in surface
waters will affect the results.
Statistical Characteristics:
Accuracy and Precision: Results of duplicate determinations of end-point
temperatures should differ by no more than 6 F. Corresponding differences
in volume of distillate should not exceed 2 ml.
Time of Measurement (Max. Freq., Recovery Period, etc.): Not stated
Calibration Requirements: See Reference (1)
Data Outputs: Visual observations, manually recorded.
Special Sampling Requirements (Collection, Storage, Handling):
See Reference (1)
References:
(1) "Standard Method to Test For Distillation of Petroleum Products" ASTM
Desisnation D216-54. ASTM Book of Standards (Part 17), American Society
for Testing and Materials, Philadelphia, Pennsylvania (1968).
(2) Kawahara, F.K., Laboratory Guide for the Identification of Petroleum
Products, Federal Water Pollution Control Administration, Division of
Water Quality Research, Cincinnati, Ohio, January 1969.
G-7
-------
No. G-8
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Hydrocarbons
Medium: Petroleum Products
Name of Measurement Method: Gas chromatography
Principal Detection Technique: Gas chromatography
Purpose of Measurement (Important Applications); For identifying classified,
volatile petroleum products such as napthas, gasoline, jet fuel and kerosene.
Summary of Method: The hydrocarbons are separated from the crude oil with a
packed prefractionator column, collected in a liquid nitrogen trap, and then
released into either of two capillary columns through a stream splitter. The
individual components are detected by hydrogen-flame ionization as they emerge
from the column. Components through C_. and the ten lowest boiling C0 sire well
/ o
resolved in four hours on a 500-foot capillary column with 1-octadecene.
Limitations:
Range of Applicability: Gas oils, paraffins, white oils, and motor oils can
be identified if they are volatile under the conditions of analysis. The
identification of heavier products, such as residual oils and asphalt, is
limited.
Interferences: Not Given
Pitfalls; Special Precautions: Time and temperature of the environment, as
well as the fuel volatility, must be considered in matching the unknown with
the reference sample. An increase of only 3°C on the octadene column causes
at least one pair of compounds to elute together.
Statistical Characteristics:
Accuracy; Accuracy was estimated by analyzing synthetic blends made to simulate
crude oil and by analyzing crude oils previously examined with packed columns.
Average deviation from mean values are 3% relative.
Precision: Uncertainties in the results generally are less than 6% relative.
Time of Measurement: Not Given
Calibration Requirements: Reference sample
Comments by Users: A temperature of 30 C on the octadene column gives optimum
results. It may be desirable to consider other methods of analysis. A wide
variety of techniques is included in the reference list.
Data Outputs: Not given
Special Sampling Requirements (Collection. Storage, Handling): Collect sample
with a widemouth glass filtering funnel with stopcock, a paint-free dustpan with
stopcock, or a large household mop with wringer attachment. Preserve by the removal
of air and exclusion of light from the sample.
References:
(1) Kawahara, F.D., Laboratory Guide for the Identification of Petroleum Products,
U.S. Department of the Interior, January, 1969.
(2) Martin, R.L., and Winters, J.C., Anal. Chem.. 31, 1954 (1959).
(3) Martin, R.L. and Winters, J.C., Ibid, «.. 1930 (1963).
(4) Adlaid, E.R., Creaser, L.F., and Mathews, Ph.D. Anal. Chem. 44. 64, 1972.
(5) Done, J.N. and Reid, H.K., Separ. Sci. 5, 825, 1970.
(6) Kahn, L. McKenna, G.F., and Casper, L. Preprints, Am. Chem. Soc. meet'g, Houston
February 22, 1970
(7) Kawahara, F.K., Journal of Chromatographic Science Vol. 10. 629 (1972).
(8) Levy, E.M. Hater Res. 6. 57, 1972.
(9) Thruston, A.D. and Knight, R.W. Environ. Sci. Technol. 5. 64 (1971)
(10) Zltko, V. and Carson, W.V. Tech. Rept. No. 317, Fisheries Res. Bd. of Canada, 1970.
(11) Krieder, R.E.. 1971 Conference on Prevention and Control of Oil Spills, June 15-17,
1971 Washington, D.C. pages 119-124.
G-8
-------
No. G-9
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Identification of Heavy Crude and Processed Oils
Medium: Hater, Sediments, and Tissue
Name of Measurement Method: Baird Atomic Corporation Method
Principal Detection Techniques: Fluorescence and phosphorescence; spectrophotometry
at 77°K.
Purpose of Measurement (Important Applications): Passive tagging of oils
Summary of Method: The oils are dissolved in methylcyclohexane and cooled to 77°K.
The emissions spectra at 290 mu and 340 mp are compared to the spectra of known oil
samples.
Limitations:
Range of Applicability; Heavy crude and processed oils.
Interferences: None cited
Pitfalls; Special Precautions; Technique has not been established for
weathered oils.
Statistical Characteristics:
Accuracy and Precision: Not stated
Time of Measurement; Not stated
Calibration Requirements; Not stated
Data Outputs: Analog instrumental reading, graphically recorded
Special Sampling Requirements (Collection, Storage. Handling): Not stated
References: "Development of a Low Temperature Molecular Method for Oils" by
Baird-Atomic Corporation, EPA Program // 16020 GBW, Contract 68-01-0146.
G-9
-------
No. G-10
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Identification of Heavier Liquid Petroleum Products
Medium; Petroleum Products
Name of Measurement Method: Infrared spectrum
Principal Detection Technique: Infrared spectrum
Purpose of Measurement (Important Application): Identification of heavier residual fuel
oils and asphalts.
Summary of Method: Liquids may be examined in solution or neat. Liquids (neat) are
tested between plates. Mobile liquids may also be handled in cells. When solutions
are used, the solvent and sample should be dry and transparent in the range of
measurement. Carbon tetrachloride, carbon disulfide, and chloroform are the solvents
frequently used. For examining trace amounts, microcavity cells are used with a beam
condenser.
Limitations:
Range of Applicability: Liquids
Interferences: Water, sodium sulfate, halogenated compounds. When carbon tetra-
chloride and chloroform are used as solvents, compensating cells must be used.
Pitfalls; Special Precautions: If the sample has been unduly exposed to environ-
mental factors, such as air, sunlight, or temperature, peroxidative changes are
considered. Volatile petroleum products, such as naphthas and gasoline, must have
on-the-spot collection after the spill for useful information to be obtained. The
sample should be free of moisture and solvents which may interfere with the spectrum.
Statistical Characteristics:
Accuracy: By use of discriminant function analysis 98% of 147 replicates may be
classified correctly with a probability of 0.70.
Precision: Not Given
Time of Measurement: Prepared samples may be analyzed in 30 minutes.
Calibration Requirements: The infrared spectrometer must be calibrated so that the
absorption bands of the instrument's spectrum coincide with those established for a
standard polystyrene film.
Comments by Users; A reasonable prediction as to product type and identification can
be made by comparing five or six ratios of infrared absorbances.
Data Outputs: Absorbances are determined by the base-line technique, i.e., length of
vertical line which intersects the line tangential to the two proximate inflections.
Special Sampling Requirements (Collection. Storage. Handling): Collect sample with a
widemouth glass filtering funnel with stopcock, a paint-free dustpan with stopcock, or
a large household mop with wringer attachment. Preserve by the removal of air and
exclusion of light from the sample.
References:
(1) Kawahara, Fred K., Laboratory Guide for the Identification of Petroleum Products,
Federal Water Pollution Control Administration, Division of Water Quality Research,
Cincinnati, Ohio, January, 1969.
(2) Kawahara, Fred K. and Ballinger, D.G. Ind. and Eng. Chem. Res, and Develop.
Vol. 9, No. 4, page 553 (1970).
(3) Kawahara, Fred K. Journal of Chromatographic Science Vol. 10. 629 (1972).
G-10
-------
No. G-U
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Identification of Heavier Solid Petroleum Products
Medium: Petroleum Products
Name of Measurement Method: Infrared spectrum
Principal Detection Technique: Infrared spectrum
Purpose of Measurement (Important Applications) : Identification of heavier solid
petroleum products
Summary of Method: Solids are examined as a mull prepared by grinding the solid
with a drop of Nujol. The mull is placed between two plates as a film. Solids
may also be examined as discs made from the material mixed by vibration with
dried potassium bromide. In a die under pressure, the discs are pressed. The
infrared spectrum is then measured at several frequencies and matched with a
known reference standard. Neat solution may be tested between salt plates.
Limitations:
Range of Applicability: Solids
Interferences: Water and sodiun sulfate, halogonated compounds. When
chloroform is used as solvent, compensating cells must be used.
Pitfalls; Special Precautions: If the sample has been unduly exposed ro
environmental factors, such as air, sunlight, or temperature, peroxidative
changes are considered. Volatile petroleum products such as naphthas and gas-
oline must have on-the-spot collection after the spill for useful information
to be obtained.
Statistical Characteristics:
Accuracy: By use of discriminant function analyses, 98% of these samples
(tested) may be classified with a probability of 0.70.
Time of Measurement: Not stated
Calibration Requirements: The infrared spectrometer must be calibrated so that the
absorption bands of the instrument's spectrum coincide with those established for a
known or reference sample.
Comments by Users: A reasonable prediction as to product type and identification
can be made by comparing five or six ratios of infrared absorbances.
Data Outputs: Absorbances are determined by the base-line technique, i.e., the
length of the vertical line, which intersects the line tangential to the two
proximate inflections, is measured.
Special Sampling Requirements (Collaction, Storage. Handling): Collect sample with
a clean scoop or stick; place in a jar. Remove air and exclude light.
References:
(1) Kawahara, Fred K., Laboratory Guide for the Identification of Petroleum
Products, Federal Water Pollution Control Administration, Division of Water
Quality Research, Cincinnati, Ohio, January, 1969.
(2) Kawahara, Fred K. and Ballinger, D.G. Ind. Eng. Chem. Res. Develop. Vol. 9
No. A page 553 (1970).
G-ll
-------
No. G-12
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Identification of Weathered or Unweathered Oils.
Medium; Water, sediments, and tissue
Name of Measurement Method: Woods Hole Oceanographic Institute Method
Principal Detection Techniques: Gas chromatography (flame ionization)
Purpose of Measurement (Important Applications): Passive tagging of oils
Summary of Method: Oils are dissolved in carbon disulfide and injected into the GC.
The column is 50 feet x 0.02 inches (open tubular support coated—SCOT) column packed
with nonpolar liquid silicone OV-101, rated at 25,000 effective plates. Oil chroma-
tograms are compared visually, and certain features are abstracted, tabulated and
compared to the chromatograms generated by candidate unweathered oil samples.
Limitations:
Range of Applicability: Not stated
Interferences: Samples which have undergone unusual bacterial alteration, contain
high levels of indigenous hydrocarbons; mixtures of oils and samples having under-
gone unusually prolonged weathering require special treatment.
Pitfalls; Special Precautions: Tabulated indices of oils that exhibit considerable
weathering should not be compared directly with the indices of unweathered oils.
Statistical Characteristics:
Accuracy: 16 out of 17 unweathered oils used for this test accompanied
35 simulated oil spill samples. Correct "definite correlation" was achieved
in 74 percent of the cases, and only one "probable correlation" was incorrect.
Precision: Tabulated indices of individual oils remain quite stable from
column to column.
Time of Measurement: Not stated
Calibration Requirements: Method requires frequent evaluation of system performance
by injecting a standard oil that yields a repeatable known chromatogram.
Data Outputs: Analog instrument reading, graphically recorded
Special Sampling Requirements (Collection, Storage. Handling): Sample should be
refrigerated if held for more than a few days. Glass or metal containers are
required for sampling.
References: Zaifirion, 0., filumer, M. and Myers, J., "Correlation of Oils and Oil
Products by Gas Chromatography," Woods Hole Oceanographic Institution Report No. 62-55
(July 1972).
G-12
-------
No. G-13
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Melting Point
Medium; Petroleum Products
Name of Measurement Method: Drop melting point of petroleum wax (ASTM D 127-49)
Principal Detection Technique: Thermometry
Purpose of Measurement (Important Applications): To determine the drop melting
point of petrolatum and other highly viscuous waxes
Summary of Method: A sample of the material to be tested is melted. The bulb
of a chilled thermometer is dipped into the liquid sample and quickly withdrawn.
The wax that clings to the thermometer bulb begins to congeal while in the air
at room temperature. Then the wax-coated thermometer is submerged in water
at 60 F. A second sample is prepared in the same manner.
Both thermometers with wax-coated bulbs are held by corks in test
tubes so that the bulbs are a specified distance above the bottom of the test
tubes. The test tubes are placed in a water bath, and the temperature slowly
raised. The temperature at which the first drop of wax falls from each
thermometer is recorded. The average of the two readings is reported as the
drop melting point.
Limitations:
Range of Applicability: Specific temperature ranges are not given
Interferences: None identified
Pitfalls; Special Precautions: None stated
Statistical Characteristics:
Accuracy and Precision: Duplicate tests by the same analyst should
yield results within 1.4 F. Test results by different laboratories
should fall within 2.2F.
Time of Measurement: Not stated, but assumed to be relatively rapid
(several tests per hour).
Calibration Requirements: See Reference 1
Comments by Users; Petroleum waxes may be identified by FID gas chromatography
(Knight).
Data Outputs: Visual observations, manually recorded.
Special Sampling Requirements (Collection, Storage, Handling): Not specified.
References: (1) "Standard Method of Test for Drop Melting Point of Petroleum
Wax, Including Petrolatum", ASTM Designation D 127-63, 1964
Book of ASTM Methods (Part 18), American Society for Testing
and Materials.Philadelphia, Pennsylvania.
(2) Kawahara, Fred K., Laboratory Guide for the Identification of
Petroleum Products, Federal Water Pollution Control Administration,
Division of Water Quality Research, Cincinnati, Ohio, January 1969.
(3) Knight, H.S. Anal. Chem. 39, 1452 (1967).
G-13
-------
No. G-U
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Melting Point of Paraffin Wax
Medium; Petroleum products
Name of Measurement Method: Melting point of petroleum wax (cooling curve)
(ASTM D 87-66)
Principal Detection Technique: Thermometry
Purpose of Measurement (Important Applications): If the petroleum product
is found to be insoluble or partly soluble in chloroform, a melting
point is determined.
Summary of Method: A sample of the material is heated at least 15 F above its
melting point, and placed in a test tube fitted with a thermometer with bulb
in the molten sample. Test tube is placed in an air bath surrounded by a water
bath maintained at 60 to 80 F. Thermometer is read and recorded every IS seconds
until 5 consecutive readings agree within 0.2F (or at least 3 minutes after
the temperature begins to fall following a series of readings that agree within
0.2F). The average of the five consecutive readings (corrected for thermometer
scale error where necessary) is reported as the melting point (cooling curve).
Limitations;
Range of Applicability: Applicable to petroleum wax paraffins but not to
waxes of the petrolatum group, the petroleum ceresin group, or blends of
these groups with paraffins.
Sensitivity; 0.1 F
Interferences: None identified other than those mentioned under Range
of Applicability
Pitfalls; Special Precautions: None cited
Statistical Characteristics;
Accuracy and Precision: For samples within the melting point range of
120 to 145 F,duplicate determinations by the same analyst should be within
0.2 F. Results for duplicate samples by different laboratories should be
within 1.0 F.
Time of Measurement: Not stated, but fairly rapid (several per hour).
Calibration Requirements: See Reference (1)
Comments by Users: Paraffinic waxes may be identified by FID gas chromatography
(Knight) and by mass spectrometry (Stevenson and Polgar)
Data Outputs; Visual observations, manually recorded
Special Sampling Requirements (Collection, Storage, Handling): None stated
References;
(1) "Standard Method of Test for Melting Point of Petroleum Wax (Cooling Curve)"
ASTM Designation D 87-66, Book of ASTM Standards (Part 18), American
Society for Testing and Materials, Philadelphia, Pennsylvania (1967).
(2) Kawahara, Fred K., Laboratory Guide for the Identification of
Petroleum Products, Federal Water Pollution Control Administration,
Division of Water Quality Research, Cincinnati, Ohio, January 1969.
(3) Knight, H.S. Anal. Chem. 39. 1542 (1967).
(4) Stevenson, D.P. and Polgar, A.G. NASA Contractor Report CR 519 (July 1966).
(5) Kawahara, F.K. Journal of Chromatographic Science Vol. 10. 629 (1972).
G-14
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No. G-15
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Mercaptans*
Medium: Crude oil
Name of Measurement Method: Doctor Test
Principal Detection Technique: Precipitation
Purpose of Measurement (Important Applications): Detect the presence of mercaptans
in crude oils.
Summary of Method: Dissolve sodium hydroxide in distilled water and add lead
oxide. Shake the mixture, permit to stand one day, and then filter. The sample is
then shaken with the freshly filtered sodium plumbite solution. Sulfur is added and
the solution shaken again. If the mixture is discolored, the test is positive. If
the sulfur or the mixture remains unchanged or yellow, the test mixture is mercaptan-
free.
Limitations:
Range of Applicability: Not Given
Interferences: Not Given
Pitfalls, Special Precautions: Not Given
Statistical Characteristics:
Accuracy: Not Given
Precision: Not Given
Time of Measurement: Mixture has to stand one day.
Calibration Requirements: Not Given
Comments by Users: Gas chromatographic techniques for measuring mercaptans are
included in the reference list.
Data Outputs: Visual
Special Sampling Requirements (Collection. Storage. Handling): Collect sample
with a widemouth glass filtering funnel with stopcock, a paint-free dustpan with
stopcock, or a large household mop with wringer attachment. Preserve by the
removal of air and exclusion of light from the sample.
References:
(1) Kawahara, F.K. , Laboratory Guide for the Identification of Petroleum Products,
Federal Water Pollution Control Administration, Division of Water Quality
Research, Cincinnati, Ohio, January 1969.
(2) Kawahara, F.K. Anal. Chem. 40. 1009 (1968)
(3) Kawahara, F.K. Journal of Chromatographic Science Vol. 10. 629 (1972).
(4) Baker, R.A. J. Amer. Water Works Assoc. 58. 751 (1966)
(5) Brand, V.T. and Keyworth, D.A. Anal. Chem. 37. 1424 (1965).
*Also see Summary No. G-22
G-15
-------
No. G-16
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Molecular Weight
Medium! Petroleum Products
Name of Measurement Method: Rast Method
Principal Detection Technique: Weight and Temperature
Purpose of Measurement (Important Applications) : Of value for determining low and
high boiling petroleum products.
Summary of Method: The dried residue of the sample is placed into a weighed test
tube and weighed, d-camphor is added and the residue melted in a heated oil bath.
The tube is swirled to dissolve the contents, then cooled. The resulting solid
is powdered. The melting point of several samples from the mixture is determined
and averaged. The melting point of the original camphor is taken. The molecular
weight is then calculated (see Reference (1) for equation.)
Limitations:
Range of Applicability: Not given
Interferences; Not given
Pitfalls; Special Precautions; Not given
Statistical Characteristics:
Accuracy: Melting temperature is averaged for several samples from a
mixture
Precision: Not given
Time of Measurement: Not given
Calibration Requirements: Thermometer should read to 0.2 F.
Comments by Users: This method may be replaced by the ebulloscopic or mass
spectroscopic method for the volatile materials.
Data Outputs: Weight and temperature
Special Sampling Requirements (Collection. Storage, Handling): Collect sample
with a widemouth glass filtering funnel with stopcock, a paint-free dustpan
with stopcock, or a large household mop with wringer attachment. Preserve
by the removal of air and exclusion of light from the sample.
References: (1) Kawahara, Fred K., Laboratory Guide for the Identification
of Petroleum Products, Federal Water Pollution Control
Administration, Division of Water Quality Research,
Cincinnati, Ohio, January 1969.
(2) McElvain, S. M., "The Characterization of Organic Compounds",
The MacMillan Company, New York, 1945, pp. 36-37.
G-16
-------
No. G-17
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Petroleum Oils (Definition of oil is based on this procedure).
Medium: Water
Name of Measurement: Method: Quantitative Analysis of Oil in Water Dispersion
Principal Detection Techniques; Infrared Spectrophotometry
Purpose of Measurement (Important Applications): Identification of the particular
oil and its quantitative determinations in the water column are essential to
properly monitor and assess potential biological damage resulting from oil spill
incidents.
Summary of Method; Salt and acid added to the sample which is then extracted with
carbon tetrachloride or Freon 113, using a separatory funnel. The extract is measured
by infrared Spectrophotometry.
Limitations:
Sensitivity: Minimum detection limit <0.05 mg/1
Interferences; (Freon or CC1-) - Any solvent extractable organics.
Pitfalls; Special Precautions: Carbon tetrachloride has a TLV of 10 mg/1
Statistical Characteristics:
Accuracy and Precision: No data available
Time of Measurement;
Calibration Requirements; Freon is not usable for preparing IR standards of heavy
oils(2>.
Comments by Users: Carbon tetrachloride is more efficient than Freon 113 for
extracting high concentrations of viscous oils (1000 centistokes at JOO°F) from
water dispersion.
Data Outputs: Analog instrumental reading
Special Sampling Requirements (Collection, Storage, Handling): Sample is collected
in a glass stoppered bottle and acidified at the time of collection.
References;
(1) Method submitted for inclusion in subsequent issue of Laboratory
Guide for Identification of Petroleum Products, (current issue
dated January 1969) Division of Water Quality Research,
Cincinnati, Ohio.
(2) Kawahara, Fred K., Laboratory Guide for the Identification of
Petroleum Products, Federal Water Pollution Control Administration,
Division of Water Quality Research, Cincinnati, Ohio, January 1969.
G-17
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No. G-18
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Saturates, Olefins, and Aroraatics
Medium: Petroleum Produces
Name of Measurement Method: FIA Method D 1319-61T
Principal Detection Technique: Adsorption Chromatography
Purpose of Measurement (Important Applications): The determination of the saturates,
olefins, and aromatics (including aromatic olefins) in petroleum fractions that distill
below 600°F.
Summary of Method: The sample containing traces of fluorescent dye is introduced
into a small glass adsorption column. Silica gel is used to adsorb the sample.
Alcohol is then used to desorb and develop the sample. The hydrocarbons are separated
by their adsorption affinities. The fluorescent dyes mark the boundaries. The volume
percentage is determined by measuring the length of each zone of the column.
Limitations:
Range of Applicability: Not Given
Interferences; Not Given
Pitfalls; Special Precautions; Not Given
Statistical Characteristics:
Accuracy: Not Given
Precision: Reproducibilicy within about 3 percent for experienced operators
Time of Measurement: Not Given
o
Calibration Requirements: Ultraviolet light source with radiation at 3650 A
Comments by Users: This is an older method. Other methods of analyses, such as
chromatographic mass spectrometric, and nuclear magnetic resonance, are included
in the reference list.
Data Outputs: Measured lengths of zones in column
Special Sampling Requirements (Collection, Storage. Handling): Collect sample
with a widemouth glass filtering funnel with stopcock, a paint-free dustpan with
stopcock, or a large household mop with wringer attachment. Preserve by the
removal of air and exclusion of light from the sample.
References:
(1) Kawahara, F.K., Laboratory Guide for the Identification of Petroleum Products,
Federal Water Pollution Control Administration, Division of Water Quality
Research, Cincinnati, Ohio, January 1969.
(2) "ASTM Standards on Petroleum Products and Lubricants" prepared by ASTM
Committee 0-2 on Petroleum Products and Lubricants, November 1957.
(3) Mair, B.J. and Mayer, T.J. Anal. Chen. 36. 351 (1964).
(4) Clemans, C.A., Leach, P.W., and Altshuller, Anal. Chem. 35. 1546 (1963).
(5) Dawson, H.J. Anal. Chem. 36. 1852 (1964).
(6) Marquat, J.R., Dellow, G.B., and Freitas, E.R. Anal. Chem. 40. 1633 (1968).
(7) Chamberlain, M.F. Anal. Chem. 31. 56 (1959).
(8) Jungnickel, J.L. and Forbes, J.W. Anal. Chem. 35. 938 (1963).
(9) Kawahara, F.K. Journal of Chromatographic Science Vol. 10. 629 (1972)
(normal paraffins).
G-18
-------
No. G-19
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Solubility
Medium: Petroleum Products
Name of Measurement Method; Not Given
Principal Detection Technique: Solubility
Purpose of Measurement (Important Applications): To predict product type by
observing behavior in organic solvents (a preliminary test).
Summary of Method: The sample is separated and concentrated. From the thoroughly
dried concentrated residue, free of water and extracting solvent, take a 0.2 gm
portion and place in a 20 ml vial. Add 7 ml of hexane and stir. Observe solubility.
Repeat the test in both diethyl ether and in chloroform. Compare with Solubility
Chart (as given in Reference*cited below) for identification of residue.
Limitations:
Range of Applicability: Not Given
Interferences: Not Given
Pitfalls; Special Precautions: Applicable to singular products.
Statistical Characteristics:
Accuracy: Not Given
Precision: Not Given
Time of Measurement: 30 minutes
Calibration Requirements: Not Given
Comments by Users: Especially useful for identifying the heavier petroleum products,
asphalts, greases, and residual fuel oils.
Data Outputs: Visual
Special Sampling Requirements (Collection. Storage. Handling): Collect sample with
a widemouth glass filtering funnel with stopcock, a paint-free dustpan with stopcock,
or a large household mop with wringer attachment. Preserve by the removal of air and
exclusion of light from the sample.
*
References: QKawahara. Fred K., Laboratory Guide for the Identification
of Petroleum Products, Federal Water Pollution Control
Administration, Division of Water Quality Research,
Cincinnati, Ohio, January 1969.
2)Kawahara, F.K. Journal of Chromatographic Science Vol. 10. 629.
(1972).
G-19
-------
No. G-20
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Specific Gravity
Medium: Petroleum Products
Name of Measurement Method: Specific Gravity of Road Oils, Road Tars, etc.,
ASTMD70-52 (Lycrometer).
Principal Detection Technique:
Purpose of Measurement (Important Applications): Is intended for the determination
of the specific gravity of road oils, road tars, asphalt cements and soft tar pitches.
Summary of Method: To determine the specific gravity of road oils or road tars that
flow readily, the material is brought to a temperature of 25 C and poured into a
pycnometer until it is full. The stopper is inserted, with the pycnometer and its
contents at 25 C, all excess material is forced through the opening and carefully
wiped off. The pycnometer with contents is weighed and the specific gravity is
subsequently calculated. If the petroleum products like asphalt cement and pitches
are too viscous, a small quantity of the material is brought to a fluid condition and
poured into a dry, slightly worked pycnometer to half fill it. The pycnometer is
cooled to room temperature, stoppered, and weighed. It is then filled with freshly
boiled distilled water and firmly stoppered, and completely immersed in a beaker of
freshly boiled distilled water maintained at 25 C. Finally the pycnometer is taken
from water, wiped dry, and weighed again. The specific gravity is then calculated at
77/77F(25/25 C).
Limitations:
Range of Applicability: Not stated
Interferences: Not stated
Pitfalls; Special Precautions: Only freshly boiled distilled water should be
used. Care should be taken to prevent expansion and overflow of contents
from the heat of the hand. The presence of air bubbles should be eliminated in
filling pycnometer.
Statistical Characteristics:
Accuracy: None stated
Reproducibility: Should be within a range of 0.005.
Time of Measurement (Max. Freq., Recovery Period, etc.): Not stated
Calibration Requirements: See Reference (1) for calibrations of pycnometer.
Data Outputs: Visual Scale readings, manually recorded.
Special Sampling Requirements (Collection. Storage. Handling): None stated
References:
(1) "Standard Method of Test for Specific Gravity of Road Oils, Road Tars,
Asphalt Cement, and Soft Tar Pitches" ASTM Designation D70-52, (Reapproved
1968), American Society for Testing Materials, Philadelphia, Pennsylvania,
(1972).
(2) Kawahara, F.K., Laboratory Guide for the Identification of Petroleum
Products, Federal Water Pollution Control Administration, Division of Water
Quality Research, Cincinnati, Ohio, January 1969.
G-20
-------
No. G-21
SUMMARY OF ANALYTICAL METHOD
Parameter(s) measured; Specific Gravity of Solids
Medium: Petroleum Products
Name of Measurement Method: Specific Gravity of Solid Pitch and Asphalt
(Displacement Method) ASTM D71
Principal Detection Technique: Gravimetric
Purpose of Measurement (Important Applications): For solid petroleum products.
Summary of Method:
Specific gravity is determined by water displacement. Two fragments of the sample
are selected. Each is suspended from a thin, tare-weighed wire, and weighed first
in air and again while suspended in water at 25.0 C. The specific gravity at 25/25 C
is then calculated.
Limitations:
Range of Applicability: Range of specific gravities not stated, but metnod is
applicable to soft pitches and asphalts with softening point above 70 C.
Interferences: Not identified
Pitfalls; Special Precautions;
Natural homogeneous fragments free of cracks should be used where possible.
Use of cast samples is not recommended because of the difficulty of preventing
capture of air bubbles in the sample. (ASTM methods D61 or D2319 describe cast-
ing procedures to be used when necessary.)
Statistical Characteristics:
Accuracy and Precision: Duplicate results by the same operator should not differ
by more than 0.005. Arithmetic averages for duplicate determinations, as per-
formed by different laboratories, should not differ by more than 0.007.
Time of Measurement (Max. Freq.. Recovery Period, etc.): Not stated
Calibration Requirements: No unusual requirements.
Data Outputs: Visual scale readings, manually recorded.
Special Sampling requirements (Collection. Storage, Handling): Sample fragments are
selected from well mixed bulk samples. (See ASTM Method D140) .
References:
(1) "Standard Method of Test for Specific Gravity of Solid Pitch and Asphalt
(Displacement Method)" ASTM Designation D71-72a, ASTM Book of Standards (Part
) American Society for Testing and Materials, Philadelphia, Pennsylvania (1972).
(2) Kawahara, F.K., Laboratory Guide for the Identification of Petroleum Products,
Federal Water Pollution Control Administration, Division of Water Quality
Research, Cincinnati, Ohio, January 1969.
G-21
-------
No. G-22
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Trace Constituents (Mercaptans and Phenols; also
Metals, Nitrogen and Sulfur).
Medium; Petroleum Products
Name of Measurement Method: Depends on constituent being analyzed.
Principal Detection Technique: Atomic Absorption, Electron Capture Gas
Chromatography, Emission Spectrometry, Titration.
Purpose of Measurement (Important Applications): To determine presence and
concentration of several materials found in trace quantities in petroleum.
Summary of Method: The methods employed depend upon which constituents are
being analyzed. In general, the following methods would be used for the types
of trace constituents listed.
Material
Metals (especially nickel,
vanadium, also iron and
copper)
Mercaptans and Phenols
Nitrogen
Sulfur
Limitations:
Statistical Characteristics:
Calibration Procedures:
Special Sampling Requirements
(Collection, Storage, Handling):
References;
(1)
Method References
Atomic Absorption (6)
Mobil Oil Method 245
Gas Chromatography (1),(2),(3),
(Electron Capture Detection) (4), (5).
Kjeldahl Procedure. Nitrogen
as ammonia is distilled into
boric acid solution, then
titrated with standard sulfuric
acid using methyl purple as an
indicator.
X-ray Spectroscopy, Bomb, (7), (8), (9),
or High Temperature Methods respectively
Details not given in primary
Reference (Ref.l). See indi-
vidual references for additional
information
Kawahara, Fred K., Laboratory Guide for the Identification of Petroleum
Products and Lubricants," prepared by ASTM Committee D-2 on Petroleum
Products and Lubricants, November 1957.
(2) Gamble, L.W. and Jones, W.H., Anal Chem 27. 1456 (1955).
(3) Kawahara, F.K., Anal Chem 40 1009 (1968).
(4) Kawahara, F.K., Journal of Chromatographic Science, Vol. 10,
629 (1972).
(5) Kawahara, F.K., Preprint, American Chemical Society Meeting at Los
Angeles; 1971. Division of Water, Air and Waste Chemistry.
(6) Kapp, J.F. and Kroner, R.C., Applied Spectroscopy, 19, No. 5, 155 (1965).
(7) ASTM Designation D2622-67 (X-ray spectrographic).
(8) ASTM Designation D129-64 (Bomb Method).
(9) ASTM Designation D1552-64 (High Temperature Method).
G-22
-------
No. G-23
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Viscosity
Medium: Petroleum Products
Name of Measurement Method: Kinematic viscosity of transparant and opaque
liquids (ASTM D 445-66)
Principal Detection Technique: Timer
Purpose of Measurement (Important Applications): To determine viscosity as
one step in the characterization of petroleum products.
Summary of Method: The time required for a given volume of the test liquid
to flow under gravity through the capillary of a calibrated viscometer is
measured under controlled and measured conditions of driving head and
temperature. The measured time is multiplied by a calibration constant
for the apparatus to yield the kinematic viscosity. (A procedure is given
for calculating the dynamic viscosity from the kinematic viscosity and
density of the test material.)
Limitations:
Range of Applicability: Not specifically stated. Differs with
characteristics of viscometer. Various apparatus identified range
from 0.4 to 300,000 centistokes.
Interferences: None identified
Pitfalls; Special Precautions: The actual viscosities mav deviate
strongly from the reference viscosities due to differences in composition and
process.
Statistical Characteristics:
Accuracy and Precision: In measuring viscosity of transparent oils between
60 and 212F, duplicate results by the same operator using the same apparatus
would be expected to fall within 0.35 percent of the mean of the two
determinations. For replicate tests by different laboratories results
should be within 0.7 percent of their mean.
Time of Measurement: Not stated, but assumed rapid (several per hour)
Calibration Requirements: No unusual requirements. See Reference (1) for
details.
Comments by Users: Consideration of the API gravity, with sulphur values,
infrared data, and boiling point range will facilitate identification of the
product. Viscosity measurements are applicable to lube oils, No. 4 oils, No.5
oils, and asphalts.
Data Outputs: Visual readings, manually recorded
Special Sampling Requirements (Collection. Storage. Handling): Temperature of the
bulk sample should be adjusted and the sample stirred or shaken to insure thorough
mixing prior to withdrawing test sample.
References:
(1) "Standard Method of Test for Kinematic Viscosity of Transparent and
Opaque Liquids (And the Calculation of Dynamic Viscosity)," ASTM
Designation D 445-72. Book of ASTM Standards, American Society for Testing
and Materials, Philadelphia, Pennsylvania.
(2) Kawahara, Fred K., Laboratory Guide for the Identification of
Petroleum Products, Federal Water Pollution Control Administration,
Division of Water Quality Research, Cincinnati, Ohio, January, 1969.
G-23
-------
No. G-24
SUHKAR-; OF ANALYTICAL METHOD
Parameter(s) Measured: Viscosity
Medium: Oil
Name of Measurement Method: Saybolt viscosity
Principal Detection Technique: Timer, Saybolt viscometer (ASTM D 88-56)
Purpose of Measurement (Important Applications): To determine the viscosity
of petroleum products as part of the characterization of such materials.
(Waxy products can be treated by a special procedure described in Reference
(D.)
Summary of Method: The time required for a given volume (60 ml) of the
test material to flow under gravity through a calibrated orifice is
measured under specified, measured conditions of head and temperature
(between 70 and 210F). The sample flows from a container of specified
design held in a water bath into a receiving flask of specified design.
The efflux time is measured by a timer to the nearest 0.1 sec. The measured
time is corrected by an orifice factor.
Limitations:
Range of Applicability: Not specificallv stated. Assumed to cover the
range from about 25 sec. to over 1000 sec.
Sensitivity; 0.1 second
Interferences; Dust, water vapor
Pitfalls, Special Precautions: None identified
Statistical Characteristics:
Accuracy and Precision: Not stated
Time of Measurement: Not stated
Calibration Requirements: Apparatus should be calibrated periodically.
See Reference (1) .
Data Outputs: Visual observations, manually recorded
Special Sampling Requirements (Collection, Storage. Handling): Not stated
References:
(1) "Standard Method of Test for Saybolt Viscosity," ASTM Designation 88-56,
1969 Book of ASTM Standards (Pert 17), American Society for Testing and
Materials, Philadelphia, Pennsylvania.
(2) Kawahara, Fred K., Laboratory Guide for the Identification of
Petroleum Products, Federal Water Pollution Control Administration,
Division of Water Quality Research, Cincinnati, Ohio, January, 1969.
G-24
-------
H. BIOLOGICAL METHODS
-------
H-l
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Algal Growth Potential
Medium: Water
Name of Measurement Method: Bottle test method
Principal Detection Techniques; Volumetric. Gravimetric, etc. (depends on
method used to indicate alga growth).
Purpose of Measurement (Important Applications): Algal assays are conducted to
determine the effects of various discharges on the growth of alga or to determine
whether or not various compounds or water samples are toxic or inhibitory to
algae.
Summary of Method: After inoclulation of test organisms the sample is
incubated at 24 + 2 C under cool white fluorescent lighting. During
incubation, algal growth is determined by cell counting, or algal biomass
or the chlorophyll analysis methods at predetermined intervals. The collected
data is used to determine the maximum standing crop and the maximum specific
growth rate.
Limitations;
Range of Applicability: Not stated
Interferences: Not stated
Pitfalls; Special Precautions: When trace nutrients are being studied
special glassware such as Vycor or polycarbonate containers should be used.
Statistical Characteristics:
Accuracy; Not stated
Precision; Excellent agreement in data using this method was
obtained by eight participating laboratories.
Time of Measurement: The analysis is continued until there is less than
5 percent per day increase in biomass.
Calibration Requirements: See individual method in Reference cited below.
Data Outputs: Visual counts
Special Sampling Requirements (Collection, Storage, Handling): Sample pretreatment
is required when determinations are being made of (1) growth-limiting soluble
nutrients or (2) amount of algal biomass that can be grown from all nutrients
in'water.
References; Biological Field and Laboratory Methods, U. S. Environ-
mental Protection Agency, National Environmental Research
Center, Analytical Quality Control Laboratory, Cincinnati,
Ohio (1972) (Preliminary Draft).
H-l
-------
H-2
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Age, firowth and Condition of Fish
Medium: Water
Name of Measurement Method: Laboratory Analysis for Sublethal or Chronic
effects of Pollution
Principal Detection Techniques: Visual observation
Purpose of Measurement (Important Applications): It is possible to detect
changes in water quality by studying the growth rate, general health, and
well beine of a fish.
Summary of Method:
1. The length-frequency method of age determination
depends on the fact that fish size varies with age.
2. Length-weight (coefficient of condition) studied by
regression analysis.
3. The age of fish is reflected in zones or bands in hard
structures such as scales, otoliths and vertebrae.
4. The general well-being of fish is determined by
disease from fungus, open sores, ulcers, fin rot,
emaciation, etc. and is manifested during examination.
Limitations:
Range of Applicability: Not stated
Interferences: Not stated
Pitfalls; Special Precautions: Not stated
Statistical Characteristics: Not stated
Accuracy: Not stated
Precision: Not stated
Time of Measurement: Not stated
Calibration Requirements: Not stated
Special Sampling Requirements (Collection, Storage, Handling): Not stated
References: Biological Field and Laboratory Methods, U. S. Environ-
mental Protection Agency, National Environmental Research
Center, Analytical Quality Control Laboratory, Cincinnati,
Ohio (1972) (Preliminary Draft).
H-2
-------
H-3
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Change in Che Taste of Fish Produced by Chemical
Pollutants.
Medium: Water
Name of Measurement Methods: Flesh tainting
Principal Detection Techniques: Taste
Purpose of Measurement (Important Applications): Sub-lethal concentra-
tion of chemicals are often responsible for imparting an unpleasant taste
to fish flesh. This procedure will successfully relate the unacceptable
flavor produced in native fish to a particular waste source.
Summary of Method: All fish are held in pollution-free water for a period
of 10 days. At least three of the fish are cleaned and frozen with dry
ice and the remaining fish are transferred to the test sites and placed
in portable cages. After exposure, all the fish are dressed, cooked,
flaked and mixed. The samples are served to lab testing panel and judged
on the basis of flavor and desirability on a point scale.
Limitations;
Range of Applicability: Not stated
Interferences; None.
Pitfalls; Special Precautions: Uniform taste quality should be
assured before exposure of test fish
Statistical Characteristics:
Accuracy; Not applicable
Precision: Not applicable
Time of Measurement (Max. Freq.. Recovery Period, etc.): Approxi-
mately 2 weeks
Calibration Requirements: None required
Comments by Users; The test panel should be trained in fish tainting
and should be given acceptable samples for comparison
Data Outputs: Personal sensing
Special Sampling Requirements (Collection. Storage. Handling): Not stated
References: Biological Field and Laboratory Methods, U. S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio (1972)
(Preliminary Draft).
H-3
-------
H-4
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Species Identification of Fish
Medium: Water
Name of Measurement Method; Species identification
Principal Detection Technique; Visual examination
Purpose of Measurement (Important Applications): To the public the
condition of the fishery is a very meaningful index of water quality.
Summary of Method: Individual specimens are identified by the use of national
of regional taxonomic keys and descriptions or ty comparison to a reference
collection which has been verified by appropriate specialists. Ideally,
both methods are utilized, one providing a check on the other.
Limitations:
Range of Applicability: Not stated
Interferences: Not stated
Pitfalls; Special Precautions: Inadequate descriptions, unclear keys,
cryptic species, inexperience, requires subjective judgements.
Statistical Characteristics:
Accuracy: Depends on the completeness of reference list
Precision: Not stated
Time of Measurement (Max. Freq.. Recovery Period, etc.): Not stated
Calibration Requirements: Not stated
Data Outputs: Species list
Special Sampling Requirements (Collection. Storage. Handling): Fish
should be preserved in the field in 10 percent formalin. Following
fixation, the fish are washed and permanently preserved in isopropyl
alcohol.
References: Biological Field and Laboratory Methods, U. S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft).
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H-5
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Toxicity of Pollutants to Fish (Marine and Fresh Water)
and Macroinvertebrates
Medium; Water
Name of Measurement Method: Bioassay
Principal Detection Technique:
Purpose of Measurement (Important Applications): Bioassays are conducted to
evaluate the toxicity of effluents or other materials, determine permissible
effluent discharge rates, etc. to organisms.
Summary of Method: Experimental organisms are subjected to a series of con-
centrations of a known or suspected toxicant under controlled conditions.
The time required for the toxicant to kill any given percentage of the
organisms (usually SO percent) is observed and recorded.
Limitations:
Range of Applicability; Static assays are suitable to detect and evaluate
toxicity that is not associated with excessive oxygen demand and that is
due to relatively stable substances. Continuous-flow bioassays are used
mainly to test industrial effluents and chemicals that have high
biochemical oxygen demands, are unstable or volatile, or are removed
appreciably from solution by precipitation in the test fish.
Interferences: Not stated
Pitfalls; Special Precautions: For the determination of permissible effluent
discharge rates, sensitive species important in the receiving water should be
the species.
Statistical Characteristics:
Accuracy: Not stated
Precision: Not stated
Time of Measurement; The time for acute mortality test is usually
4-7 days. The time for chronic mortality test should be related
to the life stage or life cycle of the organisms.
Calibration Requirements: Not applicable
Data Outputs: Count
Special Sampling Requirements (Collection. Storage, Handling): Environmental
conditions should be controlled during the test.
References:
Biological Field and Laboratory Methods, U. S. Environmental Protection
Agency, National Environmental Research Center, Analytical Quality Control
Laboratory, Cincinnati, Ohio (1972) (Preliminary Draft).
H-5
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H-6
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Benthic Macroinvertebrate Bioraass
Medium: Water
Name of Measurement Method: Ash Free Weight
Principal Detection Technique: Gravimetric
Purpose of Measurement (Important Applications): Biomass is necessary in
estimates of secondary productivity.
Summary of Method: The sample is soaked in distilled water, centrifuged,
and weighed to the nearest 0.1 mg (wet weight). The sample is then oven
dried, vacuum dried or freezed dried, weighed and ashed.
Limitations;
Range of Applicability: Macroinvertebrate
Interferences; Hard parts (shells, tec.) can introduce errors.
Pitfalls; Special Precautions: Use of wet weight is not recommended
unless it can be equated to dry weight by a determination of
suitable conversion factor.
Freeze drying has a major disadvantage in that it requires a
minimum of four hours drying time for drying to a constant
weight.
Statistical Characteristics:
Accuracy: Not stated
Precision: Not stated
Time of Measurement: Oven drying - 4 hours; or vacuum drying - 15-30
minutes; or freeze drying - 4 hours; ashing - 1 hour.
Calibration Requirements: Not stated
Comments by Users: Freeze drying method has advantages over oven drying
method because the organisms remain intact for further identification and
cooling the material in desiccators after drying is not necessary.
Data Outputs: Visual scale reading
Special Sampling Requirements (Collection. Storage, Handling): Not stated
References: Biological Field and Laboratory Methods, U. S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft).
H-6
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H-7
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Benthic Macroinvertebrate Species Identification
Medium: Water
Name of Measurement Method; Taxonomic identification of Macroinverte-
brate.
Principal Detection Techniques: Visual observation
Purpose of Measurement (Important Applications): Benthic macroinvertebrates
In an aquatic ecosystem are very sensitive to stress; therefore, specie identi-
fication serves as a useful tool for detecting environmental perturbations
resulting from introduced contaminants.
Summary of Method: The taxonomic level to which animals are identified
depends on the needs, experience, and available resources. Identification
of organisms is made under a steroscopic microscope and the generic and
specific identifications are determined following an examination of a
slide-mounted specimen with a compound microscope.
Limitations:
Range of Applicability: Macroinvertebrates
Interferences: Opaque tissue should be cleared before analysis.
Pitfalls; Special Precautions: Formalin should not be used for
preserving samples of macroinvertebrate.
Statistical Characteristics:
Accuracy: The accuracy of identification will depend greatly on the
available taxonomic literature.
Precision: Not stated
Time of Measurement; Not stated
Calibration Requirements; Taxonomic literature required for species ident-
ification.
Data Outputs: Visual observation
Special Sampling Requirements (Collection, Storage. Handling); Sample
should be preserved in 70 percent ethanol. The sample should be sieved
before analysis.
References:
Biological Field and Laboratory Methods, U. S. Environmental Protection
Agency, National Environmental Research Center, Analytical Quality Control
Laboratory, Cincinnati, Ohio (1972) (Preliminary Draft).
H-7
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H-8
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Substrate Particle Size.
Medium: Water
Name of Measurement Method: Particle size analysis
Principal Detection Technique: Physical Separation
Purpose of Measurement (Important Applications): In macroinvertebrate studies,
the effects of water quality changes may be inseparable from the effects of
substrate changes. The object of size analysis is to obtain numerical, sta-
tistical and possibly graphical data, which will serve to characterize a
sediment in terms of the frequency distribution of grain size diameters.
Summary of Method: A particle size analysis is conducted on at least one
sample and preferably replicate samples from each site using standard sieve:'
and classification is made by modified Wentworth method. The samples are
washed through the sieves with distilled water.
Limitations:
Range of Applicability: Less than ,004mm in diameter to areater than
256mm in diameter (Range of Wentworth Classification Method)
Interferences: Not stated
Pitfalls; Special Precautions: If these qualitative samples are to be
used for determining the effects of introduced contaminants, then one
must bear in mind that only the fauna from sites having similar
substrates in terms of organic content, soil particle size, vegetative
cover, and detritus will provide data for comparison.
Statistical Characteristics: Not stated
Accuracy: Not stated
Reproducibility: Not stated
Time of Measurement: Not stated
Calibration Requirements: None
Data Outputs: Dry and ash-free weight of material retained by each size
of sieve.
Special Sampling Requirements (Collection. Storage. Handling): Raw
sediment should be refrigerated if there is a substantial lapse of time
between collection and analysis.
References:
Biological Field and Laboratory Methods, U. S. Environmental Protection
Agency, National Environmental Research Center, Analytical Quality Control
Laboratory, Cincinnati, Ohio (1972) (Preliminary Draft).
H-8
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H-9
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Biomass of Macrophytes
Medium: Water
Name of Measurement Method: Dryweight biomass
Principal Detection Techniques: Gravimetric
Purpose of Measurement (Important Applications): Estimates of growth rates
related to pollution such as nutrient stimulation, can be accomplished by
standing crop estimates at predetermined intervals.
Summary of Method: A sample is taken from a small defined area with
conspicuous borders. The wet weight of material is obtained after the
plants have drained for a period of time. The sample is then dried for
24 hours at 105 C and reweighed. The dry weight of vegetation per unit
area is then calculated.
Limitations:
Range of Applicability: Not stated
Interferences: Not stated
Pitfalls; Special Precautions: Not stated
Statistical Characteristics:
Accuracy: Not stated
Precision: Not stated
Time of Measurement: Not stated
Calibration Requirements: Not stated
Data Outputs: Mechanical scale reading.
Special Sampling Requirements (Collection. Storage, Handling): Before beginning
a quantitative investigation it is desirable to have a statistical study design
which will assist in determining the best sampling procedure, sampling area size,
and number of samples.
References; Biological Field and Laboratory Methods, U. S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft).
H-9
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H-10
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Diatom Species Identification
Medium: Water
Name of Measurement Method: Diatom species proportional count method
Principal Detection Technique: Visual observation
Purpose of Measurement (Important Applications):
Provides information on indicator organisms and community diversity
Summary of Method: The diatoms are concentrated by centrifugation followed
by sedimentation. The diatom concentrate is placed on an 18 mm covcrglass
and dried on a hotplate at 95 C followed by the oxidization of organic
matter. The hot coverglass is inverted and placed on a drop of hyrax on a
25x75 mm microscope slide. A protective coating of clear lacquer is
sprayed on the frosted end of the slide and the excess hyrax is scraped
from around the coverglass. Two hundred fifty diatoms are identified and
counted at high magnification under oil. If the slide has very few diatoms,
the analysis is limited to the number of cells encountered in 45 minutes of
scanning.
Limitations:
Range of Applicability: Diatoms
Interferences: Silt
Pitfalls; Special Precautions: If the dried sample is obscured by soluble
solids, the sample should be washed with distilled water.
Statistical Characteristics:
Accuracy: Not stated
Precision; Not stated
Time of Measurement: One hour
Calibration Requirements: Ocular and stage micrometer
Data Outputs: Number of individuals per species
Special Sampling Requirements (Collection, Storage, Handling); Depends upon
the location and type of sample taken, see Reference. If plankton counts are
less than 1000 per ml, the diatoms should be concentrated from a larger volume
of sample (one to five liters) by allowing them to settle out.
References: Biological Field and Laboratory Methods, U.S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft)
H-10
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H-ll
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Volume of Periphyton
Medium: Water
Name of Measurement Method: Displacement Method
Principal Detection Technique: Volumetric
Purpose of Measurement (Important Applications: Estimate of the standing
stock of periphyton.
Summary of Method: A known volume of water is added to a thoroughly drained
sample. The difference between the volume of the periphyton samples
plus the added water and the volume of water alone is the volume of the
total amount of periphyton in the sample.
Limitations:
Range of Applicability: Periphyton, only when large growths of
periphyton permit removal of excess water readily.
Interferences: Not stated
Pitfalls; Special Precautions: Excess fluid should be
removed from the sample.
Statistical Characteristics:
Accuracy: Not stated
Precision: Not stated
Time of Measurement: Not stated
Calibration Requirements: Graduated cylinder should be used for volume
measurements.
Data Outputs; Volume measurement (visual)
Special Sampling Requirements (Collection, Storage, Handling): The
preferred preservative is neutral or slightly basic formalin.
References: Biological Field and Laboratory Methods, U. S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft).
H-ll
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H-12
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Phytoplankton and Periphyton Cell Councs and Identi-
fication
Medium: Water
Name of Measurement Method: Sedguick-Raf ter (S-R)
Principal Detection Technique: Visual Observation
Purpose of Measurement (Important Applications): Provide information on the standing
crop, indicator organisms and community diversity.
Summary of Method: A 24x60 mm, No. 1 coverglass is placed diagonally across the
S-R cell and a large tore pipet or eyedropper is used to transfer a one/ial ali-
quot of a well-mixed sample into the open corner of the Sedgwick-Rafter chamber.
The S-R cell is allowed to stand for at least 15 minutes to permit settling.
The analysis may then proceed in either of two ways: (1) depending on the
density of organisms, two to four "strips" the length of the cells are examined
and all forms that are totally or partially covered by the whipple-grid are
enumerated; or (2) a minimum of ten random whipple fields are examined in at
least two identically prepared S-R cells and forms that are totally or partially
covered by the whipple grid are enumerated.
Limitations;
Range of Applicability: Phytoplankters and Periphyters
Interferences: In samples where algae concentrations are extreme or
where turbidity is high the sample must be diluted or concentrated.
Pitfalls; Special Precautions; The depth of the counting chamber
precludes the use of the A5x or lOOx objectives. Collection of
phytoplankton by nets or pumps is not recommended.
Statistical Characteristics:
Accuracy; Not stated
Precision; Provides reasonably reproducible information when used
with a calibrated microscope with an eyepiece measuring device.
Time of Measurement; 1 hour
Calibration Requirements! Each combination of oculars and objectives is
calibrated against a stage micrometer.
Data Outputs; Manual count
Special Sampling Requirements (Collection. Storage, Handling): The pretreatment
of the sample depends on the concentration of organisms present. When phytoplan-
ton densities are less than 500/ml, approximately 6 liters of sample is required.
References: Biological Field and Laboratory Methods, U.S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio (1972)
(Preliminary Draft) -2
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H-13
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Cell volume of Plankton and Periphyton
Medium: Water
Name of Measurement Method: Microscopic Volumetric Method
Principal Detection Technique: Visual
Purpose of Measurement (Important Applications): Standing crop
estimate gives an indication as to water productivity.
Summary of Method: An aliquot of sample is concentrated and examined
wet at a 1000 x magnification with a microscope equipped with a calibrated
ocular micrometer. The optical measurements are made with the micrometer. The
average volume per organism is determined and multiplied by the number of
organisms per milliliter.
Limitations:
Range of Applicability: Phytoplankton, bacteria, oeriphyton
Interferences; Not stated
Pitfalls; Special Precautions: Not stated
Statistical Characteristics:
Accuracy; Not stated
Precision: Not stated
Time of Measurement: Not stated
Calibration Requirements: The exact magnification with any set oculars
must be calibrated.
Data Outputs: Visual examination
Special Sampling Requirements (Collection. Storage. Handling): The pre-
ferred preservative is neutral or slightly basic formalin.
References: Biological Field and Laboratory Methods, U. S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft).
H-13
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H-14
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Chorophyll a_ of Phytoplankton and Periphyton
Mediuni: Water
Name • of Measurement Method: In_ vitro - Fluorometric Method
Principal Detection Technique; Fluorometric
Purpose of Measurement (Important Applications): All algae contain chlornnhvl] a..
Measurement ~o£ this pigment can yield an estimate of standine crnn.
Summary of Method: The sample is centrifuged, macerated, steeped in 90% acetone,
at 4 C for 24 hours and clarified by centrifugation. The decanted extract has an
optimum sensitivity at excitation and emission wavelengths of 430 and 663 nm, res-
pectively.
Limitations:
Range of Applicability: Not stated
Interferences: Pheophytin a_
Pitfalls; Special Precautions; Evaporation of the extract should be avoided.
Statistical Characteristics:
Accuracy: Method permits accurate determination of much lower concentra-
tion of pigment than the other methods cited.
Precision; Not stated
Time of Measurement: Not stated
Calibration Requirements: The fluorometer must be calibrated with a chlorophyll
solution of known concentration.
Comments by Users; This method is more sensitive than the photometric method.
Data Output: Not stated. Assumed to be analog or digital electrical signal.
Special Sampling Requirements (Collection. Storage, Handling): If the analysis
will be delayed, store frozen. The stored samples must be kept in the dark to
avoid photochemical breakdown of the chlorophyll.
References: Biological Field and Laboratory Methods, U.S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio (1972)
(Preliminary Draft)
H-14
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H-15
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Chlorophyll a_, b_, and c_ o£ Phytoplankton and Periphyton
Medium; Water
Name of Measurement Method: In Vitro - Trichromatic Method
Principal Detect ion Technique: Spectrophotometric
Purpose of Measurement (Important Applications): All algae contain chlorphyll
Measurement of these pigments can yield an estimate of standing crop and
taxonomic composition.
Summary of Method; The sample is concentrated, macerated, steeped in 90% acetone,
at 4 C for 24 hours, and clarified by ccntrifugation. The optical density of
the decanted extract is determined at 750, 663, 645, and 630 run using 90%
acetone blank. The 750 run reading is used to correct for turbidity and the
other readings are inserted into SCOR/UNESCO equations for calculating chloro-
phyll a^, ]}, and c_.
Limitations:
Range of Applicability: Not stated
Interferences: None stated
Pitfalls; Special Precautions: Precautions should te taken to minimize
evaporation. Pheophytin, a natural degradation product of chlorophyll,
has an absorption peak in the same region of the visible spectrum as
chlorophyll a_ and could be a source of error in chlorophyll determination.
Statistical characteristics:
Accuracy: Not stated
Precision: Not stated
Time of Measurement: Not stated
Calibration Requirements: No unusual requirements
Data Outputs: Analog or digital electrical signal
Special Sampling Requirements (Collection, Storage, Handling) : If the analysis
will be delayed, store frozen. The stored samples must be kept in the dark to
avoid photochemical breakdown of the chlorophyll. Maximum storage time is 30
days.
References: Biological Field and Laboratory Methods, U.S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality ControlLaboratory, Cincinnati, Ohio (1972)
(Preliminary Draft)
' H-15
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H-16
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Phytoplankton and Periphyton Species Composition
Medium: Water
Name of Measurement Method: Species identification
Principal Detection Technique: Visual examination
Purpose of Measurement (Important Applications); The identification of
Tndividual species of phytoplankton may provide information on indicator
organisms, species diversity, and therefore the degree of pollution.
Summary of Method: Following an initial examination of the sample to
obtain an estimate of population density, etc., the phytoplankters are
identified to the desired taxonomlc level and tallied under a standard
system.
Limitations:
Range of Applicability: Plankton, periphyton
Interferences: None identified
Pitfalls; Special Precautions: Examination is preferably done before
sample is preserved. The beginner is strongly warned against the
deceiving and nonvalid simplicity often found in the identification
of plankton.
Statistical Characteristics:
Accuracy: Not applicable
Precision: Not applicable
Time of Measurement: One hour
Calibration Requirements: Not applicable
Data Outputs; Number of species and the number of individuals per species
Special Sampling Requirements (Collection. Storage. Handling): In cases
where it has been shown that preservation has no effects on the identifi-
cation of organisms, a preservative should be used if storage is necessary.
References: Biological Field and Laboratory Methods, U. S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft).
H-16
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H-17
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured; Cell Counts and Identification of Phytoplankton
Medium: Water
Name of Measurement Method: Bacterial counting cells and hemocytometers
Principal Detection Techniques: Visual observation
Purpose of Measurement (Important Applications): Provides information on
standing crop, (abundance and biomass) indicator organisms and community diversity.
Summary of Method: The sample is introduced into cells which are precisely-
matched glass slides with a finely-ruled grid on a counting plate fitted
with a specially ground cover slip. All forms which fall within the gridded
area of the cell are identified and counted. The number of the various
organisms found in the gridded area of the cell is multiplied by the appropriate
factor to obtain the count.
Limitations:
Range of Applicability: Not stated
Interferences: None identified
Pitfalls; Special Precautions: The analyst is advised to follow carefully
the specific uifecnions accompanying the chanter or cell. Collection of
phytoplankton by nets or pumps is not recommended. For statistical pur-
poses a normal sample must be either concentrated or a large number of
mounts per sample should be examined.
Statistical Characteristics;
Accuracy: Not stated
Precision: Not stated
Time of Measurement: 1 hour
Calibration Requirements: None
Data Outputs: Manual count
Special Sampling Requirements (Collection, Storage. Handling): Depends upon
the location and type of sample; see Reference. Samples must be concentrated
when densities are below 500/ml. Approximately 6 liters of samples are
required.
References; Biological Field and Laboratory Methods, U.S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft).
H-17
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H-18
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Cell Counts and Identification of Phytoplankton
Medium: Water
Name of Measurement Method: Inverted microscope method
Principal Detection Technique: Visual observation
Purpose of Measurement (Important Applications): Provides information on algal
standing crop, (abundance and biomass) indicator organisms and community diversity.
Summary of Method; The method uses an inverted microscope in conjunction with
a cylindrical counting chamber with a clear glass bottom. A sample is trans-
ferred to the counting chamber and allowed to settle. The chamber is placed
on the microscope stage and examined using either the 20x, 45x or lOOx oil
immersion lens. Either the strip or random field counts are made.
Limitations:
Range of Applicability: Not stated
Interferences: None identified
Pitfalls; Special Precautions; Collection of phytoplankton by nets or
pumps is not recommended.
Statistical Characteristics:
Accuracy; Not stated
Precision: Not stated
Time of Measurement: 4 hours per 10 mm of sample height in the chamber
is allowed for sedimentation. Count requires 1 hour
Calibration Requirements: Use stage and ocular micrometers
Data Outputs: Manual count
Special Sampling Requirements (Collection, Storage, Handling) : Depends on
the location and type of sample taken; see Reference.
References; Biological Field and Laboratory Methods, U.S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft).
H-18
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H-19
SUMMARY OF ANALYTICAL METHOD
Parameter (s) Measured: Cell Counts and Identification of Phytoplankon
Medium: Water
Name .of Measurement Method; Membrane filter method
Principal Detection Technique: Visual observation
Purpose of Measurement (Important Applications): Provides information on
standing crop (abundance and biomass), indicator organisms, and community diversity.
Method permits the use of high magnification for enumeration of small plankters.
Summary of Method; A water sample of known volume is passed through the
membrane filter under a vacuum. The filter is allowed to clear and the
organisms enumerated. The occurrence of each species in 30 random fields
is recorded.and multiplied by a conversion factor to obtain the total count
of each species.
Limitations;
Range of Applicability: Not stated
Interferences: Significant amounts of suspended matter may obscure
or crush the organisms
Pitfalls; Special Precautions: In coastal and marine waters the filter
is rinsed with distilled water to remove salt. Collection of phyto-
plankton by nets or pumps is not recommended.
Statistical Characteristics:
Accuracy: Not stated
Precision: ± 16Z CL
Time of Measurement: Relatively rapid processing of samples, (1 hour)
although total time required for the complete analysis if 48-50 hours.
Calibration Requirements: Use stage and ocular micrometers
Data Outputs: Manual count
Special Sampling Requirements (Collection, Storage. Handling): Depends upon
the location and type of sample taken. See Reference. Samples must be cone.
when phytoplankton densities are less than 500/ral. Approximately 6 liters
of sample are required.
References: Biological Field and Laboratory Methods, U.S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft).
H-19
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H-20
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Cell Counts and Identification of PhvtonlankLon
Medium: Water
Name of Measurement Method; Palmer-Maloney Mannoplankton Cell
Principal Detection Techniques; Visual observation
Purpose of Measurement (Important Applications): Provides information on
standing crop, indicator organisms and community diversity.
Summary of Method: An aliquot of well mixed sample is introduced into one
of the 2x5 mm channels on either side of the circular Palmer-Maloney
Nannoplankton cell with cover slip in place. After 10 minutes, the sample
is examined under the high-dry objective (45x) and at least 20 whipple fields
are counted.
Limitations:
Range of Applicability: The circular chamber used was especially
designed for enumerating nannoplankton with a high-dry objective
(45x).
Interferences: Not stated
Pitfalls; special precautions: The cell should not be used Cor routine
counting unless the samples have counts exceeding 20,000/ml. Collection
of phytoplanton by net or pumps is not recommended.
Statistical Characteristics:
Accuracy: Not stated
Precision: Not stated
Time of Measurement; 1 hour
Calibration Requirements: The microscope is calibrated using an ocular and
stage micrometer
Data Outputs: Manual count
Special Sampling Requirements (Collection, Storage, Handling): Depends upon
location and type of sample, see Reference. Samples muse be cone, when
densities are below 500/ml. Approximately 6 liters of sample are required.
References: Biological Field and Laboratory Methods, U.S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft)
H-20
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H-21
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Cell Surface Area of Phytoplankton
Medium: Water
Name of Measurement Method: Not stated
Principal Detection Technique: Visual observation
Purpose of Measurement (Important Applications): Determination of cell surface
area of phytoplankton is another indicator of plankton abundance.
Summary of Method: Measure the dimension of several representative individuals
of each major species microscopically. From the linear dimensions compute
the average surface area per species. Multiply the area per species by the
number of organisms per milliliter.
Limitations:
Range of Applicability: Phytoplankton
Interferences: Not stated
Pitfalls; Special Precautions: Not stated
Statistical Characteristics:
Accuracy: Not stated
Precision: Not stated
Time of Measurement: Not stated
Calibration Requirements: Ocular and stage micrometer
Data Outputs: Visual observation
Special Sampling Requirements (Collection. Storage. Handling): Depends on the
location and type of sample taken,1 see Reference.
References; Biological Field and Laboratory Methods, 1). S. Environ-
mental Protection Agency, National Environmental Research
Center, Analytical Quality Control Laboratory, Cincinnati,
Ohio (1972) (Preliminary Draft).
H-21
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H-22
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Chlorophyll a_ of Phytoplankton
Medium: Water
Name of Measurement Method; In Vitro - Monochromatic Method
Principal Detection Technique; SDectronhntninotric
Purpose of Measurement (Important Applications): All algae contain chlorphy.il a.
Measurement of this pigment can yield an estimate of standing croc.
Summary of Method: Chlorophyll £i can be estimated independently of the other
chlorophylls by measuring the optical density of the pigment extract of 665 nn
only, and inserting it into the following equation: Ca -=13.4Dgx,.. (Dggs is
the optical density, corrected for turbidity by subtracting the OD-750 nablank).
Limitations;
Range of Applicability; Not stated
Interferences: Not stated
Pitfalls; Special Precautions: Precautions should be taken to minimize
evaporation. Pheophytin a_, a natural degradation product of chlorophyll,
has an absorption peak in the same region of Lhe visible spectrum as
chlorophyll
-------
H-23
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Chlorophyll £ of Phytoplankton
Medium: Water
Name of Measurement Method: In vivo method
Principal Detection Technique: Fluorescence
Purpose of Measurement (Important Applications): All algae contain
chlorophyll a_. Measurement of this pigment can yield an estimate of
standing crop.
Summary of Method (Short Paragraph): The raw sample is placed
directly in cuvette, and fluorescence is determined.
Limitations:
Range of Applicability: Scale deflection should be between 15 and
90 units
Interferences: Phaephytin
Pitfalls; Special Precautions: This method is less efficient than
the extraction method, yielding about one-tenth as much fluorescence
per unit weight as the same amount in solution.
Statistical Characteristics:
Sensitivity: Method is more sensitive than the spectrophotometer method.
Precision: The precision of the method using natural population shows
for ten samples a maximum variation of 15 percent.
Time of Measurement: Less than 2 hours
Calibration Requirements: The fluorometer should be calibrated with a
chlorophyll extract which has been analyzed with a spectrofluorometer.
Data Outputs: Analog or digital electrical signal
Special Sampling Requirements (Collection, Storage. Handling): Prolonged
storage of extracts (greater than 5 days) under refrigeration and darkness
should be avoided. Fluorescence of extracts kept at room temperatures and
in light are stable for at least ten hours.
References:
(1) Yentsch, C.S. and D. W. Menzel, "A Method for the Determination
of Phytoplankton Chlorophyll and Phaeophytin by Fluorescence,"
Deep-Sea Research 10. 221-281 (1963).
(2) Biological Field and Laboratory Methods, U.S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft).
H-23
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H-24
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: In-Situ Productivity of Phvtoplankton
Medium: Water
14
Name of Measurement Method: Carbon Method
Principal Detection Technique: Radioactive assay
Purpose of Measurement (Important Applications): Phytoplankton productivity
measurements indicate the rate of uptake of inorganic carbon by phytoplankton
during photosynthesis and are useful in determining the effects of pollutants
and nutrients on the aquatic community.
Summary of Method: A solution of radioactive carbonate is added to light
and dark bottles which have been filled with samples taken from preselected
depths in the euphotic zone. Following in situ incubation (u? to four hours)
the plankton is collected on a membrane filter, dried in a desiccator, and
assayed for radioactivity. The quantity of carbon fixed is proportional to
the fraction of radioactive carbon assimilated. If measurements are reouired
for the entire photoperiod, samples may be taken at overlapping four-hour
periods or the data mav be adjusted based on the solar radiation profile.
Limitations:
Range of Applicability: Phytoplankton
Interferences: Not stated
Pitfalls; Special Precautions: Carbon in the filtered sample should
yield the number of counts required for statistical significance.
Statistical Characteristics:
Accuracy: Not stated
Sensitivity: Method is more sensitive than the oxygen method,
but fails to account for the organic materials that leach
from cells during the incubation period
Time of Measurement: (Sample' should be Incubated for at least two hours.)
Calibration Requirements: None
Comments by Users: Method affords a direct measurement of carbon uptake and
measures only photosynthesis.
Data Outputs: Instrument count
Special Sampling Requirements (Collection, Storage, Handling): Not stated
References:
(1) Biological Field and Laboratory Methods, U. S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft).
(2) Standard Methods for the Examination of Water and Waste
Water, 13th Edition, American Public Health Association,
et al., Washington, D. C. (1971).
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H-25
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: In Situ Productivity of Phytoplankton
Medium: Water
Name of Measurement Method: Oxygen Method
Principal Detection Technique: Titrimetric (Dissolved oxygen measurement)
Purpose of Measurement (Important Applications): Phytoplankton productivity
measurements indicate the rate of uptake of inorganic carbon by phytoplankton
during photosynthesis and are useful in determining the effects of pollutants
and nutrients on the aquatic community.
Summary of Method: Samples are taken from preselected depths in the euphotic
zone and placed in duplicate clear, darkened and initial analysis bottles.
The duplicate clear and darkened bottles are suspended at the depth from
which the samples are taken and allowed to incubate. At the end of the
exposure period the dissolved oxygen of the samples is measured. The increase
in oxygen concentration in the light bottle during incubation represents net
production and the loss of oxygen in the dark bottles is an estimate of
respiration.
Limitations:
Range of Applicability: Phytoplankton
Interferences: Not stated
Pitfalls; Special Precautions: The incubation period should not be
long enough to allow oxygen-gas bubbles to form in the clear bottles
or dissolved oxygen to be depleted in the dark bottles. The solar
radiation profile in addition to the photosynthetic rate during the
incubation period should be used to adjust data to represent pro-
ductivity for the entire photoperiod.
Statistical Characteristics:
Accuracy and Precision: Not stated
Time of Measurement: Samples should be incubated for at least two hours.
Calibration Requirements: None
Comments by Users: Chief advantages of the oxygen method are that it provides
estimates of gross and net productivity and respiration and that the analysis
can be performed both with inexpensive laboratory equipment and common reagents.
Data Outputs: Visual observation (titrimetric) or analog or digital
electrical signal (electrometric DO method).
Special Sampling Requirements (Collection. Storage. Handling): If the dissolved
oxygen is not measured immediately, it should be fixed and protected from di»-n-t
sunlight.
References:
(1) Biological Field and Laboratory Methods, U. S. Environmental
Protection Agency, National Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
(1972) (Preliminary Draft).
(2) Standard Methods for the Examination of Water and Waste
Water, 13th Edition, American Public Health Association,
et al.. Washington, D. C. (1971).
IL-25
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H-26
SUMMARY OF ANALYTICAL METHOD
Parameter(s) Measured: Zooplankton Volume and Species Identification
Medium: Water
Name of Measurement Method; Volumetric Determination
Principal Detection Technique: Volumetric Determination; Visual Observation
Purpose of Measurement (IraporLan:: Applications): Measurement of zooplankton
Volu:ne provides arT index to Lhe standing crop (biomass) of natural zooplankto
population-
Summary of Method:
The sample is screened, placed into a conical container graduated in
milliliters, allowed to settle for five minutes, and the settled volume
is recorded. The sample is then stirred and a one ml subsample is with-
drawn from the container with a Stempel pipette. The subsample is
examined under a dissecting microscope for enumeration of zooplankton
Limitations:
Range of Applicability; Rot if era, cladocera, copepods and other large
zooplankton forms.
Interferences: None stated
Pitfalls; Special Precautions: None stated
Statistical Characteristics:
Accuracy and Precision: Not stated
Time of Measurement: Less than one hour
Calibration Requirements: None required
Data Outputs: Visual observation, manual reading
Specla] Sampling Requirements (Collection, Storage, Handling): Depends upon
location and type of sample taken. See Reference.
References; Biological Field and Laboratory Methods, U.S. Environmental
Protection Agency, "ationnl Environmental Research Center,
Analytical Quality Control Laboratory, Cincinnati, Ohio
* (1972) (Preliminary Draft)
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LIST OF PRIMARY REFERENCE SOURCES
1. AQCL. Informal compilation of six Analytical Methods and
Provisional Methods for Mercury and Methylmercury, provided by
Analytical Quality Control Laboratory, National Environmental
Research Center, U. S. Environmental Protection Agency,
Cincinnati, Ohio, 1972.
2. ASTM. Book of ASTM Standards, American Society for Testing and
Materials, 1916 Race Street, Philadelphia, Pennsylvania. Part 11,
(Designation 070-52), 1972.
3. , Part 11 (Designation D71-72a), 1972.
4. , Part 17 (D86-67), 1968.
5. , Part 17 (D88-56), 1969.
6. , Part 17 (D216-54), 1965.
7. , Part 17 (D445-72), 1972.
8. , Part 17 (D850-70), 1970.
9. , Part 17 (D941-55), 1968.
10. , Part 17 (D1217-55), 1968.
11. , Part 18 (D87-66), 1967.
12. , Part 18 (D127-63), 1964.
13. , Part 18 (D287-67), 1968.
14. Bender, D. F., H. Stierli and U. L. Peterson, Editors, Physical.
Chemical, and Microbiological Methods of Solid Waste Testing,
U. S. Environmental Protection Agency, National Environmental
Research Center, Cincinnati, Ohio, 1973. ( In print)
15. Biological Field and Laboratory Methods. U. S. Environmental
Protection Agency, National Environmental Research Center,
Cincinnati, Ohio, 1972. (Preliminary copy)
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16. Buelow, R. W., J. K. Carswell, and J. M. Symons, "An Improved
Method for Determining Organics in Water by Activated Carbon and
Solvent Extraction," U. S. Environmental Protection Agency,
National Environmental Research Center, Cincinnati, Ohio, July
1972. (Fre-publication copy)
17. Clements, John B., Informal compilation of Analytical Methods for
Air Pollution, provided by John B. Clements, U. S. Environmental
Protection Agency, National Environmental Research Center,
Research Triangle Park, N. C. (Letter dated October 5, 1972)
18. "Determination of Petroleum Oil." Preliminary Method description
received from Oil Spills Research Branch, U. S. Environmental
Protection Agency, National Environmental Research Center,
Edison, New Jersey, December 1972. (This method has been submitted
for inclusion in subsequent issues of Laboratory Guide for
Identification of Petroleum Products. U. S. Environmental Pro-
tection Agency, Cincinnati, Ohio, 1969.)
19. "Development of Low Temperature Molecular Method for Oil," Baird
Atomic Corporation, No. 16020 GBW, EPA Contract 68-01-0146.
(Method description received from Oil Spills Research Branch,
U. S. Environmental Protection Agency, National Environmental
Research Center, Edison, New Jersey.
20. Douglas, Geneva S., (Editor), Radioassay Procedures for
Environmental Samples. National Center for Radiological Health,
U. S. Public Health Service, Rockville, Maryland, January 1967.
21. Federal Register. Volume 36, Number 84, April 30, 1971.
22. , Volume 36, Number 235, December 7, 1971.
23. , Volume 36, Number 247, Thursday, December 23, 1971.
24. Jones, Frederick B., Southwestern Radiological Health Laboratory
Handbook of Radiochemical Analytical Methods. Report No. SWHRL-11,
U. S. Public Health Service, Southwestern Radiological Health
Laboratory. (Now the Western Environmental Research Laboratory
of the U. S. Environmental Protection Agency), Las Vegas, Nevada,
March 1970. (Reprint January 1972)
25. Kawahara, Fred K., Laboratory Guide for the Identification of
Petroleum Products, Federal Water Pollution Control Administra-
tion, Division of Water Quality Research, Cincinnati, Ohio,
January 1969.
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26. Kopp, John F., Mary C. Longbottom, and Larry B. Lobring,
"'Cold Vapor1 Method for Determining Mercury," Journal of the
American Water Works Association, Volume 64, page 20, January 1972.
27. Kreiger, H. L. and S. Gold, Procedures for the Radiochemical Analysis
of Nuclear Reactor Aeneous Wastes. Report Number EPA-4A-72-XXXX,
U. S. Environmental Protection Agency, National Environmental
Research Center, Radiochemistry and Nuclear Engineering Research
Laboratory, Cincinnati, Ohio. (Undated preliminary draft, 1972)
28. Methods for the Chemical Analysis of Water and Wastes. U. S.
Environmental Protection Agency, National Environmental Research
Center, Analytical Quality Control Laboratory, Cincinnati, Ohio,
1971.
29. Methods for Organic Pesticides in Water and Wastewatcr. U. S.
Environmental Protection Agency, National Environmental Research
Center, Cincinnati, Ohio, 1971.
30. Morgan, George, E. C. Tabor, C. Golden, and H. Clements,
"Automated Laboratory Procedures for the Analysis of Air
Pollutants," presented at the Technicon Symposium, Automation
in Analytical Chemistry. New York, N. Y., October 19, 1966.
31. Morgan, George, C. Golden and E. C. Tabor, "New and Improved
Procedures for Gas Sampling and Analysis in the National Air
Sampling Network," presented at the Technicon Symposium,
Automation in Analytical Chemistry, New York, N. Y., October 19,
1966.
32. O'Keeffe, Andrew, Informal compilation of Analytical Methods for
Air Pollutants, provided by Andrew O'Keeffe, U. S. Environmental
Protection Agency, National Environmental Research Center,
Research Triangle Park, N. C. (Ca. November 1972)
33. Porter, C. R. et al.(Editors), Procedures for Determination of
Stable Elements and Radionuclides in Environmental Samples.
PHS Publication No. 999-RH-10, U. S. Public Health Service,
Division of Radiological Health, Washington, D. C., January 1965.
34. Procedures for Radiochemical Analysis of Nuclear Reactor Aqueous
Solutions. Report No. EPA-4A-72-XXXX (Draft), National Environ-
mental Research Center, U. S. Environmental Protection Agency,
Cincinnati, Ohio, 1972. (Note: This is the same document as
Ref. 27 above.)
H-29
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35. Standard Methods for Examination of Water and Wastewater, 13th
Edition, American Public Health Association, et al., Washington,
D. C., 1971.
36. Strong, Ann (Editor), Procedures for Radlochemical Analysis at the
Eastern Environmental Radiation Laboratory. EERL Report No. 7X-XXXX
(Draft), Eastern Environmental Research Laboratory, U. S.
Environmental Protection Agency, Montgomery, Alabama. (Undated;
Ca. 1972)
37. Thompson, J. F. (Editor), Analysis of Pesticide Residues in Human
and Environmental Samples, U. S. Environmental Protection Agency,
Perrine Primate Research Laboratories, Perrine, Florida,
January 1971.
38. Thurston, A. D., and R. W. Knight, "Characterization of Crude
and Residual-Type Oils by Fluorescent Spectroscopy," Environmental
Science and Technology. 5_:64-69 (1971).
39. Zaifirion, 0., et al., "Correlation of Oils and Oil Products by
Gas Chromatography," Woods Hole Oceanographic Institution,
Report No. 62-55, July 1, 1962. (Method description received from
Oil Spills Research Branch, U. S. Environmental Protection Agency,
National Environmental Research Center, Edison, New Jersey.)
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