United States
          Environmental Protection
          Agency
Office of Water
Engineering and Analysis Division (4303)
Washington, DC 20460
EPA-821-B-96-003
July 1996
4»EPA    Guidelines and Format for Methods to
          Be Proposed at 40 CFR Part 136 or
          Part 141
                                                > Printed on Recycled Paper

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Guidelines and Format for Methods to be
 Proposed at 40 CFR Part 136 or Part 141
               Prepared by

          Analytical Methods Staff
   Engineering and. Analysis Division (4303)
       Office of Science and Technology
              Office of Water
    U. S. Environmental Protection Agency
              Washington, DC
                 July 1996

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                                                                  Method Guidelines and Format
                                   Disclaimer

This document has been reviewed by the Analytical Methods Staff of the Engineering
and Analysis Division in EPA's Office of Science and Technology.  This document
presents guidance on method format and content as contemplated by EPA as part of its
initiative to streamline the water methods approval program. Mention of trade names
or commercial products does not constitute endorsement or recommendation for use.
                                                                                July 1996

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 Method GuKfe/jrces and Format
                                    Table of Contents

 Introduction	1

 1.0    Elements	 2

 1.1     Cover page	2
 1.2     Title page	:	2
 13     Acknowledgments  	3
 1.4     Disclaimer	3
 1.5     Table of contents	 . 4
 1.6     Introduction	4
 1.7     Notice of performance-based method  	4
 1.8     Body of method	4

 2.0    Format		,	 5

 2.1     Page numbering	5
 2.2     Method identification	5
 23     Method date .	 ,	5
 2,4     Font	5
 2.5     Margins	5
 2.6     Justification	6
 2.7     Line spacing  	•	,	6
 2.8     Method sections	6
 2.9     Section headings and numbering  	•	'. .,	6
 2.10    Indentation	 6
 2.11    Electronic submission	 6
 2.12    References	7

 3.0     Conventions  .	7

 3.1     Capitalization, italics, underlining, and boldface	7
 3.2     Punctuation	.8
 33     Footnotes	8
 3.4     Text notes	 .  8
 3.5     Equations	 9
 3.6     Tables and Figures	9
 3.7     Trademarks	9
 3.8     Text references	9
 3.9     Units, symbols, abbreviations, and acronyms	9
 3.10    Numerals	10
 3.11    Significant digits	11
3.12    Order of magnitude	12
3.13    Rounding	12

4.0     Content	12

4.1     Scope and application		13
4.2    Summary of Method	14

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                                                                      Method Guidelines and Format
4.3    Definitions . .		14
4.4    Interferences	.15
4.5    Safety				15
4.6    Equipment and Supplies  . ,	16
4.7    Reagents and Standards	.	 17
4.8    Sample Collection, Preservation, and Storage	J	 17
4.9    Quality Control . .	18
4.10   Calibration and Standardization	. . 20
4.11   Procedure		20
4.12   Data Analysis and Calculations	 21
4.13   Method Performance	22
4.14   Pollution Prevention	22
4.15   Waste Management	.23
4.16   References	 .	..	 . 23
4.17   Tables, Diagrams, Flowcharts, and Validation Data  	•.	23
4.18   Glossary	24
Appendices

Appendix A

Appendix B
Standard Acronyms, Abbreviations, and Symbols

Example of Method Format
"Method 1664: N-Hexane Extractable Material (HEM) and Silica Gel Treated N-
Hexane Extractable Material (SGT-HEM) by Extraction and Gravimetry (Oil and
Grease and Total Petroleum Hydrocarbons)"
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                                                                         Method Guidelines and Format
Introduction

The guidelines and format presented in this document are to be used by EPA and other organizations
in preparing new analytical methods for proposal and promulgation under CWA Section 304(h) and
SDWA Section 1445(a).  These guidelines, in general, follow the "Guidelines and Format for EMSL-
Cincinnati Methods" and the American Society for Testing and Materials (ASTM) requirements as
stated in "Form and Style for ASTM Standards," November 1994 (13-000001-94). These guidelines
and format are a detailed amplification of the Environmental Monitoring Methods Council (EMMC)
format. A guideline and format from another organization may be used provided that it is
standardized and contains the same elements contained in this document.  For example, the method
formats from Standard Methods for Examination of Water and Wastewater, ASTM, AOAC-
International, and the U.S. Geological Survey may be used because these formats are documented and
adhered to by these organizations. Methods produced or approved by organizations that allow random
formats must be revised into a the format presented in the guidelines and format presented in this
document, or into another standardized format, before submission for proposal at 40 CFR part 136 or
141.

The "Guidelines and Format for Methods to be Proposed at 40 CFR part 136 or part 141" (the
"Method Guidelines and Format") have been prepared to promote consistency among analytical
methods and to streamline the method promulgation process.  The elements given in these Method
Guidelines and Format are mandatory for all methods proposed at 40 CFR part 136 or 141. This
document is presented in four sections that describe standard elements that must be included in the
method, required method format, conventions to be used when preparing the method, and required
method content.                    .

OW BAD Method 1664, N-Hexane Extractable Material and Silica Gel Treated N-Hexane Extractable
Material by Extraction and Gravimetry (Oil and Grease and Total Petroleum Hydrocarbons), is given
hi Appendix B as an example of a method that adheres to these Method Guidelines and Format.

Questions and comments concerning Method Guidelines and Format should be addressed to:

W. A. Telliard
USEPA Office of Water
Analytical Methods Staff
Mail Code 4303
401 M Street, S.W.
Washington, DC 20460
202/260-7120

Requests for additional copies of this publication should be directed to:

Water Resource Center
Mail Code RC-4100
401 M Street, S.W.
Washington, D.C. 20460
202/260-7786
                                             , 1
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 Atelftod Gukterms and Format
 1.0    Elements

 1.1     Cover page
        For methods submitted to EPA from other organizations or individuals, no cover page is
        required. Prior to method publication, EPA will prepare the cover page in the standard EPA
        format, as shown in the sample method in Appendix B.  The cover page will use black ink on
        white or colored paper stock and may include a cover graphic that illustrates the method.

        EPA will assign a three- or four-digit method number that correlates with the EPA method
        series to which the method belongs.  The method number is included as the first part of the
        method title on the cover page.
1.2    Title page
       There are two types of title page: a title page prepared by an organization or individual that is
       submitting a method to EPA, and the final tide page that appears in the EPA-published
       method,

       1.2.1    Individuals or organizations submitting methods to EPA  should include the following
               information on the title page of the method:
               •      Method title
               •      Date
               •      Sponsoring organization with address and telephone number

               1.2.1.1  When tiding the method, use a concise title that cites (in sequence) the
                      particular analyte(s) or property being determined, the type of sample or
                      sample matrix(ces) to which the method is applicable, as appropriate, and the
                      determinative technique or instrumentation. Apply the following guidelines in
                      titling methods:

                      •      If the method applies to numerous matrices (such as water, soil,
                             sediment, sludge, tissue, and others), it may not be practical to include
                             matrices in the title; however, if the method applies to a single matrix
                             or a limited number of matrices, the matrix(ces) should be specified in
                            .the title.

                      •      If the method is used to determine a number of analytes or properties,
                             analytes or properties can be named as a group (e.g., trace elements),
                             and the names of specific analytes or properties omitted.

                      •      Avoid the use of the terms "analysis of..." or "determination of..." in
                             method titles, since these terms are understood within the context of
                             the term "method."

                      •      Method titles should use abbreviations  or acronyms for familiar parts
                             of the method title, e.g., HRGC/HRMS.  The acronym or abbreviation
                             should be defined at first use in the method.
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                                                                         Method Guidelines and Format
                             Examples of suitable method titles are:

                             •      Mercury in Water by Oxidation, Purge and Trap, and Cold
                                    Vapor Atomic Fluorescence Spectrometry

                             •      Tetra- through Octa- Chlorinated Dioxins and Furans by
                                    Isotope Dilution HRGC/HRMS

               1.2.1.2  For a methods manual, use a title that identifies the category of methods
                      included in the manual.  Examples of suitable methods manual titles are:

                      •  .   Analytical Methods for Pulp and Paper Industry Wastewater

                      •      Analytical Methods for the Determination of Pollutants in
                             Pharmaceutical Manufacturing Industry Wastewater

       1.2.2    Before publishing the method, EPA will generate a title page that mimics the cover
               page (excluding any cover graphics).

1.3    Acknowledgments

       Acknowledgments should identify the author  and editor, and provide credit to researchers, peer
       reviewers, and organizations or individuals that contributed directly and substantively in the
       development and writing of the method.  These acknowledgements are independent of
       references listed at the end of the method.
1.4
Disclaimer
       The disclaimer may appear on the same page with the acknowledgments or may be on the
       page following the acknowledgments.  It may contain one or more disclaimer statements.  All
       disclaimers should include the following statement:

       •      The mention of trade names or commercial products does not constitute endorsement
              or recommendation for use.

       The disclaimer may not state explicitly or imply that EPA has granted any approval of the
       method.  Once the method has been validated and submitted to EPA for proposal, however,
       the following statement may be included:

       •      This method has been submitted to the U.S. Environmental Protection Agency for use
              in EPA's water programs but has not been approved for use by EPA.

       For draft methods, include the following statement:

       •      This method is in draft form.  It has not been released by the U.S. Environmental
              Protection Agency and should not be construed as an Agency-endorsed method.  It is
              being circulated for comments on its technical merit.

       When preparing the method for proposal at 40 CFR part 136 or 141, EPA will edit the
       disclaimer to cite the Agency review process that the method has undergone.
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 Afetfxx/ GukteHnes and Format
1.5     Table of contents

        A table of contents is required for methods manuals and is recommended for single methods
        that exceed 25 pages in length. The table of contents should cite the titles and page numbers
        of all first- and second-order headings (see section 2.9, "Section headings") and all tables and
        figures.

1.6     Introduction

        In the introduction, provide background on the method, describe the purpose of the method,
        and include a summary-level description of the method.  Identify the name, organization,
        address,  and telephone number to contact for questions regarding the method.

        When preparing the validated method for submission to EPA for proposal at 40 CFR part 136
        or 141, include the following instructions at the end of the introduction:

        •      Questions concerning this method or its application should be addressed to:

              W. A. Telliard
              USEPA Office of Water
              Analytical Methods Staff
              Mail Code 4303
              401 M Street, S.W.
              Washington, DC 20460
              202/260-7120

        •      Requests for additional copies of this publication should be directed to:

              Water Resource Center
              Mail Code RC-4100
              401 M Street, S.W.
              Washington, DC 20460
              202/260-7786

1.7     Notice of performance-based method

        All methods prepared should be performance-based and should contain the  following notice on
        a separate page directly preceding the body of the method.

        •      Note:  This method is performance-based. The laboratory is permitted to modify or
              omit any step or procedure, provided that all performance requirements set forth in this
              method are met.  The laboratory may not omit any quality control analyses.  The terms
              "shall" "must," and "may not" indicate steps and procedures required for producing
              reliable results.  The terms "should" and  "may"  indicate optional steps that may be
              modified or omitted if the laboratory can demonstrate that the modified method
              produces results equivalent or superior to results produced by this method.

1.8     Body of method

        The body of the method must be presented in the EMMC format.  See Section 4.0 for a
        detailed description of this format.
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                                                                         Method Guidelines and Format
 2.0    Format
2.1     Page numbering

        Page numbers should appear in the bottom center of the page. For methods prepared double-
        sided, page numbers may appear on the outside bottom comer of the page (i.e., on the bottom
        right for right-hand pages and on the bottom left for left-hand pages).

        2.1.1    Numbering front matter -- Number the front matter (i.e., everything preceding the body
               of the method) consecutively using lower-case Roman numerals.  The numerals should
               appear on the bottom of each page of the front matter, except for the cover and title
               pages. The cover page is unnumbered.  The title page holds the place of page i but
               the numeral is not displayed.

        2.1.2    Numbering body of method — Number the body of the method consecutively with
               Arabic numerals on the bottom of each page, starting with the number 1.

2.2 ,    Method identification                                                       .

        2.2.1    The method introduction page(s) should contain a header that identifies the method
               number and revision number or  letter. The first page of the body of the method
               should start with the method number and title in the top center of the page (preceding
               1.0 Scope and Application), with no header, as shown in Appendix A.  Each pursuant
               page of the method should contain a header that identifies the method number and
               revision number or letter. The header also must be separated from the main body of
               the method by a horizontal line running the width of the page.

        2.2.2    If the method was assigned a non-EPA method number during its development and
               validation,  when preparing the method for submission to EPA for proposal at 40 CFR
               part 136 or 141, edit the header  to reflect the method number assigned by EPA (i.e.,
               Method 1664).
2.3
Method date
       The date of the method (month and year) should appear on the bottom of each page of the
       method.
2.4
Font
       For text, use an 11-point Times Roman font (typeface). For first-order headings,'use a bold,
       14-point Univers font. For section numbering, use a bold, 12-point Univers font. For headers
       and footers, use an italics, 9-point Univers font. Univers or Times Roman fonts may be used .
       in tables as appropriate.  If Univers is unavailable, Helvetica may be substituted.
2.5     Margins
       Left and right margins should be one inch.  The header should be 0.5 inch from the top of the
       page,  with the text starting one inch from the top of the page.  The page number should
       appear 0.5 inch from the bottom of the page, with the text starting one inch from the bottom
       of the page.
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 Method Gofcfe/wes and Format
 2.6     Justification

        Use left justification for text. This results in a ragged-right margin.

 2,7     Line spacing

        The method should be single-spaced.  (If preferred, 1.1 line spacing can be used to enhance
        readability.) One blank line should appear between each paragraph and section.

 2,8     Method sections

        Each method must contain the sections given in the EMMC method format. See Section 4.0
        for a detailed description of this format. If a section does not apply to a particular method,
        include the section with a statement that it is not applicable to that method.

 2.9     Section headings and numbering

        Use the Modified Decimal Numbering (MDN) system to organize material presented in
        methods and methods manuals.  In this system, each method section and subsection is assigned
        a unique number that shows the relationship of a specific section/subsection to all previous
        sections/subsections and allows for easy reference.  This numbering system is used in this
        document and in the example method that appears in Appendix A.

        The first-order headings are the  17 sections identified in Section 1.7, "Body of Method,"
        starting with 1.0 Scope and Application. First-order headings must  appear on a separate line,
        with a blank line appearing between the heading and the section text.  Subsections are
        numbered and may or may not have a heading preceding the text. Second-order headings or
        sections are numbered 1.1, 1.2, 1.3, 1.4, etc.  Third-order headings or sections are numbered
        1.1.1, 1.1.2, 1.1.3, etc.  Fourth-order headings or sections are numbered 1.1.1.1, 1.1.1.2,
        1.1.1.3, etc.

        Do not number beyond the fourth-order heading or section.  If additional subdivisions are
        necessary, use (a), (b), (c), etc. to identify further divisions.  Use of subdivisions below the
        fourth-order Beading or section should be avoided where possible by organizing the material
        differently.

2.10    Indentation                                              .

        First-order headings should appear flush left. Each subsequent order heading should be block-
        indented to align with the text of the previous order heading. This indentation method is
        illustrated in this document and in Method 1664 in Appendix A.

2.11     Electronic submission

        Methods and methods manuals must be prepared and submitted to EPA in both hardcopy and
        electronic formats.

        2.11.1  Hardcopy methods should be produced in black type on white or off-white recycled
               paper  and printed or copied double-sided.
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                                                                           Method Guidelines and Foi.-nat
        2.11.2 Electronic methods must be submitted in machine-readable format, either ASCII or
             ,  WordPerfect 5.1 or later.

        2.11.3  To enable anyone accessing a method electronically to be certain they have retrieved
             ^  the entire section or method accessed, include a "section end" notice at the .end of each
               first-order section. This is illustrated as follows:

                         ************  End of Section 4.0 ************

2.12    References

        Use the following format for order, content, and punctuation when listing references.
                         /                                            ••    .   ,

        2.12.1   Books — author's name or names (initials last), title of book (underline, period, no
               quotation marks), name of publisher, address of publisher (city and state), year of
               publication, and page number, if applicable

        2.12.2  Magazines and Journals — author's name or names  (initials last), "title of paper"
               (quotation marks, comma), volume number, issue number (this may  be omitted if the
              journal page numbers are continuous throughout the volume), date of publications, and
               page numbers.  Example:  Jones, J.J., and Smith, R.R., "Correlation  of Brinell
               Hardness and Tensile Strength, Materials in Design Engineering.  Vol. 10, No. 2,
               February 1958,  pp. 52-67.  A list of common journal abbreviations is given in
               Appendix C.

        2.12.3  Proceedings, Transactions, Reports, Bulletins, etc. — author's name or names (initials
               last), "title of paper" {in quotation marks), name of publication (underline, no quotation
              -marks, comma), name of publisher, volume number, if any date of publication,and
               page numbers.

        2.12.4  Symposium Volumes or Other Books Comprising Collections of Papers — Follow style
               for books, above and add title of paper, in quotes, after author's name.

        2.12.5  Patents — patent number and data.

        2.12.6  EPA methods — Method number and name, EPA report number, U.S: Environmental
               Protection Agency, laboratory and/or office, location, date.

3.0     Conventions

3.1      Capitalization, italics, underlining, and boldface

      '  3.1.1    Capitalization

               3.1.1.1  For first-order headings (numbered 1.0, 2.0, 3.0, etc.), use initial capitalization
                      of major words.                        \

               3.1.1.2  For second-, third-, or fourth-order headings, capitalize the first word of the
                      heading only.
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 Me food Guidelines and Fomat
         3A 3.   Italics—Italicize words or blocks of text for emphasis.  Equations and notes
                interspersed in the text also should be italicized.

         3.1.3   Underlining—Underline words that are defined in the Definitions section (or glossary).
                Use underlining in tables as appropriate for clear presentation of material. Do not use
                underlining for emphasis; use italics instead but avoid overuse of emphasis.

         3.1.4   Boldface—Boldface the following items:
                •      the method number and title on the cover page, title page, and page  1 of the
                       method
                •      Acknowledgments, Disclaimer, and Introduction headings
                •      first-order headings
                •      section numbering
                •      equation numbers
                *      the word "Note:" preceding text notes.

 3.2     Punctuation

        3.2.1    Always use a comma after the second to last entry in a series.

        3.2.2    A dash may be used between a subheading and text that directly follows the
                subheading.  There should be no blank space before or after the dash, e.g., "Matrix
                Spikes—The laboratory must spike..."

        3.2.3    As a general rule, use a hyphen  in compound modifiers  to avoid ambiguity, e.g., 1-L
                flask.  (In some cases, the hyphen can be left out  without ambiguity, e.g., toxic
                chemical waste.)  Do not use a hyphen after an adverb ending in "ly," e.g., commonly
                accepted practice.

        3.2.4    Bullets are not to be used in the body of the method. If used in introductory material,
                the text following the bullet should start with a capital letter.  Short bullets do not
                require periods at the end; long (multiple-line) bullets do.  Semicolons or commas
                should not be used  after bulleted text.
3.3
Footnotes
        Use footnotes only in tables.  Footnotes should be designated with numbers or lower case
        letters in superscript, and should appear below the body of the table.
3.4     Text notes
        Notes may be used within the text to highlight important information regarding use of the
        method. Use a margin-to-margin line across the page both preceding and following the note to
        set it off from the text.                         '                                      i
3.5     Equations
        Equations should be numbered Equation 1, Equation 2, etc., consecutively as they appear in
        the text.  Use a margin-to-margin line across the page both preceding and following the
        equation to set it off from the text.  Equations should be presented in italics.  The equation is
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                                                                           Method Guidelines'and Format
        followed by "where:" and a list of terms used in the equation (e.g., n = number of samples, x
        = concentration in each sample).         ,

3.6     Tables and Figures

        Tables and figures appear in Section 17.0.

        3.6.1    Number tables and figures consecutively with arabic numerals, and give each a title
               that is complete and descriptive.                             .    '     -    .

        3.6.2    In  table column headings, specify the quantity being tabulated, followed by the units
               of measurement shown in parentheses.  For example, "Amount spiked (ug/L)".

        3.6.3    Place table and figure titles above the information presented.

        3.6.4    Figures may be enclosed in a box if desired.

3.7     Trademarks

        3.7.1    Avoid the use of trademarks or brand names whenever possible.  For examples, use
               the term "borosilicate glass" rather than the trademarks Pyrex or Kimax; use
               "fluoropolymer" rather than Teflon.  (See Section 4.6.4.)

        3.7.2    When a trademark or brand name is used, capitalize it.

3.8     Text references                                                   •

        Text references are references to other  locations within the method, not references to any
        outside source. References to other sources appear in Section 16.0.  Do not incorporate
        essential information into the method by referring to another method.

        In the method text, refer to other sections of the method capitalizing the word "Section."
        Section references should appear in parentheses at the end of the phrase or sentence to which
        the reference applies, for example, (Section 9.6).

3.9     Units, symbols, abbreviations, and acronyms

        3.9.1    Units and symbols from the international metric  system (SI, from the French name, Le
               Systeme International d Unites) are to be used. SI is based on seven basic units that
               are dimensionally independent.  The SI unit pf time is the second (symbol = s) which
               should be used if practical.  The SI unit of volume is the cubic meter (symbol = m3)
               but the spectral name liter (symbol  = L) can be used for liquids and gases.  Although .
               the SI unit for mass is kilogram (symbol = kg), the use of gram (g) with or without
               prefixes is appropriate.

        3.9.2    Symbols, not abbreviations, should  be used for units. Symbols are not followed by a
               period except when  used at the end of a sentence. Unit symbols are written in lower
               case except for the symbol for  liter (L) or where the unit name was derived from a
               proper name, such as Pa, from  Pascal. When  a quantity is expressed as a numerical
               value and a unit symbol, a space should be left between them, except between the
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July 1996

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Melted Guidelines and Fomat
               number and symbol for degree Celsius (20°C) and for degree, minute, and second of
               plane angle.

       3.9.'3    Use commonly accepted abbreviations in tables as appropriate to conserve space.

       3.9.4    Use commonly accepted acronyms and abbreviations in text and tables.  An acronym
               is a word formed from the first or first few letters of other words; everything else is an
               abbreviation.  In many cases, an acronym or abbreviation is more readily identifiable
               than its narrative counterpart.  Always spell out the term the first time it is used and
               follow  it with the acronym or abbreviation shown in parentheses, e.g., material safety
               data sheet (MSDS), relative percent difference (RPD), or United States Environmental
               Protection Agency  (EPA).  Acronyms and nearly all abbreviations have no periods or
               spaces  between  letters. As depicted in these examples, although the acronym or
               abbreviation is capitalized, the narrative version of it is not capitalized unless it is a
               proper  name such as a government agency, society, or association. Once an acronym
               or abbreviation is introduced in this manner, use only the acronym or abbreviation
               subsequently.

       3.9.5    When a long word  or phrase for which there is no standard acronym or abbreviation is
               used frequently, it may be replaced by an acronym or abbreviation that is explained
               when it first occurs. For example, relative centrifugal force (RCF).

       3.9.6    A list of common symbols, abbreviations, and acronyms is included in Appendix B to
               this document.

3.10   Numerals

       3.10.1   Spell out single-digit numbers (one through nine), with the following exceptions:

               3.10.1.1        Use numerals when the quantity is partly fractional, e.g.,  1.15, 1- Yz.

               3.10.1.2        Use numerals when the number is followed by a unit symbol, e.g., 1
                              m,  9%, 3 ppm. In the method text, units should be spelled out, so the
                              numbers one through nine associated with the units would be spelled
                              out also  (e.g., one meter, nine percent, three palrts per million).

               3.10.1.3        Use numerals to identify equations and tables (e.g., Equation 2, Table
                              5).

               3.10.1.4        In  sentences containing multiple numbers, if some numbers must be
                              numerals, use numerals for all (e.g., 2 tests and 16 weighings).

       3.10.2  Use numerals for multiple-digit numbers (10 and above), with the following
               exceptions:

               3.10.2.1        Do not begin a sentence with a numeral.  When the numeral is spelled
                              out, also spell out the unit following (e.g., One gram is usually
                              sufficient.)
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                                                                           Method Guidelines and Format
               3.10.2.2         Spell out round numbers that are used in an indefinite sense (e.g., a
                              hundred feet or so).

        3.10.3  When a number is used as an adjective, insert a hyphen between the number and the
               unit symbol (e.g., 100-mL volumetric flask, 1-L sample).

        3.10.4  When writing decimal numbers of value less than one, place a zero before the decimal
               point (e.g., 0.45 g).

        3.10.5  Do not point-off numbers of four figures (1234) except in tables when they occur in a
               column containing numbers of more than four figures.. Point-off numbers of more than
               four figures, using commas with no spaces (e.g.,  1,325,000).

        3.10.6  In expressing ranges and ratios in text, use 1 to 10 or 1:10, not 1-10.  A hyphen may
               be used for ranges in tables.

3.11     Significant digits

        Handle numbers with careful regard for correspondence between the data accuracy and the
        given number of digits. The number of significant digits should neither sacrifice nor
        exaggerate accuracy.

        3.11.1   Any digit that is necessary to define the specific value or quantity is significant.  For
               example, when measured to the nearest-1 m, a distance may be 157 m, which has
               three significant figures; when measured to the nearest 0.1 m, the distance may be
               157.4 m, which has four significant figures.                             :

        3.11.2  When adding or subtracting numbers with different degrees of precision, the answer
               should contain  no digits farther to the right than the least precise number.  Numbers
               should first be rounded to one digit farther'to the right than that of the least precise
               number.  The answer is then rounded to the same number of significant figures as the
               least precise number.

        3.11.3  For multiplication and division, the product or quotient should contain no more
               significant figures than are contained in the number with the fewest significant figures.

        3.11.4  Examples to distinguish the addition/subtraction and multiplication/division rules are:

               Addition:
               113.2 +  1.43 = 114.63, rounded to 114.6

               Subtraction:
               113.1 - 1.43 =  111.77, rounded to  111.8

               Multiplication:
               113.2 x  1.43 = 161.876, (rounded to 162)
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Method Gofete&jes and Format
               Division:
               113.1 -r 1.43 = 79.16, rounded to 79.2

               Note:  The product and quotient above should contain only three significant figures
               because the number 1.43 contains only three significant figures.  The above sum and
               difference, however, contain four significant figures, because digits that occur to the
               right of the last significant in the least precise number are rounded.

3,12   Order of magnitude

       Zeros may be used to indicate a specific value or to indicate the order of magnitude of a
       number. For example, in the  number 203,185,000, representing population rounded to
       thousands, the first six digits are significant. The last three digits are zeros that indicate the
       order of magnitude.

3.13   Rounding

       3.13.1  When the first digit discarded is less than five, the last digit retained is not changed.

       3.13.2  When the first digit discarded is five or greater, or when  five is followed by a digit
               other than zero, the last digit retained is increased by one.

       3.13.3  When the first digit discarded is exactly five followed only by zeros, the  last digit
               retained is rounded upward if it is an odd number and is  not adjusted if it is an  even
               number.

4.0   Content

In accordance with EMMC format, each analytical method must contain  17  specific topical sections in
a designated order. The required order and content of these sections are  listed and described below.
All of these sections are mandatory for all methods.

        1.0     Scope and  Application
       2.0     Summary of Method
       3.0     Definitions
       4.0     Interferences
       5.0     Safety
       6.0     Equipment and Supplies
       7.0     Reagents and Standards
        8.0     Sample Collection Preservation and Storage
        9.0     Quality Control
        10.0   Calibration and Standardization
        11.0   Procedure
        12.0   Data Analysis and Calculations
        13.0   Method Performance
        14.0   Pollution Prevention
        15.0   Waste Management
        16.0   References
        17.0   Tables, Diagrams, Flowcharts, and  Validation Data
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                                                                           Method Guidelines ana! Format
Starting with Section 11.0 Procedure, additional numbered sections may be inserted as required by the
particular method; however, the sections listed above must appear in each method in the order listed.
See Appendix B for examples of content described in this section.                    .

Note:  Subsections within each of the 17 required sections do not need to correlate directly to the
subsections included here.  In other words, the information mentioned  in 4.1.1 below might be covered
in two or more subsections in a method.

4.1    Scope and application

       This section outlines the purpose, range, limitations, and intended use of the method, and
       identifies target analytes.

       4.1.1    Define the purpose and intended use of the method.  State what the method is based
               upon, noting any relationship of the method to other existing analytical methods.
               Indicate whether the method is associated with a sampling method. Include the
               following statement:                                ,

               •       This method is for use in the Environmental Protection Agency's (EPA's) data
                      gathering and monitoring programs under the Clean Water Act, the Resource
                      Conservation and Recovery Act, the Comprehensive Environmental Response,
                      Compensation and Liability Act, and the Safe Drinking Water Act.

       4.1.2    List analytes that can be measured by the method, including each analyte's Chemical
               Abstracts Service Registry  Number (CASRN). If regulations cite other than the most
               commonly used analyte name, refer to the regulation.  For pesticides, use "acceptable
               common names." The use of registered trade names is permitted.

       4.1.3    Identify the matrix(ces) for which the method has been found satisfactory.

       4.1.4    Indicate the statistically determined method detection limit (MDL) and the analyte
               concentration range over which the method is applicable. State the matrix(ces) in
               which MDL was determined.  If the MDL is not available, report an instrumental
               detection limit and define how it was derived.  Indicate the minimum level (ML) and
               water quality criteria if appropriate to  the analyte and method.

       4.1.5    Describe method limitations, such as "This method is not applicable to saline water,"
               or "This method is not intended for determination of metals at concentrations normally
               found in treated and untreated discharges from industrial facilities." Indicate any
               means of recognizing cases where the method may not  be applicable to the sample
               under test.

       4.1.6    List any restrictions that may apply, such as "This method is restricted to use by or
               under the supervision of analysts experienced in ..."

       4.1.7    Include the following statement regarding performance-based methods:

               •       This method is performance-based. The laboratory is permitted to omit any
                      step or modify any procedure (e.g., to overcome interferences, to lower the
                      cost of measurements), provided that all performance requirements in this
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                       method are met.  Requirements for establishing method equivalency are given
                       in Section 9.1.2.

        4.1.8    Include the following statements:

                •      Each laboratory that uses this method must demonstrate the ability to generate
                       acceptable results using the procedure in Section 9.1.2.

 42     Summary of Method

        This section provides an overview of the method procedure and quality assurance.

        4.2.1    Outline, specifying amounts of sample and reagent, the procedure that is followed to
                determine the presence or absence of the listed analytes.  Include any sample
                pretreatment, such as filtration or digestion.  In this description, identify the basic steps
                involved in performing the  method, but omit the details that are a necessary part of the
                complete statement of procedure.

                4.2.1.1  For chemical methods, state the type of procedure (colorimetric, electrometric,
                       volumetric, etc.) and describe the source  of color, major chemical reaction,
                       including pertinent chemical equations, etc. For instrumental methods, state the
                       technique.

                4J2.1.2  Use the passive voice, e.g., "Instrumental drift is corrected by using internal
                       standardization," rather than "Correct instrumental drift by using internal
                       standardization."

        4.2.2    Identify the determinative step in the method.

        4.2.3    State in a summary fashion how  quality is assured  in the method.

        4.2.4    List options to the method,  if applicable.

4.3     Definitions

        This section includes definitions of  terms, acronyms, and abbreviations used in the method.  If
        preferred, definitions may be provided in a glossary at the end of the method or manual. In
        this case, the definitions section must still appear hi the method, with a notation that
        definitions are provided in a glossary at the end of the method.  Refer  to the specific section
        number of the glossary.

        4.3.1    Include an introductory statement as follows:

                •       The definitions and  purposes  below are specific to this method, but have been
                       conformed to common usage as much as  possible.

        4.3.2    List units of weight and measure and their abbreviations or acronyms used in the
                method.
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                                                                             Method Guidelines and Format
        4.3.3   Alphabetically list and define terms, acronyms, and abbreviations used in the method.
                Where appropriate, include the purpose (e.g., The purpose of the field blank is to
                determine if the field of sample transporting procedures and environments have
                contaminated the sample).

        4.3.4   Include definitions of the terms may, may not, must, and should, as follows:

                •       May: This  action, activity, or procedural step is neither required nor prohibited.
                •       May not: This action, activity, or procedural step is prohibited.
                •       Must: This action, activity, or procedural step is required.
                •       Shall: This action, activity, or procedural step is suggested but not required.
                       Should: This action, activity, or procedural step is suggested but not required.
 4.4
Interferences

This section identifies known or potential interferences that may occur during use of the
method, and describes ways to reduce or eliminate interferences.
        4.4.1
        4.42
       Describe any known or potential problem(s) (e.g., sample or equipment contamination,
       instrument noise) that may be encountered during the performance of the method and
       the source of the problem(s).  Recommend techniques to avoid or minimize the
       problem(s) (e.g., ways to reduce sample or equipment contamination, or instrument
       noise).

       Identify any substances, ions, or properties that are known to or likely to cause
       interference and the amounts that are known to or likely to interfere.  Sometimes, this
       information can be obtained only by observation during the analysis.  In such cases,.
       include appropriate notes under "Procedure" or "Data Analysis and Calculations."
4.5    Safety
       This section describes special precautions needed to ensure personnel safety during the
       performance of the method.  Procedures described here should be limited to those which are
       above and beyond good laboratory practices.  The section must contain information regarding
       specific toxicity of analytes or reagents.
       4.5.1
       4.5.2
       Identify and warn analysts of potential hazards associated with using the method (e.g.,
       toxicity or carcinogenicity of analytes or reagents, explosions, fire, radiation).
       Recommend techniques to minimize hazards where possible (e.g., performing
       operations in a hood or glove box).

       Where the toxicity or carcinogenicity of each compound or reagent has not been
       precisely determined, include the following statement:

       •      The toxicity of carcinogenicity of each analyte or reagent has not been
              precisely determined; however, each chemical should be treated as a potential
              health hazard.  Exposure to these chemicals should be reduced to the lowest
              possible level. It is suggested that the laboratory perform personal hygiene
              monitoring of each analyst using this method and that the results of this
              monitoring be made available to the analyst.
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       453    Indicate the steps in the procedure at which hazards that could damage equipment may
               occur by use of the word CAUTION in boldface type, followed by the details of the
               precautionary measures that must be taken. If any step in the procedure could result in
               personal injury or death, include the word WARNING in boldface type, followed by
               the details of the protective measures  that must be taken.

       4.5.4    Include the following statements:

                      This method does not address all safety issues associated with its use.  The
                      laboratory is responsible for maintaining a safe work environment and a
                      current awareness file of OSHA regulations regarding the safe handling of the
                      chemicals specified in this method. A reference file of material safety data
                      sheets (MSDSs)  should be available to all personnel involved in these
                      analyses.  Additional information  on laboratory safety can be found in
                      References	.                                  .

4.6    Equipment and Supplies

       This section lists and describes all nonconsumable supplies and equipment needed to perform
       the method.

       4.6.1    Include the following statement as a note preceding the list of equipment and supplies:

               Note:  Brand names, suppliers, and part numbers are cited for illustrative purposes
               only. No endorsement is implied.  Equivalent performance may be achieved using
               equipment and  materials other than those specified here,  but demonstration of
               equivalent performance  that meets the requirements of this method is the responsibility
               of the laboratory.

        4 62   Categorize and list required equipment and supplies by the logical order of use;  e.g.,
               sampling equipment, equipment for glassware cleaning, equipment for calibration,
               equipment for sample extraction, etc.. Do not list common laboratory equipment, but
               do include special, or modified forms of unusual sizes or numbers of common
               equipment that are required or that may require special preparation.

        4.6.3   Describe the essential features of each required item.  Include schematic drawings as
               needed to clarify or supplement apparatus descriptions.

        464   Avoid the use  of trademarks, brand names, trade names, or suppliers unless a specific
               manufacturer's product is required for a well-defined reason or the availability of the
               product  is limited (i.e.,  the apparatus is unique or unusual).  For example, when special
               types of glassware are required, such as heat-resistant, chemical-resistant, etc., state the
                significant characteristic desired rather than a trademark ("borosilicate glass" rather
                than Pyrex or Kimax).  If only a single source is known, that supplier may be
                identified.

         4.6.5   Whenever a brand name is used, include "or equivalent" following  the brand name or
                part number to demonstrate that use of another product is acceptable.

         4.6.6   Include any special glassware cleaning instructions.
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       4.6.7   List special facilities required, such as a special room for handling hazardous materials.

4.7    Reagents and Standards

       This section lists and describes all reagents and standards required to perform the method, and
       provides preparation instructions and/or suggested suppliers as appropriate.

       4.7.1    List the name of the reagent and the necessary purity, followed by any descriptive
               terms.  List reagents in a logical order (e.g., by order of occurrence or use, by group).
               The method should require that reagents be ACS Reagent Grade unless otherwise
               specified.                 .

       4.7.2    Spell out the full name of inorganic reagents when first used, and include within
               parentheses the exact chemical formula, showing its water of crystallization, etc.
               Subsequently, refer to inorganic compounds by formula if they can be specified clearly
               in this way.  As exceptions, always spell out the word "water" and the names of
               substances in their elemental state (e.g., "lead" not "Pb," "oxygen" not "02").

       4.7.3    Spell out organic, organometallic, or complex inorganic compounds; chemical
               formulae are not necessary. Cite the CASRN to avoid ambiguity.

       4.7.4    Avoid the use of trademarks and names of patented products. Use chemical names
               and common names, unless a specific product is  required for a well-defined reason.
               The use of registered trade names is permitted.

       4.7.5    Unique  and unusual reagents can be named by brand.  Whenever a brand name is
              used, include "or equivalent" following the brand name to demonstrate that another
              product can be used.

       4.7.6   Specify the concentration of inorganic reagents in applicable terms, as follows:
              Concentrated acids and bases

              Dilute acids and bases


            .  Nonstandardized solutions
                                                    density

                                                    volume ratio, x + y (x volume of reagent
                                                    added to y volume by water)

                                                    normality, expressed decimally; or the
                                                    equivalent of 1 mL of solution in terms of
                                                    grams of a given element expressed as 1 mL =
                                                    x.xx g of...

       4.7.7    Specify filter paper by describing the significant characteristic such as porosity, rate of
               filtering ash content, etc., or by reference to ASTM Specification Dl 100 for Filter
               Paper for Use in Chemical Analysis.

4.8    Sample Collection,  Preservation, and Storage                          .              *

       This section provides requirements and instructions for collecting, preserving, and storing
       samples.
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       4.8.1    Give detailed directions for collecting, filtering (if applicable), preserving, shipping,
               and storing-samples.

       4.8.2    Use preservation procedures and holding times consistent with those specified .in
               current EPA publications or regulations and with other methods for the same analytes.

4.9    Quality Control                                                               -

       This section cites the procedures  and analyses required to fully document the quality  of data
       generated by the method. The required components of the laboratory's quality assurance (QA)
       program and specific quality control (QC) analyses are described in this section.  For each QC
       analysis, the complete analytical procedure, the frequency of required analyses, and
       interpretation of results are specified.                                    ^

       Note:  To ensure data quality, water methods must specify a comprehensive laboratory QA
       program. The minimum QC requirements that must be included in methods proposed at 40
       CFR Part 136 or Part 141 are specified in [use the Federal Register citation by which this
       streamlining initiative is promulgated].  The method must specify QC acceptance criteria in
       accordance with Chapter 3, "Quality Control Requirements", of the Guide to Method
       Flexibility and Approval of EPA  Water Methods included in the  notice referenced above.

       4.9.1    Include the following statements in the first subsection (Section 9.1):

               •       Each laboratory that uses this method is required to operate a formal  quality
                       assurance program (Reference	).  The minimum requirements of this
                       program consist of an initial demonstration of laboratory capability, ongoing
                       analyses of standards and blanks as a test of continued performance, and
                       [complete as appropriate to the method	]. Laboratory
                       performance is compared to established performance criteria to determine if the
                       results of analyses meet the performance characteristics of the method.

               •       The analyst shall make an initial demonstration of  the ability to generate
                       acceptable accuracy and precision with this method.  This ability is established
                       as described in Section 9.2.

        4.92   In Section 9.1, cite any options that the analyst is permitted, e.g., alternate extraction,
               concentration, or cleanup procedures; changes in columns or detectors.  Specify that
               the analyst is required to repeat the required initial demonstration of laboratory
               capability each time a modification is made to the method.. Include the following
               statements:

                »       Each time a modification is made to the method, the analyst is required to
                       repeat the procedure in Section 9.2.  If the change will affect the  detection
                       limit of the method, the laboratory is required to demonstrate that the MDL
                       (40 CFR Part 136, Appendix B) is lower than the  MDL for that analyte in this
                       method, or one-third the regulatory compliance level, whichever is higher.  If
                       the change will affect calibration, the analyst must recalibrate the instrument
                       according to Section 10.

                •       Changes that degrade  method performance are not allowed. If an analytical
                       technique other than the techniques specified hi this method is used, that
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                                                                      Method Guidelines and Format
                technique must have a specificity equal to or better than the specificity of the
                techniques in this method for the analytes of interest.

        •       The laboratory is required to maintain records of modifications made to this
                method.  These records include the following, at a minimum:
                       The names, titles, addresses, and telephone numbers of the analyst(s)
                       who performed the analyses and modification, and of the quality
                       control officer who witnessed and will verify the analyses and
                       modification.              -   .
                       A listing of analytes measured, by name and CASRN.
                -       A narrative stating reason(s) for the modification(s).
                       Results from all QC tests comparing the modified method to this
                       method, including:
                       (a)    Calibration (Section 10)
                       (b)    Calibration verification (Section 9.5)
                       (c)    Initial precision and recovery (Section 9.2.2)
                       (d)    Analysis of blanks (Section 9.4)
                       (e)    Accuracy assessment (Section 9.3)
                       (f)     Ongoing precision and recovery (Section 9.6)

                       Data that will allow an independent reviewer to  validate each
                       determination by tracing the instrument output (weight or other signal)
                       to the final result.  These data are to include:
                       (a)     Sample numbers and other identifiers
                       (b)    Extraction dates
                       (c)     Analysis dates and times
                       (d)    Analysis sequence/run chronology
                       (e)     Sample weight or volume
                       (f)     Extract volume
                       (g)    Make and model of analytical balance and weights traceable to
                              NIST                    ' •
                       (h)     Copies of logbooks, printer tapes, and other recordings of raw
                              data                                         •
                       (i)     Data system outputs, and other data to link the raw data to the
                              results reported

4.9.3    In the remainder of Section 9.1, outline the QC requirements that will be described in
        the section, and the purpose for each type of QC (e.g., blanks, matrix spikes/matrix
        spike duplicates, calibration verification).

4.9.4    In Section 9.2, describe in detail the initial demonstration of laboratory capability.

4.9.5    Describe the procedure for  matrix spikes, calculating percent recoveries, and
        calculating relative percent  difference for duplicates.

4.9.6    Provide instructions for analysis of blanks, e.g., laboratory reagent blanks, method
        blanks.

4.9.7    Specify requirements for calibration verification.

4.9.8 •   Provide instructions for analysis of ongoing precision and recovery standards.
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 Method GutdeHnes and Format
         4.9.9   Include requirements for analysis of quality control samples (QCS).

         4.9.10  Include the following statement at the end of Section 9.0:

                •       Depending upon specific program requirements, field replicates and field
                        spikes of the analytes of interest into samples may be required to assess the
                        precision and accuracy of the sampling and sample transporting techniques.

 4.10     Calibration and Standardization

         This section describes the method/instrument calibration and standardization process, and
         required calibration verification. Corrective actions are described for cases when performance
         specifications are not met.

         4.10.1   Specify operating conditions or refer to manufacturer's recommended operating
                conditions.  If appropriate, specify a precalibration routine as needed to document
                instrument stability.

        4.10.2   Give detailed instructions for the use of standards to prepare calibration lines or tables.
                Include the number of calibration standards, the need for blanks, the frequency of
                calibration checks, the critical range, etc.

        4.10.3   Give detailed instructions for internal standardization, including number and
                concentration of internal standards.

        4.10.4   Include instructions for calibration data storage.

4.11    Procedure

        This section describes  the sample processing and instrumental analysis steps of the method,
        and provides detailed instructions to analysts.

        4.11.1   For methods used for determination of a method-defined analyte, include the following
                statement in the introductory portion of Section 11.0 Procedure:

                •       This method is entirely empirical. Acceptable results can be obtained only by
                       strict adherence to all details.

                Do not include this statement in methods for which the analyte is a chemical or
                physical parameter, the characteristics of which are known (e.g., oil and grease, COD,
                BOD).

        4.11.2   Include in proper sequence detailed directions for performing the analysis.

                4.11.2.1        Include steps that are essential to the process and avoid unnecessarily
                              restrictive instructions.

                4.11.2.2        Organize the procedure by logical  order of activity, e.g., sample
                              preparation, extraction, analysis.
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                                                                             Method Guidelines and Format
               4.11.2.3        Describe the procedure in the imperative mood, present tense, e.g.,
                              "Heat the sample aliquot," rather than "The sample aliquot should be
                              heated." Comments and descriptive information that are not in the
                              imperative mood may be included, as appropriate.

               4.11.2.4        Write the text so that it is concise and easily understandable.

               4.11.2.5        When alternative procedures are given, state which is preferred.

        4.11.3  In chemical methods, specify the size of sample aliquot and indicate the required
               measurement accuracy.  (There is no need to weigh a sample to five significant figures
               in a spectrophotbmetric method where the final absorbance measurement yields data
               with only three significant figures).

        4.11.4  Include "Notes" throughout the procedure to highlight critical points.  Include notes of
               "WARNING" or "CAUTION" as appropriate to identify known or potential hazards to
               the analyst or the equipment, respectively.            ,

        4.11.5  Indicate steps in which timing is critical, e.g., if a determination may riot be
               interrupted overnight. For a color reaction,  indicate how long the color is stable.

4.12    Data Analysis and Calculations

        This section provides instructions for analyzing data, and equations and definitions of constants
        used to calculate final sample analysis results.

        4.12.1  Calculations—Provide directions for calculating the results of the analysis, including
               any equations.
               4.12.1.1
               4.12.1.2
               4.12.1.3
               4.12.1.4
Use the imperative mood, e.g., "Report results to three significant
figures," rather than "Results should be reported to three significant
figures."

Where there may be ambiguity of meaning, spell out names in the text
(e.g., total Kjeldahl nitrogen) but use the abbreviations (e.g., TKN) in
text where the meaning is clear, and in equations.

Define the symbols used in the equation immediately under the
equation.

Use numerical values for any constants:  Identify dilution factors,
titration factors, etc:
       4.12.2   Reporting results

               4.12.2.1         Indicate the units in which the results are to be reported (e.g., ug/L,
                              mg/kg).

               4.12.2.2         If the sample is a solid material such as a sediment or sludge, indicate
                              whether results are to be reported as wet weight or dry weight.
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Method GuKfe/ines and Format
               4.12.2.3        Specify the number of significant figures to be reported.

               4.12.2.4        Require that all values obtained by various QC procedures are reported
                              along with the calculated results of the analysis.

       4.12.3  Interpretation of results - Use this heading in place of Calculations when the results of
               the analysis must be expressed in descriptive form, relative terms, or abstract values.
               List and define the descriptive terms or classifications used.

4.13   Method Performance

       This section provides method performance criteria for the method, including precision/bias
       statements regarding detection limits and source/limitations of data produced using the method.

       Note: Requirements for validating new methods are specified in [cite the volume and page
       number of the Federal Register in which the streamlining is promulgated].

       4.13.1   Explain how the method was validated.  Provide a detailed description of method
               performance, including data on precision, bias, detection limits (including the method
               by which they were determined and matrices to which they apply), and statistical
               procedures used to develop performance specifications.

                      Note:  This information can be provided through reference to the method
                      validation study.

       4.13.2  At a minimum, state single-operator precision and accuracy on reagent water. If other
               sample types have been investigated, also provide this information for them.

       4.13.3  If a collaborative study has been completed, describe the study and report the number
               of participating operators and laboratories, spike concentrations, level of replication,
               types of background waters, and any other significant aspects.  If the study has been
               documented, cite the study report and include it in the References section.  When
               citing reference documentation, the details of the study do not have to be included in
               this section.

4.14   Pollution Prevention

       This  section describes aspects of the method  that minimize or prevent pollution known to be
       or potentially attributable to the method.

       4.14.1  Cite potential  sources of pollution  attributable to the method.

       4.145  Recommend ways,to minimize pollution.

4.15   Waste Management

       This section describes minimization and proper disposal of waste and samples.

        4.15.1  Include the following statement as the first subsection:
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             .   •       It is the laboratory's responsibility to comply with all federal, state,and local
                       regulations governing waste management, particularly the hazardous waste
                       identification rules and land disposal restrictions, and to protect the air, water,
                       and land by minimizing and controlling all releases from fume hoods and
                       bench operations. Compliance with all sewage discharge permits and
                       regulations is also required.

        4.15.2  Provide instructions for sample and waste handling and disposal.

        4.15.3  Include the following statement as the last subsection:

               •       For further information on waste management, consult "The Waste
                       Management Manual for Laboratory Personnel," and "Less is Better:
                       Laboratory Chemical Management for Waste Reduction," both available from
                       the American Chemical Society's Department of Government Relations and
                       Science Policy, 1155 16th Street N.W., Washington DC, 20036.

4.16    References

        This section lists references for source documents and  publications that  contain ancillary
        information.

        Note: Each method should be a free-standing document, providing all information necessary
        for the method user to perform the method may be found. References within a method should
        be restricted to associated or source  material.  Procedural steps or instructions should not be
        referenced as being found elsewhere, but should be included in total within the method.

        4.16.1   Include references  for other, related EPA methods; and published studies/articles
               relating to method  performance, techniques, or analytes, and health and safety.

        4.16.2   List references in the order cited in the method, and assign each reference an
               identification number using arabic numerals.

        4.16.3   As a rule, do not list documents that are not readily accessible to the reader (e.g.,
               unpublished theses, personal communications, private correspondence).  If it is,
               important to list these types of documents, identify where the reader may obtain a
               copy of the document.

4.17    Tables,  Diagrams, Flowcharts, and Validation  Data               .

        This section contains all method tables and figures (diagrams and flowcharts), and may contain
        validation data referenced in the body of the method.

        4.17.1   In addition to tables and figures, include additional useful information.  Examples of
               such information include:

               4.17.1.1        Notes on significance  and interpretation of the method, used to  amplify
                             the statement in the text.
               4.17.1.2
Development of equations used in the calculations.
                                               23
                                                                                         July 1996

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Method Guidelines and Format
               4.17.1.3

4.18    Glossary
Charts or supplementary information for computations.
       This optional section contains a glossary of terms, acronyms, abbreviations, and symbols used
       in the method.
                                                                  • • \       •               *
       Note: This information may appear in the Definitions section of the method (Section 3.0) or
       may be included in a glossary at the end of the method.

       4.18.1   In the first subsection of the glossary, identify units of weight and measure used in the
               method and their abbreviations.

       4.18.2  In the second subsection, define key terms and all acronyms used in the method.

               4.18.2.1         List terms, acronyms, and abbreviations alphabetically.

               4.18.2.2        Definitions should appear only once.  Where an acronym or
                              abbreviation represents a term that is defined under its full name,
                              reference the full name as the definition for acronym or abbreviation.
My 1996
                                                24

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                                           Method Guidelines and Format
                  Appendix A



Standard Acronyms, Abbreviations, and Symbols

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                                                                         Method Guidelines and Format
 ampere
 average
 calibration standard
 centimeter
 cubic centimeter
 day
 degree Celsius
, diameter
 equation
 figure
 foot                      ,
 gallon
 gas chromatograph/chromatography
 gel permeation chromatograph/
  chromatography
 gram
 grams per liter
 greater than
 high performance liquid
  chromatograph/chromatography
 high resolution GC   '
 high resolution MS
 hour
 hydrogen ion concentration,
  negative logarithm of
 inch                       ,
 initial precision and recovery
 inside diameter
 instrument detection limit
 Kuderna-Danish concentrator
 kilogram
 laboratory control sample
 laboratory duplicate
 laboratory fortified blank
 laboratory fortified sample matrix
 laboratory reagent blank •
 less than
 linear dynamic range
 liter
 logarithm (common)
 logarithm (natural)
 mass spectrometer/spectrometry
 mass to charge ratio
 matrix spike
 matrix spike duplicate
 maximum
 meta
 method detection limit
 meter
 microgram
 microliter
 amp
 avg
 CAL
 cm
 cm3
 (do not abbreviate)
 °C
 dia
 Eq     '
 Fig. (only when followed by' a numeral)
 ft   .
 gal
 GC
 GPC
g
HPLC
HRGC
HRMS
h

PH
in.
IPR
ID
IDL
K-D
kg
LCS
LD
LFB
LFM
LRB
<
LDR
L
log
log e or In
MS
m/z
MS
MSD
max
m-
MDI,
m
"g
uL
                                             A-1
                                                                                      July 1996

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 Method Sidelines and Format
 milliequivalent
 milligram
 milligram per gram
 milligram per Liter
 milligram per milliliter
 milliliter
 millimeter
 millimeter of mercury (pressure)
 millisecond
 millivolt
 minimum
 minimum level
 minute
 molal
 molar        «
 molecular ion
 mole
 month
 most probable number
 nanogram
 nanogram per liter
 nanometer
 normal
 number
 ongoing precision and recovery
 ortho
 outside diameter
 page
 pages
 para
 part per billion
 part per million
 part per quadrillion
 part per trillion
 per
 percent
 pico (prefix)
 picogram
 pound
 pounds-per-square inch gauge
•precision and recovery
 quality assurance
 quality control
 quality control sample
 quart
 reference
 relative centrifugal force
 relative percent difference
 relative response
 relative standard deviation
 response factor
 meq
 mg
 mg/g
 mg/L
 mg/mL
 mL
 mm
 mm Hg
 ms
 mV
 min
 ML
 min
 (do not abbreviate)
 M
 M                           •
 rnol
 (do not abbreviate)
 MPN
 ng
 ng/L
 nm
 N
 No. (only when followed by a numeral)
 OPR
 o-
 OD
 P-
 pp.
P-
 ppb
 ppm
 ppq
 ppt
 / (when used in expressions with unit symbols)
 %
 P
 Pg
 Ib
 psig
 PAR
 QA
 QC
 QCS
 qt
 Ref
 RCF
 RPD
 RR     '
 RSD
 RF
My 1996
   A-2

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                                                                           IWetfiocf Guidelines and Format
 revolutions per minute
 second
 selected ion current profile
 solid phase extraction
 Soxhlet/Dean-Stark extractor
 specific gravity
 micrometer
 volt
 volume (of a publication)
 volume per unit volume
 watt
 weight per unit volume
year
 rpm
 s                    •
 SICP
 SPE
 SDS
 sp gr
 um
 V
 Vol. (only when followed by a numeral)
 v/v
W
w/v
(do not abbreviate)
                                             A-3
                                                                                       July 1996

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                                                       Method Guidelines and fortnaf
                            Appendix B


                    Example of Method Format

"Method 1664: N-Hexane Extractable Material (HEM) and Silica Gel Treated
 N-Hexane Extractable Material (SGT-HEM) by Extraction and Gravimetry
          (Oil and Grease and Total Petroleum Hydrocarbons)"

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                                  Method  1664
     N-Hexane Extractable Material (HEM) and Silica Gel Treated N-
                    Hexane Extractable Material (SGT-HEM)
                           by Extraction and Gravimetry
            (Oil  and Grease and Total  Petroleum Hydrocarbons)
1.0   Scope and Application
 1.1
 1.2
 1.3
1.4
1.5
1,6
1.7
 This method is for determination of n-hexane extractable material (HEM) and n-hexane extracta-
 ble material that is not adsorbed by silica gel (SGT-HEM) in surface and saline waters and
 industrial and domestic aqueous wastes.  Extractable materials that may be determined are
 relatively non-volatile hydrocarbons, vegetable oils, animal fats, waxes, soaps, .greases, and
 related materials.  The method is based on prior Environmental Protection Agency (EPA) and
 association methods for determination of "oil and grease" and "total petroleum hydrocarbons"
 (References 16.1 and 16.2).
 This method is for use in the Environmental Protection Agency's (EPA's) survey and monitoring
 programs under the Clean Water, Act.  "Oil and grease" is a conventional pollutant defined in the
 Act and codified at 40 CFR 401.16. The term "n-hexane extractable material" reflects that this
 method can be applied to materials other than oils and greases. Similarly, the term "silica gel
 treated n-hexane extractable material" reflects that this method can be applied to materials other
 than aliphatic petroleum hydrocarbons that are not adsorbed by silica gel.
 This method is not applicable to measurement of materials that volatilize at temperatures below
 approximately 85°C.  Petroleum fuels from gasoline through #2 fuel oil may be partially lost in
 the solvent removal operation.
 Some crude oils and heavy fuel oils contain a significant percentage of materials that are not
 soluble in n-hexane.  Accordingly, recoveries of these materials may be low.
 This method is capable of measuring HEM and SGT-HEM in the range of 5 to 1000 mg/L, and
 may be extended to higher levels by analysis of a smaller sample volume collected separately.
 For this method, the Method Detection Limit (MDL; 40 CFR 136, Appendix B) has been
 determined as 1.4 mg/L for HEM and 1.6 mg/L for SGT-HEM (Reference 16.9), and the Mini-
 mum Level (ML; Reference 16.3) has been set at 5.0 mg/L for HEM and SGT-HEM (Reference
 16.9).
This method is "performance-based".  The analyst is permitted to modify the method to over-
come interferences or lower the cost of measurements, provided that all performance criteria in
 this method are met.  The requirements for establishing method equivalency are given in Section
 9.1.2.                                         '
April 1995

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   1.8   Any modification of this method, beyond those expressly permitted, shall be considered a major
        modification subject to application and approval of alternate test procedures under 40 CFR 136.4
        and 136.5.
   1.9   Each laboratory that uses this method must demonstrate the ability to  generate acceptable results
        using the procedure in Section 9.2.

  2.0   Summary of Method

   2.1   A 1-L sample is acidified to pH <2 and serially extracted three times with n-hexane in a
        separatory funnel.  The extract is dried over sodium sulfate.
   2.2   The solvent is evaporated from the extract and the HEM is weighed.  If the HEM is to be used
        for determination of SGT-HEM, the HEM is redissolved in n-hexane.
   2.3   For SGT-HEM determination, an amount  of silica gel proportionate to the amount of HEM is
        added to flic solution containing the redissolved HEM to remove adsorbable materials. The
        solution is filtered to remove the silica gel, the solvent is evaporated, and the SGT-HEM is
        weighed.
   2.4   Quality is assured through calibration and testing  of the extraction, concentration, and gravimet-
        ric systems.

  3.0   Definitions

   3.1   HEM and SGT-HEM are method-defined  analytes; i.e., the  definitions of both HEM and SGT-
        HEM are dependent on the procedure used.  The nature of the oils and/or greases, and the
        presence of extractable non-oily  matter in  the sample will influence the material measured and
        interpretation of results.
  32.   Definitions for terms used in this method are given in the glossary at the, end of the method.

,  4.0   Interferences

  4.1   Solvents, reagents, glassware, and other sample-processing hardware may yield artifacts  that
        affect results.  Specific selection of reagents and purification of solvents may be required.
  4.2   All materials used in the analysis shall be  demonstrated to be free from interferences under the
        conditions of analysis by running laboratory blanks as described in Section 9.4.
  4.3   Glassware is cleaned by washing in hot water containing detergent, rinsing with tap and distilled
        water, and rinsing with solvent or baking.  Boiling flasks that will contain the extracted  residue
        are dried in an oven at 105-115°C and stored in a desiccator.
  4.4   Sodium sulfate and silica gel fines have the potential to inflate results  for HEM and SGT-HEM •
        by passing through the filter paper.  If the filter paper specified in this method is inadequate for
        removal of these fines, use of a 0.45-micron filter is recommended.
  4.5   Interferences extracted  from samples will vary considerably from source to source, depending
        upon the diversity of the site being samplecl.
                                                                                          April 1995

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5.0   Safety
 5.2
 5.3
 5.4
 5.1   The toxicity or carcinogenicity of each reagent used in this method has not been precisely
      determined; however, each chemical should be treated as a potential health hazard. Exposure to
      these chemicals should be reduced to the lowest possible level.  It is suggested that the laborato-
      ry perform personal hygiene monitoring of each analyst using this method and that the results of
      this monitoring be made available to the analyst.
      n-Hexane has  been shown to have increased neurotoxic effects over other .hexanes and some
      other solvents. Inhalation of n-hexane should be minimized by performing all operations with n-
      hexane in a hood or well-ventilated area.                  -
      Unknown samples may contain high concentrations of volatile toxic compounds. Sample
      containers should be opened in a hood and handled with gloves to prevent exposure.
      This method does not address all safety  issues  associated with its use.  The laboratory is respon-
      sible for maintaining a safe work environment  and a current awareness file of OSHA regulations
      regarding the safe handling of the chemicals specified in this method,  A reference file of
      material safety data sheets (MSDSs) should be available to all personnel involved in  these
      analyses.  Additional information on laboratory safety can be found in  References  16.4-1(5.6.

6.0   Equipment and Supplies

   Note:    Brand names, suppliers, and part  numbers are for illustrative purposes only. No
   endorsement is implied.  Equivalent performance may be achieved using apparatus and materials
   other than those specified here, but demonstration of equivalent performance that meets the
   requirements of this method is the responsibility of the laboratory.

 6.1   Sampling equipment.
       •6.1.1  Sample collection bottles—Glass, approximately  1-L, with PTFE-lined screw  cap.

   Note:    In those instances necessitating collection of a smaller aliquot, a smaller sample
   container may be used.
6.2
       6.1.2  Cleaning.
                                  /          ,
             6.1.2.1  Bottles—Detergent water wash, tap water rinse, cap with aluminum foil, and bake
                    at 200-250°C for 1 h minimum prior to use. Solvent rinse may be used in place
                    of baking.
             6.1.2.2  Liners for screw  caps—Detergent water wash, tap water and solvent rinse, and
                    bake at 110-200°C for 1 h minimum prior to use.
       6.1.3  Bottles and liners must be lot-certified to be free of artifacts by running laboratory blanks
             according to this method (per Section 9.4). If blanks from bottles and/or liners without
             cleaning or with  fewer cleaning steps than required above show no detectable materials,
             the bottle and liner cleaning  steps that do not eliminate these artifacts may be omitted.
      Equipment for glassware cleaning.
       6.2.1  Laboratory  sink with overhead fume hood.
April 1995

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       6.2.2  Oven—Capable of maintaining a temperature within ± 5°C in the range of 1QO-250°C.
6.3   Equipment for calibration.
       6.3.1  Analytical Balance—Capable of weighing 0.1 mg.
       6.3.2  Volumetric flask—Glass, 100-mL.
       6.3.3  Vials—Assorted sizes, with FTFE-lined screw caps.  _
       6.3.4  Volumetric pipette—Glass, 5-mL.
6.4   Equipment for sample extraction.
                                        '
       6.4.1  Balance—Top loading, capable of weighing 500-2000 g within '± 1 %.
       6.4.2  Glass stirring rod.                                         .
       6.4.3  Separatory funnel—Glass, 2000-mL, with PTFE stopcock.
       6.4.4  Funnel—Large, glass, for pouring sample into separatory funnel.
               «
       6.4.5  Centrifuge—Capable of spinning at least four 100-mL glass centrifuge tubes at 2400 rpm
             minimum.
       6.4.6  Centrifuge tubes—100-mL glass.
6.5   Equipment for removal of water, sodium sulfate, and silica gel fines.
       6.5.1  Funnel—Analytical, glass.
       6.5.2  Filter paper—Whatman No. 40 (or equivalent), to fit funnel.
6.6   Equipment for solvent evaporation.  •
                                           *
       6.6.1  Water bath or Steam bath—Capable of maintaining a temperature of at least 85°C.
       6.6.2  Flask—Boiling, I25-mL (Corning No. 4100 or equivalent).
       6.6.3  Distilling head—Claisen (VWR Scientific No. 26339-005, or equivalent), includes
             Claisen-type connecting tube and condenser.
       6.6.4  Distilling adaptor (attached to the distilling head and to the waste collection flask for
             recovery,of solvent).
       6.6.5  Waste collection flask (attached to the distilling adaptor for collection of the distilled sol
             vent).
       6.6.6  Ice bath or recirculating chiller (to aid in the condensation and collection of the distilled
             solvent).
       6.6.7  Vacuum, pump or other source of vacuum.
       6.6.8  Tongs, for handling the boiling flask (Baxter Scientific Products No. T5007-2, or equiva-
             lent).
       6.6.9  Desiccator—Cabinet- or jar-type, capable of keeping the boiling flask (Section 6.6.2) dry
             during cooling.
6.7   Equipment for removal of adsorbable materials.
       6.7.1  Magnetic stirrer.
       6.7.2  PTFE-coated magnetic stirring bars.
       6.7.3  Graduated cylinder—500-mL, capable of measuring ± 5 mL.
                                                                                          April 1995

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                                                                                        Method 1664
        6.7.4  Pipettes—Assorted sizes, calibrated to within ± 0.5 percent.

 7.0   Reagents and Standards

  7.1   Reagent water—Water in which HEM is not detected at or above the Minimum Level of this
       method.  Bottled distilled water, or water prepared by passage of tap water through activated
       carbon have been shown to be acceptable sources of reagent water.
  7.2   Hydrochloric or sulfuric acid—ACS, 1:1.  Mix equal volumes of concentrated HC1 or H2SO4 and
       reagent water.
       n-Hexane—85% purity, 99.0% min. saturated C6 isomers,  residue less than  1 mg/L.
       Acetone—ACS, residue less than 1 mg/L.
 7.5   Sodium sulfate—ACS,  granular anhydrous.                                  '
  7.3
  7.4
    Note:    Powdered sodium sulfate should not be used because traces of water may cause it to
    solidify.


 7.6  Boiling chips—Silicon carbide or fluoropolymer.
 7.7  Silica gel—Anhydrous, 75 - 150 micrometers, Davisil Grade 923 (Supelco 21447-7A, or equiva-
      lent). Dry at 200-250°C for 24 h minimum and store in a desiccator or tightly sealed container.
      Determine the n-hexane soluble material content of the silica gel by extracting 30 g of silica gel
      with n-hexane and evaporating to dryness. The silica gel must contain less than 5 mg of n-
      hexane soluble material per 30 g (< 0.17 mg/g).
      Hexadecane—98% minimum purity.                 -
      Stearic acid—98% minimum purity.
      Hexadecane/stearic acid (1:1) spiking solution—Prepare in acetone at a concentration of 4
      mg/mL each.    ,

      7.10.1  Place 400 ± 4 mg stearic acid and 400 ± 4-mg hexadecane in a 100-mL volumetric flask
             and fill to the mark with acetone.
 7.8
 7.9
7.10
   Note:   The solution may require warming for complete dissolution of stearic acid.


      7.10.2  After the hexadecane and stearic acid have dissolved, transfer the solution to a 100-150
             mL vial with fluoropolymer-lined cap. Mark the solution level on the vial arid store in
             the dark at room temperature.

      7.10.3  Immediately prior to use, verify the.level on the vial and bring to volume with acetone,
             if required.  Warm to redissolve all visible precipitate.

   Note:   If there is doubt of the concentration, remove 5.00 ± 0.0,5 mL with a volumetric pipet, place
   in a tared weighing pan, and evaporate to dryness in a fume hood. The weight must be 40 ± 1 mg.
April 1995

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 Method 1664
7.11   Precision and recovery (PAR) standard—Spike 5.00 ± 0.05 mL of the hexadecane/stearic acid
      spiking solution (Section 7.10) into 950-1050 mL of reagent water to produce concentrations of
      approximately 20 mg/L each of hexadecane and stearic acid. The PAR standard is used for the
      determination of initial precision and recovery (Section 9.2.2) and ongoing precision and recovery
      (Section 9.6).
7.12   The spiking solutions should be checked frequently for signs of degradation or evaporation using
      the test noted in Section 7.10.3, and must be replaced after six months, or sooner if degradation has
      occurred.                                                   '

8.0   Sample Collection, Preservation, and Storage

 8.1   Collect approximately one liter of representative sample in a glass bottle following conventional
      For those instances in which samples are thought to consist of complex matrices containing sub-
      stances (such as particulates or detergents) that may interfere with the extraction procedure, a
      smaller sample may need to be collected for analysis, sampling practices (Reference 16.7), except
      that the bottle must not be pre-rinsed with sample before collection.  To allow for potential QC
      failures, it is recommended that additional sample aliquots be collected.
        8.1.1  If analysis is to be delayed for more than a few hours, adjust the sample pH to less than 2
              with HC1 or H,SO4 solution (Section 7.2) at the time of collection, and refrigerate  at 0-4°C
              (40 CFR 136, Table II). To establish the volume of HC1 or H2SO4 required, collect a
              separate aliquot, adjust the pH of this aliquot to less than 2 with acid, and add the volume of
              acid determined to each sample bottle prior to collection. Do not dip pH paper, a pH
              electrode, a stirring rod, or other materials into a sample that will be used for HEM or SGT-
              HEM determination because substances in the sample may adhere to these materials.
        8.1.2  If a sample is known or suspected to contain greater than 1000 mg/L of extractable material,
              collect a proportionately smaller volume of sample (the volume required will depend upon
              the estimated amount of extractable material) in a glass bottle. Add a proportionately
              smaller amount of HC1 or H2SO4 solution to the smaller sample if preservation is necessary.
 82  Collect an additional two aliquots (1 L, additional smaller volume, or both) of a sample for each set
      often samples or less for the matrix spike and matrix spike duplicate.

    Note:   For those circumstances requiring the collection of multiple aliquots of one sample, each
    aliquot is to be collected in either of the following ways:  1) collect the total volume needed in one
    container, homogenize by mixing with a stir bar until a vortex forms, and siphon into individual
    bottles using a glass tube, 2) collect simultaneously in parallel, if possible, or 3) collect as grab
    samples in rapid succession.

 8.3  The high probability that extractable matter may adhere to sampling equipment and result in
       measurements that are biased low precludes the collection of composite samples for determination
       of oil and grease. Therefore, samples must be collected as grab samples.  If a composite measure-
       ment is required, individual grab samples collected at prescribed time intervals must be analyzed
       separately and the concentrations averaged.

  _                               .                                                          April1995

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                                                                                         Method 1664
  8.4   All samples must be refrigerated at 0-4°C from the time of collection until extraction (40 CFR 136
       Table II).
  8.5   All samples must be analyzed within 28 days of the date and time of collection (40 CFR 136  Table
       ID-

 9.0   Quality Control
  9.1
Each laboratory that uses this method is required to operate a formal quality assurance program
(Reference 16.8). The minimum requirements of this program consist of an initial demonstration of
laboratory capability, ongoing analyses of standards and blanks as a test of continued performance,
and analyses of matrix spike (MS) and matrix spike duplicate (MSD) samplesto assess accuracy
and precision.  Laboratory performance is compared to established performance criteria to deter-
mine if the results of analyses meet the -performance characteristics of the method.
 9.1.1  The analyst shall make an initial demonstration of the ability to generate acceptable accura-
       cy and precision with this method. This ability is established as described in Section 9.2.
 9.1.2  In recognition of advances that are occurring in analytical technology, the analyst is permit-
       ted certain options to improve separations or lower the. costs of measurements, provided that
       all performance specifications are met. these options include alternate extraction and
       concentration devices and procedures such as solid-phase extraction and Kuderna-Danish
       concentration.  Alternate determinative techniques, such as infra-red spectroscopy or
       immuno-assay, and changes that degrade method performance, are not allowed. If an
       analytical technique other than the techniques specified in this method is used, that tech-
       nique must have a specificity equal to or better than the specificity of the techniques in this
       method for HEM and/or SGT-HEM in the sample of interest. Specificity is defined as
       producing results equivalent to the results produced by this method for analytical standards
       (Section 9.2.2) and, where applicable, environmental samples (Section 9.2.3), and that meet
       all of the QC criteria stated in this method.
      9.1.2.1   Each time a modification is made to this method, the analyst is required to repeat
              the IPR test in Section 9.2.2 to demonstrate that the modification produces results
              equivalent to or better than results produced by this method. If the detection limit
              of the method will be  affected by the modification, the analyst must demonstrate
              that the MDL (40 CFR 136, Appendix B) is less than or equal to the MDL in this
              method or one-third the regulatory compliance level, whichever is higher. If the
              modified method is to be used for compliance monitoring, the discharger must also
              demonstrate that the modified method recovers an amount of HEM and/or SGT-
              HEM equivalent to the amount recovered by this method on each specific dischar-
              ge. The tests required for this equivalency demonstration are given in Section 9,2.3.
      9.1.2.2 "  The laboratory is required to maintain records of modifications made to this
              method.  These records include the following, at a minimum:
              9.1.2.2.1  The names,  titles, addresses, and telephone numbers of the anajfyst(s) who
                      performed the analyses and modification, and of the quality control offi-
                      cer who witnessed and will verify the analyses and modification.
April 1995'

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Method 1664
                    9.1.2.2.2 A listing of pollutant(s) measured (HEM and/or SGT-HEM).
                    9.1.2.2.3 A narrative stating reason(s) for the modification.  •
                    9.1.2.2.4 Results from all quality control (QC) tests comparing the modified
                            method to this method, including:
                            (a)  Calibration (Section 10).
                            (b)  Calibration verification (Section 9.5).
                            (c)  Initial precision and recovery (Section 9.2.2).
                            (d)  Analysis of blanks (Section 9.4).
                            (e)  Accuracy assessment (Section 9.3).
                            (f)  Ongoing precision and recovery (Section 9.6).
              • ,   9.1.2.2.5 .Data that will allow an independent reviewer to validate each determina-
                            tion by tracing the instrument output (weight or other signal) to the final
                            result.  These data are to  include:
                            (a) Sample numbers and other identifiers,
                            (b) Extraction dates.
                            (c) Analysis dates and times.
                            (d) Analysis sequence/run chronology.
                            (e) Sample weight or volume (Section 11.1.4).
                            (f) Extract volume for SGT-HEM (Section 11.5.2).
                            (g) Make andlnodel of analytical balance and weights traceable to
                                NIST.
                           , (h) Copies of logbooks, printer tapes, and other recordings of raw data.
                           ' (i) Data system outputs, and other data to link the raw data to the results
                                reported.
      9.1.3  Analyses of matrix spike and matrix spike duplicate samples are required to demonstrate
            method accuracy and precision and to monitor matrix interferences (interferences caused by
            the sample matrix).  The procedure and QC criteria for spiking are described in Section 9.3.
      9.1.4  Analyses of laboratory blanks are required to demonstrate freedom from contamination.
            The procedure and criteria for analysis of a blank are described in Section 9.4.
      9.1.5  The laboratory shall, on an ongoing basis, demonstrate through calibration verification and
            analysis of the ongoing precision and recovery sample that the analysis system is in control.
            These procedures are described in Sections 9.5 and 9.6, respectively.
      9.1.6  The laboratory should maintain records to define the quality of data that is generated.
            Development of accuracy statements is described in Sections 9.3.7 and 9.6.3.
      9.1.7  Accompanying QC for the determination of HEM and/or SGT-HEM is required per analyti-
            cal batch. An analytical batch is a set of samples extracted at the same time, to a maximum
            of 10 samples. Each analytical batch of 10 or fewer samples must be accompanied by a
            laboratory blank (Section 9.4), an ongoing precision and recovery sample (OPR, Section
            9.6), and a matrix spike and matrix spike duplicate (MS/MSD, Section 9.3), resulting in a
            minimum of five analyses (1 sample, 1 blank, 1 OPR, .1 MS, and  1 MSD) and a maximum
            of 14 analyses (10 samples,  1  blank, 1 OPR, 1 MS, and 1 MSD) in the batch. If greater than

                                                                                    ,   April1995

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  9.2
	—	   :	   '	     Method 1664

         10 samples are to be extracted at one time, the samples must be separated into analytical
        batches of 10 or fewer samples.                        .
 Initial demonstration of laboratory capability.
  9.2.1  Method Detection Limit (MDL)—To establish the ability to detect HEM and SGT-HEM,
        the analyst shall determine the MDL per the procedure in 40 CFR 136, Appendix B using
        the apparatus, reagents, and standards that will be .used in the practice of this method.  An
        MDL less than or equal to the MDL in Section 1:6 must be achieved prior to the practice of
        this method.

  9.2.2  Initial precision and recovery (IPR)—To establish the ability to generate acceptable preci-
        sion and accuracy, the analyst shall perform the following operations:
       9A2.1  Extract and evaporate four samples of the PAR standard (Section 7.11) according to
               the procedure beginning in Section 11.
       9.2.2.2  Using the results of the set of four analyses, compute the average percent recovery
               (X) and the standard deviation of the percent recovery (s) for HEM and for SGT-
               HEM (if determined). Use the following equation for calculation of the standard
               deviation of the percent recovery:   .
                                                            /

                                    Equation 1
                                                 n - I
                                 where:
                                 n = Number of samples
                                 x = Concentration in each sample
             9.2.2.3  Compare s and X with the corresponding limits for initial precision and recovery in
                     Table 1. If s and X meet the acceptance criteria, system performance is acceptable
                     and analysis of samples may begin. If, however, s exceeds the precision limit or X
                     falls outside the range for recovery, system performance is unacceptable. In this
                     event correct the problem, and repeat the test.
       9.2.3  Equivalency demonstration for application of a method modification to compliance moni-
             toring—To establish the ability of a modification of this method to recover an amount of
             HEM and/or SGT-HEM equivalent to the amount recovered by this method from a specific
             discharge, proceed as follows:
             9.2.3.1 ^Collect, extract, concentrate, and weigh the 'HEM or SGT-HEM in two sets of four
                    aliquots of unspiked wastewater. One set of four wastewater aliquots is .analyzed
                    according to the protocol in Section 11 of this method and the other set of four -
                    aliquots is analyzed using the modified method.
April 1995

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Method 1664
            9.2.3.2 Calculate the average percent recovery of HEM and SGT-HEM for the set of results
                   from this method and for the set of results from the modified method. The average
                   percent recovery using the modified method must be 79 to 114 percent of the aver-
                   age percent recovery produced by this method for HEM and 66 to 114 percent of
                   the average percent recovery produced by this method for SGT-HEM. If not, the
                   modified method may not be used.

   Note:   If the average concentration of the four results produced using this method and the
   average concentration of the four results produced using the modified method are below the
   Minimum Level (Section 1.6),  and if the equivalency test of the modified method is passed for spikes   .
   of reference standards into reagent water (Section 9.2.2), the modified method is deemed to be
   equivalent tothis method for determining HEM arid or SGT-HEM on that specific discharge.

9.3  Matrix spikes—The laboratory must spike, in duplicate, a minimum of 10 percent of all samples
     (one sample in each batch of ten samples) from a given sampling site or, if for compliance monitor-
     ing, from a given discharge. The two sample aliquots shall be spiked with the hexadecane/stearic
     acid spiking solution (Section 7.10).
      9.3.1  The concentration of the spike in the sample shall be determined as follows:
           9.3,1.1  If, as in compliance monitoring, the concentration of HEM or SGT-HEM in the
                   sample is being checked against a regulatory concentration limit, the spiking level
                   shall be at that limit or at 1 to 5 times higher than the background concentration of
                   the sample (determined in Section 9.3.2), whichever concentration is higher.
           9.3.1.2 If the concentration of HEM or SGT-HEM in a sample is not being checked against
                   a limit, the spike shall be at the concentration of the precision and recovery standard
                   (Section 7.11) or at 1 to 5 times higher than the background concentration, which-
                   ever concentration is higher.
      9.3.2  Analyze one sample aliquot out of each set of ten samples from each site or discharge
            according to the procedure beginning in Section 11 to determine the  background concen-
            tration (B) of HEM or SGT-HEM.
            9.3.2.1  If necessary, prepare a standard solution appropriate to produce a level in the sam-
                   ple at the regulatory compliance limit or at 1 to 5 times the background concentra-
                   tion (per Section 9.3.1).
            9.3.2.2 Spike two additional sample aliquots with the spiking solution and analyze these
                   aliquots to  determine the concentration after spiking (A).
      9.3.3  Calculate the percent recovery (P)  of HEM or SGT-HEM in each aliquot using the follow-
            ing equation:
W
                                                                                        April 1995

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                                                                                       Method 1'664
                                           Equation 2
                                        P =
                                              100 (A - B)
                  where:
                  A  = Measured concentration of analyte, after spiking
                  B  = Measured background concentration of HEM or SGT-HEM
                  T  = True concentration of the spike (40 mg/L)
              When determining SGT-HEM, the true concentration (T) must be divided by 2-to reflect the
              concentration of hexadecane that remains after removal of stearic acid (20 mg/L).
        9.3.4  Compare the percent recovery of the HEM or SGT-HEM with the corresponding QC
              acceptance criteria in Table 1.                                 .    '

             9.3.4.1  If the results of the spike fail the acceptance criteria, and the recovery of the QC
                    standard in the ongoing precision and recovery test (Section 9.6) for the analytical
                    batch is within the acceptance criteria in Table 1, an interference is present. In this
                    case, the result may not be reported for regulatory compliance purposes and the
                    analyst must assess the potential cause for the interference. If the interference is
                    attributable to sampling, the site or discharge should be resampled.  If the interfer-
                    ence is attributable to a method deficiency, the analyst must modify the method,
                    repeat the tests required in Section 9.1.2, and repeat the analysis of the sample and
                    theMS/MSD.
             9.3.4.2  If the results of both the spike and the ongoing precision and recovery test fail the
                    acceptance criteria, the analytical system is judged to be out of control, and the
                    problem shall be identified and corrected, and the sample reanalyzed.
       9.3.5  Compute the relative percent difference (RPD) between the two results (not between the
             two recoveries) using the following equation:
                                          Equation 3
                                  RPD =
           where:
                                          (D, + D2)/2
x 100
           D1  = Concentration of HEM or SGT-HEM in the sample
           D2  = Concentration of HEM or SGT-HEM in the second (duplicate) sample
April 1995
                                                                                             11

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Method 1664
       9.3.6  The relative percent difference for duplicates shall meet the acceptance criteria in Table 1.
             If the criteria are not met, the analytical system is judged to be out of control, and the
             problem must be immediately identified and corrected, and the analytical batch reanalyzed.
       9.3.7  As part of the QC program for the laboratory, method precision and accuracy for samples
             should be assessed and records should be maintained. After the analysis of five spiked
             samples in which the recovery passes the test in Section 9.3.4, compute the average percent
             recovery (PJ and the standard deviation of the percent recovery (sp). Express the accuracy
             assessment as a percent recovery interval from Pa - 2sp to Pa + 2sp.  For example, if Pa =
             90% and sp = 10% for five analyses of HEM or SGT-HEM, the accuracy interval is ex-
             pressed as 70-110%. Update the accuracy assessment on a regular basis (e.g., after each
             five to  ten new accuracy measurements).
               *
9.4  Laboratory  blanks—Laboratory reagent water blanks are analyzed to demonstrate freedom from
     contamination.
       9.4.1  Extract and concentrate a laboratory reagent water blank initially (i.e. with the tests in
             Section 9.2) and with each analytical batch. The blank must be subjected to the same
             procedural steps as a sample.
       9.4.2  If material is detected in the blank at a concentration greater than the Minimum Level
             (Section 1.6), analysis of samples is  halted until the source of contamination is eliminated
             and a blank shows no evidence of contamination.  All samples must be associated with an
             uncontaminated method blank before the results may be reported for regulatory compliance
             purposes.
9.5  Calibration  verification—Verify calibration of the balance per Section 10 before and after each
     analytical batch of 14 or fewer measurements.  (The 14 measurements will normally be 10 samples,
     1 blank, 1 OPR, 1 MS, and 1 MSD.)  If calibration is not verified after the measurements, recali-
     brate the balance and reweigh the batch.
9.6  Ongoing precision and recovery—To demonstrate that the analysis system is in control, and
     acceptable precision and accuracy is being maintained with each analytical  batch, the analyst shall
     perform the following operations:
       9.6.1  Extract and concentrate a precision and recovery standard (Section 7.11) with each analyti-
             cal batch according to the procedure beginning in Section 11.
       9.6.2  Compare the concentration with the  limits for ongoing precision and recovery in Table 1. If
             the  concentration is in the range specified, the extraction, evaporation, and weighing pro-
             cesses are in control and analysis of blanks and samples may proceed.  If, however, the
             concentration is not in the specified range, the analytical process  is  not in control. In this
             event, correct the problem, re-extract the analytical batch, and repeat the ongoing precision
             and recovery te'st.
       9.6.3  The laboratory should add results that pass the specification in Section 9.6.2 to IPR and
             previous OPR data and update QC charts to form  a graphic representation of continued
             laboratory performance.  The laboratory should also develop a statement of laboratory data
             quality for each analyte by calculating the average percent recovery (R) and the standard
12
April 1995

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                                                                                         Method 1664
   9.7
        deviation of the percent recovery (sr). Express the accuracy as a recovery interval from
        R - 2sr to R + 2sr. For example, if R = 95% and sr = 5%, the accuracy is 85% to 105%.
 Quality control sample (QCS)—It is suggested that the laboratory obtain a quality control sample
 from a source different from the source for the hexadecane and stearic acid used routinely in this
 method (Sections 7.8 and 7.9), and that the QCS be used for verification of the concentrations of
 HEM and SGT-HEM using the procedure given in the note in Section 7.10.3.                  ;
 The specifications contained in this method can be met if the apparatus used is scrupulously cleaned
 and dedicated for the determination of HEM and SGT-HEM. The standards used for initial preci-
 sion and recovery (IPR, Section 9.2.2), matrix spikes (MS/MSD, Section 9.3), and ongoing preci-
 sion and recovery (OPR, Section 9.6) should be identical, so that the most precise results will be
obtained.
   9.8
  9.9
         *
Depending upon specific program requirements, field replicates and field spikes of the analytes of
interest into samples may be required to assess the precision and accuracy of the sampling and
sample transporting techniques.
10.0   Calibration and Standardization

 .10.1   Calibrate the analytical balance at 2 mg and 1000 mg using class "S" weights.
 10.2   Calibration shall be within ± 10% (i.e. ±0.2 mg) at 2 mg and ± 0.5% (i.e. ±5 mg) at 1000 mg.  If
        values are not within these limits, recalibcate the balance.

11.0   Procedure
  This method is entirely empirical. Precise and accurate results can be obtained only by strict adherence to
  all details.

     Note:   The procedure below is based on the preparation, extraction, and analysis of a 1 L sample
     volume. If a smaller volume of sample is collected for analysis, the laboratory may need to adjust
     the size of the labware used in order to compensate for the smaller volume being processed.
     Commensurately smaller volumes of reagents (i.e. HCl or H^O4, n-hexane, and sodium sulfate)
     may be used.

 11.1   Preparation of the analytical batch.
        11.1.1  Bring the analytical batch of samples, including the sampte aliquots for the MS and MSD,
              to room temperature.
       11.1.2  Place approximately 1000 mL (950-1050 mL) of reagent water (Section 7.1) in a clean
              sample bottle to serve as the laboratory blank.
       11.1.3  Prepare the OPR (Section 9.6) using the PAR standard (Section 7.11).
       11.1.4  Either mark the sample bottle at the water meniscus or weigh the bottle for later deter-
              mination of sample volume. Weighing will be more accurate. Mark or weigh the MS and
              MSD.
 April 1995
                                                                                               13

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 Method 1664
11.2   pH verification.
       11.2.1  Verify that the pH of the sample is less than 2 using the following procedure:
            11.2.1.1  Dip a glass stirring rod into the well mixed sample.
            11.2.1.2  Withdraw the stirring rod and allow a drop of the sample to fall on or touch the pH
                     paper.

    Note:    Do not dip the pH paper into the bottle or touch it to the sample on the lid.

            11.2.1.3  Rinse the stirring rod with a small portion of n-hexane that will be used for extrac-
                     tion (to ensure that no extractable material is lost on the stirring rod). Collect the
               * -    rinsate in the separately funnel to be used for sample extraction.
       11.2J2  If the sample is at neutral pH, add 5-6 mL of HC1 or H2SO4 solution (Section 7.2) to the 1
              liter sample. If the sample is at high pH, use a proportionately larger amount of HC1 or
              H2SO4 solution.  If a smaller sample volume was collected, use a proportionately smaller
              amount of HC1 or H,SO4 solution.
       11.2.3  Replace the cap and shake the bottle to mix thoroughly. Check the pH of the sample using
              the procedure in Section 11.2.1. If necessary, add more acid to the sample and retest.
       11.2.4  Add the appropriate amount of HC1 or H2SO4 solution to the blank, OPR, MS, and MSD.
                                           %
11.3  Extraction
       11.3.1 Tare a clean boiling flask containing 3-5 boiling chips as follows:
            11.3.1.1  Place the flask containing the chips in an oven at 105-115°C for a minimum of 2 h
                     to dry the flask and chips.
            11.3.1.2  Remove from the oven and immediately transfer to cool to room temperature in a
                     desiccator.
            11.3.1.3  When cool, remove from the desiccator with tongs and weigh immediately on a
                     calibrated balance (Section  10).
       11.35 Pour the sample into the separatory funnel.
       11.3.3 Add 30 mL n-hexane to the sample bottle and seal  the bottle with the original bottle cap.
             Shake the bottle to rinse all interior surfaces of the bottle, including the lid of the  bottle cap.
             Pour the solvent into the separatory funnel.
       11.3.4 Extract the sample by shaking the separatory funnel vigorously for 2 minutes with periodic
             venting into a hood to release excess pressure.
       11.3.5 Allow the organic phase to separate from the aqueous phase for a minimum of 10 minutes.
             If an emulsion forms between the phases and the emulsion is greater than one-third the
              volume of the solvent layer, the analyst must employ mechanical techniques to complete the
             phase separation.  The optimum technique depends upon the sample, but may include
              stirring, filtration  through glass wool, use of solvent phase separation paper, centrifugation,
             use of an ultrasonic bath with ice, addition of NaCl, or other physical methods. Alternative-
 14
April 1995

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                                                                                         Method 1664
               ly, solid-phase, continuous, or other extraction techniques may be used to prevent emulsion
               formation, provided that the requirements in Section 9.1.2 are met.
        11.3.6   Drain the aqueous layer (lower layer) into the original sample container, Drain a small
               amount of the organic layer into the sample container to minimize the amount of water
               remaining in the separatory funnel.

    Note:   The amount of water remaining with the n-hexane must be minimized to prevent dissolu-
    tion or clumping of the sodium sulfate in the solution drying process.

       11.3.7  Place approximately 10 g anhydrous Na^O,, in a filter funnel and rinse with a small portion
              of n-hexane. Discard the rinsate.
    Note:
The specific properties of a sample may necessitate the use of larger amounts ofNa2SO4
       11.3.8  Drain the n-hexane layer (upper layer) from the separatory funnel through the Na^O,, into
              the preweighed boiling flask containing the boiling chips (Section 11.3.1.3).
       11.3.9  Repeat the extraction (Sections 11.3.3-11.3.6 and 11.3.8) twice more with fresh 30-mL
              portions of n-hexane, combining the extracts in the boiling flask.
      11.3.10  Rinse the tip of the separatory funnel, the filter paper, and the funnel with 2-3 small (3-5
              mL) portions of n-hexane. Collect the rinsings in the flask.
      11.3.11  A milky extract indicates the presence of water.  If the.extract is milky, allow the solution to
              stand for up to one hour to allow the water to settle. Decant the solvent layer (upper layer)
              through sodium sulfate to remove any excess water as in Sections 11.3.7 and 11.3.8.
      11.3.12  If only SGT-HEM is to be determined, proceed to Section 11.5.
11.4  Solvent evaporation.
       11.4.1  Connect the boiling flask to the distilling head apparatus and evaporate the solvent by
              immersing the lower half of the flask in a water bath or a steam bath.  Adjust the water
              temperature as required to complete the concentration in less than 30 minutes. Collect the
              solvent for reused
     . 11.4.2 When the temperature in the distilling head reaches 70°C or the flask appears almost dry,
             remove the distilling head. Sweep out the flask for 15 seconds with air to remove solvent
             vapor by inserting a glass tube connected to a vacuum source. Using tongs, immediately
             remove the flask from the heat source and wipe the outside surface dry to remove moisture
             and fingerprints.  .

   Note:    The analyst should carefully monitor the flask during the final stages of evaporation to
   assure that all of the solvent is removed and at the same time to prevent loss of the more volatile
   sample constituents.
April 1995
                                                                                               15

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 Msthod1664
       11.4.3  Inspect the residue in the boiling flask for crystals. Crystal formation is an indication that
              sodium sulfate may have dissolved and passed into the boiling flask. This may happen if
              the drying capacity of the sodium sulfate is exceeded or if the sample is not adjusted to a
              low pH. If crystals are observed, redissolve the extract in n-hexane, filter into another tared
              boiling flask, and repeat the evaporation procedure (Sections 11.4.1-11.4.2).
       11.4.4  Cool the boiling flask to room temperature in a desiccator and maintain in the desiccator for
              30 minutes minimum. Remove with tongs and weigh immediately to determine the weight
              of the material in the flask.
            11.4.4.1  If the extract was from the HEM procedure, determine the HEM (Wh) by subtract-
                     ing the tare weight (Section  11.3.1) from the total weight of the flask.
            11.4,4.2  If the extract was from the SGT-HEM procedure (Section 11.5.5), determine the
                    weight of SGT-HEM (Ws) by subtracting the tare weight from the total weight of
                    the flask.
       11.4.5  Determine the original sample volume (Vs) in liters by filling the sample bottle to the mark
              with water and measuring the volume of water in a 1 to 2 L graduated cylinder.  If the
              sample weight was used (Section 11.1.4), weigh the empty bottle and cap and determine Vs
              by difference,  assuming a sample density of 1.00.
11.5  SGT-HEM determination.
       11.5.1  Silica gel capacity—To ensure that the capacity of the silica gel will not be exceeded, the
              amount of HEM must be less than 100 mg or, if above 100 mg, must be known.
            11.5.1.1 If it is  known that the amount of HEM is less than 100 mg, the analyst may proceed
                    with the determination of SGT-HEM per Sections 11.5.3-11.5.5 without determina-
                    tion of HEM.
            11.5.1.2 If, however, the amount of HEM is not known, HEM must first be determined using
                    the procedure in Sections 11.3-11.4.
       11.52 Extractable materials in silica gel—Because the capacity of silica gel is not known for all
             substances, it is presumed that 3 g will adsorb  100 mg of all adsorbable materials. The
             amount of silica gel that can be used for adsorption in the SGT-HEM procedure below has
             been limited to 30 g because of concerns about possible extractable impurities in the silica  •
             gel. Therefore, if the extract contains more than  1000 mg of HEM, split the extract per the
             following procedure:
            11.5.2.1 Add 85-90 mL of n-hexane to the boiling flask to redissolve the HEM. If neces-
                    sary, heat the solution on an  explosion-proof hotplate or in a water bath to com-
                    pletely redissolve the HEM.
            11.5.2.2 Transfer the extract to a 100-mL volumetric flask.  Rinse the boiling flask sequen-
                    tially with 2-3 small portions of n-hexane and add to the volumetric flask. Dilute to
                    the mark with n-hexane.
            11.52.3 Calculate the extract volume that contains 1000 mg of extractable material accord-
                    ing to  the following equation:
                                                                                         April 1995

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                                                                                         Method 1664
                                             Equation 4
                                                  1000 Vt

                     where:                                           •
                     Va =  Volume of aliquot to be withdrawn (mL)
                     Vt =  Total volume of solvent used in Section 11.5.2.2 (mL)
                     Wk =  Weight of extractable material HEM measurement (mg)
             11.32.4  Using a calibrated pipet, remove the volume to be withdrawn (VJ and return to the
                      boiling flask.  Dilute to approximately 100 mL with n-hexane.
      ,  11.5.3  Adsorption with silica gel
             11.5.3.1  Add 3.0 ± 0.3 g of anhydrous silica gel (Section 7.7) to the boiling flask for every
                      lOOmgofHEM, or fraction thereof, to a maximum of 30 g of silica gel. Forexam-
                <      pie, if the weight of HEM is 735 mg, add 3 x 8 = 24 g of silica gel.
             11.5.3.2  Add a fluoropolymer-coated stirring bar to the flask and stir the solution on a mag-
                      netic stirrer for a minimum of 5 minutes.
       11.5.4 Filter the solution through n-hexane moistened filter paper into a pre-dried, tared boiling
              flask containing several boiling chips. Rinse the silica gel and filter paper with several
              small amounts of n-hexane to complete the transfer.
       11.5.5 Evaporate the solution and determine the weight of SGT-HEM per Section 11.4.

12.0   Data Analysis and Calculations
 12.1
n-Hexane extractable material—Calculate the concentration of HEM ("oil and grease") in the
sample per the following equation:
                                           Equation 5
                                     HEM
                                                        
-------
  Method1664
       for Wb.  If the extract was split to decrease the total amount of material to 1,000 mg, determine the
       corrected total weight of SGT-HEM in the un-split extract (Wc) using the following equation:
                                           Equation 6
                                      Wc (mg) =    -Wd (mg)
                                                  a
    where:
    Wd a Weight in the portion of the extract split for adsorption (Sections 11.5.2.4 and 11.4.4.2)
    Vt and  Va are as defined in Equation 4
       Use the corrected total weight of SGT-HEM in the unsplit extract (Wc) to determine the total SGT-
       HEM in the sample by substituting Wc for Wh in Equation 5.
 12.3   Reporting
       12^.1  Samples—Report results to three significant figures for HEM and SGT-HEM found above
              the ML (Section 1.6) in all samples. Report results below the ML as < 5 mg/L for HEM
              and SGT-HEM, or as required by the permitting authority or permit.
                                           »
       12.3.2  Report results to three significant figures for HEM and SGT-HEM found above the MDL
              (Section 1.6) in all blanks. Do not report results below the MDL unless required by the
              permitting authority or in the permit.

13.0   Method Performance
       This method was validated through single laboratory studies and an inter-laboratory method valida-
       tion study (Reference 16.9).

14.0   Pollution Prevention

 14.1   The solvents used in this method pose little threat to the environment when recycled and managed
       properly.
 14.2   Standards should be prepared in volumes consistent with laboratory use to minimize the volume of
       expired standards to be disposed.

15.0   Waste Management

 15.1   It is the laboratory's responsibility to comply with all federal, state, and local regulations governing
       waste management, particularly the hazardous waste identification rules and land disposal restric-
       tions, and to protect the air, water, and land by minimizing and controlling all releases from fume
       hoods and bench operations.  Compliance with all sewage discharge permits and regulations is also
       required.
  18
                                                                                         April 1995

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                                                                                      Method 1664
 15.2  Samples preserved with HC1 or H2SO4 to pH < 2 are hazardous and must be neutralized before
       being disposed; or must be handled as hazardous waste.           •
 15.3  For further information on waste management, consult "The Waste Management Manual for
       Laboratory Personnel", and "Less is Better: Laboratory Chemical Management for Waste Reduc-
       tion", both available from the American Chemical Society's Department of Government Relations
       and Science Policy, 1155 16th Street N.W., Washington, D.C. 20036.. •

16.0   References

 16.1   "Methods for Chemical Analysis of Water and Wastes", 3rd Edition, Environmental Protection
       Agency, Environmental Monitoring Systems Laboratory-Cincinnati (EMSL-Ci), Cincinnati, Ohio
       45268, EPA-600/4-79-020, Method 413.1, (1983).
 16,2  • "Standard Methods for the Examination of Water and Wastewater", 18th Edition, American Public
       Health Association, 1015 Fifteenth Street, NW, Washington, D.C. 20005, Method 5520B and
       Method 5520F,,( 1992).
       40 CFR 136, Appendix A, Methods 1624 and 1625.
       "Carcinogens - Working With Carcinogens," Department of Health, Education, and Welfare, Public
      Health Service, Center for Disease Control, National Institute for Occupational Safety and Health,
      Publication No. 77-206, August 1977.
      "OSHA Safety and Health Standards, General Industry," (29 CFR 1910), Occupational Safety and
      Health Administration, OSHA 2206 (Revised, January 1976).
      "Safety in Academic Chemistry Laboratories," American Chemical  Society, Committee on Chemi-
      cal Safety, 3rd Edition, 1979.
      "Standard Practices for Sampling Water," ASTM Annual Book of Standards, Part 31, D3370-76,
      American Society for Testing and Materials, 1916 Race Street, Philadelphia, PA 19103-1187, 1980.
      "Handbook of Analytical Quality Control in Water and Wastewater  Laboratories," USEPA, EMSL-
      Ci, Cincinnati, OH 45268, EPA-600/4-79-019, March 1979.
      Report of the Method 1664 Validation Studies, April 1995. Available from the Sample Control
      Center (operated by DynCorp Environmental Programs Division), 300 N. Lee Street, Alexandria,
      VA 22314, (703) 519-1140.
16.3
16.4


16.5

16.6

16.7

16.8

16.9
April 1995
                                                                                           19

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  Method 1664
17.0   Tables
  Table 1. Acceptance Criteria for Performance Tests
     Acceptance Criterion
Section
Limit (%)
     Initial precision and recovery
         HEM Precision (s)
         HEM Recovery (X)
         SGT-HEM Precision (s)
         SGT-HEM Recovery (X)
   9.2.2
  9.2.2.2
  9.2.2.2
  9.2.2.2
  9.2.2.2
       10
   83-101
       13
   83-116
     Matrix spike/matrix spike duplicate
         HEM Recovery
         HEM RPD
         SGT-HEM Recovery
         SGT-HEM RPD
    9.3
   9.3.4
   9.3.5
   9.3.4
   9.3.5
   79-114
       18
   66-114
       24
    Ongoing precision and
    recovery
         HEM Recovery
         SGT-HEM Recovery
    9.6

    9.6
    9.6
   79-114
   66-114
 20
                                                 April 1995

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                                                                                         Method 1664
 18.0   Glossary of Definitions and Purposes
  18.1
 18.2
  The definitions and purposes are specific to this method but have been conformed to common usage
  as much as possible.            .

  Units of weight and measure and their abbreviations
  18.1.1   Symbols
         °C            degrees Celsius
         <             less than                                   .
         %             percent
         ±             plus or minus
  18.1.2   Alphabetical characters
               g
               h
               L
               mg
                      gram
                      hour
                      liter
                      milligram
        mg/g   milligram per gram
        mg/L          milligram per liter
        mg/mL        milligram per milliliter
        niL           milliliter                                                    ,
        No.           number         *
        rpm           revolutions per minute
 Definitions, acronyms, and abbreviations
 18.2.1  Anajytei The HEM or SGT-HEM tested for by this method.
 18.2.2  Analytical batch:  The set of samples extracted at the same time, to a maximum of 10
        samples. Each analytical batch of 10 or fewer samples must be accompanied by a laborato-
        ry blank (Section 9.4), an ongoing precision and recovery sample (OPR, Section 9.6), and a
        matrix spike and matrix spike duplicate (MS/MSD, Section 9.3), resulting in a minimum of
        five analyses (1 sample, 1  blank, 1 OPR, 1 MS, and 1 MSD) and a maximum of 14 analyses
        (10 samples, 1 blank, 1 OPR, 1 MS, and 1 MSD) in the batch. If greater than 10 samples
        are to be extracted at one time, the samples must be separated into analytical batches of 10
        or fewer samples.
18.2.3  Field blank:  An aliquot of reagent water that is placed in a sample container in the labora-
       tory or in the field and treated as  a sample in all respects, including exposure to sampling
       site conditions, storage, preservation, and all analytical procedures. The purpose of the
       field blank is to determine if the field or sample transporting procedures and environments
       have contaminated the sampie.
18.2.4  HEM:  See n-Hexane extractable material.
18'2'5  n-Hexane extractable material: The material that is extracted from a sample and determined
       by this method.
18.2.6  IPR: See initial precision and recovery.                             -
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Method1664
 22
      18.2.7 Initial precision and recovery (IPR): Four aliqiiots of the diluted PAR analyzed to establish
            the ability to generate acceptable precision and accuracy. An IPR is performed the first
            time this method is used and any time the method or instrumentation is modified.
      18.2.8 Laboratory blank (method blank): An aliquot of reagent water that is treated exactly as a
            sample including exposure to all glassware, equipment, solvents, reagents, internal stan-
            dards, and surrogates that are used with samples.  The laboratory blank is used to determine
            if analytes or interferences are present in the laboratory environment, the reagents, or the
            apparatus.
      182.9 Laboratory control sample (LCS): See Ongoing precision and recovery standard (OPR).
     185.10 Matrix  spike (MS) and matrix spike duplicate (MSP): Aliquots of an. environmental
            sample to which known quantities of the analytes are added in the laboratory. The MS and
            MSD are prepared and/or analyzed exactly like a field sample.  Their purpose is to quantify
            any additional bias and imprecision caused by the sample matrix.  The background concen-
            trations of the analytes in the sample matrix must be determined in a separate aliquot and
            the measured values in the MS and MSD corrected for background concentrations.
     18.2.11 May: This action, activity, or procedural step is neither required nor prohibited.
     18.2.12 May not: This action, activity, or procedural step is prohibited.
     18.2.13 Method Detection Limit: The lowest level at which an analyte can be detected with 99
            percent confidence that the analyte concentration is greater than zero.
     18.2.14 Minimum Level (ML): The lowest level at which the entire analytical system gives a
            recognizable signal and acceptable calibration point for the analyte. It is equivalent to the
            concentration of the lowest calibration standard, assuming that all method-specified sample
            weights, volumes, and cleanup procedures have been employed.
     18.2.15 Must:  This action, activity, or procedural step is required.
     18.2.16 Ongoing precision and recovery standard fOPR. also called a laboratory control sample):  A
            laboratory blank spiked with known quantities of analytes. The OPR is analyzed exactly
            like a sample.  Its purpose is to assure that the results produced by the laboratory remain
            within  the limits specified in this method for precision and accuracy.
     18.2.17  OPR:  See Ongoing precision and recovery standard.
     185.18  PAR:  See Precision and recovery standard.
     185.19  Precision and recovery standard: Secondary standard that is diluted and spiked to form the
             IPR and OPR.                                                         ,
     18.250  Quality control sample (PCS): A sample containing analytes of interest at known concen-
             trations.  The QCS is obtained from a source external to the laboratory or is prepared from
             standards obtained from a different source than the calibration standards. The purpose is to
             check  laboratory performance using test materials that have been prepared independently
             from the normal preparation process.
     18551  Reagent water: Water demonstrated to be free from HEM and SGT-HEM and. potentially
             interfering substances at or above the Minimum Level of this method.

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      18.222 SGT^HEM: See Silica gel treated n-hexane extractable material.
      18.2.23 Should:  This action, activity, or procedural step is suggested but not required.
      18-2-24 Silica gel treated n-hexane extractable material: n-Hexane extractable material (HEM) that
              is not adsorbed by silica gel.
      18.2.25 Stock solution: A solution containing an analyte that is prepared using a reference material
              traceable to EPA, the National Institute of Science and Technology (NIST), or a source that
     i   _.   • will attest to the purity and authenticity of the reference material.
April 1995
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