SW846PU31
PROPOSED UPDATE III
Cover Sheet
THIS PACKET CONTAINS NEW AND REVISED MATERIAL
BEING PROPOSED FOR INCLUSION IN:
TEST METHODS FOR EVALUATING SOLID WASTE
PHYSICAL/CHEMICAL METHODS
(SW-846) THIRD EDITION
Contents:
1. Cover sheet. (What you are currently reading)
2. Instructions. Read this section! It explains how proposed Update III
relates to the rest of your SW-846.
3. Proposed Update III Disclaimer. Table of Contents, and Preface. The
Table of Contents (dated January 1995) lists all of the methods (Third
Edition, Updates I, II, IIA, IIB, and proposed Update III) in the order
in which they will appear in the manual when Update III is finalized.
4. Revised Chapter Two: Choosing the Right Method
5. Revised Chapter Three and new/revised methods for inorganic analyses.
6. Revised Chapter Four and new/revised methods for organic analyses.
7. Revised Chapter Five and new/revised methods for miscellaneous
analyses.
8. Revised Chapter Six and new/revised methods for properties analyses.
9. Revised Chapter Eight (revised section separation sheets only).
10. Revised Chapter Ten and new/revised methods for sampling.
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Ftoor
Chicago, IL 60604-3590
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f
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INSTRUCTIONS
SW-846, a methods manual, is a "living" document that changes when new data
and advances in analytical techniques are incorporated into the manual as new
or revised methods. Periodically, the Agency proposes and finalizes these new
and revised methods as updates to the manual. To date, the Agency has
issued Final Updates I, II, IIA, IIB, and Proposed Update III.
These instructions include directions on where to find information on getting
your basic manual up-to-date and what to do with your Proposed Update III
package. The Agency will release additional proposed and final updates in the
future. New instructions, to supersede these, will be included with each of
those updates. However, in general, final updates should always be
incorporated into SW-846 in chronological order (e.g. Update I should be
incorporated before Update II).
The following definitions are provided to you as a guide:
New subscribers are defined as individuals who have recently (6-8 weeks) placed an
order with the GPO and have received new copies of the 4 (four) volume set of the
Third Edition, a copy of Final Update I, a copy of Final Update II/IIA, a copy of
Final Update IIB, and a copy of Proposed Update III.
Previous subscribers are defined as individuals that have received copies of the
Third Edition and other SW-846 Updates (including proposed Updates) in the past
and have just received their Proposed Update III package in the mail.
BACKGROUND INFORMATION
A number of SW-846 update packages have been released to the public since the original
Third Edition was released. The dates and labels on these packages can be confusing. The
following is a brief summary of what new subscribers and previous subscribers should check
upon receipt of the Proposed Update III package:
Instructions - 1 Proposed Update III
January 1995
-------
NEW SUBSCRIBERS - If you are a new subscriber, you should perform the following tasks
before addressing your new Proposed Update III:
• Place the original Third Edition of SW-846 (September 1986) in the properly labeled
four 3-ring notebooks according to the instructions in Update IIB.
• Incorporate Final Update I (July 1992) into the manual according to the instructions
in Update IIB.
• Incorporate Final Updates II (September 1994) and HA (August 1993) into the
manual according to the instructions in Update IIB.
• Incorporate Update IIB (January 1995) into the manual according to the
instructions in Update IIB.
PREVIOUS SUBSCRIBERS - If you are a previous subscriber, it is important to establish
exactly what is currently contained in your manual before addressing Proposed Update III.
If your manual is properly updated, the ONLY white pages in the document should be
dated September 1986 (Third Edition), July 1992 (Final Update I), August 1993 (Final
Update HA), September 1994 (Final Update II), and January 1995 (Final Update IIB).
Remove (and recycle or archive) any white pages from your manual that have any other
dates. There may also be colored pages (e.g., yellow pages for Proposed Update II) inserted
in the manual. Remove all yellow, blue, or green pages from the manual. These colored
pages represent proposed (not promulgated) versions of methods and chapters. Some
individuals may have chosen to keep their copies of proposed versions in separate binders
and thus removal from SW-846 is not necessary.
The table on the next page (entitled "A Brief History of the SW-846, Third Edition and Its
Updates") can be used as an aid to understanding the update history of SW-846, Third
Edition. Finalized (promulgated) updates are printed in bold and underlined. An
individual or organization that has held an SW-846 GPO subscription for several years may
have received copies of any or all of the updates.
Instructions - 2 Proposed Update III
January 1995
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A BRIEF HISTORY OF THE SW-846, THIRD EDITION AND ITS UPDATES
Package
Third Edition
Proposed Update I
Final Update I
(Accidently Released)
Proposed Update II
(Accidently Released)
Final Update I
Proposed Update II
Proposed Update IIA*
(Available from EPA by
request only.)
Final Update IIA* (Included
with Final Update II.)
Final Update II
Final Update IIB**
Proposed Update III
Date Listed on Methods
September 1986
December 1987
November 1990
November 1990
July 1992
November 1992
October 1992
August 1993
September 1994
January 1995
January 1995
Color of Paper
White
Green
White
Blue
White
Yellow
White
White
White
White
Pink
Status of Package
Finalized (Promulgated)
Obsolete
Obsolete! Never formally
finalized.
Obsolete! Never formally
proposed.
Finalized (Promulgated)
Obsolete
Obsolete
Finalized (Promulgated)
Finalized (Promulgated)
Finalized (Promulgated)
Proposed
* Contains only Method 4010.
** Contains only a revised Table of Contents, a revised Chapter Six, and revised Methods 9040B
and 9045C
PROPOSED UPDATE III
Update III has been proposed by the USEPA Office of Solid Waste for official inclusion in
the SW-846 methods manual. The Proposed Update III package includes 37 revised
methods, six revised chapters, other revised parts (i.e., the Table of Contents, Disclaimer,
and Preface) and 61 new methods. The term "proposed" indicates that the USEPA is
allowing the public the opportunity to comment on the Proposed Update III material (e.g.,
submit suggestions or recommendations regarding the content of the methods).
Regarding one of the revised chapters, the Agency has revised Chapter Eight to reflect the
proposed new location of Method 9040B in that chapter. The Agency wishes to move
Method 9040B from Chapter Six, "Properties", to Chapter Eight, "Methods for Determining
Characteristics". Chapter Eight is the more appropriate location for Method 9040B since
Instructions - 3
Proposed Update III
January 1995
-------
it is the method promulgated for pH measurements in support of determinations for the
Corrosivity Characteristic, see 40 CFR § 261.22(a)(l). (The method itself has not been
revised and is not open for comment.) In addition, the Agency has added and revised
section numbers and section titles in Chapter Four to accommodate new organic methods.
Specifically, the Agency has added a section 4.3.5, "Miscellaneous Spectrometric Methods",
and moved the "Miscellaneous Screening Methods" from section 4.4 to a new section 4.5.
Section 4.4 will now contain all of the immunoassay methods, most of which will be added
as part of Update III when made final.
In order to distinguish proposed updates from finalized (promulgated) updates, each
proposed update is printed on colored paper. (Final updates are printed on white paper.)
The Proposed Update III package is printed on pink paper. "January 1995" is the date
found in the lower right-hand corner of each page in the Proposed Update III package.
(Note: Methods 9040B and 9045C of SW-846 are also dated January 1995, but are printed
on white paper, and are part of the final and promulgated Update IIB package. These
methods are not open for comment at this time.)
A proposed rule has been published in the Federal Register in association with this
proposed update package. It formally announces the proposed changes to the SW-846
manual and states that comments on the proposed rule and the Proposed Update III
package must be submitted within 60 days after the date of publication of the proposed rule.
SW-846 methods not contained in this package are not open to comment from the public.
In addition, as explained in the proposed rule, only sections 3.2, 6.2, 7.2, 7.3, and 7.4 of
proposed Update III Method 9095A are open to comment.
As explained in the "Addresses" section of the proposed rule, the public should submit an
original and two copies of their comments to the Docket Clerk (OS-305), U.S.
Environmental Protection Agency, 401 M Street, SW, Washington, DC 20460. EPA is also
asking prospective commenters to voluntarily submit one additional copy of their comments
on labeled personal computer diskettes in ASCII (TEXT) format or a word processing
format that can be converted to ASCII (TEXT). It is essential to specify on the disk label
the word processing software and version/edition as well as the commenter's name. This
will allow EPA to convert the comments into one of the word processing formats utilized
by the Agency. Please use mailing envelopes designed to physically protect the submitted
diskettes. EPA emphasizes that submission of comments on diskettes is not mandatory, nor
will it result in any advantage or disadvantage to any commenter. Rather, EPA is
experimenting with this procedure as an attempt to expedite our internal review process and
response to comments. This expedited procedure is in conjunction with the Agency's
"Paperless Office Effort" campaign.
Proposed methods do not become an official part of SW-846 until after the Agency
addresses the comments, publishes a final rule in the Federal Register announcing the
promulgation of the update, and publishes a final (promulgated) version of the update
Instructions - 4 Proposed Update III
January 1995
-------
package for distribution. A final update package may be different from the proposed update
package to reflect technical or editorial changes made to the manual in response to public
comment or for other reasons.
In addition to requesting comment on the material in the Proposed Update III package, the
Agency is also requesting comment on the removal of 14 packed column GC and two other
methods from SW-846. The packed column methods have been superseded by capillary
column methods or other techniques that provide better resolution, selectivity and sensitivity.
The table to follow is a list of the methods being proposed for deletion from the manual.
METHODS BEING PROPOSED FOR REMOVAL FROM SW-846
Method
Number
5040A
8010B
8020A
8030A
8040A
8060
8080A
8090
8110
8120A
8140
8150B
8240B
8250A
9200
9252A
Title
Analysis of Sorbent Cartridges from Volatile Organic Sampling Train
(VOST): Gas Chromatography/Mass Spectrometry Technique
Halogenated Volatile Organics by Gas Chromatography
Aromatic Volatile Organics by Gas Chromatography
Acrolein and Acrylonitrile by Gas Chromatography
Phenols by Gas Chromatography
Phthalate Esters
Organochlorine Pesticides and Polychlorinated Biphenyls by Gas
Chromatography
Nitroaromatics and Cyclic Ketones
Haloethers by Gas Chromatography
Chlorinated Hydrocarbons by Gas Chromatography
Organophosphorus Pesticides
Chlorinated Herbicides by Gas Chromatography
Volatile Organics by Gas Chromatography/Mass Spectrometry
(GC/MS)
Semivolatile Organic Compounds by Gas Chromatography/Mass
Spectrometry (GC/MS)
Nitrate
Chloride (Titrimetric, Mercuric Nitrate)
Instructions - 5
Proposed Update III
January 1995
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HANDLING OF PROPOSED UPDATE III
Since these are only proposed methods and chapters, the material in Proposed Update III
does not change anything in the official promulgated version of the manual (i.e., SW-846,
Third Edition, as updated by Updates I, II, IIA, and IIB). The user should not remove any
white pages from the manual at this time. Some subscribers incorporate proposed updates
in their manual, without removing any white pages, e.g., they retain the proposed and
previously promulgated versions of methods side-by-side in the manual. However, this
update is particularly large and the four binders provided with SW-846 may not
accommodate all of the pages, particularly in Volume IB, which contains the organic
methods. Therefore, regarding the placement and storage of this proposed update, the
Agency recommends one of the following:
1. The subscriber may place the pink sheets in the manual (without removing the white
pages of promulgated methods) in the order that they appear in the new Update III
Table of Contents. Due to the volume of material in Proposed Update III, the
subscriber can split the material in any volume (e.g., Volume IIB) into two parts and
place one part into an extra binder supplied by the subscriber.
2. Instead of inserting the proposed methods into the manual with the promulgated
methods, the subscriber may instead simply place the entire Proposed Update III
package into a separate binder supplied by the subscriber.
IN SUMMARY
To summarize these instructions, please note the following important points:
This package contains Proposed Update III. The USEPA is proposing these methods
for inclusion in SW-846.
The public may submit comments to the EPA regarding these methods in paper
and/or electronic format. SW-846 methods not contained in this package are not
open to comment from the public.
Do not remove any white pages from your copy of SW-846 at this time. Proposed
methods do not become an official part of SW-846 until after the Agency addresses
the comments, publishes a final rule in the Federal Register announcing the
promulgation of the update, and publishes a final (promulgated) version of the
update package for distribution.
If you have properly inserted all other updates, PROPOSED UPDATE III WILL
NOT FIT IN THE EXISTING FOUR 3-RING BINDER NOTEBOOKS
PROVIDED WITH THE MANUAL. You may either insert (without replacing any
Instructions - 6 Proposed Update III
January 1995
-------
white pages) Proposed Update III and split some of a volume into your own separate
binder, or you may simply not insert the Proposed Update III into the manual and
instead keep the proposed methods in your own separate binder.
ASSISTANCE
After reading these instructions, if you have any difficulties understanding the status of the
package or have technical questions regarding the methods, you may telephone the Methods
Information Communication Exchange (MICE) at 703-821-4690 for help. If you have
questions concerning your SW-846 U.S. Government Printing Office (GPO) subscription, you
should telephone the GPO at 202-512-1806. If you did not purchase your SW-846 from the
GPO, the GPO will not be able to help you.
SW-846 AVAILABILITY ON CD-ROM
A CD-ROM version of Test Methods for Evaluating Solid Waste, Physical/Chemical Methods
(SW-846) is being developed by EPA in cooperation with the National Technical
Information Service (NTIS). On a single disc, it will include all text and figures found in
the promulgated version of SW-846 as updated by Updates I, II, IIA, and IIB. It will also
include Proposed Update III to SW-846. It can be used for word searching (e.g, analytes,
keywords); and to cut and paste or export text and diagrams to update or develop laboratory
standard operating procedures (SOPs). This SW-846 CD-ROM is scheduled for release in
the Fall of 1995. To order by phone, call NTIS at (703) 487-4650 and request order number
PB95-503249LLC.
Instructions - 7 Proposed Update III
January 1995
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DISCLAIMER
The mention of trade names or commercial products does not constitute
endorsement or recommendation for use by the U.S. Environmental Protection
Agency.
SW-846 methods are designed to be used with equipment from any manufacturer
that results in suitable method performance (as assessed by accuracy, precision,
detection limits and matrix compatibility). In several SW-846 methods, equipment
specifications and settings are given for the specific instrument used during
method development, or subsequently approved for use in the method. These
references are made to provide the best possible guidance to laboratories using
this manual. Equipment not specified in the method may be used as long as the
laboratory achieves equivalent or superior method performance, or performance
appropriate for the intended testing application. If alternate equipment is
used, the laboratory must follow the manufacturer's instructions for their
particular instrument.
Since many types and sizes of glassware and supplies are commercially
available, and since it is possible to prepare reagents and standards in many
different ways, those specified in these methods may be replaced by any similar
types as long as this substitution does not affect the overall quality of the
analyses.
DISCLAIMER - 1 Revision 2
January 1995
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TABLE OF CONTENTS
VOLUME ONE
SECTION A
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
ACKNOWLEDGEMENTS
PART I METHODS FOR ANALYTES AND PROPERTIES
CHAPTER ONE -- QUALITY CONTROL
1.0 Introduction
2.0 QA Project Plan
3.0 Field Operations
4.0 Laboratory Operations
5.0 Definitions
6.0 References
CHAPTER TWO -- CHOOSING THE CORRECT PROCEDURE
2.1 Purpose
2.2 Required Information
2.3 Implementing the Guidance
2.4 Characteristics
2.5 Ground Water
2.6 References
CHAPTER THREE -- INORGANIC ANALYTES
3.1 Sampling Considerations
3.2 Sample Preparation Methods
Method 3005A: Acid Digestion of Waters for Total Recoverable or
Dissolved Metals for Analysis by Flame Atomic Absorption
(FLAA) or Inductively Coupled Plasma (ICP) Spectroscopy
Method 3010A: Acid Digestion of Aqueous Samples and Extracts for Total
Metals for Analysis by Flame Atomic Absorption (FLAA) or
Inductively Coupled Plasma (ICP) Spectroscopy
Method 3015: Microwave Assisted Acid Digestion of Aqueous Samples and
Extracts
CONTENTS - 1 Revision 4
January 1995
-------
Method 3020A:
Method 3031:
Method 3040A:
Method 3050B:
Method 3051:
Method 3052:
Method 3060A:
Acid Digestion of Aqueous Samples and Extracts for Total
Metals for Analysis by Graphite Furnace Atomic
Absorption (GFAA) Spectroscopy
Acid Digestion of Oils for Metals Analysis by FLAA or
ICP Spectroscopy
Dissolution Procedure for Oils, Greases, or Waxes
Acid Digestion of Sediments, Sludges, and Soils
Microwave Assisted Acid Digestion of Sediments, Sludges,
Soils, and Oils
Microwave Assisted Acid Digestion of Siliceous and
Organically Based Matrices
Alkaline Digestion for Hexavalent Chromium
3.3 Methods for Determination of Inorganic Analytes
Method 0060:
Method 0061:
Method 6010B:
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
6020:
7000A:
7020:
7040:
7041:
7060A:
7061A:
7062:
7063:
7080A:
7081:
7090:
7091:
7130:
7131A:
7140:
7190:
7191:
7195:
7196A:
7197:
7198:
7199:
7200:
7201:
7210:
7211:
7380:
7381:
7420:
Determination of Metals in Stack Emissions
Determination of Hexavalent Chromium Emissions from
Stationary Sources
Inductively Coupled Plasma - Atomic Emission
Spectroscopy
Inductively Coupled Plasma - Mass Spectrometry
Atomic Absorption Methods
Aluminum (AA, Direct Aspiration)
Antimony (AA, Direct Aspiration)
Furnace Technique)
Furnace Technique)
Gaseous Hydride)
Arsenic (AA, Borohydride Reduction)
Aqueous Samples and Extracts by Anodic
Antimony (AA,
Arsenic (AA,
Arsenic (AA,
Antimony and
Arsenic in
(AA,
Stripping Voltammetry (ASV)
Barium (AA, Direct Aspiration)
Barium (AA, Furnace Technique)
Beryllium (AA, Direct Aspiration)
Beryllium (AA, Furnace Technique)
Cadmium (AA, Direct Aspiration)
Furnace Technique)
Direct Aspiration)
Direct Aspiration)
Furnace Technique)
Hexavalent (Coprecipitation)
Hexavalent (Colorimetric)
Hexavalent (Chelation/Extraction)
Hexavalent (Differential Pulse Polarography)
Determination of Hexavalent Chromium in Drinking Water,
Groundwater and Industrial Wastewater Effluents by Ion
Chromatography
Cobalt (AA, Direct Aspiration)
Cobalt (AA, Furnace Technique)
Copper (AA, Direct Aspiration)
Copper (AA, Furnace Technique)
Iron (AA, Direct Aspiration)
Iron (AA, Furnace Technique)
Lead (AA, Direct Aspiration)
Cadmium (AA,
Calcium (AA,
Chromium (AA
Chromium
Chromium,
Chromium,
Chromium,
Chromium,
CONTENTS - 2
Revision 4
January 1995
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Method
Method
Method
Method
Method
Method
Method
7421:
7430:
7450:
7460:
7461:
7470A:
7471A:
Method 7472:
Method 7480:
Method 7481:
Method 7520:
Method 7521:
Method 7550:
Method 7580:
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
7610:
7740:
7741A:
7742:
7760A:
7761:
7770:
7780:
7840:
7841:
7870:
7910:
7911:
7950:
7951:
Lead (AA, Furnace Technique)
Lithium (AA, Direct Aspiration)
Magnesium (AA, Direct Aspiration)
Manganese (AA, Direct Aspiration)
Manganese (AA, Furnace Technique)
Mercury in Liquid Waste (Manual Cold-Vapor Technique)
Mercury in Solid or Semi sol id Waste (Manual Cold-Vapor
Technique)
Mercury in Aqueous Samples and
Stripping Voltammetry (ASV)
Molybdenum (AA, Direct Aspiration)
(AA, Furnace Technique)
Direct Aspiration)
Furnace Method)
Direct Aspiration)
(P4) by Solvent
Extracts by Anodic
Molybdenum
Nickel (AA,
Nickel (AA,
Osmium (AA,
White Phosphorus
Chromatography
Potassium (AA, Direct Aspiration)
Selenium (AA, Furnace Technique)
Selenium (AA, Gaseous Hydride)
Selenium (AA, Borohydride Reduction)
Silver (AA, Direct Aspiration)
Silver (AA, Furnace Technique)
Sodium (AA, Direct Aspiration)
Strontium (AA, Direct Aspiration)
Thallium (AA, Direct Aspiration)
Thallium (AA, Furnace Technique)
Tin (AA, Direct Aspiration)
Vanadium (AA, Direct Aspiration)
Vanadium (AA, Furnace Technique)
Zinc (AA, Direct Aspiration)
Zinc (AA, Furnace Technique)
Extraction and Gas
APPENDIX -- COMPANY REFERENCES
NOTE; A suffix of "A" in the method number indicates revision one
(the method has been revised once). A suffix of "B" in the method
number indicates revision two (the method has been revised twice).
A suffix of "C" in the method number indicates revision three (the
method has been revised three times). In order to properly document
the method used for analysis, the entire method number including the
suffix letter designation (e.g., A, B, or C) must be identified by the
analyst. A method reference found within the RCRA regulations and the
text of SW-846 methods and chapters refers to the latest promulgated
revision of the method, even though the method number does not include
the appropriate letter suffix.
CONTENTS - 3
Revision 4
January 1995
-------
VOLUME ONE
SECTION B
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
ACKNOWLEDGEMENTS
CHAPTER ONE, REPRINTED -- QUALITY CONTROL
1.0 Introduction
2.0 QA Project Plan
3.0 Field Operations
4.0 Laboratory Operations
5.0 Definitions
6.0 References
CHAPTER FOUR -- ORGANIC ANALYTES
4.1 Sampling Considerations
4.2 Sample Preparation Methods
4.2.1
Method
Method
Method
Method
Method
Method
Method
Extractions and Preparations
3500B:
3510C:
3520C:
3535:
3540C:
3541:
3542:
Method 3545:
Method 3550B:
Method 3560:
Method 3561:
Method 3580A:
Method 3585:
Method 5000:
Method 5021:
Method 5030B:
Organic Extraction and Sample Preparation
Separatory Funnel Liquid-Liquid Extraction
Continuous Liquid-Liquid Extraction
Solid Phase Extraction (SPE)
Soxhlet Extraction
Automated Soxhlet Extraction
Extraction of Semivolatile Analytes Collected Using
Modified Method 5 (Method 0010) Sampling Train
Accelerated Solvent Extraction
Ultrasonic Extraction
Supercritical Fluid Extraction of Total Recoverable
Petroleum Hydrocarbons (TRPH)
Supercritical Fluid Extraction of Polynuclear Aromatic
Hydrocarbons
Waste Dilution
Waste Dilution for Volatile Organics
Sample Preparation for Volatile Organic Compounds
Volatile Organic Compounds in Soils and Other Solid
Matrices Using Equilibrium Headspace
Purge-and-Trap for Aqueous Samples
CONTENTS - 4
Revision 4
January 1995
-------
Method 5031:
Method 5032:
Method 5035:
Method 5041A:
Volatile, Nonpurgeable, Water-Soluble Compounds by
Azeotropic Distillation
Volatile Organic Compounds by Vacuum Distillation
Closed-System Purge-and-Trap and Extraction for Volatile
Organics in Soil and Waste Samples
Analysis for Desorption of Sorbent Cartridges from
Volatile Organic Sampling Train (VOST): Capillary GC/MS
Technique
4.2.2
Cleanup
Method 3600C:
Method 3610B:
Method 3611B:
Method
Method
Method
Method
Method
Method
3620B:
3630C:
3640A:
3650B:
3660B:
3665A:
Cleanup
Alumina Cleanup
Alumina Column
Petroleum Wastes
Florisil Cleanup
Silica Gel Cleanup
Gel-Permeation Cleanup
Acid-Base Partition Cleanup
Sulfur Cleanup
Sulfuric Acid/Permanganate Cleanup
Cleanup and Separation of
4.3 Determination of Organic Analytes
4.3.1 Gas Chromatographic Methods
Method 8000B:
Method 8011:
Method 8015B:
Method 8021B:
Method 8031:
Method 8032A:
Method 8033:
Method 8041:
Method 8061A:
Method 8070A:
Method 8081A:
Method 8082:
Method 8091:
Method 8100:
Method 8111:
Determinative Chromatographic Separations
1,2-Dibromoethane and l,2-Dibromo-3-chloropropane by
Microextraction and Gas Chromatography
Nonhalogenated Organics Using GC/FID
Halogenated Volatiles by Gas Chromatography Using
Photoionization and Electrolytic Conductivity Detectors
in Series: Capillary Column Technique
Acrylonitrile by Gas Chromatography
Acrylamide by Gas Chromatography
Acetonitrile by Gas Chromatography with Nitrogen-
Phosphorus Detection
Phenols by Gas Chromatography: Capillary Column
Technique
Phthalate Esters by Capillary Gas Chromatography with
Electron Capture Detection (GC/ECD)
Nitrosamines by Gas Chromatography
Organochlorine Pesticides by Capillary Column Gas
Chromatography
Polychlorinated Biphenyls (PCBs) by Capillary Column Gas
Chromatography
Nitroaromatics and Cyclic Ketones: Capillary Column
Technique
Polynuclear Aromatic Hydrocarbons
Haloethers: Capillary Column Technique
CONTENTS - 5
Revision 4
January 1995
-------
Method 8121:
Method 8131:
Method 8141A:
Method 8151A:
Chlorinated Hydrocarbons
Capillary Column Technique
by Gas Chromatography:
Aniline and Selected Derivatives by GC: Capillary
Column Technique
Organophosphorus Compounds
Capillary Column Technique
Chlorinated Herbicides by GC Using
Pentafluorobenzylation Derivatization:
Technique
by Gas Chromatography:
Methylation or
Capillary Column
4.3.2
Method 8260B
Gas Chromatographic/Mass Spectroscopic Methods
Method 8270C
Method 8280A
Method 8290:
Volatile Organic Compounds by Gas Chromatography/Mass
Spectrometry (GC/MS): Capillary Column Technique
Semivolatile Organic Compounds by Gas
Chromatography/Mass Spectrometry (GC/MS): Capillary
Column Technique
The Analysis of Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans by High Resolution Gas
Chromatography/Low Resolution Mass Spectrometry
(HRGC/LRMS)
Signal-to-Noise Determination Methods
Recommended Safety and Handling Procedures for
PCDDs/PCDFs
Polychlorinated Dibenzodioxins (PCDDs) and
Polychlorinated Dibenzofurans (PCDFs) by High-Resolution
Gas Chromatography/High-Resolution Mass Spectrometry
(HRGC/HRMS)
Attachment A: Procedures for the Collection, Handling,
Analysis, and Reporting of Wipe Tests Performed
within the Laboratory
Appendix A:
Appendix B:
4.3.3
High Performance Liquid Chromatographic Methods
Method 8310:
Method 8315A:
Appendix
Method 8316:
Method 8318:
Method 8321A:
Method 8325:
Polynuclear Aromatic Hydrocarbons
Determination of Carbonyl Compounds by High Performance
Liquid Chromatography (HPLC)
Recrystallization of 2,4-Dinitrophenylhydrazine
(DNPH)
Acrylamide, Acrylonitrile and Acrolein by High
Performance Liquid Chromatography (HPLC)
N-Methylcarbamates by High Performance Liquid
Chromatography (HPLC)
Solvent Extractable Non-Volatile Compounds by High
Performance Liquid Chromatography/Thermospray/Mass
Spectrometry (HPLC/TS/MS) or Ultraviolet (UV) Detection
Solvent Extractable Non-Volatile Compounds by High
Performance Liquid Chromatography/Particle Beam/Mass
Spectrometry (HPLC/PB/MS)
CONTENTS - 6
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Method 8330: Nitroaromatics and Nitramines by High Performance Liquid
Chromatography (HPLC)
Method 8331: Tetrazene by Reverse Phase High Performance Liquid
Chromatography (HPLC)
Method 8332: Nitroglycerine by High Performance Liquid Chromatography
4.3.4 Infrared Methods
Method 8410: Gas Chromatography/Fourier Transform Infrared (GC/FT-IR)
Spectrometry for Semi volatile Organics: Capillary
Column
Method 8430: Analysis of Bis(2-chloroethyl)ether Hydrolysis Products
by Direct Aqueous Injection GC/FT-IR
Method 8440: Total Recoverable Petroleum Hydrocarbons by Infrared
Spectrophotometry
4.3.5 Miscellaneous Spectrometric Methods
Method 8520: Continuous Measurement of Formaldehyde in Ambient Air
4.4 Immunoassay Methods
Method 4000: Immunoassay
Method 4010A: Screening for Pentachlorophenol by Immunoassay
Method 4015: Screening for 2,4-Dichlorophenoxyacetic Acid by
Immunoassay
Method 4020: Screening for Polychlorinated Biphenyls by Immunoassay
Method 4030: Soil Screening for Petroleum Hydrocarbons by Immunoassay
Method 4035: Soil Screening for Polynuclear Aromatic Hydrocarbons
(PAHs) by Immunoassay
Method 4040: Soil Screening for Toxaphene by Immunoassay
Method 4041: Soil Screening for Chlordane by Immunoassay
Method 4042: Soil Screening for DDT by Immunoassay
Method 4050: TNT Explosives in Water and Soils by Immunoassay
Method 4051: Hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX) in Soil
and Water by Immunoassay
4.5 Miscellaneous Screening Methods
Method 3810: Headspace
Method 3820: Hexadecane Extraction and Screening of Purgeable
Organics
Method 8275A: Semi volatile Organic Compounds (PAHs and PCBs) in
Soils/Sludges and Solid Wastes Using Thermal
Extraction/Gas Chromatography/Mass Spectrometry
(TE/GC/MS)
Method 8515: Colorimetric Screening Method for Trinitrotoluene (TNT)
in Soil
Method 9078: Screening Test Method for Polychlorinated Biphenyls in
Soil
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Method 9079:
Screening Test Method for Polychlorinated Biphenyls in
Transformer Oil
APPENDIX -- COMPANY REFERENCES
i
NOTE; A suffix of "A" in the method number indicates revision one
(the method has been revised once). A suffix of "B" in the method
number indicates revision two (the method has been revised twice).
A suffix of "C" in the method number indicates revision three (the
method has been revised three times). In order to properly document
the method used for analysis, the entire method number including the
suffix letter designation (e.g., A, B, or C) must be identified by the
analyst. A method reference found within the RCRA regulations and the
text of SW-846 methods and chapters refers to the latest promulgated
revision of the method, even though the method number does not include
the appropriate letter suffix.
CONTENTS - 8
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VOLUME ONE
SECTION C
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
CHAPTER ONE, REPRINTED -- QUALITY CONTROL
1.0 Introduction
2.0 QA Project Plan
3.0 Field Operations
4.0 Laboratory Operations
-5.0 Definitions
6.0 References
CHAPTER FIVE -- MISCELLANEOUS TEST METHODS
Method
Method
Method
Method
Method
Method
Method
5050:
9010A:
9012A:
9013:
9020B:
9021:
9022:
Method 9023:
Method 9030A:
Method 9031:
Method 9035:
Method 9036:
Method 9038:
Method 9056:
Method 9057:
Method 9060:
Method 9065:
Method 9066:
Method 9067:
Method 9070:
Method 9071A:
Bomb Preparation Method for Solid Waste
Total and Amenable Cyanide (Colorimetric, Manual)
Total and Amenable Cyanide (Colorimetric, Automated UV)
Cyanide Extraction Procedure for Solids and Oils
Total Organic Hal ides (TOX)
Purgeable Organic Hal ides (POX)
Total Organic Hal ides (TOX) by Neutron Activation
Analysis
Extractable Organic Hal ides (EOX) in Solids
Acid-Soluble and Acid-Insoluble Sulfides
Extractable Sulfides
Sulfate (Colorimetric, Automated, Chloranilate)
Sulfate (Colorimetric, Automated, Methylthymol Blue, AA
ID
Sulfate (Turbidimetric)
Determination of Inorganic Anions by Ion Chromatography
Determination of Chloride from HC1/HC12 Emission
Sampling Train (Methods 0050 and 0051) by Anion
Chromatography
Total Organic Carbon
Phenol ics (Spectrophotometric, Manual 4-AAP with
Distillation)
Phenolics (Colorimetric, Automated 4-AAP with
Distillation)
Phenolics (Spectrophotometric, MBTH with Distillation)
Total Recoverable Oil & Grease (Gravimetric, Separatory
Funnel Extraction)
Oil and Grease Extraction Method for Sludge and Sediment
Samples
CONTENTS - 9
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Method 9075:
Method 9076:
Method 9077:
Method A:
Method B:
Method C:
Method 9131:
Method 9132:
Method 9210:
Method 9211:
Method 9212:
Method 9213:
Method 9214:
Method 9215:
Method 9250:
Method 9251:
Method 9253:
Method 9320:
Test Method for Total Chlorine in New and Used Petroleum
Products by X-Ray Fluorescence Spectrometry (XRF)
Test Method for Total Chlorine in New and Used Petroleum
Products by Oxidative Combustion and Microcoulometry
Test Methods for Total Chlorine in New and Used
Petroleum Products (Field Test Kit Methods)
Fixed End Point Test Kit Method
Reverse Titration Quantitative End Point Test Kit
Method
Direct Titration Quantitative End Point Test Kit Method
Total Coliform: Multiple Tube Fermentation Technique
Total Coliform: Membrane Filter Technique
Potentiometric Determination of Nitrate in Aqueous
Samples with Ion-Selective Electrode
Potentiometric Determination of Bromide in Aqueous
Samples with Ion-Selective Electrode
Potentiometric Determination of Chloride in Aqueous
Samples with Ion-Selective Electrode
Potentiometric Determination of Cyanide in Aqueous
Samples and Distillates with Ion-Selective Electrode
Potentiometric Determination of Fluoride in Aqueous
Samples with Ion-Selective Electrode
Potentiometric Determination of Sulfide in Aqueous
Samples and Distillates with Ion-Selective Electrode
Chloride (Colorimetric, Automated Ferricyanide AAI)
Chloride (Colorimetric, Automated Ferricyanide AAII)
Chloride (Titrimetric, Silver Nitrate)
Radium-228
CHAPTER SIX -- PROPERTIES
Method 1030:
Method 1120:
Method 1312:
Method 1320:
Method 1330A:
Method 9041A:
Method 9045C:
Method 9050A:
Method 9080:
Method 9081:
Method 9090A:
Method 9095A:
Method 9096:
Appendix A:
Method 9100:
Method 9310:
Method 9315:
Ignitability of Solids
Dermal Corrosion
Synthetic Precipitation Leaching Procedure
Multiple Extraction Procedure
Extraction Procedure for Oily Wastes
pH Paper Method
Soil and Waste pH
Specific Conductance
Cation-Exchange Capacity of Soils
Cation-Exchange Capacity of Soils
Compatibility Test for Wastes and
Paint Filter Liquids Test
Liquid Release Test (LRT) Procedure
Liquid Release Test Pre-Test
Saturated Hydraulic Conductivity, Saturated Leachate
Conductivity, and Intrinsic Permeability
Gross Alpha and Gross Beta
Alpha-Emitting Radium Isotopes
(Ammonium Acetate)
(Sodium Acetate)
Membrane Liners
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PART II CHARACTERISTICS
CHAPTER SEVEN -- INTRODUCTION AND REGULATORY DEFINITIONS
7.1 Ignitability
7.2 Corrosivity
7.3 Reactivity
Test Method to Determine Hydrogen Cyanide Released from Wastes
Test Method to Determine Hydrogen Sulfide Released from Wastes
7.4 Toxicity Characteristic Leaching Procedure
CHAPTER EIGHT -- METHODS FOR DETERMINING CHARACTERISTICS
8.1 Ignitability
Method 1010:
1
Method 1020A:
8.3
8.4
Pensky-Martens Closed-Cup Method for Determining
Ignitability
Setaflash Closed-Cup Method for Determining Ignitability
8.2 Corrosivity
Method 9040B:
Method 1110:
Reactivity
Toxicity
Method 1310A:
Method 1311:
pH Electrometric Measurement
Corrosivity Toward Steel
Extraction Procedure (EP) Toxicity Test Method and
Structural Integrity Test
Toxicity Characteristic Leaching Procedure
APPENDIX -- COMPANY REFERENCES
NOTE: A suffix of "A" in the method number indicates revision one
(the method has been revised once). A suffix of "B" in the method
number indicates revision two (the method has been revised twice).
A suffix of "C" in the method number indicates revision three (the
method has been revised three times). In order to properly document
the method used for analysis, the entire method number including the
suffix letter designation (e.g., A, B, or C) must be identified by the
analyst. A method reference found within the RCRA regulations and the
text of SW-846 methods and chapters refers to the latest promulgated
revision of the method, even though the method number does not include
the appropriate letter suffix.
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VOLUME TWO
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
CHAPTER ONE, REPRINTED -- QUALITY CONTROL
1.0 Introduction
2.0 QA Project Plan
3.0 Field Operations
4.0 Laboratory Operations
5.0 Definitions
6.0 References
PART III SAMPLING
CHAPTER NINE -- SAMPLING PLAN
9.1 Design and Development
9.2 Implementation
CHAPTER TEN -- SAMPLING METHODS
Method 0010:
Appendix A:
Appendix B:
Method 0011:
Method 0020:
Method 0023A:
Method 0030:
Method 0031:
Method 0040:
Method 0050:
Method 0051:
Method 0100:
Modified Method 5 Sampling Train
Preparation of XAD-2 Sorbent Resin
Total Chromatographable Organic Material Analysis
Sampling for Formaldehyde Emissions from Stationary
Sources
Source Assessment Sampling System (SASS)
Sampling Method for Polychlorinated Dibenzo-p-Dioxins
and Polychlorinated Dibenzofuran Emissions from
Stationary Sources
Volatile Organic Sampling Train
Sampling Method for Volatile Organic Compounds (SMVOC)
Sampling of Principal Organic Hazardous Constituents
from Combustion Sources Using Tedlar® Bags
Isokinetic HC1/C12 Emission Sampling Train
Midget Impinger HC1/C12 Emission Sampling Train
Sampling for Formaldehyde and Other Carbonyl Compounds
in Indoor Air
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PART IV MONITORING
CHAPTER ELEVEN -- GROUND WATER MONITORING
11.1 Background and Objectives
11.2 Relationship to the Regulations and to Other Documents
11.3 Revisions and Additions
11.4 Acceptable Designs and Practices
11.5 Unacceptable Designs and Practices
CHAPTER TWELVE -- LAND TREATMENT MONITORING
12.1 Background
12.2 Treatment Zone
12.3 Regulatory Definition
12.4 Monitoring and Sampling Strategy
12.5 Analysis
12.6 References and Bibliography
CHAPTER THIRTEEN - INCINERATION
13.1 Introduction
13.2 Regulatory Definition
13.3 Waste Characterization Strategy
13.4 Stack-Gas Effluent Characterization Strategy
13.5 Additional Effluent Characterization Strategy
13.6 Selection of Specific Sampling and Analysis Methods
13.7 References
APPENDIX -- COMPANY REFERENCES
NOTE; A suffix of "A" in the method number indicates revision one
(the method has been revised once). A suffix of "B" in the method
number indicates revision two (the method has been revised twice).
A suffix of "C" in the method number indicates revision three (the
method has been revised three times). In order to properly document
the method used for analysis, the entire method number including the
suffix letter designation (e.g., A, B, or C) must be identified by the
analyst. A method reference found within the RCRA regulations and the
text of SW-846 methods and chapters refers to the latest promulgated
revision of the method, even though the method number does not include
the appropriate letter suffix.
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PREFACE AND OVERVIEW
PURPOSE OF THE MANUAL
Test Methods for Evaluating Solid IVaste (SW-846) provides a unified, up-to-date
source of information on sampling and analysis related to compliance with RCRA
regulations. It brings together into one reference all sampling and testing
methodologies approved by the Office of Solid Waste for use in implementing the RCRA
regulatory program. The manual provides methodologies for collecting and testing
representative samples of waste and other materials to be monitored. Aspects of
sampling and testing in SW-846 include quality control, sampling plan development and
implementation, analysis of inorganic and organic constituents, the estimation of
intrinsic physical properties, and the appraisal of waste characteristics.
The procedures described in this manual are meant to be comprehensive and
detailed, coupled with the realization that the problems encountered in sampling and
analytical situations require a certain amount of flexibility. The solutions to these
problems will depend, in part, on the skill, training, and experience of the analyst.
For some situations, it is possible to use this manual in rote fashion. In other
situations, it will require a combination of technical abilities, using the manual as
guidance rather than in a step-by-step, word-by-word fashion. Although this puts an
extra burden on the user, it is unavoidable because of the variety of sampling and
analytical conditions found with hazardous wastes.
ORGANIZATION AND FORMAT
This manual is divided into two volumes and thirteen chapters. Volume I focuses
on laboratory activities and is divided into three sections: IA, IB, and 1C. Volume
IA deals with quality control procedures, selection of appropriate test methods, and
analytical methods for inorganic species. Volume IB consists of methods for organic
analytes. Volume 1C includes a variety of test methods for miscellaneous analytes and
properties, including for use in evaluating whether a waste exhibits certain hazardous
waste characteristics. Volume II deals with sample acquisition and includes quality
control, sampling plan design and implementation, and field sampling methods.
Discussions regarding ground water monitoring, land treatment monitoring, and
incineration are also included in Volume II.
Volume I begins with an overview of the quality control procedures that should
be adhered to during application of the sampling and analysis methods. The quality
control chapter (Chapter One) and the method chapters are interdependent. The
analytical procedures cannot be used without a thorough understanding of the quality
control requirements and the means to implement them. This understanding can be
achieved only by reviewing Chapter One and the analytical methods together. It is
expected that individual laboratories, using SW-846 as the reference source, will
select appropriate methods and develop a standard operating procedure (SOP) to be
followed by the laboratory. The SOP should incorporate the pertinent information from
this manual adopted to the specific needs and circumstances of the individual
laboratory as well as to the materials to be evaluated.
The method selection chapter (Chapter Two) presents a comprehensive discussion
of the application of these methods to various matrices in the determination of groups
PREFACE - 1
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of analytes or specific analytes. It aids the chemist in constructing the correct
analytical method from the array of procedures which may cover the
matrix/analyte/concentration combination of interests. The section discusses the
objective of the testing program and its relationship to the choice of an analytical
method. Flow charts and tables provide guidance in the selection of the correct
analytical procedures to form the appropriate method.
The analytical methods are separated into distinct procedures describing
specific, independent analytical operations. These include extraction, digestion,
cleanup, and determination. This format allows linking of the various steps in the
analysis according to the type of sample (e.g., water, soil, sludge, still bottom);
analytes(s) of interest, needed sensitivity, and available analytical instrumentation.
However, Chapters Five (Miscellaneous) and Six (Properties) give complete methods which
are not amenable to such segmentation to form discrete procedures. The introductory
material at the beginning of Chapters Three (Inorganic Analytes) and Four (Organic
Analytes) contains information on sample handling and preservation, safety, and sample
preparation.
Part II, Characteristics, of Volume I describes the hazardous waste
characteristics (Chapter Seven) and methods used to determine if the waste is hazardous
because it exhibits a particular characteristic (Chapters Seven and Eight).
Volume II gives background information on statistical and nonstatistical aspects
of sampling. It also presents practical sampling techniques appropriate for situations
presenting a variety of physical conditions.
Information regarding the regulatory aspects of several monitoring categories is
also found in Volume II. These categories include ground water monitoring (Chapter
Eleven), land treatment (Chapter Twelve), and incineration (Chapter Thirteen). The
purpose of this guidance is to orient the user to the analytical objective, and to
assist in the development of data quality objectives, sampling plans, and SOPs.
Significant interferences, or other problems, may be encountered with certain
samples. In these situations, the analyst is advised to contact the Chief, Methods
Section (5304), Technical Assessment Branch, Office of Solid Waste, US EPA, Washington,
DC 20460 (202-260-4761) for assistance. The manual is intended to serve all those
with a need to evaluate solid waste. Your comments, corrections, suggestions, and
questions concerning any material contained in, or omitted from, this manual will be
gratefully appreciated. Please direct your comments to the above address.
SW-846 METHOD NUMBERS
When published as a new method to SW-846, a method's number does not include a
letter suffix. However, each time the method is revised and promulgated as part of an
SW-846 update, it receives a new letter suffix, i.e, a suffix of "A" indicates revision
one of that method, a suffix of "B" indicates revision two, etc. In order to properly
document the SW-846 method used during analysis, the entire method number including the
suffix letter designation must be identified by the analyst. In addition, a method
reference found within the RCRA regulations and the text of SW-846 methods and chapters
always refers to the latest promulgated revision of the method, even if the method
number at those locations does not include the appropriate letter suffix.
PREFACE - 2
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CHAPTER TWO
CHOOSING THE CORRECT PROCEDURE
2.1 PURPOSE
The purpose of this chapter is to aid the analyst in choosing the
appropriate methods for sample analyses, based upon the sample matrix and the
analytes to be determined.
2.1.1 Trace Analysis vs. Macroanalysis
Through the choice of sample size and concentration procedures, the methods
presented in SW-846 were designed to address the problem of "trace" analyses
(<1000 ppm), and have been developed for an optimized working range. These
methods are also applicable to "minor" (1000 ppm - 10,000 ppm) and "major"
(>10,000 ppm) analyses, as well, through use of appropriate sample preparation
techniques that result in analyte concentrations within that optimized range.
Such sample preparation techniques include:
1) adjustment of size of sample prepared for analysis,
2) adjustment of injection volumes,
3) dilution or concentration of sample,
4) elimination of concentration steps prescribed for "trace" analyses,
and
5) direct injection (of samples to be analyzed for volatile
constituents).
The performance data presented in each of these methods were generated from
"trace" analyses, and may not be applicable to "minor" and "major" analyses.
Generally, extraction efficiency improves as concentration increases.
CAUTION: Great care should be taken when performing trace analyses after the
analysis of concentrated samples, given the possibility of
contamination.
2.1.2 Choice of Apparatus and Preparation of Reagents
Since many types and sizes of glassware and supplies are commercially
available, and since it is possible to prepare reagents and standards in many
different ways, the apparatus, reagents, and volumes specified in these methods
may be replaced by any similar types as long as this substitution does not affect
the overall quality of the analyses.
2.1.3 Quality Control Criteria Precedence
Chapter One contains general quality control (QC) guidance for analyses
using SW-846 methods. QC guidance specific to a given analytical technique
(e.g., extraction, cleanup, sample introduction, or analysis) may be found in
Methods 3500, 3600, 5000, 7000, and 8000. Method-specific QC criteria may be
found in Sec. 8.0 of each individual method (or in Sec. 11.0 of air sampling
methods). When inconsistencies exist between the information in these locations,
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method-specific QC criteria take precedence over both technique-specific criteria
and those criteria given in Chapter One, and technique-specific QC criteria take
precedence over the criteria in Chapter One.
2.2 REQUIRED INFORMATION
In order to choose the correct combination of methods to comprise the
appropriate analytical procedure, some basic information is required.
2.2.1 Physical State(s) of Sample
The phase characteristics of the sample must be known. There are several
general categories of phases into which the sample may be categorized, including:
Aqueous Oil or other Organic Liquid
Sludge TCLP or EP Extract
Solid Stack Sampling (VOST) Condensate
Ground Water Multiphase Sample
There may be a substantial degree of overlap between the phases listed
above and it may be useful to further divide these phases in certain instances.
A multiphase sample may be a combination of aqueous, organic liquid, sludge,
and/or solid phases, and generally must undergo a phase separation as the first
step in the analytical procedure.
2.2.2 Analytes
Analytes may be divided into various classes based on the determinative
methods which are used to identify and quantify them. The most basic
differentiation is between organic (e.g., carbon-containing) analytes and
inorganic (e.g., metals and anions) analytes.
Table 2-1 alphabetically lists the analytes SW-846 organic determinative
methods. Tables 2-2A and 2-2B list the organic analytes that may be prepared
using Method 3650. Table 2-3 lists the organic analytes that are collected from
stack gas effluents using the volatile organic sampling train (VOST) methodology.
Tables 2-4 through 2-34 list the analytes by organic determinative method.
Table 2-35 indicates which methods are applicable to inorganic analytes.
2.2.3 Detection Limits
Some regulations may require a specific sensitivity or detection limit for
an analysis, as in the determination of analytes for the Toxicity Characteristic
(TC) or for delisting petitions. Drinking water detection limits, for those
specific organic and metallic analytes covered by the National Primary Drinking
Water Regulations, are desired in the analysis of ground water.
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2.2.4 Analytical Objective
Knowledge of the analytical objective will be useful in the choice of
sample preparation procedures and in the selection of a determinative method.
This is especially true when the sample has more than one phase. Knowledge of
the analytical objective may not be possible or desirable at all management
levels, but that information should be transmitted to the analytical laboratory
management to ensure that the correct techniques are used during the analytical
effort.
2.2.5 Detection and Monitoring
The strategy for detection of compounds in environmental or process samples
may be contrasted with the strategy for collecting monitoring data. Detection
samples define initial conditions. When there is little information available
about the composition of the sample source, e.g., a well or process stream, mass
spectral identification of organic analytes leads to fewer false positive
results. Thus, the most practical form of detection for organic analytes is
often mass spectral identification. However, where the sensitivity requirements
exceed those that can be achieved using mass spectral method (e.g., GC/MS or
HPLC/MS), it may be necessary to employ a more sensitive detection method (e.g.,
electron capture). In these instances, the risk of false positive results may
be minimized by confirming the results through a second analysis with a
dissimilar detector or chromatographic column. Thus, the choice of technique for
organic analytes may be governed by the detection limit requirements and
potential interferents.
Similarly, the choice of technique for metals is governed by the detection
limit requirements and potential interferents.
In contrast, monitoring samples are analyzed to confirm existing and on-
going conditions, tracking the presence or absence of known constituents in an
environmental or process matrix. In well-defined matrices and under stable
analytical conditions, less compound-specific detection modes may be used, as the
risk of false positive results is less.
2.2.6 Sample Containers, Preservations, and Holding Times
Appropriate sample containers, sample preservation techniques, and sample
holding times for aqueous matrices are listed in Table 2-36, near the end of this
chapter. Similar information may be found in Table 3-1 of Chapter Three
(inorganic analytes) and Table 4-1 of Chapter Four (organic analytes). Samples
must be extracted and analyzed within the specified holding times for the results
to be considered reflective of total concentrations. Analytical data generated
outside of the specified holding times must be considered to be minimum values
only. Such data may be used to demonstrate that a waste is hazardous where it
shows the concentration of a constituent to be above the regulatory threshold but
cannot be used to demonstrate that a waste is not hazardous.
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2.3 IMPLEMENTING THE GUIDANCE
The choice of the appropriate sequence of methods depends on the
information required and on the experience of the analyst. Figure 2-1 summarizes
the organic analysis options available. Appropriate selection is confirmed by
the quality control results. The use of the recommended procedures, whether they
are approved or mandatory, does not release the analyst from demonstrating the
correct execution of the method.
2.3.1 Extraction and Sample Preparation Procedures for Organic Analytes
Methods for preparing samples for organic analytes are shown in Table 2-37.
Method 3500 and associated methods should be consulted for further details on
preparing the sample for analysis.
2.3.1.1 Aqueous Samples
Methods 3510 and 3520 may be used for extraction of the semivolatile
organic compounds from aqueous samples. The choice of a preparative
method depends on the sample. Method 3510, a separatory funnel liquid-
liquid extraction technique, is appropriate for samples which will not
form a persistent emulsion interface between the sample and the extraction
solvent. The formation of an emulsion that cannot be broken up by
mechanical techniques will prevent proper extraction of the sample.
Method 3520, a continuous liquid-liquid extraction technique, may be used
for any aqueous sample and will minimize emulsion formation.
Method 3535 is solid-phase extraction technique that has been tested
for organochlorine pesticides and phthalate esters and may be applicable
to other semivolatile and extractable compounds as well. The aqueous
sample is passed through a solid sorbent material which traps the
analytes. They are then eluted from the solid-phase sorbent with a small
volume of organic solvent. This technique may be used to minimize the
volumes of organic solvents that are employed, but may not be appropriate
for aqueous samples with high suspended solids contents.
2.3.1.1.1 Basic or Neutral Extraction of Semivolatile
Analytes
The solvent extract obtained by performing Method 3510, 3520,
or 3535 at a neutral or basic pH will contain the neutral organic
compounds and the organic bases of interest. Refer to Table 1 in
the extraction methods (3510 and/or 3520) for guidance on the
requirements for pH adjustment prior to extraction and analysis.
2.3.1.1.2 Acidic Extraction of Phenols and Acid Analytes
The solvent extract obtained by performing Method 3510, 3520,
or 3535 at a pH less than or equal to 2 will contain the phenols and
acid extractable organics of interest.
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2.3.1.2 Solid Samples
Soxhlet extraction (Methods 3540 and 3541), ultrasonic extraction
(Method 3550), and accelerated solvent extraction (Method 3545) may be
used with solid samples. Consolidated samples should be ground finely
enough to pass through a 1 mm sieve. In limited applications, waste
dilution (Methods 3580 and 3585) may be used if the entire sample is
soluble in the specified solvent.
Methods 3540, 3541, 3545, and 3550 are neutral-pH extraction
techniques and therefore, depending on the analysis requirements, acid-
base partition cleanup (Method 3650) may be necessary. Method 3650 will
only be needed if chromatographic interferences are severe enough to
prevent detection of the analytes of interest. This separation will be
most important if a GC method is chosen for analysis of the sample. If
GC/MS is used, the ion selectivity of the technique may compensate for
chromatographic interferences.
There are two extraction procedures for solid samples that employ
supercritical fluid extraction (SFE). Method 3560 is a technique for the
extraction of petroleum hydrocarbons from various solid matrices using
carbon dioxide at elevated temperature and pressure. Method 3561 may be
used to extract polynuclear aromatic hydrocarbons (PAHs) from solid
matrices using supercritical carbon dioxide.
2.3.1.3 Oils and Organic Liquids
Method 3580, waste dilution, may be used to prepare oils and organic
liquid samples for analysis of semivolatile and extractable organic
analytes by GC or GC/MS. Method 3585 may be employed for the preparation
of these matrices for volatiles analysis by GC or GC/MS. To avoid
overloading the analytical detection system, care must be exercised to
ensure that proper dilutions are made. Methods 3580 and 3585 give
guidance on performing waste dilutions.
To remove interferences for semivolatiles and extractables, Method
3611 (Alumina cleanup) may be performed on an oil sample directly, without
prior sample preparation.
Method 3650 is the only other preparative procedure for oils and
other organic liquids. This procedure is a back extraction into an
aqueous phase. It is generally introduced as a cleanup procedure for
extracts rather than as a preparative procedure. Oils generally have a
high concentration of semivolatile compounds and, therefore, preparation
by Method 3650 should be done on a relatively small aliquot of the sample.
Generally, extraction of 1 ml of oil will be sufficient to obtain a
saturated aqueous phase and avoid emulsions.
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2.3.1.4 Sludge Samples
Determining the appropriate methods for analysis of sludges is
complicated because of the lack of precise definitions of sludges with
respect to the relative percent of liquid and solid components. There is
no set ratio of liquid to solid which enables the analyst to determine
which of the three extraction methods cited is the most appropriate.
Sludges may be classified into three categories: liquid sludges, solid
sludges, and emulsions, but with appreciable overlap.
If the sample is an organic sludge (solid material and organic
liquid, as opposed to an aqueous sludge), the sample should be handled as
a multiphase sample.
2.3.1.4.1 Liquid Sludges
Use of Method 3510 or Method 3520 may be applicable to sludges
that behave like and have the consistency of aqueous liquids.
Ultrasonic extraction (Method 3550) and Soxhlet (Method 3540)
procedures will, most likely, be ineffective because of the
overwhelming presence of the liquid aqueous phase.
2.3.1.4.2 Solid Sludges
Soxhlet extraction (Methods 3540 and 3541), accelerated
solvent (Method 3545) extraction, and ultrasonic extraction (Method
3550) will be more effective when applied to sludge samples that
resemble solids. Samples may be dried or centrifuged to form solid
materials for subsequent determination of semivolatile compounds.
Using Method 3650, Acid-Base Partition Cleanup, on the extract
may be necessary, depending on whether chromatographic interferences
prevent determination of the analytes of interest.
2.3.1.4.3 Emulsions
Attempts should be made to break up and separate the phases of
an emulsion. Several techniques are effective in breaking emulsions
or separating the phases of emulsions, including:
1. Freezing/thawing: Certain emulsions will separate if exposed
to temperatures below 0°C.
2. Salting out: Addition of a salt to make the aqueous phase of
an emulsion too polar to support a less polar phase promotes
separation.
3. Centrifugation: Centrifugal force may separate emulsion
components by density.
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4. Addition of water or ethanol: Emulsion polymers may be
destabilized when a preponderance of the aqueous phase is
added.
If techniques for breaking emulsions fail, use Method 3520.
If the emulsion can be broken, the different phases (aqueous, solid,
or organic liquid) may then be analyzed separately.
2.3.1.5 Multiphase Samples
Choice of the procedure for separating multiphase samples is highly
dependent on the objective of the analysis. With a sample in which some
of the phases tend to separate rapidly, the percent weight or volume of
each phase should be calculated and each phase should be individually
analyzed for the required analytes.
An alternate approach is to obtain a homogeneous sample and attempt
a single analysis on the combination of phases. This approach will give
no information on the abundance of the analytes in the individual phases
other than what can be implied by solubility.
A third alternative is to select phases of interest and to analyze
only those selected phases. This tactic must be consistent with the
sampling/analysis objectives or it will yield insufficient information for
the time and resources expended. The phases selected should be compared
with Figure 2-1 and Table 2-37 for further guidance.
2.3.2 Cleanup Procedures
Each category in Table 2-38, Cleanup of Organic Analyte Extracts,
corresponds to one of the possible determinative methods available in the manual.
Cleanups employed are determined by the analytes of interest within the extract.
However, the necessity of performing cleanup may also depend upon the matrix from
which the extract was developed. Cleanup of a sample may be done exactly as
instructed in the cleanup method for some of the analytes. There are some
instances when cleanup using one of the methods may only proceed after the
procedure is modified to optimize recovery and separation. Several cleanup
techniques may be possible for each analyte category. The information provided
is not meant to imply that any or all of these methods must be used for the
analysis to be acceptable. Extracts with components which interfere with
spectral or chromatographic determinations are expected to be subjected to
cleanup procedures.
The analyst's discretion must determine the necessity for cleanup
procedures, as there are no clear cut criteria for indicating their use. Method
3600 and associated methods should be consulted for further details on extract
cleanup.
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2.3.3 Determinative Procedures
The determinative methods for organic analytes have been divided into three
categories, as shown in Table 2-39: gas chromatography/mass spectrometry
(GC/MS); specific detection methods, i.e., gas chromatography (GC) with specific
non-MS detectors; and high performance liquid chromatography (HPLC). This
division is intended to help an analyst choose which determinative method will
apply. Under each analyte column, SW-846 method numbers have been indicated, if
appropriate, for the determination of the analyte. A blank has been left if no
chromatographic determinative method is available.
Generally, the MS procedures are more specific but less sensitive than the
appropriate gas chromatographic/specific detection method.
Method 8000 gives a general description of the techniques of gas
chromatography and high performance liquid chromatography. Method 8000 should
be consulted prior to application of any of the gas chromatographic methods.
Method 8081 (organochlorine pesticides), Method 8082 (polychlorinated
biphenyls), Method 8141 (organophosphorus pesticides), and Method 8151
(chlorinated herbicides), are preferred over GC/MS because of the combination of
selectivity and sensitivity of the flame photometric, nitrogen-phosphorus, and
electron capture detectors.
Method 8260 is a GC/MS method for volatile analytes, which employs a
capillary column. A variety of sample introduction techniques may be used with
Method 8260, including Methods 5021, 5030, 5031, and 3585. A GC with a selective
detector is also useful for the determination of volatile organic compounds in
a monitoring scenario, as described in Sec. 2.2.5.
Method 8270 is a GC/MS method for semivolatile analytes, which employs a
capillary column.
Table 2-39 lists several GC and HPLC methods that apply to only a small
number of analytes. Methods 8031 and 8033 are GC methods for acrolein,
acrylonitrile, and acetonitrile. Methods 8315 and 8316 are HPLC methods for
these three analytes. Method 8316 also addresses acrlyamide, which may be
analyzed by Method 8032.
HPLC methods have been developed for other types of analytes, most notably
carbamates (Method 8318), azo dyes and organophosphorus pesticides (Method 8321),
PAHs (Method 8310), explosives (Methods 8330 and 8331), and some volatile
organics (Methods 8315 and 8316).
Method 8430 utilizes a Fourier Transform Infrared Spectrometer (FT-IR)
coupled to a gas chromotograph to determine bis(2-chloroethyl) ether and its
hydrolysis products. The sample is introduced by direct aqueous injection.
Method 8440 may be employed for the determination of total recoverable petroleum
hydrocarbons (TRPH) in solid samples by infrared (IR) spectrophotometry. The
samples may be extracted with supercritical carbon dioxide, using Method 3560.
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2.4 CHARACTERISTICS
Figure 2-2 outlines a sequence for determining if a waste exhibits one or
more of the characteristics of a hazardous waste.
2.4.1 EP and TCLP extracts
The leachate obtained from using either the EP (Figure 2-3A) or the TCLP
(Figure 2-3B) is an aqueous sample, and therefore, requires further solvent
extraction prior to the analysis of semivolatile compounds.
The TCLP leachate is solvent extracted with methylene chloride at a pH > 11
and at a pH <2 by either Method 3510 or 3520. Method 3510 should be used unless
the formation of emulsions between the sample and the solvent prevent proper
extraction. If this problem is encountered, Method 3520 should be employed.
The solvent extract obtained by performing either Method 3510 or 3520 at
a basic or neutral pH will contain the base/neutral compounds of interest. Refer
to the specific determinative method for guidance on the pH requirements for
extraction prior to analysis. Method 5031 (Azeotropic Distillation) may be used
as an effective preparative method for pyridine.
Due to the high concentration of acetate in the TCLP extract, it is
recommended that purge-and-trap be used to introduce the volatile sample into the
gas chromatograph.
2.5 GROUND WATER
Appropriate analysis schemes for the determination of analytes in ground
water are presented in Figures 2-4A, 2-4B, and 2-4C. Quantitation limits for the
inorganic analytes should correspond to the drinking water limits which are
avail able.
2.5.1 Special Techniques for Inorganic Analytes
All atomic absorption analyses should employ appropriate background
correction systems whenever spectral interferences could be present. Several
background correction techniques are employed in modern atomic absorption
spectrometers. Matrix modification can complement background correction in some
cases. Since no approach to interference correction is completely effective in
all cases, the analyst should attempt to verify the adequacy of correction. If
the interferant is known (e.g., high concentrations of iron in the determination
of selenium), accurate analyses of synthetic solutions of the interferant (with
and without analyte) could establish the efficacy of the background correction.
If the nature of the interferant is not established, good agreement of analytical
results using two substantially different wavelengths could substantiate the
adequacy of the background correction.
To reduce matrix interferences, all graphite furnace atomic absorption
(GFAA) analyses should be performed using techniques which maximize an isothermal
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environment within the furnace cell. Data indicate that two such techniques,
L'vov platform and the Delayed Atomization Cuvette (DAC), are equivalent in this
respect, and produce high quality results.
All furnace atomic absorption analysis should be carried out using the best
matrix modifier for the analysis. Some examples of modifiers are listed below.
(See also the appropriate methods.)
Element(s) Modifier(s)
As and Se Nickel nitrate, palladium
Pb Phosphoric acid, ammonium phosphate, palladium
Cd Ammonium phosphate, palladium
Sb Ammonium nitrate, palladium
Tl Platinum, palladium
The ICP calibration standards must match the acid composition and strength
of the acids contained in the samples. Acid strengths in the ICP calibration
standards should be stated in the raw data.
2.5.2 Special Techniques for Indicated Analytes and Anions
If an Auto-Analyzer is used to read the cyanide distillates, the
spectrophotometer must be used with a 50 mm path length cell. If a sample is
found to contain cyanide, the sample must be redistilled a second time and
analyzed to confirm the presence of the cyanide. The second distillation must
fall within the 14-day holding time.
2.6 REFERENCES
1. Barcelona, M.J. "TOC Determinations in Ground Water"; Ground Water 1984,
22(1), 18-24.
2. Riggin, R.; et al. Development and Evaluation of Methods for Total Organic
Halide and Purgeable Organic Halide in Wastewater; U.S. Environmental
Protection Agency. Office of Research and Development. Environmental
Monitoring and Support Laboratory. ORD Publication Offices of Center for
Environmental Research Information: Cincinnati, OH, 1984; EPA-600/4-84-008.
3. McKee, G.; et al. Determination of Inorganic Anions in Water by Ion
Chromatoqraphy; (Technical addition to Methods for Chemical Analysis of
Water and Wastewater, EPA 600/4-79-020), U.S. Environmental Protection
Agency. Environmental Monitoring and Support Laboratory. ORD Publication
Offices of Center for Environmental Research Information: Cincinnati, OH,
1984; EPA-600/4-84-017.
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TABLE 2-1
DETERMINATIVE METHODS FOR ORGANIC ANALYTES
Analyte Applicable Method(s)
Acenaphthene 8100, 8270, 8275, 8310, 8410
Acenaphthylene 8100, 8270, 8275, 8310, 8410
Acetaldehyde 8315
Acetone 8015, 8260, 8315
Acetonitrile 8015, 8033, 8260
Acetophenone 8270
2-Acetylaminofluorene 8270
l-Acetyl-2-thiourea 8270
Acifluorfen 8151
Acrolein (Propenal) 8015, 8260, 8315, 8316
Acrylamide 8032, 8316
Acrylonitrile 8015, 8031, 8260, 8316
Alachlor 8081
Aldicarb (Temik) 8318, 8321
Aldicarb sulfone 8318, 8321
Aldicarb sulfoxide 8321
Aldrin 8081, 8270
Ally! alcohol 8015, 8260
Ally! chloride 8021, 8260
2-Aminoanthraquinone 8270
Aminoazobenzene 8270
4-Aminobiphenyl 8270
Aminocarb 8321
2-Amino-4,6-dinitrotoluene (2-Am-DNT) 8330
4-Amino-2,6-dinitrotoluene (4-Am-DNT) 8330
3-Amino-9-ethylcarbazole 8270
Anilazine 8270
Aniline 8131, 8270
o-Anisidine 8270
Anthracene 8100, 8270, 8275, 8310, 8410
Aramite 8270
Aroclor-1016 (PCB-1016) 8082, 8270
Aroclor-1221 (PCB-1221) 8082, 8270
Aroclor-1232 (PCB-1232) 8082, 8270
Aroclor-1242 (PCB-1242) 8082, 8270
Aroclor-1248 (PCB-1248) 8082, 8270
Aroclor-1254 (PCB-1254) 8082, 8270
Aroclor-1260 (PCB-1260) 8082, 8270
Aspon 8141
Asulam 8321
Atrazine 8141
Azinphos-ethyl 8141
Azinphos-methyl 8141, 8270
Barban 8270, 8321
Baygon (Propoxur) 8318, 8321
Bendiocarb 8321
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TABLE 2-1. (Continued)
Analyte Applicable Method(s)
Benefin 8091
Benomyl 8321
Bentazon 8151
Benzal chloride 8121
Benzaldehyde 8315
Benz(a)anthracene 8100, 8270, 8275, 8310, 8410
Benzene 8021, 8260
Benzenethiol (Thiophenol) 8270
Benzidine 8270, 8325
Benzo(b)fluoranthene 8100, 8270, 8275, 8310
Benzo(j)fluoranthene 8100
Benzojkjfluoranthene 8100, 8270, 8275, 8310
Benzoic acid 8270, 8410
Benzo(g,h,i)perylene 8100, 8270, 8275, 8310
Benzo(a)pyrene 8100, 8270, 8275, 8310, 8410
p-Benzoquinone 8270
Benzotrichloride 8121
Benzoylprop ethyl 8325
Benzyl alcohol 8270
Benzyl benzoate 8061
Benzyl chloride 8021, 8121, 8260
a-BHC (a-Hexachlorocyclohexane) 8081, 8121, 8270
(8-BHC (/3-Hexachlorocyclohexane) 8081, 8121, 8270
S-BHC (5-Hexachlorocyclohexane) 8081, 8121, 8270
7-BHC (Lindane, 7-Hexachlorocyclohexane) 8081, 8121, 8270
Bis(2-chloroethoxy)methane 8111, 8270, 8410
Bis(2-chloroethyl) ether 8111, 8270, 8410, 8430
Bis(2-chloroethyl)sulfide 8260
Bis(2-chloroisopropyl) ether 8021, 8111, 8270, 8410
Bis(2-n-butoxyethyl) phthalate 8061
Bis(2-ethoxyethyl) phthalate 8061
Bis(2-ethylhexyl) phthalate 8061, 8270, 8410
Bis(2-methoxyethyl) phthalate 8061
Bis(4-methyl-2-pentyl)-phthalate 8061
Bolstar (Sulprofos) 8141
Bromacil 8321
Bromoacetone 8021, 8260
4-Bromoaniline 8131
Bromobenzene 8021, 8260
Bromochloromethane 8021, 8260
2-Bromo-6-chloro-4-nitroaniline 8131
Bromodichloromethane 8021, 8260
2-Bromo-4,6-dinitroanil ine 8131
4-Bromofluorobenzene 8260
Bromoform 8021, 8260
Bromomethane 8021, 8260
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TABLE 2-1. (Continued)
Analyte Applicable Method(s)
4-Bromophenyl phenyl ether 8111, 8270, 8275, 8410
Bromoxynil 8270
Butanal 8315
1-Butanol (n-Butyl alcohol) 8015
n-Butanol 8260
2-Butanone (Methyl ethyl ketone, MEK) 8015, 8260
Butralin 8091
n-Butyl alcohol (1-Butanol) 8015
t-Butyl alcohol 8015
n-Butylbenzene 8021, 8260
sec-Butyl benzene 8021, 8260
tert-Butylbenzene 8021, 8260
Butyl benzyl phthalate 8061, 8270, 8410
2-sec-Butyl-4,6-dinitrophenol (DNBP, Dinoseb) 8041, 8151, 8270, 8321
Caffeine 8321
Captafol 8081, 8270
Captan 8270
Carbaryl (Sevin) 8270, 8318, 8321, 8325
Carbendazim 8321
Carbofuran (Furaden) 8270, 8318, 8321
Carbon disulfide 8260
Carbon tetrachloride 8021, 8260
Carbophenothion 8141, 8270
Chloral hydrate 8260
Chloramben 8151
Chlordane (technical) 8270
a-Chlordane 8081
•y-Chlordane 8081
Chlorfenvinphos 8141, 8270
Chloroacetonitrile 8260
2-Chloroacrylonitrile 8015
2-Chloroaniline 8131
3-Chloroaniline 8131
4-Chloroaniline 8131, 8270, 8410
Chlorobenzene 8021, 8260
Chlorobenzilate 8081, 8270
2-Chlorobiphenyl 8082, 8275
2-Chloro-l,3-butadiene (Chloroprene) 8021, 8260
1-Chlorobutane 8260
Chlorodibromomethane (Dibromochloromethane) 8021, 8260
2-Chloro-4,6-dinitroaniline 8131
l-Chloro-2,4-dinitrobenzene 8091
l-Chloro-3,4-dinitrobenzene 8091
Chloroethane 8021, 8260
2-Chloroethanol 8021, 8260, 8430
2-(2-Chloroethoxy)ethanol 8430
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TABLE 2-1. (Continued)
Analyte Applicable Method(s)
2-Chloroethyl vinyl ether 8021, 8260
Chloroform 8021, 8260
1-Chlorohexane 8260
Chloromethane 8021, 8260
5-Chloro-2-methylaniline ; 8270
Chloromethyl methyl ether 8021
2-Chloro-5-methylphenol 8041
4-Chloro-2-methylphenol 8041
4-Chloro-3-methylphenol 8041, 8270, 8410
3-(Chloromethyl)pyridine hydrochloride 8270
1-Chloronaphthalene 8270, 8275
2-Chloronaphthalene 8121, 8270, 8410
Chloroneb 8081
2-Chloro-4-nitroaniline 8131
4-Chloro-2-nitroaniline 8131
l-Chloro-2-nitrobenzene 8091
l-Chloro-4-nitrobenzene 8091
2-Chloro-6-nitrotoluene 8091
4-Chloro-2-nitrotoluene 8091
4-Chloro-3-nitrotoluene 8091
2-Chlorophenol 8041, 8270, 8410
3-Chlorophenol 8041
4-Chlorophenol 8041, 8410
4-Chloro-l,2-phenylenediamine 8270
4-Chloro-l,3-phenylenediamine 8270
4-Chlorophenyl phenyl ether 8111, 8270, 8410
2-Chlorophenyl 4-nitrophenyl ether 8111
3-Chlorophenyl 4-nitrophenyl ether 8111
4-Chlorophenyl 4-nitrophenyl ether 8111
o-Chlorophenyl thiourea 8325
Chloroprene (2-Chloro-l,3-butadiene) 8021, 8260
3-Chloropropionitrile 8260
Chloropropham 8321
Chloropropylate 8081
Chlorothalonil 8081
2-Chlorotoluene 8021, 8260
4-Chlorotoluene 8021, 8260
Chloroxuron 8321
Chlorpyrifos 8141
Chlorpyrifos methyl 8141
Chrysene 8100, 8270, 8275, 8310, 8410
Coumaphos 8141, 8270
Coumarin Dyes 8321
p-Cresidine 8270
o-Cresol (2-Methylphenol) 8041, 8270, 8410
m-Cresol (3-Methylphenol) 8041, 8270
p-Cresol (4-Methylphenol) 8041, 8270, 8275, 8410
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TABLE 2-1. (Continued)
Analyte Applicable Method(s)
Crotonaldehyde 8015, 8260, 8315
Crotoxyphos 8141, 8270
Cyclohexanone 8315
2-Cyclohexyl-4,6-dinitrophenol 8041, 8270
2,4-D 8151, 8321
Dalapon 8151, 8321
2,4-DB 8151, 8321
DBCP (l,2-Dibromo-3-chloropropane) 8011, 8021, 8081, 8260, 8270
2,4-D, butoxyethanol ester 8321
DCM (Dichloromethane, Methylene chloride) 8021, 8260
DCPA 8081
DCPA diacid 8151
4,4'-DDD 8081, 8270
4,4'-DDE 8081, 8270
4,4'-DDT 8081, 8270
DDVP (Dichlorvos, Dichlorovos) 8141, 8270, 8321
2,2',3,3'4,4'5,5',6,6'-Decachlorobiphenyl 8275
Decanal 8315
Demeton-0, and Demeton-S 8141, 8270
2,4-D, ethylhexyl ester 8321
Diallate 8081, 8270
Diamyl phthalate 8061
2,4-Diaminotoluene 8270
Diazinon 8141
Dibenz(a,h)acridine 8100
Dibenz(a,j)acridine 8100, 8270
Dibenz(a,h)anthracene 8100, 8270, 8275, 8310
7H-Dibenzo(c,g)carbazole 8100
Dibenzofuran 8270, 8275, 8410
Dibenzo(a,e)pyrene 8100, 8270
Dibenzo(a,h)pyrene 8100
Dibenzo(a,i)pyrene 8100
Dibenzothiophene 8275
Dibromochloromethane (Chlorodibromomethane) 8021, 8260
l,2-Dibromo-3-chloropropane (DBCP) 8011, 8260, 8270
1,2-Dibromoethane (EDB, Ethylene dibromide) 8011, 8021, 8260
Dibromofluoromethane 8260
Dibromomethane 8021, 8260
2,6-Dibromo-4-nitroaniline 8131
2,4-Dibromophenyl 4-nitrophenyl ether 8111
Di-n-butyl phthalate 8061, 8270, 8410
Dicamba 8151, 8321
Dichlone 8081, 8270
3,4-Dichloroaniline 8131
1,2-Dichlorobenzene 8021, 8121, 8260, 8270, 8410
1,3-Dichlorobenzene 8021, 8121, 8260, 8270, 8410
1,4-Dichlorobenzene 8021, 8121, 8260, 8270, 8410
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TABLE 2-1. (Continued)
Analyte Applicable Method(s)
3,3'-Dichlorobenzidine 8270,8325
3,5-Dichlorobenzoic acid 8151
2,3-Dichlorobiphenyl 8082, 8275
3,3'-Dichlorobiphenyl 8275
cis-l,4-Dichloro-2-butene 8260
trans-l,4-Dichloro-2-butene 8260
Dichlorodifluoromethane 8021, 8260
1,1-Dichloroethane 8021, 8260
1,2-Dichloroethane 8021, 8260
1,1-Dichloroethene (Vinylidene chloride) 8021, 8260
cis-l,2-Dichloroethene 8021, 8260
trans-l,2-Dichloroethene 8021, 8260
Dichlorofenthion 8141
Dichloromethane (DCM, Methylene chloride) 8021, 8260
2,6-Dichloro-4-nitroaniline 8131
2,3-Dichloronitrobenzene 8091
2,4-Dichloronitrobenzene 8091
3,5-Dichloronitrobenzene 8091
3,4-Dichloronitrobenzene 8091
2,5-Dichloronitrobenzene 8091
2,3-Dichlorophenol 8041
2,4-Dichlorophenol 8041, 8270, 8410
2,5-Dichlorophenol 8041
2,6-Dichlorophenol 8041, 8270
3,4-Dichlorophenol 8041
3,5-Dichlorophenol 8041
2,4-Dichlorophenol 3-methyl-4-nitrophenyl ether 8111
2,6-Dichlorophenyl 4-nitrophenyl ether 8111
3,5-Dichlorophenyl 4-nitrophenyl ether 8111
2,5-Dichlorophenyl 4-nitrophenyl ether 8111
2,4-Dichlorophenyl 4-nitrophenyl ether 8111
2,3-Dichlorophenyl 4-nitrophenyl ether 8111
3,4-Dichlorophenyl 4-nitrophenyl ether 8111
Dichloroprop (Dichlorprop) 8151, 8321
1,2-Dichloropropane 8021, 8260
1,3-Dichloropropane 8021, 8260
2,2-Dichloropropane 8021, 8260
l,3-Dichloro-2-propanol 8021, 8260
1,1-Dichloropropene 8021, 8260
cis-l,3-Dichloropropene 8021, 8260
trans-l,3-Dichloropropene 8021, 8260
Dichlorovos (DDVP, Dichlorvos) 8141, 8270, 8321
Dichlorprop (Dichloroprop) 8151, 8321
Dichlorvos (DDVP, Dichlorovos) 8141, 8270, 8321
Dicrotophos 8141, 8270
Dicofol 8081
Dicyclohexyl phthalate 8061
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TABLE 2-1. (Continued)
Analyte Applicable Method(s)
Dieldrin 8081, 8270
1,2,3,4-Diepoxybutane 8260
Diesel range hydrocarbons 8015, 8440
Diethylene glycol 8430
Diethyl ether 8015, 8260
Diethyl phthalate 8061, 8270, 8410
Diethylstilbestrol 8270
Diethyl sulfate 8270
1,4-Difluorobenzene 8260
Dihexyl phthalate 8061
Dihydrosaffrole 8270
Diisobutyl phthalate 8061
Dimethoate 8141, 8270, 8321
3,3'-Dimethoxybenzidine 8270, 8325
Dimethylaminoazobenzene 8270
2,5-Dimethylbenzaldehyde 8315
7,12-Dimethylbenz(a)anthracene 8270
3,3'-Dimethylbenzidine 8270, 8325
a,a-Dimethylphenethylamine 8270
2,3-Dimethylphenol 8041
2,4-Dimethylphenol 8041, 8270
2,5-Dimethylphenol 8041
2,6-Dimethylphenol 8041
3,4-Dimethylphenol 8041
Dimethyl phthalate 8061, 8270, 8410
Dinitramine 8091
2,4-Dinitroaniline 8131
1,2-Dinitrobenzene 8091, 8270
1,3-Dinitrobenzene (1,3-DNB) 8091, 8270, 8330
1,4-Dinitrobenzene 8091, 8270
4,6-Dinitro-2-methylphenol 8270, 8410
2,4-Dinitrophenol 8041, 8270, 8410
2,5-Dinitrophenol 8041
2,4-Dinitrotoluene (2,4-DNT) 8091, 8270, 8330, 8410
2,6-Dinitrotoluene (2,6-DNT) 8091, 8270, 8330, 8410
Dinocap 8270
Dinonyl phthalate 8061
Dinoseb (2-sec-Butyl-4,6-dinitrophenol, DNBP) 8041, 8151, 8270, 8321
Di-n-octyl phthalate 8061, 8270, 8410
Dioxacarb 8318
1,4-Dioxane 8015, 8260
Dioxathion 8141, 8270
Di-n-propyl phthalate 8410
Diphenylamine 8270
5,5-Diphenylhydantoin 8270
1,2-Diphenylhydrazine 8270
TWO - 17 Revision 3
January 1995
-------
TABLE 2-1. (Continued)
Analyte Applicable Method(s)
Disperse Blue 3 8321
Disperse Blue 14 8321
Disperse Brown 1 8321
Disperse Orange 3 8321
Disperse Orange 30 8321
Disperse Red 1 8321
Disperse Red 5 8321
Disperse Red 13 8321
Disperse Red 60 8321
Disperse Yellow 5 8321
Disulfoton 8141, 8270, 8321
Diuron 8321, 8325
1,3-DNB (1,3-Dinitrobenzene) 8091, 8270, 8330
DNBP (2-sec-Butyl-4,6-dinitrophenol, Dinoseb) 8151, 8270, 8321
2,4-DNT (2,4-Dinitrotoluene) 8091, 8270, 8275, 8330, 8410
2,6-DNT (2,6-Dinitrotoluene) 8091, 8270, 8330, 8410
EDB (1,2-Dibromoethane, Ethylene dibromide) 8011, 8021, 8260
Endosulfan I 8081, 8270
Endosulfan II 8081, 8270
Endosulfan sulfate 8081, 8270
Endrin 8081, 8270
Endrin aldehyde 8081, 8270
Endrin ketone 8081, 8270
Epichlorohydrin 8021, 8260
EPN 8141, 8270
Ethanol 8015, 8260
Ethion 8141, 8270
Ethoprop 8141
Ethyl acetate 8015, 8260
Ethyl benzene 8021, 8260
Ethyl carbamate 8270
Ethyl cyanide (Propionitrile) 8015, 8260
Ethylene dibromide (EDB, 1,2-Dibromoethane) 8011, 8021, 8260
Ethylene glycol 8015, 8430
Ethylene oxide 8015, 8260
Ethyl methacrylate 8260
Ethyl methanesulfonate 8270
Etridiazole 8081
Famphur 8141, 8270, 8321
Fenitrothion 8141
Fensulfothion 8141, 8270, 8321
Fenthion 8141, 8270
Fenuron 8321
Fluchloralin 8270
Fluometuron 8321
Fluoranthene 8100, 8270, 8275, 8310, 8410
Fluorene 8100, 8270, 8275, 8310, 8410
TWO - 18 Revision 3
January 1995
-------
TABLE 2-1. (Continued)
Analyte Applicable Method(s)
Fluorescent Brightener 61 8321
Fluorescent Brightener 236 8321
Fluorobenzene 8260
2-Fluorobiphenyl 8270
2-Fluorophenol 8270
Fonophos 8141
Formaldehyde 8315
Furaden (Carbofuran) 8270, 8318, 8321
Gasoline range of hydrocarbons 8015
Halowax-1000 8081
Halowax-1001 8081
Halowax-1013 8081
Halowax-1014 8081
Halowax-1051 8081
Halowax-1099 8081
Heptachlor 8081, 8270
2,2',3,3',4,4',5-Heptachlorobiphenyl 8082, 8275
2,2',3,4,4',5,5'-Heptachlorobiphenyl 8082, 8275
2,2',3',4,4/,5',6-Heptachlorobiphenyl 8082
2,2',3,4',5,5',6-Heptachlorobiphenyl 8082, 8275
Heptachlor epoxide 8081, 8270
Heptanal 8315
Hexachlorobenzene 8081, 8121, 8270, 8275, 8410
2,2',3,3,4,4'-Hexachlorobiphenyl 8275
2,2',3,4,4',5-Hexachlorobiphenyl 8082, 8275
2,2',3,4,5,5'-Hexachlorobiphenyl 8082
2,2',3,5,5',6-Hexachlorobiphenyl 8082
2,2',4,4,5,5'-Hexachlorobiphenyl 8082
Hexachlorobutadiene 8021, 8121, 8260, 8270, 8410
a-Hexachlorocyclohexane (a-BHC) 8081, 8121, 8270
0-Hexachlorocyclohexane (/3-BHC) 8081, 8121, 8270
5-Hexachlorocyclohexane (6-BHC) 8081, 8121, 8270
7-Hexachlorocyclohexane (-y-BHC, Lindane) 8081, 8121, 8270
Hexachlorocyclopentadiene 8081, 8121, 8270, 8410
Hexachloroethane 8121, 8260, 8270, 8410
Hexachlorophene 8270
Hexachloropropene 8270
Hexafluoro-2-methyl-2-propanol 8015
Hexafluoro-2-propanol 8015
Hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX) 8330
Hexamethylphosphoramide (HMPA) 8141, 8270
Hexanal 8315
2-Hexanone 8260
Hexyl 2-ethylhexyl phthalate 8061
HMPA (Hexamethylphosphoramide) 8141, 8270
HMX (Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine) 8330
TWO - 19 Revision 3
January 1995
-------
TABLE 2-1. (Continued)
Analyte Applicable Method(s)
1,2,3,4,6,7,8-HpCDD 8280, 8290
HpCDD, total 8280
1,2,3,4,6,7,8-HpCDF 8280, 8290
1,2,3,4,7,8,9-HpCDF 8280, 8290
HpCDF, total 8280
1,2,3,4,7,8-HxCDD 8280, 8290
1,2,3,6,7,8-HxCDD 8280, 8290
1,2,3,7,8,9-HxCDD 8280, 8290
HxCDD, total 8280
1,2,3,4,7,8-HxCDF 8280, 8290
1,2,3,6,7,8-HxCDF 8280, 8290
1,2,3,7,8,9-HxCDF 8280, 8290
2,3,4,6,7,8-HxCDF 8280, 8290
HxCDF 8280
Hydroquinone 8270
3-Hydroxycarbofuran 8318, 8321
5-Hydroxydicamba 8151
2-Hydroxypropionitrile 8260
Indeno(l,2,3-cd)pyrene 8100, 8270, 8275, 8310
lodomethane (Methyl iodide) 8260
Isobutyl alcohol (2-Methyl-l-propanol) 8015, 8260
Isodrin 8081, 8270
Isophorone 8270, 8410
Isopropalin 8091
Isopropyl alcohol (2-Propanol) 8015, 8260
Isopropylbenzene 8021, 8260
p-Isopropyltoluene 8021, 8260
Isosafrole 8270
Isovaleraldehyde 8315
Jet fuel 8015, 8440
Kepone 8081, 8270
Lannate (Methomyl) 8318, 8321
Leptophos 8141, 8270
Lindane (7-Hexachlorocyclohexane, 7-BHC) 8081, 8121, 8270
Linuron (Lorox) 8321, 8325
Lorox (Linuron) 8321, 8325
Malathion 8141, 8270
Maleic anhydride 8270
Malononitrile 8260
MCPA 8151, 8321
MCPP 8151, 8321
Merphos 8141, 8321
Mestranol 8270
Mesurol (Methiocarb) 8318, 8321
Methacrylonitrile 8260
Methanol 8015, 8260
TWO - 20 Revision 3
January 1995
-------
TABLE 2-1. (Continued)
Analyte Applicable Method(s)
Methapyrilene 8270
Methiocarb (Mesurol) 8318, 8321
Methomyl (Lannate) 8318, 8321
Methoxychlor 8081, 8270
Methyl acrylate 8260
2-Methyl-l-propanol (Isobutyl alcohol) 8015, 8260
Methyl-t-butyl ether 8260
3-Methylcholanthrene 8100, 8270
4,4'-Methylenebis(2-chloroaniline) 8270
4,4/-Methylenebis(N,N-dimethylaniline) 8270
Methyl ethyl ketone (MEK, 2-Butanone) 8015, 8260
Methylene chloride (Dichloromethane, DCM) 8021, 8260
Methyl iodide (lodomethane) 8260
Methyl isobutyl ketone (MIBK, 4-Methyl-2-pentanone) 8015, 8260
Methyl methacrylate 8260
Methyl methanesulfonate 8270
2-Methylnaphthalene 8270, 8410
Methyl parathion 8270, 8321
4-Methyl-2-pentanone (MIBK, Methyl isobutyl ketone) 8015, 8260
2-Methylphenol (o-Cresol) 8041, 8270, 8410
3-Methylphenol (m-Cresol) 8041, 8270
4-Methylphenol (p-Cresol) 8041, 8270, 8410
2-Methylpyridine (2-Picoline) 8015, 8260, 8270
Methyl-2,4,6-trinitrophenylnitramine (Tetryl) 8330
Mevinphos 8141, 8270
Mexacarbate 8270, 8321
MIBK (Methyl isobutyl ketone, 4-Methyl-2-pentanone) 8015, 8260
Mirex 8081, 8270
Monocrotophos 8141, 8270, 8321
Monuron 8321, 8325
Naled 8141, 8270, 8321
Naphthalene 8021, 8100, 8260, 8270, 8275, 8310, 8410
NB (Nitrobenzene) 8091, 8260, 8270, 8330, 8410
1,2-Naphthoquinone 8091
1,4-Naphthoquinone 8270, 8091
1-Naphthylamine 8270
2-Naphthylamine 8270
Neburon 8321
Nicotine 8270
5-Nitroacenaphthene 8270
2-Nitroaniline 8131, 8270, 8410
3-Nitroaniline 8131, 8270, 8410
4-Nitroaniline 8131, 8270, 8410
5-Nitro-o-anisidine 8270
Nitrobenzene (NB) 8091, 8260, 8270, 8330, 8410
4-Nitrobiphenyl 8270
Nitrofen 8081, 8270
TWO - 21 Revision 3
January 1995
-------
TABLE 2-1. (Continued)
Analyte Applicable Method(s)
Nitroglycerin 8332
2-Nitrophenol 8041, 8270, 8410
3-Nitrophenol 8041
4-Nitrophenol 8041, 8151, 8270, 8410
4-Nitrophenyl phenyl ether 8111
2-Nitropropane 8260
Nitroquinoline-1-oxide 8270
N-Nitrosodi-n-butylamine 8015, 8260, 8270
N-Nitrosodiethylamine 8270
N-Nitrosodimethylamine 8070, 8270, 8410
N-Nitrosodi-n-butylamine (N-Nitrosodibutylamine) 8015, 8260, 8270
N-Nitrosodiphenylamine 8070, 8270, 8410
N-Nitrosodi-n-propylamine 8070, 8270, 8410
N-Nitrosomethylethylamine 8270
N-Nitrosomorpholine 8270
N-Nitrosopiperidine 8270
N-Nitrosopyrrolidine 8270
2-Nitrotoluene (o-Nitrotoluene, 2-NT) 8091, 8330
3-Nitrotoluene (m-Nitrotoluene, 3-NT) 8091, 8330
4-Nitrotoluene (p-Nitrotoluene, 4-NT) 8091, 8330
o-Nitrotoluene (2-Nitrotoluene, 2-NT) 8091, 8330
m-Nitrotoluene (3-Nitrotoluene, 3-NT) 8091, 8330
p-Nitrotoluene (4-Nitrotoluene, 4-NT) 8091, 8330
5-Nitro-o-toluidine 8270
trans-Nonachlor 8081
2,2'3,3'4,4'5,5'6-Nonachlorobiphenyl 8082, 8275
Nonanal 8315
2-NT (2-Nitrotoluene, o-Nitrotoluene) 8091, 8330
3-NT (3-Nitrotoluene, m-Nitrotoluene) 8091, 8330
4-NT (4-Nitrotoluene, p-Nitrotoluene) 8091, 8330
OCDD 8280, 8290
OCDF 8280, 8290
2,2',3,3',4,4'5,5'-Octachlorobiphenyl 8275
Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine (HMX) 8330
Octamethyl pyrophosphoramide 8270
Octanal 8315
Oxamyl 8321
4,4'-Oxydianiline 8270
Paraldehyde 8015, 8260
Parathion 8270
Parathion, ethyl 8141
Parathion, methyl 8141
PCB-1016 (Aroclor-1016) 8082, 8270
PCB-1221 (Aroclor-1221) 8082, 8270
PCB-1232 (Aroclor-1232) 8082, 8270
PCB-1242 (Aroclor-1242) 8082, 8270
PCB-1248 (Aroclor-1248) 8082, 8270
TWO - 22 Revision 3
January 1995
-------
TABLE 2-1. (Continued)
Analyte Applicable Method(s)
PCB-1254 (Aroclor-1254) 8082, 8270
PCB-1260 (Aroclor-1260) 8082, 8270
PCNB 8081
1,2,3,7,8-PeCDD 8280, 8290
PeCDD, total 8280
1,2,3,7,8-PeCDF 8280, 8290
2,3,4,7,8-PeCDF 8280, 8290
PeCDF, total 8280
Pendimethaline (Penoxalin) 8091
Penoxalin (Pendimethaline 8091
Pentachlorobenzene 8121, 8270
2,2',3,4,5'-Pentachlorobiphenyl 8082
2,2',4,5,5'-Pentachlorobiphenyl 8082, 8275
2,3,3',4',6-Pentachlorobiphenyl 8082
2,3',4,4',5-Pentachlorobiphenyl 8275
Pentachloroethane 8260
Pentachloronitrobenzene 8091, 8270
Pentachlorophenol 8041, 8151, 8270, 8410
Pentafluorobenzene 8260
Pentanal (Valeraldehyde) 8315
2-Pentanone 8015, 8260
Permethrin 8081
Perthane 8081
Phenacetin 8270
Phenanthrene 8100, 8270, 8275, 8310, 8410
Phenobarbital 8270
Phenol 8041, 8270, 8410
1,4-Phenylenediamine 8270
Phorate 8141, 8270, 8321
Phosalone 8270
Phosmet 8141, 8270
Phosphamidon 8141, 8270
Phthalic anhydride 8270
Picloram 8151
2-Picoline (2-Methylpyridine) 8015, 8260, 8270
Piperonyl sulfoxide 8270
Profluralin 8091
Promecarb 8318
Pronamide 8270
Propachlor 8081, 8321
Propanal (Propionaldehyde) 8315, 8321
1-Propanol 8015, 8260
2-Propanol (Isopropyl alcohol) 8015, 8260
Propargyl alcohol 8260
Propenal (Acrolein) 8260, 8315
Propham 8321
B-Propiolactone 8260
TWO - 23 Revision 3
January 1995
-------
TABLE 2-1. (Continued)
Analyte Applicable Method(s)
Propionaldehyde (Propanal) 8315
Propionitrile (Ethyl cyanide) 8015, 8260
Propoxur (Baygon) 8318, 8321
n-Propylamine 8260
n-Propylbenzene 8021, 8260
Propylthiouracil 8270
Prothiophos (Tokuthion) 8141
Pyrene 8100, 8270, 8275, 8310, 8410
Pyridine 8015, 8260, 8270
RDX (Hexahydro-l,3,5-trinitro-l,3,5-triazine) 8330
Resorcinol 8270
Ronnel 8141
Rotenone 8325
Safrole 8270
Sevin (Carbaryl) 8270, 8318, 8321, 8325
Siduron 8321, 8325
Simazine 8141
Silvex (2,4,5-TP) 8151, 8321
Solvent Red 3 8321
Solvent Red 23 8321
Stirophos (Tetrachlorvinphos) 8141, 8270
Strobane 8081
Strychnine 8270, 8321
Styrene 8021, 8260
Sul fall ate 8270
Sulfotepp 8141
Sulprofos (Bolstar) 8141
2,4,5-T 8151, 8321
2,4,5-T, butoxyethanol ester 8321
2,4,5-T, butyl ester 8321
2,3,7,8-TCDD 8280, 8290
TCDD, total 8280
2,3,7,8-TCDF 8280, 8290
TCDF, total 8280
Tebuthiuron 8321
Temik (Aldicarb) 8318, 8321
TEPP 8141
Terbufos 8141, 8270
Terphenyl 8270
1,2,3,4-Tetrachlorobenzene 8121
1,2,3,5-Tetrachlorobenzene 8121
1,2,4,5-Tetrachlorobenzene 8121, 8270
2,2',3,5'-Tetrachlorobiphenyl 8082, 8275
2,2',4,5'-Tetrachlorobiphenyl 8275
2,2',5,5'-Tetrachlorobiphenyl 8082, 8275
2,3',4,4'-Tetrachlorobiphenyl 8082, 8275
1,1,1,2-Tetrachloroethane 8021, 8260
TWO - 24 Revision 3
January 1995
-------
TABLE 2-1. (Continued)
Analyte Applicable Method(s)
1,1,2,2-Tetrachloroethane 8021, 8260
Tetrachloroethene 8021, 8260
2,3,4,5-Tetrachlorophenol 8041
2,3,4,6-Tetrachlorophenol 8041, 8270
2,3,5,6-Tetrachlorophenol 8041
2,3,4,5-Tetrachloronitrobenzene 8091
2,3,5,6-Tetrachloronitrobenzene 8091
Tetrachlorvinphos (Stirophos) 8141, 8270
Tetraethyl dithiopyrophosphate 8270
Tetraethyl pyrophosphate 8270
Tetrazene 8331
Tetryl (Methyl-2,4,6-trinitrophenylnitramine) 8330
Thiofanox 8321
Thionazin (Zinophos) 8141, 8270
Thiophenol (Benzenethiol) 8270
1,3,5-TNB (1,3,5-Trinitrobenzene) 8270, 8330
2,4,5-TNT (2,4,6-Trinitrobenzene) 8330
TOCP (Tri-o-cresylphosphate) 8141
Tokuthion (Prothiophos) 8141
m-Tolualdehyde 8315
o-Tolualdehyde 8315
p-Tolualdehyde 8315
Toluene 8021, 8260
Toluene diisocyanate 8270
o-Toluidine 8015, 8270
Toxaphene 8081, 8270
2,4,5-TP (Silvex) 8151, 8321
2,4,6-Tribromophenol 8270
2,4,6-Trichloroaniline 8131
2,4,5-Trichloroaniline 8131
1,2,3-Trichlorobenzene 8021, 8121, 8260
1,2,4-Trichlorobenzene 8021, 8121, 8260, 8270, 8275, 8410
2,2',5-Trichlorobiphenyl 8082, 8275
2,3',5-Trichlorobiphenyl 8275
2,4',5-Trichlorobiphenyl 8082, 8275
1,3,5-Trichlorobenzene 8121
1,1,1-Trichloroethane 8021, 8260
1,1,2-Trichloroethane 8021, 8260
Trichloroethene 8021, 8260
Trichlorofluoromethane 8021, 8260
Trichlorfon 8141, 8321
Trichloronate 8141
l,2,3-Trichloro-4-nitrobenzene 8091
l,2,4-Trichloro-5-nitrobenzene 8091
2,4,6-Trichloronitrobenzene 8091
2,3,4-Trichlorophenol 8041
2,3,5-Trichlorophenol 8041
TWO - 25 Revision 3
January 1995
-------
TABLE 2-1. (Continued)
Analyte Applicable Method(s)
2,3,6-Trichlorophenol 8041
2,4,5-Trichlorophenol 8041, 8270, 8410
2,4,6-Trichlorophenol 8041, 8270, 8410
2,4,6-Trichlorophenyl 4-nitrophenyl ether 8111
2,3,6-Trichlorophenyl 4-nitrophenyl ether 8111
2,3,5-Trichlorophenyl 4-nitrophenyl ether 8111
2,4,5-Trichlorophenyl 4-nitrophenyl ether 8111
3,4,5-Trichlorophenyl 4-nitrophenyl ether 8111
2,3,4-Trichlorophenyl 4-nitrophenyl ether 8111
1,2,3-Trichloropropane 8021, 8260
0,0,0-Triethyl phosphorothioate 8270
Trifluralin 8091, 8081, 8270
2,4,5-Trimethylaniline 8270
1,2,4-Trimethylbenzene 8021, 8260
1,3,5-Trimethylbenzene 8021, 8260
Trimethyl phosphate 8270
1,3,5-Trinitrobenzene (1,3,5-TNB) 8270, 8330
2,4,6-Trinitrobenzene (2,4,6-TNT) 8330
Tris-BP (Tris-(2,3-dibromopropyl) phosphate) 8270, 8321
Tri-o-cresylphosphate (TOCP) 8141
Tri-p-tolyl phosphate 8270
Tris-(2,3-dibromopropyl) phosphate (Tris-BP) 8270, 8321
Valeraldehyde (Pentanal) 8315
Vinyl acetate 8260
Vinyl chloride 8021, 8260
Vinylidene chloride (1,1-Dichloroethene) 8021, 8260
o-Xylene 8021, 8260
m-Xylene 8021, 8260
p-Xylene 8021, 8260
Zinophos (Thionazin) 8141, 8270
TWO - 26 Revision 3
January 1995
-------
TABLE 2-2A
METHOD 3650 (ACID-BASE PARTITION CLEANUP) - BASE/NEUTRAL FRACTION
Benz{a)anthracene Hexachlorobenzene
Benzo(a)pyrene Hexachlorobutadiene
Benzo(b)fluoranthene Hexachloroethane
Chiordane Hexachlorocyclopentadi ene
Chlorinated dibenzodioxins Naphthalene
Chrysene Nitrobenzene
Creosote Phorate
Dichlorobenzene(s) 2-Picoline
Dinitrobenzene Pyridine
2,4-Di n i trotoluene Tetrachlorobenzene(s)
Heptachlor Toxaphene
TABLE 2-2B
METHOD 3650 (ACID-BASE PARTITION CLEANUP) - ACID FRACTION
2-Chlorophenol 4-Nitrophenol
Cresol(s) Pentachlorophenol
Creosote Phenol
Dichlorophenoxyacetic acid Tetrachlorophenol(s)
2,4-Dimethylphenol Trichlorophenol(s)
4,6-Dinitro-o-cresol 2,4,5-TP (Silvex)
TWO - 27 Revision 3
January 1995
-------
TABLE 2-3
METHOD 5041 - SORBENT CARTRIDGES FROM VOLATILE ORGANIC SAMPLING TRAIN (VOST)
Acetone
Acrylonitrile
Benzene
Bromodichloromethane
Bromoform3
Bromomethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chiorodi brompmethane
Chloroethane
Chloroform
Chloromethane
Dibromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethyl benzene3
lodomethane
Methylene chloride
Styrene3
1,1,2,2-Tetrachloroethane3
Tetrachloroethene
Toluene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane3
Vinyl chloride
Xylenes3
3 Boiling point of this compound is above 132°C. Method 0030 is not
appropriate for quantitative sampling of this analyte.
b Boiling point of this compound is below 30°C. Special precautions must be
taken when sampling for this analyte by Method 0030. Refer to Sec. 1.3 of
Method 5041 for discussion.
TWO - 28
Revision 3
January 1995
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TABLE 2-4
METHOD 8011 (MICROEXTRACTION AND GAS CHROMATOGRAPHY)
l,2-Dibromo-3-chloropropane (DBCP)
1,2-Dibromoethane (EDB)
TABLE 2-5
METHOD 8015 (GC/FID) - NONHALOGENATED VOLATILES
Acetone
Acetonitrile
Acrolein
Acrylonitrile
Allyl alcohol
1-Butanol (n-Butyl alcohol)
t-Butyl alcohol
2-Chioroacrylonitri1e
Crotonaldehyde
Diethyl ether
1,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
Ethylene oxide
Hexafluoro-2-propanol
Hexafluoro-2-methyl -2-propanol
Isobutyl alcohol
Isopropyl alcohol
Methanol
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
N-Nitroso-di-n-butyl amine
Paraldehyde
2-Pentanone
2-Picoline
1-Propanol
Propionitrile
Pyridine
o-Toluidine
Gasoline range organics
Diesel range organics
Jet Fuel
TWO - 29
Revision 3
January 1995
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TABLE 2-6
METHOD 8021 (GC, PHOTOIONIZATION AND ELECTROLYTIC CONDUCTIVITY DETECTORS)
HALOGENATED VOLATILES
Ally! chloride
Benzene
Benzyl chloride
Bis(2-chloroisopropyl)
ether
Bromoacetone
Bromobenzene
Bromochloromethane
Bromodi chloromethane
Bromoform
Bromomethane
n-Butylbenzene
sec-Butyl benzene
tert-Butylbenzene
Carbon tetrachloride
Chlorobenzene
Chlorodi bromomethane
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
Chloromethyl methyl ether
Chloroprene
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
l,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Dichlorodifluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-l,2-Dichloroethene
trans-1,2-Dichloroethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
l,3-Dichloro-2-propanol
1,1-Dichloropropene
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Epichlorhydrin
Ethyl benzene
Hexachlorobutadiene
Isopropylbenzene
p-Isopropyltoluene
Methylene chloride
Naphthalene
n-Propylbenzene
Styrene
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chlorof1uoromethane
1,2,3-Trichloropropane
1,2,4-Trimethylbenzene
1,3,5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
TABLE 2-7
METHODS 8031 AND 8032 (GC) AND 8033 (GC WITH NITROGEN-PHOSPHORUS DETECTION)
Method 8031:
Method 8032:
Method 8033:
Acrylonitrile
Acrylamide
Acetonitrile
TWO - 30
Revision 3
January 1995
-------
TABLE 2-8
METHOD 8041 (GC) - PHENOLS
2-Chioro-5-methylphenol
4-Chloro-2-methyl phenol
4-Chloro-3-methyl phenol
2-Chlorophenol
3-Chlorophenol
4-Chlorophenol
2-Cyclohexyl-4,6-dinitro-
phenol
2,3-Dichlorophenol
2,4-Dichlorophenol
2,5-Dichlorophenol
2,6-Dichlorophenol
3,4-Dichlorophenol
3,5-Dichlorophenol
2,3-Dimethylphenol
2,4-Dimethylphenol
2,5-Dimethylphenol
2,6-Dimethylphenol
3,4-Dimethyl phenol
2,4-Dinitrophenol
2,5-Dinitrophenol
Dinoseb
2-Methylphenol (o-Cresol)
3-Methylphenol (m-Cresol)
4-Methylphenol (p-Cresol)
2-Nitrophenol
3-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,3,4,5-Tetrachlorophenol
2,3,4,6-Tetrachlorophenol
2,3,5,6-Tetrachlorophenol
2,3,4-Trichlorophenol
2,3,5-Trichlorophenol
2,3,6-Trichlorophenol
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
TABLE 2-9
METHOD 8061 (GC/ECD) - PHTHALATE ESTERS
Benzyl benzoate
Bis(2-n-butoxyethyl) phthalate
Bis(2-ethoxyethyl) phthalate
Bis(2-ethylhexyl) phthalate
Bis(2-methoxyethyl) phthalate
Bis(4-methyl-2-pentyl )-
phthalate
Butyl benzyl phthalate
Diamyl phthalate
Dicyclohexyl phthalate
Dihexyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dinonyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Hexyl 2-ethylhexyl phthalate
TABLE 2-10
METHOD 8070 (GC) - NITROSAMINES
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
TWO - 31
Revision 3
January 1995
-------
METHOD 8081 (GC) -
TABLE 2-11
ORGANOCHLORINE PESTICIDES AND PCBs
Alachlor
Aldrin
a-BHC
,8-BHC
5-BHC
7-BHC (Lindane)
Captafol
Chlorobenzilate
a-Chlordane
7-Chlordane
Chloroneb
Chloropropylate
Chlorothalonil
DBCP
DC PA
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dial late
Dichlone
Dicofol
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
Etridiazole
Halowax-1000
Halowax-1001
Halowax-1013
Halowax-1014
Halowax-1051
Halowax-1099
Heptachlor
Heptachlor
epoxide
Hexachlorobenzene
Hexachlorocyclo-
pentadiene
Isodrin
Kepone
Methoxychlor
Mi rex
Nitrofen
trans-Nonachlor
PCNB
Permethrin
Perthane
Propachlor
Strobane
Toxaphene
Trifluralin
TWO - 32
Revision 3
January 1995
-------
TABLE 2-12
METHOD 8082 (GC) - POLYCHLORINATED BIPHENYLS
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
2-Chlorobiphenyl
2,3-Dichlorobiphenyl
2,2',5-Trichlorobiphenyl
2,4',5-Trichlorobiphenyl
2,2',3,5'-Tetrachlorobiphenyl
2,2',5,5'-Tetrachlorobiphenyl
2,3',4,4'-Tetrachlorobiphenyl
2,2',3,4,5'-Pentachlorobiphenyl
2,2',4,5,5'-Pentachlorobiphenyl
2,3,3',4',6-Pentachlorobiphenyl
2,2',3,4,4',5-Hexachlorobiphenyl
2,2',3,4,5,5'-Hexachlorobiphenyl
2,2',3,5,5',6-Hexachlorobiphenyl
2,2',4,4,5,5'-Hexachlorobiphenyl
2,2',3,3',4,4',5-Heptachlorobiphenyl
2,2',3,4,4',5,5'-Heptachlorobiphenyl
2,2',3',4,4',5',6-Heptachloro-
biphenyl
2,2',3,4',5,5',6-Heptachlorobiphenyl
2,2',3,3',4,4',5,5',6-Nonachloro-
biphenyl
TABLE 2-13
METHOD 8091 (GC) - NITROAROMATICS AND CYCLIC KETONES
Benefin
Butralin
1-Chioro-2,4-dinitrobenzene
1-Chioro-3,4-dinitrobenzene
1-Chioro-2-nitrobenzene
l-Chloro-4-nitrobenzene
2-Chloro-6-nitrotoluene
4-Chloro-2-nitrotoluene
4-Chloro-3-nitrotoluene
2,3-Dichloronitrobenzene
2,4-Dichloronitrobenzene
3,5-Dichloronitrobenzene
3,4-Dichloronitrobenzene
2,5-Dichloronitrobenzene
Dinitramine
1,2-Dinitrobenzene
1,3-Dinitrobenzene
1,4-Dinitrobenzene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Isopropalin
1,2-Naphthoquinone
1,4-Naphthoquinone
Nitrobenzene
2-Nitrotoluene
3-Nitrotoluene
4-Nitrotoluene
Penoxalin [Pendimethalin]
Pentachloronitrobenzene
Profluralin
2,3,4,5-Tetrachloronitrobenzene
2,3,5,6-Tetrachloronitrobenzene
l,2,3-Trichloro-4-nitrobenzene
l,2,4-Trichloro-5-nitrobenzene
2,4,6-Trichloronitrobenzene
Trifluralin
TWO - 33
Revision 3
January 1995
-------
TABLE 2-14
METHODS 8100 - POLYNUCLEAR AROMATIC HYDROCARBONS
Acenaphthene
Acenaphthylene
Anthracene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(j)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Chrysene
Dibenz(a,h)acridine
Dibenz(a,jjacridine
Dibenz(a,h)anthracene
7H-Dibenzo(c,g)carbazole
Dibenzo(a,e)pyrene
Dibenzo(a,h)pyrene
Dibenzo(a,ijpyrene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
3-Methylcholanthrene
Naphthalene
Phenanthrene
Pyrene
TABLE 2-15
METHOD 8111 (GC) - HALOETHERS
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
4-Bromophenyl phenyl ether
4-Chlorophenyl phenyl ether
2-Chlorophenyl 4-nitrophenyl ether
3-Chlorophenyl 4-nitrophenyl ether
4-Chlorophenyl 4-nitrophenyl ether
2,4-Dibromophenyl 4-nitrophenyl
ether
2,4-Dichlorophenyl 3-methyl-4-
nitrophenyl ether
2,6-Dichlorophenyl 4-nitrophenyl
ether
3,5-Dichlorophenyl 4-nitrophenyl
ether
2,5-Dichlorophenyl 4-nitrophenyl
ether
2,4-Dichlorophenyl 4-nitrophenyl
ether
2,3-Dichlorophenyl 4-nitrophenyl
ether
3,4-Dichlorophenyl 4-nitrophenyl
ether
4-Nitrophenyl phenyl ether
2,4,6-Trichlorophenyl 4-nitrophenyl
ether
2,3,6-Trichlorophenyl 4-nitrophenyl
ether
2,3,5-Trichlorophenyl 4-nitrophenyl
ether
2,4,5-Trichlorophenyl 4-nitrophenyl
ether
3,4,5-Trichlorophenyl 4-nitrophenyl
ether
2,3,4-Trichlorophenyl 4-nitrophenyl
ether
TWO - 34
Revision 3
January 1995
-------
TABLE 2-16
METHOD 8121 (GC) - CHLORINATED HYDROCARBONS
Benzal chloride
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadiene
a-Hexachlorocyclohexane
[a-BHC]
/3-Hexach"1 orocycl ohexane
[jg-BHC]
5-Hexachlorocyclohexane
[6-BHC]
7-Hexachlorocyclohexane [7-BHC]
Hexachlorocyclopentadi ene
Hexachloroethane
Pentachlorobenzene
1,2,3,4-Tetrachlorobenzene
1,2,3,5-Tetrachlorobenzene
1,2,4,5-Tetrachlorobenzene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,3,5-Trichlorobenzene
TABLE 2-17
METHOD 8131 (GC) - ANILINE AND SELECTED DERIVATIVES
Aniline
4-Bromoaniline
2-Bromo-6-chloro-4-nitroanilne
2-Bromo-4,6-dintroaniline
2-Chloroaniline
3-Chloroaniline
4-Chloroaniline
2-Chloro-4,6-dinitroaniline
2-Chloro-4-nitroaniline
4-Chloro-2-nitroaniline
2,6-Dibromo-4-nitroanil ine
3,4-Dichloroaniline
2,6-Dichloro-4-nitroaniline
2,4-Dinitroaniline
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
2,4,6-Trichloroaniline
2,4,5-Trichloroaniline
TWO - 35
Revision 3
January 1995
-------
TABLE 2-18
METHOD 8141 (GC) - ORGANOPHOSPHORUS COMPOUNDS
Aspon Fenthion
Atrazine Fonophos
Azinphos-ethyl Hexamethylphosphoramide (HMPA)
Azinphos-methyl Leptophos
Bolstar (Sulprofos) Malathion
Carbophenothion Merphos
Chlorofenvinphos Mevinphos
Chlorpyrifos Monocrotophos
Chlorpyrifos methyl Naled
Coumaphos Parathion, ethyl
Crotoxyphos Parathion, methyl
Demeton-0, and -S Phorate
Diazinon Phosmet
Dichlorofenthion Phosphamidon
Dichlorvos (DDVP) Ronnel
Dicrotophos Simazine
Dimethoate Stirophos (Tetrachlorvinphos)
Dioxathion Sulfotepp
Disulfoton TEPP
EPN Terbufos
Ethion Thionazin (Zinophos)
Ethoprop Tokuthion (Prothiophos)
Famphur Trichlorfon
Fenitrothion Trichloronate
Fensulfothion Tri-o-cresylphosphate (TOCP)
TABLE 2-19
METHOD 8151 (GC USING METHYLATION OR PENTAFLUOROBENZYLATION DERIVATIZATON)
CHLORINATED HERBICIDES
Acifluorfen Dicamba MCPP
Bentazon 3,5-Dichlorobenzoic 4-Nitrophenol
Chloramben acid Pentachlorophenol
2,4-D Dichloroprop Picloram
Dalapon Dinoseb 2,4,5-TP (Silvex)
2,4-DB 5-Hydroxydicamba 2,4,5-T
DCPA diacid MCPA
TWO - 36 Revision 3
January 1995
-------
TABLE 2-20
METHOD 8260 (GC/MS)- VOLATILE ORGANIC COMPOUNDS
Acetone
Acetonitrile
Acrolein (Propenal)
Acrylonitrile
Ally! alcohol
Allyl chloride
Benzene
Benzyl chloride
Bis(2-chloroethyl)-
sulfide
Bromoacetone
Bromobenzene
Bromochloromethane
Bromodichloromethane
4-Bromofluorobenzene
Bromoform
Bromomethane
n-Butanol
2-Butanone (MEK)
t-Butyl alcohol
n-Butylbenzene
sec-Butyl benzene
tert-Butylbenzene
Carbon disulfide
Carbon tetrachloride
Chloral hydrate
Chloroacetonitrile
Chlorobenzene
1-Chlorobutane
Chi orodi bromomethane
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl
ether
Chloroform
1-Chlorohexane
Chioromethane
Chloroprene
3-Chloropropionitrile
2-Chlorotoluene
4-Chlorotoluene
Crotonaldehyde
l,2-Dibromo-3-
chloropropane
1,2-Dibromoethane
Di bromof1uoromethane
Dibromomethane
1,2-Di chlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
cis-l,4-Dichloro-
2-butene
trans-l,4-Dichloro-2-
butene
Dichlorodifl uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-1,2-Dichloroethene
trans-l,2-Dichloro-
ethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
l,3-Dichloro-2-propanol
1,1-Dichloropropene
cis-l,3-Dichloropropene
trans-l,3-Dichloro-
propene
1,2,3,4-Diepoxybutane
Diethyl ether
1,4-Difluorobenzene
1,4-Dioxane
Epichlorohydrin
Ethanol
Ethyl acetate
Ethyl benzene
Ethylene oxide
Ethyl methacrylate
Fluorobenzene
Hexachlorobutadiene
Hexachloroethane
2-Hexanone
2-Hydroxypropionitrile
lodomethane
Isobutyl alcohol
Isopropylbenzene
p-Isopropyltoluene
Malononitrile
Methacrylonitrile
Methanol
Methyl-t-butyl ether
Methylene chloride
Methyl acrylate
Methyl methacrylate
4-Methyl-2-pentanone
(MIBK)
Naphthalene
Nitrobenzene
2-Nitropropane
N-Nitroso-di-n-
butylamine
Paraldehyde
Pentachloroethane
Pentafluorobenzene
2-Pentanone
2-Picoline
1-Propanol
2-Propanol
Propargyl alcohol
B-Propiolactone
Propionitrile (Ethyl
cyanide)
n-Propylamine
n-Propylbenzene
Pyridine
Styrene
1,1,1,2-Tetrachloro-
ethane
1,1,2,2-Tetrachloro-
ethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chlorof1uoromethane
1,2,3-Trichloropropane
1,2,4-Trimethyl benzene
1,3,5-Trimethyl benzene
Vinyl acetate
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
TWO - 37
Revision 3
January 1995
-------
TABLE 2-21
METHOD 8270 (GC/MS) - SEMIVOLATILE ORGANIC COMPOUNDS
Acenaphthene
Acenaphthylene
Acetophenone
2-Acetylami nof1uorene
l-Acetyl-2-thiourea
Aldrin
2-Aminoanthraquinone
Aminoazobenzene
4-Aminobiphenyl
3-Amino-9-ethyl-
carbazole
Anilazine
Aniline
o-Anisidine
Anthracene
Aramite
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Azinphos-methyl
Barban
Benz(a)anthracene
Benzidine
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzoic acid
Benzo(g,h,i)perylene
Benzo(a)pyrene
p-Benzoquinone
Benzyl alcohol
a-BHC
/3-BHC
5-BHC
7-BHC (Lindane)
Bis(2-chloroethoxy)-
methane
Bis(2-chloroethyl)
ether
Bis(2-chloroisopropyl
ether
Bis(2-ethylhexyl)
phthalate
4-Bromophenyl phenyl
ether
Bromoxynil
Butyl benzyl phthalate
Captafol
Captan
Carbaryl
Carbofuran
Carbophenothion
Chlordane (technical)
Chlorfenvinphos
4-Chloroaniline
Chlorobenzilate
5-Chloro-2-methyl-
aniline
4-Chloro-3-methyl phenol
3-(Chloromethyl)-
pyridine hydro-
chloride
1-Chloronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chloro-l,2-phenylene-
diamine
4-Chloro-l,3-phenylene-
diamine
4-Chlorophenyl phenyl
ether
Chrysene
Coumaphos
p-Cresidine
Crotoxyphos
2-Cyclohexyl-4,6-
dinitrophenol
4,4'-DDD
4,4'-DDE
4,4'-DDT
Demeton-0
Demeton-S
Diallate (cis or trans)
2,4-Diaminotoluene
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
Dibenzofuran
Dibenzo(a,e)pyrene
l,2-Dibromo-3-
chloropropane
Di-n-butyl phthalate
Dichlone
1,2-Di chlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos
Dicrotophos
Dieldrin
Diethyl phthalate
Diethylstilbestrol
Diethyl sulfate
Dihydrosaffrole
Dimethoate
3,3'-Dimethoxybenzidine
Dimethyl ami noazobenzene
7,12-Dimethylbenz(a)-
anthracene
3,3'-Dimethylbenzidine
a,o;-Dimethylphenethyl -
amine
2,4-Dimethylphenol
Dimethyl phthalate
1,2-Dinitrobenzene
1,3-Dinitrobenzene
1,4-Dinitrobenzene
4,6-Dinitro-2-methyl-
phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap
Dinoseb
Dioxathion
Diphenylamine
5,5-Di phenylhydantoi n
1,2-Diphenylhydrazine
Di-n-octyl phthalate
Disulfoton
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
EPN
Ethion
Ethyl carbamate
Ethyl methanesulfonate
Famphur
Fensulfothion
Fenthion
TWO - 38
Revision 3
January 1995
-------
TABLE 2-21 (CONTINUED)
Fluchloralin
Fluoranthene
Fluorene
2-Fluorobiphenyl
2-Fluorophenol
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclo-
pentadiene
Hexachloroethane
Hexachlorophene
Hexachloropropene
Hexamethylphosphoramide
Hydroquinone
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
Isosafrole
Kepone
Leptophos
Malathion
Maleic anhydride
Mestranol
Methapyrilene
Methoxychlor
3-Methylcholanthrene
4,4'-Methylenebis-
(2-chloroaniline)
4,4'-Methylenebis-
(N,N-dimethyl aniline)
Methyl methanesulfonate
2-Methylnaphthalene
Methyl parathion
2-Methylphenol
3-Methylphenol
4-Methylphenol
Mevinphos
Mexacarbate
Mi rex
Monocrotophos
Naled
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
Nicotine
5-Nitroacenaphthene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
5-Nitro-o-anisidine
Nitrobenzene
4-Nitrobiphenyl
Nitrofen
2-Nitrophenol
4-Nitrophenol
Nitroquino!ine-1-oxide
N-Nitrosodi-n-
butylatnine
N-Nitrosodiethylamine
N-Nitrosodimethyl amine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propyl-
amine
N-Ni trosomethylethyl -
amine
N-Nitrosomorpholine
N-Nitrosopiperidine
N-Nitrosopyrrol idine
5-Nitro-o-toluidine
Octamethyl pyrophos-
phoramide
4,4'-Oxydianiline
Parathion
Pentachlorobenzene
Pentachloron i trobenzene
Pentachlorophenol
Phenacetin
Phenanthrene
Phenobarbital
Phenol
1,4-Phenylenediamine
Phorate
Phosalone
Phosmet
Phosphamidion
Phthalic anhydride
2-Picoline
Piperonyl sulfoxide
Pronamide
Propylthiouracil
Pyrene
Pyridine
Resorcinol
Safrole
Strychnine
Sulfall ate
Terbufos
Terphenyl
1,2,4,5-Tetrachloro
benzene
2,3,4,6-Tetrachloro-
phenol
Tetrachlorvinphos
Tetraethyl dithio-
pyrophosphate
Tetraethyl
pyrophosphate
Thionazine
Thiophenol
(Benzenethiol)
Toluene diisocyanate
o-Toluidine
Toxaphene
2,4,6-Tribromophenol
1,2,4-Trichlorobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
0,0,0-Triethyl
phosphorothioate
Trifluralin
2,4,5-Trimethylaniline
Trimethyl phosphate
1,3,5-Trinitrobenzene
Tris(2,3-dibromopropyl)
phosphate
Tri-p-tolyl phosphate
TWO - 39
Revision 3
January 1995
-------
TABLE 2-22
METHOD 8275 (TE/GC/MS) - SEMIVOLATILE ORGANIC COMPOUNDS (SCREENING)
Acenaphthene
Acenaphthylene
Anthracene
Benz(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene
4-Bromophenyl phenyl
ether
1-Chioronaphthalene
Chrysene
Dibenxofuran
Dibenz(a,h)anthracene
Dibenzothiophene
Fluoranthene
Fluorene
Hexachlorobenzene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
2-Chlorobiphenyl
3,3'-Dichlorobiphenyl
2,2',5-Trichloro-
biphenyl
2,3',5-Trichloro-
biphenyl
2,4',5-Trichloro-
biphenyl
2,2',5,5'-Tetrachloro-
biphenyl
2,2'4,5'-Tetrachloro-
biphenyl
2,2'3,5'-Tetrachloro-
biphenyl
2,3',4,4'-Tetrachloro-
biphenyl
2,2',4,5,5'-Penta-
chl orobiphenyl
2,3',4,4',5-Penta-
chlorobiphenyl
2,2',3,4,4',5'-
Hexachlorobiphenyl
22' 33' 44'-
£.,£. 5O>O jtjT1
Hexachlorobi phenyl
2,2',3,4',5,5',6-
Heptachlorobiphenyl
2 2' 3 4 4' 5 5'-
£ , C. ,O,t,t ,3,3
Heptachlorobiphenyl
2 2' 3 3' 4 4' 5-
{-•,(- ,J,O ,^,^ »3
Heptachlorobiphenyl
2,2',3,3',4,4'5,5'-
Octachlorobiphenyl
2,2',3,3'4,4'5,5',6-
Nonachlorobiphenyl
2,2',3,3'4,4'5,5',6,6'
Decachlorobiphenyl
TABLE 2-23
METHODS 8280 (HRGC/LRMS) AND 8290 (HRGC/HRMS) -
POLYCHLORINATED DIBENZO-p-DIOXINS (PCDDs)
AND POLYCHLORINATED DIBENZOFURANS (PCDFs)
2,3,7,8-TCDD
TCDD, total*
1,2,3,7,8-PeCDD
PeCDD, total*
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
HxCDD, total*
1,2,3,4,6,7,8-HpCDD
HpCDD, total*
OCDD
2,3,7,8-TCDF
TCDF, total*
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
PeCDF, total*
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
HxCDF, total*
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
HpCDF, total*
OCDF
* Analyte of only Method 8280.
TWO - 40
Revision 3
January 1995
-------
TABLE 2-24
METHOD 8310 (HPLC) - POLYNUCLEAR AROMATIC HYDROCARBONS
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
TABLE 2-25
METHOD 8315 - CARBONYL COMPOUNDS
Acetaldehyde
Acetone
Acrolein
Benzaldehyde
Butanal (Butyraldehyde)
Crotonaldehyde
Cyclohexanone
Decanal
2,5-Dimethylbenzaldehyde
Formaldehyde
Heptanal
Hexanal (Hexaldehyde)
Isovaleraldehyde
Nonanal
Octanal
Pentanal (Valeraldehyde)
Propanal
(Propionaldehyde)
m-Tolualdehyde
o-Tolualdehyde
p-Tolualdehyde
TWO - 41
Revision 3
January 1995
-------
TABLE 2-26
METHOD 8316 (HPLC) M
Aery!amide
Acrylonitrile
Acrolein
TABLE 2-27
METHOD 8318 (HPLC) - N-METHYLCARBAMATES
Aldicarb (Temik)
Aldicarb sulfone
Carbaryl (Sevin)
Carbofuran (Furadan)
Dioxacarb
3-Hydroxycarbofuran
Methiocarb (Mesurol)
Methomyl (Lannate)
Promecarb
Propoxur (Baygon)
TWO - 42 Revision 3
January 1995
-------
TABLE 2-28. METHOD 8321 (HPLC/TS/MS) - NON-VOLATILE ORGANIC COMPOUNDS
Azo Dyes
Disperse Red 1
Disperse Red 5
Disperse Red 13
Disperse Yellow 5
Disperse Orange 3
Disperse Orange 30
Disperse Brown 1
Solvent Red 3
Solvent Red 23
Anthraquinone Dyes
Disperse Blue 3
Disperse Blue 14
Disperse Red 60
Coumarin Dyes
Fluorescent Briqhteners
Fluorescent Brightener 61
Chlorinated Phenoxyacid Compounds
2,4-D
2,4-D, butoxyethanol ester
2,4-D, ethylhexyl ester
2,4-DB
Dalapon
Dicamba
Dichlorprop
Dinoseb
MCPA
MCPP
Silvex (2,4,5-TP)
2,4,5-T
2,4,5-T, butyl ester
2,4,5-T, butoxyethanol ester
Alkaloids
Strychnine
Caffeine
Organophosphorus Compounds
Asulam
Fensulfothion
Dichlorvos
Dimethoate
Disulfoton
Merphos
Methomyl
Methyl parathion
Monocrotophos
Famphur
Naled
Phorate
Trichlorfon
Thiofanox
Tris-(2,3-dibromopropyl) phosphate
(Tris-BP)
Fluorescent Brightener 236
Carbamates
Aldicarb
Aldicarb sulfone
Aldicarb sulfoxide
Aminocarb
Barban
Benomyl
Bromacil
Bendiocarb
Carbaryl
Carbendazim
Carbofuran
3-Hydroxy-carbofuran
Chloroxuron
Chloropropham
Diuron
Fenuron
Fluometuron
Linuron
Methiocarb
Methomyl
Mexacarbate
Monuron
Neburon
Oxamyl
Propachlor
Propham
Propoxur
Siduron
Tebuthiuron
TWO - 43
Revision 3
January 1995
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TABLE 2-29
METHOD 8325 (HPLC/PB/MS) - NON-VOLATILE ORGANIC COMPOUNDS
Benzidine
Benzoylprop ethyl
Carbaryl
o-Chlorophenyl thiourea
3,3'-Dichlorobenzidine
3,3'-Dimethoxybenzidine
3,3'-Dimethylbenzidine
Diuron
Linuron (Lorox)
Monuron
Rotenone
Siduron
TABLE 2-30
METHOD 8330 (HPLC) - NITROAROMATICS AND NITRAMINES
4-Amino-2,6-dinitrotoluene
(4-Am-DNT)
2-Amino-4,6-dinitrotoluene
(2-Am-DNT)
1,3-Dinitrobenzene (1,3-DNB)
2,4-Dinitrotoluene (2,4-DNT)
2,6-Dinitrotoluene (2,6-DNT)
Hexahydro-l,3,5-trinitro-
1,3,5-triazine (RDX)
Methyl-2,4,6-trinitrophenyl-
nitramine (Tetryl)
Nitrobenzene (NB)
2-Nitrotoluene (2-NT)
3-Nitrotoluene (3-NT)
4-Nitrotoluene (4-NT)
Octahydro-1,3,5,7-tetrani tro-
1,3,5,7-tetrazocine (HMX)
1,3,5-Trinitrobenzene (1,3,5-TNB)
2,4,6-Trinitrotoluene (2,4,6-TNT)
TABLE 2-31
METHOD 8331 (REVERSE PHASE HPLC)
Tetrazene
TABLE 2-32
METHOD 8332 (HPLC)
Nitroglycerine
TWO - 44
Revision 3
January 1995
-------
TABLE 2-33
METHOD 8410 - SEMIVOLATILES
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzole acid
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
4-Chloroaniline
4-Chloro-3-methyl phenol
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Dibenzofuran
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
2,4-Dichlorophenol
Diethyl phthalate
Dimethyl phthalate
4,6-Dinitro-2-methylphenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Di-n-propyl phthalate
Fluoranthene
Fluorene
Hexachlorobenzene
1,3-Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
Isophorone
2-Methyl naphthalene
2-Methylphenol
4-Methylphenol
Naphthalene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitroso-di-n-propylamine
Pentachlorophenol
Phenanthrene
Phenol
Pyrene
1,2,4-Trichlorobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
TABLE 2-34
METHOD 8430 (GC/FT-IR) - BIS(2-CHLOROETHYL)ETHER AND ITS HYDROLYSIS PRODUCTS
Bis(2-chloroethyl)ether
2-Chloroethanol
2-(2-Chloroethoxy)ethanol
Diethylene glycol
Ethylene glycol
TWO - 45
Revision 3
January 1995
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TABLE 2-35
ANALYSIS METHODS FOR INORGANIC ANALYTES
Compound Applicable Method(s)
Aluminum 6010, 6020, 7020
Antimony 6010, 6020, 7040, 7041, 7062
Arsenic 6010, 6020, 7060, 7061, 7062, 7063
Barium 6010, 6020, 7080, 7081
Beryllium 6010, 6020, 7090, 7091
Bromide 9056, 9211
Cadmium 6010, 6020, 7130, 7131
Calcium 6010, 7140
Chloride 9056, 9057, 9212, 9250, 9251, 9253
Chromium 6010, 6020, 7190, 7191
Chromium, hexavalent 7195, 7196, 7197, 7198, 7199
Cobalt ... 6010, 6020, 7200, 7201
Copper 6010, 6020, 7210, 7211
Cyanide 9010, 9012, 9013, 9213
Fluoride 9056, 9214
Iron 6010, 7380, 7381
Lead 6010, 6020, 7420, 7421
Lithium 6010, 7430
Magnesium 6010, 7450
Manganese 6010, 6020, 7460, 7461
Mercury 7470, 7471, 7472
Molybdenum 6010, 7480, 7481
Nickel 6010, 6020, 7520, 7521
Nitrate 9056, 9210
Nitrite 9056
Osmium 7550
Phosphate 9056
Phosphorus 6010
Phosphorus, white 7580
Potassium 6010, 7610
Selenium 6010, 7740, 7741, 7742
Silver 6010, 6020, 7760, 7761
Sodium 6010, 7770
Strontium 6010, 7780
Sulfate 9035, 9036, 9038, 9056
Sulfide 9030, 9031, 9215
Thallium 6010, 6020, 7840, 7841
Tin 7870
Vanadium 6010, 7910, 7911
Zinc 6010, 6020, 7950, 7951
TWO - 46 Revision 3
January 1995
-------
TABLE 2-36
CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TIMES FOR AQUEOUS MATRICESA
Name
Bacterial Tests:
Col i form, total
Inorganic Tests:
Chloride
Cyanide, total and amenable
to chlorination
Hydrogen ion (pH)
Nitrate
Sulfate
Sulfide
Metals:
Chromium VI
Mercury
Metals, except chromium VI
and mercury
Organic Tests:
Acrolein and acrylonitri le
Benzi dines
Chlorinated hydrocarbons
Dioxins and Furans
Haloethers
Nitroaromatics and
cyclic ketones
Nitrosamines
Oil and grease
Organic carbon, total (TOO
PCBs
Pesticides
Phenols
Phthalate esters
Polynuclear aromatic
hydrocarbons
Purgeable aromatic
hydrocarbons
Purgeable Halocarbons
Total organic halides (TOX)
Radiological Tests:
Alpha, beta and radium
Container1
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
G, Teflon- lined
septum
G, Teflon- lined
cap
G, Teflon- lined
cap
G, Teflon-lined
cap
G, Teflon- lined
cap
G, Teflon- lined
cap
G, Teflon- lined
cap
G
P, G
G, Teflon- lined
cap
G, Teflon- lined
cap
G, Teflon-lined
cap
G, Teflon- lined
cap
G, Teflon- lined
cap
G, Teflon- lined
septum
G, Teflon- lined
septum
G, Teflon-lined
cap
P, G
Preservation
Cool, 4°C, 0.008% Na2S203
None required
Cool, 4°C; if oxidizing
agents present add 5 mL
0.1N NaAs02 per L or 0.06 g
of ascorbic acid per L;
adjust pH>12 with 50% NaOH.
See Method 9010 for other
interferences.
None required
Cool, 4°C
Cool, 4°C
Cool, 4°C, add zinc acetate
Cool, 4°C
HN03 to pH<2
HN03 to pH<2
Cool, 4°C, 0.008% Na2S2033,
Adjust pH to 4-5
Cool, 4°C, 0.008% Na2S2033,
Cool, 4°C, 0.008% Na2S2033
Cool, 4°C, 0.008% Na2S2033
Cool, 4°C, 0.008% Na2S2033
Cool, 4°C, 0.008% Na2S2033
store in dark
Cool, 4°C, 0.008% Na2S2033,
store in dark
Cool, 4°C2
Cool, 4°C2
Cool, 4°C
Cool, 4°C
Cool, 4°C, 0.008% Na2S2033
Cool, 4°C
Cool, 4°C, 0.008% Na2S2033
store in dark
Cool, 4°C, 0.008% Na2S2032'3
Cool, 4°C, 0.008% Na2S2033
Cool, 4°C2
HN03 to pH<2
Maximum holding time
6 hours
28 days
14 days
24 hours
48 hours
28 days
7 days
24 hours
28 days
6 months
14 days
7 days until extraction.
after extraction
7 days until extraction.
after extraction
7 days until extraction.
after extraction
7 days until extraction,
after extraction
7 days until extraction.
after extraction
7 days until extraction,
after extraction
28 days
28 days
7 days until extraction,
after extraction
7 days until extraction,
after extraction
7 days until extraction,
after extraction
7 days until extraction,
after extraction
7 days until extraction,
after extraction
14 days
14 days
28 days
6 months
40 days
40 days
40 days
40 days
40 days
40 days
40 days
40 days
40 days
40 days
40 days
A Table excerpted, in part, from Table II, 49 FR 209, October 26, 1984, p 28.
1 Polyethylene (P) or Glass (G)
2 Adjust to pH«2 with H2S04, HCl or solid NaHS04. Free chlorine must be removed prior to adjustment.
3 Free chlorine must be removed by the appropriate addition of Na2S203.
TWO - 47
Revision 3
January 1995
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TABLE 2-37. PREPARATION METHODS FOR ORGANIC ANALYTES
Analyte Type
Acid Extractable
Acrolein, Acrylonitrile,
and Acetonitrile
Acryl amide
Aniline and Selected
Derivatives
Aromatic Volatiles
Base/Neutral Extractable
Carbamates
Chlorinated Herbicides
Chlorinated Hydrocarbons
Dyes
Explosives
Formaldehyde
Haloethers
Halogenated Volatiles
Nitroaromatic and Cyclic
Ketones
Matrix
Aqueous1
3510
3520
(pH < 2)
5031
80324
3510
3520
(pH >11)
503111
5030
5032
3510
3520
(pH >11)
83185
81516
(pH < 2)
3510
3520
(PH 7)
3510
3520
83307
83318
83 159
3510
3520
5030
5032
3510
3520
(pH 5-9)
Solids
3540
3541
3545
3550
5031
3540
3541
3545
3550
5021
5032
5035
3540
3541
3545
3550
83 185
81516
3540
3541
3550
3540
3541
3545
3550
83307
83318
83 159
3540
3541
3545
3550
5021
5032
5035
3540
3541
3545
3550
Sludges and
Emulsions1-2
3520
(pH < 2)
5031
3520
(pH >11)
5030
5032
3520
(pH >11)
83185
81516
(pH<2)
3520
(pH 7)
5030
3520
(pH 5-9)
Organic
Liquids,
Tars, Oils
3650
35803
3585
35803
3585
3650
35803
83185
35803
35803
3585
35803
TWO - 48
Revision 3
January 1995
-------
TABLE 2-37
PREPARATION METHODS FOR ORGANIC ANALYTES
(continued)
Analyte Type
Nitrosamines
Non-halogenated Volatiles
Organochlorine Pesticides
Organophosphorus Pesticides
Phenols
Phthalate Esters
Polychlorinated Biphenyls
PCDDs and PCDFs
Polynuclear Aromatic
Hydrocarbons
Volatile Organics
Matrix
Aqueous1
3510
3520
5031
5032
3510
3520
3535
(pH 5-9)
3510
3520
(pH 6-8)
3510
3520
(PH < 2)
3510
3520
3535
(PH 7)
3510
3520
3535
(pH 6-8)
828010
829010
3510
3520
(PH 7)
5030
5031
5032
Solids
3540
3541
3545
3550
5021
5031
5032
3540
3541
3545
3550
3540
3541
3545
3540
3541
3545
3550
3540
3541
3545
3550
3540
3541
3545
828010
829010
3540
3541
3545
3550
3561
5021
5031
5032
5035
Sludges and
Emulsions1'2
5021
5031
5032
3520
(pH 5-9)
3520
(pH 6-8)
3520
(PH < 2)
3520
(PH 7)
3520
(pH 6-8)
828010
829010
3520
(PH 7)
5021
5030
5031
5032
Organic
Liquids,
Tars, Oils
5032
3585
35803
35803
3650
35803
35803
35803
828010
829010
35803
3585
Footnotes are on the following page.
TWO - 49
Revision 3
January 1995
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TABLE 2-37
PREPARATION METHODS FOR ORGANIC ANALYTES
(continued)
Footnotes for Table 2-37
1 The pH at which extraction should be performed is shown in parentheses.
2 If attempts to break an emulsion are unsuccessful, these methods may be used.
3 Method 3580 is only appropriate if the sample is soluble in the specified solvent.
4 Method 8032 contains the extraction, cleanup, and determinative procedures for this
analyte.
5 Method 8318 contains the extraction, cleanup, and determinative procedures for these
analytes.
6 Method 8151 contains the extraction, cleanup, and determinative procedures for these
analytes.
7 Method 8330 contains the extraction, cleanup, and determinative procedures for these
analytes.
8 Method 8331 is for Tetrazene only, and contains the extraction, cleanup, and
determinative procedures for this analyte.
9 Method 8315 contains the extraction, cleanup, and determinative procedures for this
analyte.
10 Methods 8280 and 8290 contain the extraction, cleanup, and determinative procedures
for these analytes.
11 Method 5031 may be used when only aniline is to be determined.
TWO - 50 Revision 3
January 1995
-------
TABLE 2-38. CLEANUP METHODS FOR ORGANIC ANALYTE EXTRACTS
Analyte Type
Acid Extractable
Base/Neutral Extractable
Carbamates
Chlorinated Herbicides
Chlorinated Hydrocarbons
Haloethers
Nitroaromatics & Cyclic Ketones
Nitrosamines
Organochlorine Pesticides
Organophosphorus Pesticides
Phenols
Phthalate Esters
Polychlorinated Biphenyls
Polychlorinated Dibenzo-p-Dioxins
and Polychlorinated Dibenzofurans
Polynuclear Aromatic Hydrocarbons
Method
3650
3650
83181
81512
3620
3640
3620
3640
3620
3640
3610
3620
3630
3640
3660
3620
3630
3640
3650
3610
3611
3620
3640
3620
3630
3640
3660
3665
82803
82903
3610
3611
3630
3640
3650
1 Method 8318 contains the extraction, cleanup, and determinative procedures
for these analytes.
2 Method 8151 contains the extraction, cleanup, and determinative procedures
for these analytes.
3 Methods 8280 and 8290 contain the extraction, cleanup, and determinative
procedures for these analytes.
TWO - 51
Revision 3
January 1995
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TABLE 2-39. DETERMINATIVE METHODS ORGANIC ANALYTES
Analyte Type
Acid Extractable
Acrolein, Acrylonitrile,
Acetonitrile
Acryl amide
Aniline and Selected
Derivatives
Aromatic Volatiles
Base/Neutral Extractable
Carbamates
Chlorinated Herbicides
Chlorinated Hydrocarbons
Dyes
Explosives
Formaldehyde
Haloethers
Halogenated Volatiles
Nitroaromatics and Cyclic
Ketones
Nitrosoamines
Non-halogenated Volatiles
Organochlorine Pesticides
Organophosphorus Pesticides
Phenols
Petroleum Hydrocarbons
Phthalate Esters
Polychlorinated Biphenyls
PCDDs and PCDFs
Polynuclear Aromatic
Hydrocarbons
Volatile Organics
GC/MS
Method
8270
8260
8260
8270
8260
8270
82703
8270
8270
8260
8270
8270
8260
82703
82703
8270
8270
82703
8280
8290
8270
8260
Specific GC
Method
8031
80331
8032
8131
8021
8151
8121
8111
8011, 8021
8091
8070
8015
8081
8141
8041
8015
8061
8082
8100
8011, 8015,
8021, 8031,
8032, 8033
HPLC
Method
83 152
8316
8316
83254
8318, 8321
8321
8321
8330,
8331, 8332
8315
83305
8321
8310
8315
8316
Of these analytes, Method 8033 is for acetonitrile only.
Of these analytes, Method 8315 is for acrolein only.
This method is an alternative confirmation method, not the method of choice.
Benzidines and related compounds.
Nitroaromatics (see "Explosives").
TWO - 52
Revision 3
January 1995
-------
CO
a
I— 4
=»
cr
' O
CM CO
LU OC.
al O
=) U.
C3
CL.
O
oo
*—«
00
cc
o
-------
FIGURE 2-2
SCHEMATIC OF SEQUENCE TO DETERMINE
IF A WASTE IS HAZARDOUS BY CHARACTERISTIC
What is
physical state
of waste?
Perform Paint
Filter Test
(Method 9095)
Nonhazardous
for corrosivity
characteristic
Methods 1110 and 9040
Yes
Methods 1010 or 1020
YBS
DOT(49CFR 173300)
-^C^~Hazaroous~^)
Generator Knowledge
OT(49CFR173.151)
TWO - 54
Revision 3
January 1995
-------
FIGURE 2-2
(Continued)
Nonnazardous
for ignitability
characteristic
Reactive CN
and Sulfide Tests
Does waste
generate toxic
gas'
Nonhazardous
for toxic gas generation
(reactivity) characteristic
Is total
concen. of TC
constituents •*• 20 <
TC regulatory
limif
Nonhazardous
for toxicity
characteristic
Is waste
leachable and
Nonhazardous
for toxiaty
characteristic
TWO - 55
Revision 3
January 1995
-------
FIGURE 2-3A
EP
Sample
1310
3010
(7760 Ag)
6010
Ba--
Cr --
Ag --
-- As
-- Cd
-- Pb
-- Se
7470
Hg
3510
Neutral
8151
Herbicides
8081
Pesticides
TWO - 56
Revision 3
January 1995
-------
FIGURE 2-3B
.COMMENDED SW-846 METHODS OF ANALYSIS FOR TCLP LEACHATES
Sample
TCLP
3010
7470
Hg
3510
Neutral
8260
Volatile
Organics
3510
(Acidic
and
Basic)
8151
Herbic-
ides
Ba -
Cr -
Ag -
- As
- Cd
- Pb
- Se
TWO - 57
Revision 3
January 1995
-------
FIGURE 2-4A.
GROUND WATER ANALYSIS: ORGANIC ANALYTES
VGA
Semivolatiles
8260
3510 or
3520
8270
Organic
Sample
Pesticides
3510 or
3520
Neutral
3620, 3640,
and/or 3660
Herbicides
Dioxins
8151
8280 or
8290
8081
1 - Optional: Cleanup required only if interferences prevent analysis.
TWO - 58
Revision 3
January 1995
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FIGURE 2-4B.
GROUND WATER ANALYSIS: INDICATOR ANALYTES
Indicator
Analyte(s)
1 - Barcelona, 1984, (See Reference 1)
2 - Riggin, 1984, (See Reference 2)
TWO - 59
Revision 3
January 1995
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FIGURE 2-4C.
GROUND WATER ANALYSIS: INORGANIC ANALYTES
( GROUND WATER
V SAMPLE
SAMPLE PREPARATION
3005 OR 3015
i
SAMPLE PREPARATION
3015 OR 3020
i
I
Ag, Al, As, Ba, Be,
Cd, Co, Cr. Cu, Fe,
Mg, Mn, Mo, Ni, Pb,
Sb, Se, Tl, V, Zn
Ag. Al, As, Ba, Be,
Cd, Co, Cr, Cu, Mn,
Ni. Pb. Sb, Tl, Zn
Ag-7760
Ba-7080
Cd-7130
Cr-7190
Fe-7380
Mn-7460
Ni - 7520
Sb-7040
TI-7840
Zn-7950
AI-7020
Be -7090
Co -7200
Cu-7210
Mg - 7450
Mo -7480
Pb-7420
Sn - 7870
V • 7910
Ag-7761'
Ba-7081'
Be -7091
Cd-7131
Co - 7201
Cr-7191
Cu-7211*
Fe-7381"
Mn- 746T
Mo - 7481
Pb - 7421
Tl - 7841
Sb-7041'
7062*
V-7911
Zn-7951*
* Follow the digestion procedures as detailed in the individual
determinative methods.
1 When analyzing for total dissolved metals, digestion is not
necessary if the samples are filtered at the time of
collection, and then acidified to the same concentration as the standards
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CHAPTER THREE
INORGANIC ANALYTES
3.1 SAMPLING CONSIDERATIONS
3.1.1 Introduction
This manual contains procedures for the analysis of inorganic analytes in
a variety of matrices. These methods are written as specific steps in the
overall analysis scheme -- sample handling and preservation, sample digestion or
preparation, and sample analysis for specific inorganic components. From these
methods, the analyst must assemble a total analytical protocol which is
appropriate for the sample to be analyzed and for the information required. This
introduction discusses the options available in general terms, provides
background information on the analytical techniques, and highlights some of the
considerations to be made when selecting a total analysis protocol.
3.1.2 Definition of Terms
Optimum concentration range: A range, defined by limits expressed in
concentration, below which scale expansion must be used and above which curve
correction should be considered. This range will vary with the sensitivity of
the instrument and the operating conditions employed.
Sensitivity: (a) Atomic Absorption: The concentration in milligrams of
metal per liter that produces an absorption of 1%; (b) Inductively Coupled Plasma
(ICP): The slope of the analytical curve, i.e., the functnfnal relationship
between emission intensity and concentration. .;
Method detection limit (MDL): The minimum concentration of a substance
that can be measured and reported with 99% confidence that the analyte
concentration is greater than zero. The MDL is determined from analysis of a
sample in a given matrix containing the analyte which has been processed through
the preparative procedure.
Total recoverable metals: The concentration of metals in an unfiltered
sample following treatment with hot dilute mineral acid (Method 3005).
Dissolved metals: The concentration of metals determined in a sample after
the sample is filtered through a 0.45-um filter (Method 3005).
Suspended metals: The concentration of metals determined in the
portion of a sample that is retained by a 0.45-um filter (Method 3005).
Total metals: The concentration of metals determined in a sample following
digestion by Methods 3010, 3015, 3020, 3050, 3051, or 3052.
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Instrument detection limit (IDL): The concentration equivalent to a signal
due to the analyte which is equal to three times the standard deviation of a
series of 7 replicate measurements of a reagent blank's signal at the same
wavelength.
Interference check sample (ICS): A solution containing both interfering
and analyte elements of known concentration that can be used to verify background
and interelement correction factors.
Initial calibration verification (ICV) standard: A certified or
independently prepared solution used to verify the accuracy of the initial
calibration. For ICP analysis, it must be run at each wavelength used in the
analysis.
Continuing calibration verification (CCV): Used to assure calibration
accuracy during each analysis run. It must be run for each analyte as described
in the particular analytical method. At a minimum, it should be analyzed at the
beginning of the run and after the last analytical sample. Its concentration
should be at or near the mid-range levels of the calibration curve.
Calibration standards: A series of known standard solutions used by the
analyst for calibration of the instrument (i.e., preparation of the analytical
curve).
Linear dynamic range: The concentration range over which the analytical
curve remains linear.
Method blank: A volume of reagent water processed through each sample
preparation procedure.
Calibration blank: A volume of reagent water acidified with the same
amounts of acids as were the standards and samples.
Laboratory control standard: A volume of reagent water spiked with known
concentrations of analytes and carried through the preparation and analysis
procedure as a sample. It is used to monitor loss/recovery values.
Method of standard addition (MSA): The standard-addition technique
involves the use of the unknown and the unknown plus several known amounts of
standard. See Method 7000, Section 8.7 for detailed instructions.
Sample holding time: The storage time allowed between sample collection
and sample analysis when the designated preservation and storage techniques are
employed.
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3.1.3 Sample Handling and Preservation
Sample holding times, digestion volumes and suggested collection volumes
are listed in Table 3-1. The sample volumes required depend upon the number of
different digestion procedures necessary for analysis. This may be determined
by the application of graphite-furnace atomic absorption spectrometry (GFAA),
flame atomic absorption spectrometry (FLAA), inductively coupled argon plasma
emission spectrometry (ICP), hydride-generation atomic absorption spectrometry
(HGAA), inductively coupled plasma mass spectrometry (ICP-MS) or cold-vapor
atomic absorption spectrometry (CVAA) techniques, each of which may require
different digestion procedures. The indicated volumes in Table 3-1 refer to that
required for the individual digestion procedures and recommended sample
collection volumes.
In the determination of trace metals, containers can introduce either
positive or negative errors in the measurement of trace metals by (a)
contributing contaminants through leaching or surface desorption, and (b)
depleting concentrations through adsorption. Thus the collection and treatment
of the sample prior to analysis require particular attention. The following
cleaning treatment sequence has been determined to be adequate to minimize
contamination in the sample bottle, whether borosilicate glass, linear
polyethylene, polypropylene, or Teflon: detergent, tap water, 1:1 nitric acid,
tap water, 1:1 hydrochloric acid, tap water, and reagent water.
NOTE: Chromic acid should not be used to clean glassware, especially
if chromium is to be included in the analytical scheme. Commercial,
non-chromate products (e.g., Nochromix) may be used in place of
chromic acid if adequate cleaning is documented by an analytical
quality control program. (Chromic acid should also not be used with
plastic bottles.)
3.1.4
The toxicity or carcinogenicity of each reagent used in these methods has
not been precisely defined. However, each chemical compound should be treated
as a potential health hazard. From this viewpoint, exposure to these chemicals
must be reduced to the lowest possible level by whatever means available. The
laboratory is responsible for maintaining a current awareness file of OSHA
regulations regarding the safe handling of the chemicals specified in these
methods. A reference file of material data-handling sheets should also be made
available to all personnel involved in the chemical analysis. Additional
references to laboratory safety are available. They are:
1. "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.
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2. "OSHA Safety and Health Standards, General Industry" (29 CFR 1910)',
Occupational Safety and Health Administration, OSHA 2206, revised
January 1976.
3. "Proposed OSHA Safety and Health Standards, Laboratories," Occupational
Safety and Health Administration, Federal Register, July 24, 1986, p. 26660.
4. "Safety in Academic Chemistry Laboratories," American Chemical Society
Publication, Committee on Chemical Safety, 3rd edition, 1979.
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TABLE 3-1.
SAMPLE HOLDING TIMES, REQUIRED DIGESTION VOLUMES AND RECOMMENDED COLLECTION
VOLUMES FOR INORGANIC DETERMINATIONS IN AQUEOUS AND SOLID SAMPLES
Measurement
Digestion
Vol. Req.
(tnL)a
Collection
Volume (mL)J
Treatment/
Preservative
Holding Timeb
Inorganic Analytes (except hexavalent chromium and mercury):
Aqueous
Total
Dissolved
Suspended
Solid
Total
Chromium VI:
Aqueous
Solid
Mercury:
Aqueous
Total
Dissolved
Solid
Total
100
100
100
2 9
100
2.5 g
100
100
0.2 g
600
600
600
200 g
400
100 g
400
400
200 g
HN03 to pH <2
6 months
Filter on site;
HN03 to pH <2
6 months
Filter on site
6 months
6 months
24 hours
One month to
extraction, 4 days
after extraction
HN03 to pH <2
28 days
Filter;
HN03 to pH <2
28 days
28 days
aUnless stated otherwise.
bAll non-aqueous samples and all aqueous samples that are to be analyzed for
hexavalent chromium must be stored at 4°C ± 2°C until analyzed, either glass or
plastic containers may be used.
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3.2 SAMPLE PREPARATION METHODS
The methods in SW-846 for sample digestion or preparation are as
follows1:
Method 3005 prepares ground water and surface water samples for total
recoverable and dissolved metal determinations by FLAA, ICP-AES, or ICP-MS. The
unfiltered or filtered sample is heated with dilute HC1 and HN03 prior to metal
determination.
Method 3010 prepares waste samples for total metal determinations by
FLAA, ICP-AES, or ICP-MS. The samples are vigorously digested with nitric acid
followed by dilution with hydrochloric acid. The method is applicable to aqueous
samples, EP and mobility-procedure extracts.
Method 3015 prepares aqueous samples, mobility-procedure extracts, and
wastes that contain suspended solids for total metal determinations by FLAA,
GFAA, ICP-AES, or ICP-MS. Nitric acid is added to the sample in a Teflon
digestion vessel and heated in a microwave unit prior to metals determination.
Method 3020 prepares waste samples for total metals determinations by
furnace GFAA or ICP-MS. The samples are vigorously digested with nitric acid
followed by dilution with nitric acid. The method is applicable to aqueous
samples, EP and mobility-procedure extracts.
Method 3031 prepares waste oils, oil sludges, tars, waxes, paints,
paint sludges and other viscous petroleum products for analysis by FLAA and ICP-
AES. The samples are vigorously digested with nictric acid, sulfuric acid,
hydrochloric acid, and potassium permanganate prior to analysis.
Method 3040 prepares oily waste samples for determination of soluble
metals by FLAA, GFAA, and ICP-AES methods. The samples are dissolved and diluted
in organic solvent prior to analysis. The method is applicable to the organic
extract in the oily waste EP procedure and other samples high in oil, grease, or
wax content.
Method 3050 prepares waste samples for total metals determinations by
FLAA and ICP-AES, or ICP-MS. The samples are vigorously digested in nitric acid
and hydrogen peroxide followed by dilution with either nitric or hydrochloric
acid. The method is applicable to soils, sludges, and solid waste samples.
Method 3051 prepares sludges, sediments, soils and oils for total metal
determinations by FLAA, GFAA, ICP-AES or ICP-MS. Nitric acid is added to the
representative sample in a fluorocarbon digestion vessel and heated in a
microwave unit prior to metals determination.
1 Please note that chlorine is an interferent in ICP-MS analyses and its use
should be discouraged except when absolutely necessary.
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Method 3052 prepares siliceous and organically based matrices including
ash, biological tissue, oil, oil contaminated soil, sediment, sludge, and soil
for analysis by FLAA, CVAA, GFAA, ICP-AES, and ICP-MS. Nitric acid and
hydrofluoric acid are added to a representative sample in a fluorocarbon
digestion vessel and heated in a microwave unit prior to analysis.
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METHOD 3031
ACID DIGESTION OF OILS FOR METALS
ANALYSIS BY FLAA OR ICP SPECTROSCOPY
1.0 SCOPE AND APPLICATION
1.1 This method is an acid digestion procedure for analysis of oils,
oil sludges, tars, waxes, paints, paint sludges and other viscous petroleum
products for the sixteen toxic elements listed below:
Antimony Arsenic Barium Beryllium
Cadmium Chromium Cobalt Copper
Lead Molybdenum Nickel Selenium
Silver Thallium Vanadium Zinc
The resulting digestate can be analyzed by either flame atomic absorption
spectroscopy (FLAA) or inductively coupled plasma atomic emission spectroscopy
(ICP-AES).
1.2 The large concentration of manganese present in the digestate of
Method 3031 can interfere with the determination of low concentrations of
arsenic which is important for the recycled oil regulations. As an optional
step, manganese may be removed from the digestate by forming a manganese
phosphate precipitate. The remaining liquid can be analyzed by either flame
atomic absorption spectroscopy (FAA) or inductively coupled plasma (ICP-AES).
Chlorides can be removed by the use of nitric acid for analysis by graphite
furnace atomic absorption spectroscopy (GFAA) for arsenic. These clean-up
procedures may be applicable to other elements as can be demonstrated by
appropriate procedures (Sec. 7.11).
2.0 SUMMARY OF METHOD
2.1 A representative 0.5-gram sample is mixed with 0.5 grams of
finely ground potassium permanganate and heated to 100°C. After cooling to
room temperature, 1.5 mL of concentrated sulfuric acid is added while
stirring. A strong exothermic reaction occurs, after which the sample is
heated to near dryness. The digestate is treated with 10 mL of concentrated
nitric acid and 2 mL concentrated hydrochloric acid, heated to 95°C, and again
brought to near dryness. After cooling, 5 mL of concentrated HC1 is added,
the digestate is again heated to 95°C and is then filtered. The filter is
washed with hot concentrated HC1. The filter paper is transferred to a
digestion flask, treated with 5 mL of concentrated hydrochloric acid, and
heated to 95°C to dissolve the filter. The digestate is filtered, and the
filtrates are combined. The sample is brought to volume and analyzed by ICP-
AES or Flame AAS.
WARNING; THIS PROCEDURE SHOULD NOT BE ATTEMPTED BY INEXPERIENCED
PERSONNEL. MANY OF THE REACTIONS ARE STRONGLY EXOTHERMIC AND CAN RESULT
IN SPLATTERING OR IN THE GENERATION OF GASES. GLOVES, FACESHIELDS, AND
LAB COATS MUST BE WORN WHEN WORKING WITH ACIDS. IT IS STRONGLY
RECOMMENDED THAT THE ADDITION OF SULFURIC ACID BE PERFORMED BEHIND A
GLASS SHIELD OR SASH.
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2.2 To remove the manganese, the digestate is neutralized with
concentrated ammonium hydroxide. Water and ammonium phosphate are added and
the digestate is stirred while a precipitate of manganese ammonium phosphate
is formed. When the precipitation is complete, the digestate is filtered.
The ammonia is then boiled off. The sample is brought to volume and analyzed
on either ICP-AES or FAA. For GFAA analysis, the volume is reduced and
allowed to cool. Concentrated HN03 is added and the solution is heated. When
the reaction is complete, bring to volume and analyze by GFAA.
3.0 INTERFERENCES
3.1 Most grades of potassium permanganate have elemental impurities
that will interfere with the analysis. It is important that the permanganate
be checked for purity. Background correction setting on an ICP-AES that are
appropriate to the digestates of other matrices will not be effective for the
digestates of oils. Background correction settings must be chosen for this
unique digestate. These digestates can have very high solids, which may
necessitate the use of internal standards, dilutions, or method of standard
addition, manganese is a very strong emitter and has many analytical lines.
analytical wavelengths must be chosen with care to avoid or minimize spectral
overlap. Inter-element correction for manganese can be used for those
instruments with that capability.
3.2 Excess ammonium hydroxide will result in the solubilization of
some manganese.
4.0 APPARATUS AND MATERIALS
4.1 Beakers - 250 ml, or equivalent.
4.2 Thermometer (0° - 200°C) or other temperature sensing device.
4.3 Filter paper - Whatman No. 41, or equivalent.
4.4 Funnels - polypropylene, or equivalent.
4.5 Heating device or hot plate.
4.6 Volumetric flasks, of suitable precision and accuracy.
NOTE: All glassware should be acid washed.
5.0 REAGENTS
5.1 Reagent Water. Reagent water will be interference free. All
references to water in the method refer to reagent water unless otherwise
specified. Refer to Chapter One of SW-846 for a definition of reagent water.
5.2 Nitric acid, concentrated, reagent grade (cone. HN03). Acid
should be analyzed to determine level of impurities. If method blank is
< MDL, then the acid can be used.
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5.3 Hydrochloric acid, concentrated, reagent grade (cone. HC1).
Acid should be analyzed to determine level of impurities. If method blank is
< MDL, then the acid can be used.
5.4 Sulfuric acid, concentrated, reagent grade (cone. H2S04). Acid
should be analyzed to determine level of impurities. If method blank is
< MDL, then the acid can be used.
5.5 Potassium permanganate - Ultra-pure grade. Reagent should be
analyzed to determine level of impurities. If method blank is < MDL, then the
reagent can be used.
5.6 Organometallic standards - scandium and/or yittrium may be used
as internal standards for most samples. Standards traceable to NIST Standard
No. 1085, for wear metals in oil, may be used.
5.7 Base oil, analyte-free. Oil should be analyzed to determine
level of impurities. If method blank is < MDL, then the reagent can be used.
5.8 Ammonium hydroxide, concentrated, reagent grade - Reagent should
be analyzed to determine level of impurities. If method blank is
< MDL, then the acid can be used.
5.9 Ammonium phosphate, reagent grade - Reagent should be analyzed
to determine level of impurities. If method blank is
< MDL, then the acid can be used.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual.
6.2 All sample containers must be pre-washed with detergents, acids,
and water. See Chapter Three, Step 3.1.3, for further information.
6.3 Samples should be processed and analyzed as soon as possible.
7.0 PROCEDURES
7.1 Homogenize sample and then take a representative sample of 0.5
grams (± O.Olg) and place in a beaker. Larger or smaller sample sizes can be
used if needed.
7.2 Add 0.5 grams of potassium permanganate powder. If larger
sample sizes are used, increase the amount of potassium permanganate so that
the ratio of oil to potassium permanganate is still 1:1. Mix the oil and
permangante thoroughly until homogeneous. Thick oils and tars that cannot be
mixed should be heated to achieve mixing (the oil may react mildly). It is
important to record the amount of potassium permanganate used for each sample
if analysis is by ICP-AES and correction is to be made for the amount of
manganese.
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If more than 10% of the sample is aromatic material, such as xylene,
then the reaction will be incomplete. If this is the case, increase the
amount of potassium permanganate. If the sample is a mixture of oil and other
non-organic materials, reduce the amount of potassium permanganate.
NOTE: All steps requiring the use of acids should be conducted
under a fume hood by properly trained personnel using
appropriate laboratory safety equipment. This should include
face shields and latex gloves.
7.3 Add 1.0 mL of concentrated H2S04, stir with glass rod and place
the beaker down. If larger sample sizes are used, increase the volume of
sulfuric acid so that ratio of oil to sulfuric acid is Ig to 2mL. The H2S04
can be added dropwise or all at once, depending on analytical needs.
(Generally, dropwise is preferred with low reporting limits are needed.) The
reaction can take several seconds to begin, but when it occurs it will be very
quick, vigorous, and exothermic. Generally larger sample sizes will react
faster than smaller. Likewise, lower average molecular weight materials will
react faster than heavier. Do not be mislead by an initial lack of
reactivity. A grey-white vapor will be ejected from the beaker (S03) and
splatting and bubbling can occur. The beaker will become very hot. This step
is complete when no more gases are given and the sample should be a thick
black lumpy past. Allow the beaker to cool to the degree necessary.
NOTE: Care must be taken when working with very light organic
materials, such as diesel fuels, as they may flash. Generally,
the lower the average molecular weight of the material
correlates to a greater danger of flashing. The danger of
flashing is reduced by adding the sulfuric acid dropwise.
NOTE: If more than 10% of the sample is aromatic material, such
as xylene, only a little grey-white vapor will form, this will
reduce accuracy and complicate nebulization. If there is a
significant amount of non-hydrocarbon material, a sputtering
reaction will occur and black Mn02 particulates will be given
off. See Step 7.2.
7.4 Add 2 ml of concentrated HN03 and stir. This reaction will be
slightly exothermic. If larger sample sizes are used, it is not always
necessary to increase the volume of HN03 proportionately, depending on
analytical needs. Some reddish-brown vapor (N02) may be given off. Allow the
reaction to continue until complete, that is when the digestate no longer
gives off fumes. Allow the beaker to cool as needed.
7.5 Then add 10 ml of concentrated HC1 and stir. If larger sample
sizes are used, it is not always necessary to increase the volume of HC1
proportionately, depending on analytical needs. This reaction will be
slightly exothermic and gas formation and foaming will occur. Lighter oils
will foam more than will heavier oils. If excess foaming occurs, add water to
prevent sample loss. Allow the beaker to cool as needed.
7.6 Heat the beaker until there is no further gas evolution.
(temperature should not exceed 150° C to prevent volatilization). There may
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be additional foaming or other milder reactions on the hot plate which may
result in overflow from the beaker. If excess foaming occurs, either remove
the beaker from the place until foaming subsides or add sufficient water to
prevent overflow. The final digestate should be a clear yellow liquid with
black or dark reddish-brown particulates.
7.7 Filter the digestate through Whatman 41 filter paper and collect
filtrate in a volumetric flask or beaker.
7.8 Wash the digestion beaker and filter paper, while still in the
funnel, with no more than 5 ml of hot HC1.
NOTE: The purpose of this next step is to recover antimony,
barium, and silver that may not have been complete solubilized.
If the sample is not being prepared for these analytes, the next
step may be skipped.
7.9 (Optional) After having washed the filter paper, remove the filter
and residue from the funnel and place in back in the beaker. Add 5 ml of
cone. HC1 and place the beaker back on the heating source until the filter
paper dissolves (temperature should not exceed 150° C to prevent
volatilization). Remove the beaker from the heating source and wash the cover
and sides with reagent grade water and then filter the residue and collect the
filtrate in the same flask or beaker as steps 7.6 and 7.7. If a volumetric
flask is used, bring to volume after the filtrate has cooled.
7.10 (Optional) If the filtrate is collected in a beaker, the filtrate
can be heated again on the hot plate to drive off excess HC1. This can reduce
matrix effects in sample introduction (temperature should not exceed 150° C to
prevent volatilization). When sufficient HC1 has been removed, remove the
beaker from the hot plate, allow to cool, and then transfer the contents to a
volumetric flask and bring to volume. However, if too much HC1 is removed,
barium, silver and antimony can be lost.
7.11 Analyze the filtrate by either ICP_AES or FAAS. Depending on the
final volume selected, the total solids in the digestate may be high enough to
cause nebulization problems. This can be corrected for by following step 7.9
and/or using internal standards and/or other matrix correction procedures.
Manganese Removal Steps
NOTE: The purpose of these next steps is to remove the
manganese in the digest by precipitating it as manganese
ammonium phosphate under alkaline conditions. Elements that do
not form insoluble phosphates, such as arsenic, are filtered out
and can be analyzed at lower concentrations,
7.12 Take the digestate, or portion of digestate and reduce the volume
to remove as much HC1 as possible without going below 10 ml. Then add cone.
NH4OH until pH is 7 or greater. For most matrices, the digestate will change
colors (often from yellow to brown) at pH 7. A mild exothermic reaction will
occur immediately.
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7.13 Add at least 2 g ammonium phosphate for each 1 g of potassium
permanganate used in the digestion and stir. An excess of phosphate is needed
for good analyte recovery. Then add enough water and mix to ensure maximum
precipitation. A pink or yellow silky amorphous precipitate, manganese
ammonium phosphate, will form. If too much NH4OH is used some of the
manganese ammonium phosphate can be solubilized. Stir until precipitation is
complete. Some ammonium phosphate may remain unreacted at the bottom of the
beaker.
7.14 Filter the digestate through Whatman 41 filter paper (or
equivalent) and collect filtrate in a volumetric flask or beaker.
7.15 Heat the filtrate to volatilize the ammonia (temperature should
not exceed 150" C to prevent volatilization), the volume of filtrate can be
reduced by heating to no less than 10 ml. IF too much water is removed any
ammonium chloride formed will solidify. If this occurs, either add enough
water to dissolve the solids or filter out the solids and wash the residue
with deionized water. A third alternative is to use nitric acid to destroy
the ammonium chloride by using step 7.16.
7.16 The filtrate can be analyzed by ICP-AES or FAAS. The chlorides in
the digestate will prevent the analysis by GFAAS.
7.17 To analyze the digestate by GFAAS, reduce the volume as much as
possible. Cool and add sufficient cone. HN03 to drive off all chlorides.
Heat gently and a mild exothermic reaction will occur. When no more reddish-
brown gas (N02) is given off, the reaction is complete and the digestate can
be cooled and taken to volume. This liquid can be analyzed by ICP-AES, FAAS,
or GFAAS.
8.0 QUALITY CONTROL
8.1 All quality control measures described in Chapter One should be
fol1 owed.
8.2 For each analytical batch of samples processed, method blanks
should be carried throughout the entire sample-preparation and analytical
process. The blank will be useful in determining if samples are being
contaminated. Do not subtract measured blank values from sample results. Use
blanks to determine the source of contamination and eliminate it.
NOTE: This blank MUST include an analyte-free oil or explosive
reactions can occur.
8.3 Duplicate samples should be processed on a routine basis. A
duplicate sample is a sample brought through the whole sample preparation and
analytical process. Refer to Chapter One for the proper protocol.
8.4 Organometallic standard reference materials (SRMs) or laboratory
control samples spiked with organo-metallic standards should be employed to
determine accuracy. Recoveries of SRMs and/or spikes should be +/- 25% of
their true values.
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9.0 METHOD PERFORMANCE
Refer to Tables 1, 2, 3, and 4.
10.0 REFERENCES
1. HMU 800, Acid Digestion of Oils for Metals Analysis by FLAA or ICP
Spectroscopy, Southern California Laboratories.
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Table 1
Performance Data Using SRM 1085"
Element
Silver
Chromium
Copper
Molybdenum
Nickel
Lead
Vanadium
8 n = 5
Analyte
Silver
Silver
Chromium
Chromium
Copper
Copper
Molybdenum
Nickel
Nickel
Lead
Lead
Vanadium
True
Value
306
296
295
303
303
297
292
Percent
Method of
Analysis
ICP-AES
FAAS
ICP-AES
FAAS
ICP-AES
FAAS
ICP-AES
ICP-AES
FAAS
ICP-AES
FAAS
ICP-AES
Mean
Value
283
295
291
283
261
297
393
Tabl
Recoveries and
True
Value
306
306
296
296
295
295
303
303
303
297
297
292
Percent
Recovery SD
e 2
Standard
Mean
Value
302
254
278
240
301
250
282
262
237
246
260
292
92 35
100 14
99 11
93 23
86 8.
100 17
135 12
Deviations86
Percent
Recovery
98
83
94
81
102
85
93
86
78
83
88
100
6
Standard
Deviations
22
6.7
19
16
24
11
12
24
9.3
17
4.2
14
8 Procedures tested using NIST SRM 1085.
b n = 12
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Table 3
Mean Measured Values for Oil Standards by Simultaneous ICP-AESa
Analyte
Silver
Arsenic
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Molybdenum
Nickel
Lead
Antimony
Selenium
Thallium
Vanadium
Zinc
500 jug/g 100 /yg/g
472
146
31.0
575
442
441
487
566
529
458
360
667°
350
NA
512
512
90.2
67.9
26.6
113
83.5
82.3
95.2
114
95.7
86.4
62.0
84.3
93.0
72.2
98.2
93.2
Concentration
50 /yg/g 25 fjg/g
46.2
39.0
8.4
56.6
43.87
42.4
50.5
55.6
48.7
46.4
30.3
68.3
50.1
37.6
49.8
43.8
23.1
18.1
5.8
28.2
21.6
20.7
27.6
25.5
26.1
25.1
16.1
42.3
25.8
28.1
27.6
16.8
5.0/yg/g
5.15 (l)b
1.8 (l)b
4.67
6.26
3.96
3.36
10.1
3.11
6.47
5.19
3.34
20.4
11.8
10.9
13.6
1.6
2.5/yg/g
2.3 (l)b
<1
2.17
3.25
1.67
0.69
7.09
0.50
3.64
4.80
3.05
7.22
11.6
<1
7.88
<1
a n = 8
b Numbers in parenthesis represent the number of "less than" values,
0 The highest standard for antimony was 1000 //g/g.
NA = Not Analyzed
3031 - 9
Revision 0
January 1995
-------
Table 4
Standard Deviations for Oil Standards by Simultaneous ICP-AES
Analyte 500 /yg/g
Silver
Arsenic
Barium
Beryl 1 i urn
Cadmium
Cobalt
Chromium
Copper
Molybdenum
Nickel
Lead
Antimony
Selenium
Thallium
Vandium
Zinc
14
3.1
0.88
3.4
2.1
2.1
2.6
3.3
3.2
2.3
1.5
34C
5.7
NA
3.8
2.4
100 jug/g
3.6
4.1
9.2
1.5
1.7
1.8
6.5
2.2
1.6
2.6
9.8
2.5
5.4
8.5
4.4
2.8
Concentration
50 fjg/g 25 fjg/g
1.1
1.7
4.0
1.5
0.73
0.69
1.3
1.9
0.62
0.08
5.6
1.6
6.8
13
0.84
3.0
4.1
1.9
5.9
0.41
0.66
1.3
4.0
1.2
1.0
7.5
2.4
2.7
8.0
18
7.2
3.2
5.0//g/g
6.3
1.1
0.30
0.35
0.53
0.24
4.5
1.7
0.69
1.2
1.6
3.7
6.4
8.2
11
4.7
2.5/^/g
0.46
b
0.18
0.46
0.26
0.30
5.1
b
0.36
2.0
3.5
1.7
4.3
b
8.3
b
8 n - 5
b The results were non-detects.
c The highest antimony standard was 1000 //g/g.
NA = Not Analyzed
3031 - 10 Revision 0
January 1995
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METHOD 3031
ACID DIGESTION OF OILS
ANALYSIS_BI FLAA OR ICP
FOR METALS
SPECTROSCOPY
1
r
7.1 Homogenize
sample.
i
r
7.2 Add potasium
permanganate
powder and heat.
1
f
7.3 Add concentrated
H2S04tO
permanganate
mixture.
>
r
7.4 Add
concentration HNOj
i
f
7.5 Add
concentrated HCI.
>
f
7.6 Filter digestate.
i
f
7,7 Rinse filter paper
and containment
vessel into the flask
containing digestate.
^
r
7.8 Add 5 mL
concentrated HCI
and reheat.
>
'
7.9 Analyze by
ICP-AES or
flame.
,
\t
3031 - 11
Revision 0
January 1995
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METHOD 3040A
DISSOLUTION PROCEDURE FOR OILS, GREASES, OR WAXES
1.0 SCOPE AND APPLICATION
1.1 This method is used for the preparation of samples containing oils,
greases, or waxes for analysis by atomic absorption spectroscopy (AAS) or
inductively coupled plasma emission spectroscopy (ICP) for the following metals:
Antimony Copper
Arsenic Iron
Barium Lead
Beryllium Manganese
Cadmium Nickel
Chromium Vanadium
1.2 This method is a solvent dissolution procedure, not a digestion
procedure. This procedure can be very useful in the analysis of crude oil, but
with spent or used oil high in particulate material it is less effective; most
particulate material is not dissolved, and therefore the analysis is not a
"total" metal determination. Because the highest percentage of metals is
expected to be contained in the particulate material, oil analysis using Method
3040A will not provide an adequate estimate of the total metals concentration.
Caution: Overheating of oils and solvents can result in an
explosion or fire, caution should be taken.
1.3 This method is applicable for the dissolution of multi-phasic aqueous
wastes containing either oils, greases, or waxes. If a waste is multi-phasic it
can be determined by using Method 3040A in combination with one of the other
sample preparation methods.
Caution: The analysis of solvents in an ICP should only be conducted
after consultation with the manufacturer.
1.4 This method is suitable for conducting analyses in support of TCLP
determinations if the percent solids, as conducted according to the procedures
specified in the Method 1311, are below 0.5%.
2.0 SUMMARY OF METHOD
2.1 A representative sample is dissolved in an appropriate solvent (e.g.,
xylene, kerosene, or methyl isobutyl ketone). Organometallic standards are
prepared using the same solvent, and the samples and standards are analyzed by
AAS or ICP.
3040A - 1 Revision 1
January 1995
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3.0 INTERFERENCES
3.1 Diluted samples and diluted organometallic standards are often
unstable. Once standards and samples are diluted, they should be analyzed as
soon as possible.
3.2 Solvent blanks should be used to rinse nebulizers thoroughly
following aspiration of high concentration standards or samples.
3.3 Viscosity differences can result in different rates of sample
introduction; therefore, all analyses shall be performed by the method of
standard addition or internal standardization (only for ICP). Peristaltic pumps
often prove useful when analysis is performed by ICP. In addition, a mass-flow
controller may also alleviate some viscosity problems.
4.0 APPARATUS AND MATERIALS
4.1 Volumetric glassware or equivalent.
4.2 Analytical balance, 300 g capacity, minimum + O.Olg.
4.3 Atomic absorption spectrometer: With an auxiliary oxidant control
and a mechanism for background correction.
4.4 Inductively coupled plasma emission spectrometer system: With a
mechanism for background correction and interelement interference correction.
A peristaltic pump is optional.
5.0 REAGENTS
5.1 Methyl isobutyl ketone (MIBK).
5.2 Xylene.
5.3 Kerosene.
5.4 Organometallic standards - scandium and yittrium may be used as
internal standards for most samples. Standards traceable to NIST Standard No.
1085, for wear metals in oil, may be used. (Two possible sources are Conostan
Division, Conoco Speciality Products, Inc., P.O. Box 1267, Ponca City, OK 74601,
and the U.S. Department of Commerce, National Institutes of Standards and
Technology, Washington, DC 20234).
5.5 Base Oil.
5.6 Stabilizer.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual.
3040A - 2 Revision 1
January 1995
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6.2 Samples shall be stored in an undiluted state at room temperature.
6.3 Samples should be processed and analyzed as soon as possible.
7.0 PROCEDURE
7.1 Weigh out a 2 gram representative sample of the waste or extract.
Separate and weigh the phases if more than one phase is present.
7.2 Weigh an aliquot of the organic phase and dilute the aliquot in the
appropriate solvent. Warming facilitates the subsampling of crude-type oils and
greases and wax-type wastes. Xylene or kerosene are usually the preferred
solvent for longer-chain hydrocarbons and for most analyses performed by TCP.
The longer-chain hydrocarbons usually require a minimum of a 1:10 (W/W) dilution,
and lighter oils may require only a 1:5 (W/W) dilution if low detection limits
are required.
7.3 Prepare a series of standards using the base oil and diluting by the
same factor used for the samples. Add the internal standard before diluting.
The concentration of the internal standard should be in the middle of the
concentration range.
7.4 If the sample contains particulates, the result may be variable
depending on whether the particles are aspirated into the instrument. Samples
may be centrifuged after dilution to remove particulates from the solution prior
to analysis.
7.5 All metals must be analyzed by the method of standard additions if
an internal standard is not used. Because the method of standard additions can
account only for multiplicative interferences (matrix or physical interferences),
the analytical program must account for additive interference (nonspecific
absorption and scattering in AAS and nonspecific emission and interelement
interference in ICP) by employing background correction when using the ICP.
7.6 Sample preparation for the method of standard additions can be
performed on a weight or volume basis. Sample aliquots of viscous wastes should
be weighed. Weigh identical amounts of the sample into three wide-mouth vials.
Dilute the first vial such that the final concentration falls on the lower end
of the linear portion of the calibration curve and significantly above the
detection limit. Add sufficient standard to the second aliquot to increase the
sample concentration by approximately 50%. Adjust the third sample concentration
so that it is approximately twice that of the first. The second and third
aliquots are then diluted to the same final volume as the first aliquot. Because
of the wide variability in waste samples, and the problems encountered with
analyzing them, the analyst's best judgement must be used to permit efficient use
of this method.
7.7 Set up and calibrate the analytical instrumentation according to the
manufacturer's directions for nonaqueous samples.
7.8 Report data as the weighted average for all sample phases.
3040A - 3 Revision 1
January 1995
-------
[(Pi * C,) + (P2 * C2)]/PT = CF
P, = weight of the first phase (Kg)
P2 = weight of the second phase (Kg)
CT = concentration of the first phase (mg/Kg)
C2 = concentration of the second phase (mg/Kg)
PT = weight of both phases (Kg)
CF = final concentration of waste (mg/Kg)
8.0 QUALITY CONTROL
8.1 Preparation blanks (e.g., Conostan base oil or mineral oil plus
reagents) should be carried through the complete sample-preparation and
analytical process on a routine basis. These blanks will be useful in detecting
and determining the magnitude of any sample contamination. Refer to Chapter One.
8.2 Replicate samples should be processed on a routine basis. Replicate
samples will be used to determine precision. Refer to Chapter One.
8.3 Samples and standards should be diluted as closely as possible to the
time of analysis.
8.4 All analyses must be performed by the method of standard additions
if an internal standard is not used. See Method 7000, Section 8.7, for further
information.
8.5 Data must be corrected for background absorption and emission and
interelement interferences.
9.0 METHOD PERFORMANCE
9.1 Refer to Tables 1 and 2 for a single lab study.
10.0 REFERENCES
1. Used Oil Characterization Sampling and Analysis Program. Draft Final Report.
February 15, 1991.
3040A - 4 Revision 1
January 1995
-------
TABLE 1 - METHOD
PERFORMANCE DATA
SINGLE LAB STUDY: ASSESSMENT OF ACCURACY
ANALYTE
Arsenic
Cadmium
Chromium
Lead
Barium
# ANALYSES
2
20
20
20
20
MEAN PERCENT
SPIKE RECOVERY
76
100.6
107.2
97.4
97.0
STANDARD
DEVIATION OUTLIERSA
39.6 1
16.8 4
13.1 2
20.2 2
30.7 4
TABLE 2 - METHOD
PERFORMANCE DATA
SINGLE LAB STUDY: ASSESSMENT OF PRECISION
ANALYTE
Arsenic
Cadmium
Chromium
Lead
Barium
# REPLICATE
PAIRS
1
10
10
10
10
RELATIVE %
DIFFERENCE
73
1.8
2.8
4.1
5.9
STANDARD
DEVIATION OUTLIERS6
1
1.9 0
1.9 0
6.6 1
12.1 1
B
- Percent recovery outside of the laboratory's 80 - 120 % acceptance criteria.
Outliers included in statistical analysis.
- RPD outside of the laboratory's 20 % acceptance criteria.
Outliers included in statistical analysis.
3040A - 5
Revision 1
January 1995
-------
METHOD 3040A
DISSOLUTION PROCEDURE FOR OILS. GREASES, OR WAXES
i
^
r
7 1 Weigh out 2 grams of sample
7.2 Separate and weigh phases
7.2 Weigh aliquot of organic phase;
dilute with appropriate method.
I
7 3 Prepare series of spike sample.
7.4 If sample contains particulatet centrifuge
7 5 Analyze metals by standard additions
method.
7.6 Weigh sample into 3 vials; dilute
1st vial; add standard to 2nd vial to
increase concentration by 50%; adjust
3rd vial concentration to twice the
concentration of the 1st vial.
7 7 Set up and calibrate analytical
instrumentation.
7 8 Report data as weighted avg.
3040A - 6
Revision 1
January 1995
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METHOD 3050B
ACID DIGESTION OF SEDIMENTS, SLUDGES, AND SOILS
1.0 SCOPE AND APPLICATION
1.1 This method has been written to provide two separate digestion
procedures, one for the preparation of sediments, sludges, and soil samples for
analysis by flame atomic absorption spectroscopy (FLAA) or inductively coupled
plasma atomic emission spectroscopy (ICP-AES) and one for the preparation of
sediments, sludges, and soil samples for analysis of samples by Graphite Furnace
AA (GFAA) or inductively coupled plasma mass spectrometry (ICP-MS). The extracts
from these two procedures are not interchangeable and should only be used with
the analytical determinations outlined in this section. Samples prepared by this
method may be analyzed by ICP-AES for all the listed metals as long as the
detecion limits are adequate for the required end-use of the data. Alternative
determinative techniques may be used if they are scientifically valid and the QC
criteria of the method, including those dealing with interferences, can be
achieved. The recommended determinative techniques for each element are listed
below:
FLAA GFAA/ICP-MS
Aluminum Magnesium Arsenic
Antimony Manganese Beryllium
Barium Molybdenum Cadmium
Beryllium Nickel Chromium
Cadmium Potassium Cobalt
Calcium Silver Iron
Chromium Sodium Lead
Cobalt Thallium Molybdenum
Copper Vanadium Selenium
Iron Zinc Thallium
Lead Vanadium
2.0 SUMMARY OF METHOD
2.1 For the digestion of samples for GFAA or ICP-MS analyses, a
representative 1-2 gram (wet weight) or 1 gram (dry weight) sample is digested
in repeated additions of nitric acid and repeated additions of hydrogen peroxide.
The digestate is then reduced in volume or heated for two hours and analyzed by
GFAA or ICP-MS. For FLAA/ICP-AES analyses, 10 mL of cone. HC1 is added to the
digestate from the GFAA/ICP-MS digestion. After refluxing for 15 minutes, the
sample is made to volume and is now ready for analysis by FLAA/ICP-MS. In an
optional step to increase the solubility of some metals (see Sec. 7.4:NOTE), this
digestate is filtered, and the filter paper and residue are washed, first with
5 mL of hot hydrochloric acid and then 20 mL of hot deionized water. Filter
paper and residue are returned to the digestion flask, refluxed with 5 mL
concentrated hydrochloric acid, and then filtered again. A separate sample shall
be dried for a total % solids determination if needed.
3050B - 1 Revision 2
January 1995
-------
3.0 INTERFERENCES
3.1 Sludge samples can contain diverse matrix types, each of which may
present its own analytical challenge. Spiked samples and any relevant standard
reference material should be processed in accordance with the quality control
requirements given in Sec. 8.0, to aid in determining whether Method 3050B is
applicable to a given waste.
4.0 APPARATUS AND MATERIALS
4.1 Digestion Vessels - 250-mL.
4.2 Watch glasses - ribbed.
4.3 Drying ovens - able to maintain 30°C + 4°C.
4.4 Thermometer - 0-200°C.
4.5 Filter paper - Whatman No. 41 or equivalent.
4.6 Centrifuge and centrifuge tubes.
4.7 Analytical balance - able to accurately weigh to 0.01 g.
4.8 Heating source - Adjustable and able to maintain a temperature of 90-
95°C. (e.g., hot plate, block digester, microwave, etc.)
4.9 Funnel or equivalent.
4.10 Graduated cylinder or equivalent.
4.11 Volumetric Flasks - 100-mL.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination. If the purity of a reagent
is questionable, analyze the reagent to determine the level of impurities. The
reagent blank must be less than the MDL in order to be used.
5.2 Reagent Water. Reagent water will be interference free. All
references to water in the method refer to reagent water unless otherwise
specified. Refer to Chapter One for a definition of reagent water.
5.3 Nitric acid (concentrated), HN03. Acid should be analyzed to
determine level of impurities. If method blank is < MDL, the acid can be used.
3050B - 2 Revision 2
January 1995
-------
5.4 Hydrochloric acid (concentrated), HC1. Acid should be analyzed to
determine level of impurities. If method blank is < MDL, the acid can be used.
5.5 Hydrogen peroxide (30%), H202. Oxidant should be analyzed to
determine level of impurities. If method blank is < MDL, the acid can be used.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
water. Plastic and glass containers are both suitable. See Chapter Three, Step
3.1.3, for further information.
6.3 Nonaqueous samples should be refrigerated upon receipt and analyzed
as soon as possible.
6.4 It can be difficult to obtain a representative sample with wet or
damp materials. Wet samples may be dried, crushed, and ground to reduce
subsample variability as long as drying does not affect the extraction of the
analytes of interest in the sample. If insoluble compounds are formed by drying,
then the sample must be analyzed as received.
7.0 PROCEDURE
7.1 Mix the sample thoroughly to achieve homogeneity and sieve if
necessary using a USS #10 sieve. All equipment used for homogenization should
be cleaned according to the guidance in Sec. 6.0 to minimize the potential of
cross-contamination. For each digestion procedure, weigh to the nearest 0,01 g
and transfer a 1-2 g sample (wet weight) or 1 g sample (dry weight) to a
digestion vessel. For samples with low percent solids a larger sample size may
be used as long as digestion is completed.
NOTE: All steps requiring the use of acids should be conducted under
a fume hood by properly trained personnel using appropriate
laboratory safety equipment. The use of an acid vapor scrubber
system for waste minimization is encouraged.
7.2 For the digestion of samples for analysis by GFAA or ICP-MS, add 10
mL of 1:1 HN03, mix the slurry, and cover with a watch glass or vapor recovery
device. Heat the sample to 95°C and reflux for 10 to 15 minutes without boiling.
Allow the sample to cool, add 5 mL of concentrated HN03, replace the cover, and
reflux for 30 minutes. If brown fumes are generated, indicating oxidation of the
sample by HN03, repeat this step (addition of 5 mL of cone. HN03) over and over
until no brown fumes are given off by the sample indicating the complete reaction
with HN03. Using a ribbed watch glass or vapor recovery system, either allow the
solution to evaporate to approximately 5 mL without boiling or heat at 95°C
without boiling for two hours. Maintain a covering of solution over the bottom
of the vessel at all times.
3050B - 3 Revision 2
January 1995
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7.2.1 After Step 7.2 has been completed and the sample has cooled,
add 2 ml of water and 3 ml of 30% H202. Cover the vessel with a watch
glass or vapor recovery device and return the covered vessel to the heat
source for warming and to start the peroxide reaction. Care must be taken
to ensure that losses do not occur due to excessively vigorous
effervescence. Heat until effervescence subsides and cool the vessel.
7.2.2 Continue to add 30% H202 in 1-mL aliquots with warming until
the effervescence is minimal or until the general sample appearance is
unchanged.
NOTE: Do not add more than a total of 10 ml 30% H202.
7.2.3 Cover the sample with a ribbed watch glass or vapor recovery
device and continue heating the acid-peroxide digestate until the volume
has been reduced to approximately 5 mL or heat at 95°C without boiling for
two hours. Maintain a covering of solution over the bottom of the vessel
at all times.
7.2.4 After cooling, dilute to 100 ml with water. Particulates in
the digestate should then be removed by filtration, by centrifugation, or
by allowing the sample to settle. The sample is now ready for analysis by
GFAA or ICP-MS.
7.2.4.1 Filtration - Filter through Whatman No. 41 filter
paper (or equivalent).
7.2.4.2 Centrifugation - Centrifugation at 2,000-3,000 rpm
for 10 minutes is usually sufficient to clear the supernatant.
7.2.4.3 The diluted digestate solution contains
approximately 5% (v/v) HN03. For analysis, withdraw aliquots of
appropriate volume and add any required reagent or matrix modifier.
7.3 For the analysis of samples for FLAA or ICP-AES, add 10 mL cone. HC1
to the sample digest from 7.2.3 and cover with a watch glass or vapor recovery
device. Place the sample on/in the heating source and reflux at 95°C for 15
minutes.
7.4 Filter the digestate through Whatman No. 41 filter paper (or
equivalent) and collect filtrate in a 100-mL volumetric flask. Make to volume and
analyze by FLAA or ICP-AES.
NOTE; Sec. 7.5 is only allowed for antimony, barium, lead, and
silver, and may be used to improve the solubilities and recoveries
of these analytes when necessary. These steps are optional and are
not required on a routine basis.
7.5 Add 2.5 mL cone. HN03 and 10 mL cone. HC1 to a 1-2 g sample (wet
weight) or 1 g sample (dry weight) and cover with a watchglass or vapor recovery
device. Place the sample on/in the heating source and reflux for 15 minutes.
3050B - 4 Revision 2
January 1995
-------
7.5.1 Filter the digestate through Whatman No. 41 filter paper
(or equivalent) and collect filtrate in a 100-mL volumetric flask.
Wash the filter paper, while still in the funnel, with no more than
5 ml of hot (95°C) HC1, then with 20 mL of hot (95°C) reagent water.
Collect washings in the same 100-mL volumetric flask.
7.5.2 Remove the filter and residue from the funnel, and place them
back in the vessel. Add 5 ml of cone. HC1, place the vessel back on the
heating source, and heat at 95°C until the filter paper dissolves. Remove
the vessel from the heating source and wash the cover and sides with
reagent water. Filter the residue and collect the filtrate in the same
100-mL volumetric flask. Allow filtrate to cool, then dilute to volume.
NOTE: High concentrations of metal salts with temperature-sensitive
solubilities can result in the formation of precipitates upon
cooling of primary and/or secondary filtrates. If precipitation
occurs in the flask upon cooling, do not dilute to volume.
7.5.3 If a precipitate forms on the bottom of a flask, add up to 10
mL of concentrated HC1 to dissolve the precipitate. After precipitate is
dissolved, dilute to volume with reagent water. Analyze by FLAA or ICP-
AES.
7.6 Calculations
7.6.1 The concentrations determined are to be reported on the
basis of the actual weight of the sample. If a dry weight analysis is
desired, then the percent solids of the sample must also be provided.
7.6.2 If percent solids is desired, a separate determination of
percent solids must be performed on a homogeneous aliquot of the sample.
8.0 QUALITY CONTROL
8.1 All quality control measures described in Chapter One should be
followed.
8.2 For each batch of samples processed, a method blank should be carried
throughout the entire sample preparation and analytical process according to the
frequency described in Chapter One. These blanks will be useful in determining
if samples are being contaminated. Refer to Chapter One for the proper protocol
when analyzing method blanks.
8.3 Spiked replicate samples should be processed on a routine basis.
Spiked replicate samples will be used to determine precision. The criteria of
the determinative method will dictate frequency, but 5% is recommended. Refer
to Chapter One for the proper protocol when analyzing spiked replicates.
8.4 Standard reference materials (SRM) must be employed to determine
accuracy. A SRM should be included with each batch of samples processed and
whenever a new sample matrix is being analyzed. Refer to Chapter One for the
proper protocol when analyzing SRMs.
3050B - 5 Revision 2
January 1995
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8.5 Limitations for the FLAA and ICP-AES optional digestion procedure:
The approximate linear upper range for a 2.00-g sample size.
Ag 2,000 mg/kg
As 1,000,000 mg/kg
Ba 2,500 mg/kg
Be 1,000,000 mg/Kg
Cd 1,000,000 mg/kg
Co 1,000,000 mg/kg
Cr 1,000,000 mg/kg
Cu 1,000,000 mg/kg
Mo 1,000,000 mg/kg
Ni 1,000,000 mg/kg
Pb 200,000 mg/kg
Sb 200,000 mg/kg
Se 1,000,000 mg/kg
Tl 1,000,000 mg/kg
V 1,000,000 mg/kg
Zn 1,000,000 mg/kg
NOTE: These ranges will vary with sample matrix, molecular form,
and size.
9.0 METHOD PERFORMANCE
9.1 In a single laboratory, the recoveries of the three matrices
presented in Table 1 through Table 3 were obtained using the FLAA and ICP-AES
digestion procedure. The spiked samples were analyzed in duplicate. Table 4
represents results of analysis of NIST Standard Reference Materials that were
obtained using both atmospheric pressure microwave digestion techniques and hot-
plate digestion procedures.
10.0 REFERENCES
1. Rohrbough, W.G.; et al . Reagent Chemicals, American Chemical Society
Specifications, 7th ed.; American Chemical Society: Washington, DC, 1986.
2. 1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
3. Edgell, K.; USEPA Method Study 37 - SW-846 Method 3050 Acid Digestion of
Sediments. Sludges, and Soils. EPA Contract No. 68-03-3254, November 1988.
4. Kimbrough, David E., and Wakakuwa, Janice R. Acid Digestion for Sediments,
Sludges, Soils, and Solid Wastes. A Proposed Alternative to EPA SW 846 Method
3050, Environmental Science and Technology, Vol. 23, Page 898, July 1989.
5. Kimbrough, David E., and Wakakuwa, Janice R. Report of an Inter! aboratory
Study Comparing EPA SW 846 Method 3050 and an Alternative Method from the
California Department of Health Services, Fifth Annual Waste Testing and Quality
Assurance Symposium, Volume I, July 1989. Reprinted in Solid Waste Testing and
3050B - 6 Revision 2
January 1995
-------
Quality Assurance: Third Volume, ASTM STP 1075, Page 231, C.E. Tatsch, Ed.,
American Society for Testing and Materials, Philadelphia, 1991.
6. Kimbrough, David E., and Wakakuwa, Janice R. A Study of the Linear Ranges
of Several Acid Digestion Procedures. Environmental Science and Technology, Vol.
26, Page 173, January 1992. Presented Sixth Annual Waste Testing and Quality
Assurance Symposium, July 1990.
7. Kimbrough, David E., and Wakakuwa, Janice R. A Study of the Linear Ranges
of Several Acid Digestion Procedures, Sixth Annual Waste Testing and Quality
Assurance Symposium, Reprinted in Solid Waste Testing and Quality Assurance:
Fourth Volume, ASTM STP 1076, Ed., American Society for Testing and Materials,
Philadelphia, 1992.
3050B - 7 Revision 2
January 1995
-------
TABLE 1
STANDARD RECOVERY8
Percent Recovery
i
Analyte
Ag
As
Ba
Be
Cd
Co
Cr
Cu
Mo
Ni
Pb
Sb
Se
Tl
V
Zn
,11 values are percent
iulti standard; n = 3.
3050A
9.5
86
97
96
101
99
98
87
97
98
97
87
94
96
93
99
recovery.
3050B w/option
98
102
103
102
99
105
94
94
96
92
95
88
91
96
103
95
Samples: 4 ml of 100
mg/mL
3050B - 8
Revision 2
January 1995
-------
TABLE 2
Percent Recovery"'0
Sample 4435 Sample 4766 Sample HJ Average
3050A 3050B 3050A 3050B 3050A 3050B 3050A 3050B
Ag
As
Ba
Be
Cd
Co
Cr
Cu
Mo
Ni
Pb
Sb
Se
Tl
V
Zn
9.8
70
85
94
92
90
90
81
79
88
82
28
84
88
84
96
103
102
94
102
88
94
95
88
92
93
92
84
89
87
97
106
15
80
78
108
91
87
89
85
83
93
80
23
81
69
86
78
89
95
95
98
95
95
94
87
98
100
91
77
96
95
96
75
56
83
b
99
95
89
72
70
87
87
77
46
99
66
90
b
93
102
b
94
97
93
101
106
103
101
91
76
96
67
88
b
27
77
81
99
93
89
83
77
83
92
81
32
85
74
87
87
95
100
94
97
94
94
97
94
98
98
91
79
94
83
93
99
a - Samples: 4 ml of 100 mg/mL multi-standard in 2 g of sample. Each value is
percent recovery and is the average of duplicate spikes.
b - Unable to accurately quantitate due to high background values.
c - Method 3050B using optional section
3050B - 9 Revision 2
January 1995
-------
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METHOD 3050B
ACID DIGESTION OF SEDIMENTS, SLUDGES, AND SOILS
7.3 Add 10 mL con-
centrated HCI to the
digest from 7.2.3 and
cover reflux for
15 minutes.
7.1 Mix sample
to homogeneity.
7.2 Add 10 mL VI
HNO3and reflux for
s*. 1 0 minutes.
7.2 Add 5 mL cone
HNO3and reflux for
30 mini.; repeat
until dig. is complete
evaporate to
5 mL; cool.
7.2.1 - 7.2.2 Add
2 mL water and 3 mL
30% HjOj continue
to add 1 mL aliquots
of HzO2 until bubbling
subsides.
7.3.1 Filter,
lakt to volume.
7.2.4 Filter/centrifuge.
if necessary, dilute
to 100 mL with water.
Only for Sb, Ba, Pb, and Ag
if required
7.4 Analyze by
FLAA or ICP-AES.
7 2.3 Analyze by
GFAA or ICP-MS.
7.8
Calculations.
7.5 Add 2.5 mL cone.
NNO and 10 ml cone.
HCI to sample reflux
for 1 5 minutes.
7 5.1 Filter digeltate
and collect in
volumetric flask.
7.5.1 Wash filter paper
with 5 mL hot HCI and
then with 20 ml hot
reagent water. Collect
in same 1 00 mL flask
as filtrate
7.5.2 Remove filter
and residues and place
back in vessel. Add
5 mL HCL and heat
filter; collect in same
flask as filtrate.
7 5.3 If precipitate
forms add up to
10 mL HC! to dissolve.
Dilute to volume.
7.5.3 Analyze by
FLAA or ICP-AES
3050B - 12
Revision 2
January 1995
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METHOD 3052
MICROWAVE ASSISTED ACID DIGESTION OF SILICEOUS AND ORGANICALLY BASED MATRICES
1.0 SCOPE AND APPLICATION
1.1 This method is applicable to the microwave assisted acid digestion of
siliceous matrices, organic matrices and other complex matrices. Ashes,
biological tissues, oils, oil contaminated soils, sediments, sludges, and soils
may be digested using this method for total decomposition (relative to the target
analyte list) and if analysis is required. This method is applicable for the
following elements:
Aluminum Cadmium Iron Molybdenum Sodium
Antimony Calcium Lead Nickel Strontium
Arsenic Chromium Magnesium Potassium Thallium
Boron Cobalt Manganese Selenium Vanadium
Barium Copper Mercury Silver Zinc
Beryllium
Other elements and matrices may be analyzed by this method if performance is
demonstrated for the analytes of interest, in the matrices of interest, at the
concentration levels of interest (see Sec. 8.0).
1.2 This method is provided as a rapid multi-element, microwave assisted
acid digestion prior to analysis protocol so that decisions can be made about the
site or material. Digests and alternative procedures produced by the method are
suitable for analysis by flame atomic absorption spectroscopy (FLAAS), cold vapor
atomic absorption spectroscopy (CVAAS), graphite furnace atomic absorption
spectroscopy (GFAAS), inductively coupled plasma atomic emission spectroscopy
(ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS) and other
analytical elemental analysis techniques where applicable. Due to the rapid
advances in microwave technology, consult your manufacturer's recommended
instructions for guidance on their microwave digestion system and refer to the
SW-846 "DISCLAIMER" when conducting analyses using Method 3052.
1.3 The goal of this method is total sample decomposition and with
judicious choice of acid combinations this is achievable for most matrices (see
Sec. 3.2). Selection of reagents which give the highest recoveries for the
target analytes is considered the optimum method condition.
2.0 SUMMARY OF METHOD
2.1 A representative sample of up to 0.5 g is digested in 9 mL of
concentrated nitric acid and usually 3 mL hydrofluoric acid for 15 minutes using
microwave heating with a suitable laboratory microwave system. The method has
several additional alternative acid and reagent combinations including
hydrochloric acid and hydrogen peroxide. The method has provisions for scaling
up the sample size to a maximum of 1.0 g. The sample and acid are placed in
appropriate fluorocarbon microwave vessels. The vessel is sealed and heated in
3052 - 1 Revision 0
January 1995
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the microwave system. The temperature profile is specified to permit specific
reactions and incorporates reaching 180 ± 5°C in approximately less than 5.5
minutes and remaining at 180 ± 5°C for 9.5 minutes for the completion of specific
reactions (Ref. 1, 2, 3, 4). After cooling, the vessel contents may be filtered,
centrifuged, or allowed to settle and then decanted, diluted to volume, and
analyzed by the appropriate SW-846 method (Ref. 5).
3.0 INTERFERENCES
3.1 Gaseous digestion reaction products, very reactive, or volatile
materials may create high pressures when heated and may cause venting of the
vessels with potential loss of sample and analytes. The complete decomposition
of either carbonates, or organic samples, may cause enough pressure to vent the
vessel if the sample size is greater than 0.25 g. Variations of the method due
to very reactive materials are specifically addressed in Sees. 7.3.4 and 7.3.6.1.
3.2 Most samples will be totally dissolved by this method with judicious
choice of the acid combinations. A few refractory sample matrix compounds, such
as Ti02, alumina, and other oxides may not be totally dissolved. In some cases
they may contain target analyte elements.
4.0 APPARATUS AND MATERIALS
4.1 Microwave apparatus requirements.
4.1.1 The temperature performance requirements necessitate the
microwave decomposition system to sense the temperature to within ± 2.5°C
and automatically adjust the microwave field output power within 2 seconds
of sensing. Temperature sensors should be accurate to ± 2°C (including
the final reaction temperature of 180°C); verification at two points > 50°
C apart should be determined periodically. Temperature feedback control
provides the primary control performance mechanism for the method. Due to
the flexibility in the reagents used to achieve total analysis,
temperature feedback control is necessary for reproducible microwave
heating.
Alternatively, for a specific set of reagent(s) combination(s),
quantity, and specific vessel type, a calibration control mechanism can be
developed similar to previous microwave methods (see Method 3051 in Ref
5). Through calibration of the microwave power, vessel load and heat
loss, the reaction temperature profile described in Sec. 7.3.6 can be
reproduced. The calibration settings are specific for the number and type
of vessel used and for the microwave system in addition to the variation
in reagent combinations. Therefore no specific calibration settings are
provided in this method. These settings may be developed by using
temperature monitoring equipment for each specific set of equipment and
reagent combination. They may only be used if not altered as previously
described in other methods such as 3051 and 3015. In this circumstance,
3052 - 2 Revision 0
January 1995
-------
the microwave system provides programmable power with a minimum of 600 W,
which can be programmed to within ± 12 W of the required power. Typical
systems provide a nominal 600 W to 1200 W of power (Ref. 1, 2, 6).
Calibration control provides backward compatibility with older laboratory
microwave systems without temperature monitoring or feedback control and
with lower cost microwave systems for some repetitive analyses. Older
lower pressure vessels may not be compatible.
4.1.2 The microwave unit cavity is corrosion resistant and well
ventilated. All electronics are protected against corrosion for safe
operation.
CAUTION: There are many safety and operational recommendations
specific to the model and manufacturer of the microwave equipment
used in individual laboratories. A listing of these specific
suggestions is beyond the scope of this method and require the
analyst to consult the specific equipment manual, manufacturer, and
literature for proper and safe operation of the microwave equipment
and vessels.
4.1.3 The method requires essentially microwave transparent and
reagent resistant materials such as fluorocarbon polymers (examples are
PFA or TFM) to contain acids and samples. For higher pressure capabilities
the vessel may be contained within layers of different microwave
transparent materials for strength, durability, and safety. The vessels'
internal volume should be at least 50 ml, capable of withstanding
pressures of at least 30 atm (30 bar or 435 psi), and capable of
controlled pressure relief. These specifications are to provide an
appropriate, safe, and durable reaction vessel of which there are many
adequate designs by many suppliers.
CAUTION: The outer layers of vessels are frequently not as acid or
reagent resistant as the liner material and must not be chemically
degraded or physically damaged to retain the performance and safety
required. Routine examination of the vessel materials may be
required to ensure their safe use.
CAUTION: The second safety concern relates to the use of sealed
containers without pressure relief devices. Temperature is the
important variable controlling the reaction. Pressure is needed to
attain elevated temperatures, but must be safely contained.
However, many digestion vessels constructed from certain
fluorocarbons may crack, burst, or explode in the unit under certain
pressures. Only fluorocarbon (such as PFA or TFM and others)
containers with pressure relief mechanisms or containers with
fluorocarbon liners and pressure relief mechanisms are considered
acceptable.
Users are therefore advised not to use domestic (kitchen) type
microwave ovens or to use inappropriate sealed containers without
pressure relief for microwave acid digestions by this method. Use
3052 - 3 Revision 0
January 1995
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of laboratory-grade microwave equipment is required to prevent
safety hazards. For further details, consult References 3 and 7.
4.1.4 A rotating turntable is employed to insure homogeneous
distribution of microwave radiation within most systems (Ref. 1). The
speed of the turntable should be a minimum of 3 rpm.
CAUTION: Laboratories should not use domestic (kitchen) type
microwave ovens for this method. There are several significant
safety issues. First, when an acid such as nitric is used to effect
sample digestion in microwave units in open vessel(s), or sealed
vessel equipment, there is the potential for the acid gas vapor
released to corrode the safety devices that prevent the microwave
magnetron from shutting off when the door is opened. This can
result in operator exposure to microwave energy. Use of a system
with isolated and corrosion resistant safety devices prevents this
from occurring.
4.2 Volumetric ware, volumetric flasks, and graduated cylinders, 50 and
100 ml capacity or equivalent.
4.3 Filter paper, qualitative or equivalent.
4.4 Filter funnel, polypropylene, polyethylene or equivalent.
4.5 Analytical balance, of appropriate capacity, with a minimum ± 0.0001
g or appropriate precision for the weighing of the sample. Optionally, the
vessel with sample and reagents may be weighed before and after microwave
processing to evaluate the seal integrity in some vessel types.
5.0 REAGENTS
5.1 All reagents should be of appropriate purity or high purity (acids for
example, should be sub-boiling distilled where possible) to minimize the blank
levels due to elemental contamination. All references to water in the method
refer to reagent water (Ref. 8). Other reagent grades may be used, provided it
is first ascertained that the reagent is of sufficient purity to permit its use
without lessening the accuracy of the determination. If the purity of a reagent
is questionable, analyze the reagent to determine the level of impurities. The
reagent blank must be less than the MDL in order to be used.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
water. Plastic and glass containers are both suitable. See Chapter Three, Sec.
3.1.3 of this manual, for further information.
3052 - 4 Revision 0
January 1995
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6.3 Refer to Chapter Three for the appropriate holding times and storage
conditions.
7.0 PROCEDURE
7.1 Temperature control of closed vessel microwave instruments provides the
main feedback control performance mechanism for the method. Control requires a
temperature sensor in one or more vessels during the entire decomposition. The
microwave decomposition system should sense the temperature to within ± 2.5°C and
permit adjustment of the microwave output power within 2 seconds.
7.2 All digestion vessels and volumetric ware must be carefully acid washed
and rinsed with reagent water. When switching between high concentration samples
and low concentration samples, all digestion vessels (fluoropolymer liners only)
should be cleaned by leaching with hot (1:1) hydrochloric acid (greater than
80°C, but less than boiling) for a minimum of two hours followed with hot (1:1)
nitric acid (greater than 80°C, but less than boiling) for a minimum of two hours
and rinsed with reagent water and dried in a clean environment. This cleaning
procedure should also be used whenever the prior use of the digestion vessels is
unknown or cross contamination from vessels is suspected. Polymeric or glass
volumetric ware (not used with HF) and storage containers should be cleaned by
leaching with more dilute acids (approximately 10% V/V) appropriate for the
specific plastics used and then rinsed with reagent water and dried in a clean
environment. To avoid precipitation of silver, ensure that all HC1 has been
rinsed from the vessels.
7.3 Sample Digestion
7.3.1 Weigh a well-mixed sample to the nearest 0.001 g into an
appropriate vessel equipped with a pressure relief mechanism. For soils,
ash, sediments, sludges, and siliceous wastes, initially use no more than
0.5 g. For oil or oil contaminated soils, initially use no more than 0.25
9-
7.3.2 Add 9 ± 0.1 ml concentrated nitric acid and 3 ± 0.1 ml
concentrated hydrofluoric acid to the vessel in a fume hood. If the
approximate silicon dioxide content of the sample is known, the quantity
of hydrofluoric acid may be varied from 0 to 5 ml for stoichiometric
reasons. Samples with higher concentrations of silicon dioxide (> 70%)
may require higher concentrations of hydrofluoric acid (> 3 ml HF).
Alternatively samples with lower concentrations of silicon dioxide (< 10%
to 0%) may require much less hydrofluoric acid (0.5 ml to 0 ml). Examples
are presented in Table 1, 2, 3, and 6.
7.3.3 The addition of other reagents with the original acids prior
to digestion may permit more complete oxidation of organic sample
constituents, address specific decomposition chemistry requirements, or
address specific elemental stability and solubility problems.
3052 - 5 Revision 0
January 1995
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The addition of 2 ± 2 ml concentrated hydrochloric acid to the
nitric and hydrofluoric acids is appropriate for the stabilization of Ag,
Ba, and Sb and high concentrations of Fe and Al in solution. The amount
of HC1 needed will vary depending on the matrix and the concentration of
the analytes. The addition of hydrochloric acid may; however, limit the
techniques or increase the difficulties of analysis. Examples are
presented in Table 4.
The addition of hydrogen peroxide (30%) in small or catalytic
quantities (such as 0.1 to 2 ml) may aid in the complete oxidation of
organic matter.
The addition of water (double deionized) may (0 to 5 ml) improve the
solubility of minerals and prevent temperature spikes due to exothermic
reactions.
CAUTION: The use of microwave equipment with temperature feedback
control is required to control the unfamiliar reactions of unique or
undemonstrated reagent combinations of unknown samples. These tests
may require additional vessel requirements such as increased
pressure capabilities.
CAUTION: Only one acid mixture or quantity may be used in a single
batch in the microwave to insure consistent reaction conditions
between all vessels and monitored conditions. This limitation is
due to the current practice of monitoring a representative vessel
and applying a uniform microwave field to reproduce these reaction
conditions within a group of vessels being simultaneously heated.
CAUTION: Toxic nitrogen oxide(s), hydrogen fluoride, and toxic
chlorine (from the addition of hydrochloric acid) fumes are usually
produced during digestion. Therefore, all steps involving open or
the opening of microwave vessels must be performed in a properly
operating fume ventilation system.
CAUTION: The analyst should wear protective gloves and face
protection and must not at any time permit a solution containing
hydrofluoric acid to come in contact with skin or lungs.
CAUTION: The addition of hydrochloric acid must be from
concentrated hydrochloric acid and not from a premixed combination
of acids as a buildup of chlorine gas will result from a premixed
acid solution.
CAUTION: When digesting samples containing volatile or easily
oxidized organic compounds, initially weigh no more than 0.10 g and
observe the reaction before capping the vessel. If a vigorous
reaction occurs, allow the reaction to cease before capping the
vessel. If no appreciable reaction occurs, a sample weight up to
0.25 g can be used.
3052 - 6 Revision 0
January 1995
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CAUTION: The addition of hydrogen peroxide should only be done when
the reactive components of the sample are known. Hydrogen peroxide
may react rapidly and violently on easily oxidizable materials and
should not be added if the sample may contain large quantities of
easily oxidizable organic constituents.
7.3.4 The analyst should be aware of the potential for a vigorous
reaction. If a vigorous reaction occurs upon the initial addition of
reagent or the sample is suspected of containing easily oxidizable
materials, allow the sample to predigest in the uncapped digestion vessel.
Heat may be added in this step for safety considerations (for example the
rapid release of carbon dioxide from carbonates, easily oxidized organic
matter, etc.). Once the initial reaction has ceased, the sample may
continue through the digestion procedure.
7.3.5 Seal the vessel according to the manufacturer's directions.
Properly place the vessel in the microwave system according to the
manufacturer's recommended specifications and connect appropriate
temperature and pressure sensors to vessels according to manufacturer's
specifications.
7.3.6 This method is a performance based method, designed to
achieve or approach total decomposition of the sample through achieving
specific reaction conditions. The temperature of each sample should rise
to 180 ± 5°C in approximately 5.5 minutes and remain at 180 + 5°C for 9.5
minutes. The temperature-time and pressure-time profile are given for a
standard soil sample in Figure 1. The number of samples simultaneously
digested is dependent on the analyst. The number may range from 1 to the
maximum number of vessels that the microwave units magnetron can heat
according to the manufacturer's or literature specifications (the number
will depend on the power of the unit, the quantity and combination of
reagents, and the heat loss from the vessels).
The pressure should peak between 5 and 15 minutes for most samples
(Ref. 2, 3, 6). If the pressure exceeds the pressure limits of the
vessel, the pressure will be reduced by the relief mechanism of the
vessel.
7.3.6.1 For reactive substances, the heating profile may be
altered for safety purposes. The decomposition is primarily
controlled by maintaining the reagents at 180 ± 5°C for 9.5 minutes,
therefore the time it takes to heat the samples to 180°C ± 5°C is
not critical. The samples may be heated at a slower rate to prevent
potential uncontrollable exothermic reactions. The time to reach
180 ± 5°C may be increased to 10 minutes provided that 180 ± 5°C is
subsequently maintained for 9.5 minutes. Decomposition profiles are
presented in Figures 1 & 2. The extreme difference in pressure is
due to the gaseous digestion products.
7.3.6.2 Calibration control is applicable in reproducing this
method provided the power in watts versus time parameters are
3052 - 7 Revision 0
January 1995
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determined to reproduce the specifications listed in 7.3.6. The
calibration settings will be specific to the quantity and
combination of reagents, quantity of vessels, and heat loss
characteristics of the vessels (Ref 1). If calibration control is
being used, any vessels containing acids for analytical blank
purposes are counted as sample vessels and when fewer than the
recommended number of samples are to be digested, the remaining
vessels should be filled with the same acid mixture to achieve the
full complement of vessels. This provides an energy balance, since
the microwave power absorbed is proportional to the total absorbed
mass in the cavity (Ref. 1). Irradiate each group of vessels using
the predetermined calibration settings. (Different vessel types
should not be mixed).
7.3.7 At the end of the microwave program, allow the vessels to
cool for a minimum of 5 minutes before removing them from the microwave
system. When the vessels have cooled to near room temperature, determine
if the microwave vessels have maintained a seal throughout the digestion.
Due to the wide variability of vessel designs, a single procedure is not
appropriate. For vessels that are sealed as discrete separate entities,
the vessel weight may be taken before and after digestion to evaluate seal
integrity. If the weight loss of sample exceeds 1% of the weight of the
sample and reagents, then the sample is considered compromised. For
vessels with burst disks, a careful visual inspection of the disk may
identify compromised vessels. For vessels with resealing pressure relief
mechanisms, an auditory or sometimes a physical sign indicates a vessel
has vented.
7.3.8 Complete the preparation of the sample by carefully uncapping
and venting each vessel in a fume hood. Vent the vessels using the
procedure recommended by the vessel manufacturer. Transfer the sample to
an acid-cleaned bottle. If the digested sample contains particulates
which may clog nebulizers or interfere with injection of the sample into
the instrument, the sample may be centrifuged, allowed to settle, or
filtered.
7.3.8.1 Centrifugation: Centrifugation at 2,000 - 3,000 rpm
for 10 minutes is usually sufficient to clear the supernatant.
7.3.8.2 Settling: If undissolved material remains such as
Ti02, or other refractory oxides, allow the sample to stand until
the supernatant is clear. Allowing a sample to stand overnight will
usually accomplish this. If it does not, centrifuge or filter the
sample.
7.3.8.3 Filtering: If necessary, the filtering apparatus
must be thoroughly cleaned and prerinsed with dilute (approximately
10% V/V) nitric acid. Filter the sample through qualitative filter
paper into a second acid-cleaned container.
3052 - 8 Revision 0
January 1995
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7.3.9 If the hydrofluoric acid concentration is a consideration in
the analysis technique such as with ICP methods, boric acid may be added
to permit the complexation of fluoride to protect the quartz plasma torch.
The amount of acid added may be varied, depending on the equipment and the
analysis procedure. If this option is used, alterations in the
measurement procedure to adjust for the boric acid and any bias it may
cause are necessary. This addition will prevent the measurement of boron
as one of the elemental constituents in the sample. Alternatively, a
hydrofluoric acid resistant ICP torch may be used and the addition of
boric acid would be unnecessary for this analytical configuration. All
major manufacturers have hydrofluoric resistant components available for
the analysis of solutions containing hydrofluoric acid.
7.3.10 The removal or reduction of the quantity of the hydrochloric
and hydrofluoric acids prior to analysis may be desirable. The chemistry
and volatility of the analytes of interest should be considered and
evaluated when using this alternative. Evaporation to near dryness in a
controlled environment with controlled pure gas and neutralizing and
collection of exhaust interactions is an alternative where appropriate.
This manipulation may be performed in the microwave system, if the system
is capable of this function, or external to the microwave system in more
common apparatus(s). This option must be tested and validated to
determine analyte retention and loss and should be accompanied by
equipment validation possibly using the standard addition method and
standard reference materials. This alternative may be used to alter
either the acid concentration and/or acid composition. Note: The final
solution typically requires nitric acid to maintain appropriate sample
solution acidity and stability of the elements. Commonly, a 2% (v/v)
nitric acid concentration is desirable. Examples of analysis performed
with and without removal of the hydrofluoric acid are presented in Table
5. Waste minimization techniques should be used to capture reagent fumes.
This procedure should be tested and validated in the apparatus and on
standards before using on unknown samples.
7.3.11 Transfer or decant the sample into volumetric ware and dilute
the digest to a known volume. The digest is now ready for analysis for
elements of interest using appropriate elemental analysis techniques
and/or SW-846 methods.
7.3.12 Sample size may be scaled-up from 0.1, 0.25, or 0.5 g to 1.0
g through a series of 0.2 g sample size increments. Scale-up can produce
different reaction conditions and/or produce increasing gaseous reaction
products. Increases in sample size may not require alteration of the acid
quantity or combination, but other reagents may be added to permit a more
complete decomposition and oxidation of organic and other sample
constituents where necessary (such as increasing the HF for the complete
destruction of silicates). Each step of the scale-up must demonstrate
safe operation before continuing.
7.4 Calculations: The concentrations determined are to be reported on the
basis of the actual weight of the original sample.
3052 - 9 Revision 0
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7.5 Calibration of Microwave Equipment
NOTE: If the microwave unit uses temperature feedback control to
follow performance specifications of the method, then the
calibration procedure will not be necessary.
7.5.1 Calibration is the normalization and reproduction of a
microwave field strength to permit reagent and energy coupling in a
predictable and reproducible manner. It balances reagent heating and heat
loss from the vessels and is equipment dependent due to the heat retention
and loss characteristics of the specific vessel. Available power is
evaluated to permit the microwave field output in watts to be transferred
from one microwave system to another.
Use of calibration to control this reaction requires balancing output
power, coupled energy, and heat loss to reproduce the temperature heating
profile in Sec. 7.3.6. The conditions for each acid mixture and each
batch containing the same specified number of vessels must be determined
individually. Only identical acid mixtures and vessel models and
specified numbers of vessels may be used in a given batch.
7.5.2 For cavity type microwave equipment, this is accomplished by
measuring the temperature rise in 1 kg of water exposed to microwave
radiation for a fixed period of time. The analyst can relate power in
watts to the partial power setting of the system. The calibration format
required for laboratory microwave systems depends on the type of
electronic system used by the manufacturer to provide partial microwave
power. Few systems have an accurate and precise linear relationship
between percent power settings and absorbed power. Where linear circuits
have been utilized, the calibration curve can be determined by a three-
point calibration method (7.5.4), otherwise, the analyst must use the
multiple point calibration method (7.5.3).
7.5.3 The multiple point calibration involves the measurement of
absorbed power over a large range of power settings. Typically, for a 600
W unit, the following power settings are measured; 100, 99, 98, 97, 95,
90, 80, 70, 60, 50, and 40% using the procedure described in Sec. 7.5.5.
This data is clustered about the customary working power ranges.
Nonlinearity has been commonly encountered at the upper end of the
calibration. If the system's electronics are known to have nonlinear
deviations in any region of proportional power control, it will be
necessary to make a set of measurements that bracket the power to be used.
The final calibration point should be at the partial power setting that
will be used in the test. This setting should be checked periodically to
evaluate the integrity of the calibration. If a significant change is
detected (± 10 W), then the entire calibration should be reevaluated.
7.5.4 The three-point calibration involves the measurement of
absorbed power at three different power settings. Measure the power at
100% and 50% using the procedure described in Sec. 7.5.5. From the 2-
point line calculate the power setting corresponding to the required power
3052 - 10 Revision 0
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in watts specified in the procedure. Measure the absorbed power at that
partial power setting. If the measured absorbed power does not correspond
to the specified power within ± 10 W, use the multiple point calibration
in 7.5.3. This point should also be used to periodically verify the
integrity of the calibration.
7.5.5 Equilibrate a large volume of water to room temperature (23
± 2°C). One kg of reagent water is weighed (1,000.0 g + 0.1 g) into a
fluorocarbon beaker or a beaker made of some other material that does not
significantly absorb microwave energy (glass absorbs microwave energy and
is not recommended). The initial temperature of the water should be 23 ±
2°C measured to ± 0.05°C. The covered beaker is circulated continuously
(in the normal sample path) through the microwave field for 2 minutes at
the desired partial power setting with the system's exhaust fan on maximum
(as it will be during normal operation). The beaker is removed and the
water vigorously stirred. Use a magnetic stirring bar inserted
immediately after microwave irradiation and record the maximum temperature
within the first 30 seconds to ± 0.05°C. Use a new sample for each
additional measurement. If the water is reused, both the water and the
beaker must have returned to 23 ± 2"C. Three measurements at each power
setting should be made.
The absorbed power is determined by the following relationship:
(K) (Cp) (m) (DT)
Eq. 1 P =
Where:
P = the apparent power absorbed by the sample in watts (W) (W=joule/sec-1)
K = the conversion factor for thermochemical calories/sec"1 to watts (=4.184)
Cp = the heat capacity, thermal capacity, or specific heat (cal/g"1 °C-1) of water
m = the mass of the water sample in grams (g)
DT = the final temperature minus the initial temperature (°C)
t = the time in seconds (s)
Using the experimental conditions of 2 minutes and 1 kg of distilled water
(heat capacity at 25 °C is 0.9997 cal/g'VT1) the calibration equation
simplifies to:
Eq. 2 P = (DT) (34.86)
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NOTE: Stable line voltage is necessary for accurate and reproducible
calibration and operation. The line voltage should be within
manufacturer's specification, and during measurement and operation
should not vary by more than ± 5 V. Electronic components in most
microwave units are matched to the system's function and output.
When any part of the high voltage circuit, power source, or control
components in the system have been serviced or replaced, it will be
necessary to recheck the system's calibration. If the power output
has changed significantly (± 10 W), then the entire calibration
should be reevaluated.
8.0 QUALITY CONTROL
8.1 All quality control data must be maintained and available for reference
or inspection for a period of three years. This method is restricted to use by,
or under supervision of, experienced analysts. Refer to the appropriate section
of Chapter One for additional quality control guidance.
8.2 Duplicate samples should be processed on a routine basis. A duplicate
sample is a sample brought through the whole sample preparation and analytical
process. A duplicate sample should be processed with each analytical batch or
every 20 samples, whichever is the greater number. A duplicate sample should be
prepared for each matrix type (i.e., soil, sludge, etc.). The relative percent
difference between replicate determinations is to be calculated as follows:
D - D
RPD =
(D + D
where:
RPD = relative percent difference.
D, = first sample value.
D2 = second sample value (replicate).
(A control limit of + 20% RPD shall be used for sample values
greater than ten times the instrument detection limit.)
8.3 Spiked samples and/or matrix matching standard reference materials
(SRMs) should be included with each group of samples processed or every 20
samples, whichever is the greater number. A spiked sample should also be
included whenever a new sample matrix is being analyzed. Spike sample recovery
and/or SRMs are to be within ± 20% of the actual value.
8.4 Blank samples should be prepared using the same reagents and quantities
used in sample preparation, placed in vessels of the same type, and processed
with the samples.
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8.5 Other alternate method performance quality control criteria may be
allowed as long as they meet the data quality objectives of the analysis.
9.0 METHOD PERFORMANCE
9.1 Precision: Precision data for Method 3052, is presented in tables at
the end of the document. Values are given as concentration ± the standard
deviation.
9.2 The performance criteria are provided in an example in Figure 1. The
temperature profile will be within ± 5°C of the mean of the temperature profile,
but the pressure curve will vary depending on the acid mixture and gaseous
digestion products and the thermal insulating properties of the vessel.
10.0 REFERENCES
1. Introduction to Microwave Sample Preparation: Theory and Practice, Kingston,
H. M. and Jassie, L. B., Eds.; ACS Professional Reference Book Series; American
Chemical Society: Washington, DC, 1988.
2. Kingston, H. M., Walter, P. J., Comparison of Microwave Versus Conventional
Dissolution for Environmental Applications, Spectroscopy, Vol. 7 No. 9,20-
27,1992.
3. Kingston, H. M., Haswell, S, Microwave Enhanced Chemistry, ACS Professional
Reference Book Series; American Chemical Society: Washington, DC, 1995. (in
press)
4. Kingston, H. M.; Walter, P. 0.; Lorentzen, E. M. L.; Lusnak, G. P. Report to
NIST Office of Standard Reference Materials, The Performance of Leaching Studies
on Soil SRMs 2710 and 2711, Duquesne University, Pittsburgh, PA, 1994.
5. Test Methods for Evaluating Solid Waste, Physical/Chemical Methods, 3rd ed;
U.S. Environmental Protection Agency, Office of Solid Waste and Emergency
Response. U.S. Government Printing Office: Washington, DC, 1986; SW-846.
6. Kingston, H. M. EPA IAG #DWI-393254-01-0 January 1-March 31, 1988, quarterly
Report.
7. Kingston, H. M. and Jassie, L. B., "Safety Guidelines for Microwave Systems
in the Analytical Laboratory". In Introduction to Microwave Acid Decomposition:
Theory and Practice; Kingston, H. M. and Jassie, L. B,, eds.; ACS Professional
Reference Book Series; American Chemical Society: Washington, DC, 1988.
8. 1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM, Philadelphia, PA, 1985, D1193-77.
9. Kingston, H. M.; Walter, P. J.; Link, D. D. Validation Study and
Unpublished Data, Duquesne University, Pittsburgh, PA, 1995.
3052 - 13 Revision 0
January 1995
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200
9 150 -
9ml HNO and 3ml HF
12
10
8
Ul
Ul
0 5 10 15
time (mln)
Figure 1: Typical Reaction Profile for the Digestion of a Soil
(Ref 4 and 9)
£
u.
200
150
100
50
0
9ml HNO t and 0.5ml HF
~0.3g Waste Oil
t 11 [ i \ ..i.i 1 t i i
20
15
(Q
(A
ift
m
5
0
20
0 5 „ 107 , x 15
time (mln)
Figure 2: Typical Reaction Profile for the Digestion of a Oil (Ref
9)
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TABLE 1.
ANALYSIS OF NIST SRM 2704
(COMPILATION OF REFERENCES 2 AND 9)
NIST SRM 2704 - Buffalo River Sediment
Element
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Phosphorus
Selenium
Sulfur
Thallium
Uranium
Zinc
Analyzed Value
(mg/Kg)
23.4 ± 2.6
3.5 ± 1.2
132.9 ± 1.3
98.0 ± 4.2
155 ± 9.2
1.49 ± 0.14
43.6 ± 3.9
1.016 ± 0.016
(mg/g)
1.13 ± 0.9
3.56 ± 0.16
1.15 ± 0.22
2.97 ± 0.04
441.9 + 0.8
Certified Value
(mg/Kg)
23.4 ± 0.8
3.45 ± 0.22
135 ± 5
98.6 ± 5.0
161 ± 17
1.44 ± 0.07
44.1 ± 3.0
0.998 ± 0.028
(mg/g)
(1.1)
1.2 ± 0.2
3.13 ± 0.13
438 ± 12
Percent Recovery
100
101
98
99
96
103
99
102
103
—
96
95
L 101
Digestion with 9 mL HN03 and 4 mL HF.
Temperature and pressure conditions as described in Sec. 7.3.6 and similar to
Figure 1.
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TABLE 2.
ANALYSIS OF NIST SRM 2710
(COMPILATION OF REFERENCES 4 AND 9)
NIST SRM 2710 - Montana Soil: Highly Elevated Trace Element Concentrations
Element
Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Zinc
Analyzed Value
(mg/Kg)
39.3 ± 0.9
21.9 ± 0.7
34.0 ± 3.2
2902 ± 83
5425 ± 251
13.5 ± 1.0
36.6 ± 0.5
7007 ± 111
Certified Value
(mg/Kg)
38.4 ± 3.0
21.8 ± 0.2
(39)
2950 ± 130
5532 ± 80
14.3 ± 1.0
35.3 ± 1.5
6952 ± 91
Percent Recovery
102
100
87
98
98
94
104
101
Digestion with either 9 mL HN03 and 4 mL HF or 9 mL HN03, 3 mL HF, and 2 mL
HC1.
Temperature and pressure conditions as described in Sec. 7.3.6 and similar to
Figure 1.
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TABLE 3.
ANALYSIS OF NIST SRM 2711
(COMPILATION OF REFERENCES 4 AND 9)
NIST SRM 2711 - Montana Soil: Moderately Elevated
Trace Element Concentrations
Element
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Zinc
Analyzed Value
(mg/Kg)
40.5 ± 1.0
45.5 ± 1.0
106.8 ± 3.4
1161 ± 49
19.6 ± 0.9
4.3 + 1.0
342 ± 9.4
Certified Value
(mg/Kg)
41.70 ± 0.25
(47)
114 ± 2
1162 ± 31
20.6 ± 1.1
4.63 ± 0.39
350.4 ± 4.8
Percent Recovery
97
97
94
100
95
93
98
Digestion with 9 mL HN03 and 4 mL HF.
Temperature and pressure conditions as described in Sec. 7.3.6 and similar to
Figure 1.
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TABLE 4.
STABLILIZATION AND RECOVERY OF ELEMENTS WITH HC1
(REFERENCE 9)
NIST SRM 2710 - Montana Soil: Highly Elevated Trace Element Concentrations
Element
Antimony
Silver
HN03 & HF
Analyzed Value
(mg/Kg)
33.1 ± 2.1
10.6 ± 4.5
Percent
Recovery
86
30
HN03, HF & HC1
Analyzed Value
(mg/Kg)
39.3 ± 0.9
36.6 ± 0.5
Percent
Recovery
102
104
Certified
Value
(mg/Kg)
38.4 ± 3.0
35.3 ± 1.5
HN03 & HF - Digestion used 9 mL & 3 mL respectively.
HN03, HF, & HC1 - Digestion used 9 mL, 3 mL, & 2 mL respectively.
Temperature and pressure conditions as described in Sec. 7.3.6 and similar to
Figure 1.
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TABLE 5.
FUMING OFF HYDROFLUORIC ACIT WITH MICROWAVE EVAPORATION SYSTEM
(REFERENCE 9)
NIST SRM 2710 - Montana Soil: Highly Elevated Trace Element Concentrations
Element
Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Zinc
Direct
Analyzed Value
(rag/Kg)
39.3 ± 0.9
21.9 ± 0.7
34.0 ± 3.2
2902 ± 83
5425 ± 251
13.5 ± 1.0
36.6 ± 0.5
7007 ± 111
Percent
Recovery
102
100
87
98
98
106
104
101
Fumed
Analyzed Value
(mg/Kg)
39.4 ± 0.9
23.3 ± 1.6
32.4 ± 0.4
2870 ± 150
5502 ± 106
13.5 ± 0.8
38.9 ± 1.1
6992 ± 132
Percent
Recovery
103
107
83
97
99
106
110
101
Certified
Value
(mg/Kg)
38.4 ± 3.0
21.8 ± 0.2
(39)
2950 ± 130
5532 ± 80
14.3 ± 1.0
35.3 ± 1.5
6952 ± 91
Direct - Digestion used 9 mL HN03 and 3 mL HC1 or 9 mL HN03, 3 mL HF, and
2 mL HC1.
Fumed - Digestion used 9 mL HN03 & 3 mL HC1 followed by the removal of the HF.
Temperature and pressure conditions as described in Sec. 7.3.6 and similar to
Figure 1. The digest solution was fumed in a microwave system under vacuum to
-1 mL and 3 mL HC1 added. The digest solution was fumed to ~1 mL and 3 mL
HN03 added. The solution was fumed for a final step to -1 mL and
quantitatively transferred and diluted to final volume.
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TABLE 6.
ANALYSIS OF NIST SRM 1084a
(REFERENCE 9)
NIST SRM 1084a - Wear Metals in Oil (100 ppm)
Element
Chromium
Copper
Lead
Nickel
Silver
Analyzed Value
(mg/Kg)
98.1 ± 1.1
102.4 ± 2.4
99.2 ± 2.3
99.2 ± 2.4
102.7 ± 2.2
Certified Value
(mg/Kg)
98.3 ± 0.8
100.0 ± 1.9
101.1 ± 1.3
99.7 ± 1.6
101.4 ± 1.5
Percent Recovery
100
102
98
99
101
Digestion with 9 mL HN03 & 0.5 mL HF.
Temperature and pressure conditions as described in Sec. 7.3.6 and similar to
Figure 2.
3052 - 20
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January 1995
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METHOD 3052
MICROWAVE ASSISTED ACID DIGESTION OF SILICEOUS
AND ORGANICALLY BASED MATRICES
7.1 Establish
temp, control of
closed microwave
vessel.
7.2 Wash and rinse
digestion vessel.
7.3 Perform sample
digestion.
7.4 Perform
calculations.
7.5 Perform
calibration of
microwave
equipment.
3052 - 21
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METHOD 3060A
ALKALINE DIGESTION FOR HEXAVALENT CHROMIUM
1.0 SCOPE AND APPLICATION
1.1 Method 3060A is an alkaline digestion procedure for extracting
hexavalent chromium [Cr(VI)] from soluble, adsorbed, and precipitated forms of
chromium compounds in soils, sludges, sediments, and some industrial waste
materials. To quantify total Cr(VI) in a solid matrix, three criteria must be
satisfied: (a) the extracting solution must solubilize all forms of Cr(VI), (b)
the conditions of the extraction must not induce reduction of native Cr(VI) to
Cr(III), and (c) the method must not cause oxidation of native Cr(III) contained
in the sample to Cr(VI). Method 3060A meets these criteria for a wide spectrum
of solid matrices. Under the alkaline conditions of the extraction, minimal
reduction of Cr(VI) or oxidation of native Cr(III) occurs. The addition of Mg2+
in a phosphate buffer to the alkaline solution has been shown to suppress
oxidation if observed. The accuracy of the extraction procedure is assessed
using spike recovery data for soluble and insoluble forms of Cr(VI) (e.g.,
K2Cr207 and PbCrOJ, coupled with measurement of ancillary soil properties,
indicative of the potential for the soil to maintain a Cr(VI) spike during
digestion, such as oxidation-reduction potential (ORP), pH, organic matter
content, ferrous iron, and sulfides. Recovery of an insoluble Cr(VI) spike can
be used to assess the first two criteria, and method-induced oxidation is minimal
except in soils high in Mn and amended with soluble Cr(III) salts or freshly
precipitated Cr(OH)3.
1.2 The quantification of Cr(VI) in Method 3060A digests should be
performed using SW-846 Method 7196A (colorimetric) or SW-846 Method 7199 (ion
chromatography).
2.0 SUMMARY OF METHOD
2.1 This method uses an alkaline digestion to solubilize both water-
insoluble and water-soluble Cr(VI) compounds in solid waste samples. The pH of
the digestate must be carefully adjusted during the digestion procedure. Failure
to meet the pH specifications will necessitate redigestion of the samples.
2.2 The sample is digested using 0.28M Na2C0.3/0.5M NaOH solution and
heating at 90-95°C for 60 minutes to dissolve the Cr(VI) and stabilize it against
reduction to Cr(III).
2.3 The Cr(VI) reaction with diphenylcarbazide is the most common method
for analysis of Cr(VI) solubilized in the alkaline digestate. The use of
diphenylcarbazide has been well established in the colorimetric procedure (SW-846
Method 7196A), in rapid-test field kits and in the ion chromatographic method for
Cr(VI) (SW-846 Method 7199). It is highly selective for Cr(VI), and few
interferences are encountered when it is used on alkaline digestates.
3060A-1 Revision 1
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3.0 INTERFERENCES
3.1 When analyzing a sample digest for total Cr(VI), it is appropriate
to determine the reducing/oxidizing tendency of each sample matrix. This can be
accomplished by characterization of each sample for additional analytical
parameters, such as pH (SW-846 Method 9045), ferrous iron (ASTM Method D3872-86),
sulfides (SW-846 Method 9030) and Oxidation Reduction Potential (ORP) (ASTM
Method D 1498-76). Other indirect indicators of reducing/oxidizing tendency
include Total Organic Carbon (TOC), Chemical Oxygen Demand (COD), and Biochemical
Oxygen Demand (BOD). Analysis of these additional parameters establishes the
tendency of Cr(VI) to exist in the unspiked sample(s) and assists in the
interpretation of QC data for matrix spike recoveries outside conventionally
accepted criteria.
3.2 Certain substances, not typically found in the alkaline digests of
soils, may interfere in the analytical methods for Cr(VI) following alkaline
extraction if the concentration of these interferences are high and the Cr(VI)
concentration is low. Refer to SW-846 Methods 7196A and 7199 for a discussion
of the specific agents that interfere with Cr(VI) quantification.
3.3 For waste materials suspected of containing soluble Cr(III)
concentrations greater than four times the laboratory Cr(VI) reporting limit,
Cr(VI) results obtained using Method 3060A may be biased high due to method
induced oxidation. The addition of Mg2+, in a phosphate buffer, to the alkaline
extraction solution has been shown to suppress oxidation and is added (sec. 7.3)
if oxidation is observed or suspected. The presence of soluble Cr(III) can be
approximated by extracting sample with deionized water (ASTM methods D4646-87,
D5233-92 or D3987-85) and analyzing the resultant leachate for both Cr(VI) and
total Cr. The difference between the two values approximates soluble Cr(III).
3.4 One of the most insoluble forms of chromate in alkaline solution,
barium chromate, may require additional heating time to effect complete
dissolution in some soil matrices.
4.0 APPARATUS AND MATERIALS
4.1 Beakers or equivalent: borosilicate glassware, 250-mL, with watch
glass covers or equivalent.
4.2 Graduated Cylinder: 100-mL or equivalent.
4.3 Volumetric Flasks: Class A glassware, 1000-mL and 100-mL with
stoppers or equivalent.
4.4 Filtration Apparatus.
4.5 Filter membranes (0.45 jum). Preferably cellulosic or polycarbonate
membranes.
3060A-2 Revision 1
January 1995
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4.6 Heating Device - capable of maintaining the digestion solution at 90
- 95°C with continuous auto stirring capability or equivalent.
4.7 Volumetric pipettes: Class A glassware, assorted sizes, as
necessary.
4.8 Calibrated pH meter.
4.9 Calibrated balance.
4.10 Thermometer (NIST-Certified or equivalent) or other appropriate
temperature sensing device.
5.0 REAGENTS
5.1 Nitric acid: HN03, concentrated, analytical reagent grade or
spectrograde quality. Store at 20-25'C in the dark. Discard if the solution has
a yellow tinge; this is indicative of photoreduction of N03' to N02.
5.2 Sodium carbonate: Na2C03, anhydrous, analytical reagent grade. Store
at 20-25°C in a tightly sealed container.
5.3 Sodium hydroxide: NaOH, analytical reagent grade. Store at 20-25°C
in tightly sealed container.
5.4 Magnesium Chloride: MgCl2 (anhydrous), analytical reagent grade.
392.18 mg MgCl2 is equivalent to 100 mg Mg2+. Store at 20-25°C in a tightly
sealed container.
5.5 Phosphate Buffer:
5.5.1 K2HP04: analytical reagent grade.
5.5.2 KH2P04: analytical reagent grade.
5.5.3 0.5M K2HP04/0.5M KH2P04 buffer at pH 7: Dissolve 87.09 g
K2HP04 and 68.04 g KH2P04 into 700 ml of distilled deionized water.
Transfer to a 1L volumetric flask and dilute to volume.
5.6 Lead Chromate: PbCr04, analytical reagent grade. The insoluble
matrix spike is prepared by adding 10-20 mg PbCr04 to a separate aliquot. Store
under dry conditions at 20-25°C in a tightly sealed container.
5.7 Digestion solution: Dissolve 20.0 ± 0.05 g NaOH and 30.0 ± 0.05 g
Na2C03 in distilled deionized water in a one-liter volumetric flask and dilute
to the mark. Store the solution in a tightly capped polyethylene bottle at 20-
25"C and prepare fresh monthly. The pH of the digestion solution must be checked
before using. The pH must be 11.5 or greater; if not, discard.
3060A-3 Revision 1
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5.8 Potassium Dichromate, K2Cr207, spiking solution (1000 mg/L Cr (VI):
Dissolve 2.829 g of dried (105°C) K2Cr207 in distilled deionized water in a one-
liter volumetric flask and dilute to the mark. Alternatively, a 1000 mg/L Cr
(VI) certified primary standard solution can be used (Fisher AAS standard or
equivalent). Store at 20-25°C in a tightly sealed container for up to six
months.
5.8.1 Matrix spiking solution (100 mg/L Cr (VI)): Add 10.0 mL of
the 1000 mg/L K2Cr207 spiking solution (Section 5.8) to a 100 mL volumetric
flask and dilute to volume with distilled deionized water. Mix well.
5.9 Sulfuric acid (H2S04), 10% (v/v) (1.8M): Add 10 mL of concentrated
H2S04 to approximately 70 mL of distilled deionized water. Mix well and let
cool. Dilute to a final volume of 100 mL with distilled deionized water.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Samples must have been collected using a sampling plan that addresses
the considerations discussed in Chapter Nine of this manual.
6.2 Samples should be collected using devices and placed in containers
that do not contain stainless steel (e.g., plastic or glass).
6.3 Samples should be stored field-moist at 4 ± 2°C until analysis.
6.4 Hexavalent chromium has been shown (interlaboratory studies) to be
quantitatively stable in field-moist soil samples for at least one month from
sample collection. In addition, Cr (VI) has also been shown (interlaboratory
studies) to be stable in the alkaline digestate for up to 96 hours after
extraction from soil.
7.0 PROCEDURE
7.1 Adjust the temperature setting of each heating device used in the
alkaline digestion by preparing and monitoring a temperature blank (a 250 mL
beaker filled with 50 mLs digestion solution (Section 5.7)). Maintain a solution
temperature of 90 - 95 °C as measured with a NIST-calibrated thermometer or
equivalent.
7.2 Place 2.5 ± 0.10 g of the as received sample into a clean and labeled
250 mL beaker. The sample should be mixed thoroughly before the aliquot is
removed.
7.3 Add 50 mL of digestion solution (Section 5.7) to each sample. Add
392.18 mg of MgCl2 (Section 5.4) and 0.5 mL of 1.0 M phosphate buffer (Section
5.5.3). Cover all samples with watch glasses. The Mg2+ is used to suppress
oxidation of certain forms of Cr(III) (such as soluble forms) that can be
oxidized to Cr(VI) during the procedure.
7.4 Stir the samples continuously (unheated) for at least five minutes
using a stirring bar.
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7.5 Heat the samples and maintain a temperature range of 90 - 95°C with
constant stirring for 60 minutes at temperature.
7.6 Gradually cool each solution to room temperature and transfer it
quantitatively to the filtration apparatus with distilled deionized water rinses
and filter through a 0.45 jum membrane filter. Rinse the inside of the filter
flask and filter pad with distilled deionized water and transfer the filtrate and
the rinses to a clean 250-mL beaker.
NOTE: The remaining sol id after filtration of the matrix spike in
Section 7.6 should be saved for possible use in assessing low Cr(VI)
matrix spike recoveries. See Section 8.5.2. for additional details.
Store the filtered solid at 4 ± 2°C.
7.7 Place a magnetic stirring bar into the sample digest beaker, place
the vessel on a stirrer, and, with constant stirring, slowly add concentrated
nitric acid solution to the beaker dropwise. Adjust the pH of the solution to
7.5 ± 0.5 and monitor the pH with a pH meter. If the pH of the digest should
drop below 7.0, discard the solution and redigest. If overshooting pH 7.5 ± 0.5
occurs repeatedly, prepare a diluted nitric acid solution and repeat digestion
procedure.
CAUTION: C02 will be evolved. This step should be performed in a
fume hood.
7.8 Remove the stirring bar and rinse, collecting the rinsate in the
beaker. Transfer quantitatively the contents of the beaker to a 100 ml
volumetric flask and adjust the sample volume to 100 ml (to the mark for the
volumetric flask) with distilled deionized water. Mix well.
7.9 The sample digestates are now ready to be analyzed. Determine the
Cr(VI) concentration in mg/kg by SW-846 Method 7196A (colorimetrically by UV-Vis
spectrometry) or 7199 (colorimetrically by Ion Chromatography). SW-846 Method
7199 may be preferable for highly colored and/or turbid digests, since organic
acids imparting color to the digest are separated from Cr042" prior to post-column
colorimetric analysis by diphenylcarbazide in SW-846 Method 7199.
7.10 CALCULATIONS
7.10.1 Sample Concentration
„ A x D x E
Cone. =
B x C
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where: A = Concentration observed in the digest
B = Initial moist sample weight (g)
C = % Solids/100
D = Dilution factor
E = Final digest volume (ml)
7.10.2 Relative Percent Difference
RPD = (S ~ D) x 100
where: S = Initial sample result
D = Duplicate sample result
7.10.3 Spike Recovery
PERCENT RECOVERY = (55J? " SK) x 100
SA
where: SSR = Spike sample result
SR = Sample (unspiked) result
SA = Spike added
8.0 QUALITY CONTROL
8.1 The following Quality Control (QC) analyses must be performed per
digestion batch as discussed in Chapter One.
8.2 A preparation blank must be prepared and analyzed with each digestion
batch, as discussed in Chapter One, and detected Cr(VI) concentrations must be
less than the method detection limit or one-tenth the concentration of the lowest
sample, whichever is greater or the entire batch must be redigested.
8.3 Laboratory Control Sample (LCS): As an additional determination of
method performance, utilize the matrix spike solution prepared in Section 5.8.1
or the solid matrix spike agent, PbCr04 (Section 5.6) to spike into 50 mL of
digestion solution (Section 5.7). Alternatively, the use of a certified solid
reference material (if available) is recommended. Recovery must be within the
3060A-6 Revision 1
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certified acceptance range or a recovery range of 80 to 120% or the sample batch
must be reanalyzed.
8.4 A separately prepared duplicate soil sample must be analyzed at a
frequency of one per batch as discussed in Chapter One. Duplicate samples must
have a Relative Percent Difference (RPD) of < 20%, if both the original and the
duplicate are > four times the laboratory reporting limit. A control limit of
± the laboratory reporting limit is used when either the original or the
duplicate sample is < four times the laboratory reporting limit.
8.5 Both soluble and insoluble pre-digestion matrix spikes must be
analyzed at a frequency of one per batch of < 20 field samples. The soluble
matrix spike should be spiked with 1.0 ml of the spiking solution prepared in
Section 5.8.1 (equivalent to 40 mg/kg Cr(VI)) or at twice the sample
concentration, whichever is greater. The insoluble matrix spike is prepared by
adding 10-20 mg of PbCr04 (Section 5.6) to a separate sample aliquot. It is used
to evaluate the dissolution during the digestion process. Both matrix spikes are
then carried through the digestion process contained in Section 7.0. More
frequent matrix spikes must be analyzed if the soil characteristics within the
analytical batch appear to have significant variability based on visual
observation. An acceptance range for matrix spike recoveries is 75 - 125%. If
the matrix spike recoveries are not within these recovery limits, the entire
batch must be redigested/reanalyzed. If upon reanalysis the matrix spike is not
within the recovery limits, but the LCS is within criteria specified in Section
8.3, information such as that specified on Figure 1 and in Section 3.1 should be
carefully evaluated, as the Cr(VI) data may be valid for use despite the
perceived "QC failure." The information on Figure 1 and discussed below is
provided to interpret ancillary parameter data in conjunction with data on spike
recoveries:
8.5.1 When pre-digestion matrix spike recoveries for Cr(VI) are less
than acceptance range minimum criterion (75%), this is indicative of
highly reducing samples (e.g., anoxic sediments) with no measurable native
Cr(VI) in the unspiked sample (assuming the criteria in Section 8.3 are
met). Such a result indicates that the combined and interacting
influences of ORP, pH and reducing agents (e.g., organic acids, Fe2+ and
sulfides) caused reduction of Cr(VI) spikes.
Oxidation-reduction potentials below the bold diagonal line on
Fig. 2 indicates a reducing soil for Cr(VI). The downward slope to the
right indicates that the Eh value, at which Cr(VI) is expected to be
reduced, decreases with increasing pH. The solubility and quantity of
organic constituents will influence reduction of Cr(VI). The presence of
H2S or other strong odors indicate a reducing environment for Cr(VI). In
general, acidic conditions accelerate reduction of Cr(VI) in soils, and
alkaline conditions tend to stabilize Cr(VI) against reduction. If spike
recoveries are not within the recovery limits, the reductive nature of the
sample must be documented.
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8.5.2 If a low or zero percent pre-digestion matrix spike recovery
is obtained, an alternate approach can be used to determine the potential
contribution of the sample matrix to Cr(VI) reduction. This approach
consists of performing a mass balance, whereby total chromium is analyzed
(Method 3050) for two samples: (1) a separate unspiked aliquot of the
sample previously used for spiking, and (2) the digested solids remaining
after the alkaline digestion and filtration of the matrix spike (i.e., the
filtered solids from the matrix spike in Section 7.6).
The difference between the total chromium measurements should be
approximately equal to the amount of the spike added to the matrix spike.
If the LCS (Section 8.3) met the acceptance criteria and the Cr(VI) spike
is accounted for in the filtered solids as total chromium, it is likely
that the reduction of the Cr(VI) to insoluble Cr(III) resulted from the
reducing matrix of the original sample subjected to Cr(VI) spiking.
8.6 A post-digestion Cr(VI) matrix spike must be analyzed per batch as
discussed in Chapter One. The post-digestion matrix spike concentration should
be equivalent to 40 mg/kg or twice the sample concentration observed in the
unspiked aliquot of the test sample, whichever is greater.
8.6.1 Dilute the sample aliquot to a minimum extent, if necessary,
so that the absorbance reading for both the unspiked sample aliquot and
spiked aliquot are within the initial calibration curve.
8.6.2 A guideline for the post-digestion matrix spike recovery is
85-115% recovery. If not achieved, consider the corrective
actions/guidance on data use specified in Section 8.5. These digestates
may contain soluble reducing agents for Cr(VI), such as fulvic acids.
9.0 METHOD PERFORMANCE
9.1 A commercial laboratory analyzed soil/sediment samples containing
Cr(VI) with the following results:
Mean native Mean Cr(VI) Matrix
2" Cr(VI) Cone. Spike Cone. Spike Rec.
(mq/kq) Range
Sample
Type
COPR"
Soil Blends
Loam
Clay
COPR8
Eh (mV)b
500
640
740
510
£H
7.2
6.3
2.9
8.6
s
(ppm)c
.0
.0
.0
.0
(mq/kq)
4.1
ND
ND
759
42.0
62.5
63.1
813
89.8% -
116%
65.0% -
70.3%
37.8% -
71.1%
85.5% -
94.8%
3060A-8
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Sample
Type Eh (mV)b
Anoxic Sediment 330
s2-
{>H (ppm)°
6.3 25.0
Mean native
Cr(VI) Cone.
(mq/kq)
ND
Mean Cr(VI) Matrix
Spike Cone. Spike Rec.
(mq/kq) Range
381
0%
Quartz Sand
640
5.4 <10.0
ND
9.8
75.5% -
86.3%
Note:
a
ND
b
c
COPR - Chromite ore processing residue
Not detected
Corrected for the reference electrode
Field measurement
10.0 REFERENCES
10.1 United States Environmental Protection Agency, 1982. Test Methods
for Evaluating Solid Wastes, Physical/Chemical Methods. SW-846, Second Edition.
Office of Solid Waste and Emergency Response, Washington, D.C.
10.2 New Jersey Department of Environmental Protection and Energy
(NJDEPE). NJDEPE Modified Methods 3060/7196A. 1992.
10.3 R. Vitale, G. Mussoline, J. Petura, B. James, 1993. A Method
Evaluation Study of an Alkaline Digestion (Modified Method 3060) Followed by
Colorimetric Determination (Method 7196A) for the Analysis for Hexavalent
Chromium in Solid Matrices. Environmental Standards, Inc. Valley Forge, PA
19482.
10.4 Zatka, V.J., 1985. Speciation of Hexavalent Chromium in Welding
Fumes Interference by Air Oxidation of Chromium. J. Ray Gordon Research
Laboratory, INCO Limited, Sheridan Park, Mississauga, Ontario L5K 1Z9, Am. Ind.
Hyg. Assoc. J., 46(6):327-331.
10.5 U.S. EPA (United States Environmental Protection Agency), 1982. Test
Methods for Evaluating Solid Wastes, Physical/Chemical Methods. SW-846, Second
Edition. Office of Solid Waste and Emergency Response, Washington, D.C.
10.6 ASTM (American Society for Testing and Materials), 1981. Standard
Practice for Oxidation Reduction Potential of Water. ASTM Designation: D1498-76.
10.7 Vitale, R.J., Mussoline, G.R., Petura, J.C. and James, B.R. 1994.
Hexavalent Chromium Extraction from Soils: Evaluation of an Alkaline Digestion
Method. J. Environ. Qua!. 23: 1249-1256 In Press.
3060A-9
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FIGURE 1
QUALITY CONTROL FLOW CHART
Field Collection
of Sample*
Field Homogenlzatlon
of Sample*
I
Field Characterization of
Samplea for OR* and pH
Olgeetlon of Field Samplea
+ QC Samplea
Optionally, characterize
•ample for OK*. Fa2*
pH and SulfMee to
detennlne if aample
exhibit* reducing condition.
Additional parameter*
to characterize aample
include TOC. BOO. and
COD If reducing conditions
are auapected.
Sample Analyal*
(7198A or 7199)
No
Waa LCS
ithin 80-120
recovery or within
the certified
acceptance
range?
We* CrIVII
Matrix Spike
Sample within
76-126*
recovery?
Waa
concentration o
epike added greater
than four time*
indigene ue
level of
r(VD?
Report aample
reoult* without
qualification.
Report aampl* reault*.
Concentration of the
matrix apike added wee
inelgnlflcant with
reepect to idlgenoue
level of Cr(VI).
Alternately redlgeet
uaing higher matrix
aplka level.
Yea
Wee
Matrix Spike
Recovery
>126tt?
Waa
Matrix Spike
Recovery
<76%?
Characterize aample for
ORP. FE *? pH and aulfMee
to determine if aample
exhlbtta reducing condition.
Additional parameter* to
characterize aampl*
include TOC. BOO. and
COO if reducing condltlone
are auapected.
3060A-10
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FIGURE 1
QUALITY CONTROL FLOW CHART (Continued)
Doas
sample contain
suJfides (rotten egg
odor or
measurable Si')?
Report value and indicate
sample exhibits highly
reducing condition.
Report value and indicate
sample exhibit* highly
reducing condition.
I No
Plot Eh vs. pH of sample
on Figure 2.
Does
the point fall
below line A
on Figure 2?
Report value and indicate
sample exhibits reducing
condition.
Report sample results as
qualified due to low matrix
spike recovery
OR
Redigest and reanalyze
samples and QC to confirm
matrix effect.
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FIGURE 2
Eh/pH Phase Diagram
The dashed lines define Eh-pH boundaries commonly encountered In soils and sediments.
2000
>
£
-C
LJ
1600 —
1200
800 —
400
0 I—
-400 —
A: HCr04~/Cr(OH)3
oxidizing |
J
-800
PH
Note the Eh values plotted on this diagram are corrected for the reference electrode voltage:
244 mV units must be added to the measured value when a separate calomel electrode is used, or
199 mV units must be added if a combination platinum electrode is used.
10
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METHOD 3060
ALKALINE DIGESTION FOR HEXAVALENT CHROMIUM
f Start j
^
r
7.1 Equilibrate heating device
temperature to 90-96° C.
7.2 Weigh 2.5 +/•
0.1 Og cample.
7.3 - 7.4 Add reagente,
stir for 5 minute*.
7.5 Heat sample at
90 - 95°C for 90 mmutee.
7.6 Cool, filter digestate
through 0.46 um filter.
7.7 While atimng, adjust filtrate
to pH 7.5 +/- 0.6 by dropwise
addition of HNO3 .
7.8 Bring to final volume.
Analyze sample by
SW-846 Methods 7196A
or 7199.
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3.3 METHODS FOR DETERMINATION OF INORGANIC ANALYTES
This section of the manual contains seven analytical techniques for
trace inorganic analyte determinations: inductively coupled argon plasma atomic
emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry
(ICP-MS), direct-aspiration or flame atomic absorption spectrometry (FLAA),
graphite-furnace atomic absorption spectrometry (GFAA), hydride-generation atomic
absorption spectrometry (HGAA), cold-vapor atomic absorption spectrometry (CVAA),
and several procedures for hexavalent chromium analysis. Each of these is
briefly discussed below in terms of advantages, disadvantages, and cautions for
analysis of wastes.
ICP's primary advantage is that it allows simultaneous or rapid
sequential determination of many elements in a short time. The primary
disadvantage of ICP is background radiation from other elements and the plasma
gases. Although all ICP instruments utilize high-resolution optics and back-
ground correction to minimize these interferences, analysis for traces of
inorganic analytes in the presence of a large excess of a single analyte is
difficult. Examples would be traces of inorganic analytes in an alloy or traces
of metals in a limed (high calcium) waste. ICP and Flame AA have comparable
detection limits (within a factor of 4) except that ICP exhibits greater
sensitivity for refractories (Al, Ba, etc.). Furnace AA, in general, will
exhibit lower detection limits than either ICP or FLAA. Detection limits are
drastically improved when ICP-MS is used. In general ICP-MS exhibits greater
sensitivity than either GFAA or FLAA for most elements. The greatest
disadvantage of ICP-MS is isobaric elemental interferences. These are caused by
different elements forming atomic ions with the same nominal mass-to-charge
ratio. Mathematical correction for interfering ions can minimize these
interferences.
Flame AAS (FLAA) direct aspiration determinations, as opposed to ICP,
are normally completed as single element analyses and are relatively free of
interelement spectral interferences. Either a nitrous-oxide/acetylene or
air/acetylene flame is used as an energy source for dissociating the aspirated
sample into the free atomic state, making analyte atoms available for absorption
of light. In the analysis of some elements, the temperature or type of flame
used is critical. If the proper flame and analytical conditions are not used,
chemical and ionization interferences can occur.
Graphite Furnace AAS (GFAA) replaces the flame with an electrically
heated graphite furnace. The furnace allows for gradual heating of the sample
aliquot in several stages. Thus, the processes of dissolution, drying,
decomposition of organic and inorganic molecules and salts, and formation of
atoms which must occur in a flame or ICP in a few milliseconds may be allowed to
occur over a much longer time period and at controlled temperatures in the
furnace. This allows an experienced analyst to remove unwanted matrix components
by using temperature programming and/or matrix modifiers. The major advantage
of this technique is that it affords extremely low detection limits. It is the
easiest to perform on relatively clean samples. Because this technique is so
THREE - 8 Revision 3
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sensitive, interferences can be a real problem; finding the optimum combination
of digestion, heating times and temperatures, and matrix modifiers can be a
challenge for complex matrices.
Hydride AA utilizes a chemical reduction to reduce and separate arsenic
or selenium selectively from a sample digestate. The technique therefore has the
advantage of being able to isolate these two elements from complex samples which
may cause interferences for other analytical procedures. Significant
interferences have been reported when any of the following is present: 1) easily
reduced metals (Cu, Ag, Hg); 2) high concentrations of transition metals (>200
mg/L); 3) oxidizing agents (oxides of nitrogen) remaining following sample
digestion.
Cold-Vapor AA uses a chemical reduction to reduce mercury selectively.
The procedure is extremely sensitive but is subject to interferences from some
volatile organics, chlorine, and sulfur compounds.
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METHOD 0060
DETERMINATION OF METALS IN STACK EMISSIONS
1.0 SCOPE AND APPLICATION
1.1 This method is used to determine the concentration of metals in stack
emissions from hazardous waste incinerators and similar combustion processes.
Using the detection limits shown, the following parameters can be determined by
this method:
TABLE 1. ESTIMATED IDLS FOR METALS DETERMINED BY METHOD 0060
Analyte
Antimony (Sb)
Arsenic (As)
Barium (Ba)
Beryllium (Be)
Cadmium (Cd)
Total chromium (Cr)
Copper (Cu)
Lead (Pb)
Manganese (Mn)
Mercury (Hg)
Nickel (Ni)
Phosphorus (P)
Selenium (Se)
Silver (Ag)
Thallium (Tl)
Zinc (Zn)
ICP-AES3
/vg/L
40e
60
2
0.3
4
7
6
50
2
20
60
80
7
40
2
Flame AASb
A/g/L
200e
2f
100
5
5
50
20
100
10
40
2f
10
100
5
GFAASC
/vg/L
3e
1
0.2
0.1
1
1
2
1
CVAASd
W/L
0.2
a Estimated IDLs by ICP-AES, Method 6010.
b Estimated IDLs by direct aspiration Flame AAS, Method 7000.
c Estimated IDLs by Graphite Furnace AAS, Method 7000.
d Estimated IDL by Cold Vapor AAS, Method 7470.
e Detection limit for Sb may be higher depending on digestion used.
f Estimated IDLs for As & Se by Hydride AAS, Method 7000.
1.2 This method may also be used for the determination of particulate
emissions following the additional procedures described in Section 7.1.5.2.
Modifications to the sample recovery and analysis procedures described in the
particulate emissions protocol may potentially impact the front-half mercury
determination. Field tests to date have shown that of the total amount of
mercury measured by the method, only 0 to <2% was measured in the front half.
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Therefore, it is tentatively concluded, based on the above data, that particulate
emissions may be measured by this train, without significantly altering the
mercury results.
1.3 For the analyses described in this methodology and for similar
analyses, the response for Inductively Coupled Plasma Atomic Emission
Spectroscopy (ICP-AES) is linear over several orders of magnitude. Samples
containing metal concentrations in the micrograms per milliliter (/yg/L) to
milligrams per liter (mg/L) range in the analytical finish solution can be
analyzed using this technique. Samples containing greater than approximately 50
mg/L of chromium, lead, or arsenic should be diluted to that level or lower for
final analysis. Samples containing greater than approximately 20 mg/L of cadmium
should be diluted to that level before analysis.
1.4 The actual method detection limits are sample dependent and may vary
as the sample matrix affects the limits. Method detection limits for antimony
can also be dependent on the digestion method used and may be considerably higher
than the estimated detection limits. Method detection limits for all analytes
may differ from the estimated detection limits when hydrofluoric acid digestion
is used. For more information on MDLs, refer to Chapter One.
1.5 The complexity of this methodology is such that to obtain reliable
results, the testers (including analysts) should be experienced and knowledgeable
in source sampling, in handling and preparing (including mixing) reagents as
discussed, and in using adequate safety procedures and protective equipment.
2.0 SUMMARY
2.1 The stack sample is withdrawn isokinetically from the source.
Particulate emissions are collected in the probe and on a heated filter and
gaseous emissions are collected in a series of chilled impingers. Two impingers
are empty, two impingers contain an aqueous solution of dilute nitric acid
combined with dilute hydrogen peroxide, two (or one) other impingers contain
acidic potassium permanganate solution, and the last impinger contains a
desiccant.
2.2 Sampling train components are recovered and digested in separate
front-half and back-half fractions. Materials collected in the sampling train
are acid digested to dissolve inorganics and to remove organic constituents that
may create analytical interferences. Acid digestion is performed by using
prescribed SW-846 digestion techniques.
2.3 The nitric acid and hydrogen peroxide impinger solution, the
hydrochloric acid rinse solution, the acidic potassium permanganate impinger
solution, and the probe rinse and digested filter solutions are analyzed for
mercury by Cold Vapor Atomic Absorption Spectroscopy (CVAAS). All of the
sampling train catches except for the permanganate solution are analyzed for Cr,
Cd, Ni, Mn, Be, Cu, Zn, Pb, Se, P, Ti, Ag, Sb, Ba, and As by ICP-AES or Atomic
Absorption Spectroscopy (AAS). If antimony, arsenic, cadmium, lead, selenium,
and thallium require greater analytical sensitivity than can be obtained by ICP-
AES, then Graphite Furnace Atomic Absorption Spectroscopy (GFAAS) is used for the
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analysis. Additionally, if desired, the tester may use AAS for analyses of all
metals if the resulting in-stack method detection limits meet the goal of the
testing program.
2.4 For convenience, aliquots of each digested sample Fraction 1A plus
Fraction 2A can be combined for a single analytical determination, proportionally
with respect to the original Fractions 1A and 2A. Fraction 1A is normally
diluted to 300 ml following digestion prior to analysis and the concentrated
Fraction 2A is normally diluted to 150 ml following digestion and prior to
analysis.
2.5 The efficiency of the analytical procedure is quantified by the
analysis of spiked quality control samples containing each of the target metals
and/or other quality assurance measures including actual sample matrix effects
checks.
3.0 INTERFERENCES
3.1 Refer to the appropriate determinative method for instructions on
minimization of interferences.
4.0 APPARATUS AND MATERIALS
4.1 Sampling train - A schematic of the sampling train is shown in Figure
A-l. It is similar to the EPA Method 5 train. The sampling train consists of
the following components.
4.1.1 Probe nozzle (probe tip) and borosilicate or quartz
glass probe liner - Same as Method 5, Sections 2.1.1 and 2.1.2, except
that glass nozzles are required unless an alternate probe tip prevents the
possibility of contamination or interference of the sample with its
materials of construction. If a probe tip other than glass is used, no
correction of the stack sample test results can be made because of the
effect on the results by the probe tip.
4.1.2 Pitot tube and differential pressure gauge - Same as
Method 2, Sections 2.1 and 2.2, respectively.
4.1.3 Filters - Quartz fiber or glass fiber filters without
organic binders shall be used. The filters shall contain less than 1.3
ug/in.2 of each of the metals to be measured. Analytical results provided
by filter manufacturers are acceptable. However, if no such results are
available, filter blanks must be analyzed for each target metal prior to
emission testing. The filters should exhibit at least 99.95 percent
efficiency (<0.05 percent penetration) on 0.3 micron dioctyl phthalate
smoke particles. The filter efficiency test shall be conducted in
accordance with ASTM Standard Method D2986-71 (incorporated by reference).
For particulate determination in sources containing S02 or S03, the filter
material must be of a type that is unreactive to S02 or S03, as described
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8
I
JS
to
o
g
w
1
0060 - 4
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in Method 5. Quartz fiber filters that meet these requirements are
recommended.
4.1.4 Filter holder - Glass, same as Method 5, Section 2.1.5,
except that a Teflon filter support or other non-metallic, non-
contaminating support must be used to replace the glass frit.
4.1.5 Filter heating system - Same as Method 5, Section 2.1.6.
4.1.6 Condenser
4.1.6.1 The following system shall be used for the
condensation and collection of gaseous metals and for determining
the moisture content of the stack gas. The condensing system should
consist of three to seven impingers connected in series with leak-
free ground glass fittings or other leak-free, non-contaminating
fittings. The first impinger is optional and is recommended as a
moisture knockout trap for use during test conditions which require
such a trap. The first impinger shall be empty. The second and
third impingers shall contain known quantities of a nitric
acid/hydrogen peroxide solution (Section 5.8). The fourth shall be
empty. The fifth and sixth impingers shall contain a known quantity
of acidic potassium permanganate solution (Section 5.12), and the
last impinger shall contain a known quantity of silica gel or
equivalent desiccant. A thermometer capable of measuring to within
1°C (2°F) shall be placed at the outlet of the last impinger.
4.1.6.2 The first impinger shall be appropriately sized for
a potentially large moisture catch and constructed generally as
described for the first impinger in Method 5, Section 2.1.7. The
second impinger (or the first HN03/H202 impinger) shall also be as
described for the first impinger in Method 5. The third impinger
(or, in any case, the impinger used as the second HN03/H202 impinger)
shall be the same as the Greenburg-Smith impinger with the standard
tip described as the second impinger in Method 5, Section 2.1.7.
All other impingers used in the metals train are the same as the
first HN03/H202 impinger.
4.1.6.3 When the moisture knockout impinger is not needed, it
is removed from the train and the other impingers remain the same.
If mercury analysis is not to be performed, the potassium
permanganate impingers and the empty impinger preceding them are
removed.
4.1.7 Metering system, barometer, and gas density
determination equipment - Same as Method 5, Sections 2.1.8 through 2.1.10,
respectively.
4.1.8 Teflon tape - For capping openings and sealing
connections, if necessary, on the sampling train.
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4.2 Sample recovery. Same as Method 5, Sections 2.2.1 through 2.2.8,
with the following exceptions and additions:
4.2.1 Non-metallic probe-liner and probe-nozzle brushes or
swabs - For quantitative recovery of materials collected in the front half
of the sampling train. Description of acceptable all-Teflon component
brushes or swabs to be included in EPA's Emission Measurement Technical
Information Center (EMTIC) files.
4.2.2 Sample storage containers - Glass bottles, 1000 mL and
500 mL, with Teflon-lined caps which are non-reactive to oxidizing
solutions, shall be used for samples and blanks containing KMn04.
Polyethylene bottles may be used for other sample types.
4.2.3 Polypropylene tweezers and/or plastic gloves - For
recovery of the filter from the sampling train filter holder.
4.3 Sample preparation and analysis equipment.
4.3.1 Refer to the appropriate preparation and analytical
techniques for the proper apparatus and materials. Refer to Section 7.2
for a description of preparation techniques.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents conform to the specifications
established by the Committee on Analytical Reagents of the American Chemical
Society, where such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
5.2 Reagent Water. Refer to Chapter One for a definition of reagent
water. Analyze the water for all target metals prior to field use. All target
metals should be less than the MDL.
5.3 Nitric acid, concentrated - Baker Instra-analyzed or equivalent.
5.4 Nitric acid (0.1 M) - Add, with stirring, 6.3 mL of concentrated HN03
to a flask containing approximately 900 mL of water. Dilute to 1000 mL with
water. Mix well. The reagent shall contain less than 2 jjg/l of each target
metal.
5.5 Nitric acid, 10 percent (V/V). Add, with stirring, 500 mL of
concentrated HN03 to a flask containing approximately 4000 mL of water. Dilute
to 5000 mL with water. Mix well. Reagent shall contain less than 2 /vg/L of each
target metal.
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5.6 Nitric acid, 5 percent (V/V). Add, with stirring, 50 ml of
concentrated HN03 to 800 ml of water. Dilute to a 1000 ml with water. Reagent
shall contain less than 2 //g/L of each target metal.
5.7 Nitric acid, 50 percent (V/V). Add, with stirring, 125 ml of
concentrated HN03 to a flask containing approximately 100 ml of water. Dilute
to 250 mL with water. Mix well. Reagent shall contain less than 2/yg/L of each
target metal.
5.8 Nitric acid (HN03)/hydrogen peroxide (H202) absorbing solution, 5
percent HN03/10 percent H202 Add carefully, with stirring, 50 ml of concentrated
HN03 to a 1000-mL volumetric flask containing 500 mL of water. Carefully add 333
mL of 30% H202 to the flask. Dilute to volume with water. The reagent shall
contain less than 2/yg/L of each target metal.
5.9 Hydrochloric acid (8M), HC1 - Carefully add with stirring 690 mL of
concentrated HC1 to a flask containing 250 mL of water. Dilute to 1000 mL with
water. Mix well. The reagent shall contain less than/yg/L of Hg.
5.10 Hydrogen peroxide, 30 percent (V/V).
5.11 Potassium permanganate, 5 percent (W/V).
5.12 Acidic potassium permanganate (KMn04) absorbing solution, 4 percent
KMn04 (W/V), 10 percent H2S04 (V/V) - Prepare fresh daily. Carefully mix 100 mL
of concentrated H2S04 into 800 mL of water. Add water, with stirring, to make
a volume of 1000 mL. This solution is 10% H2S04 (V/V). Dissolve, with stirring,
40 g of KMn04 into sufficient 10% H2S04 to make a volume of 1 liter. Prepare and
store in glass bottles to prevent degradation. The reagent shall contain less
than 2 //g/L of Hg.
CAUTION: To prevent autocatalytic decomposition of the permanganate
solution, filter the solution through Whatman 541 filter paper.
Also, due to reaction of the potassium permanganate with the acid,
there may be pressure buildup in the sample storage bottle; these
bottles should not be fully filled and should be vented both to
relieve excess pressure and prevent explosion due to pressure
buildup. Venting is highly recommended, but should not allow
contamination of the solution; a No. 70-72 hole drilled in the
container cap and Teflon liner is suggested.
5.13 Sulfuric acid, concentrated.
5.14 Silica gel and crushed ice - Same as EPA Method 5, Sections 3.1.2 and
3.1.4, respectively.
5.15 Hydrofluoric acid, concentrated.
5.16 Refer to the appropriate preparation and analytical technique for
reagent and standard preparation procedures.
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6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Sampling. The complexity of this method is such that, to obtain
reliable results, testers should be trained and experienced with the test
procedures.
6.1.1 Pretest preparation. Follow the same general procedure
given in Method 5, Section 4.1.1, except that, unless particulate
emissions are to be determined, the filter need not be desiccated or
weighed. All sampling train glassware should first be rinsed with hot tap
water and then washed in hot soapy water. Next, glassware should be
rinsed three times with tap water, followed by three additional rinses
with reagent water. All glassware should then be soaked in a 10% (V/V)
nitric acid solution for a minimum of 4 hours, rinsed three times with
reagent water, rinsed a final time with acetone, and allowed to air dry.
All glassware openings where contamination can occur should be covered
until the sampling train is assembled, prior to sampling.
6.1.2 Sampling train calibration. Maintain a laboratory log
of all calibrations. Calibrate the sampling train components according to
the indicated sections of Method 5: probe nozzle (Section 5.1); pitot
tube (Section 5.2); metering system (Section 5.3); probe heater (Section
5.4); temperature gauges (Section 5.5); leak-check of the metering system
(Section 5.6); and barometer (Section 5.7).
6.1.3 Preliminary determinations. Same as Method 5, Section
4.1.2.
6.1.4 Preparation of Sampling Train.
6.1.4.1 Follow the same general procedures given in Method 5,
Section 4.1.3, except place 100 mL of the nitric acid/hydrogen
peroxide solution (Section 5.8) in each of the two HN03/H202
impingers (normally the second and third impingers) as shown in
Figure A-l. Place 100 mL of the acidic potassium permanganate
absorbing solution (Section 5.12) in each of the two permanganate
impingers. Transfer approximately 200 to 300 g of preweighed silica
gel from its container to the last impinger. Alternatively, the
silica gel may be weighed directly in the impinger just prior to
train assembly.
6.1.4.2 Several options are available to the tester based on
the sampling conditions. The empty first impinger is not needed if
the moisture to be collected in the impingers is calculated or
determined to be less than 100 mL. If necessary, use as applicable
to this methodology the procedure described in Section 7.1.1 of EPA
Method 101A, 40 CFR Part 61, Appendix B, to maintain the desired
color in the last permanganate impinger.
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6.1.4.3 Retain for reagent blanks, volumes of the nitric
acid/hydrogen peroxide solution and 100 ml of the acidic potassium
permanganate solution. These reagent blanks should be labeled and
analyzed as described in Section 7. Set up the sampling train as
shown in Figure A-l. If necessary to ensure leak-free sampling
train connections, Teflon tape or other non-contaminating material
should be used instead of silicone grease to prevent contamination.
CAUTION: Extreme care should be taken to prevent contamination
within the train. Prevent the mercury collection reagent (acidic
potassium permanganate) from contacting any glassware of the train
which is washed and analyzed for manganese. Prevent hydrogen
peroxide from mixing with the acidic potassium permanganate.
6.1.4.4 Alternatively, mercury emissions can be measured in
a separate train which measures only mercury emissions by using EPA
Method 101A with the modifications described below (and with the
further modification that the permanganate containers shall be
processed as described in the Section 5.12 caution comment. This
alternative method is applicable for measurement of mercury and
manganese emissions, and it may be of special interest to sources
which must measure both mercury and manganese emissions. [Section
7.2.1 of Method 101A shall be modified as follows after the 250 to
400-mL KMn04 rinse: To remove any precipitated material and any
residual brown deposits on the glassware following the permanganate
rinse, rinse with approximately 100 ml of the reagent water.
Carefully add this water rinse, assuring transfer of all loose
precipitated materials from the three permanganate impingers into
the permanganate Container No. 1. If no visible deposits remain
after this water rinse, do not rinse with HC1. However, if deposits
do remain on the glassware after this water rinse, wash the impinger
surfaces with 25 ml of 8M HC1, and place the wash in a separate
sample container labeled Container No. 1A containing 200 ml of
water. Wash the impinger walls and stem with the HC'I by turning the
impinger on its side and rotating it so that the HC1 contacts all
inside surfaces. Use a total of only 25 ml of 8M HC1 for rinsing
all permanganate impingers combined. Rinse the first impinger, then
pour the actual rinse used for the first impinger into the 25 mL of
8M HC1 rinse carefully with stirring into Container No. 1A. Analyze
the HC1 rinse separately by carefully diluting, with stirring, the
contents of Container No. 1A to 500 ml with reagent water. Filter
(if necessary) through Whatman 40 filter paper, and then analyze for
mercury according to Section 7.4.7, except limit the aliquot size to
a maximum of 10 ml. Prepare and analyze a blank by using the same
procedure as that used by Container No. 1A, except add 5 ml of 8M
HC1 with stirring to 40 mL of water, then dilute to 100 ml with
reagent water. Then analyze the blank as instructed for the sample
from Container No. 1A. Because the previous separate permanganate
solution rinse (Section 7.1.5.5) and water rinse (as modified in
these guidelines) have the capability to recover a very high
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percentage of the mercury from the permanganate impingers, the
amount of mercury in the HC1 rinse in Container No. 1A may be very
small, possibly even insignificantly small. However, add the total
of any mercury analyzed and calculated for the HC1 rinse sample
Container No. 1A to that calculated from the mercury sample from
(Section 7.1.5.5) which contains the separate permanganate rinse
(and water rinse as modified herein) for calculation of the total
sample mercury concentration.]
6.1.5 Leak-check procedures. Follow the leak-check procedures
given in Method 5, Section 4.1.4.1 (Pretest Leak-Check), Section 4.1.4.2
(Leak-Checks During the Sample Run), and Section 4.1.4.3 (Post-Test Leak-
Checks).
6.1.6 Sampling train operation. Follow the procedures given
in Method 5, Section 4.1.5. For each run, record the data required on a
data sheet such as the one shown in Figure 5-2 of Method 5.
6.1.7 Calculation of percent isokinetic. Same as Method 5,
Section 4.1.6.
7.0 PROCEDURE
7.1 Sample recovery. Begin cleanup procedures as soon as the probe is
removed from the stack at the end of a sampling period.
7.1.1 The probe should be allowed to cool prior to sample
recovery. When it can be safely handled, wipe off all external
particulate matter near the tip of the probe nozzle and place a rinsed,
non-contaminating cap over the probe nozzle to prevent losing or gaining
particulate matter. Do not cap the probe tip tightly while the sampling
train is cooling. This normally causes a vacuum to form in the filter
holder, thus causing the undesired result of drawing liquid from the
impingers into the filter.
7.1.2 Before moving the sampling train to the cleanup site,
remove the umbilical cord from the last impinger and cap the impinger.
Cap off the filter holder outlet and impinger inlet. Use non-
contaminating caps, whether ground-glass stoppers, plastic caps, serum
caps, or Teflon tape to close these openings.
7.1.3 Alternatively, the train can be disassembled before the
probe and filter holder/oven are completely cooled, if this procedure is
followed: Initially disconnect the filter holder outlet/impinger inlet
and loosely cap the open ends. Then disconnect the probe from the filter
holder or cyclone inlet and loosely cap the open ends. Cap the probe tip
and remove the umbilical cord as previously described.
7.1.4 Transfer the probe and filter-impinger assembly to a
cleanup area that is clean and protected from the wind and other potential
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causes of contamination or loss of sample. Inspect the train before and
during disassembly and note any abnormal conditions.
7.1.5 The sample is recovered and treated as follows (see
schematic in Figure A-2). Assure that all items necessary for recovery of
the sample do not contaminate it.
7.1.5.1 Container No. 1 (filter). Carefully remove the filter
from the filter holder and place it in its identified petri dish
container. Acid-washed polypropylene or Teflon coated tweezers or
clean disposable surgical gloves rinsed with water should be used to
handle the filters. If it is necessary to fold the filter, make
certain the particulate cake is inside the fold. Carefully transfer
the filter and any particulate matter or filter fibers that adhere
to the filter holder gasket to the petri dish by using a dry (acid-
cleaned) nylon bristle brush. Do not use any metal-containing
materials when recovering this train. Seal the labeled petri dish.
NOTE: Follow the procedure in Section 7.1.5.2 only if
determination of particulate emissions are desired in
addition to metals emissions. If only metals emissions
are to be determined, skip Section 7.1.5.2 and go to
Section 7.1.5.3.
7.1.5.2 Container No. 2 (acetone rinse).
7.1.5.2.1 Taking care to see that dust on the outside
of the probe or other exterior surfaces does not get into the
sample, quantitatively recover particulate matter and any
condensate from the probe nozzle, probe fitting (fittings made
of plastic such as Teflon, polypropylene, etc. are recommended
to prevent contamination by metal fittings. Further, if
desired a single glass piece may be used, but it is not a
requirement of this methodology), probe liner, and front half
of the filter holder by washing these components with 100 ml
of acetone and placing the wash in a glass container. The use
of exactly 100 mL is necessary for the subsequent blank
correction procedures. Reagent water may be used instead of
acetone. In these cases, save a water blank. Perform the
acetone rinses as follows: Carefully remove the probe nozzle
and clean the inside surface by rinsing with acetone from a
wash bottle and brushing with a non-metallic brush. Brush
until the acetone rinse shows no visible particles, after
which make a final rinse of the inside surface with acetone.
Brush and rinse the sample exposed inside of the Swagelok
fitting with acetone in a similar way until no visible
particles remain.
0060 - 11 Revision 0
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0060 - 12
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7.1.5.2.2 Rinse the probe liner with acetone by tilting
and rotating the probe while squirting acetone into its upper
end so that all inside surfaces will be wetted with acetone.
Allow the acetone to drain from the lower end into the sample
container. A funnel may be used to aid in transferring liquid
washings to the container. Follow the acetone rinse with a
nonmetallic probe brush. Hold the probe in an inclined
position, squirt acetone into the upper end as the probe brush
is being pushed with a twisting action through the probe; hold
a sample container underneath the lower end of the probe, and
catch any acetone and particulate matter which is brushed
through the probe. Rinse and brush three times or more until
no visible particulate matter is carried out with the acetone
or until none remains in the probe liner on visual inspection.
Rinse the brush with acetone, and quantitatively collect these
washings in the sample container. After the brushing, make a
final acetone rinse of the probe as described above.
7.1.5.2.3 It is recommended that two people clean the
probe to minimize sample losses. Between sampling runs, keep
brushes clean and protected from contamination.
7.1.5.2.4 Clean the inside of the front half of the
filter holder by rubbing the surfaces with a nylon bristle
brush and rinsing with acetone. Rinse each surface three
times or more if needed to remove visible particulate. Make
a final rinse of the brush and filter holder. Make a final
rinse of the brush and filter holder. After all acetone
washings and particulate matter have been collected in the
sample container, tighten the lid on the sample container so
that acetone will not leak out when it is shipped to the
laboratory. Mark the height of the fluid level to determine
whether or not leakage occurred during transport. Label the
container clearly to identify its contents.
7.1.5.3 Container No. 3 (probe rinse). Keep the probe assembly
clean and free from contamination as described in Section 7.1.5.2 during
the 0.1M nitric acid rinse described below. Rinse the probe liner, probe
nozzle, and filter, and front half of the filter holder thoroughly with
100 ml of 0.1 M nitric acid and place the wash into a sample storage
container.
NOTE: The use of exactly 100 ml is necessary for the subsequent
blank correction procedures. Perform the rinses as applicable and
generally as described in Method 12, Section 5.2.2. Record the
volume of the combined rinse. Mark the height of the fluid level on
the outside of the storage container and use this mark to determine
if leakage occurs during transport. Seal the container and clearly
label the contents. Finally, rinse the nozzle, probe liner, and
front half of the filter holder with water followed by acetone and
discard these rinses.
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7.1.5.4 Container No. 4 (Impingers 1 through 3, HN03/H202 impingers
and moisture knockout impinger, when used, contents and rinses). Due to
the potentially large quantity of liquid involved, the tester may palace
the impinger solutions from Impingers 1, 2, and 3 in more than one
container. Measure the liquid in the first three impingers volumetrically
to within 0.5 ml using a graduated cylinder. Record the volume of liquid
present. This information is required to calculate the moisture content
of the sampled flue gas. Clean each of the first three impingers, the
filter support, the back half of the filter housing, and connecting
glassware by thoroughly rinsing with 100 mL of 0.1 M nitric acid using the
procedure as applicable and generally as described in Method 12, Section
5.2.4.
NOTE: The use of exactly 100 ml of 0.1 M nitric acid rinse is
necessary for the subsequent blank correction procedures. Combine
the rinses and impinger solutions, measure and record the volume.
Mark the height of the fluid level on outside of container to
determine if leakage occurs during transport. Seal the container
and clearly label the contents.
7.1.5.5 Containers No. 5A (0.1M HN03), 5B (KMn04/H2S04 absorbing
solution), and 5C (8M HC1 rinse and dilution). If mercury is not being
measured in this train, then Impingers 4, 5, and 6, as shown in Figure A-
1, are not necessary and may be eliminated.
7.1.5.5.1 Pour all the liquid, if any, from the impinger
which was empty at the start of the run (normally Impinger 4) and
which precedes the two permanganate impingers into a graduated
cylinder and measure the volume to within 0.5 ml. This information
is required to calculate the moisture content of the sampled flue
gas. Place the liquid in Sample Container No. 5A. Rinse the
impinger (No. 4) with 100 ml of 0.1M HN03 and place this into
Container No. 5A. Pour all the liquid from the two permanganate
impingers into a graduated cylinder and measure the volume to within
0.5 ml. This information is required to calculate the moisture
content of the sampled flue gas. Place this KMn04 absorbing
solution stack sample from the two permanganate impingers into
Container No. 5B. Using 100 ml total of the fresh acidified
potassium permanganate solution, rinse the permanganate impinger and
connecting glass pieces a minimum of three times. Place the rinses
into Container No. 5B, carefully assuring transfer of all loose
precipitated materials from the two impingers into Container No. 5B.
Using 100 ml total of water, rinse the permanganate impingers and
connecting glass pieces a minimum of three times, and place the
rinses into Container No. 5B, carefully assuring transfer of all
loose precipitated material, if any, from the two impingers into
Container No. 5B. Mark the height of the fluid level on the outside
of the bottle to determine if leakage occurs during transport. See
the following note and properly prepare the bottle and clearly label
the contents.
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NOTE: Due to the potential reaction of the potassium permanganate
with the acid, there may be pressure buildup in the sample storage
bottle. These bottles shall not be filled full and shall be vented
to relieve excess pressure. Venting is required. A No. 70-72 hole
drilled in the container cap and Teflon liner is suggested.
7.1.5.5.2 If no visible deposits remain after the above
described water rinse, do not rinse with HC1. However, if deposits
do remain on the glassware after this water rinse, wash the impinger
surfaces with 25 ml of 8M HC1, and place the wash in a separate
sample container labeled Container No. 5C that contains 200 ml of
water. Wash the impinger walls and stem with the HC1 by turning the
impinger on its side and rotating it so that the HC1 contacts all
inside surfaces. Use a total of only 25 ml of 8M HC1 for rinsing
both permanganate impingers combined. Rinse the first impinger,
then pour the actual rinse used for the first impinger into the
second impinger for its rinse. Finally, pour the 25 ml of 8M HC1
rinse carefully with stirring into Container No. 5C. Mark the
height of the fluid level on the outside of the bottle to determine
if leakage occurs during transport.
7.1.5.6 Container No. 6 (silica gel). Note the color of the
indicating silica gel to determine whether it has been completely spent
and make a notation of its condition. Transfer the silica gel from its
impinger to its original container and seal. The tester may use a funnel
to pour the silica gel and a rubber policeman to remove the silica gel
from the impinger. The small amount of particles that may adhere to the
impinger wall need not be removed. Do not use water or other liquids to
transfer the silica gel since weight gained in the silica gel impinger is
used for moisture calculations. Alternatively, if a balance is available
in the field, record the weight of the spent silica gel (or silica gel
plus impinger) to the nearest 0.5g.
7.1.5.7 Container No. 7 (acetone blank). If particulate emissions
are to be determined, at least once during each field test, place 100-mL
portion of the acetone used in the sample recovery process into a labeled
container for use in the front-half field reagent blank. Seal the
container.
7.1.5.8 Container No. 8A (0.1 M nitric acid blank). At least once
during each field test, place 300 ml of the 0.1 M nitric acid solution
used in the sample recovery process into a labeled container for use in
the sample recovery process into a labeled container for use in the front-
half and back-half field reagent blanks. Seal the container.
7.1.5.9 Container No. 8B (water blank). At least once during each
field test, place 100 mL of the water used in the sample recovery process
into a labeled Container No. 8B. Seal the container.
7.1.5.10 Container No. 9 (5 percent nitric acid/10 percent hydrogen
peroxide blank). At least once during each field test, place 200 ml of
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the 5% nitric acid/10% hydrogen peroxide solution used as the nitric acid
impinger reagent into a labeled container for use in the back-half field
reagent blank. Seal the container.
7.1.5.11 Container No. 10 (acidified potassium permanganate blank).
At least once during each field test, place 100 ml of the acidified
potassium permanganate solution used as the impinger solution and in the
sample recovery process into a labeled container for use in the back-half
field reagent blank for mercury analysis. Prepare the container as
described in Section 7.2.5.5.1 note.
7.1.5.12 Container No. 11 (8M HC1 blank). At least once during
each field test, place 200 mL of water into a sample container. Then pour
25 ml of 8M HC1 carefully with stirring into the 200 ml of water in the
container. Mix well and seal the container.
7.1.5.13 Container No. 12 (filter blank). Once during each field
test, place an unused filter from the same lot as the sampling filters in
a labeled petri dish. Seal the petri dish. This will be used in the
front-half field reagent blank.
7.2 Sample preparation. Note the level of the liquid in each of the
containers and confirm on the analysis sheet whether or not leakage occurred
during transport. If a noticeable amount of leakage has occurred either void the
sample or use approved methods to correct the final results. A diagram
illustrating sample preparation and analysis procedures for each of the sample
train components is shown in Figure A-3.
NOTE: Follow the appropriate sample preparation procedures:
Method 3010: Acid Digestion of Aqueous Samples and
Extracts for Total Metals for Analysis by FLAA or
ICP.
Method 3015: Microwave Assisted Acid Digestion Digestion
of Aqueous Samples and Extracts.
Method 3050: Acid Digestion of Sediments, Sludges, and
Soils.
Method 3051: Microwave Assisted Acid Digestion of
Sludges, Soils, and Oils.
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Figure A-3. Sampling Preparation and Analysis Scheme
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If the sampling train uses an optional cyclone, the cyclone catch should be
prepared and digested using the same procedures described for the filters and
combined with the digested filter samples.
7.2.1 Container No. 1 (filter). If particulate emissions are
being determined, then desiccate the filter and filter catch without added
heat and weigh to a constant weight as described in Section 4.3 of Method
5. For analysis of metals, divide the filter with its filter catch into
portions containing approximately 0.5 g each and place into the analyst's
choice of either individual fluorocarbon based microwave pressure relief
vessels or Parr® Bombs. Add 6 ml of concentrated nitric acid and 4 ml of
concentrated hydrofluoric acid to each vessel. For microwave heating,
microwave the sample according to the parameters defined in Method 3051.
For conventional heating, heat the Parr® Bombs in an oven at 140°C (285°F)
for 6 hours following the manufacturer's recommendations for Bomb loading,
assembly and disassembly, cleaning, and handling. Cool the samples to
room temperature and combine with the acid digested probe rinse as
required in Section 7.3.3.
NOTE: Hydrofluoric acid (HF) has been identified as an exceptional
health and contact hazard. Burns and other symptoms can be sever
and may not appear immediately. The analyst should perform all
operations with HF under appropriate laboratory conditions (i.e., in
a fume hood suitable for HF work), should be fully informed
regarding the appropriate safety data (e.g., all hazard warnings,
storage and handling requirements, spill cleanup procedures, and
emergency treatments for exposure), and should wear the appropriate
laboratory protective equipment (e.g., goggles, face shield, lab
coat, rubber apron, long rubber gloves) when preparing and handling
digestates and other solutions containing HF.
7.2.2 Container No. 2 (acetone rinse). Measure the liquid in
this container either volumetrically to +1 ml or gravimetrically to ±0.5
g. Transfer the contents to an acid-cleaned tared 250-mL beaker and
evaporate to dryness at ambient temperature and pressure. If particulate
emissions are being determined, desiccate for 24 hours without added heat,
weigh to a constant weight according to the procedures described in
Section 4.3 of Method 5, and report the results to the nearest 0.1 mg.
Redissolve the residue with 10 ml concentrated nitric acid and carefully,
with stirring, combine the resultant sample including all liquid and any
particulate matter with Container No. 3 prior to beginning the Section
7.3.3.
7.2.3 Container No. 3 (probe rinse). The pH of this sample
shall be 2 or lower. If the pH is higher, the sample should be acidified
by careful addition, with stirring, with concentrated nitric acid to pH 2.
The sample should be rinsed into a beaker with water and the beaker should
be covered with a ribbed watchglass. The sample volume should be reduced
0060 - 18 Revision 0
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to approximately 20 ml by heating on a hot plate at a temperature just
below boiling. Then follow one of the digestion procedures listed below.
7.2.3.1 Digest the sample using the appropriate method
(Method 3010, 3015, or Parr Bomb), using the HF modification and
then continuing to follow the procedures described in Section 7.2.1.
7.2.3.2 Combine the digestate prepared in Section 7.2.1.
The resultant combined sample is a Fraction 1 precursor. Filter the
combined solution of the acid digested filter and probe rinse
samples using Whatman 541 filter paper. Dilute to 300 ml (or the
appropriate volume for the expected metals concentration) with
water. This dilution is Fraction 1. Measure and record the volume
of the Fraction 1 solution to within 0.1 ml. Quantitatively remove
a 50-mL aliquot and label as Fraction IB. Label the remaining 250
ml portion as Fraction 1A. Fraction 1A is used for ICP-AES or AAS
analysis. Fraction IB is used for the determination of front-half
mercury.
7.2.4 Container No. 4 (Impingers 1-3). Measure and record the
total volume of this sample (Fraction 2) to within 0.5 mL. Remove a 75-to
100-mL aliquot for mercury analysis and label as Fraction 2B. Label the
remaining portion of Container No. 4 as aliquot Fraction 2A. Aliquot
Fraction 2A defines the volume of 2A prior to digestion. All of aliquot
Fraction 2A is digested to produce concentrated Fraction 2A. Concentrated
Fraction 2A defines the volume of 2A after digestion which is normally 150
mL. Concentrated Fraction 2A is analyzed for all the metals except
mercury. The Fraction 2B aliquot should be prepared and analyzed for
mercury as described in Section 7.4.7. Fraction 2A shall be pH 2 or
lower. If necessary, use concentrated nitric acid to lower Fraction 2A to
pH 2. The sample should be rinsed into a beaker with water and the beaker
should be covered with a ribbed watchglass. The sample volume should be
reduced to approximately 20 mL by heating on a hot plate at a temperature
just below boiling. Then follow either of the digestion procedures below.
7.2.4.1 Method 3015: Microwave Assisted Acid Digestion of
Aqueous Samples and Extracts. Cool, filter the sample, and dilute
to 150 mL (or the appropriate volume for the expected metals
concentrations) with water. This dilution is concentrated Fraction
2A. Measure and record the volume of the Fraction 2A solution to
within 0.1 mL.
7.2.4.2 Method 3010: Acid Digestion of Aqueous Samples and
Extracts for Total Metals for Analysis by FLAA and ICP. Cool,
filter the sample, and dilute to 150 mL ( or the appropriate volume
for the expected metals concentrations) with water. This dilution
is concentrated Fraction 2A. Measure and record the volume of the
Fraction 2A solution to within 0.1 mL.
7.2.5 Container Nos. 5A, 5B, and 5C (Impingers 4, 5, and 6). Keep
these samples separate from each other.
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7.2.5.1 Measure and record the volumes of 5A and 5B each to
within 0.5 ml. Dilute Sample 5C to 500 ml with water. The Samples
5A, 5B, and 5C are referred to respectively as Fractions 3A, 3B, and
3C. Follow the analysis procedures described in Section 7.4.,
7.2.5.2 Because the permanganate rinse and water rinse have
the capability to recover a high percentage of the mercury from the
permanganate impingers, the amount of mercury in the HC1 rinse
(Fraction 3C) may be very small, possibly even insignificantly
small. However, as instructed in this method, add the total of any
mercury measured in and calculated for the HC1 rinse (Fraction 3C)
to that for Fractions IB, 2B, 3A, and 3B for calculation of the
total sample mercury concentration.
7.2.6 Container No. 6 (silica gel). Weigh the spent silica gel (or
silica gel plus impinger) to the nearest 0.5 g using a balance. (This
step may be conducted in the field).
7.3 Calibration
7.3.1 Refer to the appropriate analytical methods for the proper
calibration procedures.
7.4 Sample analysis.
7.4.1 For each sampling train, seven individual samples are
generated for analysis. A schematic identifying each sample and the
prescribed sample preparation and analysis scheme is shown in Figure A-3.
The first two samples, labeled Fractions 1A and IB, consist of the
digested samples from the front half of the train. Fraction 1A is for
ICP-AES and AAS analysis as described in Section 7.4.5. Fraction IB is
for determination of front-half mercury as described in Section 7.4.7.
7.4.2 The back half of the train was used to prepare the third
through seventh samples. The third and fourth samples, labeled Fractions
2A and 2B, contain the digested samples from the moisture knockout, if
used, and HN03/H202 Impingers 1 through 3. Fraction 2A is for ICP-AES or
AAS analysis. Fraction 2B will be analyzed for mercury.
7.4.3 Samples 5A, 5B, and 5C are labeled Fractions 3A, 3B, and 3C,
respectively. They consist of the impinger contents and rinses from the
empty Impinger 4 and the permanganate Impingers 5 and 6. These samples
are analyzed for mercury as described in Section 7.4.7. The total back-
half mercury catch is determined from the sum of Fraction 2B and Fraction
3A, 3B, and 3C.
7.4.4 Initially, analyze all samples for iron, aluminum, and all
the target metals except mercury . If iron and aluminum are present in
the sample, the sample may have to be diluted so that each of these
0060 - 20 Revision 0
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elements is at a concentration of less than 50 ppm to reduce their
spectral interferences on arsenic, cadmium, chromium, and lead.
NOTE: When analyzing samples in a hydrofluoric acid matrix, an
alumina torch should be used. Since all front-half samples
will contain hydrofluoric acid, use an alumina torch.
7.4.5 ICP-AES analysis. Fraction 1A and Fraction 2A are analyzed
by ICP-AES using EPA SW-846 Method 6010. Refer to method 6010 for the
proper analytical procedures.
7.4.6 AAS by direct aspiration and/or graphite furnace. If
analysis of metals in Fraction 1A and Fraction 2A using graphite furnace
or direct aspiration AAS is desired, Table A-2 should also be consulted to
determine possible interferences and techniques to use for their
minimization. Refer to SW-846 Vol. 1A to determine the appropriate
analytical protocol.
7.4.7 Cold vapor AAS mercury analysis. Fraction IB, Fraction 2B,
and Fraction 3A, 3B, and 3C should be analyzed separately for mercury
using cold vapor atomic absorption spectroscopy following the method
outlined in EPA SW-846 Method 7470. Refer to Method 7470 for the proper
analytical protocol. If no prior knowledge exists of the expected amount
of mercury in the sample, dilute a 1-mL to 10-mL aliquot of each original
sample to 100 ml. Record the amount of the aliquot used for dilution to
100 ml. A 5-mL aliquot is suggested for the first dilution to 100 mL. To
determine the stack emission value for mercury, the amount of the aliquot
of the sample used for dilution and analysis is dependent on the amount of
mercury in the aliquot: the total amount of mercury in the aliquot used
for analysis must be less than 1 ug, and within the range (zero to 1000
ng) of the calibration curve.
7.5 Calculations
7.5.1 Dry gas volume. Using the data from this test, calculate
Vm
-------
7.5.4.1 Fraction 1A, front half, metals (except Hg).
Calculate the amount of each metal collected in Fraction 1 of the
sampling train using the following equation:
Mfh = Ca1 Fd VsolnJ Eq. I1
where:
Mfh = total mass of each metal (except Hg)
collected in the front half of the sampling
train (Fraction 1), ug.
Ca1 = concentration of metal in sample Fraction
1A as read from the standard curve (ug/mL).
Fd = dilution factor (Fd = the inverse of the
fractional portion of the concentrated
sample in the solution actually used in the
instrument to produce the reading Ca1. For
example, when a 2 mL volume of Fraction 1A
is diluted to 10 mL, Fd = 5).
Vso,n1 = total volume of digested sample solution
(Fraction 1), ml.
7.5.4.2 Fraction 2A, back half, metals (except Hg).
Calculate the amount of each metal collected in Fraction 2 of the
sampling train using the following equation.
Mbh « Ca2 Fa Va Eq. 21
where:
Mbh = total mass of each metal (except Hg)
collected in the back half of the sampling
train (Fraction 2), ug.
Ca2 = concentration of metal in sample
concentrated Fraction 2A, as read from the
standard curve (ug/mL).
Fa = aliquot factor, volume of Fraction 2
divided by volume of aliquot Fraction 2A.
Va = total volume of digested sample solution
(concentrated Fraction 2A), ml. See
Section 6.1.4.1 or 6.1.4.2 as applicable.
7.5.4.3 Total train, metals (except Hg). Calculate the total
amount of each of the quantified metals collected in the sampling
train as follows:
1If Fractions 1A and 2A are combined, proportional aliquots must be used.
Appropriate changes must be made in Equations 1-3 to reflect this approach.
0060 - 22 Revision 0
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Mt = (M,h - Mfhb) + (Mbh - Mbhb) Eq. 31
where:
Mt = total mass of each metal (separately stated
for each metal) collected in the sampling
train, ug.
Mfhb = bank correction value for mass of metal
detected in front-half field reagent blank,
ug.
Mbhb = blank correction value for mass of metal
detected in back-half field reagent blank,
ug.
NOTE: If the measured blank value for the front half (Mfhb) is in the
range 0.0 to A ug [where A ug equals the value determined by
multiplying 1.4 ug/in.2 times the actual area in square inches of
the filter used in the emission sample], Mfhb may be used to correct
the emission sample value (Mfh); if Mfhb exceeds A ug, the greater of
the two following values may be used: A ug, or the lesser value of
Mfhb or 5 percent of Mfh.
If the measured blank value for the back half (Mbhb) is in the range
0.0 to 1 ug, Mbhb may be used to correct the emission sample value
(Mbh); if Mbhb exceeds 1 ug, the greater of the two following values
may be used: 1 ug or 5 percent of Mbh.
7.5.5 Mercury in source sample.
7.5.5.1 Fraction IB, front half, Hg. Calculate the amount of
mercury collected in the front half, Fraction 1, of the sampling
train using the following equation:
Qfh
Hgfh = x Vsolnl Eq. 4
M1B
where:
Hgfh = total mass of mercury collected in the
front half of the sampling train (Fraction
1), ug.
Qfh = quantity of mercury in analyzed sample, ug.
Vsoln1 = total volume of digested sample solution
(Fraction 1), ml.
1If Fractions 1A and 2A are combined, proportional aliquots must be used.
Appropriate changes must be made in Equations 1-3 to reflect this approach.
0060 - 23 Revision 0
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'f1B
volume of Fraction IB analyzed, mL.
following Note.
See the
NOTE: Vf1B is the actual amount of Fraction IB analyzed. For
example, if 1 ml of Fraction IB were diluted to 100 mL to bring it
into the proper analytical range, and 1 ml of the 100 ml dilution
was analyzed, Vf1B would be 0.01.
7.5.5.2 Fraction 2B and Fractions 3A, 3B, and 3C, back half,
Hg. Calculate the amount of mercury collected in Fraction 2 using
Equation 5 and Fractions 3A, 3B, and 3C using Equation 6. Calculate
the total amount of mercury collected in the back half of the
sampling train using Equation 7.
'f2B
where:
Qbh2
Hgbh2 x v,
Hgbh2
Qbh2
V2B
soln-2
Eq. 5
total mass of mercury collected in Fraction
2, ug.
quantity of mercury in analyzed sample, ug.
total volume of Fraction 2, ml.
volume of Fraction 2B analyzed, ml (see the
following note).
NOTE: Vf2b is the actual amount of Fraction 2B analyzed. For
example, if 1 mL of Fraction 2B were diluted to 10 mL to bring it
into the proper analytical range, and 5 mL of the 10-mL dilution was
analyzed, Vf2b would be 0.5.Use Equation 6 to calculate separately
the back-half mercury for Fractions 3A, 3B, and 3C.
Hg
where:
H9bh3(A.B,
Qbh3(A,B,C I
"f3|A.B,C)
u
ysoln,3(A,B,C)
•
-------
Hgbh = Hgbh2 + Hgbh3A + Hgbh3B + Hgbh3C Eq. 7
where:
Hgbh = total mass of mercury collected in the back
half of the sampling train, ug.
7.5.5.3 Total train mercury catch. Calculate the total
amount of mercury collected in the sampling train using Equation 8.
Hgt = (Hgfh - Hgfhb) + (Hgbh - Hgbhb) Eq. 8
where:
Hgt = total mass of mercury collected in the
sampling train, ug.
Hgfhb = blank correction value for mass of mercury
detected in front-half field reagent blank,
ug.
Hgbhb = blank correction value for mass of mercury
detected in back-half field reagent blank,
ug.
NOTE: If the total of the measured blank values (Hgfhb + Hgbhb) is in
the range of 0 to 6 ug, then the total may be used to correct the
emission sample value (Hgfh + Hgbh); if it exceeds 6 ug, the greater
of the following two values may be used: 6 ug or 5 percent of the
emission sample value (Hgfh + Hgbh).
7.5.6 Metal concentration of stack gas. Calculate each metal
separately for the cadmium, total chromium, arsenic, nickel, manganese,
beryllium, copper, lead, phosphorus, thallium, silver, barium, zinc,
selenium, antimony, and mercury concentrations in the stack gas (dry
basis, adjusted to standard conditions) as follows:
C8 = K4 (Mt/Vm(std)) Eq. 9
where:
Cs = concentration of each metal in the stack gas,
mg/dscm.
K4 = 10"3 mg/ug.
Mt = total mass of each metal collected in the
sampling train, ug; (substitute Hgt for Mt
for the mercury calculation).
Vm(std) = volume of gas sample as measured by the dry
gas meter, corrected to dry standard
conditions, dscm.
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7.5.7 Isokinetic variation and acceptable results. Same as Method
5, Sections 6.11 and 6.12, respectively.
8.0 QUALITY CONTROL
8.1 Sampling Blanks.
8.1.1 Field Reagent Blanks (FRBs). When analyzed, the blank
samples in Container Nos. 7 through 12 shall be processed, digested, and
analyzed as follows. Digest and process one of the filters from Container
No. 12 contents per Section 7.2.1, 100 mL from Container No. 7 per Section
7.2.2, and 100 mL from Container No. 8 per Section 7.2.3. This produces
Fraction Blank 1A and Fraction Blank IB from Fraction Blank 1. (If
desired, the other two filters may be digested separately according to
Section 7.2.1, diluted separately to 300 mL each, and analyzed separately
to produce a blank value for each of the two additional filters. If these
analyses are performed, they will produce two additional values for each
of Fraction Blank 1A and Fraction Blank IB. The three Fraction Blank 1A
values will be calculated as three values of Mfhb in Equation 3 of Section
7.5.4.3, then the three values shall be totalled and divided by three to
become the value Mfhb to be used in the computation of Mt by Equation 3.
Similarly, the three Fraction Blank IB values will be calculated
separately as three values, {.otalled, averaged, and used as the value for
Hgfhb in Equation 8 of Section 7.5.5.3. The analyses of the two extra
filters are optional and are not a requirement of this method, but if the
analyses are performed, the results must be considered as described
above.) Combine 100 mL of Container No. 8A with 200 mL of the contents of
Container No. 9 and digest and process the resultant volume per Section
6.1.4. This produces concentrated Fraction Blank 2A and Fraction Blank 2B
from Fraction Blank 2. A 100-mL portion of Container No. 8A is Fraction
Blank 3A. Combine 100 mL of the contents of Container No. 10 with 33 mL
of the contents of Container No. 8B. This produces Fraction Blank 3B.
(Use 400 mL as the volume of Fraction Blank 3B when calculating the blank
value. Use the actual volumes when calculating all the other blank
values). Dilute 225 mL of the contents of Container No. 11 to 500 mL with
water. This produces Fraction Blank 3C. Analyze Fraction Blank 1A and
Fraction Blank 2A per Section 7.2.4.1 and/or Section 7.2.4.1 Analyze
Fraction Blank IB, Fraction Blank 2B, and Fraction Blank 3A, 3B, and 3C
per Section 7.2.4.1. The analysis of Fraction Blank 1A produces the
front-half reagent blank correction values for the metals except mercury;
the analysis of Fraction Blank IB produces the front-half reagent blank
correction value for mercury. The analysis of Fraction Blank 2A produces
the back-half reagent blank correction values for the metals except
mercury, while separate analysis of Fraction Blanks 2B and 3 produce the
back-half reagent blank correction value for mercury.
8.1.2 Field Sampling Train Blanks (FSTBs). FSTBs must be
submitted with the samples collected at each site. The FSTBs include the
0060 - 26 Revision 0
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sample bottles containing aliquots of sample recovery solvents, unused
filters, and resin cartridges. At aminimum, one complete sampling train
will be assembled in the field staging area, taken to the sampling area,
and leak-checked at the beginning and end of the testing (or for the same
total number of times as the actual test train). The filter housing and
probe of the blank train will be heated during the sample test. The train
will be recovered as if it were an actual test sample. No gaseous sample
will be passed through the sampling train.
8.1.3 Laboratory Reagent Blanks (LRBs). An attempt may be
made to determine if the laboratory reagents used in section 7.2 caused
contamination. They should be analyzed by the procedures in section 7.4.
The administrator will determine whether the laboratory blank reagent
values can be used in the calculation of the stationary source test
results.
8.2 Quality Control Samples. The following quality control samples
should be analyzed. All appropriate Chapter One quality control procedures
should be followed.
8.2.1 ICP-AES analysis. Follow the quality control shown in
Chapter One and Section 8 of Method 6010.
8.2.2 Direct aspiration and/or graphite furnace AAS analysis
for antimony, arsenic, barium, beryllium, cadmium, copper, chromium, lead,
nickel, manganese, mercury, phosphorus, selenium, silver, thallium, and
zinc. All samples should be analyzed in duplicate. Perform a post-
digestion spike on at least one front-half sample and one back-half sample
or one combined sample. If recoveries of less than 75 percent or greater
than 125 percent are obtained for the post-digestion spike, analyze each
sample by the method of standard additions.
8.2.3 Cold vapor AAS analysis for mercury. All samples should
be analyzed in duplicate. Perform a post-digestion spike on one sample
from the nitric acid impinger portion ( must be within 25% or samples must
be analyzed by the method of standard additions).
9.0 METHOD PERFORMANCE
9.1 To ensure optimum sensitivity in obtaining the measurements, the
concentrations of target metals in the solutions are suggested to be at least ten
times the analytical detection limits. Under certain conditions, and with
greater care in the analytical procedure, this concentration can be as low as
approximately three times the analytical detection limit. In all cases, on at
least one sample (run) in the source test and for each metal analyzed, repetitive
analyses, method of standard additions (MSA), serial dilution, or matrix spike
addition, etc., shall be used to establish the quality of the data.
0060 - 27 Revision 0
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9.2 Actual in-stack method detection limits will be determined based on
actual source sampling parameters and analytical results as described above. If
required, the method in-stack detection limits can be made more sensitive than
those shown in Table 2 for a specific test by using one or more of the following
options:
o A 1-hour sampling run collects a stack gas sampling volume of about
1.25 m3. If the sampling time is increased and 5 m3 are collected,
the in-stack method detection limits would be one fourth of the
values shown in Table A-l (i.e., the method is four times more
sensitive than an hour run). Larger sample volumes would make the
method more sensitive again.
o The in-stack detection limits assume that all of the sample is
digested (with exception of the aliquot for mercury) and the final
liquid volumes for analysis are 300 ml for the front half (Fraction
1) and 150 ml for the back half (Fraction 2A). If the volume of the
front half is concentrated from 300 ml to 30 ml, the front half in-
stack detection limits would be one tenth of the values shown above
(ten times more sensitive). If the back-half volume is concentrated
from 150 ml to 25 ml, the in-stack detection limits would be one
sixth of the above values. Matrix effects checks are necessary on
analyses of samples and typically are of greater significance for
samples that have been concentrated to less than the normal sample
volume. Reduction to a volume of less than 25 mL may not allow
redissolving of the residue and may increase interference by other
compounds.
o When both of the above two improvements are used on one sample at
the same time, the resultant improvements are multiplicative. For
example, where stack gas volume is increased by a factor of five and
the total liquid sample digested volume of both the front and back
halves is reduced by factor of six, the in-stack method detection
limit is reduced by a factor of thirty (the method is thirty times
more sensitive).
o Conversely, reducing stack gas sample volume and increasing sample
liquid volume will increase detection limits (i.e., the method would
be less sensitive). The front-half and back-half samples (Fractions
1A plus 2A) can be combined proportionally prior to analysis. The
resultant liquid volume (excluding the mercury fractions, which must
be analyzed separately) is recorded. Combining the sample as
described does not allow determination (whether front or back half)
of where in the train the sample was captured. The in-stack method
detection limit then becomes a single value for all metals except
mercury, for which the contribution of the mercury fraction must be
considered.
o The above discussion assumes no blank correction.
0060 - 28 Revision 0
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9.3 Precision. The precision measurements (relative standard deviation)
for each metal detected in a method development test at a sewage sludge
incinerator, are as follows: Sb (12.7%), As (13.5%), Ba (20.6%), Cd (11.5%), Cr
(11.2%), Cu (11.5%), Pb (11.6%), P (14.6%), Se (15.3%), Tl (12.3%), and Zn
(11.8%). The precision for nickel was 7.7% for another test conducted at a
source simulator. Beryllium, manganese, and silver were not detected in the
tests; however, based on the analytical sensitivity of the ICP-AES for these
metals, it is assumed that their precision values should be similar to those for
the other metals, when detected at similar levels.
9.4 Using (1) the procedures described in this method, (2) the analytical
detection limits listed in Section 1, (3) a volume of 300 ml for the front half
and 150 ml for the back-half samples, and (4) a stack gas sample volume of 1.25
m3, the corresponding in-stack method detection limits are presented in Table A-2
and calculated as shown:
A x B = D
C
where:
A = analytical detection limit, ug/mL.
B = volume of sample prior to aliquot for analysis, ml.
C = stack sample volume, dscm (dsm3).
D = in-stack detection limit, ug/m3.
Values in Table A-2 are calculated for the front and back half and/or the total
train.
10.0 REFERENCES
1. Method 303F in Standard Methods for the Examination of Water Wastewater,
15th Edition, 1980. Available from the American Public Health Association, 1015
18th Street, N.W., Washington, D.C. 20036.
2. EPA Methods 6010, 7000, 7041, 7060, 7131, 7421, 7470, 7740, and 7841, Test
Methods for Evaluating Solid Waste: Physical/Chemical Methods. SW-846 Third
Edition. September 1988. Office of Solid Waste and Emergency Response, U.S.
Environmental Protection Agency, Washington, D.C. 20460.
3. EPA Method 200.7, Code of Federal Regulations, Title 40, Part 136, Appendix
C. July 1, 1987.
4. EPA Methods 1 through 5, Code of Federal Regulations, Title 40, Part 60,
Appendix A, July 1, 1987.
5. EPA Method 12, Code of Federal Regulations, Title 40, Part 60, Appendix A,
July 1, 1987.
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6. ASTM Standard Method D2986-71, available from the American Society for
Testing and Materials, 1916 Race Street, Philadelphia, PA 19103.
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Metal
TABLE 2. IN-STACK METHOD DETECTION LIMITS (ug/m3)
FOR TRAIN FRACTIONS USING ICP-AES AND AAS
Front Half
Fraction 1
Probe and Filter
BacKHalf
Fraction 2
Impingers 1-3
Back Half
Fraction 3
Impingers 4-5
Total Train
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Manganese
Mercury
Nickel
Phosphorus
Selenium
Silver
Thallium
Zinc
7.7 (0.7)*
12.7 (0.3)*
0.5
0.07 (0.05)*
1.0 (0.02)*
1.7 (0.2)*
1.4
10.1 (0.2)*
0.5 (0.2)*
0.6**
3.6
18.0
18.0 (0.5)*
1.7
9.6 (0.2)*
0.5
3.8 (0.4)*
6.4 (0.1)*
0.3
0.04 (0.03)*
0.5 (0.01)*
0.8 (0.1)*
0.7
5.0 (0.1)*
0.2 (0.1)*
3.0** 2.0**
1.8
9.0
9.0 (0.3)*
0.9
4.8 (0.1)*
0.3
11.5 (1.1)*
19.1 (0.4)*
0.8
0.11 (0.08)*
1.5 (0.03)*
2.5 (0.3)*
2.1
15.1 (0.3)*
0.7 (0.3)*
5.6**
5.4
27.0
27.0 (0.8)*
2.6
14.4 (0.3)*
0.8
( )* Detection limit when analyzed by GFAAS.
** Detection limit when analyzed by CVAAS, estimated for back-half and total
train.
NOTE:Actual method in-stack detection limits will be determined based on
actual source sampling parameters and analytical results as described
earlier in this section.
0060 - 31
Revision 0
January 1995
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METHOD 0060
DETERMINATION OF METALS IN STACK EMMISIONS
6 1.4.4 Alternatively, Hg can
be measured in seperate train
by Method 101A.
6.1.1 - 6.1.2 Prepare sampling train
glassware, filter (if requires) and
calibrate sampling train components.
6.1.3 - 6.1.4.3 Setup sampling train as
shown in Fig. A-1. Add reagents to
appropriate impingers and retain
volumes of each reagent for reagent
blands. Omit impingers No. 4, 5, and 6
(1 empty impinger and 2 KMNO impingers)
if Hg is not required.
6.1.5 - 6.1 .7 Leak check sampling train,
perform sampling operation and calculate
percent isokenetic.
7.1.1 - 7.1.4 Parti ally disassemble sampling
train, cap-off sample train inlets, transfer
assemble to cleanup area.
7.1.5 Sample Recovery: Recover filter
and place in container No. 1 (7.1.5.1)
if particulate emissions are required
(7.1.5.2-7.1.5.2.4) rinse probe nozzle
and fittings with acetone or water,
collect rinses, label as container No. 2.
7.1.5.3 If particulate emissions are not
required, rinse probe liner, nozzle, and
filter with 100 ml 0.1 N HN03, collect
rinses, label as container No. 3.
0060 - 35
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METHOD 0060 (CONT.)
DETERMINATION OF METALS IN STACK EMISSIONS
7.1.5.4 Measure volume of liquid
in impingers 1-3, rinse impingers,
combine liquids and rinses into
container No. 4.
7 1 5.5 - 7 1.5.6 Measure volume of liquid
in impinger 4, combine with rinses into
container 5A Measure volume of KMnO
impingers (5&6). combine with rinses into
container 5B. If visible deposits remain,
(7 1 5.5.2I rinse with 8N HCL, collect
rinses, label as container No. 5C.
7 1.5.6 Transfer silica gel from
impingr 7, to container No. 6,
record weight.
7.2 Sample Preparation: Prepare
filter (7.2.1). rinses (7 2.2-7.2.3)
and impinger solutions (7.2.4-
7.2.5) for analysis by the appropriate
sample preparation procedure:
Method 3010/3015/3050/
3051/3055 (7.2).
7 2.6 Weigh spent silica gel
if not weighed in the field.
7.3 Instrument Calibration: Calibrate
appropriate instrumentation (ICP-AES/
AAS direct aspiration and/or graphite
furnace/cold vapor AAS mercury
analyses prior to sample analysis).
7.4 Sample Analysis: 7.4.1 - 7.4.7
Analyze the seven individual samples
from each sampling train using the
appropriate analytical method. Follow
all QC procedures in Section 8.0.
7.5 Calculations: Calculate dry gas
volume, water vapor content, stack
gas velocity,a nd metals content
using equations or references in
7.5.1 - 7 5.7.
0060 - 36
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METHOD 0061
DETERMINATION OF HEXAVALENT CHROMIUM EMISSIONS
FROM STATIONARY SOURCES
1.0 SCOPE AND APPLICATION
1.1 This method provides procedures for the determination of hexavalent
chromium (Cr+6) emissions from hazardous waste incinerators, municipal waste
incinerators, municipal waste combustors, and sewage sludge incinerators. With
the approval of the Administrator, this method may also be used to measure total
chromium. The sampling train, constructed of Teflon components, has only been
evaluated at temperatures of less than 300°F. Trains constructed of other
materials, for testing at higher temperatures, are currently being evaluated.
1.2 Range: If employing a preconcentration procedure, the lower limit
of the detection range can be extended to 16 nanograms per dry standard cubic
meter (ng/dscm) with a 3 dscm gas sample (0.1 ppb in solution). With sample
dilution, there is no upper limit. Follow your manufacturer's specific
instructions on employing the preconcentration procedure for these analyses.
2.0 SUMMARY OF METHOD
2.1 For incinerators and combustors, the Cr+6 emissions are collected
isokinetically from the source: To eliminate the possibility of Cr + 6 reduction
between the nozzle and impinger, the emission samples are collected with a
recirculatory train where the impinger reagent is continuously recirculated to
the nozzle. Recovery procedures include a post-sampling purge and filtration.
The impinger train samples are analyzed for Cr+6 by an ion chromatograph equipped
with a post-column reactor and a visible wavelength detector. The IC/PCR
separates the Cr+6 as chromate (Cr04=) from other diphenylcarbazide reactions
that occur in the post-column reactor. To increase sensitivity for trace levels
of chromium, a preconcentration system may also be used in conjunction with the
IC/PCR.
3.0 INTERFERENCES
3.1 Components in the sample mat'rix may cause Cr+6 to convert to
trivalent chromium (Cr+3) or cause Cr+3 to convert to Cr+e. A post-sampling
nitrogen purge and sample filtration are included to eliminate many of these
interferences.
3.2 The chromatographic separation of Cr+6 using ion chromatography
reduces the potential for other metals to interfere with the post-column
reaction. For the IC/PCR analysis, only compounds that coelute with Cr+e and
affect the diphenylcarbazide reaction will cause interference.
3.3 Sample cross-contamination that can occur when high-level and low-
level samples or standards are analyzed alternately is eliminated by thorough
0061 - 1 Revision 0
January 1995
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purging of the sample loop. Purging can easily be obtained by increasing the
injection volume of the samples to ten times the size of the sample loop.
4.0 APPARATUS
4.1 Sampling Train: Schematics of the recirculatory sampling trains
employed in this method are shown in Figures 1 and 2. The recirculatory train
is readily assembled from commercially available components. All portions of the
train in contact with the sample are either glass, quartz, Tygon, or Teflon, and
are to be cleaned as per Section 6.0. The metering system is identical to that
specified by Method 5 (see section 3.8.1); the sampling train consists of the
following components:
4.1.1 Probe Nozzle: Glass or Teflon with a sharp, tapered leading
edge. The angle of taper shall be < 30° and the taper shall be on the
outside to preserve a constant internal diameter. The probe nozzle shall
be of the button-hook or elbow design, unless otherwise specified by the
Administrator. A range of nozzle sizes suitable for isokinetic sampling
should be available, e.g., 0.32 to 1.27 cm (1/8 to 1/2 in.) -- or larger
if higher volume sample trains are used -- inside diameter (ID) nozzles in
increments of 0.16 cm (1/16 in.). Each nozzle shall be calibrated
according to the procedures outlined in Section 7.1.1.
4.1.2 Teflon Aspirator or Pump/Sprayer Assembly: Teflon aspirator
capable of recirculating absorbing reagent at 50 mL/min while operating at
0.75 cfm. Alternatively, a pump/sprayer assembly may be used instead of
the Teflon aspirator. A Teflon union-T is connected behind the nozzle to
provide the absorbing reagent/sample gas mix; a peristaltic pump is used
to recirculate the absorbing reagent at a flow rate of at least 50 mL/min.
Teflon fittings, Teflon ferrules, and Teflon nuts are used to connect a
glass or Teflon nozzle, recirculation line, and sample line to the Teflon
aspirator or union-T. Tygon, C-flex or other suitable inert tubing for
use with peristaltic pump.
4.1.3 Teflon Sample Line: Teflon, 3/8" ID, of suitable length to
connect aspirator (or T-union) to first Teflon impinger.
4.1.4 Teflon Recirculation Line: Teflon, 1/4" O.D. and 1/8" I.D.,
of suitable length to connect first impinger to aspirator (or T-union).
4.1.5 Teflon Impingers: Four Teflon impingers; Teflon tubes and
fittings, such as made by Savillex*, can be used to construct impingers 2"
diameter by 12" long, with vacuum-tight 3/8" O.D. Teflon compression
fittings. Alternatively, standard glass impingers that have been Teflon-
lined, with Teflon stems and U-tubes, may be used. Inlet fittings on
impinger top to be bored through to accept 3/8" O.D. tubing as impinger
stem. The second and third 3/8" OD Teflon stem has a 1/4" OD Teflon tube,
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January 1995
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TEFLON IMPINGERS
Figure 1 Schematic of recirculatory impinger train with aspirator assembly.
0061 - 3
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TEFLON IMPINGERS
Figure 2 Schematic of recirculatory impinger train with aspirator assembly.
0061 - 4
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January 1995
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2" long, inserted at its impinger stem should extend to 2" from impinger
bottom, high enough in the impinger reagent to prevent air from entering
recirculating line; the second and third impinger stems should extend to 1/2"
from impinger bottom. The first impinger should include a 1/4" O.D. Teflon
compression fitting for recirculation line. The fourth impinger serves as a
knockout impinger to trap solution carried over from the previous impingers.
NOTE: Mention of trade names or specific product does not constitute
endorsement by the Environmental Protection Agency.
4.1.6 Glass Impinger: Silica gel impinger, Vacuum-tight impingers,
capable of containing 400 g. of silica gel, with compatible fittings. The
silica gel impinger will have a modified stem (1/2" ID at tip of stem).
4.1.7 Thermometer, (identical to that specified by Method 5) at the
outlet of the silica gel impinger, to monitor the exit temperature of the
gas.
4.1.8 Metering System, Barometer, and Gas Density Determinations
Equipment: Same as Method 0010, Section 4.1.3.9 through 4.1.3.11,
respectively.
4.2 Sample Recovery: Clean all items for sample handling or storage with
10% nitric acid solution by soaking, where possible, and rinse thoroughly with
reagent water before use.
4.2.1 Nitrogen Purge Line: Inert tubing and fittings capable of
delivering 0 to 1 scf/min (continuously adjustable) of nitrogen gas to the
impinger train from a standard gas cylinder (See Figure 3). Standard 3/8-
inch Teflon regulator and needle valve may be used.
4.2.2 Wash Bottles: Two polyethylene wash bottles, for reagent
water-nitric rinse solution.
4.2.3 Sample Storage Containers: Polyethylene, with leak-free screw
cap, 500-mL or 1000-mL.
4.2.4 1000-mL Graduated Cylinder and Balance.
4.2.5 Plastic Storage Containers: Air tight containers to store
silica gel.
4.2.6 Funnel and Rubber Policeman: To aid in transfer of silica gel
from impinger to storage container; not necessary if silica gel is weighed
directly in the impinger.
0061 - 5 Revision 0
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TEFLON IMPINGERS
Figure 3 Schematic of post test nitrogen purge system
LHTTTTTTO
0061 - 6
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4.3 Sample Preparation for Analysis: Sample preparation prior to analysis
includes purging the sample train immediately following the sample run, and
filtering the recovered sample to remove particulate matter immediately following
recovery.
4.3.1 Beakers, Funnels, Volumetric Flasks, Volumetric Pipets, and
Graduated Cylinders: Assorted sizes, Teflon or glass, for preparation of
samples, sample dilution, and preparation of calibration standards.
Prepare initially following procedure described in Section 5.1.3 and rinse
between use with 0.1 M HN03 and reagent water.
4.3.2 Filtration Apparatus: Teflon, or equivalent, for filtering
samples, and Teflon filter holder. Teflon impinger components have been
found to be satisfactory as a sample reservoir for pressure filtration
using nitrogen.
4.4 Ion Chromatograph: Refer to Section 4.0 of Metttod 7199 for instrument
and equipment specifications.
4.4.1 Preconcentrator: System in-line with the ion chromatorgaph.
OR
4.5 Sample preconcentration system: A high performance ion chromatograph
(HPIC) non-metallic column with acceptable anion retention characteristics and
sample loading rates as described in the analytical method.
5.0 REAGENTS
5.1 All reagents should, at a minimum, conform to the specifications
established by the Committee on Analytical Reagents of the American Chemical
Society, where such specifications are available. All prepared reagents should
be checked by IC/PCR analysis for Cr+6 to assure that contamination is below the
analytical detection limit for direct injection or, if selected,
preconcentration. If total chromium is also to be determined, the reagents
should also be checked by the analytical technique selected to assure that
contamination is below the analytical detection limit.
5.2 Sampling.
5.2.1 Reagent water: Reagent water shall be interferences free.
All references to water in the method refer to reagent water unless
otherwise specified. A definition of reagent water can be found in
Chapter One.
5.2.2 Potassium Hydroxide, 0.1 M: Add 5.6 gm of KOH(s) to
approximately 900 ml of reagent water and let dissolve. Dilute to 1000 ml
with reagent water.
0061 - 7 Revision 0
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NOTE: At sources with high concentrations of acids and/or S02, the
concentration of KOH should be increased to 0.5 M to insure that the
pH of the solution is above 8.5 after sampling.
5.2.3 Silica Gel and Crushed Ice: Same as Method 5, Sections 3.1.2
and 3.1.4, respectively.
5.3 Sample Recovery: The reagents used in sample recovery are as follows:
5.3.1 Water: Same as subsection 5.2.1.
5.3.2 Nitric Acid, 0.1 M: Add 6.3 mL of concentrated HN03 (70
percent) to a graduated cylinder containing approximately 900 ml of
reagent water. Dilute to 1000 ml with reagent water, and mix well.
5.3.3 pFMndicator Strip: pH indicator capable of determining pH
of solution between the pH range of 7 and 12, at 0.5 pH intervals.
5.4 Sample Preparation
5.4.1 Reagent water: Same as subsection 5.2.1.
5.4.2 Nitric Acid, 0.1 M: Same as subsection 5.3.2.
5.4.3 Filters: Acetate membrane, or equivalent, filters with 0.45
micrometer or smaller pore size to remove insoluble material.
5.5 Analysis
5.5.1 Refer to Section 5.0 of Method 7199 for instruction on
preparation of analytical reagents.
5.6 Performance Audit Sample: A performance audit sample should analyzed
in conjunction with the samples. The audit sample should be prepared in a
suitable sample matrix at a concentration similar to the actual field samples.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Refer to Section 6.0 of Method 7199 for the proper procedures when
collecting, preserving, and handling samples.
6.2 If sample preconcentration is used, dropwise addition of the ammonium
sulfate/ammonium hydroxide buffer may not be appropriate, since the added sulfate
may lead to premature overloading of the column.
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7.0 PROCEDURE
CAUTION: Wear Safety Glasses At All Times During This Test Method.
7.1 Sampling: The complexity of this method is such that to obtain
reliable results, testers should be trained and experienced with test procedures.
7.1.1 Sample Train Calibration: Calibrate the sample train
components according to the indicated sections of Method 5: Probe Nozzle
(Section 5.1); Pitot Tube (Section 5.2); Metering System (Section 5.3);
Temperature Gauges (Section 5.5); Leak-Check of the Metering System
(Section 5.6); and Barometer (Section 5.7).
7.1.2 Pretest Preparation: All components shall be maintained and
calibrated according to the procedures described in APTD-0576, unless
otherwise specified herein. Rinse all sample train components from the
glass nozzle up to the silica gel impinger and sample containers with hot
tap water followed by washing with hot soapy water. Next, rinse the train
components and sample containers three times with tap water followed by
three rinses with reagent water. All the components and container should
then be soaked overnight, or a minimum of 4 hours, in a 10 % (v/v) nitric
acid solution, then rinsed three times with reagent water. Allow the
components to air dry prior to covering all openings with Parafilm, or
equivalent.
7.1.3 Preliminary Determinations: Same as Method 5, Section 4.1.2.
7.1.4 Preparation of Sampling Train: Measure 300 ml of 0.1 M KOH
into a graduated cylinder (or tare-weighed precleaned polyethylene
container). Place approximately 140 ml of the 0.1 M KOH reagent in the
first Teflon impinger. Split the rest of the 0.1 M KOH between the second
and third Teflon impingers. The next Teflon impinger is left dry. Place
a preweighed 200-to 400-g portion of indicating silica gel in the final
glass impinger. (For sampling periods in excess of two hours, or for high
moisture sites, 400-g of silica gel is recommended). Retain reagent
blanks of the 0.1 M KOH equal to the volumes used with the field samples.
7.1.5 Leak-Check Procedures: Follow the leak-check procedures given
in Method 5. Section 4.1.4.1 (Pretest Leak-Check), Section 4.1.4.2 (Leak-
Checks during the Sample Run), and Section 4.1.4.3 (Post-Test Leak-
Checks).
7.1.6 Sampling Train Operation: Follow the procedures given in
Method 5, Section 4.1.5. The sampling train should be iced down with
water and ice to insure heat transfer with the Teflon impingers.
NOTE: If the gas to be sampled is above 200°F, it may be necessary
to wrap three or four feet. If the Teflon sample and recirculating
lines inside the ice bath to keep the recirculated reagent cool
enough so it does not turn to steam.
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For each run, record the data required on a data sheet such as the
one shown in Figure 5-2 of Method 5. At the end of the sampling run,
determine the pH of the reagent in the first impinger using a pH indicator
strip. The pH of the solution shall be greater than 8.5. If the pH is
not above 8.5, discard the solution. Prepare a clean sampling train as
described above using 0.5 M KOH instead of 0.1 M KOH, as noted in Section
5.2.2. Leak-check and operate the sampling train as described above.
Repeat the sampling run.
7.1.7 Calculation of Percent Isokinetic: Same as Method 5, Section
4.1.6.
7.2 Post-test Nitrogen Purge. The nitrogen purge is used as a safeguard
against the conversion of hexavalent chromium to the trivalent oxidation state.
The purge is effective in the removal of S02 from the impinger contents. Attach
the nitrogen purge line to the input of the impinger train. Check to insure the
output of the impinger train is open, and that the recirculating line is capped
off. Open the nitrogen gas flow slowly and adjust the delivery rate to 10 L/min.
Check the recirculating line to insure that the pressure is not forcing the
impinger reagent out through this line. Continue the purge under these
conditions for one-half hour periodically checking the flow rate.
7.3 Sample Recovery: Begin cleanup procedures as soon as the train
assembly has been purged at the end of the sampling run. The probe assembly may
be disconnected from the sample train prior to sample purging. The probe
assembly should be allowed to cool prior to sample recovery. Disconnect the
umbilical cord from the sample train. When the probe assembly can be safely
handled, wipe off all external particulate matter near the tip of the nozzle, and
cap the nozzle prior to transporting the sample train to a clean up area that is
clean and protected from the wind and other potential causes of contamination or
loss of sample. Inspect the train before and during disassembly and note any
abnormal conditions.
7.3.1 Container No. 1 (Impingers 1 through 3): Disconnect the first
impinger form the second impinger and disconnect the recirculation line
form the aspirator or peristaltic pump. Drain the Teflon impingers into
a precleaned graduated cylinder or tare-weighted precleaned polyethylene
sample container and measure the volume of the liquid to within 1 ml or 1
gm. Record the volume of liquid present as this information is required
to calculate the moisture content of the flue gas sample. If necessary,
transfer the sample from the graduated cylinder to a precleaned
polyethylene sample container. With reagent water, rinse four times the
insides of the glass nozzle, the aspirator, the sample and recirculation
lines, the impingers, and the connecting tubing, and combine the rinses
with the impinger solution in the sample container.
7.3.2 Container No. 2 (HN03 rinse optional for total chromium):
With 0.1 M HN03, rinse three times the entire train assembly, from the
nozzle to the fourth impinger, and combine the rinses into a separate
precleaned polyethylene sample container for possible total chromium
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analysis. Repeat the rinse procedure a final time with reagent water, and
discard the water rinses. Mark the Height of the fluid level on the
container or, alternatively if a balance is available, weigh the container
and record the weight to permit determination of any leakage during
transport. Label the container clearly to identify its contents.
7.3.3 Container No. 3 (Silica Gel): Note the color of the
indicating silica gel to determine if it has been completely spent.
Quantitatively transfer the silica gel from its impinger to the original
container, and seal the container. A funnel and a rubber policeman may be
used to aid in the transfer. The small amount of particulate that may
adhere to the impinger wall need not be removed. Do not use water or
other liquids to transfer the silica gel. Alternatively, if a balance is
available in the field, record the weight of the spent silica gel (or the
silica gel plus impinger) to the nearest 0.5 g.
7.3.4 Container No 4 (0.1 M KOH Blank): Once during each field
test, place a volume of reagent equal to the volume placed in the sample
train into a precleaned polyethylene sample container, and seal the
container. Mark the height of the fluid level on the container or,
alternatively if a balance is available, weigh the container and record
the weight to permit determination of any leakage during transport. Label
the container clearly to identify its contents.
7.3.5 Container No. 5 (reagent water Blank): Once during each field
test, place a volume of reagent water equal to the volume employed to
rinse the sample train into a precleaned polyethylene sample container,
and seal the container. Mark the height of the fluid level on the
container or, alternatively if a balance is available, weigh the container
and record the weight to permit determination of any leakage during
transport. Label the container clearly to identify its contents.
7.3.6 Container No. 6 (0.1 M HN03 Blank): Once during each field
test if total chromium is to be determined, place a volume of 0.1 M HN03
reagent equal to the volume employed to rinse the sample train into a
precleaned polyethylene sample container, and seal the container. Mark
the height of the fluid level on the container or, alternatively if a
balance is available, weigh the container and record the weight to permit
determination of any leakage during transport. Label the container
clearly to identify its contents.
7.4 Sample Preparation: For determination of Cr+6, the sample should be
filtered immediately following recovery to remove any insoluble matter. Nitrogen
gas may be used as a pressure assist to the filtration process (see Figure Cr -
4). Filter the entire impinger sample through a 0.45 micrometer acetate filter
(or equivalent), and collect the filtrate in a 1000-mL graduated cylinder. Rinse
the sample container with reagent water three separate times and pass these
rinses through the filter, and add the rinses to the sample filtrate. Rinse the
Teflon reservoir with reagent water three separate times and pass these rinses
through the filter, and add the rinses to the sample. Determine the final volume
0061 - 11 Revision 0
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of the filtrate and rinses and return them to the rinsed polyethylene sample
container. Label the container clearly to identify its contents. Rinse the
Teflon reservoir once with 0.1 M HN03 and once with reagent water and discard
these rinses. If total chromium is to be determined, quantitatively recover the
filter and residue and place them in a vial. (The acetate filter may be digested
with 5 ml of 70% nitric acid; this digestion solution may then be diluted with
reagent water for total chromium analysis by inductively coupled plasma atomic
emission or graphite furnace atomic absorption spectrometric methods.)
NOTE: If the source has a large amount of particulate in the
effluent stream, testing teams may wish to filter the sample twice,
once through a 2-5 micrometer filter, then through the 0.45
micrometer filter.
7.4.1 Container No. 2 (HN03 rinse, optional for total chromium):
This sample shall be analyzed in accordance with the selected procedure
for total chromium analysis. At a minimum, the sample should be subjected
to a digestion procedure sufficient to solubilize all chromium present.
7.4.2 Container 3 (Silica Gel): Weigh the spent silica gel to the
nearest 0.5 g using a balance. (This step may be conducted in the field.)
7.5 Sample Analysis: The Cr+6 content of the sample filtrate is
determined by ion chromatography coupled with a post column reactor (IC/PCR).
Method 7199 should be used for this analysis. To increase sensitivity for trace
levels of chromium, a preconcentration system is also used in conjuction with the
IC/PCR. Prior to preconcentration and/or analysis, all field samples will be
filtered through a 0.45 urn filter. This fitration should be conducted just
prior to sample injection/analysis.
7.5.1 Preconcentration: The preconcentration is accomplished
by selectively retaining the analyte on a solid absorbent, followed by
removal of the analyte from the absorbent.
Refer to Section 7.0 of Method 7199 for the proper sample analysis protocol.
7.6 Calculations
7.6.1 Dry Gas Volume: Using the data form the test, calculate
Vm(std), the dry gas sample volume at standard conditions as outlined in
Section 6.3 of Method 5.
7.6.2 Volume of Water Vapor and Moisture Content: Using the data
form the test, calculate Vw(8td) and Bws, the volume of water vapor and the
moisture content of the stack gas, respectively, using Equations 5-2 and
5-3 of Method 5.
7.6.3 Stack Gas Velocity: Using the data form the test and
Equations 2-9 of Method 2, calculate the average stack gas velocity.
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7.6.4 Total ug Cr+6 Per Sample. Calculate as described below:
m = (S-B) x Vls x d
Where:
m = Mass of Cr+e in the sample, ug,
S = Concentration of Sample, ug Cr+6/mL,
B = Concentration of blank, ug Cr+6/mL,
V|8 = Volume of sample after filtration, ml, and,
d = Dilution factor (1 if not diluted).
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for the appropriate quality control procedures.
9.0 METHOD PERFORMANCE
9.1 Sensitivity: A minimum detection limit of 8 ng/dscm with a 3 dscm
gas sample can be achieved by preconcentration (0.05 ppb in solution). Follow
instrument manufacturers instructions for sample preconcentration.
9.2 Precision: The precision of the IC/PCR with sample preconcentration
is 5 to 10 percent. The overall precision for sewage sludge incinerators
emitting 120 ng/dscm of Cr+e and 3.5 ug/dscm of total chromium is 25% and 9% for
Cr+6 and total chromium, respectively; for hazardous waste incinerators emitting
300 ng/dscm of Cr+e it is 20%.
9.3 Refer to Section 9.0 of Method 7199 for additional analytical method
performance information.
10.0 REFERENCES
1. Carver, Anna C.; Laboratory and Field Evaluation of the Methodology for
Determining Hexavalent Chromium Emissions from Stationary Sources. EPA No.
600/3-92/052, February 1992.
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METHOD 0061
DETERMINATION OF HEXAVALENT CHROMIUM EMISSIONS
FROM STATIONARY SOURCES
71.1 Calibrate sample train
components according to
Section 5 of Method S.
I
7. 1 2 Decontaminate all sample
train components and containers.
Allow components to air dry
i
7 1 4 Set up sample collection
train, connect Teflon impingers
and glass impmger in series,
add reagents.
i
Place 200 - 400 grams of
preweighted silica gel in final
glass impmger
I
7.1 5 Perform teak-chec*
procedures given m Section 4
of Method S.
I
7 1 .6 Perform sampling run
following procedures given in
Mettod 5, Section 4.
At the end of the sampling run
check the pH of the first Impmger
Yas
Discard solution, dean sampling
equipment, add 0 SN KOH to
impingers instead of 0 1 N KOH.
Leak check system and repeat
sampling run
7 1 7 Calculate Percent IsoMnedc.
7 2 Attach nitrogen purge to
input of sampling tram, purge
system lor 30 mm at lOL/mm.
I
7 3 Disconnect sample tram and
move to cleanup and sample
recovery area.
7 3 1 Disconnect impingers,
transfer and measure volume of
liquid m impingers 1 - 3, rinse
sampling components and combine
with impmger solutions. Label
as container No. 1
7 3.2 (Optional for total chromium)
Rinse entire sampling tram with
0 1 N HNQ up to fourth impmger,
combine nnses, labiei as
container No. 2.
733 Quantitatively transfer silica
gel from last impinger to original
container If possible, weigh
assembly
i
73.4-7 3.6 Collect volumes of
reagents equivalent to volumes
used dunng the sampling for
blank analysis
7 4 Sample preparation' Cr*s
Filter entire impmger sample
through 0 45um acetate filter
Rinse container and filtration unit.
combine with filtrate Determine
final volume
0061 - 14
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METHOD 0061
DETERMINATION OF HEXAVALENT CHROMIUM EMISSIONS
FROM STATIONARY SOURCES (Cont.)
Recover filter and residue,
digest with 5 ml 70% HNO3,
analyze by ICP/AA
7 6 Sample Analysis
Analyze sample filtrate for
Cr"6 by Method 7199
(Ion Chromatography)
I
76.1 - 7 6 4 Calculate total
ug Cr*6 per sample (7 6.4)
0061 - 15
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METHOD 6010B
INDUCTIVELY COUPLED .PLASMA-ATOMIC EMISSION SPECTROSCOPY
1.0 SCOPE AND APPLICATION
1.1 Inductively coupled plasma-atomic emission spectroscopy (ICP-AES)
determines trace elements, including metals, in solution. The method is
applicable to all of the elements listed in Table 1. All matrices, including
ground water, aqueous samples, TCLP and EP extracts, industrial and organic
wastes, soils, sludges, sediments, and other solid wastes, require digestion
prior to analysis. Refer to Chapter Three for the appropriate digestion
procedures.
1.2 Table 1 lists the elements for which this method is applicable.
Detection limits, sensitivity, and the optimum and linear concentration ranges
of the elements can vary with the wavelength, spectrometer, matrix and operating
conditions. Table 1 lists the recommended analytical wavelengths and estimated
instrumental detection limits for the elements in clean aqueous sample matrices.
The detection limit data may be used to estimate instrument and method
performance for other sample matrices.
1.3 Users of the method should state the data quality objectives prior
to analysis and must document and have on file the required initial demonstration
performance data described in the following sections prior to using the method
for analysis.
1.4 Use of this method is restricted to spectroscopists who are
knowledgeable in the correction of spectral, chemical, and physical interferences
described in this method.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis, samples must be solubilized or digested using
appropriate Sample Preparation Methods (e.g. Chapter Three).
2.2 This method describes multielemental determinations by ICP-AES using
sequential or simultaneous instruments. The instrument measures characteristic
emission spectra by optical spectrometry. Samples are nebulized and the
resulting aerosol is transported to the plasma torch. Element-specific emission
spectra are produced by a radio-frequency inductively coupled plasma. The
spectra are dispersed by a grating spectrometer, and the intensities of the
emission lines are monitored by photosensitive devices such as diode arrays or
photomultiplier tube(s). Background correction is required for trace element
determination. Background must be measured adjacent to analyte lines on samples
during analysis. The position selected for the background-intensity measurement,
on either or both sides of the analytical line, will be determined by the
complexity of the spectrum adjacent to the analyte line. The position used should
be as free as possible from spectral interference and should reflect the same
change in background intensity as occurs at the analyte wavelength measured.
Background correction is not required in cases of line broadening where a
6010B - 1 Revision 2
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background correction measurement would actually degrade the analytical result.
The possibility of additional interferences named in Section 3.0 should also be
recognized and appropriate corrections made; tests for their presence are
described in Step 8.5.
3.0 INTERFERENCES
3.1 Spectral interferences are caused by background emission from
continuous or recombination phenomena, stray light from the line emission of high
concentration elements, overlap of a spectral line from another element, or
unresolved overlap of molecular band spectra.
3.1.1 Background emission and stray light can usually be
compensated for by subtracting the background emission determined by
measurements adjacent to the analyte wavelength peak. Spectral scans of
samples or single element solutions in the analyte regions may indicate
when alternate wavelengths are desirable because of severe spectral
interference. These scans will also show whether the most appropriate
estimate of the background emission is provided by an interpolation from
measurements on both sides of the wavelength peak or by measured emission
on only one side. The locations selected for the measurement of
background intensity will be determined by the complexity of the spectrum
adjacent to the wavelength peak. The locations used for routine
measurement must be free of off-line spectral interference (interelement
or molecular) or adequately corrected to reflect the same change in
background intensity as occurs at the wavelength peak.
3.1.2 Spectral overlaps may be avoided by using an alternate
wavelength or can be compensated by equations that correct for
interelement contributions. Instruments that use equations for
interelement correction require the interfering elements be analyzed at
the same time as the element of interest. When operative and uncorrected,
interferences will produce false positive determinations and be reported
as analyte concentrations. More extensive information on interferant
effects at various wavelengths and resolutions is available in reference
wavelength tables and books. Users may apply interelement correction
factors determined on their instruments with tested concentration ranges
to compensate (off line or on line) for the effects of interfering
elements. Some potential spectral interferences observed for the
recommended wavelengths are given in Table 2. The interferences listed
are only those that occur between method analytes. Only interferences of
a direct overlap nature are listed. These overlaps were observed with a
single instrument having a working resolution of 0.035 nm.
3.1.3 When using interelement correction factors, the interference
is expressed as analyte concentration equivalents (i.e. false analyte
concentrations) arising from 100 mg/L of the interference element. For
example, assume that As is to be determined (at 193.696 nm) in a sample
containing approximately 10 mg/L of Al. According to Table 2, 100 mg/L of
Al would yield a false signal for As equivalent to approximately 1.3 mg/L.
6010B - 2 Revision 2
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Therefore, the presence of 10 mg/L of Al would result in a false signal
for As equivalent to approximately 0.13 mg/L. The user is cautioned that
other instruments may exhibit somewhat different levels of interference
than those shown in Table 2. The interference effects must be evaluated
for each individual instrument since the intensities will vary.
3.1.4 Interelement corrections will vary for the same emission line
among instruments because of differences in resolution, as determined by
the grating, the entrance and exit slit widths, and by the order of
dispersion. Interelement corrections will also vary depending upon the
choice of background correction points. Selecting a background correction
point where an interfering emission line may appear should be avoided when
practical. Interelement corrections that constitute a major portion of an
emission signal may not yield accurate data. Users should not forget that
some samples may contain uncommon elements that could contribute spectral
interferences.
3.1.5 The interference effects must be evaluated for each
individual instrument whether configured as a sequential or simultaneous
instrument. For each instrument, intensities will vary not only with
optical resolution but also with operating conditions (such as power,
viewing height and argon flow rate). When using the recommended
wavelengths, the analyst is required to determine and document for each
wavelength the effect from referenced interferences (Table 2) as well as
any other suspected interferences that may be specific to the instrument
or matrix. The analyst is required to utilize a computer routine for
automatic correction on all analyses.
3.1.6 To determine the appropriate location for off-line background
correction, the user must scan the area on either side adjacent to the
wavelength and record the apparent emission intensity from all other
method analytes. This spectral information must be documented and kept on
file. The location selected for background correction must be either free
of off-line interelement spectral interference or a computer routine must
be used for automatic correction on all determinations. If a wavelength
other than the recommended wavelength is used, the analyst must determine
and document both the overlapping and nearby spectral interference effects
from all method analytes and common elements and provide for their
automatic correction on all analyses. Tests to determine spectral
interference must be done using analyte concentrations that will
adequately describe the interference. Normally, 100 mg/L single element
solutions are sufficient; however, for analytes such as iron that may be
found at high concentration, a more appropriate test would be to use a
concentration near the upper analytical range limit.
3.1.7 Users of sequential instruments must verify the absence of
spectral interference by scanning over a range of 0.5 nm centered on the
wavelength of interest for several samples. The range for lead, for
example, would be from 220.6 to 220.1 nm. This procedure must be repeated
whenever a new matrix is to be analyzed and when a new calibration curve
is to be prepared. Samples that show an elevated background emission
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across the range may be background corrected by applying a correction
factor equal to the emission adjacent to the line or at two points on
either side of the line and interpolating between them. An alternate
wavelength that does not exhibit a background shift or spectral overlap
may also be used.
3.1.8 If the correction routine is operating properly, the
determined apparent analyte(s) concentration from analysis of each
interference solution should fall within a specific concentration range
around the calibration blank. The concentration range is calculated by
multiplying the concentration of the interfering element by the value of
the correction factor being tested and divided by 10. If after the
subtraction of the calibration blank the apparent analyte concentration
outside of this range in either a positive or negative direction, a change
in the correction factor of more than 10% should be suspected. The cause
of the change should be determined and corrected and the correction factor
updated. The interference check solutions should be analyzed more than
once to confirm a change has occurred. Adequate rinse time between
solutions and before analysis of the calibration blank will assist in the
confirmation.
3.1.9 When interelement corrections are applied, their accuracy
should be verified, daily, by analyzing spectral interference check
solutions. If the correction factors tested on a daily basis are found to
be within the 10% criteria for 5 consecutive days, the required
verification frequency of those factors in compliance may be extended to
a weekly basis. Also, if the nature of the samples analyzed is such they
do not contain concentrations of the interfering elements at the 10 mg/L
level, daily verification is not required. All interelement spectral
correction factors must be verified every six months and updated, if
necessary. Standard solution should be inspected to ensure that there is
no contamination that may be perceived as a spectral interference.
3.1.10 When interelement corrections are not used, verification of
absence of interferences is required.
3.1.10.1 One method is to use a computer software routine for
comparing the determinative data to limits files for notifying the
analyst when an interfering element is detected in the sample at a
concentration that will produce either an apparent false positive
concentration, (i.e., greater than) the analyte instrument detection
limit, or false negative analyte concentration, (i.e., less than the
lower control limit of the calibration blank defined for a 99%
confidence interval).
3.1.10.2 Another method is to analyze an Interference Check
Solution(s) which contains similar concentrations of the major
components of the samples (>10 mg/L) on a continuing basis to verify
the absence of effects at the wavelengths selected. These data must
be kept on file with the sample analysis data. If the check
solution confirms an operative interference that is > 10% of the
6010B - 4 Revision 2
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analyte concentration, the analyte must be determined using (1)
analytical and background correction wavelengths (or spectral
regions) free of the interference, (2) by an alternative wavelength,
or (3) by another documented test procedure.
3.2 Physical interferences are effects associated with the sample
nebulization and transport processes. Changes in viscosity and surface tension
can cause significant inaccuracies, especially in samples containing high
dissolved solids or high acid concentrations. If physical interferences are
present, they must be reduced by diluting the sample or by using a peristaltic
pump, by using an internal standard or by using a high solids nebulizer. Another
problem that can occur with high dissolved solids is salt buildup at the tip of
the nebulizer, affecting aerosol flow rate and causing instrumental drift. The
problem can be controlled by wetting the argon prior to nebulization, using a tip
washer, using a high solids nebulizer or diluting the sample. Also, it has been
reported that better control of the argon flow rate, especially to the nebulizer,
improves instrument performance; this is accomplished with the use of mass flow
controllers.
3.3 Chemical interferences include molecular compound formation,
ionization effects, and solute vaporization effects. Normally, these effects are
not significant with the ICP technique, but if observed, can be minimized by
careful selection of operating conditions (incident power, observation position,
and so forth), by buffering of the sample, by matrix matching, and by standard
addition procedures. Chemical interferences are highly dependent on matrix type
and the specific analyte element.
3.4 Memory interferences result when analytes in a previous sample
contribute to the signals measured in a new sample. Memory effects can result
from sample deposition on the uptake tubing to the nebulizer and from the build
up of sample material in the plasma torch and spray chamber. The site where
these effects occur is dependent on the element and can be minimized by flushing
the system with a rinse blank between samples. The possibility of memory
interferences should be recognized within an analytical run and suitable rinse
times should be used to reduce them. The rinse times necessary for a particular
element must be estimated prior to analysis. This may be achieved by aspirating
a standard containing elements at a concentration ten times the usual amount or
at the top of the linear dynamic range. The aspiration time for this sample
should be the same as a normal sample analysis period, followed by analysis of
the rinse blank at designated intervals. The length of time required to reduce
analyte signals to within a factor of two of the method detection limit should
be noted. Until the required rinse time is established, this method requires a
rinse period of at least 60 seconds between samples and standards. If a memory
interference is suspected, the sample must be reanalyzed after a rinse period of
sufficient length.
3.5 Users are advised that high salt concentrations can cause analyte
signal suppressions and confuse interference tests. If the instrument does not
display negative values, fortify the interference check solution with the
elements of interest at 0.5 to 1 mg/L and circumscribe the added standard
concentration accordingly, with the appropriate 10% concentration range for
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testing. In the absence of measurable analyte, overcorrection could go
undetected if a negative value is reported as zero.
3.6 The dashes in Table 2 indicate that no measurable interferences were
observed even at higher interferant concentrations. Generally, interferences
were discernible if they produced peaks, or background shifts, corresponding to
2 to 5% of the peaks generated by the analyte concentrations.
4.0 APPARATUS AND MATERIALS
4.1 Inductively coupled argon plasma emission spectrometer:
4.1.1 Computer-controlled emission spectrometer with background
correction.
4.1.2 Radio-frequency generator compliant with FCC regulations.
4.1.3 Optional mass flow controller for argon gas supply.
4.1.4 Optional peristaltic pump.
4.1.5 Optional Autosampler.
4.1.6 Argon gas supply - high purity.
4.2 Operating conditions - The analyst should follow the instructions
provided by the instrument manufacturer.
4.2.1 Before using this procedure to analyze samples, there must be
data available documenting initial demonstration of performance. The
required data document the selection criteria of background correction
points; analytical dynamic ranges, the applicable equations, and the upper
limits of those ranges; the method and instrument detection limits; and
the determination and verification of interelement correction factors or
other routines for correcting spectral interferences. This data must be
generated using the same instrument, operating conditions and calibration
routine to be used for sample analysis. These documented data must be
kept on file and be available for review by the data user or auditor.
4.2.1 Specific wavelengths are listed in Table 1. Other
wavelengths may be substituted if they can provide the needed sensitivity
and are corrected for spectral interference. Because of differences among
various makes and models of spectrometers, specific instrument operating
conditions cannot be provided. The instrument and operating conditions
utilized for determination must be capable of providing data of acceptable
quality to the program and data user. The analyst should follow the
instructions provided by the instrument manufacturer unless other
conditions provide similar or better performance for a task. Operating
conditions for aqueous solutions usually vary from 1100 to 1200 watts
forward power, 14 to 18 mm viewing height, 15 to 19 liters/min argon
coolant flow, 0.6 to 1.5 L/min argon aerosol flow, 1 to 1.8 mL/min sample
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pumping rate with a 1 minute preflush time and measurement time near 1
second per wavelength peak for sequential instruments and 10 seconds per
sample for simultaneous instruments. Reproduction of the Cu/Mn intensity
ratio at 324.754 nm and 257.610 nm respectively, by adjusting the argon
aerosol flow has been recommended as a way to achieve repeatable
interference correction factors.
4.2.2 The plasma operating conditions need to be optimized prior to
use of the instrument. The following procedure is recommended. The
purpose of plasma optimization is to provide a maximum signal to
background ratio for some of the least sensitive elements in the
analytical array. The use of a mass flow controller to regulate the
nebulizer gas flow rate greatly facilitates the procedure.
4.2.2.1 Ignite the plasma and select an appropriate incident
RF power. Allow the instrument to become thermally stable before
beginning, about 30 to 60 minutes of operation. While aspirating a
1000 ug/L solution of yttrium, follow the instrument manufacturer's
instructions and adjust the aerosol carrier gas flow rate through
the nebulizer so a definitive blue emission region of the plasma
extends approximately from 5 to 20 mm above the top of the load
coil. Record the nebulizer gas flow rate or pressure setting for
future reference. The yttrium solution can also be used for coarse
optical alignment of the torch by observing the overlay of the blue
light over the entrance slit to the detectors.
4.2.2.2 After establishing the nebulizer gas flow rate,
determine the solution uptake rate of the nebulizer in mL/min by
aspirating a known volume of calibration blank for a period of at
least three minutes. Divide the volume aspirated by the time in
minutes and record the uptake rate; set the peristaltic pump to
deliver the rate in a steady even flow.
4.2.2.3 Profile the instrument to align it optically as it
will be used during analysis. The following procedure can be used
for both horizontal and vertical optimization, but is written for
vertical. Aspirate a solution containing 10 ug/L of several
selected elements. These elements can be As, Se, Tl or Pb as the
least sensitive of the elements and most needing to be optimize or
others representing analytical judgement (V, Cr, Cu, Li and Mn are
also used with success). Collect intensity data at the wavelength
peak for each analyte at 1 mm intervals from 14 to 18 mm above the
load coil. (This region of the plasma is referred to as the
analytical zone.) Repeat the process using the calibration blank.
Determine the net signal to blank intensity ratio for each analyte
for each viewing height setting. Choose the height for viewing the
plasma that provides the best net intensity ratios for the elements
analyzed or the highest intensity ratio for the least sensitive
element.
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4.2.2.4 The instrument operating condition finally selected
as being optimum should provide the lowest reliable instrument
detection limits and method detection limits.
4.2.2.5 If either the instrument operating conditions, such
as incident power or nebulizer gas flow rate are changed, or a new
torch injector tube with a different orifice internal diameter is
installed, the plasma and viewing height should be re-optimized.
4.2.2.6 After completing the initial optimization of
operating conditions, but before analyzing samples, the laboratory
must establish and initially verify an interelement spectral
interference correction routine to be used during sample analysis.
A general description concerning spectral interference and the
analytical requirements for background correction in particular are
discussed in the section on interferences. To determine the
appropriate location for background correction and to establish the
interelement interference correction routine, repeated spectral
scans around the analytical wavelength and repeated analyses of
single elements solutions may be required. Criteria for determining
an interelement spectral interference is an apparent positive or
negative concentration for the analyte that is outside the 3 sigma
control limits of the calibration blank for the analyte. The upper
control limit is the analyte instrument detection limit. Once
established the entire routine must be periodically verified every
six months. Only a portion of the correction routine must be
verified more frequently or on a daily basis. Initial and periodic
verification of the routine should be kept on file. Special cases
where continual verification is required are described elsewhere.
4.2.2.7 Before daily calibration and after the instrument
warmup period, the nebulizer gas flow rate must be reset to the
determined optimized flow. If a mass flow controller is being used,
it should be set to the recorded optimized flow rate, In order to
maintain valid spectral interelement correction routines the
nebulizer gas flow rate should be the same (< 2% change) from day to
day.
4.2.3 For operation with organic solvents, use of the auxiliary
argon inlet is recommended, as are solvent-resistant tubing, increased
plasma (coolant) argon flow, decreased nebulizer flow, and increased RF
power to obtain stable operation and precise measurements.
4.2.4 Sensitivity, instrumental detection limit, precision, linear
dynamic range, and interference effects must be established for each
individual analyte line on each particular instrument. All measurements
must be within the instrument linear range where the correction factors
are valid.
4.2.4.1 Method detection limits must be established for all
wavelengths utilized, using fortified matrices. An MDL must be
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established by the laboratory for each type of matrix commonly
analyzed. Refer to Chapter One for guidance on determining MDLs.
4.2.5.2 Determination of limits using reagent water represent
a best case situation and do not represent possible matrix effects
of real world samples.
4.2.5.3 If additional confirmation is desired, reanalyze the
seven replicate aliquots on two more non consecutive days and again
calculate the method detection limit values for each day. An
average of the three values for each analyte may provide for a more
appropriate estimate. Successful analysis of samples with added
analytes or using method of standard additions can give confidence
in the method detection limit values determined in reagent water.
4.2.5.4 The upper limit of the linear dynamic range must be
established for each wavelength utilized by determining the signal
responses from a minimum for three, preferably five, different
concentration standards across the range. One of these should be
near the upper limit of the range. The ranges which may be used for
the analysis of samples should be judged by the analyst from the
resulting data. The data, calculations and rationale for the choice
of range made should be documented and kept on file. The upper
range limit should be an observed signal no more than 10% below the
level extrapolated from lower standards. Determined analyte
concentrations that are above the upper range limit must be diluted
and reanalyzed. The analyst should also be aware that if an
interelement correction from an analyte above the linear range
exists, a second analyte where the interelement correction has been
applied may be inaccurately reported. New dynamic ranges should be
determined whenever there is a significant change in instrument
response. For those analytes that periodically approach the upper
limit, the range should be checked every six months. For those
analytes that are known interferences, and are present at above the
linear range, the analyst should ensure that the interelement
correction has not been inaccurately applied.
NOTE: Many of the alkali and alkaline earth metals have non-
linear response curves due to ionization and self absorption
effects. These curves may be used if the instrument allows;
however the effective range must be checked and the second
order curve fit should have a correlation coefficient of 0.999
or better. Third order fits are not acceptable. These non-
linear response curves should be revalidated and recalculated
every six months. These curves are much more sensitive to
changes in operating conditions than the linear lines and
should be checked whenever there have been a moderate
equipment changes.
4.2.5 The analyst must (1) verify that the instrument configuration
and operating conditions satisfy the analytical requirements and (2)
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maintain quality control data confirming instrument performance and
analytical results.
4.3 Volumetric flasks of suitable precision and accuracy.
4.4 Volumetric pipets of suitable precision and accuracy.
5.0 REAGENTS
5.1 Reagent or trace metals grade chemicals shall be used in all tests.
Unless otherwise indicated, it is intended that all reagents shall conform to the
specifications of the Committee on Analytical Reagents of the American Chemical
Society, where such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination. If the
purity of a reagent is in question analyze for contamination. If the
concentration of the contamination is less than the MDL then the reagent is
acceptable.
5.1.1 Hydrochloric acid (cone), HC1.
5.1.2 Hydrochloric acid (1:1), HC1. Add 500 ml concentrated HC1 to
400 ml water and dilute to 1 liter in an appropriately sized beaker.
5.1.3 Nitric acid (cone), HN03.
5.1.4 Nitric acid (1:1), HN03. Add 500 ml concentrated HN03 to
400 ml water and dilute to 1 liter in an appropriately sized beaker.
5.2 Reagent Water. All references to water in the method refer to reagent
water unless otherwise specified. Reagent water will be interference free.
Refer to Chapter One for a definition of reagent water.
5.3 Standard stock solutions may be purchased or prepared from ultra-
high purity grade chemicals or metals (99.99 to 99.999% pure). All salts must
be dried for 1 hour at 105°C, unless otherwise specified.
Note: This section does not apply when analyzing samples that have been
prepared by Method 3040.
CAUTION: Many metal salts are extremely toxic if inhaled or swallowed.
Wash hands thoroughly after handling.
Typical stock solution preparation procedures follow. Concentrations are
calculated based upon the weight of pure metal added, or with the use of the
element fraction and the weight of the metal salt added.
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Metal
Concentration (pp.) .
Metal salts
Concentration (pp.) . «"<"* '
(L)
5.3.1 Aluminum solution, stock, 1 mL = 1000 ug Al : Dissolve
1.000 g of aluminum metal, weighed accurately to at least four significant
figures, in an acid mixture of 4.0 ml of (1:1) HC1 and 1.0 ml of
concentrated HN03 in a beaker. Warm beaker slowly to effect solution. When
dissolution is complete, transfer solution quantitatively to a 1-liter
flask, add an additional 10.0 ml of (1:1) HC1 and dilute to volume with
reagent water.
NOTE: Weight of analyte is expressed to four significant
figures for consistency with the weights below because rounding to two decimal
places can contribute up to 4 % error for some of the compounds.
5.3.2 Antimony solution, stock, 1 ml = 1000 ug Sb: Dissolve
2.6673 g K(SbO)C4H406 (element fraction Sb = 0.3749), weighed accurately
to at least four significant figures, in water, add 10 ml (1:1) HC1 , and
dilute to volume in a 1,000 ml volumetric flask with water.
5.3.3 Arsenic solution, stock, 1 mL = 1000 ug As: Dissolve 1.3203
g of As203 (element fraction As = 0.7574), weighed accurately to at least
four significant figures, in 100 ml of water containing 0.4 g NaOH.
Acidify the solution with 2 ml concentrated HN03 and dilute to volume in
a 1,000 mL volumetric flask with water.
5.3.4 Barium solution, stock, 1 mL = 1000 ug Ba: Dissolve 1.5163 g
BaCl2 (element fraction Ba = 0.6595), dried at 250°C for 2 hours, weighed
accurately to at least four significant figures, in 10 mL water with 1 mL
(1:1) HC1. Add 10.0 mL (1:1) HC1 and dilute to volume in a 1,000 mL
volumetric flask with water.
5.3.5 Beryllium solution, stock, 1 mL = 1000 ug Be: Do not dry.
Dissolve 19.6463 g BeS04 4H20 (element fraction Be = 0.0509), weighed
accurately to at least four significant figures, in water, add 10.0 mL
concentrated HN03, and dilute to volume in a 1,000 mL volumetric flask with
water.
5.3.6 Boron solution, stock, 1 mL = 1000 ug B: Do not dry.
Dissolve 5.716 g anhydrous H3B03 (B fraction = 0.1749), weighed accurately
to at least four significant figures, in reagent water and dilute in a 1-L
volumetric flask with reagent water. Transfer immediately after mixing in
a clean Teflon® bottle to minimize any leaching of boron from the glass
volumetric container. Use of a non-glass volumetric flask is recommended
to avoid boron contamination from glassware.
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5.3.7 Cadmium solution, stock, 1 mL = 1000 ug Cd: Dissolve 1.1423
g CdO (element fraction Cd = 0.8754), weighed accurately to at least four
significant figures, in a minimum amount of (1:1) HN03. Heat to increase
rate of dissolution. Add 10.0 mL concentrated HN03 and dilute to volume
in a 1,000 mL volumetric flask with water.
5.3.8 Calcium solution, stock, 1 mL = 1000 ug Ca: Suspend 2.4969 g
CaC03 (element Ca fraction = 0.4005), dried at 180°C for 1 hour before
weighing, weighed accurately to at least four significant figures, in
water and dissolve cautiously with a minimum amount of (1:1) HN03. Add
10.0 mL concentrated HN03 and dilute to volume in a 1,000 ml volumetric
flask with water.
5.3.9 Chromium solution, stock, 1 mL = 1000 ug Cr: Dissolve
1.9231 g Cr03 (element fraction Cr = 0.5200), weighed accurately to at
least four significant figures, in water. When solution is complete,
acidify with 10 mL concentrated HN03 and dilute to volume in a 1,000 mi-
volumetric flask with water.
5.3.10 Cobalt solution, stock, 1 mL = 1000 ug Co: Dissolve 1.00 g
of cobalt metal, weighed accurately to at least four significant figures,
in a minimum amount of (1:1) HN03. Add 10.0 mL (1:1) HC1 and dilute to
volume in a 1,000 mL volumetric flask with water.
5.3.11 Copper solution, stock, 1 mL = 1000 ug Cu: Dissolve 1.2564
g CuO (element fraction Cu = 0.7989), weighed accurately to at least four
significant figures), in a minimum amount of (1:1) HN03. Add 10.0 mL
concentrated HN03 and dilute to volume in a 1,000 mL volumetric flask with
water.
5.3.12 Iron solution, stock, 1 mL = 1000 ug Fe: Dissolve 1.4298 g
Fe203 (element fraction Fe = 0.6994), weighed accurately to at least four
significant figures, in a warm mixture of 20 mL (1:1) HC1 and 2 mL of
concentrated HN03. Cool, add an additional 5.0 mL of concentrated HN03,
and dilute to volume in a 1,000 mL volumetric flask with water.
5.3.13 Lead solution, stock, 1 mL = 1000 ug Pb: Dissolve 1.5985 g
Pb(N03)2 (element fraction Pb = 0.6256), weighed accurately to at least
four significant figures, in a minimum amount of (1:1) HN03. Add 10 mL
(1:1) HN03 and dilute to volume in a 1,000 mL volumetric flask with water.
5.3.14 Lithium solution, stock, 1 mL = 1000 ug Li: Dissolve
5.3248 g lithium carbonate (element fraction Li = 0.1878), weighed
accurately to at least four significant figures, in a minimum amount of
(1:1) HC1 and dilute to volume in a 1,000 mL volumetric flask with water.
5.3.15 Magnesium solution, stock, 1 mL = 1000 ug Mg: Dissolve
1.6584 g MgO (element fraction Mg = 0.6030), weighed accurately to at
least four significant figures, in a minimum amount of (1:1) HN03. Add
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10.0 ml (1:1) concentrated HN03 and dilute to volume in a 1,000 mL
volumetric flask with water.
5.3.16 Manganese solution, stock, 1 ml = 1000 ug Mn: Dissolve
1.00 g of manganese metal, weighed accurately to at least four significant
figures, in acid mixture (10 ml concentrated HC1 and 1 mL concentrated
HN03) and dilute to volume in a 1,000 ml volumetric flask with water.
5.3.17 Mercury solution, stock, 1 mL = 1000 ug Hg: Do not dry,
highly toxic element. Dissolve 1.354 g HgCl2 (Hg fraction = 0.7388) in
reagent water. Add 50.0 ml concentrated HN03 and dilute to volume in 1 1-L
volumetric flask with reagent water.
5.3.18 Molybdenum solution, stock, 1 mL = 1000 ug Mo: Dissolve
1.7325 g (NH4)6Mo7024.4H20 (element fraction Mo = 0.5772), weighed
accurately to at least four significant figures, in water and dilute to
volume in a 1,000 mL volumetric flask with water.
5.3.19 Nickel solution, stock, 1 mL = 1000 ug Ni: Dissolve 1.00 g
of nickel metal, weighed accurately to at least four significant figures,
in 10.0 mL hot concentrated HN03, cool, and dilute to volume in a 1,000 mL
volumetric flask with water.
5.3.20 Phosphate solution, stock, 1 mL = 1000 ug P: Dissolve
4.3937 g anhydrous KH2P04 (element fraction P = 0.2276), weighed accurately
to at least four significant figures, in water. Dilute to volume in a
1,000 mL volumetric flask with water.
5.3.21 Potassium solution, stock, 1 mL = 1000 ug K: Dissolve
1.9069 g KC1 (element fraction K = 0.5244) dried at 110°C, weighed
accurately to at least four significant figures, in water, and dilute to
volume in a 1,000 mL volumetric flask with water.
5.3.22 Selenium solution, stock, 1 mL = 1000 ug Se: Do not dry.
Dissolve 1.6332 g H2Se03 (element fraction Se = 0.6123), weighed accurately
to at least four significant figures, in water and dilute to volume in a
1,000 mL volumetric flask with water.
5.3.23 Silica solution, stock, 1 mL = 1000 ug Si02: Do not dry.
Dissolve 2.964 g NH4SiF6, weighed accurately to at least four significant
figures, in 200 mL (1:20) HC1 with heating at 85°C to effect dissolution.
Let solution cool and dilute to volume in a 1-L volumetric flask with
reagent water.
5.3.24 Silver solution, stock, 1 mL = 1000 ug Ag: Dissolve
1.5748 g AgN03 (element fraction Ag = 0.6350), weighed accurately to at
least four significant figures, in water and 10 mL concentrated HN03.
Dilute to volume in a 1,000 mL volumetric flask with water.
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5.3.25 Sodium solution, stock, 1 ml = 1000 ug Na: Dissolve 2.5419
g NaCl (element fraction Na = 0.3934), weighed accurately to at least four
significant figures, in water. Add 10.0 ml concentrated HN03 and dilute to
volume in a 1,000 ml volumetric flask with water.
5.3.26 Strontium solution, stock, 1 ml = 1000 ug Sr: Dissolve
2.4154 g of strontium nitrate (Sr(N03)2) (element fraction Sr = 0.4140),
weighed accurately to at least four significant figures, in a 1-liter
flask containing 10 ml of concentrated HC1 and 700 ml of water. Dilute to
volume in a 1,000 ml volumetric flask with water.
5.3.27 Thallium solution, stock, 1 ml = 1000 ug Tl: Dissolve
1.3034 g T1N03 (element fraction Tl = 0.7672), weighed accurately to at
least four significant figures, in water. Add 10.0 ml concentrated HN03 and
dilute to volume in a 1,000 ml volumetric flask with water.
5.3.28 Tin solution, stock, 1 ml = 1000 ug Sn: Dissolve 1.000 g Sn
shot, weighed accurately to at least 4 significant figures, in 200 ml
(1:1) HC1 with heating to effect dissolution. Let solution cool and
dilute with (1:1) HC1 in a 1-L volumetric flask.
5.3.29 Vanadium solution, stock, 1 ml = 1000 ug V: Dissolve
2.2957 g NH4V03 (element fraction V = 0.4356), weighed accurately to at
least four significant figures, in a minimum amount of concentrated HN03.
Heat to increase rate of dissolution. Add 10.0 ml concentrated HN03 and
dilute to volume in a 1,000 ml volumetric flask with water.
5.3.30 Zinc solution, stock, 1 ml = 1000 ug Zn: Dissolve 1.2447 g
ZnO (element fraction Zn = 0.8034), weighed accurately to at least four
significant figures, in a minimum amount of dilute HN03. Add 10.0 ml
concentrated HN03 and dilute to volume in a 1,000 ml volumetric flask with
water.
5.4 Mixed calibration standard solutions - Prepare mixed calibration
standard solutions by combining appropriate volumes of the stock solutions in
volumetric flasks (see Table 3). Add 2 ml (1:1) HN03 and 10 ml of (1:1) HCl and
dilute to 100 ml with water. Prior to preparing the mixed standards, each stock
solution should be analyzed separately to determine possible spectral
interference or the presence of impurities. Care should be taken when preparing
the mixed standards to ensure that the elements are compatible and stable
together. Transfer the mixed standard solutions to FEP fluorocarbon or
previously unused polyethylene or polypropylene bottles for storage. Fresh mixed
standards should be prepared, as needed, with the realization that concentration
can change on aging. Calibration standards must be initially verified using a
quality control sample (see Step 5.8) and monitored weekly for stability. Some
typical calibration standard combinations are listed in Table 3. All mixtures
should then be scanned using a sequential spectrometer to verify the absence of
interelement spectral interference in the recommended mixed standard solutions.
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NOTE:If the addition of silver to the recommended acid combination results
in an initial precipitation, add 15 mL of water and warm the flask until
the solution clears. Cool and dilute to 100 ml with water. For this acid
combination, the silver concentration should be limited to 2 mg/L. Silver
under these conditions is stable in a tap-water matrix for 30 days.
Higher concentrations of silver require additional HC1.
5.5 Two types of blanks are required for the analysis for samples prepared
by any method other than 3040. The calibration blank is used in establishing the
analytical curve, and the method blank is used to identify possible contamination
resulting from varying amounts of the acids used in the sample processing.
5.5.1 The calibration blank is prepared by acidifying reagent water
to the same concentrations of the acids found in the standards and
samples. Prepare a sufficient quantity to flush the system between
standards and samples.
5.5.2 The method blank must contain all of the reagents in the same
volumes as used in the processing of the samples. The method blank must
be carried through the complete procedure and contain the same acid
concentration in the final solution as the sample solution used for
analysis.
5.6 The check standard is prepared by the analyst by combining compatible
elements from a standard source different than that of the calibration standard
and at concentrations within the linear working range of the instrument (see Step
8.6.1.1 for use).
5.7 Calibration verification samples should be prepared in the same acid
matrix using the same standards used for calibration at 10 times the lowest
standard.
5.8 The interference check solution is prepared to contain known
concentrations of interfering elements that will provide an adequate test of the
correction factors. Spike the sample with the elements of interest, particularly
those with known interferences at approximate concentrations of 10 times the
instrumental detection limits. In the absence of measurable analyte,
overcorrection could go undetected because a negative value could be reported as
zero. If the particular instrument will display overcorrection as a negative
number, this spiking procedure will not be necessary.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material in Chapter Three, Inorganic Analytes,
Steps 3.1 through 3.3.
7.0 PROCEDURE
7.1 Preliminary treatment of most matrices is necessary because of the
complexity and variability of sample matrices. Groundwater samples which have
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been prefiltered and acidified will not need acid digestion. Samples which are
not digested must either use an internal standard or be matrix matched with the
standards. Solubil ization and digestion procedures are presented in Sample
Preparation Methods (Chapter Three, Inorganic Analytes).
7.2 Set up the instrument with proper operating parameters established in
Step 4.2. The instrument must be allowed to become thermally stable before
beginning (usually requiring at least 30 minutes of operation prior to
cal ibration).
7.3 Profile and calibrate the instrument according to the instrument
manufacturer's recommended procedures, using the typical mixed calibration
standard solutions described in Step 5.4. Flush the system with the calibration
blank (Step 5.5.1) between each standard or as the manufacturer recommends. (Use
the average intensity of multiple exposures for both standardization and sample
analysis to reduce random error.) The calibration curve must consist of a
minimum of a blank and a standard.
7.4 For all analytes and determinations, the laboratory must analyze a
check standard and a calibration blank immediately following daily calibration,
after every tenth sample and at the end of the sample run. The calibration
verification must be analyzed immediately following daily calibration. Analysis
of the check standard, calibration verification, and calibration blank must
verify that the instrument is within ± 10% of calibration with relative standard
deviation < 3% from replicate (minimum of two) integrations. If the calibration
cannot be verified within the specified limits, reanalyze either the calibration
verification solution or the check standard (or both). If the second analysis
confirms calibration to be outside the limits, the sample analysis must be
discontinued, the cause determined and the instrument recalibrated. All samples
following the last acceptable calibration verification solution or check standard
must be reanalyzed. The analysis data of the calibration blank, check standard,
and calibration verification solution must be kept on file with the sample
analysis data.
7.5 Flush the system with the calibration blank solution for at least
1 minute (Step 5.5.1) before the analysis of each sample (see Note to Step 7.3).
7.6 Calculations: If dilutions were performed, the appropriate factors
must be applied to sample values. All results should be reported with up to
three significant figures.
7.7 The MSA should be used if an interference is suspected or a new matrix
is encountered. When the method of standard additions is used, standards are
added at one or more levels to portions of a prepared samples. This technique
compensates for enhancement or depression of an analyte signal by a matrix. It
will not correct for additive interferences, such as contamination, interelement
interferences, or baseline shifts. This technique is valid in the linear range
when the interference effect is constant over the range, the added analyte
responds the same as the endogenous analyte, and the signal is corrected for
additive interferences. The simplest version of this technique is the single
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addition method. This procedure calls for two identical aliquots of the sample
solution to be taken. To the first aliquot, a small volume of standard is added;
while to the second aliquot, a volume of acid blank is added equal to the
standard addition. The sample concentration is calculated by: multiplying the
intensity value for the unfortified aliquot by the volume (Liters) and
concentration (mg/L or mg/Kg) of the standard addition to make the numerator; the
difference in intensities for the fortified sample and unfortified sample is
multiplied by the volume (Liters) of the sample aliquot for the denominator. The
quotient is the sample concentration.
For more than one fortified portion of the prepared sample, linear
regression analysis can be applied using a computer or calculator program to
obtain the concentration of the sample solution.
7.8 An alternative to using the method of standard additions is the
internal standard technique. Add one or more elements not in the samples and
verified not to cause an interelement spectral interference to the samples,
standards and blanks; yttrium or scandium are often used. The concentration
should be sufficient for optimum precision but not so high as to alter the salt
concentration of the matrix. The element intensity is used by the instrument as
an internal standard to ratio the analyte intensity signals for both calibration
and quantitation. This technique is very useful in overcoming matrix
interferences especially in high solids matrices.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection. All quality control measures described in Chapter One
should be followed.
8.2 Dilute and reanalyze samples that exceed the linear calibration limit
or use an alternate, less sensitive line for which quality control data is
already established.
8.3 Employ a minimum of one method blank per sample batch to determine if
contamination or any memory effects are occurring. A method blank is a volume
of reagent water carried through the same preparation process as a sample.
8.4 Analyze matrix spiked duplicate samples at a frequency of one per
matrix batch. A matrix duplicate sample is a sample brought through the entire
sample preparation and analytical process in duplicate.
8.4.1.1 The relative percent difference between matrix
duplicate determinations is to be calculated as follows:
RPD =
Dl
„ x 100
(D1 + DJ/2
where:
RPD = relative percent difference.
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DT = first sample value.
D2 = second sample value (replicate).
(A control limit of ± 20% RPD or within the documented
historical acceptance limits for each matrix shall be used for
sample values greater than ten times the instrument detection
limit.)
8.4.1.2 The spiked sample or spiked duplicate sample recovery
is to be within ± 25% of the actual value or within the documented
historical acceptance limits for each matrix.
8.5 It is recommended that whenever a new or unusual sample matrix is
encountered, a series of tests be performed prior to reporting concentration data
for analyte elements. These tests, as outlined in Steps 8.5.1 and 8.5.2, will
ensure that neither positive nor negative interferences are operating on any of
the analyte elements to distort the accuracy of the reported values.
8.5.1 Dilution Test: If the analyte concentration is sufficiently
high (minimally, a factor of 10 above the instrumental detection limit
after dilution), an analysis of a 1:4 dilution should agree within ± 10%
of the original determination. If not, a chemical or physical
interference effect should be suspected.
8.5.2 Post Digestion spike addition: An analyte spike added to a
portion of a prepared sample, or its dilution, should be recovered to
within 75% to 125% of the known value. The spike addition should produce
a minimum level of 10 times and a maximum of 100 times the instrumental
detection limit. If the spike is not recovered within the specified
limits, a matrix effect should be suspected.
CAUTION:If spectral overlap is suspected, use of computerized
compensation, an alternate wavelength, or comparison with an
alternate method is recommended.
8.6 Check the instrument standardization by analyzing appropriate QC
samples as follows.
8.6.1 Verify calibration with the Calibration Verification Standard
immediately following daily calibration. Verify calibration with the
check standard (Step 5.6) immediately following daily calibration, after
every 10 samples and at the end of the analytical run. Use a calibration
blank (Step 5.5.1) immediately following daily calibration, after every 10
samples and at the end of the analytical run.
8.6.1.1 The results of the calibration verification are to
agree within 10% of the expected value; if not, terminate the
analysis, correct the problem, and recalibrate the instrument.
6010B - 18 Revision 2
January 1995
-------
8.6.1.2 The results of the check standard are to agree within
10% of the expected value; if not, terminate the analysis, correct
the problem, and recalibrate the instrument.
8.6.1.3 The results of the calibration blank are to agree
within three standard deviations of the mean blank value. If not,
repeat the analysis two more times and average the results. If the
average is not within three standard deviations of the background
mean, terminate the analysis, correct the problem, recalibrate, and
reanalyze the previous 10 samples. If the blank is less than 1/10
the concentration of the lowest sample, the analysis need not be
terminated.
8.6.2 Verify the interelement and background correction factors at
the beginning and end of an analytical run or twice during every 8-hour
work shift, whichever is more frequent. Do this by analyzing the
interference check sample (Step 5.8). Results should be within ± 20% of
the true value.
9.0 METHOD PERFORMANCE
9.1 In an EPA round-robin Phase 1 study, seven laboratories applied the
ICP technique to acid-distilled water matrices that had been spiked with various
metal concentrates. Table 4 lists the true values, the mean reported values, and
the mean percent relative standard deviations.
9.2 Performance data for aqueous solutions and solid samples from a
multilaboratory study (9) are provided in Tables 5 and 6.
10.0 REFERENCES
1. Boumans, P.W.J.M. Line Coincidence Tables for Inductively Coupled Plasma
Atomic Emission Spectrometry, 2nd Edition. Pergamon Press, Oxford, United
Kingdom, 1984.
2. Sampling and Analysis Methods for Hazardous Waste Combustion; U.S.
Environmental Protection Agency; Air and Energy Engineering Research Laboratory,
Office of Research and Development: Research Triangle Park, NC, 1984; Prepared
by Arthur D. Little, Inc.
3. Rohrbough, W.G.; et al. Reagent Chemicals, American Chemical Society
Specifications, 7th ed.; American Chemical Society: Washington, DC, 1986.
4. 1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
5. Jones, C.L. et al. An Inter!aboratory Study of Inductively Coupled Plasma
Atomic Emission Spectroscopy Method 6010 and Digestion Method 3050. EPA-600/4-
87-032, U.S. Environmental Protection Agency, LasVegas, Nevada, 1987.
6010B - 19 Revision 2
January 1995
-------
TABLE 1
RECOMMENDED WAVELENGTHS AND ESTIMATED INSTRUMENTAL DETECTION LIMITS
Detection
Element
Aluminum
Antimony
Arsenic
Barium
Beryl! ium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Phosphorus
Potassium
Selenium
Silica (Si02)
Silver
Sodium
Strontium
Thall ium
Tin
Vanadium
Zinc
Wavelengtha(nm)
308.215
206.833
193.696
455.403
313.042
249.678x2
226.502
317.933
267.716
228.616
324.754
259.940
220.353
670.784
279.079
257.610
194.227x2
202.030
231.604x2
213.618
766.491
196.026
251.611
328.068
588.995
407.771
190.864
189.980x2
292.402
213.856x2
Estimated
Limitb (ug/L)
30
21
35
0.87
0.18
3.8
2.3
6.7
4.7
4.7
3.6
4.1
28
2.8
20
0.93
17
5.3
10
51
See note c
50
17
4.7
19
0.28
27
17
5.0
1.2
aThe wavelengths listed (where x2 indicates second order) are recommended
because of their sensitivity and overall acceptance. Other wavelengths may be
substituted (e.g. in the case of an interference) if they can provide the needed
sensitivity and are treated with the same corrective techniques for spectral
interference (see Step 3.1). In time, other elements may be added as more
information becomes available and as required.
The estimated instrumental detection limits shown are provided as a guide
for an instrumental limit. The actual method detection limits are sample
dependent and may vary as the sample matrix varies.
GHighly dependent on operating conditions and plasma position.
6010B - 20
Revision 2
January 1995
-------
TABLE 2 POTENTIAL SOIL INTERFERENCES
ANALYTE CONCENTRATION EQUIVALENTS ARISING FROM
INTERFERENCE AT THE 100-mg/L LEVEL0
Analyte
Wavelength
(nm) Al
Ca Cr
Interferanta'b
Cu Fe Mg Mn
Ni
Ti
Aluminum
Antimony
Arsenic
308.215
206.833
193.696
0.47 --
1.3 --
2.9 -- 0.08 --
0.44 --
0.21 --
0.25
1.4
0.45
1.1
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
455.403
313.042
226.502
317.933
267.716
228.616
324.754
0.04 0.05
Iron 259.940
Lead 220.353
Magnesium 279.079
Manganese 257.610
0.08
0.03
0.17 --
0.02 0.11
0.005 -- 0.01
0.03 -- -- 0.02
0.01 0.01 0.04 --
0.003 -- 0.04 --
0.005 -- -- 0.03
0.003 --
0.12 --
0.13 -- 0.25 --
0.002 0.002 --
0.03
0.15
0.05
0.03
0.04
0.02
0.07 0.12
Molybdenum 202.030 0.05 -- -- -- 0.03 --
Nickel 231.604
Selenium 196.026 0.23 -- -- -- 0.09 --
Sodium 588.995 -- -- -- -- -- -- -- -- 0.08 --
Thallium
Vanadium
Zinc
190.864 0.30 --
292.402 -- -- 0.05 -- 0.005 -- -- -- 0.02 --
213.856 -- -- -- 0.14 -- -- -- 0.29 --
aDashes indicate that no interference was observed even when interferents were
introduced at the following levels:
Al - 1000 mg/L Mg - 1000 mg/L
Ca - 1000 mg/L Mn - 200 mg/L
Cr - 200 mg/L Tl - 200 mg/L
Cu - 200 mg/L V - 200 mg/L
Fe - 1000 mg/L
The figures recorded as analyte concentrations are not the actual observed
concentrations; to obtain those figures, add the listed concentration to the
interferant figure.
Interferences will be affected by background choice and other interferences may
be present.
6010B - 21
Revision 2
January 1995
-------
TABLE 3
MIXED STANDARD SOLUTIONS
i
Solution
Elements
I
II
III
IV
V
VI
Be, Cd, Mn, Pb, Se and Zn
Ba, Co, Cu, Fe, and V
As, Mo
Al, Ca, Cr, K, Na, Ni,Li, and Sr
Ag (see Note to Step 5.4), Mg, Sb, and Tl
P
6010B - 22
Revision 2
January 1995
-------
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TABLE 5
ICP-AES PRECISION AND ACCURACY FOR AQUEOUS SOLUTIONS*
Element
Al
Sb
As
Ba
Be
Cd
Ca
Cr
Co
Cu
Fe
Pb
Mg
Mn
Mo
Ni
K
Se
Ag
Na
Tl
V
Zn
Mean
Cone.
(mg/L)
14.8
15.1
14.7
3.66
3.78
3.61
15.0
3.75
3.52
3.58
14.8
14.4
14.1
3.70
3.70
3.70
14.1
15.3
3.69
14.0
15.1
3.51
3.57
Nb
8
8
7
7
8
8
8
8
8
8
8
7
8
8
8
7
8
8
6
8
7
8
8
RSDb
(%)
6.3
7.7
6.4
3.1
5.8
7.0
7.4
8.2
5.9
5.6
5.9
5.9
6.5
4.3
6.9
5.7
6.6
7.5
9.1
4.2
8.5
6.6
8.3
Accuracy0
(% of nominal)
100
102
99
99
102
97
101
101
95
97
100
97
96
100
100
100
95
104
100
95
102
95
96
AThese performance values are independent of sample preparation because the labs
analyzed portions of the same solutions
bN = Number of measurements for mean and relative standard deviation (RSD).
°Accuracy is expressed as a percentage of the nominal value for each analyte in
acidified, multi-element solutions.
6010B - 24
Revision 2
January 1995
-------
TABLE 6
ICP-AES PRECISION AND BIAS FOR SOLID WASTE DIGESTSA
Element
Al
Sb
As
Ba
Be
Cd
Ca
Cr
Co
Cu
Fe
Pb
Mg
Mn
Mo
Ni
K
Se
Ag
Na
Tl
V
Zn
Spiked Coal Fly Ash
(NIST-SRM 1633a)
Mean
Cone. RSDb
(mg/L) Nb (%)
330
3.4
21
133
4.0
0.97
87
2.1
1.2
1.9
602
4.6
15
1.8
891
1.6
46
6.4
1.4
20
6.7
1010
2.2
8
6
8
8
8
6
6
7
6
6
8
7
8
7
8
6
8
5
3
8
4
5
6
16
73
83
8.7
57
5.7
5.6
36
21
9.7
8.8
22
15
14
19
8.1
4.2
16
17
49
22
7.5
7.6
Bias0
(%AAS)
104
96
270
101
460
101
208
106
94
118
102
94
110
104
105
91
98
73
140
130
260
100
93
Spiked Electroplating Sludge
Mean
Cone. RSDb Biasc
(mg/L) Nb (%) (%AAS)
127
5.3
5.2
1.6
0.9
2.9
954
154
1.0
156
603
25
35
5.9
1.4
9.5
51
8.7
0.75
1380
5.0
1.2
266
8
7
7
8
7
7
7
7
7
8
7
7
8
7
7
7
8
7
7
8
7
6
7
13
24
8.6
20
9.9
9.9
7.0
7.8
11
7.8
5.6
5.6
20
9.6
36
9.6
5.8
13
19
9.8
20
11
2.5
110
120
87
58
110
90
97
93
85
97
98
98
84
95
110
90
82
101
270
95
180
80
101
AThese performance values are independent of sample preparation because the labs
analyzed portions of the same digests.
bN = Number of measurements for mean and relative standard deviation (RSD).
cBias for the ICP-AES data is expressed as a percentage of atomic absorption
spectroscopy (AAS) data for the same digests.
6010B - 25
Revision 2
January 1995
-------
METHOD 6010B
INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROSCOPY
Q Start J
IT
7.1 Pretreatment
of the sample.
7.2 Instrument
setup.
7.3 Instrument
calibration.
7.4 Run calibration
verification and
calibration blank and
analyze to determine
if calibration
acceptable.
7.5 Flush system
with calibration
blank before analysis
of each sample.
I
7.6 Perform
calculations.
7.7 - 7.8 Perform any
corrective measures
necessary fo
accurate analysis.
i
6010B - 26
Revision 2
January 1995
-------
METHOD 7063
ARSENIC IN AQUEOUS SAMPLES AND EXTRACTS
BY ANODIC STRIPPING VOLTAMMETRY (ASV)
1.0 SCOPE AND APPLICATION
1.1 This method is applicable for laboratory determinations of free
dissolved arsenic in drinking water, natural surface water, seawater, and in
domestic and industrial wastewater, and in soil extracts.
1.2 Arsenic concentrations in the linear calibration range of 0.3 to 300
/ig/L may be quantified. The upper concentration range may be extended by sample
dilution, by decreasing the analyte deposition time, or by increasing the
stripping current.
1.3 The method detection limit for free arsenic is about 0.1 jug/L.
1.4 The method is equally sensitive for As(III) and As(V).
2.0 SUMMARY OF METHOD
Standards and samples are made acidic and rendered electrically conductive
by adding hydrochloric acid. Free dissolved arsenic is quantified by anodic
stripping, at a potential of +145 mV with respect to the saturated calomel
electrode (SCE), from a conditioned gold metal film deposited on a glassy carbon
electrode (GCE).
3.0 INTERFERENCES
3.1 Dissolved antimony and bismuth are positive interferences. Dissolved
copper, at concentrations greater than 1 mg/L, is also a positive interference.
3.2 Turbid samples must be filtered through a borosilicate glass filter
with 0.45-^m pores to preclude physical erosion of the GCE gold film.
3.3 Some wet deposition samples may have insufficient electrical
conductivity for proper operation of the ASV instrumentation. This problem is
obviated hy making the solutions 2 M in HCL.
3.4 When the analysis is performed according to the instructions given
below, the following ions, compounds, and sample conditions are known not to
interfere with the quantitation of arsenic; seawater salts, water-soluble organic
compounds such as sugars and tannic acid, and dissolved copper at concentrations
less than 100 times the arsenic concentration.
7063 - 1 Revision 0
January 1995
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4.0. APPARATUS AND MATERIALS
4.1 ASV instrumentation (Radiometer TraceLab, or equivalent), including
potentiostat, electrodes, stirrer, sample stand, polyethylene sample cups, and
GCE polishing powder.
4.2 Computer, as recommended by ASV instrumentation manufacturer.
4.3 Plastic syringe and a nylon syringe filter with 0.45-^m pores.
4.4 Adjustable pipetters with polyethylene tips.
4.5 pH meter or pH indicator paper.
4.6 General laboratory glassware, including beakers, graduated cyl inders,
volumetric flasks, etc.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
5.2 Reagent Water. Reagent water is interference free. All references
to water in the method refer to reagent water unless otherwise specified.
5.3 Hydrochloric acid, (concentrated 12 M).
5.3.1 Hydrochloric acid (2 M), dilute 167 ml of concentrated
hydrochloric acid to 1 liter with reagent water.
5.3.2 Hydrochloric acid (0.1 M), dilute 50 mL of the 2M hydrochloric
acid solution to 1 liter with reagent water.
5.4 Gold Stock Standard (1000 mg/L Au): Stock solutions are commercially
available as spectrophotometric standards.
5.4.1 Gold-plating solution, (50 mg/L Au dissolved in 0.1 M HCL):
prepare by diluting 2.5 mL of a 1,000 mg/L Au spectrophotometric standard
solution to 50 mL with 0.1 M HCL.
5.5 Arsenic Stock Standard (1000 mg/L of arsenic): Stock solutions are
commercially available as spectrophotometric standards.
7063 - 2 Revision 0
January 1995
-------
5.5.1 Arsenic intermediate standard solution, 1,000 jug/L arsenic:
Dilute 100 juL of the stock standard to 100 ml with 2% HN03. Prepare
weekly.
5.5.2 Arsenic Working Standards: These standards should be prepared
from the arsenic intermediate standard to be used as calibration standards
at the time of analysis. Prepare at least five working standards over the
linear calibration range of 0.3 jug/L to 300 /j,g/L by diluting appropriate
aliquots of the intermediate arsenic stock solution with 2% HN03. The
actual concentration of the working standards should cover the anticipated
range of sample concentrations.
6.0 SAMPLE HANDLING, PRESERVATION, AND HANDLING
6.1 All samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
reagent water. Plastic and glass containers are both suitable.
6.3 At the time of sampling, the sample must be acidified to a pH <2 with
nitric acid.
6.4 While samples to be analyzed for free dissolved arsenic do not
require refrigeration, they should be stored out of direct sunlight in an area
no warmer than room temperature.
7.0 PROCEDURE
7.1 Analysis of an aqueous sample for free dissolved arsenic by ASV
involves three major steps. First, the GCE electrode must be prepared for use
by plating on a thin film of gold; the gold working electrode is then
conditioned, and finally, the concentration of free arsenic in the samples are
determined.
7.2 Set up ASV instrumentation, electrodes, and computer according to the
manufacturer's recommended procedures. Enter the appropriate program and
required data parameters into the computer as directed by the instrument
software.
7.3 Before applying a gold film to the GCE, the electrode must be
thoroughly cleaned. Electrode cleanliness is checked by rinsing the GCE with
water. After gently shaking off excess water, the entire electrode should be
coated with a thin, flat, unbroken water film. If necessary, clean the GCE by
wiping it with a wet, soft paper towel, polishing it with polishing powder, and
rinsing it thoroughly with water. Keep the cleaned electrode immersed in water
or in air saturated with water vapor.
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7.4 Place 50 mL of the gold-plating solution (Sec. 5.4.1) or an
appropriate volume as recommended by the instrument manufacturer, into a beaker.
Immerse the electrodes in the gold-plating solution and initiate the GCE gold-
plating program as instructed by the instrument manufacturer.
7.5 Following deposition of GCE gold film, the electrode must be
conditioned prior to actual sample analysis. Unconditioned electrodes may
produce irreproducible arsenic peak areas. Condition electrodes by analyzing an
arsenic-free 2 M HCL reagent solution (see 5.3.1) or by analyzing a sample
adjusted to contain 2 M HCL (to a 25 ml sample, add 5 ml of concentrated HCL, mix
well), according to manufacture's recommended procedures.
7.6 When the conditioning procedure is complete, rinse the electrodes
with reagent water and store the electrodes in reagent water until ready to
analyze the calibration standards or samples.
7.7 Following the instrument manufacturer's recommended calibration
procedures, construct a calibration curve by analyzing five working calibration
standards (Sec. 5.5.2);
7.7.1 To 25 mL working standard, add 5 mL concentrated HCL, mix.
7.7.2 Immerse the electrodes into the working standard and record
instrument response. Rinse the electrodes thoroughly with reagent water
between each standard. Construct a calibration curve by recording the
instrument response (peak area or peak height) versus the standard
concentration.
7.8 Analyze the samples by aliquoting 25 mL of sample into a beaker.
Allow the temperature of the sample to equilibrate to room temperature (within
the range of 20 °C to 30 °C) if necessary. Add 5 mL of concentrated HCL to the
sample and mix. Immerse the electrodes into the sample and record instrument
response. Determine sample concentration from the calibration curve.
Note: Depending on the composition of the samples, a single application of
the gold film may suffice for analysis of up to a dozen or more samples.
Highly corrosive and oxidizing samples may corrode the gold film and
degrade the instrument response, requiring the re-application of the gold
film. The analyst must monitor performance of the electrode by analyzing
a mid-range check standard every ten samples. A low recovery for the
check standard indicates that the electrode must be renewed. Follow the
procedures in Sec. 7.3 through 7.5 to renew the gold film on the GCE.
Following the renewal of the electrode, the instrument calibration must be
verified by analyzing a mid-range standard. If the recovery of the
standard is within 10% of the true value, a new calibration curve need not
be run.
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8.0 QUALITY CONTROL
8.1 Initial Calibration Verification standard (ICV): The ICV contains
a known arsenic concentration and is obtained from an independent source. The
ICV recovery must be within the range 90% to 110%. If it is not, the source of
error must be found and corrected. An acceptable ICV must be analyzed prior to
analyzing samples. The ICV also serves as a laboratory control sample.
8.2 Continuing Calibration Verification standard (CCV): After a set of
10 or fewer samples has been analyzed, and after the final sample has been
analyzed, a CCV containing a known arsenic concentration must be analyzed. The
CCV recovery must be within the range 90% to 110%. If it is not, the source of
error must be found and corrected (see the note in Sec. 7.9) All samples
analyzed since the last acceptable CCV must be re-analyzed.
8.3 Reagent blank: A reagent blank must be analyzed with each analytical
batch or 20 samples, whichever is more frequent. A reagent blank is reagent
water treated as a sample. The indicated concentration of the reagent blank must
not be more than 0.1 jug/L of arsenic. If more than 0.1 jug/L of arsenic is
detected in the blank, sample carryover or reagent contamination is indicated.
The problem must be corrected before analyzing more samples.
8.4 At least one matrix spike (MS) and one matrix spike duplicate (MSD)
shall be included in each analytical batch or 20 samples: A matrix duplicate may
be substituted for the MSD provided that the concentration of arsenic in the
sample selected for duplicate analysis is greater than the limit of detection.
The spike should increase the concentration of free arsenic in the spiked sample
by 50% to 200%. The volume of the spike must be no more than 1% of the sample
volume.
8.4.1 The spike recovery should within the range 75% to 125%. If
the recovery of the spike is outside ± 25%, the problem should be
identified and corrected. If a matrix interference is suspected, a second
sample aliquot should be spiked to confirm the spike recovery. If the
spike recovery is still outside the range of ± 25%, all samples must be
quantified by the method of standard additions. Refer to Method 7000 for
information on the method of standard additions.
8.4.2 The duplicate samples (MS/MSD and/or Sample/Sample duplicate)
must give results having a difference not greater than 20% of the mean of
the duplicate results. If the difference is greater than 20% of the mean,
the source of error must be found and corrected.
9.0 METHOD PERFORMANCE
9.1 In a single-laboratory evaluation, standards with known arsenic
concentrations were analyzed according to the instructions given above. The
results are listed in Tables A-l and A-2.
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9.2 In a single-laboratory evaluation, known amounts of arsenic were
added to environmental water samples and soil extracts. The results are listed
in Table A-3.
9.3 In a single-laboratory evaluation, known amounts of arsenic were
added to environmental water samples and soil extracts. The resulting solutions
were analyzed according to the instruction given above and by graphite furnace
atomic absorption spectrophotometry (GFAA). The results are listed in Table A-4.
10.0 REFERENCES
1. Pyle, Steven; Miller, Eric Leroy; Quantifying Arsenic In Aqueous Solutions
By Anodic Stripping Voltametry, Contract EMSL-LV/ORD/USEPA.
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TABLE A-l. ACCURACY AND PRECISION OF ARSENIC (III) DETERMINATIONS
Arsenic (III)
Concentration (jug/L)
0.700
7.00
70.0
Arsenic (III) Recovery
i°/\
(/o)
102
98
100
Relative Standard
Deviation (%)
14
2
5
TABLE A-2. ACCURACY AND PRECISION OF ARSENIC (V) DETERMINATIONS
Arsenic (V)
Concentration (M9/L)
0.700
7.00
70.0
Arsenic (V) Recovery
t°/\
\'°)
99
100
99
Relative Standard
Deviation (%)
10
1
2
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TABLE A-3. QUANTIFYING ARSENIC IN ENVIRONMENTAL SAMPLES BY ASV
Sample
Identification
Tap Water
Tap Water + 1 g/L
Ascorbic Acid
A12544
(Water
A12545
(Water)
A12582
(Water)
A12582
(Water)
A24228
(Water)
A24228
(Water)
A22949
(Water)
A22949
(Water)
A22949
(Water)
A23274
(Soil Extract)
A23274
(Soil Extract)
A23275
(Soil Extract)
A23275
(Soil Extract)
Arsenic Added
(M9/L)
20.0
20.0
10.0
5.00
10.0
20.0
10.0
20.0
10.0
20.0
50.0
10.0
20.0
10.0
30.0
Arsenic Found
(M9/L)
Not Detected
20.2
9.3
5.11
10.0
19.8
10.6
20.5
9.9
20.2
48.2
12.3
22.1
10.5
31.6
Recovery
0%
101%
93%
102%
100%
99%
106%
103%
99%
101%
96%
101%
99%
105%
105%
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TABLE A-4. COMPARISON OF ASV AND GFAA RESULTS
FOR ARSENIC IN ENVIRONMENTAL SAMPLES
Sample
Identification
A12545
(Water)
A12582
(Water)
A22949
(Water)
A23274
(Soil Extract)
A23275
(Soil Extract)
Arsenic Added
Arsenic Found,
5.00
10.0
50.0
10.0
30.0
5.11
10.0
48.2
12.3
31.6
Arsenic Found,
GFAA
5.08
9.91
54.0
12.9
31.5
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METHOD 7063
ARSENIC IN AQUEOUS SAMPLES AND EXTRACTS
BY ANODIC STRIPPING VOLTAMMETRY (ASV)
7.2 Set up ASV
instrumentation
according to
manufacturer's
recommended
procedures.
7.3 Clean GCE.
7.4 - 7.5 Deposit gold
film on the GCE,
condition electrode.
7.7.1 - 7.7.2 Add
5 mL HCI to 25 mL
working standard;
immerse electrode
and record response.
Construct calibration
curve.
7.3 - 7.4 Clean GCE,
renew gold film.
7.8 Verify calibration
with mid-range
standard.
No
7.8 Add 5 mL HCI
to 25 ml aliquot of
samples, analyze.
I
7.8 Calculate sample
concentration by
comparing sample
response to
calibration curve.
7.8 Verify operation
of GCE by analyzing
a mid-range
check standard.
Is
recovery
within
+ /- 10%?
7.8 Continue analysis
of samples.
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METHOD 7199
DETERMINATION OF HEXAVALENT CHROMIUM IN DRINKING WATER, GROUNDWATER AND
INDUSTRIAL WASTEWATER EFFLUENTS BY ION CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 This method provides procedures for the determination of hexavalent
chromium in drinking water, groundwater, and industrial wastewater effluents.
1.2 The method detection limits for the above matrices are listed in
Table 1. The MDL obtained by an individual laboratory for a specific matrix may
differ from those listed depending on the nature of the sample and the
instrumentation used.
1.3 Samples containing high levels of anionic species such as sulfate and
chloride may cause column overload. Samples containing high levels of organics
or sulfides cause rapid reduction of soluble Cr(VI) to Cr(III). Samples must be
stored at 4°C and analyzed within twenty-four hours of collection.
1.4 This method should be used by analysts experienced in the use of ion
chromatography and in the interpretation of ion chromatograms.
2.0 SUMMARY OF METHOD
2.1 An aqueous sample is filtered through a 0.45 /zm filter and the
filtrate is adjusted to a pH of 9 to 9.5 with a buffer solution. A measured
volume of the sample (50-250 juL) is introduced into the ion chromatograph. A
guard column removes organics from the sample before the Cr(VI) as Cr042" is
separated on an anion exchange separator column. Post-column derivatization of
the Cr(VI) with diphenylcarbazide is followed by detection of the colored complex
at 530 nm.
3.0 INTERFERENCES
3.1 Interferences which affect the accurate determination of Cr(VI) may
come from several sources.
3.1.1 Contamination - A trace amount of Cr is sometimes found in
reagent grade salts. Since a concentrated buffer solution is used in this
method to adjust the pH of samples, reagent blanks should be analyzed to
assess for potential Cr(VI) contamination. Contamination can also come
from improperly cleaned glassware or contact or caustic or acidic reagents
of samples with stainless steel or pigmented material.
3.1.2 Reduction of Cr(VI) to Cr(III) can occur in the presence of
reducing species in an acidic medium. However, at a pH of 6.5 or
greater, Cr042"which is less reactive than the HCr04", is the predominant
species.
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3.1.3 Overloading of the analytical column capacity with high
concentrations of anionic species, especially chloride and sulfate, will
cause a loss of Cr(VI). The column specified in this method can handle
samples containing up to 5% sodium sulfate or 2% sodium chloride (1).
Poor recoveries from fortified samples and tailing peaks are typical
manifestations of column overload.
4.0 APPARATUS AND MATERIALS
4.1 Ion Chromatograph.
4.1.1 Instrument equipped with a pump capable of withstanding a
minimum backpressure of 2000 psi and of delivering a constant flow in the
range of 1-5 mL/min and containing no metal parts in the sample, eluant or
reagent flow path.
4.1.2 Helium gas supply (High purity, 99.995%).
4.1.3 Pressurized eluant container, plastic, one or two liter size.
4.1.4 Sample loops of various sizes (50 - 250
4.1.5 A pressurized reagent delivery module with a mixing tee and
beaded mixing coil .
4.1.6 Guard Column - A column placed before the separator column
containing a sorbent capable of removing strongly absorbing organics and
particles that would otherwise damage the separator column (Dionex lonPac
NG1 or equivalent) .
4.1.7 Analytical Column - A column packed with a high capacity anion
exchange resin capable of resolving Cr04 from other sample constituents
(Dionex lonPack AS7 or equivalent).
4.1.8 Postcolumn reactor - Mixing tee, or membrane reactor, with
reaction coil. Must be compatible with flows from 0 to 2 mL/min.
4.1.9 A low- volume flow- through cell visible lamp detector containing
no metal parts in contact with the eluant flow path. Detection wavelength
is at 530 nm.
4.1.10 Recorder, integrator, or computer for receiving analog or
digital signals for recording detector response (peak height or area) as
a function of time.
4.2 Labware - All reusable glassware (glass, quartz, polyethylene,
Teflon, etc.) including the sample containers should be soaked overnight in
laboratory grade detergent and water, rinsed with water, and soaked for four
hours in a mixture of dilute nitric and hydrochloric acid (1+2+9) followed by
rinsing with tap water and Reagent water.
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NOTE: Chromic acid must not be used for the cleaning of glassware.
4.2.1 Volumetric flasks and a graduated cylinder - of acceptable
precision and accuracy.
4.2.2 Assorted calibrated pipettes - of acceptable precision and
accuracy.
4.2.3 Disposable syringes - 10-mL, with male luer-lock fittings.
4.2.4 Syringe filters - 0.45-jum.
4.2.5 Storage bottle - high density polyproplene, 1-L capacity.
4.2.6 pH meter - to read pH range 0-14 with accuracy ± 0.03 pH.
4.2.7 Filter discs - 0.45-jum pore, 7.3-cm diameter (Gelman Aero BOA,
Mfr. No. 4262, or equivalent).
4.2.8 Plastic syringe filtration unit (Baxter Scientific, Cat. No.
1240 IN, or equivalent).
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents conform to the specifications
established by the Committee on Analytical Reagents of the American Chemical
Society, where such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
5.1.1 Ammonium hydroxide, NH4OH, (sp.gr. 0.902) (CAS RN 1336-21-6).
5.1.2 Ammonium sulfate, (NH4)2 S04 (CAS RN 7783-20-2).
5.1.3 1,5 Diphenylcarbazide (CAS RN 140-22-7).
5.1.4 Methanol, HPLC grade.
5.1.5 Sulfuric acid, concentrated (sp.gr. 1.84).
5.2 Reagent water. Reagent water shall be interference-free and should
conform to the performance specifications of ASTM Type I water. All references
to water in the method refer to reagent water unless otherwise specified. A
definition of reagent water can be found in Chapter One.
5.3 Cr(VI) Stock Solution (1000 mg/L). Dissolve 4.501 g of Na2Cr04*4H20
in reagent water and dilute to one liter. Transfer to a polypropylene storage
container.
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5.4 Quality control sample (QCS). Obtained and prepared from an
independent source (EPA, MIST or from a commercial source). Dilute an aliquot
according to the instructions and analyze with samples. If an EPA or NIST
reference sample is not available, a mid-range standard, prepared from an
independent commercial source, may be used.
5.5 Eluant. Dissolve 33 g of ammonium sulfate in 500 mL of reagent water
and add 6.5 ml of ammonium hydroxide. Dilute to one liter with reagent water.
5.6 Post-column reagent. Dissolve 0.5 g of 1,5 diphenylcarbazide in 100
ml of HPLC grade methanol. Add to about 500 ml of Reagent water containing 28
ml of 98% sulfuric acid while stirring. Dilute with reagent water to one liter
in a volumetric flask. Reagent is stable for four or five days, but should only
be prepared in one liter quantities as needed.
5.7 Buffer Solution. Dissolve 33 g of ammonium sulfate in 75 ml of
reagent water and add 6.5 mL of ammonium hydroxide. Dilute to 100 ml with
reagent water.
6.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING
6.1 Prior to the collection of the sample, consideration should be given
to the type of data required so that appropriate preservation and pretreatment
steps can be taken. Filtration and pH adjustment should be performed at the time
of sample collection or as soon thereafter as practically possible.
6.2 For the determination of dissolved Cr(VI), the sample should be
filtered through a 0.45-/im filter. Use a portion of the sample to rinse the
syringe filtration unit and filter and then collect the required volume of
filtrate. Adjust the pH of the sample to 9-9.5 by dropwise addition of buffer
solution (Section 5.7), periodically checking the pH with the pH meter or narrow
pH-range pH paper. Approximately 10 mL of sample are sufficient for three 1C
analyses.
6.3 Ship and store the samples at 4°C in 125-mL narrow-mouth, high-
density polypropylene containers, or equivalent. Bring to ambient temperature
prior to analysis. Samples should be analyzed within 24 hours of collection.
7.0 PROCEDURE
7.1 Sample preparation. Allow pH-adjusted samples to equilibrate to
ambient temperature prior to analysis. Samples that have not been pH adjusted
should be adjusted as described in Section 6.2.
7.2 Calibration. Calibrate the instrument using a minimum of a
calibration blank and three calibration standards bracketing the anticipated
concentration range of the samples. The calibration range must cover no more
than two orders of magnitude. Calibration standards should be prepared from the
Cr(VI) stock standard (Section 5.3) by appropriate dilution with reagent water
7199 - 4 Revision 0
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in volumetric flasks. The standards should be adjusted to a pH of 9-9.5 with the
buffer solution prior to final dilution.
7.2.1 Establish ion chromatographic operating conditions as
indicated in Table 2 or as instructed by the instrument manufacturer. The
flow rate of the eluant pump is set at 1.5 mL/min and the pressure of the
reagent delivery module adjusted so that the final flow rate from the
detector is 2.0 mL/min. This requires manual adjustment and measurement
of the fi.nal flow using a graduated cylinder and a stop watch. A warm-up
period of approximately 30 minutes after the flow rate has been adjusted
is recommended and the flow rate should be checked prior to calibration
and sample analysis.
7.2.2 Injection loop size is chosen based on standard and sample
concentrations and the selected attenuator setting. A 250-juL loop was
used to establish the method detection limits in Table 1. A 50-juL loop
is normally sufficient for higher concentrations. The sample volume used
to load the injection loop should be at least 10 times the loop size so
that all tubing in contact with sample is thoroughly flushed with new
sample to prevent cross contamination.
7.2.3 A calibration curve of analyte response (peak height or area)
versus analyte concentration should be constructed. The coefficient of
correlation for the curve should be 0.999 or greater.
7.3 Instrument performance. Check the performance of the instrument and
verify the calibration using data gathered from analyses of laboratory blanks,
calibration standards and the quality control sample.
7.3.1 After the calibration has been established, it must be
verified by analyzing a QCS. If the measured concentration exceeds ± 5%
of the established value, a second analysis should be performed. If the
measured concentration still exceeds ± 5% the established value, the
analysis should be terminated until the source of the problem is
identified and corrected.
7.3.2 To verify that the instrument is properly calibrated on a
continuing basis, run a laboratory blank and a calibration check standard
every ten analyses. If the measured concentration of the analyte deviates
from the true concentration by more than ± 5%, re-analyze the calibration
check standard. If this check standard deviates by more than ± 5%, the
instrument must be recalibrated and the previous ten samples re-analyzed.
The instrument response from the calibration check may be used for
recalibration purposes. Refer to Section 7.2 for instrument calibration
procedures.
7.4 Sample Analysis. Draw into a new, unused syringe approximately 3 ml
of sample and attach a syringe filter to the syringe. Discard 0.5 mL through the
filter and load the remaining sample (equal to at least 10X the sample loop
volume) into sample loop. Samples having concentrations higher than the
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established calibration range must be diluted into the calibration range and re-
analyzed. Each sample should be injected twice and the Relative Standard
Deviation of the duplicates should be less than 20% or the sample data must be
qualified.
7.5 Calculations.
7.5.1 From the calibration curve the concentration of the sample can
be determined. For the above procedure, if there is no. dilution, the
concentration of the sample should be reported as
7.5.2 The QC data obtained during the analyses provide an indication
of the quality of the sample data and should be provided with the sample
results.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for the appropriate quality control procedures.
8.2 All quality control data should be maintained and available for easy
reference or inspection.
8.3 Calibration curves should be composed of a minimum of a blank and
three standards.
8.4 Samples exceeding the highest calibration standard must be diluted
and re-analyzed.
8.5 A minimum of one method blank sample per sample batch must be
analyzed to check for contamination. A method blank is reagent water prepared
by adjusting the pH to between 9 and 9.5 with the same volume of buffer as used
for the samples.
8.6 A minimum of one duplicate sample and one matrix spike sample per
sample batch must be analyzed for each analytical batch to check for duplicate
precision and matrix-spike recovery.
8.7 A quality control sample (QCS) must be analyzed at the beginning of
each analytical run to validate the instrument calibration.
9.0 METHOD PERFORMANCE
9.1 Instrument operating conditions used for single laboratory testing
of the method are summarized in Table 2. Dissolved Cr(VI) method detection
limits are listed in Table 1.
9.2 Data obtained from single laboratory testing of the method are
summarized in Table 3 for five water samples representing drinking water,
deionized water, groundwater, treated municipal sewage wastewater, and treated
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electroplating wastewater. Samples were fortified with 100 and 1000 p.g/1 of
Cr(VI), and recoveries were determined.
9.3 Pooled Precision and Accuracy: This method was tested by 21
volunteer laboratories in a joint study by USEPA and the American Society for
Testing and Materials (ASTM). Mean recovery and accuracy for Cr(VI) (as Cr042")
was determined from the retained data of 13 laboratories in reagent water,
drinking water, groundwater, and various industrial wastewaters. For reagent
water, the mean recovery and the overall, and single-analyst relative standard
deviations were 105%, 7.8%, and 3.9%, respectively. Table 4 contains the linear
equations that describe the single-analyst standard deviation and mean recovery
of Cr(VI) in reagent water.
10.0 REFERENCES
1. Dionex Technical Note No. 26, May 1990.
2. Glaser, J.A., Foerst, D.L., McKee, G.D., Quave, S.A., and Budde,
W.L., "Trace Analyses for Wastewaters", Environmental Science and
Technology, Vol. 15, No. 12, 1981, pp. 1426-1435.
3. Edgell, K., Longbottom, J., and Joyce, R., "Determination of
Dissolved Hexavalent Chromium in Drinking Water, Groundwater, and
Industrial Wastewater Effluents by Ion Chromatography: Collaborative
Study", (Internal EPA report, 1992).
4. Arar, Elizabeth J., and Pfaff, John D., "Determination of Dissolved
Hexavalent Chromium in Industrial Wastewater Effluents by Ion
Chromatography and Post-Column Derivatization with
Diphenylcarbazide", Journal of Chromatography, 546 (1991) 335-340.
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Table 1. Method Detection Limit for Cr(VI)
Matrix Type
Reagent Water
Drinking Water
Ground Water
Primary Sewage
Wastewater
Electroplating
Wastewater
Retention Time
(min)
3.8
3.8
3.8
3.8
3.8
Method Detection Limit18'
wq/L
0.4
0.3
0.3
0.3
0.3
(a)
MDL concentrations are computed for final analysis solution (Section 8.2.2)
Table 2. Ion Chromatographic Conditions
Columns: Guard Column - Dionex lonpac NGI
Separator Column - Dionex lonPac AS7
Eluant: 250 mM (NHJ2S04
100 mM NH4
Flow Rate =1.5 mL/min
Post-Column Reagent: 2mM Diphenylcarbohydrazide
10% v/v CH3OH
1 N H2S04
Flow rate =0.5 mL/min
Detector: Visible 530 nm
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Table 3. Single-laboratory Precision and Accuracy
Sample Type
Reagent Water
Drinking Water
Ground Water
Primary Sewage
Wastewater
Effluent
Electroplating
Wastewater
Effluent
Cr(VI)
(/vg/L)(a)
100
1000
100
1000
100
1000
100
1000
100
1000
Percent
Mean Recovery
100
100
105
98
98
96
100
104
99
101
RpD(bi
0.8
0.0
6.7
1.5
0.0
0.8
0.7
2.7
0.4
0.4
(al Sample fortified at this concentration level.
(b> RPD - relative percent difference between duplicates.
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Table 4. Single-Analyst Precision, Overall Precision and Recovery
From Multilaboratory Study
Reagent Water Matrix Water
(6-960 fjg/l) (6-960//g/L)
Mean Recovery X = 1.020C + 0.592 X = 0.989C - 0.411
Overall Standard SR= 0.035X + 0.893 SR= 0.059X + 1.055
Deviation
Single-Analyst SR= 0.021X + 0.375 SR= 0.041X + 0.393
Standard-Devi ation
X = Mean concentration; //g/L, exclusive of outliers.
C = True value, /yg/L.
SR= Overall standard deviation.
SR= Single-Analyst standard deviation.
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METHOD 7199
DETERMINATION OF HEXAVALENT CHROMIUM IN DRINKING WATER. GROUNDWATER AND
INDUSTRIAL WASTEWATER EFFLUENTS BY ION CHROMATOGRAPHY
7.1 Sample Preparation: Adjust sample pH
to 9 - 9.5, allow sample to equiliberat* to
ambient temperature.
7 2.1 - 7.2 2 Establish instrument operating
conditions and flow rate; select sampling loop.
7.2.3 - 7.3 Calibrate with a minimum of three
standards, verify instrument performance
and calibration with blank analyses,
standards and QCS.
Repeat analysis of QCS,
if not within +/- 5% T.V.
7.3.2 Verify continuing instrument
calibration every 10 analytical samples
with calibration check standard and blank.
Recalibrate and reanalyze
previous tan samples.
Yes
Continue analysis.
7.5 Calculate sample concentration frort
calibration curve, report as ug/L.
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METHOD 7472
MERCURY IN AQUEOUS SAMPLES AND EXTRACTS
BY ANODIC STRIPPING VOLTAMMETRY (ASV)
1.0 SCOPE AND APPLICATION
1.1 This method is applicable for laboratory determinations of
dissolved organic and inorganic divalent mercury ions and compounds (Hg(IIJ)
in drinking water, natural surface water, seawater, in domestic and industrial
wastewater, and in aqueous soil extracts. Solid matrices must be solubilized
by acid digested prior to quantitation by ASV.
1.2 Dissolved Hg(II) in the form of mercury ions and un- ionized
organic and inorganic mercury compounds may be quantified in the concentration
range 0.1 to 10,000 p.g/1 Hg. The upper concentration range may be extended
by sample dilution, increasing the stripping current and/or by decreasing the
analyte deposition time.
1.3 This method cannot be used for direct determination of water-
insoluble mercury compounds. Analytes containing mercury in this form must be
chemically processed to liberate Hg(II) before the determination.
1.4 The method detection limit for Hg(II) is 0.1 jug/L using a 10-
minute plating time and 3 /^g/L using a 1-minute plating time.
2.0 SUMMARY OF METHOD
2.1 Standards and samples are made 0.1 M in CV and are rendered
electrically conductive by adding concentrated hydrochloric acid (HCL) or
solid sodium chloride (NaCl). Hg(II) is quantified by anodic stripping, at a
potential of +500 mV with respect to an saturated calomel electrode (SCE),
from a gold metal film deposited on a glassy carbon electrode (GCE).
3.0 INTERFERENCES
3.1 ASV cannot distinguish between organic and inorganic divalent
mercury compounds.
3.2 Turbid samples should be filtered through a borosilicate glass
fiber filter with 0.45-jLim pores to preclude physical erosion of the GCE film.
3.3 Highly corrosive and oxidizing samples may corrode the gold film
on the GCE and degrade the instrument response. The performance of the GCE
electrode must be monitored by analysis of a mid-range calibration standard.
Low recovery on the calibration standard may require re-cleaning and re-
application of the gold film.
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3.4 Samples containing tannic acid in concentrations greater than 100
mg/L cannot be analyzed for mercury by ASV.
3.5 Some wet deposition samples may have insufficient electrical
conductivity for proper operation of the ASV instrumentation. This problem is
obviated by making the samples 0.1 M in HCL.
4.0. APPARATUS AND MATERIALS
4.1 ASV instrumentation (Radiometer TraceLab, or equivalent),
including potentiostat, electrodes, stirrer, sample stand, polyethylene sample
cups, and GCE polishing powder.
4.2 Computer, as recommended by ASV instrumentation manufacturer.
4.3 Plastic syringe and a nylon syringe filter with 0.2-fjm pores.
4.4 Polyethylene graduated cylinder, 50-mL, Class B, TC/TD.
4.5 Adjustable pipetters with polyethylene tips.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents shall conform to the
specifications of the Committee on Analytical Reagents of the American
Chemical Society, where such specifications are available. Other grades may
be used, provided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of the
determination.
5.2 Reagent Water. Reagent water is interference free. All
references to water in the method refer to reagent water unless otherwise
specified.
5.3 Hydrochloric acid, (concentrated 12 M)
5.3.1 Hydrochloric acid (0.1 M), dilute 8.3 ml concentrated HCL
to 1 liter with reagent water.
5.4 Sodium Chloride, fine crystals.
5.5 Gold Stock Standard (1000 mg/L), stock solutions are commercially
available as spectrophotometric standards.
5.5.1 Gold-plating solution, (50 mg/L Au in 0.1 M HCL), or as
recommended by the GCE manufacturer: prepare by diluting 2.5 mL of a
1000 mg/L gold spectrophotometric standard to 50 mL with 0.1 M HCL.
5.6 Mercury Stock Standard (1000 mg/L), stock solutions are
commercially available as spectrophotometric standards.
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5.6.1 Mercury intermediate standard solution, 1,000/yg/L mercury:
dilute 100//L of the stock standard to 100 mL with 2% HN03. Prepare
weekly.
5.6.2 Mercury Working Standards: These standards should be
prepared from the mercury intermediate standard to be used as
calibration standards at the time of analysis. Prepare at least five
working standards over the expected sample concentration range. Prepare
working standards by diluting an appropriate aliquot of the intermediate
mercury stock solution with 2% HN03.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, acids,
and reagent water. Plastic and glass containers are both suitable.
6.3 At the time of sampling, the sample must be acidified to a pH <2
with nitric acid.
6.4 While samples to be analyzed for free dissolved mercury do not
require refrigeration, they should be stored out of direct sunlight in an area
no warmer than room temperature.
7.0 PROCEDURE
7.1 Analysis of aqueous samples for free dissolved mercury by ASV
involves two major steps. First, the GCE electrode is cleaned and prepared
for use by plating on a thin film of gold. The gold-plated electrode is then
used to analyze calibration standards and samples.
7.2 Set up ASV instrumentation, electrodes, and computer according to
the manufacturer's recommended procedures. Enter the appropriate program and
required data parameters into the computer as directed by the instrument
software.
7.3 Before applying a gold film to the GCE, the electrode must be
thoroughly cleaned. Electrode cleanliness is checked by rinsing the GCE with
water. After gently shaking off excess water, the electrode should be coated
with a thin, flat, continuous water film. If necessary, clean the GCE by
wiping it with a wet, soft paper towel, polish it with polishing powder, and
rinse it thoroughly with water. Keep the cleaned electrode immersed in water.
7.4 Place 50 mL of the gold-plating solution (Sec. 5.5.1) or an
appropriate volume as recommended by the instrument manufacturer, into a
beaker. Immerse the electrodes in the gold-plating solution and initiate the
GCE gold-plating program as instructed by the instrument manufacturer.
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7.5 Remove the electrodes from the plating solution and rinse well
with water. Keep the electrodes immersed in reagent water until ready to
analyze samples.
7.6 The instrument response is calibrated by preparing a calibration
curve with mercury standards (Sec 5.6.2). The same stripping current and
plating time settings that are used for analyzing samples must be used for
preparing the calibration curve.
7.7 Prior to instrument calibration, all calibration standards and
samples must be made 0.1 M in Cl". Using a graduated cylinder, measure 30 ml
of each calibration standard and sample into a sample cup. Add 0.25 mL of 12
M HCL (Sec 5.3) or 0.18 g of solid NaCl (Sec 5.4) to the standard or sample
and mix. Samples must be allowed to equilibrate to room temperature (within
the range 20 "C to 30 °C) if necessary.
7.8 Following the instrument manufacturer's recommended calibration
procedures, construct a calibration curve by analyzing five working
calibration standards. Immerse the electrodes into 30 ml of the prepared
working standard (Sec 7.7) and record instrument response. Rinse the
electrodes thoroughly with reagent water between each standard. Construct a
calibration curve by recording the instrument response (peak area) versus the
standard concentration.
7.9 Store the electrodes in reagent water until ready to analyze
another sample.
7.10 Analyze the samples for Hg (II) by aliquoting 30 ml of the
prepared sample (Sec. 7.7) into a sample cup. Immerse the electrodes into the
sample and record instrument response. Determine the sample concentration
from the calibration curve.
Note: Depending on the composition of the samples, a single
application of the gold film may suffice for analysis of up to a
dozen or more samples. Highly corrosive and oxidizing samples may
corrode the gold film and degrade the instrument response,
requiring the re-application of the gold film. The analyst must
monitor performance of the electrode by analyzing a mid-range
check standard every ten samples. A low recovery for the check
standard indicates that the electrode must be renewed. Follow the
procedures in Sec. 7.3 through 7.5 to renew the gold film on the
GCE. Following the renewal of the electrode, the instrument
calibration must be verified by analyzing a mid-range standard. If
the recovery of the standard is within 10% of the true value, a
new calibration curve need not be run and the analyst may continue
with the analysis.
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8.0 QUALITY CONTROL
8.1 Initial Calibration Verification standard (ICV): The ICV contains
a known Hg(II) concentration and is obtained from an independent source. The
ICV recovery must be within the range 90% to 110%. If it is not, the source
of error must be found and corrected. An acceptable ICV must be analyzed
prior to analyzing samples. The ICV also serves as a laboratory control
sample.
8.2 Continuing Calibration Verification standard (CCV): After a set
of not more than 10 samples has been analyzed, and after the final sample has
been analyzed, a CCV containing a known mercury concentration must be
analyzed. The CCV recovery must be within the range 90% to 110%. If it is
not, the source of error must be found and corrected (See the note in Sec.
7.10) All samples analyzed since the last acceptable CCV must be re-analyzed.
8.3 Reagent blank: A reagent blank must be analyzed with each
analytical batch or 20 samples, whichever is more frequent. A reagent blank
is reagent water treated as a sample. The indicated concentration of the
reagent blank must be less than the lower detection limit of Hg(II). If it is
not, sample carryover or reagent contamination is indicated. The problem must
be corrected before analyzing more samples.
8.4 At least one matrix spike (MS) and one matrix spike duplicate
(MSD) shall be included in each analytical batch or 20 samples: A matrix
duplicate may be substituted for the MSD provided that the concentration of
mercury in the sample selected for duplicate analysis is greater than the
limit of detection. The spike should increase the concentration of free
Hg(II) in the spiked sample by 50% to 200%. The volume of the spike must be
no more than 1% of the sample volume.
8.4.1 The spike recovery must be within the range 75% to 125%.
If it is not, the source of error must be found and corrected. If a
matrix interference is suspected, a second sample aliquot should be
spiked to confirm the spike recovery. If the spike recovery is still
outside the range of ± 25%, all samples must be quantified by the method
of standard additions. Refer to Method 7000 for information on the
method of standard additions.
8.4.2 The duplicate samples (MS/MSD and/or Sample/Sample
duplicate) should give results having a difference not greater than 20%
of the mean of the duplicate results. If the difference is greater than
20% of the mean, the source of error must be found and corrected.
9.0 METHOD PERFORMANCE
9.1 In a single-laboratory evaluation, standards with known Hg(II)
concentrations were analyzed in quintuplicate according to the instructions
given above. The results are listed in Table 1.
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TABLE 1. ACCURACY AND PRECISION OF MERCURY ANALYSIS
Mercury Concentration
(M9/L)
5.00
15.0
50.0
Mercury Recovery
(%)
97
101
97
Relative Standard
Deviation (%)
3.8
0.9
1.2
9.2 In a single laboratory evaluation, the precision and accuracy of
ASV was compared to an EPA-approved spectrophotometric method by analyzing a 1
fj.g/1 and 5 /*g/L standard of mercury (II) ten times each. The results of this
comparison are listed in Table 2.
TABLE 2. COMPARISON OF ASV AND SPECTROPHOTOMETRIC METHOD FOR QUANTIFYING
DISSOLVED MERCURY
Analytical Method:
Response in yug/L and
(RSD,%) for a 1 /xg/L Hg
(II) standard
Response in yug/L and
(RSD, %) for a 5 ^g/L
Hg (II) standard
Voltammetry 1.0 5.1
(5.2) (2.1)
Spectrophotometric 1.1 5.0
(6.2) (5.7)
10.0 REFERENCES
1. Pyle, Steven; Miller, Eric Leroy; Quantifying Mercury In Aqueous
Solutions By Anodic Stripping Voltammetry, EMSL-LV/ORD/USEPA.
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METHOD 7472
MERCURY IN AQUEOUS SAMPLES AND EXTRACTS
BY ANODIC STRIPPING VQLTAMMETRY (ASV)
7.2 Set up ASV
instrumentation
according to
manufacturer's
procedures.
7.10 Analyze a 30 ml_
aliquot of sample,
calculate sample
cone, from
calibration curve.
7.3 Clean GCE.
i
7
r
4 Apply gold film
to GCE.
7.10 Verify operation
of GCE by analyzing
a mid-range check
standard every
1 0 samples.
7.7 Add 0.25 mL of
12 M HCI or 0.18 g
NaCL to all standards
and samples.
7,3 - 7.4 Clean GCE,
renew gold film.
7.8 Analyze 5
calibration standards,
construct a
calibration curve.
7.10 Verify calibration
with mid-range
standard.
Is
recovery
within + /
10%?
7.10 Continue
analysis.
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METHOD 7521
NICKEL (ATOMIC ABSORPTION, FURNACE METHOD)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 If interferences are suspected, see Section 3.0 of Method 7000.
3.2 In addition to the normal interferences experienced during graphite
furnace analysis, nickel analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix components during atomization. Background
correction is strongly recommended.
3.3 Severe memory effects for nickel may occur in graphite furnace tubes
used for arsenic or selenium analysis by Methods 7060 and 7740, resulting from
the use of a nickel nitrate matrix modifier in those methods. Use of graphite
furnace tubes and contact rings for nickel analysis that are separate from those
used for arsenic and selenium analyses is strongly recommended.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000. Due to the
widespread use of a nickel-nitrate modifier for atomic absorption analyses, a
dedicated instrument is recommended when conducting analyses by this method. If
a dedicated instrument is not available, the furnace tubes and contact rings
should be changed prior to using this methodology.
4.2 Instrument parameters (general):
4.2.1 Drying time and temp.: 30 sec at 125°C.
4.2.2 Ashing time and temp.: 30 sec at 800°C.
4.2.3 Atomizing time and temp.: 10 sec at 2700°C.
4.2.4 Purge gas: Argon or nitrogen.
4.2.5 Wavelength: 232.0 nm.
4.2.6 Background correction: Recommended.
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4.2.7 Other operating parameters should be set as specified by the
particular instrument manufacturer.
NOTE: The above concentration values and instrument conditions are
for a Perkin-Elmer HGA-2100, based on the use of a 20-uL injection,
continuous-flow purge gas, and nonpyrolytic graphite. Smaller size
furnace devices or those employing faster rates of atomization can
be operated using lower atomization temperatures for shorter time
periods than the above-recommended settings.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards
5.2.1 Stock solution - Do not dry reagent. Dissolve 4.953 g of
nickel nitrate hexahydrate, Ni(N03)2»6H20 (analytical reagent grade) in
reagent water and dilute to 1.000 L in a volumetric flask. Alternatively,
procure a certified standard from a supplier and verify concentration by
comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of acid and at the same acid
concentration as in the prepared samples to be analyzed (0.5% v/v HN03).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Step 3.1.3, "Sample Handling and Preparation."
7.0 PROCEDURE
7.1 Sample preparation - The procedures for preparation of the sample are
given in Chapter Three, Step 3.2.
7.2 See Method 7000, Step 7.3, "Furnace Technique."
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are not available at this time.
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9.2 The performance characteristics for an aqueous sample free of
interferences are as follows:
Optimum concentration range: 5-50 ug/L.
Estimated detection limit: 1 ug/L.
10.0 REFERENCES
1. Methods for the Chemical Analysis of Water and Wastes, U.S. Environmental
Protection Agency, Office of Research and Development, Environmental Monitoring
and Support Laboratory, ORD Publication Offices of the Center for Environmental
Research Information, Cincinnati, OH, 1983; EPA-600/4-79-020.
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METHOD 7521
NICKEL (ATOMIC ABSORPTION. FURNACE METHOD)
>
5.0
r
Prepare sample.
See Section 3.2
of Chapter 3 for
sample preparation.
See Section 7.3 of
Method 7000 for
'Furnance Technique"
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METHOD 7580
WHITE PHOSPHORUS (P,) BY SOLVENT EXTRACTION AND GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Method 7580 may be used to determine the concentration of white
phosphorus (P4) (CAS Registry No. 7723-14-0) in soil, sediment, and water
samples.
1.2 This method includes two different extraction procedures for water
samples. The first procedure provides sensitivity on the order of 0.01 /Ltg/L,
and may be used to assess compliance with Federal water quality criteria. The
second procedure provides sensitivity on the order of 0.1 /xg/L. The method
includes one procedure for the extraction of soil/sediment samples which provides
sensitivity on the order of 1 jiig/kg.
1.3 White phosphorus is a toxic, synthetic substance that has been used
in poisons, smoke-screens, matches, and fireworks, and has been used as a raw
material in the production of phosphoric acid. It has been used in smoke-
producing munitions since World War I. White phosphorus is thermodynamically
unstable in the presence of atmospheric oxygen. As a result, until recently, the
prospect of long-term environmental contamination from smoke munitions was
considered unlikely. However, a catastrophic die-off of waterfowl at a US
military facility has been traced to the presence of P4 in salt marsh sediments,
and lead to the realization that P4 can persist in anoxic sedimentary
environments.
1.4 While this method is included in Chapter Three, Metallic Analytes,
the sample preparation, extraction, and analytical techniques employed are
closely related to those described in Chapter Four for organic analytes.
Therefore, this method has been written as a stand-alone procedure, describing
both the extraction and analytical techniques. Analysts should refer to Method
8000 for additional information on gas chromatographic procedures.
1.5 This method is restricted to use by, or under the supervision of,
analysts experienced in solvent extraction and gas chromatography. Each analyst
must demonstrate the ability to generate acceptable results using this method.
1.6 Because P4 will spontaneously combust in air, the procedures for the
preparation of standards described in Section 5 require the use of a glove box
or other suitable enclosed area purged with nitrogen.
2.0 SUMMARY OF METHOD
2.1 Water samples are extracted by one of two procedures, depending on
the sensitivity required.
2.1.1 For the more sensitive procedure, a 500 ml water sample is
extracted with 50 ml of diethyl ether. The extract is concentrated by back
extraction with reagent water, yielding a final extract volume of
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approximately 1.0 ml. A 1.0 ,uL aliquot of this extract is injected into
a gas chromatograph (GC) equipped with a nitrogen-phosphorus detector
(NPD). This procedure provides sensitivity on the order of 0.01 ^g/L, and
may be used to assess compliance with Federal water quality criteria.
2.1.2 When a less sensitive method is required for water samples,
a 30 ml water sample is extracted once with 3.0 ml of isooctane. A 1.0 nl
aliquot of the extract is analyzed by GC/NPD. This procedure provides
sensitivity on the order of 0.1 jitg/L.
2.2 Wet soil or sediment samples are analyzed by extracting a 40 g wet-
weight aliquot of the sample with a mixture of 10.0 ml of degassed reagent water
and 10.0 ml of isooctane. The extraction is performed in a glass jar on a
platform shaker for 18 hours. A 1.0 jj.1 aliquot of the extract is analyzed by
GC/NPD. This procedure provides sensitivity on the order of 1 M9/kg.
2.3 The concentration of P4 in the extract is calculated using peak area
(or height) and an external standard calibration procedure. The sample
concentration is determined from the extract concentration using the final volume
of the sample extract, sample volume (water samples) or sample weight
(soils/sediments). Results for soils and sediments are reported on a wet-weight
basis.
2.4 Separate calibrations are required for water and soil/sediment
samples because the sample extracts are prepared in different solvents (diethyl
ether and isooctane).
3.0 INTERFERENCES
To date, no chromatographic interferences with this determination have been
reported, in part due to the selectivity of the nitrogen-phosphorus detector.
This procedure offers several advantages compared to other procedures described
in the literature which determine P4 by converting it to phosphate, in that
background concentrations of phosphate are quite common in many water and
sediment samples.
4.0 APPARATUS AND MATERIALS
4.1 500-mL separatory funnels with PTFE stopcocks, for water sample
extraction (larger separatory funnels may be employed).
4.2 125-mL separatory funnels with PTFE stopcocks, for back extraction
of water samples.
4.3 40-mL amber glass vials (for less sensitive water method).
4.4 120-mL glass vials or jars with PTFE-lined screw caps.
4.5 500-mL graduated cylinder.
4.6 10-mL graduated cylinder.
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4.7 4-L (or larger) amber glass bottle with PTFE-lined screw cap (for
preparation of the aqueous spiking solution).
4.8 250-mL and 50-mL glass volumetric flasks, with ground-glass stoppers.
4.9 Disposable pasteur pipets.
4.10 Vortex mixer.
4.11 Platform shaker, with table to hold 120-mL vials or jars used for
soil extractions.
4.12 Glove box or other suitable system to handle P4 under a nitrogen
atmosphere, complete with purified nitrogen source, gas regulator, and tubing.
4.13 Analytical balance, capable of weighing 0.1 mg.
4.14 Forceps, for handling P4.
4.15 Gas-tight syringe, 10 /xL.
4.16 Razor blades or scalpels, for cutting P4.
4.17 Gas chromatograph, capable of isothermal operation at 80°C, equipped
with a nitrogen-phosphorus detector, data system, and all relevant accessories.
4.18 GC column, 15 m wide-bore capillary column, 1% methyl silicone,
3.0 jim film thickness (DB-1, or equivalent).
4.19 Glass vacuum filtration apparatus for degassing reagent water
(Supelco 5-8062, or equivalent).
5.0 REAGENTS
Unless otherwise specified, all reagents will be at least ACS reagent
grade. All reagents must be checked for purity and contaminants through the
analysis of method blanks (see Sec. 8.2).
5.1 White phosphorus, (99% purity), Aldrich Chemical, or equivalent.
5.2 Isooctane (2,2,4-trimethylpentane), ACS spectrophotometric grade.
5.3 Diethyl ether, pesticide grade.
5.4 Water, ASTM regent grade. The reagent water must be degassed in a
glass vacuum filtration apparatus or other suitable device to remove any traces
of oxygen. Oxygen may also be removed from the reagent water by heating the
water to 90"C and purging it with clean helium or nitrogen, as is done for
reagent water used in the analysis of volatile organics (see Chapter One).
5.5 Nitrogen, prepurified, for glove box.
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5.6 Nitrogen, zero grade, for GC carrier gas.
5.7 Hydrogen, zero grade, for NPD detector.
5.8 Preparation of calibration stock standard in isooctane: The
instrument calibration standards for soil/sediment samples and for water samples
extracted with isooctane (Sec. 7.6) are prepared in isooctane. A separate set
of calibration standards is required for water samples extracted with diethyl
ether (see Sec. 5.9).
5.8.1 Cut several pieces of P4 to the appropriate size under
degassed water in a nitrogen atmosphere. Care should be taken to ensure
that each piece of freshly cut P4 is lustrous on all surfaces. Each piece
should be dried under a gentle stream of nitrogen.
5.8.2 Place a small freshly cut piece of P4 (approx. 90 mg) into
a preweighed 250-mL volumetric flask containing a small amount of
isooctane.
5.8.3 Weigh the flask containing the isooctane and piece of P4 to
determine the mass of P4 by difference.
5.8.4 Bring the flask to volume with isooctane and shake until the
P4 dissolves. Protect the flask from light by wrapping the flask in
aluminum foil.
5.8.5 Calculate the concentration of P4 in the volumetric flask.
5.8.6 Using the calibration stock standard, prepare 5 calibration
standards in isooctane over the linear range of the calibration curve. The
lowest concentration standard should be set at or below a sample
concentration of 1 M9A9- For a 40 g (wet weight) sample and a 1 nl
injection volume, the concentration of the lowest standard will be
approximately 4 /zg/L in isooctane. To demonstrate the 0.1 /ig/L sensitivity
for the water sample procedure in Sec. 7.6, the concentration of the lowest
standard must be approximately 1 jug/L in isooctane. The remaining
standards should span the linear working range of the chromatographic
system (see Method 8000 for a discussion of five-point initial calibration
standards).
5.8.7 Store any working stock solutions and calibration standards
in the dark at 4°C.
5.9 Preparation of calibration stock standard in diethyl ether
Because of the volatility of diethyl ether, it is likely that calibration
standards and stock standards for the water samples extracted by the diethyl
ether procedure in Sec. 7.3 will have to be prepared more frequently than those
standards in isooctane for the soil/sediment samples procedure.
5.9.1 Using the isooctane calibration stock standard prepared in
Sections 5.8.1 - 5.8.5, prepare 5 calibration standards in diethyl ether
over the linear range of the calibration curve. Since the stock standard
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is diluted by a factor of approximately 5000, the small amount of isooctane
is insignificant. The lowest concentration standard should be set at or
below a sample concentration of 0.01 jug/L. For a 500-mL water sample, a
1.0 ml final extract volume, and a 1 /itL injection volume, the concentration
of the standard will be approximately 5 M9/L in diethyl ether. The
remaining standards should span the linear working range of the
chromatographic system (see Method 8000 for a discussion of five-point
initial calibration standards).
5.9.2 Store any working stock solutions and calibration standards
in the dark at -20°C.
5.10 Preparation of the aqueous stock solution of P4 - The solubility of
P4 in water is approximately 3 mg/L. The following instructions involve the
preparation of a stock solution from an excess of P4 (i.e., this should produce
a saturated solution of P4 in water).
5.10.1 Cut a piece of P4 weighing at least 15 mg, under degassed
water in a nitrogen atmosphere such as a glove box. Care should be taken
to ensure that the piece of freshly cut P4 is lustrous on all surfaces.
The piece should be dried under a gentle stream of nitrogen.
5.10.2 Maintaining the nitrogen atmosphere, place the freshly cut
piece of P4 into an amber glass container with a PTFE-lined cap and at
least a 4 L capacity.
5.10.3 Fill the container with Type I, degassed reagent grade water,
leaving no headspace.
5.10.4 Seal the container, remove it from the nitrogen atmosphere,
and constantly agitate the mixture for at least 60 days.
5.10.5 As noted above, this procedure involves the use of an excess
of P4. After 60 days, the concentration of the P4 in the aqueous stock
solution must be determined by extraction with isooctane and analysis using
the procedures in Sec. 7.6.
5.11 Preparation of the aqueous spiking solutions - Two different aqueous
spiking solutions are required for preparation of matrix spike/matrix spike
duplicate aliquots. One solution is used for spiking water samples. The other
solution is used for spiking soil/sediment samples.
5.11.1 Based on the concentration of the stock solution determined
in Sec. 7.6, prepare an aqueous spiking solution at a concentration of 5
/ng/L by diluting the stock solution. A 1.0 ml volume of this spiking
solution added to a 500 ml sample will produce a concentration of
approximately 0.01 jug/L of P4.
5.11.2 Based on the concentration of the stock solution determined
in Sec. 7.6, prepare a soil spiking solution at a concentration of 40 /xg/L
by diluting the stock solution. A 1.0 ml volume of this spiking solution
7580 - 5 Revision 0
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added to a 40 g wet soil sample will produce a concentration of
approximately 1 M9/kg of P4.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 White phosphorus is released into the environment from smoke
munitions in the form of small, discrete particles. These particles persist in
soils, sediments, and may occur as suspended or colloidal particles in anoxic
waters. Therefore, some samples or sample aliquots from a given location may
contain P4 particles while others do not. The nature and distribution of P4
contamination from other, non-military, sources has not been studied, but sample
collection procedures should address the likelihood that P4 is present in
discrete particles, and must be designed to ensure that multiple representative
samples of the matrix of interest are collected. In addition, soil and sediment
samples must be carefully homogenized and subsampled.
6.2 Because P4 will oxidize on contact with oxygen, care must be taken
to limit the contact of the sample with the atmosphere and to minimize any
introduction of air into the samples. In addition, work by Walsh and Nadeau
(Ref. 1) and others indicate that P4 may be subject to losses as a result of
volatilization from the sample.
6.2.1 Aqueous samples should be poured gently into the sample
container to minimize agitation which might drive off the volatile P4. If
bubbling does occur while transferring the sample to the container, the
sample should be discarded and another sample collected. Each container
should be filled with sample until it overflows. Each container should be
tightly sealed with a PTFE-lined cap. The container should then be
inverted to check for air bubbles. If any air bubbles are present, a new
sample must be collected.
6.2.2 Containers for soil samples should be filled as completely
as possible, eliminating as much free air space as practical.
6.3 Samples are preserved by cooling to approximately 4°C. Do NOT adjust
the pH of water samples or add chemical preservatives, as these may oxidize the
P4.
6.4 EPA has not established formal holding times for samples containing
P4. However, preliminary data suggest that water samples should be stored at
approximately 4°C in the dark, and should be extracted within 5 days of
collection. Soil/sediment samples should be stored at approximately 4°C, in the
dark, and kept tightly sealed to prevent loss of moisture. When stored in this
manner, preliminary data indicate that soil/sediment samples may be held
indefinitely.
6.5 Due to the volatility of diethyl ether, water sample extracts
prepared with diethyl ether (Sec. 7.3) should be analyzed within 8 hours of
extraction, and extracts should be stored in tightly capped containers in a
refrigerator until analysis.
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6.6 Isooctane extracts of soil/sediment samples (Sec. 7.4) and of water
samples (using the less sensitive alternative extraction procedure in Sec. 7.6)
should be stored in tightly capped containers in a refrigerator and analyzed
within 30 days of extraction.
7.0 PROCEDURE
7.1 Establish the instrument operation conditions, using the information
below as guidance.
Column: DB-1, 15 m by 0.53 mm ID with 3.0 urn film thickness
Oven Temp: 80°C (isothermal)
Carrier Gas: Nitrogen
Flow Rate: 30 mL/min
Using these conditions, P4 will elute between 2.5 and 3.0 minutes, and the entire
chromatographic run will typically be less than 5 minutes. Optimize the
performance to minimize interferences and maximize sensitivity. Document the
operating conditions used.
7.2 Initial calibration
Because of the different solvents used for soil/sediment samples and water
samples (by the more sensitive method), separate initial five-point calibrations
are required for each solvent. In addition, the nitrogen-phosphorus detector may
present problems with long-term stability. Therefore, a 5-point initial
calibration must be performed at the beginning of each 12-hour analytical shift
during which samples are to be analyzed. The calibration procedures are the same
for both solvents, and only the calibration associated with samples to be
analyzed that day must be run on that day (i.e., if only water samples will be
analyzed, only the calibration standards in diethyl ether need to be analyzed
that day).
As a practical matter, if both water and soil/sediment analyses are to be
performed, the water sample extracts in diethyl ether should be analyzed first,
to avoid evaporation of the solvent. If water samples are extracted using the
less sensitive procedure involving isooctane, then both water and soil/sediment
extracts may be analyzed using the same initial calibration in isooctane.
Perform either of the initial calibrations each day, using the procedure
outlined below. See Method 8000 for further details of external standard
calibration procedures.
7.2.1 The instrument is calibrated by injecting 1.0 /xL aliquots of
each calibration standard. To avoid "memory effects," vary the order of
the five standards, or analyze from lowest concentration to highest.
7.2.2 Calculate the calibration factor (CF) for the initial
calibration curve as follows:
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Area of the peak
(Standard concentration in ng/uL)(uL injected)
Peak height may be used for calculating the calibration factor, but may not
be as representative to small, broad, or oddly shaped peaks.
7.2.3 The linearity of the calibration is evaluated on the basis
of the relative standard deviation of the five calibration factors, in
accordance with Method 8000. Calculate the mean CF, the standard deviation
(SD) of the CFs, and the relative standard deviation (RSD), as follows.
mean CF = CF =
I (CF-CF):
SD =
n-1
RSD = — x 100
CF
where n is the number of initial calibration standards analyzed.
The calculation of a calibration factor is analogous to the
calculation of the slope of a regression line forced through the origin
(0,0). Data from the U. S. Army Corps of Engineers indicates that the NPD
response is linear over a range of at least 20-fold, and passes through the
origin. In order to be used for sample analyses, the RSD of the initial
calibration must be less than or equal to 15%. As noted above, the initial
calibration must be performed at the beginning of each analytical shift
during which samples will be analyzed.
7.3 Water sample extraction - diethyl ether extraction procedure
providing sensitivity of approximately 0.01 M9/L- See Sec. 7.6 for the less
sensitive isooctane alternative extraction procedure.
7.3.1 Carefully transfer a 500-mL aliquot of the water sample to
a 500-mL separatory funnel (a larger separatory funnel may be employed).
Add 50 mL of diethyl ether, and shake the separatory funnel for 5 minutes
with periodic venting. Allow the sample to stand for 15 minutes, or until
phase separation occurs.
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Optional Step: Add 16 g of sodium chloride to the mixture of
liquids in the separatory funnel to increase and stabilize the ionic
strength of the water sample and aid in the phase separation during
the extraction. If the sample is seawater, addition of the sodium
chloride is not necessary.
7.3.2 Diethyl ether is relatively soluble in water and the
solubility is greatly affected by temperature. After phase separation,
collect the diethyl ether (usually 3-10 ml) in a 10-mL graduated cylinder,
and record the exact volume. Note: The volume of the ether layer will
depend on the temperature and the ionic strength of the water sample.
7.3.3 For ease of application in a production laboratory
environment, adjust the volume of the diethyl ether extract to a constant
volume of 10.0 ml at this point. The extract is then concentrated by back
extraction with reagent water in Sec. 7.3.4. The advantage of the use of
a constant extract volume here is that it minimizes the need to recalculate
the volume of reagent water required for each sample extract, although the
latter approach may be employed. See Sec. 7.7 for details of the
calculation of the volume of reagent water required.
7.3.4 The volume of the diethyl ether extract is reduced to
approximately 1.0 ml by back-extraction with reagent water. Transfer the
diethyl ether extract to a 125-mL separatory funnel and add 99.2 ml of
reagent water. Shake for 1 minute.
7.3.5 After phase separation, collect the remaining diethyl ether
phase in a 10-mL (or smaller) graduated cylinder and record the exact
volume. Tightly cap the graduated cylinder until the extract is analyzed.
See Sec. 6.4 for a discussion of holding times for these sample extracts.
7.3.6 If no diethyl ether phase separates, check the temperature
of the solution. If the temperature is significantly below 25eC, then all
of the diethyl ether may remain in solution. There are three practical
solutions to this problem.
7.3.6.1 Warm the solution in the separatory funnel to 25°C,
and allow the phases to separate.
7.3.6.2 Add small volumes (0.5 ml or less) of fresh diethyl
ether to the solution, shake the separatory funnel, and allow the
phases to separate. Continue adding fresh ether until the
solubility of the ether in the reagent water is exceeded and the
extract has been concentrated to approximately 1.0 ml.
7.3.6.3 If this problem persists, calculate the volume of
reagent water required at the temperature of the solution (i.e., the
ambient laboratory temperature), using Sec. 7.7 and the solubility
and density of diethyl ether at the new temperature, and extract
another aliquot of the sample and use the newly calculated volume of
reagent water for back extraction.
7.3.7 Prepare the water matrix spike/matrix spike duplicate
(MS/MSD) aliquots by adding 500 ml of the water sample selected for spiking
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7.4.1 Carefully homogenize the soil/sediment sample in its original
container using a spatula. Weigh out 40 g of the homogenized wet sample
into a pre-weighed 120-mL glass jar.
7.4.2 Weigh out a separate 5-10 g aliquot of each sample for use
in determining the percent moisture. Air-dry each sample in a fume hood
for at least a day, then dry this aliquot at 105°C for 24 hours and
reweigh. The percent moisture is calculated as:
n 4. . 4. wet weight (g) -dry weight (g) -..
Percent moisture = 2 IZi £ ± i±ix 100
wet weight (g)
As noted in Sec. 2.3, soil/sediment P4 concentrations are reported on a
wet-weight basis using this method. However, the percent moisture is
reported separately so that the data user can make comparisons between
samples and perform dry weight calculations as necessary.
7.4.3 Add 10.0 ml (9.0 ml for spiked soil samples) of degassed
Type I reagent water and 10.0 ml of isooctane the sample in the glass jar
from Sec. 7.4.1, and seal the jar with the PTFE-lined cap.
7.4.4 Vortex the jar for 1 minute.
7.4.5 Place the jars on a platform shaker, and shake for 18 hours
(or overnight) at 2500 rpm.
7.4.6 After removing the samples from the platform shaker, let the
samples stand for about 15 minutes to allow phase separation. If a clear
isooctane layer does not form, centrifuge a portion of the sample for 5 min
at 2500 rpm.
7.4.7 Using a disposable Pasteur pipet, transfer an aliquot of the
isooctane layer to a suitable labeled storage vial with a PTFE-lined cap.
See Sec. 6.4 for a discussion of holding times for these sample extracts.
7.4.8 Prepare the MS/MSD aliquots by weighing out two additional
40-g aliquots of the soil/sediment sample chosen for spiking into clean
120-mL glass jars. Add 1.0 ml of the aqueous spiking solution (Sec.
5.11.2) to each jar. Seal each jar immediately, and swirl it until the
contents are mixed (approximately five times). Allow the samples to
equilibrate for 24 hours before extraction. After 24 hours, extract the
samples, beginning at Sec. 7.4.3.
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7.5 Sample analysis
7.5.1 Allow the sample extract to warm to room temperature and
inject 1.0 /zL of the extract (water or soil/sediment) into the GC, using
a 10 /nL gas tight syringe. Record the retention time and peak area (peak
height optional) of P4 in the sample extract.
7.5.2 Calculate the concentration of P4 in the water samples as
follows:
C (ng/L) =
CF x V8 x Vf
where: As = Area of the sample peak
Vf = Final extract volume in L
Vs = Volume of sample extracted in L
Vi = Volume injected in L
and
CF = Average calibration factor from the initial
calibration in diethyl ether
7.5.3 Calculate the concentration of P4 in the soil/sediment
samples as follows:
A x V.
C (ng/g) = • f
CF x Mg x Vj
where: As = Area of the sample peak
Vf = Final extract volume in L
Ms = Mass of sample extracted in g
V| = Volume injected in L
and
CF = Average calibration factor from the initial
calibration in isooctane
Using the units above, the concentration will be in ng/g, which is
equivalent to /zg/kg.
For water samples extracted with the isooctane procedure (Sec. 7.6),
perform the calculation as described in Sec. 7.6.5.
7.6 Alternative water sample extraction procedure providing sensitivity
of approximately 0.1 fj.g/1. This procedure must be used to determine the
concentration of the aqueous stock solution in Sec. 5.10.
7.6.1 Add 30 ml of the water sample (or the aqueous stock solution)
to a 40-mL vial with a PTFE-lined cap. Add 3.0 ml of isooctane to the vial
and cap it tightly.
7.6.2 Shake the vial for 5 minutes, and let stand to allow the
phases to separate.
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7.6.3 Remove the isooctane layer with a disposable Pasteur pipet.
7.6.4 Analyze a 1.0 /xL aliquot of the isooctane using the
procedure in Sec. 7.5.1.
7.6.5 Calculate the concentration of P4 using the equation in Sec.
7.5.3, using 0.0030 L (3.0 ml) as the final extract volume and 0.030 L (30
mL) as the sample volume. Substituting the sample volume for the mass (Ms)
in Sec. 7.5.3 will result in a concentration in units of ng/L.
7.7 Calculation of the volume of reagent water needed to concentrate the
diethyl ether extract to 1.0 mL.
Diethyl ether is very soluble in water, and given the solubility and the
density of diethyl ether, the volume of ether that will dissolve in a known
volume of reagent grade water can be calculated. By reversing the calculation,
the volume of reagent water that would be necessary to dissolve a specific
portion of a diethyl ether extract can be determined. Since the P4 will remain
in the free ether phase, the diethyl ether extract can be safely and effectively
be concentrated by back extraction with reagent water.
7.7.1 Both the solubility and density of diethyl ether vary with
temperature. At 25°C, the solubility of ether in water is 6.05%, on a
weight/weight basis. The density of diethyl ether is 0.7076 g/mL at 25eC.
The density of reagent water at 25°C is 0.997 g/mL. Reducing the volume
of ether in Sec. 7.3.3, 10 mL, to 1.0 mL will require dissolving 9.0 mL of
ether in reagent water.
7.7.2 The volume of "excess" ether is 9.0 mL.
7.7.3 The mass of this ether is (9.0 mL x 0.7076 g/mL) = 6.37 g.
7.7.4 The mass of an aqueous solution saturated with 6.37 g of
ether is (6.37 g)/(0.0605) = 105.3 g.
7.7.5 The mass of water in that aqueous solution is (105.3 - 6.37),
or 98.9 g.
7.7.6 The volume of water required to dissolve 9.0 mL of ether
is (98.9 g)/(0.997 g/mL) = 99.2 mL. Therefore, 99.2 mL of reagent
water are added to the diethyl ether extract in Sec. 7.3.4.
7.7.7 Using these relationships, the volume of reagent water needed
to concentrate other volumes of diethyl ether can also be calculated.
Also, similar calculations can be made for temperatures other than 25°C.
For instance, at 20°C, the solubility of diethyl ether in reagent water is
6.89% (w/w), the density of diethyl ether is 0.7133 g/mL, and the density
of water is 0.9982 g/mL. Substituting these values into the calculations
shown above, the volume of reagent water required to concentrate 10.0 mL
of diethyl ether to 1.0 mL at 20°C is 91.7 mL.
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7.7.8 Table 1 lists the volumes of reagent water needed to
concentrate diethyl ether extracts of various volumes less than 10.0 ml to
a final volume of 1.0 ml, for both 20 and 25°C.
7.8 Solid-phase micro-extraction (SPME)
Data from the U. S. Army Corps of Engineers suggest that SPME may be a
useful technique for the analysis of P4. It may be used to screen samples for
P4, by simply exposing the SPME fiber to the water sample, or adding reagent
water to a soil/sediment sample and exposing the fiber to the headspace. The
fiber is then thermally desorbed in a heated injection port of the GC. Such
screening results may be used to differentiate between water samples that require
the added sensitivity of the diethyl ether extraction and those that may be
adequately treated with the isooctance procedure.
Additionally, SPME may offer an alternative to the use of either solvent
in the determination of P4 in environmental samples. Further work in this area
is on-going at the U. S. Army Corps of Engineers, and may be added to later
revisions of this method.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses this method is required to operate a formal
quality control program. The minimum requirements of this program consist of an
initial demonstration of laboratory capability and an ongoing analysis of spiked
samples to evaluate and document data quality. The laboratory must maintain
records to document the quality of the data generated. Ongoing data quality
checks are compared with established performance criteria to determine if the
results of analyses meet the performance characteristics of the method. When
results of sample spikes indicate atypical method performance, a quality control
reference sample must be analyzed to confirm that the measurements were performed
in an in-control mode of operation.
8.2 Before processing any samples, and with each batch of samples (up to
a maximum of 20 environmental samples of a similar matrix), the analyst should
demonstrate, through the analysis of a method blank, that interferences from the
analytical system, glassware, and reagents are under control.
8.2.1 Each time a set of samples is extracted or there is a change
in reagents, a method blank should be processed as a safeguard against
chronic laboratory contamination.
8.2.2 The method blank should be carried through all stages of
sample preparation and measurement.
8.2.3 For water samples, the method blank consists of a 500 mL
volume of reagent water carried through the entire analytical procedure.
8.2.4 For soil/sediment samples, the method blank may be prepared
from a 20-g aliquot of a dry soil/sediment sample from an area not
contaminated with P4, or 20-g of clean dry sand. The 20-g aliquot is mixed
with 20 mL of reagent water and allowed to stand for one hour.
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NOTE: In order to be acceptable, neither the water method blank nor the
soil/sediment method blank may contain any P4 detectable by this
method. All samples associated with a contaminated method blank
should be re-extracted and reanalyzed.
8.3 Prior to the analysis of any sample extracts, the analyst must
perform an initial five-point calibration that meets the performance
specifications in Sec. 7.2.3. This initial calibration must be repeated at the
beginning of each 12-hour analytical shift during which samples are analyzed.
The initial calibration must be performed using the same solvent as the sample
extracts to be analyzed, i.e., separate initial calibrations are required for
diethyl ether and isooctane.
8.4 The analyst must verify the initial calibration periodically during
the course of sample analyses to ensure that the response of the NPD has not
drifted. The calibration is verified using the mid-point (i.e., third of five)
standard from the initial calibration, as described below.
8.4.1 A total of 10 extracts, including blanks, samples, and MS/MSD
aliquots may be analyzed following an initial calibration that meets the
specifications in Sec. 7.2.3. After the injection of the tenth extract,
the mid-point calibration standard must be injected to verify the
calibration.
8.4.2 Based on the response of the calibration verification
standard, calculate the calibration factor according to Sec. 7.2.2.
8.4.3 Calculate the percent difference (%D) between the calibration
factor calculated from the calibration verification standard (CFJ and the
mean calibration factor from the initial calibration at the beginning of
the analytical shift, as follows.
CT -CF
% Difference = * x 100
CF
8.4.4 In order for analysis of samples to continue, the %D must be
within ± 15%. Otherwise, analysis must be halted until a new initial
calibration is performed.
8.4.5 If the calibration verification meets the ± 15% QC limit,
then sample analyses may continue, continuing to use the mean CF from the
initial calibration for calculating sample concentrations.
8.4.6 The calibration must be verified after the analysis of each
set of 10 extracts of sample, blanks, MS/MSD. The injection of the
calibration verification standard itself is not counted as part of the 10
injections. Analyses may continue in this fashion, with calibration
verification standards analyzed after each 10 sample extracts, until the
end of the 12-hour analytical shift, or until the verification standard
fails to meet the ± 15% QC limit.
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8.5 Initial demonstration of capability
The ability of the analyst to generate acceptable accuracy and precision
using this method is demonstrated through the analysis of spiked aliquots of
reagent water, as described below.
8.5.1 Four 500-mL aliquots of reagent water are spiked with the
aqueous spiking solution (Sec. 5.11.1) to produce a concentration of
approximately 0.01 ^tg/L of P4.
8.5.2 The four aliquots are analyzed according to the procedure
used for water samples, beginning in Sec. 7.3.
8.5.3 Calculate the recovery of P4 in each aliquot, using the
formula below.
C
Recovery = %R = — x 100
Cn
where:
C8 = Measured concentration of the spiked sample aliquot
Cn = Nominal (or theoretical) concentration of the spiked sample
aliquot
8.5.4 Calculate the mean recovery and the standard deviation of the
four recoveries.
8.5.5 The mean recovery must be within the range 30-130%, and the
standard deviation of the recoveries must be less than or equal to 30%.
These specifications were developed from data provided by the U. S. Army
Corps of Engineers, and represent a 95% confidence interval for the
recovery of P4 spiked into four aliquots at approximately 0.01 /xg/L (See
Table 3). Data from the Corps of Engineers suggest that recoveries in
water other than reagent water (i.e., pond water, tap water, etc.) may be
higher than in reagent water, perhaps because of the effects of ionic
strength or dissolved constituents on the solubility of P4.
8.5.6 If the mean recovery or the standard deviation of the
recoveries falls outside of these limits, then the analyst must examine the
entire analytical process, correct problems or inconsistencies, and repeat
this test, beginning at Sec. 8.5.1.
8.6 The laboratory must, on an ongoing basis, prepare and analyze matrix
spike and matrix spike duplicate samples to assess the precision and accuracy of
the procedure. The MS/MSD aliquots are prepared and analyzed as described in
Sees. 7.3.6 and 7.4.8. MS/MSD aliquots should be prepared each batch of samples
(up to a maximum of 20 environmental samples of a similar matrix). For
laboratories analyzing one to ten samples per month, at least one pair of MS/MSD
must be analyzed each month.
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The laboratory should develop QC limits for MS/MSD recoveries and precision
(RPD), using the procedures in Method 8000. In the absence of laboratory-
specific QC limits, the MS/MSD aliquots must have recoveries in the range 75-125%
and an RPD less than or equal to 25%.
9.0 METHOD PERFORMANCE
9.1 The Method Detection Limit (MDL) is defined in Sec. 5.0 of Chapter
One. MDL values were determined in reagent water, well water, and surface (pond)
water, spiked at approximately 0.01 ^9/L, and are shown in Table 4. These MDL
values were calculated from the results of 10 spiked aliquots of each matrix.
9.2 MDLs were determined for three soil types by spiking the soils with
an aqueous solution containing P4. The MDL values are shown in Table 5, and were
determined in clean sand, a sandy loam soil (Lebanon soil), and soil from the
Rocky Mountain Arsenal (USAEC Soil). None of these soils were taken from areas
where smoke munitions have been employed, and therefore were not expected to
contain any P4. These soil samples were spiked with P4 at concentrations of
approximately 1-2 M9Ag.
9.3 To date, only single laboratory performance data have been generated.
Those data indicate that there may be problems with the recovery of P4 from soils
containing high concentrations of metals. Therefore, laboratories employing this
method are encouraged to develop in-house performance data including MDLs and
accuracy and precision data for routinely encountered matrices. These data
should be developed in accordance with the procedures outlined in Method 8000.
10.0 REFERENCES
1. Walsh, M.E. and B. Nadeau, "Preliminary Evaluation of the Analytical
Holding Time for White Phosphorus in Surface Water," U.S. Army Cold Regions
Research and Engineering Laboratory, Hanover, NH, CRREL Report 94-13.
2. Taylor, S. and M.E. Walsh, "Optimization of an Analytical Method for
Determining White Phosphorus in Contaminated Sediments," U.S. Army Cold
Regions Research and Engineering Laboratory, Hanover, NH, CRREL Report 92-
21.
3. Walsh, M. E., and S. Taylor, 1993, "Analytical Method for White Phosphorus
in Munitions-Contaminated Sediments," Analytica Chimica Acta, 282: 55-61.
4. Walsh, M.E., 1995, "Analytical Method for White Phosphorus in Water,"
Bulletin of Environmental Contamination and Toxicology, 54(3).
5. Budavari, S., et a/., eds., 1989, The Merck Index, Merck & Co., Rahway, NJ.
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TABLE 1
VOLUME OF REAGENT WATER REQUIRED TO CONCENTRATE DIETHYL ETHER EXTRACTS TO A
1.0 ml FINAL VOLUME AT 20'C AND 25°C
Volume of Diethyl
Ether
Volume of Reagent Water
Required at 20°C
Volume of Reagent Water
Required at 25°C
10.00
9.75
9.50
9.25
9.00
8.75
8.50
8.25
8.00
7.75
7.50
7.25
7.00
6.75
6.50
6.25
6.00
5.75
5.50
5.25
5.00
4.75
4.50
4.25
4.00
3.75
3.50
3.25
3.00
2.75
2.50
2.25
2.00
1.75
1.50
1.25
91.7
89.3
86.9
84.5
82.1
79.7
77.3
74.8
72.4
70.0
67.6
65.2
62.8
60.4
57.9
55.5
53.1
50.7
48.3
45.9
43.5
41.0
38.6
36.2
33.8
31.4
29.0
26.6
24.1
21.7
19.3
16.9
14.5
12.1
9.7
7.2
99.2
96.4
93.7
90.9
88.2
85.4
82.7
79.9
77.1
74.4
71.6
68.9
66.1
63.4
60.6
57.9
55.1
52.4
49.6
46.8
44.1
41.3
38.6
35.8
33.1
30.3
27.6
24.8
22.0
19.3
16.5
13.8
11.0
8.3
5.5
2.8
Solubility of diethyl ether in water is 6.05% (w/w) at 25°C and 6.89% at 20°C.
Density of diethyl ether is 0.7076 g/mL at 25°C and 0.7133 g/mL at 20°C.
Density of water is 0.997 g/mL at 5°C and 0.9982 g/mL at 20°C.
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TABLE 2
RECOVERY OF P4 FROM SPIKED WATER SAMPLES
(ALL VALUES GIVEN AS PERCENT RECOVERY)
Reagent Water Well Water Pond Water
52
77
44
68
69
68
57
64
56
66
46
94
87
124
74
91
91
99
91
90
92
86
99
82
80
83
84
68
56
68
Mean
Recovery 62.1 88.7 79.8
Standard
Deviation 9.7 19.6 12.6
Spike Level 0.012 0.0097 0.0101
The concentration results for these replicate samples were used to calculate the
MDL values in Table 4.
The two lowest and two highest concentration values from each set of replicates
were used to establish the recovery and precision specifications in Sec. 8.5.
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Mean
Recovery
Standard
Deviation
Spike Level
TABLE 3
RECOVERY OF P4 FROM SPIKED SOIL SAMPLES
(ALL VALUES GIVEN AS PERCENT RECOVERY)
Sand
92.5
4.1
1.99
Lebanon Soil
85.9
12.4
1.24
USAEC Soil
90
90
97
94
96
85
89
94
92
98
98
66
86
87
93
82
86
66
102
94
76
68
73
74
76
74
74
71
74
70
73.0
2.5
0.97
The concentration results for these replicate samples were used to calculate the
MDL values in Table 5.
The two lowest and two highest concentration values from each set of replicates
were used to establish the recovery and precision specifications in Sec. 8.5.
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TABLE 4
METHOD DETECTION LIMITS CALCULATED FOR THREE WATER TYPES
Reagent Water Well Water Pond Water
MDL (M9/L) 0.008 0.009 0.008
These MDLs were calculated from the analyses of 10 replicate aliquots of
each water type spiked with P4 at 0.0097 to 0.012 M9/L. The MDLs were calculated
as the Student's t value for 10 replicates (2.821) multiplied by the standard
deviation of the results for each water type.
TABLE 5
METHOD DETECTION LIMITS CALCULATED FOR THREE SOIL TYPES
Sand Lebanon Soil USAEC Soil
MDL (/ig/kg) 0.02 0.43 0.07
These MDLs were calculated from the analyses of 10 replicate aliquots of
each soil type spiked with P4 at 0.97 to 1.99 Atg/kg. The MDLs were calculated
as the Student's t value for 10 replicates (2.821) multiplied by the standard
deviation of the results for each soil type.
As can be seen, the MDL values vary significantly. However, if one
compares the spiked concentration for each matrix with the MDL value, it is clear
that both the Sand and USAEC Soil were not spiked within 3-5 times the estimated
detection limit (as required, see Chapter One). The ratio of the spiking level
to the MDL for Sand was 9.7, and 14 for the USAEC Soil. In contrast, the ratio
for the Lebanon Soil is 2.9. Therefore, the MDL for Lebanon Soil should be
considered as more representative of the method performance than either of the
other values because it is closer to the 3-5 times the estimated detection limit
range.
7580 - 20 Revision 0
January 1995
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METHOD 7580
WHITE PHOSPHORUS (P.) BY SOLVENT EXTRACTION AND GAS CHRQMATOGRAPHY
7.1 - 7.2 Establish
instrument operating
conditions and perform
the initial calibration.
Soil/Sediment
Is it a
water sampl
or a soil/sedimen
sample?
Water
7.4 Perform soil/
sediment
sample extraction.
7.3 Perform water
sample extraction.
7.6 Perform spike
concentration
determination.
7.7 Determine volume of
reagent water necessary
for concentration.
7.8 Perform the solid-
phase micro-extraction.
7580 - 21
Revision 0
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CHAPTER FOUR
ORGANIC ANALYTES
4.1 SAMPLING CONSIDERATIONS
4.1.1 Introduction
Following the initial and critical step of designing a sampling plan
(Chapter Nine) is the implementation of that plan such that a representative
sample of the solid waste is collected. Once the sample has been collected it
must be stored and preserved to maintain the chemical and physical properties
that it possessed at the time of collection. The sample type, type of containers
and their preparation, possible forms of contamination, and preservation methods
are all items which must be thoroughly examined in order to maintain the
integrity of the samples. This section highlights considerations which must be
addressed in order to maintain a sample's integrity and representativeness. This
section is, however, applicable only to trace analyses.
Quality Control (QC) requirements need not be met for all compounds
presented in the Table of Analytes for the method in use, rather, they must be
met for all compounds reported. A report of non-detect is considered a
quantitative report, and must meet all applicable QC requirements for that
compound and the method used.
4.1.2 Sample Handling and Preservation
This section deals separately with volatile and semivolatile organics.
Refer to Chapter Two and Table 4-1 of this section for sample containers, sample
preservation, and sample holding time information.
Volatile Orqanics
Standard 40 ml glass screw-cap VOA vials with Teflon lined silicone septa
may be used for liquid matrices. Special 40 ml VOA vials for purge-and-trap of
solid samples are described in Method 5035. VOA vials for headspace analysis of
solid samples are described in Method 5021. Standard 125 ml widemouth glass
containers may be used for Methods 5031 and 5032. The vials and septa should be
washed with soap and water and rinsed with distilled deionized water. After
thoroughly cleaning the vials and septa, they should be placed in an oven and
dried at 100°C for approximately one hour.
NOTE: Do not heat the septa for extended periods of time (i.e., more than one
hour, because the silicone begins to slowly degrade at 105°C).
When collecting the samples, liquids and solids should be introduced into
the vials gently to reduce agitation which might drive off volatile compounds.
In general, liquid samples should be poured into the vial without
introducing any air bubbles within the vial as it is being filled. Should
bubbling occur as a result of violent pouring, the sample must be poured out and
the vial refilled. The vials should be completely filled at the time of
sampling, so that when the septum cap is fitted and sealed, and the vial
inverted, no headspace is visible. The sample should be hermetically sealed in
FOUR - 1 Revision 3
January 1995
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the vial at the time of sampling, and must not be opened prior to analysis to
preserve their integrity.
Due to differing solubility and diffusion properties of gases in
LIQUID matrices at different temperatures, it is possible for the
sample to generate some headspace during storage. This headspace
will appear in the form of micro bubbles, and should not invalidate
a sample for volatiles analysis.
The presence of a macro bubble in a sample vial generally indicates
either improper sampling technique or a source of gas evolution
within the sample. The latter case is usually accompanied by a
buildup of pressure within the vial, (e.g. carbonate-containing
samples preserved with acid). Studies conducted by the USEPA
(EMSL-Ci, unpublished data) indicate that "pea-sized" bubbles (i.e.,
bubbles not exceeding 1/4 inch or 6 mm in diameter) did not
adversely affect volatiles data. These bubbles were generally
encountered in wastewater samples, which are more susceptible to
variations in gas solubility than are groundwater samples.
Immediately prior to analysis of liquid samples, the aliquot to be analyzed
should be taken from the vial using the instructions from the appropriate sample
introduction technique:
For smaller analysis volumes, a gas-tight syringe may be inserted
directly through the septum of the vial to withdraw the sample.
For larger analysis volumes, (e.g. purge-and-trap analyses) the
sample may be carefully poured into the syringe barrel. Opening a
volatile sample to pour a sample into a syringe destroys the
validity of the sample for future analysis. Therefore, if there is
only one VOA vial, it is strongly recommended that the analyst fill
a second syringe at this time to protect against possible loss of
sample integrity. This second sample is maintained only until such
time as the analyst has determined that the first sample has been
analyzed properly.
If these guidelines are not followed, the validity of the data generated from the
samples may be suspect.
VOA vials for samples with solid or semi-solid matrices (e.g., sludges)
should be filled according to the guidance given in the appropriate 5000 series
sample introduction method (see Table 4-1) to be used. When 125-mL widemouth
glass continers are used, the containers should be filled as completely as
possible. The 125-mL vials should be tapped slightly as they are filled to try
and eliminate as much free air space as possible. A minimum of two vials should
also be filled per sample location.
At least two VOA vials should be filled and labeled immediately at the
point at which the sample is collected. They should NOT be filled near a running
motor or any type of exhaust system because discharged fumes and vapors may
contaminate the samples. The two vials from each sampling location should then
be sealed in separate plastic bags to prevent cross-contamination between
samples, particularly if the sampled waste is suspected of containing high levels
FOUR - 2 Revision 3
January 1995
-------
of volatile organics. (Activated carbon may also be included in the bags to
prevent cross-contamination from highly contaminated samples). VOA samples may
also be contaminated by diffusion of volatile organics through the septum during
shipment and storage. To monitor possible contamination, a trip blank prepared
from organic-free reagent water (as defined in Chapter One) should be carried
throughout the sampling, storage, and shipping process.
Semivolatile Organics (including Pesticides, PCBs and Herbicides.)
Containers used to collect samples for the determination of semivolatile
organic compounds should be soap and water washed followed by methanol (or
isopropanol) rinsing (see Sec. 4.1.4 for specific instructions on glassware
cleaning). The sample containers should be of glass or Teflon, and have screw-
caps with Teflon lined septa. In situations where Teflon is not available,
solvent-rinsed aluminum foil may be used as a liner. However, acidic or basic
samples may react with the aluminum foil, causing eventual contamination of the
sample. Plastic containers or lids may NOT be used for the storage of samples
due to the possibility of sample contamination from the phthalate esters and
other hydrocarbons within the plastic. Sample containers should be filled with
care so as to prevent any portion of the collected sample coming in contact with
the sampler's gloves, thus causing contamination. Samples should not be
collected or stored in the presence of exhaust fumes. If the sample comes in
contact with the sampler (e.g. if an automatic sampler is used), run organic-free
reagent water through the sampler and use as a field blank.
4.1.3
Safety should always be the primary consideration in the collection of
samples. A thorough understanding of the waste production process, as well as
all of the potential hazards making up the waste, should be investigated whenever
possible. The site should be visually evaluated just prior to sampling to
determine additional safety measures. Minimum protection of gloves and safety
glasses should be worn to prevent sample contact with the skin and eyes. A
respirator should be worn even when working outdoors if organic vapors are
present. More hazardous sampling missions may require the use of supplied air
and special clothing.
4.1.4 Cleaning of Glassware
In the analysis of samples containing components in the parts per billion
range, the preparation of scrupulously clean glassware is necessary. Failure to
do so can lead to a myriad of problems in the interpretation of the final
chromatograms due to the presence of extraneous peaks resulting from
contamination. Particular care must be taken with glassware such as Soxhlet
extractors, Kuderna-Danish evaporative concentrators, sampling-train components,
or any other glassware coming in contact with an extract that will be evaporated
to a smaller volume. The process of concentrating the compounds of interest in
this operation may similarly concentrate the contaminating substance(s), which
may seriously distort the results.
The basic cleaning steps are:
1. Removal of surface residuals immediately after use;
FOUR - 3 Revision 3
January 1995
-------
2. Hot soak to loosen and float most particulate material;
3. Hot water rinse to flush away floated participates;
4. Soak with an oxidizing agent to destroy traces of organic compounds;
5. Hot water rinse to flush away materials loosened by the deep penetrant
soak;
6. Distilled water rinse to remove metallic deposits from the tap water;
7. Alcohol, e.g., isopropanol or methanol, rinse to flush off any final
traces of organic materials and remove the water; and
8. Flushing the item immediately before use with some of the same solvent
that will be used in the analysis.
Each of these eight fundamental steps are discussed here in the order in
which they appeared on the preceding page.
1. As soon possible after glassware (i.e., beakers, pipets, flasks, or
bottles) has come in contact with sample or standards, the glassware
should be flushed with alcohol before it is placed in the hot
detergent soak. If this is not done, the soak bath may serve to
contaminate all other glassware placed therein.
2. The hot soak consists of a bath of a suitable detergent in water of
50°C or higher. The detergent, powder or liquid, should be entirely
synthetic and not a fatty acid base. There are very few areas of the
country where the water hardness is sufficiently low to avoid the
formation of some hard-water scum resulting from the reaction between
calcium and magnesium salts with a fatty acid soap. This hard-water
scum or curd would have an affinity particularly for many chlorinated
compounds and, being almost wholly water-insoluble, would deposit on
all glassware in the bath in a thin film.
There are many suitable detergents on the wholesale and retail market.
Most of the common liquid dishwashing detergents sold at retail are
satisfactory but are more expensive than other comparable products
sold industrially. Alconox, in powder or tablet form, is manufactured
by Alconox, Inc., New York, and is marketed by a number of laboratory
supply firms. Sparkleen, another powdered product, is distributed by
Fisher Scientific Company.
3. No comments required.
4. The most common and highly effective oxidizing agent for removal of
traces of organic compounds is the traditional chromic acid solution
made up of concentrated sulfuric acid and potassium or sodium
dichromate. For maximum efficiency, the soak solution should be hot
(40-50°C). Safety precautions must be rigidly observed in the
handling of this solution. Prescribed safety gear should include
safety goggles, rubber gloves, and apron. The bench area where this
FOUR - 4 Revision 3
January 1995
-------
operation is conducted should be covered with fluorocarbon sheeting
because spattering will disintegrate any unprotected surfaces.
The potential hazards of using chromic-sulfuric acid mixture are great
and have been well publicized. There are now commercially available
substitutes that possess the advantage of safety in handling. These
are biodegradable concentrates with a claimed cleaning strength equal
to the chromic acid solution. They are alkaline, equivalent to ca.
0.1 N NaOH upon dilution, and are claimed to remove dried blood,
silicone greases, distillation residues, insoluble organic residues,
etc. They are further claimed to remove radioactive traces and will
not attack glass or exert a corrosive effect on skin or clothing. One
such product is "Chem Solv 2157," manufactured by Mallinckrodt and
available through laboratory supply firms. Another comparable product
is "Detex," a product of Borer-Chemie, Solothurn, Switzerland.
5, 6, and 7. No comments required.
8. There is always a possibility that between the time of washing and the
next use, the glassware could pick up some contamination from either
the air or direct contact. To ensure against this, it is good
practice to flush the item immediately before use with some of the
same solvent that will be used in the analysis.
The drying and storage of the cleaned glassware is of critical importance
to prevent the beneficial effects of the scrupulous cleaning from being
nullified. Pegboard drying is not recommended. It is recommended that
laboratory glassware and equipment be dried at 100°C. Under no circumstances
should such small items be left in the open without protective covering. The
dust cloud raised by the daily sweeping of the laboratory floor can most
effectively recontaminate the clean glassware.
As an alternate to solvent rinsing, the glassware can be heated to a
minimum of 300°C to vaporize any organics. Do not use this high temperature
treatment on volumetric glassware, glassware with ground glass joints, or
sintered glassware.
4.1.5 High Concentration Samples
Cross contamination of trace concentration samples may occur when
prepared in the same laboratory with high concentration samples. Ideally,
if both type samples are being handled, a laboratory and glassware
dedicated solely to the preparation of high concentration samples would be
available for this purpose. If this is not feasible, as a minimum when
preparing high concentration samples, disposable glassware should be used
or, at least, glassware dedicated entirely to the high concentration
samples. Avoid cleaning glassware used for both trace and high
concentration samples in the same area.
FOUR - 5 Revision 3
January 1995
-------
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4.2 SAMPLE PREPARATION METHODS
4.2.1 EXTRACTIONS AND PREPARATIONS
The following methods are included in this section:
Method
Method
Method
Method
Method
Method
Method
3500B:
3510C:
3520C:
3535:
3540C:
3541:
3542:
Method 3545:
Method 3550B:
Method 3560:
Method 3561:
Method 3580A:
Method 3585:
Method 5000:
Method 5021:
Method 5030B:
Method 5031:
Method 5032:
Method 5035:
Method 5041A:
Organic Extraction and Sample Preparation
Separatory Funnel Liquid-Liquid Extraction
Continuous Liquid-Liquid Extraction
Solid Phase Extraction (SPE)
Soxhlet Extraction
Automated Soxhlet Extraction
Extraction of Semivolatile Analytes Collected
Using Modified Method 5 (Method 0010) Sampling
Train
Accelerated Solvent Extraction
Ultrasonic Extraction
Supercritical Fluid Extraction of Total
Recoverable Petroleum Hydrocarbons (TRPH)
Supercritical Fluid Extraction of Polynuclear
Aromatic Hydrocarbons
Waste Dilution
Waste Dilution for Volatile Organics
Sample Preparation for Volatile Organic Compounds
Volatile Organic Compounds in Soils and Other
Solid Matrices Using Equilibrium Headspace
Apparatus
Purge-and-Trap for Aqueous Samples
Volatile, Nonpurgeable, Water-Soluble Compounds
by Azeotropic Distillation
Volatile Organic Compounds by Vacuum Distillation
Closed-System Purge-and-Trap and Extraction for
Volatile Organics in Soil and Waste Samples
Analysis of Sorbent Cartridges from Volatile
Organic Sampling Train (VOST): Capillary GC/MS
Technique
FOUR - 8
Revision 3
January 1995
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METHOD 3500B
ORGANIC EXTRACTION AND SAMPLE PREPARATION
1.0 SCOPE AND APPLICATION
1.1 Method 3500 provides general guidance on the selection of methods used
in the quantitative extraction (or dilution) of samples for analysis by one of
the semivolatile or nonvolatile determinative methods. Cleanup and/or analysis
of the resultant extracts are described in Chapter Two as well as in Method 3600
(Cleanup) and Method 8000 (Analysis).
1.2 The following table lists the extraction methods, the matrix and the
analyte category.
SAMPLE EXTRACTION METHODS FOR SEMIVOLATILES AND NONVOLATILES
Method #
3510
3520
3535
3540
3541
3542
3545
3550
3560/
3561
3580
Matrix
Aqueous
Aqueous
Aqueous
Solids
Solids
Air Sampling Train
Solids
Solids
Solids
Non-aqueous Solvent
Soluble Waste
Extraction Type
Separatory Funnel
Liquid-Liquid
Extraction
Continuous Liquid-
Liquid Extraction
Solid-Phase
Extraction (SPE)
Soxhlet Extraction
Automated Soxhlet
Extraction
Separatory Funnel &
Soxhlet Extraction
Accelerated Solvent
Extraction (ASE)
(Heat & Pressure)
Ultrasonic
Extraction
Supercritical Fluid
Extraction (SFE)
Solvent Dilution
Analytes
Semivolatile &
Nonvolatile Organics
Semivolatile &
Nonvolatile Organics
Semivolatile &
Nonvolatile Organics
Semivolatile &
Nonvolatile Organics
Polychlorinated
Biphenyls,
Organochlorine
Pesticides, &
Semivolatiles
Semivolatile Organics
Semivolatile &
Nonvolatile Organics
Semivolatile &
Nonvolatile Orgajiics
Semivolatile Petroleum
Hydrocarbons &
Polynuclear Aromatic
Hydrocarbons
Semivolatile &
Nonvolatile Organics
3500B - 1
Revision 2
January 1995
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1.3 Method 3580 may be used for the solvent dilution of non-aqueous
semivolatile and nonvolatile organic samples prior to cleanup and/or analysis.
1.4 Methods 3545, 3560, and 3561 are techniques that utilize pressurized
solvent extraction to reduce the amount of solvent needed to extract target
analytes and reduce the extraction time when compared to more traditional
techniques such as Soxhlet extraction.
2.0 SUMMARY OF METHOD
2.1 A sample of a known volume or weight is extracted with solvent or
diluted with solvent. Method choices for aqueous samples include liquid-liquid
extraction by separatory funnel or by continuous extractor and solid-phase
extraction (SPE). Method choices for soil/sediment and solid waste samples
include standard solvent extraction methods utilizing either Soxhlet, automated
Soxhlet, or ultrasonic extraction. Solids may also be extracted using
pressurized extraction techniques such as supercritical fluid extraction or
heated accelerated solvent extraction.
2.2 The resultant extract is dried and concentrated in a Kuderna-Danish
(K-D) apparatus. Other concentration devices or techniques may be used in place
of the Kuderna-Danish concentrator if the quality control requirements of the
determinative methods are met (Method 8000, Sec. 8.0).
NOTE: Solvent recovery apparatus is recommended for use in methods that require
the use of Kuderna-Danish evaporative concentrators. EPA recommends the
incorporation of this type of reclamation system as a method to implement
an emissions reduction program.
2.3 See Sec. 7.0 for additional guidance to assist in selection of the
appropriate method.
3.0 INTERFERENCES
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield artifacts and/or interferences to sample analysis. All these materials
must be demonstrated to be free from interferences under the conditions of the
analysis by analyzing method blanks. Specific selection of reagents and
purification of solvents by distillation in all-glass systems may be necessary.
Refer to each method for specific guidance on quality control procedures and to
Chapter Four for guidance on the cleaning of glassware.
3.2 Interferences coextracted from the samples will vary considerably from
source to source. If analysis of an extracted sample is prevented due to
interferences, further cleanup of the sample extract may be necessary. Refer to
Method 3600 for guidance on cleanup procedures.
3.3 Phthalate esters contaminate many types of products commonly found in
the laboratory. Plastics, in particular, must be avoided because phthalates are
commonly used as plasticizers and are easily extracted from plastic materials.
Serious phthalate contamination may result at any time if consistent quality
control is not practiced.
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3.4 Soap residue (e.g. sodium dodecyl sulfate), which results in a basic
pH on glassware surfaces, may cause degradation of certain analytes.
Specifically, Aldrin, Heptachlor, and most organophosphorus pesticides will
degrade in this situation. This problem is especially pronounced with glassware
that may be difficult to rinse (e.g., 500-mL K-D flask). These items should be
hand-rinsed very carefully to avoid this problem.
4.0 APPARATUS AND MATERIALS
4.1 Refer to the specific method of interest for a description of the
apparatus and materials needed.
4.2 Solvent recovery apparatus is recommended for use in methods that
require the use of Kuderna-Danish evaporative concentrators. Incorporation of
this apparatus may be required by State or local municipality regulations that
govern air emissions of volatile organics. EPA recommends the incorporation of
this type of reclamation system as a method to implement an emissions reduction
program. Solvent recovery is a means to conform with waste minimization and
pollution prevention initiatives.
5.0 REAGENTS
5.1 Refer to the specific method of interest for a description of the
solvents needed.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water as defined in Chapter One.
5.3 Stock standards for spiking solutions - Stock solutions may be
prepared from pure standard materials or purchased as certified solutions. The
stock solutions used for the calibration standards are acceptable (dilutions must
be made in a water miscible solvent) except for the quality control check sample
stock concentrate which must be prepared independently to serve as a check on the
accuracy of the calibration solution.
5.3.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure compound. Dissolve the compound in a water miscible
solvent (i.e. methanol, acetone, isopropanol etc.) and dilute to volume in
a 10-mL volumetric flask. If compound purity is 96 percent or greater, the
weight can be used without correction to calculate the concentration of the
stock standard solution. Commercially-prepared stock standard solutions
can be used at any concentration if they are certified by the manufacturer
or by an independent source.
5.3.2 Stock standard solutions should be stored in Teflon®-sealed
containers at 4'C or below. The solutions should be checked frequently for
stability. Refer to the determinative method for holding times of the
stock solutions.
5.4 Surrogate standards - A surrogate (i.e., a compound that is chemically
similar to the analyte group but is not expected to occur in an environmental
sample) should be added to each sample, blank, laboratory control sample (LCS),
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and matrix spike sample just prior to extraction or processing. The recovery
of the surrogate standard is used to monitor for unusual matrix effects, gross
sample processing errors, etc. Surrogate recovery is evaluated for acceptance
by determining whether the measured concentration falls within the acceptance
limits.
5.4.1 Recommended surrogates for certain analyte groups are listed
in Table 1. For methods where no recommended surrogates are listed, the
lab is free to select compounds that fall within the definition provided
above. Even compounds that are on the method target analyte list may be
used as a surrogate as long as historical data are available to ensure
their absence at a given site. Normally one or more standards are added
for each analyte group.
5.4.2 Prepare a surrogate spiking concentrate by mixing stock
standards prepared above and diluting with a water miscible solvent.
Commercially prepared spiking solutions are acceptable. The concentration
for semivolatile/nonvolatile organic and pesticide analyses should be such
that a 1-mL aliquot into 1000 mL of a sample provides the concentrations
listed in Table 1. Where volumes of less than 1000 mL are extracted,
adjust the volume of surrogate standard proportionately. For matrices
other than water, 1 mL of surrogate standard is still the normal spiking
volume. However, if gel permeation chromatography will be used for sample
cleanup, 2 mL should be added to the sample. See Table 1 for recommended
surrogates and concentrations (in an aqueous sample). The spiking volumes
are normally listed in each extraction method. Where concentrations are
not listed, a concentration of 10 times the quantitation limit is
recommended. If the surrogate quantitation limit is unknown, the average
quantitation limit of method target analytes may be utilized to estimate
a surrogate quantitation limit.
5.5 Matrix spike standards - The following are recommended matrix spike
standard mixtures for a few analyte groups. Prepare a matrix spike concentrate
by mixing stock standards prepared above and diluting with a water miscible
solvent. Commercially-prepared spiking solutions are acceptable. The matrix
spike standards should be independent of the calibration standard. A few methods
provide guidance on concentrations and the selection of compounds for matrix
spikes (see Table 2).
5.5.1 Base/neutral and acid matrix spiking solution - Prepare a
spiking solution in methanol that contains each of the following
base/neutral compounds at 100 mg/L and the acid compounds at 200 mg/L for
water and sediment/soil samples. The concentration of these compounds
should be five times higher for waste samples.
Base/neutrals Acids
1,2,4-Trichlorobenzene Pentachlorophenol
Acenaphthene Phenol
2,4-Dinitrotoluene 2-Chlorophenol
Pyrene 4-Chloro-3-methylphenol
N-Nitroso-di-n-propylamine 4-Nitrophenol
1,4-Di chlorobenzene
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5.5.2 Organochlorine pesticide matrix spiking solution - Prepare a
spiking solution in acetone or methanol that contains the following
pesticides in the concentrations listed for water and sediment/soil. The
concentration should be five times higher for waste samples.
Pesticide Concentration (mq/L)
Lindane 0.2
Heptachlor 0.2
Aldrin 0.2
Dieldrin 0.5
Endrin 0.5
4,4'-DDT 0.5
5.5.3 For methods with no guidance, select five or more analytes
(select all analytes for methods with five or less) from each analyte group
for use in a spiking solution. Where matrix spike concentrations in the
sample are not listed it should be at or below the regulatory concentration
or, 1 to 5 times higher than the background concentration, whichever,
concentration would be larger.
5.6 Laboratory control spike standard - Use the matrix spike standard
prepared in Sec. 5.5 as the spike standard for the laboratory control sample
(LCS). The LCS should be spiked at the same concentration as the matrix spike.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
See Chapters Two and Four for guidance on sample collection.
7.0 PROCEDURE
7.1 Water, soil/sediment, sludge, and waste samples requiring analysis for
semivolatile and nonvolatile organic compounds (within this broad category are
special subsets of analytes, i.e., the different groups of pesticides,
explosives, PCBs etc.), must undergo solvent extraction prior to analysis. This
manual contains method choices that are dependent on the matrix, the physical
properties of the analytes, the sophistication and cost of equipment available
to a given laboratory, and the turn-around time required for sample preparation.
7.1.1 The laboratory should be responsible for ensuring that the
method chosen will provide acceptable extraction efficiency for the target
analytes in a given matrix. In general, Method 3520 - Continuous Extractor
for aqueous samples and Method 3540 - Soxhlet Extraction for solid samples
are considered the standard for a broad range of those matrices. Depending
on the requirements of the QA Project Plan, it may be necessary to verify
that any other SW-846 method (or non-SW-846 method) chosen for sample
extraction does provide appropriate extraction efficiency for the analytes
of concern from matrices at a given RCRA site. When performing method
comparisons, they must be performed on a site sample expected to contain
some of the target analytes rather than on spiked samples. Analyze four
portions of the well homogenized sample using the standard extraction
method and four portions by the extraction method of interest. For a
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method to be acceptable when comparing the means of the two sets of data,
the RSD must be < 20% for aqueous samples and < 30% for solid samples.
7.1.2 Each method has QC requirements that normally include the
addition of surrogates to each sample and QC samples plus the inclusion of
a matrix spike/ matrix spike duplicate (or matrix spike and duplicate
samples), a laboratory control sample, and a reagent blank, in each sample
extraction batch. The decision on whether to prepare and analyze duplicate
samples or a matrix spike/matrix spike duplicate must be based on a
knowledge of the samples in the extraction batch. If the sample selected
for duplicate analysis is known to contain target analytes, then precision
data will result. However, if the samples are unknown or expected to be
free of target analytes, then the batch should include the matrix
spike/matrix spike duplicate to ensure that precision data will be
generated within that extraction batch.
7.2 Method 3510 - Applicable to the extraction and concentration of
water-insoluble and slightly water-soluble organics from aqueous samples. A
measured volume of sample is solvent extracted using a separatory funnel. The
extract is dried, concentrated and, if necessary, exchanged into a solvent
compatible with further analysis. Separatory funnel extraction utilizes
relatively inexpensive glassware and is fairly rapid (three, 2-minute extractions
followed by filtration) but is labor intensive, uses fairly large volumes of
solvent and is subject to emulsion problems. Method 3520 should be used if an
emulsion forms between the solvent-sample phases, which cannot be broken by
mechanical techniques.
7.3 Method 3520 - Applicable to the extraction and concentration of
water-insoluble and slightly water-soluble organics from aqueous samples. A
measured volume of sample is extracted with an organic solvent in a continuous
liquid-liquid extractor. The solvent must have a density greater than that of
the sample. The extract is dried, concentrated and, if necessary, exchanged into
a solvent compatible with further analysis. Continuous extractors are excellent
for samples with particulates (of up to 1% solids) that cause emulsions, provide
more efficient extraction of analytes that are more difficult to extract and once
loaded, require no hands-on manipulation. However, they require more expensive
glassware, use fairly large volumes of solvent and extraction time is rather
lengthy (6 to 24 hours).
7.4 Method 3535 - Applicable to the extraction and concentration of
water-insoluble and slightly water-soluble organics from aqueous samples. A
measured volume of water is pumped through an appropriate medium (e.g., disk or
cartridge) containing a solid phase that effects the extraction of organics from
water. A small volume of extraction solvent is passed through the medium to
elute the compounds of interest. The eluant is dried, concentrated and, if
necessary, exchanged into a solvent compatible with further analysis.
Appropriate solid-phase extraction media allow extraction of water containing
particulates, are relatively fast and use small volumes of solvent. However,
they do require some specialized pieces of equipment.
7.5 Method 3540 - This method is applicable to the extraction of
nonvolatile and semivolatile organic compounds from solids such as soils,
relatively dry sludges, and solid wastes. A solid sample is mixed with anhydrous
sodium sulfate, placed into an extraction thimble or between two plugs of glass
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wool, and extracted using an appropriate solvent in a Soxhlet extractor. The
extract is concentrated and, if necessary, exchanged into a solvent compatible
with further analysis. Soxhlet extraction uses relatively inexpensive glassware,
once loaded requires no hands-on manipulation, provides efficient extraction, but
is rather lengthy (16 to 24 hours) and uses fairly large volumes of solvent. It
is considered a rugged extraction method because there are very few variables
that can adversely affect extraction efficiency.
7.6 Method 3541 - This method utilizes a modified Soxhlet extractor and
is applicable to the extraction of semivolatile/nonvolatile organic compounds
from solids such as soils, relatively dry sludges, and solid wastes. A solid
sample is mixed with anhydrous sodium sulfate, placed into an extraction thimble
or between two plugs of glass wool, and extracted using an appropriate solvent
in an automated Soxhlet extractor. This device allows the extraction thimble to
be lowered into the boiling liquid for the first hour and then extracted in the
normal thimble position for one additional hour. The automated Soxhlet allows
equivalent extraction efficiency in 2 hours, combines the concentration step
within the same device but requires a rather expensive device.
7.7 Method 3542 - This method is applicable to the extraction of
semivolatile organic compounds from the Method 0010 air sampling train. The
solid trapping material (i.e., glass or quartz fiber filter and porous polymeric
adsorbent resin) are extracted using Soxhlet extraction and the condensate and
impinger fluid are extracted using separatory funnel extraction.
7.8 Method 3545 - This method is applicable to the extraction of
nonvolatile/semivolatile organic compounds from solids such as soils, relatively
dry sludges, and solid wastes. A solid sample is mixed with anhydrous sodium
sulfate, placed into an extraction cell and extracted under pressure with small
volumes of solvent. The extract is concentrated and, if necessary, exchanged
into a solvent compatible with further analysis. The method is rapid and
efficient, in that it uses small volumes of solvent, but does require the use of
an expensive extraction device.
7.9 Method 3550 - This method is applicable to the extraction of
nonvolatile and semivolatile organic compounds from solids such as soils,
sludges, and wastes using the technique of ultrasonic extraction. Two procedures
are detailed depending upon the expected concentration of organics in the sample;
a low concentration and a high concentration method. In both, a known weight of
sample is mixed with anhydrous sodium sulfate and solvent extracted using
ultrasonic extraction. The extract is dried, concentrated and, if necessary,
exchanged into a solvent compatible with further analysis. Ultrasonic extraction
is fairly rapid (three, 3-minute extractions followed by filtration) but uses
relatively large volumes of solvent, requires a somewhat expensive device and
requires following the details of the method very closely to achieve acceptable
extraction efficiency (proper tuning of the ultrasonic device is very critical).
This technique is much less efficient than the other extraction techniques
described in this section. This is most evident with very non-polar organic
compounds (e.g. PCBs, etc.) that are normally strongly adsorbed to the soil
matrix. It is not appropriate for use with organophosphorus compounds, because
it may cause the destruction of some of the target analytes during the extraction
procedure.
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7.10 Methods 3560 and 3561 - These methods are applicable to the extraction
of total petroleum hydrocarbons and PAHs from solids such as soils, sludges, and
wastes using the technique of supercritical fluid extraction (SFE). SFE normally
uses C02 (which may contain very small volumes of solvent modifiers). Therefore,
there is no solvent waste for disposal, may be automated, provides relatively
rapid extraction, but, is currently limited to total petroleum hydrocarbons and
PAHs. It also requires a rather expensive device and sample size is more
limited. Research on SFE is currently focusing on optimizing supercritical fluid
conditions to allow efficient extraction of a broader range of RCRA analytes in
a broad range of environmental matrices.
7.11 Method 3580 - This method describes the technique of solvent dilution
of non-aqueous waste samples. It is designed for wastes that may contain organic
chemicals at a level greater than 20,000 mg/kg and that are soluble in the
dilution solvent. When using this method, the analyst must use caution in the
addition of surrogate compounds, so as not to dilute out the surrogate response
when diluting the sample.
7.12 Sample analysis - Following preparation of a sample by one of the
methods described above, the sample is ready for further analysis. Samples
prepared for semivolatile/nonvolatile analysis may, if necessary, undergo cleanup
(See Method 3600) prior to application of a specific determinative method.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific guidance on quality control
procedures. Each laboratory using SW-846 methods should maintain a formal
quality assurance program. Each extraction batch of 20 or less samples should
contain: a reagent blank; either a matrix spike/matrix spike duplicate or a
matrix spike and duplicate samples; and a laboratory control sample, unless the
determinative method provides other guidance.
8.2 Initial Demonstration of Proficiency - Each laboratory must
demonstrate initial proficiency with each sample preparation and determinative
method combination it utilizes, by generating data of acceptable accuracy and
precision for target analytes in a clean reference matrix. This will include a
combination of the sample extraction method (usually a 3500 series method for
extractable organics) and the determinative method (an 8000 series method). The
laboratory should also repeat the following operations whenever new staff are
trained or significant changes in instrumentation are made.
8.2.1 The reference samples are prepared from a spiking solution
containing each analyte of interest. The reference sample concentrate
(spiking solution) may be prepared from pure standard materials, or
purchased as certified solutions. If prepared by the laboratory, the
reference sample concentrate should be made using stock standards prepared
independently from those used for calibration.
8.2.2 The procedure for preparation of the reference sample
concentrate is dependent upon the method being evaluated. Guidance for
reference sample concentrations for certain methods are listed below. In
other cases, the determinative methods contain guidance on preparing the
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reference sample concentrate and the reference sample. If no guidance is
provided, prepare a reference sample concentrate in methanol (or other
water miscible solvent). Spike at the concentration the method performance
data are based on. The spike volume added to water should not exceed 1
mL/L so that the spike solvent will not decrease extraction efficiency.
If the method lacks performance data, prepare a reference standard
concentrate at such a concentration that the spike will provide a
concentration in the clean matrix that is 10 - 50 times the MDL for each
analyte in that matrix.
The concentration of the target analytes in the reference sample may
need to be adjusted to more accurately reflect the concentrations that will
be analyzed in the laboratory. If the concentration of an analyte is being
evaluated relative to a regulatory limit, see Sec. 8.3.3 for information
on selecting an appropriate spiking level.
8.2.3 To evaluate the performance of the total analytical process,
the reference samples must be handled in exactly the same manner as actual
samples. Therefore, 1 ml (unless the method specifies a different volume)
of the reference sample concentrate is spiked into each of four (minimum
number of replicates) 1-L aliquots of organic-free reagent water (now
called the reference sample), extracted as per the method. For matrices
other than water or for determinative methods that specify a different
volume of water, add 1.0 ml of the reference sample concentrate to at least
four replicates of the volume or weight of sample specified in the method.
Use a clean matrix for spiking purposes (one that does not have any target
or interference compounds) e.g., organic-free reagent water for the water
matrix or sand or soil (free of organic interferences) for the solid
matrix.
8.2.4 Preparation of reference samples
8.2.4.1 Method 8041 - Phenols: The QC reference sample
concentrate should contain each analyte at 100 mg/L in 2-propanol.
8.2.4.2 Method 8061 - Phthalate esters: The QC reference
sample concentrate should contain the following analytes at the
following concentrations in acetone: butyl benzyl phthalate, 10 mg/L;
bis(2-ethylhexyl)phthalate, 50 mg/L; di-n-octyl phthalate, 50 mg/L;
and any other phthalate at 25 mg/L.
8.2.4.3 Method 8070 - Nitrosamines: The QC reference sample
concentrate should contain each analyte at 20 mg/L in isooctane.
8.2.4.4 Method 8081 - Organochlorine pesticides: The QC
reference sample concentrate should contain each single-component
analyte at the following concentrations in acetone: 4,4'-DDD, 10
mg/L; 4,4'-DDT, 10 mg/L; endosulfan II, 10 mg/L; endosulfan sulfate,
10 mg/L; and any other single-component pesticide at 2 mg/L. If the
method is only to be used to analyze chlordane or toxaphene, the QC
reference sample concentrate should contain the most representative
multicomponent parameter at a concentration of 50 mg/L in acetone.
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8.2.4.5 Method 8082 - PCBs: The QC reference sample
concentrate should contain the most representative multicomponent
parameter at a concentration of 50 mg/L in acetone.
8.2.4.6 Method 8091 - Nitroaromatics and Cyclic Ketones:
The QC reference sample concentrate should contain each analyte at the
following concentrations in acetone: each dinitrotoluene at 20 mg/L;
and isophorone and nitrobenzene at 100 mg/L.
8.2.4.7 Method 8100 - Polynuclear aromatic hydrocarbons:
The QC reference sample concentrate should contain each analyte at the
following concentrations in acetonitrile: naphthalene, 100 mg/L;
acenaphthylene, 100 mg/L; acenaphthene, 100 mg/L; fluorene, 100 mg/L;
phenanthrene, 100 mg/L; anthracene, 100 mg/L; benzo(k)fluoranthene 5
mg/L; and any other PAH at 10 mg/L.
8.2.4.8 Method 8111 - Haloethers: The QC reference sample
concentrate should contain each analyte at a concentration of 20 mg/L
in isooctane.
8.2.4.9 Method 8121 - Chlorinated hydrocarbons: The QC
reference sample concentrate should contain each analyte at the
following concentrations in acetone: hexachloro-substituted
hydrocarbons, 10 mg/L; and any other chlorinated hydrocarbon, 100
mg/L.
8.2.4.10 Method 8131 - Aniline and selected derivatives: The
QC reference sample concentrate should contain each analyte at the
following concentrations in acetone at a concentration 1,000 times
more concentrated than the selected spike concentration.
8.2.4.11 Method 8141 - Organophosphorus compounds: The QC
reference sample concentrate should contain each analyte in acetone
at a concentration 1,000 times more concentrated than the selected
spike concentration.
8.2.4.12 Method 8151 - Chlorinated herbicides: The QC
reference sample concentrate should contain each analyte in acetone
at a concentration 1,000 times more concentrated than the selected
spike concentration.
8.2.4.13 Method 8260 - Volatile organics: The QC reference
sample concentrate should contain each analyte in methanol at a
concentration of 10 mg/L. This concentrate is spiked into 100 mL of
organic-free reagent water, producing enough reference sample for four
aliquots of up to 25 mL each.
8.2.4.14 Method 8270 - Semivolatile organics: The QC
reference sample concentrate should contain each analyte in acetone
at a concentration of 100 mg/L.
8.2.4.15 Method 8310 - Polynuclear aromatic hydrocarbons:
The QC reference sample concentrate should contain each analyte at the
following concentrations in acetonitrile: naphthalene, 100 mg/L;
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acenaphthylene, 100 mg/L; acenaphthene, 100 mg/L; fluorene, 100 mg/L;
phenanthrene, 100 mg/L; anthracene, 100 mg/L; benzo(k)fluoranthene,
5 mg/L; and any other PAH at 10 mg/L.
8.2.5 Analyze at least four replicate aliquots of the well-mixed
reference samples by the same procedures used to analyze actual samples
(Sec. 7.0 of each of the methods). This will include a combination of the
sample preparation method (usually a 3500 series method for extractable
organics) and the determinative method (an 8000 series method). Follow the
guidance on data calculation and interpretation presented in Method 8000,
Sec. 8.0.
8.2.6 The following methods contain specific extraction and sample
preparation requirements applicable only to that method. Refer to these
individual methods for extraction and preparation procedures required prior
to instrumental analysis, and for information on the preparation of QC
reference samples.
8.2.6.1 Method 8275 - Thermal Chromatography/Mass
Spectrometry (TC/MS) for Screening Semivolatile Organic Compounds.
8.2.6.2 Method 8280 - Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans.
8.2.6.3 Method 8290 - Polychlorinated Dibenzo-p-dioxins and
Polychlorinated Dibenzofurans.
8.2.6.4 Method 8318 - N-Methylcarbamates by High Performance
Liquid Chromatography (HPLC).
8.2.6.5 Method 8321 - Solvent Extractable Non-Volatile
Compounds by High Performance Liquid Chromatography/Thermospray/Mass
Spectrometry (HPLC/TS/MS) or Ultra-Violet (UV) Detection.
8.2.6.6 Method 8325 - Nonvolatiles by High Performance
Liquid Chromatography/Particle-Beam/Mass Spectrometry (HPLC/PB/MS) or
Ultra-Violet (UV) Detection.
8.2.6.7 Method 8330 - Nitroaromatics and Nitramines by High
Performance Liquid Chromatography (HPLC).
8.2.6.8 Method 8331 - Tetrazine by Reverse Phase High
Performance Liquid Chromatography (HPLC).
8.2.6.9 Method 8332 - Nitroglycerine by High Performance
Liquid Chromatography (HPLC) or Thin Layer Chromatography (TLC).
8.2.6.10 Method 8410 - Gas Chromatography/Fourier Transform
Infrared (GC/FT-IR) Spectrometry for Semivolatile Organics.
8.2.6.11 Method 8430 - Bis-(chloroethyl )ether and Hydrolysis
Products by GC/FT-IR.
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8.2.6.12 Method 8440 - Total Recoverable Petroleum
Hydrocarbons (TRPH) by Infrared (IR) Detection.
8.3 Sample Quality Control for Preparation and Analysis
8.3.1 Documenting the effect of the matrix should include the
analysis of at least one matrix spike and one duplicate unspiked sample or
one'tnatrix spike/matrix spike duplicate pair per analytical batch. The
decision on whether to prepare and analyze duplicate samples or a matrix
spike/matrix spike duplicate must be based on a knowledge of the samples
in the sample batch. If samples are expected to contain target analytes,
then laboratories may use one matrix spike and a duplicate analysis of an
unspiked field sample. If samples are not expected to contain target
analytes, the laboratories should use a matrix spike and matrix spike
duplicate pair. See Sec. 5.5 for additional guidance on matrix spike
preparation.
8.3.2 A Laboratory Control Sample (LCS) should be included with each
analytical batch. The LCS consists of an aliquot of a clean (control)
matrix similar to the sample matrix and of the same weight or volume:
e.g., organic-free reagent water for the water matrix or sand or soil (free
of organic interferences) for the solid matrix. The LCS is spiked with the
same analytes at the same concentrations as the matrix spike. When the
results of the matrix spike analysis indicate a potential problem due to
the sample matrix itself, the LCS results are used to verify that the
laboratory can perform the analysis in a clean matrix.
8.3.3 The concentration of the matrix spike sample and/or the LCS
should be determined as described in the following sections.
K 8.3.3.1 If, as in compliance monitoring, the concentration
of a specific analyte in the sample is being checked against a
regulatory concentration limit, the spike should be at or below the
regulatory limit, or 1 - 5 times the background concentration (if
historical data are available), whichever concentration is higher.
8.3.3.2 If historical data are not available, it is
suggested that an uncontaminated sample of the same matrix from the
site be submitted for matrix spiking purposes to ensure that high
concentrations of target analytes and/or interferences will not
"prevent calculation of recoveries.
8.3.3.3 If the concentration of a specific analyte in a
sample is not being checked against a limit specific to that analyte,
then the spike should be at the same concentration as the reference
sample (Sec. 8.2.4) or 20 times the estimated quantitation limit (EQL)
in the matrix of interest. It is again suggested that a background
sample of the same matrix from the site be submitted as a sample for
matrix spiking purposes.
8.3.4 Analyze these QC samples (the LCS and the matrix spikes or the
optional matrix duplicates) following the procedure (Sec. 7.0) of the
selected determinative method. Calculate and evaluate the QC data as
outlined in Sec. 8.0 of Method 8000.
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8.3.5 Blanks - Use of method blanks and other blanks are necessary
to track contamination of samples during the sampling and analysis
processes. Refer to Chapter One for specific quality control procedures.
8.3.6 Surrogates - A surrogate is a compound that is chemically
similar to the analyte group but not expected to occur in an environmental
sample. Surrogate should be added to all samples when specified in the
appropriate determinative method (See Table 2). See Sec. 5.4 for the
definition of surrogates and additional guidance on surrogates.
8.4 The laboratory must have procedures in place for documenting and
charting the effect of the matrix on method performance. Refer to Chapter One
and Method 8000 for specific guidance on developing method performance data.
9.0 METHOD PERFORMANCE
9.1 The recovery of surrogates is used to monitor unusual matrix effects,
sample processing problems, etc. The recovery of matrix spiking compounds
indicates the presence or absence of unusual matrix effects.
9.2 The performance of each 3500 method will be dictated by the overall
performance of the sample preparation in combination with the cleanup method
and/or the analytical determinative method.
10.0 REFERENCES
None required.
3500B - 13 Revision 2
January 1995
-------
TABLE 1
SURROGATES FOR SW-846 CHROMATOGRAPHIC METHODS
FOR SEMIVOLATILE AND NONVOLATILE COMPOUNDS
Method
Number
8041
8061
8070
8081
8082
8091
8100
8111
8121
8131
8141
8151
8270
8275
8280
Method Name
Phenols by GC
Phthalates by GC
Nitrosamines by
GC, Packed Column
Organochlorine
Pesticides by GC
Polychlorinated
Biphenyls by GC
Nitroaromatics by
GC
PAHs by GC,
Packed Column
Haloethers by GC
Chlorinated
Hydrocarbons by
GC
Anilines by GC
Organophosphorus
Pesticides by GC
Acid Herbicides
by GC
Semivolatiles by
GC/MS
Thermal Chromato-
graphy/MS for
Semivolatiles
PCDDs & PCDFs by
LR/MS
Suggested Surrogates
2-Fluorophenol , and
2,4,6-Tribromophenol
Diphenyl phthalate, Diphenyl
isophthalate, and Dibenzyl
phthalate
None Listed""
2,4,5,6-Tetrachloro-m-xylene,
and Decachlorobiphenyl
Decachlorobiphenyl
2-Fluorobiphenyl
2-Fluorobiphenyl , and
1-Fluoronaphthalene
None Listed""
a,2,6-Trichlorotoluene,
2,3,4,5,6-Pentachlorotoluene,
and 1,4-Dichloronaphthalene
None Listed"
None Listed*"
2,4-Dichlorophenylacetic acid
Phenol-d6, 2-Fluorophenol ,
2,4,6-Tribromophenol, Nitro-
benzene-d5, 2-Fluorobiphenyl,
and p-Terphenyl-d14
Not Listed""
Internal standards added at
time of extraction. No
surrogates.
Suggested Water
Concentration
200 M9/L
25 M9/L
100 M9/L
1 M9/L
NA
100 M9/L
100 M9/L
100 M9/L
1 M9/L (for
surrogates 1&2)
10 jitg/L (other
surrogates)
NA
NA
5 M9/L
Base/Neutrals
100 jLig/L &
Acids 200 jug/L
NA
NA
3500B - 14
Revision 2
January 1995
-------
TABLE 1
(continued)
Method
Number
8290
8310
8318
8321
8325
8330
8331
8332
8410
8430
8440
Method Name
PCDDs & PCDFs by
HR/MS
PAHs by HPLC
Carbamates by
HPLC
Nonvolatiles by
HPLC/TS/MS or
UV/VIS
Nonvolatiles by
HPLC/PB/MS or
UV/Vis
Explosives by
HPLC
Tetrazine by HPLC
Nitroglycerine by
HPLC or TLC
GC/FT-IR for
Semivolatiles
Bis-(chloroethyl )
ether and hydro-
lysis products by
GC/FT-IR
Total Recoverable
Petroleum Hydro-
carbons by IR
Suggested Surrogates
Internal standards added at
time of extraction. No
surrogates.
Decafluorobiphenyl
None Listed""
None Listed"
Benzidine-dg, Caffeine-15N2,
3,3' -dichlorobenzidine-d6,
bis-(perfluorophenyl)-
phenylphosphine oxide
None Listed""
None Listed"
None Listed"
None Listed"
None Listed"
None Listed"
Suggested Water
Concentration
NA
NA
NA
NA
50 /jg/L in
water
NA
NA
NA
NA
NA
NA
Surrogate compounds selected should be similar in analytical behavior to
the analytes of interest, but which are not expected to be present in the
sample matrix or extract.
GC
HR
LR
NA
TS
PB
MS
Gas chromatography
High Resolution
Low Resolution
Not Available
Thermospray
Particle Beam
Mass Spectrometer
NOTE: Unless otherwise
techniques.
HPLC = High Performance Liquid Chromatography
PCDD = Polychlorinated Dibenzo~2-dioxins
PCDF = Polychlorinated Dibenzofurans
FT-IR = Fourier Transform Infrared Detector
UV/Vis = Ultraviolet/Visible Detector
TLC = Thin Layer Chromatography
IR = Infrared Detector
specified, all GC methods are capillary column
3500B - 15
Revision 2
January 1995
-------
TABLE 2
MATRIX SPIKES FOR SW-846 CHROMATOGRAPHIC METHODS
FOR SEMIVOLATILE AND NONVOLATILE COMPOUNDS
Method
Number
8041
8061
8070
8081
8082
8091
8100
8111
8121
8131
8141
8151
8270
8275
8280
8290
Method Name
Phenols by GC
Phthalates by GC
Nitrosamines by
GC, Packed Column
Organochlorine
Pesticides by GC
Polychlorinated
Biphenyls by GC
Nitroaromatics by
GC, Packed Column
PAHs by GC,
Packed Column
Haloethers by GC
Chlorinated
Hydrocarbons by
GC
Anilines by GC
Organophosphorus
Pesticides by GC
Acid Herbicides
by GC
Semivolatiles by
GC/MS
Thermal
Chromatography/MS
for Semivolatiles
PCDDs & PCDFs by
LR/MS
PCDDs & PCDFs by
HR/MS
Suggested Matrix Spike Compounds
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Lindane, Heptachlor, Aldrin,
Dieldrin, Endrin, and 4,4'-DDT
Spike Aroclors 1016 and 1260 or
individual PCB congeners of
interest
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
1,2,4-Trichlorobenzene, Ace-
naphthene, 2,4-Dinitrotoluene,
Pyrene, N-Nitroso-di-n-propylamine,
1,4-Dichlorobenzene, Penta-
chlorophenol , Phenol, 2-Chloro-
phenol , 4-Chloro-3-methylphenol ,
and 4-Nitrophenol
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Suggested
Water Cone.
NA
NA
NA
1 - 10 M9/L
NA
NA
NA
NA
NA
NA
NA
NA
100 M9/L for
base/neutral
compounds
and 200 jug/L
for acid
compounds
NA
NA
1 ng/L (ppt)
3500B - 16
Revision 2
January 1995
-------
TABLE 2
(continued)
Method
Number
8310
8321
8325
8330
8331
8332
8410
8430
8440
Method Name
PAHs by HPLC
Nonvolatiles by
HPLC/TS/MS or
UV/VIS
Nonvolatiles by
HPLC/PB/MS or
UV/Vis
Explosives by
HPLC
Tetrazine by HPLC
Nitroglycerine by
HPLC or TLC
GC/FT-IR for
Semivolatiles
Bis-(chloroethyl )
ether and
hydrolysis
products by
GC/FT-IR
Total Recoverable
Petroleum
Hydrocarbons by
IR
Suggested Matrix Spike Compounds
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Spike with analyte of interest
Spike with analyte of interest
Primarily a qualitative method
Spike analytes of interest
Spike analytes of interest
Suggested
Water Cone.
NA
NA
NA
NA
NA
NA
NA
100 Mg/L
NA
GC = Gas chromatography
HR = High Resolution
LR = Low Resolution
NA = Not Available
TS = Thermospray
PB = Particle Beam
MS = Mass Spectrometer
HPLC = High Performance Liquid Chromatography
PCDD = Polychlorinated Dibenzo-g-dioxins
PCDF = Polychlorinated Dibenzofurans
FT-IR = Fourier Transform Infrared Detector
UV/Vis = Ultraviolet/Visible Detector
TLC = Thin Layer Chromatography
IR = Infrared Detector
NOTE: Unless otherwise specified all
techniques.
GC methods are capillary column
3500B - 17
Revision 2
January 1995
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METHOD 3510C
SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a procedure for isolating organic compounds from
aqueous samples. The method also describes concentration techniques suitable for
preparing the extract for the appropriate determinative methods described in
Section 4.3 of Chapter Four.
1.2 This method is applicable to the isolation and concentration of water-
insoluble and slightly water-soluble organics in preparation for a variety of
chromatographic procedures.
1.3 This method is restricted to use by or under the supervision of
trained analysts. Each analyst must demonstrate the ability to generate
acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 A measured volume of sample, usually 1 liter, at a specified pH (see
Table 1), is serially extracted with methylene chloride using a separatory
funnel.
2.2 The extract is dried, concentrated (if necessary), and, as necessary,
exchanged into a solvent compatible with the cleanup or determinative method to
be used (see Table 1 for appropriate exchange solvents).
3.0 INTERFERENCES
3.1 Refer to Method 3500.
3.2 The decomposition of some analytes has been demonstrated under basic
extraction conditions. Organochlorine pesticides may dechlorinate, phthalate
esters may exchange, and phenols may react to form tannates. These reactions
increase with increasing pH, and are decreased by the shorter reaction times
available in Method 3510. Method 3510 is preferred over Method 3520 for the
analysis of these classes of compounds. However, the recovery of phenols may be
optimized by using Method 3520, and performing the initial extraction at the acid
pH.
4.0 APPARATUS AND MATERIALS
4.1 Separatory funnel - 2-liter, with Teflon® stopcock.
4.2 Drying column - 20 mm ID Pyrex® chromatographic column with Pyrex®
glass wool at bottom and a Teflon® stopcock.
3510C - 1 Revision 3
January 1995
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NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without
frits may be purchased. Use a small pad of Pyrex® glass wool to
retain the adsorbent. Prewash the glass wool pad with 50 ml of
acetone followed by 50 mL of elution solvent prior to packing the
column with adsorbent.
4.3 Kuderna-Danish (K-D) apparatus.
4.3.1 Concentrator tube - 10-mL, graduated (Kontes K-570050-1025 or
equivalent). A ground-glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.3.3 Snyder column - Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column - Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
NOTE: The following glassware is recommended for the purpose of solvent
recovery during the concentration procedures requiring the use of
Kuderna-Danish evaporative concentrators. Incorporation of this
apparatus may be required by State or local municipality
regulations that govern air emissions of volatile organics. EPA
recommends the incorporation of this type of reclamation system as
a method to implement an emissions reduction program. Solvent
recovery is a means to conform with waste minimization and
pollution prevention initiatives.
4.4 Solvent vapor recovery system (Kontes K-545000-1006 or K-547300-0000,
Ace Glass 6614-30, or equivalent).
4.5 Boiling chips - Solvent-extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.6 Water bath - Heated, with concentric ring cover, capable of
temperature control (± 5°C). The bath should be used in a hood.
4.7 Vials - 2-mL, glass with Teflon®-!ined screw-caps or crimp tops.
4.8 pH indicator paper - pH range including the desired extraction pH.
4.9 Erlenmeyer flask - 250-mL.
4.10 Syringe - 5-mL.
4.11 Graduated cylinder - 1-liter.
3510C - 2 Revision 3
January 1995
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5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination. Reagents should be
stored in glass to prevent the leaching of contaminants from plastic containers.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium hydroxide solution (ION), NaOH. Dissolve 40 g NaOH in organic-
free reagent water and dilute to 100 ml.
5.4 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating to
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.5 Sulfuric acid solution (1:1 v/v), H2S04. Slowly add 50 ml of H2S04
(sp. gr. 1.84) to 50 ml of organic-free reagent water.
5.6 Extraction/exchange solvents - All solvents must be pesticide quality
or equivalent.
5.6.1 Methylene chloride, CH2C12, boiling point 39°C.
5.6.2 Hexane, C6H14, boiling point 68.7°C.
5.6.3 2-Propanol, CH3CH(OH)CH3, boiling point 82.38C.
5.6.4 Cyclohexane, C6H12, boiling point 80.7°C.
5.6.5 Acetonitrile, CH3CN, boiling point 81.6°C.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
See the introductory material to this chapter, Organic Analytes,
Section 4.1,
7.0 PROCEDURE
7.1 Using a 1-liter graduated cylinder, measure 1 liter (nominal) of
sample and transfer it quantitatively to the separatory funnel. If high
concentrations are anticipated, a smaller volume may be used and then diluted
with organic-free reagent water to 1 liter.
3510C - 3 Revision 3
January 1995
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7.2 Check the pH of the sample with wide-range pH paper and, if necessary,
adjust the pH to that indicated in Table 1 using 1:1 (v/v) sulfuric acid or
10 N sodium hydroxide.
7.3 Add 1.0 ml of the surrogate standards to all samples, spikes, and
blanks (see Method 3500 and the determinative method to be used for details on
the surrogate standard solution and the matrix spike solution).
7.3.1 For the sample in each analytical batch selected for spiking,
add 1.0 ml of the matrix spiking standard.
7.3.2 For base/neutral-acid analysis, the amount added of the
surrogates and matrix spiking compounds should result in a final
concentration of 100 ng//il_ of each base/neutral analyte and 200 ng/^L of
each acid analyte in the extract to be analyzed (assuming a 1 juL
injection). If Method 3640, Gel-Permeation Cleanup, is to be used, add
twice the volume of surrogates and matrix spiking compounds since half the
extract is lost due to loading of the GPC column.
7.4 Add 60 ml of methylene chloride to the separatory funnel.
7.5 Seal and shake the separatory funnel vigorously for 1-2 minutes with
periodic venting to release excess pressure.
NOTE: Methylene chloride creates excessive pressure very rapidly;
therefore, initial venting should be done immediately after the
separatory funnel has been sealed and shaken once. The separatory
funnel should be vented into a hood to avoid exposure of the analyst
to solvent vapors.
7.6 Allow the organic layer to separate from the water phase for a minimum
of 10 minutes. If the emulsion interface between layers is more than one-third
the size of the solvent layer, the analyst must employ mechanical techniques to
complete the phase separation. The optimum technique depends upon the sample and
may include stirring, filtration of the emulsion through glass wool,
centrifugation, or other physical methods. Collect the solvent extract in an
Erlenmeyer flask. If the emulsion cannot be broken (recovery of < 80% of the
methylene chloride, corrected for the water solubility of methylene chloride),
transfer the sample, solvent, and emulsion into the extraction chamber of a
continuous extractor and proceed as described in Method 3520, Continuous Liquid-
Liquid Extraction.
7.7 Repeat the extraction two more times using fresh portions of solvent
(Sees. 7.3 through 7.5). Combine the three solvent extracts.
7.8 If further pH adjustment and extraction is required, adjust the pH of
the aqueous phase to the desired pH indicated in Table 1. Serially extract three
times with 60 mL of methylene chloride, as outlined in Sees. 7.3 through 7.5.
Collect and combine the extracts and label the combined extract appropriately.
7.9 If performing GC/MS analysis (Method 8270), the acid/neutral and base
extracts may be combined prior to concentration. However, in some situations,
separate concentration and analysis of the acid/neutral and base extracts may be
preferable (e.g. if for regulatory purposes the presence or absence of specific
3510C - 4 Revision 3
January 1995
-------
acid/neutral or base compounds at low concentrations must be determined, separate
extract analyses may be warranted).
7.10 Perform the concentration (if necessary) using the Kuderna-Danish
Technique (Sees. 7.11.1 through 7.11.6).
7.11 K-D technique
7.11.1 Assemble a Kuderna-Danish (K-D) concentrator (Sec. 4.3) by
attaching a 10-mL concentrator tube to a 500-mL evaporation flask.
7.11.2 Attach the solvent vapor recovery glassware (condenser and
collection device) (Sec. 4.4) to the Snyder column of the K-D apparatus
following manufacturer's instructions.
7.11.3 Dry the extract by passing it through a drying column
containing about 10 cm of anhydrous sodium sulfate. Collect the dried
extract in a K-D concentrator. Rinse the Erlenmeyer flask, which contained
the solvent extract, with 20 - 30 ml of methylene chloride and add it to
the column to complete the quantitative transfer.
7.11.4 Add one or two clean boiling chips to the flask and attach a
three-ball Snyder column. Prewet the Snyder column by adding about 1 mL
of methylene chloride to the top of the column. Place the K-D apparatus
on a hot water bath (15 - 20°C above the boiling point of the solvent) so
that the concentrator tube is partially immersed in the hot water and the
entire lower rounded surface of the flask is bathed with hot vapor. Adjust
the vertical position of the apparatus and the water temperature as
required to complete the concentration in 10 - 20 minutes. At the proper
rate of distillation the balls of the column will actively chatter, but the
chambers will not flood. When the apparent volume of liquid reaches 1 ml,
remove the K-D apparatus from the water bath and allow it to drain and cool
for at least 10 minutes.
7.11.5 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 mL of the exchange solvent,
a new boiling chip, and reattach the Snyder column. Concentrate the
extract, as described in Sec. 7.11.4, raising the temperature of the water
bath, if necessary, to maintain proper distillation.
7.11.6 Remove the Snyder column and rinse the flask and its lower
joints into the concentrator tube with 1 - 2 mL of methylene chloride or
exchange solvent. If sulfur crystals are a problem, proceed to Method 3660
for cleanup. The extract may be further concentrated by using the
technique outlined in Sec. 7.12 or adjusted to 10.0 mL with the solvent
last used.
7.12 If further concentration is indicated in Table 1, either the micro-
Snyder column technique (7.12.1) or nitrogen blowdown technique (7.12.2) is used
to adjust the extract to the final volume required.
3510C - 5 Revision 3
January 1995
-------
7.12.1 Micro-Snyder column technique
If further concentration is indicated in Table 1, add another
clean boiling chip to the concentrator tube and attach a two-ball
micro-Snyder column. Prewet the column by adding 0.5 ml of methylene
chloride or exchange solvent to the top of the column. Place the K-D
apparatus in a hot water bath so that the concentrator tube is
partially immersed in the hot water. Adjust the vertical position of
the apparatus and the water temperature, as required, to complete the
concentration in 5 - 10 minutes. At the proper rate of distillation
the balls of the column will actively chatter, but the chambers will
not flood. When the apparent volume of liquid reaches 0.5 mL, remove
the K-D apparatus from the water bath and allow it to drain and cool
for at least 10 minutes. Remove the Snyder column and rinse the flask
and its lower joints into the concentrator tube with 0.2 ml of
extraction solvent. Adjust the final volume to 1.0 - 2.0 ml, as
indicated in Table 1, with solvent.
7.12.2 Nitrogen blowdown technique
7.12.2.1 Place the concentrator tube in a warm bath (35°C)
and evaporate the solvent volume to 0.5 mL using a gentle stream of
clean, dry nitrogen (filtered through a column of activated carbon).
CAUTION: New plastic tubing must not be used between the carbon trap
and the sample, since it may introduce contaminants.
7.12.2.2 The internal wall of the tube must be rinsed several
times with methylene chloride or appropriate solvent during the
operation. During evaporation, the tube must be positioned to avoid
water condensation (i.e., the solvent level should be below the level
of the water bath). Under normal procedures, the extract must not be
allowed to become dry.
CAUTION: When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost.
7.13 The extract may now be analyzed for the target analytes using the
appropriate determinative technique(s) (see Sec. 4.3 of this Chapter). If
analysis of the extract will not be performed immediately, stopper the
concentrator tube and store refrigerated. If the extract will be stored longer
than 2 days it should be transferred to a vial with a Teflon®-!ined screw-cap or
crimp top, and labeled appropriately.
8.0 QUALITY CONTROL
8.1 Any reagent blanks, matrix spikes, or replicate samples should be
subjected to exactly the same analytical procedures as those used on actual
samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
3510C - 6 Revision 3
January 1995
-------
9.0 METHOD PERFORMANCE
Refer to the determinative methods for performance data.
10.0 REFERENCES
None.
3510C - 7 Revision 3
January 1995
-------
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METHOD 3510C
SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
7.1 Measure
sample into
separatory funnel.
7.2 Check
and adjust pH.
7.3 Add appropriate
surrogate and matrix
spiking standards.
7.8 Adjust
pH.
7.3 - 7.7
Extract 3 times
with methylene
chloride.
Yes
7.8 Is
extraction at
2nd pH
required?
7.8 Collect and
combine extracts.
7.9
GC/MS
nalysis (Method
8270) being
performed?
7.9 Combine acid/
neutral and base
extracts prior to
concentration, if
appropriate.
7.10 - 7.11
Concentrate
extract.
7.1 1.5
Is solvent
exchange
required?
7.11.5 Add
exchange solvent,
reconcentrate
extract.
7.12 Further
concentrate extract
if necessary;
adjust final volume.
7.12 Perform
determinative
method.
3510C - 9
Revision 3
January 1995
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METHOD 3520C
CONTINUOUS LIQUID-LIQUID EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a procedure for isolating organic compounds from
aqueous samples. The method also describes concentration techniques suitable for
preparing the extract for the appropriate determinative steps described in
Section 4.3 of Chapter Four.
1.2 This method is applicable to the isolation and concentration of water-
insoluble and slightly soluble organics in preparation for a variety of
chromatographic procedures.
1.3 Method 3520 is designed for extraction solvents with greater density
than the sample. Continuous extraction devices are available for extraction
solvents that are less dense than the sample. The analyst must demonstrate the
effectiveness of any such automatic extraction device before employing it in
sample extraction.
1.4 This method is restricted to use by or under the supervision of
trained analysts. Each analyst must demonstrate the ability to generate
acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 A measured volume of sample, usually 1 liter, is placed into a
continuous liquid-liquid extractor, adjusted, if necessary, to a specific pH (see
Table 1), and extracted with organic solvent for 18 - 24 hours.
2.2 The extract is dried, concentrated (if necessary), and, as necessary,
exchanged into a solvent compatible with the cleanup or determinative method
being employed (see Table 1 for appropriate exchange solvents).
3.0 INTERFERENCES
3.1 Refer to Method 3500.
3.2 The decomposition of some analytes has been demonstrated under basic
extraction conditions required to separate analytes. Organochlorine pesticides
may dechlorinate, phthalate esters may exchange, and phenols may react to form
tannates. These reactions increase with increasing pH, and are decreased by the
shorter reaction times available in Method 3510. Method 3510 is preferred over
Method 3520 for the analysis of these classes of compounds. However, the
recovery of phenols may be optimized by using Method 3520 and performing the
initial extraction at the acid pH.
3520C - 1 Revision 3
January 1995
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4.0 APPARATUS AND MATERIALS
4.1 Continuous liquid-liquid extractor - Equipped with Teflon® or glass
connecting joints and stopcocks requiring no lubrication (Kontes 584200-0000,
584500-0000, 583250-0000, or equivalent).
4.2 Drying column - 20 mm ID Pyrex® chromatographic column with Pyrex®
glass wool at bottom and a Teflon® stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without
frits may be purchased. Use a small pad of Pyrex® glass wool to
retain the adsorbent. Prewash the glass wool pad with 50 ml of
acetone followed by 50 ml of elution solvent prior to packing the
column with adsorbent.
4.3 Kuderna-Danish (K-D) apparatus
4.3.1 Concentrator tube - 10-mL graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.3.2
equivalent).
equivalent.
Evaporation
Attach to
flask - 500-mL
concentrator tube
(Kontes K-570001-500 or
with springs, clamps, or
4.3.3 Snyder column -
equivalent).
4.3.4 Snyder column -
equivalent).
Three-ball macro (Kontes K-503000-0121 or
Two-ball micro (Kontes K-569001-0219 or
4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
NOTE: The following glassware is recommended for the purpose of solvent
recovery during the concentration procedures requiring the use of
Kuderna-Danish evaporative concentrators. Incorporation of this
apparatus may be required by State or local municipality
regulations that govern air emissions of volatile organics. EPA
recommends the incorporation of this type of reclamation system as
a method to implement an emissions reduction program. Solvent
recovery is a means to conform with waste minimization and
pollution prevention initiatives.
4.4 Solvent vapor recovery system (Kontes K-545000-1006 or K-547300-0000,
Ace Glass 6614-30, or equivalent).
4.5 Boiling chips - Solvent-extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.6 Water bath - Heated, with concentric ring cover, capable of
temperature control (± 5CC). The bath should be used in a hood.
4.7 Vials - 2-mL, glass with Teflon®-!ined screw-caps or crimp tops.
3520C - 2
Revision 3
January 1995
-------
4.8 pH indicator paper - pH range including the desired extraction pH.
4.9 Heating mantle - Rheostat controlled.
4.10 Syringe - 5-mL.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination. Reagents should be
stored in glass to prevent the leaching of contaminants from plastic containers.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium hydroxide solution (ION), NaOH. Dissolve 40 g NaOH in organic-
free reagent water and dilute to 100 ml.
5.4 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.5 Sulfuric acid solution (1:1 v/v), H2S04. Slowly add 50 ml of H2S04
(sp. gr. 1.84) to 50 mL of organic-free reagent water.
5.6 Extraction/exchange solvents - All solvents must be pesticide quality
or equivalent.
5.6.1 Methylene chloride, CH2C12, boiling point 39°C.
5.6.2 Hexane, C6H14, boiling point 68.7°C.
5.6.3 2-Propanol, CH3CH(OH)CH3, boiling point 82.3°C.
5.6.4 Cyclohexane, C6H12, boiling point 80.7°C.
5.6.5 Acetonitrile, CH3CN, boiling point 81.6°C.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
See the introductory material to this chapter, Organic Analytes,
Section 4.1.
3520C - 3 Revision 3
January 1995
-------
7.0 PROCEDURE
7.1 Using a 1-liter graduated cylinder, measure 1 liter (nominal) of
sample and transfer it quantitatively to the continuous extractor. If high
concentrations are anticipated, a smaller volume may be used and then diluted
with organic-free reagent water to 1 liter.
7.2 Check the pH of the sample with wide-range pH paper and adjust the pH,
if necessary, to the pH indicated in Table 1 using 1:1 (v/v) sulfuric acid or
10 N sodium hydroxide.
7.3 Pipet 1.0 ml of the surrogate standard spiking solution into each
sample into the extractor and mix well. (See Method 3500 and the determinative
method to be used, for details on the surrogate standard solution and the matrix
spike solution.)
7.3.1 For the sample in each analytical batch selected for spiking,
add 1.0 ml of the matrix spiking standard.
7.3.2 For base/neutral-acid analysis, the amount of the surrogates
and matrix spiking compounds added to the sample should result in a final
concentration of 100 ng//il_ of each base/neutral analyte and 200 ng//A of
each acid analyte in the extract to be analyzed (assuming a 1 /xL
injection). If Method 3640, Gel-Permeation Cleanup, is to be used, add
twice the volume of surrogates and matrix spiking compounds since half the
extract is lost due to loading of the GPC column.
7.4 Add 300 - 500 ml of methylene chloride to the distilling flask. Add
several boiling chips to the flask.
7.5 Add sufficient water to the extractor to ensure proper operation and
extract for 18 - 24 hours.
7.6 Allow the extractor to cool, then detach the boiling flask. If
extraction at a secondary pH is not required (see Table 1), the extract is dried
and concentrated using one of the techniques described in Sees. 7.10 - 7.11.
7.7 If a pH adjustment and second extraction is required (see Table 1),
carefully, while stirring, adjust the pH of the aqueous phase to the second pH
indicated in Table 1. Attach a clean distilling flask containing 500 ml of
methylene chloride to the continuous extractor. Extract for 18 - 24 hours, allow
to cool, and detach the distilling flask.
7.8 If performing GC/MS analysis (Method 8270), the acid/neutral and base
extracts may be combined prior to concentration. However, in some situations,
separate concentration and analysis of the acid/neutral and base extracts may be
preferable (e.g. if for regulatory purposes the presence or absence of specific
acid/neutral and base compounds at low concentrations must be determined,
separate extract analyses may be warranted).
7.9 Perform concentration (if necessary) using the Kuderna-Danish
technique (Sees. 7.10.1 through 7.10.6).
3520C - 4 Revision 3
January 1995
-------
7.10 K-D technique
7.10.1 Assemble a Kuderna-Danish (K-D) concentrator (Sec. 4.3) by
attaching a 10-mL concentrator tube to a 500-mL evaporation flask.
7.10.2 Attach the solvent vapor recovery glassware (condenser and
collection device) (Sec. 4.4) to the Snyder column of the K-D apparatus
following manufacturer's instructions.
7.10.3 Dry the extract by passing it through a drying column
containing about 10 cm of anhydrous sodium sulfate. Collect the dried
extract in a K-D concentrator. Rinse the Erlenmeyer flask, which contained
the solvent extract, with 20 - 30 mL of methylene chloride and add it to
the column to complete the quantitative transfer.
7.10.4 Add one or two clean boiling chips to the flask and attach a
three-ball Snyder column. Prewet the Snyder column by adding about 1 mL
of methylene chloride to the top of the column. Place the K-D apparatus
on a hot water bath (15 - 20°C above the boiling point of the solvent) so
that the concentrator tube is partially immersed in the hot water and the
entire lower rounded surface of the flask is bathed with hot vapor. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete the concentration in 10 - 20 minutes. At the proper
rate of distillation the balls of the column will actively chatter, but the
chambers will not flood. When the apparent volume of liquid reaches 1 mL,
remove the K-D apparatus from the water bath and allow it to drain and cool
for at least 10 minutes.
7.10.5 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 mL of the exchange solvent,
a new boiling chip, and reattach the Snyder column. Concentrate the
extract, as described in Sec. 7.10.4, raising the temperature of the water
bath, if necessary, to maintain proper distillation.
7.10.6 Remove the Snyder column and rinse the flask and its lower
joints into the concentrator tube with 1 - 2 mL of methylene chloride or
exchange solvent. If sulfur crystals are a problem, proceed to Method 3660
for cleanup. The extract may be further concentrated by using the
techniques outlined in Sec. 7.11 or adjusted to 10.0 mL with the solvent
last used.
7.11 If further concentration is indicated in Table 1, either the micro-
Snyder column technique (7.11.1) or nitrogen blowdown technique (7.11.2) is used
to adjust the extract to the final volume required.
7.11.1 Micro-Snyder column technique
Add another one or two clean boiling chips to the concentrator
tube and attach a two-ball micro-Snyder column. Prewet the column by
adding 0.5 mL of methylene chloride or exchange solvent to the top of
the column. Place the K-D apparatus in a hot water bath so that the
concentrator tube is partially immersed in the hot water. Adjust the
vertical position of the apparatus and the water temperature, as
required, to complete the concentration in 5 - 10 minutes. At the
3520C - 5 Revision 3
January 1995
-------
proper rate of distillation the balls of the column will actively
chatter, but the chambers will not flood. When the apparent volume
of liquid reaches 0.5 ml, remove the K-D apparatus from the water bath
and allow it to drain and cool for at least 10 minutes. Remove the
Snyder column, rinse the flask and its lower joints into the
concentrator tube with 0.2 ml of methylene chloride or exchange
solvent, and adjust the final volume to 1.0 to 2.0 ml, as indicated
in Table 1, with solvent.
7.11.2 Nitrogen blowdown technique
7.11.2.1 Place the concentrator tube in a warm bath (35°C)
and evaporate the solvent volume to 0.5 ml using a gentle stream of
clean, dry nitrogen (filtered through a column of activated carbon).
CAUTION: New plastic tubing must not be used between the carbon trap
and the sample, since it may introduce contaminants.
7.11.2.2 The internal wall of the tube must be rinsed several
times with methylene chloride or appropriate solvent during the
operation. During evaporation, the tube must be positioned to avoid
water condensation (i.e., the solvent level should be below the level
of the water bath). Under normal procedures, the extract must not be
allowed to become dry.
CAUTION: When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost.
7.12 The extract may now be analyzed for the target analytes using the
appropriate determinative technique(s) (see Sec. 4.3 of this Chapter). If
analysis of the extract will not be performed immediately, stopper the
concentrator tube and store refrigerated. If the extract will be stored longer
than 2 days it should be transferred to a vial with a Teflon®-!ined screw-cap or
crimp top, and labeled appropriately.
8.0 QUALITY CONTROL
8.1 Any reagent blanks, matrix spikes, or replicate samples should be
subjected to exactly the same analytical procedures as those used on actual
samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample-preparation procedures.
9.0 METHOD PERFORMANCE
Refer to the determinative methods for performance data.
10.0 REFERENCES
None.
3520C - 6 Revision 3
January 1995
-------
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METHOD 3520C
CONTINUOUS LIQUID-LIQUID EXTRACTION
7.1 Measure sample
into extractor.
7.2 Check and
adjust pH.
7.3 Add appropriate
surrogate and matrix
spiking standards.
7.4 Add methylene
chloride to distilling
flask.
7.5 Add reagent
water to extractor;
extract for 18-24 hours;
collect extract.
7.6 Is
extraction
at 2nd pH
required?
7.7 Adjust pH of
aqueous phase; extract
for 18-24 hours with
clean flask and fresh
solvent.
7.8
GC/MS
analysis (Metho
8270) being
performed?
7.8 Combine extracts
prior to concentration,
if appropriate.
7.9 Concentrate
extract.
7.10.5
Is solvent
exchange
required?
7.10.5 Add exchange
solvent, concentrate
extract.
7.1 1 Further
concentrate extract
if necessary; adjust
final volume.
7.1 2 Perform
determinative
method.
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METHOD 3535
SOLID-PHASE EXTRACTION (SPE)
1.0 SCOPE AND APPLICATION
1.1 This method describes a procedure for isolating target organic
analytes from aqueous samples using solid-phase extraction media. The method
describes conditions for extracting organochlorine pesticides and phthalate
esters from aqueous matrices including groundwater, wastewater and TCLP leachates
using disk extraction media. Performance data for these extractions are provided
in Method 8081 (organochlorine pesticides) and Method 8061 (phthalate esters).
The technique may also be applicable to semivolatiles and other extractable
compounds.
1.2 This method also provides procedures for concentrating extracts and
for solvent exchange.
1.3 The method may be used for the extraction of additional target
analytes or other solid-phase media if the analyst demonstrates adequate
performance (e.g., recovery of 70 - 130%) using spiked sample matrices and an
appropriate analytical finish from Chapter Four (Sec. 4.3). Organic-free reagent
water is not considered appropriate for conducting such performance studies.
1.4 Solid-phase extraction is called liquid-solid extraction in EPA
Drinking Water Methods.
1.5 This method is restricted to use by or under the supervision of
trained analysts. Each analyst must demonstrate the ability to generate
acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 A measured volume of sample is adjusted to a specified pH (see Table
1) and then extracted using a Solid-phase Extraction (SPE) device.
2.2 Target analytes are eluted from the solid-phase media using methylene
chloride or another specified solvent. The resulting solvent extract is dried
using sodium sulfate and concentrated.
2.3 The concentrated extract may be exchanged into a solvent compatible
with subsequent cleanup procedures (Chapter Four, Section 4.2) or determinative
procedures (Chapter Four, Section 4.3) employed for the measurement of the target
analytes.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
3.2 The decomposition of some analytes has been demonstrated under basic
extraction conditions. Organochlorine pesticides may dechlorinate and phthalate
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esters may hydrolyze. The rates of these reactions increase with increasing pH
and reaction times.
3.3 Bonded phase silicas (e.g., C18) will hydrolyze on prolonged exposure
to aqueous samples with pH less than 2 or greater than 9. Hydrolysis will
increase at the extremes of this pH range and with longer contact times.
Hydrolysis may reduce extraction efficiency or cause baseline irregularities.
Styrene divinylbenzene (SDB) extraction disks should be considered when
hydrolysis is a problem.
3.4 Phthalates are a ubiquitous laboratory contaminant. All glass
extraction apparatus should be used for this method because phthalates are used
as release agents when molding rigid plastic (e.g., PVC). A method blank as
described in Chapter One should be analyzed, demonstrating that there is no
phthalate contamination of the sodium sulfate or other reagents specified in this
method.
3.5 Sample particulates may clog the solid-phase media and result in
extremely slow sample extractions. Use of an appropriate filter aid will result
in shorter extractions without loss of method performance if clogging is a
problem.
4.0 APPARATUS AND MATERIALS
4.1 Solid-phase extraction system - Empore~ manifold with 3-90 mm or 6-
47 mm standard filter apparatus, or equivalent. Automatic or robotic sample
preparation systems designed for solid-phase media may be utilized for this
method if adequate performance is achieved and all quality control requirements
are satisfied.
4.1.1 Manifold station - (Fisher Scientific 14-378-1B [3-place], 14-
378-1A [6-place], or equivalent).
4.1.2 Standard Filter Apparatus - (Fisher Scientific 14-378-2A
[47-mm], 14-378-2B [90-mm], or equivalent), consisting of a sample
reservoir, clamp, fritted disk and filtration head with drip tip.
4.1.3 Tube, collection - 60-mL (Kimble 609-58-A16, or equivalent).
The collection tube should be of appropriate I.D. and length for the drip
tip of the standard filter apparatus to be positioned well into the neck
of the tube to prevent splattering.
4.1.4 Filter flask - 2-L with a ground glass receiver joint (Kontes
K-953828-0000, or equivalent) (optional). May be used to carry out
individual disk extractions with the standard filter apparatus and
collection vial in an ALL GLASS SYSTEM.
4.2 Solid-phase Extraction Disks - Empore™, 47- or 90-mm, or equivalent.
Guidance for selecting the specific disk is provided in Table 1.
4.2.1 C18 disks - (Fisher Scientific 14-378E [47-mm], 14-378F [90-
mm], or equivalent).
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4.2.2 Styrene divinylbenzene (SDB-XC) disks - (Fisher Scientific 14-
378H [47-mm], 14-378J, or equivalent).
4.3 Filtration aid (optional).
4.3.1 Filter Aid 400 - (Fisher Scientific 14-378-3, or equivalent).
4.3.2 In-situ glass micro-fiber prefilter - (Whatman GMF 150, 1
micron pore size, or equivalent).
4.4 Drying column - 22-mm ID Pyrex® chromatographic column with a Teflon®
stopcock (Kontes K-420530-0242, or equivalent).
NOTE: Fritted glass discs used to retain sodium sulfate in some columns are
difficult to decontaminate after contact with highly contaminated or
viscous extracts. Columns suitable for this method use a small pad of
Pyrex® glass wool to retain the drying agent.
4.5 Kuderna-Danish (K-D) apparatus.
4.5.1 Concentrator tube - 10-mL, graduated (Kontes K-570050-1025,
or equivalent). A ground-glass stopper is used to prevent evaporation of
extracts during short-term storage.
4.5.2 Evaporation flask - 500-mL (Kontes K-570001-500, or
equivalent). Attach to concentrator tube using springs or clamps.
4.5.3 Snyder column - Three-ball macro- (Kontes K-503000-0121, or
equivalent).
4.5.4 Snyder column - Two-ball micro- (Kontes K-569001-0219, or
equivalent) (optional).
4.5.5 Springs - 1/2 inch (Kontes K-662750, or equivalent).
Note: The glassware in Sec. 4.6 is recommended for the purpose of solvent
recovery during the concentration procedures (Sees. 7.13 and 7.14.1)
requiring the use of Kuderna-Danish evaporative concentrators.
Incorporation of this apparatus may be required by State or local
municipality regulations that govern air emissions of volatile organics.
The EPA recommends the incorporation of this type of reclamation system
as a method to implement an emissions reduction program. Solvent
recovery is a means to conform with waste minimization and pollution
prevention initiatives.
4.6 Solvent Vapor Recovery System (Kontes 545000-1006 or K-547300-0000,
Ace Glass 6614-30, or equivalent).
4.7 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide, or equivalent).
4.8 Water bath - Heated, with concentric ring cover, capable of
temperature control to ± 5°C. The bath should be used in a hood.
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4.9 N-Evap - Nitrogen blowdown apparatus, 12- or 24-position (Organomation
Model 112, or equivalent) (optional).
4.10 Vials, glass - Sizes as appropriate, e.g., 2-mL or 10-mL with PTFE-
fluorocarbon-lined screw caps or crimp tops for storage of extracts.
4.11 pH indicator paper - Wide pH range (Fisher Scientific 14-850-13B, or
equivalent).
4.12 Vacuum system - Capable of maintaining a vacuum of approximately 66 cm
(26 inches) of mercury.
4.13 Graduated cylinder - Sizes as appropriate.
4.14 Pipets, disposable (Fisher Scientific 13-678-20C, or equivalent).
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without decreasing the accuracy of the determination. Reagents should be
stored in glass to prevent the leaching of contaminants from plastic containers.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium sulfate (granular, anhydrous), Na2S04 - Purify by heating at
400eC for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride.
5.4 Solutions for adjusting the pH of samples before extraction.
5.4.1 Sulfuric acid solution (1:1 v/v), H2S04 - Slowly add 50 mL of
H2S04 (sp. gr. 1.84) to 50 ml of organic-free reagent water.
5.4.2 Sodium hydroxide solution (ION), NaOH - Dissolve 40 g NaOH in
organic-free reagent water and dilute to 100 ml.
5.5 Extraction, washing, and exchange solvents - All solvent smust be
pesticide quality or equivalent.
5.5.1 Methylene chloride, CH2C12.
5.5.2 Hexane, C6H14.
5.5.3 Ethyl acetate, CH3C(OH)OCH2CH3.
5.5.4 Acetonitrile, CH3CN.
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5.5.5 Methanol, CH3OH.
5.5.6 Acetone, (CH3)2CO.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
See the introductory material to this chapter, Organic Analytes, Sec. 4.1.
7.0 PROCEDURE
7.1 Using a graduated cylinder, measure a 1-liter sample. Take care to
minimize any loss of sample particulates during this step.
7.1.1 Add 5.0 mL of methanol and any surrogate standards specified
in the determinative method to all samples and blanks.
7.1.2 Prepare matrix spikes by adding specified matrix spike
standards to representative sample replicates. The frequency with which
matrix spikes are prepared and analyzed is described in Chapter One or as
part of the determinative method.
7.1.3 If cleanup procedures are to be employed that result in the
loss of extract, adjust the amount of surrogate and spiking cocktail(s)
accordingly. In the case of Method 3640, Gel Permeation Cleanup, double
the amount of standards to compensate for the loss of one half of the
extract concentrate when loading the GPC column.
7.1.4 If high concentrations of target analytes are anticipated to
be present in samples, a smaller volume may be extracted.
7.2 Check the pH of the sample with wide-range pH paper and, if necessary,
adjust the pH to the range listed in Table 1. If pH adjustment is required,
ensure that analytes are not lost in precipitates or flocculated material.
7.3 Assemble a manifold for multiple extractions (Figure 1) using 47-mm
or 90-mm Empore™ disks. Use a filter flask with the standard filter apparatus
for single extractions. If samples contain significant quantities of
particulates, the use of a filter aid or prefilter is advisable. Empore™ Filter
Aid 400 or Whatman GMF 150 prefilters are recommended.
7.3.1 Pour about 40 g of Filter Aid 400 onto the surface of the disk
after assembling the standard filter apparatus.
7.3.2 Place the Whatman GMF 150 on top of the Empore™ disk prior to
clamping the glass reservoir into the standard filter apparatus.
7.4 Wash the extraction apparatus and disk with 20 mL of methylene
chloride introduced by rinsing down the sides of the glass reservoir. Pull a
small amount of solvent through the disk with a vacuum; turn off the vacuum and
allow the disk to soak for about one minute. Pull the remaining solvent through
the disk and allow the disk to dry.
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7.4.1 When using a filtration aid, adjust the volume of all wash
solvents so the entire filtration bed is submerged.
7.4.2 In subsequent conditioning steps, volumes should be adjusted
so that a level of solvent is always maintained above the entire filter
bed.
7.5 Continue to wash the extraction apparatus and disk by adding 10 mL of
acetone down the sides of the glass reservoir. Pull a small amount of solvent
through the disk with a vacuum; turn off the vacuum and allow the disk to soak
for about one minute. Pull the remaining solvent through the disk and allow the
disk to dry. When using a filtration aid, adjust the volume of acetone so that
the entire filtration bed is submerged.
7.6 Pre-wet (condition) the disk by adding 20 ml of methanol to the
reservoir, pulling a small amount through the disk and then letting it soak for
about one minute. Pull most of the remaining methanol through the disk, leaving
3 - 5 mm of methanol above the surface of the disk. From this point until the
sample extraction has been completed, the surface of the disk should not be
allowed to go dry. THIS IS A CRITICAL STEP FOR A UNIFORM FLOW AND GOOD RECOVERY.
7.6.1 The disk is composed of hydrophobic materials which will not
pass water unless they are pre-wetted with a water-miscible solvent.
Should a disk accidentally go dry during the conditioning step, the
methanol pre-wetting and water washing steps must be repeated prior to
adding the sample.
7.6.2 When using a filtration aid, adjust the volume of conditioning
solvents so that the entire filtration bed remains submerged until the
extraction is completed.
7.7 Rinse the disk by adding 20 mL of organic-free reagent water to the
disk and drawing most through, leaving 3 - 5 mm of water above the surface of the
disk.
7.8 Add a water sample, blank or matrix spike (Sec. 7.1) to the reservoir
and, under full vacuum, filter as quickly as the vacuum will allow (at least 10
minutes). Transfer as much of the measured volume of water as possible. After
the sample has passed through the solid-phase media, dry the disk by maintaining
vacuum for about 3 minutes.
NOTE: With heavily particle-laden samples, allow the sediment in the sample to
settle; decant as much liquid as is practical into the reservoir. After
most of the aqueous portion of the sample has passed through the disk,
swirl the portion of the sample containing sediment and add it to the
reservoir. Use additional portions of organic-free reagent water to
transfer any remaining particulates to the reservoir. Particulates must
be transferred to the reservoir before all of the aqueous sample has
passed through the disk.
7.9 Remove the entire standard filter assembly (do not disassemble) from
the manifold and insert a collection tube. The collection tube should have
sufficient capacity to hold all of the elution solvents. The drip tip of the
filtration apparatus should be seated sufficiently below the neck of the
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collection tube to prevent analyte loss due to splattering when vacuum is
applied. When using a filter flask for single extractions, empty the water from
the flask before inserting the collection tube.
7.10 Add 5.0 mL of acetone to the disk. Allow the acetone to spread out
evenly across the disk (or inert filter) then quickly turn the vacuum on and off
to pull the first drops of acetone through the disk. Allow the disk to soak for
15 to 20 seconds before proceeding to Sec. 7.11.
7.10.1 The initial elution with a water-miscible solvent, i.e.,
acetone, improves the recovery of analytes trapped in water-filled pores
of the sorbent. Use of a water-miscible solvent is particularly critical
when methylene chloride is used as the second elution solvent.
7.10.2 When using a filtration aid, adjust the volume of eluting
solvent so that the entire filtration bed is initially submerged.
7.11 Add 15 ml of methylene chloride (or other suitable elution solvent,
see Table 1) to the sample bottle. Rinse the bottle thoroughly and, with the
initial portion of acetone still on the disk, transfer the solvent to the disk
with a disposable pipette, rinsing down the sides of the filtration reservoir in
the process. Draw about half of the solvent through the disk and then release
the vacuum. Allow the remaining elution solvent to soak the disk and particulate
for about one minute before drawing the remaining solvent through the disk under
vacuum. When using a filtration aid, adjust the volume of elution solvent so
that the entire filtration bed is initially submerged.
7.12 Repeat Sec. 7.11 with a second 15-mL aliquot of elution solvent (see
Table 1).
7.13 K-D concentration technique.
7.13.1 Assemble a Kuderna-Danish (K-D) concentrator by attaching a
10-mL concentrator tube to a 500-mL evaporation flask.
7.13.2 Dry the combined extracts in the collection tube (Sees. 7.10-
7.12) by passing them through a drying column containing about 10 g of
anhydrous sodium sulfate. Collect the dried extract in the K-D
concentrator. Use acidified sodium sulfate (Method 8151) if acidic
analytes are to be measured.
7.13.3 Rinse the collection tube and drying column into the K-D flask
with an additional 20-mL portion of solvent in order to achieve a
quantitative transfer.
7.13.4 Add one or two clean boiling chips to the flask and attach a
three-ball Snyder column. Attach the solvent vapor recovery glassware
(condenser and collection device, see Sec. 4.6) to the Snyder column of the
K-D apparatus, following manufacturer's instructions. Prewet the Snyder
column by adding about 1 mL of methylene chloride to the top of the column.
Place the K-D apparatus on a hot water bath (15 - 20°C above the boiling
point of the solvent) so that the concentrator tube is partially immersed
in the hot water and the entire lower rounded surface of the flask is
bathed with hot vapor. Adjust the vertical position of the apparatus and
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the water temperature as required to complete the concentration in 10 - 20
minutes. At the proper rate of distillation the balls of the column will
actively chatter, but the chambers will not flood. When the apparent
volume of liquid reaches 1 ml_, remove the K-D apparatus from the water bath
and allow it to drain and cool for at least 10 minutes.
7.13.4.1 If a solvent exchange is required (as indicated in
Table 1), momentarily remove the Snyder column, add 50 ml of the
exchange solvent and a new boiling chip.
7.13.4.2 Reattach the Snyder column. Concentrate the
extract, raising the temperature of the water bath, if necessary, to
maintain a proper distillation rate.
7.13.5 Remove the Snyder column. Rinse the K-D flask and the lower
joints of the Snyder column into the concentrator tube with 1 - 2 ml of
solvent. The extract may be further concentrated by using a technique
outlined in Sec. 7.14 or adjusted to a final volume of 5.0 - 10.0 ml using
an appropriate solvent (Table 1).
7.14 If further concentration is required, use either the micro-Snyder
column technique (7.14.1) or nitrogen blowdown technique (7.14.2).
7.14.1 Micro-Snyder column technique.
7.14.1.1 Add a fresh clean boiling chip to the concentrator
tube and attach a two-ball micro-Snyder column directly to the
concentrator tube. Attach the solvent vapor recovery glassware
(condenser and collection device) to the micro-Snyder column of the
K-D apparatus, following manufacturer's instructions. Prewet the
Snyder column by adding 0.5 ml of methylene chloride or the exchange
solvent to the top of the column. Place the micro-concentration
apparatus in a hot water bath so that the concentrator tube is
partially immersed in the hot water. Adjust the vertical position of
the apparatus and the water temperature, as required, to complete the
concentration in 5 - 10 minutes. At the proper rate of distillation
the balls of the column will actively chatter, but the chambers will
not flood.
7.14.1.2 When the apparent volume of liquid reaches 0.5 ml,
remove the apparatus from the water bath and allow it to drain and
cool for at least 10 minutes. Remove the Snyder column and rinse its
lower joints into the concentrator tube with 0.2 ml of solvent.
Adjust the final extract volume to 1.0 - 2.0 ml.
7.14.2 Nitrogen blowdown technique.
7.14.2.1 Place the concentrator tube in a warm bath (30°C)
and evaporate the solvent volume to 0.5 ml using a gentle stream of
clean, dry nitrogen (filtered through a column of activated carbon).
CAUTION: New plastic tubing must not be used between the carbon trap and the
sample, since it may introduce phthalate interferences.
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7.14.2.2 Rinse down the internal wall of the concentrator
tube several times with solvent during the nitrogen blowdown. During
evaporation, position the concentrator tube to avoid condensing water
into the extract. Under normal procedures, the extract must not be
allowed to become dry.
CAUTION: When the volume of solvent is reduced below 1 ml, some semivolatile
analytes such as cresols may be lost.
7.15 The extract may now be subjected to cleanup procedures or analyzed for
the target analytes using the appropriate determinative technique(s). If further
handling of the extract will not be performed immediately, stopper the
concentrator tube and store in a refrigerator. If the extract will be stored
longer than 2 days, it should be transferred to a vial with a Teflon® lined
screw-cap, and labeled appropriately. In no case should the recommended holding
times for analytical procedures provided in Chapter Four, Table 4-1 be exceeded.
8.0 QUALITY CONTROL
8.1 Any reagent blanks or matrix spike samples should be subjected to
exactly the same analytical procedures as those used on actual samples.
8.2 Refer to Chapter One for general quality control procedures and Method
3500 for specific QC procedures for extraction and sample preparation.
9.0 METHOD PERFORMANCE
Refer to the determinative methods listed in Table 1 for performance data.
10.0 REFERENCES
1. Lopez-Avila, V., Beckert, W., et. al., "Single Laboratory Evaluation of
Method 8060 - Phthalate Esters", EPA/600/4-89/039.
2. Tomkins, B.A., Merriweather, R., et. al., "Determination of Eight
Organochlorine Pesticides at Low Nanogram/Liter Concentrations in
Groundwater Using Filter Disk Extraction and Gas Chromatography", JAOAC
International, 75(6), pps. 1091-1099 (1992).
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FIGURE 1
DISK EXTRACTION APPARATUS
Reservoir
Clamp
Empore™
Extraction Disk
Base
(Fritted or with Screen)
Drip Tube
Filter Flask or Manifold
3535 - 10
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METHOD 3535
SOLID-PHASE EXTRACTION (SPE)
7.1 Measure 1 L of sample.
Add MeOH and surrogates as
specified in determinative
method. Prepare matrix spikes.
7 2 Adjust pH to range listed
in Table 1 .
7 3 Assemble manifold for
multiple extractions.
7 3.1
Do samples
contain significant
particulates?
7 4 Wash extraction apparatus
and disk with methylene chloride.
7.5 Wash extraction apparatus
and disk with acetone.
7.6 PreWet disk with MeOH. Do not
allow disk to dry before extraction
has been completed.
7.7 Rinse disk with water.
7.8 Filter sample, blank, or
matrix spike as quickly as the
vacuum will allow. Dry the disk
under vacuum for 3 minutes
7.9 Remove standard filter assembly
and insert collection tube
7.10 Add acetone to disk.
7.11 - 7.12 Add 15 mL of methylene
chloride to the sample bottle Rinse
Repeat.
7.13.1 Assemble K-D concentrator.
7.13.2 Dry combined extracts in
collection tube by passing them
through drying column of anhydrous
sodium sulfate Collect dried
extract in concentrator
7.13.3 Rinse collection tube and
drying column into K-D flask
7.13.4 Add boiling chips to flask.
Attach 3-ball Snyder column.
Complete the concentration in
10-20 mins. Remove K-D apparatus
from water bath and allow it to dram
and cool for at least 10 mins.
3535 - 12
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METHOD 3535
SOLID-PHASE EXTRACTION (SPE) (Continued)
7.13.4.1 Remove Snyder
column. AddSO mL of
exchange solvent and
new boiling chip. Reattach
column and concentrate
the extract.
7135 Remove Snyder Column.
Yes
7.14.1.1 Add fresh boiling
chip to concentrator tube
and attach 2-ball micro-
Snyder Column. Prewet.
Complete concentration
in 5-10 minutes
7 13 5 Adjust extract to final
volume of 5-10 ml
7 1 4.2 1 Place concentrator tube in
warm bath and evaporate solvent
volume to 0 5 mL using N? .
7 15 Cleanup or analyze
extract.
7.14.1 2 Remove
apparatus from water
bath and allow to drain
and cool for 10 mms
Adjust final extract
volume to 1-2 mL.
3535 - 13
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METHOD 3540C
SOXHLET EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 Method 3540 is a procedure for extracting nonvolatile and
semivolatile organic compounds from solids such as soils, sludges, and wastes.
The Soxhlet extraction process ensures intimate contact of the sample matrix
with the extraction solvent.
1.2 This method is applicable to the isolation and concentration of
water-insoluble and slightly water soluble organics in preparation for a
variety of chromatographic procedures.
1.3 This method is restricted to use by or under the supervision of
trained analysts. Each analyst must demonstrate the ability to generate
acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 The solid sample is mixed with anhydrous sodium sulfate, placed in
an extraction thimble or between two plugs of glass wool, and extracted using
an appropriate solvent in a Soxhlet extractor.
2.2 The extract is then dried, concentrated (if necessary), and, as
necessary, exchanged into a solvent compatible with the cleanup or
determinative step being employed.
3.0 INTERFERENCES
Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Soxhlet extractor - 40 mm ID, with 500-mL round bottom flask.
4.2 Drying column - 20 mm ID Pyrex® chromatographic column with Pyrex®
glass wool at bottom.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without
frits may be purchased. Use a small pad of Pyrex® glass wool to
retain the adsorbent. Prewash the glass wool pad with 50 mL of
acetone followed by 50 mL of elution solvent prior to packing the
column with adsorbent.
3540C - 1 Revision 3
January 1995
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4.3 Kuderna-Danish (K-D) apparatus
4.3.1 Concentrator tube - 10-mL, graduated (Kontes K-570050-1025
or equivalent), A ground-glass stopper is used to prevent evaporation
of extracts.
4.3.2 Evaporation flask - 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.3.3 Snyder column - Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column - Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
NOTE: The following glassware is recommended for the purpose of solvent
recovery during the concentration procedures requiring the use of
Kuderna-Danish evaporative concentrators. Incorporation of this
apparatus may be required by State or local municipality regulations
that govern air emissions of volatile organics. EPA recommends the
incorporation of this type of reclamation system as a method to
implement an emissions reduction program. Solvent recovery is a
means to conform with waste minimization and pollution prevention
initiatives.
4.4 Solvent vapor recovery system (Kontes K-545000-1006 or K-547300-
0000, Ace Glass 6614-30, or equivalent).
4.5 Boiling chips - Solvent-extracted, approximately 10/40 mesh
(silicon carbide or equivalent).
4.6 Water bath - Heated, with concentric ring cover, capable of
temperature control (± 5°C). The bath should be used in a hood.
4.7 Vials - Glass, 2-mL capacity, with Teflon®-!ined screw or crimp
top.
4.8 Glass or paper thimble or glass wool - Contaminant-free.
4.9 Heating mantle - Rheostat controlled.
4.10 Disposable glass pasteur pipet and bulb.
4.11 Apparatus for determining percent dry weight.
4.11.1 Drying oven - capable of maintaining 105°C.
4.11.2 Desiccator.
4.11.3 Crucibles - Porcelain or disposable aluminum.
3540C - 2 Revision 3
January 1995
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4.12 Apparatus for grinding
4.13 Analytical balance - capable of weighing to 0.0001 g.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests.
Unless otherwise indicated, it is intended that all reagents shall conform to
the specifications of the Committee on Analytical Reagents of the American
Chemical Society, where such specifications are available. Other grades may
be used, provided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of the
determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene
chloride, a method blank must be analyzed, demonstrating that there is no
interference from the sodium sulfate.
5.4 Extraction solvents - All solvents must be pesticide quality or
equivalent.
5.4.1 Soil/sediment and aqueous sludge samples shall be extracted
using either of the following solvent systems:
5.4.1.1 Acetone/Hexane (1:1) (v/v), CH3COCH3/C6H14.
NOTE: This solvent system has lower disposal cost and lower
toxicity.
5.4.1.2 Methylene chloride/Acetone (1:1 v/v),
CH2C12/CH3COCH3.
5.4.2 Other samples shall be extracted using the following:
5.4.2.1 Methylene chloride, CH2C12.
5.4.2.2 Toluene/Methanol (10:1) (v/v), C6H5CH3/CH3OH.
5.5 Exchange solvents - All solvents must be pesticide quality or
equivalent.
5.5.1 Hexane, C6H14.
5.5.2 2-Propanol, (CH3)2CHOH.
5.5.3 Cyclohexane, C6H12.
3540C - 3 Revision 3
January 1995
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5.5.4 Acetonitrile, CH3CN.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Sample Handling
7.1.1 Sediment/soil samples - Decant and discard any water layer
on a sediment sample. Mix sample thoroughly, especially composited
samples. Discard any foreign objects such as sticks, leaves, and rocks.
7.1.2 Waste samples - Samples consisting of multiple phases must
be prepared by the phase separation method in Chapter Two before
extraction. This extraction procedure is for solids only.
7.1.3 Dry waste samples amenable to grinding - Grind or otherwise
subdivide the waste so that it either passes through a 1-mm sieve or can
be extruded through a 1-mm hole. Introduce sufficient sample into the
grinding apparatus to yield at least 10 g after grinding.
7.1.4 Gummy, fibrous, or oily materials not amenable to grinding
should be cut, shredded, or otherwise reduced in size to allow mixing
and maximum exposure of the sample surfaces for the extraction. The
addition of anhydrous sodium sulfate to the sample (1:1) may make the
mixture amenable to grinding.
7.2 Determination of percent dry weight - When sample results are to be
calculated on a dry weight basis, a second portion of sample should be weighed
at the same time as the portion used for analytical determination.
WARNING: The drying oven should be contained in a hood or be vented.
Significant laboratory contamination may result from drying a
heavily contaminated sample.
Immediately after weighing the sample for extraction, weigh 5 - 10 g of
the sample into a tared crucible. Dry this aliquot overnight at 105°C. Allow
to cool in a desiccator before weighing. Calculate the % dry weight as
follows:
„. , . , . g of dry sample ,nn
% dry weight = — xlOO
g of sample
7.3 Blend 10 g of the solid sample with 10 g of anhydrous sodium
sulfate and place in an extraction thimble. The extraction thimble must drain
freely for the duration of the extraction period. A glass wool plug above and
3540C - 4 Revision 3
January 1995
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below the sample in the Soxhlet extractor is an acceptable alternative for the
thimble.
7.3.1 Add 1.0 ml of the surrogate standard spiking solution onto
the sample (see Method 3500 for details on the surrogate standard and
matrix spiking solutions).
7,3.2 For the sample in each analytical batch selected for
spiking, add 1.0 mL of the matrix spiking standard.
7.3.3 For base/neutral-acid analysis, the amount added of the
surrogates and matrix spiking compounds should result in a final
concentration of 100 ng/VL of each base/neutral analyte and 200 ng/^L of
each acid analyte in the extract to be analyzed (assuming a 1 juL
injection). If Method 3640, Gel Permeation Chromatography Cleanup, is
to be used, add twice the volume of surrogates and matrix spiking
compounds since half the extract is lost due to loading of the GPC
column.
7.4 Place approximately 300 ml of the extraction solvent (Sec. 5.4)
into a 500-mL round bottom flask containing one or two clean boiling chips.
Attach the flask to the extractor and extract the sample for 16 - 24 hours at
4-6 cycles/hour.
7.5 Allow the extract to cool after the extraction is complete.
7.6 Assemble a Kuderna-Danish (K-D) concentrator (Sec. 4.3), if
necessary, by attaching a 10-mL concentrator tube to a 500-mL evaporation
flask.
7.7 Attach the solvent vapor recovery glassware (condenser and
collection device) (Sec. 4.4) to the Snyder column of the K-D apparatus
following manufacturer's instructions.
7.8 Dry the extract by passing it through a drying column containing
about 10 cm of anhydrous sodium sulfate. Collect the dried extract in a K-D
concentrator. Wash the extractor flask and sodium sulfate column with 100 to
125 ml of extraction solvent to complete the quantitative transfer.
7.9 Add one or two clean boiling chips to the flask and attach a three-
ball Snyder column. Prewet the Snyder column by adding about 1 ml of
methylene chloride to the top of the column. Place the K-D apparatus on a hot
water bath (15 - 20°C above the boiling point of the solvent) so that the
concentrator tube is partially immersed in the hot water and the entire lower
rounded surface of the flask is bathed with hot vapor. Adjust the vertical
position of the apparatus and the water temperature, as required, to complete
the concentration in 10 - 20 minutes. At the proper rate of distillation the
balls of the column will actively chatter, but the chambers will not flood.
When the apparent volume of liquid reaches 1-2 ml, remove the K-D apparatus
from the water bath and allow it to drain and cool for at least 10 minutes.
7.10 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add approximately 50 ml of the exchange
solvent and a new boiling chip, and reattach the Snyder column. Concentrate
3540C - 5 Revision 3
January 1995
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the extract as described in Sec. 7.9, raising the temperature of the water
bath, if necessary, to maintain proper distillation. When the apparent volume
again reaches 1-2 ml, remove the K-D apparatus from the water batch and
allow it to drain and cool for at least 10 minutes.
7.11 Remove the Snyder column and rinse the flask and its lower joints
into the concentrator tube with 1 - 2 ml of methylene chloride or exchange
solvent. If sulfur crystals are a problem, proceed to Method 3660 for
cleanup. The extract may be further concentrated by using the techniques
described in Sec. 7.12 or adjusted to 10.0 ml with the solvent last used.
7.12 If further concentration is indicated in Table 1, either micro
Snyder column technique (Sec. 7.12.1) or nitrogen blowdown technique (Sec.
7.12.2) is used to adjust the extract to the final volume required.
7.12.1 Micro Snyder column technique
7.12.1.1 Add another one or two clean boiling chips to the
concentrator tube and attach a two-ball micro Snyder column.
Prewet the column by adding about 0.5 ml. of methylene chloride or
exchange solvent to the top of the column. Place the K-D apparatus
in a hot water bath so that the concentrator tube is partially
immersed in the hot water. Adjust the vertical position of the
apparatus and the water temperature, as required, to complete the
concentration in 5 - 10 minutes. At the proper rate of
distillation the balls of the column will actively chatter, but the
chambers will not flood.
7.12.1.2 When the apparent volume of liquid reaches 0.5 mL,
remove the K-D apparatus from the water bath and allow it to drain
and cool for at least 10 minutes. Remove the Snyder column and
rinse the flask and its lower joints with about 0.2 ml of solvent
and add to the concentrator tube. Adjust the final volume to 1.0 -
2.0 ml, as indicated in Table 1, with solvent.
7.12.2 Nitrogen blowdown technique
7.12.2.1 Place the concentrator tube in a warm water bath
(approximately 35'C) and evaporate the solvent volume to the
required level using a gentle stream of clean, dry nitrogen
(filtered through a column of activated carbon).
CAUTION: Do not use plasticized tubing between the carbon trap and the
sample, since it may introduce contaminants.
7.12.2.2 The internal wall of the tube must be rinsed
several times with the appropriate solvent during the operation.
During evaporation, the solvent level in the tube must be
positioned to prevent water from condensing into the sample (i.e.,
the solvent level should be below the level of the water bath).
Under normal operating conditions, the extract should not be
allowed to become dry.
3540C - 6 Revision 3
January 1995
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CAUTION: When the volume of solvent is reduced below 1 mL, semivolatile
analytes may be lost.
7.13 The extracts obtained may now be analyzed for the target analytes
using the appropriate organic technique(s) (see Sec. 4.3 of this Chapter). If
analysis of the extract will not be performed immediately, stopper the
concentrator tube and refrigerate. If the extract will be stored longer than
2 days, it should be transferred to a vial with a Teflon®-!ined screw cap or
crimp top, and labeled appropriately.
8.0 QUALITY CONTROL
8.1 Any reagent blanks, matrix spikes, or replicate samples should be
subjected to exactly the same analytical procedures as those used on actual
samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
9.0 METHOD PERFORMANCE
Refer to the determinative methods for performance data.
10.0 REFERENCES
None.
3540C - 7 Revision 3
January 1995
-------
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METHOD 3540C
SOXHLET EXTRACTION
7.1 Select appropriate
sample handling
technique.
7.2 Determine
sample % dry
weight.
7.3 Add appropriate
surrogate and matrix
spiking standards.
7.4 Add extraction
solvent to flask;
extract for 16-24
hours.
7.5 Collect
extract.
7.8 Dry extract
with sodium
sulfate.
7.9 Concentrate
extract using
K-D apparatus.
7.11
Are sulfur
crystals
present?
7.12 Perform
determinative
method.
7.10
Is solvent
exchange
required?
7.10 Add exchange
solvent reconcentrate
extract.
Proceed to
Method 3660
for cleanup.
3540C - 9
Revision 3
January 1995
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METHOD 3542
EXTRACTION OF SEMIVOLATILE ANALYTES COLLECTED USING
MODIFIED METHOD 5 (METHOD 0010) SAMPLING TRAIN
1.0 SCOPE AND APPLICATION
1.1 This method describes the extraction of semivolatile organic compounds
from samples collected by the EPA SW-846 Method 0010. This method replaces
Section 8.1 of Method 0010 (Modified Method 5 Sampling Train, also known as
SemiVOST) and Sections 7.1 and 7.2 of Method 8270 (Gas Chromatography/ Mass
Spectrometry for Semivolatile Organics: Capillary Column Technique), which deal
with sample preparation. These sections discuss sample preparation procedures.
Section 8.1 of Method 0010 addresses preparation of Method 0010 train components
for analysis with very little detail. Sections 7.1 and 7.2 of Method 8270
address preparation of water, soil/sediment, and water matrices. Analytical
procedures described in Section 7.3 of Method 8270 are relevant, with the
exception that the final volume of the extracts of the Method 0010 train
components must be 5 ml, with surrogate compound concentrations as indicated in
this method.
1.2 Although this sample preparation technique is intended primarily for
gas chromatography/mass spectrometric (GC/MS) analysis following Method 8270, the
extracts prepared according to this method may be used with other analytical
methods. The Method 0010 sampling train collects semivolatile organic compounds
with boiling points above lOO'C. Some of these semivolatile organic compounds
may not be amenable to gas Chromatography and will require the application of
high performance liquid Chromatography (HPLC) for quantitative analysis. The use
of HPLC coupled with mass spectrometry (HPLC/MS) is an analytical technique that
may also be applied. A solvent exchange from methylene chloride to a more polar
solvent such as acetonitrile or extraction with a solvent other than methylene
chloride will probably be required for successful application of HPLC techniques.
Some semivolatile analytes may require derivatization for successful GC/MS
analysis.
1.3 This method is restricted to use by or under the supervision of
analysts experienced in the extraction and concentration of semivolatile organic
compounds from the components of Method 0010 trains. Each analyst must
demonstrate the ability to generate acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 Samples generated by the Method 0010 Sampling Train (Method 0010
Sampling Train, Figure 1) are separated into six parts:
a) a particulate matter filter (labeled in Method 0010 as Container
No. 1);
b) a front half rinse (labeled in Method 0010 as Container No. 2);
3542 - 1 Revision 0
January 1995
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c) condenser rinse and rinse of all sampling train components located
between the filter and the sorbent module (labeled in Method 0010
as Container No. 5);
d) sorbent trap section of the organic module (labeled in Method 0010
as Container No. 3);
e) any condensate and condensate rinse (labeled in Method 0010 as
Container No. 4); and
f) silica gel (labeled in Method 0010 as Container No. 6).
2.2 The overall sample preparation scheme (flowchart) is shown in Figure
3. The six parts recovered from the Method 0010 sampling train yield three 5-mL
extracts to be analyzed according to the analytical procedures of Method 8270.
2.2.1 The particulate matter filter is extracted by Soxhlet
(Method 3540), with exceptions as noted).
2.2.2 The front half rinse is filtered, and any filtrate is added
to the particulate matter filter for Soxhlet extraction. The front half
rinse is a 50:50 mixture of methanol and methylene chloride generated by
rinsing the probe and the front half of the filter holder in the
Method 0010 train. The front half rinse is extracted with methylene
chloride by separatory funnel (Method 3510, with exceptions as noted) after
sufficient organic-free reagent water has been added to make the methylene
chloride separate as a distinct phase from the methanol/water.
2.2.3 The extracts from the filter and front half rinse are
combined, moisture is removed by filtering through anhydrous sodium sulfate
(Na2S04), and the combined extract is concentrated using a Kuderna-
Danish (K-D) sample concentrator (Method 3540) to a final volume of 5 ml.
The final sample concentration to 5 ml can be performed more accurately by
reducing the volume of the sample using a gentle stream of nitrogen or by
using a micro-K-D.
2.2.4 The condensate and condensate rinse fractions consist of the
aqueous contents of the first impinger of the Method 0010 sampling train
and the 50:50 methanol/methylene chloride rinse of the first impinger of
the Method 0010 sampling train. The condensate and condensate rinse
fractions are combined and extracted with methylene chloride using a
separatory funnel after sufficient organic-free reagent water has been
added to make the methylene chloride separate from the methanol/water
following the procedures of Method 3510 (with exceptions as noted).
2.2.5 After an initial methylene chloride extraction without pH
adjustment, the pH of the combined condensate/condensate rinse fraction is
determined. If the condensate/condensate rinse fraction is acid (pH < 7),
the pH is adjusted to a level less than 2 and the methylene chloride
extraction is repeated. The pH of the condensate/condensate rinse fraction
is then made basic (pH > 12), and the methylene chloride extraction is
repeated. The methylene chloride extracts are combined, and moisture is
removed by filtration through a bed of anhydrous Na2S04. If the
3542 - 2 Revision 0
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condensate/condensate rinse fraction is found to be basic after the initial
methylene chloride extraction, the pH adjustment sequence is reversed: a
basic extraction is performed prior to an acid extraction, the methylene
chloride extracts are combined, the moisture is removed, and the extract
is concentrated to a volume of 5 ml.
2.2.6 The XAD-2® sampling module is combined with the filter holder
back half rinse and the 50:50 methylene chloride/methanol condenser rinse
and extracted by Soxhlet (Method 3540, with exceptions as noted). Organic-
free reagent water is added to the extract to ensure the separation of
methanol/water from the methylene chloride, and a water extraction of the
methylene chloride extract is performed. Moisture is removed from the
methylene chloride extract, which is then concentrated to a final volume
of 5 mL for analysis.
2.2.7 The contents of the remaining impingers are usually archived,
but may be extracted by separatory funnel. The silica gel is reused after
regeneration by heating to remove moisture.
3.0 INTERFERENCES
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware. All of these
materials must be routinely demonstrated to be free from interferences under the
conditions of the analysis by preparing and analyzing laboratory method (or
reagent) blanks.
3.1.1 Glassware must be cleaned thoroughly before using. The
glassware should be washed with laboratory detergent in hot water followed
by rinsing with tap water and distilled water. The glassware may be
cleaned by baking in a glassware oven at 400°C for at least one hour.
After the glassware has cooled, the glassware should be rinsed three times
with methanol and three times with methylene chloride. Volumetric
glassware should not be heated to 400°C. Rather, after washing and
rinsing, volumetric glassware may be rinsed with methanol followed by
methylene chloride and allowed to dry in air.
3.1.2 The use of high purity reagents and solvents helps to minimize
interference problems in sample analysis.
3.2 Matrix interferences in the analysis may be caused by components of
the sampling matrix that are extracted from the samples. If matrix interferences
interfere with the analysis, sample cleanup procedures (e.g., Method 3620 or
Method 3610) may be employed to remove or mitigate the interferences.
4.0 APPARATUS AND MATERIALS
4.1 Soxhlet extractor - 40 mm I.D., with 50-mL round bottom flask and
condenser.
4.2 Boiling chips - Teflon®, solvent rinsed with methylene chloride,
approximately 10/40 mesh.
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4.3 Forceps - Rinsed with methylene chloride before use.
4.4 Separatory funnel - 250-mL or larger, with Teflon® stopcock.
4.5 Amber glass jar - 500-mL with Teflon®-lined screw cap.
4.6 Glass funnel - Long stem.
4.7 Kuderna-Danish (K-D) apparatus.
4.7.1 Concentrator tube - 10-mL graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts.
4.7.2 Evaporation flask - 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.7.3 Snyder column - Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.7.4 Snyder column - Two-ball micro (Kontes K-569001-0219 or
equivalent).
NOTE: The glassware in Sec. 4.8 is recommended for the purpose of solvent
recovery during the concentration procedures (Sec. 7.2.3 and 7.3.4)
requiring the use of Kuderna-Danish evaporative concentrators.
Incorporation of this apparatus may be required by State or local
municipality regulations that govern air emissions of volatile organics.
EPA recommends the incorporation of this type of reclamation system as
a method to implement an emissions reduction program. Solvent recovery
is a means to conform with waste minimization and pollution prevention
initiatives.
4.8 Solvent vapor recovery system - (Kontes 545000-1006 or K-547300-0000,
Ace Glass 6614-30, or equivalent).
4.9 Glass wool - Non-silanized, pre-cleaned by Soxhlet extraction with
methylene chloride. Air dry, store in pre-cleaned 500-mL jar.
4.10 Vials - 7- to 10-mL capacity, calibrated (calibrated centrifuge tubes
may also be used).
4.11 Heating mantle - Rheostat-controlled.
4.12 Water bath - Heated, with concentric ring cover, capable of
temperature control 80eC ± 5°C. The water bath should be used in a hood.
4.13 Gas-tight syringe - 5-mL to 10-mL capacity. Gas-tight syringes have
a glass barrel, with a Teflon® plunger to form an effective seal. The lack of
contact with metal and the sealing properties make these syringes very useful for
transferring liquid solutions.
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4.14 Nitrogen blowdown apparatus - Analytical evaporator such as The Meyer
N-EVAP Model 111 (Organomation Associates Inc., South Berlin, MA 01549) or
equivalent.
4.15 Filter - Glass- or quartz-fiber filters, without organic binder. The
filters should be the same as those used in the Method 0010 sampling train.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, all reagents shall conform to the specifications of the Committee on
Analytical Reagents of the American Chemical Society, where such specifications
are available. Other grades may be used, provided it is first ascertained that
the reagent is of sufficient purity to permit its use without compromising the
integrity of the sample.
5.2 Methanol, CH3OH - Pesticide quality or equivalent.
5.3 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.4 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.5 Sodium hydroxide solution (10 Molar) - Dissolve 40 g of sodium
hydroxide (NaOH, ACS reagent grade) in organic-free reagent water and dilute to
100 ml.
5.6 Sulfuric acid (9 Molar), H2S04 - Slowly add 50 ml of concentrated 18 M
H2S04 (ACS reagent grade, specific gravity 1.84) to 50 ml of organic-free reagent
water.
5.7 Sodium sulfate, Na2S04 - ACS, reagent grade, granular, anhydrous.
Purify by heating at 400°C for four hours in a shallow tray.
5.8 Surrogate stock solution - Either surrogates (e.g., the surrogates
used in Method 8270) or isotopically-labeled analogs of the compounds of interest
should be spiked into the Method 0010 train components prior to extraction. Both
surrogate and isotopically-labeled analogs may be used, if desired. A surrogate
(i.e., a compound not expected to occur in an environmental sample but chemically
similar to analytes) should be added to each sample, blank, and method spike just
prior to extraction. The recovery of the surrogate is used to monitor for
unusual matrix effects or sample processing errors. Normally three or more
surrogate are added for each analyte group. The surrogate stock solution may be
prepared from pure standard materials or purchased as a certified solution.
Prepare the stock solution in methylene chloride, using assayed liquids or
solids, as appropriate.
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5.8.1 The following compounds are the surrogates recommended in
SW-846 Method 8270:
Acid Base/Neutral
2-Fluorophenol 2-Fluorobiphenyl
2,4,6-Tribromophenol Nitrobenzene-d5
Phenol-de Terphenyl-d14
5.8.2 Prepare a surrogate stock solution in methylene chloride that
contains the surrogate compounds at a concentration of 5000 g/mL for the
acidic compounds, and 2500 g/mL for base/neutral compounds. Prepare the
stock surrogate solution by accurately weighing 0.50 ± 0.05 g each of
2-fluorobiphenyl, p-terphenyl-du, and nitrobenzene-d5, and 1.00 ± 0.05 g
each of 2,4,6-tribromophenol, phenol-de, and 2-fluorophenol. Dissolve the
materials in methylene chloride and dilute to volume in a 200-mL volumetric
flask. When compound purity is assayed to be 96% or greater, the weight
may be used without correction to calculate the concentration of the stock
solution.
5.8.3 Transfer the stock solution into Teflon®-sealed screw-cap
bottles sized to minimize headspace. Store at 4°C and protect from light.
Stock solutions should be checked regularly for signs of degradation or
evaporation, especially just prior to preparing spiking solutions. Allow
solutions to come to room temperature before use.
5.8.4 Stock solutions should be replaced after one year, or sooner
if analysis indicates a problem.
5.9 Surrogate spiking solution - Prepare a surrogate spiking solution by
transferring a 10-mL aliquot of the surrogate stock solution (using a 10-mL
volumetric pipet) into a 50-mL volumetric flask containing approximately 20 ml
of methylene chloride. Dilute to a final volume of 50 ml with methylene
chloride.
5.9.1 Transfer the surrogate spiking solution into Teflon®-sealed
screw-cap bottles appropriately sized to minimize headspace. Store at 4°C
and protect from light. Spiking solutions should be checked regularly for
signs of degradation or evaporation, especially just prior to use.
5.9.2 Surrogate spiking solutions should be replaced after six
months, or sooner if analysis indicates a problem.
5.10 Isotopically-labeled analog stock solution - Either surrogates (e.g.,
the surrogate standards used in Method 8270) or isotopically-labeled analogs of
the compounds of interest must be spiked into the Method 0010 train components
prior to extraction. Both surrogates and isotopically-labeled analogs may be
used, if desired. The use of isotopically-labeled analogs is optional but highly
recommended. Common isotopic labels which are used include deuterium and
carbon-13; homologs and fluorinated analogs of the compounds of interest may also
be used. To assess extraction efficiency, use of an isotopically-labeled analog
of the compound of interest is essential. The isotopically-labeled analog is
spiked into the matrix immediately prior to extraction, and losses of the spiked
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compound can be attributed to the sample extraction/concentration process. An
isotopically-labeled analog stock solution can be made from pure standard
materials or purchased as a certified solution. Even though the use of
isotopically-labeled analogs is optional, each compound to be quantitated needs
to be represented by a specific recovery standard, whether in the surrogate
mixture (Sec. 5.8) or in a separate spike.
5.10.1 Prepare an isotopically-labeled analog stock solution by
accurately weighing approximately 0.250 g of each of the materials to be
used. Dissolve in methylene chloride and dilute to volume with methylene
chloride in a 200-mL volumetric flask. When compound purity is assayed to
be 96% or greater, the weight may be used without correction to calculate
the concentration of the stock solution.
5.10.2 Transfer the stock solution into Teflon®-sealed screw-cap
bottles sized to minimize headspace. Store at 4°C and protect from light.
Stock solutions should be checked regularly for signs of degradation,
evaporation, or isotope exchange, especially just prior to preparing
spiking solutions from them. Allow solution to come to room temperature
before use.
5.10.3 Stock solutions should be replaced after one year, or sooner
if analysis indicates a problem.
5.11 Isotopically-labeled analog spiking solution
5.11.1 Prepare the isotopically-labeled analog standard by
transferring a 10-mL aliquot of the stock isotopically-labeled analog stock
solution (using a 10-mL volumetric pipet) into a 50-mL volumetric flask
containing approximately 20 ml of methylene chloride. Dilute to volume
with methylene chloride. The concentration of the spiking solution should
allow the isotopically-labeled analogs to be observed in the final sample
in approximately the middle of the calibration range for the gas
chromatograph/mass spectrometer, assuming 100% recovery.
5.11.2 Transfer the solution into Teflon®-sealed screw-cap bottles
sized to minimize headspace. Store at 4°C and protect from light. Spiking
solutions should be checked regularly for signs of degradation or
evaporation, especially just prior to use. Allow solutions to come to room
temperature prior to use.
5.11.3 Spiking solutions should be replaced after six months, or
sooner if analysis indicates a problem.
5.12 Stock method spike solution - A method spike consists of a spike of
a clean matrix (i.e., clean, dry XAD-2®, clean, dry filter, or water) with a
solution containing the compounds of interest (the method spike solution). The
compound recoveries obtained from a method spike demonstrate that the compounds
of interest can be recovered from the matrix, and aid in elucidating the effects
of the field matrix. The method spike solution can be made from pure standard
materials or purchased as certified solutions. The compounds of interest for the
field test should be used as components of the method spike solution. A method
spike is generated by spiking clean XAD-2® or clean organic-free reagent water.
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5.12.1 Prepare a stock method spike solution by accurately weighing
0.05 g of each of the compounds of interest. Dissolve the materials in
methylene chloride and dilute to volume in a 50-mL volumetric flask. When
compound purity is assayed to be 96% or greater, the weight may be used
without correction to calculate the concentration of the stock solution.
5.12.2 Transfer the stock method spike solution into Teflon®-sealed
screw-cap bottles sized to minimize headspace. Store at 4°C and protect
from light. Stock solutions should be checked regularly for signs of
degradation or evaporation, especially just prior to preparing spiking
solutions from them.
5.12.3 Stock solutions should be replaced after one year, or sooner
if analysis indicates a problem.
5.13 Method spike standard solution
5.13.1 Prepare the method spike standard solution by transferring a
25-mL aliquot of the stock method spike solution (using a 25-mL volumetric
pipet) into a 100-mL volumetric flask containing approximately 20 mL of
methylene chloride. Dilute to volume with methylene chloride.
5.13.2 Transfer the method spike standard solution into Teflon®-! ined
screw-cap bottles appropriately sized to minimize headspace. Store at 4"C
and protect from light. Spiking solutions should be checked regularly for
signs of degradation or evaporation, especially just prior to use.
5.13.3 Spiking solutions should be replaced after six months, or
sooner if analysis indicates a problem.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 The six components from each Method 0010 sampling train (Figure 1)
should be stored at 4°C between the time of sampling and extraction.
6.2 Each sample should be extracted within 14 days of collection and
analyzed within 40 days of extraction. The extracted sample should be stored at
4°C.
7.0 PROCEDURE
7.1 The sample preparation procedure for the six parts of the Method 0010
train will result in three sample extracts for analysis:
a) Particulate matter filter and front half rinse;
b) Condensate and condensate rinse; and
c) XAD-2® and condenser/back half rinse.
7.2 Particulate matter filter and front half rinse
7.2.1 Filter - The filter is identified as Container No. 1 in Method
0010.
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7.2.1.1 Using clean forceps, place about 10 Teflon® boiling
chips into the bottom of the round bottom flask of the Soxhlet
extractor and connect the Soxhlet extractor to the round bottom flask.
7.2.1.2 Using a clean syringe or volumetric pipet, add a 1-
mL aliquot of the surrogate spiking solution (Sec. 5.9) to the filter.
If isotopically-labeled analogs are being used, the isotopically-
labeled analog solution (Sec. 5.11) may be added at this time. If a
method spike is being prepared, the method spike solution (Sec. 5.13)
may be added at this time.
7.2.1.2.1 To ensure proper filter spiking, use a
volume of approximately 1 ml of spiking solution. Leave the
filter in the petri dish, particulate material on top, for
spiking. Add the 1 ml of spiking solution uniformly onto the
particulate-coated surface of the filter in the petri dish by
spotting small volumes at multiple filter locations, using a
syringe.
7.2.1.2.2 Repeat the spiking process with
isotopically-labeled standards or method spike solution, if
these solutions are being used.
7.2.1.3 Using clean forceps, place the particulate matter
filter into a glass thimble and position the glass thimble in the
Soxhlet extractor, making sure that the filter will be completely
submerged in the methylene chloride with each cycle of the Soxhlet
extractor. Place a piece of pre-cleaned unsilanized glass wool on top
of the filter in the Soxhlet extractor to keep the filter in place.
Rinse the petri dish three times with methylene chloride and add
rinses to the Soxhlet.
7.2.1.4 The front half rinse (Container No. 2) may contain
particulate material which has been removed from the probe. This
particulate material should be extracted with the filter.
7.2.1.4.1 To separate particulate matter from the
front half rinse, filter the front half rinse. To avoid
introducing any contamination, use the same type of filter
which has been used in the Method 0010 train, from the same
lot as the filter in the Method 0010 train. Filter the Front
Half Rinse, rinse Container No. 2 three times with 10-mL
aliquots of methylene chloride, and filter the methylene
chloride rinses.
7.2.1.4.2 Transfer the filter with any particulate
matter to the Soxhlet extractor with the original filter from
the Method 0010 train. Extract the two filters together.
7.2.1.4.3 Return the liquid portion of Container
No. 2 to its original container for subsequent extraction or,
alternatively, the front half rinse can be filtered directly
into a separatory funnel for extraction of the liquid portion
of the front half rinse.
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7.2.1.5 Slowly add methylene chloride to the Soxhlet
extractor containing the two filters through the Soxhlet (with
condenser removed), allowing the Soxhlet to cycle. Add sufficient
solvent to fill the round bottom flask approximately half full and
submerge the thimble containing the filters.
7.2.1.6 Place a heating mantle under the round bottom flask
and connect the upper joint of the Soxhlet to a condenser, making sure
that the coolant is flowing through the condenser.
7.2.1.7 Allow the sample to extract for 18 hours, cycling
approximately once every thirty minutes.
7.2.1.8 After cooling, disconnect the extractor from the
condenser. Tilt the Soxhlet slightly until the remaining solvent has
drained into the round bottom flask.
7.2.1.9 Transfer the extract from the round bottom flask
into a 500-mL amber glass bottle with Teflon®-!ined screw cap. The
bottle should have been rinsed three times each with methanol and
methylene chloride. Rinse the round bottom flask three times with
approximately 10-mL aliquots of methylene chloride and transfer the
rinses to the amber bottle. Store the filter extract at 4°C until
extraction of the filtered front half rinse has been completed.
7.2.2 Front half rinse - The front half rinse is identified as
Container No. 2 in Method 0010.
7.2.2.1 Transfer the liquid contents of the filtered front
half rinse sample to a separatory funnel of appropriate size for the
volume of the sample (a typical front half rinse sample is 200 to
300 ml). Rinse the sample container three times with 10-mL aliquots
of methylene chloride, transferring the rinses to the separatory
funnel after each rinse.
7.2.2.2 Because the front half rinse sample consists of a
mixture of methanol and methylene chloride, sufficient organic-free
reagent water must be added to the separatory funnel to cause the
organic and aqueous/methanol phases to separate into two distinct
layers. The methylene chloride layer will be at the bottom of the
separatory funnel. Continue to add water until the bottom layer
(methylene chloride) does not increase in volume. An increase in
volume can be monitored by marking the separatory funnel at the
position of the phase separation.
NOTE: The front half rinse is not spiked with any surrogate, isotopic
analog, or method spike solutions because the extract from the
front half rinse is combined with the extract from the particulate
matter filter sample.
7.2.2.3 Add additional methylene chloride, if necessary, so
that the ratio of water/methanol to methylene chloride is
approximately 3:1. Add sodium hydroxide (Sec. 5.5) until pH of the
water layer is > 11 (but < 14). Use wide-range pH paper to determine
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pH. Shake vigorously for 2 minutes with rapid arm motion, with
periodic venting to release excess pressure. Allow the organic layer
to separate for at least 10 minutes. Collect the methylene chloride
extract in a 500-mL amber glass bottle with Teflon®-!ined screw cap,
which has been rinsed three times each with methanol and methylene
chloride.
7.2.2.4 Add a second volume of methylene chloride
(approximately the same volume as the first extraction) to the
separatory funnel and repeat the extraction procedure, combining the
methylene chloride extracts in the amber bottle.
7.2.2.5 Perform a third extraction in the same manner.
7.2.2.6 Acidify the water to a pH <2 (but > 0) with sulfuric
acid (Sec. 5.6) and repeat Sec. 7.2.2.4 three times. Measure pH with
wide-range pH paper.
7.2.3 Concentration of filter and front half rinse extracts - The
combined extracts and rinses of extract storage bottles will have a total
volume of 1 liter or more.
7.2.3.1 Assemble a Kuderna-Danish concentrator by attaching
a 10-mL concentrator tube to a 500-mL evaporative flask with clips or
springs. Using a clean pair of forceps, place about five Teflon®
boiling chips into the concentrator tube. If the volume of extract
to be concentrated is greater than 500 ml, repeat the concentration
as many times as required using the same 500-rnL evaporative flask and
systematically adding remaining extract. If repeated concentrations
are performed, use new boiling chips each time.
7.2.3.2 Using a clean pair of forceps, place a small portion
of precleaned unsilanized glass wool in the bottom of a long stem
funnel, and pour a 2.54-cm (1-in) layer of cleaned sodium sulfate
(Sec. 5.7) on top of the glass wool (use more sodium sulfate, if
possible; fill the funnel to within approximately 1.27 cm (0.5 in)
of the top).
7.2.3.3 Rinse the sodium sulfate contained in the funnel
three times with methylene chloride; discard the rinses. Support the
funnel in a ring or clamp above the flask to prevent tipping.
7.2.3.4 Place the funnel into the upper opening of the K-D
flask and slowly pour extracts from the Filter and Front Half Rinse
through the sodium sulfate. Rinse the amber jars containing the
extracts three times, using approximately 10 ml of methylene chloride
each time. Add the rinses to the funnel. Rinse the sodium sulfate
with methylene chloride to complete the transfer.
NOTE: During this process, monitor the condition of the sodium sulfate
to determine that the bed of sodium sulfate is not solidifying and
exceeding its drying capacity. If the sodium sulfate bed can be
stirred and is still free-flowing, effective moisture removal from
the extracts is occurring. If the sodium sulfate bed has begun to
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solidify, do not add more extract. Replace the sodium sulfate
bed, re-dry the contents of the K-D flask, and continue drying the
extracts.
7.2.3.5 Attach a three-ball macro Snyder column to the
evaporative flask. Prewet the Snyder column by adding about 2 ml of
methylene chloride to the top. Attach the solvent vapor recovery
glassware (condenser and collection device) to the Snyder column of
the K-D apparatus, following manufacturer's instructions. Place the
K-D apparatus on a hot water bath (80 - 85°C) so that the concentrator
tube is partially immersed in hot water. Adjust the vertical position
of the apparatus and the water temperature as required to complete the
concentration in 20 to 30 minutes. Rinse sides of K-D during
concentration with a small volume of methylene chloride. When the
apparent volume of the liquid reaches 6-8 mL, remove the K-D apparatus
from the water bath and allow the apparatus to cool and drain for at
least 10 minutes.
NOTE: Never let the extract in the concentrator tube go to dryness even
though additional solvent is present in the upper portion of the
K-D apparatus.
NOTE: If the sample concentration is not completed within the
anticipated period of time, check the temperature of the water
bath and check the composition of the sample. If the methanol has
not been completely removed from the methylene chloride extract by
the procedures described in Sees. 7.2.2.2 and 7.2.2.3, residual
methanol will concentrate far slower than a methylene chloride
extract and analytes will be lost in the concentration step. A
sample containing methanol which has been concentrating for a
prolonged period of time cannot be recovered, but extracts which
contain residual methanol and have not yet been concentrated can
be recovered by performing the procedures in Sees. 7.2.2.2 and
7.2.2.3 again.
7.2.3.6 Remove the Snyder column and evaporative flask.
With a clean pair of forceps, add two new Teflon® boiling chips to the
concentrator tube. Attach a two-ball micro Snyder column to the
concentrator tube. Attach the solvent vapor recovery glassware
(condenser and collection device) to the Snyder column of the K-D
apparatus, following manufacturer's instructions. Prewet the Snyder
column with about 0.5 ml of methylene chloride. Place the K-D
apparatus on the hot water bath so that the concentrator tube is
partially immersed in hot water, supporting the tube with a clamp.
When the apparent volume of the liquid reaches 4 - 5 mL, remove the
K-D apparatus from the water bath and allow the apparatus to cool and
drain for at least 10 minutes. If the volume is greater than 5 mL,
add a new boiling chip to the concentrator tube, prewet the Snyder
column, and concentrate again on the hot water bath. Transfer the
extract to a calibrated vial or centrifuge tube, rinse concentrator
tube with a minimum volume of methylene chloride and add rinses to the
vial, and add methylene chloride, if necessary, to attain a final
volume of 5 mL.
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Alternatively, the final concentration may be performed by
blowing the surface of the solvent with a gentle stream of nitrogen
using a glass disposable pipet to direct the stream of nitrogen. When
the nitrogen blowdown technique is used, care must be taken to
carefully rinse the sides of the vessel using a minimum quantity of
methylene chloride to ensure that analytes are in the methylene
chloride solution, not deposited on the sides of the glass container.
Perform the blowdown procedure in a calibrated vial or centrifuge tube
which does not contain boiling chips. The final extract volume must
be 5 ml.
7.2.3.7 Transfer the extract to a 10-mL glass storage vial
with a Teflon®-!ined screw cap. Label the extract as Front Half Rinse
and Particulate Filter, and store at 4°C until analysis (Sec. 7.3 and
following Sections, Method 8270). Mark the liquid level on the vial
to monitor solvent evaporation during storage.
7.3 Condensate and condensate rinse - The condensate is identified as
Container No. 4 in Method 0010; the condensate rinse is Container No. 5.
7.3.1 Transfer the contents of both the condensate and the
condensate rinse samples to a clean separatory funnel (expected volume of
both containers is approximately 500 ml). Rinse each of the sample
containers with three aliquots of methylene chloride (approximately 10 ml
each), transferring the rinses to the separatory funnel.
7.3.2 Using a clean syringe or volumetric pipet, add a 1-mL aliquot
of the surrogate solution (Sec. 5.9) to the liquid in the separatory
funnel. If isotopically-labeled analogs are being used, the isotopically-
labeled analog solution (Sec. 5.11) should be added to the separatory
funnel.
7.3.3 Perform an initial methylene chloride extraction of the
combined condensate/condensate rinse which has been spiked with appropriate
spiking solution(s). Add organic-free reagent water as needed to ensure
separation of phases. After the initial methylene chloride extraction,
check the pH of the condensate/condensate rinse solution with wide-range
pH paper.
7.3.3.1 If the solution is acidic (pH < 7), add acid until
the pH is < 2 but > 0 and perform another methylene chloride
extraction. Then make the condensate/condensate rinse solution basic
(pH > 11 but < 14) and perform another methylene chloride extraction.
Combine methylene chloride extracts, remove moisture, and concentrate
for analysis.
7.3.3.2 If, after the initial methylene chloride extraction,
the condensate/condensate rinse solution is basic, increase pH until
the pH is > 11 but < 14, and perform another methylene chloride
extraction. Then make the condensate/condensate rinse solution acidic
(pH < 2 but > 0) and perform another methylene chloride extraction.
Combine the methylene chloride extracts, remove moisture, and
concentrate the extract for analysis.
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7.3.4 Refer to Sec. 7.2.2.2 and following sections for extraction
and concentration of the condensate/condensate rinse extract.
7.4 XAD-2® - The sorbent trap section of the organic module is identified
as Container No. 3 in Method 0010. The sorbent trap section of the organic
module shall be used as a sample transport container.
7.4.1 Using clean forceps, place about 10 Teflon® boiling chips in
the bottom of the round bottom flask of the Soxhlet extractor and connect
the Soxhlet extractor to the round bottom flask.
7.4.2 Transfer the XAD-2® to the extraction thimble. Remove the
glass wool plug from the XAD-2® trap and add to the thimble of the Soxhlet
extractor. If ground glass stoppers are used to seal the sorbent trap
during shipment, these ground glass stoppers should be rinsed with
methylene chloride and the rinsate added to the round bottom flask of the
Soxhlet extractor.
7.4.2.1 If the XAD-2® is dry (i.e., free-flowing), pour the
XAD-2® directly into the thimble (or directly into the Soxhlet
extractor) and rinse the trap with methylene chloride, adding the
rinses to the round bottom flask.
7.4.2.2 If the XAD-2® is wet, removal from the trap may be
difficult. To accomplish the transfer, flush the resin from the trap
using a Teflon® wash bottle containing methylene chloride.
Alternatively, acidic water (pH < 2) can be used to wash the walls of
the XAD-2® trap. Collect the resin and solvent in a clean 500-mL
beaker. Transfer the XAD-2®/methylene chloride from the beaker to the
extraction thimble, taking care that no solvent is lost.
Alternatively, the XAD-2® can be transferred directly to the Soxhlet
extractor and the methylene chloride rinse and transfer solvent
allowed to drain through the XAD-2® to the round bottom flask. Rinse
the beaker several times with methylene chloride, pouring the rinses
through the XAD-2® bed once the extraction thimble is in the Soxhlet
extractor. Be sure that a glass wool plug is in place above the XAD-
2® to ensure that the XAD-2® does not float out of the thimble.
NOTE: Under no circumstances should methanol or acetone be used to transfer
the resin.
7.4.2.3 Alternative approaches to transfer of XAD-2® from
the trap to the extraction thimble are discussed below.
7.4.2.3.1 The XAD-2® can be transferred directly
to the Soxhlet extractor and the methylene chloride rinse and
transfer solvent allowed to drain through the XAD-2® to the
round bottom flask. If ground glass stoppers are used to
seal the sorbent trap during shipment, these ground glass
stoppers should be rinsed with methylene chloride and the
rinsate added to the round bottom flask of the Soxhlet
extractor. To remove the XAD-2® from the sampling module,
remove the glass wool from the end of the XAD-2® sampling
module. Place this glass wool in the Soxhlet extractor to
3542 - 14 Revision 0
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ensure thorough extraction of the glass wool. If the XAD-2®
is being transferred directly to the Soxhlet extractor, place
a small piece of pre-cleaned glass wool in the side-arm of
the Soxhlet extractor to ensure that no XAD-2® enters the
side-arm of the Soxhlet extractor. Invert the XAD-2®
sampling module (glass frit up) over an extraction thimble
contained in a beaker, or directly over the Soxhlet extractor
with pre-cleaned glass wool in the bottom, as shown in Figure
2. Add approximately 5 to 10 ml of methylene chloride above
the glass frit of the sampling module. Connect a rubber
pipet filler bulb with check valve that has been fitted with
a ball joint to the XAD-2® sampling module. Using air
pressure created by squeezing the bulb, gently but firmly
push the methylene chloride through the frit, forcing the
XAD-2® out of the sampling module. Avoid allowing methylene
chloride to be pulled up into the bulb, since the sample will
be compromised if methylene chloride is pulled up into the
bulb and allowed to become part of the extract. This process
will need to be repeated 3 to 5 times. Use a Teflon® wash
bottle containing methylene chloride to rinse the walls of
the sampling module to transfer XAD-2® which has been
retained on the walls of the sampling module after transfer
of XAD-2® to the Soxhlet. A methylene chloride rinse of the
walls will not remove all of the XAD-2®, but after 3 to
5 rinses of the walls of the sampling module, no more than a
monolayer of XAD-2® particles should be retained. If more
than a monolayer of XAD-2® remains, additional rinses are
required. The glass wool in the side arm of the Soxhlet
extractor must be removed and added to the Soxhlet.
NOTE: Under no conditions should methanol or acetone be used in the transfer
of the XAD-2®.
7.4.2.3.2 Alternatively, the wet XAD-2® may be
transferred from the sampling module to a piece of cleaned
aluminum foil by inverting the trap (glass frit up) and
tapping the trap on a solid surface covered with the cleaned
aluminum foil. This process is slow and may result in
breakage of the sampling module. If ground glass stoppers
are used to seal the sorbent trap during shipment, these
ground glass stoppers should be rinsed with methylene
chloride and the rinsate added to the round bottom flask of
the Soxhlet extractor. After the majority of the XAD-2® has
been removed from the trap by tapping, the XAD-2® on the
aluminum foil may be transferred to the extraction thimble.
The sampling module should be rinsed with methylene chloride
to flush the remaining XAD-2® particles adhering to the glass
wall into the extraction thimble. After all XAD-2® has been
transferred into the Soxhlet thimble, add a plug of glass
wool to the top of the XAD-2® to hold the resin in place.
7.4.3 With the XAD-2® in the Soxhlet extractor and glass wool on top
of the XAD-2®, use a clean syringe or volumetric pipet to add a 1-mL
aliquot of the surrogate spiking solution to the XAD-2®. Be sure that the
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needle of the syringe penetrates the XAD-2® bed to a depth of at least 1.27
cm (0.5 in). If isotopically-labeled standard solution or method spike
solution is being used, these solutions should be spiked at this time.
7.4.4 Container No. 5 contains the methylene chloride/methanol rinse
of the condenser and all train components from the back half of the filter
holder to the XAD-2® sampling module. These rinses consist of 50:50
methanol:methylene chloride. Transfer the contents of Container No. 5 to
a separatory funnel and rinse the container with three 10-mL aliquots of
methylene chloride. Add the rinses to the separatory funnel. Sufficient
organic-free reagent water must be added to the separatory funnel to cause
the organic and aqueous phases to separate into two distinct layers. Refer
to Sec. 7.2.2.2 and following sections for preparation of a methylene
chloride extract from Container No. 5. Add the methylene chloride layer
from the separatory funnel directly to the Soxhlet extractor containing the
XAD-2® or collect the methylene chloride extract in a container and
transfer from this container to the Soxhlet containing the XAD-2®. Pour
the methylene chloride extract of the condenser and back half rinses
through the XAD-2® in the Soxhlet extractor; rinse the container or
separatory funnel 3 times with approximately 10-mL aliquots of methylene
chloride and add the rinses to the Soxhlet.
7.4.5 Add additional methylene chloride to the Soxhlet extractor,
if necessary, pouring approximately 300-400 ml through the XAD-2® bed so
that the round bottom flask is approximately half-full and the XAD-2® bed
is covered.
7.4.6 Place a heating mantle under the round bottom flask and
connect the upper joint of the Soxhlet extractor to a condenser.
NOTE: Start the extraction process immediately after spiking is completed
to ensure that no volatilization of organic compounds from the resin
or any spiking solutions occurs before the extraction process is
started.
7.4.7 Allow the sample to extract for at least 18 hours but not more
than 24 hours, cycling once every 25 - 30 minutes.
NOTE: Be sure that cooling water for the condensers is cold and circulating.
Watch the extractor through two or three cycles to ensure that the
extractor is working properly.
7.4.8 After the Soxhlet extractor has been cooled, disconnect the
extractor from the condenser and tilt the extractor slightly until the
remaining solvent in the Soxhlet has drained into the round bottom flask.
7.4.9 Inspect the contents of the round bottom flask to determine
whether there is a visible water layer on top of the methylene chloride.
If no water layer is observed, transfer the extract into a 500-mL amber
glass bottle with Teflon®-lined screw cap for storage (Sec. 7.2.1.8), or
proceed directly with removal of moisture and concentration of the extract
(Sec. 7.2.3.1). If a water layer is observed in the Soxhlet round bottom
flask, transfer the contents to a separatory funnel, rinsing the round
bottom flask three times with methylene chloride and adding the rinsings
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to the separatory funnel. Drain the methylene chloride from the separatory
funnel and store in an amber glass bottle. Then perform an acid/base
extraction of the water layer remaining in the separatory funnel (Sec.
7.3.3). Add the methylene chloride extract from the acid/base extraction
to the methylene chloride extract from the round bottom flask in the amber
glass jar. Store the extract in the amber glass bottle at 4°C for
subsequent removal of moisture and concentration following the steps
outlined in Sec. 7.2.3.1.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific Quality Control procedures.
8.2 A method blank consists of a clean filter, clean dry XAD-2®, or
organic-free reagent water, which is spiked with surrogates prior to extraction.
The method blank is extracted and concentrated using the same procedures as the
corresponding sample matrix. One method blank is extracted and analyzed for
every ten samples.
8.3 A method spike consists of a clean filter, XAD-2®, or organic-free
reagent water, which -is spiked with surrogates, isotopically-labeled standards,
if used, and method spike solution, if used, prior to extraction. The method
spike is extracted and concentrated using the same procedures as the
corresponding sample matrix. At least one method spike is extracted and analyzed
for every matrix, with a frequency of one method spike for every twenty samples.
9.0 METHOD PERFORMANCE
9.1 Method Performance Evaluation - Evaluation of analytical procedures
for a selected series of compounds must include the sample preparation procedures
and each associated analytical determination. The analytical procedures should
be challenged by the test compounds spiked at appropriate levels and carried
through all the procedures.
9.2 Method Detection Limits - The overall method detection limits (lower
and upper) need to be determined on a compound-by-compound basis because
different compounds may exhibit different collection, retention, and extraction
efficiencies as well as instrument minimum detection limits. The method
detection limit needs to be quoted relative to a given sample volume. The upper
limits for the method need to be determined relative to compound retention
volumes (breakthrough).
9.3 Method Precision and Bias - The overall method precision and bias
needs to be determined on a compound-by-compound basis at a given concentration
level. The method precision value would include a combined variability due to
sampling, sample preparation, and instrumental analysis. The method bias would
be dependent upon the collection, retention, and extraction efficiency of the
train components. The surrogate recoveries shown below represent mean
recoveries for surrogates in all Method 0010 matrices in a field dynamic spiking
study.
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10.0 REFERENCES
1. Bursey, J., Homolya, J., McAllister, R., and McGaughey, J., Laboratory and
Field Evaluation of the SemiVOST Method, Vols. 1 and 2, U. S. Environmental
Protection Agency, EPA/600/4-851/075A, 075B. 1985.
2. Test Methods for Evaluating Solid Waste. Physical/Chemical Methods, SW-846
Manual, 3rd ed., Document No. 955-001-00000-1. Available from the
Superintendent of Documents, U. S. Government Printing Office, Washington,
DC. November, 1986.
3. Handbook. Quality Assurance/Quality Control (QA/QC) Procedures for
Hazardous Waste Incineration, EPA-625/6-89-023, Cincinnati, OH. 1990.
4. Bursey, J., Merrill, R., McAllister, R., and McGaughey, J., Laboratory
Validation of VOST and SemiVOST for Halogenated Hydrocarbons from the Clean
Air Act Amendments List, Vols. 1 and 2, U. S. Environmental Protection
Agency, EPA 600/R-93/123a and b, (NTIS PB93-227163 and PB93-227171)
Research Triangle Park, NC. July. 1993.
5. McGaughey, J., Bursey, J., and Merrill, R., Field Test of a Generic Method
for Halogenated Hydrocarbons, U. S. Environmental Protection Agency,
EPA 600/R-93/101, (NTIS PB 93-212181), Research Triangle Park, NC. July,
1993.
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TABLE 1
PRECISION AND BIAS VALUES FOR METHOD 35421
Compound
2-Fluorophenol
Phenol -d5
Nitrobenzene-d5
2-Fluorobiphenyl
2,4,6-Tribromophenol
Terphenyl-du
Mean
Recovery
74.6
77.8
65.6
75.9
67.0
78.6
Standard
Deviation
28.6
27.7
32.5
30.3
34.0
32.4
Relative Standard
Deviation (%)
38.3
35.6
49.6
39.9
50.7
41.3
1 The surrogate recovery values shown in Table 1 represent mean recoveries for
surrogates in all Method 0010 matrices in a field dynamic spiking study.
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FIGURE 1
METHOD 0010 SAMPLING TRAIN
Stac*
i
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FIGURE 2
TRANSFER OF WET XAD-2®
Rubber
Bulb
M*O,a add«d to XAD-23 Trap
T«flon
-------
FIGURE 3
SAMPLE PREPARATION SCHEME (FLOWCHART) USING MODIFIED METHOD 5 (METHOD 0010) TRAIN
XAO-2«
(Container 3)
Spike with Surrogates (and
Isotopically-Labeled Analogs)
Impinger Contents
i (Impingers 2 and 3)
Archive
Soxhlet Extraction
XAD-2® Extract
Add Sufficient Water
to Separate into Two
Phases; Separata
Extract Water Layer with
CH2CI2 Adjust pH and Do
Acid/Base or Base/Acid Extraction
Combine Ct-fe Cl 2 Extracts
Rinse ail of Glassware Between
Back Half of Filter Holder and
XAD-2® (Filter Holder Back Half
Connector, and Condenser)
with CH jCI ^CH pH
(Container 5)
Silica Gel
(Impinger 4)
(Container 5)
Weigh in the Field
Regenerate
Re-use
Remove Moisture
with Na SO
Concentrate to 5mL
Analyze by GC/MS
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FIGURE 3 (continued)
SAMPLE PREPARATION FLOWCHART USING MODIFIED METHOD 5 (METHOD 0010) TRAIN
^r^n-M?" i Rinse of impinger 1 i Rarticulate Matter
flmpingerl) . CK CL/CH.OH rittar L—
Container4) ' 223 finer -^
(Cnntainar 11
i
1
_| |^ .
j
I Spike with Surrogates,
Tlsotopically -Labeled
' Analogs
Spike with Surrogates and •
Isotopicaily-Labeled Analogs wm
TSoxhlet Extraction
cw n
2 2
Separatory Funnel Extraction !
separate phases)
y ?
y
Extract water Layer with j _
CH, Cl 2, Adjust pH and do CH a
Acid/Base or Base/Acid 1. 2
Extraction E*™*
' Comhina rwnrin |^^
Combine CHjCI 2 Extracrs ^^ Extracts ~~"
1
1
T T
F
Remove Moisture with NajSO^ Remove Moisture with N^ SO4
T T
|
Concentrate to 5mL Concentrate to 5mL
f T
Analyze by GC/MS Analyze by GC/MS
front naff Rinse,
Front Half of Ffter Holder,
-i Probe and Nozzle
f^LJ /•*] //"*IJ /^LJ
Wfij Olj/^" T»"'
(Container 2)
T
Filter Add Filter to
Paniculate Matter Filter
T
Separatory Funnel
Extraction
(Add H20 if necessary to
separate phases)
T
Extract Water Layer with
CH2 Cl j. Adjust pH and do
Acid/Base or Base/Acid
Extraction
f
Save CHj CI2 Layer
(Bottom)
3542 - 23
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METHOD 3545
ACCELERATED SOLVENT EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 Method 3545 is a procedure for extracting water insoluble or slightly
water soluble semivolatile organic compounds from soils, clays, sediments,
sludges, and waste solids. The method uses elevated temperature (100°C) and
pressure (1500 - 2000 psi) to achieve analyte recoveries equivalent to those from
Soxhlet extraction, using less solvent and taking significantly less time than
the Soxhlet procedure. This procedure was developed and validated on a
commercially-available, automated extraction system.
1.2 This method is applicable to the extraction of semivolatile organic
compounds, organophosphorus pesticides, organochlorine pesticides, chlorinated
herbicides, and PCBs, which may then be analyzed by a variety of chromatographic
procedures.
1.3 This method has been validated for solid matrices containing 250 to
12,500 M9/kg of semivolatile organic compounds, 250 to 2500 M9/kg of
organophosphorus pesticides, 5 to 250 /^g/kg of organochlorine pesticides, 50 to
5000 M9/kg °f chlorinated herbicides, and 1 to 1400 /zg/kg of PCBs.
1.4 This method is applicable to solid samples only, and is most effective
on dry materials with small particle sizes. Therefore, waste samples must
undergo phase separation, as described in Chapter Two, and only the solid phase
material is to be extracted by this procedure. If possible, soil/sediment
samples may be air-dried and ground to a fine powder prior to extraction.
Alternatively, if the loss of analytes during drying is a concern, soil/sediment
samples may be mixed with anhydrous sodium sulfate. The total mass of material
to be prepared depends on the specifications of the determinative method and the
sensitivity required for the analysis, but 10 - 30 g of material are usually
necessary and can be accommodated by this extraction procedure.
1.5 This method is restricted to use by or under the supervision of
trained analysts. Each analyst must demonstrate the ability to generate
acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 Samples are mixed with anhydrous sodium sulfate or are air dried, then
ground to 100 - 200 mesh (150 urn to 75 /im), and loaded into the extraction cell.
2.2 The powdered sample is equilibrated for 5 minutes and extracted for
5 minutes using elevated temperature (100°C), elevated pressure (1500-2000 psi),
and the appropriate solvent system. The solvent systems utilized for this
procedure include:
2.2.1 1:1 acetone/hexane for organochlorine pesticides and PCBs
2.2.2 1:1 methylene chloride/acetone for semivolatile organics
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2.2.3 1:1 methylene chloride/acetone for organophosphorus pesticides
2.2.4 2:1 acetone/methylene chloride acidified with phosphoric acid
for chlorinated herbicides
2.3 The extraction cell is allowed to cool to room temperature and the
solvent is collected in a glass vial.
2.4 The extract may be concentrated, if necessary, and, as needed,
exchanged into a solvent compatible with the cleanup or determinative step being
employed.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
3.2 If necessary, Florisil and/or sulfur cleanup procedures may be
employed. In such cases, proceed with Method 3620 and/or Method 3660.
4.0 APPARATUS AND MATERIALS
4.1 Automated accelerated solvent extractor - Dionex Accelerated Solvent
Extractor (or equivalent) with appropriately-sized extraction cells. Currently,
cells are available that will accommodate 10 g, 20 g and 30 g samples. Cells
should be made of stainless steel or other material capable of withstanding the
pressure requirements (2000+ psi) necessary for this procedure.
4.2 Apparatus for determining percent dry weight
4.2.1 Oven - drying
4.2.2 Desiccator
4.2.3 Crucibles - porcelain or disposable aluminum
4.3 Apparatus for grinding - capable of reducing particle size to < 1 mm.
4.4 Analytical balance - capable to weighing to 0.01 g.
4.5 Vials for collection of extracts - 40-mL or 60-mL, pre-cleaned, open
top screw-cap with PTFE-lined silicone septum (Dionex 049459, 049460, 049461,
049462 or equivalent).
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
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5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
then a method blank must be analyzed demonstrating that there is no interference
from the sodium sulfate.
5.4 Phosphoric acid solution (see Sec. 5.5.5). Prepare a 1:1 (v/v)
solution of 85% phosphoric acid (H3P04) in organic-free reagent water.
5.5 Extraction solvents
The extraction solvent to be employed depends on the analytes to be
extracted, as described below. All solvents should be pesticide quality or
equivalent.
5.5.1 Organochlorine pesticides are extracted with acetone/hexane
(1:1, v/v), CH3COCH3/C6H14.
5.5.2 Semi volatile organics are extracted with methylene
chloride/acetone (1:1, v/v), CH2C12/CH3COCH3.
5.5.3 PCBs are extracted with hexane/acetone (1:1, v/v),
C6H14/CH3COCH3.
5.5.4 Organophosphorus pesticides are extracted with methylene
chloride/acetone (1:1, v/v), CH2C12/CH3COCH3.
5.5.5 Chlorinated herbicides are extracted with acetone/methylene
chloride/phosphoric acid solution (250:125:15, v/v/v) CH3COCH3/CH2C12/H3P04.
Make fresh before each use.
5.6 Nitrogen gas, high purity. For purging the extraction cell.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
See the introductory material to this chapter, Organic Analysis,
Sec. 4.1.
7.0 PROCEDURE
7.1 Sample preparation
7.1.1 Sediment/soil samples - Decant and discard any water layer on
a sediment sample. Mix the sample thoroughly, especially composited
samples. Discard any foreign objects such as sticks, leaves, and rocks.
Air dry the sample at room temperature for 48 hours in a glass tray or on
hexane-rinsed aluminum foil. Alternatively, mix the sample with an equal
volume of anhydrous sodium sulfate until a free-flowing powder is obtained.
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NOTE: Dry, finely-ground soil/sediment allows the best extraction efficiency
for nonvolatile, nonpolar organics, e.g., 4,4'-DDT, PCBs, etc. Air-
drying may not be appropriate for the analysis of the more volatile
organochlorine pesticides (e.g., the BHCs) or the more volatile of the
semivolatile organics because of losses during the drying process.
7.1.2. Waste samples - Multiphase waste samples must be prepared by
the phase separation method in Chapter Two before extraction. This
extraction procedure is for solids only.
7.1.3 Dry sediment/soil and dry waste samples amenable to grinding -
Grind or otherwise reduce the particle size of the waste so that it either
passes through a 1 mm sieve or can be extruded through a 1 mm hole.
Disassemble grinder between samples, according to manufacturer's
instructions, and decontaminate with soap and water, followed by acetone
and hexane rinses.
NOTE: The note in Sec. 7.1.1 also applies to the grinding process.
7.1.4 Gummy, fibrous, or oily materials not amenable to grinding
should be cut, shredded, or otherwise reduced in size to allow mixing and
maximum exposure of the sample surfaces for the extraction. The addition
of anhydrous sodium sulfate to the sample (1:1) may make the mixture
amenable to grinding.
7.2 Determination of percent dry weight - When sample results are to be
calculated on a dry weight basis, a second portion of sample should be weighed
at the same time as the portion used for analytical determination.
WARNING: The drying oven should be contained in a hood or vented.
Significant laboratory contamination may result from drying a
heavily contaminated sample.
7.2.1 Immediately after weighing the sample for extraction, weigh
5 - 10 g of the sample into a tared crucible. Dry this aliquot overnight
at 105eC. Allow to cool in a desiccator before weighing. Calculate the
% dry weight as follows:
... ... g of dry sample .nn
% dry weight = — x 100
g of sample
7.3 Grind a sufficient weight of the dried sample from Sec. 7.1 to yield
the sample weight needed for the determinative method (usually 10 - 30 g). Grind
the sample until it passes through a 10 mesh sieve.
7.4 Transfer the ground sample to an extraction cell of the appropriate
size for the analysis. Generally, an 11-mL cell will hold 10 g of sample, a 22-
ml_ cell will hold 20 g of sample, and a 33-mL cell will hold 30 g of sample.
7.5 Add the surrogates listed in the determinative method to each sample.
Add the matrix spike/matrix spike duplicate compounds listed in the determinative
method to the two additional aliquots of the sample selected for spiking.
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7.6 Place the extraction cells into the autosampler tray.
7.7 Load the collection tray with the appropriate number (one per sample)
of 40-mL or 60-mL, precleaned, capped vials with septa.
7.8 Recommended extraction conditions
Oven temperature: 100°C
Pressure: 1500 - 2000 psi
Static time: 5 min (after 5 min pre-heat equilibration)
Flush volume: 0.6 times the cell volume
Nitrogen purge: 45 sec at 150 psi
7.8.1 Optimize the conditions, as needed, according to the
manufacturer's instructions. In general, the pressure is not a critical
parameter, as the purpose of pressurizing the extraction cell is to prevent
the solvent from boiling at the extraction temperature and to ensure that
the solvent remains in intimate contact with the sample. Any pressure in
the range of 1500 - 2000 psi should suffice.
7.8.2 Once established, the same pressure should be used for all
samples extracted for the same analysis type.
7.9 Begin the extraction according to the manufacturer's instructions.
7.10 Collect each extract in a clean 40-mL or 60-mL vial. Allow the
extracts to cool after the extractions are complete. Collected extracts will be
approximately 1.2 to 1.4 times the cell volume.
7.11 The extract is now ready for cleanup or analysis, depending on the
extent of interferants. Refer to Method 3600 for guidance on selecting
appropriate cleanup methods. Certain cleanup and/or determinative methods may
require a solvent exchange prior to cleanup and/or sample analysis.
7.12 The extraction of chlorinated herbicides uses phosphoric acid in the
extraction solvent. Therefore, after extractions are completed, the extractor
should be rinsed by pumping acetone through all lines.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 8000 for guidance on quality control
procedures. Refer to Method 3500 for specific guidance on extraction and sample
preparation procedures.
8.2 Before processing any samples, the analyst should demonstrate that all
parts of the equipment in contact with the sample and reagents are interference-
free. This is accomplished through the analysis of a solid matrix method blank
(e.g., clean sand). Each time samples are extracted, and when there is a change
in reagents, a method blank needs to be extracted and analyzed for the compounds
of interest. The method blank should be carried through all stages of the sample
preparation and measurement.
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8.3 Standard quality assurance practices should be used with this method.
Field duplicates should be collected to validate the precision of the sampling
procedures. A matrix spike/matrix spike duplicate, or matrix spike and duplicate
sample analysis, and a laboratory control sample should be prepared and analyzed
with each batch of samples prepared by this procedure, unless the determinative
method provides other guidance.
8.4 Surrogate standards should be added to all samples when listed in the
appropriate determinative method.
9.0 METHOD PERFORMANCE
9.1 Chlorinated pesticides and semivolatile organics
Single-laboratory accuracy data were obtained for chlorinated pesticides
and semivolatile organics at three different spiking concentrations in three
different soil types. Spiking concentrations ranged from 5 to 250 Aig/kg f°r the
chlorinated pesticides and from 250 to 12500 M9/kg for the semivolatiles.
Spiked samples were extracted both by the Dionex Accelerated Solvent Extraction
system and by a Perstorp Environmental Soxtec™ (automated Soxhlet). Extracts
were analyzed either by Method 8270 or Method 8081. Method blanks, spikes and
spike duplicates were included for the low concentration spikes; matrix spikes
were included for all other concentrations. The data are reported in detail in
Reference 1, and represent seven replicate extractions and analyses for each
sample. Data summary tables are included in Methods 8270 and 8081.
9.2 Organophosphorus pesticides and chlorinated herbicides
Single-laboratory accuracy data were obtained for Organophosphorus
pesticides (OPPs) and chlorinated herbicides at two different spiking
concentrations in three different soil types. Spiking concentrations ranged from
250 to 2500 jug/kg for the OPPs and from 50 to 5000 /xg/kg for the chlorinated
herbicides. Chlorinated herbicides were spiked with a mixture of the free acid
and the ester (1:1). Spiked samples were extracted both by the Dionex
Accelerated Solvent Extractor and by Soxhlet for the OPPs. Extracts were
analyzed by Method 8141. Spiked chlorinated herbicides were extracted by the
Dionex Accelerated Solvent Extractor and by the shaking method described in
Method 8151. Extracts were analyzed by Method 8151. Method blanks, spikes and
spike duplicates were included for the low concentration spikes; matrix spikes
were included for all other concentrations. The data are reported in detail in
Reference 2, and represent seven replicate extractions and analyses for each
sample. Data summary tables are included in Methods 8141 and 8151.
9.3 PCBs
Single-laboratory accuracy data were obtained for PCBs from a soil sample
with PCB content certified by NIST (Standard Reference Material, SRM 1939, River
Sediment). A PCB-contaminated soil was purchased from a commercial source.
Spiking or certified concentrations ranged from 1 to 1400 jug/kg. Samples were
extracted by the Dionex Accelerated Solvent Extractor and by Soxtec™ (Perstorp
Environmental). Extracts were analyzed using Method 8082. Method blanks, spikes
and spike duplicates were included. The data are reported in Reference 2, and
3545 - 6 Revision 0
January 1995
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represent seven replicate extractions and analyses for each sample. Data summary
tables are included in Method 8082.
10.0 REFERENCES
1. B. Richter, Ezzell, J., and Felix, D., "Single Laboratory Method Validation
Report. Extraction of TCL/PPL (Target Compound List/Priority Pollutant
List) BNAs and Pesticides using Accelerated Solvent Extraction (ASE) with
Analytical Validation by GC/MS and GC/ECD"; Document 116064.A, Dionex
Corporation, June 16, 1994.
2. B. Richter, Ezzell, J., and Felix, D., "Single Laboratory Method Validation
Report. Extraction of TCL/PPL (Target Compound List/Priority Pollutant
List) OPPs, Chlorinated Herbicides and PCBs using Accelerated Solvent
Extraction (ASE)". Document 101124, Dionex Corporation, December 2, 1994).
3545 - 7 Revision 0
January 1995
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METHOD 3545
ACCELERATED SOLVENT EXTRACTION
>
'
7.1 Prepare
sample.
i
r
7.2 Determine
sample % dry
weight.
>
r
7.3 Grind sufficient
weight of the dried
sample.
^
r
7.4 Transfer ground
sample to an
extraction cell.
>
r
7.5 Add surrogates
and matrix spiking
standards.
>,
7.6 Place extraction
cells into auto
sampling train.
>
f
7.7 Load
collection tray.
1
r
7.8 Optimize
conditions of
extractor.
^
r
7.9 Begin
extraction.
i
r
7.10 Collect
extracts and
allow to cool.
>
r
7.1 1 Perform
cleanup or
determinative
method.
3545 - 8
Revision 0
January 1995
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METHOD 3550B
ULTRASONIC EXTRACTION
See Disclaimer. See manufacturer's specifications for operational settings.
1.0 SCOPE AND APPLICATION
1.1 Method 3550 is a procedure for extracting nonvolatile and semi volatile
organic compounds from solids such as soils, sludges, and wastes. The ultrasonic
process ensures intimate contact of the sample matrix with the extraction
solvent.
1.2 The method is divided into two sections, based on the expected
concentration of organics in the sample. The low concentration method
(individual organic components of less than or equal to 20 mg/kg) uses a larger
sample size and a more rigorous extraction procedure (lower concentrations are
more difficult to extract). The medium/high concentration method (individual
organic components of greater than 20 mg/kg) is much simpler and therefore
faster.
1.3 It is highly recommended that the extracts be cleaned up prior to
analysis. See Chapter Four (Cleanup), Sec. 4.2.2, for applicable methods.
1.4 Ultrasonic extraction is not as rigorous a method as other extraction
methods for soil/solids. Therefore it is critical that the method be followed
explicitly to maximize its limited extraction efficiency. This requires that:
The necessary equipment must be used (a 3/4" horn and a minimum of 300
watts of power);
The horn is properly maintained (tuned prior to use according to
manufacturer's instructions and that the tip of the horn is not worn);
The samples are properly prepared (the sample is thoroughly mixed with
anhydrous sodium sulfate so that it exists as a free flowing powder
prior to the addition of solvent);
The correct extraction procedure is followed (three extractions are
performed with the proper solvent, the ultrasonic extraction is
performed in the specified pulse mode and the tip is positioned just
below the solvent surface but above the sample); and,
There is visible observation of a very active mixing of the sample
throughout the solvent when the energy pulse is activated.
1.5 Very non-polar organic compounds (e.g. PCBs, etc.) that are strongly
adsorbed to the soil matrix are known to be extracted less efficiently using
ultrasonic extraction. Preliminary results indicate that use of the 1/4" horn
tip for extracting high concentrations (greater than 20 mg/kg) of very non-polar
compounds is inappropriate. Instead, use the 3/4" horn to maintain good
extraction efficiency.
1.6 Ultrasonic extraction is not appropriate for use with organophosphorus
compounds because it may cause the destruction of some of the target analytes
during the extraction procedure.
3550B - 1 Revision 2
January 1995
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1.7 This method is restricted to use by or under the supervision of
trained analysts. Each analyst must demonstrate the ability to generate
acceptable results with this method.
1.8 This method is not appropriate for applications where high extraction
efficiencies of analytes at very low concentrations is necessary (e.g.,
demonstration of effectiveness of corrective action).
2.0 SUMMARY OF METHOD
2.1 Low concentration method - A 30-g sample is mixed with anhydrous
sodium sulfate to form a free-flowing powder. This is solvent extracted three
times using ultrasonic extraction. The extract is separated from the sample by
vacuum filtration or centrifugation. The extract is ready for cleanup and/or
analysis following concentration.
2.2 Medium/high concentration method - A 2-g sample is mixed with
anhydrous sodium sulfate to form a free-flowing powder. This is solvent
extracted once using ultrasonic extraction. A portion of the extract is removed
for cleanup and/or analysis.
3.0 INTERFERENCES
Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Apparatus for grinding dry waste samples.
4.2 Ultrasonic preparation - A horn-type device equipped with a titanium
tip, or a device that will give equivalent performance, shall be used.
4.2.1 Ultrasonic Disrupter - The disrupter must have a minimum power
wattage of 300 watts, with pulsing capability. A device designed to reduce
the cavitation sound is recommended. Follow the manufacturers instructions
for preparing the disrupter for extraction of samples with low and
medium/high concentration.
4.2.2 Use a 3/4" horn for the low concentration method and a 1/8"
tapered microtip attached to a 1/2" horn for the medium/high concentration
method.
4.3 Sonabox - Recommended with above disrupters for decreasing cavitation
sound (Heat Systems - Ultrasonics, Inc., Model 432B or equivalent).
4.4 Apparatus for determining percent dry weight.
4.4.1 Drying oven - capable of maintaining 105°C.
4.4.2 Desiccator.
3550B - 2 Revision 2
January 1995
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4.4.3 Crucibles - Porcelain or disposable aluminum.
4.5 Pasteur glass pipets - 1-mL, disposable.
4.6 Beakers - 400-mL.
4.7 Vacuum or pressure filtration apparatus.
4.7.1 Buchner funnel.
4.7.2 Filter paper - Whatman No. 41 or equivalent.
4.8 Kuderna-Danish (K-D) apparatus.
4.8.1 Concentrator tube - 10-mL, graduated (Kontes K-570050-1025 or
equivalent). A ground-glass stopper is used to prevent evaporation of
extracts.
4.8.2 Evaporation flask - 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.8.3 Snyder column - Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.8.4 Snyder column - Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.8.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
NOTE: The following glassware is recommended for the purpose of solvent
recovery during the concentration procedures requiring the use of
Kuderna-Danish evaporative concentrators. Incorporation of this
apparatus may be required by State or local municipality regulations
that govern air emissions of volatile organics. EPA recommends the
incorporation of this type of reclamation system as a method to
implement an emissions reduction program. Solvent recovery is a means
to conform with waste minimization and pollution prevention initiatives.
4.9 Solvent vapor recovery system (Kontes K-545000-1006 or K-547300-0000,
Ace Glass 6614-30, or equivalent).
4.10 Boiling chips - Solvent-extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.11 Water bath - Heated, with concentric ring cover, capable of
temperature control (± 5°C). The batch should be used in a hood.
4.12 Balance - Top-loading, capable of accurately weighing to the nearest
0.01 g.
4.13 Vials - 2-mL, for GC autosampler, with Teflon-lined screw caps or
crimp tops.
3550B - 3 Revision 2
January 1995
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4.14 Glass scintillation vials - 20-mL, with Teflon-lined screw caps.
4.15 Spatula - Stainless steel or Teflon.
4.16 Drying column - 20 mm ID Pyrex chromatographic column with Pyrex glass
wool at bottom.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without frits
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 mL of acetone followed by
50 mL of elution solvent prior to packing the column with adsorbent.
4.17 Syringe - 5-mL.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise specified, it is intended that all inorganic reagents shall conform to
the specifications of the Committee on Analytical Reagents of the American
Chemical Society, where such specifications are available. Other grades may be
used, provided it is first ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.4 Extraction solvents - All solvents must be pesticide quality or
equivalent.
5.4.1 Low concentration soil/sediment and aqueous sludge samples
shall be extracted using a solvent system that gives optimum, reproducible,
recovery for the matrix/analyte combination to be measured. Suitable
solvent choices are given in Table 1.
5.4.2 Methylene chloride:Acetone, CH2C12:CH3COCH3 (1:1, v:v).
5.4.3 Methylene chloride, CH2C12.
5.4.4 Hexane, C6H14.
5.5 Exchange solvents - All solvents must be pesticide quality or
equivalent.
5.5.1 Hexane, C6H14.
3550B - 4 Revision 2
January 1995
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5.5.2 2-Propanol, (CH3)2CHOH.
5.5.3 Cyclohexane, C6H12.
5.5.4 Acetonitrile, CH3CN.
5.5.5 Methanol, CH3OH.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
See the introductory material to this Chapter, Organic Analytes, Sec. 4.1.
7.0 PROCEDURE
7.1 Sample handling
7.1.1 Sediment/soil samples - Decant and discard any water layer on
a sediment sample. Mix sample thoroughly, especially composited samples.
Discard any foreign objects such as sticks, leaves, and rocks.
7.1.2 Waste samples - Samples consisting of multiple phases must be
prepared by the phase separation method in Chapter Two before extraction.
This extraction procedure is for solids only.
7.1.3 Dry waste samples amenable to grinding - Grind or otherwise
subdivide the waste so that it either passes through a 1-mm sieve or can
be extruded through a 1-mm hole. Introduce sufficient sample into the
grinding apparatus to yield at least 10 g after grinding.
7.1.4 Gummy, fibrous, or oily materials not amenable to grinding
should be cut, shredded, or otherwise reduced in size to allow mixing and
maximum exposure of the sample surfaces for the extraction. The addition
of anhydrous sodium sulfate to the sample (1:1) may make the mixture
amenable to grinding.
7.2 Determination of percent dry weight - When sample results are to be
calculated on a dry weight basis, a second portion of sample should be weighed
out at the same time as the portion used for analytical determination.
WARNING: The drying oven should be contained in a hood or vented. Significant
laboratory contamination may result from drying a heavily contaminated
sample.
Immediately after weighing the sample for extraction, weigh 5-10 g of the
sample into a tared crucible. Dry this aliquot overnight at 105°C. Allow to
cool in a desiccator before weighing. Calculate the % dry weight as follows:
... ... g of dry sample ....
% dry weight = — x 100
g of sample
3550B - 5 Revision 2
January 1995
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7.3 Extraction method for samples expected to contain low concentrations
of organics and pesticides (less than or equal to 20 mg/kg):
7,3.1 The following steps should be performed rapidly to avoid loss
of the more volatile extractables.
7.3.1.1 Weigh approximately 30 g of sample into a 400-mL
beaker. Record the weight to the nearest 0.1 g.
7.3.1.2 Nonporous or wet samples (gummy or clay type) that
do not have a free-flowing sandy texture must be mixed with 60 g of
anhydrous sodium sulfate, using a spatula. If required, more sodium
sulfate may be added. After addition of sodium sulfate, the sample
should be free flowing.
7.3.1.3 Add 1 ml of surrogate standards to all samples,
spikes, standards, and blanks (see Method 3500 for details on the
surrogate standard solution and the matrix spike solution).
7.3.1.4 For the sample in each analytical batch selected for
spiking, add 1.0 ml of the matrix spiking standard.
7.3.1.5 For base/neutral-acid analysis, the amount added of
the surrogates and matrix spiking compounds should result in a final
concentration of 100 ng/^L of each base/neutral analyte and 200 ng//xL
of each acid analyte in the extract to be analyzed (assuming a 1 nl
injection). If Method 3640, Gel-Permeation Cleanup, is to be used,
add twice the volume of surrogates and matrix spiking compounds since
half of the extract is lost due to loading of the GPC column.
7.3.1.6 Immediately add 100 ml of 1:1 methylene
chlorideracetone.
7.3.2 Place the bottom surface of the tip of the #207 (or
equivalent) 3/4 inch disrupter horn about 1/2 inch below the surface of the
solvent, but above the sediment layer.
NOTE: Be sure the horn is properly tuned according to the manufacturer's
instructions.
7.3.3 Extract ultrasonically for 3 minutes, with output control knob
set at 10 (full power) and with mode switch on Pulse (pulsing energy rather
than continuous energy) and percent-duty cycle knob set at 50% (energy on
50% of time and off 50% of time). Do not use microtip probe.
7.3.4 Decant the extract and filter it through Whatman No. 41 filter
paper (or equivalent) in a Buchner funnel that is attached to a clean 500-
mL filtration flask. Alternatively, decant the extract into a centrifuge
bottle and centrifuge at low speed to remove particles.
7.3.5 Repeat the extraction two or more times with two additional
100-mL portions of solvent. Decant off the solvent after each ultrasonic
extraction. On the final ultrasonic extraction, pour the entire sample
into the Buchner funnel and rinse with extraction solvent. Apply a vacuum
3550B - 6 Revision 2
January 1995
-------
to the filtration flask, and collect the solvent extract. Continue
filtration until all visible solvent is removed from the funnel, but do not
attempt to completely dry the sample, as the continued application of a
vacuum may result in the loss of some analytes. Alternatively, if
centrifugation is used in Sec. 7.3.4, transfer the entire sample to the
centrifuge bottle. Centrifuge at low speed, and then decant the solvent
from the bottle.
7.3.6 Assemble a Kuderna-Danish (K-D) concentrator (if necessary)
by attaching a 10-mL concentrator tube to a 500-mL evaporator flask.
Attach the solvent vapor recovery glassware (condenser and collection
device) to the Snyder column of the Kuderna-Danish apparatus following
manufacturer's instructions. Transfer filtered extract to a 500-mL
evaporator flask and proceed to the next section.
7.3.7 Add one to two clean boiling chips to the evaporation flask,
and attach a three-ball Snyder column. Prewet the Snyder column by adding
about 1 ml methylene chloride to the top. Place the K-D apparatus on a hot
water bath (80 - 90°C) so that the concentrator tube is partially immersed
in the hot water and the entire lower rounded surface of the flask is
bathed with hot vapor. Adjust the vertical position of the apparatus and
the water temperature, as required, to complete the concentration in 10 -
15 min. At the proper rate of distillation the balls of the column will
actively chatter, but the chambers will not flood with condensed solvent.
When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus
and allow it to drain and cool for at least 10 min.
7.3.8 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 ml of the exchange solvent and
a new boiling chip, and re-attach the Snyder column. Concentrate the
extract as described in Sec. 7.3.10, raising the temperature of the water
bath, if necessary, to maintain proper distillation. When the apparent
volume again reaches 1 - 2 ml, remove the K-D apparatus and allow it to
drain and cool for at least 10 minutes.
7.3.9 Remove the Snyder column and rinse the flask and its lower
joints into the concentrator tube with 1 - 2 ml of methylene chloride or
exchange solvent. If sulfur crystals are a problem, proceed to Method 3660
for cleanup. The extract may be further concentrated by using the
technique outlined in Sec. 7.3.10 or adjusted to 10.0 ml with the solvent
last used.
7.3.10 If further concentration is indicated in Table 1, either micro
Snyder column technique (Sec. 7.3.10.1) or nitrogen blowdown technique
(Sec. 7.3.10.2) may be used to adjust the extract to the final volume
required.
7.3.10.1 Micro Snyder column technique
7.3.10.1.1 Add a clean boiling chip and attach a
two-ball micro Snyder column to the concentrator tube.
Prewet the column by adding approximately 0.5 ml of methylene
chloride or exchange solvent through the top. Place the
apparatus in the hot water bath. Adjust the vertical
3550B - 7 Revision 2
January 1995
-------
position and the water temperature, as required, to complete
the concentration in 5-10 minutes. At the proper rate of
distillation the balls of the column will actively chatter,
but the chambers will not flood. When the liquid reaches an
apparent volume of approximately 0.5 ml, remove the apparatus
from the water bath and allow to drain and cool for at least
10 minutes. Remove the micro Snyder column and rinse its
lower joint with approximately 0.2 ml of appropriate solvent
and add to the concentrator tube. Adjust the final volume to
the volume required for cleanup or for the determinative
method (see Table 1).
7.3.10.2 Nitrogen blowdown technique
7.3.10.2.1 Place the concentrator tube in a warm
water bath (approximately 35°C) and evaporate the solvent
volume to the required level using a gentle stream of clean,
dry nitrogen (filtered through a column of activated carbon).
CAUTION: Do not use plasticized tubing between the carbon trap and the sample,
since it may introduce contaminants.
7.3.10.2.2 The internal wall of the tube must be
rinsed down several times with the appropriate solvent during
the operation. During evaporation, the solvent level in the
tube must be positioned to prevent water from condensing into
the sample (i.e., the solvent level should be below the level
of the water bath). Under normal operating conditions, the
extract should not be allowed to become dry.
CAUTION: When the volume of solvent is reduced below 1 ml, semivolatile analytes
may be lost.
7.4 Extraction method for samples expected to contain high concentrations
of organics (greater than 20 mg/kg):
7.4.1 Transfer approximately 2 g (record weight to the nearest 0.1
g) of sample to a 20-mL vial. Wipe the mouth of the vial with a tissue to
remove any sample material. Record the exact weight of sample taken. Cap
the vial before proceeding with the next sample to avoid any cross
contamination.
7.4.2 Add 2 g of anhydrous sodium sulfate to sample in the 20-mL
vial and mix well.
7.4.3 Surrogates are added to all samples, spikes, and blanks (see
Method 3500 for details on the surrogate spiking solution and on the matrix
spike solution).
7.4.3.1 Add 1.0 ml of surrogate spiking solution to sample
mixture.
7.4.3.2 For the sample in each analytical batch selected for
spiking, add 1.0 ml of the matrix spiking standard.
3550B - 8 Revision 2
January 1995
-------
7.4.3.3 For base/neutral-acid analysis, the amount added of
the surrogates and matrix spiking compounds should result in a final
concentration of 100 ng//LiL of each base/neutral analyte and 200 ng//A
of each acid analyte in the extract to be analyzed (assuming a 1 /xL
injection). If Method 3640, Gel-Permeation Cleanup, is to be used,
add twice the volume of surrogates and matrix spiking compounds since
half the extract is lost due to loading of the GPC column.
7.4.4 Immediately add whatever volume of solvent is necessary to
bring the final volume to 10.0 ml considering the added volume of
surrogates and matrix spikes. Disrupt the sample with the 1/8 in. tapered
microtip ultrasonic probe for 2 minutes at output control setting 5 and
with mode switch on pulse and percent duty cycle at 50%. Extraction
solvents are:
7.4.4.1 For nonpolar compounds (i.e., organochlorine
pesticides and PCBs), use hexane or appropriate
solvent.
7.4.4.2 For other semivolatile organics, use methylene
chloride.
7.4.5 Loosely pack disposable Pasteur pipets with 2 to 3 cm Pyrex
glass wool plugs. Filter the extract through the glass wool and collect
5.0 ml in a concentrator tube if further concentration is required. Follow
Sec. 7.3.10 for details on concentration. Normally, the 5.0-mL extract is
concentrated to approximately 1.0 mL or less.
7.4.6 The extract is ready for cleanup or analysis, depending on the
extent of interfering co-extractives.
7.5 If analysis of the extract will not be performed immediately, stopper
the concentrator tube and refrigerate. If the extract will be stored longer than
2 days, it should be transferred to a vial with a Teflon-lined cap and labeled
appropriately.
8.0 QUALITY CONTROL
8.1 Any reagent blanks, matrix spike, and replicate samples should be
subjected to exactly the same analytical procedures as those used on actual
samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
9.0 METHOD PERFORMANCE
Refer to the determinative method for performance data.
3550B - 9 Revision 2
January 1995
-------
10.0 REFERENCES
1. U.S. EPA, Inter!aboratory Comparison Study: Methods for Volatile and Semi-
Volatile Compounds, Environmental Monitoring Systems Laboratory, Office of
Research and Development, Las Vegas, NV, EPA 600/4-84-027, 1984.
2. Christopher S. Hein, Paul J. Marsden, Arthur S. Shurtleff, "Evaluation of
Methods 3540 (Soxhlet) and 3550 (Sonication) for Evaluation of Appendix IX
Analytes from Solid Samples", S-CUBED, Report for EPA Contract 68-03-33-75,
Work Assignment No. 03, Document No. SSS-R-88-9436, October 1988.
3550B - 10 Revision 2
January 1995
-------
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METHOD 35506
ULTRASONIC EXTRACTION
>
r
7.1 Prepare samples
using appropriate
technique for the
waste matrix.
>
f
7.2 Determine the
percent dry weight
of the sample.
7.4.1 - 7.4.2 Mix
sample with anhydrous
sodium sulfate.
7.4.3 Add surrogate
standards to all
samples, spikes,
and blanks.
Is organic
concentration
expected to be
< 20 mg/kg?
7.3.1 Mix sample with
anhydrous sodium
sulfate.
7.3.1 Add surrogate
standards to all
samples, spikes,
and blanks.
7.4.4 Adjust volume;
disrupt sample with
tapered microtip
ultrasonic probe.
7.3.2 - 7.3.5
Ultrasomcally
extract sample at least
3 times with 3/4 inch
disruptor horn.
7.4.5 Filter extract
through glass wool.
7.4.5
Is further
concentration
required?
7.3.6 Dry and collect
extract in
concentrator.
7.3.7 Concentrate
extract.
x^Perform cleanups.
( or determinative j
\^ method. J
3550B - 13
Revision 2
January 1995
-------
METHOD 355CB
(continued)
7.3.8
solvent
Add exchange
; re-concentrate
extract.
/ 7 3
^ Yes / 80|V
"^ V sxcn
fcJ
7.3.9 Use Method
3660 for cleanup.
7.3.9 Do
sulfur
crystals
form?
7.3.10 Further
concentrate and/or
adjust volume.
erform cleanup
or determinative
method.
3550B - 14
Revision 2
January 1995
-------
METHOD 3560
SUPERCRITICAL FLUID EXTRACTION OF TOTAL RECOVERABLE PETROLEUM HYDROCARBONS
1.0 SCOPE AND APPLICATION
1.1 Method 3560 describes the extraction with supercritical fluids of
total recoverable petroleum hydrocarbons (TRPHs) from soils, sediments, fly ash,
and other solid materials, which are amenable to extraction with conventional
solvents. The method is suitable for use with any supercritical fluid extraction
(SFE) system that allows extraction conditions (e.g., pressure, temperature,
flowrate) to be adjusted to achieve separation of the TRPHs from the matrices of
concern.
1.2 Method 3560 is not suitable for the extraction of low-boiling TRPHs
such as gasoline.
1.3 This method is restricted to use by or under the supervision of
trained analysts. Each analyst must demonstrate the ability to generate
acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 A known amount of sample is transferred to the extraction vessel. The
sample is then extracted in the dynamic mode for up to 30 min with supercritical
carbon dioxide at 340 atm, 80°C and a gas flow rate of 500 - 1000 mL/min.
2.2 After depressurization of the carbon dioxide, the extracted TRPHs are
collected in 3 ml of tetrachloroethene or other appropriate solvent (see Sec.
5.3), or on a sorbent material, depending on the SFE system used. In the latter
case, the analytes are collected by rinsing the sorbent material with
tetrachloroethene or other suitable solvent.
2,3 After collection, the TRPHs are analyzed by the appropriate
determinative method.
3.0 INTERFERENCES
3.1 The analyst must demonstrate through the analysis of reagent blanks
(collection solvent treated as per Sec. 7.4) that the supercritical fluid
extraction system is free from interferants. To do this, perform a simulated
extraction using an empty extraction vessel and a known amount of carbon dioxide
under the same conditions as those used for sample extraction, and determine the
background contamination by analyzing the extract by the appropriate
determinative method (e.g. Methods 8015 or 8440). If glass wool and a drying
agent are used with the sample, these materials should be included when
performing a reagent blank check.
3560 - 1 Revision 0
January 1995
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3.2 The extraction vessel(s), the frits, the restrictor(s), and the
multi-port valve may retain solutes whenever high-concentration samples are
extracted. It is, therefore, good practice to clean the extraction system after
each extraction. Replacement of the restrictor may be necessary when reagent
blanks indicate carryover. At least one reagent blank should be prepared and
analyzed daily when the instrument is in use. Furthermore, reagent blanks should
be prepared and analyzed after each extraction of a high-concentration sample
(concentration in the high ppm range). If reagent blanks continue to indicate
contamination, even after replacement of the extraction vessel and the
restrictor, the multi-port valve must be cleaned.
4.0 APPARATUS AND MATERIALS
4.1 Supercritical fluid extractor and associated hardware.
WARNING: A safety feature to prevent overpressurization is required on the
extractor. This feature should be designed to protect the
laboratory personnel and the instrument from possible injuries or
damage resulting from equipment failure under high pressure.
4.1.2 Extraction vessel - Stainless-steel vessel with end fittings
and 0.5-or 2-/zm frits. Use the extraction vessel supplied by the
manufacturer of the SFE system being used. The PEEK (polyether ether
ketone) extraction vessels supplied by Isco, Inc. are acceptable for use
with the Isco SFE system.
Fittings used for the extraction vessel must be capable of
withstanding the required extraction pressures. The maximum operating
pressure for most extractors is 500 atm. However, extractors with higher
pressure ratings are available. Check with the manufacturer of the
particular extraction system on the maximum operating pressure and
temperature for that system. Make sure that the extraction vessels are
rated for such pressures and temperatures.
4.1.3 Restrictor - 50 /um ID x 150 or 375 jum OD x 25 to 60 cm length
piece of uncoated fused-silica tubing (J&W Scientific or equivalent).
Other restrictors may be used including tapered restrictors, static pinhole
restrictors, frit restrictors and variable orifice restrictors (manual and
computer-controlled), or crimped metal tubing. Check with the manufacturer
of the SFE system on the advantages and disadvantages of the various
restrictor designs.
4.1.4 Collection device - The extracted TRPHs can be collected
either in vials containing solvent, or they can be trapped on a sorbent
material (e.g., octadecyl-bonded silica, stainless steel beads).
4.1.4.1 When the analytes are collected in solvent, install
the restrictor through a hole made through the cap and septum of the
vial, and position the restrictor end about 0.5 inch from the bottom
of the vial. A syringe needle should also be inserted through the
3560 - 2 Revision 0
January 1995
-------
septum of the vial (with the tip positioned just below the septum) to
prevent buildup of pressure in the vial. Use the type of vials
appropriate for the SFE system used.
4.1.4.2 When the analytes are trapped on a sorbent material,
it is important to ensure that breakthrough of the analytes from the
trap does not occur. Desorption from the trapping medium can be
accomplished by increasing the temperature of the trap and using a
solvent to remove the analytes. Use the conditions suggested by the
manufacturer of the particular system to recover the analytes.
4.2 Carbon dioxide cylinder balance (optional) - Balances from White
Associates, Catalog No. 30, Scott Specialty Gases Model 5588D, or equivalent, can
be used to monitor the fluid usage. Such a device is useful because carbon
dioxide tanks used for SFE are not equipped with regulators. This makes it
difficult to determine when the tank needs to be replaced.
4.3 Tools required include: screwdriver (flat-blade), adjustable wrench,
pliers, tubing cutter, and various small open-end wrenches for small fittings.
4.4 Magnesium sulfate monohydrate - may be used as received.
4.5 Silanized glass wool - requires high-temperature treatment (bake in
a muffle furnace at 400°C for 2 to 4 hours) prior to use to remove any petroleum
hydrocarbons.
5.0 REAGENTS
5.1 Carbon dioxide, C02 - Either supercritical fluid chromatography (SFC)
or SFE-grade C02 is acceptable for use in SFE. Aluminum cylinders are preferred
over steel cylinders. The cylinders are fitted with eductor tubes, and their
contents are under 1500 psi of helium head pressure.
5.2 Carbon dioxide (C02) for cryogenic cooling - Certain parts of some
models of extractors (i.e., the high-pressure pump head and the analyte trap)
must be cooled during use. The carbon dioxide used for this purpose must be dry
(< 50 ppm water content), and it must be supplied in tanks with a full-length
eductor tube.
5.3 Tetrachloroethene, C2C14 (spectrophotometric grade) - Used for the
collection of TRPHs for determination by IR. Analyze a reagent blank to ensure
no interferences are present at the TRPH wavelengths. Chlorofluorocarbons are
not suitable for use with this method because of risk to the ozone layer.
5.4 Other appropriate pesticide-quality solvents may be used for the
collection of TRPHs for determination by GC (i.e., methylene chloride).
Chlorofluorocarbons are not suitable for use with this method because of risk to
the ozone layer.
3560 - 3 Revision 0
January 1995
-------
5.5 Copper filings - Copper filings added to remove elemental sulfur must
have a shiny bright appearance to be effective. To remove oxides, treat with
dilute nitric acid, rinse with reagent water to remove all traces of acid, rinse
with acetone (copper will darken if acid is still present), and dry under a
stream of nitrogen.
5.6 Drying agents - Anhydrous magnesium sulfate or diatomaceous earth.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Solid samples should be collected and stored as any other solid
samples containing semivolatile organics.
6.2 See Chapter Four for guidance relating to semivolatile organics
(including holding times).
7.0 PROCEDURE
7.1 Determination of sample % dry weight - In certain cases, sample
results are desired based on a dry-weight basis. When such data are desired, a
separate portion of sample for this determination should be weighed out at the
same time as the portion used for analytical determination.
WARNING: The drying oven should be contained in a hood or should be vented.
Significant laboratory contamination may result from a heavily
contaminated hazardous waste sample.
Immediately after weighing the sample for extraction, weigh an additional
5 - 10 g of the remaining sample into a tared crucible. Dry this aliquot
overnight at 105°C. Allow to cool in a desiccator before weighing. Calculate
the % dry weight as follows:
,, , ... g of dry sample .nn
% dry weight = — x 100
g of sample
7.2 Safety considerations - Read Section 11.0 "Safety" before attempting
to perform this procedure.
7.3 Sample handling
7.3.1 Decant and discard any water layer on a sediment sample. Mix
the sample thoroughly, especially composited samples. Discard any foreign
objects such as sticks, leaves and rocks.
7.3.2 Weigh 3 g of sample into a precleaned aluminum dish. A drying
agent (e.g., anhydrous magnesium sulfate or diatomaceous earth) may be
added to samples that contain water in excess of 20% to increase porosity
or to bind water. Alternatively, magnesium sulfate monohydrate is an
3560 - 4 Revision 0
January 1995
-------
excellent drying agent, and the amount of heat released (compared to
anhydrous magnesium sulfate) is small, thereby minimizing the loss of
volatile petroleum hydrocarbons. The amount of the drying agent will
depend on the water content of the sample. Typically, a ratio of 1:1 works
well for wet soils and sediment materials. However, a certain amount of
water (up to 20 percent) in the sample has been shown to improve recoveries
from certain matrices; therefore, if the sample is dry, water may
optionally be added to bring the moisture content to approximately 20
percent.
7.3.2.1 If drying agent has been added to the sample, store
the mixture of sample and drying agent for several hours (preferably
overnight) at 4°C, with a minimum of headspace. This additional
storage time is necessary to achieve acceptable analyte recovery.
This step is not necessary if the alternate conditions described in
Sec. 7.4.2.1 are used.
7.3.3 Transfer the weighed sample to a clean extraction vessel. The
volume of the extraction vessel should match the sample volume. Use two
plugs of silanized glass wool to hold the sample in place and fill the void
volume (alternatively, drying agent or clean sand can be used to fill the
void volume). Attach the end fittings, and install the extraction vessel
in the oven. Always use clean frits for each extraction vessel.
7.4 Sample extraction
7.4.1 Fill the collection vessel with 3 ml of tetrachloroethene or
other appropriate collection solvent. Chlorofluorocarbons are not suitable
for use with this method because of risk to the ozone layer.
7.4.2 Set the pressure at 340 atm and the temperature at 80°C.
Follow the manufacturer's instructions in setting up the instrument.
Extract for 30 minutes in the dynamic mode. Note the safety precautions
in Section 11.0 on venting the instrument into a chemical fume hood.
7.4.2.1 Alternatively, extract with a pressure greater than
or equal to 340 atm at 150°C for 25 minutes, and a gas flow rate of
3500 to 4000 mL/min. These parameters dry the sample during the
extraction, thus extended drying is not necessary for wet samples
(Sec. 7.3.2.1).
7.4.2.2 A sorbent trap maintained above 0°C may be necessary
for effective analyte trapping. The restrictor should resist plugging
by water, since water released from the sample may pass through the
restrictor.
7.4.3 After the extraction time has elapsed, the system should
automatically switch to the equilibrate mode. At this point, remove the
collection vessel (s) containing the extract. Since the depressurization
of the carbon dioxide at the end of the restrictor outlet results in a gas
flowrate of about 500 to 1000 mL/min, part of the collection solvent will
3560 - 5 Revision 0
January 1995
-------
evaporate during the extraction. However, cooling caused by the rapid
expansion of the carbon dioxide limits the loss of solvent, so that
approximately 2 ml remains (when tetrachloroethene is used) after a 30 min
extraction. To prevent the collection solvent from freezing, place the
collection vial in a beaker with warm water (approximately 25"C). The
extract is then brought to the desired volume, or concentrated further.
See Method 3510 for concentration techniques by micro Kuderna-Danish or
nitrogen blowdown. Concentration must be performed in a chemical fume hood
to prevent contamination of the laboratory environment.
7.4.4 The extract is ready for analysis by Method 8015,
Non-halogenated Volatile Organics by Gas Chromatography, or Method 8440,
Total Recoverable Petroleum Hydrocarbons by Infrared Spectrophotometry.
7.5 SFE System Maintenance
7.5.1 Depressurize the system following the manufacturer's
instructions.
7.5.2 After extraction of an especially tarry sample, the frits may
require replacement to ensure adequate extraction fluid flow through the
restrictor. In addition, very fine particles contained in samples can clog
the frits necessitating replacement.
7.5.3 Clean the extraction vessel after each sample. The cleaning
procedure depends on the type of sample. After removing the bulk of the
extracted sample from the extraction vessel, the cell should be scrubbed
with an ionic detergent, water, and a bottle brush. After extraction of
tarry materials, use solvent rinses or an ultrasonic bath to clean the
extraction vessel.
7.5.4 For samples known to contain elemental sulfur, use copper
filings to remove the dissolved sulfur from the fluid. The copper filings
(1 to 2 g per sample) can be packed in a separate extraction vessel
connected to the outlet end of the sample extraction vessel, or they can
be mixed with the sample, and a plug of copper filings can be loaded in the
extraction vessel with the sample such that any sulfur extracted by the
carbon dioxide can be removed before the stream of carbon dioxide
containing the analytes reaches the restrictor.
7.5.5 The procedure to be followed in emptying the syringe pump
depends upon the type of fluid being used. In the case of carbon dioxide,
which is a gas at ambient temperature and pressure, it is only necessary
to vent the gas to a fume hood by allowing it to expand across the purge
valve. Follow the manufacturer's instructions in emptying the syringe
pump.
7.5.6 To change fluid supply cylinders on a system with a syringe
pump, it is necessary to empty the syringe pump as described in Sec. 7.5.5.
Upon completion of the emptying procedure, the piston will be at its
3560 - 6 Revision 0
January 1995
-------
maximum extension, and the syringe pump outlet valve and purge valve will
be open. Then proceed as follows:
7.5.6.1 Connect the new fluid supply cylinder to the syringe
pump inlet line, and open the supply cylinder valve.
7.5.6.2 Open the pump inlet valve. The new fluid will flow
through the inlet line to the syringe pump and out through the vent.
7.5.6.3 Close the syringe pump outlet valve and the
vent/purge valve.
7.5.7 Restrictor removal and installation - Follow manufacturer's
instructions. When using fused-silica restrictors, it may be necessary to
replace the restrictor after each sample, especially when extracting
samples contaminated with heavy oils.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 8000 for specific quality control
procedures and to Method 3500 for sample preparation quality control procedures.
8.2 Each time samples are extracted, and when there is a change in
reagents, a reagent blank should be prepared and analyzed for the compounds of
interest as a safeguard against chronic laboratory contamination. Any reagent
blanks, matrix spike samples, or replicate samples should be subjected to exactly
the same analytical procedures (Sec. 7.4) as those used on actual samples.
8.3 All instrument operating conditions and parameters must be recorded.
9.0 METHOD PERFORMANCE
9.1 Refer to Methods 8440 and 8015 for performance data.
9.2 Use standard reference materials to establish the performance of the
method with contaminated samples.
10.0 REFERENCES
1. Lopez-Avila, V., N.S. Dodhiwala, J. Benedicto, and R. Young, (W. Beckert,
Project Officer), "SFE/IR for the Determination of Petroleum Hydrocarbons
in Soils and Sediments", EPA 600/X-92-046, US EPA, Environmental Monitoring
Systems Laboratory, Las Vegas, NV, April, 1992.
2. Pyle, S.M., and M.M. Setty, "Supercritical Fluid Extraction of High-Sulfur
Soils with Use of a Copper Scavenger", Talanta, 1991, 38 (10), 1125-1128.
3560 - 7 Revision 0
January 1995
-------
3. Bruce, M.L., "Supercritical Fluid Extraction (SFE) of Total Petroleum
Hydrocarbons (TPHs) with Analysis by Infrared Spectroscopy", Proceedings
of the Eighth Annual Waste Testing and Quality Assurance Symposium, July,
1992.
11.0 SAFETY
11.1 When liquid carbon dioxide comes in contact with skin, it can cause
"burns" because of its low temperature (-78'C). Burns are especially severe when
C02 is modified with organic liquids.
11.2 The extraction fluid, which may contain a modifier, usually exhausts
through an exhaust gas and liquid waste port on the rear of the panel of the
extractor. This port must be connected to a chemical fume hood to prevent
contamination of the laboratory atmosphere.
11.3 Combining modifiers with supercritical fluids requires an
understanding and evaluation of the potential chemical interaction between the
modifier and the supercritical fluid, and between the supercritical fluid or
modifier and the analyte(s) or matrix.
11.4 When carbon dioxide is used for cryogenic cooling, typical coolant
consumption is 5 L/min, which results in a carbon dioxide level of 900 ppm for
a room of 4.5 m x 3.0 m x 2.5 m, assuming 10 air exchanges per hour. The NIOSH
time-weighted average (TWA) concentration is 9000 ppm (American Conference of
Governmental Industrial Hygienists, 1991-1992).
3560 - 8 Revision 0
January 1995
-------
METHOD 3560
SUPERCRITICAL FLUID EXTRACTION OF TOTAL RECOVERABLE PETROLEUM HYDROCARBONS
>
r
7.1 Determine sample
% dry weight.
>
r
7.3 Clean and weigh
sample. Add drying
agent if necessary.
Transfer weighed
portion to
extraction vessel.
>
r
7.4.1 Fill collection
vessel with solvent.
^
f
7.4.2 Follow
manufacturer's
instructions for 7.4.3
sample extraction.
^
r
7.4.4 Analyze sample
by Method 8015 or
Method 8440.
^
r
7.5 Follow
manufacturer's
instructions for
system maintenance.
^
'
3560 - 9
-------
METHOD 3561
SUPERCRITICAL FLUID EXTRACTION OF POLYNUCLEAR AROMATIC HYDROCARBONS
1.0 SCOPE AND APPLICATION
1.1 Method 3561 describes the extraction with supercritical fluids of
polynuclear aromatic hydrocarbons (PAHs) from soils, sediments, fly ash, and
other solid materials, which are amenable to extraction with conventional
solvents. The method is suitable for use with any supercritical fluid extraction
(SFE) system that allows extraction conditions (e.g., pressure, temperature,
flowrate) to be adjusted to achieve separation of the PAHs from the matrices of
concern. The following compounds may be determined by this method:
Compound CAS Noa
Acenaphthene 83-32-9
Acenaphthylene 208-96-8
Anthracene 120-12-7
Benz(a)anthracene 56-55-3
Benzo(b)fluoranthene 205-99-2
Benzo(k)fluoranthene 207-08-9
Benzo(g,h,i)perylene 191-24-2
Benzo(a)pyrene 50-32-8
Chrysene 218-01-9
Dibenz(a,h)anthracene 53-70-3
Fluoranthene 206-44-0
Fluorene 86-73-7
Indeno(l,2,3-cd)pyrene 193-39-5
Naphthalene 91-20-3
Phenanthrene 85-01-8
Pyrene 129-00-0
a Chemical Abstracts Registry Number
1.2 Method 3561 is not suitable for the extraction of PAHs from liquid
samples without some treatment to the liquid prior to introduction into the SFE
to "stabilize" the liquid to avoid the sample being extruded through the end
pieces of the extraction vessel without the benefit of SFE.
1.3 The extraction conditions listed in this procedure (Sec. 7.5) were
used to develop the data using a variable restrictor and solid trapping media
referenced in Sec. 9.2. Other extraction conditions and equipment are acceptable
as long as appropriate method performance is demonstrated. The method
performance demonstration should be based on the extraction of a certified
sample, not on spiked soil/solids. Alternatively, a comparison of SFE and
Soxhlet extraction data using an environmentally contaminated PAH sample may be
performed. Follow the guidance for the initial demonstration of laboratory
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proficiency found in Section 8.0 of Method 3500, but utilize a weathered sample
instead of a spiked sample.
1.4 This method is restricted to use by or under the supervision of
trained analysts. Each analyst must demonstrate the ability to generate
acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 The method is divided into three discrete steps. The extraction
conditions for the first two steps are designed to ensure the best recovery for
the range of volatilities found among the PAHs. The third step is used as a
final sweep of modifier within the system. It should be noted that the
separation of the PAHs into the two arbitrary classes of the "more volatile PAHs"
(step 1) and the "lesser volatile PAHs" (step 2) is not a clean separation of
compounds, but a rough group separation depending upon the actual compounds and
their relative abundance in the sample matrix. The net sum of the two groups is
recombined in the end and thus empirically does not depend upon a discrete
definition or naming of the compounds in each group.
2.1.1 Step 1 - The more volatile PAHs are extracted and recovered
in this step using pure C02 at moderately low density and temperature and
with cold trapping on an ODS trap. These PAHs are reconstituted into an
autosampler vial with 0.8 ml collected fraction volume.
2.1.2 Step 2 - The lesser volatile PAHs are removed in this step
using a mixture of C02 with water and methanol as the extraction fluid,
higher operating temperature and density in the extraction region, and a
higher temperature in the trapping region with the ODS. The PAHs are not
reconstituted directly after the second step.
2.1.3 Step 3 - A short third step with pure C02 (but with all other
conditions as in the second step) is used to purge the system of modifier
before depressurization. The analytes recovered in the second step (and
possibly, any moved during the beginning of the third step) are
reconstituted in the same autosampler vial containing the first fraction,
using another 0.8-mL collected fraction volume. Therefore, all recovered
analytes are merged automatically into a single fraction to be analyzed by
HPLC.
2.2 There are also optional extraction solvents and SFE extraction
conditions provided that are more amenable to GC and GC/MS analysis.
3.0 INTERFERENCES
3.1 The analyst must demonstrate through the analysis of reagent blanks
(collection solvent treated as per Sec. 7.4) that the supercritical fluid
extraction system is free from interferants. To do this, perform a simulated
extraction using an empty extraction vessel and a known amount of carbon dioxide
under the same conditions as those used for sample extraction, and determine the
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background contamination by analyzing the extract by the appropriate
determinative method.
3.2 The extraction vessel(s), the end-frits, the nozzle [restrictor(s)],
and the multi-port valve(s) may retain solutes whenever high-concentration
samples are extracted. It is, therefore, good practice to clean the extraction
system after such extractions. Replacement of suspected parts of the system
should be done when reagent blanks indicate carryover. At least one reagent
blank should be prepared and analyzed daily when the instrument is in use.
Furthermore, reagent blanks should be prepared and analyzed after each extraction
of a high-concentration sample (high part per million or mg/Kg range). If
reagent blanks continue to indicate contamination, even after replacement of the
extraction vessel (and the restrictor, if a fixed restrictor system is used), the
multi-port valve must be cleaned. The operator must be ever vigilant against
impurities arising from liquid solvents and carbon dioxide itself. Avoid any
apparatus, valves, solenoids, and other hardware that contain lubricants, and
chlorofluorohydrocarbon materials that can serve as background contaminant
sources.
3.3 When using modifiers, it is important to consider that the modifiers
at collection regions that are colder than the boiling point of the modifier(s)
may cause some modifier condensation in that region. Depending upon the specific
design of the instrumentation and the quantities of modifiers used within a step,
there is a potential problem of flooding the collection region and thereby losing
the analytes of interest. With SFE instrumentation employing solid (packed)
traps for the collection and concentration of the extracted components, a
convenient guideline is to think of the trap as a packed GC column during the
extraction step (the C02 and any modifiers are the gaseous mobile phase) and as
a packed LC column during the reconstitution step. Therefore, migration during
the "GC-column-like" operation should be minimized by the selection of various
parameters: trap temperature, chemical activity of the packing, expended flow
rates, and extraction times (how long the migration has to proceed). Migration
during the "LC-column-like" operation should be controlled to trade-off
band-broadening with elution time through the use of reconstitution solvent flow
rate and composition and the trap temperature during reconstitution.
3.4 Refer to Method 3500, Section 3.0 for general extraction interference
guidance.
4.0 APPARATUS AND MATERIALS
4.1 Supercritical fluid extractor and associated hardware - Any
supercritical fluid extraction system that can achieve the extraction conditions
and performance specifications detailed in this procedure may be used.
Figure 1 depicts a typical supercritical fluid extractor system, including
a carbon dioxide source, a pumping system (liquid carbon dioxide), an extraction
thimble, a restriction device, and analyte collection device, temperature control
systems for several zones, and an overall system controller. The lower left-hand
side of Figure 1 depicts a cylinder of liquid carbon dioxide, which is the
extractant fluid. The carbon dioxide is provided as a liquid-gas mixture.
Because the liquid is the more dense of the two phases, it is drawn from the
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bottom of the tank with an eductor tube. It is essential that a full-length
eductor tube is installed in the cylinder, regardless of the grade of carbon
dioxide used. The carbon dioxide remains a liquid throughout the pumping or
compression zones, and passes through small-diameter metal tubing as it
approaches the extraction thimble. Some systems may include a preheating zone
in front of the extraction zone, so that supercritical temperature, pressure, and
density conditions are applied immediately to the analyte matrix in the thimble.
Analytes are collected just beyond the exit end of the restrictor, either 1) on
an impinged surface, such as a small, packed trap, or 2) in an empty vial or a
vial containing an appropriate liquid.
WARNING: A safety feature to prevent over-pressurization is required on the
extractor. This feature should be designed to protect the laboratory
personnel and the instrument from possible injuries or damage
resulting from equipment failure under high pressure.
4.1.1 Extraction vessel - Stainless-steel vessel with end fittings
with 2 jum frits. Use the extraction vessel supplied by the manufacturer
of the SFE system being used. Fittings used for the extraction vessel must
be capable of withstanding the required extraction pressures. The maximum
operating pressure for most extractors is 450 atm. Check with the
manufacturer of the particular extraction system on the maximum operating
pressure and temperature for that system. Make sure that the extraction
vessels are rated for such pressures and temperatures.
4.1.2 Restrictor - This method was developed with continuously
variable nozzle restrictors which do not have a need to avoid water in the
sample. If a fixed restrictor is used, additional validation must be done
to verify that water from the sample moisture does not adversely affect GC
or GC/MS chromatography. Indeed, this method depends upon continuous
addition of enough water to exceed the solubility limit in water
supercritical (and sub-critical) carbon dioxide fluid.
4.1.3 Collection device - This method is based on a solid trap used
at both sub-ambient and above ambient temperatures for different sub-sets
of the method. However, data are also presented on the use of a liquid
trap (see Sec. 9.0).
4.1.3.1 When the analytes are collected in solvent, care
must be taken in validation of the method, particularly for the first
eight PAH compounds (Method 8310 elution order) which are often poorly
recovered in liquid traps. The use of a glass wool plug in the inner
tube of the collection vial improves recoveries. Flow must not be so
high as to reduce the collection solvent to dryness. A 15-mL
collection solvent volume is recommended.
4.1.3.2 When the analytes are trapped on a sorbent material,
use ODS (Hypersil ODS was used to develop the method performance data
for the solid sorbent trap), 30-40 micrometer particle diameter
commonly used in solid phase extraction (SPE) cartridges. Other
trapping materials have also been found to provide acceptable results,
e.g. diol, however, if other material is used it should demonstrate
equivalent trapping efficiency to the ODS.
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4.2 Carbon dioxide cylinder balance (optional) - Balances from White
Associates, Catalog No. 30, or Scott Specialty Gases Model 5588D, or equivalent,
can be used to monitor the fluid usage. Such a device is useful because carbon
dioxide tanks used for SFE are not equipped with regulators. This makes it
difficult to determine when the tank needs to be replaced.
4.3 Filter paper disks to be placed at both ends of the sample. Disks may
be cored from Whatman Qualitative filter paper, Catalog No. 1003-055, or
equivalent; or from Baxter glass fiber filter paper, 0.5 /urn, Catalog No.
F232.2-21, or equivalent.
5.0 REAGENTS
5.1 Carbon dioxide, C02 - Either supercritical fluid chromatography (SFC)-
grade or SFE-grade C02 is acceptable for use in SFE. Aluminum cylinders are
preferred over steel cylinders. The cylinders are fitted with eductor tubes or
siphon tubes depending upon the definition of the supplier.
5.2 Carbon dioxide (C02) for cryogenic cooling - Certain parts of some
models of extractors (i.e., the high-pressure pump head and the analyte trap)
must be cooled during use. The carbon dioxide used for this purpose must be dry,
and should be supplied in tanks with full-length eductor tubes.
5.3 Modifiers (also called co-solvents) were added to the bulk C02
extraction fluid through the use of a separate (stand-alone) HPLC pump with the
output joined in a TEE-piece to the flowing carbon dioxide stream after the
carbon dioxide pump but before the extraction vessel. The modifier solvents are
methanol, water, and methylene chloride (HPLC grade), forming extraction fluid
mixtures of 95/1/4 (v/v/v) C02/methanol/water for HPLC analysis and 95/1/4
(v/v/v) C02/methanol/methylene chloride in the case where GC or GC/MS was used
for the analytical measurement. There are concerns about the 4% water modifier
leaving residual water in the collection trap that could have a detrimental
effect on the gas chromatographic separation. Hence, the extraction fluid
composition of 95/1/4 (v/v/v) C02/water/methanol should be altered to 95/1/4
(v/v/v) C02/methylene chloride/methanol - with some of the other parameters in
the SFE method modified slightly as described in Section 7.0.
5.4 Reconstitution solvents - The reconstitution solvents dispensed by the
SFE instruments using solid phase trapping may be the same material used for
liquid trapping. This method was developed only with sub-ambient solid trapping.
These same solvents were used to prepare the internal and external standard
solutions. A 50/50 (v/v) mixture of acetonitrile/tetrahydrofuran (THF) was used
when HPLC analysis was chosen: both were HPLC grade. A 75/25 (v/v) mixture of
methylene chloride/isooctane was used when GC/MS was chosen for the analytical
measurement. In addition, data from a different laboratory using a liquid trap
are referenced in Sec. 9.3.
5.5 Internal standards - The recommended internal standard for HPLC
analysis is biphenyl. Prepare a stock solution at a concentration of 20 g/L in
a 50/50 (v/v) acetonitrile/THF mixture. The internal standards specified in
Method 8270 may be used for GC/MS analysis.
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5.6 Surrogates - Recommended surrogates are bromobenzene (early eluter)
and p-quaterphenyl (late eluter available from ChemService, West Chester, PA).
Prepare a stock solution at a concentration of 10 g/L in a 50/50 (v/v)
acetonitrile/THF mixture. Apply 150-/iL aliquots to the soil samples within the
extraction vessels at the exit end of the flow-through vessels. It has been
observed that very small volumes (10 pi) of a concentrated surrogate mixture
(100-1000 g/L) often gave poor recoveries while adding larger volumes of more
dilute surrogate solution to the sample matrix achieved the expected recoveries.
5.7 Copper powder (electrolytic grade) - Added to samples which contain
elemental sulfur. It is pretreated by sequentially rinsing 20 g with 150 mL of
organic-free reagent water, 150 ml of acetone, 150 ml of hexane, and then drying
in a rotary evaporator. The powder is then kept under argon until used. Copper
powder must have a shiny bright appearance to be effective. If it has oxidized
and turned dark it should not be used.
5.8 Sodium sulfate, anhydrous (12-60 mesh), Baker Analyzed or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this Chapter, Organic Analytes, Sec.
4.1.
6.2 Solid samples for this procedure should be collected and stored as any
other solid samples containing semivolatile organics.
7.0 PROCEDURE
7.1 Sample handling - Decant and discard any water layer on a sediment
sample. Mix the sample thoroughly, especially composited samples. Discard any
foreign objects such as pieces of wood, glass, sticks, leaves and rocks.
7.2 Determination of sample % dry weight - In certain cases, sample
results are desired based on dry-weight basis. When such data are desired, a
separate portion of sample for this determination should be weighed out at the
same time as the portion used for analytical determination. Also, a moisture
content in the sample between 10 - 50% for the GC/MS extraction method, provided
the best extraction efficiency for the procedure as written. Therefore,
determination of % moisture is necessary in this case.
WARNING: The drying oven should be contained in a hood or vented. Significant
laboratory contamination may result from a heavily contaminated
hazardous waste sample.
7.2.1 Immediately after weighing the sample for extraction, weigh
an additional 5 - 10 g of the sample into a tared crucible. Determine the
% dry weight of the sample by drying overnight at 105'C. Allow to cool in
a desiccator before weighing.
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7.2.2 Calculate the % dry weight as follows:
-. , ... g of dry sample ,nn
% dry weight = — x 100
g of sample
7.3 Safety considerations - Read Sec. 11.0 "Safety" before attempting to
perform this procedure.
7.4 Sample grinding and homogenization.
NOTE: Sample grinding is a critical step in the SFE process. The soil/solid
must be a fine particle to ensure efficient extraction.
7.4.1 Mix at least 100 grams of sample with an equal volume of
carbon dioxide solid "snow" prepared from the extraction grade carbon
dioxide. Place this in a small food-type chopper, and grind for about one
minute. Place the chopped sample on a clean surface and allow the carbon
dioxide to sublime away. As soon as the sample appears free-flowing and
without the solid carbon dioxide, weigh the sample and place in the
extraction vessel. This procedure will ensure the homogeneity of the
sample without loss of the volatile analytes and also retains the original
moisture content of the sample.
7.4.2 Weigh 2.0 to 3.0 g of the homogenized sample into a
pre-cleaned aluminum dish. (Up to 10 g of sample can be extracted using
the conditions outlined in this procedure.) If sample moisture content
exceeds 50%, add a plug (1 - 2 g) of anhydrous sodium sulfate (Sec. 5.8)
next to the frit in the extraction vessel. Do not add any drying agent of
any kind directly to the sample. This method depends upon the controlled
addition of water throughout the procedure. Any drying agents will
interfere with the process.
7.4.3 For samples known to contain elemental sulfur, use copper
powder (electrolytic grade) to remove the dissolved sulfur from the sample
and carbon dioxide eluant. The copper powder (1 to 2 grams per sample) can
be packed in a separate vessel between the extraction vessel and the nozzle
(restrictor) or better, mixed with the sample in the extraction vessel
itself. Alternatively, a plug of copper powder may be placed in the
extraction vessel beyond the sample before the exit-frits.
7.4.4 Transfer half of the weighed sample to the extraction vessel.
Add 150 (j,L of surrogate solution to the sample in the vessel and then add
the remainder of the sample material. To ensure efficient extraction, it
is very important that the extraction vessel be completely full to avoid
any dead volume. If any dead volume exists, fill the space with an inert,
porous material, e.g., pre-cleaned Pyrex® glass wool, Celite®, etc.
7.5 Sample extraction - This section contains recommended extraction
parameters for both HPLC and GC (including GC/MS) analyses.
NOTE: The C02/modifiers used for GC or GC/MS analysis extract more efficiently
when the soil moisture content is between 10 to 50%. If the sample
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content is less than 10%, add 0.5 ml of water per gram of sample to the
sample before placing it in the extraction vessel.
7.5.1 The following conditions for Step 1 (collection of the more
volatile PAHs) are grouped according to function.
7.5.1.1 Extraction
Pressure: 1750 psi (120 bar)
Density: 0.30 g/mL
Extraction chamber temperature: 80°C
Extraction fluid composition: C02
Static equilibration time: 10 minutes
Dynamic extraction time: 10 minutes
Extraction fluid flow rate: 2.0 mL/min
Resultant thimble-volumes-swept = 9.1 (this is equivalent to 20 ml of
liquid carbon dioxide at a reference temperature of 4.0°C, density
0.96 g/mL or 19.2 g of carbon dioxide).
7.5.1.2 Collection (during extraction)
Trap packing: ODS
Trap temperature: -5°C
Nozzle temperature: 80°C (variable restrictor)
7.5.1.3 Reconstitution (of collected extracts)
Rinse solvent for HPLC: 50/50 (v/v) THF/acetonitrile
Rinse solvent for GC: 75/25 (v/v) CH2Cl2/isooctane
Collected fraction volume: 0.8 ml
Trap temperature: 60°C
Nozzle temperature: 45°C (variable restrictor)
Rinse solvent flow rate: 1.0 mL/min
The extract should be properly labeled with fraction designation and
vial number.
7.5.2 The following conditions for Step 2 (collection of the lesser
volatile PAHs) are grouped according to function.
7.5.2.1 Extraction •
Pessure: 4900 psi (338 bar)
Density: 0.63 g/mL
Extraction chamber temperature: 120°C
Extraction fluid for HPLC: 95/1/4 (v/v/v)
C02/methanol/water
Extraction fluid for GC: 95/1/4 (v/v/v)
C02/methanol/CH2Cl2
Static equilibration time: 10 minutes
Dynamic extraction time: 30 minutes
Extraction fluid flow rate: 4.0 mL/min
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Resultant thimble-volumes-swept = 25 (equivalent to 120 ml of liquid
carbon dioxide at reference temperature of 4.0°C, density 1.06 g/mL
or 127 g of carbon dioxide).
7.5.2.2 Collection (during Extraction)
Trap packing: ODS
Trap temperature: 80°C
Nozzle temperature: 80°C (variable restrictor)
7.5.2.3 Reconstitution (of collected extracts) - none.
7.5.3 The following conditions for Step 3 (final sweep of modifiers)
are grouped according to function.
7.5.3.1 Extraction
Pressure: 4900 psi (338 bar)
Density: 0.63 g/mL
Extraction chamber temperature: 120°C
Extraction fluid composition: C02
Static equilibration time: 5 minutes
Dynamic extraction time: 10 minutes
C02 flow rate: 4.0 mL/min
Resultant thimble-volumes-swept = 8 (equivalent to 40 mi of liquid
carbon dioxide at reference temperature of 4.0°C, density 1.06 g/mL
or 42.4 g carbon dioxide).
7.5.3.2 Collection (during Extraction)
Trap packing: ODS
Trap temperature: 80°C
Nozzle temperature: 80°C (variable restrictor)
NOTE: All three steps consume a total of 188.6 g of carbon dioxide.
7.5.3.3 Reconstitution (of collected extracts)
Rinse solvent for HPLC: 50/50 (v/v) THF/acetonitrile
Rinse solvent for GC: 75/25 (v/v) CH2Cl2/isooctane
Collected fraction volume: 0.8 mL
Trap temperature for HPLC: 80°C
Trap temperature for GC: 60°C
Nozzle temperature: 45°C (variable restrictor)
Rinse solvent flow rate: 1.0 mL/min
The extract should be properly labeled with fraction destination and
vial number.
7.5.4 The combined extract volumes consist of 1.6 mL. The extract
is ready for the analysis by Methods 8310 (HPLC), 8270 (GC/MS), or 8100
(GC/FID). Note that there are no performance data available on the
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analysis of SFE PAH extracts by Method 8100. Furthermore, the procedure
is more susceptible to interferences in complex samples.
NOTE: If a fixed restrictor and liquid trapping are used, a restrictor
temperature in the range of 100 to 150°C is recommended.
7.5.5 When GC or GC/MS analysis procedures are to be used and sulfur
interference becomes apparent at time of analysis, Method 3660 may be used
to remove the sulfur from the extract.
7.6 SFE System Maintenance
7.6.1 Depressurize the system following the manufacturer's
instructions.
7.6.2 After extraction of an especially "tarry" sample, the
end-frits of the extraction vessel may require replacement if not extensive
cleanup to ensure adequate extraction fluid flow without excessive pressure
drop due to the system plumbing. In addition, very fine particles may clog
the exit frit requiring its replacement. By placing a layer of inert
material such as Celite® or sea sand above the sample prior to the exit
frit (and placing disks of filter paper on top of the inert material), this
maintenance may be delayed for some period of operation.
7.6.3 Clean the extraction vessel after each extraction sample. The
cleaning procedure depends upon the type of sample. After removing the
bulk of the extracted sample matrix from the extraction vessel, the cell
and end-frits should be scrubbed with an aqueous detergent, water and a
stiff brush. Placing the parts in an ultrasonic bath with a warm detergent
solution is very helpful. The parts should be rinsed with reagent water.
The ultrasonic bath treatment should then be repeated with either methyl
alcohol or acetone or both followed by air drying.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 8000 for specific Quality Control
procedures and to Method 3500 for sample preparation quality control procedures.
8.2 Each time samples are extracted, and when there is a change in
reagents, a reagent blank should be prepared and analyzed for the compounds of
interest as a safeguard against chronic laboratory contamination. Any reagent
blanks, matrix spike samples, or replicate samples should be subjected to exactly
the same analytical procedures (Sec. 7.4) as those used on actual samples.
8.3 All instrument operation conditions and parameters should be recorded.
9.0 METHOD PERFORMANCE
9.1 Using Method 8310, an HPLC method with either UV/Vis or fluorescence
detection, expected minimum detection limits are between 0.010 - 1.00 mg/Kg
depending upon the actual analyte and detector. The estimated quantitation
limits (EQLs) would range from 0.10 - 10 mg/Kg depending on analyte and detector.
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Using Method 8270, a GC/MS method, expected minimum detection limits are
approximately 0.70 mg/kg. The estimated quantitation limits (EQLs) for GC/MS
would be approximately 7 mg/Kg. The MDLs and EQLs listed above are based on a
3-g sample.
9.2 Single laboratory precision and accuracy data based on this method
(using a variable restrictor and solid trapping material) were obtained for the
method analytes by the extraction of two reference materials (one a lake sediment
from Environment Canada and the other a marine sediment from the National Science
and Engineering Research Council of Canada, both naturally contaminated with
PAHs). The SEE instrument used for these extractions was a Hewlett-Packard Model
7680. Analysis was by GC/MS. The data were taken from Reference 2. Average
recoveries from six replicate extractions ranged from 85 to 148% (overall average
of 100%) based on the certified value (or a Soxhlet value if a certified value
was unavailable for a specific analyte) for the lake sediment. Average
recoveries from three replicate extractions ranged from 73 to 133% (overall
average of 92%) based on the certified value for the marine sediment. The data
are found in a table in Method 8270.
9.3 Single laboratory precision and accuracy data based on the use of a
fixed restrictor and liquid trapping were obtained for twelve of the method
analytes by the extraction of a certified reference material obtained from Fisher
Scientific (a soil naturally contaminated with PAHs). The SFE instrument used
for these extractions was a Dionex Model 703-M. Analysis was by GC/MS. The data
were taken from Reference 4. Average recoveries from four replicate extractions
ranged from 60 to 122% (overall average of 89%) based on the certified value.
Following are the instrument conditions that were utilized to extract a 3.4 g
sample: Pressure - 300 atm; Time - 60 min.; Extraction fluid - C02; Modifier -
10% 1:1 (v/v) methanol/methylene chloride; Oven temperature - 80°C; Restrictor
temperature - 120°C; and, Trapping fluid - chloroform (methylene chloride has
also been used). The data are found in a table in Method 8270.
9.4 Single laboratory precision and accuracy data based on this method
(using a variable restrictor and solid trapping material) were obtained for the
method analytes by the extraction of a well-characterized reference material
naturally contaminated with PAHs. The SFE instrument used for these extractions
was a Hewlett-Packard Model 7680. Analysis was by HPLC. The data were taken
from Reference 3. Average recoveries from three replicate extractions ranged
from 85.7 to 153% (overall average of 107%) based on the Soxhlet value. The data
may be presented in a future revision of Method 8310.
10.0 REFERENCES
1. D.R. Gere, C.R. Knipe, P. Castelli, J. Hedrick, L.G. Randall, J. Orolin,
H. Schulenberg-Schell, R. Schuster, H.B. Lee, and L. Doherty "Bridging the
Automation Gap between Sample Preparation and Analysis: SFE, GC, GC/MSD and
HPLC Applied to Environmental Samples", J. Chromatographic Science 31(7)
245-258 (July 1993).
2. H.B. Lee, T.E. Peart, R.L. Hong-You, and D.R. Gere, "Supercritical Carbon
Dioxide Extraction of Polycyclic Aromatic Hydrocarbons from Sediments", J.
Chromatography, A 653 83-91 (1993).
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3. Personal communication from H. Schulenberg-Schel1, Hewlett-Packard
Waldbronn Site, #8 Hewlett-Packard Strasse, D7517 Waldbronn 2, Germany.
4. Personal communication from Sue Warner, EPA Region 3, Central Regional
Laboratory, 839 Bestgate Road, Annapolis, MD 21401.
5. W. Beckert, "An Overview of the EPA's Supercritical Fluid Extraction (SFE)
Methods Development Program," ACS Symposium: Supercritical Fluids in
Analytical Chemistry sponsored by the Division of Analytical Chemistry at
the 201st National Meeting of the American Chemical Society, Atlanta, GA,
April 14-19, 1991.
6. V. Lopez-Avila, N.S. Dodhiwala, and J. Benedicto, Evaluation of Various
Supercritical Fluid Extraction Systems for Extracting Organics from
Environmental Samples, Final Report for Work Assignment 1-1, EPA Contract
68-C1-0029, Environmental Monitoring Systems Laboratory, Office of Research
and Development, U.S. Environmental Protection Agency, Las Vegas, NV
89119, February, 1992.
7. S. Bowadt and B. Johansson, "Analysis of PCB's in Sulfur-Containing
Sediments by Off-line SFE", Analytical Chemistry, 66, No. 5, 667, (1994).
11.0 SAFETY
11.1 When liquid carbon dioxide comes in contact with skin, it can cause
"burns" because of its low temperature (-78°C). Burns are especially severe when
C02 is modified with organic liquids.
11.2 The extraction fluid, which may contain a modifier, usually exhausts
through an exhaust gas and liquid waste port on the rear of the panel of the
extractor. This port must be connected to a chemical fume hood to prevent
contamination of the laboratory atmosphere.
11.3 Combining modifiers with supercritical fluids requires an
understanding and evaluation of the potential chemical interaction between the
modifier and the supercritical fluid, and between the supercritical fluid or
modifier and the analyte(s) or matrix.
11.4 When carbon dioxide is used for cryogenic cooling, typical coolant
consumption is 5 L/min, which results in a carbon dioxide level of 900 ppm for
a room of 4.5 m x 3.0 m x 2.5 m, assuming 10 air exchanges per hour.
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Pit I HOD 3561
SUPERCRITICAL FLUID EXTRACTION OF POLYNUCLEAR AROMATIC HYDROCARBONS
7 1 Use appropriate
•ample handling.
7.2 Determine aample
% dry weight.
7.4.1 Grind 4
homogenize
•ample with dry ice.
7.4.2 We.gh 2-3 g
of urn pie.
7 4.3 Add copper
powder to •ample.
7 4.4Tranefer
weighed temple to
extraction veeaei and
add aurrogatea.
7.6 Sample
extraction.
7.6.1 Collection of
more volatile PAHa.
7.6.2 Collection of
non-volatile PAHa.
7.6.3 Final modifier
•weep.
7 6.4 Combine extract*
and perform determin-
ative method
HPLC (Method 8310)
GC/M8 (Method 8270)
or GC (Method 6100.)
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METHOD 3585
WASTE DILUTION FOR VOLATILE ORGANICS
1.0 SCOPE AND APPLICATION
1.1 This method describes a solvent dilution of a non-aqueous waste sample
prior to direct injection analysis. It is designed for use in conjunction with
GC or GC/MS analysis of wastes that may contain organic chemicals at a
concentration greater than 1 mg/kg and that are soluble in the dilution solvent.
Method 3585 has adequate sensitivity to determine the regulatory concentrations
of the Toxicity Characteristic (TC) Rule.
1.2 This method may be used with n-hexadecane for direct injection of
target volatiles in oily matrices.
1.3 Use of a 1 - 2 /iL injection of a 1:1 dilution can be used to provide
detection limits of 0.5 ppm for volatile target analytes with a sensitive GC/MS.
1.4 This method is restricted to use by or under the supervision of
trained analysts. Each analyst must demonstrate the ability to generate
acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 Highly contaminated or highly complex samples may be diluted prior to
analysis for volatiles using direct injection.
2.2 One gram of sample is weighed into a capped tube or volumetric flask.
The sample is diluted to 2.0 - 10.0 mL with n-hexadecane or other appropriate
solvent.
2.3 Diluted samples are injected into the GC or GC/MS for analysis.
3.0 INTERFERENCES
3.1 Use of a direct injection procedure will result in considerable
contamination of injection ports, injection port liners, GC columns, and
detectors. A Pyrex® wool plug should be placed into the injection port liner and
the liner should be changed after every 12 hours of sample analysis.
3.2 The solvent used for waste dilution may contain volatile contaminants
that could interfere with analyses.
3.2.1 n-Hexadecane elutes after target volatiles. However, volatile
impurities in n-hexadecane may interfere with analyses.
3.2.2 Each lot of n-hexadecane (or any other solvent used for
dilution) must be analyzed for impurities prior to use.
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3.3 The presence of methanol and other oxygenated solvents in samples may
lead to baseline humps that interfere with qualitative and quantitative analysis
of early eluting target analytes when direct injection is employed.
4.0 APPARATUS AND MATERIALS
4.1 Glass scintillation vials - At least 20-mL, with Teflon®- or aluminum
foil-lined screw-cap, or equivalent.
4.2 Spatula - Stainless steel or Teflon®.
4.3 Balance - Capable of weighing 100 g to the nearest 0.01 g.
4.4 Vials and caps - 2-mL, for GC autosampler.
4.5 Disposable pipets - Pasteur.
4.6 Test tube rack.
4.7 Pyrex® glass wool.
4.8 Volumetric flasks, Class A - 2- or 10-mL (optional).
4.9 Direct injection liner (HP catalogue #18740-80200 or equivalent) -
Modify with a 1-cm plug of Pyrex® wool placed approximately 50-60 mm down the
length of the injection port (towards the oven). A 0.53 mm ID column is mounted
1 cm into the liner from the oven side of the injection port, according to
manufacturer's specifications. Following is an example of the placement of the
glass wool in the liner.
ptu.ro.
Figure 1 Modified Injector
5.0 REAGENTS
n-Hexadecane, C16H34 - Pesticide quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
See the introductory material to this chapter, Organic Analytes, Sec. 4.1.
7.0 PROCEDURE
7.1 Samples consisting of multiple phases must be prepared by the phase
separation method (Chapter Two) before extraction. The oil phase is prepared as
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outlined below. An aqueous phase is prepared and analyzed following the guidance
in Method 5030.
7.2 The sample dilution may be performed in a 2- or 10-mL volumetric
flask. If disposable glassware is preferred, the 10-dram vial may be calibrated
for use. Pipet 2.0 ml of methanol into the vial and mark the bottom of the
meniscus. Discard this solvent. Dry the vial.
7.3 Transfer approximately 1 g of the oil phase of the sample to a vial
or volumetric flask (record weight to the nearest 0.1 g). Wipe the mouth of the
vial with a tissue to remove any sample material. Cap the vial before proceeding
with the next sample to avoid any cross-contamination.
7.4 Immediately dilute to volume with n-hexadecane or other appropriate
solvent. The choice of solvents is dependent on the nature of the target
analytes. n-Hexadecane is late eluting and, therefore, presents no solvent
interference for the majority of volatile organics. An early eluting solvent,
e.g., pentane or hexane, may be chosen if the target analytes are mid to late
eluting.
7.5 Add surrogate spiking solution, if required, for the analytical method
to be employed.
7.6 Cap and shake the sample for 2 minutes.
7.7 The extract is ready for analysis by GC Methods 8015 or 8021, or by
GC/MS Method 8260.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One, Method 8000, and the analytical method to be
employed, for specific quality control procedures.
8.2 Each time samples are prepared and analyzed, and when there is a
change in reagents, a reagent blank should be prepared and analyzed for the
compounds of interest as a safeguard against chronic laboratory contamination.
Any reagent blanks, matrix spike samples, or replicate samples should be
subjected to exactly the same analytical procedures as those used on actual
samples.
8.3 Standard quality assurance practices should be used with this method.
Field duplicates should be collected to validate the precision of the sampling
technique. Each analysis batch of 20 or fewer samples must contain: a reagent
blank; either a matrix spike/matrix spike duplicate or a matrix spike and
duplicate sample analysis; and a laboratory control sample, unless the
determinative method provides other guidance.
8.4 Surrogates should be added to all samples when specified in the
appropriate determinative method.
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9.0 METHOD PERFORMANCE
Refer to the determinative methods for performance data.
10.0 REFERENCES
1. Marsden, P.J., Colby, B.N., and Helms, C.L., "Determining TCLP
Volatiles at Regulatory Levels in Waste Oil", Proceedings of the
Eighth Annual Waste Testing and Quality Assurance Symposium, July,
1992.
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METHOD 3585
WASTE DILUTION FOR VOLATILES
Is
sample
multiphase?
Oil phase
or aqueous
phase to be
analyzed?
See Phase
Separation Method,
Chapter Two.
Prepare and analyze
by Method 5030.
7.2 - 7.4 Perform
sample dilution with
appropriate solvent.
7.5 Add surrogate
spiking solution if
required by
determinative
method.
7.6 Cap and shake
sample and solvent
for 2 minutes.
Perform
determinative
method.
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METHOD 5000
SAMPLE PREPARATION FOR VOLATILE ORGANIC COMPOUNDS
1.0 SCOPE AND APPLICATION
1.1 Method 5000 provides general guidance on the selection of sample
preparation methods (purge-and-trap, extraction, azeotropic distillation, vacuum
distillation, dilution, headspace, etc.) for introducing volatile organic
compounds into a detection device (outlined in the determinative methods). The
matrices include aqueous, soil/sediment, solid waste, organic solvents, air, and
oily waste. Other waste matrices may be adaptable to one or more of the listed
preparation methods.
1.2 Method 5000 also provides specific information pertaining to analyte
interferences, preparation of calibration and spiking standards, and specific
quality control that should be applied to each preparative method.
1.3 The following table is presented as a reference guide to sample
preparation techniques for volatile organic compounds:
SAMPLE PREPARATION METHODS FOR VOLATILE ORGANICS
Method #
3585
5021
5030
5031
5032
5035
5041
Matrix
Oily waste
Solids
Aqueous
Aqueous
Aqueous & solids
Solids, organic
solvents, oily waste
Air sampled by VOST
Preparation Type
Solvent dilution
Automated
headspace
Purge-and-trap
Azeotropic
distillation
Vacuum
distillation
Closed system
Purge-and-trap
Purge-and-trap
from VOST
Analytes
VOCs
VOCs
VOCs
Polar VOCs
Non polar and
polar VOCs
VOCs
Volatile POHCs
VOCs = Volatile Organic Compounds
VOST = Volatile Organic Sampling Train
POHCs = Principal Organic Hazardous Constituents
1.4 Method 3585 provides guidance for dilution and direct injection of
oily waste samples (e.g. waste oil or oily waste that filters during TCLP sample
preparation) for volatile organic analysis.
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1.5 The following table is presented as a reference guide to air sampling
methods found in Chapter Ten that interface with the volatile organic methods:
AIR SAMPLING METHODS FOR VOLATILE ORGANIC COMPOUNDS
FROM CHAPTER TEN OF SW-846
Method #
0011
0030
0031
0040
0100
Sampling Method
Aqueous solution
of DNPH
Resin/charcoal
Resin/Anasorb
747
Tedlar® bag
DNPH coated
silica gel
Sample Preparation
Solvent extraction
Purge-and-trap by
5041
Purge-and-trap by
5041
Direct analysis
with sample loop
Solvent extraction
Analytes
Formaldehyde plus
aldehydes & ketones
Volatile organics
Volatile organics
Volatile organics
Formaldehyde plus
aldehydes & ketones
DNPH = Dinitrophenylhydrazine
2.0 SUMMARY OF METHOD
2.1 Method 5000 provides general information that is common to each of the
methods listed in Sec. 1.0. Specifically this includes: interference problems
that are common to any volatile organic sample preparation method; preparation
of calibration standards, internal standards, surrogate spikes, laboratory
control samples (LCSs), and matrix spikes; a brief summary of each of the
methods; and the specific quality control that should be applied to each of the
preparative methods.
2.2
interface
matrices.
Table 1 provides guidance on which sample preparation methods
with each volatile organic determinative method, for a variety of
3.0 INTERFERENCES
3.1 Samples requiring analysis for volatile organic compounds can be
contaminated by diffusion of volatile organics (particularly chlorofluorocarbons
and methylene chloride) through the sample container septum during shipment and
storage. A field blank prepared from organic-free reagent water and carried
through sampling and subsequent storage and handling can serve as a check on such
contamination.
3.2 Solvents, reagents, glassware, and other sample processing hardware
may yield artifacts and/or interferences to sample analysis. All these materials
must be demonstrated to be free from interferences under the conditions of the
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analysis by analyzing method blanks. Specific selection of reagents and
purification of solvents by distillation in all-glass systems may be necessary.
Refer to each method for specific guidance on quality control procedures and to
Chapter Four for guidance on the cleaning of glassware.
3.3 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are analyzed sequentially. Whenever an unusually
concentrated sample is analyzed, it should be followed by an analysis of
organic-free reagent water to check for cross-contamination. Therefore, frequent
bake-out and purging of the entire system may be required. This is especially
true for purge-and-trap systems which are often subject to such contamination.
3.4 The laboratory where volatile analysis is performed should be
completely free of solvents.
3.4.1 Special precautions must be taken to determine methylene
chloride. The analytical and sample storage area should be isolated from
all atmospheric sources of methylene chloride, otherwise random background
levels will result.
3.4.2 Since methylene chloride will permeate through PTFE tubing,
all GC carrier gas lines and purge gas plumbing should be constructed of
stainless steel or copper tubing.
3.4.3 Laboratory worker's clothing previously exposed to methylene
chloride fumes during common liquid/liquid extraction procedures can
contribute to sample contamination.
3.4.4 The presence of other organic solvents in the laboratory
where volatile organics are analyzed will also lead to random background
levels and the same precautions must be taken.
3.5 Interference problems specific to the sample preparation methods are
discussed in the individual methods.
4.0 APPARATUS AND MATERIALS
Refer to the specific method of interest for a description of the apparatus
and materials needed.
5.0 REAGENTS
5.1 Refer to the specific method of interest for a description of the
solvents and other reagents needed.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water as defined in Chapter One.
5.3 Stock standards for spiking solutions - Stock solutions may be
prepared from pure standard materials or purchased as certified solutions. The
stock solutions used for the calibration standards are acceptable (dilutions must
be made in a water miscible solvent) except for the quality control check sample
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stock concentrate which must be prepared independently to serve as a check on the
accuracy of the calibration solution.
5.3.1 Purgeable stock standards - Prepare stock standards in
methanol using assayed liquids or gases, as appropriate. Because of the
toxicity of some of the organohalides, primary dilutions of these
materials should be prepared in a hood.
5.3.1.1 Place about 9.8 ml of methanol in a 10 ml, tared,
ground-glass-stoppered volumetric flask. Allow the flask to stand,
unstoppered, for about 10 min or until all alcohol-wetted surfaces
have dried. Weigh the flask to the nearest 0.0001 g.
5.3.1.2 Using a 100 jtiL syringe, immediately add two or more
drops of assayed reference material to the flask, then reweigh. The
liquid must fall directly into the alcohol without contacting the
neck of the flask.
5.3.1.3 Reweigh, dilute to volume, stopper, then mix by
inverting the flask several times. Calculate the concentration in
milligrams per liter (mg/L) from the net gain in weight. When
compound purity is assayed to be 96% or greater, the weight may be
used without correction to calculate the concentration of the stock
standard. Commercially prepared stock standards may be used at any
concentration if they are certified by the manufacturer or by an
independent source.
5.3.1.4 Transfer the stock standard solution into a
Teflon®-sealed screw-cap bottle. Store, with minimal headspace, at
-10°C to -20eC and protect from light.
5.3.1.5 Refer to the determinative method for holding times
of the stock solutions.
5.3.2 Non-purgeable stock standards - Non-purgeable stock solutions
may be prepared from pure standard materials or purchased as certified
solutions. Refer to the individual determinative method for additional
guidance.
5.4 Surrogate standards - A surrogate standard (i.e., a compound that is
chemically similar to the analyte group but not expected to occur in an
environmental sample) should be added to each sample, blank, laboratory control
sample and matrix spike sample just prior to extraction or processing. The
recovery of the surrogate standard is used to monitor for unusual matrix effects,
gross sample processing errors, etc. Surrogate recovery is evaluated for
acceptance by determining whether the measured concentration falls within the
acceptance limits.
5.4.1 Recommended surrogates for certain analyte groups are listed
in Table 2. For methods where no recommended surrogates are listed, the
laboratory is free to select compounds that fall within the definition
provided above. Even compounds that are on the method analyte list may be
used as surrogates as long as historical data are available to ensure
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their absence at a given site. Normally one or more surrogates are added
for each analyte group.
5.4.2 Prepare a surrogate spiking concentrate by mixing stock
standards prepared above and diluting with a water-miscible solvent.
Commercially-prepared spiking solutions are acceptable. The concentration
for volatile organic analysis by purge-and-trap should be such that a 10
H\. aliquot when added directly to 5 ml of sample provides the
concentrations listed in Table 2. The spiking volumes are normally listed
in each preparation method. Where concentrations are not specified, a
concentration in the sample of 10 times the estimated quantitation limit
is recommended. If the surrogate quantitation limit is unknown, the
average estimated quantitation limit of method target analytes may be
utilized to estimate a surrogate quantitation limit.
5.5 Matrix spike standards - Prepare a matrix spike concentrate by mixing
stock standards as prepared above and diluting with a water miscible solvent.
Commercially prepared spiking solutions are acceptable. The stock standards are
to be independent of the calibration standard.
5.5.1 A few methods provide guidance on concentrations and the
selection of compounds for matrix spikes (see Table 3). For example, the
recommended purgeable matrix spiking solution for Methods 8021 and 8260 is
as follows: Prepare a spiking solution in methanol that contains the
following compounds at a concentration of 25 mg/L.
Purqeable orqanics
1,1-Dichloroethene
Trichloroethene
Chlorobenzene
Toluene
Benzene
5.5.2 For methods with no guidance, select five or more analytes
(select all analytes for methods with five or less) from each analyte
group for use in a spiking solution. Where matrix spike concentrations in
the sample are not listed it should be at or below the regulatory
concentration or, 1 to 5 times higher than the background concentration,
whichever, concentration would be larger.
5.6 Laboratory control spike standard - Use the matrix spike standard
prepared in Sec. 5.5 as the spike standard for the laboratory control sample
(LCS). The LCS should be spiked at the same concentration as the matrix spike.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
See Chapters Two and Four for guidance on sample collection, preservation,
and handling.
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7.0 PROCEDURE
Water, soil/sediment, sludge, and waste samples requiring analysis for
volatile organics are extracted and/or introduced into the GC and/or GC/MS system
by various methods (see Table 1). This manual contains method choices that are
dependent on the matrix, the physical properties of the analytes, the
sophistication and cost of equipment available to a given laboratory, and the
turn-around time required for sample preparation. The following is a brief
summary of each of the sample preparation/introduction techniques:
7.1 Method 3585: This method describes a solvent dilution (hexadecane)
technique followed by direct injection into a sensitive GC/MS system for the
analysis of volatiles in oily waste. Method 3585 has adequate sensitivity to
determine the regulatory concentrations for TCLP oily waste that filters. Direct
injection is very simple, provides quick turnaround and requires no special
hardware. However, the GC/MS system must be quite sensitive, has the potential
for instrument contamination and is more subject to matrix difficulties. Method
3585 lends itself best when performing analysis for small groups of samples.
7.2 Method 5021: This method describes an automated headspace analysis
for soils and other solid matrices. The solid sample is placed in a tared
septum-sealed vial at time of sampling. A matrix modifier is added containing
internal and/or surrogate standards. The sample vial is placed into an automated
equilibrium headspace sampler which automatically equilibrates the sample at 85"C
and mixes it by mechanical vibration. A measured volume of headspace is
automatically introduced into a GC or GC/MS system for volatile organic analysis.
The method is automated and causes no equipment contamination, however, it does
require a relatively expensive automated headspace device.
7.3 Method 5030: This method describes the technique of purge-and-trap
for the introduction of purgeable organics into a gas chromatograph. This
procedure is applicable for use with aqueous samples and aqueous miscible
extracts prepared by Method 5035. An inert gas is bubbled through the-sample,
which will efficiently transfer the purgeable organics from the aqueous phase to
the vapor phase. The vapor phase is swept through a sorbent trap where the
purgeables are trapped. After purging is completed, the trap is heated and
backflushed with the inert gas to desorb the purgeables onto a gas
chromatographic column. Purge-and-trap is easily automated, provides good
precision and accuracy, but, is limited to analytes that purge efficiently from
water and requires expensive purge-and-trap devices. The system is easily
contaminated by samples containing compounds at mg/L concentrations. This
procedure may be used for the analysis of gasoline in various aqueous matrices.
7.4 Method 5031: This method describes an azeotropic distillation
technique for the analysis of nonpurgeable, water soluble, volatile organics in
aqueous samples. The sample is distilled in an azeotropic distillation apparatus
(guidance for an optional micro-distillation apparatus is also included) followed
by direct aqueous injection from the analyte enriched distillate into a GC or
GC/MS system. The method is not readily automated except for the GC/MS analysis,
requires a 1 hour distillation and covers a limited group of analytes.
7.5 Method 5032: This method describes a closed system vacuum
distillation technique for the analysis of volatile organics including
nonpurgeable, water soluble, volatile organics in aqueous samples. The sample
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is introduced into a sample flask which is then attached to the vacuum
distillation apparatus. The sample chamber pressure is reduced and remains at
approximately 10 torr (vapor pressure of water) as water is removed from the
sample. The vapor is passed over a condenser coil chilled to a temperature of
-10eC or less, which results in the condensation of water vapor. The uncondensed
distillate is cryogenically trapped on a section of 1/8 inch stainless steel
tubing chilled to the temperature of liquid nitrogen (-196°C). After an
appropriate distillation period, which may vary due to matrix or analyte group,
the condensate contained in the cryotrap is thermally desorbed and transferred
to the gas chromatograph using helium carrier gas. This method very efficiently
extracts organics from a variety of matrices. The method requires a vacuum
system, cryogenic cooling, and is not readily automated, except for the GC/MS
analysis.
7.6 Method 5035: This method describes a closed-system purge-and-trap for
the analysis of volatile organics that are purgeable from a water/soil matrix at
40°C. It is amenable to soil/sediment and any solid waste sample of a
consistency similar to soil. It differs from the original soil method in Method
5030 in that a sample (normally 5 g) is placed into the sample vial at time of
sampling. The sample remains hermetically sealed from sampling through analysis
as the closed-system purge-and-trap device automatically adds a measured amount
of organic-free reagent water and standards and then performs the purge-and-trap
process. The method provides more accurate data than the original method because
the sample container is not opened. However, it does require a purge-and-trap
device specially modified to add the water and standards without breaking the
hermetic seal. It also includes a technique for the extraction of oily waste
using methanol. This procedure may be used for the analysis of gasoline in
various solid matrices.
7.7 Method 5041: This method is applicable to the analysis of sorbent
cartridges from a volatile organic sampling train (VOST). The sorbent cartridges
are placed in a thermal desorber which in turn is attached to a standard purge-
and-trap device. Analysis may be by GC or GC/MS
7.8 Sample analysis - For samples requiring volatile organic analysis,
sample handling devices in some of the methods described above are interfaced
directly to a gas chromatograph or gas chromatographic/mass spectrometer system.
A few of the sample preparation methods require injection of an extract or
distillate into the GC or GC/MS. See Table 1 for more guidance on which sample
preparation methods interface to each determinative method.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 8000 for specific quality control
procedures. Each laboratory using SW-846 methods should maintain a formal
quality assurance program.
8.2 Initial Demonstration of Proficiency - Each laboratory must
demonstrate initial proficiency with each sample preparation and determinative
method combination it utilizes, by generating data of acceptable accuracy and
precision for target analytes in a clean reference matrix. This will include a
combination of the sample preparation method (usually a 5000 series method for
volatile organics) and the determinative method (an 8000 series method). The
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laboratory must also repeat the following operations whenever new staff are
trained or significant changes in instrumentation are made.
8.2.1 The reference samples are prepared from a spiking solution
containing each analyte of interest. The reference sample concentrate
(spiking solution) may be prepared from pure standard materials, or
purchased as certified solutions. If prepared by the laboratory, the
reference sample concentrate must be made using stock standards prepared
independently from those used for calibration.
8.2.2 The procedure for preparation of the reference sample
concentrate is dependent upon the method being evaluated. Guidance for
reference sample concentrations for certain methods are listed below. In
other cases, the determinative methods contain guidance on preparing the
reference sample concentrate and the reference sample. If no guidance is
provided, prepare a reference sample concentrate in methanol. Spike at
the concentration the method performance data is based on. The spike
volume added to water should not exceed 1 mi/I so that the spike solvent
will not decrease extraction efficiency. If the method lacks performance
data, prepare a reference standard concentrate at such a concentration
that the spike will provide a concentration in the clean matrix that is 10
- 50 times the MDL for each analyte in that matrix.
The concentration of the target analytes in the reference sample may
need to be adjusted to more accurately reflect the concentrations that
will be analyzed in the laboratory. If the concentration of an analyte is
being evaluated relative to a regulatory limit, see Sec. 8.3.3 for
information on selecting an appropriate spiking level.
8.2.3 To evaluate the performance of the total analytical process,
the reference samples must be handled in exactly the same manner as actual
samples. Use a clean matrix for spiking purposes (one that does not have
any target or interference compounds) e.g., organic-free reagent water for
the water matrix or sand or soil (free of organic interferences) for the
solid matrix. Because of the volatility of these compounds, the spike
must be introduced directly into the matrix while the matrix is in a
sealed container (e.g., a gas tight syringe or purge device).
8.2.4 Preparation of reference samples
8.2.4.1 When analyzing aqueous samples by purge-and-trap
Method 5030, prepare reference sample concentrates containing each
target analyte at a concentration of 10 mg/L in methanol. For water
samples, spike 100 ml of organic-free reagent water with 200 /uL
which provides a 20 p,g/L concentration in the reference sample.
Quickly transfer the spiked water to four, 5-mL gas-tight syringes.
The samples are ready for analysis using Method 5030 and the
appropriate determinative method.
8.2.4.2 When analyzing soil or other solid samples by purge-
and-trap by Method 5035, add 10 /iL of reference sample concentrate
directly to the purge device as specified in Sec. 7.0. For oily
waste analysis by Method 3585 or the high concentration technique in
Method 5035, add 10 pi of reference sample concentrate (dissolved
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in methanol) directly to the oily waste just prior to the addition
of the extraction solvent. The concentration in the oily waste
should be 10 - 50 times greater than the determinative method MDL
for each analyte. Prepare four replicates.
8.2.4.3 When analyzing matrices using equilibrium headspace
Method 5021, azeotropic distillation Method 5031, or vacuum
distillation by Method 5032, prepare the reference sample
concentrate as per Sec. 8.2.4.1. Add sufficient reference sample
concentrate to the volume of organic-free reagent water specified in
these methods to provide a concentration in the water that is 10 -
50 times greater than the determinative method MDL for each analyte.
Prepare four replicates.
8.2.4.4 For methods 8031, 8032, 8315 and 8316, analyze four
portions of the water sample volume specified in each method, spiked
at a concentration that is 10 - 50 times greater than the
determinative method MDL for each analyte.
8.2.5 Analyze replicate aliquots (at least four) of the well-mixed
reference samples by the same procedures used to analyze actual samples
(Sec. 7.0 of each of the methods). This will include a combination of the
sample preparation method (usually a 5000 series method for volatile
organics) and the determinative method (an 8000 series method). Follow
the guidance on data calculation and interpretation presented in Method
8000, Sec. 8.0.
8.3 Sample Quality Control for Preparation and Analysis
8.3.1 Documenting the effect of the matrix should include the
analysis of at least one matrix spike and one duplicate unspiked sample or
one matrix spike/matrix spike duplicate pair per analytical batch. The
decision on whether to prepare and analyze duplicate samples or a matrix
spike/matrix spike duplicate must be based on a knowledge of the samples
in the sample batch. If samples are expected to contain target analytes,
then laboratories may use one matrix spike and a duplicate analysis of an
unspiked field sample. If samples are not expected to contain target
analytes, the laboratories should use a matrix spike and matrix spike
duplicate pair. See Sec. 5.5 for additional guidance on matrix spike
preparation.
8.3.2 A Laboratory Control Sample (LCS) should be included with
each analytical batch. The LCS consists of an aliquot of a clean
(control) matrix similar to the sample matrix and of the same weight or
volume. The LCS is spiked with the same analytes at the same
concentrations as the matrix spike. When the results of the matrix spike
analysis indicates a potential problem due to the sample matrix itself,
the LCS results are used to verify that the laboratory can perform the
analysis in a clean matrix.
For the laboratory control sample, use a clean matrix for spiking
purposes (one that does not have any target or interference compounds)
e.g., organic-free reagent water for the water matrix or sand or soil
(free of organic interferences) for the solid matrix. Because of the
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volatility of these compounds, the spike must be introduced directly into
the matrix while the matrix is in a sealed container (e.g., a gas tight
syringe or purge device).
8.3.3 The concentration of the matrix spike sample and/or the LCS
should be determined as described in the following Sections.
8.3.3.1 If, as in compliance monitoring, the concentration of
a specific analyte in the sample is being checked against a
regulatory concentration limit, the spike should be at or below the
regulatory limit, or 1 - 5 times the background concentration (if
historical data are available), whichever concentration is higher.
If historical data are not available, it is suggested that an
uncontaminated sample of the same matrix from the site be submitted
for matrix spiking purposes to ensure that high concentrations of
target analytes and/or interferences will not prevent calculation of
recoveries.
8.3.3.2 If the concentration of a specific analyte in a
sample is not being checked against a limit specific to that
analyte, then the spike should be at the same concentration as the
reference sample (Sec. 8.2.4) or 20 times the estimated quantitation
limit (EQL) in the matrix of interest. It is again suggested that
a background sample of the same matrix from the site be submitted as
a sample for matrix spiking purposes.
8.3.4 Analyze these QC samples (the LCS and the matrix spikes or
the optional matrix duplicates) following the procedure (Sec. 7.0) of the
selected determinative method. Calculate and evaluate the QC data as
outlined in Sec. 8.0 of Method 8000.
8.3.5 Blanks - Use of method blanks and other blanks are necessary
to track contamination of samples during the sampling and analysis
processes. Refer to Chapter One for specific quality control procedures.
8.3.6 Surrogates - A surrogate standard is a compound that is
chemically similar to the analyte group but not expected to occur in an
environmental sample. Surrogate standards should be added to all samples
when specified in the appropriate determinative method (See Table 2). See
Sec. 5.4 for the definition of surrogates and additional guidance on
surrogates.
8.4 The laboratory must have procedures in place for documenting and
charting the effect of the matrix on method performance. Refer to Chapter One
and Method 8000 for specific guidance on developing method performance data.
9.0 METHOD PERFORMANCE
9.1 The recovery of surrogate standards is used to monitor unusual matrix
effects, sample processing problems, etc, in each sample. The recovery of matrix
spiking compounds, when compared to laboratory control sample (LCS) recoveries,
indicates the presence or absence of unusual matrix effects.
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9.2 The performance of each 5000 series method will be dictated by the
overall performance of the sample preparation in combination with the analytical
determinative method.
9.3 Multi-lab and/or single-lab performance data are found at the end of
most 8000 series analytical methods.
10.0 REFERENCES
None required.
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TABLE 1
COMBINATIONS OF VOLATILE ORGANIC SAMPLE PREPARATION
AND DETERMINATIVE METHODS FOR SW-846
Method
#
8011
8015
8021
8031
8032
8033
8260
8315
8316
Method Name
EDB & DBCP by GC/ECD
Nonhalogenated VOCs by
GC/FID
Halogenated and
Aromatic VOCs by
GC/ELCD & PID
Acrylonitrile by
GC/NPD
Acryl amide by GC/ECD
Acetonitrile by GC/NPD
Volatile Organic
Compounds by GC/MS
Carbonyl Compounds by
HPLC
Acryl amide and
Acrylonitrile by HPLC
Aqueous
Samples
8011
5030,
5031, 5032
5030, 5032
8031,
5030, 5032
8032
5031
5030,
5031, 5032
8315
8316
Soil/Solid
Samples
NL
5021, 5031
5032, 5035
5021,
5032, 5035
5032, 5035
NL
NL
5021, 5031
5032, 5035
8315
NL
Waste
Samples
NL
5032,
5035
5032,
5035
5032,
5035
NL
NL
5032,
5035
8315
NL
Air
Samples
NL
NL
NL
NL
NL
NL
0030, 0031/
5041, 0040
0011, 0100/
8315
NL
NL = None listed
GC = Gas Chromatography
EDB = Ethylene Dibromide (1,2-dibromoethane)
ECD = Electron Capture Detector
FID = Flame lonization Detector
NPD = Nitrogen-Phosphorus Detector
PID = Photoionization Detector
DBCP = l,2-Dibromo-3-chloropropane
VOCs = Volatile Organic Compounds
ELCD = Electrolytic Conductivity Detector
GC/MS = Gas Chromatography/Mass Spectrometry
HPLC = High Performance Liquid Chromatography
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TABLE 2
SURROGATES FOR SW-846 CHROMATOGRAPHIC METHODS
FOR VOLATILE ORGANIC COMPOUNDS
Method
#
8011
8015
8021
8031
8032
8033
8260
8315
8316
Method Name
EDB & DBCP by GC/ECD
Nonhalogenated VOCs by
GC/FID
Halogenated and
Aromatic VOCs by
GC/ELCD & PID
Acrylonitrile by
GC/NPD
Acryl amide by GC/ECD
Acetonitrile by GC/NPD
Volatile Organic
Compounds by GC/MS
Carbonyl Compounds by
HPLC
Acryl amide and
Acrylonitrile by HPLC
Suggested Surrogates
NL
NL
Bromochl oromethane ,
2-bromo-l-chloropropane,
1,4-dichlorobutane
NL
NL
NL
Toluene-d8,
l,2-dichloroethane-d4,
4-bromofluorobenzene (BFB),
dibromofluoromethane
NL
NL
Suggested Water
Concentration
NL
NL
150 ng/5 mL
sample
NL
NL
NL
250 ng/5 mL
water
NL
NL
NL = None listed
GC = Gas Chromatography
EDB = Ethylene Dibromide (1,2-dibromoethane)
ECD = Electron Capture Detector
FID = Flame lonization Detector
NPD = Nitrogen-Phosphorus Detector
PID = Photoionization Detector
DBCP = l,2-Dibromo-3-chloropropane
VOCs = Volatile Organic Compounds
HECD = Electrolytic Conductivity Detector
GC/MS = Gas Chromatography/Mass Spectrometry
HPLC = High Performance Liquid Chromatography
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TABLE 3
MATRIX SPIKES FOR SW-846 CHROMATOGRAPHIC METHODS
FOR VOLATILE ORGANIC COMPOUNDS
Method
#
8011
8015
8021
8031
8032
8033
8260
8315
8316
Method Name
EDB & DBCP by GC/ECD
Nonhalogenated VOCs by
GC/FID
Halogenated and
Aromatic VOCs by
GC/ELCD & PID
Acrylonitrile by GC/NPD
Acryl amide by GC/ECD
Acetonitrile by GC/NPD
Volatile Organic
Compounds by GC/MS
Carbonyl Compounds by
HPLC
Acryl amide and
Acrylonitrile by HPLC
Specified Matrix Spiking
Compounds
Spike with analytes of
interest.
Spike with analytes of
interest.
1,1-Dichloroethene,
trichloroethene, benzene,
toluene, chlorobenzene
Spike with analyte of
interest.
Spike with analyte of
interest.
Spike with analyte of
interest.
1,1-Dichloroethene,
trichloroethene, benzene,
toluene, chlorobenzene
Spike with analytes of
interest.
Spike with analytes of
interest.
Concentration in
a Water Sample
NL
NL
250 ng/5 mL
sample or 50
M9/L
NL
NL
NL
250 ng/5 mL
sample or 50
M9/L
NL
NL
NL = None listed
GC = Gas Chromatography
EDB = Ethylene Dibromide (1,2-dibromoethane)
ECD = Electron Capture Detector
FID = Flame lonization Detector
NPD = Nitrogen-Phosphorus Detector
PID = Photoionization Detector
DBCP = l,2-Dibromo-3-chloropropane
VOCs = Volatile Organic Compounds
HECD = Electrolytic Conductivity Detector
GC/MS = Gas Chromatography/Mass Spectrometry
HPLC = High Performance Liquid Chromatography
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METHOD 5021
VOLATILE ORGANIC COMPOUNDS IN SOILS AND OTHER SOLID MATRICES
USING EQUILIBRIUM HEADSPACE ANALYSIS
1.0 SCOPE AND APPLICATION
1.1 Method 5021 is a general purpose method for the preparation of
volatile organic compounds (VOCs) in soils/sediments and solid wastes for
determination by gas chromatography (GC) or gas chromatography/mass spectrometry
(GC/MS). The method is applicable to a wide range of organic compounds that have
sufficiently high volatility to be effectively removed from soil samples using
an equilibrium headspace procedure. The following compounds have been determined
in soils using Method 5021:
Compound CAS No.'
Benzene 71-43-2
Bromochloromethane 74-97-5
Bromodichloromethane 75-27-4
Bromoform 75-25-2
Bromomethane 74-83-9
Carbon tetrachloride 56-23-5
Chlorobenzene 108-90-7
Chloroethane 75-00-3
Chloroform 67-66-3
Chloromethane 74-87-3
Dibromochloromethane 124-48-1
l,2-Dibromo-3-chloropropane 96-12-8
1,2-Dibromoethane 106-93-4
Dibromomethane 74-95-3
1,2-Dichlorobenzene 95-50-1
1,3-Dichlorobenzene 541-73-1
1,4-Dichlorobenzene 106-46-7
Dichlorodifluoromethane 75-71-8
1,1-Dichloroethane 75-34-3
1,2-Dichloroethane 107-06-2
1,1-Dichloroethene 75-35-4
trans-1,2-Dichloroethene 156-60-5
1,2-Dichloropropane 78-87-5
Ethylbenzene 100-41-4
Hexachlorobutadiene 87-68-3
Methylene chloride 75-09-2
Naphthalene 91-20-3
Styrene 100-42-5
1,1,1,2-Tetrachloroethane 630-20-6
1,1,2,2-Tetrachloroethane 79-34-5
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Compound CAS No."
Tetrachloroethene 127-18-4
Toluene 108-88-3
1,2,4-Trichlorobenzene 120-82-1
1,1,1-Trichloroethane 71-55-6
1,1,2-Trichloroethane 79-00-5
Trichloroethene 79-01-6
Trichlorofluoromethane 75-69-4
1,2,3-Trichloropropane 96-18-4
Vinyl chloride 75-01-4
o-Xylene 95-47-6
m-Xylene 108-38-3
p-Xylene 106-42-3
Gasoline Range Petroleum Hydrocarbons
a Chemical Abstract Services Registry Number.
1.2 Method detection limits (MDL), using Method 8260, are compound,
matrix, and instrument dependent and vary from approximately 0.1 to 3.4 M9/kg.
The applicable concentration range of this method is approximately 10 or 20
jug/kg to 200 M9/kg. Analytes that are inefficiently extracted from the soil
will not be detected when present at low concentrations, but they can be measured
with acceptable accuracy and precision when present in sufficient concentrations.
1.3 The following compounds may also be analyzed by this procedure or may
be used as surrogates:
Compound Name CAS No."
Bromobenzene 108-86-1
n-Butylbenzene 104-51-8
sec-Butyl benzene 135-98-8
tert-Butylbenzene 98-06-6
2-Chlorotoluene 95-49-8
4-Chlorotoluene 106-43-4
cis-l,2-Dichloroethene 156-59-4
1,3-Dichloropropane 142-28-9
2,2-Dichloropropane 590-20-7
1,1-Dichloropropene 563-58-6
Isopropylbenzene 98-82-8
4-Isopropyltoluene 99-87-6
n-Propylbenzene 103-65-1
1,2,3-Trichlorobenzene 87-61-6
1,2,4-Trimethylbenzene 95-63-6
1,3,5-Trimethylbenzene 108-67-8
" Chemical Abstract Services Registry Number.
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1.4 Alternatively, the method may be utilized as an automated sample
introduction device as a means for screening samples for volatile organics. A
suggested configuration is to interface it to Method 8021 but use very minimal
calibration and quality control, i.e., a reagent blank and a single calibration
standard, to obtain semiquantitative data.
1.5 Method 5021 may be applicable to other compounds that have sufficient
volatility to be removed from the soil matrix using the conditions described in
this method. It may also be applicable to both listed and non-listed target
analytes in other matrices.
1.6 This method is restricted to use by, or under the supervision of,
analysts experienced in volatile organic analysis in general and specifically the
use of equilibrium headspace devices interfaced to the determinative method
selected by the analyst.
2.0 SUMMARY OF METHOD
2.1 Volatile organic compounds (VOCs) are determined from at least a 2 g
soil sample by placing the sample into a crimp-seal or screw top glass headspace
vial at time of sampling. Each soil sample is fortified with a matrix modifying
solution and internal standards and surrogate compounds. This may be done either
in the field or in the laboratory upon receipt of samples. Additional sample is
collected in a VOA vial for dry weight determination and for high concentration
determination if the sample concentration requires it. In the laboratory, the
vials are rotated to allow for diffusion of the internal standards and surrogates
throughout the matrix. The vials are placed in the autosampler carousel and
maintained at room temperature. Approximately 1 hour prior to analysis, the
individual vials are moved to a heated zone and allowed to equilibrate. The
sample is then mixed by mechanical vibration while the elevated temperature is
maintained. The autosampler then pressurizes the vial with helium, allows a
portion to enter a sample loop which is then swept through a heated transfer line
onto the GC column. Determinative analysis is performed using the appropriate
GC or GC/MS method.
3.0 INTERFERENCES
3.1 Volatile organic analyses are subject to major interference problems
because of the prevalence of volatile organics in a laboratory. See Method 5000,
Sec. 3.0 for common problems and precautions to be followed.
3.2 The sample matrix itself can cause severe interferences by one of
several processes or a combination of these processes. These include, but are
not necessarily limited to, the absorption potential of the soil, the biological
activity of the soil, and the actual composition of the soil. Soils high in oily
material and organic sludge wastes inhibit the partitioning of the volatile
target analytes into the headspace, therefore, recoveries will be low. This so-
called "matrix effect" can be difficult, if not impossible, to overcome. It is
recommended that surrogates or additional deuterated compounds (for GC/MS
methods) be added to a matrix and analyzed to determine the percent recovery of
these compounds. The calculated percent recovery can give some indication of the
degree of the matrix effect, but not necessarily correct for it. Alternatively,
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the use of the high concentration procedure in this method should minimize the
problem with oily waste and other organic sludge wastes.
4.0 EQUIPMENT AND SUPPLIES
4.1 Sample Containers - Clear glass, 22 ml soil vials, compatible with the
analytical system. The vial must be capable of being hermetically sealed in the
field (either crimp cap or screw cap) and be equipped with a Teflon®-!ined septum
which demonstrates minimum bleed at elevated temperatures while maintaining the
seal. Ideally, the vials and septa should have a uniform tare weight. Prior to
use, wash the vials and septa with detergent solution, then rinse with tap
followed by distilled water. Place vials and septa in an oven at 105'C for 1
hour, then remove and allow to cool. Store in an area free of organic solvents.
4.2 Headspace System - The system described in this method utilizes a
totally automated equilibrium headspace analyzer. Such systems are available
from several commercial sources. The system used must meet the following
specifications.
4.2.1 It must be capable of establishing a reproducible equilibrium
at elevated temperatures between a wide variety of sample types and the
headspace. Once this is done, the system must be capable of accurately
injecting a representative portion of the headspace into a gas
chromatograph fitted with a capillary column. This must be accomplished
without adversely affecting the chromatography or the detector. The
conditions selected for the equipment used in developing this method are
listed in Sec. 7.0. Other equipment and conditions may be used if the
analyst generates and records accuracy, precision, and MDL data that are
comparable to the data in Sec. 9.0 of Method 8260. The equipment used to
develop this method and generate the accuracy and precision data listed in
Method 8260 was a Tekmar Model 7000 Equilibrium Headspace Autosampler and
a Tekmar 7050 Carousel (Tekmar Co., 7143 East Kemper Road, Cincinnati, OH
45249).
4.3 Field Sampling Equipment
4.3.1 A soil sampler which delivers at least 2 g of soil is
necessary, e.g., Purge-and-Trap Soil Sampler Model 3780PT (Associated
Design and Manufacturing Company, 814 North Henry Street, Alexandria, VA
22314), or equivalent.
4.3.2 An automatic syringe or bottle-top dispenser calibrated to
deliver 10.0 ml of matrix modifier solution, e.g., Automatic Vaccinator
Model C1377SN (NASCO, 901 Jamesville Ave., P.O. Box 901, Fort Atkinson, WI
53538), or equivalent.
4.3.3 An automatic syringe calibrated to deliver internal standards
and surrogate analytes.
4.3.4 Crimping tool for sample vials. If using screw top vials,
this is not needed.
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4.4 Miscellaneous Equipment
4.4.1 VGA vials - 40 or 60 ml VGA vials with Teflon®-faced septa
and crimp seal caps or screw top caps. These vials will be used for
sample screening, high concentration analysis (if needed) and dry weight
determination.
5.0 REAGENTS
5.1 Organic-Free Reagent Water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.2 Methanol, CH3OH - Pesticide quality or equivalent. Store away from
other solvents. Purchase in small quantities (\ Liter or 1 Liter size) to
minimize contamination.
5.3 See the determinative method and Method 5000 for guidance on the
preparation of stock standards and a secondary standard for internal standards,
calibration standards, and surrogates.
5.3.1 Calibration spiking solutions - Prepare five spiking
solutions in methanol that contain all the target analytes and the
surrogate standards. The concentrations of the calibration solutions
should be such that the addition of 1.0 juL of each to the 22 mL vials will
bracket the analytical range of the detector, e.g., for Method 8260 the
suggested concentration range for target analytes and surrogates is 5, 10,
20, 40 and 50 mg/L. The suggested concentration of internal standards is
20 mg/L (internal standards may be omitted for the GC methods if desired).
The internal standard may be added separately using 1.0 juL or premixed
with the calibration standards maintaining a 20 mg/L concentration in each
calibration standard. These concentrations may vary depending on the
relative sensitivity of the GC/MS system or any other determinative method
that is utilized.
5.3.2 Internal and surrogate standards - Follow the recommendations
of the determinative methods for the selection of internal and surrogate
standards. A concentration of 20 mg/L in methanol for both internal and
surrogate standards will be needed for spiking each sample. If
determination is by GC, external standard calibration may be preferred and
the internal standard is omitted. The concentration may vary depending on
the relative sensitivity of the GC/MS system or any other determinative
method that is utilized.
5.4 Blank Preparation - Transfer 10.0 mL (Sec. 5.6) of matrix modifying
solution to a sample vial. Add the prescribed amounts of the internal standards
and surrogate compounds, and seal the vial. Place it in the autosampler and
analyze in the same manner as an unknown sample. Analyzing the blank in this way
will indicate possible problems with the autosampler as well as the headspace
device.
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5.5 Preparation of Calibration Standards - Prepare calibration standards
in the same manner as the blanks (Sec. 5.4) using the standards prepared in Sec.
5.3.1.
5.6 Matrix Modifying Solution - Using a pH meter, add concentrated
phosphoric acid (H3P04) dropwise to 500 ml of organic-free reagent water until
the pH is 2. Add 180 g of NaCl. Mix well until all components are dissolved.
Analyze a 10.0 ml portion from each batch per Sec. 5.4 to verify that the
solution is free of contaminants. Store in a sealed bottle in an area free of
organic chemicals at 4'C.
WARNING: The matrix modifying solution may not be appropriate for soil
samples having organic carbon content. See Sec. 6.1.2.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Two alternative procedures are presented for low concentration sample
collection in special headspace sample vials. In either case, collect 3 or 4
vials of sample from each sampling point to allow sample reanalysis if necessary.
In addition, a separate portion of sample is taken for dry weight determination
and high concentration analysis (if necessary). Prepare a trip blank in the
laboratory prior to shipping the sample vials to the field. Add 10.0 mL of
matrix modifying solution to a clean 22 mL sample vial (Sec. 4.1). The internal
and surrogate standards are added just prior to analysis.
6.1.1 Without matrix modifying solution and standards - Standard 22
mL crimp cap or screw top glass headspace vials (Sec. 4.1) with
Teflon®-faced septa are used. Add 2-3 cm (approximately 2 g) of the soil
sample (using the purge-and-trap soil sampler, Sec. 4.3.1) to a tared 22
mL headspace vial and seal immediately with the Teflon® side of the septum
facing toward the sample. The samples should be introduced into the vials
gently to reduce agitation which might drive off volatile compounds.
NOTE: If high concentrations of volatile organics are expected (greater than 200
M9Ag), collection of the sample in the 22 mL vial without the addition
of matrix modifying solution allows direct addition of methanol as per the
high concentration method in Sec. 7.5.
6.1.2 With matrix modifying solution and standards - Add 2-3 cm
(approximately 2 g) of soil sample to a tared 22 mL soil vial using a
purge-and-trap soil sampler (Sec. 4.3.1). Add 10.0 mL of matrix modifying
solution and the appropriate amount of internal and surrogate standards
called for in the determinative method. Seal the vial immediately with
the Teflon® side of the septum facing toward the sample. The sample must
remain hermetically sealed until the septum is punctured by the headspace
analyzer.
WARNING: Preliminary indications are that soil samples having organic carbon
content may yield low recoveries when the matrix modifying solution
(Sec. 5.6) is used. The matrix modifying solution may not be
appropriate for these samples.
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6.1.3 Prepare a field blank by adding 10.0 mL of matrix modifying
solution plus internal and surrogate standards to a clean 22 mL vial.
NOTE: The addition of the matrix modifying solution and the internal and
surrogate standards at the time of sampling (Sec. 6.1.2) is the preferred
option unless high concentrations of volatile organics are expected. The
matrix modifying solution minimizes dehydrohalogenation reactions through
pH adjustment, eliminates biodegradation of the analytes and minimizes
losses of analytes by volatility since the vial is not opened in the
laboratory. The downside is increased opportunity for contamination of
the matrix modifier and standards in a field sampling situation. Also,
skilled personnel are required to precisely and accurately add the matrix
modifying solution, and especially the internal and surrogate standards.
These problems are minimized when added in the laboratory (Sec. 6.1.1),
however, there is the likelihood of significant losses of volatile
analytes when the vial is reopened in the laboratory.
6.1.4 Fill a 40 or 60 ml VGA vial from each sampling point to use
for dry weight determination, sample screening and for high concentration
analysis (if necessary). Sample screening is optional since there is no
danger of contaminating the headspace device because of carryover from a
high concentration sample.
6.2 Sample Storage
6.2.1 Store samples at 4°C until analysis. The sample storage area
must be free of organic solvent vapors.
6.2.2 All samples should be analyzed within 14 days of collection.
Samples not analyzed within this period must be noted and data are
considered minimum values.
7.0 PROCEDURE
7.1 Sample screening - This method (using the low concentration approach),
used in conjunction with either Methods 8015 (GC/FID) or 8021 (GC/PID/ELCD), may
be used as a sample screening method prior to any of the sample introduction -
GC/MS configurations to assist the analyst in determining the approximate
concentration of volatile organics present in a sample. This is especially
critical prior to the use of volatile organic analysis by purge-and-trap to
prevent the contamination of the system by high concentration samples. It can
also be helpful prior to the use of this headspace method, to determine whether
to proceed with the low concentration method or the high concentration method.
High concentrations of volatiles will not contaminate the headspace device.
However, it may create contamination problems in the GC or GC/MS system.
Whenever this method is utilized for sample screening, very minimal calibration
and QC are suggested. In most cases, a reagent blank and a single point
calibration are sufficient.
7.2 Determination of sample % dry weight - In certain cases, sample
results are desired based on dry-weight basis. When such data are desired, a
portion of sample for this determination should be weighed out from the 40 or 60
mL VOA vial (Sec. 6.1.3).
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WARNING: The drying oven should be contained in a hood or vented.
Significant laboratory contamination may result from a heavily
contaminated hazardous waste sample.
7.2.1 Immediately after weighing the sample for extraction, weigh
5-10 g of the sample into a tared crucible. Determine the % dry weight of
the sample by drying overnight at 105°C. Allow to cool in a desiccator
before weighing. Calculate the % dry weight as follows:
% dry weight = q of dry sample x 100
g of sample
7.3 The Low Concentration Method utilizing an equilibrium headspace
technique is found in Sec. 7.4 and sample preparation for the High Concentration
Method is found in Sec. 7.5. The high concentration method is recommended for
samples that obviously contain oily material or organic sludge waste (see Sec.
3.3). See Method 5000, Sec. 7.0 for guidance on the selection of a GC or GC/MS
determinative method. For the analysis of gasoline, use Method 8021 with GC/PID
for BTEX in series with Method 8015 with the GC/FID detector for hydrocarbons.
If GC/MS analysis is preferred for BTEX in gasoline, follow Method 8260.
7.4 Low concentration method for soil/sediment and solid waste amenable
to the equilibrium headspace method. (Approximate concentration range of 0.5 to
200 jug/kg - the concentration range is dependent upon the determinative method
and the sensitivity of each analyte.)
7.4.1 Calibration: Prior to using this introduction technique for
any GC or GC/MS method, the system must be calibrated. General
calibration procedures are discussed in Method 8000, while the
determinative methods and Method 5000 provide specific information on
calibration and preparation of standards. Normally, external standard
calibration is preferred for the GC methods because of possible
interference problems with internal standards. If interferences are not
a problem, based on historical data, internal standard calibration is
acceptable. The GC/MS methods normally utilize internal standard
calibration. The GC/MS methods require instrument tuning prior to
proceeding with calibration.
7.4.1.1 Initial calibration: Prepare five 22 mL vials, as
described, in Sec. 5.5, and a reagent blank (Sec. 5.4), and proceed
according to Sec. 7.4.2 and the determinative method selected. The
mixing step is eliminated since no soil is present in the vial.
7.4.1.2 Calibration verification: Prepare a single 22 mL
vial as described in Sec. 5.5 by spiking with the midconcentration
calibration standard. Proceed according to Sec. 7.4.2.4 (beginning
by placing the vial into the autosampler) and the determinative
method.
7.4.2 Headspace operating conditions - The conditions described
throughout Sec. 7.4 were experimentally optimized using the equipment
described in Sec. 4.2.1. If other systems are utilized, it is recommended
that the manufacturer's conditions be followed. However, the criteria for
this configuration in Method 8260 must be met or exceeded.
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7.4.2.1 This method is designed for a 2 g sample size. The
sample is prepared in the field by adding 2 g of the soil sample to
the 22 ml crimp-seal or screw top glass headspace vial as described
in Sec. 6.1.
7.4.2.2 Prior to analysis, weigh the sealed vial and its
contents to 0.01 g. If the matrix modifying solution was added at
the time of sampling (Sec. 6.1.2), the tare weight includes the 10
ml of matrix modifying solution.
7.4.2.3 If the matrix modifying solution was not added at the
time of sampling (Sec. 6.1.1), unseal the vial, rapidly add 10.0 ml
of matrix modifying solution and 1 nl of the 20 mg/L internal (if
necessary) and surrogate standards (individually or as a mixture).
Immediately reseal the vial.
NOTE: Only open and prepare one vial at a time to minimize loss of volatile
organics.
7.4.2.4 Mix the samples (on a rotator or shaker) for at least
2 min. Place the vials in the autosampler carrousel at room
temperature. The individual vials are moved to a heating zone, and
allowed to equilibrate for 50 min at 85°C. Each sample is then
mixed by mechanical vibration for 10 min at a mix power of 7.67
Watts while maintaining the temperature at 85°C. The vial is
allowed to pressure equilibrate for 5 sec. The autosampler then
raises the vial causing a stationary needle to puncture the septum,
and pressurize the vial with helium at 10 psi.
7.4.2.5 The pressurized headspace is then vented through a 1
mL sample loop to the atmosphere for 15 sec. The sample is
equilibrated within the loop for 5 sec. Finally the carrier gas, at
a flow rate of 1.0 mL/min, backflushes the sample loop sweeping the
sample through the heated transfer line onto the GC column.
7.4.2.6 Proceed with the analysis as per the determinative
method of choice.
7.5 High concentration method
7.5.1 If the sample was collected by Sec. 6.1.1 with no matrix
modifying solution added at time of sampling, add 10.0 ml of methanol to
the high level soil sample within the tared 22 ml vial. (Weigh the sample
to the nearest 0.01 g prior to the addition of methanol.)
7.5.2 Otherwise, transfer approximately 2 g of sample from the 40
or 60 ml VOA vial into a tared 22 ml sample vial (Sec. 5.1). Add 10.0 mL
of methanol.
7.5.3 Mix by shaking for 10 min at room temperature. Decant 2 mL
of the methanol to a screw top vial with Teflon® faced septa and seal.
Withdraw 10 juL, or appropriate volume of extract from Table 2, and inject
into a 22 mL vial containing 10.0 mL of matrix modifying solution and
internal standards (if required) and surrogates. Analyze by the headspace
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procedure by placing the vial into the autosampler and proceeding with
Sec. 7.4.2.4.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 5000 for sample preparation QC procedures.
8.2 Before processing any samples, the analyst should demonstrate through
the analysis of an organic-free reagent water method blank that all glassware and
reagents are interference free. Each time a set of samples is extracted, or
there is a change in reagents, a method blank should be processed as a safeguard
against chronic laboratory contamination. The blank samples should be carried
through all stages of the sample preparation and measurement.
8.3 Initial Demonstration of Proficiency - Each laboratory must
demonstrate initial proficiency with each sample preparation and determinative
method combination it utilizes, by generating data of acceptable accuracy and
precision for target analytes in a clean matrix. The laboratory must also repeat
the following operations whenever new staff are trained or significant changes
in instrumentation are made. See Sec. 8.0 of Methods 5000 and 8000 for
information on how to accomplish this demonstration.
8.4 Sample Quality Control for Preparation and Analysis - See Sec. 8.0 in
Method 5000 and Method 8000 for procedures to follow to demonstrate acceptable
continuing performance on each set of samples to be analyzed. This includes the
method blank, either a matrix spike/matrix spike duplicate or a matrix spike and
duplicate sample analysis, a laboratory control sample (LCS) and the addition of
surrogates to each sample and QC sample.
8.5 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices that are
most productive depend upon the needs of the laboratory and the nature of the
samples. Whenever possible, the laboratory should analyze standard reference
materials and participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE
9.1 Single laboratory accuracy and precision data were obtained for the
method analytes in two soil matrices: sand and a surface garden soil. These data
are found in tables in Method 8260.
10.0 REFERENCES
1. Flores, P., Bellar, T., "Determination of Volatile Organic Compounds in
Soils using Equilibrium Headspace Analysis and Capillary Column Gas
Chromatography/Mass Spectrometry", U.S. Environmental Protection Agency,
Office of Research and Development, Environmental Monitoring Systems
Laboratory, Cincinnati, OH, December, 1992.
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2. Code of Federal Regulations, 40, Ch. 1, Part 136, Appendix B.
3. loffe, B.V., Vitenberg, A.G., "Headspace Analysis and Related Methods in
Gas Chromatography", John Wiley and Sons, 1984.
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TABLE 1
DETERMINATIVE METHODS INTERFACED TO METHOD 5021
Method Method Name
Number
i
8015 Nonhalogenated Volatile Organics Using GC/FID
8021 Halogenated and Aromatic Volatiles by GC with Detectors in
Series: Capillary Column
8260 Volatile Organics by GC/MS: Capillary Column
TABLE 2
QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF
HIGH-CONCENTRATION SOILS/SEDIMENTS
Approximate Volume of
Concentration Range Methanol Extract8
500-10,000 Mg/kg 100 ML
1,000-20,000 jug/kg 50 ML
5,000-100,000 M9/kg 10 ML
25,000-500,000 M9/kg 100 ML of 1/50 dilution b
Calculate appropriate dilution factor for concentrations exceeding this
table.
* The volume of methanol added to 5 mL of water being purged should be
kept constant. Therefore, add to the 5 mL syringe whatever volume
of methanol is necessary to maintain a volume of 100 ML added to the
syringe.
b Dilute an aliquot of the methanol extract and then take 100 ML for
analysis.
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METHOD 5021
VOLATILE ORGANIC COMPOUNDS IN SOILS AND OTHER SOLID MATRICES
USING EQUILIBRIUM HEADSPACE ANALYSIS
7.2 Determine sample
dry weight.
7.3
Choose low or
high concentration
method bated on
sample
make-up.
7.4.1 Perform calibration
and verify.
Low Cone. Method
High Cone
Method
7.4.2
Was 10 0 mL
of matrix modifyin
solution added to
samples at the
time of sample
collection?
7.4.2 Rapidly add 10.0 mL
of matrix modifying solution
and 1>iL of internal and
surrogate standard.
7.5.1
Were
sample* collecte
without addition of
matrix modifying
solution?
7.4.2 Weigh the sealed
vials to 0.01 g.
7.5.2 Tranafer approx.
2g of sample into a
tared 22 mL sample
vial and add 10.0 mL
of methanol.
7.4.2.4 Mix samples on
rotator or shaker for at
least 2 minutet.
7.5.3 Mix by shaking
for 10 mm. at room temp.
Decant 2 mL of methanol.
7.4.2.4 - 7.4.2.5 Place
samples in auto-sampler
to be heated, equilibrated,
vibrated, pressurized with
helium, and injected.
7.5.3 Withdraw appropriate
volume of extract and
inject into 22 mL vial
containing 10.0 mL of
matrix modifying
solution and internal
standards and surrogates.
7.4.2.6 Proceed with
analyst* as par the
determinative method
of choice.
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METHOD 5030B
PURGE-AND-TRAP FOR AQUEOUS SAMPLES
1.0 SCOPE AND APPLICATION
1.1 This method describes a purge-and-trap procedure for the analysis of
volatile organic compounds (VOCs) in aqueous samples and water miscible liquid
samples. It also describes the analysis of high concentration soil and waste
sample extracts prepared in Method 5035. The gas chromatographic determinative
steps are found in Methods 8015 and 8021. The method is also applicable to GC/MS
Method 8260.
1.2 Method 5030 can be used for most volatile organic compounds that have
boiling points below 200°C and are insoluble or slightly soluble in water.
Volatile water-soluble compounds can be included in this analytical technique;
however, quantitation limits (by GC or GC/MS) are approximately ten times higher
because of poor purging efficiency. The method is also limited to compounds that
elute as sharp peaks from a GC column packed with graphitized carbon lightly
coated with a carbowax or a coated capillary column. Such compounds include low
molecular weight halogenated hydrocarbons, aromatics, ketones, nitriles,
acetates, acrylates, ethers, and sulfides.
1.3 Method 5030, in conjunction with Method 8015 (GC/FID), may be used
for the analysis of the aliphatic hydrocarbon fraction in the light ends of total
petroleum hydrocarbons, e.g., gasoline. For the aromatic fraction (BTEX), use
Method 5030 and Method 8021 (GC/PID). A total determinative analysis of gasoline
fractions may be obtained using Methods 8021 GC/PID) in series with Method 8015.
1.4 Water samples can be analyzed directly for volatile organic compounds
by purge-and-trap extraction and gas chromatography. Higher concentrations of
these analytes in water can be determined by direct injection of the sample into
the chromatographic system or by dilution of the sample prior to the purge-and-
trap process.
1.5 This method is restricted to use by or under the supervision of
trained analysts. Each analyst must demonstrate the ability to generate
acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 Aqueous Samples: An inert gas is bubbled through a portion of the
aqueous sample at ambient temperature, and the volatile components are
efficiently transferred from the aqueous phase to the vapor phase. The vapor is
swept through a sorbent column where the volatile components are adsorbed. After
purging is completed, the sorbent column is heated and backflushed with inert gas
to desorb the components onto a gas chromatographic column.
2.2 High Concentration Extracts from Method 5035: An aliquot of the
extract prepared in Method 5035 is combined with organic free reagent water in
the purging chamber. It is then analyzed by purge-and-trap GC or GC/MS
following the normal aqueous method.
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3.0 INTERFERENCES
3.1 Impurities in the purge gas, and from organic compounds out-gassing
from the plumbing ahead of the trap, account for the majority of contamination
problems. The analytical system must be demonstrated to be free from
contamination under the conditions of the analysis by running laboratory reagent
blanks. The use of non-polytetrafluoroethylene (non-PTFE) plastic coating,
non-PTFE thread sealants, or flow controllers with rubber components in the
purging device must be avoided, since such materials out-gas organic compounds
which will be concentrated in the trap during the purge operation. These
compounds will result in interferences or false positives in the determinative
step.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal of
the sample vial during shipment and storage. A trip blank prepared from
organic-free reagent water and carried through sampling and handling protocols
serves as a check on such contamination.
3.3 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are analyzed sequentially. Whenever an unusually
concentrated sample is analyzed, it should be followed by an analysis of
organic-free reagent water to check for cross-contamination. The trap and other
parts of the system are subject to contamination. Therefore, frequent bake-out
and purging of the entire system may be required.
3.4 The laboratory where volatiles analysis is performed should be
completely free of solvents. Special precautions must be taken to determine
methylene chloride. The analytical and sample storage areas should be isolated
from all atmospheric sources of methylene chloride. Otherwise random background
levels will result. Since methylene chloride will permeate through PTFE tubing,
all GC carrier gas lines and purge gas plumbing should be constructed of
stainless steel or copper tubing. Laboratory workers' clothing previously
exposed to methylene chloride fumes during common liquid/liquid extraction
procedures can contribute to sample contamination. The presence of other organic
solvents in the laboratory where volatile organics are analyzed will also lead
to random background levels and the same precautions must be taken.
4.0 APPARATUS AND MATERIALS
4.1 Microsyringes - 10 /nL, 25 jxL, 100 /iL, 250 juL, 500 /uL, and 1,000 /iL.
These syringes should be equipped with a 20 gauge (0.006 in ID) needle having a
length sufficient to extend from the sample inlet to within 1 cm of the glass
frit in the purging device. The needle length will depend upon the dimensions
of the purging device employed.
4.2 Syringe valve - Two-way, with Luer ends (three each), if applicable
to the purging device.
4.3 Two 5-mL glass hypodermic syringes with Luer-Lok tip (other sizes are
acceptable depending on sample volume used).
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4.4 Volumetric flasks, Class A - 10 mL and 100 mL, with ground-glass
stoppers.
4.5 Vials - 2 ml, for GC autosampler.
4.6 Purge-and-trap device: The purge-and-trap device consists of three
separate pieces of equipment: the sample purger, the trap, and the desorber.
Several complete devices are commercially available.
4.6.1 The recommended purging chamber is designed to accept 5 ml
samples with a water column at least 3 cm deep. The gaseous headspace
between the water column and the trap must have a total volume of less
than 15 ml. The purge gas must pass through the water column as finely
divided bubbles with a diameter of less than 3 mm at the origin. The
purge gas must be introduced no more than 5 mm from the base of the water
column. The sample purger, illustrated in Figure 1, meets these design
criteria. Alternate sample purge devices may be used, provided equivalent
or improved performance is demonstrated.
4.6.2 The trap used to develop this method was 25 cm long with an
inside diameter of 0.105 in. Starting from the inlet, the trap contains
the following amounts of adsorbents: 1/3 of 2,6-diphenylene oxide
polymer, 1/3 of silica gel, and 1/3 of coconut charcoal. It is
recommended that 1.0 cm of methyl silicone-coated packing be inserted at
the inlet to extend the life of the trap (see Figures 2 and 3). If it is
not necessary to analyze for dichlorodifluoromethane or other
fluorocarbons of similar volatility, the charcoal can be eliminated and
the polymer increased to fill 2/3 of the trap. If only compounds boiling
above 35°C are to be analyzed, both the silica gel and charcoal can be
eliminated and the polymer increased to fill the entire trap. Before
initial use, the trap should be conditioned overnight at 180°C by
backflushing with an inert gas flow of at least 20 mL/min. Vent the trap
effluent to the hood, not to the analytical column. Prior to daily use,
the trap should be conditioned for 10 min at 180°C with backflushing. The
trap may be vented to the analytical column during daily conditioning;
however, the column must be run through the temperature program prior to
analysis of samples.
4.6.3 The desorber must be capable of rapidly heating the trap to
180°C for desorption. The polymer section of the trap should not be
heated higher than 180°C, and the remaining sections should not exceed
220°C during bake-out mode. The desorber design illustrated in Figures 2
and 3 meet these criteria.
4.6.4 The purge-and-trap device may be assembled as a separate unit
or may be coupled to a gas chromatograph, as shown in Figures 4 and 5.
4.6.5 Trap Packing Materials
4.6.5.1 2,6-Diphenylene oxide polymer - 60/80 mesh,
chromatographic grade (Tenax GC or equivalent).
4.6.5.2 Methyl silicone packing - OV-1 (3%) on
Chromosorb-W, 60/80 mesh or equivalent.
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4.6.5.3 Silica gel - 35/60 mesh, Davison, grade 15 or
equivalent.
4.6.5.4 Coconut charcoal - Prepare from Barnebey Cheney,
CA-580-26, or equivalent, by crushing through 26 mesh screen.
4.6.5.5 Alternate Trap Materials: A number of hydrophobic
carbon molecular sieve and graphitized carbon black materials have
been developed. Various combinations of these materials have been
shown to provide retention properties similar to the Tenax\Silica
gel\Carbon trap. Alternate trap construction with such materials is
allowed, provided that the adsorption and desorption characteristics
obtained achieve equivalent or better method sensitivity and
precision in comparison to the performance documented in the
Determinative Method.
4.6.5.5.1 The following alternatives have been shown
to be viable for most analytes of concern:
7.6-cm Carbopack™ B/1.3-cm Carboseive™ S-III
VOCARB 3000 - 10.0-cm Carbopack™ B /6.0-cm Carboxin™ 1000/
1.0-cm Carboxin™ 1001
VOCARB 4000 - 8.5-cm Carbopack™ C/lO.O-cm Carbopack™
B/6.0-cm Carboxin™ 1000/1.0-cm Carboxin™ 1001
These combinations require rapid heating to desorption
temperatures of 245°C to 270°C (follow manufacturer's
instructions). At these increased temperatures, catalytic and
thermal decomposition of analytes has been reported. The
VOCARB 4000 combination has also been demonstrated to
catalytically break down 2-chloroethyl vinyl ether, and to
partially decompose 2,2-dichloropropane. Bromoform and
bromomethane have shown some thermal decomposition.
4.6.5.5.2 The amount of thermal decomposition products
formed must be routinely tracked by daily monitoring of the
formation of chloromethane and bromomethane. A daily check
standard containing surrogates, internal standards, and
20 M9/L bromoform must be analyzed prior to the analysis of
the daily check standard. If levels of chloromethane or
bromomethane exceed 0.5 jug/L, then the trap may be too
contaminated with salts or tightly bound contamination for
analysis to continue. The trap must be replaced and the
system recalibrated.
NOTE: Even newly constructed traps may have become contaminated prior to their
first use from airborne vapors. These highly adsorptive materials must be
kept tightly sealed in an area of minimum organic vapor contamination.
4.7 Heater or heated oil bath - capable of maintaining the purging
chamber to within 1°C, over a temperature range from ambient to 100°C.
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4.8 Capillary GC Columns - Any GC column that meets the performance
specifications of the determinative method may be used. See the specific
determinative method for recommended columns, conditions and retention times.
4.8.1 The wide-bore columns have the capacity to accept the standard
gas flows from the trap during thermal desorption, and chromatography can
begin with the onset of thermal desorption. Depending on the pumping
capacity of the MS, an additional interface between the end of the column
and the MS may be required. An open split interface , an all-glass jet
separator, or a cryogenic (Sec. 4.8.2) device are acceptable interfaces.
The type of interface and its adjustments can have a significant impact on
the method detection limits. Other interfaces can be used if the
performance specifications described in this method can be achieved.
4.8.2 A system using a narrow bore column will require lower gas
flows of approximately 2-4 mL/minute. Because of these low desorption
flows, early eluting analytes need to be refocussed to elute in a narrow
band. This refocussing may be carried out by using a cryogenic interface.
This type of interface usually uses liquid nitrogen to condense the
desorbed sample components in a narrow band on an uncoated fused silica
precolumn. When all components have been desorbed form the trap, the
interface is rapidly heated under a stream of carrier gas to transfer the
analytes to the analytical column. The end of the analytical column
should be placed within a few mm of the MS ion source. A potential
problem with this interface is blockage of the interface by ice caused by
desorbing water from the trap. This condition will result in a major loss
in sensitivity and chromatographic resolution. Low surrogate compound
recoveries can be a sign that this is occurring.
5.0 REAGENTS
5.1 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.2 See the determinative method and Method 5000 for guidance on internal
and surrogate standards.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Refer to the introductory material to this chapter, Organic Analytes,
Sec. 4.1. Samples should be stored in capped bottles, with minimum headspace,
at 4°C or less in an area free of solvent fumes. The size of any bubble caused
by degassing upon cooling the sample should not exceed 5-6 mm. When a bubble
is present, also observe the cap and septum to ensure that a proper seal was made
at time of sampling. Is there any evidence of leakage? If the sample was
improperly sealed, the sample should be discarded.
6.2 All samples should be analyzed within 14 days of collection. Samples
not analyzed within this period must be noted and data are considered minimum
values.
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7.0 PROCEDURE
7.1 The purge-and-trap technique for aqueous samples is found in Sec. 7.2
and guidance for analysis of solvent extracts from the High Concentration Method
in Method 5035 is found in Sec. 7.3. The gas chromatographic determinative steps
are found in Methods 8015 and 8021. The method is also applicable to GC/MS
Method 8260. For the analysis of gasoline, use Method 8021 with GC/PID for BTEX
in series with Method 8015 with the GC/FID detector for hydrocarbons.
7.2 This section provides guidance on the analysis of aqueous samples and
samples that are water miscible, by purge-and-trap analysis.
7.2.1 Initial calibration: Prior to using this introduction
technique for any GC method, the system must be calibrated. General
calibration procedures are discussed in Method 8000, while the specific
determinative methods and Method 5000 give details on preparation of
standards. The GC/MS methods require instrument tuning prior to
proceeding with calibration.
7.2.1.1 Assemble a purge-and-trap device that meets the
specification in Sec. 4.6. Condition the Tenax trap overnight at
180°C (condition other traps at the manufacturers recommended
temperature) in the purge mode with an inert gas flow of at least
20 mL/min. Prior to use, condition the trap daily for 10 min while
backflushing at 180°C with the column at 220°C.
7.2.1.2 Connect the purge-and-trap device to a gas
chromatograph or gas chromatograph/mass spectrometer system.
7.2.1.3 Prepare the final solutions containing the
required concentrations of calibration standards, including
surrogate standards, directly in the purging device. Add 5.0 ml of
organic-free reagent water to the purging device. The organic-free
reagent water is added to the purging device using a 5 ml glass
syringe (a 10 ml or 25 ml syringe may be used if preferred) fitted
with a 15 cm 20-gauge needle. The needle is inserted through the
sample inlet shown in Figure 1. The internal diameter of the
14-gauge needle that forms the sample inlet will permit insertion of
the 20-gauge needle. Next, using a 10 pi or 25 ]LtL micro-syringe
equipped with a long needle (Sec. 4.1), take a volume of the
secondary dilution solution containing appropriate concentrations of
the calibration standards. Add the aliquot of calibration solution
directly to the organic-free reagent water in the purging device by
inserting the needle through the sample inlet. When discharging the
contents of the micro-syringe, be sure that the end of the syringe
needle is well beneath the surface of the organic-free reagent
water. Similarly, add 10.0 juL of the internal standard solution.
Close the 2-way syringe valve at the sample inlet. (The calibration
standard, internal standard and surrogate standard may be added
directly to the organic free reagent water in the syringe prior to
transferring the water to the purging device, see Sec. 7.2.4.7).
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7.2.1.4 Follow the purge-and-trap analysis as outlined in
Sec. 7.2.4.
7.2.1.5 Calculate response factors (RF) or calibration
factors (CF) for each analyte of interest using the procedure
described in Method 8000.
7.2.1.6 The average CF (external standards) or RF
(internal standards) must be calculated for each compound. For
GC/MS analysis, a system performance check must be made before this
calibration curve is used (see Method 8260). If the purge-and-trap
procedure is used with Method 8021, evaluate the response for the
following four compounds: chloromethane; 1,1-dichloroethane;
bromoform; and 1,1,2,2-tetrachloroethane. They are used to check
for proper purge flow and to check for degradation caused by
contaminated lines or active sites in the system.
7.2.1.6.1 Chloromethane: This compound is the most
likely compound to be lost if the purge flow is too fast.
7.2.1.6.2 Bromoform: This compound is one of the
compounds most likely to be purged very poorly if the purge
flow is too slow. Cold spots and/or active sites in the
transfer lines may adversely affect response.
7.2.1.6.3 1 , 1 , 2 , 2-Tetrachl oroet h ane and
1,1-dichloroethane: These compounds are degraded by
contaminated transfer lines in purge-and-trap systems and/or
active sites in trapping materials.
7.2.1.7 The analytes in Method 8021 normally are not as
strongly affected by small changes in purge flow or system
contamination. When analyzing for very late eluting compounds with
Method 8021 (i.e., hexachlorobutadiene, 1,2,3-trichlorobenzene,
etc.), cross contamination and memory effects from a high
concentration sample or even the standard are a common problem.
Extra rinsing of the purge chamber after analysis normally corrects
this. The newer purge-and-trap systems often overcome this problem
with better bakeout of the system following the purge-and-trap
process. Also, the charcoal traps retain less moisture and decrease
the problem.
7.2.2 Calibration verification: Refer to Method 8000 for details on
calibration verification.
7.2.2.1 To prepare a calibration standard, inject an
appropriate volume of a primary dilution standard to an aliquot of
organic free reagent water in a volumetric flask, a gas tight
• syringe, or to a purge device, and inject an appropriate amount of
internal standard to the organic free reagent water. Be sure the
same amount of internal standard is added to each standard and
sample. The volume of organic free reagent water used for
calibration must be the same volume used for sample analysis
(normally 5 ml). The surrogate and internal standard solutions must
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be added with a syringe needle long enough to ensure addition below
the surface of the water. Assemble the purge-and-trap device as
outlined in 4.6. Follow the guidance for the purge-and-trap
procedure in Sec. 7.2.4. Ongoing GC or GC/MS calibration criteria
must be met as specified in Method 8000 before analyzing samples.
7.2.3 Sample screening
7.2.3.1 Screening of the sample prior to purge-and-trap
analysis will provide guidance on whether sample dilution is
necessary and will prevent contamination of the purge-and-trap
system. Two screening techniques that can be utilized are: the use
of an automated headspace sampler (Method 5021) interfaced to a gas
chromatograph (GC), equipped with a photo ionization detector (PID),
in series with an electrolytic conductivity detector (HECD); and,
extraction of the sample with hexadecane (Method 3820) and analysis
of the extract on a GC with a FID and/or an ECD.
7.2.4 Sample introduction and purging
7.2.4.1 All samples and standard solutions must be allowed
to warm to ambient temperature before analysis.
7.2.4.2 Assemble the purge-and-trap device. The operating
conditions for the GC and GC/MS are given in Sec. 7.0 of the
specific determinative method to be employed. Whole oven cooling
may be needed for certain GC columns and/or certain GC/MS systems to
achieve adequate resolution of the gases. Normally a 30 meter
wide-bore column will require cooling the GC oven to 25°C or below
for resolution of the gases.
7.2.4.3 GC or GC/MS calibration verification criteria must
be met (Method 8000) before analyzing samples.
7.2.4.4 Adjust the purge gas flow rate (nitrogen or
helium) to 25-40 mL/min (also see Table 1 for guidance on specific
analyte groups), on the purge-and-trap device. Optimize the flow
rate to provide the best response for chloromethane and bromoform,
if these compounds are analytes. Excessive flow rate reduces
chloromethane response, whereas insufficient flow reduces bromoform
response.
7.2.4.5 Remove the plunger from a 5 ml syringe and attach
a closed syringe valve. Open the sample or standard bottle, which
has been allowed to come to ambient temperature, and carefully pour
the sample into the syringe barrel to just short of overflowing.
Replace the syringe plunger and compress the sample. Open the
syringe valve and vent any residual air while adjusting the sample
volume to 5.0 ml. This process of taking an aliquot destroys the
validity of the liquid sample for future analysis; therefore, if
there is only one VOA vial, the analyst should fill a second syringe
at this time to protect against possible loss of sample integrity.
This second sample is maintained only until such time when the
analyst has determined that the first sample has been analyzed
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properly. Filling one 10 or 25 ml syringe would allow the use of
only one syringe. If a second analysis is needed from a syringe, it
must be analyzed within 24 hr. Care must be taken to prevent air
from leaking into the syringe.
7.2.4.6 The following procedure is appropriate for
diluting purgeable samples. All steps must be performed without
delays until the diluted sample is in a gas-tight syringe.
7.2.4.6.1 Dilutions may be made in volumetric flasks
(10 ml to 100 ml). Select the volumetric flask that will
allow for the necessary dilution. Intermediate dilutions may
be necessary for extremely large dilutions.
7.2.4.6.2 Calculate the approximate volume of
organic-free reagent water to be added to the volumetric flask
selected and add slightly less than this quantity of
organic-free reagent water to the flask.
7.2.4.6.3 Inject the proper aliquot of samples from
the syringe prepared in Sec. 7.2.4.5 into the flask. Aliquots
of less than 1 ml are not recommended. Dilute the sample to
the mark with organic-free reagent water. Cap the flask,
invert, and shake three times. Repeat the above procedure for
additional dilutions.
7.2.4.6.4 Fill a 5 ml syringe with the diluted sample
as in Sec. 7.2.4.5.
7.2.4.7 Add 10.0 juL of surrogate spiking solution (found
in each determinative method, Sec. 5.0) and, if applicable, 10.0 /zL
of internal standard spiking solution through the valve bore of the
syringe; then close the valve. The surrogate and internal standards
may be mixed and added as a single spiking solution. Matrix spiking
solutions, if indicated, should be added (10.0 juL) to the sample at
this time.
7.2.4.8 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device. Open the syringe valves and
inject the sample into the purging chamber.
7.2.4.9 Close both valves and purge the sample for the
time and at the temperature specified in Table 1. For GC/MS
analysis using Method 8260, purge time is 11 minutes at ambient
temperature.
7.2.5 Sample desorption
7.2.5.1 Non-cryogenic interface - After the 11 minute
purge (also see Table 1 for guidance on specific analyte groups),
place the purge-and-trap system in the desorb mode and preheat the
trap to 180°C (temperature may vary depending on the trap material)
without a flow of desorption gas. Certain purge-and-trap systems
5030B - 9 Revision 2
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allow the use of a dry purge at this point to eliminate excess
moisture from the gas lines. Then simultaneously, start the flow of
desorption gas at 15 mL/minute (10 mL/minute may be adequate for
certain traps) for about four minutes (1.5 min is normally adequate
for analytes in Method 8015); begin the temperature program of the
gas chromatograph; and, start data acquisition. The 15 mL/minute
desorption gas flow rate pertains to the standard silica gel trap
and a GC equipped with a wide bore capillary column.
7.2.5.2 Cryogenic interface - After the 11 minute purge,
place the purge-and-trap system in the desorb mode, make sure the
cryogenic interface is -150°C or lower, and rapidly heat the trap to
180°C (temperature may vary depending on the trap material) while
backflushing with an inert gas at 4 mL/minute for about 5 minutes
(1.5 min is normally adequate for analytes in Method 8015). At the
end of the 5-minute desorption cycle, rapidly heat the cryogenic
trap to 250°C; simultaneously begin the temperature program of the
gas chromatograph, and, start the data acquisition.
7.2.6 Trap Reconditioning
7.2.6.1 After desorbing the sample, recondition the trap
by returning the purge-and-trap device to the purge mode. Wait 15
sec; then close the syringe valve on the purging device to begin gas
flow through the trap. The trap temperature should be maintained at
180°C for Methods 8021 and 8260, and 210°C for Method 8015. Trap
temperatures up to 220°C may be employed. However, the higher
temperatures will shorten the useful life of the trap. (Trap
temperatures may vary depending on the trap material). After
approximately 7 min, turn off the trap heater and open the syringe
valve to stop the gas flow through the trap. When cool, the trap is
ready for the next sample.
7.2.6.2 While the trap is being desorbed into the gas
chromatograph, empty the purging chamber. Wash the chamber with a
minimum of two 5 mL flushes of organic free reagent water (or
methanol followed by organic free reagent water) to avoid carryover
of volatile organics into subsequent analyses.
7.2.7 Interpretation and calculation of data
7.2.7.1 If the initial analysis of a sample or a dilution
of the sample has a concentration of analytes that exceeds the
initial calibration range, the sample must be reanalyzed at a higher
dilution. When a sample is analyzed that has saturated response
from a compound, this analysis must be followed by the analysis of
organic free reagent water. If the blank analysis is not free of
interferences, the system must be decontaminated. Sample analysis
may not resume until a blank can meet the organic-free reagent water
criteria specified in Chapter One.
7.2.7.2 All dilutions should keep the response of the
major constituents (previously saturated peaks) in the upper half of
the linear range of the curve. Proceed to Method 8000 and the
5030B - 10 Revision 2
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specific determinative method for details on calculating analyte
response.
7.2.8 Analysis of water-miscible liquids
7.2.8.1 Water-miscible liquids are analyzed as water
samples after first diluting them at least 50-fold with organic-free
reagent water.
7.2.8.2 Initial and serial dilutions can be prepared by
pipetting 2 mL of the sample into a 100 ml volumetric flask and
diluting to volume with organic-free reagent water. Transfer
immediately to a 5 ml gas-tight syringe.
7.2.8.3 Alternatively, prepare dilutions directly in a
5 ml syringe filled with organic-free reagent water by adding at
least 20.0 ,LiL, but not more than 100.0 /uL of liquid sample. The
sample is ready for addition of surrogate and, if applicable,
internal and matrix spiking standards.
7.3 This section provides guidance on the analysis of solvent extracts
from High Concentration Samples prepared by Method 5035.
7.3.1 The GC or GC/MS system should be set up as in Sec. 7.0 of the
specific determinative method. This should be done prior to the addition
of the solvent extract to organic-free reagent water.
7.3.2 Table 2 can be used to determine the volume of solvent extract
to add to the 5 mL of organic-free reagent water for analysis. If a
screening procedure was followed, use the estimated concentration to
determine the appropriate volume. Otherwise, estimate the concentration
range of the sample from the low-concentration analysis to determine the
appropriate volume. If the sample was submitted as a high-concentration
sample, start with 100.0 juL. All dilutions must keep the response of the
major constituents (previously saturated peaks) in the upper half of the
linear range of the curve.
7.3.3 Remove the plunger from a 5.0 ml Luer-lok type syringe
equipped with a syringe valve and fill until overflowing with organic-free
reagent water. Replace the plunger and compress the water to vent trapped
air. Adjust the volume to 4.9 ml. Pull the plunger back to 5.0 mL to
allow volume for the addition of the sample extract and of standards. Add
10.0 /xL of internal standard solution. Also add the volume of solvent
extract determined in Sec. 7.3.2 and a volume of the same solvent used in
Method 5035 to total 100.0 /zL (excluding methanol in standards).
7.3.4 Attach the syringe-syringe valve assembly to the syringe valve
on the purging device. Open the syringe valve and inject the
water/methanol sample into the purging chamber.
7.3.5 Proceed with the analysis as outlined in the specific
determinative method. Analyze all reagent blanks on the same instrument
5030B - 11 Revision 2
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as that used for the samples. The standards and blanks should also
contain 100.0 juL of methanol to simulate the sample conditions.
7.4 Sample analysis:
7.4.1 The samples prepared by this method may be analyzed by Methods
8015, 8021, and 8260. Refer to these methods for appropriate analysis
conditions. For the analysis of gasoline, use Method 8021 with GC/PID for
BTEX in series with Method 8015 with the GC/FID detector for hydrocarbons.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 5000 for sample preparation QC procedures.
8.2 Before processing any samples, the analyst should demonstrate through
the analysis of an organic-free reagent water method blank that all glassware and
reagents are interference free. Each time a set of samples is extracted, or
there is a change in reagents, a method blank should be processed as a safeguard
against chronic laboratory contamination. The blank samples should be carried
through all stages of the sample preparation and measurement.
8.3 Standard quality assurance practices should be used with this method.
Field duplicates should be collected to validate the precision of the sampling
technique. Each analysis batch of 20 or less samples must contain: a reagent
blank; either a matrix spike/matrix spike duplicate or a matrix spike and
duplicate sample analysis; and a laboratory control sample, unless the
determinative method provides other guidance.
8.4 Surrogate standards should be added to all samples when specified in
the appropriate determinative method
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
Final Rule and Proposed Rule," October 26, 1984.
2. Bellar, T., "Measurement of Volatile Organic Compounds in Soils Using
Modified Purge-and-Trap and Capillary Gas Chromatography/Mass
Spectrometry", U.S. Environmental Protection Agency, Environmental
Monitoring Systems Laboratory, Cincinnati, OH, November, 1991.
5030B - 12 Revision 2
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TABLE 1
PURGE-AND-TRAP OPERATING PARAMETERS
Purge gas
Purge gas flow rate (mL/min)
Purge time (min)
Purge temperature (°C)
Desorb temperature (°C)
Backflush inert gas
flow (mL/min)
Desorb time (min)
8015
N2 or He
20
15.0 ±0.1
85 ±2
180
20-60
1.5
Analysis Method
8021/8260
N2 or He
40
11.0 ±0.1
Ambient
180
20-601
4
1 The desorption flow rate for Method 8021 with a wide bore capillary column
will optimize at approximately 10 to 15 mL/minute.
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TABLE 2
QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF
HIGH-CONCENTRATION SOILS/SEDIMENTS
Approximate Volume of
Concentration Range Methanol Extract8
500-10,000 jxg/kg 100 /*L
1,000-20,000 Mg/kg 50 /*L
5,000-100,000 M9/kg 10 ni
25,000-500,000 Mg/kg 100 /uL of 1/50 dilution6
Calculate appropriate dilution factor for concentrations exceeding this table.
8 The volume of methanol added to 5 mL of water being purged should be kept
constant. Therefore, add to the 5 mL syringe whatever volume of methanol
is necessary to maintain a volume of 100 ^l added to the syringe.
b Dilute an aliquot of the methanol extract and then take 100 nl for
analysis.
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FIGURE 1
EXAMPLE OF PURGING DEVICE
CtfT 1M M O.O
7 CM 20 OMJQC STMMOf NC
OO
/^ STAINLESS STEEL
5030B - 15
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FIGURE 2
EXAMPLE OF TRAP PACKINGS AND CONSTRUCTION
TO INCLUDE DESORB CAPABILITY
PACKING OCTAM.
CONSTRUCTION OCTAA.
*• S MM
-------
FIGURE 3
SCHEMATIC OF TYPICAL PURGE AND TRAP DEVICE
PURGE MODE
CARWERGAS
PLOW CONTROL
PRESSURE
REGULATOR
UOU10 INJECTION PORTS
i—COLUMN OVEN
UW-,
UUUV
CONFIRMATORY COLUMN
TO DETECTOR
ANALYTICAL COLUMN
PURGE GAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
OPTIONAL **ORT COLUMN
SELECTION VALVE
TRAP INLET
TRAP
2TC
PURGING
DEVICE
NOTE
ALL UNES BETWEEN TRAP
AND OC SHOULD BE HEATED
TO «TC
5030B - 17
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FIGURE 4
SCHEMATIC OF TYPICAL PURGE AND TRAP DEVICE
DESORB MODE
CARRfcTROAB
FLOW CONTROL
PRESSURE
REGULATOR
UOUK) INJfCnON PORTS
— COLUMN OVEN
OPTIONAL *PORT COLUMN
SELECTION VALVE
CONFIRMATORY COLUMN
TO DETECTOR
ANALYTICAL COLUMN
PU«G€GAS
R.OW CONTROL
13X MOLECULAR
SIEVE FILTER
NOTE
ALL UNES BETWEEN TRAP
AND OC SHOULD BE HEATED
TO«TC
5030B - 18
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METHOD 5030B
PURGE-AND-TRAP FOR AQUEOUS SAMPLES
Use Method 8015 (GC/FID) for
hydrocarbons and 3021
(GC/PID) for BTEX
Solvent Extract from
High Concentration
Method in 5035
7 3 1 Set up GC or GC/MS system as described in
Section 7.0 of determinative method to be used
732 Use Table 3 to determine volume of extract
to add to 5 ml water for analysis
I
733 Fill 5 mL Luerlock Syringe until overflowing
with water Replace plunger and compress water.
Adjust volume to 4.9 mL Add 10 uL internal std.,
volume of extract determined in Section 7.3 2, and
same solvent used in Method 5035 to total 100 uL
7 3.4 Attach syringe-syringe valve assembly to
syringe valve on purging device Inject water/
MeOH sample into purging chamber
I
735 Analyze as per specific determinative
method.
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METHOD 5030B
continued
Aqueous or water-misable sample
7 2 1 Perform initial GC calibration using Methods 5000,8000. and the
determinative method to be used Perform instrument tuning prior to
calibration for QC/MS
.1 Assemble purge-and-trap device per Section 4 6.
Condition Tenax trap
2 Connect purge-and-trap device to GC or GC/MS
.3 Prepare calibrator) stds directly in purging device Add
5 ml water to device with a synnge Uptake appropriate
volume of standard with a rricro-synnge and add to water in device
Add 10 uL of internal std. Close synnge valve Introduce
sample and purge as per Section 7 Z4
I
7.2.2 Perform calibration verification as required by Method 8000
1 Prepare calibration std by injecting appropriate
volume of primary std. to water and adding
appropriate amount of internal std
7 2.3 Screen sample if necessary
7.2.4 Sample introduction and purging
.1 Warm samples to room temp. (7 2.8' Dilute water-mtscible
liquids at least 50x with water)
4 Adjust purge gas flow rate
5 Pour sample into synnge barrel just short of overflowing
Replace plunger and compress sample Open valve
and vent while adjusting volume to 5 mU
6 Dilute sample if necessary.
7 Add 10 uL of surrogate spiking soln and 10 uL of internal
std.. if required
.8 Attach synnge-synnge valve assembly to synnge valve on
purging device Open valves and inject sample into purging
chamber
9 Close valves and purge as per Table 2
5030B - 20
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METHOD 5030B
continued
7.2.5 Sample desorption
7.2.5.1 Place system in desorb mode
and preheat trap to 180C without
gas flow Simultaneously start flow
of gas, temp, program of GC, and
data acquisition.
7.2.5.2 Place system in desorb mode
and rapidly heat trap to 180C while
backflushing with inert gas for 5 min.
Rapidly heat trap to 250C.
Simultaneously begin temp, program
of GC and data acquisition.
7.2.6
Recondition
trap
727 Interpret data and
calculate results.
5030B - 21
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METHOD 5031
VOLATILE. NONPURGEABLE. WATER-SOLUBLE COMPOUNDS BY AZEOTROPIC DISTILLATION
1.0 SCOPE AND APPLICATION
1.1 This method describes a procedure for separation of nonpurgeable,
water-soluble, and volatile organic compounds in aqueous samples or leachates
from solid matrices using azeotropic distillation. The appropriate gas
chromatographic/mass spectrometric (GC/MS) determinative steps are found in
Method 8260. The appropriate gas chromatographic/flame ionization (GC/FID)
determinative steps are found in Method 8015. This separation method should
be used as an alternative to Method 5030 for compounds that are difficult to
purge and trap. Method 5031 is useful in the determination of the following
compounds:
Compound Name CAS No."
Acetone 67-64-1
Acetonitrile 75-05-8
Acrolein 107-02-8
Acrylonitrile 107-13-1
Allyl alcohol 107-18-6
1-Butanol 104-51-8
t-Butyl alcohol 75-65-0
Crotonaldehyde 123-73-9
1,4-Dioxane 123-91-1
Ethanol 64-17-5
Ethyl Acetate 141-78-6
Ethylene oxide 75-21-8
Isobutyl alcohol 78-83-1
Methanol 67-56-1
Methyl ethyl ketone 78-93-3
Methyl isobutyl ketone 108-10-1
N-Nitroso-di-n-butylamine 924-16-3
Paraldehyde 123-63-7
2-Pentanone 107-87-9
2-Picoline 109-06-8
1-Propanol 71-23-8
2-Propanol 67-63-0
Propionitrile 107-12-0
Pyridine 110-86-1
o-Toluidine 95-53-4
" Chemical Abstract Services Registry Number
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1.2 Additional compounds may be separated successfully using this
method. However, use of this method to detect and measure additional analytes
may be done only after the laboratory obtains acceptable accuracy and
precision data for each additional analyte. In general, compounds that form a
water azeotrope that is greater than 50% analyte, with this azeotrope boiling
at less than 100°C, can be successfully distilled. The initial study to
determine the ability of this method to separate compounds found that the
following compounds perform poorly in this method:5
Compound CAS No. Compound CAS No.
Aniline 62-53-3 Methacrylonitrile 126-98-7
Dimethylformamide 68-12-2 Phenol 108-95-2
2-Ethoxyethanol 110-80-5 Propargyl alcohol 107-19-7
1.3 The method detection limits (MDLs) and analyte concentration
ranges are listed in the appropriate determinative methods. The MDL for a
sample may differ from those listed, depending on the nature of interferences
in the sample matrix.
1.4 This method is restricted to use by or under the supervision of
analysts experienced in procedures involving quantitative separation
techniques. Each analyst must demonstrate the ability to generate acceptable
results with this method.
2.0 SUMMARY OF METHOD
2.1 An azeotrope is a liquid mixture of two or more substances which
behaves like a single substance, in that it boils at a constant temperature
and the vapors released have a constant composition. Azeotropic distillation
is a technique which uses the ability of selected organic compounds to form
binary azeotropes with water to facilitate the separation of the compounds
from a complex matrix.
2.2 Macrodistillation technique: One liter of the sample is buffered
to pH 7, spiked with the surrogate spiking solution, and brought to boiling in
a 2 L distillation flask. The polar, volatile organic compounds (VOCs)
distill into the distillate chamber for 1 hour, and are retained there
(Figure 1). The condensate overflows back into the pot and contacts the
rising steam. The VOCs are stripped from the steam and are recycled back into
the distillate chamber. Analytes are detected and quantitated by either
direct aqueous injection GC/MS or GC/FID.
2.3 Microdistillation technique: An aliquot (normally 5 g or 40 ml)
of sample is azeotropically distilled, and the first 100 /xL of distillate are
collected. The water soluble volatile organic compounds are concentrated into
the distillate using a microdistillation system. Most semi- and non-volatile
interferences remain in the boiling flask. Use of an internal standard is
recommended to improve method precision. Concentration factors are typically
one and two orders of magnitude for soil and water matrices, respectively.
The distillation takes five to six minutes. Analytes are detected and
quantitated by either direct aqueous injection GC/MS or GC/FID.
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3.0 INTERFERENCES
3.1 Method interference may be caused by contaminants in solvents,
reagents, glassware and other sample processing hardware that lead to discrete
artifacts and/or elevated baselines in the chromatograms. All of these
materials must be routinely demonstrated to be free from interferences under
the conditions of the analysis by running laboratory method blanks.
3.1.1 Glassware must be scrupulously cleaned. Clean all glassware
as soon as possible after use by rinsing with the last solvent used.
This should be followed by detergent washing with hot water, and rinses
with tap water and organic-free reagent water. It should then be
drained dry, and heated in a laboratory oven at 150°C for several hours
before use. After drying and cooling, glassware should be stored in a
clean environment to prevent any accumulation of dust or other
contaminants. Phenol and aniline are particularly difficult to clean
from glassware.
3.1.2 Interfering contamination may occur when a sample containing
low concentrations of volatile organic compounds is analyzed immediately
after a sample containing high concentrations. One or more blanks
should be run to check for cross-contamination.
3.1.3 After analysis of a sample containing high concentrations of
volatile organic compounds, one or more blanks should be analyzed to
check for cross contamination.
3.2 Matrix interferences may be caused by contaminants that are in the
sample. The extent of matrix interferences will vary considerably from source
to source, depending upon the nature and diversity of the matrix being
sampled. If significant interferences occur in subsequent samples, additional
cleanup may be necessary.
4.0 APPARATUS AND MATERIALS
4.1 Macrodistillation System:
4.1.1 Round bottom flask, 2 L, 14/20 ground glass joint.
4.1.2 Vigreux column, 20 cm long, 14/20 ground glass joint.
4.1.3 Modified Nielson-Kryger apparatus (Figure 1). This
glassware can be made by a glassblower, or a similar apparatus can be
purchased and then modified by a glassblower according to the dimensions
given in Figure 1.
4.1.4 Recirculating, submersible pumps - One for each distillation
apparatus. Alternatively, a water chiller may be used in place of a
recirculating submersible pump, with ice water, if the chiller can
maintain a temperature of 0°C to 5eC in all distillation condensers.
4.1.5 Five-gallon container - Preferably insulated, holds ice
water to maintain condenser temperature.
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4.1.6 Volumetric glassware - 10 ml class A volumetric flasks and
volumetric pipets of various sizes, 1 to 3 ml.
4.1.7 Sample/standard vials - 4 dram glass Teflon®-! ined screw cap
or crimp top vials.
4.1.8 pH Paper - narrow range (6.0-8.0).
4.2 Microdistillation System:
4.2.1 Wadsworth MicroVOC3 System", Shamrock Glass, or equivalent:
4.2.1.1 Round bottom flask, 100 ml, 14/20 ground glass
joint.
4.2.1.2 Fractionation column, 14/20 ground glass joint,
1.6 cm OD, 1.3 cm ID, 60 cm length (see Figure 2).
4.2.1.3 Pipe insulation, polyurethane foam, 1.5 inch OD,
0.5 inch ID, 55 cm in length.
4.2.1.4 Glass beads, 5 mm OD.
4.2.1.5 Keck clamps for 14/20 ground glass joint.
4.2.1.6 Glass reducing union, 14/20 ground glass joint
to 6 mm OD tube (see Figure 3).
4.2.1.7 Stainless steel reducing union, 1/16 inch to 1/4
inch.
4.2.1.8 Air condenser, Teflon® tubing, 1/16 inch OD to
1/32 inch ID (40 cm in length, or equivalent).
4.2.2 Support stand with rod, 1 meter.
4.2.3 Three finger clamps.
4.2.4 Heating mantle, Glas-Col, 115 volts, 230 watts, STM 400, or
equivalent.
4.2.5 Temperature controller, Glas-Col PL-115-Cordtrol, 115 volts,
600 watts, or equivalent.
4.2.6 Porous carbon boiling chips, VWR Catalog No. 26397-409, or
equivalent.
4.2.7 Autosampler vials - glass, with Teflon®-!ined screw cap or
top vials.
4.2.8 Autosampler vial inserts, 100 jitL - The vial may be
calibrated by dispensing a known volume of liquid into it, and marking
the side of the vial.
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4.3 Balance - Analytical, capable of weighing 0.0001 g.
4.4 Microsyringes - Various sizes.
5.0 REAGENTS
5.1 Reagent-grade chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents shall conform to the
specifications of the Committee on Analytical Reagents of the American
Chemical Society, where such specifications are available. Other grades may
be used, provided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of the
determination.
5.2 Organic-free Reagent Water - All references to water in this
method refer to organic-free reagent water as defined in Chapter One.
5.3 Potassium phosphate, monobasic, KH2P04 (macrodistillation
technique).
5.4 Sodium phosphate, dibasic, Na2HP04 (macrodistillation technique).
5.5 Sodium chloride, NaCl (macrodistillation technique).
5.6 Stock Standard Solutions - Prepared from pure standard materials
or from purchased certified solutions.
5.6.1 Prepare, in organic-free reagent water, a set of stock
standard solutions each containing one of the target analytes. Place
about 9.0 ml of organic-free reagent water in a 10 ml tared, ground-
glass stoppered volumetric flask. Weigh the flask to the interest
0.0001 g. Add the assayed reference material, as described below:
5.6.1.1 Liquids - Using a 100 /zL syringe, immediately
add two or more drops of assayed reference material to the flask
using the known density as an approximate guide to place 0.100 g
in the flask. The liquid must fall directly into the water
without contacting the neck of the flask.
5.6.1.2 Solids - Add enough material to achieve
approximately 0.100 g in the flask.
NOTE: The solubility of N-nitroso-di-n-butylamine in water is approximately
1000 mg/L. All other stock solutions should be 10,000 mg/L.
5.6.2 Reweigh, dilute to volume, stopper, and then mix by
inverting the flask several times. Calculate the concentration in
milligrams per liter (mg/L) from the net gain in weight. When compound
purity is assayed to be 96% or greater, the weight may be used without
correction to calculate the concentration of the stock standard.
Commercially prepared stock standards may be used at any concentration
if they are certified by the manufacturer or by an independent source.
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5.6.3 Transfer the stock standard solution into a Teflon®-sealed
screw cap bottle. Store, with minimal headspace, at 4°C, and protect
from light.
5.6.4 Prepare fresh stock standard every month. Reactive
compounds, such as acrylonitrile and N-nitroso-di-n-butylamine, may need
to be prepared more frequently. Standards must be monitored closely.
See individual determinative methods for calibration requirements.
5.7 Secondary dilution standards - Using stock standard solutions,
prepare secondary dilution standards, in organic-free reagent water,
containing the compounds of interest, either singly or mixed together.
Secondary dilution standards should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them. Store in a vial with minimal headspace for 1 week only.
5.8 Stock Surrogate Solutions and Surrogate Spiking Solution
5.8.1 GC/MS Surrogates - Recommended surrogates for GC/MS analysis
(Method 8260) include de-acetone, d3-acetonitrile, d3-methanol, d5-
pyridine, d8-l,4-dioxane, and d5-phenol. Although not all the analytes
will have corresponding surrogates readily available, their use allows
very accurate quantitation by isotope dilution methods. The stock
surrogate solutions should be prepared as in Sec. 5.6, and a surrogate
spiking solution should be prepared from the stocks at a concentration
so that addition of 50 /iL of the spiking solution to the sample will
produce a sample distillate with a concentration in the middle of the
instrument calibration range, nominally 1000 mg/L. Each sample
undergoing GC/MS analysis must be spiked with the spiking solution prior
to distillation (nominal 50 jug added to the sample).
5.8.2 GC/FID Surrogates - Fluorinated alcohols and ketones may be
used as surrogates when GC/FID analysis (Method 8015) is used, provided
that the surrogates do not coelute with the target analytes. No single
surrogate can be recommended, at present, when every compound listed in
Sec. 1.1 is included in the analyte list. Nominally 50 jug of each
fluorinated surrogate should be added to each sample prior to
distillation.
NOTE: For small volume samples, the use of a spike volume greater than 200 /iL
may excessively dilute the sample and reduce analyte recovery.
5.9 Internal standards
5.9.1 GC/MS Internal Standards - The recommended internal
standards when using GC/MS analysis (Method 8260) are du-diglyme
(diethylene glycol dimethyl ether), d6-isopropyl alcohol, d7-dimethyl
formamide, and d5-benzyl alcohol. Other compounds may be used as
internal standards provided they exhibit similar retention times to the
compounds being detected. Care should be taken to avoid acquiring
compounds in which active hydrogens are deuterium labeled, and which
would exchange with the aqueous matrix. It is recommended that the
secondary dilution standard be prepared at a concentration of 1000 mg/L.
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Each distillate will be spiked at a concentration corresponding to 10
ppm of the internal standards after distillation and just before GC/MS
analysis.
5.9.2 GC/FID Internal Standards - Halogenated alcohols, ketones,
and nitriles may be used as internal standards when GC/FID analysis
(Method 8015) is used. The recommended internal standards are
hexafluoro-2-propanol, hexafluoro-2-methyl-2-propanol, and 2-
chloroacetonitrile. Nominally 5 to 50 ^g of each internal standard
should be added to each sample prior to distillation. The total spike
volume should be less than 1 ml to avoid excessively diluting the sample
and lowering analyte recovery. Ethanol or other alcohols may be used as
internal standards, provided that they are neither target analytes nor
present in the sample.
5.10 Calibration standards
5.10.1 Prepare calibration standards using the recommended
analyte, surrogate, and internal standard concentrations as specified in
the appropriate determinative method (Methods 8015 or 8260). All
calibration standards should be prepared by the same procedure as the
samples to be analyzed.
5.11 All standards should be stored at 4°C in Teflon®-!ined, screw-
capped vials with minimal headspace.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this Chapter, Organic Analytes,
Sec. 4.1.
NOTE: At this time, the effect of reducing agents or preservatives on method
performance has not been evaluated. Preservation of samples is
difficult because almost all preservatives could potentially interfere
with the analysis. Storage at 4°C appears to be the best way to
preserve most samples until analysis.
6.2 Samples should be analyzed within 14 days of sample collection.
6.3 The distillate should be stored at 4°C prior to analysis. It is
recommended that the distillate be analyzed within 24 hours of distillation.
Distillates must be analyzed within 7 days of distillation.
7.0 PROCEDURE
7.1 Macrodistillation procedure:
7.1.1 Set up the azeotropic distillation apparatus as shown in
Figure 1. Fill the 5 gallon insulated container with ice and water, or
connect the condenser to a chiller. It is very important to maintain a
temperature of 0°C to 5°C in the condensers.
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7.1.2 Measure all aliquot of sample with a 1000 mL graduated
cylinder, and transfer it to a 1 L Erlenmeyer flask. Add 3.40 g KH2P04,
and 3.55 g Na2HP04, and slowly stir with a stir bar and stir plate until
dissolved. Check the pH with narrow range pH paper. The pH of the
sample should be between 6.8 and 7.0. Add more Na2HP04 if too acidic,
or more KH2P04 if too basic.
7.1.3 Transfer the buffered sample to a 2 L round-bottomed flask.
Add 250 g of NaCl. Addition of salt has been shown to increase method
efficiency for some of the compounds.
7.1.4 Spike the sample with 50 /zL surrogate spiking solution (See
Sec. 5.8).
7.1.5 Attach the Vigreux column to the flask and then the
condenser.
7.1.6 Turn on the circulating pumps or chiller and heating
mantles. After boiling has begun, the heating mantle voltage can be
reduced approximately 10% to 15% to maintain an even boiling.
7.1.7 30 min after boiling begins, use a 5 ml syringe to remove
the distillate from the reservoir and place it into a preweighed
Teflon®-!ined screw cap vial. Take a second sample after an additional
30 minutes have elapsed and combine it with the first sample. Determine
the weight of the distillate.
7.1.8 Add an amount of internal standard spiking solution so that
the distillate will have a concentration of 10 mg/L. (For example, a 6
ml distillate would need 60 pg of internal standard). Mix well and
store at 4°C until analysis.
7.2 Microdistillation procedure
7.2.1 Aqueous samples
7.2.1.1 Add 40 ml of the well-mixed sample to a 100 ml
round bottom flask. A smaller volume may be used if sample volume
is limited, but the concentration factor will be reduced
accordingly.
7.2.1.2 Add appropriate volumes of the surrogate
standards, internal standards and matrix spiking solutions.
7.2.1.3 Add 5 to 10 boiling chips to the flask, and
place the flask in the heating mantle.
7.2.2 Solid samples
7.2.2.1 Add 5 g of sample to a 100 ml round bottom
flask.
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7.2.2.2 Add appropriate volumes of the surrogate
standards, internal standards, and matrix spiking solutions.
7.2.2.3 Add 40 ml of organic-free reagent water to the
flask, and place the flask in the heating mantle.
7.2.3 Assemble the micro distillation system (see Figure 4).
7.2.3.1 Attach the air condenser to the stainless steel
reducing union (see Figure 3). The air condenser and reducing
unions must be completely dry to avoid diluting or contaminating
the distillate.
7.2.3.2 Fill the fractionation column with glass beads.
The fractionation column and glass beads must be completely dry.
7.2.3.3 Insulate the column with polyurethane foam.
Attach the fractionation column to the 100 ml round bottom flask.
Adjust a three finger clamp to hold the column upright
7.2.3.4 Attach the reducing union assembly to the top of
the fractionation column, and hold in place with a Keck or three-
finger clamp.
7.2.3.5 Place the free end of the air condenser into the
collection vial.
7.2.4 Heat the sample at a rate sufficient to bring it to a boil
in 2-4 minutes for water samples, and 3-5 minutes for solid samples.
Using the heating mantle assembly described in Sec. 4.2.4, these rates
correspond to settings of 75% and 60% on the rheostat, respectively.
7.2.5 Collect the first 100 /xL of distillate in a calibrated
microvial.
7.2.5.1 Some bubbles may be present in the condenser.
This may make collecting exactly 100 juL difficult, but acceptable
results can be obtained with practice.
NOTE: Once steam begins to collect at the top of the fractionation column, it
normally takes less than 10 seconds for 100 pi of distillate to be
collected.
7.2.5.2 As the distillate collects in the collection
vial, slowly back the air condenser tube out of the micro-vial as
it fills. This allows the bubbles to escape without dislodging
the distillate from the micro-vial. Remove the free end of the
condenser from the vial when the collected volume reaches 100 /LtL.
7.2.5.3 A larger volume of distillate may be collected
by using a larger vial. In this case, the concentration factor
will be reduced accordingly. Collecting a larger volume will
require longer condensation times, and may require water cooling
of the condenser. The steam flow rate continues to increase after
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the first 100 p.1 of distillate is produced. This flow can
overwhelm the cooling capacity of the air condenser. Lengthening
the condenser to 100 cm may also be helpful.
NOTE: When 100 /A of distillate is collected from a 40 ml or 5 g sample, the
theoretical concentration factors are 400 and 50, respectively. Typical
absolute recoveries of target analytes are 10% to 40%. Thus, the actual
concentration factor is about 2 orders of magnitude for water samples
and 1 order of magnitude for solid samples. Distilling all calibration
standards compensates for low absolute recoveries.
7.2.6 Cap the collection vial and store at 4°C until the
distillate is analyzed.
7.2.7 Turn off the heating mantle and allow the system to cool.
Do not attempt to disassemble the apparatus while it is hot.
Significant steam pressure has built up within the system during
distillation. Disassembly could lead to a sudden release of steam. The
use of a smaller ID condenser or higher heating rates is not
recommended, since this may cause the steam within the system to reach
an unsafe pressure.
7.3 Sample Analysis
7.3.1 The samples prepared by this method may be analyzed by the
appropriate GC or GC/MS method, such as Methods 8015 and 8260. Refer to
these methods for appropriate analysis conditions.
7.3.2 All distillates and standards must be allowed to warm to
ambient temperature before analysis.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 8000 for specific quality control
procedures.
8.2 To establish the ability to generate data of acceptable accuracy
and precision refer to Method 8000 and the determinative method to be used.
9.0 METHOD PERFORMANCE
9.1 See Methods 8015 and 8260 for performance data.
10.0 REFERENCES
1. Peters, T.L. "Steam Distillation Apparatus for Concentration of Trace
Water Soluble Organics"; Anal Chem., 1980, 52(1), 211-213.
2. Cramer, P.M., Wilner, J., and Stanley, J.S., "Final Report: Method for
Polar, Water Soluble, Nonpurgeable Volatile Organics (VOCs)", For U.S.
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EPA, Environmental Monitoring Support Laboratory, EPA Contract No. 68-
C8-0041.
3. Lee, R.P., Bruce, M.L., and Stephens, M.W., "Test Method Petition to
Distill Water Soluble Volatile Organic Compounds from Aqueous Samples by
Azeotropic Microdistillation", submitted by Wadsworth/ALERT Laboratories
Inc., N. Canton, OH, January, 1991.
4. Bruce, M.L., Lee, R.P., and Stephens, M.W., "Concentration of Water
Soluble Volatile Organic Compounds from Aqueous Samples by Azeotropic
Microdistillation", Environ. Sci. Techno!., 1992, 26, 160-163.
11.0 SAFETY
11.1 The following target analytes are known or suspect to be human
carcinogens: acrylonitrile and 1,4-dioxane. Pure standard materials and
stock standard solutions of these compounds should be handled in a hood.
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FIGURE 1.
AZEOTROPIC MACRODISTILLATION SYSTEM
32mm
Cooling water
Collection Chamber
(Volume » 5 mi.)
Overflow tube
(4 mm OD)
Stopcock
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FIGURE 2.
FRACTIONATION COLUMN
14/20 Ground Glass
Glass
indentations
14/20 Ground Glass
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FIGURE 3.
AIR CONDENSER AND REDUCING UNIONS
i
Air Condenser
Stainless Steal
Reducing Union
A OD Teflon® Tube
Glass Reducing Union
6 mm 00 Tube
14/20 Ground Glass Joint
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FIGURE 4.
AZEOTROPIC MICRODISTILLATION SYSTEM
Collection Vial
Fractionation Column
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METHOD 5031
VOLATILE, NONPURGEABLE, WATER-SOLUBLE COMPOUNDS BY AZEOTROPIC DISTILLATION
7.1.1 Set up azeotrople
distillation apparatus.
Maintain a temp, of
0-5°C in condensers.
7.1.2 Transfer 1 L sample
to Erlenmeyer flask. Add
KH2P04 and Na2HP04.
Dissolve. Adjust pH.
I
7.1.3 Transfer buffered
sample to 2 L round-
bottom and add NaCI.
7.1 .4 Spike sample with
surrogate spiking solution.
7.1.5 Attach Vigreux
column and condenser.
7.1.6 Turn on pumps or
chiller and heating mantles
Maintain even boil.
7.2.1.1 Transfer 40 ml
sample to 100 ml
round-bottom.
7.1.7 Boil 30 mm. Remove
distillate and place into pre-
weighed vial. Boil 30 mm.
more. Remove distillate and
combine with first sample.
Weigh.
7.1 .8 Add internal std.
spiking soln. to distillate
concentration of 10 ug/mL.
Mix and store at
4C until analysis.
7.2.2.1 Add 5g of
sample to 1 00 mL
round-bottom.
7.2.2.2 Add appropriate
volumes of surrogate
stds., internal stds. and
matrix spiking solution.
7.2.2.3 Add 40 mL
of organic-free
reagent water.
7.2.1.2 Add appropriate
volumes of surrogate stds.
internal stds., and matrix
spiking solutions.
7.2.1
.3 Add boiling
chips.
1
7.2.4 Assemble
microdistillation
system as in Figure 4.
7.2.5 Heat to boiling
in 2-4 min.
7.2.6 Collect the 1st
lOOuL distillate in a
calibrated microvial.
7.2.7 Cap vial and store
at 4°C until analysis.
7.2.8 Allow system to
cool then disassemble.
7.3 Analyze
by appropriate
GC or GC/MS
method.
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METHOD 5032
VOLATILE ORGANIC COMPOUNDS BY VACUUM DISTILLATION
1.0 SCOPE AND APPLICATION
1.1 Method 5032 is used to determine volatile organic compounds in a
variety of liquid, solid, oily waste matrices, and animal tissues. This method
is applicable to nearly all types of matrices regardless of water, soil,
sediment, sludge, oil, and biota content. Method 5032 is useful in the
determination of the following compounds:
Compound Name
Acetone
Acrolein
Acrylonitrile
Benzene
Bromodichloromethane
Bromoform
Bromomethane
2-Butanone
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chi orodi bromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Di bromomethane
l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethanol
Ethyl benzene
Ethyl methacrylate
2-Hexanone
lodomethane
Methylene chloride
4-Methyl -2-pentanone
Styrene
1,1,2 , 2-Tetrachl oroethane
CAS No.8
67-64-1
107-02-8
107-13-1
71-43-2
75-27-4
75-25-2
74-83-9
78-93-3
75-15-0
56-23-5
108-90-7
124-48-1
75-00-3
110-75-8
67-66-3
74-87-3
74-95-3
764-41-0
75-71-8
75-35-4
107-06-2
75-35-3
156-60-5
78-87-5
10061-01-5
10061-02-6
64-17-5
100-41-4
97-63-2
591-78-6
74-88-4
75-09-2
108-10-1
100-42-5
79-34-5
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Compound Name CAS No.a
Tetrachloroethene 127-18-4
Toluene 108-88-3
1,1,1-Trichloroethane 71-55-6
1,1,2-Trichloroethane 79-00-5
Trichloroethene 79-01-6
Trichlorofluoromethane 75-69-4
1,2,3-Trichloropropane 96-18-4
Vinyl acetate 108-05-4
Vinyl chloride 75-00-3
m-Xylene 108-38-3
p-Xylene 106-42-3
o-Xylene 95-47-6
8 Chemical Abstract Services Registry Number.
1.2 This method can be used to quantify most volatile organic compounds
that have a boiling point below 180°C and are insoluble or slightly soluble in
water. Reference Method 8260 for a list of compounds, retention times, and their
characteristic ions that have been evaluated on the vacuum distillation GC/MS
system. Method 8260 also presents a list of compounds that represent a wide
range of physical properties. These compounds have been minimally investigated
to assist in identifying potential analytes of this method.
1.3 The method detection limits (MDL) determined are identified in tables
located in Method 8260. Samples that require dilution will have proportionately
higher detection limits.
1.4 Method 5032 is based on a vacuum distillation and cryogenic trapping
procedure followed by gas chromatography/mass spectrometry. Alternate columns
and detectors may be substituted when appropriate.
1.5 This method is restricted to use by, or under the supervision of,
experienced personnel who are familiar with the techniques of vacuum distillation
and experienced in the use of gas chromatographs and mass spectrometers as a
quantitative tool. Each analyst must demonstrate the ability to generate
acceptable results with this method.
2.0 SUMMARY OF METHOD
2.1 The sample is introduced into a sample flask which is then attached
to the apparatus (Figure 1). The sample chamber pressure is reduced using a
vacuum pump and remains at approximately 10 torr (vapor pressure of water) as
water is removed from the sample. The vapor is passed over a condenser coil
chilled to a temperature of -10°C or less, which results in the condensation of
water vapor. The uncondensed distillate is cryogenically trapped on a section
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of 1/8 inch stainless steel tubing chilled to the temperature of liquid nitrogen
(-196°C). After an appropriate distillation period which may vary due to matrix
or analyte. group, the condensate contained in the cryotrap is thermally desorbed
and transferred to the gas chromatograph using helium carrier gas.
2.2 It is emphasized that the apparatus conditions are optimized to remove
analyte from the sample matrix and isolate water from the distillate. The
conditions may be varied to optimize the method for a given analyte or group of
analytes. The length of time required for distillation may vary due to matrix
effects or the analyte group of interest. Operating parameters may be varied to
achieve optimum analyte recovery.
3.0 INTERFERENCES
3.1 Method interference may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to discrete
artifacts and/or elevated baseline in the chromatograms.
3.1.1 Interferences distilled from the sample will vary from source
to source, depending on the particular sample or matrix. The analytical
system should be checked to insure freedom from interferences by analyzing
method blanks under identical conditions of analysis.
3.1.2 The apparatus can be decontaminated with a ten minute
evacuation of the distillation apparatus while the condenser coils are
heated to 45°C.
3.2 The laboratory where analysis is to be performed should be completely
free of solvents. Many common solvents, most notably acetone and methylene
chloride, are frequently found in laboratories at low levels. The sample
receiving chamber should be loaded in a clean environment to eliminate this
problem.
trip blanks
e. It is
are
3.3 Samples may be contaminated during shipment. Field and •
should be analyzed to insure integrity of the transported sampl_.
recommended that wherever possible, samples aliquots and surrogates
transferred directly to sample flasks in the field, weighed and sealed using
0-ring connections.
3.4 Impurities in purge gas and from organic compounds out-gassing from
plumbing account for the majority of contamination problems. The analytical
system must be demonstrated to be free from contamination under the conditions
of the analysis by including laboratory reagent blanks. All gas lines should be
equipped with hydrocarbon and oxygen removal traps.
4.0 APPARATUS AND MATERIALS
4.1 Microsyringes: 10 ^U 25 /uL, 100 »L, 250 jttL, 500 juL, and 1000 ^uL.
These syringes should be equipped with a 20 gauge (0.006 in. ID) needle.
4.2 Syringe: 5 ml and 10 ml gas tight, with Luer Lock tip and needles.
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4.3 Balance: Analytical, capable of accurately weighing 0.0001 g, and a
top loading balance capable of weighing 0.1 g.
4.4 Balance weights: Stainless steel S-class weights ranging from 5 mg
to 100 g.
4.5 Sample Flask: 100 ml Pyrex® bulb joined to a 15 mm ID Pyrex® 0-ring
connector. The flask must be capable of being pumped down to a pressure of
10 mtorr without implosion. The flask is sealed for sample storage with a Buna-N
0-ring, a 15 mm ID 0-ring connector cap, and a pinch clamp.
4.6 Vacuum distillation apparatus (See Figure 1): The basic apparatus
consists of a sample chamber connected to a condenser which is attached to a
heated six port valve (V4). The sampling valve is connected to the following;
1) condenser (by way of Vacuum Pump Valve - V3)
2) vacuum pump
3) cryotrap
4) gas chromatograph/mass spectrometer
The sampling valve (V4) is heated to prevent condensation and potential
carryover.
The circulating system which supplies the condenser coils consists of a
cryogenic cooler with reservoir and an elevated temperature bath (45°C). The
coolant reservoir may be filled with isopropyl alcohol or other appropriate fluid
such as salt water. The fluid is circulated through the condenser coils with a
peristaltic pump and the alternating of bath fluids are accomplished by the
circulating fluid valve (V3).
The apparatus is heated to a temperature sufficient to prevent condensation
of analytes onto condenser walls, valves, and connections. The temperature of
the transfer line from the sampling valve to the gas chromatograph should be
heated to the upper temperature utilized by the GC program.
Pi rani gauges are recommended at the sample chamber, condenser and vacuum
pump for distillation monitoring. Edwards pirani gauge model 1001 with pirani
gauge head model PRH10K or equivalent.
The dimensions of the various parts of the apparatus are as follows:
1) The loop on which the sample is condensed is an 8 inch by 1/8 inch
stainless steel piece of tubing.
2) The condenser is 12 inches long and 2 inches in diameter. The ends
are made of 1/2 inch ground glass and are secured to all stainless
steel joints by the use of 1/2 inch Buna rubber 0-rings. The cooling
coils within the condenser are made of 3/16 inch glass which
terminate as 1/4 inch tubing fittings on the exterior of the
condensers.
3) The cooling liquid passing through the condenser is routed from the
refrigerant reservoir using 1/4 inch pure silicone tubing.
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4) The tubing between the GC inlet and the six port valve is made of
1/16 inch capillary fused silica lined stainless steel.
5) The sampling chamber valve (VI) and the vacuum pump valve V3) are
made of 1/2 inch stainless steel.
6) The circulating fluid valve (V2) is made of 1/4 inch brass.
7) The six port sampling valve (V4) is made of stainless steel with
Teflon® internal parts.
4.7 Gas chromatograph/ mass spectrometer system:
4.7.1 Gas chromatograph: An analytical system complete with a
temperature-programmable gas chromatograph and all required accessories
including syringes, analytical columns, and gases.
4.7.2 Column: 30 m by 0.7 mm ID fused silica capillary column
chemically bonded with methylphenyl cyanopropyl silicone J&W DB-624, or
equivalent, 3.0 /xm film thickness.
4.7.3 Mass spectrometer: Capable of scanning from 35-350 amu
every 2 sec. or less, using 70 volts (nominal) electron energy in the
electron impact mode and producing a mass spectrum that meets all the
criteria listed in Method 8260 when 50 ng of 4-bromofluorobenzene (BFB) is
injected through the gas chromatograph inlet.
4.7.4 Gas chromatograph/ mass spectrometer heated jet separator
interface: A heated glass jet separator interface capable of removing
from 10 to 40 mL/min of helium from the exit end of the wide bore
capillary column. The interface should have the ability to be heated
through a range of 100 to 220°C.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Methanol: CH3OH, purge and trap grade or equivalent. Store apart
from other solvents.
5.4 Standard solutions: Stock solutions may be prepared from pure
standard materials or purchased as certified solutions. Prepare stock standard
solutions in methanol, using assayed liquids or gases, as appropriate.
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5.4.1 Place about 9.8 ml of methanol in a 10 ml tared, ground-glass-
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 min or until all alcohol-wetted surfaces have dried. Weigh the
flask to the nearest 0.1 mg.
5.4.2 Add the assayed reference material, as described below.
5.4.2.1 Liquids: Using a 100 pi syringe, immediately add two
or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
5.4.2.2 Gases: To prepare standards for any compounds that
boil below 30°C (e.g., bromomethane, chloroethane, chloromethane, or
vinyl chloride), fill a 5 ml valved gas-tight syringe with the
reference standard to the 5.0 mL mark. Lower the needle to 5 mm
above the methanol meniscus. Slowly introduce the reference
standard above the surface of the liquid. The heavy gas will
rapidly dissolve in the methanol. Standards may also be prepared by
using a lecture bottle equipped with a septum. Attach Teflon®
tubing to the side-arm relief valve and direct a gentle stream of
gas onto the methanol meniscus.
5.4.3 Reweigh, dilute to volume, stopper, and mix by inverting the
flask several times. Calculate the concentration in micrograms per
micro!iter (jig//iL) from the net gain in weight. When compound purity is
assayed to be 96% or greater, the weight may be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.4.4 Transfer the stock standard solution into a Teflon®-sealed
screw cap bottle. Store, with minimal headspace, at -10 to -20°C and
protect from light.
5.4.5 Prepare fresh gas standards every two months. Reactive
compounds such as 2-chloroethylvinyl ether and styrene may need to be
prepared more frequently. All other standards must be replaced after six
months, or sooner if comparison with check standards indicates a problem.
5.5 Secondary dilution standards: Using stock standard solutions, prepare
in methanol secondary dilution standards containing the compounds of interest,
either singly or mixed together. Secondary dilution standards must be stored
with minimal headspace and should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards from
them.
5.6 Surrogate standards: The surrogates recommended are toluene-d8, 4-
bromofluorobenzene, and l,2-dichloroethane-d4. Other compounds may be used as
surrogates, depending upon the analysis requirements. A stock surrogate solution
in methanol should be prepared as described in Section 5.1, and a surrogate
standard spiking solution should be prepared from the stock at a concentration
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of 25 ng/ml in methanol . Each sample undergoing GC/MS analysis must be spiked
with 10 juL of the surrogate spiking solution prior to analysis.
5.7 Internal Standards: It is recommended that one or more internal
standards be selected from: bromochloromethane, 1,4-difluorobenzene, vinyl
chloride-dg, chlorobenzene-d5. The compound(s) selected should demonstrate
minimal matrix effects. Other compounds maybe used as internal standards as long
as they have retention times similar to the compounds being detected by GC/MS.
Method 8260 should be reviewed to select compounds appropriate for the matrix
being tested. Prepare internal standard stock and secondary dilution standards
in methanol using the procedures described in Sections 5.1 and 5.2. It is
recommended that the secondary dilution standard should be prepared at a
concentration of 25 /j.g/ml of each internal standard compound. Addition of 10
fj,L of this standard to 5.0 ml of sample or calibration standard would be the
equivalent of 50 M9/L-
5.8 4-Bromofluorobenzene (BFB) standard: A standard solution containing
25 ng/^L of BFB in methanol should be prepared.
5.9 Calibration standards: Calibration standards at minimum of five
concentration levels should be prepared from the secondary dilution of stock
standards (see Sections 5.1 and 5.2). Prepare these solutions in reagent water
or purge and trap grade methanol. One of the concentration levels should be at
a concentration near, but above, the method detection limit. The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples and should not exceed the working range of the GC/MS
system. Each standard should contain each analyte for detection by this method
(e.g., some or all of the compounds listed in Method 8260 may be included).
Store for one week or less at -10 to -20°C in a vial with minimal headspace.
5.10 Matrix spiking standards: matrix spiking standards should be prepared
from volatile organic compounds which will be representative of the compounds
being investigated. The suggested compounds are 1,2-dichloroethene,
trichloroethene, chlorobenzene, toluene, and benzene. The standard should be
prepared in methanol, with each compound present at a concentration of 25
5.11 Great care must be taken to maintain the integrity of all standard
solutions. It is recommended that all standards by stored at -10 to -20°C in
screw-cap amber bottles with Teflon® liners.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1 .
6.2 Samples to be analyzed for volatile compounds should be stored
separately from standards and other samples.
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7.0 PROCEDURE
7.1 Recommended GC/MS operating conditions:
Electron energy: 70 volts (nominal)
Mass range: 35-350 amu
Scan time: To give 8 scans/peak but not to exceed 3
sec/scan
Initial column temperature: 10°C
Initial hold time: 3.0 min
Column ramp rate: 5.0°C/min
Final column temperature: 230°C
Final hold time: 1.0 min
7.2 Initial calibration for vacuum distillation procedure:
7.2.1 Turn the six port sampling valve (V4) handle to the load
position.
7.2.2 Place a styrofoam cup under the sample loop and secure in
place. Loop the cup with liquid N2. Recharge the styrofoam cup under the
sample loop throughout the distillation with liquid N2 as necessary.
7.2.3 Turn the sample chamber valve (VI) to the off position and
remove the sample container.
7.2.4 Load the standard, containing surrogates and internal
standards, into the sample flask and attach to the apparatus.
7.2.5 Turn the coolant/heat valve (V2) to circulate coolant through
the condenser coils. Be sure all connections are complete and sealed
properly. Open the sample chamber valve to begin the distillation.
Continue distillation for 10 minutes.
NOTE: IF PIRANI GAUGES ARE USED: After five minutes of distillation the Pirani
gauge at the vacuum pump should indicate about 0.1 torr, and the Pirani
gauge at the condenser and should indicate 250 torr or less. After ten
minutes of distillation the Pirani gauge at the sample chamber should read
approximately 10 torr. If these pressures are not attained a leak may be
present and the distillation may not be successful. Distillation
performance surrogates should be evaluated for acceptability of
distillation.
7.2.6 Setup the data system for acquisition of the data file. This
may be done prior to the beginning of step 1. While distillation times
may be variable depending on sample matrix, the data system should be
ready and the GC oven at equilibrium by the time the distillation is
complete.
7.2.7 Once the distillation is complete GC/MS analyses may be
performed. Turn the sampling valve handle to the inject position while
maintaining the styrofoam cup with liquid N2 in place. Rapidly remove the
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styrofoam cup and replace with the beaker of (90°C) hot tap water and
commence GC/MS data acquisition.
7.2.8 Once acquisition has begun the sample chamber valve may be
closed and the sample flask removed.
7.2.9 The distillation apparatus can then readied for the next
analyses. This is performed by switching the vacuum pump valve (V3) to
the vacuum pump position which disconnects the vacuum stream to the
sampling valve (V4). The condenser circulating fluid is then switched to
the heated fluid (45°C) by switching valve V2. Evacuate the distillation
system for 10 minutes. It is recommended that a liquid nitrogen cooling
trap be placed between valve V3 and the vacuum pump to prevent degradation
of the vacuum due to overload of moisture in the vacuum pump oil.
7.3 Calibration response factors: Calculate according to Method 8260.
7.4 Sample preparation:
7.4.1 Liquid: Liquid samples should be stored with minimal or no
headspace to minimize the loss of highly volatile analytes. Samples may
be preserved with ascorbic acid to stop biological degradation which may
occur in water samples.
7.4.2 Solid/Soil: Solid and soil samples should be rapidly
withdrawn from their sample container and weighed while still cold. The
sample is then rapidly transferred to the sample chamber and secured to
prevent loss of analytes.
7.4.3 Tissue: Tissue samples which are fleshy may have to be minced
into smaller pieces to get them through the neck of the sample chamber.
This is best accomplished by freezing the sample in liquid nitrogen before
any additional processing takes place. Biota containing leaves and other
softer samples may be minced using clean scissors.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 8000 for specific quality control
procedures.
8.2 Before processing any samples, the analyst should demonstrate through
the analysis of a reagent water method blank that all glassware and reagents are
interference free. Each time a set of samples is analyzed, or there is a change
in reagents, a method blank should be processed as a safeguard against laboratory
contamination. The blank samples should be carried through all stages of sample
preparation and measurement.
8.3 To establish the ability to generate data of acceptable accuracy and
precision refer to Method 8000 and the determinative method to be used.
8.4 Matrix and distillation performance surrogates.
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8.4.1 Matrix effects and distillation performance may be monitored
separately through the use of surrogates. Compounds that have
demonstrated minimal matrix effects such as vinyl chloride-d3 and
bromochloromethane may be added directly to the matrix and used as an
internal standard. Tables located in Method 8260 present recovery data
from water, soil and oil matrices that should be considered when selecting
surrogates. Compounds that have demonstrated matrix effects and/or
distillation losses (i.e., pyridine-d5, 2-fluorophenol for matrix effects
and l,2-dichlorobenzene-d4 for distillation performance) are recommended
as surrogates.
8.4.2 The use of multiple matrix surrogates and multiple
distillation performance surrogates are recommended. It is recommended
that distillation effect surrogates be relatively insoluble in water.
Matrix monitoring compounds should be selected to bracket the physical
properties of the analytes of interest. If matrix effects have been shown
or are suspected for a chosen distillation surrogate compound, the
distillation surrogates should be added to the sample flask in an open
mini-vial suspended above the sample by a wire stand. Multiple surrogates
for monitoring one or more classes of compounds are recommended for
evaluating matrix effects.
8.5 Standard quality assurance practices should be used with this method.
Field replicates should be collected to validate the precision of the sampling
technique. Laboratory replicates should be analyzed to validate the precision
of the analysis. Fortified samples should be carried through all stages of
sample preparation and measurement; they should be analyzed to validate the
sensitivity and accuracy of the analysis. If the fortified samples do not
indicate sufficient sensitivity to detect <1 /ig/g of the analytes in the sample,
then the sensitivity of the instrument should be increased, or a larger amount
of the sample should be used.
9.0 METHOD PERFORMANCE
9.1 Performance data for Method 5032 are provided in tables in Method
8260.
10.0 REFERENCES
1. Hiatt, M.H. "Analysis of Fish and Sediment For Volatile Priority
Pollutants", Analytical Chemistry 1981, 53 (9), 1541.
2. Hiatt, M.H. "Determination of Volatile Organic Compounds in Fish Samples by
Vacuum Distillation and Fused Silica Capillary Gas Chromatography/Mass
Spectrometry"; Analytical Chemistry 1983, 55 (3), 506.
3. United States Patent 4,600,559. "Vacuum Extractor with Cryogenic
Concentration and Capillary Interface", held by the U.S. EPA.
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Gas Chromalograph/ Mass Spectrometer
Sampling Valve (V4)
*. Vacuum
Pump
— Vacuum
Pump Valve V3
Condenser
Sample
Chamber
Cryotrap
Sample
Chamber
Valve
(V1)
Refrigerent
Bath
; Circulating Fluid
Valve (V2)
Figure 1
VACUUM DISTILLATION CONFIGURATION
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METHOD 5032
VOLATILE ORGANIC COMPOUNDS BY VACUUM DISTILLATION
>
r
Sample
preparation.
>
t
7.1 Establish
instrument set-up.
>
r
7.2 Calibrate for
and perform vacuum
distillation.
>
r
7.2.7 Begin GC/MS
data acquisition.
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METHOD 5035
CLOSED-SYSTEM PURGE-AND-TRAP AND EXTRACTION FOR
VOLATILE ORGANICS IN SOIL AND WASTE SAMPLES
1.0 SCOPE AND APPLICATION
1.1 This method describes a closed-system purge-and-trap process for the
analysis of low concentrations of volatile organic compounds (VOCs) in
soils/sediments and solid waste. Guidance is also provided for sample
preparation of soils, solid waste and non-aqueous liquids with high
concentrations of volatile organics. The gas chromatographic determinative steps
are found in Methods 8015 and 8021. The method is also applicable to GC/MS
Method 8260.
1.2 The low soil method differs from the low soil/sediment method in the
original Method 5030 because the hermetic seal of the sample vial is never broken
from time of sampling to time of analysis. Since the sample is never exposed to
the atmosphere after sampling, the loss of VOCs is negligible. Therefore,
concentration data obtained using Method 5035 would be expected to be higher and
more representative of the soil contamination at time of sampling, than that
obtained using the original low soil method (i.e. subsampling a portion of sample
from the sample vial in the laboratory). The applicable concentration range of
the low soil method is dependent on the determinative method, matrix, and
compound. However, it will generally fall in the 0.5 to 200 /xg/kg range. The
estimated quantitation limit range for high concentration analysis of soil and
waste samples will be in the 1 to 20 mg/kg range. However, this is highly
dependent on interferences.
1.3 Method 5035 can be used for most volatile organic compounds that have
boiling points below 200°C and are insoluble or slightly soluble in water.
Volatile, water-soluble compounds can be included in this analytical technique;
however, quantitation limits (by GC or GC/MS) are approximately ten times higher
because of poor purging efficiency. The method is also limited to compounds that
elute as sharp peaks from a GC column packed with graphitized carbon lightly
coated with a carbowax or a coated capillary column. Such compounds include low
molecular weight halogenated hydrocarbons, aromatics, ketones, nitriles,
acetates, acrylates, ethers, and sulfides.
1.4 Method 5035, in conjunction with Method 8015 (GC/FID), may be used for
the analysis of the aliphatic hydrocarbon fraction in the light ends of total
petroleum hydrocarbons, e.g., gasoline. For the aromatic fraction (BTEX), use
Method 5035 and Method 8021 (GC/PID). A total determinative analysis of gasoline
fractions may be obtained using Method 8021 in series with Method 8015.
1.5 Samples should be screened, prior to application of this method, to
avoid contamination of the purge-and-trap system by samples that fall beyond the
concentration range of the low concentration method.
1.6 This method is restricted to use by or under the supervision of
trained analysts. Each analyst must demonstrate the ability to generate
acceptable results with this method.
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2.0 SUMMARY OF METHOD
2.1 Low Concentration Method: Volatile organic compounds (VOCs) are
determined from a 5 g soil sample by placing the sample, at time of collection,
into a specially designed, fritted, 40-mL vial. A stirring bar is added and, if
desired, preservative may be added as well. The vial is then sealed and shipped
to a laboratory or appropriate analysis site. The entire vial is then placed,
unopened, into the instrument carousel. Immediately before analysis, water,
surrogate standards and internal standards are automatically added without
breaking the hermetic seal on the sample vial. The slurry is preheated to 40°C,
then purged by passing an inert gas through the bottom of the vial while
mechanical agitation is being provided by the magnetic stirring bar. Purged
components then travel via a transfer line to a trap. When purging is complete,
the trap is heated and backflushed with helium to desorb the trapped sample
components into a gas chromatographic (GC) column interfaced to a mass
spectrometer (MS) or a specific detector, depending on the determinative method
selected.
2.2 High Concentration Method: If the sample introduction technique in
Sec. 2.1 is not applicable, a portion of the sample is dispersed in a water
miscible solvent to dissolve the volatile organic constituents. An aliquot of
the solution is combined with water in a specially designed purging chamber. It
is then analyzed by purge-and-trap GC following the water purge-and-trap method
(Method 5030).
3.0 INTERFERENCES
3.1 Impurities in the purge gas and from organic compounds out-gassing
from the plumbing ahead of the trap account for the majority of contamination
problems. The analytical system must be demonstrated to be free from
contamination under the conditions of the analysis by running laboratory reagent
blanks. The use of non-polytetrafluoroethylene (non-PTFE) plastic coating,
non-PTFE thread sealants, or flow controllers with rubber components in the
purging device must be avoided, since such materials out-gas organic compounds
which will be concentrated in the trap during the purge operation. These
compounds will result in interferences or false positives in the determinative
step.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal of
the sample vial during shipment and storage. A trip blank prepared from
organic-free reagent water and carried through sampling and handling protocols
serves as a check on such contamination.
3.3 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are analyzed sequentially. Whenever an unusually
concentrated sample is analyzed, it should be followed by an analysis of
organic-free reagent water to check for cross-contamination. The trap and other
parts of the system are subject to contamination. Therefore, frequent bake-out
and purging of the entire system may be required.
3.4 The laboratory where volatile analysis is performed should be
completely free of solvents. Special precautions must be taken to determine
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methylene chloride. The analytical and sample storage area should be isolated
from all atmospheric sources of methylene chloride, otherwise random background
levels will result. Since methylene chloride will permeate through PTFE tubing,
all GC carrier gas lines and purge gas plumbing should be constructed of
stainless steel or copper tubing. Laboratory workers' clothing previously
exposed to methylene chloride fumes during common liquid/liquid extraction
procedures can contribute to sample contamination. The presence of other organic
solvents in the laboratory where volatile organics are analyzed will also lead
to random background levels and the same precautions must be taken.
4.0 APPARATUS AND MATERIALS
4.1 Sample Containers/Purge Device - 40-mL clear soil vials with a special
frit (Figure 1) available from Dynatech Precision Sampling Corporation (or
equivalent). Each vial should be equipped with two PTFE-faced silicone septa (or
equivalent) which demonstrate minimal bleed at elevated temperatures. Prior to
use, wash vials and septa with detergent and rinse with tap and distilled water.
Allow the vials and septa to air dry at room temperature, place in a 105°C oven
for one hour, then remove and allow to cool in an area known to be free of
organics. Be sure the PTFE side of each septum is toward the sample.
4.2 Purge-and-Trap System - The system used for purging and trapping
consists of two pieces of equipment linked together to form a hybrid system. The
first piece of equipment performs as the automated sample preparation and purging
device while the other piece of equipment contains the trap and functions as the
desorber. Systems are commercially available from several sources that meet all
of the following specifications.
NOTE: The equipment used to develop this method was a Dynatech PTA-30 W/S
Autosampler (Dynatech Precision Sampling Corporation, 8275 West El Cajon
Drive, Baton Rouge, LA 70815). See the Disclaimer at the front of this
manual for guidance on the use of alternative equipment.
4.2.1 The purging device should be capable of accepting the 40-mL
soil vial and maintaining the vial at 40°C while the inert gas is allowed
to pass through the sample effectively purging it. The device should also
be capable of introducing 19 mL of organic-free reagent water into the
purging device without venting the headspace of the vial. It should also
be capable of stirring the sample during purging. The analytes being
purged must be allowed to escape the vial through an inert transfer line
maintained at an elevated temperature. After passing through the transfer
line, the analytes are then allowed to concentrate on a trap.
4.2.2 The trap used to develop this method was 25 centimeters long,
had an inside diameter of 0.105 inches and was packed with
Carbopack/Carbosieve (Supelco, Inc.). Traps that demonstrate similar
hydrophobic and retention properties may be used. The trap must
demonstrate sufficient adsorption and desorption characteristics to meet
the method MDLs of all the target analytes for a given Project and the QC
requirements in Method 8000 and the Determinative Method. The most
difficult are the gases and especially dichlorodifluoromethane. Also,
demonstrate that the trap is capable of desorbing the late eluting target
analytes.
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NOTE: Check the response of the brominated compounds when using these
alternative charcoal traps (especially Vocarb 4000), as some degradation
has been noted relating to the higher desorption temperatures (especially
temperatures above 240 - 250"C). 2-Chloroethyl vinyl ether is degraded on
Vocarb 4000 but performs adequately when Vocarb 3000 is used. The primary
criteria, as stated above, is that all target analytes meet the MDL
requirements for a given project.
4.2.2.1 The desorber for the above trap must be capable of
rapidly heating the trap to 245"C prior to the beginning of the flow
of desorption gas. Several commercial desorbers (purge-and-trap
units) are available.
4.2.3 The standard trap used in previous EPA purge-and-trap methods
is also acceptable. This trap is 25 cm long and has an inside diameter of
at least 0.105 in. Starting from the inlet, the trap contains the
following amounts of adsorbents: 1/3 of 2,6-diphenylene oxide polymer,
1/3 of silica gel, and 1/3 of coconut charcoal. It is recommended that
1.0 cm of methyl silicone-coated packing be inserted at the inlet to
extend the life of the trap. If it is not necessary to analyze for
dichlorodifluoromethane or other fluorocarbons of similar volatility, the
charcoal can be eliminated and the polymer increased to fill 2/3 of the
trap. If only compounds boiling above 35'C are to be analyzed, both the
silica gel and charcoal can be eliminated and the polymer increased to
fill the entire trap. Before initial use, this trap should be conditioned
overnight at 180'C by backflushing with an inert gas flow of at least
20 mL/min. Vent the trap effluent to the hood, not to the analytical
column. Prior to daily use, the trap should be conditioned for 10 min at
180"C with backflushing. The trap may be vented to the analytical column
during daily conditioning; however, the column must be run through the
temperature program prior to analysis of samples.
4.2.3.1 Trap Packing Materials
4.2.3.1.1 2,6-Diphenylene oxide polymer - 60/80 mesh,
chromatographic grade (Tenax GC or equivalent).
4.2.3.1.2 Methyl silicone packing - OV-1 (3%) on
Chromosorb-W, 60/80 mesh or equivalent.
4.2.3.1.3 Silica gel - 35/60 mesh, Davison, grade 15 or
equivalent.
4.2.3.1.4 Coconut charcoal - Prepare from Barnebey
Cheney, CA-580-26, or equivalent, by crushing through 26 mesh
screen.
4.2.3.2 The desorber for the trap must be capable of rapidly
heating the trap to 180"C for desorption. The polymer section of
the trap should not be heated higher than 180°C, and the remaining
sections should not exceed 2208C during the bake-out mode.
4.2.3.3 Prior to initial use, condition the trap overnight at
180°C in the purge mode with an inert gas flow of at least
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20 mL/min. Prior to daily use, condition the trap for 10 min while
backflushing at 180'C with the GC column at 220°C.
4.3 Syringe and Syringe Valves
4.3.1 Two 25-mL glass hypodermic syringes with Luer-Lok (or
equivalent) tip (other sizes are acceptable depending on sample volume
used).
4.3.2 Three 2-way syringe valves with Luer ends.
4.3.3 One 25-^1 micro syringe with a 2 inch x 0.006 inch ID, 22/j
bevel needle (Hamilton #702N or equivalent).
4.3.4 Micro syringes - 10, 100 /iL.
4.3.5 Syringes - 0.5, 1.0, and 5-mL, gas tight with shut-off valve.
4.4 Miscellaneous
4.4.1 Glass vials - 60 ml, septum sealed, to collect samples for
screening, dry weight determination, and high concentration analysis (if
needed).
4.4.2 Top-loading balance - 0.1 g.
4.4.3 Glass scintillation vials - 20 ml, with screw-caps and
Teflon® liners or glass culture tubes with screw-caps and Teflon® liners.
4.4.4 Volumetric flasks, Class A - 10 mL and 100 ml_, with
ground-glass stoppers.
4.4.5 Vials - 2 ml, for GC autosampler.
4.4.6 Spatula - Stainless steel.
4.4.7 Disposable pipets - Pasteur.
5.0 REAGENTS
5.1 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.2 Methanol, CH3OH - Pesticide quality or equivalent. Store away from
other solvents.
5.3 Polyethylene glycol, H(OCH2CH2)nOH - Free of interferences at the
detection limit of the target analytes.
5.4 See the determinative method and Method 5000 for guidance on internal
and surrogate standards.
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6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Sample Collection - Refer to the introductory material to this
chapter, Organic Analytes, Sec. 4.1.
6.1.1 Weigh the assembled soil sample vial containing the stirring
bar to 0.1 g. Ship the tared sampling vial to the sampling site with the
seals intact. Open the large chamber containing the stirring bar, and add
about 5 grams (2-3 centimeters) of soil on top of the stirring bar (wear
gloves whenever handling the tared containers). Immediately seal and
store at 4°C. (Samples may be weighed in the field if a means is
available to weigh to 0.1 g.) Do not interchange seals and stirring bars
with other soil vials. It is advisable to collect duplicate samples in
the special tared sample/purge vials in case reanalysis of the sample is
required.
6.1.2 Collect additional duplicate aliquots of each sample in 60 mL
glass vials (septum sealed) for screening, dry weight determination, and
high concentration analysis (if needed).
6.2 Sample Storage - Refer to the introductory material to this chapter,
Organic Analytes, Sec. 4.1.
6.2.1 Store samples at 4°C until analysis. The sample storage area
should be free of organic solvent vapors.
6.2.2 All samples should be analyzed within 14 days of collection.
Samples not analyzed within this period must be noted and data are
considered minimum values.
7.0 PROCEDURE
7.1 The Low Concentration Method utilizing a closed-system purge-and-trap
technique is found in Sec. 7.2 and sample preparation for the High Concentration
Method is found in Sec. 7.3. The gas chromatographic determinative steps are
found in Methods 8015 and 8021. The method is also applicable to GC/MS Method
8260. For the analysis of gasoline, use Method 8021 with GC/PID for BTEX in
series with Method 8015 with the GC/FID detector for hydrocarbons.
7.2 Low Concentration Method for Soil/Sediment and Solid Waste Amenable
to the Closed-system Purge-and-Trap Method (Approximate concentration range of
0.5 to 200 jug/kg - the concentration range is dependent upon the determinative
method and the sensitivity of each analyte.)
7.2.1 Initial calibration: Prior to using this introduction
technique for any GC or GC/MS method, the system must be calibrated.
General calibration procedures are discussed in Method 8000, while the
determinative methods and Method 5000 provide specific information on
calibration and preparation of standards. Normally, external standard
calibration is preferred for the GC methods because of possible
interference problems with internal standards. If interferences are not
a problem, based on historical data, internal standard calibration is
acceptable. The GC/MS methods normally utilize internal standard
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calibration. The GC/MS methods require instrument tuning prior to
proceeding with calibration.
7.2.1.1 Assemble a purge-and-trap device that meets the
specification in Sec. 4.2 and is interfaced to a gas chromatograph
or a gas chromatograph/mass spectrometer system. Before initial
use, a Carbopack/Carbosieve trap should be conditioned overnight at
245°C by backflushing with an inert gas flow of at least 20
mL/minute. (If other trapping materials are substituted for the
Carbopack/Carbosieve, follow the manufacturers recommendations for
conditioning. See Sec. 4.2.3.3 for guidance on conditioning the
trap.) Vent the trap effluent to the room, not to the analytical
column. Prior to daily use, the trap should be conditioned for 10
minutes at 245°C with backflushing. The trap may be vented to the
analytical column during daily conditioning; however, the column
must be run through the temperature program prior to analysis of
samples.
7.2.1.2 To prepare a calibration standard, inject an
appropriate volume of a primary dilution standard (containing
analytes and surrogates) to an aliquot of organic-free reagent water
in a volumetric flask, a gas tight syringe, or to 10 ml of this
solution in a soil vial, and inject an appropriate amount of
internal standards to the organic-free reagent water. Be sure that
the same amount of internal standards are added to each standard and
sample. The volume of organic-free reagent water used for
calibration must be the same volume used for sample analysis
(normally 10 ml). The surrogate and internal standard solutions
must be added with a syringe needle long enough to ensure addition
below the surface of the water. Prior to purging, heat the sample
vial to 40°C for 1.5 minutes.
NOTE: The device on the autosampler that introduces the solution containing the
internal standards and surrogates must be disabled during calibration.
Aqueous standards are not stable and should be discarded after one hour
unless transferred to a sample bottle (or gas tight syringe) with no
headspace and sealed immediately.
7.2.1.3 Carry out the purge-and-trap procedure as outlined in
Sec. 7.2.4.4.
7.2.1.4 Calculate response factors (RF) or calibration
factors (CF) for each analyte of interest using the procedure
described in Method 8000.
7.2.1.5 The average CF (external standards) or RF (internal
standards must be calculated for each compound. For GC/MS analysis,
a system performance check must be made before this calibration
curve is used (see Method 8260). If the purge-and-trap procedure is
used with Method 8021, evaluate the response for the following four
compounds: chloromethane; 1,1-dichloroethane; bromoform; and
1,1,2,2-tetrachloroethane. They are used to check for proper purge
flow and to check for degradation caused by contaminated lines or
active sites in the system.
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7.2.1.5.1 Chloromethane: This compound is the most
likely compound to be lost if the purge flow is too fast.
7.2.1.5.2 Bromoform: This compound is one of the
compounds most likely to be purged very poorly if the purge
flow is too slow. Cold spots and/or active sites in the
transfer lines may adversely affect response.
7.2.1.5.3 Tetrachloroethane and 1,1-dichloroethane:
These compounds are degraded by contaminated transfer lines in
purge-and-trap systems and/or active sites in trapping
materials.
7.2.1.6 When analyzing for very late eluting compounds with
Method 8021 (i.e., hexachlorobutadiene, 1,2,3-trichlorobenzene,
etc.), cross contamination and memory effects from a high
concentration sample or even the standard are a common problem.
Extra rinsing of the purge chamber after analysis normally corrects
this. The newer purge-and-trap systems often overcome this problem
with better bakeout of the system following the purge-and-trap
process. Also, the charcoal traps retain less moisture and decrease
the problem.
7.2.2 Calibration verification: Refer to Method 8000 for details
on calibration verification.
7.2.2.2 To prepare a calibration standard, inject an
appropriate volume of a primary dilution standard (containing
analytes and surrogates) to an aliquot of organic-free reagent water
in a volumetric flask, a gas tight syringe, or to 10 ml of this
solution in a soil vial, and inject an appropriate amount of
internal standards to the organic-free reagent water. Be sure the
same amount of internal standards are added to each standard and
sample. The volume of organic-free reagent water used for
calibration must be the same volume used for sample analysis
(normally 10 mL). The surrogate and internal standard solutions
must be added with a syringe needle long enough to ensure addition
below the surface of the water. Assemble the purge-and-trap device
as outlined in 7.2.4.2. Prior to purging, heat the sample vial to
40°C for 1.5 minutes. Follow the guidance for the purge-and-trap
procedure in Sec. 7.2.4.4. GC or GC/MS calibration verification
criteria must be met as specified in Method 8000 before analyzing
samples.
NOTE: The device on the autosampler that introduces the solution containing the
internal standards and surrogates must be disabled during calibration.
Aqueous standards are not stable and should be discarded after one hour
unless transferred to a sample bottle (or gas tight syringe) with no
headspace and sealed immediately.
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7.2.3 Sample screening
7.2.3.1 It is highly recommended that all samples be screened
prior to the purge-and-trap GC or GC/MS analysis. These samples may
contain percent quantities of purgeable organics that will
contaminate the purge-and-trap system thereby requiring extensive
cleanup and instrument downtime. See Sec. 7.2.3.2 for suggested
screening techniques. Use the screening data to determine whether
to use the Low Concentration closed-system purge-and-trap or to
prepare samples by the High Concentration method.
7.2.3.2 Two suggested screening techniques are: the use of
an automated headspace sampler (Method 5021) interfaced to a gas
chromatograph (GC) equipped with a photo ionization detector (PID)
and an electrolytic conductivity detector (HECD) in series; or,
extraction of the sample with hexadecane (Method 3820) and analysis
of the extract on a GC equipped with a FID and/or an ECD. Use the
Low Concentration closed-system purge-and-trap if the estimated
concentration falls within the calibration range of the selected
determinative method. If the concentration exceeds the calibration
range, then prepare the samples by the High Concentration method
(Sec. 7.3).
7.2.4 Sample purge-and-trap
7.2.4.1 This method is designed for a 5-g sample size, but
other amounts (1 to 10 g) may be used. The soil vial is
hermetically sealed at the sampling site, and MUST remain so to
guarantee the validity of the sample. Gloves must be worn when
handling the sample vial since the vial has been tared. If any soil
is noted on the exterior of the vial or cap, it must be carefully
removed prior to weighing. Weigh the vial and contents to the
nearest 0.1 g unless the sample weight was determined in the field.
7.2.4.2 Assemble a purge-and-trap device that meets the
specification in Sec. 4.2. Before initial use, a
Carbopack/Carbosieve trap should be conditioned overnight at 245°C
by backflushing with an inert gas flow of at least 20 mL/minute.
(If other trapping materials are substituted for the
Carbopack/Carbosieve, follow the manufacturers recommendations for
conditioning. See Sec. 4.2.3.3 for guidance on conditioning the
trap.) Vent the trap effluent to the room, not to the analytical
column. Prior to daily use, the trap should be conditioned for 10
minutes at 245°C with backflushing. The trap may be vented to the
analytical column during daily conditioning; however, the column
must be run through the temperature program prior to analysis of
samples.
7.2.4.3 Without disturbing the hermetic seal on the sample
vial, add 10 mL of organic-free reagent water, the internal
standards, and the surrogate compounds. This is carried out using
the automated sampler. Other volumes of organic-free reagent water
may be used. However, it is imperative that all samples, blanks,
and calibration standards have exactly the same final volume of
5035 - 9 Revision 0
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organic-free reagent water. For the sample selected for matrix
spiking, add 10 /iL of the matrix spike solution specified in Sec.
5.0 of Method 5000. The concentration for a 5 g sample would be
equivalent to 50 M9/kg of each matrix spike analyte. Prior to
purging, heat the sample vial to 40°C for 1.5 minutes.
7.2.4.4 Purge the sample at a flow rate of 40 mL/minute (the
flow rate may vary from 20 to 40 mL/min depending in the target
analyte group) with helium or another inert gas for 11 minutes while
the sample is being agitated. The purged analytes are allowed to
flow out of the vial through a glass-lined transfer line to a trap
packed with suitable sorbent materials.
7.2.5 Sample Desorption
7.2.5.1 Non-cryogenic interface - After the 11 minute purge,
place the purge-and-trap system in the desorb mode and preheat the
trap to 245°C without a flow of desorption gas. Then,
simultaneously, start the flow of desorption gas at 10 mL/minute for
about four minutes (1.5 min is normally adequate for analytes in
Method 8015); begin the temperature program of the gas
chromatograph; and start data acquisition.
7.2.5.2 Cryogenic interface - After the 11 minute purge,
place the purge-and-trap system in the desorb mode, make sure the
cryogenic interface is -150°C or lower, and rapidly heat the trap to
245eC while backflushing with an inert gas at 4 mL/minute for about
5 minutes (1.5 min is normally adequate for analytes in Methods
8015). At the end of the 5-minute desorption cycle, rapidly heat
the cryogenic trap to 250"C; simultaneously begin the temperature
program of the gas chromatograph and start the data acquisition.
7.2.6 Trap Reconditioning
7.2.6.1 After desorbing the sample for 4 minutes, recondition
the trap by returning the purge-and-trap system to the purge mode.
Maintain the trap temperature at 245°C (dependent on trap packing
materials). After approximately 10 minutes, turn off the trap
heater and halt the purge flow through the trap. When the trap is
cool the next sample can be analyzed.
7.2.7 Data Interpretation
7.2.7.1 Perform qualitative and quantitative analysis on the
data following the guidance given in the determinative method and
Method 8000. If concentrations of any target analyte exceeds the
calibration range of the analyte, it will be necessary to reanalyze
the sample by the High Concentration Method.
7.2.8 Determination of % Dry Weight
7.2.8.1 Weigh 5-10 g of the sample from the 60 mL VGA vial
into a tared crucible.
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NOTE: It Is highly recommended that no samples for dry weight determination be
withdrawn from the 60 ml VGA vial until it is certain that no analytical
samples will be needed for High Concentration analysis. This is to
minimize loss of volatiles and to avoid sample contamination from the
laboratory atmosphere.
7.2.8.2 Determine the % dry weight of the sample by drying
overnight at 105"C. Allow to cool in a desiccator before weighing:
% dry weight = q of dry sample x 100
g of sample
WARNING: The drying oven should be contained in a hood or vented.
Significant laboratory contamination may result from a heavily
contaminated hazardous waste sample.
7.3 High Concentration Method for Soil, Solid Waste and Nonaqueous Liquid
Waste with Concentrations Generally Greater Than 200
7.3.1 The method for soil is based on a methanol extraction. A
waste sample is either extracted or diluted, depending on its solubility
in methanol. Wastes (i.e. petroleum and coke wastes) that are insoluble
in methanol are diluted with hexadecane (Sec. 7.3.1.6) or possibly
polyethylene glycol (PEG). (Perform a solubility test with about one gram
of sample and 10 mL of each solvent if the solubility is unknown, before
proceeding. Discard this test solution.) An aliquot of the extract is
added to organic-free reagent water containing surrogate and, if
applicable, internal and matrix spiking standards. This is analyzed
according to Method 5030.
7.3.1.1 The sample (for volatile organics) consists of the
entire contents of the sample container. Do not discard any
supernatant liquids. Mix the contents of the sample container with
a narrow metal spatula.
7.3.1.2 For soil and solid waste that is insoluble in
methanol, weigh 4 g (wet weight) of sample into a tared 20 ml vial.
Use a top-loading balance. Note and record the actual weight to 0.1
gram and determine the percent dry weight of the sample using the
procedure in Sec. 7.1.8. Quickly add 9.0 mL of methanol; then add
1.0 mL of the surrogate spiking solution to the vial. Cap and shake
for 2 min.
7.3.1.3 For waste that is soluble in methanol or PEG weigh
1 g (wet weight) into a tared scintillation vial or culture tube or
a 10 mL volumetric flask. (If a vial or tube is used, it must be
calibrated prior to use. Pipet 10.0 mL of methanol into the vial
and mark the bottom of the meniscus. Discard this solvent.)
Quickly add 1.0 mL of surrogate spiking solution to the vial or
flask and dilute to 10.0 mL with the appropriate solvent. Shake the
vial to mix the contents. For certain oily liquids, the following
methanol dilution/extraction has proved effective. Shake 1 g of
oily liquid with 10 mL of methanol (2 minute shake) which results in
the target analytes being extracted into the methanol along with the
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majority of the oily waste (some of the oil may still be floating on
the surface). If oil is floating on the surface, transfer 1 to 2 ml
to a clean GC vial using a Pasteur pipet. Ensure that no oil is
transferred to the vial. Add 10 - 50 /j.1 of the methanol extract to
5 ml of organic-free reagent water for purge-and-trap analysis.
Prior to using this technique, test it by spiking a 1 g aliquot of
the oily waste with a matrix spike mixture of the analytes of
concern (10 - 50 jiL of the matrix spike standard dissolved in
methanol). Shake the vial to disperse the matrix spike throughout
the oil prior to adding the 10 mL of methanol extraction solvent.
Compare the data with single-lab data for oily waste presented in
Method 8260. If recovery is not within the limits presented for the
majority of compounds, use the hexadecane dilution technique in Sec.
7.3.1.6.
NOTE: Sections 7.3.1.1 through 7.3.1.3 must be performed rapidly and without
interruption to avoid loss of volatile organics. These steps must be
performed in a laboratory free from solvent fumes.
7.3.1.4 Pipet approximately 1 mL of the extract into a GC
vial for storage, using a disposable pipet. The remainder may be
discarded. Transfer approximately 1 mL of solvent used for
extraction or dissolution to a separate GC vial for use as the
method blank for each set of samples.
7.3.1.5 The extracts must be stored at 4°C in the dark, prior
to analysis. An appropriate aliquot of the extract (see Table 2)
will be added to 5 mL of organic-free reagent water and analyzed as
per Method 5030. Proceed to Sec. 7.0 in Method 5030 and follow the
guidance for the analysis of high concentration samples.
7.3.1.6 For waste, soil or solids, where methanol or PEG are
not effective solvents (e.g., those samples consisting primarily of
petroleum or coking waste) dilute or extract with hexadecane
following the guidance in Method 3585.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 5000 for sample preparation QC procedures.
8.2 Before processing any samples, the analyst should demonstrate through
the analysis of an organic-free reagent water method blank that all glassware and
reagents are interference free. Each time a set of samples is extracted, or
there is a change in reagents, a method blank should be processed as a safeguard
against chronic laboratory contamination. The blank samples should be carried
through all stages of the sample preparation and measurement.
8.3 Standard quality assurance practices should be used with this method.
Field duplicates should be collected to validate the precision of the sampling
technique. Each analysis batch of 20 or less samples must contain: a reagent
blank; either a matrix spike/matrix spike duplicate or a matrix spike and
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duplicate sample analysis; and a laboratory control sample, unless the
determinative method provides other guidance.
8.4 Surrogate standards should be added to all samples when specified in
the appropriate determinative method.
9.0 METHOD PERFORMANCE
9.1 Single laboratory accuracy and precision data were obtained for the
method analytes in three soil matrices, sand, a soil collected 10 feet below the
surface of a hazardous landfill, called C-Horizon, and a surface garden soil.
Each sample was fortified with the analytes at a concentration of 20 ng/5 g,
which is equivalent to 4 jug/kg. These data are listed in tables found in Method
8260.
9.2 Single laboratory accuracy and precision data were obtained for
certain method analytes when extracting oily liquid using methanol as the
extraction solvent. The data are presented in a table in Method 8260. The
compounds were spiked into three portions of an oily liquid (taken from a waste
site) following the procedure for matrix spiking described in Sec. 7.3.1.3. This
represents a worst case set of data based on recovery data from many sources of
oily liquid.
10.0 REFERENCES
1. Bellar, T., "Measurement of Volatile Organic Compounds in Soils Using
Modified Purge-and-Trap and Capillary Gas Chromatography/Mass
Spectrometry" U.S. Environmental Protection Agency, Environmental
Monitoring Systems Laboratory, Cincinnati, OH, November 1991.
2. Strattan, L., Private communication on methanol extraction of oil, U.S.
Environmental Protection Agency, National Enforcement Investigations
Center, Denver, CO, October, 1992.
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TABLE 1
QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF
HIGH-CONCENTRATION SOILS/SEDIMENTS
Approximate Volume of
Concentration Range Methanol Extract8
500-10,000 /ig/kg 100 juL
1,000-20,000 MgAg so pi
5,000-100,000 /zg/kg 10 ^L
25,000-500,000 jug/kg 100 juL of 1/50 dilution6
Calculate appropriate dilution factor for concentrations exceeding this table.
8 The volume of methanol added to 5 mL of water being purged should be kept
constant. Therefore, add to the 5 mL syringe whatever volume of methanol
is necessary to maintain a volume of 100 fj,L added to the syringe.
b Dilute an aliquot of the methanol extract and then take 100 /zL for
analysis.
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FIGURE 1
DYNATECH SOIL VIAL
DYNATECH
SOIL VIAL
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72.1 & 72.2 Interface
purge & trap system to
GC or GC/MS system
and calibrate as per
proper 8000 method.
I
723 Screen sample to
ensure that it is low
concentration.
7 2.4 1 Weigh sample
unless weight was
determined in the field
7242 Prepare the
purge & trap system for
sample analysis.
724.3 Add 10 ml of
reagent water plus
surrogates and internal
standards if required.
7244 Purge the sample
at 40 C for 11 minutes
7.2.5.1 Desorption
conditions for
non-cryogenic interface.
METHOD 5035
CLOSED-SYSTEM PURGE-AND-TRAP
73 1.2 Weigh 4 g into a
20 ml vial. Add 9 ml of
methanol and 1 ml of
surrogate spike. Shake
for 2 minutes
7.3.1.4 Transfer 1 ml
of extract into a GC
vial.
73.1.3 Weigh 1 g into
a vial. Add 1 mL of
surrogate spike and
dilute to 10 ml with
methanol.
Hexadecane Soluble
7.3.1.6 Go to Method
3585.
7.3 1 5 Proceed to
Section 7 of Method
5030 for guidance on
purge & trap analysis
by GC or GC/MS.
7 2 5.2 Desorption
conditions for cryogenic
interface
7.2.6.1 Recondition
trap at appropriate temp.
\
I
7.2.7.1 Data
interpretation based on
appropriate 8000 method.
7.2.8 Determine % dry
weight for soil/sediment.
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METHOD 5041A
ANALYSIS FOR DESORPTION OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC
SAMPLING TRAIN (VOST): CAPILLARY GC/MS TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 This method describes the desorption of volatile principal organic
hazardous constituents (POHCs) collected from the stack gas effluents of
hazardous waste incinerators using the VOST methodology (1) with analysis by
GC/MS (Method 8260). For a comprehensive description of the VOST sampling
methodology see Method 0030. The following compounds may be determined by this
method:
Compound
CAS No.1
Acetone
Acrylonitrile
Benzene
Bromodi chl oromethane
Bromoformb
Bromomethane0
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chlorodibromomethane
Chl oroethane0
Chloroform
Chl oromethane0
Dibromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethyl benzene6
lodomethane
Methylene chloride
Styrene6
1,1,2 , 2-Tetrachl oroethaneb
Tetrachl oroethene
Toluene
1,1,1 -Trichl oroethane
1 , 1 , 2-Trichl oroethane
67-64-1
107-13-1
71-43-2
75-27-4
75-25-2
74-83-9
75-15-0
56-23-5
108-90-7
124-48-1
75-00-3
67-66-3
74-87-3
74-95-3
75-35-3
107-06-2
75-35-4
156-60-5
78-87-5
10061-01-5
10061-02-6
100-41-4
74-88-4
75-09-2
100-42-5
79-34-5
127-18-4
108-88-3
71-55-6
79-00-5
(continued)
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Compound CAS No.a
Trichloroethene 79-01-6
Trichlorofluoromethane 75-69-4
l,2,3-Trichloropropaneb 96-18-4
Vinyl chloride6 75-01-4
Xylenesb
a Chemical Abstract Services Registry Number.
b Boiling point of this compound is above 132°C. Method 0030 is not
appropriate for quantitative sampling of this analyte.
c Boiling point of this compound is below 30°C. Special precautions
must be taken when sampling for this analyte by Method 0030. Refer
to Section 1.3 for discussion.
1.2 This method is most successfully applied to the analysis of non-polar
organic compounds with boiling points between 30°C and 100°C. Data are applied
to the calculation of destruction and removal efficiency (ORE), with limitations
discussed below.
1.3 This method may be applied to analysis of many compounds which boil
above 100"C, but Method 0030 is always inappropriate for collection of compounds
with boiling points above 132'C. All target analytes with boiling points greater
than 132eC are so noted in the target analyte list presented in Section 1.1. Use
of Method 0030 for collection of compounds boiling between 100'C and 132°C is
often possible, and must be decided based on case by case inspection of
information such as sampling method collection efficiency, tube desorption
efficiency, and analytical method precision and bias. An organic compound with
a boiling point below 30°C may break through the sorbent under the conditions
used for sample collection. Quantitative values obtained for compounds with
boiling points below 30"C must be qualified, since the value obtained represents
a minimum value for the compound if breakthrough has occurred. In certain cases,
additional QC measures may have been taken during sampling very low boilers with
Method 0030. This information should be considered during the data
interpretation stage.
1.4 When Method 5041 is used for survey analyses, values for compounds
boiling above 132°C may be reported and qualified since the quantity obtained
represents a minimum value for the compound. These minimum values should not be
used for trial burn ORE calculations or to prove insignificant risk.
1.5 The VOST analytical methodology can be used to quantitate volatile
organic compounds that are insoluble or slightly soluble in water. When
volatile, water soluble compounds are included in the VOST organic compound
analyte list, quantitation limits can be expected to be approximately ten times
higher than quantitation limits for water insoluble compounds (if the compounds
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can be recovered at all) because the purging efficiency from water (and possibly
from Tenax-GC®) is poor.
1.6 Overall sensitivity of the method is dependent upon the level of
interferences encountered in the sample and the presence of detectable
concentrations of volatile POHCs in blanks. The target detection limit of this
method is 0.1 jug/m3 (ng/L) of flue gas, to permit calculation of a ORE equal to
or greater than 99.99% for volatile POHCs which may be present in the waste
stream at 100 ppm. The upper end of the range of applicability of this method
is limited by the dynamic range of the analytical instrumentation, the overall
loading of organic compounds on the exposed tubes, and breakthrough of the
volatile POHCs on the sorbent traps used to collect the sample. Method 8260
presents method detection limits for a range of volatile compounds analyzed by
this method interfaced to a GC/MS with wide bore capillary methodology.
1.7 This method is restricted to use by, or under the supervision of,
analysts experienced in the use of sorbent media, purge-and-trap systems, and gas
chromatograph/mass spectrometers, and skilled in the interpretation of mass
spectra and their use as a quantitative tool.
2.0 SUMMARY OF METHOD
2.1 The sorbent tubes are thermally desorbed by heating and purging with
organic-free helium. The gaseous effluent from the tubes is bubbled through
pre-purged organic-free reagent water and trapped on an analytical sorbent trap
in a purge-and-trap unit (Figure 2).
2.2 After desorption, the analytical sorbent trap is heated rapidly and
the gas flow from the analytical trap is directed to the head of a wide-bore
column under subambient conditions.
2.3 The volatile organic compounds desorbed from the analytical trap are
determined by Method 8260 (Figure 3).
3.0 INTERFERENCES
3.1 Sorbent tubes which are to be analyzed for volatile organic compounds
can be contaminated by diffusion of volatile organic compounds (particularly
Freon® refrigerants and common organic solvents) through the external container
(even through a Teflon®-!ined screw cap on a glass container) and the Swagelok®
sorbent tube caps during shipment and storage. The sorbent tubes can also be
contaminated if organic solvents are present in the analytical laboratory. The
use of blanks is essential to assess the extent of any contamination. Field
blanks need to be prepared and taken to the field. The end caps of the tubes are
removed for the period of time required to exchange two pairs of traps on the
VOST sampling apparatus. The tubes are recapped and shipped and handled exactly
as the actual field samples are shipped and handled. At least one pair of field
blanks is included with each six pairs of sample cartridges collected.
3.2 At least one pair of blank cartridges (one Tenax-GC®, one
Tenax-GC®/charcoal) must be included with shipment of cartridges to a hazardous
5041A - 3 Revision 1
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waste incinerator site as trip blanks. These trip blanks are treated like field
blanks except that the end caps are not removed during storage at the site. This
pair of traps are analyzed to monitor potential contamination which may occur
during storage and shipment.
3.3 Analytical system blanks are needed to demonstrate that contamination
of the purge-and-trap unit and the gas chromatograph/mass spectrometer has not
occurred or that, in the event of analysis of sorbent tubes with very high
concentrations of organic compounds, no compound carryover is occurring. Tenax®
from the same preparation batch as the Tenax® used for field sampling should be
used in the preparation of the method (laboratory) blanks. A sufficient number
of cleaned Tenax® tubes from the same batch as the field samples should be
reserved in the laboratory for use as blanks.
3.4 Cross contamination can occur whenever low-concentration samples are
analyzed after high-concentration samples, or when several high-concentration
samples are analyzed sequentially. When an unusually concentrated sample is
analyzed, this analysis should be followed by a method blank to establish that
the analytical system is free of contamination. If analysis of a blank
demonstrates that the system is contaminated, an additional bake cycle should be
used. If the analytical system is still contaminated after additional baking,
routine system maintenance should be performed: the analytical trap should be
changed and conditioned, routine column maintenance should be performed (or
replacement of the column and conditioning of the new column, if necessary), and
bakeout of the ion source (or cleaning of the ion source and rods, if required).
After system maintenance has been performed, analysis of a blank is needed to
demonstrate that the cleanliness of the system is acceptable.
3.5 Impurities in the purge gas and from organic compounds out-gassing in
tubing account for the majority of contamination problems. The analytical system
must be demonstrated to be free from contamination under the conditions of the
analysis by analyzing two sets of clean, blank sorbent tubes with organic-free
reagent purge water as system blanks. The analytical system is acceptably clean
when these two sets of blank tubes show values for the analytes which are within
one standard deviation of the normal system blank. Use of plastic coatings,
non-Teflon® thread sealants, or flow controllers with rubber components should
be avoided.
3.6 VOST tubes are handled in the laboratory to spike standards and to
position the tubes within the desorption apparatus. When sorbent media are
handled in the laboratory atmosphere, contamination is possible if there are
organic solvents in use anywhere in the laboratory. It is therefore necessary
to make daily use of system blanks to monitor the cleanliness of the sorbents and
the absence of contamination from the analytical system. A single set of system
blank tubes shall be exposed to normal laboratory handling procedures and
analyzed as a sample. This sample should be within one standard deviation of
normal VOST tube blanks to demonstrate lack of contamination of the sorbent
media.
3.7 If the emission source has a high concentration of non-target organic
compounds (for example, hydrocarbons at concentrations of hundreds of ppm), the
presence of these non-target compounds will interfere with the performance of the
VOST analytical methodology. If one or more of the compounds of interest
saturates the chromatographic and mass spectrometric instrumentation, no
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quantitative calculations can be made and the tubes which have been sampled under
the same conditions will yield no valid data for any of the saturated compounds.
In the presence of a very high organic loading, even if the compounds of interest
are not saturated, the instrumentation is so saturated that the linear range has
been surpassed. When instrument saturation occurs, it is possible that compounds
of interest cannot even be identified correctly because a saturated mass
spectrometer may mis-assign masses. Even if compounds of interest can be
identified, accurate quantitative calculations are impossible at detector
saturation. No determination can be made at detector saturation, even if the
target compound itself is not saturated. At detector saturation, a negative bias
will be encountered in analytical measurements and no accurate calculation can
be made for the Destruction and Removal Efficiency if analytical values may be
biased negatively.
3.8 The recoveries of the surrogate compounds, which are spiked on the
VOST tubes immediately before analysis, should be monitored carefully as an
overall indicator of the performance of the methodology. Since the matrix of
stack emissions is so variable, only a general guideline for recovery of 50-150%
can be used for surrogates. The analyst cannot use the surrogate recoveries as
a guide for correction of compound recoveries. The surrogates are valuable only
as a general indicator of correct operation of the methodology. If surrogates
are not observed or if recovery of one or more of the surrogates is outside the
50-150% range, the VOST methodology is not operating correctly. The cause of the
failure in the methodology is not obvious. The matrix of stack emissions
contains large amounts of water, may be highly acidic, and may contain large
amounts of target and non-target organic compounds. Chemical and surface
interactions may be occurring on the tubes. If recoveries of surrogate compounds
are extremely low or surrogate compounds cannot even be identified in the
analytical process, then failure to observe an analyte may or may not imply that
the compound of interest has been removed from the emissions with a high degree
of efficiency (that is, the Destruction and Removal Efficiency for that analyte
is high).
4.0 APPARATUS AND MATERIALS
4.1 Tube desorption apparatus: Acceptable performance of the methodology
requires:
1) temperature regulation to ensure that tube temperature during
desorption is regulated to 180°C ± 10°;
2) good contact between tubes and the heating apparatus to ensure that
the sorbent bed is thoroughly and uniformly heated to facilitate
desorption of organic compounds; and
3) gas-tight connections to the ends of the tubes to ensure flow of
desorption gas through the tubes without leakage during the
heating/desorption process. A simple clamshell heater which will
hold tubes which are 3/4" in outer diameter will perform acceptably
as a desorption apparatus.
4.2 Purge-and-trap device: The purge-and-trap device is described in
Method 5030, Section 4.0.
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4.2.1 The cartridge thermal desorption apparatus is connected to
the sample purge vessel by 1/8" Teflon® tubing (unheated transfer line).
The tubing which connects the desorption chamber to the sample purge
vessel should be as short as is practical.
4.2.2 The sample purge vessel is required to hold 5 ml of
organic-free reagent water, through which the gaseous effluent from the
VOST tubes is routed.
4.3 The gas chromatograph/mass spectrometer/data system and recommended
GC columns are described in Method 8260, Section 4.0.
4.4 Wrenches: 9/16", 1/2", 7/16", and 5/16".
4.5 Teflon® tubing: 1/8" diameter.
4.6 Syringes: 25 juL syringes (2), 10 p.1 syringes (2).
4.7 Fittings: 1/4" nuts, 1/8" nuts, 1/16" nuts, 1/4" to 1/8" union, 1/4"
to 1/4" union, 1/4" to 1/16" union.
4.8 Adjustable stand to raise the level of the desorption unit, if
necessary.
4.9 Volumetric flasks: 5 ml, class A with ground glass stopper.
4.10 Injector port or equivalent, heated to 180"C for loading standards
onto VOST tubes prior to analysis.
4.11 Vials: 2 ml, with Teflon®-lined screw caps or crimp tops.
4.12 Syringe: 5 mL, gas-tight with shutoff valve.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
NOTE: It is advisable to maintain the stock of organic-free reagent water
generated for use in the purge-and-trap apparatus with a continuous stream
of inert gas bubbled through the water. Continuous bubbling of the inert
gas maintains a positive pressure of inert gas above the water as a
safeguard against contamination.
5041A - 6 Revision 1
January 1995
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5.3 Methanol, CH3OH. Pesticide quality or equivalent. To avoid
contamination with other laboratory solvents, it is advisable to maintain a
separate stock of methanol for the preparation of standards for VOST analysis and
to regulate the use of this methanol very carefully.
5.4 Surrogate standards: The recommended surrogates are listed in Method
8260, Section 5.0. A stock surrogate compound solution in high purity methanol
should be prepared as described in Section 5.0, Method 8260, and a surrogate
standard spiking solution should be prepared from the stock at a concentration
of 250 M9/10 mL in high purity methanol. Each pair of VOST tubes (or each
individual VOST tube, if the tubes are analyzed separately) must be spiked with
10 )LtL of the surrogate spiking solution prior to GC/MS analysis.
5.5 Internal standards: The recommended internal standards for GC/MS
analysis are listed in Method 8260, Section 5.0. Prepare internal standard stock
and secondary dilution standards in high purity methanol using the procedures
described in Section 5.0 of Method 8260. The secondary dilution standard should
be prepared at a concentration of 25 mg/L of each of the internal standard
compounds. Addition of 10 juL of this internal standard solution to each pair
of VOST tubes (or to each VOST tube, if the tubes are analyzed individually) is
the equivalent of 250 ng total.
5.6 Great care must be taken to maintain the integrity of all standard
solutions. All standards of volatile compounds in methanol should be stored at
-10°C to -20"C in amber bottles with Teflon®-!ined screw caps or crimp tops.
In addition, careful attention must be paid to the use of syringes designated for
a specific purpose or for use with only a single standard solution since cross
contamination of volatile organic standards can occurs very readily.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Method 0030 for the VOST Sampling Methodology.
6.2 VOST samples are collected on paired cartridges. The first of the
pair of sorbent cartridges is packed with approximately 1.6 g of Tenax-GC®
resin. The second cartridge of the pair is packed with Tenax-GC® and petroleum
based charcoal (3:1 by volume; approximately 1 g of each). In sampling, the
emissions gas stream passes through the Tenax-GC® layer first and then through
the charcoal layer. The Tenax-GC® is cleaned and reused; charcoal is not reused
when tubes are prepared. Sorbent is cleaned and the tubes are packed. The tubes
are desorbed and subjected to a blank check prior to being sent to the field.
When the tubes are used for sampling (see Figure 5 for a schematic diagram of the
Volatile Organic Sampling Train (VOST)), cooling water is circulated to the
condensers and the temperature of the cooling water is maintained near 0"C. The
end caps of the sorbent cartridges are placed in a clean, screw capped glass
container during sample collection.
6.3 After the apparatus is leak checked, sample collection is accomplished
by opening the valve to the first condenser, turning on the pump, and sampling
at a rate of 1 liter/min for 20 minutes. The volume of sample for any pair of
traps should not exceed 20 liters. An alternative set of conditions for sample
collection requires sampling at a reduced flow rate, where the overall volume of
5041A - 7 Revision 1
January 1995
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sample collected is 5 liters at a rate of 0.25 L/min for 20 minutes. The 20
minute period is necessary for collecting an integrated sample.
6.4 Following collection of 20 liters of sample, the train is leak checked
a second time at the highest pressure drop encountered during the run to minimize
the chance of vacuum desorption of organics from the Tenax®.
6.5 The train is returned to atmospheric pressure and the two sorbent
cartridges are removed. The end caps are replaced and the cartridges are placed
in a suitable environment for storage and transport until analysis. The sample
is considered invalid if the leak test does not meet specifications.
6.6 A new pair of cartridges is placed in the VOST, the VOST is leak
checked, and the sample collection process is repeated until six pairs of traps
have been exposed.
6.7 All sample cartridges are kept in coolers on cold packs after exposure
and during shipment. Upon receipt at the laboratory, the cartridges are stored
in a refrigerator at 4°C until analysis.
i
7.0 PROCEDURE
7.1 Recommended operating conditions for cartridge desorber and
purge-and-trap unit, are:
Cartridge Desorption Oven
Desorb Temperature
Desorb Time
Desorption Gas Flow
Desorption/Carrier Gas
Purge-and-Trap Concentrator
Analytical Trap Desorption Flow
Purge Temperature
Purge Time
Analytical Trap Desorb Temp.
Analytical Trap Desorb Time
Gas Chromatograph
Column
Carrier Gas Flow
Makeup Gas Flow
Injector Temperature
Transfer Oven Temperature
Initial Temperature
Initial Hold Time
Program Rate
Final Temperature
Final Hold Time
180'C
11 minutes
40 mL/min
Helium, Grade
5.0
2.5 mL/min
Ambient
11 minutes
180°C
5 minutes
helium
30 m x 0.53 mm ID,
(J&W Scientific), 3
thickness, or equivalent
15 mL/min
15 mL/min
200°C
240°C
5°C
2 minutes
6°C/min
coated with DB-624
m film
240°C
1 minute or until
elution ceases
5041A - 8
Revision 1
January 1995
i
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Mass Spectrometer
Manifold Temperature 105*C
Scan Rate 1 sec/cycle
Mass Range 35-260 amu
Electron Energy 70 eV (nominal)
Source Temperature According to manufacturer's
specifications
7.2 Each GC/MS system must be hardware tuned to meet the BFB criteria in
Method 8260.
7.3 Assemble and operate a purge-and-trap device as per Method 5030.
7.4 Connect the purge-and-trap device to a gas chromatograph.
7.5 Assemble a VOST tube desorption apparatus which meets the requirements
of Section 4.1.
7.6 Connect the VOST tube desorption apparatus to the purge-and-trap unit.
7.7 Spiking standards onto VOST tubes: For this procedure, the system
will be calibrated using the internal standard procedure. Internal standards,
surrogates, and calibration standards in methanolic solution will be spiked onto
cleaned VOST tubes for proper calibration of the system. These standards are
spiked onto VOST tubes using the flash evaporation technique. To perform flash
evaporation, the injector of a gas chromatograph or an equivalent piece of
equipment is required.
7.7.1 Prepare a syringe with the appropriate volume of methanolic
standard solution (either surrogates, internal standards, or calibration
compounds).
7.7.2 With the injector port heated to 180°C, and with an inert gas
flow of 10 mL/min through the injector port, connect the paired VOST tubes
(connected as in Figure 1, with gas flow in the same direction as the
sampling gas flow) to the injector port; tighten with a wrench so that
there is no leakage of gas. If separate tubes are being analyzed, an
individual Tenax® or Tenax®/charcoal tube is connected to the injector.
7.7.3 After directing the gas flow through the VOST tubes, slowly
inject the first standard solution over a period of 25 seconds. Wait for
5 seconds before withdrawing the syringe from the injector port.
7.7.4 Inject a second standard (if required) over a period of 25
seconds and wait for 5 seconds before withdrawing the syringe from the
injector port.
7.7.5 Repeat the sequence above, as required, until all of the
necessary compounds are spiked onto the VOST tubes.
7.7.6 Wait for 30 seconds, with gas flow, after the last spike
before disconnecting the tubes. The total time the tubes are connected to
the injector port with gas flow should not exceed 2.5 minutes. Total gas
flow through the tubes during the spiking process should not exceed 25 mL
5041A - 9 Revision 1
January 1995
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to prevent break-through of adsorbed compounds during the spiking process.
To allow more time for connecting and disconnecting tubes, an on/off valve
may be installed in the gas line to the injector port so that gas is not
flowing through the tubes during the connection/disconnection process.
7.8 Prepare the purge-and-trap unit with 5 ml of organic-free reagent
water in the purge vessel.
7.9 Connect the paired VOST tubes to the gas lines in the tube desorption
unit. The tubes must be connected so that the gas flow during desorption will
be opposite to the flow of gas during sampling: i.e., the tube desorption gas
passes through the charcoal portion of the tube first. An on/off valve may be
installed in the gas line leading to the tube desorption unit in order to prevent
flow of gas through the tubes during the connection process.
7.10 Initiate tube desorption/purge and heating of the VOST tubes in the
desorption apparatus.
7.11 Cool the oven of the gas chromatograph to subambient temperature with
liquid nitrogen.
7.12 Prepare the GC/MS system for data acquisition as per Method 8260.
7.13 At the conclusion of the tube/water purge time, attach the analytical
trap to the gas chromatograph, adjust the purge-and-trap device to the desorb
mode, and initiate the gas chromatographic program and the GC/MS data
acquisition. Perform the remainder of the purge and trap process as described
in Method 5030, Section 7.0.
7.14 Initial calibration for the analysis of VOST tubes: It is essential
that calibration be performed in the mode in which analysis will be performed.
If tubes are being analyzed as pairs, calibration standards should be prepared
on paired tubes. If tubes are being analyzed individually, a calibration should
be performed on individual Tenax® only tubes and Tenax®/charcoal tubes.
7.14.1 Prepare the calibration standards by spiking VOST tubes
using the procedure described in Section 7.7. Spike each pair of VOST
tubes (or each of the individual tubes) immediately before analysis.
Perform the calibration analyses in order from low concentration to high
to minimize the compound carryover. Add 5.0 ml of organic-free reagent
water to the purging vessel. Initiate tube desorb/purge according to the
procedure.
7.14.2 Continue the initial calibration process as described in
Method 8260, Section 7.0. The same criteria for SPCC, CCC and linearity
must be met.
7.15 GC/MS Calibration Verification
7.15.1 Prior to the analysis of samples, purge 5-50 ng of the
4-bromofluorobenzene standard. The resultant mass spectrum for BFB must
meet all of the criteria given in Method 8260 before sample analysis
begins. These criteria must be demonstrated every twelve hours of
operation.
5041A - 10 Revision 1
January 1995
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7.15.2 Perform calibration verification as per Method 8260, Section
7.0. The same criteria for SPCC, linearity and internal standard response
check must be met. See the next section for special guidance on the CCCs.
7.15.3 If the percent difference for any compound is greater than
20, the laboratory should consider this a warning limit. Benzene, toluene,
and styrene will have problems with response factors if Tenax®
decomposition occurs (either as a result of sampling exposure or
temperature degradation), since these compounds are decomposition products
of Tenax®. If the percent difference for each CCC is less than 25%, the
initial calibration is assumed to be valid. If the criterion of percent
difference less than 25% is not met for any one CCC, corrective action
MUST be taken. If a source of the problem cannot be determined after
corrective action is taken, a new five-point calibration curve MUST be
generated. The criteria for the CCCs MUST be met before quantitative
analysis can begin.
7.15.4 Internal standard responses and retention times in the
calibration verification standard must be evaluated immediately after or
during data acquisition. A factor which may influence the retention times
of the internal standards on sample tubes is the level of overall organic
compound loading on the VOST tubes. If the VOST tubes are very highly
loaded with either a single compound or with multiple compounds, retention
times for standards and compounds of interest will be affected. If the
area for the primary ion of any of the internal standards changes by a
factor of two (-50% to +100%) from the last calibration verification
standard, the gas chromatograph and mass spectrometer should be inspected
for malfunctions and corrections must be made, as appropriate. If the
level of organic loading of samples is high, areas for the primary ions of
both compounds of interest and standards will be adversely affected.
Calibration verification standards should not be subject to variation,
since the concentrations of organic compounds on these samples are set to
be within the linear range of the instrumentation. If instrument
malfunction has occurred, analyses of samples performed under conditions
of malfunction may be invalidated.
7.16 GC/MS Analysis of Samples
7.16.1 Set up the cartridge desorption unit, purge-and-trap unit
(Method 5030), and GC/MS (Method 8260) as described above or as described
in the indicated methods.
7.16.2 BFB tuning criteria and GC/MS calibration verification
criteria in Method 8260 must be met before analyzing samples. (See Sec.
7.15)
7.16.3 Adjust the helium purge gas flow rate (through the
cartridges and purge vessel) to approximately 40 mL/min. Optimize the
flow rate to provide the best response for chloromethane and bromoform, if
these compounds are analytes. A flow rate which is too high reduces the
recovery of chloromethane, and an insufficient gas flow rate reduces the
recovery of bromoform.
5041A - 11 Revision 1
January 1995
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7.16.4 The first analysis performed after the tuning check and the
calibration or calibration verification should be a method blank. The
method blank consists of clean VOST tubes (both Tenax® and
Tenax®/charcoal) which are spiked with surrogate compounds and internal
standards according to the procedure described in Section 7.7. The tubes
which are used for the method blanks should be from the same batch of
sorbent as the sorbent used for the field samples. After the tubes are
cleaned and prepared for shipment to the field, sufficient pairs of tubes
should be retained from the same batch in the laboratory to provide method
blanks during the analysis.
7.16.5 Use organic-free reagent water as described in Chapter One
for the purge vessel.
7.16.6 If the analysis of a pair of VOST tubes has a concentration
of analytes that exceeds the initial calibration range, no reanalysis of
desorbed VOST tubes is possible. An additional calibration point can be
added to bracket the higher concentration encountered in the samples so
that the calibration database encompasses six or more points.
Alternatively, the data may be flagged in the report as "extrapolated
beyond the upper range of the calibration."
7.16.7 The use of the secondary ions shown in Method 8260 is
permissible only in the case of interference with the primary quantitation
ion. Use of secondary ions to calculate compound concentration in the
case of saturation of the primary ion is not an acceptable procedure,
since a negative bias of an unpredictable magnitude is introduced into the
quantitative data when saturation of the mass spectrum of a compound is
encountered.
7.16.8 If high organic loadings, either of a single compound or of
multiple compounds, are encountered, it is vital that a method blank be
analyzed prior to the analysis of another sample to demonstrate that no
compound carryover is occurring. If concentrations of organic compounds
are sufficiently high that carryover problems are profound, extensive
bakeout of the purge-and-trap unit is necessary. More extensive guidance
on corrective maintenance of the purge and trap and GC/MS system are found
in Section 7.0 of their respective methods (Method 5030 and Method 8260).
7.17 Qualitative analysis: Follow the procedure on qualitative analysis
found in Section 7.0 of Method 8260.
7.18 Quantitative analysis: See Method 8260 for overall information on
alternative approaches to quantitation.
7.18.1 Calculate the amount in ng of each identified analyte from
the VOST tubes following the guidance on calculations presented in Section
7.0 of Method 8260.
7.18.2 The choice of methods for evaluating data collected using
the VOST methodology for incinerator trial burns is a regulatory decision.
Contact the local regulatory agencies to which VOST data are submitted for
information on data reporting preferences.
5041A - 12 Revision 1
January 1995
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7.18.3 The total amount of the POHCs of interest collected on a
pair of traps should be summed.
7.18.4 The occurrence of high concentrations of analytes on method
blank cartridges indicates possible residual contamination of sorbent
cartridges prior to shipment and use at the sampling site. Data with high
associated blank values must be qualified with respect to validity, and
all blank data should be reported separately. No blank corrections should
be made in this case. Whether or not data of this type can be applied to
the determination of destruction and removal efficiency is a regulatory
decision. Continued observation of high concentrations of analytes on
blank sorbent cartridges indicates that procedures for cleanup and quality
control for the sampling tubes are inadequate. Corrective action must be
applied to tube preparation and monitoring procedures to maintain method
blank concentrations below detection limits for analytes.
7.18.5 Where applicable, an estimate of concentration for
noncalibrated components in the sample may be made. Follow the guidance
in Method 8260, Section 7.0 that covers this issue.
7.18.6 If any internal standard recoveries fall outside the control
limits established in Section 8.4, data for all analytes determined for
that cartridge(s) must be qualified with the observation. Report results
without correction for surrogate compound recovery data. When duplicates
are analyzed, report the data obtained with the sample results.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Section 8.0 of Methods 5000 and 8000 for
specific quality control procedures. Each laboratory using SW-846 methods should
maintain a formal quality assurance program.
8.2 Before processing any samples, the analyst should demonstrate, through
the analysis of a method blank (laboratory blank sorbent tubes, reagent water
purge) that interferences from the analytical system, glassware, sorbent tube
preparation, and reagents are under control. Each time a new batch of sorbent
tubes is analyzed, a method blank should be processed as a safeguard against
chronic laboratory contamination. Blank tubes which have been carried through
all the stages of sorbent preparation and handling should be used in the
analysis.
8.3 Initial Demonstration of Proficiency - Each laboratory must
demonstrate initial proficiency with each sample preparation and determinative
method combination it utilizes, by generating data of acceptable accuracy and
precision for target analytes in a clean matrix. The laboratory should also
repeat the following operations whenever new staff are trained or significant
changes in instrumentation are made. See Section 8.0 of Methods 5000 and 8000
for information on how to accomplish this demonstration.
8.3.1 A reference sample concentrate is needed containing each
analyte at a concentration of 10 mg/L in high purity methanol. The
reference sample concentrate may be prepared from pure standard materials
or purchased as certified solutions. If the reference sample concentrate
5041A - 13 Revision 1
January 1995
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is prepared by the laboratory, it must be prepared using stock standards
prepared independently from the stock standards used for calibration.
8.3.2 Spike four pairs of cleaned, prepared VOST tubes with 10 ^L
of the QC check sample concentrate and analyze these spiked VOST tubes
according to the method beginning in Section 7.0.
8.3.3 Calculate the average recovery (X) in ng and the standard
deviation of the recovery (s) in ng for each analyte using the results of
the four analyses.
8.3.4 The average recovery and standard deviation must fall within
the expected range for determination of volatile organic compounds using
the VOST analytical methodology. The expected range for recovery of
volatile organic compounds using this method is 50-150%. Standard
deviation will be compound dependent, but should, in general, range from
15 to 30 ng. More detailed method performance criteria must be generated
from historical records in the laboratory or from interlaboratory studies
coordinated by the Environmental Protection Agency. Since the additional
steps of sorbent tube spiking and desorption are superimposed upon the
methodology of Method 8260, direct transposition of Method 8260 criteria
is questionable. If the recovery and standard deviation for all analytes
meet the acceptance criteria, the system performance is acceptable and the
analysis of field samples may begin. If any individual standard deviation
exceeds the precision limit or any individual recovery falls outside the
range for accuracy, then the system performance is unacceptable for that
analyte. See also further information on this subject found in Method
8000, Section 8.0.
8.4 Sample Quality Control for Preparation and Analysis - See Section 8.0
in Method 5000 and Method 8000 for procedures to follow to demonstrate acceptable
continuing performance on each set of samples to be analyzed. This includes the
method blank (Section 8.2), a laboratory control sample (LCS) and the addition
of surrogates to each sample and QC sample.
8.4.1 The LCS is prepared by spiking reference sample concentrate
(noted in Section 8.3) onto a clean VOST tube.
8.4.2 If surrogate recovery is not within the limits established by
the laboratory, the following procedures are necessary: (1) Verify that
there are no errors in calculations, preparation of surrogate spiking
solutions, and preparation of internal standard spiking solutions. Also,
verify that instrument performance criteria have been met. (2) Recalculate
the data and/or analyze a replicate sample, if replicates are available.
(3) If all instrument performance criteria are met and recovery of
surrogates from spiked blank VOST tubes (analysis of a method blank) is
acceptable, the problem is due to the matrix. Emissions samples may be
highly acidic and may be highly loaded with target and non target organic
compounds. Both of these conditions will affect the ability to recover
surrogate compounds which are spiked on the field samples. The surrogate
compound recovery is thus a valuable indicator of the interactions of
sampled compounds with the matrix. If surrogates spiked immediately
before analysis cannot be observed with acceptable recovery, the
implications for target organic analytes which have been sampled in the
5041A - 14 Revision 1
January 1995
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field must be assessed very carefully. If chemical or other interactions
are occurring on the exposed tubes, the failure to observe an analyte may
not necessarily imply that the Destruction and Removal Efficiency for that
analyte is high.
9.0 METHOD PERFORMANCE
9.1 Method detection limit (MDL) is defined in Chapter One. The MDL
actually achieved in a given analysis will vary depending upon instrument
sensitivity and the effects of the matrix.
9.2 The MDL concentrations for VOST analytes can be found in Section 9.0
of Method 8260.
10.0 REFERENCES
1. Protocol for Collection and Analysis of Volatile POHCs Using VOST.
EPA/600/8-84-007, March, 1984.
2. Validation of the Volatile Organic Sampling Train (VOST) Protocol.
Volumes I and II. EPA/600/4-86-014A, January, 1986.
3. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for
Analysis of Pollutants Under the Clean Water Act, Method 624," October 26,
1984.
4. Bellar, T. A., and J.J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
739-744, 1974.
5. Bellar, T. A., and J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds," in Van Hall, ed., Measurement of Organic Pollutants in Water
and Wastewater, ASTM STP 686, pp 108-129, 1979.
5041A - 15 Revision 1
January 1995
-------
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METHOD 5041A
ANALYSIS FOR DESORPTION OF SORBENT CARTRIDGES FROM
VOLATILE ORGANIC SAMPLING TRAIN (VOST): CAPILLARY COLUMN TECHNIQUE
7.1 Establish
conditions for
cartridge desorp-
tion oven, purge-
and-trap concentrator,
GC, and MS.
7.2 Tune GC/MS
with BFB and
check calibration
curve (see
Section 7.1 5).
7.3 - 7.6
Assemble the
system.
7.7. Calibrate the
instrument system
using the internal std.
procedure. Stds. and
calibration compounds
are spiked into cleaned
VOST tubes using the
flash evaporation
technique.
7.8 Prep the
purge-and-trap
unit with 5 mL
organic-free
reagent water.
7.9 Connect
paired VOST
tubes to the
gas lines for
desorption.
7.10 Initiate
tube desorption/
purge and
heating.
7.1 1 Set the GC
oven to subambient
temperature
with liquid
nitrogen.
7.12 Prep the
GC/MS system
for data
aquisition.
7.13 After the tube/
water purge time,
attach the
analytical trap to
the GC/MS for
desorption.
7.14 Perform initial
calibration of VOST
tubes.
7.15 Calibrate GC/MS
and perform SPCC
and CCC calibration
verification.
7.16 GC/MS
analysis of
samples.
7.17 Qualitative
analysis of data;
refer to
Method 8260,
Section 7.0.
7.18 Quantitative
analysis of data for
compounds of
interest.
( Stop |
5041A - 21
Revision 1
January 1995
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4.2 SAMPLE PREPARATION METHODS
4.2.2 CLEANUP
The following methods are included in this section:
Method 3600C:
Method 3610B:
Method 3611B:
Method
Method
Method
Method
Method
Method
3620B:
3630C:
3640A:
3650B:
3660B:
3665A:
Cleanup
Alumina Cleanup
Alumina Column Cleanup and Separation of
Petroleum Wastes
Florisil Cleanup
Silica Gel Cleanup
Gel-Permeation Cleanup
Acid-Base Partition Cleanup
Sulfur Cleanup
Sulfuric Acid/Permanganate Cleanup
FOUR - 9
Revision 3
January 1995
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