SW84632
FINAL (PROMULGATED) UPDATES II AND MA
Cover Sheet
THIS PACKET CONTAINS NEW AND REVISED MATERIAL
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. This section explains how to put together your SW-846
manual.
A. Instructions for New Subscribers.
B. Instructions for Previous Subscribers.
3. Method Status Table. The Method Status Table is a sequentially
numbered listing of all SW-846 methods and their current status.
4. Revised Update II Table of Contents. The Table of Contents (dated
September 1994) lists all of the methods (Third Edition, Update I, and
Updates II and IIA) in the order in which they should appear in the
manual.
5. Revised Chapter Two: Choosing the Right Method
6. Revised Chapter Three and new/revised methods for metals analyses.
7. Revised Chapter Four and new/revised methods for organic analyses.
8. Revised Chapter Five and new/revised methods for miscellaneous
analyses.
9. Revised Chapter Six and new/revised methods for properties analyses.
10. Revised Chapter Seven: Introduction and Regulatory Definitions
11. Revised Chapter Eight (Revised section separation sheets only)
-------
INSTRUCTIONS
SW-846 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 issues these methods as updates to the
manual. To date, the Agency has issued Final Updates I, II, and IIA. These
instructions include directions on getting the basic manual up-to-date and
incorporating Final Updates II and IIA into your SW-846. 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).
If you have any difficulty with these directions, you may telephone the Methods
Information Communication Exchange (MICE) at 703-821-4789 for help. If
you have questions concerning your SW-846 U.S. Government Printing Office
(GPO) subscription, you should telephone the GPO at 202-512-2303. If you
did not purchase your SW-846 from the GPO, the GPO will not be able to help
you.
FINAL UPDATE IIA; Final Update IIA contains only one method, Method
4010, dated August 1993. This method was promulgated on January 4, 1994
(59 FR 458). It should be inserted into the manual according to the location
specified in the Final Update II Table of Contents (dated September 1994).
FINAL UPDATE II; Final Update II has been promulgated and is now
officially part of SW-846. These instructions for insertion of Final Update II
are divided into two (2) sections: Section A - Instructions for New Subscribers
and Section B - Instructions for Previous Subscribers.
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, and a copy of Final Updates II and IIA.
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 Final Update II and IIA package in the mail.
Update II and IIA Instructions - 1 Final
-------
Please use the following instructions for new subscribers or previous V
subscribers in sequence to piece together your new SW-846 manual.
A. INSTRUCTIONS FOR NEW SUBSCRIBERS
i. If you have not already done so, open the packages that contain the Third Edition of
SW-846. The Third Edition should include 4 (four) volumes of material (i.e. Volumes
IA, IB, 1C, and II) and will be dated "September 1986" in the lower right hand corner
of each page. Four 3-ring binders (one binder for each volume) and a set of tabs
should also be included. You should place each volume of material in the
appropriately labeled 3-ring binder and insert the tabs. Check the Table of Contents
(dated September 1986) if you have any questions about the order of the methods or
about which volume the methods should be inserted into.
You will be missing some methods from the Third Edition since any Third Edition
September 1986 material, that was superseded by Final Update I July 1992 material.
has already been removed from your copy of the Third Edition.
ii. If you have not already done so, open the package that contains Final Update I. Final
Update I should be a single package printed on white paper with the date "July 1992"
in the lower right hand corner of each page. This package contains new methods and
revised methods. In order to have a complete SW-846 manual, you should insert the
new and revised July 1992 material using the Table of Contents (dated July 1992) at
the front of Final Update I to identify the correct location for each chapter and
method.
Since you are a new subscriber to SW-846, you need not be concerned about the
removal or replacement of the previous version of Update I, as discussed in item (A)
of the Final Update I instructions. Again, any Third Edition September 1986 material
that was superseded by Final Update I July 1992 material, has already been removed
from your copy of the Third Edition. For example, your copy of the Third Edition does
not contain a copy of the September 1986 version of Chapter One because it was
superseded by the July 1992 revision of Chapter One contained in your Final Update
I package.
Final Update I also includes copies of September 1986 "replacement methods" which
are included with your copy of Final Update I and are discussed in item (E) in the
Final Update I instructions. You should not insert the replacement methods! The
replacement methods were sent to subscribers before final Update II was released.
Update II and IIA Instructions - 2 Final
-------
The Disclaimer and Chapter One at the front of Update I should also be photocopied
3 times and inserted at the front of volumes IB, 1C, and II in order to complete the
manual.
Note: Update I does not contain any changes to Volume II other than the
insertion of the Disclaimer and Chapter One. Also, some methods will have an
"A" after the method number. The "A" methods have been revised once.
iii. Finally, open the package labeled Final Updates II and IIA. Final Updates II and IIA
should be a single package printed on white paper. Update II has the date "September
1994" in the lower right hand corner of each page. Update IIA (Method 4010) has the
date "August 1993" in the lower right hand corner of each page. This package contains
new methods and revised methods. In order to have a complete SW-846 manual, you
should insert the new methods and use the revised September 1994 methods to replace
older Third Edition and Final Update I methods that are out of date. Use the Table
of Contents (September 1994) at the front of Final Update II to identify the correct
location for each chapter and method.
The Abstract and Table of Contents at the front of Final Update II should also be
photocopied 3 times and inserted at the front of volumes IB, 1C, and II in order to
complete the manual.
Please Note:
• Update II does not contain any changes to Volume II other than the insertion of
the Abstract and Table of Contents.
• Some methods will have an "A" or a "B" after the method number. The "A"
methods have been revised once. The "B" methods have been revised twice.
• Methods 5100, 5110, and 9200A were included in the Proposed Update II
(November 1992) package but are not included in the Final Update II (September
1994) package. The final Federal Register Rule for Update II explains why these
methods were not finalized (promulgated).
Update II and IIA Instructions - 3 Final
-------
B. INSTRUCTIONS FOR PREVIOUS SUBSCRIBERS
i. Background Information: A number of SW-846 update packages have been released
to the public since the original Third Edition was released. The number and labels on
these packages can be confusing. The following table titled "A Brief History of the
SW-846 Third Edition and Updates" has been provided as an aid. Currently finalized
(promulgated) methods have been printed in bold. 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 following documents:
A BRIEF HISTORY OF THE SW-846 THIRD EDITION AND 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 by request only.)
Final Update HA* (Included
with Final Update II.)
Final Update II
Date Listed on Methods
September 1986
December 1987
November 1990
November 1990
July 1992
November 1992
October 1992
August 1993
September 1994
Color of Paper
White
Green
White
Blue
White
Yellow
White
White
White
Status of Package
Finalized (Promulgated)
Obsolete
Obsolete! Never formally
finalized.
Obsolete! Never formally
proposed.
Finalized (Promulgated)
Obsolete
Obsolete
Finalized (Promulgated)
Finalized (Promulgated)
* Contains only Method 4010.
ii. In order to begin updating the manual it is important to establish exactly what is
currently contained in the manual that you have. If the manual has been properly
updated, the ONLY white pages in the document should be dated September 1986
(Third Edition) and July 1992 (Final Update I). Remove and discard (or archive) any
white pages from your manual that have any date other than September 1986 and July
1992.
There may also be yellow pages dated September 1992 (Proposed Update II) inserted
in the manual. Remove and discard all yellow pages or other colored pages (green or
blue) from the manual. Some individuals may have chosen to keep their copy of
Proposed Update II in a separate binder and removal will not be necessary.
U ?date II and IIA
Instructions - 4
Final
-------
iii. Open the package labeled Final Updates II and IIA. Final Updates II and IIA should
be a single package printed on white paper. Update II has the date "September 1994"
in the lower right hand corner of each page. Update IIA (Method 4010) has the date
"August 1993" in the lower right hand corner of each page. This package contains new
methods and revised methods. In order to have a complete SW-846 manual, you
should insert the new methods and use the revised September 1994 methods to replace
older Third Edition and Final Update I methods that are out of date. Use the Table
of Contents (September 1994) at the front of Final Update II to identify the correct
location for each chapter and method.
The Abstract and Table of Contents at the front of Final Update II should also be
photocopied 3 times and inserted at the front of volumes IB, 1C, and II in order to
complete the manual.
Please Note:
• Update II does not contain any changes to Volume II other than the insertion of
the Abstract and Table of Contents.
• Some methods will have an "A" or a "B" after the method number. The "A"
methods have been revised once. The "B" methods have been revised twice.
dit,> cu.n 2- o, 5
• Methods 5100, 5110, and 9200A were included in the Proposed Update II
(November 1992) package but are not included in the Final Update II (September
1994) package. The final Federal Register Rule for Update II explains why these
methods were not finalized (promulgated).
Update II and IIA Instructions - 5 Final
-------
METHOD STATUS TABLE
SW-846, THIRD EDITION, UPDATES I, II, AND HA
September 1994
Use this table as a reference guide to identify the
promulgation status of SW-846 methods.
The methods in this table are listed sequentially by
number.
This table should not be used as a Table of Contents for
SW-846. Refer to the Table of Contents found in Final
Update II (dated September 1994) for the order in which
the methods appear in SW-846.
prot«*ion Agency
-------
SW-846 METHOD STATUS TABLE
September 1994
NETH NO.
THIRD ED
DATED
9/86
0010
0020
0030
1010
1020
1110
1310
"
HETH NO.
FINAL
UPDATE I
DATED
7/92
~ "*
~ ~
~ ~
_ ••
1020A
~ ~
1310A
1311
NETH NO.
FINAL
UPDT. II
DATED
9/94
"
"™ ~
~ ~
"" ~
— —
_ _
™* ™
1312
NETHOD TITLE
Modified Method 5
Sampling Train
Source Assessment
Sampling System
(SASS)
Volatile Organic
Sampling Train
Pensky-Martens
Closed-Cup Method
for Determining
Ignitability
Setaflash Closed-Cup
Method for
Determining
Ignitability
Corrosivity Toward
Steel
Extraction Procedure
(EP) Toxicity Test
Method and
Structural Integrity
Test
Toxicity
Characteristic
Leaching Procedure
Synthetic
Precipitation
Leaching Procedure
SU-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol II
Chap 10
Vol II
Chap 10
Vol II
Chap 10
Vol 1C
Chap 8
Sec 8.1
Vol 1C
Chap 8
Sec 8.1
Vol 1C
Chap 8
Sec 8.2
Vol 1C
Chap 8
Sec 8.4
Vol 1C
Chap 8
Sec 8.4
Vol 1C
Chap 6
CURRENT
PROMUL-
GATED
METHOD
0010
Rev 0
9/86
0020
Rev 0
9/86
0030
Rev 0
9/86
1010
Rev 0
9/86
1020A
Rev 1
7/92
1110
Rev 0
9/86
1310A
Rev 1
7/92
1311
Rev 0
7/92
1312
Rev 0
9/94
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
1320
1330
3005
3010
3020
3040
3050
NETH NO.
FINAL
UPDATE I
DATED
7/92
"
1330A
3005A
3010A
•* —
3020A
~ —
3050A
NETH NO.
FINAL
UPDT. II
DATED
9/94
"
— ~
3015
~" ~*
"
METHOD TITLE
Multiple Extraction
Procedure
Extraction Procedure
for Oily Wastes
Acid Digestion of
Waters for Total
Recoverable or
Dissolved Metals for
Analysis by FLAA or
ICP Spectroscopy
Acid Digestion of
Aqueous Samples and
Extracts for Total
Metals for Analysis
by FLAA or ICP
Spectroscopy
Microwave Assisted
Acid Digestion of
Aqueous Samples and
Extracts
Acid Digestion of
Aqueous Samples and
Extracts for Total
Metals for Analysis
by GFAA Spectroscopy
Dissolution
Procedure for Oils,
Greases, or Waxes
Acid Digestion of
Sediments, Sludges,
and Soils
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
CURRENT
PROMUL-
GATED
METHOD
1320
Rev 0
9/86
1330A
Rev 1
7/92
3005A
Rev 1
7/92
3010A
Rev 1
7/92
3015
Rev 0
9/94
3020A
Rev 1
7/92
3040
Rev 0
9/86
3050A
Rev 1
7/92
-------
SW-846 HETHOD STATUS TABLE (9/94), CONTINUED
NETH NO.
THIRD ED
DATED
9/86
~ ""
3500
3510
3520
3540
~ "•
3550
3580
3600
METH NO.
FINAL
UPDATE I
DATED
7/92
™* —
3500A
3510A
3520A
3540A
~ ~
— ~*
3580A
3600A
NETH NO.
FINAL
UPDT. II
DATED
9/94
3051
™ ~
3510B
3520B
3540B
3541
3550A
"
3600B
HETHOD TITLE
Microwave Assisted
Acid Digestion of
Sediments, Sludges,
Soils, and Oils
Organic Extraction
and Sample
Preparation
Separatory Funnel
Liquid-Liquid
Extraction
Continuous Liquid-
Liquid Extraction
Soxhlet Extraction
Automated Soxhlet
Extraction
Ultrasonic Extrac-
tion
Waste Dilution
Cleanup
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.2
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.2
CURRENT
PROMUL-
GATED
NETHOD
3051
Rev 0
9/94
3500A
Rev 1
7/92
3510B
Rev 2
9/94
3520B
Rev 2
9/94
3540B
Rev 2
9/94
3541
Rev 0
9/94
3550A
Rev 1
9/94
3580A
Rev 1
7/92
3600B
Rev 2
9/94
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
3610
3611
3620
3630
3640
3650
3660
"
3810
METH NO.
FINAL
UPDATE I
DATED
7/92
3610A
3611A
3620A
3630A
"• ^
3650A
3660A
"
"
METH NO.
FINAL
UPDT. II
DATED
9/94
— —
~* ~
— ~
3630B
3640A
~ ~
~ ~
3665
"
METHOD TITLE
Alumina Column
Cleanup
Alumina Column
Cleanup and
Separation of
Petroleum Wastes
Florisil Column
Cleanup
Silica Gel Cleanup
Gel -Permeation
Cleanup
Acid-Base Partition
Cleanup
Sulfur Cleanup
Sulfuric
Acid/Permanganate
Cleanup
Headspace
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec 4.4
CURRENT
PROMUL-
GATED
METHOD
3610A
Rev 1
7/92
3611A
Rev 1
7/92
3620A
Rev 1
7/92
3630B
Rev 2
9/94
3640A
Rev 1
9/94
3650A
Rev 1
7/92
3660A
Rev 1
7/92
3665
Rev 0
9/94
3810
Rev 0
9/86
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
3820
5030
5040
"
6010
METH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
5030A
"
6010A
METH NO.
FINAL
UPDT. II
DATED
9/94
~ ~
4010
(Update
IIA,
dated
8/93)
_ _
5040A
5041
5050
METHOD TITLE
Hexadecane
Extraction and
Screening of
Purgeable Organics
Screening for
Pentachlorophenol
by Immunoassay
Purge-and-Trap
Analysis of Sorbent
Cartridges from
Volatile Organic
Sampling Train
(VOST) : Gas
Chromatography/Mass
Spectrometry
Technique
Protocol for
Analysis of Sorbent
Cartridges from
Volatile Organic
Sampling Train
(VOST): Wide-bore
Capillary Column
Technique
Bomb Preparation
Method for Solid
Waste
Inductively Coupled
Plasma-Atomic
Emission
Spectroscopy
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec 4.4
Vol IB
Chap 4
Sec 4.4
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol 1C
Chap 5
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
3820
Rev 0
9/86
4010
Rev 0
8/93
5030A
Rev 1
7/92
5040A
Rev 1
9/94
5041
Rev 0
9/94
5050
Rev 0
9/94
6010A
Rev 1
7/92
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
— ~
7000
7020
7040
7041
7060
7061
~* ™*
7080
METH NO.
FINAL
UPDATE I
DATED
7/92
~ •"•
7000A
~ ~
~ ™
~ *~
~* ~~
7061A
"
— •*
METH NO.
FINAL
UPDT. II
DATED
9/94
6020
~ ~
~ "
— _
_ •*
7060A
"
7062
7080A
METHOD TITLE
Inductively Coupled
Plasma - Mass
Spectrometry
Atomic Absorption
Methods
Aluminum (Atomic
Absorption, Direct
Aspiration)
Antimony (Atomic
Absorption, Direct
Aspiration)
Antimony (Atomic
Absorption, Furnace
Technique)
Arsenic (Atomic
Absorption, Furnace
Technique)
Arsenic (Atomic
Absorption, Gaseous
Hydride)
Antimony and Arsenic
(Atomic Absorption,
Borohydride
Reduction)
Barium (Atomic
Absorption, Direct
Aspiration)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
6020
Rev 0
9/94
7000A
Rev 1
7/92
7020
Rev 0
9/86
7040
Rev 0
9/86
7041
Rev 0
9/86
7060A
Rev 1
9/94
7061A
Rev 1
7/92
7062
Rev 0
9/94
7080A
Rev 1
9/94
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
NETH NO.
THIRD ED
DATED
9/86
7420
7421
_ _.
7450
7460
"
7470
7471
7480
NETH NO.
FINAL
UPDATE I
DATED
7/92
_ _
— —
7430
_ _
7461
"
"
NETH NO.
FINAL
UPDT. II
DATED
9/94
"~ —
~ ~
— —
_ _
~ ~
"
7470A
7471A
"
METHOD TITLE
Lead (Atomic
Absorption, Direct
Aspiration)
Lead (Atomic
Absorption, Furnace
Technique)
Lithium (Atomic
Absorption, Direct
Aspiration)
Magnesium (Atomic
Absorption, Direct
Aspiration)
Manganese (Atomic
Absorption, Direct
Aspiration)
Manganese (Atomic
Absorption, Furnace
Technique)
Mercury in Liquid
Waste (Manual Cold-
Vapor Technique)
Mercury in Solid or
Semi sol id Waste
(Manual Cold-Vapor
Technique)
Molybdenum (Atomic
Absorption, Direct
Aspiration)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7420
Rev 0
9/86
7421
Rev 0
9/86
7430
Rev 0
7/92
7450
Rev 0
9/86
7460
Rev 0
9/86
7461
Rev 0
7/92
7470A
Rev 1
9/94
7471A
Rev 1
9/94
7480
Rev 0
9/86
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
7481
7520
7550
7610
7740
7741
~ ~
7760
"
METH NO.
FINAL
UPDATE I
DATED
7/92
"
"
"
™* ~
~ ~
*" ~
7760A
7761
METH NO.
FINAL
UPDT. II
DATED
9/94
"" ~
*" ~
"™ ~"
"
"" ~
7741A
7742
"
"
METHOD TITLE
Molybdenum (Atomic
Absorption, Furnace
Technique)
Nickel (Atomic
Absorption, Direct
Aspiration)
Osmium (Atomic
Absorption, Direct
Aspiration)
Potassium (Atomic
Absorption, Direct
Aspiration)
Selenium (Atomic
Absorption, Furnace
Technique)
Selenium (Atomic
Absorption, Gaseous
Hydride)
Selenium (Atomic
Absorption,
Borohydride
Reduction)
Silver (Atomic
Absorption, Direct
Aspiration)
Silver (Atomic
Absorption, Furnace
Technique)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7481
Rev 0
9/86
7520
Rev 0
9/86
7550
Rev 0
9/86
7610
Rev 0
9/86
7740
Rev 0
9/86
7741A
Rev 1
9/94
7742
Rev 0
9/94
7760A
Rev 1
7/92
7761
Rev 0
7/92
10
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
NETH NO.
THIRD ED
DATED
9/86
7770
~ —
7840
7841
7870
7910
7911
7950
"
NETH NO.
FINAL
UPDATE I
DATED
7/92
*" ~
7780
— —
~ ~
~ ~
"
~* ~
"
7951
NETH NO.
FINAL
UPDT. II
DATED
9/94
~ **
~ ~
•" ~
~ ~
~ ~
"* ~
*" ~
"
"
METHOD TITLE
Sodium (Atomic
Absorption, Direct
Aspiration)
Strontium (Atomic
Absorption, Direct
Aspiration)
Thallium (Atomic
Absorption, Direct
Aspiration)
Thallium (Atomic
Absorption, Furnace
Technique)
Tin (Atomic
Absorption, Direct
Aspiration)
Vanadium (Atomic
Absorption, Direct
Aspiration)
Vanadium (Atomic
Absorption, Furnace
Technique)
Zinc (Atomic
Absorption, Direct
Aspiration)
Zinc (Atomic
Absorption, Furnace
Technique)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7770
Rev 0
9/86
7780
Rev 0
7/92
7840
Rev 0
9/86
7841
Rev 0
9/86
7870
Rev 0
9/86
7910
Rev 0
9/86
7911
Rev 0
9/86
7950
Rev 0
9/86
7951
Rev 0
7/92
11
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
NETH NO.
THIRD ED
DATED
9/86
8000
8010
8015
8020
8030
— —
NETH NO.
FINAL
UPDATE I
DATED
7/92
8000A
801 OA
8011
80 ISA
"* ~
8021
8030A
"
NETH NO.
FINAL
UPDT. II
DATED
9/94
"
8010B
*" *"
8020A
8021A
™ «•
8031
METHOD TITLE
Gas Chromatography
Halogenated Volatile
Organics by Gas
Chromatography
1,2-Dibromoethane
and l,2-Dibromo-3-
chloropropane by
Microextraction and
Gas Chromatography
Nonhalogenated
Volatile Organics by
Gas Chromatography
Aromatic Volatile
Organics by Gas
Chromatography
Halogenated
Volatiles by Gas
Chromatography Using
Photoionization and
Electrolytic
Conductivity
Detectors in Series:
Capillary Column
Technique
Acrolein and
Acrylonitrile by Gas
Chromatography
Acrylonitrile by Gas
Chromatography
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
CURRENT
PROMUL-
GATED
METHOD
8000A
Rev 1
7/92
8010B
Rev 2 '
9/94
8011
Rev 0
7/92
80 ISA
Rev 1
7/92
8020A
Rev 1
9/94
8021A
Rev 1
9/94
8030A
Rev 1
7/92
8031
Rev 0
9/94
12
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
NETH NO.
THIRD ED
DATED
9/86
— —
8040
8060
"
8080
8090
HETH NO.
FINAL
UPDATE I
DATED
7/92
*. _
8040A
lm ~
8070
NETH NO.
FINAL
UPDT. II
DATED
9/94
8032
"™ ~
~ ~
8061
"
8080A
8081
NETHOD TITLE
Acryl amide by Gas
Chromatography
Phenols by Gas
Chromatography
Phthalate Esters
Phthalate Esters by
Capillary Gas
Chromatography with
Electron Capture
Detection (GC/ECD)
Nitrosamines by Gas
Chromatography
Organochlorine Pes-
ticides and
Polychlorinated
Biphenyls by Gas
Chromatography
Organochlorine
Pesticides and PCBs
as Aroclors by Gas
Chromatography:
Capillary Column
Technique
Nitroaromatics and
Cyclic Ketones
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
CURRENT
PROMUL-
GATED
METHOD
8032
Rev 0
9/94
8040A
Rev 1
7/92
8060
Rev 0
9/86
8061
Rev 0
9/94
8070
Rev 0
7/92
8080A
Rev 1
9/94
8081
Rev 0
9/94
8090
Rev 0
9/86
13
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
HETH NO.
THIRD ED
DATED
9/86
8100
— _•
8120
8140
8150
METH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
8110
_ _
_ _
8141
8150A
METH NO.
FINAL
UPDT. II
DATED
9/94
~ ~
~ ~
8120A
8121
"
8141A
8150B
8151
METHOD TITLE
Polynuclear Aromatic
Hydrocarbons
Haloethers by Gas
Chromatography
Chlorinated
Hydrocarbons by Gas
Chromatography
Chlorinated
Hydrocarbons by Gas
Chromatography:
Capillary Column
Technique
Organophosphorus
Pesticides
Organophosphorus
Compounds by Gas
Chromatography:
Capillary Column
Technique
Chlorinated
Herbicides by Gas
Chromatography
Chlorinated
Herbicides by GC
Using Methyl ati on or
Pentafluorobenzyl-
ation Derivati-
zation: Capillary
Column Technique
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
CURRENT
PROMUL-
GATED
METHOD
8100
Rev 0
9/86
8110
Rev 0
7/92
8120A
Rev 1
9/94
8121
Rev 0
9/94
8140
Rev 0
9/86
8141A
Rev 1
9/94
8150B
Rev 2
9/94
8151
Rev 0
9/94
14
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
8240
8250
8270
8280
METH NO.
FINAL
UPDATE I
DATED
7/92
8240A
8260
8270A
METH NO.
FINAL
UPDT. II
DATED
9/94
8240B
8250A
8260A
8270B
8275
METHOD TITLE
Volatile Organic
Compounds by Gas
Chromatography/Mass
Spectrometry (GC/MS)
Semivolatile Organic
Compounds
by Gas
Chromatography/Mass
Spectrometry (GC/MS)
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
Thermal
Chromatography/Mass
Spectrometry (TC/MS)
for Screening
Semivolatile Organic
Compounds
The Analysis of
Polychlorinated
Dibenzo-p-Dioxins
and Polychlorinated
Dibenzofurans
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec 4.4
Vol IB
Chap 4
Sec
4.3.2
CURRENT
PROMUL-
GATED
METHOD
8240B
Rev 2
9/94
8250A
Rev 1
9/94
8260A
Rev 1
9/94
8270B
Rev 2
9/94
8275
Rev 0
9/94
8280
Rev 0
9/86
15
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
8310
"
METH NO.
FINAL
UPDATE I
DATED
7/92
_ •»
"
METH NO.
FINAL
UPDT. II
DATED
9/94
8290
"
8315
8316
8318
METHOD TITLE
Polychlorinated
Dibenzodioxins
(PCDDs) and
Polychlorlnated
Dibenzofurans
(PCDFs) by High-
Resolution Gas
Chromatography/High-
Resolution Mass
Spectrometry
(HRGC/HRMS)
Polynuclear Aromatic
Hydrocarbons
Determination of
Carbonyl Compounds
by High Performance
Liquid
Chromatography
(HPLC)
Aery 1 amide,
Acrylonitrile and
Acrolein by High
Performance Liquid
Chromatography
(HPLC)
N-Methyl carbamates
by High Performance
Liquid Chroma-
tography (HPLC)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
CURRENT
PROMUL-
GATED
METHOD
8290
Rev 0
9/94
8310
Rev 0
9/86
8315
Rev 0
9/94
8316
Rev 0
9/94
8318
Rev 0
9/94
€
16
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
NETH NO.
THIRD ED
DATED
9/86
9010
9012
NETH NO.
FINAL
UPDATE I
DATED
7/92
9010A
"
NETH NO.
FINAL
UPDT. II
DATED
9/94
8321
8330
8331
8410
~ "
"
NETHOD TITLE
Solvent Extractable
Non-Volatile
Compounds by High
Performance Liquid
Chromatography/Ther-
mospray/Mass
Spectrometry
(HPLC/TSP/MS) or
Ultraviolet (UV)
Detection
Nitroaromatics and
Nitramines by High
Performance Liquid
Chromatography
(HPLC)
Tetrazene by Reverse
Phase High
Performance Liquid
Chromatography
(HPLC)
Gas Chroma-
tography/Fourier
Transform Infrared
(GC/FT-IR) Spec-
trometry for
Semi volatile
Organics: Capillary
Column
Total and Amenable
Cyanide
(Colorimetric,
Manual)
Total and Amenable
Cyanide
(Colorimetric,
Automated UV)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.4
Vol 1C
Chap 5
Vol 1C
Chap 5
CURRENT
PROMUL-
GATED
METHOD
8321
Rev 0
9/94
8330
Rev 0
9/94
8331
Rev 0
9/94
8410
Rev 0
9/94
9010A
Rev 1
7/92
9012
Rev 0
9/86
17
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
HETH NO.
THIRD ED
DATED
9/86
— —
9020
~ *~
9022
9030
9035
9036
9038
HETH NO.
FINAL
UPDATE I
DATED
7/92
9013
9020A
9021
-, _
9030A
9031
"
"
HETH NO.
FINAL
UPDT. II
DATED
9/94
— *•
9020B
"
~ "*
_ _
"
"
METHOD TITLE
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
Acid-Soluble and
Acid-Insoluble
Sulfides
Extractable Sulfides
Sulfate
(Colorimetric,
Automated,
Chloranilate)
Sulfate
(Colorimetric,
Automated,
Methyl thymol Blue,
AA II)
Sulfate
(Turbidimetric)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
CURRENT
PROMUL-
GATED
METHOD
9013
Rev 0
7/92
9020B
Rev 2
9/94
9021
Rev 0
7/92
9022
Rev 0
9/86
9030A
Rev 1
7/92
9031
Rev 0
7/92
9035
Rev 0
9/86
9036
Rev 0
9/86
9038
Rev 0
9/86
18
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9040
9041
9045
9050
"
9060
9065
9066
9067
NETH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
9041A
9045A
~ ~
~" "*
•™ ~
*"* ™
"
"
NETH NO.
FINAL
UPDT. II
DATED
9/94
9040A
~ —
9045B
"
9056
~ ~
"
"
METHOD TITLE
pH Electrometric
Measurement
pH Paper Method
Soil and Waste pH
Specific Conductance
Determination of
Inorganic An ions by
Ion Chromatography
Total Organic Carbon
Phenol ics
(Spectrophotometri c ,
Manual 4-AAP with
Distillation)
Phenol ics
(Colorimetric,
Automated 4-AAP with
Distillation)
Phenol ics
(Spectrophotometri c,
MBTH with
Distillation)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
CURRENT
PROMUL-
GATED
METHOD
9040A
Rev 1
9/94
9041A
Rev 1
7/92
9045B
Rev 2
9/94
9050
Rev 0
9/86
9056
Rev 0
9/94
9060
Rev 0
9/86
9065
Rev 0
9/86
9066
Rev 0
9/86
9067
Rev 0
9/86
19
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9070
9071
9080
9081
NETH NO.
FINAL
UPDATE I
DATED
7/92
— —
"
METH NO.
FINAL
UPDT. II
DATED
9/94
9071A
9075
9076
9077
"" ~
"
METHOD TITLE
Total Recoverable
Oil & Grease
(Gravimetric,
Separatory Funnel
Extraction)
Oil and Grease
Extraction Method
for Sludge and
Sediment
Samples
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)
Cation- Exchange
Capacity of Soils
(Ammonium Acetate)
Cation-Exchange
Capacity of Soils
(Sodium Acetate)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 6
Vol 1C
Chap 6
CURRENT
PROMUL-
GATED
METHOD
9070
Rev 0
9/86
9071A
Rev 1
9/94
9075
Rev 0
9/94
9076
Rev 0
9/94
9077
Rev 0
9/94
9080
Rev 0
9/86
9081
Rev 0
9/86
20
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9090
9095
™* ~
9100
9131
9132
9200
9250
9251
NETH NO.
FINAL
UPDATE I
DATED
7/92
9090A
*™ ~
_ _
— _
_ _
-» ~
"
METH NO.
FINAL
UPDT. II
DATED
9/94
~ ~
™* ••
9096
~ ~
~ ~
"
"
METHOD TITLE
Compatibility Test
for Wastes and
Membrane Liners
Paint Filter Liquids
Test
Liquid Release Test
(LRT) Procedure
Saturated Hydraulic
Conductivity,
Saturated Leachate
Conductivity, and
Intrinsic
Permeability
Total Col i form:
Multiple Tube
Fermentation
Technique
Total Col i form:
Membrane Filter
Technique
Nitrate
Chloride
(Colorimetric,
Automated
Ferri cyanide AAI)
Chloride
(Colorimetric,
Automated
Ferri cyanide AAI I)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
CURRENT
PROMUL-
GATED
METHOD
9090A
Rev 1
7/92
9095
Rev 0
9/86
9096
Rev 0
9/94
9100
Rev 0
9/86
9131
Rev 0
9/86
9132
Rev 0
9/86
9200
Rev 0
9/86
9250
Rev 0
9/86
9251
Rev 0
9/86
21
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9252
_ _
9310
9315
9320
HCN Test
Method
H2S Test
Method
METH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
™ ~
** ~
~ ~
_ _
HCN Test
Method
H2S Test
Method
METH NO.
FINAL
UPDT. II
DATED
9/94
9252A
9253
~ —
** ~
~" ~
HCN Test
Method
H2S Test
Method
NETHOD TITLE
Chloride
(Titrimetric,
Mercuric Nitrate)
Chloride
(Titrimetric, Silver
Nitrate)
Gross Alpha and
Gross Beta
Alpha-Emitting
Radium Isotopes
Radium- 228
Test Method to
Determine Hydrogen
Cyanide Released
from Wastes
Test Method to
Determine Hydrogen
Sulfide Released
from Wastes
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 5
Vol 1C
Chap 7
Sec 7.3
Vol 1C
Chap 7
Sec 7.3
CURRENT
PROMUL-
GATED
METHOD
9252A
Rev 1
9/94
9253
Rev 0
9/94
9310
Rev 0
9/86
9315
Rev 0
9/86
9320
Rev 0
9/86
Guidance
Method
Only
Guidance
Method
Only
€
22
-------
a./
VOLUME ONE,
SECTION A
|
U s Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12UUlOor „ --v ,..f
fhiraso IL 60604-3590 Revision 0
Chicago, IL ou Date
-------
U.S. eiwlfonmwtil Pwtectkm Agency
i
For rale by the Superintendent of Documents, tl.S. Government Printing Office Watblnirton, D.C. 20402
-------
DISCLAIMER
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. 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 0
July 1992
-------
ABSTRACT
Test Methods for Evaluating Solid Waste, Physical/Chemical Methods (SW-846)
provides test procedures and guidance which are recommended for use in conducting
the evaluations and measurements needed to comply with the Resource Conservation
and Recovery Act (RCRA), Public Law 94-580, as amended. These methods are
approved by the U.S. Environmental Protection Agency for obtaining data to
satisfy the requirements of 40 CFR Parts 122 through 270 promulgated under RCRA,
as amended. This manual presents the state-of-the-art in routine analytical
tested adapted for the RCRA program. It contains procedures for field and
laboratory quality control, sampling, determining hazardous constituents in
wastes, determining the hazardous characteristics of wastes (toxicity,
ignitability, reactivity, and corrosivity), and for determining physical
properties of wastes. It also contains guidance on how to select appropriate
methods.
Several of the hazardous waste regulations under Subtitle C of RCRA require
that specific testing methods described in SW-846 be employed for certain
applications. Refer to 40 Code of Federal Regulations (CFR), Parts 260 through
270, for those specific requirements. Any reliable analytical method may be used
to meet other requirements under Subtitle C of RCRA.
U.S. Environmental Protection Agency
Region 5, Library (PL. 12j)
ABSTRACT - 1 Revision 2
September 1994
-------
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 -- METALLIC 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 2
September 1994
-------
Method 3020A:
Method 3040:
Method 3050A:
Method 3051:
Acid Digestion of Aqueous Samples and Extracts for Total
Metals for Analysis by Graphite Furnace Atomic
Absorption (GFAA) 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
3.3 Methods for Determination of Metals
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
Method
Method
Method
Method
Method
Method
6010A:
6020:
7000A:
7020:
7040:
7041:
7060A:
7061A:
7062:
7080A:
7081:
7090:
7091:
7130:
7131A:
7140:
7190:
7191:
7195:
7196A:
7197:
7198:
7200:
7201:
7210:
7211:
7380:
7381:
7420:
7421:
7430:
7450:
7460:
7461:
7470A:
7471A:
Method 7480:
Method 7481:
Method 7520:
Method 7550:
Method 7610:
Method 7740:
Inductively Coupled Plasma-Atomic Emission Spectroscopy
Inductively Coupled Plasma - Mass Spectrometry
Atomic Absorption Methods
Aluminum (AA, Direct Aspiration)
Antimony (AA, Direct Aspiration)
Antimony (AA, Furnace Technique)
Arsenic (AA, Furnace Technique)
Arsenic (AA, Gaseous Hydride)
Antimony and Arsenic (AA, Borohydride Reduction)
Barium (AA, Direct Aspiration)
Barium (AA, Furnace Technique)
Beryllium (AA, Direct Aspiration)
Beryllium (AA, Furnace Technique)
Cadmium (AA, Direct Aspiration)
Cadmium (AA, Furnace Technique)
Calcium (AA, Direct Aspiration)
Chromium (AA, Direct Aspiration)
Chromium (AA, Furnace Technique)
Chromium, Hexavalent (Coprecipitation)
Chromium, Hexavalent (Colorimetric)
Chromium, Hexavalent (Chelation/Extraction)
Chromium, Hexavalent (Differential Pulse Polarography)
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)
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 Semisolid Waste (Manual Cold-Vapor
Technique)
Molybdenum (AA, Direct Aspiration)
Molybdenum (AA, Furnace Technique)
Nickel (AA, Direct Aspiration)
Osmium (AA, Direct Aspiration)
Potassium (AA, Direct Aspiration)
Selenium (AA, Furnace Technique)
CONTENTS - 2
Revision 2
September 1994
-------
Method 7741A: Selenium (AA, Gaseous Hydride)
Method 7742: Selenium (AA, Borohydride Reduction)
Method 7760A: Silver (AA, Direct Aspiration)
Method 7761: Silver (AA, Furnace Technique)
Method 7770: Sodium (AA, Direct Aspiration)
Method 7780: Strontium (AA, Direct Aspiration)
Method 7840: Thallium (AA, Direct Aspiration)
Method 7841: Thallium (AA, Furnace Technique)
Method 7870: Tin (AA, Direct Aspiration)
Method 7910: Vanadium (AA, Direct Aspiration)
Method 7911: Vanadium (AA, Furnace Technique)
Method 7950: Zinc (AA, Direct Aspiration)
Method 7951: Zinc (AA, Furnace Technique)
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). In
order to properly document the method used for analysis, the entire
method number Including the suffix letter designation (e.g., A or B)
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 2
September 1994
-------
VOLUME ONE
SECTION B
i
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 Extractions and Preparations
Method 3500A: Organic Extraction and Sample Preparation
Method 3510B: Separatory Funnel Liquid-Liquid Extraction
Method 3520B: Continuous Liquid-Liquid Extraction
Method 3540B: Soxhlet Extraction
Method 3541: Automated Soxhlet Extraction
Method 3550A: Ultrasonic Extraction
Method 3580A: Waste Dilution
Method 5030A: Purge-and-Trap
Method 5040A: Analysis of Sorbent Cartridges from Volatile Organic
Sampling Train (VOST): Gas Chromatography/Mass
Spectrometry Technique
Method 5041: Protocol for Analysis of Sorbent Cartridges from
Volatile Organic Sampling Train (VOST): Wide-bore
Capillary Column Technique
Method 5100: Determination of the Volatile Organic Concentration of
Waste Samples
Method 5110: Determination of Organic Phase Vapor Pressure in Waste
Samples
4.2.2 Cleanup
Method 3600B: Cleanup
Method 3610A: Alumina Column Cleanup
CONTENTS - 4 Revision 2
September 1994
-------
Method 3611A:
Method
Method
Method
Method
Method
Method
3620A:
3630B:
3640A:
3650A:
3660A:
3665:
Alumina Column Cleanup and Separation of
Petroleum Wastes
Florisil Column Cleanup
Silica Gel Cleanup
Gel-Permeation Cleanup
Acid-Base Partition Cleanup
Sulfur Cleanup
Sulfuric Acid/Permanganate Cleanup
4.3 Determination of Organic Analytes
4.3.1
Gas Chromatographic Methods
Method 8000A:
Method 8010B:
Method 8011:
Method 8015A:
Method 8020A:
Method 8021A:
Method
Method
Method
Method
Method
Method
8030A:
8031:
8032:
8040A:
8060:
8061:
Method 8070:
Method 8080A:
Method 8081:
Method 8090:
Method 8100:
Method 8110:
Method 8120A:
Method 8121:
Method 8140:
Method 8141A:
Method 81SOB:
Method 8151:
Gas Chromatography
Halogenated Volatile Organics by Gas Chromatography
1,2-Dibromoethane and l,2-Dibromo-3-chloropropane by
Microextraction and Gas Chromatography
Nonhalogenated Volatile Organics by Gas Chromatography
Aromatic Volatile Organics by Gas Chromatography
Halogenated Volatiles by Gas Chromatography Using
Photoionization and Electrolytic Conductivity Detectors
in Series: Capillary Column Technique
Acrolein and Acrylonitrile by Gas Chromatography
Acrylonitrile by Gas Chromatography
Acrylamide by Gas Chromatography
Phenols by Gas Chromatography
Phthalate Esters
Phthalate Esters by Capillary Gas Chromatography with
Electron Capture Detection (GC/ECD)
Nitrosamines by Gas Chromatography
Organochlorine Pesticides and Polychlorinated Biphenyls
by Gas Chromatography
Organochlorine Pesticides and PCBs as Aroclors by Gas
Chromatography: Capillary Column Technique
Nitroaromatics and Cyclic Ketones
Polynuclear Aromatic Hydrocarbons
Haloethers by Gas Chromatography
Chlorinated Hydrocarbons by Gas Chromatography
Chlorinated Hydrocarbons by Gas Chromatography:
Capillary Column Technique
Organophosphorus Pesticides
Organophosphorus Compounds by Gas Chromatography:
Capillary Column Technique
Chlorinated Herbicides by Gas Chromatography
Chlorinated Herbicides by GC Using Methylation or
Pentaf 1 uorobenzylation Deri vatization: Capi 11 ary Column
Technique
CONTENTS - 5
Revision 2
September 1994
-------
4.3.2
Gas Chromatographic/Mass Spectroscopic Methods
Method 8240B:
Method 8250A:
Method 8260A:
Method 8270B:
Method 8280:
Appendix A:
Appendix B:
Method 8290:
Appendix A:
Volatile Organic Compounds by Gas Chromatography/Mass
Spectrometry (GC/MS)
Semivolatile Organic Compounds by Gas
Chromatography/Mass Spectrometry (GC/MS)
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
Polychlorinated Dibenzofurans
Signal-to-Noise Determination Methods
Recommended Safety and Handling Procedures
PCDDs/PCDFs
Polychlorinated Dibenzodioxins (PCDDs)
Polychlorinated Dibenzofurans (PCDFs) by High-Resolution
Gas Chromatography/High-Resolution Mass Spectrometry
(HRGC/HRMS)
Procedures for the Collection, Handling,
Analysis, and Reporting of Wipe Tests Performed
within the Laboratory
and
for
and
4.3.3
Method 8310:
Method 8315:
Appendix A:
Method 8316:
Method 8318:
Method 8321:
Method 8330:
Method 8331:
High Performance Liquid Chromatographic Methods
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/TSP/MS) or Ultraviolet (UV) Detection
Nitroaromatics and Nitramines by High Performance Liquid
Chromatography (HPLC)
Tetrazene by Reverse Phase High Performance Liquid
Chromatography (HPLC)
4.3.4
Method 8410:
Fourier Transform Infrared Methods
Gas Chromatography/Fourier Transform Infrared (GC/FT-IR)
Spectrometry for Semivolatile Organics: Capillary
Column
CONTENTS - 6
Revision 2
September 1994
-------
4.4 Miscellaneous Screening Methods
Method 3810: Headspace
Method 3820: Hexadecane Extraction and Screening of Purgeable
Organics
Method 4010: Screening for Pentachlorophenol by Immunoassay
Method 8275: Thermal Chromatography/Mass Spectrometry (TC/MS) for
Screening Semivolatile Organic Compounds
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). In
order to properly document the method used for analysis, the entire
method number Including the suffix letter designation (e.g., A or B)
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 - 7 Revision 2
September 1994
-------
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
Nethod
Method
Method
Method
Method
Method
5050:
9010A:
9012:
9013:
9020B:
9021:
9022:
Method 9030A:
Method 9031:
Nethod 9035:
Method 9036:
Method 9038:
Method 9056:
Method 9060:
Method 9065:
Method 9066:
Method 9067:
Method 9070:
Method 9071A:
Method 9075:
Method 9076:
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
Acid-Soluble and Acid-Insoluble Sulfides
Extractable Sulfides
Sulfate (Colorimetric, Automated, Chloranilate)
Sulfate (Colorimetric, Automated, Methylthymol Blue, AA
II)
Sulfate (Turbidimetric)
Determination of Inorganic Anions by Ion Chromatography
Total Organic Carbon
Phenolics (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
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
i
CONTENTS - 8
Revision 2
September 1994
-------
Method 9077:
Method A:
Method B:
Method C:
Method 9131:
Method 9132:
Method 9200:
Method 9250:
Method 9251:
Method 9252A:
Method 9253:
Method 9320:
CHAPTER SIX -- PROPERTIES
Method 1312:
Method 1320:
Method 1330A:
Method 9040A:
Method 9041A:
Method 9045B:
Method 9050:
Method 9080:
Method 9081:
Method 9090A:
Method 9095:
Method 9096:
Appendix A:
Method 9100:
Method 9310:
Method 9315:
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
Nitrate
Chloride (Colorimetric, Automated Ferricyanide AAI)
Chloride (Colorimetric, Automated Ferricyanide AAII)
Chloride (Titrimetric, Mercuric Nitrate)
Chloride (Titrimetric, Silver Nitrate)
Radium-228
Synthetic Precipitation Leaching Procedure
Multiple Extraction Procedure
Extraction Procedure for Oily Wastes
pH Electrometric Measurement
pH Paper Method
Soil and Waste pH
Specific Conductance
Cation-Exchange Capacity of Soils (Ammonium Acetate)
Cation-Exchange Capacity of Soils (Sodium Acetate)
Compatibility Test for Wastes and Membrane Liners
Paint Filter Liquids Test
Liquid Release Test (LRT) Procedure
LRT Pre-Test
Saturated Hydraulic Conductivity, Saturated Leachate
Conductivity, and Intrinsic Permeability
Gross Alpha and Gross Beta
Alpha-Emitting Radium Isotopes
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
CONTENTS - 9
Revision 2
September 1994
-------
CHAPTER EIGHT -- METHODS FOR DETERMINING CHARACTERISTICS
8.1 Ignitability
Method 1010: Pensky-Martens Closed-Cup Method for Determining
Ignitability
Method 1020A: Setaflash Closed-Cup Method for Determining Ignitability
8.2 Corrosivity
Method 1110: Corrosivity Toward Steel
8.3 Reactivity
8.4 Toxicity
Method 1310A: Extraction Procedure (EP) Toxicity Test Method and
Structural Integrity Test
Method 1311: 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). In
order to properly document the method used for analysis, the entire
method number Including the suffix letter designation (e.g., A or B)
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 - 10 Revision 2
September 1994
-------
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: Modified Method 5 Sampling Train
Appendix A: Preparation of XAD-2 Sorbent Resin
Appendix B: Total Chromatographable Organic Material Analysis
Method 0020: Source Assessment Sampling System (SASS)
Method 0030: Volatile Organic Sampling Train
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
CONTENTS - 11 Revision 2
September 1994
-------
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). In
order to properly document the method used for analysis, the entire
method number Including the suffix letter designation (e.g., A or B)
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 - 12 Revision 2
September 1994
-------
PREFACE AND OVERVIEW
PURPOSE OF THE MANUAL
Test Methods for Evaluating Solid Waste (SW-846) 1s Intended to provide 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 methodology approved by the Office of Solid Waste for use
1n Implementing the RCRA regulatory program. The manual provides methodology
for collecting and testing representative samples of waste and other materials
to be monitored. Aspects of sampling and testing covered 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 1n 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, 1n part, on the skill, training,
and experience of the analyst. For some situations, it is possible to use
this manual 1n 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, 1t 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. Volume I focuses on laboratory
activities and is divided for convenience into three sections. Volume IA
deals with quality control, selection of appropriate test methods, and
analytical methods for metallic species. Volume IB consists of methods for
organic analytes. Volume 1C includes a variety of test methods for
miscellaneous analytes and properties for use in evaluating the waste
characteristics. Volume II deals with sample acquisition and Includes quality
control, sampling plan design and implementation, and field sampling methods.
Included for the convenience of sampling personnel are discusssions of the
ground water, land treatment, and incineration monitoring regulations.
Volume I begins with an overview of the quality control procedures to be
imposed upon the sampling and analytical methods. The quality control chapter
(Chapter One) and the methods 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 be reviewing Chapter One and the analytical methods together.
It 1s expected that Individual laboratories, using SW-846 as the reference
PREFACE - 1
Revision 0
Date September 1986
-------
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 1n the
determination of groups of analytes or specific analytes. It aids the chemist
In constructing the correct analytical method from the array of procedures
which may cover the matrlx/analyte/concentratlon combination of Interests.
The section discusses the objective of the testing program and Us
relationship to the choice of an analytical method. Flow charts are presented
along with tables to guide 1n 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. The chapters describing Miscellaneous
Test Methods and Properties, however, give complete methods which are not
amenable to such segmentation to form discrete procedures.
The Introductory material at the beginning of each section containing
analytical procedures presents Information on sample handling and
preservation, safety, and sample preparation.
Part II of Volume I (Chapters Seven and Eight) describes the
characteristics of a waste. Sections following the regulatory descriptions
contain the methods used to determine if the waste 1s hazardous because 1t
exhibits a particular characteristic.
Volume II gives background information on statistical and nonstatistlcal
aspects of sampling. It also presents practical sampling techniques
appropriate for situations presenting a variety of physical conditions.
A discussion of the regulatory requirements with respect to several
monitoring categories is also given 1n this volume. These include ground
water monitoring, land treatment, and incineration. The purpose of this
guidance is to orient the user to the objective of the analysis, and to assist
in developing data quality objectives, sampling plans, and laboratory SOP's.
Significant interferences, or other problems, may be encountered with
certain samples. In these situations, the analyst is advised to contact the
Chief, Methods Section (WH-562B) Technical Assessment Branch, Office of Solid
Waste, US EPA, Washington, DC 20460 (202-382-4761) for assistance. The
manual 1s 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.
PREFACE - 2
Revision 0
Date September 1986
-------
CHAPTER ONE
TABLE OF CONTENTS
Secti
1.0
2.0
3.0
on
INTRODUCTION
QA PROJECT PLAN
2.1 DATA QUALITY OBJECTIVES
2.2 PROJECT OBJECTIVES
2.3 SAMPLE COLLECTION
2.4 ANALYSIS AND TESTING
2.5 QUALITY CONTROL
2.6 PROJECT DOCUMENTATION
2.7 ORGANIZATION PERFORMING FIELD OR LABORATORY
OPERATIONS
2.7.1 Performance Evaluation
2.7.2 Internal Assessment by QA Function
2.7.3 External Assessment
2.7.4 On-Site Evaluation
2.7.4.1 Field Activities
2.7.4.2 Laboratory Activities
2.7.5 QA Reports
FIELD OPERATIONS
3.1 FIELD LOGISTICS
3.2 EQUIPMENT/INSTRUMENTATION
3.3 OPERATING PROCEDURES
3.3.1 Sample Management
3.3.2 Reagent/Standard Preparation
3.3.3 Decontamination
3.3.4 Sample Collection
3.3.5 Field Measurements
3.3.6 Equipment Calibration And Maintenance . . . .
3.3.7 Corrective Action
3.3.8 Data Reduction and Validation
3.3.9 Reporting
3.3.10 Records Management
3.3.11 Waste Disposal
3.4 FIELD QA AND QC REQUIREMENTS
3.4.1 Control Samples
3.4.2 Acceptance Criteria
3.4.3 Deviations
3.4.4 Corrective Action
3.4.5 Data Handling
3.5 QUALITY ASSURANCE REVIEW
3.6 FIELD RECORDS
Paqe
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ONE - i Revision 1
July 1992
-------
TABLE OF CONTENTS
(continued)
Section
4.0
5.0
6.0
INDEX
LABORATORY OPERATIONS
4.1 FACILITIES
4.2 EQUIPMENT/INSTRUMENTATION
4.3 OPERATING PROCEDURES
4.3.1 Sample Management
4.3.2 Reagent/Standard Preparation
4.3.3 General Laboratory Techniques
4.3.4 Test Methods
4.3.5 Equipment Calibration and Maintenance . . . .
4.3.6 QC
4.3.7 Corrective Action
4.3.8 Data Reduction and Validation
4.3.9 Reporting
4.3.10 Records Management
4.3.11 Waste Disposal
4.4 LABORATORY QA AND QC PROCEDURES
4.4.1 Method Proficiency
4.4.2 Control Limits
4.4.3 Laboratory Control Procedures
4.4.4 Deviations
4.4.5 Corrective Action
4.4.6 Data Handling
4.5 QUALITY ASSURANCE REVIEW
4.6 LABORATORY RECORDS
DEFINITIONS
REFERENCES
Page
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ONE - ii Revision 1
July 1992
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CHAPTER ONE
QUALITY CONTROL
1.0 INTRODUCTION
It is the goal of the U.S. Environmental Protection Agency's (EPA's)
quality assurance (QA) program to ensure that all data be scientifically valid,
defensible, and of known precision and accuracy. The data should be of
sufficient known quality to withstand scientific and legal challenge relative to
the use for which the data are obtained. The QA program is management's tool for
achieving this goal.
For RCRA analyses, the recommended minimum requirements for a QA program
and the associated quality control (QC) procedures are provided in this chapter.
The data acquired from QC procedures are used to estimate the quality of
analytical data, to determine the need for corrective action in response to
identified deficiencies, and to interpret results after corrective action
procedures are implemented. Method-specific QC procedures are incorporated in
the individual methods since they are not applied universally.
A total program to generate data of acceptable quality should include both
a QA component, which encompasses the management procedures and controls, as well
as an operational day-to-day QC component. This chapter defines fundamental
elements of such a data collection program. Data collection efforts involve:
1. design of a project plan to achieve the data quality objectives
(DQOs);
2. implementation of the project plan; and
3. assessment of the data to determine if the DQOs are met.
The project plan may be a sampling and analysis plan or a waste analysis plan if
it covers the QA/QC goals of the Chapter, or it may be a Quality Assurance
Project Plan as described later in this chapter.
This chapter identifies the minimal QC components that should be used in
the performance of sampling and analyses, including the QC information which
should be documented. Guidance is provided to construct QA programs for field
and laboratory work conducted in support of the RCRA program.
2.0 QA PROJECT PLAN
It is recommended that all projects which generate environment-related data
in support of RCRA have a QA Project Plan (QAPjP) or equivalent. In some
instances, a sampling and analysis plan or a waste analysis plan may be
equivalent if it covers all of the QA/QC goals outlined in this chapter. In
addition, a separate QAPjP need not be prepared for routine analyses or
activities where the procedures to be followed are described in a Standard
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Operating Procedures manual or similar document and include the elements of a
QAPjP. These documents should be available and referenced in the documentation
and/or records for the analysis activities. The term "QAPjP" in this chapter
refers to any of these QA/QC documents.
The QAPjP should detail the QA/QC goals and protocols for a specific data
collection activity. The QAPjP sets forth a plan for sampling and analysis
activities that will generate data of a quality commensurate with their intended
use. QAPjP elements should include a description of the project and its
objectives; a statement of the DQOs of the project; identification of those in-
volved in the data collection and their responsibilities and authorities;
reference to (or inclusion of) the specific sample collection and analysis
procedures that will be followed for all aspects of the project; enumeration of
QC procedures to be followed; and descriptions of all project documentation.
Additional elements should be included in the QAPjP if needed to address all
quality related aspects of the data collection project. Elements should be
omitted only when they are inappropriate for the project or when absence of those
elements will not affect the quality of data obtained for the project (see
reference 1).
The role and importance of DQOs and project documentation are discussed
below in Sections 2.1 through 2.6. Management and organization play a critical
role in determining the effectiveness of a QA/QC program and ensuring that all
required procedures are followed. Section 2.7 discusses the elements of an
organization's QA program that have been found to ensure an effective program.
Field operations and laboratory operations (along with applicable QC procedures)
are discussed in Sections 3 and 4, respectively.
2.1 DATA QUALITY OBJECTIVES
Data quality objectives (DQOs) for the data collection activity describe
the overall level of uncertainty that a decision-maker is willing to accept in
results derived from environmental data. This uncertainty is used to specify the
quality of the measurement data required, usually in terms of objectives for
precision, bias, representativeness, comparability and completeness. The DQOs
should be defined prior to the initiation of the field and laboratory work. The
field and laboratory organizations performing the work should be aware of the
DQOs so that their personnel may make informed decisions during the course of the
project to attain those DQOs. More detailed information on DQOs is available
from the U.S. EPA Quality Assurance Management Staff (QAMS) (see references 2 and
4).
2.2 PROJECT OBJECTIVES
A statement of the project objectives and how the objectives are to be
attained should be concisely stated and sufficiently detailed to permit clear
understanding by all parties involved in the data collection effort. This
includes a statement of what problem is to be solved and the information required
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in the process. It also includes appropriate statements of the DQOs (i.e., the
acceptable level of uncertainty in the information).
2.3 SAMPLE COLLECTION
Sampling procedures, locations, equipment, and sample preservation and
handling requirements should be specified in the QAPjP. Further details on
quality assurance procedures for field operations are described in Section 3 of
this chapter. The OSW is developing policies and procedures for sampling in a
planned revision of Chapter Nine of this manual. Specific procedures for
groundwater sampling are provided in Chapter Eleven of this manual.
2.4 ANALYSIS AND TESTING
Analytes and properties of concern, analytical and testing procedures to
be employed, required detection limits, and requirements for precision and bias
should be specified. All applicable regulatory requirements and the project DQOs
should be considered when developing the specifications. Further details on the
procedures for analytical operations are described in Section 4 of this chapter.
2.5 QUALITY CONTROL
The quality assurance program should address both field and laboratory
activities. Quality control procedures should be specified for estimating the
precision and bias of the data. Recommended minimum requirements for QC samples
have been established by EPA and should be met in order to satisfy recommended
minimum criteria for acceptable data quality. Further details on procedures for
field and laboratory operations are described in Sections 3 and 4, respectively,
of this chapter.
2.6 PROJECT DOCUMENTATION
Documents should be prepared and maintained in conjunction with the data
collection effort. Project documentation should be sufficient to allow review
of all aspects of the work being performed. The QAPjP discussed in Sections 3
and 4 is one important document that should be maintained.
The length of storage time for project records should comply with
regulatory requirements, organizational policy, or project requirements,
whichever is more stringent. It is recommended that documentation be stored for
three years from submission of the project final report.
Documentation should be secured in a facility that adequately
addresses/minimizes its deterioration for the length of time that it is to be
retained. A system allowing for the expedient retrieval of information should
exist.
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Access to archived information should be controlled to maintain the
integrity of the data. Procedures should be developed to identify those
individuals with access to the data.
2.7 ORGANIZATION PERFORMING FIELD OR LABORATORY OPERATIONS
Proper design and structure of the organization facilitates effective and
efficient transfer of information and helps to prevent important procedures from
being overlooked.
The organizational structure, functional responsibilities, levels of
authority, job descriptions, and lines of communication for all project
activities should be established and documented. One person may cover more than
one organizational function. Each project participant should have a clear
understanding of his or her duties and responsibilities and the relationship of
those responsibilities to the overall data collection effort.
The management of each organization participating in a project involving
data collection activities should establish that organization's operational and
QA policies. This information should be documented in the QAPjP. The management
should ensure that (1) the appropriate methodologies are followed as documented
in the QAPjPs; (2) personnel clearly understand their duties and
responsibilities; (3) each staff member has access to appropriate project
documents; (4) any deviations from the QAPjP are communicated to the project
management and documented; and (5) communication occurs between the field,
laboratory, and project management, as specified in the QAPjP. In addition, each
organization should ensure that their activities do not increase the risk to
humans or the environment at or about the project location. Certain projects may
require specific policies or a Health and Safety Plan to provide this assurance.
The management of the participating field or laboratory organization should
establish personnel qualifications and training requirements for the project.
Each person participating in the project should have the education, training,
technical knowledge, and experience, or a combination thereof, to enable that
individual to perform assigned functions. Training should be provided for each
staff member as necessary to perform their functions properly. Personnel
qualifications should be documented in terms of education, experience, and
training, and periodically reviewed to ensure adequacy to current
responsibilities.
Each participating field organization or laboratory organization should
have a designated QA function (i.e., a team or individual trained in QA) to
monitor operations to ensure that the equipment, personnel, activities,
procedures, and documentation conform with the QAPjP. To the extent possible,
the QA monitoring function should be entirely separate from, and independent of,
personnel engaged in the work being monitored. The QA function should be
responsible for the QA review.
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2.7.1 Performance Evaluation
Performance evaluation studies are used to measure the performance of the
laboratory on unknown samples. Performance evaluation samples are typically
submitted to the laboratory as blind samples by an independent outside source.
The results are compared to predetermined acceptance limits. Performance
evaluation samples can also be submitted to the laboratory as part of the QA
function during internal assessment of laboratory performance. Records of all
performance evaluation studies should be maintained by the laboratory. Problems
identified through participation in performance evaluation studies should be
immediately investigated and corrected.
2.7.2 Internal Assessment by QA Function
Personnel performing field and laboratory activities are responsible for
continually monitoring individual compliance with the QAPjP. The QA function
should review procedures, results and calculations to determine compliance with
the QAPjP. The results of this internal assessment should be reported to
management with requirements for a plan to correct observed deficiencies.
2.7.3 External Assessment
The field and laboratory activities may be reviewed by personnel external
to the organization. Such an assessment is an extremely valuable method for
identifying overlooked problems. The results of the external assessment should
be submitted to management with requirements for a plan to correct observed
deficiencies.
2.7.4 On-Site Evaluation
On-site evaluations may be conducted as part of both internal and external
assessments. The focus of an on-site evaluation is to evaluate the degree of
conformance of project activities with the applicable QAPjP. On-site evaluations
may include, but are not limited to, a complete review of facilities, staff,
training, instrumentation, procedures, methods, sample collection, analyses, QA
policies and procedures related to the generation of environmental data. Records
of each evaluation should include the date of the evaluation, location, the areas
reviewed, the person performing the evaluation, findings and problems, and
actions recommended and taken to resolve problems. Any problems identified that
are likely to affect data integrity should be brought immediately to the
attention of management.
2.7.4.1 Field Activities
The review of field activities should be conducted by one or more persons
knowledgeable in the activities being reviewed and include evaluating, at a
minimum, the following subjects:
Completeness of Field Reports -- This review determines whether all
requirements for field activities in the QAPjP have been fulfilled, that
complete records exist for each field activity, and that the procedures
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specified in the QAPjP have been implemented. Emphasis on field
documentation will help assure sample integrity and sufficient technical
information to recreate each field event. The results of this
completeness check should be documented, and environmental data affected
by incomplete records should be identified.
Identification of Valid Samples -- This review involves interpretation and
evaluation of the field records to detect problems affecting the repre-
sentativeness of environmental samples. Examples of items that might
indicate potentially invalid samples include improper well development,
improperly screened wells, instability of pH or conductivity, and collec-
tion of volatiles near internal combustion engines. The field records
should be evaluated against the QAPjP and SOPs. The reviewer should docu-
ment the sample validity and identify the environmental data associated
with any poor or incorrect field work.
Correlation of Field Test Data -- This review involves comparing any
available results of field measurements obtained by more than one method.
For example, surface geophysical methods should correlate with direct
methods of site geologic characterization such as lithologic logs
constructed during drilling operations.
Identification of Anomalous Field Test Data -- This review identifies any
anomalous field test data. For example, a water temperature for one well
that is 5 degrees higher than any other well temperature in the same
aquifer should be noted. The reviewer should evaluate the impact of
anomalous field measurement results on the associated environmental data.
Validation of Field Analyses -- This review validates and documents all
data from field analysis that are generated in situ or from a mobile
laboratory as specified in Section 2.7.4.2. The reviewer should document
whether the QC checks meet the acceptance criteria, and whether corrective
actions were taken for any analysis performed when acceptance criteria
were exceeded.
2.7.4.2 Laboratory Activities
The review of laboratory data should be conducted by one or more persons
knowledgeable in laboratory activities and include evaluating, at a minimum, the
following subjects:
Completeness of Laboratory Records -- This review determines whether: (1)
all samples and analyses required by the QAPjP have been processed, (2)
complete records exist for each analysis and the associated QC samples,
and that (3) the procedures specified in the QAPjP have been implemented.
The results of the completeness check should be documented, and
environmental data affected by incomplete records should be identified.
Evaluation of Data with Respect to Detection and Quantitation Limits --
This review compares analytical results to required quantitation limits.
Reviewers should document instances where detection or quantitation limits
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exceed regulatory limits, action levels, or target concentrations
specified in the QAPjP.
Evaluation of Data with Respect to Control Limits -- This review compares
the results of QC and calibration check samples to control criteria.
Corrective action should be implemented for data not within control
limits. The reviewer should check that corrective action reports, and the
results of reanalysis, are available. The review should determine
whether samples associated with out-of-control QC data are identified in
a written record of the data review, and whether an assessment of the
utility of such analytical results is recorded.
Review of Holding Time Data -- This review compares sample holding times
to those required by the QAPjP, and notes all deviations.
Review of Performance Evaluation (PE) Results -- PE study results can be
helpful in evaluating the impact of out-of-control conditions. This review
documents any recurring trends or problems evident in PE studies and
evaluates their effect on environmental data.
Correlation of Laboratory Data -- This review determines whether the
results of data obtained from related laboratory tests, e.g., Purgeable
Organic Halides (POX) and Volatile Organics, are documented, and whether
the significance of any differences is discussed in the reports.
2.7.5 QA Reports
There should be periodic reporting of pertinent QA/QC information to the
project management to allow assessment of the overall effectiveness of the QA
program. There are three major types of QA reports to project management:
Periodic Report on Key QA Activities -- Provides summary of key QA activi-
ties during the period, stressing measures that are being taken to improve
data quality; describes significant quality problems observed and
corrective actions taken; reports information regarding any changes in
certification/accreditation status; describes involvement in resolution of
quality issues with clients or agencies; reports any QA organizational
changes; and provides notice of the distribution of revised documents
controlled by the QA organization (i.e., procedures).
Report on Measurement Quality Indicators -- Includes the assessment of QC
data gathered over the period, the frequency of analyses repeated due to
unacceptable QC performance, and, if possible, the reason for the unac-
ceptable performance and corrective action taken.
Reports on QA Assessments -- Includes the results of the assessments and
the plan for correcting identified deficiencies; submitted immediately
following any internal or external on-site evaluation or upon receipt of
the results of any performance evaluation studies.
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3.0 FIELD OPERATIONS
The field operations should be conducted in such a way as to provide
reliable information that meets the DQOs. To achieve this, certain minimal
policies and procedures should be implemented. The OSW is considering revisions
of Chapter Nine and Eleven of this manual. Supplemental information and guidance
is available in the RCRA Ground-Water Monitoring Technical Enforcement Guidance
Document (TEGD) (Reference 3). The project documentation should contain the
information specified below.
3.1 FIELD LOGISTICS
The QAPjP should describe the type(s) of field operations to be performed
and the appropriate area(s) in which to perform the work. The QAPjP should
address ventilation, protection from extreme weather and temperatures, access to
stable power, and provision for water and gases of required purity.
Whenever practical, the sampling site facilities should be examined prior
to the start of work to ensure that all required items are available. The actual
area of sampling should be examined to ensure that trucks, drilling equipment,
and personnel have adequate access to the site.
The determination as to whether sample shipping is necessary should be made
during planning for the project. This need is established by evaluating the
analyses to be performed, sample holding times, and location of the site and the
laboratory. Shipping or transporting of samples to a laboratory should be done
within a timeframe such that recommended holding times are met.
Samples should be packaged, labelled, preserved (e.g., preservative added,
iced, etc.), and documented in an area which is free of contamination and
provides for secure storage. The level of custody and whether sample storage is
needed should be addressed in the QAPjP.
Storage areas for solvents, reagents, standards, and reference materials
should be adequate to preserve their identity, concentration, purity, and
stability prior to use.
Decontamination of sampling equipment may be performed at the location
where sampling occurs, prior to going to the sampling site, or in designated
areas near the sampling site. Project documentation should specify where and how
this work is accomplished. If decontamination is to be done at the site, water
and solvents of appropriate purity should be available. The method of
accomplishing decontamination, including the required materials, solvents, and
water purity should be specified.
During the sampling process and during on-site or in situ analyses, waste
materials are sometimes generated. The method for storage and disposal of these
waste materials that complies with applicable local, state and Federal
regulations should be specified. Adequate facilities should be provided for the
collection and storage of all wastes, and these facilities should be operated so
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as to minimize environmental contamination. Waste storage and disposal
facilities should comply with applicable federal, state, and local regulations.
The location of long-term and short-term storage for field records, and the
measures to ensure the integrity of the data should be specified.
3.2 EQUIPMENT/INSTRUMENTATION
The equipment, instrumentation, and supplies at the sampling site should
be specified and should be appropriate to accomplish the activities planned. The
equipment and instrumentation should meet the requirements of specifications,
methods, and procedures as specified in the QAPjP.
3.3 OPERATING PROCEDURES
The QAPjP should describe or make reference to all field activities that
may affect data quality. For routinely performed activities, standard operating
procedures (SOPs) are often prepared to ensure consistency and to save time and
effort in preparing QAPjPs. Any deviation from an established procedure during
a data collection activity should be documented. The procedures should be
available for the indicated activities, and should include, at a minimum, the
information described below.
3.3.1 Sample Management
The numbering and labeling system, chain-of-custody procedures, and how the
samples are to be tracked from collection to shipment or receipt by the
laboratory should be specified. Sample management procedures should also specify
the holding times, volumes of sample required by the laboratory, required
preservatives, and shipping requirements.
3.3.2 Reagent/Standard Preparation
The procedures describing how to prepare standards and reagents should be
specified. Information concerning specific grades of materials used in reagent
and standard preparation, appropriate glassware and containers for preparation
and storage, and labeling and record keeping for stocks and dilutions should be
included.
3.3.3 Decontamination
The procedures describing decontamination of field equipment before and
during the sample collection process should be specified. These procedures
should include cleaning materials used, the order of washing and rinsing with the
cleaning materials, requirements for protecting or covering cleaned equipment,
and procedures for disposing of cleaning materials.
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3.3.4 Sample Collection
The procedures describing how the sampling operations are actually
performed in the field should be specified. A simple reference to standard
methods is not sufficient, unless a procedure is performed exactly as described
in the published method. Methods from source documents published by the EPA,
American Society for Testing and Materials, U.S. Department of the Interior,
National Water Well Association, American Petroleum Institute, or other
recognized organizations with appropriate expertise should be used, if possible.
The procedures for sample collection should include at least the following:
• Applicability of the procedure,
• Equipment required,
• Detailed description of procedures to be followed in collecting the
samples,
• Common problems encountered and corrective actions to be followed, and
• Precautions to be taken.
3.3.5 Field Measurements
The procedures describing all methods used in the field to determine a
chemical or physical parameter should be described in detail. The procedures
should address criteria from Section 4, as appropriate.
3.3.6 Equipment Calibration And Maintenance
The procedures describing how to ensure that field equipment and
instrumentation are in working order should be specified. These describe
calibration procedures and schedules, maintenance procedures and schedules,
maintenance logs, and service arrangements for equipment. Calibration and
maintenance of field equipment and instrumentation should be in accordance with
manufacturers' specifications or applicable test specifications and should be
documented.
3.3.7 Corrective Action
The procedures describing how to identify and correct deficiencies in the
sample collection process should be specified. These should include specific
steps to take in correcting deficiencies such as performing additional
decontamination of equipment, resampling, or additional training of field
personnel. The procedures should specify that each corrective action should be
documented with a description of the deficiency and the corrective action taken*
and should include the person(s) responsible for implementing the corrective
action.
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3.3.8 Data Reduction and Validation
The procedures describing how to compute results from field measurements
and to review and validate these data should be specified. They should include
all formulas used to calculate results and procedures used to independently
verify that field measurement results are correct.
3.3.9 Reporting
The procedures describing the process for reporting the results of field
activities should be specified.
3.3.10 Records Management
The procedures describing the means for generating, controlling, and
archiving project-specific records and field operations records should be
specified. These procedures should detail record generation and control and the
requirements for record retention, including type, time, security, and retrieval
and disposal authorities.
Project-specific records relate to field work performed for a project.
These records may include correspondence, chain-of-custody records, field
notes, all reports issued as a result of the work, and procedures used.
Field operations records document overall field operations and may include
equipment performance and maintenance logs, personnel files, general field
procedures, and corrective action reports.
3.3.11 Waste Disposal
The procedures describing the methods for disposal of waste materials
resulting from field operations should be specified.
3.4 FIELD QA AND QC REQUIREMENTS
The QAPjP should describe how the following elements of the field QC
program will be implemented.
3.4.1 Control Samples
Control samples are QC samples that are introduced into a process to
monitor the performance of the system. Control samples, which may include blanks
(e.g., trip, equipment, and laboratory), duplicates, spikes, analytical
standards, and reference materials, can be used in different phases of the data
collection process beginning with sampling and continuing through transportation,
storage, and analysis.
Each day of sampling, at least one field duplicate and one equipment
rinsate should be collected for each matrix sampled. If this frequency is not
appropriate for the sampling equipment and method, then the appropriate changes
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should be^TeaHy identified in the QAPjP. When samples are collected for
volatile organic analysis, a trip blank is also recommended for each day that
samples are collected. In addition, for each sampling batch (20 samples of one
matrix type), enough volume should be collected for at least one sample so as to
allow the laboratory to prepare one matrix spike and either one matrix duplicate
or one matrix spike duplicate for each analytical method employed. This means
that the following control samples are recommended:
•Field duplicate (one per day per matrix type)
•Equipment rinsate (one per day per matrix type)
•Trip blank (one per day, volatile organics only)
•Matrix spike (one per batch [20 samples of each matrix type])
•Matrix duplicate or matrix spike duplicate (one per batch)
Additional control samples may be necessary in order to assure data quality to
meet the project-specific DQOs.
3.4.2 Acceptance Criteria
Procedures should be in place for establishing acceptance criteria for
field activities described in the QAPjP. Acceptance criteria may be qualitative
or quantitative. Field events or data that fall outside of established
acceptance criteria may indicate a problem with the sampling process that should
be investigated.
3.4.3 Deviations
All deviations from plan should be documented as to the extent of, and
reason for, the deviation. Any activity not performed in accordance with
procedures or QAPjPs is considered a deviation from plan. Deviations from plan
may or may not affect data quality.
3.4.4 Corrective Action
Errors, deficiencies, deviations, certain field events, or data that fall
outside established acceptance criteria should be investigated. In some in-
stances, corrective action may be needed to resolve the problem and restore
proper functioning to the system. The investigation of the problem and any
subsequent corrective action taken should be documented.
3.4.5 Data Handling
All field measurement data should be reduced according to protocols
described or referenced in the QAPjP. Computer programs used for data reduction
should be validated before use and verified on a regular basis. All information
used in the calculations should be recorded to enable reconstruction of the final
result at a later date.
Data should be reported in accordance with the requirements of the end-user
as described in the QAPjP.
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3.5 QUALITY ASSURANCE REVIEW
The QA Review consists of internal and external assessments to ensure that
QA/QC procedures are in use and to ensure that field staff conform to these
procedures. QA review should be conducted as deemed appropriate and necessary.
3.6 FIELD RECORDS
Records provide the direct evidence and support for the necessary technical
interpretations, judgments, and discussions concerning project activities. These
records, particularly those that are anticipated to be used as evidentiary data,
should directly support current or ongoing technical studies and activities and
should provide the historical evidence needed for later reviews and analyses.
Records should be legible, identifiable, and retrievable and protected against
damage, deterioration, or loss. The discussion in this section (3.6) outlines
recommended procedures for record keeping. Organizations which conduct field
sampling should develop appropriate record keeping procedures which satisfy
relevant technical and legal requirements.
Field records generally consist of bound field notebooks with prenumbered
pages, sample collection forms, personnel qualification and training forms,
sample location maps, equipment maintenance and calibration forms, chain-of-
custody forms, sample analysis request forms, and field change request forms.
All records should be written in indelible ink.
Procedures for reviewing, approving, and revising field records should be
clearly defined, with the lines of authority included. It is recommended that
all documentation errors should be corrected by drawing a single line through the
error so it remains legible and should be initialed by the responsible
individual, along with the date of change. The correction should be written
adjacent to the error.
Records should include (but are not limited to) the following:
Calibration Records & Traceability of Standards/Reagents -- Calibration is
a reproducible reference point to which all sample measurements can be
correlated. A sound calibration program should include provisions for
documentation of frequency, conditions, standards, and records reflecting
the calibration history of a measurement system. The accuracy of the
calibration standards is important because all data will be in reference
to the standards used. A program for verifying and documenting the
accuracy of all working standards against primary grade standards should
be routinely followed.
Sample Collection -- To ensure maximum utility of the sampling effort and
resulting data, documentation of the sampling protocol, as performed in
the field, is essential. It is recommended that sample collection records
contain, at a minimum, the names of persons conducting the activity,
sample number, sample location, equipment used, climatic conditions,
documentation of adherence to protocol, and unusual observations. The
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actual sample collection record is usually one of the following: a bound
field notebook with prenumbered pages, a pre-printed form, or digitized
information on a computer tape or disc.
Chain-of-Custody Records -- The chain-of-custody involving the possession
of samples from the time they are obtained until they are disposed or
shipped off-site should be documented as specified in the QAPjP and should
include the following information: (1) the project name; (2) signatures
of samplers; (3) the sample number, date and time of collection, and grab
or composite sample designation; (4) signatures of individuals involved in
sample transfer; and (5) if applicable, the air bill or other shipping
number.
Maps and Drawings -- Project planning documents and reports often contain
maps. The maps are used to document the location of sample collection
points and monitoring wells and as a means of presenting environmental
data. Information used to prepare maps and drawings is normally obtained
through field surveys, property surveys, surveys of monitoring wells,
aerial photography or photogrammetric mapping. The final, approved maps
and/or drawings should have a revision number and date and should be sub-
ject to the same controls as other project records.
QC Samples -- Documentation for generation of QC samples, such as trip and
equipment rinsate blanks, duplicate samples, and any field spikes should
be maintained.
Deviations -- All deviations from procedural documents and the QAPjP
should be recorded in the site logbook.
Reports -- A copy of any report issued and any supporting documentation
should be retained.
4.0 LABORATORY OPERATIONS
The laboratory should conduct its operations in such a way as to provide
reliable information. To achieve this, certain minimal policies and procedures
should be implemented.
4.1 FACILITIES
The QAPjP should address all facility-related issues that may impact
project data quality. Each laboratory should be of suitable size and
construction to facilitate the proper conduct of the analyses. Adequate bench
space or working area per analyst should be provided. The space requirement per
analyst depends on the equipment or apparatus that is being utilized, the number
of samples that the analyst is expected to handle at any one time, and the number
of operations that are to be performed concurrently by a single analyst. Other
issues to be considered include, but are not limited to, ventilation, lighting,
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control of dust and drafts, protection from extreme temperatures, and access to
a source of stable power.
Laboratories should be designed so that there is adequate separation of
functions to ensure that no laboratory activity has an adverse effect on the
analyses. The laboratory may require specialized facilities such as a perchloric
acid hood or glovebox.
Separate space for laboratory operations and appropriate ancillary support
should be provided, as needed, for the performance of routine and specialized
procedures.
As necessary to ensure secure storage and prevent contamination or
misidentification, there should be adequate facilities for receipt and storage
of samples. The level of custody required and any special requirements for
storage such as refrigeration should be described in planning documents.
Storage areas for reagents, solvents, standards, and reference materials
should be adequate to preserve their identity, concentration, purity, and
stability.
Adequate facilities should be provided for the collection and storage of
all wastes, and these facilities should be operated so as to minimize environ-
mental contamination. Waste storage and disposal facilities should comply with
applicable federal, state, and local regulations.
The location of long-term and short-term storage of laboratory records and
the measures to ensure the integrity of the data should be specified.
4.2 EQUIPMENT/INSTRUMENTATION
Equipment and instrumentation should meet the requirements and specifica-
tions of the specific test methods and other procedures as specified in the
QAPjP. The laboratory should maintain an equipment/instrument description list
that includes the manufacturer, model number, year of purchase, accessories, and
any modifications, updates, or upgrades that have been made.
4.3 OPERATING PROCEDURES
The QAPjP should describe or make reference to all laboratory activities
that may affect data quality. For routinely performed activities, SOPs are often
prepared to ensure consistency and to save time and effort in preparing QAPjPs.
Any deviation from an established procedure during a data collection activity
should be documented. It is recommended that procedures be available for the
indicated activities, and include, at a minimum, the information described
below.
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4.3.1 Sample Management
The procedures describing the receipt, handling, scheduling, and storage
of samples should be specified.
Sample Receipt and Handling -- These procedures describe the precautions
to be used in opening sample shipment containers and how to verify that
chain-of-custody has been maintained, examine samples for damage, check
for proper preservatives and temperature, and log samples into the
laboratory sample streams.
Sample Scheduling -- These procedures describe the sample scheduling in
the laboratory and includes procedures used to ensure that holding time
requirements are met.
Sample Storage -- These procedures describe the storage conditions for all
samples, verification and documentation of daily storage temperature, and
how to ensure that custody of the samples is maintained while in the
laboratory.
4.3.2 Reagent/Standard Preparation
The procedures describing how to prepare standards and reagents should be
specified. Information concerning specific grades of materials used in reagent
and standard preparation, appropriate glassware and containers for preparation
and storage, and labeling and recordkeeping for stocks and dilutions should be
included.
4.3.3 General Laboratory Techniques
The procedures describing all essentials of laboratory operations that are
not addressed elsewhere should be specified. These techniques should include,
but are not limited to, glassware cleaning procedures, operation of analytical
balances, pipetting techniques, and use of volumetric glassware.
4.3.4 Test Methods
Procedures for test methods describing how the analyses are actually
performed in the laboratory should be specified. A simple reference to standard
methods is not sufficient, unless the analysis is performed exactly as described
in the published method. Whenever methods from SW-846 are not appropriate,
recognized methods from source documents published by the EPA, American Public
Health Association (APHA), American Society for Testing and Materials (ASTM), the
National Institute for Occupational Safety and Health (NIOSH), or other
recognized organizations with appropriate expertise should be used, if possible.
The documentation of the actual laboratory procedures for analytical methods
should include the following:
Sample Preparation and Analysis Procedures -- These include applicable
holding time, extraction, digestion, or preparation steps as appropriate
to the method; procedures for determining the appropriate dilution to
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analyze; and any other information required to perform the analysis
accurately and consistently.
Instrument Standardization -- This includes concentration(s) and frequency
of analysis of calibration standards, linear range of the method, and
calibration acceptance criteria.
Sample Data -- This includes recording requirements and documentation in-
cluding sample identification number, analyst, data verification, date of
analysis and verification, and computational method(s).
Precision and Bias -- This includes all analytes for which the method is
applicable and the conditions for use of this information.
Detection and Reporting Limits -- This includes all analytes in the
method.
Test-Specific QC -- This describes QC activities applicable to the
specific test and references any applicable QC procedures.
4.3.5 Equipment Calibration and Maintenance
The procedures describing how to ensure that laboratory equipment and
instrumentation are in working order should be specified. These procedures
include calibration procedures and schedules, maintenance procedures and
schedules, maintenance logs, service arrangements for all equipment, and spare
parts available in-house. Calibration and maintenance of laboratory equipment
and instrumentation should be in accordance with manufacturers' specifications
or applicable test specifications and should be documented.
4.3.6 QC
The type, purpose, and frequency of QC samples to be analyzed in the
laboratory and the acceptance criteria should be specified. Information should
include the applicability of the QC sample to the analytical process, the
statistical treatment of the data, and the responsibility of laboratory staff and
management in generating and using the data. Further details on development of
project-specific QC protocols are described in Section 4.4.
4.3.7 Corrective Action
The procedures describing how to identify and correct deficiencies in the
analytical process should be specified. These should include specific steps to
take in correcting the deficiencies such as preparation of new standards and
reagents, recalibration and restandardization of equipment, reanalysis of
samples, or additional training of laboratory personnel in methods and
procedures. The procedures should specify that each corrective action should be
documented with a description of the deficiency and the corrective action taken,
and should include the person(s) responsible for implementing the corrective
action.
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4.3.8 Data Reduction and Validation
The procedures describing how to review and validate the data should be
specified. They should include procedures for computing and interpreting the
results from QC samples, and independent procedures to verify that the analytical
results are reported correctly. In addition, routine procedures used to monitor
precision and bias, including evaluations of reagent, equipment rinsate, and trip
blanks, calibration standards, control samples, duplicate and matrix spike
samples, and surrogate recovery, should be detailed in the procedures. More
detailed validation procedures should be performed when required in the contract
or QAPjP.
4.3.9 Reporting
The procedures describing the process for reporting the analytical results
should be specified.
4.3.10 Records Management
The procedures describing the means for generating, controlling, and
archiving laboratory records should be specified. The procedures should detail
record generation and control, and the requirements for record retention, includ-
ing type, time, security, and retrieval and disposal authorities.
Project-specific records may include correspondence, chain-of-custody
records, request for analysis, calibration data records, raw and finished
analytical and QC data, data reports, and procedures used.
Laboratory operations records may include laboratory notebooks, instrument
performance logs and maintenance logs in bound notebooks with prenumbered
pages; laboratory benchsheets; software documentation; control charts;
reference material certification; personnel files; laboratory procedures;
and corrective action reports.
4.3.11 Waste Disposal
The procedures describing the methods for disposal of chemicals including
standard and reagent solutions, process waste, and samples should be specified.
4.4 LABORATORY QA AND QC PROCEDURES
The QAPjP should describe how the following required elements of the
laboratory QC program are to be implemented.
4.4.1 Method Proficiency
Procedures should be in place for demonstrating proficiency with each
analytical method routinely used in the laboratory. These should include
procedures for demonstrating the precision and bias of the method as performed
by the laboratory and procedures for determining the method detection limit
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(MDL). All terminology, procedures and frequency of determinations associated
with the laboratory's establishment of the MDL and the reporting limit should be
well-defined and well-documented. Documented precision, bias, and MDL
information should be maintained for all methods performed in the laboratory.
4.4.2 Control Limits
Procedures should be in place for establishing and updating control limits
for analysis. Control limits should be established to evaluate laboratory
precision and bias based on the analysis of control samples. Typically, control
limits for bias are based on the historical mean recovery plus or minus three
standard deviation units, and control limits for precision range from zero (no
difference between duplicate control samples) to the historical mean relative
percent difference plus three standard deviation units. Procedures should be in
place for monitoring historical performance and should include graphical (control
charts) and/or tabular presentations of the data.
4.4.3 Laboratory Control Procedures
Procedures should be in place for demonstrating that the laboratory is in
control during each data collection activity. Analytical data generated with
laboratory control samples that fall within prescribed limits are judged to be
generated while the laboratory was in control. Data generated with laboratory
control samples that fall outside the established control limits are judged to
be generated during an "out-of-control" situation. These data are considered
suspect and should be repeated or reported with qualifiers.
Laboratory Control Samples -- Laboratory control samples should be
analyzed for each analytical method when appropriate for the method. A
laboratory control sample consists of either a control matrix spiked with
analytes representative of the target analytes or a certified reference
material.
Laboratory control sample(s) should be analyzed with each batch of samples
processed to verify that the precision and bias of the analytical process
are within control limits. The results of the laboratory control
sample(s) are compared to control limits established for both precision
and bias to determine usability of the data.
Method Blank -- When appropriate for the method, a method blank should be
analyzed with each batch of samples processed to assess contamination
levels in the laboratory. Guidelines should be in place for accepting or
rejecting data based on the level of contamination in the blank.
Procedures should be in place for documenting the effect of the matrix on
method performance. When appropriate for the method, there should be at least
one matrix spike and either one matrix duplicate or one matrix spike duplicate
per analytical batch. Additional control samples may be necessary to assure data
quality to meet the project-specific DQOs.
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Matrix-Specific Bias -- Procedures should be in place for determining the
bias of the method due to the matrix. These procedures should include
preparation and analysis of matrix spikes, selection and use of surrogates
for organic methods, and the method of standard additions for metal and
inorganic methods. When the concentration of the analyte in the sample is
greater than 0.1%, no spike is necessary.
Matrix-Specific Precision -- Procedures should be in place for determining
the precision of the method for a specific matrix. These procedures
should include analysis of matrix duplicates and/or matrix spike
duplicates. The frequency of use of these techniques should be based on
the DQO for the data collection activity.
Matrix-Specific Detection Limit -- Procedures should be in place for
determining the MDL for a specific matrix type (e.g., wastewater treatment
sludge, contaminated soil, etc).
4.4.4 Deviations
Any activity not performed in accordance with laboratory procedures or
QAPjPs is considered a deviation from plan. All deviations from plan should be
documented as to the extent of, and reason for, the deviation.
4.4.5 Corrective Action
Errors, deficiencies, deviations, or laboratory events or data that fall
outside of established acceptance criteria should be investigated. In some
instances, corrective action may be needed to resolve the problem and restore
proper functioning to the analytical system. The investigation of the problem
and any subsequent corrective action taken should be documented.
4.4.6 Data Handling
Data resulting from the analyses of samples should be reduced according to
protocols described in the laboratory procedures. Computer programs used for
data reduction should be validated before use and verified on a regular basis.
All information used in the calculations (e.g., raw data, calibration files,
tuning records, results of standard additions, interference check results, and
blank- or background-correction protocols) should be recorded in order to enable
reconstruction of the final result at a later date. Information on the
preparation of the sample (e.g., weight or volume of sample used, percent dry
weight for solids, extract volume, dilution factor used) should also be
maintained in order to enable reconstruction of the final result at a later date.
All data should be reviewed by a second analyst or supervisor according to
laboratory procedures to ensure that calculations are correct and to detect
transcription errors. Spot checks should be performed on computer calculations
to verify program validity. Errors detected in the review process should be
referred to the analyst(s) for corrective action. Data should be reported in
accordance with the requirements of the end-user. It is recommended that the
supporting documentation include at a minimum:
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Laboratory name and address.
Sample information (including unique sample identification, sample
collection date and time, date of sample receipt, and date(s) of sample
preparation and analysis).
Analytical results reported with an appropriate number of significant
figures.
Detection limits that reflect dilutions, interferences, or correction for
equivalent dry weight.
Method reference.
Appropriate QC results (correlation with sample batch should be traceable
and documented).
Data qualifiers with appropriate references and narrative on the quality
of the results.
4.5 QUALITY ASSURANCE REVIEW
The QA review consists of internal and external assessments to ensure that
QA/QC procedures are in use and to ensure that laboratory staff conform to these
procedures. QA review should be conducted as deemed appropriate and necessary.
4.6 LABORATORY RECORDS
Records provide the direct evidence and support for the necessary technical
interpretations, judgements, and discussions concerning project activities.
These records, particularly those that are anticipated to be used as evidentiary
data, should directly support technical studies and activities, and provide the
historical evidence needed for later reviews and analyses. Records should be
legible, identifiable, and retrievable, and protected against damage,
deterioration, or loss. The discussion in this section (4.6) outlines
recommended procedures for record keeping. Organizations which conduct field
sampling should develop appropriate record keeping procedures which satisfy
relevant technical and legal requirements.
Laboratory records generally consist of bound notebooks with prenumbered
pages, personnel qualification and training forms, equipment maintenance and
calibration forms, chain-of-custody forms, sample analysis request forms, and
analytical change request forms. All records should be written in indelible ink.
Procedures for reviewing, approving, and revising laboratory records should
be clearly defined, with the lines of authority included. Any documentation
errors should be corrected by drawing a single line through the error so that it
remains legible and should be initialed by the responsible individual, along with
the date of change. The correction is written adjacent to the error.
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Strip-chart recorder printouts should be signed by the person who performed
the instrumental analysis. If corrections need to be made in computerized data,
a system parallel to the corrections for handwritten data should be in place.
Records of sample management should be available to permit the re-creation
of an analytical event for review in the case of an audit or investigation of a
dubious result.
Laboratory records should include, at least, the following:
Operating Procedures -- Procedures should be available to those performing
the task outlined. Any revisions to laboratory procedures should be
written, dated, and distributed to all affected individuals to ensure
implementation of changes. Areas covered by operating procedures are
given in Sections 3.3 and 4.3.
Quality Assurance Plans -- The QAPjP should be on file.
Equipment Maintenance Documentation -- A history of the maintenance record
of each system serves as an indication of the adequacy of maintenance
schedules and parts inventory. As appropriate, the maintenance guidelines
of the equipment manufacturer should be followed. When maintenance is
necessary, it should be documented in either standard forms or in
logbooks. Maintenance procedures should be clearly defined and written
for each measurement system and required support equipment.
Proficiency -- Proficiency information on all compounds reported should be
maintained and should include (1) precision; (2) bias; (3) method detec-
tion limits; (4) spike recovery, where applicable; (5) surrogate recovery,
where applicable; (6) checks on reagent purity, where applicable; and
(7) checks on glassware cleanliness, where applicable.
Calibration Records & Traceability of Standards/Reagents -- Calibration is
a reproducible reference point to which all sample measurements can be
correlated. A sound calibration program should include provisions for
documenting frequency, conditions, standards, and records reflecting the
calibration history of a measurement system. The accuracy of the
calibration standards is important because all data will be in reference
to the standards used. A program for verifying and documenting the
accuracy and traceability of all working standards against appropriate
primary grade standards or the highest quality standards available should
be routinely followed.
Sample Management -- All required records pertaining to sample management
should be maintained and updated regularly. These include chain-of-
custody forms, sample receipt forms, and sample disposition records.
Original Data -- The raw data and calculated results for all samples
should be maintained in laboratory notebooks, logs, benchsheets, files or
other sample tracking or data entry forms. Instrumental output should be
stored in a computer file or a hardcopy report.
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QC Data -- The raw data and calculated results for all QC and field
samples and standards should be maintained in the manner described in the
preceding paragraph. Documentation should allow correlation of sample
results with associated QC data. Documentation should also include the
source and lot numbers of standards for traceability. QC samples include,
but are not limited to, control samples, method blanks, matrix spikes, and
matrix spike duplicates.
Correspondence -- Project correspondence can provide evidence supporting
technical interpretations. Correspondence pertinent to the project should
be kept and placed in the project files.
Deviations -- All deviations from procedural and planning documents should
be recorded in laboratory notebooks. Deviations from QAPjPs should be
reviewed and approved by the authorized personnel who performed the
original technical review or by their designees.
Final Report -- A copy of any report issued and any supporting documenta-
tion should be retained.
5.0 DEFINITIONS
The following terms are defined for use in this document:
ACCURACY
BATCH:
BIAS:
The closeness of agreement between an observed value and
an accepted reference value. When applied to a set of
observed values, accuracy will be a combination of a
random component and of a common systematic error (or
bias) component.
A group of samples which behave similarly with respect to
the sampling or the testing procedures being employed and
which are processed as a unit (see Section 3.4.1 for field
samples and Section 4.4.3 for laboratory samples). For QC
purposes, if the number of samples in a group is greater
than 20, then each group of 20 samples or less will all be
handled as a separate batch.
The deviation due to matrix effects of the measured value
(xs - xu) from a known spiked amount. Bias can be assessed
by comparing a measured value to an accepted reference
value in a sample of known concentration or by determining
the recovery of a known amount of contaminant spiked into
a sample (matrix spike). Thus, the bias (B) due to matrix
effects based on a matrix spike is calculated as:
where:
B = (x. - xu ) - K
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BLANK:
CONTROL SAMPLE:
DATA QUALITY
OBJECTIVES (DQOs)
DATA VALIDATION:
DUPLICATE:
EQUIPMENT BLANK:
EQUIPMENT RINSATE:
ESTIMATED
QUANTITATION
LIMIT (EQL):
xs = measured value for spiked sample,
xu = measured value for unspiked sample, and
K = known value of the spike in the sample.
Using the following equation yields the percent recovery
%R = 100 (xs - xj/ K
see Equipment Rinsate, Method Blank, Trip Blank.
A QC sample introduced into a process to monitor the
performance of the system.
A statement of the overall level of uncertainty that a
decision-maker is willing to accept in results derived
from environmental data (see reference 2, EPA/QAMS, July
16, 1986). This is qualitatively distinct from quality
measurements such as precision, bias, and detection limit.
The process of evaluating the available data against the
project DQOs to make sure that the objectives are met.
Data validation may be very
depending on project DQOs. The
will include analytical results,
data, and may also include field
rigorous, or cursory,
available data reviewed
field QC data and lab QC
records.
see Matrix Duplicate,
Duplicate.
see Equipment Rinsate.
Field Duplicate, Matrix Spike
A sample of analyte-free media which has been used to
rinse the sampling equipment. It is collected after
completion of decontamination and prior to sampling. This
blank is useful in documenting adequate decontamination of
sampling equipment.
The lowest concentration that can be reliably achieved
within specified limits of precision and accuracy during
routine laboratory operating conditions. The EQL is
generally 5 to 10 times the MDL. However, it may be
nominally chosen within these guidelines to simplify data
reporting. For many analytes the EQL analyte
concentration is selected as the lowest non-zero standard
in the calibration curve. Sample EQLs are highly matrix-
dependent. The EQLs in SW-846 are provided for guidance
and may not always be achievable.
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FIELD DUPLICATES:
LABORATORY CONTROL
SAMPLE:
MATRIX:
MATRIX DUPLICATE:
MATRIX SPIKE:
MATRIX SPIKE
DUPLICATES:
METHOD BLANK:
METHOD DETECTION
LIMIT (MDL):
Independent samples which are collected as close as
possible to the same point in space and time. They are
two separate samples taken from the same source, stored in
separate containers, and analyzed independently. These
duplicates are useful in documenting the precision of the^
sampling process.
A known matrix spiked with compound(s) representative of
the target analytes. This is used to document laboratory
performance.
The component or substrate (e.g., surface water, drinking
water) which contains the analyte of interest.
An intralaboratory split sample which is used to document
the precision of a method in a given sample matrix.
An aliquot of sample spiked with a known concentration of
target analyte(s). The spiking occurs prior to sample
preparation and analysis. A matrix spike is used to
document the bias of a method in a given sample matrix.
Intralaboratory split samples spiked with identical
concentrations of target analyte(s). The spiking occurs
prior to sample preparation and analysis. They are used
to document the precision and bias of a method in a given
sample matrix.
An analyte-free matrix to which all reagents are added in
the same volumes or proportions as used in sample
processing. The method blank should be carried through
the complete sample preparation and analytical procedure.
The method blank is used to document contamination
resulting from the analytical process.
For a method blank to be acceptable for use with the
accompanying samples, the concentration in the blank of
any analyte of concern should not be higher than the
highest of either:
(l)The method detection limit, or
(2)Five percent of the regulatory limit for that analyte,
or
(3)Five percent of the measured concentration in the
sample.
The minimum concentration of a substance that can be
measured and reported with 99% confidence that the analyte
concentration is greater than zero and is determined from
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analysis of a sample in a given matrix type containing
the analyte.
For operational purposes, when it is necessary to
determine the MDL in the matrix, the MDL should be
determined by multiplying the appropriate one-sided 99% t-
statistic by the standard deviation obtained from a
minimum of three analyses of a matrix spike containing the
analyte of interest at a concentration three to five times
the estimated MDL, where the t-statistic is obtained from
standard references or the table below.
No. of samples; t-statistic
3 6.96
4 4.54
5 3.75
6 3.36
7 3.14
8 3.00
9 2.90
10 2.82
Estimate the MDL as follows:
Obtain the concentration value that corresponds to:
a) an instrument signal/noise ratio within the range of
2.5 to 5.0, or
b) the region of the standard curve where there is a
significant change in sensitivity (i.e., a break in the
slope of the standard curve).
Determine the variance (S2) for each analyte as follows:
n-1
where Xi = the ith measurement of the variable x
and x = the average value of x;
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Determine the standard deviation (s) for each analyte as
follows:
1/2
Determine the MDL for each analyte as follows:
ORGANIC-FREE
REAGENT WATER:
PRECISION:
MDL
'(n-1, o = .99)
(S)
where t(n_., 99. is the one-sided t-statistic appropriate
for the number'or samples used to determine (s), at the 99
percent level.
For volatiles, all references to water in the methods
refer to water in which an interferant is not observed at
the method detection limit of the compounds of interest.
Organic-free reagent water can be generated by passing tap
water through a carbon filter bed containing about 1 pound
of activated carbon. A water purification system may be
used to generate organic-free deionized water.
Organic-free reagent water may also be prepared by boiling
water for 15 minutes and, subsequently, while maintaining
the temperature at 90°C, bubbling a contaminant-free inert
gas through the water for 1 hour.
For semivolatiles and nonvolatiles, all references to
water in the methods refer to water in which an
interferant is not observed at the method detection limit
of the compounds of interest. Organic-free reagent water
can be generated by passing tap water through a carbon
filter bed containing about 1 pound of activated carbon.
A water purification system may be used to generate
organic-free deionized water.
The agreement among a set of replicate measurements
without assumption of knowledge of the true value.
Precision is estimated by means of duplicate/replicate
analyses. These samples should contain concentrations of
analyte above the MDL, and may involve the use of matrix
spikes. The most commonly used estimates of precision are
the relative standard deviation (RSD) or the coefficient
of variation (CV),
RSD = CV = 100 S/x,
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PROJECT:
QUALITY ASSURANCE
PROJECT PLAN
(QAPJP):
RCRA:
REAGENT BLANK:
REAGENT GRADE:
REAGENT WATER:
REFERENCE MATERIAL:
SPLIT SAMPLES:
STANDARD ADDITION:
STANDARD CURVE:
wjiere:
x = the arithmetic mean of the Xj measurements, and S =
variance; and the relative percent difference (RPD) when
only two samples are available.
RPD = 100
- x2)/{(Xl + x2)/2}].
Single or multiple data collection activities that are
related through the same planning sequence.
An orderly assemblage of detailed procedures designed to
produce data of sufficient quality to meet the data
quality objectives for a specific data collection
activity.
The Resource Conservation and Recovery Act.
See Method Blank.
Analytical reagent (AR) grade, ACS reagent grade, and
reagent grade are synonymous terms for reagents which
conform to the current specifications of the Committee on
Analytical Reagents of the American Chemical Society.
Water that has been generated by any method which would
achieve the performance specifications for ASTM Type II
water. For organic analyses, see the definition of
organic-free reagent water.
A material containing known quantities of target analytes
in solution or in a homogeneous matrix. It is used to
document the bias of the analytical process.
Aliquots of sample taken from the same container and
analyzed independently. In cases where aliquots of
samples are impossible to obtain, field duplicate samples
should be taken for the matrix duplicate analysis. These
are usually taken after mixing or compositing and are used
to document intra- or interlaboratory precision.
The practice of adding a known amount of an analyte to a
sample immediately prior to analysis. It is typically
used to evaluate interferences.
A plot of concentrations of known analyte standards versus
the instrument response to the analyte. Calibration
standards are prepared by successively diluting a standard
solution to produce working standards which cover the
working range of the instrument. Standards should be
prepared at the frequency specified in the appropriate
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section. The calibration standards should be prepared
using the same type of acid or solvent and at the same
concentration as will result in the samples following
sample preparation. This is applicable to organic and
inorganic chemical analyses.
SURROGATE: An organic compound which is similar to the target
analyte(s) in chemical composition and behavior in the
analytical process, but which is not normally found in
environmental samples.
TRIP BLANK: A sample of analyte-free media taken from the laboratory
to the sampling site and returned to the laboratory
unopened. A trip blank is used to document contamination
attributable to shipping and field handling procedures.
This type of blank is useful in documenting contamination
of volatile organics samples.
6.0 REFERENCES
1. Interim Guidelines and Specifications for Preparing Quality Assurance
Project Plans, QAMS-005/80, December 29, 1980, Office of Monitoring Systems
and Quality Assurance, ORD, U.S. EPA, Washington, DC 20460.
2. Development of Data Quality Objectives, Description of Stages I and II, July
16, 1986, Quality Assurance Management Staff, ORD, U.S. EPA, Washington, DC
20460.
3. RCRA Ground-Water Monitoring Technical Enforcement Guidance Document,
September, 1986, Office of Waste Programs Enforcement. OSWER, U.S. EPA,
Washington, DC, 20460.
4. DQO Training Software, Version 6.5, December, 1988, Quality Assurance
Management Staff, ORD, U.S. EPA, Washington, DC 20460.
5. Preparing Perfect Project Plans, EPA/600/9-89/087, October 1989, Risk
Reduction Engineering Laboratory (Guy Simes), Cincinnati OH.
6. ASTM Method D 1129-77, Specification for Reagent Water. 1991 Annual Book
of ASTM Standards. Volume 11.01 Water and Environmental Technology.
7. Generation of Environmental Data Related to Waste Management Activities
(Draft). February 1989. ASTM.
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INDEX
Accuracy 1, 13, 22, 23*, 24
Batch 12, 19, 21, 23*
Bias 2, 3, 17-20, 22, 23*-25, 28
Blank 11, 12, 14, 18-20, 23*, 24, 25, 28, 29
Equipment Rinsate 11, 12, 14, 18, 24*
Method Blank 19, 24, 25*, 28
Reagent Blank 28*
Trip Blank 12, 18, 24, 29*
Chain-of-Custody 9, 11, 13, 14, 18, 21, 22
Control Chart 18, 19
Control Sample 11, 12, 18, 19, 23, 24*
Data Quality Objectives (DQO) 1-3, 8, 12, 19, 20, 24", 28
Decision-maker 2, 24
Duplicate 11, 12, 14, 18-20, 23, 24", 25, 27, 28
Field Duplicate 11, 12, 24, 25", 28
Matrix Duplicate 12, 19, 20, 24, 25", 28
Matrix Spike Duplicate 12, 19, 20, 23, 24, 25"
Equipment Blank 11, 24"
Equipment Rinsate 11, 12, 14, 18, 24"
Estimated Quantitation Limit (EQL) 24"
Field Duplicate 12, 24, 25", 28
Laboratory Control Sample 19, 25"
Matrix 11, 12, 18-20, 23-25*, 26-28
Matrix Duplicate 12, 19, 20, 24, 25", 28
Matrix Spike 12, 18-20, 23, 25", 26, 27
Matrix Spike Duplicate 12, 19, 20, 23, 24, 25"
Method Blank 19, 24, 25", 28
Method Detection Limit (MDL) 18-20, 22, 24, 25*-27
Organic-Free Reagent Water 27", 28
Precision 1-3, 17-20, 22, 24, 25, 27*, 28
Project 1-5, 7, 8, 11-14, 17-19, 21, 23, 24, 28*
Quality Assurance Project Plan (QAPjP) 1-9, 11, 12, 14, 15, 18, 20, 22, 23, 28*
RCRA 1, 8, 28"
Reagent Blank 28*
Reagent Grade 28*
Reagent Water 27, 28*
Reference Material 8, 11, 15, 18, 19, 28*
Split Samples 25, 28"
Standard Addition 20, 28*
Standard Curve 26, 28"
Surrogate 18, 20, 22, 29"
Trip Blank 12, 18, 24, 29*
Definition of term.
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CHAPTER TWO
CHOOSING THE CORRECT PROCEDURE
2.1 PURPOSE
This chapter aids the analyst in choosing the appropriate methods for
samples, based upon sample matrix and the analytes to be determined.
2.1.1 Trace Analysis vs. Macroanalvsis
The methods presented in SW-846 were designed through sample sizing and
concentration procedures 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 as to "trace" analyses, through use of appropriate sample preparation
techniques that result in analyte concentration 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,
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: Care should be taken when analyzing samples for trace analyses
subsequent to analysis of concentrated samples due to 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, 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.
2.2 REQUIRED INFORMATION
In order to choose the correct combination of methods to form the
appropriate analytical procedure, some basic information is required.
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2.2.1 Physical State(s) of Sample
The phase characteristics of the sample must be known. There are several
general categories of phases in which the sample may be categorized:
Aqueous Oil and Organic Liquid
Sludges Solids
Multiphase Samples EP and TCLP Extracts
Ground Water
2.2.2 Analytes
Analytes are divided into classes based on the determinative methods which
are used to identify and quantify them. Table 2-1 lists the organic analytes of
SVI-846 methods, Table 2-2 lists the analytes that may be prepared using Method
3650, and Table 2-3 lists the analytes that are collected from stack gas
effluents using VOST methodology. Tables 2-4 through 2-31 list the target
analytes of each organic determinative method. Some of the analytes appear on
more than one table, as they may be determined using any of several methods.
Table 2-32 indicates which methods are applicable to inorganic target analytes.
2.2.3 Detection Limits Required
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 Interim Primary
Drinking Water Standards, are desired in the analysis of ground water.
2.2.4 Analytical Objective
Knowledge of the analytical objective will be useful in the choice of
aliquoting 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 being applied to 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 monitoring samples. 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, given the analytical
requirements, is mass spectral identification. The choice of technique for
metals is governed by the detection limit requirements and potential
interferents.
Monitoring samples, on the other hand, are analyzed to confirm existing and
on-going conditions, tracking the presence or absence of constituents in an
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environmental or process matrix. In well defined and stable analytical
conditions and matrices less compound-specific detection modes may be used.
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 2-33, 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/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.
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
Methods for preparing organic analytes are shown in Table 2-34. Method
3500 and associated methods should be consulted for further details on preparing
the sample for analysis.
2.3.1.1 Aqueous Samples
The choice of a preparative method depends on the sample. Methods
3510 and 3520 may be used for extraction of the semivolatile organic
compounds. Method 3510, a separatory funnel extraction, is appropriate
for samples which will not form a persistent emulsion interphase 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 liquid-liquid continuous
extraction, may be used for any aqueous sample; this method will minimize
emulsion formation.
2.3.1.1.1 Basic or Neutral Extraction of Semivolatiles
The solvent extract obtained by performing either Method 3510
or 3520 at a neutral or basic pH will contain the compounds of
interest. Refer to Table 1 in the extraction methods (3510 and/or
3520) for guidance on the pH requirements for extraction prior to
analysis.
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2.3.1.1.2 Acidic Extraction of Phenols and Acids
The extract obtained by performing either Method 3510 or 3520
at a pH less than or equal to 2 will contain the phenols and acid
extractables.
2.3.1.2 Solid Samples
Soxhlet (Methods 3540 and 3541) and ultrasonic (Method 3550)
extractions are used with solid samples. Consolidated samples should be
ground finely enough to pass through a 1 mm sieve. In limited
applications, waste dilution (Method 3580) may be used if the entire
sample is soluble in the specified solvent.
Methods 3540% and 3541 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.
2.3.1.3 Oils and Organic Liquids
Method 3580, waste dilution, may be used and the resultant sample
analyzed directly by GC or GC/MS. To avoid overloading the analytical
detection system, care must be exercised to ensure that proper dilutions
are made. Method 3580 gives guidance on performing waste dilutions.
To remove interferences, Method 3611 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.
2.3.1.4 Sludge Samples
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. If the sludge is an organic sludge (solid material and
organic liquid, as opposed to an aqueous sludge), the sample should be
handled as a multiphase sample.
Determining the appropriate methods for analysis of sludges is
complicated because of the lack of precise definition of sludges with
respect to the relative percent of liquid and solid components. They may
be classified into three categories but with appreciable overlap.
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2.3.1.4.1 Liquids
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 Solids
Soxhlet (Methods 3540 and 3541) 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.
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.
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 aliquoting multiphase samples is very
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
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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 Tables 2-34 through 2-36 for further guidance.
2.3.2 Cleanup Procedures
Each category in Table 2-35, 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.
2.3.3 Determinative Procedures
The determinative methods for organic analytes have been divided into three
categories, shown in Table 2-36: gas chromatography/mass spectrometry (GC/MS);
specific detection methods, i.e., gas chromatography (GC); 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 technique of gas
chromatography. This method should be consulted prior to application of any of
the gas chromatographic methods.
Methods 8080 and 8081, for organochlorine pesticides and polychlorinated
biphenyls, Methods 8140 and 8141, for organophosphorus pesticides, and Me'thods
8150 and 8151, for 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.
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Methods 8240 and 8260 are both GC/MS methods for volatile analytes. Method
8240 uses a packed column whereas Method 8260 employs a capillary column. Better
chromatographic separation of the volatile compounds may be obtained by using
Method 8260 rather than 8240. Performance criteria will be based on Method 8260.
Method 5030 has been combined with both Method 8240 and 8260, with which it was
used exclusively. A GC with a selective detector is also useful for the
determination of volatile organic compounds in a monitoring scenario, described
in Sec. 2.2.5.
Methods 8250 and 8270 are both GC/MS methods for semi volatile analytes.
Method 8250 uses a packed column whereas Method 8270 employs a capillary column.
Better chromatographic separation of the semi volatile compounds may be obtained
by using Method 8270 rather than 8250. Performance criteria will be based on
Method 8270.
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.
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
metallic analytes should correspond to the drinking water limits which are
available.
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2.5.1 Special Techniques for Metal Analvtes
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
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 Analvtes 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.
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2. Riggin, R.; et al. Development and Evaluation of Methods for Total Organic
Halide and Purqeable 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 bv Ion
Chromatographv; (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 ANALYTICAL METHODS FOR ORGANIC COMPOUNDS
Compound
Applicable Method(s)
i
Acenaphthene
Acenaphthylene
Acetaldehyde
Acetone
Acetonitrile
Acetophenone
2-Acetylami nof1uorene
1-Acetyl-2-thiourea
Acifluorfen
Acrolein (Propenal)
Acrylamide
Acrylonitrile
Alachlor
Aldicarb (Temik)
Aldicarb Sulfone
Aldrin
Allyl alcohol
Allyl chloride
2-Ami noanthraqui none
Aminoazobenzene
4-Aminobiphenyl
2-Amino-4,6-dinitrotoluene (2-Am-DNT)
4-Amino-2,6-dinitrotoluene (4-Am-DNT)
3-Ami no-9-ethylcarbazole
Anilazine
Aniline
o-Anisidine
Anthracene
Aramite
Aroclor-1016 (PCB-1016)
Aroclor-1221 (PCB-1221)
Aroclor-1232 (PCB-1232)
Aroclor-1242 (PCB-1242)
Aroclor-1248 (PCB-1248)
Aroclor-1254 (PCB-1254)
Aroclor-1260 (PCB-1260)
Aspon
Asulam
Atrazine
Azinphos-ethyl
Azinphos-methyl
Barban
Bentazon
8100, 8250/8270, 8310, 8410
8100, 8250/8270, 8310, 8410
8315
8240/8260, 8315
8240/8260
8250/8270
8270
8270
8151
8030/8031, 8240/8260, 8315,
8316
8032, 8316
8030/8031, 8240/8260, 8316
8081
8318
8318
8080/8081, 8250/8270, 8275
8240/8260
8010, 8240/8260
8270
8270
8250/8270
8330
8330
8270
8270
8250/8270
8270
8100, 8250/8270, 8310, 8410
8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8141
8321
8141
8141
8140/8141, 8270
8270
8151
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TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Benzal chloride
Benzaldehyde
Benz(a)anthracene
Benzene
Benzidine
Benzo(b)fluoranthene
Benzo(j)f1uoranthene
Benzo(k)f1uoranthene
Benzoic acid
Benzo(g,h,i)perylene
Benzo(a)pyrene
p-Benzoquinone
Benzotrichloride
Benzyl alcohol
Benzyl benzoate
Benzyl chloride
BHC (Hexachlorocyclohexane)
a-BHC (alpha-Hexachlorocyclohexane)
/3-BHC (beta-Hexachl orocycl ohexane)
8-BHC (delta-Hexachlorocyclohexane)
•y-BHC (Lindane, gamma-Hexachlorocycl ohexane)
Bi s(2-Chloroethoxy)methane
Bis(2-Chloroethyl)ether
Bi s(2-Chloroethyl)sulfide
Bis(2-Chloroisopropyl) ether
Bis(2-Ethylhexyl) phthalate
Bolstar (Sulprofos)
Bromoacetone
Bromobenzene
Bromochloromethane
Bromodi chloromethane
4-Bromofluorobenzene
Bromoform
Bromomethane
4-Bromophenyl phenyl ether
Bromoxynil
Butanal
n-Butanol
2-Butanone (Methyl ethyl ketone, MEK)
n-Butylbenzene
sec-Butyl benzene
tert-Butylbenzene
Butyl benzyl phthalate
8121
8315
8100, 8250/8270, 8310, 8410
8020, 8021, 8240/8260
8250/8270
8100, 8250/8270, 8310
8100
8100, 8250/8270, 8275, 8310
8250/8270, 8410
8100, 8250/8270, 8310
8100, 8250/8270, 8275, 8310,
8410
8270
8121
8250/8270
8061
8010, 8121, 8240/8260
8120
8080/8081, 8121, 8250/8270
8080/8081, 8121, 8250/8270
8080/8081, 8121, 8250/8270
8080/8081, 8121, 8250/8270
8010, 8110, 8250/8270, 8410
8110, 8250/8270, 8410
8240/8260
8010, 8110, 8250/8270, 8410
8060/8061, 8250/8270, 8410
8140/8141
8010, 8240/8260
8010, 8021, 8260
8021, 8240/8260
8010, 8021, 8240/8260
8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8110, 8250/8270, 8410
8270
8315
8260
8015, 8240/8260
8021, 8260
8021, 8260
8021, 8260
8060/8061, 8250/8270, 8410
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Revision 2
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TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
2-sec-Butyl-4,6-dinitrophenol (DNBP, Dinoseb)
Captafol
Captan
Carbaryl (Sevin)
Carbazole
Carbofuran (Furaden)
Carbon disulfide
Carbon tetrachloride
Carbophenothion (Carbofenthion)
Chloral hydrate
Chloramben
Chlordane (technical)
a-Chlordane
7-Chlordane
Chlorfenvinphos
Chloroacetonitrile
4-Chloroaniline
Chlorobenzene
Chiorobenzilate
2-Chloro-l,3-butadiene
1-Chlorobutane
Chiorodibromomethane (Dibromochloromethane)
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane
Chioromethane
5-Chloro-2-methylaniline
Chloromethyl methyl ether
4-Chloro-3-methylphenol
Chloroneb
3-(Chloromethyl)pyridine hydrochloride
1-Chioronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenol
4-Chloro-l,2-phenylenediamine
4-Chloro-l,3-phenylenediamine
4-Chlorophenyl phenyl ether
Chloroprene
3-Chloropropene
3-Chloropropionitrile
Chloropropylate
8040, 8150/8151, 8270, 8321
8081, 8270
8081, 8270
8270, 8318
8275
8270, 8318
8240/8260
8010, 8021, 8240/8260
8141, 8270
8240/8260
8151
8080, 8250/8270
8081
8081
8141, 8270
8260
8250/8270, 8410
8010, 8020, 8021, 8240/8260
8081, 8270
8260
8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8240/8260
8010, 8240/8260
8010, 8021, 8240/8260
8010, 8260
8010, 8021, 8240/8260
8270
8010
8040, 8250/8270, 8275, 8410
8081
8270
8250/8270, 8275
8120/8121, 8250/8270, 8410
8040, 8250/8270, 8275, 8410
8410
8270
8270
8110, 8250/8270, 8410
8010, 8240/8260
8260
8240/8260
8081
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TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Chlorothalonil
2-Chlorotoluene
4-Chlorotoluene
Chlorpyrifos
Chlorpyrifos methyl
Chrysene
Coumaphos
Coumarin Dyes
p-Cresidine
o-Cresol (2-Methylphenol)
m-Cresol (3-Methylphenol)
p-Cresol (4-Methylphenol)
Cresols (Methylphenols, Cresylic acids)
Crotonaldehyde
Crotoxyphos
Cyclohexanone
2-Cyclohexyl-4,6-dinitrophenol
2,4-D
Dalapon
2,4-DB
DBCP
2,4-D, butoxyethanol ester
DC PA
DCPA diacid
4,4'-DDD
4,4'-DDE
4,4'-DDT
Decanal
Demeton-0, and -S
2,4-D,ethylhexyl ester
Dial!ate
2,4-Diaminotoluene
Diazinon
Dibenz(a,h)acridine
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
7H-Dibenzo(c,g)carbazole
Dibenzofuran
Dibenzo(a,e)pyrene
Dibenzo(a,h)pyrene
Dibenzo(a,i)pyrene
Dibenzothiophene
Di bromochloromethane (Chiorodi bromomethane)
1,2-Di bromo-3-chloropropane
8081
8021, 8260
8010, 8021, 8260
8140/8141
8141
8100, 8250/8270, 8310, 8410
8140/8141, 8270
8321
8270
8250/8270, 8410
8270
8250/8270, 8275, 8410
8040
8260, 8315
8141, 8270
8315
8040, 8270
8150/8151, 8321
8150/8151, 8321
8150/8151, 8321
8081
8321
8081
8151
8080/8081, 8250/8270
8080/8081, 8270
8080/8081, 8250/8270
8315
8140/8141, 8270
8321
8081, 8270
8270
8140/8141
8100
8100, 8250/8270
8100, 8250/8270, 8310
8100
8250/8270, 8410
8100, 8270
8100
8100
8275
8010, 8021, 8240/8260
8010, 8011, 8240/8260, 8270
TWO - 13
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
1,2-Dibromoethane (Ethylene dibromide)
Di bromof1uoromethane
Dibromomethane
Di-n-butyl phthalate
Dicamba
Dichlone
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
3,5-Dichlorobenzoic acid
l,4-Dichloro-2-butene
cis-l,4-Dichloro-2-butene
trans-l,4-Dichloro-2-butene
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene (Vinylidene chloride)
ci s-1,2-Di chloroethene
trans-1,2-Dichloroethene
Dichlorofenthion
Dichloromethane (Methylene chloride)
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorprop
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Di chloropropane
l,3-Dichloro-2-propanol
1,1-Dichloropropene
cis-l,3-Dichloropropene
trans-1,3-Dichloropropene
Dichlorvos (Dichlorovos)
Dichrotophos
Dicofol
Dieldrin
1,2,3,4-Di epoxybutane
Diethyl ether
Diethyl phthalate
Diethylstilbestrol
Diethyl sulfate
8010, 8011, 8021, 8240/8260
8260
8010, 8021, 8240/8260
8060/8061, 8250/8270, 8410
8150/8151, 8321
8081, 8270
8010, 8020, 8021, 8120/8121,
8250/8270, 8260, 8410
8010, 8020, 8021, 8120/8121,
8250/8270, 8260, 8410
8010, 8020, 8021, 8120/8121,
8250/8270, 8260, 8410
8250/8270
8151
8010, 8240
8260
8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8021, 8260
8010, 8021, 8240/8260
8141
8010, 8021, 8240/8260
8040, 8250/8270, 8275, 8410
8040, 8250/8270
8150/8151, 8321
8010, 8021, 8240/8260
8021, 8260
8021, 8260
8010, 8240/8260
8021, 8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8140/8141, 8270, 8321
8141, 8270
8081
8080/8081, 8250/8270
8240/8260
8015, 8260
8060/8061, 8250/8270, 8410
8270
8270
TWO - 14
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
1,4-Difluorobenzene
Dihydrosaffrole
Dimethoate
3,3'-Dimethoxybenzidine
Dimethylaminoazobenzene
2,5-Dimethylbenzaldehyde
7,12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine
a,a-Dimethylphenethylamine
2,4-Dimethylphenol
Dimethyl phthalate
Dinitrobenzene
1,2-Dinitrobenzene
1,3-Dinitrobenzene (1,3-DNB)
1,4-Dinitrobenzene
4,6-Dinitro-2-methylphenol
2,4-Dinitrophenol
2,4-Dinitrotoluene (2,4-DNT)
2,6-Dinitrotoluene (2,6-DNT)
Dinocap
Dinoseb (2-sec-Butyl-4,6-dinitrophenol, DNBP)
Di-n-octyl phthalate
Di-n-propyl phthalate
Dioxacarb
1,4-Dioxane
Dioxathion
Diphenylamine
5,5-Di phenylhydantoi n
1,2-Diphenylhydrazine
Disperse Blue 3
Disperse Blue 14
Disperse Brown 1
Disperse Orange 3
Disperse Orange 30
Disperse Red 1
Disperse Red 5
Disperse Red 13
Disperse Red 60
Disperse Yellow 5
Disulfoton
Endosulfan I
Endosulfan II
Endosulfan sulfate
8240/8260
8270
8141, 8270, 8321
8270
8250/8270
8315
8250/8270
8270
8250/8270
8040, 8250/8270
8060/8061, 8250/8270, 8410
8090
8270
8270, 8330
8270
8250/8270, 8410
8040, 8250/8270, 8410
8090, 8250/8270, 8275, 8330,
8410
8090, 8250/8270, 8330, 8410
8270
8040, 8150/8151, 8270, 8321
8060/8061, 8250/8270, 8410
8410
8318
8240/8260
8141, 8270
8250/8270, 8275
8270
8250/8270
8321
8321
8321
8321
8321
8321
8321
8321
8321
8321
8140/8141, 8270, 8321
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
TWO - 15
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound Applicable Method(s)
Endrin 8080/8081, 8250/8270
Endrin aldehyde 8080/8081, 8250/8270
Endrin ketone 8081, 8250/8270
Epichlorohydrin 8010, 8240/8260
EPN 8141, 8270
Ethanol (Ethyl alcohol) 8015, 8240/8260
Ethion 8141, 8270
Ethoprop 8140/8141
Ethyl acetate 8260
Ethyl benzene 8020, 8021, 8240/8260
Ethyl carbamate 8270
Ethylene dibromide 8010, 8011, 8021, 8240/8260
Ethylene oxide 8240/8260
Ethyl methacrylate 8240/8260
Ethyl methanesulfonate 8250/8270
Ethyl parathion 8270
Etridiazole 8081
Famphur 8141, 8270, 8321
Fenitrothion 8141
Fensulfothion 8140/8141, 8270, 8321
Fenthion 8140/8141, 8270
Fluchloralin 8270
Fluoranthene 8100, 8250/8270, 8310, 8410
Fluorene 8100, 8250/8270, 8275, 8310,
8410
Fluorescent Brightener 61 8321
Fluorescent Brightener 236 8321
Fluorobenzene 8260
2-Fluorobiphenyl 8250/8270
2-Fluorophenol 8250/8270
Fonophos 8141
Formaldehyde 8315
Halowax-1000 8081
Halowax-1001 8081
Halowax-1013 8081
Hal owax-1014 8081
Halowax-1051 8081
Hal owax-1099 8081
Heptachlor 8080/8081, 8250/8270
Heptachlor epoxide 8080/8081, 8250/8270
Heptanal 8315
Hexachlorobenzene 8081, 8120/8121, 8250/8270,
8275, 8410
TWO - 16 Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Hexachlorobutadiene (1,3-Hexachlorobutadiene)
Hexachlorocyclohexane
a-Hexachlorocyclohexane (a-BHC)
0-Hexachl orocycl ohexane (/3-BHC)
S-Hexachlorocyclohexane (5-BHC)
7-Hexachlorocyclohexane (7-BHC)
Hexachlorocyclopentadi ene
Hexachloroethane
Hexachlorophene
Hexachloropropene
Hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX)
Hexamethylphosphoramide (HMPA)
Hexanal
2-Hexanone
HMX
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,
1,2,3,4,7,
1,
1,
1.
L
L
8,9-HpCDF
8-HxCDD
2,3,6,7,8-HxCDD
2,3,7,8,9-HxCDD
2,3,4,7,8-HxCDF
2,3,6,7,8-HxCDF
2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
Hydroquinone
3-Hydroxycarbofuran
5-Hydroxydicamba
2-Hydroxypropi oni tri1e
Indeno(l,2,3-cd)pyrene
lodomethane
Isobutyl alcohol (2-Methyl-l-propanol)
Isodrin
Isophorone
Isopropylbenzene
p-Isopropyltoluene
Isosafrole
8021, 8120/8121, 8250/8270,
8260, 8410
8120
8080/8081, 8120/8121, 8250,
8270
8080/8081, 8120/8121, 8250,
8270
8080/8081, 8120/8121, 8250,
8270
8080/8081, 8120/8121, 8250,
8270
8081, 8120/8121, 8250/8270,
8410
8120/8121, 8250/8270, 8260,
8410
8270
8270
8330
8141, 8270
8315
8240/8260
8330
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8270
8318
8151
8240/8260
8100, 8250/8270, 8310
8240/8260
8240/8260
8081, 8270
8090, 8250/8270, 8410
8021, 8260
8021, 8260
8270
TWO - 17
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Isovaleraldehyde
Kepone
Leptophos
Malathion
Maleic anhydride
Malononitrile
MCPA
MCPP
Merphos
Mestranol
Methacrylonitrile
Methanol
Methapyrilene
Methiocarb (Mesurol)
Methomyl (Lannate)
Methoxychlor (4,4'-Methoxychlor)
Methyl acrylate
Methyl-t-butyl ether
3-Methylcholanthrene
2-Methyl-4,6-dinitrophenol
4,4'-Methylenebis(2-chloroaniline)
4,4'-Methylenebis(N,N-dimethylaniline)
Methyl ethyl ketone (MEK, 2-Butanone)
Methylene chloride (Dichloromethane)
Methyl iodide
Methyl isobutyl ketone (4-Methyl-2-pentanone)
Methyl methacrylate
Methyl methanesulfonate
2-Methylnaphthal ene
2-Methyl-5-nitroaniline
Methyl parathion
4-Methyl-2-pentanone (Methyl isobutyl ketone)
2-Methylphenol (o-Cresol)
3-Methylphenol (m-Cresol)
4-Methylphenol (p-Cresol)
2-Methylpyridine
Methyl-2,4,6-trinitrophenylnitramine (Tetryl)
Mevinphos
Mexacarbate
Mi rex
Monochrotophos
Naled
Naphthalene
8315
8081, 8270
8141, 8270
8141, 8270
8270
8240/8260
8150/8151, 8321
8150/8151, 8321
8140/8141, 8321
8270
8240/8260
8260
8270
8318
8318, 8321
8080/8081, 8250/8270
8260
8260
8100, 8250/8270
8040
8270
8270
8015, 8240/8260
8010, 8021, 8240/8260
8010, 8240/8260
8015, 8240/8260
8240/8260
8250/8270
8250/8270, 8410
8270
8270, 8321
8015, 8240/8260
8250/8270, 8410
8270
8250/8270, 8275, 8410
8270
8330
8140/8141, 8270
8270
8081, 8270
8141, 8270, 8321
8140/8141, 8270, 8321
8021, 8100, 8250/8270, 8260,
8275, 8310, 8410
TWO - 18
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Naphthoquinone
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
Nicotine
5-Nitroacenaphthene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
5-Nitro-o-anisidine
Nitrobenzene (NB)
4-Nitrobiphenyl
Nitrofen
2-Nitrophenol
4-Nitrophenol
2-Nitropropane
Nitroquinoline-1-oxide
N-Ni trosodi butyl amine
N-Nitrosodiethyl amine
N-Nitrosodimethylamine
N-Ni trosodi phenylami ne
N-Ni trosodi-n-propylamine
N-Ni trosomethylethyl ami ne
N-Nitrosomorpholine
N-Nitrosopiperidine
N-Nitrosopyrrolidine
o-Nitrotoluene (2-NT)
m-Nitrotoluene (3-NT)
p-Nitrotoluene (4-NT)
5-Nitro-o-toluidine
trans-Nonachlor
Nonanal
OCDD
OCDF
Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine
(HMX)
Octamethyl pyrophosphoramide
Octanal
4,4'-Oxydianiline
Parathion
Parathion, ethyl
Parathion, methyl
PCB-1016 (Aroclor-1016)
8090
8270
8250/8270
8250/8270
8270
8270
8250/8270, 8410
8250/8270, 8410
8250/8270, 8410
8270
8090, 8250/8270, 8260, 8330,
8410
8270
8081, 8270
8040, 8250/8270, 8410
8040, 8151, 8250/8270, 8410
8260
8270
8250/8270
8270
8070, 8250/8270, 8410
8070, 8250/8270, 8410
8070, 8250/8270, 8410
8270
8270
8250/8270
8270
8330
8330
8330
8270
8081
8315
8280/8290
8280/8290
8330
8270
8315
8270
8270
8141
8140/8141
8080/8081, 8250/8270
TWO - 19
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
PCB-1221 (Aroclor-1221)
PCB-1232 (Aroclor-1232)
PCB-1242 (Aroclor-1242)
PCB-1248 (Aroclor-1248)
PCB-1254 (Aroclor-1254)
PCB-1260 (Aroclor-1260)
PCNB
1,2,3,4,7-PeCDD
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Pentachlorobenzene
Pentachloroethane
Pentachlorohexane
Pentachloronitrobenzene
Pentachlorophenol
Pentaf1uorobenzene
Pentanal
trans-Permethrin
Perthane
Phenacetin
Phenanthrene
Phenobarbital
Phenol
1,4-Phenylenediamine
Phorate
Phosalone
Phosmet
Phosphamidion
Phthalic anhydride
Picloram
2-Picoline
Piperonyl sulfoxide
Promecarb
Pronamide
Propachlor
Propanal
Propargyl alcohol
6-Propiolactone
Propionitrile
Propoxur (Baygon)
n-Propylamine
n-Propylbenzene
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8081
8280/8290
8280/8290
8280/8290
8280/8290
8121, 8250/8270
8240/8260
8120
8250/8270
8040, 8151, 8250/8270, 8410
8260, 4010
8315
8081
8081
8250/8270
8100, 8250/8270, 8275, 8310,
8410
8270
8040, 8250/8270, 8410
8270
8140/8141, 8270, 8321
8270
8141, 8270
8141, 8270
8270
8151
8240/8260, 8250/8270
8270
8318
8250/8270
8081
8315
8240/8260
8240/8260
8240/8260
8318
8240/8260
8021, 8260
TWO - 20
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Propylthiouracil
Pyrene
Pyridine
RDX
Resorcinol
Ronnel
Safrole
Simazine
Solvent Red 3
Solvent Red 23
Stirophos (Tetrachlorvinphos)
Strobane
Strychnine
Styrene
Sulfall ate
Sulfotepp
2,4,5-T
2,4,5-T, butoxyethanol ester
2,4,5-T, butyl ester
1,2,3,4-TCDD
1,2,7,8-TCDD
1,2,8,9-TCDD
1,3,6,8-TCDD
1,3,7,8-TCDD
1,3,7,9-TCDD
2,3,7,8-TCDD
1,2,7,8-TCDF
2,3,7,8-TCDF
TEPP
Terbuphos (Terbufos)
Terphenyl
1,2,3,4-Tetrachlorobenzene
1,2,3,5-Tetrachlorobenzene
1,2,4,5-Tetrachlorobenzene
Tetrachlorobenzenes
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
2,3,4,6-Tetrachlorophenol
Tetrachlorophenols
Tetrachlorvinphos (Stirophos)
Tetraethyl dithiopyrophosphate
Tetraethyl pyrophosphate
8270
8100, 8250/8270, 8275, 8310,
8410
8240/8260, 8270
8330
8270
8140/8141
8270
8141
8321
8321
8140/8141, 8270
8081
8270, 8321
8021, 8240/8260
8270
8141
8150/8151, 8321
8321
8321
8280
8280
8280
8280
8280
8280
8280/8290
8280
8280/8290
8141
8141, 8270
8250/8270
8121
8121
8121, 8250/8270
8120
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8250/8270
8040
8140/8141, 8270
8270
8270
TWO - 21
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Tetrazene
Thiofanox
Thionazine
Thiophenol (Benzenethiol)
TOCP (Tri-o-cresylphosphate)
Tokuthion (Prothiofos)
m-Tolualdehyde
o-Tolualdehyde
p-Tolualdehyde
Toluene
Toluene diisocyanate
o-Toluidine
Toxaphene
2,4,5-TP (Silvex)
2,4,6-Tribromophenol
1,2,3-Trichlorobenzene
1,2,4-Tri chlorobenzene
1,3,5-Tri chlorobenzene
1,1,1-Trichloroethane
1,1,2-Tri chloroethane
Trichloroethene
Trichlorofluoromethane
Trichlorfon
Trichloronate
2,4,5-Tri chlorophenol
2,4,6-Trichlorophenol
Trichlorophenols
1,2,3-Tri chloropropane
0,0,0-Triethyl phosphorothioate
Trifluralin
2,4,5-Trimethylaniline
1,2,4-Trimethylbenzene
1,3,5-Trimethylbenzene
Trimethyl phosphate
1,3,5-Trinitrobenzene (1,3,5-TNB)
2,4,6-Trinitrotoluene (2,4,6-TNT)
Tri-o-cresyl phosphate (TOCP)
Tri-p-tolyl phosphate
Tris(2,3-Dibromopropyl) phosphate (Tris-BP)
Vinyl acetate
Vinyl chloride
8331
8321
8141, 8270
8270
8141
8140/8141
8315
8315
8315
8020, 8021, 8240/8260
8270
8270
8080/8081, 8250/8270
8150/8151, 8321
8250/8270
8021, 8121, 8260
8021, 8120/8121, 8250/8270,
8260, 8410
8121
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8141, 8321
8140/8141
8250/8270, 8410
8040, 8250/8270, 8410
8040
8010, 8021, 8240/8260
8270
8081, 8270
8270
8021, 8260
8021, 8260
8270
8270, 8330
8330
8141
8270
8270, 8321
8240/8260
8010, 8021, 8240/8260
TWO - 22
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound Applicable Method(s)
o-Xylene 8021, 8260
m-Xylene 8021, 8260
p-Xylene 8021, 8260
Xylene (Total) 8020, 8240
TABLE 2-2A.
METHOD 3650 - BASE/NEUTRAL FRACTION
Benz(a)anthracene Hexachlorobenzene
Benzo(a)pyrene Hexachlorobutadiene
Benzo(b)fluoranthene Hexachloroethane
Chi ordane Hexachlorocyclopentadi ene
Chlorinated dibenzodioxlns Naphthalene
Chrysene Nitrobenzene
Creosote Phorate
Dichlorobenzene(s) 2-Picoline
Dinitrobenzene Pyridine
2,4-Dinitrotoluene Tetrachlorobenzene(s)
Heptachlor Toxaphene
TABLE 2-2B.
METHOD 3650 - ACID FRACTION
2-Chlorophenol 4-Nitrophenol
Cresol(s) Pentachlorophenol
Creosote Phenol
Dichlorophenoxyacetic acid Tetrachlorophenol(s)
2,4-Dimethyl phenol Trichlorophenol(s)
4,6-Dinitro-o-cresol 2,4,5-TP (Silvex)
TWO - 23 Revision 2
September 1994
-------
TABLE 2-3.
METHOD 5041 - SORBENT CARTRIDGES FROM
VOLATILE ORGANIC SAMPLING TRAIN (VOST)
Acetone 1,2-Dichloropropane
Acrylonitrlle cis-l,3-Dichloropropene
Benzene trans-l,3-Dichloropropene
Bromodichloromethane Ethyl benzene3
Bromoform8 lodomethane
Bromomethane Methylene chloride
Carbon disulfide Styrene3
Carbon tetrachloride 1,1,2,2-Tetrachloroethane3
Chlorobenzene Tetrachloroethene
Chlorodibrompmethane Toluene
Chi oroethane 1,1,1-Tri chloroethane
Chloroform 1,1,2-Trichloroethane
Chloromethane Trichloroethene
Di bromomethane Tri chlorof1uoromethane
1,1-Di chloroethane 1,2,3-Tri chloropropane3
1,2-Dichloroethane Vinyl chloride
1,1-Dichloroethene Xylenes3
trans-l,2-Dichloroethene
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 - 24 Revision 2
September 1994
-------
TABLE 2-4.
METHOD 8010 - HALOGENATED VOLATILES
AHyl chloride
Benzyl chloride
Bi s(2-chloroethoxy)methane
Bis(2-chloroisopropyl) ether
Bromoacetone
Bromobenzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane
Chloromethane
Chloromethyl methyl ether
Chloroprene
4-Chlorotoluene
Di bromochloromethane
l,2-Dibromo-3-chloropropane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Di chlorobenzene
l,4-Dichloro-2-butene
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene (Vinylidene chloride)
trans-1,2-Dichloroethene
Dichloromethane (Methylene Chloride)
1,2-Di chloropropane
1,3-Di chloro-2-propanol
cis-l,3-Dichloropropene
trans-1,3-Di chloropropene
Epichlorhydrin
Ethylene dibromide
Methyl iodide
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
Tetrachloroethene
1,1,1-Trichloroethane
1,1,2-Tri chloroethane
Trichloroethene
Tri chlorof1uoromethane
1,2,3-Tri chloropropane
Vinyl chloride
For Method 8011, see Table 2-7
TABLE 2-5.
METHOD 8015 - NONHALOGENATED VOLATILES
TABLE 2-6.
METHOD 8020 - AROMATIC VOLATILES
Di ethyl ether
Ethanol
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
Toluene
Xylenes
TWO - 25
Revision 2
September 1994
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TABLE 2-7.
METHOD 8021 (METHOD 8011*) - HAL06ENATED AND AROMATIC VOLATILES
Benzene 1,3-Dichloropropane
Bromobenzene 2,2-Dichloropropane
Bromochloromethane 1,1-Di chloropropene
Bromodi chloromethane ci s-1,3-Di chloropropene
Bromoform trans-1,3-Di chloropropene
Bromomethane Ethyl benzene
n-Butylbenzene Hexachlorobutadi ene
sec-Butyl benzene Isopropylbenzene
tert-Butylbenzene p-Isopropyltoluene
Carbon tetrachloride Methylene chloride (DCM)
Chlorobenzene Naphthalene
Chlorodibromomethane n-Propylbenzene
Chloroethane Styrene
Chloroform 1,1,1,2-Tetrachloroethane
Chloromethane 1,1,2,2-Tetrachloroethane
2-Chlorotoluene Tetrachloroethene
4-Chlorotoluene Toluene
l,2-Dibromo-3-chloropropane* 1,2,3-Trichlorobenzene
1,2-Dibromoethane* 1,2,4-Trichlorobenzene
Di bromomethane 1,1,1-Tri chloroethane
1,2-Di chlorobenzene 1,1,2-Tri chloroethane
1,3-Di chlorobenzene Tri chloroethene
1,4-Di chlorobenzene Tri chlorof1uoromethane
Di chlorodi f1uoromethane 1,2,3-Tri chloropropane
1,1-Dichloroethane 1,2,4-Trimethylbenzene
1,2-Di chloroethane 1,3,5-Tri methyl benzene
1,1-Dichloroethene (Vinylidene chloride) Vinyl chloride
cis-l,2-Dichloroethene o-Xylene
trans-1,2-Di chloroethene m-Xylene
1,2-Dichloropropane p-Xylene
* Indicates the only two target analytes of Method 8011. These constituents are
also target analytes of Method 8021.
TABLE 2-8. TABLE 2-9
METHODS 8030/8031 - METHOD 8032 -
ACROLEIN, ACRYLONITRILE ACRYLAMIDE
Acrolein (Propenal)* Acrylamide
Acrylonitrile
* Target analyte of Method 8030 only.
TWO - 26 Revision 2
September 1994
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TABLE 2-10.
METHOD 8040 - PHENOLS
2-sec-Butyl-4,6-dinitrophenol (DNBP, Dinoseb)
4-Chloro-3-methylphenol
2-Chlorophenol
Cresols (Methylphenols)
2-Cyclohexyl-4,6-di ni trophenol
2,4-Dichlorophenol
2,6-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
Tetrachlorophenols
2,4,6-Trichlorophenol
Trichlorophenols
TABLE 2-11.
METHODS 8060/8061 - PHTHALATE ESTERS
Benzyl benzoate*
Butyl benzyl phthalate
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
* Target analyte of Method 8061 only.
TABLE 2-12.
METHOD 8070 - NITROSAMINES
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
TWO - 27
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September 1994
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TABLE 2-13.
METHODS 8080/8081 - ORGANOCHLORINE PESTICIDES AND PCBs
Aroclor-1016 (PCB-1016)
Aroclor-1221 (PCB-1221)
Aroclor-1232 (PCB-1232)
Aroclor-1242 (PCB-1242)
Aroclor-1248 (PCB-1248)
Aroclor-1254 (PCB-1254)
Aroclor-1260 (PCB-1260)
Alachlor*
Aldrin
a-BHC
0-BHC
5-BHC
7-BHC (Lindane)
Captafol*
Captan*
Chiorobenzilate*
Chlordane (technical)**
a-Chlordane*
y-Chlordane*
Chloroneb*
Chloropropylate*
Chlorothalonil*
DBCP*
DC PA*
4,4'-DDD
4,4'-DDE
4,4'-DDT
Diallate*
Dichlone*
Dicofol*
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone*
Etridiazole*
Halowax-1000*
Halowax-1001*
Halowax-1013*
* Target analyte of Method 8081 only.
** Target analyte of Method 8080 only.
Halowax-1014*
Halowax-1051*
Halowax-1099*
Heptachlor
Heptachlor epoxide
Hexachlorobenzene*
Hexachlorocyclo-
pentadiene*
Isodrin*
Kepone*
Methoxychlor
Mi rex*
Nitrofen*
trans-Nonachlor*
PCNB*
trans-Permethrin*
Perthane*
Propachlor*
Strobane*
Toxaphene
Trifluralin*
TABLE 2-14.
METHOD 8090 - NITROAROMATICS AND
CYCLIC KETONES
Dinitrobenzene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Isophorone
Naphthoquinone
Nitrobenzene
TWO - 28
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September 1994
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TABLE 2-15.
METHODS 8100 - POLYNUCLEAR AROMATIC HYDROCARBONS
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)fl uoranthene
Benzo(j)f 1uoranthene
Benzo(k)f1uoranthene
Benzo (g,h,i)perylene
Benzo(a)pyrene
Chrysene
Dibenz(a,h)acridine
Dibenz(a,j)acridine
D1benzo(a,h)anthracene
7H-Dibenzo(c,g)carbazole
Dibenzo(a,e)pyrene
Dibenzo(a,h)pyrene
Dibenzo(a,i)pyrene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
3-Methylcholanthrene
Naphthalene
Phenanthrene
Pyrene
TABLE 2-16
METHOD 8110 - HALOETHERS
Bi s(2-Chloroethoxy)methane
Bis(2-Chloroethyl) ether
Bis(2-Chloroisopropyl) ether
4-Bromophenyl phenyl ether
4-Chlorophenyl phenyl ether
TABLE 2-17.
METHODS 8120/8121 - CHLORINATED HYDROCARBONS
Benzal chloride*
Benzotrichloride*
Benzyl chloride*
2-Chloronaphthalene
1,2-Di chlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadi ene
Hexachlorocyclohexane**
a-Hexachlorocyclohexane (a-BHC)*
)S-Hexachl orocycl ohexane (/3-BHC)*
6-Hexachlorocyclohexane (6-BHC)*
Y-Hexachlorocyclohexane (y-BHC)*
Hexachlorocyclopentadi ene
Hexachloroethane
Pentachlorobenzene*
Pentachlorohexane**
Tetrachlorobenzenes**
1,2,3,4-Tetrachlorobenzene*
1,2,3,5-Tetrachlorobenzene*
1,2,4,5-Tetrachlorobenzene*
1,2,3-Tri chlorobenzene*
1,2,4-Tri chlorobenzene
1,3,5-Tri chlorobenzene*
* Target analyte of Method 8121 only.
** Target analyte of Method 8120 only.
TWO - 29
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TABLE 2-18.
METHODS 8140/8141 - ORGANOPHOSPHORUS COMPOUNDS
(PACKED AND CAPILLARY COLUMNS)
Aspon* Fenthion
Atrazine* Fonophos*
Azinphos ethyl* Hexamethylphosphoramide* (HMPA)
Azinphos methyl Leptophos*
Bolstar (Sulprofos) Malathion*
Carbophenothion* Merphos
Chlorofenvinphos* Mevinphos
Chlorpyrifos Monochrotophos*
Chlorpyrifos methyl* Naled
Coumaphos Parathion, ethyl*
Crotoxypos* Parathion, methyl
Demeton-0, and -S Phorate
Diazinon Phosmet*
Dichlorofenthion* Phosphamidon*
Dichlorvos (DDVP) Ronnel
Dichrotophos* Simazine*
Dimethoate* Stirophos (Tetrachlorvinphos)
Dioxathion* Sulfotep*
Disulfoton TEPP*
EPN* Terbufos*
Ethion* Thionazin*
Ethoprop Tokuthion (Prothiofos)
Famphur* Trichlorfon*
Fenitrothion* Trichloronate
Fensulfothion Tri-o-cresylphosphate (TOCP)*
* Target analyte of Method 8141 only.
TABLE 2-19.
METHODS 8150/8151 - CHLORINATED HERBICIDES
Acifluorfen* Dicamba MCPA
Bentazon* 3,5-Dichlorobenzoic acid* MCPP
Chloramben* Dichlorprop 4-Nitrophenol*
2,4-D Dinoseb (DNBP) Pentachlorophenol*
Dalapon 5-Hydroxydicamba* Picloram*
2,4-DB 2,4,5-TP (Silvex)
DCPA diacid* 2,4,5-T
* Target analyte of Method 8151 only.
TWO - 30 Revision 2
September 1994
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Acetone
Acetonitrile
Acrolein (Propenal)
Acrylonitrile
Ally! alcohol
Allyl chloride
Benzene
Benzyl chloride
Bis(Z-chloroethyl) sulfide
Bromoacetone
Bromobenzene*
Bromochloromethane
Bromodichloromethane
4-Bromof1uorobenzene
Bromoform
Bromomethane
n-Butanol*
2-Butanone (Methyl ethyl
ketone)
n-Butylbenzene*
sec-Butyl benzene*
tert-Butylbenzene*
Carbon disulfide
Carbon tetrachloride
Chloral hydrate
Chioroaceton i tri1e*
Chlorobenzene
2-Chloro-l,3-butadiene*
1-Chlorobutane*
Chiorodi bromomethane
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane*
Chioromethane
Chloroprene
3-Chloropropene*
3-Chioropropi oni tri1e
2-Chlorotoluene*
4-Chlorotoluene*
Crotonaldehyde*
TABLE 2-20.
METHODS 8240/8260 - VOLATILES
l,2-Dibromo-3-
chloropropane
1,2-Dibromoethane
Dibromomethane
Di bromof1uoromethane*
1,2-Di chlorobenzene*
1,3-Dichlorobenzene*
1,4-Di chlorobenzene*
l,4-Dichloro-2-butene**
cis-l,4-Dichloro-
2-butene*
trans-l,4-Dichloro-2-
butene*
l,4-Dichloro-2-butene**
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
ci s-1,2-Di chloroethene*
trans-1,2-Dichloroethene
1,2-Dichloropropane
1,3-Dichloropropane*
2,2-Di chloropropane*
l,3-Dichloro-2-propanol
1,1-Di chloropropene*
cis-l,3-Dichloropropene
trans-1,3-Dichloropropene
1,2,3,4-Diepoxybutane
Diethyl ether*
1,4-Di f1uorobenzene
1,4-Dioxane
Epichlorohydrin
Ethanol
Ethyl acetate*
Ethyl benzene
Ethylene oxide
Ethyl methacrylate
Fluorobenzene*
Hexachlorobutadiene*
Hexachloroethane*
2-Hexanone
2-Hydroxypropionitrile
lodotnethane
Isobutyl alcohol
Isopropylbenzene*
p-Isopropyltoluene*
Malononitrile
Methacrylonitrile
Methanol*
Methyl acrylate*
Methyl-t-butyl ether*
Methylene chloride (DCM)
Methyl iodide
Methyl methacrylate
4-Methyl-2-pentanone
(MIBK)
Naphthalene*
Nitrobenzene*
2-Nitropropane*
Pentachloroethane
Pentaf1uorobenzene*
2-Picoline
Propargyl alcohol
B-Propiolactone
Propionitrile
n-Propylamine
n-Propylbenzene*
Pyridine
Styrene
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,2,3-Tri chlorobenzene*
1,2,4-Tri chlorobenzene*
1,1,1-Tri chloroethane
1,1,2-Tri chloroethane
Trichloroethene
Tri chlorof1uoromethane
1,2,3-Trichloropropane
1,2,4-Trimethylbenzene*
1,3,5-Trimethylbenzene*
Vinyl acetate
Vinyl chloride
Xylene (Total)**
o-Xylene*
m-Xylene*
p-Xylene*
* Target analyte of Method 8260 only.
** Target analyte of Method 8240 only.
TWO - 31
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September 1994
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TABLE 2-21.
METHODS 8250/8270 - SEMIVOLATILES
Acenaphthene
Acenaphthylene
Acetophenone
2-Acetylami nof1uorene*
1-Acetyl-2-thi ourea*
Aldrin
2-Aminoanthraquinone*
Aminoazobenzene*
4-Aminobiphenyl
3-Amino-9-ethylcarbazole*
Anilazine*
Aniline
o-Anisidine*
Anthracene
Aramite*
Aroclor-1016 (PCB-1016)
Aroclor-1221 (PCB-1221)
Aroclor-1232 (PCB-1232)
Aroclor-1242 (PCB-1242)
Aroclor-1248 (PCB-1248)
Aroclor-1254 (PCB-1254)
Aroclor-1260 (PCB-1268)
Azinphos-methyl*
Barban*
Benz(a)anthracene
Benzidine
Benzo(b)f1uoranthene
Benzo(k)f1uoranthene
Benzoic acid
Benzo(g,h,i)perylene
Benzo(a)pyrene
p-Benzoquinone*
Benzyl alcohol
a-BHC
)8-BHC
5-BHC
•y-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
2-sec-Butyl-4,6-dinitrophenol (Dinoseb)*
Captafol*
Captan*
Carbaryl*
Carbofuran*
Carbophenothion*
Chlordane (technical)
Chlorfenvinphos*
4-Chloroaniline
Chiorobenzilate*
5-Chloro-2-methylaniline*
4-Chloro-3-methyl phenol
3-(Chloromethyl)pyridine hydrochloride*
1-Chloronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chloro-l,2-phenylenediamine*
4-Chloro-l,3-phenylenediamine*
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
Di benzo(a,e)pyrene*
l,2-Dibromo-3-chloropropane*
Di-n-butyl phthalate
Dichlone*
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos*
Dicrotophos*
Dieldrin
Diethyl phthalate
Di ethylsti1bestrol*
Diethyl sulfate*
Dihydrosaffrole*
Dimethoate*
3,3'-Dimethoxybenzidine*
Dimethyl aminoazobenzene
TWO - 32
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September 1994
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TABLE 2-21.
METHODS 8250/8270 - SEMIVOLATILES (CONTINUED)
7,12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine*
a,a-Dimethylphenethylamine
2,4-Dimethylphenol
Dimethyl phthalate
1,2-Dinitrobenzene*
1,3-Dinitrobenzene*
1,4-Dinitrobenzene*
4,6-Dinitro-2-methylphenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap*
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
Ethyl parathion*
Famphur*
Fensulfothion*
Fenthion*
Fluchloralin*
Fluoranthene
Fluorene
2-Fluorobiphenyl
2-Fluorophenol
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadi ene
Hexachlorocyclopentadi ene
Hexachloroethane
Hexachlorophene*
Hexachloropropene*
Hexamethyl phosphoratnide*
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-dimethylaniline)*
Methyl methanesulfonate
2-Methylnaphtha!ene
2-Methyl-5-nitroaniline*
Methyl parathion*
2-Methylphenol (o-Cresol)
3-Methylphenol (m-Cresol)*
4-Methylphenol (p-Cresol)
2-Methylpyridine*
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
Nitroquinoline-1-oxide*
N-Nitrosodibutyl amine
N-Nitrosodiethyl amine*
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
TWO - 33
Revision 2
September 1994
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TABLE 2-21.
METHODS 8250/8270 - SEMIVOLATILES (CONTINUED)
N-Nitrosomethylethylamine*
N-Nitrosomorpholine*
N-Nitrosopiperi dine
N-Nitrosopyrrolidine*
5-Nitro-o-toluidine*
Octamethyl pyrophosphoramide*
4,4'-Oxydianiline*
Parathion*
Pentachlorobenzene
Pentachloroni trobenzene
Pentachlorophenol
Phenacetin
Phenanthrene
Phenobarbital*
Phenol
1,4-Phenylenediamine*
Phorate*
Phosalone*
Phosmet*
Phosphamidion*
Phthalic anhydride*
2-Picoline
Piperonyl sulfoxide*
Pronamide
Propylthiouracil*
'yrene
}yr idine*
Resorcinol*
Safrole*
Strychnine*
Sulfall ate*
* Target analyte of Method 8270 only.
Terbuphos*
Terphenyl
1,2,4,5-Tetrachlorobenzene
2,3,4,6-Tetrachlorophenol
Tetrachlorvinphos (Stirophos)*
Tetraethyl dithiopyrophosphate*
Tetraethyl pyrophosphate*
Thionazine*
Thiophenol (Benzenethiol)*
Toluene diisocyanate*
o-Toluidine*
Toxaphene
2,4,6-Tribromophenol
1,2,4-Tri chlorobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
0,0,0-Triethyl phosphorothioate*
Trifluralin*
2,4,5-Trimethylaniline*
Trimethyl phosphate*
1,3,5-Tri n i trobenzene*
Tris(2,3-dibromopropyl) phosphate*
Tri-p-tolyl phosphate*
TABLE 2-22.
METHOD 8275 - SEMIVOLATILES (SCREENING)
Aldrin
Benzo(k)fluoranthene
Benzo(a)pyrene
Carbazole
4-Chloro-3-methylphenol
1-Chloronaphthalene
2-Chlorophenol
Dibenzothiophene
2,4-Dichlorophenol
2,4-Dinitrotoluene
Diphenylamine
Fluorene
Hexachlorobenzene
4-Methylphenol
Naphthalene
Phenanthrene
Pyrene
TWO - 34
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2,3,7,8-TCDD
1,2,3,4-TCDD*
1,3,6,8-TCDD*
1,3,7,9-TCDD*
1,3,7,8-TCDD*
1,2,7,8-TCDD*
1,2,8,9-TCDD*
TABLE 2-23.
METHODS 8280/8290 - DIOXINS AND DIBENZOFURANS
1,2,3,4,7-PeCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
* Target analyte of 8280 only
1,2,7,8-TCDF
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
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
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
TABLE 2-24.
METHOD 8310 - POLYNUCLEAR AROMATIC HYDROCARBONS
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo (b)fl uoranthene
Benzo(g,h,i)perylene
Benzo(k)f1uoranthene
Chrysene
Di benzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
TWO - 35
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September 1994
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TABLE 2-25.
METHOD 8315 - CARBONYL COMPOUNDS
Acetaldehyde Heptanal
Acetone Hexanal (Hexaldehyde)
Acrolein (Propanol) Isovaleraldehyde
Benzaldehyde Nonanal
Butanal (Butyraldehyde) Octanal
Crotonaldehyde Pentanal (Valeraldehyde)
Cyclohexanone Propanal (Propionaldehyde)
Decanal m-Tolualdehyde
2,5-Dimethylbenzaldehyde o-Tolualdehyde
Formaldehyde p-Tolualdehyde
TABLE 2-26. TABLE 2-27.
METHOD 8316 - ACRYLAMIDE, METHOD 8318 - N-METHYLCARBAMATES
ACRYLONITRILE AND ACROLEIN
Aldicarb (Temik)
Acrolein (Propanol) Aldicarb Sulfone
Acrylamide Carbaryl (Sevin)
Acrylonitrile Carbofuran (Furadan)
Dioxacarb
3-Hydroxycarbofuran
Methiocarb (Mesurol)
Methomyl (Lannate)
Promecarb
Propoxur (Baygon)
TWO - 36 Revision 2
September 1994
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TABLE 2-28.
METHOD 8321 - NONVOLATILES
Azo Dves
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 Dves
Disperse Blue 3
Disperse Blue 14
Disperse Red 60
Coumarin Dyes
(Fluorescent Brighteners)
Fluorescent Brightener 61
Fluorescent Brightener 236
Chlorinated Phenoxvacid 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
Orqanophosphorus Compounds
Asulam
Dichlorvos
Dimethoate
Disulfoton
Famphur
Fensulfothion
Merphos
Methomyl
Methyl parathion
Monocrotophos
Naled
Phorate
Trichlorfon
Thiofanox
Tris-(2,3-dibromopropyl) phosphate,
(Tris-BP)
TWO - 37
Revision 2
September 1994
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TABLE 2-29.
METHOD 8330 - 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-l,3,5-triazine (RDX)
Methyl-2,4,6-tri ni trophenylnitramine (Tetryl)
Nitrobenzene (NB)
2-Nitrotoluene (2-NT)
3-Nitrotoluene (3-NT)
4-Nitrotoluene (4-NT)
Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine (HMX)
1,3,5-Trinitrobenzene (1,3,5-TNB)
2,4,6-Trinitrotoluene (2,4,6-TNT)
TABLE 2-30.
METHOD 8331 - TETRAZENE
Tetrazene
TWO - 38 Revision 2
September 1994
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TABLE 2-31
METHOD 8410 - SEMIVOLATILES
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)pyrene
Benzole acid
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropyl)ether
Bi s(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
4-Chloroaniline
4-Chloro-3-methylphenol
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Dibenzofuran
Di-n-butyl phthalate
1,2-Di chlorobenzene
1,3-Di chlorobenzene
1,4-Di chlorobenzene
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
Hexachlorocycl opentadi ene
Hexachloroethane
Isophorone
2-Methylnaphthalene
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-Tri chlorophenol
2,4,6-Trichlorophenol
TWO - 39
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TABLE 2-32.
ANALYSIS METHODS FOR INORGANIC COMPOUNDS
Compound
Aluminum
Antimony
Arsenic
Barium
Beryl 1 i urn
Bromide
Cadmium
Calcium
Chloride
Chromium
Chromium, hexavalent
Cobalt
Copper
Cyanide
Fluoride
Iron
Lead
Lithium
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Nitrate
Nitrite
Osmium
Phosphate
Phosphorus
Potassium
Selenium
Silver
Sodium
Strontium
Sulfate
Sulfide
Thallium
Tin
Vanadium
Zinc
Applicable Method (s)
6010,
6010,
6010,
6010,
6010,
9056
6010,
6010,
9056,
6010,
7195,
6010,
6010,
9010,
9056
6010,
6010,
6010,
6010,
6010,
7470,
6010,
6010,
9056,
9056
7550
9056
6010
6010,
6010,
6010,
6010,
6010,
9035,
9030,
6010,
7870
6010,
6010,
6020,
6020,
6020,
6020,
6020,
6020,
7140
9250,
6020,
7196,
6020,
6020,
9012,
7380,
6020,
7430
7450
6020,
7471
7480,
6020,
9200
7610
7740,
6020,
7770
7780
9036,
9031
6020,
7910,
6020,
7020
7040,
7060,
7080,
7090,
7130,
9251,
7190,
7197,
7200,
7210,
9013
7381
7420,
7460,
7481
7520
7741,
7760,
9038,
7840,
7911
7950,
7041,
7061,
7081
7091
7131
9252,
7191
7198
7201
7211
7421
7461
7742
7761
9056
7841
7951
7062
7062
9253
TWO - 40
Revision 2
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TABLE 2-33.
CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TIMES FOR AQUEOUS MATRICESA
Name
Container
Preservation
Maximum holding time
Bacterial Tests:
Coliform, total P, G
Inorganic Tests:
Chloride P, G
Cyanide, total and amenable P, G
to chlorination
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.
6 hours
28 days
14 days
Hydrogen ion (pH)
Nitrate
Sulfate
Sulfide
Metals:
Chromium VI
Mercury
Metals, except chromium VI
and mercury
Organic Tests:
Acrolein and acrylonitri le
Benzidines
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 ha I ides (TOX)
Radiological Tests:
Alpha, beta and radium
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
None required
Cool, 4°C
Cool, 4°C
Coot, 4°C, add zinc acetate
Cool, 4°C
HNO, to pH<2
HN03 to pH<2
Cool, 4°C, 0.008% Na2S2033,
Adjust pH to 4-5
Cool, 4°C, 0.008% Na2S2033,
Adjust pH to 6-9, store in
dark
Cool, 4°C, 0.008% Na2S20,
n
Cool, 4°C, 0.008% Na2S203
Cool, 4°C, 0.008% Na2S2033
Cool, 4°C, 0.008% Na2S2033
store in dark
Cool, 4°C, 0.008% Na2S203,
store in dark
Cool, 4°C,
Cool, 4°CZ
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% Na2S203 '3
Cool, 4°C, 0.008% Na2S2033
Cool, 4°CZ
HN03 to pH<2
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
1
Table excerpted, in part, from Table II, 49 FR 209, October 26, 1984, p 28.
Polyethylene (P) or Glass (G)
Adjust to pH<2 with H2SO,, HCl or solid NaHSO,.
Free chlorine must be removed prior to addition of HCl by the appropriate addition of Na2S203.
TWO - 41
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September 1994
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TABLE 2-34. PREPARATION METHODS FOR ORGANIC ANALYTES
Acids
Acrolein
Acrylonitrile
Acetonitrile
Aromatic Volatiles
Base/Neutral
Chlorinated
Herbicides
Chlorinated
Hydrocarbons
Halogenated
Volatiles
Nitroaromatic and
Cyclic Ketones
Non-halogenated
Volatiles
Organochlorine
Pesticides and PCBs
Organophosphorus
Pesticides
Phenols
Phthalate Esters
Polynuclear
Aromatic
Hydrocarbons
Volatile Orqanics
Aqueous (pH)3
3510
3520
(PH <2)
5030
5030
3510
3520
(pH >11)
8150
8151
(PH <2)
3510
3520
(PH 7)
5030
3510
3520
(pH 5-9)
5030
3510
3520
3665
(pH 5-9)
3510
3520
(pH 6-8)
3510
3520
(PH <2)
3510
3520
(pH 7)
3510
3520
(PH 7)
5030
Solids
3540, 3541
3550
35802
5030
5030
3540
3541
3550
35802
8150
8151,
35802
3540
3541
3550
35802
5030
3540
3541
3550
35802
5030
3540
3541
35802
3665
3540
3541
35802
3540
3541
3550
35802
3540
3541
3550
35802
3540, 3541
3550
35802
5030
Sludges
Emulsions1 (pH)
3520
(pH <2)
5030
5030
3520
(pH >11)
8150
8151
(PH <2)
3520
(pH 7)
5030
3520
(pH 5-9)
5030
3520
(pH 5-9)
3520
(pH 6-8)
3520
(pH <2)
3520
(pH 7)
3520
(pH 7)
5030
Oils
3650
35802
5030
5030
3650
35802
35802
35802
5030
35802
5030
35802
35802
3650
35802
35802
3560
35802
5030
1 If attempts to break up emulsions are unsuccessful, these methods may be used.
2 Method 3580 is only appropriate if the sample is soluble in the specified solvent.
3
pH at which extraction should be performed.
TWO - 42
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TABLE 2-35.
CLEANUP OF ORGANIC ANALYTE EXTRACTS
Analyte Type
Acids
Base/Neutral
Chlorinated
Herbicides
Chlorinated
Hydrocarbons
Nitroaromatics &
Cyclic Ketones
Organophosphorus
Pesticides
Organochlorine
Pesticides &
PCBs
Phenols
Phthalate
Esters
Polynuclear
Aromatic
Hydrocarbons
Method(s)
3650
3650
8150
8151
3620
3640
3620
3640
3620
3620
3630
3640
3660
3665
3630
3640
3650
3610
3611
3620
3640
3610
3611
3630
3640
TWO - 43
Revision 2
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TABLE 2-36.
DETERMINATION OF ORGANIC ANALYTES
GC/MS Determination
Methods
Specific GC Detection
Methods
HPLC
SEMIVOLATILES
Acids
Base/Neutral
Carbamates
Chlorinated Herbicides
Chlorinated Hydrocarbons
Dyes
Explosives
Haloethers
Nitroaromatics and Cyclic
Ketones
Nitrosoamines
Organochlorine Pesticides and
PCBs
Organophosphorous Pesticides
Phenol s
Phthalate Esters
Polynuclear Aromatic
Hydrocarbons
8270
8250
8270
8250
8270*
8270
8250
8270
8250
8270
8250
8270
8250
8270*
8270*
8270
8250
8270
8250
8270
8250
8150
8151
8120
8121
8110
8090
8070
8080
8081
8140
8141
8040
8060
8061
8100
8318
8321
8330
8331
8321
8310
VOLATILES
Acrolein, Acrylonitrile,
Acetonitrile
Acryl amide
Aromatic Volatiles
Formaldehyde
Halogenated Volatiles
Non-halogenated Volatiles
Volatile Organics
8240
8260
8240
8260
8240
8260
8240
8240
8260
8030
8031
8032
8020
8021
8010
8011
8021
8015
8010
8011
8020
8021
8030
8031
8316
8315
8316
8315
8315
8316
*This method is an alternative confirmation method. It is not the method of choice.
TWO - 44
Revision 2
September 1994
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OO
o
I—I
a.
.O
-------
FIGURE 2-2.
SCHEMATIC OF SEQUENCE TO DETERMINE
IF A WASTE IS HAZARDOUS BY CHARACTERISTIC
DOT (49 CFR 173 300)
Is
waste
reactive to
air and/or
water?
C hazardous by\
reason of i
ignitability J
laracteristic^/
Is waste
explosive?
Generator Knowledge
DOT (49 CFR 173.151)
What is
physical state
of waste?
Is waste
ignitable?
Hazardous^)
Perform Paint
Filter Test
(Method 9095)
Methods 1110 and 9040
Yes
Is waste
corrosive?
/" Nonhazardous ^
( for corrosivity )
\c;haracteristi(;/
Methods 1010 or 1020
Yes
TWO - 46
Revision 2
September 1994
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FIGURE 2-2.
(Continued)
Nonhazardous
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-r 20 <
TC regulatory
limit?
Is waste
leachable and
toxic?
(Method 1311)
Nonhazardous
for toxicity
characteristic
Nonhazardous^N.
for toxicity J
characteristic^/
TWO - 47
Revision 2
September 1994
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FIGURE 2-3A.
EP
Sample
1310
3010
(7760 Ag)
6010
7470
Hg
3510
Neutral
8150
8151
Herbicides
Ba--
Cr --
Ag --
-- As
-- Cd
-- Pb
-- Se
8080
8081
Pesticides
TWO - 48
Revision 2
September 1994
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FIGURE 2-3B.
RECOMMENDED SW-846 METHODS OF ANALYSIS FOR TCLP LEACHATES
3010
6010
Ba -
Cr -
Ag -
- As
- Cd
- Pb
- Se
1
7470
Hg
Sample
.
TCLP
1
3510
Neutral
8240 3510
8260 (Acidic
Volatile and
Organics Basic)
,
8080
8081
Pestic-
ides
8270
Semi vol-
atile
Orqanics
1
8150
8151
Herbic-
ides
TWO - 49
Revision 2
September 1994
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FIGURE 2-4A.
GROUND WATER ANALYSIS
Organic
Sample
1
VOA
, * ,
8240 or
8260
1
Semivolatiles
, I
3510 or
3520
, I
8270 or
8250
i
\ ' \ t
Pesticides
1
Herbicides Dioxins
1 1
3510 or
3520
Neutral
I
1 3620, 3640
and/or 3660
\
8080
81 50 8280
1 -Optional: Cleanup required only if interferences prevent analysis
TWO - 50
Revision 2
September 1994
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FIGURE 2-4B.
INDICATOR ANALYTE
Indicator
Analyte(s)
1
POC
1 - Barcelona, 1984, (See Reference 1)
2 - Riggin, 1984, (See Reference 2)
TWO - 51
Revision 2
September 1994
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FIGURE 2-4C.
GROUND WATER
( GROUND WATER1 )
V SAMPLE J
SAMPLE PREPARATION
3005 OR 3015
SAMPLE PREPARATION
3015 OR 3020
I
Ag, Al, As, Ba, Be,
Cd, Co, Cr, Cu, Fe,
Mg, Mn, Mo, Ni, Pb,
Sb, Se, Ti, V, Zn
Ag, Al, As, Ba, Be,
Cd, Co, Cr, Cu, Mn,
Ni, Pb. Sb, TI, Zn
Ag - 7760
Ba - 7080
Cd-7130
Cr-7190
Fe -7380
Mn - 7460
Ni - 7520
Sb - 7040
TI - 7840
Zn - 7950
Al - 7020
Be -7090
Co - 7200
Cu-7210
Mg - 7450
Mo - 7480
Pb - 7420
Sn - 7870
V - 7910
i
Ag- 7761'
Ba - 7081 *
Be - 7091
Cd-7131
Co - 7201
Cr-7191
Cu - 721 1*
Fe-7381*
Mn-7461'
Mo - 7481
Pb - 7421
TI - 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
TWO - 52
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CHAPTER THREE
METALLIC ANALYTES
3.1 SAMPLING CONSIDERATIONS
3.1.1 Introduction
This manual contains procedures for the analysis of metals 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 metal 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 functional 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 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 or 3051.
THREE - 1 Revision 2
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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 standard (ICV): 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.
THREE - 2 Revision 2
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3.1.3 Sample Handling and Preservation
Sample holding times, digestion procedures and suggested collection volumes
are listed in Table 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 Safety
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.
THREE - 3 Revision 2
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TABLE 3-1.
SAMPLE HOLDING TIMES, REQUIRED DIGESTION VOLUMES AND RECOMMENDED COLLECTION
VOLUMES FOR METAL DETERMINATIONS IN AQUEOUS AND SOLID SAMPLES
Measurement
Digestion
Vol. Req.a
(mL)
Collection
Volume (mL)a
Treatment/
Preservative
Holding Time0
Metals (except hexavalent chromium and mercury):
Aqueous
Total
Dissolved
Suspended
Solid
Total
Chromium VI:b
Aqueous
Solid
Mercury:
Aqueous
Total
Dissolved
100
100
100
2g
100
Solid
Total
100
100
0.2g
600
600
600
200g
400
400
200g
HN03 to pH <2
6 months
Filter on site;
HN03 to pH <2
6 months
Filter on site
6 months
6 months
400 24 hr
200g
HN03 to pH <2
28 days
Filter;
HN03 to pH <2
28 days
28 days
"Unless stated otherwise.
bThe holding time for the analysis of hexavalent chromium in solid samples has
not yet been determined. A holding time of "as soon as possible" is recommended.
CA11 non-aqueous samples and all aqueous samples that are to be analyzed for
mercury and hexavalent chromium must be stored at 4°C ± 2°C until analyzed,
either glass or plastic containers may be used.
THREE - 4
Revision 2
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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.
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 metals determination 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 determination 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 determination 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 determination 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 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 determination 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
metals determination by FLAA, GFAA, ICP-AES or ICP-MS. Nitric acid is added to
THREE - 5 Revision 2
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the representative sample in a Teflon 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.
THREE - 6 Revision 2
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METHOD 3005A
ACID DIGESTION OF WATERS FOR TOTAL RECOVERABLE OR
DISSOLVED METALS FOR ANALYSIS BY FLAA OR ICP SPECTROSCOPY
1.0 SCOPE AND APPLICATION
1.1 Method 3005 is an acid digestion procedure used to prepare surface
and ground water samples for analysis by flame atomic absorption spectroscopy
(FLAA) or by inductively coupled argon plasma spectroscopy (ICP). Samples
prepared by Method 3005 may be analyzed by AAS or ICP for the following metals:
Aluminum Magnesium
Antimony** Manganese
Arsenic* Molybdenum
Barium Nickel
Beryllium Potassium
Cadmium Selenium*
Calcium Silver
Chromium Sodium
Cobalt Thallium
Copper Vanadium
Iron Zinc
Lead
* ICP only
**May be analyzed by ICP, FLAA, or GFAA
1.2 When analyzing for total dissolved metals filter the sample, at the
time of collection, prior to acidification with nitric acid.
2.0 SUMMARY OF METHOD
2.1 Total recoverable metals - The entire sample is acidified at the time
of collection with nitric acid. At the time of analysis the sample is heated
with acid and substantially reduced in volume. The digestate is filtered and
diluted to volume, and is then ready for analysis.
2.2 Dissolved metals - The sample is filtered through a 0.45-/zm filter
at the time of collection and the liquid phase is then acidified at the time of
collection with nitric acid. Samples for dissolved metals do not need to be
digested as long as the acid concentrations have been adjusted to the same
concentration as in the standards.
3.0 INTERFERENCES
3.1 The analyst should be cautioned that this digestion procedure may not
be sufficiently vigorous to destroy some metal complexes.
3005A - 1 Revision 1
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Precipitation will cause a lowering of the silver concentration and therefore an
inaccurate analysis.
4.0 APPARATUS AND MATERIALS
4.1 Griffin beakers of assorted sizes or equivalent.
4.2 Watch glasses or equivalent.
4.3 Qualitative filter paper and filter funnels.
4.4 Graduated cylinder or equivalent.
4.5 Electric hot plate or equivalent - adjustable and capable of
maintaining a temperature of 90-95°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 Reagent Water. Reagent water shall 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), HNO,. Acid should be analyzed to
determine level of impurities. If method blame is < MDL, then acid can be used.
5.4 Hydrochloric acid (concentrated), HC1. Acid should be analyzed to
determine level of impurities. If method blank is < MDL, then 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. Both plastic and glass containers are suitable.
6.3 Sampling
6.3.1 Total recoverable metals - All samples must be acidified at
the time of collection with HN03 (5 ml/I).
6.3.2 Dissolved metals - All samples must be filtered through a
0.45-/im filter and then acidified at the time of collection with HNO,
(5 ml/I).
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7.0 PROCEDURE
7.1 Transfer a 100-mL aliquot of well-mixed sample to a beaker.
7.2 For metals that are to be analyzed, add 2 mL of concentrated HN03 and
5 ml of concentrated HC1. The sample is covered with a ribbed watch glass or
other suitable covers and heated on a steam bath, hot plate or other heating
source at 90 to 95°C until the volume has been reduced to 15-20 ml.
CAUTION: Do not boil. Antimony is easily lost by volatilization from
hydrochloric acid media.
7.3 Remove the beaker and allow to cool. Wash down the beaker walls and
watch glass with water and, when necessary, filter or centrifuge the sample to
remove silicates and other insoluble material that could clog the nebulizer.
Filtration should be done only if there is concern that insoluble materials may
clog the nebulizer; this additional step is liable to cause sample contamination
unless the filter and filtering apparatus are thoroughly cleaned and prerinsed
with dilute HN03.
7.4 Adjust the final volume to 100 ml with reagent water.
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, blanks should be
carried throughout the entire sample preparation and analytical process. These
blanks will be useful in determining if samples are being contaminated. Refer
to Chapter One for the proper protocol when analyzing blanks.
8.3 Replicate samples should be processed on a routine basis. A
replicate sample is a sample brought through the whole sample preparation and
analytical process. Replicate samples will be used to determine precision. The
sample load will dictate the frequency, but 5% is recommended. Refer to Chapter
One for the proper protocol when analyzing replicates.
8.4 Spiked samples or standard reference materials should be employed to
determine accuracy. A spiked sample should be included with each batch. Refer
to Chapter One for the proper protocol when analyzing spikes.
9.0 METHOD PERFORMANCE
9.1 No data provided.
3005A - 3 Revision 1
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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.
i
3005A - 4
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METHOD 3005A
ACID DIGESTION OF WATERS FOR TOTAL RECOVERABLE OR
DISSOLVED METALS FOR ANALYSIS BY FLAA OR ICP SPECTROSCOPY
Start
7.1 Tr«n»fmr
aliquot of
(ample to
beaker
7 2 Add
concentrated
HNO, and HC1
7.2 H.at
•ample to
reduce volume
7.3 Cool
beaker;
filter if
necenary
7.4 Adjutt
final volume
Stop
3005A - 5
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METHOD 3010A
ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS FOR
TOTAL METALS FOR ANALYSIS BY FLAA OR ICP SPECTROSCOPY
1.0 SCOPE AND APPLICATION
1.1 This digestion procedure is used for the preparation of aqueous
samples, EP and mobility-procedure extracts, and wastes that contain suspended
solids for analysis, by flame atomic absorption spectroscopy (FLAA) or
inductively coupled argon plasma spectroscopy (ICP). The procedure is used to
determine total metals.
1.2 Samples prepared by Method 3010 may be analyzed by FLAA or ICP for
the following:
Aluminum Magnesium
*Arsenic Manganese
Barium Molybdenum
Beryllium Nickel
Cadmium Potassium
Calcium *Selenium
Chromium Sodium
Cobalt Thallium
Copper Vanadium
Iron Zinc
Lead
* Analysis by ICP
NOTE: See Method 7760 for the digestion and FLAA analysis of Silver.
1.3 This digestion procedure is not suitable for samples which will be
analyzed by graphite furnace atomic absorption spectroscopy because hydrochloric
acid can cause interferences during furnace atomization. Consult Method 3020A
for samples requiring graphite furnace analysis.
2.0 SUMMARY OF METHOD
2.1 A mixture of nitric acid and the material to be analyzed is refluxed
in a covered Griffin beaker. This step is repeated with additional portions of
nitric acid until the digestate is light in color or until its color has
stabilized. After the digestate has been brought to a low volume, it is refluxed
with hydrochloric acid and brought up to volume. If sample should go to dryness,
it must be discarded and the sample reprepared.
3.0 INTERFERENCES
3.1 Interferences are discussed in the referring analytical method.
3010A - 1 Revision 1
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4.0 APPARATUS AND MATERIALS
4.1 Griffin beakers - 150-mL or equivalent.
4.2 Watch glasses - Ribbed and plain or equivalent.
4.3 Qualitative filter paper or centrifugation equipment.
4.4 Graduated cylinder or equivalent - lOOmL.
4.5 Funnel or equivalent.
4.6 Hot plate or equivalent heating source - adjustable and capable of
maintaining a temperature of 90-95°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 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 levels of impurities. If method blank is < MDL, the acid can be used.
5.4 Hydrochloric acid (1:1), HC1. Prepared from water and hydrochloric
acid. Hydrochloric acid 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 Aqueous wastewaters must be acidified to a pH of < 2 with HN03.
7.0 PROCEDURE
7.1 Transfer a 100-mL representative aliquot of the well-mixed sample to
a 150-mL Griffin beaker and add 3 mL of concentrated HNO,. Cover the beaker with
a ribbed watch glass or equivalent. Place the bealcer on a hot plate or
3010A - 2 Revision 1
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equivalent heating source and cautiously evaporate to a low volume (5 ml), making
certain that the sample does not boil and that no portion of the bottom of the
beaker is allowed to go dry. Cool the beaker and add another 3-mL portion of
concentrated HNQj. Cover the beaker with a nonribbed watch glass and return to
the hot plate, increase the temperature of the hot plate so that a gentle reflux
action occurs.
NOTE: If a sample is allowed to go to dryness, low recoveries will result.
Should this occur, discard the sample and reprepare.
7.2 Continue heating, adding additional acid as necessary, until the
digestion is complete (generally indicated when the digestate is light in color
or does not change in appearance with continued refluxing). Again, uncover the
beaker or use a ribbed watch glass, and evaporate to a low volume (3 ml), not
allowing any portion of the bottom of the beaker to go dry. Cool the beaker.
Add a small quantity of 1:1 HC1 (10 mL/100 ml of final solution), cover the
beaker, and reflux for an additional 15 minutes to dissolve any precipitate or
residue resulting from evaporation.
7.3 Wash down the beaker walls and watch glass with water and, when
necessary, filter or centrifuge the sample to remove silicates and other
insoluble material that could clog the nebulizer. Filtration should be done only
if there is concern that insoluble materials may clog the nebulizer. This
additional step can cause sample contamination unless the filter and filtering
apparatus are thoroughly cleaned. Rinse the filter and filter apparatus with
dilute nitric acid and discard the rinsate. Filter the sample and adjust the
final volume to 100 ml with reagent water and the final acid concentration to
10%. The sample is now ready for analysis.
8.0 QUALITY CONTROL
8.1 All quality control measures described in Chapter One should be
followed.
8.2 For each analytical batch of samples processed, blanks should be
carried throughout the entire sample-preparation and analytical process. These
blanks will be useful in determining if samples are being contaminated. Refer
to Chapter One for the proper protocol when analyzing blanks.
8.3 Replicate samples should be processed on a routine basis. A
replicate sample is a sample brought through the whole sample preparation and
analytical process. A replicate sample should be processed with each analytical
batch or every 20 samples, whichever is greater. Refer to Chapter One for the
proper protocol when analyzing replicates.
8.4 Spiked samples or standard reference materials should be employed to
determine accuracy. A spiked sample 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 spikes.
8.5 The method of standard addition shall be used for the analysis of all
EP extracts and delisting petitions (see Method 7000, Step 8.7). Although not
required, use of the method of standard addition is recommended for any sample
3010A - 3 Revision 1
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that is suspected of having an interference.
9.0 METHOD PERFORMANCE
9.1 No data provided.
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.
3010A - 4 Revision 1
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METHOD 3010A
ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS
FOR TOTAL METALS ANALYSIS BY FLAA OR ICP SPECTROSCOPY
Start
7.1 Trantfar *aapli
aliquot to baakar,
add concantratad
HNO.
7.1 H.at to
avaporata to low
voluaa, cool, and
add concantratad
HNO,
7.1 Rahaat,
incraaaa
taaparatura to
craata gantla
raflux action
7.2 Haat to
complata digaation,
avaporata,add
KCl,warn baakar
7.3 Filtar if
nacaoary and
adjuat voluma
3010A - 5
Revision 1
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METHOD 3015
MICROWAVE ASSISTED ACID DIGESTION OF AQUEOUS
SAMPLES AND EXTRACTS
1.0 SCOPE AND APPLICATION
1.1 This digestion procedure is used for the preparation of aqueous
samples, mobility-procedure extracts, and wastes that contain suspended solids
for analysis, by flame atomic absorption spectroscopy (FLAA), graphite furnace
absorption spectroscopy (GFAA), inductively coupled argon plasma spectroscopy
(ICP), or inductively coupled argon plasma mass spectrometry (ICP-MS). The
procedure is a hot acid leach for determining available metals. 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 3015.
1.2 Samples prepared by Method 3015 using nitric acid digestion may be
analyzed by FLAA, GFAA, ICP-AES, or ICP-MS for the following:
Aluminum Lead
Antimony Magnesium
Arsenic* Manganese
Barium Molybdenum
Beryllium Nickel
Cadmium Potassium
Calcium Selenium*
Chromium Silver
Cobalt Sodium
Copper Thallium
Iron Vanadium
Zinc
*Cannot be analyzed by FLAA
2.0 SUMMARY OF METHOD
2.1 A representative 45 mL aqueous sample is digested in 5 mL of
concentrated nitric acid in a fluorocarbon (PFA or TFM) digestion vessel for 20
minutes using microwave heating. After the digestion process, the sample is
cooled, and then filtered, centrifuged, or allowed to settle in a clean sample
bottle prior to analysis.
3.0 INTERFERENCES
3.1 Many samples that contain organics, such as TCLP extracts, will
result in higher vessel pressures which have the potential to cause venting of
the vessels. Venting can result in either loss of analytes and/or sample, which
must be avoided. A smaller sample size can be used but the final water volume
3015 - 1 Revision 0
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prior to nitric acid addition must remain at 45 ml. This is required to retain
the heat characteristics of the calibration procedure. Limits of quantitation
will change with sample quantity (dilution) as with instrumentation."
4.0 APPARATUS AND MATERIALS
4.1 Microwave apparatus requirements
4.1.1 The microwave unit provides programmable power with a
minimum of 574 W, which can be programmed to within + 10 W of the
required power. Typical units provide a nominal 600 W to 1200 W of
power. Temperature monitoring and control of the microwave unit are
desirable.
4.1.2 The microwave unit cavity is corrosion resistant and
well ventilated.
4.1.3 All electronics are protected against corrosion for safe
operation.
4.1.4 The system requires fluorocarbon (PFA or TFM) digestion
vessels (120 mL capacity) capable of withstanding pressures up to 7.5
± 0.7 atm (110 ± 10 psig) and capable of controlled pressure relief at
pressures exceeding 7.5 ± 0.7 atm (110 ± 10 psig).
4.1.5 A rotating turntable is employed to insure homogeneous
distribution of microwave radiation within the unit. The speed of the
turntable should be a minimum of 3 rpm.
CAUTION: Those laboratories now using or contemplating the use of
kitchen type microwave ovens for this method should be aware of
several significant safety issues. First, when an acid such as
nitric is used to assist sample digestion in microwave units in
open vessels, or sealed vessels equipped with venting features,
there is the potential for the acid gases 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 unit with corrosion resistant safety
devices prevents this from occurring.
CAUTION: The second safety concern relates to the use of sealed
containers without pressure relief valves in the unit. Tempera-
ture is the important variable controlling the reaction. Pressure
is needed to attain elevated temperatures but must be safely con-
tained. However, many digestion vessels constructed from certain
fluorocarbons may crack, burst, or explode in the oven under
certain pressures. Only unlined fluorocarbon (PFA or TFM)
containers with pressure relief mechanisms or containers with
fluorocarbon (PFA or TFM) liners and pressure relief mechanisms
are considered acceptable at present.
3015 - 2 Revision 0
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Users are therefore advised not to use kitchen type microwave
ovens or to use sealed containers without pressure relief valves
for microwave acid digestions by this method. Use of laboratory
grade microwave equipment is required to prevent safety hazards.
For further information consult reference 1.
CAUTION: In addition, there are many safety and operational
recommendations specific to the model and manufacturer of the
microwave equipment used in individual laboratories. These
specific suggestions are 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.
4.2 Volumetric graduated cylinder, 50 or 100 ml capacity or equivalent.
4.3 Filter paper, qualitative or equivalent.
4.4 Analytical balance, 300 g capacity, minimum accuracy ± 0.01 g.
4.5 Filter funnel, glass or disposable polypropylene.
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 shall be interference free. All
references to water in the method refer to reagent water unless otherwise specif-
ied (Ref. 2).
5.3 Concentrated nitric acid, HNO,. Acid should be analyzed to
determine levels of impurities. If the method blank is less than the 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 containers are preferable. See Chapter Three, Step 3.1.3 of this
manual, for further information.
6.3 Aqueous waste waters must be acidified to a pH of < 2 with HN03.
3015 - 3 Revision 0
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7.0 PROCEDURE
7.1 Calibration of Microwave Equipment
NOTE: If the microwave unit uses temperature feedback control
capable of replicating the performance specifications of the
method, then the calibration procedure may be omitted.
7.1.1 Measurement of the available power for heating is
evaluated so that absolute power in watts may be transferred from one
microwave unit to another. 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 unit. The
calibration format required for laboratory microwave units depends on
the type of electronic system used by the manufacturer to provide
partial microwave power. Few units 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 deter-
mined by a three-point calibration method (7.1.3), otherwise, the
analyst must use the multiple point calibration method (7.1.2).
7.1.2 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 section
7.1.4. This data is clustered about the customary working power ranges.
Nonlinearity has been commonly encountered at the upper end of the
calibration. If the unit'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.
7.1.3 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 section 7.1.4, and
calculate the power setting corresponding to the required power in watts
specified in the procedure from the (2-point) line. 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 7.1.2. This point should also be used to
periodically verify the integrity of the calibration.
7.1.4 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 (PFA or TFM) beaker or a beaker made of some other
material that does not significantly absorb microwave energy (glass
3015 - 4 Revision 0
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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 unit'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
P - (K) (Cp) (m) (AT)
Eq. 1
Where:
P = the apparent power absorbed by the sample in watts (W).
(W=joule-sec )
K = the conversion factor for thermochemical calories-sec"1 to watts
(=4.184)
C * 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)
AT = 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 •"C"1) the calibration
equation simplifies to:
P = (AT) (34.86)
NOTE: Stable line voltage is necessary for accurate and reproduc-
ible calibration and operation. The line voltage should be within
manufacturer's specification, and during measurement and operation
not vary by more than ±2 V. A constant power supply may be
necessary for microwave use if the source of the line voltage is
unstable.
3015 - 5 Revision 0
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Electronic components in most microwave units are matched to the units'
function and output. When any part of the high voltage circuit, power
source, or control components in the unit have been serviced or
replaced, it will be necessary to recheck the units' calibration power.
If the power output has changed significantly (±10 W), then the entire
calibration should be reevaluated.
7.2 All digestion vessels and volumetric ware must be carefully acid
washed and rinsed with reagent water. When switching between high solids
(concentrated) samples and low solids (low concentration) samples all digestion
vessels 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, 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 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 environ-
ment. In addition, to avoid precipitation of silver, ensure that all HC1 has
been rinsed from the vessels.
7.3 Sample Digestion
7.3.1 Weigh the fluorocarbon (PFA or TFM) digestion vessel, valve
and cap assembly to 0.01 g prior to use.
7.3.2 A 45 ml aliquot of a well shaken sample is measured in a
graduated cylinder. This aliquot is poured into the digestion vessel
with the number of the vessel recorded on the preparation sheet.
7.3.3 A blank sample of reagent water is treated in the same
manner along with spikes and duplicates.
7.3.4 Add 5 mL of concentrated nitric acid to each vessel that
will be used. Check to make sure the pressure relief disks are in the
caps with the smooth side toward the sample and start the caps a few
turns on the vessels. Finish tightening the caps in the capping station
which will tighten them to a uniform torque pressure of 12 ft-lbs.
(16 N-m) or to the manufacturers recommended specifications. Weigh each
capped vessel to the nearest 0.01 g.
CAUTION: Toxic nitrogen oxide fumes may be evolved, therefore all
work must be performed in a properly operating ventilation system.
The analyst should also be aware of the potential for a vigorous
reaction. If a vigorous reaction occurs, allow to cool before
capping the vessel.
7.3.5 Evenly distributed the vessels in the carousel according
to the manufacturer's recommended specifications. Blanks are treated
as samples for the purpose of balancing the power input. When fewer
3015 - 6 Revision 0
September 1994
-------
than the recommended number of samples are digested, the remaining
vessels should be filled with 45 ml of reagent water and 5 ml of nitric
acid to achieve the full compliment of vessels. This provides an energy
balance since the microwave power absorbed is proportional to the total
mass in the cavity (Ref. 1).
7.3.6 Program the microwave unit according to the manufacturer's
recommended specifications and, if used, connect the pressure vessels
to the central overflow vessel with PFA-fluorocarbon tubes. The chosen
sequence will bring the samples to 160°C ± 4°C in 10 minutes and will
permit a slow rise to 165-170 °C during the second 10 minutes (Ref. 3).
Start the turntable motor and be sure the vent fan is running on high
and the turntable is turning. Start the microwave generator.
7.3.6.1 Newer microwave units are capable of higher
power that permit digestion of a larger number of samples per
batch. If the analyst wishes to digest more samples at a time,
the analyst may use different power settings as long as they
result in the same time and temperature conditions defined in
7.3.6. That is, any sequence of power that brings the samples to
1608C ± 4°C in 10 minutes and permits a slow rise to 165-170eC
during the second 10 minutes (Ref. 2).
Issues of safety, structural integrity (both temperature and
pressure limitations), heat loss, chemical compatibility,
microwave absorption of vessel material, and energy transport will
be considerations made in choosing alternative vessels. If all
of the considerations are met and the appropriate power settings
are provided to reproduce the reaction conditions defined in
7.3.6, then these alternative vessels may be used (Ref. 1,3)
7.3.7 At the end of the microwave program, allow the vessels
to cool for at least 5 minutes in the unit before removal to avoid
possible injury if a vessel vents immediately after microwave heating.
The samples may be cooled outside the unit by removing the carousel and
allowing the samples to cool on the bench or in a water bath. When the
vessels have cooled to room temperature, weigh and record the weight of
each vessel assembly. If the weight of the sample plus acid has
decreased by more than 10% discard the sample.
7.3.8 Complete the preparation of the sample by carefully
uncapping and venting each vessel in a fume hood. Transfer the sample
to an acid-cleaned bottle. If the digested sample contains par-
ticulates 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.
3015 - 7 Revision 0
September 1994
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7.3.8.2 Settling: 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: 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.
7.3.9 The concentration values obtained from analysis must be
corrected for the dilution factor from the acid addition. If the sample
will be analyzed by ICP-MS additional dilution will generally be
necessary. For example, the sample may be diluted by a factor of 20
with reagent water and the acid strength adjusted back to 10% prior to
analysis. The dilutions used should be recorded and the measured con-
centrations adjusted accordingly (e.g., for a 45 ml sample and 5 ml of
acid the correction factor is 1.11).
8.0 QUALITY CONTROL
8.1 All quality control measures described in Chapter One, of this
Manual, should be followed.
8.2 For each analytical batch of samples processed, analytical reagent
blanks (also field blanks if they were taken) should be carried throughout the
entire sample preparation and analytical process. These blanks will be useful
in determining if samples are being contaminated.
8.3 Duplicate samples should be processed on a routine basis. A
duplicate sample is a real 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.
8.4 Spiked samples or standard reference materials should be employed
to determine accuracy. A spiked sample should be included with each group of
samples processed and whenever a new sample matrix is being analyzed.
9.0 METHOD PERFORMANCE
9.1 Refer to Table 1 for a summary of performance data.
3015 - 8 Revision 0
September 1994
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10.0 REFERENCES
1. Introduction to Microwave Sample Preparation: Theory and Practice.
Kingston, H. M.; Jassie, L. B., Eds.; ACS Professional Reference Book
Series: American Chemical Society, Washington, DC, 1988; Ch 6 & 11.
2. 1985 Annual Book of ASTM Standards. Vol. 11.01; "Standard Specification
for Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
3. Kingston, H. M., Final Report EPA IAG #DWI3932541-01-I, September 30,
1988, Appendix A.
4. Shannon, M., Alternate Test Procedure Application, USEPA Region V,
Central Regional Laboratory, 536 S. Clark Street, Chicago, IL 60606,
1989.
5. Kingston, H. M., Walter, P. J., "Comparison of Microwave Versus
Conventional Dissolution for Environmental Applications", Spectroscopy,
vol. 7 No. 9,20-27,1992.
6. Sosinski, P., and Sze C., "Absolute Accuracy Study, Microwave Digestion
Method 3015 (Nitric acid only)"; EPA Region III Central Regional
Laboratory, 1991.
3015 - 9 Revision 0
September 1994
-------
TABLE 1
MICROWAVE DIGESTION METHOD 3015 (Nitric Acid Only)
Ele»
Al
Al
Al
Al
Ba
Ba
Ba
Cd
Cd
Cd
Cd
Zn
Zn
Zn
Zn
As
As
Co
Co
K
K
Ni
Ni
Ni
Pb
Pb
Pb
Pb
Sb
Sb
Se
Se
Tl
Tl
V
V
Be
Be
Ca
Ca
Material
Tm-11
Tm-12
T-107
T-109
Tm-11
Tm-12
T-107
Tm-11
Tm-12
T-107
T-109
Tm-11
Tm-12
T-107
T-109
T-107
T-109
Tm-11
Tm-12
T-95
T-109
Tm-11
Tm-12
T-109
Tm-11
Tm-12
T-107
T-109
UP980-1
WP980-2
T-95
T-107
UP980-1
WP980-2
Tm-11
Tm-12
T-107
T-109
T-107
T-109
Certified
Mean
510.0
2687.0
220.0
113.0
450.0
2529.0
192.0
40.8
237.0
14.3
12.1
55.4
314.0
75.8
74.0
10.8
8.15
227.0
1067.0
4700.0
2330.0
264.0
1234.0
57.0
275.0
1326.0
26.0
34.9
16.9
101.5
60.1
11.0
50.0
6.3
491.0
2319.0
11.0
22.1
11700.0
35400.0
Observed
Mean
485.5
2770.6
213.5
117.7
441.4
2431.4
196.6
44.6
242.3
12.4
10.3
55.9
316.5
81.6
69.9
12.8
90.6
242.6
1153.3
5080.3
2601.5
284.3
1293.0
60.8
275.9
1359.0
30.0
39.3
18.3
108.9
65.9
13.0
55.1
7.0
532.6
2412.8
11.3
25.6
12364.0
38885.0
Std. Dev.
26.3
88.2
19.3
30.6
23.4
70.3
15.9
2.1
8
0.9
1.7
2.6
8.9
3.3
4.1
0.84
11.0
14.1
35.9
784
383.4
16.5
39.4
3.09
32.2
35.0
0.2
1.2
0.47
34.4
2.6
0.9
2
0.52
26.1
60.6
0.53
0.91
783.6
999
Relative
Standard
Deviation
5.4
3.2
9.0
2.6
5.3
2.9
8.1
4.7
3.3
7.2
16.5
4.6
2.8
4.0
5.8
6.5
12.2
5.8
3.1
15.4
14.7
5.8
3.0
5.0
11.7
2.6
0.66
3.0
2.6
31.6
3.94
6.9
3.6
7.4
4.9
2.5
4.7
3.6
6.3
2.6
Relative
Bias
-4. 80%
3.11%
-2.95%
4.16%
-1.90%
-3.86%
2. 44%
9.46%
2.25%
-12.94%
-14.55%
1.06%
0.82%
7.68%
-5.46%
19.26%
11.26%
6.90%
8.09%
8.09%
11.65%
7.71%
4.79%
6.72%
0.36%
2.49%
15.65%
12.69%
8.27%
7.33%
9.77%
19.00%
10.26%
11.66%
8.48%
4.05%
3.00%
15.97%
5.68%
9.84%
3015 - 10
Revision 0
September 1994
-------
TABLE 1 (continued)
El em
Ca
Ca
Mg
Mg
Mg
Na
Na
Na
Cr
Cr
Cr
Cr
Cu
Cu
Cu
Cu
Fe
Fe
Fe
Fe
Mn
Mn
Mn
Mn
Ag
Material
T-107
T-109
T-95
T-107
T-109
T-95
T-107
T-109
Tm-11
Tm-12
T-107
T-109
Tm-11
Tm-12
T-107
T-109
Tm-11
Tm-12
T-107
T-109
Tm-11
Tm-12
T-107
T-109
WS378-1
Certified
Mean
11700.0
35400.0
32800.0
2100.0
9310.0
190000.0
20700.0
12000.0
52.1
299.0
13.0
18.7
46.3
288.0
30.0
21.4
249.0
1089.0
52.0
106.0
46.0
263.0
45.0
34.0
46.0
Observed
Mean
12364.0
38885.0
35002.0
2246.7
10221.7
218130.0
22528.0
13799.5
64.3
346.0
22.3
32.6
76.5
324.0
42.3
54.0
289.3
1182.5
63.8
134.0
60.9
304.4
52.6
46.6
19.4
Std. Dev.
783.6
999
1900
110.5
218.6
10700
1060
516.2
4.1
9.8
1.5
6.4
4.4
8.9
4.0
3.6
16.4
43.5
8.7
6.6
3.2
9.1
3.1
3.0
5.6
Relative
Standard
Deviation
6.3
2.6
5.4
4.9
2.1
4.9
4.7
3.7
6.4
2.8
6.7
19.6
5.7
2.7
9.4
6.7
5.7
3.7
13.6
4.9
5.2
3.0
5.9
6.4
2.9
Relative
Bias
5.68%
9.84%
6.71%
6.99%
9.79%
14.81%
8.83%
15.00%
23.51%
15.74%
71.77%
74.71%
65.36%
12.52%
41.17%
152.38%
16.18%
8.59%
22.69%
26.50%
32.48%
15.77%
17.09%
37.18%
-57.83%
3015 - 11
Revision 0
September 1994
-------
METHOD 3015
MICROWAVE ASSISTED ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS
7.1 Calibrate
the miorewavo
equipment.
7.2 AeM wee
•nd HjO rlneo
•II dioeotian
OUoeware.
7.3.2 Moaeuro
46 mL aliquot
Into the
dlfeetlon
7.3.3 UM blank
eamploe of
p In
7.3,4 Add
eono*ntrat*
HNOato
7.3.( Plae*
v*«««li in tn«
blank* It n«e«**rv
to
7.3.6 Ploe*
tho eorouool
in ovon. hoot
•eoording to
powor program.
7.3.7 Allow
oool «o thoy
•ra nat hot
ta touch.
7.3.1 r>looo
••mola in
aeid-ol«anod
bottlo.
7.S.*1-7.3.8.3
Contri«ugo.
aottlo, and
firtar aampla.
7.3.9 Carroet
oonoamration
valuoi for
tho dilution
footer.
I
3015 - 12
Revision 0
September 1994
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METHOD 3020A
ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS
FOR TOTAL METALS FOR ANALYSIS BY GFAA SPECTROSCOPY
1.0 SCOPE AND APPLICATION
1.1 This digestion procedure is used for the preparation of aqueous
samples, mobility-procedure extracts, and wastes that contain suspended solids
for analysis by furnace atomic absorption spectroscopy (GFAA) for the metals
listed below. The procedure is used to determine the total amount of the metal
in the sample.
1.2 Samples prepared by Method 3020 may be analyzed by GFAA for the
following metals:
Beryllium Lead
Cadmium Molybdenum
Chromium Thallium
Cobalt Vanadium
NOTE; For the digestion and GFAA analysis of arsenic and selenium, see
Methods 7060 and 7740. For the digestion and GFAA analysis of
silver, see Method 7761.
2.0 SUMMARY OF METHOD
2.1 A mixture of nitric acid and the material to be analyzed is refluxed
in a covered Griffin beaker. This step is repeated with additional portions of
nitric acid until the digestate is light in color or until its color has
stabilized. After the digestate has been brought to a low volume, it is cooled
and brought up in dilute nitric acid such that the final dilution contains 3%
(v/v) nitric acid. This percentage will vary depending on the amount of acid
used to complete the digestion. If the sample contains suspended solids, it must
be centrifuged, filtered, or allowed to settle.
3.0 INTERFERENCES
3.1 Interferences are discussed in the referring analytical method.
4.0 APPARATUS AND MATERIALS
4.1 Griffin beakers - 150-mL, or equivalent.
4.2 Watch glasses - ribbed or equivalent.
3020A - 1 Revision 1
July 1992
'0
-------
4.3 Qualitative filter paper or centrifugation equipment.
4.4 Funnel or equivalent.
4.5 Graduated Cylinder - lOOmL.
4.6 Electric hot plate or equivalent - adjustable and capable of
maintaining a temperature of 90-95°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 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 levels 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 Aqueous wastewaters must be acidified to a pH of < 2 with HNO
3'
7.0 PROCEDURE
7.1 Transfer a 100-mL representative aliquot of the well-mixed sample to
a 150-mL Griffin beaker and add 3 mL of concentrated HN03. Cover the beaker with
a ribbed watch glass. Place the beaker on a hot plate and cautiously evaporate
to a low volume (5 mL), making certain that the sample does not boil and that no
portion of the bottom of the beaker is allowed to go dry. Cool the beaker and
add another 3-mL portion of concentrated HN03. Cover the beaker with a non-
ribbed watch glass and return to the hot plate. Increase the temperature of the
hot plate so that a gentle reflux action occurs.
3020A - 2 Revision 1
July 1992
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7.2 Continue heating, adding additional acid as necessary, until the
digestion is complete (generally indicated when the digestate is light in color
or does not change in appearance with continued refluxing). When the digestion
is complete, evaporate to a low volume (3 ml); use a ribbed watch glass, not
allowing any portion of the bottom of the beaker to go dry. Remove the beaker
and add approximately 10 ml of water, mix, and continue warming the beaker for
10 to 15 minutes to allow additional solubilization of any residue to occur.
7.3 Remove the beaker from the hot plate and wash down the beaker walls
and watch glass with water. When necessary, filter or centrifuge the sample to
remove silicates and other insoluble material that may interfere with injecting
the sample into the graphite atomizer. (This additional step can cause sample
contamination unless the filter and filtering apparatus are thoroughly cleaned
and prerinsed with dilute HN03.) Adjust to the final volume of 100 ml with
water. The sample is now ready for analysis.
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, method blanks should be carried
throughout the entire sample preparation and analytical process. These blanks
will be useful in determining if samples are being contaminated. Refer to
Chapter One for the proper protocol when analyzing blanks.
8.3 Replicate samples should be processed on a routine basis. Replicate
samples will be used to determine precision. The sample load will dictate
frequency, but 5% is recommended. Refer to Chapter One for the proper protocol
when analyzing replicates.
8.4 Spiked samples or standard reference materials should be employed to
determine accuracy. A spiked sample should be included with each batch of
samples processed or 5% and whenever a new sample matrix is being analyzed.
Refer to Chapter One for the proper protocol when analyzing spikes.
8.5 The concentration of all calibration standards should be verified
against a quality control check sample obtained from an outside source. Refer
to Chapter One for the proper protocol.
8.6 The method of standard addition shall be used for the analysis of all
EP extracts. See Method 7000, Step 8.7, for further information.
9.0 METHOD PERFORMANCE
9.1 No data provided.
3020A - 3 Revision 1
July 1992
-------
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.
3020A - 4 Revision 1
July 1992
-------
METHOD 3020A
ACID DIGESTION FOR AQUEOUS SAMPLES AND EXTRACTS
FOR TOTAL METALS FOR ANALYSIS BY GFAA SPECTROSCOPY
Start
7.1 Put sample
aliquot in
beaker, add
concentrated
HNO,,evaporate to
low volume
7.1 Cool beaker,add
concentrated
HNO,,heat until
gentle raflux
action occur*
7 2 Haat to
complete digestion,
evaporata to low
volume,cool
7 2 Add reagent
watar,warm to
dissolve any
precipitate or
re»idue
7 3 Filter or
centrifuge if
necessary and
adjust volume
3020A - 5
Revision 1
July 1992
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METHOD 3040
DISSOLUTION PROCEDURE FOR OILS. GREASES. OR WAXES
1.0 SCOPE AND APPLICATION
1.1 Method 3040 is used for the preparation of samples containing oils,
greases, or waxes for analysis by atomic absorption spectroscopy (AAS) or
inductively coupjed argon plasma emission spectroscopy (ICP) for the following
metals:
Antimony
Beryl 1 i urn
Cadmium
Chromium
Copper
Iron
Manganese
Nickel
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 parti cul ate material it is less effective;
most parti cul ate 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 3040 will not provide an adequate estimate of the total metals
concentration.
2.0 SUMMARY OF METHOD
2.1 A representative sample is dissolved in an appropriate solvent
(e.g., xylene or methyl isobutyl ketone). Organometal11c standards are
prepared using the same solvent, and the samples and standards are analyzed by
AAS or ICP.
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. Peristaltic pumps often prove useful when analysis is
performed by ICP.
3040 - 1
Revision 0
Date September 1986
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4.0 APPARATUS AND MATERIALS
4.1 Volumetric glassware.
4.2 Balance.
4.3 Atomic absorption spectrometer; With an auxiliary oxldant control
and a mechanism for background correction.
4.4 Inductively coupled argon plasma emission spectrometer system; With
a mechanism?orbackground correctionandInterelementinterference
correction. A peristaltic pump 1s optional.
5.0 REAGENTS
5.1 Methyl Isobutyl ketone (MIBK).
5.2 Xylene.
5.3 Organometal11c standards (two possible sources are Conostan
Division, Conoco SpecialityProducts, Inc., P.O. Box 1267, Ponca City, OK
74601, and the U.S. Department of Commerce, National Bureau of Standards,
Washington, DC 20234).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed 1n Chapter Nine of this manual.
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-g 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 is usually the preferred solvent for
longer-chain hydrocarbons and for most analyses performed by ICP. The longer-
chain hydrocarbons usually require a minimum of a 1:10 dilution, and lighter
oils may require only a 1:5 dilution if low detection limits are required.
7.3 All metals must be analyzed by the method of standard additions.
Because the method of standard additions can account only for multiplicative
interferences (matrix or physical interferences), the analytical program must
3040 - 2
Revision 0
Date September 1986
-------
account for additive Interference (nonspecific absorption and scattering 1n
AAS and nonspecific emission and Interelement Interference 1n ICP) by
employing background correction.
7.4 Sample preparation for the method of standard additions can be
performed on a weight or volume basis. Sample allquots 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 1t 1s approximately twice that of the first. The
second and third allquots are then diluted to the same final volume as the
first aliquot.
7.5 Set up and calibrate the analytical Instrumentation according to the
manufacturer's directions for nonaqueous samples.
7.6 Report data as the weighted average for all sample phases.
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.
8.2 Duplicate samples should be processed on a routine basis. Duplicate
samples will be used to determine precision. The sample load will dictate the
frequency, but 20% 1s recommended.
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.
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 No data provided.
10.0 REFERENCES
10.1 None required.
3040 - 3
Revision 0
Date September 1986
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METHOD 3040
DISSOLUTION PROCEDURE FOR OILS. GREASE. OR MAXES
7.1
o
Weigh out
2 g of
•ample
7.4
Weigh sample
into 3 vials:
dilute 1st vial: add
standard to 2nd vial
to increase cone. by
SOX; adjust 3rd vial
cone, to twice the
cone, of the 1st vial
Is more than
one phase
present?
Separate and
weigh phases
7.4
I Dilute
second and
third aliquots
to same volume
as first
7.2
J Weigh
aliquot
of organic
phase: dilute
with appropr.
solvent
Set up
and calibrate
analytical
instrumentation
7.3
I Analyre
octal* by
standard
additions
•method
7.6
Report data as
weighted
everege
f Stop J
3040 - 4
Revision 0
Date September 1986
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METHOD 3050A
ACID DIGESTION OF SEDIMENTS, SLUDGES, AND SOILS
1.0 SCOPE AND APPLICATION
1.1 This method is an acid digestion procedure used to prepare sediments,
sludges, and soil samples for analysis by flame or furnace atomic absorption
spectroscopy (FLAA and GFAA, respectively) or by inductively coupled argon plasma
spectroscopy (ICP). Samples prepared by this method may be analyzed by ICP for
all the listed metals, or by FLAA or GFAA as indicated below (see also Step 2.1):
FLAA GFAA
Aluminum Magnesium Arsenic
Barium Manganese Beryllium
Beryllium Molybdenum Cadmium
Cadmium Nickel Chromium
Calcium Osmium Cobalt
Chromium Potassium Iron
Cobalt Silver Lead
Copper Sodium Molybdenum
Iron Thallium Selenium
Lead Vanadium Thallium
Zinc Vanadium
NOTE: See Method 7760 for FLAA preparation for Silver.
2.0 SUMMARY OF METHOD
2.1 A representative 1- to 2-g (wet weight) sample is digested in nitric
acid and hydrogen peroxide. The digestate is then refluxed with either nitric
acid or hydrochloric acid. Hydrochloric acid is used for flame AA and ICP
analyses and nitric acid is used for furnace AA work. Dilute hydrochloric acid
is used as the final reflux acid for (1) the ICP analysis of As and Se, and (2)
he flame AA or ICP analysis of Ag, Al, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Mg,
Mo, Na, Ni, Os, Pb, Tl, V, and Zn. Dilute nitric acid is employed as the
final dilution acid for the furnace AA analysis of As, Be, Cd, Cr, Co, Fe, Pb,
Mo, Se, Tl, and V. The diluted samples have an approximate acid concentration
of 5.0% (v/v). A separate sample shall be dried for a total % solids
determination.
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 to aid in determining whether Method 3050
is applicable to a given waste.
3050A - 1 Revision 1
July 1992
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4.0 APPARATUS AND MATERIALS
4.1 Conical Phillips beakers - 250-mL, or equivalent.
4.2 Watch glasses ribbed or equivalent.
4.3 Drying ovens - That can be maintained at 30° C.
4.4 Thermometer - That covers range of 0-200°C.
4.5 Filter paper - Whatman No. 41 or equivalent.
4.6 Centrifuge and centrifuge tubes.
4.7 Analytical Balance - Capable of accurately weighing to the
nearest 0.01 g.
4.8 Electric Hot Plate or equivalent - Adjustable and capable of
maintaining a temperature of 90-95°C.
4.9 Glass Funnel or equivalent.
4.10 Graduated cylinder 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. 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.
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.
5.4 Hydrogen peroxide (30%), H202. Oxidant should be analyzed to
determine level of impurities.
3050A - 2 Revision 1
July 1992
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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 shall be refrigerated upon receipt and analyzed
as soon as possible.
7.0 PROCEDURE
7.1 Mix the sample thoroughly to achieve homogeneity. For each digestion
procedure, weigh to the nearest 0.01 g and transfer to a conical beaker 1.00-2.00
g of sample. For samples with low percent solids a larger sample size may be
used as long as digestion is completed.
7.2 Add 10 mL of 1:1 HN03, mix the slurry, and cover with a watch glass.
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 watch glass, and
reflux for 30 minutes. Repeat this last step to ensure complete oxidation.
Using a ribbed watch glass, allow the solution to evaporate to 5 mL without
boiling, while maintaining a covering of solution over the bottom of the beaker.
7.3 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 beaker with a watch glass and return
the covered beaker to the hot plate 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 beaker.
7.4 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.
7.5 If the sample is being prepared for (a) the ICP analysis of As and
Se, or (b) the flame AA or ICP analysis of Ag, Al, Ba, Be, Ca, Cd, Co, Cr, Cu,
Fe, K, Mg, Mn, Mo, Na, Ni, Os, Pb, Tl, V, and Zn, then add 5 mL of concentrated
HC1 and 10 mL of water, return the covered beaker to the hot plate, and reflux
for an additional 15 minutes without boiling. After cooling, dilute to a 100 mL
volume with water. Particulates in the digestate that may clog the nebulizer
should be removed by filtration, by centrifugation, or by allowing the sample to
settle.
7.5.1 Filtration - Filter through Whatman No. 41 filter paper (or
equivalent).
3050A - 3 Revision 1
July 1992
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7.5.2 Centrifugation - Centrifugation at 2,000-3,000 rpm for
10 minutes is usually sufficient to clear the supernatant.
7.5.3 The diluted sample has an approximate acid concentration of
5.0% (v/v) HC1 and 5.0% (v/v) HN03. The sample is now ready for analysis.
7.6 If the sample is being prepared for the furnace analysis of As, Be,
Cd, Co, Cr, Fe, Mo, Pb, Se, Tl, and V, cover the sample with a ribbed watch glass
and continue heating the acid-peroxide digestate until the volume has been
reduced to approximately 5 ml. 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.
7.6.1 Filtration - Filter through Whatman No. 41 filter paper (or
equivalent).
7.6.2 Centrifugation - Centrifugation at 2,000-3,000 rpm for
10 minutes is usually sufficient to clear the supernatant.
7.6.3 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. The sample is now ready for
analysis.
7.7 Calculations
7.7.1 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.
7.7.2 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, preparation blanks should be
carried throughout the entire sample preparation and analytical process. These
blanks will be useful in determining if samples are being contaminated. Refer
to Chapter One for the proper protocol when analyzing blanks.
8.3 Replicate samples should be processed on a routine basis. Replicate
samples will be used to determine precision. The sample load will dictate
frequency, but 5% is recommended. Refer to Chapter One for the proper protocol
when analyzing replicates.
8.4 Spiked samples or standard reference materials must be employed to
determine accuracy. A spiked sample should be included with each batch of
3050A - 4 Revision 1
July 1992
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samples processed and whenever a new sample matrix is being analyzed. Refer to
Chapter One for the proper protocol when analyzing spikes.
8.5 The concentration of all calibration standards should be verified
against a quality control check sample obtained from an outside source.
9.0 METHOD PERFORMANCE
9.1 No data provided.
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.
3050A - 5 Revision 1
July 1992
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METHOD 3050A
ACID DIGESTION OF SEDIMENTS, SLUDGES, AND SOILS
Start
Furnace
analysis
for As, Be,
Cd , Co , Cr ,
Fe, Mo, Pb,
Se, Tl, V
7.6 Continue
heating to
reduce volume
7.6 Dilute with
reagent water
and filter
particulates in
digastate
7.1 Mix
sample; take
1-2 g portion
for each
diges tion
7 2 Add HNO,,
reflux;repeat
HNO, raflux
until solution
i* 5 ml
7.3 Add raagant
watar and H,0t;
heat baakar to
start peroxide
reaction
7 4 Continue
adding H,0,
with heating
7.7.1 Report
concentrations,
and % solids of
sample for dry
weight analysis
ICP or Flame AA
analysis for
As, Ag, Al Ba,
Be, Ca, Cd
Cu, Fe
Mn, Mo
Ni, 0., Pb
Tl, V, Zn
Co,
K,
Na,
Sa,
7.S Add
concentrated
HC1 and
reagent
water; reflux
7.5 Cool;diluta
with reagent
water, filter
partculates in
digastate
7.7.2 If %
solids
required,use
homogeneous
sample aliquot
Stop
3050A - 6
Revision 1
July 1992
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METHOD 3051
MICROWAVE ASSISTED ACID DIGESTION OF SEDIMENTS,
SLUDGES, SOILS, AND OILS
1.0 SCOPE AND APPLICATION
1.1 This method is applicable to the microwave assisted acid digestion of
sludges, sediments, soils, and oils 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
1.2 This method is provided as an alternative to Method 3050. It is
intended to provide a rapid multielement acid leach digestion prior to analysis
so that decisions can be made about site cleanup levels, the need for TCLP
testing of a waste and whether a BOAT process is providing acceptable
performance. If a decomposition including hydrochloric acid is required for
certain elements, it is recommended that Method 3050A be used. Digests produced
by the method are suitable for analysis by flame atomic absorption (FLAA),
graphite furnace atomic absorption (GFAA), inductively coupled plasma emission
spectroscopy (ICP-ES) and inductively coupled plasma mass spectrometry (ICP-MS).
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 3051.
2.0 SUMMARY OF METHOD
2.1 A representative sample of up to 0.5 g is digested in 10 mL of
concentrated nitric acid for 10 min using microwave heating with a suitable
laboratory microwave unit. The sample and acid are placed in a fluorocarbon (PFA
or TFM) microwave vessel. The vessel is capped and heated in the microwave unit.
After cooling, the vessel contents are filtered, centrifuged, or allowed to
settle and then diluted to volume and analyzed by the appropriate SW-846 method
(Ref. 1).
3.0 INTERFERENCES
3.1 Very reactive or volatile materials that may create high pressures
when heated may cause venting of the vessels with potential loss of sample and
analytes. The complete decomposition of either carbonates, or carbon based
samples, may cause enough pressure to vent the vessel if the sample size is
greater than 0.25 g when used in the 120 mL vessels with a pressure relief device
that has an upper limit of 7.5+ 0.7 atm (110 ± 10 psi).
3051 - 1 Revision 0
September 1994
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4.0 APPARATUS AND MATERIALS
4.1 Microwave apparatus requirements.
4.1.1 The microwave unit provides programmable power with a
minimum of 574 W, which can be programmed to within ± 10 W of the required
power. Typical units provide a nominal 600 W to 1200 W of power.
Pressure, or especially temperature, monitoring and control of the
microwave unit are desirable.
4.1.2 The microwave unit cavity is corrosion resistant and well
ventilated.
4.1.3 All electronics are protected against corrosion for safe
operation.
4.1.4 The system requires fluorocarbon (PFA or TFM) digestion
vessels (120 ml capacity) capable of withstanding pressures up to 7.5 ±
0.7 atm (110 ± 10 psi) and capable of controlled pressure relief at
pressures exceeding 7.5 ± 0.7 atm (110 ± 10 psi).
4.1.5 A rotating turntable is employed to insure homogeneous
distribution of microwave radiation within the unit. The speed of the
turntable should be a minimum of 3 rpm.
CAUTION: Those laboratories now using or contemplating the
use of kitchen type microwave ovens for this method should be
aware of several signifant safety issues. First, when an acid
such as nitric is used to assist sample digestion in microwave
units in open vessels, or sealed vesselsequippedres, there is
the potential for the acid gases 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 unit with
corrosion resistant safety devices prevents this from
occurring.
CAUTION: The second safety concern relates to the use of
sealed containers without pressure relief valves in the unit.
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 unlined
fluorocarbon (PFA or TFM) containers with pressure relief
mecahnisms or containers with PFA-fluorocarbon liners and
pressure relief mechanisms are considered acceptable at
present.
Users are therefore advised not to use kitchen type microwave
ovens or to use sealed containers without pressure relief
3051 - 2 Revision 0
September 1994
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valves for microwave acid digestions by this method. Use of
laboratory-grade microwave equipment is required to prevent
safety hazards. For further details consult reference 2.
CAUTION: There are many safety and operational
recommendations specific to the model and manufacturer of the
microwave equipment used in individual laboratories. These
specific suggestions are 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.
4.2 Volumetric graduated cylinder, 50 or 100 ml capacity or equivalent.
4.3 Filter paper, qualitative or equivalent.
4.4 Filter funnel, glass or disposable polypropylene.
4.5 Analytical balance, 300 g capacity, and minimum ± 0.01 g.
5.0 REAGENTS
5.1 All acids should be sub-boiling distilled where possible to minimize
the blank levels due to metallic contamination. Other 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.
5.1.1 Concentrated nitric acid, HN03. Acid should be analyzed to
determine levels of impurity. If the method blank is less than the MDL,
the acid can be used.
5.2 Reagent Water. Reagent water shall be interference free. All
references to water in the method refer to reagent water unless otherwise
specified (Ref. 3).
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.
6.3 Samples must be refrigerated upon receipt and analyzed as soon as
possible.
3051 - 3 Revision 0
September 1994
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7.0 PROCEDURE
7.1 Calibration of Microwave Equipment
NOTE: If the microwave unit uses temperature feedback control
capable of replicating the performance specifications of the method,
then the calibration procedure may be omitted.
7.1.1 Measurement of the available power for heating is evaluated
so that absolute power in watts may be transferred from one microwave unit
to another. 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 unit. The calibration format
required for laboratory microwave units depends on the type of electronic
system used by the manufacturer to provide partial microwave power. Few
units 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 (7.1.3), otherwise, the analyst must use the multiple
point calibration method (7.1.2).
7.1.2 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 section
7.1.4. This data is clustered about the customary working power ranges.
Nonlinearity has been commonly encountered at the upper end of the
calibration. If the unit'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.
7.1.3 The three-point calibration involves the measurement of
absorbed power at three different power settings. Measure the power at
100% and 50% using athe procedure described in section 7.1.4. From the
2-point line calculate the power setting corresponding to the required
power 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 7.1.2. This point should also be used to periodically
verify the integrity of the calibration.
7.1.4 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
3051 - 4 Revision 0
September 1994
-------
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 unit'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:
P = (K) (Cp) (m) (AT)
Eq. 1
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)
AT = 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~1-°C"1) the calibration equation
simplifies to:
Eq. 2 P = (AT) (34.86)
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 ±2 V. A constant power
supply may be necessary for microwave use if the source of the
line voltage is unstable.
Electronic components in most microwave units are matched to the
units' function and output. When any part of the high voltage
3051 - 5 Revision 0
September 1994
-------
circuit, power source, or control components in the unit have been
serviced or replaced, it will be necessary to recheck the units'
calibration. If the power output has changed significantly (±10 W),
then the entire calibration should be reevaluated.
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 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 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 the fluorocarbon (PFA or TFM) digestion vessel, valve
and capassembly to 0.001 g prior to use.
7.3.2 Weigh a well-mixed sample to the nearest 0.001 g into the
fluorocarbon sample vessel equipped with a single-ported cap and a
pressure relief valve. For soils, sediments, and sludges use no more than
0.500 g. For oils use no more than 0.250 g.
7.3.3 Add 10 + 0.1 ml concentrated nitric acid in a fume hood.
If a vigorous reaction occurs, allow the reaction to stop before capping
the vessel. Cap the vessel and torque the cap to 12 ft-lbs (16 N-m) or
according to the unit manufacturer's directions. Weigh the vessels to the
nearest 0.001 g. Place the vessels in the microwave carousel.
CAUTION: Toxic nitrogen oxide fumes may be evolved, therefore all
work must be performed in a properly operating ventilation system.
The analyst should also be aware of the potential for a vigorous
reaction. If a vigorous reaction occurs, allow to cool before
capping the vessel.
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.
3051 - 6 Revision 0
September 1994
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CAUTION: All samples known or suspected of containing more than 5-
10% organic material should be predigested in a hood for at least 15
minutes.
7.3.4 Properly place the carousel in the microwave unit according
to the manufacturer's recommended specifications and, if used, connect the
pressure vessels to the central overflow vessel with PFA-fluorocarbon
tubes. Any vessels containing 10 ml of nitric acid for analytical blank
purposes are counted as sample vessels. When fewer than the recommended
number of samples are to be digested, the remaining vessels should be
filled with 10 ml of nitric acid to achieve the full complement of
vessels. This provides an energy balance since the microwave power
absorbed is proportional to the total mass in the cavity (Ref. 4).
Irradiate each group of sample vessels for 10 minutes. The temperature of
each sample should rise to 175 °C in less than 5.5 minutes and remain
between 170-180 °C for the balance of the 10 minute irradiation period.
The pressure should peak at less than 6 atm for most soil, sludge, and
sediment samples (Ref. 5). The pressure will exceed these limits in the
case of high concentrations of carbonate or organic compounds. In these
cases the pressure will be limited by the relief pressure of the vessel to
7.5 ± 0.7 atm (110 ± 10 psi). All vessels should be sealed according to
the manufacturers recommended specifications.
7.3.4.1 Newer microwave units are capable of higher power (W)
that permits digestion of a larger number of samples per batch. If
the analyst wishes to digest more samples at a time, the analyst may
use different values of power as long as they result in the same
time and temperature conditions defined in 7.3.4. That is, any
sequence of power that brings the samples to 175°C in 5.5 minutes
and permits a slow rise to 175 - 180°C during the remaining 4.5
minutes (Ref. 5).
Issues of safety, structural integrity (both temperature and
pressure limitations), heat loss, chemical compatibility, microwave
absorption of vessel material, and energy transport will be
considerations made in choosing alternative vessels. If all of the
considerations are met and the appropriate power settings provided
to reproduce the reaction conditions defined in 7.3.4, then these
alternative vessels may be used (Ref. 1,2).
7.3.5 At the end of the microwave program, allow the vessels to
cool for a minimum of 5 minutes before removing them from the microwave
unit. When the vessels have cooled to room temperature, weigh and record
the weight of each vessel assembly. If the weight of acid plus sample
has decreased by more than 10 percent from the original weight,
discard the sample. Determine the reason for the weight loss. These are
typically attributed to loss of vessel seal integrity, use of a digestion
time longer than 10 minutes, too large a sample, or improper heating
conditions. Once the source of the loss has been corrected, prepare
a new sample or set of samples for digestion beginning at 7.3.1.
3051 - 7 Revision 0
September 1994
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7.3.6 Complete the preparation of the sample by carefully uncapping
and venting each vessel in a fume hood. 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.
7.3.6.1 Centrifugation: Centrifugation at 2,000-3,000 rpm
for 10 minutes is usually sufficient to clear the supernatant.
7.3.6.2 Settling: 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.
7.3.6.3 Filtering: 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.
7.3.7 Dilute the digest to a known volume ensuring that the samples
and standards are matrix matched. The digest is now ready for analysis
for elements of interest using the appropriate SVI-846 method.
7.4 Calculations: The concentrations determined are to be reported on the
basis of the actual weight of the original sample.
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.).
8.3 Spiked samples or standard reference materials 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.
9.0 METHOD PERFORMANCE
9.1 Precision: Precision data for Method 3051, as determined by the
statistical examination of inter!aboratory test results, is located in Tables 1
and 2.
3051 - 8 Revision 0
September 1994
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9.2 Repeatability: If successive results are obtained by the same analyst
with the same apparatus under constant operating conditions on identical test
material, then the difference between these successive results will not, with 95%
probability, exceed the repeatability value. For example, in the case of lead,
an average of only 1 case in 20 would exceed
0.206 x
in the long run, where x is one result in /xj/g (Ref. 6).
9.3 Reproducibility: If two successive measurements are made independently
by each of two different analysts working in different laboratories on identical
test material, then the difference between the average result for each analyst
will not, with 95% probability, exceed the reproducibility value. For example,
in the case of lead, an average of only 1 case in 20 would exceed
0.303 x
in the long run, where x is the average of two successive measurements in /yg/g
(Ref. 2).
As can be seen in Table 1, repeatability and reproducibility differ between
elements, and usually depend on that element's concentration. Table 2 provides
an example of how users of the method can determine expected values for
repeatability and reproducibility; nominal values of lead have been used for this
model (Ref. 6).
9.4 Bias: In the case of SRM 1085 - Wear Metals in Oil, the bias of this
test method is different for each element. An estimate of bias, as shown in
Table 3, is:
Bias = Amount found - Amount expected.
However, the bias estimate inherits both the uncertainty in the
measurements made using Method 3051 and the uncertainty on the certificate, so
whether the bias is real or only due to measurement error must also be con-
sidered. The concentrations found for Al, Cr, and Cu using Method 3051 fall
within their certified ranges on SRM 1085, and 95% confidence intervals for Fe
and Ni overlap with their respective certified ranges; therefore, the observed
biases for these elements are probably due to chance and should be considered
insignificant. Biases should not be estimated at all for Ag and Pb because these
elements were not certified. Therefore, the only two elements considered in this
table for which the bias estimates are significant are Mg and Mo.
10.0 REFERENCES
1. 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.
3051 - 9 Revision 0
September 1994
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2. Kingston, H. M. and L. B. Jassie, "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.
3. 1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard Specification
for Reagent Water ; ASTM, Philadelphia, PA, 1985, D1193-77.
4. 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.
5. Kingston, H. M. EPA IAG #DWI-393254-01-0 January 1-March 31, 1988,
quarterly Report.
6. Binstock, D. A., Yeager, W. M., Grohse, P. M. and Gaskill, A. Validation
of a Method for Determining Elements in Solid Waste by Microwave Diges-
tion, Research Triangle Institute Technical Report Draft, RTI Project
Number 321U-3579-24, November, 1989, prepared for the Office of Solid
Waste, U.S. Environmental Protection Agency, Washington, DC 20460.
7. Kingston, H. M., Walter, P. J., "Comparison of Microwave Versus
Conventional Dissolution for Environmental Applications", Spectroscopy,
vol. 7 No. 9,20-27,1992.
3051 - 10 Revision 0
September 1994
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TABLE 1.
EQUATIONS RELATING REPEATABILITY AND REPRODUCIBILITY TO MEAN
CONCENTRATION OF DUPLICATE DETERMINATION WITH 95 PERCENT CONFIDENCE
Element Repeatability Reproducibility
Ag
Al
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Mg
Mn
Mo
Ni
Pb
Sr
V
Zn
0.195X8
0.232X
12. 9b
0.238X
0.082b
0.356X
0.385X
0.291X
0.187X
0.212X
0.257X
0.238X
1.96X1/2°
0.701X
0.212X
0.206X
0.283X
1.03X1/2
3.82X1/2
0.314X
0.444X
22. 6b
0.421X
0.082b
1.27X
0.571X
0.529X
0.195X
0.322X
0.348X
0.399X
4.02X1/2
0.857X
0.390X
0.303X
0.368X
2.23X1/2
7.69X1/2
"Log transformed variable based on one-way analysis of variance.
""Repeatability and reproducibility were independent of concentration.
°Square root transformed variable based on one-way analysis of variance.
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TABLE 2.
REPEATABILITY AND REPRODUCIBILITY FOR LEAD
BY METHOD 3051
Average Value Repeatability Reproducibilitv
50
100
200
300
400
500
10.3
20.6
41.2
61.8
82.4
103
15.2
30.3
60.6
90.9
121
152
All results are in mg/Kg
3051 - 12 Revision 0
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TABLE 3.
RECOVERY AND BIAS DATA FOR SRM 1085 - WEAR METALS IN OIL
Element
Amount
Expected
(Certified
Range)
Amount
Found*
(95% Conf
Interval)
Absolute
Bias
Relative
Bias
(Percent)
Significant
(due to more
than chance)
Ag
Al
Cr
Cu
Fe
Mg
Mo
Ni
Pb
(291)**
296+4
298±5
295±10
300±4
297±3
292+11
303+7
(305)**
All values in mg/Kg
234±16
295+12
293±10
289±9
311+14
270±11
238+11
293+9
279±8
-1
-5
-6
+11
-27
-54
-10
0
-2
-2
+4
-9
-18
-3
No
No
No
No
Yes
Yes
No
*Results taken from table 4-7, Ref. 2.
**Value not certified, so should not be used in bias detection and estimation.
3051 - 13
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September 1994
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METHOD 3051
(MICROWAVE ASSISTED ACID DIGESTION OF SEDIMENTS, SLUDGES, SOILS, AND OILS)
Hn
weight
decreased >
10% from
original?
3051 - 14
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Septenter 1994
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METHOD 3540
SOXHLET EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 Method 3540 is a procedure for extracting nonvolatile and semi-
volatile 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.
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. The extract is then dried,
concentrated, and, as necessary, exchanged into a solvent compatible with the
cleanup or determinative step being employed.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Soxhlet extractor; 40-mm I.D., with 500-mL round-bottom flask.
4.2 Drying column; 20-mm I.D. 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). 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.
3540 - 1
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Date September 1986
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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).
4.4 Boiling chips: Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.5 Water bath; Heated, with concentric ring cover, capable of
temperature control[+5*C). The bath should be used in a hood.
4.6 Vials; Glass, 2-mL capacity, with Teflon-lined screw cap.
4.7 Glass or paper thimble or glass wool; Contaminant free.
4.8 Heating mantle; Rheostat controlled.
4.9 Syringe; 5-mL.
4.10 Apparatus for determining percent moisture;
4.10.1 Oven: Drying.
4.10.2 Desiccator.
4.10.3 Crucibles: Porcelain.
4.11 Apparatus for grinding: If the sample will not pass through a 1-mm
standard sieve or cannot be extruded through a 1-mm opening, it should be
processed into a homogeneous sample that meets these requirements. Fisher
Mortar Model 155 Grinder, Fisher Scientific Co., Catalogue Number 8-323, or an
equivalent brand and model, is recommended for sample processing. This
grinder should handle most solid samples, except gummy, fibrous, or oily
materials.
5.0 REAGENTS
5.1 Reagent water; Reagent water is defined as water in which an
interferent is not observed at the method detection limit of the compounds of
interest.
5.2 Sodium sulfate; (ACS) Granular anhydrous (purified by washing with
methylene chloride followed by heating at 400*C for 4 hr in a shallow tray).
5.3 Extraction solvents;
5.3.1 Soil/sediment and aqueous sludge samples shall be extracted
using either of the following solvent systems.
3540 - 2
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Date September 1986
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5.3.1.1 Toluene/Methanol: 10:1 (v/v), pesticide quality or
equivalent.
5.3.1.2 Acetone/Hexane: 1:1 (v/v), pesticide quality or
equivalent.
5.3.2 Other samples shall be extracted using the following:
5.3.2.1 Methylene chloride: pesticide quality or equivalent.
5.4 Exchange solvents; Hexane, 2-propanol, cyclohexane, acetonitrile
(pesticide quality or equivalent).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 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 multiphases must be
prepared by the phase separation method in Chapter Two before extraction.
This 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.
7.2 Determination of percent moisture; In certain cases, sample results
are desired based on a dry-weight basis. When such data is desired, a portion
of sample for moisture determination should be weighed out at the same time as
the portion used for analytical determination.
7.2.1 Immediately after weighing the sample for extraction, weigh
5-10 g of the sample into a tared crucible. Determine the percent
moisture by drying overnight at 105*C. Allow to cool in a desiccator
before weighing:
3540 - 3
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Date September 1986
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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 below
the sample in the Soxhlet extractor is an acceptable alternative for the
thimble. 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.) For the sample in each analytical batch selected for
spiking, add 1.0 ml of the matrix spiking standard. For base/neutral-acid
analysis, the amount added of the surrogates and matrix spiking compounds
should result in a final concentration of 100 ng/uL of each base/neutral
analyte and 200 ng/uL of each acid analyte in the extract to be analyzed
(assuming a 1 uL 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 Place 300 ml of the extraction solvent (Section 5.3) 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 hr.
7.5 Allow the extract to cool after the extraction is complete.
7.6 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL
concentrator tube to a 500-mL evaporation flask.
7.7 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
100-125 ml of extraction solvent to complete the quantitative transfer.
7.8 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 min. 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 min.
7.9 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 Paragraph 7.6, raising the temperature of the water bath, if
necessary, to maintain proper distillation.
7.10 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 Paragraph 7.9 or adjusted to 10.0 ml with the solvent last used.
3540 - 4
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Date September 1986
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TABLE 1. SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040a
8060
8080
8090
8100
8120
8140
S250Y
8270a,C
8310
Extraction
PH
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
hexane
none
hexane
hexane
none
none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
hexane
cyclohexane
hexane
hexane
_
-
~"
Volune
of extract
required
for
cleanup (mL)
1.0
2.0
10.0
2.0
2.0
2.0
10.0
_
-
"
Final
extract
volune
for
analysis (mL)
1.0, 10. Ob
10.0
10.0
1.0
1.0
1.0
10.0
1.0
1.0
1.0
10 obtain separate acid and base/neutral extracts, Method 3650 should be performed following
concentration of the extract to 10.0 mL.
Phenols may be analyzed, by Method 8040, using a 1.0 mL 2-propanol extract by GC/FID. Method 8040
also contains an optional derivatization procedure for phenols which results in a 10 mL hexane
extract to be analyzed by GC/ECD.
The specificity of OC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for
guidance on the cleanup procedures available if required.
3540 - 5
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Date September 1986
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7.11 If further concentration Is indicated in Table 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 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 min. 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 min. Remove the Snyder column and rinse the flask and
its lower joints into the concentrator tube with 0.2 mL of solvent. Adjust
the final volume to 1.0-2.0 ml, as Indicated 1n Table 1, with solvent.
7.12 The extracts obtained may now be analyzed for analyte content using
a variety of organic techniques (see Section 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 Teflon-sealed screw-cap vial
and labeled appropriately.
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 specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
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.
3540 - 6
Revision
Date September 1986
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METHOD 3540
SOXHLET EXTRACTION
7. 1
Use
appropriate
•ample handling
technique
7.6
Assemble K-O
concentrator
7.2
Determine
percent
moisture
7.3
7. 7
4.6
Dry and collect
extract In K-O
concentrator
Add
appropriate
surrogate and
matrix spiking
standards
7.4
4.6
Concentrate
using Snyder
column and K-D
apparatus
Place
methylene
chlor Jde:
acetone In
flask; extract
for 16-24 hrs
Reconcentrate
using Snyder
column and K-O
apparatus
Analyze using
organic
techniques
3540 - 7
Revision p
Date September 1986
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METHOD 3550
SONICATION EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 Method 3550 Is a procedure for extracting nonvolatile and semi-
volatlle organic compounds from sol Ids such as soils, sludges, and wastes.
The sonication 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 <[20 mg/kg) uses a larger sample size and a
more rigorous extraction procedure (lower concentrations are more difficult to
extract). The high concentration method (individual organic components of
>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 Cleanup, Section 4.2.2 of Chapter Four, for applicable methods.
2.0 SUMMARY OF METHOD
2.1 Low concentration method; A 30-g sample 1s mixed with anhydrous
sodium sulfate to form a free-flowing powder. This is solvent extracted three
times using sonication. 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 High concentration method; A 2-g sample 1s mixed with anhydrous
sodium sulfate to form a free-flowing powder. This is solvent extracted once
using sonication. A portion of the extract is removed for cleanup and/or
analysis.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Apparatus for grinding; If the sample will not pass through a 1-mm
standard sieve or cannot be extruded through a 1-mm opening, it should be
processed into a homogeneous sample that meets these requirements. Fisher
Mortar Model 155 Grinder, Fisher Scientific Co., Catalogue Number 8-323, or an
equivalent brand and model, is recommended for sample processing. This
grinder should handle most solid samples, except gummy, fibrous, or oily
materials.
3550 - 1
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Date September 1986
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4.2 Sonication; A horn-type sonicator equipped with a titanium tip
should be used. The following sonicator, or an equivalent brand and model, is
recommended:
Ultrasonic cell disrupter: Heat Systems - Ultrasonics, Inc., Model
W-385 (475 watt) sonicator or equivalent (Power wattage must be a
minimum of 375 with pulsing capability and No. 200 1/2" Tapped
Disrupter Horn) plus No. 207 3/4" Tapped Disrupter Horn, and No. 419
1/8" Standard Tapered microtip probe.
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 moisture:
4.4.1 Oven: Drying.
4.4.2 Desiccator.
4.4.3 Crucibles: Porcelain.
4.5 Pasteur glass pipets; Disposable, 1-mL.
4.6 Beakers: 400-mL.
4.7 Vacuum 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).
4.8.2 Evaporator flask: 500-mL (Kontes K-570001-0500 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).
4.9 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.10 Water bath: Heated, with concentric ring cover, capable of
temperature control (15*C). The bath should be used in a hood.
3550 - 2
Revision
Date September 1986
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4.11 Balance: Top-loading, capable of accurately weighing 0.01 g.
4.12 Vials and caps; 2-mL for GC auto-sampler.
4.13 Glass scintillation vials: At least 20-mL, with screw-cap and
Teflon or aluminum foil liner.
4.14 Spatula: Stainless steel or Teflon.
4.15 Drying column; 20-mm I.D. 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.
4.16 Syringe; 5-mL.
5.0 REAGENTS
5.1 Sodium sulfate: Anhydrous and reagent grade, heated at 400*C for
4 hr, cooled in a desiccator, and stored in a glass bottle. Baker anhydrous
powder, catalog #73898, or equivalent.
5.2 Extraction solvents: Methylene chloride:acetone (1:1, v:v),
methylene chloride, hexane (pesticide quality or equivalent).
5.3 Exchange solvents: Hexane, 2-propanol, cyclohexane, acetonitrile
(pesticide quality or equivalent).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 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 multiphases must be
prepared by the phase separation method in Chapter Two before extraction.
This procedure is for solids only.
3550 - 3
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Date September 1986
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7.1.3 Dry waste samples amenable to grinding: Grind or otherwise
subdivide the waste so that it either passes through a 1-mrn 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.
7.2 Determination of percent moisture; In certain cases, sample results
are desired based on a dry-weight basis. When such data is desired, a portion
of sample for moisture determination should be weighed out at the same time as
the portion used for analytical determination.
7.2.1 Immediately after weighing the sample for extraction, weigh
5-10 g of the sample into a tared crucible. Determine the percent
moisture by drying overnight at 105*C. Allow to cool in a desiccator
before weighing:
q of sampl- qdry sample x 100 = % mo1sture
7.3 Determination of pH (if required): Transfer 50 g of sample to a
100-mL beaker. Add 50 ml of water and stir for 1 hr. Determine the pH of
sample with glass electrode and pH meter while stirring. Discard this portion
of sample.
7.4 Extraction method for samples expected to contain low concentrations
of organics and pesticides «20 mg/kg);
7.4.1 The following step should be performed rapidly to avoid loss
of the more volatile extractables. Weigh approximately 30 g of sample
into a 400-mL beaker. Record the weight to the nearest 0.1 g. Non-
porous 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. The sample should be free-flowing at this point. Add
1 ml of surrogate standards to all samples, spikes, and blanks (see
Method 3500 for details on the surrogate standard solution and the matrix
spike solution). For the sample in each analytical batch selected for
spiking, add 1.0 ml of the matrix spiking standard. For base/neutral-
acid analysis, the amount added of the surrogates and matrix spiking
compounds should result in a final concentration of 100 ng/uL of each
base/neutral analyte and 200 ng/uL of each acid analyte in the extract to
be analyzed (assuming a 1 uL 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. Immediately add 100 ml of 1:1 methylene chloride:acetone.
7.4.2 Place the bottom surface of the tip of the #207 3/4 in.
disrupter horn about 1/2 in. below the surface of the solvent, but above
the sediment layer.
7.4.3 Sonicate for 3 min, with output control knob set at 10 and
with mode switch on Pulse and percent-duty cycle knob set at 50%. Do NOT
use microtip probe.
3550 - 4
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Date September 1986
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7.4.4 Decant and filter extracts through Whatman No. 41 filter
paper using vacuum filtration or centrifuge and decant extraction
solvent.
7.4.5 Repeat the extraction two or more times with two additional
100-mL portions of solvent. Decant off the extraction solvent after each
sonication. On the final sonication, pour the entire sample into the
Buchner funnel and rinse with extraction solvent.
7.4.6 Assemble a Kuderna-Danish (K-D) concentrator by attaching a
10-mL concentrator tube to a 500-mL evaporative flask.
7.4.7 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 100-125 ml of extraction solvent to complete the
quantitative transfer.
7.4.8 Add one or two clean boiling chips to the evaporative 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.
7.4.9 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 Paragraph 7.4.8, raising the temperature of the
water bath, if necessary, to maintain proper distillation.
7.4.10 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 Paragraph 7.4.11 or adjusted to 10.0 ml with the
solvent last used.
7.4.11 Add a clean boiling chip and attach a two-ball micro-Snyder
column to the concentrator tube. Prewet the column by adding approxi-
mately 0.5 ml of methylene chloride or exchange solvent through the top.
Place the apparatus in the hot water bath. Adjust the vertical position
and the water temperature, as required, to complete the concentration in
5-10 min. At the proper rate of distillation, the balls of the column
will actively chatter, but the chambers will not flood. When the liquid
3550 - 5
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TABLE 1. SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
80403
8060
8080
8090
8100
8120
8140
8250a,C
8270a,C
8310
Extraction
pH
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
hexane
none
hexane
hexane
none
none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
hexane
cyclohexane
hexane
hexane
_
-
"
Volune
of extract
required
for
cleanup (mL)
1.0
2.0
10.0
2.0
2.0
2.0
10.0
_
-
"
Final
extract
volume
for
analysis (mL)
1.0, 10. Ob
10.0
10.0
1.0
1.0
1.0
10.0
1.0
1.0
1.0
TO obtain separate acid and base/neutral extracts, Method 3650 should be performed following
concentration of the extract to 10.0 mL.
Phenols may be analyzed, by Method 8040, using a 1.0 mL 2-propanol extract by GC/FID. Method 8040
also contains an optional derivatization procedure for phenols which results in a 10 mL hexane
extract to be analyzed by GC/ECD.
The specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for
guidance on the cleanup procedures available if required.
3550 - 6
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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 min.
Remove the micro-Snyder column and rinse its lower joint into the
concentrator tube with approximately 0.2 ml of appropriate solvent.
Adjust the final volume to the volume required for cleanup or for the
determinative method (see Table 1).
7.4.12 Transfer the concentrated extract to a clean screw-cap vial.
Seal the vial with a Teflon-lined lid and mark the level on the vial.
Label with the sample number and fraction and store in the dark at 4*C
until ready for analysis or cleanup.
7.5 Extraction method for samples expected to contain high concen-
trations of organics (>20 mg/kg):
7.5.1 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.
7.5.2 Add 2 g of anhydrous sodium sulfate to sample in the 20-mL
vial and mix well.
7.5.3 Surrogate standards are added to all samples, spikes, and
blanks (see Method 3500 for details on the surrogate standard solution
and on the matrix spike solution). Add 2.0 mL of surrogate spiking
solution to sample mixture. For the sample in each analytical batch
selected for spiking, add 2.0 mL of the matrix spiking standard. For
base/neutral-acid analysis, the amount added of the surrogates and matrix
spiking compounds should result in a final concentration of 200 ng/uL of
each base/neutral analyte and 400 ng/uL of each acid analyte in the
extract to be analyzed (assuming a 1 uL 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.
7.5.4 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 min at output control setting 5
and with mode switch on pulse and percent duty cycle of 50%. Extraction
solvents are:
1. Nonpolar compounds, i.e., organochlorine pesticides and
PCBs: hexane.
2. Extractable priority pollutants: methylene chloride.
7.5.5 Loosely pack disposable Pasteur pipets with 2- to 3-cm Pyrex
glass-wool plugs. Filter the extract through the glass wool and collect
3550 - 7
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5.0 ml in a concentrator tube if further concentration is required.
Follow Paragraphs 7.4.6 through 7.4.12 for details on concentration.
Normally, the 5.0 ml extract is concentrated to 1.0 ml.
7.5.6 The extract is ready for cleanup or analysis, depending on
the extent of interfering co-extractives.
8.0 QUALITY CONTROL
8.1 Any reagent blanks or matrix spike samples should be subject 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
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. U.S. EPA, Interlaboratory 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.
3550 - 8
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, METHOD 3550
SONICATION EXTRACTION
Start
7. 1
Prepare
samples using
approprlate
method tor the
waste ma tr1x
7 .2
7 .5.3
Add anhydrous
sod lum sul1 ate
to sample
Determine
the percent
of moisture In
the sample
7.3
7,5.3
7.4.1
Add
surrogate
standards to
•11 samples.
spikes, and
blanks
Add
surrogate
standards
to all samples.
spikes, and
blanks
Determine pH
of sample
7.4
Sonicate sample
•t least 3
times
7.5.4 Adjust
vo lume;
disrupt sample
with tapered
mlcrotlp ultra-
sonic probe
o
16 further
concentration
required?
s
7.S.S
Fllte
gl<
r through
ss wool
7.4.8
Cone
extr
collec
conce
7.4.9
Add exchange
solvent:
concentrate
extract
Is • solvent
exchange
required?
3550 - 9
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METHOD 3S5O
SONICATION EXTRACTION
(Continued)
o
Use Matnod 366O
tor cleanup
Partner
concentrate
»nd/or adjust
volume
3550 - 10
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METHOD 3580
WASTE DILUTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a solvent dilution of a non-aqueous waste
sample prior to cleanup and/or analysis. 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.
1.2 It is recommended that an aliquot of the diluted sample be cleaned
up. See the Cleanup section of this chapter for methods (Section 4.2.2).
2.0 SUMMARY OF METHOD
2.1 One gram of sample is weighed into a capped tube, and the sample is
diluted to 10.0 mL with an appropriate solvent.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Glass scintillation vials; At least 20-mL, with Teflon or aluminum-
foil-lined screw-cap.,
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 pi pets; Pasteur.
4.6 Test tube rack.
4.7 Pyrex glass wool.
4.8 Volumetric flasks; 10-mL (optional).
5.0 REAGENTS
5.1 Sodium sulfate: (ACS) Granular, anhydrous (purified by heating at
400*C for 4 hr in a shallow tray).
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5.2 Solvents: Methylene chloride and hexane (pesticide quality or
equi valentJT
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1-.
7.0 PROCEDURE
7.1 Samples consisting of multiphases must be prepared by the phase
separation method (Chapter Two) before extraction.
7.2 The sample dilution may be performed in a 10-mL volumetric flask.
If disposable glassware is preferred, the 20-mL scintillation vial may be
calibrated for use. Simply pi pet 10.0 mL of extraction solvent into the
scintillation vial and mark the bottom of the meniscus. Discard this solvent.
7.3 Transfer approximately 1 g of each phase (record weight to the
nearest 0.1 g) of the sample to separate 20-mL vials or 10-mL volumetric
flasks. 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 Add 2.0 mL surrogate spiking solution to all samples and blanks.
For the sample in each analytical batch selected for spiking, add 2.0 mL of
the matrix spiking standard. For base/neutral-acid analysis, the amount added
of the surrogates and matrix spiking compounds should result in a final
concentration of 200 ng/uL of each base/neutral analyte and 400 ng/uL of each
acid analyte in the extract to be analyzed (assuming a 1 uL 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. See Method 3500 for details on the surrogate
standard and matrix spiking solutions.
7.5 Immediately dilute to 10 mL with the appropriate solvent. For
compounds to be analyzed by GC/ECD, e.g., organochlorine pesticides and PCBs,
the dilution solvent should be hexane. For base/neutral and acid semivolatile
priority pollutants, use methylene chloride. If dilution is to be cleaned up
by gel permeation chromatography (Method 3640), use methylene chloride as the
dilution solvent for all compounds.
7.6 Add 2.0 g of anhydrous sodium sulfate to the sample.
7.7 Cap and shake the sample for 2 min.
7.8 Loosely pack disposable Pasteur pipets with 2-3 cm glass wool plugs.
Filter the extract through the glass wool and collect 5 mL of the extract in a
tube or vial.
3580 - 2
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Date September 1986
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7.9 The extract is ready for cleanup or analysis, depending on the
extent of interfering co-extractives.
8.0 QUALITY CONTROL
8.1 Any reagent blanks and 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 specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
10.1 None applicable.
3580 - 3
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METHOD 3580
WASTE DILUTION
Does sample
contain more than
one phase?
Use phase
separation
method
(chapter 2)
Transfer i
Of each phase
to separate
vials or flasks
I Add
—I surrogate
spiking
solutIon to
all samples
and blanks
matrix spiking
standard to
sample selected
for spiking
7.5
Dilute with
approprlate
solvent
7.6
Add anhydrous
ammonium
sulfate
7.7 I
Cap and shake
7.8
Filter through
glass wool
3580 - 4
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METHOD 3500
ORGANIC EXTRACTION AND SAMPLE PREPARATION
1.0 SCOPE AND APPLICATION
1.1 The 3500 Methods are procedures for quantitatively extracting
nonvolatile and semi volatile organic compounds from various sample matrices.
Cleanup and/or analysis of the resultant extracts are described in Chapter
Four, Sections 4.2.2 and 4.3, respectively.
1.2 Method 3580 describes a solvent dilution technique that may be used
on non-aqueous nonvolatile and semi volatile organic samples prior to cleanup
and/or analysis.
1.3 The 5000 Methods are procedures for preparing samples containing
volatile organic compounds for quantitative analysis.
1.4 Refer to the specific method of interest for further details.
2.0 SUMMARY OF METHOD
2.1 3500 Methods; A sample of a known volume or weight is solvent
extracted. The resultant extract is dried and then concentrated in a Kuderna-
Danish 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, Section 8.0).
2.2 5000 Methods; Refer to the specific method of interest.
3.0 INTERFERENCES
3.1 Samples requiring analysis for volatile organic compounds, can be
contaminated by diffusion of volatile organics (particularly chlorofluoro-
carbons and methylene chloride) through the sample container septum during
shipment and storage. A field blank prepared from reagent water and carried
through sampling and subsequent storage and handling can serve as a check on
such contamination.
3.2 Solvents, reagent, 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 required. Refer to Chapter One for specific guidance on quality control
procedures.
3.3 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.
3500 - 1
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3.4 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.
3.5 Glassware contamination resulting in analyte degradation; Soap
residue on glassware may cause degradation of certain analytes. Specifically,
aldrin, heptachlor, and most organophosphorous 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.
5.0 REAGENTS
5.1 Refer to the specific method of interest for a description of the
solvents needed.
5.2 Stock standards; Stock solutions may be prepared from pure standard
materials or purchased as certified solutions..
5.2.1 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.
5.2.1.1 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 0.1 mg.
5.2.1.2 Using a 100-uL 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.
5.2.1.3 Reweigh, dilute to volume, stopper, then mix by
inverting the flask several times. Calculate the concentration in
micrograms per microliter (ug/uL) 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.
3500 - 2
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Date September 1986
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5.2.1.4 Transfer the stock standard solution into a Teflon-
sealed screw-cap bottle. Store, with minimal headspace, at -10*C to
-20*C and protect from light.
5.2.1.5 All standards must be replaced after 1 month, or
sooner if comparison with check standards indicates a problem.
5.2.2 Semi volatile stock standards: Base/neutral and acid stock
standards are prepared in methanol. Organochlorine pesticide standards
are prepared in acetone.
5.2.2.1 Stock standard solutions should be stored in Teflon-
sealed containers at 4*C. The solutions should be checked
frequently for stability. These solutions must be replaced after
six months, or sooner if comparison with quality control check
samples indicate a problem.
5.3 Surrogate standards: A surrogate standard (i.e., a chemically inert
compound not expected to occur in an environmental sample) should be added to
each sample, blank, 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. Recommended surrogates for
different analyte groups follow; however, these compounds, or others that
better correspond to the analyte group, may be used for other analyte groups
as well. Normally three or more standards are added for each analyte group.
5.3.1 Base/neutral and acid surrogate spiking solutions: The
following are recommended surrogate standards.
Base/neutral Acid
2-Fluorobiphenyl 2-Fluorophenol
Nitrobenzene-ds 2,4,6-Tribromophenol
Terphenyl-di4 Phenol-d5
5.3.1.1 Prepare a surrogate standard spiking solution in
methanol that contains the base/neutral compounds at a concentration
of 100 ug/mL, and the acid compounds at 200 ug/mL for water and
sediment/soil samples (low- and medium-level). For waste samples,
the concentration should be 500 ug/mL for base/neutrals and 1000
ug/mL for acids.
5.3.2 Organochlorine pesticide surrogate spiking solution: The
following are recommended surrogate standards for Organochlorine
pesticides.
Organochlorine pesticides
Dibutylchlorendate (DBC)
2,4,5,6-Tetrachloro-meta-xylene (TCMX)
3500 - 3
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Date September 1986
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5.3.2.1 Prepare a surrogate standard spiking solution at a
concentration of 1 ug/mL in acetone for water and sediment/soil
samples. For waste samples, the concentration should be 5 ug/mL.
5.3.3 Purgeable surrogate spiking solution: The following are
recommended surrogate standards for volatile organics.
Purgeable organics
p-Bromof1uorobenzene
l,2-Dichloroethane-d4
Toluene-ds
5.3.3.1 Prepare a surrogate spiking solution (as described in
Paragraph 5.2.1 or through secondary dilution of the stock standard)
in methanol containing the surrogate standards at a concentration of
25 ug/mL.
5.4 Matrix spike standards; Select five or more analytes from each
analyte group for use in a spiking solution. The following are
recommended matrix spike standard mixtures for a few analyte groups.
These compounds, or others that better correspond to the analyte
group, may be used for other analyte groups as well.
5.4.1 Base/neutral and acid matrix spiking solution: Prepare a
spiking solution in methanol that contains each of the following
base/neutral compounds at 100 ug/mL and the acid compounds at 200 ug/mL
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-Ni troso-di-n-propylami ne 4-Ni trophenol
1,4-Di chlorobenzene
5.4.2 Organochlorine pesticide matrix spiking solution: Prepare a
spiking solution in acetone or methanol that contains the following
pesticides in the concentrations specified for water and sediment/soil.
The concentration should be five times higher for waste samples.
Pesticide Concentration (ug/mL)
Lindane 0.2
Heptachlor 0.2
Aldrin 0.2
Dieldrin 0.5
Endrin 0.5
4,4'-DDT 0.5
3500 - 4
Revision
Date September 1986
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5.4.3 Purgeable matrix spiking solution: Prepare a spiking
solution in methanol that contains the following compounds at a
concentration of 25 ug/tnL.
Purgeable organics
1,1-Dichloroethene
Trichloroethene
Chlorobenzene
Toluene
Benzene
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to the Organic Analyte Chapter,
Section 4.1.
7.0 PROCEDURE
7.1 Semi volatile organic sample extraction; Water, soil/sediment,
sludge, and!wastesamplesrequiringanalysisfor base/neutral and acid
extractables and/or organochlorine pesticides must undergo solvent extraction
prior to analysis. This manual contains four methods that may be used for
this purpose: Method 3510; Method 3520; Method 3540; and Method 3550. The
method that should be used on a particular sample, is highly dependent upon
the physical characteristics of that sample. Therefore, review these four
methods prior to choosing one in particular. Appropriate surrogate standards
and, 1f necessary, matrix spiking solutions are added to the sample prior to
extraction for all four methods.
7.1.1 Method 3510: Applicable to the extraction and concentration
of water-insoluble and slightly water-soluble organics from aqueous
samples. A measured volume of sample 1s solvent extracted using a
separatory funnel. The extract is dried, concentrated and, if necessary,
exchanged into a solvent compatible with further analysis. Method 3520
should be used if an emulsion forms between the solvent-sample phases,
which can not be broken up by mechanical techniques.
7.1.2 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. The limitations of Method 3510 concerning solvent-
sample phase separation do not interfere with this procedure.
3500 - 5
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7.1.3 Method 3540: This is a procedure for extracting nonvolatile
and semi volatile organic compounds from solids such as soils, sludges,
and 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 a Soxhlet extractor. The
extract is dried, concentrated and, if necessary, exchanged into a
solvent compatible with further analysis.
7.1.4 Method 3550: This method is applicable to the extraction of
nonvolatile and semi volatile organic compounds from solids such as soils,
sludges, and wastes using the technique of sonication. 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 sonication. The extract is dried, concentrated and, if
necessary, exchanged into a solvent compatible with further analysis.
7.1.5 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.
7.2 Volatile organic sample preparation; There are three methods for
volatile sample preparation: Method 5030; Method 5040; and direct injection.
Method 5030 is the most widely applicable procedure for analysis of volatile
organics, while the direct injection technique may have limited applicability
to aqueous matrices.
7.2.1 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
directly and to solids, wastes, soils/sediments, and water-miscible
liquids following appropriate preparation. 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. Prior to
application of the purge-and-trap procedure, all samples (including
blanks, spikes, and duplicates) should be spiked with surrogate standards
and, if required, with matrix spiking compounds.
7.2.2 Method 5040: This method is applicable to the investigation
of sorbent cartridges from volatile organic sampling train (VOST).
7.3 Sample analysis; Following preparation of a sample by one of the
methods described above, the sample is ready for further analysis. For
samples requiring volatile organic analysis, application of one of the three
methods described above is followed directly by gas chromatographic analysis
(Methods 8010, 8015, 8020, or 8030). Samples prepared for semivolatile
analysis may, if necessary, undergo cleanup (See Method 3600) prior to
application of a specific determinative method.
3500 - 6
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8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific guidance on quality control
procedures.
8.2 Before processing any samples, the analyst should demonstrate
through the analysis of a reagent water blank that all glassware and reagents
are interference free. Each time a set of samples are processed, a method
blank(s) 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 Surrogate standards should be added to all samples when specified in
the appropriate determinative method in Chapter Four, Section 4.3.
8.4 A reagent blank, a matrix spike, and a duplicate or matrix spike
duplicate must be performed for each analytical batch (up to a maximum of 20
samples) analyzed.
8.5 For GC or GC/MS analysis, the analytical system performance must be
verified by analyzing quality control (QC) check samples. Method 8000,
Section 8.0 discusses in detail the process of verification; however,
preparation of the QC check sample concentrate is dependent upon the method
being evaluated.
8.5.1 Volatile organic QC check samples: QC check sample
concentrates containing each analyte of interest are spiked into reagent
water (defined as the QC check sample) and analyzed by purge-and-trap
(Method 5030). The concentration of each analyte in the QC check sample
is 20 ug/L. The evaluation of system performance is discussed in detail
in Method 8000, beginning with Paragraph 8.6.
8.5.2 Semivolatile organic QC check samples: To evaluate the
performance of the analytical method, the QC check samples must be
handled in exactly the same manner as actual samples. Therefore, 1.0 mL
of the QC check sample concentrate is spiked into each of four 1-L
aliquots of reagent water (now called the QC check sample), extracted,
and then analyzed by GC. The variety of semi volatile analytes which may
be analyzed by GC is such that the concentration of the QC check sample
concentrate is different for the different analytical techniques
presented in the manual. Method 8000 discusses in detail the procedure
of verifying the detection system once the QC check sample has been
prepared. The concentrations of the QC check sample concentrate for the
various methods are as follows:
8.5.2.1 Method 8040 - Phenols; The QC check sample
concentrate should contain each analyte at a concentration of
100 ug/mL in 2-propanol.
8.5.2.2 Method 8060 - Phthalate esters; The QC check sample
concentrate should contain thefollowinganalytes at the following
concentrations in acetone: butyl benzyl phthalate, 10 ug/mL; bis(2-
ethylhexyl)phthalate, 50 ug/mL; di-n-octylphthalate, 50 ug/mL; and
any other phthalate at 25 ug/mL.
3500 - 7
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8.5.2.3 Method 8080 - Organochlorine pesticides and PCBs: The
QC check sampTeconcentrate shouldcontain each single-component
analyte at the following concentrations in acetone: 4,4'-DDD, 10
ug/mL; 4,4'-DDT, 10 ug/mL; endosulfan II, 10 ug/mL; endosulfan
sulfate, 10 ug/mL; and any other single-component pesticide at 2
ug/mL. If the method is only to be used to analyze PCBs, chlordane,
or toxaphene, the QC check sample concentrate should contain the
most representative multicomponent parameter at a concentration of
50 ug/mL in acetone.
8.5.2.4 Method 8090 - Nitroaromatics and Cyclic Ketones: The
QC check sampleconcentrateshouldcontaineachanalyte at the
following concentrations in acetone: each dinitrotoluene at
20 ug/mL; and isophorone and nitrobenzene at 100 ug/mL.
8.5.2.5 Method 8100 - Polynuclear aromatic hydrocarbons: The
QC check sampleconcentrateshouldcontaineachanalyte at the
following concentrations in acetonitrile: naphthalene, 100 ug/mL;
acenaphthylene, 100 ug/mL; acenaphthene, 100 ug/mL; fluorene,
100 ug/mL; phenanthrene, 100 ug/mL; anthracene, 100 ug/mL;
benzo(k)fluoranthene 5 ug/mL; and any other PAH at 10 ug/mL.
8.5.2.6 Method 8120 - Chlorinated hydrocarbons; The QC check
sample concentrate should contain each analyte at the following
concentrations in acetone: hexachloro-substituted hydrocarbons,
10 ug/mL; and any other chlorinated hydrocarbon, 100 ug/mL.
9.0 METHOD PERFORMANCE
9.1 The recovery of surrogate standards 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 this method will be dictated by the overall
performance of the sample preparation in combination with the
analytical determinative method.
10.0 REFERENCES
10.1 None required.
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F Z
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3.3 METHODS FOR DETERMINATION OF METALS
This section of the manual contains seven analytical techniques for
trace metal 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 metals
in the presence of a large excess of a single metal is difficult. Examples would
be traces of metals 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 of 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 desolvation, 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
sensitive, interferences can be a real problem; finding the optimum combination
of digestion, heating times and temperatures, and matrix modifiers can be a
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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 6010A
INDUCTIVELY COUPLED PLASMA-ATOM1C EMISSION SPECTROSCOPY
1.0 SCOPE AND APPLICATION
1.1 Inductively coupled plasma-atomic emission spectroscopy (ICP)
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.
1.2 Elements for which Method 6010 is applicable are listed in Table 1.
Detection limits, sensitivity, and optimum ranges of the metals will vary with
the matrices and model of spectrometer. The data shown in Table 1 provide
estimated detection limits for clean aqueous samples using pneumatic
nebulization. Use of this method is restricted to spectroscopists who are
knowledgeable in the correction of spectral, chemical, and physical
interferences.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis, samples must be solubilized or digested using
appropriate Sample Preparation Methods (e.g. Methods 3005-3050). When analyzing
for dissolved constituents, acid digestion is not necessary if the samples are
filtered and acid preserved prior to analysis.
2.2 Method 6010 describes the simultaneous, or sequential, multielemental
determination of elements by ICP. The method measures element-emitted light by
optical spectrometry. Samples are nebulized and the resulting aerosol is
transported to the plasma torch. Element-specific atomic-line emission spectra
are produced by a radio-frequency inductively coupled plasma. The spectra are
dispersed by a grating spectrometer, and the intensities of the lines are
monitored by photomultiplier tubes. 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 must be free of spectral interference and 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 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.
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TABLE 1.
RECOMMENDED WAVELENGTHS AND ESTIMATED INSTRUMENTAL DETECTION LIMITS
Detection
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Selenium
Silver
Sodium
Strontium
Thallium
Vanadium
Zinc
Wavelength8 (nm)
308.215
206.833
193.696
455.403
313.042
226.502
317.933
267.716
228.616
324.754
259.940
220.353
670.784
279.079
257.610
202.030
231.604
213.618
766.491
196.026
328.068
588.995
407.771
190.864
292.402
213.856
Estimated
Limit (ug/L)
45
32
53
2
0.3
4
10
7
7
6
7
42
5
30
2
8
15
51
See note c
75
7
29
0.3
40
8
2
i
wavelengths listed are recommended because of their sensitivity and
overall acceptance. Other wavelengths may be substituted 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.
estimated instrumental detection limits shown are taken from
Reference 1 in Section 10.0 below. They are given as a guide for an
instrumental limit. The actual method detection limits are sample dependent
and may vary as the sample matrix varies.
Highly dependent on operating conditions and plasma position.
Re
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3.0 INTERFERENCES
3.1 Spectral interferences are caused by: (1) overlap of a spectral line
from another element at the analytical or background measurement wavelengths; (2)
unresolved overlap of molecular band spectra; (3) background contribution from
continuum or recombination phenomena; and (4) stray light from the line emission
of high-concentration elements. Spectral overlap can be compensated for by
computer-correcting the raw data after monitoring and measuring the interfering
element. Unresolved overlap requires selection of an alternate wavelength.
Background contribution and stray light can usually be compensated for by a
background correction adjacent to the analyte line.
Users of all ICP instruments must verify the absence of spectral
interference from an element in a sample for which there is no instrument
detection channel. Recommended wavelengths are listed in Table 1 and potential
spectral interferences for the recommended wavelengths are given in Table 2. The
data in Table 2 are intended as rudimentary guides for indicating potential
interferences; for this purpose, linear relations between concentration and
intensity for the analytes and the interferents can be assumed.
3.1.1 Element-specific 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. 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 with operating conditions, power, viewing
height, argon flow rate, etc. The user should be aware of the possibility
of interferences other than those specified in Table 2 and that analysts
should be aware of these interferences when conducting analyses.
3.1.2 The dashes in Table 2 indicate that no measurable
interferences were observed even at higher interferent 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.
3.1.3 At present, information on the listed silver and potassium
wavelengths is not available, but it has been reported that second-order
energy from the magnesium 383.231-nm wavelength interferes with the listed
potassium line at 766.491 nm.
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TABLE 2.
ANALYTE CONCENTRATION EQUIVALENTS ARISING FROM
INTERFERENCE AT THE 100-mg/L LEVEL
Interferent
a,b
Analyte
Wavelength --•
(run) Al
Ca Cr Cu Fe
Mg Mn
N1
Tl
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Selenium
Sodium
Thallium
Vanadium
Zinc
308.215
206.833
193.696
455.403
313.042
226.502
317.933
267.716
228.616
324.754
259.940
220.353
279.079
257.610
202.030
231.604
196.026
588.995
190.864
292.402
213.856
0.47 --
1.3 --
__
__
__
--
—
0.17 --
0.02
0.005 --
0.05 --
__
0.23 --
__
0.30 --
__
- -
2.9
0.44
_ _
--
_ _
0.08
--
0.03
--
—
--
0.11
0.01
—
--
--
--
0.05
--
0.21
0.08 --
--
_ — __ __
--
0.03 --
0.01 0.01 0.04
0.003 -- 0.04
0.005 --
0.003 --
0.12
__
0.13 -- 0.25
0.002 0.002 --
0.03 --
_.
0.09 --
__
__
0.005 --
0.14 -
0.25
--
_. _ _ _
0.04
0.02 --
0.03
__
0.03 0.15
0.05
— —
_.
0.07
— —
_ _
__
__
0.08
_.
0.02
0.29 --
1.4
0.45
1.1
0.05
0.03
0.04
--
0.02
—
--
0.12
—
--
--
--
--
--
Cashes indicate that no interference was observed even when interferents were
introduced at the following levels:
Al -
Ca -
Cr -
Cu -
Fe -
1000 mg/L
1000 mg/L
200 mg/L
200 mg/L
1000 mg/L
Mg
Mn
Tl
V
1000 mg/L
200 mg/L
200 mg/L
200 mg/L
figures recorded as analyte concentrations are not the actual observed
concentrations; to obtain those figures, add the listed concentration to the
interferent figure.
6010A - 4
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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. Differences in solution volatility
can also cause inaccuracies when organic solvents are involved. If physical
interferences are present, they must be reduced by diluting the sample or by
using a peristaltic pump. Another problem that can occur with high dissolved
solids is salt buildup at the tip of the nebulizer, which affects aerosol flow
rate and causes instrumental drift. The problem can be controlled by wetting the
argon prior to nebulization, using a tip washer, or diluting the sample.
Changing the nebulizer and removing salt buildup at the tip of the torch sample
injector can be used as an additional measure to control salt buildup. Also, it
has been reported that better control of the argon flow rate 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. If observed, they 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.
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 Argon gas supply - Welding grade or better.
4.2 Operating conditions - The analyst should follow the instructions
provided by the instrument manufacturer. 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. Sensitivity,
instrumental detection limit, precision, linear dynamic range, and interference
effects must be established for each individual analyte line on that particular
instrument. All measurements must be within the instrument linear range where
spectral interference correction factors are valid. The analyst must (1) verify
that the instrument configuration and operating conditions satisfy the analytical
requirements and (2) maintain quality control data confirming instrument
performance and analytical results.
4.3 Class A volumetric flasks
4.4 Class A volumetric pipets
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4.5 Analytical balance - capable of accurate measurement to 4 significant
figures.
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 in question analyze for contamination. If the concentration 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 appropriate 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 appropriate 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.
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 mole
fraction and the weight of the metal salt added.
Metal
Concentration (ppm) -
Metal salts
Concentration (pp.) -
5.3.1 Aluminum solution, stock, 1 ml = 1000 ug Al: Dissolve 1.0 g
of aluminum metal, weighed accurately to at least four significant
figures, in an acid mixture of 4 ml of (1:1) HC1 and 1 ml of concentrated
HN03 in a beaker. Warm gently to effect solution. When solution is
complete, transfer quantitatively to a liter flask, add an additional
6010A - 6 Revision 1
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10 ml of (1:1) HC1 and dilute to volume in a 1,000 ml volumetric flask
with water.
5.3.2 Antimony solution, stock, 1 ml = 1000 ug Sb: Dissolve
2.70 g K(SbO)C4H,06 (mole 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 1.30 g
of ASp03 (mole 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 1.50 g
BaCl2 (mole 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 19.7 g BeS04'4H20 (mole 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 Cadmium solution, stock, 1 mL = 1000 ug Cd: Dissolve 1.10 g
CdO (mole 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.
5.3.7 Calcium solution, stock, 1 mL = 1000 ug Ca: Suspend 2.50 g
CaCO, (mole 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.
5.3.8 Chromium solution, stock, 1 mL = 1000 ug Cr: Dissolve
1.90 g CrO, (mole 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 mL volumetric
flask with water.
5.3.9 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) HNO,. Add 10.0 mL (1:1) HC1 and dilute to
volume in a 1,000 mL volumetric flask with water.
5.3.10 Copper solution, stock, 1 mL = 1000 ug Cu: Dissolve 1.30 g
CuO (mole fraction Cu = 0.7989), weighed accurately to at least four
significant figures), in a minimum amount of (1:1) HN03. Add 10.0 mL
6010A - 7 Revision 1
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concentrated HN03 and dilute to volume in a 1,000 mL volumetric flask with
water.
5.3.11 Iron solution, stock, 1 ml = 1000 ug Fe: Dissolve 1.40 g
Fe203 (mole 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.
5.3.12 Lead solution, stock, 1 mL = 1000 ug Pb: Dissolve 1.60 g
Pb(NO,)2 (mole 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.
5.3.13 Lithium solution, stock, 1 mL = 1000 ug Li: Dissolve 5.324 g
lithium carbonate (mole 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.
5.3.14 Magnesium solution, stock, 1 mL = 1000 ug Mg: Dissolve
1.70 g MgO (mole fraction Mg = 0.6030), weighed accurately to at least
four significant figures, in a minimum amount of (1:1) HN03. Add 10.0 mL
(1:1) concentrated HN03 and dilute to volume in a 1,000 mL volumetric flask
with water.
5.3.15 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.
5.3.16 Molybdenum solution, stock, 1 mL = 1000 ug Mo: Dissolve
2.00 g (NH,)6Mo7024.4HpO (mole 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.
5.3.17 Nickel solution, stock, 1 mL = 1000 ug Mi: 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.
5.3.18 Phosphate solution, stock, 1 mL = 1000 ug P: Dissolve
4.393 g anhydrous KH?P04 (mole 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.
5.3.19 Potassium solution, stock, 1 mL = 1000 ug K: Dissolve 1.90 g
KC1 (mole 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.
5.3.20 Selenium solution, stock, 1 mL = 1000 ug Se: Do not dry.
Dissolve 1.70 g H2Se03 (mole fraction Se = 0.6123), weighed accurately to
6010A - 8 Revision 1
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at least four significant figures, in water and dilute to volume in a
1,000 mL volumetric flask with water.
5.3.21 Silver solution, stock, 1 ml = 1000 ug Ag: Dissolve
1.60 g AgNO, (mole 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.
5.3.22 Sodium solution, stock, 1 ml = 1000 ug Na: Dissolve 2.50 g
NaCl (mole 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.
5.3.23 Strontium solution, stock, 1 ml = 1000 ug Sr: Dissolve
2.415 g of strontium nitrate (Sr(NO,)2) (mole fraction 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.
5.3.24 Thallium solution, stock, 1 mL = 1000 ug Tl: Dissolve
1.30 g T1NO, (mole 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.
5.3.25 Vanadium solution, stock, 1 mL = 1000 ug V: Dissolve 2.30 g
NH403 (mole 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 ana dilute to
volume in a 1,000 mL volumetric flask with water.
5.3.26 Zinc solution, stock, 1 mL = 1000 ug Zn: Dissolve 1.20 g
ZnO (mole fraction Zn = 0.8034), weighed accurately to at least four
significant figures, in a minimum amount of dilute HNO,. 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). Matrix match with the appropriate acids 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.
6010A - 9 Revision 1
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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.
TABLE 3.
MIXED STANDARD SOLUTIONS
Solution Elements
I Be, Cd, Mn, Pb, Se and Zn
II Ba, Co, Cu, Fe, and V
III As, Mo
IV Al, Ca, Cr, K, Na, Ni,Li,& Sr
V Ag (see Note to Step 5.4), Mg, Sb, and Tl
VI P
5.5 Two types of blanks are required for the analysis. The calibration
blank is used in establishing the analytical curve, and the reagent blank is used
to correct for 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 the reagents and 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 instrument check standard is prepared by the analyst by combining
compatible elements at concentrations equivalent to the midpoint of their
respective calibration curves (see Step 8.6.1.1 for use). The instrument check
standard should be prepared from a source independent from that used in the
calibration standards.
5.7 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 at approximate
6010A - 10 Revision 1
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5.7 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 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.
5.8 The quality control sample should be prepared in the same acid matrix
as the calibration standards at 10 times the instrumental detection limits and
in accordance with the instructions provided by the supplier.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the material in Chapter Three, Metallic 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. Water samples which have been
prefiltered and acidified will not need acid digestion as long as the samples and
standards are matrix matched. Solubilization and digestion procedures are
presented in Sample Preparation Methods (Methods 3005A-3050A).
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
calibration).
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 should consist of a
blank and three standards.
7.4 Before beginning the sample run, reanalyze the highest mixed
calibration standard as if it were a sample. Concentration values obtained should
not deviate from the actual values by more than 5% (or the established control
limits, whichever is lower). If they do, follow the recommendations of the
instrument manufacturer to correct for this condition.
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).
Analyze the instrument check standard (Step 5.6) and the calibration blank (Step
5.5.1) after each 10 samples.
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8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection. Refer to Chapter One for additional quality control
procedures.
8.2 Dilute and reanalyze samples that are more concentrated than 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 acidified with the same amounts of acids as were the standards
and samples.
8.4 Analyze one replicate sample for every twenty samples or per
analytical batch, whichever is more frequent. A replicate sample is a sample
brought through the whole sample preparation and analytical process in duplicate.
Refer to Chapter One for a more detailed description of an analytical batch.
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 the analyst 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 Serial dilution: 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 check
standards as follows.
8.6.1 Verify calibration every 10 samples and at the end of the
analytical run, using a calibration blank (Step 5.5.1) and a check
standard (Step 5.6).
8.6.1.1 The results of the check standard are to agree within
10% of the expected value; if not, terminate the analysis, correct
the problem, and reanalyze the previous ten samples.
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8.6.1.2 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.
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 solution (Step 5.7). Results should be within ± 20% of
the true value obtained in Step 8.6.1.1.
8.6.3 Spiked replicate samples are to be analyzed at a frequency
of 5% or per analytical batch, whichever is more frequent.
8.6.3.1 The relative percent difference between replicate
determinations is to be calculated as follows:
Dl ' D2
RPD =
(D + D
where:
RPD = relative percent difference.
D1 = 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.)
8.6.3.2 The spiked replicate sample recovery is to be within
+ 20% of the actual 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 In a single laboratory evaluation, seven wastes were analyzed for 22
elements by this method. The mean percent relative standard deviation from
triplicate analyses for all elements and wastes was 9 ± 2%. The mean percent
recovery of spiked elements for all wastes was 93 + 6%. Spike levels ranged from
100 ug/L to 100 mg/L. The wastes included sludges and industrial wastewaters.
6010A - 13 Revision 1
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10.0 REFERENCES
1. Hinge, R.K.; Peterson, V.J.; Fassel, V.A. Inductively Coupled Plasma-Atomic
Emission Spectroscopy; Prominent Lines (final report, March 1977 -February 1978);
EPA-600/4-79-017, Environmental Research Laboratory, Athens, GA, March 1979; Ames
Laboratory: Ames IA.
2. Test Methods: Methods for Organic Chemical Analysis of Municipal and
Industrial 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, 1982;
EPA-600/4-82-057.
3. Patel, B.K.; Raab, G.A.; et al. Report on a Single Laboratory Evaluation
of Inductively Coupled Optical Emission Method 6010; EPA Contract No. 68-03-3050,
December 1984.
4. 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, 1986; Prepared
by Arthur D. Little, Inc.
5. Bowmand, P.W.J.M. Line Coincidence Tables for Inductively Coupled Plasma
Atomic Emission Spectrometry, 2nd ed.; Pergamon: 1984.
6. Rohrbough, W.G.; et al. Reagent Chemicals, American Chemical Society
Specifications, 7th ed.; American Chemical Society: Washington, DC, 1986. ^^
7. 1985 Annual Book of ASTM Standards. Vol. 11.01; "Standard Specification for '
Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
6010A - 14 Revision 1
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TABLE 4.
ICP PRECISION AND ACCURACY DATA8
Sample No. 1
Sample No. 2
Sample No. 3
Ele-
ment
Be
Mn
V
As
Cr
Cu
Fe
Al
Cd
Co
Ni
Pb
Zn
Sec
Mean Re-
True ported Meaa
Value Value SD D
(ug/L) (ug/L) (%)
750
350
750
200
150
250
600
700
50
700
250
250
200
40
733
345
749
208
149
235
594
696
48
512
245
236
201
32
6.2
2.7
1.8
7.5
3.8
5.1
3.0
5.6
12
10
5.8
16
5.6
21.9
True
Value
(ug/L)
20
15
70
22
10
11
20
60
2.5
20
30
24
16
6
ported
Value
(ug/L)
20
15
69
19
10
11
19
62
2.9
20
28
30
19
8.5
Mean Re- Mean Re-
Mean. True ported Mean.
SD15 Value Value SD D
(%) (ug/L) (ug/L) (%)
9.8
6.7
2.9
23
18
40
15
33
16
4.1
11
32
45
42
180
100
170
60
50
70
180
160
14
120
60
80
80
10
176
99
169
63
50
67
178
161
13
108
55
80
82
8.5
5.2
3.3
1.1
17
3.3
7.9
6.0
13
16
21
14
14
9.4
8.3
all elements were analyzed by all laboratories.
standard deviation.
°Results for Se are from two laboratories.
6010A - 15
Revision 1
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METHOD 6010A
INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROSCOPY
I. H.O
acidified, \ No
pre-filtered?
I* sample
oils .greases
waxes?
Ii sample
queous or
•olid?
7.1 U..
Mathad 300S
7.2 Sat up
and stabilize
instrument
7 1 Use
Hathod 3020
and Mathod
7000
7.1 U..
Hathod 3010
7 3 Profile
and calibrate
ins trument
7 4 Reanalyze
highest mixed
calibration
standard
7.5 Flush
system and
analyze
sample
7.5 Analyze
check standard
and calibration
blank after
each 10 samples
Adjust
instrument per
manufacturer
recommendations
i
7 6 Calculate
concentrations
Stop
6010A - 16
Revision 1
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METHOD 6020
INDUCTIVELY COUPLED PLASMA - MASS SPECTROMETRY
1.0 SCOPE AND APPLICATION
1.1 Inductively coupled plasma-mass spectrometry (ICP-MS) is applicable
to the determination of sub-^g/L concentrations of a large number of elements in
water samples and in waste extracts or digests [1,2]. When dissolved
constituents are required, samples must be filtered and acid-preserved prior to
analysis. No digestion is required prior to analysis for dissolved elements in
water samples. Acid digestion prior to filtration and analysis is required for
groundwater, aqueous samples, industrial wastes, soils, sludges, sediments, and
other solid wastes for which total (acid-leachable) elements are required.
1.2 ICP-MS has been applied to the determination of over 60 elements in
various matrices. Analytes for which EPA has demonstrated the acceptability of
Method 6020 in a multi-laboratory study on solid wastes are listed in Table 1.
Acceptability of the method for an element was based upon the multi-laboratory
performance compared with that of either furnace atomic absorption spectroscopy
or inductively coupled plasma-atomic emission spectroscopy. It should be noted
that the multi-laboratory study was conducted in 1986. Multi-laboratory
performance data for the listed elements (and others) are provided in Section 9.
Instrument detection limits, sensitivities, and linear ranges will vary with the
matrices, instrumentation, and operating conditions. In relatively simple
matrices, detection limits will generally be below 0.02/vg/L.
1.3 If Method 6020 is used to determine any analyte not listed in Table
1, it is the responsibility of the analyst to demonstrate the accuracy and
precision of the Method in the waste to be analyzed. The analyst is always
required to monitor potential sources of interferences and take appropriate
action to ensure data of known quality (see Section 8.4).
1.4 Use of this method is restricted to spectroscopists who are
knowledgeable in the recognition and in the correction of spectral, chemical, and
physical interferences in ICP-MS.
1.5 An appropriate internal standard is required for each analyte
determined by ICP-MS. Recommended internal standards are 6Li, 45Sc, 89Y, 103Rh,
115In, 159Tb, 165Ho, and 209Bi. The lithium internal standard should have an
enriched abundance of 6Li, so that interference from lithium native to the sample
is minimized. Other elements may need to be used as internal standards when
samples contain significant amounts of the recommended internal standards.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis, samples which require total ("acid-leachable")
values must be digested using appropriate sample preparation methods (such as
Methods 3005 - 3051).
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2.2 Method 6020 describes the multi-elemental determination of analytes
by ICP-MS. The method measures ions produced by a radio-frequency inductively
coupled plasma. Analyte species originating in a liquid are nebulized and the
resulting aerosol transported by argon gas into the plasma torch. The ions
produced are entrained in the plasma gas and introduced, by means of an
interface, into a mass spectrometer. The ions produced in the plasma are sorted
according to their mass-to-charge ratios and quantified with a channel electron
multiplier. Interferences must be assessed and valid corrections applied or the
data flagged to indicate problems. Interference correction must include
compensation for background ions contributed by the plasma gas, reagents, and
constituents of the sample matrix.
3.0 INTERFERENCES
3.1 Isobaric elemental interferences in ICP-MS are caused by isotopes of
different elements forming atomic ions with the same nominal mass-to-charge ratio
(m/z). A data system must be used to correct for these interferences. This
involves determining the signal for another isotope of the interfering element
and subtracting the appropriate signal from the analyte isotope signal. Since
commercial ICP-MS instruments nominally provide unit resolution at 10% of the
peak height, very high ion currents at adjacent masses can also contribute to ion
signals at the mass of interest. Although this type of interference is uncommon,
it is not easily corrected, and samples exhibiting a significant problem of this
type could require resolution improvement, matrix separation, or analysis using
another verified and documented isoptope, or use of another method.
3.2 Isobaric molecular and doubly-charged ion interferences in ICP-MS are
caused by ions consisting of more than one atom or charge, respectively. Most
isobaric interferences that could affect ICP-MS determinations have been
identified in the literature [3,4]. Examples include ArCl+ ions on the 75As
signal and MoO+ ions on the cadmium isotopes. While the approach used to
correct for molecular isobaric interferences is demonstrated below using the
natural isotope abundances from the literature [5], the most precise coefficients
for an instrument can be determined from the ratio of the net isotope signals
observed for a standard solution at a concentration providing suitable (<1
percent) counting statistics. Because the 35C1 natural abundance of 75.77
percent is 3.13 times the 37C1 abundance of 24.23 percent, the chloride
correction for arsenic can be calculated (approximately) as follows (where the
38Ar37Cl+ contribution at m/z 75 is a negligible 0.06 percent of the 40Ar35Cl +
signal):
corrected arsenic signal (using natural isotopes abundances for
coefficient approximations) =
(m/z 75 signal) - (3.13) (m/z 77 signal) + (2.73) (m/z 82 signal),
(where the final term adjusts for any selenium contribution at 77 m/z),
NOTE: Arsenic values can be biased high by this type of equation when the
net signal at m/z 82 is caused by ions other than Se+, (e.g., 81BrH+ from
bromine wastes [6]).
6020-2 Revision 0
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Similarly,
corrected cadmium signal (using natural isotopes abundances for
coefficient approximations) =
(m/z 114 signal) - (0.027)(m/z 118 signal) - (1.63)(m/z 108 signal),
(where last 2 terms adjust for any tin or MoO+ contributions at m/z 114).
NOTE: Cadmium values will be biased low by this type of equation when
92ZrO+ ions contribute at m/z 108, but use of m/z 111 for Cd is even
subject to direct (94ZrOH+) and indirect (90ZrO+) additive interferences
when Zr is present.
NOTE: As for the arsenic equation above, the coefficients in the Cd
equation are ONLY illustrative. The most appropriate coefficients for an
instrument can be determined from the ratio of the net isotope signals
observed for a standard solution at a concentration providing suitable (<1
percent) counting precision.
The accuracy of these types of equations is based upon the constancy of the
OBSERVED isotopic ratios for the interfering species. Corrections that presume
a constant fraction of a molecular ion relative to the "parent" ion have not been
found [7] to be reliable, e.g., oxide levels can vary. If a correction for an
oxide ion is based upon the ratio of parent-to-oxide ion intensities, the
correction must be adjusted for the degree of oxide formation by the use of an
appropriate oxide internal standard previously demonstrated to form a similar
level of oxide as the interferant. This type of correction has been reported [7]
for oxide-ion corrections using ThO+/Th+ for the determination of rare earth
elements. The use of aerosol desolvation and/or mixed plasmas have been shown
to greatly reduce molecular interferences [8], These techniques can be used
provided that method detection limits, accuracy, and precision requirements for
analysis of the samples can be met.
3.3 Physical interferences are associated with the sample nebulization and
transport processes as well as with ion-transmission efficiencies. Nebulization
and transport processes can be affected if a matrix component causes a change in
surface tension or viscosity. Changes in matrix composition can cause
significant signal suppression or enhancement [9]. Dissolved solids can deposit
on the nebulizer tip of a pneumatic nebulizer and on the interface skimmers
(reducing the orifice size and the instrument performance). Total solid levels
below 0.2% (2,000 mg/L) have been currently recommended [10] to minimize solid
deposition. An internal standard can be used to correct for physical
interferences, if it is carefully matched to the analyte so that the two elements
are similarly affected by matrix changes [11]. When the intensity level of an
internal standard is less than 30 percent or greater than 120 percent of the
intensity of the first standard used during calibration, the sample must be
reanalyzed after a fivefold (1+4) or greater dilution has been performed.
3.4 Memory interferences can occur when there are large concentration
differences between samples or standards which are analyzed sequentially. Sample
6020-3 Revision 0
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deposition on the sampler and skimmer cones, spray chamber design, and the type
of nebulizer affect the extent of the memory interferences which are observed.
The rinse period between samples must be long enough to eliminate significant
memory interference.
4.0 APPARATUS AND MATERIALS
4.1 Inductively coupled plasma-mass spectrometer:
4.1.1 A system capable of providing resolution, better than or
equal to amu at 10% peak height is required. The system must have a mass
range from at least 6 to 240 amu and a data system that allows corrections
for isobaric interferences and the application of the internal standard
technique. Use of a mass-flow controller for the nebulizer argon and a
peristaltic pump for the sample solution are recommended.
4.1.2 Argon gas supply: high-purity grade (99.99%).
5.0 REAGENTS
5.1 Acids used in the preparation of standards and for sample processing
must be of high purity. Redistilled acids are recommended because of the high
sensitivity of ICP-MS. Nitric acid at less than 2 per cent (v/v) is required for
ICP-MS to minimize damage to the interface and to minimize isobaric molecular-ion
interferences with the analytes. Many more molecular-ion interferences are
observed on the analytes when hydrochloric and sulfuric acids are used [3,4].
Concentrations of antimony and silver between 50-500 /jg/l require 1% (v/v) HC1
for stability; for concentrations above 500 /jq/L Ag, additional HC1 will be
needed.
5.2 Reagent water: 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 Standard stock solutions may be purchased or prepared from ultra-high
purity grade chemicals or metals (99.99 or greater purity ). See Method 6010A,
Section 5.3, for instructions on preparing standard solutions from solids.
5.3.1 Bismuth internal standard solution, stock, 1 mL = 100//g Bi:
Dissolve 0.1115 g Bi203 in a minimum amount of dilute HN03. Add 10 ml
cone. HN03 and dilute to 1,000 ml with reagent water.
5.3.2 Holmium internal standard solution, stock, 1 mL = 100//g Ho:
Dissolve 0.1757 g Ho2(C03)2-5H20 in 10 mL reagent water and 10 mL HN03.
After dissolution is complete, warm the solution to degas. Add 10 mL
cone. HN03 and dilute to 1,000 mL with reagent water.
5.3.3 Indium internal standard solution, stock, 1 mL = 100 ^g In:
Dissolve 0.1000 g indium metal in 10 mL cone. HN03. Dilute to 1,000 mL
with reagent water.
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5.3.4 Lithium internal standard solution, stock, 1 ml = 100 fjg 6Li:
Dissolve 0.6312 g 95-atom-% 6Li, Li2C03 in 10 ml of reagent water and 10 ml
HN03. After dissolution is complete, warm the solution to degas. Add
10 ml cone. HN03 and dilute to 1,000 ml with reagent water.
5.3.5 Rhodium internal standard solution, stock, 1 ml = 100 //g Rh:
Dissolve 0.3593 g ammonium hexachlororhodate (III) (NH4)3RhCl6 in 10 ml
reagent water. Add 100 ml cone. HC1 and dilute to 1,000 ml with reagent
water.
5.3.6 Scandium internal standard solution, stock, 1 ml = 100/yg Sc:
Dissolve 0.15343 g Sc203 in 10 ml (1+1) hot HN03. Add 5 ml cone. HN03 and
dilute to 1,000 ml with reagent water.
5.3.7 Terbium internal standard solution, stock, 1 ml = 100//g Tb:
Dissolve 0.1828 g Tb2(C03)3-5H20 in 10 ml (1+1) HN03. After dissolution is
complete, warm the solution to degas. Add 5 ml cone. HN03 and dilute to
1,000 ml with reagent water.
5.3.8 Yttrium internal standard solution, stock, 1 ml = 100 /yg Y:
Dissolve 0.2316 g Y2(C03)3.3H20 in 10 ml (1+1) HN03. Add 5 ml cone. HN03
and dilute to 1,000 ml with reagent water.
5.3.9 Titanium solution, stock, 1 ml = 100 fjg Ti: Dissolve 0.4133 g
(NH4)2TiF6 in reagent water. Add 2 drops cone. HF and dilute to 1,000 ml
with reagent water.
5.3.10 Molybdenum solution, stock, 1 mL = 100 jjg Mo: Dissolve
0.2043 g (NH4)2Mo04 in reagent water. Dilute to 1,000 mL with reagent
water.
5.4 Mixed calibration standard solutions are prepared by diluting the
stock-standard solutions to levels in the linear range for the instrument in a
solvent consisting of 1 percent (v/v) HN03 in reagent water. The calibration
standard solutions must contain a suitable concentration of an appropriate
internal standard for each analyte. Internal standards may be added on-line at
the time of analysis using a second channel of the peristaltic pump and an
appropriate mixing manifold.) Generally, an internal standard should be no more
than 50 amu removed from the analyte. Recommended internal standards include
6Li, 45Sc, 89Y, 103Rh, 1l5In, 159Tb, ^Ho, and 209Bi. Prior to preparing the mixed
standards, each stock solution must be analyzed separately to determine possible
spectral interferences or the presence of impurities. Care must be taken when
preparing the mixed standards that the elements are compatible and stable.
Transfer the mixed standard solutions to freshly acid-cleaned FEP fluorocarbon
bottles for storage. Fresh mixed standards must be prepared as needed with the
realization that concentrations can change on aging. Calibration standards must
be initially verified using a quality control standard (see Section 5.7) and
monitored weekly for stability.
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5.5 Blanks: Three types of blanks are required for the analysis. The
calibration blank is used in establishing the calibration curve. The
preparation blank is used to monitor for possible contamination resulting from
the sample preparation procedure. The rinse blank is used to flush the system
between all samples and standards.
5.5.1 The calibration blank consists of the same concentration(s)
of the same acid(s) used to prepare the final dilution of the calibrating
solutions of the analytes [often 1 percent HN03 (v/v) in reagent water]
along with the selected concentrations of internal standards such that
there is an appropriate internal standard element for each of the
analytes. Use of HC1 for antimony and silver is cited in Section 5.1
5.5.2 The preparation (or reagent) blank must be carried through
the complete preparation procedure and contain the same volumes of
reagents as the sample solutions.
5.5.3 The rinse blank consists of 1 to 2 percent HN03 (v/v) in
reagent water. Prepare a sufficient quantity to flush the system between
standards and samples.
NOTE: The ICS solutions in Table 2 are intended to evaluate
corrections for known interferences on only the analytes in Table 1.
If Method 6020 is used to determine an element not listed in Table
1, it is the responsibility of the analyst to modify the ICS
solutions, or prepare an alternative ICS solution, to allow adequate
verification of correction of interferences on the unlisted element
(see section 8.4).
5.6 The interference check solution (ICS) is prepared to contain known
concentrations of interfering elements that will demonstrate the magnitude of
interferences and provide an adequate test of any corrections. Chloride in the
ICS provides a means to evaluate software corrections for chloride-related
interferences such as 35C11V on 5V and 40Ar35Cl+ on 75As+. Iron is used to
demonstrate adequate resolution of the spectrometer for the determination of
manganese. Molybdenum serves to indicate oxide effects on cadmium isotopes. The
other components are present to evaluate the ability of the measurement system
to correct for various molecular-ion isobaric interferences. The ICS is used to
verify that the interference levels are corrected by the data system within
quality control limits.
5.6.1 These solutions must be prepared from ultra-pure reagents.
They can be obtained commercially or prepared by the following procedure.
5.6.1.1 Mixed ICS solution I may be prepared by adding
13.903 g A1(N03)3-9H20, 2.498 g CaC03 (dried at 180 C for 1 h before
weighing), 1.000 g Fe, 1.658 g MgO, 2.305 g Na2C03, and 1.767 g K2C03
to 25 ml of reagent water. Slowly add 40 mL of (1+1) HN03. After
dissolution is complete, warm the solution to degas. Cool and
dilute to 1,000 ml with reagent water.
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5.6.1.2 Mixed ICS solution II may be prepared by slowly
adding 7.444 g 85 % H3P04, 6.373 g 96% H2S04, 40.024 g 37% HC1, and
10.664 g citric acid C607H8 to 100 ml of reagent water. Dilute to
1,000 ml with reagent water.
5.6.1.3 Mixed ICS solution III may be prepared by adding
1.00 ml each of 100-/yg/mL arsenic, cadmium, chromium, cobalt,
copper, manganese, nickel, silver, and zinc stock solutions to about
50 ml reagent water. Add 2.0 ml concentrated HN03, and dilute to
100.0 ml with reagent water.
5.6.1.4 Working ICS Solutions
5.6.1.4.1 ICS-A may be prepared by adding 10.0 ml of
mixed ICS solution I (5.7.1.1), 2.0 ml each of 100-/vg/mL
titanium stock solution (5.3.9) and molybdenum stock solution
(5.3.10), and 5.0 ml of mixed ICS solution II (5.7.1.2).
Dilute to 100 ml with reagent water. ICS solution A must be
prepared fresh weekly.
5.6.1.4.2 ICS-AB may be prepared by adding 10.0 ml of
mixed ICS solution I (5.7.1.1), 2.0 ml each of 100-//g/mL
titanium stock solution (5.3.9) and molybdenum stock solution
(5.3.10), 5.0 ml of mixed ICS solution II (5.7.1.2), and
2.0 ml of Mixed ICS solution III (5.7.1.3). Dilute to 100 ml
with reagent water. Although the ICS solution AB must be
prepared fresh weekly, the analyst should be aware that the
solution may precipitate silver more quickly.
5.7 The quality control standard is the initial calibration verification
solution (ICV), which must be prepared in the same acid matrix as the calibration
standards. This solution must be an independent standard near the midpoint of
the linear range at a concentration other than that used for instrument
calibration. An independent standard is defined as a standard composed of the
analytes from a source different from those used in the standards for instrument
calibration.
5.8 Mass spectrometer tuning solution. A solution containing elements
representing all of the mass regions of interest (for example, 10/yg/L of Li, Co,
In, and Tl) must be prepared to verify that the resolution and mass calibration
of the instrument are within the required specifications (see Section 7.5). This
solution is also used to verify that the instrument has reached thermal stability
(See Section 7.4).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Sample collection procedures should address the considerations
described in Chapter Nine of this Manual.
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6.2 See the introductory material in Chapter Three, Inorganic Analytes,
Sections 3.1.3 for information on sample handling and preservation. Only
polyethylene or fluorocarbon (TFE or PFA) containers are recommended for use in
Method 6020.
7.0 PROCEDURE
7.1 Solubilization and digestion procedures are presented in the Sample
Preparation Methods (e.g., Methods 3005 - 3051).
7.2 Initiate appropriate operating configuration of the instruments
computer according to the instrument manufacturer's instructions.
7.3 Set up the instrument with the proper operating parameters according
to the instrument manufacturer's instructions.
7.4 Operating conditions: The analyst should follow the instructions
provided by the instrument manufacturer. Allow at least 30 minutes for the
instrument to equilibrate before analyzing any samples. This must be verified
by analyzing a tuning solution (Section 5.8) at least four times with relative
standard deviations of < 5% for the analytes contained in the tuning solution.
NOTE: Precautions must be taken to protect the channel electron
multiplier from high ion currents. The channel electron multiplier
suffers from fatigue after being exposed to high ion currents. This
fatigue can last from several seconds to hours depending on the
extent of exposure. During this time period, response factors are
constantly changing, which invalidates the calibration curve, causes
instability, and invalidates sample analyses.
7.5 Conduct mass calibration and resolution checks in the mass regions of
interest. The mass calibration and resolution parameters are required criteria
which must be met prior to any samples being analyzed. If the mass calibration
differs more than 0.1 amu from the true value, then the mass calibration must be
adjusted to the correct value. The resolution must also be verified to be less
than 0.9 amu full width at 10 percent peak height.
7.6 Calibrate the instrument for the analytes of interest (recommended
isotopes for the analytes in Table 1 are provided in Table 3), using the
calibration blank and at least a single initial calibration standard according
to the instrument manufacturer's procedure. Flush the system with the rinse
blank (5.5.3) between each standard solution. Use the average of at leastthree
integrations for both calibration and sample analyses.
7.7 All masses which could affect data quality should be monitored to
determine potential effects from matrix components on the analyte peaks. The
recommended isotopes to be monitored are liste in Table 3.
7.8 Immediately after the calibration has been established, the
calibration must be verified and documented for every analyte by the analysis of
the calibration verification solution (Section 5.7). When measurements exceed
6020-8 Revision 0
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± 10% of the accepted value, the analyses must be terminated, the problem
corrected, the instrument recalibrated, and the new calibration verified. Any
samples analyzed under an out-of-control calibration must be reanalyzed. During
the course of an analytical run, the instrument may be "resloped" or recalibrated
to correct for instrument drift. A recalibration must then be followed
immediately by a new analysis of a CCV and CCB before any further samples may be
analyzed.
7.9 Flush the system with the rinse blank solution (5.5.3) until the
signal levels return to the method's levels of quantitation (usually about 30
seconds) before the analysis of each sample (see Section 7.7). Nebulize each
sample until a steady-state signal is achieved (usually about 30 seconds) prior
to collecting data. Analyze the calibration verification solution (Section 5.6)
and the calibration blank (Section 5.5.1) at a frequency of at least once every
10 analytical samples. Flow-injection systems may be used as long as they can
meet the performance criteria of this method.
7.10 Dilute and reanalyze samples that are more concentrated than the
linear range for an analyte (or species needed for a correction) or measure an
alternate less-abundant isotope. The linearity at the alternate mass must be
confirmed by appropriate calibration (see Sec. 7.6 and 7.8).
7.11 Calculations: The quantitative values shall be reported in
appropriate units, such as micrograms per liter (jjg/L) for aqueous samples and
milligrams per kilogram (mg/kg) for solid samples. If dilutions were performed,
the appropriate corrections must be applied to the sample values.
7.11.1 If appropriate, or required, calculate results for solids on
a dry-weight basis as follows:
(1) A separate determination of percent solids must be
performed.
(2) The concentrations determined in the digest are to be
reported on the basis of the dry weight of the sample.
Concentration (dry weight)(mg/kg) = •: x
W X o
Where,
C = Digest Concentration (mg/L)
V = Final volume in liters after sample preparation
W = Weight in kg of wet sample
% Solids
100
Calculations should include appropriate interference corrections (see
Section 3.2 for examples), internal-standard normalization, and the
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summation of signals at 206, 207, and 208 m/z for lead (to compensate for
any differences in the abundances of these isotopes between samples and
standards).
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and be available for
easy reference or inspection.
8.2 Instrument Detection Limits (IDLs) in /jg/l can be estimated by
calculating the average of the standard deviations of the three runs on three
non-consecutive days from the analysis of a reagent blank solution with seven
consecutive measurements per day. Each measurement must be performed as though
it were a separate analytical sample (i.e., each measurement must be followed by
a rinse and/or any other procedure normally performed between the analysis of
separate samples). IDLs must be determined at least every three months and kept
with the instrument log book. Refer to Chapter One for additional guidance.
8.3 The intensities of all internal standards must be monitored for every
analysis. When the intensity of any internal standard fails to fall between 30
and 120 percent of the intensity of that internal standard in the initial
calibration standard, the following procedure is followed. The sample must be
diluted fivefold (1+4) and reanalyzed with the addition of appropriate amounts
of internal standards. This procedure must be repeated until the internal -
standard intensities fall within the prescribed window. The intensity levels of
the internal standards for the calibration blank (Section 5.5.1) and instrument
check standard (Section 5.6) must agree within ± 20 percent of the intensity
level of the internal standard of the original calibration solution. If they do
not agree, terminate the analysis, correct the problem, recalibrate, verify the
new calibration, and reanalyze the affected samples.
8.4 To obtain analyte data of known quality, it is necessary to measure
more than the analytes of interest in order to apply corrections or to determine
whether interference corrections are necessary. If the concentrations of
interference sources (such as C, Cl, Mo, Zr, W) are such that, at the correction
factor, the analyte is less than the limit of quantification and the
concentration of interferents are insignificant, then the data may go
uncorrected. Note that monitoring the interference sources does not necessarily
require monitoring the interferant itself, but that a molecular species may be
monitored to indicate the presence of the interferent. When correcttion
equations are used, all QC criteria must also be met. Extensive QC for
interference corrections are required at all times. The monitored masses must
include those elements whose hydrogen, oxygen, hydroxyl, chlorine, nitrogen,
carbon and sulfur molecular ions could impact the analytes of interest.
Unsuspected interferences may be detected by adding pure major matrix components
to a sample to observe any impact on the analyte signals. When an interference
source is present, the sample elements impacted must be flagged to indicate (a)
the percentage interference correction applied to the data or (b) an uncorrected
interference by virtue of the elemental equation used for quantitation. The
isotope proportions for an element or molecular-ion cluster provide information
useful for quality assurance.
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NOTE: Only isobaric elemental, molecular, and doubly charged interference
corrections which use the observed isotopic-response ratios or parent-to-
oxide ratios (provided an oxide internal standard is used as described in
Section 3.2) for each instrument system are acceptable corrections for use
in Method 6020.
8.5 Dilution Test: If the analyte concentration is within the linear
dynamic range of the instrument and sufficiently high (minimally, a factor of at
least 100 times greater than the concentration in the reagent blank, refer to
Section 5.5.2), an analysis of a fivefold (1+4) dilution must agree within ± 10%
of the original determination. If not, an interference effect must be suspected.
One dilution test must be included for each twenty samples (or less) of each
matrix in a batch.
8.6 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
percent of the known value or within the laboratory derived acceptance criteria.
The spike addition should be based on the indigenous concentration of each
element of interest in the sample. If the spike is not recovered within the
specified limits, the sample must be diluted and reanalyzed to compensate for the
matrix effect. Results must agree to within 10% of the original determination.
The use of a standard-addition analysis procedure may also be used to compensate
for this effect (Refer to Method 7000).
8.7 A Laboratory Control Sample (LCS) should be analyzed for each analyte
using the same sample preparations, analytical methods and QA/QC procedures
employed for the test samples. One LCS should be prepared and analyzed for each
sample batch at a frequency of one LCS for each 20 samples or less.
8.8 Check the instrument calibration by analyzing appropriate quality
control solutions as follows:
8.8.1 Check instrument calibration using a calibration blank
(Section 5.5.1) and the initial calibration verification solution
(Sections 5.7 and 7.9).
8.8.2 Verify calibration at a frequency of every 10 analytical
samples with the instrument check standard (Section 5.6) and the
calibration blank (Section 5.5.1). These solutions must also be analyzed
for each analyte at the beginning of the analysis and after the last
sample.
8.8.3 The results of the initial calibration verification solution
and the instrument check standard must agree within ± 10% of the expected
value. If not, terminate the analysis, correct the problem, and
recalibrate the instrument. Any sample analyzed under an out-of-control
calibration must be reanalyzed .
8.8.4 The results of the calibration blank must be less than 3
times the current IDL for each element. If this is not the case, the
reason for the out-of-control condition must be found and corrected, and
6020-11 Revision 0
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affected samples must be reanalyzed. If the laboratory consistently has
concentrations greater than 3 times the IDL, the IDL may be indicative of
an estimated IDL and should be re-evaluated.
8.9 Verify the magnitude of elemental and molecular-ion isobaric
interferences and the adequacy of any corrections at the beginning of an
analytical run or once every 12 hours, whichever is more frequent. Do this by
analyzing the interference check solutions A and AB. The analyst should be aware
that precipitation from solution AB may occur with some elements, specifically
silver. Refer to Section 3.0 for a discussion on intereferences and potential
solutions to those intereferences if additional guidance is needed.
at a
8.10 Analyze one duplicate sample for every matrix in a batch
frequency of one matrix duplicate for every 20 samples.
8.10.1 The relative percent difference (RPD) between duplicate
determinations must be calculated as follows:
ID, - D2 |
RPD = x 100
(D, + D2)/2
where:
RPD = relative percent difference.
D, = first sample value.
D2 = second sample value (duplicate)
A control limit of 20% RPD should not be exceeded for analyte values
greater than 100 times the instrumental detection limit. If this limit is
exceeded, the reason for the out-of-control situation must be found and
corrected, and any samples analyzed during the out-of-control condition
must be reanalyzed.
9.0 METHOD PERFORMANCE
9.1 In an EPA multi-laboratory study, 10 laboratories applied the
ICP-MS technique to both aqueous and solid samples. TABLE 4 summarizes the
method performance data for aqueous samples. Performance data for solid samples
is provided in TABLE 5.
10.0 REFERENCES
1. Horlick, G., et al., Spectrochim. Acta 40B, 1555 (1985).
2. Gray, A.L., Spectrochim. Acta 40B, 1525 (1985); 41B, 151 (1986).
3. Tan, S.H., and Horlick, G., Appl. Spectrosc. 40, 445 (1986).
4. Vaughan, M.A., and Horlick, G., Appl. Spectrosc. 40, 434 (1986).
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5. Holden, N.E., "Table of the Isotopes," in Lide, D.R., Ed., CRC Handbook of
Chemistry and Physics, 74th Ed., CRC Press, Boca Raton, FL, 1993.
6. Hinners, T.A., Heithmar, E., Rissmann, E., and Smith, D., Winter Conference
on Plasma Spectrochemistry, Abstract THP18; p. 237, San Diego, CA (1994).
7. Lichte, F.E., et al., Anal. Chem. 59, 1150 (1987).
8. Evans E.H., and Ebdon, L., J. Anal. At. Spectrom. 4, 299 (1989).
9. Beauchemin, D., et al., Spectrochim. Acta 42B, 467 (1987).
10. Houk, R.S., Anal. Chem. 58, 97A (1986).
11. Thompson, J.J., and Houk, R.S., Appl. Spectrosc. 41, 801 (1987).
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TABLE 1. ELEMENTS APPROVED FOR ICP-MS DETERMINATION
Element CAS* #
Aluminum 7429-90-5
Antimony 7440-36-0
Arsenic 7440-38-2
Barium 7440-39-3
Beryllium 7440-41-7
Cadmium 7440-43-9
Chromium 7440-47-3
Cobalt 7440-48-4
Copper 7440-50-8
Lead 7439-92-1
Manganese 7439-96-5
Nickel 7440-02-0
Silver 7440-22-4
Thallium 7440-28-0
Zinc 7440-66-6
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TABLE 2. RECOMMENDED INTERFERENCE CHECK SAMPLE COMPONENTS AND CONCENTRATIONS
Solution
component
Al
Ca
Fe
Mg
Na
P
K
S
C
Cl
Mo
Ti
As
Cd
Cr
Co
Cu
Mn
Ni
Ag
Zn
Solution A
Concentration (mg/L)
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
200.0
1000.0
2.0
2.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Solution AB
Concentration (mg/L)
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
200.0
1000.0
2.0
2.0
0.0200
0.0200
0.0200
0.0200
0.0200
0.0200
0.0200
0.0200
0.0200
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TABLE 3. RECOMMENDED ISOTOPES FOR SELECTED ELEMENTS
Mass Element of interest
27 Aluminum
121, 123 Antimony
75 Arsenic
138, 137, 136, 135. 134 Barium
9 Beryllium
209 Bismuth (IS)
114. 112, 111. 110, 113, 116, 106 Cadmium
42, 43, 44, 46, 48 Calcium (I)
35, 37, (77, 82)a Chlorine (I)
52, 53, 50, 54 Chromium
59 Cobalt
63, 65 Copper
165 Holmium (IS)
115, 113 Indium (IS)
56, 54, 57, 58 Iron (I)
139 Lanthanum (I)
208, 207. 206, 204 Lead
6*7 7 Lithium (IS)
24, 25, 26 Magnesium (I)
55 Manganese
98, 96, 92, 97, 94, (108)a Molybdenum (I)
58, 60, 62, 61, 64 Nickel
39 Potassium (I)
103 Rhodium (IS)
45 Scandium (IS)
107. 109 Silver
23 Sodium (I)
159 Terbium (IS)
205, 203 Thallium
120, 118 Tin (I)
89 Yttrium (IS)
64, 66, 68, 67, 70 Zinc
NOTE: Method 6020 is recommended for only those analytes listed in Table
1. Other elements are included in this table because they are potential
interferents (labeled I) in the determination of recommended analytes, or because
they are commonly used internal standards (labeled IS). Isotopes are listed in
descending order of natural abundance. The most generally useful isotopes are
underlined and in boldface, although certain matrices may require the use of
alternative isotopes. a These masses are also useful for interference correction
(Section 3.2). b Internal standard must be enriched in the 6Li isotope. This
minimizes interference from indigenous lithium.
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TABLE 4.
SOLUTIONS
ICP-MS MULTI-LABORATORY PRECISION AND ACCURACY DATA FOR AQUEOUS
Element
Comparability3
Range
%RSD
Range
Nb Sc
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
95 - 100
d
97 - 114
91 - 99
103 - 107
98 - 102
99 - 107
95 - 105
101 - 104
85 - 101
91 - 900
71 - 137
98 - 102
95 - 101
98 - 101
101 - 114
102 - 107
104 - 105
82 - 104
88 - 97
107 - 142
93 - 102
11
5.0
7.1
4.3
8.6
4.6
5.7
13
8.2
6.1
11
11
10
8.8
6.1
9.9
15
5.2
24
9.7
23
6.8
- 14
- 7.6
- 48
- 9.0
- 14
- 7.2
- 23
- 27
- 8.5
- 27
- 150
- 23
- 15
- 15
- 6.7
- 19
- 25
- 7.7
- 43
- 12
- 68
- 17
14 -
16 -
12 -
16 -
13 -
18 -
17 -
16 -
18 -
17 -
10 -
17 -
16 -
18 -
18 -
11 -
12 -
13 -
9 -
18 -
8 -
16 -
14
16
14
16
14
20
18
18
18
18
12
18
16
18
18
12
12
16
10
18
13
18
4
3
4
5
3
3
5
4
3
5
5
6
5
4
2
5
3
2
5
3
3
5
a Comparability refers to the percent agreement of mean ICP-MS values to those
of the reference technique, N is the range of the number of ICP-MS
measurements where the analyte values exceed the limit of quantitation (3.3 times
the average IDL value). c S is the number of samples with results greater
than the limit of quantitation. d No comparability values are provided for
antimony because of evidence that the reference data is affected by an
interference.
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TABLE 5. ICP-MS MULT I-LABORATORY PRECISION AND ACCURACY DATA FOR SOLID MATRICES
Element
Comparability8
Range
%RSD
Range Nb
Sc
Aluminum
Antimony
Arsenic
Barium
Beryl 1i urn
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
83 - 101
d
79 - 102
100 - 102
50 - 87
93 - 100
95 - 109
77 - 98
43 - 102
90 - 109
87 - 99
90 - 104
89 - 111
80 - 108
87 - 117
97 - 137
81
43 - 112
100 - 146
91
83 - 147
84 - 124
11 - 39
12 - 21
12 - 23
4.3 - 17
19 - 34
6.2 - 25
4.1 - 27
11 - 32
15 - 30
9.0 - 25
6.7 - 21
5.9 - 28
7.6 - 37
11 - 40
9.2 - 29
11 - 62
39
12 - 33
14 - 77
33
20 - 70
14 - 42
13 - 14
15 - 16
16 - 16
15 - 16
12 - 14
19 - 20
15 - 17
17 - 18
17 - 18
18 - 18
12 - 12
15 - 18
15 - 16
16 - 18
16 - 18
10 - 12
12
15 - 15
8 - 10
18
6 - 14
18 - 18
7
2
7
7
5
5
7
7
6
7
7
7
7
7
7
5
1
3
5
1
7
7
a Comparability refers to the percent agreement of mean ICP-MS values to those
of the reference technique. b N is the range of the number of ICP-MS
measurements where the analyte values exceed the limit of quantitation (3.3 times
the average IDL value). c S is the number of samples with results greater
than the limit of quantitation. d No comparability values are provided for
antimony because of evidence that the reference data is affected by an
interference.
6020-18
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METHOD 6020
INDUCTIVELY COUPLED PLASMA - MASS SPECTROMETRY
7.9 Anah/ia
cheek atandard
•nd calibration
blank afttr
•aeh 1 0 Mmpiaa.
4
7.9 Fluah
ayatom and
analyza
aampla
6020-19
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METHOD 7000A
ATOMIC ABSORPTION METHODS
1.0 SCOPE AND APPLICATION
1.1 Metals in solution may be readily determined by atomic absorption
spectroscopy. The method is simple, rapid, and applicable to a large number of
metals in drinking, surface, and saline waters and domestic and industrial
wastes. While drinking water free of particulate matter may be analyzed directly,
ground water, other aqueous samples, EP extracts, industrial wastes, soils,
sludges, sediments, and other solid wastes require digestion prior to analysis
for both total and acid Teachable metals. Analysis for dissolved elements does
not require digestion if the sample has been filtered and acidified.
1.2 Detection limits, sensitivity, and optimum ranges of the metals will
vary with the matrices and models of atomic absorption spectrophotometers. The
data shown in Table 1 provide some indication of the detection limits obtainable
by direct aspiration and by furnace techniques. For clean aqueous samples, the
detection limits shown in the table by direct aspiration may be extended downward
with scale expansion and upward by using a less sensitive wavelength or by
rotating the burner head. Detection limits by direct aspiration may also be
extended through concentration of the sample and/or through solvent extraction
techniques. For certain samples, lower concentrations may also be determined
using the furnace techniques. The detection limits given in Table 1 are somewhat
dependent on equipment (such as the type of spectrophotometer and furnace
accessory, the energy source, the degree of electrical expansion of the output
signal), and are greatly dependent on sample matrix. Detection limits should be
established, empirically, for each matrix type analyzed. When using furnace
techniques, however, the analyst should be cautioned as to possible chemical
reactions occurring at elevated temperatures which may result in either
suppression or enhancement of the analysis element. To ensure valid data with
furnace techniques, the analyst must examine each matrix for interference effects
(see Step 3.2.1) and, if detected, treat them accordingly, using either
successive dilution, matrix modification, or method of standard additions (see
Step 8.7).
1.3 Where direct-aspiration atomic absorption techniques do not provide
adequate sensitivity, reference is made to specialized procedures (in addition
to the furnace procedure) such as the gaseous-hydride method for arsenic and
selenium and the cold-vapor technique for mercury.
2.0 SUMMARY OF METHOD
2.1 Although methods have been reported for the analysis of solids by
atomic absorption spectroscopy, the technique generally is limited to metals in
solution or solubilized through some form of sample processing.
2.2 Preliminary treatment of waste water, ground water, EP extracts, and
industrial waste is always necessary because of the complexity and variability
of sample matrix. Solids, slurries, and suspended material must be subjected to
a solubilization process before analysis. This process may vary because of the
7000A - 1 Revision 1
July 1992
-------
metals to be determined and the nature of the sample being analyzed. Solubili-
zation and digestion procedures are presented in Step 3.2 (Sample Preparation
Methods).
2.3 In direct-aspiration atomic absorption spectroscopy, a sample is
aspirated and atomized in a flame. A light beam from a hollow cathode lamp or an
electrodeless discharge lamp is directed through the flame into a monochromator,
and onto a detector that measures the amount of absorbed light. Absorption
depends upon the presence of free unexcited ground-state atoms in the flame.
Because the wavelength of the light beam is characteristic of only the metal
being determined, the light energy absorbed by the flame is a measure of the
concentration of that metal in the sample. This principle is the basis of atomic
absorption spectroscopy.
2.4 When using the furnace technique in conjunction with an atomic
absorption spectrophotometer, a representative aliquot of a sample is placed in
the graphite tube in the furnace, evaporated to dryness, charred, and atomized.
As a greater percentage of available analyte atoms is vaporized and dissociated
for absorption in the tube rather than the flame, the use of smaller sample
volumes or detection of lower concentrations of elements is possible. The
principle is essentially the same as with direct aspiration atomic absorption,
except that a furnace, rather than a flame, is used to atomize the sample.
Radiation from a given excited element is passed through the vapor containing
ground-state atoms of that element. The intensity of the transmitted radiation
decreases in proportion to the amount of the ground-state element in the vapor.
The metal atoms to be measured are placed in the beam of radiation by increasing
the temperature of the furnace, thereby causing the injected specimen to be
volatilized. A monochromator isolates the characteristic radiation from the
hollow cathode lamp or electrodeless discharge lamp, and a photosensitive device
measures the attenuated transmitted radiation.
3.0 INTERFERENCES
3.1 Direct aspiration
3.1.1 The most troublesome type of interference in atomic
absorption spectrophotometry is usually termed "chemical" and is caused by
lack of absorption of atoms bound in molecular combination in the flame.
This phenomenon can occur when the flame is not sufficiently hot to
dissociate the molecule, as in the case of phosphate interference with
magnesium, or when the dissociated atom is immediately oxidized to a
compound that will not dissociate further at the temperature of the flame.
The addition of lanthanum will overcome phosphate interference in
magnesium, calcium, and barium determinations. Similarly, silica
interference in the determination of manganese can be eliminated by the
addition of calcium.
3.1.2 Chemical interferences may also be eliminated by separating
the metal from the interfering material. Although complexing agents are
employed primarily to increase the sensitivity of the analysis, they may
also be used to eliminate or reduce interferences.
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3.1.3 The presence of high dissolved solids in the sample may
result in an interference from nonatomic absorbance such as light
scattering. If background correction is not available, a nonabsorbing
wavelength should be checked. Preferably, samples containing high solids
should be extracted.
3.1.4 lonization interferences occur when the flame temperature is
sufficiently high to generate the removal of an electron from a neutral
atom, giving a positively charged ion. This type of interference can
generally be controlled by the addition, to both standard and sample
solutions, of a large excess (1,000 mg/L) of an easily ionized element
such as K, Na, Li or Cs.
3.1.5 Spectral interference can occur when an absorbing wavelength
of an element present in the sample but not being determined falls within
the width of the absorption line of the element of interest. The results
of the determination will then be erroneously high, due to the
contribution of the interfering element to the atomic absorption signal.
Interference can also occur when resonant energy from another element in
a multielement lamp, or from a metal impurity in the lamp cathode, falls
within the bandpass of the slit setting when that other metal is present
in the sample. This type of interference may sometimes be reduced by
narrowing the slit width.
3.1.6 Samples and standards should be monitored for viscosity
differences that may alter the aspiration rate.
3.1.7 All metals are not equally stable in the digestate,
especially if it contains only nitric acid, not nitric acid and
hydrochloric acid. The digestate should be analyzed as soon as possible,
with preference given to Sn, Sb, Mo, Ba, and Ag.
3.2 Furnace procedure
3.2.1 Although the problem of oxide formation is greatly reduced
with furnace procedures because atomization occurs in an inert atmosphere,
the technique is still subject to chemical interferences. The composition
of the sample matrix can have a major effect on the analysis. It is those
effects which must be determined and taken into consideration in the
analysis of each different matrix encountered. To help verify the absence
of matrix or chemical interference, the serial dilution technique (see
Step 8.6) may be used. Those samples which indicate the presence of
interference should be treated in one or more of the following ways:
1. Successively dilute and reanalyze the samples to eliminate
interferences.
2. Modify the sample matrix either to remove interferences or to
stabilize the analyte. Examples are the addition of ammonium
nitrate to remove alkali chlorides and the addition of
ammonium phosphate to retain cadmium. The mixing of hydrogen
with the inert purge gas has also been used to suppress
chemical interference. The hydrogen acts as a reducing agent
and aids in molecular dissociation.
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3. Analyze the sample by method of standard additions while
noticing the precautions and limitations of its use (see Step
8.7.2).
3.2.2 Gases generated in the furnace during atomization may have
molecular absorption bands encompassing the analytical wavelength. When
this occurs, use either background correction or choose an alternate
wavelength. Background correction may also compensate for nonspecific
broad-band absorotion interferenre.
waveiengin. oacKgrouna correction
broad-band absorption interference
3.2.3 Continuum background correction cannot correct for all types
of background interference. When the background interference cannot be
compensated for, chemically remove the analyte or use an alternate form of
background correction, e.g., Zeeman background correction.
3.2.4 Interference from a smoke-producing sample matrix can
sometimes be reduced by extending the charring time at a higher
temperature or utilizing an ashing cycle in the presence of air. Care
must be taken, however, to prevent loss of the analyte.
3.2.5 Samples containing large amounts of organic materials should
be oxidized by conventional acid digestion before being placed in the
furnace. In this way, broad-band absorption will be minimized.
3.2.6 Anion interference studies in the graphite furnace indicate
that, under conditions other than isothermal, the nitrate anion is
preferred. Therefore, nitric acid is preferable for any digestion or
solubilization step. If another acid in addition to nitric acid is
required, a minimum amount should be used. This applies particularly to
hydrochloric and, to a lesser extent, to sulfuric and phosphoric acids.
3.2.7 Carbide formation resulting from the chemical environment of
the furnace has been observed. Molybdenum may be cited as an example. When
carbides form, the metal is released very slowly from the resulting metal
carbide as atomization continues. Molybdenum may require 30 seconds or
more atomization time before the signal returns to baseline levels.
Carbide formation is greatly reduced and the sensitivity increased with
the use of pyrolytically coated graphite. Elements that readily form
carbides are noted with the symbol (p) in Table 1.
3.2.8 For comments on spectral interference, see Step 3.1.5.
3.2.9 Cross-contamination and contamination of the sample can be
major sources of error because of the extreme sensitivities achieved with
the furnace. The sample preparation work area should be kept scrupulously
clean. All glassware should be cleaned as directed in Step 4.8. Pipet
tips are a frequent source of contamination. If suspected, they should be
acid soaked with 1:5 nitric acid and rinsed thoroughly with tap and
reagent water. The use of a better grade of pipet tip can greatly reduce
this problem. Special attention should be given to reagent blanks in both
analysis and in the correction of analytical results. Lastly, pyrolytic
graphite, because of the production process and handling, can become
contaminated. As many as five to ten high-temperature burns may be
required to clean the tube before use.
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4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer - Single- or dual-channel,
single- or double-beam instrument having a grating monochromator, photomultiplier
detector, adjustable slits, a wavelength range of 190 to 800 nm, and provisions
for interfacing with a graphical display.
4.2 Burner - The burner recommended by the particular instrument
manufacturer should be used. For certain elements the nitrous oxide burner is
required.
4.3 Hollow cathode lamps - Single-element lamps are preferred but
multielement lamps may be used. Electrodeless discharge lamps may also be used
when available. Other types of lamps meeting the performance criteria of this
method may be used.
4.4 Graphite furnace - Any furnace device capable of reaching the
specified temperatures is satisfactory.
4.5 Graphical display and recorder - A recorder is recommended for
furnace work so that there will be a permanent record and that any problems with
the analysis such as drift, incomplete atomization, losses during charring,
changes in sensitivity, peak shape, etc., can be easily recognized.
4.6 Pipets - Microliter, with disposable tips. Sizes can range from 5 to
100 uL as required. Pipet tips should be checked as a possible source of
contamination prior to their use. The accuracy of automatic pipets must be
verified daily. Class A pipets can be used for the measurement of volumes larger
than 1 ml_.
4.7 Pressure-reducing valves - The supplies of fuel and oxidant should
be maintained at pressures somewhat higher than the controlled operating pressure
of the instrument by suitable valves.
4.8 Glassware - All glassware, polypropylene, or Teflon containers,
including sample bottles, flasks and pipets, should be washed in the following
sequence: detergent, tap water, 1:1 nitric acid, tap water, 1:1 hydrochloric
acid, tap water, and reagent water. (Chromic acid should not be used as a
cleaning agent for glassware if chromium is to be included in the analytical
scheme.) If it can be documented through an active analytical quality control
program using spiked samples and reagent blanks that certain steps in the
cleaning procedure are not required for routine samples, those steps may be
eliminated from the procedure.
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
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without lessening the accuracy of the determination. All reagents should be
analyzed to provide proof that all constituents are below the MDLs.
5.2 Reagent water. All references to water in this method refer to
reagent water unless otherwise specified. Reagent grade water will be of at
least 16 Mega Ohm quality.
5.3 Nitric acid (concentrated), HN03. Use a spectrograde acid certified
for AA use. Prepare a 1:1 dilution with water by adding the concentrated acid to
an equal volume of water. If the reagent blank is less than the IDL, the acid
may be used.
5.4 Hydrochloric acid (1:1), HC1. Use a spectrograde acid certified for
AA use. Prepare a 1:1 dilution with water by adding the concentrated acid to an
equal volume of water. If the reagent blank is less than the IDL, the acid may
be used.
5.5 Fuel and oxidant - High purity acetylene is generally acceptable. Air
may be supplied from a compressed air line, a laboratory compressor, or a
cylinder of compressed air and should be clean and dry. Nitrous oxide is also
required for certain determinations. Standard, commercially available argon and
nitrogen are required for furnace work.
5.6 Stock standard metal solutions - Stock standard solutions are prepared
from high purity metals, oxides, or nonhygroscopic salts using water and
redistilled nitric or hydrochloric acids. (See individual methods for specific
instructions.) Sulfuric or phosphoric acids should be avoided as they produce
an adverse effect on many elements. The stock solutions are prepared at
concentrations of 1,000 mg of the metal per liter. Commercially available
standard solutions may also be used. Where the sample viscosity, surface tension,
and components cannot be accurately matched with standards, the method of
standard addition (MSA) may be used (see Step 8.7).
5.7 Calibration standards - For those instruments which do not read out
directly in concentration, a calibration curve is prepared to cover the
appropriate concentration range. Usually, this means the preparation of
standards which produce an absorbance of 0.0 to 0.7. Calibration standards are
prepared by diluting the stock metal solutions at the time of analysis. For best
results, calibration standards should be prepared fresh each time a batch of
samples is analyzed. Prepare a blank and at least three calibration standards in
graduated amounts in the appropriate range of the linear part of the curve. The
calibration standards should be prepared using the same type of acid or
combination of acids and at the same concentration as will result in the samples
following processing. Beginning with the blank and working toward the highest
standard, aspirate the solutions and record the readings. Repeat the operation
with both the calibration standards and the samples a sufficient number of times
to secure a reliable average reading for each solution. Calibration standards for
furnace procedures should be prepared as described on the individual sheets for
that metal. Calibration curves are always required.
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6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material in Chapter Three, Metallic Analytes.
7.0 PROCEDURE
7.1 Preliminary treatment of waste water, ground water, EP extracts, and
industrial waste is always necessary because of the complexity and variability
of sample matrices. Solids, slurries, and suspended material must be subjected
to a solubilization process before analysis. This process may vary because of the
metals to be determined and the nature of the sample being analyzed.
Solubilization and digestion procedures are presented in Chapter Three, Step 3.2,
Sample Preparation Methods. Samples which are to be analyzed for dissolved
constituents need not be digested if they have been filtered and acidified.
7.2 Direct aspiration (flame) procedure
7.2.1 Differences between the various makes and models of
satisfactory atomic absorption spectrophotometers prevent the formulation
of detailed instructions applicable to every instrument. The analyst
should follow the manufacturer's operating instructions for a particular
instrument. In general, after choosing the proper lamp for the analysis,
allow the lamp to warm up for a minimum of 15 minutes, unless operated in
a double-beam mode. During this period, align the instrument, position the
monochromator at the correct wavelength, select the proper monochromator
slit width, and adjust the current according to the manufacturer's
recommendation. Subsequently, light the flame and regulate the flow of
fuel and oxidant. Adjust the burner and nebulizer flow rate for maximum
percent absorption and stability. Balance the photometer. Run a series of
standards of the element under analysis. Construct a calibration curve by
plotting the concentrations of the standards against absorbances. Set the
curve corrector of a direct reading instrument to read out the proper
concentration. Aspirate the samples and determine the concentrations
either directly or from the calibration curve. Standards must be run each
time a sample or series of samples is run.
7.3 Furnace procedure
7.3.1 Furnace devices (flameless atomization) are a most useful
means of extending detection limits. Because of differences between
various makes and models of satisfactory instruments, no detailed
operating instructions can be given for each instrument. Instead, the
analyst should follow the instructions provided by the manufacturer of a
particular instrument.
7.3.2 Background correction is important when using flameless
atomization, especially below 350 nm. Certain samples, when atomized, may
absorb or scatter light from the lamp. This can be caused by the presence
of gaseous molecular species, salt particles, or smoke in the sample beam.
If no correction is made, sample absorbance will be greater than it should
be, and the analytical result will be erroneously high. Zeeman background
correction is effective in overcoming composition or structured background
7000A - 7 Revision 1
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interferences. It is particularly useful when analyzing for As in the
presence of Al and when analyzing for Se in the presence of Fe.
7.3.3 Memory effects occur when the analyte is not totally
volatilized during atomization. This condition depends on several factors:
volatility of the element and its chemical form, whether pyrolytic
graphite is used, the rate of atomization, and furnace design. This
situation is detected through blank burns. The tube should be cleaned by
operating the furnace at full power for the required time period, as
needed, at regular intervals during the series of determinations.
7.3.4 Inject a measured micro!iter aliquot of sample into the
furnace and atomize. If the concentration found is greater than the
highest standard, the sample should be diluted in the same acid matrix and
reanalyzed. The use of multiple injections can improve accuracy and help
detect furnace pipetting errors.
7.3.5 To verify the absence of interference, follow the serial
dilution procedure given in Step 8.6.
7.3.6 A check standard should be run after approximately every 10
sample injections. Standards are run in part to monitor the life and
performance of the graphite tube. Lack of reproducibility or significant
change in the signal for the standard indicates that the tube should be
replaced. Tube life depends on sample matrix and atomization temperature.
A conservative estimate would be that a tube will last at least 50
firings. A pyrolytic coating will extend that estimated life by a factor
of three.
7.4 Calculation
7.4.1 For determination of metal concentration by direct aspiration
and furnace: Read the metal value from the calibration curve or directly
from the read-out system of the instrument.
7.4.2 If dilution of sample was required:
ug/L metal in sample = A (C_+_B)
C
where:
A = ug/L of metal in diluted aliquot from calibration curve.
B = Acid blank matrix used for dilution, mL.
C = Sample aliquot, mL.
7.4.3 For solid samples, report all concentrations in consistent
units based on wet weight. Hence:
ug metal/kg sample = A x V
W
where:
A = ug/L of metal in processed sample from calibration curve.
V = Final volume of the processed sample, mL.
W = Weight of sample, grams.
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7.4.4 Different injection volumes must not be used for samples and
standards. Instead, the sample should be diluted and the same size
injection volume be used for both samples and standards. If dilution of
the sample was required:
ug/L of metal in sample = Z ( C + B)
C
where:
Z = ug/L of metal read from calibration curve or read-out system.
B = Acid blank matrix used for dilution mL.
C = Sample aliquot, ml.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection.
8.2 A calibration curve must be prepared each day with a minimum of a
calibration blank and three standards. After calibration, the calibration curve
must be verified by use of at least a calibration blank and a calibration check
standard (made from a reference material or other independent standard material)
at or near the mid-range. The calibration reference standard must be measured
within 10 % of it's true value for the curve to be considered valid.
8.3 If more than 10 samples per day are analyzed, the working standard
curve must be verified by measuring satisfactorily a mid-range standard or
reference standard after every 10 samples. This sample value must be within 20%
of the true value, or the previous ten samples need to be reanalyzed.
8.4 At least one matrix spike and one matrix spike duplicate sample shall
be included in each analytical batch. A laboratory control sample shall also be
processed with each sample batch. Refer to Chapter One for more information.
8.5 Where the sample matrix is so complex that viscosity, surface tension,
and components cannot be accurately matched with standards, the method of
standard addition (MSA) is recommended (see Section 8.7 below). Section 8.6
provides tests to evaluate the need for using the MSA.
8.6 Interference tests
8.6.1 Dilution test - For each analytical batch select one typical sample
for serial dilution to determine whether interferences are present. The
concentration of the analyte should be at least 25 times the estimated detection
limit. Determine the apparent concentration in the undiluted sample. Dilute the
sample by a minimum of five fold (1+4) and reanalyze. If all of the samples in
the batch are below 10 times the detection limits, perform the spike recovery
analysis described below. Agreement within 10% between the concentration for the
undiluted sample and five times the concentration for the diluted sample
indicates the absence of interferences, and such samples may be analyzed without
using the method of standard additions.
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8.6.2 Recovery test - If results from the dilution test do not agree, a
matrix interference may be suspected and a spiked sample should be analyzed to
help confirm the finding from the dilution test. Withdraw another aliquot of the
test sample and add a known amount of analyte to bring the concentration of the
analyte to 2 to 5 times the original concentration. If all of the samples in the
batch have analyte concentrations below the detection limit, spike the selected
sample at 20 times the detection limit. Analyze the spiked sample and calculate
the spike recovery. If the recovery is less than 85% or greater than 115%, the
method of standard additions shall be used for all samples in the batch.
8.7 Method of standard additions - The standard addition technique
involves adding known amounts of standard to one or more aliquots of the
processed sample solution. This technique compensates for a sample constituent
that enhances or depresses the analyte signal, thus producing a different slope
from that of the calibration standards. It will not correct for additive
interferences which cause a baseline shift. The method of standard additions
shall be used for analysis of all EP extracts, on all analyses submitted as part
of a delisting petition, and whenever a new sample matrix is being analyzed.
8.7.1 The simplest version of this technique is the single-addition
method, in which two identical aliquots of the sample solution, each of
volume Vx, are taken. To the first (labeled A) is added a known volume Vs
of a standard analyte solution of concentration Cs. To the second aliquot
(labeled B) is added the same volume Vs of the solvent. The analytical
signals of A and B are measured and corrected for nonanalyte signals. The
unknown sample concentration Cx is calculated:
C
X
(SA-SB)VX
where SA and SB are the analytical signals (corrected for the blank) of
solutions A and B, respectively. Vs and Cs should be chosen so that SA is
roughly twice SB on the average, avoiding excess dilution of the sample.
If a separation or concentration step is used, the additions are best made
first and carried through the entire procedure.
8.7.2 Improved results can be obtained by employing a series of
standard additions. To equal volumes of the sample are added a series of
standard solutions containing different known quantities of the analyte,
and all solutions are diluted to the same final volume. For example,
addition 1 should be prepared so that the resulting concentration is
approximately 50 percent of the expected absorbance from the endogenous
analyte in the sample. Additions 2 and 3 should be prepared so that the
concentrations are approximately 100 and 150 percent of the expected
endogenous sample absorbance. The absorbance of each solution is
determined and then plotted on the vertical axis of a graph, with the
concentrations of the known standards plotted on the horizontal axis. When
the resulting line is extrapolated to zero absorbance, the point of
interception of the abscissa is the endogenous concentration of the
analyte in the sample. The abscissa on the left of the ordinate is scaled
the same as on the right side, but in the opposite direction from the
7000A - 10 Revision 1
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ordinate. An example of a plot so obtained is shown in Figure 1. A linear
regression program may be used to obtain the intercept concentration.
8.7.3 For the results of this MSA technique to be valid, the
following limitations must be taken into consideration:
1. The apparent concentrations from the calibration curve must be
linear over the concentration range of concern. For the best
results, the slope of the MSA plot should be nearly the same
as the slope of the standard curve. If the slope is
significantly different (greater than 20%), caution should be
exercised.
2. The effect of the interference should not vary as the ratio of
analyte concentration to sample matrix changes, and the
standard addition should respond in a similar manner as the
analyte.
3. The determination must be free of spectral interference and
corrected for nonspecific background interference.
8.8 All quality control measures described in Chapter One should be
followed.
9.0 METHOD PERFORMANCE
9.1 See individual methods.
10.0 REFERENCES
1. Methods for 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 Center for Environmental
Research Information: Cincinnati, OH, 1983; EPA-600/4-79-020.
2. Rohrbough, W.G.; et al. Reagent Chemicals, American Chemical Society
Specifications, 7th ed.; American Chemical Society: Washington, DC, 1986.
3. 1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
7000A - 11 Revision 1
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TABLE 1.
ATOMIC ABSORPTION CONCENTRATION RANGES
Metal
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Mercury
Molybdenum(p)
Nickel
Osmium
Potassium
Selenium
Silver
Sodium
Strontium
Thallium
Tin
Vanadium(p)
Zinc
Detection Limit
(mg/L)
0.1
0.2
0.002
0.1
0.005
0.005
0.01
0.05
0.05
0.02
0.03
0.1
0.002
0.001
0.01
0.0002
0.1
0.04
0.03
0.01
0.002
0.01
0.002
0.03
0.1
0.8
0.2
0.005
Sensitivity
(mg/L)
1
0.5
0.4
0.025
0.025
0.08
0.25
0.2
0.1
0.12
0.5
0.04
0.007
0.05
0.4
0.15
1
0.04
0.06
0.015
0.15
0.5
4
0.8
0.02
Furnace Procedure4'0
Detection Limit
(ug/L)
..
3
1
2
0.2
0.1
--
1
1
1
1
1
--
0.2
1
--
2
0.2
--
--
1
--
4
0.05
i
NOTE:
The symbol (p) indicates the use of pyrolytic graphite with
the furnace procedure.
aFor furnace sensitivity values, consult instrument operating manual.
Gaseous hydride method.
'ihe listed furnace values are those expected when using a 20-uL injection and
normal gas flow, except in the cases of arsenic and selenium, where gas interrupt
is used.
vapor technique.
7000A - 12
Revision 1
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FIGURE 1.
STANDARD ADDITION PLOT
CD
o
CO
.a
o
CO
Zero
Absorbance
Concentration
Cone, of Addn 0 Addn 1 Addn 2 Addn 3
Sample No Addn Addn of 50% Addn of 100% Addn of 150%
of Expected of Expected of Expected
Amount Amount Amount
7000A - 13
Revision 1
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METHOD 7000A
ATOMIC ABSORPTION METHODS
c
7.1 Solubili2«
and digeftt
•ample (tee
Chapter 3,
Section 3 2)
7.2 1 Choo««
and prepare
hollow tub*
cathode lamp
7.3.1 Follow
operating
in»tructlon*
fron instrument
manufacturer
7.2.1 ftdjust
and align
equipment
7.2.1 Light
flan* and
regulate
7.21 Run
•tandard*
7.3.3 Clean
tub*
732 Hake
background
correction
7 3.4 Inject
and atomize
part of
(ample
7 2.1 Construct
calibration
curve and *et
curve corrector
7.2 1
A*pirate
•ample
7.3 4 Dilutfl
• atnpl*
7 3.5 U.«
intarf«r«nc«
t«»t» to varify
abvanca of
interfarBnc*
7.2.1 Run a
check
itandard
7 4 Determine
concentration!
7 3 6 Run
check
•tandard
Stop
7000A - 14
Revision 1
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METHOD 7020
ALUMINUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Aluminum may be as much as 15% ionized in a nitrous-oxide/acetylene
flame. Use of an ionization suppressor (1,000 ug/mL K as KC1) as in Method
7000, Paragraph 3.1.4, will eliminate this interference.
3.3 Aluminum is a very common contaminant, and great care should be
taken to avoid contamination.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Aluminum hollow cathode lamp.
4.2.2 Wavelength: 324.7 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards:
5.2.1 Stock solution: Dissolve 1.000 g of aluminum metal in dilute
HC1 with gentle warming. Dilute to 1 liter with Type II water. Alterna-
tively, procure a certified standard from a supplier and verify by
comparison with a second standard.
7020 - 1
Revision
Date September 1986
-------
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
concentration as will result in the sample to be analyzed after
processing. Samples and standards should also contain 2 ml KC1/100 ml
solution (Paragraph 3.2 above).
5.3 Potassium chloride solution; Dissolve 95 g potassium chloride (KC1)
in Type II water and dilute to 1 liter.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 202.1 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 5-50 mg/L, with a wavelength of 309.3 nm.
Sensitivity: 1 mg/L.
Detection limit: 0.1 mg/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
Method 202.1, December 1982.
7020 - 2
Revision
Date September 1986
-------
METHOD 7020
ALUMINUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.O
Prepare
standards
7.1
For
sample
preparation see
chapter 3.
section 3.2
7.2
Analyze using
Method 700O.
Section 7.2
f Stop J
7020 - 3
Revision o
Date September 1986
-------
METHOD 7040
ANTIMONY (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 In the presence of lead (1,000 mg/L), a spectral interference may
occur at the 217.6-nm resonance line. In this case, the 231.1-nm antimony
line should be used.
3.3 Increasing the acid concentrations decreases the antimony
absorption. To avoid this effect, the acid concentration in the samples and
in the standards should be matched.
3.4 Excess concentrations of copper and nickel (and possibly other
elements), as well as acids, can interfere with antimony analyses. If the
sample contains these matrix types, either matrices of the standards should be
matched to those of the sample or the sample should be analyzed using a
nitrous oxide/acetylene flame.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Antimony hollow cathode lamp or electrode!ess discharge lamp.
4.2.2 Wavelength: 217.6 nm (primary); 231.1 nm (secondary).
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Air.
4.2.5 Type of flame: Fuel lean.
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
7040 - 1
Revision 0
Date September 1986
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5.2 Preparation of standards;
5.2.1 Stock solution: Carefully weigh 2.7426 g of antimony
potassium tartrate, K(SbO)C4H406* 1/2^0 (analytical reagent grade), and
dissolve in Type II water. Dilute to 1 liter with Type II water; 1 ml =
1 mg Sb (1,000 mg/L). Alternatively, procure a certified standard from a
supplier and verify 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 contain 0.2% (v/v) HN03 and 1-2% v/v HC1, prepared using the same
types of acid and at the same concentrations as in the sample after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Method 3005. Method 3005, a soft digestion, is presently the
only digestion procedure recommended for Sb. It yields better recoveries than
either Method 3010 or Method 3050. There 1s no hard digestion for Sb at this
time.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration Procedure.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 1-40 mg/L with a wavelength of 217.6 nm.
Sensitivity: 0.5 mg/L.
Detection limit: 0.2 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 5.0 and 15 mg
Sb/L gave the standard deviations of +0.08 and +0.1, respectively. Recoveries
at these levels were 96% and 97%, respectively.
9.3 For concentrations of antimony below 0.35 mg/L, the furnace
procedure (Method 7041) is recommended.
7040 - 2
Revision 0
Date September 1986
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10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 204.1.
7040 - 3
Revision
Date September 1986
-------
METHOD 70*0
ANTIMONY (ATOMIC ABSORPTION. DIRECT ASPIRATION)
I Start J
5
.0
Prepare
standards
7.1
prepar
ch
sect!
For
sample
ation-
apter
on 3.1
sea
3.
.3
7.Z
Analyza using
Method 7000.
Section 7.a
f Stop J
7040 - 4
Revision 0
Date September 1986
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METHOD 7041
ANTIMONY (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000 1f interferences are suspected.
3.2 High lead concentration may cause a measurable spectral interference
on the 217.6-nm line. If this interference is expected, the secondary
wavelength should be employed or Zeeman background correction used.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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: 217.6 nm (primary); 231.1 nm (alternate).
4.2.6 Background correction: Required.
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
sizes of 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.
7041 - 1
Revision
Date September 1986
-------
5.2 Preparation of standards;
5.2.1 Stock solution: Carefully weigh 2.7426 g of antimony
potassium tartrate (analytical reagent grade) and dissolve in Type II
water. Dilute to 1 liter with Type II water; 1 mL = 1 mg Sb
(1,000 mg/L). Alternatively, procure a certified standard from a
supplier and verify 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 contain 0.2% (v/v) HN03 and 1-2% (v/v) HCl, prepared using the
same types of acid and at the same concentrations as in the sample after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparat1on; The procedures for preparation of the sample
are given in Method 3005.Method 3005, a soft digestion, is presently the
only digestion procedure recommended for Sb. It yields better recoveries than
either Method 3010 or Method 3050. There 1s no hard digestion for Sb at this
time.
NOTE: The addition of HCl acid to the digestate prevents the furnace
analysis of this digestate for many other metals.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
is given in Method 7000, Paragraph 7.4.
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.
9.2 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 20-300 ug/L.
Detection limit: 3 ug/L.
7041 - 2
Revision
Date September 1986
-------
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 204.2.
7041 - 3
Revision
Date September 1986
-------
METHOD 7O41
ANTIMONY (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
f Start j
5.0
Prepare
standards
7.1
prepar
ct
sec
For
cample
•atton seo
apter -3.
tlon 3.2
7.2
Analyze using
Method 7000.
Section 7.3.
calculation 7.4
f Stop J
7041 - 4
Revision 0
Date September 1986
-------
METHOD 7060A
ARSENIC (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 Method 7060 is an atomic absorption procedure approved for
determining the concentration of arsenic in wastes, mobility procedure extracts,
soils, and ground water. All samples must be subjected to an appropriate
dissolution step prior to analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis by Method 7060, samples must be prepared in order
to convert organic forms of arsenic to inorganic forms, to minimize organic
interferences, and to convert the sample to a suitable solution for analysis.
The sample preparation procedure varies depending on the sample matrix. Aqueous
samples are subjected to the acid digestion procedure described in this method.
Sludge samples are prepared using the procedure described in Method 3050.
2.2 Following the appropriate dissolution of the sample, a representative
aliquot of the digestate is spiked with a nickel nitrate solution and is placed
manually or by means of an automatic sampler into a graphite tube furnace. The
sample aliquot is then slowly evaporated to dryness, charred (ashed), and
atomized. The absorption of hollow cathode or EDL radiation during atomization
will be proportional to the arsenic concentration. Other modifiers may be used
in place of nickel nitrate if the analyst documents the chemical and
concentration used.
2.3 The typical detection limit for water samples using this method is
1 ug/L. This detection limit may not be achievable when analyzing waste samples.
3.0 INTERFERENCES
3.1 Elemental arsenic and many of its compounds are volatile; therefore,
samples may be subject to losses of arsenic during sample preparation. Spike
samples and relevant standard reference materials should be processed to
determine if the chosen dissolution method is appropriate.
3.2 Likewise, caution must be employed during the selection of
temperature and times for the dry and char (ash) cycles. A matrix modifier such
as nickel nitrate must be added to all digestates prior to analysis to minimize
volatilization losses during drying and ashing.
3.3 In addition to the normal interferences experienced during graphite
furnace analysis, arsenic analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix components during atomization. Arsenic
analysis is particularly susceptible to these problems because of its low
analytical wavelength (193.7 nm). Simultaneous background correction must be
employed to avoid erroneously high results. Aluminum is a severe positive
interferent in the analysis of arsenic, especially using D2 arc background
7060A - 1 Revision 1
September 1994
-------
correction. Although Zeeman background correction is very useful in this
situation, use of any appropriate background correction technique is acceptable.
3.4 If the analyte is not completely volatilized and removed from the
furnace during atomization, memory effects will occur. If this situation is
detected by means of blank burns, the tube should be cleaned by operating the
furnace at full power at regular intervals in the analytical scheme.
4.0 APPARATUS AND MATERIALS
4.1 Griffin beaker or equivalent: 250 ml.
4.2 Class A Volumetric flasks: 10-mL.
4.3 Atomic absorption spectrophotometer: Single or dual channel, single-
or double-beam instrument having a grating monochromator, photo-multiplier
detector, adjustable slits, a wavelength range of 190 to 800 nm, and provisions
for simultaneous background correction and interfacing with a suitable recording
device.
4.4 Arsenic hollow cathode lamp, or electrodeless discharge lamp (EDL):
EDLs provide better sensitivity for arsenic analysis.
4.5 Graphite furnace: Any graphite furnace device with the appropriate
temperature and timing controls.
4.6 Data systems recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any problems
with the analysis such as drift, incomplete atomization, losses during charring,
changes in sensitivity, etc., can easily be recognized.
4.7 Pipets: Microliter with disposable tips. Sizes can range from
5 to 1,000 uL, as required.
5.0 REAGENTS
5.1 Reagent water: Water should be monitored for impurities.
All references to water will refer to reagent water.
5.2 Concentrated nitric acid: Acid should be analyzed to determine levels
of impurities. If a method blank using the acid is
-------
5.5 Nickel nitrate solution (5%): Dissolve 24.780 g of ACS reagent grade
Ni(N03)26H20 or equivalent in reagent water and dilute to 100 mL.
5.6 Nickel nitrate solution (1%): Dilute 20 ml of the 5% nickel nitrate
to 100 mL with reagent water.
5.7 Arsenic working standards: Prepare dilutions of the stock solution
to be used as calibration standards at the time of the analysis. Withdraw
appropriate aliquots of the stock solution, add concentrated HN03, 30% H202, and
5% nickel nitrate solution or other appropriate matrix modifier. Amounts added
should be representative of the concentrations found in the samples. Dilute to
100 ml with reagent water.
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
reagent water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used if very volatile arsenic compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric acid and
refrigerated prior to analysis.
6.5 Although waste samples do not need to be refrigerated sample handling
and storage must comply with the minimum requirements established in Chapter One.
7.0 PROCEDURE
7.1 Sample preparation: Aqueous samples should be prepared in the manner
described in Paragraphs 7.1.1-7.1.3. Sludge-type samples should be prepared
according to Method 3050A. The applicability of a sample-preparation technique
to a new matrix type must be demonstrated by analyzing spiked samples and/or
relevant standard reference materials.
7.1.1 Transfer a known volume of well-mixed sample to a 250-mL
Griffin beaker or equivalent; add 2 mL of 30% H202 and sufficient
concentrated HN03 to result in an acid concentration of 1% (v/v). Heat,
until digestion is complete, at 95°C or until the volume is slightly less
than 50 mL.
7.1.2 Cool, transfer to a volumetric flask, and bring back to 50
mL with reagent water.
7.1.3 Pipet 5 mL of this digested solution into a 10-mL volumetric
flask, add 1 mL of the 1% nickel nitrate solution or other appropriate
matrix modifier, and dilute to 10 mL with reagent water. The sample is
now ready for injection into the furnace.
7060A - 3 Revision 1
September 1994
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7.2 The 193.7-nm wavelength line and a background correction system are
required. Follow the manufacturer's suggestions for all other spectrophotometer
parameters.
7.3 Furnace parameters suggested by the manufacturer should be employed
as guidelines. Because temperature-sensing mechanisms and temperature
controllers can vary between instruments or with time, the validity of the
furnace parameters must be periodically confirmed by systematically altering the
furnace parameters while analyzing a standard. In this manner, losses of analyte
due to overly high temperature settings or losses in sensitivity due to less than
optimum settings can be minimized. Similar verification of furnace parameters
may be required for complex sample matrices.
7.4 Inject a measured microliter aliquot of sample into the furnace and
atomize. If the concentration found is greater than the highest standard, the
sample should be diluted in the same acid matrix and reanalyzed. The use of
multiple injections can improve accuracy and help detect furnace pipetting
errors.
8.0 QUALITY CONTROL
8.1 Refer to section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 206.2 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The optimal concentration range for aqueous samples using this method
is 5-100 ug/L. Concentration ranges for non-aqueous samples will vary with
matrix type.
9.3 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 206.2.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7060A - 4 Revision 1
September 1994
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Contaminated soil 3050 2.0, 1.8 ug/g
Oily soil 3050 3.3, 3.8 ug/g
NBS SRM 1646 Estuarine sediment 3050 8.1, 8.33 ug/ga
Emission control dust 3050 430, 350 ug/g
aBias of -30 and -28% from expected, respectively.
7060A - 5 Revision 1
September 1994
-------
METHOD 7060A
ARSENIC (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
7.1.1 Tranafer
•aaple to
beaker,add H.O.
and cane. HNO.,
heat
7.1 Prepare
aaaplea
according to
Method 3050
7.1.2 Cool
and bring to
voluM with
reagent water
7.1.3 Pipet
aolution into
fla«k, add
nickel nitrate,
dilute
7.2 Set up
inatruaent
operating
parameter
7.3
Periodically
verify
furnace
paraa>eter*
7.4 Inject
aliquot of
aaaple into
furnace,
atoaite
7.4 Beeord A»
eeneentration
7 4 Dilute
aajiple and
reanalyze
Stop
7060A - 6
Revision 1
September 1994
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METHOD 7061A
ARSENIC (ATOMIC ABSORPTION, GASEOUS HYDRIDE)
1.0 SCOPE AND APPLICATION
1.1 Method 7061 is an atomic absorption procedure for determining the
concentration of arsenic in wastes, mobility procedure extracts, soils, and
ground water. Method 7061A is approved only for sample matrices that do not
contain high concentrations of chromium, copper, mercury, nickel, silver, cobalt,
and molybdenum. All samples must be subjected to an appropriate dissolution step
prior to analysis. Spiked samples and relevant standard reference materials are
employed to determine the applicability of the method to a given waste.
2.0 SUMMARY OF METHOD
2.1 Samples are prepared according to the nitric/sulfuric acid digestion
procedure described in this method (Step 7.1). Next, the arsenic in the
digestate is reduced to the trivalent form with tin chloride. The trivalent
arsenic is then converted to a volatile hydride using hydrogen produced from a
zinc/hydrochloric acid reaction.
2.2 The volatile hydride is swept into an argon-hydrogen flame located
in the optical path of an atomic absorption spectrophotometer. The resulting
absorption of the lamp radiation is proportional to the arsenic concentration.
2.3 The typical detection limit for this method is 0.002 mg/L.
3.0 INTERFERENCES
3.1 High concentrations of chromium, cobalt, copper, mercury, molybdenum,
nickel, and silver can cause analytical interferences.
3.2 Traces of nitric acid left following the sample work-up can result
in analytical interferences. Nitric acid must be distilled off by heating the
sample until fumes of sulfur trioxide (S03) are observed.
3.3 Elemental arsenic and many of its compounds are volatile; therefore,
certain samples may be subject to losses of arsenic during sample preparation.
4.0 APPARATUS AND MATERIALS
4.1 Beaker or equivalent - 100-mL.
4.2 Electric hot plate or equivalent - adjustable and capable of
maintaining a temperature of 90-95°C.
7061A - 1 Revision 1
July 1992
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4.3.1 Medicine dropper - Capable of fitting into a size "0" rubber
stopper and delivering 1.5 ml.
4.3.2 Pear-shaped reaction flask - 50-mL, with two 14/20 necks
(Scientific Glass JM-5835 or equivalent).
4.3.3 Gas inlet-outlet tube - Constructed from a micro cold-finger
condenser (JM-3325) by cutting the portion below the 14/20 ground-glass
joint.
4.3.4 Magnetic stirrer - To homogenize the zinc slurry.
4.3.5 Polyethylene drying tube - 10-cm, filled with glass to
prevent particulate matter from entering the burner.
4.3.6 Flow meter - Capable of measuring 1 liter/min.
4.3.7 Class A volumetric flasks.
4.3.8 Graduated cylinder or equivalent.
4.4 Atomic absorption spectrophotometer - Single or dual channel, single-
or double-beam instrument having a grating monochromator, photo-multiplier
detector, adjustable slits, a wavelength range of 190 to 800 nm, and provisions
for interfacing with a strip-chart recorder.
4.5 Burner - Recommended by the particular instrument manufacturer for
the argon-hydrogen flame.
4.6 Arsenic hollow cathode lamp or arsenic electrodeless discharge lamp.
4.7 Strip-chart recorder.
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 will be interferent free. All
references to water in the method refer to reagent water unless otherwise
specified.
5.3 Nitric acid (concentrated), HNO,. Acid should be analyzed to
determine levels of impurities. If a methoa blank is < MDL, the acid can be
used.
7061A - 2 Revision 1
July 1992
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5.4 Sulfuric acid (concentrated), H2S04. Acid should be analyzed to
determine levels of impurities. If a method blank is < MDL, the acid can be
used.
5.5 Hydrochloric acid (concentrated), HC1. Acid should be analyzed to
determine levels of impurities. If a method blank is < MDL, the acid can be
used.
5.6 Diluent - Add 100 ml 18N H2SO, and 400 ml concentrated HC1 to 400 ml
water and dilute to a final volume of 1 liter with water.
5.7 Potassium iodide solution - Dissolve 20 g KI in 100 mL water.
5.8 Stannous chloride solution - Dissolve 100 g SnCl2 in 100 ml
concentrated HC1.
5.9 Arsenic solutions
5.9.1 Arsenic standard solution (1,000 mg/L) - Either procure a
certified aqueous standard from a supplier and verify by comparison with
a second standard, or dissolve 1.320 g of arsenic trioxide As203 in 100 ml
of water containing 4 g NaOH. Acidify the solution with 20 ml
concentrated HN03 and dilute to 1 liter.
5.9.2 Intermediate arsenic solution - Pipet 1 ml stock arsenic
solution into a 100-mL volumetric flask and bring to volume with water
containing 1.5 ml concentrated HN03/liter (1 ml = 10 ug As).
5.9.3 Standard arsenic solution - Pipet 10 ml intermediate arsenic
solution into a 100-mL volumetric flask and bring to volume with water
containing 1.5 mL concentrated HN03/liter (1 mL = 1 ug As).
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.
6.3 Special containers (e.g. containers used for volatile organic
analysis) may have to be used if very volatile arsenic compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of < 2 with nitric acid.
6.5 Nonaqueous samples shall be refrigerated, when possible, and analyzed
as soon as possible.
7061A - 3 Revision 1
July 1992
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7.0 PROCEDURE
7.1 Place a 50-mL aliquot of digested sample (or, in the case of analysis
of EP extracts, 50 ml) of the material to be analyzed in a 100-mL beaker. Add
10 ml concentrated HNO, and 12 mL 18N H2S04. Evaporate the sample in the hood
on an electric hot plate until white SO, fumes are observed (a volume of about
20 mL). Do not let the sample char. If charring occurs, immediately turn off
the heat, cool, and add an additional 3 ml of HN03. Continue to add additional
HN03 in order to maintain an excess (as evidenced by the formation of brown
fumes). Do not let the solution darken, because arsenic may be reduced and lost.
When the sample remains colorless or straw yellow during evolution of S03 fumes,
the digestion is complete. Cool the sample, add about 25 ml water, and again
evaporate until S03 fumes are produced in order to expel oxides of nitrogen.
Cool. Transfer the digested sample to a 100-mL volumetric flask. Add 40 ml of
concentrated HC1 and bring to volume with water.
7.2 Prepare working standards from the standard arsenic solution.
Transfer 0, 0.5, 1.0, 1.5, 2.0, and 2.5 mL of standard to 100-mL volumetric
flasks and bring to volume with diluent. These concentrations will be 0, 5, 10,
15, 20, and 25 ug As/liter.
7.3 If EP extracts are being analyzed or if a matrix interference is
encountered, take the 15-, 20-, and 25-mg/liter standards and quantitatively
transfer 25 mL of each of these standards into separate 50-mL volumetric flasks.
Add 10 mL of the prepared sample to each flask. Bring to volume with water
containing 1.5 mL HCl/liter.
7.4 Add 10 mL of prepared sample to a 50-mL volumetric flask. Bring to
volume with water containing 1.5 mL HCl/liter. This is the zero addition
aliquot.
NOTE: The absorbance from the zero addition aliquot will be one-fifth that
produced by the prepared sample. The absorbance from the spiked
samples will be one-half that produced by the standards plus the
contribution from one-fifth of the prepared sample. Keeping these
absorbances in mind will assist in judging the correct dilutions to
produce optimum absorbance.
7.5 Transfer a 25-mL portion of the digested sample or standard to the
reaction vessel and add 1 mL KI solution. Add 0.5 mL SnCl2 solution. Allow at
least 10 minutes for the metal to be reduced to its lowest oxidation state.
Attach the reaction vessel to the special gas inlet-outlet glassware. Fill the
medicine dropper with 1.50 mL zinc slurry that has been kept in suspension with
the magnetic stirrer. Firmly insert the stopper containing the medicine dropper
into the side neck of the reaction vessel. Squeeze the bulb to introduce the
zinc slurry into the sample or standard solution. The metal hydride will produce
a peak almost immediately. After the recorder pen begins to return to the base
line, the reaction vessel can be removed.
CAUTION: Arsine is very toxic. Precautions must be taken to avoid
inhaling arsine gas.
7061A - 4 Revision 1
July 1992
-------
7.6 Use the 193.7-nm wavelength and background correction for the
analysis of arsenic.
7.7 Follow the manufacturer's instructions for operating an argon-
hydrogen flame. The argon-hydrogen flame is colorless; therefore, it may be
useful to aspirate a low concentration of sodium to ensure that ignition has
occurred.
7.8 If the method of standard additions was employed, plot the
absorbances of spiked samples and blank vs. the concentrations. The extrapolated
value will be one-fifth the concentration of the original sample. If the plot
does not result in a straight line, a nonlinear interference is present. This
problem can sometimes be overcome by dilution or addition of other reagents if
there is some knowledge about the waste. If the method of standard additions was
not required, then the concentration can be part of the calibration curve.
8.0 QUALITY CONTROL
8.1 Refer to section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 206.3 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods For Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 206.3.
2. Rohrbough, W.G.; et al. Reagent Chemicals, American Chemical Society
Specifications, 7th ed.; American Chemical Society: Washington, DC, 1986.
3. 1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
7061A - 5 Revision 1
July 1992
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METHOD 7061A
ARSENIC (ATOMIC ABSORPTION, GASEOUS HYDRIDE)
7.1 Turn off
heat,cool,
and add HNO.
7.3 Tr«n»fer
standard* to
flask*,add
•ample,bring
to volume
C Start J
7.1 Place
aliquot of
dige*ted
•ample in
beaker
7.1 Add
concentrated
HNO, and H.SO.;
evaporate
•ample
7.1 Continue
adding HNO.
to complete
digestion
7.1 Cool
•ample,add
reagent H,0,
evaporate,cool
7.1 Transfer
digested *ample
to flaik.add
cone HC1,bring
to volume
7 . 2 Prepare
stand*
irds .
transfer to
flasks
bring
to volume
7 4 Add
prepared samplt
to flask,bring
to volume,use
a* blank
7.S Transfer
portion of
digested sample
or standard to
reaction vessel
7.5 Add KI
solution, and
SnCl,
solution
7.5 Reduce
metal to its
lowest
oxidation
state
7.5 Attach
vessel to gas
glassware,fill
dropper with Zn
s1urry
7.S Introduce
Zn slurry
into sample
or standard
solution
7 6 Use
193.7-nm wave-
length and
background
correction
7.7 To operate
argon hydrogen
flame,follow
manufacturer
instructions
method of
•tandard
addition
u*ed?
7.8 Plot
abaorbanee* of
•piked (ample*
blank v*.
concentration*
7.8 Have
concentration
be part of
calibration
c
Stop
7061A - 6
Revision 1
July 1992
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METHOD 7062
ANTIMONY AND ARSENIC (ATOMIC ABSORPTION, BOROHYDRIDE REDUCTION)
1.0 SCOPE AND APPLICATION
1.1 Method 7062 is an atomic absorption procedure for determining 1 jjg/l
to 400//g/L concentrations of antimony and arsenic in wastes, mobility procedure
extracts, soils, and ground water. Method 7062 is approved for sample matrices
that contain up to a total of 4000 mg/L concentrations of cobalt, copper, iron,
mercury, or nickel. A solid sample can contain up to 40% by weight of the
interferents before exceeding 4000 mg/L in a digested sample. All samples
including aqueous matrices must be subjected to an appropriate dissolution step
prior to analysis. Spiked samples and relevant standard reference materials are
used to determine the applicability of the method to a given waste.
2.0 SUMMARY OF METHOD
2.1 Samples are prepared according to the nitric acid digestion procedure
described in Method 3010 for aqueous and extract samples and the
nitric/peroxide/hydrochloric acid digestion procedure described in Method 3050
(furnace AA option) for sediments, soils, and sludges. Excess peroxide is
removed by evaporating samples to near dryness at the end of the digestion
followed by degassing the samples upon addition of urea. L-cysteine is then
added as a masking agent. Next, the antimony and arsenic in the digest are
reduced to the trivalent forms with potassium iodide. The trivalent antimony and
arsenic are then converted to volatile hydrides using hydrogen produced from the
reaction of the acidified sample with sodium borohydride in a continuous-flow
hydride generator.
2.2 The volatile hydrides are swept into, and decompose in, a heated
quartz cell located in the optical path of an atomic absorption
spectrophotometer. The resulting absorption of the lamp radiation is
proportional to the arsenic or antimony concentration.
2.3 The typical detection limit for this method is l.Opg/L.
3.0 INTERFERENCES
3.1 Very high (>4000 mg/L) concentrations of cobalt, copper, iron,
mercury, and nickel can cause analytical interferences through precipitation as
reduced metals and associated blockage of transfer lines and fittings.
3.2 Traces of peroxides left following the sample work-up can result in
analytical interferences. Peroxides must be removed by evaporating each sample
to near dryness followed by reaction with urea and allowing sufficient time for.
degassing before analysis (see Sections 7.1 and 7.2).
7062-1 Revision 0
September 1994
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3.3 Even after acid digestion, organic compounds will remain in the
sample. These flame gases and these organic compounds can absorb at the
analytical wavelengths and background correction must be used.
4.0 APPARATUS AND MATERIALS
4.1 Electric hot plate: Large enough to hold at least several 100 mL
Pyrex digestion beakers.
4.2 A continuous-flow hydride generator: A commercially available
continuous-flow sodium borohydride/HCl hydride generator or a generator
constructed similarly to that shown in Figure 1 (P. S. Analytical or equivalent).
4.2.1 Peristaltic Pump: A four-channel, variable-speed peristaltic
pump to permit regulation of liquid-stream flow rates (Ismatec Reglo-100
or equivalent). Pump speed and tubing diameters should be adjusted to
provide the following flow rates: sample/blank flow = 4.2 mL/min;
borohydride flow = 2.1 mL/min; and potassium iodide flow = 0.5 mL/min.
4.2.2 Sampling Valve (optional): A sampling valve (found in the
P. S. Analytical Hydride Generation System or equivalent) that allows
switching between samples and blanks (rinse solution) without introduction
of air into the system will provide more signal stability.
4.2.3 Transfer Tubing and Connectors: Transfer tubing (1 mm I.D.),
mixing T's, and connectors are made of a fluorocarbon (PFA or TFM) and are
of compatible sizes to form tight, leak-proof connections (Latchat,
Technicon, etc. flow injection apparatus accessories or equivalent).
4.2.4 Mixing Coil: A 20-turn coil made by wrapping transfer tubing
around a 1-cm diameter by 5-cm long plastic or glass rod (see Figure 1).
4.2.5 Mixing Coil Heater, if appropriate: A 250-mL Erlenmeyer
flask containing 100 mL of water heated to boiling on a dedicated one-
beaker hotplate (Corning PC-35 or equivalent). The mixing coil in 4.2.4
is immersed in the boiling water to speed kinetics of the hydride forming
reactions and increase solubility of interfering reduced metal
precipitates.
4.2.6 Gas-Liquid Separator: A glass apparatus for collecting and
separating liquid and gaseous products (P.T. Analytical accessory or
equivalent) which allows the liquid fraction to drain to waste and gaseous
products above the liquid to be swept by a regulated carrier gas (argon)
out of the cell for analysis. To avoid undue carrier gas dilution, the
gas volume above the liquid should not exceed 20 mL. See Figure 1 for an
acceptable separator shape.
4.2.7 Condenser: Moisture picked up by the carrier gas must be
removed before encountering the hot absorbance cell. The moist carrier
gas with the hydrides is dried by passing the gasses through a small (< 25
7062-2 Revision 0
September 1994
-------
ml) volume condenser coil (Ace Glass Model 6020-02 or equivalent) that is
cooled to 5°C by a water chiller (Neslab RTE-110 or equivalent). Cool tap-
water in place of a chiller is acceptable.
4.2.8 Flow Meter/Regulator: A meter capable of regulating up to 1
L/min of argon carrier gas is recommended.
4.3 Absorbance Cell: A 17 cm or longer quartz tube T-cell (windowless is
strongly suggested) is recommended, as shown in Figure 1 (Varian Model VGA-76
accessory or equivalent). The cell is held in place by a holder that positions
the cell about 1 cm over a conventional AA air-acetylene burner head. In
operation, the cell is heated to around 900°C.
4.4 Atomic absorption spectrophotometer: Single or dual channel, single-
or double-beam instrument having a grating monochromator, photomultiplier
detector, adjustable slits, a wavelength range of 190 to 800 nm, and provisions
for interfacing with an appropriate recording device.
4.5 Burner: As recommended by the particular instrument manufacturer for
an air-acetylene flame. An appropriate mounting bracket attached to the burner
that suspends the quartz absorbance cell between 1 and 2 cm above the burner slot
is required.
4.6 Antimony and arsenic hollow cathode lamps or antimony and arsenic
electrodeless discharge lamps and power supply. Super-charged hollow-cathode
lamps or EDL lamps are recommended for maximum sensitivity.
4.7 Strip-chart recorder (optional): Connect to output of
spectrophotometer.
5.0 REAGENTS
5.1 Reagent water: Water must be monitored for impurities. Refer to
Chapter 1 for definition of Reagent water.
5.2 Concentrated nitric acid (HN03): Acid must be analyzed to determine
levels of impurities. If a method blank is
-------
QUARTZ CELL
A A BURNER
TO
CHILLER
DISCONNECTED)
OURI NO S*/8n
... ftMALYJIS J
OM/L1QUIO
SEPARATOR
_—» DRAIN
20 TORN COIL
(TEFLON)
HOTPLATE-
MALWt
(•LANK)
Figure 1. Continuous-flow sodium borohydride/hydride generator apparatus set-up
and an AAS sample introduction system.
7062-4
Revision 0
September 1994
-------
5.6 Urea (H2NCONH2): A 5.00-g portion of reagent grade urea must be added
to a 25-mL aliquot of each sample for removal of excess peroxide through
degassing (see Section 7.2).
5.7 L-cysteine (C6H12N204S2): A 1.00-g portion of reagent grade L-cystine
must be added to a 25-mL aliquot of each sample for masking the effects of
suppressing transition metals (see Section 7.2).
5.8 20% Potassium iodide (KI): A 20% KI solution (20 g reagent-grade KI
dissolved and brought to volume in 100 ml reagent water) must be prepared for
reduction of antimony and arsenic to their +3 valence states.
5.9 4% Sodium borohydride (NaBH4): A 4% sodium borohydride solution (20
g reagent-grade NaBH4 plus 2 g sodium hydroxide dissolved in 500 ml of reagent
water) must be prepared for conversion of the antimony and arsenic to their
hydrides.
5.10 Analyte solutions:
5.10.1 Antimony and arsenic stock standard solution (1,000 mg/L):
Either procure certified aqueous standards from a supplier and verify by
comparison with a second standard, or dissolve 1.197 g of antimony
trioxide Sb203 and 1.320 g of arsenic trioxide As203 in 100 ml of reagent
water containing 4 g NaOH. Acidify the solution with 20 ml concentrated
HN03 and dilute to 1 liter.
5.10.2 Intermediate antimony and arsenic solution: Pipet 1 ml
stock antimony and arsenic solution into a 100-mL volumetric flask and
bring to volume with reagent water containing 1.5 ml concentrated
HN03/liter (1 mL = 10 fjg each of Sb and As).
5.10.3 Standard antimony and arsenic solution: Pipet 10 mL
intermediate antimony and arsenic solution into a 100-mL volumetric flask
and bring to volume with reagent water containing 1.5 mL concentrated
HN03/liter (1 mL = 1 jjg each of Sb and As).
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
reagent water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used if very volatile antimony and arsenic compounds are
suspected to be present in the samples.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric acid.
7062-5 Revision 0
September 1994
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6.5 Nonaqueous samples shall be refrigerated, when possible, and analyzed
as soon as possible.
7.0 PROCEDURE
7.1 Place a 100-mL portion of an aqueous sample or extract or 1.000 g of
a dried solid sample in a 250-mL digestion beaker. Digest aqueous samples and
extracts according to Method 3010. Digest solid samples according to Method 3050
(furnace AA option) with the following modifications: add 5 ml of concentrated
hydrochloric acid just prior to the final volume reduction stage to aid in
antimony recovery; the final volume reduction should be to less than 5 ml but not
to dryness to adequately remove excess hydrogen peroxide (see note). After
dilution to volume, further dilution with diluent may be necessary if analytes
are known to exceed 400 fjg/l or if interferents are expected to exceed 4000 mg/L
in the digestate.
Note: For solid digestions, the volume reduction stage is critical
to obtain accurate data, especially for arsenic. Close monitoring
of each sample is necessary when this critical stage is reached.
7.2 Prepare samples for hydride analysis by adding 5.00 g urea, 1.00 g L-
cysteine, and 20 mL concentrated HC1 to a 25-mL aliquot of digested sample in a
50-mL volumetric flask. Heat in a water bath until the L-cysteine has dissolved
and effervescence has subsided (At least 30 minutes is suggested. If
effervescense is still seen, repeat step 7.1 with more volume reduction.). Bring
flask to volume with reagent water before analyzing. A 1:1 dilution correction
must be made in the final concentration calculations.
7.3 Prepare working standards from the standard antimony and arsenic
solution. Transfer 0, 0.5, 1.0, 1.5, 2.0, and 2.5 ml of standard to 100-mL
volumetric flasks and bring to volume with diluent. These concentrations will
be 0, 5, 10, 15, 20, and 25 //g Sb and As/liter.
7.4 If EP extracts (Method 1310) are being analyzed for arsenic, the
method of standard additions must be used. Spike appropriate amounts of
intermediate or standard antimony and arsenic solution to three 25 ml aliquots
of each unknown. Spiking volumes should be kept less than 0.250 ml to avoid
excessive spiking dilution errors.
7.5 Set up instrumentation and hydride generation apparatus and fill
reagent containers. The sample and blank flows should be set around 4.2 mL/min,
the borohydride flow around 2.1 mL/min, and the potassium iodide flow around 0.5
mL/min. The argon carrier gas flow is adjusted to about 200 mL/min. For the AA,
use the 217.6-nm wavelength and 0.7-nm slit width (or manufacturer's recommended
slit-width) without background correction if analyzing for antimony. Use the
193.7-nm wavelength and 0.7-nm slit width (or manufacturer's recommended slit-
width) with background correction for the analysis of arsenic. Begin all flows
and allow 10 minutes for warm-up.
7062-6 Revision 0
September 1994
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7.6 Place sample feed line into a prepared sample solution and start pump
to begin hydride generation. Wait for a maximum steady-state signal on the
strip-chart recorder or output meter. Switch to blank sample and watch for
signal to decline to baseline before switching to the next sample and beginning
the next analysis. Run standards first (low to high), then unknowns. Include
appropriate QA/QC solutions, as required. Prepare calibration curves and convert
absorbances to concentration. If a heating coil is not being used, KI must be
added to the samples and heated for thirty minutes to ensure reduction.
CAUTION: The hydrides of antimony and arsenic are very toxic.
Precautions must be taken to avoid inhaling the gas.
7.7 If the method of standard additions was employed, plot the measured
concentration of the spiked samples and unspiked sample versus the spiked
concentrations. The spiked concentration axis intercept will be the method of
standard additions concentration. If the plot does not result in a straight
line, a nonlinear interference is present. This problem can sometimes be
overcome by dilution or addition of other reagents if there is some knowledge
about the waste. If the method of standard additions was not required, then the
concentration is determined from a standard calibration curve.
8.0 QUALITY CONTROL
8.1 See section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The relative standard deviations obtained by a single laboratory for
7 replicates of a contaminated soil were 18% for antimony at 9.1 ug/L in solution
and 4.6% for arsenic at 68 ug/L in solution. The average percent recovery of the
analysis of an 8/yg/L spike on ten different samples is 103.7% for arsenic and
95.6% for antimony.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 206.3.
2. "Evaluation of Hydride Atomic Absorption Methods for Antimony, Arsenic,
Selenium, and Tin", an EMSL-LV internal report under Contract 68-03-3249,
Job Order 70.16, prepared for T. A. Hinners by D. E. Dobb, and J. D.
Lindner of Lockheed Engineering and Sciences Co., and L. V. Beach of the
Varian Corporation.
7062-7 Revision 0
September 1994
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METHOD 7062
ANTIMONY AND ARSENIC (ATOMIC ABSORPTION, BOROHYDRIDE REDUCTION)
7.1 Use Method
3050 (furnace AA
option) to digest
1.0 g sample.
7.1 Add
concentrated
HCI.
7.1 Do final
volume
reduction and
dilution, as
described
Yes
7.1 Further
dilute with
diluent.
7.2 Add to
aliquot urea:
L-cysteine, HCI:
heat H20 bath;
bring to volume.
7.3 Prepare
standards from
standard stock
solutions ot Sb
and As.
7.6 - 7.6 Analyze
the sample
using hydride
generation
apparatus.
7.6 • 7.7 Determine
Sb and As cone.
from standard
calibration
curve.
7.1 Use
Method 3010
to digest 100
ml sample.
7.4 Use the
method of
standard
additions on EP
extracts, only.
7.6 -7.6 Analyze
the sample
using hydride
generation
apparatus.
7.7 Determine
Sb and As
concentrations
by Method of
Standard Additions.
Stop
7062-8
Revision 0
September 1994
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METHOD 7080A
BARIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 High hollow cathode current settings and a narrow spectral band pass
must be used, because both barium and calcium emit strongly at barium's
analytical wavelength.
3.3 Barium undergoes significant ionization in the nitrous oxide/
acetylene flame, resulting in a significant decrease in sensitivity. All
samples and standards must contain a ionization suppressant. The type of
suppressant and concentration used must be documented.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Barium hollow cathode lamp.
4.2.2 Wavelength: 553.6 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxidant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards:
5.2.1 Stock solution: Dissolve 1.7787 g barium chloride
(BaCl22H20) analytical reagent grade in reagent water and dilute to 1
liter (1000 mg/L). Alternatively, procure a certified standard from a
supplier and verify 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
7080A - 1 Revision 1
September 1994
-------
should be prepared using the same type of acid and at the same
concentration as will result in the sample to be analyzed after
processing. All calibration standards and samples should contain the
ionization suppressant.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation: The procedures for preparation of the sample are
given in Chapter Three, Section 3.2.
7.2 See Method 7000, Section 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 1-20 mg/L with a wavelength of 553.6 nm.
Sensitivity: 0.4 mg/L.
Detection limit: 0.1 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic waste
effluent, digested with Method 3010, at concentrations of 0.4 and 2 mg Ba/L gave
standard deviations of +0.043 and ±0.13, respectively. Recoveries at these
levels were 94% and 113%, respectively.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 208.1.
7080A - 2 Revision 1
September 1994
-------
METHOD 7080A
BARIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
( Start J
5.2 Prepare
standards.
7.1 For sample
preparation see
Chapter 3, Section
3.2.
7.2 Analyze using
Method 7000
Section 7.2.
f Stop J
7080A - 3
Revision 1
September 1994
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METHOD 7081
BARIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000.
3.2 Barium is known to form a barium carbide in the graphite furnace.
This less volatile carbide can cause losses of sensitivity and memory effects.
3.3 The long residence time and the high concentration of the analyte in
the optical path of the graphite furnace can lead to severe physical and chemical
interferences. Furnace parameters must be optimized to minimize these effects.
3.4 Because of possible chemical interaction, nitrogen should not be used
as a purge gas.
3.5 Halide acids should not be used.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 1200°C.
4.2.3 Atomizing time and temp: 10 sec at 2800°C.
4.2.4 Purge gas: Argon (nitrogen should not be used).
4.2.5 Wavelength: 553.6 nm.
4.2.6 Background correction: Not required.
7081 - 1 Revision 0
July 1992
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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 - Dissolve 1.7787 g barium chloride
(BaCl2 2H20, analytical reagent grade) in water and dilute to 1 liter.
Alternatively, procure a certified standard from a supplier and verify 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
concentrations as in the sample after processing (0.5% v/v HN03).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Step 3.1.3, Sample Handling and Preservation.
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 ASSURANCE
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.
7081 - 2 Revision 0
July 1992
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10.0 REFERENCES
1. Methods for Chemical Analysis of Mater and Wastes; 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, 1983; EPA-600/4-79-020.
7081 - 3 Revision 0
July 1992
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METHOD 7081
BARIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
Start
5.0 Pr«par«
standard*
7 1 For aampla
preparation »••
Chaptar 3, Saetion
3.2
7 2 Analyza uung
M.lhod 700C
Section 7 3
Stop
7081 - 4
Revision 0
July 1992
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METHOD 7090
BERYLLIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Background correction may be required because nonspecific absorption
and light scattering can be significant at the analytical wavelength.
3.3 Concentrations of aluminum greater than 500 ppm may suppress
beryllium absorbance. The addition of 0.1% fluoride has been found effective
in eliminating this interference. High concentrations of magnesium and
silicon cause similar problems and require the use of the method of standard
additions.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Beryllium hollow cathode lamp.
4.2.2 Wavelength: 234.9 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 11.6586 g beryllium sulfate, BeSO^
in Type II water containing 2 mL nitric acid and dilute to 1 liter.
7090 - 1
Revision
Date September 1986
-------
Beryllium metal can also be dissolved 1n H2S04. Alternatively, procure a
certified standard from a supplier and verify 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 add and at the same
concentration as will result 1n the sample to be analyzed after
processing (0.5% v/v HMOs).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample Preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.05-2 mg/L with a wavelength of 234.9 nm.
Sensitivity: 0.025 mg/L.
Detection limit: 0.005 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 0.01 and 0.25
mg/L gave standard deviations of +0.001 and +0.002, respectively. Recoveries
at these levels were 100% and 97%, respectively.
9.3 For concentrations of beryllium below 0.02 mg/L, the furnace proce-
dure (Method 7091) is recommended.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 210.1.
7090 - 2
Revision
Date September 1986
-------
METHOD 709O
BERYLLIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
C
5.0
Prepare
standards
7.1
1 For
•ample
preparation see
chapter 3.
section 3.2
7.Z
Analyze ualng
Method 700O.
Section 7.2
f Stop J
7090 - 3
Revision 0
Date September 1986
-------
METHOD 7091
BERYLLIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 The long residence time and high concentrations of the atomized
sample in the optical path of the graphite furnace can result 1n severe
physical and chemical interferences. Furnace parameters must be optimized to
minimize these effects.
3.3 In addition to the normal interferences experienced during graphite
furnace analysis, beryllium analysis can suffer from severe nonspecific ab-
sorption and light scattering caused by matrix components during atomlzation.
Simultaneous background correction is required to avoid erroneously high
results.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 1000*C.
4.2.3 Atomizing time and temp: 10 sec at 2800*C.
4.2.4 Purge gas: Argon.
4.2.5 Wavelength: 234.9 nm.
4.2.6 Background correction: Required.
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
sizes of furnace devices or those employing faster rates of
atomization can be operated using lower atomlzation temperatures
for shorter time periods than the above-recommended settings.
7091 - 1
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 11.6586 g beryllium sulfate, BeS04,
In Type II water containing 2 ml concentrated nitric acid and dilute to
1 liter. Beryllium metal can also be dissolved in acid. Alternatively,
procure a certified standard from a supplier and verify by comparison
with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as cali-
bration standards at the time of analysis. The calibration standards
should be prepared using the same type of acid and at the same
concentrations as in the sample after processing (0.5% v/v HN03).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample Preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
is given in Method 7000, Paragraph 7.4.
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.
9.2 The performance characteristics for an aqueous sample free of inter-
ferences are;
Optimum concentration range: 1-30 ug/L.
Detection limit: 0.2 ug/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 210.2.
7091 - 2
Revision 0
Date September 1986
-------
METHOD 7091
BERYLLIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
Prepare
et*nderds
7.1
prepar
cl-
•ec
For '
•ample
•atlon aee
i»pter 3.
tlon 3.2
7.Z
Analyze using
Method 7000.
Section 7.3.
calculation 7.4
f Stop J
7091 - 3
Revision 0
Date September 1986
-------
METHOD 7130
CADMIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Nonspecific absorption and light scattering can be significant at
the analytical wavelength. Thus background correction is required.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Cadmium hollow cathode lamp.
4.2.2 Wavelength: 228.8 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g cadmium metal (analytical
reagent grade) in 20 mL of 1:1 HNOs and dilute to 1 liter with Type II
water. Alternatively, procure a certified standard from a supplier and
verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as cali-
bration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
7130 - 1
Revision
Date September 1986
-------
concentration as will result 1n the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.05-2 mg/L with a wavelength of 228.8 nm.
Sensitivity: 0.025 mg/L.
Detection Hm1t: 0.005 mg/L.
9.2 For concentrations of cadmium below 0.02 mg/L, the furnace procedure
(Method 7131) 1s recommended.
9.3 Precision and accuracy data are available 1n Method 213.1 of Methods
for Chemical Analysis of Water and Wastes.
9.4 The data shown 1n Table 1 were obtained from records of state and
contractor laboratories. The data are Intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 213.1.
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7130 - 2
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Emission control dust 3050 2,770, 1,590 ug/g
Wastewater treatment sludge 3050 12,000, 13,000 ug/g
7130 - 3
Revision
Date September 1986
-------
METHOD 7130
CADMIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
9.0
Prepare
atandards
7.1 1
1 For
•ample
preparation see
chapter 3.
section 3.2
7.2 {
Analyze using
Method 7000.
Section 7.2
f Stop J
7130 - 4
Revision 0
Date September 1986
-------
METHOD 7131A
CADMIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 In addition to the normal interferences experienced during graphite
furnace analysis, cadmium analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix components during atomization. Simultaneous
background correction is required to avoid erroneously high results.
3.3 Excess chloride may cause premature volatilization of cadmium.
Ammonium phosphate used as a matrix modifier minimizes this loss. Other
modifiers may be used as long as it is documented with the type of suppressant
and concentration.
3.4 Many plastic pipet tips (yellow) contain cadmium. Use "cadmium-
free" tips.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 500°C.
4.2.3 Atomizing time and temp: 10 sec at 1900°C.
4.2.4 Purge gas: Argon.
4.2.5 Wavelength: 228.8 nm.
4.2.6 Background correction: Required.
4.2.7 Other operating parameters should be set as specified by the
particular instrument manufacturer.
7131A - 1 Revision 1
September 1994
-------
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 sizes
of 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: Dissolve 1.000 g of cadmium metal
(analytical reagent grade) in 20 ml of 1:1 HN03 and dilute to 1 liter with
reagent water. Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock cadmium solution to be used
as calibration standards at the time of analysis. To each 100 ml of
standard and sample alike add 2.0 ml of the ammonium phosphate solution.
The calibration standards should be prepared to contain 0.5% (v/v) HN03.
5.2.3 Ammonium phosphate solution (40%): Dissolve 40 g of
ammonium phosphate, (NH4)2HP04 (analytical reagent grade), in reagent water
and dilute to 100 ml.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation: The procedures for preparation of the sample are
provided in Chapter Three, Section 3.2.
7.2 See Method 7000, Section 7.3, Furnace Procedure. The calculation is
provided in Method 7000, Section 7.4.
8.0 QUALITY CONTROL
8.1 Refer to Section 8.0 of Method 7000 .
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 213.2 of Methods
for Chemical Analysis of Water and Wastes.
7131A - 2 Revision 1
September 1994
-------
9.2 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 0.5-10 ug/L.
Detection limit: 0.1 ug/L.
9.3 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 213.2.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7131A - 3 Revision 1
September 1994
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Lagoon soil 3050 0.10, 0.095 ug/g
NBS SRM 1646 Estuarine sediment 3050 0.35 ug/ga
Solvent extract of oily waste 3030 1.39, 1.09 ug/L
aBias of -3% from expected value.
7131A - 4 Revision 1
September 1994
-------
METHOD 7131A
CADMIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
f Start J
>
f
5.2 Prepare
standards.
>
r
7. 1 For sample
preparation see
Chapter 3, Section
3.2.
>
t
7.2 Analyze using
Method 7000
Section 7.3.
>
\f
( Stop J
7131A - 5
Revision 1
September 1994
-------
METHOD 7140
CALCIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000.
3.2 All elements forming stable oxyanions (P, B, Si, Cr, S, V, Ti, Al,
etc.) will complex calcium and interfere unless lanthanum is added. Addition
of lanthanum to prepared samples rarely presents a problem because virtually
all environmental samples contain sufficient calcium to require dilution to be
in the linear range of the method.
3.3 P04, 504, and Al are interferents. High concentrations of Mg, Na,
and K interfere.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Calcium hollow cathode lamp.
4.2.2 Wavelength: 422.7 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Nitrous oxide.
4.2.5 Type of flame: Stoichiometric.
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Suspend 2.500 g of CaCOa (analytical reagent
grade, dried for 1 hr at 180*C) 1n Type II water and dissolve by adding a
7140 - 1
Revision
Date September 1986
-------
minimum of dilute HC1. Dilute to 1 liter with Type II water.
Alternatively, procure a certified standard from a supplier and verify 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
concentration as will result in the sample to be analyzed after
processing, including 1 ml of lanthanum chloride per 10 ml sample or
standard (see Paragraph 5.2.3).
5.2.3 Lanthanum chloride solution: Dissolve 29 g 13203 in 250 ml
concentrated HC1 -
CAUTION: REACTION IS VIOLENT -
and dilute to 500 mL with Type II water.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 215.1 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 0.2-7 mg/L with a wavelength of 422.7 nm.
Sensitivity: 0.08 mg/L.
Detection limit: 0.01 mg/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 215.1.
7140 - 2
Revision 0
Date September 1986
-------
METHOD 7140
CALCIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
f Start J
s.o
Prepare
standards
7.1
SI
preparat
chat
sect!
•or
imple
.Ion see
iter 3.
on 3.2
J.2 1
Analyze using
Method 7000.
Section 7.2
f Stop J
7140 - 3
Revision 0
Date September 1986
-------
METHOD 7190
CHROMIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 An ionization interference may occur if the samples have a signifi-
cantly higher alkali metal content than the standards. If this interference
is encountered, an ionization suppressant (KC1) should be added to both
samples and standards.
3.3 Background correction may be required because nonspecific absorption
and scattering can be significant at the analytical wavelength. Background
correction with certain instruments may be difficult at this wavelength due to
low-intensity output from hydrogen or deuterium lamps. Consult the specific
instrument manufacturer's literature for details.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Chromium hollow cathode lamp.
4.2.2 Wavelength: 357.9 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
7190 - 1
Revision
Date September 1986
-------
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.923 g of chromium trloxlde (003,
analytical reagent grade) 1n Type II water, acidify with redistilled
HN03, and dilute to 1 liter. Alternatively, procure a certified standard
from a supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as cali-
bration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentration as will result 1n the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given In Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
Interferences are;
Optimum concentration range: 0.5-10 mg/L with a wavelength of 357.9 nm.
Sensitivity: 0.25 mg/L.
Detection limit: 0.05 mg/L.
9.2 For concentrations of chromium below 0.2 mg/L, the furnace procedure
(Method 7191) 1s recommended.
9.3 Precision and accuracy data are available 1n Method 218.1 of Methods
for Chemical Analysis of Water and Wastes.
9.4 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
7190 - 2
Revision
Date September 1986
-------
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 218.1.
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7190 - 3
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Wastewater treatment sludge 3050 6,100, 6,000 ug/g
Emission control dust 3050 2.0, 2.8 ug/g
7190 - 4
Revision
Date September 1986
-------
METHOD 719O
CHROMIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
C
5.O
Prepare
•tandarda
7. 1
prepar
cf
• ec
For
•ample
•atlon sea
lapter 3,
:tion 3.2
7.2
Analyz« using
Method 7000.
Section 7.2
f Stop J
7190 - 5
Revision 0
Date September 1986
-------
METHOD 7191
CHROMIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Low concentrations of calcium and/or phosphate may cause
interferences; at concentrations above 200 mg/L, calcium's effect is constant
and eliminates the effect of phosphate. Calcium nitrate is therefore added to
ensure a known constant effect.
3.3 Nitrogen should not be used as the purge gas because of a possible
CN band interference.
3.4 Background correction may be required because nonspecific absorption
and scattering can be significant at the analytical wavelength. Background
correction with certain instruments may be difficult at this wavelength due to
low-intensity output from hydrogen or deuterium lamps. Consult the specific
instrument manufacturer's literature for details.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 1000'C.
4.2.3 Atomizing time and temp: 10 sec at 2700*C.
4.2.4 Purge gas: Argon (nitrogen should not be used).
4.2.5 Wavelength: 357.9 nm.
4.2.6 Background correction: Not required.
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,
7191 - 1
Revision 0
Date September 1986
-------
continuous-flow purge gas, and nonpyrolytic graphite. Smaller
sizes of furnace devices or those employing faster rates of
atomization can be operated using lower atomlzatlon 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: Dissolve 1.923 g of chromium tr1oxide (CrOs,
analytical reagent grade) 1n Type II water, acidify with redistilled
HN03, and dilute to 1 liter. Alternatively, procure a certified standard
from a supplier and verify 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. These standards should be
prepared to contain 0.5% (v/v) HN03; 1 ml of 30% ^2 and 1 ml of calcium
nitrate solution, Section 5.2.3, may be added to lessen interferences
(see Section 3.0).
5.2.3 Calcium nitrate solution: Dissolve 11.8 g of calcium
nitrate, Ca(N03)2*4H20 (analytical reagent grade), 1n Type II water and
dilute to 1 liter.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
is given in Method 7000, Paragraph 7.4.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 218.2 of Methods
for Chemical Analysis of Water and Wastes.
7191 - 2
Revision
Date September 1986
-------
9.2 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 5-100 ug/L.
Detection limit: 1 ug/L.
9.3 The data shown In Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 218.2.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7191 - 3
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sampl e
Matrix
Paint primer
Contaminated soil
Oily lagoon soil
NBS SRM 1646 Estuarine sediment
EPA QC Sludge
NBS SRM 1085, Wear Metals in
lubricating oil
Preparation
Method
3050
3050
3050
3050
3050
3050
Laboratory
Replicates
2.7, 2.8 mg/g
12.0, 12.3 ug/g
69.6, 70.3 ug/g
42, 47 ug/ga
156 ug/gb
311, 356 ug/gc
aBias of -45 and -38% from expected, respectively.
bfiias of -24% from expected.
cB1as of +4 and +19% from expected, respectively.
7191 - 4
Revision 0
Date September 1986
-------
METHOD 7191
CHROMIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
5
il
Prepare
atandarda
7.1
I For
aampla
preparation «e«
chapter 3.
aectlon 3.2
7.Z |
Analyze ualng
Method 7000.
Section 7.3.
calculation 7.4
f Stop J
7191 - 5
Revision 0
Date September 1986
-------
METHOD 7195
CHROMIUM, HEXAVALENT (COPRECIPITATION)
1.0 SCOPE AND APPLICATION
1.1 Method 7195 1s to be used to determine the concentration of dis-
solved hexavalent chromium [Cr(VI)] In Extraction Procedure (EP) toxlclty
characteristic extracts and ground waters. This method may also be applicable
to certain domestic and Industrial wastes, provided that no Interfering
substances are present (see Paragraph 3.1 below).
1.2 Method 7195 may be used to analyze samples containing more than 5 ug
of Cr(VI) per liter. Either flame or furnace atomic absorption spectroscopy
(Methods 7190 and 7191) can be used with copreclpltatlon.
2.0 SUMMARY OF METHOD
2.1 Method 7195 is based on the separation of Cr(VI) from solution by
coprecipltation of lead chromate with lead sulfate 1n a solution of acetic
add. After separation, the supernate [containing Cr(III)] is drawn off and
the precipitate is washed to remove occluded Cr(III). The Cr(VI) is then
reduced and resolubillzed in nitric acid and quantified as Cr(III) by either
flame or furnace atomic absorption spectroscopy (Methods 7190 and 7191).
3.0 INTERFERENCES
3.1 Extracts containing either sulfate or chloride 1n concentrations
above 1,000 mg/L should be diluted prior to analysis.
4.0 APPARATUS AND MATERIALS
4.1 Filtering flask; Heavy wall, 1-1 Her capacity.
4.2 Centrifuge tubes; Heavy duty, conical, graduated, glass-stoppered,
10-mL capacity.
4.3 Pasteur pipets; Borosilicate glass, 6.8 cm.
4.4 Centrifuge; Any centrifuge capable of reaching 2,000 rpm and
accepting the centrifuge tubes described in Section 4.2 may be used.
4.5 pH meter; A wide variety of instruments are commercially available
and suitable for this work.
4.6 Test tube mixer; Any mixer capable of imparting a thorough vortex
is acceptable.
7195 - 1
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Lead nitrate solution; Dissolve 33.1 g of lead nitrate, Pb(N03)2
(analytical reagent grade), in Type II water and dilute to 100 mL.
5.3 Ammonium sulfate solution; Dissolve 2.7 g of ammonium sulfate,
(analytical reagent grade), 1n Type II water and dilute to 100 ml.
5.4 Calcium nitrate solution; Dissolve 11.8 g of calcium nitrate,
*4H20 (analytical reagent grade), 1n Type II water and dilute to
100 ml (1 ml = 20 mg Ca) .
5.5 Nitric acid; Concentrated, distilled reagent grade or spectrograde
quality.
5.6 Acetic acid, glacial, 10% (v/v): Dilute 10 ml glacial acetic acid,
CH3COOH (ACS reagent grade), to 100 ml with Type II water.
5.7 Ammonium hydroxide, 10% (v/v); Dilute 10 ml concentrated ammonium
hydroxide, NH40H (analytical reagent grade), to 100 ml with Type II water.
5.8 Hydrogen peroxide, 30%; ACS reagent grade.
5.9 Potassium dichromate standard solution; Dissolve 28.285 g of dried
potassium dichromate, I^C^Oy (analytical reagent grade), in Type II water and
dilute to 1 liter (1 mL = 10 mg Cr).
5.10 Trivalent chromium working stock solution; To 50 ml of the potas-
sium dichromate standard solution, add 1 ml of 30% \\2®2 and 1 mL concentrated
HN03 and dilute to 100 ml with Type II water (1 ml = 5.0 mg trivalent chro-
mium). Prepare fresh monthly, or as needed.
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 Since the stability of Cr(VI) in EP extracts is not completely
understood at this time, the analysis should be carried out as soon as
possible.
6.3 To retard the chemical activity of hexavalent chromium, samples and
extracts should be stored at 4*C until analyzed. The maximum holding time
prior to analysis 1s 24 hr.
7195 - 2
Revision
Date September 1986
-------
7.0 PROCEDURE
7.1 Transfer a 50-mL portion of the sample to a 100-mL Griffin beaker
and adjust to a pH of 3.5 + 0.3 by adding volumes of 10% acetic acid dropwlse.
Proceed Immediately to Step 7.2, taking no longer than 15 mln between these
steps.
NOTE: Care must be exercised not to take the pH below 3. If the pH is
inadvertently lowered to <3, 10% NfyOH should be used to readjust
the pH to 3.5 + 0.3.
7.2 Pi pet a 10-mL aliquot of the adjusted sample into a centrifuge tube.
Add 100 uL of the lead nitrate solution, stopper the tube, mix the sample, and
allow to stand for 3 min.
7.3 After the formation of lead chromate, to help retain Cr(III) complex
in solution, add 0.5 ml glacial acetic acid, stopper, and mix.
7.4 To provide adequate lead sulfate for coprecipitation, add 100 uL of
ammonium sulfate solution, stopper, and mix.
7.5 Place the stoppered centrifuge tube in the centrifuge, making sure
that the tube is properly counterbalanced. Start the centrifuge and slowly
increase the speed to 2,000 rpm in small increments over a period of 5 min.
Hold at 2,000 rpm for 1 min.
NOTE: The speed of the centrifuge must be increased slowly to ensure
complete coprecipitation.
7.6 After centrifuging, remove the tube and withdraw and discard the
supernate using either the apparatus detailed in Figure 1 or careful
decantation. If using the vacuum apparatus, the pasteur pipet is lowered into
the tube and the supernate 1s sucked over into the filtering flask. With
care, the supernate can be withdrawn to within approximately 0.1 ml above the
precipitate. Wash the precipitate with 5 ml Type II water and repeat steps
7.5 and 7.6; then proceed to 7.7.
7.7 To the remaining precipitate, add 0.5 ml concentrated HN03, 100 uL
30% H202, and 100 uL calcium nitrate solution. Stopper the tube and mix,
using a vortex mixer to disrupt the precipitate and solubllize the lead
chromate. Dilute to 10 ml, mix, and analyze in the same manner as the
calibration standard.
7.8 Flame atomic absorption; At the time of analysis, prepare a blank
and a series of at leastfourcalibration standards from the Cr(III) working
stock that will adequately bracket the sample and cover a concentration range
of 1 to 10 mg Cr/L. Add to the blank and each standard, before diluting to
final volume, 1 ml 30% \\2®2, 5 ml concentrated HNOs, and 1 ml calcium nitrate
solution for each 100 ml of prepared solution. These calibration standards
should be prepared fresh weekly, or as needed. Refer to Method 7090 for more
detail.
7195 - 3
Revision 0
Date September 1986
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7.9 Furnace atomic absorption; At the time of analysis, prepare a blank
and a series of at leastfour calibration standards from the Cr(III) working
stock that will adequately bracket the sample and cover a concentration range
of 5 to 100 ug Cr/L. Add to the blank and each standard, before diluting to
final volume, 1 ml 30% ^03, 5 ml concentrated HN03, and 1 ml calcium nitrate
solution for each 100 ml of prepared solution. These calibration standards
should be prepared fresh weekly, or as needed. Refer to Method 7191 for more
detail.
7.10 Verification;
7.10.1 For every sample matrix analyzed, verification is required
to ensure that neither a reducing condition nor chemical interference is
affecting precipitation. This must be accomplished by analyzing a second
10-mL aliquot of the pH-adjusted filtrate that has been spiked with
Cr(VI). The amount of spike added should double the concentration found
in the original aliquot. Under no circumstance should the increase be
less than 30 ug/L Cr(VI). To verify the absence of an interference, the
spike recovery must be between 85% and 115%.
7.10.2 If addition of the spike extends the concentration beyond
the calibration curve, the analysis solution should be diluted with blank
solution and the calculated results adjusted accordingly.
7.10.3 If the result of verification indicates a suppressive
interference, the sample should be diluted and reanalyzed. If necessary,
use furnace atomic absorption to achieve the optimal concentration range.
7.10.4 If the interference persists after sample dilution, an
alternative method (Method 7197, Chelation/Extraction, or Method 7196,
Colorimetric) should be used.
7.11 Acidic extracts that yield recoveries of less than 85% should be
retested to determine if the low spike recovery is due to the presence of
residual reducing agent. This determination shall be performed by first
making an aliquot of the extract alkaline (pH 8.0-8.5) using 1 N sodium
hydroxide and then respiking and analyzing. If a spike recovery of 85-115% is
obtained in the alkaline aliquot of an acidic extract that initially was found
to contain less than 5 mg/L Cr(VI), one can conclude that the analytical
method has been verified.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
7195 - 4
Revision 0
Date September 1986
-------
8.3 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Verify calibration with an independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 10 samples. A duplicate
sample 1s a sample brought through the whole sample preparation and analytical
process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a del 1 sting petition, and whenever a new sample matrix is being
analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 218.5 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 218.5.
•
7195 - 5
Revision
Date September 1986
-------
METHOD 7195
HEXAVALENT CHROMIUM: COPRECIPITATION METHOD
7. 1
Transfer sample
to beaker;
adjust PH
7.2
7.6
Remove
tube; discard
supernate: wash
precipitate;
repeat 7.5. 7.6
Pipet adjusted cample
Into centrifuge tube;
add l«ad nitrate
solution: mix : let
stand
7.3
7.7
Add cone
1 HNOi.
SOX HjOz and
•calcium nitrate
solution: mix;
dilute: analyze
Add glacial
acetic acid;
mix
7.4
7.9
Prepare blank and
series of
standards covering
concentration range
or S to 100 ug
Cr/lUer
Add ammonium
sulfate
solution: mix
7.9
Furnace
Flame
Which type of
atomic absorption
is used?
7.8
Prepare blank and
series of
standards covering
concentration range
of 1 to 10 mg
Cr/liter
Add 30X
cone HNOj. and
calcium nitrate
solution to
each; analyze
7.e
Add 30X
H,0t.
cone HNOj and
calcium nitrate
solution to
each: analyze
7.3
Place tube in
centrifuge:
centrifuge
7.10.1
Verify
by analyzing
second aliquot
of spiked
filtrate
o
7195 - 6
Revision 0
Date September 1986
-------
METHOD 7195
HEXAVALENT CHROMIUM: COPHECIPITATION METHOD
(Continued)
^^i w
Is suppresslve >v
Interference
Indicated?
Dilute sample
and reanalyze
7.12 |
If no valid
results, and chromium
more than threshold
amount of hexavalent
chromium, sample
exihiblte EP toxiclty
Analytic
method
verified: waste
not hazardous
f Stop J
7195 - 7
Revision Q
Date September 1986
-------
METHOD 7196A
CHROMIUM, HEXAVALENT (COLORIMETRIC)
1.0 SCOPE AND APPLICATION
1.1 Method 7196 is used to determine the concentration of dissolved
hexavalent chromium [Cr(VI)] in EP/TCLP characteristic extracts and ground
waters. This method may also be applicable to certain domestic and industrial
wastes, provided that no interfering substances are present (see Paragraph 3.1
below).
1.2 Method 7196 may be used to analyze samples containing from 0.5 to
50 mg of Cr(VI) per liter.
2.0 SUMMARY OF METHOD
2.1 Dissolved hexavalent chromium, in the absence of interfering amounts
of substances such as molybdenum, vanadium, and mercury, may be determined
colorimetrically by reaction with diphenylcarbazide in acid solution. A red-
violet color of unknown composition is produced. The reaction is very sensitive,
the absorbancy index per gram atom of chromium being about 40,000 at 540 nm.
Addition of an excess of diphenylcarbazide yields the red-violet product, and its
absorbance is measured photometrically at 540 nm.
3.0 INTERFERENCES
3.1 The chromium reaction with diphenylcarbazide is usually free from
interferences. However, certain substances may interfere if the chromium
concentration is relatively low. Hexavalent molybdenum and mercury salts also
react to form color with the reagent; however, the red-violet intensities
produced are much lower than those for chromium at the specified pH.
Concentrations of up to 200 mg/L of molybdenum and mercury can be tolerated.
Vanadium interferes strongly, but concentrations up to 10 times that of chromium
will not cause trouble.
3.2 Iron in concentrations greater than 1 mg/L may produce a yellow
color, but the ferric iron color is not strong and difficulty is not normally
encountered if the absorbance is measured photometrically at the appropriate
wavelength.
4.0 APPARATUS AND MATERIALS
4.1 Colorimetric equipment: One of the following is required: Either
a spectrophotometer, for use at 540 nm, providing a light path of 1 cm or longer,
or a filter photometer, providing a light path of 1 cm or longer and equipped
with a greenish-yellow filter having maximum transmittance near
540 nm.
7196A - 1 Revision 1
July 1992
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5.0 REAGENTS
5.1 Reagent water: Reagent water should be monitored for
impurities.
5.2 Potassium dichromate stock solution: Dissolve 141.4 mg of dried
potassium dichromate, K2Cr,07 (analytical reagent grade), in reagent water and
dilute to 1 liter (1 ml = 50 ug Cr).
5.3 Potassium dichromate standard solution: Dilute 10.00 ml potassium
dichromate stock solution to 100 ml (1 ml = 5 ug Cr).
5.4 Sulfuric acid, 10% (v/v): Dilute 10 ml of distilled reagent grade
or spectrograde quality sulfuric acid, H2S04, to 100 ml with reagent water.
5.5 Diphenylcarbazide solution: Dissolve 250 mg 1,5-diphenylcarbazide
in 50 ml acetone. Store in a brown bottle. Discard when the solution becomes
discolored.
5.6 Acetone (analytical reagent grade): Avoid or redistill material that
comes in containers with metal or metal-lined caps.
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 Since the stability of Cr(VI) in extracts is not completely
understood at this time, the analysis should be carried out as soon as possible.
6.3 To retard the chemical activity of hexavalent chromium, the samples
and extracts should be stored at 4°C until analyzed. The maximum holding time
prior to analysis of the samples or extracts is 24 hr. The 24 hr holding time
begins after extraction.
7.0 PROCEDURE
7.1 Color development and measurement: Transfer 95 mL of the extract to
be tested to a 100-mL volumetric flask. Add 2.0 mL diphenylcarbazide solution
and mix. Add H2S04 solution to give a pH of 2 + 0.5, dilute to 100 mL with
reagent water, and let stand 5 to 10 min for full color development. Transfer
an appropriate portion of the solution to a 1-cm absorption cell and measure its
absorbance at 540 nm. Use reagent water as a reference. Correct the absorbance
reading of the sample by subtracting the absorbance of a blank carried through
the method (see Note below). An aliquot of the sample containing all reagents
except diphenylcarbazide should be prepared and used to correct the sample for
turbidity (i.e., a turbidity blank). From the corrected absorbance, determine
the mg/L of chromium present by reference to the calibration curve.
NOTE: If the solution is turbid after dilution to 100 mL in Step 7.1,
above, take an absorbance reading before adding the carbazide
7196A - 2 Revision 1
July 1992
-------
reagent and correct the absorbance reading of the final colored
solution by subtracting the absorbance measured previously.
7.2 Preparation of calibration curve:
7.2.1 To compensate for possible slight losses of chromium during
digestion or other operations of the analysis, treat the chromium
standards by the same procedure as the sample. Accordingly, pipet a
chromium standard solution in measured volumes into 250-mL beakers or
conical flasks to generate standard concentrations ranging from 0.5 to
5 mg/L Cr(VI) when diluted to the appropriate volume.
7.2.2 Develop the color of the standards as for the samples.
Transfer a suitable portion of each colored solution to a 1-cm absorption
cell and measure the absorbance at 540 nm. As reference, use reagent
water. Correct the absorbance readings of the standards by subtracting
the absorbance of a reagent blank carried through the method. Construct
a calibration curve by plotting corrected absorbance values against mg/L
of Cr(VI).
7.3 Verification:
7.3.1 For every sample matrix analyzed, verification is required to
ensure that neither a reducing condition nor chemical interference is
affecting color development. This must be accomplished by analyzing a
second 10-mL aliquot of the pH-adjusted filtrate that has been spiked with
Cr(VI). The amount of spike added should double the concentration found
in the original aliquot. Under no circumstances should the increase be
less than 30 /ig Cr(VI)/liter. To verify the absence of an interference,
the spike recovery must be between 85% and 115%.
7.3.2 If addition of the spike extends the concentration beyond the
calibration curve, the analysis solution should be diluted with blank
solution and the calculated results adjusted accordingly.
7.3.3 If the result of verification indicates a suppressive
interference, the sample should be diluted and reanalyzed.
7.3.4 If the interference persists after sample dilution, an
alternative method (Method 7195, Coprecipitation, or Method 7197,
Chelation/Extraction) should be used.
7.4 Acidic extracts that yield recoveries of less than 85% should be
retested to determine if the low spike recovery is due to the presence of
residual reducing agent. This determination shall be performed by first making
an aliquot of the extract alkaline (pH 8.0-8.5) using 1 N sodium hydroxide and
then respiking and analyzing. If a spike recovery of 85-115% is obtained in the
alkaline aliquot of an acidic extract that initially was found to contain less
than 5 mg/L Cr(VI), one can conclude that the analytical method has been
verified.
7196A - 3 Revision 1
July 1992
-------
7.5 Analyze all extracts, all samples analyzed as part of a deli sting
petition, and all samples that suffer from matrix interferences by the method of
standard additions (see Method 7000, Section 8.7).
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection. Refer to Chapter One for more information.
8.2 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.3 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.4 Verify calibration with an independently prepared check standard
every 15 samples.
8.5 Run one matrix spike replicate or one replicate sample for every ten
samples. A duplicate sample is a sample brought through the whole sample
preparation and analytical process. Refer to Chapter One for more information
concerning matrix spikes and matrix spike duplicates.
8.6 The method of standard additions (see Method 7000, Section 8.7) shall
be used for the analysis of all extracts, on all analyses submitted as part of
a delisting petition, and whenever a new sample matrix is being analyzed.
9.0 METHOD PERFORMANCE
9.1 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Methods 218.4 and 218.5.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7196A - 4 Revision 1
July 1992
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample
Matrix
Preparation
Method
Laboratory
Replicates
Wastewater treatment
sludge Not known
Sediment from chemical
storage area 3060
0.096, 0.107 ug/g
115, 117 ug/g
7196A - 5
Revision 1
July 1992
-------
METHOD 7196A
CHROMIUM, HEXAVALENT (COLORIMETRIC)
Start
? 1 Transfer
extract to
flask,add
diphenyIcarbazide
solution,and nix
for color
development
7 1 Add H,SO«
solution.dilute,let
stand,measure the
correct absorbance
reading,and
determine Cr
present
7 2.1 Treat Cr
standards by the
same procedure as
sample,pipet Cr
standard solution
into beaker
722 Develop color
for standards,
measure and correct
reading,construct
calibration curve
731 Analy2e a
second aliquot of
pK adjusted
filtrate spiked
with Cr(VI) for
verification
7.3.2 Dilute
•piked aanplt
with blink
solution,
adjutt recult*
Ye«
Do**
• pike cone
xeeed calibr
curve?
I.
•upre»»iv»
interferene
indicated
7.3.3 Dilute
•••pie end
7.4 Prepare an
alkaline
aliquot «itk IN
NaOH,«pike
•a>ple,analyie
7 4 Analytical
method i» verified
Stop
7196A - 6
Revision 1
July 1992
-------
METHOD 7197
CHROMIUM, HEXAVALENT (CHELATION/EXTRACTION)
1.0 SCOPE AND APPLICATION
1.1 Method 7197 1s approved for determining the concentration of
dissolved hexavalent chromium [Cr(VI)] 1n Extraction Procedure (EP) toxicity
characteristic extracts and ground waters. This method may also be applicable
to certain domestic and Industrial wastes, provided that no interfering
substances are present (see Paragraph 3.1).
1.2 Method 7197 may be used to analyze samples containing from 1.0 to
25 ug of Cr(VI) per liter.
2.0 SUMMARY OF METHOD
2.1 Method 7197 1s based on the chelation of hexavalent chromium with
ammonium pyrrolidlne dlthlocarbamate (APDC) and extraction with methyl
Isobutyl ketone (MIBK). The extract is aspirated into the flame of an atomic
absorption spectrophotometer.
3.0 INTERFERENCES
3.1 High concentrations of other metals may Interfere.
4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer; Single or dual channel,
single- ordouble-beaminstrument,having a grating monochromator,
photomultiplier detector, adjustable slits, and provisions for background
correction.
4.2 Chromium hollow cathode lamp.
4.3 Strip-chart recorder (optional).
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Ammonium pyrrolidine dithlocarbamate (APDC) solution: Dissolve
1.0 g APDC in Type II water and dilute to 100 mL. Prepare fresh daily.
5.3 Bromphenol blue Indicator solution; Dissolve 0.1 g bromphenol blue
1n 100 mL 50% ethanol.
7197 - 1
Revision
Date September 1986
-------
5.4 Potassium dlchromate standard solution I (1.0 ml = 100 ug Cr):
Dissolve 0.2829 g pure dried potassium dichromate, I^C^O/, in Type II water
and dilute to 1,000 mL.
5.5 Potassium dichromate standard solution II (1.0 mL = 10.0 ug Cr):
Dilute 100 mL chromium standard solution I to 1 liter with Type II water.
5.6 Potassium dichromate standard solution III (1.0 mL = 0.10 ug Cr):
Dilute 10.0 ml chromium standard solution II to 1 liter with Type II water.
5.7 Methyl isobutyl ketone (MIBK), analytical reagent grade: Avoid or
redistill material that comes in contact with metal or metal-lined caps.
5.8 Sodium hydroxide solution, 1 M: Dissolve to 40 g sodium hydroxide,
NaOH (ASC reagent grade), in Type II water and dilute to 1 liter.
5.9 Sulfuric acid, 0.12 M: Slowly add 6.5 ml distilled reagent grade or
spectrograde-quality sulfuric acid, ^$04, to Type II water and dilute to 1
liter.
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 Because the stability of Cr(VI) in EP extracts is not completely
understood at this time, the chelation and extraction should be carried out as
soon as possible.
6.3 To retard the chemical activity of hexavalent chromium, the samples
and extracts should be stored at 4*C until analyzed.
7.0 PROCEDURE
7.1 Pi pet a volume of extract containing less than 2.5 ug chromium
(100 mL maximum) Into a 200-mL volumetric flask and adjust the volume to
approximately 100 mL.
7.2 Prepare a blank and sufficient standards and adjust the volume of
each to approximately 100 mL.
7.3 Add 2 drops of bromphenol blue indicator solution. (The adjustment
of pH to 2.4, Step 7.4, may be made with a pH meter instead of using an
indicator.)
7.4 Adjust the pH by addition of 1 M NaOH solution dropwise until a blue
color persists. Add 0.12 M H?S04 dropwise until the blue color just disap-
pears in both the standards and sample. Then add 2.0 mL of 0.12 M H2S04 in
excess. The pH at this point should be 2.4.
7197 - 2
Revision 0
Date September 1986
-------
7.5 Add 5.0 ml APDC solution and mix. The pH should then be approxi-
mately 2.8.
7.6 Add 10.0 ml MIBK and shake vigorously for 3 mln.
7.7 Allow the layers to separate and add Type II water until the ketone
layer 1s completely 1n the neck of the flask.
7.8 Aspirate the ketone layer and record the scale reading for each
sample and standard against the blank. Repeat, and average the duplicate
results.
7.9 Determine the mg/Hter of Cr(VI) in each sample from a plot of scale
readings of standards. A working curve must be prepared with each set of
samples.
7.10 Verification;
7.10.1 For every sample matrix analyzed, verification 1s required
to ensure that neither a reducing condition nor chemical interference is
affecting chelatlon. This must be accomplished by analyzing a second 10-
mL aliquot of the pH-adjusted filtrate that has been spiked with Cr(VI).
The amount of spike added should double the concentration found 1n the
original aliquot. Under no circumstances should the Increase be less
than 30 ug/L Cr(VI). To verify the absence of an interference, the spike
recovery must be between 85% and 115%.
7.10.2 If addition of the spike extends the concentration beyond
the calibration curve, the analysis solution should be diluted with blank
solution and the calculated results adjusted accordingly.
7.10.3 If the result of verification Indicates a suppressive
interference, the sample should be diluted and reanalyzed.
7.10.4 If the Interference persists after sample dilution, an
alternative method (Method 7195, Coprecipitation, or Method 7196,
Color1metric) should be used.
7.11 Acidic extracts that yield recoveries of less than 85% should be
retested to determine 1f the low spike recovery Is due to the presence of
residual reducing agent. This determination shall be performed by first
making an aliquot of the extract alkaline (pH 8.0-8.5) using 1 N sodium
hydroxide and then resplklng and analyzing. If a spike recovery of 85-115% is
obtained in the alkaline aliquot of an acidic extract that Initially was found
to contain less than 5 mg/L Cr(VI), one can conclude that the analytical
method has been verified.
7197 - 3
Revision 0
Date September 1986
-------
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples if they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine 1f
contamination or any memory effects are occurring.
8.5 Verify calibration with an Independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 10 samples. A duplicate
sample 1s a sample brought through the whole sample preparation and analytical
process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a del 1 sting petition, and whenever a new sample matrix 1s being
analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 218.4 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 218.4.
7197 - 4
Revision
Date September 1986
-------
METHOD 7197
HEXAVALENT CHROMIUM (CHELATION/EXTHACTION)
( Start 1
7. 1
Plpet extract
Into flask:
adjust volume
7.2
Prepare
blank and
standards:
adjust volume
of each
7.3
Add bromphenol
blue Indicator
solution
7 .A
Allow layers to
separate: add
Type II water
Adjust pH by
adding NaOH;
add
7.8
Aspirate
ketone
layer; record
scale readings:
repeat: average
results
7197 - 5
Revision 0
Date September 1986
-------
METHOD 7197
HEXAVALENT CHROMIUM (CHEUATION /EXTRACTION)
(Continued)
JLU
Determine
Cr (IV) in each
sample: prepare
working curves
7.10.1 Verify
I every
sample matrix
by analyzing
second aliquot
spiked filtrate
Is cone.
beyond
calibration
curve?
analysis
solution with
blank solution;
adjust results
Is there a
suppresslve
interference?
Dilute sample
and reanalyze
Use alternative
method
Analytical
method verified
-waste Is not
hazardous
If no valid
results and chromium
concentration over
threshold limits.
sample exhibits
EP toxlclty
f Stop J
7197 - 6
Revision 0
Date September 1986
-------
METHOD 7198
CHROMIUM, HEXAVALENT (DIFFERENTIAL PULSE POLAROGRAPHY)
1.0 SCOPE AND APPLICATION
1.1 This method is used to determine the concentration of hexavalent
chromium [Cr(VI)] in natural and waste waters and in EP extracts.
1.2 The method can quantitate chromium 1n concentrations of up to
1.0 mg/L to 5.0 mg/L, depending on the mercury drop size. Higher concentra-
tions can be determined by dilution.
1.3 The lower limit of detection for Cr(VI) 1s 10 ug/L for the
instrumental conditions given in this method. The limit of detection could be
easily lowered by changing these conditions.
2.0 SUMMARY OF METHOD
2.1 Method 7198 measures the peak current produced from the reduction of
Cr(VI) to Cr(III) at a dropping mercury electrode during a differential pulse
voltage ramp.
2.2 The method described herein uses 0.125 M NH40H-0.125 M NH4C1 as the
supporting electrolyte. In this electrolyte, Cr(VI) reduction results in peak
current occurring at the peak potential (Ep) of -0.250 V vs. Ag/AgCl.
2.3 Alternative supporting electrolytes, such as those given in Table 1,
may be used.
2.4 The technique of standard additions must be used to quantitate the
Cr(VI) content.
3.0 INTERFERENCES
3.1 Copper ion at concentrations higher than the Cr(VI) concentration is
a potential Interference due to peak overlap when using the 0.125 M ammoniacal
electrolyte. Increasing the ammoniacal electrolyte concentration to 0.5 M
shifts the copper peak cathodically (Ep = -0.4 V), eliminating the
Interference at a copper-to-chromium ratio of 10:1 (Figure 1).
3.2 Reductants such as ferrous iron, sulflte, and sulflde will reduce
Cr(VI) to Cr(III); thus it is imperative to analyze the samples as soon as
possible.
4.0 APPARATUS AND MATERIALS
4.1 Polarographic 1nstrumentation; Capable of performing differential
pulse analyses, including recorder or plotter.
7198 - 1
Revision 0
Date September 1986
-------
2.0-
1.5-
Current x 102 nA
18 Jan 82 No. 1
Sample: DPP
Initial E: -0.100 V
Final E: -0.450 V
Peak 1: -0.292 V
2.047 E2nA
4.0-
3.0-
Current x 102 nA
18 Jan 82 No. 2
Sample: DPP
Initial E: -0.100V
Final E: -0.450 V
Peak 1: -0.256 V
2.680 E1 nA
Peak 2: -0.396 V
9.740E1 nA
-0.2 -0.4
-0.2 -0.4
A. 20 ppm Cu, 2.5 ppm Cr, 0.1 N buffer.
B. 20 ppm Cu, 2.5 ppm Cr, 0.5 N buffer.
Figure 1. Two polarograms illustrating shift in copper peak at higher ammoniacal
electrolyte concentrations.
7198 - 2
Revision 0
Date September 1986
-------
TABLE 1. POLAROGRAPHY OF HEXAVALENT CHROMIUM
Supporting electrolyte
Peak potential (vs. SCE)
1 M NaOH
1 M Pyr1d1ne, 1 M NaOH
1 M NH4OH, 1 M NH4C1
0.1 M NH40H, 0.1 M (^4)2 Tartrate
0.2 M KC1, 0.3 M Tr1ethanolam1ne, pH 9
1 M Na2S04
0.1 M NH4OH, 0.1 M NH4C1
-0.85
-1.48
-0.36
-0.244
-0.28
-0.23
-0.25
7198 - 3
Revision 0
Date September 1986
-------
4.2 Dropping mercury electrode assembly: Capable of performing
differential pulse analyses.
4.3 Counter electrode: Platinum wire.
4.4 Reference electrode; Ag/AgCl or SCE, with a slow-leakage fritted
tip (unfired Vycor).
4.5 Nitrogen gas and cell outgassing assembly.
4.6 Micropipets and disposable tips.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Chromium standard solution I, 1.0 ml = 100 ug Cr: Should be made
daily from a 1,000-ppm standard stock solution made with Type II water.
5.3 Chromium standard solution II, 1.0 ml = 10 ug Cr: Should be made
daily from a 1,000-ppm standard stock solution made with Type II water.
5.4 Chromium standard solution III, 1.0 ml = 1 ug Cr: Dilute 10 ml
chromium standard solution II to 100 ml with Type II water.
5.5 Ammoniacal electrolyte, 2.5 N: Dissolve 33.3 g of NfyCl in 150 ml
of Type II water, add 42.2 ml of concentrated NfyOH, and dilute to 250 ml.
5.6 Concentrated nitric acid; Acid should be analyzed to determine
levels of impurities.ITimpurities are detected, all analyses should be
blank-corrected.
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 Stability of Cr(VI) is not completely understood at this time.
Therefore, the analysis should be carried out as soon as possible.
6.3 If the analysis cannot be performed within 24 hr, take an aliquot of
the sample and add a known amount of Cr(VI) (0.1 mg/L for natural waters,
1 mg/L for wastewaters, and 5 mg/L for EP extracts). Analyze this known
additional sample at the same time the sample is analyzed to determine whether
Cr(VI) was reduced during storage.
6.4 To retard the chemical activity of Cr(VI), the sample should be
transported and stored at 4*C until time of analysis.
7198 - 4
Revision
Date September 1986
-------
7.0 PROCEDURE
7.1 Soak the voltammetric cells overnight in 1 + 1 HNC-3 and/or 1 + 1
aqua regia.
7.2 Rinse the electrode assembly with Type II water, then with 1 N HMOs,
and finally with Type II water prior to and in between sample analyses.
7.3 The instrument should be set using the following instrumental
parameters.
7.3.1 Mode: Differential pulse.
7.3.2 Scan rate: 2 mV/sec.
7.3.3 Drop time: 1 sec.
7.3.4 Initial potential: -0.05 V + 0.05 V vs. Ag/AgCl.
7.3.5 Final potential: -0.50 V + 0.10 V vs. Ag/AgCl.
7.3.6 Pulse height: 0.05 V.
7.3.7 Deaeratlon time: 240 sec or less initially, 30 sec between
standard additions.
7.4 Analysis:
7.4.1 Pipet a volume of sample containing less than 10 ug Cr(VI)
into a voltammetric cell (the maximum volume depends on the voltammetric
cell volume, usually 10 ml).
7.4.2 Add 0.5 ml of the ammoniacal electrolyte and adjust volume to
10 ml with Type II water.
7.4.3 Place the electrode assembly in the solution and outgas with
nitrogen for at least 120 sec.
7.4.4 Engage the electrode assembly to the polarographic analyzer
and displace at least 10 mercury drops before initiating the voltage ramp
and obtaining the polarogram.
7.4.5 Figure 2 gives typical differential pulse polarograms.
7.5 Prior to the analysis of any samples, and during analysis at a
frequency of at least once every 10 samples, verify that the cell contamina-
tion is less than 10 ug/L Cr by analyzing deminerallzed water and the appro-
priate volume of supporting electrolyte in a manner similar to the procedure
described in 7.4.3 and 7.4.4.
7.6 Calibration;
7.6.1 After running a differential pulse polarogram on the sample
solution, quantitate the chromium using the technique of standard
addition.
7198 - 5
Revision 0
Date September 1986
-------
2.0-
1.5-
Current x 10^ nA
26 Oct 81 No. 1
Standard No. 1 DPP
Initial E: 0.000 V
Final E: -0.350 V
Peak 1: -0.160V
1.181E2nA
250.0 ppb
2.0-
1.5-
Current x 10^ n A
26 OCT 81 No. 1
Standard No. 2 DPP
Initial E: 0.000 V
Final E: -0.350 V
Peak 1:-0.154 V
1.146E3nA
2.500 ppm
-0.1 -0.3
-0.1 -0.3
Figure 2. Typical differential pulse polarogram at 0.25 ppm and 2.5 ppm Cr
in 0.1 N buffer.
7198 - 6
Revision 0
Date September 1986
-------
7.6.2 Three standard additions should be made to obtain the best
precision and accuracy. The first standard addition should be approxi-
mately one-half the concentration of the sample, the second equal to that
of the sample, and the third about 1.5 times the sample concentration.
The total volume due to standard additions should not exceed the cell
value by more than 10%.
7.6.3 Add an appropriate aliquot of chromium standard solution I,
II, or III to the sample 1n the cell. Deaerate for 30 sec to mix the
solution and remove oxygen added with the known addition.
7.6.4 Repeat the analysis procedure, beginning with Step 7.4.4 for
each standard addition.
7.7 Calculations;
7.7.1 Calculate the concentration of chromium determined by each
standard addition procedure as follows:
c
-
.
i - tjv, + (tr i,)v vu
where:
ij = Current peak height for the sample (nA);
1j = Current peak height for the sample plus standard (nA);
Vu = Volume of sample in the cell (ml);
Vj = Volume of standard taken for spiking (ml);
V = Volume in cell prior to standard addition;
Cs = Concentration of standard used to spike (mg/L); and
Cu = Concentration of the unknown in the sample (mg/L).
7.7.2 Some microprocessor polarographic systems will perform
these calculations automatically.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection.
8.2 If necessary, dilute samples so that they fall within the working
range.
7198 - 7
Revision
Date September 1986
-------
8.3 Quant1 tat1on must be performed by the method of standard additions
(see Method 7000, Section 8.7).
8.4 Verify calibration with an Independently prepared check standard
every 15 samples (see Chapter One, Section 1.1.8).
8.5 Standards should be compared to a reference standard on a routine
basis.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data for this method are summarized 1n
Table 2.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 218.4 and 218.5.
7198 - 8
Revision
Date September 1986
-------
TABLE 2. PRECISION AND ACCURACY OF THE DPP OF HEXAVALENT CHROMIUM
2a. Precision
Sample type No. of replicates
Average value
% RSD
Leachatea
1.87
0.69
2b. Accuracy (spike recovery data)
Spike level No. of Average %
Sample type (mg/L) samples recovery
Standard
deviation of
% recovery
EP extracts
5.0
8
92.8
6.4
2c. Methods comparison
D1ff. pulse
polarography
APDC extrac-
tion ICAP-OES
Ion chromatography
coupled to ICAP-OES
Value3
1.87
1.84
1.91
al_eachate sample from a waste disposal site.
7198 - 9
Revision 0
Date September 1986
-------
METHOD ?i9a
HEXAVALENT CHROMIUM (DIFFERENTIAL PULSE POLAROGRAPH)
C
7. 1
Soak
voltemmetrIc
cells overnight
7.4.31 Place
lelactrode
assembly In
solution:
outgas with
nitrogen
7.2
fllnse
electrode
assembly before
and between
sample analyses
7.3
Engage electrode
assembly: displace
mercury droos:
initiate voltage
ramp; obtain
polargram
Set instrument
7.4.1
7.S
of chromium
standard
solution:
deaerate
Prior
to ana
during analysis
verify that
eel 1 contamin.
is < 10 ug/1 Cr
Plpet
sample
with hexavalant
chromium into
voltammetrlc
cell
7.6.1
7.6.4
Repeat
for each
standard
addition
starting with
section 7.4.4
Run
differential
pulse
polarogram on
sample solution
7.
Add ammonlacal
electrolyte:
adjust volume
7.7
Calculate
concentration
of chromium
7.6.ll
Ouantltate
chromium using
technique of
standard add.
f Stop J
7198 - 10
Revision Q
Date September 1986
-------
METHOD 7200
COBALT (ATOMIC ABSORPTION. DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 If Interferences are suspected.
3.2 Excesses of other transition metals may slightly depress the
response of cobalt. Matrix matching or the method of standard additions 1s
recommended.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Cobalt hollow cathode lamp.
4.2.2 Wavelength: 240.7 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: A1r.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g of cobalt metal (analytical
reagent grade) 1n 20 mL of 1:1 HNC"3 and dilute to 1 liter with Type II
water. Chloride or nitrate salts of cobalt (II) may be used. Although
numerous hydrated forms exist, they are not recommended unless the exact
composition of the compound 1s known. Alternatively, procure a certified
standard from a supplier and verify by comparison with a second standard.
7200 - 1
Revision
Date September 1986
-------
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 add and at the same
concentration as will result in the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 0.5-5 mg/L with a wavelength of 240.7 nm.
Sensitivity: 0.2 mg/L.
Detection limit: 0.05 mg/L.
9.2 In a single laboratory, analysis of a mixed Industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 0.2, 1, and 5
mg/L gave standard deviations of +0.013, +0.01, and +0.05, respectively.
Recoveries at these levels were 98% and 97%, respectively.
9.3 For concentrations of cobalt below 0.1 mg/L, the furnace procedure
(Method 7201) is recommended.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 219.1.
7200 - 2
Revision
Date September 1986
-------
METHOD 7200
COBALT (ATOMIC ABSORPTION. DIRECT ASPIRATION)
C
5.0
Prepare
standards
7.1
1 For
sample
preparation see
chapter 3.
section 3.1.3
7.2
Analyze using
Method 7000.
Section 7.2
( Stop J
7200 - 3
Revision 0
Date September 1986
-------
METHOD 7201
COBALT (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000 if Interferences are suspected.
3.2 Excess chloride may Interfere. It is necessary to verify by
standard additions that the interference is absent.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 900*C.
4.2.3 Atomizing time and temp: 10 sec at 2700*C.
4.2.4 Purge gas: Argon.
4.2.5 Wavelength: 240.7 nm.
4.2.6 Background correction: Required.
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
sizes of 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.
7201 - 1
Revision
Date September 1986
-------
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g of cobalt metal (analytical
reagent grade) 1n 20 ml of 1:1 HMOs and dilute to 1 liter with Type II
water. Chloride or nitrate salts of cobalt (II) may be used. Although
numerous hydrated forms exist, they are not recommended unless the exact
composition of the compound 1s known. Alternatively, procure a certified
standard from a supplier and verify 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 add and at the same
concentrations as 1n the sample after processing (0.5% v/v
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure.
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.
9.2 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 5-100 ug/L.
Detection limit: 1 ug/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 219.2.
7201 - 2
Revision
Date September 1986
-------
METHOD 7ZO1
COBALT (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
5.O
Prepare
standards
7. 1
For
sample
preparation see
chapter 3.
section 3.2
7.2
Analyze using
Method 7000.
Section 7.3.
f Stop J
7201 - 3
Revision Q
Date September 1986
-------
METHOD 7210
COPPER (ATOMIC ABSORPTION. DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000.
3.2 Background correction may be required because nonspecific absorption
and scattering can be significant at the analytical wavelength. Background
correction with certain Instruments may be difficult at this wavelength due to
low-intensity output from hydrogen or deuterium lamps. Consult specific
instrument manufacturer's literature for details.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Copper hollow cathode lamp.
4.2.2 Wavelength: 324.7 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: A1r.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Recommended, if possible.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.00 g of electrolytic copper
(analytical reagent grade) in 5 mL of redistilled HNOs and dilute to
1 liter with Type II water. Alternatively, procure a certified standard
from a supplier and verify by comparison with a second standard.
7210 - 1
Revision
Date September 1986
-------
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 add and at the same concentra-
tion as will result In the sample to be analyzed after processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.2-5 mg/L with a wavelength of 324.7 nm.
Sensitivity: 0.1 mg/L.
Detection limit: 0.02 mg/L.
9.2 Precision and accuracy data are available 1n Method 220.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 220.1.
7210 - 2
Revision
Date September 1986
-------
METHOD 721O
COPPER (ATOMIC ABSORPTION. OIHECT ASPIRATION)
C
5.O 1
Prepare
standards
7.1
Si
preparat
Chaf
sect!
7.2
'or
imple
.Ion see
iter 3.
ion 3.2
Analyze using
Method 7000.
Section 7.2
( stop j
7210 - 3
Revision 0
Date September 1986
-------
METHOD 7211
COPPER (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
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 Background correction may be required since nonspecific absorption
and scattering can be significant at the analytical wavelength. Background
correction with certain instruments may be difficult at this wavelength due to
low intensity output from hydrogen or deuterium lamps. Consult specific
instrument manufacturer's literature for details.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 900°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: 324.7 nm.
4.2.6 Background correction: Recommended.
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.
7211 - 1 Revision 0
July 1992
-------
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards
5.2.1 Stock solution - Dissolve 1.00 g of electrolytic copper
(analytical regent grade) in 5 ml redistilled HNO, and dilute to 1 liter
with water. Alternatively, procure a certified standard from a supplier
and verify 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
concentrations as in the sample to be analyzed after processing (0.5%
v/v HN03).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Step 3.1.3, Sample Handling and Preservation.
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.
9.2 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 5-100 ug/L.
Detection limit: 1 ug/L.
7211 - 2 Revision 0
July 1992
-------
10.0 REFERENCES
1. Methods for 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 Center for
Environmental Research Information: Cincinnati, OH, 1983; EPA-600/4-79-020.
7211 - 3 Revision 0
July 1992
-------
METHOD 7211
COPPER (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
Start
S.0 Pnpar*
•tandard*
7.1 For «ampl«
preparation •••
Chapter 3, Section
3 2
i
7.2 Analyi* uung
M.thod 7000
Section 7.3
Stop
7211 - 4
Revision 0
July 1992
-------
METHOD 7380
IRON (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 If interferences are suspected.
3.2 Iron 1s a universal contaminant, and great care should be taken to
avoid contamination.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Iron hollow cathode lamp.
4.2.2 Wavelength: 248.3 nm (primary); 248.8, 271.9, 302.1, 252.7,
or 372.0 nm (alternates).
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g iron wire (analytical
reagent grade) in 10 mL redistilled HN03 and Type II water and dilute to
1 liter with Type II water. Note that iron passivates in concentrated
HN03, and thus some water should be present. Alternatively, procure a
certified standard from a supplier and verify by comparison with a second
standard.
7380 - 1
Revision
Date September 1986
-------
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 add and at the same
concentration as will result 1n the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 0.3-5 mg/L with a wavelength of 248.3 nm.
Sensitivity: 0.12 mg/L.
Detection limit: 0.03 mg/L.
9.2 Precision and accuracy data are available In Method 236.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 236.1.
7380 - 2
Revision
Date September 1986
-------
METHOD 7380
IRON (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.O
Prepare
standards
7.1
1 For
sample
preparation 'sec
chapter 3.
section 3.2
Analyze using
Method 7000.
Section 7.2
f Stop J
7380 - 3
Revision 0
Date September 1986
-------
METHOD 7381
IRON (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000.
3.2 Iron is a universal contaminant, particularly at the low levels
determined by this method. Great care should be taken to avoid contamination.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 1000°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: 248.3 nm.
4.2.6 Background Correction: Recommended.
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.
7381 - 1 Revision 0
July 1992
-------
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards
5.2.1 Stock solution - Dissolve 1.000 g iron wire (analytical
reagent grade) in 10 ml redistilled HN03 and water and dilute to 1 liter
with water. Note that iron passivates in concentrated HNO, and, thus, some
water should be present. Alternatively, procure a certified standard from
a supplier and verify 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
concentrations as in the sample to be analyzed after processing (0.5% v/v
HN03).
6.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING
6.1 See Chapter Three, Step 3.1.3, Sample Handling and Preservation.
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.
9.2 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 5-100 ug/L.
Detection limit: 1 ug/L.
7381 - 2 Revision 0
July 1992
-------
10.0 REFERENCES
1. Methods for 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 Center for Environmental
Research Information: Cincinnati, OH, 1983; EPA-600/4-79-020.
7381 - 3 Revision 0
July 1992
-------
METHOD 7381
IRON (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
Start
5.0 Prepare
(tandard*
7.1 For *ampl«
preparation »••
Chapter 3, Section
3.2
7.2 Analyze u«ing
Method 7000
Section 7.3
i
Stop
7381 - 4
Revision 0
July 1992
-------
METHOD 7420
LEAD (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 If Interferences are suspected.
3.2 Background correction Is required at either wavelength.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Lead hollow cathode lamp.
4.2.2 Wavelength: 283.3 nm (primary); 217.0 nm (alternate).
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: A1r.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.599 g of lead nitrate,
(analytical reagent grade), in Type II water, acidify with 10 mL
redistilled HN03, and dilute to 1 liter with Type II water. Alterna-
tively, procure a certified standard from a supplier and verify 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
concentration as will result in the sample to be analyzed after
processing.
7420 - 1
Revision 0
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given In Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 1-20 mg/L with a wavelength of 283.3 nm.
Sensitivity: 0.5 mg/L.
Detection limit: 0.1 mg/L.
9.2 For concentrations of lead below 0.2 mg/L, the furnace technique
(Method 7421) 1s recommended.
9.3 Precision and accuracy data are available 1n Method 239.1 of Methods
for Chemical Analysis of Water and Wastes.
9.4 The data shown In Table 1 were obtained from records of state and
contractor laboratories. The data are Intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 239.1.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7420 - 2
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Wastewater treatment sludge 3050 450, 404 ug/g
Emission control dust 3050 42,500, 63,600 ug/g
7420 - 3
Revision
Date September 1986
-------
METHOD 742O
LEAD (ATOMIC ABSORPTION. DIRECT ASPIRATION)
s.o
Prepare
standards
7. 1
For
sample
preparation see
chapter. 3.
section 3.2
7.2
Analyze using
Method 7000.
Section 7.2
f Stop J
7420 - 4
Revision 0
Date September 1986
-------
METHOD 7421
LEAD (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Background correction 1s required.
3.3 If poor recoveries are obtained, a matrix modifier may be necessary.
Add 10 uL of phosphoric acid (Paragraph 5.3) to 1 ml of prepared sample 1n the
furnace sampler cup and mix well.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 500'C.
4.2.3 Atomizing time and temp: 10 sec at 2700*C.
4.2.4 Purge gas: Argon.
4.2.5 Wavelength: 283.3 nm.
4.2.6 Background correction: Required.
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
Perkln-Elmer HGA-2100, based on the use of a 20-uL injection,
continuous-flow purge gas, and nonpyrolytlc graphite. Smaller
sizes of furnace devices or those employing faster rates of
atomizatlon can be operated using lower atomlzation temperatures
for shorter time periods than the above-recommended settings.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
7421 - 1
Revision
Date September 1986
-------
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.599 g of lead nitrate, Pb(NOs)2
(analytical reagent grade), In Type II water, acidify with 10 ml
redistilled HN03, and dilute to 1 liter with Type II water. Alterna-
tively, procure a certified standard from a supplier and verify 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 add and at the same
concentrations as in the sample after processing (0.5% v/v HNOs).
5.3 Phosphoric acid; Reagent grade.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
is given in Method 7000, Paragraph 7.4.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 239.2 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 5-100 ug/L.
Detection limit: 1 ug/L.
9.3 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
7421 - 2
Revision
Date September 1986
-------
10.0 REFERENCES
1. Lead by Flameless Atomic Absorption with Phosphate Matrix Modification,
Atomic Spectroscopy, !_ (1980), no. 3, pp. 80-81.
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7421 - 3
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample
Matrix
Contaminated soil
Paint primer
Lagoon soil
NBS SRM 1646 Estuarlne sediment
NBS SRM 1085 Wear metals 1n
lubricating oil
Solvent extracted oily waste
Preparation
Method
3050
3050
3050
3050
3030
3030
Laboratory
Replicates
163, 120 mg/g
0.55, 0.63 mg/g
10.1, 10.0 ug/g
23.7 ug/g*
274, 298 ug/gb
9, 18 ug/L
aB1as of -16% from expected.
&B1as of -10 and -2% from expected, respectively,
7421 - 4
Revision 0
Date September 1986
-------
METHOD 7431
LEAD (ATOMIC ABSORPTION. FURNAC6 TECHNIQUE)
C
5.0
Prepare
standards
7. 1
prepar
ct
sec
For
sample
•ation see
lapter 3.
tion 3.2
7.2
Analyze using
Method 7000.
Section 7.3.
calculation 7.4
( Stop J
7421 - 5
Revision 0
Date September 1986
-------
METHOD 7430
LITHIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Lithium hollow cathode lamp.
4.2.2 Wavelength: 670.8 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxidant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background Correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards
5.2.1 Stock solution: (1.0 mL = 1.0 mg Li). Dissolve 5.324 g
lithium carbonate, Li,C03, in a minimum volume of 1:1 HC1 and dilute to
1 liter with water. Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
7430 - 1 Revision 0
July 1992
-------
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 as the samples used to
prepare the samples and cover the range of expected concentrations in the
samples.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Step 3.1.3, Sample Handling and Preservation.
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 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 0.1-2 mg/L at a wavelength of 670.8 nm.
Sensitivity: 0.04 mg/L.
Detection limit: 0.002 mg/L.
10.0 REFERENCES
1. Standard Methods for the Examination of Water and Wastewater, 16th ed.;
Greenberg, A.E.; Trussell, R.R.; Clesceri, L.S., Eds.; American Water
Works Association, Water Pollution Control Federation, American Public
Health Association: Washington, DC, 1985.
7430 - 2 Revision 0
July 1992
-------
METHOD 7430
LITHIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
Start
S.0 Prepare
•tandardi
7.1 For »ample
preparation, •••
Chapter 3, Step 3.2
7 2 Analyze using
Method 7000, Step
7.2
Stop
7430 - 3
Revision 0
July 1992
-------
METHOD 7450
MAGNESIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 All elements forming stable oxyanions (P, B, Si, Cr, S, V, Ti, Al,
etc.) will complex magnesium and interfere unless lanthanum is added. (See
Method 7000, Paragraph 3.1.1.) Addition of lanthanum to prepared samples
rarely presents a problem because virtually all environmental samples contain
sufficient magnesium to require dilution to be in the linear range of the
method.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Magnesium hollow cathode lamp.
4.2.2 Wavelength: 285.2 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g of magnesium metal
(analytical reagent grade) in 20 mL 1:1 HNOs and dilute to 1 liter with
Type II water. Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
7450 - 1
Revision 0
Date September 1986
-------
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 add and at the same
concentration as will result 1n the sample to be analyzed after
processing, Including 1 ml lanthanum solution per 10 ml solution (see
Paragraph 3.2).
5.2.3 Lanthanum chloride solution: Dissolve 29 g 13203 in 250 ml
concentrated HC1 -
(CAUTION: REACTION IS VIOLENT!) -
and dilute to 500 ml with Type II water.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 0.02-0.05 mg/L with a wavelength of 285.2
nm.
Sensitivity: 0.007 mg/L.
Detection limit: 0.001 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 2.1 and 8.2
mg/L gave standard deviations of +0.1 and +0.2, respectively. Recoveries at
both of these levels were 100%.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 242.1.
7450 - 2
Revision
Date September 1986
-------
METHOD 7450
MAGNESIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
Prepare
standards
7.,
. - 1 For
sample
preparation see
chapter 3.
section 3.2
7.2
Analyze using
Method 7000.
Section 7.2
f StOP J
7450 - 3
Revision 0
Date September 1986
-------
METHOD 7460
MANGANESE (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Background correction is required.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Manganese hollow cathode lamp.
4.2.2 Wavelength: 279.5 nm (primary); 403.1 nm (alternate).
4.2.3 Fuel: Acetylene.
4.2.4 Oxidant: Air.
4.2.5 Type of flame: Slightly oxidizing (slightly fuel-lean to
stoichiometric).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards:
5.2.1 Stock solution: Dissolve 1.000 g manganese metal (analytical
reagent grade) in 10 mL redistilled HN03 and dilute to 1 liter with
Type II water. Alternatively, procure a certified standard from a
supplier and verify 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 add and at the same
concentration as will result 1n the sample to be analyzed after
processing.
7460 - 1
Revision 0
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 0.1-3 mg/L with a wavelength of 279.5 nm.
Sensitivity: 0.05 mg/L.
Detection limit: 0.01 mg/L.
9.2 Precision and accuracy data are available 1n Method 243.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 243.1.
7460 - 2
Revision
Date September 1986
-------
METHOD 7460
MANGANESE (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5
0 1
Prepare
standards
7. 1
prepar
cf
set
For
sample
-ation see
lapter 3.
tlon 3.2
7 .Z
Analyze using
Method 7OOO.
Section 7.3
f Stop J
7460 - 3
Revision 0
Date September 1986
-------
METHOD 7461
MANGANESE (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000.
3.2 Background correction must be used.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 1000°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: 279.5 nm.
4.2.6 Background correction: Required.
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.
7461 - 1 Revision 0
July 1992
-------
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards
5.2.1 Stock solution - Dissolve 1.000 g manganese metal
(analytical reagent grade) in 10 ml redistilled HN03 and dilute to 1 liter
with water. Alternatively, procure a certified standard from a supplier
and verify 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 calibrations standards
should be prepared using the same type of acid and at the same
concentrations as in the sample after processing (0.5% v/v HN03).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Step 3.1.3, Sample Handling and Preservation.
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.
9.2 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 1-30 ug/L.
Detection limit: 0.2 ug/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Hastes; 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, 1983; EPA-600/4-79-020.
7461 - 2 Revision 0
July 1992
-------
METHOD 7461
MANGANESE (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
Start
5.0 Prepare
«tandard«
7 1 For iample
preparation mm*
Chapter 3, Section
3.2
7.2 Analyze uiing
Method 7000
Section 7 3
Stop
7461 - 3
Revision 0
July 1992
-------
METHOD 7470A
MERCURY IN LIQUID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 Method 7470 is a cold-vapor atomic absorption procedure approved for
determining the concentration of mercury in mobility-procedure extracts, aqueous
wastes, and ground waters. (Method 7470 can also be used for analyzing certain
solid and sludge-type wastes; however, Method 7471 is usually the method of
choice for these waste types.) All samples must be subjected to an appropriate
dissolution step prior to analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis, the liquid samples must be prepared according to
the procedure discussed in this method.
2.2 Method 7470, a cold-vapor atomic absorption technique, is based on
the absorption of radiation at 253.7-nm by mercury vapor. The mercury is reduced
to the elemental state and aerated from solution in a closed system. The mercury
vapor passes through a cell positioned in the light path of an atomic absorption
spectrophotometer. Absorbance (peak height) is measured as a function of mercury
concentration.
2.3 The typical detection limit for this method is 0.0002 mg/L.
3.0 INTERFERENCES
3.1 Potassium permanganate is added to eliminate possible interference
from sulfide. Concentrations as high as 20 mg/L of sulfide as sodium sulfide do
not interfere with the recovery of added inorganic mercury from reagent water.
3.2 Copper has also been reported to interfere; however, copper concen-
trations as high as 10 mg/L had no effect on recovery of mercury from spiked
samples.
3.3 Seawaters, brines, and industrial effluents high in chlorides require
additional permanganate (as much as 25 mL) because, during the oxidation step,
chlorides are converted to free chlorine, which also absorbs radiation of 253.7
nm. Care must therefore be taken to ensure that free chlorine is absent before
the mercury is reduced and swept into the cell. This may be accomplished by
using an excess of hydroxylamine sulfate reagent (25 mL). In addition, the dead
air space in the BOD bottle must be purged before adding stannous sulfate. Both
inorganic and organic mercury spikes have been quantitatively recovered from
seawater by using this technique.
3.4 Certain volatile organic materials that absorb at this wavelength may
also cause interference. A preliminary run without reagents should determine if
this type of interference is present.
7470A - 1 Revision 1
September 1994
-------
4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer or equivalent: Any atomic
absorption unit with an open sample presentation area in which to mount the
absorption cell is suitable. Instrument settings recommended by the particular
manufacturer should be followed. Instruments designed specifically for the
measurement of mercury using the cold-vapor technique are commercially available
and may be substituted for the atomic absorption spectrophotometer.
4.2 Mercury hollow cathode lamp or electrodeless discharge lamp.
4.3 Recorder: Any multirange variable-speed recorder that is compatible
with the UV detection system is suitable.
4.4 Absorption cell: Standard spectrophotometer cells 10 cm long with
quartz end windows may be used. Suitable cells may be constructed from Plexiglas
tubing, 1 in. O.D. x 4.5 in. The ends are ground perpendicular to the
longitudinal axis, and quartz windows (1 in. diameter x 1/16 in. thickness) are
cemented in place. The cell is strapped to a burner for support and aligned in
the light beam by use of two 2-in. x 2-in. cards. One-in.-diameter holes are cut
in the middle of each card. The cards are then placed over each end of the cell.
The cell is then positioned and adjusted vertically and horizontally to give the
maximum transmittance.
4.5 Air pump: Any peristaltic pump capable of delivering 1 liter air/min
may be used. A Masterflex pump with electronic speed control has been found to
be satisfactory.
4.6 Flowmeter: Capable of measuring an air flow of 1 liter/min.
4.7 Aeration tubing: A straight glass frit with a coarse porosity. Tygon
tubing is used for passage of the mercury vapor from the sample bottle to the
absorption cell and return.
4.8 Drying tube: 6-in. x 3/4-in.-diameter tube containing 20 g of mag-
nesium perchlorate or a small reading lamp with 60-W bulb which may be used to
prevent condensation of moisture inside the cell. The lamp should be positioned
to shine on the absorption cell so that the air temperature in the cell is about
10°C above ambient.
4.9 The cold-vapor generator is assembled as shown in Figure 1 of
reference 1 or according to the instrument manufacturers instructions. The
apparatus shown in Figure 1 is a closed system. An open system, where the
mercury vapor is passed through the absorption cell only once, may be used
instead of the closed system. Because mercury vapor is toxic, precaution must
be taken to avoid its inhalation. Therefore, a bypass has been included in the
system either to vent the mercury vapor into an exhaust hood or to pass the vapor
through some absorbing medium, such as:
1. Equal volumes of 0.1 M KMn04 and 10% H2S04; or
2. 0.25% Iodine in a 3% KI solution.
7470A - 2 Revision 1
September 1994
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A specially treated charcoal that will adsorb mercury vapor is also
available from Barnebey and Cheney, East 8th Avenue and North Cassidy
Street, Columbus, Ohio 43219, Cat. #580-13 or #580-22.
4.10 Hot plate or equivalent - Adjustable and capable of maintaining a
temperature of 90-95°C.
4.11 Graduated cylinder or equivalent.
5.0 REAGENTS
5.1 Reagent Water: Reagent water will be interference free. All
references to water in this method will refer to reagent water unless otherwise
specified.
5.2 Sulfuric acid (H2S04), concentrated: Reagent grade.
5.3 Sulfuric acid, 0.5 N: Dilute 14.0 ml of concentrated sulfuric acid
to 1.0 liter.
5.4 Nitric acid (HN03), concentrated: Reagent grade of low mercury
content. If a high reagent blank is obtained, it may be necessary to distill the
nitric acid.
5.5 Stannous sulfate: Add 25 g stannous sulfate to 250 ml of 0.5 N
H2S04. This mixture is a suspension and should be stirred continuously during
use. (Stannous chloride may be used in place of stannous sulfate.)
5.6 Sodium chloride-hydroxylamine sulfate solution: Dissolve 12 g of
sodium chloride and 12 g of hydroxylamine sulfate in reagent water and dilute to
100 ml. (Hydroxylamine hydrochloride may be used in place of hydroxylamine
sulfate.)
5.7 Potassium permanganate, mercury-free, 5% solution (w/v): Dissolve
5 g of potassium permanganate in 100 mL of reagent water.
5.8 Potassium persulfate, 5% solution (w/v): Dissolve 5 g of potassium
persulfate in 100 ml of reagent water.
5.9 Stock mercury solution: Dissolve 0.1354 g of mercuric chloride in
75 ml of reagent water. Add 10 ml of concentrated HN03 and adjust the volume to
100.0 ml (1 ml = 1 mg Hg). Stock solutions may also be purchased.
5.10 Mercury working standard: Make successive dilutions of the stock
mercury solution to obtain a working standard containing 0.1 ug per ml. This
working standard and the dilutions of the stock mercury solution should be
prepared fresh daily. Acidity of the working standard should be maintained at
0.15% nitric acid. This acid should be added to the flask, as needed, before
addition of the aliquot.
7470A - 3 Revision 1
September 1994
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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
reagent water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH <2 with HN03. The
suggested maximum holding times for mercury is 28 days.
6.4 Nonaqueous samples shall be refrigerated, when possible, and analyzed
as soon as possible.
7.0 PROCEDURE
7.1 Sample preparation: Transfer 100 mL, or an aliquot diluted to
100 mL, containing <1.0 g of mercury, to a 300-mL BOD bottle or equivalent. Add
5 mL of H2S04 and 2.5 mL of concentrated HN03, mixing after each addition. Add
15 mL of potassium permanganate solution to each sample bottle. Sewage samples
may require additional permanganate. Ensure that equal amounts of permanganate
are added to standards and blanks. Shake and add additional portions of
potassium permanganate solution, if necessary, until the purple color persists
for at least 15 min. Add 8 mL of potassium persulfate to each bottle and heat
for 2 hr in a water bath maintained at 95°C. Cool and add 6 mL of sodium
chloride-hydroxylamine sulfate to reduce the excess permanganate. After a delay
of at least 30 sec, add 5 mL of stannous sulfate, immediately attach the bottle
to the aeration apparatus, and continue as described in Paragraph 7.3.
7.2 Standard preparation: Transfer 0-, 0.5-, 1.0-, 2.0-, 5.0-, and 10.0-
mL aliquots of the mercury working standard, containing 0-1.0 ug of mercury, to
a series of 300-mL BOD bottles. Add enough reagent water to each bottle to make
a total volume of 100 mL. Mix thoroughly and add 5 mL of concentrated H2S04 and
2.5 mL of concentrated HN03 to each bottle. Add 15 mL of KMn04 solution to each
bottle and allow to stand at least 15 min. Add 8 mL of potassium persulfate to
each bottle and heat for 2 hr in a water bath maintained at 95°C. Cool and add
6 mL of sodium chloride-hydroxylamine sulfate solution to reduce the excess
permanganate. When the solution has been decolorized, wait 30 sec, add 5 mL of
the stannous sulfate solution, immediately attach the bottle to the aeration
apparatus, and continue as described in Paragraph 7.3.
7.3 Analysis: At this point the sample is allowed to stand quietly
without manual agitation. The circulating pump, which has previously been
adjusted to a rate of 1 liter/min, is allowed to run continuously. The
absorbance will increase and reach a maximum within 30 sec. As soon as the
recorder pen levels off (approximately 1 min), open the bypass valve and continue
the aeration until the absorbance returns to its minimum value. Close the bypass
valve, remove the stopper and frit from the BOD bottle, and continue the
aeration. Because of instrument variation refer to the manufacturers recommended
operating conditions when using this method.
7470A - 4 Revision 1
September 1994
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7.4 Construct a calibration curve by plotting the absorbances of stan-
dards versus micrograms of mercury. Determine the peak height of the unknown
from the chart and read the mercury value from the standard curve. Duplicates,
spiked samples, and check standards should be routinely analyzed.
7.5 Calculate metal concentrations (1) by the method of standard
additions, or (2) from a calibration curve. All dilution or concentration
factors must be taken into account. Concentrations reported for multiphased or
wet samples must be appropriately qualified (e.g., 5 ug/g dry weight).
8.0 QUALITY CONTROL
8.1 Refer to section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 245.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 245.1.
7470A - 5 Revision 1
September 1994
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METHOD 7470A
MERCURY IN LIQUID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
Sample Preparation
Standard Preparation
7.1 Transfer aliquot
to bottle, add H2S04
and HNOi and mix.
7.1 Add KMn04
and shake.
7.2 Tranafer aliquot
of the Hg working
•tandard to
bottle.
7.2 Add raagent
water, mix, add
concentrated
HjSC^and
7.1 Add more
permanganate
if neceeaary.
7.1 Add
potassium
pereulfete, heat
for 2 hrs., cool.
7.2 Add KMn04
potaaaium
peraulfate, heat
for 2 hrs. and cool.
7.2 Add eodium
chloride-
hydroxylamine
eulfate, wait 30
eeconda.
7.1 Add sodium
chloride-
hydroxylamine
sulfate, wait 30
seconds.
7.1 Add atannoua
sulfate, attach
to aeretion
apparatus.
7.3 Analyze
aample.
7.2 Add stannous
aulfate, attach
to aeration
apparatue.
7.4 Conatruct
calibration
curve, determine
peak height and
Hg value.
7.4 Routinely
analyze duplicates,
spiked samples.
7.5 Calculate
metal
concentrations.
( Stop J
7470A - 6
Revision 1
September 1994
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METHOD 7471A
MERCURY IN SOLID OR SEMISOLID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 Method 7471 is approved for measuring total mercury (organic and
inorganic) in soils, sediments, bottom deposits, and sludge-type materials. All
samples must be subjected to an appropriate dissolution step prior to analysis.
If this dissolution procedure is not sufficient to dissolve a specific matrix
type or sample, then this method is not applicable for that matrix.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis, the solid or semi-solid samples must be prepared
according to the procedures discussed in this method.
2.2 Method 7471, a cold-vapor atomic absorption method, is based on the
absorption of radiation at the 253.7-nm wavelength by mercury vapor. The mercury
is reduced to the elemental state and aerated from solution in a closed system.
The mercury vapor passes through a cell positioned in the light path of an atomic
absorption spectrophotometer. Absorbance (peak height) is measured as a function
of mercury concentration.
2.3 The typical instrument detection limit (IDL) for this method is
0.0002 mg/L.
3.0 INTERFERENCES
3.1 Potassium permanganate is added to eliminate possible interference
from sulfide. Concentrations as high as 20 mg/Kg of sulfide, as sodium sulfide,
do not interfere with the recovery of added inorganic mercury in reagent water.
3.2 Copper has also been reported to interfere; however, copper concen-
trations as high as 10 mg/Kg had no effect on recovery of mercury from spiked
samples.
3.3 Samples high in chlorides require additional permanganate (as much
as 25 ml) because, during the oxidation step, chlorides are converted to free
chlorine, which also absorbs radiation of 253 nm. Care must therefore be taken
to ensure that free chlorine is absent before the mercury is reduced and swept
into the cell. This may be accomplished by using an excess of hydroxylamine
sulfate reagent (25 ml). In addition, the dead air space in the BOD bottle must
be purged before adding stannous sulfate.
3.4 Certain volatile organic materials that absorb at this wavelength may
also cause interference. A preliminary run without reagents should determine if
this type of interference is present.
4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer or equivalent: Any atomic
absorption unit with an open sample presentation area in which to mount the
7471A - 1 Revision 1
September 1994
-------
absorption cell is suitable. Instrument settings recommended by the particular
manufacturer should be followed. Instruments designed specifically for the
measurement of mercury using the cold-vapor technique are commercially available
and may be substituted for the atomic absorption spectrophotometer.
4.2 Mercury hollow cathode lamp or electrodeless discharge lamp.
4.3 Recorder: Any multirange variable-speed recorder that is compatible
with the UV detection system is suitable.
4.4 Absorption cell: Standard spectrophotometer cells 10 cm long with
quartz end windows may be used. Suitable cells may be constructed from Plexiglas
tubing, 1 in. O.D. x 4.5 in. The ends are ground perpendicular to the
longitudinal axis, and quartz windows (1 in. diameter x 1/16 in. thickness) are
cemented in place. The cell is strapped to a burner for support and aligned in
the light beam by use of two 2-in. x 2-in. cards. One-in.-diameter holes are cut
in the middle of each card. The cards are then placed over each end of the cell.
The cell is then positioned and adjusted vertically and horizontally to give the
maximum transmittance.
4.5 Air pump: Any peristaltic pump capable of del ivering 1 L/min air may
be used. A Masterflex pump with electronic speed control has been found to be
satisfactory.
4.6 Flowmeter: Capable of measuring an air flow of 1 L/min.
4.7 Aeration tubing: A straight glass frit with a coarse porosity. Tygon
tubing is used for passage of the mercury vapor from the sample bottle to the
absorption cell and return.
4.8 Drying tube: 6-in. x 3/4-in.-diameter tube containing 20 g of
magnesium perch!orate or a small reading lamp with 60-W bulb which may be used
to prevent condensation of moisture inside the cell. The lamp should be
positioned to shine on the absorption cell so that the air temperature in the
cell is about 10°C above ambient.
4.9 The cold-vapor generator is assembled as shown in Figure 1 of
reference 1 or according to the instrument manufacturers instructions. The
apparatus shown in Figure 1 is a closed system. An open system, where the
mercury vapor is passed through the absorption cell only once, may be used
instead of the closed system. Because mercury vapor is toxic, precaution must be
taken to avoid its inhalation. Therefore, a bypass has been included in the
system either to vent the mercury vapor into an exhaust hood or to pass the
vapor through some absorbing medium, such as:
1. equal volumes of 0.1 M KMn04 and 10% H2S04, or
2. 0.25% iodine in a 3% KI solution.
A specially treated charcoal that will adsorb mercury vapor is also
available from Barneby and Cheney, East 8th Avenue and North Cassidy
Street, Columbus, Ohio 43219, Cat. #580-13 or #580-22.
7471A - 2 Revision 1
September 1994
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4.10 Hot plate or equivalent - Adjustable and capable of maintaining a
temperature of 90-95°C.
4.11 Graduated cylinder or equivalent.
5.0 REAGENTS
5.1 Reagent Water: Reagent water will be interference free. All
references to water in this method refer to reagent water unless otherwise
specified.
5.2 Aqua regia: Prepare immediately before use by carefully adding three
volumes of concentrated HC1 to one volume of concentrated HN03.
5.3 Sulfuric acid, 0.5 N: Dilute 14.0 ml of concentrated sulfuric acid
to 1 liter.
5.4 Stannous sulfate: Add 25 g stannous sulfate to 250 ml of 0.5 N
sulfuric acid. This mixture is a suspension and should be stirred continuously
during use. A 10% solution of stannous chloride can be substituted for stannous
sulfate.
5.5 Sodium chloride-hydroxylamine sulfate solution: Dissolve 12 g of
sodium chloride and 12 g of hydroxylamine sulfate in reagent water and dilute to
100 ml. Hydroxylamine hydrochloride may be used in place of hydroxylamine
sulfate.
5.6 Potassium permanganate, mercury-free, 5% solution (w/v): Dissolve
5 g of potassium permanganate in 100 ml of reagent water.
5.7 Mercury stock solution: Dissolve 0.1354 g of mercuric chloride in
75 ml of reagent water. Add 10 ml of concentrated nitric acid and adjust the
volume to 100.0 ml (1.0 ml = 1.0 mg Hg).
5.8 Mercury working standard: Make successive dilutions of the stock
mercury solution to obtain a working standard containing 0.1 ug/mL. This working
standard and the dilution of the stock mercury solutions should be prepared fresh
daily. Acidity of the working standard should be maintained at 0.15% nitric
acid. This acid should be added to the flask, as needed, before adding the
aliquot.
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
reagent water. Plastic and glass containers are both suitable.
6.3 Non-aqueous samples shall be refrigerated, when possible, and
analyzed as soon as possible."
7471A - 3 Revision 1
September 1994
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7.0 PROCEDURE
7.1 Sample preparation: Weigh triplicate 0.2-g portions of untreated
sample and place in the bottom of a BOD bottle. Add 5 ml of reagent water and
5 ml of aqua regia. Heat 2 min in a water bath at 95°C. Cool; then add 50 ml
reagent water and 15 ml potassium permanganate solution to each sample bottle.
Mix thoroughly and place in the water bath for 30 min at 95°C. Cool and add 6
mL of sodium chloride-hydroxylamine sulfate to reduce the excess permanganate.
CAUTION: Do this addition under a hood, as C12 could be evolved.
Add 55 ml of reagent water. Treating each bottle individually, add
5 mL of stannous sulfate and immediately attach the bottle to the
aeration apparatus. Continue as described under step 7.4.
7.2 An alternate digestion procedure employing an autoclave may also be
used. In this method, 5 ml of concentrated H2S04 and 2 ml of concentrated HN03
are added to the 0.2 g of sample. Add 5 ml of saturated KMn04 solution and cover
the bottle with a piece of aluminum foil. The samples are autoclaved at 121°C
and 15 Ib for 15 min. Cool, dilute to a volume of 100 ml with reagent water, and
add 6 ml of sodium chloride-hydroxylamine sulfate solution to reduce the excess
permanganate. Purge the dead air space and continue as described under step 7.4.
Refer to the caution statement in section 7.1 for the proper protocol in reducing
the excess permanganate solution and adding stannous sulfate.
7.3 Standard preparation: Transfer 0.0-, 0.5-, 1.0-, 2.0-, 5.0-, and 10-
mL aliquots of the mercury working standard, containing 0-1.0 ug of mercury, to
a series of 300-mL BOD bottles or equivalent. Add enough reagent water to each
bottle to make a total volume of 10 ml. Add 5 mL of aqua regia and heat 2 min
in a water bath at 95°C. Allow the sample to cool; add 50 mL reagent water and
15 mL of KMn04 solution to each bottle and return to the water bath for 30
min. Cool and add 6 mL of sodium chloride-hydroxylamine sulfate solution to
reduce the excess permanganate. Add 50 mL of reagent water. Treating each
bottle individually, add 5 mL of stannous sulfate solution, immediately attach
the bottle to the aeration apparatus, and continue as described in
Step 7.4.
7.4 Analysis: At this point, the sample is allowed to stand quietly
without manual agitation. The circulating pump, which has previously been
adjusted to a rate of 1 L/min, is allowed to run continuously. The absorbance,
as exhibited either on the spectrophotometer or the recorder, will increase and
reach maximum within 30 sec. As soon as the recorder pen levels off
(approximately 1 min), open the bypass valve and continue the aeration until the
absorbance returns to its minimum value. Close the bypass valve, remove the
fritted tubing from the BOD bottle, and continue the aeration.
7.5 Construct a calibration curve by plotting the absorbances of stan-
dards versus micrograms of mercury. Determine the peak height of the unknown
from the chart and read the mercury value from the standard curve. Duplicates,
spiked samples, and check standards should be routinely analyzed.
7.6 Calculate metal concentrations: (1) by the method of standard
additions, (2) from a calibration curve, or (3) directly from the instrument's
concentration read-out. All dilution or concentration factors must be taken into
7471A - 4 Revision 1
September 1994
-------
account. Concentrations reported for multiphased or wet samples must be
appropriately qualified (e.g., 5 ug/g dry weight).
8.0 QUALITY CONTROL
8.1 Refer to section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 245.5 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 245.5.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7471A - 5 Revision 1
September 1994
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Emission control dust Not known 12, 12 ug/g
Wastewater treatment sludge Not known 0.4, 0.28 ug/g
7471A - 6 Revision 1
September 1994
-------
METHOD 7471A
MERCURY IN SOLID OR SEMISOLID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
( -" )
Sample Preparation
Standard Preparation
/ Typ
f Dige
>v Met!
1
r
9 of \TV2P<>
lod? >/
Type
f 1
7.1 Weigh triplicate
samples, and reagent
water and
aqua regia.
1
r
7.1 Heat, cool,
add reagent water
and KMn04.
1
>
>
r
7.3 Transfer aliquot*
of Hg working
standards to
bottle*.
,
r
7.3 Add reagent
water to volume,
and aqua regia,
heat and cool.
r
7.2 Add
KMn04, cover,
heat and cool,
dilute with
reagent water.
L
7.1 Heat, cool,
add sodium
chlonde-
hydroxylamme
sulfate.
I
7.2 Add sodium
chlonde-
hydroxylamine
sulfate, purge
dead air space.
i
7.1 Add reagent
water, stannou*
sulfate, attach
to aeration
apparatus.
w
\r
7.4 Analyze
sample.
1
7.5 Construct
calibration
curve; determine
peak height and
Hg value.
1
7.5 Routinely
analyze duplicates,
spiked samples.
J
r
7.3 Add reagent
water and KMnO4
solution, heat
and cool.
4
7.3 Add sodium
chloride-
hydroxylamme
sulfate and
reagent water.
i
7.C
stannoi
appi
'
Add
s sulfate,
o aeration
iratus.
7.6 Calculate
metal
concentrations.
( Stop j
7471A - 7
Revision 1
September 1994
-------
METHOD 7480
MOLYBDENUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Interferences in an air/acetylene flame from Ca, Sr, $04, and Fe are
severe. These interferences are greatly reduced in the nitrous oxide flame
and by addition of 1,000 mg/L aluminum to samples and standards.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Molybdenum hollow cathode lamp.
4.2.2 Wavelength: 313.3 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxidant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.840 g of ammonium molybdate,
(NH4)sMo7024*4H20 (analytical reagent grade), in Type II water and dilute
to 1 liter; 1 mL = 1 mg Mo (1,000 mg/L). Alternatively, procure a
certified standard from a supplier and verify by comparison with a second
standard.
7480 - 1
Revision
Date September 1986
-------
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 add and at the same
concentration as will result 1n the sample to be analyzed after
processing. The samples and standards should also contain 1,000 mg/L
aluminum (see Paragraph 5.2.3).
5.2.3 Aluminum nitrate solution: Dissolve 139 g aluminum nitrate,
A1(N03)3*9H20, in 150 ml of Type II water; heat to effect solution.
Allow to cool and make up to 200 mL. To each 100 ml of standard and
sample alike, add 2 ml of the aluminum nitrate solution.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 1-40 mg/L with a wavelength of 313.3 nm.
Sensitivity: 0.4 mg/L.
Detection limit: 0.1 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 0.3, 1.5, and
7.5 mg/L gave standard deviations of +0.007, +0.02, and +0.07, respectively.
Recoveries at these levels were 100%, 96%, and 95%, respectively.
9.3 For concentrations of molybdenum below 0.2 mg/L, the furnace
technique (Method 7481) is recommended.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 246.1.
7480 - 2
Revision 0
Date September 1986
-------
METHOD 7ABO
MOLYBDENUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
C
5.O
Prepare
standards
7.1
For
sample
preparation see
chapter 3.
section 3.2
7.2
Analyze using
Method 7OOO.
Section 7.Z
( Stop J
7480 - 3
Revision 0
Date September 1986
-------
METHOD 7481
MOLYBDENUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Molybdenum is prone to carbide formation. Use a pyrolytically
coated graphite tube.
3.3 Memory effects are possible, and cleaning of the furnace may be
required after analysis of more concentrated samples or standards.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 1400*C.
4.2.3 Atomizing time and temp: 5 sec at 2800*C.
4.2.4 Purge gas: Argon (nitrogen should not be used).
4.2.5 Wavelength: 313.3 nm.
4.2.6 Background correction: Required.
4.2.7 Other operating parameters should be set as specified by the
particular instrument manufacturer.
4.2.8 Pyrolytically coated graphite tube.
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 sizes of 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.
7481 - 1
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.840 g of ammonium molybdate,
(NH4)6M07024'4H20 (analytical reagent grade), 1n Type II water and
dilute to 1 liter; 1 mL = 1 mg Mo (1,000 mg/L). Alternatively, procure a
certified standard from a supplier and verify 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
concentrations as in the sample after processing (0.5% v/v
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
is given in Method 7000, Paragraph 7.4.
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.
9.2 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 3-60 ug/L.
Detection limit: 1 ug/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 246.2.
7481 - 2
Revision 0
Date September 1986
-------
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-------
METHOD 7520
NICKEL (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Background correction is required.
3.3 High concentrations of iron, cobalt, or chromium may interfere,
requiring either matrix matching or use of a nitrous-oxide/acetylene flame.
3.4 A nonresonance line of Ni at 232.14 nm causes nonlinear calibration
curves at moderate to high nickel concentrations, requiring sample dilution or
use of the 352.4-nm line.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Nickel hollow cathode lamp.
4.2.2 Wavelength: 232.0 nm (primary); 352.4 nm (alternate).
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g nickel metal (analytical
reagent grade) or 4.953 g nickel nitrate, Ni(N03)2*6H20 (analytical
reagent grade), in 10 mL HNOs and dilute to 1 liter with Type II water.
7520 - 1
Revision 0
Date September 1986
-------
Alternatively, procure a certified standard from a supplier and verify 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
concentration as will result in the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 0.3-5 mg/L with a wavelength of 232.0 nm.
Sensitivity: 0.15 mg/L.
Detection limit: 0.04 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 0.2, 1.0, and
5.0 mg/L gave standard deviations of +0.011, +0.02, and +0.04, respectively.
Recoveries at these levels were 100%, 97%, and 93%, respectively.
9.3 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
7520 - 2
Revision
Date September 1986
-------
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 249.1
2. Gaskm, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7520 - 3
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Wastewater treatment sludge 3050 13,000, 10,400 ug/g
7520 - 4
Revision 0
Date September 1986
-------
METHOD 7520
NICKEL (ATOMIC ABSORPTION. DIRECT ASPIRATION)
Start
5.0
Prepare
standards
7. 1
P^epar
ct
sec
For
samp le
atlon see
apter 3.
tion 3.2
7.2
Ana] yze
Method
Section
us Ing
7000,
7.2
Stop
7520 - 5
Revision o
Date September 1986
-------
METHOD 7550
OSMIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 Method 7550 is an atomic absorption procedure approved for
determining the concentration of osmium 1n wastes, mobility procedure
extracts, soils, and ground water. All samples must be subjected to an
appropriate dissolution step prior to analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis by Method 7550, samples must be prepared for
direct aspiration. The method of sample preparation will vary according to
the sample matrix. Aqueous samples are subjected to the acid digestion
procedure discussed in this method. Sludge samples are prepared using the
procedure described in Method 3050. For samples containing oils, greases, or
waxes, the procedure described in Method 3040 may be applicable. Due to the
very volatile nature of some osmium compounds, the applicability of a method
to a sample must be verified by means of spiked samples or standard reference
materials, or both.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot is aspirated into a nitrous oxide/acetylene flame. The resulting
absorption of hollow cathode radiation will be proportional to the osmium
concentration. Background correction must be employed for all analyses.
2.3 The typical detection limit for this method is 0.3 mg/L; typical
sensitivity 1s 1 mg/L.
3.0 INTERFERENCES
3.1 Background correction is required because nonspecific absorption and
light scattering can be significant at the analytical wavelength.
3.2 Due to the volatility of osmium, standards must be made on a daily
basis, and the applicability of sample-preparation techniques must be verified
for the sample matrices of Interest.
3.3 Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.
3.4 Osmium and its compounds are extremely toxic; therefore, extreme
care must be taken to ensure that samples and standards are handled properly
and that all exhaust gases are properly vented.
7550 - 1
Revision 0
Date September 1986
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4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer; Single- or dual-channel,
single- ordouble-beamInstrumentwithagrating monochromator, photomul-
tlpller detector, adjustable slits, and provisions for background correction.
4.2 Osmium hollow cathode lamp.
4.3 Strip-chart recorder (optional).
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid (HN03): Add should be analyzed to
determine levels of impurities.IT" a method blank using the acide 1s
-------
6.4 Nonaqueous samples shall be refrigerated, when possible, and
analyzed as soon as possible.
7.0 PROCEDURE
7.1 Sample preparation; Aqueous samples should be prepared according to
the procedure describedTrT Paragraph 7.2. Sludge-type samples should be
prepared according to Method 3050; samples containing oils, greases, or waxes
may be prepared according to Method 3040. The applicability of a sample
preparation technique to a new matrix type must be demonstrated by analyzing
spiked samples, relevant standard reference materials, or both.
7.2 Sample preparation of aqueous samples;
7.2.1 Transfer a representative 100-mL aliquot of the well-mixed
sample to a Griffin beaker and add 1 ml of concentrated HN03.
7.2.2 Place the beaker on a steam bath or hot plate and warm for 15
mln. Cool the beaker and, 1f necessary, filter or centrifuge to remove
Insoluble material.
7.2.3 Add 1 ml of concentrated H2S04 and adjust the volume back to
100 ml. The sample 1s now ready for analysis.
7.3 The 290.0-nm wavelength line and background correction shall be
employed.
7.4 A fuel-rich nitrous oxide/acetylene flame shall be used.
7.5 Follow the manufacturer's operating Instructions for all other
Instrument parameters.
7.6 Either (1) run a series of osmium standards and construct a
calibration curve by plotting the concentrations of the standards against the
absorbances, or (2) for the method of standard additions, plot added
concentration versus absorbance. For Instruments that read directly in
concentration, set the curve corrector to read out the proper concentration.
7.7 Analyze all EP extracts, all samples analyzed as part of a deli sting
petition, and all samples that suffer from matrix interferences by the method
of standard additions.
7.8 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.9 Calculate metal concentrations: (1) by the method of standard
additions, (2) from a calibration curve, or (3) directly from the Instrument's
concentration read-out. All dilution or concentration factors must be taken
into account.
7550 - 3
Revision 0
Date September 1986
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8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples 1f they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine If
contamination or any memory effects are occurring.
8.5 Verify calibration with an Independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 10 samples. A duplicate
sample 1s a sample brought through the entire sample preparation and
analytical process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a del 1 sting petition, and whenever a new sample matrix 1s being
analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are not available at this time.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 252.1.
7550 - 4
Revision
Date September 1986
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METHOD 7SSO
OSMIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION METHOD)
C
Samples containing
oils, greases.
or wanes
Sludge-type
^ * wwv «: w 71-
samples
ror sampje '
preparation
aliquot of
sample to
beaker: add
cone. HN03
Use Method 3050
Use Method 3040
Warm Beaker;
cool and filter
If necessary
Add cone.
H,SO«: adjust
volume
7.3-5
Adjust
Instrument
parameters
7.6
Plot
callbrat ion
curve
7.7
Analyze
by method of
standard
additions
7.B
Routinely
analyze
duplicates.
spiked samples
and check
standards
7.9
Calculate natal
concentrations
f Stop J
7550 - 5
Revision 0
Date September 1986
-------
METHOD 7610
POTASSIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 In air/acetylene or other high-temperature flames (>2800*C), potas-
sium can experience partial ionization, which indirectly affects absorption
sensitivity. The presence of other alkali salts in the sample can reduce this
ionization and thereby enhance analytical results. The ionization-suppressive
effect of sodium is small if the ratio of Na to K is under 10. Any enhance-
ment due to sodium can be stabilized by adding excess sodium (1,000 ug/mL) to
both sample and standard solutions. If more stringent control of ionization
is required, the addition of cesium should be considered. Reagent blanks
should be analyzed to correct for potassium impurities in the buffer stock.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Potassium hollow cathode lamp.
4.2.2 Wavelength: 766.5 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxidant: Air.
4.2.5 Type of flame: Slightly oxidizing (fuel lean).
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
7610 - 1
Revision
Date September 1986
-------
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.907 g of potassium chloride, KC1
(analytical reagent grade), dried at 110*C 1n Type II water and dilute to
1 liter with Type II water. Alternatively, procure a certified standard
from a supplier and verify 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
concentration as will result In the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation: The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.1-2 mg/L with a wavelength of 766.5 nm.
Sensitivity: 0.04 mg/L.
Detection limit: 0.01 mg/L.
9.2 In a single laboratory, analysis of a mixed Industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 1.6 and 6.3
mg/L gave standard deviations of +0.2 and +0.5, respectively. Recoveries at
these levels were 103% and 102%, respectively.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 258.1.
7610 - 2
Revision
Date September 1986
-------
METHOD 761O
POTASSIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.O
Prepare
standards
7. 1
prepar
cl-
sec
For
sample
atton see
apter 3.
tlon 3.2
7.2
Analyze using
Method 7000.
Section 7.2
f Stop J
7610 - 3
Revision 0
Date September 1986
-------
METHOD 7740
SELENIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 Method 7740 Is an atomic absorption procedure approved for
determining the concentration of selenium in wastes, mobility-procedure
extracts, soils, and ground water. All samples must be subjected to an
appropriate dissolution step prior to analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis by Method 7740, samples must be prepared in order
to convert organic forms of selenium to inorganic forms, to minimize organic
interferences, and to convert samples to suitable solutions for analysis. The
sample-preparation procedure varies, depending on the sample matrix. Aqueous
samples are subjected to the acid-digestion procedure described in this
method. Sludge samples are prepared using the procedure described in Method
3050.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot 1s placed manually or by means of an automatic sampler into a
graphite tube furnace. The sample aliquot is then slowly evaporated to
dryness, charred (ashed), and atomized. The absorption of lamp radiation
during atomization will be proportional to the selenium concentration.
2.3 The typical detection limit for this method is 2 ug/L.
3.0 INTERFERENCES
3.1 Elemental selenium and many of Its compounds are volatile;
therefore, samples may be subject to losses of selenium during sample
preparation. Spike samples and relevant standard reference materials should
be processed to determine if the chosen dissolution method 1s appropriate.
3.2 Likewise, caution must be employed during the selection of
temperature and times for the dry and char (ash) cycles. A nickel nitrate
solution must be added to all dlgestates prior to analysis to minimize
volatilization losses during drying and ashing.
3.3 In addition to the normal interferences experienced during graphite
furnace analysis, selenium analysis can suffer from severe nonspecific
absorption and light scattering caused by matrix components during
atomization. Selenium analysis is particularly susceptible to these problems
because of its low analytical wavelength (196.0 nm). Simultaneous background
correction is required to avoid erroneously high results. High iron levels
can give overcorrection with deuterium background. Zeeman background
correction can be useful in this situation.
7740 - 1
Revision 0
Date September 1986
-------
3.4 If the analyte 1s not completely volatilized and removed from the
furnace during atomlzatlon, memory effects will occur. If this situation 1s
detected, the tube should be cleaned by operating the furnace at full power at
regular intervals In the analytical scheme.
3.5 Selenium analysis suffers interference from chlorides (>800 mg/L)
and sulfate (>200 mg/L). The addition of nickel nitrate such that the final
concentration is 1% nickel will lessen this interference.
4.0 APPARATUS AND MATERIALS
4.1 250-mL Griffin beaker.
4.2 10-mL volumetric flasks.
4.3 Atomic absorption spectrophptometer; Single- or dual-channel,
single- or double-beam instrument with a grating monochromator, photomulti-
plier detector, adjustable slits, a wavelength range of 190-800 nm, and
provisions for simultaneous background correction and interfacing with a
strip-chart recorder.
4.4 Selenium hollow cathode lamp, or electrode! ess discharge lamp (EDL);
EDLs provide better sensitivity for the analysis of Se.
4.5 Graphite furnace; Any graphite furnace device with the appropriate
temperature and timing controls.
4.6 Strip-chart recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any problems
with the analysis, such as drift, Incomplete atomization, losses during
charring, changes in sensitivity, etc., can easily be recognized.
4.7 Pi pets; Microliter with disposable tips. Sizes can range from
5 to 1,000 uL, as required.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid (HNOs); Acid should be analyzed to
determine levels of impurities. Tf~a method blank made with the acid is
-------
5.4 Selenium standard stock solution (1,000 mg/L): Either procure a
certified aqueous standard fromasupplier and verify by comparison with a
second standard, or dissolve 0.3453 g of selenlous add (actual assay 94.6%
H2Se03, analyticaTreagent grade) or equivalent in Type II water and dilute to
200 mL.
5.5 Nickel nitrate solution (5%): Dissolve 24.780 g of ACS reagent
grade Ni(N03)2*6H20 or equivalent in Type II water and dilute to 100 ml.
5.6 Nickel nitrate solution (1%): Dilute 20 ml of the 5% nickel nitrate
to 100 ml with Type II water.
5.7 Selenium working standards; Prepare dilutions of the stock solution
to be used as calibration standards at the time of the analysis. Withdraw
appropriate aliquots of the stock solution, add 1 ml of concentrated HN03,
2 ml of 30% H202, and 2 ml of the 5% nickel nitrate solution. Dilute to
100 ml with Type II water.
5.8 Air; Cleaned and dried through a suitable filter to remove oil,
water, and other foreign substances. The source may be a compressor or a
cylinder of industrial-grade compressed air.
5.9 Hydrogen; Suitable for instrumental analysis.
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
Type II water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used 1f very volatile selenium compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric acid.
6.5 Nonaqueous samples shall be refrigerated, when possible, and
analyzed as soon as possible.
7.0 PROCEDURE
7.1 Sample preparation; Aqueous samples should be prepared 1n the
manner described inSteps7.1.1 to 7.1.3. Sludge-type samples should be
prepared according to Method 3050. The applicability of a sample-preparation
technique to a new matrix type must be demonstrated by analyzing spiked
samples and/or relevant standard reference materials.
7740 - 3
Revision
Date September 1986
-------
7.1.1 Transfer 100 mL of well-mixed sample to a 250-mL Griffin
beaker; add 2 ml of 30% ^2 and sufficient concentrated HN03 to result
in an acid concentration of 1% (v/v). Heat for 1 hr at 95*C or until the
volume is slightly less than 50 mL.
7.1.2 Cool and bring back to 50 ml with Type II water.
7.1.3 Pi pet 5 ml of this digested solution into a 10-mL volumetric
flask, add 1 ml of the 1% nickel nitrate solution, and dilute to 10 ml
with Type II water. The sample is now ready for injection into the
furnace.
7.2 The 196.0-nm wavelength line and a background correction system must
be employed. Follow the manufacturer's suggestions for all other spectropho-
tometer parameters.
7.3 Furnace parameters suggested by the manufacturer should be employed
as guidelines. Because temperature-sensing mechanisms and temperature
controllers can vary between instruments or with time, the validity of the
furnace parameters must be periodically confirmed by systematically altering
the furnace parameters while analyzing a standard. In this manner, losses of
analyte due to overly high temperature settings or losses in sensitivity due
to less than optimum settings can be minimized. Similar verification of
furnace parameters may be required for complex sample matrices.
7.4 Inject a measured uL-al1quot of sample into the furnace and atomize.
If the concentration found is greater than the highest standard, the sample
should be diluted in the same acid matrix and reanalyzed. The use of multiple
injections can improve accuracy and help detect furnace pipetting errors.
7.5 Analyze all EP extracts, all samples analyzed as part of a deli sting
petition, and all samples that suffer from matrix interferences by the method
of standard additions.
7.6 Run a check standard after approximately every 10 sample Injections.
Standards are run in part to monitor the life and performance of the graphite
tube. Lack of reproducibility or significant change in the signal for the
standard indicates that the tube should be replaced.
7.7 Duplicates, spiked samples, and check standards should be analyzed
every 20 samples.
7.8 Calculate metal concentrations: (1) by the method of standard
additions, (2) from a calibration curve, or (3) directly from the instrument's
concentration read-out. All dilution or concentration factors must be taken
into account.
7740 - 4
Revision
Date September 1986
-------
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Verify calibration with an independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 10 samples. A duplicate
sample is a sample brought through the entire sample preparation and
analytical process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a deli sting petition, and whenever a new sample matrix is being
analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 270.2 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 270.2.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7740 - 5
Revision 0
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Emission control dust 3050 14, 11 ug/g
7740 - 6
Revision
Date September 1986
-------
METHOD 7740
SELENIUM (ATOMIC ABSORPTION. FURNACE METHOD)
Type of sample
for sample
preparat ion
7.1 . 11 Transfer
1 portion
of sample to
beaker; add 30X
HzOi and cone.
HNO,
heat
7. 1.2
Cool: bring to
volume
7.1.3
Plpet
digested
solution
into flask; add
nickel nitrate
solution:dilute
Sludge-type
samples
7. l
Prepare sample
according to
Method 3050
7740 - 7
Revision 0
Date September 1986
-------
METHOD 7740
SELENIUM (ATOMIC ABSORPTION FURNACE METHOD)
(Cont inued)
7.2
Set Instrument
parameters
7.3
7.5
Analyze
method of
standard
addition
Periodically
check validity
of furnace
parameters
7.4
7.6 I
Run
check standard
after 10 sample
Injections
Inject sample
into furnace:
atomize
Is
concentration
> highest
standard?
Dilute sample
and reanalyze
7.7
Routinely
analyze
duplicates.
spiked samples.
and check
standards
7.8
Calculate metal
concentrations
( Stop J
7740 - 8
Revision 0
Date September 1986
-------
METHOD 7741A
SELENIUM (ATOMIC ABSORPTION, GASEOUS HYDRIDE)
1.0 SCOPE AND APPLICATION
1.1 Method 7741 is an atomic absorption procedure that is approved for
determining the concentration of selenium in wastes, mobility-procedure extracts,
soils, and ground water, provided that the sample matrix does not contain high
concentrations of chromium, copper, mercury, silver, cobalt, or molybdenum. All
samples must be subjected to an appropriate dissolution step prior to analysis.
Spiked samples and relevant standard reference materials are employed to
determine applicability of the method to a given waste. If interferences are
present the analyst should consider using Method 7740.
2.0 SUMMARY OF METHOD
2.1 Samples are prepared according to the nitric/sulfuric acid digestion
procedure described in this method. Next, the selenium in the digestate is
reduced to Se(IV) with tin chloride. The Se(IV) is then converted to a volatile
hydride with hydrogen produced from a zinc/HCl or sodium borohydrate/HCl
reaction.
2.2 The volatile hydride is swept into an argon-hydrogen flame located
in the optical path of an atomic absorption spectrophotometer; the resulting
absorbance is proportional to the selenium concentration.
2.3 The typical detection limit for this method is 0.002 mg/L.
3.0 INTERFERENCES
3.1 High concentrations of chromium, cobalt, copper, mercury, molybdenum,
nickel, and silver can cause analytical interferences.
3.2 Traces of nitric acid left following the sample work-up can result
in analytical interferences. Nitric acid must be distilled off the sample by
heating the sample until fumes of S03 are observed.
3.3 Elemental selenium and many of its compounds are volatile; therefore,
certain samples may be subject to losses of selenium during sample preparation.
4.0 APPARATUS AND MATERIALS
4.1 100-mL beaker.
4.2 Electric hot plate or equivalent - Adjustable and capable of
maintaining a temperature of 90-95°C.
4.3 A commercially available zinc slurry hydride generator or a generator
constructed from the following material (see Figure 1):
7741A - 1 Revision 1
September 1994
-------
4.3.1 Medicine dropper: Fitted into a size "0" rubber stopper
capable of delivering 1.5 ml.
4.3.2 Reaction flask: 50-mL, pear-shaped, with two 14/20 necks
(Scientific Glass, JM-5835).
4.3.3 Gas inlet-outlet tube: Constructed from a micro cold-finger
condenser (JM-3325) by cutting the portion below the 14/20 ground-glass
joint.
4.3.4 Magnetic stirrer: To homogenize the zinc slurry.
4.3.5 Polyethylene drying tube: 10-cm, filled with glass wool to
prevent particulate matter from entering the burner.
4.3.6 Flow meter: Capable of measuring 1 liter/min.
4.4 Atomic absorption spectrophotometer: Singleordual channel, single-
or double-beam instrument with a grating monochromator, photomultipl ier detector,
adjustable slits, a wavelength range of 190-800 nm, and provisions for
interfacing with a strip-chart recorder and simultaneous background correction.
4.5 Burner: Recommended by the particular instrument manufacturer for
the argon-hydrogen flame.
4.6 Selenium hollow cathode lamp or electrodeless discharge lamp.
4.7 Strip-chart recorder (optional).
5.0 REAGENTS
5.1 Reagent water: Water should be monitored for impurities. Reagent
water will be interference free. All references to water will refer to reagent
water.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
levels of impurities. If a method blank made with the acid is
-------
5.7 Stannous chloride solution: Dissolve 100 g SnCl2 in 100 ml of
concentrated HC1.
5.8 Selenium standard stock solution: 1,000 mg/L solution may be
purchased, or prepared as follows: Dissolve 0.3453 g of selenious acid (assay
94.6% of H2Se03) in reagent water. Add to a 200-mL volumetric flask and bring
to volume (1 ml = 1 mg Se).
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
reagent water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used if very volatile selenium compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric acid.
6.5 Nonaqueous samples shall be refrigerated, when possible, and analyzed
as soon as possible.
7.0 PROCEDURE
7.1 Sample preparation:
7.1.1 To a 50-mL aliquot of digested sample (or, in the case of
extracts, a 50-mL sample) add 10 mL of concentrated HN03 and 12 mL of
18 N H2S04. Evaporate the sample on a hot plate until white S03 fumes are
observed (a volume of about 20 mL). Do not let it char. If it chars,
stop the digestion, cool, and add additional HN03. Maintain an excess of
HN03 (evidence of brown fumes) and do not let the solution darken because
selenium may be reduced and lost. When the sample remains colorless or
straw yellow during evolution of S03 fumes, the digestion is complete.
Caution: Venting reaction vessels should be done with
caution and only under a fume hood or well ventilated
area.
7.1.2 Cool the sample, add about 25 mL reagent water, and again
evaporate to S03 fumes just to expel oxides of nitrogen. Cool. Add 40 mL
concentrated HC1 and bring to a volume of 100 mL with reagent water.
7.2 Prepare working standards from the standard stock solutions. The
following procedures provide standards in the optimum range.
7.2.1 To prepare a working stock solution, pipet 1 mL standard
stock solution (see Paragraph 5.8) into a 1-liter volumetric flask. Bring
to volume with reagent water containing 1.5 mL concentrated HN03/liter.
The concentration of this solution is 1 mg Se/L (1 mL = 1 ug Se).
7741A - 3 Revision 1
September 1994
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7.2.2 Prepare six working standards by transferring 0, 0.5, 1.0,
1.5, 2.0, and 2.5 ml of the working stock solution (see Paragraph 7.2.1)
into 100-mL volumetric flasks. Bring to volume with diluent. The
concentrations of these working standards are 0, 5, 10, 15, 20, and 25 ug
Se/L.
7.3 Standard additions:
7.3.1 Take the 15-, 20-, and 25-ug standards and transfer
quantitatively 25 ml from each into separate 50-mL volumetric flasks. Add
10 ml of the prepared sample to each. Bring to volume with reagent water
containing 1.5 ml HN03/liter.
7.3.2 Add 10 ml of prepared sample to a 50-mL volumetric flask.
Bring to volume with reagent water containing 1.5 ml HN03/liter. This is
the blank.
7.4 Follow the manufacturer's instructions for operating an argon-
hydrogen flame. The argon-hydrogen flame is colorless; therefore, it may be
useful to aspirate a low concentration of sodium to ensure that ignition has
occurred.
7.5 The 196.0-nm wavelength shall be used for the analysis of selenium.
7.6 Transfer a 25-mL portion of the digested sample or standard to the
reaction vessel. Add 0.5 ml SnCl2 solution. Allow at least 10 min for the metal
to be reduced to its lowest oxidation state. Attach the reaction vessel to the
special gas inlet-outlet glassware. Fill the medicine dropper with 1.50 ml
sodium borohydrate or zinc slurry that has been kept in suspension with the
magnetic stirrer. Firmly insert the stopper containing the medicine dropper into
the side neck of the reaction vessel. Squeeze the bulb to introduce the zinc
slurry or sodium borohydrate into the sample or standard solution. The metal
hydride will produce a peak almost immediately. When the recorder pen returns
partway to the base line, remove the reaction vessel.
8.0 QUALITY CONTROL
8rl Refer to section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 270.3 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 270.3.
7741A - 4 Revision 1
September 1994
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METHOD 7741A
SELENIUM (ATOMIC ABSORPTION, GASEOUS HYDRIDE)
C Start J
Standard Preparation
Sample Preparation
7.2.1 Pip.t
• toek
•olution into
flack; bring
to volume
7.2.2 Prepare 6
£• working
•tandarda from
•took; bring to
volvun
7.3.1 Tranafer
3 standard
portion*,add
•ample,bring to
volume
7.1.1 Add
concentrated
H.SO. and UNO.
to cample and
avaporata
7.1.1 Stop
digeation,cool,
add HMO.
7.1.2 Cool
•ample,add
reagent water,
evaporate,cool
7.3.2 To
prepare blank
add aampla to a
flaak and bring
to volume
7.4 Fallow
instruction*
for operating
irgon-hydrogen
flame
7.5 Uae 196.0
nm wavelength
7.1.2 Add
concentrated
HC1 and bring
to volume
7.6 Tranafer
digevted aamplfl
to reaction
veaael,add
SnCl,
7.6 Allow to
•tand,attach
vaaael to
glauware ,add
2n alurry
7.6 Record Se
concentration
C
Stop
7741A - 5
Revision 1
Septenter 1994
-------
METHOD 7742
SELENIUM (ATOMIC ABSORPTION, BOROHYDRIDE REDUCTION)
1.0 SCOPE AND APPLICATION
1.1 Method 7742 is an atomic absorption procedure for determining 3
to 750 fjg/l concentrations of selenium in wastes, mobility procedure extracts,
soils, and ground water. Method 7742 is approved for sample matrices that
contain a total of up to 1000 mg/L concentrations of cobalt, copper, iron,
mercury, and nickel. A solid sample can contain up to 10% by weight of the
interferents before exceeding 1000 mg/L in a digested sample. All samples
including aqueous matrices must be subjected to an appropriate dissolution step
prior to analysis. Spiked samples and relevant standard reference materials are
employed to determine the applicability of the method to a given waste.
2.0 SUMMARY OF METHOD
2.1 Samples are prepared according to the nitric acid digestion procedure
described in Method 3010 for aqueous and extract samples and the
nitric/peroxide/hydrochloric acid digestion procedure described in Method 3050
(furnace AA option) for sediments, soils, and sludges. Excess peroxide is
removed by evaporating samples to near-dryness at the end of the digestion
followed by dilution to volume and degassing the samples upon addition of urea.
The selenium is converted to the +4 oxidation state during digestion in HC1.
After a 1:10 dilution, selenium is then converted to its volatile hydride using
hydrogen produced from the reaction of the acidified sample with sodium
borohydride in a continuous-flow hydride generator.
2.2 The volatile hydrides are swept into, and decompose in, a heated
quartz absorption cell located in the optical path of an atomic absorption
spectrophotometer. The resulting absorption of the lamp radiation is
proportional to the selenium concentration.
2.3 The typical detection limit for this method is 3//g/L.
3.0 INTERFERENCES
3.1 Very high (>1000 mg/L) concentrations of cobalt, copper, iron,
mercury, and, nickel can cause analytical interferences through precipitation as
reduced metals and associated blockage of transfer lines and fittings.
3.2 Traces of peroxides left following the sample work-up can result in
analytical interferences. Peroxides must be removed by evaporating each sample
to near-dryness followed by reacting each sample with urea and allowing
sufficient time for degassing before analysis (see Sections 7.1 and 7.2).
3.3 Even after acid digestion, flame gases and organic compounds may
remain in the sample. Flame gases and organic compounds can absorb at the
analytical wavelengths and background correction should be used.
7742-1 Revision 0
September 1994
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4.0 APPARATUS AND MATERIALS
4.1 Electric hot plate: Large enough to hold at least several 100 mL
Pyrex digestion beakers.
4.2 A continuous-flow hydride generator: A commercially available
continuous-flow sodium borohydride/HCl hydride generator or a generator
constructed similarly to that shown in Figure 1 (P. S. Analytical or equivalent).
4.2.1 Peristaltic Pump: A four-channel, variable-speed peristaltic
pump to permit regulation of liquid-stream flow rates (Ismatec Reglo-100
or equivalent). Pump speed and tubing diameters should be adjusted to
provide the following flow rates: sample/blank flow = 4.2 mL/min;
borohydride flow = 2.1 mL/min.
4.2.2 Sampling Valve (optional): A sampling valve (found in the
P. S. Analytical Hydride Generation System or equivalent) that allows
switching between samples and blanks (rinse solution) without introduction
of air into the system will provide more signal stability.
4.2.3 Transfer Tubing and Connectors: Transfer tubing (1 mm I.D.),
mixing T's, and connectors are made of fluorocarbon (PFA or TFM) and are
of compatible sizes to form tight, leak-proof connections (Latchat,
Technicon, etc. flow injection apparatus accessories or equivalent).
4.2.4 Mixing Coil: A 20-turn coil made by wrapping transfer tubing
around a 1-cm diameter by 5-cm long plastic or glass rod (see Figure 1).
4.2.5 Mixing Coil Heater, if appropriate: A 250-mL Erlenmeyer
flask containing 100 mL of water heated to boiling on a dedicated one-
beaker hotplate (Corning PC-35 or equivalent). The mixing coil in 4.2.4
is immersed in the boiling water to speed kinetics of the hydride forming
reactions and increase solubility of interfering reduced metal
precipitates.
4.2.6 Gas-Liquid Separator: A glass apparatus for collecting and
separating liquid and gaseous products (P. S. Analytical accessory or
equivalent) which allows the liquid fraction to drain to waste and gaseous
products above the liquid to be swept by a regulated carrier gas (argon)
out of the cell for analysis. To avoid undue carrier gas dilution, the
gas volume above the liquid should not exceed 20 mL. See Figure 1 for an
acceptable separator shape.
4.2.7 Condenser: Moisture picked up by the carrier gas must be
removed before encountering the hot absorbance cell. The moist carrier
gas with the hydrides is dried by passing the gasses through a small (< 25
mL) volume condenser coil (Ace Glass Model 6020-02 or equivalent) that is
cooled to 5°C by a water chiller (Neslab RTE-110 or equivalent). Cool tap-
water in place of a chiller is acceptable.
7742-2 Revision 0
September 1994
-------
4.2.8 Flow Meter/Regulator: A meter capable of regulating up to 1
L/min of argon carrier gas is recommended.
4.3 Absorbance Cell: A 17-cm or longer quartz tube T-cell (windowless is
strongly suggested) is recommended, as shown in Figure 1 (Varian Model VGA-76
accessory or equivalent). The cell is held in place by a holder that positions
the cell about 1 cm over a conventional AA air-acetylene burner head. In
operation, the cell is heated to around 900°C.
4.4 Atomic absorption spectrophotometer: Single- or dual- channel,
single- or double-beam instrument having a grating monochromator, photomultiplier
detector, adjustable slits, a wavelength range of 190 to 800 nm, and provisions
for interfacing with an appropriate recording device.
4.5 Burner: As recommended by the particular instrument manufacturer for
an air-acetylene flame. An appropriate mounting bracket attached to the burner
that suspends the quartz absorbance cell between 1 and 2 cm above the burner slot
is required.
4.6 Selenium hollow cathode lamp or selenium electrodeless discharge lamp
and power supply. Super-charged hollow-cathode lamps or EDL lamps are
recommended for maximum sensitivity.
4.7 Strip-chart recorder (optional): Connect to output of
spectrophotometer.
5.0 REAGENTS
5.1 Reagent water : Water must be monitored for impurities. Refer to
Chapter 1 for definition of Reagent water.
5.2 Concentrated nitric acid (HN03): Acid must be analyzed to determine
levels of impurities. If a method blank is
-------
QUARTZ CELL
A A OURNER
TO
CHILLER
'•01SCONNECTE
OUR INO S*X8n
. ntlOLVStS
OASXLIOUIO
SEPARATOR
__—# DRAIN
20 TURN COIL
(TEFLON)
HOTPLATE
VALVE .
(•LANK)
Figure 1. Continuous-flow sodium borohydride/hydride generator apparatus setup
and an AAS sample introduction system
7742-4
Revision 0
September 1994
-------
5.7 4% Sodium Borohydride (NaBHJ: A 4 % sodium borohydride solution (20
g reagent-grade NaBH4 plus 2 g sodium hydroxide dissolved in 500 mL of reagent
water) must be prepared for conversion of the selenium to its hydride.
5.8 Selenium solutions:
5.8.1 Selenium standard stock solution (1,000 mg/L): Either
procure certified aqueous standards from a supplier and verify by
comparison with a second standard, or dissolve 0.3453 g of selenious acid
(assay 96.6% of H2Se03) in 200 ml of reagent water (1 ml = 1 mg Se).
5.8.2 Selenium working stock solution: Pi pet 1 ml selenium
standard stock solution into all volumetric flask and bring to volume
with reagent water containing 1.5 mL concentrated HN03/liter. The
concentration of this solution is 1 mg Se/L (1 ml = 1 fjq Se).
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
reagent water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used if very volatile selenium compounds are suspected
to be present in the samples.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric acid.
6.5 Nonaqueous samples shall be refrigerated, when possible, and analyzed
as soon as possible.
7.0 PROCEDURE
7.1 Place a 100-mL portion of an aqueous sample or extract or 1.000 g of
a dried solid sample in a 250-mL digestion beaker. Digest aqueous samples and
extracts according to Method 3010. Digest solid samples according to Method 3050
(furnace AA option) with the following modifications: add 5 mL of concentrated
hydrochloric acid just prior to the final volume reduction stage to aid in
conversion of selenium to its plus four state; the final volume reduction should
be to less than 5 mL but not to dryness to adequately remove excess hydrogen
peroxide (see note). After dilution to volume, further dilution with diluent may
be necessary if the analyte is known to exceed 750 /jg/L or if interferents are
expected to exceed a total of 1000 mg/L in the digestate.
Note: For solid digestions, the volume reduction stage is critical
to obtain accurate data. Close monitoring of each sample is
necessary when this critical stage in the digestion is reached.
7742-5 Revision 0
September 1994
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7.2 Prepare samples for hydride analysis by adding 1.00 g urea, and 20 mL
concentrated HC1 to a 5.00 ml aliquot of digested sample in a 50-mL volumetric
flask. Heat in a water bath to dissolve salts and reduce selenium (at least 30
minutes is suggested). Bring flask to volume with reagent water before
analyzing. A ten-fold dilution correction must be made in the final
concentration calculations.
7.3 Prepare working standards from the standard stock selenium solution.
Transfer 0, 0.5, 1.0, 1.5, 2.0, and 2.5 ml of standard to 100-mL volumetric
flasks and bring to volume with diluent. These concentrations will be 0, 5, 10,
15, 20, and 25/yg Se/L.
7.4 If EP extracts (Method 1310) are being analyzed for selenium, the
method of standard additions must be used. Spike appropriate amounts of working
standard selenium solution to three 25 ml aliquots of each unknown. Spiking
volumes should be kept less than 0.250 ml to avoid excessive spiking dilution
errors.
7.5 Set up instrumentation and hydride generation apparatus and fill
reagent containers. The sample and blank flows should be set around 4.2 mL/min,
and the borohydride flow around 2.1 mL/min. The argon carrier gas flow is
adjusted to about 200 mL/min. For the AA, use the 196.0-nm wavelength and 2.0-nm
slit width (or manufacturer's recommended slit-width) with background correction.
Begin all flows and allow the instrument to warm-up according to the instrument
manufacturer's instructions.
7.6 Place sample feed line into a prepared sample solution and start pump
to begin hydride generation. Wait for a maximum steady-state signal on the
strip-chart recorder. Switch to blank sample and watch for signal to decline to
baseline before switching to the next sample and beginning the next analysis.
Run standards first (low to high), then unknowns. Include appropriate QA/QC
solutions, as required. Prepare calibration curves and convert absorbances to
concentration. See following analytical flowchart.
CAUTION: The hydride of selenium is very toxic. Precautions must be taken
to avoid inhaling the gas.
7.7 If the method of standard additions was employed, plot the measured
concentration of the spiked samples and unspiked sample versus the spiked
concentrations. The spiked concentration axis intercept will be the method of
standard additions concentration. If the plot does not result in a straight
line, a nonlinear interference is present. This problem can sometimes be
overcome by dilution or addition of other reagents if there is some knowledge
about the waste. If the method of standard additions was not required, then the
concentration is determined from a standard calibration curve.
8.0 QUALITY CONTROL
8.1 Refer to Section 8.0 of Method 7000.
7742-6 Revision 0
September 1994
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9.0 METHOD PERFORMANCE
9.1 The relative standard deviation obtained by a single laboratory for
7 replicates of a contaminated soil was 18% for selenium at 8.2 ug/L in solution.
The average percent recovery of the analysis of an 2 jjg/L spike on ten different
samples is 100.5% for selenium.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 206.3.
2. "Evaluation of Hydride Atomic Absorption Methods for Antimony, Arsenic,
Selenium, and Tin", an EMSL-LV internal report under Contract 68-03-3249,
Job Order 70.16, prepared for T. A. Hinners by D. E. Dobb, and J. D.
Lindner of Lockheed Engineering and Sciences Co., and L. V. Beach of the
Varian Corporation.
7742-7 Revision 0
September 1994
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METHOD 7742
SELENIUM (ATOMIC ABSORPTION, BOROHYDRIDE REDUCTION)
7.1 Use Method
3050 (furnace AA
option) to digest
1.0 g sample.
7.1 - 7.4
Digest with
H203as
described in
Method 3050.
7.5 Add
concentrated
HCI.
7.6 Do final
volume
reduction and
dilution, as
described.
7.1 Further
dilute with
diluent.
7.1 Use
Method 3010
to digest 100
ml sample.
7.2 Add urea
and cone. HCI to
aliquot; heat in
H20 bath;
bring to volume.
7.3 Prepare
working
standards from
standard stock
Se solution.
7.4 Use the
method of
standard
additions on
extracts, only.
7.4 Spike 3
aliquote with
working
standard Se
solution.
7.5 -7.6 Analyze
the sample
using hydride
generation
apparatus.
7.5 - 7.6 Analyze
the sample
using hydride
generation
apparatus.
7.7 Determine
Se
concentrations
from linear
plot.
7.7 Determine
Se cone, from
standard
calibration
curve.
Stop
7742-8
Revision 0
September 1994
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METHOD 7760A
SILVER (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 Method 7760 is an atomic absorption procedure approved for determining
the concentration of silver (CAS Registry Number 7440-22-4) in wastes, mobility
procedure extracts, soils, and ground water. All samples must be subjected to an
appropriate dissolution step prior to analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis by Method 7760, samples must be prepared for direct
aspiration. The method of sample preparation will vary according to the sample
matrix. Aqueous samples are subjected to the acid-digestion procedure described
in this method.
2.2 Following the appropriate dissolution of the sample, a representative
aliquot is aspirated into an air/acetylene flame. The resulting absorption of
hollow cathode radiation will be proportional to the silver concentration.
Background correction must be employed for all analyses.
2.3 The typical detection limit for this method is 0.01 mg/L; typical
sensitivity is 0.06 mg/L.
3.0 INTERFERENCES
3.1 Background correction is required because nonspecific absorption and
light scattering may occur at the analytical wavelength.
3.2 Silver nitrate solutions are light-sensitive and have the tendency to
plate out on container walls. Thus silver standards should be stored in brown
bottles.
3.3 Silver chloride is insoluble; therefore, hydrochloric acid should be
avoided unless the silver is already in solution as a chloride complex.
3.4 Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.
4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer: Single-or dual-channel, single-
or double-beam instrument with a grating monochromator, photomultiplier detector,
adjustable slits, and provisions for background correction.
4.2 Silver hollow cathode lamp.
7760A - 1 Revision 1
July 1992
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4.3 Strip-chart recorder (optional).
4.4 Graduated cylinder or equivalent.
4.5 Hot plate or equivalent - adjustable and capable of maintaining a
temperature of 90-95°C.
4.6 Ribbed watchglasses 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.
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 Nitric Acid (concentrated), HN03.
5.4 Ammonium Hydroxide (concentrated), NH4OH.
5.5 Silver Stock Standard Solution (1,000 mg/L), AgN03. Dissolve 0.7874
g anhydrous silver nitrate in water. Add 5 ml HNO, and bring to volume in a 500-
mL volumetric flask (1 ml = 1 mg Ag). Alternatively, procure a certified aqueous
standard from a supplier and verify by comparison with a second standard.
5.6 Silver working standards - These standards should be prepared from
silver stock solution to be used as calibration standards at the time of
analysis. These standards should be prepared with nitric acid and at the same
concentrations as the analytical solution.
5.7 Iodine solution (IN). Dissolve 20 g potassium iodide (KI), in 50 ml
of water. Add 12.7 g iodine (I2) and dilute to 100 ml. Store in a brown bottle.
5.8 Cyanogen iodide solution. Add 4.0 ml ammonium hydroxide, 6.5 g
potassium cyanide (KCN), and 5.0 ml of iodine solution to 50 ml of water. Mix and
dilute to 100 ml with water. Do not keep longer than 2 weeks.
CAUTION: This reagent cannot be mixed with any acid solutions because
toxic hydrogen cyanide will be produced.
5.9 Air.
5.10 Acetylene.
7760A - 2 Revision 1
July 1992
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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
reagent water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH < 2 with nitric acid.
6.4 When possible, standards and samples should be stored in the dark and
in brown bottles.
6.5 Nonaqueous samples shall be refrigerated, when possible, and analyzed
as soon as possible.
7.0 PROCEDURE
7.1 Sample preparation - Aqueous samples should be prepared according to
Steps 7.2 and 7.3. The applicability of a sample preparation technique to a new
matrix type must be demonstrated by analyzing spiked samples and/or relevant
standard reference materials.
7.2 Preparation of aqueous samples
7.2.1 Transfer a representative aliquot of the well-mixed sample to
a beaker and add 3 mL of concentrated HNO,. Cover the beaker with a ribbed
watch glass. Place the beaker on a hot plate and cautiously evaporate to
near dryness, making certain that the sample does not boil. DO NOT BAKE.
Cool the beaker and add another 3-mL portion of concentrated HN03. Cover
the beaker with a watch glass and return to the hot plate. Increase the
temperature of the hot plate so that a gentle reflux action occurs.
NOTE: If the sample contains thiosulfates, this step may result in
splatter of sample out of the beaker as the sample approaches
dryness. This has been reported to occur with certain photographic
types of samples.
7.2.2 Continue heating, adding additional acid, as necessary, until
the digestion is complete (generally indicated when the digestate is light
in color or does not change in appearance with continued refluxing).
Again, evaporate to near dryness and cool the beaker. Add a small quantity
of HN03 so that the final dilution contains 0.5% (v/v) HN03 and warm the
beaker to dissolve any precipitate or residue resulting from evaporation.
7.2.3 Wash down the beaker walls and watch glass with water and,
when necessary, filter the sample to remove silicates and other insoluble
material that could clog the nebulizer. Adjust the volume to some
predetermined value based on the expected metal concentrations. The sample
is now ready for analysis.
7760A - 3 Revision 1
July 1992
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7.3 If plating out of AgCl is suspected, the precipitate can be
redissolved by adding cyanogen iodide to the sample. This can be done only after
digestion and after neutralization of the sample to a pH > 7 to prevent formation
of toxic cyanide under acid conditions. In this case do not adjust the sample
volume to the predetermined value until the sample has been neutralized to pH >
7 and cyanogen iodide has been added. If cyanogen iodide addition to the sample
is necessary, then the standards must be treated in the same manner. Cyanogen
iodide must not be added to the acidified silver standards. New standards must
be made, as directed in Steps 5.5 and 5.6, except that the acid addition step
must be omitted. For example, to obtain a 100 mg/L working standard, transfer 10
ml of stock solution to a small beaker. Add water to make about 70 ml. Make the
solution basic (pH above 7) with ammonium hydroxide. Rinse the pH meter
electrodes into the solution with water. Add 1 ml cyanogen iodide and allow to
stand 1 hour. Transfer quantitatively to a 100-mL volumetric flask and bring to
volume with water.
CAUTION; CNI reagent can be added only after digestion to prevent
formation of toxic cyanide under acidic conditions. CNI
reagent must not be added to the acidified silver standards.
NOTE: Once the sample or sample aliquot has been treated with the
CNI reagent and diluted per instruction, the solution has a
cyanide concentration of approximately 260 mg/L. A solution of
that cyanide concentration must be considered a potential
hazardous waste and must be disposed of using an approved
safety plan in accordance with local authority requirements.
Until such time that a detailed disposal plan can be fully
documented and approved, the use of the CNI reagent should be
avoided.
7.4 The 328.1 nm wavelength line and background correction shall be
employed.
7.5 An oxidizing air-acetylene flame shall be used.
7.6 Follow the manufacturer's operating instructions for all other
spectrophotometer parameters.
8.0 QUALITY CONTROL
8.1 Refer to section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 272.1 of "Methods
for Chemical Analysis of Water and Wastes."
9.2 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
7760A - 4 Revision 1
July 1992
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10.0 REFERENCES
1. Methods for 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 Center for Environmental
Research Information: Cincinnati, OH, 1983; EPA-600/4-79-020.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, December 1987.
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"; ATSM: Philadelphia, PA, 1985; D1193-77.
7760A - 5 Revision 1
July 1992
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TABLE 1.
METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Wastewater treatment sludge 3050 2.3, 1.6 mg/Kg
Emission control dust 3050 1.8, 4.2 mg/Kg
i
i
7760A - 6 Revision 1
July 1992
-------
METHOD 7760A
SILVER (ATOMIC ABSORPTION, DIRECT ASPIRATION)
721 Transfer
sample aliquot to
beaker,add cone
HNO,,evaporate to
near dryness,cool,
add cone HNO,,heat
so gentle reflux
action occurs
7.2.2 Compl.t.
digeilion,«vaporate
to near drjrna»» ,
cool,add cone HNOB,
warm to di«*olv«
any pracipitat* or
r»idu*
7.2 3 Filter sample
if necessary,adjust
volume with water
7.3 Neutralize
sample,add cyanogen
iodide to dissolve
precipitate,remake
standards omitting
acid,transfer
aliquot of stock
solution to beaker,
add water
7.1 Prepare sample
according to Method
3040
7 1 Prepare sample
according to Method
3050
7.3 Adjust pH with
NH,OH.rinse
electrode into
solution with
water,add cyanogen
iodide,wait 1
hour,transfer to
flask,bring to
volume with water
7.4-7.6 Set
instrument
parameters
7.7 Construct
calibration curve
7.8 Analy2e by
•thod of standard
addition if
necessary
7 9 Calculate metal
concentration
Stop
7760A - 7
Revision 1
July 1992
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METHOD 7761
SILVER (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 Method 7761 is an atomic absorption procedure approved for
determining the concentration of silver in wastes, mobility procedure extracts,
soils, and ground water. All samples must be subjected to an appropriate
dissolution procedure.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 In addition to the normal interferences experienced during graphite
furnace analysis, silver analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix components during atomization.
Simultaneous background correction must be employed to avoid erroneously high
results.
3.3 If the analyte is not completely volatilized and removed from the
furnace during atomization, memory effects will occur. If this situation is
detected, the tube should be cleaned by operating the furnace at higher
atomization temperatures.
3.4 Silver nitrate solutions are light sensitive and have the tendency
to plate out on container walls. Thus, silver standards should be stored in
brown bottles.
3.5 Silver chloride is insoluble; therefore, hydrochloric acid should be
avoided unless the silver is already in solution as a chloride complex.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 400°C.
4.2.3 Atomizing Time and Temp: 10 sec at 2700°C.
7761 - 1 Revision 0
July 1992
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4.2.4 Purge Gas Atmosphere: Argon.
4.2.5 Wavelength: 328.1 nm.
4.2.6 Background Correction: Required.
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 non-pyrolytic
graphite and are to be used as guidelines only. 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 Silver Stock Standard Solution (1,000 mg/L), AgN03. Dissolve 0.7874 g
anhydrous silver nitrate (AgN03), analytical reagent grade, water. Add 5 ml
concentrated nitric acid (HN03) and bring to volume in a 500 ml volumetric flask
(1 mL = 1 mg Ag). Alternatively, procure a certified standard from a supplier
and verify by comparison with a second standard.
5.3 Silver working standards - These standards should be prepared with
nitric acid such that the final acid concentration is 0.5% (v/v) HN03.
5.4 Ammonium hydroxide (concentrated), (NH4OH). Base should be analyzed
to determine levels of impurities. If impurities are detected, all analyses
should be blank-corrected.
5.5 Iodine solution (IN). Dissolve 20 g potassium iodide (KI), analytical
reagent grade, in 50 ml water. Add 12.7 g iodine (I2), analytical reagent grade,
and dilute to 100 ml with water. Store in a brown bottle.
5.6 Cyanogen iodide solution. To 50 ml water add 4.0 ml concentrated
NH,OH, 6.5 g potassium cyanide (KCN), and 5.0 mL of iodine solution. Mix and
dilute to 100 ml with water. Do not keep longer than 2 weeks.
CAUTION: This reagent cannot be mixed with any acid solutions since
highly toxic hydrogen cyanide will be produced.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Step 3.1.3, Sample Handling and Preservation.
7761 - 2 Revision 0
July 1992
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6.2 Standards and samples should be stored in the dark, in brown bottles,
and refrigerated.
7.0 PROCEDURE
7.1 Sample preparation - Aqueous samples should be prepared according to
Steps 7.2 and 7.3. The applicability of a sample preparation technique to a new
matrix type must be demonstrated by analyzing spiked samples and/or relevant
standard reference materials.
7.2 Preparation of aqueous samples
7.2.1 Transfer a representative aliquot of the well-mixed sample to
a beaker and add 3 ml of concentrated HN03. Cover the beaker with a watch
glass. Place the beaker on the hot plate and cautiously evaporate to near
dryness, making certain that the sample does not boil. DO NOT BAKE. Cool
the beaker and add another 3-mL portion of concentrated HN03. Cover the
beaker with a watch glass and return to the hot plate. Increase the
temperature of the hot plate so that a gentle reflux action occurs.
NOTE: If the sample contains thiosulfates, this step may result in
splatter of sample out of the beaker as the sample approaches
dryness. This has been reported to occur with certain types
of photographic wastes.
7.2.2 Continue heating, adding additional acid, as necessary, until
the digestion is complete (generally indicated when the digestate is light
in color or does not change in appearance with continued refluxing).
Again, evaporate to near dryness and cool the beaker. Add a small
quantity of HN03 so that the final dilution contains 0.5% (v/v) HN03 and
warm the beaker to dissolve any precipitate or residue resulting from
evaporation.
7.2.3 Wash down the beaker walls and watch glass with water and,
when necessary, filter the sample to remove silicates and other insoluble
material that could clog the nebulizer. Adjust the volume to some
predetermined value based on the expected metal concentrations. The sample
is now ready for analysis.
7.3 If plating out of AgCl is suspected, the precipitate can be
redissolved by adding cyanogen iodide to the sample. This can be done only after
digestion and after neutralization of the sample to a pH > 7 to prevent formation
of toxic cyanide under acid conditions. In this case, do not adjust the sample
volume to the predetermined value until the sample has been neutralized to pH >
7 and cyanogen iodide has been added. If cyanogen iodide addition to the sample
is necessary, then the standards must be treated in the same manner. Cyanogen
iodide must not be added to the acidified silver standards. New standards must
be made, as directed in Step 5.2, except that the acid addition step must be
omitted. For example, to obtain a 100 mg/L working standard, transfer 10 ml of
stock solution to a small beaker. Add water to make about 70 ml. Make the
solution basic (pH above 7) with NH4OH. Rinse the pH meter electrodes into the
7761 - 3 Revision 0
July 1992
-------
solution with water. Add 1 ml cyanogen iodide and allow to stand 1 hour.
Transfer quantitatively to a 100-mL volumetric flask and bring to volume with
water.
CAUTION: CNI reagent can be added only after digestion to prevent
formation of toxic cyanide under acidic conditions. CNI
reagent must not be added to the acidified silver standards.
NOTE: Once the sample or sample aliquot has been treated with the CNI reagent
and diluted per instruction, the solution has a cyanide concentration of
approximately 260 mg/L. A solution of that cyanide concentration must be
considered a potential hazardous waste and must be disposed of using an
approved safety plan in accordance with local authority requirements.
Until such time that a detailed disposal plan can be fully documented and
approved, the use of the CNI reagent should be avoided.
7.4 The 328.1-nm wavelength line and background correction shall be used.
7.5 Following the manufacturer's operating instructions for all other
spectrophotometer parameters.
7.6 Furnace parameters suggested by the manufacturer should be employed
as guidelines. Since temperature-sensing mechanisms and temperature controllers
can vary between instruments or with time, the validity of the furnace parameters
must be periodically confirmed by systematically altering the furnace parameters
while analyzing a standard. In this manner, losses of analyte due to higher than
necessary temperature settings or losses in sensitivity due to less than optimum
settings can be minimized. Similar verification of furnace parameters may be
required for complex sample matrices.
7.7 Inject a measured uL aliquot of sample into the furnace and atomize.
If the concentration found is greater than the highest standard, the sample
should be diluted in the same acid matrix and reanalyzed. The use of multiple
injections can improve accuracy and help detect furnace pipetting errors.
7.8 Either (1) run a series of silver standards and construct a
calibration curve by plotting the concentrations of the standards against the
absorbances or (2) for the method of standard additions, plot added concentration
versus abosrbance. For instruments that read directly in concentration, set the
curve corrector to read out the proper concentration.
7.9 Analyze, by the method of standard additions, all EP extracts, all
samples analyzed as part of a delisting petition, and all samples that suffer
from matrix interferences.
7.10 Calculate metal concentrations by (1) the method of standard
additions, or (2) from a calibration curve, or (3) directly from the instrument's
concentration readout. All dilution or concentration factors must be taken into
account. Concentrations reported for multiphased samples must be appropriately
qualified.
7761 - 4 Revision 0
July 1992
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8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection.
8.2 Calibration curves must be composed of a minimum of a calibration
blank and three standards. A calibration curve must be prepared each day.
8.3 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one reagent blank per sample batch or every 20
samples to determine if contamination or any memory effects are occurring.
8.5 Verify calibration with an independently prepared quality control
reference sample every 10 samples.
8.6 Run one spiked replicate sample for every 10 samples or per
analytical batch, whichever is more frequent. A replicate sample is a sample
brought through the entire sample preparation process.
8.7 Duplicates, spiked samples, and check standards should be routinely
analyzed. Refer to Chapter One for the proper protocol.
8.8 The method of standard additions (see Method 7000, Step 8.7) shall
be used for the analysis of all EP extracts, on all analyses submitted as part
of a delisting petition, and whenever a new sample matrix is being analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 272.2 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 1-25 ug/L.
Detection limit: 0.2 ug/L.
10.0 REFERENCES
1. Methods for 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 Center for Environmental
Research Information: Cincinnati, OH, 1983; EPA-600/4-79-020.
7761 - 5 Revision 0
July 1992
-------
METHOD 7761
SILVER (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
7.1 Must
demonstrate
applicability of
preparation
technique to other
matrix types by
analyzing spiked
samples and
reference material*
7.2.1 Transfer
•ample aliquot to
beaker; add cone.
HNOi; evaporate to
near dryness; cool;
add cone. HNO,;
heat to gentle
reflux action
occur*
7.2.2 Complete
digestion;
evaporate to near
dryneas; cool; add
cone. HNOi; warm to
dissolve any
precipitate or
residue
Ye*
7 2.3 Filter temple
if necessary;
adjust volume with
water
7.3 Neutralize
(ample; add cyanogen
iodide to dissolve
precipitate; remake
»tandard* omitting
acid; transfer
aliquot of stoek
solution to beaker;
add water
7.3 Adjust pH with
NH.OH; rinse
electrodes into
soln with water;
add cyanogen
iodide; wait 1
hour; transfer to
flask; bring to
volume with water
7.4-7.6 Sat
instrument
parameters
7.7 Inject sample
aliquot; dilute if
necessary
7.8 Construct
calibration curve
i
7.9-7.10 Analyze
sample
7.10 Calculate
•tal concentration
Stop
7761 - 6
Revision 0
July 1992
-------
METHOD 7770
SODIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 lonlzation interferences can affect analysis for sodium; therefore,
samples and standards must be matrix matched or an ionization suppressant
employed.
3.3 Sodium is a universal contaminant, and great care should be taken to
avoid contamination.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Sodium hollow cathode lamp.
4.2.2 Wavelength: 589.6 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 2.542 g sodium chloride, NaCl
(analytical reagent grade), in Type II water, acidify with 10 mL
redistilled HN03, and dilute to 1 liter with Type II water.
Alternatively, procure a certified standard from a supplier and verify by
comparison with a second standard.
7770 - 1
Revision 0
Date September 1986
-------
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 add and at the same
concentration as will result 1n the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.03-1 mg/L with a wavelength of 589.6 nm.
Sensitivity: 0.015 mg/L.
Detection limit: 0.002 mg/L.
9.2 In a single laboratory, analysis of a mixed Industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 8.2 and 52
mg/L gave standard deviations of +0.1 and +0.8, respectively. Recoveries at
these levels were 102% and 100%, respectively.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 273.1.
7770 - 2
Revision
Date September 1986
-------
METHOD 7770
SODIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standards
7. 1
For
sample
preparation see
chapter 3.
section 3.2
7.2
Analyze using
Method 7000.
Section 7.3
f Stop J
7770 - 3
Revision 0
Date September 1986
-------
METHOD 7780
STRONTIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000.
3.2 Chemical interference caused by silicon, aluminum, and phosphate are
controlled by adding lanthanum chloride. Potassium chloride is added to suppress
the ionization of strontium. All samples and standards should contain 1 ml of
lanthanum chloride/potassium chloride solution (Step 5.3) per 10 ml of solution.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Strontium hollow cathode lamp.
4.2.2 Wavelength: 460.7 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxidant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards
7780 - 1 Revision 0
July 1992
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5.2.1 Stock solution: (1.0 ml = 1.0 mg Sr). Dissolve 2.415 g of
strontium nitrate, Sr(N03)2, in 10 ml of concentrated HC1 and 700 ml of
water. Dilute to 1 liter with water. Alternatively, procure a certified
standard from a supplier and verify 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 as the samples and cover
the range of expected concentrations in the samples. Calibration standards
should also contain 1 ml of lanthanum chloride/potassium chloride solution
per 10 ml.
5.3 Lanthanum Chloride/Potassium Chloride Solution. Dissolve 11.73 g of
lanthanum oxide, La203, in a minimum amount of concentrated hydrochloric acid
(approximately 50 ml). Add 1.91 g of potassium chloride, KC1. Allow solution to
cool to room temperature and dilute to 100 ml with water.
CAUTION: REACTION IS VIOLENT! Add acid slowly and in small portions to
control the reaction rate upon mixing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Step 3.1.3, Sample Handling and Preservation.
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 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 0.3 - 5 mg/L at a wavelength of 460.7 nm.
Sensitivity: 0.15 mg/L.
Detection limit: 0.03 mg/L.
9.1.1 Recoveries of known amounts of strontium in a series of
prepared standards were as given in Table 1.
7780 - 2 Revision 0
July 1992
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10.0 REFERENCES
1. Annual Book of ASTM Standards; ASTM; Philadelphia, PA, 1983; D3920.
7780 - 3 Revision 0
July 1992
-------
TABLE 1.
RECOVERY
Amount
added,
mg/L
Amount
found ,
mg/L
Significant
(95 %
% confidence
Bias Bias level)
1.00
0.50
0.10
Reagent Water Type II
0.998 -0.002 -0.2
0.503 -1-0.003 +0.6
0.102 +0.002 +2
Water of Choice
no
no
no
1.00
0.50
0.10
1.03
0.504
0.086
+0.03
+0.004
-0.014
+ 3
+ 0.8
-14
no
no
no
Reference:
Annual Book of ASTM Standards; ASTM: Philadelphia, PA,
1983; D3920.
7780 - 4
Revision 0
July 1992
-------
METHOD 7780
STRONTIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
Start
S.0 Prepare
standard*
7.1 For lanple
preparation • ••
Chapter 3, Section
3.2
7.2 Analyze u»ing
Method 7000
Section 7.2
Stop
7780 - 5
Revision 0
July 1992
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METHOD 7840
THALLIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Background correction is required.
3.3 Hydrochloric add should not be used.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Thallium hollow cathode lamp.
4.2.2 Wavelength: 276.8 nnt.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.303 g thallium nitrate, T1N03
(analytical reagent grade), in Type II water, acidify with 10 mL
concentrated HN03, and dilute to 1 liter with Type II water. Alterna-
tively, procure a certified standard from a supplier and verify by
comparison with a second standard.
7840 - 1
Revision
Date September 1986
-------
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
concentration as will result 1n the sample to be analyzed after
processing (0.5% v/v
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 1-20 mg/L with a wavelength of 276.8 nm.
Sensitivity: 0.5 mg/L.
Detection limit: 0.1 mg/L.
9.2 In a single laboratory, analysis of a mixed Industrial -domestic
waste effluent, digested with Method 3010, at concentrations of 0.6, 3, and 15
mg/L gave standard deviations of +0.018, +0.05, and +0.2, respectively.
Recoveries at these levels were 100%, 98%, and~98%, respectively.
9.3 For concentrations of thallium below 0.2 mg/L, the furnace technique
(Method 7841) is recommended.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 279.1.
7840 - 2
Revision
Date September 1986
-------
METHOD 7840
THALLIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standards
7. 1
prepar
cl-
sec
For
sample
•atlorv see
\apter 3.
:tion 3.2
7.2
Analyze using
Method 70OO.
Section 7.2
f Stop J
7840 - 3
Revision 0
Date September 1986
-------
METHOD 7841
THALLIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Background correction 1s required.
3.3 Hydrochloric add or excessive chloride will cause volatilization of
thallium at low temperatures. Verification that losses are not occurring, by
spiked samples or standard additions, must be made for each sample matrix.
3.4 Palladium is a suitable matrix modifier for thallium analysis.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 400*C.
4.2.3 Atomizing time and temp: 10 sec at 2400*C.
4.2.4 Purge gas: Argon or nitrogen.
4.2.5 Wavelength: 276.8 nm.
4.2.6 Background correction: Required.
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
sizes of 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.
7841 - 1
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.303 g thallium nitrate, T1N03
(analytical reagent grade), 1n Type II water, acidify with 10 ml
concentrated HNOs, and dilute to 1 liter with Type II water. Alterna-
tively, procure a certified standard from a supplier and verify 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
concentrations as 1n the sample after processing (0.5% v/v
5.3 Palladium chloride: Weigh 0.25 g of PdCl2 to the nearest 0.0001 g.
Dissolve 1n 10 ml of 1:1 HNOs and dilute to 1 liter with Type II water. Use
equal volumes of sample and palladium solution.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
1s given 1n Method 7000, Paragraph 7.4.
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.
9.2 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 5-100 ug/L.
Detection limit: 1 ug/L.
7841 - 2
Revision
Date September 1986
-------
10.0 REFERENCES
1. Application of Matrix-Modification 1n Determination of Thallium in
Wastewater by Graphite-Furnace Atomic-Absorption Spectrometry, Talanta, 31(2)
(1984), pp. 150-152.
7841 - 3
Revision
Date September 1986
-------
METHOD 7841
THALLIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
5.0
Prepare
standards
7. 1
prepar
ct-
sec
7.2
For
sample
atlon see
apter 3.
tlon 3.2
Analyze using
Method 700O.
Section 7.2:
Calculation 7.4
f Stop J
7841 - 4
Revision 0
Date September 1986
-------
METHOD 7870
TIN (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Tin hollow cathode lamp.
4.2.2 Wavelength: 286.3 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxidant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5«2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g of tin metal (analytical
reagent grade) in 100 mL of concentrated HC1 and dilute to 1 liter with
Type II water. Alternatively, procure a certified standard from a
supplier and verify 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
concentration as will result in the sample to be analyzed after
processing.
7870 - 1
Revision
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 10-300 mg/L with a wavelength of 286.3 nm.
Sensitivity: 4 mg/L.
Detection limit: 0.8 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 4, 20, and 60
mg/L gave standard deviations of +0.25, +0.5, and +0.5, respectively.
Recoveries at these levels were 96%, 101%, and 101%, respectively.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 282.1.
7870 - 2
Revision
Date September 1986
-------
METHOD 7B7O
TIN (ATOMIC ABSORPTION. DIRECT ASPIRATION)
s.
O
Prepare
standards
7.1
1 For
sample
preparation see
chapter 3.
section 3.2
7.2
Analyze using
Method 7000.
Section 7.2
f Stop J
7870 - 3
Revision 0
Date September 1986
-------
METHOD 7910
VANADIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Background correction may be required.
3.3 High concentrations of aluminum or titanium, or the presence of Bi,
Cr, Co, Fe, acetic acid, phosphoric acid, surfactants, detergents, or alkali
metals, may interfere. The interference can be controlled by adding
1,000 mg/L aluminum to samples and standards.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Vanadium hollow cathode lamp.
4.2.2 Wavelength: 318.4 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.7854 g of vanadium pentoxide,
¥205 (analytical reagent grade), in 10 mL of concentrated nitric acid and
dilute to 1 liter with Type II water. Alternatively, procure a certified
standard from a supplier and verify by comparison with a second standard.
7910 - 1
Revision
Date September 1986
-------
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 add and at the same
concentration as will result 1n the sample to be analyzed after
processing. In addition, 2 ml of the aluminum nitrate solution described
In Paragraph 5.2.3 should be added to each 100 ml of standards and
samples.
5.2.3 Aluminum nitrate solution: Dissolve 139 g aluminum nitrate
(A1[N03]3«9H20) In 150 ml Type II water; heat to complete dissolution.
Allow to cool and dilute to 200 ml with Type II water. All samples and
standards should contain 2 ml of this solution per 100 ml.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 2-100 mg/L with a wavelength of 318.4 nm.
Sensitivity: 0.8 mg/L.
Detection limit: 0.2 mg/L.
9.2 In a single laboratory), analysis of a mixed Industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 2, 10, and 50
mg/L gave standard deviations of +0.1, +0.1, and +0.2, respectively.
Recoveries at these levels were 100%, 95%, and 97%, respectively.
9.3 For concentrations of vanadium below 0.5 mg/L, the furnace technique
(Method 7911) 1s recommended.
7910 - 2
Revision
Date September 1986
-------
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 286.1.
7910 - 3
Revision
Date September 1986
-------
METHOD 791O
VANADIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
s.o
Prepare
standards
7.1
prepar
ch
sec
For
sample
atlon see
apter 3.
tlon 3. a
7.2
Analyze using
Method 7000.
Section 7.Z
( Stop J
7910
Revision 0
Date September 1986
-------
METHOD 7911
VANADIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Background correction is required.
3.3 Vanadium is refractory and prone to form carbides. Consequently,
memory effects are common, and care should be taken to clean the furnace
before and after analysis.
3.4 Nitrogen should not be used as a purge gas.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 1400*C.
4.2.3 Atomizing time and temp: 15 sec at 2800*C.
4.2.4 Purge gas: Argon (nitrogen should not be used).
4.2.5 Wavelength: 318.4 nm.
4.2.6 Background correction: Required.
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
sizes of 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.
7911 - 1
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.7854 g of vanadium pentoxlde,
V2®5 (analytical reagent grade), 1n 10 mL of concentrated nitric add and
dilute to 1 liter with Type II water. Alternatively, procure a certified
standard from a supplier and verify 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
concentrations as in the sample after processing (0.5% v/v
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
is given in Method 7000, Paragraph 7.4.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 286.2 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The performance characteristics for an aqueous sample free of
interferences are;
Optimum concentration range: 10-200 ug/L.
Detection limit: 4 ug/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 286.2.
7911 - 2
Revision 0
Date September 1986
-------
METHOD 7911
VANADIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
5.O
Prepare
standards
7. 1
f
• I
preparat
chat
sect!
•or
imple
.Ion see
>ter 3.
ion .3.2
7.2 |
Analyze using
Method 70OO.
Section 7.2:
calculation 7.4
f Stop J
7911 - 3
Revision 0
Date September 1986
-------
METHOD 7950
ZINC (ATOMIC ABSORPTION, DIRECT ASPIRATION)
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 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 High levels of silicon, copper, or phosphate may interfere. Addi-
tion of strontium (1,500 mg/L) removes the copper and phosphate interference.
3.3 Zinc is a universal contaminant, and great care should be taken to
avoid contamination.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Zinc hollow cathode lamp.
4.2.2 Wavelength: 213.9 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g zinc metal (analytical
reagent grade) in 10 ml of concentrated nitric acid and dilute to 1 liter
with Type II water. Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
7950 - 1
Revision 0
Date September 1986
-------
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 concentra-
tion as will result in the sample to be analyzed after processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 0.05-1 mg/L with a wavelength of 213.9 nm.
Sensitivity: 0.02 mg/L.
Detection limit: 0.005 mg/L.
9.2 For concentrations of zinc below 0.01 mg/L, the furnace technique
(Method 7951) is recommended.
9.3 Precision and accuracy data are available in Method 289.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 289.1.
7950 - 2
Revision
Date September 1986
-------
METHOD 7950
ZINC (ATOMIC ABSORPTION. OIRCCT ASPIRATION)
5.0
Prepare
standards
7.1
For
sample
preparation see
chapter 3.
section 3.2
7 .Z
Analyze using
Method 7OOO.
Section 7.2
f Stop J
7950 - 3
Revision 0
Date September 1986
-------
METHOD 7951
ZINC (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
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 See Section 3.0 of Method 7000.
3.2 Background correction should be used.
3.3 Zinc is a universal contaminant. Because of this and the high
sensitivity of this method, great care should be taken to avoid contamination.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
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 400°C.
4.2.3 Atomizing time and temp: 10 sec at 2500°C.
4.2.4 Purge gas: Argon or nitrogen.
4.2.5 Wavelength: 213.9 nm.
4.2.6 Background correction: Required.
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
7951 - 1 Revision 0
July 1992
-------
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 - Dissolve 1.000 g zinc metal (analytical
reagent grade) in 10 mL of concentrated nitric acid and dilute to 1 liter
with water. Alternatively, procure a certified standard from a supplier
and verify 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
concentrations as in the sample after processing (0.5% v/v HN03).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Step 3.1.3, Sample Handling and Preservation.
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.
9.2 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 0.2-4 ug/L.
Detection limit: 0.05 ug/L.
7951 - 2 Revision 0
July 1992
-------
10.0 REFERENCES
1. Methods for 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 Center for Environmental
Research Information: Cincinnati, OH, 1983; EPA-600/4-79-020.
7951 - 3 Revision 0
July 1992
-------
METHOD 7951
ZINC (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
i
Start
5.0 Pr«par«
•tandard*
7.1 For «ampl«
preparation •••
Chapter 3, Section
3.2
7.2 Analyz* using
M.thod 7000
Section 7.3
Stop
7951 - 4
Revision 0
July 1992
-------
APPENDIX
COMPANY REFERENCES
The following listing of frequently-used addresses Is provided for the
convenience of users of this manual. No endorsement 1s Intended or Implied.
Ace Glass Company
1342 N.W. Boulevard
P.O. Box 688
Vlneland, NJ 08360
(609) 692-3333
Aldrlch Chemical Company
Department T
P.O. Box 355
Milwaukee, WI 53201
Alpha Products
5570 - T W. 70th Place
Chicago, IL 60638
(312) 586-9810
Barneby and Cheney Company
E. 8th Avenue and N. Cassldy Street
P.O. Box 2526
Columbus, OH 43219
(614) 258-9501
Bio - Rad Laboratories
2200 Wright Avenue
Richmond, CA 94804
(415) 234-4130
Burdick & Jackson Lab Inc.
1953 S. Harvey Street
Muskegon, MO 49442
Calgon Corporation
P.O. Box 717
Pittsburgh, PA 15230
(412) 777-8000
Conostan Division
Conoco Speciality Products, Inc.
P.O. Box 1267
Ponca City, OK 74601
(405) 767-3456
COMPANIES - 1
Revision
Date September 1986
-------
Corning Glass Works
Houghton Park
Corning, NY 14830
(315) 974-9000
Dohrmann, Division of Xertex Corporation
3240 - T Scott Boulevard
Santa Clara, CA 95050
(408) 727-6000
(800) 538-7708
E. M. Laboratories, Inc.
500 Executive Boulevard
Elmsford, NY 10523
Fisher Scientific Co.
203 Fisher Building
Pittsburgh, PA 15219
(412) 562-8300
General Electric Corporation
3135 Easton Turnpike
Fairfield, CT 06431
(203) 373-2211
Graham Manufactory Co., Inc.
20 Florence Avenue
Batavia, NY 14020
(716) 343-2216
Hamilton Industries
1316 18th Street
Two Rivers, WI 54241
(414) 793-1121
ICN Life Sciences Group
3300 Hyland Avenue
Costa Mesa, CA 92626
Johns - Manvllle Corporation
P.O. Box 5108
Denver, CO 80217
Kontes Glass Company
8000 Spruce Street
Vineland, NJ 08360
Millipore Corporation
80 Ashby Road
Bedford, MA 01730
(617) 275-9200
(800) 225-1380
COMPANIES - 2
Revision 0
Date September 1986
------- |